The MP-AES 4200 using microwave plasma and an atomic emission spectroscopy detector provide a new and improved instrument to the analytical field. In this project will the performance of the equipment be evaluated in controlled NaCl-heavy matrices for selected metals (Cu, Zn, Li) and the result from this will be used to optimize a method for specific samples. These samples consist of combustion ashes from the incineration of hazardous waste and are provided by the company SAKAB AB. The sample preparation consisted of several cycles of L/S 10 followed by microwave assisted dissolution with concentrated HNO3, aqua regia or 18.2 MΩ. An extended amount of metals were quantified for these samples (Al, As, Ba, Ca, Cd, Cr, Cu, Fe, K, Li, Mn, Na, Ni, Pb, V, Zn) and most (not Ca, Li, K or Na) were compared with an ICP-MS instrument equipped with a collision cell used for the elements As, Fe and V. A final experiment was made on an L/S 10 of the samples to attempt to separate the metals from the salt with ion exchange, something that would make it possible to recycle this otherwise unused waste. The detection limits were all in the low μg L-1 except for Cd, Mn and Zn, which were between 2-4 μg L-1. The MP-AES was found to be able to handle matrices up to 5 g L-1 NaCl without a significant loss of response and provided near identical results to the ICP-MS for the elements that could be compared, this did not included the elements not quantified with the ICP-MS or V which was the only element under the limit of detection for the MP-AES. The experiment where an attempt was made to separate the metals from the salt was proven successful after treatment of bark compost and another type of waste ash as cation exchangers.

The production of silver-loaded zeolites either by ion exchange method or by isomorphous substitution of silver ions into zeolites frameworks and their antimicrobial activity is presented. Silver-loaded zeolites produced by ion-exchange in this work include silver-exchanged zeolite X, silver-exchanged zeolite A and silver-exchanged high-alumina Phillipsite. Silver-doped Analcime was produced by isomorphous substitution of silver ions into the Analcime framework. The silver-loaded zeolites were characterized by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, particle size analysis and Fourier transformed infrared (FTIR) spectroscopy. Studies showed that the amount of silver ions loaded into the zeolites frameworks differed for each zeolite. XRD analysis showed little or no changes in the phase purity of all zeolites before and after ion exchange or before and after substitution of silver ions. SEM analysis and particle size analysis showed that the morphology of each zeolite particles was closely related before and after ion exchanged or before and after substitution of silver ions. The antimicrobial activity of these silver-loaded zeolites was investigated by exposing Escherichia coli K12W-T, Staphylococcus aureus NCIMB6571 and Pseudomonas aeruginosa NCIMB8295 suspended in tryptone soya broth (TSB) to the silver-loaded zeolites. The first stage of the investigation involved the exposure of the strains to silver-loaded zeolites in TSB for a duration of 24 hours at different concentration of silver-loaded zeolites. The second stage involved the exposure of the strains to silver-loaded zeolites in TSB over a period of two hours. The persistency of antimicrobial activity of silver-loaded zeolites was investigated by retrieving each silver-loaded zeolite from the first exposure cultures, washed copiously with de-ionised water and adding to fresh bacterial suspensions. To understand the mode of antimicrobial activity of the silver-loaded zeolites, the uptake of silver ions by the strains, composition of fatty acid, as well as the DNA content of Escherichia coli K12W-T was studied. The results obtained showed silver ions appeared to elute from the zeolites frameworks into the TSB in anomalous trend. All three microorganisms were completely inhibited within one hour with the silver-loaded zeolites retaining their antimicrobial activity. The release of silver ions from the zeolites frameworks followed first-order kinetics with varying rate constants and half-lives. The fatty acid composition of all strains as well as the DNA content of Escherichia coli K12W-T were affected by the action of silver ions.

Single-frequency and mode-locked silver film ion-exchanged glass waveguide lasers as well as all-optical clock recovery based on birefringent fiber resonators have been experimentally and theoretically studied. The theory, modeling and fabrication process of silver film ion-exchange techniques, have been discussed and presented.The UV-written gratings on both IOG-1 active and passive glass have been studied. For the first time, with a high quality narrowband grating UV-printed on the passive section of a hybrid glass, a DBR waveguide single-frequency laser is demonstrated with the linewidth less than 1 MHz and the output power of 9 mW.Novel saturable absorbers based on a fiber taper embedded in carbon nanotubes (CNTs)/polymer composite were demonstrated. The saturable absorbers were utilized to build mode-locked fiber lasers, which were studied experimentally. A mode-locked ring laser utilizing an Er-Yb-codoped glass waveguide as the gain medium was also demonstrated. In addition, short cavity mode-locked waveguide lasers with CNTs film on the top were theoretically investigated, which shows a short cavity mode-locked waveguide laser is very promising.A new concept to perform multi-channel multi-rate all-optical clock recovery based on birefringent fiber-optic waveguide resonators was discussed. The concept has been advanced to polarization-insensitive operation. The experimental results, obtained as a proof-of-concept, agree well with numerical simulations.

A range of porous solid adsorbents were synthesised and their ability to separate and capture carbon dioxide (CO2) from gas mixtures was examined. CO2 separation from flue gas – a type of exhaust gas from fossil fuel combustion that consists of CO2 mixed with mainly nitrogen and biogas (consists of CO2 mixed with mainly methane) were explicitly considered. The selected adsorbents were chosen partly due to their narrow pore sizes. Narrow pores can differentiate gas molecules of different sizes via a kinetic separation mechanism: a large gas molecule should find it more difficult to enter a narrow pore. CO2 has the smallest kinetic diameter in zeolites when compared with the other two gases in this study. Narrow pore adsorbents can therefore, show enhanced kinetic selectivity to adsorb CO2 from a gas mixture. The adsorbents tested in this study included mixed cation zeolite A, zeolite ZK-4, a range of aluminophosphates and silicoaluminophosphates, as well as two types of titanium silicates (ETS-4, CTS-1). These adsorbents were compared with one another from different aspects such as CO2 capacity, CO2 selectivity, cyclic performance, working capacity, cost of synthesis, etc. Each of the tested adsorbents has its advantages and disadvantages. Serval phosphates were identified as potentially good CO2 adsorbents, but the high cost of their synthesis must be addressed in order to develop these adsorbents for applications. / <p>At the time of the doctoral defence the following papers were unpublished and had a status as follows: Papers 4-8: Manuscripts.</p>

Natural organic matter (NOM) is present in all surface waters as a result of decaying vegetation, biological activity, and organic soil. Alternative NOM removal processes such as anion exchange resins (AERs) have shown NOM removals typically ranging between 50 to 90%, with up to 99% removal achieved in some cases. The first portion of this study evaluated the performance of two AERs; a conventional Type 1 AER and magnetic ion exchange resin (i.e. MIEX®) for NOM removal from surface water quantified by UV254, dissolved organic carbon (DOC), and specific UV absorbance (SUVA). Samples were also characterized for chloride, sulphate, and chloride-to-sulphate mass ratio (CSMR) to provide additional information on water quality characteristics of AER treated waters. Overall, the results showed that both AERS were effective for removing NOM. However, the MIEX® resin provided greater removal of NOM with shorter contact times compared to the conventional resin investigated. Water treated with MIEX® resin showed significantly higher chloride and lower sulphate concentrations than the conventional AER. Higher CSMR values were found with MIEX® treated water compared to conventional AER system, although both resins showed CSMR much greater than 0.5, which can increase galvanic corrosion effects with lead. Bench-scale jar tests were conducted to investigate the impact of temperature on the efficacy of three NOM removal treatment technologies; enhanced coagulation with alum, MIEX® and a combined MIEX® treatment followed by coagulation with a low dose of alum. Higher settled water turbidity was observed during cold water operating conditions for all three processes. At cold-water operating conditions, DOC removal was reduced with combined MIEX® -Alum treatment, and UV254 removal was impacted for both MIEX® and MIEX® -Alum processes. The combined MIEX®-Alum process was found to provide the lowest THMFP and HAAFP at both temperatures to concentrations lower than current regulatory maximum acceptable concentration (MAC) guidelines in Canada. Surface charge analysis experiments were performed at bench-scale using synthetic water containing humic acid to determine the relationship between NOM and the charge of AER-treated waters. Further bench and pilot-scale studies were performed to investigate the use of surface charge measurements to monitor and optimize NOM removal during treatment with AER systems. Strong correlations were observed between UV254 and respective charge measurements (i.e. ZP, SC) of AER-treated synthetic and raw waters. The results of this research has shown that it is possible to use charge to optimize the MIEX® process for NOM removal. Additionally, it was found that SC measurements could be used as an operational tool for AER processes, where deviations in SC from optimum treatment would indicate the requirement for fresh resin addition or resin regeneration.

Facile procedures based on hyphenated ion-exchange chromatography (IEC) and inductively coupled plasma mass spectrometry (ICP-MS) were developed to determine conditional stability constants, speciate chromium species and investigate the reduction of Cr(VI). 1. Improvements were made to a method previously developed to determine the conditional stability constant, Kf’, and chelation number, n, using IEC-ICP-MS. This method allowed the accurate determination of the conditional stability constant of a simple system. However, the corresponding chelation number was significantly different to the expected value because the principal assumption, i.e. that the ligand was in excess, was not realized in the experimentation. Furthermore, it neglected complexes other than that formed with EDTA4-. By taking into account these factors, accurate Kf’ and n were obtained for Co-EDTA and Zn-EDTA systems. 2. A simple method was developed for chromium speciation analysis at sub-µg L-1 level in potable water by IEC-ICP-MS. Cr(VI) and Cr(III) were separated on IonPac® AG-7 guard column within 7.5 minutes using gradient elution with 0.1 M ammonium nitrate and 0.8 M nitric acid. H2 collision/reaction interface gas eliminated chlorine-based and carbon-based polyatomic interferences on Cr detection. Water samples were analyzed directly, without any pretreatment. The accuracy of the method was verified through accurate analysis of riverine water certified reference material. Limits of detection of 0.02 and 0.04 µg L-1 for Cr(VI) and Cr(III), respectively, were obtained. 3. This speciation analysis method was then used for kinetics studies of Cr(VI) reduction in acidified riverine water. Water was spiked with Cr(VI), with or without Cr(III), and evolution of each Cr species with time was monitored by speciation analysis, showing that the reduction of Cr(VI) was a pseudo first order reaction. By plotting the logarithm of the peak area ratio of the instant Cr(VI) concentration over that of the original spiking versus time, the reaction rate constant was obtained as the slope. The reduction rate increased with decreasing pH and increasing temperature. The activation energy of the reaction at pH 1.3 was calculated using an Arrhenius plot. This method offers the advantages of small sample consumption, minimal sample manipulation, and easy data interpretation. / Thesis (Ph.D, Chemistry) -- Queen's University, 2010-09-30 08:05:27.342

The current study investigated application of natural adsorbents in brine treatment. Brines are hypersaline waters generated in power stations and mining industries rich in Mg2+, K+, Ca2+, Na+, SO4 2- , Cl- and traces of heavy metals, thus there is a need for these brines to be treated to recover potable water and remove problematic elements. Natural adsorbents have been successfully used in waste water treatment because of their high surface area and high adsorptive properties when they are conditioned with acid or base. The investigation of pH showed that natural adsorbents did not perform well at low pH of 4 and 6. The adsorbents were able to work efficiently at the natural pH of 8.52 of the brine solution. These results show that natural adsorbents hold great potential to remove cationic major components and selected heavy metal species from industrial brine wastewater. Heterogeneity of natural adsorbents samples, even when they have the same origin, could be a problem when wastewater treatment systems utilizing natural clinoptilolite and bentonite are planned to be developed. Therefore, it is very important to characterize the reserves fully in order to make them attractive in developing treatment technologies.

Renewable power generation from the controlled mixing of sea and fresh water is relatively unexplored when compared to the development for solar, wind, and other sustainable power alternatives. When global river discharge was taken into account, an estimated 2.6 TW of obtainable energy exists in untapped salinity gradients. Reverse electrodialysis is one proposed power-generating mechanism for harnessing energy from brackish environments and relies on the transport of aqueous salt ions through an apparatus of ion-exchange membranes. In this thesis, operational parameters, including flow direction, salinity composition, and membrane selectivity, are investigated. For optimal performance, I have employed counter-current flow mode with monovalent ion selective membranes and pure 0.5 M NaCl saline solution. The results show that a maximum open circuit voltage (OCV) level of 2.01 V is obtained with an active membrane area of 0.0756 m². The presence of multivalent ions in the feed solutions hinders OCV levels, but the effects are reduced with monovalent-selective membranes. Preliminary results are insightful; in order to increase the commercially viability of this technology, future work is needed to enhance the performance properties of the ion exchange membranes.

Baculoviruses are versatile viruses that can be used as biopestisides, or for the production of recombinant protein and vaccines. Baculoviruses have also been found to be able to transfer genes to mammalian cells. This finding opened the door for the application of baculovirus vectors in human gene therapy. However, the mass production of clinical grade baculovirus vectors is challenging. Downstream processing has now become the bottle-neck of the manufacturing process. In this work, an anion exchange chromatography-based process was investigated for the purification of recombinant baculovirus vectors using a novel hydrogel based membrane (Natrix Separations Ltd.). Crude recombinant baculovirus supernatant from infected insect cell cultures was first subjected to a clarification process consisting of centrifugation and filtration. The pH of the viral solution was adjusted and then passed through a fast protein liquid chromatography system consisting of the ion exchange membrane. After washing weakly bound impurities, the captured baculoviruses are recovered by an elution step. Overall, baculoviruses strongly associated with the membrane; however, this interaction which was much physical as it was chemical, could not be entirely reversed and baculovirus was lost in the process. Product purity has also been evaluated and up to 85% of total protein reduction was determined. The significant losses of baculovirus observed have indicated major limitations in using this membrane for the purification of baculovirus.

iv The recovery of lactic acid from its dilute aqueous solutions is a major problem. The ester of lactic acid, namely, methyl lactate has a wide range of applications. The esterification of an aqueous solution of lactic acid with methanol is a reversible reaction. As excess of amount water is present in the reaction mixture, the conversion is greatly restricted by the chemical reaction equilibrium limitations. In this study the esterification kinetics of lactic acid with methanol both in the absence and presence of an ion exchange resin as a heterogeneous acid catalyst was investigated with isothermal batch experiments between 40 - 70 0 C and at atmospheric pressure. Self-polymerization of lactic acid was enlightened by considering the hydrolysis reaction of lactoyllactic acid at the reaction temperatures and at various initial concentrations. Both homogeneous and heterogeneous reaction rate constants were evaluated. Methyl lactate process development was also investigated. The process was based on the recovery of 10% lactic acid by reaction with methanol in a absorption column using ion-exchange resin Lewatit SPC-112 H+. The effect of various parameters including lactic acid concentration or reactant molar ratio, lactic acid feed flow rate, methanol and inert carrier rate on reactor performance were studied. The reaction of methyl lactate formation over the ion exchange resin catalyst was observed to be slower than the mass transfer rate whereas mass transfer of methanol in gas phase was the limiting step for methanol transfer to the liquid mixture. Mass transfer of water from liquid phase to the gas phase was controlled by the mass transfer resistance of liquid phase. Thus, it can be concluded that the counter-current gas-liquid reactors with acidic solid catalysts can be used as simultaneous reaction and separation equipment.