Advertisement

Environmental Science and Pollution Research

, Volume 22, Issue 15, pp 11372–11386 | Cite as

Photolytic and thin TiO2 film assisted photocatalytic degradation of sulfamethazine in aqueous solution

  • Sandra BabićEmail author
  • Mirta Zrnčić
  • Davor Ljubas
  • Lidija Ćurković
  • Irena Škorić
Research Article

Abstract

This paper deals with the photolytic and the photocatalytic degradation of sulfonamide antibiotic sulfamethazine (SMT) dissolved in Milli-Q water and in synthetic wastewater. Besides the direct photolysis, oxidation processes including UV/H2O2, UV/TiO2, and UV/TiO2/H2O2 using UV-A and UV-C radiation were investigated. Pseudo-first-order kinetics was observed for the degradation of SMT in all investigated processes. Additions of an electron acceptor (H2O2) and a catalyst (TiO2 film) accelerated the photolytic degradation of SMT for both the UV-A- and the UV-C-based processes. The most efficient process was UV-C/TiO2/H2O2 with complete degradation of SMT obtained in 10 min. The UV-A-based processes have been less efficient in terms of irradiation time required to totally degrade SMT than the UV-C-based processes. It was also confirmed that different wastewater components can significantly reduce the degradation rate of SMT. An almost ninefold reduction in the rate constant of SMT was observed for the specific synthetic wastewater. Although UV-A radiation experiments need more time and energy (2.7 times more electrical energy was consumed per gram of demineralized SMT) than UV-C experiments, they have a potential for practical use since natural UV-A solar radiation could be used here, which lowers the overall cost of the treatment. Five degradation products were detected during the degradation processes, and their structural formulae are presented. The structural formulae were elucidated based on mass spectra fragmentation pattern obtained using the tandem mass spectrometry (MS/MS) and NMR analysis.

Keywords

Titanium dioxide film Pharmaceuticals Sulfamethazine Photolysis Photocatalysis Photodegradation path Wastewater 

Notes

Acknowledgements

This study was partially supported by the University of Zagreb within the framework of the Short-Term Research Funding 2013-No. 2: “Advanced Water Treatment Technologies.”

Supplementary material

11356_2015_4338_MOESM1_ESM.docx (67 kb)
ESM 1 (DOCX 66 kb)

References

  1. Abellan MN, Bayarri B, Gimenez J, Costa J (2007) Photocatalytic degradation of sulfamethoxazole in aqueous suspension of TiO2. Appl Catal B-Environ 74:233–241CrossRefGoogle Scholar
  2. Ahmed S, Rasul MG, Brown R, Hashib MA (2011) Influence of parameters on the heterogenous photocatalytic degradation of pesticides and phenolic contaminants in wastewater: a short review. J Environ Manage 92:311–330CrossRefGoogle Scholar
  3. Alaton IA, Balcioglu IA, Bahnemann DW (2002) Advanced oxidation of a reactive dye bath effluent: comparison of O3, H2O2/UV-C and TiO2/UV-A processes. Water Res 36:1143–1154CrossRefGoogle Scholar
  4. Amalric L, Guillard C, Pichat P (1994) Use of catalase and superoxide dismutase to assess the roles of hydrogen peroxide and superoxide in the TiO2 or ZnO photocatalytic destruction of 1,2-dimethoxybenzene in water. Res Chem Intermediat 20:579–594CrossRefGoogle Scholar
  5. Baxendale JH, Wilson JA (1957) The photolysis of hydrogen peroxide at high light intensities. Trans Faraday Soc 53:344–356CrossRefGoogle Scholar
  6. Behera SK, Kim HW, Oh J-E, Park H-S (2011) Occurrence and removal of antibiotics, hormones and several other pharmaceuticals in wastewater treatment plants of the largest industrial city of Korea. Sci Total Environ 409:4351–4360CrossRefGoogle Scholar
  7. Benitez FJ, Acero JL, Real FJ, Roldan G, Rodriguez E (2013) Photolysis of model emerging contaminants in ultra-pure water: kinetics, by-products formation and degradation pathways. Water Res 47:870–880CrossRefGoogle Scholar
  8. Bolton JR, Bircher KG, Tumas W, Tolman CA (2001) Figures-of-merit for the technical development and application of advanced oxidation technologies for both electric- and solar-driven systems (IUPAC technical report). Pure App Chem 73:627–637CrossRefGoogle Scholar
  9. Boreen AL, Arnold WA, McNeill K (2005) Triplet-sensitized photodegradation of sulfa drugs containing six-membered heterocyclic groups: identification of an SO2 extrusion photoproduct. Environ Sci Technol 39:3630–3638CrossRefGoogle Scholar
  10. Calza P, Medana C, Pazzi M, Baiocchi C, Pelizzetti E (2004) Photocatalytic transformations of sulphonamides on titanium dioxide. Appl Catal B-Environ 53:63–69CrossRefGoogle Scholar
  11. Carballa M, Omil F, Lema JM, Llompart M, García-Jares C, Rodríguez I, Gómez M, Ternes T (2004) Behavior of pharmaceuticals, cosmetics and hormones in a sewage treatment plant. Water Res 38:2918–2926CrossRefGoogle Scholar
  12. Chelme-Ayala P, El-Din MG, Smith DW (2010) Degradation of bromoxynil and trifluralin in natural water by direct photolysis and UV plus H2O2 advanced oxidation process. Water Res 44:2221–2228CrossRefGoogle Scholar
  13. Chen J-Q, Hu Z-J, Wang D, Gao C-J, Ji R (2010) Photocatalytic mineralization of dimethoate in aqueous solution using TiO2: parameters and by-products analysis. Desalination 258:28–33CrossRefGoogle Scholar
  14. Collado N, Rodriguez-Mozaz S, Gros M, Rubirola A, Barceló D, Comas J, Rodriguez-Roda I, Buttiglieri G (2014) Pharmaceuticals occurrence in a WWTP with significant industrial contribution and its input into the river system. Environ Pollut 185:202–212CrossRefGoogle Scholar
  15. Ćurković L, Ljubas D, Šegota S, Bačić I (2014) Photocatalytic degradation of Lissamine Green B dye by using nanostructured sol-gel TiO2 films. J Alloy Compd 604:309–316CrossRefGoogle Scholar
  16. Esplugas S, Giménez J, Contreras S, Pascual E, Rodríguez M (2002) Comparison of different advanced oxidation processes for phenol degradation. Water Res 36:1034–1042CrossRefGoogle Scholar
  17. García-Galán MJ, Rodríguez-Rodríguez CE, Vicent T, Caminal G, Díaz-Cruz MS, Barceló D (2011) Biodegradation of sulfamethazine by Trametes versicolor: removal from sewage sludge and identification of intermediate products by UPLC-QqTOF-MS. Sci Total Environ 409:5505–5512CrossRefGoogle Scholar
  18. García-Galán MJ, Frömel T, Müller J, Peschka M, Knepper T, Díaz-Cruz S, Barceló D (2012) Biodegradation studies of N4-acetylsulfapyridine and N4-acetylsulfamethazine in environmental water applying mass spectrometry techniques. Anal Bioanal Chem 402:2885–2896CrossRefGoogle Scholar
  19. Garcia-Galan MJ, Diaz-Cruz MS, Barcelo D (2012) Kinetic studies and characterization of photolytic products of sulfamethazine, sulfapyridine and their acetylated metabolites in water under simulated solar irradiation. Water Res 46:711–722CrossRefGoogle Scholar
  20. Gros M, Petrović M, Barceló D (2006) Development of a multi-residue analytical methodology based on liquid chromatography–tandem mass spectrometry (LC–MS/MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters. Talanta 70:678–690CrossRefGoogle Scholar
  21. Gros M, Petrović M, Ginebreda A, Barceló D (2010) Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard indexes. Environ Int 36:15–26CrossRefGoogle Scholar
  22. Grujić S, Vasiljević T, Laušević M (2009) Determination of multiple pharmaceutical classes in surface and ground waters by liquid chromatography–ion trap–tandem mass spectrometry. J Chromatogr A 1216:4989–5000CrossRefGoogle Scholar
  23. Guillard C, Lachheb H, Houas A, Ksibi M, Elaloui E, Herrmann J-M (2003) Naphthalene degradation in water by heterogeneous photocatalysis: an investigation of the influence of inorganic anions. J Photoch Photobio A 158:27–36CrossRefGoogle Scholar
  24. Hu L, Flanders PM, Miller PL, Strathmann TJ (2007) Oxidation of sulfametoxazole and related antimicrobial agents by TiO2 photocatalysis. Water Res 41:2612–2626CrossRefGoogle Scholar
  25. Ito M, Fukahori S, Fujiwara T (2014) Adsotptive removal and photocatalytic decomposition of sulfamethazine in secondary effluent using TiO2-zeolite composites. Environ Sci Pollut 21:834–842CrossRefGoogle Scholar
  26. Jelić A, Petrović M, Barceló D (2009) Multi-residue method for trace level determination of pharmaceuticals in solid samples using pressurized liquid extraction followed by liquid chromatography/quadrupole-linear ion trap mass spectrometry. Talanta 80:363–371CrossRefGoogle Scholar
  27. Jelic A, Gros M, Ginebreda A, Cespedes-Sanchez R, Ventura F, Petrovic M, Barcelo D (2011) Occurrence, partition and removal of pharmaceuticals in sewage water and sludge during wastewater treatment. Water Res 45:1165–1176CrossRefGoogle Scholar
  28. Jelic A, Gros M, Petrović M, Ginebreda A, Barceló D (2012) Occurrence and elimination of pharmaceuticals during conventional wastewater treatment. In: Guasch H, Ginebreda A, Geiszinger A (eds) Emerging and priority pollutants in rivers. Springer, Berlin, pp 1–24CrossRefGoogle Scholar
  29. Kaniou S, Pitarakis K, Barlagianni I, Poulios I (2005) Photocatalytic oxidation of sulfamethazine. Chemosphere 60:372–380CrossRefGoogle Scholar
  30. Klavarioti M, Mantzavinos D, Kassinos D (2009) Removal of residual pharmaceuticals from aqueous systems by advanced oxidation processes. Environ Int 35:402–417CrossRefGoogle Scholar
  31. Kopf P, Gilbert E, Eberle SH (2000) TiO2 photocatalytic oxidation of monochloroacetic acid and pyridine: influence of ozone. J Photoch Photobio A 136:163–168CrossRefGoogle Scholar
  32. Lair A, Ferronato C, Chovelon J-M, Herrmann J-M (2008) Naphthalene degradation in water by heterogeneous photocatalysis: an investigation of the influence of inorganic anions. J Photoch Photobio A 193:193–203CrossRefGoogle Scholar
  33. Lindberg RH, Wennberg P, Johansson MI, Tysklind M, Andersson BAV (2005) Screening of human antibiotic substances and determination of weekly mass flows in five sewage treatment plants in Sweden. Environ Sci Technol 39:3421–3429CrossRefGoogle Scholar
  34. Ljubas D (2005) Solar photocatalysis—a possible step in drinking water treatment. Energy 30:1699–1710CrossRefGoogle Scholar
  35. Luo Y, Guoa W, Ngo HH, Nghiemb LD, Hai FI, Zhang J, Liang S, Wang XC (2014) A review on the occurrence of micropollutants in the aquatic environment and their fate and removal during wastewater treatment. Sci Total Environ 473–474:619–641CrossRefGoogle Scholar
  36. Mahmoodi NM, Armani M, Lymaee NY, Gharanjig K (2007) Photocatalytic degradation of agricultural N-heterocyclic organic pollutants using immobilized nanoparticles of titania. J Hazard Mater 145:65–71CrossRefGoogle Scholar
  37. Maurino V, Minero C, Pelizzetti E, Piccinini P, Serpone N, Hidaka H (1997) The fate of organic nitrogen under photocatalytic conditions: degradation of nitrophenols and aminophenols on irradiated TiO2. J Photoch Photobio A 109:171–176CrossRefGoogle Scholar
  38. Naeem K, Feng O (2008) Parameters effect on heterogenous photocatalysed degradation of phenol in aqueous dispersion of TiO2. J Envirn Sci 21:527–533Google Scholar
  39. Nasuhoglu D, Yargeau V, Berk D (2011) Photo-removal of sulfametoxazole (SMX) by photolytic and photocatalytic processes in batch reactor under UV-C radiation (λmax = 254 nm). J Hazard Mater 186:67–75CrossRefGoogle Scholar
  40. Oppenländer T (2003) Photochemical purification of water and air. Wiley-VCH Verlag, WeinheimGoogle Scholar
  41. Pablos C, Marugán J, van Grieken R, Serrano E (2013) Emerging micropollutant oxidation during disinfection processes using UV-C, UV-C/H2O2, UV-A/TiO2 and UV-A/TiO2/H2O2. Water Res 47:1237–1245CrossRefGoogle Scholar
  42. Periša M, Babić S, Škorić I, Frömel T, Knepper TP (2013) Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts. Environ Sci Pollut 20:8934–8946CrossRefGoogle Scholar
  43. Petrovic M, de Alda MJL, Diaz-Cruz S, Postigo C, Radjenovic J, Gros M, Barceló D (2009) Fate and removal of pharmaceuticals and illicit drugs in conventional and membrane bioreactor wastewater treatment plants and by riverbank filtration. Philos Trans R Soc, A 67:3979–4003CrossRefGoogle Scholar
  44. Rabindranathan S, Devipriya S, Yesodharan S (2003) Photocatalytic degradation of phosphamidon on semiconductor oxides. J Hazard Mater 102:217–229CrossRefGoogle Scholar
  45. Rivera-Utrilla J, Sánchez-Polo M, Ferro-García MA, Prados-Joya G, Ocampo-Pérez R (2013) Pharmaceuticals as emerging contaminants and their removal from water. A review. Chemosphere 93:1268–1287CrossRefGoogle Scholar
  46. Schwarz J, Aust MO, Thiele-Bruhn S (2010) Metabolites from fungal laccase-catalysed transformation of sulphonamides. Chemosphere 81:1469–1476CrossRefGoogle Scholar
  47. Šegota S, Ćurković L, Ljubas D, Svetličić V, Fiamengo Houra I, Tomašić N (2011) Synthesis, characterization and photocatalytic properties of sol-gel TiO2 films. Ceram Int 37:1153–1160CrossRefGoogle Scholar
  48. Shifu C, Yunzhang L (2007) Study on the photocatalytic degradation of glyphosate by TiO2 photocatalysis. Chemosphere 67:1010–1017CrossRefGoogle Scholar
  49. Tanaka K, Hisanaga T, Harada K (1990) Photocatalytic degradation of organochlorine compounds in suspended TiO2. J Photoch Photobio A 54:113–118CrossRefGoogle Scholar
  50. Tong AYC, Braund R, Warren DS, Peake BM (2012) TiO2-assisted photodegradation of pharmaceuticals—a review. Cent Eur J Chem 10:989–1027CrossRefGoogle Scholar
  51. Trovo AG, Nogueira RFP, Aguera A, Sirtori C, Fernandez-Alba AR (2009) Photodegradation of sulfamethoxazole in various aqueous media: persistence, toxicity and photoproducts assessment. Chemosphere 77:1292–1298CrossRefGoogle Scholar
  52. Verlicchi P, Galleti A, Petrović M, Barceló D (2010) Hospital effluents as a source of emerging pollutants: an overview of micropollutants and sustainable treatment options. J Hydrol 389:416–428CrossRefGoogle Scholar
  53. Verlicchi P, Zambello E, Al Aukidy M (2013) Removal of pharmaceuticals by conventional wastewater treatment plants. In: Petrovic M, Barceló D, Pérez S (eds) Analysis, removal, effects and risk of pharmaceuticals in the water cycle. Elsevier, Amsterdam, pp 231–286Google Scholar
  54. Wang Y, Hong C-S (1999) Effect of hydrogen peroxide, periodate and persulfate on photocatalysis of 2-chlorobiphenyl in aqueous TiO2 suspensions. Water Res 33:2031–2036CrossRefGoogle Scholar
  55. Wang K, Zhang J, Lou L, Yang S, Chen Y (2004) UV or visible light induced photodegradation of AO7 on TiO2 particles: the influence of inorganic anions. J Photoch Photobio A 165:201–207CrossRefGoogle Scholar
  56. Wang C, Zhu L, Wei M, Chen P, Shan G (2012) Photolytic reaction mechanism and impacts of coexisting substances on photodegradation of bisphenol A by Bi2WO6 in water. Water Res 46:845–853CrossRefGoogle Scholar
  57. Wöhrle D, Tausch MW, Stohrer W-D (1998) Photochemistry-concepts, methods, experiments. Wiley-VCH, Weinheim (in German)Google Scholar
  58. Wu R, Chena C, Chen M, Lu C (2009) Titanium dioxide-mediated heterogenous photocatalytic degradation of terbufos: parameter study and reaction pathways. J Hazard Mater 162:945–953CrossRefGoogle Scholar
  59. Yang H, Li G, An T, Gao Y, Fu J (2010) Photocatalytic degradation kinetics and mechanism of environmental pharmaceuticals in aqueous suspension of TiO2: a case of sulfa drugs. Catal Today 153:200–207CrossRefGoogle Scholar
  60. Zessela K, Mohring S, Hamscher G, Kietzmann M, Stahl J (2014) Biocompatibility and antibacterial activity of photolytic products of sulfonamides. Chemosphere 100:167–174CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  • Sandra Babić
    • 1
    Email author
  • Mirta Zrnčić
    • 1
  • Davor Ljubas
    • 2
  • Lidija Ćurković
    • 3
  • Irena Škorić
    • 4
  1. 1.Department of Analytical Chemistry, Faculty of Chemical Engineering and TechnologyUniversity of ZagrebZagrebCroatia
  2. 2.Department of Energy, Power Engineering and Environment, Faculty of Mechanical Engineering and Naval ArchitectureUniversity of ZagrebZagrebCroatia
  3. 3.Department of Materials, Faculty of Mechanical Engineering and Naval ArchitectureUniversity of ZagrebZagrebCroatia
  4. 4.Department of Organic Chemistry, Faculty of Chemical Engineering and TechnologyUniversity of ZagrebZagrebCroatia

Personalised recommendations