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Photo-Fenton degradation of the pharmaceuticals ciprofloxacin and fluoxetine after anaerobic pre-treatment of hospital effluent

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Abstract

This work evaluated the photo-Fenton degradation of two pharmaceuticals extensively used in human medicine, ciprofloxacin (CIP), and fluoxetine (FLU) when present in an anaerobic pre-treated hospital effluent (HE) at low concentration (100 μg L−1). Operational parameters such as concentration of hydrogen peroxide, iron, and initial pH as well as the effect of iron citrate complex were evaluated considering the degradation of the pharmaceuticals. Iron citrate complex (Fecit) influenced significantly FLU degradation at pH 4.5 achieving 80 % after 20 min, while with iron nitrate only 36 % degradation was obtained after the same time. However, only a slight effect was observed on CIP degradation, achieving 86 % with Fecit and 75 % with Fe(NO3)3, after 20 min. Samples of HE used in this work were previously treated in an anaerobic reactor followed by sand filtration; however, the presence of pharmaceuticals was detected. Degradation of both FLU and CIP was significantly hindered when present in HE, due to the relatively high content of organic (39.6 mg L−1) and inorganic (12.5 mg L−1) carbon, which may have consumed ·OH in side reactions. However, the iron cycle reduction was not affected by the matrix in the presence of citrate. Despite the recalcitrance of the matrix (no total organic carbon removal), it was possible to achieve over 50 % degradation of both pharmaceuticals after 90 min.

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References

  • Abrahamson HB, Rezvani AB, Brushmiller JG (1994) Photochemical and spectroscopic studies of complexes, of iron(III) with citric acid and other carboxylic acids. Inorg Chim Acta 226:117–127

    Article  CAS  Google Scholar 

  • Bader H, Sturzenegger V, Hoigné J (1988) Photometric method for the determination of low concentrations of hydrogen peroxide by the peroxidase catalyzed oxidation of N,N-diethyl-p-phenylenediamine (DPD). Water Res 22:1109–1115

    Article  CAS  Google Scholar 

  • Bongaerts GP, Hoogkamp-Korstanje JA (1993) In vitro activities of BAY Y3118, ciprofloxacin, ofloxacin and fleroxacin against gram-positive and gram-negative pathogens from respiratory tract and soft tissue infections. Antimicrob Agents Chemother 37:2017–2019

    Article  CAS  Google Scholar 

  • Chu S, Metcalfe CD (2007) Analysis of paroxetine, fluoxetine and norfluoxetine in fish tissues using pressurized liquid extraction, mixed mode solid phase extraction cleanup and liquid chromatography-tandem mass spectrometry. J Chromatogr A 1116:112–118

    Article  Google Scholar 

  • Eldin F, Suliman O, Sultan SM (1996) Talanta 43:559–568

    Article  CAS  Google Scholar 

  • Emerick RW, Manning J, Tchobanoglous G, Darby JL (1999) Impact of bacteria and dosing frequency on the removal of virus within intermittently dosed biological filters. Small Flows Q 1(1):36–41

    Google Scholar 

  • Faust BC, Hoigné J (1990) Photolysis of Fe(III)-hidroxy complexes as sources of OH radicals in clouds, fog and rain. Atmos Environ 24:79–89

    Article  Google Scholar 

  • Faust BC, Zeep RG (1993) Photochemistry of aqueous iron (III)-polycarboxylate complexes: role in the chemistry of atmospheric and surface water. Environ Sci Technol 27:2417–2522

    Google Scholar 

  • Foran CM, Weston J, Slattery M, Brooks BW, Huggett DB (2004) Reproductive assessment of Japanese medaka (Oryzias latipes) following a four-week fluoxetine (SSRI) exposure. Arch Environ Contam Toxicol 46:511–517

    Article  CAS  Google Scholar 

  • Fortune WB, Mellon MG (1938) Determination of iron with o-phenanthroline. Ind Eng Chem Anal Ed 10:60–64

    Article  CAS  Google Scholar 

  • Gross M, Mitchell D (1990) Virus removal by sand filtration of septic tank effluent. J Environ Eng 116:711720

    Article  Google Scholar 

  • Heberer T (2002) Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. Toxicol Lett 131:5–17

    Article  CAS  Google Scholar 

  • Henry TB, Black MC (2008) Acute and chronic toxicity of fluoxetine (selective serotonin reuptake inhibitor) in western mosquitofish. Arch Environ Contam Toxicol 54:325–330

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Kosjek T, Perko S, Zigon D, Heath E (2013) Fluorouracil in the environment: analysis, occurrence, degradation and transformation. J Chromatogr A 1290:62–72

    Article  CAS  Google Scholar 

  • Martínez-Bueno MJ, Agüera A, Gómez MJ, Hernando MD, García-Reyes JF, Fernández-Alba AR (2007) Application of liquid chromatography/quadrupole-linear ion trap mass spectrometry and time-of-flight mass spectrometry to the determination of pharmaceuticals and related contaminants in wastewater. Anal Chem 79:9372–9384

    Article  Google Scholar 

  • Martins AF, Vasconcelos TG, Henriques DM, Frank CS, König A, Kümmerer K (2008) Concentration of ciprofloxacin in Brazilian hospital effluent and preliminary risk assessment: a case study. Clean 36:264–269

    CAS  Google Scholar 

  • Michael-Kordatou I, Michael C, Duan X, He X, Dionysiou DD, Mills MA, Fatta-Kassinos D (2015) Dissolved effluent organic matter: characteristics and potential implications in wastewater treatment and reuse applications. Water Res 77:213–248

    Article  CAS  Google Scholar 

  • Nogueira RFP, Guimarães JR (2000) Photodegradation of dichloroacetic acid and 2,4-dichlorophenol by ferrioxalate/H2O2 system. Water Res 34:895–901

    Article  CAS  Google Scholar 

  • Nogueira RFP, Silva MRA, Trovó AG (2005) Influence of the iron source on the solar photo-Fenton degradation of different classes of organic compounds. Sol Energy 79:384–392

    Article  CAS  Google Scholar 

  • Ou X, Quan X, Chen S, Zhang F, Zhao Y (2008) Photocatalytic reaction by Fe(III)–citrate complex and its effect on the photodegradation of atrazine in aqueous solution. J Photochem Photobiol A197:382–388

    Article  Google Scholar 

  • Pauwels B, Ngwa F, Deconinck S, Verstraete W (2006) Effluent quality of a conventional activated sludge and a membrane bioreactor system treating hospital wastewater. Environ Technol 27:395–402

    Article  CAS  Google Scholar 

  • Perini JAL, Perez-Moya M, Nogueira RFP (2013) Photo-Fenton degradation kinetics of low ciprofloxacin concentration using different iron sources and pH. J Photochem Photobiol A 259:53–58

    Article  CAS  Google Scholar 

  • Pignatello JJ (1992) Dark and photoassisted Fe3+-catalyzed degradation of chlorophenoxy herbicides by hydrogen peroxide. Environ Sci Technol 26:944–951

    Article  CAS  Google Scholar 

  • Rodil R, Quintana JB, Concha-Graña E, López-Mahía P, Muniategui-Lorenzo S, Prada-Rodríguez D (2012) Emerging pollutants in sewage, surface and drinking water in Galicia (NW Spain). Chemosphere 86:1040–1049

    Article  CAS  Google Scholar 

  • Ruppert G, Bauer R, Heisler G, Novalic S (1993) Mineralization of cyclic organic water contaminants by the photo-Fenton reaction—influence of structure and substituents. Chemosphere 27:1339–1347

  • Santos LHMLM, Gros M, Rodriguez-Mozaz S, Delerue-Matos C, Pena A, Barceló D, Montenegro MCBSM (2013) Contribution of hospital effluents to the load of pharmaceuticals in urban wastewaters: identification of ecologically relevant pharmaceuticals. Sci Total Environ 461-462:302–316

    Article  CAS  Google Scholar 

  • Silva MRA, Trovó AG, Nogueira RFP (2007) Degradation of the herbicide tebuthiuron using solar photo-Fenton process and ferric citrate complex at circumneutral pH. J Photochem Photobiol A: Chem 191:187–192

    Article  CAS  Google Scholar 

  • Soares PA, Batalha M, Souza SMAGU, Boaventura RAR, Vilar VJP (2015) Enhancement of a solar photo-Fenton reaction with ferric-organic ligands for the treatment of acrylic-textile dyeing wastewater. J Environ Manag 152:120–231

    Article  CAS  Google Scholar 

  • Tonon D, Tonetti AL, Coraucci FB, Bueno DAC (2015) Wastewater treatment by anaerobic filter and sand filter: hydraulic loading rates for removing organic matter, phosphorus, pathogens and nitrogen in tropical countries. Ecol Eng 82:583–589

    Article  Google Scholar 

  • Trovó AG, Melo SAS, Nogueira RFP (2008) Photodegradation of the pharmaceuticals amoxicillin, bezafibrate and paracetamol by the photo-Fenton process— application to sewage treatment plant effluent. J Photochem Photobiol A: Chem 198:215–220

  • Vázquez MMP, Vázquez PP, Galera MM, García MDG, Uclés A (2013) Ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction coupled with liquid chromatography-quadrupole-linear ion trap-mass spectrometry for simultaneous analysis of pharmaceuticals in wastewaters. J Chromatogr A 1291:19–26

    Article  Google Scholar 

  • Verlicchi P, Galletti A, Petrovic 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 

  • Vieno N, Tuhkanen T, Kronberg L (2007) Elimination of pharmaceuticals in sewage treatment plants in Finland. Water Res 41:1001–1012

    Article  CAS  Google Scholar 

  • Yuan S, Jiang X, Xia X, Zhang H, Zheng S (2013) Detection, occurrence and fate of 22 psychiatric pharmaceuticals in psychiatric hospital and municipal wastewater treatment plants in Beijing, China. Chemosphere 90:2520–2525

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors thank CNPq (Process 308649/2015-0) and FAPESP (2015/21732-5) for support of this work and for scholarship (Process 151022/2014-3) awarded to J.A.L. Perini and CAPES for the scholarship awarded to B. C. Silva.

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Authors and Affiliations

  1. Department of Analytical Chemistry, Institute of Chemistry of Araraquara, UNESP—Univ Estadual Paulista, P.O. Box 355, Araraquara, SP, 14801-970, Brazil

    João A. de Lima Perini, Beatriz Costa e Silva & Raquel F. Pupo Nogueira

  2. School of Civil Engineering, Architecture and Urban Design—FEC, UNICAMP—University of Campinas, P.O. Box 6021, Campinas, SP, 13083-852, Brazil

    Adriano L. Tonetti

Authors
  1. João A. de Lima Perini
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  2. Beatriz Costa e Silva
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  3. Adriano L. Tonetti
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  4. Raquel F. Pupo Nogueira
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Correspondence to Raquel F. Pupo Nogueira.

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Responsible editor: Philippe Garrigues

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Perini, J.A.d.L., Silva, B.C.e., Tonetti, A.L. et al. Photo-Fenton degradation of the pharmaceuticals ciprofloxacin and fluoxetine after anaerobic pre-treatment of hospital effluent. Environ Sci Pollut Res 24, 6233–6240 (2017). https://doi.org/10.1007/s11356-016-7416-4

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  • DOI: https://doi.org/10.1007/s11356-016-7416-4

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