Kinetics of hydrogen peroxide quenching following UV/H₂O₂ advanced oxidation by thiosulfate, bisulfite, and chlorine in drinking water treatment

Abstract

● H₂O₂ quenching rates by Cl/S-based chemicals were measured

● Chlorine takes seconds-to-minutes to quench H₂O₂ at common water pH

● The form of chlorine (gas vs . hypochlorite) affects the H₂O₂ quenching rate

● H₂O₂ quenching rates by chlorine in different conditions were predicted

Residual H₂O₂ from UV/H₂O₂ treatment can be quenched by thiosulfate, bisulfite, and chlorine, but the kinetics of these reactions have not been reported under the full range of practical conditions. In this study, the rates of H₂O₂ quenching by these compounds were compared in different water matrices, temperatures, pH, and when using different forms of bisulfite and chlorine. In general, it was confirmed that thiosulfate would be too slow to serve as a quenching agent in most practical scenarios. At pH 7–8.5, chlorine tends to quench H₂O₂ more than 20 times faster than bisulfite in the various conditions tested. An important observation was that in lightly-buffered water (e.g., alkalinity of 20 mg/L as CaCO₃), the form of chlorine can have a large impact on quenching rate, with gaseous chlorine slowing the reaction due to its lowering of the pH, and hypochlorite having the opposite effect. These impacts will become less significant when water buffer capacity (i.e., alkalinity) increases (e.g., to 80 mg/L as CaCO₃). In addition, water temperature should be considered as the time required to quench H₂O₂ by chlorine at 4 °C is up to 3 times longer than at 20 °C.

Graphical abstract

Keywords

UV/H ₂O ₂ / H ₂O ₂ quenching / Chlorine type / Water alkalinity / Temperature

References

[1] Breytenbach L, van Pareen W, Pienaar J J, van Eldik R. (1994). The influence of organic acids and metal ions on the kinetics of the oxidation of sulfur(IV) by hydrogen peroxide. Atmospheric Environment, 28(15): 2451–2459

[2] Dotson A D, Keen V S, Metz D, Linden K G. (2010). UV/H₂O₂ treatment of drinking water increases post-chlorination DBP formation. Water Research, 44(12): 3703–3713

[3] Held A M, Halko D J, Hurst J K. (1978). Mechanisms of chlorine oxidation of hydrogen peroxide. Journal of the American Chemical Society, 100(18): 5732–5740

[4] Hoffmann M R, Edwards J O. (1975). Kinetics of the oxidation of sulfite by hydrogen peroxide in acidic solution. Journal of Physical Chemistry, 79(20): 2096–2098

[5] Huang Y, Nie Z, Wang C, Li Y, Xu M, Hofmann R. (2018). Quenching H₂O₂ residuals after UV/H₂O₂ oxidation using GAC in drinking water treatment. Environmental Science. Water Research & Technology, 4(10): 1662–1670

[6] Kan E, Koh C I, Lee K, Kang J. (2015). Decomposition of aqueous chlorinated contaminants by UV irradiation with H₂O₂. Frontiers of Environmental Science & Engineering, 9(3): 429–435

[7] Kerker M. (1957). The ionization of sulfuric acid. Journal of the American Chemical Society, 79(14): 3664–3667

[8] Kruithof J C, Kamp P C, Martijn B J. (2007). UV/H₂O₂ treatment: a practical solution for organic contaminant control and primary disinfection. Ozone Science and Engineering, 29(4): 273–280

[9] Lagrange J, Pallares C, Wenger G, Lagrange P. (1993). Electrolyte effects on aqueous atmospheric oxidation of sulphur dioxide by hydrogen peroxide. Atmospheric Environment. Part A, General Topics, 27(2): 129–137

[10] Lister M W. (1952). The decomposition of hypochlorous acid. Canadian Journal of Chemistry, 30(11): 879–889

[11] Liu W, Andrews S A, Stefan M I, Bolton J R. (2003). Optimal methods for quenching H₂O₂ residuals prior to UFC testing. Water Research, 37(15): 3697–3703

[12] Lu S, Wang N, Wang C. (2018). Oxidation and biotoxicity assessment of microcystin-LR using different AOPs based on UV, O₃ and H₂O₂. Frontiers of Environmental Science & Engineering, 12(3): 12

[13] Lu Y, Gao Q, Xu L, Zhao Y, Epstein I R. (2010). Oxygen-sulfur species distribution and kinetic analysis in the hydrogen peroxide-thiosulfate system. Inorganic Chemistry, 49(13): 6026–6034

[14] Maaß F, Elias H, Wannowius K J. (1999). Kinetics of the oxidation of hydrogen sulfite by hydrogen peroxide in aqueous solution. Atmospheric Environment, 33(27): 4413–4419

[15] Mader P M. (1958). Kinetics of the hydrogen peroxide-sulfite reaction in alkaline solution. Journal of the American Chemical Society, 80(11): 2634–2639

[16] Sharma V K, Yu X, McDonald T J, Jinadatha C, Dionysiou D D, Feng M. (2019). Elimination of antibiotic resistance genes and control of horizontal transfer risk by UV-based treatment of drinking water: a mini review. Frontiers of Environmental Science & Engineering, 13(3): 37

[17] StefanM I (2017). Chapter 2: UV/Hydrogen Peroxide Process. Advanced Oxidation Processes for Water Treatment: Fundamentals and Application, 7–123

[18] Wang C, Hofmann M, Safari A, Viole I, Andrews S, Hofmann R. (2019). Chlorine is preferred over bisulfite for H₂O₂ quenching following UV-AOP drinking water treatment. Water Research, 165(15): 115000

[19] Wang T X, Margerum D W. (1994). Kinetics of reversible chlorine hydrolysis: temperature dependence and general-acid/base-assisted mechanisms. Inorganic Chemistry, 33(6): 1050–1055

[20] van Klassen N, Marchington D, McGowan H C E. (1994). H₂O₂ Determination by the I₃⁻ method and by KMnO₄ Titration. Analytical Chemistry, 66(18): 2921–2925

[21] van McArdle J, Hoffmann M R. (1983). Kinetics and mechanism of the oxidation of aquated sulfur dioxide by hydrogen peroxide at low pH. Journal of Physical Chemistry, 87: 5425–5429

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