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.

Castles in the air: the life, times and influence of the Reverend Moses Harvey (1820-1901).

The period from 1874 to 1901 was a time of significant transition in the economic and political life of Newfoundland. Twenty years into responsible government and with Confederation on the backburner, the colony’s politicians turned their attention to economic diversification, landward development and carving out the island’s place in the British Empire. The period saw both economic prosperity and retrenchment; the construction of a trans-insular railway; the adoption of policies to foster agriculture, forestry, manufacturing and mining; and diplomatic efforts to resolve France’s outstanding claims on the northwest coast of the island. At the same time, the government made an attempt to intervene directly in its primary industry, the fisheries. It created a Fisheries Commission in 1889 that recommended conservation measures and artificial propagation as ways to restore the health of some of the island’s fish stocks. They also proposed new methods of curing, packaging and marketing Newfoundland’s cod, as well as a complete overhaul of the truck system. A major player in both the public and private debates surrounding all of these subjects was the Reverend Moses Harvey. Along with being minister of the Free Church of Scotland in St. John’s, Harvey was one of Newfoundland’s most active promoters in the late nineteenth century. He served as the media mouthpiece for both Prime Minister William Whiteway and Prime Minister Robert Thorburn; editing the Evening Mercury – the official organ of the Liberal Party and then the Reform Party – from 1882 to 1883 and 1885 until 1890. As well, Harvey wrote regular columns on Newfoundland issues for newspapers in London, New York, Boston, Montreal, Toronto, and Halifax. He also produced numerous books, articles, encyclopedia entries, and travel guides outlining the island’s attractions and its vast economic potential. In short, Harvey made a significant contribution in shaping the way residents and the outside world viewed Newfoundland during this period. This thesis examines late nineteenth-century Newfoundland through the writing of Moses Harvey. The biographical approach offers a fuller, more nuanced account of some of the major historical themes of the period including the politics of progress, opening up the interior, railway construction and attitudes toward the fisheries. It also provides an insider’s prospective on what led to some of the major political decisions, policy positions or compromises taken by the Whiteway and Thorburn governments. Finally, a more detailed review of Harvey’s work exposes the practical and political differences that he had with people like D.W. Prowse and Bishop Michael Howley. While these so-called “boomers” in Newfoundland’s historiography agreed on broad themes, they parted ways over what should be done with the fisheries and how best to channel the colony’s growing sense of nationalism.