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Degradation of anti-inflammatory drug ketoprofen by electro-oxidation: comparison of electro-Fenton and anodic oxidation processes

  • Electrochemical advanced oxidation processes for removal of toxic/persistent organic pollutants from water
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Abstract

The electrochemical degradation of the nonsteroidal anti-inflammatory drug ketoprofen in tap water has been studied using electro-Fenton (EF) and anodic oxidation (AO) processes with platinium (Pt) and boron-doped diamond (BDD) anodes and carbon felt cathode. Fast degradation of the parent drug molecule and its degradation intermediates leading to complete mineralization was achieved by BDD/carbon felt, Pt/carbon felt, and AO with BDD anode. The obtained results showed that oxidative degradation rate of ketoprofen and mineralization of its aqueous solution increased by increasing applied current. Degradation kinetics fitted well to a pseudo-first-order reaction. Absolute rate constant of the oxidation of ketoprofen by electrochemically generated hydroxyl radicals was determined to be (2.8 ± 0.1) × 109 M−1 s−1 by using competition kinetic method. Several reaction intermediates such as 3-hydroxybenzoic acid, pyrogallol, catechol, benzophenone, benzoic acid, and hydroquinone were identified by high-performance liquid chromatography (HPLC) analyses. The formation, identification, and evolution of short-chain aliphatic carboxylic acids like formic, acetic, oxalic, glycolic, and glyoxylic acids were monitored with ion exclusion chromatography. Based on the identified aromatic/cyclic intermediates and carboxylic acids as end products before mineralization, a plausible mineralization pathway was proposed. The evolution of the toxicity during treatments was also monitored using Microtox method, showing a faster detoxification with higher applied current values.

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References

  • Beltran De Heredia J, Torregrosa J, Dominguez JR, Peres JA (2001) Kinetic model for phenolic compound oxidation by Fenton’s reagent. Chemosphere 45:85–90

    Article  CAS  Google Scholar 

  • Bendz D, Paxéus NA, Ginn TR, Loge FJ (2005) Occurrence and fate of pharmaceutically active compounds in the environment, a case study: Höje River in Sweden. J Hazard Mater 122:195–204

    Article  CAS  Google Scholar 

  • Benitez FJ, Acero JL, Real FJ, Rubio FJ, Leal AI (2001) The role of hydroxyl radicals for the decomposition of p-hydroxy phenylacetic acid in aqueous solutions. Water Res 35:1338–1343

    Article  CAS  Google Scholar 

  • Boye B, Dieng MM, Brillas E (2002) Degradation of herbicide 4-chlorophenoxyacetic acid by advanced electrochemical oxidation methods. Environ Sci Technol 36:3030–3035

    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 

  • Camacho-Muñoz D, Martín J, Santos JL, Aparicio I, Alonso E (2010) Occurrence, temporal evolution and risk assessment of pharmaceutically active compounds in Doñana Park (Spain). J Hazard Mater 183:602–608

    Article  Google Scholar 

  • Cañizares P, García-Gómez J, Lobato J, Rodrigo MA (2004) Modeling of wastewater electro-oxidation processes part I. General description and application to inactive electrodes. Ind Eng Chem Res 43:1915–1922

    Article  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, 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 

  • Fatta-Kassinos D, Vasquez MI, Kümmerer K (2011) Transformation products of pharmaceuticals in surface waters and wastewater formed during photolysis and advanced oxidation processes—degradation, elucidation of byproducts and assessment of their biological potency. Chemosphere 85:693–709

    Article  CAS  Google Scholar 

  • Fent K, Weston AA, Caminada D (2006) Ecotoxicology of human pharmaceuticals. Aquat Toxicol 76:122–159

    Article  CAS  Google Scholar 

  • González T, Domínguez JR, Palo P, Sánchez-Martín J, Cuerda-Correa EM (2011) Development and optimization of the BDD-electrochemical oxidation of the antibiotic trimethoprim in aqueous solution. Desalination 280:197–202

    Article  Google Scholar 

  • Halling-Sørensen B, Nors Nielsen S, Lanzky PF, Ingerslev F, Holten Lützhøft HC, Jørgensen SE (1998) Occurrence, fate and effects of pharmaceutical substances in the environment—a review. Chemosphere 36:357–393

    Article  Google Scholar 

  • Hanna K, Chiron S, Oturan MA (2005) Coupling enhanced water solubilization with cyclodextrin to indirect electrochemical treatment for pentachlorophenol contaminated soil remediation. Water Res 39:2763–2773

    Article  CAS  Google Scholar 

  • Jones OA, Lester JN, Voulvoulis N (2005) Pharmaceuticals: a threat to drinking water? Trends Biotechnol 23:163–167

    Article  CAS  Google Scholar 

  • 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 78:334–341

    Article  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 

  • Lindqvist N, Tuhkanen T, Kronberg L (2005) Occurrence of acidic pharmaceuticals in raw and treated sewages and in receiving waters. Water Res 39:2219–2228

    Article  CAS  Google Scholar 

  • Marco-Urrea E, Pérez-Trujillo M, Cruz-Morató C, Caminal G, Vicent T (2010) White-rot fungus-mediated degradation of the analgesic ketoprofen and identification of intermediates by HPLC–DAD–MS and NMR. Chemosphere 78:474–481

    Article  CAS  Google Scholar 

  • Matamoros V, Duhec A, Albaigés J, Bayona J (2009) Photodegradation of carbamazepine, ibuprofen, ketoprofen and 17α-ethinylestradiol in fresh and seawater. Water Air Soil Pollut 196:161–168

    Article  CAS  Google Scholar 

  • Mei Fun Choong A, Lay-Ming Teo S, Lene Leow J, Ling Koh H, Chi Lui Ho PA (2006) Preliminary ecotoxicity study of pharmaceuticals in the marine environment. J Toxicol Environ Health A 69:1959–1970

    Article  Google Scholar 

  • Murati M, Oturan N, Aaron JJ, Dirany A, Tassin B, Zdravkovski Z, Oturan M (2012) Degradation and mineralization of sulcotrione and mesotrione in aqueous medium by the electro-Fenton process: a kinetic study. Environ Sci Pollut Res 19:1563–1573

    Article  CAS  Google Scholar 

  • Murugananthan M, Yoshihara S, Rakuma T, Uehara N, Shirakashi T (2007) Electrochemical degradation of 17β-estradiol (E2) at boron-doped diamond (Si/BDD) thin film electrode. Electrochim Acta 52:3242–3249

    Article  CAS  Google Scholar 

  • Nikolaou A, Meric S, Fatta D (2007) Occurrence patterns of pharmaceuticals in water and wastewater environments. Anal Bioanal Chem 387:1225–1234

    Article  CAS  Google Scholar 

  • 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 30:475–482

    Article  CAS  Google Scholar 

  • Oturan MA, Pinson J (1995) Hydroxylation by electrochemically generated OH radicals. Mono- and polyhydroxylation of benzoic acid: products and isomer distribution. J Phys Chem 99:13948–13954

    Article  CAS  Google Scholar 

  • 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 334:103–109

    Article  CAS  Google Scholar 

  • Oturan MA, Oturan N, Lahitte C, Trevin S (2001) Production of hydroxyl radicals by electrochemically assisted Fenton’s reagent: application to the mineralization of an organic micropollutant, pentachlorophenol. J Electroanal Chem 507:96–102

    Article  CAS  Google Scholar 

  • Oturan MA, Sirés I, Oturan N, Pérocheau S, Laborde J-L, Trévin S (2008a) Sonoelectro-Fenton process: a novel hybrid technique for the destruction of organic pollutants in water. J Electroanal Chem 624:329–332

    Article  CAS  Google Scholar 

  • Oturan MA, Pimentel M, Oturan N, Sirés I (2008b) Reaction sequence for the mineralization of the short-chain carboxylic acids usually formed upon cleavage of aromatics during electrochemical Fenton treatment. Electrochim Acta 54:173–182

    Article  CAS  Google Scholar 

  • Oturan N, Panizza M, Oturan MA (2009) Cold incineration of chlorophenols in aqueous solution by advanced electrochemical process electro-Fenton. Effect of number and position of chlorine atoms on the degradation kinetics. J Phys Chem A 113:10988–10993

    Article  CAS  Google Scholar 

  • Oturan N, Brillas E, Oturan MA (2012) Unprecedented total mineralization of atrazine and cyanuric acid by anodic oxidation and electro-Fenton with a boron-doped diamond anode. Environ Chem Lett 10:165–170

    Article  CAS  Google Scholar 

  • Özcan A, Şahin Y, Oturan MA (2008a) Removal of propham from water by using electro-Fenton technology: kinetics and mechanism. Chemosphere 73:737–744

    Article  Google Scholar 

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

    Article  Google Scholar 

  • Özcan A, Şahin Y, Savaş Koparal A, 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 616:71–78

    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 

  • Pignatello JJ (1992) Dark and photoassisted iron(3+)-catalyzed degradation of chlorophenoxy herbicides by hydrogen peroxide. Environ Sci Technol 26:944–951

    Article  CAS  Google Scholar 

  • Real FJ, Benitez FJ, Acero JL, Sagasti JJP, Casas F (2009) Kinetics of the chemical oxidation of the pharmaceuticals primidone, ketoprofen, and diatrizoate in ultrapure and natural waters. Ind Eng Chem Res 48:3380–3388

    Article  CAS  Google Scholar 

  • Rodrigo MA, Michaud PA, Duo I, Panizza M, Cerisola G, Comninellis C (2001) Oxidation of 4-chlorophenol at boron-doped diamond electrode for wastewater treatment. J Electrochem Soc 148:D60–D64

    Article  CAS  Google Scholar 

  • Rodrigo MA, Cañizares P, Sánchez-Carretero A, Sáez C (2010) Use of conductive-diamond electrochemical oxidation for wastewater treatment. Catal Today 151:173–177

    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 (2007) 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 (2010) Electrochemical degradation of β-blockers. Studies on single and multicomponent synthetic aqueous solutions. Water Res 44:3109–3120

    Article  Google Scholar 

  • Skoumal M, Rodríguez RM, Cabot PL, Centellas F, Garrido JA, Arias C, Brillas E (2009) Electro-Fenton, UVA photoelectro-Fenton and solar photoelectro-Fenton degradation of the drug ibuprofen in acid aqueous medium using platinum and boron-doped diamond anodes. Electrochim Acta 54:2077–2085

    Article  CAS  Google Scholar 

  • Stackelberg PE, Furlong ET, Meyer MT, Zaugg SD, Henderson AK, Reissman DB (2004) Persistence of pharmaceutical compounds and other organic wastewater contaminants in a conventional drinking-water-treatment plant. Sci Total Environ 329:99–113

    Article  CAS  Google Scholar 

  • Szabó RK, Megyeri C, Illés E, Gajda-Schrantz K, Mazellier P, Dombi A (2011) Phototransformation of ibuprofen and ketoprofen in aqueous solutions. Chemosphere 84:1658–1663

    Article  Google Scholar 

  • Taggart MA, Senacha KR, Green RE, Jhala YV, Raghavan B, Rahmani AR, Cuthbert R, Pain DJ, Meharg AA (2007) Diclofenac residues in carcasses of domestic ungulates available to vultures in India. Environ Int 33:759–765

    Article  CAS  Google Scholar 

  • Thomas AT (1998) Occurrence of drugs in German sewage treatment plants and rivers. Water Res 32:3245–3260

    Article  Google Scholar 

  • Thomas H (2002a) Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. Toxicol Lett 131:5–17

    Article  Google Scholar 

  • Thomas H (2002b) Tracking persistent pharmaceutical residues from municipal sewage to drinking water. J Hydrol 266:175–189

    Article  Google Scholar 

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Acknowledgments

Ling Feng is a doctoral research fellow of the Erasmus Mundus Joint Doctorate program ETeCoS3 (Environmental Technologies for Contaminated Solids, Soils and Sediments) under the grant agreement FPA no. 2010-0009.

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Correspondence to Giovanni Esposito or Mehmet A. Oturan.

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Responsible editor: Philippe Garrigues

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Feng, L., Oturan, N., van Hullebusch, E.D. et al. Degradation of anti-inflammatory drug ketoprofen by electro-oxidation: comparison of electro-Fenton and anodic oxidation processes. Environ Sci Pollut Res 21, 8406–8416 (2014). https://doi.org/10.1007/s11356-014-2774-2

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