No description available.

This thesis investigates the relationships between mercury (Hg) and stable isotope of carbon (δ13C) in marine pelagic zooplankton (Calanus spp., Themisto spp. and Euchaeta spp.) with water mass characteristics in the North Water Polynya (NOW) and in the Mackenzie shelf – Amundsen Gulf area. Two ship based sampling field expeditions were carried out in late summer of 2005 and 2006 in both regions on board the CCGS Amundsen. In the North Water (NOW) polynya, higher levels of water Hg, depleted δ18O, lower salinity and lower nitrate levels were measured at sampling locations near the Prince of Wales glacier (POW) on the eastern coast of Ellesmere Island in the Smith Sound area. These results suggest that the glacier may be a source of Hg to this region which, in turn, is responsible for the correspondingly high concentrations of THg and MMHg measured in Calanus spp. and Euchaeta spp. at the same locations. The Mackenzie shelf – Amundsen Gulf region was characterized by fresher surface water properties (low salinity and depleted δ18O) in the western part and was strongly linked to the influence of the Mackenzie River. Higher THg concentrations in zooplankton were associated with larger fractions of both meteoric water and sea-ice melt. These findings suggest that in the western Arctic, inorganic Hg uptake in zooplankton via-absorption near surface water was highly driven by freshwater inputs into the system. Based on the analysis of three main genus Calanus spp. (mostly adult females Calanus hyperboreus), Euchaeta spp. and Themisto spp. (mostly adult Themisto libellula), THg and MMHg concentrations were the highest in the carnivorous copepod Euchaeta spp. in the North Water polynya followed by the omnivorous hyperiid amphipod Themisto spp. The herbivorous copepod Calanus spp. had both the lowest THg and MMHg concentrations in the Eastern and the Western Arctic. In addition, the Western Arctic is the area in which each zooplankton genus had the most depleted carbon and the most enriched nitrogen. The highest concentrations of THg in Calanus spp., Euchaeta spp. and Themisto spp. were measured in the Western Arctic as well as the highest MMHg in Calanus spp. and Themisto spp. The highest %MMHg was calculated in the Archipelago for Themisto spp., in the Eastern Arctic for Euchaeta spp. and in the Western Arctic for Calanus spp. The relationships observed between THg, MMHg, %MMHg and δ13C in all three major zooplankton taxa and water mass properties were in agreement with what have been previously described in the literature. Our findings suggested that both Hg and δ13C can be used as tracers to help understand zooplankton vertical distribution, feeding ecology and ultimately to predict climate changes impact at lower trophic level in the pelagic food web. The implications for marine mammals foraging in these regions are also discussed.

Mercury (Hg) is one of the primary contaminants of concern in the Arctic marine ecosystem. Methyl Hg (MeHg) is known to biomagnify in food webs. During the International Polar Year - Circumpolar Flaw Lead study, sea ice, seawater, bottom ice algae, phytoplankton and the herbivorous copepods were collected from the Amundsen Gulf to test whether ice algae and phytoplankton assimilate Hg from their habitat, and whether Hg bioaccumulates from the seawater to the primary consumers. Sea ice algae were found to accumulate Hg primarily from the bulk bottom ice, and the sea ice algae bloom depleted Hg stored within the bottom section of the ice. Furthermore, biodilution of Hg was observed to occur in sea ice algae. Higher concentrations of Hg were also found in phytoplankton and in grazing copepods. A positive correlation between MeHg and trophic level suggests the occurrence of MeHg biomagnification even at these low trophic positions.

No description available.

No description available.

This thesis investigates the relationships between mercury (Hg) and stable isotope of carbon (δ13C) in marine pelagic zooplankton (Calanus spp., Themisto spp. and Euchaeta spp.) with water mass characteristics in the North Water Polynya (NOW) and in the Mackenzie shelf – Amundsen Gulf area. Two ship based sampling field expeditions were carried out in late summer of 2005 and 2006 in both regions on board the CCGS Amundsen. In the North Water (NOW) polynya, higher levels of water Hg, depleted δ18O, lower salinity and lower nitrate levels were measured at sampling locations near the Prince of Wales glacier (POW) on the eastern coast of Ellesmere Island in the Smith Sound area. These results suggest that the glacier may be a source of Hg to this region which, in turn, is responsible for the correspondingly high concentrations of THg and MMHg measured in Calanus spp. and Euchaeta spp. at the same locations. The Mackenzie shelf – Amundsen Gulf region was characterized by fresher surface water properties (low salinity and depleted δ18O) in the western part and was strongly linked to the influence of the Mackenzie River. Higher THg concentrations in zooplankton were associated with larger fractions of both meteoric water and sea-ice melt. These findings suggest that in the western Arctic, inorganic Hg uptake in zooplankton via-absorption near surface water was highly driven by freshwater inputs into the system. Based on the analysis of three main genus Calanus spp. (mostly adult females Calanus hyperboreus), Euchaeta spp. and Themisto spp. (mostly adult Themisto libellula), THg and MMHg concentrations were the highest in the carnivorous copepod Euchaeta spp. in the North Water polynya followed by the omnivorous hyperiid amphipod Themisto spp. The herbivorous copepod Calanus spp. had both the lowest THg and MMHg concentrations in the Eastern and the Western Arctic. In addition, the Western Arctic is the area in which each zooplankton genus had the most depleted carbon and the most enriched nitrogen. The highest concentrations of THg in Calanus spp., Euchaeta spp. and Themisto spp. were measured in the Western Arctic as well as the highest MMHg in Calanus spp. and Themisto spp. The highest %MMHg was calculated in the Archipelago for Themisto spp., in the Eastern Arctic for Euchaeta spp. and in the Western Arctic for Calanus spp. The relationships observed between THg, MMHg, %MMHg and δ13C in all three major zooplankton taxa and water mass properties were in agreement with what have been previously described in the literature. Our findings suggested that both Hg and δ13C can be used as tracers to help understand zooplankton vertical distribution, feeding ecology and ultimately to predict climate changes impact at lower trophic level in the pelagic food web. The implications for marine mammals foraging in these regions are also discussed.

Mercury (Hg) is one of the primary contaminants of concern in the Arctic marine ecosystem. Methyl Hg (MeHg) is known to biomagnify in food webs. During the International Polar Year - Circumpolar Flaw Lead study, sea ice, seawater, bottom ice algae, phytoplankton and the herbivorous copepods were collected from the Amundsen Gulf to test whether ice algae and phytoplankton assimilate Hg from their habitat, and whether Hg bioaccumulates from the seawater to the primary consumers. Sea ice algae were found to accumulate Hg primarily from the bulk bottom ice, and the sea ice algae bloom depleted Hg stored within the bottom section of the ice. Furthermore, biodilution of Hg was observed to occur in sea ice algae. Higher concentrations of Hg were also found in phytoplankton and in grazing copepods. A positive correlation between MeHg and trophic level suggests the occurrence of MeHg biomagnification even at these low trophic positions.

The development of a capillary electrophoresis (CE) method for the determination of inorganic and organo mercury species as their dithizone sulphonate (DzS) complexes using coated capillary columns is described. The complexes were pre-formed before injection and detection was by direct measurement of the visible absorbance of the complexes. Dithizone sulphonate was used in place of cysteine to separate methyl mercury in the final stage of a simplified Westoo extraction procedure. The method was than applied to the analysis of methyl mercury in a crab and several fish meat samples. Good quantitative performance is demonstrated by spiking experiments and analysis of DORM-1 certified reference material. The method was found to be very sensitive and a detection limit of 2 µg Kgˉ¹ could be achieved for a l0g sample of fish flesh. A CE method for the determination of uranium (VI) as the arsenazo III complex was developed and the effect of interfering metal ions was studied. The calibration was found to be linear from 10 µg 1ˉ¹ -10 mg 1ˉ¹ using gravity injections and a detection limit of less than 1 µg 1ˉ¹ was achieved with electrokinetic injection. A study was made of injection techniques and their applicability to the enhancement of sensitivity in synthetic standards and environmental samples. The effect of capillary surface chemistry on the peak shape of the migrating uranyl-arsenazo III was also studied using fused silica capillaries with two different internal coatings and three polymeric capillaries. A study was also carried out on the construction and investigation of a post-capillary reactor for the determination of trace metals by UV-Vis absorption after formation of intensely absorbing coloured complexes. The main principle of operation was based on the infusion of the colorimetric reagent into a small 50µm gap between the separation capillary and the reaction capillary. The gap was enclosed by a permeable membrane and the flow of reagent was achieved by the application of a slight pressure to the post-capillary reactor cell. Two reagents were studied, namely, xylenol orange (XO) and 4 (2-pyridylazo) resorcinol (PAR), for the separation and detection of copper (U), cadmium (II), cobalt (II), nickel (II), zinc (II), and manganese (II). Lead (II) was also included in the XO system.

Azolla filiculoides has been evaluated for the adsorption of trace toxic metals from aqueous solution. The adsorption performance of the material was compared with commercial resins and fitted using the Langmuir and Freundlich models. The Freundlich model described the adsorption of copper and cadmium. Whilst the Langmuir isotherm had the better fit of the mercury data. The assumptions of the Freundlich model include multi-layer adsorption and different functional group binding. Conversely the Langmuir model suggests mono-layer adsorption and can infer single group reactivity. The pH effect on the uptake of the metals was investigated and an increase in removal was observed at higher pH with all the metals studied. The material has been thoroughly characterised using physical methods, such as, scanning electron microscopy X-ray photoelectron spectroscopy and electrophoretic mobility measurements. This enabled conclusions to be made regarding the surface functionality of the solid. Chemical characterisation included direct titrations, revealing a gradual dissociation of acidic groups as the pH increased within the experimental range. Kjeldahl nitrogen and amino acid analysis of several biological materials that have been used in metal sorption experiments showed A. filiculoides as having a large proportion of these cell constituents. The kinetics of metal ion uptake by the biosorbent was investigated and compared with commercially available resins. The kinetics are slower than conventional ion exchange resins and carbon adsorbents but entirely adequate for utilisation in a column process. The mechanism hypothesized for metal ion removal by the biosorbent is primarily attributed to ionogenic groups exchanging ions for copper and cadmium removal. Mercury on the other hand is said to be predominantly involved in a reduction-precipitation reaction on the surface of the adsorbent. Regeneration was successfully accomplished for copper and cadmium after minicolumn trials, with greater than 95 % elution of the metals using 0.1M HCI. The mini column trials showed a sharp breakthrough for these metals singularly and a dynamic equilibrium was observed during multi-metal processing. Mercury removal was much slower and more difficult with the same eluant, achieving a maximum of 50% removal. A method for a semi-continuous biosorbent process has been evaluated and proven to be successful in processing metal laden solution.

Most S-nitrosothiols (RSNO) are unstable in aqueous solution and decompose to release nitric oxide. This is catalysed by copper ions. A mechanistic study of NO formation from S-nitrosoglutathione (GSNO), the nitroso derivative of the most abundant thiol in the body, was carried out. This relatively stable S-nitrosothiol decomposed in the presence of reduced glutathione and copper ions. The products were identified as nitric oxide and oxidised glutathione, observed as a complex of copper. The role of reduced glutathione was two fold. Firstly, it reduced Cu(^2+) to produce the active Cu(^+) catalytic species and regenerated the catalyst from the oxidised glutathione complex. Spectrophotometric kinetic measurements, under pseudo first order conditions ([GSNO]»[Cu(^2+)]) showed no conventional order with respect to nitrosothiol. This was attributed to the inconstant concentration of available copper during reaction due to the ability of reduced glutathione to complex Cu(^+) and oxidised glutathione to complex Cu(^2+). An investigation of thiol induced decomposition of GSNO and other more stable nitrosothiols showed the reaction to be first order with respect to thiol and nitrosothiol. The rate equation was determined and has been explained in terms of a radical mechanism involving rate limiting attack of the thiyl radical on the RS-NO bond. The decomposition of S-nitrosothiols via the mercuric ion was also investigated. Reactions were stoichiometric rather than catalytic, and the products determined to be H(_2)NO(_2)(^+) and RSHg(^+). The rate equation was established and the reaction found to be first order in S-nitrosothiol and Hg(^2+). Second order rate constants obtained for a variety of nitrosothiols showed no dependency of the rate of the reaction on the structure of R. A mechanism was proposed involving direct attact of the Hg(^2+) ion on S of the nitroso group, reflecting the high affinity of the metal ion for the sulfur atom. Similarly, an investigation into Ag(^+) mediated S-nitrosothiol decomposition showed the reaction to be stoichiometric. Nitric oxide was not a product of this reaction.