Previous studies on fishes exposed to effluent from the Key Lake uranium mill in northern Saskatchewan have demonstrated elevated lipids in young-of-the-year pike (Esox lucius), deformities in larval pike and decreased survival of fathead minnows (Pimephales promelas). The objectives of this thesis were to evaluate possible factors that could be contributing to altered bioenergetics of juvenile northern pike inhabiting lakes receiving effluent from the Key Lake operation and to examine the effects of effluent exposure on biomarkers of oxidative stress and histopathology of target organs. Although glycogen and triglycerides stores were significantly greater in pike from exposure lakes compared to the reference, triglycerides stores of juvenile pike prey items showed no overall differences among lakes. Measures of parasitism, however, were negatively correlated with pike bioenergetics thereby reflecting a possible energetic cost of parasitism on reference lake fish. The degree of infection by intestinal parasites and gill monogeneans was greatest in reference pike and intermediate in low exposure pike, whereas high exposure pike harboured no parasites. <p>Arsenic, nickel and selenium are elevated in lakes downstream of the Key Lake mill and have been shown to be associated with increased reactive oxygen species (ROS) in biological systems causing oxidative stress. The potential for oxidative stress was assessed in pike liver and kidney using several biomarkers. Overall, the concentrations of total, reduced and oxidized glutathione and the ratio of oxidized to reduced glutathione did not differ significantly among exposure and reference pike. The activity of glutathione peroxidase was greater in high exposure than reference liver whereas, contrary to predictions, lipid peroxidation was greater in reference than exposure pike tissues. <p>Histopathological evaluations revealed greater kidney and gill pathology in reference lake pike, whereas for liver, hepatocyte morphology differed among lakes without any clear signs of pathology. Trace metal analyses of muscle showed that eight elements (arsenic, cobalt, copper, iron, molybdenum, selenium, thallium, uranium) were significantly elevated in exposure pike. These results provide only limited evidence of oxidative stress in exposure pike tissues and no evidence of histopathology despite indications that metals are bioaccumulating in tissue. Overall, the results from this thesis suggest that the health and condition of juvenile northern pike living downstream of the Key Lake uranium mill may not be compromised by effluent exposure.

Past monitoring has noted benthic macroinvertebrate community impairment downstream of both the Key Lake and Rabbit Lake uranium operations in northern Saskatchewan, Canada. The objective of this research was to try to identify the cause(s) of these impacts using a weight-of-evidence approach. Given that sediments generally accumulate contaminants that are related to metal mining activities (such as metals and radionuclides), the initial hypothesis for this research was that contaminated sediments were the primary cause of benthic community impairment at both operations.<p>In 2003 and 2004 a Sediment Quality Triad (SQT) approach confirmed the presence of an effect on benthic community structure, in addition to significant differences in surface-water, pore-water and whole-sediment chemistry at the immediate down-stream exposure sites at both uranium operations. However, no significant adverse effects were noted in 10-d whole-sediment bioassays with <i>Hyalella azteca</i>, although this lack of response could be partially due to sediment pore-water dilution resulting from the automated clean overlying water renewal process employed. Potential causes of benthic community impairment identified through the 2003 and 2004 SQTs for Key Lake include physical sediment composition, surface water pH and total ammonia, in addition to pore-water total ammonia and arsenic. Potential stressors identified at Rabbit Lake included high surface water manganese and uranium concentrations, and increases in pore-water total ammonia, manganese, iron, arsenic, and uranium levels.<p>In the summer of 2004, 4-d in-situ bioassays using <i>H. azteca</i> were conducted along with the SQTs to investigate the role both contaminated surface water and sediment played in benthic community impairment in-situ. Results from the Key Lake in-situ bioassay demonstrated that surface-water was the primary cause of acute toxicity to <i>H. azteca</i>. Results from the Rabbit Lake in-situ study also demonstrated that surface water as the primary cause of acute toxicity to <i>H. azteca</i>, although the relationship was not as strong. The cause of in-situ toxicity at Key Lake could not be correlated with any of the variables measured within the in-situ study, including trace metals, total ammonia, and pH. Of the measured constituents at Rabbit Lake, only concentrations of uranium in both surface water and pore-water were suspected of causing the observed in-situ mortality. Two data sets from two methods of surface water and pore-water collection supported these conclusions.<p>Due to time constraints and stronger cause-effect relationships, efforts were focused on the in-situ toxicity observed at Key Lake. Surface water collected in 2004 at the time of the related in-situ study was also found to be acutely toxic to <i>H. azteca</i> in separate laboratory surface water bioassays, thus verifying that contaminated surface water, not sediment, was the primary cause of the observed in-situ <i>H. azteca</i> mortality. Further information revealed that organic mill-process chemicals, which have been previously linked with sporadic effluent toxicity, were released at the Key Lake operation during the time of the in-situ experiment and associated surface water collection. Additional surface water samples collected in June and August, 2005, were not acutely toxic to <i>H. azteca</i>. Furthermore, a second bioassay with archived surface waters from the initial 2004 collection demonstrated that the water was no longer acutely toxic (i.e., acute toxicity disappeared after one-year storage). Chemistry comparisons of the toxic and non-toxic surface water samples, verified that trace metals, ammonia, pH, and major ions, including sulphate, were not the cause of toxicity, leaving only organic mill-process chemicals as a possible cause. Subsequent 4-d laboratory toxicity tests demonstrated that these process chemicals (kerosene, amine, and isodecanol) are toxic to H. azteca at the levels released in 2004, and are therefore believed to be the cause of the <i>H. azteca</i> mortality seen in the earlier in-situ experiment.<p>In short, this weight-of-evidence research provided new information on the possible causes of benthic macroinvertebrate community impairment downstream of both the Key Lake and Rabbit Lake uranium operations.

Past monitoring has noted benthic macroinvertebrate community impairment downstream of both the Key Lake and Rabbit Lake uranium operations in northern Saskatchewan, Canada. The objective of this research was to try to identify the cause(s) of these impacts using a weight-of-evidence approach. Given that sediments generally accumulate contaminants that are related to metal mining activities (such as metals and radionuclides), the initial hypothesis for this research was that contaminated sediments were the primary cause of benthic community impairment at both operations.<p>In 2003 and 2004 a Sediment Quality Triad (SQT) approach confirmed the presence of an effect on benthic community structure, in addition to significant differences in surface-water, pore-water and whole-sediment chemistry at the immediate down-stream exposure sites at both uranium operations. However, no significant adverse effects were noted in 10-d whole-sediment bioassays with <i>Hyalella azteca</i>, although this lack of response could be partially due to sediment pore-water dilution resulting from the automated clean overlying water renewal process employed. Potential causes of benthic community impairment identified through the 2003 and 2004 SQTs for Key Lake include physical sediment composition, surface water pH and total ammonia, in addition to pore-water total ammonia and arsenic. Potential stressors identified at Rabbit Lake included high surface water manganese and uranium concentrations, and increases in pore-water total ammonia, manganese, iron, arsenic, and uranium levels.<p>In the summer of 2004, 4-d in-situ bioassays using <i>H. azteca</i> were conducted along with the SQTs to investigate the role both contaminated surface water and sediment played in benthic community impairment in-situ. Results from the Key Lake in-situ bioassay demonstrated that surface-water was the primary cause of acute toxicity to <i>H. azteca</i>. Results from the Rabbit Lake in-situ study also demonstrated that surface water as the primary cause of acute toxicity to <i>H. azteca</i>, although the relationship was not as strong. The cause of in-situ toxicity at Key Lake could not be correlated with any of the variables measured within the in-situ study, including trace metals, total ammonia, and pH. Of the measured constituents at Rabbit Lake, only concentrations of uranium in both surface water and pore-water were suspected of causing the observed in-situ mortality. Two data sets from two methods of surface water and pore-water collection supported these conclusions.<p>Due to time constraints and stronger cause-effect relationships, efforts were focused on the in-situ toxicity observed at Key Lake. Surface water collected in 2004 at the time of the related in-situ study was also found to be acutely toxic to <i>H. azteca</i> in separate laboratory surface water bioassays, thus verifying that contaminated surface water, not sediment, was the primary cause of the observed in-situ <i>H. azteca</i> mortality. Further information revealed that organic mill-process chemicals, which have been previously linked with sporadic effluent toxicity, were released at the Key Lake operation during the time of the in-situ experiment and associated surface water collection. Additional surface water samples collected in June and August, 2005, were not acutely toxic to <i>H. azteca</i>. Furthermore, a second bioassay with archived surface waters from the initial 2004 collection demonstrated that the water was no longer acutely toxic (i.e., acute toxicity disappeared after one-year storage). Chemistry comparisons of the toxic and non-toxic surface water samples, verified that trace metals, ammonia, pH, and major ions, including sulphate, were not the cause of toxicity, leaving only organic mill-process chemicals as a possible cause. Subsequent 4-d laboratory toxicity tests demonstrated that these process chemicals (kerosene, amine, and isodecanol) are toxic to H. azteca at the levels released in 2004, and are therefore believed to be the cause of the <i>H. azteca</i> mortality seen in the earlier in-situ experiment.<p>In short, this weight-of-evidence research provided new information on the possible causes of benthic macroinvertebrate community impairment downstream of both the Key Lake and Rabbit Lake uranium operations.

Previous studies on fishes exposed to effluent from the Key Lake uranium mill in northern Saskatchewan have demonstrated elevated lipids in young-of-the-year pike (Esox lucius), deformities in larval pike and decreased survival of fathead minnows (Pimephales promelas). The objectives of this thesis were to evaluate possible factors that could be contributing to altered bioenergetics of juvenile northern pike inhabiting lakes receiving effluent from the Key Lake operation and to examine the effects of effluent exposure on biomarkers of oxidative stress and histopathology of target organs. Although glycogen and triglycerides stores were significantly greater in pike from exposure lakes compared to the reference, triglycerides stores of juvenile pike prey items showed no overall differences among lakes. Measures of parasitism, however, were negatively correlated with pike bioenergetics thereby reflecting a possible energetic cost of parasitism on reference lake fish. The degree of infection by intestinal parasites and gill monogeneans was greatest in reference pike and intermediate in low exposure pike, whereas high exposure pike harboured no parasites. <p>Arsenic, nickel and selenium are elevated in lakes downstream of the Key Lake mill and have been shown to be associated with increased reactive oxygen species (ROS) in biological systems causing oxidative stress. The potential for oxidative stress was assessed in pike liver and kidney using several biomarkers. Overall, the concentrations of total, reduced and oxidized glutathione and the ratio of oxidized to reduced glutathione did not differ significantly among exposure and reference pike. The activity of glutathione peroxidase was greater in high exposure than reference liver whereas, contrary to predictions, lipid peroxidation was greater in reference than exposure pike tissues. <p>Histopathological evaluations revealed greater kidney and gill pathology in reference lake pike, whereas for liver, hepatocyte morphology differed among lakes without any clear signs of pathology. Trace metal analyses of muscle showed that eight elements (arsenic, cobalt, copper, iron, molybdenum, selenium, thallium, uranium) were significantly elevated in exposure pike. These results provide only limited evidence of oxidative stress in exposure pike tissues and no evidence of histopathology despite indications that metals are bioaccumulating in tissue. Overall, the results from this thesis suggest that the health and condition of juvenile northern pike living downstream of the Key Lake uranium mill may not be compromised by effluent exposure.

The As- and Mo- bearing secondary mineral phases formed during the neutralization of uranium mill wastes were studied for a variety of ore blends including current and future ore sources at the Key Lake milling operation, northern Saskatchewan, Canada. A lab-scale plant model was employed to characterize secondary precipitates obtained during the mill waste neutralization process. Three scenarios of ore blends were processed through the lab-scale plant to produce mill waste solutions for neutralization before combination into final tailings. Slurry samples (n = 12) were collected from the secondary precipitates formed during the neutralization of mill wastes (raffinate) by precipitation with Ca(OH)2 (slaked lime) from pH 1.5 to 10.5. Synchrotron based X-ray absorption spectroscopy of mill and lab-scale plant precipitates showed arsenate adsorbed to ferrihydrite was the dominant As mineral phase regardless of pH or sample blend (53-77%), with fractional contributions from ferric arsenates, and adsorption to aluminum phases (AlOHSO4, As(OH)3 and hydrotalcite). Molybdate adsorbed to ferrihydrite was the dominant Mo mineral phase, regardless of pH or sample blend, with fractional contribution decreasing with increasing pH, and minor contributions from calcium molybdate, ferric molybdate and nickel molybdate. These results were used in geochemical modelling to predict the source terms for these mineral phases in tailings facilities. Sequestration of As and Mo in the model showed solubility was controlled by adsorption to both Fe and Al oxide surfaces as well as by direct precipitation with other dissolved constituents (Ni, Ca and SO4).The models developed pH profiles of mineral phase precipitation to explain the solubility of As, Mo, Fe, Al, Mg and Ni during sequestration from pH 1.5 to 10.5 that were consistent regardless of ore blend used in simulations. Since adsorption of anions to the surface of ferrihydrite has been shown to slow conversion to crystalline forms of Fe oxides (goethite and hematite) and sequestration of arsenate effectively controls As solubility at high pH (pH >10), As-bearing mineral phases are expected to be stable for thousands of years. With adsorption as well as direct precipitation considered, Mo phases though effectively sequestering below pH 8, became unstable and released Mo back into the tailings porewater (pH >10), as predicted by the thermodynamic model. Historical data obtained from as-discharged tailings as well as previously published U mill tailings studies agree with these findings.