Frank Lake, Alberta, Canada) Zhu, Dongnan Master Thesis

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UNIVERSITY OF CALGARY

Wastewater treatment assessment in a flooded wetland using water and mass balances (Frank Lake, Alberta, Canada)

Dongnan Zhu

A THESIS

SUBMITTED TO THE FACULTY OF GRADUATE STUDIES

IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE

DEGREE OF MASTER OF SCIENCE

GRADUATE PROGRAM IN GEOLOGY AND GEOPHYSICS

CALGARY, ALBERTA

APRIL, 2017

Abstract

Wetlands are increasingly used to treat wastewater for small municipalities and industries. The evaluation of wetland treatment efficiency typically involves comparing solute inflow and outflow concentrations, or investigating the export of nutrients per unit wetland area. A more holistic approach, which included seasonal changes in water quality and solute mass balances, yielded improved understanding about where nutrients are being stored in a wetland, the long-term treatment capabilities, and downstream impacts on water quality.

The study area is Frank Lake (FL), a wetland complex in southern Alberta, Canada, which has received municipal and slaughterhouse wastewater since 1989. Average annual water, chloride and nutrient mass balances between 1993 to 2015 suggest that: i) the lake received roughly equivalent volumes of annual inflow from three sources: spring melt (via ephemeral creeks), precipitation, and wastewater; ii) about two-thirds of the lake’s water loss was via evaporation, and one-third was via discharge into the receiving watershed; iii) about one-fourth of the annual chloride mass flux into FL (estimated at 845 ± 18 tons/yr) was stored in the lake sediment and shoreline soils, while the remaining three-fourths was discharged into the receiving watershed; iv) more than 60% of the annual phosphorus mass flux was discharged into the receiving watershed (and the remainder stored in the lake sediment and shoreline soils); and v) about 6% of the nitrogen was discharged into the receiving watershed.

Frank Lake water quality varied seasonally, with the lowest chloride (tracer) concentrations observed soon after spring melt. Decreased ephemeral creek inflow combined with evaporation during the open-water season (from May to November) resulted in increasing chloride concentrations that annually exceeded surface water quality guidelines. The highest chloride concentrations (up to 1442 mg/L) were observed in pore water in the peripheral soils were attributed to transpiration pumping. Chloride concentrations in a single lake sediment core suggest diffusion has transferred up to 500 tons of chloride to the lake sediment since 1989.

Increasing salt and phosphorus accumulation in sediment and peripheral soils are a long-term concern at FL. An estimated 6,000 tons of chloride stored in the lake have caused soil electrical conductivity values to exceed agricultural criteria in some shoreline areas. This salt, and an estimated 220 tons of phosphorus accumulated in near shore and lake sediments since 1989, could be released into the receiving water body during an extreme runoff event. Although there was no evidence of halide precipitation, phosphorus and calcium minerals are present in the lake sediment.

Water quality impacts on the receiving watershed, the Little Bow River (LBR), were significant. Average annual discharge and mass flux estimations from FL were similar to increases observed in the LBR in historic data, when FL effluent roughly doubled the average annual flow, and increased mass fluxes by 80, 20, and 235 times for chloride, nitrogen, and phosphorus, respectively. Surface water quality standards were routinely exceeded in the LBR for chloride, electrical conductivity and phosphorus downstream (but not upstream) of the FL discharge.

Frank Lake is not a sustainable approach to wastewater effluent treatment in its current form.

iii

Acknowledgments

I would like to express my deep gratitude to Cathryn Ryan, my amazing supervisor, for her patient guidance, enthusiastic encouragement and super useful suggestions of this research work. I enjoyed the time so much during work with her.

I would also like to thank Wendell Koning, Greg Wagner, Jianxun He and Steven Goudey for their advice and assistance. Deeply thanks to David Bethune for his review of my thesis and Michael Weiser for his very helpful suggestions. A million thanks to Farzin Malekani for his lab assistance.

My grateful thanks are also extended to Hongbin Gao, Nadine Taube Leanneski Janet, Kim Sena, Bianca Rocha, Tiago Morais and Jakub Ryban for their field support and lab assistance; thanks to Cecilia Chung, Ping Wu, James Zettel, Haley Magdalina, Samantha Eggink, David Bethune and Wayne Ling for their field support. Thanks Kasi Viswanathan for his MATLAB assistance. Thanks Biao Sun and Mike Wang for their ArcGIS assistance. Thanks Igor Pavlovskii and Qixin Chang for their advice and help.

I wish to thank my officemates for their support

Last but not least, I wish to thank my family, Xueqin Zhu and Yang Liu for their encouragement throughout my study.

Table of contents

Abstract ...... ii

Acknowledgments ...... iv

Table of contents ...... v

List of Tables ...... vii

List of Figures ...... viii

List of Appendices ...... xii

List of Abbreviations ...... xvii

1. Background ...... 1

1.1 Introduction...... 1

1.2 Study area ...... 8

2. Materials and Methods ...... 10

2.1 Geochemical and isotopic analyses ...... 10

2.2 Shoreline soil and mini-piezometers installation and sampling` ...... 12

2.3 Sediment core analysis ...... 13

2.3.1 Sediment total phosphorus analysis ...... 13

2.3.2 Sediment total organic carbon analysis ...... 13

2.3.3 Sediment total nitrogen analysis ...... 14

2.3.4 Sediment hydraulic conductivity analysis ...... 14

2.4 Annual water balance and mass balance ...... 15

2.5 Little Bow River discharge calculation (only 1997) ...... 17

3. Results and Discussion ...... 19

3.1 Average annual water balance ...... 19

3.2 Isotopic composition of water and evidence for evaporation ...... 20

3.3 Chloride distribution and average annual mass balance ...... 22

3.4 Frank Lake Basin 1 sediment core ...... 26

3.5 Geochemistry ...... 30

3.6 Water quality overview ...... 33

3.7 Phosphorus and nitrogen average annual mass flux and fate ...... 34

3.8 Long-term function of Frank Lake and its impact on the Little Bow River ... 36

4. Conclusions ...... 37

References ...... 41

Tables ...... 53

Figures ...... 55

Appendices ...... 67

List of Tables

Table 1. Estimated mass, and annual average storage rate of total nitrogen, total phosphorus and chloride in post-1989 lake sediment samples from a single 20 cm deep core taken from Basin 1 of Frank Lake on February 19, 2015...... 53

Table 2. Frank Lake basin water quality overview. Chloride (CCME, 2011), nitrate

(CCME, 2012), phosphorus (CCME, 2004), dissolved oxygen (AEP, 1997), sodium absorption ratio (S.A.R., AAFRD, 2002) and electrical conductivity (EC, AAFRD,

2002) are shown in the table with average value (bolded), standard deviation, number and percentage that exceeded guidelines. Little Bow River (after 1993) downstream included all available data regardless of Frank Lake discharge. Frank

Lake (1990-1992), Little Bow River and DO pre-dawn data were provided by Alberta

Environment and Parks...... 54

vii

List of Figures

Little Bow River Upstream and Downstream and discharge location to Frank Lake’s

Basin 1 (Wastewater Influent); c) detail view of research area showing three basins, lake nearshore & shoreline sediment & shallow groundwater sampling locations

(sampled on August 18, 2013 and May 12, 2015 for lake nearshore and shallow groundwater, but shoreline sediment was only sampled once on May 12, 2015), lake interior (Sampled on Aug 18, 2013) and regular sampling locations

(Wastewater Influent, Basins 1, 2 and 3 Outlet; sampled biweekly from 2012 to

2015). 55

Fig. 2. Wastewater influent discharge and chloride with time. 1990s’ discharge data were collected by Alberta Environment and Parks; 1990s’ chloride data were from

Sosiak, 1994. Discharge and chloride data, 2012 to 2015, were from current study.

2000s; App. E); Masses of chloride, nitrogen and phosphorus from precipitation are not included since they are negligible relative to the other fluxes. The ΔV and ΔF terms refer to the residual annual volumes and mass fluxes, respectively, that are not accounted for in the mass balances. The ΔF is assumed to accumulate in the lake sediments and shoreline areas...... 57

viii

Creeks), and wastewater influent. Average values for each type of sample were shown with 95% confidence intervals. The green line (δD = 5.4 δ18O - 49) was consistent with evaporation of the ”calculated source water”. The tendency for higher water isotope values in the summer, and lower isotope values in the winter was based on the data plotted with Julian Day (App. D), and lake interior samples and nearshore Frank Lake samples were collected on August 18, 2013 and May 12,

2015. Shallow Basin 1 sediments were from the lake bottom to 10.4 cm in depth, while the deep sediment samples were from 10.4 to 20 cm in depth...... 58

Fig. 5. Box and whisker plot of Cl and δ18O concentrations in i) potential water sources for Frank Lake: Highwood River (Chao, 2011), Mazeppa and Blackie

Creeks, groundwater (as measured in regional water wells, Alberta Water Well

Information Database, App. F), wastewater influent (from the town of High River and a meat packaging plant) and lake source mixture (calculated based on water balance by one third of creeks water, one third of precipitation and one third of

Wastewater Influent); ii) Frank Lake (Basin 1, 2, and 3 outlets, nearshore areas of the lake and Basin 1 water sampled at frozen periods under ice (Bayley et al., 1995); iii) Frank Lake subsurface water: mini-piezometer groundwater samples, the lake shoreline pore water and pore water of sediment sampled from the centre of Basin 1; iv) Little Bow River sampled up and downstream of Frank Lake outlet (AENV, unpublished data, 1982-2005). The Alberta Surface Water Quality (AB SWQ) and long-term guidelines (120 mg/L, CCME, 2011) is shown in blue, and the Canadian

Drinking Water Objective (CDWG, 250 mg/L, Health Canada, 2014) is shown in pink.

Only long-term sampling data were used for the potential water sources and Frank

Lake water samples. T-test indicate data with the same letters in the Box and

Whisker plots between Frank Lake water and subsurface water were significantly different (p = 0.05). Significantly differences for potential water sources were not considered. (see next page)...... 59

Fig. 6. Dual plot of δ18O and chloride in pore water and lake water samples, with calculated changes associated with evaporation shown by solid lines. The calculated increases in δ18O were based on relatively humidity value of Blackie station (67%, Alberta Agriculture and Forestry, 2016), with the percentage of residual water indicated by black dots (Skrzypek et al., 2015)...... 61

Fig. 7. Total nitrogen, total phosphorus, and total organic carbon in core sampled from Basin 1 lake sediments (on Feb 19, 2015), and δ18O and chloride in sediment pore water, plotted against depth in sediment. Dashed line indicates depth of sediments deposited after wastewater diversion to Frank Lake began in 1989. Red symbols plotted at the lake water – sediment interface (i.e. at ‘zero’ depth) indicate the average (and 95% confidence interval) for chloride concentration and δ18O values in water sampled from Basin 1 Outlet in this study during the open water season (2012-2015). The blue symbols represent the average (and 95% confidence interval) for chloride concentration and δ18O values in water sampled from Basin 1 of the chloride concentration from under-ice, winter lake sampling data from 1994

(Bayley et al., 1995) and the δ18O values from three under – ice, lake water samples

(collected on February 19, 2015), respectively...... 62

Fig. 8. Piper plots of Frank Lake Basin. Fig. 8a. Difference in piper plot of

Wastewater influent water samples from the period 1990 to 1993 (Alberta

Environment and Parks data) and 2012 to 2015 (this research program); Fig. 8b.

Piper plot of water samples in Frank Lake Basin showing lake water mixed by lake potential water sources (Ephemeral creeks and Wastewater influent). Data were collected in this study from 2012 to 2015; and Fig. 8c. Piper plot of water samples in

Basin 3 Outlet and Little Bow River (LBR) showing the effects of LBR by Frank Lake discharge. Data were collected by Alberta Environment and Parks except Basin 3

Outlet (2012 to 2015), which were sampled by this research program...... 63

Fig. 9. Box plots of chloride concentrations in Wastewater Influent, Basin 1 Outlet, and Basin 3 Outlet for two periods 1990-1999 (Alberta Environment and Parks data) and 2012-2015 (data obtained by this research program)...... 66

List of Appendices

Appendix A. Photos of winter discharge of Basin 3 Outlet ...... 67

Appendix A-a. Basin 3 Outlet at December 1st 2013 showing discharge to the

Little Bow River (photo credit: Greg Wagner) ...... 67

Appendix A-b. Basin 3 Outlet at January 2nd 2014 showing discharge to the

Little Bow River (photo credit: Greg Wagner) ...... 68

Appendix A-c. Basin 3 Outlet at February 9th 2014 showing discharge to the

Little Bow River (photo credit: Greg Wagner) ...... 69

Appendix A-d. Basin 3 Outlet at March 10th 2014 showing discharge to the

Little Bow River (photo credit: Greg Wagner) ...... 70

Appendix A-e. Basin 3 Outlet at November 19th 2014 showing discharge to

the Little Bow River (photo credit: Alberta Environment and Parks) ...... 71

Appendix A-f. Basin 3 Outlet at December 8th 2014 showing discharge to the

Little Bow River (photo credit: Greg Wagner) ...... 72

Appendix A-g. Basin 3 Outlet at December 9th 2014 showing discharge to the

Little Bow River (photo credit: Greg Wagner) ...... 73

Appendix A-h. Basin 3 Outlet at December 21st 2014 showing discharge to

the Little Bow River (photo credit: Greg Wagner) ...... 74

Appendix A-i. Basin 3 Outlet at February 23rd 2015 showing discharge to the

Little Bow River (photo credit: Greg Wagner) ...... 75

xii

Appendix A-j. Basin 3 Outlet at March 15th 2015 showing discharge to the

Little Bow River (photo credit: Greg Wagner) ...... 76

Appendix B. Temperature, precipitation and evaporation plots of Blackie Station

(4km away of Frank Lake, 2012 to 2015 daily average, Alberta Agriculture and

Forestry, 2016)...... 77

Appendix C. MATLAB input code ...... 78

Appendix D. Basin 1 sediment core particle size percentage between 0.02 to 200 um with d10 ( the particle size at which 10% of the soil is finer), “-“ means unavailable ...... 79

Appendix E. Julian day plots of Frank Lake basin ...... 87

Appendix E-a. Julian day of discharge of Blackie creek, Mazeppa Creek,

Wastewater Influent, Basin 1 Outlet, Basin 2 Outlet and Basin 3 Outlet. Data

were provided by Alberta Environment except 2012 to 2015 that were

measured by fieldwork with an velocity meter for this study (legends are same

for all julian day plots) ...... 87

Appendix E-b. Julian day of total nitrogen of Blackie creek, Mazeppa Creek,

Wastewater influent, Basin 1 Outlet, Basin 2 Outlet, Basin 3 Outlet Little Bow

River (LBR) Upstream and LBR Downstream. All data was provided by Alberta

Environment except 2012 to 2015 that were analyzed by lab work for this study.

...... 88

Appendix E-c. Julian day of total phosphorus of Blackie creek, Mazeppa Creek,

Wastewater influent, Basin 1 Outlet, Basin 2 Outlet, Basin 3 Outlet, Little Bow

xiii

River (LBR) Upstream and LBR Downstream. All data was provided by Alberta

Environment except 2012 to 2015 that were analyzed by lab work for this study.

...... 89

Appendix E-d. Julian day of Chloride of Blackie creek, Mazeppa Creek,

Wastewater influent, Basin 1 Outlet, Basin 2 Outlet, Basin 3 Outlet Little Bow

River (LBR) Upstream and LBR Downstream. All data was provided by Alberta

Environment except 2012 to 2015 that were analyzed by lab work for this study.

...... 90

Appendix E-e. Julian day of D of Blackie creek, Mazeppa Creek, Wastewater

influent, Basin 1 Outlet, Basin 2 Outlet and Basin 3. All data were analyzed by

lab work for this study (2012-2015)...... 91

Appendix E-f. Julian day of 18O of Blackie creek, Mazeppa Creek,

Wastewater influent, Basin 1 Outlet, Basin 2 Outlet and Basin 3. All data were

analyzed by lab work for this study (2012-2015)...... 92

Appendix F. All relative data of Frank Lake Basin (“-“ means unavailable) ...... 93

Appendix F-a. Wastewater Influent data (2012 – 2015) ...... 93

Appendix F-b. Basin 1 Outlet data (2012 – 2015) ...... 94

Appendix F-c. Basin 2 Outlet data (2012 – 2015) ...... 95

Appendix F-d. Basin 3 Outlet data (2012 – 2015) ...... 96

Appendix F-e. Ephemeral creeks data (2012 – 2015) ...... 97

Appendix F-f. Frank Lake subsurface data (2012 – 2015) ...... 98

xiv

Appendix F-g. Frank Lake shoreline and interior data (2012 – 2015) ...... 99

Appendix F-h. Frank Lake Basin 1 sediment core data (sampled at the

deepest area of Basin 1 on February 19, 2015) ...... 100

Appendix F-i. Frank Lake Wastewater Influent data (2006 – 2011, Alberta

Environment and Parks) ...... 101

Appendix F-j. Frank Lake Basin 1 Outlet, and Basin 2 Outlet data (1995 and

1997, Alberta Environment and Parks) ...... 102

Appendix F-k. Frank Lake Basin 3 Outlet data (1996 – 2011, Alberta

Environment and Parks) ...... 103

Appendix F-l. Frank Lake creeks data (1996, 1997 and 1999, Alberta

Environment and Parks) ...... 105

Appendix F-m. Little Bow River upstream data (1982 – 2010, Alberta

Environment and Parks) ...... 106

Appendix F-n. Little Bow River downstream data (1982 – 2010, Alberta

Environment and Parks) ...... 107

Appendix G. Local groundwater chloride data close to Frank Lake, which collected by Alberta Water Well Information Database ...... 108

Appendix H. Schematic diagram of the average annual water balance, chloride balance, total nitrogen balance and total phosphorus balance for each basin of

Frank Lake based on data shown in Table 1; Mass precipitation of chloride, nitrogen and phosphorus are not included since these are negligible relative to the other fluxes. ΔV and ΔF are fluxes not accounted for...... 109

Appendix I. Time-weighted average annual chloride and 18O based on Julian day plots (Jan: 350 mg/L; Feb: 400 mg/L; Mar: 200 mg/L; April: 80 mg/L; May: 110 mg/L;

June: 150 mg/L; July: 200 mg/L; Aug:220 mg/L; Sep: 250 mg/L, Qct: 290 mg/L; Nov:

310 mg/L; Dec: 350 mg/L, Total is 2910 mg/L, and time weighted average annual is

243 mg/L ; Jan: -11 ‰; Feb: -16 ‰; Mar: -21 ‰; April: -20 ‰; May: -15 ‰; June: -

11 ‰; July: -6 ‰; Aug:-5.5 ‰; Sep: -5 ‰, Qct: -6 ‰; Nov: -8 ‰; Dec: -11 ‰, Total is -135 ‰, and time weighted average annual is -11 ‰ ) ...... 110

Appendix J. 1-D diffusion model of chloride and 18O of Frank Lake Basin 1 sediment...... 111

Appendix K. Dissolved Oxygen plots of Frank Lake ...... 112

Appendix K-a. Dissolved Oxygen plots of Basin 1 Outlet (unpublished data of

year 2013, Alberta Environment and Parks) ...... 112

Appendix K-b. Dissolved Oxygen plots of Basin 2 Outlet (unpublished data of

year 2013, Alberta Environment and Parks) ...... 113

Appendix K-c. Dissolved Oxygen plots of Basin 3 Outlet (unpublished data of

year 2013, Alberta Environment and Parks) ...... 114

Appendix L. Microprobe results on sediment sample that showing phosphorus and calcium ions are bonded together (two images of the same sample of Basin 1 which was sampled in August, 2013) ...... 115

xvi

List of Abbreviations

AEP Alberta Environment and Parks

AWWID Alberta Water Well Information Database

CCME Canadian Council of Ministers of the Environment

CW Constructed Wetland

DO Dissolved Oxygen

DU Ducks Unlimited

EC Electrical Conductivity

FL Frank Lake

LBR Little Bow River

N Nitrogen

NADB North American Treatment Wetland Data base

P Phosphorus

S.A.R. Sodium Absorption Ratio

TDS Total Dissolved Solids

USEPA United States Environmental Protection Agency

WW Influent Wastewater Influent

xvii

1. Background

1.1 Introduction

Wastewater effluent treatment is a challenge, particularly for small communities and rural industries that lack significant wastewater treatment facilities (Crites and Tchabongalous, 1998; Kivaisi, 2001; Luederitz et al., 2001; Westerhoff et al.,

2014). Many communities store their treated wastewater in lagoons for periodic discharge to rivers, while others rely on wetland treatment (Zhou and Hosomi,

2008; Mcjannet et al 2012).

Wetlands are areas “where water is the primary factor controlling the environment and the associated plant and animal life” (Niering, 1985).

Historically, wetlands were called swamps, marshes, bogs, fens or sloughs, depending on existing plant and water conditions, and on geographic setting

(Kadlec and Wallace, 2009). Wetlands are widely used for wastewater treatment because they retain a higher proportion of total nutrient loading, compared to effluent discharge to lakes and rivers (Saunders and Kalff, 2001). About 80% of more than 1700 U.S. wetlands treated wastewater for populations of less than

5000 people (Wallace and Knight, 2004). Hundreds of thousands of wetlands are now used around the world to treat wastewater (Mitsch and Gosselink, 1993;

Bachand and Horne, 2000; Vymazal, 2011).

Although natural wetlands are often used (Ronkanen and Klove 2007), constructed wetlands (CW) are increasingly being constructed close to wastewater outlets to maximize treatment efficiency (with a particular focus on

nutrients) (Vymazel, 2010). Constructed wetlands, seek to mimic natural wetland ecosystems by combining physical, chemical, and biological processes (USEPA,

2000; Mitsch and Gosselink, 2000).

The first significant wetland treatment experiments were conducted in Germany in the early 1950s (Seidel, 1953). Much of wetland treatment research has been focused on understanding specific nutrient retention processes to optimize CW design, often using laboratory and macrocosm experiments (Westerhoff et al.,

2014). Natural wetland treatment research is less common and tends to focus on whole wetland treatment systems (i.e. from the wastewater influent to the wetland effluent; Raisin et al., 1999; Lenters et al., 2011). Since nitrogen (N) and phosphorus (P) removal mechanisms are different, research tends to be conducted independently on each nutrient.

The potential fate of nutrients include: i) plant harvest, ii) discharge to receiving water bodies, iii) release to the atmosphere in the gas form (for N only), and iv) storage in the organic or mineral form in the wetland sediments and/or shoreline soils. Although wetland researchers tend to consider all nutrient losses from the water column as “export”, we differentiate here between export from the wetland system and storage within the wetland and shoreline areas. Wetland bottom sediment or shoreline soil nutrient storage is not a long-term processes. For instance, the capacity of P sorption can decline over short time periods with continued effluent application as the sorption sites become saturated (Dale,

1983). Similarly, ‘stored’ nutrients could be released to receiving water bodies during extreme precipitation or flood events, or cause soil salinization issues

(Reddy, 1999).

Wetland N treatment processes include ammonium adsorption (Dunne and

Reddy, 2005), sedimentation (Vohla et al., 2005), microbial assimilation

(Vymazal, 2001), nitrification – denitrification (Hunt et al., 2005), and ammonia volatilization (Reddy and Patrick, 1984). Since wetlands tend to have standing water (with low oxygen concentrations during non-sunlight periods) and high organic matter (from wastewater), extensive denitrification tends to occur.

Denitrification, the reduction of nitrate to nitrogen gas is typically the primary mechanism of N export, removing between 45 to 97% of influent wastewater mass flux (Taylor et al., 2005; Dowens et al., 1997).

Although N sedimentation and uptake by aquatic plants are also major removal mechanisms (Saunders and Kalff, 2001), these processes do not transfer N from the wetland to the atmosphere. Although denitrification, as opposed to plant uptake, is sometimes assumed to be the main mechanism for nitrate removal, mass balance calculations (Bachand and Horne, 2000), or other confirmative analysis (e.g. stable isotopes and tracers) (Ronkanen and Klove, 2007) are not always conducted to confirm denitrification has occurred. Removal by denitrification (3.0 - 3.3 g N m-2 d-1) was far greater than either sedimentation

(0.16 - 0.27 g N m-2 d-1) or plant uptake (0.19 - 0.33 g N m-2 d-1) in three experimental wetlands in New Zealand (Van Oostrom, 1995).

Uptake by plants has variable success as a P removal mechanism. Kim and

Geary (2001) found less than 5% of the P load in municipal wastewater was

taken up by wetland plants. In contrast, Wu et al. (2011) found that plant uptake was a significant removal process for nutrients, removing up to 52% of N and 34% of P, respectively. Systems with free-floating plants may achieve higher removal of N via plant uptake due to multiple harvests each year (Vymalzal, 2007).

Since P does not have a gaseous form and is thus not exported to the atmosphere, treatment involves storage, primarily in sediments (Reddy, 1999).

Adsorption and mineral precipitation (e.g. apatite, struvite, vivianite; Kadlec and

Wallace, 2009) are the two primary P storage mechanisms in natural wetlands, but are not necessarily a limitless sink for P. Phosphorus removal by mineral precipitation is only effective when the geochemistry is oversaturated with respect to phosphate mineral saturation indices. Similarly, the saturation of sorption sites may limit sorption.

The common failure to measure P loading (i.e. the product of discharge and concentration) makes the evaluation of removal efficacy questionable. Reddy

(1999) suggested that comparing influent and effluent concentrations was insufficient for P treatment, however, few studies have collected sufficient data to measure average annual influent and effluent loads. Vymalzal (2007) measured effluent total P concentrations were from 40 to 60% of influent concentrations in various types of CW, however, P loading was not measured. Wetland treatment efficiency is also assessed on an area basis, with total P removal rates ranging between 45 and 75 g N m−2 yr−1 depending on the wetland type and inflow loading (Vymalzal, 2007).

Some of the approaches used to assess the efficacy of wetland treatment are borrowed from the field of wastewater engineering. The simplest treatment efficiency assessment compares the influent vs. effluent concentrations (e.g. 10 to 98% concentration reduction for total P in 18 non-forested wetlands; NADB,

1993; USEPA, 1999). Although unstated, this approach assumes that influent and effluent discharges are equivalent.

Engineering solutions are increasingly being designed to overcome limitations in natural treatment processes by enhancing natural treatment with the addition of supplemental materials such as the use of expanded clay aggregates and the addition of iron and aluminum oxides, however these methods are not well tested nor extensively used (Kadlec and Wallace, 2009). Engineering approaches to increase phosphate mineral precipitation of wastewater in wetlands (e.g. add iron into wastewater), are increasingly being evaluated (Wilfert et al., 2015), but are still not common. Given the relatively low rate of phosphate removal, P treatment requires very large land areas or alternative treatment methods (USEPA, 1993).

In addition, P that is stored in a wetland can be lost downstream in flood events

(Hickey and Gibbs, 2009).

The seasonal influence on wetland treatment performance can be particularly important in a cold climate, as plant dormancy may affect biological processes near or below freezing temperatures (Faulwetter et al., 2009). Bacterial growth and metabolic rates are strongly reduced with decreasing temperature (Atlas and

Bartha, 1998). Nitrification activity was inhibited between 6 and 10 ◦C and denitrification activity was detected only above 5 ◦C (Werker et al., 2002),

explaining why little nutrient removal occurs over the winter season (USEPA,

1988; Reed et al., 1995). Reduced N and P removal was also measured in the summer in one temperature study (55% to 32% for N, and 35% to 28% for P, respectively). Colder temperatures decrease nutrient uptake by plants (Allen et al., 2002, Stein and Hook, 2005). A few studies have measured better-than- expected winter removal efficiency (Jenssen et al., 1993) and hypothesized that enhancement of aerobic and more efficient microbial degradation of organic matter due to an increased redox potential in colder temperatures (Stein and

Hook, 2005).

Although the evaluation of wetland nutrient export on receiving water bodies has long been recommended (Reddy, 1999), no studies have evaluated the relative impact on flow and water quality on water bodies downstream of wetlands.

Wetland water balances have long been recognized as important (USEPA, 1999), however only one study conducted a wetland water balance and found a 97% groundwater contribution to the wetland (Raisin et al., 1999). Although stable isotopes analysis has long been recognized as a useful tool in water balances

(Turner et al., 1984; Zhu et al., 2014), no published wetland studies have used water isotopes. Similarly, relatively few studies have considered water, tracers, salt and/or a nutrient mass balance, nor the long term fate of nutrients and salt.

The few wetland studies that have reported mass balances for N (Bishay and

Kadlec, 2005; Kadlec et al. 2005), did not consider water and/or tracer mass balances.

Given the lack of holistic wetland treatment efficiency assessments, combined

with increasing use of wetlands to treat of wastewater effluent, the author evaluated the use of a natural wetland (Frank Lake (FL), Alberta, Canada), which has been used to treat increasing amounts of municipal and slaughterhouse effluent since 1989. Earlier research on FL, which considered only influent and effluent nutrient concentrations (White and Bayley, 1999; White et al., 2000;

White and Bayley, 2001) concluded that up to 64% of P in the influent wastewater was removal annually by FL.

This study is a more holistic assessment of wastewater treatment in a natural wetland and includes mass balances of influent/effluent discharge, chloride, N, and P concentrations; and the ultimate fate of salt and nutrients including the overall impact on receiving water bodies and peripheral soil,.

The evaluation included:

a) Review of historic data (influent/effluent discharge, lake water quality, and

climate data),

b) Sampling and analysis of water samples from influent and effluent points,

lake water, and groundwater over a three year time period for water

18 2 quality parameters and stable isotopes ( Owater and Hwater).

c) Sampling and analysis of lake and shoreline sediments.

d) Evaluation of water quality impacts on the receiving water, the Little Bow

River (LBR), using historic data up and downstream of the FL discharge

into the LBR.

1.2 Study area

Frank Lake is a 10 km2 natural lowland area in southern Alberta, located about

45 km south of Calgary that has been receiving treated municipal and slaughterhouse wastewater since 1989 (Fig.1).

Ducks Unlimited (DU) and other groups have long recognized the geographical importance of the FL region as a staging and breeding area for thousands of birds (Bayley et al., 1995). The FL is considered the most significant marsh for waterfowl in southern Alberta. As a result, the FL region is important locally and provincially for the breeding of colonial water birds, migratory birds, staging geese, staging ducks, and for rare, threatened, and endangered species (Poston et al., 1990, Wallis et al., 1996).

As far back as 1945, DU sought an approach to create FL, and, in 1975 DU was ultimately successful in building a weir to regulate water levels to protect against flooding and droughts, hence supporting a continuous waterfowl population

(Bayley et al., 1995). Prior to this, FL was intermittently wet and dry (Bayley et al.,

1995), with no natural outflow recorded until 1953. In 1953, Alberta Environment drained FL due to an exceptionally high runoff.

In 1983, FL dried out completely despite the presence of the weir and remained dry until 1989 when the Municipal District of Foothills was licensed to divert wastewater effluent from the Town of High River and the Cargill Meat Processing plant near High River to FL (Sosiak, 1994). At the same time, DU was also licensed to divert water from the Highwood River to FL to compensate for high

evaporation losses by FL (Sosiak, 1994). In addition to regulating FL water levels, wastewater diversion to FL alleviated previous issues of wastewater effluent discharge to the Highwood River (e.g. fish kills and algae blooms; Alberta

Environment, 1990). All the various sources of wastewater flow to FL via a subsurface pipeline from a common lift station 12 kilometers away (Bayley et al.,

1995). By July 1993, the lake was refilled to a satisfactory level. Although water from the Highwood River was initially used to dilute the wastewater influent, this practice was changed in 1994 and since that time the only source of water to FL has been wastewater (White and Bayley, 2000).

Frank Lake consists of three separate basins, with control weirs at each basin outlet. Basin 1 is 5.1 km2, Basin 2 is 3.6 km2 and Basin 3 is 1.4 km2 ( Digel,

1997). Basin 1 is managed to maintain a water depth of 1.0 m, and tends to have excessive vegetation, while Basin 2 has the same water depth as Basin 1 but much less vegetation (Digel, 1997; White and Bayley 1997). Basin 3 is the shallowest water level (0.3 m or less) and also supports abundant vegetation

(Digel, 1997). The total storage in FL’s three basins is approximately, 1.3 × 107 m3 at capacity, and 6×106 m3 at a normal operating level (Digel, 1997). The lake water level is typically the lowest in the winter, increases in the spring to capacity when ephemeral creeks discharge to the lake, and then decreases to the normal operating level over the summer. Two seasonal creeks, Mazeppa and Blackie, discharge to the FL from the north and west of the lake.

Treated effluent from Cargill Ltd. and the Town of High River enters FL via a combined side discharge into Basin 1 (Fig. 1). Initially, Wastewater (WW) Influent

discharge rates were 1.2 × 106 m3 per year for the Town of High River, and 7.8 ×

105 m3 per year for Cargill Ltd. (Digel, 1997). The average total annual volume of combined effluent was approximately 2.3 × 106 m3 (Digel, 1997). Wastewater

Influent chloride concentration and discharge rate have both increased on a decadal scale (Fig. 2). The first outflow from FL (since 1989) to the receiving water body, the LBR, began in 1996 through a constructed canal after the lake basins were filled and the water levels stabilized (Sosiak, 2011).

The semi-arid climate of FL region has an annual average air temperature of

2.3 °C, an average annual precipitation of 450 mm (mostly occurring between

May to July), and an estimated annual potential evaporation of 862 mm (Alberta

Agriculture and Forestry, 2016). The lake water is usually frozen from mid-

November to mid-May. A mean residence time of 0.8 year can be estimated for

FL water based on an average lake volume of 1.0 × 107 m3/year; and an average annual outflow discharge of 12 × 106 m3/year. Significant short-circuiting between each of the three basins inlet and outlet may be occurring (Personal

Communication, W. Koning, Alberta Environment and Parks Limnologist).

2. Materials and Methods

2.1 Geochemical and isotopic analyses

Surface water samples from four locations (WW Influent, Basin 1 Outlet, Basin 2

Outlet and Basin 3 Outlet) were collected biweekly from 10 cm below the water surface during the ice-free months between March 2012 and November 2015.

The 14 mini-piezometers, and adjacent lake water, were sampled on August 18,

2013 and May 12, 2015. Nine lake water samples from widely distributed interior locations were also collected on August 18, 2013 (Fig. 1).

Analysis of field parameters included electrical conductivity (EC), temperature, pH, and dissolved oxygen (DO). Samples were stored on ice or at 4 °C. Alkalinity was measured in the field by titration with a HACH kit (with the addition of bromocresol and titration with H2SO4).

Subsurface water and surface water samples collected for laboratory analysis were filtered through 0.45-μm filters within 8 h of sampling and separated into the aliquots for analysis: 1) cations (except ammonium; acidified to a pH < 2 using

HNO3), 2) ammonium (field acidified to a pH < 2 with ultra pure H2SO4), 3) anions

(no treatment), 4) total phosphorus (no treatment), 5) and δ18O and δ2H (no treatment). The filter apparatus and bottles were rinsed with distilled and sample water between samples. All sample analyses were conducted at the University of

Calgary as follows.

Major ion analyses were conducted by ion chromatography using a Dionex DX-

120 chromatograph with an analytical uncertainty of ±1 %. Total P was determined by alkaline persullfate digestion followed by Dionex DX-120 chromatograph. Stable isotope analysis of oxygen and hydrogen was conducted using a CO2 equilibration unit coupled with an IRMS (Finnigan MAT Delta S). The isotope ratios of 18O/16O and 2H/1H are expressed in delta notations of their relative abundances as deviations in per mil (‰) from the international standard

Vienna Standard Mean Ocean Water (VSMOW). The analytical uncertainty of the

δ18O and δ2H measurements is ±0.1 and ±1‰, respectively. For most samples (>

97%) , ion charge balances were less than 3%. Saturation indexes were calculated using the Geochemist’s Workbench.

2.2 Shoreline soil and mini-piezometers installation and sampling`

Thirteen soil cores (consisting of ten samples, each 5 cm in depth, for a total depth of 50 cm) were collected from locations near the lake shoreline. One soil sample was also taken from southwest of FL where visible white precipitate was present (Fig. 1).

Soil mineralogy was assessed using x-ray diffraction at the University of Calgary.

Soil water extractions were also conducted by shaking 5 g soil in 50 ml of distilled water for 1 h, followed by filtering and by major ion analyses as described in previously.

Fourteen mini-piezometers (MPs) were installed along the shoreline to measure vertical groundwater gradients at the groundwater-surface water interface and sample shallow groundwater in each of 2013 and 2015. The MPs were installed to about 0.6 m depth in the sediments below the lake near the shore. The MPs equilibrated for at least 24 h (checked two different days) prior to measurement of the static level using a Solinst model 101 P7 handheld water level meter).

Samples were collected using a Buerkle Sampler peristaltic pump and PE tubing on the day after installation. Vertical hydraulic gradients were estimated by dividing the difference in head measured between the mini-piezometers and the lake stage by the distance between the lake bottom and middle of the mini-

piezometer screen (Baxter and Hauer, 2003). Propagation of errors in vertical gradient estimations (which assumed water level measurement errors of ±0.005 m and MP screen mid-point depth measurement error of ±0.075 m) showed that gradients ≤0.05 were not significantly different from zero.

2.3 Sediment core analysis

A single sediment sample was taken under 60 cm of ice at the deepest area of

Basin 1 on February 19, 2015 (Fig. 1). The 20 cm length core which was collected with a Livingstone Corer (Deevey, 1964) and sampled at 2 cm intervals for the analysis of total nitrogen, total phosphorus, total organic carbon, water isotopes and chloride (see above for analytical methods).

2.3.1 Sediment total phosphorus analysis

Sediment samples were dried at 105 °C for 24 hours and passed through a 0.5- mm sieve before analysis. Dry sediment was ignited in a muffle furnace in a porcelain crucible (550 °C for 1h). After cooling, the residue was washed into a

100ml Erlenmeyer flask with 25 ml 1 N HCl and boiled for 15 min on a hot plate.

The sample was diluted to 100 ml in a volumetric flask, and orthophosphate was determined using the perchloric acid method (Andersen, 1976).

2.3.2 Sediment total organic carbon analysis

Sediment samples were oven dried at 105 °C for 24 hours and ground, then passed through a 0.5-mm sieve before analysis. For measurement of loss-on- ignition (LOI), 200 mg of soil were added to glass beakers, placed in a muffle

furnace at 550 °C for 4 h, cooled to room temperature in desiccators, and weighed. LOI was measured as the difference between the oven-dry soil mass and the soil mass after combustion, divided by the oven-dry soil mass (Schulte and Hopkins 1996) as follows:

LOI550 = ((DW105–DW550)/DW105)*100

where LOI550 represents LOI at 550 °C (as a percentage), DW105 represents the dry weight of the sample before combustion and DW550 the dry weight of the sample after heating to 550 °C. Dean (1974) showed a strong correlation between LOI at 550 °C and organic carbon content determined chromatographically in lake sediments.

2.3.3 Sediment total nitrogen analysis

Sediment samples were oven dried at 105 °C for 24 hours and ground, then pass through a 0.5-mm sieve before analysis. For determination of total nitrogen, samples were subsequently treated with 3 and 20% HCl at 80 °C to remove any carbonates and then measured with the CNS-2000 analyzer (Haberzettl et al.,

2005).

2.3.4 Sediment hydraulic conductivity analysis

Grain size analyses on air-dried soil samples were measured by Malvern

Mastersizer 2000 particle size analyzer (Sperazza et al., 2004). A series of 100 sieve sizes were used ranging from 0.02 to 2000 μm (App. D). The particle size at which 10% of the soil is finer, d10, was used to calculate hydraulic conductivity

(K) using Hazen Formula (Fetter, 2000).

The Hazen formula which is applicable for sandy soils is defined as:

where ρ is fluid density at a given temperature (1000 kg/m3 at 4 ℃), g is

2 acceleration due to gravity (9.8 m/s ), μ is dynamic viscosity (kg/ms) , CHZ is sorting coefficient (10 x 10-4).

2.4 Annual water balance and mass balance

Data were collected from two periods (1990-1999 and 2012-2015). The first period was when the Alberta Environment and Parks (AEP) conducted a monitoring program on FL and the second period was for this research project.

The discharge into Blackie Creek, Mazappa Creek, WW Influent, Basin 1 Outlet,

Basin 2 Outlet and Basin 3 Outlet was recorded biweekly using the velocity-area method. The winter discharge data were estimated by photo evidence provided by Greg Wegner (Athene Environmental Limited; App. A). The maximum monthly mean precipitation and evaporation (using data taken from Agriculture and Agri-

Food Canada’s Blackie Station, which is 4 km northwest of FL) occurs in June and July, respectively (App. B, Alberta Agriculture and Forestry, 2016). The mean annual precipitation of FL was 450 mm/yr (Alberta Agriculture and Forestry,

2016). The mean annual shallow lake evaporation, estimated using monthly values of temperature, humidity, and sunshine duration (Morton, 1983) collected

from the Blackie weather station. The average annual value, 782.5 mm/yr, was similar to provincial estimates (Alberta Environment and Sustainable

Development, 2013). Transpiration was not calculated since the area of plant growth is not well known.

The weekly discharge and water quality data collected from these time ranges were input into MATLAB (App. C) to produce a random matrix (100 × 52) for each week of the year. The average annual data were used in the water and mass balances as follows:

where

3  (L in one year) is the average annual WW Influent discharge entering

FL;

3  (L in one year) is the average annual ephemeral creek discharge

entering FL;

 P (L over the entire lake area in one year) is the annual precipitation;

2 2  (L ) is the lake area, 10.1 km ;

3  (L in one year) is the average annual Basin 3 Outlet discharge leaving

FL;

 (L over the entire lake area in one year) is the annual evaporation;

 (L3 in one year) is the annual lake storage, as zero (see above)

 (L3 in one year) is the net annual component of the lake water balance that

is not accounted for by the above inputs or outputs and thus assumed to be

either input or output of groundwater.

Similarly, an average annual mass (chloride, nitrogen and phosphorous) balance for FL consisted of:

Where the average annual chloride, nitrogen, or phosphorous concentrations

(M/L) were

 for the WW Influent entering FL;

 for the ephemeral creeks entering FL;

 for the precipitation entering FL,

 for the Basin 3 Outlet leaving FL;

 was the residual chloride, nitrogen or phosphorous fluxes (M in one year)

not accounted for in the annual mass balance.

Mass loss from plant uptake was not included in the mass balance, since plant harvest did not occur.

Inland precipitation typically contains relatively low concentrations of chloride, total N and total P (i.e. chloride: 0.2 mg/L, Junge and Werby, 1958; total N:

<0.1kg/ha per year, NADP, 2000; 10μg/L, Ahn, 1999). This makes the estimated annual mass of chloride, total N and total P associated with precipitation negligible in the mass balance (i.e. <0.005 % of QIn for chloride, <0.002 % of QIn for total N and <0.002 % of QIn for total P).

2.5 Little Bow River discharge calculation (only 1997)

The discharge rate of the LBR up and downstream of the Basin 3 outlet was calculated by mass balance based on known factors from 1997 (discharge rate of

Basin 3 Outlet, chloride, total nitrogen and total phosphorous concentration of

Basin 3 Outlet, LBR upstream, and downstream) as follows:

⑴

⑵

Substituting (2) to (1), we have

which can be rearranged to:

where the chloride, total nitrogen, or total phosphorus concentration were

COut for the Basin 3 Outlet, mg/l;

CLBR up for the LBR upstream, mg/l;

CLBR down for the LBR downstream, mg/l;

and the discharge were

3 QOut for the Basin 3 Outlet, m /s;

3 QLBR up for the LBR upstream, m /s;

3 QLBR down for LBR downstream, m /s;

3. Results and Discussion

3.1 Average annual water balance

The average annual water and ion mass balances were conducted to understand

FL’s nutrient treatment efficiency. A net average annual evaporation deficit was observed (Fig. 3), with an estimated average annual evaporation rate, 7.9 × 106 m3/a, that was almost twice that of precipitation (4.6 × 106 m3/a). Although ephemeral creek discharge occurred over a short period (i.e. spring runoff, usually beginning in the middle of March, and ending in middle of April, depending on the year; App. E), its contribution was significant, and equivalent to about one third of FL’s average annual input. The water balance thus showed that the WW Influent, precipitation, and ephemeral creek flows each provided about one-third of FL’s average annual water input to the lake, while evaporation was the single largest average annual volumetric water loss. The average annual discharge from FL (3.6 x 106 m3/a), estimated at the Basin 3 Outlet was equivalent to less than half of that lost by evaporation.

Although measurement of overwinter discharge rates from the Basin 3 Outlet to the receiving water body were not available, photographic evidence of discharge was available for ten days between December 1, 2013 and March 15, 2015 (App.

A). The relatively low stage evident in the photographs suggests that winter flows were intermittent and small compared to spring and summer periods, but in the absence of routine flow monitoring, overwinter discharge rates are poorly understood.

The groundwater component (ΔV) is estimated 0.49 ± 0.05 x 106 m3/yr which is small relative to the other fluxes (i.e. 4.1 % of ∑QIN (QWW, QEC and precipitation) and 4.2 % of ∑QOUT (ET and QOUT; Fig. 3). This is consistent with the low hydraulic gradient (< 0.05) measured in the groundwater below the lake (App. F) and the low permeability glacial till below FL (10 - 350 m; Cummings et al., 2012).

Thus, there does not appear to be a significant amount of groundwater flowing into or out of FL.

3.2 Isotopic composition of water and evidence for evaporation

Frank Lake’s isotopic water composition ranged from −21.48 to 3.1 ‰ for δ18O, and −166.44 to −36.83 ‰ for δ2H (Fig. 4). Water from Mazeppa and Blackie

Creeks had the lowest values for water isotopes (-24.35 to -18.48 ‰ for δ18O and

-188.54 to -151.19 ‰ for δ2H), while the WW Influent had the most consistent stable isotope composition (-18.24 to -12.96 ‰ for δ18O and -141.49 to -126.32 ‰ for δ2H). The creek waters and WW Influent sampled in this study plotted near the local meteoric water line, as did the regional precipitation (Peng et al., 2004;

Fig. 4), indicating none of these waters had undergone significant evaporation.

An estimated volume-averaged ‘source’ isotopic composition for the lake was calculated by combining the estimated volumetric contribution from the three main water sources to FL identified in the average annual water balance with their corresponding isotopic compositions (using the isotopic composition for

Calgary precipitation; Peng et al., 2004). This provided a calculated ‘composite’

FL source water mixture of −18.0 ‰ for δ18O, and −143.9 ‰ for δ2H (Fig. 4).

The isotopic composition of pore water sampled from sediments along the shoreline and lake interior, shallow groundwater from mini-piezometers, and FL water (Basin 1 Outlet, Basin 2 Outlet, and Basin 3 Outlet, in addition to samples from the lake interior and lake shoreline) had relatively large δ18O and δ2H values, and plotted along a line on the dual isotope plot that was consistent with evaporation (Fig. 4). The evaporation line intersects the composite FL source water mixture (i.e. one third of WW Influent, one third precipitation and one third

Mazeppa and Blackie Creeks) samples, suggesting the composite FL source mixture is a reasonable estimate of the main initial source of the water prior to evaporation. The slope of the evaporation line (5.3) is consistent with that expected for evaporation in a semi-arid climate (Clark and Fritz, 1997).

Increasing evaporation-induced water loss occurred as water flowed through the three basins in FL, as indicated by successively higher average values of δ18O and δ2H between the composite source mixture, Basin 1, Basin 2, and Basin 3

Outlet (Fig. 5). The most extensive evaporation effect was observed in a FL sample from Basin 3 Outlet, on September 27th, 2012 (3.1 ‰ for δ18O, and

−36.83 ‰ for δ2H; App. E), while and the highest average (Fig. 4) and median

(Fig. 5) value of unfrozen lake water δ18O was found in near shore lake samples

(12 samples collected on two dates only; App. F).

Time series of water isotopes and chloride concentrations also showed a clear seasonal variation in evaporation (App. E), with the lowest evaporation measured in the spring, when seasonal ephemeral creek flows dilute the lake water, and the highest evaporation observed in the late summer.

Unfortunately, the similarity in the isotopic composition of regional well water samples (median value of δ18O = -18.5 ‰; Cheung et al., 2010; Fig. 4 and 5) and lake source water (median value of δ18O = -18.7 ‰; Fig. 4 and 5) prevented the use of water isotopes to evaluate whether significant groundwater ‘through flow’ occurrs in FL.

3.3 Chloride distribution and average annual mass balance

Both chloride concentration and discharge volume have increased in the WW

Influent over time (Fig. 2). This is reflected in an increase in the annual average

WW Influent chloride flux from 288 ± 21 tons/yr between 1990 and 1993 (Sosiak,

1994) to 1018 ± 39 tons between 2012 and 2015 (Fig. 2).

In the 2012 to 2015 sampling program, FL chloride concentrations ranged from

22 to 565 mg/L in the three lake basin outlets (App. F), with a median value of

190 mg/L (Fig. 5). Median chloride concentrations increased as water travelled through the three basins. The Basin 3 Outlet had the highest chloride concentration measured (565 mg/L on date; App. F) and the highest median concentration (204 mg/L) in the basin outlet sampling program (Fig. 5). High chloride concentrations were also found in the nearshore areas (Aug 6, 2013 and

May 12, 2015), where the highest median chloride concentration (214 mg/L) for lake water was measured (Fig. 5). The nearshore chloride concentrations were higher than the outlet samples on the same day, indicating nearshore areas could be more extensively evaporated than the lake interior, which is consistent with their isotopic composition (Fig. 4). This is likely due to short-circuiting of

water between basin inlet and outlets, with longer residence times in nearshore areas (Personal Communication, W. Koning, Limnologist, Alberta Environment and Parks).

Chloride concentrations in shallow groundwater sampled from mini-piezometers and pore water from sediments tended to be higher than lake water sampled at the basin outlets (Fig. 5). Although the median chloride concentration of mini- piezometer groundwater (305 mg/L) was the highest of all sample types observed during the open water season, chloride concentrations in the shoreline sediment porewater (which had a median concentration of 218 mg/L) were more variable, and included the highest concentration measured in the sampling program (1442 mg/L; Fig. 5). This suggests that chloride is being stored in the sediment porewater and shallow groundwater in the shoreline areas of the lake.

The overall relationship between chloride concentration and water isotopes in

Basin 1 Outlet and Basin 2 Outlet of FL suggests evaporation-induced increases in δ18O values and chloride concentrations occurred in a predictable manner between the composite lake source water (i.e. precipitation, ephemeral creeks, and WW Influent), Basin 1 Outlet, and Basin 2 Outlet (Fig. 6). In contrast, the chloride concentrations in shoreline sediments and groundwater sampled from mini-piezometers, and to a lesser extent Basin 3 Outlet, were relatively elevated

(Fig. 6). This suggests a process that increases chloride concentration without significantly affecting water isotope composition occurred in the subsurface water of the shoreline sediments (i.e. groundwater from mini-piezometers and pore water from shoreline sediments) and in Basin 3.

“Transpiration pumping” is a plant process that transports water from the root zone to above-ground plant material, but leaves most of the dissolved solutes in the root area (Kadlec et al., 1987; Kadlec, 1999; Heagle et al., 2007 and Heagle et al., 2013). The vegetation of prairie wetlands tends to be salt tolerant since extensive transpiration pumping around the edge of natural wetlands is common, with high salt concentrations in the wetland periphery (Kantrud et al., 1989;

Heagle et al., 2007).

While evaporation causes isotopic fractionation, with progressively higher isotopic values in residual water, transpiration does not result in significant fractionation in water isotopes (Akker et al., 2011). The transpiration “pump” thus tends to concentrate ions in root areas, but does not change isotopic composition of the water remaining in the root zone. Transpiration pumping would cause elevated chloride concentrations in absence of elevated δ18O values, as observed in mini-piezometers and soil water in lake shoreline (Fig. 6). Thus, it appears that the relatively high chloride concentration in subsurface water in FL’s shoreline areas were related to transpiration pumping, and could represent an area of long term chloride deposition and storage. Extensive transpiration pumping in Basin 3 in particular may have resulted in the higher chloride concentrations (Fig. 6). This is consistent with the relatively shallow water depth and more extensive vegetation in Basin 3, compared to Basins 1 and 2 (Digel,

1997). Isotopic evolution of FL during evaporation with an average relative humidity of 67% (2012 to 2015 at Balckie station, Alberta Agriculture and

Forestry, 2016) is shown with solid points explaining the residual water at given

percentages (Skrzypek et al., 2015) of the initial source water (Fig. 6).

The 2012 - 2015 annual chloride mass balance estimated that a chloride flux of

845 ± 18 t/a entered the lake, almost exclusively from WW Influent (Fig. 3). More than three-fourths of this flux (640 ± 46 t/a) discharged to the LBR, while about one-fourth (230 ± 16 t/a) either remained in the lake water, was deposited on nearshore sediments or migrated into low-permeability sediments in the groundwater surrounding and below FL. The deposition of chloride in the shoreline subsurface by transpiration pumping likely contributes to the average annual chloride storage, as would lake sediment deposition.

Chloride concentrations in regional well waters are relatively low (median = 18 mg/L; Fig. 5, APP. G) relative to FL (median = 182 mg/L; Fig. 5) compared to FL, groundwater near FL and the sediments pore water. If significant groundwater

“through flow” were occurring in FL, it would does not contribute to chloride storage in the lake, and is similarly not contributing significant volumes of water to FL’s average annual water balance. Thus, the chloride storage in FL appears to occur in the lake, the groundwater connected to the lake and shoreline sediments. Approximately 43% of the chloride storage is in Basin 1 compared to

25% for Basin 2 and 30% for Basin 3 (App. H). The slightly higher amount in

Basin 1 may be a result of a higher rate of sedimentation in that basin as it receives the full strength wastewater or possibly due to higher transpiration pumping associated with a relatively high density of shoreline plants in Basin 1.

An estimated 6,000 tons of chloride from wastewater effluent has been stored in

the lake since 1989 with all three basins acting as chloride sinks, presumably due to lake sediment deposition and transpiration pumping-induced deposition in the shoreline areas. This estimate is based on the assumption that the chloride influent mass flux observed during the period 1990 - 1993 continued to 2005 and the observed flux during the period 2012 - 2015 is representative of the period

2005 – 2016.

3.4 Frank Lake Basin 1 sediment core

Chloride concentrations in lake sediment pore water are discussed here in the context of a single lake sediment core sampled from under 61 cm of ice on

February 19, 2015 from the deepest area of Basin 1 (Fig. 1). The sediment organic carbon, total N, and total P concentrations decreased rapidly with depth to a depth of 10.4 cm, below which the values became more or less constant (Fig.

7). The elevated shallow chloride concentrations likely result from sediment that was deposited after WW Influent diversion to FL began in 1989. The decreased slope and values for total N, total P, and total organic carbon below 10.4 cm depth interpreted as ‘background’ or pre-WW influent sediment. The 10.4 cm post-1989 sediment depth represents an average sedimentation rate of 0.4 cm/year.

Although sediment concentrations can be assumed to be constant after deposition (Meyers, 1994), dissolved solutes in pore water would be subject to transport by advection and dispersion. Pore water extracted from the lake sediment showed elevated chloride concentrations (227 to 482 mg/L) relative to

the Basin 1 Outlet samples taken during the period 2012-2015 of this study

(average = 123 mg/L, std dev = 47, n = 28; plotted at the sediment-lake interface

(i.e. zero depth) in red on Fig. 7). The highest sediment pore water chloride concentration (452 mg/L) was found in the shallowest sediment sample, below which concentrations decreased with depth. Although the shallow chloride concentrations were significantly higher than those found in the 2012-2015 Basin

1 Outlet samples, they were similar to those measured from under-ice, winter lake samples from Basin 1 (average = 396 mg/L, std dev = 220, n = 8; Bayley et al., 1995, plotted at the sediment-lake interface figure (i.e. zero depth) in blue on

Fig. 7).

During slow ice formation from aqueous salt solutions, the ions and chemical compounds remain concentrated in the liquid part and are excluded from the ice crystal formation. This results in relatively high chloride, total N and total P concentrations in the residual, unfrozen water underlying the ice (Lind et al.,

2001; Yang et al. 2016). Since the lake sediment core was sampled during the winter (February 19, 2015), the high chloride, total N and total P concentrations in the shallowest sediment samples likely reflect lake chloride, total N and total P concentrations that were elevated in winter. Using an average lake depth of 1 m, and the measured ice thickness of 61 cm when the core was sampled on

February 19, 2015, the solute exclusion by winter ice formation would be expected to more than double chloride concentrations in the residual lake water, which is consistent with that observed (Fig. 7).

In addition to increasing chloride, total N and total P concentrations in underlying

lake water, ice formation also affects the water isotope composition of the residual, unfrozen water. The isotopic fractionation of water during freezing is significant, with the heavier molecules preferentially incorporated in ice, leaving lighter molecules in the unfrozen liquid (α = 1.00291; Lehmann and Siegenthaler,

1991; Clark and Fritz, 1997). The freezing of a significant fraction of the FL water column would thus result in a significantly lower δ18O value in the residual, unfrozen water below the lake ice (Gibson and Prowse, 2002). The estimated

δ18O in remaining lake water would be about -16.8 ‰, which is within the range of δ18O values observed in three under-ice lake water samples collected on the day the lake sediment core was sampled (-15.83 ± 1.24 ‰, plotted at the lake water-sediment interface in blue on Fig. 7).

Thus, the lake sediment pore water isotope and chloride concentration profiles reflect winter variations in the lake water caused by ice formation. Seasonal lake water variations are propagated into the sediments by diffusion, resulting in seasonally variable lake sediment profiles (Kolak et al., 1999, Garvelmann et al.,

2012 and Levy et al., 2014). While an average annual source water isotopic composition and chloride concentration controls the diffusion rate into deeper sediments, the water isotope values in shallow sediment fluctuate between the seasonal extremes (Fig. 7). The deeper (i.e. summer) pore water underwent more extensive evaporation than the shallower (i.e. winter) pore water, which is also consistent with expected seasonal variations (Fig. 4). The relatively low δ18O values (median = -18.5 ‰; Fig. 5) and much lower Cl concentration (median = 18 mg/L; Fig. 5) in regional well water suggests little groundwater exchange occurs

with the lake, and transport in the porewater would be dominantly by diffusion.

Furthermore, the low hydraulic gradient in the groundwater (App. F) and the relatively low hydraulic conductivity of the lake sediments (average = 7.5 × 10-7 m/s, std dev = 4.7 × 10-7 m/s, n = 23), suggested limited interaction between groundwater and lake water.

The time-weighted, average annual δ18O (-11.3 ‰) and chloride (243 mg/L) values (App. I) were used to model the average annual boundary values of diffusion at the lake water-sediment interface (Fig. 7, App. J), and background values of 18 mg/L chloride and -18.5 ‰ for δ18O (from regional well water samples; Cheung et al., 2010) were assumed to exist beneath the lake prior to its wastewater filling. The resulting vertical profiles (shown in grey of Fig. 7) after 26 years (i.e. since 1989) show that transport by diffusion caused relative concentration values to increase by more than 5% to about three meters depth, while the diffusion front is apparent to a depth of more than ten meters (App. J). If we assume the chloride mass observed in the upper three meters of the Basin 1 lake sediment pore water was found in similar concentrations throughout all three basins (i.e. the area of FL) and allowed to deposit over a period of 26 years

(since 1989) then a total of 507 tons Cl would have been stored in the lake sediments. This is much less than the ~6000 tons estimated by the chloride mass balance. The estimated annual deposition of chloride by diffusion into lake sediments ranged from 8.8 tons to 9.3 tons between 2012-2015. This is also less than the annual residual chloride mass for Basin 1 calculated the chloride mass balance (101 ± 4 tons, App. H). This suggests that transpiration pumping in the

peripheral lake soils stores more chloride than the lake sediments.

While chloride mass storage in lake sediment and shoreline soils is occurring at

FL, the rates and total amount are not well constrained by a single lake sediment core.

3.5 Geochemistry

The WW Influent major ion geochemistry in the two monitoring periods (1990 -

1993 and 2012 - 2015) showed an increase in total dissolved solids (TDS) (Fig.

8a), which is consistent with the observed increase in Cl concentration (Fig. 2).

The WW influent formed a mixing line that was dominated by relative contribution of Na + K in the cation ternary diagram, and showed a mixed contribution of the three end members in the anion ternary.

Frank Lake’s major ions also tended to be dominated by Na + K in cations, with a

2- more dominant contribution from SO4 in anions relative to the WW influent, and also seasonally variable TDS (Fig. 8b). In the later time period, FL’s major ion geochemistry was consistent with a mixture of ephemeral creeks (which dominantly occurs in March and April; App. E) and WW Influent (Fig. 8b). The water balance suggests that ephemeral creeks and WW Influent provide an average of about two-thirds (7.5 × 106 m3/a) of the lake water annually, with precipitation contributing the remaining one third (4.5 × 106 m3/a). Although the geochemistry of precipitation is not represented on Fig. 8b, low major ion concentrations expected in precipitation (Freeze and Cherry, 1979) would mainly dilute the relatively high WW Influent concentrations thus lowering the

concentrations of each ion (i.e. TDS) but not their relative concentrations of major ions as shown on the Piper Plot.

Seasonal dilution of FL’s major ion concentrations (e.g. chloride) was evident in

March and April, when ephemeral creek discharges were high (App. E) and major ion concentrations and TDS were relatively low (Fig. 8b), and in the early summer when precipitation rates were relatively high (App. B). As meltwater-fed spring season discharge of ephemeral creeks and early summer precipitation rates decreased and average daily temperatures increased, seasonal evaporation increased and the chloride concentration in FL tended to increase, typically exceeding that of the WW Influent by late summer (App. B and E). This seasonal evaporation effect contributed to the relative high annual variability in

TDS (Fig. 8b).

Geochemically, the most significant change between the WW Influent and FL

2- was an increased contribution of SO4 to the anion charge in FL, which was likely related to oxidation of reduced sulphur from the WW Influent in FL. The dissolved oxygen concentrations were high during daytime sampling events at all sampling locations in FL (Table 2). This was likely due to the dominance of water column photosynthesis in FL during daylight hours (Cohen et al., 2013).

Overnight dissolved oxygen concentrations were significantly lower (frequently approaching non-detectable concentrations), reflecting the dominance of water column respiration at night (App. K). Increasing TDS with flow from Basin 1 through to Basin 3 was similarly attributed to seasonal evaporation (as discussed above) and increased sulfide oxidation.

The LBR upstream and downstream of the FL outlet showed no change in major ion composition prior to the diversion of WW Influent into FL was initiated in 1989

(Fig. 8c). After this time, the major ion composition indicates that LBR downstream of FL’s discharge channel has been affected by the lake’s discharge

(Fig. 8c). The post-1989 major ion geochemistry formed a mixing line between

LBR upstream and FL outlet, with the variation in degree of mixing likely a function of the seasonal nature of FL discharge (which is not monitored) and seasonal variations in LBR flow.

Most of the lake water samples were over-saturated for a number of carbonate minerals (i.e. 90% of samples were oversaturated for aragonite (CaCO3), 87% of samples were oversaturated for calcite (CaCO3), 86% of samples were oversaturated for dolomite (CaMg(CO3)2), 83% of samples were oversaturated for huntite (Mg3Ca(CO3)4), 76% of samples were oversaturated for magnesite

(MgCO3) and 79% of samples were oversaturated for monohydrocalcite

(CaCO3·H 2O), respectively). Few lake water samples were over-saturated for hydroxide minerals (i.e. only 4% of samples were oversaturated for artinite

(Mg2(CO3)(OH)2·3H2O), 3% of samples were oversaturated for brucite (Mg(OH)2) and 5% of samples were oversaturated for hydromagnesite

(Mg5(CO3)4(OH)2·4H2O), respectively). Although saturation indices could not be calculated for common phosphate minerals due to the lack of aluminum analyses, microprobe evidence also supported the presence of calcium phosphate minerals in the lake sediment (App. L).

3.6 Water quality overview

Wastewater Influent was the main source of salt and nutrients in FL. Chloride

(CCME, 2011), nitrate (CCME, 2012) and dissolved oxygen (AEP, 1997) concentrations exceeded the long-term surface water guidelines of the Protection of Aquatic Life in 100%, 88% and 96% of the 2012-2015 samples, respectively

(Table 2). The average nitrate concentration of WW Influent (41 mg/L) which is

- 14 times the surface water guideline (3 mg NO3 N/L). Irrigation guidelines

(AAFRD, 2002) were also exceeded in WW Influent for the sodium absorption ratio (S.A.R.) and EC for the later time period (2012 - 2015). It should also be noted that the average chloride concentration of the WW Influent has more than doubled since the 1990s (Table 2).

The chloride concentrations in the majority of FL water samples (68% in Basin 1,

97% in Basin 2, and 91% in Basin 3) also exceeded surface water guidelines

(CCME, 2011) for the 2012-2015 sampling period. However, back in the 1990s, less than half of the samples exceeded these guidelines (Table 2, Fig. 9). The nitrate concentrations in FL were lower than the WW Influent, suggesting that FL effectively removed nitrogen. The majority of FL water (＞90%) exceeded the

Irrigation Water Quality” guidelines for S.A.R and EC and some of the samples were even in the range of “Hazardous” (AAFRD, 2002). Dilution of WW Influent water in Basin 1 by precipitation and ephemeral spring runoff resulted in higher water quality at the Basin 1 Outlet than in WW Influent. Also, the effect of increased evaporation as water passes through Basin 2 and Basin 3 resulted in

higher salt concentrations in these basins relative to Basin 1 (although concentrations in all three basins remained lower than the WW Influent; Table 2).

The highest chloride concentrations (and EC values) were observed in groundwater sampled from mini-piezometers and shoreline sediments. They all exceeded the Alberta Tier 1 Groundwater Remediation Guidelines (Cl and S.A.R. and/or EC, AEP, 2016, Table 2), indicating that an increase in salt accumulation within sediment and shoreline soils are a long-term concern at FL.

Major ion concentrations of the LBR exceeded surface water quality guidelines for chloride, nitrate, S.A.R. and EC (CCME, 2011; CCME, 2012 and AAFRD,

2002 Table 2). As expected, the concentration of major ions was consistently higher in the LBR downstream of the FL discharge than downstream after 1993, when discharge of WW Influent to FL began.

Phosphorus was exceeded for the Hyper-eutrophic Surface Water Guideline value (0.1 mg P/L; CCME, 2004) for all WW Influent, lake water and creek samples in all periods (Table 2). The effect of FL discharge in the LBR downstream caused 80% of the river samples to consistently exceed P concentration guidelines (compared to few exceedences before FL discharge began).

3.7 Phosphorus and nitrogen average annual mass flux and fate

An estimated 50% (8.6 ± 0.4 tons) of the wastewater P discharged to FL was stored in lake and shoreline sediments (mainly in Basin 1, App. H). The

remainder was presumably discharged to the LBR system (see below). Although the form of sediment P in the lake sediment and shoreline was not clear, the only

P mineral for which sufficient geochemical data were available to estimate saturation indices, apatite, was consistently oversaturated (Table 2). Microprobe evidence also supported Ca-P minerals in the sediment (App. L).

A trend is observed of increasing P and N concentrations at the Basin 3 Outlet throughout the fall season (App. E). This suggests winter discharge may have relatively high P and N concentrations. Also, elevated P concentrations are typically observed when DO concentrations are low (i.e. winter or night period;

Uehlinger, 2006). Typically low winter DO concentrations (i.e. consistently less than 0.05 mg/L; Bayley et al., 1995-2) suggest that winter discharge to the LBR, may have high P concentrations. Solute exclusion during overwinter ice formation (Yang et al., 2016) may further increase winter P concentrations in FL.

The estimation of the total mass of P stored in the lake and shoreline sediment is challenged by a lack of historic data on WW Influent P concentrations. Based on one sediment core, an estimated 254 tons of total P is stored in the Basin 1 sediments, which is equivalent to an average annual P deposition of about 9.8 tons (Table 1).

The average annual N mass balance suggests that about 95% of the N in the

WW Influent was either stored in FL or lost to the atmosphere, as N2 gas (Fig.1 and App. H). Based on the single sediment core, an estimated 49 tons total N was annually added to Basin 1 (Table 1), suggesting that significant masses of N

were lost as atmospheric N2 since 197 tons N was stored in the lake based on mass balance (Table 1 and App. H). Nonetheless, increased total N concentrations were observed in the LBR downstream of the FL outlet after 1989

(Table 2).

3.8 Long-term function of Frank Lake and its impact on the Little Bow River

Treated water from FL has been discharged to the LBR since 1992 via the Basin

3 Outlet, with an estimated average annual flow of 3.6×106 m3 (Fig. 3). Water quality in the LBR has been significantly affected by FL discharge, with frequent exceedances of chloride, phosphorous, S.A.R. and EC (Table 2).

Three-fourths of an estimated 845 tons of chloride annually discharging to FL in the WW Influent (i.e. 640 tons) flowed into the LBR, causing the average chloride concentration of the LBR to increase from an average of 1.4 mg/L before wastewater discharge to FL began to 78 mg/L after discharge began (Table 2).

Given FL contributes up to 58% of the LBR’s flow (based on limited data available for 1997), this concentration increase corresponds to a greater than 80 times increase in the Cl mass flux to the LBR. It should be noted that chloride concentrations in the WW Influent (Fig. 2) increased from 123 mg/L during 1990 -

1993 to 257 mg/L during 2012 - 2015 (Table 2) thus there may be an ongoing trend of increasing chloride concentrations in the WW Influent.

Frank Lake’s treatment efficiency for P is poor. Annually more than half (11 tons), of the total P loading to FL flows into the LBR (Fig. 2). The elevated P concentration at the Basin 3 Outlet (2.7 mg/L; Table 2) caused the P

concentration in the LBR downstream of FL (0.9 mg/L) to increase by one order of magnitude, with frequent exceedances of water quality guidelines (Table 2).

The FL discharge water caused the total mass flux in the LBR to increase by greater than 230 times.

Although about 244 tons N were loaded to FL by WW Influent annually, only 5% of this mass was discharged to the LBR, suggesting FL’s N treatment efficiency is high. Nonetheless, there was still a significant impact on the LBR system, with an increase in total N concentration from 0.4 mg/L above the FL outlet to 2.3 mg/L below the outlet (Table 2), which was equivalent to a mass flux increase of >20 times. The mechanism for loss of N is likely denitrification as FL has a high organic loading and generally low oxygen levels (Vymazel, 2007).

Frank Lake is clearly accumulating salt and nutrients in the water column and the sediments surrounding and below the lake. Although chloride mass loading to the

LBR has increased with time (Fig. 2, Table 2, Fig. 9), the long-term rates of nutrient fluxes are not clear. Similarly, although increased nutrient concentrations were observed in late fall (App. E), the overwinter concentrations and flows are not known at this time. Salts and nutrients could be also released to the LBR during a significant hydrologic event.

4. Conclusions

Effective wetland treatment efficiency assessments can benefit from a holistic approach that is: i) underpinned by a physical and chemical water balance, ii) considers annual mass fluxes of a conservative parameter in addition to the

parameters of concern, and iii) considers the ultimate fate(s) of parameters of concern in both the receiving water bodies and within the wetland itself. Many wetland efficiencies are based simply on inlet and outlet concentrations

(Luederitz et al., 2001, Steer et al., 2002 and Plamondona et al 2006). Although some wetland efficiency studies consider water and nutrient mass balances

(Raisin et al, 1999, Borin and Tocchetto, 2007 and Wu et al., 2013) and consider seasonal variations (Lenters et al., 2011; Wu et al., 2013-2), the use of a non- reactive tracer (e.g. chloride) and water isotopes to understand evaporation is not common.

This more holistic evaluation of a natural wetland, FL (Alberta) provided the following conclusions:

• Wastewater Influent, precipitation, and ephemeral creek flows (i.e. spring

runoff) each provided about one-third of FL’s average annual water inflow.

The small residual (~4 ± 4%) of the water balance is likely due to

groundwater input, which is consistent with the low permeability sediments

surrounding the lake. The isotopic composition and geochemical mixtures

of the source water are also consistent with the average annual water

balance;

• The highest water quality in FL was observed immediately after spring

runoff from ephemeral creeks (March and April) and seasonally high

precipitation (June and July). These effects dilute the residual water in FL

from the previous year. During the summer, increasing evaporation rates

resulted in increasing ion and nutrient concentrations and water quality

deterioration;

• About 30% of the chloride entering FL annually is stored within its basin,

either in the water column, the shoreline sediments or the lake bottom

sediments. The remainder was discharged from FL via the Basin 3 Outlet,

where discharge water contributed up to 58% of the LBR’s flow, and

caused a > 80 times increase in Cl mass flux.

• The storage of chloride in near shore sediments, which was attributed to

transpiration pumping, leads to soil water EC values that are above fertility

and irrigation guidelines.

• Chloride concentrations in a single lake sediment core suggest diffusion

has transferred up to 500 tons of chloride from the lake water column to

the sediment below the lake since 1989.

• About 50% of the wastewater P discharged to FL was stored in the lake

(mainly in Basin 1). The remainder was discharged to the LBR, where it

caused mass fluxes to increase by >230 times. The sediment samples

collected in Basin 1 suggest significant P storage is occurring, at least

partly in mineral form. The sediment core samples collected in Basin 1

suggest 254 tons P have accumulated in the near shore sediments and

sediments below the lake.

• Although a N mass balance is difficult due to gaseous losses by

denitrification, an estimated 5% of wastewater N was exported to the LBR

system, in which N mass fluxes increased by > 20 times after receiving FL

discharge. The sediment core samples collected in Basin 1 suggest 1275

tons N have accumulated in shoreline and lake sediments of Basin 1.

• Frank Lake discharge has caused significant increases in chloride, P, and

N concentrations and mass fluxes in the LBR. Given the evidence that

WW If influent loading to FL continues to increase with time, and FL

continues to fill with sediments (currently estimated at a rate of 0.4

cm/year), these mass fluxes will increase. Frank Lake is not a sustainable

approach for effective WW effluent treatment in its current form.

This study illustrates various tools that can be used to assess wetland treatment efficiency. These tools permit a number of conclusions with respect to salt and nutrient fate in FL, including their accumulation in sediments near the shore and below the lake and their discharge to the LBR.

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Tables

Total soil nutrients Estimated pore water concentrations from diffusion modeling depth (cm) Total Nitrogen (tons) Total Phosphorus (tons) depth (m) Chloride (tons) 1.5 to 2 58.2 10.8 0 – 0.6 266 3.5 to 4 58.6 14.7 0.6 – 1.2 134 5.5 to 6 60.4 11.3 1.2 – 1.8 68 7.5 to 8 71.6 13.3 1.8 – 2.4 29 9.5 to 10 57.7 11.0 2.4- 3.0 10 Total mass stored (post 1275 254 Total mass stored (post 1989) 507 1989) Estimated annual average rate of 49.0 9.8 annual average 19.5 deposition (tons/yr) Residual annual Residual annual volumes of mass balance volumes of 197 8.4 101 (tons/yr) mass balance (tons/yr)

Table 2. Frank Lake basin water quality overview. Chloride (CCME, 2011), nitrate (CCME, 2012), phosphorus (CCME, 2004), dissolved oxygen (AEP, 1997), sodium absorption ratio (S.A.R., AAFRD, 2002) and electrical conductivity (EC, AAFRD, 2002) are shown in the table with average value (bolded), standard deviation, number and percentage that exceeded guidelines. Little Bow River (after 1993) downstream included all available data regardless of Frank Lake discharge. Frank Lake (1990-1992), Little Bow River and DO pre-dawn data were provided by Alberta Environment and Parks.

Figures

Fig. 1. Location map including a) country scale with study area; b) Frank Lake basin showing Bow, Highwood, and Little Bow Rivers, High River and Blackie towns, two ephemeral creeks (Blackie and Mazeppa Creeks), Wastewater Influent pipeline, Little Bow River Upstream and Downstream and discharge location to Frank Lake’s Basin 1 (Wastewater Influent); c) detail view of research area showing three basins, lake nearshore & shoreline sediment & shallow groundwater sampling locations (sampled on August 18, 2013 and May 12, 2015 for lake nearshore and shallow groundwater, but shoreline sediment was only sampled once on May 12, 2015), lake interior (Sampled on Aug 18, 2013) and regular sampling locations (Wastewater Influent, Basins 1, 2 and 3 Outlet; sampled biweekly from 2012 to 2015).

Fig. 2. Wastewater influent discharge and chloride with time. 1990s’ discharge data were collected by Alberta Environment and Parks; 1990s’ chloride data were from Sosiak, 1994. Discharge and chloride data, 2012 to 2015, were from current study.

Fig. 3. Schematic diagram of the average annual water balance, chloride balance, total nitrogen balance and total phosphorus balance for Frank Lake (based mainly on 2012 – 2015 data, but also includes sparse available data for the 1990s and 2000s; App. E); Masses of chloride, nitrogen and phosphorus from precipitation are not included since they are negligible relative to the other fluxes. The ΔV and ΔF terms refer to the residual annual volumes and mass fluxes, respectively, that are not accounted for in the mass balances. The ΔF is assumed to accumulate in the lake sediments and shoreline areas.

Fig. 4. Dual isotope plot for δ18O and δ2H in water samples. The composite lake source mixture was based on roughly equal volumetric contributions with isotopic composition of Calgary precipitation, ephemeral creeks (Mazeppa and Blackie Creeks), and wastewater influent. Average values for each type of sample were shown with 95% confidence intervals. The green line (δD = 5.4 δ18O - 49) was consistent with evaporation of the ”calculated source water”. The tendency for higher water isotope values in the summer, and lower isotope values in the winter was based on the data plotted with Julian Day (App. D), and lake interior samples and nearshore Frank Lake samples were collected on August 18, 2013 and May 12, 2015. Shallow Basin 1 sediments were from the lake bottom to 10.4 cm in depth, while the deep sediment samples were from 10.4 to 20 cm in depth.

Fig. 5. Box and whisker plot of Cl and δ18O concentrations in i) potential water sources for Frank Lake: Highwood River (Chao, 2011), Mazeppa and Blackie Creeks, groundwater (as measured in regional water wells, Alberta Water Well Information Database, App. F), wastewater influent (from the town of High River and a meat packaging plant) and lake source mixture (calculated based on water balance by one third of creeks water, one third of precipitation and one third of Wastewater Influent); ii) Frank Lake (Basin 1, 2, and 3 outlets, nearshore areas of the lake and Basin 1 water sampled at frozen periods under ice (Bayley et al., 1995); iii) Frank Lake subsurface water: mini-piezometer groundwater samples, the lake shoreline pore water and pore water of sediment sampled from the centre of Basin 1; iv) Little Bow River sampled up and downstream of Frank Lake outlet (AENV, unpublished data, 1982-2005). The Alberta Surface Water Quality (AB SWQ) and long-term guidelines (120 mg/L, CCME, 2011) are shown in blue, and the Canadian Drinking Water Objective (CDWG, 250 mg/L, Health Canada, 2014) are shown in pink. Only long-term sampling data were used for the potential water sources and Frank Lake water samples. Data with the same letters in the box and whisker indicate data for which non-parametric tests showed values were significantly different (p = 0.05). Significantly differences for potential water sources were not considered. (see next page).

18 Fig. 6. Dual plot of δ O and chloride in pore water and lake water samples, with calculated changes associated with evaporation shown by solid lines. The calculated increases in δ18O were based on relatively humidity value of Blackie station (67%, Alberta Agriculture and Forestry, 2016), with the percentage of residual water indicated by black dots (Skrzypek et al., 2015).

Fig. 8. Piper plots of Frank Lake Basin. Fig. 8a. Difference in piper plot of Wastewater influent water samples from the period 1990 to 1993 (Alberta Environment and Parks data) and 2012 to 2015 (this research program); Fig. 8b. Piper plot of water samples in Frank Lake Basin showing lake water mixed by lake potential water sources (Ephemeral creeks and Wastewater influent). Data were collected in this study from 2012 to 2015; and Fig. 8c. Piper plot of water samples in Basin 3 Outlet and Little Bow River (LBR) showing the effects of LBR by Frank Lake discharge. Data were collected by Alberta Environment and Parks except Basin 3 Outlet (2012 to 2015), which were sampled by this research program. Fig. 8a

Fig. 8b

Fig. 8c

Appendices

Appendix A. Photos of winter discharge of Basin 3 Outlet

Appendix A-a. Basin 3 Outlet at December 1st 2013 showing discharge to the Little Bow River (photo credit: Greg Wagner)

Appendix A-b. Basin 3 Outlet at January 2nd 2014 showing discharge to the Little Bow River (photo credit: Greg Wagner)

Appendix A-c. Basin 3 Outlet at February 9th 2014 showing discharge to the Little Bow River (photo credit: Greg Wagner)

Appendix A-d. Basin 3 Outlet at March 10th 2014 showing discharge to the Little Bow River (photo credit: Greg Wagner)

Appendix A-e. Basin 3 Outlet at November 19th 2014 showing discharge to the Little Bow River (photo credit: Alberta Environment and Parks)

Appendix A-f. Basin 3 Outlet at December 8th 2014 showing discharge to the Little Bow River (photo credit: Greg Wagner)

Appendix A-g. Basin 3 Outlet at December 9th 2014 showing discharge to the Little Bow River (photo credit: Greg Wagner)

Appendix A-h. Basin 3 Outlet at December 21st 2014 showing discharge to the Little Bow River (photo credit: Greg Wagner)

Appendix A-i. Basin 3 Outlet at February 23rd 2015 showing discharge to the Little Bow River (photo credit: Greg Wagner)

Appendix A-j. Basin 3 Outlet at March 15th 2015 showing discharge to the Little Bow River (photo credit: Greg Wagner)

Appendix B. Temperature, precipitation and evaporation plots of Blackie Station (4km away of Frank Lake, 2012 to 2015 daily average, Alberta Agriculture and Forestry, 2016).

Appendix C. MATLAB input code

clear clc %%To run the code click F5 a=importdata('N-EFF.csv'); %%%%%%%Here you need to change the corresponding input file name nanData = isnan(a); index = 1:numel(a); data2 = a; nsample=100; finData=data2; PETURB=[];

%%%Sampling starts From here%%%%%%%% for j=2:length(finData(1,:))

xmini=min(finData(:,j)); xmaxi=max(finData(:,j)); peturb = LHSU(xmini,xmaxi,nsample); PETURB=[PETURB peturb]; end boxplot(PETURB) %%%OUTPUT is PETURB%%%%%%%%%%%%%%%%%%%%%%%%%%%

Appendix D. Basin 1 sediment core particle size percentage between 0.02 to 200 um with d10 ( the particle size at which 10% of the soil is finer), “-“ means unavailable

Particle size ( um) Sample Name d 10 0.020 0.022 0.025 0.028 0.032 0.036 0.040 0.045 0.050 0.056 0.063 0.071 0.080 0.089 1 11.621 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 2 12.087 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 3 17.918 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 4 22.239 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 5 27.045 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 6 26.751 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 7 25.211 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 8 27.797 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 9 33.899 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 10 34.775 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 11 28.441 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 12 49.911 um percentage (%) - 0 0 0 0 0 0 0 0 0 0 0 0 0 13 56.002 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 14 43.095 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 15 38.061 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 16 45.404 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 17 33.095 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 18 45.003 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 19 39.715 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 20 35.062 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 21 36.321 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 22 37.517 um - 0 0 0 0 0 0 0 0 0 0 0 0 0 23 30.467 um - 0 0 0 0 0 0 0 0 0 0 0 0 0

Particle size ( um) Sample Name 0.100 0.112 0.126 0.142 0.159 0.178 0.200 0.224 0.252 0.283 0.317 0.356 0.399 0.448 0.502 0.564 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 6 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 7 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 8 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 9 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 11 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 12 percentage (%) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 13 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 14 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 15 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 16 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 17 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 18 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 19 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 21 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 22 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 23 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Particle size ( um) Sample Name 0.632 0.710 0.796 0.893 1.002 1.125 1.262 1.416 1.589 1.783 2.000 2.244 2.518 2.825 3.170 1 0 0 0 0 0 0 0 0 0 0.035436 0.081 0.169 0.236 0.308 0.380 2 0 0 0 0 0 0 0 0 0 0 0.048 0.147 0.222 0.293 0.360 3 0 0 0 0 0 0 0 0 0 0 0.026 0.083 0.138 0.188 0.235 4 0 0 0 0 0 0 0 0 0 0 0.019 0.061 0.106 0.147 0.185 5 0 0 0 0 0 0 0 0 0 0 0.000 0.010 0.092 0.121 0.157 6 0 0 0 0 0 0 0 0 0 0 0.015 0.061 0.092 0.123 0.159 7 0 0 0 0 0 0 0 0 0 0 0.015 0.063 0.095 0.127 0.163 8 0 0 0 0 0 0 0 0 0 0 0.015 0.060 0.089 0.118 0.151 9 0 0 0 0 0 0 0 0 0 0 0.000 0.008 0.077 0.100 0.128 10 0 0 0 0 0 0 0 0 0 0 0.000 0.007 0.066 0.087 0.113 11 0 0 0 0 0 0 0 0 0 0 0.000 0.009 0.086 0.112 0.144 12 percentage (%) 0 0 0 0 0 0 0 0 0 0 0.000 0.005 0.054 0.073 0.090 13 0 0 0 0 0 0 0 0 0 0 0.000 0.005 0.054 0.071 0.087 14 0 0 0 0 0 0 0 0 0 0 0.000 0.008 0.075 0.094 0.119 15 0 0 0 0 0 0 0 0 0 0 0.000 0.008 0.081 0.102 0.127 16 0 0 0 0 0 0 0 0 0 0 0.000 0.006 0.062 0.083 0.101 17 0 0 0 0 0 0 0 0 0 0 0.017 0.066 0.091 0.117 0.146 18 0 0 0 0 0 0 0 0 0 0 0.000 0.006 0.062 0.082 0.099 19 0 0 0 0 0 0 0 0 0 0 0.000 0.007 0.064 0.083 0.105 20 0 0 0 0 0 0 0 0 0 0 0.000 0.005 0.056 0.078 0.097 21 0 0 0 0 0 0 0 0 0 0 0.000 0.005 0.056 0.079 0.099 22 0 0 0 0 0 0 0 0 0 0 0.000 0.000 0.051 0.069 0.087 23 0 0 0 0 0 0 0 0 0 0 0.016 0.063 0.090 0.118 0.148

Particle size ( um) Sample Name 3.557 3.991 4.477 5.024 5.637 6.325 7.096 7.962 8.934 10.024 11.247 12.619 14.159 15.887 17.825 1 0.446 0.511 0.573 0.635 0.697 0.760 0.825 0.892 0.964 1.038 1.118 1.203 1.295 1.394 1.500 2 0.427 0.490 0.552 0.613 0.675 0.737 0.802 0.868 0.938 1.012 1.091 1.176 1.269 1.371 1.484 3 0.282 0.327 0.370 0.413 0.456 0.499 0.543 0.587 0.635 0.686 0.743 0.807 0.882 0.971 1.076 4 0.224 0.260 0.295 0.329 0.363 0.396 0.431 0.465 0.503 0.543 0.589 0.643 0.708 0.788 0.886 5 0.185 0.215 0.243 0.270 0.297 0.324 0.351 0.380 0.411 0.445 0.484 0.529 0.583 0.648 0.725 6 0.187 0.216 0.244 0.270 0.297 0.324 0.352 0.381 0.413 0.448 0.489 0.535 0.591 0.656 0.734 7 0.193 0.223 0.252 0.281 0.309 0.338 0.369 0.401 0.436 0.474 0.518 0.568 0.629 0.701 0.786 8 0.177 0.204 0.230 0.255 0.281 0.307 0.335 0.364 0.396 0.432 0.472 0.518 0.573 0.636 0.710 9 0.150 0.172 0.192 0.211 0.231 0.250 0.270 0.291 0.315 0.341 0.372 0.409 0.454 0.507 0.572 10 0.134 0.154 0.173 0.191 0.208 0.226 0.244 0.264 0.286 0.311 0.342 0.380 0.427 0.484 0.555 11 0.169 0.196 0.220 0.244 0.267 0.291 0.316 0.342 0.371 0.403 0.442 0.488 0.544 0.612 0.695 12 percentage (%) 0.107 0.123 0.137 0.150 0.163 0.175 0.188 0.200 0.215 0.230 0.249 0.272 0.300 0.335 0.378 13 0.103 0.117 0.131 0.144 0.157 0.169 0.182 0.195 0.209 0.223 0.239 0.257 0.279 0.306 0.339 14 0.138 0.158 0.176 0.194 0.211 0.228 0.246 0.263 0.281 0.300 0.322 0.346 0.375 0.409 0.450 15 0.148 0.169 0.189 0.208 0.228 0.247 0.268 0.289 0.311 0.336 0.363 0.394 0.429 0.470 0.518 16 0.119 0.136 0.152 0.168 0.183 0.198 0.214 0.231 0.249 0.269 0.292 0.318 0.349 0.387 0.431 17 0.170 0.193 0.214 0.235 0.254 0.274 0.294 0.314 0.337 0.362 0.391 0.425 0.466 0.515 0.574 18 0.117 0.134 0.150 0.166 0.181 0.196 0.211 0.227 0.244 0.262 0.282 0.305 0.332 0.367 0.409 19 0.123 0.142 0.158 0.174 0.190 0.206 0.222 0.240 0.259 0.280 0.306 0.336 0.373 0.419 0.475 20 0.116 0.133 0.149 0.163 0.178 0.193 0.210 0.228 0.250 0.276 0.309 0.350 0.402 0.467 0.548 21 0.120 0.139 0.157 0.174 0.190 0.206 0.222 0.238 0.256 0.276 0.300 0.330 0.370 0.422 0.490 22 0.108 0.126 0.142 0.158 0.172 0.186 0.199 0.212 0.226 0.241 0.259 0.284 0.318 0.367 0.435 23 0.172 0.196 0.216 0.236 0.254 0.273 0.291 0.311 0.334 0.360 0.393 0.434 0.485 0.549 0.627

Particle size ( um) Sample Name 20.000 22.440 25.179 28.251 31.698 35.566 39.905 44.774 50.238 56.368 63.246 70.963 79.621 89.337 1 1.618 1.744 1.882 2.027 2.180 2.334 2.487 2.636 2.773 2.902 3.018 3.124 3.218 3.304 2 1.612 1.754 1.914 2.088 2.278 2.480 2.690 2.906 3.120 3.334 3.538 3.735 3.912 4.067 3 1.203 1.351 1.526 1.722 1.943 2.179 2.426 2.679 2.926 3.169 3.395 3.609 3.800 3.970 4 1.006 1.148 1.318 1.509 1.721 1.945 2.175 2.404 2.620 2.823 3.002 3.164 3.305 3.432 5 0.819 0.928 1.056 1.198 1.355 1.521 1.690 1.860 2.023 2.182 2.331 2.476 2.618 2.762 6 0.826 0.931 1.052 1.183 1.325 1.471 1.617 1.760 1.894 2.022 2.143 2.264 2.389 2.528 7 0.890 1.009 1.148 1.301 1.467 1.640 1.811 1.976 2.124 2.255 2.362 2.447 2.514 2.569 8 0.798 0.898 1.012 1.137 1.272 1.411 1.550 1.686 1.812 1.931 2.037 2.137 2.233 2.335 9 0.649 0.738 0.842 0.955 1.078 1.206 1.337 1.469 1.597 1.729 1.862 2.006 2.167 2.353 10 0.640 0.740 0.856 0.983 1.122 1.266 1.411 1.554 1.690 1.825 1.957 2.095 2.246 2.421 11 0.797 0.915 1.054 1.208 1.376 1.552 1.728 1.900 2.058 2.205 2.333 2.451 2.560 2.671 12 percentage (%) 0.432 0.494 0.567 0.646 0.731 0.817 0.900 0.980 1.052 1.121 1.189 1.268 1.368 1.505 13 0.380 0.429 0.488 0.555 0.631 0.710 0.790 0.868 0.939 1.003 1.059 1.114 1.172 1.248 14 0.500 0.558 0.626 0.700 0.779 0.857 0.929 0.992 1.040 1.073 1.092 1.106 1.124 1.164 15 0.574 0.637 0.709 0.786 0.868 0.948 1.024 1.090 1.142 1.181 1.206 1.224 1.244 1.280 16 0.484 0.545 0.615 0.692 0.775 0.858 0.940 1.016 1.083 1.141 1.191 1.240 1.296 1.371 17 0.645 0.726 0.819 0.919 1.025 1.129 1.228 1.316 1.388 1.445 1.488 1.522 1.559 1.611 18 0.462 0.526 0.604 0.693 0.794 0.902 1.014 1.123 1.222 1.309 1.377 1.427 1.460 1.482 19 0.544 0.624 0.720 0.825 0.940 1.059 1.176 1.286 1.380 1.457 1.512 1.545 1.560 1.565 20 0.647 0.763 0.900 1.051 1.219 1.394 1.573 1.749 1.915 2.070 2.206 2.327 2.431 2.524 21 0.579 0.689 0.825 0.983 1.164 1.360 1.565 1.773 1.970 2.157 2.319 2.460 2.576 2.674 22 0.527 0.646 0.799 0.983 1.200 1.444 1.710 1.991 2.272 2.554 2.817 3.067 3.292 3.495 23 0.724 0.835 0.965 1.105 1.254 1.405 1.550 1.685 1.803 1.905 1.992 2.072 2.155 2.254

Particle size ( um) Sample Name 100.237 112.468 126.191 141.589 158.866 178.250 200.000 224.404 251.785 282.508 316.979 355.656 1 3.381 3.447 3.502 3.540 3.554 3.539 3.485 3.388 3.245 3.056 2.830 2.565 2 4.188 4.266 4.290 4.250 4.137 3.950 3.685 3.354 2.970 2.550 2.126 1.708 3 4.114 4.228 4.308 4.346 4.334 4.267 4.136 3.938 3.678 3.358 2.998 2.600 4 3.548 3.657 3.762 3.862 3.953 4.024 4.067 4.066 4.011 3.892 3.708 3.451 5 2.913 3.074 3.249 3.433 3.627 3.818 3.999 4.151 4.261 4.313 4.294 4.191 6 2.689 2.876 3.097 3.345 3.621 3.902 4.176 4.417 4.599 4.701 4.702 4.587 7 2.623 2.684 2.765 2.871 3.011 3.179 3.372 3.574 3.768 3.937 4.058 4.113 8 2.448 2.581 2.743 2.933 3.158 3.404 3.667 3.923 4.155 4.341 4.456 4.483 9 2.572 2.826 3.121 3.442 3.789 4.134 4.461 4.739 4.945 5.055 5.051 4.923 10 2.628 2.872 3.162 3.483 3.836 4.191 4.532 4.826 5.046 5.167 5.167 5.034 11 2.791 2.927 3.089 3.271 3.478 3.689 3.896 4.074 4.205 4.269 4.254 4.149 12 percentage (%) 1.695 1.950 2.287 2.697 3.189 3.729 4.303 4.864 5.371 5.782 6.049 6.144 13 1.358 1.519 1.752 2.066 2.481 2.984 3.572 4.210 4.859 5.473 5.985 6.353 14 1.248 1.393 1.626 1.955 2.397 2.934 3.560 4.231 4.902 5.524 6.027 6.369 15 1.349 1.470 1.663 1.938 2.311 2.767 3.304 3.885 4.472 5.025 5.483 5.811 16 1.482 1.642 1.871 2.174 2.566 3.030 3.561 4.127 4.689 5.207 5.626 5.912 17 1.694 1.824 2.017 2.275 2.611 3.004 3.446 3.903 4.340 4.722 5.004 5.161 18 1.505 1.544 1.616 1.740 1.938 2.214 2.581 3.029 3.539 4.087 4.620 5.107 19 1.572 1.594 1.649 1.754 1.927 2.173 2.501 2.903 3.363 3.858 4.344 4.793 20 2.608 2.689 2.775 2.869 2.977 3.099 3.237 3.385 3.538 3.688 3.819 3.920 21 2.759 2.840 2.928 3.030 3.155 3.302 3.472 3.654 3.836 4.002 4.130 4.202 22 3.676 3.833 3.971 4.085 4.177 4.239 4.266 4.251 4.189 4.076 3.912 3.695 23 2.383 2.551 2.772 3.038 3.353 3.692 4.039 4.360 4.625 4.806 4.876 4.820

Particle size ( um) Sample Name 399.052 447.744 502.377 563.677 632.456 709.627 796.214 893.367 1002.374 1124.683 1261.915 1415.892 1 2.280 1.974 1.664 1.356 1.062 0.787 0.539 0.339 0.122 0.041 0 0 2 1.333 1.001 0.729 0.514 0.352 0.240 0.158 0.099 0.069 0.026 0 0 3 2.196 1.786 1.398 1.041 0.715 0.467 0.238 0.007 0 0 0 0 4 3.138 2.770 2.369 1.950 1.536 1.142 0.787 0.503 0.208 0.082 0 0 5 4.003 3.725 3.373 2.958 2.505 2.045 1.592 1.186 0.830 0.545 0.328 0.181 6 4.356 4.010 3.573 3.067 2.528 1.994 1.485 1.044 0.664 0.397 0.181 0.000 7 4.085 3.963 3.745 3.435 3.046 2.603 2.121 1.648 1.197 0.810 0.497 0.276 8 4.408 4.225 3.942 3.570 3.132 2.658 2.164 1.693 1.253 0.878 0.570 0.340 9 4.674 4.309 3.854 3.333 2.778 2.228 1.700 1.236 0.833 0.527 0.285 0.122 10 4.771 4.380 3.888 3.319 2.710 2.106 1.524 1.011 0.605 0.230 0.054 0 11 3.959 3.687 3.352 2.972 2.567 2.162 1.765 1.403 1.074 0.796 0.565 0.383 12 percentage (%) 6.046 5.753 5.284 4.671 3.959 3.209 2.456 1.772 1.163 0.697 0.327 0.079 13 6.517 6.455 6.158 5.641 4.943 4.131 3.252 2.407 1.617 0.991 0.478 0.123 14 6.495 6.386 6.041 5.480 4.748 3.915 3.030 2.195 1.423 0.835 0.348 0.005 15 5.960 5.913 5.665 5.231 4.644 3.960 3.217 2.495 1.818 1.245 0.784 0.446 16 6.017 5.927 5.639 5.170 4.556 3.853 3.101 2.379 1.712 1.156 0.714 0.398 17 5.166 5.016 4.721 4.308 3.812 3.281 2.743 2.247 1.800 1.424 1.108 0.844 18 5.477 5.702 5.742 5.586 5.239 4.733 4.096 3.405 2.691 2.030 1.447 0.973 19 5.141 5.362 5.417 5.294 4.995 4.547 3.979 3.359 2.719 2.125 1.593 1.147 20 3.971 3.961 3.877 3.714 3.471 3.161 2.791 2.396 1.986 1.599 1.242 0.930 21 4.197 4.104 3.916 3.637 3.279 2.869 2.422 1.983 1.561 1.192 0.875 0.618 22 3.437 3.136 2.811 2.469 2.122 1.785 1.460 1.166 0.899 0.673 0.484 0.333 23 4.637 4.330 3.922 3.440 2.916 2.387 1.872 1.410 1.003 0.673 0.417 0.239

Particle size ( um) Sample Name 1588.656 1782.502 2000.000 1 0 0 0 2 0 0 0 3 0 0 0 4 0 0 0 5 0.074 0.042 0 6 0.000 0.000 0 7 0.109 0.058 0 8 0.187 0.079 0.038 9 0.027 0 0 10 0 0 0 11 0.254 0.136 0.078 12 percentage (%) 0.014 0 0 13 0.023 0 0 14 0 0 0 15 0.228 0.085 0.034 16 0.198 0.071 0.027 17 0.624 0.401 0.228 18 0.617 0.343 0.172 19 0.793 0.480 0.260 20 0.669 0.419 0.233 21 0.429 0.240 0.143 22 0.224 0.121 0.070 23 0.104 0.054 0.013

Appendix E. Julian day plots of Frank Lake basin Appendix E-a. Julian day of discharge of Blackie creek, Mazeppa Creek, Wastewater Influent, Basin 1 Outlet, Basin 2 Outlet and Basin 3 Outlet. Data were provided by Alberta Environment except 2012 to 2015 that were measured by fieldwork with an velocity meter for this study (legends are same for all julian day plots)

Appendix E-b. Julian day of total nitrogen of Blackie creek, Mazeppa Creek, Wastewater influent, Basin 1 Outlet, Basin 2 Outlet, Basin 3 Outlet Little Bow River (LBR) Upstream and LBR Downstream. All data was provided by Alberta Environment except 2012 to 2015 that were analyzed by lab work for this study.

Appendix E-c. Julian day of total phosphorus of Blackie creek, Mazeppa Creek, Wastewater influent, Basin 1 Outlet, Basin 2 Outlet, Basin 3 Outlet, Little Bow River (LBR) Upstream and LBR Downstream. All data was provided by Alberta Environment except 2012 to 2015 that were analyzed by lab work for this study.

Appendix E-d. Julian day of Chloride of Blackie creek, Mazeppa Creek, Wastewater influent, Basin 1 Outlet, Basin 2 Outlet, Basin 3 Outlet Little Bow River (LBR) Upstream and LBR Downstream. All data was provided by Alberta Environment except 2012 to 2015 that were analyzed by lab work for this study.

Appendix E-e. Julian day of D of Blackie creek, Mazeppa Creek, Wastewater influent, Basin 1 Outlet, Basin 2 Outlet and Basin 3. All data were analyzed by lab work for this study (2012-2015).

Appendix E-f. Julian day of 18O of Blackie creek, Mazeppa Creek, Wastewater influent, Basin 1 Outlet, Basin 2 Outlet and Basin 3. All data were analyzed by lab work for this study (2012-2015).

Appendix F. All relative data of Frank Lake Basin (“-“ means unavailable) Appendix F-a. Wastewater Influent data (2012 – 2015)

ms/cm mg/L ℃ m3/s mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L ‰ ‰ Date 2 18 EC pH DO TEMP. Discharge Cl SO4 HCO3 NO3 Ca Mg Na K NH4 TDS TDP TP TN  H  O Jun-4-12 - - - - - 184 228 429 3 62 34 204 39 24 1181 4.34 >3 - -140.2 -17.3 Jun-7-12 1.8 7.5 2.6 18 0.18 196 246 317 18 83 38 235 38 18 1153 4.09 - - -128.4 -13.6 Jun-18-12 1.9 7.3 2.6 20.9 0.14 199 218 405 37 81 40 273 46 11 1261 3.72 4.8 - -137.2 -16.6 Jul-3-12 1.7 7.1 2.8 21.4 0.13 173 302 322 31 92 51 216 32 13 1188 4.04 5.3 - -136.9 -17.1 Jul-18-12 2.0 7.1 2.0 25.8 0.14 252 269 234 67 78 38 288 48 9 1206 3.94 4.9 - -136.2 -16.7 Jul-30-12 1.8 7.2 2.0 25.2 0.12 187 275 307 55 83 43 281 45 <0.1 1221 3.52 4.8 - -129.9 -14.6 Aug-13-12 1.8 7.1 2.3 24.9 0.13 187 269 310 64 84 42 277 46 <0.1 1215 3.71 - - -134.2 -16.2 Aug-27-12 2.2 7.2 - 22.7 0.13 306 252 383 54 81 38 357 48 11 1466 4.31 - - -133.6 -16.1 Sep-11-12 2.1 7.3 7.7 20.1 0.11 238 238 312 52 88 42 328 47 <0.1 1293 6.19 - - -133.4 -16.8 Sep-27-12 2.1 7.1 2.0 22.3 0.15 248 253 254 73 82 36 312 47 2 1232 4.03 - - -133.7 -16.3 Oct-9-12 1.9 7.3 2.0 18.2 0.14 167 236 342 <0.1 81 36 263 44 6 1168 3.93 - - -126.3 -13.0 Oct-22-12 1.9 7.4 2.2 16.9 0.13 181 216 620 2 75 33 278 43 9 1446 3.46 - - -137.5 -16.9 Dec-31-12 2.7 7.8 - - - 330 250 520 27 81 33 300 49 46 1500 - 4.4 - - - Mar-11-13 - - - - 0.12 238 232 298 78 90 34 297 62 19 1250 - - - -141.5 -18.2 Apr-5-13 2.0 7.2 2.9 12.7 0.14 188 232 559 1 88 32 291 56 <0.1 1446 - - - - - Apr-16-13 - - - - - 190 190 293 - 72 27 200 45 - 1100 - - - - May-8-13 2.0 7.4 - 18.3 0.12 307 227 366 31 77 27 377 58 <0.1 1438 - - - - - May-23-13 - - - - - 270 210 378 - 69 31 290 54 - 1300 - - - - Jun-4-13 - - - - - 200 220 537 - 73 31 250 46 - 1200 - - - - Jun-18-13 2.5 7.4 2.1 22 0.15 378 248 415 56 63 31 405 60 <0.1 1601 - - - -125.0 -13.0 Jul-8-13 - - - - - 480 170 757 - 82 27 470 66 - 1700 - - - - Jul-20-13 1.6 7.4 2.6 25.1 0.20 152 253 454 7 105 31 216 30 <0.1 1241 2.85 - - -129.9 -16.6 Jul-25-13 - - - - - 170 230 452 - 98 44 210 34 - 1100 - - - - Aug-18-13 2.0 7.7 2.3 26.1 0.13 231 254 468 0 89 40 359 57 <0.1 1499 5.86 - - -128.4 -16.3 Oct-23-13 2.1 7.7 3.2 17.1 0.12 167 323 590 13 117 50 262 40 14 1549 1.70 - - -126.5 -15.8 Mar-17-14 - - - - - 180 230 440 - 87 34 200 40 - 1100 - - -138.3 -17.7 Apr-15-14 - - - - 0.10 190 210 380 - 79 34 200 37 - 1100 - - -138.6 -18.1 May-7-14 - - - - 0.16 240 190 370 - 65 29 290 55 - 1200 - - -135.5 -17.2 May-22-14 - - - - 0.11 190 240 350 - 97 41 230 40 - 1300 - - - - Jun-11-14 - - - - - 190 280 400 - 81 38 240 41 - 1300 - - -134.2 -16.9 Jun-24-14 - - - - - 180 270 370 - 85 43 230 38 - 1200 - - - - Jul-9-14 - - - - 0.09 170 290 400 - 95 45 230 43 - 1300 - - -134.8 -17.7 Jul-28-14 - - - - 0.11 160 380 350 - 100 53 220 34 - 1400 - - - - Aug-15-14 - - - - 0.16 190 240 200 - 78 37 300 58 - 1400 - - - - Sep-23-14 - - - - - 170 310 310 - 91 46 210 38 - 1300 - - - - May-12-15 - - - - - 325 238 244 71 89 35 335 45 9 - - - - - Jan-5-15 2.5 7.0 4.3 8.5 - 260 250 350 54 110 46 280 46 10 1400 2.70 3.8 67 - - Feb-23-15 2.2 7.2 3.4 12.8 - 270 220 340 51 83 34 290 52 12 1400 3.80 4.5 68 - - Apr-10-15 1.8 7.1 2.0 15.7 0.13 170 200 260 54 83 31 190 37 10 1100 2.20 3.3 67 - - Apr-24-15 2.0 7.3 2.0 17.8 0.14 230 220 380 23 87 32 210 36 10 1100 1.80 2.5 36 - - May-6-15 2.2 7.0 2.9 15.3 0.10 270 230 210 72 99 38 260 36 12 1400 3.10 4.7 87 - - May-26-15 3.1 7.1 1.8 21.0 - 560 - - 60 78 34 450 49 12 1800 3.50 4.4 68 - - Jun-10-15 - - - - - 690 - - 47 80 37 520 53 9 2000 2.50 3.5 59 - - Jun-30-15 2.6 7.0 1.9 24.0 - 330 - - 59 86 36 330 42 14 1500 2.20 3.0 72 - - Jul-27-15 - - - - - 530 - - 53 74 32 410 49 9 1800 3.70 4.6 65 - - Jul-27-15 3.0 6.9 2.0 23.8 0.10 ------Aug-19-15 3.1 7.0 1.6 23.2 0.11 630 - - 43 82 36 460 55 9 1900 2.40 3.2 53 - - Sep-10-15 2.1 7.1 2.0 20.5 0.11 220 - - 42 86 39 290 48 8 1300 3.40 4.6 51 - -

Appendix F-b. Basin 1 Outlet data (2012 – 2015)

ms/cm - mg/L ℃ m3/s mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L ‰ ‰ Date 2 18 EC pH DO TEMP. discharge Cl SO4 HCO3 NO3 Ca Mg Na K NH4 TDS TDP TP TN  H  O Jun-4th-12 - - - - - 167 423 325 0.11 46 47 219 43 <0.1 1270 0.69 1.62 - -102.28 -9.16 Jun-7th-12 1.64 9.55 8.6 13.1 0.155 151 377 325 <0.1 47 47 263 42 <0.1 1251 0.73 - - -99.33 -8.99 Jun-18th-12 1.65 9.34 7.04 15.4 0.127 152 407 376 <0.1 44 49 279 42 0.27 1349 0.84 1.4 - -98.27 -9.08 Jul-3rd-12 1.814 8.18 6.43 17.4 0.066 149 425 451 <0.1 66 60 279 46 <0.1 1477 2.43 2.7 - -97.94 -9.85 Jul-18th-12 1.856 8.57 8.9 24 0.066 159 422 495 0.32 65 56 293 48 1.84 1539 3.14 3.5 - -92.91 -8.16 Jul-30th-12 1.874 9.36 15.34 22 0.039 174 434 447 <0.1 66 55 306 47 <0.1 1529 1.43 2.4 - -91.08 -7.96 Aug-13th-12 1.98 9.57 10.23 18.9 0.088 184 462 517 <0.1 66 58 335 54 <0.1 1677 1.07 - - -85.81 -6.78 Aug-27th-12 1.96 9.55 - 18.1 0.030 203 440 429 <0.1 45 49 341 51 <0.1 1557 1.01 - - -83.96 -5.9 Sep-11th-12 2.11 8.36 9.36 13.6 0.025 223 585 478 <0.1 58 63 383 57 <0.1 1846 0.51 - - -82.28 -6.91 Sep-27th-12 2.27 9.47 4.77 12.4 0.022 224 559 454 0.28 57 61 385 55 <0.1 1795 0.86 - - -83.29 -6.64 Oct-9th-12 2.39 9.25 9.2 7.6 0.021 236 577 486 <0.1 61 61 406 57 <0.1 1885 0.70 - - -81.75 -6.09 Oct-22nd-12 2.46 8.3 9.06 1.6 0.031 222 660 551 2.25 71 74 425 58 <0.1 2062 0.90 - - -82.08 -6.36 Apr-5th-13 0.98 7.89 8.89 1.7 1.041 88 211 268 6.90 48 31 208 37 <0.1 891 - - - - - Apr-16th-13 - - - - - 110 210 281 - 46 28 140 30 - 730 - - - - - May-8th-13 2.02 9.53 - 13.4 - 205 497 712 1.52 79 62 383 58 <0.1 1996 - - - - - May-23rd-13 - - - - - 160 320 399 - 57 38 210 40 - 1000 - - - - - Jun-4th-13 - - - - - 180 410 541 - 72 54 270 51 - 1300 - - - - - Jun-18th-13 1.92 8.2 4.18 18.7 0.236 156 326 481 5.01 68 40 259 47 <0.1 1376 - - - -112.59 -11.91 Jul-8th-13 - - - - - 180 360 488 - 74 48 250 46 - 1200 - - - - - Jul-20th-13 1.992 8.95 6.01 23.1 0.054 197 375 515 1.07 125 40 328 48 <0.1 1628 2.47 - - -94.07 -8.52 Jul-25th-13 - - - - - 15 180 554 - 66 47 270 45 - 870 - - - - - Aug-18th-13 1.97 9.82 15.95 26.6 0.081 202 397 578 0.02 76 55 342 50 <0.1 1701 0.59 - - -86.14 -6.48 Oct-23rd-13 2.06 9.41 15.2 7.7 0.038 223 491 554 <0.1 74 62 389 56 <0.1 1848 1.36 - - -91.00 -8.81 17-Mar-14 - - - - - 74 170 210 - 34 21 100 27 - 550 - - - - - 15-Apr-14 - - - - 1.470 25 96 130 - 22 13 43 19 - 290 - - - -166.44 -21.48 7-May-14 - - - - - 71 190 190 - 37 23 120 26 - 590 - - - -147.44 -17.96 22-May-14 - - - - - 78 200 200 - 46 29 130 32 - 650 - - - - - 11-Jun-14 - - - - - 93 190 320 - 49 29 130 31 - 700 - - - -135.19 -15.76 24-Jun-14 - - - - - 110 240 330 - 57 36 160 36 - 840 - - - - - 9-Jul-14 - - - - 0.025 84 200 240 - 57 34 140 30 - 720 - - - -127.58 -14.81 28-Jul-14 - - - - 0.103 95 240 230 - 59 36 180 37 - 840 - - - -119.09 -12.95 15-Aug-14 - - - - 0.095 110 250 200 - 54 39 190 39 - 860 - - - - - 23-Sep-14 - - - - - 130 300 170 - 53 41 210 41 - 980 - - - - - 10-Apr-15 1.822 8.91 10.85 7.532 - 160 330 390 3.40 61 47 230 44 0.21 1100 1.30 1.9 6.5 - - 24-Apr-15 - 9.65 10.74 8.44 1.486 150 300 190 5.20 48 37 190 36 0.1 970 0.51 1.4 11 - - 06-May-15 1.653 9.67 11.24 10.44 0.822 170 310 170 2.50 43 40 250 43 0.099 1000 0.31 2.2 14 - - 26-May-15 1.722 9.59 2.74 15.69 - 180 - - 0.55 32 39 260 45 0.71 1000 1.30 3.5 16 - - 10-Jun-15 - - - - - 200 - - 0.09 66 57 290 56 1.8 1300 2.40 2.9 6.8 - - 30-Jun-15 2.259 8.43 8.38 23.04 - 270 - - 1.10 54 43 320 53 3.8 1300 2.80 5 16 - - 27-Jul-15 - - - - - 320 - - 0.04 53 47 360 57 0.25 1500 0.86 2.1 13 - - 27-Jul-15 2.29 9.21 3.55 16.29 0.065 ------19-Aug-15 2.554 9.18 4.52 17.4 0.028 380 - - 0.17 49 43 400 58 1.2 1600 1.50 2.2 6 - - 10-Sep-15 2.518 8.69 6.38 11.69 0.032 310 - - 0.73 61 53 420 64 1.7 1500 1.90 2.2 5.6 - -

Appendix F-c. Basin 2 Outlet data (2012 – 2015)

m ms/cm mg/L ℃ m3/s mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L ‰ ‰ Date 2 18 Depth EC pH DO TEMP. discharge Cl SO4 HCO3 NO3 Ca Mg Na K NH4 TDS TDP TP TN  H  O Jun-4th-12 ------170 518 432 <0.1 66 52 243 54 0.13 1534 2.20 >3 - -97.8 -8.73 Jun-7th-12 - 1.835 9.14 9.85 14.7 0.092 154 471 427 <0.1 80 65 286 52 <0.1 1536 1.68 - - -94.8 -8.34 Jun-18th-12 - 1.87 8.91 9.1 14.7 0.118 165 474 529 <0.1 82 68 306 54 0.12 1679 1.49 1.6 - -90.75 -6.78 Jul-3rd-12 - 1.848 8.31 6.6 16.6 0.110 150 425 532 <0.1 75 62 282 49 <0.1 1577 2.71 2.8 - -96.45 -9.3 Jul-18th-12 - 1.923 9.1 16.5 24.5 0.028 145 411 542 <0.1 68 57 279 47 <0.1 1550 1.40 1.4 - -87.82 -6.88 Jul-30th-12 - 2.02 6.74 15.43 25.4 0 171 492 478 <0.1 60 62 329 56 <0.1 1647 0.66 0.8 - -84.86 -6.66 Aug-13th-12 - 2.13 9.85 14.25 21.9 0 187 535 486 <0.1 53 60 368 61 <0.1 1750 0.79 - - -76.8 -4.86 Aug-27th-12 - 2.25 9.76 - 23.9 0 191 544 505 <0.1 54 57 373 65 <0.1 1789 0.57 - - -77 -5.3 Sep-11th-12 - 2.65 9.22 10 10.8 0 259 791 586 <0.1 63 84 472 86 <0.1 2340 1.57 - - -72.77 -4.84 Sep-27th-12 - 3.22 8.37 0.17 10.9 0 273 837 664 <0.1 88 96 516 88 0.28 2562 3.62 - - -64.6 -3.12 Oct-9th-12 - 2.53 8.67 6.77 10.4 0 216 596 651 - 77 82 406 70 <0.1 2097 3.54 - - -77.76 -5.97 Oct-22nd-12 - 2.43 8.51 9.66 0.5 0 210 587 686 0.11 85 83 402 67 <0.1 2120 3.27 - - -81.38 -6.88 Apr-5th-13 - 2.33 8.54 21.2 5.3 0.360 230 604 625 2.85 98 86 508 71 <0.1 2222 - - - - - Apr-16th-13 ------210 520 603 - 79 66 330 53 - 1600 - - - - - May-8th-13 - 2.25 9.42 - 14.3 0.182 211 519 693 1.54 81 66 400 60 <0.1 2030 - - - - - Jun-18th-13 - 2.35 8.42 10.4 19.8 0.102 191 484 564 1.67 73 44 361 56 <0.1 1773 - - - -93.03 -6.89 Jul-20th-13 - 2.19 9.66 16.03 22.5 0.003 210 532 447 <0.1 44 73 386 62 <0.1 1752 0.67 - - -81.84 -6.31 Aug-18th-13 - 3.01 8.814 21.71 24.1 - 229 547 537 0.01 44 69 429 66 <0.1 1921 0.42 - - -80.67 -6.35 Oct-23rd-13 - 2.38 9.38 6.04 8.7 - 248 583 620 <0.1 68 74 454 70 <0.1 2117 2.62 - - -81.08 -7.37 17-Mar-14 ------300 690 670 - 81 79 460 72 - 2000 - - - - - 15-Apr-14 - - - - - 2.240 53 160 190 - 30 20 87 25 - 470 - - - -162.34 -20.49 7-May-14 - - - - - 1.110 140 310 260 - 44 39 210 37 - 960 - - - -128.88 -14.78 22-May-14 - - - - - 0.924 150 310 250 - 52 41 230 42 - 1000 - - - - - 11-Jun-14 ------160 310 390 - 53 40 200 42 - 1000 - - - -124.37 -14.21 24-Jun-14 ------150 310 410 - 62 45 220 45 - 1100 - - - - - 9-Jul-14 - - - - - 0.164 150 340 430 - 70 50 230 48 - 1100 - - - -118.60 -12.93 28-Jul-14 - - - - - 0.069 170 350 490 - 80 56 270 57 - 1300 - - - -111.99 -11.91 15-Aug-14 - - - - - 0.050 170 350 430 - 74 54 260 53 - 1200 - - - - - 23-Sep-14 - - - - - 0.164 160 340 380 - 74 53 250 51 - 1200 - - - - - 24-Apr-15 - 2.01 8.94 9.4 7.78 0.239 170 370 450 1.10 62 51 250 47 0.08 1200 1.30 2.1 4.7 - - 06-May-15 - 1.97 9.28 12.2 10.88 0.225 170 360 330 L0.015 62 53 280 52 0.07 1200 0.92 1.9 6.4 - - 12-May-15 ------170 393 525 0.17 60 58 316 56 ------99.00 -10.20 26-May-15 - 2.098 8.88 5.59 14.51 - 190 - - 0.13 65 53 290 51 0.50 1300 1.50 2.3 5.2 - - 10-Jun-15 ------200 - - 0.12 72 60 300 58 1.60 1400 2.50 2.8 5.3 - - 30-Jun-15 - 2.256 8.84 12.95 22.71 0.005 180 - - 0.38 74 56 300 57 0.18 1400 2.40 2.7 3.4 - - 27-Jul-15 ------210 - - 0.00 53 56 350 65 0.10 1500 0.63 1 4.5 - - 27-Jul-15 - 2.284 9.39 1.89 13.98 ------

Appendix F-d. Basin 3 Outlet data (2012 – 2015)

ms/cm mg/L ℃ m3/s mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L ‰ ‰ Date 2 18 EC pH DO TEMP. discharge Cl SO4 HCO3 NO3 Ca Mg Na K NH4 TDS TDP TP TN  H  O Jun-4th-12 - - - - - 218 668 561 <0.1 92 85 406 69 <0.1 2100 3.64 >3 - -93.4 -7.98 Jun-7th-12 1.842 8.64 10.62 14.2 0.115 141 518 329 <0.1 74 63 286 21 <0.1 1432 1.93 - - -83.92 -8.29 Jun-18th-12 2.14 8.28 3.72 15.4 0.108 185 561 600 <0.1 92 79 353 60 <0.1 1931 2.65 2.3 - -93.85 -7.98 Jul-3rd-12 1.99 8.11 7.2 17.8 0.072 155 478 517 <0.1 81 68 305 55 <0.1 1659 2.75 2.8 - -91.21 -8.75 Jul-18th-12 2.46 8.31 8.93 23.2 0.055 189 531 737 <0.1 84 73 380 62 <0.1 2057 2.26 2.3 - -76.19 -5.49 Jul-30th-12 2.82 8.59 2.99 20.9 0.001 248 760 720 <0.1 100 97 485 79 <0.1 2489 1.96 2 - -61.65 -2.22 Aug-13th-12 3.19 8.99 7.75 18.9 0 314 919 756 <0.1 92 105 585 90 <0.1 2862 1.35 - - -61.58 -1.89 Aug-27th-12 3.34 9.74 - 17 0 348 978 695 <0.1 63 82 624 99 <0.1 2889 0.79 - - -46.54 3.06 Sep-11th-12 3.82 9.44 9.76 9.8 0 478 1286 710 <0.1 47 104 819 118 <0.1 3562 0.88 - - -43.33 2.02 Sep-27th-12 - 9.74 - - 0 565 1535 830 <0.1 50 122 974 145 <0.1 4220 1.35 - - -36.83 3.1 Oct-9th-12 - - - - 0 ------Oct-22nd-12 - - - - 0 ------Apr-5th-13 3.42 8.34 11.67 4.6 0.044 269 848 759 0.31 133 109 603 83 <0.1 2805 - - - - - Apr-16th-13 - - - - - 220 630 590 - 83 73 360 61 - 1700 - - - - - May-8th-13 2.35 9.97 - 15.1 0.101 246 664 678 0.08 79 82 475 71 <0.1 2294 - - - - - May-23rd-13 - - - - - 240 660 672 - 88 75 370 62 - 1800 - - - - - Jun-4th-13 - - - - - 180 490 583 - 82 62 310 59 - 1500 - - - - - Jun-18th-13 2.74 8.63 5.54 18.4 0.095 219 617 683 0 86 42 439 65 <0.1 2150 - - - -89.1 -6.92 Jul-8th-13 - - - - - 240 660 670 - 92 70 410 67 - 1800 - - - - - Jul-20th-13 3.01 8.71 3.87 23.3 - 278 733 883 <0.1 122 94 587 87 <0.1 2785 2.98 - - -63.10 -1.49 Jul-25th-13 - - - - - 220 570 730 - 110 82 420 77 - 1800 - - - - - Aug-18th-13 2.25 10.29 14.2 18.9 - 305 748 386 0.0205 53 51 530 73 <0.1 2146 2.47 - - -72.82 -4.91 Oct-23rd-13 3.18 8.73 8.94 9.1 - 317 795 693 <0.1 93 91 562 81 <0.1 2633 2.07 - - -82.82 -7.81 17-Mar-14 - - - - - 22 80 110 - 23 10 30 23 - 250 - - - -167.85 -20.75 15-Apr-14 - - - - 1.110 79 180 230 - 40 23 110 30 - 580 - - - -160.48 -20.19 7-May-14 - - - - 1.140 98 220 250 - 38 28 150 30 - 710 - - - -138.32 -16.25 22-May-14 - - - - 0.989 140 300 350 - 58 45 230 45 - 1000 - - - - - 11-Jun-14 - - - - - 170 330 430 - 55 43 220 45 - 1100 - - - -120.11 -13.55 24-Jun-14 - - - - - 150 310 460 - 59 46 220 46 - 1100 - - - - - 9-Jul-14 - - - - 0.204 160 350 550 - 70 55 270 53 - 1200 - - - -109.15 -11.39 28-Jul-14 - - - - 0.196 190 380 660 - 81 61 320 62 - 1500 - - - -103.55 -9.91 16-Aug-14 - - - - 0.287 200 390 650 - 76 61 340 62 - 1500 - - - - - 19-Nov-14 - - - - - 270 730 810 - 110 92 450 79 - 2100 - - - - - 24-Mar-15 - - - - - 170 450 540 0.013 77 65 310 49 L0.05 1400 2.20 2.4 2.4 - - 10-Apr-15 1.958 8.17 6.2 7.5 0.824 160 370 500 0.025 69 52 240 45 0.076 1200 1.70 1.9 2.2 - - 24-Apr-15 2.344 8.7 9.62 6.23 0.280 190 460 560 <0.1 72 57 290 52 0.077 1400 1.70 2.5 4.3 - - 6-May-15 2.479 8.85 9.63 9.93 0.184 200 490 540 <0.1 88 69 380 64 0.058 1600 2.10 2.8 6.7 - - 12-May-15 - - - - - 199 454 537 0.101 76 62 364 61 ------26-May-15 2.686 8.24 2.36 15.01 - 220 - - 0.0057 88 68 380 66 0.51 1700 3.50 3.7 3.8 - - 10-Jun-15 - - - - - 240 - - 0.25 91 76 380 77 1.7 1800 4.80 4.9 6 - - 30-Jun-15 2.985 8.28 8.26 23.81 - 250 - - 0.039 90 71 410 77 1.8 1800 4.20 4.8 5.3 - - 27-Jul-15 3.355 8.79 13.57 19.93 ------

Appendix F-e. Ephemeral creeks data (2012 – 2015)

ms/cm mg/L ℃ m3/s mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L ‰ ‰ Date Sample name 2 18 EC pH DO TEMP. discharge Cl SO4 HCO3 NO3 Ca Mg Na K NH4 TDS TDP TP TN  H  O Apr-5th-13 Blackie Creek 0.854 8.09 12.49 6.47 0.094 6 312 146 0.21 49 30 86 28.2187 <0.1 658 - - - - - 17-Mar-14 Blackie Creek - - - - - 4 43 68 - 14 6 8 22 - 140 - - - -183.30 -23.40 15-Apr-14 Blackie Creek - - - - 0.370 8 190 130 - 33 20 60 21 - 390 - - - -176.91 -22.37 7-May-14 Blackie Creek - - - - 0.033 24 470 270 - 68 50 140 22 - 920 - - - -154.56 -18.41 24-Jun-14 Blackie Creek - - - - - 31 1200 370 - 160 120 280 26 - 2000 - - - - - 24-Mar-15 Blackie Creek - - - - - 21 320 220 <0.1 57 44 110 25 <0.1 700 0.7 0.76 1.9 - - 10-Apr-15 Blackie Creek - - - - 0 ------6-May-15 Blackie Creek - - - - 0 ------26-May-15 Blackie Creek - - - - 0 ------Apr-5th-13 Mazeppa Creek 0.594 8.05 10.21 6.81 0.369 4 169 156 0.31 40 19 56 24.0693 <0.1 468 - - - - - 17-Mar-14 Mazeppa Creek - - - - - 6 51 74 - 17 7 13 22 - 160 - - - -188.54 -24.35 15-Apr-14 Mazeppa Creek - - - - 0.143 8 210 190 - 45 25 66 18 - 470 - - - -170.92 -21.46 7-May-14 Mazeppa Creek - - - - 0.144 ------7-May-14 Mazeppa Creek - - - - - 17 660 360 - 99 68 190 16 - 1200 - - - -151.19 -18.48 24-Jun-14 Mazeppa Creek - - - - - 17 640 340 - 110 66 190 22 - 1200 - - - - - 24-Mar-15 Mazeppa Creek - - - - - 12 390 250 0.003 68 39 140 18 <0.1 810 0.22 0.27 1.2 - - 06-May-15 Mazeppa Creek - - - - 0 ------26-May-15 Mazeppa Creek - - - - 0 ------17-Mar-14 unknown creek 1 - - - - - 3 ------171.93 -21.9 17-Mar-14 unknown creek 2 - - - - - 15 ------181.00 -23.16 17-Mar-14 unknown creek 3 - - - - - 2 ------179.90 -22.90 17-Mar-14 unknown creek 4 - - - - - 6 ------171.05 -20.98 17-Mar-14 unknown creek 5 - - - - - 4 ------171.00 -20.97

Appendix F-f. Frank Lake subsurface data (2012 – 2015)

mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L ‰ ‰ Date Sample name 2 18 Gradient Cl SO4 HCO3 NO3 Ca Mg Na K NH4 TDS TDP  H  O Oct-23rd-13 mini-piezometer Basin 1 Outlet 0.015 320 444 769 <0.1 133 72 358 70 <0.1 2167 1.252 -120.81 -13.84 Oct-23rd-13 mini-piezometer Basin 2 Outlet 0.032 301 2361 711 <0.1 161 260 819 84 <0.1 4698 0.901 -98.53 -9.7 Oct-23rd-13 mini-piezometer Basin 3 Outlet -0.01 310 346 1210 <0.1 65 75 680 64 <0.1 2750 1.988 -81.11 -5.78 May-12th-15 mini-piezometer Basin 1 Outlet 0.023 233 499 720 0.153 81 70 442 62 1.4 - - - - May-12th-15 mini-piezometer Basin 2 Outlet 0.041 382 2131 1312 0.112 284 204 845 108 6.9 - - -111.00 -12.00 May-12th-15 mini-piezometer Basin 3 Outlet -0.032 251 514 - - 149 103 465 73 3.3 - - -106.00 -10.90 May-12th-15 mini-piezometer 1 0.104 245 650 - - 83 77 486 71 0.5 - - -101.00 -9.90 May-12th-15 mini-piezometer 2 0 320 882 - - 101 106 595 82 - - - -101.00 -9.90 May-12th-15 mini-piezometer 3 0.033 357 1343 - - 190 145 762 105 1.7 - - -100.00 -8.90 May-12th-15 mini-piezometer 4 0.014 381 1519 - - 234 147 632 120 2.4 - - -88.00 -7.40 May-12th-15 mini-piezometer 5 0.029 246 3231 - - 271 257 860 97 6.0 - - -102.00 -10.30 May-12th-15 mini-piezometer 6 0 581 5421 - - 422 525 1608 118 0.0 - - -110.00 -11.10 May-12th-15 mini-piezometer 7 -0.022 430 3365 1513 - 374 314 1084 84 5.8 - - - - May-12th-15 mini-piezometer 8 0.041 297 1655 - 3.977 218 213 517 81 1.1 - - -133.00 -16.00 May-12th-15 mini-piezometer 9 0.036 233 519 - - 83 72 510 69 1.5 - - -98.00 -9.50 May-12th-15 mini-piezometer 10 -0.037 283 2354 - 21.331 267 231 564 75 24.7 - - -132.00 -17.30 May-12th-15 mini-piezometer 11 0 192 1880 - 0.221 158 182 549 71 4.9 - - -110.00 -12.10 May-12th-15 mini-piezometer 12 0.029 273 1568 - - 176 154 656 63 2.5 - - -104.00 -10.80 May-12th-15 mini-piezometer 13 0.042 454 2691 - - 430 257 1004 78 6.6 - - -106.00 -11.10 May-12th-15 mini-piezometer 14 0.02 497 1554 - - 196 153 890 74 - - - -111.00 -11.80 May-12th-15 Shoreline pore water 1 - 166 1854 ------May-12th-15 Shoreline pore water 2 - 779 9625 ------112 -12.1 May-12th-15 Shoreline pore water 3 - 203 5075 ------100 -9.8 May-12th-15 Shoreline pore water 4 - 261 1525 ------100 -9.8 May-12th-15 Shoreline pore water 5 - 196 911 ------92 -8.4 May-12th-15 Shoreline pore water 6 - 161 551 ------100 -9.8 May-12th-15 Shoreline pore water 7 - 262 1570 ------May-12th-15 Shoreline pore water 8 - 454 1964 ------May-12th-15 Shoreline pore water 9 - 558 3324 ------98 -9.5 May-12th-15 Shoreline pore water 10 - 1442 7718 ------100 -9.5 May-12th-15 Shoreline pore water 11 - 60 678 ------120 -13.7 May-12th-15 Shoreline pore water 12 - 234 2648 ------114 -12.2 May-12th-15 Shoreline pore water 13 - 169 1802 ------96 -9.1 May-12th-15 Shoreline pore water 14 - 94 770 ------100 -9.6

Appendix F-g. Frank Lake shoreline and interior data (2012 – 2015)

m ms/cm mg/L ℃ mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L ‰ ‰ Date Sample name 2 18 Depth EC pH DO TEMP. Cl SO4 HCO3 NO3 Ca Mg Na K NH4 TDS TDP  H  O Aug-18th-13 lake interior water 1 0.6 1.925 9.76 14.4 19.7 194 379 481 0.086 77 55 331 47 <0.1 1563 0.910 -89.86 -7.39 Aug-18th-13 lake interior water 2 0.5 1.968 10.12 12.09 19.3 245 309 386 0.088 44 36 350 46 <0.1 1416 0.469 -95.59 -8.75 Aug-18th-13 lake interior water 3 0.7 1.767 8.76 13.81 19.8 183 278 520 1.518 101 43 270 45 3.1712 1439 3.195 -119.97 -13.69 Aug-18th-13 lake interior water 4 0.6 1.88 9.58 15.5 20.9 168 471 459 0.077 71 55 335 47 <0.1 1606 0.503 -86.53 -6.74 Aug-18th-13 lake interior water 5 0.7 1.912 9.09 13.48 20.4 166 425 488 0.082 80 60 321 48 <0.1 1587 1.097 -93.07 -8.29 Aug-18th-13 lake interior water 6 0.5 1.922 8.77 11.82 20.4 187 397 498 0.077 82 58 330 48 <0.1 1599 1.714 -90.35 -7.4 Aug-18th-13 lake interior water 7 0.5 1.85 9.3 13.29 20 170 426 473 0.000 79 58 322 46 <0.1 1575 0.920 -94.97 -9.11 Aug-18th-13 lake interior water 8 1.2 2.36 8.86 9.3 20.8 216 540 564 0.115 83 73 401 66 <0.1 1944 1.318 -86.2 -7.28 Aug-18th-13 lake interior water 9 0.6 2.09 10.69 19.91 24.7 218 543 393 0.093 31 50 406 64 <0.1 1705 0.203 -85.94 -7.15 Aug-18th-13 nearshore lake water 13-1 - 2.26 - - - 272 607 937 0.023 83 83 514 75 <0.1 2570 1.360 -73.32 -4.68 Aug-18th-13 nearshore lake water 13-2 - 2.87 - - - 267 598 481 0.017 83 92 508 77 <0.1 2107 2.091 -78.21 -5.74 Aug-18th-13 nearshore lake water 13-3 - 2.41 - - - 199 652 454 0.030 72 58 426 56 <0.1 1917 0.523 -75.29 -4.59 Aug-18th-13 nearshore lake water 13-4 - 3.13 - - - 305 757 447 0.026 140 103 572 87 <0.1 2411 2.453 -69.77 -2.9 Aug-18th-13 nearshore lake water 13-5 - 2.15 - - - 212 436 781 0.045 82 59 373 53 <0.1 1996 1.147 -91.53 -8.19 Aug-18th-13 nearshore lake water 13-6 - 2.78 - - - 171 711 676 0.020 132 116 499 51 <0.1 2356 0.899 -77.02 -5.29 Aug-18th-13 nearshore lake water 13-7 - 2.51 - - - 191 689 725 0.036 101 81 431 67 <0.1 2284 2.567 -73.8 -4.51 Aug-18th-13 nearshore lake water 13-8 - 2.51 - - - 241 421 364 0.034 88 58 390 57 <0.1 1619 1.829 -89.21 -7.49 Aug-18th-13 nearshore lake water 13-9 - 2.4 - - - 223 409 876 0.017 55 50 375 52 <0.1 2040 0.409 -84.7 -6.29 May-12th-15 nearshore lake water 15-1 - - - - - 285 705 974 - 119 104 553 85 0.5 - - - - May-12th-15 nearshore lake water 15-2 - - - - - 163 356 464 - 36 44 293 48 - - - - - May-12th-15 nearshore lake water 15-3 - - - - - 160 318 305 1.275 38 40 267 46 - - - - - May-12th-15 nearshore lake water 15-4 - - - - - 163 364 512 0.092 63 49 299 54 - - - -101.00 -10.70 May-12th-15 nearshore lake water 15-5 - - - - - 163 353 - - 33 39 277 45 0.4 - - - - May-12th-15 nearshore lake water 15-6 - - - - - 172 391 473 - 58 55 306 55 - - - -101.00 -10.40 May-12th-15 nearshore lake water 15-7 - - - - - 192 309 - 1.660 48 40 290 46 0.5 - - - - May-12th-15 nearshore lake water 15-8 - - - - - 179 382 564 - 63 56 305 55 0.6 - - - - May-12th-15 nearshore lake water 15-9 - - - - - 280 872 732 - 137 108 511 82 3.3 - - - - May-12th-15 nearshore lake water 15-10 - - - - - 281 868 508 - 135 107 503 83 3.5 - - - - May-12th-15 nearshore lake water 15-11 - - - - - 215 496 - - 80 65 391 59 1.6 - - - - May-12th-15 nearshore lake water 15-12 - - - - - 229 532 478 - 45 57 328 58 - - - - - May-12th-15 nearshore lake water 15-13 - - - - - 302 707 - - 124 108 576 88 1.1 - - - -

Appendix F-h. Frank Lake Basin 1 sediment core data (sampled at the deepest area of Basin 1 on February 19, 2015)

cm mg/L (‰) (‰) mg/g % depth Cl 18O TN TP TOC 0.5 452 -14.38 - - - 1 357 - - - - 1.5 344 - - - - 2 321 -14.27 1.194 2.212 4.807 2.5 352 - - - - 3 307 - - - - 3.5 308 -14.02 - - - 4 305 - 0.725 1.822 4.725 4.5 306 - - - - 5 277 -13.66 - - - 5.5 282 - - - - 6 286 - 0.548 1.022 4.314 6.5 268 -13.25 - - - 7 268 - - - - 7.5 269 - - - - 8 251 -12.21 0.455 0.844 3.443 8.5 255 - - - - 9 234 - - - - 9.5 242 -12.05 - - - 10 214 - 0.393 0.747 2.082 10.5 234 - - - - 11 227 -12.26 - - - 11.5 238 - - - - 12 219 - 0.356 0.733 1.777 12.5 218 -12.07 - - - 13 222 - - - - 13.5 212 - - - - 14 203 -11.82 0.321 0.696 1.639 14.5 208 - - - - 15 205 - - - - 15.5 213 -11.92 - - - 16 216 - 0.328 0.669 1.672 16.5 201 - - - - 17 203 -11.75 - - - 17.5 200 - - - - 18 197 - 0.354 0.698 1.684 18.5 211 -11.67 - - - 19 208 - - - - 19.5 277 - 0.3 0.618 1.404

100

Appendix F-i. Frank Lake Wastewater Influent data (2006 – 2011, Alberta Environment and Parks)

ms/cm mg/L ℃ mg/L mg/L mg/L mg/L Date EC pH DO TEMP. NO3 NH4 TDP TP 08-Jun-06 - - - - 67.9 11.6 3.48 4.33 26-Jul-06 - - - - 69.2 1 3.4 3.78 02-Oct-06 - - - - 86.7 0.72 4.46 4.75 23-Apr-07 1.642 7.34 2.11 13.91 37.9 12 4.28 4.59 23-May-07 1.929 7.39 1.43 17.72 47.7 9.56 4.34 4.77 10-Jul-07 1.721 8.56 1.75 24.55 37.1 2.36 3.26 3.6 19-Jul-07 1.705 7.47 2.24 28.05 1.83 3.97 3.29 3.76 22-Apr-08 1.999 6.95 3.78 13.97 63 9.9 5 5.4 03-Jun-08 1.856 7.38 1.66 19.27 46 14 4.9 5.1 29-Jul-08 2.173 7.39 3.23 25 74 9 3.4 4.6 18-Aug-08 1.845 7.31 2.42 24.93 38 1.6 3.4 3.7 26-Apr-10 1.848 7.01 1.78 18.4 80 10 4.7 4.9 27-May-10 2.076 6.9 3.52 20.33 80 9.9 4.7 5 14-Jun-10 1.895 6.96 3.98 20.79 56 6.9 5.5 5.9 30-Jul-10 1.805 7.35 1.9 26.34 15 3.9 4 4.5 09-Sep-10 2.238 7.04 2.13 20.86 71 2.2 4.1 4.3 26-Apr-11 1.983 6.82 1.69 14.94 62 11 3.9 4.2 25-May-11 1.948 7.23 1.77 18.05 75 24 5.6 6.1 28-Jun-11 1.93 7.24 2.2 20.34 53 11 4.7 5.5 18-Jul-11 1.95 7.27 1.96 25.38 32 8.7 4.9 5.2 31-Aug-11 2.151 7.26 2.39 25.39 30 11 4.9 5.2 26-Sep-11 2.228 7.3 2 20.79 52 11 4.8 5.3

101

Appendix F-j. Frank Lake Basin 1 Outlet, and Basin 2 Outlet data (1995 and 1997, Alberta Environment and Parks)

ms/cm mg/L ℃ mg/L mg/L mg/L mg/L Date Sample name EC pH DO TEMP. NH4 TDP TP TN 26-Jun-97 Basin 1 Outlet 0.829 8.86 11.62 16.29 0.15 2.9 3.32 2.48 10-Jul-97 Basin 1 Outlet 0.912 9.04 4.75 19.02 0.91 0.424 0.444 3.65 22-Jul-97 Basin 1 Outlet 0.95 9.31 6.61 20.08 0.85 1.24 1.57 8.16 11-Aug-97 Basin 1 Outlet 0.937 9.77 9.65 16.63 0.36 0.818 1.09 2.46 22-Aug-97 Basin 1 Outlet 0.901 9.79 7.08 16.05 0.25 0.679 0.875 - 24-Mar-95 Basin 2 Outlet ------7.2 - 26-Jun-97 Basin 2 Outlet 1.064 8.57 7.3 18.2 0.17 3.48 3.8 1.9 10-Jul-97 Basin 2 Outlet 1.11 9.16 7.86 19.32 0.12 0.403 0.442 2.31 22-Jul-97 Basin 2 Outlet 1.111 9.48 8.19 20.94 0.08 1.69 2.15 2.74 11-Aug-97 Basin 2 Outlet 1.082 9.87 8.92 15.59 0.08 0.635 1.13 2.31 22-Aug-97 Basin 2 Outlet 1.103 10.16 8.78 16.5 0.09 0.457 0.746 -

102

Appendix F-k. Frank Lake Basin 3 Outlet data (1996 – 2011, Alberta Environment and Parks)

ms/cm mg/L ℃ m3/s mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L Date EC pH DO TEMP. discharge Cl SO4 HCO3 NO3 Ca Mg Na K NH4 TDS TDP TP TN 11-Jun-96 1.193 8.95 6.39 16.06 0.301 116 128 345 0.009 55 30 158 36 1.03 721 1.85 1.9 - 18-Jun-96 1.197 8.61 1.87 13.04 0.293 127 124 367 <0.003 54 27 158 38 0.1 725 1.7 1.76 2 24-Jun-96 1.21 7.94 1.66 12.81 0.318 118 112 411 0.11 57 29 156 36 0.04 722 2.95 3.05 2.46 02-Jul-96 1.363 7.73 0.36 20.92 0.348 129 114 485 0.233 63 37 178 40 0.09 820 4.9 5.11 3.78 09-Jul-96 1.484 7.65 0.31 19.2 0.204 152 125 550 0.01 65 39 188 42 0.06 900 4.4 5.01 3.56 17-Jul-96 1.56 7.88 0.7 19.08 0.154 159 109 608 0.014 72 30 200 36 0.1 924 4.52 5.98 4.46 23-Jul-96 1.6 8.05 1.95 20.51 0.099 164 125 584 <0.03 71 36 193 42 0.1 935 4.15 4.22 3.15 01-Aug-96 1.65 7.99 1.96 20.71 0.079 167 97.5 638 <0.003 74 39 206 47 1.01 961 3.7 4.17 6.2 07-Aug-96 1.55 8.42 3.69 17.17 0.043 167 106 550 <0.01 75 41 220 46 0.17 947 2.55 2.97 5.55 15-Aug-96 1.54 8.59 4.14 19.25 0.028 166 105 562 <0.01 73 39 228 48 0.15 956 2.12 3.36 9.8 22-Aug-96 1.59 8.65 7.28 17.39 0.01 173 108 568 0.014 70 38 235 47 0.14 973 1.82 2.95 10 28-Aug-96 1.67 8.49 3.38 17.37 0.008 190 150 522 <0.003 72 31 205 39 0.15 966 1.96 2.07 1.68 06-Sep-96 1.61 8.36 7.48 12.89 <0.001 202 178 514 0.029 61 30 238 44 0.67 1017 2.11 2.66 4.73 19-Mar-97 0.631 8.06 10.39 1.13 0.017 66 53.9 226 0.101 35 18 76.3 26 0.17 391 1.04 1.16 2.05 25-Mar-97 0.691 7.8 10.89 4.99 0.259 66 76.6 218 0.17 33 17 92.5 26 0.19 425 1.68 2 0.71 02-Apr-97 0.883 8.11 11.62 4.83 0.557 97 96.5 284 0.159 40 22 129 31 0.1 565 2.27 2.49 2.58 07-Apr-97 0.957 8.38 16.23 2.1 0.842 100 110 279 0.124 32 22 135 31 0.18 582 2.43 2.56 2.9 15-Apr-97 0.985 9.06 16.98 5.74 0.784 105 105 260 0.105 36 23 144 30 0.09 594 2.68 3.01 3.01 22-Apr-97 1.024 8.87 11.65 10.36 0.828 114 113 281 <0.003 37 23 147 32 0.03 626 2.43 2.6 4.4 28-Apr-97 1.045 8.7 7.63 9.13 0.893 103 109 301 0.03 38 24 153 33 0.05 627 2.82 2.98 10.4 05-May-97 1.048 8.86 8.56 10.3 0.793 109 108 305 <0.003 37 25 146 31 0.05 630 3.46 3.54 1.6 12-May-97 1.094 8.86 11.14 18.86 0.753 116 107 331 0.01 44 27 158 36 0.05 675 3.17 3.17 0.71 22-May-97 1.107 8.44 7.2 7.16 0.577 114 108 360 0.014 47 28 157 36 0.07 687 3.48 3.52 2.93 29-May-97 0.962 8.58 9.65 20.39 0.616 101 87.7 318 0.019 39 23 122 29 0.08 578 3.19 3.43 1.52 05-Jun-97 1.076 7.48 1.53 16.33 0.575 111 90.6 382 0.017 47 28 150 36 0.14 666 4.04 4.86 2.84 10-Jun-97 1.123 7.9 5.68 22.59 0.512 110 99 408 0.051 50 29 155 37 0.12 697 4.04 4.09 2.75 16-Jun-97 1.118 7.68 5.07 21.5 0.35 110 92.7 416 0.023 53 30 155 37 0.1 700 4.52 5 2.22 26-Jun-97 1.117 7.66 5.16 19.05 0.307 118 108 414 <0.003 52 29 152 34 0.08 712 3.88 4.16 1.55 03-Jul-97 1.221 7.57 2.3 17.29 0.237 111 106 436 0.004 58 31 164 37 0.21 736 3.85 4.25 2.88 10-Jul-97 1.296 7.68 3.73 20.04 0.188 113 116 477 <0.01 49 31 164 36 0.18 750 0.87 0.898 3.1 15-Jul-97 1.28 8.09 2.23 19.87 0.155 134 109 500 0.007 61 33 177 40 0.16 815 3.59 3.63 3.31 22-Jul-97 1.302 8.6 6.66 20.24 0.104 139 108 502 0.016 64 36 194 44 0.24 857 3.59 3.68 3.67 28-Jul-97 1.39 8.55 3.33 20.73 0.095 138 89.1 535 0.017 61 35 193 43 0.32 845 2.65 2.91 3.82 08-Aug-97 1.396 8.68 1.29 17.29 0.044 158 86.5 555 0.037 57 34 208 46 0.92 887 2.42 3 4.14 11-Aug-97 1.295 8.96 2.27 17.73 0.055 147 98.8 483 0.036 51 30 189 40 0.56 822 1.48 1.75 3.07 22-Aug-97 1.217 8.94 1.94 18.22 0.027 153 98.4 466 0.041 52 30 199 43 0.39 837 1.26 1.71 - 27-Aug-97 1.182 9.19 1.87 17.14 0.02 124 123 324 0.051 41 21 181 37 0.51 720 0.928 1.26 3.75 04-Sep-97 1.307 9.05 2.15 17.53 0.013 136 122 388 0.111 48 25 200 40 0.57 782 1.13 1.4 4.13 21-Jul-98 1.203 7.83 3.92 19.53 0.077 86 125 475 0.006 65 35 147 42 0.2 768 3.44 3.6 2.94 06-Aug-98 1.442 8.8 2.1 21.37 0.096 174 134 424 0.014 48 31 217 43 0.26 878 1.42 1.58 3.79 19-Aug-98 1.239 8.98 4.68 15.09 0.089 184 143 454 0.018 47 30 228 43 0.26 946 1.36 1.39 2.48 03-Sep-98 1.74 8.97 2.39 18.41 0.037 213 170 462 0.012 46 30 275 52 0.33 1060 1.71 1.74 2.15 12-Apr-99 1.873 9.14 10.63 4.25 - 266 222 447 <0.003 50 37 311 47 0.01 1200 1.14 1.52 0.66 31-Mar-00 ------2.31 - 01-Apr-00 ------2.21 - 02-Apr-00 ------2.34 - 03-Apr-00 ------2.73 - 04-Apr-00 ------3.2 - 05-Apr-00 2.53 8.52 10.02 3.91 ------0.05 - 3.5 3.82 - 05-Apr-00 ------4.11 - 06-Apr-00 ------3.79 - 07-Apr-00 ------3.91 - 08-Apr-00 ------4.02 - 09-Apr-00 ------3.7 - 10-Apr-00 ------3.62 - 11-Apr-00 ------3.84 - 12-Apr-00 ------3.2 - 13-Apr-00 ------3.85 - 14-Apr-00 ------4.02 - 15-Apr-00 ------3.88 - 16-Apr-00 ------4.02 - 17-Apr-00 2.345 8.5 9.99 4.73 ------0.08 - 2.72 3.95 - 17-Apr-00 ------3 - 18-Apr-00 ------2.88 - 19-Apr-00 ------2.83 - 20-Apr-00 ------2.87 - 21-Apr-00 ------3.06 - 22-Apr-00 ------2.88 - 23-Apr-00 ------3.52 - 24-Apr-00 ------4 - 25-Apr-00 ------4.06 -

103

ms/cm mg/L ℃ m3/s mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L Date EC pH DO TEMP. discharge Cl SO4 HCO3 NO3 Ca Mg Na K NH4 TDS TDP TP TN 26-Apr-00 ------4.14 - 27-Apr-00 ------3.67 - 28-Apr-00 ------3.66 - 29-Apr-00 ------3.5 - 30-Apr-00 ------3.7 - 01-May-00 ------3.15 - 02-May-00 ------3.58 - 03-May-00 3.19 8.56 6.04 11.79 ------0.15 - 3.18 3.3 - 03-May-00 ------4.06 - 04-May-00 ------3.99 - 05-May-00 ------4.06 - 06-May-00 ------3.95 - 07-May-00 ------4.14 - 08-May-00 ------3.85 - 09-May-00 ------4.17 - 10-May-00 ------3.02 - 11-May-00 ------3.45 - 12-May-00 ------3.38 - 13-May-00 ------3.83 - 14-May-00 ------3.29 - 15-May-00 ------3.56 - 16-May-00 ------3.31 - 17-May-00 ------3.11 - 17-May-00 3.343 8.84 10.84 16.72 ------0.12 - 3.06 3.8 - 18-May-00 ------3.16 - 19-May-00 ------3.46 - 20-May-00 ------3.22 - 21-May-00 ------3.35 - 22-May-00 ------2.73 - 23-May-00 ------2.45 - 05-Jul-00 ------2.19 - 06-Jul-00 3.004 8.56 3.86 17.39 ------0.19 - 2.99 3.52 - 06-Jul-00 ------2.44 - 07-Jul-00 ------2.46 - 08-Jul-00 ------2.4 - 09-Jul-00 ------2.47 - 10-Jul-00 ------2.35 - 11-Jul-00 ------2.38 - 12-Jul-00 ------1.98 - 10-Apr-03 1.467 8.4 9.59 8.33 - - - - 0.005 - - - - 0.03 - 1.4 1.89 - 23-Apr-03 2.086 8.83 10.12 12.58 ------0.06 - 1.72 1.75 - 13-May-03 2.125 9.04 10.72 16.73 ------0.05 - 1.58 1.63 - 10-Jun-03 2.851 8.3 3.21 15.1 - - - - 0.003 - - - - <0.01 - 1.81 1.85 - 04-Jul-03 2.742 7.88 3.17 21.12 - - - - 0.003 - - - - 0.41 - 3.48 3.58 - 21-Jul-03 3.352 8.1 2.95 23.52 - - - - 0.007 - - - - 1.18 - 3.95 3.95 - 14-Jun-05 1.81 7.72 2.11 15.15 - - - - 0.01 - - - - 0.42 - 1.76 1.96 - 30-Jun-05 1.811 7.96 3.59 16.14 - - - - 0.056 - - - - 0.57 - 1.72 1.78 - 14-Jul-05 2.377 7.81 2.01 21.76 - - - - <0.003 - - - - 0.12 - 2.23 2.38 - 29-Jul-05 2.742 7.79 2.51 20.6 - - - - 0.01 - - - - 0.23 - 2.77 2.87 - 01-Sep-05 2.958 8.02 3.29 17.14 - - - - 0.03 - - - - 0.16 - 2.42 2.5 - 28-Sep-05 2.537 8.01 2.97 7.09 - - - - 0.028 - - - - 0.06 - 1.62 1.68 - 08-Jun-06 ------0.138 - - - - 0.74 - 3.67 3.87 - 26-Jul-06 ------0.007 - - - - 0.43 - 2.55 2.71 - 02-Oct-06 ------0.114 - - - - 1.51 - 1.57 1.89 - 23-Apr-07 2.024 8.88 10.92 8.32 0.387 - - - <0.003 - - - - 0.06 - 1.24 1.45 - 23-May-07 2.143 8.42 7.45 8.68 - - - - 0.137 - - - - 0.17 - 1.74 1.81 - 10-Jul-07 2.752 10.01 6.11 18 - - - - 0.01 - - - - 0.21 - 3.04 3.24 - 19-Jul-07 1.921 8.73 3.79 23.58 - - - - <0.003 - - - - 0.19 - 2.88 3.08 - 22-Apr-08 3.156 7.88 14.69 2.71 0.082 - - - 0.006 - - - - 0.12 - 2.3 3 - 03-Jun-08 2.727 8.69 7.19 13.67 0.12 - - - 0.47 - - - - 0.24 - 2.9 3 - 29-Jul-08 3.587 8.51 5.16 20.28 0.018 - - - 0.021 - - - - 0.34 - 3.7 3.9 - 18-Aug-08 4.118 8.51 4.94 20.16 0.014 - - - 0.004 - - - - 0.24 - 3.9 4.6 - 26-Apr-10 3.299 8.85 9.65 0.06 - - - - <0.003 - - - - 0.11 - 2.1 2.6 - 27-May-10 3.063 8.48 8.36 9.75 - - - - 0.006 - - - - 0.21 - 1.5 1.7 - 14-Jun-10 2.879 8.27 9.53 19.47 - - - - <0.003 - - - - 0.1 - 2.4 2.5 - 30-Jul-10 3.308 8.46 6.82 20.67 - - - - <0.003 - - - - 0.23 - 3.7 3.8 - 09-Sep-10 3.505 8.44 2.49 11.04 - - - - 0.061 - - - - 0.24 - 2.3 2.4 - 26-Apr-11 1.237 8.69 17.82 11 - - - - 1.6 - - - - <0.05 - 1.2 1.9 - 25-May-11 1.542 8.08 2.91 11.29 - - - - 0.019 - - - - 0.3 - 1.8 1.9 - 28-Jun-11 1.515 7.8 2.69 18.72 - - - - 0.024 - - - - 0.45 - 2.2 2.3 - 18-Jul-11 1.692 8.4 8.64 27.22 - - - - 0.022 - - - - 0.21 - 2.1 2.2 - 31-Aug-11 2.239 7.73 0.91 12.82 - - - - <0.003 - - - - 0.22 - 2.9 3.1 - 26-Sep-11 2.378 8.01 4.95 10.46 - - - - 0.003 - - - - 0.19 - 2.4 2.5 -

104

Appendix F-l. Frank Lake creeks data (1996, 1997 and 1999, Alberta Environment and Parks)

ms/cm mg/L ℃ m3/s mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L Date Sample name EC pH DO TEMP. discharge Cl SO4 HCO3 NO3 Ca Mg Na K NH4 TDS TDP TP TN 04-Feb-97 Blackie Creek ------0.512 - 04-Feb-97 Blackie Creek 0.229 7.48 11.9 4.48 0.076 ------0.04 - 0.449 0.534 4.82 04-Mar-97 Blackie Creek ------0.511 - 19-Mar-97 Blackie Creek 0.204 6.81 7.72 0.86 0.19 ------1.77 - 1.4 1.7 4.11 20-Mar-97 Blackie Creek ------0.577 - 20-Mar-97 Blackie Creek 0.083 6.98 10.8 0.51 2.79 ------0.37 - 0.462 0.554 2.55 21-Mar-97 Blackie Creek ------0.951 - 22-Mar-97 Blackie Creek ------0.958 - 23-Mar-97 Blackie Creek ------0.7 - 24-Mar-97 Blackie Creek ------0.68 - 25-Mar-97 Blackie Creek ------0.597 - 25-Mar-97 Blackie Creek 0.164 7.03 11.7 4.22 1.5 ------0.08 - 0.561 0.647 3.46 26-Mar-97 Blackie Creek ------0.601 - 27-Mar-97 Blackie Creek ------0.54 - 28-Mar-97 Blackie Creek ------0.54 - 02-Apr-97 Blackie Creek ------0.512 - 02-Apr-97 Blackie Creek 0.229 7.48 11.9 4.48 0.076 ------0.04 - 0.449 0.534 4.82 03-Apr-97 Blackie Creek ------0.511 - 05-Apr-97 Blackie Creek ------0.555 - 07-Apr-97 Blackie Creek 0.291 7.74 14.1 1.06 0.016 ------0.04 - 0.431 0.494 1.18 15-Apr-97 Blackie Creek - - - - <0.001 ------04-May-97 Blackie Creek ------0.555 - 04-Jul-97 Blackie Creek 0.291 7.74 14.1 1.06 0.016 ------0.04 - 0.431 0.494 1.18 07-May-99 Blackie Creek 1.928 8.09 8.26 20.98 0.034 ------<0.01 - 1.96 2.21 2.34 05-Jul-99 Blackie Creek 1.928 8.09 8.26 20.98 0.034 ------<0.01 - 1.96 2.21 2.34 14-Mar-96 Mazeppa Creek 1.399 7.47 9.83 0.53 5.14 5 13.4 51.8 - 9.2 3.2 5.6 19.3 0.44 87 0.85 1 - 04-Jan-97 Mazeppa Creek ------0.462 - 04-Feb-97 Mazeppa Creek ------0.458 - 04-Feb-97 Mazeppa Creek 0.386 7.35 8.87 2.2 0.051 ------0.03 - 0.424 0.452 1.64 04-Mar-97 Mazeppa Creek ------0.425 - 19-Mar-97 Mazeppa Creek 0.068 7.03 11.3 0.24 1.483 ------0.24 - 0.105 0.145 1.07 20-Mar-97 Mazeppa Creek ------0.578 - 20-Mar-97 Mazeppa Creek 0.104 7.16 10.2 0.67 4 ------0.34 - 0.502 0.617 2.48 21-Mar-97 Mazeppa Creek ------0.7 - 22-Mar-97 Mazeppa Creek ------0.665 - 23-Mar-97 Mazeppa Creek ------0.667 - 24-Mar-97 Mazeppa Creek ------0.677 - 25-Mar-97 Mazeppa Creek ------0.576 - 25-Mar-97 Mazeppa Creek 0.177 7.2 11.4 3.08 2.59 ------0.11 - 0.519 0.651 3.76 26-Mar-97 Mazeppa Creek ------0.555 - 27-Mar-97 Mazeppa Creek ------0.545 - 28-Mar-97 Mazeppa Creek ------0.537 - 29-Mar-97 Mazeppa Creek ------0.485 - 30-Mar-97 Mazeppa Creek ------0.455 - 31-Mar-97 Mazeppa Creek ------0.487 - 01-Apr-97 Mazeppa Creek ------0.462 - 02-Apr-97 Mazeppa Creek ------0.458 - 02-Apr-97 Mazeppa Creek 0.386 7.35 8.87 2.2 0.051 ------0.03 - 0.424 0.452 1.64 03-Apr-97 Mazeppa Creek ------0.425 - 05-Apr-97 Mazeppa Creek ------0.436 - 07-Apr-97 Mazeppa Creek 0.586 7.68 8.94 1.53 <0.001 ------0.03 - 0.333 0.389 1.1 04-May-97 Mazeppa Creek ------0.436 - 04-Jul-97 Mazeppa Creek 0.586 7.68 8.94 1.53 <0.001 ------0.03 - 0.333 0.389 1.1

105

Appendix F-m. Little Bow River upstream data (1982 – 2010, Alberta Environment and Parks)

ms/cm mg/L ℃ mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L Date EC pH DO TEMP. Cl SO4 HCO3 NO3 Ca Mg Na K NH4 TDS TDP TP TN 22-May-97 0.36 8.17 10.45 7.23 2 43.5 180 - 53.5 13.7 7.98 0.9 0.01 212 0.02 0.064 0.715 5-Jun-97 0.394 7.97 8.94 15.53 4 55.6 191 - 53.2 16.5 15.2 1.19 0.03 241 0.004 0.026 0.27 15-Jul-97 0.319 7.85 7.62 18.5 1 36.3 182 - 49.5 14 6.43 0.74 <0.01 199 0.008 0.019 0.214 11-Aug-97 0.316 8.18 8.34 15.96 ------0.02 - <0.003 0.009 0.14 4-Sep-97 0.373 7.61 6.72 16.92 ------0.01 - <0.003 0.011 0.29 21-Jul-98 0.388 8.22 8.34 18.55 ------0.01 - 0.005 0.028 0.34 6-Aug-98 0.362 8.32 9.49 22.08 ------0.01 - <0.003 0.016 0.28 19-Aug-98 0.366 8.26 9.08 14.43 ------0.01 - <0.003 0.014 0.19 3-Sep-98 0.409 8.1 7.81 17.19 - - - <0.003 - - - - 0.02 - 0.004 0.023 0.28 22-Mar-99 0.362 7.94 10.31 -0.15 ------0.12 - 0.005 0.072 0.78 29-Mar-99 0.382 8.08 11.33 2.12 ------0.18 - 0.004 0.133 1.04 6-Apr-99 0.429 8.12 10.5 6.19 ------0.19 - <0.003 0.106 1.41 12-Apr-99 0.429 8.18 10.39 4.48 ------0.2 - <0.003 0.153 0.9 19-Apr-99 0.452 8.11 8.65 11.93 ------0.14 - 0.003 0.113 1.21 26-Apr-99 0.459 8.22 8.77 12.86 ------0.07 - 0.004 0.095 0.96 3-May-99 0.39 8.23 10.01 8.64 ------0.03 - <0.003 0.105 0.61 10-May-99 0.367 8.28 10.83 6.43 ------0.02 - <0.003 0.083 0.39 17-May-99 0.394 8.35 10.27 9.91 ------<0.01 - <0.003 0.053 0.28 25-May-99 0.361 8.29 8.71 17.3 ------<0.01 - 0.062 0.072 0.64 31-May-99 0.288 8.32 9.62 10.8 ------<0.01 - 0.015 0.053 0.36 7-Jun-99 0.322 8.65 9.72 13.22 ------<0.01 - 0.018 0.027 0.14 19-Jul-99 0.322 7.69 7.13 13.71 ------<0.01 - 0.011 0.037 0.31 23-Aug-99 0.422 8.42 10.11 17.42 ------<0.01 - <0.003 0.011 0.34 20-Sep-99 0.371 8.38 10.53 12.4 ------<0.01 - 0.006 0.021 0.09 20-Oct-99 0.44 7.67 11.61 5.73 ------0.03 - 0.005 0.03 0.42 18-Nov-99 0.376 8.01 11.24 2.08 ------0.12 - 0.005 0.069 0.75 9-Dec-99 0.452 7.76 10.26 -0.17 ------0.08 - 0.005 0.033 0.54 27-Jan-00 0.422 7.17 8.81 -0.13 ------0.05 - <0.003 0.071 0.73 17-Feb-00 0.452 7.26 9.6 -0.15 ------0.03 - 0.003 0.113 0.69 24-Mar-00 0.398 7.77 10.97 -0.14 ------0.07 - <0.003 0.175 0.81 5-Apr-00 0.403 8.05 10.78 4.48 ------0.15 - <0.003 0.201 - 12-Apr-00 0.424 8.1 10.23 6.76 ------0.09 - 0.005 0.182 - 17-Apr-00 0.444 7.99 11.05 5.82 ------0.08 - 0.005 0.18 - 27-Apr-00 0.426 8.13 9.52 9.47 ------0.02 - <0.003 0.056 - 3-May-00 0.408 7.99 9.31 12.08 ------0.1 - <0.003 0.069 - 10-May-00 0.322 8.02 9.65 10.13 ------0.04 - <0.003 0.105 - 16-May-00 0.382 8.24 9.07 13.53 ------0.02 - <0.003 0.09 - 24-May-00 0.373 8.07 9.08 10.8 ------<0.01 - <0.003 0.053 - 29-May-00 0.329 7.83 8.48 11.5 ------<0.01 - <0.003 0.068 - 2-Jun-00 ------0.004 - - 6-Jun-00 0.355 8.31 8.63 15.87 ------<0.01 - 0.055 0.058 - 14-Jun-00 0.282 8.34 9.02 15.61 ------0.02 - 0.018 0.048 - 20-Jun-00 0.322 8.26 9.08 14.5 ------<0.01 - <0.003 0.041 - 18-Jul-00 0.283 8.19 8.53 19.09 ------0.02 - 0.004 0.021 - 31-Aug-00 0.365 8.27 10.63 12.66 ------<0.01 - <0.003 0.01 - 23-Apr-03 0.467 8 8.95 11.48 ------0.01 - 0.007 0.045 - 13-May-03 0.402 7.8 9.02 11.87 ------<0.01 - <0.003 0.063 - 10-Jun-03 0.298 7.86 9.25 12.2 - - - 0.003 - - - - 0.03 - 0.005 0.018 - 4-Jul-03 0.344 7.84 8.64 16.66 - - - <0.003 - - - - 0.01 - 0.02 0.028 - 21-Jul-03 0.44 8.56 11.08 23.81 - - - 0.008 - - - - 0.06 - 0.005 0.02 - 14-Jun-05 0.547 7.94 8.65 13.54 - - - 0.648 - - - - 0.11 - 0.015 0.14 - 30-Jun-05 0.646 7.96 8.1 17.67 - - - 0.846 - - - - 0.31 - 0.034 0.139 - 14-Jul-05 0.547 8.25 10.61 20.18 - - - 0.669 - - - - 0.02 - <0.003 0.004 - 29-Jul-05 0.483 8.41 11.47 21.14 - - - 0.419 - - - - 0.05 - 0.006 0.011 - 1-Sep-05 0.428 8.61 13.08 16.03 - - - 0.294 - - - - 0.09 - 0.003 0.007 - 28-Sep-05 0.584 8.43 11.87 6.71 - - - 0.717 - - - - 0.02 - 0.004 0.009 - 8-Jun-06 ------0.059 - - - - 0.02 - 0.003 0.021 - 26-Jul-06 ------0.007 - - - - 0.1 - 0.006 0.012 - 2-Oct-06 ------0.111 - - - - 0.08 - 0.003 0.012 - 23-Apr-07 0.63 8.23 11.35 7.77 - - - 0.179 - - - - 0.03 - 0.006 0.055 - 23-May-07 0.452 8.34 11.35 9.81 - - - 0.083 - - - - 0.05 - <0.003 0.023 - 10-Jul-07 0.336 9.65 9.41 17.31 - - - 0.018 - - - - <0.05 - 0.006 0.011 - 19-Jul-07 0.303 8.21 7.59 23.31 - - - <0.003 - - - - <0.05 - 0.008 0.018 - 22-Apr-08 0.416 8.05 13.58 1.67 - - - 0.15 - - - - 0.1 - 0.004 0.25 - 3-Jun-08 0.477 7.76 8.91 12.54 - - - 0.35 - - - - 0.1 - 0.003 0.12 - 29-Jul-08 0.348 8.51 9.05 18.94 - - - 0.012 - - - - <0.05 - 0.005 0.016 - 18-Aug-08 0.361 8.19 8.12 19.56 - - - <0.003 - - - - <0.05 - 0.004 0.016 - 26-Apr-10 0.429 7.98 10.91 7.97 - - - 0.04 - - - - <0.05 - 0.006 0.021 - 27-May-10 0.357 7.87 10.68 10.03 - - - <0.003 - - - - <0.05 - 0.005 0.004 - 14-Jun-10 0.383 8.13 9.26 17.16 - - - <0.003 - - - - <0.05 - 0.005 0.023 - 30-Jul-10 0.356 8.32 8.9 19.11 - - - <0.003 - - - - 0.05 - 0.005 0.012 - 9-Sep-10 0.398 8.17 10.36 10.36 - - - <0.003 - - - - 0.27 - 0.008 0.011 -

106

Appendix F-n. Little Bow River downstream data (1982 – 2010, Alberta Environment and Parks)

ms/cm mg/L ℃ mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L Date EC pH DO TEMP. Cl SO4 HCO3 NO3 Ca Mg Na K NH4 TDS TDP TP TN 10-Feb-82 - - 4.35 0 2 75 - - 81.6 21.2 13 2.01 0.18 - 0.034 0.039 - 12-Feb-82 - - 1.2 ------26-Mar-82 - - 7.8 0 5 79 - - 68.4 20.5 19 2.4 0.19 - 0.081 0.105 - 21-Apr-82 - - 8.5 2.5 3 63 - - 48.7 16 18 2.43 0.18 - 0.042 0.06 - 19-May-82 - - 8.75 - 2 61 - - 56 17.1 13.9 1.5 0.12 - 0.016 0.044 - 8-Jun-82 - - 9.7 10 1 41.7 - - 46.8 12.4 9.6 1.4 0.17 - 0.006 0.039 - 7-Jul-82 - - 10.05 16 1 33 - - 50.2 13 7.5 0.76 <0.01 - 0.006 0.024 - 12-Jul-82 - - 8.5 - 1 29.8 - - 43 12.5 6.5 0.8 <0.01 - 0.007 0.022 - 17-Aug-82 - - 9.45 16 1 39.9 - - 43.5 14 5.4 0.67 0.03 - 0.004 0.02 - 13-Sep-82 - - 9.9 8 1 47 - - 47.9 16.2 8.4 1.03 <0.01 - 0.007 0.018 - 12-Oct-82 - - - 6 1 45.2 - - 48.2 18.5 6.2 0.99 <0.01 - 0.005 0.02 - 30-May-90 0.415 8 9.2 11.7 3 38.4 180.41 - 46 11.2 9.4 1.5 0.13 - 0.015 0.175 - 19-Jun-90 0.303 8.1 9 17 1 29.4 182.85 - 48.5 11.9 5.3 0.85 0.02 - 0.005 0.055 - 10-Jul-90 0.322 8 7.5 19.3 0 23.9 179.19 - 45.3 10.6 3.7 0.65 0.02 - 0.008 0.016 - 31-Jul-90 0.314 8.3 9 20.7 1 25.6 173.1 - 44.3 11.5 4 0.62 <0.01 - 0.008 0.025 - 22-Aug-90 0.359 7.1 8 16.2 1 34.8 195 - 48.5 13.6 6 0.93 <0.01 - 0.005 0.023 - 11-Sep-90 0.351 8.2 9.9 16.8 1 45.2 175.5 - 42.5 14.6 7.2 1.11 0.02 - 0.006 0.025 - 2-Oct-90 0.402 7.4 10 7.4 1 49.8 198.7 - 55.2 16.3 6.5 1.25 0.06 - <0.003 0.035 - 23-Oct-90 0.429 7.7 12.5 0.2 1 49.5 225.5 - 60.1 15.3 7.2 1.05 0.04 - <0.003 0.024 - 20-Nov-90 0.451 8 12.8 0 3 52.4 240.1 - 60.9 16 7.3 1.08 0.1 - 0.004 0.023 - 2-Jan-91 0.515 6.1 - 0 2 54.5 275.5 - 74.5 18 7.55 1.35 0.08 - 0.004 0.03 - 22-Jan-91 0.505 6.7 - 0 1 73 251.1 - 70 18.6 7.8 1.5 0.04 - 0.029 0.037 - 20-Feb-91 0.455 7.2 - 0 2 69.5 221.9 - 60.7 16.2 9.5 1.41 0.05 - 0.01 0.051 - 19-Mar-91 0.446 7.1 9.4 0 2 54.8 195 - 57.5 15.2 8.95 1.27 0.02 - 0.006 0.027 - 23-Apr-91 0.437 7.9 9.7 11 2 53.7 202.4 - 58.4 15.1 9.1 1.18 0.02 - 0.004 0.073 - 24-Apr-91 - 7.9 9.7 ------9-Jul-96 0.573 7.87 6.83 17.66 ------0.02 - 0.345 0.391 0.413 7-Aug-96 0.439 8 8.2 15.26 ------0.04 - 0.2 0.201 0.47 2-Apr-97 0.675 7.9 10.98 5.15 54 87.8 255 - 55.2 20.2 75.5 17 0.07 441 1.01 1.02 1.59 22-May-97 0.818 8.41 9.81 7.67 76 86 296 - 49.2 23 103 22.8 0.1 521 2.28 2.3 2.41 5-Jun-97 1.017 7.84 7.36 18.24 92 96.5 358 - 48 27 137 32 0.2 622 3.38 3.62 2.39 15-Jul-97 0.596 8.03 7.96 19.27 26 51.5 239 - 52 17.9 38.9 7.74 0.01 316 0.654 0.971 0.675 11-Aug-97 0.429 8.3 8.65 16.2 30 56.6 243 - 46.2 18.3 44.6 8.53 0.13 327 0.432 0.503 0.857 4-Sep-97 0.414 7.68 7 17.03 5 53.2 204 - 53.4 16 13.6 2.2 0.03 245 0.035 0.065 0.463 21-Jul-98 0.767 8.16 8.16 19.3 34 110 300 - 58.6 27 72 16.3 0.08 478 1.16 1.39 1.29 6-Aug-98 0.706 8.21 8.77 21.69 19 59.7 210 - 44.8 19 34.3 5.6 0.03 310 0.183 0.25 0.56 19-Aug-98 0.692 8.46 8.41 15.13 72 99.3 276 - 40.3 19.8 94.1 15.4 0.07 485 0.35 0.443 1.22 3-Sep-98 0.627 8.28 7.8 17.22 42 87.9 246 0.066 48 19.9 69.2 14.2 0.06 410 0.19 0.211 0.65 23-Apr-03 0.746 8.19 9.43 12.58 ------0.03 - 0.415 0.599 - 13-May-03 1.003 8.48 9.37 13.3 ------<0.01 - 0.402 0.771 - 10-Jun-03 0.769 8.09 8.08 13.09 - - - 0.009 - - - - <0.01 - 0.169 0.181 - 4-Jul-03 0.818 8.01 8.92 17.83 - - - 0.012 - - - - 0.01 - 0.352 0.41 - 21-Jul-03 0.547 8.53 11.27 24.09 - - - 0.026 - - - - 0.03 - 0.031 0.057 - 14-Jun-05 0.961 8.01 9.16 14.68 - - - 0.57 - - - - 0.12 - 0.116 0.181 - 30-Jun-05 0.529 7.73 7.84 20.11 - - - 0.307 - - - - 0.32 - 0.657 0.744 - 14-Jul-05 0.818 8.22 10.54 20.69 - - - 0.575 - - - - 0.05 - 0.306 0.311 - 29-Jul-05 1.276 8.2 10.4 21.47 - - - 0.337 - - - - 0.11 - 0.71 0.904 - 1-Sep-05 1.223 8.4 11.94 16.5 - - - 0.233 - - - - 0.06 - 0.536 0.569 - 28-Sep-05 1.943 8.23 10.57 7.35 - - - 0.474 - - - - 0.1 - 0.799 0.78 - 8-Jun-06 ------0.065 - - - - 0.05 - 0.182 0.266 - 26-Jul-06 ------0.148 - - - - 0.22 - 1.3 1.72 - 2-Oct-06 ------0.241 - - - - 0.43 - 0.367 0.352 - 23-Apr-07 1.306 8.67 11.57 8.48 - - - 0.154 - - - - 0.04 - 0.236 0.359 - 23-May-07 1.461 8.64 11.48 10.29 - - - 0.064 - - - - <0.05 - 0.102 0.14 - 10-Jul-07 0.552 9.77 9.6 17.42 - - - 0.034 - - - - <0.05 - 0.077 0.159 - 19-Jul-07 0.435 8.24 7.93 23.51 - - - 0.015 - - - - <0.05 - 0.067 0.071 - 22-Apr-08 0.414 7.71 13.62 1.77 - - - 0.16 - - - - 0.1 - 0.01 0.25 - 3-Jun-08 0.989 8.23 9.05 12.86 - - - 0.34 - - - - 0.05 - 0.004 0.13 - 29-Jul-08 0.543 8.5 9.98 19.29 - - - 0.02 - - - - <0.05 - 0.063 0.078 - 18-Aug-08 0.456 8.26 8.16 19.47 - - - 0.003 - - - - <0.05 - 0.068 0.087 - 26-Apr-10 0.49 8.1 10.66 8.2 - - - 0.011 - - - - <0.05 - 0.1 0.081 - 27-May-10 0.363 7.86 10.58 10.02 - - - <0.003 - - - - <0.05 - 0.006 0.025 - 14-Jun-10 1.452 8.32 9.93 17.8 - - - <0.003 - - - - <0.05 - 0.005 0.052 - 30-Jul-10 0.77 8.48 9.52 19.34 - - - 0.007 - - - - 0.07 - 0.41 0.45 - 9-Sep-10 0.409 8.17 9.04 10.36 - - - <0.003 - - - - <0.05 - 0.017 0.04 -

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Appendix G. Local groundwater chloride data close to Frank Lake, which collected by Alberta Water Well Information Database

NAME ID LATITUDE LONGITUDE Cl- NAME ID LATITUDE LONGITUDE Cl- 1-17-021-27-W4 1161980 50.779624 -113.704016 8.4 mg/L NW-24-017-25-W4 1187755 50.455003 -113.317583 13.2 mg/L 13-15-020-26-W4 1161166 50.702583 -113.533527 1 mg/L NE-13-017-25-W4 1183631 50.436264 -113.300978 16.7 mg/L 13-15-020-26-W4 1161168 50.702242 -113.53392 9.1 mg/L SE-16-017-25-W4 1183511 50.432402 -113.369991 20.3 mg/L 13-15-020-26-W4 1161170 50.702333 -113.533611 2.4 mg/L SE-18-017-25-W4 1183615 50.426645 -113.417959 94 mg/L 2-15-020-26-W4 1161990 50.691249 -113.522611 3 mg/L SW-18-017-25-W4 1183611 50.427371 -113.430584 455 mg/L 2-15-020-26-W4 1161992 50.690001 -113.524311 1.8 mg/L NE-01-017-25-W4 1186171 50.409506 -113.302285 29 mg/L 4-21-020-27-W4 1161932 50.703672 -113.697372 5.8 mg/L SE-06-017-25-W4 1183519 50.398208 -113.421197 14.8 mg/L 4-24-020-27-W4 1161174 50.706586 -113.624637 50.4 mg/L NE-16-017-25-W4 1183515 50.440004 -113.36947 48.2 mg/L 4-26-020-27-W4 1161176 50.720472 -113.647344 29 mg/L NW-18-017-24-W4 1163847 50.438523 -113.29934 12.4 mg/L 5-24-020-27-W4 1161458 50.707666 -113.625388 13.3 mg/L NW-08-017-24-W4 1163791 50.422698 -113.272311 132 mg/L 8-23-020-27-W4 1161172 50.708611 -113.630444 5.1 mg/L NW-08-017-24-W4 1183499 50.419615 -113.25657 401 mg/L 3-14-020-27-W4 1161138 50.689115 -113.644926 7.9 mg/L SE-07-017-24-W4 1187751 50.412012 -113.278322 16.4 mg/L NW-28-022-26-W4 1211413 50.524306 -113.254361 10.7 mg/L NW-06-017-24-W4 1186455 50.404609 -113.299318 11.8 mg/L 4-16-018-24-W4 1161926 50.51686 -113.251469 38.2 mg/L NW-18-016-24-W4 1163827 50.351612 -113.297724 90.3 mg/L 4-16-018-24-W4 1161928 50.516977 -113.252219 39 mg/L NE-31-016-24-W4 1163835 50.390502 -113.279625 7.3 mg/L 2-16-018-24-W4 1161178 50.514303 -113.241421 3.8 mg/L 4-23-016-27-W4 1162056 50.357214 -113.61569 42.8 mg/L SW-10-018-27-W4 1183571 50.503517 -113.633203 20.5 mg/L 4-05-016-27-W4 1161234 50.313522 -113.684603 26.5 mg/L NW-02-018-27-W4 1183579 50.492188 -113.610716 18.4 mg/L 14-34-016-26-W4 1183535 50.396288 -113.516023 9.1 mg/L NW-02-018-27-W4 1183587 50.492765 -113.609874 20.8 mg/L 14-34-016-26-W4 1183539 50.396733 -113.492537 18.9 mg/L 12-02-017-28-W4 1161420 50.405633 -113.75475 5.6 mg/L SW-34-016-26-W4 1183559 50.389186 -113.499218 26 mg/L 3-02-017-28-W4 1161938 50.398166 -113.751722 N/A NE-24-016-26-W4 1183619 50.367669 -113.438402 89.6 mg/L 1-03-017-28-W4 1160662 50.400837 -113.764854 6.4 mg/L NE-24-016-26-W4 1163855 50.364457 -113.44363 26.7 mg/L NW-35-017-27-W4 1183627 50.484245 -113.610729 16.4 mg/L NE-07-016-26-W4 1183495 50.337972 -113.563289 68.9 mg/L NE-26-017-27-W4 1183591 50.470146 -113.598889 14.2 mg/L NE-07-016-26-W4 1183503 50.338048 -113.563124 37 mg/L 2-20-017-27-W4 1160796 50.442472 -113.676777 9.8 mg/L NE-07-016-26-W4 1186155 50.338056 -113.563153 71.4 mg/L 2-20-017-27-W4 1162058 50.442472 -113.677694 23.9 mg/L NE-03-016-26-W4 1183595 50.322076 -113.487813 105 mg/L SW-22-017-27-W4 1180923 50.442339 -113.630551 17.7 mg/L NE-02-016-26-W4 1183599 50.317237 -113.473062 54.9 mg/L SE-14-017-27-W4 1187439 50.42754 -113.6003 24.1 mg/L 4-01-016-26-W4 1196047 50.313111 -113.459916 77.3 mg/L SW-14-017-27-W4 1187447 50.427683 -113.61874 39 mg/L NE-34-016-25-W4 1163843 50.391177 -113.354946 6.1 mg/L SE-16-017-27-W4 1180919 50.426565 -113.645025 18.8 mg/L SW-30-016-25-W4 1183551 50.378415 -113.436407 28.6 mg/L SE-16-017-27-W4 1187431 50.426752 -113.644697 21 mg/L SW-30-016-25-W4 1183547 50.374246 -113.429344 35.5 mg/L SW-12-017-27-W4 1180247 50.416953 -113.614305 13.1 mg/L SW-30-016-25-W4 1183555 50.373021 -113.429394 15.7 mg/L SW-11-017-27-W4 1187435 50.418319 -113.617154 14.4 mg/L NW-22-016-25-W4 1179759 50.367539 -113.366096 7 mg/L SW-11-017-27-W4 1187443 50.416102 -113.620931 40.8 mg/L NW-22-016-25-W4 1183479 50.367563 -113.366196 3.7 mg/L SW-11-017-27-W4 1180915 50.411909 -113.610227 13.3 mg/L SW-21-016-25-W4 1183623 50.354627 -113.391731 9.2 mg/L SW-11-017-27-W4 1187463 50.41184 -113.620865 11.2 mg/L NE-16-016-25-W4 1183487 50.349288 -113.390212 5 mg/L SW-01-017-27-W4 1183643 50.397465 -113.598104 26.8 mg/L SW-16-016-25-W4 1163815 50.339546 -113.385856 88.8 mg/L SE-13-018-26-W4 1183563 50.469625 -113.438896 29.6 mg/L SW-16-016-25-W4 1163819 50.339445 -113.385499 142 mg/L NW-02-017-26-W4 1186175 50.404973 -113.475264 17.4 mg/L SW-16-016-25-W4 1163823 50.33959 -113.381079 30.2 mg/L SW-30-017-25-W4 1186983 50.460312 -113.436909 30.1 mg/L - - - - -

108

Appendix H. Schematic diagram of the average annual water balance, chloride balance, total nitrogen balance and total phosphorus balance for each basin of Frank Lake based on data shown in Table 1; Mass precipitation of chloride, nitrogen and phosphorus are not included since these are negligible relative to the other fluxes. ΔV and ΔF are fluxes not accounted for.

109

Appendix I. Time-weighted average annual chloride and 18O based on Julian day plots (Jan: 350 mg/L; Feb: 400 mg/L; Mar: 200 mg/L; April: 80 mg/L; May: 110 mg/L; June: 150 mg/L; July: 200 mg/L; Aug:220 mg/L; Sep: 250 mg/L, Qct: 290 mg/L; Nov: 310 mg/L; Dec: 350 mg/L, Total is 2910 mg/L, and time weighted average annual is 243 mg/L ; Jan: -11 ‰; Feb: -16 ‰; Mar: -21 ‰; April: -20 ‰; May: -15 ‰; June: -11 ‰; July: -6 ‰; Aug:-5.5 ‰; Sep: -5 ‰, Qct: -6 ‰; Nov: - 8 ‰; Dec: -11 ‰, Total is -135 ‰, and time weighted average annual is -11 ‰ )

110

Appendix J. 1-D diffusion model of chloride and 18O of Frank Lake Basin 1 sediment.

Cl (mg/l) 18O (‰) 0 100 200 300 -20 -18 -16 -14 -12 -10 0 0

2 2

4 4 Depth (m) Depth 6 (m) Depth 6

8 8

10 10

111

Appendix K. Dissolved Oxygen plots of Frank Lake Appendix K-a. Dissolved Oxygen plots of Basin 1 Outlet (unpublished data of year 2013, Alberta Environment and Parks)

112

Appendix K-b. Dissolved Oxygen plots of Basin 2 Outlet (unpublished data of year 2013, Alberta Environment and Parks)

113

Appendix K-c. Dissolved Oxygen plots of Basin 3 Outlet (unpublished data of year 2013, Alberta Environment and Parks)

114

Appendix L. Microprobe results on sediment sample that showing phosphorus and calcium ions are bonded together (two images of the same sample of Basin 1 which was sampled in August, 2013)

115