Skip to main content
SpringerLink
Log in

Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics, reaction intermediates, and toxicity assessment

  • Electrochemical advanced oxidation processes for removal of toxic/persistent organic pollutants from water
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

The degradation of 230 mL of a 0.6-mM sulfanilamide solution in 0.05 M Na2SO4 of pH 3.0 has been studied by electro-Fenton process. The electrolytic cell contained either a Pt or boron-doped diamond (BDD) anode and a carbon-felt cathode. Under these conditions, organics are oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between initially added (and then electrochemically regenerated) Fe2+ and cathodically generated H2O2. From the decay of sulfanilamide concentration determined by reversed-phase liquid chromatography, an optimum Fe2+ concentration of 0.20 mM in both cells was found. The drug disappeared more rapidly using BDD than Pt, and, in both cases, it was more quickly removed with raising applied current. Almost total mineralization was achieved using the BDD/carbon-felt cell, whereas the alternative use of Pt anode led to a slightly lower mineralization degree. In both cells, the degradation rate was accelerated at higher current but with the concomitant fall of mineralization current efficiency due to the greater increase in rate of the parasitic reactions of hydroxyl radicals. Reversed-phase liquid chromatography allowed the identification of catechol, resorcinol, hydroquinone, p-benzoquinone, and 1,2,4-trihydroxybenzene as aromatic intermediates, whereas ion exclusion chromatography revealed the formation of malic, maleic, fumaric, acetic, oxalic, formic, and oxamic acids. NH4 +, NO3 −, and SO4 2− ions were released during the electro-Fenton process. A plausible reaction sequence for sulfanilamide mineralization involving all detected intermediates has been proposed. The toxicity of the solution was assessed from the Vibrio fischeri bacteria luminescence inhibition. Although it acquired its maximum value at short electrolysis time, the solution was completely detoxified at the end of the electro-Fenton treatment, regardless of the anode used.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  • Andreozzi R, Caprio V, Ciniglia C, De Champdoré M, Lo Giudice R, Marotta R, Zuccato E (2004) Antibiotics in the environment: occurrence in Italian STPs, fate, and preliminary assessment on algal toxicity of amoxicillin. Environ Sci Technol 38:6832–6838

    Article  CAS  Google Scholar 

  • Besse J-P, Garric J (2008) Human pharmaceuticals in surface waters. Implementation of a prioritization methodology and application to the French situation. Toxicol Lett 176:104–123

    Article  CAS  Google Scholar 

  • Boye B, Dieng MM, Brillas E (2003) Electrochemical degradation of 2,4,5-trichlorophenoxyacetic acid in aqueous medium by peroxi-coagulation. Effect of pH and UV light. Electrochim Acta 48:781–790

    Article  CAS  Google Scholar 

  • Brillas E, Sirés I, Oturan MA (2009) Electro-Fenton process and related electrochemical technologies based on Fenton’s reaction chemistry. Chem Rev 109:6570–6631

    Article  CAS  Google Scholar 

  • Campagnolo ER, Johnson KR, Karpati A, Rubin CS, Kolpin DW, Meyer MT, Esteban JE, Currier RW, Smith K, Thu KM, McGeehin M (2002) Antimicrobial residues in animal waste and water resources proximal to large-scale swine and poultry feeding operations. Sci Total Environ 299:89–95

    Article  CAS  Google Scholar 

  • Capleton AC, Courage C, Rumsby P, Holmes P, Stutt E, Boxall ABA, Levy LS (2006) Prioritising veterinary medicines according to their potential indirect human exposure and toxicity profile. Toxicol Lett 163:213–223

    Article  CAS  Google Scholar 

  • Clara M, Strenn B, Gans O, Martinez E, Kreuzinger N, Kroiss H (2005) Removal of selected pharmaceuticals, fragrances and endocrine disrupting compounds in a membrane bioreactor and conventional wastewater treatment plants. Water Res 39:4797–4807

    Article  CAS  Google Scholar 

  • Crane M, Watts C, Boucard T (2006) Chronic aquatic environmental risks from exposure to human pharmaceuticals. Sci Total Environ 367:23–41

    Article  CAS  Google Scholar 

  • Cruz-Gonzalez 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 160:199–206

    Article  CAS  Google Scholar 

  • Daughton CG, Ternes TA (1999) Pharmaceuticals and personal care products in the environment: agents of subtle change? Environ Health Perspect 107:907–938

    Article  CAS  Google Scholar 

  • Dirany A, Sirés I, Oturan N, Oturan MA (2010) Electrochemical abatement of the antibiotic sulfamethoxazole from water. Chemosphere 81:594–602

    Article  CAS  Google Scholar 

  • Dirany A, Efremova-Aaron S, Oturan N, Sirés I, Oturan MA, Aaron J-J (2011) Study of the toxicity of sulfamethoxazole and its degradation products in water by a bioluminescence method during application of the electro-Fenton treatment. Anal Bioanal Chem 400:353–360

    Article  CAS  Google Scholar 

  • Dirany A, Sirés I, Oturan N, Özcan A, Oturan MA (2012) Electrochemical treatment of the antibiotic sulfachloropyridazine: kinetics, reaction pathways, and toxicity evolution. Environ Sci Technol 46:4074–4082

    Article  CAS  Google Scholar 

  • El-Ghenymy A, Garrido JA, Rodríguez RM, Cabot PL, Centellas F, Arias C, Brillas E (2013a) Degradation of sulfanilamide in acidic medium by anodic oxidation with a boron-doped diamond anode. J Electroanal Chem 689:149–157

    Article  CAS  Google Scholar 

  • El-Ghenymy A, Cabot PL, Centellas F, Garrido JA, Rodríguez RM, Arias C, Brillas E (2013b) Electrochemical incineration of the antimicrobial sulfamethazine at a boron-doped diamond anode. Electrochim Acta 90:254–264

    Article  CAS  Google Scholar 

  • Garcia-Segura S, Garrido JA, Rodríguez RM, Cabot PL, Centellas F, Arias C, Brillas E (2012) Mineralization of flumequine in acidic medium by electro-Fenton and photoelectro-Fenton processes. Water Res 46:2067–2076

    Article  CAS  Google Scholar 

  • 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 73:678–684

    Article  CAS  Google Scholar 

  • Hamza M, Abdelhedi R, Brillas E, Sirés I (2009) Comparative electrochemical degradation of the triphenylmethane dye methyl violet with boron-doped diamond and Pt anodes. J Electroanal Chem 627:41–50

    Article  CAS  Google Scholar 

  • Homem V, Santos L (2011) Degradation and removal methods of antibiotics from aqueous matrices—a review. J Environ Manag 92:2304–2347

    Article  CAS  Google Scholar 

  • Isarain-Chávez E, Arias C, Cabot PL, Centellas F, Rodríguez RM, Garrido JA, Brillas E (2010) Mineralization of the drug beta-blocker atenolol by electro-Fenton and photoelectro-Fenton using an air-diffusion cathode for H2O2 electrogeneration combined with a carbon-felt cathode for Fe2+ regeneration. Appl Catal B Environ 96:361–369

    Article  Google Scholar 

  • Jarnheimer P, Ottoson J, Lindberg R, Stenström T, Johansson M, Tysklind M, Winner M, Olsen B (2004) Fluoroquinolone antibiotics in a hospital sewage line; occurrence, distribution and impact on bacterial resistance. Scand J Infect Dis 36:725–755

    Google Scholar 

  • Jia A, Hu J, Wu X, Peng H, Wu S, Dong Z (2011) Occurrence and source apportionment of sulfonamides and their metabolites in Liaodong Bay and the adjacent Liao River basin, North China. Environ Toxicol Chem 30:1252–1260

    Google Scholar 

  • Kay P, Blackwell PA, Boxall ABA (2005) A lysimeter experiment to investigate the leaching of veterinary antibiotics through a clay soil and comparison with field data. Environ Pollut 134:333–341

    Article  CAS  Google Scholar 

  • Khataee AR, Safarpour M, Zarei M, Aber S (2011) Electrochemical generation of H2O2 using immobilized carbon nanotubes on graphite electrode fed with air: investigation of operational parameters. J Electroanal Chem 659:63–68

    Article  CAS  Google Scholar 

  • Khetan SK, Collins TJ (2007) Human pharmaceuticals in the aquatic environment: a challenge to green chemistry. Chem Rev 107:2319–2364

    Article  CAS  Google Scholar 

  • Kim Y, Choi K, Jung J, Park S, Kim P-G, Park J (2007) Aquatic toxicity of acetaminophen, carbamazepine, cimetidine, diltiazem and six major sulfonamides, and their potential ecological risks in Korea. Environ Int 33:370–375

    Article  CAS  Google Scholar 

  • Klavarioti M, Mantzavinos D, Kassinos D (2009) Removal of residual pharmaceuticals from aqueous systems by advanced oxidation processes. Environ Int 35:402–417

    Article  CAS  Google Scholar 

  • Kümmerer K (2009) Antibiotics in the aquatic environment—a review—part I. Chemosphere 75:417–434

    Article  Google Scholar 

  • Liu L, Zhao G, Wu M, Lei Y, Geng R (2009) Electrochemical degradation of chlorobenzene on boron-doped diamond and platinum electrodes. J Hazard Mater 168:179–186

    Article  CAS  Google Scholar 

  • Luo Y, Xu L, Rysz M, Wang Y, Zhang H, Alvarez PJJ (2011) Occurrence and transport of tetracycline, sulfonamide, quinolone, and macrolide antibiotics in the Haihe river basin, China. Environ Sci Technol 45:1827–1833

    Google Scholar 

  • McClellan K, Halden RU (2010) Occurrence and loss over three years of 72 pharmaceuticals and personal care products from biosolids-soil mixtures in outdoor mesocosms. Water Res 44:6011–6020

    Article  Google Scholar 

  • Munir M, Wong K, Xagoraraki I (2011) Release of antibiotic resistant bacteria and genes in the effluent and biosolids of five wastewater utilities in Michigan. Water Res 45:681–693

    Article  CAS  Google Scholar 

  • Oturan N, Oturan MA (2005) Degradation of three pesticides used in viticulture by electrogenerated Fenton’s reagent. Agron Sustain Dev 25:267–270

    Article  CAS  Google Scholar 

  • Oturan N, Trajkovska S, Oturan MA, Couderchet M, Aaron J-J (2008) Study of the toxicity of diuron and its metabolites formed in aqueous medium during application of the electrochemical advanced oxidation process “electro-Fenton”. Chemosphere 73:1550–1556

    Article  CAS  Google Scholar 

  • Özcan A, Sahin Y, Savas Koparal A, Oturan MA (2008a) Carbon sponge as a new 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 616:71–78

    Article  Google Scholar 

  • Özcan A, Şahin Y, Koparal AS, Oturan MA (2008b) Degradation of picloram by the electro-Fenton process. J Hazard Mater 153:718–727

    Article  Google Scholar 

  • Özcan A, Şahin Y, Koparal AS, Oturan MA (2008c) Propham mineralization in aqueous medium by anodic oxidation using boron-doped diamond anode. Experimental parameters’ influence on degradation kinetics and mineralization efficiency. Water Res 42:2889–2898

    Article  Google Scholar 

  • Panizza M, Cerisola G (2009) Direct and mediated anodic oxidation of organic pollutants. Chem Rev 109:6541–6569

    Article  CAS  Google Scholar 

  • Panizza M, Oturan MA (2011) Degradation of Alizarin Red by electro-Fenton process using a graphite-felt cathode. Electrochim Acta 56:7084–7087

    Article  CAS  Google Scholar 

  • Pomati F, Orlandi C, Clerici M, Luciani F, Zuccato E (2008) Effects and interactions in an environmentally relevant mixture of pharmaceuticals. Toxicol Sci 102:129–137

    Article  CAS  Google Scholar 

  • Ramírez C, Saldaña A, Hernández B, Acero R, Guerra A, Garcia-Segura S, Brillas E, Peralta-Hernández JM (2013) Electrochemical oxidation of methyl orange azo dye at pilot flow plant using BDD technology. J Ind Eng Chem 19:571–579

    Article  Google Scholar 

  • Sarmah AK, Meyer MT, Boxall ABA (2006) A global perspective on the use, sales, exposure pathways, occurrence, fate and effects of veterinary antibiotics (VAs) in the environment. Chemosphere 65:725–759

    Article  CAS  Google Scholar 

  • Sim W-J, Lee J-W, Oh J-E (2010) Occurrence and fate of pharmaceuticals in wastewater treatment plants and rivers in Korea. Environ Pollut 158:1938–1947

    Article  CAS  Google Scholar 

  • Sirés I, Brillas E (2012) Remediation of water pollution caused by pharmaceutical residues based on electrochemical separation and degradation technologies: a review. Environ Int 40:212–229

    Article  Google Scholar 

  • Sirés I, Garrido JA, Rodríguez RM, Brillas E, Oturan N, Oturan MA (2007a) Catalytic behavior of the Fe3+/Fe2+ system in the electro-Fenton degradation of the antimicrobial chlorophene. Appl Catal B Environ 72:382–394

    Article  Google Scholar 

  • Sirés I, Oturan N, Oturan MA, Rodríguez RM, Garrido JA, Brillas E (2007b) Electro-Fenton degradation of antimicrobials triclosan and triclocarban. Electrochim Acta 52:5493–5503

    Article  Google Scholar 

  • Sirés I, Centellas F, Garrido JA, Rodríguez RM, Arias C, Cabot PL, Brillas E (2007c) Mineralization of clofibric acid by electrochemical advanced oxidation processes using a boron-doped diamond anode and Fe2+ and UVA light as catalysts. Appl Catal B Environ 72:373–381

    Article  Google Scholar 

  • Vieno N, Tuhkanen T, Kronberg L (2007) Elimination of pharmaceuticals in sewage treatment plants in Finland. Water Res 41:1001–1012

    Article  CAS  Google Scholar 

  • Zarei M, Khataee AR, Ordikhani-Seyedlar R, Fathinia M (2010) Photoelectro-Fenton combined with photocatalytic process for degradation of an azo dye using supported TiO2 nanoparticles and carbon nanotube cathode: neural network modeling. Electrochim Acta 55:7259–7265

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The grant awarded to A. El-Ghenymy by MEC (Ministerio de Educación y Ciencia, Spain) and financial support from MICINN (Ministerio de Ciencia e Innovación, Spain) under project CTQ2010-16164/BQU, co-financed with FEDER funds, are acknowledged.

Conflict of interest

The author(s) confirm that this article content has no conflicts of interest.

Author information

Authors and Affiliations

  1. Laboratori d’Electroquímica dels Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Spain

    Abdellatif El-Ghenymy, Rosa María Rodríguez & Enric Brillas

  2. Laboratoire Géomatériaux et Environnement (LGE), Université Paris-Est, EA 4508, UPEMLV, 77454, Marne-la-Vallée, France

    Nihal Oturan & Mehmet A. Oturan

Authors
  1. Abdellatif El-Ghenymy
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Rosa María Rodríguez
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Enric Brillas
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Nihal Oturan
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Mehmet A. Oturan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Enric Brillas.

Additional information

Responsible editor: Philippe Garrigues

Rights and permissions

Reprints and permissions

About this article

Cite this article

El-Ghenymy, A., Rodríguez, R.M., Brillas, E. et al. Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics, reaction intermediates, and toxicity assessment. Environ Sci Pollut Res 21, 8368–8378 (2014). https://doi.org/10.1007/s11356-014-2773-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-014-2773-3

Keywords

Search

Navigation