Analysis of N-nitrosames in water using micellar electrokinetic chromatography (MEKC) and development of online and offline methods of extraction and enrichment of neutral polar analytes

Evaluation of the quality of the environment is essential for human wellness as pollutants in trace amounts can cause serious health problem. Nitrosamines are a group of compounds that are considered potential carcinogens and can be found in drinking water (as disinfection byproducts), foods, beverages and cosmetics. To monitor the level of these compounds to minimize daily intakes, fast and reliable analytical techniques are required. As these compounds are relatively highly polar, extraction and enrichment from environmental samples (aqueous) are challenging. Also, the trend of analytical techniques toward the reduction of sample size and minimization of organic solvent use demands new methods of analysis. In light of fulfilling these requirements, a new method of online preconcentration tailored to an electrokinetic chromatography is introduced. In this method, electroosmotic flow (EOF) was suppressed to increase the interaction time between analyte and micellar phase, therefore the only force to mobilize the neutral analytes is the interaction of analyte with moving micelles. In absence of EOF, polarity of applied potential was switched (negative or positive) to force (anionic or cationic) micelles to move toward the detector. To avoid the excessive band broadening due to longer analysis time caused by slow moving micelles, auxiliary pressure was introduced to boost the micelle movement toward the detector using an in house designed and built apparatus. Applying the external auxiliary pressure significantly reduced the analysis times without compromising separation efficiency. Parameters, such as type of surfactants, composition of background electrolyte (BGE), type of capillary, matrix effect, organic modifiers, etc., were evaluated in optimization of the method. The enrichment factors for targeted analytes were impressive, particularly; cationic surfactants were shown to be suitable for analysis of nitrosamines due to their ability to act as hydrogen bond donors. Ammonium perfluorooctanoate (APFO) also showed remarkable results in term of peak shapes and number of theoretical plates. It was shown that the separation results were best when a high conductivity sample was paired with a BGE of lower conductivity. Using higher surfactant concentrations (up to 200 mM SDS) than usual (50 mM SDS) for micellar electrokinetic chromatography (MEKC) improved the sweeping. A new method for micro-extraction and enrichment of highly polar neutral analytes (N-Nitrosamines in particular) based on three-phase drop micro-extraction was introduced and its performance studied. In this method, a new device using some easy-to-find components was fabricated and its operation and application demonstrated. Compared to conventional extraction methods (liquid-liquid extraction), consumption of organic solvents and operation times were significantly lower.

Novel double-sided linear generator for the wave energy conversion

The direct drive point absorber is a robust and efficient system for wave energy harvesting, where the linear generator represents the most complex part of the system. Therefore, its design and optimization are crucial tasks. The tubular shape of a linear generator’s magnetic circuit offers better permanent magnet flux encapsulation and reduction in radial forces on the translator due to its symmetry. A double stator topology can improve the power density of the linear tubular machine. Common designs employ a set of aligned stators on each side of a translator with radially magnetized permanent magnets. Such designs require doubling the amount of permanent magnet material and lead to an increase in the cogging force. The design presented in this thesis utilizes a translator with buried axially magnetized magnets and axially shifted positioning of the two stators such that no additional magnetic material, compared to single side machine, is required. In addition to the conservation of magnetic material, a significant improvement in the cogging force occurs in the two phase topology, while the double sided three phase system produces more power at the cost of a small increase in the cogging force. The analytical and the FEM models of the generator are described and their results compared to the experimental results. In general, the experimental results compare favourably with theoretical predictions. However, the experimentally observed permanent magnet flux leakage in the double sided machine is larger than predicted theoretically, which can be justified by the limitations in the prototype fabrication and resulting deviations from the theoretical analysis.

Three-dimensional tomographic reconstruction of an exceptionally well preserved ichnological assemblage from the Stainmore Foundation, Carboniferous, UK

This Ph.D. thesis addresses current issues with ichnotaxonomic practice, and characterizes an exceptionally well preserved ichnological assemblage from the Carboniferous Stainmore Formation, Northumberland, United Kingdom. Samples were collected from closely localized float representative of various units throughout the succession, which was deposited in a storm-dominated marine shoreface. Three dominant ichnotaxa were selected for three-dimensional morphological analysis due to their complicated morphology and/or unclear taxonomic status: 1) Dactyloidites jordii isp. nov.; 2) Beaconites capronus, and; 3) Neoeione moniliformis comb. nov. Using serial grinding and photography, these ichnotaxa were ground and modelled in true colour. High-resolution models of three taxa produced in this study are the basis of the first complete three-dimensional consideration of the traces, and forms the basis for refined palaeobiological and ethological analysis of these taxa. Dactyloidites jordii isp. nov. is a stellate to palmate burrow composed of numerous long, narrow rays that exhibit three orders of branching arranged into tiered galleries radiating from a central shaft. It is considered to be the feeding structure produced by a vermiform organism. Beaconites capronus is a winding trace with distinctly chevron-shaped, meniscate backfill demonstrated herein to backfill the vertical shafts associated with its burrows in a comparable fashion to the horizontal portion of the burrow. This lack of a surface connection would result in the trace making organism being exposed to low-oxygen porewater. Coping with this porewater dysoxia could be approached by burrowing organisms in a number of ways: 1) revisiting the sediment-water interface; 2) creating periodic shafts; or 3) employing anaerobic metabolism. Neoeione moniliformis was originally introduced as Eione moniliformis, however, the genus Eione Tate, 1859 is a junior homonym of Eione Rafinesque, 1814. This led to the transfer of Eione moniliformis to Parataenidium. Through careful examination and three-dimensional characterization of topotypes, the transfer to Parataenidium moniliformis is demonstrated herein to be problematic, as Parataenidium refers to primarily horizontal burrows with two distinct layers and Eione moniliformis is composed of one distinct level. As such, the new ichnogenus Neoeione is created to accommodate Neoeione moniliformis.