Removal of 2,4-Dichlorophenoxyacetic acid from water and organic by-product minimization by catalytic ozonation

  • Asogan N. Gounden
  • Sooboo Singh
  • Sreekantha B. JonnalagaddaEmail author
Research Article



2,4-dichlorophenoxyacetic acid (2,4-DCPA acid) is a toxic herbicide. Earlier studies to remove 2,4-DCPA acid from water used expensive and/or toxic reagents, resulting in the formation of toxic organic by-products (Org-BPs). This study evaluates the removal of 2,4-DCPA acid from aqueous media using uncatalysed and catalytic ozonation with Fe doped with Ni and Co respectively.


Mixed metal oxides of Ni and Co loaded on Fe respectively, prepared by co-precipitation and physical mixing were used as catalyst for ozone facilitated oxidation degradation of 2,4-DCPA acid. Their surface properties were determined by employing SEM, BET and NH3-TPD. HPLC, IC and TOC data were used for quantifying substrate and oxidation products.


Conversion of 2,4-DCPA acid increased from 38% in acidic water to 73% in basic water, however, only 26% of the total carbon was removed and 9.5% in the form of Org-BPs. With 7:3 Fe:Ni (Co-ppt) catalyst (surface area 253 m2 g−1; particle size 236 nm), 97% of pollutant was converted. Most importantly, 92% of carbon was removed and Org-BP formation was minimized to 1.5%. With 7:3 Fe:Ni (Mixed) catalyst (surface area 12 m2 g−1; particle size 1274 nm), 68% of 2,4-DCPA acid was converted, while 23% of TOC was removed, however, 66% of Org-BP’s still remained.


In uncatalysed ozonation degradation of 2,4-DCPA acid improved with the increase in hydroxide ion concentration. Ozonation in presence of 7:3 Fe:Ni (Co-ppt) catalyst resulted in highest activity for dechlorination, TOC removal and Org-BP minimization, thus improving the quality of contaminated water.


Catalytic ozonation 7:3 Fe:Ni (co-ppt) Total organic carbon Organic by-products 



The authors are thankful for the financial support from Mangosuthu University of Technology, University of Kwa-Zulu Natal and the National Research Foundation for successful completion of this invaluable work.

Author’s contributions

ANG conducted all the lab analysis and drafted this manuscript. All authors contributed to the review and finalization of this manuscript. All authors read and approved the final manuscript.

Compliance with ethical standards

Competing interests

The authors declare that they have no competing interests.

Consent for publication

Not applicable.

Ethics approval and consent to participate

Not applicable.


  1. 1.
    Mazza A, Piscitelli P, Neglia C, Rosa GD, Iannuzzi L. Illegal dumping of toxic waste and its effect on human health in Campania, Italy. Int J Environ Res Public Health. 2015;2(6):6818–31.CrossRefGoogle Scholar
  2. 2.
    Rahnama-Moghadam S, Hillis LD, Lange RA. Chapter 3 - environmental toxins and the heart A2 - Ramachandran, Meenakshisundaram, in Heart and toxins. Boston: Academic Press; 2015. p. 75–132.Google Scholar
  3. 3.
    Khoshnood M, Azizian S. Adsorption of 2,4-dichlorophenoxyacetic acid pesticide by graphitic carbon nanostructures prepared from biomasses. J Ind Eng Chem. 2012;18(5):1796–800.CrossRefGoogle Scholar
  4. 4.
    Bekbölet M, Yenigün O, Yücel I. Sorption studies of 2,4-D on selected soils. Water Air Soil Pollut. 1999;111(1):75–88.CrossRefGoogle Scholar
  5. 5.
    Tsyganok AI, Otsuka K. Selective dechlorination of chlorinated phenoxy herbicides in aqueous medium by electrocatalytic reduction over palladium-loaded carbon felt. Appl Catal B Environ. 1999;22(1):15–26.CrossRefGoogle Scholar
  6. 6.
    Kwan CY. Chu W. a study of the reaction mechanisms of the degradation of 2,4-dichlorophenoxyacetic acid by oxalate-mediated photooxidation. Water Res. 2004;38(19):4213–21.CrossRefGoogle Scholar
  7. 7.
    Rodríguez JL, Valenzuela MA, Poznyak T, Lartundo L, Chairez I. Reactivity of NiO for 2,4-D degradation with ozone: XPS studies. J Hazard Mater. 2013;262:472–81.CrossRefGoogle Scholar
  8. 8.
    Guzman-Perez CA, Soltan J, Robertson J. Catalytic ozonation of 2,4-dichlorophenoxyacetic acid using alumina in the presence of a radical scavenger. J Enviro Sci Health B. 2012;47(6):544–52.CrossRefGoogle Scholar
  9. 9.
    Soni KC, Shekar SC. Catalytic oxidation of bis (2-chloroethyl) ether on vanadia titania nanocatalyst. Arab J Chem. 2017:1–11.Google Scholar
  10. 10.
    Shahamat YD, Farzadkia M, Nasseri S, Mahvi AH, Gholami M, Esrafili A. Magnetic heterogeneous catalytic ozonation: a new removal method for phenol in industrial wastewater. J Environ Health Sci Eng. 2014;12(1):1–12.CrossRefGoogle Scholar
  11. 11.
    Beller M, Bolm C. Transition metals for organic synthesis. Weinheim: Wiley-VCH; 2004.CrossRefGoogle Scholar
  12. 12.
    Rakness K, Gordon G, Langlais B, Masschelein W, Matsumoto N, Richard Y, et al. Guideline for measurement of ozone concentration in the process gas from an ozone generator. Ozone: science. Engineering. 1996;18(3):209–29.Google Scholar
  13. 13.
    Kuo WS. Synergistic effects of combination of photolysis and ozonation on destruction of chlorophenols in water. Chemosphere. 1999;39(11):1853–60.CrossRefGoogle Scholar
  14. 14.
    Straehelin S, Hoigné J. Mechanism and kinetics of decomposition of ozone in water: rate of initiation by hydroxide ions and hydrogen peroxide. Environ Sci Technol. 1982;16:676–81.CrossRefGoogle Scholar
  15. 15.
    Gottschalk C, Libra JA, Saupe A. Ozonation of water and wastewater. In: Wiley-VCH; 2000.Google Scholar
  16. 16.
    Gounden AN, Singh S, Jonnalagadda SB. Simultaneous removal of 2,4,6-tribromophenol from water and bromate ion minimization by ozonation. J Hazard Mater. 2018;357:415–23.CrossRefGoogle Scholar
  17. 17.
    Staehelin J, Hoigné J. Decomposition of ozone in water in the presence of organic solutes acting as promoters and inhibitors of radical chain reactions. Environ Sci Technol. 1985;19:1206–13.CrossRefGoogle Scholar
  18. 18.
    Way TY, Wan CC. Heterogeneous photocatalytic oxidation of phenol with titanium dioxide powders. Ind Eng Chem Res. 1991;30:1293–300.CrossRefGoogle Scholar
  19. 19.
    Staehelin J, Hoigné J. Decomposition of ozone in water. Environ Sci Technol. 1982;16:676–81.CrossRefGoogle Scholar
  20. 20.
    Martins RC, Quinta-Ferreira RM. Catalytic ozonation of phenolic acids over a Mn–Ce–O catalyst. Appl Catal B Environ. 2009;90(1):268–77.CrossRefGoogle Scholar
  21. 21.
    Wu Z, Zhang L, Guan Q, Fu M, Ye D. Wu T. catalytic oxidation of toluene over au–co supported on SBA-15. Mater Res Bull. 2015;70:567–72.CrossRefGoogle Scholar
  22. 22.
    Wang Y, Xie Y, Sun H, Xiao J, Cao H, Wang S. 2D/2D nano-hybrids of γ-MnO2 on reduced graphene oxide for catalytic ozonation and coupling peroxymonosulfate activation. J Hazard Mater. 2016;301:6–64.Google Scholar
  23. 23.
    Nawrocki J, Fijołek L. Effect of aluminium oxide contaminants on the process of ozone decomposition in water. Appl Catal B Environ. 2013;142-3:533–7.CrossRefGoogle Scholar
  24. 24.
    Ikhlaq A, Brown DR, Kasprzyk-Hordern B. Catalytic ozonation for the removal of organic contaminants in water on alumina. Appl Catal B Environ. 2015;165:408–18.CrossRefGoogle Scholar
  25. 25.
    Jung H, Ahn Y, Choi H, Kim IS. Catalytic decomposition of ozone and para-chlorobenzoic acid (pCBA) in the presence of nanosized ZnO. Appl Catal B Environ. 2006;66(3–4):288–94.CrossRefGoogle Scholar
  26. 26.
    Silva GHR, Daniel LA, Bruning H, Rulkens WH. Anaerobic effluent disinfection using ozone: by-products formation. Bioresour Technol. 2010;10:6981–6.CrossRefGoogle Scholar
  27. 27.
    García O, Isarain-Chávez E, Garcia-Segura S, Brillas E, Peralta-Hernández JM. Study of the catalytic ozonation of humic substances in water and their ozonation by-products. Ozone Sci Eng. 1996;18:195–208.CrossRefGoogle Scholar

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© Springer Nature Switzerland AG 2018

Authors and Affiliations

  1. 1.Department of ChemistryMangosuthu University of TechnologyJacobsSouth Africa
  2. 2.School of Chemistry & PhysicsUniversity of KwaZulu-NatalDurbanSouth Africa

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