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Oil sands process water and tailings pond contaminant transport and fate : physical, chemical and biological… Lévesque, Céleste Marie 2014

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  OIL SANDS PROCESS WATER AND TAILINGS POND CONTAMINANT TRANSPORT AND FATE: PHYSICAL, CHEMICAL AND BIOLOGICAL PROCESSES by Céleste Marie Lévesque  B.Sc., The University of Saskatchewan, 2001  A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF  MASTER OF SCIENCE in THE FACULTY OF GRADUATE AND POSTDOCTORAL STUDIES (Chemical and Biological Engineering)  THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver)  July 2014  © Céleste Marie Lévesque, 2014 ii  Abstract The Alberta Oil Sands development has been in operation since the 1960s, where innovations in technology in bitumen extraction have resulted in adaptive management of environmental sensitivities to Oil Sands Process-affected Water (OSPW) and tailings. This research assessed all the potential processes that OSPW constituents might undergo in the tailings impoundments in order to theorize on their ultimate fate. A conceptual tailing pond model was created, the first of its kind as there have been no attempts in the existing literature, and a tool for future management of these facilities. The development of a model is quite complex where the objectives are defined (e.g. OSPW constituents) and the various physical, chemical, biological, geochemical, hydrological and limnological processes involved. This research was conducted by one individual, while such integration and analysis would typically be tackled by a team of multidisciplinary experts.   The scope of this research included the OSPW produced from oil sands open-pit mining, extraction and processing of bitumen. The crushing of ore and chemical additives affect water chemistry through the release of ions, salts, metals and organic compounds. Oil sands mines generate process affected water high in contaminants and the high degree of water recycling further concentrates these substances. The spatial and geological focus comprised the Athabasca ore deposit, with special attention on the Fort McMurray area and particular examination of the Mildred Lake Settling basin. A thorough literature review was conducted where the data and concepts from various scientific sources were utilized as a basis in the creation of a Tailings Pond Model, to conceptualize the physical, chemical and biological processes within a typical tailings settling basin.  iii  All further refinement and upgrading of the bitumen, processing of coke or other by-products were out of scope. Technological innovations in bitumen extraction and assisted tailings consolidation have resulted in more complex constituent compositions. The physical, chemical and biological processes occurring within a tailings pond are multifaceted making it difficult to model the ultimate fates of various substances. Chemical oxidation and bacterial decomposition have been shown to decrease toxicity of certain contaminants of greater concern.   iv  Preface The research did not require ethics approval; all sources have been cited and included in the bibliography. The following study was not previously published in whole or in part, and was designed, carried out, and analyzed solely by the author, Céleste Lévesque.   v  Table of Contents  Abstract .................................................................................................................................... ii Preface ...................................................................................................................................... iv Table of Contents ...................................................................................................................... v List of Tables ............................................................................................................................ ix List of Figures............................................................................................................................ x List of Abbreviations ............................................................................................................. xiii Acknowledgements ................................................................................................................. xvi Dedication .............................................................................................................................. xvii Chapter 1: Introduction ............................................................................................................ 1 1.1 Geological origin of the ore deposit .............................................................................2 1.2 Environmental setting ..................................................................................................3 1.3 Alberta oil sands history ..............................................................................................4 1.4 Mining .........................................................................................................................6 1.4.1 Bitumen extraction and processing ...........................................................................6 1.4.2 Mine engineering and tailings pond design............................................................. 10 1.4.3 Reclamation activities ............................................................................................ 12 Chapter 2: Materials and Methods ........................................................................................ 14 2.1 Methods ..................................................................................................................... 14 Chapter 3: Results ................................................................................................................... 16 3.1 Literature review ....................................................................................................... 16 3.2 Oil sands process water properties ............................................................................. 17 vi  3.2.1 Physical variables .................................................................................................. 18 3.2.1.1 Major ions ...................................................................................................... 24 3.2.1.2 Organic compounds ....................................................................................... 27 3.2.1.3 Nutrients ........................................................................................................ 32 3.2.1.4 Elements ........................................................................................................ 36 3.2.1.5 Biology .......................................................................................................... 42 3.3 OSPW CCME water quality index ............................................................................. 43 3.4 OSPW parameters data source comparison ................................................................ 47 3.5 Ecological effects ...................................................................................................... 54 3.5.1 Athabasca watershed .............................................................................................. 54 3.5.2 OSPW toxicological effects ................................................................................... 55 3.6 Tailings pond processes ............................................................................................. 61 3.6.1 Overview ............................................................................................................... 61 3.6.2 Physical processes: limnology ................................................................................ 64 3.6.2.1 Properties of water ......................................................................................... 64 3.6.2.2 Meteorological variables ................................................................................ 64 3.6.2.3 Circulation ..................................................................................................... 65 3.6.2.3.1 Dimictic .................................................................................................... 66 3.6.2.3.2 Meromixis ................................................................................................ 67 3.6.2.4 Role of ice cover ............................................................................................ 68 3.6.2.5 Settling........................................................................................................... 68 3.6.3 Chemical and biological processes ......................................................................... 70 3.6.3.1 Partitioning .................................................................................................... 70 vii  3.6.3.2 Degradation.................................................................................................... 72 3.6.3.3 Seepage .......................................................................................................... 75 3.7 Tailings pond conceptual model ................................................................................. 77 Chapter 4: Discussion ............................................................................................................. 86 4.1 Literature review ....................................................................................................... 86 4.2 Oil sands process water properties ............................................................................. 88 4.2.1 Physical variables .................................................................................................. 88 4.2.2 Major ions ............................................................................................................. 89 4.2.3 Organic compounds ............................................................................................... 90 4.2.4 Nutrients ................................................................................................................ 91 4.2.5 Elements ................................................................................................................ 92 4.2.6 Biology .................................................................................................................. 94 4.3 OSPW CCME water quality index ............................................................................. 96 4.4 OSPW parameters data source comparison ................................................................ 98 4.5 Ecological effects .................................................................................................... 100 4.5.1 Athabasca watershed ............................................................................................ 100 4.5.2 OSPW toxicological effects ................................................................................. 101 4.6 Tailings pond processes ........................................................................................... 103 4.6.1 Physical processes: limnology .............................................................................. 103 4.6.2 Chemical and biological processes ....................................................................... 105 4.7 Tailings pond conceptual model ............................................................................... 108 Chapter 5: Conclusion .......................................................................................................... 111 Bibliography .......................................................................................................................... 115 viii  Appendices ............................................................................................................................ 126 Appendix A Literature Reviewed ........................................................................................ 126 A.1 Sub-Appendix literature reviewed and number of times articles are cited in literature. Certain sources such as theses and websites typically were not cited. ............... 126 A.2 Sub-Appendix literature reviewed and was not used in thesis. Certain sources such as theses and websites typically were not cited. ............................................................... 129 Appendix B CCME Data ..................................................................................................... 135 B.1 Sub-Appendix CCME tested data ......................................................................... 135 B.2 Sub-Appendix CCME output data ........................................................................ 144  ix  List of Tables  Table 3.1   The OSPW characterization data from17 scientific sources: physical variables (mg/L). ...................................................................................................................................... 20 Table 3.2   The OSPW characterization data from17 scientific sources: major ions (mg/L)........ 26 Table 3.3   The OSPW characterization data from17 scientific sources: organic compounds (mg/L). ...................................................................................................................................... 30 Table 3.4   The OSPW characterization data from17 scientific sources: nutrients (mg/L). ......... 34 Table 3.5   The OSPW characterization data from17 scientific sources: elements (mg/L). ......... 39  x  List of Figures  Figure 1.1  The Alberta Oil Sands deposits are located in northern and eastern Alberta, Canada (Government of Alberta, 2012). ..................................................................................................5 Figure 1.2  The typical process of bitumen extraction and tailings release. Retrieved from Chalaturnyk et al. (2002). ............................................................................................................7 Figure 1.3  Diagram of oil sands grains characteristics with relative locations of water, bitumen, sand and fine (clay) particles. Retrieved from Scott (2007). .........................................................8 Figure 1.4  Tailings settling pond cross section. Image retrieved from Zubot (2010). ................. 11 Figure 3.1  Literature review total number of scientific articles reviewed by category. .............. 17 Figure 3.2 The OSPW characterization log 10 transformed data for 17 scientific sources: Physical variables. ..................................................................................................................... 19 Figure 3.3 The OSPW characterization from 17 scientific sources: physical variables BOD, COD, DOC and TOC, mean concentrations with standard error. ............................................... 21 Figure 3.4 The OSPW characterization from 17 scientific sources: physical variables dissolved oxygen (DO), pH and temperature, mean concentrations (mg/L unless otherwise noted) with standard error. ........................................................................................................................... 22 Figure 3.5 The OSPW characterization from 17 scientific sources: physical variables alkalinity, conductivity, hardness, TDS and TSS, mean concentrations (mg/L unless otherwise noted) with standard error. ........................................................................................................................... 23 Figure 3.6 The OSPW characterization log 10 transformed data for 17 scientific sources: major ions. The dots show all outliers, while line in the box represents median value and the whiskers above and below are 90th and 10th percentiles. ......................................................................... 25 xi  Figure 3.7 The OSPW characterization from17 scientific sources: major ions mean concentrations (mg/L) with standard error. ................................................................................ 27 Figure 3.8 The OSPW characterization log 10 transformed data for 17 scientific sources: organic compounds. The dots show all outliers, while line in the box represents median value and the whiskers above and below are 90th and 10th percentiles. .......................................................... 29 Figure 3.9 The OSPW characterization from 17 scientific sources: organic compounds mean concentration (mg/L) with standard error. ................................................................................. 31 Figure 3.10 The OSPW characterization log 10 transformed data for 17 scientific sources: nutrients. The dots show all outliers, while line in the box represents median value and the whiskers above and below are 90th and 10th percentiles. .......................................................... 33 Figure 3.11 The OSPW characterization from 17 scientific sources: nutrients mean concentrations (mg/L) with standard error. ................................................................................ 35 Figure 3.12 The OSPW characterization log 10 transformed data for 17 scientific sources: elements. The dots show all outliers, while line in the box represents median value and the whiskers above and below are 90th and 10th percentiles. .......................................................... 38 Figure 3.13 The OSPW characterization from 17 scientific sources: metals mean concentration (mg/L) with standard error. ....................................................................................................... 41 Figure 3.14 The CCME water quality index (WQI) calculations for the 17 sources of data on OSPW properties, in evaluated against the percent of completeness of data for WQI variables. . 46 Figure 3.15 The comparison of water quality from three data sources: pH. ................................ 48 Figure 3.16 The comparison of water quality from three data sources: conductivity .................. 48 Figure 3.17 The comparison of water quality from three data sources: chloride, sodium and sulphate. .................................................................................................................................... 49 xii  Figure 3.18 The comparison of water quality from three data sources: ammonia, calcium, carbonate, potassium, magnesium, and naphthenic acids. .......................................................... 51 Figure 3.19 The comparison of water quality from three data sources: aluminum, boron, iron, strontium and vanadium. ........................................................................................................... 52 Figure 3.20 The comparison of water quality from three data sources: manganese and molybdenum. ............................................................................................................................ 53 Figure 3.21  Tailings settling pond cross section (to the left image retrieved from Zubot (2010)) with conceptual Tailings Pond Model compartments (to the right). ........................................... 61 Figure 3.22  Tailings pond conceptual input and output of all compartments. ............................ 63 Figure 3.23  Alberta Oil Sands conceptual Tailings Pond Model overview of conventional variables. ................................................................................................................................... 79 Figure 3.24  Alberta Oil Sands conceptual Tailings Pond Model overview of ions. ................... 81 Figure 3.25  Alberta Oil Sands conceptual Tailings Pond Model overview of organic compounds. ................................................................................................................................................. 83 Figure 3.26  Alberta Oil Sands conceptual Tailings Pond Model overview of elements. ............ 85  xiii  List of Abbreviations BOD  Biochemical Oxygen Demand BTEX  Benzene Toluene Ethylbenzene Xylene C  Celsius CAPP   Canadian Association of Petroleum Producers CaSO4 2H2 Gypsum CCME  Canadian Council of the Ministers of the Environment CH4  Methane  CHWE  Clark Hot Water Extraction cm  Centimeter cm3  Cubic Centimeter CO2  Carbon Dioxide COD  Chemical Oxygen Demand CT  Composite/Consolidated Tailings d  Day DOC  Dissolved Organic Carbon EPL   End Pit Lake EROD  ethoxyresorufin O-deethylase FFT  Fluid Fine Tailings g  Gram GST   Glutathione S-Transferase  H2S   Hydrogen Sulphide IEA   International Energy Agency xiv  IR   Visible Infrared km  Kilometer km2  Square Kilometer L  Liter LPO  Lipid Peroxidation M  Meter m2  Square Meter m3  Cubic Meter m/e  Mass-To-Charge Ratio μg  Microgram mg  Milligram MFT  Mature Fine Tailings MLSB  Mildred Lake Settling Basin μS  Microseimens n  Number NaOH   Sodium Hydroxide NAs  Naphthenic Acids NOx   Oxides of Nitrogen OCs   Organic Compounds OSLO   Other Six Lease Owners OSPW  Oil Sands Process-affected Water PAC   Polycyclic Aromatic Compound PAHs  Polycyclic Aromatic Hydrocarbons xv  pm   Picometer ppb  Part Per Billion RAMP  Regional Aquatics Monitoring Program RBC   Red Blood Cells SARA  Saturates Aromatics Resins Asphaltenes TDS  Total Dissolved Solids TSS  Total Suspended Solids UV   Ultraviolet  VOCs   Volatile Organic Compounds wt %  Weight Percentage WQI   Water Quality Index x  Times (multiplication) xvi  Acknowledgements I would like to thank my supervisor, Dr. Susan Baldwin, for her guidance during the course of this research. I would also like to thank the members of my advisory committee, Dr. D. Posarac and Dr. D. van Zyl, for their time and advice. I would like to acknowledge my funding source as Total E&P Canada Ltd.  I would like to thank the Chemical and Biological Engineering Graduate program students and staff for their support over the years. I offer my enduring gratitude to the faculty, staff and my fellow students at UBC, who have inspired and enlightened me. In particular, I would like to thank the professors in the departments of Chemical and Biological Engineering, Civil Engineering, Earth and Ocean Science, and Geography, for sharing their knowledge and excellent instruction. I am thankful for the support and encouragement from the students, staff and faculty of the Toxicology Graduate Program, at the University of Saskatchewan (USASK). I am grateful for the past decade of experience with USASK Toxicology Centre, under the mentorship of many valued scientists who helped shape the way I conduct science; Dr. Karsten Liber, Dr. Lynn Weber, Dr. Monique Dubé, and Dr. David Janz. Many thanks to Dr. Doug Smith (Zoology) and the late Pat Clay (Botany), at the USASK Department of Biology, for the many years teaching alongside them and their influential knowledge in understanding the most basic to complex organisms, their structure and function and phylogeny. I would like to thank my past supervisor, Phil Curry, with the Ministry of Population Health, Government of Saskatchewan, for his valued advice and encouragement in my pursuing a Master of Science.  I would like to thank my family and friends who provided encouragement. I would like to thank the hard times, where perseverance prevailed, for it is those times which brings out a person’s true character, and that which does not break you can indeed make you stronger. xvii  Dedication  To my family, friends and mentors, Thank you for your support and encouragement, from where I draw my inspiration. With all my love, to my mother and late father, if it hadn’t been for you I would not be here. Thank you1  Chapter 1: Introduction  The Alberta Oil Sands development has been in operation since the 1960s, where innovations in technology in bitumen extraction have resulted in adaptive management of environmental sensitivities to Oil Sands Process-affected Water (OSPW) and tailings. This research assessed all the potential processes that OSPW constituents might undergo in the tailings impoundments in order to speculate on their ultimate fate. A conceptual tailing pond model was created, a tool for future management of these facilities and the first of its kind as there have been no attempts in the existing literature. The development of a model is quite complex where first the objectives are defined (e.g. OSPW constituents) and the various physical, chemical, biological, geochemical, hydrological and limnological processes involved. This research was conducted by one individual, while such integration and analysis would typically be tackled by a team of multidisciplinary experts. A great contribution of this work was to highlight gaps in our knowledge about processes taking place in OSPW tailings ponds; particularly in the areas of high risk (e.g. mixing within tailings ponds, speciation of metals, volatilization, airborne emissions). The scope of this research included the spatial and geological focus comprised the Athabasca ore deposit, with special attention on the Fort McMurray area and particular examination of the Mildred Lake Settling basin. The intent was to create a consistent and thorough research, since ore bodies contain unique characteristics and each area has special geospatially related environmental concerns. The variations in chemical composition and physical properties of OSPW and tailings are primarily due to variations in the ore and operations of extraction. The engineering problem was to determine the probable concentrations 2  and ultimate fates of various substances of OSPW in a tailings pond. The exact composition of tailings has not been determined by the scientific literature, due to the high complexity of organic compounds which are yet to be identified. Oil sands mines generate process affected water containing many different types of constituents and the high degree of water recycling further concentrates these substances along with introducing additional chemicals in the process (e.g. assisted tailings consolidation) and influencing water chemistry (e.g. alkalinity, hardness, pH). The aqueous chemical properties of OSPW are examined with consideration of influences from crushing and mixing with recycled process water. The chemical additives used to assist in dewatering are examined in overview as to how these may alter the concentrations of bulk contaminants in the OSPW. All further refinement and upgrading of the bitumen were out of scope and there is no examination of the processing of coke or other by-products.  1.1 Geological origin of the ore deposit  The oil sands resource is found in a 140,000 square kilometers (km²) section of northern Alberta (Jordaan, 2012). The Athabasca ore deposit is 42,000 km2 (Rogers et al., 2002). The origin of natural gas and crude oil has been theorized to be the result of compression and heating of ancient organic materials such as kerogen (Nji, 2010). The key components include endothermic reactions at high temperature and pressure, followed by bacterial action which produces natural gas. The heavy bitumous tar was created by biodegradation of conventional crude oil by bacteria to produce high density and high in viscosity crude and water washing may also play a role in the process (Rubinstein et al., 1977). 3  The Alberta oil sands bitumen deposit are composed of approximately 20% bitumen, 5% water, 75% sand, silts and clays and 1% particulate materials (Merlin, 2007). Bitumen contains high levels of sulfur, nitrogen, and various heavy metals. Metals typically associated with bitumen include iron, nickel, copper, vanadium, titanium, and zirconium (Cao et al., 2007; Nji, 2010). The major constituents of crude oil are paraffins (alkanes which are saturated straight chain hydrocarbons), cycloparaffins (naphthenic hydrocarbons), aromatic hydrocarbons, and polynuclear aromatics (asphaltenes) (Nji, 2010). These four constituents of saturates, aromatics, resins, asphaltenes (SARA) compose conventional crude oil and bitumen, with latter with higher levels of aromatic components. Athabasca Bitumen was shown to contain 16.3% saturates, 39.8% aromatics, 28.5% resins, 14.7% asphaltenes, and 0.7% solids. The main elements of petroleum are carbon, hydrogen, nitrogen, oxygen and sulfur.  1.2 Environmental setting  Athabasca oil sands are located in the boreal plains region of Alberta, Canada, located approximately 400 km north east of Edmonton (Parsons, 2007). The region is characterized by fens and bogs, which are dominated by black spruce (Picea mariana) in the lowland areas, while trembling aspen (Populus tremuloides) and jack pine (Pinus banksiana) forests typify the upland regions. The lakes in the area are generally small, eutrophic and high in dissolved organic carbon. The Peace River runs through the unexploited surficial deposits of oil sands, while the Athabasca River and its tributaries traverse the bitumen laden surface deposits and areas where surface mining and processing occur. The general area forms a slight depression with the Stony 4  Mountains to the east and the Birch Mountains located to the north-west, which undergoes periodic flooding from the Athabasca River (Hall et al., 2012).  1.3 Alberta oil sands history  The Alberta oil (tar) sands are a unique source of petroleum in the world. The International Energy Agency (IEA) estimated this resource is estimated to contain 1.75 to 2.5 trillion barrels of oil which is larger than the 112 billion in Iraq and 250 billion in Saudi Arabia (Levi, 2009). These bitumen deposits are located in northern and eastern Alberta and comprising of approximately 140,200 square kilometers (Figure 1.1) (Government of Alberta, 2012). The primary deposits include: Peace River, Athabasca, and Cold Lake (Chastko, 2004).  The deposits of tar sands were well known by First Nations in the area (Chastko, 2004). The tar-like substance would seep out from the banks of the Athabasca River, on hot summer days, where it was gathered (Oil Sands Info Mine, 2012). A traditional use of the thick bitumen was to make a mixture with spruce fir sap, used as a sealant when making or patching canoes (Chastko, 2004).  5   Figure 1.1  The Alberta Oil Sands deposits are located in northern and eastern Alberta, Canada (Government of Alberta, 2012).  The Mines Branch of Canada (Sydney C Ells) and the University of Alberta (Dr. Adolph Lehman), worked on extraction methods to separate the oil from the tar sands; the former through superheated steam and the later chemical emulsifiers (Chastko, 2004). The province of Alberta established the Scientific and Industrial Research Council (also known as the Alberta Research Council) research by Dr Karl Clark which would focus on hot water separation (similar method to Ells). The Clark Hot Water Extraction process (CHWE) was developed in 1967 by Great Canadian Oil Sands (now Suncorp Energy Inc) (Masliyah et al., 2004). Syncrude Canada Ltd started commercial operations at Fort McMurray in the 1970s. Albian Sands Energy Inc was operational in 2003. Open-pit mine operations typically use trucks and shovels (Masliyah et al., 2004). Proprietary processing technologies varied where Syncrude used the Other Six Lease Owners (OSLO) cold water process, low energy extraction, while Albian uses the paraffinic 6  froth treatment. During the 1990s pipelines oil sands slurry hydrotransport was introduced in replacement for tumblers which used traditional hot water process.  Approximately 663 km2 have been disturbed, while only approximately 10 percent (over 67 km2) have been reclaimed (Government of Alberta, 2012). The recovery process is highly water intensive, typically 7.5 to 10 barrels of water is required per barrel of oil produced (Government of Alberta, 2012). Water conservation efforts have included recycling used water. Recycling requires additional barrels of water, as little as 0.5 for in situ and 3 to 4.5 for mining (Canadian Association of Petroleum Producers (CAPP), 2012). The Oil Sands Operation in Northern Alberta produces an estimated 1.2-1.6 x 109 m3 per day of process affected water tailings (Government of Alberta, 2011; Kelly et al., 2009). Government regulations stipulate a zero discharge policy to ground or surface waters, wherein all Oil Sands Process-affected Water must be contained (Kannel et al., 2012). Industrial innovations have included improvements in the active management of OSPW and containment in settling basins and tailings ponds.  1.4 Mining  1.4.1 Bitumen extraction and processing  The bitumen deposits are primarily found in quartz sand, fieldspar, mica flakes, and clays (the most common are koalinite and illite, while chlorite, montmorillonite, calcite and dolomite also present) (Scott, 2007). The overburden (50 - 825 m thick) of muskeg, glacial till and Cretaceous bedrock is removed through open-pit mining. Open-pit mine operations typically use trucks and shovels (Masliyah et al., 2004). Processing bitumen ore typically begins with crushing 7  and mixing with recycle process water in mixing boxes and stirred tanks (Figure 1.2). The extraction plant typically blends hot water and caustic soda (sodium hydroxide, NaOH) to separate the bitumen from the mineral solids (Cao et al., 2007) (Figure 1.3). Syncrude utilized cyclo-feeders, while Suncor rotary breakers to reduce the size of the pieces and aid the release of bitumen from sand grains (Masliyah et al., 2004). Proprietary processing technologies vary among Syncrude Canada Ltd and Albian Sands Energy Inc; where the former used the OSLO cold water process, low energy extraction, while the later used the paraffinic froth treatment Oil sands slurry hydrotransport replaced tumblers which used traditional hot water process.    Figure 1.2  The typical process of bitumen extraction and tailings release. Retrieved from Chalaturnyk et al. (2002).  8  The froth treatment, where chemical additives and air are introduced into the tumblers and hydrotransport pipelines, results in the entrainment of mineral solids and the removal of water by gravity settling and centrifuging (Cao et al., 2007; Masliyah et al., 2004). Syncrude and Suncor use solvent naphtha, while Albian use paraffinic diluent hexane which initiates the precipitation of asphaltenes, and the formation of bitumen froth (containing water and solids) (Masliyah et al., 2004). Aerated bitumen floats and is skimmed off via gravity separation vessels. Air is introduced again to recover the remaining bitumen droplets which were previously unaerated. The froth consists of 60% bitumen, 30% water, and 10% solids. The average recovery rate of bitumen is 88-95%. Froth tailing typically contains 2% residual bitumen which was not liberated from mineral matter (quartz, kaolinite, illite, montmorillonite clay, heavy metals), equivalent to 6 million barrels of oil lost per year (Cao et al., 2007).    Figure 1.3  Diagram of oil sands grains characteristics with relative locations of water, bitumen, sand and fine (clay) particles. Retrieved from Scott (2007). 9  At high temperatures bitumen tends to engulf solid particles (Cao et al., 2007). Temperature in the tumblers is typically 75 degree Celsius (°C), while Syncrude hydrotransport is 35 °C (Masliyah et al., 2004). The typical temperature needed during frothing is 40-55 °C. Alkalinity improves liberation of bitumen through electrostatic repulsion from particle charges (Cao et al., 2007). Sodium hydroxide (NaOH) or caustic soda improves the floatation of bitumen droplets, through the release of surfactants such as carboxylates. The extraction pulp is high in dissolved ions Ca2+, HCO3-, K+, Mg2+, Na+, SO4 2-. NaOH tends to precipitate ions of Ca2+, Fe2+ and Mg2+. Clays and mineral slimes covered by solvent-insoluble humic substances are partially hydrophobic and bitumen will adhere to clays and mineral slimes. In addition, the liberation of bitumen from quartz sand can be decreased by the presence of hydrolyzable metal cations (within certain pH limits). Bitumen recovery is also decreased with high concentrations of K+ and Na+. The charge on a bitumen droplet originates from the carboxylic and phenolic groups, which both can bond to Ca2+. The liberation of bitumen tends to be impossible in the presence of calcium ions when pH is above 10. The clay mineral montmorillonite affects bitumen floatation in the presence of Ca2+ (40 mg/L). The coagulation of bitumen and silica is activated in the presence of CaOH+ which promotes the adsorption anionic surfactants making silica surfaces hydrophobic. Although, silica reacts with CaOH+ and it does not with Ca+. Naphthenic acids (NAs) are non-volatile, chemically stable, and act as surfactants (Clemente et al., 2005). The Syncrude property ore contains on average 200 mg NAs per kg.  Naphthenic acids are found in a dissolved state in the neutral or slightly alkaline effluent waters and precipitate in acidic conditions (e.g. sodium salts of naphthenic acid). The effluent from the extraction plant will undergo solid-liquid separation in the tailings pond where clarified water is recycled back to extraction plant (Masliyah et al., 2004). An 10  estimated 4 m3 of slurry waste is produced per cubic meter of mined oil sands (Holowenko et al., 2000). Suncor and Syncrude use CT processes which add gypsum to MFT to consolidate fines with coarse sand into non-segregating mixture deposited in geotechnical manner enhance dewatering and used in reclamation, while Albian uses cyclone and flocculants to thicken (Masliyah et al., 2004). Gypsum, chemical formula CaSO4·2H2O, is an acid salt which causes the release of Na+, calcite precipitate, and Ca+2 in solution (MacKinnon et al., 2001). Chemical treatment in ore extraction and to enhance settling rates in tailings result in effluent high in dissolved ions which are primarily comprised of sodium, chloride, sulphate and bicarbonate (Holden et al., 2011).  1.4.2 Mine engineering and tailings pond design  Land surface mining footprint comprises mine sites, overburden storage, tailings ponds, end pit lakes, and linear features such as networks of seismic lines, access roads, and pipelines (Jordaan, 2012; McKenna et al., 2012). The active management and containment of oil sands process affected water is the result of a zero discharge policy to ground or surface waters (Kannel et al., 2012). The construction of tailings dams involves a starter dam and tailings are released into the settling basin in an upstream method (Klohn, 1997). Mildred Lake Settling Basin (MLSB) was established in 1978 and is the oldest and largest active tailings pond, with a surface area of 10 km2 and containing over 600 million m3 (in 2005) (Kannel et al., 2012; Xiumei et al., 2009). Recent studies suggest that the residence time of seepage through the tailings dam wall was over 20 years and that pore water within these sand dikes are under anoxic conditions. Oil Sands Process-affected Water (OSPW) and fine tailings 11  slurry (30-55% weight solids to liquids) are discharged into MLSB, where solids from the liquefied tailings form beaches (e.g. quartz sand, fieldspar, mica flakes, and clays) (Klohn, 1997; Leung et al., 2001; Scott, 2007). The tailings pond shows stratification and compartmentalization, where free water forms the uppermost layer, followed by fine fluid tailings and mature fine tailings (Figure 1.4) (Zubot, 2010). The total time for sedimentation and self-weight consolidation of fines has been estimated at 125-150 years (Eckert et al., 1996). Consolidated tailings (CT) technology expedites the process of dewatering tailings through chemical additives (e.g. Gypsum, Flocculants) and cyclone technology (Masliyah et al., 2004). The clarified water is then recycled in the extraction plant. As a consequence of recycling OSPW the chemical constituents become more concentrated (Leung et al., 2001).    Figure 1.4  Tailings settling pond cross section. Image retrieved from Zubot (2010).   12  1.4.3 Reclamation activities  Since the late 1980s, Syncrude Canada has constructed and monitored a series of mesocosms to investigate the toxicological properties and ecological effects of various analogues of reclamation options (Leung et al., 2001). Reclamation of terrestrial landscape include dewatered fine tailings mixed with sand, buried, and soil capped (Allen, 2008). Artificially created wetlands and lakes from mined-out areas include the capping of FFT with OSPW and clean river water. Pilot ponds have been created since the 1980s have shown colonization by aquatic plants and microbes and subsequent microbial degradation of toxic components (e.g. NAs). Approximately 663 km2 have been disturbed, and approximately 10 percent (over 67 km2) have been reclaimed, of which some date back over 40 years (Government of Alberta, 2012; Sobkowicz, 2012). Areas gradually reclaimed include the toes of dumps and dykes. Pond reclamation can be challenging, particularly if underlain with soft tailings. There are approximately 30 proposed end pit lakes (EPL) as permanent features on reclaimed mined land, located within a post-mining pit, with a bottom composed of tailings (Hrynyshyn et al., 2012; McKenna et al., 2012). These constructed with FFT and capped with freshwater from surface runoff, and groundwater which infiltrates through percolation and capillary action (hydraulic conductivity of the bed and wall materials will determine the rate of groundwater infiltration). The flow of water in and out of aquifers contains the possible liability of contaminant transport and contamination of groundwater. The consolidation of FFT will cause pore water to be released into the water cap layer. Additional process-related materials have been proposed to be stored in the EPL, such as MFT, petroleum coke, OSPW, overburden and sand. The EPL are meant to be comparable to the natural conditions. The only comparable 13  anthropogenic features in existence are the Syncrude Canada’s Base Mine Lake demonstration lake and test wetlands. Although, non-oil sands pit lakes exist in Alberta, where four coal mine pit lakes have been created.  14  Chapter 2: Materials and Methods  2.1  Methods  The following literature review of scientific journal articles was performed through key word searches utilizing the UBC database search through the Web of Knowledge SM version 5.9, via the sub database of the Web of Science®. The number of times an article was cited, mentioned in peer-reviewed journals, was documented. All literature sources were reviewed on equal standing, examination was based on relevancy of content.  The primary intent in summarizing the OSPW constituents and tailings pond processes was with special attention on the Athabasca ore deposit, with special attention on the Fort McMurray area and particular examination of the Mildred Lake Settling basin (MLSB). Literature on MLSB was considered most relevant. While a broad spectrum of literature was reviewed in attempts to elucidate the pathways of the OSPW constituents from possible sources to physical, chemical and biological processes within a tailings pond.  The key words utilized in the search engine included: tar sands, oil sands, Alberta, Athabasca, characterization, bitumen, tailings, pond, basin, metals, organics, salts, naphthenic acids, polyaromatic hydrocarbons,  toxicity, methanogens, microbiological, microbes, bacteria, treatment, processing, extraction, oil sands process water, free water, pore water, dike, hydrology, geology, origin, ore, ecological, effects, watershed, water quality, settling, sedimentation, consolidation, mature fine tailings, fine fluid tailings, attenuation, seepage, groundwater, multiphase flow, engineering. Additional information was searched through the internet for industrial and regulatory information pertaining to the former key words.  15  The data from scientific articles and academic theses were analyzed for the purpose of characterizing the physical, chemical, and biological properties of the OSPW and tailings, at various stages from release to over time in the tailings settling pond. The OSPW and tailings were summarized in terms of physical and chemical parameters, and concentrations of elements, ions, organic compounds and nutrients. These parameters were then compared to the Canadian Council of the Ministers of the Environment (CCME) water quality guidelines for the protection of aquatic health. The CCME has only made guidelines for some physical, chemical, metals and organic and inorganic constituents. In addition, the data was analyzed with the CCME Water Quality Index Calculator. The mine processes, such as crushing, mixing and addition of chemicals, were reviewed for influences in the water chemical properties of OSPW and ultimate fate of bulk contaminants in a settling basin or tailings pond. The first step was to define the OSPW constituents, followed by a close examination of the various physical, chemical, biological, geochemical, hydrological and limnological processes involved.  In addition, an investigation was conducted on existing research on the contaminant concentrations within the OSPW and tailings pond over time. The data and concepts from these sources were used as a basis in the creation of a Tailings Pond Model, to conceptualize the physical, chemical and biological processes within a typical tailings settling basin. All sources were reviewed for pertinent information and thus treated equally, despite the number of times cited in published in peer reviewed articles. The information was assessed against current theories and facts in the fields of mine engineering, toxicology, microbiology, kinetics and limnology.  16  Chapter 3: Results  3.1 Literature review The following thesis is a summary of 85 literary sources which were the most significant and relevant in information (Appendix A.1). While an additional 36 articles had been reviewed, these were determined to have less contribution (Appendix A.2). The literature reviewed included eight key categories: characterization, geochemical, geology, limnology, microbiology, mine engineering, toxicology, and treatment. The literature reviewed is summarized in Figure 3.1. These included: characterization of the OSPW properties (n=24), geochemical processes known to occur (n=2), geology of the Oil Sands (n=3), limnology of water bodies in general and tailings ponds (n=12), microbiology including microbial related research within the Oil Sands and the biological make-up of the MLSB (n=13), mine engineering in the Alberta Oil Sands region (n=12), toxicology including research on the possible effects of the OSPW constituents on biological life processes and ecology (n=14), treatment  with past and current operations in the Alberta Oil Sands and innovative alternatives (n=5). Certain sources of information such as theses and websites were typically not cited or mentioned in peer-reviewed journals.  17   Figure 3.1  Literature review total number of scientific articles reviewed by category.   3.2 Oil sands process water properties  The characterization of the OSPW and tailings was compiled through a summary of 17 journal articles and academic theses, see the following: Allen 2008; Baker et al 2012; Debenest et al 2012; El-Din et al 2011; Holden et al 2011; Holowenko et al 2000; Hrynyshyn et al 2012; Leung et al 2003; Ma 2012; Mackinnon et al 2001; Peng et al 2004; Sansom 2010; Scott et al, 2008; Tompkins 2009; Van den Heuvel et al 1999; Xiumei et al 2009; Zubot 2010. The sample sizes varied for the various parameters, due to differences in analysis and reporting.     18  3.2.1 Physical variables  The physical parameters are shown in Figure 3.2, where data was log 10 transformed for the purpose of showing data variability ranges. The physical variables data is summarized in Table 3.1 and Figures 3.3, 3.4 and 3.5. OSPW and tailings typically have a pH ranging from 8.0-8.4, and moderately high hardness 91-405 mg/L, and alkalinity ranging from 113-966 mg/L. Conductivity averaging at 2259 μS/cm with average total suspended solids (TSS) 828 mg/L and total dissolved solids (TDS) 2175 mg/L. Dissolved organic carbon (DOC) averaged at 52 mg/L with a biochemical oxygen demand (BOD) ranging from 0.5-70 mg/L and chemical oxygen demand (COD) 86-973 mg/L.    19   Figure 3.2 The OSPW characterization log 10 transformed data for 17 scientific sources: Physical variables. The dots show all outliers, while line in the box represents median value and the whiskers above and below are 90th and 10th percentiles.         Physical variables0 1 2 3 4 5 6 7 8 9 10 11 12 13Log10 Data-101234Alkalinity BOD  COD Cond  DO DOC Hardness pH TDS Temp TOC TSS    20   Table 3.1   The OSPW characterization data from17 scientific sources: physical variables (mg/L). Physical Variable units n Mean Std Dev Std. Error Max Min Median  CCME Alkalinity mg/L 21 501.33 286.21 62.46 966 113 439   BOD mg/L 12 13.7 19.03 5.49 70 0.5 6.45   COD mg/L 14 289.21 221.61 59.23 973 86 216.5   Conductivity μS/cm 81 2259.31 1265.05 140.56 4920 256 2280   DO mg/L 48 6.86 4.28 0.62 14.5 0.25 8.1 6.51 - 9.52  DOC mg/L 21 51.95 7.62 1.66 67 35.8 52   Hardness mg/L 3 202.67 175.54 101.348 405 91 112   pH  95 8.29 0.70 0.07 12 5 8.25 6.5 - 9.0 TDS mg/L 22 2175.82 639.18 136.27 3000 565 2215.5   Temperature ˚C 45 19.14 3.84 0.57 24.1 9.5 19.5   TOC mg/L 2 49 7.071 5 54 44 49   TSS mg/L 11 828.18 630.19 190.01 2310 200 600 53 - 254  1. for cold water biota: other life stages = 6.5 mg/L  2. for cold water biota: early life stages = 9.5 mg/L 3. Maximum average increase of 5 mg/L from background levels for longer term exposures (e.g., inputs lasting between 24 h and 30 d). 4. Maximum increase of 25 mg/L from background levels for any short-term exposure (e.g., 24-h period).           21     Figure 3.3 The OSPW characterization from 17 scientific sources: physical variables BOD, COD, DOC and TOC, mean concentrations with standard error.   Physical variablesBOD COD DOC TOCMean (mg/L)010020030040022      Figure 3.4 The OSPW characterization from 17 scientific sources: physical variables dissolved oxygen (DO), pH and temperature, mean concentrations (mg/L unless otherwise noted) with standard error. 1. pH units 2. Temperature (˚C)     Physical variablesDO pH TemperatureMean (mg/L)05101520252 1 23    Figure 3.5 The OSPW characterization from 17 scientific sources: physical variables alkalinity, conductivity, hardness, TDS and TSS, mean concentrations (mg/L unless otherwise noted) with standard error.  1. Conductivity (μS/cm)                  Physical variablesAlkalinity Conductivity Hardness TDS TSSMean (mg/L)0500100015002000250030001 24  3.2.1.1 Major ions  The OSPW and tailings content of ions in order of descending mean concentration: Na+, Cl-, SO42-, Ca2+, Mg2+, K+, CN-, Fe 2+, S2-, Hg+ (Figure 3.6). The OSPW major ions concentrations and examination against CCME guideline objectives are summarized in Table 3.2. All ions, in exception to those where there was a lack of guidelines, exceeded the CCME objectives (Figure 3.7). The extraction process slurry typically contains polyvalent metal ions such as Ca2+, Fe2+ and Mg2+ (Baker et al., 2012). Fresh tailings OSPW is alkaline (pH >8.5) and can contain 70-120 mg/L of Ca+2 in solution and 1000 mg/L of sulphate (MacKinnon et al., 2001). The recycling of OSPW, stored in tailings ponds, for use in treatment processes result in the concentration of ions and other chemical constituents over time (Holden et al., 2011). Tailings pond water has shown over time a dramatic increase in sodium, chloride, sulphate, bicarbonate, and ammonia; where respective exceedences from reference Athabasca River values are by magnitudes of 40, 90, 30, 8, and 200 times, respectively (Allen, 2008).  25    Figure 3.6 The OSPW characterization log 10 transformed data for 17 scientific sources: major ions. The dots show all outliers, while line in the box represents median value and the whiskers above and below are 90th and 10th percentiles.        IonsLog10 Data-6-4-2024         Ca2+      Cl-     CN-      Fe2+      Hg+     K+ Mg2+ Na+ S2- SO42-  26  Table 3.2   The OSPW characterization data from17 scientific sources: major ions (mg/L). Major Ions n Mean Std Dev Std. Error Max Min Median  CCME¹ CCME² Ca2+ 107 27.88 29.721 2.873 200 3.4 18     Cl- 100 302.154 255.53 25.553 970 4.4 257.5 120 640 CN- 12 0.966 3.163 0.913 11 0.0025 0.0065 0.005   Fe 2+ 36 0.705 2.069 0.345 12.5 0 0.2 0.3   Hg+ 5 0.0000434 0.00000853 0.00000382 0.00005 0.00003 0.000047 0.000026   K+ 87 9.367 11.205 1.201 96 0.5 9     Mg2+ 97 18.672 19.945 2.025 139 2.1 11.7     Na+ 109 513.252 315.15 30.186 1170 0.8 544 10%³   S2- 11 0.68 1.914 0.577 6.4 0.005 0.01     SO42- 101 294.976 345.802 34.409 1800 0 204     1. Long term 2. Short term 3. Maximum fluctuation is by more than 10% of the natural level. Salinity of the world’s oceans ranges from 32–38% with an average of 35%.  27   Figure 3.7 The OSPW characterization from17 scientific sources: major ions mean concentrations (mg/L) with standard error. *Mean exceeds the CCME Water Quality Guideline for the protection of aquatic life long term effects.   3.2.1.2 Organic compounds  The OSPW and tailings content of organic compounds in order of descending mean concentration: bicarbonate (HCO3-) (1290- 70 mg/L), tannin/lignin (565- 1 mg/L), NAs (130-0.005 mg/L), carbonate (CO3 2-) (335- 0 mg/L), bitumen (92- 0.094 mg/L), total hydrocarbon (22-1 mg/L), phenols (53- 0.0053 mg/L), toluene (6.3- 1 mg/L), benzene (6-0.2 mg/L), polycyclic aromatic hydrocarbons (PAHs) gp5 (1.2- 0.01 mg/L), m&p xylene (0.4 mg/L), ethylbenzene (0.2 mg/L), o-xylene (0.2 mg/L) (Figure 3.8). These organic compound IonsCa2+ Cl- CN- Fe 2+ Hg+ K+ Mg2+ Na+ S2- SO42-Mean (mg/L)0100200300400500600* * * * 28  concentrations and CCME guideline objective values are summarized in Table 3.3. All compounds for which there were CCME guideline values were in exceedence (Figure 3.9). The effluent from oil sands extraction processes contains various other organic components such as asphaltenes, creosols, humic and fulvic acids, and phthalates (Leung et al., 2001).   Bitumen concentrations vary and some Suncor ponds ranged from 9 to 31 mg/L. NAs are released into the OSPW (typically 20-120 mg/L) during the alkaline extraction conditions (Xiumei et al., 2009). Clemente and Fedorak (2005) reported tailings pond NA content assessed at being as high as 50 mg/L. Frank (2008) described tailings water with pH 8-9 and stipulated that at those conditions the NAs would be in the form of sodium naphthenate salts. The consolidation of MFT has shown to release pore water containing high levels of dissolved organics (naphthenic acids, 70-100 mg/L) (Leung et al., 2001).  29   Figure 3.8 The OSPW characterization log 10 transformed data for 17 scientific sources: organic compounds. The dots show all outliers, while line in the box represents median value and the whiskers above and below are 90th and 10th percentiles.       Organic compounds0 1 2 3 4 5 6 7 8 9 10 11 12 13 14Log10 Data-4-3-2-101234Benzene Bicarbonate Bitumen Carbonate Ethylbenzene m&p xylenes NAs 0-xylene PAH gp5 Phenols Tannin/Lignin Toluene Total Hydrocarbon  30  Table 3.3   The OSPW characterization data from17 scientific sources: organic compounds (mg/L). Organic Compounds n Mean Std Dev Std. Error Max Min Median  CCME¹ CCME Benzene 3 2.267 3.239 1.87 6 0.2 0.6 0.0013² 0.006³ Bicarbonate  90 655.422 342.858 36.14 1290 75 664     Bitumen 6 28.182 33.195 13.552 92 0.094 18.5     Carbonate  51 36.471 53.923 7.551 335 0 21     Ethylbenzene 1 0.2 -- -- 0.2 0.2 0.2 0.09   m&p xylene 1 0.4 -- -- 0.4 0.4 0.4     NAs 96 39.479 30.375 3.1 130 0.005 44.15     o-xylene 1 0.2 -- -- 0.2 0.2 0.2     PAH gp5 5 0.62 0.574 0.257 1.2 0.01 0.59     Phenols 16 3.443 13.223 3.306 53 0.0005 0.0185 0.004   Tannin/Lignin 9 64.833 187.566 62.522 565 1 2     Toluene 3 3.433 2.676 1.545 6.3 1 3 0.002   Total Hydrocarbon 8 8.387 7.271 2.571 22 1 5.75      1. Long term 2. Monochlorobenze 3. Pentachlorobenzene 31  Organic compoundsBenzeneBicarbonate (HCO3-)BitumenCarbonate (CO3 2-)Ethylbenzenem&p xyleneNAso-xylenePAH gp5PhenolsTannin/LigninTolueneTotal HydrocarbonMean (mg/L)0200400600800 Figure 3.9 The OSPW characterization from 17 scientific sources: organic compounds mean concentration (mg/L) with standard error. *Mean exceeds the CCME Water Quality Guideline for the protection of aquatic life long term effects.       * * * * 32  3.2.1.3 Nutrients  The OSPW and tailings composition of nutrients includes the following, in order of descending mean concentration: nitrate (NO3-) (34 mg/L), total nitrogen (6 mg/L), ammonia (6 mg/L), total phosphorus (1 mg/L), nitrite (NO2) (1mg/L), orthophosphate (PO4 3-) (0.9 mg/L), nitrite and nitrate (NO2 + NO3-) (0.03 mg/L). The nutrient concentration ranges for all data from 17 scientific sources are shown in Figure 3.10. The nutrient sample sizes and data described with CCME guideline values are summarized in Table 3.4. The following nutrients which exceeded the CCME guideline limits included: ammonia, nitrate, nitrite and total phosphorus (Figure 3.11).   33   Figure 3.10 The OSPW characterization log 10 transformed data for 17 scientific sources: nutrients. The dots show all outliers, while line in the box represents median value and the whiskers above and below are 90th and 10th percentiles.           Nutrients1 2 3 4 5 6 7Log10 Data-3-2-10123Ammonia Nitrite Nitrate + Nitrite Nitrate Phosphate Total Nitrogen Total Phosphorous  34  Table 3.4   The OSPW characterization data from17 scientific sources: nutrients (mg/L). Nutrients n Mean Std Dev Std. Error Max Min Median  CCME¹ CCME² Ammonia 90 5.545 11.208 1.181 94.4 0.005 2.24 0.067³   Nitrate 4 34.487 20.914 10.457 49 4.65 42.15 13 550 NO2 + NO3- 9 0.0254 0.0216 0.0072 0.06 0.002 0.022     Nitrite 3 0.976 0.821 0.474 1.45 0.028 1.45 0.06   PO4 3- 2 0.85 0 0 0.85 0.85 0.85     TN 11 6.457 3.434 1.035 13 1.75 5.8     Total Phosphorus 12 1.165 3.916 1.131 13.6 0.005 0.015 0.01-0.02⁴   1. Long term 2. Long term 3. Ammonia at pH 9 and temperature 20˚C 4. Mesotrophic (natural reference systems) 35    Figure 3.11 The OSPW characterization from 17 scientific sources: nutrients mean concentrations (mg/L) with standard error. *Mean exceeds the CCME Water Quality Guideline for the protection of aquatic life long term effects.       NutrientsAmmoniaNitrate (NO3-)NO2 + NO3-Nitrite (NO2)PO4 3-TNTotal PhosporusMean (mg/L)01020304050* * * * 36  3.2.1.4 Elements  The OSPW and tailings element content is predominantly sulphur ranging in concentration from 539 to 0.001 mg/L. Review of 17 literary sources of data revealed the following metals  in order of descending mean concentration: S (93 mg/L), Mg (19 mg/L), La (3 mg/L), F (3 mg/L), Si (2 mg/L), Al (2 mg/L), B (1 mg/L), Fe (0.7 mg/L), V (0.7 mg/L), Br (0.6 mg/L), Sr (0.4 mg/L), As (0.2 mg/L), Ag (0.2 mg/L), Mo (0.1 mg/L), Ba (0.1 mg/L), Mn (0.1 mg/L), Li (0.08 mg/L), Sn (0.03 mg/L), Zn (0.02 mg/L), Ni (0.02 mg/L), Ti (0.02 mg/L), Cu (0.02 mg/L), P (0.02 mg/L), Pb (0.01 mg/L), Cr (0.01 mg/L), Zr (0.01 mg/L),  Co (0.009 mg/L), Sb (0.007 mg/L), Se (0.007 mg/L), U (0.006 mg/L), Cd (0.003 mg/L), Be (0.002 mg/L), Tl (0.002 mg/L), Hg (0.00004 mg/L), Y (0.00002 mg/L). The data ranges for these metals are shown in Figure 3.12.  Kelly and associates (2010) highlighted the oil sands industrial activities resulted in the increased loading of certain metals which included: Ag, As, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Se, Ti, and Zn. Analysis of pore water from CT, MFT, and native shallow wetland sediment contained As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, K, La, Mg, Mn, Mo, Ni, Pb, Rb, Sr, Y, Zn. Sansom (2010) indicated that OSPW from various tailings ponds indicated the presence of elements including Al, B, Cr, Cu, Fe, Li, Mn, Mo, Ni, P, Pb, S, Sb, Se, Si, Sr, Ti, V, Zn, Zr. Research by Zubot (2010) indicated that chemical analysis of fresh OSPW contained As (6 ppb), Cd (<1 ppb), Cu (1ppb), Cn (1 ppm), Hg (0.1 ppb), Pb (2 ppb), Ni (15 ppb), Se (15 ppb), V (20 ppb) and Zn (10 ppb). Analysis of trace metals in pore water from MFT and CT tend to have similar concentrations of As, Cu, La, Pb, and Y (Baker et al., 2012). Dubenest and associates 37  (2012) reported OSPW enrichment factors (EF) vanadium (EF = 66), aluminum (EF = 64), iron (EF = 52.5), and chromium (EF=39).  The analyses of 17 scientific sources of data indicate that the mean concentrations were assessed in relation to the CCME water quality guidelines for protection of aquatic life, as summarized in Table 3.5. The following metals exceeded the CCME guidelines: Ag, Al, As, Cd, Cr, Cu, F, Hg, Mo, Pb, Se, and Tl (Figure 3.13). In addition, although the following metal concentration means did not exceed the CCME guidelines their range in data had for the following: B, Fe, Zn. The concentration of P was equivalent to the CCME limit. Allen (2008) reported that those metals which have exceeded CCME by 50 – 100 % include Al, As, Cr, Cu, Fe, Ni, Pb, and Zn. Baker and associates (2012) indicated that the natural sediments and oil sands tailings on Syncrude lease property showed many trace metals exceeding the CCME guidelines, these included As, Cd, Cr, Cu, Mn and Mo.   38  Elements0 5 10 15 20 25 30 35Log10 Data-6-4-2024 Figure 3.12 The OSPW characterization log 10 transformed data for 17 scientific sources: elements. The dots show all outliers, while line in the box represents median value and the whiskers above and below are 90th and 10th percentiles.     Ag Al As B Ba Be Br Cd Co Cr Cu F-  Fe Hg La Li Mg Mn Mo Ni P Pb S Sb Se Si Sn Sr Ti Tl U V Y Zn Zr  39  Table 3.5   The OSPW characterization data from17 scientific sources: elements (mg/L). Elements n Mean Std Dev Std. Error Max Min Median  CCME¹ CCME² Ag 2 0.235 0.332 0.235 0.47 0.00005 0.235 0.0001   Al 16 1.556 4.632 1.158 18.9 0.072 0.435 0.1³   As 10 0.238 0.724 0.229 2.3 0.001 0.00855 0.005   B 76 1.355 1.086 0.125 4 0.0024 1.265 1.5 29 Ba 11 0.117 0.0768 0.0232 0.265 0.0016 0.1     Be 5 0.00226 0.00154 0.000687 0.0047 0.0005 0.002     Br 4 0.583 0.402 0.201 0.93 0.0022 0.7     Cd 8 0.00349 0.00425 0.0015 0.01 0.00008 0.00155 0.00009 0.001 Co 9 0.00879 0.0104 0.00346 0.025 0.00039 0.0036     Cr 8 0.0102 0.0106 0.00376 0.0332 0.0025 0.00485 0.001⁴   Cu 9 0.0171 0.0238 0.00795 0.076 0.001 0.0081 0.00261⁵   F 25 3.324 11.072 2.214 56 0.000047 0.6 0.12   Fe 36 0.705 2.069 0.345 12.5 0 0.2 0.3   Hg 5 0.0000434 0.00000853 0.00000382 0.00005 0.00003 0.000047 0.000026   La 3 3.334 5.773 3.333 10 0.00014 0.00066     Li 6 0.0845 0.0709 0.029 0.188 0.03 0.0495     Mg 97 18.672 19.945 2.025 139 2.1 11.7     Mn 21 0.111 0.0942 0.0206 0.3 0 0.1     Mo 15 0.148 0.167 0.043 0.5 0.00463 0.1 0.073   Ni 9 0.0201 0.0206 0.00688 0.0514 0.0012 0.011 0.10417⁶   P 2 0.015 0 0 0.015 0.015 0.015 0.01-0.02⁷   Pb 8 0.0128 0.0182 0.00642 0.0544 0.0003 0.00805 0.00368⁸   S 71 92.921 107.664 12.777 539 0.001 59.4     Sb 6 0.00733 0.00985 0.00402 0.02 0.0001 0.00185     Se 7 0.00724 0.00878 0.00332 0.02 0.001 0.003 0.001   Si 72 2.499 2.094 0.247 6.4 0.00017 1.85     Sn 1 0.025   0.025 0.025 0.025     40  Elements n Mean Std Dev Std. Error Max Min Median  CCME¹ CCME² Sr 77 0.372 0.317 0.0361 2.2 0.09 0.26     Ti 4 0.019 0.0131 0.00656 0.03 0.004 0.021     Tl 2 0.00158 0.00216 0.00152 0.0031 0.00005 0.00158 0.0008   U 1 0.0056   0.0056 0.0056 0.0056 0.015 0.033 V 11 0.688 1.017 0.307 3.04 0.001 0.05     Y 2 0.0000201 0.0000147 0.0000104 0.0000305 0.00000975 0.0000201   Zn 8 0.0215 0.0143 0.00506 0.0466 0.0094 0.0165 0.03   Zr 2 0.01 0 0 0.01 0.01 0.01     1. Long term 2. Short term 3. 100 µg/L if pH ≥ 6.5 4. Hexavalent (Cr(VI)) 5. Hardness 112 mg/L (At hardness >180 mg/L, the CWQG is 0.004 mg/L) 6. Hardness 112 mg/L (At hardness >180 mg/L, the CWQG is 0.150 mg/L) 7. Mesotrophic (natural reference systems) 8. Hardness 112 mg/L (At hardness >180 mg/L, the CWQG is 0.007 mg/L)   41   ElementsAgAlAsBBaBeBrCdCoCrCu FFeHgLaLiMgMnMoNiPPb SSbSeSiSnSrTiTlU V YZnZrMean (mg/L)020406080100120  Figure 3.13 The OSPW characterization from 17 scientific sources: metals mean concentration (mg/L) with standard error. *Mean exceeds the CCME Water Quality Guideline for the protection of aquatic life long term effects.         * * * * * * * * * * * * * * * * 42  3.2.1.5 Biology  The phytoplankton communities, apparently tolerant species to OSPW, include Botryococcus braunnii and Chlamydomonas spp. (Chlorophyta), Cryptomonas spp. and C. depressum (Cryptophyta), Ochromonas spp. and Chromulina spp. (Chrysophyta), Oscillatoria spp. (Cyanophyta), and Navicula spp. and Nitzschia spp. (Bacillariophyta) (Leung et al., 2001). Chlorophyta and Euglenophyta were among the most successful followed by Botryococcus braunni and Pandorina morum. These species appeared to be tolerant occurring within the settling basins with moderate naphthenate levels (8-21 mg/L) and in the MLSB. Herman and associates (1994) identified indigenous oil sands tailings bacteria which included: Pseudomonas stutzeri, Alcaligenes denitrificans, Acinetobacter calcoaceticus, Psedomonas fluorescens and Kurthia species. Del Rio and associates (2006) isolated Pseudomonas putida, Pseudomonas fluorescens from OSPW exposure areas. These organisms are capable of degrading organic compounds such as NAs. Baker and associates (2012) identified the presence of naturally occurring macrophytic alga, Chara species, which is capable of colonizing tailings, as well as, the invertebrates which included snails (Gastropoda: Lymnaeidae), dragonflies (Odonata: Aeshnidae) and larval chironomids (Diptera: Chironomidae: Chironomini).         43  3.3 OSPW CCME water quality index  The Canadian Environmental Quality Guidelines provide nationally endorsed recommended guidelines for chemical-specific substances, although not all substances currently have guidelines. The Canadian Council of the Ministers of the Environment (CCME) Canadian water quality guidelines for the protection of aquatic life, water quality index (WQI) (version 1.0) analyses certain conventional physical parameters, ionic, nutrient and metal content, in comparison to the guideline objectives (CCME, 2011). The WQI is highly utilized by academic, government and private sectors in Canada, as it provides a technique in rating the overall water quality. The tested and output data used in this study are found in Appendix A. The physical parameters consist of dissolved oxygen, hardness and pH. The ions and nutrients include ammonia, chloride, nitrate, total nitrogen, phosphorous and the abundance of primary producers as chlorophyll content (which provides insight into the ecology and possible nutrient content). The concentrations of metals consist of the following: Ag, Al, As, Cd, Cr-III, Cr-VI, Cu, Fe, Hg, MeHg (methyl mercury), Mo, Ni, Pb, Se, Tl, and Zn. The WQI score rates from 100, best water quality, to 0 the poorest water quality. The OSPW characterization data from 17 scientific sources was analyzed for the type of variables which did not meet the water quality objectives, the frequency of failing to meet the guidelines, and the amount or amplitude by which exceeded the recommended limits. The parameters and sample sizes were variable, due to differences in analysis and reporting. The following variables with respective number of sources: Ag (n=1), Al (n=2), As (n=3), Cd (n=4), Cl (n=7), Cr IV (n=4), Cu (n=4), Fe (n=4), Hg (n=2), Mo (n=3), NH3 (n=8), NO3- (n=1), P (n=5), pH (n=2), Se (n=2), Tl (n=1), Zn (n=2).  44  The WQI scores have been evaluated against the percent of completeness of data for the variables calculated (Figure 3.14). Some of the higher WQI scores are associated with lack of data and very few of the WQI variables were provided. El Din (2011) and Scott (2008) did not provide data for the specific variables being analyzed by the WQI calculator, the WQI value of 100 was due to deficiency of data. In addition, Tompkins (2009) was deficient in data and scored a WQI of 60, with chloride exceeding guideline objective by 5 times.  Leung (et al., 2003) and Peng (et al., 2004) respectively scored WQI 53 and 51, both lacked data, while Leung phosphorus exceeded objectives by a multiplication of times (x) 7 and Peng chloride exceeded by x 2- 7. Hrynyshyn (et al., 2012) sampling year of 1997 was poor in data, scoring a WQI 42, while the years of 2003 and 2007 had a moderate amount of data and scored 21 and 22. The following variables exceeded the water quality guideline objectives:  Ag x 4700, Al x 2-5, As x 2- 460, Cl x 5, Cd x 15- 40, Cr VI x 4, Cu x 10, Hg x 2, Mo x 7, P x 2- 680, Se x 3- 4, and Tl x 4. Mackinnon (et al., 2001) significantly lacked data, had a WQI score of 40, and 2 of 8 samples exceeded pH upper and lower limits. Ma (2012) had few data and the WQI score was 39, where chloride exceeded by x 2, and nitrate by x 3. Allen (2008) had a WQI score of 36, lacked all data except ammonia which exceeded the guidelines by x 933. Xiumei (et al., 2009) scored WQI 22, however, only contained data on two parameters, where ammonia exceeded by x 267- 1667 and chloride by x 2- 4. Holowenko (et al., 2000) had few data, the WQI score ranged from 21- 24; where ammonia x 447- 667, and chloride x 1.3- 4.  Van den Heuvel (et al., 1999) had adequate data and scored WQI 48, with the water quality guideline objectives exceeded in the following: Cd x 38, Cr (VI) x 3, NH3 x 5, and P x 4. Baker (et al., 2012) encompassed a moderate amount of data with a WQI of 37, where As exceeded up to 6 times, Cd x 2- 4, Cr (VI) x 3- 5, Cu x 3, Pb x 27, Fe and Zn by x 1.5. Holden (et 45  al., 2011) had few data and scored WQI 31, where NH3 x 135, and Cl- x 2.5. Sansom (2010) with a fair amount of data, WQI score ranged 16-18, with the following variables exceeding objectives: Al x 2- 9, NH3 x 7-2293, Cl x 1.4-5, DO in excess 1.5 and below by 9 times, Fe x 2-6, Mo x 1.4-7, and pH excess by x 1.04. Zubot (2010) with a complete data, had the WQI score range from 13-25, where guidelines were exceeding in the following: NH3 x 233-1000, chloride x 3-7, Cd x 5-250, Cr (IV) x 3-15, Cu x 8, DO x 11-1.6 below limit, Fe x 1.1, Hg x 2, Mo x 1.4-2, nitrate x 4, pH in excess x 1.01, phosphorus x 2, and Se x 2-20. 46   Figure 3.14 The CCME water quality index (WQI) calculations for the 17 sources of data on OSPW properties, in evaluated against the percent of completeness of data for WQI variables.    Data sourceSansom 2010Debenest et al 2012Xiumei et al 2009Holowenko et al 2000Zubot 2010Hrynyshyn et al 2012Holden et al 2011Allen 2008Baker et al 2012Ma 2012Mackinnon et al 2001Van den Heuvel et al 1999Peng et al 2004Leung et al 2003Tompkins 2009El-Din et al 2011Scott et al 2008020406080100120WQI score % data completeness Poor Best 47  3.4 OSPW parameters data source comparison  The following is a comparison of three sources of data which provide insight into water quality within the oil sands mining operations. Van den Heuvel (et al., 1999) site is a demonstration pond (57 4.94' N, 111 41.40' W), with an area of 4 hectares and a maximum depth of 2.9 meters, it contains 70,000 m3 MFT capped with 70,000 m3 surface water. The demonstration pond was constructed in 1993, for the purpose as a test site to assess remediation (e.g. such as end pit lake), and the data provided was from sampling for 2 years following completion. Zubot (2010) provides data from an active tailings pond sampled from 1997-2009. These data may provide insight into possible effects of age and technological innovations in oil sands extraction and enhanced settling of tailings. Sansom (2010) sampled from 2007-2008, the higher values correspond to from fresh OSPW at point source of discharge, active tailings pond, and drainage ditches, while lower values to the reference site of Mildred lake.  The OSPW and tailings are quite alkaline as shown in Figure 3.15 and the demonstration pond exceeds the most neutral pH values for the reference Mildred Lake. The conductivity of fresh OSPW is an approximate 17 times increase from the reference Mildred lake (Figure 3.16). The demonstration pond has conductivity similar to that of a drainage ditch or seepage from a waste site area. Sulphate concentrations from Sansom (2010) are 4 times the maximum concentration as Zubot (2010), likely due to point source of sample and differences in chemical additives (Figure 3.17). The sulphate may be reduced over time in conditions favoring sulphate reducing microbes. The demonstration pond has sodium and chloride content comparable to that of a drainage ditch or seepage from a waste site area, however sulphate content was higher like that of a tailings pond (Figure 3.17).  48    Figure 3.15 The comparison of water quality from three data sources: pH.   Figure 3.16 The comparison of water quality from three data sources: conductivity  Data source1 2 3pH6.57.07.58.08.59.09.5Data source1 2 3Conductivity ( microS/cm)0100020003000400050006000Van den Heuvel et al 1999 Zubot 2010 Sansom 2010  Van den Heuvel et al 1999 Zubot 2010 Sansom 2010  49  Figure 3.17 The comparison of water quality from three data sources: chloride, sodium and sulphate.        Cl (mg/L)020040060080010001200140016001800Na (mg/L)020040060080010001200140016001800Data source1 2 3Sulphate (mg/L)020040060080010001200140016001800Van den Heuvel et al 1999 Zubot 2010 Sansom 2010  50  All three data sources had similar trends in concentration of ammonia, calcium, potassium, magnesium, and naphthenic acids, although most abundant in fresh OSPW (Figure 3.18). The demonstration pond has a marked increased concentration of carbonate in comparison to OSPW either fresh or in a settling basin. The demonstration pond, tailings pond and drainage ditch had similar concentrations of metals including: aluminum, boron, iron, strontium and vanadium (Figure 3.19). However, there were reduced concentrations of manganese and molybdenum in the demonstration pond (Figure 3.20).  51     ammonia (mg/L)0100200300400Ca (mg/L)0100200300400Data source1 2 3Carbonate (mg/L)01003004   K (mg/L)0100200300400Mg (mg/L)0100200300400Data source1 2 3NAs (mg/L)01002003400 Figure 3.18 The comparison of water quality from three data sources: ammonia, calcium, carbonate, potassium, magnesium, and naphthenic acids.    52                        Figure 3.19 The comparison of water quality from three data sources: aluminum, boron, iron, strontium and vanadium.       Van den Heuvel et al 1999 Zubot 2010 Sansom 2010   Van den Heuvel et al 1999 Zubot 2010 Sansom 2010 53                  Figure 3.20 The comparison of water quality from three data sources: manganese and molybdenum.           Van den Heuvel et al 1999 Zubot 2010 Sansom 2010 54  3.5 Ecological effects 3.5.1 Athabasca watershed  The Regional Aquatics Monitoring Program (RAMP) (2012) which conducts environmental monitoring and research conducted in the Athabasca oil sands region regularly tests for the metals Ag, Al, As, B, Ba, Be, Bi, Ca, Cd, Cl, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, S, Sb, Se, Sn, Sr, Tl, Th, Ti, U, V, Zn. RAMP reported moderate changes in water quality from regional reference conditions, at Athabasca River, Steepbank River, Beaver River, McLean Creek, Mills Creek, Eymundson Creek; based on water quality index scores of 60-80 calculated with the CCME water quality index calculator. Gueguen and associates (2011) reported concentrations of Cd, Cu and Pb were above the Canadian and Albertan guidelines for the protection of aquatic life at sites in the Athabasca watershed near the oil sands development. Conly and associates (2007) reported the results of surveys which were conducted between 1998 and 2000 in tributaries of the Athabasca River which flowed through reaches with exposure to natural oil sand deposits, bed and suspended sediments of the Mackay, Steepbank, and Ells rivers showed metals As, Cd, Co, Cu, Fe, Mn, Ni, Pb, Sr, V, Zn. Polyaromatic hydrocarbons (PAHs) are found in the watershed of the Athabasca River, with concentrations of 0.009 mg/L from naturally occurring sources in upstream areas while 0.2 mg/L downstream areas impacted through contribution by industrial extraction activities that increased mobilization of total PAHs in the area (Leung et al., 2001). Land disturbances which expose the bitumen to wind and erosion, enhance bitumen transport to surface waters which leach out the most available polycyclic aromatic compounds (PAC) (Kelly et al., 2009). Previous studies found that in the lower Mackenzie River basin, flooding events of the Athabasca River is 55  an important vector that naturally supplies bitumen-sourced PACs to the Athabasca Delta (Yunker et al., 1993; Headley et al., 2002). Hall and associates (2012) findings suggested natural erosion is a major process in delivering PACs, with spring freshet key in mobilization and transport. Kelly and associates (2009) determined that PAH contaminated dust was deposited with snow, where samples contained up to 4.8 mg/L of PAHs at the end of winter; which could be a source of contamination through spring melt into the river systems. It was estimated that within 50 km of the oil sands upgrading facilities, airborne particulates may result in the deposition of 11,400 tonnes containing 391 kg of polycyclic aromatic compounds (of which 168 kg dissolved), over 4 months into snowpack.  3.5.2 OSPW toxicological effects  There are no surface water quality guidelines for naphthenates in Canada or the United States. The phytoplankton communities, apparently tolerant species, occurring within the settling basins with moderate naphthenate levels (8-21 mg/L) include Botryococcus braunnii and Chlamydomonas spp. (Chlorophyta), Cryptomonas spp. and C. depressum (Cryptophyta), Ochromonas spp. and Chromulina spp. (Chrysophyta), Oscillatoria spp. (Cyanophyta), and Navicula spp. and Nitzschia spp. (Bacillariophyta). Chlorophyta and Euglenophyta were among the most successful while Botryococcus braunni and Pandorina morum appeared to be tolerant. The toxicity of PAHs included research on the effects of OSPW in fathead minnow (Pimephales promelas) larvae exposure resulted in larval mortality directly correlated to the cytochrome P4501A1 activity (Gagné et al., 2011). The observed toxicity was linked to three or 56  more aromatic ring PAHs. It was determined that only PAHs with high molecular weight tended to induce genetoxicity, while smaller PAHs (e.g. three to four aromatic rings) induced glutathione S-transferase (GST) activity. Reproduction impairment in fathead minnow exposed to aged oil sands tailing pond water, approximately over 15 years and containing 10 mg/L NAs, completely inhibited spawning and diminished male secondary sexual characteristics (Kavanagh et al., 2011). In addition, research by Gentes (2006) on native populations of tree swallows (Tachycineta bicolor) in the Oil Sands mining areas had decreased reproductive success, where an increased nestling mortality, with rates of 100% at sites with highest PAH and NA concentrations.  The elements which were identified in section 3.2 as exceeding the CCME water quality guidelines for the protection of aquatic life include: Ag, Al, As, B, Cd, Cr, Cu, F, Fe, Hg, Mo, Ni, P, Pb, Se, Tl, U and Zn. Some elements are bioaccumulative (e.g. Ag, B, Hg, Se, Tl). The toxicity of Ag is primarily understood through research on rainbow trout (CCME, 2014). The mechanisms of toxicity involve disruption of ionic balance through competition with Na+ channels. In fish the organ first affected are the gills, where Na+ and Cl- regulation is disrupted, causing circulation breakdown. Accumulation of silver results in irreversible binding which inhibits enzyme activity of the basolateral Na+K+-adenosinetriphosphatase, resulting in ionoregulatory disruption and to the extent of damage, subsequent death. The existing research on Arsenic (As) does not indicate that it is capable of biomagnifying (CCME, 2014). The uptake of As is at sorption sites where there is competition from P, the interaction can reduce As uptake. Fish, invertebrates and plants have exhibited As toxicity. Some adverse effects include increased mortality, decreased ecological communities abundance, and behavioral changes in animals. 57  Elemental boron (B) is insoluble and inert in aqueous solutions, however, in alkaline conditions forms borate ions (CCME, 2014). Boron readily undergoes adsorption-desorption reactions with sediments; dependent upon pH (7.5-9.0) and concentration. The naturally stable forms of B, undissociated boric acid (B(OH)3) and complex polyanions (e.g., B(OH)4-) are highly soluble and long lasting. Boron enters an organism through active and passive transport and does not appear to biomagnify in the aquatic food chain. B is an essential nutrient, however, beyond certain threshold levels cause mortality and teratogenesis (e.g. rainbow trout). Cadmium (Cd) in solution may be present as hydrated ions, chloride salts, and may chelate with inorganic ligands, or organic ligands (CCME, 2014). Toxicity and mobility is dependent upon pH, alkalinity, hardness and organic matter. Cd is non-essential element which blocks calcium uptake channels, and resulting in hypocalcaemia. Toxicity of Cd has been shown to be decreased by increased hardness (abundance of Ca2+ and Mg2+). Chromium (Cr) exists in different aquatic states, where (III) is most common and stable by forming highly insoluble oxides, hydroxides, phosphates and strong tendency to adsorption to surfaces (CCME, 2014). Cr (VI) compounds are highly soluble, strongly oxidizing, have a long residence time and infiltrate biological membranes with ease and can cause mortality. Copper is an essential trace element, where detrimental effects include sublethal behavioral effects (e.g. decreased predator avoidance response), increased mortality and decreased biological diversity (CCME, 2014). The extents of these effects occurring are difficult to predict from concentrations alone, other influential factors include species sensitivity, endpoints and other factors that affect bioavailability (e.g. physicochemical, feeding behavior and uptake rates, geochemical). 58  Fluoride (F) toxicity include impaired reproduction and reduced hatchability and sublethal effects in fish which included disrupted  migration patterns (CCME, 2014). Toxicity to aquatic organisms and plants is enhanced by the presence of metals, especially aluminium. Fluoride forms soluble complexes with Al under acidic conditions (e.g. pH<5), low hardness, and availability of ion-exchange material (e.g. bentonite clays). Mercury (Hg) is considered one of the most toxic, with numerous chemical compounds which are quite stable (CCME, 2014). Methylmercury (MeHg) is very toxic to fish, invertebrates, and plants, it accumulates readily in aquatic biota and is more than ten times as toxic as HgCl2. Inorganic Hg is known to cause detrimental effects such as significantly decreased growth, impaired development (e.g. deformities), decreased survival and mortality. Toxicity significantly increases with temperature, while reduced with salinity, selenium, and dissolved oxygen content. Molybdenum (Mo) is an essential element, which readily forms organometallic complexes, predominantly molybdenum sulphide (MoS2), molybdate (MoO42-), and bimolybdate (HMoO4-) (CCME, 2014). Mo form is pH dependent where MoO42- predominates in alkaline conditions and forms complexes in acidic conditions (e.g. with Fe and Al). Current research does not show bioaccumulation in fish. Some adverse effects include decreased number of offspring, inhibited growth and mortality at various concentrations. There are several physical, chemical and biological factors which influence the transport and fate of Nickel (CCME, 2014). The most important may be pH, followed by the presence of organic materials, hydroxides, clay minerals, cations, and ligands. Nickel (Ni) readily adheres to negatively charged surfaces. Ni is absorbed through gut, transported throughout the body, where it accumulates in the kidneys. 59  Phosphorus is an essential nutrient which can increase plant and algal productivity and biomass (CCME, 2014). However, in excess of guideline thresholds can cause undesirable effects in biodiversity, increased turbidity, excess of biomass and organic matter and anoxic conditions. Lead (Pb) readily adsorbs to clays and organic matter (CCME, 2014). Toxicity effects are diverse and can include changes in behavior, dehydration, muscle spasms, impacted gastrointestinal tract, reproductive dysfunction and death. Some research indicates that some lead salts are genotoxic, however evidence for carcinogenesis is inconclusive. Selenium (Se) is considered an essential metal in animal nutrition, due to its role in enzyme glutathione peroxidase which inhibits oxidation by peroxides and hydroperoxides (Pyrzynska, 2002; Pyrzynska, 1998). Selenium is thought to protect immune system cells, slows ageing processes, protects against cancer and prevents heavy metal toxic effects. However, the concentration range for Se nutritional requirements is limited (e.g. humans 55μg daily intake). Excessive elemental Se can be excreted through the hair, urine, and exhaled breath (e.g. methylated selenides). Inorganic forms of selenium, selenite (SeIV) and selenate (SeVI) are metabolized differently. Selenite transported into red blood cells (RBC) where glutathione reduces selenite to selenide which travels to the plasma and then to the liver where it binds to albumin. Selenate moves out of bloodstream, is not uptaken by RBCs, to the liver where it is reduced by glutathione to selenide, which is then transformed into organic selenoproteins or methylated compounds.  Methylated selenides excreted into urine and breath. Plants, fungi and microbes can transform inorganic forms into volatile organic forms (e.g. dimethylselenide). Selenium is closely associated with sulfur, the similar ionic radius (Se 198pm; S 189pm) allows for ionic substitution of Se for sulfur in organic compounds. Selenocycteine is considered highly 60  toxic due to replacement of sulfurcysteine, results in the loss of enzyme activity due to presence at sites on selenoproteins. Thallium (Tl) under alkaline conditions adsorbs to montmorillonite clay (pH 8.1) and binds to humic acids (CCME, 2014). Uranium has a tendency to partition into sediments and reversibly bind to mineral surfaces. Accumulation in fish tends to occur in bones, scales and gonads. Research indicates that U is not readily bioaccumulate due to a low assimilation capacity. Some adverse effects include reproductive impairment and mortality. Zinc is an essential element, which has a strong affinity binding to particles (e.g. iron and manganese oxides) and organic matter. Some adverse effects include behavioral changes, mortality and decreased diversity and abundance.               61  3.6 Tailings pond processes  3.6.1 Overview  Oil sands tailings ponds undergo natural and artificially assisted enhancement of physical division (e.g. settling) of the process affected water and tailings into compartments three main include the free water on the surface of the pond, with fine tailings below (in fluid state) and the bottom layer of mature fine tailings (Bordenave et al., 2010; Chalaturnyk et al., 2002; Fedorak et al., 2003). The volumes and boundaries of the tailings pond compartments can change over time. There are various physical, chemical and biological processes which occur within the various compartments of a tailings pond. A conceptual model diagram of a tailing pond compared to the drawing by Zubot (2010) is seen in Figure 3.21.     Figure 3.21  Tailings settling pond cross section (to the left image retrieved from Zubot (2010)) with conceptual Tailings Pond Model compartments (to the right).  Mature Fine Tailings Soil  OSPW Free Water   Fine Fluid Tailings       Pipe Outflow 62  The various inputs and outputs into a tailings pond are conceptualized in Figure 3.22.  The OSPW enters the system, where solids precipitate and there is stratification of various compounds into the various compartments (Baedecker et al., 2011; Vandenberg et al., 2012). Volatile compounds such as gases will evolve out of the pond and into the atmosphere (e.g. methane (CH4), volatile organic compounds (VOCs), hydrogen sulphide (H2S), oxides of nitrogen (NOx), organic compounds (OCs)). Water will also be lost through evaporation and some seepage, while gain may also occur through precipitation, seepage and from ground water through capillary action, percolation and osmotic suction.                63                             Figure 3.22  Tailings pond conceptual input and output of all compartments. Dissolution H2O, ions, metals, OCs Seepage H2O Soil  Absorption (e.g. ion exchange, van der Waals, filtration) Mature Fine Tailings  Biodegradation (e.g. methanogenesis)  Adsorption (e.g.  ion exchange)  Consolidation H2O Percolation H2O Percolation H2O, ions, metals, OCs Dissolution CH4, VOCs, NOx Sand, clay, metals, OCs Precipitation, Settling Mixing (flow, density, convection, wind) OSPW Free Water  UV, Oxidation, Reduction  Chemical speciation Fine Fluid Tailings  Biodegradation (e.g. sulphate reductions)  Adsorption (e.g. ion exchange) Sand, clay, metals, OCs CH4, VOCs, H2S, NOx O2, UV, H2O H2O CH4, VOCs, H2S, NOx Evaporation Precipitation, Settling H2O Percolation H2O Percolation 64  3.6.2 Physical processes: limnology  3.6.2.1 Properties of water  The molecular properties of water are unique (Lampert et al., 2007). Ice melts at 0 °C and water is most dense at 4 °C. In ice, water molecules are widely spaced forming a crystalline matrix with a relatively low density. The difference in density between ice and liquid water (at 0 °C) is 8.5%, which allows for ice to float on the water surface. In comparison, the water density of 0 °C is less dense than 4 °C by a difference of approximately 0.13 g/L, while 4 °C and 20 °C is 1.77 g/L. This density gradient allows for the thermal separation of water into layers of different temperatures and density. Although there are no specific limnology studies on tailings ponds, these basic concepts are applicable. The high salinity and warm temperature of OSPW would drive density and thermal driven convection and possible stratification.  3.6.2.2 Meteorological variables  Most of the exchange of heat between a body of water and the environment takes place through the water surface, where, solar radiation entering a water body, especially the long wavelengths, is absorbed near the surface and transformed into heat (Lampert et al., 2007). However, heat does not remain where it is absorbed; wind and density of water play large roles in thermal distribution and circulation within water bodies. In water bodies solar radiation absorption of short-wave radiation (e.g. ultraviolet (UV)) occurs within uppermost few centimeters of the epiliminion surface, while visible light may reach depths of tens of meters 65  (e.g. visible infrared (IR)) (Girgis and Smith, 1980). Heat energy is primarily lost through wind induced convection and emission of long-wave radiation (Edinger et al., 1968; Pham et al., 2008). Mass fluxes such as precipitation may also influence heat transfer. The body of water may undergo spatial and temporal fluxes due to atmospheric influences on the heat balance at the water surface (Livingstone, 2003).  Although there are no specific limnology studies on mixing and convection in tailings ponds, these former basic concepts are applicable. The salinity and temperature of OSPW would drive density and thermal driven convection. In addition, the dark oil film covering the surface would enhance solar heating during the summer, while ice cover in winter would reflect solar radiation. Jiang and associates (2013) describe wind driven wave action on tailings ponds, such as MLSB, and indicate that tailings pond design includes a water cap to facilitate settling of solids and to reduce the resuspension of fine solids. The importance of this design is in maintaining a low TSS for recycling water for use in operations.   3.6.2.3 Circulation  The vertical temperature distribution in water bodies is dependent upon surface heating, and the propagation of heat (e.g. via molecular diffusion, convection, eddy viscosity) (Girgis and Smith, 1980). The extent of circulation patterns and heat exchange within a water body will be dependent on the physical dimensions (Bennett, 1978). Heat exchange will occur at the surface, where temporal atmospheric variations will influence heat gain and loss. These variations will influence vertical mixing. Depth is correlated with heat loss, whereby deeper water bodies can store a significant amount of heat in the water during the heating period in the summer which 66  tend to promote reduced total heat loss in fall and winter (Hostetler et al., 1990). Fall cooling and wind storms may enhance vertical mixing and result in increased depth of the epiliminion (Alvarez-Cobelas et al., 2005; Bennett, 1978).  Spring heating, melting ice produces low density water (0 °C), which through solar heating increases in temperature and density resulting in high density water (4 °C) which sinks contributing to vertical mixing and the downward transport of heat (Bennett, 1978; Jonas et al., 2003; Noges et al., 2011; Read, 2012). In addition, mixing aided by spring winds, and conduction at the surface is expedited due to low thermal resistance and relatively light winds can easily complete circulation (Welch, 1952). This period may be named the overturn or turnover period (Bennett, 1978). Rapidly rising atmospheric temperatures in summer will result in thermocline development, where heat transfer to the hypolimnion is greatly reduced.  3.6.2.3.1 Dimictic  The most common type of thermal cycling in water bodies of temperate latitudes is dimictic where mixing occurs twice a year; in spring and fall (Lampert et al., 2007; Mishra et al., 2011; Wetzel, 1983). Colder air temperatures and decreased solar radiation in the fall will facilitate surface cooling, whereby denser surface water will then sink causing a turn-over. Typically in temperate regions, winter temperatures may drop low enough that surface ice is formed. In spring, winter ice will melt and cold (denser) melt water will sink resulting in a second turn-over. Dimictic water bodies may experience stratification twice a year, winter and summer. In winter, water is most likely to achieve maximum density (4 °C) and lake stratification will be stable in the presence of ice cover to insulate from wind mixing. 67  Warmer air temperature and increased solar radiation during summer result in the most evident thermal stratification, where warmer water lies above colder water; the top layer being the epilimnion and the bottom layer the hypolimnion (may have a 10 °C difference) (Read, 2012; Welch, 1952). Summer circulation typically occurs in the epilimnion. Winter may be referred to as a stagnation period, where a permanent ice cover will insulate the water body from the influences of wind, the lowermost layer is typically 4 °C and warmer than the uppermost layers; a thermal profile in reverse from summer. Holowenko and associates (2000) reported stratification in MLSB temperature depth profile in July 1998. Data collected on temperature (˚C) and corresponding depth sampled: 22˚C at 1m, 14˚C at 5 m, 13.5˚C at 8 m, 12.5˚C at 10 m, 11˚C at 15 m, and 11.5˚C at 20 m. In addition, temperature within the FFT layer fluctuates from 11-15 ˚C within a one year cycle.  3.6.2.3.2 Meromixis  Stratification can be affected by a salinity gradient, where denser more saline water accumulated at the bottom. In meromixis, the water body has the deepest section permanently isolated from the uppermost layers (Hrynyshyn et al., 2012). This salinity-driven density gradient results in a lack of turnover. In addition, winter ice-cover can purge salts which then accumulate at the bottom, resulting in a freshwater capped uppermost layer. Meromixis may occur in Oil Sands settling basins due to the high salt concentrations. Holowenko et al. (2000) sampled the Mildred Lake settling basin, in 1997 and 1998, at various interval depths from 1m to 20 m, however, the water quality data did not appear to reveal any significant difference in salt and ions concentrations from upper to deeper depths. 68  3.6.2.4 Role of ice cover  Most temperate water bodies experience an ice-free period that is typically from late spring to early fall (Mishra et al., 2011). Wave action during winter on an ice-free surface may result in deeper mixed layer and weaker thermocline (Bennett, 1978). Ice free surfaces enhance heat loss, whereby the water surface is exposed to cool winter air. Ice cover aids in the prevention of heat losses, this cover greatly reduces convective forces (e.g. wind), while diffusion of heat may occur at the molecular level (Hostetler et al., 1990; Kirillin et al., 2012; Mishra et al., 2011; Rouse, 2009). The length of the stratified period is related to the timing of turnover, where early ice break-up may lead to greater accumulation of heat (heat storage) within a water body which could result in a later winter freeze-up.  3.6.2.5 Settling  The oil sands extraction processing produces a slurry of liquid waste containing salt constituents, fines (clays and silts), residual bitumen, and various organic and inorganic components (Leung et al., 2001). Tailings are composed of fine suspended particles, metals, anionic aromatic and aliphatic hydrocarbons (Gagné et al., 2011). The major clay components of the Fort McMurray formation are (40-70 weight percentage (wt %), illite (28-45 wt %) and montmorillonite (1-15 wt %); the latter  has the highest affinity to water (swelling when hydrated) and the largest cation exchange capacity, while illite and kaolinite are repelled (Chalaturnyk et al., 2002). Low energy extraction, such as OSLO cold water process (35˚C), produces a tailings effluent slurry with better consolidation and reduced volume of process 69  water. The caustic (NaOH) hot water treatment results in a clay water slurry where formations of water-in-bitumen emulsions and dispersal of clays in water are created. This slurry mixture contains sand particles (82 wt %), dispersed fines with a diameter smaller than 44 μm (17 wt %), water and residual bitumen (1 wt %).  At discharge of tailings into the ponds coarse sand particles quickly separate and settled to form beaches and the containment dikes (Chalaturnyk et al., 2002; Xiumei et al., 2009). The fine tails accumulate in the tailing ponds, initially fines will settle out quickly, while others remain in suspension for years and it may take a few years for a 10% reduction; consolidating into mature fine tails (MFT) (approximately >35 wt % fines). Mature fine tails have a very slow rate of consolidation and will remain in a fluid state for decades. Organic materials present, such as humic acids and asphaltenes bind to clays, which act as clay dispersants. Studies have shown that pH increases above 10 (OH- ions) or below 6 (H+ ions) will encourage settling. NAs are naturally occurring surfactants and are released to OSPW (20-120 mg/L) during the alkaline extraction conditions. Frank (2008) reported tailings water pH 8-9 and stipulated that at those conditions the NAs would be in the form of sodium naphthenate salts (density 1.059 g/cm3 at 20 °C). The surfaces of these ponds are covered by oil films, ranging from monolayer to several centimeters thick and NAs have been reported to concentrate at the surface (Xiumei, 2009).  Tailings consolidation has been shown to be increased with methanogenic activity, with different classes of microorganisms contributing to increased tailings aggregation and sedimentation (Bordenave et al., 2010). Microbial activities are shown to improve tailings densification, where sedimentation processes occur at the top of a tailings column and consolidation near the bottom. The estimated rate of densification of mature fine tailings is 150 years (Eckert et al., 1996). Methanogenic activity has been shown to accelerate the process with 70  an estimated densification within less than 1 year which would take 15 years without microbial activity (Fedorak, 2003).  Metals interact with inorganic and organic molecules and particles (Gueguen et al., 2011). The mobility and potential biological effects of trace metals is related to physical speciation. The molecular weight will affect distribution, residence time, concentrations, adsorption to particles, and whether they will remain suspended in the water column or settle to underlying sediments. The binding of metals to dissolved organic matter, through ligands, increases their residence time in the free water. In this form metals are generally less bioavailable, and uptake across cell membranes is likely improbable due to size. OSPW has increased loading of Ag, As, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Se, Ti and Zn (Kelly et al., 2010). Some elements identified tend to be associated with particulates included Be, Hg, Ni, and Pb. Sites upstream and near the oil sands development (n=11) showed particulate and dissolved phases of Cd, Co, Cu, Ni and Pb (Gueguen et al., 2011). The concentrations of Cd and, Cu and Pb at some sites, were above the Canadian and Albertan guidelines for the protection of aquatic life.  3.6.3 Chemical and biological processes  3.6.3.1 Partitioning  The partitioning of various ions, elements and organic compounds within tailings ponds are interlinked between solid, aqueous and organic phases. OSPW is high in bicarbonate, Cl, Na, and S. The geology of the Athabasca basin is glacial till which is low in Ca, K, Mg, and Na 71  (Holden et al., 2011). Na has a high affinity to bind to clay in tailings and concentration is positively correlated with sorption rate. Ca and Mg ions are released into dissolved phase from clay through Na induced desorption, dissolution of sulphate salts, and precipitation of carbonate mineral phase. Increased concentrations of Ca and Mg will drive the formation of Ca and Mg sulphate salts. At oversaturation sulphate salts remain in solution while carbonate salts will precipitate. Cl ions tend to remain in solution and less likely to interact with clays. Elements partition through binding to organics forming protoporphynn-metal complexes, with Ag, Cd, Cu, Hg, Ni, Pb and Zn (Allen, 2008; Baker, 2012). Precipitation into MFT tends to include As, Ba, Ca, Co, Cr, Fe, Ga, K, La, Mg, Mn, Mo, Rb, Sr and Y. Certain elements associate with particulates, Be, Cd, Co, Cu, Hg, Ni and Pb. Although, some of these elements are also in the dissolved state, Cd, Co, Cu, Ni and Pb; indicating a tendency to more susceptible to adsorption and desorption. Enrichment of OSPW is through leaching of natural ore and parent materials (e.g. sand, clay) and chemical processing additives (e.g. gypsum acid salt, hydrogen sulphide) (Van den Heuvel et al., 1999). Processing and treatment tend to release from the ore and clays certain elements, B, La, Li, S, Sr, Y, Zn. The components of bitumen include maltenes (saturates, resins, aromatics) which tend to be liquid at ambient temperature and remain soluble, while asphaltenes remain insoluble and partition into the MFT (Nji, 2010). Interfacial tension between water oil interfaces are pH dependent and indigenous surfactants (e.g. NAs) relax the interfacial tension (Kelesoglu et al., 2011). Interfacial tension decreases when the adsorption rate is greater than the desorption rate. As the pH in the aqueous phase increases, the acidic surfactant may change from nonionic to ionic forms. NAs tend to partition between oil and water during production (e.g. naphtenate "scales" from sodium-rich emulsions, calcium naphthenate deposits) (Mohammed et al., 2009). 72  During oil sand processing the formation of stable water oil emulsions may be the result of the formation of sodium salt from monoprotic naphthenic acids (Nordgard et al., 2012).  Molecular weight of the NAs influence the rate of partition into the water phase, increased with lower molecular weight (Mohammed et al., 2009). NAs partitioned into the water phase may dissociate with normal equilibrium and form a precipitate (e.g. calcium salt). Also, the portioning of NA is a function of pH with precipitation of salts occurring at lower pH (Nordgard et al., 2012).  3.6.3.2 Degradation  The variable organic constituents of OSPW provide sources of carbon for aerobic and anaerobic microorganisms (Scott, 2007). The nutrient availability is a limiting factor in biodegradation. Continuous input of fresh tailings hinders biodegradation of more complex organic compounds (e.g. NAs). The complexity of the molecules contribute to their greater recalcitrance, where NAs with longer alkanoic groups and or additional alkyl substitutions on the ring and or quaternary carbons. NAs are the last carbon source for microbes, to be degraded following the depletion of other more easily metabolized compounds, due to their toxic or inhibitory nature to microorgansims.  Natural attenuation of NAs in tailings ponds has been described by Herman and associates (1994) to be the result of aerobic microbial degradation and subsequent reduced toxicity. Holowenko and associates (2002) reported reduced toxicity in aged process affected water. An investigation into the change in naphthenic acid isomer groups in OSPW over time indicated a reduction in NAs with less than 21 carbon atoms, while higher molecular weight appeared to be less biodegradable. Holowenko et al (2001) showed alicyclic ring cleavage and 73  subsequent degradation possible under anaerobic conditions. Some limiting factors in biodegradation include mixing efficiency (bioavailability of substrate), temperature, pH, concentration dissolved oxygen, nutrients (e.g. N and P).  Continuous input of fresh tailings to the ponds might hinder biodegradation of NAs because of excess available organic compounds (NAs are the last step when carbon sources are used up). Commercial NAs are more biodegradable than those from oil sands origin (Scott, 2007). Herman and associates noted that in microbial degradation of commercial NAs, converted approximately 50% of the organic carbon into carbon dioxide (CO2) and acute toxicity testing with Microtox revealed complete absence of detectable toxicity following the biodegradation of NAs.  Tailings pond and seepage water on the Suncor property containing moderate naphthenate levels (8–21 mg/L), were populated by many tolerant phytoplankton taxa, including Botryococcus braunnii and Chlamydomonas spp. (Chlorophyta), Cryptomonas spp. and C. depressum (Cryptophyta), Ochromonas spp. and Chromulina spp. (Chrysophyta), Oscillatoria spp. (Cyanophyta), and Navicula spp. and Nitzschia spp. (Bacillariophyta) (Leung et al., 2001). Botryococcus braunni and Pandorina morum were the most tolerant to MFT and Mildred Lake settling basin water. Chlorophyta and Euglenophyta were among the most successful groups in mesocosm NA exposure studies.  Scott (2007) indicated that research has discovered some newly emerging treatment options to break-down the recalcitrant nature of NAs. Chemical oxidation (e.g. UV irradiation, ozonation) can alter chemical structure of recalcitrant compounds facilitating microbial degradation. Ozonation pretreatment to microbiological processes has shown to improve biodegradability by removing compounds toxic to microorganisms, reducing molecular weight of organic contaminants, or by changing the form of the organic contaminants to more 74  susceptible to microbial attack. This pretreatment has been used in various industries to enhance effluent treatment such as pulp and paper, olive oil production, petrochemical, and wastewater from oil field drilling. The demonstrated treatment which is most effective consists of 5 minutes of ozonation and 12 h biodegradation which result in a 50% decrease of total organic carbon. Interestingly additional ozonation proves detrimental to the process as ozonation longer than 5 minutes will result in transformation into recalcitrant compounds essentially less biodegradable.  The Mildred Lake settling basin, fluid surface area of 10 km2, has over the past 20 years shown methanogenic activity, where surface bubbling activity was observed in the 1990s on south side and has since moved north (Holowenko et al., 2000; Xiumei et al., 2009). The gas flux is estimated 60-80% methane, equivalent to 12g CH4/m2/day (Holowenko et al., 2000).  The methane percolation enhances transport of NAs from tailings pore water into capping water layers. Holowenko and associates reported the interface of free capped water and fine tailings to occur at 2.5 to 3 meters below the surface (based on 1997 and 1998 sample collection). Sampling determined sulphate reducing bacteria to be located at the surface water (1 m), while below 5 m the methanogenesis which inhibited sulphate bacteria. The rate of methanogenesis is slower at low temperatures and the water bodies in the region typically experiences ice cover for approximately 6 months. In addition, winter ice cover typically produces anoxic conditions. Beta-oxidations of NA side chains yield acetic acid and H2 which are substrates for methanogens; acetate stimulates methane production (Holowenko et al., 2001). Continuous input of fresh tailings to the ponds might hinder biodegradation of NAs because of excess available and more easily degraded organic compounds; since typically microbes utilize NAs when other sources are depleted (Scott 2007). 75   A variety of anaerobic microbes, such as methanogens, sulphate- and nitrate-reducing bacteria have been found in tailings ponds and microbial metabolism causes major emissions of methane and carbon dioxide (Bordenave et al., 2010). The addition of nitrate is known to lower methane production. Under methanogenic and nitrate-reducing conditions larger particles (50– 100 µm) tended to be more depleted in Al and Si and more enriched in C and P.  3.6.3.3 Seepage  The Mildred Lake settling basins have an estimated total time for dyke seepage as 20 years (Xiumei et al., 2009). The sediment is considered to be under anoxic conditions. Analysis of pore water from within the dykes contains higher amounts of NAs which have not undergone biodegradation. Micropore size can deny access to decomposer organisms (Ladd et al., 1993). Ladd and associates (1993) identified increased survival of bacteria and fungi in clay soil, with silt and coarse clay fractions. Microbial access into empty space was assisted through drier conditions, and resulted in aerobic activity when air filled these pores. Movement in the vadose zone undergoes filtration through mechanical, straining, and attachment (Sen, 2011). Particles with an electric surface charge, known as colloids, include silicate clays, iron, aluminum oxides, mineral, and humic. Adsorption through electrostatic and van der Waals forces is weak and reversible, while adhesion by physical and chemical attachment, tend to be irreversible. The geological origin of oil sands tailings ponds constructed materials are from glacial till sediments (Holden et al., 2011). Research in clay mineralogy, indicate that the glacial till sediments have a decreased abundance of cations of calcium, magnesium, sodium and potassium, while OSPW contains high concentrations of sodium, chloride, sulphate and 76  bicarbonate ions. Calcium and magnesium may be displaced from clay through ion exchange with sodium in OSPW; which may result in precipitation of sulphate and or carbonate minerals. Holden’s research revealed a linear response for sodium in cation sorption with increasingly concentrated process affected water. Soluble calcium, magnesium and potassium salts complicated the mechanism of desorption. OSPW appears to be oversaturated in dissolved carbonate and sulphate, where carbonate salts tend to precipitate out, while sulphate salts remain dissolved. Calcium and magnesium showed a similarly constant rate of release into solution over varying concentrations, although the former tended to be two fold in magnitude. The mechanism at which calcium and magnesium are released into solution included the dissolution of sulphate salts, sodium-induced desorption, and precipitation of the carbonate mineral phase. Holden et al. (2011) reported that increased saturation of OSPW will result in the dissolution of pre-existing calcium and magnesium sulphate salts. Chloride ions tend to remain in solution, and do not interact with sediments or pore water; ions are not taken up or released. The interactions of naphthenic acids with native soils have not been researched in depth; particularly in regard to adsorption and ion exchange.          77  3.7 Tailings pond conceptual model  The following conceptual model of an oil sands tailings pond, based on data from MLSB, is a first of its kind. Literature review revealed gaps in attempts to define the objectives for modeling and create a conceptual model. A model was created specifically for the sediment transport of TSS in MLSB (Jiang et al., 2013). The modelling software was COSED-UF, also known as the integrated three-dimensional (3D) hydrodynamic and sediment transport mode (ICOSED-UF 3-D) (University of Florida). The use of this hydrodynamic model proved to be difficult and required additional modifications and calibrations. Vandenberg and associates (2012) describe the theory behind modeling hydrodynamic water quality of reclamation areas in the oil sands affected landscape, through conceptual modeling and the utilization of software.  The process of modeling is quite complicated given the various physical, chemical, biological, geochemical, hydrological and limnological processes involved.  Chemical modeling such as water and mass balance in 0-D can be achieved through simple software (e.g. Microsoft Excel) and could be combined with geochemical model (e.g. PHREEQC (Parkhurst and Appelo, 1999)). Physical and chemical modeling may include variables such as depth in 1-D (e.g. DYRESM coupled with CAEDYM (Hipsey et al., 2006), or lateral and depth as 2-D (e.g. CE-QUAL-W2 (Cole and Wells, 2008), MIKE21 (Danish Hydraulic Institute, 2011), or as a 3-D hydrodynamic and water quality model (e.g. MODFLOW (Harbaugh et al., 2000)). Attempts to predict water quality in proposed reclamation through the creation of pit lakes, appear to remain in theory, as there were no modeling results published.  The following conceptual Tailings Pond Model defines the physical, chemical and biological characteristics and processes. The conventional variables within the compartments of 78  the conceptual Tailings Pond Model are described in Figure 3.23. The tailings pond is composed of three main compartments: free water, fine fluid tailings (FFT), and mature fine tailings (MFT). Holowenko and associates (2000) sampling of MLSB, in 1997 and 1998, the interface of free water and FFT was 2.5-3 m below the water surface. Research conducted by Jiang and associates (2013) sampled MLSB, confirmed a surface area of 12 km2. The uppermost layer was defined as the free water cap, had a depth of 5 meters, and was observed as a mixed layer, typically affected by wind. The FFT was sampled as having a depth of 1 meter and a sharp increase in TSS from 0.1% at the free water to 15% in the FFT. The MFT, with a TSS 60%, was described as stationary; however intense wind and wave action could resuspend fines. Fines tend to aggregate in flocculation, settle and deposit onto the MFT. Vertical mixing can resuspend fines, and could be due to the following forces: heat exchange at water surface, wind driven currents and waves, and density gradients. The surface of the pond is covered in a film of oil approximately 1 cm thick and can range to several centimeters (Holowenko et al., 2000; Xiumei et al 2009).  The pond exhibits stratification with the separation of oil film and free water, furthermore, denser more saline water forms a cap of highly saline water covering the mature fine tailings. The suspension of clay, silt and other particles is driven by mixing from the inflow of fresh OSPW, seasonal variation in freeze and thaw, wind, and convection. Settling of particles assisted gravity and enhanced through microbial action. The consolidation of MFT will release highly saline pore water. Hydraulic transport occurs between the bed and banks of the pond and the lower soil, which is connected to groundwater aquifers. Interestingly, both the pressure exerted by the immense weight of the pond above and the high salinity and solute content help drive the flow of fresh water into the pond through percolation, and osmotic suction (Vandenberg et al., 2012). 79  The surface is considered aerobic up to 1 meter in depth based on research conducted by Holowenko et al (2000). However, in the winter the ice cover, lasting approximately 6 months, produces anoxic conditions. The sulphate reducing bacteria occupy this 1 meter; below this would be anaerobic conditions suitable for methanogens and nitrogen reducing bacteria. The Mildred lake settling basin has a gas flux on surface 60-80% flux gas methane, approximately 12g CH4/m2/day.    Figure 3.23  Alberta Oil Sands conceptual Tailings Pond Model overview of conventional variables.    Mature Fine Tailings Soil    OSPW Free Water   Fine Fluid Tailings           CAP WATER PORE WATER Methanogens Nitrogen reducing bacteria ANAEROBIC 1 m- 3m OIL High Salinity Suspended clay, silt, & other particles Compacted sand, clay & other Alkaline pH > 8.5 AEROBIC Percolation, Capillary Action, Osmotic Suction Percolation Adsorption Precipitation Settling Suspension Dissolution Volatilization 3-5 m 1 m 80  OSPW rich in salts and ions enters the tailings pond. Bitumen extraction treatment including hot water, caustic soda (NaOH), cyclone or tumblers and aeration initiate the precipitation and settling of quartz sand, fieldspar, mica flakes and clays. Further treatment in assisted consolidation of tailings, additive of gypsum (CaSO4·2H2O) will result in Na+ and Ca2+ ions (70-120 mg/L), sulphate (1000 mg/L), as well as, calcite precipitate (MacKinnon et al., 2001). The free water compartment will contain a high concentration of Ca2+, Cl-, Fe2+, HCO3-, K+, Mg2+, Na+, S, SO42; of which Cl will remain in solution, while Ca2+, Fe2+ and Mg2+ will precipitate (Holden et al., 2011) (Figure 3.24). The settling precipitate will pass into the fine fluid tailings compartment where biodegradation in the form of sulphate reductions, adsorption as ion exchange, sodium-induced desorption, sorption of Ca2+ and Mg2+ with Na producing sulphate and carbonate minerals. As a result sulphate (SO42-) and carbonate (HCO3) minerals precipitate and settle into the next compartment of mature fine tailings. The sands and clays within the mature fine tailings undergo cation exchange and release Al3+, Cl-, Na+ and leach Fe and Mg.  The densification of tailings results in the release of pore water which is highly saline (salt 0.2 mg/L) (Leung et al., 2003). Percolation occurs at the boundary of the tailings pond base, composed of tailing placed on top of the original parent material, soil (or mixture of sand) and or bedrock. Some ions may be absorbed by the soil through ion exchange, van der Waals forces and filtration (MacKinnon et al., 2001; Peng et al., 2004). Water moves from the settling pond into lower ground layers and probable subsurface flow (Vandenberg et al., 2012). In addition to capillary action, the weight of the tailings and high salt and solute concentration encourages fresh water from subsurface ground water to move into the pond through percolation and osmotic suction. The rate of hydrological movement is dependent upon the porosity and hydraulic 81  potential of the materials. Fresh water can enter the mature fine tailings compartment, and further add to the dissolution of Al3+, Ca2+, Cl-, Fe2+, Mg2+, Na+, and sulphate (SO42-) salts. Dissolution of Ca2+, Cl-, Na+ and SO42-, within the FFT can be followed by transport into the uppermost free water compartment.     Figure 3.24  Alberta Oil Sands conceptual Tailings Pond Model overview of ions.  Fresh OSPW is quite alkaline and as a result approximately 20-30 % of the NAs will be in the form of naphthenate salts (density 1.059 g/cm3), while partitioning and precipitating as calcium and sodium naphthenate salts (Figure 3.25) (Whitby, 2010). The free water will contain Mature Fine Tailings Soil    OSPW Free Water   Fine Fluid Tailings           CAP WATER OIL Consolidation release saline pore water Adsorption of ions to sand and clay Sorption to minerals Sand clay Percolation of saline water Salts and ions Precipitation Settling Stratification (density) Dissolution Adsorption of ions to sand and clay  Evaporation Percolation, Capillary Action, Osmotic Suction 82  dissolved alkanes and NAs. The oil film will attract other low molecular weight organic compounds such as NAs. Higher density salts (e.g. sodium naphthenate salts) will stratify to bottom of the fine fluid tailings, while lower maltenes remain soluble. The soluble constituents of bitumen remain liquid at ambient temperature, these maltenes include the following with their appropriate density: saturates (900 kg/m3), resins (1058 kg/m3) and aromatics (1003 kg/m3) (Nji, 2010). While the asphaltene constituents are insoluble and solid at room temperature, with a density of 1192 kg/m3. BTEX, PAHs, tri-methylbenzenes, tetra-methylbenzenes, naphthelenes, cyclohexane will undergo degradation through ion exchange and adsorption to settling particulates.  Clays bind to humic acids and asphaltenes, in addition, bitumen adheres to clays and mineral slimes covering the clays. The particulates and clays of FFT will settled into the MFT compartment where tri-methylbenzenes, tetra-methylbenzenes, naphthelenes, cyclohexanes are less soluble and stay in MFT longer. The densification of MFT will release pore water highly concentrated in certain substances (e.g. NAs 70-100mg/L). Degradation of organic compounds will occur under aerobic (e.g. fermentation producing CO2) and anoxic conditions (e.g. methanogenesis producing CH4). Methanogens will degrade larger less recalcitrant organic compounds producing methane gas (at rate of 12 g/m2/day), percolation of gases from pore water will aid in NA transport to upper layers. Dissolution (e.g. SAR (maltenes), NAs) and volatilization (e.g. n-alkanes C6-C9>C10-C12; toluene>>o-xylene>benzene>>m-xylene>ethylbenzene>>p-xylene) will drive movement through the upper compartments to the atmosphere (Baedecker et al., 2011).  83   Figure 3.25  Alberta Oil Sands conceptual Tailings Pond Model overview of organic compounds.   The free water compartment contains dissolved metals which have been shown to significantly exceed the CCME guidelines: Al, As, Cd, Cr, Cu, Fe, Mn, Mo, Pb, Zn (Allen 2008, Baker 2012, Kelly 2010, RAMP 2012, Sansom 2010). Other typically dissolved elements present include B, Be, Li, P, S, Sb, Se, Ti, V, Zr. Some metals bind to organic compounds forming protoporphyrin-metal complexes (e.g. Ag, Cd, Cu, Hg, Ni, Pb, Zn), which undergo precipitation, settling and resuspension from the free water to the MFT. Precipitation and settling of metals occurs through the upper to lowermost compartments (e.g. As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, K, La, Mg, Mn, Mo, Ni, Pb, Rb, Sr, Y, Zn) (Figure 3.26). Some elements are naturally associated Mature Fine Tailings Soil    OSPW Free Water   Fine Fluid Tailings           CAP WATER OIL (e.g. UV, ozone) Adsorption to sand and clay Sand clay Percolation of saline water Partitioning Precipitation Settling Stratification (density) Dissolution Volatilization Convection flow Capillary action of fresh water Adsorption to sand and clay Organic compounds Consolidation release saline pore water. Volatiles release from pore water aids the percolation of organic compounds. Microbial enhanced settling Microbial degradation Chemical oxidation  Volatilization 84  with clay minerals (e.g. La, Y), and both sands and clays (B, Li, S, Sr, Zn), while others become associated with particulates (e.g. Al, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Hg, Ni, Pb, Ti, U, V). The pore water of MFT contains persistently stable concentrations of As, Cu, La, Pb and Y. The other metals within pore water include: Ba, Ca, Cd, Co, Cr, Fe, Ga, K, Mg, Mn, Mo, Ni, Rb, Sr, and Zn. Percolation of water into the surrounding soil transports metals, which then may be retained in the soil through ion exchange, van der Waals, and filtration, by close association with colloids of silicate clays, iron, aluminum oxides, minerals and humic substances.  Selenium and sulfur can undergo ionic substitution with minerals such as chalcopyrite (CuFeS2) as selenopyrite (SeFeS), pyrite (FeS2) and galena (PbS) (Pyrzynska, 1998; Pyrzynska, 2002). Elemental Se can associate with cations (e.g. Ca2+, Mg2+); however, inorganic anions of selenite (SeIV) and selenate (VI) do not react.  Selenite has a higher solubility than selenate, pH sensitive (precipitates at pH 6 during the caustic soda treatment) and is the most dominant form in saline water. Decomposition of selenates produces oxygen and highly insoluble metal-selenides (e.g. mercury, silver, copper, cadmium, arsenic and tin) which tend to settle becoming associated with bottom sediments. Selenium can react with reduced sulfur compounds forming insoluble selenosulphides (e.g. Se2S3). Sulphates decompose into metal oxides, sulfur oxides and oxygen. Microbes can transform inorganic forms of selenium into volatile organic compounds (e.g. methylated selenides).  85   Figure 3.26  Alberta Oil Sands conceptual Tailings Pond Model overview of elements.   Mature Fine Tailings Soil    OSPW Free Water   Fine Fluid Tailings           CAP WATER OIL clay Percolation of water Precipitation Settling Dissolution Volatilization Convection flow Capillary action of fresh water Adsorption to clay Metals Consolidation release pore water. Volatiles release from pore water aids the percolation of metals. Microbial degradation Dissolved Volatilization  oxidation Particulates and metal complexes Adsorption to clay Bound to particulates and organic compounds  - + 86  Chapter 4: Discussion  4.1 Literature review  The literature review was extensive and thorough of peer-reviewed articles, theses and industrial sources. There were discrepancies within sources of data, in terms of spectrum of OSPW constituents analyzed and reported. The predominant research appeared to be on NAs by toxicological risk assessments, characterization of molecular forms present in OSPW, treatment and the mechanisms involved in degradation. The majority of research included commercial NAs which were determined to be easier to degrade by microbes, due low molecular mass and structure with predominantly unsubstituted or alkyl-sub cyclohexane carboxylic acids (Herman et al., 1994; Whitby, 2010).  The research available on PAHs was not as extensive and some researchers have indicated that these compounds could be more a concern than NAs (Gagné et al., 2011; Gentes, 2006). There is a lack of information on the mechanisms and effects of PAHs (particularly light compounds) and NAs on both liver function etoxyresorufin-O-deethylase (EROD) and glutathione S-transferase (GST) activities. The toxicity of PAHs is theorized to also involve oxidative stress and cell damage due to lipid peroxidation. The current research contains knowledge gaps in the possible compounding effects of various OSPW constituents on toxicology and treatment, in addition to the chemical processes occurring within the OSPW including complexation of different substances and metal speciation. In addition, further research is needed into the factors contributing to the variability in OSPW properties and constituents (e.g. geospatial ore compositions, chemical additives, changes in operations, recycling OSPW). 87  The current literature lacks any attempt to analyze existing research and integrate the information into an all-inclusive review, as well as, as to attempt the creation of conceptual tailings pond model. This thesis is research first of its kind, to analyze and integrate most known scientific sources of information on the physical, chemical and biological properties and processes of the Alberta oil sands regions OSPW, tailings pond and affected landscape. This research was conducted by one individual, while such integration and analysis would typically be tackled by a team of multidisciplinary experts. A conceptual Tailings Pond Model was created, incorporating a broad-spectrum of complex processes into a comprehensive package.                 88  4.2 Oil sands process water properties  4.2.1 Physical variables  The OSPW typically is alkaline with high hardness, conductivity, TSS and TDS. The alkalinity and conductivity (e.g. high ion content) can be the result of both chemical treatments in ore extraction (e.g. use of caustic soda NaOH) and CT technology to enhance settling rates in tailings (e.g. addition of gypsum acid salt CaSO4 2H2O) (Holden et al., 2011). The alkalinity will drive chemical processes, such as the precipitation of NAs as sodium napthenate salts. The treatments to adjust pH such as addition of sulphuric acid (H2SO4) (e.g. 650g concentrate per m3 CT) result in ions leached from clays (e.g. Ca+2, Na+), and elevated concentrations of Al, Fe, Mg, and SO4-2 (MacKinnon et al., 2001). The oil sands typically contain minerals which include quartz, kaolinite, and illite, clay minerals such as montmorillonite and some heavy minerals (Cao et al., 2007). Fine fluid tailings composed of sand and fluidized clay particles, these suspended solids are potential sites of adsorption by organic compounds, ions and metals, as well as, potential contributors of these through loss by desorption. Bitumen tends to adhere to clays and mineral slimes covering clays. The high DOC indicate sufficient content dissolved organic carbon and other sources of carbon (e.g. hydrocarbons such as NAs) for microbial oxidation reduction reactions (e.g. sulphur reducers, methanogens). There is a lack of research on the effects of operation processes on physical variables over time in active tailings ponds, nor the rates of these processes (e.g. microbial effects on decreasing TSS and TOC).  89  4.2.2 Major ions  The OSPW and tailings have been shown to have high ion content, in particular the following ions  in order of descending mean concentration: Na+, Cl-, SO42-, Ca2+, Mg2+, K+, CN-, Fe 2+, S2-, Hg+. The high ion content is the result of both chemical treatments in ore extraction (e.g. NaOH) and CT technology (e.g. CaSO4) which result in the dissolution of ions primarily comprised of sodium, chloride, sulphate, calcium and magnesium (Holden et al., 2011). The dissolution of sulphate, sodium and chloride from oil sands and associated clays are also a contributing factor (Van den Heuvel et al., 1999). The OSPW is stored in tailings ponds, and recycled for use in treatment processes; consequently ions and other chemical constituents becoming more concentrated over time (Holden et al., 2011). Research has demonstrated that tailings pond water ion concentrations (e.g. Cl-, HCO3- , Na+, SO42-, NH3) exceed reference Athabasca River by 40-200 fold (Allen, 2008). The ionic constituents of OSPW, in exception to those where there was a lack of guidelines, exceeded the CCME guideline objectives. Consolidated tailings (CT) technology results in effluent with high salinity, and calcium content (MacKinnon et al., 2001). Some chemical treatments may include acid, lime, acid/lime combinations, gypsum, alum and organic polymers. The process promotes the coagulation of clays which increases the salinity due to the exchange of cations (Al3+, Ca2+, Na+) on the surface of the clays, along with the leaching of Al, Fe and Mg. Gypsum promotes the release of water low in particles but high in naphthenic acids, salts and major ions (e.g. Ca2+, Cl-, Na+, HCO3- and SO42-) (Leung et al., 2001). The addition of sulphuric acid (e.g. treatment to adjust pH) result in ions leaching of  Ca+2  and Na+ from clays, elevated concentrations of polyvalent cations, as well as, Al, Fe, Mg, and SO4-2 (MacKinnon et al., 2001). The current research lacks knowledge on the 90  rates in the release of ions and salts from the various sources (e.g. ore, chemical additives), as well as, any possible attenuation and roles biota may play in transport and fate.  4.2.3 Organic compounds  The effluent from oil sands extraction processes contains various other organic components such as asphaltenes, creosols, humic and fulvic acids, and phthalates (Leung et al., 2001). The OSPW and tailings content of organic compounds exceeded the CCME guidelines for all compounds for which there were guidelines. The examination of data from 17 scientific sources determined the following organic compounds present in OSPW in order of descending mean concentration: bicarbonate, tannin/lignin, NAs, carbonate, bitumen, total hydrocarbon, phenols, toluene, benzene, PAHs, m&p xylene, ethylbenzene, o-xylene.   Naphthenic acids are a complex mixture of mono- and poly-cyclic alkanes (predominantly cyclohexanes and cyclopentanes) that contain carboxylated aliphatic side chains of various lengths (Herman et al., 1994). This family of compounds composed mostly of carboxylated cyclic aliphatic hydrocarbons is a major class of alkali-extractable organics (Gagné et al., 2011). Naphthenic acids are a group of relatively low-molecular-weight (<500 m/e) carboxylic acids, with varying numbers (zero to five) of polycyclic aliphatic ring structures and aliphatic side chains of various sizes (Leung et al., 2001). The exact composition of tailings has not been determined by the scientific literature, due to the high complexity of organic compounds which are yet to be identified. The chemical treatments of caustic soda and gypsum result in tailings high in bicarbonate (Holden et al., 2011). The alkaline extraction treatments would release NAs into OSPW, which 91  at pH 8-9 NAs would form sodium naphthenate salts (Frank, 2008; Xiumei et al., 2009). These salts would tend to partition and precipitate to lower depths. The variability in concentration of NAs may be associated with fresh OSPW at time of release and the age and depth of the tailings pond free water. NAs with a lower molecular weight are very soluble and tend to associate with oil films at the tailings pond surface. There is a lack of research into the rates of release and concentrations of organic compounds from the various sources (e.g. oil sands ore, chemical additives), nor the chemical structure, chemical reactions, and ultimate transport and fate.  4.2.4 Nutrients  The OSPW and tailings nutrients concentration data from 17 scientific sources revealed the following mean concentration order of descending: nitrate, total nitrogen, ammonia, total phosphorus, nitrite, orthophosphate, total nitrite and nitrate. Those nutrients which exceeded the CCME guideline limits included: ammonia, nitrate, nitrite and total phosphorus. Reclamation planning strategies have included end-pit lakes (EPLs) in mined-out areas, and research has included the construction and monitoring of demonstration ponds, where MFT was capped with fresh water and allowed further recharge through precipitation, surface runoff and groundwater percolation (Allen, 2008). Researchers have quantified reduced toxicity in these ponds over several months to years. The presence of aquatic plants, aeration and nutrients have been shown to increase detoxification rates through constituent taken up by producers and stimulating microbial populations which degrade compounds such as NAs. In addition, certain environmental elements affecting NA degradation include nutrient availability, as well as, temperature, oxygen, pH, redox potential, and sunlight (Whitby, 2010). 92  The processes in the fate and transport of elements and other constituents involve partitioning and degradation, as well as attenuation by vegetation such as selective metal uptake by certain species (Hrynyshyn et al., 2012). However, decomposition of organic material releases elements and compounds which had been taken up by biological matter. The fates of nutrients are closely associated with cycling of organic matter, ecological food web cycles and vegetation. There is a lack of research on the relative rates of release of nutrients from various sources (e.g. ore, chemical additives), nor the forms, chemical reactions and possible ultimate transport and fates. Further research is needed on which biota may play a more active role in possible remediation of water quality.  4.2.5 Elements  The OSPW and tailings element content is predominantly sulphur (539 to 0.001 mg/L), this may be due to the natural sulphur content of the ore and parent materials (e.g. sand, clays), which leaching occurs during processing (Nji, 2010; Van den Heuvel et al., 1999). In addition, chemical additives containing sulphur such as gypsum acid salt and hydrogen sulphide contribute to the sulphur content. Review of 17 literary sources of data revealed the following metals  in order of descending mean concentration: S, Mg, La, F, Si, Al, B, Fe, V, Br, Sr, As, Ag, Mo, Ba, Mn, Li, Sn, Zn, Ni, Ti, Cu, P, Pb, Cr, Zr, Co, Sb, Se, U, Cd, Be, Tl, Hg, Y.  The enrichment of certain elements (e.g. Al, Cr, Fe, V) have been identified where these are likely released from ore and parent materials such as clays (Dubenest et al., 2012). However, the exact source of these elements have not been studied in depth and some may be due to chemical additives in the maintenance of processing plants (e.g. Cr). Rare earth elements of La 93  and Y tend to be associated with clay minerals and typical in FFT where clay is fluidized (Baker et al., 2012). Increased levels of boron, lithium, strontium, sulphate and zinc were identified as the likely result of oil sands and associated clays (Van den Heuvel et al., 1999). Metals found in higher concentrations near the development than upstream and a significant proportion are bound to organic matrix protoporphyrin-metal complexes, typically include cadmium, copper, lead, mercury, nickel, silver, and zinc (Gagné et al., 2011).  The analyses of 17 scientific sources of data indicate that the following metals (mean concentration) exceeded the CCME guidelines: Ag, Al, As, Cd, Cr, Cu, F, Hg, Mo, Pb, Se, and Tl. In addition to the data ranges for B, Fe and Zn, while P was at the CCME limit. The metals which tend to bind to organics forming protoporphyrin-metal complexes include: Ag, Cd, Cu, Hg, Ni, Pb and Zn (Allen, 2008; Baker, 2012). The elements which tend to precipitate into tailings sediments include: As, Ba, Ca, Co, Cr, Fe, Ga, K, La, Mg, Mn, Mo, Rb, Sr and Y. The FFT is made up of fluidized clay where La and Y are associated with clay minerals. Hg tends to associate with particulates, while Cd, Co, Cu, Ni and Pb tend to be associated with particulates and also in dissolved phases. All of the former metals have been found in MFT pore water. As, Cu, La, Pb, and Y tend to have concentrations persistently similar in CT and MFT. In addition, Al, B, Be, Li, P, S, Sb, Se, Ti, V and Zr have also been found in tailings ponds (Kelly, 2010; Sansom, 2010). Be tends to associate with particulates. The source of B, Li, S, Sr, and Zn have been indicated as the oil sands ore and clays. The treatments to adjust pH, such as the addition of sulphuric acid results in elevated concentrations of Al, Fe, Mg, and SO4-2; some of which may be leached from clays (MacKinnon et al., 2001).  There is a lack of knowledge on the rates of release of elements from the various sources (e.g. ore, chemical additives), as well as, the possible attenuation rates. The existing research has 94  been typically on specific elements, there is a lack of study into the additive effects of multiple elements, as well as, varying water quality conditions on speciation, chemical reactions, and ultimate transport and fate.  4.2.6 Biology  The indigenous oil sands tailings bacteria of Pseudomonas stutzeri, and Alcaligenes denitrificans have been identified as capable of degrading NAs, by the mineralization carboxylic acid groups or oxidation aliphatic side chain degrade cycloalkane ring (Herman et al., 1994). The other bacteria present in tailings include Acinetobacter calcoaceticus, Psedomonas fluorescens and Kurthia species, which are capable of degrading tailings extract by mineralizing hexadecane. Bacteria capable of degrading NAs include Acinetobacter anitratum, Alcaligenes faecalis, Corynebacterium cyclohexanicum, and Arthrobacter, however, it is not known whether these species occur in the Oil Sands affected landscape (Whitby, 2010). The phytoplankton communities, apparently tolerant species to OSPW, include Botryococcus braunnii and Chlamydomonas species (spp.) (Chlorophyta), Cryptomonas spp. and C. depressum (Cryptophyta), Ochromonas spp. and Chromulina spp. (Chrysophyta), Oscillatoria spp. (Cyanophyta), and Navicula spp. and Nitzschia spp. (Bacillariophyta) (Leung et al., 2001). Chlorophyta and Euglenophyta were among the most successful followed by Botryococcus braunni and Pandorina morum. These species appeared to be tolerant occurring within the settling basins, of the MLSB and area, with moderate naphthenate levels (8-21 mg/L). Indigenous oil sands tailings bacteria include: Pseudomonas stutzeri, Alcaligenes denitrificans, Acinetobacter calcoaceticus, Psedomonas fluorescens and Kurthia species (Herman et al., 1994).  95  The microbial degradation of NAs by these bacteria was determined to be through the oxidization of aliphatic side chain and degradation of the cycloalkane ring. Del Rio and associates (2006) isolated Pseudomonas putida, Pseudomonas fluorescens from OSPW exposure areas. These organisms are also capable of degrading organic compounds such as NAs. Microbial activity can be measured through monitoring CO2 production, and dissolved oxygen reduction. Commercial mixtures NAs are more readily biodegraded and detoxified than organic acids present in oil sands tailings which may be more resistant to microbial degradation. Baker and associates (2012) identified the presence of naturally occurring macrophytic alga, Chara spp., which is capable of colonizing tailings, as well as, the invertebrates which included snails (Gastropoda: Lymnaeidae), dragonflies (Odonata: Aeshnidae) and larval chironomids (Diptera: Chironomidae: Chironomini). Chara spp. exhibited a tendency to accumulate higher concentrations of V (x 3 of reference), Ni (x 1.5 of reference), La, and Y. Chironomids generally had the highest mean concentrations of every metal measured compared to the other two taxa, which accumulated at a lower rate, including very high concentrations of V (913.1 ± 236.3 mg/L). The increased tissue metal concentrations in snails were associated with exposure to high environmental concentrations.  The treatment additive of gypsum may be a major contributing factor in the metals content in compacted tailings. Further research is needed to determine which biota species are involved in the degradation and possible attenuation of various OSPW constituents, as well as, the rates of these processes.    96  4.3 OSPW CCME water quality index  The CCME Canadian water quality guidelines for the protection of aquatic life, water quality index (WQI) analysis of 17 scientific sources of data identified certain conventional physical parameters, ionic, nutrient and metal content, which exceeded the guideline objectives. The WQI scores are rated, where 100 indicates best water quality, and 0 the poorest. The differences between the data appeared to be from completeness of data, quantity of parameters analyzed and reported. Some of the higher WQI scores which indicated better water quality conditions were associated with lack of data where very few of the WQI variables were provided.  The variables which failed to meet the WQI objectives, with respective exceedence ranges: Ag (x 4700), Al (x 2-9), As (1-460), Cd (x 2-250), Cl (x 1-7), Cr IV (x 3-15), Cu (x 1-10), Fe (x 1-6), Hg (x 2), Mo (x 1-7), NH3 (x 3-2293), NO3- (x 4), P (x 2-680), pH (x 1.01-1.04), Se (x 2-20), Tl (x 4), Zn (x 1-1.5). The amplitude by which the recommended limits were exceeded was quite significant in certain data sets. The frequency of data failing to meet WQI objectives was related to the quantity of data provided, where incomplete and lacking data was prominent in the majority of the scientific resources. The 17 scientific sources were inconsistent in the reporting of OSPW constituents.  El Din (2011), Holden (et al., 2011), Leung (et al., 2003), Ma (2012), Mackinnon (et al., 2001), Peng (et al., 2004), Scott (2008), Tompkins (2009) were deficient in completeness of data for proper WQI testing, resulting in moderate WQI scores. Hrynyshyn (et al. 2012) sampling data quantity was better for the years of 2003 and 2007, where certain variables far exceeded the objectives: Ag (x 4700), Al (x 2-5), As (x 2-460), Cl (x 5), Cd (x 15-40), Cr VI (x 4), Cu (x 10), 97  Hg (x 2), Mo (x 7), P (x 2- 680), Se (x 3- 4), and Tl (x 4). Allen (2008), Holowenko (et al., 2000) and Xiumei (et al., 2009) lacked most data, and respectively scored WQI (36, 22, 21) due to the excessive exceedence of NH3 (x 933, x 267-1667, x 447-667) and chloride (n/a, x 2-4, x 1.3-4). Baker (et al., 2012) and Van den Heuvel (et al., 1999) had adequate data, with a moderate WQI scores 48 and 37, respectively where the water quality guideline objectives exceeded in the following: As (x 0.2, x 1-6), Cd (x 38, x 2-4), Cr (VI) (x 3, x 3-5), Cu (x1, x 3), Fe (x 4.8, x 1.5), NH3 (x 5, n/a), P (x 4, x 27), Zn (x 1, x 1.5).  The two sources which had the most complete set of data for WQI testing: Sansom (2010) and Zubot (2010). Sansom (2010) had a fair dataset for testing WQI, scoring ranged from 16-18, with the following variables with respective exceedences: Al (x 2-9), NH3 (x 7-2293), Cl (x 1.4-5), Fe (x 2-6), Mo (x 1.4-7), and pH (x 1.04). Zubot (2010) had the most complete set of data, with a WQI score range from 13-25, with the respective guidelines exceedences: NH3 (x 233-1000), Cl (x 3-7), Cd (x 5-250), Cr (IV) (x 3-15), Cu (x 8), DO (x 11-1.6 below limit), Fe (x 1.1), Hg (x 2), Mo (x 1.4-2), nitrate (x 4), pH (x 1.01), P (x 2), and Se (x 2-20).         98  4.4 OSPW parameters data source comparison  A comparison of three literary sources of data was conducted to assess any obvious trends in concentrations of various OSPW constituents. The data sources which were considered most complete in datasets had been determined in the former WQI assessment (see section 4.3), these included: Sansom (2010), Van den Heuvel (et al., 1999), and Zubot (2010). The Van den Heuvel (et al., 1999) data described a demonstration pond, created for testing reclamation methods, containing MFT and sampled from date of construction 1993 to1995. Zubot (2010) sampled an active tailings pond from 1997-2009, where data variability could be the result of OSPW age, modifications in tailings extraction and CT technologies and differences in chemical additives. Sansom (2010) analyzed fresh OSPW from point source, tailings pond, mine site ditches and reference sites (e.g. Mildred Lake). The alkaline pH of the tailings pond and demonstration pond remained above the neutral conditions existing at the reference site of Mildred Lake. Fresh OSPW had conductivity 17 times values from Mildred Lake. Drainage ditches and seepage sites tended to have consistently unchanged high conductivity. In addition, sulphate levels in fresh OSPW from Sansom (2010) were 4 times that of tailings pond data from Zubot (2010), likely due to source of the samples, age and differences in chemical additives. The demonstration pond had concentrations of Cl and Na equivalent to active drainage ditches. Fresh OSPW had the highest concentrations of Ca, K, Mg, NAs and NH3. The demonstration pond has a marked increased concentration of carbonate in comparison to OSPW either fresh or in a settling basin. The demonstration pond had the highest concentration of carbonate, the source is unknown; however, it could possibly be due to the addition of lime as a treatment in construction for the prevention of acid rock leachate and to 99  encourage the precipitation of heavy metals. Lime treatment is to create alkaline conditions, to precipitate heavy metals, such as Cu, Fe, Zn at pH of 9.5 and other metals such as Cd and Ni at pH 10.5-11 (Aubé, 2004). The tested remediation through demonstration ponds reveals that the pH remained unchanged and alkaline. The conductivity, Ca, K, Mg, NAs, NH3 and SO42- concentrations appear to reduce over time, likely due to naturally occurring physical, chemical and biological processes. The metals concentrations for Al, B, Fe, Sr and V remained consistent from tailings pond, ditches and demonstration pond. The demonstration pond had reduced concentrations of Mn and Mo. There may be some biological and chemical processes acting on metal speciation, and partitioning, ultimately affecting the transport and fate. The man-made construction of the demonstration pond likely included the addition of a lime additive, where the decreased concentrations of Mn and Mo are due to precipitation driven by alkaline conditions. There were certain metals which remained unchanged in concentration: Al, B, Fe, Sr and V. The processes influencing transport and fate of these elements appear to be less affective in attenuation in tailings ponds and other treatment options.        100  4.5 Ecological effects  4.5.1 Athabasca watershed  The RAMP reported that reference sites within the Athabasca River watershed (Athabasca River, Steepbank River, Beaver River, McLean Creek, Mills Creek and Eymundson Creek) scored WQI range 60-80, indicating moderate to good water quality conditions. The Athabasca River near the oil sands development had Cd, Cu and Pb exceed CCME and Alberta water quality guidelines (Gueguen et al., 2011). In addition, the tributaries, from 1998-2000, had elevated concentrations of As, Cd, Co, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn (Conly et al., 2007). PAHs concentrations varied from 0.009 mg/L upstream of the oil sands development to 0.2 mg/L downstream (Leung et al., 2001). The exposure of the oil sands landscape makes it more susceptible to mobilization of constituents through flooding, wind and erosion (Headley et al., 2002; Leung et al., 2001; Yunker et al., 1993). The Athabasca River is known to frequently flood this landscape and this is thought to be a major contributing factor to increased PAC levels in the Athabasca Delta watershed. The data provided suggest that metals which tend to be persistent in the environment include: As, Cd, Co, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn. The attenuation of metals occurs naturally and is encouraged through chemical additives (e.g. Gypsum, Lime). Alkaline conditions induce the precipitation of metals in tailings ponds, removing them from the dissolved mobile state to a more stable state; potentially creating a sink for heavy metals. In addition, the RAMP program regularly tests a broad range of metals, and data should indicate trends in possible transport and fate of these constituents. However, inconsistencies in environmental 101  sampling, laboratory analysis and reporting would greatly encumber any usability and value of the data.  4.5.2 OSPW toxicological effects  The principal cause of toxicity associated with MFT and CT tailings is thought to be naphthenic acids, which are present as sodium naphthenates in dissolved form (Leung et al., 2001). The lack of water quality guidelines for naphthenates in Canada or the United States necessitates the need for some preliminary objective limits given the vast majority research has found detrimental effects in biota.  There are some phytoplankton communities, present in settling basins which are apparently tolerant to moderate naphthenate levels (8-21 mg/L). Chlorophyta and Euglenophyta are the most abundant species. Fathead minnows (Pimephales promelas) exhibited reproduction impairment, inhibition of spawning and diminished male secondary sexual characteristics (Kavanagh et al., 2011). Similarly tree swallows in the Oil Sands mining areas had decreased reproductive success, and increased nestling mortality with rates of 100% at sites with highest PAH and NA concentrations (Gentes, 2006). There is a lack of information on the effects of light PAHs and NAs on both EROD and GST processes.  The toxicity of PAHs tends to be the result of oxidative stress which could result in major cellular damage, in particular during biotransformation this could lead to lipid peroxidation (LPO) or genotoxicity (Gagné et al., 2011). The effects of PAHs on fathead minnow larvae resulted in mortality which was directly correlated to the cytochrome P4501A1 activity. The observed toxicity was linked to three or more aromatic ring PAHs. Some medium (3-4 aromatic 102  rings) and heavy PAHs (e.g. pyrene and benzo(a)pyrene) are recognized as immunosuppressive, genotoxic and carcinogenic. Genetoxicity involves phase one biotransformation of cytochrome (P4501A1 or 7-ethoxyresorufin O-deethylase, EROD) to produce DNA-reactive transitional phases. Only PAHs high in molecular weight tended to induce genetoxicity, while smaller PAHs (e.g. three to four aromatic rings) induced glutathione S-transferase (GST) activity.  The process affected water contains high concentrations of various elements, of which those identified in section 3.2 as exceeding the CCME water quality guidelines for the protection of aquatic life included: Ag, Al, As, B, Cd, Cr, Cu, F, Fe, Hg, Mo, Ni, P, Pb, Se, Tl, U and Zn. Some elements are bioaccumulative (e.g. Ag, B, Se, Tl). Certain elements toxicological mode of action is through disruption of ion channels. Silver binds to sodium channels, disrupting sodium and chloride regulation, resulting in tissue damage, and subsequent death. Boron, mercury and selenium are known to cause reproductive impairment, teratogenesis, decreased survival and increased mortality. Lead is genotoxic and causes reproductive dysfunction. In addition, Mo adverse effects include decreased number of offspring and inhibited growth. Nickel tends to accumulate in the kidneys. Chromium (VI) is strongly oxidizing, moves through biological membranes with ease and results in detrimental effects on various organ systems and death. Some elements have a tendency to bind to minerals, and particles, such as Tl, U and Zn. Adverse effects of U can include reproductive impairment and mortality. Zinc levels exceeding recommended objectives can result behavioral changes, mortality and decreased diversity and abundance.     103  4.6 Tailings pond processes  4.6.1 Physical processes: limnology  The limnology of tailings ponds are an area of research which has not been studied and present significant knowledge gaps. However, the basic concepts of limnology can be applied to understanding the physical processes. The molecular properties of water are fixed and applicable to all water bodies. The densities of water vary and depend upon thermal and saline conditions which then drive convection and stratification (thermal separation). The density of water from order of least to most dense for a given temperature include: 20 °C, 0 °C and 4 °C (Lampert et al., 2007).  Solar radiation absorption of short-wave radiation (e.g. UV) occurs within uppermost few centimeters of the epiliminion surface, while visible light may reach depths of tens of meters (e.g. visible infrared (IR)) (Girgis, and Smith, 1980). Dark surfaces absorb more UV and the dark oil film covering the surface would enhance solar heating during the summer. Ice cover in winter would reflect solar radiation back into the atmosphere. Heat exchange occurs at the surface, where temporal atmospheric variations influence heat gain and loss. The vertical temperature distribution is dependent upon surface heating, and the propagation of heat (e.g. via molecular diffusion, convection, eddy viscosity). The extent of circulation patterns, vertical mixing and heat exchange within a water body will be dependent on the physical dimensions (Bennett, 1978).  Heat energy is primarily lost through wind induced convection and emission of long-wave radiation (Edinger et al., 1968; Pham et al., 2008). Mass fluxes such as precipitation may 104  also influence heat transfer. Atmospheric influences on heat balance may occur in spatial and temporal fluxes, such as fall cooling and wind storms which enhance vertical mixing (Alvarez-Cobelas et al., 2005; Bennett, 1978; Livingstone, 2003). Jiang and associates (2013) reported wind driven wave action in MLSB. Mixing and conduction at the surface is expedited due to low thermal resistance and relatively light winds can easily complete circulation (Welch, 1952). Winter ice cover insulates from the influences of wind, reduces heat loss, while diffusion of heat may occur at the molecular level (Hostetler et al; 1990; Kirillin et al., 2012; Lampert et al., 2007; Mishra et al., 2011; Rouse, 2009). Winter thermal stratification would have the lowermost layer typically at 4 °C; warmer than the uppermost layers. The thermal profile would reverse at spring turnover where a thermocline would develop in the summer, as in dimictic water bodies. Holowenko and associates (2000) reported summer stratification in MLSB temperature depth profile. The temperature within the FFT layer fluctuates from 11-15 ˚C within a one year cycle. Winter ice-cover can purge salts which then accumulate at the bottom, resulting in a freshwater capped uppermost layer (Hrynyshyn et al., 2012). Salinity driven stratification would result in denser more saline water at the bottom. Meromixis could occur in Oil Sands settling basins due to the high salt concentrations. However, Holowenko et al (2000) sampled the Mildred Lake settling basin, in 1997 and 1998, at various interval depths from 1m to 20 m, and stratification was measured and the water quality data did not reveal any significant difference in salt and ions concentrations from upper to deeper depths. MLSB likely displays a dimictic circulation pattern. Jiang and associates (2013) indicates that tailings pond design includes a water cap to facilitate settling of solids and to reduce wind driven resuspension of fine solids. This is 105  important in maintaining a low TSS for recycling water for use in operations. Tailings at discharge quickly separate with coarse sand particles settling to form beaches and the containment dikes (Chalaturnyk et al., 2002, Xiumei et al., 2009). The fine tails accumulate in the tailing ponds, initially fines will settle out quickly, while others remain in suspension for years (e.g. 150 years to consolidate into MFT). Microorganisms, such as methanogens, have been shown to accelerate tailings aggregation and sedimentation (e.g. rate increase of 15%) (Bordenave et al., 2010).   4.6.2 Chemical and biological processes  The geology of the Athabasca basin is glacial till which is low in Ca, K, Mg, and Na, while OSPW is highly concentrated in bicarbonate, Cl, Na, and S (Holden et al., 2011). The various constituents (ions, elements and organic compounds) within tailings ponds undergo processes which include partitioning between solid, aqueous and organic phases. The ion of special concern is Cl because these tend to remain in solution and are less likely to undergo sorption. This could prove difficult in treatment to remove these ions. Sodium has a high affinity to bind to clay in tailings where sorption increases positively with concentration. OSPW oversaturated with ions, drives the formation of Ca and Mg sulphate salts, where sulphate salts remain in solution while carbonate salts will precipitate.  The treatment of ore and parent materials leaches elements and chemical processing further enriches the OSPW (e.g. gypsum acid salt, hydrogen sulphide) (Van den Heuvel et al., 1999). Particular elements associated with leaching ore and clays include: B, La, Li, S, Sr, Y, Zn. Elements partition through binding to organics forming protoporphynn-metal complexes, with 106  Ag, Cd, Cu, Hg, Ni, Pb and Zn (Allen, 2008; Baker, 2012). The elements which tend to precipitate into the MFT include As, Ba, Ca, Co, Cr, Fe, Ga, K, La, Mg, Mn, Mo, Rb, Sr and Y. The sorption to particulates within the FFT includes certain elements Be, Cd, Co, Cu, Hg, Ni and Pb. The elements most susceptible to sorption and desorption include Cd, Co, Cu, Ni and Pb.  The organic constituents partition in the water column where maltenes (saturates, resins, aromatics) remain soluble, while asphaltenes are insoluble and tend to associate with the MFT (Nji, 2010). NAs tend to partition forming sodium salts which tend to accumulate within the oil film covering the surface of the tailings pond (Mohammed et al., 2009; Nordgard et al., 2012).  The variable organic constituents of OSPW provide sources of carbon for aerobic and anaerobic microorganisms (Scott, 2007). NAs are toxic and inhibitory to microorgansims and tend to be the last source of carbon utilized by microbial metabolism. The availability of carbon will limit biodegradation, where continuous input of fresh tailings hinders biodegradation of more complex organic compounds (e.g. NAs). The complexity of the molecular structure of NAs contribute to recalcitrance, where a higher molecular weight, longer alkanoic groups and or additional alkyl substitutions on the ring and or quaternary carbons are the most difficult to degrade (Holowenko et al., 2002).  Natural attenuation and subsequent reduced toxicity of NAs through aerobic microbial degradation in tailings ponds was described by Herman and associates (1994). In addition, NAs are not biodegraded while undergoing seepage through the walls of the impoundment dyke walls (Xiumei et al., 2009). The reason for this may be due to micropore size which can deny access to decomposer organisms (Ladd et al., 1993). Most research on NA degradation has been on commercial NAs, which have been shown to be more biodegradable than those from oil sands origin (Scott, 2007). Some limiting factors in biodegradation include mixing efficiency 107  (bioavailability of substrate), temperature, pH, concentration dissolved oxygen, nutrients (e.g. N and P) (Holowenko et al., 2001).  Research on treatment options has indicated pretreatment for recalcitrant compounds would facilitate biodegradation (Scott, 2007). Chemical oxidation, such as ozonation, alters chemical structure of recalcitrant compounds (e.g. NAs) thereby improving biodegradability. The most effective pretreatment ozonation consisted of 5 minutes, followed by 12 hours of biodegradation, to result in the effective 50% reduction in total organic carbon. The research indicated that further ozonation, beyond 5 minutes, could result in the retransformation into recalcitrant forms.  Tolerant phytoplankton taxa have been identified to occur in the MLSB under naphthenate levels of 8–21 mg/L, where Botryococcus braunni and Pandorina morum were the most tolerant (Leung et al., 2001). NA exposure studies have indicated Chlorophyta and Euglenophyta were among the most successful groups. These primary producers clearly exhibit a role in the utilization of carbon from a napthenate source, which may prove important in an ecological food-web context.  A variety of anaerobic microbes, such as methanogens, sulphate- and nitrate-reducing bacteria have been found in tailings ponds and microbial metabolism causes major emissions of methane and carbon dioxide (Bordenave et al., 2010). The Mildred Lake settling basin (surface area of 10 km2) has over the past 20 years shown methanogenic activity with an estimated gas flux of 60-80% methane, equivalent to 12g CH4/m2/day (Holowenko et al., 2000; Xiumei et al., 2009).  The methane percolation assists the transport of NAs from pore water of fine tailings into capping water layers. The gaseous emissions from MLSB are currently uncontrolled and are an input to atmospheric greenhouse gases. 108  4.7 Tailings pond conceptual model  The oil sands tailings pond conceptual model (focus on MLSB) developed within this research is the first of its kind. There are significant gaps in research and there have been no attempts to create a conceptual model, let alone define the objectives for modeling. The process of modeling is quite complicated given the various physical, chemical, biological, geochemical, hydrological and limnological processes involved.  There are numerous steps in the creation of a model, the first include defining the objectives, then creating a conceptual model and finally utilizing various computer software, for each of the various components and processes, to aid in the creation of a working predictive model (Vandenberg et al., 2012). A model was created specifically for the sediment transport of TSS in MLSB, however, proved to be difficult and required additional modifications and calibrations (Jiang et al., 2013). Some literature indicate that the idea of modeling reclamation areas such as pit end lakes exist, however, attempts at modelling remain in theory, as there were no modeling results published.  This research has defined the objectives of modeling and developed a conceptual Tailings Pond Model which described and explained the physical, chemical and biological characteristics and processes. The tailings pond is composed of three main compartments: free water, fine fluid tailings (FFT), and mature fine tailings (MFT). MLSB has a surface area of 12 km2, where the interface of the FFT and MFT is located at approximately 5 meters (Holowenko et al., 2000; Jiang et al., 2013). The tailings pond exhibits stratification where the surface is covered in a film of oil (e.g. 1 to several cm thickness), and highly saline water forms a layer over the MFT (Holowenko et al., 2000; Xiumei et al 2009). The free water contains dissolved alkanes, and maltenes (Whitby 2010). The oil film will attract other low molecular weight organic compounds 109  such as NAs, while approximately 20-30 % of the NAs will be in the form of naphthenate salts which partition to the bottom.  The assisted consolidation of tailings through the addition of gypsum directly results in high concentrations of salts and ions (e.g. Ca2+, Na+, SO42-) (MacKinnon et al., 2001). The free water compartment will contain a high concentration of Ca2+, Cl-, Fe2+, HCO3-, K+, Mg2+, Na+, S, SO42; of which Cl will remain in solution, while Ca2+, Fe2+ and Mg2+ will precipitate (Holden et al., 2011).  Naturally occurring elements associated with parent sands and clays (B, La, Li, S, Sr, Y, Zn), and others that become associated with particulates (e.g. Al, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Hg, Ni, Pb, Ti, U, V), are susceptible to settling and resuspension (Allen 2008; Baker 2012; Kelly 2010; RAMP 2012; Sansom, 2010). The free water compartment contains dissolved elements which have been shown to significantly exceed the CCME guidelines (e.g. Al, As, Cd, Cr, Cu, Fe, Mn, Mo, Pb, Zn), while others also persistent (e.g. B, Be, Li, P, S, Sb, Se, Ti, V, Zr). Precipitation and settling of elements from free water to lowermost compartments (e.g. As, Cd, Cu, Cr, Ba, Ca, Co, Fe, Ga, K, La, Mg, Mn, Mo, Ni, Pb, Rb, Sr, Y, Zn), while  some bind to organic compounds forming protoporphyrin-metal complexes (e.g. Ag, Cd, Cu, Hg, Ni, Pb, Zn).  The pore water of MFT contains persistent elements (e.g. As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, K, La, Mg, Mn, Mo, Ni, Pb, Rb, Sr, Y, and Zn), percolation into surrounding soil would have limited retention. The interaction of OSPW and native sediments result in displacement of ions and hydraulic transport is driven by capillary action, and percolation, where water moves freely between the unlined bed and banks of the pond and groundwater (Holden et al., 2011; Vandenberg et al., 2012).  110  The most influential physical processes include wind driven wave action causing mixing, winter ice cover preventing such mixing, solar radiation driven heating, seasonal turnover, OSPW recharge from operations and settling. The flux from recharge of warm recycled highly saline OSPW drives temperature and density driven circulation. These physical processes affect the suspension of clay, silt and other particles. The settling of fine particulates is enhanced through microbial action (e.g. increase 15%) (Fedorak, 2003). Research has measured significant methanogenic activity within MLSB (e.g. 12g CH4/m2/day) (Holowenko et al., 2000). The free water and FFT layers are aerobic and contain sulphate reducing bacteria within the top 1 meter depth, while below this there are anaerobic conditions which are suitable for methanogens and nitrogen reducing bacteria.  This research found the existing research lacked in understanding the microbial transformation of elements from inorganic forms to volatile organic compounds (e.g. selenium to methylated selenides) and elemental speciation (Pyrzynska, 1998; Pyrzynska, 2002). The percolation of volatile gases from pore water will aid in the transport of constituents (e.g. NAs) to upper layers (Holowenko et al., 2000). Volatile compounds such as gases will evolve out of the pond and into the atmosphere (e.g. methane, volatile organic compounds, hydrogen sulphide, oxides of nitrogen, organic compounds) (Baedecker et al., 2011; Vandenberg et al., 2012).    111  Chapter 5: Conclusion  Innovations in technology have improved bitumen extraction and included lower energy consumption and greater water recycling. The Oil Sands Process-affected Water (OSPW) and tailings produced from bitumen extraction are consequently more complex in substance composition, concentration of contaminants and changes in water chemistry. The probable concentration and ultimate fate of the various substances in tailings are affected by processes occurring within the tailings ponds. The pathway of salts, metals, hydrocarbons and acids fractions of OSPW over time in tailings ponds are multifaceted and can include chemical (e.g. partitioning, ion exchange, dissolution, adsorption and desorption) and biological processes (e.g. microbiological degradation). The author took on this research as an individual, broaching a wide topic, the integration and analysis which would typically be tackled by a team of multidisciplinary experts. The engineering problem was to determine the probable concentrations and ultimate fates of various substances of OSPW in a tailings pond. Microbial degradation has been shown to both reduce the content of toxic substances such as NAs and encourage aggregation and consolidation of suspended fractions (e.g. fines). The organic constituents are sources of carbon for aerobic and anaerobic microorganisms (Scott, 2007). Due to the recalcitrant nature of naphthenic acids, they are the last carbon source utilized (Holowenko et al., 2002). Microbial degradation of NAs reduces their toxicity and therefore continuous input of fresh OPSW may hinder optimal natural attenuation in tailings ponds (Herman et al., 1994). The vast majority of the existing research on NA degradation has been on commercial NAs, which have been shown to be more biodegradable than those from oil sands origin (Scott, 2007). 112  Chemical oxidation (e.g. UV irradiation, ozonation) tends to alter the chemical structure of recalcitrant compounds facilitating microbial degradation (Scott 2007). Ozonation pretreatment to microbiological processes has shown to improve biodegradability. Future innovations in the treatment of OSPW should combine ozonation and microbiological treatments. Treatment to remove constituents would also be important in operations, as bitumen recovery is decreased by high concentrations of ions (e.g. K+, Na+) and hydrolysable metal cations (Cao et al., 2007). Interestingly NAs are natural surfactants and may assist in bitumen recovery (Clemente et al., 2005). However, additives in assisted tailings consolidation such as Gypsum (CaSO4·2H2O) result in significant increases in calcium, calcium carbonate and sodium. The slurry of OSPW and tailings at discharge into the pond is 30-55% weight solids to liquids. The total time for self-weight sedimentation and consolidation of fines is estimated to be 125-150 years (Eckert et al., 1996). Consolidation of fines is enhanced through microorganisms (e.g. methanogens) (Bordenave et al., 2010). The flux of continuous discharge into a pond may result in mixing and resuspension of fines. Significant methanogenic activity has been shown in MLSB, operations to encourage natural attenuation and settling may prove energy efficient. The gaseous emissions from MLSB are currently uncontrolled and are an input to atmospheric greenhouse gases. Atmospheric emissions have been described by Kelly and associates (2009) where PAH contaminated snow, contained up to 4.8 mg/L of PAHs. It was estimated that PAHs were deposited associated with particulates, however, the exact source and modes of transmission need further research. The mining related land disturbances expose the landscape to the forces of wind and erosion, enhancing the transport of constituents. The oil sand landscape is found within the lower Mackenzie River basin, where flooding events are frequent (Headley et al., 2002; 113  Yunker et al., 1993). The Athabasca River is the major waterway in the area and flooding has been identified as a major contributor in the mobilization and transport of PACs (Hall et al., 2012).  The goal of this research was achieved where explanation was provided for the pathways of salts, metals, hydrocarbons and acids fractions of OSPW in tailings ponds. The special examination of the Mildred Lake Settling basin proved to better elucidate these factors and prevented the encroachment of unknown variables. In addition, the reduced scope included the examination of processing prior to coke refinement, which focused consideration of the components influencing changes in water quality. The historical influences have included innovations in bitumen recovery and assisted tailings consolidation. These technological changes create a challenge in the comprehensive appreciation of how these factors affect the processes occurring in tailings impoundments over time. In addition, the exact composition of tailings has not been determined by the scientific literature, due to the high complexity of organic compounds which are yet to be identified. The physical, chemical and biological processes occurring within a tailings pond are multifaceted making it difficult to model the ultimate fates of various substances.  This research is the first of its kind, to analyze and integrate most known scientific sources of information on the physical, chemical and biological properties and processes of the Alberta oil sands regions OSPW, tailings pond and affected landscape. This thesis defined the objectives to modeling and a conceptual model was created; the first two steps in the creation of a working predictive model.  The distinct significance of this research was in the development of a conceptual Tailings Pond Model, where the broad-spectrum of complex processes were incorporated into a comprehensive package. Current and past research in the field was 114  highlighted and their overall significance to the working hypotheses on the oil sands affected landscape. 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Limnology. Saunders College. Whitby, C., 2010. Microbial naphthenic acid degradation. Advances in Applied Microbiology 70, 93-125. Xiumei, H; MacKinnon, MD; Martin, JW. 2009. Estimating the in situ biodegradation of naphthenic acids in oil sands process waters by HPLC/HRMS. Chemosphere 76, 63-70. Yunker MB, Macdonald RW, Cretney WJ, Fowler BR, McLaughlin FA. 1993. Alkane, terpene, and polycyclic aromatic hydrocarbon geochemistry of the Mackenzie River and Mackenzie shelf: Riverine contributions to the Beaufort Sea coastal sediment. Geochim Cosmochim Acta 57, 3041-3061. Zubot, WA. 2010. Removal of naphthenic acids from oil sands process water using petroleum coke. MSc Thesis. University of Alberta, Edmonton, Canada. 126  Appendices  Appendix A  Literature Reviewed  A.1 Sub-Appendix literature reviewed and number of times articles are cited in literature. Certain sources such as theses and websites typically were not cited. Articles Times Cited (#) Characterization 274 Cao et al., 2007 3 Chalaturnyk et al., 2002 22 Clemente, 2004 0 Conly et al., 2007 4 Gagné et al., 2011 1 Gueguen et al., 2011 2 Hall et al., 2012 0 Kelesoglu et al., 2011 0 Kelly et al., 2009 24 Levi, 2009 0 Ma, 2012 0 MacKinnon et al., 2001 4 Masliyah et al., 2004 71 Mohammed et al., 2009 1 Nji, 2010 0 Nordgard et al., 2012 1 Pyrzynska, 1998 41 Pyrzynska, 2002 43 RAMP, 2012 0 Rogers et al., 2002 57 Sansom, 2010 0 Tompkins, 2009 0 Zubot, 2010 0 Geochemical 113 Holden et al., 2011 2 Yunker et al., 1993 111  127  Articles Times Cited (#) Geology 193 Headley et al., 2002 5 Ladd et al., 1993 103 Rubinstein et al., 1977 85 Limnology 139 Alvarez-Cobelas et al., 2005 6 Bennett, 1978 0 Girgis and Smith, 1980 0 Hostetler and Bartlein, 1990 110 Jonas et al., 2003 11 Kirillin et al., 2012 4 Mishra et al., 2011 4 Noges et al., 2011 0 Read, 2012 0 Rouse, 2009 4 Welch, 1952 0 Wetzel,1983 0 Microbial 337 Baedecker et al., 2011 0 Bordenave et al., 2010 5 Fedorak et al., 2003 0 Herman et al., 1994 85 Holowenko et al., 2000 34 Holowenko et al., 2001 43 Holowenko et al., 2002 91 Kannel et al., 2012 3 Leung et al., 2001 25 McNab and Narasimhan, 1995. 19 Scott, 2007 0 Sen, 2011 4 Xiumei et al., 2009 28           128  Articles Times Cited (#) Mine Engineering 0 Aubé, 2004 0 CAPP, 2012 0 Chastko, 2004 0 Government of Alberta, 2011 0 Government of Alberta, 2012 0 Hrynyshyn et al., 2012 0 Jiang et al., 2013 0 Klohn, 1997 0 McKenna et al., 2012 0 Oil sands info mine, 2012 0 Sobkowicz, 2012 0 Vandenberg et al., 2012 0 Toxicology 389 Baker et al., 2012 0 CCME, 2011 0 Clemente et al., 2005 111 Debenest et al., 2012 0 Frank, 2008 77 Gentes, 2006   Jordaan, 2012 0 Kavanagh et al., 2011 28 Kelly et al., 2010 27 Leung et al., 2003 62 Merlin Ibarra, 2007 0 Parsons, 2007 0 Rogers et al., 2002 57 Van den Heuvel et al., 1999 27 Treatment 127 Allen, 2008 50 El-Din et al., 2011 6 Peng et al., 2004 14 Scott et al., 2008 38 Whitby, 2010 19 Grand Total 1572   129   A.2 Sub-Appendix literature reviewed and was not used in thesis. Certain sources such as theses and websites typically were not cited. Articles Times Cited (#) Characterization 121 Clemente, J.S., MacKinnon, M.D., Fedorak, P.M., 2004. Aerobic biodegradation of two commercial naphthenic acids preparations. Environmental Science and Technology 38(4), 1009-1016. 41 Guéguen, C., Burns, D.C., McDonald, A., Ring, B., 2012. Structural and optical characterization of dissolved organic matter from the lower Athabasca River, Canada. Chemosphere 87, 932-937. 0 Headley, J.V., Crosley, B., Conly, F.M., Quagraine, E.K., 2005. The characterization and distribution of inorganic chemicals in tributary waters of the lower Athabasca River, oilsands region, Canada. Journal of Environmental Science and Health Part A: Toxic/Hazardous Substances & Environmental Engineering 40(1), 1-27. 6 Ibarra, M., del Carmen, M., 2007. The application of a GC-MS method to detect naphthenic acids in natural waters, rat liver, plasma, and plant tissues. M.Sc. thesis, University of Alberta, Department of Civil and Environmental Engineering. 0 Kasperski, K.L., 1992. A review of properties and treatment of oil sands tailings. Aostra J. Res. 8, 11–53. 0 Scott, A.C., MacKinnon, M.D., Fedorak, P.M., 2005. Naphthenic acids in athabasca oil sands tailings waters are less biodegradable than commercial naphthenic acids . Environmental Science & Technology 39(21), 8388-8394. 44 130   Articles Times Cited (#) Taylor, S.D., Czarnecki, J., Masliyah, J., 2001. Refractive index measurements of diluted bitumen solutions. Fuel 80(14),  2013-2018. 13 Zhao, S.Q., Kotlyar, L.S., Woods, J.R., Sparks, B.D., Gao, J.S., Kung, J., Chung, K.H., 2002. A benchmark assessment of residues: comparison of Athabasca bitumen with conventional and heavy crudes. Fuel 81(6), 737–746. 17 Geochemical 5 Chen, L., Kost, D., Dick, D.A., 2010. Petroleum coke circulating fluidized bed combustion product effects on soil and water quality. Soil Science 175(6), 270–277. 5 Geology 66 Philippi, G.T., 1977. Depth, time and mechanism of origin of heavy to medium-gravity naphthenic crude oils. Geochimica et Cosmochimica Acta 41(1), 33-52. 66 Microbial 161 Dutta, T.K., Harayama, S. 2001. Biodegradation of n-alkylcycloalkanes and n-alkylbenzenes via new pathways in Alcanivorax sp. strain. Applied and Environmental Microbiology 67(4), 1970-1974. 42 Fedorak, P.M., Coy, D.L., Salloum, M.J., Dudas, M.J., 2002. Methanogenic potential of tailings samples from oil sands extraction plants. Canadian Journal of Microbiology 48(1), 21. 19   131  Articles Times Cited (#) Hadwin, A.K.M., Del Rio, L.F., Pinto, L.J., Painter, M.,  Routledge, R., Moore, M.M., 2006. Microbial communities in wetlands of the Athabasca oil sands: genetic and metabolic characterization. Fems Microbiology Ecology 55(1), 68-78. 20 Johnson, R.J., West, C.E., Swaih, A.M., Folwell, B.D., Smith, B.E., Rowland, S.J., Whitby, C., 2012. Aerobic biotransformation of alkyl branched aromatic alkanoic naphthenic acids via two different pathways by a new isolate of Mycobacteriumemi. Environmental Microbiology 14(4), 872-882. 1 Misiti, T., Tandukar, M.,  Tezel, U.,  Pavlostathis, S.G., 2013. Inhibition and biotransformation potential of naphthenic acids under different electron accepting conditions. Water Research 47(1), 406-418. 0 Quagraine, E.K., Peterson, H.G., Headley, J.V., 2005. In situ bioremediation of naphthenic acids contaminated tailing pond waters in the Athabasca oil sands region-demonstrated field studies and plausible options: a review. Journal of Environmental Science and Health Part A: Toxic/Hazardous Substances & Environmental Engineering 40(3), 685-722. 47 Saddique, T., Gupta, R., Fedorak, P.M.,  MacKinnon, M.D., Foght, J.M., 2008. A first approximation kinetic model to predict methane generation from an oil sands tailings settling basin. Chemosphere 72, 1573-1580. 11   132  Articles Times Cited (#) Smith, B.E., Lewis, A., Belt, S., Whitby, C., Rawland, S., 2008. Effects of alkyl chain branching on the biotransformation of naphthenic acids. Environmental Science and Technology 42(24), 9323-9328. 21 Mine Engineering 0 Shell Canada Limited, 2007. Jackpine Mine Expansion and Pierre River Mine Project Application and Environmental Impact Assessment. Volumes 4. Submitted to Alberta Energy and Utilities Board and Alberta Environment, December, 2007. Calgary, AB. Availbale from: <http://s01.static-shell.com/content/dam/shell-new/local/country/can/downloads/pdf/aboutshell/aosp/vol-4a-eia-aquaticresources.pdf.> 0 Multiphase flow 29  Joekar-Niasar, V., van Dijke, M.I.J., Hassanizadeh, S.M., 2012. Pore-scale modeling of multiphase flow and transport: achievements and perspectives. Transport in porous media 94(2), 461-464. 0 Joekar-Niasar, V., Hassanizadeh, S.M., Leijnse, A., 2008. Insights into the relationships among capillary pressure, saturation, interfacial area and relative permeability using pore-network modeling. Transp. Porous. Med. 74, 201–219. 28 Karadimitriou, N. K., Hassanizadeh, S.M., 2012. A review of micromodels and their use in two-phase flow studies. Vadose Zone Journal 11(3), 1-21. 1 Parker, J.C., 1989. Multiphase flow and transport in porous media. Reviews of geophysics 27(3), 311-328. 0   133  Articles Times Cited (#) Toxicology 90 Colavecchia, M.V., Backus, S.M., Hodson, P.V., Parrott, J.L., 2004. Toxicity of oil sands to early life stages of fathead minnows (Pimephales promelas). Environ. Toxicol. Chem. 23, 1709–1718. 47 Hebert, C.E., Weseloh, D.V.,  MacMillan, S., Campbell, D., Nordstrom, W., 2011. Metals and polycyclic aromatic hydrocarbons in colonial waterbird eggs from Lake Athabasca and the Peace-Athabasca Delta, Canada.  Environmental Toxicology and Chemistry 30(5), 1178-1183. 1 Neroa, V., Farwella, A.,  Lee, L.E.J., Van Meerc, T.,  MacKinnond, M.D., Dixon, D.G., 2006.  The effects of salinity on naphthenic acid toxicity to yellow perch: gill and liver histopathology. Ecotoxicology and Environmental Safety 65(2), 252-264. 33 Palmer, L.J., Hogan, N.S., van den Heuvel, M.R., 2012. Phylogenetic analysis and molecular methods for the detection of lymphocystis disease virus from yellow perch, Perca flavescens (Mitchell). Journal of Fish Diseases 35 (9), 661-670. 0 Puttaswamy, N., Turcotte, D., Liber K., 2010. Variation in toxicity response of Ceriodaphnia dubia to Athabasca oil sands coke leachates. Chemosphere 80(5), 489–97. 7 Sansom, B., Vo, N.T.K., Kavanagh, R., Hanner, R., MacKinnon, M., Dixon, D.G.,  2013. Rapid assessment of the toxicity of oil sands process-affected waters using fish cell lines. In Vitro Cellular & Developmental Biology-Animal 49(1), 52-65. 0   134  Articles Times Cited (#) Squires, A.J., 2005. Ecotoxicological assessment of using coke in aquatic reclamation strategies at the Alberta oil sands. Master of Science Thesis, University of Saskatchewan. 0 Squires, A.J., Liber, K., 2004. Ecotoxicological assessment of using oil sands coke in aquatic reclamation strategies. Conference:  31st Annual Aquatic Toxicity Workshop  Location: Charlottetown, PE, Canada. Canadian Technical Report of Fisheries and Aquatic Sciences 2562,  54.   0 Wiklund, J.A., Hall, R.I., Wolfe, B.B., Edwards, W.D., Farwell, A.J., Dixon, D.G., 2012. Has Alberta oil sands development increased far-field delivery of airborne contaminants to the Peace-Athabasca Delta? Science of the Total Environment 433, 379-382. 2 Treatment 87 Allen, E.W., 2008. Process water treatment in Canada's oil sands industry: II. A review of emerging technologies. Journal of Environmental Engineering and Science 7(5), 499-524. 17 Caughill, D.L., Morgenstern, N.R., Scott, J.D. 1993. Geotechnics of nonsegregating oil sand tailings. Canadian Geotechnical Journal 30(5), 801-811. 7 Knight, R.L., Kadlec, R.H., Ohlendorf, H.M., 1999. The use of treatment wetlands for petroleum industry effluents. Environ. Sci. Technol. 33 (7), 973–980. 63 MacKinnon, M., Boerger, H., 1986. Description of two treatments for detoxifying oil sands tailings pond water. Water Pollut. Res. J. Can. 21, 496-512. 0 Grand Total 559    135  Appendix B  CCME Data B.1 Sub-Appendix CCME tested data The tested data was created automatically by the CCME Water Quality Index calculator, with colour-coded cells where grey data exceeded objective by less than 10 times, yellow data exceeded objective by 10-25 times and red data exceeded objectives by over 25 times. 136  Station NumberSampleDateIndexPeriodhardnessPb (Lead)ObjectivePb (Lead)Ag (Silver)ObjectiveAg (Silver) pHAlObjectiveAl (Aluminum)AmmoniaObjectiveAmmoniaAs (Arsenic)ObjectiveAs (Arsenic)ChlorideObjectiveChlorideAllen 2008 2007 2007 1122 (999.00) 0.1 -9998.00 0.10(999.0000) 0.0152 14.00 5 (999.00) 150 (999.00)Allen 2008 2007 2007 112 2 (999.00) 0.1 -999 8.40 0.10 (999.0000) 0.0152 (999.00) 5 (999.00) 150 (999.00)Allen 2008 2007 2007 112 2 (999.00) 0.1 -999 9.00 0.10 (999.0000) 0.0152 (999.00) 5 (999.00) 150 (999.00)Allen 2008 2007 2007 112 2 (999.00) 0.1 -999 9.00 0.10 (999.0000) 0.0152 (999.00) 5 (999.00) 150 (999.00)Allen 2008 2007 2007 112 2 (999.00) 0.1 -999 9.00 0.10 (999.0000) 0.0152 (999.00) 5 (999.00) 150 (999.00)Allen 2008 2007 2007 112 2 (999.00) 0.1 -999 9.00 0.10 (999.0000) 0.0152 (999.00) 5 (999.00) 150 (999.00)Allen 2008 2007 2007 91 2 (999.00) 0.1 -999 9.00 0.10 (999.0000) 0.0152 (999.00) 5 (999.00) 150 (999.00)Allen 2008 2007 2007 112 2 (999.00) 0.1 -999 9.00 0.10 (999.0000) 0.0152 (999.00) 5 (999.00) 150 (999.00)Baker et al 2012 2011 2011 112 2 54.40 0.1 -999 7.87 0.10 (999.0000) 0.0152 (999.00) 5 31.10 150 (999.00)Baker et al 2012 2011 2011 112 2 0.70 0.1 -999 7.47 0.10 (999.0000) 0.0152 (999.00) 5 7.10 150 (999.00)Baker et al 2012 2011 2011 112 2 (999.00) 0.1 -999 9.00 0.10 (999.0000) 0.0152 (999.00) 5 (999.00) 150 (999.00)Baker et al 2012 2011 2011 112 2 (999.00) 0.1 -999 9.00 0.10 (999.0000) 0.0152 (999.00) 5 (999.00) 150 (999.00)Debenest et al 2012 2011 2011 112 2 14.70 0.1 -999 9.00 0.10 18.9000 0.0152 (999.00) 5 5.90 150 (999.00)El-Din et al 2011 2010 2010 112 2 (999.00) 0.1 (999) 8.70 0.10 (999.0000) 0.0152 (999.00) 5 (999.00) 150 (999.00)Holden et al 2011 2010 2010 112 2 (999.00) 0.1 (999) 8.60 0.10 -999 0.0152 2.02 5 (999.00) 150 374.51Holowenko et al 2000 1997 1997 112 2 -999 0.1 -999 8.10 0.10 -999 0.0152 6.7 5 -999 150 536.00Holowenko et al 2000 1997 1997 112 2 -999 0.1 -999 9.00 0.10 -999 0.0152 8.8 5 -999 150 195.00Holowenko et al 2000 1997 1997 112 2 -999 0.1 -999 9.00 0.10 -999 0.0152 7.6 5 -999 150 265.00Holowenko et al 2000 1997 1997 112 2 -999 0.1 -999 9.00 0.10 -999 0.0152 7.5 5 -999 150 284.00Holowenko et al 2000 1997 1997 112 2 -999 0.1 -999 9.00 0.10 -999 0.0152 7.5 5 -999 150 298.00Holowenko et al 20001998 1998 112 2 (999.00) 0.1 (999) 8.30 0.10 -999 0.0152 9 5 (999.00) 150 634.00Holowenko et al 20001998 1998 112 2 (999.00) 0.1 (999) 8.30 0.10 -999 0.0152 10 5 (999.00) 150 386.00Holowenko et al 20001998 1998 112 2 (999.00) 0.1 (999) 9.00 0.10 -999 0.0152 10 5 (999.00) 150 307.00Holowenko et al 20001998 1998 112 2 (999.00) 0.1 (999) 8.30 0.10 -999 0.0152 10 5 (999.00) 150 301.00Holowenko et al 20001998 1998 112 2 (999.00) 0.1 (999) 8.50 0.10 -999 0.0152 9.3 5 (999.00) 150 150.00Holowenko et al 20001998 1998 112 2 (999.00) 0.1 (999) 8.50 0.10 -999 0.0152 8.7 5 (999.00) 150 127.00Hrynyshyn et al 2012 1997 1997 112 2 (999.00) 0.1 (999) 8.10 0.10 -999 0.0152 0.35 5 (999.00) 150 52.00Hrynyshyn et al 2012 2003 2003 112 2 (999.00) 0.1 (999) 8.20 0.10 (999.0000) 0.0152 14 5 (999.00) 150 540.00Hrynyshyn et al 2012 2007 2007 405 7 1.40 0.1 470 9.00 0.10 0.1300 0.0152 (999.00) 5 2300.00 150 (999.00)Hrynyshyn et al 2012 2007 2007 112 2 (999.00) 0.1 (999) 9.00 0.10 (999.0000) 0.0152 5.00 5 10.00 150 800.00Hrynyshyn et al 2012 2007 2007 112 2 (999.00) 0.1 (999) 9.00 0.10 (999.0000) 0.0152 10.00 5 10.00 150 600.00Hrynyshyn et al 2012 2007 2007 112 2 (999.00) 0.1 (999) 9.00 0.10 (999.0000) 0.0152 7.00 5 10.00 150 800.00Hrynyshyn et al 2012 2007 2007 112 2 1.20 0.1 (999) 9.00 0.10 0.4700 0.0152 6.40 5 2.20 150 139.00Leung et al 2003 2002 2002 112.00 2 (999.00) 0.1 (999) 8.69 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 113.00Ma 2012 2011 2011 112.00 2 (999.00) 0.1 (999) 9.00 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 336.00Mackinnon et al 20012000 2000 112.00 2 (999.00) 0.1 (999) 8.50 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Mackinnon et al 20012000 2000 112.00 2 (999.00) 0.1 (999) 9.00 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Mackinnon et al 20012000 2000 112.00 2 (999.00) 0.1 (999) 5.00 0.01 (999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Mackinnon et al 20012000 2000 112.00 2 (999.00) 0.1 (999) 12.00 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Mackinnon et al 20012000 2000 112.00 2 (999.00) 0.1 (999) 8.20 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Mackinnon et al 20012000 2000 112.00 2 (999.00) 0.1 (999) 8.10 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Mackinnon et al 20012000 2000 112.00 2 (999.00) 0.1 (999) 8.20 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Mackinnon et al 20012000 2000 112.00 2 (999.00) 0.1 (999) 9.00 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Peng et al 2004 2003 2003 112.00 2 (999.00) 0.1 (999) 8.50 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 330.00Peng et al 2004 2003 2003 112.00 2 (999.00) 0.1 (999) 7.80 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 225.00Peng et al 2004 2003 2003 112.00 2 (999.00) 0.1 (999) 8.00 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 300.00Peng et al 2004 2003 2003 112.00 2 (999.00) 0.1 (999) 8.30 0.10 (999.00) 0.0152 (999.00) 5 (999.00) 150 760.00Sansom 2010 2007 2007 112.00 2 (999.00) 0.1 (999) 8.10 0.10 (999.00) 0.0152 0.18 5 (999.00) 150 240.00Sansom 2010 2007 2007 112.00 2 (999.00) 0.1 (999) 8.20 0.10 (999.00) 0.0152 0.29 5 (999.00) 150 320.00Sansom 2010 2007 2007 112.00 2 (999.00) 0.1 (999) 7.70 0.10 (999.00) 0.0152 0.01 5 (999.00) 150 650.00Sansom 2010 2007 2007 112.00 2 (999.00) 0.1 (999) 7.60 0.10 (999.00) 0.0152 16.90 5 (999.00) 150 440.00Sansom 2010 2007 2007 112.00 2 (999.00) 0.1 (999) 8.24 0.10 (999.00) 0.0152 0.29 5 (999.00) 150 4.60Data for PH Objective 137  Station NumberSampleDateIndexPeriodhardnessPb (Lead)ObjectivePb (Lead)Ag (Silver)ObjectiveAg (Silver) pHAlObjectiveAl (Aluminum)AmmoniaObjectiveAmmoniaAs (Arsenic)ObjectiveAs (Arsenic)ChlorideObjectiveChlorideSansom 2010 2007 2007 112.002 (999.00) 0.1 (999)8.39 0.10(999.00) 0.0152 0.27 5 (999.00) 150 35.00Sansom 2010 2007 2007 112.002 (999.00) 0.1 (999)8.39 0.10(999.00) 0.0152 0.30 5 (999.00) 150 31.00Sansom 2010 2007 2007 112.002 (999.00) 0.1 (999)8.53 0.10(999.00) 0.0152 0.28 5 (999.00) 150 27.00Sansom 2010 2007 2007 112.002 (999.00) 0.1 (999)8.80 0.10(999.00) 0.0152 2.10 5 (999.00) 150 140.00Sansom 2010 2007 2007 112.002 (999.00) 0.1 (999)8.77 0.10(999.00) 0.0152 0.21 5 (999.00) 150 34.00Sansom 2010 2007 2007 1122 -999 0.1 -9998.98 0.100.6 0.0152 0.18 5 -999 150 240Sansom 2010 2007 2007 1122 -999 0.1 -9998.91 0.100.7 0.0152 0.29 5 -999 150 320Sansom 2010 2007 2007 1122 -999 0.1 -9998.90 0.100.1 0.0152 0.35 5 -999 150 110Sansom 2010 2007 2007 1122 -999 0.1 -9998.85 0.10-999 0.0152 0.21 5 -999 150 14Sansom 2010 2007 2007 1122 -999 0.1 -9998.51 0.10-999 0.0152 0.01 5 -999 150 650Sansom 2010 2007 2007 1122 -999 0.1 -9997.77 0.10-999 0.0152 2.31 5 -999 150 220Sansom 2010 2007 2007 1122 -999 0.1 -9998.16 0.10-999 0.0152 0.01 5 -999 150 480Sansom 2010 2007 2007 1122 -999 0.1 -9998.31 0.10-999 0.0152 0.16 5 -999 150 12Sansom 2010 2007 2007 1122 -999 0.1 -9997.02 0.10-999 0.0152 0.23 5 -999 150 150Sansom 2010 2007 2007 112.002 (999.00) 0.1 (999)7.53 0.10(999.00) 0.0152 2.72 5 (999.00) 150 240.00Sansom 2010 2007 2007 112.002 (999.00) 0.1 (999)7.93 0.100.33 0.0152 16.90 5 (999.00) 150 440.00Sansom 2010 2007 2007 112.002 (999.00) 0.1 (999)8.36 0.10(999.00) 0.0152 13.40 5 (999.00) 150 530.00Sansom 2010 2007 2007 112.002 (999.00) 0.1 (999)8.25 0.10(999.00) 0.0152 2.60 5 (999.00) 150 250.00Sansom 2010 2007 2007 112.002 (999.00) 0.1 (999)7.34 0.10(999.00) 0.0152 14.90 5 (999.00) 150 520.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.83 0.10(999.00) 0.0152 0.01 5 (999.00) 150 38.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)7.64 0.10(999.00) 0.0152 0.01 5 (999.00) 150 4.40Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.25 0.10(999.00) 0.0152 0.22 5 (999.00) 150 43.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.11 0.100.60 0.0152 0.56 5 (999.00) 150 17.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.32 0.10(999.00) 0.0152 0.01 5 (999.00) 150 4.70Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)7.57 0.10(999.00) 0.0152 30.80 5 (999.00) 150 5.10Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.19 0.10(999.00) 0.0152 94.40 5 (999.00) 150 37.90Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.69 0.10(999.00) 0.0152 0.18 5 (999.00) 150 6.50Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.91 0.10(999.00) 0.0152 0.17 5 (999.00) 150 25.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)7.69 0.10(999.00) 0.0152 0.12 5 (999.00) 150 5.60Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.00 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.35 0.10(999.00) 0.0152 0.70 5 (999.00) 150 33.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.52 0.10(999.00) 0.0152 0.14 5 (999.00) 150 29.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.96 0.10(999.00) 0.0152 0.23 5 (999.00) 150 140.00Data for PH Objective 138   Station NumberSampleDateIndexPeriodhardnessPb (Lead)ObjectivePb (Lead)Ag (Silver)ObjectiveAg (Silver) pHAlObjectiveAl (Aluminum)AmmoniaObjectiveAmmoniaAs (Arsenic)ObjectiveAs (Arsenic)ChlorideObjectiveChlorideSansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.03 0.10(999.00) 0.0152 0.34 5 (999.00) 150 37.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.20 0.100.60 0.0152 0.28 5 (999.00) 150 230.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.81 0.100.90 0.0152 0.01 5 (999.00) 150 310.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)9.06 0.100.20 0.0152 0.15 5 (999.00) 150 112.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)7.83 0.10(999.00) 0.0152 0.01 5 (999.00) 150 12.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.61 0.10(999.00) 0.0152 0.01 5 (999.00) 150 15.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.72 0.10(999.00) 0.0152 0.01 5 (999.00) 150 690.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.93 0.10(999.00) 0.0152 0.10 5 (999.00) 150 69.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)7.56 0.10(999.00) 0.0152 2.17 5 (999.00) 150 210.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)7.96 0.10(999.00) 0.0152 0.51 5 (999.00) 150 250.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.07 0.10(999.00) 0.0152 0.01 5 (999.00) 150 340.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)7.49 0.10(999.00) 0.0152 0.01 5 (999.00) 150 130.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.94 0.100.40 0.0152 0.01 5 (999.00) 150 55.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)7.59 0.10(999.00) 0.0152 2.81 5 (999.00) 150 250.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)7.20 0.10(999.00) 0.0152 2.70 5 (999.00) 150 280.00Sansom 2010 2008 2008 112.002 (999.00) 0.1 (999)8.22 0.10(999.00) 0.0152 0.01 5 (999.00) 150 8.00Scott et al 2008 2007 2007 112.002 (999.00) 0.1 (999)8.20 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 (999.00)Tompkins 2009 2008 2008 112.002 (999.00) 0.1 (999)8.40 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 75.00Tompkins 2009 2008 2008 1122 -999 0.1 -9999.00 0.10-999 0.0152 -999 5 -999 150 550Van den Heuvel et al 19991995 1995 1122 -999 0.1 -9998.50 0.100.072 0.0152 0.07 5 1 150 36.1Xiumei et al 2009 2006 2006 1122 -999 0.1 -9999.00 0.10-999 0.0152 25 5 -999 150 350Xiumei et al 2009 2006 2006 1122 -999 0.1 -9999.00 0.10-999 0.0152 15 5 -999 150 510Xiumei et al 2009 2006 2006 1122 -999 0.1 -9999.00 0.10-999 0.0152 5 5 -999 150 375Xiumei et al 2009 2006 2006 1122 -999 0.1 -9999.00 0.10-999 0.0152 15 5 -999 150 570Xiumei et al 2009 2006 2006 1122 -999 0.1 -9999.00 0.10-999 0.0152 5 5 -999 150 291Xiumei et al 2009 2006 2006 1122 -999 0.1 -9999.00 0.10-999 0.0152 4 5 -999 150 101Zubot 2010 1997 1997 1122 -999 0.1 -9997.80 0.10-999 0.0152 5.1 5 -999 150 375Zubot 2010 1998 1998 1122 -999 0.1 -9997.80 0.10-999 0.0152 6.3 5 -999 150 390Zubot 2010 1999 1999 1122 -999 0.1 -9998.10 0.10-999 0.0152 4.1 5 -999 150 610Zubot 2010 2000 2000 112.002 (999.00) 0.1 (999)8.09 0.10(999.00) 0.0152 3.50 5 (999.00) 150 910.00Zubot 2010 2001 2001 112.002 (999.00) 0.1 (999)8.20 0.10(999.00) 0.0152 3.80 5 (999.00) 150 970.00Zubot 2010 2002 2002 112.002 (999.00) 0.1 (999)8.13 0.10(999.00) 0.0152 4.40 5 (999.00) 150 925.00Zubot 2010 2003 2003 112.002 (999.00) 0.1 (999)8.17 0.10(999.00) 0.0152 4.40 5 (999.00) 150 860.00Zubot 2010 2004 2004 112.002 (999.00) 0.1 (999)8.02 0.10(999.00) 0.0152 7.00 5 (999.00) 150 750.00Zubot 2010 2005 2005 112.002 (999.00) 0.1 (999)8.12 0.10(999.00) 0.0152 5.90 5 (999.00) 150 610.00Zubot 2010 2006 2006 112.002 (999.00) 0.1 (999)8.05 0.10(999.00) 0.0152 4.90 5 (999.00) 150 570.00Zubot 2010 2007 2007 112.002 (999.00) 0.1 (999)8.10 0.10(999.00) 0.0152 15.00 5 (999.00) 150 490.00Zubot 2010 2009 2009 112.002 15.00 0.1 (999)9.10 0.100.10 0.0152 (999.00) 5 (999.00) 150 520.00Zubot 2010 2009 2009 112.002 15.00 0.1 (999)9.10 0.100.20 0.0152 (999.00) 5 (999.00) 150 520.00Zubot 2010 2009 2009 112.002 0.30 0.1 09.00 0.100.59 0.0152 (999.00) 5 5.20 150 (999.00)Zubot 2010 2009 2009 112.002 (999.00) 0.1 (999)8.50 0.10(999.00) 0.0152 (999.00) 5 (999.00) 150 520.00Data for PH Objective139  Station NumberSampleDatehardnessCdObjectiveCd (Cadmium)Cr-III (Chromium III)ObjectiveCr-III (Chromium III)Cr-VI (Chromium VI)ObjectiveCr-VI (Chromium VI)hardnessCuObjectiveCu (Copper)DO (Dissolved Oxygen)ObjectiveDO (Dissolved Oxygen)Fe (Iron)ObjectiveFe (Iron)Hg (Inorganic Mercury)ObjectiveHg (Inorganic Mercury)MeHg (Methyl Mercury)ObjectiveAllen 2008 2007 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Allen 2008 2007 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Allen 2008 2007 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Allen 2008 2007 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Allen 2008 2007 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Allen 2008 2007 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Allen 2008 2007 91.00 0.03(999.00) 8.9 -999 1 -99991.00 2.18(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Allen 2008 2007 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Baker et al 2012 2011 112.00 0.040.17 8.9 -999 1 5.3112.00 2.618.10 9.5 ~ 5.5 -999 300 397.8 0.026 -999 0.004Baker et al 2012 2011 112.00 0.040.08 8.9 -999 1 3.4112.00 2.611.30 9.5 ~ 5.5 -999 300 350.4 0.026 -999 0.004Baker et al 2012 2011 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Baker et al 2012 2011 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Debenest et al 2012 2011 112.00 0.04(999.00) 8.9 -999 1 33.2112.00 2.6123.00 9.5 ~ 5.5 -999 300 12500 0.026 -999 0.004El-Din et al 2011 2010 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Holden et al 2011 2010 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Holowenko et al 2000 1997 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Holowenko et al 2000 1997 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Holowenko et al 2000 1997 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Holowenko et al 2000 1997 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Holowenko et al 2000 1997 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Holowenko et al 20001998 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Holowenko et al 20001998 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Holowenko et al 20001998 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Holowenko et al 20001998 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Holowenko et al 20001998 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Holowenko et al 20001998 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Hrynyshyn et al 2012 1997 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Hrynyshyn et al 2012 2003 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Hrynyshyn et al 2012 2007 405.00 0.114.40 8.9 -999 1 -999405.00 7.8176.00 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Hrynyshyn et al 2012 2007 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 10 0.026 0.05 0.004Hrynyshyn et al 2012 2007 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 200 0.026 0.03 0.004Hrynyshyn et al 2012 2007 112.00 0.04(999.00) 8.9 -999 1 -999112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 40 0.026 0.04 0.004Hrynyshyn et al 2012 2007 112.00 0.041.60 8.9 -999 1 4.4112.00 2.612.50 9.5 ~ 5.5 -999 300 76 0.026 0.047 0.004Leung et al 2003 2002 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Ma 2012 2011 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Mackinnon et al 20012000 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Mackinnon et al 20012000 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Mackinnon et al 20012000 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Mackinnon et al 20012000 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Mackinnon et al 20012000 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Mackinnon et al 20012000 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Mackinnon et al 20012000 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Mackinnon et al 20012000 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Peng et al 2004 2003 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Peng et al 2004 2003 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Peng et al 2004 2003 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Peng et al 2004 2003 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 11.2 300 -999 0.026 -999 0.004Data for Cd Objective Data for Cu Objective 140  Station NumberSampleDatehardnessCdObjectiveCd (Cadmium)Cr-III (Chromium III)ObjectiveCr-III (Chromium III)Cr-VI (Chromium VI)ObjectiveCr-VI (Chromium VI)hardnessCuObjectiveCu (Copper)DO (Dissolved Oxygen)ObjectiveDO (Dissolved Oxygen)Fe (Iron)ObjectiveFe (Iron)Hg (Inorganic Mercury)ObjectiveHg (Inorganic Mercury)MeHg (Methyl Mercury)ObjectiveSansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 12.5 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 10.8 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 11.4 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 12.6 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 11.8 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 9.1 300 200 0.026 -999 0.004Sansom 2010 2007 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 8.6 300 200 0.026 -999 0.004Sansom 2010 2007 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 10.7 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 14.5 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 11.1 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 0.8 300 1900 0.026 -999 0.004Sansom 2010 2007 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 8.2 300 500 0.026 -999 0.004Sansom 2010 2007 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 9.7 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 6.4 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 1.9 300 200 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 300 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 900 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 8 300 100 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 3.2 300 900 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 2.3 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 10.1 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 5.9 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 100 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 300 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 100 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 1000 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 200 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 1200 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 200 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 6.8 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 8.7 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 9.3 300 -999 0.026 -999 0.004Data for Cd Objective Data for Cu Objective 141  Station NumberSampleDatehardnessCdObjectiveCd (Cadmium)Cr-III (Chromium III)ObjectiveCr-III (Chromium III)Cr-VI (Chromium VI)ObjectiveCr-VI (Chromium VI)hardnessCuObjectiveCu (Copper)DO (Dissolved Oxygen)ObjectiveDO (Dissolved Oxygen)Fe (Iron)ObjectiveFe (Iron)Hg (Inorganic Mercury)ObjectiveHg (Inorganic Mercury)MeHg (Methyl Mercury)ObjectiveSansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 12.2 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 6.3 300 100 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 8.6 300 300 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 9.7 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 9.7 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 3.1 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 10.3 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 11.2 300 100 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 0.6 300 1000 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 7.9 300 200 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 6.1 300 1200 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 5.4 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 11.3 300 200 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 1.8 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 1 300 -999 0.026 -999 0.004Sansom 2010 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 9.1 300 -999 0.026 -999 0.004Scott et al 2008 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Tompkins 2009 2008 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Tompkins 2009 2008 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Van den Heuvel et al 19991995 112.00 0.041.5 8.9 -999 1 3112.00 2.612.2 9.5 ~ 5.5 -999 300 62 0.026 -999 0.004Xiumei et al 2009 2006 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Xiumei et al 2009 2006 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Xiumei et al 2009 2006 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Xiumei et al 2009 2006 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Xiumei et al 2009 2006 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Xiumei et al 2009 2006 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Zubot 2010 1997 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Zubot 2010 1998 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Zubot 2010 1999 112.00 0.04-999 8.9 -999 1 -999112.00 2.61-999 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Zubot 2010 2000 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 0.5 300 -999 0.026 -999 0.004Zubot 2010 2001 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 1 300 -999 0.026 -999 0.004Zubot 2010 2002 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 1 300 -999 0.026 -999 0.004Zubot 2010 2003 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 1.2 300 -999 0.026 -999 0.004Zubot 2010 2004 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 0.25 300 -999 0.026 -999 0.004Zubot 2010 2005 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 1.2 300 -999 0.026 -999 0.004Zubot 2010 2006 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 0.5 300 -999 0.026 -999 0.004Zubot 2010 2007 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 3.5 300 -999 0.026 -999 0.004Zubot 2010 2009 112.00 0.0410.00 8.9 (999.00) 1 15.00112.00 2.6120.00 9.5 ~ 5.5 -999 300 10 0.026 -999 0.004Zubot 2010 2009 112.00 0.0410.00 8.9 (999.00) 1 15.00112.00 2.6120.00 9.5 ~ 5.5 -999 300 10 0.026 -999 0.004Zubot 2010 2009 112.00 0.040.20 8.9 (999.00) 1 2.50112.00 2.611.00 9.5 ~ 5.5 -999 300 318 0.026 0.05 0.004Zubot 2010 2009 112.00 0.04(999.00) 8.9 (999.00) 1 (999.00)112.00 2.61(999.00) 9.5 ~ 5.5 -999 300 -999 0.026 -999 0.004Data for Cd Objective Data for Cu Objective 142  seasonalStation NumberSampleDateMeHg (Methyl Mercury)Mo (Molybdenum)ObjectiveMo (Molybdenum)hardnessNiObjectiveNi (Nickel)Nitrate (NO3)ObjectiveNitrate (NO3)pHObjectivepHPhosphorousObjectivePhosphorousSe (Selenium)ObjectiveSe (Selenium)Th (Thallium)ObjectiveTh (Thallium)Zn (Zinc)ObjectiveZn (Zinc)Allen 2008 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.00 0.02 -999 1 -999 0.8 -999 30 (999.00)Allen 2008 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.40 0.02 -999 1 -999 0.8 -999 30 (999.00)Allen 2008 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 (999.00)Allen 2008 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 (999.00)Allen 2008 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 (999.00)Allen 2008 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 (999.00)Allen 2008 2007-999 73 -99991.00 88.97(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 (999.00)Allen 2008 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 (999.00)Baker et al 2012 2011-999 73 6.32112.00 104.175.10 13 -999 6.5 ~ 9 7.87 0.02 -999 1 -999 0.8 -999 30 46.60Baker et al 2012 2011-999 73 4.63112.00 104.173.20 13 -999 6.5 ~ 9 7.47 0.02 -999 1 -999 0.8 -999 30 9.40Baker et al 2012 2011-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 (999.00)Baker et al 2012 2011-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 (999.00)Debenest et al 2012 2011-999 73 6.1112.00 104.1751.40 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 39.10El-Din et al 2011 2010-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.70 0.02 -999 1 -999 0.8 -999 30 -999Holden et al 2011 2010-999 73 -999112.00 104.17(999.00) 13 4.65 6.5 ~ 9 8.60 0.02 -999 1 -999 0.8 -999 30 -999Holowenko et al 2000 1997-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 8.1 0.02 -999 1 -999 0.8 -999 30 -999Holowenko et al 2000 1997-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 9 0.02 -999 1 -999 0.8 -999 30 -999Holowenko et al 2000 1997-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 9 0.02 -999 1 -999 0.8 -999 30 -999Holowenko et al 2000 1997-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 9 0.02 -999 1 -999 0.8 -999 30 -999Holowenko et al 2000 1997-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 9 0.02 -999 1 -999 0.8 -999 30 -999Holowenko et al 20001998-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.30 0.02 -999 1 -999 0.8 -999 30 -999Holowenko et al 20001998-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.30 0.02 -999 1 -999 0.8 -999 30 -999Holowenko et al 20001998-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Holowenko et al 20001998-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.30 0.02 -999 1 -999 0.8 -999 30 -999Holowenko et al 20001998-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.50 0.02 -999 1 -999 0.8 -999 30 -999Holowenko et al 20001998-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.50 0.02 -999 1 -999 0.8 -999 30 -999Hrynyshyn et al 2012 1997-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.10 0.02 -999 1 -999 0.8 -999 30 -999Hrynyshyn et al 2012 2003-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.20 0.02 -999 1 -999 0.8 -999 30 -999Hrynyshyn et al 2012 2007-999 73 -999405.00 276.711.20 13 -999 6.5 ~ 9 9.00 0.02 13.6 1 -999 0.8 3.1 30 -999Hrynyshyn et al 2012 2007-999 73 500112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 1 0.8 -999 30 -999Hrynyshyn et al 2012 2007-999 73 30112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 3 0.8 -999 30 -999Hrynyshyn et al 2012 2007-999 73 50112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 4 0.8 -999 30 -999Hrynyshyn et al 2012 2007-999 73 -999112.00 104.1712.00 13 -999 6.5 ~ 9 9.00 0.02 0.055 1 1 0.8 -999 30 20Leung et al 2003 2002-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.69 0.02 0.14 1 -999 0.8 -999 30 -999Ma 2012 2011-999 73 -999112.00 104.17(999.00) 13 35.3 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Mackinnon et al 20012000-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.50 0.02 -999 1 -999 0.8 -999 30 -999Mackinnon et al 20012000-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Mackinnon et al 20012000-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 5.00 0.02 -999 1 -999 0.8 -999 30 -999Mackinnon et al 20012000-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 12.00 0.02 -999 1 -999 0.8 -999 30 -999Mackinnon et al 20012000-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.20 0.02 -999 1 -999 0.8 -999 30 -999Mackinnon et al 20012000-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.10 0.02 -999 1 -999 0.8 -999 30 -999Mackinnon et al 20012000-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.20 0.02 -999 1 -999 0.8 -999 30 -999Mackinnon et al 20012000-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Peng et al 2004 2003-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.50 0.02 -999 1 -999 0.8 -999 30 -999Peng et al 2004 2003-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 7.80 0.02 -999 1 -999 0.8 -999 30 -999Peng et al 2004 2003-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.00 0.02 -999 1 -999 0.8 -999 30 -999Peng et al 2004 2003-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.30 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.10 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.20 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 7.70 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 7.60 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.24 0.02 -999 1 -999 0.8 -999 30 -999Data for Ni Objective 143   seasonalStation NumberSampleDateMeHg (Methyl Mercury)Mo (Molybdenum)ObjectiveMo (Molybdenum)hardnessNiObjectiveNi (Nickel)Nitrate (NO3)ObjectiveNitrate (NO3)pHObjectivepHPhosphorousObjectivePhosphorousSe (Selenium)ObjectiveSe (Selenium)Th (Thallium)ObjectiveTh (Thallium)Zn (Zinc)ObjectiveZn (Zinc)Sansom 2010 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.39 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.39 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.53 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.80 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.77 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 8.98 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 8.91 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 8.9 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 8.85 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 8.51 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 7.77 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 8.16 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 8.31 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17-999 13 -999 6.5 ~ 9 7.02 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 7.53 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 500112.00 104.17(999.00) 13 -999 6.5 ~ 9 7.93 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 200112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.36 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 100112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.25 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2007-999 73 200112.00 104.17(999.00) 13 -999 6.5 ~ 9 7.34 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.83 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 7.64 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.25 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 300112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.11 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.32 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 7.57 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.19 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.69 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.91 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 7.69 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 9.00 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.35 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.52 0.02 -999 1 -999 0.8 -999 30 -999Sansom 2010 2008-999 73 -999112.00 104.17(999.00) 13 -999 6.5 ~ 9 8.96 0.02 -999 1 -999 0.8 -999 30 -999Data for Ni Objective144   B.2 Sub-Appendix CCME output data   StationIndex PeriodF1F2F3CCME WQISum ofFailedTestsNormalizedSum of theExcursions(nse)NumberofSamplesTotalNumber ofVariablesActual# ofVariablesTestedNumberofTestsNumberof FailedtestsNumberof PassedTestsNumber ofTestsBelow DetectionLimitsAllen 2008 2007 50.0 11.1 99.0 35.6 920.05 102.23 8 22 2 9 1 8 0Baker et al 2012 2011 70.0 50.0 67.9 36.7 46.55 2.12 4 22 10 22 11 11 0Debenest et al 2012 2011 70.0 70.0 96.5 20.2 275.53 27.55 1 22 10 10 7 3 0El-Din et al 2011 2010 0.0 0.0 0.0 100.0 0.00 0.00 1 22 1 1 0 1 0Holden et al 2011 2010 50.0 50.0 97.1 30.7 133.39 33.35 1 22 4 4 2 2 0Holowenko et al 2000 1997 66.7 66.7 99.4 20.9 2507.10 167.14 5 22 3 15 10 5 0Holowenko et al 2000 1998 66.7 55.6 99.5 23.8 3750.85 208.38 6 22 3 18 10 8 0Hrynyshyn et al 2012 1997 33.3 33.3 88.0 42.4 22.03 7.34 1 22 3 3 1 2 0Hrynyshyn et al 2012 2003 66.7 66.7 99.7 20.8 922.65 307.55 1 22 3 3 2 1 0Hrynyshyn et al 2012 2007 72.2 57.1 99.4 21.8 7831.85 159.83 5 22 18 49 28 21 0Leung et al 2003 2002 33.3 33.3 66.7 52.9 6.00 2.00 1 22 3 3 1 2 0Ma 2012 2011 66.7 66.7 49.6 38.5 2.96 0.99 1 22 3 3 2 1 0Mackinnon et al 2001 2000 100.0 25.0 7.3 40.3 0.63 0.08 8 22 1 8 2 6 0Peng et al 2004 2003 50.0 50.0 45.8 51.4 6.77 0.85 4 22 2 8 4 4 0Sansom 2010 2007 85.7 55.4 98.0 18.3 4979.89 49.31 24 22 7 101 56 45 0Sansom 2010 2008 100.0 37.0 98.3 16.3 9034.92 58.67 48 22 7 154 57 97 0Scott et al 2008 2007 0.0 0.0 0.0 100.0 0.00 0.00 1 22 1 1 0 1 0Tompkins 2009 2008 50.0 25.0 40.0 60.3 2.67 0.67 2 22 2 4 1 3 0Van den Heuvel et al 1999 1995 30.8 30.8 78.8 48.0 48.20 3.71 1 22 13 13 4 9 0Xiumei et al 2009 2006 66.7 61.1 99.6 22.3 4542.45 252.36 6 22 3 18 11 7 0Zubot 2010 1997 66.7 66.7 99.1 21.0 336.03 112.01 1 22 3 3 2 1 0Zubot 2010 1998 66.7 66.7 99.3 20.9 415.07 138.36 1 22 3 3 2 1 0Zubot 2010 1999 66.7 66.7 98.9 21.1 271.80 90.60 1 22 3 3 2 1 0Zubot 2010 2000 60.0 60.0 98.0 25.2 244.33 48.87 1 22 5 5 3 2 0Zubot 2010 2001 60.0 60.0 98.1 25.1 258.97 51.79 1 22 5 5 3 2 0Zubot 2010 2002 60.0 60.0 98.4 25.0 298.14 59.63 1 22 5 5 3 2 0Zubot 2010 2003 60.0 60.0 98.3 25.0 296.79 59.36 1 22 5 5 3 2 0Zubot 2010 2004 60.0 60.0 99.0 24.7 484.53 96.91 1 22 5 5 3 2 0Zubot 2010 2005 60.0 60.0 98.7 24.8 393.81 78.76 1 22 5 5 3 2 0Zubot 2010 2006 80.0 80.0 98.5 13.4 335.17 67.03 1 22 5 5 4 1 0Zubot 2010 2007 60.0 60.0 99.5 24.5 988.68 197.74 1 22 5 5 3 2 0Zubot 2010 2009 76.5 65.1 93.9 20.6 666.24 15.49 4 22 17 43 28 15 0   

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