Efficient Removal of Metronidazole by the Photo-Fenton Process with a Magnetic Fe3O4@PBC Composite
Publication: Journal of Environmental Engineering
Volume 146, Issue 7
Abstract
-coated pretreated biochars (@PBC) were prepared for the first time by a Fe(III)-ethanol solution impregnation-calcination method. When photo-Fenton catalysts were used, their effectiveness in removing metronidazole (MNZ) from aqueous media was evaluated. @PBC samples were characterized by X-ray diffraction, scanning electron microscope, vibrating sample magnetometer, X-ray photoelectron spectroscopy, and Brunauer–Emmett–Teller methods. The results showed that coating was successfully formed on the surface of pretreated biochar, and @PBC can be separated by applying an external magnetic field. The coating of did not change the pore structure and maintained a high surface area of the biochar. Fe loading significantly affected the photo-Fenton degradation and adsorption ability of MNZ. The highest MNZ removal rate and the greatest catalytic ability were found in the PBC-6.6Fe sample containing 6.6% Fe by mass. Various operating parameters, such as solution pH, concentration, and MNZ concentration, were tested during MNZ’s photo-Fenton catalytic degradation. The results indicate that the highest MNZ degradation efficiency can be derived from a moderate acidic solution, and the optimal pH is 3. Using PBC-6.6Fe, the increase of concentration from 30 to promotes the degradation of photo-Fenton, and both an excessive and an increase in MNZ concentration suppressed the process. Under the conditions of PBC-6.6Fe, , , and initial pH of 3, 95.1% of MNZ was degraded. The PBC-6.6Fe had good stability, and its removal efficiency was still over 92% after five repeated uses. This study confirmed that •OH played a dominant role, while and played a weaker role in the photo-Fenton system. The results indicated that @PBC served as a prospective visible-light-driven catalyst similar to Fenton for the treatment of wastewater containing MNZ.
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Data Availability Statement
All data, models, and code generated or used during the study appear in the published article.
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (21677046) and the Natural Science Foundation of Hebei Province (B2017205146).
References
Aboudalle, A., H. Djelal, F. Fourcade, L. Domergue, A. A. Assadi, T. Lendormi, S. Taha, and A. Amrane. 2018. “Metronidazole removal by means of a combined system coupling an electro-Fenton process and a conventional biological treatment: By-products monitoring and performance enhancement.” J. Hazard. Mater. 359 (Oct): 85–95. https://doi.org/10.1016/j.jhazmat.2018.07.006.
Alcañiz-Monge, J., M. A. Á. Lillo-Ródenas, A. Bueno-López, and M. A. J. Illán-Gómez. 2007. “The influence of iron chloride addition to the precursor pitch on the formation of activated carbon fibers.” Microporous Mesoporous Mater. 100 (1–3): 202–209. https://doi.org/10.1016/j.micromeso.2006.10.043.
Baiju, A., R. Gandhimathi, S. T. Ramesh, and P. V. Nidheesh. 2018. “Combined heterogeneous electro-Fenton and biological process for the treatment of stabilized landfill leachate.” J. Environ. Manage. 210 (Mar): 328–337. https://doi.org/10.1016/j.jenvman.2018.01.019.
Bansal, P., A. Verma, C. Mehta, and V. K. Sangal. 2019. “Potential use of waste foundry sand in dual process (photocatalysis and photo-Fenton) for the effective removal of phenazone from water: Slurry and fixed-bed approach.” J. Environ. Manage. 233 (Mar): 793–801. https://doi.org/10.1016/j.jenvman.2018.10.005.
Bendesky, A., D. Menéndez, and P. Ostrosky-Wegman. 2002. “Is metronidazole carcinogenic?” Mutat. Res. Rev. Mutat. Res. 511 (2): 133–144. https://doi.org/10.1016/S1383-5742(02)00007-8.
Cai, C., Z. Zhang, L. Jin, S. Ni, Z. Hui, and D. D. Dionysiou. 2016. “Visible light-assisted heterogeneous Fenton with for the degradation of Orange II in water.” Appl. Catal., B 182 (Mar): 456–468. https://doi.org/10.1016/j.apcatb.2015.09.056.
Cheng, W., M. Yang, Y. Xie, B. Liang, Z. Fang, and E. P. Tsang. 2013. “Enhancement of mineralization of metronidazole by the electro-Fenton process with a coated titanium anode.” Chem. Eng. J. 220 (Mar): 214–220. https://doi.org/10.1016/j.cej.2013.01.055.
Fang, Z., J. Chen, X. Qiu, X. Qiu, C. Wen, and L. Zhu. 2011. “Effective removal of antibiotic metronidazole from water by nanoscale zero-valent iron particles.” Desalination 268 (1–3): 60–67. https://doi.org/10.1016/j.desal.2010.09.051.
Ferro-Garci, R. U. A. 1987. “Gasification of active carbons of different texture impregnated with nickel, cobalt and iron.” Carbon 25 (5): 703–708. https://doi.org/10.1016/0008-6223(87)90226-0.
Hou, L., L. Wang, S. Royer, and H. Zhang. 2016. “Ultrasound-assisted heterogeneous Fenton-like degradation of tetracycline over a magnetite catalyst.” J. Hazard. Mater. 302 (Jan): 458–467. https://doi.org/10.1016/j.jhazmat.2015.09.033.
Hu, L., H. He, D. Xia, Y. Huang, J. Xu, H. Li, C. He, W. Yang, D. Shu, and P. K. Wong. 2018. “Highly efficient performance and conversion pathway of photocatalytic oxidation on self-stabilized indirect Z-Scheme g-.” ACS Appl. Mater. Interfaces 10 (22): 18693–18708. https://doi.org/10.1021/acsami.8b03250.
Hu, X., Y. Deng, Z. Gao, B. Liu, and C. Sun. 2012. “Transformation and reduction of androgenic activity of 17α-methyltestosterone in system.” Appl. Catal., B 127 (Oct): 167–174. https://doi.org/10.1016/j.apcatb.2012.08.018.
Hua, Z., W. Ma, X. Bai, R. Feng, L. Yu, X. Zhang, and Z. Dai. 2014. “Heterogeneous Fenton degradation of bisphenol A catalyzed by efficient adsorptive nanocomposites.” Environ. Sci. Pollut. Res. 21 (12): 7737–7745. https://doi.org/10.1007/s11356-014-2728-8.
Kakavandi, B., A. Takdastan, N. Jaafarzadeh, M. Azizi, A. Mirzaei, and A. Azari. 2016. “Application of catalyzing heterogeneous UV-Fenton system for tetracycline removal with a focus on optimization by a response surface method.” J. Photochem. Photobiol., A. 314 (Jan): 178–188. https://doi.org/10.1016/j.jphotochem.2015.08.008.
Katsuki, K., H. Hiroe, and W. Yoshimasa. 2007. “Elimination of selected acidic pharmaceuticals from municipal wastewater by an activated sludge system and membrane bioreactors.” Environ. Sci. Technol. 41 (10): 3708–3714. https://doi.org/10.1021/es061684z.
Klavarioti, M., D. Mantzavinos, and D. Kassinos. 2009. “Removal of residual pharmaceuticals from aqueous systems by advanced oxidation processes.” Environ. Int. 35 (2): 402–417. https://doi.org/10.1016/j.envint.2008.07.009.
Kourdali, S., A. Badis, A. Boucherit, K. Boudjema, and A. Saiba. 2018. “Electrochemical disinfection of bacterial contamination: Effectiveness and modeling study of E. coli inactivation by electro-Fenton, electro-peroxi-coagulation and electrocoagulation.” J. Environ. Manage. 226 (Nov): 106–119. https://doi.org/10.1016/j.jenvman.2018.08.038.
Kremer, M. L. 1985. “Complex” versus “free radical” mechanism for the catalytic decomposition of by ferric ions.” Int. J. Chem. Kinet. 17 (12): 1299–1314. https://doi.org/10.1002/kin.550171207.
Li, F., Y. Li, M. Chai, B. Li, Y. hao, X. Wang, and R. Liu. 2016. “One-step construction of {001} facet-exposed BiOCl hybridized with for enhanced molecular oxygen activation.” Catal. Sci. Technol. 6 (22): 7985–7995. https://doi.org/10.1039/C6CY01306F.
Li, F., Y. Zhao, Q. Wang, X. Wang, Y. Hao, R. Liu, and D. Zhao. 2015. “Enhanced visible-light photocatalytic activity of active heterojunctions synthesized via surface hydroxyl modification.” J. Hazard. Mater. 283 (Feb): 371–381. https://doi.org/10.1016/j.jhazmat.2014.09.035.
Lin, H., Y. Liu, J. Deng, S. Xie, X. Zhao, J. Yang, K. Zhang, Z. Han, and H. Dai. 2017. “Graphitic carbon nitride-supported iron oxides: High-performance photocatalysts for the visible-light-driven degradation of 4-nitrophenol.” J. Photochem. Photobiol., A. 336 (Mar): 105–114. https://doi.org/10.1016/j.jphotochem.2016.12.026.
Liu, W., J. Qian, K. Wang, H. Xu, D. Jiang, Q. Liu, X. Yang, and H. Li. 2013. “Magnetically separable nanoparticles-decorated reduced graphene oxide nanocomposite for catalytic wet hydrogen peroxide oxidation.” J. Inorg. Organomet. Polym. Mater. 23 (4): 907–916. https://doi.org/10.1007/s10904-013-9863-4.
Manjunath, S. V., M. Kumar, H. H. Ngo, and W. Guo. 2017. “Metronidazole removal in powder-activated carbon and concrete-containing graphene adsorption systems: Estimation of kinetic, equilibrium and thermodynamic parameters and optimization of adsorption by a central composite design.” J. Environ. Sci. Health 52 (14): 1–15. https://doi.org/10.1080/10934529.2017.1357406.
Minella, M., G. Marchetti, E. D. Laurentiis, M. Malandrino, V. Maurino, C. Minero, D. Vione, and K. Hanna. 2014. “Photo-Fenton oxidation of phenol with magnetite as iron source.” Appl. Catal., B 154–155 (Jul): 102–109. https://doi.org/10.1016/j.apcatb.2014.02.006.
Oliveira, L. C. A., E. Pereira, I. R. Guimaraes, A. Vallone, M. Pereira, J. P. Mesquita, and K. Sapag. 2009. “Preparation of activated carbons from coffee husks utilizing and as activating agents.” J. Hazard. Mater. 165 (1–3): 87–94. https://doi.org/10.1016/j.jhazmat.2008.09.064.
Oller, I., S. Malato, and J. A. Sánchez-Pérez. 2011. “Combination of advanced oxidation processes and biological treatments for wastewater decontamination—A review.” Sci. Total Environ. 409 (20): 4141–4166. https://doi.org/10.1016/j.scitotenv.2010.08.061.
Rahim Pouran, S., A. A. Abdul Raman, and W. M. A. Wan Daud. 2014. “Review on the application of modified iron oxides as heterogeneous catalysts in Fenton reactions.” J. Cleaner Prod. 64 (Feb): 24–35. https://doi.org/10.1016/j.jclepro.2013.09.013.
Ramírez-Pereda, B., A. Álvarez-Gallegos, J. G. Rangel-Peraza, and Y. A. Bustos-Terrones. 2018. “Kinetics of Acid Orange 7 oxidation by using carbon fiber and reticulated vitreous carbon in an electro-Fenton process.” J. Environ. Manage. 213 (Feb): 279–287. https://doi.org/10.1016/j.jenvman.2018.01.022.
Rivera-Utrilla, J., G. Prados-Joya, M. Sánchez-Polo, M. A. Ferro-García, and I. Bautista-Toledo. 2009. “Removal of nitroimidazole antibiotics from aqueous solution by adsorption/bioadsorption on activated carbon.” J. Hazard. Mater. 170 (1): 298–305. https://doi.org/10.1016/j.jhazmat.2009.04.096.
Rivera-Utrilla, J., M. Sánchez-Polo, M. Á. Ferro-García, G. Prados-Joya, and R. Ocampo-Pérez. 2013. “Pharmaceuticals as emerging contaminants and their removal from water. A review.” Chemosphere 93 (7): 1268–1287. https://doi.org/10.1016/j.chemosphere.2013.07.059.
Rubeena, K. K., P. Hari Prasad Reddy, A. R. Laiju, and P. V. Nidheesh. 2018. “Iron impregnated biochars as heterogeneous Fenton catalyst for the degradation of acid red 1 dye.” J. Environ. Manage. 226 (15): 320–328. https://doi.org/10.1016/j.jenvman.2018.08.055.
Shemer, H., Y. K. Kunukcu, and K. G. Linden. 2006. “Degradation of the pharmaceutical Metronidazole via UV, Fenton and photo-Fenton processes.” Chemosphere 63 (2): 269–276. https://doi.org/10.1016/j.chemosphere.2005.07.029.
Tekin, G., G. Ersöz, and S. Atalay. 2018. “Visible light assisted Fenton oxidation of tartrazine using metal doped bismuth oxyhalides as novel photocatalysts.” J. Environ. Manage. 228 (Dec): 441–450. https://doi.org/10.1016/j.jenvman.2018.08.099.
Vertzoni, M., A. Carlsson, B. Abrahamsson, K. Goumas, and C. Reppas. 2011. “Degradation kinetics of metronidazole and olsalazine by bacteria in ascending colon and in feces of healthy adults.” Int. J. Pharm. 413 (1–2): 81–86. https://doi.org/10.1016/j.ijpharm.2011.04.028.
Wang, J., and L. Chu. 2016. “Irradiation treatment of pharmaceutical and personal care products (PPCPs) in water and wastewater: An overview.” Radiat. Phys. Chem. 125 (Aug): 56–64. https://doi.org/10.1016/j.radphyschem.2016.03.012.
Wang, X., A. Wang, and J. Ma. 2017. “Visible-light-driven photocatalytic removal of antibiotics by newly designed nanocomposites.” J. Hazard. Mater. 336 (Aug): 81. https://doi.org/10.1016/j.jhazmat.2017.04.012.
Wink, D. A., R. W. Nims, M. F. Desrosiers, P. C. Ford, and L. K. Keefer. 1991. “A kinetic investigation of intermediates formed during the Fenton reagent mediated degradation of N-nitrosodimethylamine: Evidence for an oxidative pathway not involving hydroxyl radical.” Chem. Res. Toxicol. 4 (5): 510. https://doi.org/10.1021/tx00023a002.
Yao, Y., L. Fang, Y. Zhu, F. Wei, X. Liu, L. Chao, and S. Wang. 2015. “Magnetic core–shell hybrids for visible light photocatalysis of Orange II.” J. Hazard. Mater. 297 (30): 224–233. https://doi.org/10.1016/j.jhazmat.2015.04.046.
Zhang, K., Y. Liu, J. Deng, S. Xie, and H. Dai. 2018. “Co−Pd/BiVO4: High-performance photocatalysts for the degradation of phenol under visible light irradiation.” Appl. Catal., B 224 (May): 350–359. https://doi.org/10.1016/j.apcatb.2017.10.044.
Zhang, S., Z. Sun, H. Chen, T. Ren, and Q. Yang. 2017. “Degradation of 3,4-dichlorobenzotrifluoride by heterogeneous Fenton-like system.” Acta Scientiae Circumstantiae 37 (4): 1374–1381.
Zhao, G., J. Gao, S. Shen, M. Liu, D. Li, M. Wu, and Y. Lei. 2009. “Ultrasound enhanced electrochemical oxidation of phenol and phthalic acid on boron-doped diamond electrode.” J. Hazard. Mater. 172 (2–3): 1076–1081. https://doi.org/10.1016/j.jhazmat.2009.07.113.
Zulin, H., M. Wenqiang, B. Xue, F. Ranran, Y. Lu, Z. Xiaoyuan, and D. Zhangyan. 2014. “Heterogeneous Fenton degradation of bisphenol A catalyzed by efficient adsorptive nanocomposites.” Environ. Sci. Pollut. Res. 21 (12): 7737–7745. https://doi.org/10.1007/s11356-014-2728-8.
Zúñiga-Benítez, H., and G. A. Peñuela. 2018. “Application of solar photo-Fenton for benzophenone-type UV filters removal.” J. Environ. Manage. 217 (Jul): 929–938. https://doi.org/10.1016/j.jenvman.2018.03.075.
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Published In
Journal of Environmental Engineering
Volume 146 • Issue 7 • July 2020
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©2020 American Society of Civil Engineers.
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Received: Oct 12, 2019
Accepted: Jan 16, 2020
Published online: Apr 25, 2020
Published in print: Jul 1, 2020
Discussion open until: Sep 25, 2020
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