Supporting Information for

Degradation of Benzophenone-3 by the Ozonation in Aqueous Solution: Kinetics, Intermediates and Toxicity

Yang Guo 1, Qiaoxin Lin 1, Bingbing Xu 2 **, Fei Qi 1 *

1. Beijing Key Lab for Source Control Technology of Water Pollution, College of Environmental Science and Engineering, Beijing Forestry University, Beijing, 100083, P.R. China.

2. State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing, 100012, P.R. China.

* Corresponding author, Prof. Fei Qi,

Tel.: 86 10 62336615; Fax: 86 10 62336596

Email address: ;

** Co-corresponding author, Ph.D Bingbing Xu

Tel.: 86 10 84915159; Fax: 86 10 84934181

Email address:

Text S1

The unsaturation degree of molecular structure (Ω1) is equal to sum over the numbers of double bonds, duplicate the triple bonds and rings. While the unsaturation of molecular formula (Ω2) can be calculated as:

Ω2 = (2C+2-H)/2 (1)

where C and H are the numbers of carbon atom and hydrogen atom, respectively. And oxygen has no contribution to the unsaturation of molecular formula.

Table S1 The values of second order kinetic constant at different pH

pH / 2.42 / 3.34 / 4.33 / 5.26 / 6.10 / 7.16
[O3]0 (mg/L) / 1.0 / 1.0 / 1.0 / 1.0 / 1.0 / 1.0
[BP-3]0 (mg/L) / 1.5 / 1.5 / 1.5 / 1.5 / 1.5 / 1.5
R2 / 0.993 / 0.993 / 0.970 / 0.998 / 0．970 / 0.999
kO3 (M-1s-1) / 72.00 / 105.83 / 125.60 / 200.99 / 259.12 / 820.82

Table S2 Water quality of the surface water

Hardness (mg/L) / Alkalinity (mg/L) / PIa (O2, mg/L) / pH / TOC(mg/L)
291 / 277.73 / 1.523 / 7.68 / 8.41

a Permanganate index (O2, mg/L)

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Table S3 Summary of identified intermediates in the molecular ozone oxidation

Compound / RT a, min / MW b / MS ions and detection mode c / MS2 spectrum ions / Structure formula
BP-3 / 10.8 / 228.08 / 229.04(+) / 105.06, 151.03 /
C1 / 9.6 / 244.07 / 245.03(+) / 105.02, 167.01 /
C2 / 8.4 / 260.07 / 259.08(-) / 105.02, 155.02, 183.13 /
C3 / 5.7 / 218.06 / 217.10(-) / 105.01, 141.03 /
C4 / 11.2 / 234.05 / 233.15(-) / ___ /
C5 / 11.8 / 234.05 / 233.04(-) / 105.02, 157.03 /
C6 / 7.2 / 276.06 / 277.01(+) / 121.08, 183.04 /
C7 / 9.1 / 250.05 / 251.02(+) / ___ /
C8 / 10.9 / 250.05 / 251.22(+) / 121.06, 157.04 /
C9 / 8.6 / 266.04 / 265.21(-) / 109.03, 137.01 /
C10 / 10.6 / 240.03 / 239.07(-) / ___ /
C11 / 9.4 / 224.03 / 225.14(+) / ___ /
C12 / 8.0 / 214.06 / 215.05(+) / 105.16, 137.05 /

a Retention time (min)

b Molecular Weight

c Mode: positive (+) or negative (-)

Table S4 The unsaturation degrees of the molecular structure (Ω1) and molecular formula (Ω2) of intermediates generated from the molecular ozone oxidation

Compound / C / H / O / / / / Unsaturation
（Ω1） / Unsaturation
（Ω2）
C1 / 14 / 12 / 4 / 0 / 2 / 1 / 9 / 9
C2 / 14 / 12 / 5 / 0 / 2 / 1 / 9 / 9
C3 / 12 / 10 / 4 / 1 / 1 / 3 / 8 / 8
C4 / 12 / 10 / 5 / 1 / 1 / 3 / 8 / 8
C5 / 12 / 10 / 5 / 1 / 1 / 3 / 8 / 8
C6 / 14 / 12 / 6 / 0 / 2 / 1 / 9 / 9
C7 / 12 / 10 / 6 / 1 / 1 / 3 / 8 / 8
C8 / 12 / 10 / 6 / 1 / 1 / 3 / 8 / 8
C9 / 12 / 10 / 7 / 1 / 1 / 3 / 8 / 8
C10 / 10 / 8 / 7 / 2 / 0 / 5 / 7 / 7
C11 / 10 / 8 / 6 / 2 / 0 / 5 / 7 / 7
C12 / 13 / 10 / 3 / 0 / 2 / 1 / 9 / 9

Table S5 Summary of identified intermediates during ·OH oxidation

Compound / RTa, min / MWb / MS ions and detection mode c / MS2 spectrum ions / Structure formula
BP3 / 10.8 / 228.08 / 229.03(+) / 105.04, 151.01 /
P1 / 6.6 / 244.07 / 245.03(+) / 121.03, 151.01 /
P2 / 9.6 / 244.07 / 245.13(+) / 105.03, 167.02 /
P3 / 13.5 / 260.07 / 259.21(-) / 137.04, 151.02 /
P4 / 13.9 / 260.07 / 259.25(-) / 121.31, 166.85 /
P5 / 8.4 / 260.07 / 259.06(-) / ___ /
P6 / 11.6 / 292.06 / 293.04(+) / ___ /


P7 / 7.3 / 258.05 / 259.01(+) / 105.06, 181.18 /
P8 / 6.1 / 276.06 / 277.24(+) / ___ /
P9 / 12.7 / 274.05 / 275.21(+) / ___ /
P10 / 8.0 / 214.06 / 215.02(+) / 105.03, 137.05 /
P11 / 10.0 / 230.06 / 231.07(+) / ___ /

P12 / 2.0 / 168.04 / 168.99(+) / 150.87 /
P13 / 17.2 / 184.04 / 184.93(+) / ___ /
P14 / 7.2 / 276.06 / 277.08(+) / 121.13, 183.06 /
P15 / 7.6 / 290.04 / 291.12(+) / ___ /
P16 / 12.2 / 306.64 / 307.12(+) / ___ /
P17 / 9.2 / 246.05 / 247.01(+) / 121.23, 153.11 /
P18 / 6.8 / 246.05 / 246.90(+) / ___ /


Table S6 The unsaturation degrees of the molecular structure (Ω1) and molecular formula (Ω2) of intermediates generated from ·OH oxidation

Compound / C / H / O / / / / Unsaturation
（Ω1） / Unsaturation
（Ω2）
P1 / 14 / 12 / 4 / 0 / 2 / 1 / 9 / 9
P2 / 14 / 12 / 4 / 0 / 2 / 1 / 9 / 9
P3 / 14 / 12 / 5 / 0 / 2 / 1 / 9 / 9
P4 / 14 / 12 / 5 / 0 / 2 / 1 / 9 / 9
P5 / 14 / 12 / 5 / 0 / 2 / 1 / 9 / 9
P6 / 14 / 12 / 7 / 2 / 1 / 3 / 9 / 9
P7 / 14 / 10 / 5 / 0 / 2 / 2 / 10 / 10
P8 / 14 / 12 / 6 / 2 / 1 / 3 / 9 / 9
P9 / 14 / 10 / 6 / 0 / 2 / 2 / 10 / 10
P10 / 13 / 10 / 3 / 0 / 2 / 1 / 9 / 9
P11 / 13 / 10 / 4 / 0 / 2 / 1 / 9 / 9
P12 / 8 / 8 / 4 / 0 / 1 / 1 / 5 / 5
P13 / 8 / 8 / 5 / 0 / 1 / 1 / 5 / 5
P14 / 14 / 12 / 6 / 0 / 2 / 1 / 9 / 9
P15 / 14 / 10 / 7 / 0 / 2 / 2 / 10 / 10
P16 / 14 / 10 / 8 / 2 / 1 / 4 / 10 / 10
P17 / 13 / 10 / 5 / 0 / 2 / 1 / 9 / 9
P18 / 13 / 10 / 5 / 0 / 2 / 1 / 9 / 9

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Fig. S1 Mass fraction of each intermediate in the molecular ozone oxidation


Fig S2. Mass fraction of each intermediate during ·OH oxidation

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