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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

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2018 Impact Factor: 3.883

Front. Environ. Sci. Eng.    2023, Vol. 17 Issue (12) : 147    https://doi.org/10.1007/s11783-023-1747-4
RESEARCH ARTICLE
Kinetics of hydrogen peroxide quenching following UV/H2O2 advanced oxidation by thiosulfate, bisulfite, and chlorine in drinking water treatment
Tianyi Chen, Lizbeth Taylor-Edmonds, Susan Andrews, Ron Hofmann()
Department of Civil and Mineral Engineering, University of Toronto, Toronto, Ontario M5S 1A4, Canada
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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.

Keywords UV/H2O2      H2O2 quenching      Chlorine type      Water alkalinity      Temperature     
Corresponding Author(s): Ron Hofmann   
Issue Date: 17 July 2023
 Cite this article:   
Tianyi Chen,Lizbeth Taylor-Edmonds,Susan Andrews, et al. Kinetics of hydrogen peroxide quenching following UV/H2O2 advanced oxidation by thiosulfate, bisulfite, and chlorine in drinking water treatment[J]. Front. Environ. Sci. Eng., 2023, 17(12): 147.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-023-1747-4
https://academic.hep.com.cn/fese/EN/Y2023/V17/I12/147
Source T = 4 °C T = 20 °C
pH 5 7 9 5 7 9
This study Thiosulfate 0.015 ±0.000 0.013 ±0.001 0.013 ±0.002 0.073 ±0.021 0.085 ±0.004 0.059 ±0.025
Bisulfite 447 ±100 5.9 ±3.4 0.13 ±0.026 525 ±53 10 ±4.9 0.29 ±0.029
Chlorine 2.5 ±0.3 348 ±13 1528 ±153 16 ±5 803 ±66 4318 ±131
Literature values Thiosulfatea NA* NA NA 0.040 0.027 0.022
Bisulfiteb 39–531c 0.4–5.3c 0.030d 250–910c 2.5–9.1c 0.22d
Chlorinee 3 270 1159 10 750 3220
Tab.1  Measured observed second-order rate constant (kobs, mol/(L·s)) in this study and the literature for H2O2 reactions with thiosulfate, bisulfite, and chlorine in Milli-Q water at pH 5–9 and temperatures of 4 and 20 °C
Reaction T = 4 °C T = 20 °C
This study Literature values This study Literature values
Bisulfite 1.3 ± 0.79 0.020–0.27a 2.1 ± 1.2 0.13–0.46b
Chlorine 810 ± 8.5 880–996c 2250 ± 128 2520–2845c
Tab.2  Observed second-order rate constants (kobs, mol/(L·s)) for bisulfite and chlorine reactions with H2O2 measured in the natural water sample in this study and reported in the literature at the same pH (8.3) at water temperatures of 4 and 20 °C
Reaction T = 4 °C T = 20 °C
This study Literature values This study Literature values
H2O2 dose, mg/L (chlorine dose, mg/L as Cl2) 5 (10) 10 (20) 5 (10) 10 (20)
Sulfite 0.16 0.11 0.42 0.28
Bisulfite 0.77 1.9 0.11–0.41a 1.2 3.0 0.71b
Sulfite (SO2) 1.1 8.1 3.0 16
Chlorine (NaOCl) 808 820 883–996c 2161 2342 2522–2845c
Chlorine (Cl2 gas) 117 67 575 328
Tab.3  Observed second-order rate constants (kobs, mol/(L·s)) for the reaction of H2O2 with equimolar bisulfite and chlorine of different forms, measured in natural water samples (pH 8.3) in this study and in Milli-Q water, reported in the literature (pH 8.3) at 4 and 20 °C, H2O2 doses at 5 and 10 mg/L
Fig.1  Simulated time (lines) and time calculated based on experimental results (dots) to quench 95% of H2O2 (t0.95) by equimolar chlorine at initial H2O2 dose of 2 mg/L (a1–a2), 5 mg/L (b1–b2), and 10 mg/L (c1–c2) at 4 °C (left) and 20 °C (right). Gaseous and hypochlorite chlorine considered. Alkalinity (alk) in units of mg/L as CaCO3. “Theory” line assumes constant pH. Error bars for experimental results represent standard deviation.
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