THE USE OF HAY AND SAWDUST TO PROMOTE THE REMOVAL OF SELENIUM AND NITRATE IN COAL MINE DRAINAGE: A SATURATED UP FLOW COLUMN EXPERIMENT by Nicholas Weste Dumaresq B.Sc. McGill University, 2006 B.A.Sc. University of Northern British Columbia, 2011 THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN NATURAL RESOURCES & ENVIRONMENTAL STUDIES UNIVERSITY OF NORTHERN BRITISH COLUMBIA June 2018 ©Nicholas Dumaresq, 2018 Abstract A saturated up-flow column experiment was conducted to compare the ability of locally-available organic amendments (hay and sawdust) to foster reducing conditions and attenuate permit-exceeding concentrations of sulfate, nitrate, and selenium in effluent from a British Columbia coal mine. Mine effluent was continuously passed through columns containing one or both amendments mixed with mine-sourced rock, and indicators of organic decomposition and redox conditions were quantified in influent and effluents. Over the 180day trial, effluent from hay-amended columns exhibited the highest removal of target parameters (up to 99.9%, 98.6%, and 77.5% removal of nitrate, selenium, and sulfate, respectively), although performance decreased over time, suggesting possible long-term performance concerns. In contrast, sawdust-amended columns fostered only partial denitrification and no sulfate removal, which could be linked to the more recalcitrant nature of the organic matrix. Effluents from all columns amended with organics would require further treatment before discharge to a receiving environment. ii Table of Contents Abstract ........................................................................................................................................... ii Table of Contents ........................................................................................................................... iii List of Figures ................................................................................................................................ vi List of Tables ................................................................................................................................ vii Glossary ............................................................................................................................................ Acknowledgement ......................................................................................................................... iv Section 1: Introduction and Literature Review ............................................................................... 1 1.1 Brule Mine and Need for Research ................................................................................. 1 1.2 Redox Processes Associated with Oxidation of Organic Matter .................................... 3 1.3 Nitrogen .......................................................................................................................... 8 1.3.1 Overview and Source at the Brule Mine ........................................................... 8 1.3.2 Speciation and Redox Behaviour .................................................................... 10 1.3.3 Behaviour in waste rock environments ........................................................... 11 1.4 Sulfur............................................................................................................................. 12 1.4.1 Overview ......................................................................................................... 12 1.4.2 Speciation and Redox Behaviour .................................................................... 14 1.4.3 Behaviour in waste rock environments ........................................................... 14 1.4.4 Metal-Sulfide Precipitation.............................................................................. 15 1.5 Selenium ....................................................................................................................... 17 1.5.1 Overview & Presence in Geologic Material .................................................... 17 1.5.2 Toxicity............................................................................................................ 19 1.5.3 Attenuation Pathways and Remobilization...................................................... 21 1.6 Other Redox Sensitive Parameters................................................................................ 26 1.7 Biologically Mediated Processes for Mine Water Treatment ....................................... 27 1.7.1 Bioremediation ................................................................................................ 27 1.7.2 Role of Organic Substrate................................................................................ 29 1.8 Brule Mine Stratigraphy and Mineralogy ..................................................................... 31 1.9 Column Design Review ................................................................................................ 32 1.10 Research Objectives and Approach .............................................................................. 34 1.11 Readily Available Organic Substrate in NEBC ............................................................ 35 Section 2: Materials and Methods................................................................................................. 38 2.1 Overview ....................................................................................................................... 38 2.2 Materials ....................................................................................................................... 38 2.2.1 Treatments ....................................................................................................... 39 2.2.2 Column Design ................................................................................................ 39 2.2.3 Hay................................................................................................................... 40 2.2.4 Sawdust ............................................................................................................ 41 2.2.5 Crushed Mine Waste Rock .............................................................................. 42 2.2.6 Mine Water ...................................................................................................... 42 2.3 Experimental Design ..................................................................................................... 43 2.4 Analytical Methodology ............................................................................................... 50 2.4.1 Hay Preparation ............................................................................................... 50 iii 2.5 2.4.2 Sawdust Preparation ........................................................................................ 51 2.4.3 Crushed Mine Waste Rock Preparation........................................................... 51 2.4.4 Sample Collection and Chemical Analysis .................................................... 53 2.4.5 Column operation ............................................................................................ 56 Quality Assurance and Quality Control (QAQC) ......................................................... 57 2.5.1 Field (independent of ALS) ............................................................................. 57 2.5.2 Laboratory ....................................................................................................... 58 Section 3: Results.......................................................................................................................... 60 3.1 Overview ....................................................................................................................... 60 3.2 Data Quality .................................................................................................................. 61 3.2.1. Data Issues Arising from Column Blockages.................................................. 62 3.2.2. Operational Issues Affecting Results .............................................................. 62 3.3 Amendment Characterization ....................................................................................... 64 3.3.1 Waste Rock ...................................................................................................... 64 3.3.2 Organic Substrates ........................................................................................... 65 3.4 Influent Characterization .............................................................................................. 65 3.4.1 Overview ......................................................................................................... 65 3.4.2 Consistency of Influent Water ......................................................................... 68 3.4.3 Influent Water Chemical Characterization ...................................................... 69 3.5 Effluent Characterization. ............................................................................................. 72 3.5.1 Overview ......................................................................................................... 72 3.5.2 Column 1 - Hay and Waste rock ..................................................................... 73 3.5.3 Column 2 - Waste Rock only .......................................................................... 78 3.5.4 Column 5 – Hay, Sawdust and Waste Rock .................................................... 82 3.5.5 Column 6 - Sawdust and Waste Rock ............................................................. 87 3.6 Qualitative Observations ............................................................................................... 91 Section 4: Discussion .................................................................................................................... 93 4.1 Overview ....................................................................................................................... 93 4.2 Organic Amendment Performance ............................................................................... 94 4.2.1 Comparison of Amendment Nutrient Properties ............................................. 94 4.2.2 Direct Products of Organic Matter Degradation.............................................. 96 4.2.3 Redox Parameters Measured in Effluents ....................................................... 97 4.3 Biogeochemical Processes Governing the Speciation and Behaviour of Se and NO 3-105 4.3.1 Reaction Pathways and Mechanisms Governing Removal ........................... 105 4.3.2 Attenuation Products and Long-term Stability .............................................. 109 4.3.3 Results of Geochemical Modeling ................................................................. 110 4.4 Environmental Relevance and Effect of Other Reaction Products ............................. 110 4.4.1 Trace Elements .............................................................................................. 111 4.4.2 Comparison of Effluent with British Columbia Water Quality Guidelines. . 111 4.5 Implications for Field Scale Application of Biological Reactors ............................... 113 4.5.1 Combined Application................................................................................... 114 4.5.2 Amendment Conditioning ............................................................................. 115 4.5.3 Performance and Implementation Considerations ......................................... 116 iv Section 5: Conclusion ................................................................................................................. 120 References ................................................................................................................................... 121 Appendix A – Eh-pH Diagrams ..................................................................................................... A Appendix B – Photographs ............................................................................................................. B Appendix C – Specifications .......................................................................................................... C Appendix D – Results .................................................................................................................... D v List of Figures Figure 1.1: Se-SO42- correlation in Brule Mine test and discharge effluents ............................... 18 Figure 2.1: Column with 1 cm layer of Ottawa Sand overlain by organic amendment............... 41 Figure 2.2: Experimental configuration during sampling events. ................................................ 44 Figure 2.3: Sample collection containers with inlet and outlet tubes individually valved. ......... 47 Figure 2.4: An inverted column during maintenance. ................................................................. 48 Figure 2.5: Up flow 15 mL polypropylene containers ................................................................. 49 Figure 2.6: Experimental setup – configured for normal flow through operations ..................... 50 Figure 2.7: Cone and quarter method in progress. ....................................................................... 52 Figure 2.8: Residual fines left on the plastic sheeting after a cone and quartering event ............ 53 Figure 3.1: Gas bubbles building up at the top of column 1. ....................................................... 63 Figure 3.2: Column influent and effluent Se(IV) concentrations ................................................... 66 Figure 3.3: Column 5 effluent Se species concentrations ............................................................ 66 Figure 3.4: Influent and effluent SO42- concentrations throughout the experiment. .................... 72 Figure 3.5: Week 4 water quality samples ................................................................................... 91 Figure 4.1: Schematic of reactions expected to have occurred within column 1......................... 95 Figure 4.2: SO42- concentrations in influent and effluents plotted as a function of time ........... 103 vi List of Tables Table 1.1: Potential reactions and Gibbs free energies for reduction ........................................... 5 Table 1.2: Summary of research used to determine CMWR: organics ratio ............................... 37 Table 2.1: Treatment mass and volume of substrates utilized within experimental columns...... 39 Table 2.2: Hold times, preservatives, minimum volumes, and containers for parameters .......... 56 Table 3.1: Initial void space and estimated combined mass lost in first 5 days........................... 63 Table 3.2: Average particle size distribution of three CMWR samples....................................... 64 vii Glossary Symbol Description Nomenclature ABA ALS ANFO BC BCR BOD CMWR CoA COC CRM DDNRA DOC dw ee.g. E. coli EFL Eh ΔG°' HDPE IAP ICP-MS ID Ksp LCS llnl Lorax MB MDL minteq.v4 MoE MS NIST NEBC Acid Base Accounting ALS Environmental Laboratories Ammonium Nitrate Fuel Oil British Columbia BioChemical reactor Biological Oxygen Demand Crushed Mine Waste Rock Criteria of Acceptability Contaminant of Concern Certified Reference Material Dissolved Dissimilatory Nitrate Reduction to Ammonia Dissolved Organic Carbon Dry Weight Electron Exempli Gratia Escherichia coli Enhanced Forestry Lab at the University of Northern British Columbia Oxidation/Reduction Potential Standard Gibbs Free Energy High-Density PolyEthylene Ion Activation Product Inductively Coupled Plasma Mass Spectrometry Inner Diameter Equilibrium Solubility Constant Laboratory Control Samples Lawrence Livermore National Laboratory PHREEQC database Lorax Environmental Services Method Blank Method Detection Limit Minteq International Inc. PHREEQC database Ministry of Environment Matrix Spike National Institute of Standards and Technology North East British Columbia NSERC OD ORP PES PHREEQC ppb ppm PTFE PVDF QAQC Redox RPD RPM SI TTN TOC Trent UNBC USEPA, EPA UV VCB WQG ZVI Natural Sciences and Engineering Research Council of Canada Outer Diameter Oxidation/Reduction Potential Polyethersulfone Geochemical Equilibrium Modelling Software parts per billion Parts Per Million Polytetrafluoroethylene Polyvinylidene fluoride Quality Assurance & Quality Control Reduction-Oxidation Relative Percent Difference Revolutions per Minute Saturation Index Total Total Nitrogen Total Organic Carbon Trent University Water Quality Center University of Northern British Columbia United States Environmental Protection Agency Ultraviolet Verified Clean Bottle Water Quality Guideline Zero Valent Iron Chemicals Ag Al As Ba Bo C Ca CaCO3 Cd CH2O (CH2O)106(NH3)16(H3PO4) ClCO2 Co Cr Silver Aluminum Arsenic Barium Boron Carbon Calcium Calcium Carbonate Cadmium Formaldehyde Redfield Molecule Chloride Carbon Dioxide Cobalt Chromium i Cu FFe Fe(II) Fe(III) FeOOH FeS2 H H2O H3O+ H2S H2SO4 Hg HNO3 HPO4Mg Mn MnO2 Mo N N2 NaOH NH3 NH4+ NH4NO4 Ni NO NO2 NO2NO3N2O O O2 P Pb S S0 S2S2n S2O32SnO62- Copper Fluoride Iron Ferrous Iron with an oxidation number of (+2) Ferric Iron with an oxidation number of (+3) Goethite Pyrite Hydrogen Water Hydronium Ion Hydrogen Sulfide Sulfuric Acid Mercury Nitric Acid Hydrogen Phosphate Magnesium Manganese Manganese Dioxide, Mn(IV) Molybdenum Nitrogen Nitrogen Gas Sodium Hydroxide Ammonia Ammonium Ammonium Nitrate Nickel Nitrogen Monoxide Nitrogen Dioxide Nitrite Nitrate Nitrous Oxide Oxygen Oxygen Gas Phosphorous Lead Sulfur Elemental Sulfur, S(0) Sulfide Polysulfides Thiosulfate Polythionates ii SO32SO42Sb Se Se0 Se2SeO32SeO42Si Sr Tl U Zn Zn(O2C2H3)2 Sulfite Sulfate Antimony Selenium Elemental Selenium, Se(0) Selenide Selenite, Se(IV) Selenate, Se(VI) Silicon Strontium Thallium Uranium Zinc Zinc Acetate Units of Measure " °C cm cm3 g kg kJ km L m2 mg min mL mm mM mV nm μg μm Inch Degree Celsius Centimeter Cubic Centimeter Gram Kilogram Kilojoule Kilometer Liter Square Meter Milligram Minute Millilitre Millimeter Millimole Millivolt Nanometer Microgram Micrometer iii Acknowledgement This research was funded jointly and generously by Walter Canadian Coal Partnership (no longer in operation), a subsidiary of Walter Energy, Inc. and the Natural Sciences and Engineering Research Council of Canada, through an Engage Grant awarded to my supervisor, Dr. Mike Rutherford. The funding of these partners, and the guidance (and patience) of Dr. Rutherford have been greatly appreciated. The help and direction of Al Martin, of Lorax Environmental, and his willingness to have Lorax technical staff provide guidance through difficult times has also been of tremendous value. The efforts of Dr. Joselito Arocena were very helpful in shaping the course of the experiment, and the availability and support of Dr. Bill McGill to help finalize the thesis have also been instrumental. The support provided by the curators of the Enhanced Forestry Laboratory, John Orlowsky and Doug Thompson, have benefited the research. The wisdom of Dr. Jack Adams in assisting with the experimental design in its early stages was appreciated. Lastly, the various technical staff at the University of Northern British Columbia who have provided laboratory access, instrument demonstrations, method explanations, and overall technical support deserve recognition. iv Section 1: Introduction and Literature Review 1.1 Brule Mine and Need for Research The Brule open-pit coal mine (Brule Mine) is located in the eastern foothills of the Rocky Mountains (Peace River Regional District) approximately 57 kilometers (km) by road south of Chetwynd, British Columbia (BC). Mine access is via Highway 29, approximately 25 km south of Chetwynd by way of the Sukunka Forest Service Road, and then 12 km along the Blind Creek Road (Walter Energy, 2015). The mine is currently owned by Conuma Coal Resources Limited and produces a premium low volatile pulverized coal injection product. Open pit coal mining operations consist of blasting, stripping, excavating, trucking and dumping large quantities of waste rock (Dreher & Finkelman, 1992). During the mining process, large pits are created in the landscape (Hochbaum & Chen, 2000), which are then partially backfilled with fragmented waste rock. The porosity, grain size and typically unsaturated characteristics of waste rock make this material susceptible to oxidative weathering, sulfide (S2-) mineral oxidation and associated metal leaching (Dreher & Finkelman, 1992). In the context of coal mines in BC, naturally-occurring, relatively insoluble selenium (Se) is associated with pyrite (FeS 2) and can oxidize to more soluble oxyanions1 on the freshly exposed surfaces of the fragmented waste rock (Kennedy, at al., 2012). This geological weathering can produce elevated concentrations of soluble Se 1 Oxyanion: an ion with the generic formula AxOyz− (where A represents a chemical element and O represents an oxygen atom) 1 oxyanions (selenate - SeO42- and selenite - SeO32-) and sulfate (SO42-) in drainages reporting from waste rock facilities (Wellen, et al., 2015). As a result of blasting activities, elevated concentrations of nitrate (NO3-), an oxyanion of nitrogen (N), are also a common feature to coal mine waste rock drainages (Tiwary, 2001). The high concentrations of each of these specific contaminants of concern (COCs) pose risks to aquatic receptors through chronic and acute toxicity. In this regard, Se, SO42-, and NO3- in effluents are of concern to mines, surrounding communities, First Nations, and local, provincial, and federal regulatory bodies. Over time, the void spaces in the backfilled mining pits may be filled with water from surface and groundwater inflows. These pits are then referred to as ‘saturated backfills’. Saturated backfills have been shown to attenuate soluble Se and NO 3- from mine contact waters through microbially mediated processes, due to the long residence time of water in the pits and the presence of organic carbonaceous wastes which result in suboxic environments (Bianchin, et al., 2012). There is therefore an interest in studying conditions which promote microbial populations in suboxic saturated backfill environments and the corresponding attenuation of NO3- and Se from mine contacted waters. A greater understanding of biogeochemical processes occurring in mine effluents may lead to more effective Se and NO 3management strategies at the Brule Mine as well as in the mining industry as a whole. This research seeks to provide a greater understanding of the processes that lead to the anaerobic attenuation of oxyanions of N, Se, and S from Brule Mine effluents with the longterm goal of helping the mine develop operational scale-technologies for lowering concentrations of these COCs in discharge effluents. The following section will provide an overview of reduction-oxidation (redox) processes and the role of specific COCs in balancing reactions resulting from the oxidation of 2 organic matter. Specifics of the COCs are also presented, including their source and concentration in the effluent of the Brule Mine, speciation and oxidation/reduction potential (ORP, Eh) behaviour, and behaviour in waste rock environments. Aqueous concentrations of these COCs in the downstream receiving environment of the Brule Mine have been presented based on data current to May 2015. Nitrate and S are discussed individually, with specific attention directed at the ability of S to form metal-sulfide precipitants. Selenium is the focus of the research and is presented in greater detail. A brief review of existing research into the bioremediation of these COCs, bacterially mediated organic decomposition, and column reactor design is also presented. 1.2 Redox Processes Associated with Oxidation of Organic Matter In a balanced reaction, the gain of electrons (reduction) of a compound (or other chemical species) is offset by a corresponding loss of electrons (oxidation) of another compound, resulting in no change in total charge. In natural systems, biomass decomposition is mostly an oxidative process, and releases electrons for which acceptors must be present (Van Der Weijden, 1992). The half-reaction for the oxidation of a low molecular weight organic carbon (C) molecule is shown by Equation (1) below: (1) {CH2O} + 5 H2O → CO2(g) + 4 H3O+(aq) + 4 eIn aerobic aquatic systems, bacteria use oxygen (O) as their terminal electron acceptor, which balances Equation (1), as shown in the corresponding reducing half reaction in Equation (2) (Van Der Weijden, 1992). (2) O2(g) + 4 H3O+ + 4 e- → 6 H2O Anaerobic aquatic systems, or low O2 environments, such as sediments, wetland soils, stratified and lentic environments, and areas with insufficient O 2 recharge, have conditions in 3 which communities of bacteria using other electron acceptors can proliferate (Nealson & Meyers, 1992; Schlesinger & Bernhardt, 2013). These communities catalyze reactions in which electrons produced during organic decomposition (Equation (1)) are reduced via alternate electron acceptors. Equations (3) through (7) below show the corresponding reduction half-reactions specific to alternate electron acceptors: NO 3- (3), manganese dioxide (MnO2) (4), goethite (FeOOH) (5), SeO42- (6), and SO42- (7). The stoichiometric coefficients would need to be modified to provide a balanced reaction with Equation (1): (3) 2 NO3- (aq) + 12 H3O+ + 10 e- → N2(g) + 18 H2O2 (4) MnO2(s) + 4 H3O+ + 2 e- → Mn2+(aq) + 12 H2O (5) FeOOH(s) +3 H3O+ + e- → Fe2+(aq) + 5 H2O (6) SeO42-(aq) + 8 H3O+ + 6 e- → Se(s) + 12 H2O (7) SO42-(aq) + 9 H3O+ + 8 e- → HS-(g) + 13 H2O While numerous other electron acceptors exist, the ones depicted in Equations (3) through (7) are distinct because they undergo a phase change during reduction (Martin, et al., 2013).3 This attribute is important; aqueous concentrations of N, Se, and S will decrease as conditions become more suboxic, while those of iron (Fe) and manganese (Mn) will increase. 2 The reduction of NO3- to nitrogen gas (N2) is referred to as denitrification. Note: it is not the conversion between redox states that drives phase change, and no phase change is absolute. Each chemical species in the system must reach thermodynamic equilibrium, which is governed principally by pressure and temperature. This equilibrium will determine its phase. For the purposes of the discussion presented herein, standard temperature and pressure conditions (298.15K, 101325 Pa) will be assumed. The relatively high melting and low boiling points of some chemical species (i.e. elemental Se melts at approximately 494 K, while N2 boils at 77.2 K) will dictate their state. The National Institute of Standards and Technology (NIST) website provides compound-specific (but not ion-specific) constants for calculating equilibrium states at as functions of pressure and temperature. 3 4 Comparing time-sequenced ion concentrations of a liquid undergoing a chemical transformation can provide insight into ORP dynamics. In this regard, profiling for this suite of redox reaction products has been used to evaluate Eh gradients in stratified marine and lacustrine settings, as well as within suboxic groundwater systems (Spencer & Brewer, 1971). The order in which alternate electron acceptors are reduced is theoretically linked to the magnitude of the Gibbs free energies associated with their respective reduction potentials (Froelich, et al., 1979). In natural systems, the reduction of O 2 produces a large Gibbs free energy and will be preferentially reduced over less energetic electron acceptors. When O 2 levels are depleted, ORP will decrease, favouring the next most efficient electron acceptor (Froelich, et al., 1979). The amount of energy obtained from the reaction is proportional to the magnitude of the Gibbs free energy, and as a result, the reaction sequence follows the hierarchy of energy yields. Relative amounts of energy, obtained from the oxidation of hydrogen (H) as O2, NO3-, SeO42-, SeO32-, and SO42- are reduced, are displayed in Table 1.1.4 According to this data, NO3- should be reduced after O2, but before SeO42-. Table 1.1: Potential reactions and Gibbs free energies for reduction of selected oxidized compounds with concurrent oxidation of H, reproduced from Nerenberg & Rittman (2004) Compound O2 NO3SeO42SeO32SO42- Probable Reduction Reaction(s) O2+ 2 H2 → 2 H2O 2 NO3- + 5 H2 + 2 H+ → 1 N2 + 6 H2O SeO42- + 3 H2 +2 H+ →Se0 + 4 H2O HSeO32- + 2 H2 +H+ →Se0 + 3 H2O 2 SO42- + 8 H2 + 3 H+ → H2S + HS- + 8 H2O ∆G°’ (KJ (e-)-1)* -123 -112 -71 -65 -19 * ∆G°’ is the standard Gibbs free energy at pH = 7 4 The table reproduced from Nerenberg & Rittman (2004) does not show the Gibbs free energies of the reductions of Fe and Mn, as they were not displayed in the referenced material. These reactions are important for the scope of this experiment and are discussed later in the thesis 5 Depending on the form of oxidized Mn mineral (i.e. birnessite, pryolusite) Mn reduction (not shown in Table 1.1) can occur preferentially or subsequently to that of NO 3(Froelich, et al., 1979). In a flowing aerated stream, rates of O 2 replenishment often match those of reductive consumption, and as such, redox levels necessary for the reduction of SO 42may not be achieved. When O2 concentrations fall below bacteria specific thresholds, facultative bacteria can utilize NO3- as a terminal electron acceptor. Examples of facultative anaerobic genera which accomplish NO3- reduction are Pseudomonas, Micrococcus, Bacillus, and Achromobacter (Camargo, et al., 2005). Similarly, bacteria will generally reduce NO 3- before SeO42- (Steinberg, et al., 1992). Contrary to the above general assertions regarding the dependence of electron acceptor consumption on the energy yield, specific bacteria have been shown to reduce electron acceptors in alternate orders due to their specific affinities or inhibitions (Marietou, et al., 2009). Examples of bacteria deviating from the order suggested by the available energies include Thiosphaera pantotropha, which uses NO3- concurrently as the electron acceptor in oxygenated environments (Robertson & Kuenen, 1984), and Thauera selenatis, which use SeO42- and NO3- concurrently (Oremlund, et al., 1999). Recent publications have also shown the existence of obligate aerobic bacteria that reduce Se (IV) (selenite) in the presence of O2 (Zheng, et al., 2014). In the above discussion, chemical speciation is discussed as a function solely of ORP (or Eh), measured in millivolts (mV), however speciation is also a function of pH. E h-pH diagrams show the dominant aqueous and stable solid phases of an element on a plane as a function of redox potential on the vertical axis, and pH on the horizontal axis (Takeno, 2005). By knowing these variables, the oxidation state of an element can be reasonably predicted. 6 This can lead to greater understanding of the solute transport in groundwater, if elemental concentrations, pH, and ORP are known (Takeno, 2005). E h-pH diagrams for Se, N, and S are shown in Appendix A, as found in Takeno (2005). These diagrams can be referenced in the upcoming discussion of oxidation states of these elements. Speciation in the field often differs with respect to thermodynamic predictions as a result of kinetic constraints and biological activity (Sharma, et al., 2015). Stoichiometrically balanced reactions showing the oxidation of a representative organic molecule are shown below (Van Der Weijden, 1992). This organic molecule (CH2O)106(NH3)16(H3PO4) takes into account observed C:N: phosphorous (P) ratios in pelagic phytoplankton and is referred to as the Redfield molecule (Van Der Weijden, 1992). Parameters measured in standard laboratory analysis and used to elucidate redox conditions are displayed in bold font, while the electron acceptors in each reaction are underlined. (8) (CH2O)106(NH3)16(H3PO4) + 138 O2 → 106 CO2 +16 NO3- + HPO42- + 18 H+ + 122 H2O (9) (CH2O)106(NH3)16(H3PO4) + 84.8 NO3- → 7.2 CO2 + 98.8 HCO3- + 16 NH4+ + 42.4 N2 + HPO42- + 49.6 H2O (10) (CH2O)106(NH3)16(H3PO4) + 236 MnO2 + 364 CO2 + 104 H2O → 470 HCO3- + 8 N2 + 236 Mn2+ + HPO42(11) (CH2O)106(NH3)16(H3PO4) + 424 FeO2H + 756 CO2 → 862 HCO3- + 8 N2 + 16 NH4+ + 424 Fe2+ + HPO42- + 120 H2O (12) (CH2O)106(NH3)16(H3PO4) + 53 SO42- → 39 CO2 + 67 HCO3- + 16 NH4+ + HPO42- + 53 HS- + 39 H2O 7 The above reactions are important, as they show both how organics (like the Redfield molecule) can be decomposed (oxidized) and how corresponding electron acceptors are reduced. Equations (8) through (12) show that the P in the original organic molecule will be released as soluble hydrogen phosphate (HPO42-), and as such, is an indication of organic decomposition. Equations (9) through (12) show that the suboxic diagenesis of organic matter results in the formation of bicarbonate (Herbert, et al., 2000) which will increase alkalinity (Van Der Weijden, 1992). This is simplified in Equation (13) which shows a low molecular weight organic C molecule being oxidized and SO 42- being reduced. Note that this bicarbonate production is a result of the reaction in Equations (9) through (12), but not (8), indicating that an increase in alkalinity is indicative of anaerobic and facultative systems. Also shown in Equations (9), (11) and (12) is the production of ammonium (NH4+), which is an important biproduct of decomposition reactions. (13) 2 CH2O + SO42- → 2 HCO3- + H2S While Se has not been shown, it could be represented similarly to S in Equation (12). Equation (14) shows an approximation of SeO42- reduction in the presence of the Redfield Molecule. (14) (CH2O)106(NH3)16(H3PO4) + 53 SeO42- → 39 CO2 + 67 HCO3- + 16 NH4+ + HPO42- + 53 HSe- + 39 H2O 1.3 Nitrogen 1.3.1 Overview and Source at the Brule Mine Nitrogen is an important element which affects the species composition, diversity, dynamics, and functioning of aquatic and terrestrial ecosystems (Vitousek, et al., 1997). Nitrogen is used in many industrial processes ranging from fertilizer manufacture to 8 explosives manufacturing. It is a main component in the commonly used mining explosive Ammonium Nitrate Fuel Oil (ANFO). Both pure phase ANFO and ANFO slurries were used at the Brule Mine to fracture consolidated rock and access the coal deposits (source: site investigations). ANFO is composed of more than 90% prilled ammonium nitrate (NH 4NO3), the remainder being fuel oil, and the exact mix varies by producer (Orica, 2015). Slurries are composed of NH4NO3 and other chemicals held in suspension. Ammonium nitrate is extremely soluble in water (1183 g L-1), with the dissolved product potentially becoming an aqueous mixture of NH4+ and NO3- ions that can be toxic to aquatic organisms (Pommen, 1983). Nitrate and ammonia (NH3) effects are similar in their toxicity to salmonids and are likely to be found together as a result of explosive use (Pommen, 1983). Nitrate toxicity to aquatic invertebrates is correlated positively to both concentration and exposure times (Camargo, et al., 2005), and negatively to body size (Camargo & Ward, 1992). Nitrate sensitivity is greater in freshwater aquatic organisms than marine animals and its main toxic effect on freshwater invertebrates is due to its conversion of O 2 bearing pigments (e.g., hemoglobin, hemocyanin) to forms that can no longer bind O 2 (e.g., methemoglobin) (Camargo, et al., 2005). Nitrate, nitrite (NO2-), and NH3 resulting from explosive use can affect aquatic life in multiple ways which are not mutually exclusive: they can serve as nutrients for aquatic organisms (including plants), they can have direct toxic effects on animals, or they can directly or indirectly lower dissolved oxygen (DO) levels (e.g. through eutrophication or nitrification) (Pommen, 1983). During detonation, trace amounts of unconsumed ANFO are deposited on waste rock and ore. Under complete combustion (ideal) conditions, all N in ANFO and slurries will become gaseous N2. But, under normal, less ideal conditions, an equivalent of 6% of 9 explosive-sourced N can be available for leaching in the form of NO 3-, NO2- and NH3 (Pommen, 1983). Small concentrations of intermediary compounds, resulting from incomplete combustion or detonation, can also be produced as nitrogen monoxide (NO), nitrous oxide (N2O), and nitrogen dioxide (NO2). Nitrogen oxides and NH4+ are expected to be released as gas into the air, but a small fraction will likely stay in the waste rock and become dissolved in the water. These compounds and NO 2 then either oxidize directly or indirectly (via intermediary compounds) to NO3- in water. Incomplete combustion can result from several factors including explosive wetness, poor handling and spillage, and faulty detonation sequences resulting in missed holes (Morin & Hutt, 2009). 1.3.2 Speciation and Redox Behaviour Nitrogen can occur in many oxidation states, each with varying levels of toxicity. The states that are relevant to this experiment are primarily: NO 3- (+5), NO2- (+3), and NH4+ (-3), with less important states being, NO (+2), N2O (+1), and N2 (0) (Camargo, et al., 2005). In biological material, N is almost exclusively found in its fully reduced state, N (-3) (Cabello, et al., 2004). In the presence of high concentrations of S2-, an alternate NO3- reduction pathway may take place. It has been suggested that dissimilatory nitrate reduction to ammonium (DNRA) results from the inhibition of regular denitrification (Soomo & Gardner, 2002). Recent research indicates that using acetate as the substrate (electron donor), NO 3- limiting conditions result in a proliferation of DNRA activities, whereas in substrate limiting conditions, denitrification bacteria dominate. In conditions of limited NO 3- and substrate, both processes are possible, and co-occurrence will result in complete reduction of NO 3- (Van den Berg, et al., 2016). 10 Studies have shown that Desulfobulbus propionicus, a species of chemoautotrophic bacteria, and the facultative chemolithoautotroph Thioploca species are able to oxidize S2- in the presence of NO3- and NO2- in controlled laboratory experiments (Dannenberg, et al., 1992; Otte, et al., 1999). When hydrogen sulfide (H2S) was tested for its ability to enhance NO3reduction, its presence resulted in greater NH4+ production (Brunet & Garcia-Gil, 1996). The direct coupling of Fe oxidation to denitrification and or NO3- reduction to NH3 as a result of anaerobic enzymatic action has also been observed (Weber, et al., 2006). Conversely, NH 3 oxidation to NO2- can be paired with Fe (or alternatively Mn) reduction (Kuypers, et al., 2018). The same freshwater sediment bacteria that reduce ferric iron (Fe(III)) can subsequently oxidize it coupled with NO3- reduction (Weber, et al., 2006). 1.3.3 Behaviour in waste rock environments Cumulative explicit N mass balances cannot easily be verified for ANFO explosions, as these are open systems and the atmosphere (79% N2) provides a large source and sink of N. Multiple processes also occur simultaneously, often rapidly, making it challenging (if not impossible) to use changes in the concentration of any particular species to quantify individual processes and sources of various N constituents (Morin & Hutt, 2009). A study of ANFO and slurry use at a BC open pit coal mine found that approximately 95% of the N discharged in mine effluents could be traced back to explosive use and that wet conditions increased explosive-N losses to the environment (Ferguson & Leask, 1988). Another study of these explosives, also in BC open pit coal mines, found that most of the effluent N was in the form of NO3--N (87%), with NH3-N (11%) and NO2--N (2%) concentrations comparatively small (Pommen, 1983). 11 An assessment of the behaviour of N at a BC open pit coal mine found that the majority of explosive related N released into the environment came from waste rock. Waste rock sourced N accounted for 60-100% of N found in the receiving river, depending on the season, and an estimated 45% of the total N entering groundwaters and rivers (Pommen, 1983). Nitrate concentrations in the receiving waters of the Brule Mine have been increasing, peaking at 40.6 milligram (mg) per liter (L) in the month of August 2014, exceeding maximum BC Water Quality Guideline (WQG) for the protection of freshwater life of 32.8 mg L-1, and the 30-day average WQG of 3.0 mg L-1 (Nordin, et al., 2009; Walter Energy, 2015). At the Brule Mine, a NO3- management plan was developed in 2013 at the request of regulators, but its implementation did not, over the course of 2013 and 2014, halt the increasing annual average concentrations noted at the mine (Walter Energy, 2015). A photo provided in Appendix B shows ANFO dripped on the ground between blast holes on an active blasting pattern at the mine. Average NO2- concentrations have been increasing in the receiving water of the mine on an annual basis since 2006 (Walter Energy, 2015), but did not exceed the WQG which is calculated as a function of chloride (Cl-) concentration (Nordin, et al., 2009): 1.4 Sulfur 1.4.1 Overview Sulfur, a chalcogen, is present in igneous and sedimentary rocks in its reduced form, S2- (Meays & Nordin, 2013). Sulfur occurs in coal deposits in inorganic forms typically including S2- and SO42- (Calkins, 1994). Sulfur is also present in coal in organic forms, which are mostly components of the macromolecular network (Calkins, 1994). The S contained in 12 coal originates from seawater, fresh water, vegetation and extraneous mineral matter (Ryan & Ledda, 1997). Different exposures to these sources is a factor leading to the variability of S content in coals formed at different times and different locations. Sulfur present in concentrations greater than a few tenths of a percent likely results from a depositional environment where brackish or sea water, containing SO 42-, has permeated the formation (Calkins, 1993). Bacterial reduction produces H2S, which then reacts with the metals in the water to produce metal-sulfides. An example of this is Fe reacting with S 2- in the water to produce FeS2. Hydrogen sulfide can also react with organics to produce organic S compounds (Calkins, 1994). Pyrite can also be formed synergistically in the early stages of coal formation (Diehl, et al., 2012). Pyrite can be locally enriched in potentially toxic trace elements such as Se, arsenic (As), mercury (Hg), lead (Pb) and nickel (Ni) (Diehl, et al., 2012). Unweathered FeS2-containing rock and coal surfaces are exposed to geoclimatic forces after blasting and stripping. Oxidized S enters the water table as a result of the reaction shown in Equation (15). This reaction shows a S 2- (in this case FeS2) combining with oxygen to yield SO42-, which occurs predominantly at neutral pH (Neculita, et al., 2007): (15) FeS2 (s) + 7/2 O2 + H2O → Fe2+ + 2 SO42- + 2 H+ Factors such as pH, temperature, surface area and the presence of Fe and S oxidizing bacteria can affect the rate of FeS2 oxidation (Nordstrom, 1982). The conversion of SO 42- to S2- is reversible and governed by biological, physical, and chemical factors (Meays & Nordin, 2013). In reducing conditions, the presence of aqueous S2- complexes with Fe(II) and the FeS2- compounds precipitate quickly out of solution (Couture, et al., 2010). 13 Anthropogenic sources of SO42- are not limited to mining; the ion is released to aquatic environments through wastes from other industries including smelting, kraft pulp and paper and textile production, tanneries, agriculture, and waste water treatment (Meays & Nordin, 2013). Studies have noted a link between elevated SO 42- concentrations and increased catharsis in humans, but the World Health Organization has not proposed a healthbased guideline for SO42- in drinking water (World Health Organization, 2004). 1.4.2 Speciation and Redox Behaviour Sulfur can occupy a large range of oxidation states between -2 to +6, which makes it important in a variety of biogeochemical processes (Luther, et al., 1985). Bacterially mediated S reduction has been studied extensively. In O 2 depleted aquatic systems, SO42- is usually the most abundant water-soluble electron acceptor (Knossow, et al., 2015). Sulfide oxidation can occur in aqueous systems either microbially or abiotically and result in the formation of SO42- or numerous intermediary oxidative compounds including polysulfides (S 20 222n), elemental S (S ), thiosulfate (S2O3 ), polythionates (SnO6 ), and sulfite (SO3 ) with S oxidation states of 0, 0, jointly -2 and +6, variable depending on n, and 4, respectively (Knossow, et al., 2015). 1.4.3 Behaviour in waste rock environments Pyrite oxidation to soluble S compounds occurs in unsaturated backfill and can be a significant source of groundwater and surface water contamination (Molson, et al., 2005). The rate of FeS2 oxidation in waste rock environments is often limited by both S 2- supply and O2 at the mineral grain surface (Molson, et al., 2005). In saturated, lentic environments, FeS 2 oxidation is limited as the rate of O2 diffusion in water is approximately four orders of magnitude less than in air. Fine grain sizes in the waste rock environments can retain 14 moisture after precipitation events, limiting O2 permeation, and in turn FeS2 oxidation, while larger grain size fragments tend to dry quicker (Molson, et al., 2005). Conversely, fine grain sizes have significantly more reactive surface areas (per unit volume) than coarse fragments, which increase FeS2-O interactions. Another factor affecting the rate at which contaminants flow to the environment in saturated environments is the development of preferential flow paths through the waste rock environment, as backfills likely display heterogenous physical characteristics. Sulfate concentrations in the receiving waters of the Brule Mine increased leading up to 2014 and peaked at 406 mg L-1 in the month of July 2014 but did not exceed the WQG (Walter Energy, 2015). The WQG 30-day average concentration for the protection of freshwater life is an increasing stepped function proportional to hardness levels (mg L -1 CaCO3) (Meays & Nordin, 2013). Hardness levels observed in the receiving water of the mine correspond to a SO 42- WQG of 429 mg L-1 (Walter Energy, 2015). 1.4.4 Metal-Sulfide Precipitation Metal-sulfide precipitation is a process that has been studied at length for its applications in hydrometallurgical treatment of ores and effluents (Lewis, 2010). In engineered systems, S2- precipitation can be induced using solid, liquid, and gaseous S 2sources, (Lewis, 2010). Metal-sulfide compounds can be present as complexes, nanoclusters, or colloids. Equation (13) which is shown again below, shows the production of both bicarbonate and H2S (Herbert, et al., 2000). (13) 2 CH2O + SO42- → 2 HCO3- + H2S Aqueous H2S and other dissolved metals and non-metals including ferrous iron (Fe(II)), As, Cadmium (Cd), Cobalt (Co), Copper (Cu), Ni, Pb, and Zn may react together and 15 precipitate as thermodynamically stable sulfides with low solubilities, (Herbert, et al., 2000; Jong & Parry, 2003) as shown in Equations (16) through (19) for a metal M2+ (Lewis, 2010): (16) H2S ↔ HS- + H+ (17) HS- ↔ S2- + H+ (18) M2+ + S2- ↔ MS(s) (19) M2+ + HS- ↔ MS(s) + H+ pH largely governs the concentrations of the various S species in the above equations (H2S, HS-, and S2-). The combination of a high H2S vapour pressure and Fe-S2- precipitation precludes a mass balance of aqueous components in an open system from occurring due to S losses to both gaseous and solid phases. Reducing conditions which drive the solubilisation of reduced Mn, Fe, and As species (discussed further in Section 1.6) also result in increased S2- concentrations. Reduced Fe(II) will consume the available soluble S2- species initially, and other metals may be sequestered through co-precipitation with, or adsorption onto Fe-S 2- minerals (Couture, et al., 2010). In the case of As specifically, only when all available Fe(II) has become complexed with S 2- will reduced As ions become available to complex the remaining aqueous S 2-, forming As-S2minerals (Couture, et al., 2010). Couture, et al. (2010) discuss a comprehensive list of studies that point to the importance of As adsorption onto Fe oxyhydroxides, but also point out that temperature and the presence of natural organic matter can greatly reduce rate of adsorption of the former onto the latter. Hydrogen sulfide, bacteria and other reductants can also increase concentrations of metals adsorbed to Fe hydroxides via reductive dissolution of Fe(III) to the more soluble Fe(II). 16 1.5 Selenium 1.5.1 Overview & Presence in Geologic Material Selenium is a metalloid that occurs in four oxidation states (-2, 0, +4, and +6), all of which can be found in soils (Lussier, et al., 2003). Selenium and S have similar chemistries and are both located in group 16 of the periodic table (Seby, et al., 2001). The higher two oxidation states of Se are commonly found as oxyanions SeO32- (+4) and SeO42- (+6). Selenium is found in both organic and inorganic forms (Hansen, et al., 1998). At high ORP (above 450 mV) and neutral pH, SeO42- predominates (Masscheleyn, et al., 1990). Selenate, the most oxidized form, has high solubility and low adsorption capacities (Seby, et al., 2001), and exists as a tetrahedral oxyanion in solution as biselenate or SeO 42- (Peak, 2006). At moderate redox potentials, SeO32- is the dominant species, and its mobility is governed by adsorption/desorption on metal hydroxide surfaces (Seby, et al., 2001). Selenite (+4) exists as a weak diprotic acid (H2SeO3, H2SeO31-, H2SeO32-) depending on the solution pH (Peak, 2006). In Section 1.4.1, the inclusion of FeS2 during coal formation was discussed, and its reoxidization was linked to the presence of SO42- in the mine effluents. In the following section, a similar correlation will be established between the presence of FeS 2 and the presence of aqueous Se. Selenium concentrations in FeS 2 can vary over many scales, from microscopic to regional, due to varying concentrations of Se distributed in the different morphologies of FeS2. Selenium concentrations vary also because of the multiple S oxidation and reduction cycles during formation of the FeS2 (Diehl, et al., 2012). These cycles are based on changing biotic, chemical and physical conditions (Diehl, et al., 2012). In an examination of the distribution and origin of trace elements in coal samples from the United 17 Kingdom, a ratio of 0.566:1 (Se to FeS2) was established between concentration increases of Se and concentrations of FeS2 (Spears, et al., 1999). The presence of Se in the absence of FeS2 also indicated that not all of the Se was contained within FeS 2 (Spears, et al., 1999). The chemical oxidation of Se-bearing FeS2 produces SeO42- and SeO32-, which are highly soluble and exist primarily as ions in solution or adsorbed to charged surfaces of clay minerals (Kulp & Pratt, 2004). Figure 1.1: Se-SO42- correlation in multiple Brule Mine test and discharge effluents, reproduced from Western Canadian Coal (2006) The almost linear correlation between SO42- and Se in various test and discharge locations was documented in the Brule Mine’s Environmental Assessment Application, shown in Figure 1.1 (Western Canadian Coal, 2006), which suggest oxidation of S and Se at the mine occurs concurrently. 18 In coal samples taken from Kentucky, Alabama and West Virginia, Se concentrations in FeS2-filled veins had concentrations of 200 parts per million (ppm), 80 ppm, and 270 ppm, respectively (Diehl, et al., 2012), but whole ore concentrations were not given. Brule Mine Se concentrations range from 1.6-4.2 ppm in rocks and 0.5-2.1 ppm in coal, based on 2012-2013 analyses (Walter Energy, 2015), which are substantial given the 0.05 ppm crustal abundance of the earth (Lakin, 1973; Taylor, 1964). These concentrations are not unique to north east British Columbia (NEBC); a mine in southeastern BC has an average Se concentration in coal of 1.9 ppm. By comparison, the global Se average in coal is 1.0-1.6 mg Se kg -1, and some mines in Russia and China have concentrations of up to 43 mg Se kg-1 (Lussier, et al., 2003; Sharma, et al., 2015). Other sources of Se mobilization include agricultural practices in previously submerged areas. Anthropogenic modification of hydrologic regimes has caused substantial changes in the biogeochemical cycle of naturally occurring soil trace elements (Lemly, et al., 1993). As shales erode and oxidize, Se-rich soils can form, and subsequent large-scale irrigation practises can mobilize oxidized Se into surface waters. In California, the collection of low-Se concentration irrigation drainage in a reservoir where evaporative losses were significant led to a concentration of Se in which teratogenic effects on wildlife were observed in the early 1980s (Green, et al., 2003). Elemental Se usually remains in the form of nanoparticles in colloidal suspension, resulting from the presence of extracellular polymeric substances and or proteins (Buchs, et al., 2013; Jain, et al., 2017) 1.5.2 Toxicity Bioavailability and toxicity of Se depend heavily on the oxidation state, with SeO 32being 5-10 times more toxic than SeO42- (Amweg, et al., 2003). Organic-Se2- is taken up by 19 algae 1000 times more easily than inorganic forms, making it the most bioavailable form of Se (Pahler, et al., 2007). The environmental ecotoxicology of Se is complicated because it has a narrow margin of safe concentrations between deficiency and toxicity (to aquatic organisms). Selenium has three levels of bioactivity: (i) trace levels which are required for growth and development, (ii) incremental levels which are stored while homeostatic functions are maintained, and (iii) elevated levels which result in toxic effects (Hamilton, 2004). The primary pathway of Se into fish tissue is absorption through the gut, however it can also be absorbed through the gill and epidermis (Hamilton, 2004). Selenium bioaccumulates and this property makes it especially dangerous; concentrations of 5 parts per billion (ppb) in the lentic environment of Belews Lake, North Carolina, resulted in detrital food pathways that were 510 – 1395 times greater, and planktonic food pathways that were 770 times greater than water borne concentrations (Lemly, 1999). Biomagnification has resulted in approximately 1.5 to 6-fold increases of Se concentrations between plankton, invertebrates and fish, but this effect has not been detected between forage and predatory fish (Muscatello & Janz, 2009). Pairing the above facts with the heightened bioavailability of organic-Se 2- suggests that the presence of reduced organic Se in aqueous systems is a concern. An evaluation of the ecological risk of Se based solely on aqueous concentrations is difficult, due to the redox condition sensitivity and significantly different properties associated with each redox state of the metalloid (Sharma, et al., 2015). In the previously described Kesterson Reservoir, Se concentrations in the food chain were linked to death and deformity of embryos of nesting waterfowl (Wu, 2004). Birds and 20 fish excrete excess dietary Se into eggs with possible consequences of reduced egg hatchability, teratogenicity, and increased juvenile mortality (Lemly, 1998). At Se levels slightly exceeding those where homeostatic functions are maintained, toxicity presents itself in carcinogenesis, cytotoxicity, and genotoxicity (Santos, et al., 2015). Selenosis (poisoning due to chronic excessive Se intake), has been also associated with neurological impairment (Sharma, et al., 2015). Deficient levels have caused symptoms of liver necrosis to present in rats, metabolic diseases such as ‘white muscle disease’ and ‘illthrift’ to present in calves, and liver damage and exudative diathesis in pigs and chicks, respectively (Hartikainen, 2005). In Finland, inadequate Se intake was shown to be the cause of nutritional disorders in pigs (affecting profitability) and as a result, all commerical animal feeds have been supplemented with SeO32- since 1969 (Hartikainen, 2005) 1.5.3 Attenuation Pathways and Remobilization Treatment of Se containing waters can be achieved by physical, chemical and biological technologies (Tan, et al., 2016). These include chemical reduction, membrane separation and coagulation-based processes, and microbial methods (Santos, et al., 2015). Ion exchange and adsorption are also viewed as simple and low costs methods, using organic synthetic resins, oxides, carbon-based adsorbents, and biosorbents and adsorbents derived from natural wastes (Santos, et al., 2015). Multiple commercial systems have been tested at various scales ranging from bench scale to full field scale (and developed for immediate commercial use). A comprehensive list of technologies, showing their development stage, key design considerations, advantages/disadvantages, and capital and operating costs is presented in CH2M Hill (2010). Variations in water characteristics make it difficult to identify a single best treatment option. 21 Biological removal of aqueous Se can be achieved by phytoremedial and microbial treatments. The bioavailability of Se to plants and organisms, and not the Se content, is responsible for the element’s uptake in plants and organisms and dictates its entrance into food chains (Winkel, et al., 2012) Soluble Se concentrations have been reduced via phytoremediation by species including Polypogon monspeliensis, Typha angustifolia, Typha domingensis, and Typha latifolia. These species have biologically volatilized selenides (Se 2-) from oil refinery wastewaters near San Francisco Bay (Hansen, et al., 1998). Seleniumvolatilization rates by Brassica juncea were shown to be 2-3 times higher for plants supplied with SeO32- compared to SeO42- (de Souza, et al., 1998). In a vegetated wetland analysis where 62.9% of the total Se inflow mass was removed, most of the Se was retained in the sediment, and less than 5% was retained in the plant tissues (Lin & Terry, 2003). The same study reported that different plant species had different volatilization rates, and rates were seasonally dependant. Microbial enhancements of the phytoreductive effects facilitate 35% of plant Se volatilization and 70% of plant tissue accumulation in Indian Mustard (Brassica juncea) (de Souza, et al., 1999). Phytoremediation of both SeO 42- and SeO32- has been shown to be effective, but volatilization rates reported for one study ranged from less than 5 µg m -2 day-1 to 274.4 +/- 99.9 µg m-2 day-1 (Lin & Terry, 2003). In another study, plant volatilization of Se oxyanions was reported in the order of µg Se day-1 m-2 leaf area (Terry et al., 1992). These rates of Se attenuation suggest that this mechanism is applicable in low flow conditions where significant space is available for wetland development. A concern of biological processes, including phytoremediation of oxidized Se compounds, is the possibility of generating more highly toxic compounds, such as selenomethionine, which is 10,000 times more toxic than SeO 42- (Murphy, 1988). 22 Microbial reduction of Se oxyanion concentrations is achieved via assimilatory and dissimilatory processes. In assimilation, oxyanions are transported into the cells by different permeases, then reduced (Eswayah, et al., 2016). In seliniferous environments, assimilitory reduction is expected to contribute minimally, while dissimiltory reduction is considered to be the dominant form of removal (Eswayah, et al., 2016). Dissimilatory reduction occurs when anaerobic microbial respiration reduces oxyanions of Se while a variety of electron donors are utilized (Eswayah, et al., 2016), as described in Section 1. Selenate is reduced to SeO32-, which is then reduced to Se0, with further reduction to organic and inorganic Se2- possible. Selenium-reducing bacteria have been identified and tested in both water (Losi & Frankenberger, 1997) and sediments (Siddique, et al., 2007; Fujita, et al., 2002). Specific strains of bacteria are more effective at reducing SeO42- to SeO32-, while others are more effective at reducing SeO32- to Se0 (Fujita, et al., 2002). Concentrations of Se in water can affect the development of Azospirillum brasilense (Se-reducing microbial) which stalls in the lag phases of growth as concentrations of SeO32- increased from 1 to 5mM (Vogel, et al., 2018). Bacillus sp. SF-1 is an effective reducer of SeO42- to elemental Se but not further (Fujita, et al., 2002). Adsorption experiments at neutral pH have shown that SeO 32- readily adsorbed to wetland sediments, while SeO42- did not (Baldwin & Al, 2003). In another adsorption experiment, at least 50% of SeO32- adsorbed onto different oxy-hydroxides of Fe in the first 10 minutes, with equilibrium being reached in about 2 hours, and adsorption decreased as temperature increased from 298-308 Kelvin (Parida, et al., 1997). Parida, et al., (1997) also found a sharp decrease in percent adsorbed in multiple trials as pH increased past approximately 7.25-7.50 standard units. Another study has shown adsorption to decrease with 23 increasing pH but noted no specific significance of the 7.25-7.50 pH range (Balistrieri & Chao, 1987). The decrease in adsorption at increasing pH is due to the balance shown in Equations (20) and (21) below (S-OH being the surface hydroxyl group and S-SeO3- and SHSeO3 being the adsorbed SeO32- species) (Parida, et al., 1997; Balistrieri & Chao, 1987): (20) S-OH + H+ + SeO32- ↔ S-SeO3- + H2O (21) S-OH + 2 H+ + SeO3-2 ↔ S-HSeO3 + H2O Adsorption of Se-2 and Se(IV) onto Fe minerals (FeS2 and Fe-oxyhydroxides) has been observed at pH less than 8, and these behaviours may be explained by the oxidation of the FeS2 surface (Naveau, et al., 2007; Tachi, et al., 1998). The reduction of SeO32- to Se0 can occur via numerous mechanisms, and this reaction can be catalyzed by reductases including periplasmic NO2- reductases and dimethyl sulfoxide reductases (Eswayah, et al., 2016). Engineered systems for the treatment of SeO 42- and SeO32are often designed with the reduction to Se0 in mind, but these oxyanions are readily reduced to Se2- (Herbel, et al., 2003). An important requirement in the design of any engineered removal system is the understanding of the physical and chemical properties of Se species present (Jain, et al., 2017) Elemental Se, generally appearing in the form of Se nanoparticles (Eswayah, et al., 2016), is of little toxicity and can be more easily removed from the aqueous phase due to its insolubility compared to oxyanions (Fujita, et al., 2002). The mechanisms involved in the formation of Se nanoparticles, and their physical and chemical formations have not been fully characterized (Eswayah, et al., 2016). Aqueous concentrations of Se can be measured by Inductively Coupled Plasma Mass Spectrometry (ICP-MS), but differentiating between the various forms (oxygenated and 24 reduced) requires additional measures. High-performance liquid chromatography coupled to a collision cell inductively coupled plasma mass spectrometer is a cost-effective method for quantifying selenium species to sub parts per billion levels (ALS Global). A concern of remediation strategies that remove soluble Se through reduction is the unknown long-term stability of the reduced precipitates, which is dependent on the quality and ORP of the water. Kinetic reoxidation of Se nanoparticles will be accelerated, compared with larger particle sizes, due to the higher surface to volume ratio (Winkel, et al., 2012). Another factor affecting long term Se stability is the sloughing off of biological solids, which may contain elevated concentrations of Se (CH2M Hill, 2013). A concern with microbially reduced Se is the propensity of Se0 to form stable colloidal suspensions, which do not settle quickly via gravity, however these can be disrupted by pH, cation concentrations, and dissolved organic matter (Buchs, et al., 2013). The remobilization rate of reduced Se (through subsequent exposure to oxygenated conditions) was low in undisturbed columns subjected to aerated simulated groundwater (Simonton, et al., 2000). Selenium levels were however very close to the maximum concentrations established by the United States Environmental Protection Agency (EPA) Resource Conservation and Recovery Act standards for hazardous waste (1.0 mg L -1) in effluents from a leaching procedure on the substrate from these columns (Simonton, et al., 2000). While the main focus of the above text has been bioremedial attenuation pathways, reduction in Se concentrations can also be achieved by conventional desalting, adsorption, and chemical reduction schemes (Murphy, 1988). Chemical reduction methods using ferrous hydroxide are common (USA Patent No. US 6183644 B1, 2000). Chemical reduction with 25 zero valent iron (ZVI) has also been investigated, with earlier trials resulting in quick cementation of the Fe filings (Santos, et al., 2015). Recent studies have shown the oxidized Fe products can have reduced Se embedded in their solid structure (Santos, et al., 2015). Disadvantages of ZVI include the long hydraulic residence times required (typically greater than 4 hours of contact time), pH and temperature dependence, costs related to sludge disposal, and the passivation of ZVI (CH2M Hill, 2010). At the Brule Mine, Se concentrations in the receiving waters have been increasing, peaking at 69 μg L-1 in the month of August 2014 (Walter Energy, 2015), a value that exceeds the WQG maximum concentration of 2 μg L-1 (Beatty & Russo, 2014). 1.6 Other Redox Sensitive Parameters Other redox sensitive parameters that are present in mine water include O 2, Fe, Mn, and As. The regulatory compliance sampling location at the Brule Mine is in a creek immediately downstream of a large elevation change, and the water is rapidly flowing. As a result, samples collected at this location are assumed to be exhibit high redox potentials. Groundwater in the vicinity of the mine has shown high levels of reduced Fe(II) (source: site investigations). Natural groundwaters containing Fe(II) are not stable under ambient conditions: Fe concentrations are lowered by oxidation and precipitation at rates governed by diffusion of O2 through air (Hem & Cropper, 1962). Oxidized Fe(III) is insoluble at neutral pH ranges. The result of this behaviour is observable in the discharge of artesian wells; groundwater with low redox potentials flowing from well taps and splashing on the ground will often run clear but leave a rust layer on the ground (splashing of the water rapidly introduces O2). 26 Manganese speciation behaviour is similar to that of Fe: reduced species are soluble, while oxidized species are less soluble and precipitate. These special characteristics of Fe and Mn help identify the spatial distribution of redox conditions in waters where these constituents are present (i.e. landfill leachate plumes) and also help to identify the governing redox environments (Bjerg, et al., 1995). They also identify redox zones in ocean waters and sediments, where deeper zones contain soluble species, and shallow ones contain particulate forms of the metals (Spencer & Brewer, 1971). Arsenic mobility is strongly linked to its redox state as well, with its reduced form being adsorbed much less strongly to the surfaces of metal oxides than the oxidized form (Newman, et al., 1998). Arsenic toxicity is similar to Se toxicity in the fact that it causes toxic and teratogenic effects in micromolar concentrations, and its crustal abundance is relatively low (Stolz & Oremland, 1999). 1.7 Biologically Mediated Processes for Mine Water Treatment Mining wastes have been generated for centuries, and a variety of engineered systems have utilized bacteria to provide dissimilatory reduction of metal and organic contaminants. Techniques for using alternate electron acceptors such as NO 3- and Fe(III) have also been developed (Lovley, 1995). Alternatively, electro-biochemical transformations can be achieved through the utilization of a charge provided from an electrode to reduce oxyanions (Opara, et al., 2014). 1.7.1 Bioremediation In contrast to many organic molecules that can be ‘broken down’ as part of the remedial action, examples of which are some volatile organic compounds, the process of dissimilatory reduction can result in increased volatility or reduced solubility of contaminants, as presented in Equations (9) through (12). Examples of contaminants whose reduction leads 27 to an increase in volatility are NO3- and Hg, and those whose reduction leads to a decrease in solubility are uranium (U), chromium (Cr), Se, and Pb (Lovley, 1995). Microbial treatment systems designed to enhance Se reduction can be divided into passive, semi-passive and active. Gusek (2002) defines passive treatment as a ‘process of sequentially removing metals and/or acidity in a natural-looking, man-made bio-system that capitalizes on ecological and geochemical reactions. The process requires no power and no chemicals after construction and lasts for decades with minimal human help’. The benefits of these passive systems are that they can be operated in remote locations, in harsh climates, with little or no power and maintenance (Gusek, 2002). Interestingly, temperatures approaching (or below) 0°C have not been reported to have a significant effect on the performance of Se-remediating bioreactors (Baldwin, et al., 2015; Opara, et al., 2014; Luek, et al., 2014), though in the 20-50°C range, the greatest conversion of SeO 42- to SeO32occurred at 30°C (Hageman, et al., 2013). The processes involved in passive and semi-passive bioreactors include the development of biologically active suboxic zones for Se-reduction, filtering of suspended material, and adsorption and exchange of Se bearing ions with plant, soil and other biological materials. Semi-passive treatments are those which require active management (e.g., ongoing fertilization or addition of organic amendment) to sustain desired conditions and processes (Martin, et al., 2009). Many laboratory experiments have reduced soluble Se concentrations using organics such as manure (Pahler, et al., 2007), yeast extract (Oremlund, et al., 1999), glucose (Dungan & Frankenberger, 1999), ethanol (Luo, et al., 2008) protein, egg albumen, casein and gluten (Frankenberger & Arshad, 2001), hay, sawdust, and manure (Baldwin, et al., 2015), mulch, 28 manure and bone meal (Luek, et al., 2014) among others as the source of electrons (provided via organic decomposition). Columns of organic substrate from the Wolverine River (Yukon Territory) and gravel amended with various amounts of manure, treated sewage effluent, zero valent iron, alfalfa and wood chips (including a control) achieved reductions in Se concentrations in water sourced from the Wolverine Mine (Mioska, 2012). The introduction of WQG exceedances of Escherichia coli (E. coli) into downstream environments due to the use of manure as the organic substrate has been reported (Luek, 2014). Active treatment systems for Se reduction are design specific. One such design implements a selective screening process to isolate Se reducing bacteria, and then establishes them on a high-density biofilm in an anaerobic reactor with an ideal nutrient and sugar concentration to facilitate the development of reducing conditions. Selenium-contaminated water is passed through the reactor, and a specialized nutrient feed is metered into the reactor creating the electron donor state which facilitates Se reduction (USA Patent No. US 6183644 B1, 2000). Teck Coal commissioned an active selenium reduction treatment system on Feb 17th, 2016 near its Line Creek facility in southeastern BC. The project has an estimated capital cost of 80 million dollars and an annual operating cost of 5 million dollars (Will, 2012). 1.7.2 Role of Organic Substrate In environmental systems, the decomposition of organic compounds provides energy for chemoorganotrophic organisms, and a pathway for the mineralization of organic molecules. As described in Section 1.2, the oxidation of organic molecules is coupled with the reduction of various electron acceptors. Numerous factors impacting the rate of organic decomposition include bacterial population and diversity, physical environment at both 29 regional and microclimate scales (moisture content, pH, temperature and O 2 content), and the chemical nature of the environment and material to be decomposed (e.g., nutrient availability, and the complexity of the molecules). In low O2 environments, decomposition rates may also be limited by availability of alternate electron acceptors. Carbon:N ratios, C:P ratios, other nutrient contents, and lignin content have been shown to affect decomposition rates. Decomposer organisms typically have high N and P contents, and this translates to high N and P nutritional requirements (Enriquez, et al., 1993). Elevated N and P contents should lead to high rates of microbial mass production, and low rates should lead to nutrient controlled remineralisation (Enriquez, et al., 1993). The effect of O2 on organic decomposition has been studied at length, particularly in pelagic sediments. A comparison of aerobic and anaerobic C mineralization showed that aerobic mineralization was approximately 10 times faster than anaerobic mineralization (Kristensen, et al., 1995). Woody debris is mostly composed of cellulose, hemicellulose and lignin (Schmidt, 2006). In the early stage of decomposition of wood materials, bacteria and fungi can degrade simple soluble substrates, pectin, and easily accessible cellulose and hemi-cellulose. Once these readily available substrates are degraded, the degradation of the remaining lignocellulose is dominated by slow growing, saprotrophic, ligno-cellulytic fungi (van der Wal, et al., 2007). Some Actinobacteria, such as Nocardia and Streptomyces, also have a limited ability to degrade lignin (Horwath, 2015). Fungal decay of wood only occurs in the presence of O2 (Blanchette, et al., 1989). A limiting factor in the decomposition of wood by these fungi is often N content. Much research has been devoted to the effect of N additions on litter decomposition and studies have shown both a direct correlation of N additions to mass lost or 30 respiration and no effect between the two (van der Wal, et al., 2007). In a review of available studies, Enriquez, et al. (1993) showed that across all plant types, a positive correlation existed between decay rates and N content, decay rates and P content, and a negative correlation existed between degradation and lignin content. Bacteria are expected to demonstrate a greater response to N addition than are fungi, as fungi are thought to be more efficient in re-allocation or use of N (van der Wal, et al., 2007). Small particles of organic matter are expected to decompose faster than larger particles, due to their increased surface area providing greater access to substrates, and larger surface for bacterial growth (van der Wal, et al., 2007). 1.8 Brule Mine Stratigraphy and Mineralogy The general stratigraphy of the mine consists of three coal seams, hosted primarily within interlayered siltstones and mudstones (Western Canadian Coal, 2006). Sandstone is the least abundant rock type. Petrography and Rietveld XRD analysis demonstrates that the waste rock mineral assemblage is composed primarily of quartz, carbonate, muscovite and kaolinite (PetraScience, 2005). Pyrite is the main S 2- mineral (Western Canadian Coal, 2006). With regards to carbonate mineralogy, siltstones are dominated by calcium carbonate (CaCO3), while mudstones contain roughly equivalent proportions of Fe-carbonate and CaCO3 (Western Canadian Coal, 2006). A sample of mudstone from the mine contained 0.2%, 3.1%, 4.0%, and 1.6% of FeS2, calcite, siderite, and ankerite, respectively (Western Canadian Coal, 2006). A sample of siltstone contained 0.3%, 9.0%, 3.8%, and 6.3% of FeS 2, calcite, siderite, and ankerite, respectively (Western Canadian Coal, 2006). The results of acid-base accounting (ABA) and mineralogy suggest that total S occurs mainly as S2- minerals and organic S. During any oxidizing events S 2- and organic S are 31 expected to oxidize rapidly and slowly, respectively. In waste rock, an acceptable assumption is that all S is bound up in FeS2, while in coal, the greater presence of organic S invalidates the above assumption (Western Canadian Coal, 2006). 1.9 Column Design Review Many studies investigating the fate and transport of pesticides, explosives, microbes, heavy metals and non-aqueous phase liquids as well as evapotranspiration, use soil columns in both saturated and unsaturated regimes (Lewis & Sjostrom, 2010). Column design can be partitioned into two broad categories: packed (disturbed) components and monolithic columns of intact soil. Packed (and if possible screened) contents are typically more homogeneous than monoliths, which is expected to allow greater reproducibility, while monoliths will likely better reproduce field conditions at the expense of reproducibility (Lewis & Sjostrom, 2010). Multiple studies have reported that experimental results have changed as a result of the choice between packed and monolithic components. Packing may lead to homogeneous columns avoiding the formation of stratifying layers or preferential flow pathways. Up-flow column reactors, in which water flows in an upwards direction, entering the base and exiting the top, reduce the development of preferential flow paths and last longer as they do not promote compaction of the column materials (URS Corporation, 2003). Upflow reactor fluids are driven by a pump, and this promotes complete saturation (Electric Power Research Institute, 1991). Column systems that achieve influent delivery through a small tube or port, rather than uniformly to the entire cross section, have less uniformity of flow as column size increases (Electric Power Research Institute, 1991). This issue can be overcome with the use of porous endplates (Electric Power Research Institute, 1991). Lewis & Sjostrom (2010) summarize a soil column study in which the inlet orifice had a radius less than the 32 column radius, and the resulting effect was non-uniformity of velocity profiles at the end, and the height of the zone of influence was calculated to be up to 1.5 times the column radius. Sidewall flow, and for soils, macropore flow, can also influence flow regimes through saturated columns. For example, flow velocity at a column wall was found to be 1.1 – 1.45 times the flow velocity in the column center, and that sidewall flow increases with larger soil particles (Lewis & Sjostrom, 2010). Ensuring complete saturation is also important to achieve uniform flow, as pockets of gas can substantially influence the flow of liquids through pore spaces. As a result, a week-long period of static saturation will allow entrapped air to dissolve and disperse in pore liquids of soils (Lewis & Sjostrom, 2010). Another method of removing air from the column in to flood the column with carbon dioxide (CO 2), as this gas is several orders of magnitude more soluble than the component gases of air, resulting in faster dissolution of CO2 bubbles when compared with air (Lewis & Sjostrom, 2010). Steel, acrylic, or glass accounted for over 60% of experimental setups documented in a review by Lewis & Sjostrom (2010). Factors that determine material choice include: a) whether transparency is required, b) the structural requirement of the material, c) whether the material will chemically affect the processes internal to the column (inertness), d) the ease of installing instrumentation, and e) any cost or availability considerations pertaining to the material of choice (Lewis & Sjostrom, 2010). Saturated columns (of soil) should have a baffle zone as least as thick as the column diameter, at both the inlet and outlet of the column, to avoid non-ideal flow patterns (Lewis & Sjostrom, 2010). To avoid sidewall effects, it is recommended that a 1:4 ratio of diameter to length be applied for cylindrical columns. 33 1.10 Research Objectives and Approach A saturated up-flow column reactor study was used to identify ways of promoting Se removal and denitrification (i.e. NO3- removal) from mine effluent. In the experiment, toe seep effluent (characterized earlier) was pumped at a metered rate through columns containing Crushed Mine Waste Rock (CMWR) and locally available organic amendments. The decomposing amendments provided the electrons required for the reduction of species of interest (O2, NO3-, SeO42-, SeO32- and SO42-) and fostered the necessary conditions for the proliferation of bacteria required for the experiment. The experiment was conducted at the University of Northern British Columbia (UNBC) within the Enhanced Forestry Laboratory (EFL) to control climatic interferences. The experiment was initially set up to address the following questions: a) Which of two easily available (to the Brule Mine) organic amendments is best suited as an electron donor for promoting Se removal from Brule Mine effluent? How do the two amendments differ in their kinetics (time to onset of reducing conditions) and longevity (how appropriate redox conditions are maintained) in regard to their ability to foster conditions conducive to denitrification and Se removal within waste rock environments? An original subpart of the above question was ‘How does an increase in mass of a single amendment affect the reaction kinetics?’ but limitations to the scale and size of the experiment prevented this consideration to be addressed. b) What are the biogeochemical mechanisms governing the speciation and behavior of Se and N in waste rock pore waters in response to these organic amendments? c) How does the use of organic amendments and CMWR in a saturated low-flow, toe seep effluent environment affect column effluent water quality? i.e. in addition to Se and 34 NO3-, will the concentration of any other parameter of environmental relevance be significantly affected by the column conditions? To address these questions, an experiment was performed comparing organic amendments in a saturated CMWR environment for their ability to foster Se reducing and denitrification conditions. The effluents of up-flow column reactors containing various treatments were collected on a weekly or bi-weekly schedule and analyzed to infer intercolumn conditions, and to examine amendment effects on effluent water quality. The potential for contaminant remobilization through oxidation or complexation has not been evaluated in this research. The short-term nature of this experiment also did not allow for adequate exploration into effects from material aging, matrix clogging, or remobilization of attenuated elements. The column experiment was designed and operated while a full-scale biochemical reactor (BCR) was constructed at the Brule Mine. Insights derived from the bench scale column study were expected to aid in overcoming some of the technical, permitting, and operational challenges encountered during future implementations of BCRs, as the Brule Mine had forecasted the need for at least two more operational scale units at the mine site. 1.11 Readily Available Organic Substrate in NEBC Organic amendments (C sources) used in the full-scale BCR at the Brule Mine were chosen for inclusion in the column study. The following criteria were used by the mine administrators to find appropriate C sources:  Cost: the volume required for field scale application in a bioreactor is expected to be substantial, and an annual ‘top-up’ may be required to compensate for organic decomposition and losses to throughput water. These factors put constraints on the 35 unit cost of the amendment. While short chained organic compounds have been used in published experiments, their cost was prohibitive in the scale required at the mine;  Abundance and proximity to the mine: Shipping amendments to the remote location of the mine was a major cost of the project. Successful Se bio-attenuation using food processing wastes as C sources had been proposed by Bioremedial Technologies Inc. (Matt Perry, personal communication, 2013), but the cost of transporting these wastes from major industrial centers was prohibitive. In addition, if the project could use a waste or by-product of a local industry, it could benefit the industry and increase the social license of the mine; and,  Reactivity: The material must be considered relatively inert in the event of a spill or large-scale release to the sensitive surrounding watershed. The mine housed a 150person capacity work camp, complete with sewage treatment lagoon. It was decided early on by project stakeholders that using sewage as the organic amendment would cause unnecessary logistic and regulatory complications, and possible guideline exceeding concentrations of E. coli. After eliminating organic amendments which did not meet the above criteria, there were two remaining options. The first option was sawdust from a local sawmill, considered a waste stream and burned in a large beehive burner (note: the sawdust is now being burned in an electrical cogeneration plant). The second option was old bales of hay no longer suitable for livestock feed (e.g. bales of hay having been exposed to at least one winter in fields of farmers). An additional benefit of this old hay was that because of moisture and aged conditions, bacterial decomposition had likely already begun, some microbes of which were possibly anaerobic. 36 Multiple considerations indicated that the inclusion of CMWR as an amendment in the columns was appropriate including;  The need to use similar volumetric ratios of tailing material to organic matter to other studies, in the event that comparison of results between experiments is necessary or appropriate (see Table 1.2);  The importance of creating an experiment that was comparable and thus applicable to the bioreactor design being implemented at the Brule Mine;  The assumed effect of CMWR would be to increase the overall porosity of the columns to achieve less clogging (due to increased particle size).  The increased specific gravity of CMWR with respect to both the organic amendments and water, which was anticipated to result in less accumulation of fines in the upper (effluent) valves of the column (i.e. the CMWR could ‘hold’ the amendment in place). Table 1.2: Summary of research used to determine CMWR: organics ratio Number #1 #2 #3 #4 Article Author Evaluation of in situ layers for treatment of acid mine Hulshof, et drainage: a field al. comparison Microbial and nutrient investigation into the use Hulshof, et of in situ layers for al. treatment of tailings effluent Transport and attenuation of metal(loid)s in mine Lindsay, et tailings amended with al. organic C: column experiments Year Quantity 2006 Tailings: organic matter (om) - 4:1 volumetric ratio 2003 Column components tailings: om - 4:1 volumetric ratio Results Pulp residue was more effective at generating anaerobic conditions than woodchips, likely due to composition and 'respiration rates' High SO42- reduction initially observed then reduced over time due to complete consumption of labile C Column Increased attenuation of certain compositions 0, 2, parameters and mobilization of 2011 & 5 vol. % others at 5 vol. % (more than 2% & amendment 0%) Managing pore-water quality in mine tailings by Lindsay, et 2009 inducing microbial SO42al. reduction "Amendment of tailings with a Field scale cell: small and dispersed mass of organic 0.6 % weight & 5 C resulted in a general decrease in % volume C mass transport of S2- oxidation products" 37 Section 2: Materials and Methods 2.1 Overview In order to address the research questions outlined in Section 1.9, a column experiment was designed with support from Lorax Environmental Services (Lorax) and the supervisory committee. The experiment was executed with technical help from Lorax and operational support from the UNBC EFL curators. Organic amendments were collected from sources local to the mine, and inorganic materials were sourced from the mine. Laboratory materials were collected from UNBC Chemstores, equipment providers, and specialty manufacturers as needed. To properly quantify the effect of individual column amendments on redox conditions, column influent and effluent liquids were collected and characterized for elemental and ion concentrations. Organic amendments were submitted to ALS Environmental Laboratories (ALS) for chemical characterization. Subject to funding constraints, a collection schedule was initiated and followed (the details of which are presented in Section 2.4.5.2). A rigorous Quality Assurance and Quality Control (QAQC) sample collection and submission plan was created. 2.2 Materials In the following descriptions, all dimensions are provided in metric. As needed, imperial units are provided immediately after in parentheses to indicate that the original unit of measure was imperial and was converted for the thesis. An example is the size of tubing – specifications are provided by the manufacturer in standard imperial units (e.g., 1/16", 1/8") 38 but are reported herein as metric (e.g., 1.59 mm (1/16") and 3.18 mm (1/8")). Where original measurements were metric, no imperial units follow. 2.2.1 Treatments Attempts were made to obtain a chemical characterization of the amendments and where practical, particle size distributions. Amendment ratios were chosen at a volumetric ratio of 4 units of CMWR:1 unit of organic matter, to reflect published studies (shown in Table 1.2). To determine if there was a synergistic effect of a combine (hay and sawdust ) application, a treatment consisting of a volumetric ratio of 8 units of CMWR:1 unit of hay:1 unit of sawdust was used, which maintained the 4 units of CMWR:1 unit of organic matter. To quantify the potential leaching effects of CMWR in the effluent water, a column consisting of only CMWR was created as well. Amendment masses and volumes were as displayed in Table 2.1.5 Table 2.1: Treatment mass6 and volume of substrates utilized within experimental columns Column 1 2 5 6 Crushed Mine Waste Rock Sawdust Hay Total Solids Mass (kg) Volume (L) Mass (kg) Volume (L) Mass (kg) Volume (L) Mass (kg) Volume (L) 3.575 2.565 0.192 0.640 3.767 3.205 3.700 2.565 3.700 2.565 3.725 2.565 0.070 0.320 0.096 0.320 3.891 3.205 3.700 2.565 0.141 0.640 3.841 3.205 2.2.2 Column Design The column design was provided Lorax and constructed by Dimension 3 Plastics Limited, of Burnaby, BC. Column specifications are provided in detail in Appendix C. 5 Results have been dismissed from two columns, as the experimental design was not rigorous enough to properly quantify all of the variables. 6 Treatment mass refers to mass of amendment in the state they were when added to the columns and should not be interpreted to mean dry mass. 39 While the columns did not match design criteria suggested in Section 1.8, the design and manufacturing process had been perfected by Lorax and Dimension 3 Plastics Limited through previous iterations. Six columns were received at UNBC on October 20, 2014. The columns were modelled after up flow packed bed reactors. A 3.18-mm (1/8”) thick plastic plate, 1.59 mm (1/16”) smaller than the column inner diameter (ID), with machined flow dispersing grooves radiating from the center to small holes drilled through the plate, was placed in the bottom of each column to help minimize the development of preferential flow paths. This plate was overlain with a 1 cm layer of boil-sterilized 20-30 mesh Ottawa Sand to distribute the flow equally through the cross-sectional area of the column (please refer to Appendix B for an image of the sand layer). The column specific mixture of CMWR and organic amendment was placed on top of the flow dispersing media. Please refer to Figure 2.1 for an image of a saturated column, taken after 1 week of operation. 2.2.3 Hay Hay was sourced from the Brule Mine BCR project. The mine had accumulated approximately 1400 round bales of hay from farms in the vicinity of the mine. One contractor was responsible for the collection of hay bales sturdy enough to be handled by a forklift, but no longer suitable for livestock feed. This system of hay procurement provided ease of management as only one contractor required access to the mine. Unfortunately, this system lacked sufficient accountability to specify exactly where the hay was grown, how long it had been since its harvest, and the species distribution. 40 Figure 2.1: Column with 1 cm layer of Ottawa Sand overlain by organic amendment mixed with CMWR. 2.2.4 Sawdust Spent sawdust was collected from the West Fraser Sawmill (3598 W Fraser 89, Chetwynd, BC) on June 3rd, 2013, directly from the milling process waste stream conveyor belt. According to the mill operators, the mill was processing approximately 99% White Spruce (Picea glauca), all sourced from within a 200-km radius from the mill. The mill regularly ran other species including Lodgepole Pine (Pinus contorta) and Subalpine Fir (Abies lasiocarpa) (Source: Field Notes, 2013). The sawdust is assumed to be from softwood species. Samples were stored in sealed 20 L buckets and transported to UNBC in early September. 41 2.2.5 Crushed Mine Waste Rock Previously mined (waste) rock was regularly crushed to make gravel for road maintenance at the Brule Mine. As part of the crushing process, gravel was screened to remove fines less than 19.1 millimeter (mm) (3/4"). These smaller diameter fraction (rejects smaller than 19.1 mm) from the 2013-2014 period were placed in 20 L sealed buckets in August 2014 and transported from the mine to UNBC, to be used as CMWR. 2.2.6 Mine Water A 1000 L (1 m x 1 m x 1 m) polyethylene tote, previously used for transporting grape concentrate for wine production, was purchased from Hobby Brews (Prince George B.C.). The tote was cleaned with muriatic acid (31.45% strength) and triple rinsed with de-ionized water supplied by UNBC (the entire process was repeated twice). The tote was then filled with water collected from a toe seep historically characterized by high levels of mine signatures. A 51 mm (2") trash pump and hose were used to transfer the water on Friday, October 10th, 2014. Prior to filling the tote, toe seep water was pumped though the trash pump for 10 minutes to flush out any accumulated debris and contaminants in the pump housing. The following measures were implemented to maintain a static water chemistry over the duration of the experiment:  To prevent ultraviolet (UV) light from entering the tank, which could cause biofouling, the growth of algae, and could change the water chemistry, a black fabric tarp was wrapped around the tote, extending from the floor to the top of the tote and held in place with tape and staples; and, 42  To maintain oxic conditions in the tote, a 4.5-Watt, 5.4 L min -1 fish tank aerator was installed and left running from Wednesday October 15th until the end of the experiment. Lines from the aerator were connected to fish tank air dispersion stones at the bottom of the tote, which resulted in a constant bubbling of O 2 through the mine water. To accommodate the air supply and water extraction (column supply) lines, three 2.54-centimeter (cm) diameter (1") holes were drilled into the lid of the water tote. A wooden platform was fabricated to sit on top of the tote to serve as a workspace and a hole was cut in the platform to allow access to the lid (located at the center of the tote surface). In periods of no maintenance or sampling, any clear plastic exposed lines were also loosely covered with aluminum (Al) foil to further prevent light from accelerating biofouling. 2.3 Experimental Design Lorax provided a column design template. An annotated photograph of the design (Figure 2.2) and descriptions of the individual elements are provided below. 43 Figure 2.2: Experimental configuration during sampling events – annotated to reflect the description of Section 2.3. A) 1 x 1000 L polyethylene tote of toe seep water (described in detail above in Section 2.2.6). B) 1 x 8-channel standard-speed digital dispensing pump provided a consistent flow volume to each column. The pump drive and corresponding flow rates were verified by a NIST Traceable Calibration Report (provided in Appendix C) as part of the procurement process. C) 6 x column (described in detail above in Section 2.2.2). D) 6 x sample collection container (see Figure 2.3): 500 milliliter (mL) polypropylene bottle with two 5.56 mm (7/32") diameter holes drilled in the top 44 and plugged with an inlet and an outlet line. These lines were polytetrafluoroethylene (PTFE) 1.59 mm (1/16") ID by 3.18 mm (1/8") outer diameter (OD) tubes inserted in softer C-Flex 3.18 mm (1/8") ID by 6.35 mm (1/4") OD tubing. The softer tubing created an airtight seal between the 5.56 mm ID hole and the 3.18 mm OD tube. Both inlet and outlet lines end in 4-way valves (stopcock with male Luer lock connections, shown in Appendix B). The inlet tubing delivered liquid into the container, and extended to the bottom of the container, while the outlet line allowed venting of displaced gas (N 2) and extended approximately 2-cm into the container. The tubing used in the experiment was predominantly PTFE 1.59 mm (1/16") ID by 3.175 mm (1/8") OD, and this tubing is referred to as ‘typical’ in the following description. Special tubing was required for column attachments and the pump housing. All connections (except for the column fittings) were male or female polypropylene Luer lock 1.59 mm (1/16") hose barb adapter fittings. Four-way stopcock valves were placed between each successive piece of tubing or apparatus so that in the event of biofouling, plugging, or trouble shooting, individual sections of the system could be isolated, tested and or removed without introducing air to the otherwise saturated system. The influent delivery and effluent collection system was identical for each column, so the description below describes the path of fluid through the system and continues to reference Figure 2.2. E) The collection line, consisting of typical tubing, was taped to a weight so it would hang suspended in the 1000 L tote. This prevented the line from either floating on the water surface and drawing in air or resting on the bottom and drawing in 45 sediment. The line extended from inside the tote to a 4-way valve immediately preceding the pump. F) Departing the 4-way valve was 0.79 mm (1/32”) ID tygon tubing which sat in a dedicated pump channel. The pump was external to the tubing, and as such, did not impact the water quality. The tygon tubing is more resistant to the wear caused by the pump than the typical tubing. G) The next section of typical tubing conveyed water from the pump to a 4-way valve at the bottom (inlet) of the column (in Figure 2.2 this is difficult to see as these lines were run from the pump to each column underneath the wooden workspace). H) A small piece of 1.59 mm (1/16") ID viton tubing connected the 4-way valve to the inlet port (or bottom) of the column via a 3.18 mm x 3.18 mm (1/8" x 1/8") polyvinylidene fluoride (PVDF) compression fitting. Viton tubing was chosen for its compatibility with the compression fitting (this is clearly displayed in Figure 2.4, which shows an inverted column, but cannot be seen in Figure 2.2). I) Upon exiting the column through the outlet (top) 3.18 mm x 3.18 mm (1/8" x 1/8") PVDF compression fitting, 1.59 mm (1/16") ID viton tubing conveyed the water to a 4-way valve. J) During sampling events the 4-way valve was configured to direct flow into an N 2purged sample collection container described in D) (above) and shown in Figure 2.3. The configuration shown in Figure 2.2 is for sampling events. As the container was filled with the column effluent, displaced N 2 would flow out the effluent line. The end of the effluent line was submerged in a container of tap 46 water. The submerged effluent line ensured that N 2 could bubble out, but air could not flow up the line, and the introduction of O 2 in the sample was prevented. Figure 2.3: Sample collection containers, with inlet and outlet tubes individually valved to allow N2 purging and sample collection in an O2 depleted environment. The containers would be connected in series to a N2 cannister and purged for 5 minutes then individually sealed (under positive N2 pressure) and hooked up to the sampling system. A good indication that the system was working properly was bubbling out of the submerged effluent lines when the valves were opened. This system of positive pressure verification was only established after week 2. 47 Figure 2.4: An inverted column during maintenance - changing a leaking influent hose (on the bottom). Note the 3.18 mm x 3.18 mm (1/8" x 1/8") compression fitting on the column bottom. This allowed tubing to be firmly sealed to the column bottom. A similar fitting was attach attached to the effluent (top) side. In order to get a representative sample for pH, ORP, and DO measurements, the connection from I) (above) was connected to the bottom of a 15 mL polypropylene vial, allowing effluent to flow up through the vial. The multimeter probe would be inserted into each vial from the top and would measure saturated liquid flow. The vials for all columns were mounted on a single board and are shown in Figure 2.5. 48 Figure 2.5: Up flow 15 mL polypropylene containers into which the multimeter probes were inserted. During normal operations (not sampling events) typical tubing connected the 4-way valve to an overflow collection jug, as shown in Figure 2.6. The collection jugs were maintained at a higher elevation than the columns to prevent siphoning of column liquids. On a weekly basis, the collection jugs would be compared and drained. Any variance in the volumes of effluents from the columns would indicate tube plugging, pump tube rupture or system failure, and signalled that corrective action was required. 49 Figure 2.6: Experimental setup – configured for normal flow through operations (columns were not yet connected to overflow collection jugs) 2.4 Analytical Methodology A list of the analyses performed, and the specific methods employed on liquid (water) and solid (organics and CMWR) matrices can be found in Appendix C. 2.4.1 Hay Preparation On September 7th, 2014, four representative samples were pulled by hand from the bales at the mine site and transported to UNBC where 3 were shipped immediately, on September 15th, to ALS for chemical characterization. The sample not sent away for characterization was dried for a period of 7 days at ambient temperatures in the greenhouse of the EFL at UNBC, and shredded using the hammer 50 & screen mill (hammer mill) of the EFL on September 30 th, 2014. The hammer mill screen had 1.59 mm (1/16”) round openings. Individual pieces of hay, larger than the screen openings, were observed after milling, indicating that some pieces had passed lengthwise through the screen opening, requiring a second milling. The resulting volume of hay was insufficient for the experiment, and on October 4 th, 2015 a second collection of hay occurred at the mine site. The second collection was also dried for 7 days in the greenhouse and similarly milled twice. This method of particle size normalization provided no data about the distribution of grain size. The hammer mill was disassembled and cleaned with compressed air and a vacuum immediately prior to and after each use. 2.4.2 Sawdust Preparation Three samples of the sawdust were sent to ALS on September 7 th for chemical characterization. The analysis was similar to that performed for hay, but no analysis for available NH4+ was requested (as per discussions with Dr. Rutherford). Wood chips were milled twice in the hammer mill on September 30th, 2014, providing a pre-treatment similar to that of the hay samples discussed above. The hammer mill was disassembled and cleaned with compressed air and a vacuum immediately prior to and after each use. 2.4.3 Crushed Mine Waste Rock Preparation Three samples were sent to ALS for metals characterization, ABA, C content and physical tests which included SO42–S, pH, and moisture quantification. Cone and quartering methods (USEPA, 1993) were performed on a 29.2 kg sample of CMWR to maintain similar particle size distribution in the subsamples. A starting volume eight times greater than the required column volume was placed in a pile and the coning and quartering method was performed (Schumaker et al., 1989). This involves extensively mixing the rock volume in a 51 pile to achieve particle size distribution heterogeneity, and then quartering the pile to get representative subsamples (Figure 2.7). This method is not designed to provide similar masses or volumes in the subsamples and resulted in subsamples which were not comparable in size or mass. Figure 2.7: Cone and quarter method in progress. When performing the coning and quartering method, a criteria of acceptability (CoA) of 5% relative percent difference (RPD) between sample masses was chosen, where sample A is split into subsamples B & C and the RPD is given by Equation (22): (22) 𝑅𝑃𝐷 = 100% ∗ (2) | | Note: all subsample values indicate masses If the RPD exceeded 5%, the subsamples would be recombined, and the cone and quartering method would be applied again. This introduced an unintended bias: the cone and quartering method was performed on 0.254 mm (10-mil) thick plastic sheeting, but due to the angularity of the rock, the sheeting was punctured during every iteration of the method, which resulted in a loss of small fines (see Figure 2.8). An attempt was always made to recover the fines, by sweeping under the sheeting, but if the cone and quartering method was performed 52 numerous times to meet the CoA, successive re-handling of the rock may have influenced the particle size (e.g., particles becoming stuck in the broom on each sweep). Figure 2.8: Residual fines left on the plastic sheeting after a cone and quartering event. Sweeping above and below the sheeting resulted in most fines being recovered, but some losses resulted from each iteration of this method. The cone and quartering method was used again to split one CMWR subsample into 4 smaller samples. This sub sample splitting was performed on a clean laboratory bench using a dustpan and brush. On July 29 th, 2015 these samples were submitted to ALS for particle size analysis to determine what the particle size distribution of this material was. 2.4.4 Sample Collection and Chemical Analysis Column effluent was collected in the N2-purged environment of the sample containers at the experiment site (see Section 2.3). The sample containers were then moved to a fume hood where they would be placed in a 571.5 mm (22.5”) N 2 purged inflatable glove bag7, 7 The glove bags were procured after the week 2 sampling event, and O2 may have been introduced during filtering in the first 2 weeks, 53 allowing for effluent filtration and handling in an O 2 depleted environment. Filtration was achieved with plastic 50 ml Luer lock syringe, and 0.45-micrometer (μm) pore sized polyethersulfone (PES) membrane filters. In this environment the samples would be transferred into parameter specific sample shipping bottles and preserved according to ALS instructions.8 Please refer to Appendix C.4 for the list of preservation instructions (supplied by ALS) which were followed during the experiment. Samples stored in the 4 degree Celsius (°C) walk-in cooler in the EFL and were shipped on ice to ALS within 8 days of collection. Samples were analyzed for concentrations of parameters relevant to the project: dissolved metals, N species, S2-, anions, dissolved organic carbon (DOC), and total alkalinity (a complete list of parameters and methods employed by ALS can be found in Appendix C.3). Effluent samples were sent to Dr. Dirk Wallschlager at the Trent University Water Quality Center (Trent) for speciation of Se. Four species were reported: Se (VI), Se(IV), Se0 and unidentified Se species. The samples were collected four times; on week 4, 11, 19, and 24. In week 4, samples were preserved by filtration through 0.45 µm PES filter and shipped on ice by overnight courier to Trent. The laboratory technician indicated that there was still an unacceptable presence of suspended solids in the samples, and that even after re-filtering, fine suspended solids clogged the analysis column. Subsequent preservation methods included twice centrifuging the samples at 20,000 revolutions per minute (RPM) at a force of 32 647 x gravity for 45 minutes (90 minutes total) and then filtering through 0.2 µm cellulose acetate 8 In week 12, column 1 samples were not filtered, due to operator error. 54 filters prior to shipment on ice. This resolved the issue of fine solids clogging up the system in the Trent laboratory. Minimum samples volumes, preservation requirements, and hold times are presented in Table 2.2. The target collection volume of each sample was 10 mL greater than that required by the laboratory to allow for duplicate analysis if required, mitigate losses occurring during transfer, possible spillage at ALS, and any other incidental loss of volume. ALS provided all sample containers: 125 mL high density polyethylene (HDPE) verified clean bottles (VCB), regular 125 mL HDPE bottles, and 250 mL amber glass bottles. ALS also provided the following reagents for preserving samples:  1:1 Trace grade sulphuric acid (H2SO4): water mixture  3:1 Nitric acid (HNO3): water mixture  1:9 Zinc acetate (Zn(O2CCH3)2): water mixture  6N Sodium hydroxide (NaOH) solution These reagents were color coded and provided in individual doses sufficient to preserve single samples. Samples that were refrigerated for 8 days prior to shipment exceeded the EPA suggested hold times for the following parameters:  NO3- (2 days)  NO2- (2 days)  S2- (7 days) 55 Table 2.2: Hold times, preservatives, minimum volumes, and containers for parameters measured in the experiment in column influent and effluents Minimum Volume (ml) 30 5 Minimum Hold Times (days)* 14 2 – NO3- + NO2- Sample Container 125 mL HDPE (1) Zn(O2CCH3)2, shake + (2) NaOH, shake 100 7 125 mL HDPE Total Metals (1) Filter + (2) HNO3, shake 50 6 months 125 mL VCB HDPE TOC NH3 (1) Filter + (2) H2SO4, shake 10 50 28 28 250 mL Amber Glass Parameter Preservation method Alkalinity Anions None S2- *Minimum hold time of all parameters (e.g., NO - & NO - in anions), as suggested by EPA 3 2 methods. After consultation with Dr. Rutherford, Clive Dawson (supervisor of the BC Analytical Laboratory), and technical representatives from ALS, it was determined that the samples would likely remain acceptable, so long as they were chilled to 4°C, and their exposure to light was limited. This was accomplished by placing the sample vials inside a sealed cooler, which was placed in the EFL walk-in cooler. 2.4.5 Column operation The Natural Sciences and Engineering Research Council of Canada (NSERC) funding agreement covered a 6-month period, and this provided a fixed timeline for the completion of the experiment. The columns were filled on Jan 26th, 2015, and pumping was initiated on Feb 3rd, 2015, and completed on Jul 24th, 2015. 2.4.5.1 Flows Flows varied from 0.212 – 0.350 mL min-1. Short periods of no flow and high flow were required during the switching of pump lines, but these periods were generally less than 10 minutes in length. 56 2.4.5.2 Sampling Schedule The sampling schedule was determined before starting the experiment to accommodate personnel availability Mondays and Tuesdays (and every second Wednesday), and to remain within the constraints of the funding. Effluent samples were collected from columns 1 and 6 on a weekly basis, filtered, and/or preserved (as required), and stored in sealed coolers in the EFL walk in refrigerator (4°C). Samples from all columns were sampled every second week and preserved. The appropriate QAQC samples would be prepared every second week as well, and the samples from both the current and previous week would be shipped overnight via courier to ALS as one complete sample set. This arrangement was chosen to reduce number of sample sets submitted, resulting in reduced the shipping and QAQC costs. 2.5 Quality Assurance and Quality Control (QAQC) A comprehensive QAQC program was developed to determine accuracy and precision of results, operator error, and temporal variability in the results. 2.5.1 Field (independent of ALS) In every bi-weekly sample set submitted, the following samples were included as part of the QAQC program: 1. Duplicate: The liquid in a randomly sampled collection container was split and submitted as a duplicate sample. The 500 mL sample collection containers (shown in Figure 2.3) did not permit two full suites of samples (305 mL per full suite) to be generated, so S2- analysis was dropped from the duplicate suite (reducing the combined total volume of both original and duplicate sample suites 57 to 500 mL). The duplicate samples were labelled according to a code not provided to the lab. 2. Blank: Samples were either a. Filtered and preserved in the glove bag, as a measure of contamination introduced in the confined and contaminated environment inside the glove bag; or, b. Sampled directly from the Milli-Q meter in the lab and preserved, which hopefully provided a ‘true blank’. 3. Reference: A solution containing 2 mL of Refractory Element and ICP-MS Elements standard (both containing elements at 10 μg mL-1) was mixed with 396 mL Milli-Q water on January 20th, 2015 to create a reference solution. This mixture was acidified to pH<2 with 8 mL trace grade HNO3, and stored in a 500mL volumetric flask, which was wrapped in Al foil and refrigerated in a refrigerator at less than 5°C. 2.5.2 Laboratory With every submitted every sample set, ALS provided data from their internal laboratory QAQC program, with the following parameters reported: 1. Replicates: Replicate analyses are measurements of the variable of interest performed as identically as possible on two subsamples of a sample. Replicate analyses were used to assess analytical variance (Clark, 2013); 2. Certified Reference Materials (CRM) . CRMs are reference materials having one or more property values that are certified by a technically valid procedure, 58 accompanied by a certificate or other documentation is issued by a certifying authority (Clark, 2013); 3. Laboratory Control Samples (LCS): LCSs are known matrixes spiked with compounds representative of the target analytes, and used to document laboratory performance (Clark, 2013); 4. Method Blanks (MB): MBs are analyte-free samples to which all reagents are added in the same proportions as used in sample processing. MBs must be carried through the complete sample preparation and analytical procedure. MBs are used to assess contamination resulting from the analytical process (Clark, 2013); 5. Matrix Spikes (MS): MSs are aliquots of sample spiked with known concentration of target analytes. Spiking occurs prior to sample preparation and analysis. A MS is used to document the bias of a method in a given sample matrix (Clark, 2013). 59 Section 3: Results 3.1 Overview The results of the experiment are presented in this section. A detailed analysis of the QAQC measures introduced in Section 2 are presented in Appendix D.1 through D.4. Issues associated with data quality are presented in Section 3.2. Results of the materials characterization are presented in Section 3.3. The results of the column influent and effluent fluid characterizations are presented in Sections 3.4 and 3.5, respectively. Finally, qualitative observations are presented in Section 3.6. All references to levels of NO3-, NO2-, and NH3 refer to the N content of these measurements. Other parameters have been often prefixed with D- (dissolved) or T- (total). The concentrations of a specific parameter and column throughout the experiment (e.g., concentrations of D-Se in column 1 throughout the experiment) are referred to as a ‘data set’. The following describes how means were calculated when some sample concentrations were below the method detection limit (MDL). The mean of any data set, if less than 15% of data points were less than or equal to the dilution dependent MDL, was calculated by the setting these values to 50% of the MDL (EPA, 2006). In attempting to quantify means of data sets with 15-50% of the values less than or equal to the MDL, the Cohen Method (EPA, 2006) was considered, but the data follows neither normal nor log normal distributions, and as a result, cannot be approximated by this method. As such, for data sets with greater than 15% of the results less than or equal to the MDL, no mean was calculated. A ‘field measurement’ refers to a reading observed in the UNBC EFL, while a ‘lab result’ refers to a measurement obtained from an outside (not at UNBC) commercial or academic laboratory. 60 3.2 Data Quality In addition to the QAQC CoAs used to evaluate the quality of the data in Appendix D.1, results were screened for inconsistency with the rest of the data set. This was noted in a few instances and the following corrective actions were taken:  In weeks 1 and 2, procedures for sample handling (in oxygen free environments) were not fully developed. As such, the samples were not filtered in a N 2 purged glove bag. After consulting with Lorax, glove bags were procured all remaining sampling events;  Column 1 and 2 results for anion/nutrient and dissolved metals samples from week 17 did not align with those of weeks before or after. This was noted for many parameters in this category. It appears that the samples from these columns were mislabeled. The anion/nutrient and metal results from this date were corrected, and the results now align with those immediately preceding and proceeding;  In week 12, column 1 dissolved metal samples were not filtered due to operator error. The difference in sample preparation and analysis results in values that do not agree with those of previous and ensuing weeks, so this data point has been removed;  In week 19, the sample for column 2 was different from other weeks: the dilution required to compensate for interference-causing analytes was much higher, and alkalinity levels were an order of magnitude greater than all other results. This casts doubt on the validity of these results, and the alkalinity result has been removed;  In week 20, the DOC result reported for column 6 was 32.9 mg L -1, while the average of the 6 closest results (preceding and following this event) was 4.47 mg L -1. This data point has been removed as an outlier; and, 61  Multimeter readings varied wildly for DO and ORP, and the swings in the values do not seem to coincide with changes in related parameters or each other. These data have been presented in the following sections, but their validity remains in question. 3.2.1. Data Issues Arising from Column Blockages Column 1 effluent water quality was likely impacted by the frequent requirement to clear the effluent port of the column. Materials causing clogging or blocking were presumed to be organic (the specific gravity of CMWR would prevent it from blocking the PVDF effluent fitting located at the top of the column). They likely accumulated due to their small grain size (which allowed movement within the saturated pore volume of the column) and low density (which buoyed the pieces). These blockages were cleared by disconnecting the effluent tubing from the PVDF compression fitting and inserting a small piece of wire (approximately 2 mm in diameter) through the fitting. Blockages were often noticed during the 2-3-day sampling window each week, though they may have developed at any time during the unmonitored 4-5 days prior. Due to the blockage, the column was often under pressure from continuously pumping into a closed (blocked) system, and from gas generation. Please see Figure 3.1 for an image of bubbles building up in top of Column 1. When the blockage was removed, discharge velocities were enough to spray foul smelling gas, liquids and organics approximately 3 m into the air. This resulted in the possible loss of organic mass in the columns, and possibly re-oxygenation of portions of the column. Collectively, these processes may have had an impact on the quality of the data from this column. 3.2.2. Operational Issues Affecting Results After initially filling the columns, they were sealed tightly for a week, allowing entrapped air to dissolve and disperse in pore liquids of soils (Lewis & Sjostrom, 2010). 62 Unfortunately, there was a lack of supervision during this first week-long period, and the vapour pressure generated by the rapidly decomposing organic mass was sufficient to push liquids, gases, and organics through the upper gasketed seal (see Figure 2.1 for an elevation profile of a column). Table 3.1 shows the approximate void space for each column, calculated by dividing the initial mass of water required to fill each individual column by an assumed liquid density of 1 g/cm3. The mass of amendment and liquid that was lost as a result of this initial pressurization is also shown. There is no direct correlation between lost mass and lost organics, as each column may have vented a unique mixture of gas, liquid, and organics. Figure 3.1: Gas bubbles building up at the top of column 1. Rapid discharge of gas at specific periods during the column operation (at higher than average liquid flow velocities) may have contributed to organics plugging the column discharge port. Table 3.1: Initial void space and estimated combined liquid and solid mass lost in first 5 days Column 1 2 5 6 Void space cm3 1415 1612 1459 1440 Mass lost in first 5 days g 434 0 447 56 63 3.3 Amendment Characterization 3.3.1 Waste Rock 3.3.1.1 Particle Size Distribution The average particle size of the CMWR samples is shown in Table 3.2. Please see Appendix D.5 for a table of the individual results of each of the three samples. Table 3.2: Average particle size distribution of three CMWR samples Parameter Average % of Total Sample Standard Deviation % Gravel (>2mm) % Sand (2.00mm – 1.00mm) % Sand (1.00mm – 0.50mm) % Sand (0.50mm – 0.25mm) % Sand (0.25mm – 0.125mm) % Sand (0.125mm – 0.063mm) % Silt (0.063mm – 0.0312mm) % Silt (0.0312mm – 0.004mm) % Clay (<4µm) 55.2 14.3 9.8 6.2 3.5 2.2 2.3 3.9 2.5 3.15 0.45 0.98 0.67 0.39 0.25 0.30 0.32 0.20 3.3.1.2 Elemental Abundance, Acid Base Accounting, and pH The results of the chemical characterization of the CMWR are presented in tabular format in Appendix D.6. The CMWR was composed of the following dominant constituents: Calcium (Ca) (2.013%), Fe (1.527%), Al (0.757%), and P (0.243%). These values compare to upper continental crustal abundances of 2.945%, 3.089%, 7.744%, and 0.066%, respectively (Wedepohl, 1995). Given the purview of this thesis, concentrations of other elements of note are 119.3 ppm (Mn), 1233 ppm (S) and 2.833 ppm (Se), which contrast with the upper continental crustal averages of 527 ppm, 953 ppm, and 0.083 ppm, respectively (Wedepohl, 1995). The results of the ABA Test on the CMWR showed an average acid generating potential of 7.53, and an average neutralizing potential of 56.3, resulting in a net neutralizing potential of 49 (all values are reported in tonnes CaCO 3 per kiloton of rock). The CMWR had an average paste pH of 8.1. 64 3.3.2 Organic Substrates The result of the chemical characterization of the hay and the sawdust are presented in Appendices D.7 and D.8, respectively. The hay was characterized by an average Total Organic Carbon (TOC) of 44.3%, and an average Total N (TN) of 1.15%, resulting in a TOC: TN ratio (% based) of 38: 1. The sawdust was characterized by an average TOC of 47.8% and an average TN of 0.054%, resulting in a TOC: TN ratio of 890: 1. 3.4 Influent Characterization 3.4.1 Overview The results of field measurements and the chemical characterization of influent and individual column effluents are presented in raw tabular form in Appendix D.9. These results are plotted, separated by parameter, including both the influent and the effluent of each column in Appendix D.10. Dissolved-Se is presented in Appendices D.9 and D.10. Selenate, SeO32-, and any unidentified Se species detected are presented in tabular form in Appendix D.11, and graphically in Appendix D.12 in two ways:  Concentrations of Se(IV), Se(VI), and unknown species of Se, shown as percent of the cumulative Se total, are plotted in species-specific graphs to compare values between columns, an example of which is displayed in Figure 3.2; and,  Species concentrations, shown as percent of the cumulative Se total, are plotted in column-specific graphs to demonstrate the dynamic conditions as a function of time. An example of this presentation is displayed in Figure 3.3. 65 Se (IV) 100% % of Total 80% Column 1 60% Column 2 40% Column 5 Column 6 20% Inlet 0% Week 4 Week 11 Week 18 Week 24 Week Figure 3.2: Column influent and effluent Se(IV) concentrations, presented as a percentage of total Se, plotted as a function of time. Column 5 100% % of Total 80% 60% Se(IV) 40% Se(VI) 20% Unidentified 0% Week 4 Week 11 Week 18 Week 24 Week Figure 3.3: Column 5 effluent Se species concentrations presented as a percentage of total Se, plotted as a function of time. The influent water used in the column experiment was sampled and chemically characterized on a biweekly basis as a measure of consistency. The results of this characterization are presented in raw form in Appendix D.9. The results of the chemical characterizations have been input into PHREEQC using both the Lawrence Livermore National Laboratory (llnl) and Minteq International Inc. (minteq.v4) databases to determine the saturation index (SI) for specific minerals. The SI is useful to help determine whether the water is saturated, undersaturated, or supersaturated 66 (corresponding SIs of 0, less than 0, and greater than 0, respectively), with respect to the mineral in question, where the SI is defined as: SI = log10 (IAP/Ksp) And where: IAP = ion activity product Ksp = equilibrium solubility constant The SIs for individual parameters have been combined to a single set of results using the following methodology:  if a valid result (not a SI of -999.9999) was obtained from the llnl database, the result was accepted as an input for the graph;  if no valid llnl database result was obtained, but a valid result was obtained from the minteq.v4 database, the result was accepted as an input for the graph; and,  if both database results produced invalid results, no result was presented on the graph. The above approach allowed the maximum number of values to be used in generating the graphs. The input files, selected output parameters and graphed data are all provided in Appendix D.13. Consultation with members of the committee yielded the following CoA for SI results: saturation indices were only considered relevant if they were between -2.0 and 2.0, as values outside of this range may not be important in governing solute concentrations. 9 A value of -999.999 is indicative of an undefined phase, or one or more of the constituent elements not in solution (Parkhurst & Appelo) 67 In the following presentation of influent water chemical analysis, and subsequent presentation of column effluent analysis, the information is laid out in subsections: 1) Major ions and pH, and these include alkalinity, D-Ca, D-Mg, Fluoride (F -) and Cl-; 2) Nitrogen species including NO3-, NO2-, and NH3; 3) Parameters relevant to redox chemistry (unless shown in other sections) including DO, ORP, D-Fe, D-Mn, SO42-, and S2-; 4) Selenium species; and 5) Trace elements and DOC. Trace elements to be included in item 5) above were chosen after reviewing the Brule Mine 2014 Annual Water Quality Report (Walter Energy, 2015). Parameters that exceeded the WQG in 2014 are scrutinized to determine if column amendments influenced concentrations. These parameters are D-Al, D-Cd, D-Cu, D-Pb, D-Ni, and D-Zn. 10 Dissolved silver (Ag) samples had concentrations less than or equal to the MDL for all columns, so this parameter will not be discussed further. 3.4.2 Consistency of Influent Water Influent water quality results were analyzed to determine if the water was chemically constant. The analysis consisted of calculating the RPD between the minimum and maximum concentrations reported over the duration of the experiment. The RPDs exceeded 100% for 10 Fluoride exceeded the WQG in the Brule Mine’s effluent in 2014, but this parameter is reported in Major ions and pH. 68 the following parameters (if the minimum value was less than 500% of the MDL, the result is not included):  Dissolved Al, 126%;  Dissolved Mn, 162%; and  Dissolved Tl, 103%. Influent water characterization results are summarized in Section 3.4.3. The results are also discussed in Section 3.5 and are important as they present a baseline from which amendment effects can be evaluated. As evidenced by the few parameters with large RPDs (shown above) and by the following sections, influent water chemistry was rather static over the course of the experiment. 3.4.3 Influent Water Chemical Characterization 3.4.3.1 Major Ions and pH Total alkalinity concentrations in the influent water ranged from 97.8 mg L -1 in week 24 to 121 mg L-1 in weeks 2 and 3. The average for the experiment was 114 mg L-1. Influent D-Ca concentrations ranged from 178 mg L-1 in week 7 to 195 mg L-1 in week 19 and averaged 188 mg L-1. Dissolved magnesium (Mg) concentrations ranged from 107 mg L-1 in week 9 to 115 mg L-1 in week 2 and averaged 110 mg L-1. Chloride concentrations ranged from 9.5 mg L-1 in week 7 to 12.0 mg L-1 in week 2. Influent pH generally increased throughout the experiment, and the minimum value was observed in week 4 (7.16) and the maximum in week 22 (8.14). When results were approximated by a linear slope (R2 = 0.32) the slope is as shown in Equation (23). (23) pH = 0.0164x* + 7.4666 * where x is the number of weeks elapsed 69 Fluoride concentrations were always less than or equal to the dilution dependant MDL (which ranged from 0.2 mg L-1 to 0.4 mg L-1). 3.4.3.2 Nitrogen Species Influent NO3- concentrations averaged 73.5 mg L-1 over the experiment and ranged from 70.9 mg L-1 in week 7 to 75.6 mg L-1 in week 19. Nitrite concentrations only exceeded the MDL (0.01 mg L-1 or 0.02 mg L-1 depending on the dilutions required) in week 3 (0.011 mg L-1). The influent NH3 concentrations exceeded the MDL (0.005 mg L-1) in weeks 1 and 9 only (0.0069 mg L-1 and 0.0063 mg L-1, respectively). 3.4.3.3 Redox Chemistry Influent DO levels generally increased over the life of the experiment, with a minimum being observed in week 1 (57.7% saturation), peaking in week 14 (172% saturation), and averaging 103.2%. Oxidation/reduction potential readings ranged from -122 mV to 288 mV in weeks 14 and 15 these results cast doubt on the calibration and accuracy of the instrument. Concentrations of D-Fe were below MDL (0.03 mg L -1) throughout the entire experiment. Concentrations of D-Mn were above the dilution dependant MDL (0.05 - 0.1 µg L-1) for only the first four sampling events. The maximum D-Mn concentration was observed in week 2 (0.472 mg L-1). Sulfate concentrations ranged from 746 mg L-1 in week 7 to 801 mg L-1 in week 19 and averaged 778 mg L-1. No sample had a S2- concentration exceeding the MDL (0.02 mg L-1). Dissolved U concentrations ranged from 17.5 µg L-1 to 22 µg L-1 in weeks 19 and 13, respectively. Dissolved antimony (Sb) concentrations ranged from 1.72 µg L-1 to 1.98 µg L-1 in weeks 19 and 7, respectively. Dissolved Mo concentrations ranged from 3.9 µg L-1 to 4.5 µg L-1 in weeks 19 and 13, respectively. 70 3.4.3.4 Selenium Species Dissolved Se in column influents, as measured by ICP-MS analysis, ranged from a minimum in week 1 to a maximum in week 9 (104 µg L-1 and 118 µg L-1, respectively). Speciation results from Trent indicate that Se(VI) ranged from 87-94% of the cumulative Se. Concentrations of Se(IV) ranged from a minimum in week 18 (less than 0.2 μg L -1) to a maximum in week 24 (2 μg L-1). Concentrations of Se(VI) ranged from a minimum in week 4 (87.1 μg L-1) to a maximum in week 18 (91.5 μg L-1). Unidentified Se species concentrations dropped from week 4 to week 24 (11.7 μg L-1 and 3.61 μg L-1, respectively). 3.4.3.5 Trace Elements, DOC, and Solubility Controls Concentrations of D-Al were at or below the MDL (3.0 µg L-1) for every week of the experiment except weeks 9 and 22 (13.2 µg L-1 and 11.1 µg L-1 respectively). Concentrations of D-Cd did not exceed the dilution dependant MDL over the course of the experiment (0.005-0.01 µg L-1). Concentrations of D-Cu were above the MDL (0.5 µg L-1) only in week 1 (0.91 µg L-1). Concentrations of D-Pb ranged from being equal to or less than the MDL (0.05 µg L-1) in half of the samples to a maximum in week 3 (0.114 µg L-1). Concentrations of D-Ni ranged from 52.7 µg L-1 to 62.7 µg L-1 in weeks 24 and 9 respectively. Concentrations of D-Zn were less than or equal to the MDL (3.0 µg L-1) in every sample. Concentrations of DOC ranged from a minimum in week 7 (3.63 mg L -1) to a maximum in week 2 (5.06 mg L-1). The SI for calcite, dolomite, and magnesite ranged from a minimum in week 3 (0.27, 1.66, and -0.24, respectively) to a maximum in week 22 (0.92, 2.96, and 0.41 respectively). The SI for gypsum was consistent through the experiment and ranged from a minimum in week 7 (-0.73) to a maximum in week 19 (-0.67). 71 3.5 Effluent Characterization. 3.5.1 Overview Results of the effluent characterization are presented with those of the influent and shown in tabular and graphical form in Appendices 9 and 10, respectively. Parameter specific graphs plot column effluent concentrations relative to those of the influent (as a visual indicator of column performance over time). As an example, SO 42- effluent and influent concentrations are plotted together in Figure 3.4. The following sections present and compare the results, and frequently reference the data in the appendices. The water quality of each column is compared with influent water and analyzed for trends including maximums, mg L-1 minimums, and consistency. The results are analyzed in Section 4. Sulfate 900 800 700 600 500 400 300 200 100 0 Column 1 Column 2 Column 5 Column 6 Inlet 1 3 5 7 9 11 13 Week 15 17 19 21 23 Figure 3.4: Influent and effluent SO42- concentrations throughout the experiment. In addition to the influent water quality parameters discussed in Section 3.4, the void space of each column at the beginning of the experiment is presented in Table 3.1. Void space ranged from 1415 cm3 (column 1) to 1612 cm3 (column 2). 72 3.5.2 Column 1 - Hay and Waste rock 3.5.2.1 Major Ions and pH Effluent alkalinity concentrations were greater than those of the influent for the duration of the experiment. Values spiked sharply in week 2 (3880 mg L-1), a questionable data point given the pre- and proceeding values, while the mean concentration for the experiment was much lower (980 mg L-1). The lowest concentration was observed in the sample from week 24 (467 mg L-1). Effluent D-Ca concentrations were greater than those of the influent in every sample of the experiment. They spiked in the first 6 weeks of the trial, with concentrations peaking in weeks 2 (542 mg L-1) and 6 (633 mg L-1) and exhibited a minimum in week 16 (201 mg L-1). The mean concentration in the 1st quarter of the experiment was 128% higher than that of the 3rd quarter (518 mg L-1 and 227 mg L-1, respectively). Effluent D-Mg concentrations fluctuated with alternating periods above and below the influent levels. Maximum and minimum concentrations were observed in weeks 5 and 13 (135 mg L-1 and 85.4 mg L-1 respectively), and the mean was 104 mg L-1. Chloride concentrations exhibited small fluctuations over the course of the experiment and ranged from 9.6 mg L-1 – 21 mg L-1. Dilution required due to high concentrations of interference causing analytes resulted in elevated MDLs (as high as 25 mg L-1). Due to this, Cl- concentrations spiked in week 2, which may not be indicative of levels observed, but the preceding and proceeding concentrations (21 and 11 mg L-1, respectively) provide an interval in which the true concentration may be contained. Column 1 effluent pH generally increased very gradually throughout the experiment. The minimum was observed in week 6 (6.02) and the maximum in week 20 73 (6.86). Results were consistently less than those of the influent, by an average of 1.21 units. When results were approximated by a linear slope (R 2 = 0.74) the slope is as shown in Equation (24). (24) pH = 0.0298x* + 6.0651 * where x is the number of weeks elapsed Fluoride concentrations were at or below the dilution dependant MDL (ranging from 0.2 mg L-1 to 1.0 mg L-1) for samples collected in the first 12 weeks of the experiment, and sporadically afterwards. From week 13 onwards, samples that exceeded the MDL ranged from 0.22 mg L-1 to 0.31 mg L-1. 3.5.2.2 Nitrogen Species Twelve (12) of 21 column effluent sample concentrations were at or below the dilution dependant MDL for NO3- (0.05 mg L-1 – 0.10 mg L-1). A spike was observed in week 24 (22.6 mg L-1), which was the only result above 2.54 mg L-1. All effluent results were below those of the influent. Nitrite concentrations ranged from repeatedly being less than or equal to the dilution dependent MDL (0.01 mg L-1- 0.05 mg L-1) to 0.219 mg L-1 in week 18. The concentration of NH3 peaked in week 1 (8.79 mg L-1), and by week 24, it did not exceed the MDL (0.005 mg L-1). All results were greater than or equal to those of the influent. 3.5.2.3 Redox Chemistry Dissolved O, reported as percent saturation, ranged from 6.5% in week 2 to 28.8% in week 19. ORP readings ranged from 63.1 mV in week 1 to -212.8 mV in week 14. 74 Dissolved Fe concentrations exhibited a maximum of 35.2 mg L-1 in week 5, and gradually decreased with time. Concentrations were elevated in the 1 st quarter of the experiment, and in this period, they averaged 27.9 mg L-1. In the 2nd, 3rd, and 4th quarters, the concentrations averaged 4.2 mg L-1, 0.70 mg L-1, and 0.27 mg L-1, respectively. Effluent concentrations were above those of the influent for every sampling event. Concentrations of D-Mn exhibited similar tendencies as those of D-Fe, and were elevated at the beginning of the experiment, peaking 1.27 mg L-1 in week 2. Concentrations were elevated in the 1st quarter of the experiment, and in this period, they averaged 0.979 mg L-1. In the 2nd, 3rd, and 4th quarters, the concentrations averaged 0.204 mg L -1, 0.084 mg L-1, and 0.104 mg L-1, respectively. All results were above those of the influent. Effluent SO42- concentrations only exceeded those of the influent in week 1, which had the highest recorded level throughout the experiment (803 mg L-1). Concentrations dropped noticeably from week 1 to the columns lowest concentration in week 3 (175 mg L -1). After week 3, concentrations rose almost steadily until the end of the experiment, achieving a final concentration of 706 mg L-1. Sulfide concentrations in Column 1 were greater than the MDL and those of the influent for the entire experiment but did not exhibit a noticeable pattern. The maximum and minimum concentrations were observed in weeks 18 (6.7 mg L-1) and 12 (0.031 mg L-1), respectively. Concentrations of D-U were less than those of the influent for the entire experiment, and varied during the experiment: they dipped from week 1 (4.09 µg L-1) to week 3 (2.29 µg L-1), then rose to week 13 (15.6 µg L-1), and dropped to week 22 (2.85 µg L-1) before rising again in week 24 (10.7 µg L-1). 75 Concentrations of D-Sb dropped sharply from a maximum in week 1 (51.6 µg L -1) to a minimum in week 5 (2.16 µg L-1). All results were greater than those of the influent. Concentrations of D-Mo dropped from 26.9 µg L-1 in week 1 to a minimum in week 6 (0.77 µg L-1). From week 3 to 24 concentrations did not exceed 4.99 µg L -1 and were on average, below those of the influent. 3.5.2.4 Selenium Species Effluent D-Se concentrations peaked in weeks 1 and 24 (49.4 μg L-1 and 31.9 μg L-1, respectively). Effluent concentrations were below those of the influent for every sampling event. Speciation results from Trent indicate that the majority of the D-Se found in Column 1 effluent was either Se(VI) or unidentified Se species. The sum of all dissolved phase Se concentrations did not show any consistency between the results reported by Trent and those reported by ALS. The percent of Se(IV), relative to total dissolved Se reported by Trent, ranged from a minimum in week 11 (0.29% of total Se) to a maximum in week 18 (10.21%). The relative percent of Se(VI) ranged from a minimum in week 18 (6.65%) to a maximum in week 11 (75.7%). The relative percent of unidentified Se species ranged from a minimum in week 24 (20.7%) to a maximum in week 18 (83.1%). 3.5.2.5 Trace Elements, DOC, and Solubility Controls Concentrations of D-Al decreased from a maximum in week 1 (118 µg L -1) to a minimum in week 24 (7.3 µg L-1), and all results were greater than those of the influent. Concentrations of D-Cd exhibited a sharp decrease from a maximum of 0.32 µg L -1 in week 1 to 0.037 µg L-1 in week 3. The results increased again to week 6 (0.10 µg L-1) as a result of the dilution dependent MDL, and then fell to less than 0.0131 µg L -1 in the last 9 weeks of the experiment. 76 Concentrations of D-Cu were above the dilution dependant MDL (ranging from 0.5 µg L-1 to 1.0 µg L-1) in weeks 1-3, 7 and 13. Week 1 had the highest concentration (4.55 µg L -1) and all detectable results were greater than or equal to those of the influent. Concentrations of D-Pb dropped from a maximum in week 1 (1.17 µg L -1) to being marginally above, or less than equal to the MDL (0.05 µg L-1) in the 2nd half of the period, and except for those of week 22, all results were greater than or equal to those of the influent. Concentrations of D-Ni dropped from a maximum in week 1 (1.2 mg L-1) to less than 0.1 mg L-1 from week 3 to the end of the experiment. All results before week 8 were greater than, and all results after were less than those of the influent. Concentrations of D-Zn dropped sharply from a maximum in week 1 (1810 µg L -1) to 25.2 µg L-1 in week 2, down to the MDL (3.0 µg L-1) in weeks 18-20 and 22. Dissolved organic C spiked up to 1110 mg L-1 in week 2 (from an initial value of 583 mg L-1 on week 1) and then generally decreased to a minimum observed in week 20 (4.39 mg L-1). The 1st quarter average DOC concentration was 807 mg L-1 while that of the last quarter was 29.3 mg L-1. All column 1 effluents had concentrations of DOC greater than those of the influent. Saturation indices for calcite and dolomite were greater than 0 for the duration of the experiment and ranged from minimums in week 24 (0.12) and 1 (1.10) to maximums in week 2 (0.69) and 20 (2.13), respectively. The SI of magnesite was consistently less than 0 and ranged from a minimum in week 1 (-0.70) to a maximum in week 20 (-0.035). The SI of gypsum ranged from a minimum in week 3 (-1.07) to a maximum in week 1 (-0.45). The SI of FeS2, pyrrhotite, and troilite fluctuated largely. Pyrrhotite and troilite SI values were -0.78, 0.46, -0.28, and -0.68, 0.56, -0.18, in weeks 1, 3 and 5, respectively, with large negative 77 values observed in week 2 and the rest of the experiment. Siderite SI values were greater than 0 in weeks 1 through 6 and achieved a maximum in week 5 (0.19), before falling off to a minimum of -2.1 in week 22, and those of rhodochrosite fluctuated from a maximum in week 2 (-0.03) to a minimum in week 16 (-1.38). The SI of mackinawite ranged from a maximum in week 3 (0.88) to a minimum in week 15 (-1.34). 3.5.3 Column 2 - Waste Rock only 3.5.3.1 Major Ions and pH Alkalinity concentrations ranged from a minimum of 134 mg L-1 in week 1 to a maximum of 1800 mg L-1 in week 19. This result has been considered a laboratory error, as it is more than 10 times higher than the next highest concentration, observed in week 3 (151 mg L-1). As mentioned in Section 3.2, this data point has been removed. All effluent concentrations are greater than those of the influent. Every week, D-Ca concentrations were greater than those of the influent by a margin ranging from 9-22 mg L-1 and were relatively constant throughout the experiment. Average D-Mg concentrations in column 2 were consistently slightly less than those of the influent throughout the experiment (average of 104 mg L-1 and 110 mg L-1, respectively). Maximum and minimum concentrations were observed in weeks 13 and 1 (113 mg L-1 and 92.5 mg L-1, respectively). Chloride concentrations ranged from 9.7 mg L-1 – 11 mg L-1. Due to the dilution dependent MDL, Cl- concentrations plots show a spike in week 19 (25 mg L-1), which is not necessarily indicative of actual levels. Column 2 effluent pH generally increased throughout the experiment but fluctuated on a sample-by-sample basis. The minimum was observed in week 3 (6.84) and the maximum in 78 week 20 (7.98). Except for week 20, results were consistently less than those of the influent. When results were approximated by a linear slope (R 2 = 0.15) the slope is as shown in Equation (25). (25) pH = 0.0129x* + 7.0699 * where x is the number of weeks elapsed Effluent F- concentrations decreased from week 1 (0.67 mg L-1) to week 9 (0.29 mg L1 ), and then were less than the dilution dependent MDL until week 24 (0.23 mg L -1). 3.5.3.2 Nitrogen Species Column 2 effluent NO3- concentrations averaged 74.0 mg L-1 over the experiment, only 0.5 mg L-1 greater than those of the influent, and the similarity of these values is evident when inspecting the figures in Appendix D.10. Nitrite concentrations were highest in week 1 (0.134 mg L -1) and were only above the dilution dependent MDL (0.01 mg L-1-0.05 mg L-1) in the first four samples. Ammonia concentrations ranged from a maximum in week 13 (0.0913 mg L-1) to a minimum in week 24 (0.061 mg L-1). Column effluent concentrations were greater than those of the influent during every sampling event (noting again that most influent values were below the MDL). 3.5.3.3 Redox Chemistry Column 2 effluent DO, reported as percent saturation, ranged from 79.8% in week 14 to 20.0% in week 4, and was lower than the influent throughout the study. ORP readings were extremely close to those of the inlet water and ranged from -200 mV to 296 mV (in weeks 14 and 16, respectively) 79 No D-Fe concentrations exceeded the MDL (0.03 mg L-1). Concentrations of D-Mn ranged from 0.0805 mg L-1 in week 1 to 0.131 mg L-1 in week 9. Effluent concentrations of D-Mn were greater than those of the influent during every sampling event. Average SO42- concentrations were marginally higher than those of the influent (786 mg L-1 and 777 mg L-1, respectively). Concentrations fluctuated slightly throughout the study but remained relatively constant. Maximum and minimum concentrations were reported in weeks 13 and 22 (805 mg L-1 and 769 mg L-1, respectively). Effluent S2- concentrations, like those of the influent were less than or equal to the MDL (0.02 mg L-1) for every sample. Effluent concentrations of D-U were slightly less than, but followed the week by week concentration changes observed in the those of the influent. They ranged from 15.1 µg L -1 to 20 µg L-1 in weeks 11 and 3, respectively. Concentrations of D-Sb were relatively stable and ranged from 4.27 µg L -1 (max) to 3.29 µg L-1 (min) in weeks 3 and 24, respectively. All effluent concentrations were above those of the influent. Concentrations of D-Mo decreased from week 1 to 24 (24.1 µg L -1 and 9.64 µg L-1) and were 5.6 – 2.2 times greater than those of the influent, respectively. 3.5.3.4 Selenium Species Effluent D-Se concentrations were greatest in week 1, which was 32% higher than that of the influent (137 µg L-1 and 104 µg L-1, respectively). Effluent concentrations decreased very gradually over the duration of the experiment and dropped below those of the influent (approximately 2/3 into the study). The minimum effluent concentration was recorded in week 22 (89.5 µg L-1), which was 17% below that of the influent. Speciation results indicate 80 that the majority of the Se found in Column 2 effluent was Se (VI) with little or no unidentified Se and Se(IV) species. The relative percent of Se(IV) ranged from a minimum in week 4 (0.2%) to a maximum in week 24 (3.3%). The relative percent of Se (VI) decreased from a maximum in week 4 (100%) to a minimum in week 24 (91.0%). The relative percent of unidentified Se species ranged from a minimum in week 4 (0%) to a maximum in week 24 (5.75%). 3.5.3.5 Trace Elements, DOC, and Solubility Controls Concentrations of D-Al were at or below the MDL (3.0 µg L-1) for every week of the experiment. Concentrations of D-Cd ranged from a minimum in week 18 to a maximum in week 7 (1.18 µg L-1 and 1.73 µg L-1, respectively), and were consistently above those of the influent. Concentrations of D-Cu were consistently above the those of the influent. Concentrations of D-Pb were consistently less than or equal to the MDL (0.05 µg L -1). Concentrations of D-Ni gradually decreased from 143 µg L-1 in week 1 to 72.8 µg L-1 in week 24, and all results were greater than those of the influent. Concentrations of D-Zn generally decreased throughout the course of the experiment and exhibited a peak in week 3 of 90.9 µg L-1 and a minimum in week 24 of 49.8 µg L-1 and all results were greater than those of the influent. Concentrations of DOC were low and ranged from 1.04 mg L-1 to 3.07 mg L-1 in weeks 13 and 1 respectively. Effluent DOC concentrations were slightly less than those of the influent during every sampling event. The SI of calcite was below 0 in weeks 3, 11, and 15 below 0 while that of dolomite was consistently above 0. The SI of magnesite was above 0 in week 19 only, while that of rhodochrosite was always less than 0. The SI of calcite, dolomite, rhodochrosite, and magnesite ranged from minimums in week 3 (-0.18, 0.68, -1.64, and -0.77, respectively) to 81 maximums in week 19 (1.21, 3.48, -0.23, and 0.65, respectively). The SI of gypsum was less that -0.5 for the entire experiment. 3.5.4 Column 5 – Hay, Sawdust and Waste Rock 3.5.4.1 Major Ions and pH Effluent total alkalinity concentrations rose from 638 mg L-1 to a maximum of 884 mg L-1 in week 1 and 9, respectively, and then decreased to 370 mg L-1 by week 24. The average concentration in the 2nd quarter of the experiment (830 mg L-1) was 76.5% greater than that of the 4th quarter (470 mg L-1) and all concentrations were substantially greater than those of the influent water. Dissolved Ca concentrations spiked at the onset of the trial, with concentrations peaking in week 3 (328 mg L-1) from 312 mg L-1 in week 1. The concentrations gradually decreased with time, with a minimum concentration observed in week 18 (197 mg L -1). The average concentration in the 1st quarter of the experiment was 54% higher than that of the 3rd (313 mg L-1 and 203 mg L-1, respectively). Effluent concentrations exceeded those of the influent for every week of the trial, but difference between the two decreased with time. Dissolved Mg concentrations remained relatively consistent throughout the length of the experiment, with maximum and minimum concentrations observed in weeks 18 and 7 (107 mg L-1 and 87.4 mg L-1 respectively). The average concentration over the course of the experiment was 98.2 mg L-1. Concentrations of the influent exceeded those of column 5 effluent for every week of the trial. Chloride concentrations were highest in week 1 (12 mg L-1), lowest in week 7 (9.5 mg L-1), and had an average of 10.2 mg L-1. Concentrations were similar (within 1.0 mg L-1) to those of the influent over the course of the experiment. 82 Column 5 effluent pH generally increased throughout the experiment. The minimum was observed in week 5 (6.27) and the maximum in week 20 (7.07). Results were consistently less than those of the influent, by an average of 0.92 units. When results were approximated by a linear slope (R2 = 0.73) the slope is as shown in Equation (26). (26) pH = 0.0297x* + 6.3227 * where x is the number of weeks elapsed Fluoride concentrations ranged from 0.21 mg L-1 to 0.44 mg L-1 and were occasionally less than of equal to the dilution dependant MDL. 3.5.4.2 Nitrogen Species Effluent NO3- concentrations gradually increased from the dilution dependent MDL (0.05 mg L-1 to 0.1 mg L-1) in weeks 1, 5, 7, and 11 to a maximum of 23.9 mg L-1 in week 24. No week had an effluent NO3- concentration greater than 33% of its influent level. Nitrite concentrations ranged from a maximum of 19.7 mg L-1 in week 1 to a minimum of 0.021 mg L-1 in week 5. No concentration after week 1 exceeded 0.64 mg L-1. Effluent concentrations exceeded those of the influent for every week of the trial. Ammonia concentrations dropped off sharply from a maximum, observed in week 1 (7.44 mg L-1) to 0.120 mg L-1 at week 5. Then concentrations tended to slowly decrease until week 24, when they were less than or equal to the MDL (0.005 mg L-1). The average NH3 concentration (0.864 mg L-1) was more than 146 times higher in the first quarter of the experiment than the third (3.38 mg L-1 and 0.023 mg L-1, respectively). Effluent NH3 concentrations in the fourth quarter decrease further, but samples below the detection limit prevent a calculation of the average for this period. 83 3.5.4.3 Redox Chemistry Effluent DO levels, reported as percent saturation, ranged from 1.5% in week 16 to 30.7% in week 14, and levels were lower than those of the influent for every sampling event. ORP readings ranged from 29.6 mV in week 1 to -244.3 mV in week 8 and were lower than those of the influent every week except 14 and 20. Concentrations of D-Fe rose to a maximum in week 1 through 5 (3.26 mg L -1 and 15.7 mg L-1, respectively), before dropping to less than 20% of these earlier results. From week 7 onwards the concentrations ranged from 0.058 mg L-1 (week 9) to 0.619 mg L-1 (week 15). The average concentration in the first quarter of the experiment (10.1 mg L-1) was more than 32 times that of the last (0.312 mg L-1). Effluent concentrations exceeded those of the influent for every week of the trial. Dissolved Mn concentrations decreased by an order of magnitude from their maximum level in week 1 (0.887 mg L-1) to their minimum in week 19 (0.0714 mg L-1), then rebounded slightly to 0.0945 mg L-1 by week 24. The average D-Mn concentration for the 1st quarter of the experiment was more than 8 times that of the last (0.729 mg L-1 and 0.0836 mg L-1, respectively). Effluent SO42- concentrations dropped noticeably from the start of the experiment (754 mg L-1 in week 1) to week 5, when the minimum level was observed (248 mg L -1). After week 5, concentrations rose almost steadily until the end of the experiment, when they reached the maximum of 764 mg L-1. The average SO42- concentration over the course of the experiment was 554 mg L-1. Concentrations of the influent exceeded those of the column 5 for every week of the trial. 84 Sulfide concentrations were greatest during the middle of the experiment peaking in week 9 (10.9 mg L-1) increasing from below the MDL in week 1 (0.02 mg L-1) and then decreasing to 0.053 mg L-1 by week 24. Effluent concentrations exceeded those of the influent for every week of the trial. Concentrations of D-U were less than those of the influent for the entire experiment. They peaked in the weeks 1 and 18 (14.6 µg L-1 and 15.3 µg L, respectively) and exhibited a minimum in week 5 (3. 63 µg L-1). Concentrations of D-Sb were greater than those of the influent for the entire experiment. They dropped from a peak in week 1 (42.2 µg L-1) to a minimum in week 5 (1.83 µg L-1) and were less than or equal to 6.01 µg L-1 (observed in week 13), for the remainder of the experiment. Concentrations of D-Mo dropped from a maximum observed in week 1 (57 µg L -1) to a minimum in week 7 (0.753 µg L-1), and then increased to 5.82 µg L-1 by week 24. Except for the high initial concentrations, levels were comparable to those of the influent. 3.5.4.4 Selenium Species Effluent D-Se concentrations decreased from a maximum observed in week 1 (102 µg L-1) to a minimum in week 3 (2.3 µg L-1), after which all concentrations were less than or equal to 22.3 µg L-1, observed in week 17. Effluent concentrations were below those of the influent for every sampling event. Speciation results indicate that each species of Se was dominant in at least one sampling event. The relative percentage of Se (IV) ranged from a minimum in week 11 (0.5%) to a maximum in week 24 (38.3%) when it was dominant. The relative percentage of Se(VI) ranged from a minimum in week 18 (4.2%) to a maximum in week 11 (71.0%) and was dominant in weeks 4 and 11. The relative percent of unidentified 85 Se species concentrations ranged from a minimum in week 11 (28.5%) to a maximum in week 18 (91.8%), when they were dominant. 3.5.4.5 Trace Elements, DOC, and Solubility Controls Concentrations of D-Al were greater than the influent for every week in the experiment except 22 and decreased from a maximum in week 3 to a minimum in week 24 (44.5 µg L-1 and 5.4 µg L-1, respectively). Concentrations of D-Cd ranged from an initial peak in week 1 to the MDL in weeks 18-24 (3.01 µg L-1 and 0.005 µg L-1, respectively). Concentrations of D-Cu were above the MDL (0.5 µg L-1) only in weeks 1 (3.22 µg L-1), 3 (1.56 µg L-1), and 7 (0.66 µg L-1). Concentrations of D-Pb dropped from an initial high of 0.57 µg L-1 in week 1 to the MDL (0.05 µg L-1) in week 7, which was only exceeded in week 13 (0.061 µg L-1). Concentrations of D-Ni dropped from 0.918 mg L-1 to 0.0183 mg L-1 in weeks 1 and 24 respectively. Concentrations of D-Zn dropped from an initial spike of 911 µg L-1 in week 1 down to a range from the MDL (3.0 µg L-1) to 8.3 µg L-1 in the remaining sampling events. Concentrations of DOC increased from week 1-5 (165 mg L-1 and 397 mg L-1, respectively), after which they decreased. Effluent DOC concentrations were less than 14 mg L-1 after week 11 and were greater than those of the influent during every sampling event. Saturation indices for calcite and dolomite were greater than 0, while those of magnesite, rhodochrosite, and gypsum were less than 0 for the entirety of the experiment. Pyrrhotite, troilite, and mackinawite SI values ranged from a minimum in week 24 (-2.14, 2.04, and -2.01, respectively) to a maximum in week 5 (0.22, 0.33, and 0.66, respectively). The SI of siderite was greater than zero only in week 5 (0.06) and reached a minimum in week 11 (-1.91). 86 3.5.5 Column 6 - Sawdust and Waste Rock 3.5.5.1 Major Ions and pH Effluent total alkalinity levels initially rose from 186 mg L-1 in week 1 to a maximum concentration of 280 mg L-1 in week 6. From week 7 onwards, effluent concentrations did not exceed 213 mg L-1 (seen in week 8) and decreased to 174 mg L-1 by week 24. The average concentration was 204 mg L-1 and all effluent concentrations exceeded those of the influent. Calcium concentrations exhibited relatively little variation throughout the experiment, ranging from a minimum of 180 mg L-1 to a maximum to 215 mg L-1 in weeks 16 and 11, respectively. The effluent concentration of week 16 was lower than that of the influent. The average concentration was 203 mg L-1. Dissolved Mg concentrations also exhibited relatively little variation throughout the experiment, with a minimum and maximum observed in weeks 1 and 20 (93.5 mg L -1 and 117 mg L-1), respectively. The average concentration over the course of the experiment was 104 mg L-1. Effluent Cl- concentrations did not vary much from those of the influent. The effluent Cl- concentrations were highest in week 1 (15 mg L-1), then between weeks 3 and 24, they ranged from 9.8 mg L-1 to 11 mg L-1. Much of the data set in the later half of the study fell below the MDL (10 mg L-1) Column 6 effluent pH fluctuated but in general increased throughout the experiment. The minimum and maximum were observed in week 11 and 7 (6. 78 and 7.57), respectively. Results were consistently less than those of the influent, by an average of 0.53 units. When 87 results were approximated by a linear slope (R2 = 0.028) the slope is as shown in Equation (27). (27) pH = 0.0049x* + 7.0458 * where x is the number of weeks elapsed Fluoride concentrations rose to a maximum in week 2 (0.75 mg L -`) then fell to a minimum in week 16 (0.27 mg L-1). 3.5.5.2 Nitrogen Species Nitrate concentrations averaged 55.3 mg L-1 over the experiment. Concentrations decreased from week 1 (56.5 mg L-1) to the minimum in week 6 (42.9 mg L-1) and then ranged from 54.4 mg L-1 to 61.2 mg L-1 from week 7 through 24 (the maximum). Influent NO3- concentrations exceeded those of the effluent for every week of the trial. Nitrite concentrations ranged from a maximum of 2.79 mg L-1 in week 2 to a minimum of 0.16 mg L-1 in weeks 16-17 and 19-20. In weeks 15, 18 and 22, the concentrations fell below the dilution dependent MDL (0.02 mg L-1). Ammonia concentrations ranged from the maximum (0.0902 mg L -1) to the minimum (0.009 mg L-1), observed in weeks 1 and 6, respectively. No clear trend emerged during the experiment. The average NH3 concentration over the experiment was 0.0449 mg L-1. 3.5.5.3 Redox Chemistry Dissolved O2 levels, reported as percent saturation, ranged from 10.6% in week 5 to 57.6% in week 14, and levels were lower than those of the influent for every sampling event. ORP readings ranged from 104 mV in week 1 to -164 mV in week 14. Effluent concentrations of D-Fe were equal to or less than the detection limit (0.03 mg L-1) for all samples collected during the experiment. Dissolved Mn concentrations ranged 88 from their maximum level in week 6 (267 µg L-1) to their minimum in week 24 (151 µg L-1). The average D-Mn concentration for the 1st quarter of the experiment was 50% greater that of the last quarter (246 µg L-1 and 164 µg L-1, respectively). Effluent SO42- concentrations were relatively constant and did not vary greatly from those of the influent (with averages of 782 mg L-1 and 778 mg L-1 respectively). The minimum and maximum concentrations were observed in weeks 20 and 6 (767 mg L -1 and 816 mg L-1), respectively. Sulfide concentrations exceeded the MDL (0.02 mg L-1) only in weeks 1 and 3 (0.021 mg L-1 and 0.023 mg L-1, respectively). Concentrations of D-U were similar to those of the influent for the entire experiment. They achieved a minimum and maximum in weeks 19 and 6 (17 µg L -1 and 22.7 µg L-1, respectively). Concentrations of D-Sb were greater than those of the influent during the length of the experiment. Except for some minor fluctuations, concentrations were relatively constant throughout the study and ranged from a minimum in week 7 (4.83 µg L-1) to a maximum in week 22 (6.22 µg L-1). Effluent concentrations of D-Mo were less than those of the influent but steadily decreased during the experiment. They ranged from a maximum observed in weeks 1 and 2 (21.2 µg L-1) to a minimum in week 24 (11.7 µg L-1). 3.5.5.4 Selenium Species Effluent D-Se concentrations exceeded those of the influent only in week 1 (119 µg L 1 ) and generally decreased after that. The minimum concentration was observed in week 23 (23.2 µg L-1). Speciation results indicate that Se(VI) and Se(IV) were the dominant species in 2 89 sampling events each: the relative percentage of Se(IV) increased from a minimum in week 4 (1.52%) to a maximum in week 18 (88.53%), and were dominant in weeks 18 and 24. The relative percentage of Se(VI) ranged from a minimum in week 18 (1.22%) to a maximum in week 1 (85.8%), and were dominant in weeks 4 and 11, 3.5.5.5 Trace Elements, DOC, and Solubility Controls Concentrations of D-Al were at or below the MDL (5.0 µg L-1) throughout the experiment except for weeks 6 through 8, peaking in week 7 (6.6 µg L-1). Concentrations of D-Cd generally decreased from a maximum in week 1 to a minimum in week 23 (2.38 µg L -1 and 0.525 µg L-1, respectively). Concentrations of D-Cu fluctuated at first, achieving a maximum of 1.37 µg L-1 in week 5, then dropping to less than or equal to the MDL after week 15. Concentrations of D-Pb ranged from being equal to or less than the MDL (0.05 µg L -1) at both the beginning and the end of the experiment, to a maximum in week 7 (0.173 µg L -1). Concentrations of D-Ni generally decreased from 233 µg L-1 to 89.6 µg L-1 in weeks 1 and 24 respectively. Concentrations of D-Zn generally decreased from 127 µg L-1 to 58.1 µg L-1 in weeks 1 and 24 respectively. Concentrations of DOC generally decreased from week 1 to 22 (28.8 mg L -1 and 4.31 mg L-1, respectively). Effluent DOC concentrations were greater than those of the influent during every sampling event. The SI of dolomite, calcite, and magnesite each exceeded 0 for periods of time. Calcite, gypsum, and rhodochrosite SI’s ranged from a minimum in week 16 (-0.16, -0.72, and -1.36, respectively) to a maximum in weeks 7 (0.65), 6 (-0.65), and 7 (-0.39), respectively. The SI of magnesite ranged from a minimum in week 11 (-0.69) to a maximum in week 20 (0.11), while that of dolomite was consistently above zero. 90 3.6 Qualitative Observations In the 1st quarter of the experiment, continuing to a lesser extent later on, there was a significant difference in colour in the collected samples. Clear liquids were collected from influent and effluent from columns with no hay, while effluent from the hay amended columns was brown, suggesting decomposition. There was a significant amount of suspended material in the effluents from columns amended with hay, and less so from columns amended with sawdust, compared to the CMWR only column effluent, as shown in Figure 3.5. Filtration of these samples prior to shipment to Trent University lab for Se speciation was very difficult, and even after the 0.45 μm filtration step, the lab had significant difficulty analyzing the samples. Figure 3.5: Week 4 water quality samples (filtered through 0.45 µm filter). Front four samples were collected, from left to right, from column 2 (CMWR only), 5 (hay, sawdust, and CMWR), 3 (hay and CMWR – results not included in thesis), and from 1 (hay and CMWR). 91 As previously mentioned, there was a buildup of gases in the columns amended with hay, which had a very pronounced odor when vented, recorded only as ‘very, very stinky’ (evidence of H2S). No gas collection or analysis was made. 92 Section 4: Discussion 4.1 Overview The results presented in Section 3 have been analyzed and compared in this section, with the goal of addressing the research questions presented in Section 1.9, namely: a) Which of two easily available (to the Brule Mine) organic amendments is best suited as an electron donor for promoting Se removal from Brule Mine effluent? How do the two amendments differ in their kinetics (time to onset of reducing conditions) and longevity (how appropriate redox conditions are maintained) with regard to their ability to foster conditions conducive to denitrification and Se removal within waste rock environments? b) What are the biogeochemical mechanisms governing the speciation and behavior of Se and N in waste rock pore waters in response to these organic amendments? c) How does the use of organic amendments and CMWR in a saturated low-flow, toe seep effluent environment affect column effluent water quality? i.e. in addition to Se and NO3-, will the concentration of any other parameter of environmental relevance be significantly affected by the column conditions? These questions were addressed first by analyzing the characteristics of the amendments predicting organic decomposition and water quality. This was followed by assessing the factors indicative of organic matter decomposition in the columns. Indicators of organic decomposition provided a relative measure of the amount of electron donors, and the removal of target parameters likewise provided an indication of the consumption of electron acceptors. Parameters which are indicative of redox performance were analyzed as well. The performance of the amendments, specifically with respect to processes governing the behaviour of Se and N are discussed in Section 4.3, with emphasis placed on removal 93 mechanisms, speciation, attenuation pathways, reaction products and their long-term stability. Column effluent water quality was also examined for WQG exceedance. Lastly, results were evaluated to provide relevant information for field scale application, with special consideration given to downstream-environment protection during start up and operation of a large scale BCR. 4.2 Organic Amendment Performance As described in Section 3.2.4, during the experiment, column 1 experienced a loss of organics and possible entrainment of air into the column during de-clogging activities (to restore flow in the blocked system), and this may have had an impact on the time to the onset of reducing conditions, the longevity of low redox conditions, and the magnitude of the decrease in redox levels. Thus, the anaerobic performance of column 1, amended with hay and CMWR, may have been under-represented in the results of the experiment. All columns amended with organics also lost liquid and / or organic mass during the week before the pumping of liquids began (as explained in Section 3.2.2 and shown in Table 3.1). 4.2.1 Comparison of Amendment Nutrient Properties The performance of anaerobic digestion is strongly dependent on the type and composition of the material to be digested (Murto et al., 2004), which suggests that a comparison of the organic amendments could provide insight to their performance in columns. The average C:N ratio of three sawdust samples was 890:1, while that of hay was 38.5:1. An optimal C:N ratio reported for anaerobic digestion ranges between 20:1 and 35:1 (Sialve et al., 2009). Overall, the higher C:N ratio of the sawdust as compared to the hay suggests the latter is a more labile form of organic C, and could be expected to show more rapid remineralization. 94 A conceptual diagram showing column 1 and influent and effluent parameters is presented in Figure 4.1. Figure 4.1: Schematic of reactions expected to have occurred within column 1 Average P concentrations in dry sawdust were less than or equal to the MDL, while those of hay were more than an order of magnitude higher (50 and 547.3 mg kg-1, respectively). 95 Higher concentrations of P and lower C:N ratios indicate that the hay would provide a more suitable media for bacterial proliferation than the sawdust, due to the more refractory nature inferred of the sawdust materials. The sawdust may however offer benefits over longer time scales as compared to more labile forms of C. 4.2.2 Direct Products of Organic Matter Degradation Multiple parameters support the conclusion that the hay amendment, in columns 1 and 5, provided the best organic substrate for microbial decomposition including: 1. Higher effluent concentrations of P. Influent and effluent of columns with no hay had concentrations of P less than or equal to the MDL (0.3 mg kg -1). Literature suggests that nutrients in decomposing matter are governed by stoichiometric controls: N and P mineralization from plant residues may be initially immobilized from environments by decomposers until a critical concentration is achieved (Manzoni et al., 2010), after which, decomposer nutrient demand is satisfied, and excess is released. During the initial amendment chemical characterization, concentrations of P in the sawdust were less than or equal to the MDL, as were concentrations in the sawdust amended column effluent water. It is therefore likely that P concentrations did not reach the critical level for the decomposers (allowing for P release) and the lack of P was a bacterial-growth limiting factor. 2. Higher concentrations of DOC and colour. Column 1 (hay and CMWR) exhibited DOC concentrations up to 18.5 times higher than column 6 (sawdust and CMWR), and it can be assumed this number may have been higher if not for organic losses. The composition and source of DOC and colour could be attributed to sources which include: 96  Soluble organics originating from the original substrate;  Particulate material originating from the original substrate;  Substrate material altered through microbial action; and  Microbial biomass. In a similar biological denitrification experiment in up flow columns using wheat straw, periods of high NO3- reduction were coupled with high levels of DOC, colour, and original amendment mass, suggesting higher DOC and colour levels were linked to biological activity (Aslan & Turkman, 2005). 3. The presence of elevated initial NH3 concentrations in column 1 effluent are consistent with the onset of anaerobic conditions. Please refer to Section 1.2 for the stoichiometry associated with the decomposition of the Redfield molecule for the reasoning supporting this assertion. Column 1 demonstrated substantial changes in redox parameters, as measured by concentrations of parameters at the inlet and outlet. These parameters are discussed in the following sections. 4.2.3 Redox Parameters Measured in Effluents 4.2.3.1 Oxygen Unfortunately, as described in Section 3.2, direct redox level measurement of the liquid with a multimeter was deemed unreliable, and the multimeter DO readings were also questionable (e.g., results greater than 170% of saturation). Notwithstanding these limitations, there were interesting trends as columns with hay amendments tended to show the most anoxic conditions, based on DO measurements. Influent and effluent average DO concentrations ranked from highest to lowest were influent (103%), column 2 (48.6%), 97 column 6 (37.6%), column 1 (17%), and column 5 (12.1%). Out of 18 measurements, column 5 effluent DO concentrations were lower than those of column 1 twelve times, despite having twice as much hay. These results could be a manifestation of the organic losses in column 1. 4.2.3.2 Nitrogen Nitrate removal occurred in all columns amended with organic amendments. If all results less than or equal to the detection limit are replaced with the detection limit (possibly overestimating the results) and average column effluents are considered, the following reductions of NO3- were achieved: column 1 - 97.8%, column 2 – 0%, column 5 – 90.8%, and column 6 – 24.7%. These numbers suggest that column 6 (CMWR and sawdust) only achieved partial NO3- reduction, likely reflecting the more recalcitrant nature of this organic matter source (as illustrated by high C:N ratio). Evidence of NO2- in column effluents, indicating partial denitrification, is evident in columns 5 and 6 at the onset of the experiment. Nitrite presence in column 5, coupled with NO3- removal, could indicate that the production of this intermediary molecule is the result of insufficiently-low redox conditions (thermodynamic control) or inadequate hydraulic retention time (kinetic control). Incomplete denitrification, resulting in measurable concentrations of NO2-, has been reported in comparable experiments with aerobic influent (Sauthiera, et al., 1998). If column packing promoted the development of preferential flow paths, hydraulic residence time of liquids could have been greatly reduced, and this has been postulated to result in NO2- production due to incomplete denitrification (Sauthiera, et al., 1998). Furthermore, the rapid decrease of column 5 effluent NO2- concentrations between weeks 1 and 3 may be the result of the microbial population flourishing, and either a corresponding spike in demand for electron acceptors, or an increase in net immobilization. 98 In contrast, the presence of NO2- and approximately 30% NO3- reduction in column 6 might be indicative that demand for electron acceptors is satisfied with partial NO 3- reduction in this column. In Section 1.2 and specifically in Equations (9) through (12), the production of NH3 was linked to anaerobic and facultative organic decomposition. Concentrations of decomposition products in hay amended columns (1 and 5), combined with comparatively lower DO levels, indicate that anaerobic conditions were likely, and these conditions are conducive to DNRA. Small increases in effluent NH 3 concentration in weeks 6 and 11, from columns 1 and 5, respectively, may be indicative of DNRA as a method of NO 3- removal from the waters. After the NO3- levels fell below the detection limit for most of the experiment, there was still a supply of electron donors, and this could lead to conditions where DNRA bacteria would be more successful than denitrifying bacteria (van den Berg, et al., 2016). Another possible mechanism for soluble N reduction in the columns is net N immobilization into microbial biomass. Mass of organisms, microbial proliferation rates, and genomic characterization of the biomass were not quantified throughout the experiment, and therefore immobilization rates are unknown. The highest periods of microbial proliferation and N immobilization would have likely occurred during or immediately after times of high DOC. 4.2.3.3 Selenium Influent Se concentrations were relatively static over the course of the study. Column 2 effluent Se concentrations were relatively stable but dropped slightly for unknown reasons as the experiment progressed. Effluent from columns 1 and 5 showed significant reductions at the onset of the experiment. Interestingly column 6 effluent Se concentrations decreased 99 continuously over the course of the experiment by more than 60%, and the average value was 55% lower than that of the influent. This observation is inferred to reflect the presence of mildly suboxic conditions within the sawdust-amended column, where only modest rates of Se removal may be expected. This postulate is consistent with the NO 3- data, which also show only modest decreases in concentration through the column, indicative of minor rates of denitrification. The percent reduction of Se concentrations in column 6 in weeks 13-24 (compared with the influent concentration) was greater than that of NO3-. While strict thermodynamic principles would suggest that denitrification would occur prior to Se reduction (i.e. the Gibbs free energies presented in Table 1.1), literature also suggests that these may occur simultaneously (Subedi, et al., 2017; Oremlund, et al., 1999). The higher proportion of Se reduction as compared to NO3- would also be influenced by the scale of their respective concentrations, as NO3- levels are multiple of orders of magnitude greater than those of Se. As noted in Section 1, bacteria exist with preferential affinities and inhibitions with regards to specific electron acceptors (Marietou, et al., 2009). Unfortunately, genomic analysis of the bacterial population was not performed, and as such, it is unclear if this alternate reduction sequence is an outlier or a result of a preferential reduction pathway. Also, the ORPdependent order of reduction applies specifically to systems at thermodynamic and chemical equilibrium, conditions that may not have been present in the columns. When reviewing the speciation of the soluble Se, columns which had the most pronounced indications of organic decomposition and anaerobic activity still showed significant proportions of Se(VI). This observation, coupled with the Se concentration decrease (compared to influent), indicates that while a large amount of the oxyanion 100 concentration was reduced, dissolved molecules continued to pass through the column without being subjected to reducing conditions (or were re-oxidized during sample preparation). The columns may have possibly had specific areas of high anaerobic activity, reducing Se, while other areas may have been relatively inert, allowing the NO 3- and SeO42- to pass unreduced. As alluded to in Section 4.2.3.2, there may have been some short circuiting in the columns allowing liquid to pass through quickly (preferential flow paths may have developed). For example, this could have resulted from degrading organics plugging up the CMWR. 4.2.3.4 Iron and Manganese Reduced Fe and Mn, which are parameters for inferring the development of suboxic conditions, exhibited relatively high concentrations in the effluent from columns 1 and 5, coinciding with high DOC and low DO concentrations. The decrease of soluble Mn and Fe concentrations in weeks 6-8 may not indicate redox levels were changing significantly; rather, the decreases in these parameters may indicate the fixed supply of these constituents (from the CMWR surfaces) had been exhausted. Analysis of effluents from columns with no hay amendment show do not show similar initial elevations in Fe or Mn. This observation is inferred to reflect the effect of hay in promoting strongly reducing conditions, which would provide an environment for the reductive dissolution of Fe and Mn oxides from the CMWR surfaces. As evidenced by the reduction of SO42- (presented in the next section), the redox potentials in the hay-amended columns would reduce oxidized Fe and Mn rapidly. It is less likely that the Fe and Mn enrichments in the hay-amended columns were attributed to the hay itself. 101 4.2.3.5 Sulfur Compared to influent levels, a decrease in SO 42- was not observed in effluents of either column 2 or 6 . Columns 1 and 5 effluents achieved decreasing SO 42- concentrations up to week 3 (77%), and week 5 (67%), and an average reduction of 33% and 29%, respectively. Column 5 effluent S2- concentrations spiked from week 5 to 9, which coincided with the decrease in Fe. This suggests another control for the effluent concentrations of Fe may have been present: co-precipitation with S2- as ferrous sulfide. The low solubility of this metal sulfide will result in the loss of reactants from solution (Kiilerich, et al., 2017). Pyrrhotite and troilite had saturation indices slightly above 0 for columns 1 and 5 in weeks 3 and 5 respectively, indicating a possible S consumption mechanism in the columns. 11 A limitation of the experiment was that it was confined to a duration of 6 months: prevalent SO42- removal trends in hay-amended column effluents at the beginning of the experiment appeared to be ending in week 24 (refer to Figure 4.2). The data suggest that the production of electron donors (resulting from organic decomposition) was decreasing, indicating that the following questions are important: 1) How does the production of electrons vary over time, and at what point does the sawdust amended column become advantageous with respect to long-term reactivity? 2) At what point is the production of electrons from the hay amended columns insufficient for the continued reduction of Se oxyanions and denitrification? 11 Saturation indices were above zero for other Fe and Mn compounds only when these elements exhibited concentrations above zero (mackinawite, siderite), and were otherwise negative. 102 Sulfate 1000 800 Column 1 Column 2 Column 5 Column 6 Inlet mg/L 600 400 200 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Week Figure 4.2: SO42- concentrations in influent and effluents plotted as a function of time The data does not indicate if the production of S 2- inhibited microbial growth in columns 1 and 5. The creation of a S 2- tolerant bacterial community is a desired trait for treatment of acid mine drainage or other heavy metal-contaminated streams, as these communities offer the possibility of combining the removal of selenium oxyanions with sulfidic heavy metal precipitation (Lenz, et al., 2008). The BCR at the Brule is not subject to these conditions, and large spikes in SO42- reduction should be observed for any deleterious impacts on BCR functions (e.g., inhibition of microbial growth). 4.2.3.6 Alkalinity When discussing indications of reducing conditions, increased alkalinity levels should be conssidered indicators of facultative or anaerobic activity (as per Equations (9) through (12) in Section 1.2). Alternatively, alkalinity could arise from the dissolution of soluble alkalinity (calcite) on the surface of the CMWR. Dissolution-produced alkalinity would be expected to be observed at the beginning of the trial, while alkalinity generated as a product of suboxic reactions would be commensurate with denitrification and Fe(III), Mn(IV), and SO 42reduction. These interactions could occur simultaneously, and the production of alkalinity 103 could be concealed by consumption as a result of oxidation reactions (those that consume alkalinity), or carbonate mineral precipitation. To parse out the effects of calcite dissolution, effluent alkalinity concentrations from the column 2 (amended with CMWR only) were compared to those of the influent. The effluent from this column exhibited an increase in alkalinity throughout the entire experiment, ranging from 13.6% to 38.0%, suggesting a contribution from the waste rock. The persistence of elevated alkalinity in this column does not necessarily support an initial flushing event. The effluent alkalinity concentrations of organic-amended columns were greater than both the influent and the effluent from column 2, illustrating an alkalinity contribution from suboxic redox reactions. Overall however, a comprehensive interpretation of alkalinity concentrations in column effluents is hindered by the following considerations: 1. Effluent from columns amended with organics demonstrated denitrification in week 1. Parsing out effluent alkalinity increases before and after the onset of denitrification is therefore not possible. In the first half of the experiment, when the redox potential was lower (based on other indicators), effluent alkalinity concentrations in columns 1 and 5 were higher; however, no immediate increases in alkalinity were observed at the onset of SO 42- reduction. 2. Sample filtering in weeks 1 and 2 was not performed in a N 2 purged environment, and the re-introduction of O2 may have resulted in alkalinity consumption (e.g., through Fe(II) or HS- oxidation), skewing the results. 3. Saturation indices for both influent and effluents indicate that calcite and dolomite (carbonate minerals) were above their equilibrium saturation concentrations, possibly indicating alkalinity consumption through the formation of secondary carbonates. 104 4.3 Biogeochemical Processes Governing the Speciation and Behaviour of Se and NO3This section will attempt to correlate academic literature with the fluctuations of all recorded parameters to provide a conceptual understanding of the observed Se and NO 3removal mechanisms in the columns. 4.3.1 Reaction Pathways and Mechanisms Governing Removal In the anaerobic environment of the columns, possible mechanisms governing the reduction of NO3- are primarily respiratory reduction, DNRA, and microbial assimilation. The conditions for respiratory reduction and DNRA, namely low redox potential, available NO3-, and labile C (Silver, et al., 2001), are prevalent in most of the columns amended with organics: column 6 effluent did not appear to have developed low redox conditions and exhibited the lowest effluent DOC concentrations. Adsorptive losses of NO3- on to column amendments may have initially played a small role, but over the course of the experiment are not expected to have had a lasting effect because of the continued loading and competitive effect of other anions (e.g. SO 42-). Additionally, the amendments did not have the ideal adsorption properties (e.g. high surface area) that are found in activated C and activated sepiolite (Ozturk & Bektas, 2004) The primary mechanisms for soluble Se removal in the columns are assimilatory reduction, dissimilatory reduction of SeO42- to SeO32- followed by adsorption, further reduction to elemental Se and precipitation, reduction and immobilization as organic-Se 2-, and reduction and immobilization as inorganic-Se2- (e.g., co-precipitation with FeS2), and biological volatilization to dimethyl Se2- (Sharma, et al., 2015). 105 Dissimilatory reduction is expected to be the dominant mechanism of SeO 42- removal in the columns, based on indicators of organic matter decomposition and redox conditions. Adsorptive losses of SeO42- onto FeOOH has been inversely correlated to pH (Zhang & Sparks, 1990), but at the neutral pH observed in the column effluents, this removal mechanism is not predicted to be important. Rather, the dominant repositories of reduced Se in the columns are expected to be adsorbed Se (IV), elemental Se, organic-Se2-, and inorganicSe2-. Removal of SeO32- through adsorption onto soil organic matter and the oxides and oxyhydroxides of Fe, Al, and Mn is due to the large surface areas of these adsorbents, and their strong affinities for many elements and their almost universal presence in soils and sediments (Parida, et al., 1997). Balistrieri & Chao (1990) suggest that SeO 32- forms binuclear, inner-sphere complexes with amorphous Fe oxyhydroxide and monodentate, and inner-sphere complexes with MnO2. The adsorption of SeO32 on amorphous Fe oxyhydroxides is roughly 4 times greater than MnO2. However, given the reducing conditions in the columns, and promotion of reductive dissolution of Fe and Mn oxides, the potential for SeO32- adsorption onto these phases is likely limited. While the organic substrates used in the study were physically pre-treated (ground up in the hammer mill), which increased the surface area significantly and likely facilitated adsorption, CMWR had a low surface area compared to more ubiquitous soil and rock materials with very fine grain sizes (e.g., sands, silts and clays). The pH of the influent and columns amended with either CMWR or sawdust and CMWR was higher than the pH of columns containing hay. This could have been a factor limiting SeO32- adsorption in these columns, a mechanism which 106 increases with decreasing pH (Parida, et al., 1997; Balistrieri & Chao, 1990; Naveau, et al., 2007). Comparing Se speciation in the influent (90.4% Se (VI), 0.20% Se(IV), 9.4% unknown Se species) and effluent from column 6 (1.2% Se (VI), 88.5% Se(IV), 10.3% unknown Se species) in week 18 indicates that almost all SeO42- was reduced. The 75% decrease in dissolved Se concentrations for this period, paired with prevailing SeO32- concentrations suggests that Se is either  Being mostly reduced to SeO32-, and being partially adsorbed in the column, with a small component being reduced further and released, or,  Being mostly reduced past SeO32-, with the majority of the further reduced species being retained in the column. The further reduction to elemental Se and then to Se 2- is supported by the higher concentrations of unknown Se species found in column 1 (83.1%) and 5 (91.8%) effluents in week 18. Without speciation of column effluents for Se 0 and Se-2, the species of unidentified Se could not be verified. By process of elimination, the abundant unidentified soluble Se species are neither Se(VI), nor Se(IV), as these forms were identified during liquid phase speciation. This leaves dissolved organo-Se, as well as possibly colloidal elemental-Se as possible phases. Indeed, Se has been reported to form 200-400 nanometer (nm) sized elemental particles that would be expected to pass through a 0.45 micron filter (Lenz, et al., 2008; Oremlund, et al., 2004), and high concentrations of dissolved organic matter (indicated by high levels of DOC) has been reported to result in prolonged suspension times, favoring transport (Buchs, et al., 2013). Contrarily, the presence of unidentified dissolved Se in the second half of the experiment 107 suggests that Se may have been immobilized by bacteria in the earlier periods of sustained biomass growth, and the die off and subsequent decomposition of the organisms (due to declining labile C availability) released dissolved organo-Se. The presence of organo-Se compounds in sediments has been attributed more to redox conditions than substrate availability (Martin, et al., 2011), suggesting that hay amended columns, with lower redox potentials, may have produced more organo-Se. Cell lysis may have resulted in the liberation of colloidal Se0 nanoparticles (Tomei, et al., 1995), or bacteria may have reduced SeO 32- to aqueous HSe- (Herbel, et al., 2003) and both of these mechanisms represent pathways for the solubilization of phases not identifiend by the liquid speciation. The decrease in the percentage of unidentified Se in week 24 effluents could have been the result of possible poor handling procedures. Incomplete N 2 purging of the collection bottles, or ambient air introduced during multiple transfers inside the N 2 filled glove bag (i.e. from collection containers to the centrifuge vials, then later via a filtering step to the shipping VCB bottles) may have introduced a small presence of O 2. In the presence of very low concentrations of DO, a quick Se2- oxidation to Se0 is expected, as the kinetics of the reaction are fast (Smith, 2014), and the elemental Se could have precipitated during transit. Dissimilatory reduction of SeO32- followed by the formation of nanoparticles of Se0S0 was observed in environmental waters with SO42- levels of 800 mg L-1 using A. brasilense, while at lower SO42- concentrations, only Se0 nanoparticles were formed (Vogel, et al., 2018). The average column influent SO42- concentration was 777 mg L-1, suggesting Se0S0 particle formation may have occurred in the columns as well. The 400 nm size of these S-Se nanoparticles is similar to pure Se nanoparticles, and they could similarly pass through the 0.45µm filter (Vogel, et al., 2018). No information has been reported about precipitation 108 tendencies of these spheres, so their presence is possible in both the column effluent as an unidentified species, and as attenuated solid precipitates in the columns. The reduction of Se0 to FeSe is favoured over HSe - at a pH of 7 (Herbel, et al., 2003) and the retention of Se2- to FeS2 has been shown to occur via Equation (28) (Liu, et al., 2008). These processes could have caused a decrease in dissolved Se and Fe (in periods of high Fe reduction), and also limited the amount of unidentified Se noted in the effluents. The precipitation of FeSe would result in Fe concentration reductions in µg L - (limited by stoichiometric relation to Se), and would not be noticeable given the mg L - concentrations of Fe. Incorporation of Se into FeSe2 is also a removal pathway (Belzile, et al., 2000). The formation reactions of these products are proposed to be similar to those of FeS 2 formation, due to the similarity of Se and S chemistry (Smith, 2014), and attenuation in the columns via this mechanism is also possible, (28) FeS2 + HSe− → FeS + Se0 + HS− Similar to biogenic Se0 nanoparticles, the precipitation of metal selenides can be affected by their small size (5-400 nm), and their release to the environment (and out of columns) may occur as a result of colloidal suspension (Jain, et al, 2017). 4.3.2 Attenuation Products and Long-term Stability Reaction products of NO3- reduction, are either very soluble (NH3, NO2-), or have sufficiently high vapour pressure that they are present primarily in gas phases. Thus, N reaction products are not expected to have precipitated out of solution and long-term stability of these products is not a concern. The dominant removal pathways of Se in the columns is thought to be precipitation (elemental Se and organic/inorganic Se2-) and adsorption (e.g., SeO32- adsorption to mineral 109 surfaces). Though SeO4-2 was transformed from an aqueous form to an insoluble state, in the presence of an oxidizing agent, it could be re-oxidized (the re-solubilization of Se is counter productive). Fluidized bed reactor systems, which are subject to significantly more agitation than the static (unmoving) amendment column experiment performed at UNBC, require downstream liquid/solids separation systems to separate biological solids which may have sloughed off (Envirogen Technologies, 2011). This constitutes another remobilization pathway to be considered. The UNBC trial had a 0.45 μm filtration step prior to submission for metals characterization, which prevented any sloughed off biological solids from being captured in the analysis of the effluents. As a result, no information relating Se to entrained/sloughed off biomass in column effluents can be used to assess this remobilization pathway. 4.3.3 Results of Geochemical Modeling Modeling saturation indices using PHREEQC software was inconclusive for multiple minerals. The software uses an equilibrium geochemical speciation model to predict mineral behaviour. The software was intended to model static environments which are not biologically active, and as the columns were dynamic, they were not well equilibrated. The conditions were not suitable for comparison with the model. Mineral phases containing Se were not within the range of the CoA provided in Section 3.4.1. 4.4 Environmental Relevance and Effect of Other Reaction Products This study was completed to provide insight into the processes responsible for contaminant removal with BCR systems, with the long-term goal of improving the design and operations of these systems. The experiment was not designed to provide a relevant numerical prediction of BCR effluent water quality. Any conclusion drawn from the 110 observation of specific concentrations in the column effluents is only marginally applicable to the full field scale implementation. Unfortunately, biological oxygen demand (BOD) was not a parameter that was monitored or considered during the experiment. As discussed in Section 3.6, there was significant discoloration and particulate evident in the effluents in periods with high concentrations of DOC. This represents a potential pathway for oxygen depletion in downstream receiving streams. During weeks 0-8, there was a release of reduced compounds (i.e. Fe and Mn) from the water column which would also consume oxygen in the water column as they re-oxidize. Extensive precipitation of Fe and Mn oxides on stream substrates also has the potential to impact the quality of habitat for benthic invertebrates (Young, 2003). High P, N, and DOC concentrations from decomposing hay in columns 1 and 5 indicate that while the degradation of organic material in these columns was happening at an augmented rate, downstream eutrophication potential increased as well. 4.4.1 Trace Elements As was noted in the results sections, there was an initial brief increase in many parameters of environmental significance followed by a rapid decrease. This is likely a result of the flushing of soluble minerals and organic particles through the system. 4.4.2 Comparison of Effluent with British Columbia Water Quality Guidelines. Influent water in the experiment already exceeded the parameter specific WQG maxima for the protection of freshwater aquatic life. Nevertheless, a table provided in Appendix D.14 compares WQG maximums for acute toxicity to the maximum concentrations observed in column 1 effluent (MoE, 2018). Parameters with guideline exceeding levels were DO, SO4-2, D-Al, D-As, D-Co, D-Fe, D-P, D-Se, and D-Zn. Individual guidelines for DOC, 111 colour, and pH relate to upstream (unaffected) water quality, and as such, are inconclusive in the context of this analysis. Post reactor aeration would likely remediate concerns about DO and Fe concentrations (oxidized Fe will quickly precipitate out of solution). Sulfate is below the influent levels and represents a significant amelioration in water quality. Concentrations of D-Al, D-Co, D-Fe, and D-Zn exhibited initial spikes, and are the result of the flushing of soluble or redox sensitive compounds from the amendments (no long term or continuous exceedances of these WQGs are expected). An analysis of the NO2- concentration in the column 1 effluents show that the Cl dependent 30-day average WQG was exceeded in weeks 18 - 20. Effluents from column 5 exceeded the 30-day and maximum NO 2- WQG jointly in weeks 1, 9 – 11, and week 18. Lastly, the effluents from column 6 exceeded the 30-day and maximum NO2- WQG jointly in weeks 1-3. Nitrite is an intermediary compound produced during denitrification, and guideline exceeding concentrations at the beginning and end of the experiment can be rationalized. In the beginning, the colony of bacteria may not have been sufficiently developed, the organic decomposition rates may have been lower, and incomplete denitrification was likely a result, while at the end of the experiment, there was likely a lack of sufficient organic substrate being degraded to produce electrons required to complete the denitrification. Column 5 effluent NO2- concentrations in weeks 9-11 coincide with elevated NH 3 concentrations. The NH3 concentrations, oxidized in conjunction with the reduction of oxides of Fe and Mn, could result in NO2- production (Kuypers, et al., 2018). The reduction of NO3- and Se concentrations was one of the primary objectives of the research. Column 1 effluents achieved an average of 97.9% and 87.8% reduction in NO 3- and Se, resulting in an average concentration of 1.58 mg L1- and 13.4 µg L-1, respectively. While 112 the average concentration of NO3- is below the WQG (32.8 mg L-1), that of Se exceeds the WQG for the protection of freshwater species (2 µg L-1) (MoE, 2018). The effluent being treated in this experiment was from a toe seep at the mine, which is a concentrated point source of these COCs. Concentration and flow data of surface or diluted flows required to make a prediction about water quality at the final effluent point, (receiving environment) are not available. The presence of unknown Se species dissolved in column effluents is problematic, due to the high comparative bioavailability of organo-Se 2-, and the propensity of Se to bioaccumulate. 4.5 Implications for Field Scale Application of Biological Reactors As a precursor to any recommendations for field scale implementation based on the results of the experiment, it must be acknowledged that there were a number of limitations associated with this study. The three most significant limitations are as follows:  There was a lack of replicate samples, and as such, the assessment of amendment performance (even if this assessment is supported by literature) cannot be statistically examined or confirmed;  There was some inevitable operator error, due to inexperience (e.g., not handling liquid samples in N2 purged environments in the first weeks) and scheduling constraints (experimental set up was only thoroughly inspected 2 or 3 days per week); and,  As previously discussed, due to activities relating to removal of blockages in column 1 (this occurred numerous times) and leakage from the column during the initial wetting of amendments, a considerable amount of organic mass may have been lost. Although the mass of hay was doubled in column 1, the results of columns 1 and 5 are similar. 113 It is unclear whether this a result of column 1 degassing and any associated organic loss or if there were other environmental constraints limiting biomass production and organic decomposition. 4.5.1 Combined Application Effluent SO42- concentrations for columns amended with organics were similar at the end of the experiment, with those amended by hay demonstrating a trend of decreasing electron acceptor reduction. Column 1 effluents had higher concentrations of undesired parameters including colour, odour, possibly toxic Se2-, DOC, and Fe2+, and the effluent was much darker and harder to filter. Although the reductive performance of columns 1 and 5 was similar, column 5 showed less undesired parameters. These findings suggest that a combined application may have the most beneficial impact on water quality. Specifically, the application a labile C source to encourage immediate bacterial colony development, tempered with a second, more refractory organic material to sustain and maintain long term reducing conditions may achieve the lowest effluent Se concentrations over extended periods of operations. Such an application could reduce the initial loading of DOC and BOD to the receiving environment while minimizing maintenance and amendment resupply costs. The evidence at the end of the experiment suggested decreasing performance from hay (possibly a result of amendment consumption), and sawdust may provide greater longevity as an electron donor source. This is an important consideration as ideally BCRs can operate for periods of 510 years without having to replenish the organic amendment. In this regard, an important consideration when evaluating BCR design relates to logistics and costs associated with amendment resupply. If additional hay can be added on an annual or semi-annual basis, then the long-term ability of the amendment to achieve desired rates of reaction may be less 114 critical. A similar upflow column study, with an organic amendment composition of 50% dry weight (dw) hay, 20% dw woodchips, and 30% dw cow manure was able to sustain SO 42reducing conditions for 430 days (Baldwin, et al., 2015), and this result further supports the theory of a combined application. 4.5.2 Amendment Conditioning Pretreating the organics may result in greater efficiencies in BCR operations. These efficiencies could result in sawdust being acceptable as a sole amendment, or they could result in less undesirable products in BCR effluents. 4.5.2.1 Pre-treatment to Enhance Rates of Decomposition. The pre-treatment of wood by thermal, mechanical, acid, alkaline, oxidative, and chemical processes to generate simple sugars before methanogenesis was demonstrated Hendriks and Zeeman (2009), and such treatments may reduce the need for a secondary, alternate, C source for successful BCR operation. While the specific chemistries, economies and feasibilities of different pre-treatments are beyond the scope of this thesis, a summary of the requirements for an economic and effective pre-treatment for methanogenesis (Agbor, et al., 2011), adapted to denitrification, and Se- and S-oxyanion reduction systems are presented below. The process should:  Have a low capital and operational cost, low energy demand and minimal handling and preconditioning requirements;  Be effective on a wide range and loading of lignocellulosic material;  Result in the recovery of most of the lignocellulosic components in a useable form in separate fractions; and, 115  Produce no or limited amounts lignin degradation products that inhibit the growth of the target organisms for NO3-, Se, and SO42- reduction. 4.5.2.2 Prewashing To avoid having unacceptably high concentrations of soluble minerals, NO 3-, Se, and SO42- in the initial flow through the BCR, the CMWR should be rinsed in its original location (on an existing waste rock dump) prior to moving it. Additionally, the CMWR should only be placed in the BCR immediately before saturation to avoid further mineral weathering and oxidation on the surface of the CMWR. 4.5.3 Performance and Implementation Considerations The following is a list of issues that should be considered before implementing a field scale bioreactor. 1. Hydrology: The field scale BCR should not be viewed as a ‘passive’ reactor as the diurnal, meteorological, and seasonal variations in flow through the reactor will affect performance. High throughput will result in excess loading of the system and might lead to higher ORP levels and/or poor Se attenuation. Low flow conditions would result in lower redox levels than necessary for Se attenuation (but have the benefit of reducing more SO42-) and this could represent a waste of the organic amendment. To minimize seasonal flow variations, zones of upstream storage (e.g., pits) could be used to store water in periods of high flow and release water through the BCR in periods of low flow. In some cases (e.g., flood events), high flow conditions may be characterized by significant dilution and lower Se and NO 3- concentrations. For these cases, a bypass should be installed to divert flows around the BCR. 116 2. Reduction of O2 surface infiltration: The re-introduction of O2 in field-based pilotscale BCRs has been avoided with the installation of booms, mitigating wind mixing and preserving anaerobic conditions (Baldwin, et al., 2015). Freezing ambient temperatures resulting in an impermeable cover of ice and snow have also bolstered the anaerobic activities (Baldwin, et al., 2015). Reducing the resupply of O 2 by limiting permeability and advection at surface should be considered. 3. Amendment re-supply: Resupplying the BCR with organic amendments may require significant operator effort to manage BOD and eutrophication-promoting products in the effluents. For large BCRs, changes in water chemistry may be less extreme if the amendment resupply can be managed through smaller and frequent additions. A record, relating varying masses of amendment added to water quality improvements (and or deteriorations), would allow for fine tuning of future mass additions. Amendment additions could also be scheduled to coincide with the annual flow cycles, providing a higher dilution for higher levels of DOC and nutrients due to snowmelt. Baldwin, et al. (2015) suggest that an upstream surge pond be included in BCR designs into which fresh organics can be added as a re-supply method. This could be helpful, as any labile C generated during the amendment re-supply may possibly be consumed by the established biological matrix downstream. 4. As Se particles are easily transported through aqueous systems (Haygarth, 1994), and biomass sloughing or colloidal transport is a potential concern, an effluent precipitation or filtration system should be considered in the design. A membrane filter is likely not practical on an exposed BCR due to clogging and maintenance considerations, as flows and sediment loads are subject to diurnal and seasonal 117 influences. Proper sedimentation pond design, accounting for the size and relative density of reduced Se particles is important. Settlement tests could be performed to investigate the final Se speciation and mineral formation. While settling velocities have be calculated directly using density and size of these minerals (and Se 0 nanoparticles, including biogenic Se), the calculated results have correlated poorly to reality (Buchs, et al., 2013). Instead, settling velocities should be directly determined via observation, resulting in properly sized sedimentation ponds and avoiding the release of reduced Se products to the receiving streams (Buchs, et al., 2013). Alternatively, a downstream wetland with emergent vegetation could provide both a low-energy environment for further accumulation of small organic particles, and a continued source of organic material from which to develop stratified redox conditions close to the sediment surface (for long term storage of deposited Se) (Martin, et al., 2011). This should be investigated by any mines considering a BCR that have the topography and the size in land tenure to accommodate a wetland, though unfortunately the Brule has neither. As organo-Se compounds will be attenuated in a vegetative wetland used to supplement a BCR, an argument should be made that the effluent sampling (i.e. permit compliance) point for water quality should be after this additional unit. Effluents should be also periodically analyzed for the production of unanticipated by-products. 5. Design for plugging and accumulation: Any waste rock that is added should be competent and not subject to fracturing. This media provides surface area for bacteria to grow, but also provides a porous substrate to control hydraulic conductivity and mitigate short circuiting. Available pore space, amendment particle size, and 118 expected flow should be carefully considered. If the resistance to flow is too high, the height of the water column will increase, and the least resistance flowpath will be above or around the reactor. All influent and effluent infrastructure should be able to be cleaned and unplugged. In the fixed pore space of the column trial, plugging caused significant issues. 6. The volume of precipitated elemental Se, accumulated as a result of BCR activity, is relatively limited and easily managed. A comprehensive approach for reactor biomass and sludge removal at the end of the BCR life cycle should be considered before system construction. Specific consideration should be given to the final disposal of materials with significant Se accumulation. Short term draining of the BCR should be done with extreme caution, as re-oxidizing the reactor bed could result in remobilization of Se. 7. Volumes and concentrations to be treated should be analyzed considering effects on both incremental mass removal and cost. At the Brule Mine, Se is highly concentrated in specific toe seeps, and as a result, the most economical and impactful remediation strategy may be a targeted approach utilizing multiple small BCRs. While the complexity of the strategy may increase as a result of multiple reactors, the efficiency and cost savings could be significant. 119 Section 5: Conclusion A saturated, anaerobic up-flow column experiment was conducted to investigate the effectiveness of two organic amendments (hay and sawdust) for promoting microbially induced reducing conditions for the attenuation of nitrate and selenium in effluent collected from a coal mine in north eastern British Columbia. The effects of the amendments were elucidated by chemical characterization of the effluents from columns containing one or both amendments mixed with mine sourced crushed rock and the analysis of the results. Hay proved to be the most suitable for promoting reducing conditions and contaminant removal (up to 98.6% and 99.9% removal for selenium and nitrate, respectively compared to influent concentrations). 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Retrieved from Biomedcental Microbiology. 134 Appendix A. The Eh-pH diagrams for N, Se, and S are displayed in this appendix. The diagrams are the result of thermodynamic modelling, and have been produced by the National Institute of Advanced Industrial Science and Technology (Takeno, 2005) referencing the default database “thermo.dat” based on LLNL (Lawrence Livermore National Lab.) data 0.3245r46, bundled with commercially available software GWB (Geochemist’s Workbench) written by C. M. Bethke, Illinois University. When comparing the diagrams for N, Se, or S resulting from the use of other databases, there is a general agreement with the LLNL database of the dominant species. One database (SUPCRT: SUPCRT92 (Johnson et al., 1992) applied with 98 update distributed by Everette Shock from his website on the Internet) does not show the presence of elemental Se as a stable phase. This diagram is not included. Please note that the inability to secure permission for the use of the images from the author has resulted in their removal from the thesis. Please find Eh-pH diagrams for N, Se, and S on pages 153, 229, and 219, respectively in Takeno (2005). Appendix B – Photographs 1. ANFO emulsion trails on the ground at a mine 2. Luer lock image 3. Sand layer at the base of a column B Descriptions of images, starting in the upper right and proceeding clockwise) 1. ANFO emulsion trails between blast holes on a blasting pattern at the Brule Mine 2. 4-way valves (stopcock with male Luer lock connections) 3. 1 cm thick layer of partially saturated Ottawa Sand overlain by organic amendment mixed with CMWR (photo taken while filling the columns with mine water). Appendix C – Specifications 1. Lorax Supplied Column Specification 2. National Institute of Standards and Technology – Pump Calibration 3. Methods Used by ALS 4. ALS Sample Preservation Instructions C NOTE: That Lorax will supply varying Length = l and Diameter = d depending on needs. Also Lorax will supply threaded adapters for the top and bottom ports. Side View Bottom View Top View Appendix C.3 - Parameters and Methods Matrix Parameter TOC, DOC Ammonia Nutrients/Anions Total Metals Dissolved metals Sulphide Alkalinity Patricle Size - Sieve and Pipette Detailed Sulfide/sulfur Total inorganic carbon Method American Public Health Association 5310B Journal of Environmental Monitoring, 2005, 7, 37 - 42, The Royal Society of Chemistry Environmental Protection Agency 300.1 (modified) Water Environmental Protection Agency 200.2/6020A (modified) and Environmental Protection Agency SW-846 3005A/6010B Environmental Protection Agency 200.2/6020A (modified) and Environmental Protection Agency SW-846 3005A/6010B American Public Health Association 4500-S2 Sulphide American Public Health Association 2320 Alkalinity or Environmental Protection Agency 310.2 Burt, R. (2009). Soil Survey Field and Laboratory Methods Manual. Soil Survey Investigations Report No. 5. Method 3.2.1.2.2. ALS Specialty Assay Procedure - Leco Sulphur Analyzer, Gravimetric ALS Specialty Assay Procedure - Carbonate Carbon in Solid Samples by CO2 Coulometry Sobek Method – Method Code OA-VOL08 Modified Sobek Method – Method Code OA-VOL08m CMWR Sobek ABA analysis Siderite-Corrected Sobek Method – Method Code OA-VOL08s Mine Environment Neutral Drainage 2009 Method – Method Code OA-VOL08mn Paste pH – Method Code OA-ELE07 Aqua Regia Digestion (GEO-AR01) ICP-MS Metals Analysis With Finish and Aqua Regia Digest Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) Moisture American Society for Testing and Materials D2974-00 Method A Leachable Anions and Nutrients American Society for Testing and Materials 4110 IC and Environmental Protection Agency 300.1 Total N by Leco Soil Science Society of America (1996) P. 973-974 Organics Available Ammonium Canadian Society of Soil Science (1993) 4.2/COMM SOIL SCI 19(6) Metals Environmental Protection Agency 200.2/6020A (mod) Total C Method is assumed to be LECO, but cannot be confirmed Page 1 of 1 Bottle Order Request Bottle Order #: Lab: Account #: Order Created By: Expected Date: Order Priority: Ship/Pickup Via: Waybill Number: Prepared Date: Prepared By: Checked By: BR132932 VANCOUVER WCC350 Kaitlyn Gardner 11/24/2014 12:00 AM Regular Pick Up by Client ready 1 pallettx11coolers 11/24/2014 11:02 AM Stuart Mclean Date Company: Client Contact: Address: 6/1/2015 4:52 PM Brule Coal Partnership Nicholas Dumaresq Box 508 Chetwynd, BC, V0C 1J0 Phone Number: Fax Number: 250-788-3619 -- Client Job Number: ND-RESEARCH PROJECT Q48064 Initials Comments: Qty 25 Item (Analysis) General-Anions (BC) Container 125mL HDPE Bottle Colour Preservative Instructions # 3 23 Metals (BC) 125mL HDPE (VCB) Bottle Blue 1.5 mL 1:3 HNO3 23,13, 3,39 7 NH3 250mL Amber Glass Bottle Purple 1 mL 1:1 H2SO4 3,11 25 Sulfide (BC) 125mL HDPE Bottle Orange 1-2 mL Zn Acetate/1 mL 6N NaOH 3,14,15,22 6 TOC 250mL Amber Glass Bottle Purple 1 mL 1:1 H2SO4 3,11 Please note the "Instructions #" above for the sample containers and items shipped to you. Find the corresponding number below and follow the instructions/guidelines. Instructions # 3 11 13 14 15 22 23 39 Guideline Keep cool (4oC). Sulfuric acid (H2SO4): oxidizer/corrosive-in case of contact with skin, rinse affected area with excess cold water. Nitric acid (HNO3): highly toxic/corrosive- in case of contact with skin, rinse affected area with excess cold water. Sodium Hydroxide (NaOH): corrosive/toxic-in case of contact with skin, rinse affected area with excess cold water. Zinc acetate (ZnC4H6O4): toxic-in case of contact with skin, rinse affected area several times with cold water. Add the zinc acetate (reagent #1 - red cap) to an almost full bottle, cap and shake, then add the sodium hydroxide (reagent#2 - blue cap) and shake. Dissolved Metals: filter in the field, then acidify. Total Metals: acidify in the field without filtering, further digested in the laboratory. Add the contents of the blue (nitric acid) vial to the 125 or 250 mL plastic (HDPE) bottle after the sample has been added. ADDRESS: 8081 Lougheed Hwy, Suite 100, Burnaby, BC V5A 1W9 Canada | Phone: +1 604 253 4188 | Fax: +1 604 253 6700 ALS CANADA LTD Part of the ALS Group A Campbell Brothers Limited Company Appendix D – Results 1. QAQC – Results Summarized 2. QAQC – Duplicate Analysis 3. QAQC – Blank Analysis 4. QAQC – Reference Analysis 5. CMWR Particle Size Analysis 6. CMWR Chemical Characterization 7. Hay Chemical Characterization 8. Sawdust Chemical Characterization 9. Influent and Effluent Analysis – Tabulated Presentation 10. Influent and Effluent Analysis – Graphical Presentation Field Parameters i. pH ii. Dissolved Oxygen iii. ORP Anions iv. Hardness (as CaCO3) v. Total Alkalinity (as CaCO3) vi. Ammonia (as N) vii. Bromide viii. Chloride ix. Fluoride x. Nitrate (as N) xi. Nitrite (as N) xii. Sulfate xiii. Sulfide (as S) xiv. Dissolved Organic Carbon Dissolved Metals xv. Aluminum xvi. Antimony xvii. Arsenic xviii. Barium xix. Beryllium xx. Bismuth xxi. Boron xxii. Cadmium xxiii. Calcium xxiv. Chromium xxv. Cobalt xxvi. Copper xxvii. Iron D xxviii. Lead xxix. Lithium xxx. Magnesium xxxi. Manganese xxxii. Molybdenum xxxiii. Nickel xxxiv. Phosphorous xxxv. Potassium xxxvi. Selenium xxxvii. Silicon xxxviii. Silver xxxix. Sodium xl. Strontium xli. Thallium xlii. Tin xliii. Titanium xliv. Uranium xlv. Vanadium xlvi. Zinc 11. Liquid Phase Selenium Speciation – Tabulated Presentation 12. Liquid Phase Selenium Speciation – Graphical Presentation 13. PHREEQC Modelled Saturation Indices for Minerals of Interest 14. Comparison of Column 1 Effluent and British Columbia Water Quality Guidelines E Appendix D.1 QAQC Results Summarized Appendix D.1 - Quality Analysis and Quality Control (QAQC) Results Summarized D.1.1 Field (independent of ALS) D.1.1.1 Overview The CoA for duplicate field sample QAQC results is based on those proposed in the BC Field Sampling Manual (Clark, 2003) which notes that if either measurement is greater or equal to five times the MDL, RPD greater than 20% indicate a possible problem, and greater than 50% indicate a definite problem (Clark, 2003). This issue is most likely arising from contamination or lack of sample representativeness. For values within five times the MDL, results of duplicate RPD analysis are not useful predictors of data quality. The CoA for the blank sample QAQC is that no measured parameter value should exceed the MDL. The CoA for the reference sample QAQC is that the RPD between the obtained value and expected value is less than 20%, again with the qualification that the results need to be greater than 500% of the MDL for this analysis to be relevant. D.1.1.2 Duplicate Sample and duplicate analysis results are presented in tabular form in Appendix D.2, with those that exceed the CoA highlighted. These exceedances and the associated RPD values are displayed in Table D.1. Table D.1: Duplicate sample results exceeding the RPD CoA (20%). Week 5 13 15 19 22 RPD (%) 50.00 34.00 45.20 21.30 21.30 53.40 46.40 110.13 22.40 Parameter T-NH3 (as N) D-Co D-Mo T-Alkalinity (as CaCO3) D-Bo D-Se D-As NO3- (as N) NO2- (as N) Page 1 of 3 Appendix D.1 QAQC Results Summarized D.1.1.3 Blank Blank analysis results are presented in tabular form in Appendix D.3, with those that exceed the CoA highlighted. Concentrations of parameters exceeding the CoA are presented in Table D.2. D.1.1.4 Reference Samples Results of analysis of reference samples are presented in tabular form in Appendix D.4, with those that exceed the CoA highlighted. These exceedances and the associated RPD values are displayed in Table D.3 Table D.2: Blank sample results exceeding the method detection limits. Week 3 5 7 9 13 15 17 Value (in mg L-1) 0.0154 3.36 0.0058 0.000131 0.00278 0.000053 0.101 0.0057 0.0276 0.000103 0.0059 0.000176 0.052 0.000245 0.00032 2.7 0.105 0.0052 2.6 0.008 0.059 Parameter NO3DOC NO3D-Ba D-Cu D-Mn D-Si T-NH3 NO3D-Pb NO3D-Ba D-Ca D-Mo D-Sr T-Alkalinity (as CaCO3) D-Si T-NH3 T-Alkalinity (as CaCO3) NO3DOC Page 2 of 3 Appendix D.1 QAQC Results Summarized D.1.2 Lab ALS performed their own internal QAQC program, which included laboratory control samples, internal method blanks, matrix spikes, and no results were outside their limits of acceptability. Table D.3: Reference Samples Exceeding the RPD CoA (20%). Parameter D-Al D-Pb D-Mo D-Se D-Tl D-U Week 11 13 15 17 18 19 22 24 11 11 22 11 13 11 Page 3 of 3 RPD (%) 36.5 26.5 36.6 45.8 38.1 57.8 62.2 74.2 20.3 20.3 23.0 23.5 20.8 24.2 Appendix D.2 QAQC - Duplicate Analysis total concentration! not dissolved RPD > 20% RPD > 50% Result < 5x MDL Results that are acceptable or not calculated due to a lack of suitable data are labelled 'N/A' Physical Tests Samples Date Organic Carbon Anions and Nutrients Dissolved Metals Hardness (as CaCO3) Alkalinity, Total (as CaCO3) Ammonia, Total (as N) Bromide (Br) Chloride (Cl) Fluoride (F) Nitrate (as N) Nitrite (as N) Sulfate (SO4) Sulfide as S Dissolved Organic Carbon 1 1 931 930 N/A 0.50 118 116 N/A 2.0 0.0069 N/A 0.0050 1 1 N/A 1.0 11 11 N/A 10 0.4 0.4 N/A 0.40 73.6 73.5 N/A 0.10 0.02 0.02 N/A 0.020 782 781 N/A 6.0 0.02 N/A 0.020 N/A - 0.003 0.003 N/A 0.0030 0.00188 0.00184 N/A 0.00010 0.00016 0.00015 N/A 0.00010 0.0266 0.0269 N/A 0.000050 0.0001 0.0001 N/A 0.00010 0.0005 0.0005 N/A 0.00050 0.119 0.119 N/A 0.010 0.00001 0.00001 N/A 0.000010 189 190 N/A 0.050 0.0001 0.0001 N/A 0.00010 3 9 24-Feb-15 24-Feb-15 Duplicate RPD Specific MDL for Sample 3 3 N/A - 984 965 N/A 1.0 9.24 9.06 N/A 0.25 1 1 N/A 1.0 14 14 N/A 10 0.4 0.4 N/A 0.40 0.14 0.12 N/A 0.10 0.02 0.02 N/A 0.020 604 604 N/A 6.0 N/A - 810 779 N/A 50 0.358 0.299 N/A 0.0060 0.0151 0.0151 N/A 0.00020 0.0105 0.0110 N/A 0.00020 0.113 0.134 N/A 0.00010 0.0002 0.0002 N/A 0.00020 0.001 0.001 N/A 0.0010 0.452 0.442 N/A 0.020 0.00152 0.00160 N/A 0.000020 445 439 N/A 0.050 0.00685 0.00683 N/A 0.00020 4 10 5 5 880 889 N/A 0.50 293 298 N/A 2.0 0.132 0.220 50.00 0.013 0.5 0.5 10.15 0.50 10.2 10.1 N/A 5.0 0.40 0.39 N/A 0.20 28.5 28.0 N/A 0.050 0.352 0.310 N/A 0.010 776 774 N/A 3.0 0.02 N/A 0.020 15.0 14.9 N/A 1.0 0.003 0.003 N/A 0.0030 0.00578 0.00646 N/A 0.00010 0.00101 0.00107 N/A 0.00010 0.0191 0.0193 N/A 0.000050 0.0001 0.0001 N/A 0.00010 0.0005 0.0005 N/A 0.00050 0.237 0.256 N/A 0.010 0.00166 0.00170 N/A 0.000010 203 202 N/A 0.050 0.0001 0.0001 N/A 0.00010 2 8 25-MAR-15 25-MAR-15 Duplicate RPD Specific MDL for Sample 7 7 903 891 N/A 0.50 145 142 N/A 1.0 0.0747 0.0805 N/A 0.0050 <0.50 <0.50 N/A 0.50 9.7 9.5 N/A 5.0 0.31 0.30 N/A 0.20 72.7 70.8 N/A 0.050 0.014 0.016 N/A 0.010 772 752 N/A 3.0 N/A - 2.71 2.65 N/A 0.50 <0.0030 0.0268 N/A 0.0030 0.00426 0.00408 N/A 0.00010 0.00020 0.00023 N/A 0.00010 0.0164 0.0163 N/A 0.000050 <0.00010 <0.00010 N/A 0.00010 <0.00050 <0.00050 N/A 0.00050 0.202 0.201 N/A 0.010 0.00173 0.00164 N/A 0.000010 192 190 N/A 0.050 <0.00010 <0.00010 N/A 0.00010 6 12 08-APR-15 08-APR-15 Duplicate RPD Specific MDL for Sample 9 9 927 933 N/A 0.50 211 209 N/A 2.0 0.0321 0.0296 N/A 0.0050 <0.50 <0.50 N/A 0.50 10.3 10.3 N/A 5.0 0.36 0.35 N/A 0.20 54.4 54.1 N/A 0.050 0.099 0.102 N/A 0.010 786 783 N/A 3.0 N/A - 9.39 10.3 N/A 0.50 <0.0030 <0.0030 N/A 0.0030 0.00524 0.00522 N/A 0.00010 0.00081 0.00081 N/A 0.00010 0.0197 0.0196 N/A 0.000050 <0.00010 <0.00010 N/A 0.00010 <0.000050 <0.000050 N/A 0.000050 0.230 0.235 N/A 0.010 0.00136 0.00136 N/A 0.0000050 208 208 N/A 0.050 <0.00010 <0.00010 N/A 0.00010 6 12 11 11 967 961 N/A 0.50 197 196 N/A 2.0 0.0536 0.0502 N/A 0.0050 <1.0 <1.0 N/A 1.0 10 10 N/A 10 <0.40 <0.40 N/A 0.40 56.6 57.7 N/A 0.10 0.042 0.042 N/A 0.020 770 789 N/A 6.0 N/A - 7.16 7.24 N/A 0.50 <0.0030 <0.0030 N/A 0.0030 0.00487 0.00509 N/A 0.00010 0.00070 0.00068 N/A 0.00010 0.0187 0.0183 N/A 0.000050 <0.00010 <0.00010 N/A 0.00010 <0.000050 <0.000050 N/A 0.000050 0.164 0.165 N/A 0.010 0.00137 0.00131 N/A 0.0000050 215 215 N/A 0.050 <0.00010 <0.00010 N/A 0.00010 3 9 13 13 992 939 N/A 0.50 1010 870 N/A 20 1.37 1.28 N/A 0.025 <0.50 <0.50 N/A 0.50 9.9 10.0 N/A 5.0 0.37 0.36 N/A 0.20 <0.050 3.51 N/A 0.050 <0.010 0.065 N/A 0.010 329 295 N/A 3.0 29.3 N/A 4.0 74.2 76.2 N/A 5.0 0.0222 0.0227 N/A 0.0030 0.00621 0.00625 N/A 0.00010 0.0137 0.0131 N/A 0.00010 0.317 0.330 N/A 0.000050 <0.00010 <0.00010 N/A 0.00010 <0.000050 <0.000050 N/A 0.000050 0.136 0.119 N/A 0.010 0.0000204 0.0000373 58.58 0.00 229 209 4.08 0.050 0.00154 0.00161 N/A 0.00010 3 9 20-MAY-15 20-MAY-15 Duplicate RPD Specific MDL for Sample 15 15 947 953 N/A 0.50 826 667 21.30 1.0 1.53 1.68 667.00 0.050 <1.0 <1.0 N/A 1.0 <10 <10 N/A 10 <0.40 <0.40 N/A 0.40 3.79 3.86 N/A 0.10 0.139 0.150 N/A 0.020 229 230 N/A 6.0 31.6 N/A 4.0 105 107 N/A 5.0 0.0243 0.0246 N/A 0.0030 0.00612 0.00624 N/A 0.00010 0.0155 0.0149 N/A 0.00010 0.345 0.350 N/A 0.000050 <0.00010 <0.00010 N/A 0.00010 <0.000050 <0.000050 14.30 0.000050 0.143 0.177 0.0000179 0.0000259 21.25 0.010 36.53 0.0000050 212 216 3.58 0.050 0.00177 0.00173 N/A 0.00010 3 02-JUN-15 02-JUN-15 9 Duplicate RPD Specific MDL for Sample 17 17 939 920 N/A 0.50 778 713 N/A 20 3.22 3.06 N/A 0.050 <0.50 <0.50 N/A 0.50 10.0 9.9 N/A 5.0 0.33 0.33 N/A 0.20 8.61 8.45 N/A 0.050 2.17 2.15 N/A 0.010 439 436 N/A 3.0 31 N/A 10 59 58 N/A 10 0.0156 0.0146 N/A 0.0030 0.00564 0.00551 N/A 0.00010 0.0128 0.0126 N/A 0.00010 0.258 0.258 N/A 0.000050 <0.00010 <0.00010 N/A 0.00010 <0.000050 <0.000050 N/A 0.000050 0.139 0.136 N/A 0.010 0.0000138 0.0000125 N/A 0.0000050 210 206 N/A 0.050 0.00109 0.00099 N/A 0.00010 4 10 19 19 923 903 N/A 0.50 217 215 N/A 1.0 0.206 0.212 N/A 0.0050 <0.50 <0.50 N/A 0.050 9.9 10.4 N/A 0.50 0.31 0.29 N/A 0.020 46.6 48.5 N/A 0.0050 0.581 0.662 N/A 0.0010 770 802 N/A 0.30 <0.020 N/A 0.020 4.26 4.68 N/A 0.50 <0.0030 <0.0030 N/A 0.0030 0.00496 0.00488 N/A 0.00010 0.00154 0.00096 46.40 0.00010 0.0203 0.0205 9.60 0.000050 <0.00010 <0.00010 N/A 0.00010 <0.000050 <0.000050 N/A 0.000050 0.169 0.165 N/A 0.010 0.000694 0.000695 N/A 0.0000050 199 200 N/A 0.050 <0.00010 <0.00010 N/A 0.00010 Week Inlet 10-Feb-15 14 (Duplicate) 10-Feb-15 Duplicate RPD Specific MDL for Sample 11-Mar-15 11-Mar-15 Duplicate RPD Specific MDL for Sample 22-APR-15 22-APR-15 Duplicate RPD Specific MDL for Sample 05-MAY-15 05-MAY-15 Duplicate RPD Specific MDL for Sample 17-Jun-2015 17-Jun-2015 Duplicate RPD Specific MDL for Sample 7-Jul-2015 7-Jul-2015 Duplicate RPD Specific MDL for Sample Aluminum (Al)- Antimony (Sb)- Arsenic (As)Dissolved Dissolved Dissolved Barium (Ba)Dissolved Beryllium (Be)- Bismuth (Bi)Dissolved Dissolved Boron (B)Dissolved Cadmium (Cd)- Calcium (Ca)- Chromium Dissolved Dissolved (Cr)-Dissolved 1 7 22 22 1060 1050 N/A 0.50 666 704 N/A 1.0 0.0686 0.0607 N/A 0.0050 <0.25 <1.0 N/A 0.050 9.6 <10 N/A 0.50 0.31 <0.40 130.40 0.020 0.652 2.25 110.13 0.0050 0.0679 0.085 22.37 0.0010 573 581 N/A 0.30 5.5 N/A N/A 0.020 33.3 32.7 N/A 0.50 0.0186 0.0195 N/A 0.0030 0.00233 0.00247 N/A 0.00010 0.00912 0.00937 N/A 0.00010 0.381 0.400 N/A 0.000050 <0.00010 <0.00010 N/A 0.00010 <0.000050 <0.000050 N/A 0.000050 0.147 0.144 N/A 0.010 0.0000092 <0.0000050 N/A 0.0000050 254 249 N/A 0.050 0.00142 0.00141 N/A 0.00010 1 7 24 24 1010 1000 N/A 0.50 467 438 N/A 1.0 <0.0050 <0.0050 N/A 0.0050 <0.50 <0.50 N/A 0.050 10.0 9.9 N/A 0.50 <0.20 <0.20 N/A 0.020 22.6 22.4 N/A 0.0050 0.117 0.116 N/A 0.0010 706 701 N/A 0.30 0.206 0.178 N/A 0.020 FIELD FIELD N/A 0.0073 0.0060 N/A 0.0030 0.00444 0.00449 N/A 0.00010 0.00566 0.00572 N/A 0.00010 0.111 0.111 N/A 0.000050 <0.00010 <0.00010 N/A 0.00010 <0.000050 <0.000050 N/A 0.000050 0.138 0.136 N/A 0.010 <0.0000050 <0.0000050 N/A 0.0000050 238 235 N/A 0.050 0.00042 0.00038 N/A 0.00010 22-Jul-2015 22-Jul-2015 Duplicate RPD Specific MDL for Sample Page 1 of 2 Appendix D.2 QAQC - Duplicate Analysis total concentration! not dissolved RPD > 20% RPD > 50% Result < 5x MDL Results that are acceptable or not calculated due to a lack of suitable data are labelled 'N/A' Dissolved Metals Cobalt (Co)Dissolved Copper (Cu)Dissolved Iron (Fe)Dissolved Lead (Pb)Dissolved Lithium (Li)Dissolved Magnesium (Mg)Dissolved Manganese (Mn)Dissolved Molybdenum (Mo)Dissolved Nickel (Ni)Dissolved 1 1 0.0001 0.0001 N/A 0.00010 0.00091 0.00092 N/A 0.00050 0.03 0.03 N/A 0.030 0.000075 0.000082 N/A 0.000050 0.186 0.191 N/A 0.00050 111 111 N/A 0.10 0.000097 0.000085 N/A 0.000050 0.00432 0.00426 N/A 0.000050 0.0583 0.0588 N/A 0.00050 0.3 0.3 N/A 0.30 4.3 4.2 N/A 2.0 3 9 24-Feb-15 24-Feb-15 Duplicate RPD Specific MDL for Sample 3 3 0.209 0.206 N/A 0.00020 0.0075 0.0078 N/A 0.0010 26.3 25.9 N/A 0.030 0.00148 0.00162 N/A 0.00010 0.214 0.211 N/A 0.0010 87.7 86.6 N/A 0.10 1.19 1.20 N/A 0.00010 0.0152 0.0148 N/A 0.00010 1.33 1.31 N/A 0.0010 3.36 3.35 N/A 0.30 4 10 5 5 0.0372 0.0376 N/A 0.00010 0.00063 0.00075 N/A 0.00050 0.03 0.03 N/A 0.030 0.000143 0.000153 N/A 0.000050 0.193 0.206 N/A 0.00050 90.6 93.2 N/A 0.10 0.252 0.256 N/A 0.000050 0.0227 0.0246 N/A 0.000050 0.186 0.189 N/A 0.00050 2 8 25-MAR-15 25-MAR-15 Duplicate RPD Specific MDL for Sample 7 7 0.0206 0.0202 N/A 0.00010 0.00153 0.00168 N/A 0.00050 <0.030 <0.030 N/A 0.030 <0.000050 <0.000050 N/A 0.000050 0.227 0.225 N/A 0.00050 103 101 N/A 0.10 0.128 0.129 N/A 0.000050 0.0150 0.0153 N/A 0.000050 6 12 08-APR-15 08-APR-15 Duplicate RPD Specific MDL for Sample 9 9 0.0327 0.0320 N/A 0.00010 0.00066 0.00058 N/A 0.00050 <0.030 <0.030 N/A 0.030 0.000078 0.000087 N/A 0.000050 0.241 0.243 N/A 0.0010 99.0 100 N/A 0.10 0.258 0.256 N/A 0.00010 6 12 11 11 0.0223 0.0220 N/A 0.00010 0.00067 0.00065 N/A 0.00050 <0.030 <0.030 N/A 0.030 <0.000050 <0.000050 N/A 0.000050 0.187 0.192 N/A 0.0010 104 103 N/A 0.10 3 9 13 13 0.00066 0.00093 <0.00050 <0.00050 6.60 0.00050 0.419 0.132 33.96 0.00010 104.17 0.030 <0.000050 0.000060 4.40 0.000050 0.175 0.149 N/A 0.0010 Week Inlet 10-Feb-15 14 (Duplicate) 10-Feb-15 Duplicate RPD Specific MDL for Sample 11-Mar-15 11-Mar-15 Duplicate RPD Specific MDL for Sample 22-APR-15 22-APR-15 Duplicate RPD Specific MDL for Sample 05-MAY-15 05-MAY-15 Duplicate RPD Specific MDL for Sample 3 9 Phosphorus Potassium (K)- Selenium (Se)(P)-Dissolved Dissolved Dissolved Silicon (Si)Dissolved Silver (Ag)Dissolved Sodium (Na)- Strontium (Sr)- Thallium (Tl)Dissolved Dissolved Dissolved Tin (Sn)Dissolved Titanium (Ti)Dissolved 0.104 0.104 N/A 0.00010 2.46 2.46 N/A 0.050 0.00001 0.00001 N/A 0.000010 101 101 N/A 2.0 0.000024 0.000023 N/A 0.000010 0.0001 0.0001 N/A 0.00010 0.012 0.012 N/A 0.010 0.0202 0.0201 N/A 0.000010 0.001 0.001 N/A 0.0010 0.003 0.003 N/A 0.0030 107 105 N/A 2.0 0.00374 0.00382 N/A 0.00020 19.8 19.2 N/A 0.050 0.000032 0.000052 47.62 0.000020 104 101 1.60 0.784 0.000077 0.751 0.000084 less than 5 x MDL 0.000020 0.00046 0.00050 N/A 0.00020 0.042 0.040 N/A 0.010 0.00236 0.00236 N/A 0.000020 0.0221 0.0226 N/A 0.0020 0.223 0.224 N/A 0.0060 0.3 0.3 N/A 0.30 6.1 6.3 N/A 2.0 0.0286 0.0292 N/A 0.00010 2.91 2.90 N/A 0.050 0.00001 0.00001 N/A 0.000010 104 105 N/A 2.0 0.326 0.353 N/A 0.00020 0.000081 0.000089 N/A 0.000010 0.0001 0.0001 N/A 0.00010 0.012 0.012 N/A 0.010 0.0232 0.0257 N/A 0.000010 0.0028 0.0028 N/A 0.0010 0.115 0.116 N/A 0.0030 0.125 0.122 N/A 0.00050 <0.30 <0.30 N/A 0.30 5.0 4.9 N/A 2.0 0.111 0.107 N/A 0.00010 2.36 2.28 N/A 0.050 <0.000010 <0.000010 N/A 0.000010 105 103 N/A 2.0 0.353 0.350 N/A 0.00020 0.000085 0.000088 N/A 0.000010 <0.00010 <0.00010 N/A 0.00010 <0.010 <0.010 N/A 0.010 0.0189 0.0183 N/A 0.000010 <0.0010 <0.0010 N/A 0.0010 0.0830 0.0805 N/A 0.0030 0.0173 0.0171 N/A 0.000050 0.177 0.174 N/A 0.00050 <0.30 <0.30 N/A 0.30 4.9 4.9 N/A 2.0 0.0512 0.0507 N/A 0.000050 2.57 2.56 N/A 0.050 <0.000010 <0.000010 N/A 0.000010 97.9 98.1 N/A 2.0 0.341 0.335 N/A 0.00020 0.000068 0.000065 N/A 0.000010 <0.00010 <0.00010 N/A 0.00010 0.016 0.016 N/A 0.010 0.0199 0.0200 N/A 0.000010 0.00101 0.00103 N/A 0.00050 0.102 0.101 N/A 0.0030 0.184 0.183 N/A 0.00010 0.0145 0.0149 N/A 0.000050 0.134 0.133 N/A 0.00050 <0.30 <0.30 N/A 0.30 5.1 5.4 N/A 2.0 0.0456 0.0456 N/A 0.000050 2.56 2.60 N/A 0.050 <0.000010 <0.000010 N/A 0.000010 102 105 N/A 2.0 0.349 0.353 N/A 0.00020 0.000064 0.000069 N/A 0.000010 <0.00010 <0.00010 N/A 0.00010 0.014 0.014 N/A 0.010 0.0180 0.0181 N/A 0.000010 0.00057 0.00056 N/A 0.00050 0.0834 0.0822 N/A 0.0030 102 101 N/A 0.10 0.102 0.0967 N/A 0.00010 0.00154 0.00244 45.23 0.000050 0.0189 0.0202 30.80 0.00050 1.62 1.65 N/A 0.30 18.1 16.8 N/A 2.0 0.00997 0.00973 N/A 0.000050 16.6 15.5 N/A 0.050 <0.000010 <0.000010 N/A 0.000010 102 94.5 N/A 2.0 0.378 0.390 N/A 0.00020 <0.000010 <0.000010 N/A 0.000010 <0.00010 <0.00010 N/A 0.00010 0.013 <0.010 N/A 0.010 0.00606 0.00619 N/A 0.000010 0.00739 0.00755 N/A 0.00050 <0.0030 <0.0030 N/A 0.0030 0.339 0.351 N/A 0.00020 Uranium (U)- Vanadium (V)Dissolved Dissolved Zinc (Zn)Dissolved 20-MAY-15 20-MAY-15 Duplicate RPD Specific MDL for Sample 15 15 0.00081 0.00077 N/A 0.00010 <0.00050 <0.00050 N/A 0.00050 0.064 0.067 N/A 0.030 <0.000050 0.000065 N/A 0.000050 0.190 0.221 N/A 0.0010 102 101 N/A 0.10 0.0797 0.0816 N/A 0.00010 0.00194 0.00198 N/A 0.000050 0.0238 0.0240 N/A 0.00050 1.65 1.70 N/A 0.30 15.5 15.9 N/A 2.0 0.0116 0.00671 53.41 0.000050 15.5 15.9 134.20 0.050 <0.000010 <0.000010 N/A 0.000010 98.5 102 N/A 2.0 0.373 0.380 N/A 0.00020 <0.000010 <0.000010 N/A 0.000010 <0.00010 <0.00010 N/A 0.00010 0.015 0.014 N/A 0.010 0.00516 0.00514 N/A 0.000010 0.00881 0.00872 N/A 0.00050 <0.0030 <0.0030 N/A 0.0030 3 02-JUN-15 02-JUN-15 9 Duplicate RPD Specific MDL for Sample 17 17 0.00084 0.00080 N/A 0.00010 <0.00050 <0.00050 N/A 0.00050 0.120 0.122 N/A 0.030 <0.000050 <0.000050 N/A 0.000050 0.209 0.205 N/A 0.0010 101 98.2 N/A 0.10 0.0684 0.0666 N/A 0.00010 0.00208 0.00204 N/A 0.000050 0.0231 0.0218 N/A 0.00050 0.99 1.00 N/A 0.30 12.6 12.5 N/A 2.0 0.0112 0.0109 N/A 0.000050 11.6 11.5 N/A 0.050 <0.000010 <0.000010 N/A 0.000010 98.3 99.6 N/A 2.0 0.386 0.382 N/A 0.00020 <0.000010 <0.000010 N/A 0.000010 <0.00010 <0.00010 N/A 0.00010 <0.010 <0.010 N/A 0.010 0.00759 0.00769 N/A 0.000010 0.00591 0.00566 N/A 0.00050 <0.0030 <0.0030 N/A 0.0030 4 10 19 19 0.0170 0.0163 N/A 0.00010 <0.00050 <0.00050 N/A 0.00050 <0.030 <0.030 N/A 0.030 <0.000050 <0.000050 N/A 0.000050 0.192 0.186 N/A 0.0010 104 98.2 N/A 0.10 0.145 0.140 N/A 0.00010 0.0130 0.0128 N/A 0.000050 0.0972 0.0932 N/A 0.00050 <0.30 <0.30 N/A 0.30 5.0 5.1 N/A 2.0 0.0455 0.0450 N/A 0.000050 2.58 2.63 N/A 0.050 <0.000010 <0.000010 N/A 0.000010 98.4 99.0 N/A 2.0 0.322 0.318 N/A 0.00020 0.000077 0.000078 N/A 0.000010 <0.00010 <0.00010 N/A 0.00010 <0.010 <0.010 N/A 0.010 0.0175 0.0173 N/A 0.000010 0.00113 0.00105 N/A 0.00050 0.0629 0.0613 N/A 0.0030 1 7 22 22 0.00039 0.00041 N/A 0.00010 <0.00050 <0.00050 N/A 0.00050 0.055 0.050 N/A 0.030 <0.000050 <0.000050 N/A 0.000050 0.202 0.205 N/A 0.0010 103 103 N/A 0.10 0.107 0.111 N/A 0.00010 0.000818 0.000867 N/A 0.000050 0.00829 0.00833 N/A 0.00050 <0.30 <0.30 N/A 0.30 12.4 12.0 N/A 2.0 0.0177 0.0171 N/A 0.000050 12.7 12.5 N/A 0.050 <0.000010 <0.000010 N/A 0.000010 104 102 N/A 2.0 0.432 0.439 N/A 0.00020 <0.000010 <0.000010 N/A 0.000010 <0.00010 <0.00010 N/A 0.00010 <0.010 <0.010 N/A 0.010 0.00285 0.00295 N/A 0.000010 0.00478 0.00501 N/A 0.00050 <0.0030 <0.0030 N/A 0.0030 1 7 24 24 0.00076 0.00077 N/A 0.00010 <0.00050 <0.00050 N/A 0.00050 0.835 0.821 N/A 0.030 0.000057 <0.000050 N/A 0.000050 0.205 0.199 N/A 0.0010 102 101 N/A 0.10 0.115 0.116 N/A 0.00010 0.00295 0.00300 N/A 0.000050 0.0103 0.0103 N/A 0.00050 <0.30 <0.30 N/A 0.30 6.9 6.7 N/A 2.0 0.0319 0.0344 N/A 0.000050 6.45 6.39 N/A 0.050 <0.000010 <0.000010 N/A 0.000010 97.4 95.7 N/A 2.0 0.419 0.417 N/A 0.00020 <0.000010 <0.000010 N/A 0.000010 <0.00010 <0.00010 N/A 0.00010 <0.010 <0.010 N/A 0.010 0.0107 0.0104 N/A 0.000010 0.00204 0.00201 N/A 0.00050 0.0032 <0.0030 N/A 0.0030 17-Jun-2015 17-Jun-2015 Duplicate RPD Specific MDL for Sample 7-Jul-2015 7-Jul-2015 Duplicate RPD Specific MDL for Sample 22-Jul-2015 22-Jul-2015 Duplicate RPD Specific MDL for Sample Page 2 of 2 Appendix D.3 QAQC - Blank Analysis QAQC CoA exceeded Physical Tests Date 17-Feb-15 24-Feb-15 11-Mar-15 25-MAR-15 08-APR-15 22-APR-15 05-MAY-15 20-MAY-15 02-JUN-15 08-JUN-15 23-Jun-15 7-Jul-2015 22-Jul-2015 Week 2 3 5 7 9 11 13 15 17 18 20 22 24 Organic Carbon Anions and Nutrients Hardness (as CaCO3) Alkalinity, Total (as CaCO3) Ammonia, Total (as N) Bromide (Br) Chloride (Cl) Fluoride (F) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 2 2 2 1 2 2 2.7 2 2.6 2 2 2 1 0.005 0.005 0.005 0.0057 0.005 0.005 0.005 0.0052 0.005 0.005 0.005 0.005 0.005 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.005 0.0154 0.0058 0.0276 0.0059 0.005 0.05 0.005 0.0080 0.005 0.005 0.005 0.005 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 Nitrate (as N) Nitrite (as N) Sulfate (SO4) Sulfide as S 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Dissolved Metals Continued Date Week 17-Feb-15 24-Feb-15 11-Mar-15 25-MAR-15 08-APR-15 22-APR-15 05-MAY-15 20-MAY-15 02-JUN-15 08-JUN-15 23-Jun-15 7-Jul-2015 22-Jul-2015 2 3 5 7 9 11 13 15 17 18 20 22 24 Copper (Cu)Dissolved Iron (Fe)Dissolved Lead (Pb)Dissolved Lithium (Li)Dissolved Magnesium (Mg)Dissolved Manganese (Mn)Dissolved Molybdenum (Mo)Dissolved Nickel (Ni)Dissolved 0.0005 0.0005 0.00278 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.00005 0.00005 0.00005 0.000103 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.0005 0.0005 0.0005 0.0005 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.00005 0.00005 0.000053 0.00005 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.00005 0.00005 0.00005 0.00005 0.000245 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 Page 1 of 2 Phosphorus Potassium (P)-Dissolved (K)-Dissolved 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 2 2 2 2 2 2 2 2 2 2 2 2 2 Dissolved Organic Carbon 0.5 3.36 0.5 0.5 0.5 0.5 0.5 0.5 0.59 0.5 0.5 0.5 N/A Appendix D.3 QAQC - Blank Analysis QAQC CoA exceeded Dissolved Metals Date Week 17-Feb-15 24-Feb-15 11-Mar-15 25-MAR-15 08-APR-15 22-APR-15 05-MAY-15 20-MAY-15 02-JUN-15 08-JUN-15 23-Jun-15 7-Jul-2015 22-Jul-2015 2 3 5 7 9 11 13 15 17 18 20 22 24 Aluminum (Al)Dissolved Antimony (Sb)Dissolved 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 Arsenic (As)- Barium (Ba)- Beryllium (Be)- Bismuth (Bi)Dissolved Dissolved Dissolved Dissolved 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.00005 0.00005 0.000131 0.00005 0.000176 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0005 0.0005 0.0005 0.0005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 Boron (B)Dissolved Cadmium (Cd)Dissolved Calcium (Ca)Dissolved Chromium (Cr)Dissolved Cobalt (Co)Dissolved 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00001 0.00001 0.00001 0.00001 0.000005 0.000005 0.000005 0.000005 0.000005 0.000005 0.000005 0.000005 0.000005 0.05 0.05 0.05 0.05 0.052 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 Tin (Sn)Dissolved Titanium (Ti)Dissolved Uranium (U)Dissolved Vanadium (V)Dissolved Zinc (Zn)Dissolved 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.001 0.001 0.001 0.001 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 Dissolved Metals Continued Date Week Selenium (Se)Dissolved Silicon (Si)Dissolved Silver (Ag)Dissolved 17-Feb-15 24-Feb-15 11-Mar-15 25-MAR-15 08-APR-15 22-APR-15 05-MAY-15 20-MAY-15 02-JUN-15 08-JUN-15 23-Jun-15 7-Jul-2015 22-Jul-2015 2 3 5 7 9 11 13 15 17 18 20 22 24 0.0001 0.0001 0.0001 0.0001 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.05 0.05 0.101 0.05 0.05 0.05 0.105 0.05 0.05 0.05 0.05 0.05 0.05 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 Sodium (Na)- Strontium (Sr)- Thallium (Tl)Dissolved Dissolved Dissolved 2 2 2 2 2 2 2 2 2 2 2 2 2 0.0002 0.0002 0.0002 0.0002 0.00032 0.0002 0.0002 0.0002 0.0002 0.0002 0.0002 0.0002 0.0002 Page 2 of 2 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 Appendix D.4 QAQC - Reference Analysis 20% RPD exceeded Dissolved Metals Result < 5x MDL 50% RPF exceeded Samples Date Week Aluminum (Al)-Dissolved Antimony (Sb)Dissolved Arsenic (As)Dissolved Barium (Ba)Dissolved Beryllium (Be)Dissolved Bismuth (Bi)Dissolved Boron (B)Dissolved Reference Reference Reference Reference Reference Reference Reference Reference Reference Reference Reference Reference Reference Detection Limit 17-Feb-15 24-Feb-15 11-Mar-15 25-MAR-15 08-APR-15 22-APR-15 06-May-15 20-MAY-15 02-JUN-15 08-JUN-15 17-Jun-2015 7-Jul-2015 22-Jul-2015 2 3 5 7 9 11 13 15 17 18 19 22 24 0.058 0.0564 0.0510 0.0577 0.0609 0.0723 0.0653 0.0724 0.0797 0.0735 0.0906 0.0951 0.109 0.0030 0.0428 0.0556 0.0462 0.0477 0.0505 0.0471 0.0469 0.0486 0.0490 0.0496 0.0484 0.0476 0.0481 0.00010 0.0460 0.0476 0.0443 0.0468 0.0470 0.0464 0.0450 0.0463 0.0460 0.0447 0.0441 0.0472 0.0474 0.00010 0.0428 0.0465 0.0444 0.0456 0.0450 0.0438 0.0434 0.0457 0.0458 0.0455 0.0450 0.0464 0.0474 0.000050 0.0444 0.0449 0.0456 0.0438 0.0444 0.0439 0.0476 0.0443 0.0448 0.0445 0.0428 0.0461 0.0461 0.00010 <0.005 <0.00025 <0.00025 <0.00025 <0.00025 <0.00025 <0.00025 <0.00025 <0.00025 <0.00025 <0.00025 <0.00025 <0.00025 0.000050 0.1 0.053 0.058 0.061 0.068 0.077 0.080 0.082 0.089 0.095 0.103 0.140 0.190 0.050 0.0444 0.0472 0.0471 0.0477 0.0493 0.0466 0.0474 0.0481 0.0459 0.0488 0.0460 0.0466 0.0478 0.0000050 0.05 0.05 0.05 0.05 0.05 0.05 0.05 14.8% 12.0% 2.0% 14.3% 19.7% 36.5% 26.5% 36.6% 45.8% 38.1% 57.8% 62.2% 74.2% 74.2% 15.5% 10.6% 7.9% 4.7% 1.0% 6.0% 6.4% 2.8% 2.0% 0.8% 3.3% 4.9% 3.9% 15.5% 8.3% 4.9% 12.1% 6.6% 6.2% 7.5% 10.5% 7.7% 8.3% 11.2% 12.5% 5.8% 5.3% 12.5% 15.5% 7.3% 11.9% 9.2% 10.5% 13.2% 14.1% 9.0% 8.8% 9.4% 10.5% 7.5% 5.3% 15.5% 11.9% 10.7% 9.2% 13.2% 11.9% 13.0% 4.9% 12.1% 11.0% 11.6% 15.5% 8.1% 8.1% 15.5% N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A 0.0% 66.7% 5.8% 14.8% 19.8% 30.5% 42.5% 46.2% 48.5% 56.1% 62.1% 69.3% 94.7% 116.7% 116.7% Goal RPD between value and Goal Reference 17-Feb-15 Reference 24-Feb-15 Reference 11-Mar-15 Reference 25-MAR-15 Reference 08-APR-15 Reference 22-APR-15 Reference 06-May-15 Reference 20-MAY-15 Reference 02-JUN-15 Reference 08-JUN-15 Reference 17-Jun-2015 Reference 7-Jul-2015 Reference 22-Jul-2015 Max 2 3 5 7 9 11 13 15 17 18 19 22 24 Samples Date Week Reference Reference Reference Reference Reference Reference Reference Reference Reference Reference Reference Reference Reference Detection Limit Goal 17-Feb-15 24-Feb-15 11-Mar-15 25-MAR-15 08-APR-15 22-APR-15 06-May-15 20-MAY-15 02-JUN-15 08-JUN-15 17-Jun-2015 7-Jul-2015 22-Jul-2015 2 3 5 7 9 11 13 15 17 18 19 22 24 RPD between value and Goal Reference 17-Feb-15 Reference 24-Feb-15 Reference 11-Mar-15 Reference 25-MAR-15 Reference 08-APR-15 Reference 22-APR-15 Reference 06-May-15 Reference 20-MAY-15 Reference 02-JUN-15 Reference 08-JUN-15 Reference 17-Jun-2015 Reference 7-Jul-2015 Reference 22-Jul-2015 Max 2 3 5 7 9 11 13 15 17 18 19 22 24 Dissolved Metals Manganese Molybdenum (Mn)(Mo)Dissolved Dissolved 0.0449 0.0408 0.0457 0.0419 0.0421 0.0415 0.0450 0.0424 0.0465 0.0444 0.0448 0.0408 0.0431 0.0417 0.0439 0.0437 0.0458 0.0430 0.0424 0.0441 0.0442 0.0415 0.0432 0.0416 0.0449 0.0452 0.00010 0.000050 0.05 0.05 10.7% 9.0% 17.2% 10.5% 7.3% 11.0% 14.8% 13.0% 8.8% 16.5% 12.3% 14.6% 10.7% 17.2% 20.3% 17.6% 18.6% 16.5% 11.9% 20.3% 18.1% 13.4% 15.1% 12.5% 18.6% 18.3% 10.1% 20.3% Nickel (Ni)Dissolved Phosphorus Potassium (K)- Selenium (Se)- Silicon (Si)(P)-Dissolved Dissolved Dissolved Dissolved Chromium (Cr)Dissolved Cobalt (Co)Dissolved Copper (Cu)Dissolved Iron (Fe)Dissolved Lead (Pb)Dissolved Lithium (Li)Dissolved Magnesium (Mg)Dissolved 0.05 0.061 0.05 0.05 0.077 0.057 0.050 0.054 0.056 0.058 0.061 0.056 0.056 0.050 0.0429 0.0449 0.0425 0.0439 0.0433 0.0424 0.0431 0.0445 0.0438 0.0429 0.0429 0.0420 0.0434 0.00010 0.0432 0.0442 0.0426 0.0434 0.0450 0.0440 0.0432 0.0436 0.0431 0.0430 0.0435 0.0423 0.0465 0.00010 0.0425 0.0448 0.0426 0.0443 0.0444 0.0444 0.0435 0.0458 0.0430 0.0447 0.0447 0.0434 0.0473 0.00050 0.049 0.053 0.051 0.054 0.054 0.049 0.048 0.051 0.054 0.053 0.051 0.053 0.055 0.030 0.0418 0.0450 0.0439 0.0428 0.0440 0.0408 0.0422 0.0443 0.0452 0.0453 0.0435 0.0435 0.0455 0.000050 <0.0050 <0.0025 <0.0025 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 0.0010 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 <0.10 <0.10 <0.10 <0.10 <0.10 0.10 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 11.9% 5.8% 6.0% 4.7% 1.4% 7.0% 5.3% 3.9% 8.6% 2.4% 8.3% 7.0% 4.5% 11.9% 0.0% 19.8% 0.0% 0.0% 42.5% 13.1% 0.0% 7.7% 11.3% 14.8% 19.8% 11.3% 11.3% 42.5% 15.3% 10.7% 16.2% 13.0% 14.4% 16.5% 14.8% 11.6% 13.2% 15.3% 15.3% 17.4% 14.1% 17.4% 14.6% 12.3% 16.0% 14.1% 10.5% 12.8% 14.6% 13.7% 14.8% 15.1% 13.9% 16.7% 7.3% 16.7% 16.2% 11.0% 16.0% 12.1% 11.9% 11.9% 13.9% 8.8% 15.1% 11.2% 11.2% 14.1% 5.5% 16.2% 2.0% 5.8% 2.0% 7.7% 7.7% 2.0% 4.1% 2.0% 7.7% 5.8% 2.0% 5.8% 9.5% 9.5% 17.9% 10.5% 13.0% 15.5% 12.8% 20.3% 16.9% 12.1% 10.1% 9.9% 13.9% 13.9% 9.4% 20.3% N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A 0.0% N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A 0.0% Cadmium (Cd)- Calcium (Ca)Dissolved Dissolved Silver (Ag)Dissolved Sodium (Na)- Strontium (Sr)- Thallium (Tl)Dissolved Dissolved Dissolved Tin (Sn)Dissolved Titanium (Ti)- Uranium (U)- Vanadium (V)Dissolved Dissolved Dissolved Zinc (Zn)Dissolved 0.0434 0.0443 0.0437 0.0449 0.0462 0.0448 0.0434 0.0453 0.0433 0.0440 0.0431 0.0420 0.0465 0.00050 0.05 <0.30 <0.30 <0.30 <0.30 <0.30 <0.30 <0.30 <0.30 <0.30 <0.30 <0.30 <0.30 <0.30 0.30 0.05 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 2.0 0.05 0.0424 0.0420 0.0425 0.0411 0.0467 0.0444 0.0445 0.0430 0.0418 0.0423 0.0425 0.0397 0.0467 0.000050 0.05 0.224 0.268 0.312 0.429 0.544 0.643 0.784 0.937 1.09 1.16 1.29 1.69 2.04 0.050 0.050 0.0435 0.0547 0.0461 0.0493 0.0508 0.0436 0.0469 0.0490 0.0509 0.0498 0.0509 0.0483 0.0484 0.000010 0.05 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 2.0 0.05 0.0425 0.0428 0.0419 0.0431 0.0451 0.0424 0.0412 0.0437 0.0441 0.0443 0.0422 0.0424 0.0446 0.00020 0.05 0.0421 0.0446 0.0438 0.0425 0.0440 0.0395 0.0406 0.0435 0.0447 0.0447 0.0436 0.0437 0.0453 0.000010 0.05 0.0438 0.0494 0.0448 0.0475 0.0497 0.0467 0.0469 0.0482 0.0460 0.0482 0.0467 0.0464 0.0487 0.00010 0.05 0.048 0.051 0.047 0.050 0.052 0.049 0.049 0.049 0.050 0.050 0.050 0.049 0.051 0.010 0.05 0.0421 0.0441 0.0420 0.0421 0.0430 0.0392 0.0414 0.0442 0.0456 0.0450 0.0424 0.0437 0.0430 0.000010 0.05 0.044 0.0445 0.0431 0.0437 0.0443 0.0439 0.0436 0.0451 0.0438 0.0435 0.0426 0.0423 0.0461 0.00050 0.05 0.044 0.0495 0.0417 0.0423 0.0446 0.0458 0.0427 0.0452 0.0444 0.0423 0.0444 0.0437 0.0460 0.0030 0.05 14.1% 12.1% 13.4% 10.7% 7.9% 11.0% 14.1% 9.9% 14.4% 12.8% 14.8% 17.4% 7.3% 17.4% N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A 0.0% N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A 0.0% 16.5% 17.4% 16.2% 19.5% 6.8% 11.9% 11.6% 15.1% 17.9% 16.7% 16.2% 23.0% 6.8% 23.0% 127.0% 137.1% 144.8% 158.2% 166.3% 171.1% 176.0% 179.7% 182.5% 183.5% 185.1% 188.5% 190.4% 190.4% 13.9% 9.0% 8.1% 1.4% 1.6% 13.7% 6.4% 2.0% 1.8% 0.4% 1.8% 3.5% 3.3% 13.9% N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A 0.0% 16.2% 15.5% 17.6% 14.8% 10.3% 16.5% 19.3% 13.4% 12.5% 12.1% 16.9% 16.5% 11.4% 19.3% 17.2% 11.4% 13.2% 16.2% 12.8% 23.5% 20.8% 13.9% 11.2% 11.2% 13.7% 13.4% 9.9% 23.5% 13.2% 1.2% 11.0% 5.1% 0.6% 6.8% 6.4% 3.7% 8.3% 3.7% 6.8% 7.5% 2.6% 13.2% 4.1% 2.0% 6.2% 0.0% 3.9% 2.0% 2.0% 2.0% 0.0% 0.0% 0.0% 2.0% 2.0% 6.2% 17.2% 12.5% 17.4% 17.2% 15.1% 24.2% 18.8% 12.3% 9.2% 10.5% 16.5% 13.4% 15.1% 24.2% 12.8% 11.6% 14.8% 13.4% 12.1% 13.0% 13.7% 10.3% 13.2% 13.9% 16.0% 16.7% 8.1% 16.7% 12.8% 1.0% 18.1% 16.7% 11.4% 8.8% 15.7% 10.1% 11.9% 16.7% 11.9% 13.4% 8.3% 18.1% Appendix D.5 Crushed Mine Waste Rock Particle Size Analysis Client Sample ID SAMPLE 1 SAMPLE 2 SAMPLE 3 Date Sampled 29-Jul-2015 29-Jul-2015 29-Jul-2015 Units Soil Soil Soil % % % % % % % % % 57.8 14.7 8.61 5.55 3.10 2.05 2.16 3.68 2.38 50.8 14.6 11.0 7.10 4.01 2.56 2.76 4.39 2.80 57.1 13.7 9.84 5.83 3.31 2.00 2.11 3.76 2.36 Parameter % Gravel (>2mm) % Sand (2.00mm - 1.00mm) % Sand (1.00mm - 0.50mm) % Sand (0.50mm - 0.25mm) % Sand (0.25mm - 0.125mm) % Sand (0.125mm - 0.063mm) % Silt (0.063mm - 0.0312mm) % Silt (0.0312mm - 0.004mm) % Clay (<4um) Lowest Detection Limit 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Average 55.2 14.3 9.8 6.2 3.5 2.2 2.3 3.9 2.5 Appendix D.6 Parameter Crushed Mine Waste Rock Chemical Characterization SAMPLE 1 23-Jul-2015 SAMPLE 2 23-Jul-2015 SAMPLE 3 23-Jul-2015 Lowest Detection Limit Units Soil Soil Soil 0.25 0.10 0.010 % Unity % <0.25 8.1 <0.01 <0.25 8.1 0.01 <0.25 8.2 <0.01 0.050 % 0.88 0.77 0.79 1.0 0.30 1.0 1.0 0.010 Unity tCaCO3/1Kt tCaCO3/1Kt tCaCO3/1Kt Unity 2 6.3 57 51 9.12 2 8.8 57 48 6.51 2 7.5 55 48 7.33 0.010 0.050 0.10 10 0.050 0.010 10 0.010 0.010 0.020 0.050 1.0 0.10 0.20 0.050 0.050 0.20 0.020 0.0050 0.010 0.20 0.20 0.10 0.010 5.0 0.010 0.050 0.20 0.050 10 0.010 0.0010 0.10 0.10 0.20 0.010 0.010 0.20 0.010 0.010 0.010 0.020 0.20 0.20 0.0050 0.050 0.050 1.0 0.050 2.0 0.50 % ppm ppm ppm ppm ppm ppm ppm % ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm % ppm ppm ppm % ppm ppm ppm ppm ppm ppm % ppm ppm ppm ppm ppm % ppm % ppm ppm ppm ppm ppm % ppm ppm ppm ppm ppm ppm 0.8 0.78 5.8 570 0.96 0.17 10 2.06 2.12 14.75 1.15 18 6 21.1 2.21 0.11 0.2 0.06 0.035 1.64 9.1 11.5 8.2 0.27 128 0.1 2.18 33.7 0.05 830 0.26 0.006 19.1 4.7 2.9 0.34 0.05 96.5 0.1 0.01 0.04 0.03 3.9 0.6 0.005 0.05 1.73 76 12.8 171 2.5 0.77 0.98 7.1 620 0.9 0.17 10 2.64 1.94 14.95 1.09 18 7.5 23.9 2.35 0.1 0.2 0.06 0.04 1.47 9.2 12.8 7.8 0.26 115 0.13 2.89 43.6 0.05 790 0.25 0.005 18.6 4.7 2.9 0.39 0.04 93.8 0.15 0.01 0.05 0.03 4 0.7 0.005 0.05 1.9 88 13.2 199 2.5 0.7 0.89 6.2 610 0.87 0.17 10 2.35 1.98 14.2 1.04 17 6.8 21.6 1.96 0.1 0.2 0.06 0.035 1.47 8.7 12 7.1 0.25 115 0.12 2.69 37.8 0.05 790 0.22 0.005 17 4.5 2.7 0.4 0.04 90.9 0.12 0.01 0.04 0.03 3.8 0.6 0.005 0.05 1.79 86 12.1 178 2.4 0.20 % 3.2 2.8 2.9 Physical Tests (Soil) Moisture pH Acid Soluble Sulphate Sulphur Organic / Inorganic Carbon (Soil) Carbon (C) Acid Base Accounting (Soil) FIZZ RATING MPA Neutralization Potential (NP) NNP Ratio (NP/MPA) Total Metals (Soil) Aluminum (Al) Antimony (Sb) Arsenic (As) Barium (Ba) Beryllium (Be) Bismuth (Bi) Boron (B) Cadmium (Cd) Calcium (Ca) Cerium (Ce) Cesium (Cs) Chromium (Cr) Cobalt (Co) Copper (Cu) Gallium (Ga) Germanium (Ge) Gold (Au) Hafnium (Hf) Indium (In) Iron (Fe) Lanthanum (La) Lead (Pb) Lithium (Li) Magnesium (Mg) Manganese (Mn) Mercury (Hg) Molybdenum (Mo) Nickel (Ni) Niobium (Nb) Phosphorus (P) Potassium (K) Rhenium (Re) Rubidium (Rb) Scandium (Sc) Selenium (Se) Silver (Ag) Sodium (Na) Strontium (Sr) Sulfur (S) Tantalum (Ta) Tellurium (Te) Thallium (Tl) Thorium (Th) Tin (Sn) Titanium (Ti) Tungsten (W) Uranium (U) Vanadium (V) Yttrium (Y) Zinc (Zn) Zirconium (Zr) Permanent Gases (Soil) Carbon Dioxide (CO2) Appendix D.7 Hay Chemical Characterization Sample ID Date Sampled Matrix SAMPLE 1 - HAY 07-SEP-14 Soil SAMPLE 2 - HAY 07-SEP-14 Soil SAMPLE 3 - HAY 07-SEP-14 Soil Physical Tests Moisture 11.2 13.7 13.3 Leachable Anions & Nutrients Bromide (Br) Chloride (Cl) Nitrate (as N) Nitrite (as N) Sulfate (SO4) <25 2160 4.3 <0.50 1600 <25 2420 150 <0.50 2490 <25 640 10.6 <0.50 <500 Anions and Nutrients Total Nitrogen by LECO 1.22 1.19 1.04 Organic / Inorganic Carbon Total Organic Carbon 43.7 44.9 44.2 Plant Available Nutrients Available Ammonium-N 41.7 130 75.1 Metals Aluminum (Al) Antimony (Sb) Arsenic (As) Barium (Ba) Beryllium (Be) Bismuth (Bi) Cadmium (Cd) Calcium (Ca) Chromium (Cr) Cobalt (Co) Copper (Cu) Iron (Fe) Lead (Pb) Lithium (Li) Magnesium (Mg) Manganese (Mn) Molybdenum (Mo) Nickel (Ni) Phosphorus (P) Potassium (K) Selenium (Se) Silver (Ag) Sodium (Na) Strontium (Sr) Sulfur (S)-Total Thallium (Tl) Tin (Sn) Titanium (Ti) Uranium (U) Vanadium (V) Zinc (Zn) <50 <0.10 0.066 62.0 <0.20 <0.20 0.179 5310 <0.50 <0.10 3.38 84 <0.50 <5.0 966 11.3 1.37 <0.50 582 11300 0.20 <0.10 <100 20.4 1900 <0.050 <2.0 <1.0 <0.050 0.36 14.1 51 <0.10 0.060 54.9 <0.20 <0.20 0.131 5030 <0.50 <0.10 2.72 147 <0.50 <5.0 985 18.1 1.15 0.54 502 7780 <0.20 <0.10 <100 13.0 1500 <0.050 <2.0 <1.0 <0.050 0.47 15.3 <50 <0.10 <0.050 49.3 <0.20 <0.20 0.107 4510 <0.50 <0.10 2.88 74 <0.50 <5.0 893 19.0 2.64 0.57 558 9650 <0.20 <0.10 <100 15.5 1600 <0.050 <2.0 <1.0 <0.050 0.33 16.0 Appendix D.8 Sawdust Chemical Characterization Sample ID Date Sampled Matrix SAMPLE 1SAWDUST 07-SEP-14 Soil SAMPLE 2SAWDUST 07-SEP-14 Soil SAMPLE 3SAWDUST 07-SEP-14 Soil Physical Tests Moisture 17.2 16.4 17.8 Leachable Anions & Nutrients Bromide (Br) Chloride (Cl) Nitrate (as N) Nitrite (as N) Sulfate (SO4) <5.0 <50 <0.50 <0.10 <100 <5.0 <50 <0.50 <0.10 <100 <5.0 <50 <0.50 <0.10 <100 Anions and Nutrients Total Nitrogen by LECO 0.062 0.051 0.048 Organic / Inorganic Carbon Total Organic Carbon 47.5 47.8 48.0 Metals Aluminum (Al) Antimony (Sb) Arsenic (As) Barium (Ba) Beryllium (Be) Bismuth (Bi) Cadmium (Cd) Calcium (Ca) Chromium (Cr) Cobalt (Co) Copper (Cu) Iron (Fe) Lead (Pb) Lithium (Li) Magnesium (Mg) Manganese (Mn) Molybdenum (Mo) Nickel (Ni) Phosphorus (P) Potassium (K) Selenium (Se) Silver (Ag) Sodium (Na) Strontium (Sr) Sulfur (S)-Total Thallium (Tl) Tin (Sn) Titanium (Ti) Uranium (U) Vanadium (V) Zinc (Zn) <50 <0.10 <0.050 17.3 <0.20 <0.20 0.102 753 <0.50 0.22 2.38 73 <0.50 <5.0 117 34.4 <0.50 <0.50 <50 350 <0.20 <0.10 <100 2.05 2000 <0.050 <2.0 2.2 <0.050 <0.20 10.2 <50 <0.10 <0.050 16.7 <0.20 <0.20 0.095 687 <0.50 <0.10 1.97 <50 <0.50 <5.0 104 32.5 <0.50 <0.50 <50 310 <0.20 <0.10 <100 2.05 1500 <0.050 <2.0 1.3 <0.050 <0.20 9.1 <50 <0.10 <0.050 17.4 <0.20 <0.20 0.100 699 <0.50 <0.10 2.54 <50 <0.50 <5.0 100 33.5 <0.50 <0.50 <50 290 <0.20 <0.10 <100 1.95 1300 <0.050 <2.0 <1.0 <0.050 <0.20 9.7 Appendix D.9 Date 11-Feb-15 17-Feb-15 24-Feb-15 1-Mar-15 10-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 No Data 14-Apr-15 21-Apr-15 No Data 6-May-15 12-May-15 20-May-15 25-May-15 02-Jun-15 No Data 16-Jun-15 23-Jun-15 No Data 07-Jul-15 15-Jul-15 21-Jul-15 Tabulated Water Results - Dissolved Oxygen Week 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Column 1 17.10 6.50 Column 2 28.40 32.70 Column 5 9.20 20.80 Column 6 21.80 25.10 Inlet 57.70 7.47 10.80 9.90 15.60 19.90 26.90 20.00 28.50 10.60 23.40 35.30 41.68 38.50 66.50 44.30 31.10 37.86 40.70 13.10 6.20 21.00 14.10 5.53 5.70 25.50 58.10 10.60 37.90 118.00 15.80 7.50 16.30 19.80 9.40 52.20 79.80 67.53 74.20 32.10 13.00 30.70 6.00 1.50 12.30 47.30 57.60 46.10 40.30 25.70 130.90 172.30 106.25 132.00 71.10 28.80 63.40 17.40 41.05 115.40 17.23 24.60 26.70 69.80 47.00 46.70 17.30 7.31 5.40 56.30 55.20 44.80 136.50 121.30 100.83 All values are presented in units % Oxygen saturation 58.90 80.90 79.60 Appendix D.9 Date 11-Feb-15 17-Feb-15 24-Feb-15 1-Mar-15 10-Mar-15 No Data No Data 31-Mar-15 8-Apr-15 14-Apr-15 21-Apr-15 No Data No Data 12-May-15 20-May-15 25-May-15 02-Jun-15 No Data 16-Jun-15 23-Jun-15 No Data 07-Jul-15 15-Jul-15 21-Jul-15 Tabulated Water Results - ORP Week 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Column 1 63 -155 -73 -118 -71 Column 2 15 39 50 33 Column 5 30 -7 -132 -86 -100 Column 6 104 10 45 35 -2 Inlet 107 58 28 22 -107 -138 -168 -37 44 24 26 81 -244 -155 -189 -201 -30 51 36 59 34 4 1 72 -213 -140 -82 -59 -200 33 296 -37 -15 -58 -66 9 -164 45 38 23 -122 288 41 57 -105 -6 20 -114 21 6 -7 18 20 -13 7 7 71 7 7 102 8 8 -66 7 7 All values are presented in units of mV 8 7 Appendix D.9 Date 11-Feb-15 17-Feb-15 24-Feb-15 1-Mar-15 10-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 No Data 14-Apr-15 21-Apr-15 No Data 6-May-15 12-May-15 20-May-15 25-May-15 02-Jun-15 No Data 16-Jun-15 23-Jun-15 No Data 07-Jul-15 15-Jul-15 21-Jul-15 Tabulated Water Results - pH Week 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Column 1 6.19 6.11 6.13 6.08 6.04 6.02 6.35 6.41 Column 2 7.17 7.22 6.84 7.07 Column 6 7.06 7.07 6.92 7.18 6.95 6.99 7.57 7.27 Inlet 7.62 7.61 7.42 7.16 7.33 7.19 7.24 Column 5 6.42 6.30 6.31 6.32 6.27 6.45 6.62 6.77 6.54 6.46 7.51 7.00 6.85 6.67 7.24 6.78 7.82 7.66 6.67 6.45 6.40 6.51 6.67 7.15 6.96 7.02 7.21 7.28 6.78 6.58 6.83 6.86 6.90 7.04 6.97 6.95 6.83 7.01 7.71 7.44 7.59 7.61 7.88 6.56 6.86 7.28 7.98 6.83 7.07 7.09 7.53 7.59 7.81 6.61 6.81 6.59 7.18 7.56 7.19 6.97 7.02 6.75 7.27 7.36 7.01 8.14 7.99 7.67 All values are presented in units of pH 7.73 7.66 7.61 Appendix D.9 Tabulated Water Quality - Chemical Characterization Hardness (as CaCO3) Alkalinity Total Ammonia, Total (as CaCO3) (as N) Bromide (Br) Chloride (Cl) Fluoride (F) Nitrate (as N) Nitrite (as N) 0.0069 0.005 0.005 #N/A #N/A #N/A 0.005 #N/A 0.0063 #N/A 0.005 #N/A 0.005 #N/A 0.005 #N/A #N/A 0.005 0.005 1 1 1 #N/A #N/A #N/A 0.5 #N/A 0.5 #N/A 1 #N/A 0.5 #N/A 1 #N/A #N/A 0.5 0.5 11.0 12.0 10.5 #N/A #N/A #N/A 9.5 #N/A 10.2 #N/A 10.0 #N/A 10.2 #N/A 10.0 #N/A #N/A 10.3 10.4 0.4 0.4 0.2 #N/A #N/A #N/A 0.2 #N/A 0.2 #N/A 0.4 #N/A 0.2 #N/A 0.4 #N/A #N/A 0.2 0.2 73.6 72.7 73.2 #N/A #N/A #N/A 70.9 #N/A 74.1 #N/A 74.1 #N/A 74.7 #N/A 73.4 #N/A #N/A 74.0 75.6 0.02 0.02 0.011 #N/A #N/A #N/A 0.01 #N/A 0.01 #N/A 0.02 #N/A 0.010 #N/A 0.02 #N/A #N/A 0.01 0.01 #N/A #N/A 111 #N/A #N/A 0.005 #N/A #N/A 1 #N/A #N/A 10.0 #N/A #N/A 0.4 #N/A #N/A 72.4 #N/A #N/A 0.02 #N/A 908 #N/A 97.8 #N/A 0.005 #N/A 0.5 #N/A 10.0 #N/A 0.2 #N/A 73.4 #N/A 0.01 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 1530 1810 1410 #N/A 1950 2040 1220 1400 1230 #N/A 1090 964 932 996 1010 #N/A 908 971 974 1010 869 3880 1040 #N/A 1310 1410 768 981 995 #N/A 861 770 554 787 839 641 880 767 728 692 8.79 5.47 0.258 #N/A 0.72 1.61 1.03 0.991 0.715 #N/A 0.0544 0.0085 0.0168 0.0189 0.0102 0.0153 0.0107 0.0643 0.0093 0.0690 1 2.5 1 #N/A 1 1 1 1 0.5 #N/A 1 1 0.5 0.5 1 0.5 0.5 0.5 0.5 0.5 21.0 25.0 11.0 #N/A 10.0 10.0 10.0 10.0 10.1 #N/A 10.0 10.0 10.2 10.4 10.0 10.0 10.0 10.1 10.0 9.9 0.4 1 0.4 #N/A 0.4 0.4 0.4 0.4 0.2 #N/A 0.4 0.4 0.26 0.30 0.4 0.26 0.28 0.26 0.27 0.22 0.1 0.26 0.16 #N/A 2.54 2.47 0.1 0.1 0.05 #N/A 0.1 0.1 0.05 0.05 0.1 0.05 0.05 1.61 0.05 0.490 0.02 0.05 0.02 #N/A 0.070 0.038 0.026 0.02 0.01 #N/A 0.02 0.02 0.01 0.01 0.02 0.030 0.022 0.219 0.046 0.176 #N/A 1060 1040 1010 #N/A 666 674 467 #N/A 0.0686 0.0107 0.005 #N/A 0.25 0.5 0.5 #N/A 9.6 10.2 10.0 #N/A 0.31 0.28 0.2 #N/A 0.652 1.60 22.6 #N/A 0.0679 0.013 0.117 1 2 3 4 5 6 7 8 9 10 11 907 #N/A 926 #N/A #N/A #N/A 903 #N/A 951 #N/A 953 134 #N/A 151 #N/A #N/A #N/A 145 #N/A 147 #N/A 149 0.0845 #N/A 0.0806 #N/A #N/A #N/A 0.0747 #N/A 0.0786 #N/A 0.0712 1 #N/A 0.5 #N/A #N/A #N/A 0.5 #N/A 0.5 #N/A 1 11.0 #N/A 10.9 #N/A #N/A #N/A 9.7 #N/A 10.2 #N/A 10.0 0.67 #N/A 0.51 #N/A #N/A #N/A 0.31 #N/A 0.29 #N/A 0.4 74.5 #N/A 73.7 #N/A #N/A #N/A 72.7 #N/A 74.2 #N/A 73.0 0.134 #N/A 0.097 #N/A #N/A #N/A 0.014 #N/A 0.011 #N/A 0.02 Date Week Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 931 948 930 #N/A #N/A #N/A 895 #N/A 910 #N/A #N/A #N/A 934 #N/A 920 #N/A #N/A 912 932 118 121 121 #N/A #N/A #N/A 108 #N/A 116 #N/A 118 #N/A 118 #N/A 113 #N/A #N/A 114 110 #N/A #N/A 918 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 Speciation samples collected No sample collected More than 15% of results are less than or equal to the MDL, no mean calculated Results discarded due to irregularities Bold Values are less than or equal to the MDL 0-15% of values are less than or equal to the MDL, 0.5 x MDL used as replacement value in mean calculation Appendix D.9 Tabulated Water Quality - Chemical Characterization Hardness (as CaCO3) Alkalinity Total Ammonia, Total (as CaCO3) (as N) Bromide (Br) Chloride (Cl) Fluoride (F) Nitrate (as N) Nitrite (as N) #N/A 0.0913 #N/A 0.0843 #N/A 0.0827 0.0746 0.0715 #N/A 1 #N/A 1 #N/A 0.5 1 2.5 #N/A 10.0 #N/A 10.0 #N/A 9.9 11.0 25.0 #N/A 0.4 #N/A 0.4 #N/A 0.22 0.4 1 #N/A 75.6 #N/A 73.8 #N/A 72.8 74.8 74.3 #N/A 0.02 #N/A 0.02 #N/A 0.01 0.02 0.05 #N/A #N/A 147 #N/A #N/A 0.0714 #N/A #N/A 1 #N/A #N/A 10.0 #N/A #N/A 0.4 #N/A #N/A 72.7 #N/A #N/A 0.02 #N/A 939 #N/A 135 #N/A 0.0610 #N/A 0.5 #N/A 10.3 #N/A 0.23 #N/A 75.2 #N/A 0.01 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 1150 #N/A 1190 #N/A 1120 #N/A 940 #N/A 969 #N/A 976 #N/A 939 #N/A 941 #N/A 918 932 938 638 #N/A 783 #N/A 873 #N/A 771 #N/A 884 #N/A 834 #N/A 663 #N/A 624 #N/A 468 495 463 7.44 #N/A 2.57 #N/A 0.120 #N/A 0.225 #N/A 0.288 #N/A 0.485 #N/A 0.0189 #N/A 0.0084 #N/A 0.0058 0.0589 0.0069 1 #N/A 0.5 #N/A 1 #N/A 0.5 #N/A 0.5 #N/A 1 #N/A 0.5 #N/A 1 #N/A 0.5 0.5 0.5 12.0 #N/A 10.8 #N/A 10.0 #N/A 9.5 #N/A 9.9 #N/A 10.0 #N/A 10.2 #N/A 10.0 #N/A 9.8 10.2 9.8 0.44 #N/A 0.29 #N/A 0.4 #N/A 0.21 #N/A 0.22 #N/A 0.4 #N/A 0.36 #N/A 0.4 #N/A 0.30 0.32 0.29 0.1 #N/A 0.14 #N/A 0.1 #N/A 0.05 #N/A 11.9 #N/A 0.1 #N/A 9.52 #N/A 7.68 #N/A 14.8 6.59 5.18 19.7 #N/A 0.075 #N/A 0.021 #N/A 0.026 #N/A 0.438 #N/A 0.642 #N/A 0.155 #N/A 0.044 #N/A 0.028 0.359 0.055 #N/A #N/A 960 #N/A #N/A 577 #N/A #N/A 0.0063 #N/A #N/A 1 #N/A #N/A 10.0 #N/A #N/A 0.4 #N/A #N/A 7.79 #N/A #N/A 0.031 #N/A 967 #N/A 370 #N/A 0.005 #N/A 0.5 #N/A 10.2 #N/A 0.23 #N/A 23.9 #N/A 0.029 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 907 943 932 #N/A 894 939 921 972 927 #N/A 967 942 953 933 959 #N/A 894 930 940 979 186 213 220 #N/A 252 280 201 213 211 #N/A 197 194 196 199 193 183 192 202 186 199 0.0902 0.0798 0.0479 #N/A 0.0128 0.0090 0.0195 0.0374 0.0321 #N/A 0.0536 0.0398 0.0424 0.0414 0.0419 0.0504 0.0466 0.0485 0.0412 0.0338 1 1 1 #N/A 1 0.5 0.5 0.5 0.5 #N/A 1 1 0.5 0.5 1 0.5 0.5 1 0.5 0.5 15.0 14.0 10.6 #N/A 11.0 10.5 9.8 10.3 10.3 #N/A 10.0 10.0 10.2 10.4 10.0 10.0 10.0 10.0 10.0 9.9 0.68 0.75 0.53 #N/A 0.4 0.39 0.37 0.32 0.36 #N/A 0.4 0.4 0.29 0.34 0.4 0.27 0.29 0.4 0.31 0.31 56.5 50.1 48.9 #N/A 46.3 42.9 56.2 55.1 54.4 #N/A 56.6 57.8 58.9 58.0 58.6 60.9 60.2 58.3 56.4 54.7 2.18 2.79 1.44 #N/A 0.162 0.099 0.057 0.090 0.099 #N/A 0.042 0.086 0.055 0.039 0.02 0.016 0.016 0.02 0.016 0.016 #N/A 944 940 947 #N/A 199 192 174 #N/A 0.0656 0.0682 0.0410 #N/A 1 0.5 0.5 #N/A 10.0 10.1 10.0 #N/A 0.4 0.31 0.27 #N/A 54.8 54.9 61.2 #N/A 0.02 0.027 0.064 Date Week Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 12 13 14 15 16 17 18 19 20 21 22 23 24 #N/A 965 #N/A 959 #N/A 938 944 928 #N/A 145 #N/A 141 #N/A 143 147 #N/A #N/A #N/A 955 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 Speciation samples collected No sample collected More than 15% of results are less than or equal to the MDL, no mean calculated Results discarded due to irregularities Bold Values are less than or equal to the MDL 0-15% of values are less than or equal to the MDL, 0.5 x MDL used as replacement value in mean calculation Appendix D.9 Tabulated Water Quality - Chemical Characterization Dissolved Organic Carbon Aluminum (Al)- Antimony (Sb)Dissolved Dissolved Arsenic (As)Dissolved Barium (Ba)Dissolved Beryllium (Be)Dissolved 0.00188 0.00192 0.00196 #N/A #N/A #N/A 0.00198 #N/A 0.00186 #N/A 0.00189 #N/A 0.00191 #N/A 0.00187 #N/A #N/A 0.00184 0.00172 0.00016 0.00018 0.00018 #N/A #N/A #N/A 0.00017 #N/A 0.00016 #N/A 0.00015 #N/A 0.00016 #N/A 0.00017 #N/A #N/A 0.00016 0.00016 0.0266 0.0262 0.0269 #N/A #N/A #N/A 0.0267 #N/A 0.0284 #N/A 0.0265 #N/A 0.0267 #N/A 0.0247 #N/A #N/A 0.0269 0.0283 0.0001 0.0001 0.0001 #N/A #N/A #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A #N/A 0.0001 0.0001 #N/A #N/A 0.0111 #N/A #N/A 0.00185 #N/A #N/A 0.00018 #N/A #N/A 0.0269 #N/A #N/A 0.0001 #N/A #N/A #N/A 0.003 #N/A 0.00189 #N/A 0.00017 #N/A 0.0282 #N/A 0.0001 0.189 0.218 4.28 #N/A 0.81 2.05 0.62 1.58 0.82 #N/A 1.09 0.031 0.26 0.173 0.215 1.01 0.57 6.7 5.2 3.42 583 1110 629 #N/A 886 825 237 381 219 #N/A 112 #N/A 29.1 38.9 39.1 48.3 33.6 36.8 50.3 4.39 0.118 0.0929 0.0670 #N/A 0.0345 0.0383 0.0143 0.0247 0.0175 #N/A 0.0155 #N/A 0.0103 0.0140 0.0147 0.0174 0.0155 0.0125 0.0145 0.0138 0.0516 0.00577 0.00273 #N/A 0.00216 0.00219 0.00356 0.00250 0.00367 #N/A 0.00426 #N/A 0.00474 0.00523 0.00369 0.00293 0.00340 0.00265 0.00288 0.00304 0.0548 0.00391 0.00325 #N/A 0.00673 0.00858 0.00668 0.00712 0.00763 #N/A 0.00866 #N/A 0.00793 0.00865 0.00790 0.00955 0.0106 0.00817 0.00965 0.00811 0.0845 0.0818 0.473 #N/A 2.14 0.957 0.183 0.497 0.535 #N/A 0.552 #N/A 0.415 0.405 0.368 0.304 0.339 0.176 0.378 0.260 0.0002 0.0002 0.0002 #N/A 0.0005 0.001 0.0002 0.0002 0.0002 #N/A 0.0001 #N/A 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 #N/A 573 611 706 #N/A 5.5 1.32 0.206 #N/A 33.3 #N/A #N/A #N/A 0.0186 0.0156 0.0073 #N/A 0.00233 0.00222 0.00444 #N/A 0.00912 0.00697 0.00566 #N/A 0.381 0.265 0.111 #N/A 0.0001 0.0001 0.0001 796 #N/A 786 #N/A #N/A #N/A 772 #N/A 788 #N/A 775 0.02 #N/A 0.02 #N/A #N/A #N/A #N/A #N/A 0.02 #N/A 0.02 3.07 #N/A 2.17 #N/A #N/A #N/A 2.71 #N/A 2.40 #N/A 2.41 0.003 #N/A 0.003 #N/A #N/A #N/A 0.003 #N/A 0.003 #N/A 0.003 0.00416 #N/A 0.00427 #N/A #N/A #N/A 0.00426 #N/A 0.00392 #N/A 0.00357 0.00025 #N/A 0.00024 #N/A #N/A #N/A 0.00020 #N/A 0.00022 #N/A 0.00023 0.0169 #N/A 0.0177 #N/A #N/A #N/A 0.0164 #N/A 0.0180 #N/A 0.0170 0.0001 #N/A 0.0001 #N/A #N/A #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 Date Week Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 782 773 778 #N/A #N/A #N/A 746 #N/A 784 #N/A 786 #N/A 789 #N/A 772 #N/A #N/A 783 801 0.02 0.02 0.02 #N/A #N/A #N/A 0.02 #N/A 0.02 #N/A 0.02 #N/A 0.02 #N/A 0.02 #N/A #N/A 0.02 0.02 #N/A 5.06 3.74 #N/A #N/A #N/A 3.63 #N/A 4.14 #N/A 4.00 #N/A 3.83 #N/A 4.33 #N/A #N/A 4.36 4.55 0.003 0.003 0.003 #N/A #N/A #N/A 0.003 #N/A 0.0132 #N/A 0.003 #N/A 0.003 #N/A 0.003 #N/A #N/A 0.003 0.003 #N/A #N/A 764 #N/A #N/A 0.02 #N/A #N/A 3.82 #N/A 776 #N/A 0.02 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 803 719 175 #N/A 319 359 554 404 476 #N/A 456 583 517 548 509 476 553 546 487 532 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 1 2 3 4 5 6 7 8 9 10 11 Speciation samples collected Sulfate (SO4) Sulfide (as S) No sample collected More than 15% of results are less than or equal to the MDL, no mean calculated Results discarded due to irregularities Bold Values are less than or equal to the MDL 0-15% of values are less than or equal to the MDL, 0.5 x MDL used as replacement value in mean calculation Appendix D.9 Tabulated Water Quality - Chemical Characterization Arsenic (As)Dissolved Barium (Ba)Dissolved Beryllium (Be)Dissolved #N/A 0.00371 #N/A 0.00375 #N/A 0.00352 0.00363 0.00340 #N/A 0.00023 #N/A 0.00025 #N/A 0.00023 0.00022 0.00025 #N/A 0.0170 #N/A 0.0180 #N/A 0.0171 0.0174 0.0187 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 0.0001 0.0001 #N/A #N/A 0.003 #N/A #N/A 0.00351 #N/A #N/A 0.00023 #N/A #N/A 0.0188 #N/A #N/A 0.0001 #N/A #N/A #N/A 0.003 #N/A 0.00329 #N/A 0.00020 #N/A 0.0190 #N/A 0.0001 0.02 #N/A 0.88 #N/A 1.56 #N/A 7.2 #N/A 10.9 #N/A 4.6 #N/A 0.50 #N/A 0.264 #N/A 0.066 0.65 0.194 165 #N/A 277 #N/A 397 #N/A 152 #N/A 97.1 #N/A 40.3 #N/A 8.81 #N/A 12.9 #N/A 9.5 13.2 12.1 0.0284 #N/A 0.0445 #N/A 0.0356 #N/A 0.0251 #N/A 0.0150 #N/A 0.0167 #N/A 0.0083 #N/A 0.0085 #N/A 0.0070 0.0067 0.0064 0.0422 #N/A 0.00306 #N/A 0.00183 #N/A 0.00240 #N/A 0.00463 #N/A 0.00433 #N/A 0.00601 #N/A 0.00589 #N/A 0.00512 0.00470 0.00409 0.0370 #N/A 0.00470 #N/A 0.00626 #N/A 0.0106 #N/A 0.0127 #N/A 0.0146 #N/A 0.0115 #N/A 0.0107 #N/A 0.00728 0.00912 0.00818 0.0455 #N/A 0.0436 #N/A 0.314 #N/A 0.245 #N/A 0.365 #N/A 0.316 #N/A 0.200 #N/A 0.158 #N/A 0.138 0.122 0.138 0.0002 #N/A 0.0002 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 0.0001 0.0001 #N/A #N/A 643 #N/A #N/A 0.124 #N/A #N/A 11.2 #N/A #N/A 0.0075 #N/A #N/A 0.00467 #N/A #N/A 0.00717 #N/A #N/A 0.131 #N/A #N/A 0.0001 #N/A 764 #N/A 0.053 #N/A #N/A #N/A 0.0054 #N/A 0.00447 #N/A 0.00430 #N/A 0.0928 #N/A 0.0001 774 778 778 #N/A 803 816 768 784 786 #N/A 770 800 777 790 782 775 780 796 775 767 0.021 0.02 0.023 #N/A 0.02 0.02 0.02 0.02 #N/A #N/A #N/A 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 28.8 28.0 25.9 #N/A 17.5 17.0 11.7 11.3 9.39 #N/A 7.16 6.91 5.56 5.94 4.71 4.17 4.69 4.39 4.56 0.003 0.003 0.003 #N/A 0.003 0.0052 0.0066 0.0051 0.003 #N/A 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.00544 0.00557 0.00558 #N/A 0.00491 0.00512 0.00483 0.00503 0.00524 #N/A 0.00487 0.00492 0.00488 0.00548 0.00541 0.00502 0.00517 0.00568 0.00518 0.00570 0.00070 0.00049 0.00056 #N/A 0.00073 0.00095 0.00074 0.00083 0.00081 #N/A 0.00070 0.00069 0.00067 0.00082 0.00084 0.00064 0.00068 0.00074 0.00073 0.00071 0.0189 0.0188 0.0190 #N/A 0.0184 0.0197 0.0190 0.0183 0.0197 #N/A 0.0187 0.0181 0.0183 0.0189 0.0198 0.0185 0.0191 0.0189 0.0200 0.0187 0.0001 0.0001 0.0001 #N/A 0.0001 0.0005 0.0001 0.0001 0.0001 #N/A 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 #N/A 768 776 771 #N/A 0.02 0.02 0.02 #N/A 0.003 0.003 0.003 #N/A 0.00622 0.00570 0.00504 #N/A 0.00079 0.00069 0.00063 #N/A 0.0200 0.0201 0.0199 #N/A 0.0001 0.0001 0.0001 Aluminum (Al)- Antimony (Sb)Dissolved Dissolved Week Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 12 13 14 15 16 17 18 19 20 21 22 23 24 #N/A 805 #N/A 781 #N/A 769 794 780 #N/A 0.02 #N/A 0.02 #N/A 0.02 0.02 0.02 #N/A 1.04 #N/A 2.51 #N/A 2.82 2.65 2.53 #N/A 0.003 #N/A 0.003 #N/A 0.003 0.003 0.003 #N/A #N/A 769 #N/A #N/A 0.02 #N/A #N/A 2.83 #N/A 801 #N/A 0.02 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 754 #N/A 524 #N/A 248 #N/A 301 #N/A 420 #N/A 415 #N/A 598 #N/A 619 #N/A 670 654 588 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Speciation samples collected Sulfate (SO4) Sulfide (as S) Dissolved Organic Carbon Date No sample collected More than 15% of results are less than or equal to the MDL, no mean calculated #N/A #N/A 4.31 #N/A #N/A Results discarded due to irregularities Bold Values are less than or equal to the MDL 0-15% of values are less than or equal to the MDL, 0.5 x MDL used as replacement value in mean calculation Appendix D.9 Tabulated Water Quality - Chemical Characterization Bismuth (Bi)Dissolved Boron (B)Dissolved Cadmium (Cd)Dissolved 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 0.0005 0.0005 0.0005 #N/A #N/A #N/A 0.0005 #N/A 0.00005 #N/A 0.00005 #N/A 0.00005 #N/A 0.00005 #N/A #N/A 0.00005 0.00005 0.119 0.119 0.126 #N/A #N/A #N/A 0.119 #N/A 0.132 #N/A 0.103 #N/A 0.106 #N/A 0.135 #N/A #N/A 0.111 0.115 0.00001 0.00001 0.00001 #N/A #N/A #N/A 0.00001 #N/A 0.000005 #N/A 0.000005 #N/A 0.000005 #N/A 0.000005 #N/A #N/A 0.000005 0.000005 189 191 191 #N/A #N/A #N/A 178 #N/A 188 #N/A 188 #N/A 187 #N/A 191 #N/A #N/A 182 195 #N/A #N/A 0.00005 #N/A #N/A 0.096 #N/A #N/A 0.000005 #N/A 0.00005 #N/A 0.132 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 0.001 0.001 0.001 #N/A 0.0025 0.001 0.001 0.0001 0.0001 #N/A 0.00005 #N/A 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 #N/A 0.00005 0.00005 0.00005 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 1 2 3 4 5 6 7 8 9 10 11 0.0005 #N/A 0.0005 #N/A #N/A #N/A 0.0005 #N/A 0.00005 #N/A 0.00005 Date Week Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Speciation samples collected No sample collected Calcium (Ca)- Chromium (Cr)Dissolved Dissolved Cobalt (Co)Dissolved Copper (Cu)Dissolved Iron (Fe)Dissolved Lead (Pb)Dissolved 0.0001 0.0001 0.0001 #N/A #N/A #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A #N/A 0.0001 0.0001 0.00010 0.00010 0.00010 #N/A #N/A #N/A 0.00010 #N/A 0.00010 #N/A 0.00010 #N/A 0.00010 #N/A 0.00010 #N/A #N/A 0.00010 0.00010 0.00091 0.0005 0.0005 #N/A #N/A #N/A 0.0005 #N/A 0.0005 #N/A 0.0005 #N/A 0.0005 #N/A 0.0005 #N/A #N/A 0.0005 0.0005 0.03 0.03 0.03 #N/A #N/A #N/A 0.03 #N/A 0.03 #N/A 0.03 #N/A 0.03 #N/A 0.03 #N/A #N/A 0.03 0.03 0.000075 0.000089 0.000114 #N/A #N/A #N/A 0.000051 #N/A 0.00005 #N/A 0.00005 #N/A 0.000082 #N/A 0.00005 #N/A #N/A 0.00005 0.00005 #N/A #N/A 188 #N/A #N/A 0.0001 #N/A #N/A 0.00010 #N/A #N/A 0.0005 #N/A #N/A 0.03 #N/A #N/A 0.000065 #N/A 0.000005 #N/A 183 #N/A 0.0001 #N/A 0.00010 #N/A 0.0005 #N/A 0.03 #N/A 0.00005 0.533 0.555 0.446 #N/A 0.325 0.314 0.185 0.196 0.190 #N/A 0.162 #N/A 0.119 0.170 0.143 0.148 0.145 0.142 0.161 0.154 0.000320 0.000055 0.000037 #N/A 0.00005 0.00010 0.000021 0.000013 0.000014 #N/A 0.0000113 #N/A 0.0000113 0.0000143 0.0000094 0.0000118 0.0000064 0.000005 0.000005 0.0000131 440 542 418 #N/A 557 633 320 376 320 #N/A 279 #N/A 233 242 243 201 225 218 231 228 0.0106 0.00564 0.00426 #N/A 0.00316 0.0033 0.00125 0.00199 0.00154 #N/A 0.00139 #N/A 0.00120 0.00132 0.00142 0.00140 0.00132 0.00116 0.00144 0.00116 0.309 0.300 0.0168 #N/A 0.0236 0.0237 0.0129 0.00489 0.00352 #N/A 0.00246 #N/A 0.00293 0.00342 0.00173 0.00069 0.00067 0.00032 0.00040 0.00042 0.00455 0.00182 0.00067 #N/A 0.001 0.001 0.00071 0.0005 0.0005 #N/A 0.0005 #N/A 0.00068 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 26.3 25.2 20.3 #N/A 35.2 32.7 7.63 4.59 2.62 #N/A 1.80 #N/A 1.54 1.16 0.626 0.355 0.343 0.162 0.239 0.149 0.001170 0.000140 0.000130 #N/A 0.000250 0.000100 0.000220 0.000100 0.000100 #N/A 0.000100 #N/A 0.000099 0.000050 0.000050 0.000053 0.000050 0.000050 0.000050 0.000050 #N/A 0.147 0.160 0.138 #N/A 0.0000092 0.0000056 0.000005 #N/A 254 249 238 #N/A 0.00142 0.00124 0.00042 #N/A 0.00039 0.00038 0.00076 #N/A 0.0005 0.0005 0.0005 #N/A 0.055 0.063 0.835 #N/A 0.000050 0.000050 0.000057 0.198 #N/A 0.229 #N/A #N/A #N/A 0.202 #N/A 0.211 #N/A 0.160 0.00165 #N/A 0.00158 #N/A #N/A #N/A 0.00173 #N/A 0.00167 #N/A 0.00131 211 #N/A 206 #N/A #N/A #N/A 192 #N/A 207 #N/A 202 0.00010 #N/A 0.00010 #N/A #N/A #N/A 0.00010 #N/A 0.00010 #N/A 0.00010 0.0261 #N/A 0.0227 #N/A #N/A #N/A 0.0206 #N/A 0.0191 #N/A 0.0168 0.00162 #N/A 0.00107 #N/A #N/A #N/A 0.00153 #N/A 0.00124 #N/A 0.00100 0.03 #N/A 0.03 #N/A #N/A #N/A 0.03 #N/A 0.03 #N/A 0.03 0.00005 #N/A 0.00005 #N/A #N/A #N/A 0.00005 #N/A 0.00005 #N/A 0.00005 Results discarded due to irregularities More than 15% of results are less than or equal to the MDL, no mean calculated Bold Values are less than or equal to the MDL 0-15% of values are less than or equal to the MDL, 0.5 x MDL used as replacement value in mean calculation Appendix D.9 Tabulated Water Quality - Chemical Characterization Bismuth (Bi)Dissolved Boron (B)Dissolved Cadmium (Cd)Dissolved 12 13 14 15 16 17 18 19 20 21 22 23 24 #N/A 0.00005 #N/A 0.00005 #N/A 0.00005 0.00005 0.00005 #N/A 0.142 #N/A 0.159 #N/A 0.165 0.157 0.176 #N/A 0.00144 #N/A 0.00146 #N/A 0.00131 0.00118 0.00134 #N/A 200 #N/A 207 #N/A 195 197 204 #N/A #N/A 0.00005 #N/A #N/A 0.153 #N/A #N/A 0.00125 #N/A 0.00005 #N/A 0.178 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 0.001 #N/A 0.001 #N/A 0.0005 #N/A 0.0005 #N/A 0.00005 #N/A 0.00005 #N/A 0.00005 #N/A 0.00005 #N/A 0.00005 0.00005 0.00005 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Date Week Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Speciation samples collected Cobalt (Co)Dissolved Copper (Cu)Dissolved Iron (Fe)Dissolved Lead (Pb)Dissolved #N/A 0.00010 #N/A 0.00010 #N/A 0.00010 0.00010 0.00010 #N/A 0.0164 #N/A 0.0150 #N/A 0.0136 0.0140 0.0127 #N/A 0.00120 #N/A 0.00122 #N/A 0.00103 0.00097 0.00102 #N/A 0.03 #N/A 0.03 #N/A 0.03 0.03 0.03 #N/A 0.00005 #N/A 0.00005 #N/A 0.00005 0.00005 0.00005 #N/A #N/A 205 #N/A #N/A 0.0001 #N/A #N/A 0.0124 #N/A #N/A 0.00096 #N/A #N/A 0.03 #N/A #N/A 0.00005 #N/A 0.00118 #N/A 198 #N/A 0.00010 #N/A 0.0115 #N/A 0.00089 #N/A 0.03 #N/A 0.00005 0.419 #N/A 0.403 #N/A 0.306 #N/A 0.212 #N/A 0.206 #N/A 0.159 #N/A 0.117 #N/A 0.137 #N/A 0.139 0.140 0.150 0.00301 #N/A 0.000177 #N/A 0.000017 #N/A 0.000010 #N/A 0.0000151 #N/A 0.0000120 #N/A 0.0000078 #N/A 0.0000080 #N/A 0.0000062 0.000005 0.000005 312 #N/A 328 #N/A 298 #N/A 232 #N/A 229 #N/A 233 #N/A 205 #N/A 206 #N/A 204 197 207 0.00311 #N/A 0.00321 #N/A 0.00282 #N/A 0.00211 #N/A 0.00126 #N/A 0.00128 #N/A 0.00093 #N/A 0.00085 #N/A 0.00056 0.00072 0.00068 0.180 #N/A 0.0360 #N/A 0.00664 #N/A 0.00037 #N/A 0.00061 #N/A 0.00065 #N/A 0.00196 #N/A 0.00261 #N/A 0.00287 0.00168 0.00212 0.00322 #N/A 0.00156 #N/A 0.0005 #N/A 0.00066 #N/A 0.0005 #N/A 0.0005 #N/A 0.0005 #N/A 0.0005 #N/A 0.0005 0.0005 0.0005 3.26 #N/A 11.2 #N/A 15.7 #N/A 0.253 #N/A 0.058 #N/A 0.068 #N/A 0.396 #N/A 0.619 #N/A 0.555 0.536 0.526 0.00057 #N/A 0.00028 #N/A 0.000051 #N/A 0.00005 #N/A 0.00005 #N/A 0.00005 #N/A 0.000061 #N/A 0.00005 #N/A 0.00005 0.00005 0.00005 #N/A #N/A 0.00005 #N/A #N/A 0.131 #N/A #N/A 0.000005 #N/A #N/A 210 #N/A #N/A 0.00069 #N/A #N/A 0.00123 #N/A #N/A 0.0005 #N/A #N/A 0.248 #N/A #N/A 0.00005 #N/A 0.00005 #N/A 0.149 #N/A 0.000005 #N/A 212 #N/A 0.00025 #N/A 0.00116 #N/A 0.0005 #N/A 0.164 #N/A 0.00005 0.0005 0.0005 0.0005 #N/A 0.0005 0.0005 0.00005 0.00005 0.00005 #N/A 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.224 0.236 0.248 #N/A 0.209 0.252 0.178 0.211 0.230 #N/A 0.164 0.159 0.140 0.195 0.167 0.157 0.162 0.159 0.167 0.170 0.00238 0.00233 0.00209 #N/A 0.00189 0.00166 0.00175 0.00158 0.00136 #N/A 0.00137 0.00144 0.00113 0.00120 0.00105 0.00108 0.00106 0.000977 0.000989 0.000806 209 210 209 #N/A 199 206 198 215 208 #N/A 215 202 200 204 210 180 195 196 207 199 0.0001 0.0001 0.0001 #N/A 0.0001 0.0005 0.0001 0.0001 0.0001 #N/A 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0447 0.0413 0.0366 #N/A 0.0330 0.0364 0.0340 0.0322 0.0327 #N/A 0.0223 0.0198 0.0222 0.0255 0.0234 0.0184 0.0201 0.0184 0.0166 0.0182 0.00123 0.00072 0.00115 #N/A 0.0005 0.00113 0.00137 0.00056 0.00066 #N/A 0.00067 0.00095 0.00062 0.00062 0.00054 0.0005 0.0005 0.0005 0.0005 0.0005 0.03 0.03 0.03 #N/A 0.03 0.03 0.03 0.03 0.03 #N/A 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.000051 0.00005 0.00005 #N/A 0.000071 0.000114 0.000173 0.000061 0.000078 #N/A 0.00005 0.000063 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 #N/A 0.00005 0.00005 0.00005 #N/A 0.153 0.179 0.167 #N/A 0.000854 0.000525 0.00101 #N/A 205 203 199 #N/A 0.0001 0.0001 0.0001 #N/A 0.0187 0.0178 0.0162 #N/A 0.0005 0.0005 0.0005 #N/A 0.03 0.03 0.03 #N/A 0.00005 0.00005 0.00005 No sample collected Calcium (Ca)- Chromium (Cr)Dissolved Dissolved Results discarded due to irregularities More than 15% of results are less than or equal to the MDL, no mean calculated Bold Values are less than or equal to the MDL 0-15% of values are less than or equal to the MDL, 0.5 x MDL used as replacement value in mean calculation Appendix D.9 Tabulated Water Quality - Chemical Characterization Lithium (Li)Dissolved Magnesium (Mg)- Manganese (Mn)- Molybdenum Dissolved Dissolved (Mo)-Dissolved Nickel (Ni)- Phosphorous (P)- Potassium (K)- Selenium (Se)Dissolved Dissolved Dissolved Dissolved Silicon (Si)Dissolved Date Week Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 0.186 0.178 0.205 #N/A #N/A #N/A 0.208 #N/A 0.230 #N/A 0.174 #N/A 0.171 #N/A 0.215 #N/A #N/A 0.184 0.181 111 115 110 #N/A #N/A #N/A 110 #N/A 107 #N/A 112 #N/A 114 #N/A 108 #N/A #N/A 111 108 0.000097 0.000472 0.00005 #N/A #N/A #N/A 0.000056 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A #N/A 0.0001 0.0001 0.00432 0.00433 0.00424 #N/A #N/A #N/A 0.00415 #N/A 0.00402 #N/A 0.00411 #N/A 0.00450 #N/A 0.00444 #N/A #N/A 0.00430 0.00390 0.0583 0.0595 0.0570 #N/A #N/A #N/A 0.0588 #N/A 0.0627 #N/A 0.0582 #N/A 0.0591 #N/A 0.0590 #N/A #N/A 0.0571 0.0536 0.3 0.3 0.3 #N/A #N/A #N/A 0.3 #N/A 0.3 #N/A 0.3 #N/A 0.3 #N/A 0.3 #N/A #N/A 0.3 0.3 4.3 4.3 4.2 #N/A #N/A #N/A 4.3 #N/A 4.0 #N/A 4.5 #N/A 4.2 #N/A 4.0 #N/A #N/A 4.0 4.2 0.104 0.109 0.117 #N/A #N/A #N/A 0.111 #N/A 0.118 #N/A 0.106 #N/A 0.114 #N/A 0.108 #N/A #N/A 0.104 0.109 2.46 2.50 2.51 #N/A #N/A #N/A 2.59 #N/A 2.52 #N/A 2.60 #N/A 2.55 #N/A 2.62 #N/A #N/A 2.51 2.59 #N/A #N/A 0.195 #N/A #N/A 109 #N/A #N/A 0.0001 #N/A #N/A 0.00428 #N/A #N/A 0.0537 #N/A #N/A 0.3 #N/A #N/A 3.9 #N/A #N/A 0.108 #N/A #N/A 2.58 #N/A 0.204 #N/A 110 #N/A 0.0001 #N/A 0.00441 #N/A 0.0527 #N/A 0.3 #N/A 4.1 #N/A 0.107 #N/A 2.50 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 0.232 0.202 0.201 #N/A 0.211 0.224 0.201 0.176 0.229 #N/A 0.194 #N/A 0.147 0.211 0.195 0.206 0.212 0.184 0.196 0.205 104 111 90.0 #N/A 135 129 103 113 104 #N/A 95.2 #N/A 85.4 95.1 98.4 109 91.3 103 96.2 108 1.24 1.27 0.820 #N/A 0.790 0.774 0.261 0.252 0.185 #N/A 0.121 #N/A 0.0801 0.0847 0.0877 0.0848 0.0852 0.0840 0.0851 0.0905 0.0269 0.0143 0.00082 #N/A 0.00128 0.00077 0.00499 0.00199 0.00300 #N/A 0.00316 #N/A 0.00433 0.00498 0.00273 0.00151 0.00189 0.000888 0.000779 0.00135 1.20 1.07 0.0748 #N/A 0.0723 0.0940 0.0958 0.0413 0.0360 #N/A 0.0265 #N/A 0.0356 0.0368 0.0285 0.0187 0.0144 0.0114 0.0117 0.0117 0.91 0.62 1.23 #N/A 1.19 1.17 0.3 0.59 0.32 #N/A 0.3 #N/A 0.3 0.3 0.3 0.34 0.34 0.3 0.3 0.3 139 108 64.0 #N/A 47.0 41.4 23.7 23.8 17.8 #N/A 15.8 #N/A 12.0 12.2 11.6 10.2 10.7 9.0 9.6 9.0 0.0494 0.00273 0.00167 #N/A 0.00569 0.0057 0.0187 0.00580 0.0110 #N/A 0.0115 #N/A 0.0172 0.0114 0.0110 0.00661 0.0134 0.00859 0.00905 0.0167 16.1 20.0 24.2 #N/A 19.0 19.1 12.4 14.7 12.4 #N/A 12.9 #N/A 10.6 11.4 11.8 10.9 11.0 9.59 10.9 9.62 #N/A 0.202 0.209 0.205 #N/A 103 102 102 #N/A 0.107 0.122 0.115 #N/A 0.000818 0.000905 0.00295 #N/A 0.00829 0.00698 0.0103 #N/A 0.3 0.3 0.3 #N/A 12.4 10.1 6.9 #N/A 0.0177 0.0128 0.0319 #N/A 12.7 10.2 6.45 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 1 2 3 4 5 6 7 8 9 10 11 0.249 #N/A 0.238 #N/A #N/A #N/A 0.227 #N/A 0.246 #N/A 0.196 92.5 #N/A 100 #N/A #N/A #N/A 103 #N/A 106 #N/A 109 0.0805 #N/A 0.0991 #N/A #N/A #N/A 0.128 #N/A 0.131 #N/A 0.127 0.0241 #N/A 0.0206 #N/A #N/A #N/A 0.0150 #N/A 0.0129 #N/A 0.0121 0.143 #N/A 0.139 #N/A #N/A #N/A 0.125 #N/A 0.115 #N/A 0.102 0.3 #N/A 0.3 #N/A #N/A #N/A 0.3 #N/A 0.3 #N/A 0.3 4.6 #N/A 4.9 #N/A #N/A #N/A 5.0 #N/A 4.8 #N/A 5.4 0.137 #N/A 0.113 #N/A #N/A #N/A 0.111 #N/A 0.112 #N/A 0.101 2.14 #N/A 2.31 #N/A #N/A #N/A 2.36 #N/A 2.34 #N/A 2.44 Speciation samples collected No sample collected Results discarded due to irregularities More than 15% of results are less than or equal to the MDL, no mean calculated Bold Values are less than or equal to the MDL 0-15% of values are less than or equal to the MDL, 0.5 x MDL used as replacement value in mean calculation Appendix D.9 Tabulated Water Quality - Chemical Characterization Lithium (Li)Dissolved Magnesium (Mg)- Manganese (Mn)- Molybdenum Dissolved Dissolved (Mo)-Dissolved Nickel (Ni)- Phosphorous (P)- Potassium (K)- Selenium (Se)Dissolved Dissolved Dissolved Dissolved Silicon (Si)Dissolved Date Week Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 12 13 14 15 16 17 18 19 20 21 22 23 24 #N/A 0.162 #N/A 0.202 #N/A 0.221 0.182 0.201 #N/A 113 #N/A 108 #N/A 102 110 101 #N/A 0.124 #N/A 0.125 #N/A 0.122 0.125 0.123 #N/A 0.0120 #N/A 0.0107 #N/A 0.00987 0.0104 0.0101 #N/A 0.0984 #N/A 0.0928 #N/A 0.0821 0.0873 0.0810 #N/A 0.3 #N/A 0.3 #N/A 0.3 0.3 0.3 #N/A 4.8 #N/A 4.9 #N/A 4.5 4.7 4.6 #N/A 0.111 #N/A 0.108 #N/A 0.101 0.0913 0.0951 #N/A 2.31 #N/A 2.49 #N/A 2.24 2.33 2.34 #N/A #N/A 0.205 #N/A #N/A 107 #N/A #N/A 0.130 #N/A #N/A 0.0102 #N/A #N/A 0.0802 #N/A #N/A 0.3 #N/A #N/A 4.8 #N/A #N/A 0.0895 #N/A #N/A 2.50 #N/A 0.213 #N/A 108 #N/A 0.119 #N/A 0.00964 #N/A 0.0728 #N/A 0.3 #N/A 4.5 #N/A 0.0902 #N/A 2.32 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 0.217 #N/A 0.209 #N/A 0.195 #N/A 0.200 #N/A 0.234 #N/A 0.184 #N/A 0.147 #N/A 0.194 #N/A 0.207 0.187 0.185 90.0 #N/A 89.4 #N/A 90.2 #N/A 87.4 #N/A 96.2 #N/A 95.5 #N/A 104 #N/A 104 #N/A 99.2 107 102 0.887 #N/A 0.753 #N/A 0.547 #N/A 0.269 #N/A 0.177 #N/A 0.149 #N/A 0.112 #N/A 0.0911 #N/A 0.0864 0.0721 0.0714 0.0570 #N/A 0.0109 #N/A 0.00125 #N/A 0.000753 #N/A 0.00240 #N/A 0.00198 #N/A 0.00498 #N/A 0.00524 #N/A 0.00506 0.00434 0.00378 0.918 #N/A 0.252 #N/A 0.0351 #N/A 0.0153 #N/A 0.0207 #N/A 0.0234 #N/A 0.0281 #N/A 0.0381 #N/A 0.0366 0.0296 0.0328 0.55 #N/A 1.74 #N/A 2.14 #N/A 1.76 #N/A 0.95 #N/A 1.06 #N/A 0.65 #N/A 0.38 #N/A 0.3 0.36 0.3 67.4 #N/A 38.0 #N/A 25.7 #N/A 17.5 #N/A 11.5 #N/A 11.6 #N/A 9.6 #N/A 8.1 #N/A 7.6 7.4 7.3 0.102 #N/A 0.00230 #N/A 0.00471 #N/A 0.00501 #N/A 0.0198 #N/A 0.00637 #N/A 0.0178 #N/A 0.0161 #N/A 0.0223 0.00898 0.00787 10.7 #N/A 20.1 #N/A 20.0 #N/A 16.0 #N/A 10.4 #N/A 11.2 #N/A 8.40 #N/A 7.36 #N/A 6.42 6.74 6.85 #N/A #N/A 0.204 #N/A #N/A 106 #N/A #N/A 0.0850 #N/A #N/A 0.00488 #N/A #N/A 0.0184 #N/A #N/A 0.3 #N/A #N/A 7.1 #N/A #N/A 0.00939 #N/A #N/A 6.93 #N/A 0.203 #N/A 106 #N/A 0.0945 #N/A 0.00582 #N/A 0.0183 #N/A 0.3 #N/A 6.1 #N/A 0.0139 #N/A 5.46 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 0.216 0.206 0.228 #N/A 0.191 0.213 0.201 0.191 0.241 #N/A 0.187 0.177 0.165 0.213 0.206 0.215 0.215 0.192 0.194 0.213 93.5 102 99.7 #N/A 96.7 94.9 103 106 99.0 #N/A 104 107 110 103 106 116 98.6 107 103 117 0.247 0.239 0.251 #N/A 0.225 0.267 0.266 0.252 0.258 #N/A 0.184 0.165 0.167 0.190 0.178 0.159 0.169 0.159 0.157 0.167 0.0212 0.0212 0.0206 #N/A 0.0180 0.0212 0.0175 0.0167 0.0173 #N/A 0.0145 0.0156 0.0145 0.0158 0.0145 0.0121 0.0125 0.0136 0.0124 0.0136 0.233 0.212 0.187 #N/A 0.174 0.188 0.182 0.173 0.177 #N/A 0.134 0.127 0.122 0.117 0.117 0.102 0.101 0.104 0.0985 0.103 0.3 0.3 0.3 #N/A 0.3 0.3 0.3 0.3 0.3 #N/A 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 5.8 6.1 5.3 #N/A 5.5 5.19 5.4 5.3 4.9 #N/A 5.1 4.7 4.9 4.8 5.0 4.8 4.7 4.9 4.9 5.2 0.119 0.0998 0.0947 #N/A 0.0665 0.0578 0.0595 0.0599 0.0512 #N/A 0.0456 0.0407 0.0398 0.0319 0.0304 0.0326 0.0313 0.0234 0.0276 0.0234 2.51 2.64 2.65 #N/A 2.62 2.80 2.70 2.70 2.57 #N/A 2.56 2.46 2.45 2.58 2.67 2.41 2.36 2.52 2.53 2.52 #N/A 0.218 0.215 0.206 #N/A 105 105 109 #N/A 0.181 0.166 0.151 #N/A 0.0145 0.0136 0.0117 #N/A 0.101 0.0984 0.0896 #N/A 0.3 0.3 0.3 #N/A 5.0 4.7 4.7 #N/A 0.0249 0.0232 0.0422 #N/A 2.65 2.47 2.42 Speciation samples collected No sample collected Results discarded due to irregularities More than 15% of results are less than or equal to the MDL, no mean calculated Bold Values are less than or equal to the MDL 0-15% of values are less than or equal to the MDL, 0.5 x MDL used as replacement value in mean calculation Appendix D.9 Tabulated Water Quality - Chemical Characterization Silver (Ag)Dissolved Sodium (Na)- Strontium (Sr)- Thallium (Tl)Dissolved Dissolved Dissolved Tin (Sn)Dissolved Titanium (Ti)- Uranium (U)- Vanadium (V)Dissolved Dissolved Dissolved Date Week Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet Inlet 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 0.00001 0.00001 0.00001 #N/A #N/A #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 #N/A #N/A 0.00001 0.00001 101 104 103 #N/A #N/A #N/A 101 #N/A 96.2 #N/A 105 #N/A 97.4 #N/A 101 #N/A #N/A 98.6 103 0.339 0.345 0.333 #N/A #N/A #N/A 0.348 #N/A 0.332 #N/A 0.332 #N/A 0.343 #N/A 0.341 #N/A #N/A 0.327 0.311 0.000024 0.000031 0.000049 #N/A #N/A #N/A 0.000044 #N/A 0.000046 #N/A 0.000046 #N/A 0.000066 #N/A 0.000025 #N/A #N/A 0.000023 0.000021 0.0001 0.0001 0.0001 #N/A #N/A #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A #N/A 0.0001 0.0001 0.012 0.013 0.020 #N/A #N/A #N/A 0.01 #N/A 0.015 #N/A 0.013 #N/A 0.01 #N/A 0.012 #N/A #N/A 0.01 0.01 0.0202 0.0196 0.0211 #N/A #N/A #N/A 0.0198 #N/A 0.0200 #N/A 0.0190 #N/A 0.0220 #N/A 0.0205 #N/A #N/A 0.0204 0.0175 #N/A #N/A 0.00001 #N/A #N/A 104 #N/A #N/A 0.331 #N/A #N/A 0.000022 #N/A #N/A 0.0001 #N/A #N/A 0.01 #N/A #N/A 0.0203 #N/A 0.00001 #N/A 99.7 #N/A 0.340 #N/A 0.000023 #N/A 0.0001 #N/A 0.01 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 0.00002 0.00002 0.00002 #N/A 0.00005 0.00002 0.00002 0.00002 0.00002 #N/A 0.00001 #N/A 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 131 104 98.0 #N/A 103 112 97.7 105 98.1 #N/A 101 #N/A 92.0 97.9 99.3 95.2 97.6 99.6 97.7 99.1 0.785 0.953 0.800 #N/A 1.20 1.15 0.580 0.612 0.553 #N/A 0.517 #N/A 0.449 0.458 0.415 0.406 0.418 0.385 0.395 0.406 0.000548 0.000047 0.00002 #N/A 0.00005 0.0002 0.00002 0.00002 0.00002 #N/A 0.00001 #N/A 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00055 0.00034 0.0002 #N/A 0.0005 0.0002 0.0002 0.0002 0.0002 #N/A 0.0001 #N/A 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 #N/A 0.00001 0.00001 0.00001 #N/A 104 97.9 97.4 #N/A 0.432 0.445 0.419 #N/A 0.00001 0.00001 0.00001 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 1 2 3 4 5 6 7 8 9 10 11 0.00001 #N/A 0.00001 #N/A #N/A #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 129 #N/A 117 #N/A #N/A #N/A 105 #N/A 101 #N/A 103 0.352 #N/A 0.351 #N/A #N/A #N/A 0.353 #N/A 0.338 #N/A 0.341 0.000085 #N/A 0.000094 #N/A #N/A #N/A 0.000085 #N/A 0.000084 #N/A 0.000080 Speciation samples collected No sample collected Results discarded due to irregularities More than 15% of results are less than or equal to the MDL, no mean calculated Zinc (Zn)Dissolved #N/A 0.0199 0.001 0.001 0.001 #N/A #N/A #N/A 0.001 #N/A 0.0005 #N/A 0.0005 #N/A 0.0005 #N/A 0.0005 #N/A #N/A 0.0005 0.0005 #N/A #N/A 0.0005 #N/A 0.0005 0.003 0.003 0.003 #N/A #N/A #N/A 0.003 #N/A 0.003 #N/A 0.003 #N/A 0.003 #N/A 0.003 #N/A #N/A 0.003 0.003 #N/A #N/A 0.003 #N/A 0.003 0.018 0.016 0.031 #N/A 0.013 0.020 0.01 0.020 0.020 #N/A 0.016 #N/A 0.01 0.013 0.013 0.01 0.01 0.01 0.01 0.01 0.00409 0.00291 0.00229 #N/A 0.00513 0.00503 0.0110 0.00872 0.00967 #N/A 0.00939 #N/A 0.0156 0.0123 0.0102 0.0112 0.00878 0.00895 0.00616 0.00917 0.0156 0.0106 0.0103 #N/A 0.0061 0.0070 0.0032 0.0050 0.0045 #N/A 0.00463 #N/A 0.00355 0.00417 0.00433 0.00479 0.00430 0.00412 0.00449 0.00422 1.81 0.0252 0.0077 #N/A 0.005 0.006 0.0062 0.003 0.0040 #N/A 0.0054 #N/A 0.0053 0.0034 0.0063 0.0031 0.0031 0.003 0.003 0.003 #N/A 0.0001 0.0001 0.0001 #N/A 0.01 0.01 0.01 #N/A 0.00285 0.00654 0.0107 #N/A 0.00478 0.00405 0.00204 #N/A 0.003 0.0055 0.0032 0.0001 #N/A 0.0001 #N/A #N/A #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 0.012 #N/A 0.021 #N/A #N/A #N/A 0.01 #N/A 0.016 #N/A 0.013 0.0192 #N/A 0.0200 #N/A #N/A #N/A 0.0189 #N/A 0.0184 #N/A 0.0151 0.001 #N/A 0.001 #N/A #N/A #N/A 0.001 #N/A 0.0005 #N/A 0.0005 0.0808 #N/A 0.0909 #N/A #N/A #N/A 0.0830 #N/A 0.0767 #N/A 0.0700 Bold Values are less than or equal to the MDL 0-15% of values are less than or equal to the MDL, 0.5 x MDL used as replacement value in mean calculation Appendix D.9 Tabulated Water Quality - Chemical Characterization Silver (Ag)Dissolved Sodium (Na)- Strontium (Sr)- Thallium (Tl)Dissolved Dissolved Dissolved Tin (Sn)Dissolved Titanium (Ti)- Uranium (U)- Vanadium (V)Dissolved Dissolved Dissolved Zinc (Zn)Dissolved 0-Jan-00 Date Week Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 Column 2 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 12 13 14 15 16 17 18 19 20 21 22 23 24 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 0.00001 0.00001 #N/A 97.8 #N/A 101 #N/A 98.0 100 98.5 #N/A 0.356 #N/A 0.339 #N/A 0.341 0.323 0.328 #N/A 0.000084 #N/A 0.000087 #N/A 0.000087 0.000084 0.000084 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 0.0001 0.0001 #N/A 0.01 #N/A 0.014 #N/A 0.01 0.01 0.01 #N/A 0.0197 #N/A 0.0180 #N/A 0.0180 0.0176 0.0161 #N/A 0.0005 #N/A 0.0005 #N/A 0.0005 0.0005 0.0005 #N/A 0.0696 #N/A 0.0624 #N/A 0.0574 0.0623 0.0574 #N/A #N/A 0.00001 #N/A #N/A 106 #N/A #N/A 0.339 #N/A #N/A 0.000090 #N/A #N/A 0.0001 #N/A #N/A 0.01 #N/A #N/A 0.0174 #N/A #N/A 0.0005 #N/A #N/A 0.0600 #N/A 0.00001 #N/A 99.0 #N/A 0.349 #N/A 0.000087 #N/A 0.0001 #N/A 0.01 #N/A 0.0170 #N/A 0.0005 #N/A 0.0498 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 Column 5 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 0.00002 #N/A 0.00002 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 0.00001 0.00001 121 #N/A 102 #N/A 97.5 #N/A 98.5 #N/A 97.5 #N/A 98.1 #N/A 93.7 #N/A 98.4 #N/A 98.3 99.8 100 0.548 #N/A 0.522 #N/A 0.584 #N/A 0.469 #N/A 0.441 #N/A 0.444 #N/A 0.403 #N/A 0.359 #N/A 0.371 0.351 0.335 0.000511 #N/A 0.00002 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 #N/A 0.00001 0.00001 0.00001 0.0002 #N/A 0.00042 #N/A 0.00028 #N/A 0.00012 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 #N/A 0.0001 0.0001 0.0001 0.015 #N/A 0.030 #N/A 0.014 #N/A 0.01 #N/A 0.017 #N/A 0.015 #N/A 0.01 #N/A 0.013 #N/A 0.01 0.01 0.01 0.0146 #N/A 0.00571 #N/A 0.00363 #N/A 0.00580 #N/A 0.0112 #N/A 0.00906 #N/A 0.0122 #N/A 0.0135 #N/A 0.0124 0.0153 0.0111 0.0087 #N/A 0.0148 #N/A 0.0125 #N/A 0.0086 #N/A 0.00639 #N/A 0.00743 #N/A 0.00463 #N/A 0.00468 #N/A 0.00379 0.00434 0.00388 0.911 #N/A 0.0083 #N/A 0.003 #N/A 0.003 #N/A 0.0031 #N/A 0.003 #N/A 0.003 #N/A 0.0040 #N/A 0.0040 0.003 0.003 #N/A #N/A 0.00001 #N/A #N/A 104 #N/A #N/A 0.373 #N/A #N/A 0.00001 #N/A #N/A 0.0001 #N/A #N/A 0.01 #N/A #N/A 0.0118 #N/A #N/A 0.00403 #N/A #N/A 0.0049 #N/A 0.00001 #N/A 97.0 #N/A 0.383 #N/A 0.00001 #N/A 0.0001 #N/A 0.01 #N/A 0.0128 #N/A 0.00309 #N/A 0.0064 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 Column 6 10-Feb-15 17-Feb-15 24-Feb-15 2-Mar-15 11-Mar-15 17-Mar-15 24-Mar-15 31-Mar-15 7-Apr-15 14-Apr-15 22-Apr-15 29-Apr-15 6-May-15 12-May-15 19-May-15 26-May-15 2-Jun-15 8-Jun-15 17-Jun-15 23-Jun-15 30-Jun-15 7-Jul-15 14-Jul-15 22-Jul-15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 0.00001 0.000025 0.00001 #N/A 0.00001 0.00001 0.00001 0.00001 0.00001 #N/A 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 128 126 121 #N/A 110 110 106 111 97.9 #N/A 102 96.2 97.8 101 103 97.2 98.7 101 101 104 0.352 0.342 0.342 #N/A 0.324 0.343 0.345 0.339 0.341 #N/A 0.349 0.354 0.360 0.365 0.342 0.344 0.344 0.339 0.321 0.336 0.000067 0.000098 0.000063 #N/A 0.000054 0.0001 0.000063 0.000066 0.000068 #N/A 0.000064 0.000070 0.000068 0.000073 0.000072 0.000068 0.000073 0.000075 0.000071 0.000077 0.0001 0.0001 0.0001 #N/A 0.0001 0.0001 0.0001 0.0001 0.0001 #N/A 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.012 0.013 0.022 #N/A 0.012 0.017 0.01 0.015 0.016 #N/A 0.014 0.01 0.01 0.013 0.012 0.01 0.01 0.01 0.01 0.01 0.0204 0.0198 0.0217 #N/A 0.0200 0.0227 0.0208 0.0205 0.0199 #N/A 0.0180 0.0202 0.0215 0.0200 0.0192 0.0188 0.0187 0.0198 0.0170 0.0196 0.001 0.001 0.001 #N/A 0.001 0.0011 0.00091 0.00073 0.00101 #N/A 0.00057 0.00068 0.0005 0.00059 0.00052 0.0005 0.00054 0.0005 0.0005 0.0005 0.127 0.121 0.116 #N/A 0.114 0.113 0.113 0.106 0.102 #N/A 0.0834 0.0790 0.0786 0.0730 0.0705 0.0647 0.0616 0.0635 0.0630 0.0648 #N/A 0.00001 0.00001 0.00001 #N/A 108 99.1 100 #N/A 0.362 0.359 0.356 #N/A 0.000087 0.000080 0.000075 #N/A 0.0001 0.0001 0.0001 #N/A 0.01 0.01 0.01 #N/A 0.0206 0.0199 0.0177 #N/A 0.00055 0.0005 0.00057 #N/A 0.0637 0.0609 0.0581 Speciation samples collected No sample collected Results discarded due to irregularities More than 15% of results are less than or equal to the MDL, no mean calculated Bold Values are less than or equal to the MDL 0-15% of values are less than or equal to the MDL, 0.5 x MDL used as replacement value in mean calculation Appendix D.10 Combined Water Quality Results Graphed pH 8.5 Standard Units 8 7.5 Column 1 7 Column 2 Column 5 6.5 Column 6 6 Inlet 5.5 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Week Percent Saturation Dissolved Oxygen 200 180 160 140 120 100 80 60 40 20 0 Column 1 Column 2 Column 5 Column 6 Inlet 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed ORP 400 300 mV 200 Column 1 100 Column 2 0 Column 5 -100 Column 6 -200 Inlet -300 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Week 16 17 18 19 20 21 22 23 24 Hardness 2500 2000 Column 1 1500 mg/L Column 2 Column 5 1000 Column 6 Inlet 500 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed Alkalinity 4500 4000 3500 3000 Column 1 Column 2 2000 Column 5 mg/L 2500 Column 6 1500 Inlet 1000 500 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Ammonia 10 9 8 7 Column 1 mg/L 6 Column 2 5 Column 5 4 Column 6 3 Inlet 2 1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 3 Bromide 2.5 mg/L 2 Column 1 Column 2 1.5 Column 5 Column 6 1 Inlet 0.5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Chloride 30 25 mg/L 20 Column 1 Column 2 15 Column 5 Column 6 10 Inlet 5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 1.2 Fluoride 1.0 mg/L 0.8 Column 1 Column 2 0.6 Column 5 Column 6 0.4 Inlet 0.2 0.0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Nitrate 80 70 60 Column 1 mg/L 50 Column 2 40 Column 5 30 Column 6 Inlet 20 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 25 Nitrite 20 Column 1 mg/L 15 Column 2 Column 5 10 Column 6 Inlet 5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Sulfate 900 800 700 mg/L 600 Column 1 500 Column 2 400 Column 5 Column 6 300 Inlet 200 100 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 12 Sulfide 10 mg/L 8 Column 1 Column 2 6 Column 5 Column 6 4 Inlet 2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Dissolved Organic Carbon 1200 1000 mg/L 800 Column 1 Column 2 600 Column 5 Column 6 400 Inlet 200 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 140 Aluminum 120 µg/L 100 Column 1 80 Column 2 Column 5 60 Column 6 40 Inlet 20 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Antimony 60 50 µg/L 40 Column 1 Column 2 30 Column 5 Column 6 20 Inlet 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Week 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 60 Arsenic 50 µg/L 40 Column 1 Column 2 30 Column 5 Column 6 20 Inlet 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Barium 2500 2000 Column 1 1500 µg/L Column 2 Column 5 1000 Column 6 Inlet 500 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 1.2 Beryllium 1 µg/L 0.8 Column 1 Column 2 0.6 Column 5 Column 6 0.4 Inlet 0.2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Bismuth 3 2.5 µg/L 2 Column 1 Column 2 1.5 Column 5 Column 6 1 Inlet 0.5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 0.6 Boron 0.5 mg/L 0.4 Column 1 Column 2 0.3 Column 5 Column 6 0.2 Inlet 0.1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Cadmium 3.5 3 µg/L 2.5 Column 1 2 Column 2 Column 5 1.5 Column 6 1 Inlet 0.5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 700 Calcium 600 mg/L 500 Column 1 400 Column 2 Column 5 300 Column 6 200 Inlet 100 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Chromium 12 10 µg/L 8 Column 1 Column 2 6 Column 5 Column 6 4 Inlet 2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 350 Cobalt 300 µg/L 250 Column 1 200 Column 2 Column 5 150 Column 6 100 Inlet 50 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Copper 5 4.5 4 3.5 Column 1 µg/L 3 Column 2 2.5 Column 5 2 Column 6 1.5 Inlet 1 0.5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 40 Iron 35 30 Column 1 mg/L 25 Column 2 20 Column 5 15 Column 6 Inlet 10 5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Lead 1.4 1.2 µg/L 1 Column 1 0.8 Column 2 Column 5 0.6 Column 6 0.4 Inlet 0.2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 0.3 Lithium 0.25 mg/L 0.2 Column 1 Column 2 0.15 Column 5 Column 6 0.1 Inlet 0.05 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Magnesium 160 140 120 Column 1 mg/L 100 Column 2 80 Column 5 60 Column 6 Inlet 40 20 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed Manganese 1400 1200 µg/L 1000 Column 1 800 Column 2 Column 5 600 Column 6 400 Inlet 200 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Molybdenum 60 50 µg/L 40 Column 1 Column 2 30 Column 5 Column 6 20 Inlet 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 1.4 Nickel 1.2 mg/L 1 Column 1 0.8 Column 2 Column 5 0.6 Column 6 0.4 Inlet 0.2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Phosphorous 2.5 2 Column 1 mg/L 1.5 Column 2 Column 5 1 Column 6 Inlet 0.5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 160 Potassium 140 120 Column 1 mg/L 100 Column 2 80 Column 5 60 Column 6 Inlet 40 20 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Selenium 160 140 120 Column 1 µg/L 100 Column 2 80 Column 5 60 Column 6 Inlet 40 20 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 30 Silicon 25 mg/L 20 Column 1 Column 2 15 Column 5 Column 6 10 Inlet 5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Silver 0.06 0.05 µg/L 0.04 Column 1 Column 2 0.03 Column 5 Column 6 0.02 Inlet 0.01 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 140 Sodium 120 mg/L 100 Column 1 80 Column 2 Column 5 60 Column 6 40 Inlet 20 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Strontium 1.4 1.2 mg/L 1 Column 1 0.8 Column 2 Column 5 0.6 Column 6 0.4 Inlet 0.2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 0.6 Thallium 0.5 µg/L 0.4 Column 1 Column 2 0.3 Column 5 Column 6 0.2 Inlet 0.1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Tin 0.6 0.5 µg/L 0.4 Column 1 Column 2 0.3 Column 5 Column 6 0.2 Inlet 0.1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 35 Titanium 30 µg/L 25 Column 1 20 Column 2 Column 5 15 Column 6 10 Inlet 5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Uranium 25 20 Column 1 15 µg/L Column 2 Column 5 10 Column 6 Inlet 5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.10 Combined Water Quality Results Graphed 18 Vanadium 16 14 µg/L 12 Column 1 10 Column 2 8 Column 5 Column 6 6 Inlet 4 2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Zinc 2000 1800 1600 1400 Column 1 1200 µg/L Column 2 1000 Column 5 800 Column 6 600 Inlet 400 200 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.11 Liquid Phase Selenium Speciation Results Tabulated Sample Date Se(IV) Results in ppb Se(VI) Unidentified Inlet Inlet Inlet Inlet Week 4 Week 11 Week 18 Week 24 1.1 1 0.20 2.0 87.1 88 91.5 90.1 11.7 8.8 9.53108623 3.60580007 99.9 97.8 101.2 95.7 1.10% 1.02% 0.20% 2.07% 87.19% 89.98% 90.38% 94.16% 11.71% 9.00% 9.42% 3.77% Column 1 Column 1 Column 1 Column 1 Week 4 Week 11 Week 18 Week 24 0.4 0.05 0.5 0.4 1.7 13.1 0.3 4.4 3.1 4.15 3.82419641 1.25325007 5.2 17.3 4.6 6.0 7.69% 0.29% 10.21% 6.62% 32.69% 75.72% 6.65% 72.65% 59.62% 23.99% 83.13% 20.73% Column 2 Column 2 Column 2 Column 2 Week 4 Week 11 Week 18 Week 24 0.2 1 2.4 2.6 100 85 81.6 71.7 0 2.6 0.06283525 4.53280217 95.3 88.6 84 78.9 0.21% 1.13% 2.82% 3.29% 104.93% 95.94% 97.11% 90.96% 0.00% 2.93% 0.07% 5.75% Column 5 Column 5 Column 5 Column 5 Week 4 Week 11 Week 18 Week 24 0.2 0.05 0.2 1.2 3.5 6.6 0.2 0.9 2.2 2.65 4.4961756 1.0490365 5.9 9.3 4.9 3.2 3.39% 0.54% 4.08% 38.27% 59.32% 70.97% 4.16% 29.07% 37.29% 28.49% 91.76% 32.66% Column 6 Column 6 Column 6 Column 6 Week 4 Week 11 Week 18 Week 24 1.1 8.4 14.5 16.5 62 31.2 0.2 5.9 9.2 8.3 1.68178559 0 72.3 47.9 16.4 20.6 1.52% 17.54% 88.53% 80.24% 85.75% 65.14% 1.22% 28.62% 12.72% 17.33% 10.25% 0.00% Bold text indicates result at or below method detection limit Highlighted column indicates that majority concentration of Se is in this species Total Results as a % of Total Se(IV) Se(VI) Unidentified Appendix D.12 Graphed Liquid Phase Selenium Speciation Results Se (IV) 100% % of Total 80% Column 1 60% Column 2 40% Column 5 20% Column 6 Inlet 0% Week 4 Week 11 Week 18 Week 24 Week Se (VI) 120% % of Total 100% 80% Column 1 60% Column 2 40% Column 5 20% Column 6 0% Inlet Week 4 Week 11 Week 18 Week 24 Week Unidentified Se Species 100% % of Total 80% Column 1 60% Column 2 40% Column 5 20% Column 6 0% Inlet Week 4 Week 11 Week 18 Week Week 24 Appendix D.12 Graphed Liquid Phase Selenium Speciation Results Total Se Parts Per Billion 120 100 80 Column 1 60 Column 2 40 Column 5 20 Column 6 Inlet 0 Week 4 Week 11 Week 18 Week 24 Week Inlet 100% % of Total 80% 60% Se(IV) 40% Se(VI) 20% Unidentified 0% Week 4 Week 11 Week 18 Week 24 Week Column 1 100% % of Total 80% 60% Se(IV) 40% Se(VI) 20% Unidentified 0% Week 4 Week 11 Week 18 Week Week 24 Appendix D.12 Graphed Liquid Phase Selenium Speciation Results Column 2 120% % of Total 100% 80% 60% Se(IV) 40% Se(VI) 20% Unidentified 0% Week 4 Week 11 Week 18 Week 24 Week Column 5 100% % of Total 80% 60% Se(IV) 40% Se(VI) 20% Unidentified 0% Week 4 Week 11 Week 18 Week 24 Week Column 6 100% % of Total 80% 60% Se(IV) 40% Se(VI) 20% Unidentified 0% Week 4 Week 11 Week 18 Week Week 24 Appendix D.13 PHREEQC Modelled Saturation Indices for Minerals of Interest 1.4 Calcite - CaCO3 1.2 Saturation Index 1 0.8 Column 1 0.6 Column 2 0.4 Column 5 Column 6 0.2 Inlet 0 -0.2 -0.4 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Dolomite - CaMg(CO3)2 4 Saturation Index 3.5 3 Column 1 2.5 Column 2 2 Column 5 1.5 Column 6 Inlet 1 0.5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.13 PHREEQC Modelled Saturation Indices for Minerals of Interest 0.8 Magnesite - MgCO3 0.6 Saturation Index 0.4 0.2 Column 1 0 Column 2 -0.2 Column 5 Column 6 -0.4 Inlet -0.6 -0.8 -1 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Gypsum - CaSO4•2H2O 0 Saturation Index -0.2 -0.4 Column 1 Column 2 -0.6 Column 5 Column 6 -0.8 Inlet -1 -1.2 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.13 PHREEQC Modelled Saturation Indices for Minerals of Interest 15 Pyrite - FeS2 Saturation Index 10 5 Column 1 0 Column 2 Column 5 -5 Column 6 -10 Inlet -15 -20 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Pyrrhotite - Fe(1-x)S 2 0 Saturation Index -2 -4 Column 1 -6 Column 2 -8 Column 5 Column 6 -10 Inlet -12 -14 -16 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.13 PHREEQC Modelled Saturation Indices for Minerals of Interest 2 Troilite - Fe(1-x)S 0 Saturation Index -2 -4 Column 1 -6 Column 2 -8 Column 5 Column 6 -10 Inlet -12 -14 -16 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Siderite - FeCO3 0.5 Saturation Index 0 -0.5 Column 1 Column 2 -1 Column 5 Column 6 -1.5 Inlet -2 -2.5 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.13 PHREEQC Modelled Saturation Indices for Minerals of Interest 0 Rhodochrosite - MnCO3 -0.5 Saturation Index -1 -1.5 Column 1 -2 Column 2 -2.5 Column 5 Column 6 -3 Inlet -3.5 -4 -4.5 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Bornite - Cu5FeS4 70 Saturation Index 60 50 40 Column 1 30 Column 2 20 Column 5 Column 6 10 Inlet 0 -10 -20 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.13 PHREEQC Modelled Saturation Indices for Minerals of Interest 20 Chalcopyrite - CuFeS2 Saturation Index 15 10 Column 1 Column 2 5 Column 5 Column 6 0 Inlet -5 -10 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Mackinawite - (Fe,Ni)(1+x)S 1.5 Saturation Index 1 0.5 Column 1 0 Column 2 -0.5 Column 5 -1 Column 6 Inlet -1.5 -2 -2.5 1 2 3 4 5 6 7 8 9 10 11 12 13 Week 14 15 16 17 18 19 20 21 22 23 24 Appendix D.14 Comparison of Column 1 Effluent and British Columbia Water Quality Guidelines BC WQG All results in mg/L N/A Week Guideline a function of upstream concentrations pH DO > 5 Dissolved Oxygen Hardness (as N/A CaCO3) Alkalinity Total (as N/A CaCO3) A function of pH and temperature, using an average temp of 20 C, minimum pH shown Ammonia, Total in guidelines is 6.5. Guideline is inversely related to temperature (as N) Bromide (Br) Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 1 6.19 2 6.11 0.54 3 6.13 4 6.08 0.653333333 5 6.04 0.93 6 6.02 1.195 7 6.35 1.41 8 6.41 2.083333333 9 2.38 1530 1810 1410 "" 1950 2040 1220 1400 1230 869 3880 1040 "" 1310 1410 768 981 995 8.79 5.47 0.258 "" 0.72 1.61 1.03 0.991 0.715 1 2.5 1 "" 1 1 1 1 0.5 Chloride (Cl) Total Cl- < 600 21.0 25.0 11.0 "" 10.0 10.0 10.0 10.0 10.1 Fluoride (F) Total Fl- = [-51.73 + 92.57 log(10) (hardness*)] × 0.01, valid for 10-385 mg/L CaCO3 hardness, above which point a site-specific assessment may be required. A hardness of 3685 mg/L CaCO3 results in a F guideline of 1.9 0.4 1 0.4 "" 0.4 0.4 0.4 0.4 0.2 Nitrate (as N) Nitrite (as N) Sulfate (SO4) Sulphide (as S) Dissolved Organic Carbon 32.8 (Cl- < 10) NO2- < (CL-)*0.03 (Cl- > 10) NO2- < 0.60 (Water hardness ≤ 250 mg/L). Total SO4- (Water hardness > 250 mg/L). Total SO4-2 may 2 require a site-specific assessment = variable, maximum of 429 mg/L Guideline a function of upstream concentrations 0.1 0.26 0.16 "" 2.54 2.47 0.1 0.1 0.05 0.02 0.05 0.02 "" 0.070 0.038 0.026 0.02 0.01 803 719 175 "" 319 359 554 404 476 0.189 0.218 4.28 "" 0.81 2.05 0.62 1.58 0.82 583 1110 629 "" 886 825 237 381 219 000.05787 Aluminum (Al)Dissolved Antimony (Sb)Dissolved Arsenic (As)Dissolved Barium (Ba)Dissolved Beryllium (Be)Dissolved Bismuth (Bi)Dissolved Boron (B)Dissolved pH < 6.5, Al < e^[1.209 − 2.426* (pH)+0.286(pH)^2] pH ≥ 6.5 Al < 0.1 Total As < 0.005 Total B < 1.2 0.118 0.0929 0.0670 "" 0.0345 0.0383 0.0143 0.0247 0.0175 0.0516 0.00577 0.00273 "" 0.00216 0.00219 0.00356 0.00250 0.00367 0.0548 0.00391 0.00325 "" 0.00673 0.00858 0.00668 0.00712 0.00763 0.0845 0.0818 0.473 "" 2.14 0.957 0.183 0.497 0.535 0.0002 0.0002 0.0002 "" 0.0005 0.001 0.0002 0.0002 0.0002 0.001 0.001 0.001 "" 0.0025 0.001 0.001 0.0001 0.0001 0.533 0.555 0.446 "" 0.325 0.314 0.185 0.196 0.190 1 Appendix D.14 Cadmium (Cd)Dissolved Calcium (Ca)Dissolved Chromium (Cr)Dissolved Cobalt (Co)Dissolved Comparison of Column 1 Effluent and British Columbia Water Quality Guidelines Cd < 0.001*(e^[1.03 × ln(hardness) – 5.274]), applies to water hardnesses (mg/L CaCO3) between 7 – 455 mg/L. A hardness of 455 mg/L CaCO3 results in a Cd level 0f 0.0028. Higher hardness levels require possible site-specific assessment. 0.000320 0.000055 0.000037 "" 0.00005 0.00010 0.000021 0.000013 0.000014 440 542 418 "" 557 633 320 376 320 0.0106 0.00564 0.00426 "" 0.00316 0.0033 0.00125 0.00199 0.00154 Total Co < 0.110 0.309 0.300 0.0168 "" 0.0236 0.0237 0.0129 0.00489 0.00352 Total Cu < 0.001*(0.094 hardness + 2), applies to water hardnesses (mg/L CaCO3) between 13 – 400 mg/L. 400 mg/L CaCO3 of hardness corresponds to a D-Cu guideline of 0.0396 mg/L 0.00455 0.00182 0.00067 "" 0.001 0.001 0.00071 0.0005 0.0005 Iron (Fe)Dissolved 0.35 26.3 25.2 20.3 "" 35.2 32.7 7.63 4.59 2.62 Lead (Pb)Dissolved Total Pb < 0.001*(e[1.273 ln (hardness*) -1.460]), applies to water hardnesses (mg/L CaCO3) between 8 – 360 mg/L. 360 mg/L CaCO3 of hardness corresponds to a T-Pb guideline of 0.0338 mg/L 0.001170 0.000140 0.000130 "" 0.000250 0.000100 0.000220 0.000100 0.000100 0.232 0.202 0.201 "" 0.211 0.224 0.201 0.176 0.229 Copper (Cu)Dissolved Lithium (Li)Dissolved Magnesium (Mg)Dissolved Manganese (Mn)Dissolved Molybdenum (Mo)-Dissolved Nickel (Ni)Dissolved Phosphorous (P)Dissolved Potassium (K)Dissolved Selenium (Se)Dissolved Silicon (Si)Dissolved Silver (Ag)Dissolved Sodium (Na)Dissolved Strontium (Sr)Dissolved Thallium (Tl)Dissolved Tin (Sn)-Dissolved Titanium (Ti)Dissolved Uranium (U)Dissolved Vanadium (V)Dissolved Zinc (Zn)Dissolved 104 111 90.0 "" 135 129 103 113 104 Total Mn ≤ 0.01102 * hardness + 0.54, applies to water hardnesses (mg/L CaCO3) between 25-259 mg/L. 289 mg/L. Higher hardness levels require possible site-specific assessment. 289 CaCO3 of hardness corresponds to a T-Mn guideline of 3.39 mg/L 1.24 1.27 0.820 "" 0.790 0.774 0.261 0.252 0.185 Total Mo < 2 0.0269 0.0143 0.00082 "" 0.00128 0.00077 0.00499 0.00199 0.00300 1.20 1.07 0.0748 "" 0.0723 0.0940 0.0958 0.0413 0.0360 0.91 0.62 1.23 "" 1.19 1.17 0.3 0.59 0.32 139 108 64.0 "" 47.0 41.4 23.7 23.8 17.8 0.0494 0.00273 0.00167 "" 0.00569 0.0057 0.0187 0.00580 0.0110 16.1 20.0 24.2 "" 19.0 19.1 12.4 14.7 12.4 0.00002 0.00002 0.00002 "" 0.00005 0.00002 0.00002 0.00002 0.00002 131 104 98.0 "" 103 112 97.7 105 98.1 0.785 0.953 0.800 "" 1.20 1.15 0.580 0.612 0.553 0.000548 0.000047 0.00002 "" 0.00005 0.0002 0.00002 0.00002 0.00002 0.00055 0.00034 0.0002 "" 0.0005 0.0002 0.0002 0.0002 0.0002 0.018 0.016 0.031 "" 0.013 0.020 0.01 0.020 0.020 0.00409 0.00291 0.00229 "" 0.00513 0.00503 0.0110 0.00872 0.00967 0.0156 0.0106 0.0103 "" 0.0061 0.0070 0.0032 0.0050 0.0045 1.81 0.0252 0.0077 "" 0.005 0.006 0.0062 0.003 0.0040 Total P < 0.015 0.002 Hardness > 100 mg/L T-Ag < 0.003 Total Zn < 0.001*(33 + 0.75(hardness - 90)), applies to water hardness between 90 – 500 mg/L CaCO3, above which point a site-specific assessment may be required. A hardness of 500 mg/L CaCO3 gives a T-Zn guideline of 0.315 2 Appendix D.14 Comparison of Column 1 Effluent and British Columbia Water Quality Guidelines All results in mg/L Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Column 1 Week pH Dissolved Oxygen Hardness (as CaCO3) Alkalinity Total (as CaCO3) Ammonia, Total (as N) Bromide (Br) 10 6.54 11 6.46 2.613333333 12 13 6.67 1.326666667 14 6.45 0.466666667 15 6.40 1.6975 16 6.51 1.515 17 6.67 0.97 18 19 6.56 2.53 20 6.86 21 22 6.61 1.33 23 6.81 2.846666667 24 6.59 2.436666667 "" 1090 964 932 996 1010 "" 908 971 974 1010 "" 1060 1040 1010 "" 861 770 554 787 839 641 880 767 728 692 "" 666 674 467 "" 0.0544 0.0085 0.0168 0.0189 0.0102 0.0153 0.0107 0.0643 0.0093 0.0690 "" 0.0686 0.0107 0.005 "" 1 1 0.5 0.5 1 0.5 0.5 0.5 0.5 0.5 "" 0.25 0.5 0.5 Chloride (Cl) "" 10.0 10.0 10.2 10.4 10.0 10.0 10.0 10.1 10.0 9.9 "" 9.6 10.2 10.0 Fluoride (F) "" 0.4 0.4 0.26 0.30 0.4 0.26 0.28 0.26 0.27 0.22 "" 0.31 0.28 0.2 Nitrate (as N) Nitrite (as N) Sulfate (SO4) Sulphide (as S) Dissolved Organic Carbon Aluminum (Al)Dissolved Antimony (Sb)Dissolved Arsenic (As)Dissolved Barium (Ba)Dissolved Beryllium (Be)Dissolved Bismuth (Bi)Dissolved Boron (B)Dissolved "" 0.1 0.1 0.05 0.05 0.1 0.05 0.05 1.61 0.05 0.490 "" 0.652 1.60 22.6 "" 0.02 0.02 0.01 0.01 0.02 0.030 0.022 0.219 0.046 0.176 "" 0.0679 0.013 0.117 "" 456 583 517 548 509 476 553 546 487 532 "" 573 611 706 "" 1.09 0.031 0.26 0.173 0.215 1.01 0.57 6.7 5.2 3.42 "" 5.5 1.32 0.206 "" 112 "" 29.1 38.9 39.1 48.3 33.6 36.8 50.3 4.39 "" 33.3 "" "" "" 0.0155 "" 0.0103 0.0140 0.0147 0.0174 0.0155 0.0125 0.0145 0.0138 "" 0.0186 0.0156 0.0073 "" 0.00426 "" 0.00474 0.00523 0.00369 0.00293 0.00340 0.00265 0.00288 0.00304 "" 0.00233 0.00222 0.00444 "" 0.00866 "" 0.00793 0.00865 0.00790 0.00955 0.0106 0.00817 0.00965 0.00811 "" 0.00912 0.00697 0.00566 "" 0.552 "" 0.415 0.405 0.368 0.304 0.339 0.176 0.378 0.260 "" 0.381 0.265 0.111 "" 0.0001 "" 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 "" 0.0001 0.0001 0.0001 "" 0.00005 "" 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 "" 0.00005 0.00005 0.00005 "" 0.162 "" 0.119 0.170 0.143 0.148 0.145 0.142 0.161 0.154 "" 0.147 0.160 0.138 3 Appendix D.14 Cadmium (Cd)Dissolved Comparison of Column 1 Effluent and British Columbia Water Quality Guidelines "" 0.0000113 "" 0.0000113 0.0000143 0.0000094 0.0000118 0.0000064 0.000005 0.000005 0.0000131 "" 0.0000092 0.0000056 0.000005 "" 279 "" 233 242 243 201 225 218 231 228 "" 254 249 238 "" 0.00139 "" 0.00120 0.00132 0.00142 0.00140 0.00132 0.00116 0.00144 0.00116 "" 0.00142 0.00124 0.00042 "" 0.00246 "" 0.00293 0.00342 0.00173 0.00069 0.00067 0.00032 0.00040 0.00042 "" 0.00039 0.00038 0.00076 Copper (Cu)Dissolved "" 0.0005 "" 0.00068 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 "" 0.0005 0.0005 0.0005 Iron (Fe)Dissolved "" 1.80 "" 1.54 1.16 0.626 0.355 0.343 0.162 0.239 0.149 "" 0.055 0.063 0.835 Lead (Pb)Dissolved "" 0.000100 "" 0.000099 0.000050 0.000050 0.000053 0.000050 0.000050 0.000050 0.000050 "" 0.000050 0.000050 0.000057 "" 0.194 "" 0.147 0.211 0.195 0.206 0.212 0.184 0.196 0.205 "" 0.202 0.209 0.205 "" 95.2 "" 85.4 95.1 98.4 109 91.3 103 96.2 108 "" 103 102 102 "" 0.121 "" 0.0801 0.0847 0.0877 0.0848 0.0852 0.0840 0.0851 0.0905 "" 0.107 0.122 0.115 "" 0.00316 "" 0.00433 0.00498 0.00273 0.00151 0.00189 0.000888 0.000779 0.00135 "" 0.000818 0.000905 0.00295 "" 0.0265 "" 0.0356 0.0368 0.0285 0.0187 0.0144 0.0114 0.0117 0.0117 "" 0.00829 0.00698 0.0103 Calcium (Ca)Dissolved Chromium (Cr)Dissolved Cobalt (Co)Dissolved Lithium (Li)Dissolved Magnesium (Mg)Dissolved Manganese (Mn)Dissolved Molybdenum (Mo)-Dissolved Nickel (Ni)Dissolved Phosphorous (P)Dissolved Potassium (K)Dissolved Selenium (Se)Dissolved Silicon (Si)Dissolved Silver (Ag)Dissolved Sodium (Na)Dissolved Strontium (Sr)Dissolved Thallium (Tl)Dissolved Tin (Sn)-Dissolved Titanium (Ti)Dissolved Uranium (U)Dissolved Vanadium (V)Dissolved Zinc (Zn)Dissolved "" 0.3 "" 0.3 0.3 0.3 0.34 0.34 0.3 0.3 0.3 "" 0.3 0.3 0.3 "" 15.8 "" 12.0 12.2 11.6 10.2 10.7 9.0 9.6 9.0 "" 12.4 10.1 6.9 "" 0.0115 "" 0.0172 0.0114 0.0110 0.00661 0.0134 0.00859 0.00905 0.0167 "" 0.0177 0.0128 0.0319 "" 12.9 "" 10.6 11.4 11.8 10.9 11.0 9.59 10.9 9.62 "" 12.7 10.2 6.45 "" 0.00001 "" 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 "" 0.00001 0.00001 0.00001 "" 101 "" 92.0 97.9 99.3 95.2 97.6 99.6 97.7 99.1 "" 104 97.9 97.4 "" 0.517 "" 0.449 0.458 0.415 0.406 0.418 0.385 0.395 0.406 "" 0.432 0.445 0.419 "" 0.00001 "" 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 0.00001 "" 0.00001 0.00001 0.00001 "" 0.0001 "" 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 "" 0.0001 0.0001 0.0001 "" 0.016 "" 0.01 0.013 0.013 0.01 0.01 0.01 0.01 0.01 "" 0.01 0.01 0.01 "" 0.00939 "" 0.0156 0.0123 0.0102 0.0112 0.00878 0.00895 0.00616 0.00917 "" 0.00285 0.00654 0.0107 "" 0.00463 "" 0.00355 0.00417 0.00433 0.00479 0.00430 0.00412 0.00449 0.00422 "" 0.00478 0.00405 0.00204 "" 0.0054 "" 0.0053 0.0034 0.0063 0.0031 0.0031 0.003 0.003 0.003 "" 0.003 0.0055 0.0032 4