Removal of carbamazepine, ciprofloxacin and ibuprofen in real urban wastewater by using light-driven advanced oxidation processes

  • A. Monteoliva-García
  • J. Martín-Pascual
  • M. M. Muñío
  • J. M. PoyatosEmail author
Original Paper


This study focuses on the use of advanced oxidation processes as a tertiary treatment in wastewater treatment plants to degrade contaminants of emerging concern at the natural pH of the biologically treated wastewater. Different peroxide dosages and initial concentrations of a mix of three pharmaceuticals commonly present in wastewater (carbamazepine, ciprofloxacin and ibuprofen) were tested in a batch photoreactor. The addition of Fe2+ and TiO2 as catalysts was also tested with the aim of improving the degradation rate of the pharmaceuticals. Among the contaminants tested, ciprofloxacin was the pollutant that showed the best degradation. It was completely removed from water after 20 min of treatment under any of the experimental conditions assessed. High degradation percentages, between 89.83 and 100%, were achieved for ibuprofen, while carbamazepine shows the lowest degradation, ranging from 80.14 to 100%. In terms of global efficiency, a complete degradation was achieved when the concentration of the tested contaminants was similar to current concentration levels in urban wastewater effluents. The addition of the catalysts did not significantly improve the degradation rates.


Advanced oxidation processes Emerging contaminants Heterogeneous photocatalysis Kinetics Pharmaceuticals Photo-Fenton Urban wastewater reuse 



This work was supported by EMASAGRA.


  1. Afonso-Olivares C, Fernández-Rodríguez C, Ojeda-González RJ, Sosa-Ferrera Z, Santana-Rodríguez JJ, Rodríguez JMD (2016) Estimation of kinetic parameters and UV doses necessary to remove twenty-three pharmaceuticals from pre-treated urban wastewater by UV/H2O2. J Photochem Photobiol A Chem 329:130–138. CrossRefGoogle Scholar
  2. Alharbi SK, Kang J, Nghiem LD, van de Merwe JP, Leusch FDL, Price WE (2017) Photolysis and UV/H2O2 of diclofenac, sulfamethoxazole, carbamazepine, and trimethoprim: identification of their major degradation products by ESI–LC–MS and assessment of the toxicity of reaction mixtures. Process Saf Environ Prot 112:222–234. CrossRefGoogle Scholar
  3. Alvarino T, Suarez S, Lema J, Omil F (2018) Understanding the sorption and biotransformation of organic micropollutants in innovative biological wastewater treatment technologies. Sci Total Environ 615:297–306. CrossRefGoogle Scholar
  4. Carabin A, Drogui P, Robert D (2015) Photo-degradation of carbamazepine using TiO2 suspended photocatalysts. J Taiwan Inst Chem Eng 54:109–117. CrossRefGoogle Scholar
  5. De la Cruz N, Giménez J, Esplugas S, Grandjean D, De Alencastro LF, Pulgarín C (2012) Degradation of 32 emergent contaminants by UV and neutral photo-fenton in domestic wastewater effluent previously treated by activated sludge. Water Res 46:1947–1957. CrossRefGoogle Scholar
  6. Eskandari M, Goudarzi N, Moussavi SG (2017) Application of low-voltage UVC light and synthetic ZnO nanoparticles to photocatalytic degradation of ciprofloxacin in aqueous sample solutions. Water Environ J 00:1–9. CrossRefGoogle Scholar
  7. European Commision (2015) An EU action plan for the circular economy. Com 614:21. CrossRefGoogle Scholar
  8. European Commission (2016) Guidelines on integrating water reuse into water planning and management in the context of the WFD 1–95Google Scholar
  9. Fast SA, Gude VG, Truax DD, Martin J, Magbanua BS (2017) A critical evaluation of advanced oxidation processes for emerging contaminants removal. Environ Process 4:283–302. CrossRefGoogle Scholar
  10. Gallardo-Altamirano MJ, Maza-Márquez P, Peña-Herrera JM, Rodelas B, Osorio F, Pozo C (2018) Removal of anti-inflammatory/analgesic pharmaceuticals from urban wastewater in a pilot-scale A2O system: linking performance and microbial population dynamics to operating variables. Sci Total Environ 643:1481–1492. CrossRefGoogle Scholar
  11. Ganiyu SO, Van Hullebusch ED, Cretin M, Esposito G, Oturan MA (2015) Coupling of membrane filtration and advanced oxidation processes for removal of pharmaceutical residues: a critical review. Sep Purif Technol 156:891–914. CrossRefGoogle Scholar
  12. Garrido E, Camacho-Muñoz D, Martín J, Santos A, Santos JL, Aparicio I, Alonso E (2016) Monitoring of emerging pollutants in Guadiamar River basin (South of Spain): analytical method, spatial distribution and environmental risk assessment. Environ Sci Pollut Res 23:25127–25144. CrossRefGoogle Scholar
  13. Giannakis S, Gamarra Vives FA, Grandjean D, Magnet A, De Alencastro LF, Pulgarin C (2015) Effect of advanced oxidation processes on the micropollutants and the effluent organic matter contained in municipal wastewater previously treated by three different secondary methods. Water Res 84:295–306. CrossRefGoogle Scholar
  14. Haroune L, Salaun M, Ménard A, Legault CY, Bellenger JP (2014) Photocatalytic degradation of carbamazepine and three derivatives using TiO2 and ZnO: effect of pH, ionic strength, and natural organic matter. Sci Total Environ 475:16–22. CrossRefGoogle Scholar
  15. Hassani A, Khataee A, Karaca S (2015) Photocatalytic degradation of ciprofloxacin by synthesized TiO2 nanoparticles on montmorillonite: effect of operation parameters and artificial neural network modeling. J Mol Catal A Chem 409:149–161. CrossRefGoogle Scholar
  16. Jallouli N, Pastrana-Martínez LM, Ribeiro AR, Moreira NFF, Faria JL, Hentati O, Silva AMT, Ksibi M (2018) Heterogeneous photocatalytic degradation of ibuprofen in ultrapure water, municipal and pharmaceutical industry wastewaters using a TiO2/UV-LED system. Chem Eng J 334:976–984. CrossRefGoogle Scholar
  17. Kaur A, Umar A, Kansal SK (2016) Heterogeneous photocatalytic studies of analgesic and non-steroidal anti-inflammatory drugs. Appl Catal A Gen 510:134–155. CrossRefGoogle Scholar
  18. Kim I, Yamashita N, Tanaka H (2009) Photodegradation of pharmaceuticals and personal care products during UV and UV/H2O2 treatments. Chemosphere 77:518–525. CrossRefGoogle Scholar
  19. 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. CrossRefGoogle Scholar
  20. Liao QN, Ji F, Li JC, Zhan X, Hu ZH (2016) Decomposition and mineralization of sulfaquinoxaline sodium during UV/H2O2 oxidation processes. Chem Eng J 284:494–502. CrossRefGoogle Scholar
  21. Lopez-Lopez C, Martín-Pascual J, Martínez-Toledo MV, Muñío MM, Hontoria E, Poyatos JM (2015) Kinetic modelling of TOC removal by H2O2/UV, photo-Fenton and heterogeneous photocatalysis processes to treat dye-containing wastewater. Int J Environ Sci Technol 12:3255–3262. CrossRefGoogle Scholar
  22. Martín J, Santos JL, Aparicio I, Alonso E (2015) Pharmaceutically active compounds in sludge stabilization treatments: anaerobic and aerobic digestion, wastewater stabilization ponds and composting. Sci Total Environ 503–504:97–104. CrossRefGoogle Scholar
  23. Mohapatra DP, Brar SK, Tyagi RD, Picard P, Surampalli RY (2014) Analysis and advanced oxidation treatment of a persistent pharmaceutical compound in wastewater and wastewater sludge-carbamazepine. Sci Total Environ 470–471:58–75. CrossRefGoogle Scholar
  24. Nihemaiti M, Miklos DB, Hübner U, Linden KG, Drewes JE, Croué JP (2018) Removal of trace organic chemicals in wastewater effluent by UV/H2O2 and UV/PDS. Water Res 145:487–497. CrossRefGoogle Scholar
  25. Oliveira C, Gruskevica K, Juhna T, Tihomirova K, Alves A, Madeira LM (2014) Removal of paraquat pesticide with Fenton reaction in a pilot scale water system. Drink Water Eng Sci 7:11–21. CrossRefGoogle Scholar
  26. Pereira VJ, Weinberg HS, Linden KG, Singer PC (2007) UV degradation kinetics and modeling of pharmaceutical compounds in laboratory grade and surface water via direct and indirect photolysis at 254 nm. Environ Sci Technol 41:1682–1688. CrossRefGoogle Scholar
  27. Poyatos JM, Muñio MM, Almecija MC, Torres JC, Hontoria E, Osorio F (2010) Advanced oxidation processes for wastewater treatment: state of the art. Water Air Soil Pollut 205:187–204. CrossRefGoogle Scholar
  28. Rizzo L, Malato S, Antakyali D, Beretsou VG, Đolić MB, Gernjak W, Heath E, Ivancev-Tumbas I, Karaolia P, Lado Ribeiro AR, Mascolo G, McArdell CS, Schaar H, Silva AMT, Fatta-Kassinos D (2019) Consolidated vs new advanced treatment methods for the removal of contaminants of emerging concern from urban wastewater. Sci Total Environ 655:986–1008. CrossRefGoogle Scholar
  29. Rodriguez-Narvaez OM, Peralta-Hernandez JM, Goonetilleke A, Bandala ER (2017) Treatment technologies for emerging contaminants in water: a review. Chem Eng J 323:361–380. CrossRefGoogle Scholar
  30. Rozas O, Mansilla HD, Urrutia R, Baeza C, Núñez K, Rossner A (2017) Organic micropollutants (OMPs) oxidation by ozone: effect of activated carbon on toxicity abatement. Sci Total Environ 590–591:430–439. CrossRefGoogle Scholar
  31. Salimi M, Esrafili A, Gholami M, Jonidi Jafari A, Rezaei Kalantary R, Farzadkia M, Kermani M, Sobhi HR (2017) Contaminants of emerging concern: a review of new approach in AOP technologies. Environ Monit Assess. CrossRefGoogle Scholar
  32. Sauvé S, Desrosiers M (2014) A review of what is an emerging contaminant. Chem Cent J 8:1–7. CrossRefGoogle Scholar
  33. Shu Z, Bolton JR, Belosevic M, Gamal El Din M (2013) Photodegradation of emerging micropollutants using the medium-pressure UV/H2O2 advanced oxidation process. Water Res 47:2881–2889. CrossRefGoogle Scholar
  34. Shu Z, Singh A, Klamerth N, McPhedran K, Bolton JR, Belosevic M, Gamal El-Din M (2016) Pilot-scale UV/H2O2 advanced oxidation process for municipal reuse water: assessing micropollutant degradation and estrogenic impacts on goldfish (Carassius auratus L.). Water Res 101:157–166. CrossRefGoogle Scholar
  35. Soriano-Molina P, Plaza-Bolaños P, Lorenzo A, Agüera A, García Sánchez JL, Malato S, Sánchez Pérez JA (2019) Assessment of solar raceway pond reactors for removal of contaminants of emerging concern by photo-Fenton at circumneutral pH from very different municipal wastewater effluents. Chem Eng J 366:141–149. CrossRefGoogle Scholar
  36. Villegas-Guzman P, Silva-Agredo J, González-Gómez D, Giraldo-Aguirre AL, Flórez-Acosta O, Torres-Palma RA (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 Part A 50:40–48. CrossRefGoogle Scholar
  37. Yang Y, Sik Y, Kim K, Kwon EE, Fai Y (2017) Occurrences and removal of pharmaceuticals and personal care products (PPCPs) in drinking water and water/sewage treatment plants: a review. Sci Total Environ 596–597:303–320. CrossRefGoogle Scholar

Copyright information

© Islamic Azad University (IAU) 2019

Authors and Affiliations

  1. 1.Department of Civil Engineering and Institute of Water ResearchUniversity of GranadaGranadaSpain
  2. 2.Department of Chemical EngineeringUniversity of GranadaGranadaSpain

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