Tăng cường hoạt tính sinh học của hoạt động oxy hóa amoni bởi graphene oxide và titanium nanotubes

國立交通大學 環境工程研究所 碩士論文 利用氧化石墨烯及鈦酸鹽奈米管增強厭氧氨 氧化菌活性之研究 Bio-augmentation of anaerobic ammonium oxidation activity supported on graphene oxide and titanium nanotubes 研究生：屈氏青玄(Khuat Thi Thanh Huyen) 指導教授：董瑞安教授 (Dr Ruey-an Doong) Tai ngay!!! Ban co the xoa dong chu nay!!! 林志高教授 (Dr Jih-Gaw Lin) 中華民國106年 月 利用氧化石墨烯及鈦酸鹽奈米管增強厭氧氨氧化菌活性之研究 Bio-augmentation of anaerobic ammonium oxidation activity supported on graphene oxide and titanium nanotubes 研究生： Student：Thi Thanh Huyen Khuat 指導教授： Advisor：Ruey-an Doong Jih-Gaw Lin 國立交通大學 環境工程研究所 碩 士 論 文初稿 A Thesis Submitted to Institute of Environmental Engineering College of Engineering National Chiao Tung University in Partial Fulfillment of the Requirements for the Degree of Master of Science in Environmental Engineering July, 2017 Hsinchu, Taiwan 中 華 民 國 106年 月 Bio-augmentation of anaerobic ammonium oxidation activity supported on graphene oxide and titanium nanotubes Student：Thi Thanh Huyen Khuat Advisor：Ruey-an Doong Jih-Gaw Lin Institute of Environmental Engineering National Chiao Tung University ABSTRACT Nitrogen removal from wastewater is gaining worldwide attention because of the potential threat of nitrogen species to the environment Anaerobic ammonium oxidation (Anammox) is a promising method which can convert ammonium ion directly to nitrogen gas However, Anammox still faces the difficulty in the enhancement of slow growth rate of Anammox microorganisms Herein, we have systematically investigated the effect of graphene oxide (GO) and titanium nanotube (TNTs) on the Anammox biomass for nitrogen removal TNTs, the 1dimensional negatively charged nanomaterials show little effect on the enhancement of Anammox growth, presumably attributed to the strong repulsive force between TNTs and Annamox bacteria GO makes a remarkable impact on the bacterial growth After the batch incubation of 5h, the Anammox activity in the presence of 0.1 g/L GO is enhanced 14.2 % when compares with that in the absence of nanomaterial The continuous experiment also proves the applicability of using GO as an effective support to improve nitrogen removal GO utilization can enhance Anammox activity by 30% compares with that of the normal reactor after 113d of incubation In the GO induced reactor, the effluent concentrations of ammonium and nitrite decrease steadily and reach the steady state after 80d of incubation, while it takes 127 d in the i reactor without GO to achieve the steady state These results clearly demonstrate the feasibility of utilizing GO as the support for Anammox bacteria to shorten the start-up incubation time by rapid acclimation as well as to enhance the activity of Anammox bacteria Keywords: Graphene oxide, Anammox, nitrogen removal, start-up ii ACKNOWLEDGEMENT Foremost, I would like to express my sincere gratitude to my both advisors Prof Ruey-an Doong and Prof Jih-Gaw Lin for their infinite guidance, patience, generous encouragement and supports to me during my two years of studying at National Chiao Tung University Their great insight and profound knowledge was of great help for me to finish my work step by step I appreciated all the opportunities my professors offered me by giving me intellectual freedom in my work, supporting my attendance at various conferences, engaging me in new ideas, and demanding a high quality of work in all my endeavors Besides my advisors, I would like to thank the rest of my thesis committee: Prof Shen-Yi Chen and Prof Ji-Doong Gu for spending their valuabe time to help me to evaluate my thesis defense and give me some suggestion to enrich my work My deep gratitude also goes to fellow labmates in ECCL, including Akhilesh, Rama, Amber, Bin and Anh for their kindness and help in training me and for many valuable advices that given to me whenever I get stuck with my research I would be remiss if I did not thank to Dr Ankan, from his keen scientic insight and his ability to put complex ideas into simple terms to broaden and stimulated my research interest I would also like to thank to Prof Lin labmates for their help and supporting, including Mak, Jolin, Dai, and Henry Iam also fortunate to meet a great Taiwanese friend who always give me a hand without any hesitation whenever I need help Special thanks to Shila for supporting me during two years in Taiwan I woud also like to acknowledge to all other fellow labmates in ECCL for their assistances in many aspects that I can not list them all here I learnt a lot from all of you and all of you are helpful to color my stay in Taiwan iii I would also like to express my gratitude to Institute of Environmental Engineering, National Chiao Tung University for all the opportunities they have given me over the past two years Last but not the least, I would like to thank my family for their unconditional love and support they gave me during these years iv Content Index Chapter Introduction 1.1 Motivation 1.2 Objective Chapter Background and theory 2.1 Nitrogen cycle 2.2 Anaerobic ammonium oxidation 2.3 Cell structure and metabolism of Anammox Figure 2.2 Anammox cell with different compartments and three surrounding membranes.7 2.4 Reactor system used for enrichment of Anammox bacteria 2.5 Nanomaterials 12 2.5.1 Definition 12 2.5.2 Properties 12 2.6 Graphene material 12 2.6.1 Concepts and properties 12 2.6.2 Bacterial interaction with Graphene Oxide and surfaces 15 2.6.3 Anammox bacteria interact with different Graphene family materials 19 2.7 Titanium nanotubes (TNTs) 20 2.7.1 Concepts and properties 20 2.7.2 Photochemical Properties and Photocatalytic Functions 23 v 2.7.3 Parameters influencing the morphology of titanate nanotubes 25 2.7.4 Bacteria and cell interaction with titanium nanotubes 28 2.8 Interaction between bacteria and surface 29 Chapter Materials and methods 31 3.1 Synthesis 31 3.1.1 Synthesis of GO 31 3.1.2 Synthesis of TNT 33 3.2 Instrumentations 34 3.2.1 X-ray diffraction (XRD) 34 3.2.2 Raman spectroscopy 34 3.2.3 Fourier transform infrared spectroscopy (FTIR) 35 3.2.4 Transmission electron microscope (TEM) 35 3.2.5 Scanning electron microscope (SEM) 35 3.2.6 Brunauer–Emmett–Teller (BET) 36 3.2.7 UV-visible spectrometer (UV-Vis) 37 3.3 Specific Anammox activity test 37 3.3.1 Materials and Equipemnt 37 3.3.2 Theory of Specific Anammox Activity (SAA) test 38 3.4 Long-term effects of GO on Anammox activity 39 3.4.1 Microorganisms and feeding medium 39 vi 3.4.2 Reactor start-up 41 3.4.3 Operational strategy 42 3.4.4 Chemical analysis 43 3.4.5 Monitoring 44 3.5 Molecular analysis 44 3.5.1 DNA extraction, PCR amplification and clone libraries construction 44 3.5.2 Phylogenetic analysis 45 Chapter Results and discussion .45 4.1 Characterization of Graphene Oxide 45 4.1.1 XRD spectra of GO 45 4.1.2 Raman spectra of GO 46 4.1.3 FTIR spectra of GO 47 4.1.4 TEM image of GO 48 4.1.5 BET surface area of GO 49 4.1.6 Testing the vaporization of GO 50 4.2 Effect of GO on Anammox activity 51 4.2.1 Specific Anammox Activity test 51 4.2.2 Long-term effect of GO on Anammox activity 52 4.3 Characterization of TNTs 64 4.3.1 Scanning electron microscope of TNTs 64 vii 4.3 Characterization of TNTs 4.3.1 Scanning electron microscope of TNTs One dimension of Titanium nanotubes was synthesized by hydrothermal method The morphology of TNT obtained in Fig 4.16 SEM analysis can clearly show that tubular morphology was successfully formed by the anatase precursor powder in the alkaline condition under high temperature Mostly a higher degree of size control was produced The diameter of TNTs mainly smaller than 10nm In which the diameter with the size around nm takes account of 50% X Shi et al (2015) investigated that TiO2 nanotubes with smaller diameters (30 nm) can improve the adhesion of osteoblasts to the greatest extent.139 Therefore, The TNTs were synthesized might suitable for bacteria adhesion and growth Figure 4.16 Scanning electron microscope and particle distribution of TNTs 64 4.3.2 BET surface area of TNTs The N2 adsorption isotherm of TNTs belongs to the type IV isotherm, and the can be classified into the type H2.140 The N2 adsorption isotherms of TNTs were analyzed by using BJH method to estimate the average pore sizes was 6.37 nm and the total pore volume was 0.3 cm3/g The N2 adsorption isotherms were analyzed using the Brunauer-Emmett-Teller (BET) equation, allowing to obtain the specific surface area of the TNTs (𝑆BET) was 252.54 m2/g Figure 4.17 BET surface area of Titanium nanotubes 65 4.4 Long-term effect of TNT on Anammox activity Profile the concentration of NH4+-N, NO2 N, NO3 N during operational time of the Anammox process The seed sludge was collected for inoculation from a full-scale landfill leachate treatment plant in Xin-Feng, Taiwan The initial biomass concentration was 2385 mg VSS L1 The concentration of TNTs (70 mg/L) was induced into the reactor The influent NH4+-N and NO2 N was 60 mg/L From day to day 28, the concentration of NH4+-N in the effluent is quite high because of initial inoculum In the standard reactor, the concentration of NH4+-N in a range of 18.5 – 48 mg/L and this was about 27.4 – 47.7 mg/l in the reactor with TNTs adding Though the results in this phase highly fluctuate, the performance of NH4+-N removal still better compared with the reactor containing TNTs NO2- -N in the effluent fluctuated around 10 mg/L The stoichiometric molar ratio of nitrite consumption versus ammonium consumption was not calculated as a ratio in anammox equation (1.25 ± 0.1) Thus, it was hypothesized that denitrifying bacteria were still the dominant population even though anammox activity appeared in this phase From day 28 to day 45, The high concentration of ammonium was observed might be due to cell lysis phase Due to change in environmental condition (from wastewater treatment plant to the reactor), some of the biomass could not adapt and died However, half of nitrite in influent still removed Since heterotrophic denitrifying bacteria grew much faster than autotrophic anammox bacteria, denitrifying might still predominate in phase II Phase III ran from day 45 to day 95 Anammox activity occurred as both ammonia and nitrite being removed simultaneously and nitrate in effluent accumulate gradually It was also indicated the decreasing activity of denitrifying bacteria However, during phase III, the performance of nitrogen species removal in both reactor remained the same There were not any advances achieved in the reactor with TNTs compared with the absent of nano material Fig 4.18 66 Figure 4.18 Reactor performance during operation of the anammox process (g-i) profile the concentration of NH4+-N, NO2 N, NO3 N in influent and effluent in R1, control reactor; R2, reactor containing TNTs 4.5 Phylogenetic tree of anammox bacteria The functional of hzsB gene responsible for hydrazine synthesis in anammox biochemical reaction to form the intermediate hydrazine was selected and used as biomarker for detection of anammox bacteria in these two plants Nucleotide sequences, achieved in this study together with the known Anammox bacteria species and metagenomic sequences from GenBank, were combined to construct a phylogenetic tree of this study (Fig 4.19) Three genera were detected from the four samples, including Brocadia, Kuenenia and Jettenia Sample #1 and #2 were all distributed in Jettenia After more than 300 days of incubation in 67 Anammox species were dominant in both reactors (reactor without GO, reactor containing GO) The results indicate that both reactors were set up and run successfully All sequences from sample #4 were affiliated with Brocadia, and sample #3 were related to both Brocadia and Kuenenia, but the Brocadia was the dominant genera Figure 4.19 Phylogeny of hzsB gene based on NJ methods with bootstrap value 1000 The numbers beside the sample ID (#1, #2, #3, #4) are the sequence number (1.Reactor without GO , Reactor containing GO, Reactor without TNTs , Reactor containing TNTs) 4.6 Compared two kinds of nano materials in experimental operation Among huge of nanomaterials are already in use TNTs and GO were chosen for application in this experiments due to the original properties of both nano materials They have large surface area, environmentally friendly, low cost and especially is the surface structure of two material They are hydrophilic in nature The surface wettability of biomaterials has been found to be an important factor for cell-biomaterial interaction, and more hydrophilic surfaces are able to improve cell attachment and cellular behavior.141, 142 This property can affect cell-biomaterial interaction since the culture media is a water based 68 liquid and in hydrophobic surfaces, poor cell attachment could be observed.143 Beside, these two materials contain negative charge on the surface, providing the chance for some metal ions in the medium can be absorbed on the surface such as Ca2+, Fe2+ As a result, after depositing on the surface, bacteria easier to utilize the nutrients Since the result in the case of GO is better compared with TNTs, the possibility might be due to the planar structure of GO is more effectively for bacteria to contact with the surface of the material, instead of the tubular structure of TNTs That is the reason why GO could help to improve the nitrogen efficiency and shortening start-up of anammox bacteria 69 Chapter Conclusions Results obtained in this study reveals that the application of GO is an effective method to improve nitrogen removal by stimulating Anammox activity Results show the excellent activity of GO toward bacterial growth in the concentration range of 50-100 mg/L Different GO doses have been checked in batch experimentswhereas 100 mg/L GO concentration has been found the optimal value for improving Anammox process Over the optimal concentration of GO dose, Anammox activity has been reduced The maximum of 30% increase in biological activity for nitrogen removal has been observed during 113 days test Though, the extra advancement of GO was diminished after the reactor reached its stable stage, the oucome of this present work still prove the effective role of GO in shortening and enhancing the Anammox activity in start-up period Incase of TNTs, after 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