Oxytetracycline Removal with Nano Zero Valent Iron Using the Photo-oxidation Process and Optimization of Comparative Ions

Document Type : Research Paper


1 PhD Student of Civil and Environmental Engineering, Tarbiat Modares University, Tehran

2 Prof. of Civil and Environmental Engineering, Tarbiat Modares University, Tehran

3 Assoc. Prof. of Civil and Environmental Engineering, Tarbiat Modares University, Tehran


Due to their rather non-degradability and the emerging genetic resistance against them, antibiotics discharged into domestic effluents pose a serious environmental hazard while the conventional biological treatment methods are not adequately efficienct in removing them. In the present study, the chemical reaction between oxytetracycline (OTC) and nano zerovalent iron (NZVI) modified by UV-A radiation was investigated. In the batch experiments, concentration of reactants, pH, UV power, and time were optimized. In this process, the UV power was 200 W and 155 mg/L OTC in an aqueous solution was degraded after 6.5 hours using 1000 mg/L of the nano-iron powder at pH 3. TOC and COD removal efficiencies of 87, 95, 85, and 89% were achieved at 290 and 348 nm, respectively. In a similar process, no organic compounds remained after 14 hours. Based on XRD analysis, FeO and FeOOH comprised the oxide layer on the surface of the nanoparticles, which had positive effects on the photocatalytic process. Changing the parameters of ORP, pH, and DO during the process caused the photocatalytic reaction to start after 3 hours. It was also found that, due to the presence of ions such as calcium, magnesium, chloride, nitrate, sulfate, and bicarbonate in sewage and surface water compositions, it is necessary to consider their mixture in the oxytetracycline elimination process while their statistical modeling using the response surface methodology also helps in the prediction ofe the effects of these ions. Data optimization results matched thos eof the model at 95% confidence level. It was found that while bicarbonate and sulfate ions had no effect on the process, chloride and nitrate ions had more negative effects than calcium and magnesium on OTC removal since they prohibit the destruction of aromatic rings.


Main Subjects

1. Zhao, C., Deng, H., Li, Y., and Liu, Z. (2010). “Photo-degradation of oxy-tetracycline in aqueous by 5A and 13X loaded with TiO2 under UV irradiation”. Journal of Hazardous Materials, 176 (1-3), 884-892.
2. Awartani, L. S. M., (2010). “Fate of Oxy-tetracycline & D-oxycycline in soil & underground water.” Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science in Chemistry, Faculty of Graduate Studies, at An-Najah National University, Nablus, Palestine.
3. Li, K., Yediler, A., Yang, M., Schulte-Hostede, S., and Hung Wong, M. (2008). “Ozonation of oxy-tetracycline and toxicological assessment of its oxidation by-products.” Chemosphere, 72 (3), 473-478.
4. Li, D., Yang, M., Hu, J., Ren, L., Zhang, Y., and Li, K. (2008). “Determination and fate of Oxy-tetracycline and related compounds in Oxy-tetracycline production wastewater and the receiving river.” Environmental Toxicology and Chemistry, 27(1), 80-86.
5. Shaojun, J., Shourong, Z., Daqiang, Y., Lianhong, W., and Liangyan, C. (2008). “Aqueous oxy-tetracycline degradation and the toxicity change of degradation compounds in photo-irradiation process.” Journal of Environmental Sciences, 20(7), 806-813.
6. Zhao, C., Deng, H., Li, Y., and Liu, Z. (2010). “Photo-degradation of oxy-tetracycline in aqueous by 5A and 13X loaded with TiO2 under UV irradiation.” Journal of Hazardous Materials, 176 (1-3), 884-892.
7. Ötker Uslu, M., and Akmehmet Balcıoğlu, I. (2009). “Comparison of the ozonation and Fenton process performances for the treatment of antibiotic containing manure.” Science of the Total Environment, 407 (11), 3450-3458.
8. Yuan, F., Hu, C., Hu, X., Wei, D., Chen, Y., and Qu, J. (2011). “Photo-degradation and toxicity changes of antibiotics in UV and UV/H2O2 process.” Journal of Hazardous Materials, 185 (2), 1256-1263.
9. Junyapoon, S. (2005). “Use of zero valent Iron for wastewater treatment.” KMITL Sci. Tech. J., 5(3), 587-595.
10. Kassaee, M.Z., Motamedi, E., Mikhak, A., and Rahnemaie, R. (2011). “Nitrate removal from water using iron nano-particles produced by arc discharge vs. reduction.” Chemical Engineering Journal, 166(2), 490-495.
11. Nowack, B., and Bucheli, T. D. (2007). “Occurrence behavior and effects of nano-particles in the environment.” Environmental Pollution, 150 (1), 5-22.
12. Shan, Z. Z., Fu, L. J., Chao, T., Fang, Z. Q., Tian, H. J., and Bin, J. G. (2008). “Rapid decolorization of water soluble azo-dyes by nano sized zero-valent iron immobilized on the exchange resin.” Sci. China B-Chem, 51(2), 186-192.
13. Ghauch, A., Tuqan, A., and Assi, H.A. (2009). “Antibiotic removal from water: Elimination of amoxicillin and ampicillin by micro-scale and nanoscale iron particles.” Environmental Pollution, 157(7), 1626-1635.
14. Li, F.B., Li, X.Z., Liu, C.S., and Liu, T.X. (2007). “Effect of alumina on photocatalytic activity of iron oxides for bisphenol A degradation.” Journal of Hazardous Materials, 149 (1), 199-207.
15. Fu, H., Quan, X., and Zhao, H. (2005). “Photo-degradation of γ-HCH by α-Fe2O3 and the influence of fulvic acid.” Journal of Photochemistry and Photobiology A: Chemistry, 173(1), 143-149.
16. Crane, R.A., and Scott, T.B. (2012). “Nano-scale zero-valent iron: Future prospects for an emerging water treatment technology.” Journal of Hazardous Materials, (211-212), 112-125.
17. Chen, J., Qiu, X., Fang, Z., Yang, M., Pokeung, T., Gu, F., Cheng, W., and Lan, B. (2012). “Removal mechanism of antibiotic metronidazole from aquatic solutions by using nano-scale zero-valent iron particles.” Chemical Engineering Journal, (181– 182), 113-119.
18. Ghauch, A., Abou Assi, H., and Tuqan, A. (2010). “Investigating the mechanism of clofibric acid removal in Fe0/H2O systems.” Journal of Hazardous Materials, 176 (1-3), 48-55.
19. Yan, W., Herzing, A. A., Kiely, C. J., and Zhang, W. (2010). “Nano-scale zero-valent iron (nZVI): Aspects of the core-shell structure and reactions with inorganic species in water.” Journal of Contaminant Hydrology, 118 (3-4), 96-104.
20. Yin, W., Wu, J., Li, P., Wang, X., Zhu, N., Wu, P., and Yang, B. (2012). “Experimental study of zero-valent iron induced nitrobenzene reduction in groundwater: The effects of pH, iron dosage, oxygen and common dissolved anions.” Chemical Engineering Journal, 184 (1), 198-204.
21. Pavia, D. L. (1987). Introduction to spectroscopy, Department of Chemistry Western, Washington University, Bellingham, Washington by W. B. Saunders Company.
22. Granato, D., Branco, G. F., and Araújo Calado, V. M. D. (2011). “Experimental design and application of response surface methodology for process modelling and optimization: A review.” Food Research International, DOI: 10.1016/j. Foodres. 2010. 12. 008.
23. Habib, M.S. Alavi Moghaddam, S.M.R., Arami, M., and Hashemi, S. H. (2012). “Optimization of the electrocoagulation process for removal of Cr(VI) using Taguchi method.” J. of  Water and Wastewater, 22-4(80), 2-8. (In Persian)
24. Greenberg, A.E., Eaton, A.D., Mary, A., and Franson, H. (2005). Standard methods for the examination of water and wastewater, APHA, AWWA, WPCF, Washington, DC, USA.
25. Hsieh, W., Ruhsing Pan, J., Huang, C., Su, Y., and Juang, Y. (2010). “Enhance the photocatalytic activity for the degradation of organic contaminants in water by incorporating TiO2 with zero-valent iron.” Science of the Total Environment, 408 (3), 672-679.
26. Andreozzi, R., Caprio, V., and Marotta, R., (2003). “Iron (III) (hydro) oxide-mediated photo-oxidation of 2-aminophenol in aqueous solution: A kinetic study.” Water Research, 37 (15), 3682-3688.