Supporting Information. Waters

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1 Supporting Information xidation of Phenolic Endocrine Disrupting Chemicals by Potassium Permanganate in Synthetic and Real Waters Jin Jiang, Su-Yan Pang,, Jun Ma,, * and Huiling Liu State Key Laboratory of Urban Water Resource and Environment, School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin , China, College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin , China * Corresponding author: Professor Dr Jun Ma Tel: ; fax: ; majun@hit.edu.cn. Prepared on December 20, 2011 Environmental Science & Technology This file of 26 pages contained 11 figures and 4 tables. 1

2 Text S1. Stock solutions of phenolic EDCs in low µm range were first prepared in basic solutions and then neutralized following the suggestion of Lee et al. 1 Potassium ferrate of high purity (> 95%) was prepared using the method of Thompson et al., 2 and its stock solutions were freshly produced by dissolving solid samples in a 5 mm Na 2 HP 4 /1 mm borate buffer (ph = 9.2) and standardized spectrophotometrically at 510 nm (ε = 1150 M -1 cm -1 ). zone was generated from pure oxygen with a laboratory ozonizer apparatus. zone stock solutions were prepared by bubbling ozone-containing oxygen through Milli-Q water adjusted to ph 2 and standardized by the measurements of the absorbance of ozone at 260 nm (ε = 3000 M -1 cm -1 ). Stock solutions of chlorine were prepared by diluting a commercial solution of sodium hypochlorite (> 9% available chlorine) and standardized by iodometric titration. Stock solutions of Mn(VII) were prepared by dissolving the crystals of KMn 4 in Milli-Q water and standardized spectrophotometrically at 525 nm (ε = 2500 M -1 cm -1 ). Text S2. Reaction products were identified by liquid chromatography-tandem mass spectrometry performed on an AB SCIEX QTRAP 5500 outfitted with an Agilent series 1260 HPLC. Separation was achieved using an Agilent Poroshell 120 EC-C18 column ( mm, 2.7 µm). Elution was performed with 0.1% formic acid (A) and acetonitrile (B) at a flow rate of 0.2 ml/min. The gradient was as follows: B started at 5% and was increased linearly to 50% in 30 min, kept for 10 min and finally decreased to 5% in 5 min. Nitrogen was used as curtain gas, and synthetic air was used as nebulizer gas. They were operated with the flow rate of 35 and 50 L/min, respectively. The turboionspray interface was operated in the negative ion mode at V and 500. The quadruple Q 1 was used for survey scan over the mass to charge (m/z) range from 50 to 600 Da with the scan rate of 1000 Da/s. Declustering potential (DP) and entrance potential (EP) were set at -70 V and -10 V, respectively. The linear ion trap (LIT) Q 3 was used for enhanced product ion (EPI) scan with the scan rate of Da/s and the LIF fill time of 1 ms. The collision gas (CAD) was set at the medium level and the collision energy (CE) was set at -20 ~ -50 V. Text S3. The procedure for the ABTS method was as follows: 2 ml of the buffer reagent (ph = 4.2, 0.6 M acetate/0.2 M phosphate) and 2 ml of ABTS stock solution (2 mm) were added to 10 ml volumetric 2

3 flasks. Then, samples containing oxidants were added under vigorous stirring and the flasks were filled with Milli-Q water. Blank solutions were prepared by using samples without oxidants. After the complete formation of the green color (i.e., several seconds were enough for Fe(VI) and Mn(VII), while for chlorine several minutes were needed), the absorbance at 415 nm was read at a PGENERAL T6 spectrophotometer with alterable cells (1, 2, or 5 cm). The high sensitivity of the ABTS method (i.e., ε = M -1 cm -1 at 415 nm) allows a limit of detection of about 0.06 µm of Mn(VII) with a cell of 1 cm path length. 3

4 k, M -1 s -1 k, M -1 s -1 k, M -1 s E1 3 HCl ph E3 3 HCl ph 4-n-NP 3 Fe(VI) HCl ph k, M -1 s -1 k, M -1 s -1 k, M -1 s E2 3 Fe(VI) HCl ph EE2 3 Cl 2 Fe(VI) HCl ph BPA 3 Fe(VI) HCl ph Figure S1. Summary of ph-dependent second-order rate constants (k) for the reactions of selective oxidants including ozone ( 3 ), chlorine (HCl), chlorine dioxide (Cl 2 ), and ferrate (Fe(VI)) with E1, E2, E3, EE2, 4-n-NP, and BPA. Species-specific second-order rate constants and the pk a values of selected phenolic EDCs used to generate the kinetic data are provided in another excel file. 4

5 H H H H H H H H E1 E2 E3 EE2 H H H H 4-n-NP THN ECH cyclopentanone cyclopentanol Figure S2. Chemical structures of EDCs and the model compounds THN, 1-ethinyl-1-cyclohexanol (ECH), cyclopentanone, and cyclopentanol. 5

6 [E2] (µm) a ph=5,[mn(vii)]=60µm ph=6,[mn(vii)]=60µm ph=7,[mn(vii)]=60µm ph=8,[mn(vii)]=12µm ph=9,[mn(vii)]=3µm ph=10,[mn(vii)]=3µm ph=11,[mn(vii)]=1.5µm Time (min) b k obs, s [Mn(VII)] (µm) Figure S3. Time courses of E2 (0.15 µm) oxidation by Mn(VII) over the ph range of 5-11 (a), and the linear relationship between measured pseudo-first-order rate constants (k obs, s -1 ) and Mn(VII) concentration at ph 8 (b). 6

7 C/C 0 C/C BPA synthetic buffer solution surface water wastewater effluent prediction in surface water prediction in wastewater effluent [Mn(VII)] in surface water [Mn(VII)] in wastewater effluent 2 phenol Time (min) [Mn(VII)] (µm) [Mn(VII)] (µm) Figure S4. Model predictions of the oxidative removal of BPA and phenol (0.15 µm) by Mn(VII) (12 µm) in real waters. 7

8 blank [Mn(II)] = 4 µm [S 3 2- ] = 4 µm [p-hydroquinone] = 2 µm C/C Time (min) Figure S5. Effect of the simultaneous presence of reduced species including Mn(II), sulfite (S 2-3 ), and p-hydroquinone on the oxidation kinetics of E2 by Mn(VII) in synthetic buffer water at ph 8. Experimental condition: [E2] 0 = 0.15 µm, [Mn(VII)] 0 = 12 µm, [Mn(II)] = [S 2-3 ] = 4 µm, and [phydroquinone] = 2 µm. 8

9 synthetic buffer solution synthetic buffer solution + Mn 2 surface water surface water + Mn 2 C/C Time (min) Figure S6. Effect of the addition of preformed Mn 2 colloids on the oxidation kinetics of E2 by Mn(VII) in synthetic buffer solution and surface water at ph 8. Experimental condition: [E2] 0 = 0.15 µm, [Mn(VII)] 0 = 12 µm, and [Mn 2 ] = 4 µm. The colloidal Mn 2 stock solution was prepared as described previously (ref 27 in the main text) by mixing appropriate amounts of Mn(VII) and Na 2 S 2 3 stock solutions according to the following reaction stoichiometry: 2 2 S Mn + 2H 8Mn + S + H (S1) 9

10 1.0 ph=6,[mn(vii)]=60µm 1.0 ph=7,[mn(vii)]=60µm C/C C/C Time (min) Time (min) 1.0 ph=8,[mn(vii)]=3µm 1.0 ph=9,[mn(vii)]=3µm C/C C/C blank NTA pyrophosphate humic acid EDTA phosphate Time (min) Time (min) Figure S7. The influence of selected model ligands on the oxidation kinetics of E2 by Mn(VII) at ph 6-9. Experimental conditions: [E2] 0 = 0.15 µm, [phosphate] = 5 mm, [pyrophosphate] = [EDTA] = [NTA] = 5 µm, and [humic acid] = 0.25 mg C/L. 10

11 1.0 pyrophosphate pyrophosphate+p-hydroquinone pyrophosphate+mn(ii) 0.8 C/C Time (min) Figure S8. Influence of the addition of reduced species on the oxidation kinetics of E2 by Mn(VII). Experimental conditions: [E2] 0 = 0.15 µm, ph = 5, [pyrophosphate] = 5 µm, [Mn(II)] = [phydroquinone] = 0.5 µm, and [Mn(VII)] = 60 µm. 11

12 without ligand 0.15 Abs with pyrophosphate Abs wavelength (nm) Figure S9 Changes of UV-Vis spectra during the reactions between Mn(VII) and E2 in the absence or presence of pyrophosphate. Experimental condition: [E2] = 6 µm, [Mn(VII)] = 60 µm, and [pyrophosphate] = 100 µm. 12

13 5 CE 235nm Mn(III)-pyrophosphate standard (30 µm) increase with reaction time Time (min) Figure S10. Development of CE electropherogram of the reaction solution containing E2 (6 µm), Mn(VII) (60 µm), and pyrophosphate (100 µm) at ph 5 along the reaction time. 13

14 a -1.0 k obs, s -1 ln(c/c 0 ) ph=5 ph=6 ph=7 ph= Time (min) [Mn(III)-NTA] (µm) b Figure S11. Pseudo-first-order kinetic plot of E2 oxidation (0.15 µm) by Mn(III)-NTA complex ([Mn(III)]:[NTA] = 1:10) in great excess (6 µm) (a), and the initial rate constant (k obs, s -1 ) (i.e., the slope within the time period where the pseudo-first-order kinetics could be approximated) versus the concentration of Mn(III)-NTA complex at ph 8 (b). The deviation for the pseudo-first-order kinetics as the reaction progressed was also observed in our previous study, and could be ascribed to the inhibitory effect of accumulated inorganic product Mn(II) (ref 28 in the main text). 14

15 Table S1. Second-rder Rate Constants (k Mn(VII), M -1 s -1 ) for Mn(VII) Reactions with Selected EDCs, the Model Compound THN, and ther Phenolic Substrates. substrate ph E E E n-NP THN BPA TCS n.d. Phenol DCP n.d. n.d. 15

16 Table S2. xidation Products of EE2 Detected by LC-MS/MS. Product ID ESI(-) MS m/z a EE2 295 M b ESI(-) MS/MS m/z 295 c, 269, 245, 183, 159, , 245, 237, 219, 201 H 1 Proposed structure R t (min) H H H H 15.1 H , 249, 231, 205 H , 265, 239, 221, , 281, 266, 251, , 295, 269, 243 H H H H H , 299, 281, 273, 255 H H H H , 311, 285, 255 H 20.5 H H , 325, 299, 281 H H H , 341, 315, 297, H H

17 H , 357, 331, 313 H H H , 359, 331, , 345, 327, 309, 299 H H H H H H H H a The m/z values shown were for deprotonated molecular ions [M-H] -. b M represented the mass difference from the parent molecule of the product. c The bold number indicated the most abundant fragment ion. 17

18 Table S3. xidation Products of THN Detected by LC-MS/MS. Product ID ESI(-) MS m/z a THN 147 M b d ESI(-) MS/MS m/z 147, 143, 130, 119 c, , 143, 130, 119, , 127, Proposed structure H 101, , 145, 133, 119, 107 H 165, 148, 137, 121, 93, 179, 161, H 151, 143, R t (min) H 3.1 H H , 177, H H 151, , 167, 149, 121 H H 227, 183, H H 165, 243, 197, 179, 161, 151 H H H H a The m/z values shown were for deprotonated molecular ions [M-H] -. b M represented the mass difference from the parent molecule of the product. c The bold number indicated the most abundant fragment ion. d The product was confirmed using the authentic standard

19 Table S4. Literature Summary of Intermediates and Products of E2, EE2, and THN Formed During Chemical xidation Processes. Product ID number [M-H] E2 Proposed structure H xidation process Reference photo-fenton [8] [3] [3] H H H 3 [3] H photolysis [11] photolysis [11] H H 3 [3] H H photolysis [11] UV/Ti 2 [9] 19

20 H photo-fenton [8] H H photo-fenton [8] H H photo-fenton [8] H H 3 [5] H photolysis [11] H H [6] H photo-fenton [8] H H H H H 3 UV/Ti 2 photo-fenton dye-mediated photocatalysis [6, 8, 10, 12] photo-fenton UV/Ti 2 [8, 9] H H UV/Ti 2 photo-fenton 3 dye-mediated photocatalysis [5, 8-10, 12] 20

21 H photo-fenton [8] H H H photo-fenton [8] H H photo-fenton [8] H H photo-fenton [9] H H dye-mediated photocatalysis [12] H H UV/Ti 2 dye-mediated photocatalysis [10, 12] H H H 3 [6] H [6] H H H UV/Ti 2 [10] 21

22 H H H UV/Ti 2 [10] H H H H UV/Ti 2 [10] EE H H 3 [3] H 3 [3] H H 3 [14] H [14] H H H H [3] H photolysis [11] H H [3] H H 22

23 H 3 [7] H H H 3 [13] H H 3 [13] H H 3 [13] H H H 3 [3] H H H H 3 [3] H H 3 [3] H H H H 3 [3] H 23

24 H H 3 [7] H THN H 3 [3] H H H 3 [3] photolysis [11] photolysis [11] photolysis [11] H H photolysis [11] H H H photolysis [11] H photolysis [11] H Literature Cited (1) Lee, Y.; Yoon, J.; von Gunten, U. Kinetics of the oxidation of phenols and phenolic endocrine disruptors during water treatment with ferrate (Fe(VI)). Environ. Sci. Technol. 2005, 39, (2) Thompson, G. W.; ckerman, G. W.; Schreyer, J. M. Preparation and purification of potassium ferrate. J. Am. Chem. Soc. 1951, 73,

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26 (12) Diaz, M.; Luiz, M.; Alegretti, P.; Furlong, J.; Amat-Guerri, F.; Massad, W.; Criado, S.; Garcia, N. A. Visible-light-mediated photodegradation of 17β-estradiol: Kinetics, mechanism and photoproducts. J. photochem. Phtobiol. A: Chem. 2009, 202, (13) Zhang, X.; Chen, P.; Wu, F.; Deng, N.; Liu, J.; Fang, T. Degradation of 17α-ethinylestradiol in aqueous solution by ozonation. J. Hazard. Mater. 2006, 133, (14) Maniero, M. G.; Bila, D. M.; Dezotti, M. Degradation and estrogenic activity removal of 17βestradiol and 17α-ethinylestradiol by ozonation and 3 /H 2 2. Sci. Total Environ. 2008, 47,