-
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. S12 Molecular structure and MS/MS spectrum of P8 (ESI+, CE=22 eV)............................................16
Fig. S13 Molecular structure and MS/MS spectrum of P9 (ESI+, CE=22 eV)............................................17
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
Fig. S19 Effect of H2O2 does and irradiation time on degradation of ATZ (5 mg L-1) in aqueous solution
at pH of 10.0 during UV irradiation treatment. .......................................................................................23
-
S3
Fig. S20 UV-vis absorbance spectra of ATZ and its products in aqueous solutions at pH of 4.0 during
UV/H2O2 process......................................................................................................................................24
Fig. S21 UV-vis absorbance spectra of ATZ and its products in aqueous solutions at pH of 10.0 during
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. S25 Molecular structure and MS/MS spectrum of P12 (ESI+, CE=20 eV)..........................................29
Fig. S26 Molecular structure and MS/MS spectrum of P13 (ESI+, CE=15 eV)..........................................30
Fig. S27 Molecular structure and MS/MS spectrum of P14 (ESI+ and ESI-, CE=20 eV)............................31
Fig. S28 Molecular structure and MS/MS spectrum of P15 (ESI+ and ESI-, CE=20 eV)............................32
Fig. S29 Molecular structure and MS/MS spectrum of P16 (ESI+, CE=15 eV)..........................................33
Fig. S30 Molecular structure and MS/MS spectrum of P17 (ESI+, CE=18 eV)..........................................34
Fig. S31 Molecular structure and MS/MS spectrum of P18 (ESI+, CE=17 eV)..........................................35
Fig. S32 Molecular structure and MS/MS spectrum of P16 (ESI+, CE=15 eV)..........................................36
Fig. S33 Molecular structure and MS/MS spectrum of P20 (ESI+ and ESI-, CE=20 eV)............................37
Fig. S34 Molecular structure and MS/MS spectrum of P21 (ESI+ and ESI-, CE=20 eV)............................38
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
Table S4 Retention time (RT) and MS spectral information in full scan modes of ATZ and its intermediates.
.................................................................................................................................................................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
Fig. S6 Molecular structure and MS/MS spectrum of P2 (ESI+, CE=22 eV).
-
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
Fig. S7 Molecular structure and MS/MS spectrum of P3 (ESI+, CE=0 eV).
-
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
Fig. S9 Molecular structure and MS/MS spectrum of P5 (ESI+ and ESI-, CE=16 eV).
-
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
Fig. S10 Molecular structure and MS/MS spectrum of P6 (ESI+ and ESI-, CE=24 eV).
-
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
Fig. S11 Molecular structure and MS/MS spectrum of P7 (ESI+, CE=26 eV).
-
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
Fig. S12 Molecular structure and MS/MS spectrum of P8 (ESI+, CE=22 eV).
-
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
Fig. S13 Molecular structure and MS/MS spectrum of P9 (ESI+, CE=22 eV).
-
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
Fig. S14 Molecular structure and MS/MS spectrum of P10 (ESI+, CE=12 eV).
-
S19
Fig. S15 UV-vis absorbance spectra of ATZ and its products in aqueous solutions at different pH values
during sole-UV process.
-
S20
Fig. S16 UV-vis absorbance spectra of ATZ and its products in aqueous solutions at pH of 7.0 during
UV/H2O2 process.
-
S21
Fig. S17 Degradation of H2O2 in UV/H2O2 process and the dark controls at pH of 7.0.
-
S22
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.
-
S23
Fig. S19 Effect of H2O2 does and irradiation time on degradation of ATZ (5 mg L-1) in aqueous solution
at pH of 10.0 during UV irradiation treatment.
-
S24
Fig. S20 UV-vis absorbance spectra of ATZ and its products in aqueous solutions at pH of 4.0 during
UV/H2O2 process.
-
S25
Fig. S21 UV-vis absorbance spectra of ATZ and its products in aqueous solutions at pH of 10.0 during
UV/H2O2 process.
-
S26
Fig. S22 Degradation of H2O2 in UV/H2O2 process and the dark controls at pH of 4.0.
-
S27
Fig. S23 Degradation of H2O2 in UV/H2O2 process and the dark controls at pH of 10.0.
-
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
Fig. S25 Molecular structure and MS/MS spectrum of P12 (ESI+, CE=20 eV).
-
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
Fig. S26 Molecular structure and MS/MS spectrum of P13 (ESI+, CE=15 eV).
-
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
Fig. S27 Molecular structure and MS/MS spectrum of P14 (ESI+ and ESI-, CE=20 eV).
-
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
Fig. S28 Molecular structure and MS/MS spectrum of P15 (ESI+ and ESI-, CE=20 eV).
-
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
Fig. S29 Molecular structure and MS/MS spectrum of P16 (ESI+, CE=15 eV).
-
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
Fig. S30 Molecular structure and MS/MS spectrum of P17 (ESI+, CE=18 eV).
-
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
Fig. S31 Molecular structure and MS/MS spectrum of P18 (ESI+, CE=17 eV).
-
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
Fig. S32 Molecular structure and MS/MS spectrum of P16 (ESI+, CE=15 eV).
-
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
Fig. S33 Molecular structure and MS/MS spectrum of P20 (ESI+ and ESI-, CE=20 eV).
-
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
Fig. S34 Molecular structure and MS/MS spectrum of P21 (ESI+ and ESI-, CE=20 eV).
-
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
Table S2 Retention time (RT) and MS spectral information in full scan modes of ATZ and its intermediates.
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
Table S4 Retention time (RT) and MS spectral information in full scan modes of ATZ and its intermediates.
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