Reaction Mechanisms of Chlorine Dioxide with Phenolic Compounds─Influence of Different Substituents on Stoichiometric Ratios and Intrinsic Formation of Free Available Chlorine.

Chlorine dioxide (ClO2) is an oxidant applied in water treatment processes that is very effective for disinfection and abatement of inorganic and organic pollutants. Thereby phenol is the most important reaction partner of ClO2 in reactions of natural organic matter (NOM) and in pollutant degradation. It was previously reported that with specific reaction partners (e.g., phenol), free available chlorine (FAC) could form as another byproduct next to chlorite (ClO2-). This study investigates the impact of different functional groups attached to the aromatic ring of phenol on the formation of inorganic byproducts (i.e., FAC, ClO2-, chloride, and chlorate) and the overall reaction mechanism. The majority of the investigated compounds reacted with a 2:1 stoichiometry and formed 50% ClO2- and 50% FAC, regardless of the position and kind of the groups attached to the aromatic ring. The only functional groups strongly influencing the FAC formation in the ClO2 reaction with phenols were hydroxyl- and amino-substituents in ortho- and para-positions, causing 100% ClO2- and 0% FAC formation. Additionally, this class of compounds showed a pH-dependent stoichiometric ratio due to pH-dependent autoxidation. Overall, FAC is an important secondary oxidant in ClO2 based treatment processes. Synergetic effects in pollutant control and disinfection might be observable; however, the formation of halogenated byproducts needs to be considered as well.

Bacterial inactivation processes in water disinfection - mechanistic aspects of primary and secondary oxidants - A critical review.

Water disinfection during drinking water production is one of the most important processes to ensure safe drinking water, which is gaining even more importance due to the increasing impact of climate change. With specific reaction partners, chemical oxidants can form secondary oxidants, which can cause additional damage to bacteria. Cases in point are chlorine dioxide which forms free available chlorine (e.g., in the reaction with phenol) and ozone which can form hydroxyl radicals (e.g., during the reaction with natural organic matter). The present work reviews the complex interplay of all these reactive species which can occur in disinfection processes and their potential to affect disinfection processes. A quantitative overview of their disinfection strength based on inactivation kinetics and typical exposures is provided. By unifying the current data for different oxidants it was observable that cultivated wild strains (e.g., from wastewater treatment plants) are in general more resistant towards chemical oxidants compared to lab-cultivated strains from the same bacterium. Furthermore, it could be shown that for selective strains chlorine dioxide is the strongest disinfectant (highest maximum inactivation), however as a broadband disinfectant ozone showed the highest strength (highest average inactivation). Details in inactivation mechanisms regarding possible target structures and reaction mechanisms are provided. Thereby the formation of secondary oxidants and their role in inactivation of pathogens is decently discussed. Eventually, possible defense responses of bacteria and additional effects which can occur in vivo are discussed.

Reaction of Chlorine Dioxide with Saturated Nitrogen-Containing Heterocycles and Comparison with the Micropollutant Behavior in a Real Water Matrix.

Chlorine dioxide (ClO2) is a very selective oxidant that reacts with electron-rich moieties such as activated amines and thus can degrade specific N-containing micropollutants. N-containing heterocycles (NCHs) are among the most frequent moieties of pharmaceuticals. In this study, the reactions of ClO2 with ritalinic acid and cetirizine, two abundant micropollutants, and model compounds representing their NCH moiety were investigated. The pH-dependent apparent reaction rates of all NCHs with ClO2 were measured and modeled. This model showed that neutral amines are the most important species having reaction rates between 800 and 3200 M-1 s-1, while cationic amines are not reactive. Ritalinic acid, cetirizine, and their representative model compounds showed a high stoichiometric ratio of ≈5 moles ClO2 consumption per degraded ritalinic acid and ≈4 moles ClO2 consumption per degraded cetirizine, respectively. Investigation of chlorine-containing byproducts of ClO2 showed that all investigated NCHs mostly react by electron transfer and form above 80% chlorite. The reactions of the model compounds were well comparable with cetirizine and ritalinic acid, indicating that the model compounds indeed represented the reaction centers of cetirizine and ritalinic acid. Using the calculated apparent reaction rate constants, micropollutant degradation during ClO2 treatment of surface water was predicted for ritalinic acid and cetirizine with -8 to -15% and 13 to -22% error, respectively. The results indicate that in ClO2-based treatment, piperidine-containing micropollutants such as ritalinic acid can be considered not degradable, while piperazine-containing compounds such as cetirizine can be moderately degraded. This shows that NCH model compounds could be used to predict micropollutant degradation.

Chlorine Dioxide-Pollutant Transformation and Formation of Hypochlorous Acid as a Secondary Oxidant.

Chlorine dioxide (ClO2) has been used as a disinfectant in water treatment for a long time, and its use for micropollutant abatement in wastewater has recently been suggested. Surprisingly, a mechanistic understanding of ClO2 reactions in (waste)water matrices is largely lacking. The present study contributes to this mechanistic understanding by performing a detailed investigation of ClO2 reactions with organic matter using phenol as a surrogate for reactive phenolic moieties. A concept for indirectly determining HOCl using 2- and 4-bromophenol was developed. The reaction of phenol with ClO2 formed chlorite (62 ± 4% per ClO2 consumed) and hypochlorous acid (HOCl) (42 ± 3% per ClO2 consumed). The addition of ClO2 to wastewater (5 × 10-5 M ClO2) resulted in 40% atenolol and 47% metoprolol transformation. The presence of the selective HOCl scavenger glycine largely diminished their transformation, indicating that atenolol and metoprolol were transformed by a fast reaction with HOCl (e.g., k (atenolol + HOCl) = 3.5 × 104 M-1 s-1) that formed in ClO2 reactions with the wastewater matrix. The formation of HOCl may thus increase the number of transformable micropollutants in ClO2 applications. However, chlorine related byproducts may also be formed.