Optimization of the electrochemical degradation process of the antibiotic ciprofloxacin using a double-sided β-PbO2 anode in a flow reactor: kinetics, identification of oxidation intermediates and toxicity evaluation

Abstract

The electrochemical degradation of ciprofloxacin—CIP (50 mg L−1 in 0.10 mol L−1 Na2SO4) was investigated using a double-sided Ti-Pt/β-PbO2 anode in a filter-press flow reactor, with identification of oxidation intermediates and follow-up of antimicrobial activity against Escherichia coli. The effect of solution pH, flow rate, current density, and temperature on the CIP removal rate was evaluated. All of these parameters did affect the CIP removal performance; thus, optimized electrolysis conditions were further explored: pH = 10, qV = 6.5 L min−1, j = 30 mA cm−2, and θ = 25 °C. Therefore, CIP was removed within 2 h, whereas ~75% of the total organic carbon concentration (TOC) was removed after 5 h and then, the solution no longer presented antimicrobial activity. When the electrochemical degradation of CIP was investigated using a single-sided boron-doped diamond (BDD) anode, its performance in TOC removal was similar to that of the Ti-Pt/β-PbO2 anode; considering the higher oxidation power of BDD, the surprisingly good comparative performance of the Ti-Pt/β-PbO2 anode was ascribed to significantly better hydrodynamic conditions attained in the filter-press reactor used with this electrode. Five initial oxidation intermediates were identified by LC-MS/MS and completely removed after 4 h of electrolysis; since they have also been determined in other degradation processes, there must be similarities in the involved oxidation mechanisms. Five terminal oxidation intermediates (acetic, formic, oxamic, propionic, and succinic acids) were identified by LC-UV and all of them (except acetic acid) were removed after 10 h of electrolysis.

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

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

References

  1. Andrade LS, Ruotolo LAM, Rocha-Filho RC, Bocchi N, Biaggio SR, Iniesta J, García-Garcia V, Montiel V (2007) On the performance of Fe and Fe, F doped Ti-Pt/PbO2 electrodes in the electrooxidation of the blue reactive 19 dye in simulated textile wastewater. Chemosphere 66:2035–2043. https://doi.org/10.1016/j.chemosphere.2006.10.028

    Article  CAS  Google Scholar 

  2. 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

    Article  CAS  Google Scholar 

  3. Aquino JM, Irikura K, Rocha-Filho RC, Bocchi N, Biaggio SR (2010a) A comparison of electrodeposited Ti/β-PbO2 and Ti-Pt/β-PbO2 anodes in the electrochemical degradation of the direct yellow 86 dye. Quim Nova 33:2124–2129. https://doi.org/10.1590/S0100-40422010001000023

    Article  CAS  Google Scholar 

  4. Aquino JM, Rocha-Filho RC, Bocchi N, Biaggio SR (2010b) Electrochemical degradation of the reactive red 141 dye on a β-PbO2 anode assessed by the response surface methodology. J Braz Chem Soc 21:324–330. https://doi.org/10.1590/S0103-50532010000200019

    Article  CAS  Google Scholar 

  5. Aus der Beek T, Weber FA, Bermann A, Hickmann S, Ebert I, Hein A, Küster A (2016) Pharmaceuticals in the environment—global occurrences and perspectives. Environ Toxicol Chem 35:823–835. https://doi.org/10.1002/etc.3339

    Article  CAS  Google Scholar 

  6. 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. https://doi.org/10.1021/cr900136g

    Article  CAS  Google Scholar 

  7. Brocenschi RF, Rocha-Filho RC, Bocchi N, Biaggio SR (2016) Electrochemical degradation of estrone using a boron-doped diamond anode in a filter-press reactor. Electrochim Acta 197:186–193. https://doi.org/10.1016/j.electacta.2015.09.170

    Article  CAS  Google Scholar 

  8. Cañizares P, García-Gómez J, Fernandéz De Marcos I, Rodrigo MA, Lobato J (2006) Measurement of mass-transfer coefficients by an electrochemical technique. J Chem Educ 83:1204–1207. https://doi.org/10.1021/ed083p1204

    Article  Google Scholar 

  9. Chin NX, Neu HC (1984) Ciprofloxacin, a quinolone carboxylic acid compound active against aerobic and anaerobic bacteria. Antimicrob Agents Chemother 25:319–326. https://doi.org/10.1128/AAC.25.3.319

    Article  CAS  Google Scholar 

  10. Coledam DAC, Aquino JM, Silva BF, Silva AJ, Rocha-Filho RC (2016) Electrochemical mineralization of norfloxacin using distinct boron-doped diamond anodes in a filter-press reactor, with investigations of toxicity and oxidation byproducts. Electrochim Acta 213:856–864. https://doi.org/10.1016/j.electacta.2016.08.003

    Article  CAS  Google Scholar 

  11. 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

    Article  CAS  Google Scholar 

  12. Denadai M, Cass QB (2015) Simultaneous determination of fluoroquinolones in environmental water by liquid chromatography–tandem mass spectrometry with direct injection: a green approach. J Chromatogr A 1418:177–184. https://doi.org/10.1016/j.chroma.2015.09.066

    Article  CAS  Google Scholar 

  13. Dewil R, Mantzavinos D, Poulios I, Rodrigo MA (2017) New perspectives for advanced oxidation processes. J Environ Manag 195:93–99. https://doi.org/10.1016/j.jenvman.2017.04.010

    Article  CAS  Google Scholar 

  14. Domagala JM (1994) Structure-activity and structure-side-effect relationships for the quinolone antibacterials. J Antimicrob Chemother 33:685–706. https://doi.org/10.1093/jac/33.4.685

    Article  CAS  Google Scholar 

  15. Durán-Álvarez JC, Avella E, Ramírez-Zamora RM, Zanella R (2016) Photocatalytic degradation of ciprofloxacin using mono- (Au, Ag and Cu) and bi- (Au-Ag and Au-Cu) metallic nanoparticles supported on TiO2 under UV-C and simulated sunlight. Catal Today 266:175–187. https://doi.org/10.1016/j.cattod.2015.07.033

    Article  CAS  Google Scholar 

  16. Giri AS, Golder AK (2014) Ciprofloxacin degradation from aqueous solution by Fenton oxidation: reaction kinetics and degradation mechanism. RSC Adv 4:6738–6745. https://doi.org/10.1039/C3RA45709E

    Article  CAS  Google Scholar 

  17. 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

    Article  CAS  Google Scholar 

  18. Irikura K, Bocchi N, Rocha-Filho RC, Biaggio SR, Iniesta J, Montiel V (2016) Electrodegradation of the acid green 28 dye using Ti/β-PbO2 and Ti-Pt/β-PbO2 anodes. J Environ Manag 183:306–313. https://doi.org/10.1016/j.jenvman.2016.08.061

    Article  CAS  Google Scholar 

  19. Jiang C, Ji Y, Shi Y, Chen J, Cai T (2016) Sulfate radical-based oxidation of fluoroquinolone antibiotics: kinetics, mechanisms and effects of natural water matrices. Water Res 106:507–517. https://doi.org/10.1016/j.watres.2016.10.025

    Article  CAS  Google Scholar 

  20. Kapalka A, Fóti G, Comninellis C (2008) Kinetic modeling of the electrochemical mineralization of organic pollutants for wastewater treatment. J Appl Electrochem 38:7–16. https://doi.org/10.1007/s10800-007-9365-6

    Article  CAS  Google Scholar 

  21. Kapalka A, Fóti G, Comninellis C (2009) The importance of electrode material in environmental electrochemistry: formation and reactivity of free hydroxyl radicals on boron-doped diamond electrodes. Electrochim Acta 54:2018–2023. https://doi.org/10.1016/j.electacta.2008.06.045

    Article  CAS  Google Scholar 

  22. Maia AS, Ribeiro AR, Amorim CL, Barreiro JC, Cass QB, Castro PML, Tiritan ME (2014) Degradation of fluoroquinolone antibiotics and identification of metabolites/transformations products by liquid chromatography-tandem mass spectrometry. J Chromatogr A 1333:87–98. https://doi.org/10.1016/j.chroma.2014.01.069

    Article  CAS  Google Scholar 

  23. Martínez-Huitle CA, Andrade LS (2011) Electrocatalysis in wastewater treatment: recent mechanism advances. Quim Nova 34:850–858. https://doi.org/10.1590/S0100-40422011000500021

    Article  Google Scholar 

  24. Martínez-Huitle CA, Rodrigo MA, Sirés I, Scialdone O (2015) Single and coupled electrochemical processes and reactors for the abatement of organic water pollutants: a critical review. Chem Rev 115:13362–13407. https://doi.org/10.1021/acs.chemrev.5b00361

    Article  CAS  Google Scholar 

  25. Miwa DW, Malpass GRP, Machado SAS, Motheo AJ (2006) Electrochemical degradation of carbaryl on oxide electrodes. Water Res 40:3281–3289. https://doi.org/10.1016/j.watres.2006.06.033

    Article  CAS  Google Scholar 

  26. Moreira FC, Boaventura RAR, Brillas E, Vilar VJP (2017) Electrochemical advanced oxidation processes: a review on their application to synthetic and real wastewater. Appl Catal, B 202:217–261. https://doi.org/10.1016/j.apcatb.2016.08.037

    Article  CAS  Google Scholar 

  27. Nunes MJ, Monteiro N, Pacheco MJ, Lopes A, Ciríaco L (2016) Ti/β-PbO2 versus Ti/Pt/β-PbO2: influence of the platinum interlayer on the electrodegradation of tetracyclines. J Environ Sci Health, Part A: Environ Sci Eng 51:839–846. https://doi.org/10.1080/10934529.2016.1181455

    Article  CAS  Google Scholar 

  28. Panizza M, Cerisola G (2005) Application of diamond electrodes to electrochemical processes. Electrochim Acta 51:191–199. https://doi.org/10.1016/j.electacta.2005.04.023

    Article  CAS  Google Scholar 

  29. Panizza M, Cerisola G (2008) Electrochemical degradation of methyl red using BDD and PbO2 anodes. Ind Eng Chem Res 47:6816–6820. https://doi.org/10.1021/ie8001292

    Article  CAS  Google Scholar 

  30. Panizza M, Cerisola G (2009) Direct and mediated anodic oxidation of organic pollutants. Chem Rev 109:6541–6569. https://doi.org/10.1021/cr9001319

    Article  CAS  Google Scholar 

  31. Pereira GF, Rocha-Filho RC, Bocchi N, Biaggio SR (2012) Electrochemical degradation of bisphenol A using a flow reactor with a boron-doped diamond anode. Chem Eng J 198-199:282–288. https://doi.org/10.1016/j.cej.2012.05.057

    Article  CAS  Google Scholar 

  32. Pereira GF, Rocha-Filho RC, Bocchi N, Biaggio SR (2015) Electrochemical degradation of the herbicide picloram using a filter-press flow reactor with a boron-doped diamond or β-PbO2 anode. Electrochim Acta 179:588–598. https://doi.org/10.1016/j.electacta.2015.05.134

    Article  CAS  Google Scholar 

  33. Pereira GF, Silva BF, Oliveira RV, Coledam DAC, Aquino JM, Rocha-Filho RC, Bocchi N, Biaggio SR (2017) Comparative electrochemical degradation of the herbicide tebuthiuron using a flow cell with a boron-doped diamond anode and identifying degradation intermediates. Electrochim Acta 247:860–870. https://doi.org/10.1016/j.electacta.2017.07.054

    Article  CAS  Google Scholar 

  34. 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

    Article  CAS  Google Scholar 

  35. Radjenovic J, Sedlak DL (2015) Challenges and opportunities for electrochemical processes as next-generation technologies for the treatment of contaminated water. Environ Sci Technol 49:11292–11302. https://doi.org/10.1021/acs.est.5b02414

    Article  CAS  Google Scholar 

  36. Rahmani AR, Nematollahi D, Samarghandi MR, Samadi MT, Azarian G (2018) A combined advanced oxidation process: electrooxidation-ozonation for antibiotic ciprofloxacin removal from aqueous solution. J Electroanal Chem 808:82–89. https://doi.org/10.1016/j.jelechem.2017.11.067

    Article  CAS  Google Scholar 

  37. Reinholds I, Muter O, Pugajeva I, Rusko J, Perkons I, Bartkevics V (2017) Determination of pharmaceutical residues and assessment of their removal efficiency at the Daugavgriva municipal wastewater treatment plant in Riga, Latvia. Water Sci Technol 75:387–396. https://doi.org/10.2166/wst.2016.528

    Article  CAS  Google Scholar 

  38. Rocha-Filho RC, Andrade LS, Bocchi N, Biaggio SR (2014) Organic pollutants in water, direct electrochemical oxidation using PbO2. In: Kreysa G, Ota K, Savinell RF (eds) Encyclopedia of Applied Electrochemistry. Springer, New York. https://doi.org/10.1007/978-1-4419-6996-593

    Google Scholar 

  39. Särkkä H, Bhatnagar A, Sillanpää M (2015) Recent developments of electro-oxidation in water treatment—a review. J Electroanal Chem 754:46–56. https://doi.org/10.1016/j.jelechem.2015.06.016

    Article  CAS  Google Scholar 

  40. Shestakova M, Sillanpää M (2017) Electrode materials used for electrochemical oxidation compounds in wastewater. Rev Environ Sci Biotechnol 16:223–238. https://doi.org/10.1007/s11157-017-9426-1

    Article  CAS  Google Scholar 

  41. Silambarasan S, Vangnai AS (2016) Biodegradation of 4-nitroaniline by plant-growth promoting Acinetobacter sp. AVLB2 and toxicological analysis of its biodegradation metabolites. J Hazard Mater 302:426–436. https://doi.org/10.1016/j.jhazmat.2015.10.010

    Article  CAS  Google Scholar 

  42. Wächter N, Pereira GF, Rocha-Filho RC, Bocchi N, Biaggio SR (2015) Comparative electrochemical degradation of the acid yellow 49 dye using boron-doped diamond, beta-PbO2, and DSA® anodes in a flow reactor. Int J Electrochem Sci 10:1361–1371 http://www.electrochemsci.org/papers/vol10/100201361.pdf

    Google Scholar 

  43. Wang Y, Shen C, Zhang M, Zhang B, Yu Y (2016) The electrochemical degradation of ciprofloxacin using a SnO2-Sb/Ti anode: influencing factors, reaction pathways and energy demand. Chem Eng J 296:79–89. https://doi.org/10.1016/j.cej.2016.03.093

    Article  CAS  Google Scholar 

  44. Wang C, Yin L, Xu Z, Niu J, Hou L (2017) Electrochemical degradation of enrofloxacin by lead dioxide anode: kinetics, mechanism and toxicity evaluation. Chem Eng J 326:911–920. https://doi.org/10.1016/j.cej.2017.06.038

    Article  CAS  Google Scholar 

  45. Wolfson JS, Hooper DC (1989) Fluoroquinolone antimicrobial agents. Clin Microbiol Rev 2:378–424. https://doi.org/10.1128/CMR.2.4.378

    Article  CAS  Google Scholar 

  46. Yu X, Zhou M, Hu Y, Serrano KG, Yu F (2014) Recent updates on electrochemical degradation of bio-refractory organic pollutants using BDD anode: a mini review. Environ Sci Pollut Res 21:8417–8431. https://doi.org/10.1007/s11356-014-2820-0

    Article  CAS  Google Scholar 

  47. Zhanel GG, Ennis K, Vercaigne L, Walkty A, Gin AS, Embil J, Smith H, Hoban DJ (2002) A critical review of the fluoroquinolones—focus on respiratory tract infections. Drugs 62:13–59. https://doi.org/10.2165/00003495-200262010-00002

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The research funding agencies CNPq, Capes, and FAPESP—São Paulo Research Foundation (grant numbers 2009/17138-0, 2009/54040-8, and 2012/13002-9) are gratefully acknowledged for financial support and scholarships. The pharmaceutical company EMS is also gratefully acknowledged for supplying samples of CIP hydrochloride monohydrate.

Author information

Affiliations

Authors

Corresponding author

Correspondence to Romeu C. Rocha-Filho.

Additional information

Responsible editor: Bingcai Pan

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Wachter, N., Aquino, J.M., Denadai, M. et al. Optimization of the electrochemical degradation process of the antibiotic ciprofloxacin using a double-sided β-PbO2 anode in a flow reactor: kinetics, identification of oxidation intermediates and toxicity evaluation. Environ Sci Pollut Res 26, 4438–4449 (2019). https://doi.org/10.1007/s11356-018-2349-8

Download citation

Keywords

  • Electrooxidation
  • Ti-Pt/β-PbO2 anode
  • Filter-press reactor
  • Antimicrobial activity
  • BDD anode