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.

An automatic method of above-water iceberg 3-D profiling based on autonomous surface craft (ASC) using surface images and LIDAR

This thesis reports on a novel method to build a 3-D model of the above-water portion of icebergs using surface imaging. The goal is to work towards the automation of iceberg surveys, allowing an Autonomous Surface Craft (ASC) to acquire shape and size information. After collecting data and images, the core software algorithm is made up of three parts: occluding contour finding, volume intersection, and parameter estimation. A software module is designed that could be used on the ASC to perform automatic and fast processing of above-water surface image data to determine iceberg shape and size measurement and determination. The resolution of the method is calculated using data from the iceberg database of the Program of Energy Research and Development (PERD). The method was investigated using data from field trials conducted through the summer of 2014 by surveying 8 icebergs during 3 expeditions. The results were analyzed to determine iceberg characteristics. Limitations of this method are addressed including its accuracy. Surface imaging system and LIDAR system are developed to profile the above-water iceberg in 2015.

Ichnology and palaeobiology of Phoebichnus trochoides and Schaubcylindrichnus heberti comb. nov.

The three-dimensional reconstructions of Phoebichnus trochoides and Schaubcylindrichnus (Palaeophycus) heberti created as part of this thesis allow us to fully understand and characterize the three-dimensional morphology and palaeobiology of these common taxa. Three-dimensional reconstructions demonstrate that P. trochoides is a large stellate burrow composed of numerous long galleries produced by a deposit feeding organism. This study reports for the first time that the central zone is composed of stacked disk-shaped layers of highly bioturbated sediment, the radial burrows are composed of a sand-rich lining of pelleted annuli surrounding an active sand-rich fill, and the presence of subtle conical features above the radial galleries that are inferred to result from collapse cone feeding. Reconstructions of heberti demonstrate that the thick walled burrows are composed of sand-rich annular rings, are a broad U-shape, and may be either clustered or isolated. Our observations show that the morphology of heberti is inconsistent with the generic diagnosis of Palaeophycus, but is morphologically comparable to Schaubcylindrichnus, and is herein synonymised with Schaubcylindrichnus to create S. heberti comb. nov. The three-dimensional reconstructions have revealed a number of hitherto unknown morphological elements to both taxa which has facilitated new interpretations of the trace-makers behaviour. The data improves the taxonomic understanding of both P. trochoides and S. heberti which require significant taxonomic change and emendation of diagnoses at the species and genus level.