Environmental Science and Pollution Research

, Volume 24, Issue 14, pp 12556–12561 | Cite as

Fast photocatalytic degradation of pharmaceutical micropollutants and ecotoxicological effects

  • Isabella Natali SoraEmail author
  • Davide Fumagalli
Environmental Photocatalysis and Photochemistry for a Sustainable World: A Big Challenge


Aqueous solutions of ciprofloxacin (CP) and ibuprofen (IBP) in the presence of LaFeO3 photocatalyst, of H2O2, and of both LaFeO3 and H2O2 were irradiated under visible light. The degradation rate in the presence of both LaFeO3 and H2O2 after 5 h irradiation was more than 90 % for CP and 40 % for IBP, much higher than that with only H2O2 under visible light. For the sake of comparison, the experiments were also carried out in the dark, and both CP and IBP were not significantly converted. The degradation rate was enhanced by the simultaneous presence of small concentration of LaFeO3 (130 mg L−1) and H2O2 (0.003 M). However, tests on the aquatic acute toxicity indicate that the degradation products of CP and IBP induce toxic effects on aquatic organisms, consequently indicating incomplete detoxification after 5 h irradiation. The main degradation product of IBP was 4-isobutylacetophenone (4-IBAP), detected in the irradiated solutions by using UV/vis spectrophotometry. 4-IBAP was more toxic and showed a slower photocatalytic degradation than the parent compound. On the contrary, the toxicity of CP degradation products, although not negligible, was comparable to that of CP itself.


Lanthanum ferrite Aquatic toxicity tests Ibuprofen Ciprofloxacin 


  1. Ashton D, Hilton M, Thomas KV (2004) Investigating the environmental transport of human pharmaceuticals to streams in the United Kingdom. Sci Total Environ 333:167–184CrossRefGoogle Scholar
  2. Barbero N, Vione D (2016) Why dyes should not be used to test the photocatalytic activity of semiconductor oxides. Environ Sci Technol 50:2130–2131CrossRefGoogle Scholar
  3. Calamari D, Zuccato E, Castiglioni S, Bagnati R, Fanelli R (2003) Strategic survey of therapeutic drugs in the rivers Po and Lambro in northern Italy. Environ Sci Technol 37:1241–1248CrossRefGoogle Scholar
  4. Caronna T, Fontana F, Natali Sora I, Pelosato R (2009) Chemical synthesis and structural characterization of the substitution compound LaFe1-xCuxO3 (x = 0-0.40). Mat Chem Phys 116:645–648CrossRefGoogle Scholar
  5. Castiglioni S, Bagnati R, Fanelli R, Pomati F, Calamari D, Zuccato E (2006) Removal of pharmaceutical in sewage treatment plants in Italy. Environ Sci Technol 40:357–363CrossRefGoogle Scholar
  6. Caviglioli G, Valeria P, Brunella P, Sergio C, Attilia A, Gaetano B (2002) Identification of degradation products of ibuprofen arising from oxidative and thermal treatments. J Pharm Biomed Anal 30:499–509CrossRefGoogle Scholar
  7. Clara M, Stren B, Kreuzinger N (2004) Carbamazepine as a possible anthropogenic marker in the aquatic environment: investigations on the behaviour of carbamazepine in wastewater treatment and during groundwater infiltration. Water Res 38:947–954CrossRefGoogle Scholar
  8. Daughton CG, Ternes TA (1999) Pharmaceuticals and personal care products in the environment: agents of subtle change? Environ Health Perspect 107:907–938CrossRefGoogle Scholar
  9. Della Greca M, Brigante M, Isidori M, Nardelli A, Previtera L, Rubino M, Temussi F (2004) Phototransformation and ecotoxicity of the drug naproxen-Na. Environ Chem Lett 1:237–241CrossRefGoogle Scholar
  10. Dodd MC, Buffle M-O, Von Gunten U (2006) Oxidation of antibacterial molecules by aqueous ozone: moiety-specific reaction kinetics and application to ozone-based wastewater treatment. Environ Sci and Tech 40:1969–1977CrossRefGoogle Scholar
  11. Garzón LC, Martìnez F (2004) Temperature dependence of solubility for ibuprofen in some organic and aqueous solvents. J Solut Chem 33:1379–1395CrossRefGoogle Scholar
  12. Gasco-Lopez AI, Izquierdo-Hornillos R (1999) LC method development for ibuprophen and validation in different pharmaceuticals. J Pharm Biomed Anal 21:143–149CrossRefGoogle Scholar
  13. Goossens H, Ferech M, Coenen S, Stephens P (2007) Comparison of outpatient systemic antibacterial use in 2004 in the United States and 27 European countries. Clinical Infectious Disease 44:1091–1095CrossRefGoogle Scholar
  14. Hirsch R, Ternes T, Haberer K, Krantz K-L (1999) Occurrence of antibiotics in the aquatic environments. Sci Total Environ 225:109–118CrossRefGoogle Scholar
  15. Hoffmann M, Martin ST, Choi W, Bahnemann DW (1995) Environmental applications of semiconductor photocatalysis. Chem Rev 95:69–96CrossRefGoogle Scholar
  16. Hu R, Li C, Wang X, Sun Y, Jia H, Su H, Zhang Y (2012) Photocatalytic activities of LaFeO3 and La2FeTiO6 in p-chlorophenol degradation under visible light. Catalysis Comm 29:35–39CrossRefGoogle Scholar
  17. ISO 8692: 2012 Water quality—fresh water algal growth inhibition test with unicellular green algae.
  18. Johnson AC, Keller V, Dumont E, Sumpter JP (2015) Assessing the concentrations and risks of toxicity from the antibiotics ciprofloxacin, sulfamethoxazole, trimethoprim and erythromycin in European rivers. Sci Total Environ 511:747–755CrossRefGoogle Scholar
  19. Kolpin DW, Furlong ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB (2002) Pharmaceuticals, hormones, and other organic wastewater contaminants in US streams, 1999–2000: a national reconnaissance. Environ Sci Technol 36:1202–1211CrossRefGoogle Scholar
  20. Kümmerer K (2009) Antibiotics in the aquatic environment—a review—part I. Chemosphere 75:417–434CrossRefGoogle Scholar
  21. Li S, Jing L, Fu W, Yang L, Xin B, Fu H (2007) Photoinduced charge property of nanosized perovskite-type LaFeO3 and its relationships with photocatalytic activity under visible irradiation. Mater Res Bull 42:203–212CrossRefGoogle Scholar
  22. Mompelat S, Le Bot B, Thomas O (2009) Occurrence and fate of pharmaceutical products and by-products, from resource to drinking water. Environ Int 35:803–814CrossRefGoogle Scholar
  23. Natali Sora I, Fontana F, Passalacqua R, Ampelli C, Perathoner S, Centi G, Parrino F, Palmisano L (2013) Photoelectrochemical properties of doped lanthanum orthoferrites. Electrochim Acta 109:710–715CrossRefGoogle Scholar
  24. Packer JL, Werner JJ, Latch DE, McNeill K, Arnold WA (2003) Photochemical fate of pharmaceuticals in the environment: naproxen, diclofenac, clofibric acid, and ibuprofen. Aquat Sci 65:342–351CrossRefGoogle Scholar
  25. Parrino F, García-López E, Marcì G, Palmisano L, Felice V, Natali Sora I, Armelao L (2016) Cu-substituted lanthanum ferrite perovskites: preparation, characterization and photocatalytic activity in gas-solid regime under simulated solar light irradiation. J Alloys Comp 682:686–694CrossRefGoogle Scholar
  26. Peng K, Fu L, Yang H, Ouyang J (2016) Perovskite LaFeO3/montmorillonite nanocomposites: synthesis, interface characteristics and enhanced photocatalytic activity. Scientific Reports 6:19723CrossRefGoogle Scholar
  27. Ruggeri G, Ghigo G, Maurino V, Minero C, Vione D (2013) Photochemical transformation of ibuprofen into harmful 4-isobutylacetophenone: pathways, kinetics, and significance for surface waters. Water Res 47:6109–6121CrossRefGoogle Scholar
  28. Selli E, Bianchi CL, Pirola C, Cappelletti G, Ragaini V (2008) Efficiency of 1,4-dichlorobenzene degradation in water under photolysis, photocatalysis on TiO2 and sonolysis. J Hazard Mater 153:1136–1141CrossRefGoogle Scholar
  29. Su H, Jing L, Shi K, Yao C, Fu H (2010) Synthesis of large surface area LaFeO3 nanoparticles by SBA-16 template method as high active visible photocatalysts. J Nanopart Res 12:967–974CrossRefGoogle Scholar
  30. Ternes TA (1998) Occurrence of drugs in German sewage treatment plants and rivers. Water Res 32:3245–3260CrossRefGoogle Scholar
  31. Thirumalairajan S, Girija K, Hebalkar NY, Mangalaraj D, Viswanathan C, Ponpandian N (2013) Shape evolution of perovskite LaFeO3 nanostructures: a systematic investigation of growth mechanism, properties and morphology dependent photocatalytic activities. RSC Adv 3:7549–7561CrossRefGoogle Scholar
  32. UNI EN ISO 11348–3:2009 Water quality—determination of the inhibitory effect of water samples on the light emission of Vibrio fischeri (Luminescent bacteria test)—part 3: method using freeze-dried bacteria.
  33. UNI EN ISO 6341:2013 Water quality—determination of the inhibition of the mobility of Daphnia magna Straus (Cladocera, Crustacea)—acute toxicity test.
  34. Vasconcelos TG, Henriques DM, König A, Martins AF, Kümmerer K (2009) Photo-degradation of the antimicrobial ciprofloxacin at high pH: identification and biodegradability assessment of the primary by-products. Chemosphere 76:487–493CrossRefGoogle Scholar
  35. Verlicchi P, Al Aukidy M, Zambello E (2012) Occurrence of pharmaceutical compounds in urban wastewater: removal, mass load and environmental risk after secondary treatment—a review. Sci Total Environ 429:123–155CrossRefGoogle Scholar
  36. Wagenlehner FME, Kinzig-Schippers M, Sörgel F, Weidner W, Naber KG (2006) Concentrations in plasma, urinary excretion and bactericidal activity of levofloxacin (500 mg) versus ciprofloxacin (500 mg) in healthy volunteers receiving a single oral dose. Int J Antimicrobial Agents 28:551–559CrossRefGoogle Scholar
  37. Zuccato E, Castiglioni S, Fanelli R (2005) Identification of the pharmaceuticals for human use contaminating the Italian aquatic environment. J Hazard Mater 122:205–209CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  1. 1.Department of Engineering and Applied SciencesUniversity of BergamoDalmineItaly
  2. 2.INSTM R.U. BergamoUniversity of BergamoDalmineItaly

Personalised recommendations