Abstract
In this study, we report an effective degradation method for trace level beta-blockers (propranolol and acebutolol) in hospital wastewater using a new droplet flow-assisted heterogeneous electro-Fenton reactor (DFEF) system. Biogenic iron–carbon nanocomposites (RHS/C-x% Fe) as eco-friendly and low-cost heterogeneous Fenton catalysts were synthesized from rice husk via hydrolytic sol–gel routes. Here, we demonstrate the use of natural air as a nebulizing agent for fast and continuous catholyte air saturation and Fenton catalyst transfer to the cathode electrode. The effects of key operational parameters were evaluated and optimized using central composite design. Results clearly indicated that enhanced beta-blocker degradation was mainly dependent on the interactive effects of electrolysis time, current density, and catalyst dosage. Fast degradation efficiencies (≥ 99.9%) was recorded at neutral pH conditions. The decay followed pseudo-first-order kinetics with degradation rates of up to 2.72 × 10−2 and 2.54 × 10−2 min−1 for acebutolol and propranolol, respectively. The synergistic contribution of •OHbulk attributable to DFEF process and •OHadsorbed for anodic oxidation (AO) at the anode electrode significantly enhanced the degradation process. Compared to AO, the conventional flow-assisted electro-Fenton (FEF), and the batch electro-Fenton (BEF), DFEF degradation efficiency followed a decreasing order: DFEF ˃ FEF ˃ BEF˃ AO. This trend in performance was mainly due to the fast and continuous cathodic electro-generation of H2O2 and Fe2+ regeneration. Additionally, in order to elucidate degradation mechanism, we used a combination of DFEF approach with liquid chromatography-tandem mass spectrometry analysis. This approach demonstrates a simple, cleaner, and highly efficient degradation approach for trace level recalcitrant pollutants in a complex aquatic matrix, without the need for external chemical addition and pH adjustment.
Similar content being viewed by others
References
Barhoumi N, Oturan N, Ammar S, Gadri A, Oturan MA, Brillas E (2017) Enhanced degradation of the antibiotic tetracycline by heterogeneous electro-Fenton with pyrite catalysis. Environ Chem Lett 15:689–693. https://doi.org/10.1007/s10311-017-0638-y
Bezerra MA, Santelli RE, Oliveira EP, Villar LS, Escaleira LA (2008) Response surface methodology (RSM) as a tool for optimization in analytical chemistry. Talanta 76:965–977. https://doi.org/10.1016/j.talanta.2008.05.019
Brillas E, Sire I, Oturan MA et al (2009) Electro-Fenton process and related electrochemical technologies based on Fenton’s reaction chemistry. Chem Rev 109:6570–6631. https://doi.org/10.1021/cr900136g
Çelebi MS, Oturan N, Zazou H, Hamdani M, Oturan MA (2015) Electrochemical oxidation of carbaryl on platinum and boron-doped diamond anodes using electro-Fenton technology. Sep Purif Technol 156:996–1002. https://doi.org/10.1016/j.seppur.2015.07.025
Cleuvers M (2005) Initial risk assessment for three β-blockers found in the aquatic environment. Chemosphere 59:199–205. https://doi.org/10.1016/j.chemosphere.2004.11.090
Escher BI, Bramaz N, Eggen RIL, Richter M (2005) In vitro assessment of modes of toxic action of pharmaceuticals in aquatic life. Environ Sci Technol 39:3090–3100. https://doi.org/10.1021/es048590e
Fent K, Weston AA, Caminada D (2006) Ecotoxicology of human pharmaceuticals. Aquat Toxicol 76:122–159. https://doi.org/10.1016/j.aquatox.2005.09.009
Ganiyu SO, Oturan N, Raffy S, Esposito G, van Hullebusch ED, Cretin M, Oturan MA (2017) Use of sub-stoichiometric titanium oxide as a ceramic electrode in anodic oxidation and electro-Fenton degradation of the beta-blocker propranolol: degradation kinetics and mineralization pathway. Electrochim Acta 242:344–354. https://doi.org/10.1016/j.electacta.2017.05.047
Ganiyu SO, Zhou M, Martínez-huitle CA (2018) Heterogeneous electro-Fenton and photoelectro-Fenton processes: a critical review of fundamental principles and application for water/wastewater treatment. Appl Catal B Environ 235:103–129. https://doi.org/10.1016/j.apcatb.2018.04.044
Gerber SJ, Erasmus E (2018) Electronic effects of metal hexacyanoferrates: an XPS and FTIR study. Mater Chem Phys 203:73–81. https://doi.org/10.1016/j.matchemphys.2017.09.029
Hammouda SB, Fourcade F, Assadi A et al (2016) Effective heterogeneous electro-Fenton process for the degradation of a malodorous compound, indole, using iron loaded alginate beads as a reusable catalyst. Appl Catal B Environ 182:47–58. https://doi.org/10.1016/j.apcatb.2015.09.007
Huong Le TX, Esmilaire R, Drobek M et al (2016) Design of a novel fuel cell-Fenton system: a smart approach to zero energy depollution. J Mater Chem A 4:17686–17693. https://doi.org/10.1039/C6TA05443A
Isarain-Chávez E, Rodríguez RM, Garrido JA, Arias C, Centellas F, Cabot PL, Brillas E (2010) Degradation of the beta-blocker propranolol by electrochemical advanced oxidation processes based on Fenton’s reaction chemistry using a boron-doped diamond anode. Electrochim Acta 56:215–221. https://doi.org/10.1016/j.electacta.2010.08.097
Islam MA, Sakkas V, Albanis TA (2009) Application of statistical design of experiment with desirability function for the removal of organophosphorus pesticide from aqueous solution by low-cost material. J Hazard Mater 170:230–238. https://doi.org/10.1016/j.jhazmat.2009.04.106
Jurva U, Weidolf L (2015) Electrochemical generation of drug metabolites with applications in drug discovery and development. TrAC - Trends Anal Chem 70:92–99. https://doi.org/10.1016/j.trac.2015.04.010
Khataee AR, Vatanpour V, Amani Ghadim AR (2009) Decolorization of C.I. Acid Blue 9 solution by UV/Nano-TiO2, Fenton, Fenton-like, electro-Fenton and electrocoagulation processes: a comparative study. J Hazard Mater 161:1225–1233. https://doi.org/10.1016/j.jhazmat.2008.04.075
Khataee AR, Zarei M, Moradkhannejhad L (2010) Application of response surface methodology for optimization of azo dye removal by oxalate catalyzed photoelectro-Fenton process using carbon nanotube-PTFE cathode. Desalination 258:112–119. https://doi.org/10.1016/j.desal.2010.03.028
Khataee AR, Safarpour M, Zarei M, Aber S (2012) Combined heterogeneous and homogeneous photodegradation of a dye using immobilized TiO2 nanophotocatalyst and modified graphite electrode with carbon nanotubes. J Mol Catal A Chem 363–364:58–68. https://doi.org/10.1016/j.molcata.2012.05.016
Khataee A, Sajjadi S, Rahim Pouran S, Hasanzadeh A (2017) Efficient electrochemical generation of hydrogen peroxide by means of plasma-treated graphite electrode and activation in electro-Fenton. J Ind Eng Chem 56:312–320. https://doi.org/10.1016/j.jiec.2017.07.024
Li J, Liu Q, qing JQ, Lai B (2017a) Degradation of p-nitrophenol (PNP) in aqueous solution by Fe0-PM-PS system through response surface methodology (RSM). Appl Catal B Environ 200:633–646. https://doi.org/10.1016/j.apcatb.2016.07.026
Li Y, Han J, Xie B, Li Y, Zhan S, Tian Y (2017b) Synergistic degradation of antimicrobial agent ciprofloxacin in water by using 3D CeO2/RGO composite as cathode in electro-Fenton system. J Electroanal Chem 784:6–12. https://doi.org/10.1016/j.jelechem.2016.11.057
Li J, Ren Y, Lai L, Lai B (2018) Electrolysis assisted persulfate with annular iron sheet as anode for the enhanced degradation of 2, 4-dinitrophenol in aqueous solution. J Hazard Mater 344:778–787. https://doi.org/10.1016/j.jhazmat.2017.11.007
Lohmann W, Karst U (2008) Biomimetic modeling of oxidative drug metabolism: strategies, advantages and limitations. Anal Bioanal Chem 391:79–96. https://doi.org/10.1007/s00216-007-1794-x
Ma L, Zhou M, Ren G, Yang W, Liang L (2016) A highly energy-efficient flow-through electro-Fenton process for organic pollutants degradation. Electrochim Acta 200:222–230. https://doi.org/10.1016/j.electacta.2016.03.181
Mohajeri S, Aziz HA, Isa MH, Zahed MA, Adlan MN (2010) Statistical optimization of process parameters for landfill leachate treatment using electro-Fenton technique. J Hazard Mater 176:749–758. https://doi.org/10.1016/j.jhazmat.2009.11.099
Moreira FC, Boaventura RAR, Brillas E, Vilar VJP (2017) Electrochemical advanced oxidation processes: a review on their application to synthetic and real wastewaters. Appl Catal B Environ 202:217–261. https://doi.org/10.1016/j.apcatb.2016.08.037
Myers RH, Douglas C, Montgomery CMA-C (2016) Response surface methodology: process and product optimization using designed experiments, 4th Edi edn. John Wiley & Sons, Inc., New york
Nsubuga H, Basheer C, Haider MB, Bakdash R (2018) Sol-gel based biogenic silica composite as green nanosorbent for chemometric optimization of micro-solid-phase extraction of beta. J Chromatogr A 1554:16–27. https://doi.org/10.1016/j.chroma.2018.04.044
Oehlert GW (2000) A first course in design and analysis of experiments. W.H. Freeman & Co Ltd, New York, United States
Oturan N, Wu J, Zhang H, Sharma VK, Oturan MA (2013) Electrocatalytic destruction of the antibiotic tetracycline in aqueous medium by electrochemical advanced oxidation processes: effect of electrode materials. Appl Catal B Environ 140–141:92–97. https://doi.org/10.1016/j.apcatb.2013.03.035
Ouiriemmi I, Karrab A, Oturan N, Pazos M, Rozales E, Gadri A, Sanromán MÁ, Ammar S, Oturan MA (2017) Heterogeneous electro-Fenton using natural pyrite as solid catalyst for oxidative degradation of vanillic acid. J Electroanal Chem 797:69–77. https://doi.org/10.1016/j.jelechem.2017.05.028
Pillai IMS, Gupta AK (2017) Performance analysis of a continuous serpentine flow reactor for electrochemical oxidation of synthetic and real textile wastewater: energy consumption, mass transfer coefficient and economic analysis. J Environ Manag 193:524–531. https://doi.org/10.1016/j.jenvman.2017.02.046
Poza-Nogueiras V, Rosales E, Pazos M, Sanromán MÁ (2018) Current advances and trends in electro-Fenton process using heterogeneous catalysts—a review. Chemosphere 201:399–416. https://doi.org/10.1016/j.chemosphere.2018.03.002
Rahim Pouran S, Abdul Raman AA, Wan Daud WMA (2014) Review on the application of modified iron oxides as heterogeneous catalysts in Fenton reactions. J Clean Prod 64:24–35. https://doi.org/10.1016/j.jclepro.2013.09.013
Ren G, Zhou M, Liu M, Ma L, Yang H (2016) A novel vertical-flow electro-Fenton reactor for organic wastewater treatment. Chem Eng J 298:55–67. https://doi.org/10.1016/j.cej.2016.04.011
Rivera-Utrilla J, Sánchez-Polo M, Ferro-García MÁ, Prados-Joya G, Ocampo-Pérez R (2013) Pharmaceuticals as emerging contaminants and their removal from water. A review. Chemosphere 93:1268–1287. https://doi.org/10.1016/j.chemosphere.2013.07.059
Sellers RM (1980) Spectrophotometric determination of hydrogen peroxide using potassium titanium(IV) oxalate. Analyst 105:950. https://doi.org/10.1039/an9800500950
Serrano M, Chatzimitakos T, Gallego M, Stalikas CD (2016) 1-Butyl-3-aminopropyl imidazolium-functionalized graphene oxide as a nanoadsorbent for the simultaneous extraction of steroids and β-blockers via dispersive solid-phase microextraction. J Chromatogr A 1436:9–18. https://doi.org/10.1016/j.chroma.2016.01.052
Sirés I, Brillas E, Oturan MA, Rodrigo MA, Panizza M (2014) Electrochemical advanced oxidation processes: today and tomorrow. A review. Environ Sci Pollut Res 21:8336–8367. https://doi.org/10.1007/s11356-014-2783-1
Sopaj F, Oturan N, Pinson J, Podvorica F, Oturan MA (2016) Effect of the anode materials on the efficiency of the electro-Fenton process for the mineralization of the antibiotic sulfamethazine. Appl Catal B Environ 199:331–341. https://doi.org/10.1016/j.apcatb.2016.06.035
Varga R, Eke Z, Torkos K (2011) Identification of phase I metabolites of cardiovascular and anti-ulcer drugs in surface water samples with liquid-chromatography-mass spectrometry methods. Talanta 85:1920–1926. https://doi.org/10.1016/j.talanta.2011.07.020
Wilde ML, Mahmoud WMM, Kümmerer K, Martins AF (2013) Oxidation-coagulation of beta-blockers by K2FeVIO4 in hospital wastewater: assessment of degradation products and biodegradability. Sci Total Environ 452–453:137–147. https://doi.org/10.1016/j.scitotenv.2013.01.059
Wilde ML, Montipó S, Martins AF (2014) Degradation of beta-blockers in hospital wastewater by means of ozonation and Fe2+/ozonation. Water Res 48:280–295. https://doi.org/10.1016/j.watres.2013.09.039
Xiong Z, Lai B, Yang P (2018) Insight into a highly efficient electrolysis-ozone process for N,N-dimethylacetamide degradation: quantitative analysis of the role of catalytic ozonation, Fenton-like and peroxone reactions. Water Res 140:12–23. https://doi.org/10.1016/j.watres.2018.04.030
Xu A, Wei K, Zhang Y, Han W, Li J, Sun X, Shen J, Wang L (2017) A facile-operation tubular electro-Fenton system combined with oxygen evolution reaction for flutriafol degradation: modeling and parameters optimizing. Electrochim Acta 246:1200–1209. https://doi.org/10.1016/j.electacta.2017.06.133
Yamashita T, Hayes P (2008) Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials. Appl Surf Sci 254:2441–2449. https://doi.org/10.1016/j.apsusc.2007.09.063
Zhang C, Zhou M, Ren G, Yu X, Ma L, Yang J, Yu F (2015) Heterogeneous electro-Fenton using modified iron-carbon as catalyst for 2,4-dichlorophenol degradation: influence factors, mechanism and degradation pathway. Water Res 70:414–424. https://doi.org/10.1016/j.watres.2014.12.022
Acknowledgments
The authors gratefully acknowledge the funding support of the Deanship of Scientific Research at King Fahd University of Petroleum and Minerals through a Project Grant No. 151024. Hakimu is also grateful to KFUPM for sponsoring his Ph.D. studies.
Author information
Authors and Affiliations
Corresponding author
Additional information
Responsible editor: Vítor Pais Vilar
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
ESM 1
(DOCX 607 kb)
Rights and permissions
About this article
Cite this article
Nsubuga, H., Basheer, C., Jalilov, A. et al. Droplet flow-assisted heterogeneous electro-Fenton reactor for degradation of beta-blockers: response surface optimization, and mechanism elucidation. Environ Sci Pollut Res 26, 14313–14327 (2019). https://doi.org/10.1007/s11356-019-04551-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-019-04551-1