title: Predicting reactivity of model DOM compounds towards chlorine with mediated electrochemical oxidation.
abstract: Chlorine demand of a water sample depends on the characteristics of dissolved organic matter (DOM). It is an important parameter for water utilities used to assess oxidant and/or disinfectant consumption of source waters during treatment and distribution. In this study, model compounds namely resorcinol, tannic acid, vanillin, cysteine, tyrosine, and tryptophan were used to represent the reactive moieties of complex DOM mixtures. The reactivity of these compounds was evaluated in terms of Cl2demand and electron donating capacity (EDC). The EDC was determined by mediated electrochemical oxidation (MEO) which involves the use of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) as an electron shuttle. The Cl2demand of readily oxidizable compounds (resorcinol, tannic acid, vanillin, and cysteine) was found to correlate well with EDC (R2= 0.98). The EDC values (mol e-/mol C) of the model compounds are as follows: 1.18 (cysteine) > 0.77 (resorcinol) > 0.59 (vanillin) > 0.52 (tannic acid) > 0.36 (tryptophan) > 0.19 (tyrosine). To determine the effect of pre-oxidation on EDC, ozone was added (0.1 mol O3/mol C) into each model compound solution. Ozonation caused a general decrease in EDC (10-40%), chlorine demand (10-30%), and UV absorbance (10-40%), except for tyrosine which showed both increased UV275and EDC. Before and after ozonation, 24 h disinfection byproduct (DBP) formation potential tests (Cl2residual = 1.5 mg/L) were conducted to evaluate the use of EDC for DBP formation prediction. The results indicate that there was no significant correlation between the EDC of the model compounds and the formation potentials of adsorbable organic chlorine, trichloromethane, and trichloroacetic acid. This suggests that while EDC correlates with Cl2demand, chlorine consumption may not directly translate to DBP formation because oxidation reactions may dominate over substitution reactions. Overall, this study provides useful insights on the reactions of ABTS+and HOCl with model DOM compounds, and highlights the potential application of MEO for rapid determination of Cl2demand of a water sample.
authors.affiliation: The University of Queensland, Advanced Water Management Centre, Queensland, 4072, Australia.
authors.forename: Glen Andrew
authors.initials: GA
authors.lastname: de Vera
authors.affiliation: The University of Queensland, Advanced Water Management Centre, Queensland, 4072, Australia; ICRA, Catalan Institute for Water Research, Scientific and Technological Park of the University of Girona, H(2)O Building, Emili Grahit 101, 17003 Girona, Spain; ICREA, Catalan Institute for Research and Advanced Studies, 08010, Barcelona, Spain.
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Gernjak
authors.affiliation: The University of Queensland, Advanced Water Management Centre, Queensland, 4072, Australia; ICRA, Catalan Institute for Water Research, Scientific and Technological Park of the University of Girona, H(2)O Building, Emili Grahit 101, 17003 Girona, Spain. Electronic address: jradjenovic@icra.cat.
authors.forename: Jelena
authors.initials: J
authors.lastname: Radjenovic
mesh_terms: D002713:Chlorine / Q000737:chemistry*; D017606:Chlorine Compounds / Q000737:chemistry; D009930:Organic Chemicals; D010126:Ozone / Q000737:chemistry; D014874:Water Pollutants, Chemical / Q000737:chemistry; D018508:Water Purification
chemical_list: D017606:Chlorine Compounds; D009930:Organic Chemicals; D014874:Water Pollutants, Chemical; D002713:Chlorine; D010126:Ozone
keywords: Chlorine demand; Disinfection byproducts; Dissolved organic matter; Electron donating capacity; Mediated electrochemical oxidation