Abstract
Enrofloxacin (ENR) is a widely used veterinary fluoroquinolone antibiotic and is frequently detected in water environments. The degradation of ENR was examined utilizing molecular oxygen mediation using nanometer zero-valent copper (nZVC) as the catalyst in this work. The dosage of nZVC, initial pH, and reaction temperature were investigated as contributing factors to ENR degradation. The effects of Cl−, NO3−, SO42−, and humic acid on the degradation of ENR were investigated. The actual effects were evaluated using natural water. The reactive oxygen species (ROS) that participated in the reaction were identified, their generation mechanisms were elucidated, and the effects on ENR degradation were assessed. More emphasis was given to exploring ENR degradation and transformation pathways via analyses of HPLC-TOF–MS. Data showed that at 35 ℃, with an initial pH of 3 and exposed to air, an nZVC dose of 0.5 g·L−1 degraded ENR by 99.51% dramatically. HO• radicals were identified as the dominant ROS, and conversions among Cu0, Cu+, and Cu2+ played crucial roles in the generation of ROS. The destruction mechanism of ENR was speculated based on analyses of HPLC-TOF–MS results as the transformation of the piperazine ring into an oxidized state with a -COOH substitution with HO•, which caused ENR to be mineralized and converted into CO2, H2O, and \({\text{NO}}_{3}^{-}\). The ECOSAR program has been used to evaluate the toxicity of ENR and its degradation products, and oxidative degradation of nZVC significantly reduced its toxicity and increased its biodegradability. This research proposes a capable and practical method for removing ENR from water.
Similar content being viewed by others
Data availability
All data generated and analyzed in this study are available upon reasonable request. Access to data generated in this report should be sent to the corresponding author at gjh@yfi.ac.cn.
References
Boxall ABA, Kolpin DW, Halling-Sørensen B, Tolls J (2003) Peer reviewed: are veterinary medicines causing environmental risks? Environ Sci Technol 37:286A-294A. https://doi.org/10.1021/es032519b
Das Sharma D, Show S, Samanta S et al (2022) Sorptive riddance of enrofloxacin from wastewater: linear and non-linear isotherm and kinetics, safe disposal, and cost analysis. Biomass Conv Bioref. https://doi.org/10.1007/s13399-021-02172-8
de Melo Costa-Serge C, Gonçalves RGL, Rojas-Mantilla HD et al (2021) Fenton-like degradation of sulfathiazole using copper-modified MgFe-CO3 layered double hydroxide. J Hazard Mater 413:125388. https://doi.org/10.1016/j.jhazmat.2021.125388
de Sousa PVF, de Oliveira AF, da Silva AA et al (2019) Study of ciprofloxacin degradation by zero-valent copper nanoparticles. Chem Pap 73:249–260. https://doi.org/10.1007/s11696-018-0575-7
de Souza LP, Graça CAL, Teixeira ACSC, Chiavone-Filho O (2021) Degradation of 2,4,6-trichlorophenol in aqueous systems through the association of zero-valent-copper-mediated reduction and UVC/H2O2: effect of water matrix and toxicity assessment. Environ Sci Pollut R 28:24057–24066. https://doi.org/10.1007/s11356-020-11885-8
Deng J, Xu M, Chen Y et al (2019) Highly-efficient removal of norfloxacin with nanoscale zero-valent copper activated persulfate at mild temperature. Chem Eng J 366:491–503. https://doi.org/10.1016/j.cej.2019.02.073
Di J, Xia J, Ji M et al (2016) Nitrogen-doped carbon quantum dots/BiOBr ultrathin nanosheets: in situ strong coupling and improved molecular oxygen activation ability under visible light irradiation. ACS Sustain Chem Eng 4:136–146. https://doi.org/10.1021/acssuschemeng.5b00862
Dong G, Ai Z, Zhang L (2014) Total aerobic destruction of azo contaminants with nanoscale zero-valent copper at neutral pH: promotion effect of in-situ generated carbon center radicals. Water Res 66:22–30. https://doi.org/10.1016/j.watres.2014.08.011
Du L, Liu W (2012) Occurrence, fate, and ecotoxicity of antibiotics in agro-ecosystems. A review. Agron Sustain Dev 32:309–327. https://doi.org/10.1007/s13593-011-0062-9
Fang H, Oberoi AS, He Z et al (2021) Ciprofloxacin-degrading Paraclostridium sp. isolated from sulfate-reducing bacteria-enriched sludge: optimization and mechanism. Water Res 191:116808. https://doi.org/10.1016/j.watres.2021.116808
Fu Z, Xie H-B, Elm J et al (2022) Atmospheric autoxidation of organophosphate esters. Environ Sci Technol 56:6944–6955. https://doi.org/10.1021/acs.est.1c04817
Gao Y, Zhang J, Zhou J et al (2020) Persulfate activation by nano zero-valent iron for the degradation of metoprolol in water: influencing factors, degradation pathways and toxicity analysis. Rsc Adv 10:20991–20999. https://doi.org/10.1039/D0RA01273D
Gao Y, Wang Q, Ji G, Li A (2022) Degradation of antibiotic pollutants by persulfate activated with various carbon materials. Chem Eng J 429:132387. https://doi.org/10.1016/j.cej.2021.132387
Grabowski Ł, Gaffke L, Pierzynowska K et al (2022) Enrofloxacin—the ruthless killer of eukaryotic cells or the last hope in the fight against bacterial infections? Int J Mol Sci 23:3648. https://doi.org/10.3390/ijms23073648
Guo H, Ke T, Gao N et al (2017) Enhanced degradation of aqueous norfloxacin and enrofloxacin by UV-activated persulfate: kinetics, pathways and deactivation. Chem Eng J 316:471–480. https://doi.org/10.1016/j.cej.2017.01.123
Guo H, Jiang N, Wang H et al (2019) Pulsed discharge plasma assisted with graphene-WO3 nanocomposites for synergistic degradation of antibiotic enrofloxacin in water. Chem Eng J 372:226–240. https://doi.org/10.1016/j.cej.2019.04.119
Guo X-H, Yang Y, Deng Z-Y (2021) Filtrates with hydroxyl radicals prepared using Al+ Acid+ H2O2 for removing organic pollutants. ACS Omega 6:14182–14190. https://doi.org/10.1021/acsomega.1c00801
Hollanda LR, Graça CA, Andrade LM et al (2019) Non-traditional atrazine degradation induced by zero-valent-copper: process optimization by the Doehlert experimental design, intermediates detection and toxicity assessment. J Chem Technol Biot 94:1156–1164. https://doi.org/10.1002/jctb.5862
Iakovides IC, Michael-Kordatou I, Moreira NFF et al (2019) Continuous ozonation of urban wastewater: removal of antibiotics, antibiotic-resistant Escherichia coli and antibiotic resistance genes and phytotoxicity. Water Res 159:333–347. https://doi.org/10.1016/j.watres.2019.05.025
Ileri B, Dogu I (2022) Sono–degradation of reactive Blue 19 in aqueous solution and synthetic textile industry wastewater by nanoscale zero–valent aluminum. J Environ Manage 303:114200. https://doi.org/10.1016/j.jenvman.2021.114200
Jiang C, Ji Y, Shi Y et al (2016) Sulfate radical-based oxidation of fluoroquinolone antibiotics: kinetics, mechanisms and effects of natural water matrices. Water Res 106:507–517. https://doi.org/10.1016/j.watres.2016.10.025
Junza A, Saurina J, Barrón D, Minguillón C (2016) Metabolic profile modifications in milk after enrofloxacin administration studied by liquid chromatography coupled with high resolution mass spectrometry. J Chromatogr A 1460:92–99. https://doi.org/10.1016/j.chroma.2016.07.016
Khachatryan L, Vejerano E, Lomnicki S, Dellinger B (2011) Environmentally persistent free radicals (EPFRs). 1. Generation of reactive oxygen species in aqueous solutions. Environ Sci Technol 45:8559–8566. https://doi.org/10.1021/es201309c
Li Q, Li F (2021) Recent advances in molecular oxygen activation via photocatalysis and its application in oxidation reactions. Chem Eng J 421:129915. https://doi.org/10.1016/j.cej.2021.129915
Li Z, Li M, Zhang Z et al (2020) Antibiotics in aquatic environments of China: a review and meta-analysis. Ecotox Environ Safe 199:110668. https://doi.org/10.1016/j.ecoenv.2020.110668
Li J, Yang L, Lai B et al (2021) Recent progress on heterogeneous Fe-based materials induced persulfate activation for organics removal. Chem Eng J 414:128674. https://doi.org/10.1016/j.cej.2021.128674
Liu Y, Zeng X, Hu X et al (2021a) Solar-driven photocatalytic disinfection over 2D semiconductors: the generation and effects of reactive oxygen species. Sol Rrl 5:2000594. https://doi.org/10.1002/solr.202000594
Liu Y, Zhao Y, Wang J (2021b) Fenton/Fenton-like processes with in-situ production of hydrogen peroxide/hydroxyl radical for degradation of emerging contaminants: advances and prospects. J Hazard Mater 404:124191. https://doi.org/10.1016/j.jhazmat.2020.124191
Liu Y, Gao J, Wang Y et al (2022) The removal of antibiotic resistant bacteria and genes and inhibition of the horizontal gene transfer by contrastive research on sulfidated nanoscale zerovalent iron activating peroxymonosulfate or peroxydisulfate. J Hazard Mater 423:126866. https://doi.org/10.1016/j.jhazmat.2021.126866
Long J, Xu L, Zhao L et al (2020) Activation of dissolved molecular oxygen by Cu(0) for bisphenol a degradation: role of Cu(0) and formation of reactive oxygen species. Chemosphere 241:125034. https://doi.org/10.1016/j.chemosphere.2019.125034
Morales-Gutiérrez FJ, Hermo MP, Barbosa J, Barrón D (2014) High-resolution mass spectrometry applied to the identification of transformation products of quinolones from stability studies and new metabolites of enrofloxacin in chicken muscle tissues. J Pharmaceut Biomed 92:165–176. https://doi.org/10.1016/j.jpba.2014.01.014
Nihemaiti M, Permala RR, Croué J-P (2020) Reactivity of unactivated peroxymonosulfate with nitrogenous compounds. Water Res 169:115221. https://doi.org/10.1016/j.watres.2019.115221
Ouyang Y, Xu Q, Xiang Y et al (2019) Degradation of simulated organic wastewater by advanced oxidation with oxidants generated from oxygen reduction. Chinese J Chem Eng 27:850–856. https://doi.org/10.1016/j.cjche.2018.07.004
Patel M, Kumar R, Kishor K et al (2019) Pharmaceuticals of emerging concern in aquatic systems: chemistry, occurrence, effects, and removal methods. Chem Rev 119:3510–3673. https://doi.org/10.1021/acs.chemrev.8b00299
Qiao M, Ying G-G, Singer AC, Zhu Y-G (2018) Review of antibiotic resistance in China and its environment. Environ Int 110:160–172. https://doi.org/10.1016/j.envint.2017.10.016
Shi J, Huang W, Zhu H et al (2022) Facile fabrication of durable biochar/H2-TiO2 for highly efficient solar-driven degradation of enrofloxacin: properties, degradation pathways, and mechanism. ACS Omega 7:12158–12170. https://doi.org/10.1021/acsomega.2c00523
Shu W, Zhang Y, Wen D et al (2021) Anaerobic biodegradation of levofloxacin by enriched microbial consortia: effect of electron acceptors and carbon source. J Hazard Mater 414:125520. https://doi.org/10.1016/j.jhazmat.2021.125520
Sodhi KK, Singh DK (2021) Insight into the fluoroquinolone resistance, sources, ecotoxicity, and degradation with special emphasis on ciprofloxacin. J Water Process Eng 43:102218. https://doi.org/10.1016/j.jwpe.2021.102218
Sturini M, Speltini A, Maraschi F et al (2010) Photochemical degradation of marbofloxacin and enrofloxacin in natural waters. Environ Sci Technol 44:4564–4569. https://doi.org/10.1021/es100278n
Sun X, Qin Y, Zhou W (2021) Degradation of amoxicillin from water by ultrasound-zero-valent iron activated sodium persulfate. Sep Purif Technol 275:119080. https://doi.org/10.1016/j.seppur.2021.119080
Trouchon T, Lefebvre S (2016) A review of enrofloxacin for veterinary use. Open J Vet Med 6:40–58. https://doi.org/10.4236/ojvm.2016.62006
Van Boeckel TP, Brower C, Gilbert M et al (2015) Global trends in antimicrobial use in food animals. Proc Natl Acad Sci USA 112:5649–5654. https://doi.org/10.1073/pnas.1503141112
Wang J, Zhuan R (2020) Degradation of antibiotics by advanced oxidation processes: an overview. Sci Total Environ 701:135023. https://doi.org/10.1016/j.scitotenv.2019.135023
Wang C, Yin L, Xu Z et al (2017) Electrochemical degradation of enrofloxacin by lead dioxide anode: kinetics, mechanism and toxicity evaluation. Chem Eng J 326:911–920. https://doi.org/10.1016/j.cej.2017.06.038
Weidlich T (2021) The influence of copper on halogenation/dehalogenation reactions of aromatic compounds and its role in the destruction of polyhalogenated aromatic contaminants. Catalysts 11:378. https://doi.org/10.3390/catal11030378
Wen G, Wang S-J, Ma J et al (2014) Oxidative degradation of organic pollutants in aqueous solution using zero valent copper under aerobic atmosphere condition. J Hazard Mater 275:193–199. https://doi.org/10.1016/j.jhazmat.2014.05.002
Xiao Y, Lyu H, Tang J et al (2020) Effects of ball milling on the photochemistry of biochar: enrofloxacin degradation and possible mechanisms. Chem Eng J 384:123311. https://doi.org/10.1016/j.cej.2019.123311
Xu J, Liu Y, Li D et al (2022) Insights into the electrooxidation of florfenicol by a highly active La-doped Ti4O7 anode. Sep Purif Technol 291:120904. https://doi.org/10.1016/j.seppur.2022.120904
Yan W, Zhang R, Ji F, Jing C (2020) Deciphering co-catalytic mechanisms of potassium doped g-C3N4 in Fenton process. J Hazard Mater 392:122472. https://doi.org/10.1016/j.jhazmat.2020.122472
Yang B, Kookana RS, Williams M et al (2016) Oxidation of ciprofloxacin and enrofloxacin by ferrate(VI): products identification, and toxicity evaluation. J Hazard Mater 320:296–303. https://doi.org/10.1016/j.jhazmat.2016.08.040
Yang T, Mai J, Cheng H et al (2022a) UVA-LED-assisted activation of the Ferrate(VI) process for enhanced micropollutant degradation: important role of Ferrate(IV) and Ferrate(V). Environ Sci Technol 56:1221–1232. https://doi.org/10.1021/acs.est.1c03725
Yang Z, Liu Y, Wang J (2022b) MOF-derived Cu0/C activation of molecular oxygen for efficient degradation of sulfamethazine. Chem Eng J 427:131961. https://doi.org/10.1016/j.cej.2021.131961
Yu W, Yang S, Du B et al (2020) Feasibility and mechanism of enhanced 17β-estradiol degradation by the nano Zero Valent Iron-citrate system. J Hazard Mater 396:122657. https://doi.org/10.1016/j.jhazmat.2020.122657
Yu C, Huang R, Xie Y et al (2022) In-situ synthesis of N-doped biochar encapsulated Cu(0) nanoparticles with excellent Fenton-like catalytic performance and good environmental stability. Sep Purif Technol 295:121334. https://doi.org/10.1016/j.seppur.2022.121334
Zhang Q-Q, Ying G-G, Pan C-G et al (2015) Comprehensive evaluation of antibiotics emission and fate in the river basins of China: source analysis, multimedia modeling, and linkage to bacterial resistance. Environ Sci Technol 49:6772–6782. https://doi.org/10.1021/acs.est.5b00729
Zhang J, Guo J, Wu Y et al (2017) Efficient activation of ozone by zero-valent copper for the degradation of aniline in aqueous solution. J Taiwan Inst Chem E 81:335–342. https://doi.org/10.1016/j.jtice.2017.09.025
Zhang C, Xuan L, Zhang J et al (2020a) Degradation of organic contaminants through the activation of oxygen using zero valent copper coupled with sodium tripolyphosphate under neutral conditions. J Environ Sci 90:375–384. https://doi.org/10.1016/j.jes.2020.01.001
Zhang F, Zhang Y, Pu M, Niu J (2020b) Aerobic degradation of aqueous pollutants with nanoscale zero-valent aluminum in alkaline condition: Performance and mechanism especially at particle surface. J Clean Prod 244:118905. https://doi.org/10.1016/j.jclepro.2019.118905
Zhang T, Yang Y, Li X et al (2020c) Degradation of sulfamethazine by persulfate activated with nanosized zero-valent copper in combination with ultrasonic irradiation. Sep Purif Technol 239:116537. https://doi.org/10.1016/j.seppur.2020.116537
Zhang K, Deng J, Chen Y et al (2021a) Ascorbic acid enhanced ciprofloxacin degradation with nanoscale zero-valent copper activated molecular oxygen. Chemosphere 278:130354. https://doi.org/10.1016/j.chemosphere.2021.130354
Zhang L, Fu Y, Wang Z et al (2021b) Removal of diclofenac in water using peracetic acid activated by zero valent copper. Sep Purif Technol 276:119319. https://doi.org/10.1016/j.seppur.2021.119319
Zhou P, Zhang J, Zhang Y et al (2016) Activation of hydrogen peroxide during the corrosion of nanoscale zero valent copper in acidic solution. J Mol Catal a: Chem 424:115–120. https://doi.org/10.1016/j.molcata.2016.08.022
Zhou P, Zhang J, Zhang Y et al (2018a) Degradation of 2,4-dichlorophenol by activating persulfate and peroxomonosulfate using micron or nanoscale zero-valent copper. J Hazard Mater 344:1209–1219. https://doi.org/10.1016/j.jhazmat.2017.11.023
Zhou Y, Gao Y, Pang S-Y et al (2018b) Oxidation of fluoroquinolone antibiotics by peroxymonosulfate without activation: Kinetics, products, and antibacterial deactivation. Water Res 145:210–219. https://doi.org/10.1016/j.watres.2018.08.026
Zhu T, Su Z, Lai W et al (2021) Insights into the fate and removal of antibiotics and antibiotic resistance genes using biological wastewater treatment technology. Sci Total Environ 776:145906. https://doi.org/10.1016/j.scitotenv.2021.145906
Zhuan R, Wang J (2020) Degradation of diclofenac in aqueous solution by ionizing radiation in the presence of humic acid. Sep Purif Technol 234:116079. https://doi.org/10.1016/j.seppur.2019.116079
Funding
This research was supported by the Central Public-interest Scientific Institution Basal Research Fund, CAFS (NO.2020XT08, NO.2019ZD0803, NO.2020JBF07), and National Key Research and Development Program of China (2017YFC1600704).
Author information
Authors and Affiliations
Contributions
Zhiqiang Gong: data curation, writing — original draft; Junpu Xie: data curation, writing—original draft preparation; Jingxin Liu: data curation; Ting Liu: writing — review and editing; Jianwu Chen: methodology, validation; Jinping Li: supervision; Jinhua Gan: conceptualization, methodology, software supervision.
Corresponding authors
Ethics declarations
Ethics approval and consent to participate
Not applicable.
Consent for publication
Not applicable.
Competing interests
The authors declare no competing interests.
Additional information
Responsible Editor: Guilherme L. Dotto
Publisher's note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Gong, Z., Xie, J., Liu, J. et al. Oxidation towards enrofloxacin degradation over nanoscale zero-valent copper: mechanism and products. Environ Sci Pollut Res 30, 38700–38712 (2023). https://doi.org/10.1007/s11356-022-24984-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-022-24984-5