Journal of Applied Electrochemistry

, Volume 38, Issue 2, pp 151–159 | Cite as

Mixed first and zero order kinetics in the electrooxidation of sulfamethoxazole at a boron-doped diamond (BDD) anode

  • Shuhuan Li
  • Dorin Bejan
  • M. S. McDowell
  • Nigel J. Bunce
Original Paper


Pharmaceutical residues in the aquatic environment represent an emerging environmental problem, because many pharmaceuticals are refractory towards conventional waste water treatment. This study focussed on the oxidation of the sulfonamide antibiotic sulfamethoxazole (SMX) at a boron-doped diamond anode, at which reactive hydroxyl radicals are formed. Electrochemical oxidation led to mineralization with high current efficiency, but without the formation of known toxic products of partial oxidation. A “mixed” kinetic order with respect to substrate concentration was observed; the kinetics could be shifted in the direction of either diffusion control (first order in SMX) or current control (zero order in SMX) by adjusting the substrate concentration and current density. Alternatively, the electrooxidation could be described by a model, applicable to a wide range of reaction conditions, in which the kinetic orders with respect to current and initial substrate concentration were approximately 0.4 and 0.5, respectively.


Sulfamethoxazole Boron-doped diamond anode Electrochemical oxidation Diffusion vs. current control  Mineralization 



We thank the Natural Sciences and Engineering Research Council of Canada for financial support and Dr H. Lee for assistance with the bacterial assays.


  1. 1.
    Swain GM, Ramesham R (1993) Anal Chem 65:345CrossRefGoogle Scholar
  2. 2.
    Perret A, Haenni W, Niedermann P, Skinner N, Comninellis Ch, Gandini D (1998) Proc Electrochem Soc 97:275Google Scholar
  3. 3.
    Marselli B, Garcia-Gomez J, Michaud P-A, Rodrigo MA, Comninellis Ch (2003) J Electrochem Soc 150:D79CrossRefGoogle Scholar
  4. 4.
    Rodrigo MA, Michaud PA, Duo I, Panizza M, Cerisola G, Comninellis Ch (2001) J Electrochem Soc 148:D60CrossRefGoogle Scholar
  5. 5.
    Morao A, Lopez A, Pessou de Amorim M, Goncalves M (2004) Electrochim Acta 49:1587Google Scholar
  6. 6.
    Ammar S, Abdelhedi R, Flox C, Arias C, Brillas E (2006) Environ Chem Lett 4:229CrossRefGoogle Scholar
  7. 7.
    Both VM, Comninellis Ch (1999) Process/System Engineering 70:165Google Scholar
  8. 8.
    Da Pozzo A, Merli C, Sirés I, Garrido JA, Rodríguez RM, Brillas E (2005) Environ Chem Lett 3:7CrossRefGoogle Scholar
  9. 9.
    Bonin PML, Bejan D, Radovic-Hrapovic Z, Halasz H, Hawari J, Bunce NJ (2005) Environ Chem 3:125CrossRefGoogle Scholar
  10. 10.
    Waterston K, Bejan D, Bunce NJ (2006) J Appl Electrochem 36:227CrossRefGoogle Scholar
  11. 11.
    Kolpin D, Furlong E, Meyer M, Thurman E, Zaugg S, Barber L, Buxton H (2002) Environ Sci Technol 36:1202CrossRefGoogle Scholar
  12. 12.
    Ternes T (2001) ACS Symp Ser 791:39Google Scholar
  13. 13.
    Heberer T (2002) Toxicol Lett 131:5CrossRefGoogle Scholar
  14. 14.
    Carballa M, Omil F, Lema JM, Llompart M, Garcia-Jares C, Rodriguez I, Gomez M, Ternes T (2004) Water Res 38:2918CrossRefGoogle Scholar
  15. 15.
    Miao X-S, Bishay F, Chen M, Metcalfe CD (2004) Environ Sci Technol 38:3533CrossRefGoogle Scholar
  16. 16.
    Hirsch R, Ternes T, Haberer K, Kratz K-L (1999) Sci Total Environ 225:109CrossRefGoogle Scholar
  17. 17.
    Sanderson H, Johnson D, Wilson C, Brain R, Solomon K (2003) Toxicol Lett 144:383CrossRefGoogle Scholar
  18. 18.
    Ternes T, Meisenheimer M, McDowell D, Sacher F, Brauch H, Haist-Gulde B, Preuss G, Wilme U, Zulei-Seibert N (2002) Environ Sci Technol 36:3855CrossRefGoogle Scholar
  19. 19.
    Zuccato E, Calamari D, Natangelo P, Fanelli R (2000) Lancet 355:1789CrossRefGoogle Scholar
  20. 20.
    Kümmerer K (2001) Chemosphere 45:957CrossRefGoogle Scholar
  21. 21.
    Perez S, Eichhorn P, Aga DS (2005) Environ Toxicol Chem 24:1361CrossRefGoogle Scholar
  22. 22.
    Drillia P, Dokianakis SN, Fountoulakis MS, Kornaros M, Stamatelatou K, Lyberatos G (2005) J Hazard Mater 122:259CrossRefGoogle Scholar
  23. 23.
    Huber MM, Canonica S, Park G-Y, von Gunten U (2003) Environ Sci Technol 37:1016CrossRefGoogle Scholar
  24. 24.
    Huber MM, Korhonen S, Ternes TA, von Gunten U (2005) Water Res 39:3607CrossRefGoogle Scholar
  25. 25.
    Huber MM, Goegel A, Joss A, Hermann N, Loeffler D, McArdell CS, Reid A, Siegrist H, Ternes TA, Von Gunten U (2005) Environ Sci Technol 39:4290CrossRefGoogle Scholar
  26. 26.
    Sharma VK, Mishra SK, Ray AK (2006) Chemosphere 62:128CrossRefGoogle Scholar
  27. 27.
    Jørgensen SE, Halling-Sørensen B (2000) Chemosphere 40:691CrossRefGoogle Scholar
  28. 28.
    Ingerslev F, Halling-Sørensen B (2000) Environ Toxicol Chem 19:2467CrossRefGoogle Scholar
  29. 29.
    Drewes JE, Shore LS (2001) ACS Symp Ser 791:206CrossRefGoogle Scholar
  30. 30.
    Webb S, Ternes T, Gibert M, Olejniczak K (2003) Toxicol Lett 142:157CrossRefGoogle Scholar
  31. 31.
    Schwab BW, Hayes EP, Fiori JM, Mastrocco FJ, Roden MN, Cragin D, Meyerhoff RD, D’Aco VJ, Anderson PD (2005) Regul Toxicol Pharmacol 42:296CrossRefGoogle Scholar
  32. 32.
    De Souza A, Baylocq D, Pellerin F (1988) Talanta 35:875CrossRefGoogle Scholar
  33. 33.
    Lovrek M, Zorc B, Butula I (1998) Acta Pharm (Zagreb) 48:31Google Scholar
  34. 34.
    Goyal RN, Srivastava RK (1990) Indian J Chem 29A:635Google Scholar
  35. 35.
    Husain S, Krishna Murty ASR, Prasad PR, Sekar R (1995) Indian Drugs 32:336Google Scholar
  36. 36.
    Cribb AE, Spielberg SP (1992) Clin Pharmacol Ther 51:522CrossRefGoogle Scholar
  37. 37.
    Lavergne SN, Volkman EM, Maki JE, Yoder AR, Trepanier LA (2005) Toxicology 208:63CrossRefGoogle Scholar
  38. 38.
    Lehmann DF, Liu A, Newman N, Blair DC (1999) J Clin Pharmacol 39:533Google Scholar
  39. 39.
    Bard AJ, Faulkner LR (2000) Electrochemical methods: fundamentals and applications, 2nd edn. Wiley, New York, Chapter 3Google Scholar
  40. 40.
    Marusawa H, Ichikawa K, Narita N, Murakami H, Ito K, Tezuka T (2002) Bioorg Med Chem 10:2283CrossRefGoogle Scholar
  41. 41.
    Rajeshwar K, Ibanez JG (1997) Environmental electrochemistry. Academic Press, San Diego, CA, Chapter 2Google Scholar
  42. 42.
    Waterston K, Wang JW, Bejan D, Bunce NJ (2007) J Appl Electrochem 37:367CrossRefGoogle Scholar
  43. 43.
    Le Naour C, Moisy P, Arpigny S, Madic C (1999) Electrochim Acta 44:3505CrossRefGoogle Scholar
  44. 44.
    Körbahteit BK, Salih B, Tanyolac A (2001) J Chem Technol Biotechnol 77:70CrossRefGoogle Scholar
  45. 45.
    Bejankiwar R, Lalman JA, Seth R, Biswas N (2005) Water Res 39:4715CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2007

Authors and Affiliations

  • Shuhuan Li
    • 1
  • Dorin Bejan
    • 1
  • M. S. McDowell
    • 1
  • Nigel J. Bunce
    • 1
  1. 1.Department of ChemistryUniversity of GuelphGuelphCanada

Personalised recommendations