Abstract
Gemifloxacin (GEM) is a broad-spectrum quinolone antibiotic. The presence of GEM residuals in industrial and hospital wastewater has been associated with genotoxicity and antibiotic resistance. In this contribution, the photodegradation of GEM using titanium dioxide nanoparticles (TiO2NPs)/H2O2 as a catalyst was optimized to eliminate residual drug and its photodegradates with antibacterial activity. A half-factorial design was implemented, investigating the effects of pH, initial concentration, H2O2 concentration, TiO2NP loading, and irradiation time. Owing to the time-dependent, multi-transformation of GEM into a wide range of structurally related photodegradation products, the monitoring of GEM throughout the experiments was achieved using both HPLC and potentiometric ion-selective electrodes (ISE). The sensor enabled in-line tracking of residual GEM in the presence of its photodegradates in real time. Results indicated that the pH, irradiation time, and GEM initial concentration were the most significant factors. At the optimum set of experimental conditions, the reaction followed first-order reaction kinetics with a mean percentage degradation of ~ 95% in less than 30 min of irradiation time and almost complete loss of antibacterial activity against Escherichia coli. The promising results demonstrated the efficiency of UV/TiO2NP/H2O2 as a photocatalyst for the breakdown of the pharmacophore of fluoroquinolones from water samples. The high selectivity, minimal solvent consumption, and lack of harmful waste generation confirmed the superiority of in-line monitoring using ISE. Optimization and in-line monitoring protocol should be applicable also at the pharmaceutical industry scale to eliminate the risk of antibiotic resistance.
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References
Abd El-Rahman MK, Zaazaa HE, ElDin NB, Moustafa AA (2016) Just-dip-it (potentiometric ion-selective electrode): an innovative way of greening analytical chemistry. ACS Sustain Chem Eng 4:3122–3132
Ashfaq M, Khan KN, Rasool S, Mustafa G, Saif-Ur-Rehman M, Nazar MF, Sun Q, Yu C-P (2016) Occurrence and ecological risk assessment of fluoroquinolone antibiotics in hospital waste of Lahore, Pakistan. Environ Toxicol Pharmacol 42:16–22
Attallah OA, Al-Ghobashy MA, Nebsen M, Salem MY (2017) Adsorptive removal of fluoroquinolones from water by pectin-functionalized magnetic nanoparticles: process optimization using a spectrofluorimetric assay. ACS Sustain Chem Eng 5:133–145
Blánquez A, Guillén F, Rodríguez J, Arias ME, Hernández M (2016) The degradation of two fluoroquinolone based antimicrobials by sila, an alkaline laccase from streptomyces ipomoeae. World J Microbiol Biotechnol 32:1–8
Chu W, Choy W, So T (2007) The effect of solution pH and peroxide in the TiO2-induced photocatalysis of chlorinated aniline. J Hazard Mater 141:86–91
Currie LA (1999) Nomenclature in evaluation of analytical methods including detection and quantification capabilities:(IUPAC recommendations 1995). Anal Chim Acta 391:105–126
Daughton CG, Jones-Lepp TL (2001) Pharmaceuticals and personal care products in the environment, 1. American Chemical Society; distributed by Oxford university press
Guinea E, Arias C, Cabot PL, Garrido JA, Rodríguez RM, Centellas F, Brillas E (2008) Mineralization of salicylic acid in acidic aqueous medium by electrochemical advanced oxidation processes using platinum and boron-doped diamond as anode and cathodically generated hydrogen peroxide. Water Res 42:499–511
Hapeshi E, Achilleos A, Vasquez M, Michael C, Xekoukoulotakis N, Mantzavinos D, Kassinos D (2010) Drugs degrading photocatalytically: kinetics and mechanisms of ofloxacin and atenolol removal on titania suspensions. Water Res 44:1737–1746
Li W, Guo C, Su B, Xu J (2012) Photodegradation of four fluoroquinolone compounds by titanium dioxide under simulated solar light irradiation. J Chem Technol Biotechnol 87:643–650
Li M, Wei D, Zhao H, Du Y (2014) Genotoxicity of quinolones: substituents contribution and transformation products QSAR evaluation using 2D and 3D models. Chemosphere 95:220–226
Lin C-C, Lin H-Y, Hsu L-J (2016) Degradation of ofloxacin using UV/H2O2 process in a large photoreactor. Sep Purif Technol 168:57–61
Liu W, Andrews SA, Stefan MI, Bolton JR (2003) Optimal methods for quenching H 2 O 2 residuals prior to UFC testing. Water Res 37:3697–3703
Martínez-Huitle CA, Rodrigo MA, Sirés I, Scialdone O (2015) Single and coupled electrochemical processes and reactors for the abatement of organic water pollutants: a critical review. Chem Rev 115:13362–13407
Nadim A, Al-Ghobashy M, Nebsen M, Shehata M (2015a) Gallic acid magnetic nanoparticles for photocatalytic degradation of meloxicam:synthesis,characterization and application to pharmaceutical wastewater treatment. RSC Adv 5:104981–104990
Nadim A, Al-Ghobashy M, Nebsen M, A.Shehata M (2015b): Optimization of photocatalytic degradation of meloxicam using titanium dioxide nanoparticles: application to pharmaceutical wastewater analysis, treatment, and cleaning validation. Environ Sci Pollut Res 22, 15516–15525
Neyens E, Baeyens J (2003) A review of classic Fenton’s peroxidation as an advanced oxidation technique. J Hazard Mater 98:33–50
Ou H-s, Ye J-s, Ma S, Wei C-h, Gao N-y, He J-z (2016) Degradation of ciprofloxacin by UV and UV/H2O2 via multiple-wavelength ultraviolet light-emitting diodes: effectiveness, intermediates and antibacterial activity. Chem Eng J 289:391–401
Özcan A, Özcan AA, Demirci Y (2016) Evaluation of mineralization kinetics and pathway of norfloxacin removal from water by electro-fenton treatment. Chem Eng J 304:518–526
Peres M, Maniero M, Guimarães J (2015) Photocatalytic degradation of ofloxacin and evaluation of the residual antimicrobial activity. Photochem Photobiol Sci 14:556–562
Prutthiwanasan B, Phechkrajarng C, Suntornsuk L (2016) Fluorescent labelling of ciprofloxacin and norfloxacin and its application for residues analysis in surface water. Talanta 159:74–79
Rodrigues-Silva C, Maniero MG, Rath S, Guimarães JR (2013) Degradation of flumequine by photocatalysis and evaluation of antimicrobial activity. Chem Eng J 224:46–52
Singh GD, Gupta K, Shrivastawa A (2016) Uv and solar degradation of ofloxacin antibiotic. Int J Curr Microbiol App Sci 5:742–752
Sturini M, Speltini A, Maraschi F, Profumo A, Pretali L, Irastorza EA, Fasani E, Albini A (2012) Photolytic and photocatalytic degradation of fluoroquinolones in untreated river water under natural sunlight. Appl Catal B Environ 119:32–39
Sturini M, Speltini A, Maraschi F, Profumo A, Tarantino S, Gualtieri AF, Zema M (2016) Removal of fluoroquinolone contaminants from environmental waters on sepiolite and its photo-induced regeneration. Chemosphere 150:686–693
Tammam MH (2014) Photostability studies on gemifloxacin and lomefloxacin in bulk powder and dosage forms. Eur J Chem 5:73–80
Van Doorslaer X, Heynderickx PM, Demeestere K, Debevere K, Van Langenhove H, Dewulf J (2012) TiO2 mediated heterogeneous photocatalytic degradation of moxifloxacin: operational variables and scavenger study. Appl Catal B Environ 111:150–156
Acknowledgements
We thank Dr. Ayman Yassin, A/Prof. of Microbiology & Immunology, Cairo University, for his help with the antimicrobial assays.
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Ibrahim, F.A., Al-Ghobashy, M.A., Abd El-Rahman, M.K. et al. Optimization and in line potentiometric monitoring of enhanced photocatalytic degradation kinetics of gemifloxacin using TiO2 nanoparticles/H2O2 . Environ Sci Pollut Res 24, 23880–23892 (2017). https://doi.org/10.1007/s11356-017-0045-8
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DOI: https://doi.org/10.1007/s11356-017-0045-8