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A Thesis Submitted to the College Of Biological and physicochemical mechanisms affecting phosphorus and arsenic efflux from prairie reservoir sediment, Buffalo Pound Lake, SK, Canada. A Thesis Submitted to the College of Graduate and Postdoctoral Studies in Partial Fulfillment of the Requirements for the Degree Masters of Science in the Toxicology Graduate Program University of Saskatchewan Saskatoon, Saskatchewan, Canada Submitted by: Lawrence Peter D’Silva © Copyright Lawrence Peter D’Silva, January 2017. All rights reserved. PERMISSION TO USE In presenting this thesis in partial fulfillment of the requirements for a Postgraduate degree from the University of Saskatchewan, I agree that the Libraries of this University may make it freely available for inspection. I further agree that permission for copying of this thesis in any manner, in whole or in part, for scholarly purposes may be granted by the professor or professors who supervised my thesis work or, in their absence, by the Head of the Program or the Dean of the College in which my thesis work was done. It is understood that any copying or publication or use of this thesis or parts thereof for financial gain shall not be allowed without my written permission. It is also understood that due recognition shall be given to me and to the University of Saskatchewan in any scholarly use which may be made of any material in my thesis. Requests for permission to copy or to make other use of material in this thesis in whole or part should be addressed to: Chair of the Toxicology Graduate Program Toxicology Centre University of Saskatchewan 44 Campus Drive Saskatoon, Saskatchewan, Canada, S7N 5B3 i ABSTRACT Eutrophication and algal blooms pose environmental and economical issues in freshwater lakes globally. Algal bloom development is primarily attributed to phosphorus (P), which can be released from lake bottom sediments under certain environmental conditions. Simultaneous to P release, arsenic (As), which is a geochemical P analogue, can be mobilized from sediments and exert toxicity in aquatic organisms. Recent studies within the Canadian prairies have focused on concerns regarding water scarcity and the increased development of algal blooms. However, lake sediments within the Canadian prairies, which are susceptible to P and As mobilization, have received little attention. Using a regionally important freshwater lake (Buffalo Pound Lake, SK, Canada), the goal of this study was to identify environmental mechanisms and geochemistry that influenced P and As mobilization from Canadian prairie lake sediment. Laboratory sediment core incubation experiments demonstrated that warm temperatures (19°C) had the greatest influence on P mobilization from sediment, followed by high pH (pH=9.2), and then low dissolved oxygen (DO) concentrations (<1 -1 mg O2 L ). High pH had the greatest influence on As mobilization from sediment, followed by warm temperatures, and then low DO concentration. The content of total P, relatively labile P fractions, and total As in sediment were not significantly different among sites. However, concentrations of aluminum (Al) and iron (Fe), common P and As sorbents in sediment, were significant different among sites. In sediment core incubations, the site that displayed less P and As mobilization under anoxic conditions also contained greater concentrations of Al in sediment. Redox-insensitive Al likely mitigated P and As mobilization under anoxic conditions, as evident by decreased P and As mobilization. Phosphorus and As were also mobilized from sediment in situ during ephemeral periods of bottom water stratification and suboxia. Although these conditions are known to facilitate P release in Fe-poor, polymictic lakes, this paradigm appears to also apply to As mobilization. Similar to the laboratory results, less P and As were mobilized in situ from sediment containing greater Al content. ii Overall, results demonstrated that, in addition to the above environmental variables, sediment geochemistry has a major influence on P and As mobilization from sediment in this Canadian prairie lake. Overall, it is important to determine concentrations of geochemical sorbents (i.e., Fe and Al) when studying P and As mobilization in shallow freshwater lakes globally. iii ACKNOWLEDGEMENTS Firstly, I would like to thank my supervisors, Drs. Karsten Liber and Lorne Doig, for your time, instruction, guidance, and friendship throughout an otherwise arduous journey. Your continuous mentorship and support have truly helped me to become a better scientist. To my committee members, Drs. John Giesy and Helen Baulch, thank you, not only for your significant contributions to my thesis, but also your appreciable advice regarding my career and aspirations. I would also like to thank my external examiner, Dr. Joyce McBeth, for your invaluable comments on my thesis. This project could not have been possible without funding from NSERC, the Buffalo Pound Water Treatment Plant, and the Saskatchewan Water Security Agency. To my fellow be-Libers, both past and present (Kevin, Erin, Stephanie, Esteban, Sarah, Katherine, Taylor, Colleen, Danielle, Noel, Ally, and Blue), thanks for your help and support throughout my project. To the students, professors, and staff at the Toxicology Centre, thank you for a remarkable and unforgettable experience. It should not be possible for a graduate program to be so fun and successful, yet we have managed to string it together. I would like to thank my friends in Calgary for their enduring friendship, and my patient girlfriend, Rachel, for all of her love and support. Lastly and foremost, I would like to thank, and dedicate this thesis to, my greatest mentors in life, my parents. iv TABLE OF CONTENTS PERMISSION TO USE ....................................................................................................... I ABSTRACT ........................................................................................................................ II ACKNOWLEDGEMENTS .............................................................................................. IV LIST OF TABLES ......................................................................................................... VIII LIST OF FIGURES .......................................................................................................... IX LIST OF ABBREVIATIONS ........................................................................................... XI PREFACE ...................................................................................................................... XIII CHAPTER 1 GENERAL INTRODUCTION ........................................................................................... 1 1.1. Phosphorus – Geographic distribution and chemical properties ....................................... 1 1.2. Phosphorus in freshwater lakes .......................................................................................... 2 1.2.1. Sources, fate, and transport ........................................................................................ 2 1.2.2. Analytical fractions .................................................................................................... 4 1.3. Internal phosphorus loading ............................................................................................... 6 1.3.1. Mechanisms and geochemistry .................................................................................. 6 1.3.2. Eutrophication and algal blooms ................................................................................ 9 1.4. Arsenic in freshwater lakes .............................................................................................. 11 1.4.1. Sources, speciation, and behavior ............................................................................ 11 1.4.2. Arsenic toxicity ........................................................................................................ 13 1.5. Buffalo Pound Lake, Saskatchewan ................................................................................ 14 1.6. Project overview and rationale ........................................................................................ 16 1.7. Goal and objectives .......................................................................................................... 18 CHAPTER 2 PHYSICOCHEMICAL MECHANISMS GOVERNING INTERNAL PHOSPHORUS LOADING FROM PRAIRIE RESERVOIR SEDIMENT, BUFFALO POUND LAKE, SK, CANADA. ................................................................................................................. 20 2.1. Introduction ...................................................................................................................... 20 2.2. Methods and Materials ..................................................................................................... 23 2.2.1. Site description ......................................................................................................... 23 2.2.2. Sediment core incubations ........................................................................................ 26 2.2.3. Sediment geochemistry ............................................................................................ 30 2.2.4. In situ monitoring ..................................................................................................... 31 2.2.5. Chemical analyses .................................................................................................... 33 v 2.2.6. Numerical analyses ..................................................................................................
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