uv/h2o2 oxidation: kinetics, mechanism, and degradation … · 2019. 10. 30. · uv/h2o2 oxidation:...

S1

Supporting Information

Influence of solution pH on degradation of atrazine during UV and

UV/H2O2 oxidation: Kinetics, mechanism, and degradation pathways

Yucan Liua*, Kai Zhub*, Miaomiao Sua, Huayu Zhuc, Jianbo Lua, Yuxia Wangd, Jinkun Donga,

Hao Qina, Ying Wanga and Yan Zhanga

aSchool of Civil Engineering, Yantai University, Yantai 264005, China.

bCollege of resources and environment, Linyi University, Linyi 276000, China.

cSchool of chemistry & chemical engineering, Linyi University, Linyi 276000, China.

dSchool of Environmental and Municipal Engineering, North China University of Water

Resources and Electric Power, Zhengzhou, 450046, China

Corresponding author:

Yucan Liu Ph.D.

School of Civil Engineering, Yantai University

30 Qingquan Road, Yantai, 264005, China

E-mail: [email protected]

Tel: +86 0535 6902606

Fax: +86 0535 6902606

Mobile: +86 15853588482

Kai Zhu Ph.D.

College of resources and environment, Linyi University

Shuangling Road, Linyi, 276000, China

E-mail: [email protected]

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2019

S2

Contents

Text S1 Parameters of UPLC and MS for identifying UV photo-oxidation products..................................4

Fig. S1 Emission spectrum of the low-pressure mercury UV lamp. ...........................................................5

Fig. S2 Schematic diagram of photochemical reactor. ..............................................................................6

Fig. S3 Distribution for protonated and deprotonated ATZ species as a function of solution pH. ............7

Fig. S4 The EIC of photo-degradation intermediates of ATZ in solution during sole-UV treatment..........8

Fig. S5 Molecular structure and MS/MS spectrum of P1 (ESI+, CE=22 eV)................................................9

Fig. S6 Molecular structure and MS/MS spectrum of P2 (ESI+, CE=22 eV)..............................................10

Fig. S7 Molecular structure and MS/MS spectrum of P3 (ESI+, CE=0 eV)................................................11

Fig. S8 Molecular structure and MS/MS spectrum of P4 (ESI+ and ESI-, CE=23 eV)................................12

Fig. S9 Molecular structure and MS/MS spectrum of P5 (ESI+ and ESI-, CE=16 eV)................................13

Fig. S10 Molecular structure and MS/MS spectrum of P6 (ESI+ and ESI-, CE=24 eV)..............................14

Fig. S11 Molecular structure and MS/MS spectrum of P7 (ESI+, CE=26 eV)............................................15



Fig. S14 Molecular structure and MS/MS spectrum of P10 (ESI+, CE=12 eV)..........................................18

Fig. S15 UV-vis absorbance spectra of ATZ and its products in aqueous solutions at different pH values

during sole-UV process. ...........................................................................................................................19

Fig. S16 UV-vis absorbance spectra of ATZ and its products in aqueous solutions at pH of 7.0 during

UV/H2O2 process......................................................................................................................................20

Fig. S17 Degradation of H2O2 in UV/H2O2 process and the dark controls at pH of 7.0............................21

Fig. S18 Effect of H2O2 does and irradiation time on degradation of ATZ (5 mg L-1) in aqueous solution

at pH of 4.0 during UV irradiation treatment. .........................................................................................22


at pH of 10.0 during UV irradiation treatment. .......................................................................................23

S3


UV/H2O2 process......................................................................................................................................24


UV/H2O2 process......................................................................................................................................25

Fig. S22 Degradation of H2O2 in UV/H2O2 process and the dark controls at pH of 4.0............................26

Fig. S23 Degradation of H2O2 in UV/H2O2 process and the dark controls at pH of 10.0..........................27

Fig. S24 The EIC of photo-degradation intermediates of ATZ in aqueous solution at 90 min of UV

irradiation in UV/H2O2 process under different H2O2 dose. ....................................................................28



Fig. S27 Molecular structure and MS/MS spectrum of P14 (ESI+ and ESI-, CE=20 eV)............................31








Table S1 Pseudo-first-order reaction rate constants (kobs) of ATZ at different pH values in sole-UV

process.....................................................................................................................................................39

Table S2 Retention time (RT) and MS spectral information in full scan modes of ATZ and its intermediates.

.................................................................................................................................................................40

Table S3 Pseudo-first-order reaction rate constants (kobs) of ATZ (initial pH of 7.0) at different H2O2

does in UV/H2O2 process. ........................................................................................................................41


.................................................................................................................................................................42

S4

Text S1 Parameters of UPLC and MS for identifying UV photo-oxidation products.

The binary mobile phase was composed of methanol (mobile phase A) and ultrapure water (mobile

phase B), and the flow rate was 0.2 mL min-1. The elution started with 10% A for 3 minutes, the

concentration of A was increased to 70% within 18 minutes, and then the concentration of A was

increased to 100% within 22 minutes and retained for 3 minutes, finally it was dropped back to 10%

and run for 3 minutes for equilibrium before the next injection. A total acquisition time of one run

analysis was 28 min. The column temperature was maintained at 35 ºC and the injection volume was

10 μL. The source temperature and desolvation temperature were 110 ºC and 350 ºC, the capillary

voltage was 3.3 kV, and the cone voltage was 35 V. Desolvation gas (nitrogen gas) and cone gas

(nitrogen gas) flows were set at 500 L h-1 and 30 L h-1, respectively. Full scan data were acquired from

m/z 50 to 300 at an acquisition rate of 0.2 sec scan-1 in both positive electrospray ionization (ESI+)

mode and negative electrospray ionization (ESI-) mode. In order to obtain further information for

analyzing the structure of intermediates, collision induced dissociation (CID) experiments in daughter

scan were also conducted. Argon was used as collision gas in daughter scan model and its flow rate

was at 0.12 mL min-1. The collision energy for each product was optimized in the range from 15 to 35

eV.

S5

Fig. S1 Emission spectrum of the low-pressure mercury UV lamp.

S6

Fig. S2 Schematic diagram of photochemical reactor. (1) low-pressure mercury UV lamp; (2) quartz glass well; (3) sampling point; (4) magnetic stirrer; (5) magnetic stirrer apparatus; (6) thermostatic water recirculation system; (7) silicone tube. All dimensions are in millimeter (mm).

S7

Fig. S3 Distribution for protonated and deprotonated ATZ species as a function of solution pH. CTotal= CDeprotonated form + CProtonated.

S8

Time6.00 8.00 10.00 12.00 14.00 16.00

%

0

7.39

Time6.00 8.00 10.00 12.00 14.00 16.00

%

07.41

Time6.00 8.00 10.00 12.00 14.00 16.00

%

0

7.45

Time6.00 8.00 10.00 12.00 14.00 16.00

%

07.41

Time6.00 8.00 10.00 12.00 14.00 16.00

%

09.95

(A) pH=4.0

(B) pH=5.5

(C) pH=7.0

(D) pH=8.5

(E) pH=10.0

P1P2 P3

P4

P5 P6

P7 P9P8

P1P2 P3

P4

P5P6

P7 P9P8

P1 P2 P3

P4

P5 P6P7

P9P8

P1P2 P3

P4

P5 P6P7

P8

P1P2 P3

P4

P5 P6P7

P8

P9

P9P11

P10 P11

P10 P11

P10 P11

P10 P11

P10 P11

Time7.00 8.00

%

0

100 7.38

7.32

Time7.00 8.00

%

0

100 7.42

6.68 8.28 8.79

Time7.00 8.00

%

0

100 7.43

7.158.52

8.06

Time7.00 8.00

%

0

100 7.41

7.148.05

Time4.50 5.00 5.50

%

0

100 5.02

4.19 5.55

Time4.50 5.00 5.50

%

0

100 5.02

4.355.42

Time4.50 5.00 5.50

%

0

100 5.02

Time4.50 5.00 5.50

%

0

100 5.04

5.61

Time4.50 5.00 5.50

%

0

100 5.01

5.55

5.315.64

Time7.00 8.00

%

0

100 7.50

7.35

Fig. S4 The EIC of photo-degradation intermediates of ATZ in solution during sole-UV treatment.

Raw ATZ solution: 5 mg L-1; irradiation time: 120 min. (A) pH 4.0; (B) pH 5.5; (C) pH 7.0; (D) pH 8.5; (E)

pH 10.0.

S9

P1 (4-Isopropylamino-6-amino-s-triazine)

N N

N NH2HNCH3

CH3CH

ESI+ mode

m/z60 80 100 120 140 160

%

0

100 70

68

112

85154NH N

N NH2H2N

NH N

N NH2HNCH3

CH3CH

NH

NH2HN

CHN

NC

HN

HN

NH

HN

CHN

Fig. S5 Molecular structure and MS/MS spectrum of P1 (ESI+, CE=22 eV).

S10

P2 (2-Methoxy-4-methylamino-6-isopropylamino-s-triazine)

N N

N NHHN

OH

CH3

CH3CH CH3

ESI+ mode

m/z60 80 100 120 140 160 180 200

%

0

100 114

699771

184156142

NH N

N NHHN

OH

CH3

CH3CH CH3

NH N

N NHHN

OH

H3C CH3

N HN

N NHH2N

OH

CH3

HN

NH3C

H2C

NH N

NH2N

NH NH

N NH2H2NNNH

CH CH2


S11

P3 (2-Hydroxy-4-isopropylamino-6-vinylamino-s-triazine)

N N

N NHHN

OH

CH3

CH3CH CH CH2

ESI+ mode

m/z60 80 100 120 140 160 180 200 220

%

0

100 196

6557

718997 183145104 121 129 181153 216205

NH N

N NH2HN

OH

CH3

CH3CH CH CH2


S12

P4 (2-Hydroxy-4-ethylamino-6-isopropylamines-s-triazine)

N N

N NH CH2 CH3HNCH3

CH3CH

OH

ESI+ mode

m/z60 80 100 120 140 160 180 200

%

0

100 15686

6971

11497

128 198

NH N

N NH CH2 CH3HNCH3

CH3CH

OH

NH N

N NH CH2 CH3H2N

OH

NH N

N NH2H2N

OH

NH NH

N NH2H2N

N HN

N NH2

NH

NH3C

H2C

NH2

NNH

CH CH2

ESI- mode

m/z60 80 100 120 140 160 180 200

%

0

100 83

69 84 125111 154 196168

N

NH3C

H2C

N NH

N NH2N N

N NH CH3

O

N N

N NH2

O

N N

N NH CH2 CH3H2N

O

N N

N NH CH2 CH3HNH3C

O

N N

N NH CH2 CH3HNCH3

CH3CH

O

Fig. S8 Molecular structure and MS/MS spectrum of P4 (ESI+ and ESI-, CE=23 eV).

S13

P5 (2-Hydroxy-4-acetamido-6-ethylamino-s-triazine)

N N

NHN NHCH2CH3

OH

C CH3

O

ESI+ mode

m/z60 80 100 120 140 160 180 200

%

0

100 113

71

68

8596 103

114198

156139

N N

NHN NH2CH2CH3

OH

C CH3

O

NH N

NHN NH2CH2CH3

OHNH

NCH2

NC

CH2

H

NH

N HH3C

H2C

N NH

N NH2

H

NH N

N NH2

OH

NH N

NHNCH

OH

H2C

ESI- mode

m/z60 80 100 120 140 160 180 200

%

0

100 111

69 83 196137

N N

NHN NHCH2CH3

O

C CH3

ON NH

N NH2NH3C

H2CN

N N

NHNCH

O

H2C

N N

N NH2

O


S14

P6 (2-Hydroxy-4-(2-hydroxy-ethylamino)-6-vinylamino-s-triazine)

N N

N NH CH CH3HN

OH

OH

CHCH2

ESI+ mode

m/z60 80 100 120 140 160 180 200

%

0

100 85

716958

127

113 198156153

N N

N NH2 CH CH3HN

OH

OH

CHCH2

N N

N NH2 CH2 CH3H2N

OH

NH N

N NH CH3

OH

NH N

N NH2

OH

NH NH

N NH2

NH

NH3C

H2C

HN NH

HN

N N

N CH3H2N

OH

CHCH2

ESI- mode

m/z60 80 100 120 140 160 180 200

%

0

100 125

83 111 196151

N N

N NH CH CH3HN

O

OH

CHCH2

N N

N NH CH3

O

N N

N NH2

O

N NH

N NH2

N N

N CH3HN

O

CHCH2


S15

P7 (2-Hydroxy-4-acetamido-6-isopropylamino-s-triazine)

N N

N NHHN

OH

C CH3

OCH3

CH3CH

ESI+ mode

m/z60 80 100 120 140 160 180 200 220

%

0

100 86

8568

128

170212

N N

N NH2H2N

OH

C CH3

O

NH N

N NH2H2N

OH

NC

HN

HN

N N

N NH2HN

OH

C CH3

OCH3

CH3CH

NH

NH3C

H2C

NH2


S16

P8 (2-Methoxy-4-isopropylamino-6-ethylamino-s-triazine)

N N

N NH CH2 CH3HN

O CH3

CH3

CH3CH

ESI+ mode

m/z60 80 100 120 140 160 180 200 220

%

0

100 170

10097

7571

5786

83

142114 128

212182

N N

N NH2 CH2 CH3HN

O CH3

CH3

CH3CH

N N

N NH2 CH2 CH3HN

H

CH3

CH3CH

N N

N NH2 CH2 CH3H2N

O CH3

NH N

N NH2H2N

O CH3

NH N

N NH2H2N

OH

N NH

N NH CH3H2NN HN

N NH2


S17

P9 (2-Chloro-4-ethylamino-6-isopropylamino-s-triazine)

N N

NHNCH3

CH3NH CH2 CH3CH

Cl

ESI+ mode

m/z60 80 100 120 140 160 180 200 220

%

0

100 174

96

79

716890

104 146132110 138 216

N N

NHNCH3

CH3NH2 CH2 CH3CH

Cl

N N

NH2N NH2 CH2 CH3

Cl

NH N

NH2N NH2

Cl

NC

HN

HN

NH

NH3C

H2C NH

NCH2

NC

CH2

H


S18

P10 (2-Hydroxy-4-vinylamino-s-triazine)

OH

N N

N NH CH CH2

ESI+ mode

m/z50 60 70 80 90 100 110 120 130 140 150

%

0

100 139

81

72

NH

HN NH2

H2C

OH

NH N

N NH CH CH2

NH

N

C

H


S19

Fig. S15 UV-vis absorbance spectra of ATZ and its products in aqueous solutions at different pH values

during sole-UV process.

S20


UV/H2O2 process.

S21

Fig. S17 Degradation of H2O2 in UV/H2O2 process and the dark controls at pH of 7.0.

S22


at pH of 4.0 during UV irradiation treatment.

S23


at pH of 10.0 during UV irradiation treatment.

S24


UV/H2O2 process.

S25


UV/H2O2 process.

S26


S27


S28

Time4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

%

0

100

15.45

P10P12 P11 P1

P2

P14 P15P3

P4

P5P6

P7

P8 P9P13

P16

Time4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

%

0

100 15.46

P10P1 P2 P3

P4

P5P6

P7 P8

P9

Time7.00 8.00

%0

100 7.42

6.68 8.28 8.79

P11

(A) pH=7.0, H2O2=0 mg/L

(B) pH=7.0, 5 mg/L

Time4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

%

0

100 15.44

15.40(C) pH=7.0, 15 mg/L

P10

P11

P1 P2

P4

P5P6

P7

P8

P9

Time4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

%

0

10015.41(D) pH=7.0, 30 mg/L

P10 P2

P4

P5P6

P7

P8

P9

Time4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

%

0

100 15.4415.40(E) pH=7.0, 50 mg/L

P10 P1 P2

P4

P5 P6

P7

P8

P9

Time15.00 16.00 17.00 18.00

%

0

100 16.6616.4416.31

16.1715.96

15.6315.1614.79

16.7816.90

18.0717.50

Time4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

%

0

100 15.41(F) pH=4.0, 30 mg/L

P10

P9

P8

P7P6

P5

P4

P3P2

Time4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

%

0

10015.41(G) pH=10.0, 30 mg/L

P10

P11 P1

P9

P8P7

P6P5

P4

P3

Time9.60 9.80 10.00 10.20

%

0

100

P16P13P12P14

P15P3

P11

P1

P12 P13 P14

P15P3 P16

P12P11 P13 P14

P15P3 P16

P1

P12P11

P14

P15P16

P12

P21

P13

P2P20

P19P17 P18

Fig. S24 The EIC of photo-degradation intermediates of ATZ in aqueous solution at 90 min of UV

irradiation in UV/H2O2 process under different H2O2 dose.

(A) pH=7.0, 0 mg L-1 H2O2; (B) pH=7.0, 5 mg L-1 H2O2; (C) pH=7.0, 15 mg L-1 H2O2; (D) pH=7.0, 30 mg L-1

H2O2; (E) pH=7.0, 50 mg L-1 H2O2; (F) pH=4.0, 30 mg L-1 H2O2; (G) pH=10.0, 30 mg L-1 H2O2.

S29

P12 (2-Hydroxy-4-acetamido-6-isopropenylenylamino-s-triazine)

N N

N NH

OH

HN C

O

CH3 C

CH2CH3

ESI+ mode

m/z100 120 140 160 180 200 220

%

0

100 167

98

97

101

152123115

166 210168 209

N N

N NH2

OH

HN C

O

CH3 C

CH2CH3

NH N

NHNHC

CH2

NH N

N NH2HNCH3 C

CH2

168 NH N

N NH2

OH

HNCH3 C

CH2


S30

P13 (4-acetamido-s-triazine)

N N

N NH C CH3

O

ESI+ mode

m/z50 60 70 80 90 100 110 120 130 140 150

%

0

100 139

60

5797

897162 8774 84 90119104 108 132121

140148

N N

N NH2 C CH3

ONH N

N NH2


S31

P14 (2-Hydroxy-4-acetamido-6-(2-hydroxyisopropylamino)-s-triazine)

N N

N NH CH CH2HN

OH

C

OH

CH3

CH3

ESI+ mode

m/z60 80 100 120 140 160 180 200 220

%

0

100 142

756858 10085

170

212184

NH N

N NH CH CH2HN

OH

C

OH

CH3

CH3

NH N

N NH CH CH2HNH2C

OH

OH

NH N

N NH2HNH2C

OH

NH N

N NH2HNC

OH

CH3

CH3

NH NH

N

OH H

NC

HN

HN

N NH

N NH2

H

ESI- mode

m/z60 80 100 120 140 160 180 200 220

%

0

100 81

66

58

72

115

9883

111

181

166136

210182

N N

N NH CH CH2HNH3C

O

N N

N CH CH2HN

O

C

OH

H

CH3

N N

N NH CH CH2HN

O

C

OH

CH3

CH3N N

NH2N NH CH CH2

N N

N NH2

O

N NH

N

O H

N N

N NH2

ON

CHN

N


S32

P15 (2-Hydroxy-4-ethylimine-6-(2-hydroxyisopropylamino)-s-triazine)

N N

N N CH CH3HNC

OH

CH3CH3

OH

ESI+ mode

m/z60 80 100 120 140 160 180 200 220

%

0

100 170

10386

212

NH

NH3C

H2C

NH2

NH

NH NH2H2N

CH3N N

N NH CH2HNC

OH

H

H

OH

N N

N NH CH CH3HNC

OH

CH3CH3

OH

ESI- mode

m/z60 80 100 120 140 160 180 200 220

%

0

100 66167

9897

73 81

101

152123115

166 210168 209

NC

HN

N

N N

NHN

O

CH

N

NH NH2H2N

CH3

N N

N N CH CH3HNC

OH

CH3CH3

O

N N

NHNCCH3CH3

H

O

CH3N N

N N CH2

O

HNCH3


S33

P16 (2-Chloro-4-vinylamino-6-acetamido-s-triazine)

N N

NHNC

O

CH3

Cl

NH CH CH2

ESI+ mode

m/z50 75 100 125 150 175 200 225 250

%

0

100 21460

5817374

88 14711197 131 151 194 226 235 257261

N N

NH2NC

O

CH3

Cl

NH CH CH2

N N

NH2NC

O

CH3

Cl


S34

P17 (2-Hydroxy-4-(2-hydroxy-ethylamino)-6-isopropylamino-s-striazine)

N N

N

OH

HN NH CH

OH

CH3CH3

CH3CH

ESI+ mode

m/z50 75 100 125 150 175 200 225 250

%

0

100 192

129

907362 81 127105

170

143171

214

193196 236

NH N

N

OH

HN NH CH

OH

CH3CH3

CH3CH

NH N

N

O Na

HN NH CH

OH

CH3CH3

CH3CH

196 NH NN

OH

HN NH CH CH2CH3

CH3CH

NH N

N

OH

NH CH2

OH

H2N NH

HN

OH

NH CH CH2

NH N

N NH CH2 CH3

OH

HNCH3


S35

P18 (2-Hydroxy-4-ethylamino-6-(2-hydroxyisopropylamino)-s-triazine)

N N

N

OH

NH CH2 CH3NHCCH3CH3

OH

ESI+ mode

m/z50 75 100 125 150 175 200 225 250

%

0

100 214

7460 76 89 118 171130 155179 196 256250217

N N

N

Cl

HN NH2 CH CH2CH3

CH3CH


S36

P19 (2-Hydroxy-4-ethylamino-6-isopropenylenylamino-s-triazine)

N N

N NHHN

OH

C

CH2CH3 CH2 CH3

ESI+ mode

m/z50 75 100 125 150 175 200 225 250

%

0

100 196

60 74 1547684 127 179218200 254

NH N

N NH2HN

OH

C

CH2H

NH N

N NH CH3

OH

NH N

N NHHN

O Na

C

CH2CH3 CH2 CH3

NH N

N NHHN

OH

C

CH2CH3 CH2 CH3


S37

P20 (2-Hydroxy-4-(2-hydroxy-ethylamino)-6-amino-s-triazine)

N N

N NH CH

OH

CH3

OH

H2N

ESI+ mode

m/z50 75 100 125 150 175 200 225 250

%

0

100 172

7460 13011410188 160140

184

194

203 223 244

NH N

N NH CH

OH

CH3

OH

H2N

NH N

N NH CH

OH

CH3

O Na

H2N

ESI- mode

m/z50 75 100 125 150 175 200 225 250

%

0

100 170

6159 75 1179985 164147

183241202 207

N N

N NH CH

OH

CH3

O

H2N


S38

P21 (2-Chloro-4-vinylamino-6-amino-s-triazine)

N N

N NH CH CH2

Cl

H2N

ESI+ mode

m/z50 75 100 125 150 175 200 225 250

%

0

100 172

130

60 7411989 92 133151170

194

183 212 223

N N

N NH2 CH CH2

Cl

H2N

M+Na

ESI+ mode

m/z50 75 100 125 150 175 200 225 250

%

0

100 170

6158 7571 11586 100 122132 154

171260178 190

N N

N NH C CH2

Cl

H2N


S39

Table S1 Pseudo-first-order reaction rate constants (kobs) of ATZ at different pH values in sole-UV

process.

Initial solution

pH values

Final solution

pH valuesLinear correlation

coefficient (r2)

Reaction rate

constants kobs（min-

1）

Half-life time

t1/2 (min)

4.0 4.03 0.989 0.0076 91.2

5.5 5.51 0.986 0.0113 61.3

7.0 6.98 0.987 0.0150 46.2

8.5 8.46 0.989 0.0140 49.5

10.0 9.95 0.985 0.0134 51.7

Note: initial ATZ concentration: 5 mg L-1.

S40


Name RT/min MS spectral (ESI+) MS spectral (ESI-)

P1 7.42

m/z60 80 100 120 140 160 180 200 220

%

0

100 154

7165 8974 121102 198187183 221

P2 9.89

m/z60 80 100 120 140 160 180 200 220

%

0

100 184

6557 1199771 8976 115 133 153 171 206187

P3 11.90

m/z60 80 100 120 140 160 180 200 220

%

0

100 196

6557

718997 183145104 121 129 181153 216205

P4 12.60

m/z50 100 150 200 250 300 350 400 450 500

%

0

100 198

395220 417

m/z50 100 150 200 250 300 350 400 450 500

%

0

100 196

393

P5 14.06

m/z50 100 150 200 250 300 350 400 450 500

%

0

100 220

198

11371

417

395252 318 433m/z

50 100 150 200 250 300 350 400 450 500

%

0

100 196

111

75 89 137 415250218 393

P6 14.46

m/z50 100 150 200 250 300 350 400 450 500

%

0

100 220198

12765

417

395300242 252 318m/z

50 100 150 200 250 300 350 400 450 500

%

0

100 196

125

61 415250218

P7 14.88

m/z50 75 100 125 150 175 200 225 250

%

0

100 212

19865

234220

m/z50 75 100 125 150 175 200 225 250

%

0

100 210

1257560 83 99 112

196136 178166

223236 259

P8 15.20

m/z50 75 100 125 150 175 200 225 250

%

0

100 212

198129976574 121 193 220

P9 15.44

m/z50 75 100 125 150 175 200 225 250

%

0

100 216

218

238m/z

50 75 100 125 150 175 200 225 250

%

0

100 214

7560 8984 196127111 143 168

216243 259

P10 5.02

m/z50 60 70 80 90 100 110 120 130 140 150

%

0

100 139

12996 151

P11 7.54

m/z50 100 150 200 250 300 350 400

%

0

100 198

71 128 154395220 417

m/z100 150 200 250 300 350 400

%

0

100 196

123 181151 284245199 381321 393

S41

Table S3 Pseudo-first-order reaction rate constants (kobs) of ATZ (initial pH of 7.0) at different H2O2

does in UV/H2O2 process.

Initial H2O2

concentration

Final solution

pH values

Linear correlation

coefficient (r2)

Reaction rate constants

kobs（min-1）

Half-life time

t1/2 (min)

0 6.98 0.983 0.0145 46.2

5 6.95 0.979 0.0165 42.0

15 6.88 0.988 0.0118 58.7

30 6.82 0.991 0.0108 64.2

50 6.68 0.995 0.0097 71.5

S42


Name RT/min MS spectral (ESI+) MS spectral (ESI-)

P12 6.70

m/z50 75 100 125 150 175 200 225 250

%

0

100 210

7157 1078974 121 135 160141 173 179 207 232 243 258

P13 8.58

m/z50 75 100 125 150 175 200 225 250

%

0

100 139

60

97897187 104 119 149 159171 205

P14 11.38

m/z50 75 100 125 150 175 200 225 250

%

0

100 212

60234

m/z50 75 100 125 150 175 200 225 250

%

0

100 210

62 89 181115212

P15 11.64

m/z50 75 100 125 150 175 200 225 250

%

0

100 212

17060 8974 105 131

234

m/z50 75 100 125 150 175 200 225 250

%0

100 210

62 1018985 167150138 174

211

213 248

P16 16.60

m/z50 75 100 125 150 175 200 225 250

%

0

100 21460

5817374

88 14711197 131 151 194 226 235 257261

P17 3.92

m/z50 75 100 125 150 175 200 225 250

%

0

100 192

129

62 78 83 12110790170

135 159 177

214

203215

236

196

P18 7.90

m/z50 75 100 125 150 175 200 225 250

%

0

100 214

7460 76 89 118 171130 155179 196 256250217

P19 9.20

m/z50 75 100 125 150 175 200 225 250

%

0

100 196

60 74 1547684 127 179218200 254

P20 9.77

m/z50 75 100 125 150 175 200 225 250

%

0

100 172

7460 13011410188 160140

184

194

203 223 244m/z

50 75 100 125 150 175 200 225 250

%

0

100 170

6159 75 1179985 164147

183241202 207

P21 9.95

m/z50 75 100 125 150 175 200 225 250

%

0

100 172

130

60 7411989 92 133151170

194

183 212 223m/z

50 75 100 125 150 175 200 225 250

%

0

100 170

6158 7571 11586 100 122132 154

171260178 190

uv/h2o2 oxidation: kinetics, mechanism, and degradation … · 2019. 10. 30. · uv/h2o2 oxidation:...

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