Reaction Kinetics, Mechanisms and Catalysis

, Volume 108, Issue 1, pp 17–39 | Cite as

UV-assisted persulfate oxidation: the influence of cation type in the persulfate salt on the degradation kinetics of an azo dye pollutant

  • Igor PeternelEmail author
  • Hrvoje Kusic
  • Vedrana Marin
  • Natalija Koprivanac


With the aim to investigate the influence of UV-assisted persulfate oxidation operating parameters (cation type in persulfate salt, persulfate concentration and initial pH), the empirical/modeling approach applying full factorial experimental design (FFD) combined with response surface methodology (RSM) and mechanistic modeling (MM) was used. The efficiency of UV-assisted persulfate oxidation as a wastewater treatment method and the dependence on the aforementioned process parameters was evaluated in the case study where an azo dye (C.I. Acid Orange 7—AO7) was used as a model pollutant in water matrix. The FFD matrix with three independent variables representing the studied process parameters established experimental combinations, on which the UV-assisted persulfate oxidation process response, the AO7 decolorization rate was determined and correlated using RSM over quadratic polynomial equations, i.e. RSM model. The significance and accuracy of the developed RSM model was evaluated on the basis of analysis of variance and obtained statistical parameters (R 2, F, p), used also to examine the influence of studied process parameters. It was determined that the persulfate salt is the most influential process parameter, followed by rather high combined influence of initial pH and cation type, indicating the practical implications regarding the cation type. The MM used to describe the UV-assisted persulfate oxidation system showed high accuracy in predicting the AO7 degradation monitored over several parameters (decolorization, degradation of naphthalene and benzene structures, as well as overall mineralization) as well as high flexibility covering the broad pH range of application set by different cation type ion the persulfate salt.


Persulfate Oxidation UV irradiation Statistical modeling Kinetic modeling Azo dye 



We would like to acknowledge on the financial support both from the Ministry of Science, Education and Sport, Republic of Croatia (Project #125-1253092-1981).


  1. 1.
    Viessman W Jr, Hammer MJ (2005) Water supply and pollution control, 7th edn. Pearson Prentice Hall, Upper Saddle RiverGoogle Scholar
  2. 2.
    Koprivanac N, Kusic H (2009) Hazardous organic pollutants in colored wastewaters. Nova Science Publishers, HauppaugeGoogle Scholar
  3. 3.
    Gogate R, Pandit B (2004) A review of imperative technologies for wastewater treatment I: oxidation technologies at ambient conditions. Adv Environ Res 8:501–551CrossRefGoogle Scholar
  4. 4.
    Parsons S (2004) Advanced oxidation processes for water and wastewater treatment. IWA Publishing, LondonGoogle Scholar
  5. 5.
    Kusic H, Jovic M, Kos N, Koprivanac N, Marin V (2010) The comparison of photooxidation processes for the minimization of organic load of colored wastewater applying the response surface methodology. J Hazard Mater 183:189–202CrossRefGoogle Scholar
  6. 6.
    Kusic H, Juretic D, Koprivanac N, Marin V, Loncaric Bozic A (2011) Photooxidation processes for an azo dye in aqueous media: modeling of degradation kinetic and ecological parameters evaluation. J Hazard Mater 185:1558–1568CrossRefGoogle Scholar
  7. 7.
    Kamel D, Sihem A, Halima C, Tahar S (2009) Decolourization process of an azoic dye (Congo red) by photochemical methods in homogeneous medium. Desalination 247:412–422CrossRefGoogle Scholar
  8. 8.
    Rivas FJ, Beltrán FJ, Encinas A (2012) Removal of emergent contaminants: integration of ozone and photocatalysis. J Environ Manag 100:10–15CrossRefGoogle Scholar
  9. 9.
    Kralik P, Kusic H, Koprivanac N, Loncaric Bozic A (2010) Degradation of chlorinated hydrocarbons by UV/H2O2: the application of experimental design and kinetic modeling approach. Chem Eng J 158:154–166CrossRefGoogle Scholar
  10. 10.
    Antoniou MG, de la Cruz AA, Dionysiou DD (2010) Degradation of microcystin-LR using sulfate radicals generated through photolysis, thermolysis and e-transfer mechanisms. Appl Catal B 96(3–4):290–298Google Scholar
  11. 11.
    Jo CH, Dietrich AM, Tanko JM (2011) Simultaneous degradation of disinfection byproducts and earthy-musty odorants by the UV/H2O2 advanced oxidation process. Water Res 45:2507–2516CrossRefGoogle Scholar
  12. 12.
    Metz DH, Meyer M, Dotson A, Beerendonk E, Dionysiou DD (2011) The effect of UV/H2O2 treatment on disinfection by-product formation potential under simulated distribution system conditions. Water Res 45:3969–3980CrossRefGoogle Scholar
  13. 13.
    Kusic H, Koprivanac N, Loncaric Bozic A (2006) Minimization of organic pollutant content in aqueous solution by means of AOPs: UV- and ozone-based technologies. Chem Eng J 123:127–137CrossRefGoogle Scholar
  14. 14.
    Yoon S-H, Jeong S, Lee S (2012) Oxidation of bisphenol A by UV/S2O8 2−: comparison with UV/H2O2. Environ Technol 33(1):123–128CrossRefGoogle Scholar
  15. 15.
    Criquet J, Leitner NKV (2009) Degradation of acetic acid with sulfate radical generated by persulfate ions photolysis. Chemosphere 77:194–200CrossRefGoogle Scholar
  16. 16.
    Huang K-C, Couttenye RA, Hoag GE (2002) Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE). Chemosphere 49:413–420CrossRefGoogle Scholar
  17. 17.
    Salari D, Niaei A, Aber S, Rasoulifard MH (2009) The photooxidative destruction of C.I. Basic Yellow 2 using UV/S2O8 2− process in a rectangular continuous photoreactor. J Hazard Mater 166:61–66CrossRefGoogle Scholar
  18. 18.
    Beltran FJ (2003) In: Tarr MA (ed) Chemical degradation methods for wastes and pollutants, environmental and industrial applications. Marcel Dekker Inc., New YorkGoogle Scholar
  19. 19.
    Kusic H, Koprivanac N, Loncaric Bozic A (2011) Treatment of chlorophenols in water matrix by UV/ferrioxalate system: Part I. Key process parameter evaluation by response surface methodology. Desalination 279:258–268CrossRefGoogle Scholar
  20. 20.
    Kusic H, Koprivanac N, Loncaric Bozic A (2011) Treatment of chlorophenols in water matrix by UV/ferri-oxalate system: Part II. Degradation mechanisms and ecological parameters evaluation. Desalination 280:208–216CrossRefGoogle Scholar
  21. 21.
    Venkataraman K (1970) The chemistry of synthetic dyes. Academic Press, New YorkGoogle Scholar
  22. 22.
    Nicole I, De Laat J, Dore M, Duguet JP, Bonnel C (1990) Utilisation du rayonnement ultraviolet dans le traitement des eaux: mesure du flux photonique par actinometrie chimique au peroxyde d’hydrogene: use of U.V. radiation in water treatment: measurement of photonic flux by hydrogen peroxide actinometry. Water Res 24:157–168CrossRefGoogle Scholar
  23. 23.
    Dopar M, Kusic H, Koprivanac N (2011) Treatment of simulated industrial wastewater by photo-Fenton process: Part I. The optimization of process parameters using design of experiments (DOE). Chem Eng J 173:267–279CrossRefGoogle Scholar
  24. 24.
    Peternel I, Grcic I, Koprivanac N (2010) Degradation of reactive azo dye by UV/peroxodisulfate system: an experimental design approach. React Kinet Mech Cat 100:33–44Google Scholar
  25. 25.
    Frigon NL, Mathews D (1997) Practical guide to experimental design. Wiley, New YorkGoogle Scholar
  26. 26.
    Montgomery DC (2005) Design and analysis of experiments. Wiley, New YorkGoogle Scholar
  27. 27.
    Myer RH, Montgomery DC (2002) Response surface methodology: process and product optimization using designed experiment, 2nd edn. Wiley, New YorkGoogle Scholar
  28. 28.
    Kusic H, Koprivanac N, Loncaric Bozic A (2012) Application of sensitivity and flux analyses for the reduction of model predicting the photooxidative degradation of an azo dye in aqueous media. Environ Model Assess. doi: 10.1007/s10666-012-9322-6 Google Scholar
  29. 29.
    Connors KA (1990) Chemical kinetics: the study of reaction rates in solution. Wiley-VCH, New YorkGoogle Scholar
  30. 30.
    Stat-Ease (2008) Multifactor RSM Tutorial (Part 2-Optimization). Design-Expert software Version 7.1.5 User’s Guide.
  31. 31.
    Box GEP, Cox DR (1964) An analysis of transformations. J R Stat Soc B 26:211–246Google Scholar
  32. 32.
    Yetilmezsoy K, Demirel S, Vanderbei RJ (2009) Response surface modeling of Pb(II) removal from aqueous solution by Pistacia vera L.: Box–Behnken experimental design. J Hazard Mater 171:551–562CrossRefGoogle Scholar
  33. 33.
    Ray S, Lalman JA, Biswas N (2009) Using the Box–Benkhen technique to statistically model phenol photocatalytic degradation by titanium dioxide nanoparticles. Chem Eng J 150:15–24CrossRefGoogle Scholar
  34. 34.
    UNEP Publications, OECD report: persulfates. Accessed 21 May 2012
  35. 35.
    Ministry of Regional Development, Forestry and Water Management (2008) Directive on amendments of regulations for limit values of hazardous substances and other indicators in wastewater. The Official Gazette 94 (August 13, 2008), CroatiaGoogle Scholar
  36. 36.
    EC, Handbook on the Implementation of EC Environmental Legislation, Section 5: Water Protection Legislation, edited by Regional Environmental CenterGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2012

Authors and Affiliations

  • Igor Peternel
    • 1
    Email author
  • Hrvoje Kusic
    • 1
  • Vedrana Marin
    • 2
  • Natalija Koprivanac
    • 1
  1. 1.Faculty of Chemical Engineering and TechnologyUniversity of ZagrebZagrebCroatia
  2. 2.Department of Biomedical Sciences, College of MedicineFlorida State UniversityTallahasseeUSA

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