Department Water Resources and Drinking Water

Ozonation is increasingly applied in water and wastewater treatment for the abatement of micropollutants (MPs). However, the transformation products formed during ozonation (OTPs) and their fate in biological or sorptive post-treatments is largely unknown. In this project, a high-throughput approach, combining laboratory ozonation experiments and detection by liquid chromatography high-resolution mass spectrometry (LC-HR-MS/MS), was developed and applied to identify OTPs formed during ozonation of wastewater effluent for a large number of relevant MPs (total 87). For the laboratory ozonation experiments, a simplified experimental solution, consisting of surrogate organic matter (methanol and acetate), was created, which produced ozonation conditions similar to realistic conditions in terms of ozone and hydroxyl radical exposures. The 87 selected parent MPs were divided into 19 mixtures, which enabled the identification of OTPs with an optimized number of experiments. The following two approaches were considered to identify OTPs. (1) A screening of LC-HR-MS signal formation in these experiments was performed and revealed a list of 1749 potential OTP candidate signals associated to 70 parent MPs. This list can be used in future suspect screening studies. (2) A screening was performed for signals that were formed in both batch experiments and in samples of wastewater treatment plants (WWTPs). This second approach was ultimately more time-efficient and was applied to four different WWTPs with ozonation (specific ozone doses in the range 0.23-0.55 gO₃/gDOC), leading to the identification of 84 relevant OTPs of 40 parent MPs in wastewater effluent. Chemical structures could be proposed for 83 OTPs through the interpretation of MS/MS spectra and expert knowledge in ozone chemistry. Forty-eight OTPs (58%) have not been reported previously. The fate of the verified OTPs was studied in different post-treatment steps. During sand filtration, 87-89% of the OTPs were stable. In granular activated carbon (GAC) filters, OTPs were abated with decreasing efficiency with increasing run times of the filters. For example, in a GAC filter with 16,000 bed volumes, 53% of the OTPs were abated, while in a GAC filter with 35,000 bed volumes, 40% of the OTPs were abated. The highest abatement (87% of OTPs) was observed when 13 mg/L powdered activated carbon (PAC) was dosed onto a sand filter.

Organic micropollutants (MPs) are increasingly detected in water resources, which can be a concern for human health and the aquatic environment. Ultraviolet (UV) radiation based advanced oxidation processes (AOP) such as low-pressure mercury vapor arc lamp UV/H₂O₂ can be applied to abate these MPs. During UV/H₂O₂ treatment, MPs are abated primarily by photolysis and reactions with hydroxyl radicals (^•OH), which are produced in situ from H₂O₂ photolysis. Here, a model is presented that calculates the applied UV fluence (H_calc) and the ^•OH exposure (CT_•OH,calc ) from the abatement of two selected MPs, which act as internal probe compounds. Quantification of the UV fluence and hydroxyl radical exposure was generally accurate when a UV susceptible and a UV resistant probe compound were selected, and both were abated at least by 50 %, e.g., iopamidol and 5-methyl-1H-benzotriazole. Based on these key parameters a model was developed to predict the abatement of other MPs. The prediction of abatement was verified in various waters (sand filtrates of rivers Rhine and Wiese, and a tertiary wastewater effluent) and at different scales (laboratory experiments, pilot plant). The accuracy to predict the abatement of other MPs was typically within ±20 % of the respective measured abatement. The model was further assessed for its ability to estimate unknown rate constants for direct photolysis (k_UV,_MP) and reactions with ^•OH (k•_OH,_MP). In most cases, the estimated rate constants agreed well with published values, considering the uncertainty of kinetic data determined in laboratory experiments. A sensitivity analysis revealed that in typical water treatment applications, the precision of kinetic parameters (k_UV,_MP for UV susceptible and for UV resistant probe compounds) have the strongest impact on the model's accuracy.

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 UV_254. 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.

Hypochlorous acid (HOCl) is typically assumed to be the primary reactive species in free available chlorine (FAC) solutions. Lately, it has been shown that less abundant chlorine species such as chlorine monoxide (Cl₂O) and chlorine (Cl₂) can also influence the kinetics of the abatement of certain organic compounds during chlorination. In this study, the chlorination as well as bromination kinetics and mechanisms of 12 olefins (including 3 aliphatic and 9 aromatic olefins) with different structures were explored. HOCl shows a low reactivity towards the selected olefins with species-specific second-order rate constants <1.0 M⁻¹s⁻¹, about 4-6 orders of magnitude lower than those of Cl₂O and Cl₂. HOCl is the dominant chlorine species during chlorination of olefins under typical drinking water conditions, while Cl₂O and Cl₂ are likely to play important roles at high FAC concentration near circum-neutral pH (for Cl₂O) or at high Cl⁻ concentration under acidic conditions (for Cl₂). Bromination of the 12 olefins suggests that HOBr and Br₂O are the major reactive species at pH 7.5 with species-specific second-order rate constants of Br₂O nearly 3-4 orders of magnitude higher than of HOBr (ranging from <0.01 to >10³ M⁻¹s⁻¹). The reactivities of chlorine and bromine species towards olefins follow the order of HOCl < HOBr < Br₂O < Cl₂O ≈ Cl₂. Generally, electron-donating groups (e.g., CH₂OH- and CH₃-) enhances the reactivities of olefins towards chlorine and bromine species by a factor of 3-10², while electron-withdrawing groups (e.g., Cl-, Br-, NO₂-, COOH-, CHO-, -COOR, and CN-) reduce the reactivities by a factor of 3-10⁴. A reasonable linear free energy relationship (LFER) between the species-specific second-order rate constants of Br₂O or Cl₂O reactions with aromatic olefins and their Hammett σ⁺ was established with a more negative ρ value for Br₂O than for Cl₂O, indicating that Br₂O is more sensitive to substitution effects. Chlorinated products including HOCl-adducts and decarboxylated Cl-adduct were identified during chlorination of cinnamic acid by high-performance liquid chromatography/high resolution mass spectrometry (HPLC/HRMS).

Ozonation of secondary wastewater treatment plant effluent for the abatement of organic micropollutants requires an accurate process control, which can be based on monitoring ozone-induced changes in dissolved organic matter (DOM). This study presents a novel automated analytical system for monitoring changes in the electron donating capacity (EDC) and UV absorbance of DOM during ozonation. In a first step, a quantitative photometric EDC assay was developed based on electron-transfer reactions from phenolic moieties in DOM to an added chemical oxidant, the radical cation of 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS^·+). The assay is highly sensitive (limit of quantification ∼0.5 mg_DOC·L^-1) and EDC values of model DOM isolates determined by this assay were in good agreement with values determined previously by mediated electrochemical oxidation (slope = 1.01 ± 0.07, R² = 0.98). In a second step, the photometric EDC measurement method was transferred onto an automated fluidic system coupled to a photometer (EDC analyzer). The EDC analyzer was then used to monitor changes in EDC and UV absorbance of secondary wastewater effluent treated with ozone. While both parameters exhibited a dose-dependent decrease, a more pronounced decrease in EDC as compared to UV absorbance was observed at specific ozone doses up to 0.4 mg_O3·g_DOC^-1. The concentration of 17α-ethinylestradiol, a phenolic micropollutant with a high ozone reactivity, decreased proportionally to the EDC decrease. In contrast, abatement of less ozone-reactive micropollutants and bromate formation started only after a pronounced initial decrease in EDC. The on-line EDC analyzer presented herein will enable a comprehensive assessment of the combination of EDC and UV absorbance as control parameters for full-scale ozonation.

Ozonation of drinking and wastewater relies on ozone (O₃) and hydroxyl radical (^•OH) as oxidants. Both oxidants react with dissolved organic matter (DOM) and alter its composition, but the selectivity of the two oxidants and mechanisms of reactivity with DOM moieties are largely unknown. The reactions of O₃ and ^•OH with two DOM isolates were studied by varying specific ozone doses (0.1-1.3 mg-O₃/mg-C) at pH 7. Additionally, conditions that favor O₃ (i.e., addition of an ^•OH scavenger) or ^•OH (i.e., pH 11) were investigated. Ozonation decreases aromaticity, apparent molecular weight, and electron donating capacity (EDC) of DOM with large changes observed when O₃ is the main oxidant (e.g., EDC decreases 63-77% for 1.3 mg-O₃/mg-C). Both O₃ and ^•OH react with highly aromatic, reduced formulas detected using high-resolution mass spectrometry (O:C = 0.48 ± 0.12; H:C = 1.06 ± 0.23), while ^•OH also oxidizes more saturated formulas (H:C = 1.64 ± 0.26). Established reactions between model compounds and O₃ (e.g., addition of one to two oxygen atoms) or ^•OH (e.g., addition of one oxygen atom and decarboxylation) are observed and produce highly oxidized DOM (O:C > 1.0). This study provides molecular-level evidence for the selectivity of O₃ as an oxidant within DOM.

Aliphatic amines are common constituents in micropollutants and dissolved organic matter and present in elevated concentrations in wastewater-impacted source waters. Due to high reactivity, reactions of aliphatic amines with ozone are likely to occur during ozonation in water and wastewater treatment. We investigated the kinetics and mechanisms of the reactions of ozone with ethylamine, diethylamine, and triethylamine as model nitrogenous compounds. Species-specific second-order rate constants for the neutral parent amines ranged from 9.3 × 10⁴ to 2.2 × 10⁶ M⁻¹s⁻¹ and the apparent second-order rate constants at pH 7 for potential or identified transformation products were 6.8 × 10⁵ M⁻¹s⁻¹ for N,N-diethylhydroxylamine, ∼10⁵ M⁻¹s⁻¹ for N-ethylhydroxylamine, 1.9 × 10³ M⁻¹s⁻¹ for N-ethylethanimine oxide, and 3.4 M⁻¹s⁻¹ for nitroethane. Product analyses revealed that all amines were transformed to products containing a nitrogen-oxygen bond (e.g., triethylamine N-oxide and nitroethane) with high yields, i.e., 64–100% with regard to the abated target amines. These findings could be confirmed by measurements of singlet oxygen and hydroxyl radical which are formed during the amine-ozone reactions. Based on the high yields of nitroethane from ethylamine and diethylamine, a significant formation of nitroalkanes can be expected during ozonation of waters containing high levels of dissolved organic nitrogen, as expected in wastewaters or wastewater-impaired source waters. This may pose adverse effects on the aquatic environment and human health.

The abatement of organic micropollutants during oxidation processes has become an emerging issue for various urban water systems such as drinking water, wastewater, and water reuse. Reaction kinetics and mechanisms play an important role in terms of efficiency of these processes and the formation of transformation products, which are controlled by functional groups in the micropollutants and the applied oxidants. So far, the kinetic and mechanistic information on the underlying reactions was obtained by experimental studies; additionally, predictive quantitative structure–activity relationships (QSARs) were applied to determine reaction kinetics for the oxidation of emerging compounds. Since this experimental approach is very laborious and there are tens of thousands potential contaminants, alternative strategies need to be developed to predict the fate of micropollutants during oxidative water treatment. Due to significant developments in quantum chemical (QC) computations in recent years and increased computational capacity, QC-based methods have become an alternative or a supplement to the current experimental approach.
This Account provides a critical assessment of the current state-of-the-art of QC-based methods for the assessment of oxidation of micropollutants. Starting from a given input structure, QC computations need to locate energetic minima on the potential energy surface (PES). Then, useful thermodynamic and kinetic information can be estimated by different approaches: Experimentally determined reaction mechanisms can be validated by identification of transition structures on the PES, which can be obtained for addition reactions, heavy atom transfer (Cl⁺, Br⁺, O·) and H atom transfer (simultaneous proton and electron transfer) reactions. However, transition structures in the PES cannot be obtained for e^–-transfer reactions.
Second-order rate constants k for the reactions of micropollutants with chemical oxidants can be obtained by ab initio calculations or by QSARs with various QC descriptors. It has been demonstrated that second-order rate constants from ab initio calculations are within factors 3–750 of the measured values, whereas QSAR-based methods can achieve factors 2–4 compared to the experimental data. The orbital eigenvalue of the highest occupied molecular orbital (E_HOMO) is the most commonly used descriptor for QSAR-based computations of k-values.
In combination with results from experimental studies, QC computations can also be applied to investigate reaction mechanisms for verification/understanding of oxidative mechanisms, calculation of branching ratios or regioselectivity, evaluation of the experimental product distribution and assessment of substitution effects. Furthermore, other important physical-chemical constants such as unknown equilibria for species, which are not measurable due to low concentrations, or pK_a values of reactive transient species can be estimated. With further development of QC-based methods, it will become possible to implement kinetic and mechanistic information from such computations in in silico models to predict oxidative transformation of micropollutants. Such predictions can then be complemented by tailored experimental studies to confirm/falsify the computations.

In response to water scarcity and an increased recognition of the risks associated with the presence of chemical contaminants, environmental engineers have developed advanced water treatment systems that are capable of converting municipal wastewater effluent into drinking water. This practice, which is referred to as potable water reuse, typically relies upon reverse osmosis (RO) treatment followed by exposure to ultraviolet (UV) light and addition of hydrogen peroxide (H₂O₂). These two treatment processes individually are capable of controlling many of the chemical and microbial contaminants in wastewater; however, a few chemicals may still be present after treatment at concentrations that affect water quality.
Low-molecular weight (<200 Da), uncharged compounds represent the greatest challenge for RO treatment. For potable water reuse systems, compounds of greatest concern include oxidation products formed during treatment (e.g., N-nitrosodimethylamine, halogenated disinfection byproducts) and compounds present in wastewater effluent (e.g., odorous compounds, organic solvents). Although the concentrations of most of these compounds decrease to levels where they no longer compromise water quality after they encounter the second treatment barrier (i.e., UV/H₂O₂), low-molecular weight compounds that are resistant to direct photolysis and exhibit low reactivity with hydroxyl radical (·OH) may persist. While attempts to identify the compounds that pass through both barriers have accounted for approximately half of the dissolved organic carbon remaining after treatment, it is unlikely that a significant fraction of the remaining unknowns will ever be identified with current analytical techniques. Nonetheless, the toxicity-weighted concentration of certain known compounds (e.g., disinfection byproducts) is typically lower in RO-UV/H₂O₂ treated water than conventional drinking water.
To avoid the expense associated with managing the concentrate produced by RO, environmental engineers have begun to employ alternative treatment barriers. The use of alternatives such as nanofiltration, ozonation followed by biological filtration, or activated carbon filtration avoids the problems associated with the production and disposal of RO concentrate, but they may allow a larger number of chemical contaminants to pass through the treatment process. In addition to the transformation products and solvents that pose risks in the RO-UV/H₂O₂ system, these alternative barriers are challenged by larger, polar compounds that are not amenable to oxidation, such as perfluoroalkyl acids and phosphate-containing flame retardants.
To fully protect consumers who rely upon potable water reuse systems, new policies are needed to prevent chemicals that are difficult to remove during advanced treatment from entering the sewer system. By using knowledge about the composition of municipal wastewater and the mechanisms through which contaminants are removed during treatment, it should be possible to safely reuse municipal wastewater effluent as a drinking water source.

Oxidation processes are impacted by the type, concentration and reactivity of the dissolved organic matter (DOM). In this study, the reactions between various types of DOM (Suwannee River fulvic acid (SRFA), Nordic Reservoir NOM (NNOM) and Pony Lake fulvic acid (PLFA)) and two oxidants (ozone and chlorine) were studied in the pH range 2–9 by using a combination of optical measurements and electron donating capacities. The relationships between residual electron donating capacity (EDC) and residual absorbance showed a strong pH dependence for the ozone-DOM reactions with phenolic functional groups being the main reacting moieties. Relative EDC and absorbance abatements (UV₂₅₄ or UV₂₈₀) were similar at pH 2. At pH 7 or 9, the relative abatement of EDC was more pronounced than for absorbance, which could be explained by the formation of UV-absorbing products such as benzoquinone from the transformation of phenolic moieties. An increase in fluorescence abatement with increasing pH was also observed during ozonation. The increase in fluorescence quantum yields could not be attributed to formation of benzoquinone, but related to a faster abatement of phenolic moieties relative to fluorophores with low ozone reactivity.
The overall ^•OH yields as a result of DOM-induced ozone consumption increased significantly with increasing pH, which could be related to the higher reactivity of phenolic moieties at higher pH. The ^•OH yields for SRFA and PLFA were proportional to the phenolic contents, whereas for NNOM, the ^•OH yield was about 30% higher.
During chlorination of DOM at pH 7 an efficient relative EDC abatement was observed whereas the relative absorbance abatement was much less pronounced. This is due to the formation of chlorophenolic moieties, which exert a significant absorbance, and partly lose their electron donating capacity.
Pre-ozonation of SRFA leads to a decrease of chloroform and haloacetic acid formation, however, only after a threshold of > ∼50% abatement of the EDC and under conditions which are not precursor limited. The decrease in chloroform and haloacetic acid formation after the threshold EDC abatement was proportional to the relative residual EDC.

Electron-donating activated aromatic moieties, including phenols, in dissolved organic matter (DOM) partially control its reactivity with the chemical oxidants ozone and chlorine. This comparative study introduces two sensitive analytical systems to directly and selectively quantify the electron-donating capacity (EDC) of DOM, which corresponds to the number of electrons transferred from activated aromatic moieties, including phenols, to the added chemical oxidant 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonate) radical cation (i.e., ABTS^•+). The first system separates DOM by size exclusion chromatography (SEC) followed by a post-column reaction with ABTS^•+ and a spectrophotometric quantification of the reduction of ABTS^•+ by DOM. The second system employs flow-injection analysis (FIA) coupled to electrochemical detection to quantify ABTS^•+ reduction by DOM. Both systems have very low limits of quantification, allowing determination of EDC values of dilute DOM samples with <1 mg carbon per liter. When applied to ozonated and chlorinated model DOM isolates and real water samples, the two analytical systems showed that EDC values of the treated DOM decrease with increasing specific oxidant doses. The EDC decreases detected by the two systems were in overall good agreement except for one sample containing DOM with a very low EDC. The combination of EDC with UV-absorbance measurements gives further insights into the chemical reaction pathways of DOM with chemical oxidants such as ozone or chlorine. We propose the use of EDC in water treatment facilities as a readily measurable parameter to determine the content of electron-donating aromatic moieties in DOM and thereby its reactivity with added chemical oxidants.

Ozonation and subsequent post-treatments are increasingly implemented in wastewater treatment plants (WWTPs) for enhanced micropollutant abatement. While this technology is effective, micropollutant oxidation leads to the formation of ozonation transformation products (OTPs). Target and suspect screening provide information about known parent compounds and known OTPs, but for a more comprehensive picture, non-target screening is needed. Here, sampling was conducted at a full-scale WWTP to investigate OTP formation at four ozone doses (2, 3, 4, and 5 mg/L, ranging from 0.3 to 1.0 gO₃/gDOC) and subsequent changes during five post-treatment steps (i.e., sand filter, fixed bed bioreactor, moving bed bioreactor, and two granular activated carbon (GAC) filters, relatively fresh and pre-loaded). Samples were measured with online solid-phase extraction coupled to liquid chromatography high-resolution tandem mass spectrometry (LC-HRMS/MS) using electrospray ionization (ESI) in positive and negative mode. Existing non-target screening workflows were adapted to (1) examine the formation of potential OTPs at four ozone doses and (2) compare the removal of OTPs among five post-treatments. In (1), data processing included principal component analysis (PCA) and chemical knowledge on 31 possible oxidation reactions to prioritize non-target features likely to be OTPs. Between 394 and 1328 unique potential OTPs were detected in positive ESI for the four ozone doses tested; between 12 and 324 unique potential OTPs were detected in negative ESI. At a specific ozone dose of 0.5 gO₃/gDOC, 27 parent compounds were identified and were related to 69 non-target features selected as potential OTPs. Two OTPs were confirmed with reference standards (venlafaxine N-oxide and chlorothiazide); 34 other potential OTPs were in agreement with literature data and/or reaction mechanisms. In (2), hierarchical cluster analysis (HCA) was applied on profiles detected in positive ESI mode across the WWTP and revealed 11 relevant trends. OTP removal was compared among the five post-treatments and 54–83% of the non-target features that appeared after ozonation were removed, with the two GAC filters performing the best. Overall, these data analysis strategies for non-target screening provide a useful tool to understand the behavior of unknown features during ozonation and post-treatment and to prioritize certain non-targets for further identification.

Chemical oxidants have been applied in water treatment for more than a century, first as disinfectants and later to abate inorganic and organic contaminants. The challenge of oxidative abatement of organic micropollutants is the formation of transformation products with unknown (eco)toxicological consequences. Four aspects need to be considered for oxidative micropollutant abatement: (i) Reaction kinetics, controlling the efficiency of the process, (ii) mechanisms of transformation product formation, (iii) extent of formation of disinfection byproducts from the matrix, (iv) oxidation induced biological effects, resulting from transformation products and/or disinfection byproducts. It is impossible to test all the thousands of organic micropollutants in the urban water cycle experimentally to assess potential adverse outcomes of an oxidation. Rather, we need multidisciplinary and automated knowledge-based systems, which couple predictions of kinetics, transformation and disinfection byproducts and their toxicological consequences to assess the overall benefits of oxidation processes. A wide range of oxidation processes has been developed in the last decades with a recent focus on novel electricity-driven oxidation processes. To evaluate these processes, they have to be compared to established benchmark ozone- and UV-based oxidation processes by considering the energy demands, economics, the feasibilty, and the integration into future water treatment systems.

Phenolic moieties are common functional groups in organic micropollutants and in dissolved organic matter, and are exposed to ozone during drinking water and wastewater ozonation. Although unsubstituted phenol is known to yield potentially genotoxic p-benzoquinone during ozonation, little is known about the effects of substitution of the phenol ring on transformation product formation. With batch experiments employing differing ozone/target compound ratios, it is shown that para-substituted phenols (p-alkyl, p-halo, p-cyano, p-methoxy, p-formyl, p-carboxy) yield p-benzoquinones, p-substituted catechols, and 4-hydroxy-4-alkyl-cyclohexadien-1-ones as common ozonation products. Only in a few cases did para-substitution prevent the formation of these potentially harmful products. Quantum chemical calculations showed that different reaction mechanisms lead to p-benzoquinone, and that cyclohexadienone can be expected to form if no such pathway is possible. These products can thus be expected from most phenolic moieties. Kinetic considerations showed that substitution of the phenolic ring results in rather small changes of the apparent second order rate constants for phenol–ozone reactions at pH 7. Thus, in mixtures, most phenolic structures can be expected to react with ozone. However, redox cross-reactions between different transformation products, as well as hydrolysis, can be expected to further alter product distributions under realistic treatment scenarios.

We investigated the mechanisms and isotope effects associated with the N-dealkylation and N-atom oxidation of substituted N-methyl- and N,N-dimethylanilines to identify isotope fractionation trends for the assessment of oxidations of aromatic N-alkyl moieties by compound-specific isotope analysis (CSIA). In laboratory batch model systems, we determined the C, H, and N isotope enrichment factors for the oxidation by MnO₂ and horseradish peroxidase (HRP), derived apparent ¹³C-, ²H-, and ¹⁵N-kinetic isotope effects (AKIEs), and characterized reaction products. The N-atom oxidation pathway leading to radical coupling products typically exhibited inverse ¹⁵N-AKIEs (up to 0.991) and only minor ¹³C- and ²H-AKIEs. Oxidative N-dealkylation, in contrast, was subject to large normal ¹³C- and ²H-AKIEs (up to 1.019 and 3.1, respectively) and small ¹⁵N-AKIEs. Subtle changes of the compound’s electronic properties due to different types of aromatic and/or N-alkyl substituents resulted in changes of reaction mechanisms, rate-limiting step(s), and thus isotope fractionation trends. The complex sequence of electron and proton transfers during the oxidative transformation of substituted aromatic N-alkyl amines suggests highly compound- and mechanism-dependent isotope effects precluding extrapolations to other organic micropollutants reacting along the same degradation pathways.

The efficiency of ozone-based processes under various conditions was studied for the treatment of a surface water (Lake Zürich water, Switzerland) spiked with 19 micropollutants (pharmaceuticals, pesticides, industrial chemical, X-ray contrast medium, sweetener) each at 1 μg L⁻¹. Two pilot-scale ozonation reactors (4–5 m³ h⁻¹), a 4-chamber reactor and a tubular reactor were investigated by either conventional ozonation and/or the advanced oxidation process (AOP) O₃/H₂O₂. The effects of selected operational parameters, such as ozone dose (0.5–3 mg L⁻¹) and H₂O₂ dose (O₃:H₂O₂ = 1:3–3:1 (mass ratio)), and selected water quality parameters, such as pH (6.5–8.5) and initial bromide concentration (15–200 μg L⁻¹), on micropollutant abatement and bromate formation were investigated. Under the studied conditions, compounds with high second-order rate constant k_O3>10⁴ M⁻¹ s⁻¹ for their reaction with ozone were well abated (>90%) even for the lowest ozone dose of 0.5 mg/L. Conversely, the abatement efficiency of sucralose, which only reacts with hydroxyl radicals (·OH), varied between 19 and 90%. Generally, the abatement efficiency increased with higher ozone doses and higher pH and lower bromide concentrations. H₂O₂ addition accelerated the ozone conversion to radical ·OH, which enables a faster abatement of ozone-resistant micropollutants. Interestingly, the abatement of micropollutants decreased with higher bromide concentrations during conventional ozonation due to competitive ozone-consuming reactions, except for lamotrigine, due to the suspected reaction of HOBr/OBr⁻ with the primary amine moieties. In addition to the abatement of micropollutants, the evolution of the two main transformation products (TPs) of hydrochlorothiazide (HCTZ) and tramadol (TRA), chlorothiazide (CTZ) and tramadol N-oxide (TRA-NOX) respectively, was assessed by chemical analysis and kinetic modelling. Both selected TPs were quickly formed initially to reach a maximum concentration followed by a decrease of their concentrations for longer contact times. For the studied conditions, the TP's concentrations at the outlet of the reactors ranged from 0 to 61% of the initial parent compound concentration, CTZ being a more persistent TP than TRA-NOX. Finally, it was demonstrated in both reactors that the formation of bromate (BrO₃−), a potentially carcinogenic oxidation by-product, could be controlled by H₂O₂ addition with a general improvement on micropollutant abatement. Post-treatment by granular activated carbon (GAC) filtration enabled the reduction of micropollutants and TPs concentrations but no changes in bromate were observed. The combined algae assays showed that water quality was significantly improved after oxidation and GAC post-treatment, driven by the abatement of the spiked pesticides (diuron and atrazine).

Wastewater treatment plants (WWTPs) are important point sources for micropollutants, which are harmful to freshwater organisms. Ozonation of wastewater is a powerful option to abate micropollutants, but may result in the formation of the potentially toxic oxidation by-product bromate in bromide-containing wastewaters. This study investigates options to reduce bromate formation during wastewater ozonation by (i) reducing the bromide concentration of the wastewater, (ii) lowering the ozone dose during wastewater treatment and (iii) adding hydrogen peroxide to limit the lifetime of ozone and quench the intermediates of the bromate formation pathway. Two examples demonstrate that a high share of bromide in wastewater can originate from single point sources (e.g., municipal waste incinerators or landfills). The identification of major point sources requires laborious sampling campaigns, but may facilitate the reduction of the bromide load significantly. To reduce the bromate formation by lowering the ozone dose interferes with the aim to abate micropollutants. Therefore, an additional treatment is necessary to ensure the elimination of micropollutants. Experiments at a pilot-plant illustrate that a combined treatment (ozone/powdered activated carbon) allows to eliminate micropollutants with low bromate yields. Furthermore, the addition of hydrogen peroxide was investigated at bench-scale. The bromate yields could be reduced by ∼50% and 65% for a hydrogen peroxide dose of 5 and 10 mg L⁻¹, respectively. In conclusion, there are options to reduce the bromate formation during wastewater ozonation, however, they are not simple with sometimes limited efficiency.

The formation and further reactions of halamines during oxidative water treatment can be relevant for water quality. In this study, we investigated the formation and reactivity of several inorganic and organic halamines (monochloramine, N-chloromethylamine, N-chlorodimethylamine, monobromamine, dibromamine, N-bromomethylamine, N,N-dibromomethylamine, and N-bromodimethylamine) by kinetic experiments, transformation product analysis, and quantum chemical computations. Kinetic model simulations were conducted to evaluate the relevance of halamines for various water treatment scenarios. Halamines were quickly formed from the reaction of chlorine and bromine with ammonia or organic amines. Species-specific second-order rate constants for the reaction of chlorine and bromine with ammonia, methyl- and dimethylamine were in the order of 10⁶-10⁸ M⁻¹s⁻¹. The formed halamines were found to be reactive towards phenolic compounds, forming halogenated phenols via electrophilic aromatic substitution (phenol and resorcinol) or quinones via electron transfer (catechol and hydroquinone). At near neutral pH, apparent second-order rate constants for these reactions were in the order of 10⁻⁴-10⁻¹ M⁻¹s⁻¹ for chloramines and 10¹-10² M⁻¹s⁻¹ for bromamines. Quantum chemical computations were used to determine previously unknown aqueous pK_a values, gas phase bond dissociation energies (BDE) and partial atomic charges of the halamines, allowing a better understanding of their reactivities. Kinetic model simulations, based on the results of this study, showed that during chlorination inorganic and organic chloramines are the main halamines formed. However, their further reactions with organic matter are outcompeted kinetically by chlorine. During ozonation, mainly inorganic bromamines are formed, since ozone quickly oxidizes organic amines. The further reactions of bromamine are typically outcompeted by ozone and thus generally of minor importance. The use of peracetic acid for saline ballast water treatment can result in the formation of substantial amounts of bromamines, which can react with dissolved organic matter and contribute to the formation of brominated products.

Ozonation of secondary wastewater effluents can reduce the discharge of micropollutants by transforming their chemical structures. Therefore, a better understanding of the formation of transformation products during ozonation is important. In this study, a computer-based prediction platform for the kinetics and mechanisms of the reactions of ozone with organic compounds was developed to enable in silico predictions of transformation products. With the developed prediction platform, reaction kinetics expressed as second-order rate constants for the reactions of ozone with selected organic compounds (k_O3, M⁻¹ s⁻¹) can be predicted based on an adapted k_O3 prediction model from a previous study (Lee et al., Environ. Sci. Technol., 2015, 49 , 9925–9935) (average model error of about a factor of 6 for 14 compound classes with 284 model compounds). Ozone reaction mechanisms reported in the literature have been reviewed and, using chemoinformatics tools, encoded into about 340 individual reaction rules that can be generally applied to predict the transformation products of micropollutants. Predictions for k_O3 and/or transformation products were overall consistent with the experimental data for three micropollutants used as validation compounds (e.g., carbamazepine, tramadol, and triclosan). However, limitations of the current k_O3 prediction platform were also identified: ambiguous assignment of the n-th highest occupied molecular orbital energy (E_HOMO−n) to the reactive sites, potential errors associated with the use of a gas-phase geometry, and a poor k_O3 prediction for certain compounds (cetirizine). Therefore, the current prediction tool should not be considered as a substitute for experimental studies and experimental data are still required in the future to obtain a more robust prediction model. Nonetheless, the developed prediction platform, made available as a stand-alone graphical user interface (GUI) application, will provide useful information about aqueous ozone chemistry to various groups of end-users such as environmental chemists, engineers, or toxicologists.

N-Nitrosodimethylamine (NDMA) is a carcinogenic disinfection byproduct from water chloramination. Despite the identification of numerous NDMA precursors, essential parts of the reaction mechanism such as the incorporation of molecular O₂ are poorly understood. In laboratory model systems for the chloramination of secondary and tertiary amines, we investigated the kinetics of precursor disappearance and NDMA formation, quantified the stoichiometries of monochloramine (NH₂Cl) and aqueous O₂ consumption, derived ¹⁸O-kinetic isotope effects (¹⁸O-KIE) for the reactions of aqueous O₂, and studied the impact of radical scavengers on NDMA formation. Although the molar NDMA yields from five N, N-dimethylamine-containing precursors varied between 1.4% and 90%, we observed the stoichiometric removal of one O₂ per N, N-dimethylamine group of the precursor indicating that the oxygenation of N atoms did not determine the molar NDMA yield. Small ¹⁸O-KIEs between 1.0026 ± 0.0003 and 1.0092 ± 0.0009 found for all precursors as well as completely inhibited NDMA formation in the presence of radical scavengers (ABTS and trolox) imply that O₂ reacted with radical species. Our study suggests that aminyl radicals from the oxidation of organic amines by NH₂Cl and N-peroxyl radicals from the reaction of aminyl radicals with aqueous O₂ are part of the NDMA formation mechanism.

Bromide measurements and mass balances in the catchments of major Swiss rivers revealed that chemical industry and municipal waste incinerators are the most important bromide sources and account for ∼50% and ∼20%, respectively, of the ∼2000 tons of bromide discharged in the Rhine river in 2014 in Switzerland. About 100 wastewater treatment plants (WWTPs) will upgrade their treatment for micropollutant abatement in the future to comply with Swiss regulations. An upgrade with ozonation may lead to unintended bromate formation in bromide-containing wastewaters. Measured bromide concentrations were <0.05 mg L^-1 in ∼75% of 69 WWTPs, while they ranged from 0.4 to ∼50 mg L^-1 in WWTPs with specific bromide sources (e.g., municipal waste incinerators, landfill leachate, and chemical industry). Wastewater ozonation formed little bromate at specific ozone doses of ≤0.4 mg O₃/mg DOC, while the bromate yields were almost linearly correlated to the specific ozone dose for higher ozone doses. Molar bromate yields for typical specific ozone doses in wastewater treatment (0.4-0.6 mg O₃/mg DOC) are ≤3%. In a modeled extreme scenario (in which all upgraded WWTPs release 10 μg L^-1 of bromate), bromate concentrations increased by <0.4 μg L^-1 in major Swiss rivers and by several micrograms per liter in receiving water bodies with a high fraction of municipal wastewater.

Ozonation of municipal wastewater effluent has been considered in recent years as an enhanced wastewater treatment technology to abate trace organic contaminants (micropollutants). The efficiency of ozonation for micropollutant abatement depends on (1) the reactivity of ozone and OH radical (·OH) with the target micropollutant, (2) the dosage of ozone and the stability of ozone and ·OH in a given water matrix, (3) the removal of undesirable effects (e.g., biological activities) of a micropollutant after structural transformation, and (4) the biodegradability of transformation products in biological post-treatment. In this article, recent advances in predicting organic micropollutant abatement during ozonation of municipal wastewater effluents are reviewed with a focus on (i) principle-based approaches for describing and modeling the reaction kinetics of ozone and ·OH, (ii) transformation products and pathways, (iii) changes of biological activities, and (iv) biodegradation of transformation products in biological post-treatment. Using the chemical kinetics based on ozone and ·OH rate constants (i.e., compound-specific information) and exposures (i.e., water matrix-specific information), a generalized prediction of the abatement efficiency of various micropollutants in varying water quality appears to be possible. QSAR-type correlations based on Hammett coefficients or quantum chemical energy calculations or (semi)empirical models have been developed for predicting the ozone and ·OH rate constants and exposures, respectively. Models based on the ozone and ·OH reaction rules can be used to predict the transformation products of micropollutants by ozone and ·OH. Reaction rule-based models in combination with the chemical kinetics information will enable the prediction of transformation product evolution during ozonation. The biological activities of transformation products have been assessed by an effect-driven approach using in vitro bioassays. Biological activities with specific modes of action (e.g., receptor-binding activities) were found to be quite efficiently removed, upon slight structural modifications by ozone or ·OH. The formation of new biological activities has also been observed, which warrants identification of the responsible toxicophore(s) and quantitative exposure-based risk assessment. Finally, there is only limited experimental information on the biodegradability of transformation products; however, biodegradability probability models can be used to make first estimates. In future research, the discussed principle-based approaches can be more actively applied to determine and predict not only the abatement levels of the parent micropollutants but also the formation of transformation products and the consequent changes of biological activities and biodegradability, which determines the overall treatment efficiency.

Dissolved organic matter (DOM) plays a crucial role in the photochemical transformation of organic contaminants in natural aquatic systems. The present study focuses on the characterization of a specific effect previously observed for electron-rich phenols, consisting in an acceleration of the DOM-photosensitized transformation of target compounds at low concentrations (< 1 µM). This effect was hypothesized to be caused by DOM-derived "long-lived" photooxidants (LLPO). Pseudo-first-order rate constants for the transformation of several phenols, anilines, sulfonamide antibiotics and phenylureas photosensitized by Suwannee River fulvic acid were determined under steady−state irradiation using the UVA and visible wavelengths from a medium-pressure mercury lamp. A significant enhancement (by a factor of 2.4 − 16) of the first-order transformation rate constant of various electron-rich target compounds was observed for an initial concentration of 0.1 μM compared to 5 μM . This effect points to a relevant reactivity of these compounds with LLPO. For phenols and anilines the enhancement effect occurred only above certain standard one-electron oxidation potentials. From these data series the standard one-electron reduction potential of LLPO was estimated to be in the range of 1.0 − 1.3 V versus the standard hydrogen electrode. LLPO are proposed to mainly consist of phenoxyl radicals formed by photooxidation of electron-poor phenolic moieties of the DOM. The plausibility of this hypothesis was successfully tested by studying the photosensitized transformation kinetics of 3,4-dimethoxyphenol in aqueous solutions containing a model photosensitizer (2-acetonaphthone) and a model electron-poor phenol (4-cyanophenol) as DOM surrogates.

Dissolved organic matter (DOM) has been shown to inhibit the oxidation of aromatic amines initiated by excited triplet states, an effect that was attributed to the reduction of oxidation intermediates back to their parent compounds. The present study focuses on the quantification of an analogous inhibitory effect of DOM on aqueous oxidations induced by the sulfate radical (SO₄^·–). Second-order rate constants for the SO₄^·–-induced transformation of selected anilines and sulfonamide antibiotics were determined by competition kinetics in the presence and absence of DOM from three different isolates at pH 8. In the presence of 1 mg_C L^–1 of DOM, a significant reduction in the rate constant was observed for most of the compounds compared to DOM-free solutions, but for two electron-rich anilines, increases in the rate constant were measured. For 4-cyanoaniline and sulfamethoxazole, the DOM concentration dependence of the rate constant consisted of a sharp decrease up to ∼1.0 mg_C L^–1 of DOM followed by a region of slight changes or even increases for higher DOM concentrations (up to 5 mg_C L^–1). This behavior was attributed to the occurrence of the aforementioned inhibitory effect and a counteracting accelerated transformation of the contaminants due to reactions with secondary radical oxidants resulting from DOM oxidation by SO₄^·–. Both effects of inhibition and secondary oxidants should be considered when assessing the abatement of aromatic amines in SO₄^·–-based advanced oxidation processes.

Aromatic amines are aquatic contaminants for which phototransformation in surface waters can be induced by excited triplet states of dissolved organic matter (³DOM*). The first reaction step is assumed to consist of a one-electron oxidation process of the amine to produce its radical cation. In this paper, we present laser flash photolysis investigations aimed at characterizing the photoinduced, aqueous phase one-electron oxidation of 4-(dimethylamino)benzonitrile (DMABN) as a representative of this contaminant class. The production of the radical cation of DMABN (DMABN^•+) after direct photoexcitation of DMABN at 266 nm was confirmed in accord with previous experimental results. Moreover, DMABN^•+ was shown to be produced from the reactions of several excited triplet photosensitizers (carbonyl compounds) with DMABN. Second-order rate constants for the quenching of the excited triplet states by DMABN were determined to fall in the range of 3 × 10⁷–5 × 10⁹ M⁻¹ s⁻¹, and their variation was interpreted in terms of electron transfer theory using a Rehm–Weller relationship. The decay kinetics of DMABN^•+ in the presence of oxygen was dominated by a second-order component attributed to its reaction with the superoxide radical anion (O₂^•−). The first-order rate constant for the transformation of DMABN^•+ leading to photodegradation of DMABN was estimated not to exceed ≈5 × 10³ s⁻¹.

Previous studies have shown that the photodegradation of some pollutants, induced by the excited triplet states of chromophoric dissolved organic matter (³CDOM^*), can be inhibited by back-reduction processes carried out by phenolic antioxidants occurring in dissolved organic matter (DOM). Here, for the first time to our knowledge, we included such an inhibition effect into a photochemical model and applied the model predictions to sulfadiazine (SDZ), a sulfonamide antibiotic that occurs in surface waters in two forms, neutral HSDZ and anionic SDZ⁻ (pK_a = 6.5). The input parameters of the photochemical model were obtained by means of dedicated experiments, which showed that the inhibition effect was more marked for SDZ− than for HSDZ. Compared to the behavior of 2,4,6-trimethylphenol, which does not undergo antioxidant inhibition when irradiated in natural water samples, the back-reduction effect on the degradation of SDZ was proportional to the electron-donating capacity of the DOM. According to the model results, direct photolysis and ·OH reaction would account for the majority of both HSDZ and SDZ⁻ photodegradation in waters having low dissolved organic carbon (DOC < 1 mgC L^−/1). With higher DOC values (>3–4 mgC L⁻¹) and despite the back-reduction processes, the ³CDOM^* reactions are expected to account for the majority of HSDZ phototransformation. In the case of SDZ⁻ at high DOC, most of the photodegradation would be accounted for by direct photolysis. The relative importance of the triplet-sensitized phototransformation of both SDZ⁻ and (most importantly) HSDZ is expected to increase with increasing DOC, even in the presence of back reduction. An increase in water pH, favoring the occurrence of SDZ⁻ with respect to HSDZ, would enhance direct photolysis at the expense of triplet sensitization. SDZ should be fairly photolabile under summertime sunlight, with predicted half-lives ranging from a few days to a couple of months depending on water conditions.

The abatement of 9 polychloro-1,3-butadienes (CBDs) in aqueous solution by ozone, UV–C(254 nm) photolysis, and the corresponding advanced oxidation processes (AOPs) (i.e., O₃/H₂O₂ and UV/H₂O₂) was investigated. The following parameters were determined for 9 CBDs: second-order rate constants for the reactions of CBDs with ozone (k_O3) (<0.1–7.9 × 10³ M^–1 s^–1) or with hydroxyl radicals (k·_OH) (0.9 × 10⁹ – 6.5 × 10⁹ M^–1 s^–1), photon fluence-based rate constants (k′) (210–2730 m² einstein^–1), and quantum yields (Φ) (0.03–0.95 mol einstein^–1). During ozonation of CBDs in a natural groundwater, appreciable abatements (>50% at specific ozone doses of 0.5 gO₃/gDOC to ∼100% at ≥1.0 gO₃/gDOC) were achieved for tetra-CBDs followed by (Z)-1,1,2,3,4-penta-CBD and hexa-CBD. This is consistent with the magnitude of the determined k_O3 and k·_OH. The formation of bromate, a potentially carcinogenic ozonation byproduct, could be significantly reduced by addition of H₂O₂. For a typical UV disinfection dose (400 J/m²), various extents of phototransformations (10–90%) could be achieved. However, the efficient formation of photoisomers from CBDs with E/Z configuration must be taken into account because of their potential residual toxicity. Under UV–C(254 nm) photolysis conditions, no significant effect of H₂O₂ addition on CBDs abatement was observed due to an efficient direct phototransformation of CBDs.

The photochemical properties of dissolved organic matter (DOM) have been of interest to scientists and engineers since the 1970s. Upon light absorption, chromophoric DOM (CDOM) can sensitize the formation of different short-lived reactive intermediates (RIs), including hydroxyl radical (^·OH), singlet oxygen (¹O₂) and superoxide radical anion (O₂^·–). In addition, a fraction of the excited singlet states in CDOM decays into excited triplet states (³CDOM*), which are also important photochemical transients in environmental systems. These RIs have a significant impact on different processes in sunlit waters, including degradation of organic contaminants and the inactivation of pathogens. Due to their transient nature and low steady-state concentrations, the use of common analytical techniques for the direct measurement of these species is impractical. Therefore, specific probe compounds (PCs) are used. PCs include furfuryl alcohol for ¹O₂, and terephthalic acid for ^·OH. In this publication, we present a critical review of the use of PCs for the assessment of the formation of photochemically generated RIs. We first introduce the concept of a PC, including the kinetic treatment and necessary assumptions needed to conduct a specific measurement. Afterward, we present short overviews of the most studied RIs and review relevant issues regarding the use of specific PCs for their measurement. We finalize by offering recommendations regarding the use of PCs in environmental photochemistry.

Isoproturon (IPU) is a phenylurea herbicide used to control broad-leaf grasses on grain fields. Photosensitized transformation induced by excited triplet states of dissolved organic matter (³DOM*) has been identified as an important degradation pathway for IPU in sunlit waters, but the reappearance of IPU in the absence of light is observed after the initial photolysis. In this study, we elucidate the kinetics of this photodegradation and dark-reappearance cycling of IPU in the presence of DOM proxies (aromatic ketones and reference fulvic acids). Using mass spectrometry and nuclear magnetic resonance spectroscopic techniques, a semi-stable intermediate (IPU_int) was found to be responsible for IPU reversion and was identified as a hydroperoxyl derivative of IPU. IPU_int is photogenerated from incorporation of diatomic oxygen to IPU and is subjected to thermolysis whose rate depends on temperature, pH, the presence of DOM, and inorganic ions. These results are important to understand the overall aquatic fate of IPU and structurally similar compounds under diurnal conditions.

Excited triplet states of chromophoric dissolved organic matter (³CDOM*) play a major role among the reactive intermediates produced upon absorption of sunlight by surface waters. After more than two decades of research on the aquatic photochemistry of ³CDOM*, the need for improving the knowledge about the photophysical and photochemical properties of these elusive reactive species remains considerable. This critical review examines the efforts to date to characterize ³CDOM*. Information on ³CDOM* relies mainly on the use of probe compounds because of the difficulties associated with directly observing ³CDOM* using transient spectroscopic methods. Singlet molecular oxygen (¹O₂), which is a product of the reaction between ³CDOM* and dissolved oxygen, is probably the simplest indicator that can be used to estimate steady-state concentrations of ³CDOM*. There are two major modes of reaction of ³CDOM* with substrates, namely triplet energy transfer or oxidation (via electron transfer, proton-coupled electron transfer or related mechanisms). Organic molecules, including several environmental contaminants, that are susceptible to degradation by these two different reaction modes are reviewed. It is proposed that through the use of appropriate sets of probe compounds and model photosensitizers an improved estimation of the distribution of triplet energies and one-electron reduction potentials of ³CDOM* can be achieved.

Dissolved organic matter (DOM) can act as a photosensitizer and an inhibitor in the phototransformation of several nitrogen-containing organic contaminants in surface waters. The present study was performed to select a probe molecule that is suitable to measure these antagonistic properties of DOM. Out of nine studied nitrogen-containing aromatic compounds, 4-cyanoaniline, N, N-dimethyl-4-cyanoaniline (DMABN), sotalol (a β-blocker) and sulfadiazine (a sulfonamide antibiotic) exhibited a marked photosensitized transformation that could be substantially inhibited by addition of phenol as a model antioxidant. The photosensitized transformation of DMABN, the selected probe compound, was characterized in detail under UV-A and visible irradiation (λ > 320 nm) to avoid direct phototransformation. Low reactivity of DMABN with singlet oxygen was found (second-order rate constant <2 × 10⁷ M^–1 s^–1). Typically at least 85% of the reactivity of DMABN could be inhibited by DOM or the model antioxidant phenol. The photosensitized transformation of DMABN mainly proceeded (>72%) through demethylation yielding N-methyl-4-cyanoaniline and formaldehyde as primary products. In solutions of standard DOM extracts and their mixtures the phototransformation rate constant of DMABN was shown to vary nonlinearly with the DOM concentration. Model equations describing the dependence of such rate constants on DOM and model antioxidant concentrations were successfully used to fit experimental data.