Ciprofloxacin degradation in photo-Fenton and photo-catalytic processes: Degradation mechanisms and iron chelation
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摘要
Ciprofloxacin(CIP)is a broad spectrum synthetic antibiotic drug of fluoroquinolones class.CIP can act as a bidentate ligand forming iron complexes during its degradation in the photoFenton process(PFP).This work investigates on PFP for the degradation of CIP to understand the formation mechanism and stability of iron complexes under ultraviolet(UV)-light illumination.A comparison was made with the UV-photocatalysis(UV/TiO_2)process where CIP doesn't form a complex.In PFP,the optimal dose of Fe~(2+)and H_2O_2were found to be 1.25 and10 mmol/L with pH of 3.5.An optimal TiO_2dose of 1.25 g/L was determined in the UV/TiO_2process.Maximum CIP removal and mineralization efficiency of 93.1%and 47.3%were obtained in PFP against 69.7%and 27.6%in the UV/TiO_2process.The mass spectra could identify seventeen intermediate products including iron-CIP complexes in PFP,and only seven intermediate products were found in the UV/TiO_2process with a majority of common products in both the processes.The proposed mechanism supported by the mass spectra bridged the routes of CIP cleavage in the PFP and UV/TiO_2process,and the decomposition pathway of Fe~(3+)-CIP chelate complexes in PFP was also elucidated.Both in PFP and UV/TiO_2processes,the target site of HO~·radical attack was the secondary-N atom present in the piperazine ring of the CIP molecule.The death of Escherichia coli bacteria was 55.7%and 66.8%in comparison to the control media after 45 min of treatment in PFP and UV/TiO_2process,respectively.
Ciprofloxacin(CIP)is a broad spectrum synthetic antibiotic drug of fluoroquinolones class.CIP can act as a bidentate ligand forming iron complexes during its degradation in the photoFenton process(PFP).This work investigates on PFP for the degradation of CIP to understand the formation mechanism and stability of iron complexes under ultraviolet(UV)-light illumination.A comparison was made with the UV-photocatalysis(UV/TiO_2)process where CIP doesn't form a complex.In PFP,the optimal dose of Fe~(2+)and H_2O_2were found to be 1.25 and10 mmol/L with pH of 3.5.An optimal TiO_2dose of 1.25 g/L was determined in the UV/TiO_2process.Maximum CIP removal and mineralization efficiency of 93.1%and 47.3%were obtained in PFP against 69.7%and 27.6%in the UV/TiO_2process.The mass spectra could identify seventeen intermediate products including iron-CIP complexes in PFP,and only seven intermediate products were found in the UV/TiO_2process with a majority of common products in both the processes.The proposed mechanism supported by the mass spectra bridged the routes of CIP cleavage in the PFP and UV/TiO_2process,and the decomposition pathway of Fe~(3+)-CIP chelate complexes in PFP was also elucidated.Both in PFP and UV/TiO_2processes,the target site of HO~·radical attack was the secondary-N atom present in the piperazine ring of the CIP molecule.The death of Escherichia coli bacteria was 55.7%and 66.8%in comparison to the control media after 45 min of treatment in PFP and UV/TiO_2process,respectively.
Ciprofloxacin(CIP)is a broad spectrum synthetic antibiotic drug of fluoroquinolones class.CIP can act as a bidentate ligand forming iron complexes during its degradation in the photoFenton process(PFP).This work investigates on PFP for the degradation of CIP to understand the formation mechanism and stability of iron complexes under ultraviolet(UV)-light illumination.A comparison was made with the UV-photocatalysis(UV/TiO_2)process where CIP doesn't form a complex.In PFP,the optimal dose of Fe~(2+)and H_2O_2were found to be 1.25 and10 mmol/L with pH of 3.5.An optimal TiO_2dose of 1.25 g/L was determined in the UV/TiO_2process.Maximum CIP removal and mineralization efficiency of 93.1%and 47.3%were obtained in PFP against 69.7%and 27.6%in the UV/TiO_2process.The mass spectra could identify seventeen intermediate products including iron-CIP complexes in PFP,and only seven intermediate products were found in the UV/TiO_2process with a majority of common products in both the processes.The proposed mechanism supported by the mass spectra bridged the routes of CIP cleavage in the PFP and UV/TiO_2process,and the decomposition pathway of Fe~(3+)-CIP chelate complexes in PFP was also elucidated.Both in PFP and UV/TiO_2processes,the target site of HO~·radical attack was the secondary-N atom present in the piperazine ring of the CIP molecule.The death of Escherichia coli bacteria was 55.7%and 66.8%in comparison to the control media after 45 min of treatment in PFP and UV/TiO_2process,respectively.
引文
Agarwal,N.,Ray,R.S.,Farooq,M.,Pant,A.B.,Hans,R.K.,2007.Photosensitizing potential of ciprofloxacin at ambient level of UV radiation.Photochem.Photobiol.83,1226-1236.
Alvarez,J.D.,Avella,E.,Zamora,R.M.,Zanella,R.,2016.Photocatalytic degradation of ciprofloxacin using mono-(au,Ag and Cu)and bi-(Au-Ag and Au-Cu)metallic nanoparticles supported on Ti O2under UV-C and simulated sunlight.Catal.Today 266,175-187.
An,T.,Yang,H.,Li,G.,Song,W.,Cooper,J.W.,Nie,X.,2010.Kinetics and mechanism of advanced oxidation processes(AOPs)in degradation of ciprofloxacin in water.Appl.Catal.B94,288-294.
Avisar,D.,Lester,Y.,Mamane,H.,2010.p H induced polychromatic UV treatment for the removal of a mixture of SMX,OTC and CIP from water.J.Hazard.Mater.175,1068-1074.
Bandoli,G.,Dolmella,A.,Tisato,F.,Porchia,M.,Refosco,F.,2009.Mononuclear six-coordinated Ga(III)complexes:a comprehensive survey.Coord.Chem.Rev.253,56-77.
Bauer,R.,Waldner,G.,Fallmann,H.,Hager,S.,Klare,M.,Krutzler,T.,et al.,1999.The photo-Fenton reaction and the TiO2/UVprocess for wastewater treatment-Novel developments.Catal.Today 53,131-144.
Buchanan,W.,Roddick,F.,Porter,N.,Drikas,M.,2005.Fractionation of UV and UV pretreated natural organic matter from drinking water.Environ.Sci.Technol.39,4647-4654.
Carp,O.,Huisman,C.L.,Reller,A.,2004.Photoinduced reactivity of titanium dioxide.Prog.Solid State Chem.33-177.
Doorslaer,X.V.,Demeestere,K.,Heynderickx,P.M.,Langenhove,H.V.,Dewulf,J.,2011.UV-A and UV-C induced photolytic and photocatalytic degradation of aqueous ciprofloxacin and moxifloxacin:reaction kinetics and role of adsorption.Appl.Catal.B 101,540-547.
Finar,I.L.,2001.Organic Chemistry(5th ed.).Holloway,London.
Giri,A.S.,Golder,A.K.,2014a.Ciprofloxacin degradation from aqueous solution by Fenton oxidation:Reaction kinetics and degradation mechanisms.RSC Adv.4,6738-6745.
Giri,A.S.,Golder,A.K.,2014b.Chloramphenicol degradation in Fenton and photo-Fenton:formation of Fe2+-Chloramphenicol chelate and reaction pathways.Ind.Eng.Chem.Res.53(42),16196-16203.
Giri,A.S.,Golder,A.K.,2015.Drug mixture decomposition in photo-assisted Fenton process:comparison to singly treatment,evolution of inorganic ions and toxicity assay.Chemosphere 127,254-261.
Golet,E.M.,Strehler,A.,Alder,A.C.,Ginger,W.,2002.Determination of fluoroquinolone antibacterial agents in sewage sludge and sludge-treated soil using accelerated solvent extraction followed by solid-phase extraction.Anal.Chem.74,5455-5462.
Guangguo,W.,Guoping,W.,Xuchun,F.,Longgman,Z.,2003.Synthesis,crystal structure,stacking effect and antibacterial studies of a novel quaternary copper(II)complex with quinolone.Int.Molecules 8,287-296.
Gunten,U.V.,2003.Ozonation of drinking water:part I.Oxidation kinetics and product formation.Water Res.37,1443-1467.
Hesse,M.,Meier,H.,Zeeh,B.,2008.Spectroscopic Methods in Organic Chemistry(2nd ed.)Thieme:New York,pp 15-17.
Kavitha,V.,Palanivelu,K.,2004.The role of ferrous ion in Fenton and photo-Fenton processes for the degradation of phenol.Chemosphere 585,1235-1243.
Klameth,N.,Malato,S.,Aguera,A.,Fernandez-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.
Klavarioti,M.,Mantzavinos,D.,Kassinos,D.,2009.Removal of residual pharmaceuticals from aqueous systems by advanced oxidation processes.Environ.Int.35,402-417.
Knight,R.J.,Sylva,R.N.,1975.Spectrophotometric investigation of iron(III)hydrolysis in light and heavy water at 25°C.J.Inorg.Nucl.Chem.37,779-783.
Kugelmann,E.,Albert,R.C.,Bringmann,G.,Holzgrabe,U.,2011.Fenton's oxidation:a tool for the investigation of potential drug metabolites.J.Pharm.Biomed.Anal.54,1047-1058.
Lai,H.T.,Liu,S.M.,Chien,Y.H.,1995.Degradation of chloramphenicol and oxytetracycline in aquaculture pond sediments.J.Environ.Sci.Health 30,1897-1923.
Larsson,D.G.J.,de Pedro,C.,Paxeus,N.,2007.Effluent from drug manufactures contains extremely high levels of pharmaceuticals.J.Hazard.Mater.148,751-755.
Levard,C.,Mitra,S.,Yang,T.,Jew,A.D.,Badireddy,A.R.,Gregory,V.,et al.,2013.Effect of chloride on the dissolution rate of silver nanoparticles and toxicity to E.coli.Environ.Sci.Technol.47,5738-5745.
Li,H.,Lei,Y.,Fang,Y.,Xu,Y.,Zhu,L,Li,X.,2011.Photocatalytic reduction of carbon dioxide to methanol by Cu2O/Si C nanocrystallite under visible light irradiation.Nat.Gas Chem.20,145-150.
Liang,B.,Cheng,H.Y.,Kong,D.Y.,Gao,S.H.,Sun,F.,Cui,D.,et al.,2013.Accelerated reduction of chlorinated nitroaromatic antibiotic chloramphenicol by biocathode.Environ.Sci.Technol.47,5353-5361.
Lin,S.H.,Lo,C.C.,1997.Fenton process for treatment of desizing wastewater.Water Res.31,2050-2056.
Luis,A.D.,Lombranda,J.I.,Vorana,F.,Menendez,A.,2009.Kinetic study and hydrogen peroxide consumption of phenolic compounds oxidation by Fenton's reagent.Korean J.Chem.Eng.26(1),48-56.
Martinez,L.J.,Sik,R.H.,Chignell,C.F.,1998.Fluoroquinolone antimicrobials:singlet oxygen,superoxide and phototoxicity.Photochem.Photobiol.67,399-403.
Mase,T.,Sugita,M.,Mori,S.,Iwamoto,T.,Tokutome,K.,Katayama,H.,2013.Study of vanadium-modified N/Si codoped TiO2in aqueous solution and its photocatalytic activity.Chem.Eng.J.225,440-446.
Miralles-Cuevas,S.,Oller,I.,Perez,J.A.S.,Malato,S.,2014.Removal of pharmaceuticals from MWTP effluent by nanofiltration and solar photo-Fenton using two different iron complexes at neutral pH.Water Res.64,23-31.
Mjos,K.D.,Cawthray,J.F.,Judith,G.J.,Orvig,F.,Orvig,C.,2017.Gallium(III)and iron(III)complexes of quinolone Antimicrobials.Dalton Trans.45,131-146.
Moraes,J.E.F.,Quina,F.H.,Nascimento,C.A.O.,Silva,D.N.,Chiavone-Filho,O.,2004.Treatment of saline wastewater contaminated with hydrocarbons by the photo-Fenton Process.Environ.Sci.Technol.38,1183-1187.
Ou,S.H.,Ye,S.J.,Ma,S.,Wei,H.C.,Gao,N.Y.,He,J.Z.,2016.Degradation of ciprofloxacin by UV and UV/H2O2via multiplewavelength ultraviolet light-emitting diodes:Effectiveness,intermediates and antibacterial activity.Chem.Engg.J.289,391-401.
Pignatello,J.J.,Oliveros,E.,MacKay,A.,2006.Advanced oxidation processes for organic contaminant destruction based on the Fenton reaction and related chemistry.Crit.Rev.Environ.Sci.Technol.36,1-84.
Puma,G.L.,Yue,P.L.,1991.Photocatalytic oxidation of chlorophenols in single component and multi-component systems.Ind.Eng.Chem.Res.36,27-38.
Rao,Ch.V.,Golder,A.K.,2016.Development of a bio-mediated technique of silver-doping on titania.Colliod Surf.A:Physicochem.Eng.Aspects 506,557-565.
Rivas,F.J.,Beltran,F.J.,Frades,J.,Buxeda,P.,2001.Oxidation of phydroxybenzoic acid.Water Res.35(2),387-396.
Saadatjou,M.,Taghdiri,R.,Farrokhi,I.,2010.Municipal solid waste landfill leachate treatment by fenton,photo-Fenton and Fenton-like processes:effect of some variables.Environ.Health Sci.Eng.7(4),345-352.
Schwabe,U.,Paffrath,D.,2011.Arzneiverordnungs-report.Springer-Verlag.Berlin.Heidelberg,New York.
Sohrabi,M.R.,Ghavami,M.,2008.Experimental design used for Nano photo catalytic degradation of the pharmaceutical agent569 Aspirin.J.Chem.Pharm.Res.153,1235-1239.
Sykes,P.A.,2005.Guidebook to Mechanism in Organic Chemistry,6th Ed.Fellow of Christ's College:Cambridge,U.K.
Tahir,K.,Nazir,S.,Li,B.,Ahmad,A.,Nasir,T.,Khan,A.U.,Shah,S.A.,Khan,Z.U.,Yasin,G.,et al.,2016.Sapium sebiferum leaf extract mediated synthesis of palladium nanoparticles and in vitro investigation of their bacterial and photocatalytic activities.J.Photochem.Photobiol.B 164,164-173.
Ternes,T.,2003.Occurrence of drugs in German sewage treatment plants and rivers.Water Res.32(11),3245-3260.
Trovo,A.G.,Raquel,F.P.,Nogueira,A.A.,Carla,S.,2009.Photodegradation of sulfamethoxazole in various aqueous media:Persistence,toxicity and photoproducts assessment.Chemosphere 596,1292-1298.
Turel,I.,2002.The interactions of metal ions with quinolone antibacterial agents.Coordin.Coordin.Chem.Rev.232,27-47.
Zang,H.,Huang,C.H.,2005.Aquatic photochemistry of fluoroquinolone antibiotics.Environ.Sci.Technol.39,4474-4483.
Zepp,R.G.,Faust,B.C.,Hoigne,J.,1992.Photo production of hydrated electrons from natural organic solutes in aquatin environments.Environ.Sci.Technol.26,313-319.
Zhang,H.,Zhang,P.,Ji,Y.,Tian,J.,Du,Z.,2015.Photocatalytic degradation of four non-steroidal anti-inflammatory drugs in water under visible light by P25-TiO2/tetraethyl orthosilicate film and determination via ultra performance liquid chromatography electrospray tandem mass spectrometry.Chem.Eng.J.262,1108-1115.
Zhang,X.,Wang,C.,Yu,C.,Teng,B.,He,Y.,Zhao,L.,et al.,2017.Application of Ag/AgBr/GdVO4composite photocatalyst in wastewater treatment.J.Environ.Sci.63,68-75.
Zhou,W.,Moore,D.E.,2001.Photochemical decomposition of sulfamethoxazole.Int.J.Pharm.110,55-63.
Alvarez,J.D.,Avella,E.,Zamora,R.M.,Zanella,R.,2016.Photocatalytic degradation of ciprofloxacin using mono-(au,Ag and Cu)and bi-(Au-Ag and Au-Cu)metallic nanoparticles supported on Ti O2under UV-C and simulated sunlight.Catal.Today 266,175-187.
An,T.,Yang,H.,Li,G.,Song,W.,Cooper,J.W.,Nie,X.,2010.Kinetics and mechanism of advanced oxidation processes(AOPs)in degradation of ciprofloxacin in water.Appl.Catal.B94,288-294.
Avisar,D.,Lester,Y.,Mamane,H.,2010.p H induced polychromatic UV treatment for the removal of a mixture of SMX,OTC and CIP from water.J.Hazard.Mater.175,1068-1074.
Bandoli,G.,Dolmella,A.,Tisato,F.,Porchia,M.,Refosco,F.,2009.Mononuclear six-coordinated Ga(III)complexes:a comprehensive survey.Coord.Chem.Rev.253,56-77.
Bauer,R.,Waldner,G.,Fallmann,H.,Hager,S.,Klare,M.,Krutzler,T.,et al.,1999.The photo-Fenton reaction and the TiO2/UVprocess for wastewater treatment-Novel developments.Catal.Today 53,131-144.
Buchanan,W.,Roddick,F.,Porter,N.,Drikas,M.,2005.Fractionation of UV and UV pretreated natural organic matter from drinking water.Environ.Sci.Technol.39,4647-4654.
Carp,O.,Huisman,C.L.,Reller,A.,2004.Photoinduced reactivity of titanium dioxide.Prog.Solid State Chem.33-177.
Doorslaer,X.V.,Demeestere,K.,Heynderickx,P.M.,Langenhove,H.V.,Dewulf,J.,2011.UV-A and UV-C induced photolytic and photocatalytic degradation of aqueous ciprofloxacin and moxifloxacin:reaction kinetics and role of adsorption.Appl.Catal.B 101,540-547.
Finar,I.L.,2001.Organic Chemistry(5th ed.).Holloway,London.
Giri,A.S.,Golder,A.K.,2014a.Ciprofloxacin degradation from aqueous solution by Fenton oxidation:Reaction kinetics and degradation mechanisms.RSC Adv.4,6738-6745.
Giri,A.S.,Golder,A.K.,2014b.Chloramphenicol degradation in Fenton and photo-Fenton:formation of Fe2+-Chloramphenicol chelate and reaction pathways.Ind.Eng.Chem.Res.53(42),16196-16203.
Giri,A.S.,Golder,A.K.,2015.Drug mixture decomposition in photo-assisted Fenton process:comparison to singly treatment,evolution of inorganic ions and toxicity assay.Chemosphere 127,254-261.
Golet,E.M.,Strehler,A.,Alder,A.C.,Ginger,W.,2002.Determination of fluoroquinolone antibacterial agents in sewage sludge and sludge-treated soil using accelerated solvent extraction followed by solid-phase extraction.Anal.Chem.74,5455-5462.
Guangguo,W.,Guoping,W.,Xuchun,F.,Longgman,Z.,2003.Synthesis,crystal structure,stacking effect and antibacterial studies of a novel quaternary copper(II)complex with quinolone.Int.Molecules 8,287-296.
Gunten,U.V.,2003.Ozonation of drinking water:part I.Oxidation kinetics and product formation.Water Res.37,1443-1467.
Hesse,M.,Meier,H.,Zeeh,B.,2008.Spectroscopic Methods in Organic Chemistry(2nd ed.)Thieme:New York,pp 15-17.
Kavitha,V.,Palanivelu,K.,2004.The role of ferrous ion in Fenton and photo-Fenton processes for the degradation of phenol.Chemosphere 585,1235-1243.
Klameth,N.,Malato,S.,Aguera,A.,Fernandez-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.
Klavarioti,M.,Mantzavinos,D.,Kassinos,D.,2009.Removal of residual pharmaceuticals from aqueous systems by advanced oxidation processes.Environ.Int.35,402-417.
Knight,R.J.,Sylva,R.N.,1975.Spectrophotometric investigation of iron(III)hydrolysis in light and heavy water at 25°C.J.Inorg.Nucl.Chem.37,779-783.
Kugelmann,E.,Albert,R.C.,Bringmann,G.,Holzgrabe,U.,2011.Fenton's oxidation:a tool for the investigation of potential drug metabolites.J.Pharm.Biomed.Anal.54,1047-1058.
Lai,H.T.,Liu,S.M.,Chien,Y.H.,1995.Degradation of chloramphenicol and oxytetracycline in aquaculture pond sediments.J.Environ.Sci.Health 30,1897-1923.
Larsson,D.G.J.,de Pedro,C.,Paxeus,N.,2007.Effluent from drug manufactures contains extremely high levels of pharmaceuticals.J.Hazard.Mater.148,751-755.
Levard,C.,Mitra,S.,Yang,T.,Jew,A.D.,Badireddy,A.R.,Gregory,V.,et al.,2013.Effect of chloride on the dissolution rate of silver nanoparticles and toxicity to E.coli.Environ.Sci.Technol.47,5738-5745.
Li,H.,Lei,Y.,Fang,Y.,Xu,Y.,Zhu,L,Li,X.,2011.Photocatalytic reduction of carbon dioxide to methanol by Cu2O/Si C nanocrystallite under visible light irradiation.Nat.Gas Chem.20,145-150.
Liang,B.,Cheng,H.Y.,Kong,D.Y.,Gao,S.H.,Sun,F.,Cui,D.,et al.,2013.Accelerated reduction of chlorinated nitroaromatic antibiotic chloramphenicol by biocathode.Environ.Sci.Technol.47,5353-5361.
Lin,S.H.,Lo,C.C.,1997.Fenton process for treatment of desizing wastewater.Water Res.31,2050-2056.
Luis,A.D.,Lombranda,J.I.,Vorana,F.,Menendez,A.,2009.Kinetic study and hydrogen peroxide consumption of phenolic compounds oxidation by Fenton's reagent.Korean J.Chem.Eng.26(1),48-56.
Martinez,L.J.,Sik,R.H.,Chignell,C.F.,1998.Fluoroquinolone antimicrobials:singlet oxygen,superoxide and phototoxicity.Photochem.Photobiol.67,399-403.
Mase,T.,Sugita,M.,Mori,S.,Iwamoto,T.,Tokutome,K.,Katayama,H.,2013.Study of vanadium-modified N/Si codoped TiO2in aqueous solution and its photocatalytic activity.Chem.Eng.J.225,440-446.
Miralles-Cuevas,S.,Oller,I.,Perez,J.A.S.,Malato,S.,2014.Removal of pharmaceuticals from MWTP effluent by nanofiltration and solar photo-Fenton using two different iron complexes at neutral pH.Water Res.64,23-31.
Mjos,K.D.,Cawthray,J.F.,Judith,G.J.,Orvig,F.,Orvig,C.,2017.Gallium(III)and iron(III)complexes of quinolone Antimicrobials.Dalton Trans.45,131-146.
Moraes,J.E.F.,Quina,F.H.,Nascimento,C.A.O.,Silva,D.N.,Chiavone-Filho,O.,2004.Treatment of saline wastewater contaminated with hydrocarbons by the photo-Fenton Process.Environ.Sci.Technol.38,1183-1187.
Ou,S.H.,Ye,S.J.,Ma,S.,Wei,H.C.,Gao,N.Y.,He,J.Z.,2016.Degradation of ciprofloxacin by UV and UV/H2O2via multiplewavelength ultraviolet light-emitting diodes:Effectiveness,intermediates and antibacterial activity.Chem.Engg.J.289,391-401.
Pignatello,J.J.,Oliveros,E.,MacKay,A.,2006.Advanced oxidation processes for organic contaminant destruction based on the Fenton reaction and related chemistry.Crit.Rev.Environ.Sci.Technol.36,1-84.
Puma,G.L.,Yue,P.L.,1991.Photocatalytic oxidation of chlorophenols in single component and multi-component systems.Ind.Eng.Chem.Res.36,27-38.
Rao,Ch.V.,Golder,A.K.,2016.Development of a bio-mediated technique of silver-doping on titania.Colliod Surf.A:Physicochem.Eng.Aspects 506,557-565.
Rivas,F.J.,Beltran,F.J.,Frades,J.,Buxeda,P.,2001.Oxidation of phydroxybenzoic acid.Water Res.35(2),387-396.
Saadatjou,M.,Taghdiri,R.,Farrokhi,I.,2010.Municipal solid waste landfill leachate treatment by fenton,photo-Fenton and Fenton-like processes:effect of some variables.Environ.Health Sci.Eng.7(4),345-352.
Schwabe,U.,Paffrath,D.,2011.Arzneiverordnungs-report.Springer-Verlag.Berlin.Heidelberg,New York.
Sohrabi,M.R.,Ghavami,M.,2008.Experimental design used for Nano photo catalytic degradation of the pharmaceutical agent569 Aspirin.J.Chem.Pharm.Res.153,1235-1239.
Sykes,P.A.,2005.Guidebook to Mechanism in Organic Chemistry,6th Ed.Fellow of Christ's College:Cambridge,U.K.
Tahir,K.,Nazir,S.,Li,B.,Ahmad,A.,Nasir,T.,Khan,A.U.,Shah,S.A.,Khan,Z.U.,Yasin,G.,et al.,2016.Sapium sebiferum leaf extract mediated synthesis of palladium nanoparticles and in vitro investigation of their bacterial and photocatalytic activities.J.Photochem.Photobiol.B 164,164-173.
Ternes,T.,2003.Occurrence of drugs in German sewage treatment plants and rivers.Water Res.32(11),3245-3260.
Trovo,A.G.,Raquel,F.P.,Nogueira,A.A.,Carla,S.,2009.Photodegradation of sulfamethoxazole in various aqueous media:Persistence,toxicity and photoproducts assessment.Chemosphere 596,1292-1298.
Turel,I.,2002.The interactions of metal ions with quinolone antibacterial agents.Coordin.Coordin.Chem.Rev.232,27-47.
Zang,H.,Huang,C.H.,2005.Aquatic photochemistry of fluoroquinolone antibiotics.Environ.Sci.Technol.39,4474-4483.
Zepp,R.G.,Faust,B.C.,Hoigne,J.,1992.Photo production of hydrated electrons from natural organic solutes in aquatin environments.Environ.Sci.Technol.26,313-319.
Zhang,H.,Zhang,P.,Ji,Y.,Tian,J.,Du,Z.,2015.Photocatalytic degradation of four non-steroidal anti-inflammatory drugs in water under visible light by P25-TiO2/tetraethyl orthosilicate film and determination via ultra performance liquid chromatography electrospray tandem mass spectrometry.Chem.Eng.J.262,1108-1115.
Zhang,X.,Wang,C.,Yu,C.,Teng,B.,He,Y.,Zhao,L.,et al.,2017.Application of Ag/AgBr/GdVO4composite photocatalyst in wastewater treatment.J.Environ.Sci.63,68-75.
Zhou,W.,Moore,D.E.,2001.Photochemical decomposition of sulfamethoxazole.Int.J.Pharm.110,55-63.