Citation: Run Huang, Chaoting Guan, Qin Guo, Zhen Wang, Hanping Pan, Jin Jiang. Oxidation of diclofenac by permanganate: Kinetics, products and effect of inorganic reductants[J]. Chinese Chemical Letters, ;2023, 34(4): 107610. doi: 10.1016/j.cclet.2022.06.033 shu

Oxidation of diclofenac by permanganate: Kinetics, products and effect of inorganic reductants

Run Huang ^{a, b} ,
Chaoting Guan ^{a, b, *,} ,
Qin Guo ^{a, b} ,
Zhen Wang ^{a, b} ,
Hanping Pan ^{a, b} ,
Jin Jiang ^{a, b}

a.
Key Laboratory for City Cluster Environmental Safety and Green Development of the Ministry of Education, School of Ecology, Environment and Resources, Guangdong University of Technology, Guangzhou 510006, China
b.
Southern Marine Science and Engineering Guangdong Laboratory (Guangzhou), Guangzhou 511458, China

guanct@gdut.edu.cn

Received Date: 3 March 2022
Revised Date: 31 May 2022
Accepted Date: 13 June 2022
Available Online: 16 June 2022

Figures(5)

The large consumption and discharge of diclofenac (DCF) lead to its frequent detection in surface water and groundwater, posing great threats to humans and ecosystems. This study explored the oxidation kinetics of DCF by permanganate (Mn(Ⅶ)), and expounded the underlying reason for the unusual pH-dependency that was unclear in previous studies. The kinetics of DCF analogues (i.e., aromatic secondary amines) by Mn(Ⅶ) oxidation were comparatively investigated. Then, a tentative kinetic model involving the formation of an intermediate between Mn(Ⅶ) and DCF or its analogues was proposed to fit the pH-rate profile. Since DCF contained two chloro groups, and a carboxyl group which could be ionized by negative electrospray ionization, a precursor ionization scanning approach was used for the first time for detection of N-containing chlorinated oxidation products. New degradation pathways of DCF containing ring opening, carboxylation, carbonylation, electrophilic addition, hydroxylation and dehydrogenation were proposed based on the identified oxidation products. Moreover, it was demonstrated that the introduction of various reducing agents such as Mn(Ⅱ), Fe(Ⅱ) and bisulfite significantly improved the oxidation kinetics of DCF by Mn(Ⅶ). The positive effects of Mn(Ⅱ) and Fe(Ⅱ) were mainly attributed to the accelerated formation of MnO₂ that acted as a catalyst or co-oxidizer contributing to DCF degradation. The presence of bisulfite caused two-stage kinetics, where a sharp drop of DCF concentration followed by a slowdown of DCF removal. In the first stage, potent reactive manganese species (e.g., Mn(Ⅲ), Mn(Ⅴ), and Mn(Ⅵ)) and sulfate radical were generated during reaction of bisulfite with Mn(Ⅶ), whereas bisulfite was depleted fast due to excess Mn(Ⅶ) concentrations and the system became the Mn(Ⅶ)/MnO₂ system in the second stage. These results provide new insight into reaction mechanism of DCF with Mn(Ⅶ) as well as propose a feasible strategy for enhancing the treatment of DCF contaminated water by Mn(Ⅶ).
- Permanganate,
- Diclofenac,
- Aromatic secondary amines,
- Precursor ionization scanning,
- Reductant activation
1. [1]
  L. Xu, X.Y. Cui, J.B. Liao, et al., Chin. Chem. Lett. 33 (2022) (2021) 3701–3704.
2. [2]
  J. Hofmann, U. Freier, M. Wecks, S. Hohmann, Appl. Catal. B 70 (2007) 447–451. doi: 10.1016/j.apcatb.2005.11.023
3. [3]
  P. Izadi, P. Izadi, R. Salem, et al., Environ. Pollut. 267 (2020) 115370. doi: 10.1016/j.envpol.2020.115370
4. [4]
  N. Vieno, M. Sillanpää, Environ. Int. 69 (2014) 28–39. doi: 10.1016/j.envint.2014.03.021
5. [5]
  E. Vulliet, C. Cren-Olive, Environ. Pollut. 159 (2011) 2929–2934. doi: 10.1016/j.envpol.2011.04.033
6. [6]
  R. Lopez-Serna, A. Jurado, E. Vazquez-Sune, et al., Environ. Pollut. 174 (2013) 305–315. doi: 10.1016/j.envpol.2012.11.022
7. [7]
  R.X. Ma, B. Wang, S.Y. Lu, et al., Sci. Total Environ. 557 (2016) 268–275.
8. [8]
  Y.J. Zhang, S.U. Geissen, C. Gal, Chemosphere 73 (2008) 1151–1161. doi: 10.1016/j.chemosphere.2008.07.086
9. [9]
  L. Lonappan, S.K. Brar, R.K. Das, M. Verma, R.Y. Surampalli, Environ. Int. 96 (2016) 127–138. doi: 10.1016/j.envint.2016.09.014
10. [10]
  J. Schwaiger, H. Ferling, U. Mallow, H. Wintermayr, R.D. Negele, Aquat. Toxicol. 68 (2004) 141–150. doi: 10.1016/j.aquatox.2004.03.014
11. [11]
  R. Triebskorn, H. Casper, A. Heyd, et al., Aquat. Toxicol. 68 (2004) 151–166. doi: 10.1016/j.aquatox.2004.03.015
12. [12]
  H.Y. Cheng, D. Song, H.J. Liu, J.H. Qu, Chemosphere 136 (2015) 297–304. doi: 10.1016/j.chemosphere.2014.11.062
13. [13]
  B. Nas, T. Dolu, M.E. Argun, et al., Sci. Total Environ. 779 (2021) 146344. doi: 10.1016/j.scitotenv.2021.146344
14. [14]
  C.Y. Dang, F.B. Sun, H. Jiang, et al., J. Hazard. Mater. 400 (2020) 123225. doi: 10.1016/j.jhazmat.2020.123225
15. [15]
  D.X. Yang, J.L. Liang, L. Luo, et al., Chin. Chem. Lett. 32 (2021) 2534–2538. doi: 10.1016/j.cclet.2020.12.049
16. [16]
  S. Lim, J.L. Shi, U. von Gunten, D.L. McCurry, Water Res. 213 (2022) 118053. doi: 10.1016/j.watres.2022.118053
17. [17]
  Z. Wang, W. Qiu, S.Y. Pang, et al., Environ. Sci. Technol. 56 (2022) 1492–1509. doi: 10.1021/acs.est.1c04530
18. [18]
  L.H. Hu, H.M. Martin, O. Arcs-Bulted, et al., Environ. Sci. Technol. 43 (2009) 509–515. doi: 10.1021/es8023513
19. [19]
  L.H. Hu, H.M. Martin, T.J. Strathmann, Environ. Sci. Technol. 44 (2010) 6416–6422. doi: 10.1021/es101331j
20. [20]
  L.H. Hu, A.M. Stemig, K.H. Wammer, T.J. Strathmann, Environ. Sci. Technol. 45 (2011) 3635–3642. doi: 10.1021/es104234m
21. [21]
  J. Jiang, S.Y. Pang, J. Ma, H.L. Liu, Environ. Sci. Technol. 46 (2012) 1774–1781. doi: 10.1021/es2035587
22. [22]
  J. Li, S.Y. Pang, Z. Wang, et al., Water Res. 203 (2021) 117513. doi: 10.1016/j.watres.2021.117513
23. [23]
  F. Pan, H.D. Ji, P.H. Du, et al., J. Hazard. Mater. 402 (2021) 123779. doi: 10.1016/j.jhazmat.2020.123779
24. [24]
  T. Rodriguez-Alvarez, R. Rodil, J.B. Quintana, S. Trinanes, R. Cela, Water Res. 47 (2013) 3220–3230. doi: 10.1016/j.watres.2013.03.034
25. [25]
  Y. Gao, Y. Zhou, S.Y. Pang, et al., Environ. Sci. Technol. 53 (2019) 3689–3696. doi: 10.1021/acs.est.8b05306
26. [26]
  S.Y. Pang, J.B. Duan, Y. Zhou, Y. Gao, J. Jiang, Chemosphere 235 (2019) 104–112. doi: 10.1016/j.chemosphere.2019.06.156
27. [27]
  F. Xiao, X.R. Zhang, H.Y. Zhai, et al., Environ. Sci. Technol. 46 (2012) 7112–7119. doi: 10.1021/es3010656
28. [28]
  Y. Pan, X.R. Zhang, Environ. Sci. Technol. 47 (2013) 1265–1273. doi: 10.1021/es303729n
29. [29]
  H.Y. Zhai, X.R. Zhang, X.H. Zhu, J.Q. Liu, M. Ji, Environ. Sci. Technol. 48 (2014) 2579–2588. doi: 10.1021/es4034765
30. [30]
  X.R. Zhang, J.W. Talley, B. Boggess, G.Y. Ding, D. Birdsell, Environ. Sci. Technol. 42 (2008) 6598–6603. doi: 10.1021/es800855b
31. [31]
  J. Jiang, S.Y. Pang, J. Ma, Environ. Sci. Technol. 43 (2009) 8326–8331. doi: 10.1021/es901663d
32. [32]
  J. Jiang, Y. Gao, S.Y. Pang, et al., Environ. Sci. Technol. 49 (2015) 520–528. doi: 10.1021/es504796h
33. [33]
  Y. Gao, J. Jiang, Y. Zhou, et al., Environ. Sci. Technol. 52 (2018) 4785–4793. doi: 10.1021/acs.est.8b00120
34. [34]
  Y.T. Zhu, J.F. Ling, L. Li, X.H. Guan, Chin. Chem. Lett. 31 (2020) 1545–1549. doi: 10.1016/j.cclet.2019.12.036
35. [35]
  D.D. Rao, J. Chen, H.Y. Dong, et al., Water Res. 188 (2021) 116481. doi: 10.1016/j.watres.2020.116481
36. [36]
  Y. Zhou, J.P. Hu, Y. Gao, et al., Chin. Chem. Lett. 33 (2022) 447–451. doi: 10.1016/j.cclet.2021.06.036
37. [37]
  X.L. Huangfu, J. Jiang, J. Ma, Y.Z. Liu, J. Yang, Environ. Sci. Technol. 47 (2013) 10285–10292. doi: 10.1021/es4003247
38. [38]
  J.S. Du, B. Sun, J. Zhang, G.X. Hong, Environ. Sci. Technol. 46 (2012) 8860–8867. doi: 10.1021/es302076s
39. [39]
  J. Jiang, Y. Gao, S.Y. Pang, et al., Environ. Sci. Technol. 48 (2014) 10850–10858. doi: 10.1021/es5008577
40. [40]
  C.T. Guan, J. Jiang, S.Y. Pang, et al., Environ. Sci. Technol. 51 (2017) 10718–10728. doi: 10.1021/acs.est.7b02271
41. [41]
  C.T. Guan, J. Jiang, C.W. Luo, et al., Chem. Eng. J. 337 (2018) 40–50. doi: 10.1016/j.cej.2017.12.083
42. [42]
  C.W. Luo, J. Jiang, J. Ma, et al., Water Res. 96 (2016) 12–21. doi: 10.1016/j.watres.2016.03.039
43. [43]
  Y.H. Zhu, X.X. Wang, J. Zhang, et al., Environ. Sci. Technol. 53 (2019) 9063–9072. doi: 10.1021/acs.est.9b01510
44. [44]
  Y.H. Zhu, C. Zhao, J.L. Liang, et al., Water Res. 165 (2019) 114975. doi: 10.1016/j.watres.2019.114975
45. [45]
  B. Sun, X.H. Guan, J.Y. Fang, P.G. Tratnyek, Environ. Sci. Technol. 49 (2015) 12414–12421. doi: 10.1021/acs.est.5b03111
46. [46]
  C.T. Guan, Q. Guo, Z. Wang, et al., Water Res. 216 (2022) 118331. doi: 10.1016/j.watres.2022.118331
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