Abstract
Taking ciprofloxacin (CIP) as a fluoroquinolone antibiotic model, this work explores the role of common anions (sulfate, nitrate, and chloride) during the application of photoelectro-Fenton (PEF) at natural pH to degrade this type of compound in water. The system was composed of an IrO2 anode, Ti, or gas diffusion electrode (GDE) as cathode, Fe2+, and UV (254 nm). To determine the implications of these anions, the degradation pathway and efficiency of the PEF sub-processes (UV photolysis, anodic oxidation, and electro-Fenton at natural pH) were studied in the individual presence of the anions. The results highlight that degradation routes and kinetics are strongly dependent on electrolytes. When chloride and nitrate ions were present, indirect electro-chemical oxidation was identified by electro-generated HOCl and nitrogenated oxidative species, respectively. Additionally, direct photolysis and direct oxidation at the anode surface were identified as degradation routes. As a consequence of the different pathways, six primary CIP by-products were identified. Therefore, a scheme was proposed representing the pathways involved in the degradation of CIP when submitted to PEF in water with chloride, nitrate, and sulfate ions, showing the complexity of this process. Promoted by individual and synergistic actions of this process, the PEF system leads to a complete elimination of CIP with total removal of antibiotic activity against Staphylococcus aureus and Escherichia coli, and significant mineralization. Finally, the role of the anions was tested in seawater containing CIP, in which the positive contributions of the anions were partially suppressed by its OH radical scavenger action. The findings are of interest for the understanding of the degradation of antibiotics via the PEF process in different matrices containing sulfate, nitrate, and chloride ions.
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Abbreviations
- CIP:
-
Ciprofloxacin
- ECs:
-
Emergent contaminants
- DSA:
-
Dimensionally stable anode
- EF:
-
Electro-Fenton
- EO:
-
Electro-oxidation
- GDE:
-
Gas diffusional electrode
- PEF:
-
Photoelectro-Fenton
- TOC:
-
Total organic carbon
- UV:
-
Ultraviolet radiation
References
Antonin VS, Santos MC, Garcia-Segura S, Brillas E (2015) Electrochemical incineration of the antibiotic ciprofloxacin in sulfate medium and synthetic urine matrix. Water Res 83:31–41. https://doi.org/10.1016/j.watres.2015.05.066
Aquino Neto S, de Andrade AR (2009) Electrooxidation of glyphosate herbicide at different DSA® compositions: pH, concentration and supporting electrolyte effect. Electrochim Acta 54:2039–2045. https://doi.org/10.1016/j.electacta.2008.07.019
Aquino JM, Rodrigo MA, Rocha-Filho RC et al (2012) Influence of the supporting electrolyte on the electrolyses of dyes with conductive-diamond anodes. Chem Eng J 184:221–227. https://doi.org/10.1016/j.cej.2012.01.044
Babić S, Periša M, Škorić I (2013) Photolytic degradation of norfloxacin, enrofloxacin and ciprofloxacin in various aqueous media. Chemosphere 91:1635–1642. https://doi.org/10.1016/j.chemosphere.2012.12.072
Bañuelos JA, El-Ghenymy A, Rodríguez FJ et al (2014) Study of an air diffusion activated carbon packed electrode for an electro-Fenton wastewater treatment. Electrochim Acta 140:412–418. https://doi.org/10.1016/j.electacta.2014.05.078
Batchu SR, Panditi VR, O’Shea KE, Gardinali PR (2014) Photodegradation of antibiotics under simulated solar radiation: implications for their environmental fate. Sci Total Environ 470-471:299–310. https://doi.org/10.1016/j.scitotenv.2013.09.057
Bouzek K, Paidar M, Sad’ilková A, Bergmann H (2001) Electrochemical reduction of nitrate in weakly alkaline solutions. J Appl Electrochem 31:1185–1193. doi: https://doi.org/10.1023/A:1012755222981
Brillas E, Sirés I, M a O (2009) Electro-Fenton process and related electrochemical technologies based on Fenton’s reaction chemistry. Chem Rev 109:6570–6631. https://doi.org/10.1021/cr900136g
Carvalho C, Fernandes a L a et al (2007) Electrochemical degradation applied to the metabolites of Acid Orange 7 anaerobic biotreatment. Chemosphere 67:1316–1324. https://doi.org/10.1016/j.chemosphere.2006.10.062
Comninellis C (1994) Electrocatalysis in the electrochemical conversion/combustion of organic pollutants for waste water treatment. Electrochim Acta 39:1857–1862. https://doi.org/10.1016/0013-4686(94)85175-1
Coria G, Sirés I, Brillas E, Nava JL (2016) Influence of the anode material on the degradation of naproxen by Fenton-based electrochemical processes. Chem Eng J 304:817–825. doi: https://doi.org/10.1016/j.cej.2016.07.012
Couto AB, Oishi SS, Ferreira NG (2016) Enhancement of nitrate electroreduction using BDD anode and metal modified carbon fiber cathode. J Ind Eng Chem 39:210–217. https://doi.org/10.1016/j.jiec.2016.05.028
Daneshvar N, Aber S, Vatanpour V, Rasoulifard MH (2008) Electro-Fenton treatment of dye solution containing Orange II: influence of operational parameters. J Electroanal Chem 615:165–174. https://doi.org/10.1016/j.jelechem.2007.12.005
De Bel E, Dewulf J, Witte BD et al (2009) Influence of pH on the sonolysis of ciprofloxacin: biodegradability, ecotoxicity and antibiotic activity of its degradation products. Chemosphere 77:291–295. https://doi.org/10.1016/j.chemosphere.2009.07.033
Deborde M, von Gunten U (2008) Reactions of chlorine with inorganic and organic compounds during water treatment—kinetics and mechanisms: a critical review. Water Res 42:13–51. https://doi.org/10.1016/j.watres.2007.07.025
Devi LG, Munikrishnappa C, Nagaraj B, Rajashekhar KE (2013) Effect of chloride and sulfate ions on the advanced photo Fenton and modified photo Fenton degradation process of Alizarin Red S. J Mol Catal A Chem 374-375:125–131. https://doi.org/10.1016/j.molcata.2013.03.023
Dima GE, De Vooys ACA, Koper MTM (2003) Electrocatalytic reduction of nitrate at low concentration on coinage and transition-metal electrodes in acid solutions. J Electroanal Chem 554-555:15–23. https://doi.org/10.1016/S0022-0728(02)01443-2
Dodd MC, Shah AD, Von Gunten U, Huang CH (2005) Interactions of fluoroquinolone antibacterial agents with aqueous chlorine: reaction kinetics, mechanisms, and transformation pathways. Environ Sci Technol 39:7065–7076. https://doi.org/10.1021/es050054e
Espinoza C, Romero J, Villegas L, et al (2016) Mineralization of the textile dye acid yellow 42 by solar photoelectro-Fenton in a lab-pilot plant. J Hazard Mater 319:24–33. https://doi.org/10.1016/j.jhazmat.2016.03.003
Feng Y, Smith DW, Bolton JR (2007) Photolysis of aqueous free chlorine species (HOCl and OCl − ) with 254 nm ultraviolet light. J Environ Eng Sci 6:277–284. https://doi.org/10.1139/s06-052
Gatica J, Cytryn E (2013) Impact of treated wastewater irrigation on antibiotic resistance in the soil microbiome. Environ Sci Pollut Res 20:3529–3538. https://doi.org/10.1007/s11356-013-1505-4
Giraldo AL, Erazo-Erazo ED, Florez-Acosta OA et al (2015) Degradation of the antibiotic oxacillin in water by anodic oxidation with Ti/IrO2 anodes: evaluation of degradation routes, organic by-products and effects of water matrix components. Chem Eng J 279:103–114. https://doi.org/10.1016/jcej2015.04.140
Grebel JE, Pignatello JJ, W a M (2010) Effect of halide ions and carbonates on organic contaminant degradation by hydroxyl radical-based advanced oxidation processes in saline waters. Environ Sci Technol 44:6822–6828. https://doi.org/10.1021/es1010225
Guo H-G, Gao N-Y, Chu W-H et al (2013) Photochemical degradation of ciprofloxacin in UV and UV/H2O2 process: kinetics, parameters, and products. Environ Sci Pollut Res 20:3202–3213. https://doi.org/10.1007/s11356-012-1229-x
Guzman-Duque F, Pétrier C, Pulgarin C et al (2011) Effects of sonochemical parameters and inorganic ions during the sonochemical degradation of crystal violet in water. Ultrason Sonochem 18:440–446. https://doi.org/10.1016/j.ultsonch.2010.07.019
Guzmán-Duque FL, Palma-Goyes RE, González I et al (2014) Relationship between anode material, supporting electrolyte and current density during electrochemical degradation of organic compounds in water. J Hazard Mater 278:221–226. https://doi.org/10.1016/j.jhazmat.2014.05.076
Haddad T, Kümmerer K (2014) Characterization of photo-transformation products of the antibiotic drug ciprofloxacin with liquid chromatography-tandem mass spectrometry in combination with accurate mass determination using an LTQ-Orbitrap. Chemosphere 115:40–46. https://doi.org/10.1016/j.chemosphere.2014.02.013
Hu S, Zhang C, Yao H et al (2015) Intensify chemical reduction to remove nitrate from groundwater via internal microelectrolysis existing in nano-zero valent iron/granular activated carbon composite. Desalin Water Treat 57:14158–14168. https://doi.org/10.1080/19443994.2015.1062430
Klamerth N, Malato S, Agüera a, Fernández-Alba A (2013) Photo-Fenton and modified photo-Fenton at neutral pH for the treatment of emerging contaminants in wastewater treatment plant effluents: a comparison. Water Res 47:833–840. https://doi.org/10.1016/j.watres.2012.11.008
Kugelmann E, Albert CR, Bringmann G, Holzgrabe U (2011) Fenton’s oxidation: a tool for the investigation of potential drug metabolites. J Pharm Biomed Anal 54:1047–1058. https://doi.org/10.1016/j.jpba.2010.12.016
Lacasa E, Cañizares P, Llanos J, Rodrigo MA (2011) Removal of nitrates by electrolysis in non-chloride media: effect of the anode material. Sep Purif Technol 80:592–599. https://doi.org/10.1016/j.seppur.2011.06.01510.1016
Lacasa E, Cañizares P, Llanos J, Rodrigo MA (2012) Effect of the cathode material on the removal of nitrates by electrolysis in non-chloride media. J Hazard Mater 213-214:478–484. https://doi.org/10.1016/j.jhazmat.2012.02.034
Lacasa E, Tsolaki E, Sbokou Z et al (2013) Electrochemical disinfection of simulated ballast water on conductive diamond electrodes. Chem Eng J 223:516–523. https://doi.org/10.1016/j.cej.2013.03.003
Liang J, Zheng Y, Liu Z (2016) Nanowire-based Cu electrode as electrochemical sensor for detection of nitrate in water. Sensors Actuators B Chem 232:336–344. https://doi.org/10.1016/j.snb.2016.03.145
Luo H, Li C, Wu C et al (2015) Electrochemical degradation of phenol by in situ electro-generated and electro-activated hydrogen peroxide using an improved gas diffusion cathode. Electrochim Acta 186:486–493. https://doi.org/10.1016/j.electacta.2015.10.194
Malpass GRP, Miwa DW, Miwa ACP et al (2007) Photo-assisted electrochemical oxidation of atrazine on a commercial Ti/Ru0.3Ti0.7O2 DSA electrode. Environ Sci Technol 41:7120–7125. https://doi.org/10.1021/es070798n
Martínez-Huitle CA, Brillas E (2009) Decontamination of wastewaters containing synthetic organic dyes by electrochemical methods: a general review. Appl Catal B Environ 87:105–145. https://doi.org/10.1016/j.apcatb.2008.09.017
Nogueira RFP, Oliveira MC, Paterlini WC (2005) Simple and fast spectrophotometric determination of H(2)O(2) in photo-Fenton reactions using metavanadate. Talanta 66:86–91. https://doi.org/10.1016/j.talanta.2004.10.001
Palma-Goyes RE, Guzmán-Duque FL, Peñuela G et al (2010) Electrochemical degradation of crystal violet with BDD electrodes: effect of electrochemical parameters and identification of organic by-products. Chemosphere 81:26–32. https://doi.org/10.1016/j.chemosphere.2010.07.020
Panizza M, Martinez-Huitle CA (2013) Role of electrode materials for the anodic oxidation of a real landfill leachate—comparison between Ti–Ru–Sn ternary oxide, PbO2 and boron-doped diamond anode. Chemosphere 90:1455–1460. https://doi.org/10.1016/j.chemosphere.2012.09.006
Paul T, Dodd MC, Strathmann TJ (2010) Photolytic and photocatalytic decomposition of aqueous ciprofloxacin: transformation products and residual antibacterial activity. Water Res 44:3121–3132. https://doi.org/10.1016/j.watres.2010.03.002
Pérez T, Sirés I, Brillas E, Nava JL (2017) Solar photoelectro-Fenton flow plant modeling for the degradation of the antibiotic erythromycin in sulfate medium. Electrochim Acta. 228:45–56. https://doi.org/10.1016/j.electacta.2017.01.047
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 36:1–84. https://doi.org/10.1080/10643380500326564
Porras J, Bedoya C, Silva-Agredo J et al (2016) Role of humic substances in the degradation pathways and residual antibacterial activity during the photodecomposition of the antibiotic ciprofloxacin in water. Water Res 94:1–9. https://doi.org/10.1016/j.actamat.2015.02.029
Razuc M, Garrido M, Caro YS et al (2013) Hybrid hard- and soft-modeling of spectrophotometric data for monitoring of ciprofloxacin and its main photodegradation products at different pH values. Spectrochim Acta - Part A Mol Biomol Spectrosc 106:146–154. https://doi.org/10.1016/j.saa.2012.12.085
Rubio-Clemente A, Torres-Palma RA, Peñuela GA (2014) Removal of polycyclic aromatic hydrocarbons in aqueous environment by chemical treatments: a review. Sci Total Environ 478:201–225. https://doi.org/10.1016/j.scitotenv.2013.12.126
Rudolf M, Roušar I, Krýsa J (1995) Influence of ion migration on cathodic reduction of hypochlorite anions. Electrochim Acta 40:169–174. https://doi.org/10.1016/0013-4686(94)00310-W
Sánchez-Carretero A, Sáez C, Cañizares P, Rodrigo MA (2011) Electrochemical production of perchlorates using conductive diamond electrolyses. Chem Eng J 166:710–714. https://doi.org/10.1016/j.cej.2010.11.037
Serna-Galvis EA, Silva-Agredo J, Giraldo AL et al (2016) Comparative study of the effect of pharmaceutical additives on the elimination of antibiotic activity during the treatment of oxacillin in water by the photo-Fenton, TiO2-photocatalysis and electrochemical processes. Sci Total Environ 541:1431–1438. https://doi.org/10.1016/j.scitotenv.2015.10.029
Serna-Galvis EA, Ferraro F, Silva-Agredo J, Torres-Palma RA (2017a) Degradation of highly consumed fluoroquinolones, penicillins and cephalosporins in distilled water and simulated hospital wastewater by UV254 and UV254/persulfate processes. Water Res 122:128–138. https://doi.org/10.1016/j.watres.2017.05.065
Serna-Galvis EA, Jojoa-Sierra SD, Berrio-Perlaza KE et al (2017b) Structure-reactivity relationship in the degradation of three representative fluoroquinolone antibiotics in water by electrogenerated active chlorine. Chem Eng J 315:552–561. https://doi.org/10.1016/j.cej.2017.01.062
Sirés I, Brillas E, Oturan MA et al (2014) Electrochemical advanced oxidation processes: today and tomorrow. A review. Environ Sci Pollut Res 21:8336–8367. https://doi.org/10.1007/s11356-014-2783-1
Sturini M, Speltini A, Maraschi F et al (2015) Sunlight-induced degradation of fluoroquinolones in wastewater effluent: photoproducts identification and toxicity. Chemosphere 134:313–318. https://doi.org/10.1016/j.chemosphere.2015.04.081
Thiam A, Zhou M, Brillas E, Sirés I (2014) Two-step mineralization of tartrazine solutions: study of parameters and by-products during the coupling of electrocoagulation with electrochemical advanced oxidation processes. Appl Catal B Environ 150-151:116–125. https://doi.org/10.1016/j.apcatb.2013.12.011
Torres RA, Sarria V, Torres W et al (2003) Electrochemical treatment of industrial wastewater containing 5-amino-6-methyl-2-benzimidazolone: toward an electrochemical-biological coupling. Water Res 37:3118–3124. https://doi.org/10.1016/S0043-1354(03)00179-9
Vasconcelos TG, Henriques DM, König A et al (2009) Photo-degradation of the antimicrobial ciprofloxacin at high pH: identification and biodegradability assessment of the primary by-products. Chemosphere 76:487–493. https://doi.org/10.1016/j.chemosphere.2009.03.022
Villegas-Guzman P, Silva-Agredo J, Giraldo-Aguirre AL et al (2014) Enhancement and inhibition effects of water matrices during the sonochemical degradation of the antibiotic dicloxacillin. Ultrason Sonochem 22:211–219. https://doi.org/10.1016/j.ultsonch.2014.07.006
Villegas-Guzman P, Silva-Agredo J, González-Gómez D et al (2015) Evaluation of water matrix effects, experimental parameters, and the degradation pathway during the TiO2 photocatalytical treatment of the antibiotic dicloxacillin. J Environ Sci Health A Tox Hazard Subst Environ Eng 50:40–48. https://doi.org/10.1080/10934529.2015.964606
Villegas-Guzman P, Oppenheimer-Barrot S, Silva-Agredo J, Torres-Palma RA. (2017) Comparative evaluation of photo-chemical AOPs for ciprofoxacin degradation: elimination in natural waters and analysis of pH effect, primary degradation by-products, and the relationship with the antibiotic activity. Water Air Soil Pollut 228:209–214. doi: https://doi.org/10.1007/s11270-017-3388-3
Xiao R, He Z, Diaz-Rivera D et al (2014) Sonochemical degradation of ciprofloxacin and ibuprofen in the presence of matrix organic compounds. Ultrason Sonochem 21:428–435. https://doi.org/10.1016/j.ultsonch.2013.06.012
Xu W, Zhang G, Li X et al (2007) Occurrence and elimination of antibiotics at four sewage treatment plants in the Pearl River Delta (PRD), South China. Water Res 41:4526–4534. https://doi.org/10.1016/j.watres.2007.06.023
Zhou M, Särkkä H, Sillanpää M (2011) A comparative experimental study on methyl orange degradation by electrochemical oxidation on BDD and MMO electrodes. Sep Purif Technol 78:290–297. https://doi.org/10.1016/j.seppur.2011.02.013
Acknowledgements
The authors would like to thank the Swiss Agency for Development and Cooperation (SDC) and the Swiss National Science Foundation (SNSF) through the project “Treatment of the hospital wastewaters in Cote d'Ivoire and in Colombia by advanced oxidation processes”, the “Sostenibilidad” program of the Universidad de Antioquia, and Colciencias (Colombia) for the project “Desarrollo y evaluación de un sistema electroquímico asistido con luz solar para la eliminación de contaminantes emergentes en aguas (111565842980)”.
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Villegas-Guzman, P., Hofer, F., Silva-Agredo, J. et al. Role of sulfate, chloride, and nitrate anions on the degradation of fluoroquinolone antibiotics by photoelectro-Fenton. Environ Sci Pollut Res 24, 28175–28189 (2017). https://doi.org/10.1007/s11356-017-0404-5
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DOI: https://doi.org/10.1007/s11356-017-0404-5