Ha, t m t (2020) synthesis of reduced graphene oxide (rgo) for the removal of tetracycline from aqueous solutions master’s thesis, vietnam national university, hanoi

VIETNAM NATIONAL UNIVERSITY, HANOI VIETNAM JAPAN UNIVERSITY HA THI MY TRINH SYNTHESIS OF REDUCED GRAPHENE OXIDE (rGO) FOR THE REMOVAL OF TETRACYCLINE FROM AQUEOUS SOLUTIONS MASTER'S THESIS VIETNAM NATIONAL UNIVERSITY, HANOI VIETNAM JAPAN UNIVERSITY HA THI MY TRINH SYNTHESIS OF REDUCED GRAPHENE OXIDE (rGO) FOR THE REMOVAL OF TETRACYCLINE FROM AQUEOUS SOLUTIONS MAJOR: ENVIRONMENTAL ENGINEERING CODE: 8520320.01 RESEARCH SUPERVISORS: Dr TRAN DINH TRINH Dr NGUYEN THI AN HANG Hanoi, 2020 ACKNOWLEDGEMENTS This work could not have been completed without the collaboration and help of many people whom I want to thank First of all, I would also like to extend my deepest gratitude to Dr Tran Dinh Trinh, who inspired me to develop invaluable insight into a new field to me I’m also deeply indebted to Dr Nguyen Thi An Hang, who provided me with relentless support and constructive advices Many thanks to Mrs Dao Thi Huong – the laboratory technician – as well as staffs of the Master’s Program in Environmental Engineering for all practical instructions and useful contributions Thanks also go to my classmates and teammates, who enthusiastically supported me during this study Finally, I cannot begin to express my thanks to my family and friends for their patience and support until I finished this work I’d like to acknowledge the assistance of the staffs from the Academic, Research and Development Promotion Department of VNU Vietnam Japan University as well as Japan International Cooperation Agency for guiding and supporting me to complete my thesis Thank you all for everything Ha Noi, August 7th, 2020 Student Ha Thi My Trinh i TABLE OF CONTENTS Acknowledgements .i List of figures v List of tables vi List of abbreviations .vii Introduction Chapter Literature review 1.1 Antibiotics pollution .4 1.1.1 Definition, classification and sources of antibiotics Sources of antibiotics Application of antibiotic in human and veterinary dedicines 1.1.2 Occurrence of antibiotics in water and environmental effects Occurrence of antibiotics in water Effect of antibiotic residues 1.1.3 Regulations on antibiotic content in water 1.1.4 Tetracycline pollution in water .10 1.2 Technologies of the treatment of antibiotics in water 11 1.2.1 Filtration and sorption processes 11 1.2.2 Photodegradation and oxidation 12 1.2.3 Biodegradation 12 1.2.4 Other techniques 13 1.2.5 Technologies applied for the treatment of TC in water 14 1.3 Synthesis and application of rGO in antibiotic adsorption .14 1.3.1 Synthesis of rGO .15 Chemical reduction 15 Thermal reduction 15 Solvothermal/hydrothermal reduction 16 Other methods 16 1.3.2 Application of rGO in antibiotic adsorption 17 Chapter Materials and methods 18 ii 2.1 Materials .18 2.2 Methods 18 2.2.1 Literature review .18 2.2.2 Sample analysis in laboratory 18 Characterization of materials 18 a) Fourier-transform infrared spectroscopy 18 b) Energy-dispersive X-ray spectroscopy 20 c) Scanning Electron Microscopy 21 d) X-ray diffraction 22 e) Surface area and pore volume calculation 23 f) pH point of zero charge 25 Determination of Tetracycline concentration 25 2.2.3 Data calculation .26 a) Removal efficiency 26 b) Adsorption capacity 26 c) Kinetic parameters 27 d) Isotherm parameters 27 e) Thermodynamic study 28 2.2.4 Statistical analysis 28 2.3 Experiment setup 29 2.3.1 Material synthesis 29 2.3.2 Factors influencing the efficiency of TC adsorption 29 a) Contact time 29 b) pH 30 c) Dosage of rGO 30 d) Initial concentration of Tetracycline 30 2.3.3 Isotherm tests 30 2.3.4 Kinetics tests 30 2.3.5 Thermodynamic tests 31 Chapter Results and discussion 32 3.1 Material characterization 32 iii 3.1.1 Fourier-transform infrared spectroscopy 32 3.1.2 Energy-dispersive X-ray spectroscopy 33 3.1.3 X-ray diffraction 34 3.1.4 Surface area and pore volume 35 3.1.5 pH point of zero charge 37 3.2 Adsorption study 38 3.2.1 Factors influencing TC adsorption 38 a) Contact time 38 b) pH 39 c) Dosage 40 d) Initial concentration 41 e) Temperature 42 3.2.2 Adsorption isotherms 43 3.2.3 Adsorption kinetics 45 3.2.4 Adsorption thermodynamics 46 Conclusions and recommendations 48 Conclusions .48 Recommendations .48 References 50 Appendix 58 iv LIST OF FIGURES Figure 1.1 Pathways of antibiotics into water Figure 1.2 Global antibiotic consumption in livestock 2010 Figure 1.3 Legislation on antibiotics as growth promoters .7 Figure 2.1 FT-IR 4600 Jasco 20 Figure 2.2 Principle of EDX measurement .21 Figure 2.3 JSM-IT100/JED-2300 Analysis Station Plus, JEOL 21 Figure 2.4 MiniFlex 600 23 Figure 2.5 TriStar II Plus, Micromeritics 25 Figure 2.6 Calibration curve for Tetracycline 26 Figure 3.1 FT-IR result comparison of GO and rGO 32 Figure 3.2 SEM images of (a) graphite and (b) rGO 33 Figure 3.3 XRD results of GO and rGO 35 Figure 3.4 (a) N2 adsorption and desorption isotherms, (b) Types of physisorption isotherms, and (c) Types of hysteresis loops (IUPAC) 36 Figure 3.5 Pore size distribution of rGO obtained from DFT method 36 Figure 3.6 The plot of ΔpH versus pHi 38 Figure 3.7 Effect of contact time on TC adsorption by rGO 39 Figure 3.8 Effect of pH on TC adsorption by rGO 40 Figure 3.9 Effect of dosage effect on TC adsorption by rGO 41 Figure 3.10 Effect of initial concentration on TC adsorption by rGO 42 Figure 3.11 Effect of temperature on TC adsorption capacity of TC of rGO 43 Figure 3.12 Comparison of experimental data and modeled data on adsorption isotherms 43 Figure 3.13 Plot of ΔG0 against temperature (K) 46 v LIST OF TABLES Table 1.1 Antibiotics classification according to chemical structure Table 1.2 Chemical properties of tetracycline .10 Table 3.1 IR Spectrum by frequency range .33 Table 3.2 C/O ratio comparison of GO and rGO 34 Table 3.3 Properties of materials used for TC removal in previous studies 37 Table 3.4 Langmuir and Freundlich isotherm parameters on TC adsorption 44 Table 3.5 First- and Second-order kinetic parameters for TC adsorption .45 Table 3.6 Thermodynamic parameters of TC sorption process by rGO 47 Table S1 Antibiotic Resistance Alliance Science-Based PNEC Targets for Risk Assessments 58 Table S2 Removal of tetracycline antibiotics using different treatment processes 65 vi LIST OF ABBREVIATIONS BJH Barrett-Joyner-Halenda method DFT Density Functional Theory EDA Electron donor-acceptor EDX Energy-dispersive X-ray spectroscopy FT-IR Fourier-transform infrared spectroscopy GO Graphene oxide IUPAC International Union of Pure and Applied Chemistry pHpzc Point of zero charge rGO Reduced graphene oxide SEM Scanning electron microscopy TC Tetracycline WWTPs Wastewater treatment plants XRD The X-ray diffraction vii INTRODUCTION Since its discovery in 1928, antibiotics have played a very important role in human health protection and livestock industry It is estimated that millions of people have been saved from bacterial diseases (smallpox, cholera, typhoid fever, syphilis, etc.) thanks to antibiotics Antibiotics have revolutionized the treatment of bacterial diseases, which probably increase the average life span of Americans from 47 years in the early 20th century to 78.8 years (Chain et al 2016) Antibiotics are also widely known as growth stimulant in fisheries, livestock and cultivation However, besides the great health and economic benefits, antibiotics are also associated with negatively potential risks to humans and ecosystems Antibiotics were considered a persistent or “pseudo-persistent” substances because its speed of entering the environment is faster than that of its decomposition (Gothwal and Shashidhar, 2015), thus causing harms to the ecosystem One of the biggest problems was antibiotic resistance, which means bacteria were resistant to antibiotics that they are sensitive to Antibiotic abuse behavior and antibiotic production activities created an environment with sub optimal antibiotics (a dose sufficient to kill bacteria) that helped "train" bacteria that develop antibiotic-resistant individuals Many studies warned the 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Lowest Value Cefalothin N/A 2.00 2.00 Cefazolin N/A 1.00 1.00 Cefdinir N/A 0.25 0.25 Cefepime N/A 0.50 0.50 Cefixime 0.60 0.06 0.06 Cefoperazone N/A 0.50 0.50 Cefotaxime 0.12 0.13 0.12 Cefoxitin N/A 8.00 8.00 Cefpirome N/A 0.06 0.06 Cefpodoxime proxetil 1.76 0.25 0.25 Cefquinome 1.60 N/A 1.60 Ceftaroline 0.12 0.06 0.06 Ceftazidime 1.30 0.50 0.50 Ceftibuten N/A 0.25 0.25 Ceftiofur N/A 0.06 0.06 Ceftobiprole 0.23 0.25 0.23 Ceftolozane 1.90 N/A 1.90 Ceftriaxone 29.40 0.03 0.03 Cefuroxime 1.70 0.50 0.50 Cephalexin 0.21 4.00 0.21 Cephradine 0.19 N/A 0.19 59 Chloramphenicol N/A 8.00 8.00 Chlortetracycline 5.00 N/A 5.00 Ciprofloxacin 0.45 0.06 0.06 Clarithromycin 0.26 0.25 0.25 Clinafloxacin N/A 0.50 0.50 Clindamycin 0.10 1.00 0.10 Cloxacillin 20.00 0.13 0.13 Colistin (Polymyxin E) 9.00 2.00 2.00 Daptomycin 510.00 1.00 1.00 Delamanid 0.03 N/A 0.03 Doripenem 0.46 0.13 0.13 Doxycycline 25.10 2.00 2.00 Enramycin 4.80 N/A 4.80 Enrofloxacin 1.91 0.06 0.06 Ertapenem 14.00 0.13 0.13 Erythromycin 0.50 1.00 0.50 Ethambutol N/A 2.00 2.00 Faropenem N/A 0.02 0.02 Fidaxomicin 891.00 0.02 0.02 Florfenicol 38.00 2.00 2.00 Flucloxacillin 26.80 N/A 26.80 60 Fluconazole N/A 0.25 0.25 Flumequine N/A 0.25 0.25 Fosfomycin N/A 2.00 2.00 Fusidic acid N/A 0.50 0.50 0.06 0.06 Framycetine Testing ongoing Gatifloxacin N/A 0.13 0.13 Gemifloxacin N/A 0.06 0.06 Gentamicin 0.15 1.00 0.15 Imipenem 0.41 0.13 0.13 Isoniazid N/A 0.13 0.13 Kanamycin 1.05 2.00 1.05 Levofloxacin 0.52 0.25 0.25 Lincomycin 0.81 2.00 0.81 Linezolid 3.50 8.00 3.50 Loracarbef N/A 2.00 2.00 Mecillinam N/A 1.00 1.00 Meropenem 1.50 0.06 0.06 Metronidazole N/A 0.13 0.13 1.00 1.00 Minocycline Testing ongoing 61 Moxifloxacin N/A 0.13 0.13 Mupirocin N/A 0.25 0.25 Nalidixic acid N/A 16.00 16.00 Narasin N/A 0.50 0.50 N/A N/A Natamycin Testing ongoing Neomycin 0.03 2.00 0.03 Netilmicin N/A 0.50 0.50 Nitrofurantoin N/A 64.00 64.00 Norfloxacin 120.00 0.50 0.50 Ofloxacin 10.00 0.50 0.50 Oxacillin N/A 1.00 1.00 Oxytetracycline 47.00 0.50 0.50 Pefloxacin N/A 8.00 8.00 Penicillin G Procaine 16.00 0.25 0.25 Phenoxymethylpenicillin N/A 0.06 0.06 Piperacillin 4.30 0.50 0.50 Polymixin B 0.06 N/A 0.06 N/A N/A N/A 31.00 Pristinamycin Puromycin Testing ongoing 31.00 62 Retapamulin Rifampicin N/A Testing ongoing 0.06 0.06 0.06 0.06 Rifamycin N/A N/A N/A Rifaximin N/A N/A N/A Roxithromycin 6.80 1.00 1.00 Secnidazole N/A 1.00 1.00 Sparfloxacin N/A 0.06 0.06 Spectinomycin N/A 32.00 32.00 Spiramycin 1.09 0.50 0.50 Streptomycin N/A 16.00 16.00 Sulbactam N/A 16.00 16.00 Sulfadiazine 11.21 13.00 11.21 Sulfamethoxazole 0.60 16.00 0.60 Tedizolid 3.20 N/A 3.20 Teicoplanin 12.90 0.50 0.50 0.06 0.06 Telithromycin Testing ongoing Tetracycline 3.20 1.00 1.00 Thiamphenicol N/A 1.00 1.00 Tiamulin N/A 1.00 1.00 63 Ticarcillin Tigecycline N/A Testing ongoing 8.00 8.00 1.00 1.00 Tildipirosin 0.42 N/A 0.42 Tilmicosin 0.80 1.00 0.80 Tobramycin 4.30 1.00 1.00 Trimethoprim 312.45 0.50 0.50 Trovafloxacin N/A 0.03 0.03 N/A N/A Tulathromycin Testing ongoing Tylosin 0.98 4.00 0.98 Vancomycin N/A 8.00 8.00 Viomycin N/A 2.00 2.00 Virginiamycin N/A 2.00 2.00 *PNEC‐Environment (PNECENV) values are based on eco-toxicology data generated by Alliance member companies and relevant peer reviewed literature These values are intended to be protective of ecological species and incorporate assessment factors consistent with standard environmental risk methodologies **PNEC-Minimum Inhibitory Concentration (PNECMIC) values are based on the published approach and are intended to be protective of resistance promotion 64 Table S2 Removal of tetracycline antibiotics using different treatment processes Antibiotics Matrix Treatment Operating conditions Results and comments Tetracycline Distilled water Semiconductor MP UV (125 W); pH = 6.0; [TC] More than 98 % of tetracycline was photocatalysis = 10–50 mg/L; TiO2 (100 % oxidized within about h; 100 % of anatase or anatase/rutile = 4/1; total organic carbon removal using and 0.4 g/L of catalyst TiO2 (anatase/rutile) Semiconductor UV (254 nm, 365 nm); solarium 100 % degradation and 90 % total photocatalysis device (300–400 nm); TiO2 organic carbon removal (UV 254 catalyst; 05–1.0 g/L catalyst; nm; 0.5 g/L TiO2; after 120 min) Deionised water [tetracycline] = 40 mg/L; 100 % degradation and 70 % total treatment time = 120 organic carbon removal (Solarium device; 0.5 g/L TiO2; after 120 min) 50 % degradation and 10 % total organic carbon removal (UV 365 nm; 0.5 g/L TiO2; after 120 min) Ultra-pure water Distilled water Direct photolysis Electrochemical oxidation UV at 365 nm; pH=6; 73 % tetracycline degradation; 15 % [tetracycline] = 10–40 mg/L total organic carbon removal pH = 3.9–10.0, current density = More than 90 % of tetracycline 15.9–63.5 mA/cm , treatment degradation at pH = 3.9, current time = 60 min, [Na2SO4] = 0.05– density = 47.6 mA/cm2, [Na2SO4] = 0.20 mol/L, Ti/ RuO2–IrO2: 0.1 mol/L and [tetracycline] = 100 anode, stainless steel: cathode, mg/L [OH] = 0–4.20 mmol/ L, [tetracycline] = 50–200 mg/L, volume = 200 mL Distilled water Photoelectrocatalytic TiO2 photoanode, UV light (254 More than 80 % of tetracycline process nm, 2.5 mW/cm2), 0.5 V, pH = degradation 5.5, [NaSO4] = 0.02 moL/L, [tetracycline] = 10 mg/L, treatment time = h Spicked STP Photo-Fenton effluent Black light (15 W); solar irradiation; 1–10 mM H2O2; 0.20 100 % tetracycline degradation under solar irradiation mM ferrioxalate or Fe(NO3)3; Surface [tetracycline] = 24 mg/L Deionised water Distilled Water Semiconductor Xe lamp (300–800 nm); TiO2 100 % tetracycline degradation and photocatalysis and ZnO as catalyst; 0.5–1.5 g/L 50 % total organic carbon removal TiO2; 0.2–1.5 g/L ZnO; pH = 3– (after 15 min, 1.5 g/L TiO2, pH = 10 (TiO2); pH = 6–11 (ZnO); 8.7) 100 % tetracycline degradation [tetracycline] = 20 mg/L and mineralization (after 10–60 min, 1.0 g/L ZnO, pH = 11) 65 Chlortetracycline Distilled water Adsorption with aluminium oxide C = 20–110 lg/L, 0.8–3.5 g/L Rapid adsorption of tetracycline Al2O3 (43 %), chlortetracycline (57 %) and Oxytetracycline oxytetracycline (44 %) Tetracycline Chlortetracycline Aqueous Photoelectrocatalytic [tetracycline] solution process [chlortetracycline] = 10 mg/L; Oxytetracycline = 10 mg/L; About 95 % of tetracycline antibiotics degradation [oxytetracycline] = 10 mg/L; medium pressure mercury lamp Tetracycline (15 W, kC 365 nm, 21.2 lW/ cm2, [Na2SO4] = 0.1 moL/L, potential applied = 0.6–3.0 V, treatment time = 0–180 min, pH = 3–12 Chlortetracycline Aqueous Electrochemical Current intensity = 1.5 A, [Tetracycline antibiotics] final = 0.6 solution oxidation Ti/IrO2 (or Ti/PbO2) : anode, Ti: mg/L, [oxytetracycline] = 0.7 mg/L cathode, electrode gap = 10 mm, after h of treatment time Doxycycline Oxytetracycline Tetracycline Wastewater [NaCl] (or [Na2SO4]) = 1,000 animal mg, treatment time = h, husbandry [Tetracycline antibiotics] = 100 mg/L, [oxytetracycline] = 100 mg/L Chlortetracycline Doxycycline Oxytetracycline Distilled water spicked with Nanofiltration NF 200 membranes (14.6 cm2 Degradation area), pH = 7, T = 20 C antibiotics between 50 and 80 % calcium of tetracycline after 90 chloride, humic acid and NaCl Tetracycline Chlortetracycline Distilled water Oxidation/reduction Doxycycline pH = 7.0 ± 0.1, mM phosphate The efficiencies for OH reaction = buffer, T = 22.0 ± 1.0 C, Xe arc 32–60 % lamp (172 nm), [TOC] = 13 lg/L, Oxytetracycline electron pulse radiolysis (472 The efficiencies for ereaction = 15– nm, G = 5.2 10-4 m2/J 29 %, for chlortetracycline = 97 % Temperature = 25 C ± 1.0 C, pH Toxicity inhibition: surface water = 2–10, radiation dose = 1.66– (43.2 % of tetracycline, 36.3 % of 3.83 Gy/min, [HCO3-] = 0.0–7.2 chlortetracycline, Tetracycline Chlortetracycline Oxytetracycline Ultrapure water Surface water Gamma radiation 2- Tetracycline Ground water Wastewater 47.2 % meq/L, [SO4 ] = 0.0–41.0 mg/L, oxytetracycline); [NO3-] (32.7 % of tetracycline, 55.6 % of = 0.0–4.4 mg/L, [Tetracycline antibiotics] = 20– chlortetracycline, 100 mg/L oxytetracycline) 66 Ground of 44.4 water % of Chlortetracycline Doxycyline Oxytetracycline Tetracycline Spiked synthetic Coagulation and river water adsorption activated carbon with Contact time min, 10 lg/L for Synthetic water: 43–94 % removal adsorption process, 100 lg/L for of the drugs (40 mg/L of coagulant) coagulation, coagulation PACI (5–60 mg/L), granular activated River water: 44–67 % removal of the carbon filtration: calgon F400 drugs and coconut-based carbon Demeclocycline Minocycline 67 .. .VIETNAM NATIONAL UNIVERSITY, HANOI VIETNAM JAPAN UNIVERSITY HA THI MY TRINH SYNTHESIS OF REDUCED GRAPHENE OXIDE (rGO) FOR THE REMOVAL OF TETRACYCLINE FROM AQUEOUS SOLUTIONS MAJOR: ENVIRONMENTAL... the water, so that the treatment plants usually not take this kind of contaminants seriously Many studies have been carried out with the purpose of eliminating antibiotics from environments The. .. residues in the environment also paid attention As many antibiotics, their residues in environment promoted the formation and the development of antibiotic resistant microorganisms These antimicrobial