Environmental Science and Pollution Research

, Volume 19, Issue 5, pp 1563–1573 | Cite as

Degradation and mineralization of sulcotrione and mesotrione in aqueous medium by the electro-Fenton process: a kinetic study

  • Minir Murati
  • Nihal Oturan
  • Jean-Jacques Aaron
  • Ahmad Dirany
  • Bruno Tassin
  • Zoran Zdravkovski
  • Mehmet A. OturanEmail author
Research Article



The degradation and mineralization of two triketone (TRK) herbicides, including sulcotrione and mesotrione, by the electro-Fenton process (electro-Fenton using Pt anode (EF-Pt), electro-Fenton with BDD anode (EF-BDD) and anodic oxidation with BDD anode) were investigated in acidic aqueous medium.


The reactivity of both herbicides toward hydroxyl radicals was found to depend on the electron-withdrawing effect of the aromatic chlorine or nitro substituents. The degradation of sulcotrione and mesotrione obeyed apparent first-order reaction kinetics, and their absolute rate constants with hydroxyl radicals at pH 3.0 were determined by the competitive kinetics method.

Results and discussion

The hydroxylation absolute rate constant (k abs) values of both TRK herbicides ranged from 8.20 × 108 (sulcotrione) to 1.01 × 109 (mesotrione) L mol−1 s−1, whereas those of the TRK main cyclic or aromatic by-products, namely cyclohexane 1,3-dione , (2-chloro-4-methylsulphonyl) benzoic acid and 4-(methylsulphonyl)-2-nitrobenzoic acid, comprised between 5.90 × 108 and 3.29 × 109 L mol−1 s−1. The efficiency of mineralization of aqueous solutions of both TRK herbicides was evaluated in terms of total organic carbon removal. Mineralization yields of about 97–98% were reached in optimal conditions for a 6-h electro-Fenton treatment time.


The mineralization process steps involved the oxidative opening of the aromatic or cyclic TRK by-products, leading to the formation of short-chain carboxylic acids, and, then, of carbon dioxide and inorganic ions.


Triketone herbicides Electro-Fenton Hydroxyl radical Degradation Mineralization 



M. Minir Murati gratefully thanks the French Embassy in Skopje (R. Macedonia) for a doctoral grant. Dr. Ahmad Dirany acknowledges the financial support of the Paris-Est Marne-la-Vallée University for an ATER position in the “Laboratoire Géomatériaux et Environnement” (LGE) during his post-doctoral research stay in Paris.


  1. Balci B, Oturan N, Cherrier R, Oturan MA (2009a) Degradation of atrazine in aqueous medium by electrocatalytically generated hydroxyl radicals. A kinetic and mechanistic study. Water Res 43:1924–1934CrossRefGoogle Scholar
  2. Balci B, Oturan MA, Oturan N, Sirés I (2009b) Decontamination of aqueous glyphosate, (aminomethyl) phosphonic acid, and glufosinate solutions by electro-Fenton-like process with Mn2+ as the catalyst. J Agr Food Chem 57:4888–4894CrossRefGoogle Scholar
  3. Bandala ER, Peláez MA, Dionysiou DD, Gelover S, Garcia J, Macías D (2007) Degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) using cobalt-peroxymonosulfate in Fenton-like process. J Photochem Photobiol A: Chem 186:357–363CrossRefGoogle Scholar
  4. Bensalah N, Khodary A, Adel-Wahab A (2011) Kinetic and mechanistic investigations of mesotrione degradation in aqueous medium by Fenton process. J Hazard Mater 189:479–485CrossRefGoogle Scholar
  5. Bonnet JL, Bonnemoy F, Dusser M, Bohatier J (2008) Toxicity assessment of the herbicides sulcotrione and mesotrione toward two reference environmental microorganisms: Tetrahymena pyrformis and Vibrio fischeri. Arch Environ Contam Toxicol 55:576–583CrossRefGoogle Scholar
  6. Boufia-Chergui S, Oturan N, Khalaf H, Oturan MA (2010) Parametric study on the effect of the ratio [H2O2]/[Fe3+] on the photo-Fenton degradation of Basic Blue 41 cationic azo dye. J Environ Sci Health A 45:622–629CrossRefGoogle Scholar
  7. Brillas E, Baños MA, Garrido JA (2003) Mineralization of herbicide 3,6-dichloro-2-methoxybenzoic acid in aqueous medium by anodic oxidation, electro-Fenton and photoelectro-Fenton. Electrochim Acta 48:1697–1705CrossRefGoogle Scholar
  8. Brillas E, Baños MA, Skoumal M, Cabot PL, Garrido JA, Rodríguez RM (2007) Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes. Chemosphere 68:199–209CrossRefGoogle Scholar
  9. Brillas E, Sirés I, Oturan MA (2009) Electro-Fenton process and related electrochemical technologies based on Fenton’s reaction chemistry. Chem Rev 109:6570–6631CrossRefGoogle Scholar
  10. Chaabane H, Vulliet E, Joux F, Lantoine F, Conan P, Cooper JF, Coste CM (2007) Photodegradation of sulcotrione in various aquatic environments and toxicity of its photoproducts for some marine micro-organisms. Water Res 41:1781–1789CrossRefGoogle Scholar
  11. Chelme-Ayala P, El-Din MG, Smith DW (2010) Kinetics and mechanism of the degradation of two pesticides in aqueous solutions by ozonation. Chemosphere 78:557–562CrossRefGoogle Scholar
  12. Chiron S, Fernandez Alba A, Rodriguez A, Garcia Calvo E (2000) Pesticide chemical oxidation: state-of-the-art. Water Res 34:366–377CrossRefGoogle Scholar
  13. Cruz-González K, Torres-López O, García-León A, Guzmán-Mar JL, Reyes LH, Hernández-Ramírez A, Peralta-Hernández JM (2010) Determination of optimum operating parameters for Acid Yellow 36 decolorization by electro-Fenton process using BDD cathode. Chem Eng J 160:199–206CrossRefGoogle Scholar
  14. De Heredia JB, Torregrosa J, Dominguez JR, Peres JA (2001) Kinetic model for phenolic compound oxidation by Fenton’s reagent. Chemosphere 45:85–90CrossRefGoogle Scholar
  15. Diagne M, Oturan N, Oturan MA, Sirés I (2009) UV-C light-enhanced photo-Fenton oxidation of methyl parathion. Environ Chem Lett 7:261–265CrossRefGoogle Scholar
  16. Dirany A, Sirés I, Oturan N, Oturan MA (2010) Electrochemical abatement of the antibiotic sulfamethoxazole from water. Chemosphere 81:594–602CrossRefGoogle Scholar
  17. Farré MJ, Franch MI, Malato S, Ayllón JA, Peral J, Doménech X (2005) Degradation of some biorecalcitrant pesticides by homogeneous and heterogeneous photocatalytic ozonation. Chemosphere 58:1127–1133CrossRefGoogle Scholar
  18. Gallard H, De Laat J (2001) Kinetics of oxidation of chlorobenzenes and phenyl-ureas by Fe(II)/H2O2 and Fe(III)/H2O2. Evidence of reduction and oxidation reactions of intermediates by Fe(II) or Fe(III). Chemosphere 42:405–413CrossRefGoogle Scholar
  19. Guinea E, Garrido JA, Rodriguez RM, Cabot PL, Arias C, Centellas F, Brillas E (2010) Degradation of the fluoroquinolone enrofloxacin by electrochemical advanced oxidation processes based on hydrogen peroxide electrogeneration. Electrochim Acta 55:2101–2115CrossRefGoogle Scholar
  20. Haag RW, Yao D (1992) Rate constants for reaction of hydroxyl radicals with several drinking water contaminants. Environ Sci Technol 26:1005–1013CrossRefGoogle Scholar
  21. Hammami S, Oturan N, Bellakhal N, Dachraoui M, Oturan MA (2007) Oxidative degradation of direct orange 61 by electro-Fenton process using a carbon felt electrode: Application of the experimental design methodology. J Electroanal Chem 610:75–84CrossRefGoogle Scholar
  22. Hammami S, Bellakhal N, Oturan N, Oturan MA, Dachraoui M (2008) Degradation of Acid Orange 7 by electrochemically generated OH radicals in acidic aqueous medium using a boron-doped diamond or platinum anode. A mechanistic study. Chemosphere 73:678–684CrossRefGoogle Scholar
  23. Kaichouh G, Oturan N, Oturan MA, El Hourch A, El Kacemi K (2008) Mineralization of herbicides imazapyr and imazaquin in aqueous medium by, Fenton, photo-Fenton and electro-Fenton processes. Environ Technol 29:489–496CrossRefGoogle Scholar
  24. Kesraoui-Abdessalem A, Oturan N, Bellakhal N, Dachraoui M, Oturan MA (2008) Experimental design methodology applied to electro-Fenton treatment for degradation of herbicide chlortoluron. Appl Catal B-Environ 78:334–341CrossRefGoogle Scholar
  25. Kesraoui-Abdessalem A, Bellakhal N, Oturan N, Dachraoui M, Oturan MA (2010) Treatment of a mixture of three pesticides by photo- and electro-Fenton process. Desalination 250:450–455CrossRefGoogle Scholar
  26. Konstantinou KI, Albanis AT (2003) Photocatalytic transformation of pesticides in aqueous titanium dioxide suspensions using artificial and solar light: intermediates and degradation pathways. Appl Catal B-Environ 42:319–335CrossRefGoogle Scholar
  27. Kowalkowski T, Gadzala-Kopciuch M, Kosobucki R, Krupczynska K, Ligor T, Buszewski B (2007) Organic and inorganic pollution of the Vistula River basin. J Environ Sci Health A 42:421–426CrossRefGoogle Scholar
  28. Neyens E, Baeyens J (2003) Review of classic Fenton’s peroxidation as an advanced oxidation technique. J Hazard Mater 98:33–50CrossRefGoogle Scholar
  29. Oturan MA (2000) An ecologically effective water treatment technique using electrochemically generated hydroxyl radicals for in situ destruction of organic pollutants. Application to herbicide 2,4-D. J Appl Electrochem 30:477–482CrossRefGoogle Scholar
  30. Oturan N, Oturan MA (2005) Degradation of three pesticides used in viticulture by electrogenerated Fenton’s reagent. Agron Sustain Dev 25:267–270CrossRefGoogle Scholar
  31. Oturan MA, Pinson J, Bizot J, Deprez D, Terlain B (1992) Reaction of inflammation inhibitors with chemically and electrochemically generated hydroxyl radicals. J Electroanal Chem 334:103–109CrossRefGoogle Scholar
  32. Oturan MA, Pimentel M, Oturan N, Sirés I (2008a) Reaction sequence for the mineralization of the short-chain carboxylic acids usually formed upon cleavage of aromatics during electrochemical Fenton treatment. Electrochim Acta 54:173–182CrossRefGoogle Scholar
  33. Oturan N, Trajkovska S, Oturan MA, Couderchet M, Aaro JJ (2008b) Study of the toxicity of diuron and its metabolites formed in aqueous medium during application of the electrochemical advanced oxidation process “electro-Fenton”. Chemosphere 73:1550–1556CrossRefGoogle Scholar
  34. Oturan N, Panizza M, Oturan MA (2009a) Cold incineration of chlorophenols in aqueous solution by electro-Fenton process. Effect of number and position of chlorine atoms on the degradation kinetics. J Phys Chem A 113:10988–10993CrossRefGoogle Scholar
  35. Oturan N, Sirés I, Oturan MA, Brillas E (2009b) Degradation of pesticides in aqueous medium by electro-Fenton and related methods. A review. J Environ Eng Manag 19:35–255Google Scholar
  36. Oturan MA, Edelahi MC, Oturan N, Aaron JJ (2010a) Kinetics of oxidative degradation/mineralization pathways of the phenylurea herbicides diuron, monuron and fenuron in water during application of the electro-Fenton process. Appl Catal B-Environ 97:82–89CrossRefGoogle Scholar
  37. Oturan N, Zhou MH, Oturan MA (2010b) Metomyl degradation by electro-Fenton and electro-Fenton like processes: a kinetics study of the effect of the nature and concentration of some transition metal ions as catalyst. J Phys Chem A 114:10605–10611CrossRefGoogle Scholar
  38. Özcan A, Şahin Y, Koparal AS, Oturan MA (2008a) Degradation of picloram by the electro-Fenton process. J Hazard Mater 153:718–727CrossRefGoogle Scholar
  39. Özcan A, Şahin Y, Koparal AS, Oturan MA (2008b) Propham mineralization in aqueous medium by anodic oxidation using boron-doped diamond anode. Experimental parameters’ influence on degradation kinetics and mineralization efficiency. Water Res 42:2889–2898CrossRefGoogle Scholar
  40. Özcan A, Şahin Y, Koparal AS, Oturan MA (2008c) Carbon sponge as a new cathode material for the electro-Fenton process. Comparison with carbon felt cathode and application to degradation of synthetic dye Basic Blue 3 in aqueous medium. J Electroanal Chem 616:71–78CrossRefGoogle Scholar
  41. Özcan A, Oturan MA, Oturan N, Şahin Y (2009) Removal of Acid Orange 7 from water by electrochemically generated Fenton’s reagent. J Hazard Mater 163:1213–1220CrossRefGoogle Scholar
  42. Özcan A, Oturan N, Şahin Y, Oturan MA (2010) Electro-Fenton treatment of aqueous clopyralid solutions. Inter J Environ Anal Chem 90:478–486CrossRefGoogle Scholar
  43. Panizza M, Cerisola G (2001) Removal of organic pollutants from industrial wastewater by electrogenerated Fenton’s reagent. Water Res 35:3987–3992CrossRefGoogle Scholar
  44. Panizza M, Cerisola G (2005) Application of diamond electrodes to electrochemical processes. Electrochim Acta 51:191–199CrossRefGoogle Scholar
  45. Panizza M, Cerisola G (2009) Electro-Fenton degradation of synthetic dyes. Water Res 43:339–344CrossRefGoogle Scholar
  46. Panizza M, Oturan MA (2011) Degradation of Alizarin Red by electro-Fenton process using a carbon-felt cathode. Electrochim Acta 56:7084–7084CrossRefGoogle Scholar
  47. Panizza M, Delucchi M, Sires I (2010) Electrochemical process for the treatment of landfill leachate. J Appl Electrochem 40:1721–1727CrossRefGoogle Scholar
  48. Pignatello JJ, Oliveros E, MacKay A (2006) Advanced oxidation processes for organic contaminant destruction based on the Fenton reaction and related chemistry. Crit Rev Environ Sci Technol 36:1–84CrossRefGoogle Scholar
  49. Richardson SD, Thruston AD, Collette TW, Patterson KS, Lykins J, Ireland JC (1996) Identification of TiO2/UV disinfection products in drinking water. Environ Sci Technol 30:3327–3334CrossRefGoogle Scholar
  50. Ruiz EJ, Hernandez-Ramirez A, Peralta-Hernandez JM, Arias C, Brillas E (2011) Application of solar photoelectro-Fenton technology to azo dyes mineralization: Effect of current density, Fe2+ and dye concentrations. Chem Eng J 171:385–392CrossRefGoogle Scholar
  51. Sirés I, Oturan N, Guivarch E, Oturan MA (2008) Efficient removal of triphenylmethane dyes from aqueous medium by in-situ electrogenerated Fenton’s reagent at carbon-felt cathode. Chemosphere 72:592–600CrossRefGoogle Scholar
  52. Ter Halle A, Richard C (2006) Simulated solar light irradiation of mesotrione in natural waters. Environ Sci Technol 40:3842–3847CrossRefGoogle Scholar
  53. Ter Halle A, Drncova D, Richard C (2006) Phototransformation of the herbicide sulcotrione on maize cuticular wax. Environ Sci Technol 40:2989–2995CrossRefGoogle Scholar
  54. Ter Halle A, Piquet A, Richard C (2007) An actual scenario that demonstrates sulcotrione photodegradation on maize leaves after spraying. Environ Chem 4:256–259CrossRefGoogle Scholar
  55. Wiszniowski J, Ter Halle A, Richard C, Hitmi A, Ledoigt G (2009) Photodegradation product of sulcotrione and the physiological response of maize (Zea mays) and white mustard (Sinapis alba). Chemosphere 74:1224–1230CrossRefGoogle Scholar
  56. Yu BS, Zeng JB, Gong LF, Zhang MS, Zhang LM, Chen X (2007) Investigation of the photocatalytic degradation of organochlorine pesticides on a nano-TiO2 coated film. Talanta 72:1667–1674CrossRefGoogle Scholar
  57. Zhang H, Zhang DB, Zhou JY (2006) Removal of COD from landfill leachate by electro-Fenton method. J Hazard Mater 135:106–111CrossRefGoogle Scholar
  58. Zhou MH, He HJ (2007) Degradation of azo dye by three clean advanced oxidation processes: Wet oxidation, electrochemical oxidation and wet electrochemical oxidation—A comparative study. Electrochim Acta 53:1902–1910CrossRefGoogle Scholar
  59. Zhou MH, Yu QH, Lei LC (2008) The preparation and characterization of a graphite-PTFE cathode system for the decolorization of CI Acid Red 2. Dyes Pigments 77:129–136CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Minir Murati
    • 1
  • Nihal Oturan
    • 1
  • Jean-Jacques Aaron
    • 1
  • Ahmad Dirany
    • 1
  • Bruno Tassin
    • 2
  • Zoran Zdravkovski
    • 3
  • Mehmet A. Oturan
    • 1
    Email author
  1. 1.Laboratoire Géomatériaux et Environnement (LGE)Université Paris-EstMarne-La-Vallée Cedex 2France
  2. 2.Ecole Ponts ParisTech, Laboratoire Eau Environnement Systèmes UrbainsUniversité Paris-EstMarne-La-ValleeFrance
  3. 3.Institute of Chemistry, Faculty of Natural Sciences and MathematicsSs. Cyril & Methodius UniversitySkopjeMacedonia

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