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Page 1 of 74 Environmental Science: Water Research & Technology
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DOI: 10.1039/D0EW00231C
Water impact
Environmental Science: Water Research & Technology Accepted Manuscript

Chlorine dioxide (ClO2) is a chemical often used in water treatment for
pre-oxidation or disinfection. This work overviews the reactions of ClO2 with
inorganic and organic compounds in water matrix with focus on their reaction kinetics
and mechanisms. Micropollutant transformation during ClO2 oxidation relevant to
water treatment is also included. The information is essential in improving
understanding the ClO2 oxidation chemistry and byproducts formation in water

Published on 15 July 2020. Downloaded on 7/25/2020 2:02:34 AM.
treatment.
Environmental Science: Water Research & Technology Page 2 of 74
1 The Reactions of Chlorine Dioxide with Inorganic and Organic View Article Online
DOI: 10.1039/D0EW00231C
2 Compounds in Water Treatment: Kinetics and Mechanisms

3
4 Wenhui Gan†,‡,Yuexian Ge†, Yu Zhong†, Xin Yang†,*
6 † School of Environmental Science and Engineering, Guangdong Provincial Key
7 Laboratory of Environmental Pollution Control and Remediation Technology, Sun
8 Yat-sen University, Guangzhou 510275, China

9 ‡ Guangdong Provincial Engineering Research Center for Urban Water Recycling and
10 Environmental Safety, Tsinghua Shenzhen International Graduate School, Tsinghua
11 University, Shenzhen 518055, China
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14 * Corresponding author, Tel: +86-2039332690, email: yangx36@mail.sysu.edu.cn
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24 Abstract View Article Online

DOI: 10.1039/D0EW00231C
25 Chlorine dioxide (ClO2), as an alternative to chlorine, has been widely applied in

26 water treatment. In order to better understand the performance of ClO2 in water
27 treatment, the kinetics and mechanisms of ClO2 with inorganic and organic
28 compounds found in water are critically reviewed. In the case of inorganic
29 compounds, ClO2 reacts with I-, CN-, NO2-, SO32-, Fe(II) and Mn(II) rapidly at an
30 apparent second-order reaction rate constants (kapp) of 102–106 M-1s-1 at pH 7.0 and
31 barely reacts with NH4+ and Br-. In the case of organic compounds, ClO2 selectively
32 reacts with compounds with electron-rich moieties, such as phenols (kapp = 103–109
33 M-1s-1), anilines (kapp = 105–108 M-1s-1), and thiols (kapp > 108 M-1s-1). ClO2 also shows
34 high reactivity towards aliphatic tertiary amines and heterocyclic nitrogenous
35 compounds (i.e., indoles and piperidines) with kapp at 101–106 M-1s-1 at pH 7.0, but
36 low reaction reactivity with unsaturated structures (i.e., olefins and aldehydes). The
37 kapp values at pH 7.0 in ClO2 oxidation vary over 14 orders of magnitude. Electron
38 transfer is the dominant pathway for ClO2 reactions. Quantitative structure-activity
39 relationships (QSAR) can be used to predict the specie-specific secondary reaction
40 rate constants for ClO2 oxidation of compounds containing phenolic and amine
41 structures. Little modifications are expected on the structure of the parent compounds
42 upon the primary attack of ClO2, but further oxidation generally leads to the formation
43 of quinones, aldehydes and carboxylic acids. Furthermore, the transformation kinetics
44 of inorganic compounds, typical organic compounds and emerging micropollutants
45 are compared and their half-life times under typical water treatment conditions during
46 ClO2 oxidation are calculated.
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48
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49 View Article Online

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50 1. Introduction

51 Chlorine dioxide (ClO2) is a powerful oxidant and an alternative disinfectant to
52 chlorine in drinking water treatment. ClO2 is effective in removing algae (e.g.,
53 Chlamydomonas, Phormidium and Chlorella), inactivating planktonic bacteria and
54 some chlorine-resistant pathogens (e.g., Giardia lamblia and Cryptosporidium
55 parvum), and removing remove iron and manganese from source waters.1-3 ClO2 can
56 be used as a pre-oxidant to control the taste and odor problems. Meanwhile, ClO2 can
57 be added at the end of the drinking water treatment process to limit the growth of
58 microorganisms throughout the distribution systems. ClO2 has been reported as being
59 used in 8.1% of drinking water treatment plants in the United States and 32.8% of
60 those in China.4, 5 ClO2 is also widely used in drinking water treatment in some
61 European countries.6 ClO2 is also used in wastewater treatment to inactivate
62 microorganisms and to transform micropollutants and reduce the release of organic
63 halogenated byproducts.7
64 As a chemical oxidant, ClO2 is able to oxidize inorganic pollutants in water (e.g.,
65 iron(II), manganese(II), arsenic(III), etc.). Thus, ClO2 is usually applied to treat source
66 waters suffered from such inorganic contaminants. In addition, ClO2 reacts selectively
67 with organic compounds with electron-rich moieties, such as phenols, tertiary amines
68 and anilines. As a result, ClO2 exhibits promising removal of organic contaminants
69 with such moieties during water and wastewater treatment. Some literatures have
70 reported the kinetics, mechanisms and products from ClO2 oxidation of inorganic and
71 organic compounds.8-13 Hoigné and Bader published a nice summary about the
72 apparent second-order reaction rate constants for ClO2 oxidation of inorganic and
73 organic compounds, including phenols and amines.8 Rav-Acha summarized the

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74 reaction pathways of ClO2 oxidation of inorganic compounds and a variety DOI:

group ofView Article Online
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75 organic compounds.12

76 ClO2 oxidation generally proceed via electron transfer pathway.14, 15 That is,
77 chlorine substitution rarely occurs during ClO2 oxidation. Besides, concerns about
78 bromate or brominated DBPs formation can be spared in ClO2 oxidation because
79 bromide ion is unreactive towards ClO2 under typical water treatment conditions.
80 Therefore, tremendous reduction in the formation of halogenated DBPs, such as
81 trihalomethanes (THMs), haloacetic acids (HAAs), and haloacetonitriles (HANs), is

82 one of the major advantages of ClO2 over chlorine.16-18 Moreover, ClO2 exhibits
83 stable oxidation and disinfection strength with insignificant hydrolysis under a wide
84 pH range from pH 2.0 to 10.0, which makes ClO2 more practicable than chlorine in
85 treating waters at high pH.
86 In spite of these benefits, the application of ClO2 in water treatment also brings
87 some disadvantages. One major drawback is the formation of chlorite and chlorate.
88 For the dosed ClO2, 30–70% is transformed into chlorite and up to 10% is
89 transformed into chlorate. Considering the adverse health risks of chlorite and
90 chlorate (i.e., hemolytic anemia and liver damage),19 the level of chlorite and chlorate
91 are restricted in drinking waters. For example, the U.S Environmental Protection
92 Agency (USEPA) has set a maximum contaminant level (MCL) for chlorite of 1
93 mg∙L-1.20 The individual threshold of chlorite and chlorate in drinking waters are 0.7
94 mg∙L-1 in China.21 Consequently, the applied dose of ClO2 in drinking water
95 treatments is typically limited to approximately 1.4 mg∙L-1. In Germany, the dose of
96 ClO2 is even restricted at 0.12–0.16 mg∙L-1.22 In the case of wastewater treatment, the
97 applied dose of ClO2 is usually in the range of 2 to 10 mg∙L-1 depending on
98 wastewater properties to guarantee the microbial inactivation efficiency before reuse
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99 or discharge.23, 24 However, the release of residual ClO2, chlorite and chlorate toView Article Online
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100 environment may has adverse influences on the growth of aquatic organisms (e.g.,

101 algae and fishes).25, 26 Apart from chlorite and chlorate, the organic transformation
102 products from ClO2 oxidation are also observed in treated water, such as aldehydes,
103 carboxylic acids, esters, ketones, and quinones.27 The bioavailability of these
104 byproducts seemed insignificant as ClO2 treatment leads to minor or no increase of
105 assimilable organic carbon (AOC) of waters.28, 29 For micropollutants present in water
106 (e.g., pharmaceuticals and pesticides), the formation of some toxic transformation
107 products is reported.30, 31
108 This study presents an updated overview of ClO2 reaction chemistry in water and
109 wastewater treatment, especially the kinetics and mechanisms of ClO2 reactions with
110 inorganic and organic compounds. The literature reports are summarized primarily
111 based on the functional groups of the compounds, i.e., inorganic compounds (e.g., I-,
112 CN-, NO2-, SO32-, Fe(II), Mn(II) and As(III)) and organic compounds (e.g., olefins,
113 amines, phenols, anilines, thiols, amino acids, etc.). Additionally, the transformation
114 of micropollutants during ClO2 oxidation is summarized. Quantitative
115 structure-reactivity relationships (QSARs) are derived for compounds bearing amines
116 and phenols and the ClO2 reactivity with some emerging contaminants are predicted
117 accordingly. Additionally, the transformation of micropollutants during ClO2
118 oxidation is summarized. Finally, the removal of inorganic and organic compounds
119 under water treatment conditions are discussed to provide a picture of their
120 transformation in practical ClO2 treatment.
121
122 2. Physical and chemical properties of ClO2
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123 ClO2 is highly soluble in waters (about 3 g∙L-1 at 25°C) and remains as dissolved View Article Online
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124 gas in solutions. Thus, hydrolysis of ClO2 is insignificant in wide pH range of 2.0–

125 10.0. However, ClO2 can undergo disproportionation in alkaline solution to form
126 chlorite and chlorate (Eq. 1).32
127 2𝐶𝑙𝑂2 +2𝑂𝐻 ― = 𝐶𝑙𝑂2― + 𝐶𝑙𝑂3― + 𝐻2𝑂 (1)
128 Due to the instability of ClO2 gas when compressed, ClO2 is generally generated
129 on site. ClO2 is generated via mixing chlorite or chlorate salts with strong acids (e.g.,
130 H2SO4, HCl) or oxidants (e.g., Cl2, HOCl, H2O2).33 The generated ClO2 solution
131 inevitably contains unreacted raw reactants (e.g., chlorite or chlorate) or some
132 side-reaction products (e,g., Cl2) as impurities.
133 The molecular structure of ClO2 is shown in Fig. 1. The Cl-O bond length is 1.47
134 Å and the O-Cl-O angle is 117.6°. ClO2 has an absorption peak at 359 nm, with a
135 molar absorptivity of 1250 M-1cm-1. This extinction coefficient is independent of
136 temperature, pH, and ionic strength and is often used for determining ClO2
137 concentrations.
138
139 Fig. 1 The molecular structure of ClO2
140 ClO2 has an odd number of valance electrons and it is a stable radical. ClO2
141 usually reacts with organic compounds via electron transfer pathway. The organic
142 compounds serve as an electron acceptor and ClO2 per se is reduced to the chlorite
143 anion (Eq. 2). By comparison, chlorination of organic compounds usually initiates
144 with an electrophilic attack of HOCl at nucleophilic sites, which leads to formation of
145 chlorinated byproducts.34, 35 Ozonation generally proceeds with ozone addition

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146 reactions to unsaturated bonds or other electron donating moieties, resulting inView Article Online
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147 oxygen-substitution or ring cleavage.36, 37 Therefore, ClO2 oxidation is

148 mechanistically different from chlorination or ozonation processes.
149 𝐶𝑙𝑂2 + 𝑒 ― = 𝐶𝑙𝑂2― (2)
150 The redox potential for the ClO2/ClO2- couple is pH-dependent38 because of the
151 photolytic equilibrium between chlorite and chlorous acid (pKa = 1.72). In drinking
152 water treatment (pH > 4.0), the E0red(ClO2/ClO2-) is at 0.95 V.39 Chlorite generated
153 from ClO2 can be further reduced to chloride ions (E0red(ClO2-/Cl-) =1.58V) by some
154 reductive compounds (Eq. 3).40 Thus the overall reaction will be that 1 mol ClO2
155 accepts 5 mol electrons and is reduced to chloride ions.
156 𝐶𝑙𝑂2― +4𝐻 + +4𝑒 ― = 𝐶𝑙 ― +2𝐻2𝑂
157 (3)
158
159 3. ClO2 oxidation of inorganic and organic compounds
160 The generic chlorine dioxide oxidation reaction is shown in Eq. 4:
161 𝐶𝑙𝑂2 +𝐴→𝑝𝑟𝑜𝑑𝑢𝑐𝑡 (4)
162 where A is an inorganic or organic compound.
163 Previous studies have determined that the kinetics of such reactions can be well
164 described by the second-order kinetics model, as shown in Eq. 5:

𝑑[𝐴]𝑡𝑜𝑡
165 𝑑𝑡 = ― 𝑘𝑎𝑝𝑝[𝐴]𝑡𝑜𝑡[𝐶𝑙𝑂2] (5)
166 where kapp is the apparent second-order reaction rate constant and [A]tot refers to the
167 total concentrations of A species.
168 ClO2 is a neutral compound and does not hydrolyze in water. When A can
169 dissociate according to an acid-base equilibrium controlled by pH, kapp, which
7
170 characterizes the sum of the reactions of the two species HA and A-, is DOI:
a linear View Article Online
10.1039/D0EW00231C
171 function of the composition (Eq. 6).

172 𝑘𝑎𝑝𝑝 = (1 ― 𝛼)𝑘𝐻𝐴 +𝛼 ∙ 𝑘𝐴 ― = 𝑘𝐻𝐴 + 𝛼(𝑘𝐴 ― ― 𝑘𝐻𝐴) . (6)
173 kHA and kA - here represent the specific second-order reaction rate constants for the
174 reactions of ClO2 with HA and A-, respectively. α is the fraction of the compound
175 occurring in the deprotonated form (A- ) (Eq. 7).
[𝐴 ― ] 1
176 𝛼 = [𝐴 ― ] + [𝐻𝐴] = (𝑝𝐾𝑎 ― 𝑝𝐻) (7)
1 + 10
177 By using Eq. 5, lots of kinetics was obtained for the reactions between ClO2 and
178 diverse groups of inorganic and organic compounds. For the kinetic measurements,
179 stopped-flow method is usually used and the concentrations of precursors are set to be
180 5–10 times higher than ClO2 to achieve the pseudo-first-order reaction conditions.
181 The second-order reaction rates of ClO2 oxidation presented in Section 3.1, 3.2 and
182 Section 4 are mainly obtained via this method.
183 Notably, recent studies confirmed and quantified the formation of HOCl during
184 ClO2 reactions with organic compounds and NOM.15, 41, 42 Trace amount of HOCl can
185 greatly enhance the transformation efficiency of some pollutants, such as atenolol,
186 metoprolol and ciprofloxacin.41 However, most of previous studies were conducted
187 using ClO2 solutions without adding HOCl scavenger (e.g., glycine). Therefore, bias
188 may present in the reported apparent or specie-specific reaction rates for ClO2
189 oxidation because of the interferences from in situ formed HOCl during reaction,
190 especially for compounds (e.g., primary and secondary amines) with higher reactivity
191 towards HOCl than ClO2.
192
193 3.1. Oxidation of inorganic compounds
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194 ClO2 can oxidize many of the inorganic compounds found in naturalDOI:
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195 ClO2 is firstly reduced to chlorite via the single electron transfer, but chlorite might

196 not be the final reduction product. Further reduction of chlorite can occur as shown in
197 Eq. 3 with presence of some reductive inorganic compounds (e.g., iodide and
198 cyanide), despite of the much slower redox reaction in slightly acidic to neutral
199 circumstances. The speciation of the oxidation products is governed by reaction pH
200 and the molar ratio of ClO2 and the reactants. Table 1 lists the species-specific and
201 apparent second-order reaction rate constants of ClO2 reactions with inorganic
202 compounds commonly found in natural waters.
203
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204 Table 1 Reaction rate constants of ClO2 with inorganic compounds View Article Online
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Species-specific Apparent

second-order reaction second-order
Compounds rate constants (M-1s-1) reaction rate Refer

pKa T (oC)
(HA/A-) constants at pH ences
kHA kA- 7.0,
kapp (M-1s-1)
Iodide (I-) 1.4×103 1.4×103 22–24 8
Bromide (Br-) < 10-4 < 0.05 22–24 8

Cyanide (HCN/CN-) 9.4 < 10-5 8.0×103 4.0×102 22–24 8
Nitrite (HNO2/NO2-) 3.3 1.1×102 1.1×102 22–24 8
Sulfite (HSO3-/SO32-) 7.2 2.7×106 2.7×106 25 42
Ammonia
9.3 <10-6 <10-6 <10-6 22–24 8
(NH4 +/NH
3)
Iron (II) (Fe2+/FeOH+) 3×103 3.0×103 22–24 8
Manganese (II)
10.6 < 0.1 ~ 2.0×107 5.0×103 22–24 8
(Mn2+/MnOH+)
205
206 3.1.1. I-, CN-, NO2-, SO32- and HS-
207 During oxidation of aqueous iodide, ClO2 can rapidly oxidize I- to I2 (Eq. 8).38
208 Chlorite produced by the reduction of ClO2 can also react with excess I- to form I2 at
209 pH 4–8 (Eq. 9).44-46 ClO2 has also been reported to oxidize I- to iodate (IO3-), but only
210 at very low pH (1–3.5), which is not representative of the pH of source waters.46 No
211 substantial IO3- formation is observed under practical ClO2 oxidation treatment
212 conditions.47 It should be noted that ClO2 does not react with chloride and barely react
213 with bromide (< 10-4 M-1s-1).8 Since HOCl is formed during ClO2 oxidation,
214 chloramine and hypobromous acid (HOBr) is possible to form. However, only trace
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215 level of total organic bromine TOBr (< 10 μg∙L-1) was formed when 1.5 mg∙L -1 ClOView Article Online
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216 reacted with 3 mg∙L-1 Suwannee River NOM solution.48 Therefore, the side-reactions

217 between in situ formed HOCl and inorganic ions are insignificant.
218 2𝐶𝑙𝑂2 +2𝐼 ― = 2𝐶𝑙𝑂2― + 𝐼2 (8)
219 𝐶𝑙𝑂2― +4𝐻 + +4𝐼 ― = 2𝐼2 + 𝐶𝑙 ― +2𝐻2𝑂 (9)
220 Subsequently, the disproportionation of I2 leads to the formation of HOI (Eq.
221 10)49, 50 and the reaction between I2 and excessive I- results in the formation of I3- (Eq.
222 11).51
223 𝐼2 + 𝐻2𝑂⇌𝐻𝑂𝐼 + 𝐼 ― + 𝐻 + (10)
224 𝐼2 + 𝐼 ― ⇌𝐼3― (11)
225 It has been reported that I2, HOI and I3- can react with NOM in water to form
226 iodinated DBPs including iodoform (CHI3) and iodoacetic acid (IAA).44, 51 Thus,
227 formation of iodinated DBPs was observed during ClO2 oxidation of
228 iodine-containing waters.52, 53
229 Similar to iodide, the oxidation of cyanide (CN-) and nitrite (NO2-) by ClO2
230 mainly involves electron transfer reactions which generate cyanate (CNO-) and nitrate
231 (NO3-), respectively (Eq. 12–13).43, 54-56

―
232 2𝐶𝑙𝑂2 + 𝐶𝑁 ― +2𝑂𝐻 ― = 2𝐶𝑙𝑂2― + 𝐶𝑁𝑂 + 𝐻2𝑂 (12)
233 2𝐶𝑙𝑂2 + 𝑁𝑂2― + 𝐻2𝑂 = 2𝐶𝑙𝑂2― + 𝑁𝑂3― +2𝐻 + (13)
234 Chlorite is primarily produced from these reactions, which may further reduced
235 to chloride via reactions with CN- and NO2- (Eq. 14–15).
236 𝐶𝑙𝑂2― +2𝐶𝑁 ― = 𝐶𝑙 ― +2𝐶𝑁𝑂 ― (14)
237 𝐶𝑙𝑂2― +2𝑁𝑂2― = 𝐶𝑙 ― +2𝑁𝑂3― (15)
238 The mechanism of sulfite oxidation by ClO2 is more complicated due to the
239 pH-dependent distribution of aqueous sulfite (S(IV)) species

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240 ([S(IV)]=[H2SO3]+[HSO3-]+[SO32-]).39, 57-59 In addition, the molar ratio of S(IV) andView Article Online
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241 ClO2 also influences the speciation of products. The reaction stoichiometry and

242 products of ClO2 and sulfite are summarized in Scheme 1.
243
244 Scheme 1 Summary of reaction stoichiometry and products of ClO2 oxidation of
245 sulfur-containing inorganic compounds (a) SO32-; (b) HS-
246 As illustrated in Scheme 1a, in a slightly acidic solution, SO32- is oxidized to
247 sulfate and both chloride and chlorate are produced from ClO2 reduction at ClO2 to
248 SO32- molar ratio of 1:1 (Eq. 16).60 When ClO2 to SO32- molar ratio is 1:3, dithionate,
249 sulfate and chloride are generated (Eq. 17).60
250 2𝐶𝑙𝑂2 +2𝑆𝑂23 ― + 𝐻2𝑂 = 2𝑆𝑂24 ― + 𝐶𝑙 ― + 𝐶𝑙𝑂3― +2𝐻 + (16)
251 2𝐶𝑙𝑂2 +6𝑆𝑂23 ― = 𝑆2𝑂26 ― +4𝑆𝑂24 ― +2𝐶𝑙 ― (17)
252 In alkaline solutions, SO32- is oxidized to sulfate, but the species of ClO2
253 reduction products varied with the ratio of ([S(IV)]0/[ClO2]). Three competitive
254 stoichiometries have been found, with the ratio of ([S(IV)]0/[ClO2]) varying between
255 1.5 and 2.0 (Eq. 18–20):61

12
256 2𝐶𝑙𝑂2 + 𝑆𝑂23 ― +2𝑂𝐻 ― = 𝑆𝑂24 ― +2𝐶𝑙𝑂2― + 𝐻2𝑂 (18)View Article Online
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257 2𝐶𝑙𝑂2 +2𝑆𝑂23 ― +2𝑂𝐻 ― = 𝐶𝑙 ― + 𝐶𝑙𝑂3― +2𝑆𝑂24 ― + 𝐻2𝑂 (19)

258 2𝐶𝑙𝑂2 +3𝑆𝑂23 ― +2𝑂𝐻 ― = 𝐶𝑙𝑂2― + 𝐶𝑙 ― +3𝑆𝑂24 ― + 𝐻2𝑂 (20)
259 ClO2 also reacts with hydrosulfide (HS-) quickly.32 The species distribution of
260 the products depends on the pH and the molar ratios between ClO2 and reactants. As
261 illustrated in Scheme 1b, in alkaline solutions, several reactions might contribute to
262 the overall reaction stoichiometry (Eq. 21–24).62
263 8𝐶𝑙𝑂2 + 𝐻𝑆 ― +9𝑂𝐻 ― = 𝑆𝑂24 ― +8𝐶𝑙𝑂2― +5𝐻2𝑂 (21)

264 4𝐶𝑙𝑂2 + 𝐻𝑆 ― +5𝑂𝐻 ― = 𝑆𝑂24 ― +2𝐶𝑙𝑂3― +2𝐶𝑙 ― +3𝐻2𝑂 (22)
265 2𝐶𝑙𝑂2 + 𝐻𝑆 ― + 𝑂𝐻 ― = 𝑆 + 2𝐶𝑙𝑂2― + 𝐻2𝑂 (23)
266 8𝐶𝑙𝑂2 +5𝐻𝑆 ― +13𝑂𝐻 ― = 5𝑆𝑂24 ― +8𝐶𝑙 ― +9𝐻2𝑂 (24)
267 Therefore, ClO2 can rapidly remove the majority of anionic inorganic
268 contaminants under water treatment conditions. For example, hydrosulfide is
269 commonly present in municipal wastewaters, produced from biological reduction of
270 sulfates and the decomposition of sulfur-containing organic moieties. Post-treatment
271 of ClO2 can rapidly destroy hydrosulfide to abate its unpleasant smell in wastewater
272 discharges. Moreover, contamination of CN- may occur when source waters impacted
273 by discharges from electroplating industries. The level of CN- in drinking waters is
274 limited to 0.2 mg∙L-1 by USEPA due to its severe toxicity. Pretreatment with ClO2 can
275 detoxify contaminated source waters by converting CN- to much less toxic CNO-.
276 3.1.2. Fe(II), Mn(II), and As(III)
277 Soluble iron and manganese generally exist in their divalent forms, which
278 impedes drinking water treatment.63 Fe(II) and Mn(II) can be oxidized to insoluble
279 Fe(III) and Mn(III or IV) species, respectively and then removed by coagulation
280 and/or filtration in water treatment. ClO2 is often used as primary oxidant to reduce
13
281 Fe(II) and Mn(II) level in source waters in this way,, especially in small
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282 treatment plants or in circumstances like a shock increase in soluble iron or

283 manganese in the summer.64 ClO2 oxidizes Fe(II) and Mn(II) via rapid one-electron
284 transfer leading to the formation of chlorite.64-66 In addition, chlorite (E0red(ClO2-/Cl-)
285 =1.58V) can further react with Fe(II) (E0red(Fe3+/Fe2+) = 0.77V) and Mn(II)
286 (E0red(Mn3+/Mn2+) =1.50V).40 The overall reactions under water treatment conditions
287 can be summarized as in Eq. 25–26.32, 65-67
288 𝐶𝑙𝑂2 +5𝐹𝑒2 + +4𝐻 + = 5𝐹𝑒3 + + 𝐶𝑙 ― +2𝐻2𝑂

289 (25)
290 2𝐶𝑙𝑂2 +5𝑀𝑛2 + +6𝐻2𝑂 = 5𝑀𝑛𝑂2(𝑠) + 12𝐻 + +2𝐶𝑙 ― (26)
291 The reaction rate constants of ClO2 oxidation of Fe(II) and Mn(II) increase
292 greatly with increasing pH.65 The reaction rate constants of Mn(II) oxidation increases
293 from 3.2×103 M-1s-1 to 5.0×104 M-1s-1 when pH increases from 6 to 8.40 Results from
294 bench and pilot studies shows that ClO2 pre-treatment incorporated with
295 post-filtration can achieve promising removal of Fe(II) and Mn(II) (> 95%).68-70
296 It should be noted that adding dissolved ferrous sulfate (FeSO4) is an approach to
297 eliminate excess chlorite from waters to meet the regulatory standards (Eq. 27).71
298 Fe(II) rapidly reduced chlorite to chloride (kapp = 1.9×103 M-1s-1 at pH 7.0)72 and the
299 formed Fe(III) colloids can then be removed during subsequent coagulation or
300 filtration.
301 4𝐹𝑒2 + + 𝐶𝑙𝑂2― +10𝐻2𝑂⇌4𝐹𝑒(𝑂𝐻)3(𝑠) + 𝐶𝑙 ― +8𝐻 + (27)
302 In natural waters, soluble arsenic mainly exists as a combination of As(III)
303 [AsO33-] and As(V) [AsO43-].73 ClO2 can oxidize As(III) to As(V) (Eq. 28–29),
304 leading to promoted removal of arsenic in post-filtration or adsorption treatment
305 because removal of As(V) from waters is more accessible than As(III).74-76
14
306 2𝐶𝑙𝑂2 + 𝐴𝑠𝑂33 ― + 𝐻2𝑂 = 𝐴𝑠𝑂34 ― +2𝐶𝑙𝑂2― +2𝐻 + (28)View Article Online
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307 2𝐶𝑙𝑂2 +5𝐴𝑠𝑂33 ― + 𝐻2𝑂 = 5𝐴𝑠𝑂34 ― +2𝐶𝑙 ― +2𝐻 + (29)

308 Effective oxidation of As(III) to less toxic As(V) can be achieved at a pH range of 5
309 to 9 and at a ClO2 to As(III) molar ratio of 1:1. Acidic conditions and higher dose of
310 ClO2 can promote As(III) removal efficiency. 77 ClO2 removes As(III) less effectively
311 than free chlorine or permanganate in demineralized water.75, 77, 78
312
313 3.2. Oxidation of organic compounds

314 The molecular structure of ClO2 has a central chlorine atom with a Cl=O double
315 bond and a three-electron bond, where one electron tends to be associated with the
316 chlorine atom, one primarily with the oxygen atom, and one in the region between
317 them (i.e., in the bond). ClO2 therefore tends to react with organic compounds as a
318 one-electron accepter and is reduced to chlorite. That makes ClO2 a selective oxidant
319 whose reactivity generally favors organic molecules with a lone pair of electrons or π
320 electrons (e.g., tertiary amines, phenols and aniline). The DBPs from ClO2 oxidation
321 detected in water treatment are mainly chlorite, chlorate, oxidized by-products (acids,
322 aldehydes and alcohols) and some chlorinated by-products.79, 80 Tracking the
323 precursors and the formation pathways of these oxidized by-products can help to
324 optimize the use of ClO2, avoiding to a great extent the formation of toxic
325 by-products.
326 The formation of HOCl is known to correlate with the total organic chloride
327 (TOCl) formation during ClO2 oxidation of phenols.15 That raises the question on
328 what reactions causing HOCl formation. The organic molecule is generally converted
329 to a free radical after the initial electron transfer to a ClO2 molecule. It can then
330 combine with the oxygen atom of another ClO2 molecule causing the release of
15
331 HOCl.81 Exploring the reactions of ClO2 with organics from the perspective
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332 release of HOCl can provide new insight into DBP control in ClO2 treatment. This

333 section will therefore emphasize the origins of typical oxidized organic by-products
334 and the formation of HOCl during ClO2 oxidation in actual treatment situations.
335
336 3.2.1. Reaction with unsaturated olefins
337 ClO2 reactions with olefins were generally slow or negligible with rates in the
338 range of 10-3 to 1.5×102 M-1s-1(Table 2). Unsaturated carboxylic acids (e.g., cinnamic,
339 maleic and fumaric acids) are reported to be inert towards ClO2. There is dispute
340 about the extent to which ClO2’s reactions are initiated by hydrogen abstraction or
341 electron transfer. Rav-Acha and his co-workers found no isotope effect on olefins’
342 reactions in H2O and D2O, which argues against hydrogen abstraction. In view of the
343 strong solvent effect and the linear relationship between reaction rate and olefins’
344 ionization potentials, the electron transfer mechanism seems more plausible (Scheme
345 2). ClO2 attacks at the double bonds to form cation radicals, which combine rapidly
346 with another ClO2 molecule (which has unpaired electrons) to form esters. The esters
347 thus formed are unstable and convert to ketones, alcohols or acids through HOCl
348 elimination. During ClO2 oxidation of cyclohexene ( ), cyclohex-1-ene-3-one
349 ( ) and chlorocyclohen-1-ene ( ) were found to be the main products,
350 companied by other chlorinated cyclohexan-1-ol derivatives ( ).82
351 Phenyl-2-chloroethanone ( ) and phenyl-2-chloroethanol ( ) are
352 found to be main products from ClO2 oxidation of styrene ( ).83 ClO2 oxidation
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353 converts about half of indene ( ) to chlorohydrin ( ),84 suggesting the

354 significance of HOCl yields during the reaction. Relatively low chlorite formation
355 relative to the ClO2 consumed also supports the substantial formation of HOCl during
356 olefin oxidation. Only a quarter of the ClO2 consumed is reduced to chlorite when the
357 molar ratio of ClO2 to indene is 2:1 at pH 7.0.84 ClO2 oxidation of cyclohexene and
358 isoprene also has relative low chlorite conversion (< 20%).42
359 In general, fractions of olefins in NOM are minor.85 Olefins detected in surface
360 waters and domestic sewages are mainly in forms of branched or cyclic olefins (e.g.,
361 polycyclic aromatic hydrocarbon, PAH) derived from pollutions of petroleum
362 industries. However, oxidation of olefins in water treatments are unlikely to be
363 significant because due to the low concentrations of these olefinic pollutants in source
364 waters (<100 ng∙L-1) and sewages (< 500 μg∙L-1).86, 87 In addition, ClO2 reactions with
365 olefins and PAHs generally take hours to accomplish,88 which may likely occurs in
366 distribution systems with adequate ClO2 residual.
367 Table 2 Kinetics of ClO2 oxidation of selected compounds with unsaturated bonds,
368 oxygenated or sulfur-containing moieties
Apparent second-order reaction rate

Compounds T (oC) Reference
constants at pH 7.0, kapp (M-1s-1)
Olefins
Indene 1.1×102 84
(E)-Stilbene 1.3×102 84
Acenaphthylene 6.2 84
α-Methylstyrene 3.1 84
trans-α-Methylstyrene 1.2 25 89
β-Methylstyrene 3.1×101 84
17
ρ-Methylstyrene 1.6×10-1 25 89 View Article Online

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ρ-Phenylstyrene 1.0×10-1 25 89

Styrene 1.6 84
ρ-Chlorostyrene 4.1×10-1 25 89
Cyclohexene 7.2×10-1 84
Allybenzene 2.4×10-1 84
1-Hexene-3-ol < 10-2 24 8
2,4-Hexadiene-1-ol 8.6 24 8
Ketones
2-Pentanone < 3.0×10-5 24 8
Acetone < 10-5 24 8
5,5-Dimethyl-1,3-cyclohexanedione
- 24 8
(dimedone)
1,4-Benzoquinone < 5.0×10-3 90
Aldehydes
Benzaldehyde < 3.0×10-4 23 91
Butyryl aldehyde < 1.0×10-2 92
Other oxygenated compounds
2-Ethanolfuran 3.7×10-1 88
2,5-Dimethylfuran 1.2×102 8
Furfuryl alcohol 3.7×10-1 24 8
Ascorbate 1.0×107 22 13
Anisole < 2.0×10-3 24 8
Phthalic acid < 10-3 24 8
Sulfur-containing compounds
2-Methyl-2-propanethiol 7.5×108 24 8
369
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370
371 Note: modified from reference84
372 Scheme 2 Reaction pathway proposed for the ClO2 oxidation of olefins
373
374 3.2.2. Reaction with oxygenated moieties

375 3.2.2.1. Aliphatic alcohols, aldehydes, ketones and organic acids
376 ClO2 has limited reactivity towards aliphatic alcohols, aldehydes, ketones and
377 organic acids and the presence of activating electron-donor groups could enhance the
378 reactivity. In practical water treatment conditions, ClO2 is unlikely to react with the
379 alcohols, aldehydes, ketones and organic acids commonly found.
380 Alcohols are generally unlikely to convert to ketones or carboxylic acids at
381 neutral pH and moderate temperature because the relevant reaction rates are only
382 10-4–10-5 M-1s-1. The reaction rate of ClO2 oxidation of furfuryl alcohol is about 0.4
383 M-1s-1 at pH 8.0 and 23oC,8 and that is higher than the rates of other alcohols. The
384 reaction mechanism is thought to start with hydrogen abstraction as illustrated in
385 Scheme 3.
386
387 Scheme 3 Reaction pathway proposed for ClO2 oxidation of alcohols
388 The carbonyl group in aldehydes and ketones is polarized with the carbon atom
389 bearing a partial positive charge. Thus, the reactivity of aldehydes and ketones
390 towards ClO2 is limited because those groups usually favor nucleophilic attack on the
19
391 C=O bond. Hexanal and 2-methybutanal are reported not to react with DOI:
ClO 2 at
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392 moderate temperatures.93 Some aldehydes, though, can be oxidized to carboxylic

393 acids by ClO2 in neutral aqueous conditions. Oxidation of butyraldehyde to butyric
394 acid is one example, but the reaction rate is only 10-2 M-1s-1 or less.92 In addition,
395 chlorite can also oxidize aldehydes to carboxylic acids at slightly acidic or neutral
396 pH.94, 95 However, the accumulation of 10–50 μg∙L-1 of aldehydes is observed in
397 ClO2-treated waters.27 This suggests that the oxidation of aldehydes by ClO2 in water
398 treatment is so slow as to be insignificant.

399 Ketones show higher reactivity towards ClO2 than aldehydes because of the
400 stronger electron-donating effect of the R groups attached to both sides towards the
401 positive carbonyl carbon. However, low molecular weight ketones like acetone and
402 2-pentanone are generally unreactive towards ClO2, with rates lower than 10-5 M-1s-1.
403 Although the second-order reaction rate between ClO2 and protonated dimedone (pKa
404 =5.2) is about 2×104 M-1s-1, deprotonated dimedone is found to be inert with ClO2
405 oxidation.8 ClO2 can oxidize benzoquinone, but at the relatively slow rate of 5×10-3
406 M-1s-1 at pH 7.0.8 Degradation of benzoquinone to cyclopent-4-ene-1,3-dione
407 derivatives and chlorinated acetones after dealkylation occurs during ClO2
408 oxidation.96
409 Carboxylic acids are usually unreactive towards ClO2 in general and are often
410 found in ClO2-treated water. Some carboxylic acids containing specific reactive
411 groups (e.g., salicylic acids and glyoxylic acid) are exceptions.
412
413 3.2.2.2. Phenolic compounds
414 Humic substances usually have a large fraction of polyphenolics97 which serve
415 as major electron-donating groups in the oxidation of humic substances.98 That
20
416 accelerates the consumption of the oxidant and results in the formation ofView Article Online
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417 considerable amounts of DBPs.

418 Phenols react with ClO2 rapidly with rates of 103 –108 M-1s-1 at neutral pH
419 (Table 3). The reaction rate constants of dissociated phenols with ClO2 are generally
420 about six orders of magnitude higher than those of the undissociated phenols.99 High
421 pH therefore favors ClO2 oxidation of phenols. The substituents on phenols greatly
422 affect their ClO2 oxidation rates. Lee and von Gunten have developed QSARs
423 defining this and negative linear relationships between the Hammett constants
424 (∑σ-o,m,p and ∑σ+o,m,p) of the substituents on phenols and the second-order reaction
425 rate constants with ClO2 of dissociated and undissociated substituted phenols. Eq. 30–
426 31 and Fig. 2 show their results.99 The reaction rate constants decrease with increasing
427 Hammett constants, which might be attributed to higher bond dissociation energies
428 when electron-withdrawing substituents are present.100 Based on the established
429 QSAR relationship, the reactivity of emerging micropollutants and other synthetic
430 organic compounds with ClO2 can be predicted. The second-order reaction rates
431 between ClO2 and phenolic micropollutant 17α-ethinylestradiol, bisphenol A,
432 acetaminophen and triclosan can be well predicted by Eq. 31 within a prediction error
433 range of 2/3–1.5 (i.e., the ratio between the differences between prediction rates and
434 measured rates).

+
435 log (𝑘𝑃ℎ𝑂𝐻) = 0.41( ± 0.50) ― 4.69( ± 1.13) ∗ ∑𝜎𝑜,𝑚,𝑝
436 (30)
―
437 log (𝑘𝑃ℎ𝑂 ― ) = 8.03( ± 0.13) ― 3.24( ± 0.28) ∗ ∑𝜎𝑜,𝑚,𝑝
438 (31)
21

439 Table 3 Kinetics of ClO2 oxidation of phenolic compounds
Species-specific
Apparent second-order rate
Hammett constants second-order rate
Compounds pKa constants at pH 7.0, T (oC) References
constants(M-1s-1)
kapp (M-1s-1)
σ σ+ σ- HA A-
Phenol 0 0 0 10.0 4.0×10-1 4.9×107 4.9×104 24 8
2-Methylphenol -0.13 -0.20 -0.17 10.3 1.6×101 4.4×108 2.2×105 24 8
3-Methylphenol -0.07 -0.07 -0.06 10.1 < 4.0 1.0×108 7.9×104 24 8
4-Methylphenol -0.17 -0.31 -0.17 10.3 4.0×101 5.2×108 2.6×105 24 8
4-Ethylphenol -0.15 -0.3 -0.19 10.3 5.0×101 8.0×108 4.0×105 24 8
4-tert-Butylphenol -0.2 -0.26 -0.13 10.2 1.1×101 1.5×108 9.5×104 24 8
2-Carboxylphenol -0.69 -0.01 0.31 13.6 4.6×101 6.0×107 6.1×101 24 8
4-Carboxylphenol 0 -0.02 0.31 9.2 4.0×101 4.8×107 3.0×105 24 8
4-Acetylphenol 0.5 0.5 0.84 8.1 < 0.5 8.0×105 5.9×104 24 8
4-Cyanophenol 0.66 0.66 1 7.9 < 4.0×103 4.9×102 21 101
2-Chlorophenol 0.4 0.07 0.19 8.5 1.5 3.5×107 1.1×106 24 8
4-Chlorophenol 0.23 0.11 0.19 9.4 <2 3.5×107 1.4×105 24 8
4-Bromophenol 0.23 0.15 0.25 2.7×107 2.7×107 24 8
2-Hydroxyphenol -0.2 -0.60 -0.37 9.1 < 5.0×103 2.0×109 1.6×107 24 8
3-Hydroxyphenol 0.12 -0.04 0.12 9.2 4.0×101 4.8×107 3.0×105 24 8
4-Hydroxyphenol -0.37 -0.92 -0.37 3.9×104 9.0×108 9.0×108 25 43, 81
22

440 2-Methoxyphenol -0.27 -0.51 -0.37 9.9 1.0×103 1.2×109 1.5×106 24 8
3-Methoxyphenol 0.12 0.05 0.13 4.9×107 4.9×107 21 101
4-Methoxyphenol -0.27 -0.78 -0.26 10.2 2.50×104 1.7×109 1.1×106 24 8
4-Nitrophenol 0.78 0.79 1.27 7.2 1.40×10-1 4.0×103 1.6×103 24 8
4-Sulfonatophenol 0.35 0.35 0.58 8.8 <1 1.0×106 1.6×104 24 8
2,4-Dimethylphenol -0.3 -0.51 -0.34 10.6 9.0×102 2.1×109 5.3×105 24 8
2,5-Dimethylphenol -0.2 -0.27 -0.23 10.2 1.0×102 6.8×108 4.3×105 24 8
2-Methoxy-4-formylphenol 0.15 0.22 0.66 7.7 - 1.8×108 3.0×107 24 8
2,4-Dichlorophenol 0.63 0.18 0.38 7.8 < 0.6 2.2×107 3.0×106 24 8
2,4,6-Trimethylphenol -0.43 -0.72 -0.51 10.9 3.9×103 4.0×109 5.1×105 24 8
2,4,6-Trichlorophenol 1.03 0.26 0.57 6.2 < 8.0×102 5.3×106 4.6×106 24 8
Pentachlorophenol 1.77 1.06 1.31 4.7 1.4×103 1.4×103 24 8
23
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12
logk=8.03(± 0.13)-3.24(± 0.28)o,m,p

Dissociated phenols
R2=0.95 Undissociated phenols
10
Micropollutants
8
17a-ethinylestradiol
logk (M s )
Bisphenol A
-1 -1
6 Acetaminophen
Triclosan
4
2 logk=0.41(± 0.50)-4.69(± 1.13)o,m,p

R2=0.86
0
-2
-1.0 -0.5 0.0 0.5 1.0 1.5
o,m,p or  o,m,p

441
442 Fig. 2 Correlations between the second-order rate constants (logk) for the reactions of
443 ClO2 with non-dissociated phenols vs. +o,m,p (Eq. 30 and Table 3) and with
444 dissociated phenols vs. -o,m,p (Eq. 31 and Table 3). Data is obtained from ref.8, 99
445
446 The reaction pathways involved in ClO2 oxidation of phenols have been
447 investigated intensively. A two-step reaction mechanism has been proposed (Scheme
448 4a). One-electron transfer from phenolate to a ClO2 molecule first forms a phenoxyl
449 radical and chlorite, which is the rate-determining step of the reaction. Subsequently,
450 rapid oxygen transfer to the benzene ring from a second ClO2 molecule results in the
451 generation of HOCl and benzoquinone.81 The release of HOCl during ClO2 oxidation
452 of phenol has a yield of about 50% of the ClO2 consumed.15 The chlorite yields of
453 mono-hydroxy phenols upon ClO2 oxidation are in the range of 40–60%.42, 81 The
454 mechanisms for di- and tri-hydroxy phenols are similar. Bi- or tri-radicals are formed
455 which subsequently transfer to benzoquinones or ring cleavage products (Scheme 4c).
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456
457 Note: modified from reference81, 102
458 Scheme 4 Summary of reaction scheme of ClO2 oxidation of phenolic compounds (a)
459 phenol; (b) hydroquinone; (c) catechol; (d) vanillin alcohol
460 The reactions of phenols can be classified based on their oxidized products.
461 Hydroquinone and mono-hydroxy phenols (without para-substitution) tend to
462 maintain their ring structure, with quinones as the major products (Scheme 4b).98
463 They are classified as Group I compounds. Di- and tri-hydroxy phenols (e.g.,
464 resorcinol and phloroglucinol) and para-substituted mono-hydroxy phenols (e.g.,
465 p-cresol) are classified as Group II, since ring cleavage is likely to occur together with
466 the formation of carboxylic acids (e.g., oxalic and maleic acids) during ClO2 oxidation
467 (Scheme 4c).96 ClO2 oxidation of phenolic lignins (e.g., vanillin alcohol) is one of the
25
468 exceptions from that classification. Lactone ester and quinones are identified
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469 predominant products after their demethylation, rather than ring cleavage products

470 (Scheme 4d).102
471 The products of phenol oxidation vary with the ClO2 dose. When the molar
472 ratio of ClO2 to phenol is above 3, benzoquinone is the main organic product. When
473 phenol was in excess (i.e., ClO2: phenol < 1), chlorinated phenols are also detected in
474 addition to benzoquinone.81 When ClO2 is in large excess, further decomposition of
475 benzoquinone may occur, leading to the formation of ring cleavage products.
476 Degradation of benzoquinone by ClO2 takes 1–3 hours when the dose of ClO2 is 5
477 times that of the benzoquinone.42 Cyclopent-4-ene-1,3-dione derivatives and
478 chlorinated acetones are detected when excess ClO2 reacts with resorcinol and
479 mono-hydroxy phenols.96
480 Considering the prevalence of phenolic moieties in source waters, the toxicity
481 of their oxidized products is critical for the safety of treated water. Benzoquinone is
482 the most significant product and it can inhibit the growth of Pseudomonas
483 fluorescence.103 Quinones, however, might serve as carcinogens because their
484 metabolites can conjugate with glutathione and cysteine, leading to damage to certain
485 cells (e.g., liver, bladder and kidney).104, 105 In addition, quinones can act as mutagens
486 causing aneuploidy in human cells. Quinones formed in the ClO2 pre-treatment of
487 phenolic compounds can promote the formation of chloral hydrate in
488 post-chlorination.96 It should be noted that halogenated benzoquinones are reported to
489 have greater cytotoxicity than most of the regulated DBPs.106 ClO2 pre-treatment
490 might also increase the formation of halogenated benzoquinones during
491 post-chlorination. That deserves further evaluation.
492
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493 3.2.3. Reaction with sulfur-containing moieties View Article Online

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494 The sulfur content of NOM is relatively low (normally less than 3%) contributed

495 by sulfur-containing proteins or amino acids. Treatment of some chemical solutions or
496 industrial wastewater may, however, involve oxidation of sulfur-containing organic
497 compounds.
498 Oxidation of thioether (R1–S–R2) to sulfoxides and sulfones (Scheme 5a) has
499 been observed in the ClO2 oxidation of dialkyl, diaryl and dibenzyl sulfides and of the
500 amino acid methionine at moderate temperature.107, 108 At a ClO2 to thioether molar
501 ratio of 1:2, the sulfoxide (R1–SO–R2) yield reaches 90–100% without significant
502 formation of sulfones.109 When ClO2 is in excess or at equimolar ratio with thioethers,
503 sulfones (R1–SO2–R2) are the major product.110 The degradation pathways of thioether
504 micropollutants (e.g., methiocarb, ametryn, isoproturon) suggest that sulfoxides are
505 the main oxidation products with small proportions of chlorinated sulfoxides.30, 111
506 From a mechanistic point of view, the sulfur atom contains lone electron pairs which
507 are readily attacked by ClO2. The reaction might initiate through electron transfer
508 from a thioether to ClO2 to yield a cation intermediate and chlorite. Based on the
509 material balance of the elements and the observed formation of chlorinated
510 by-products, HOCl is also released. However, experimental data on the inorganic
511 products from ClO2 oxidation of thioether are too scarce to confirm each step.
512 ClO2 oxidation of thiol-containing compounds occurs rapidly due to the strong
513 nucleophilicity of the thiol group (-SH). However, thiols are less soluble in water than
514 phenols and alcohols because the S-H bond is only slightly polar and has little
515 tendency to hydrogen bond. Reactions with thiols have therefore mainly been
516 investigated in organic solvents.112 Cysteine-based amino acids or peptides (e.g.,
517 glutathione and cystine) are common thiol-containing moieties found in source
27
518 waters, and they play critical roles in biological activity. ClO2 oxidation of these
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519 is initiated by transferring one electron from disassociated RS- anion to ClO2 resulting

520 in RS• radical and chlorite formation (Scheme 5b). ClO2 oxidation of thiols mainly
521 leads to disulfides, then sulfinic (RSO2H) and sulfonic acids (RSO3H) as further
522 oxidation products with excess ClO2 and at acidic pH (Scheme 5b). It should be noted
523 that the chlorite by-product can oxidize cysteine and glutathione following pathways
524 different from those of ClO2.113, 114 Chlorite is more likely to react with RSH directly,
525 rather than with RS- anion, via oxygen transfer to form corresponding disulfides and
526 sulfonic acids. Chloride is then the main reduced product in the oxidation of cysteine,
527 cystine and glutathione, since all can further reduce chlorite. However, more
528 experimental data are needed to clarify to what extent chlorite reacts with other
529 aliphatic and aromatic thiols. ClO2 reactions with other sulfur-containing compounds
530 including thiourea (CS(NH2)2) have also been studied. Sulfinic acid, sulfonic acids
531 and disulfides are reported to be main products.115
532 The thiol concentrations in source waters are quite low. Limited results show
533 that 18.7 M thiol are present per mM dissolved organic carbon (DOC) in Suwannee
534 River NOM.116 In consideration of the 1–10 mg/L DOC levels in source water, the
535 thiol concentrations may exist at sub M to M levels. Their ClO2 consumption
536 should be minor.
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537
538 Note: modified from references109, 114
539 Scheme 5 Summary of reaction scheme of ClO2 oxidation of sulfur-containing
540 compounds (a) sulfides and (b) thiols
541
542 3.2.4. Reaction with nitrogen-containing moieties
543 Nitrogenous organic compounds are becoming more prevalent in source waters
544 due to increasing industrial and agricultural discharges,117 which poses more
545 challenges to control nitrogenous DBP formation in water treatment.
546 Table 4 lists the species-specific second-order rate constants (kClO2-A-) and the
547 apparent second-order rate constants (kapp) at pH 7.0 for ClO2 with some aliphatic
548 amines. In general, the reaction rates decrease in the order tertiary amine > secondary
549 amine > primary amine. For tertiary amines, the reaction rate constants are in the
550 range of 103–106 M-1s-1 at neutral pH, which is 2–5 orders of magnitude higher than
551 those of secondary or primary amines. Primary and secondary amines are, however,
552 more reactive in chlorination than tertiary amines.35 ClO2 reacts much faster with
553 deprotonated amines than with neutral species because the deprotonated amines are
29
554 stronger electron donors.118, 119 Therefore, pH is a critical factor in ClO2 oxidation ofView Article Online
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555 amines, and the reaction rates tend to increase with increasing pH. But substituents

556 induce strong effects on the reaction rate constants. Higher electron density on the
557 nitrogen atom of an amine favors attack ClO2 molecules. The Taft constants of
558 nitrogen substituents are plotted against the ClO2 oxidation rates of amines in Fig. 3.
559 The Taft’s constants were calculated as Eq.32:
560 σ*=∑σ*R1+σ*R2+σ*R3 (32)
561 where ∑σ*R represents the Taft constants of each substituents on the amine’s nitrogen
562 atom. The reaction rate constants increase with decreasing ∑σ*, suggesting that
563 amines with stronger electron-donating substituent groups (with smaller σ*) tend to be
564 more reactive with ClO2. Two different correlations are evident between tertiary
565 amines and secondary (and primary) amines because of the large gap between their
566 reactivities towards ClO2. The slope of the correlation for tertiary amines is lower
567 than that for the others, indicating that the effects of substituents on ClO2 reactivity
568 are more significant for secondary and primary amines. Benzylamines, however,
569 deviate from the lines for secondary and primary amines, perhaps due to different
570 reaction mechanisms. The reaction kinetics for ClO2 oxidation of ciprofloxacin
571 (secondary amine) and roxithromycin (tertiary amine) can be well predicted based on
572 the QSAR relationship of amines within a factor of 1/3–3 of measured rates.
573
574 Table 4 Kinetics of ClO2 oxidation of selected nitrogen-containing compounds
Taft kapp (M-1s-1) T

Compounds pKa kClO2-A-(M-1s-1) Ref
constants at pH 7.0 (oC)
Benzylamine 1.25 9.6 3.9×10-2 9.8×10-5 25 10
Methylamine 0.98 10.6 5.0×10-1 1.3×10-4 24 8
2-Aminoethanol 1.23 9.4 1.4×10-2 5.1×10-5 25 10
Urea - < 1×10-6 8
30
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N-Methyl-4-methoxybe DOI:
0.73 10.0 2.7×102 2.9×10-1 25 10 10.1039/D0EW00231C
nzylamine
Dimethylamine 0.49 10.7 5.0×102 10.0×10-2 24 8

Isopropylbenzylamine 0.57 9.7 9.1 1.9×10-2 25 10
Diisopropylamine 0.11 11.0 3.5×102 3.4×10-2 25 10
Diethylamine 0.29 10.5 1.0×103 3.2×10-1 120
Dibenzylamine 1.03 8.4 8.3 3.0×10-1 9
Benzyl-tert-butylamine 0.46 10.2 2.8×102 1.8×10-1 25 10
N,N-Dimethyl-3-metho
0.24 9.0 2.9×104 2.6×102 25 10
xybenzylamine
N,N-Dimethyl-4-metho
0.24 9.3 4.9×104 2.3×102 25 10
xybenzylamine
N,N-Dimethyl-4-methyl
0.24 9.2 3.5×104 2.1×102 25 10
benzylamine
N,N-Dimethyl-3-nitrob
0.48 8.2 6.2×103 3.7×102 25 10
enzylamine
N,N-Dimethyl-4-nitrob
0.50 8.1 4.5×103 3.6×102 25 10
enzylamine
N,N-Dimethyl-benzyla
0.27 9.0 2.7×104 2.5×102 25 10
mine
N,N-Dimethyl-tert-buty
-0.3 10.7 2.3×105 4.7×101 25 10
lamine
N,N-Dimethyl-3-Cl-ben
0.39 8.7 1.6×104 3.4×102 25 10
zylamine
N,N-Dimethyl-4-Cl-ben
0.35 8.8 2.0×104 2.9×102 25 10
zylamine
N,N-Dimethyl-4-F-benz
0.32 8.9 2.0×104 2.3×102 25 10
ylamine
Triethylamine -0.3 11.1 2.0×105 1.6×101 120
Trimethylamine 0 9.7 6.0×104 1.2×102 24 8
Dimethylethanolamine 0.25 9.2 9.7×103 6.1×101 119
Aniline 4.5×105 43
4-Aminoaniline 3.5×108 43
N,N-Dimethylaniline 4.4×106 43
3,4-Dicarboxylaniline 1.5×105 121
Luminol 1.0×106 121
Indole 4.9 1.2×104 59
1-Methylindole 1.6×104 59
31
View Article Online

2-Methylindole 5.7 8.1×105 59
DOI: 10.1039/D0EW00231C
3-Methylindole 5 1.9×106 59
2,3-Dimethylindole 6.1 1.1×108 59

Piperidine 0.31 1.5×10-1 59
1-Methylpiperidine 8.7×104 122
4-Methylpiperidine 4.9 3.4×106 122
N-Methylpiperidine -0.18 10.4 8.7×104 25 10
1-Hydroxypiperidine 0.31 4.0×104 104
1-Oxylpiperidine 5.0×106 122
Imidazole 1×10-4 24 8
N-tert-Butylpyrrolidine 1.3×106 10
Benzo-2,3-dihydrophth
3.0×105 123
alazine-1,4-dione
2,3-dihydrophthalazine-
1.5×105 123
1,4-dione
575
576
577 Fig. 3 Correlations between the apparent second-order reaction rate constants (logkapp)
578 for the reactions of ClO2 with primary and secondary amines and with tertiary amines
579 vs. ∑σ* (Table 4). Data is obtained from ref.8, 99
580
581 The release of HOCl has been observed in ClO2 oxidation of many organic
582 compounds and NOM in recent studies. The released HOCl has been found to play an
32
583 important role in removing atenolol, metoprolol and ciprofloxacin, which areView Article Online
DOI: 10.1039/D0EW00231C
584 secondary amines and reacting 45 orders of magnitude faster with HOCl than with

585 ClO2.41 Thus, the removal of amines in practical ClO2 treatment of waters is excepted
586 to be better than the predicted removal based on kapp with ClO2, because small
587 fractions of HOCl is often produced during ClO2 oxidation.15, 41 This phenomenon can
588 happen for compounds with very high reaction rate constants with HOCl than with
589 ClO2. By comparing the kinetics data of ClO2 reactions summarized in this study with
590 those of free chlorine reactions summarized in previous studies35, 99, 124, it was found
591 that primary amines and secondary amines generally have orders of magnitude higher
592 reaction rate constants with free chlorine than with ClO2 at pH 7.0. Thus, it is
593 reasonable to propose that the presence of HOCl in ClO2 reaction system can
594 contribute greatly to the degradation of primary amines and secondary amines.
595 One-electron oxidation is generally considered to be the initial step in most
596 reactions of aliphatic amines with ClO2, leading to the formation of an aminyl cation
597 radical and chlorite (Scheme 6a). After the rejection of an α-proton, the cation radicals
598 undergo further oxidation and generate aldehydes and an inferior amine. In the case of
599 benzylamines (Scheme 6b), whose α-hydrogens are activated by the adjacent phenyl
600 group, hydrogen abstraction also takes place to initiate the reaction, supported by a
601 significant isotope effect.9 It has been reported that hydrogen abstraction is
602 responsible for 73% of the oxidation of benzylamine and 25% of that of
603 benzyl-tert-amine.9
604
33
605 Note: adapted from reference9 View Article Online

DOI: 10.1039/D0EW00231C
606 Scheme 6 Reaction pathway proposed for ClO2 oxidation of amines

607 It should be noted that amines containing a dimethylamine group are considered
608 important precursors of nitrosamines, a potent carcinogen, in water treatment.125 ClO2
609 oxidizes most tertiary aliphatic amines quickly and converts them to secondary
610 amines, and it oxidizes secondary amines to primary amines. Both primary and
611 secondary amines are generally less reactive nitrosamine precursors in subsequent
612 chloramination as they don’t generate nitroso groups. Thus, ClO2 pre-treatment of
613 tertiary amines effectively reduces their nitrosamine formation potential.119 However,
614 reduction on nitrosamine formation with ClO2 oxidation is unpredictable when
615 different real waters are being treated. The effect depends on the type of contaminants
616 and the ClO2 oxidation conditions.119, 126, 127 Further investigations covering more
617 types of amines and oxidation conditions might help to improve understanding of the
618 mechanism of nitrosamine formation in ClO2 oxidation.
619 Turning to aromatic amines, they are widely distributed in aqueous environments
620 as degradation products of dyes in industrial wastewater or of herbicides in
621 agricultural discharges.128 Aniline and 4,4-methylenedianiline are listed in
622 Contaminant Candidate List-4 of U.S. EPA.129 Various reaction rate constants for
623 aniline with ClO2 have been reported. Huie and his co-workers determined the rate of
624 the first step of aniline oxidation to be 4.5×105 M-1s-1 at pH 6.9.43 Lee and von Gunten
625 tried to established a QSAR for ClO2 oxidation of anilines based on limited available
626 data,99 thus the credibility of the QSAR is excepted to increase with more studies on
627 this subject. ClO2 oxidation of anilines also follows a one-electron transfer
628 mechanism as its first step (Scheme 7). Since the amino group is directly attached to a
629 benzene ring, that results in a shift of electron density from the nitrogen atom to the
34
630 benzene ring. The reaction pathways and products are then different from thoseView Article Online
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631 observed with aliphatic amines. Benzoquinone is the major product with

632 p-aminophenol and azobenzene dimer as important intermediates.130
633
634 Note: modified from reference130

635 Scheme 7 Reaction pathway proposed for ClO2 oxidation of aniline
636
637 Among the amino acids, ClO2 reacts rapidly with cysteine, tyrosine and
638 tryptophan (104–107 M-1s-1) and reacts slowly with histidine, proline, alanine and
639 glycine (10-5–10-2 M-1s-1), as shown in Table 5. Other amino acids do not display
640 measurable reaction rates with ClO2.131 Amino acids are a classic type of primary
641 amine, however, the amino group is unreactive towards ClO2. The ClO2-reactive
642 amino acids contain other reactive groups such as phenolic or sulfur-containing
643 groups, and the oxidation occurs at those sites other than the primary amine groups.
644 For example, the reactive site of cysteine, a most reactive amino acid toward ClO2, is
645 believed to be the thiol group where the reaction involves an electron abstraction
646 (Scheme 8a). The cysteinyl radical forms and rapidly reacts with another ClO2
647 molecule to form a cysteinyl-ClO2 adduct, which then yields cysteic acid at acidic pH
648 or cystine under alkaline conditions.114 ClO2 oxidation of tyrosine occurs
649 predominantly at its phenolic structure, resulting in formation of dopaquinone and
650 dopachrome at pH 6–7 (Scheme 8b).132 For tryptophan, ClO2 first abstracts one
35
651 electron from the indole ring to form a neutral tryptophan radical. The radical isView Article Online
DOI: 10.1039/D0EW00231C
652 unstable and immediately reacts with a second mole of ClO2 to generate

653 N-formylkynurenine, kynurenine, 3-hydroxykynurenine and other products.133
654 Table 5 Kinetics of ClO2 oxidation of selected amino acids, peptides, and proteins
Apparent
second-order
Refere
Compounds pKa reaction rate pH T (oC)
nces
constants,
kapp (M-1s-1)
Amino acids
Cysteine 8.2 1.0×107 7.0 25.0 114
Tyrosine 9.1 1.4×105 7.0 25.0 132
N-Acetyltyrosine 2.5×105 6.2 25.0 132
Tryptophan 9.4 3.4×104 7.0 25.0 133
a-Alanine 9.9 < 1×10-2 8.0 25.0 8
Glycine 9.8 < 1×10-5 8.0 22–24 8
Proline 10.6 3.4×10-2 6.0 25.0 131
Hydroxylproline 6.9×10-2 6.0 25.0 131
Histidine 6.0 5.4×10-2 6.0 25.0 131
Peptides
Glutathione 1.4×108 5.9 25.0 11491
Proteins
Bovine serum albumin 6.4 7.0 25.0 134
Glucose-6-phosphate
9.7 7.0 25.0 134
dehydrogenase
655
656
36
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DOI: 10.1039/D0EW00231C

657
659 Scheme 8 Reaction pathway proposed for ClO2 oxidation of amino acids (a) cysteine;
660 (b) tyrosine
661
662 Denaturation of peptides or proteins is caused primarily by covalent oxidative
663 modification of their reactive cysteine, tyrosine and tryptophan residues. For
664 glutathione, a tripeptide formed by glycine, cysteine and glutamic acid, the primary
665 reactive site towards ClO2 is the thiol group and the oxidation products are similar to
666 those of cysteine.114 Treating bovine serum albumin (BSA) and glucose-6-phosphate
667 dehydrogenase (G6PD) with ClO2 converts tryptophan residues to
668 N-formylkynurenine, and tyrosine residues become 3,4-dihydroxyphenylalanine
669 (DOPA) or 2,4,5-trihydroxyphenylalanine (TOPA).134
670 Some heterocyclic nitrogen compounds (e.g., indoles, imidazoles and
671 piperidines) are also reactive towards ClO2. The oxidation rate constant of indoles is
672 about 104–108 M-1s-1,135 but oxidation of imidazole is very slow (10-4 M-1s-1)8 and the
673 rate constants of reaction with piperidine are in the range of 103–106 M-1s-1.10
674 Derivatives of these heterocyclic nitrogen compounds are found extensively in aquatic
37
675 environments. For instance, piperidine, pyrrolidine and imidazole derivatives can
DOI: beView Article Online
10.1039/D0EW00231C
676 found in alkaloids.136 There are, however, only limited reports about the ClO2

677 oxidation pathways of heterocyclic nitrogen compounds. Nevertheless, the reaction
678 pathways of ClO2 with histidine and tryptophan (Scheme 9) can give some evidences
679 for the reaction mechanisms of ClO2 oxidation of indole and imidazole structures.
680
682 Scheme 9 Reaction pathway proposed for ClO2 oxidation of (a) tryptophan and (b)
683 histidine
684
685 4. ClO2 oxidation of emerging contaminants
686 The emerging contaminants (ECs) to be discussed here are primarily synthetic
687 organic chemicals including pharmaceuticals and personal care products (PPCPs),
688 endocrine disrupting compounds (EDCs), pesticides, herbicides, cyanotoxins and
689 antibiotic resistant genes (ARGs), but there are many others. ECs have increasingly
690 been detected in aquatic environments worldwide, including in municipal
691 wastewaters, surface water, ground waters and even in water supply systems, at
692 concentrations ranging from a few ng·L-1 to a few hundred μg·L-1.138-144 The release
38
693 of ECs into the environment may cause ecological risk. ECs can interfere withView Article Online
DOI: 10.1039/D0EW00231C
694 endocrine systems of organisms, promote microbiological resistance, and accumulate

695 in plants and animals.145-147 Since the early 20th century, ARGs as ECs have been
696 found in municipal wastewaters,148, 149 surface waters and associated sediments,150,
697 151 and drinking water distribution systems.152, 153 During water treatment,
698 conventional water treatment processes like coagulation, flocculation, sedimentation
699 and filtration are generally not effective to deactivate or degrade ARGs. Oxidation by
700 ClO2 is, however, effective to remove some ECs from waters.
701 The diverse moieties in ECs lead to various reaction rate constants of ECs toward
702 ClO2. Based on chlorine dioxide’s reactivity with the main functional groups, the
703 reactivity at pH 7.0 usually decreases in the order: phenols＞anilines＞tertiary amines
704 ＞ secondary amines, as shown in Table 6. ClO2 reacts rapidly with ECs containing
705 electron-rich phenolic groups, such as 17α-ethinylestradiol, and the kapp at pH 7.0 for
706 these ECs generally exceed 104 M-1s-1.99, 154, 155 ECs containing amine groups
707 generally have reaction rate constants with ClO2 at around 103 M-1s-1 for anilines such
708 as sulfonamides,156 102 M-1s-1 for tertiary amines such as roxithromycin,99 and 10
709 M-1s-1 for secondary amines such as ciprofloxacin.157 The kapp of pharmaceuticals at
710 pH 7.0 generally range from high to low in the order tetracyclines, estrogens,
711 sulfonamides, macrolides and then fluoroquinolones. The reaction rate constants
712 within the same group also vary depending on the structures involved. For example,
713 among the fluoroquinolones, the reaction rate constants of ofloxacin and enrofloxacin,
714 which contain tertiary amines on their piperazine moieties (77.5 and 62.7 M-1s-1,
715 respectively) are higher than those of ciprofloxacin, norfloxacin, lomefloxacin or
716 pipemidic acid which contain secondary amines (1.5–13.0 M-1s-1).157 This is in good
717 agreement with the trend of faster oxidation of tertiary amines than secondary amines
39
718 by ClO2. For phenylurea herbicides containing secondary amines, diuron shows
DOI: much
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719 higher reactivity towards ClO2 than chlortoluron or isoproturon due to the different

720 functional groups on the aromatic ring.158 Regarding the algal toxin microcystin-LR,
721 the reaction rate constant with ClO2 is low at 1.24 M-1s-1 at pH 7.0.159
40

722 Table 6 Kinetics of ClO2 reactions with emerging contaminants
Species-specific second-order rate constants (M-1s-1) Apparent second-order

T Refere
Compound pKa reaction rate constants, pH
H2A+ HA A- A2- (oC) nces
kapp (M-1s-1)
Phenols (PPCPs and EDCs)
Acetaminophen 9.7 2.6 1.1×108 2.1×105 7.0 99
Bisphenol A 9.6, 10.2 4.3 2.8×108 1.8×105 7.0 99
Triclosan 8.1 1.2 8.5×106 6.3×105 7.0 99
4-n-Nonylphenol 10.7 5.9 3.6×108 7.1×104 7.0 99
17α-ethinylestradiol 10.4 <2×102 4.6×108 2.0×105 7.0 20 154
17-estradiol 10.71 ~105 7.0 20 154
Estrone 10.8 ~105 7.0 20 154
Amoxicillin ＞104 8.0 20 155
Cefadroxil ＞104 8.0 20 155
Tetracycline 3.3, 7.7, 7.2×106 2.7×107 1.3×106 7.0 22 160
41

9.3
3.3, 7.3,
Oxytetracycline 3.7×106 1.6×107 1.2×106 7.0 22 160
9.1
3.3, 7.4,
Chlorotetracycline 1.05×106 2.57×107 3.2×105 7.0 22 160
9.3
3.5, 6.9,
Iso-chlorotetracycline 3.05×105 2.13×107 2.2×105 7.0 22 160
9.4
Anilines (PPCPs)
Sulfamethoxazole 1.9, 5.6 negligible 4.8×101 6.5×103 6.1×103 7.0 20 156
Sulfamethizole 1.9, 5.3 negligible 9.0×101 3.8×103 3.9×103 7.0 20 156
Sulfadimethoxine 2.1, 6.1 negligible 3.5×101 5.3×103 4.4×103 7.0 20 156
Sulfamethazine 2.1, 7.5 negligible 9.5×102 1.2×104 4.1×103 7.0 20 156
Sulfamerazine 2.1, 6.9 negligible 9.4×102 8.9×103 5.6×103 7.0 20 156
Diclofenac 4.2 1.1×104 1.1×104 7.0 20 154
Iopromide <1.0×10-2 7.0 20 154
Tertiary amines (PPCPs)
Roxithromycin 8.8 1.4×104 2.2×102 7.0 20 154
42

Enrofloxacin 6.1, 7.7 <1.0×10-4 1.6×101 3.4×102 6.3×101 7.0 22 157
Ofloxacin 6.2, 7.8 <1.0×10-4 1.8×101 5.4×102 7.8×101 7.0 22 157
Dimethylaminophenazo
＞102 7.4 20 154
ne
Secondary amines (PPCPs)
Ciprofloxacin 6.1, 8.6 <1.0×10-4 4.5 1.9×102 7.9 7.0 22 157
Norfloxacin 6.2, 8.5 <1.0×10-4 1.01×101 1.78×102 1.3×101 7.0 22 157
Lomefloxacin 5.5, 8.8 <1.0×10-4 3.9 1.9×102 6.8 7.0 22 157
Pipemidic acid 5.4, 8.2 <1.0×10-4 1.54×10-3 24.4 1.5 7.0 22 157
Atenolol 9.6 1.0 8.0 20 41
Metoprolol 1.3 8.0 20 41
Ifosfamide <1 7.4 20 154
Others (PPCPs)
Trimethoprim 3.2, 7.1 3.76 7.00 34.1 1.9×101 7.0 22 161
Gemifibrozil 5.9×101 7.0 99
Naproxen 6.1×102 7.0 99
Antipyrine 1.4 4.8×10-1 7.0 25 162
43

Penicillin-G <0.1 6.4 20 155
Bezafibrate 3.6 <1.0×10-2 7.0 20 154
Carbamazepine <1.5×10-2 7.0 20 154
Diazepam <2.5×10-2 7.0 20 154
Ibuprofen 4.9 <1.0×10-2 7.0 20 154
Caffeine <1 7.4 20 154
Clofibric acid <1 7.4 20 154
Cyclophosphamide <1 7.4 20 154
Fenoprofen <1 7.4 20 154
Glibenclamide <10 7.4 20 154
Ketoprofen <1 7.4 20 154
Pentoxifylline ＞102 7.4 20 154
Propylphenazone ＞102 7.4 20 154
Herbicides
Chlortoluron 1.4 8.0 25 158
Isoproturon 2.1 8.0 25 158
44

Pesticides
Methiocarb 1.1 7.4 22 30
Cyanotoxins
Cylindrospermopsin 0.9 8.0 20 163
Anatoxin-a 9.36 4.7 1.2 8.0 20 163
Microcystin-LR 1.1 7.0 25 159
45
724 pH has a significant impact on the reactivity of ECs with ClO2. The secondary View Article Online
DOI: 10.1039/D0EW00231C
725 reaction rate constants of most ECs increase rapidly from pH 5.0 to 9.0, and then the

726 increase slows above pH 9.0, as shown in Fig. 4. For example, the secondary rate
727 constant of ciprofloxacin increases by more than 3 orders of magnitude from pH 5.0
728 to 10.0 and those of tetracyclines (e.g., tetracycline, oxytetracycline and
729 chlorotetracycline) increase by 4-6 orders of magnitude from pH 2.5 to 10.5. The
730 reaction rate constant of 17α-ethinylestradiol increases linearly with pH. Diclofenac,
731 however, shows no pH dependence and its second-order rate constant with ClO2
732 remains 1.05×104 M-1s-1 at any pH over 5.0. The reaction rates of penicillin-G
733 potassium salt with ClO2 at pH 3.5, 5.4 and 6.4 are 3.5, 0.35, and < 0.1 M-1s-1,
734 respectively, decreasing as the pH increases.155 For phenylurea herbicides, the
735 degradation rates of chlortoluron and isoproturon increase progressively with
736 increasing pH, while the degradation rate of diuron decreases.158 For antipyrine,
737 higher pH accelerates the reaction with ClO2 when the pH is less than 9.0, but in a
738 strongly alkaline environment (pH > 9.0) the oxidation process slows with increasing
739 pH.
740 Such pH-dependent reactivity can be explained by the protonation state of the
741 reactive groups involved, like the phenolic group of estrogens, the aniline group of
742 sulfonamides and the secondary or tertiary amino group of fluoroquinolones. The
743 specific rate constants of the deprotonated species (A-) are generally higher than those
744 of the neutral species (HA), and the reaction rate constants between cation species
745 (H2A+) and ClO2 are generally negligible. Therefore, the shifting to anionic species
746 (A-) with increasing pH from 5.0 to 10.0 generally enhances the rates of ClO2’s
747 reactions with phenolic-containing and amine-containing ECs such as estrogens,
748 sulfonamides and fluoroquinolones. Diclofenac with a pKa of 4.0 contains a carboxyl
46
749 group acting as a proton donor, and its reaction rate with ClO2 varies littleDOI:at10.1039/D0EW00231C
pHsView Article Online
750 higher than 5.0. Higher pH results in higher oxidation-reduction potential of ClO2

751 solution, making it easier to oxidize substrates.164 However, ClO2 may decompose to
752 chlorite and chlorate when the pH exceeds 9.0, causing a sharp decline in ClO2
753 concentration, which inhibits the degradation process.165 That might explain the
754 slower increase in degradation rate observed with most ECs at pH > 9.0. Nevertheless,
755 the species-specific reaction rate constants shown in Table 6 can be applied to
756 calculate apparent second-order reaction rate constants of ECs at different pHs.
757
758
759 Fig. 4 pH dependence of the apparent second-order reaction rate constants (logkapp)
760 and the half-life times (logt1/2) for reactions of ClO2 with selected emerging
761 contaminants at 20–25oC. The half-lives are calculated at a chlorine dioxide
762 concentration of 1 mg∙L-1 (15 μM).
763 The reactions between ClO2 and ECs usually proceed via electron transfer
764 pathways. The EC provides one electron to ClO2 and is activated to a radical. The
47
765 newly-formed radical can couple with ClO2 to further produce oxidation products. View Article Online
DOI: 10.1039/D0EW00231C
766 The reactive sites of typical ECs for ClO2 attack are presented in Fig. 5.

767 Taking 17α-ethinylestradiol, a highly reactive phenolic compound, for an
768 example, the phenolic group of 17α-ethinylestradiol is the first attack site for ClO2
769 producing single-electron transfers from the electron-rich phenolic group to ClO2. The
770 oxidation of 17α-ethinylestradiol by ClO2 may produce quinone-type products such as
771 hydroquinone, which is similar to those produced through ozone oxidation.166 The
772 aniline group of sulfamethoxazole is reported to be attacked initially by ClO2 resulting

773 in the formation of aminyl radical cations.167 The radical cations then deprotonate and
774 hydroxylate to form hydroxylamine, which can be further oxidized to form nitroso
775 groups.168 Moreover, the cleavage of C-S and S-N bonds may also occur, and the
776 resulting intermediates may further oxidize to sulfate ion, nitrate ion, oxalic acid and
777 other products.156 As with sulfamethoxazole, aniline moiety of diclofenac is the
778 principal reactive site involved in hydroxylation and chlorination followed by the
779 formation of aldehyde intermediates.31, 169, 170 Finally, ring structures are opened and
780 further oxidation continues. With roxithromycin, a macrolide antibiotic, ClO2 first
781 attacks the tertiary amino group, and leads to the cleavage of the C-N bond. After
782 further oxidation, roxithromycin loses the entire amino group.154 With the
783 fluoroquinolones, the piperazine ring is the major reaction site and ClO2 first attacks
784 tertiary amines (in enrofloxacin and ofloxacin) or secondary amines (in ciprofloxacin,
785 norfloxacin, lomefloxacin and pipemidic acid), generating a radical.171 Further
786 oxidation of the amine group by another ClO2 molecule results in fragmentation of the
787 piperazine ring and the formation of imine intermediates. Subsequent hydrolysis of
788 the imine intermediates leads to the formation of the dealkylated product observed in
789 the oxidation of amines by ClO2.9, 172 In spite of bearing a primary amine group in
48
790 trimethoprim, the pyrimidine ring is suspected to be most susceptible for ClODOI:
2 attack.
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791 Oxidation of trimethoprim by ClO2 leads mostly to chlorine and hydroxyl

792 substitutions at the diaminopyrimidinyl moiety as well as transformation of amino
793 groups (-NH2) to nitroso groups (-NO).161

794
795 Note: Red colors indicate the reactive sites for ClO2 attack.
796 Fig. 5 Typical emerging contaminants
797 In case of pesticides containing secondary amine group such as chlortoluron or
798 diuron, the electron-rich nitrogen atom first undergoes single-electron transfer and the
799 free radical intermediates transform into hydroxyl derivatives.111, 137 The subsequent
800 breaking of the N-C bond in the intermediates gives rise to smaller and more
801 hydrophilic products, mainly carboxylic acids and aldehydes.158 Methiocarb (MC) is a
802 commonly used sulfur-containing pesticide. During the ClO2 oxidation, addition of
803 ClO2 and OH- around the sulfur center results in an intermediate adduct MC–ClO2–
804 OH. With its cleavage, the more toxic methiocarb sulfoxide is generated by losing
49
805 HClO2, while the less toxic methiocarb sulfone is generated by HOCl loss.111, 173 InView Article Online
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806 alkaline conditions, methiocarb sulfoxide and methiocarb sulfone can be further

807 oxidized to 2,6-dimethylbenzoquinone, 2,6-dimethylhydroquinone,
808 4-chloro-3,5-dimethylphenol and other unidentified products.30
809 Microcystin-LR is an abundant algal toxin. Its conjugated double bonds are
810 reported to be the main reactive site during ClO2 oxidation. The major degradation
811 products are dihydroxy isomers of microcystin-LR, which are less toxic than the
812 parent compound.159

813 The degradation efficiency of ClO2 on ARGs is quite low. The kapp values for
814 ClO2 degradation of four 266—1017 bp amplicons of a chromosomal ARG of
815 multidrug-resistant Bacillus subtilis 1A189 ranged from 0.010 to 0.013 M−1s−1 per bp
816 during ClO2 treatment, which are lower than the rates for hydroxyl radical, ozone and
817 free chlorine.174 ARGs degradation rates in ClO2 oxidation correlates strongly with
818 the contents of 5’-guanine.174 This observation suggests that guanine is the most
819 susceptible site in ARGs degradation by ClO2 and the apparent second-order reaction
820 rate for ClO2 oxidation of guanosine 5’-monophosphate is about 4.5×102 M−1s−1 at pH
821 7.0.175 Therefore, theoretically, the ARGs degradation efficiency in ClO2 oxidation
822 depends on the nucleotide contents of specific ARGs.
823 The removal efficiency of ECs is highly dependent on the water and wastewater
824 matrix. In a study evaluating the removal of 56 PPCPs during ClO2 treatment of
825 biologically treated wastewater, better removal efficiency was observed in low COD
826 (35 mg/L COD) wastewater from the plant than that in high COD wastewater (55
827 mg/L COD) at the same ClO2 dose.176 Additionally, the removal is also highly
828 dependent on the functional groups in PPCPs (Table 5). In the 56 PPCPs’ study, about
829 1/3 of the PPCPs barely degraded even at a ClO2 dose of 20 mg/L, whereas others
50
830 were reduced by over 90% at a ClO2 dose of 0.5 mg/L.176 One advantage DOI:
of 10.1039/D0EW00231C
ClOView
2
Article Online
831 treatment is that the removal efficiency of ECs is barely affected by the presence of

832 ammonia and nitrite in water and wastewater.177 Contractively, great reduction in
833 ECs’ removal efficiency is found with increasing concentrations of ammonia and
834 nitrite during chlorination treatment.177
835
836 5. Implications and future research perspectives
837 In order to give a whole picture of the transformation of diverse groups of

838 compounds in water, Fig. 6 summarizes the available reaction rate constants for ClO2
839 and also presents their half-lives at a typical ClO2 dose of 1 mg∙L-1 and at pH 7.0. In
840 consideration of a typical recommended disinfection period of 30 min for ClO2 as
841 primary disinfectant, phenolic, anilines and heterocyclic nitrogen moieties in waters
842 are decomposed to great extent, while oxidation of olefins and ketones are more likely
843 to occur when ClO2 residual is maintained in long-distance water distribution system.
844 It should be noted that the half-lives of tertiary amines are around 30 min, indicating
845 that only partial of tertiary amines are decomposed in that disinfection period,
846 whereas primary and secondary amines are barely transformed. ClO2 can also lead to
847 promising removal of some micropollutants bearing reactive groups. Sulfonamides
848 (aniline structures) and tetracyclines (tertiary-amine and phenol-like structures) can be
849 quickly decomposed at the typical ClO2 reaction conditions. Fluoroquinolones,
850 -lactams and other pharmaceuticals have varied half-lives, dependent on their
851 specific structures. The degradation of pesticides (e.g., antipyrine and metoprolol) and
852 algal toxins (e.g., microsystins) generally takes hours to complete. As illustrated in
853 Fig. 6, the degradation extents of organic compounds bearing diverse functional
854 groups can be estimated. Therefore, we will know what types of compounds are
51
855 degraded when ClO2 is used for primary disinfection (0.5–1.4 mg∙L-1, 15–30 min) andView Article Online
DOI: 10.1039/D0EW00231C
856 secondary disinfection (0.2–0.5 mg∙L-1, 30–120 min). It will also give us guidance

857 about the doses and reaction time suitable for target pollutants removal. For example,
858 when ClO2 is applied as secondary disinfectant, enhanced decomposition of tertiary
859 amines, olefins and some micropollutants (e.g., fluoroquinolones and trimethoprim)
860 are expected, while degradation of ketones, pesticides (e.g., antipyrine and
861 metoprolol) and algal toxins (e.g., microsystins) generally takes hours to complete,
862 which are more likely to occur in long-distance water distribution system with
863 adequate ClO2 residual.
1010 10-7
109 10-6
108 10-5
107 10-4
106 10-3
105 10-2
104 10-1
kapp (M-1s-1)
103 100
102 30min 101 t1/2 (min)
101 120min
102
100 103
10-1 104
10-2 105
10-3 106
10-4 107
10-5 108
10-6 Organics Emerging contaminants 109
10-7
ic es es es ins es ols es en es ms es es ics als es ins
an in in in f d n in g n a id in t c id t
org am am am Ole ehy he nil itro olo act am ycl ibio uti tic cys
In ry y y l d P A n uin -l n c nt c e es ro
a ar iar d
a ic
cl roq β ulfo etra r a ma P ic
im nd rt an cy luo S T the ar M
Pr eco Te s ro F O ph
S ne te ic
eto He i ot
K ib
nt
n-a
No
864
865 Fig. 6 The apparent second-order reaction rate constants (kapp) and the half-life times
866 (t1/2) for reactions of ClO2 with model compounds bearing different functional groups.
867 t1/2 was calculated by assuming a ClO2 concentration of 1 mg∙L-1 (15 μM) at pH 7.0.
52
868 The horizontal dash lines represent the typical ClO2 treatment period, 30min andView Article Online
DOI: 10.1039/D0EW00231C
869 120min, respectively.

870 As discussed above, ClO2 oxidation is selective and reacts with water
871 components mainly via electron transfer pathway. Despite of the limited formation of
872 halogenated DBPs, formation of chlorite and chlorate is the biggest obstacle for ClO2
873 application. The applied dose of ClO2 needs to be carefully controlled. One should
874 bear in mind that the reactions of moieties in waters is predicted based on laboratory
875 results with model compounds, which may not fully represent the situation in real
876 water treatment. Effects of competing reactions, variation of treatment conditions and
877 the level of pollutants in waters should be taken into consideration in practice. For
878 example, ClO2 is sometimes applied to remove Fe(II) and Mn(II) in water. Though
879 chloride ions, not chlorite, are the products from ClO2 reduction by Fe(II) or Mn(II)
880 based on the reaction mechanisms illustrated in section 3.1, ClO2 also competitively
881 reacts with NOM (e.g., phenolic moieties) and quickly reduce ClO2 to chlorite. In
882 addition, the presence of NOM may affect ECs’ degradation via two ways: competing
883 consumption of ClO2 and direct interaction with micropollutants. Accelerated
884 consumption of ClO2 in real water matrixes can reduce the removal efficiency of ECs.
885 For example, the kapp of ClO2 oxidation of ciprofloxacin is about 13.2 M-1 s-1 in
886 ultrapure water at pH 7.0, whereas the measured kapp in surface water matrixes
887 reduced to 6.4 M-1s-1.157 Moreover, complexes between NOM and ECs are likely
888 formed due to the electrostatic attraction between the negatively charged NOM
889 surface and the positively charged functional groups of ECs (e.g., amine groups). The
890 formation of NOM-EC complexes may hinder the contact between ClO2 and ECs,
891 leading to impaired removal performance for ECs.178 Still, the ClO2 dose needs to be
892 handled in great care. On the other perspective, phenolic moieties in NOM are found
53
893 to be the dominant precursors of chlorite in the beginning stage of ClO2 reaction (< 5View Article Online
DOI: 10.1039/D0EW00231C
894 min).42 Transforming phenolic groups by some oxidation processes, such as

895 permanganate, ozone or ferrate, ahead of ClO2 application may be helpful to reduce
896 chlorite formation, but this deserves future justification.
897 ClO2 is helpful in reducing some DBP precursors during subsequent chlorination
898 or chloramination in drinking water treatment. ClO2 is confirmed to be very effective
899 to reduce THM precursors, predominantly due to the deterioration of phenolic
900 precursors in water.98 Therefore, in waters suffering from meeting the THM
901 regulations, ClO2 pretreatment is a useful method. ClO2 pretreatment ahead of
902 chloramination is generally useful to reduce N-nitrosamine precursors mainly due to
903 the transformation of tertiary amines unless the water is impacted by hydrazine
904 pollutants.179 ClO2 also changes the formation of nitrogenous DBPs, such as
905 haloacetonitriles, halonitromethanes, and haloacetamides, but the changes don’t have
906 a consistent trend and vary with water matrix.180 Further characterization of
907 transformation products during ClO2 oxidation and their influences on the formation
908 of emerging disinfection byproducts, especially brominated, iodinated, or aromatic
909 DBPs, in subsequent chlorination and chloramination deserves further investigation.
910 From the view of safety of ClO2-treated waters, the main concern is the
911 formation of quinones that mainly derived from oxidation of phenolic compounds and
912 undesirable inorganic by-products chlorite and chlorate. In general, waters treated by
913 ClO2 alone exhibited much lower chronic mammalian cell cytotoxicity and
914 genotoxicity than chlorinated waters, according to data from European HIWATE
915 project.6 Cautious still need to be taken that when ClO2 is applied in combination with
916 other oxidants (e.g., chloramine) because a synergistic effect of organic DBP and
917 chlorite/chlorate could contributed to higher toxicity of treated samples.48 It was
54
918 reported that treatment of wastewaters in high ammonia levels by mixing oxidant ofView Article Online
DOI: 10.1039/D0EW00231C
919 ClO2 might exhibit higher cytotoxicity than using ClO2 alone.7 Thus, further

920 investigations into featured organic products from ClO2 oxidation of different water
921 qualities are in urgent need to know better what are the suitable circumstances to
922 apply ClO2 treatment.
923 ClO2 has been studied for several decades from the aspects of reaction kinetics,
924 mechanisms, products and so on. However, the presence of HOCl in the reactions of
925 ClO2 with organic compounds and NOM is experimentally confirmed until recently.15,
926 41 Although the in situ formed HOCl is responsible for chlorinated by-products
927 formation during ClO2 oxidation, only about 7% of dosed ClO2 was involved with
928 chlorine incorporation to organic moieties overall.15 This explains the low yields of
929 chlorinated by-products during ClO2 oxidation. On the other hand, the presence of
930 trace amount of HOCl has been found to contribute to ECs’ removal.41 More studies
931 should be conducted to explore further the role of HOCl in ClO2 reaction system.
932
933 6. Conclusions
934 A varied group of inorganic and organic compounds can be transformed by ClO2.
935 ClO2 exhibits fast transformation rates of inorganic compounds including I-, CN-,
936 NO2-, SO32-, Fe(II) and Mn(II), but it does not react with ammonia or Br-. In typical
937 water treatment conditions, phenols, tertiary amines and thiols are reactive toward
938 ClO2, whereas alcohols, aldehydes, ketones, benzoquinone are less reactive.
939 Dissociated phenols and amines have faster reaction rate constants than the
940 un-dissociated forms. Quantitative relationships between structure and reaction rate
941 constants have been established for phenols and amines with electron-donating
942 substituents exhibiting faster reaction rates. For many such compounds and many
55
943 emerging contaminants, mineralization is minimal and often little modification

DOI:of theView Article Online
10.1039/D0EW00231C
944 parent compounds is observed, with the formation of quinones, aldehydes and

945 carboxylic acids. Electron transfer is the dominant reaction pathway, and ClO2 is first
946 converted to chlorite. The subsequent reaction steps are sometimes associated with the
947 release of HOCl or the formation of chloride from further reduction of chlorite by the
948 parent compounds. Except for chlorophenols, chlorinated organic products are
949 seldomly reported. Significant information on the reactivity of ClO2 with groups of
950 inorganic and organic compounds is available from the literatures. Such information
951 is essential for improving understanding of the transformation of emerging
952 contaminants and humic substances bearing diverse functional groups. It is also
953 helpful in understanding the formation trends of chlorite and the dominant organic
954 byproduct in ClO2-treated water and wastewater.
955
956 Acknowledgements:
957 This work was supported by the National Key Research and Development
958 Program of China (2017YFE0133200), National Natural Science Foundation of China
959 (21876210 and 21622706), Guangdong Provincial Science and Technology Planning
960 Project (2019A050503006 and 2017B020216005) and the China Postdoctoral Science
961 Foundation (2019M660671).
962
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Environmental Science: Water Research & Technology
DOI: 10.1039/D0EW00231C
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Graphic abstract DOI: 10.1039/D0EW00231C

inorganic
e organic
quinones NOM
aldehydes
O
Cl O contaminants
emerging
organic acids
...... ......
chlorite
The reaction kinetics and mechanisms of ClO2 reactions with inorganic and organic
compounds are overviewed.

10 1039@d0ew00231c

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or omissions in this Accepted Manuscript or any consequences arising

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Environmental Science: Water Research & Technology Accepted Manuscript

pre-oxidation or disinfection. This work overviews the reactions of ClO2 with

and mechanisms. Micropollutant transformation during ClO2 oxidation relevant to

water treatment is also included. The information is essential in improving

understanding the ClO2 oxidation chemistry and byproducts formation in water

2 Compounds in Water Treatment: Kinetics and Mechanisms

Environmental Science: Water Research & Technology Accepted Manuscript

4 Wenhui Gan†,‡,Yuexian Ge†, Yu Zhong†, Xin Yang†,*

6 † School of Environmental Science and Engineering, Guangdong Provincial Key

7 Laboratory of Environmental Pollution Control and Remediation Technology, Sun

8 Yat-sen University, Guangzhou 510275, China

10 Environmental Safety, Tsinghua Shenzhen International Graduate School, Tsinghua

11 University, Shenzhen 518055, China

14 * Corresponding author, Tel: +86-2039332690, email: yangx36@mail.sysu.edu.cn

24 Abstract View Article Online

25 Chlorine dioxide (ClO2), as an alternative to chlorine, has been widely applied in

Environmental Science: Water Research & Technology Accepted Manuscript

28 compounds found in water are critically reviewed. In the case of inorganic

34 high reactivity towards aliphatic tertiary amines and heterocyclic nitrogenous

38 transfer is the dominant pathway for ClO2 reactions. Quantitative structure-activity

39 relationships (QSAR) can be used to predict the specie-specific secondary reaction

43 of quinones, aldehydes and carboxylic acids. Furthermore, the transformation kinetics

44 of inorganic compounds, typical organic compounds and emerging micropollutants

46 ClO2 oxidation are calculated.

49 View Article Online

Environmental Science: Water Research & Technology Accepted Manuscript

52 chlorine in drinking water treatment. ClO2 is effective in removing algae (e.g.,

53 Chlamydomonas, Phormidium and Chlorella), inactivating planktonic bacteria and

54 some chlorine-resistant pathogens (e.g., Giardia lamblia and Cryptosporidium

61 European countries.6 ClO2 is also used in wastewater treatment to inactivate

62 microorganisms and to transform micropollutants and reduce the release of organic

64 As a chemical oxidant, ClO2 is able to oxidize inorganic pollutants in water (e.g.,

68 and anilines. As a result, ClO2 exhibits promising removal of organic contaminants

73 organic compounds, including phenols and amines.8 Rav-Acha summarized the

74 reaction pathways of ClO2 oxidation of inorganic compounds and a variety DOI:

Environmental Science: Water Research & Technology Accepted Manuscript

78 bromate or brominated DBPs formation can be spared in ClO2 oxidation because

80 Therefore, tremendous reduction in the formation of halogenated DBPs, such as

81 trihalomethanes (THMs), haloacetic acids (HAAs), and haloacetonitriles (HANs), is

85 treating waters at high pH.

94 mg∙L-1 in China.21 Consequently, the applied dose of ClO2 in drinking water

95 treatments is typically limited to approximately 1.4 mg∙L-1. In Germany, the dose of

97 applied dose of ClO2 is usually in the range of 2 to 10 mg∙L-1 depending on

98 wastewater properties to guarantee the microbial inactivation efficiency before reuse

Environmental Science: Water Research & Technology Accepted Manuscript

104 byproducts seemed insignificant as ClO2 treatment leads to minor or no increase of

107 products is reported.30, 31

114 of micropollutants during ClO2 oxidation is summarized. Quantitative

117 accordingly. Additionally, the transformation of micropollutants during ClO2

120 transformation in practical ClO2 treatment.

122 2. Physical and chemical properties of ClO2

Environmental Science: Water Research & Technology Accepted Manuscript

126 chlorite and chlorate (Eq. 1).32

127 2𝐶𝑙𝑂2 +2𝑂𝐻 ― = 𝐶𝑙𝑂2― + 𝐶𝑙𝑂3― + 𝐻2𝑂 (1)

132 side-reaction products (e,g., Cl2) as impurities.

135 molar absorptivity of 1250 M-1cm-1. This extinction coefficient is independent of

139 Fig. 1 The molecular structure of ClO2

145 chlorinated byproducts.34, 35 Ozonation generally proceeds with ozone addition