li eswrt aop modeling manuscript si r1 final · 2016-10-18 · 1 1 supporting information section 2...

1

SUPPORTING INFORMATION SECTION 1

2

A Mechanistic Understanding of the Degradation of Trace Organic Contaminants 3

by UV/Hydrogen Peroxide, UV/Persulfate and UV/Free Chlorine for Water Reuse 4

5

Wei Li1,2, Tushar Jain1, Kenneth Ishida3 and Haizhou Liu*1,2 6

7

1 Department of Chemical and Environmental Engineering, University of California, Riverside, 8

CA, USA 92521 9

2 Environmental Toxicology Program, University of California at Riverside, CA, USA 92521 10

3Orange County Water District, Fountain Valley, CA USA 92708 11

12

* Corresponding Author: e-mail: [email protected], phone (951) 827-2076 13

14

Submitted to Environmental Sciences: Water Research and Technology 15

Electronic Supplementary Material (ESI) for Environmental Science: Water Research & Technology.This journal is © The Royal Society of Chemistry 2016

2

Table of Content 16

Text S1 Calculation of photolysis rates .......................................................................................... 517

Text S2 Probe method to determine steady state concentration of radicals ................................... 718

Text S3 Rate constants of reactions involving radicals .................................................................. 919

Scheme S1 A diagram of the single UV flow-through reactor (UVPhox, Trojan Technology). 20

The kinetics modeling is based on the configuration of this reactor. ................................... 1121

Fig. S1 Comparison of UV/H2O2, UV/S2O82- and UV/HOCl treatment. (A) Consumption of 22

H2O2, S2O82- and HOCl by UV irradiance. (B) Log removal of organic contaminants. 23

[Oxidant]=88 µM, [contaminant]=50 nM, [Cl-]=80 µM, [inorganic carbon]=200 µM, 24

[bromide]=0.2 µM, TOC=0.15 mg C/L, pH=8, UV irradiance= 45.3 mW/cm2, UV 25

dosage=1178 mJ/cm2 in 26 seconds. .................................................................................... 1226

Fig. S2 1,4-dioxane removal byUV/H2O2, UV/S2O82- and UV/HOCl. (A) First order decay of 27

1,4-dioxane. (B) First-order decay of H2O2, S2O82- and HOCl by UV irradiance. (C) 28

contribution of radicals to 1,4-dioxane decay. [Oxidant]=2 mM, [1,4-dioxane]=250 µM, 29

[chloride]=80 µM, [inorganic carbon]=200 µM, [Br-]=0.2 µM, TOC=0.15 mg C/L, pH=5.8, 30

UV irradiance= 45.3 mW/cm2, UV dosage=1178 mJ/cm2 in 26 seconds. Dash lines are 31

modeled results. .................................................................................................................... 1332

Fig. S3 Phenol removal by UV/H2O2, UV/S2O82- and UV/HOCl. (A) First order decay of phenol. 33

(B) first order decay of H2O2, S2O82- and HOCl by UV irradiance. (C) contribution of 34

radicals to phenol decay. [Oxidant]=2 mM, [phenol]=250 µM, [Cl-]=80 µM, [inorganic 35

carbon]=200 µM, [Br-]=0.2 µM, TOC=0.15 mg C/L, pH=5.8, UV irradiance= 45.3 36

mW/cm2, UV dosage=1178 mJ/cm2 in 26 seconds. Dash lines are modeled results. .......... 1437

3

Fig. S4 Direct oxidation of 1,4-dioxane and phenol by HOCl. [Oxidant]=2 mM, 38

[contaminant]=250 µM, [Cl-]=80 µM, [inorganic carbon]=200 µM, [Br-]=0.2 µM, 39

TOC=0.15 mg C/L, pH=5.8. Dash lines are modeled results. .............................................. 1540

Fig. S5 Effect of pH on the treatment efficiency of UV/H2O2. (A) First-order degradation rates of 41

organic contaminants in treatment. (B) Radical distribution. [H2O2]=88 µM, [trace organic 42

contaminant]=50 nM, [Cl-]=0.08 mM, [inorganic carbon]=0.2 mM, [Br-]=0.2 µM, 43

TOC=0.15 mg C/L, UV irra diance=45 mW/cm2. ................................................................ 1644

Fig. S6 Effect of pH on the treatment efficiency of UV/HOCl. (A) First-order degradation rates 45

of organic contaminants in treatment. (B) Radical distribution. [HOCl]=88 µM, [trace 46

organic contaminant]=50 nM, [Cl-]=0.08 mM, [inorganic carbon]=0.2 mM, [Br-]=0.2 µM, 47

TOC=0.15 mg C/L, UV irradiance=45 mW/cm2. ................................................................. 1748

Fig. S7 Effect of chloride on the treatment efficiency of UV/H2O2. (A) First-order degradation 49

rates of organic contaminants in treatment. (B) Radical distribution. [H2O2]=88 µM, [trace 50

organic contaminant]=50 nM, pH=5.8, [inorganic carbon]=0.2 mM, [Br-]=0.2 µM, 51


Fig. S8 Effect of chloride on the treatment efficiency of UV/HOCl. (A) First-order degradation 53

rates of organic contaminants in treatment. (B) Radical distribution. [HOCl]=88 µM, [trace 54

organic contaminant]=50 nM, pH=5.8, [inorganic carbon]=0.2 mM, [Br-]=0.2 µM, 55


Fig. S9 Effect of inorganic carbon on the treatment efficiency of UV/S2O82-. (A) First-order 57

degradation rates of organic contaminants in treatment. (B) Radical distribution. [S2O82-58

]=88 µM, [trace organic contaminant]=50 nM, pH=5.8, [Cl-]=80 µM, [Br-]=0.2 µM, 59


4

Fig. S10 Effect of inorganic carbon on the treatment efficiency of UV/H2O2. (A) First-order 61

degradation rates of organic contaminants in treatment. (B) Radical distribution. [H2O2]=88 62

µM, [trace organic contaminant]=50 nM, pH=5.8, [Cl-]=80 µM, [Br-]=0.2 µM, TOC=0.15 63

mg C/L, UV irradiance=45 mW/cm2. ................................................................................... 21 64

5

Text S1 Calculation of photolysis rates 65

The photolysis rate (rp) of H2O2, S2O82- and HOCl by low-pressure high-output (LPHO) mercury 66

vapor UV lamp (λ=254nm) was calculated based on the following equation: 67

rp= - 2 ´ F × I0 × foxidant × fsolution (1) 68

F is the extinction coefficient of the oxidation, i.e., FH2O2=0.5 (Baxendale and Wilson, 1957), 69

Fpersulfate=0.7 (Mark et al., 1990), FHOCl=0.7 (Watts and Linden, 2007), FOCl-=0.52 (Nowell and 70

Hoigne, 1992). Io is volume-normalized UV irradiance from the flow-through UV reactor 71

(Scheme S1). 72

foxidant is the fraction of incident light absorbed by the oxidant. fsolution is the fraction of light 73

absorbed by the total solution, which were calculated as: 74

!"#$%&'( =+,-,+.-. (2) 75

!/"01($"' = 1 − 105(78 +.-.)0 (3) 76

εp is the molar extinction coefficient of the oxidant (M-1�cm-1), cp is the concentration of the 77

oxidant (M). εi and ci are the molar extinction coefficient and concentration for NOM and a 78

particular contaminant selected. a is the absorption coefficient of the solution at the wavelength 79

of 254 nm and l is the path length of the reactor (cm). The direct photolysis rate for NOM and a 80

particular contaminant is also calculated based on the same equations except fcontaminant is 81

calculated based on the εi and ci of the particular contaminant (refer to Table S3 for the quantum 82

yield and molar extinction coefficient). 83

The volume-normalized surface irradiance from a flow-through UV reactor (Io) was calculated as 84

follows: 85

6

:; =<=>×@=>ABCDEF×G×(

(4) 86

The flow-through UV reactor was based on a configuration widely applied in water reuse 87

facilities (Scheme S1). The hydraulic retention time of the UV reactor (t) is 26 second. The 88

energy output of the low-pressure high-output mercury vapor UV lamp (Wuv) during the 89

hydraulic retention time of the UV reactor is 1179 mJ (Trojan Technology, London, ON). The 90

UV lamp surface area (Suv) is 1302 cm2. E is the energy of one mole of photons at the 91

wavelength of 254 nm (4.72×108 mJ), V is the volume of the UV reactor (9.8 L). Consequently, 92

Io was calculated as 1.27´10-5 L-1s-1. 93

7

Text S2 Probe method to determine steady state concentration of radicals 94

Nitrobenzene, benzoic acid and N,N-dimethylaniline were utilized to probe the steady state 95

concentration of HO•, SO4•-, Cl•, Cl2

•- and CO3•-. The control experiments showed a negligible 96

direct photo-degradation for all probe compounds. Nitrobenzene exclusively reacts with HO•, 97

therefore is the best probe for HO•. First, the experimentally observed pseudo first order decay 98

rate of nitrobenzene (kobs) was obtained and [HO•]ss was calculated based on Equation 1. 99

−ln( JK LJK M

) = NOP5JK[RS∙]//V (Eq. 1) 100

[NB]t is the concentration of nitrobenzene at time t; [NB]0 is the initial concentration of 101

nitrobenzene; kHO-NB is the first-order rate constant between HO• and nitrobenzene, i.e., 3.2×109 102

M-1s-1, Neta and Dorfman, 1968). 103

[CO3•-]ss is calculated based on equation 2 analogously. 104

−ln( J,JXYZ LJ,JXYZ M

) = N[P\5J,JXYZ[]S\∙5]//V (Eq. 2) 105

kCO3-NB is the first order rate constant between CO3•- and N,N-dimethylaniline (1.4×109 M-1s-1, 106

Lilie et al, 1978). 107

[Cl•]ss and [SO4•-]ss

were simultaneously calculated using Equationa 3 and 4 108

-ln( KZ LKZ M

) = (NOP5KZ[RS∙]// + N@P_5KZ[`S_∙5]// + N[05KZ ]a∙]// V (Eq. 3) 109

-ln( b,_X Lb,_X M

) = (NOP5b,_X[RS∙]// + N@P_5b,_X[`S_∙5]// + N[05b,_X ]a∙]// V (Eq. 4) 110

8

kHO-BA=4.3×109 M-1s-1, Wander et al, 1968); kSO4-BA=1.2×109 M-1s-1, Neta et al, 1977); 1.4×109 M-111

1s-1, kCl-BA=1.8×1010 M-1s-1, Martire et al. 2001). 112

In the UV/S2O82-, the contribution of Cl2

•- to benzoic acid and 1,4-dioxane degradation was 113

minimal because the steady state concentration of Cl2•- was low and its reactivity with the 114

contaminants was lower than Cl• (Martire et al, 2001). In UV/HOCl system, the steady-state 115

concentration of Cl2•- could be high enough to make significant contribution to contaminant 116

degradation because the reverse reaction of ClOH•- with Cl- (Reaction 54 in table S1) produced a 117

significant amount of Cl2•-. Therefore, [Cl•]ss

and [Cl2•-]ss were simultaneously calculated using 118

the following equations: 119

−ln( KZ LKZ M

) = (NOP5KZ[RS∙]// + N[0c5KZ[]ac∙5]// + N[05KZ ]a∙]// V (eq 5) 120

−ln( b,_X Lb,_X M

) = (NOP5b,_X[RS∙]// + N[0c5b,_X[]ac∙5]// + N[05b,_X ]a∙]// V (eq 6) 121

kCl2-BA= 1.0×106 - 1.0×108 M-1s-1, kCl2-1,4D=1.0×106 - 1.0×108 M-1s-1 (Text S3). 122

123

9

Text S3 Rate constants of reactions involving radicals 124

The rate constants for all six compounds were mostly obtained from NIST database (NIST, 125

2015). When the value was not available, a range of the rate constant was estimated base on 126

existing known values for similar compounds. For example, the reaction mechanism of Cl• and 127

Br• are very similar to HO•, and the rates are comparable to the rates of HO• (Grebel et al., 2010, 128

NIST, 2015), thus a ±10% of HO• rate was assigned to Cl• or Br•. The estimation also based on 129

the reaction mechanism of the specific radical with different type of molecules. For example, Cl• 130

reacts fast with aromatic compounds and amine containing compounds (109-1010 M-1s-1, NIST, 131

2015), moderately fast with unsaturated aliphatic compounds (108–109 M-1s-1) and slow with 132

saturated aliphatic compounds including chlorinated or brominated compounds (104–106 M-1s-1). 133

Br• has high reaction rates with aromatic compounds (109–1010 M-1s-1) and low reactivity with 134

aliphatic alcohols (104-106 M-1s-1, NIST, 2015). 135

A relatively high reactivity also applies to Cl2•-, ClBr•-, Br2

•- and CO3•- (Yang et al., 2014, Fang et 136

al, 2014). Therefore, a ±10% rate was assigned based on known rates for any of the above 137

radicals. With a comparison of available rate constants from the NIST database, Cl2•- has high 138

reaction rates (108 M-1s-1) with unsaturated aliphatic compounds than with aromatic (106–108 M-139

1s-1). Low reactivity with unsaturated carboxylic (106 M-1 s-1). CO3•- reacts fast with compounds 140

containing amines (108–109 M-1s-1, NIST, 2015), but low reactivity with aromatic compounds 141

(104–106 M-1s-1). The rates of direct oxidation by HOCl were estimated when the literature 142

values were not available. For example, the oxidation rates for aniline, 17b-estradiol, 143

sulfamethoxazole and carbamazepine by HOCl was estimated based on their known reaction 144

10

rates with O3 (Huber et al. 2003). The direct oxidation of 1,4-dioxane by HOCl is negligible 145

based on experimental verification (Figure S1). 146

11

147

Scheme S1 A diagram of the single UV flow-through reactor (Trojan Technologies, London, 148

ON). The kinetics modeling is based on the configuration of this reactor. 149

12

150

151 Fig. S1 Comparison of UV/H2O2, UV/S2O8

2- and UV/HOCl treatment based on the kinetic 152

model. (A) Consumption of H2O2, S2O82- and HOCl by UV irradiance. (B) Log removal of 153

organic contaminants. [Oxidant]=88 µM, [contaminant]=50 nM, [Cl-]=80 µM, [inorganic 154

carbon]=200 µM, [Br-]=0.2 µM, TOC=0.15 mg C/L, pH=8, UV irradiance= 45.3 mW/cm2, UV 155

dosage=1178 mJ/cm2 in 26 seconds. 156

0 5 10 15 20 25

0.0

0.2

0.4

0.6

0.8

1.0

0 200 400 600 800 1000 1200

Reaction Time (s)

C/C

0

UV Dosage (mJ�cm-2 )

S2O8

H2O2

UV/Cl2

UV/H2O2

UV/S2O82-

UV/HOCl

A

0

1

2

3

4

5

6

Log

Rem

oval

Trace Organic Contaminant

UV-H2O2UV-S2O82-UV-Cl2

UV/H2O2

UV/S2O82-

UV/HOCl

1,4-dioxane

Carbamazepine

Phenol

17b-estradiol

AnilineSulfame-thoxazoleB

14

13

13

157

158

159 Fig. S2 1,4-dioxane removal byUV/H2O2, UV/S2O8

2- and UV/HOCl. (A) First order decay of 160

1,4-dioxane. (B) First-order decay of H2O2, S2O82- and HOCl by UV irradiance. (C) contribution 161

of radicals to 1,4-dioxane decay. [Oxidant]=2 mM, [1,4-dioxane]=250 µM, [Cl-]=80 µM, 162

[inorganic carbon]=200 µM, [Br-]=0.2 µM, TOC=0.15 mg C/L, pH=5.8, UV irradiance= 45.3 163

mW/cm2, UV dosage=1178 mJ/cm2 in 26 seconds. Dash lines are modeled results. 164 165

0 2 4 6 8 10

0.2

0.4

0.6

0.8

1.0

0 200 400 600 800 1000 1200

C/C

0 1,

4-D


Reaction Time (min)

PS e

H2O2 e

Cl2 e

UV/S2O82-

UV/H2O2

UV/HOCl

A

0 2 4 6 8 10

0.4

0.6

0.8

1.0

0 200 400 600 800 1000 1200

C/C

0 ox

idan

t


Reaction Time (min)

PS e

H2O2 e

Cl2 e

UV/S2O82-

UV/H2O2

UV/HOCl

B

14

166

167

168

Fig. S3 Phenol removal by UV/H2O2, UV/S2O82- and UV/HOCl. (A) First order decay of phenol. 169

(B) First order decay of H2O2, S2O82- and HOCl by UV irradiance. (C) Contribution of radicals to 170

phenol decay. [Oxidant]=2 mM, [phenol]=250 µM, [Cl-]=80 µM, [inorganic carbon]=200 µM, 171

[Br-]=0.2 µM, TOC=0.15 mg C/L, pH=5.8, UV irradiance= 45.3 mW/cm2, UV dosage=1178 172

mJ/cm2 in 26 seconds. Dash lines are modeled results. 173

0 2 4 6 8 10

0.0

0.2

0.4

0.6

0.8

1.0

0 200 400 600 800 1000 1200

C/C

0 ph

enol


Reaction Time (min)

PS e

H2O2 e

Series5

UV/S2O82-

UV/H2O2

UV/HOCl

A

0 2 4 6 8 10

0.0

0.2

0.4

0.6

0.8

1.0

0 200 400 600 800 1000 1200

C/C

0 ox

idan

t


Reaction Time (min)

PS e

H2O2 e

Cl2 e

UV/S2O82-

UV/H2O2

UV/HOCl

B

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Log

rem

oval

SO4.-

OH.

Cl.

CO3.-

Cl2.-

Series6

Exp ExpExpMod ModMod

UV/S2O82-

UV/HOCl

UV/H2O2

C SO4�-

HO�

Cl�

CO3�-

Cl2�-

Direct oxidation

15

174 Fig. S4 Direct oxidation of 1,4-dioxane and phenol by HOCl. [Oxidant]=2 mM, 175

[contaminant]=250 µM, [Cl-]=80 µM, [inorganic carbon]=200 µM, [Br-]=0.2 µM, TOC=0.15 mg 176

C/L, pH=5.8. Dash lines are modeled results. 177

0.0

0.2

0.4

0.6

0.8

1.0

1.2

0 2.5 5 7.5 10

C/C

0

Reaction Time (min)

1,4-dioxanephenol

16

178

179

Fig. S5 Effect of pH on the treatment efficiency of UV/H2O2 based on the kinetic model. (A) 180

First-order degradation rates of organic contaminants in treatment. (B) Radical distribution. 181

[H2O2]=88 µM, [trace organic contaminant]=50 nM, [Cl-]=0.08 mM, [inorganic carbon]=0.2 182

mM, [Br-]=0.2 µM, TOC=0.15 mg C/L, UV irradiance=45 mW/cm2. 183

0.0E+00

1.0E-16

2.0E-16

3.0E-16

4.0E-16

0.0E+00

4.0E-11

8.0E-11

1.2E-10

5.0 5.5 6.0 6.5 7.0

[Cl� ]

ss (M

)

[R� ] s

s (M

)

pH

[OH.]

[CO3.-]

[Cl.]

[HO•]ss

[CO3•-]ss

B

[Cl•]ss

17

184

185

Fig. S6 Effect of pH on the treatment efficiency of UV/HOCl based on the kinetic model. (A) 186

First-order degradation rates of organic contaminants in treatment. (B) Radical distribution. 187

[HOCl]=88 µM, [trace organic contaminant]=50 nM, [Cl-]=0.08 mM, [inorganic carbon]=0.2 188

mM, [Br-]=0.2 µM, TOC=0.15 mg C/L, UV irradiance=45 mW/cm2. 189

0.0E+00

1.0E-12

2.0E-12

3.0E-12

0.0E+00

3.0E-10

6.0E-10

9.0E-10

1.2E-09

5.0 5.5 6.0 6.5 7.0

[R� ] s

s (M

)

[CO

3�- ]

ss (M

)

pH

CO3.-]ss

[HO.]ss

[Br.-]

[Cl.]ss

[HO•]ss

[Cl•]ss

[Br•]ss

[CO3•-]ss

B

18

190

191

Fig. S7 Effect of chloride on the treatment efficiency of UV/H2O2 based on the kinetic model. 192

(A) First-order degradation rates of organic contaminants in treatment. (B) Radical distribution. 193

[H2O2]=88 µM, [trace organic contaminant]=50 nM, [inorganic carbon]=0.2 mM, [Br-]=0.2 µM, 194

pH=5.8, TOC=0.15 mg C/L, UV irradiance=45 mW/cm2. 195

0.0E+00

2.0E-11

4.0E-11

6.0E-11

8.0E-11

0 50 100 150 200 250 300

[R� ] s

s (M

)

[Cl-] (µM)

[OH.]

[CO3.-]

[HO•]ss

[CO3•-]ss

B

19

196

197

Fig. S8 Effect of chloride on the treatment efficiency of UV/HOCl based on the kinetic model. 198

(A) First-order degradation rates of organic contaminants in treatment. (B) Radical distribution. 199

[HOCl]=88 µM, [trace organic contaminant]=50 nM, [inorganic carbon]=0.2 mM, [Br-]=0.2 µM, 200


0.0E+00

1.0E-12

2.0E-12

3.0E-12

0.0E+00

4.0E-10

8.0E-10

1.2E-09

0 50 100 150 200 250 300

[R� ] s

s (M

)

[CO

3�- ]

ss (M

)

[Cl-] (µM)

[CO3.-]

[OH.]

[Cl.]

[HO•]ss

[Cl•]ss

[CO3•-]ss

B

20

202

203

Fig. S9 Effect of inorganic carbon on the treatment efficiency of UV/S2O82- based on the kinetic 204

model. (A) First-order degradation rates of organic contaminants in treatment. (B) Radical 205

distribution. [S2O82-]=88 µM, [trace organic contaminant]=50 nM, [Cl-]=80 µM, [Br-]=0.2 µM, 206


0.0E+00

8.0E-12

1.6E-11

2.4E-11

3.2E-11

30 90 150 210 270 330 390

[R� ] s

s(M

)

[TOTCO3] (µM)

[HO.]ss

[SO4.-]ss

[CO3.-]ss

[HO•]ss

[SO4•-]ss

[CO3•-]ss

B

21

208

209

Fig. S10 Effect of inorganic carbon on the treatment efficiency of UV/H2O2 based on the kinetic 210

model. (A) First-order degradation rates of organic contaminants in treatment. (B) Radical 211

distribution. [H2O2]=88 µM, [trace organic contaminant]=50 nM, [Cl-]=80 µM, [Br-]=0.2 µM, 212


-1.0E-16

2.0E-16

5.0E-16

8.0E-16

0.0E+00

4.0E-11

8.0E-11

1.2E-10

1.6E-10

30 90 150 210 270 330 390

[Cl� ]

ss a

nd [C

l 2�- ]

ss (M

)

[HO

� ] ss

and

[CO

3�- ] s

s (M

)

[TOTCO3] (µM)

[CO3.-]ss

[HO.]ss

[Cl.]ss

[Cl2.-]ss

[CO3•-]ss

[HO•]ss

B

[Cl•]ss

[Cl2•-]ss

22

Table S1 Rate constants and elemental reactions for kinetics modeling 214 215

No. Reaction Rate Constant Reference 1 RcSc

de2SR∙ 1.0×105\s-1 Calculated

2 `cSjc5de2`S_∙5 1.4×105\s-1 Calculated

3 RS]adeSR∙ + ]a∙ 3.9×105\s-1 Calculated

4 ]aS5de]a∙ + S∙5 3.2×105\s-1 Calculated

5 nSodeSR∙ + pqrstuVv 1.8×105b;s-1 Calculated

6 `cSjc5 + SR. → `cSj∙5 1.4×10yM-1s-1 Buxton et al., 1990 7 `cSjc5 + `S_∙5 → `cSj∙5 + `S_c5 6.6×10{M-1s-1 Jiang et al., 1992 8 `cSjc5 + ]a∙ → `cSj∙5 + ]a 8.8×10| M-1s-1 Yu et al., 2004 9 `cSjc5 + ]S\∙5 → `cSj∙5 + ]S\c5 3.0×10y M-1s-1 Yang et al 2014

10 `cSjc5 + `S{∙5 → `cSj∙5 + `S{c5 1.0×10{ M-1s-1 Assumed 11 `S{c5 + R8 → R`S{5 5.0×10b; M-1s-1 Yang et al 2014 12 `S{c5 + `S_∙5 → `S{∙ + `S_c5 1.0×10j M-1s-1 Das 2001 13 R`S{5 → R8 + `S{c5 2.0×10bs-1 Yang et al 2014 14 R`S{5 + SR∙ → RcS + `S{∙5 1.7×10y M-1s-1 Maruthamuthu & Neta 1977 15 `S_∙5 + RcS → R`S_c5 + SR∙ 6.6×10cs-1 Herrmann et al., 1995 16 `S_c5 + ]a∙ → `S_∙5 + ]a5 2.5×10j M-1s-1 Das 2001 17 `S_∙5 + SR5 → `S_c5 + SR∙ 7.0×10y M-1s-1 Peyton 1993 18 `S_∙5 + ]a5 → `S_c5 + ]a∙ 3.0×10j M-1s-1 Das 2001 19 `S_∙5 + SR∙ → R`S{5 1.0×10b; M-1s-1 Das 2001 20 `S_∙5 + R`S{5 → `S{∙5 + `S_c5 + R8 1.0×10| M-1s-1 Das 2001 21 R`S_5 → R8 + `S_c5 1.2×105cs-1 Calculated 22 `S_∙5 + `S_∙5 → `cSjc5 7.0×10j M-1s-1 Das 2001 23 `S{∙5 + `S{∙5 → `cSjc5 + Sc 2.2×10j M-1s-1 Das 2001 24 `S{∙5 + `S{∙5 → `S_∙5 + `S_∙5 + Sc 2.1×10j M-1s-1 Das 2001 25 `S{∙5 + RSc∙ → Sc + R`S{5 5.0×10y M-1s-1 Yermakov et al., 1995 26 RcSc → R8 + RSc5 1.3×105bs-1 Yang et al., 2014 27 R8 + RSc5 → RcSc 5.0×10b; M-1s-1 Yang et al., 2014 28 RcSc + `S_∙5 → RSc∙ + R`S_5 1.2×10y M-1s-1 Wine et al., 1989 29 RcSc + `S_∙5 → RSc∙ + `S_c5 + R8 1.2×10y M-1s-1 Maruthamuthu & Neta, 1978 30 RcSc + Sc∙5 → SR∙ + SR5 + Sc 1.3×105b M-1s-1 Weinstein & Bielski, 1979 31 RcSc + S∙5 → Sc∙5 + RcS 4.0×10j M-1s-1 Buxton et al., 1988 32 RcS → R8 + SR5 1.0×105\s-1 Yang et al., 2014 33 R8 + SR5 → RcS 1.0×10bb M-1s-1 Yang et al., 2014 34 R8 + Sc∙5 → RSc∙ 5.0×10b; M-1s-1 Ilan & Rabani, 1976 35 SR∙ + RcSc → RSc∙ + RcS 2.7×10y M-1s-1 Buxton et al., 1988 36 SR∙ + SR5 → S∙5 + RcS 1.2×10b; M-1s-1 Buxton et al., 1988 37 S∙5 + RcS → SR∙ + SR5 1.8×10{s-1 Buxton et al., 1988 38 S∙5 + RSc5 → Sc∙5 + SR5 4.0×10j M-1s-1 Buxton et al., 1988 39 S∙5 + Sc → S\∙5 3.6×10� M-1s-1 Buxton et al., 1988 40 S∙5 + Sc.5 + R8 → SR5 + Sc 6.0×10j M-1s-1 Sehested et al., 1982 41 S\∙5 → Sc + S∙5 2.6×10\s-1 Elliot & McCracken 1989 42 SR∙ + S∙5 → RSc5 1.0×10b; M-1s-1 Buxton et al., 1988

23

43 SR∙ + RSc5 → RSc∙ + SR5 7.5×10� M-1s-1 Christensen et al., 1982 44 SR∙ + RSc∙ → RcS + Sc 6.6×10� M-1s-1 Sehested et al., 1968 45 SR∙ + Sc∙5 → SR5 +Sc 7.0×10� M-1s-1 Beck, 1969 46 SR∙ + SR∙ → RcSc 3.6×10� M-1s-1 Elliot, 1989 47 SR∙ + ]a5 → ]aSR.5 4.3×10� M-1s-1 Jayson et al., 1973 48 SR∙ + R`S_5 → RcS + `S_∙5 1.7×10| M-1s-1 Heckel et al., 1966 49 RSc∙ + RSc∙ → RcSc + Sc 8.3×10{ M-1s-1 Bielski et al., 1985 50 RSc∙ + RcSc → SR∙ + RcS +Sc 3.0×10;M-1s-1 Koppenol, 1978 51 RSc∙ + Sc∙5 → RSc5 + Sc 9.7×10y M-1s-1 Bielski et al., 1985 52 RSc∙ → R8 + Sc∙5 1.6×10{ s-1 Bielski et al., 1985 53 ]aSR.5 → ]a5 + SR∙ 6.1×10� s-1 Jayson et al., 1973 54 ]aSR.5 + ]a5 → SR5 + ]ac∙5 1.0×10_ M-1s-1 Grigorev et al., 1987 55 ]aSR.5 + R8 → ]a∙ + RcS 2.1×10b; M-1s-1 Jayson et al., 1973 56 RS]a + RcSc → R]a + RcS + Sc 1.1×10_ M-1s-1 Connick 1947 57 RS]a + SR∙ → ]aS∙ + RcS 2.0×10� M-1s-1 Matthew & Anastasio, 2006 58 RS]a + Sc∙5 → ]a∙ + SR5 + Sc 7.5×10| M-1s-1 Matthew & Anastasio, 2006 59 RS]a + RSc∙ → ]a∙ + SR5 + Sc + R 7.5×10| M-1s-1 Matthew & Anastasio, 2006 60 RS]a + ]a∙ → ]aS. + R8 + ]a5 3.0×10� M-1s-1 Klaning & Thomas, 1985 61 RS]a + ]a5 → ]acSR5 1.5×10_ M-1s-1 Wang & Margerum, 1994 62 ]a∙+RcSc → R8 + ]a5 + RSc∙ 2.0×10� M-1s-1 Yu & Barker, 2003 63 ]a∙ + RcS → ]aSR.5 + R8 2.5×10{ s-1 Jayson et al., 1973 64 ]a∙ + SR5 → ]aSR.5 1.8×10b; M-1s-1 Klaning & Thomas, 1985 65 ]a∙ + ]a5 → ]ac∙5 8.5×10� M-1s-1 Yu and Barker, 2003 66 ]a∙ + ]ac → ]a\ 5.3×10j M-1s-1 Bunce et al, 1985 67 ]a∙ + ]aS5 → ]aS. + ]a5 8.3×10� M-1s-1 Klaning & Thomas, 1985 68 ]a∙ + ]a∙ → ]ac 8.8×10y M-1s-1 Wu et al., 1980 69 ]ac∙5 + ]a∙ → ]ac + ]a5 2.1×10� M-1s-1 Yu & Barker, 2003 70 ]ac∙5 + SR5 → ]a5 + ]aSR.5 4.5×10y M-1s-1 Grigorev et al., 1987 71 ]ac∙5 → ]a∙ + ]a5 6.0×10_ s-1 Yu & Barker, 2003 72 ]ac∙5 + ]ac∙5 → 2]a5+]ac 9.0×10j M-1s-1 Yu & Barker, 2003 73 ]ac∙5 + RcS → ]a5 + R]aSR 1.3×10\ s-1 Mcelroy, 1990 74 ]ac∙5 + SR∙ → RS]a + ]a5 1.0×10� M-1s-1 Wagner et al., 1986 75 ]ac∙5 + RcSc → RSc∙ + R8 + 2]a5 1.4×10{ M-1s-1 Matthew & Anastasio, 2006 76 ]ac∙5 + RSc∙ → Sc + R8 + 2]a5 3.1×10� M-1s-1 Matthew & Anastasio, 2006 77 ]ac∙5 + Sc∙5 → Sc + 2]a5 2.0×10� M-1s-1 Matthew & Anastasio, 2006 78 R]aSR → R8 + ]aSR.5 1.0×10j s-1 Mcelroy, 1990 79 R]aSR → ]a∙ + RcS 1.0×10c s-1 Mcelroy, 1990 80 R]aSR + ]a5 → ]ac∙5 + RcS 5.0×10� M-1s-1 Mcelroy, 1990 81 R8 + ]a5 → R]a 5.0×10b; M-1s-1 Yang et al 2014 82 R]a → R8 + ]a5 8.6×10b| s-1 Yang et al 2014 83 ]aS5 + RcSc → ]a5 + RcS+Sc 1.7×10{ M-1s-1 Connick 1947 84 ]aS5 + SR∙ → ]aS. + SR5 8.8×10� M-1s-1 Matthew & Anastasio, 2006 85 ]aS5 + Sc∙5 + RcS → ]a∙ + 2SR5 + Sc 2.0×10j M-1s-1 Matthew & Anastasio, 2006 86 ]ac + ]a5 → ]a\∙5 2.0×10_ M-1s-1 Ershov, 2004 87 ]ac + Sc∙5 → Sc + ]ac∙5 1.0×10� M-1s-1 Matthew & Anastasio, 2006 88 ]ac + RSc∙ → R8 + Sc + ]ac∙5 1.0×10� M-1s-1 Bjergbackke et al., 1981 89 ]ac+RcS → RS]a + ]a5 + R8 2.2×10;s-1 Wang & Margerum, 1994 90 ]ac+RcSc → 2R]a + Sc 1.3×10_ M-1s-1 Matthew & Anastasio, 2006 91 ]acSR5 → RS]a + ]a5 5.5×10� s-1 Wang & Margerum, 1994

24

92 ]a\∙5 → ]ac + ]a5 1.1×10{ s-1 Ershov, 2004 93 ]a\5+RSc∙ → ]ac∙5 + R]a + Sc 1.0×10� M-1s-1 Bjergbackke et al., 1981 94 ]a\5+Sc∙5 → ]ac∙5 + ]a5 + Sc 3.8×10� M-1s-1 Matthew & Anastasio, 2006 95 Rc]S\ → R]S\5+R8 2.5×10_ s-1 Yang et al 2014 96 Rc]S\ + SR∙ → ]S\.5+RcS + R8 1.0×10| M-1s-1 Grebel et al., 2010 97 R]S\5 + R8 → Rc]S\ 5.0×10b; M-1s-1 Yang et al 2014 98 R]S\5 → ]S\c5+R8 2.5×10; s-1 Matthew & Anastasio, 2006 99 R]S\5 + SR∙ → ]S\.5+RcS 8.6×10| M-1s-1 Buxton et al., 1988

100 R]S\5 + ]a∙ → ]S\.5 + R]a 2.2×10j M-1s-1 Mertens & von Sonntag, 1995 101 R]S\5 + ]ac∙5 → 2]a5 + R8 + ]S\.5 8.0×10y M-1s-1 Matthew & Anastasio, 2006 102 R]S\5 + `S_∙5 → ]S\.5 + `S_c5 + R8 9.1×10| M-1s-1 Dogliotti& Hayon, 1967 103 ]S\c5 + R8 → R]S\5 5.0×10b; M-1s-1 Matthew & Anastasio, 2006 104 ]S\c5 + SR∙ → ]S\.5+SR5 3.9×10j M-1s-1 Buxton et al., 1988 105 ]S\c5 + ]a∙ → ]S\.5 + ]a5 5.0×10j M-1s-1 Mertens & von Sonntag, 1995 106 ]S\c5 + ]ac∙5 → ]S\.5 + 2]a5 1.6×10j M-1s-1 Matthew & Anastasio, 2006 107 ]S\c5 + ]aS∙ → ]S\.5 + ]aS5 6.0×10c M-1s-1 Huie et al 1991 108 ]S\c5 + `S_∙5 → ]S\.5+`S_c5 2.5×10| M-1s-1 Padmaja et al 1993 109 ]S\.5+RcSc → R]S\5 + RSc∙ 4.3×10{ M-1s-1 Draganic et al., 1991 110 ]S\.5+RSc5 → ]S\c5 + RSc∙ 3.0×10y M-1s-1 Draganic et al., 1991 111 ]S\.5 + RSc5 → R]S\5 + Sc∙5 3.0×10y M-1s-1 Buxton et al., 1990 112 ]S\.5 + SR∙ → pqrstuV 3.0×10� M-1s-1 Crittenden et al., 1999 113 ]S\.5 + ]S\.5 → pqrstuV 3.0×10y M-1s-1 Crittenden et al., 1999 114 ]S\.5 + Sc∙5 → ]S\c5 + Sc 6.0×10j M-1s-1 Crittenden et al., 1999 115 ]S\.5 + 2Äq5 → ]S\c5 +Äqc5 3.4×10_ M-1s-1 Huie et al 1991 116 ]S\.5 + ]aS5 → ]S\c5 + ]aS∙ 5.1×10{ M-1s-1 Alfassi et al 1988 117 Äq5 + SR∙ → ÄqSR.5 1.1×10b; M-1s-1 Matthew & Anastasio, 2006 118 Äq5 + `S_.5 → Äq∙+`S_c5 3.5×10� M-1s-1 Redpath & Willson, 1975 119 Äq5 + R8 → +RÄq 5.0×10b; M-1s-1 Yang et al 2014 120 Äq5 + RS]a → Äq]a + SR5 1.3×105b M-1s-1 Sander et al., 1977 121 Äq5 +]ac → Äq]ac5 6.0×10� M-1s-1 Ershov, 2004 122 Äq5 + ]aSR∙5 → Äq]a.5 + SR5 1.0×10� M-1s-1 Matthew & Anastasio, 2006 123 Äq5 + ]a∙ → Äq]a.5 1.2×10b; M-1s-1 Matthew & Anastasio, 2006 124 Äq5+]ac

.5 → Äq]a.5+]a5 4.0×10� M-1s-1 Ershov, 2004 125 Äq5 + ]S\.5 → Äq∙ + ]S\c5 1.0×10{ M-1s-1 Mertens & von Sonntag, 1995 126 Äq5 + S.5 → pqrstuV 2.2×10j M-1s-1 Rabani & Zehavi, 1971 127 Äq]ac

5 → ]ac + Äq5 9.0×10\ s-1 Ershov, 2004 128 Äq]ac

5 + Äq5 → Äqc]a5 + ]a5 3.0×10j M-1s-1 Ershov, 2004 129 HBr→ R8 + Äq5 5.0×10b� s-1 Yang et al 2014 130 Äqc + Äq5 → Äq\5 9.6×10j M-1s-1 Matthew & Anastasio, 2006 131 Äqc + RSc∙ → Äqc. +Sc+R8 1.1×10j M-1s-1 Matthew & Anastasio, 2006 132 Äqc + Sc∙5 → Äqc.5+Sc 5.6×10� M-1s-1 Matthew & Anastasio, 2006 133 Äqc + RcS → RSÄq + R8 + Äq5 9.7×10bs-1 Matthew & Anastasio, 2006 134 Äqc + RcSc → RÄq + Sc 1.3×10\ M-1s-1 Wagner & Strehlow, 1987 135 Äqc + ]a5 → Äqc]a5 5.0×10_ M-1s-1 Matthew & Anastasio, 2006 136 Äqc]a5 → +Äqc + ]a5 3.8×10_ s-1 Matthew & Anastasio, 2006 137 Äqc]a5 + ]a5 → Äq]ac

5+Äq5 1.0×10{ M-1s-1 Matthew& Anastasio, 2006 138 Äq\5 → Äqc 5.5×10y s-1 Matthew & Anastasio, 2006 140 Äq\5 + RSc∙ → Äqc.5 + RÄq + Sc 1.0×10y M-1s-1 Matthew & Anastasio, 2006 141 Äq\5 + Sc∙5 → Äqc.5 + Äq5 + Sc 3.8×10� M-1s-1 Matthew & Anastasio, 2006

25

142 SÄq5 + R8 → RSÄq 5.0×10b; M-1s-1 Yang et al 2014 143 SÄq5 + RcSc → Äq5 + RcS + Sc 1.2×10| M-1s-1 von Gunten & Oliveras, 1997 144 SÄq5 + SR∙ → ÄqS∙ + SR5 4. 5×10� M-1s-1 Matthew & Anastasio, 2006 145 SÄq5 + Sc∙5 + RcS → Äq. +2SR5 + Sc 2.0×10j M-1s-1 Matthew & Anastasio, 2006 146 SÄq5 + ]S\∙5 → ]S\c5+ÄqS∙ 4.3×10y M-1s-1 Buxton & Dainton 1968 147 SÄq5 + S.5 + R8 → SR5 + ÄqS∙ 2.9×10� M-1s-1 Czapski & Treinin, 1969 148 RSÄq → R8 +SÄq5 7.9×10bs-1 Yang et al 2014 149 RSÄq + Äq5 + R8 → Äqc + RcS 5.0×10� M-1s-1 Eigen & Kustin, 1962 150 RSÄq + RSc5 → Äq5+RcS + Sc 7.6×10j M-1s-1 von Gunten & Oliveras, 1997 151 RSÄq + RcSc → RÄq + RcS + Sc 1.5×10_ M-1s-1 von Gunten & Oliveras, 1997 152 RSÄq + SR.5 → ÄqS∙ + RcS 2.0×10� M-1s-1 Matthew & Anastasio, 2006 153 RSÄq + Sc∙5 → ÄqSR∙5 + Sc 3.5×10� M-1s-1 von Gunten & Oliveras, 1997 154 RSÄq + RSc. → ÄqSR∙5 + R8 + Sc 3.5×10� M-1s-1 Matthew & Anastasio, 2006 155 RSÄq + ]a5 → Äq]a + SR5 5.6×10c M-1s-1 Sander et al., 1977 156 Äq. + RcS → ÄqSR∙5+R8 1.4×10; s-1 Klaning & Wolff, 1985 157 Äq. + SR5 → ÄqSR∙5 1.1×10b; M-1s-1 Zehavi & Rabani, 1972 158 Äq. + Äq5 → Äqc.5 1.2×10b; M-1s-1 Matthew & Anastasio, 2006 159 Äq. + Äq. → Äqc 1.0×10� M-1s-1 Matthew & Anastasio, 2006 160 Äq. + SÄq5 → Äq5 + ÄqS. 4.1×10� M-1s-1 Klaning & Wolff 1985 161 Äq. + RcSc → RSc. + Äq5 + R8 4.0×10� M-1s-1 Matthew & Anastasio, 2006 162 Äq. + RSc. → R8 + Sc + Äq5 1.6×10j M-1s-1 Matthew & Anastasio, 2006 163 Äq. + ]S\c5 → Äq5 + ]S\∙5 2.0×10| M-1s-1 Matthew & Anastasio, 2006 164 Äq. + R]S\5 → Äq5 + ]S\∙5 1.0×10| M-1s-1 Matthew & Anastasio, 2006 165 Äq. + ]a5 → Äq]a.5 1.0×10j M-1s-1 Matthew & Anastasio, 2006 166 Äqc.5 + RcSc → RSc. +2Äq5 + R8 5.0×10c M-1s-1 Matthew & Anastasio, 2006 167 Äqc.5 → Äq. + Äq5 1.9×10_s-1 Matthew & Anastasio, 2006 168 Äqc.5 + Äqc.5 → Äqc + 2Äq5 1.9×10� M-1s-1 Matthew & Anastasio, 2006 169 Äqc.5 + Äq. → Äqc + Äq5 2.0×10� M-1s-1 Matthew & Anastasio, 2006 170 Äqc.5 + RSc. → Sc + 2Äq5 + R8 1.0×10j M-1s-1 Wagner & Strehlow, 1987 171 Äqc.5 + RSc. → RSc. 4.4×10� M-1s-1 Matthew & Anastasio, 2006 172 Äqc.5 + Sc∙5 → Sc + 2Äq5 1.7×10j M-1s-1 Wagner & Strehlow, 1987 173 Äqc.5 + SÄq5 → ÄqS∙ + 2Äq5 6.2×10y M-1s-1 Matthew & Anastasio, 2006 174 Äqc.5 + SR∙ → RSÄq + Äq5 1.0×10� M-1s-1 Wagner & Strehlow, 1987 175 Äqc.5 + SR5 → ÄqSR∙5 + Äq5 2.7×10| M-1s-1 Manou et al., 1977 176 Äqc.5 + ]S\c5 →2Äq5+]S\∙5 1.1×10{ M-1s-1 Matthew & Anastasio, 2006 177 Äqc.5 + R]S\5 →2Äq5 + ]S\∙5 + R8 8.0×10_ M-1s-1 Matthew & Anastasio, 2006 178 Äqc.5 + ]a5 → Äq]a.5 + Äq5 4.3×10| M-1s-1 Ershov, 2004 179 Äqc.5 + ]ac

.5 → Äqc + 2]a5 4.0×10� M-1s-1 Matthew & Anastasio, 2006 180 ÄqSR∙5 → SR∙ + Äq5 3.3×10ys-1 Zehavi and Rabani, 1972 181 ÄqSR∙5 → Äq. + SR5 4.2×10|s-1 Zehavi and Rabani, 1972 182 ÄqSR∙5 + R8 → Äq. + RcS 4.4×10b; M-1s-1 Zehavi and Rabani, 1972 183 ÄqSR∙5 + Äq5 → Äqc.5 + SR5 1.9×10j M-1s-1 Zehavi and Rabani, 1972 184 ÄqSR∙5 + ]a5 → Äq]a.5 + SR5 1.9×10j M-1s-1 Matthew & Anastasio, 2006 185 ÄqcSR5 + R8 → Äqc + RcS 2.0×10b; M-1s-1 Eigen and Kustin, 1962 186 ÄqcSR5 → RSÄq + Äq5 5.0×10�s-1 Eigen and Kustin, 1962 187 Äq]a + RcS → RSÄq + ]a5 + R8 1.0×10{s-1 Matthew & Anastasio, 2006 188 Äq]a + RcSc → RÄq + R]a + Sc 1.3×10_ M-1s-1 Matthew & Anastasio, 2006 189 Äq]a + Sc.5 → Äq]a.5 + Sc 4.0×10� M-1s-1 Matthew & Anastasio, 2006 190 Äq]a + RSc. → Äq]a.5 + Sc + R8 5.0×10j M-1s-1 Matthew & Anastasio, 2006

26

191 Äq]a + ]a5 → Äq]ac5 1.0×10| M-1s-1 Matthew & Anastasio, 2006

192 Äq]a + Äq5 → Äqc]a5 3.0×10j M-1s-1 Matthew & Anastasio, 2006 193 Äq]a.5 + SR. → Äq]a + SR5 1.0×10� M-1s-1 Matthew & Anastasio, 2006 194 Äq]a.5 + RSc. → Äq5 + ]a5 + Sc + R8 1.0×10� M-1s-1 Matthew & Anastasio, 2006 195 Äq]a.5 + Sc.5 → Äq5 + ]a5 + Sc 6.0×10j M-1s-1 Matthew & Anastasio, 2006 196 Äq]a.5 + RcSc → Äq5 + R]a + RSc 5.0×10\ M-1s-1 Matthew & Anastasio, 2006 197 Äq]a.5 + SR5 → Äq5 + ]aSR5 3.0×10| M-1s-1 Matthew & Anastasio, 2006 198 Äq]a.5 + SR5 → ÄqSR.5 + ]a5 2.0×10y M-1s-1 Matthew & Anastasio, 2006 199 Äq]a.5 + R]S\5 → Äq5+R]a + ]S\.5 3.0×10| M-1s-1 Matthew & Anastasio, 2006 200 Äq]a.5 + ]S\c5 → Äq5 + ]a5 + ]S\.5 6.0×10| M-1s-1 Matthew & Anastasio, 2006 201 Äq]a.5 + Äq]a.5 → Äq5 + ]a5 + Äq]a 4.7×10� M-1s-1 Matthew & Anastasio, 2006 202 Äq]a.5 + ]ac

.5 →2]a5 + Äq]a 2.0×10� M-1s-1 Matthew & Anastasio, 2006 203 Äq]a.5 + Äqc.5 → Äqc + ]a5 + Äq5 4.0×10� M-1s-1 Matthew & Anastasio, 2006 204 Äq]a.5 → ]a. + Äq5 2.0×10\s-1 Donati 2002 205 Äq]a.5 → ]a5 + Äq. 6.1×10_s-1 Donati 2002 206 Äq]a.5 + Äq5 → Äqc.5 + ]a5 8.0×10� M-1s-1 Ershov, 2004 207 Äq]a.5+]a5 → ]ac

.5 + Äq5 1.1×10c M-1s-1 Ershov, 2004 208 Äqc]a5 → Äq]a + Äq5 1.7×10_s-1 Matthew & Anastasio, 2006 209 Äqc]a5 → Äq]a + ]a5 1.7×10{s-1 Ershov, 2004 210 nSo + SR. → pqrstuV 7.2×104 (mg/L)-1s-1 Jasper and Sedlak, 2013 211 nSo + `S_.5 → pqrstuV 2.5×104 (mg/L)-1s-1 Lutze et al 2015 212 nSo + ]a. → pqrstuV 1.3×104 (mg/L)-1s-1 Fang et al 2014 213 nSo + ]ac

.5 → pqrstuV 1.0×102 (mg/L)-1s-1 Assumed, refer to text S3 214 nSo +]S\.5 → pqrstuV 3.7×102 (mg/L)-1s-1 Jasper and Sedlak 2013 215 nSo + Äq. → pqrstuV 1.0×104 (mg/L)-1s-1 * 216 nSo + Äqc.5 → pqrstuV 1.0×102 (mg/L)-1s-1 * 217 nSo + Äq]a.5 → pqrstuV 1.0×102 (mg/L)-1s-1 * 218 RS]a + ÅÇÉaÉÇÑ → pqrstuV 9.0×103 M-1s-1 * 219 RS]a + 17β − ÑvVqrsÉra → pqrstuV 2.5×102 M-1s-1 * 220 RS]a + vta!ÜáÑVℎrâÜärÑa → pqrstuV 1.0×102 M-1s-1 * 221 RS]a + uÜqãÜáÑäÑpÉÇÑ → pqrstuV 1.0×102 M-1s-1 *

* Rate constants are estimated (detail in Text S3) 216

27

Table S2 Compound structure and their quantum yield, extinction coefficient and direct 217

photolysis rate 218

Compound Name

Structure

Direct Photolysis Rate

(s-1)

Reference

17b-estradiol

Negligible

Mendez et al., 2010

1,4-dioxane

Negligible

Stefan and

Bolton, 1998

Phenol

2.1 ´ 10-4*

Prahl, 2012

Aniline

Negligible

Tang et al., 2010

Carbamazepine

4.6´10-4*

Pereira et al.,

Sulfamethoxazole

1.1 ´ 10-4*

Zhang et al., 2015

Natural Organic Matter (NOM)

1.8 ´ 10-10*

Jasper et al., 2013 Doll & Frimmel,

2003 * Calculated based on Equations 1-3 in the main text. FNOM=3.7 ´ 10-5 mole/Einstein, 219

εNOM=5.0´10-2 L mg-1cm-1, Fphenol=4.15´10-2 mole/Einstein, elphenol=7.50´102 M-1cm-1, Fcarba= 220

6.0´10-4 mole/Einstein, elcarba=8.0´103 M-1cm-1 (2007), Fsmx= 7.2´10-2 mole/Einstein, 221

elsmx=1.6´104 M-1cm-1. 222

28

Table S3 Rate constants of reactions between selected organic contaminants and radicals 223 224

Contaminant HO• (M-1s-1) SO4•- (M-1 s-1) Cl• (M-1 s-1) Cl2

•- (M-1 s-1) ClOH•- (M-1 s-1)

17b-estradiol 1.4´1010 1.2´109 1.3-1.6´1010* 2.0-2.4´107 * 2.0-2.4´107 *

Rosenfeldt and Linden, 2004

Rickman et al., 2010

Phenol 6.6´109 8.8´109 2.5´1010 3.2´108 5.0-6.0´106 *

Lindsey and Tarr, 2000

Lindsey and Tarr, 2000 Alfassi et al, 1989 Alfassi et al, 1990

Aniline 8.6´109 9.0´109 4.0´1010 3.4-4.1´108 3.4-4.1´108

Qin et al., 1985 Ahmed et al., 2012 Alfassi et al., 1989

Sulfamethoxazole 4.9´109 1.3´1010 4.4~5.4´109* 4.0-4.8´108 * 4.0-4.8´108 *

Boreen et al., 2004/2005 Ahmed et al. 2012

1,4-dioxane 3.1´109 4.1´107 2.8-3.4´109* 1.0´105-6* 1.0´105-6*

Eibenberger, 1980 Huie et al., 1991

Carbamazepine 2.1´109 8.8´109 1.8-3.7´109* 2.1-2.5´106 * 2.1-2.5´106 *

Vogna et al., 2004 Huber et al., 2003 225

29

Table S3 (Continued from the previous page) 226

Contaminant CO3.- (M-1 s-1) Br. (M-1 s-1) Br2

.- (M-1 s-1) ClBr.- (M-1 s-1)

17β-estradiol 2.2´107 1.3-1.6´109* 2.0-2.4´107 * 2.0-2.4´107 *

Jasper and Sedlak, 2013

Phenol 4.9´106 5.9-7.3´108 * 6.0´106 5.0-6.0´106 *

Chen et al., 1975 Simic et al., 1974

Aniline 5.4´108 7.7-9.5´108 * 2.1´108 3.4-4.1´108

Chen et al., 1975 Qin et al., 1985

Sulfamethoxazole 4.4´108 4.4-5.4´108* 4.0-4.8´108 * 4.0-4.8´108 *


1,4-dioxane 1.0´102-6* 1.2´106 1.0´105-6* 1.0´105-6*

Chen et al., 1975 Scaiano et al., 1993

Carbamazepine 2.3´106 7.9-9.7´109* 2.1-2.5´106 * 2.1-2.5´106 *


* Rates constants are estimated base on the known reactivity of radicals with other similar compounds (details in Text S3) 227

30

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