Zeolites are well-known aluminosilicate minerals that have been widely used as adsorbents in separation, purification processes and environmental pollution control. Zeolites are used in various industrial applications due to their high cation-exchange ability, molecular sieve and cataltic properties. In order to reduce the costs of acquisition and minimise the disposal of adsorbents, both modified natural zeolite and synthetic zeolite (derived from kaolinite) were used for the purification of wastewater. The characteristic properties and applications of adsorbents are also discussed including the advantages and disadvantages of each technique. The present work involves the study of the removal of Cu2+, Fe3+, Pb2+ and Zn2+ from synthetic metal solutions using natural zeolite. Laboratory experiments were used to investigate the efficiency of adsorbents in the uptake of heavy metals from industrial wastewater. These include equilibrium tests, kinetic studies and regeneration studies. The physical and chemical characterization of the zeolites was carried out using different analytical techniques such as Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), X - Ray Diffraction (XRD), X - Ray Fluorescence (XRF), Thermogravimetric Analysis (TGA), Fourier Transform Infrared (FT-IR) Spectroscopy and Inductively Coupled Plasma-Optical Emission Spectrometer (ICP-OES). The kinetic study indicated the suitability of the natural zeolite for the removal of Cu2+, Fe3+, Pb2+ and Zn2+ ions from synthetic wastewater. Batch experiments were used to identify the effect of parameters that affect the rate of adsorption such as the effect of adsorbent mass, effect of adsorbent particle size, effect of initial solution pH, effect of initial solution concentration, effect of agitation speed and effect of pre-treatment of adsorbent and evaluated their impact on the efficiency of the zeolite in the removal of heavy metals from industrial wastewater. The kinetic studies showed that the capacity of the adsorbents for the removal of heavy metals increased with a greater mass of absorbent, increased initial solution pH, increased agitation speed, higher solution concentration as well as the application of a pre-treatment. The results from the equilibrium studies positively demonstrated that natural zeolite can be used as an excellent adsorbent for removing heavy metals from multi-component solutions. The equilibrium experiments indicated that the capacities of natural zeolite for the uptake of heavy metals increased when the initial solution pH increased. The results indicated that the maximum removal capacities Q were 22.83, 14.92, 14.49 and 17.54 mg/g natural zeolite for copper, iron, zinc, and lead respectively. Both the Langmuir and Freundlich isotherm models were used to characterize the experimental data and to assess the adsorption behaviour of natural zeolite for copper, iron, lead and zinc. The experimental data were slightly better suited to the Langmuir isotherm than the Freundlinch isotherm. The value of the correlation coefficients r2 ranged from 0.93 to 0.99 for the Langmuir isotherm and from 0.90 to 0.99 for the Freundlich isotherm. The present work also involved the study of synthetic zeolite A, which was derived from natural kaolinite. The conversion of the raw materials into zeolitic materials was carried out in two ways: first, conventional hydrothermal synthesis and second, alkaline fusion prior to hydrothermal synthesis. The results from both routes show that zeolite A was synthesised successfully. Finally, the experiments show that both natural and synthetic zeolites can be available in commercial quantities. Synthetic zeolites are more attractive for some specific applications, while the cheapness of natural zeolite may favour its use.

Atualmente são muito discutidos temas que abordam a preservação do meio ambiente, para o desenvolvimento de tecnologias de produção que não a agridam, gerando resíduos menos tóxicos e em menor quantidade. Resíduos poluentes contendo metais como o crômio, têm sido lançados nos solos e rios, degradando a água utilizada para o consumo humano. Não diferentes são os problemas decorrentes de atividades nucleares, as quais geram rejeitos nas instalações e laboratórios de pesquisa. Embora estes rejeitos não sejam lançados no meio ambiente, muitas vezes encontram-se armazenados em laboratório inadequadamente, o que pode resultar em graves acidentes. Na intenção de solucionar estes problemas, existem várias técnicas para o tratamento de rejeitos, entre elas a troca iônica eletroquímica (EIX – electrochemical ion exchange). A EIX é um processo avançado que une as vantagens da troca iônica convencional com o fato de usar como reagente o elétron, reduzindo consideravelmente o volume da solução a ser tratada. Esta técnica consiste na elaboração de um eletrodo, no qual o trocador iônico é incorporado fisicamente em uma estrutura do eletrodo com um aglutinante. Optou-se neste trabalho pela resina catiônica Amberlite CG-50 para o tratamento dos rejeitos contendo íons crômio e o trocador catiônico inorgânico fosfato de zircônio para os íons césio, pois apresentam boa estabilidade química em meio oxidante e perante radiação ionizante. A quantidade de carvão, de grafita e aglutinante para a formulação do eletrodo mais eficiente também foi estudada. Após a escolha dos melhores eletrodos, verificaram-se retenções para o Cr e para o Cs da ordem de 99,3% e 99,8%, respectivamente. A eluição completa tanto do íon crômio quanto do íon césio, sem nenhuma adição de reagentes, revelou-se uma das principais vantagens deste processo, o que torna possível a reutilização do eletrodo sem perda de sua capacidade. Com base nos resultados apresentou-se um processo contínuo de tratamento de rejeitos utilizando-se uma célula eletrolítica de fluxo (CELFLUX) de alta capacidade de retenção para o íon Cr e Cs. A alta eficiência desta célula tanto na retenção quanto na eluição, levando a uma redução importante no volume do rejeito e, até mesmo, possibilitando a reutilização dos íons separados, torna o processo altamente viável para o emprego industrial. / Nowadays, environmental preservation using technologies that do not attack it, generating non-toxic residues and reduced volumes, has been discussed. Hazardous effluents, containing metals, as chromium, have been poured in the soils and rivers, degrading the water. Not different are the problems originated from some nuclear activities that generate wastes, as in chemical research laboratories. Although those wastes are not poured in the environment, sometimes they are inadequately stored, what can cause serious accidents. With the purpose of solving this problem, there are some techniques to waste treatment, between them there is the electrochemical ion exchange (EIX). EIX is an advanced process that has advantages over traditional ion exchange and the fact of using the electron as the only reagent, reduces the volume of the solution to be treated. This technique consists of development of an electrode, where an ion exchanger is physically incorporated in an electrode structure with a binder. In this study, cationic resin Amberlite CG-50 and zirconium phosphate have been chosen for the separation of chromium and cesium from waste, respectively. They were chosen because they present high chemical stability in oxidizing media and at ionizing radiation. The quantity of charcoal, graphite and binder used in formulation of electrode have been studied either. Before choosing the best electrode, it was verified sorption percentage of 99,3% for chromium and 99,8% for cesium. The greater advantage of this process is the total elution of chromium as much as cesium, without reagents addition, being possible to reuse the electrode without losing its capacity. Beside on the results, a continuous process for the wastes containing Cr and Cs, using a flux electrolytic cell (CELFLUX) of high retention capacity, was presented. The high efficiency of this cell for both retention and elution, leading to an important reduction of waste volume, and, every more, making possible the reutilization of the ions studied, makes the process available for industrial waste treatment purposes.

The major concern of this work is the development of hierarchically porous structured zeolite composites for ion-exchange applications by deposition of a thin layer of zeolite on inexpensive porous supports which offers better efficiency in separation processes. The merits of utilization of zeolite composites in industrial applications are generally reducing mass transfer resistance and pressure drop. In addition to this they have advantages in the removal of metal ions from wastewater such as increasing the metals uptake and minimizing the volume of waste disposed especially after vitrification. This thesis presents results from a combination of experimental work and simulation study of experimental data to give isotherm and kinetic models. The experimental work shed light on the preparation of zeolite composites using zeolite X (Si/Al ~ 1.35) and clinoptilolite (Si/Al ~ 4.3), studying the performance of these composites on the removal of the Sr2+ and Mn2+ ions and then stabilization of waste materials resulting from the ion-exchange process. Clinoptilolite was hydrothermally synthesized to show the effect of non-framework cations on the removal process. The porous supports were diatomite which is naturally occurring silica and carbon which is obtained from Iraqi date stones by a thermal treatment conducted at 900°C. Coating the support surface with zeolites crystals was conducted in two different ways. The layer by layer approach, which has not previously been used, was used to prepare monolithic carbon clinoptilolite composite using a combination of sucrose/citric acid and zeolite. The other approach was modifying the support surface by ultrasonication in the presence of nanoparticles suspension prepared using ball mill to create nucleation sites and enhance the crystal attachment during hydrothermal treatment. Characterisation was implemented in each case using XRD, SEM, EDAX, TGA and BET method. Ion-exchange experimental results showed higher ion-exchange capacity obtained when the composites were used in comparison to pure zeolites, when a comparison is based on actual weight of zeolite used for removal of Sr2+ and Mn2+ ions. A study of encapsulation of ions showed that it is feasible to solidify the waste materials by vitrification and/or geopolymerization to eliminate leaching of ions to the environment. The simulation studies showed that the ion-exchange kinetic followed the pseudo second order kinetic model. This fitting indicates that the rate of ion-exchange process is controlled by a chemical reaction related to valence forces. The overall ion-exchange process is controlled by a combination of ion-exchange reaction, film diffusion and intra-particle diffusion. Moreover, the thermodynamic studies which were conducted under different temperatures revealed that the ion-exchange of Sr2+ and Mn2+ ions is practicable, spontaneous and endothermic.

Kam Yuen Kwan = 利用散射及反衝粒子飛行時間譜儀及其他表面分析儀器就LiTaO3對質子及鋰離子交換後改變之研究 / 甘婉君. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references. / Text in English; abstracts in English and Chinese. / Kam Yuen Kwan = Li yong san she ji fan chong li zi fei xing shi jian pu yi ji qi ta biao mian fen xi yi qi jiu LiTaO3 dui zhi zi ji li li zi jiao huan hou gai bian zhi yan jiu / Gan Wanjun. / Acknowledgements --- p.i / Abstract --- p.iii / Table of contents --- p.viii / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Definition of Ferroelectrics --- p.1 / Chapter 1.2 --- Common Properties of Ferroelectrics --- p.2 / Chapter 1.3 --- Polarization --- p.2 / Chapter 1.4 --- Lithium Tantalate (LiTa03) --- p.7 / Chapter 1.4.1 --- Crystal Structure --- p.8 / Chapter 1.4.2 --- Pyroelectric Effect --- p.9 / Chapter 1.4.3 --- Determination of Polarity --- p.10 / Chapter 1.4.4 --- Proton Exchange --- p.11 / Chapter 1.4.5 --- Reverse Exchange --- p.12 / Chapter 1.4.6 --- Applications --- p.13 / Chapter 1.5 --- Emerging Attentions in Surface Properties of Smart Materials --- p.14 / Chapter 1.6 --- Difficulties in Surface Studies of Ferroelectric and Related Smart Materials --- p.15 / Chapter 1.7 --- Recent Developments of TOF-SARS in Our Research Group and Its Applicability on LiTa〇3 --- p.16 / Chapter 1.8 --- Objectives of the Present Thesis Work --- p.17 / Chapter 1.9 --- Organization of the Thesis --- p.17 / Chapter 1.10 --- Reference --- p.18 / Chapter Chapter 2 --- Ion Exchange Processes and Sample Prepartion --- p.20 / Chapter 2.1 --- Fundamental of Ion Exchange Technique --- p.20 / Chapter 2.2 --- Sample Preparation --- p.22 / Chapter 2.2.1 --- Starting Material --- p.22 / Chapter 2.2.2 --- Proton Exchange Procedures --- p.23 / Chapter 2.2.3 --- Reverse Exchange Procedures --- p.23 / Chapter 2.3 --- Reference --- p.24 / Chapter Chapter 3 --- Time-of-Flight Ion Scattering and Recoiling Spectrometry (TOF-SARS) --- p.26 / Chapter 3.1 --- Introduction --- p.26 / Chapter 3.1.1 --- Physics in Elemental Analysis --- p.26 / Chapter 3.1.2 --- Physics in Structural Analysis --- p.29 / Chapter 3.2 --- Instrumentation --- p.32 / Chapter 3.2.1 --- Vacuum Chamber --- p.33 / Chapter 3.2.2 --- Pumping System --- p.35 / Chapter 3.2.3 --- Sample Manipulator --- p.35 / Chapter 3.2.4 --- Pulsed Ion Beam Line --- p.36 / Chapter 3.2.5 --- Detectors and Associated Electronics --- p.37 / Chapter 3.3 --- Reference --- p.39 / Chapter Chapter 4 --- Other Surface Science Tools Used in This Work --- p.41 / Chapter 4.1 --- Fourier Transform Infrared Spectroscopy (FTIR) --- p.41 / Chapter 4.1.1 --- Principle of FTIR --- p.41 / Chapter 4.1.2 --- Experiment --- p.42 / Chapter 4.1.3 --- Attenuated Total Reflectance (ATR) Mode of FTIR --- p.44 / Chapter 4.2 --- X-Ray Photoelectron Spectroscopy (XPS) --- p.45 / Chapter 4.2.1 --- Basic Principle of XPS --- p.45 / Chapter 4.2.2 --- Experimental Set Up --- p.48 / Chapter 4.3 --- Elastic Recoil Detection (ERD) --- p.49 / Chapter 4.3.1 --- Basic Theory of ERD --- p.49 / Chapter 4.3.2 --- Experimental Set Up --- p.50 / Chapter 4.4 --- Scanning Electron Microscope (SEM) --- p.51 / Chapter 4.4.1 --- Working Principle of SEM --- p.52 / Chapter 4.4.2 --- Experimental Set Up --- p.52 / Chapter 4.5 --- Reference --- p.53 / Chapter Chapter 5 --- Results and Discussions --- p.54 / Chapter 5.1 --- ERD Results on Incorporation of Protons --- p.54 / Chapter 5.2 --- XPS Results on Proton Exchange and Reverse Exchange --- p.56 / Chapter 5.3 --- FTIR Results on Proton Exchange and Reverse Exchange --- p.57 / Chapter 5.4 --- SEM Results on Domain-Inversion Induced by Proton Exchange --- p.59 / Chapter 5.5 --- TOF-SARS Results on Enhancement of Ion-induced Electron Emission by Proton Exchange --- p.61 / Chapter 5.5.1 --- Typical TOF-SARS Spectra - Data from Molybdenum Sample (Mo) Holder --- p.61 / Chapter 5.5.2 --- Virgin LiTa03 (0001) --- p.62 / Chapter 5.5.3 --- Possible Mechanism for the Variation of O(S) and the Electron Emission Yield --- p.65 / Chapter 5.5.4 --- The Use of O(S) Peak to Calculate the Potential Built Up upon a Change of Temperature --- p.67 / Chapter 5.5.5 --- TOF-SARS Data from the Proton and Lithium-ion Exchanged LiTa03 (0001) --- p.69 / Chapter 5.5.6 --- Plausible Mechanisms of Enhancement of Ion-induced Electron Yield induced by Proton Exchange --- p.70 / Chapter 5.6 --- Additional Discussions of the TOF-SARS Data on LiTa03 and Other Relevant Experiments --- p.75 / Chapter 5.6.1 --- Additional Discussion of the Nature of the Electron Peaks --- p.75 / Chapter 5.6.2 --- Additional Experiments on Azimuthal Angle (δ) Scans --- p.77 / Chapter 5.6.2.1 --- Data from Platinum (Pt) (111) as a Reference Test --- p.77 / Chapter 5.6.2.2 --- Azimuthal Angle Dependence of Ion-induced Electron Emission from Proton-ion Exchanged LiTa03 (0001) --- p.78 / Chapter 5.7 --- Reference --- p.80 / Chapter Chapter 6 --- Conclusion --- p.83 / Chapter Chapter 7 --- Appendix --- p.86 / Chapter 7.1 --- Caption --- p.86 / Chapter 7.2 --- Figures --- p.90

Le dessalement de l’eau de mer par osmose inverse connait un intérêt croissant depuis une vingtaine d’années afin de répondre aux besoins en eau potable et en eau d’irrigation dans de nombreuses régions dans le monde. Cependant, le bore contenu dans l’eau de mer est incomplètement éliminé par osmose inverse et des concentrations supérieures à la valeur limite de 0,3 mg/ sont obtenues. Dans cette étude, nous présentons des résultats sur l'élimination du bore de l'eau de mer en utilisant une technique hybride de résine échangeuse d'ions/microfiltration sans addition continue de résine. Une membrane de microfiltration en céramique a été utilisée pour retenir la résine échangeuse d'ions dans le réservoir d'alimentation et la boucle de circulation tandis que la solution modèle de bore ou l’eau de mer était continuellement ajoutée. Tout d'abord, des résines fines de taille moyenne 40 - 60 µm ont été obtenues par broyage et tamisage de résines commerciales (Amberlite IRA743, Diaion CRB05 et Purolite S108). Les résines ont ensuite été testées en système batch pour obtenir les cinétiques de sorption et par la technique hybride de sorption/microfiltration pour mesurer les courbes de perçage et le flux de perméat. L'effet de la dose de résine, de la concentration initiale en bore, de la pression transmembranaire et de la taille des pores de la membrane a été étudié. Dans une deuxième partie, l’effet de la taille des particules de résine sur les courbes de perçage en sortie d’une colonne a été déterminé et une comparaison entre les performances d’une colonne et d’un système hybride a été proposée. Dans une dernière partie, les isothermes et cinétiques de sorption expérimentales sont comparées à des équations classiques, et les courbes de perçage en colonne et en système hybride sont modélisées. En conclusion, il est suggéré que le procédé hybride de résine échangeuse d'ions et microfiltration sans ajout continu de résines peut être une technique possible pour l'élimination du bore / The maximum concentration suggested by the World Health Organization is 0.3 mg/L. In this study, we investigated a hybrid process for boron removal from water which associates sorption on ion exchange resin and microfiltration, without continuous resin addition. First, fine resins were obtained by grounding and sieving at 40 and 60 µm commercial resins (Amberlite IRA743, Diaion CRB05 and Purolite S108). The resins were then tested in batch to obtain the kinetics and in the hybrid sorption/microfiltration process to measure breakthrough curves and permeate flux. A ceramic microfiltration membrane was used to retain the ion exchange resin in the feed tank and the circulation loop while the boron solution was continuously added and the permeate collected for analysis. The effect of resin dosage, boron initial concentration, transmembrane pressure and membrane pore size was studied. In a second part, the effect of the size of the resin particles on the breakthrough curves measured at the outlet of a column was determined and a comparison between the performances of a column and a hybrid system are proposed. For the Amberlite IRA743 resin, the overall process was tested: reverse osmosis followed by hybrid sorption/microfiltration. The hybrid process was able to re-duce concentration of bacterial and phytoplankton cells thanks to the steric rejection by the microfiltration membrane, suggesting that the same membrane can be used as a pretreatment before reverse osmosis in a desalination plant. In a final part, the experimental isotherms and kinetics are compared with classical models, and the breakthrough curves obtained with a column and with the hybrid sys-tem are modelised. Overall, it is suggested that the hybrid process of ion exchange resin and microfiltration without continuous addition of resin may be a possible technique for boron removal

Atualmente são muito discutidos temas que abordam a preservação do meio ambiente, para o desenvolvimento de tecnologias de produção que não a agridam, gerando resíduos menos tóxicos e em menor quantidade. Resíduos poluentes contendo metais como o crômio, têm sido lançados nos solos e rios, degradando a água utilizada para o consumo humano. Não diferentes são os problemas decorrentes de atividades nucleares, as quais geram rejeitos nas instalações e laboratórios de pesquisa. Embora estes rejeitos não sejam lançados no meio ambiente, muitas vezes encontram-se armazenados em laboratório inadequadamente, o que pode resultar em graves acidentes. Na intenção de solucionar estes problemas, existem várias técnicas para o tratamento de rejeitos, entre elas a troca iônica eletroquímica (EIX – electrochemical ion exchange). A EIX é um processo avançado que une as vantagens da troca iônica convencional com o fato de usar como reagente o elétron, reduzindo consideravelmente o volume da solução a ser tratada. Esta técnica consiste na elaboração de um eletrodo, no qual o trocador iônico é incorporado fisicamente em uma estrutura do eletrodo com um aglutinante. Optou-se neste trabalho pela resina catiônica Amberlite CG-50 para o tratamento dos rejeitos contendo íons crômio e o trocador catiônico inorgânico fosfato de zircônio para os íons césio, pois apresentam boa estabilidade química em meio oxidante e perante radiação ionizante. A quantidade de carvão, de grafita e aglutinante para a formulação do eletrodo mais eficiente também foi estudada. Após a escolha dos melhores eletrodos, verificaram-se retenções para o Cr e para o Cs da ordem de 99,3% e 99,8%, respectivamente. A eluição completa tanto do íon crômio quanto do íon césio, sem nenhuma adição de reagentes, revelou-se uma das principais vantagens deste processo, o que torna possível a reutilização do eletrodo sem perda de sua capacidade. Com base nos resultados apresentou-se um processo contínuo de tratamento de rejeitos utilizando-se uma célula eletrolítica de fluxo (CELFLUX) de alta capacidade de retenção para o íon Cr e Cs. A alta eficiência desta célula tanto na retenção quanto na eluição, levando a uma redução importante no volume do rejeito e, até mesmo, possibilitando a reutilização dos íons separados, torna o processo altamente viável para o emprego industrial. / Nowadays, environmental preservation using technologies that do not attack it, generating non-toxic residues and reduced volumes, has been discussed. Hazardous effluents, containing metals, as chromium, have been poured in the soils and rivers, degrading the water. Not different are the problems originated from some nuclear activities that generate wastes, as in chemical research laboratories. Although those wastes are not poured in the environment, sometimes they are inadequately stored, what can cause serious accidents. With the purpose of solving this problem, there are some techniques to waste treatment, between them there is the electrochemical ion exchange (EIX). EIX is an advanced process that has advantages over traditional ion exchange and the fact of using the electron as the only reagent, reduces the volume of the solution to be treated. This technique consists of development of an electrode, where an ion exchanger is physically incorporated in an electrode structure with a binder. In this study, cationic resin Amberlite CG-50 and zirconium phosphate have been chosen for the separation of chromium and cesium from waste, respectively. They were chosen because they present high chemical stability in oxidizing media and at ionizing radiation. The quantity of charcoal, graphite and binder used in formulation of electrode have been studied either. Before choosing the best electrode, it was verified sorption percentage of 99,3% for chromium and 99,8% for cesium. The greater advantage of this process is the total elution of chromium as much as cesium, without reagents addition, being possible to reuse the electrode without losing its capacity. Beside on the results, a continuous process for the wastes containing Cr and Cs, using a flux electrolytic cell (CELFLUX) of high retention capacity, was presented. The high efficiency of this cell for both retention and elution, leading to an important reduction of waste volume, and, every more, making possible the reutilization of the ions studied, makes the process available for industrial waste treatment purposes.

Approximately 25% of households in the U.S. treat their wastewater onsite using conventional onsite wastewater treatment systems (OWTS). These systems typically include a septic tank or a series of septic tanks followed by a soil absorption system. They effectively remove biochemical oxygen demand (BOD), total suspended solids (TSS), fats and grease but are not designed to remove significant amounts of nitrogen. High nitrogen loading to coastal and ground waters can be dangerous to aquatic life and public health. Hence, there is a need for advanced onsite wastewater treatment systems that can effectively remove nitrogen. Making enhanced nitrogen removal for OWTS as our primary goal, a laboratory scale Hybrid Adsorption and Biological Treatment Systems (HABiTS) was developed and upon observation of its effective nitrogen removal capacity, a pilot demonstration study with two side-by-side HABiTS, one with recirculation and one without recirculation (only forward flow) were constructed and tested at the Northwest Regional Water Reclamation Facility in Hillsborough County (Florida). HABiTS employ biological nitrogen removal and ion exchange for effective nitrogen removal. HABiTS is a two-stage process which uses nitrification for the oxidation of ammonium to nitrate and ion exchange for ammonium adsorption that helps buffer transient loading and also acts as a biofilm carrier in its stage 1 biofilter and it uses tire-sulfur hybrid adsorption denitrification (T-SHAD) in its stage 2 biofilter. These sulfur pellets help promote sulfur oxidation denitrification (SOD) and tire chips are used for nitrate adsorption during transient loading conditions, as biofilm carriers for denitrifying bacteria, and can also be used as organic carbon source to promote heterotrophic denitrification because they leach organic carbon. For this research, HABiTS without recirculation is considered as the control system and the performance of HABiTS with recirculation was tested for its ability to further enhance nitrogen removal from HABiTS. Nitrified effluent recirculation is a common strategy employed in wastewater treatment for enhanced nitrogen removal. It is the reintroduction of semi-treated wastewater to pass through an anoxic pre-treatment chamber to achieve better quality effluent. Recirculation is said to improve and consistently remove nitrogen at any hydraulic loading rate and/or nitrogen concentration. This is because of the dilution of high BOD septic tank effluent with nitrified effluent which lowers COD:TKN ratio and also improves mass transfer of substrates in the stage 1 biofilter. Recirculation also provides some pre-denitrification in the pre-treatment chamber, thereby reducing nitrogen load on the system. The HABiTS with recirculation (R) was run at 1:1 ratio of nitrified effluent recirculation rate to the influent flow rate for 50 days, and at 3:1 ratio for the remaining period of this research (200 days). The forward flow system (FF) was run under constant conditions throughout the research and comparisons between the two systems were made for different water quality parameters (pH, DO, conductivity, alkalinity, TSS, chemical oxygen demand (COD), total nitrogen (TN), total phosphorus (TP) and various nitrogen species). The final effluent ammonium results showed that the system with recirculation removed consistently > 80% NH4+-N during 1:1 and 3:1 recirculation ratios whereas the forward flow system achieved 57% removal. Further, an average of 81% total inorganic nitrogen (TIN) removal from the system influent was seen in the recirculation system’s final effluent when compared to an average of 55% in forward flow system’s final effluent. This research explains in detail, the impact of nitrified effluent recirculation on enhanced nitrogen removal in onsite systems and the results presented in this thesis proved that nitrified effluent recirculation provides promising enhanced nitrogen removal in an onsite wastewater treatment system.

Urine comprises around 1% of domestic sewage volume but holds 80% of total nitrogen. Source separation is a sustainable way to wastewater management than traditional way due to low energy cost and preventing certain pollutants into wastewater treatment plants. Currently, removing and recovering nitrogen from source-separated urine has attracted more and more interests. Of them, ion exchange was used for removal and recovery of nitrogen in the form of ammonia from synthetic urine for potential application as a fertilizer in agriculture. No previous research studies were conducted to investigate the removal and recovery of nitrogen from hydrolyzed urine by ion exchange using POPs (porous organic polymers). So this study focused on evaluating the performance of POPs and comparing with clinoptilolite in synthetic hydrolyzed urine in terms of adsorption capacity (isotherm), adsorption rate (kinetics), regeneration rate, and cost. The ammonium removal from hydrolyzed urine using POPs was rapid with a high capacity of 68.03 mg/g than clinoptilolite (15.36 mg/g), and the regeneration efficiency of clinoptilolite and POPs can achieve 91% and 95.3%, respectively based single time use result. Although POPs had the better performance at one time use and multiple times use, it also had high materials cost. Additionally, the capacity of POP was estimated using the integrated ion exchange regeneration process model as 30.24 mg/g and 28.65 mg/g on cycle 10 and cycle 24, respectively. The regeneration efficiency of POPs was predicated as 45.4% and 38.4% in cycle 10 and cycle 24, respectively. The predicted capacity decreased with the number of cycles, but remained at about 55% of virgin POPs after 24 cycles, indicating POPs can maintain good performance after multiple reuses than clinoptilolite.

Metal-organic materials (MOMs) represent an emerging class of materials comprised of molecular building blocks (MBBs) linked by organic linker ligands. MOMs recently attract great attention because of their ability to exhibit permanent porosity, thereby enabling study of properties in the context of gas storage, gas separation, solid supports for sensors, catalysis and so on. Although MOMs have been studied for over 60 years, the porous nature of MOMs was not systematically and widely explored until the early 1990's. This may be one of the reasons why template-directed synthesis of MOMs remains relatively underexplored, especially when compared to other classes of porous material (e.g. zeolite and mesoporous silicates). However, the study of template-directed synthesis exhibits great significance to the research field of MOMs as these considerations: (i) to access analogues of prototypal MOM platforms that cannot be prepared directly; (2) to create porous materials with new topologies; (3) to transfer the functionality of templates to MOMs; (4) to exert fine control over structural features. In this dissertation, I chose a functional organic material, porphyrin, as templates and succeeded to synthesize a series of porphyrin-encapsulating MOMs, (porph@MOMs), in which the porphyrins were encapsulated inside the cavities as guests. Porphyrins molecules can template the formation cavities with different shapes and sizes (e.g. triangle, square or hexagon) to accommodate the porphyrins molecules when organic ligands with different size and symmetry were utilized during the synthesis. On the other hand, the porphyrins molecules can also template the formation of octahemioctahedral cages or hexahedron cages with porphyrins trapped inside, which further built the tbo, pcu, rtl, zzz, mzz networks. By selecting templated porph@MOMs as platforms, post-synthetic modifications (PSMs) of porph@MOMs were further studied. A cadmium MOM, porph@MOM-10, can undergo PSM by Mn(II) or Cu(II) via single-crystal-to-single-crystal processes. The Mn- and Cu- exchanged PSM variants exhibit catalytic activity for epoxidation of trans-stilbene. Porph@MOM-11 can serve as a platform to undergo a new PSM process involving cooperative addition of metal salts via single-crystal-to-single-crystal processes. The incorporation of the salts leads to higher H2 and CO2 volumetric uptake and higher CO2 vs CH4 selectivity. Porph@MOM-11 was also found to be a versatile platform that can undergo metal ion exchange with Cu2+ in single-crystal-to-single-crystal fashion. The use of mixed metal salt solutions (Cu2+/Cd2+) with varying ratios of metal salts enabled systematic study of the metal exchange process in porph@MOM-11 in such a manner that, at one extreme, only the Cd porphyrin moieties undergo metal ion exchange, whereas at the other extreme both the framework and the porphyrin moiety are fully exchanged. It is also observed that a concerted PSMs approach of metal ion exchange and ligand addition towards a porphyrin-walled MOM, porphMOM-1 affords a porphyrin-encapsulating MOM, porph@MOM-14, in which porphyrin anions are encapsulated in the octahemioctahedral polyhedral cage via weak interactions. Beside of the template-directed synthesis and post-synthetic modification of porph@MOMs, pre-synthetic control of metal-organic materials' structures was also studied in this dissertation. Due to the partial flexibility of 1,3-benzenedicarboxylate linkers, kagom[eacute] lattice and NbO supramolecular isomers were observed from a complexation of bulky 1,3-benzenedicarboxylate ligand to Cu(II) paddlewheel moieties. In addition, a new family of hybrid nanoball vanadium MOM structures (Hyballs) was prepared by the self-assemble of trimesic acid with tetranuclear and pentanuclear vanadium polyoxometalates. These hyballs are robust, permanently porous and their exterior surfaces facilitate cross-linking via hydrogen bonds or coordination bonds to generate pcu networks.

Water recycling by membrane treatment is widely accepted as a leading alternative water source. This separation process creates a concentrated stream (called concentrates), containing most of the pollutants in 10%-20% of the flow; and a treated water stream. As nitrogen is a major concern, environmental regulations have become more stringent, requiring additional treatment to meet effluent standards. Other concerns include organic contaminants and potential production of halogenated organics if disinfection of the reject was applied. One option to address the problem of dissolved organic nitrogen and carbon is advanced oxidation. This oxidation could lead to degradation of refractory organic materials, which are poorly removed in conventional treatment. This project aims to evaluate treatment extent and cost of alternatives for organic (particularly nitrogen) removal in reject water addressing the following research gaps: (i) identifying the key organic pollutants present in the concentrated stream, (ii) the effectiveness and optimisation of coagulation, ion exchange and advanced oxidation; (iii) apparent cost of the different treatment methods. The untreated reverse osmosis concentrates were collected from two treatment plants:- Luggage Point, and Bundamba, both near Brisbane, Queensland, Australia. The first contains more colourful of organics than the second plant. Stirred cell fractionation with ultrafiltration membranes was used to characterise the removed key pollutants, as it offers better accuracy and reproducibility compared to centrifugation fractionation. Fluorescence spectral was used to monitor and identify specific organic compounds. The largest fraction was smaller sized <1kDa. This is probably small humic substances and fulvic acids, as indicated by Excitation Emission Matrix (EEM) analysis. A smaller portion of soluble microbial products (SMPs) also contributes to the concentrates. Bundamba contains large non coloured organics including organic nitrogen with elevated ammonia-N. In contrast, Luggage Point has higher colour, inorganic carbon and conductivity with less ammonia-N. Advanced Oxidation Process (AOP) was the most effective treatment method (high removal of organics, e.g. 55% COD of initial), followed by magnetised ion exchange (MIEX) and coagulations. For UV/H2O2 AOP, the optimal operating condition 400mg.L-1 H2O2 and 3.1kWh.m-3 energy input resulted in organics removals up to 55% with complete decolourisation. The effective reduction was found in all size ranges, preferably in >1kDa. Low inorganic carbon and salinity in Bundamba may allow better overall oxidation rates. MIEX also performed better in Bundamba with organic removals up to 43% and 80% decolourisation at the optimum resin dose of 15mL.L-1. Removal was preferential in size range of >3kDa, with more proportional percentage for decolourisation. Similarly, ferric coagulation removed a wider size range of organics. Further, ferric achieved better organic removal in Luggage Point with up to 49%. At the same molar dose (1.5mM), ferric is superior to alum, especially in Bundamba where there were less hydrophobic compounds according to EEM. Alum is poor for treatment of high organics with less coloured water. MIEX with an operational cost (chemicals and power only) of $0.14-$0.20.m-3 treated water seemed to be the most effective treatment overall. The resin achieved better results with a slightly higher cost than coagulation, and had a lower environmental impact due to reduced sludge production. AOP offers better treatment, but at a higher cost ($0.47.m-3 treated). Combined alternatives may benefit the removal effectiveness. Furthermore, more specific identification of contaminants should be investigated separately to choose appropriate treatment for priority chemicals. Another issue is further investigation of costing, including capital, and full environmental impact of treatment.