Applications of capillary electrophoresis and mass spectrometry for the analysis of thiosalts

Thiosalt species are unstable, partially oxidized sulfur oxyanions formed in sulfur-rich environments but also during the flotation and milling of sulfidic minerals especially those containing pyrite (FeS₂) and pyrrhotite (Fe₍₁₋ₓ₎S, x = 0 to 0.2). Detecting and quantifying the major thiosalt species such as sulfate (SO₄²⁻), thiosulfate (S₂O₃²⁻), trithionate (S₃O₆²⁻), tetrathionate (S₄O₆²⁻) and higher polythionates (SₓO₆²⁻, where 3 ≤ x ≤ 10) in the milling process and in the treated tailings is important to understand how thiosalts are generated and provides insight into potential treatment. As these species are unstable, a fast and reliable analytical technique is required for their analysis. Three capillary zone electrophoresis (CZE) methods using indirect UV-vis detection were developed for the simultaneous separation and determination of five thiosalt anions: SO₄²⁻, S₂O₃²⁻, S₃O₆²⁻, S₄O₆²⁻ and S₅O₆²⁻. Both univariate and multivariate experimental design approaches were used to optimize the most critical factors (background electrolyte (BGE) and instrumental conditions) to achieve fast separation and quantitative analysis of the thiosalt species. The mathematically predicted responses for the multivariate experiments were in good agreement with the experimental results. Limits of detection (LODs) (S/N = 3) for the methods were between 0.09 and 0.34 μg/mL without a sample stacking technique and nearly four-fold increase in LODs with the application of field-amplified sample stacking. As direct analysis of thiosalts by mass spectrometry (MS) is limited by their low m/z values and detection in negative mode electrospray ionization (ESI), which is typically less sensitive than positive ESI, imidazolium-based (IP-L-Imid and IP-T-Imid) and phosphonium-based (IP-T-Phos) tricationic ion-pairing reagents were used to form stable high mass ions non-covalent +1 ion-pairs with these species for ESI-MS analysis and the association constants (Kassoc) determined for these ion-pairs. Kassoc values were between 6.85 × 10² M⁻¹ and 3.56 × 10⁵ M⁻¹ with the linear IP-L-Imid; 1.89 ×10³ M⁻¹ and 1.05 × 10⁵ M⁻¹ with the trigonal IP-T-Imid ion-pairs; and 7.51×10² M⁻¹ and 4.91× 10⁴ M⁻¹ with the trigonal IP-T-Phos ion-pairs. The highest formation constants were obtained for S₃O₆²⁻ and the imidazolium-based linear ion-pairing reagent (IP-L-Imid), whereas the lowest were for IP-L-Imid: SO₄²⁻ ion-pair.

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.