Skip to main content
SpringerLink
Log in

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

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

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.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  • Abellan MN, Bayarri B, Gimenez J, Costa J (2007) Photocatalytic degradation of sulfamethoxazole in aqueous suspension of TiO2. Appl Catal B-Environ 74:233–241

    Article  CAS  Google Scholar 

  • 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 92:311–330

    Article  CAS  Google Scholar 

  • 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 36:1143–1154

    Article  CAS  Google Scholar 

  • 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 20:579–594

    Article  CAS  Google Scholar 

  • Baxendale JH, Wilson JA (1957) The photolysis of hydrogen peroxide at high light intensities. Trans Faraday Soc 53:344–356

    Article  CAS  Google Scholar 

  • 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 409:4351–4360

    Article  CAS  Google Scholar 

  • 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 47:870–880

    Article  CAS  Google Scholar 

  • 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 73:627–637

    Article  CAS  Google Scholar 

  • 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 39:3630–3638

    Article  CAS  Google Scholar 

  • Calza P, Medana C, Pazzi M, Baiocchi C, Pelizzetti E (2004) Photocatalytic transformations of sulphonamides on titanium dioxide. Appl Catal B-Environ 53:63–69

    Article  CAS  Google Scholar 

  • 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 38:2918–2926

    Article  CAS  Google Scholar 

  • 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 44:2221–2228

    Article  CAS  Google Scholar 

  • 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 258:28–33

    Article  CAS  Google Scholar 

  • 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 185:202–212

    Article  CAS  Google Scholar 

  • 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 604:309–316

    Article  Google Scholar 

  • Esplugas S, Giménez J, Contreras S, Pascual E, Rodríguez M (2002) Comparison of different advanced oxidation processes for phenol degradation. Water Res 36:1034–1042

    Article  CAS  Google Scholar 

  • 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 409:5505–5512

    Article  Google Scholar 

  • 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 402:2885–2896

    Article  Google Scholar 

  • 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 46:711–722

    Article  CAS  Google Scholar 

  • 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 70:678–690

    Article  CAS  Google Scholar 

  • Gros M, Petrović M, Ginebreda A, Barceló D (2010) Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard indexes. Environ Int 36:15–26

    Article  CAS  Google Scholar 

  • 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 1216:4989–5000

    Article  Google Scholar 

  • 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 158:27–36

    Article  CAS  Google Scholar 

  • Hu L, Flanders PM, Miller PL, Strathmann TJ (2007) Oxidation of sulfametoxazole and related antimicrobial agents by TiO2 photocatalysis. Water Res 41:2612–2626

    Article  CAS  Google Scholar 

  • Ito M, Fukahori S, Fujiwara T (2014) Adsotptive removal and photocatalytic decomposition of sulfamethazine in secondary effluent using TiO2-zeolite composites. Environ Sci Pollut 21:834–842

    Article  CAS  Google Scholar 

  • 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 80:363–371

    Article  Google Scholar 

  • 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 45:1165–1176

    Article  CAS  Google Scholar 

  • 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 1–24

    Chapter  Google Scholar 

  • Kaniou S, Pitarakis K, Barlagianni I, Poulios I (2005) Photocatalytic oxidation of sulfamethazine. Chemosphere 60:372–380

    Article  CAS  Google Scholar 

  • Klavarioti M, Mantzavinos D, Kassinos D (2009) Removal of residual pharmaceuticals from aqueous systems by advanced oxidation processes. Environ Int 35:402–417

    Article  CAS  Google Scholar 

  • Kopf P, Gilbert E, Eberle SH (2000) TiO2 photocatalytic oxidation of monochloroacetic acid and pyridine: influence of ozone. J Photoch Photobio A 136:163–168

    Article  CAS  Google Scholar 

  • 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 193:193–203

    Article  CAS  Google Scholar 

  • 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 39:3421–3429

    Article  CAS  Google Scholar 

  • Ljubas D (2005) Solar photocatalysis—a possible step in drinking water treatment. Energy 30:1699–1710

    Article  CAS  Google Scholar 

  • 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 473–474:619–641

    Article  Google Scholar 

  • 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 145:65–71

    Article  CAS  Google Scholar 

  • 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 109:171–176

    Article  CAS  Google Scholar 

  • Naeem K, Feng O (2008) Parameters effect on heterogenous photocatalysed degradation of phenol in aqueous dispersion of TiO2. J Envirn Sci 21:527–533

    Google Scholar 

  • 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 186:67–75

    Article  CAS  Google Scholar 

  • Oppenländer T (2003) Photochemical purification of water and air. Wiley-VCH Verlag, Weinheim

    Google Scholar 

  • 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 47:1237–1245

    Article  CAS  Google Scholar 

  • 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 20:8934–8946

    Article  Google Scholar 

  • 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 67:3979–4003

    Article  Google Scholar 

  • Rabindranathan S, Devipriya S, Yesodharan S (2003) Photocatalytic degradation of phosphamidon on semiconductor oxides. J Hazard Mater 102:217–229

    Article  CAS  Google Scholar 

  • 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 93:1268–1287

    Article  CAS  Google Scholar 

  • Schwarz J, Aust MO, Thiele-Bruhn S (2010) Metabolites from fungal laccase-catalysed transformation of sulphonamides. Chemosphere 81:1469–1476

    Article  CAS  Google Scholar 

  • 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 37:1153–1160

    Article  Google Scholar 

  • Shifu C, Yunzhang L (2007) Study on the photocatalytic degradation of glyphosate by TiO2 photocatalysis. Chemosphere 67:1010–1017

    Article  Google Scholar 

  • Tanaka K, Hisanaga T, Harada K (1990) Photocatalytic degradation of organochlorine compounds in suspended TiO2. J Photoch Photobio A 54:113–118

    Article  Google Scholar 

  • Tong AYC, Braund R, Warren DS, Peake BM (2012) TiO2-assisted photodegradation of pharmaceuticals—a review. Cent Eur J Chem 10:989–1027

    Article  CAS  Google Scholar 

  • 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 77:1292–1298

    Article  CAS  Google Scholar 

  • 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 389:416–428

    Article  CAS  Google Scholar 

  • 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 231–286

    Google Scholar 

  • Wang Y, Hong C-S (1999) Effect of hydrogen peroxide, periodate and persulfate on photocatalysis of 2-chlorobiphenyl in aqueous TiO2 suspensions. Water Res 33:2031–2036

    Article  CAS  Google Scholar 

  • 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 165:201–207

    Article  CAS  Google Scholar 

  • 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 46:845–853

    Article  CAS  Google Scholar 

  • Wöhrle D, Tausch MW, Stohrer W-D (1998) Photochemistry-concepts, methods, experiments. Wiley-VCH, Weinheim (in German)

    Google Scholar 

  • 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 162:945–953

    Article  CAS  Google Scholar 

  • 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 153:200–207

    Article  CAS  Google Scholar 

  • Zessela K, Mohring S, Hamscher G, Kietzmann M, Stahl J (2014) Biocompatibility and antibacterial activity of photolytic products of sulfonamides. Chemosphere 100:167–174

    Article  Google Scholar 

Download references

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.”

Author information

Authors and Affiliations

  1. Department of Analytical Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb, Marulićev trg 19, 10000, Zagreb, Croatia

    Sandra Babić & Mirta Zrnčić

  2. Department of Energy, Power Engineering and Environment, Faculty of Mechanical Engineering and Naval Architecture, University of Zagreb, Zagreb, Croatia

    Davor Ljubas

  3. Department of Materials, Faculty of Mechanical Engineering and Naval Architecture, University of Zagreb, Zagreb, Croatia

    Lidija Ćurković

  4. Department of Organic Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb, Zagreb, Croatia

    Irena Škorić

Authors
  1. Sandra Babić
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mirta Zrnčić
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Davor Ljubas
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Lidija Ćurković
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Irena Škorić
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Sandra Babić.

Additional information

Responsible editor: Roland Kallenborn

Sandra Babić is a full professor, Department of Analytical Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb.

Mirta Zrnčić holds a PhD degree, Department of Analytical Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb.

Davor Ljubas is an associated professor, Department of Energy, Power Engineering and Environment, Faculty of Mechanical Engineering and Naval Architecture, University of Zagreb.

Lidija Ćurković is a full professor, Department of Materials, Faculty of Mechanical Engineering and Naval Architecture, University of Zagreb.

Irena Škorić is an associated professor, Department of Organic Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOCX 66 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Babić, S., Zrnčić, M., Ljubas, D. et al. Photolytic and thin TiO2 film assisted photocatalytic degradation of sulfamethazine in aqueous solution. Environ Sci Pollut Res 22, 11372–11386 (2015). https://doi.org/10.1007/s11356-015-4338-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-015-4338-5

Keywords

Search

Navigation