Journal Pre-proof

Removal of micropollutants by an electrochemically driven UV/chlorine process for

decentralized water treatment

Yinqiao Zhang, Huijiao Wang, Yang Li, Bin Wang, Jun Huang, Shubo Deng, Gang
Yu, Yujue Wang

PII: S0043-1354(20)30652-7
DOI: https://doi.org/10.1016/j.watres.2020.116115
Reference: WR 116115

To appear in: Water Research

Received Date: 2 December 2019

Revised Date: 22 June 2020
Accepted Date: 25 June 2020

Please cite this article as: Zhang, Y., Wang, H., Li, Y., Wang, B., Huang, J., Deng, S., Yu, G., Wang, Y.,
Removal of micropollutants by an electrochemically driven UV/chlorine process for decentralized water
treatment, Water Research (2020), doi: https://doi.org/10.1016/j.watres.2020.116115.

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 1 Removal of micropollutants by an electrochemically driven UV/chlorine

2 process for decentralized water treatment

3 Yinqiao Zhang, Huijiao Wang, Yang Li, Bin Wang, Jun Huang, Shubo Deng, Gang Yu, Yujue

4 Wang*

5 School of Environment, Beijing Key Laboratory for Emerging Organic Contaminants Control,

6 State Key Joint Laboratory of Environmental Simulation and Pollution Control, Tsinghua

7 University, Beijing 100084, China.

8
*
9 Corresponding authors. Email: wangyujue@tsinghua.edu.cn;

10

11

1
12 Abstract

13 The ultraviolet/chlorine (UV/Cl2) process is an emerging advanced oxidation technology

14 for micropollutant abatement in water and wastewater treatment. However, the application of

15 the conventional UV/Cl2 process in decentralized systems is limited by the transport and

16 management of liquid chlorine. To overcome this limitation, this study evaluated an

17 electrochemically driven UV/Cl2 (E-UV/Cl2) process for micropollutant abatement under

18 conditions simulating decentralized water treatment. The E-UV/Cl2 process combines UV

19 irradiation with in situ electrochemical Cl2 production from anodic oxidation of chloride (Cl–)

20 in source waters. The results show that with typical Cl– concentrations present in water

21 sources for decentralized systems (30–300 mg/L Cl–), sufficient amounts of chlorine could be

22 quickly electrochemically produced at the anode to enable E-UV/Cl2 process for water

23 treatment. Due to its multiple mechanisms for micropollutant abatement (direct photolysis,

24 direct electrolysis, Cl2-mediated oxidation, as well as hydroxyl radical and reactive chlorine

25 species oxidation), the E-UV/Cl2 process effectively eliminated all micropollutants

26 (trimethoprim, ciprofloxacin, metoprolol, and carbamazepine) spiked in a surface water in 5

27 min. In contrast, at least one micropollutant with ~20–80% residual concentrations could still

28 be detected in the water treated by 10 min of UV irradiation, chlorination, electrolysis, and the

29 conventional UV/Cl2 process under similar experimental conditions. The electrical energy per

30 order (EEO) for micropollutant abatement ranged from 0.15 to 1.8 kWh/m3 for the E-UV/Cl2

31 process, which is generally comparable to that for the conventional UV/Cl2 process (0.14–2.7

32 kWh/m3). These results suggest that by in-situ generating Cl2 from anodic oxidation of Cl–,

33 the E-UV/Cl2 process can overcome the barrier of the conventional UV/Cl2 process and thus

34 provide a promising technology for micropollutant abatement in decentralized water treatment

35 systems.

36 Keywords:

2
37 Advanced oxidation process; decentralized water treatment; Pharmaceutical; UV/chlorine

3
38 1. Introduction

39 Over the past decades, the growing gap between water demand and conventional water

40 supply has led to a rethinking of the current centralized water infrastructure in many regions

41 (Hodges et al. 2018, Radjenovic and Sedlak 2015, van Loosdrecht and Brdjanovic 2014). One

42 emerging solution to supplement the insufficient conventional water supply involves

43 decentralized water treatment systems that can exploit alternative water sources, such as grey

44 water and municipal wastewater effluent. However, these alternative water sources are often

45 contaminated with various trace organic pollutants (micropollutants) such as pharmaceuticals,

46 consumer products, and pesticides. To minimize their potential risks to human health,

47 micropollutants have to be sufficiently removed from the water sources prior to

48 potable/non-potable reuse (Barazesh et al. 2015, von Gunten 2018). In this regard, advanced

49 oxidation processes (AOPs) have been considered potential treatment options for

50 micropollutant removal in decentralized water treatment (Hodges et al. 2018, Radjenovic and

51 Sedlak 2015, von Gunten 2018).

52 While conventional AOPs (e.g., O3/H2O2 and UV/H2O2) have been successfully applied in

53 full-scale centralized water systems for decades, they do not fit well in decentralized systems

54 due to the need of chemical transport and storage (Barazesh et al. 2015, von Gunten 2018). In

55 contrast, electricity-driven processes such as UV irradiation and electrochemical production

56 of oxidants (e.g., •OH, Cl2, and H2O2) can avoid chemical management and therefore are

57 particularly suitable for decentralized systems (Chaplin 2019, Radjenovic and Sedlak 2015,

58 von Gunten 2018). Meanwhile, the flexibility, robustness, and modular design of

59 electricity-driven processes also make them attractive for decentralized water treatment

60 (Barazesh et al. 2015, Chaplin 2019, Radjenovic and Sedlak 2015). Therefore, it has been

61 expected that electricity-based processes may bear a huge potential in future decentralized

62 water treatment systems (Hodges et al. 2018, Radjenovic and Sedlak 2015, von Gunten 2018).

4
63 Recently, the UV/chlorine (UV/Cl2) process has emerged as a promising AOP option for

64 micropollutant removal in water and wastewater treatment (Guo et al. 2018, Jin et al. 2011,

65 Remucal and Manley 2016, Wang et al. 2019, Yang et al. 2016). The UV photolysis of free

66 chlorine (HOCl/OCl–) can lead to the formation of hydroxyl radicals (•OH) and a suite of

67 reactive chlorine species (RCS) such as Cl•, ClO•, and Cl2–•, which can in turn oxidize UV-

68 and/or chlorine-resistant micropollutants. Therefore, the UV/Cl2 process can considerably

69 enhance micropollutant abatement compared to individual UV photolysis and chlorination

70 (Guo et al. 2018, Pan et al. 2017, Remucal and Manley 2016, Wang et al. 2019, Xiang et al.

71 2016). Nevertheless, the need of transporting and managing liquid chlorine limits the

72 application of the conventional UV/Cl2 process in decentralized systems.

73 To overcome this limitation, we proposed in situ chlorine production from anodic chloride

74 (Cl–) oxidation for the application of the UV/Cl2 technology in decentralized water systems in

75 this study. Cl– is a ubiquitous halide ion in almost all water matrices, including the alterative

76 water sources proposed for decentralized systems. Therefore, this approach may offer a

77 simple way to circumvent the barrier of the UV/Cl2 technology for decentralized water

78 treatment. In previous studies, electrochemical production of Cl2 followed by UV irradiation

79 has been investigated for phenol and 1,4-dioxane removal from their synthetic solutions and

80 for ammonia removal from landfill leachate (Hurwitz et al. 2014, Kishimoto et al. 2018, Xiao

81 et al. 2009, Ye et al. 2016). The high Cl– concentrations in the synthetic solutions and leachate

82 (~890–3000 mg/L) facilitate electrochemical chlorine production, which then enhances

83 substantially the removal of target pollutants during UV irradiation. However, Cl– is typically

84 present at considerably lower concentrations in the alternative water sources proposed for

85 decentralized systems, e.g., ranging from several tens to a few hundreds of mg/L in grey water

86 and municipal wastewater effluent (Lian et al. 2017, Sanchez et al. 2010, Yao et al. 2016, Yu

87 et al. 2013, Zhang et al. 2019). Moreover, the previous studies focused on the removal of high

5
 88 concentrations of model compounds in their synthetic solutions (e.g., ~88 mg/L of

89 1,4-dioxane in sodium chloride electrolytes). The feasibility of electrochemical chlorine

90 generation at Cl– concentrations relevant to decentralized water treatment and its effect on

91 micropollutant removal in real water matrix have yet to be investigated.

92 The objective of this study was to evaluate an electrochemically driven UV/Cl2 (refer to as

93 E-UV/Cl2 hereafter) process that combines UV irradiation with in situ electrochemical

94 production of Cl2 for micropollutant removal under conditions simulating decentralized water

95 treatment. A surface water was spiked with several micropollutants that have varying UV and

96 chlorine reactivities, then treated by UV irradiation, electrolysis, E-UV/Cl2, and conventional

97 UV/Cl2 process. The performance of the different processes was compared in terms of

98 micropollutant abatement efficiency, energy consumption, and chlorinated by-product

99 formation. The mechanisms of micropollutant abatement during the E-UV/Cl2 process were

100 assessed using a chemical kinetic approach. The effects of important process and water

101 parameters (electrodes, current densities, and Cl– concentrations) of the E-UV/Cl2 were then

102 evaluated systematically.

103

104 2. Materials and methods

105 2.1. Chemicals and reagents

106 Carbamazepine, metoprolol, ciprofloxacin, and trimethoprim with purity > 98% were

107 purchased from Aladdin Reagent Co., Ltd. (Shanghai, China) and used as the model

108 micropollutants in this study. The second-order rate constants for the reaction of the model

109 micropollutants with main oxidants in the UV/Cl2 system (HOCl, •OH, Cl•, ClO•, and Cl2–•),

110 as well as their UV254 molar absorption coefficient (ε254) and quantum yield (Φ254) are

111 summarized in Table 1. All other chemicals used in this study were of analytical grade.

112 Methyl tert-butyl ether (MTBE) was obtained from Sigma-Aldrich (USA). Acetonitrile was

6
113 shipped from Fisher Scientific (USA). Sodium chloride (NaCl) was purchased from Guangfu

114 Technology Development Co., Ltd. (Tianjin, China). Sodium hypochlorite solution was

115 obtained from Macklin Biochemical Co., Ltd. (Shanghai, China). Stock solutions of

116 micropollutants were prepared with Milli-Q ultrapure water.

117

118 Table 1. The properties of model micropollutants used in this study.

119

120 2.2. Water sample

121 A surface water was sampled from a lake in the suburb of Beijing, China, then used within

122 one week for the E-UV/Cl2 experiments. Main parameters of the selected surface water are

123 shown in Table 2. The surface water had very low background concentration of the model

124 micropollutants (< 1 μg/L). To facilitate the evaluation of micropollutant removal kinetics

125 during treatment, micropollutant stock solutions were spiked in the surface water to obtain an

126 initial concentration of ~100 μg/L for each model micropollutant. In addition, small amounts

127 of NaCl were added in the surface water to adjust Cl– concentrations to 30–300 mg/L, which

128 is within the typical range of Cl– concentrations in water sources for decentralized systems

129 (e.g., grey water and municipal wastewater) (Guo et al. 2018, Sanchez et al. 2010, Yao et al.

130 2016, Yu et al. 2013).

131

132 Table 2. Main water parameters of the selected surface water.

133

134 2.3. UV irradiation, electrolysis, E-UV/Cl2, and UV/Cl2 treatment of the surface water

135 The selected surface water (700 mL) was added in a cylindrical glass reactor (28 cm height

136 and 6.5 cm inner diameter), then treated by UV irradiation alone, electrolysis alone, and the

137 E-UV/Cl2 process for 10 min (see Fig. 1 for the experimental setup). For UV irradiation

138 experiments, a low-pressure UV lamp (GPH265T5L/4 Heraeus) emitting primarily 254 nm

7
139 UV light was installed in the center of the reactor. The average UV fluence rate was measured

140 to be 0.87 mW cm–2 using the iodide/iodate chemical actinometry (Frangos et al. 2016, Rahn

141 1997). For electrolysis experiments, a pair of electrodes with an inter-electrode gap of 1 cm

142 were installed vertically in the reactor. The anode was a ruthenium- and iridium-oxide coated

143 titanium (RuO2/IrO2-Ti) plate (4 cm × 12 cm) and the cathode was a stainless steel (SS) plate

144 (4 cm × 12 cm). Electrolysis treatments were conducted under galvanostatic conditions with

145 varying currents of 200–800 mA (corresponding to current densities of 4.2–16.7 mA/cm2, Eq.

146 (1)).

j=
I
147 (1)
S

148 where j is the applied current density (mA/cm2), I is the applied current (mA), and S is the

149 area of electrode (cm2).

150 For the E-UV/Cl2 treatments, both the UV lamp and electrodes were installed in the reactor

151 in the same way as for UV irradiation alone and electrolysis alone. During the treatments, the

152 solution was vigorously agitated using a magnetic stirring bar. All experiments were repeated

153 twice, and the standard deviations are shown as error bars in the figures

154

155 Fig. 1. The experimental setup of the E-UV/Cl2 process.

156

157 2.4. Analytical methods

158 Free chlorine (hypochlorous acid/hypochlorite, HOCl/OCl–) was analyzed using the

159 N,N-diethyl-p-phenylenediamine method with a Hach chlorine detector (Pocket Colorimeter)

160 (Mao et al. 2018). For micropollutant analysis, water samples were filtered through 0.45 μm

161 membrane, then quenched with sodium sulfite. The test micropollutants were then analyzed

162 with an ultra-performance liquid chromatography/tandem mass spectrometry API 3200

8
163 LC/MS/MS system, Applied Biosystems (see Supporting Information (SI) Text S1 and Table

164 S1 for analytical details) (Guo et al. 2017). Trihalomethanes (THMs, including trichloro-,

165 bromodichloro-, dibromochloro-, and tribromomethanes (TCM, DCBM, DBCM, and TBM))

166 were extracted with MTBE and then quantified using a gas chromatograph with an electron

167 capture detector according to the USEPA Method 551.1 (USEPA 1995). Chlorate (ClO3−),

168 chlorite (ClO2−), and bromate (BrO3−) ions were measured using an ion chromatograph

169 (ICS-1100, Thermo Dionex) with a conductivity detector.

170

171 3. Results and discussion

172 3.1. Electro-generation of chlorine

173 Fig. 2 shows that during electrolysis and the E-UV/Cl2 process, the concentrations of free

174 chlorine (HOCl/OCl–) increased continuously in the surface water (added with 30–300 mg/L

175 Cl–). These observations indicate that Cl– is stably oxidized at the RuO2/IrO2-Ti anode surface

176 to form Cl2, which then quickly hydrolyzes to yield free chlorine (Eqs. (2–3))

177 (Martinez-Huitle et al. 2015), kCl2 ,H2 O = 28.6 s–1 (Wang and Margerum 1994)) in the water.

178 With increasing the initial concentration of Cl– from 30 to 300 mg/L, ~3.9–29.3 mg/L free

179 chlorine accumulated in the surface water after 10 min of electrolysis alone (Fig. 2). This

180 observation indicates that the rate of anodic oxidation of Cl– to Cl2 is mass transfer limited

181 under the test conditions, and thus increases with increasing Cl– concentrations. For a given

182 initial Cl– concentration, the concentrations of free chlorine accumulated during the E-UV/Cl2

183 process were generally ~30% lower than those during electrolysis alone. These differences

184 suggest that ~30% of the electrochemically-generated free chlorine is then photolyzed by UV

185 irradiation during the E-UV/Cl2 process. As shown in SI Fig. S1, chlorine decomposition by

186 UV photolysis followed pseudo-first-order kinetics. Therefore, with more chlorine being

187 electrochemically produced at higher Cl– concentrations, the rate of ensuing photolysis of free

9
188 chlorine to •OH and RCS also increases (Guo et al. 2018, Xiang et al. 2016).

189 2Cl– – 2e– → Cl2 (2)

190 Cl2 + H2 O → HCl + HOCl (3)

191

192 Fig. 2. Evolution of free chlorine concentrations during electrolysis and the E-UV/Cl2

193 treatment of the selected surface water. Reaction conditions: volume = 700 mL, current = 400

194 mA, UV power = 10 W, UV fluence rate = 0.87 mW cm–2.

195
196 The results shown in Fig. 2 suggest that anodic oxidation of Cl– can possibly offer a

197 feasible way to produce Cl2 on site for applying the UV/Cl2 technology in decentralized water

198 treatment systems. For instance, the conventional UV/Cl2 process typically involves adding

199 ~1–6 mg/L of free chlorine in the water, followed by ~5–20 min UV irradiation (Guo et al.

200 2018, Remucal and Manley 2016, Yang et al. 2016). In comparison, Fig. 2 shows that ~2.0–

201 14.6 mg/L of free chlorine could be quickly produced in 5 min during electrolysis of the water

202 containing 30–300 mg/L Cl–. These data confirm that sufficient amounts of chlorine can be

203 quickly electrochemically produced at typical Cl– concentrations present in water sources for

204 decentralized systems (Sanchez et al. 2010, Yu et al. 2013). Therefore, the electrochemical Cl2

205 generation can avoid the transport and storage of chlorine stocks, thus enabling the E-UV/Cl2

206 process for decentralized water treatment.

207

208 3.2. Comparison of UV, chlorination, electrolysis, E-UV/Cl2, and conventional UV/Cl2

209 3.2.1. Micropollutant abatement

210 To evaluate the effectiveness of the E-UV/Cl2 process for micropollutant abatement, four

211 model compounds that have differing UV, chlorine, and electrochemical reactivity were

10
212 spiked in the surface water (Cl– = 100 mg/L), followed by the E-UV/Cl2 treatment. For

213 comparison, the water was also treated by UV irradiation, chlorination, electrolysis, and

214 conventional UV/Cl2 process under similar reaction conditions (see Fig. 3). In general, all

215 spiked micropollutants were eliminated to below their detection limits within 5 min of the

216 E-UV/Cl2 process (Fig. 3d). In contrast, at least one micropollutant could be still detected in

217 the water after 10 min of the other four processes (Figs. 3a–c and e). This finding highlights

218 that the E-UV/Cl2 process may provide an effective way to abate micropollutants with

219 different properties (see discussion below).

220
221
222 Fig. 3. Micropollutant abatement during (a) UV irradiation, (b) chlorination, (c) electrolysis,

223 (d) E-UV/Cl2 and (e) conventional UV/Cl2 treatment of the selected surface water. Reaction

224 conditions: [Cl–]0 = 100 mg/L, current = 400 mA for electrolysis and E-UV/Cl2, [Cl2]0 = 6

225 mg/L for chlorination and UV/Cl2, UV power = 10 W, UV fluence rate = 0.87 mW cm–2.

226

227 Among the four test compounds, carbamazepine, metoprolol, and trimethoprim are

228 resistant to UV photolysis due to their low UV absorbance and/or quantum yield, whereas

229 ciprofloxacin is UV reactive (see Table 1). Therefore, only ciprofloxacin was effectively

230 abated with 10 min of UV irradiation treatment, while the other three compounds were abated

231 by generally < 20% (Fig. 3a).

232 As reported in Table 1, ciprofloxacin and trimethoprim are highly and moderately

233 reactive with free chlorine, whereas carbamazepine and metoprolol are inactive with free

234 chlorine. Consequently, ciprofloxacin and trimethoprim were quickly eliminated in ~1 and 5

235 min during chlorination (Fig. 3b). In contrast, only ~20% abatement efficiencies were

236 obtained for carbamazepine and metoprolol after 10 min of chlorination.

237 During electrolysis, pollutants can be abated by direct electron transfer to the anode (i.e.,

238 direct electrolysis) and/or mediated oxidation by electrochemically generated oxidizing

11
239 species such as •OH and chlorine (i.e., indirect electrolysis) (Panizza and Cerisola 2009). The

240 RuO2/IrO2-Ti anode used in this study has a high activity for chlorine evolution, but low

241 activity for •OH production from water discharge (Chaplin 2014, Panizza and Cerisola 2009).

242 Therefore, it is expected that pollutants are mainly abated by direct electrolysis and/or

243 oxidation with free chlorine (Cl2-mediated oxidation) during electrolysis with the

244 RuO2/IrO2-Ti anode (Barazesh et al. 2016, Jasper et al. 2016). Fig. 3c shows that

245 ciprofloxacin and trimethoprim were quickly eliminated in 2 and 3 min during chlorination

246 and electrolysis ([Cl–]0 = 100 mg/L), whereas carbamazepine and metoprolol required much

247 longer electrolysis time to eliminate (≥ 10 min). Note that while carbamazepine and

248 metoprolol have the similar chlorine reactivity (Table 1), carbamazepine was eliminated

249 considerably faster than metoprolol during electrolysis. This difference suggests that

250 carbamazepine is more electrochemically reactive than metoprolol, and can thus be more

251 quickly abated by direct electron transfer at the anode during the electrolysis process.

252 Besides the aforementioned abatement mechanisms, UV photolysis of electrochemically

253 generated free chlorine can produce a variety of radicals, including •OH, Cl•, ClO•, and Cl2–•

254 in the E-UV/Cl2 system (Kishimoto et al. 2018, Remucal and Manley 2016). •OH is a

255 non-selective oxidant and can oxidize almost all organics at nearly diffusion-controlled rates

256 (Buxton et al. 1988). On the other hand, Cl• and other RCS are selective oxidants and react

257 preferentially with organics that have electron-rich moieties (Remucal and Manley 2016).

258 Rationally, •OH and RCS can also participate in the oxidation of micropollutants during the

259 E-UV/Cl2 process, thus resulting in different extent of enhancement for the abatement of the

260 four test compounds compared to UV irradiation and electrolysis (see Figs. 3a, c–d). The most

261 significant enhancement is observed for metoprolol, which was quickly eliminated in 4 min

262 during the E-UV/Cl2 process, but only gradually abated during UV irradiation, chlorination,

263 and electrolysis. In comparison, the enhancement is less significant for ciprofloxacin and

12
264 trimethoprim since they could already be quickly abated by electrolysis alone. For

265 carbamazepine, which was abated at a moderate rate during electrolysis (eliminated in 10

266 min), moderate enhancement was obtained for its abatement during the E-UV/Cl2 process

267 (eliminated in 5 min). These observations suggest that the E-UV/Cl2 process is most

268 beneficial for enhancing the removal of micropollutants that have low UV, electrochemical,

269 and chlorine reactivities, and thus resistant to UV irradiation, chlorination, and electrolysis

270 treatment (e.g., metoprolol).

271 Fig. 3d shows that the E-UV/Cl2 process completely abated all four test compounds

272 within 5 min. According to Fig. 1, ~6 mg/L free chlorine could be electrochemically

273 generated from the anodic oxidation of Cl– during 5 min of electrolysis of the surface water.

274 Therefore, 6 mg/L free chlorine was added in the surface water, followed by 10 min of UV

275 irradiation for the conventional UV/Cl2 treatment. Due to photolysis, free chlorine

276 concentrations decreased logarithmically during the conventional UV/Cl2 process, which is in

277 contrast to the gradual increase of free chlorine concentrations during the E-UV/Cl2 process

278 (see Fig. 4a). Because of the higher initial concentration of free chlorine, higher chlorine

279 exposures (CT) were obtained in the first 5 min of the conventional UV/Cl2 process compared

280 with the E-UV/Cl2 process (Fig. 4b). Corresponding to the high initial CT, ciprofloxacin and

281 trimethoprim were quickly eliminated in 1 min during the conventional UV/Cl2 process (Figs.

282 3d and e). In addition, metoprolol was also effectively eliminated in 4 min. However,

283 carbamazepine was abated at a considerably slower rate during the UV/Cl2 process.

284 Consequently, ~18% residual concentrations of carbamazepine could still be detected in the

285 water after 10 min of the UV/Cl2 treatment. These observations are consistent with the

286 previous findings that carbamazepine is usually less efficiently removed by the conventional

287 UV/Cl2 process compared to the other three test compounds (Guo et al. 2018, Yang et al.

288 2016).

13
289

290 Fig. 4. Evolutions of (a) free chlorine concentrations and (b) chlorine exposures during the

291 electrolysis, conventional UV/Cl2, E-UV/Cl2 processes. Reaction conditions: [Cl–]0 = 100

292 mg/L, UV power = 10 W for UV/Cl2 and E-UV/Cl2, current = 400 mA for electrolysis and

293 E-UV/Cl2, [Cl2]0 = 6 mg/L for UV/Cl2, UV fluence rate = 0.87 mW cm–2.

294

295 3.2.2. Mechanisms of micropollutant abatement during electrolysis, UV/Cl2, and E-UV/Cl2

296 According to the mechanisms of micropollutant abatement during the electrolysis,

297 UV/Cl2, and E-UV/Cl2 processes, the kinetics of micropollutant abatement during the three

298 processes can be described using Eqs. (4), (5), and (6), respectively.

dP
299 – dt
= kDE P + kchlorine [chlorine][P] (4)

dP –
300 – dt
= kUV P + kchlorine chlorine P + k•OH •OH P + kCl• Cl• P + k – Cl2 • P +
Cl2 •

301 kClO• ClO• P (5)

dP
302 – dt
= kDE P + kUV P + kchlorine chlorine P + k•OH •OH P + kCl• Cl• P +

–
303 k – Cl2 • P + kClO• ClO• P (6)
Cl2 •

304 where kDE and kUV are the first-order rate constant of P abatement by direct electrolysis and

305 direct UV photolysis, respectively; kchlorine, k•OH, kCl•, k – , and kClO• are the second-order rate
Cl2 •

306 constants for the reaction of micropollutant with chlorine, •OH, Cl•, Cl2–•, and ClO•,

307 respectively.

308 By integration, Eqs. (4–6) result in

P
309 – ln P0
= kDE t + kchlorine chlorine dt (7)

P –
310 – ln = kUV t + kchlorine chlorine dt + k•OH •OH dt + kCl• Cl• dt + k – Cl2 • dt +
P0 Cl2 •

311 kClO• ClO• dt (8)

14
 = kDE t + kUV t + kchlorine
P
312 – ln P0
chlorine dt + k•OH •OH dt + kCl• Cl• dt +

–
313 k – Cl2 • dt + kClO• ClO• dt (9)
Cl2 •

314 In Eq. (7), chlorine dt (chlorine exposures, CT) can be obtained from the

315 time-integrated chlorine concentrations over a given reaction period during the electrolysis

316 process (see Fig. 4). Based on the chlorine exposures and micropollutant abatement

317 efficiencies observed during the electrolysis process, the rate constants for micropollutant

318 abatement by direct electrolysis (kDE) can be obtained by fitting the data using Eq. (7) (see SI

319 Fig. S2). Thus, the relative contribution of direct electrolysis and oxidation with chlorine to

320 micropollutant abatement (fE and fchlorine) during the electrolysis process can be estimated

321 using Eqs. (10) and (11), respectively.

kDE
322 fDE = P (10)
– ln
P0

kchlorine chlorine dt
323 fchlorine = P (11)
– ln
P0

324 As shown in Fig. 5a, due to its high chlorine reactivity, ciprofloxacin was abated almost

325 exclusively by chlorine oxidation (~100%) during the electrolysis process. In contrast, direct

326 electrolysis dominated the mechanisms of trimethoprim, carbamazepine, and metoprolol

327 abatement during the process.

328

329 Fig. 5. The relative contributions of direct electrolysis, direct UV photolysis, oxidation with

330 chlorine and radicals (•OH and RCS) for micropollutant abatement by (a) electrolysis, (b)

331 conventional UV/Cl2, and (c) the E-UV/Cl2 process. Reaction conditions: [Cl–]0 = 100 mg/L,

332 UV power = 10 W for UV/Cl2 and E-UV/Cl2, current = 400 mA for electrolysis and E-UV/Cl2,

333 [Cl2]0 = 6 mg/L for UV/Cl2, UV fluence rate = 0.87 mW cm–2.

334

15
335 Theoretically, the contribution of photolysis, electrolysis, oxidation with chlorine, •OH,

336 and each RCS for micropollutant abatement during the UV/Cl2 and E-UV/Cl2 processes can

337 also be estimated using the similar approach. For example, the contribution of UV photolysis

338 for micropollutant abatement during the UV/Cl2 and E-UV/Cl2 processes can be estimated

339 using Eq. (12).

kUV t
340 fUV = P (12)
– ln
P0

341 where kUV is the pseudo-first order rate constant observed for micropollutant abatement

342 during UV photolysis (SI Table S2). However, due to the difficulty in following the

343 concentrations of •OH and RCS, the exposures of these radicals cannot be obtained during the

344 UV/Cl2 and E-UV/Cl2 processes (Guo et al. 2018, Kishimoto et al. 2018). Therefore, it is

345 impossible to calculate the respective contribution of each radical to micropollutant abatement

346 for the two processes. Alternatively, the overall contribution of •OH and RCS (fR) to

347 micropollutant abatement during the UV/Cl2 and E-UV/Cl2 processes are collectively

348 estimated as fR using Eq. (13) and (14), respectively.

349 fR = 1 – fUV – fchlorine (13)

350 fR = 1 – fDE – fUV – fchlorine (14)

351 Fig. 5b shows that during the conventional UV/Cl2 process, ciprofloxacin was mainly

352 abated by oxidation with free chlorine. In contrast, the other three micropollutants

353 (trimethoprim, metoprolol, and carbamazepine) were abated primarily by the radicals (•OH

354 and RCS) generated from chlorine photolysis. During the UV/Cl2 process, •OH and/or Cl• are

355 usually considered the main radicals for pollutant degradation (Fang et al. 2014, Remucal and

356 Manley 2016, Xiang et al. 2016). Meanwhile, other RCS (such as Cl2–•) can contribute

357 non-negligibly to the abatement of some compounds that have high reactivity with the

358 specific RCS (Kishimoto et al. 2018, Remucal and Manley 2016). Under the test conditions of

359 this study ([Cl–] = 100 mg/L), the equilibrium concentration of ClO2–• is estimated to be ~116
16
360 times that of Cl• (calculated based on the equilibrium constant of reversible reaction (Eq. (15))

361 (Kishimoto et al. 2018)). On the other hand, the rate constants for the reaction of metoprolol

362 and trimethoprim with ClO2–• are about 1/34 and 1/11 of those with Cl•. of their kCl•,

363 respectively (see Table 1). This information suggests that ClO2–• may play an even more

364 important role than Cl• for metoprolol and trimethoprim abatement during the UV/Cl2 process.

365 This also explains the slower abatement of carbamazepine than metoprolol during the UV/Cl2

366 process (Fig. 3e); while both compounds have generally the similar •OH, Cl•, and ClO• rate

367 constants, the ClO2–• rate constant of carbamazepine is significantly lower than that of

368 metoprolol (Table 1).

–
Cl• + Cl– ⇌ Cl2 •
– [Cl2 •]
369 (K1 = –
= 5.9 × 104 M–1 ) (15)
[Cl•][Cl ]

370 Compared with the electrolysis and UV/Cl2 processes, the E-UV/Cl2 process considerably

371 accelerated the abatement of metoprolol and carbamazepine, respectively (Figs. 3c–e). As

372 shown in Fig. 5c, metoprolol was mainly abated by oxidation with •OH and RCS during the

373 E-UV/Cl2 process. This finding suggests that photolysis of electro-generated chlorine to the

374 radicals is the main mechanism for the accelerated metoprolol abatement in the E-UV/Cl2

375 process. On the other hand, the E-UV/Cl2 process accelerated carbamazepine abatement than

376 the UV/Cl2 process probably by mainly the direct electrolysis mechanism, which contributed

377 ~78% of carbamazepine abatement during the E-UV/Cl2 process. Overall, the above

378 comparisons indicate that the E-UV/Cl2 process successfully combines different mechanisms

379 - UV photolysis, direct electrolysis, chlorine-mediated oxidation, as well as •OH and RCS

380 oxidation - for micropollutant abatement. Therefore, it considerably enhanced the abatement

381 of test compounds that were less effectively removed by the other processes. These results

382 suggest that the E-UV/Cl2 process may provide a promising treatment option to ensure the

383 effective removal of various micropollutants that coexist in water sources.

384
17
385 3.2.3. Energy consumption

386 The electrical energy demand to abate the concentration of micropollutants by 1 order of

387 magnitude in 1 m3 of water (i.e., electrical energy per order (EEO), kWh/m3-log) by the UV,

388 electrolysis, UV/Cl2, and E-UV/Cl2 processes are calculated using Eqs. (16–19) (Bolton et al.

389 2001) and compared in Fig. 6. The EEO for micropollutant abatement by chlorination was not

390 calculated because with the applied chlorine dose (6 mg/L), the concentrations of metoprolol

391 and carbamazepine can only be abated by less than 40%. The EEO shown in Fig. 6 consists of

392 two parts: (i) the energy consumption for UV irradiation and electrolysis operation, and (ii)

393 the equivalent energy consumption for chlorine doses, which is calculated based on the

394 market price of calcium hypochlorite ($1000/t) and the average electricity cost (12 cent/kWh)

395 in the U.S (Guo et al. 2018). The cost of NaCl was not included in the calculation due to its

396 low price (~0.07 USD/kg) and low dosage added in the water (100 mg/L Cl–), as well as the

397 possibility of using background Cl– in the water sources of decentralized systems (e.g., grey

398 water and municipal wastewater) for chlorine production (see the discussion of Fig. 2).

Pt P
399 EEO UV = C0 = 26Vk
(16)
60Vlog
Ct

UIt UI
400 EEO Electrolysis = C0 = (17)
60Vlog 26Vk
Ct

(P + UI)t P + UI
401 EEO (E-UV/Cl2 ) = C = (18)
60Vlog( 0) 26Vk
Ct

Pt 1000rCchlorine P 1000rCchlorine
402 EEO UV/Cl2 = C0 + C0 = + C0 (19)
60Vlog log 26Vk log
Ct Ct Ct

403 where P is the nominal power of the UV lamp (W), t is the treatment time (min), C0 and Ct

404 are the concentration of a specific pharmaceuticals at times t = 0 and t, respectively (µg/L),

405 V is the solution volume (L), k is the pseudo-first order rate constant for pollutant

406 abatement (min–1) observed for the different processes (see SI Table S2), I is the current (A),

407 U is the cell voltage (V), Cchlorine is the chlorine dose used in the UV/Cl2 process (mol/L), r

18
408 is the equivalent electrical energy demand for chlorine dose (0.851 kWh/mol (Guo et al.

409 2018)).

410

411 Fig. 6. Electrical energy per order removal (EEO) for micropollutant abatement in the selected

412 surface water by UV irradiation, electrolysis, E-UV/Cl2, and conventional UV/Cl2 processes.

413 The four consecutive bars (from left to right) for each process represents carbamazepine,

414 metoprolol, trimethoprim, and ciprofloxacin, respectively. Reaction conditions: [Cl–]0 = 100

415 mg/L, UV power = 10 W, current = 400 mA for electrolysis and E-UV/Cl2, [Cl2]0 = 6 mg/L

416 for UV/Cl2, UV fluence rate = 0.87 mW cm–2.

417

418 As shown in Fig. 6, different amounts of energy were required to abate the test

419 compounds by the four processes. In general, the EEO value for the abatement of a given

420 micropollutant by UV irradiation is significantly higher than that by the other three processes.

421 This observation indicates that UV irradiation alone is not an energy-efficient way to abate

422 micropollutants, especially UV-resistant micropollutants (Barazesh et al. 2015, Miklos et al.

423 2018). For the other three processes, the EEO values varied considerably for the four test

424 compounds due to their different UV and electrochemical reactivity. Specifically, metoprolol

425 required the largest amount of energy to abate by electrolysis, whereas carbamazepine

426 required the largest amounts of energy to abate by the E-UV/Cl2 and conventional UV/Cl2

427 processes.

428 The results shown in Fig. 6 indicate that due to their different physicochemical properties,

429 different amounts of energy are required to abate the varying micropollutants by a specific

430 process. To ensure the effective abatement of various micropollutants that coexist in a water

431 source (e.g., ≥ 90% abatement for each micropollutant), the energy consumption required for

432 a specific process will be determined by the micropollutants that are the slowest removed

19
433 during the process, e.g., metoprolol for electrolysis, and carbamazepine for the E-UV/Cl2 and

434 conventional UV/Cl2 processes (see Fig. 6). Overall, for the four test compounds, the

435 E-UV/Cl2 process required ~1.8 kWh/m3 energy to abate their concentration by ≥ 90% in the

436 surface water. This value is ~5–33% smaller than that for electrolysis (~1.9 kWh/m3), the

437 conventional UV/Cl2 process (~2.7 kWh/m3), and more than one order of magnitude smaller

438 than that for UV irradiation alone (~24.9 kWh/m3). These data suggest that the E-UV/Cl2

439 process can be a competitive technology for micropollutant abatement in term of energy

440 efficiency.

441

442 3.2.4. Formation of halogenated by-products

443 The formation of halogenated by-products is a major concern associated with the

444 electrochemical processes, as well as the UV/Cl2 process for water treatment and wastewater

445 reuse (Radjenovic and Sedlak 2015, Remucal and Manley 2016, von Gunten 2018). Fig. 7a

446 shows the concentration of THMs detected in the selected surface water when the

447 concentration of carbamazepine (which is the most resistant to E-UV/Cl2 treatment among the

448 tested compounds) was removed by 90% during the different treatment processes. For the

449 same degree of micropollutant removal, ~8.5 μg/L of THMs was detected in the surface water

450 treated by UV irradiation, whereas ~24–29 μg/L of THMs were detected for the electrolysis,

451 E-UV/Cl2, and conventional UV/Cl2 processes. These observations indicate that UV

452 irradiation generates insignificant amounts of organic halogenated by-products during the

453 treatment. In contrast, due to the involvement of chlorine and/or RCS in the treatment process,

454 the electrolysis, E-UV/Cl2, and conventional UV/Cl2 process will generate certain

455 concentrations of halogenated by-products. The concentrations of THMs increased slightly in

456 the order of E-UV/Cl2, electrolysis, and conventional UV/Cl2 process (Fig. 7a), which can be

457 possibly attributed to the different chlorine exposures attained when 90% of carbamazepine

20
458 abatement was achieved during the three processes (9.6, 18, and 20 mM s at ~5, 6, and 11 min

459 of the E-UV/Cl2, electrolysis, and UV/Cl2 process, respectively).

460 Besides halogenated organics, the electrochemical and UV/Cl2 processes can generate

461 some inorganic halogenated by-products such as chlorite (ClO2–), chlorate (ClO3–), and

462 bromate (BrO3–) during water treatment (Radjenovic and Sedlak 2015, Remucal and Manley

463 2016). Due to the low concentration of bromide in the selected surface water (24 μg/L, see

464 Table 2), insignificant concentrations of BrO3– (generally < 8 μg/L) were formed in all

465 processes, which are lower than the drinking water standard for BrO3– (10 μg/L) in many

466 countries (USEPA 1998, WHO 2011). In addition, ClO2– was not detected in this study

467 because of its short lifetime and analytical sensitivity (Lin et al. 2016, Remucal and Manley

468 2016). However, ~0.26–1.08 mg/L ClO3– were detected in the water when 90% of

469 carbamazepine was abated during the electrolysis, UV/Cl2, and E-UV/Cl2 process (see Fig.

470 7b). Note that although ClO3– is currently not a regulated DBP, the World Health Organization

471 recommends a guideline value of 0.7 mg/L for drinking water due to its potential adverse

472 health effects (WHO 2011).

473 During the E-UV/Cl2 process, ClO3– can be formed from both the stepwise

474 electrochemical oxidation of Cl– at the anode (as what occurs during the electrolysis process

475 (Lin et al. 2016, Radjenovic and Sedlak 2015)) and the photolysis of chlorine and ensuing

476 radical reactions involving Cl–, •OH, and RCS (as what occur during the conventional UV/Cl2

477 process (Remucal and Manley 2016)). Nevertheless, due to the considerably shorter treatment

478 time required to abate 90% of carbamazepine by the E-UV/Cl2 process (~5 min) than the

479 conventional UV/Cl2 process (~11 min), significantly less ClO3– was formed during the

480 E-UV/Cl2 process than the conventional UV/Cl2 process (Fig. 7b).

481 Overall, the results shown in Fig. 7 indicate that the concentrations of halogenated

482 by-products detected in the E-UV/Cl2 treated water are still considerably lower than the

21
483 drinking water standard or guideline value (e.g., 80 μg/L for THMs and 0.7 mg/L for ClO3–

484 (USEPA 1998, WHO 2011)), even when a high abatement efficiency (90%) has been achieved

485 for the most resistant micropollutant. These observations suggest that by carefully controlling

486 treatment conditions (e.g., chlorine concentration and treatment time), the formation of

487 halogenated by-products may not be a serious concern for the application of the E-UV/Cl2

488 process in decentralized water treatment systems.

489

490 Fig. 7. The concentration of (a) THMs and (b) ClO3– in the surface water treated by UV

491 irradiation, electrolysis, the E-UV/Cl2, and conventional UV/Cl2 process (for a 90%

492 abatement of carbamazepine concentration). Reaction conditions: [Cl–]0 = 100 mg/L, UV

493 power = 10 W, current = 400 mA for electrolysis and E-UV/Cl2, [Cl2]0 = 6 mg/L for UV/Cl2,

494 UV fluence rate = 0.87 mW cm–2.

495

496 3.3. Effect of process and water parameters on micropollutant abatement

497 3.3.1. Anode materials

498 The results shown in Figs. 2 and 3 suggest that UV photolysis of electro-generated free

499 chlorine to •OH and RCS plays a critical role in enhancing the abatement of micropollutants

500 that are resistant to individual UV and electrolysis treatment (e.g., metoprolol). To further

501 evaluate this mechanism, we replaced the RuO2/IrO2-Ti anode with a platinum coated Ti

502 (Pt/Ti) anode and repeated the electrolysis and E-UV/Cl2 treatment of the surface water.

503 Unlike RuO2 and IrO2, Pt is ineffective at electrochemically oxidizing Cl– to Cl2 (Panizza and

504 Cerisola 2009). Indeed, SI Fig. S3 shows that free chlorine concentrations were almost

505 undetectable during electrolysis with the Pt/Ti anode, but increased continuously during

506 electrolysis with the (reaching ~13.3 mg/L at 10 min). Corresponding to this difference,

507 insignificant enhancement was observed for micropollutant abatement when UV irradiation

22
508 was combined with electrolysis using the Pt/Ti anode (Fig. 8), in contrast to what have been

509 observed for the E-UV/Cl2 process using the RuO2/IrO2-Ti anode (Fig. 3). These observations

510 confirm that the electrochemical production of Cl2 is critical for the synergistic effect on

511 micropollutant abatement during the E-UV/Cl2 process. Therefore, anodes with high chlorine

512 evolution activity should be used in the E-UV/Cl2 process.

513

514 Fig. 8. Micropollutant abatement in the selected surface water during (a) electrolysis and (b)

515 combined UV and electrolysis process with Pt/Ti anodes. Reaction conditions: [Cl–]0 = 100

516 mg/L, current = 400 mA for electrolysis and E-UV/Cl2, [Cl2]0 = 6 mg/L for UV/Cl2, UV

517 power = 10 W, UV fluence rate = 0.87 mW cm–2.

518

519 3.3.2. Applied currents

520 Fig. 9a shows that with increasing applied currents from 200 to 800 mA, faster removal

521 of carbamazepine was obtained during the E-UV/Cl2 treatment of the surface water (see SI

522 Fig. S4 for the other test compounds). Due to its low initial concentration (100 μg/L), the rate

523 of carbamazepine abatement by direct electron transfer to the anode is mass-transfer limited

524 under the tested current densities (4.2–16.7 mA/cm2) (Chaplin 2014). Therefore, the increase

525 of currents will not considerably enhance carbamazepine abatement by direct electrolysis

526 (Barazesh et al. 2016, Jasper et al. 2016). However, the increase of currents increased almost

527 linearly the rate of chlorine evolution, resulting in higher concentrations of free chlorine in the

528 surface water (see SI Fig. S5). As photolysis of free chlorine follows pseudo-first order

529 kinetics (see SI Fig. S1), the rates of •OH and RCS production increase proportionally with

530 the free chlorine concentrations (Guo et al. 2018, Pan et al. 2017), thus leading to the

531 accelerated abatement of carbamazepine at higher applied currents (Fig. 9a).

532

23
533 Fig. 9. (a) Carbamazepine abatement and (b) EEO value for test compound abatement during

534 the E-UV/Cl2 treatment of the selected surface water with varying applied currents. The three

535 consecutive bars (from left to right) for each compound represents applied currents of 200,

536 400, and 800 mA, respectively. Reaction conditions: [Cl–]0 = 100 mg/L, UV power = 10 W,

537 UV fluence rate = 0.87 mW cm–2.

538

539 While increasing applied currents accelerated electrochemical chlorine production, it also

540 increased the cell voltage (see SI Table S3). As a result, the energy consumption for chlorine

541 production increased from 0.078 to 0.15 kWh/g Cl2 as applied currents were increased from

542 200 to 800 mA (see SI for detailed calculations). For carbamazepine and trimethoprim

543 abatement, the increase in energy consumption for electrochemical chlorine production was

544 well compensated by the decrease in energy consumption for UV irradiation due to their faster

545 abatement at higher currents (see Fig. 7a and SI Fig. S4a). Consequently, the EEO values for

546 carbamazepine and trimethoprim abatement decreased considerably as applied currents were

547 increased from 200 to 400–800 mA during the E-UV/Cl2 process (Fig. 7b). In contrast, the

548 EEO value for metoprolol abatement exhibited an inflection point at 400 mA, while the EEO

549 value for ciprofloxacin abatement increased monotonically with increasing applied currents,

550 because they could already be quickly abated at 200–400 mA. Overall, the results shown in

551 Fig. 9 suggest that there exists a marginal benefit associated with applying higher currents for

552 chlorine production in the E-UV/Cl2 process. Therefore, applied currents need to be carefully

553 controlled to balance the kinetics and energy efficiency for micropollutant abatement during

554 the E-UV/Cl2 process.

555

556 3.3.3. Chloride concentrations

557 Fig. 10a shows that as the initial Cl– concentration in the surface water was increased

24
558 from 30 to 300 mg/L, carbamazepine was more rapidly abated during the E-UV/Cl2 process.

559 In addition, the abatement of other test compounds was also accelerated to varied extent (see

560 SI Fig. S6). Accompanied with the faster abatement kinetics, the EEO values for test

561 compound abatement decreased considerably at higher Cl– concentrations (Fig. 10b).

562
563 Fig. 10. (a) Carbamazepine abatement and (b) EEO value for test compound abatement during

564 the E-UV/Cl2 treatment of the selected surface water with varying initial Cl– concentrations.

565 The three consecutive bars (from left to right) for each compound represents Cl–

566 concentrations of 30, 100, and 300 mg/L, respectively. Reaction conditions: Current = 400

567 mA, UV power = 10 W, UV fluence rate = 0.87 mW cm–2.

568

569 The results shown in Fig. 10 indicate that higher Cl– concentrations are beneficial for

570 enhancing the kinetics and energy efficiency for micropollutant abatement during the

571 E-UV/Cl2 process. These enhancements can be mainly attributed to the enhanced

572 electrochemical chlorine production at higher Cl– concentrations. As shown in Fig. 2, with

573 increasing initial Cl– concentrations, free chlorine accumulated more quickly in the surface

574 water during electrolysis, This in turn accelerates the rate of •OH and RCS production from

575 chlorine photolysis. Consequently, micropollutants can be more quickly abate by the

576 oxidation with free chlorine, •OH, and RCS during the E-UV/Cl2 process with higher Cl–

577 concentrations.

578 Due to the faster abatement kinetics at higher Cl– concentrations, shorter treatment time is

579 required for micropollutant abatement during the E-UV/Cl2 process (see Fig. 10a). This

580 reduced the energy consumption of UV irradiation considerably (Fig. 10b). In addition, the

581 energy consumption for electrochemical chlorine production also decreased considerably with

582 increasing Cl– concentration, e.g., from 0.43 to 0.024 kWh/g Cl2 as the initial Cl–

583 concentration was increased from 30 to 300 mg/L (see SI Table S3). Consequently, the EEO
25
584 values for test compound abatement were substantially reduced during the E-UV/Cl2 process

585 at higher Cl– concentrations.

586

587 3.4. Practical implications

588 This study demonstrates that the E-UV/Cl2 process may provide an attractive technology

589 for decentralized water treatment in terms of the effectiveness for micropollutant abatement,

590 energy consumption, and by-product formation. With chloride concentrations (30–300 mg/L)

591 typically found in the alternative water sources for decentralized systems, chlorine can be

592 electrochemically produced on site and on demand to enable the E-UV/Cl2 process for

593 micropollutant abatement. The electrochemical chlorine production avoids the transport and

594 management of liquid chlorine, which enhances the flexibility of the process for decentralized

595 water treatment. Under the tested conditions, the E-UV/Cl2 system could process ~200 L

596 water per day (700 mL water at a treatment time of 5 min) and effectively eliminated

597 micropollutants that are resistant to conventional UV and electrochemical treatment. The

598 energy consumption of the E-UV/Cl2 process for micropollutant removal is generally

599 comparable to the conventional UV/Cl2 process (Fig. 6). The residual chlorine in the effluent

600 can provide disinfection in the distributed systems. In addition, the E-UV/Cl2 system has a

601 simple modular configuration and uses durable, low-cost chlorine-evolution electrodes (e.g.,

602 RuO2/IrO2-Ti). The treatment process is driven by electricity and can be flexibly controlled by

603 adjusting currents. These favorable characteristics of the E-UV/Cl2 system facilitate the

604 scale-up, maintenance, and operation of the E-UV/Cl2 system for decentralized water

605 treatment at a household and community level. Based on the promising results shown herein,

606 additional studies will be carried out to further optimize the E-UV/Cl2 process and evaluate its

607 performance in pilot systems. In addition, more studies are needed to evaluate the

608 toxicological consequences of water treatment by the E-UV/Cl2 process to assess the overall

26
609 benefits of the technology.

610

611 4. Conclusions

612 This proof-of-concept study introduces the electrochemically driven UV/Cl2 (E-UV/Cl2)

613 process as a promising technology for micropollutant abatement in decentralized water

614 treatment systems. By electrochemically producing chlorine from the anodic oxidation of

615 chloride present in source waters, the E-UV/Cl2 process avoids the use of chlorine stocks and

616 thus overcomes the main barrier of the conventional UV/Cl2 process for decentralized systems.

617 Owing to the multiple abatement mechanisms of the E-UV/Cl2 process, micropollutants with

618 varied properties could be effectively abated in short treatment time with acceptable energy

619 consumption. The concentrations of chlorinated by-products could be controlled below the

620 drinking water standards when high abatement efficiencies had been achieved for the test

621 compounds during the E-UV/Cl2 process. These results suggest that the E-UV/Cl2 process

622 may provide a competitive technology for micropollutant abatement in decentralized water

623 treatment systems.

624

625 Acknowledgements

626 This study is funded by the NSFC project (51878370), the National Special Program of

627 Water Pollution Control and Management (2017ZX07202), the special fund of State Key Joint

628 Laboratory of Environment Simulation and Pollution Control (18L01ESPC), Tsinghua

629 University-INDITEX Sustainable Development Fund (TISD201906), and Foshan-Tsinghua

630 Innovation Special Fund (FTISF 2019THFS01-005).

631

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755 Figure Captions

756 Fig. 1. The experimental setup of the E-UV/Cl2 process.

757 Fig. 2. Evolution of free chlorine concentrations during electrolysis and the E-UV/Cl2

758 treatment of the selected surface water. Reaction conditions: volume = 700 mL, current = 400

759 mA, UV power = 10 W, UV fluence rate = 0.87 mW cm–2.

33
760 Fig. 3. Micropollutant abatement during (a) UV irradiation, (b) chlorination, (c) electrolysis,

761 (d) E-UV/Cl2 and (e) conventional UV/Cl2 treatment of the selected surface water. Reaction

762 conditions: [Cl–]0 = 100 mg/L, current = 400 mA for electrolysis and E-UV/Cl2, [Cl2]0 = 6

763 mg/L for chlorination and UV/Cl2, UV power = 10 W, UV fluence rate = 0.87 mW cm–2.

764 Fig. 4. Evolutions of (a) free chlorine concentrations and (b) chlorine exposures during the

765 electrolysis, conventional UV/Cl2, E-UV/Cl2 processes. Reaction conditions: [Cl–]0 = 100

766 mg/L, UV power = 10 W for UV/Cl2 and E-UV/Cl2, current = 400 mA for electrolysis and

767 E-UV/Cl2, [Cl2]0 = 6 mg/L for UV/Cl2, UV fluence rate = 0.87 mW cm–2.
768 Fig. 5. The relative contributions of direct electrolysis, direct UV photolysis, oxidation with

769 chlorine and radicals (•OH and RCS) for micropollutant abatement by (a) electrolysis, (b)

770 conventional UV/Cl2, and (c) the E-UV/Cl2 process. Reaction conditions: [Cl–]0 = 100 mg/L,

771 UV power = 10 W for UV/Cl2 and E-UV/Cl2, current = 400 mA for electrolysis and E-UV/Cl2,

772 [Cl2]0 = 6 mg/L for UV/Cl2, UV fluence rate = 0.87 mW cm–2.

773 Fig. 6. Electrical energy per order removal (EEO) for micropollutant abatement in the selected

774 surface water by UV irradiation, electrolysis, E-UV/Cl2, and conventional UV/Cl2 processes.

775 The four consecutive bars (from left to right) for each process represents carbamazepine,

776 metoprolol, trimethoprim, and ciprofloxacin, respectively. Reaction conditions: [Cl–]0 = 100

777 mg/L, UV power = 10 W, current = 400 mA for electrolysis and E-UV/Cl2, [Cl2]0 = 6 mg/L

778 for UV/Cl2, UV fluence rate = 0.87 mW cm–2.

779 Fig. 7. The concentration of (a) THMs and (b) ClO3– in the surface water treated by UV

780 irradiation, electrolysis, the E-UV/Cl2, and conventional UV/Cl2 process (for a 90%

781 abatement of carbamazepine concentration). Reaction conditions: [Cl–]0 = 100 mg/L, UV

782 power = 10 W, current = 400 mA for electrolysis and E-UV/Cl2, [Cl2]0 = 6 mg/L for UV/Cl2,

34
783 UV fluence rate = 0.87 mW cm–2.

784 Fig. 8. Micropollutant abatement in the selected surface water during (a) electrolysis and (b)

785 combined UV and electrolysis process with Pt/Ti anodes. Reaction conditions: [Cl–]0 = 100

786 mg/L, current = 400 mA for electrolysis and E-UV/Cl2, [Cl2]0 = 6 mg/L for UV/Cl2, UV

787 power = 10 W, UV fluence rate = 0.87 mW cm–2.

788 Fig. 9. (a) Carbamazepine abatement and (b) EEO value for test compound abatement during

789 the E-UV/Cl2 treatment of the selected surface water with varying applied currents. The three

790 consecutive bars (from left to right) for each compound represents applied currents of 200,

791 400, and 800 mA, respectively. Reaction conditions: [Cl–]0 = 100 mg/L, UV power = 10 W,

792 UV fluence rate = 0.87 mW cm–2.

793 Fig. 10. (a) Carbamazepine abatement and (b) EEO value for test compound abatement during

794 the E-UV/Cl2 treatment of the selected surface water with varying initial Cl– concentrations.

795 The three consecutive bars (from left to right) for each compound represents Cl–

796 concentrations of 30, 100, and 300 mg/L, respectively. Reaction conditions: Current = 400

797 mA, UV power = 10 W, UV fluence rate = 0.87 mW cm–2.

35
Table 1. The properties of model micropollutants used in this study.
–1 –1
Compound kChlorine a (M–1 s–1) kHO• (M–1 s–1) kClO• (M–1 s–1) kCl–2 • (M s ) kCl• (M–1 s–1) Φ254 ε254 (M–1 cm–1)
Metoprolol 1.2 × 10–2 b 8.4 × 109 c 1.34 × 108 d 5.07 × 108 e 1.71 × 1010 e 0.56 × 10–2 f 0.56 × 103 f
Carbamazepine 1.4 × 10–2 g 9.1 × 109 c 1.97 × 108 d 0.43 × 108 e 3.30 × 1010 e 0.06 × 10–2 h 8.98 × 103 h
Ciprofloxacin 9.0 × 105 i 5.9 × 109 h - 2.19 × 108 e 1.39 × 1010 e 1.18 × 10–2 h 1.29 × 104 h
Trimethoprim 5.8 × 101 j 6.3 × 109 h 4.46 × 1010 d 1.88 × 109 e 2.11 × 1010 e 1.18 × 10–3 h 8.43 × 103 h
a
Apparent k value for the reaction of free chlorine at pH 7.5.
b
(Acero et al. 2010)
c
(Barazesh et al. 2016)
d
(Guo et al. 2018)
e
(Lei et al. 2019)
f
(Rivas et al. 2010)
g
Calculated by SI Eq. (S1)
h
(Yang et al. 2016)
i
(Dodd et al. 2005)
j
(Dodd and Huang 2007)

Table 2. Main water parameters of the selected surface water.

Parameters Value
pH 7.60
DOC (mg/L) 3.39
UV254 (cm–1) 0.036
HCO3– (mg/L) 137
CO32– (mg/L) 0.00
Cl– (mg/L) 5.5
Br– (μg/L) 24
Conductivity (µS/cm) 296 a
a
The conductivity increased to 359–1127 µS/cm when small amounts of sodium chloride were added in the
surface water to adjust Cl– concentration to 30–300 mg/L.
 Highlights

An electrochemically driven ultraviolet/chlorine (E-UV/Cl2) process was developed.

Chlorine is in situ produced from anodic oxidation of chlorine in the source water.

The E-UV/Cl2 process effectively eliminates micropollutants with varying properties.

The energy consumption of E-UV/Cl2 is similar to the conventional UV/Cl2 process.

E-UV/Cl2 offers a promising way to abate micropollutant in decentralized systems.

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: