Efficient degradation of antibiotics by photo-Fenton reactive ceramic membrane with high flux by a facile spraying method under visible LED light
Graphical abstract
Introduction
As known, antibiotics are one of the most important drugs not only for preventing and treating human bacterial infections but also used as antibacterial and growth-promoting additives for animal infectious diseases (RODRIGUEZ-MOZAZ et al., 2015; CHEN et al., 2020a). Presently, the annual production of pharmaceutical wastewater is up to 250 million tons in China (LI et al., 2020a), which contains a large number of antibiotics and nearly half of them were not well treated (ZHAO et al., 2016). Moreover, the other sources of antibiotics to the environment also include domestic sewage, medical wastewater, animal feed, aquaculture wastewater, etc. (TANG et al., 2015; BIA Ł K-BIELI Ń SKA et al., 2011). Most antibiotics enter the ecosystem through excretion and secretion after use and then migrate among surface water, groundwater, and soil, which is difficult to be effectively eliminated (ZHAO et al., 2016). As a result, antibiotics are emerged and detected in major watersheds of China, such as the Yangtze River (ZHANG et al., 2020), Pearl River (LI et al., 2018), and coastal watersheds (LI et al., 2020b), etc., ranging in concentration from hundreds of ng/L to several mg/L (ZHANG et al., 2020; LEI et al., 2019; LEE et al., 2020). Their residues are subject to re-entry into human bodies in various forms, such as through the transmission of the food chain of drinking water, meat, and vegetables, thus ultimately affecting human health (QIAO et al., 2020). Besides, the widespread low concentration of antibiotics in the ecosystem could cause resistance genes, which may result in the emergence of super-bacteria that will be a potential ecological disaster to human society (ZHANG et al., 2020; HE et al., 2021).
Many studies (TANG et al., 2015; QIAO et al., 2020) also revealed that antibiotics exhibit the characteristics of high-water solubility and resistance to biological degradation. Therefore, the eliminating technology of these micropollutants with high efficiency but low cost is highly desired. At present, various processes are used for the treatment of antibiotics, including biological technology (HE et al., 2021), reverse osmosis (LAN et al., 2019), adsorption (AZHAR et al., 2017), coagulation (LI et al., 2017), and advanced oxidation processes, such as electrochemical oxidation (SORDELLO et al., 2021), Fenton/Fenton-like oxidation (CHENG et al., 2021), TiO2 photocatalysis (SERNA-GALVIS et al., 2016), etc. However, a single process displays certain deficiencies of costly, time-consuming, low efficiency, excessive chemicals addition, and secondary pollution (AZHAR et al., 2017). So, combined with the two and above single processes of coupling techniques, bring not only synergic effects but also circumvent the disadvantages of single ones, which gradually becomes a new horizon in water and wastewater treatment. Consequently, many novel coupling technologies were proposed for the removal of micropollutants, such as combined membrane separation (YIN et al., 2021), photo-Fenton (LIU et al., 2020), electro-Fenton (LIU et al., 2015), ozone-UV/H2O2 (JUSTO et al., 2013), Fenton-SBR (BEN et al., 2009), TiO2 photocatalysis-ceramic membrane (LI et al., 2019), ozone-nanofiltration (LIU et al., 2014), ozone-ceramic membrane (ASIF et al., 2021), photo-Fenton reactive ceramic membrane (PF-CM) (SUN et al., 2018), etc. Among all these coupled processes, the PF-CM not just retains the superiority of operational simplicity, lower energy consumption, and high efficiency of photo-Fenton oxidation (SEGURA et al., 2021) but also combines the advantages of the CM separation of excellent thermal stability, corrosion resistance, and high flux (YIN et al., 2021; LI et al., 2004). Furthermore, the hydroxyl radical (·OH) generated from the photo-Fenton reaction could oxidize and decompose the pollutants on the surface of the membrane, and result in mitigating membrane fouling (FRONTISTIS et al., 2011). It's worth mentioning that the PF-CM also gives a prospect to use solar energy to cut operating costs as well. In the practice of wastewater treatment, the operation modes of PF-CM mainly include suspended (LI et al., 2020c) and fixed bed (SUN et al., 2018; SUN et al., 2020a) treatment systems. Compared with the former, the latter fixed bed system with a reactive ceramic membrane could effectively solve the loss and reuse problem of the photocatalysts (LI et al., 2020c). Therefore, the crux of this technology is to develop a PF-CM with the economy, facile preparation, visible light response activity, and stable performance (SUN et al., 2020b; XIN et al., 2021). However, to our knowledge, there are limited approaches of the covalent binding method (LIU et al., 2020; SUN et al., 2018; SUN et al., 2020b), sol-gel method (KARNIK et al., 2005), and one-pot method (CHEN et al., 2020b) for the preparation of the PF-CM, which should be further optimized to be more facile, scalable, and eco-friendly.
In this study, low-priced and easily available nano hematite (α-Fe2O3) synthesized by a solvothermal method (ZHENG et al., 2020) was used as the photo-Fenton catalyst. Then the as-prepared α-Fe2O3 was loaded to a flat ceramic membrane (CM) by a spray printing and low-temperature sintering method to form a photo-Fenton reactive membrane (α-Fe2O3-CM). And a new fixed bed reactor with visible LED lights was designed to fabricate a new system for the treatment of a model antibiotic of tetracycline hydrochloride (TC). The effect preparation parameters of printing layers and calcination temperature of α-Fe2O3-CM on TC degradation performance and permeate flux were investigated simultaneously. Furtherly, the antifouling performance and reusability of the α-Fe2O3-CM were also studied comprehensively. Finally, we performed quenching experiments to study the reactive radicals involved in the photo- Fenton process to achieve deeper insight into the degradation mechanisms of TC in the new reactive CM treatment system. This research could provide an alternative technology for a facile and scalable preparation and application of self-cleaning PF-CM with high flux for micropollutants removal in water or wastewater treatment.
Section snippets
Preparation of α-Fe2O3 nano catalyst
The α-Fe2O3 nano-catalyst was synthesized by a typic solvothermal method with a little modification (ZHENG et al., 2020; NUR MAISARAH ABDUL RASHID and NOOR HAMIZAH KHANIS, 2016; WANG et al., 2017). Detailed procedures are presented in the Supporting Materials S1.
Preparation of the α-Fe2O3-CM modules
The flat CM sheets (L × W × H = 510 mm × 150 mm × 4 mm) composed of α-Al2O3 were purchased from Huahuai new materials company of China with a nominal pore size of 0.1 μm, the porosity of 53%, and 43 water purification channels (L × W
Characterization of α-Fe2O3 nano-catalyst
The XRD analysis was performed to determine the phase compositions of the α-Fe2O3 nanoparticles, and the results are shown in Fig. 3(a). As illustrated in Fig. 3(a), the diffraction peaks at 2θ values of 24.1°, 33.2°, 35.6°, 40.9°, 49.5°, 54.1°, 57.4°, 62.4°, 64.0°, 72.2°, and 75.4°, which could be indexed to the typical crystalline phase of α-Fe2O3 with planes of {012}, {104}, {110}, {024}, {116}, {112}, {214}, {300}, {119} and {220}, respectively (JCPDS card No.33-0644) that agrees with
Conclusions
In the study, photo-Fenton reactive ceramic membrane (PF-CM) with high flux were fabricated by a facile and green spray printing method with nano hematite (α-Fe2O3). The SEM/EDS spectra of the CM and α-Fe2O3-CM revealed the α-Fe2O3 catalyst was successfully coated on the surface of CM by the spraying method. And a fixed bed water treatment system with α-Fe2O3-CM and visible LED light was constructed. The pure water flux experimental result for α-Fe2O3-CM indicated the α-Fe2O3-CM still
CRediT authorship contribution statement
Chaoqun Yan: Methodology, Software, Formal analysis, Investigation, Data curation, Writing – original draft, Writing – review & editing. Zhiliang Cheng: Conceptualization, Methodology, Resources, Writing – review & editing, Supervision, Funding acquisition. Juan Wei: Methodology, Investigation, Writing – review & editing. Qian Xu: Software, Investigation, Formal analysis. Xuan Zhang: Software, Investigation. Zejun Wei: Resources, Methodology.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
This research was sponsored by the Natural Science Foundation of Chongqing, China (cstc2020jcyj-msxmX0308), the Youth Project of Science and Technology Research Program of Chongqing Education Commission of China (KJQN202001148), and the Special Project on Transformation and Industrialization of Scientific and Technological Achievements of Banan District, Chongqing, China (2020TJZ003), the Postgraduate Innovation Project of Chongqing University of Technology (clgycx 20203067). Here we sincerely
References (69)
- et al.
Elucidating the impacts of intermittent in-situ ozonation in a ceramic membrane bioreactor: micropollutant removal, microbial community evolution and fouling mechanisms
J. Hazard Mater.
(2021) - et al.
Adsorptive removal of antibiotic sulfonamide by UiO-66 and ZIF-67 for wastewater treatment
J. Colloid Interface Sci.
(2017) - et al.
Application of tubular ceramic ultrafiltration membranes for the treatment of integrated textile wastewaters
Chem. Eng. J.
(2012) - et al.
Removal of veterinary antibiotics from sequencing batch reactor (SBR) pretreated swine wastewater by Fenton's reagent
Water Res.
(2009) - et al.
Ecotoxicity evaluation of selected sulfonamides
Chemosphere
(2011) - et al.
High-efficiency photo-Fenton Fe/g-C3N4/kaolinite catalyst for tetracycline hydrochloride degradation
Appl. Clay Sci.
(2021) - et al.
Comprehensive insights into the occurrence, distribution, risk assessment and indicator screening of antibiotics in a large drinking reservoir system
Sci. Total Environ.
(2020) - et al.
Fabrication of a super hydrophilic PVDF-g-PAA@FeOOH ultrafiltration membrane with visible light photo-Fenton self-cleaning performance
J. Membr. Sci.
(2020) - et al.
Highly efficient removal of antibiotic from biomedical wastewater using Fenton-like catalyst magnetic pullulan hydrogels
Carbohydr. Polym.
(2021) - et al.
Engineering construction of robust superhydrophobic two-tier composite membrane with interlocked structure for membrane distillation
J. Membr. Sci.
(2020)
Critical, sustainable and threshold fluxes for membrane filtration with water industry applications
Adv. Colloid Interface Sci.
Fast degradation of estrogen hormones in environmental matrices by photo-Fenton oxidation under simulated solar radiation
Chem. Eng. J.
Ultrahigh specific capacitance of α-Fe2O3 nanorods-incorporated defect-free graphene nanolayers
Energy
Recovery of biological wastewater treatment system inhibited by oxytetracycline: rebound of functional bacterial population and the impact of adsorbed oxytetracycline on antibiotic resistance
Chem. Eng. J.
A new insight into catalytic ozonation of sulfasalazine antibiotic by plasma-treated limonite nanostructures: experimental, modeling and mechanism
Chem. Eng. J.
Removal of contaminants of emerging concern (CECs) and antibiotic resistant bacteria in urban wastewater using UVA/TiO2/H2O2 photocatalysis
Chemosphere
Pharmaceuticals and organic pollution mitigation in reclamation osmosis brines by UV/H2O2 and ozone
J. Hazard Mater.
Green photo-catalyst ‘turmeric roots’ for pesticides degradation: preparation and characterizations
Mater. Lett.
High removal efficiency of antibiotic resistance genes in swine wastewater via nanofiltration and reverse osmosis processes
J. Environ. Manag.
Characteristics of veterinary antibiotics in intensive livestock farming watersheds with different liquid manure application programs using UHPLC-q-orbitrap HRMS combined with on-line SPE
Sci. Total Environ.
Spatial and seasonal variations of antibiotics in river waters in the Haihe River Catchment in China and ecotoxicological risk assessment
Environ. Int.
Membrane (RO-UF) filtration for antibiotic wastewater treatment and recovery of antibiotics
Separ. Purif. Technol.
Removal of antibiotic resistance genes from wastewater treatment plant effluent by coagulation
Water Res.
Antibiotics in water and sediments of rivers and coastal area of Zhuhai City, Pearl River estuary, south China
Sci. Total Environ.
Photocatalytic degradation of amoxicillin via TiO2 nanoparticle coupling with a novel submerged porous ceramic membrane reactor
J. Clean. Prod.
Antibiotics in aquatic environments of China: a review and meta-analysis
Ecotoxicol. Environ. Saf.
Identification of the priority antibiotics based on their detection frequency, concentration, and ecological risk in urbanized coastal water
Sci. Total Environ.
Ceramic nanocomposite membranes and membrane fouling: a review
Water Res.
Kinetics and products of PCB28 degradation through a goethite-catalyzed Fenton-like reaction
Chemosphere
Crystal plane effect of Fe2O3 with various morphologies on CO catalytic oxidation
Catal. Commun.
Removal of trace antibiotics from wastewater: a systematic study of nanofiltration combined with ozone-based advanced oxidation processes
Chem. Eng. J.
Enhanced catalytic degradation of methylene blue by α-Fe2O3/graphene oxide via heterogeneous photo-Fenton reactions
Appl. Catal. B Environ.
Enhanced photocatalytic activity over flower-like sphere Ag/Ag2CO3/BiVO4 plasmonic heterojunction photocatalyst for tetracycline degradation
Chem. Eng. J.
Photo-Fenton activation mechanism and antifouling performance of an FeOCl-coated ceramic membrane
Chem. Eng. J.
Cited by (16)
Montmorillonite-modified stabilizing SA/CMC gel spheres cross-linked by lanthanum for tetracycline hydrochloride removal
2023, Journal of Water Process EngineeringEfficient degradation of dye wastewater by catalytic ozonation reactive ceramic membrane with facile spraying of nano Ti[sbnd]Mn oxides: A pilot scale attempt
2023, Journal of Water Process EngineeringCarbon electrochemical membrane functionalized with flower cluster-like FeOOH catalyst for organic pollutants decontamination
2023, Journal of Colloid and Interface Science
- 1
These authors contributed equally to the work.