Abstract
Metronidazole (MNZ) is one of the pharmaceutical products which is considered as one of the most important pollutants in the environment due to its wide use and resistance to biodegradation. Hence, the purpose of this study is the optimization of the electrochemical degradation of the metronidazole (MNZ) antibiotic using electrochemical oxidation on a stainless steel316 coated with beta lead oxide (SS316/β-PbO2) anode. In the studied electrochemical process, the response surface methodology (RSM) involving a five-level ((pH (A) and electrolysis time (B), current density (C), and MNZ concentration (D)). The central composite design (CCD) was employed for optimizing and modeling of the electrochemical process in the degradation of MNZ. The preparation of SS316/β-PbO2 anode was accomplished using the electro-deposition method. Scanning electron microscope (SEM), energy-dispersive X-ray (EDX), and X-ray diffraction (XRD) analyses were conducted for accurate evaluation and characterization of the coated electrode. The effect of influencing factors on electrochemical degradation of MNZ was studied, and the highest MNZ degradation efficiency was observed to be 98.88% after 120 min under the optimal conditions including the supporting electrolyte concentration of 1.0 g/100 cc, the initial MNZ concentration of 30.1 mg/L, pH of 4 and the current density of 9.99 mA/cm2. The linear regression coefficient (R2) between experiments and different response values in the model was 0.99. Moreover, the statistical analysis of the results indicated that in the range studied, the most effective parameters in MNZ degradation are MNZ concentration and pH. In general, it can be concluded that the electrochemical process using SS316/β-PbO2 anode can effectively eliminate metronidazole, and it can be considered as an efficient method in the degradation of various pollutants.
Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: None declared.
Employment or leadership: None declared.
Honorarium: None declared.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
References
Abdessamad, N., H. Akrout, G. Hamdaoui, K. Elghniji, M. Ksibi, and L. Bousselmi. 2013. “Evaluation of the Efficiency of Monopolar and Bipolar BDD Electrodes For Electrochemical Oxidation of Anthraquinone Textile Synthetic Effluent for Reuse.” Chemosphere 93 (7): 1309–16, https://doi.org/10.1016/j.chemosphere.2013.07.011.Search in Google Scholar PubMed
Ahmadzadeh, S., A. Asadipour, M. Pournamdari, B. Behnam, H. R. Rahimi, and M. Dolatabadi. 2017. “Removal of Ciprofloxacin from Hospital Wastewater Using Electrocoagulation Technique by Aluminum Electrode: Optimization and Modelling through Response Surface Methodology.” Process Safety and Environmental Protection 109: 538–47, https://doi.org/10.1016/j.psep.2017.04.026.Search in Google Scholar
Ahmadzadeh, S., and M. Dolatabadi. 2018. “Electrochemical Treatment of Pharmaceutical Wastewater through Electrosynthesis of Iron Hydroxides for Practical Removal of Metronidazole.” Chemosphere 212: 533–39, https://doi.org/10.1016/j.chemosphere.2018.08.107.Search in Google Scholar PubMed
Akrout, H., S. Jellali, and L. Bousselmi. 2015. “Enhancement of Methylene Blue Removal by Anodic Oxidation using BDD Electrode Combined with Adsorption onto Sawdust.” Comptes Rendus Chimie 18 (1): 110–20, https://doi.org/10.1016/j.crci.2014.09.006.Search in Google Scholar
Ammar, H. B. 2016. “Sono-Fenton Process for Metronidazole Degradation in Aqueous Solution: Effect of Acoustic Cavitation and Peroxydisulfate Anion.” Ultrasonics sonochemistry 33: 164–9, https://doi.org/10.1016/j.ultsonch.2016.04.035.Search in Google Scholar PubMed
Ansari, A., and D. Nematollahi. 2018. “A Comprehensive Study on the Electrocatalytic Degradation, Electrochemical Behavior and Degradation Mechanism of Malachite Green using Electrodeposited Nanostructured β-PbO2 Electrodes.” Water research 144: 462–73, https://doi.org/10.1016/j.watres.2018.07.056.Search in Google Scholar PubMed
Ansari, A., and D. Nematollahi. 2020. “Convergent Paired Electrocatalytic Degradation of p-dinitrobenzene by Ti/SnO2-Sb/β-PbO2 anode. A New Insight into the Electrochemical Degradation Mechanism.” Applied Catalysis B: Environmental 261: 118226, https://doi.org/10.1016/j.apcatb.2019.118226.Search in Google Scholar
Arabatzis, I., T. Stergiopoulos, D. Andreeva, S. Kitova, S. Neophytides, and P. Falaras. 2003. “Characterization and Photocatalytic Activity of Au/TiO2 Thin Films for Azo-Dye Degradation.” Journal of Catalysis 220 (1): 127–35, https://doi.org/10.1016/S0021-9517(03)00241-0.Search in Google Scholar
Barros, W. R., J. R. Steter, M. R. Lanza, and A. J. Motheo. 2014. “Degradation of Amaranth Dye in Alkaline Medium by Ultrasonic Cavitation Coupled with Electrochemical Oxidation using a Boron-Doped Diamond Anode.” Electrochimica Acta 143: 180–87, https://doi.org/10.1016/j.electacta.2014.07.141.Search in Google Scholar
Bendesky, A., D. Menéndez, and P. Ostrosky-Wegman. 2002. “Is Metronidazole Carcinogenic?.” Mutation Research/Reviews in Mutation Research 511 (2): 133–44, https://doi.org/10.1016/S1383-5742(02)00007-8.Search in Google Scholar
Brillas, E., and C. A. Martínez-Huitle. 2015. “Decontamination of Wastewaters Containing Synthetic Organic Dyes by Electrochemical Methods. An Updated Review.” Applied Catalysis B: Environmental 166: 603–43, https://doi.org/10.1016/j.apcatb.2014.11.016.Search in Google Scholar
Çelik, A., and N. Aras Ateş. 2006. “The Frequency of Sister Chromatid Exchanges in Cultured Human Peripheral Blood Lymphocyte Treated with Metronidazole In Vitro.” Drug and Chemical Toxicology 29 (1): 85–94, 10.1080/01480540500408663.10.1080/01480540500408663Search in Google Scholar PubMed
Chianeh, F. N., and J. B. Parsa. 2016. “Electrochemical Degradation of Metronidazole from Aqueous Solutions Using Stainless Steel Anode Coated with SnO2 Nanoparticles: Experimental Design.” Journal of the Taiwan Institute of Chemical Engineers 59: 424–32, https://doi.org/10.1016/j.jtice.2015.09.019.Search in Google Scholar
Dai, Q., J. Zhou, M. Weng, X. Luo, D. Feng, and J. Chen. 2016. “Electrochemical Oxidation Metronidazole with Co Modified PbO2 Electrode: Degradation and Mechanism.” Separation and Purification Technology 166: 109–16, https://doi.org/10.1016/j.seppur.2016.04.028.Search in Google Scholar
Dargahi, A., A. Ansari, D. Nematollahi, G. Asgari, R. Shokoohi, and M. R. Samarghandi. 2019. “Parameter Optimization and Degradation Mechanism for Electrocatalytic Degradation of 2, 4-diclorophenoxyacetic acid (2, 4-D) Herbicide by Lead Dioxide Electrodes.” RSC advances 9 (9): 5064–75, https://doi.org/10.1039/C8RA10105A.Search in Google Scholar PubMed PubMed Central
Dargahi, A., M. Mohammadi, F. Amirian, A. Karami, and A. Almasi. 2017. “Phenol Removal from Oil Refinery Wastewater using Anaerobic Stabilization Pond modeling and Process Optimization using Response Surface Methodology (RSM).” Desalination and Water Treatment 87: 199–208, https://doi.org/10.5004/dwt.2017.21064.Search in Google Scholar
Dargahi, A., D. Nematollahi, G. Asgari, R. Shokoohi, A. Ansari, and M. R. Samarghandi. 2018. “Electrodegradation of 2, 4-dichlorophenoxyacetic Acid Herbicide from Aqueous Solution using Three-Dimensional Electrode Reactor with G/β-PbO2 Anode: Taguchi Optimization and Degradation Mechanism Determination.” RSC advances 8 (69): 39256–68, https://doi.org/10.1039/C8RA08471H.Search in Google Scholar
Domínguez, J. R., T. González, P. Palo, and J. Sánchez-Martín. 2010. “Anodic Oxidation of Ketoprofen on Boron-Doped Diamond (BDD) Electrodes. Role of Operative Parameters.” Chemical Engineering Journal 162 (3): 1012–8, https://doi.org/10.1016/j.cej.2010.07.010.Search in Google Scholar
El-Ghenymy, A., F. Centellas, R. M. Rodríguez, P. L. Cabot, J. A. Garrido, I. Sirés, and E. Brillas. 2015. “Comparative Use of Anodic Oxidation, Electro-Fenton and Photoelectro-Fenton with Pt or Boron-Doped Diamond Anode to Decolorize and Mineralize Malachite Green Oxalate Dye.” Electrochimica Acta 182: 247–56, https://doi.org/10.1016/j.electacta.2015.09.078.Search in Google Scholar
Frontistis, Z., D. Mantzavinos, and S. Meriç. 2018. “Degradation of Antibiotic Ampicillin on Boron-Doped Diamond Anode Using the Combined Electrochemical Oxidation-Sodium Persulfate Process.” Journal of environmental management 223: 878–87, https://doi.org/10.1016/j.jenvman.2018.06.099.Search in Google Scholar PubMed
Gao, Y. Q., N. Y. Gao, W. Wang, S. F. Kang, J. H. Xu, H. M. Xiang, and D. Q. Yin. 2018. “Ultrasound-Assisted Heterogeneous Activation of Persulfate by Nano Zero-Valent Iron (nZVI) for the Propranolol Degradation in Water.” Ultrasonics sonochemistry 49: 33–40, https://doi.org/10.1016/j.ultsonch.2018.07.001.Search in Google Scholar PubMed
Garcia-Segura, S., and E. Brillas. 2011. “Mineralization of the Recalcitrant Oxalic and Oxamic Acids by Electrochemical Advanced Oxidation Processes Using a Boron-Doped Diamond Anode.” Water research 45 (9): 2975–84 https://doi.org/10.1016/j.watres.2011.03.017.Search in Google Scholar PubMed
Hou, J., Z. Chen, J. Gao, Y. Xie, L. Li, S. Qin, Q. Wang, D. Mao, and Y. Luo. 2019. “Simultaneous Removal of Antibiotics and Antibiotic Resistance Genes from Pharmaceutical Wastewater using the Combinations of up-flow Anaerobic Sludge Bed, Anoxic-Oxic Tank, and Advanced Oxidation Technologies.” Water research 159: 511–20, https://doi.org/10.1016/j.watres.2019.05.034.Search in Google Scholar PubMed
Ingerslev, F., L. Toräng, M. L. Loke, B. Halling-Sørensen, and N. Nyholm. 2001. “Primary Biodegradation of Veterinary Antibiotics in Aerobic and Anaerobic Surface Water Simulation Systems.” Chemosphere 44 (4): 865–72, https://doi.org/10.1016/S0045-6535(00)00479-3.Search in Google Scholar PubMed
Johnson, M. B., and M. Mehrvar. 2008. “Aqueous Metronidazole Degradation by UV/H2O2 Process in Single-and Multi-Lamp Tubular Photoreactors: Kinetics and Reactor Design.” Industrial & Engineering Chemistry Research 47 (17): 6525–37, https://doi.org/10.1021/ie071637v.Search in Google Scholar
Leng, L., L. Wei, Q. Xiong, S. Xu, W. Li, S. Lv, Q. Lu, L. Wan, Z. Wen, and W. Zhou. 2019. “Use of Microalgae-Based Technology for the Removal of Antibiotics from Wastewater: A Review.” Chemosphere 238: 1–14, https://doi.org/10.1016/j.chemosphere.2019.124680.Search in Google Scholar PubMed
Liu, P., H. Zhang, Y. Feng, F. Yang, and J. Zhang. 2014. “Removal of Trace Antibiotics from Wastewater: A Systematic Study of Nanofiltration Combined with Ozone-Based Advanced Oxidation Processes.” Chemical Engineering Journal 240: 211–20, https://doi.org/10.1016/j.cej.2013.11.057.Search in Google Scholar
Méndez-Díaz, J., G. Prados-Joya, J. Rivera-Utrilla, R. Leyva-Ramos, M. Sánchez-Polo, M. Ferro-García, and N. Medellín-Castillo. 2010. “Kinetic Study of the Adsorption of Nitroimidazole Antibiotics on Activated Carbons in Aqueous Phase.” Journal of colloid and interface science 345 (2): 481–90, https://doi.org/10.1016/j.jcis.2010.01.089.Search in Google Scholar PubMed
Mohammadi, N., M. Yari, and S. Allahkaram. 2013. “Characterization of PbO2 Coating Electrodeposited onto Stainless Steel 316L Substrate for Using as PEMFC's Bipolar Plates.” Surface and Coatings Technology 236: 341–46, https://doi.org/10.1016/j.surfcoat.2013.10.010.Search in Google Scholar
Parsa, J. B., Z. Merati, and M. Abbasi. 2013. “Modeling and Optimizing of Electrochemical Oxidation of CI Reactive Orange 7 on the Ti/Sb–SnO2 as Anode via Response Surface Methodology.” Journal of Industrial and Engineering Chemistry 19 (4): 1350–55, https://doi.org/10.1016/j.jiec.2012.12.039.Search in Google Scholar
Prados-Joya, G., M. Sánchez-Polo, J. Rivera-Utrilla, and M. Ferro-Garcia. 2011. “Photodegradation of the Antibiotics Nitroimidazoles in Aqueous Solution by Ultraviolet Radiation.” Water research 45 (1): 393–403, https://doi.org/10.1016/j.watres.2010.08.015.Search in Google Scholar PubMed
Rivera-Utrilla, J., G. Prados-Joya, M. Sánchez-Polo, M. Ferro-García, and I. Bautista-Toledo. 2009. “Removal of Nitroimidazole Antibiotics from Aqueous Solution by Adsorption/Bioadsorption on Activated Carbon.” Journal of hazardous materials 170 (1): 298–305, https://doi.org/10.1016/j.jhazmat.2009.04.096.Search in Google Scholar PubMed
Samarghandi, M., A. Rahmani, G. Asgari, G. Ahmadidoost, and A. Dargahi. 2018. “Photocatalytic Removal of Cefazolin From Aqueous Solution by AC Prepared from Mango Seed+ ZnO Under UV Irradiation.” Global Nest Journal 20 (2): 399–407, https://doi.org/10.30955/gnj.002588.Search in Google Scholar
Samarghandi, M. R., G. Asgari, R. Shokoohi, A. Dargahi, and A. Arabkouhsar. 2019. “Removing Amoxicillin Antibiotic from Aqueous Solutions by Saccharomyces cerevisiae Bioadsorbent: Kinetic, Thermodynamic and Isotherm Studies.” Desalination and Water Treatment 152: 306–15, https://doi.org/10.5004/dwt.2019.23941.Search in Google Scholar
Samarghandi, M. R., M. Mohammadi, A. Karami, L. Tabandeh, A. Dargahi, and F. Amirian. 2017. “Residue analysis of pesticides, herbicides, and fungicides in various water sources using gas chromatography-mass detection.” Polish Journal of Environmental Studies 26 (5): 2189–95, https://doi.org/10.15244/pjoes/70387.Search in Google Scholar
Samarghandi, M. R., D. Nemattollahi, G. Asgari, R. Shokoohi, A. Ansari, and A. Dargahi. 2019. “Electrochemical Process for 2, 4-D Herbicide Removal from Aqueous Solutions Using Stainless Steel 316 and Graphite Anodes: Optimization Using Response Surface Methodology.” Separation Science and Technology 54 (4): 478–93, https://doi.org/10.1080/01496395.2018.1512618.Search in Google Scholar
Seid-Mohammadi, A., Z. Ghorbanian, D. Asgari, and A. Dargahi. 2019. “Degradation of cex antibiotic from aqueous environment by us/s2 o8 2–/nio process: Optimization using taguchi method and kinetic studies.” Desalination and Water Treatment 171: 444–55, https://doi.org/10.5004/dwt.2019.24777.Search in Google Scholar
Shao, P., X. Duan, J. Xu, J. Tian, W. Shi, S. Gao, M. Xu, F. Cui, and S. Wang. 2017. “Heterogeneous Activation of Peroxymonosulfate by Amorphous Boron for Degradation of Bisphenol S.” Journal of Hazardous Materials 322: 532–9, https://doi.org/10.1016/j.jhazmat.2016.10.020.Search in Google Scholar PubMed
Shao, P., J. Tian, F. Yang, X. Duan, S. Gao, W. Shi, X. Luo, F. Cui, S. Luo, and S. Wang. 2018. “Catalytic Oxidation: Identification and Regulation of Active Sites on Nanodiamonds: Establishing a Highly Efficient Catalytic System for Oxidation of Organic Contaminants (Adv. Funct. Mater. 13/2018).” Advanced Functional Materials 28 (13): 1870081, https://doi.org/10.1002/adfm.201870081.Search in Google Scholar
Sharma, A. K., B. S. Kaith, V. Tanwar, J. K. Bhatia, N. Sharma, S. Bajaj, and S. Panchal. 2019. “RSM-CCD Optimized Sodium Alginate/Gelatin Based ZNS-Nanocomposite Hydrogel for the Effective Removal of Biebrich Scarlet and Crystal Violet Dyes.” International journal of biological macromolecules 129: 214–26, https://doi.org/10.1016/j.ijbiomac.2019.02.034.Search in Google Scholar PubMed
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): 269–76, https://doi.org/10.1016/j.chemosphere.2005.07.029.Search in Google Scholar PubMed
Shokoohi, R., A. Dargahi, R. Khamutian, and Y. Vaziri. 2017a. “Evaluation of the Efficiency of Wastewater Treatment Plants in the Removal of Common Antibiotics from Municipal Wastewater in Hamadan, Iran.” Avicenna J Environ Health Eng 4 (1): e10921, https://doi.org/10.5812/ajehe.10921.Search in Google Scholar
Shokoohi, R., A. J. Jafari, A. Dargahi, and Z. Torkshavand. 2017b. “Study of the Efficiency of Bio-Filter and Activated Sludge (BF/AS) Combined Process in Phenol Removal from Aqueous Solution: Determination of Removing Model According to Response Surface Methodology (RSM).” Desalination and Water Treatment 77: 256–63, https://doi.org/10.5004/dwt.2017.20841.Search in Google Scholar
Shokoohi, R., M. Leili, A. Dargahi, Y. Vaziri, and R. Khamutian. 2017c. “Common Antibiotics in Wastewater of Sina and Besat Hospitals, Hamadan, Iran.” Archives of Hygiene Sciences 6 (2): 152–9, https://doi.org/10.29252/archhygsci.6.2.152.Search in Google Scholar
Sirés, I., E. Brillas, G. Cerisola, and M. Panizza. 2008. “Comparative Depollution of Mecoprop Aqueous Solutions by Electrochemical Incineration Using BDD and PbO2 as High Oxidation Power Anodes.” Journal of Electroanalytical Chemistry 613 (2): 151–9, https://doi.org/10.1016/j.jelechem.2007.10.023.Search in Google Scholar
Wachter, N., J. M. Aquino, M. Denadai, J. C. Barreiro, A. J. Silva, Q. B. Cass, N. Bocchi, and R. C. Rocha Filho. 2019. “Electrochemical Degradation of the Antibiotic Ciprofloxacin in a Flow Reactor Using Distinct BDD Anodes: Reaction Kinetics, Identification and Toxicity of the Degradation Products.” Chemosphere 234: 461–70, https://doi.org/10.1016/j.chemosphere.2019.06.053.Search in Google Scholar PubMed
Wang, X., R. Yin, L. Zeng, and M. Zhu. 2019. “A review of Graphene-Based Nanomaterials for Removal of Antibiotics from Aqueous Environments.” Environmental Pollution 253: 100–10, https://doi.org/10.1016/j.envpol.2019.06.067.Search in Google Scholar PubMed
Wang, Y., C. Shen, M. Zhang, B. T. Zhang, and Y. G. Yu. 2016. “The Electrochemical Degradation of Ciprofloxacin Using a SnO2–Sb/Ti Anode: Influencing Factors, Reaction Pathways and Energy Demand.” Chemical Engineering Journal 296: 79–89, https://doi.org/10.1016/j.cej.2016.03.093.Search in Google Scholar
Watkinson, A., E. Murby, and S. Costanzo. 2007. “Removal of Antibiotics in Conventional and Advanced Wastewater Treatment: Implications for Environmental Discharge and Wastewater Recycling.” Water research 41 (18): 4164–76.10.1016/j.watres.2007.04.005Search in Google Scholar PubMed
Xia, Y., and Q. Dai. 2018. “Electrochemical Degradation of Antibiotic Levofloxacin by PbO2 Electrode: Kinetics, Energy Demands and Reaction Pathways.” Chemosphere 205: 215–22, https://doi.org/10.1016/j.chemosphere.2018.04.103.Search in Google Scholar PubMed
Xia, Y., Q. Zhang, G. Li, X. Tu, Y. Zhou, and X. Hu. 2019. “Biodegradability Enhancement of Real Antibiotic Metronidazole Wastewater by a Modified Electrochemical Fenton.” Journal of the Taiwan Institute of Chemical Engineers 96: 256–63, https://doi.org/10.1016/j.jtice.2018.11.019.Search in Google Scholar
Xu, Z., X. Song, Y. Li, G. Li, and W. Luo. 2019. “Removal of Antibiotics by Sequencing-Batch Membrane Bioreactor for swine Wastewater Treatment.” Science of The Total Environment 684: 23–30, https://doi.org/10.1016/j.scitotenv.2019.05.241.Search in Google Scholar PubMed
Yang, J., X. Wang, M. Zhu, H. Liu, and J. Ma. 2014. “Investigation of PAA/PVDF–NZVI Hybrids for Metronidazole Removal: Synthesis, Characterization, and Reactivity Characteristics.” Journal of hazardous materials 264: 269–77, https://doi.org/10.1016/j.jhazmat.2013.11.037.Search in Google Scholar PubMed
Yang, L., G. Yi, Y. Hou, H. Cheng, X. Luo, S. G. Pavlostathis, S. Luo, and A. Wang. 2019. “Building Electrode with Three-Dimensional Macroporous Interface from Biocompatible Polypyrrole and Conductive Graphene Nanosheets to Achieve Highly Efficient Microbial Electrocatalysis.” Biosensors and Bioelectronics 141: 111444, https://doi.org/10.1016/j.bios.2019.111444.Search in Google Scholar PubMed
Zarei, A., H. Biglari, M. Mobini, A. Dargahi, G. Ebrahimzadeh, M. R. Narooie, E. A. Mehrizi, A. R. Yari, M. J. Mohammadi, and M. M. Baneshi. 2018. “Disinfecting Poultry Slaughterhouse Wastewater using Copper Electrodes in the Electrocoagulation Process.” Polish Journal of Environmental Studies 27 (4): 1907–12, https://doi.org/10.15244/pjoes/78150.Search in Google Scholar
Zhou, D., and L. Gao. 2007. “Effect of Electrochemical Preparation Methods on Structure and Properties of PbO2 Anodic Layer.” Electrochimica Acta 53 (4): 2060–4, https://doi.org/10.1016/j.electacta.2007.09.005.Search in Google Scholar
Supplementary Material
The online version of this article offers supplementary material (https://doi.org/10.1515/ijcre-2019-0226).
© 2020 Walter de Gruyter GmbH, Berlin/Boston