Examination of Metal Contamination Within the UNESCO Designated Rideau River Waterway By

Examination of Metal Contamination within the UNESCO Designated Rideau River Waterway by

Shannon Stephanie Marie-Paule LeBlond

A thesis submitted to the Department of Biology In conformity with the requirements for The degree of Masters of Science

QUEEN’S UNIVERSITY Kingston, Ontario, Canada September, 2009

Abstract The Rideau River Waterway, also known as the Rideau Canal, is a constructed navigation channel that links Ottawa to Kingston, Ontario. Opened in 1832, it was designated a

Canadian Heritage Site in 2003 and a UNESCO World Heritage Site in 2007. South of

Smiths Falls, the Rideau Canal consists of a series of 14 interconnected lakes, primarily used for recreational purposes, as well as commercial fishing. The objectives of this study were to examine the spatial and temporal distributions of anthropogenic elements to three headwater lakes of the Rideau Canal system and to examine the relationship between sport fish Hg and historical sediment Hg concentrations.

Utilizing paleolimnological techniques, historical records of As, Cd, Co, Cr, Cu, Hg, K,

Ni, Pb, Rb, and Zns were analyzed from chronologically deposited lake sediments.

Overall, Indian Lake, though the smallest of the three studied lakes, consistently had the highest overall As, Cd, Cu, Hg, Ni, Pb and Zn concentrations. While all peak concentrations were buried, recent surface sediment Hg, Cd, and Zn concentrations still remain above the federal interim sediment quality guideline and the concentration of Pb remains above the federal probable effect level within Indian Lake, leading to continued concern for human and ecosystem health. The general agreement between lake sediment profiles for Cd, Pb and Zn and then Cu and Ni suggest that each group of elements is primarily contributed from the same source. The similarity in trends and timing of peak iii concentrations between the study lakes and other Ontario lakes suggests large-scale, atmospheric contributions of elements to the freshwater systems in the area.

Although only historical northern pike (Esox lucius) THg tissue concentration data was available for analysis, results indicate that concentrations in fish have decreased more than 60% since the late 1970’s, while sediment THg concentrations have decreased 35% within the same time period. Overall, this study has demonstrated that the headwater lakes to the Rideau Canal are presently impacted by elements, at concentrations which are of potential concern for human health.

Co-Authorship Chapters one through four were prepared by Shannon LeBlond, who conducted most of the data collection (2007 and 2008), all data analysis, preparation of graphs, and writing of the manuscripts. Kathleen Hamilton conducted the 2006 data collection and original analysis. Cynthia Lai conducted the historical review of surrounding land uses in 2009.

Dr. Linda Campbell contributed to the research designs, interpretations and editing of this work and the manuscripts in chapters two and three.

Acknowledgements I am very grateful to all of those that have helped in both the completion of my Masters and my transition into the Queen’s community. The success of my project was largely attributable to the direction and tenacity of my supervisor Dr. Linda Campbell and all the help I received from the PEARL lab, the Analytical Services Unit and the numerous volunteers that have helped me over the years, to them, I am unbelievably thankful. I am ceaselessly grateful to Dr. Linda Campbell, for her willingness to take a chance on me and graciously welcome me into her group. For her great efforts in teaching me, her patience and her continuous help.

Thank you to all the members of the academic community at Queen’s University who have repeatedly helped me throughout my project, especially Dr. Peter Hodson, Dr. John

Smol, Dr. Allison Rutter, Dr. Graham Whitelaw and Dr. Brian Cumming. Thank you to the PEARL lab for their sampling equipment, the use of their gamma counters and all their help over the years. Without their equipment, my project would have been entirely different and I am very grateful. A particular thank you to Dr. John Smol, Dr. Brian

Cumming, Chris Grooms and Josh Thienpont for their help in sampling and data interpretation. vi

I am also highly indebted to the Analytical Services Unit at Queen’s University and particularly to Dr. Allison Rutter and Dr. Graham Cairns. All water metal samples

(except for mercury) and all sediment samples were analyzed using their facilities. For all your patience, your willingness to help and your time and efforts, I am very grateful.

Thank the Ontario Ministry of Environment, especially Mr. André Vaillancourt for their help in analyzing our fish tissue samples for mercury. It is as a result of their assistance that my project was able to go one step further in beginning to connect sediment and sport fish tissue mercury concentrations. I would also like to thank Parks Canada for their funding and sampling assistance in the first year of my project.

Thank you to all the volunteers that helped me throughout my project, especially Nikisha

Grant, Marina Arcani, Cynthia Lai and Lyndsey Cox. In addition, I would like to thank

Nikisha for all her help in the lab, especially with regard to the Tekran and my fish dissections.

A tremendous thank you to Mindi Conder for her professional help and her amazing personality, without which, life would have been a bore. For helping make life in

Kingston that much more enjoyable, both inside and outside of school, thank you so much Mindi.

I am eternally grateful to all the people that helped to make my time at Queen’s an enjoyable one. To all the labmates and pseudo labmates past and present, with whom I had the pleasure to work with, especially: Nathan Manion, Elizabeth Yanch, Elizabeth

Hatton, Eden Siwik, John Poulopoulos, Tian Fang, Roxanne Razavi, Sharilyn Kennedy, vii

Stephen McIntosh, Kristin Norris, Mark Kelly, Jon Martin, Mat Vankoughnett, Lyndsey

Cox, Cynthia Lai, Brad McKell, Curtis McDonald, SaeYun Kwon and Kathleen

Hamilton, thank you so very much.

In addition, I am very thankful to have had such wonderful housemates and a tremendous

Thursday night club. To Stephanie Brown, Marshall Horne, Benedict Drevniok and

Carlin Lindsay, thank you.

I also wish to thank my parents, Suzanne and Isidore LeBlond, who taught me to be tenacious and strive to accomplish my goals; who supported me in so many ways for so many years; and who always kept me on time and ensured my safety home. I also wish to thank my younger siblings, Sophie and Daniel LeBlond for their unfailing support and help throughout my various endeavours. Lastly, I would like to thank my four grandparents, Marie-Paule and Gaston Bellavance, as well as Bernice and Isadore

LeBlond for their unwavering love and support. viii

Table of Contents

Chapter 1 - Rideau Lakes and Historical Element Sources ...... 1 Introduction ...... 1 Bioaccumulation, Bioconcentration and Biomagnification ...... 3 Elements in the Environment ...... 4 Project Objectives ...... 8 Chapter 2 - Paleolimnological Analysis of Total Mercury within the UNESCO Designated Rideau River Waterway ...... 13 Abstract ...... 13 Introduction ...... 14 Methods and Data Analysis...... 17 Results ...... 22 Discussion ...... 28 Chapter 3 - Trace Element Trends within the UNESCO Designated Rideau River Waterway ...... 48 Abstract ...... 48 Introduction ...... 49 Methods and Data Analysis...... 51 Results ...... 55 Discussion ...... 60 Chapter 4 - General Discussion ...... 88 Findings and Implications ...... 88 Future Research ...... 92 Summary and Conclusions ...... 94 Literature Cited ...... 95 Appendix A - Timeline of Historical Events and Land-uses ...... 108 Indian Lake ...... 109 Newboro Lake ...... 111 Upper Rideau Lake ...... 114 Literature Cited ...... 117 Appendix B – Supplementary Information ...... 118

List of Tables Table 1 Compilation of federal environmental quality guidelines...... 10 Table 2 Priority listing of elements and human-health benefits ...... 11 Table 3 Measured geochemical lake characteristics during sampling events ...... 39 Table 4 Summary of total mercury concentrations ([THg]) in sport fish tissue samples ...... 40 Table 5 Comparison of potential influential factors among lakes ...... 75 Table 6 Literature compilation of trace element enrichment in sediments ...... 76

List of Figures

Figure 1 Location map...... 12 Figure 2 Detailed bathymetric mapping of study lakes ...... 41 Figure 3 Sediment sampling locations ...... 42 Figure 4 Original 210Pb, 137Cs gamma activity and loss-on-ignition profiles ...... 43 Figure 5 Original and shifted sediment total mercury (THg) concentration profiles ...... 44 Figure 6 Spatial distribution of surface sediment mercury (Hg) concentrations...... 45 Figure 7 Relative surface sediment total mercury concentrations in Indian Lake ...... 46 Figure 8 Relative surface sediment total mercury concentrations in Upper Rideau Lake ...... 47 Figure 9 Sediment concentration profiles for arsenic (As), cadmium (Cd), mercury (Hg), lead (Pb) and zinc (Zn) ...... 80 Figure 10 Sediment concentration profiles for cobalt (Co), chromium (Cr), copper (Cu), potassium (K), nickel (Ni) and rubidium (Rb) ...... 81 Figure 11 Sediment cadmium (Cd), lead (Pb) and zinc (Zn) flux profiles for Indian Lake (IL) ...... 82 Figure 12 Shifted sediment concentration profiles for arsenic (As), cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni) and zinc (Zn) ...... 83 Figure 13 Comparison of trace element profiles and historical disturbances around Indian Lake (IL) ...... 84 Figure 14 Spatial distributions of surface sediment cadmium (Cd) concentrations...... 85 Figure 15 Spatial distributions of surface sediment lead (Pb) concentrations...... 86 Figure 16 Spatial distribution of surface sediment zinc (Zn) concentrations...... 87 xi

List of Abbreviations and Acronyms As – Arsenic ASU – Analytical Services Unit CA: LA – Catchment Area to Lake Area Ratio CCME – Canadian Council of Ministers of the Environment Cd – Cadmium Co – Cobalt Cr – Chromium CRM – Certified Reference Material CRS – Constant Rate Supply CSIA – Canadian Sport Fishing Industry Association Cu – Copper CVAAS – Cold Vapour Atomic Absorption Spectrometer CVAFS – Cold Vapour Atomic Fluorescence Spectrometer HCl – Hydrochloric Acid Hg – Mercury Hg0 – Elemental Mercury

HNO3 – Nitric Acid ICP-OES – Inductively Coupled Plasma Optical Emission Spectrometer ICV – Inorganic Ventures Calibration IL – Indian Lake IPR – Initial Precision and Recovery ISQG – Interim Sediment Quality Guideline K – Potassium LOI – Loss-on-ignition xii

MeHg – Methylmercury Ni – Nickel NL – Newboro Lake OME – Ontario Ministry of Environment OPR – Ongoing Precision Recovery Pb – Lead PCB – Polychlorinated Biphenyls PEL – Probable Effect Level ppm – Parts Per Million QA/QC – Quality Assurance Quality Control Rb – Rubidium RDL – Reliable Detection Limit RL – Reporting Limit RSD – Relative Standard Deviation THg – Total Mercury UNESCO – United Nations Educational, Scientific and Cultural Organization URL – Upper Rideau Lake U.S. – United States of America USEPA – United States Environmental Protection Agency Zn – Zinc Chapter 1 – Rideau Lakes and Historical Element Sources 1

Chapter 1 - Rideau Lakes and Historical Element Sources

Introduction

The Rideau River Waterway (also known as the Rideau Canal) consists of a 202-km man-made channel stretching from Ottawa to Kingston, Ontario connected through a series of 49 locks (Figure 1). From Upper Rideau Lake (URL), the system drains north into the Ottawa River and from Newboro Lake (NL), it drains south towards Lake

Ontario. The canal provides a navigational link between the Ottawa River and Lake

Ontario. In 2000, the federally managed Rideau Canal system was designated a Canadian

Heritage River and, in 2007, it was designated a United Nations Educational, Scientific and Cultural Organization (UNESCO) World Heritage Site. Not only is the Canal historically important but it also supports an essential tourism-based industry for the area, valued around $24 million CAN annually (Parks Canada 2005). Since construction in

1832, the shores of the Rideau Canal have been extensively manipulated and have supported a number of logging, farming, mining and milling operations over the last 150 years (Appendix A; Lai 2009). Today, the lands surrounding the lakes within the Canal are primarily lined with seasonal cottages and permanent waterfront residences, interspersed with farms. Chapter 1 – Rideau Lakes and Historical Element Sources 2

While the Canal system supports a commercial fishery and extensive recreational sport fishing, there have been no published studies to date regarding overall element concentrations within the system. The Ontario Ministry of the Environment (OME) has occasionally monitored sport fish contaminant levels since the late 1970’s. Of the 14 lakes located within the Rideau Canal, the OME has established consumption advisories for sport fish based on contaminant levels for nine of them - primarily due to mercury

(Hg), polychlorinated biphenyls (PCBs) and mirex (OME 2007). The scarcity of research conducted on this system, coupled with the known consumption guidelines emphasizes the need for scientific studies in this area.

Individual portions of the Rideau Canal are managed by various provincial and federal authorities. Given that the sediment bed is regulated by Parks Canada and that the water body is regulated by Transport Canada, federal regulatory guidelines for contaminants apply. The Canadian Council of Ministers of the Environment (CCME) is an intergovernmental group responsible for the establishment of nationally consistent environmental quality guidelines, criteria and objectives (CCME 2009). Table 1 summarizes the latest guideline values updated by the CCME for the studied elements within various media.

In 2006, a preliminary study of nine lakes located within the Rideau Canal found that mean sediment concentrations exceeded Canadian federal interim sediment quality guidelines (ISQG, Table 1) for cadmium (Cd), Hg, lead (Pb) and zinc (Zn) within each lake and copper (Cu), within all but one lake (Hamilton 2007). In addition, Pb exceeded Chapter 1 – Rideau Lakes and Historical Element Sources 3 the federal probable effect level (PEL) in four of nine lakes. Overall, the highest sediment concentrations were identified in Upper Rideau Lake and Indian Lake (Hamilton 2007).

Bioaccumulation, Bioconcentration and Biomagnification

Three important concepts relating to human and ecosystem health, particularly within aquatic systems include: bioaccumulation, bioconcentration and biomagnification.

Bioaccumulation can be defined as the uptake, excretion and accumulation of a substance by an organism from its surrounding environment though any uptake mechanism. The process involves not only the uptake but also the sequestering of a substance within the organism, resulting in a higher internal concentration compared to the ambient environment. The rate at which a substance is accumulated is highly variable, depending upon a number of parameters such as, the chemical species of the substance, the organism, the method of uptake, the rate of excretion and other physical and chemical variables. Bioconcentration refers to the same processes, though it pertains specifically to the uptake of an organism from its surrounding aquatic environment. Much like bioaccumulation, it is regulated by a number of biochemical factors, particularly the octanol-water partition coefficient, which will influence the uptake, excretion and accumulation rates for individual elements. Biomagnification specifically refers to the transfer of a substance through the food chain, whereby the concentration of the substance in the prey is taken up by the predator. A summary of the bioaccumulation, bioconcentration and biomagnification potential for each of the studied elements is further described below and summarized in Table 2. Chapter 1 – Rideau Lakes and Historical Element Sources 4

Elements in the Environment

Natural releases of elements include the weathering of rocks, volcanic activities and hydrothermal vents; however, anthropogenic activities have greatly expedited the rate at which these crustal elements are released into the environment. Once in the atmosphere, elements have the ability to travel long distances before being deposited, resulting in the potential for global distributions. Remote regions, far removed from direct anthropogenic output sources, can be affected by contaminant burdens as a result of atmospheric transport mechanisms. Anthropogenic elements in freshwater aquatic systems and their impacts have been extensively studied across the northern hemisphere over the last four decades. Canada, the United States (U.S.), and various European countries have developed and implemented regulations limiting the environmental release of specific elements (Lourie 2003; ATSDR 2008a). Due to government intervention, improved technology and citizen awareness, atmospheric burdens of certain elemental contaminants such as Cd, Hg and Pb have generally been on the decline across North America (Lourie

2003; CCME 2009; Mahler, et al 2006). Although a number of studies have documented decreased element concentrations within recently deposited lake sediment layers, lakes located within the same region can also display variations in the timing of peak concentrations and magnitudes of enrichment for specific elements. It has been acknowledged in the literature that there still remains insufficient information regarding the influence of watershed specific variables which may influence the input and distribution of elements to individual lake systems (Landy, et al 1980; Callender 2003). Chapter 1 – Rideau Lakes and Historical Element Sources 5

Elemental mercury (Hg0) is a highly volatile, atmospherically mobile metal that can be converted to methylmercury (MeHg) by sulphur and iron-reducing bacteria in lakes and wetlands (Lourie 2003). Methylmercury is the most bioaccumulative form of Hg and it is known to biomagnify in foodwebs, resulting in exposure through food consumption

(primarily through fish) and increased exposure for higher trophic level species, such as humans. Methylmercury is also highly toxic due to its ability to cross the blood-brain barrier, resulting in neurological damage (Chang 1977). There has been concern over the past 30 years regarding elevated total mercury (THg) concentrations within freshwater aquatic systems. Fish collected from relatively pristine freshwater lakes located in the northern hemisphere have been found to have tissue THg concentrations greater than what can be attributed to local sources (Lindqvist, et al 1991). In areas without known point-sources, this accumulation is consistently attributed to the global atmospheric transport and deposition of Hg. Mercury is released to the environment both naturally and anthropogenically. Within Canada, the largest contribution of anthropogenic emissions comes from electrical generation, waste incineration, and non-ferrous mining and smelting (EC 2000). Other significant global sources include coal-based plants and chlor-alkali plants (Lourie 2003). Natural sources of Hg release include volcanic eruptions, the weathering of rocks and forest fires (EC 2000). For these reasons, Hg was listed third on the U.S. list of priority substances in 2007 (Table 2).

Within Ontario, commercial fisheries alone employ over 3500 individuals and generate over $110 million CAN annually (OCFA 2007). The Canadian Sport Fishing Industry

Association (CSIA) has estimated that roughly 8 million citizens fish nationally and that in 2000, angler’s spent over $6.7 billion in Canada on tourism, transportation, retail Chapter 1 – Rideau Lakes and Historical Element Sources 6 goods, boating, vehicle sales and more (CSIA 2009). As a result of the economic importance of Ontario fisheries, and fish consumption being the primary route of MeHg exposure to humans, the study of Hg in Ontario freshwater aquatic systems is of particular importance.

Arsenic (As) is a toxic metalloid (Phillips 1990) that is considered non-essential to the sustenance of life (Phillips 1990; CCME 2009).It is presently listed as the number-one priority substance in the U.S. based on its potential for threat to human health as a result of its toxicity and the likelihood of exposure for the general population (Table 2).

Arsenic is extensively used in herbicides, pesticides and fungicides (Ferguson and Gavis

1972; Phillips 1990; ATSDR 2007a), and is one of the primary components in many wood preservatives (Hingston, et al 2001). It is emitted to the atmosphere as a byproduct of metal smelting, particularly in relation to Cu smelting (Phillips 1990; ATSDR 2007a).

It has been demonstrated that atmospheric deposition can constitute up to 50% of the As burden to inland lake systems (Crecelius 1975). Due to its high affinity for waterborne particles, As is readily deposited to sediments, resulting in a higher potential exposure to benthic organisms (ATSDR 2007a; CCME 2009). The most important exposure route for humans is from the ingestion of food and drinking water (Fergusson and Gavis 1972;

ATSDR 2007a), although the precise mechanism for toxicity and uptake in humans remains unknown (Liu, et al 2002). While some forms of As have been demonstrated to bioaccumulate in aquatic organisms, it is not known to biomagnify through the foodchain

(Fergusson and Gavis 1972; ATSDR 2007a). Chapter 1 – Rideau Lakes and Historical Element Sources 7

Cadmium, Pb, and Zn are typically found within the same geological deposits and are simultaneously released to the environment through both natural and anthropogenic processes (ATSDR 2008a). Similarly, since Co, Cu, and Ni are typically geologically associated and released to the environment; these elements tend to show very similar profiles within sediment cores (Callender 2003). Cadmium, Co, Cu, Ni, and Zn are all transitional metals, while Pb is a post-transitional metal. Each of these elements has been listed as one of the top 275 priority substances in the U.S. (Table 2). The main anthropogenic, environmental releases of these metals are coal and fossil fuel combustion processes, ferrous and non-ferrous metal production, as well as waste incineration

(Nriagu 1979; Nriagu 1989; Mahler, et al 2006). As of 2003, there were six base metal smelting companies operating in Ontario, primarily producing Cu, Ni, Pb or Zn (Lourie

2003; Mohapatra and Mitchell 2005). A review of global metal emissions in 1983 found that anthropogenic contributions accounted for up to 96% of total emissions of these elements while natural sources were relatively minor (Nriagu and Pacyna 1988; Nriagu

1989). Cobalt is an exception, with estimates of higher natural emissions compared to anthropogenic emissions in the U.S., primarily from windblown soil, seawater spray, volcanic eruptions and forest fires (Lantzy and MacKenzie 1979). Chromium (Cr) is also a transitional metal, listed on the U.S. priority substance list. It is commonly used in the production of stainless steel and in electroplating (ATSDR 2008b). Although potassium

(K) and Rb are naturally occurring alkali metals which are not generally regulated as environmental contaminants, they were examined as part of this study as background elements. Cobalt, Cd, Pb and Zn has been proven to bioaccumulate and bioconcentrate

(ATSDR 2004a, 2005, 2007b, 2008a). Although Cr has not been confirmed to Chapter 1 – Rideau Lakes and Historical Element Sources 8 bioaccumulate, it has been found to bioconcentrate in aquatic organisms (ATSDR

2008b). Of these, Co, Pb and Zn have been proven not to biomagnify (ATSDR 2004a,

2005, 2007b) and there remains inconclusive evidence regarding the biomagnifications potential for Cd and Cr (ATSDR 2008a, 2008b). To date, there is little scientific evidence suggesting that Cu bioaccumulates and researchers have concluded that while there exists a low potential for bioconcentration, it does not biomagnify (ATDSR 2004b). Lastly, the bioaccumulation, bioconcentration and biomagnifications potential for Ni, K and Rb presently remain inconclusive.

Project Objectives

The objectives of this thesis work were to examine the spatial and temporal distributions of anthropogenic elements to three headwater lakes of the Rideau Canal system. The goals of this research were to: (1) confirm the presence of elevated elemental concentrations within the study lakes, (2) examine distribution patterns in hopes of identifying potential contributing sources, (3) examine the relationship between sport fish

Hg and historical sediment Hg concentrations and (4) qualitatively evaluate the influence of various watershed-specific factors.

As a result of its unique biogeochemical properties and recognized widespread impact on

Ontario freshwater lake systems, the focus of Chapter 2 is on Hg in water, sediment and sport fish. It is hypothesized that historical sediment profiles will demonstrate a decrease in recent Hg contributions to the lakes, given the decreased atmospheric inputs reported across North America. Historical Hg trends, as preserved in lake sediments, since the Chapter 1 – Rideau Lakes and Historical Element Sources 9 construction of the Canal were examined in parallel with sport fish tissue THg concentrations over-time.

In Chapter 3, the distribution trends for 10 other elements (As, Cd, Co, Cr, Cu, K, Ni, Pb,

Rb, Zn) in water and sediment are discussed within the same three study lakes. It is hypothesized that decreasing element concentrations will be identified in sediments over- time. An examination of spatial-temporal distributions patterns within the lakes, in parallel with watershed-based characteristics and localized anthropogenic factors was used to narrow the scope of potential contributing factors.

Chapter 1. Rideau Lake and Historical Element Sources 10

Table 1 Compilation of federal environmental quality guidelines Canadian Sediment Quality Drinking Water Guideline Guidelines for the Protection of (µg mL-1) a Canadian Water Aquatic Life Quality Guidelines for (µg g-1 dw) b Element the Protection of Interim Aquatic Life Sediment Maximum Acceptable Aesthetic Probable Effect (µg L-1) b Quality Concentration Objective Level (PEL) Guideline (ISQG) Arsenic (As) 0.01 - 5.0 5.9 17.0 Cadmium (Cd) 0.005 - 0.017 * 0.6 3.5 Chromium (Cr) - - 1.0 to 8.9 ** 37.3 90.0 Cobalt (Co) - - - - - Copper (Cu) - < 1.0 - 35.7 197 Lead (Pb) 0.01 - - 35.0 91.3 Mercury (Hg) 0.001 - 0.026 *** 0.17 0.486 Nickel (Ni) - - - - - Potassium (K) - - - - - Rubidium (Rb) - - - - - Zinc (Zn) - < 5.0 - 123 315 “-“ Denotes that there is no federal environmental quality guideline for the parameter within that matrix * Refers to an interim guideline which can be adjusted based on water hardness ** Dependent on the chemical species *** Refers to the inorganic form a - Health Canada (HC). 2007. Guidelines for Canadian Drinking Water Quality - Summary Table. Federal-Provincial- Territorial Committee on Drinking Water of the Federal-Provincial-Territorial Committee on Health and the Environment, Ottawa, Ontario. b - Canadian Council of Ministers of the Environment (CCME). 2009 Update. Canadian Environmental Quality Guidelines. Canadian Council of Ministers of the Environment, Winnipeg, Manitoba.

Chapter 1. Rideau Lake and Historical Element Sources 11

Table 2 Priority listing of elements and human-health benefits Priority List of Summary of Bioaccumulation, Hazardous Human-health Benefit Element Bioconcentration, and/or Substances Ranking (Toxicity and Carcinogenicity) b Biomagnification Potential a Arsenic (As) 1st None (Toxic) Bioconcentrates Bioaccumulates, bioconcentrates, may Cadmium (Cd) 7th None (Possible carcinogen) biomagnify Cr (IV) 18th Cr(III) Essential trace element Chromium (Cr) Bioconcentrates Cr 77th Cr(IV) None (Neurotoxic carciogen) Cobalt (Co) 49th Essential trace element Bioaccumulated and bioconcentrates Copper (Cu) 128th Essential trace element May bioaccumulate Lead (Pb) 2nd None (Neurotoxic) Bioaccumulates and bioconcentrates Bioaccumulates, bioconcentrates and Mercury (Hg) 3rd None (Toxic) biomagnifies Nickel (Ni) 53rd None (Neurotoxic) Unknown Radioactive form – Potassium (K) Essential trace element Unknown (40K) 217th Rubidium (Rb) Not listed None (Generally nontoxic) Unknown Zinc (Zn) 74th Essential trace element Bioaccumulates and bioconcentrates a - Agency for Toxic Substances and Disease Registry (ATSDR). 2007. 2007 CERCLA priority list of hazardous substances that will be the subject of toxicological profiles and support document. U.S. Department of Health and Human Services, Agency for Toxic Substances and Disease Registry, Division of Toxicology in cooperation with the U.S. Environmental Protection Agency, Atlanta, Georgia. b - Canadian Council of Ministers of the Environment (CCME). 2009 Update. Canadian Environmental Quality Guidelines. Canadian Council of Ministers of the Environment, Winnipeg, Manitoba.

Chapter 1. Rideau Lake and Historical Element Sources 12

Figure 1 Location map Map created from the Government of Ontario Basic Mapping (2009) Chapter 2. A Paleolimnological Analysis of Total Mercury 13

Chapter 2 - Paleolimnological Analysis of Total Mercury within the UNESCO Designated Rideau River Waterway

Abstract

The Rideau Canal is comprised of a series of lakes connected by locks linking the Ottawa

River and the Cataraqui River in Kingston, Ontario, Canada. Historically, the canal was used for the transport of local goods and people; however, it now serves an entirely recreational purpose. Mercury (Hg) in the form of methylmercury is a biomagnifying, neurotoxin that primarily affects humans via fish consumption. Given that most Ontario lakes have site-specific sport fish consumption restrictions established in part due to Hg concentrations, the study of Hg in Ontario inland lakes if of particular importance. The objectives of this study were to examine temporal sediment Hg trends over time in parallel with sport fish tissue concentrations. Sediment cores were collected from three rural lakes within the Rideau Canal analyzed for Hg concentrations and dated using 210Pb.

Northern pike (Esox lucious) were also collected in 2007 and tissue Hg concentrations were analyzed as part of the Ontario Sport Fish Monitoring Program. All three lakes displayed a decrease in sediment Hg concentrations within the last two decades, which parallel the decreased atmospheric emissions in Canada and the United States since the Chapter 2. A Paleolimnological Analysis of Total Mercury 14

1980’s. Although historical northern pike data was limited, the mean total Hg concentration appears to have decreased by almost 60% since 1979. While encouraging, additional monitoring is required to confirm the trend over-time, as well as between species and among lakes.

Introduction

The Rideau River Waterway (also known as the Rideau Canal system) is comprised of a series of 49 locks and 202 km of man-made channels stretching from Ottawa to Kingston,

ON (Figure 1). Initially designed as an alternative navigational route between Montreal and the Great Lakes, the Canal is now used entirely for recreational purposes. Indian

Lake, Newboro Lake and Upper Rideau Lake are located south of Smith Falls, Ontario within the Rideau Canal (Figure 1). Upper Rideau Lake forms the headwaters for the

Rideau Valley watershed as it descends north, towards the Ottawa River. Conversely,

Newboro Lake forms the headwaters for the Cataraqui River, which descends south, through Indian Lake, towards Kingston, Ontario. The three lakes are connected to each other and the remainder of the system, through the Newboro and Chaffey’s Mill locks.

Geologically, the lakes are underlain by dolomite, limestone, sandstone and conglomerate

(Wilson, et al 1959; Wilson, et al 1966; Henderson 1967). These lakes are primarily used for recreational purposes and the shores of each lake are predominantly lined with seasonal cottages and small towns (Figure 1). In 2000, the Rideau Canal system was designated a Canadian Heritage River and in 2007 it was designated a United Nations

Educational, Scientific and Cultural Organization (UNESCO) World Heritage Site. Not only is the Canal historically important but it also supports an important tourism-based Chapter 2. A Paleolimnological Analysis of Total Mercury 15 industry, valued around $24 million CAN annually (PC 2005) and small-scale commercial fisheries operations.

In 2006, a preliminary study indicated that seven of the lakes within the Rideau Canal system south of Smiths Falls, Ontario had mean surface sediment mercury (Hg) concentrations that exceeded the federal interim sediment quality guidelines (ISQG) of

0.17 µg g-1 (Hamilton 2007). Of those lakes, Indian Lake, Newboro Lake and Upper

Rideau Lake had some of the highest observed sediment concentrations. A subsequent review of historical land-uses (Lai 2009) identified no individual point sources amongst or in proximity to the lakes which could account for the concentrations observed was

(Appendix A).

Regrettably, it is not uncommon to find high THg sport fish tissue concentrations even in remote areas within the northern hemisphere (e.g. Lindqvist, et al 1991; St. Louis, et al

1995), primarily due to atmospheric transport and deposition (Fitzgerald, et al 1998).

With fish consumption being the primary route of methylmercury (MeHg) exposure to humans, the study of Hg in freshwater aquatic systems is of particular importance. The

Ontario Ministry of the Environment (OME) has some limited historical records of sport fish contaminant levels since the late 1970’s. Of the 14 lakes located within the Rideau

Canal, the OME has established site-specific consumption advisories for sport fish based on contaminant levels within nine of the lakes, primarily due to elevated Hg, polychlorinated biphenyls (PCBs) and Mirex (OME 2007), thus emphasizing the need for further research on contaminants in this area. Chapter 2. A Paleolimnological Analysis of Total Mercury 16

Numerous studies conducted in North America have demonstrated that THg concentrations in the atmosphere and lake sediments have increased exponentially since the late 1800’s (Engstrom and Swain 1997). As of 2000, China, South Africa, India and

Japan were the largest global contributors to anthropogenically-derived, atmospheric THg concentrations (Pacyna, et al 2006). Since 1998, the north-eastern U.S. States and eastern

Canadian provinces have formed a Regional Mercury Task Force, aimed at eliminating all anthropogenically derived sources of Hg. Since the inception of this working group,

Hg emissions have decreased by 55% in the region (NEIWPCC, et al 2007). Pilgrim, et al

(2000) acknowledged that there remains insufficient evidence to prove that such reductions will indeed have an effect on aquatic organisms; however, recent studies are beginning to demonstrate that local and regional emission reductions are having a beneficial effect on the surrounding environment (MDEP 2006; NEIWPCC 2007;

NESCAUM 2007).

Paleolimnological analysis of lake sediments enables the reconstruction of contaminant chronologies over time (Smol 2008), and numerous studies have utilized such techniques to examine anthropogenic THg contributions to freshwater systems (e.g. Couillard, et al

2008). Preliminary surface THg sediment concentrations from the Rideau Lakes

(Hamilton 2007) suggest that concentrations within Indian Lake, Newboro Lake and

Upper Rideau Lake (Figure 2 and Figure 3) are higher than would be expected, given that there are no known point-sources in or around the area (Appendix A; Lai 2009). This, coupled with the historical sport fish tissue concentrations, suggests that there exists the potential for harm to both human and aquatic ecosystem health within this system. The objectives of this study were to examine historical Hg trends, as preserved in lake Chapter 2. A Paleolimnological Analysis of Total Mercury 17 sediments, since the construction of the Rideau Canal and to examine any paralleled trends in sport fish tissue concentrations over time.

Methods and Data Analysis

A total of 34 surface sediment samples were collected from the three study lakes in 2007.

An attempt was made to collect samples from different areas within Indian Lake and

Upper Rideau Lake based on navigational maps, while samples were only collected at the locations from which fish were captured in Newboro Lake (Figure 3). In 2007, all sediment samples were collected using an acid-cleaned (10% nitric acid (HN03)) Ekman

Bottom Grab sampler (5.3 L). In 2008, one sediment core was collected from the deepest undisturbed site within each of the study lakes (IL-2, NL-7, URL-1; Table 3; Figures 2,

3) using a 7.6 cm acid-cleaned Glew (1989) gravity corer, and extruded at 1-cm intervals using a modified upright piston extruder (Glew 1988). All surface and core sample locations are summarized in Appendix B – Table 1. Dried, ground sediment samples were analyzed using a Milestone Direct Mercury Analyzer (DMA-80), which is designed to meet U.S. Environmental Protection Agency (US EPA 1998) Method 7473 and utilizes

Cold Vapour Flameless Atomic Absorption Spectrometry (CVAAS). Samples were thermally decomposed, prior to amalgamation on a gold trap and spectrophotometric quantification. The reporting limit (RL) as set by the Analytical Services Unit lab (ASU) was 5.0 ng g-1. Each run also included both a 20.0 ng and 200.0 ng aqueous, secondary source calibration check sample. In 2008, a total of eight, four and 17 sediment grab samples were analyzed from Indian Lake, Newboro Lake and Upper Rideau Lake, respectively (Figure 3, Appendix B – Table 2). Supplementary QA/QC samples included Chapter 2. A Paleolimnological Analysis of Total Mercury 18 two National Research Council of Canada (NRCC 1997) MESS-3 Certified Reference

Material (CRM) samples with results consistently within the 10% range of uncertainty for the CRM (Appendix B – Table 3); boat blanks which were consistently < 0.1 ng g-1 and

10% duplicates (Appendix B – Table 3), resulting in a relative standard deviation (RSD) of 2.1%.

In 2007, a combined total of 254 fish from 11 species were captured from Indian Lake,

Newboro Lake and Upper Rideau Lake with the aid of local commercial fishermen, using trap nets. Standard length and weight measurements were collected prior to the removal of a portion of dorso-lateral white muscle tissue. Frozen tissue samples were sent to the

Sport Fish Monitoring Program, within the OME in Toronto, ON in March of 2007.

Dried tissue samples were acid digested and analyzed for THg by CVAAS. All samples were processed according to the OME Determination of Mercury in Biomaterials by

CVAAS Method (OME 2005) and met the acceptable quality assurance, quality control

(QA/QC) requirements outlined in Procedure Manual for Analytical Method Validation

(OME 2007).

In 2008, 104 surface water samples were collected from the three study lakes and stored in acid cleaned Teflon® bottles prepared in an ultra-trace level Hg lab at Queen’s

University. Surface water samples were collected directly into the bottles. Depth water samples were also collected using a VanDorn water sampler; however, these data did not meet acceptable QA/QC targets and have not been included. In both instances, ultra-trace level clean hand/dirty hand protocols were used (Bloom, et al 1995) and all equipment was acid cleaned between samples. All samples were preserved with 2.5% v/v trace level Chapter 2. A Paleolimnological Analysis of Total Mercury 19

HNO3 in the ultra-trace level Hg lab at Queen’s University immediately upon return and stored at 4oC until analyzed. All water Hg samples were analyzed using a Tekran Series

2600, which was designed to meet U.S. EPA (2002) Method 1631 and utilizes a combination of dual stage gold pre-concentration and Cold Vapour Atomic Fluorescence

Spectrometer (CVAFS). Sample concentrations were calculated by comparing the absorbance of the sample to the absorbance from a calibration curve ranging from 0.5 to

100 pg g-1 (corrected for background levels) created from Hg standards made up from a certified 1, 000 mg L-1 Hg stock solution (NIST-3133). Summary results for the water Hg samples are presented in Appendix B – Table 4. Additional QA/QC samples included: an

Initial Precision and Recovery (IPR) solution following the standards; at least one

Ongoing Precision and Recovery (OPR) solution at the end of the run; a method blank and 10% duplicates (Appendix B – Table 6). A secondary CRM for Hg in river water

(ORMS-4 provided by the NRCC) was also used as an additional QA/QC measure

(Appendix B – Table 6). A reliable detection limit (RDL) of 0.15 pg g-1 and a RSD of

14.1% were calculated for these samples on this instrument (Appendix B – Table 6).

All 210Pb analyses for core dating (Appleby and Oldfield 1978) were completed using the facilities in the Paleoecological Environmental Assessment and Research Laboratory

(PEARL) at Queen’s University, ON. Dried, ground and weighed samples were sealed into clear plastic tubes using epoxy and the height of the samples in the tubes was measured. 210Pb, 137Cs and 214Bi isotopes were measured using a low-background Ortec

92x gamma ray spectrometer for 80 000 real time seconds, whereby the gamma activity counts within a specific ray range are used to measure the concentrations of a given isotope. 210Pb inferred dates and sedimentation rates were calculated using the Constant Chapter 2. A Paleolimnological Analysis of Total Mercury 20

Rate Supply (CRS) model described by Binford (1990). A sediment focusing factor of

1.1 was calculated for Indian Lake based on the comparison of 210Pb burden in the core

(Van Metre and Fuller 2009) and the measured mean atmospheric fallout rate for the

Dorset area lakes (Evans, et al 1986). The Dorset lakes are located approximately 200 km west of the study lakes, within southern Ontario. Loss-on-ignition (LOI) was calculated based on the percent difference in weight between ignition at 100oC for 24 hours and ignition at 420oC for 16 hours and was used as an indicator of percentage organic matter.

While the 210Pb activities profile for the Indian Lake core displayed the typical exponential decay curve, coupled with an appropriate 137Cs peak (ca. 1967; Figure 4), the profiles for Newboro Lake and Upper Rideau Lake were less ideal (Figure 4). The fluctuations around the 5-cm depth in the 210Pb profile for Newboro Lake (Figure 4), suggests a disturbance in the integrity of the core, possibly from mixing, resuspension, disturbance or slumping. The magnitude of the drop in 210Pb gamma counts between the first and third interval within the Upper Rideau Lake core suggests recent sediment slumping (Figure 4). As a result, the top two core intervals were discarded from all data analysis. Although dredging and weed harvesting has historically occurred within the

Rideau system, the potential for direct impacts on the integrity of the cores was considered limited given that the cores were collected from the deepest portions of the lakes. Nonetheless, it is possible that such activities may have affected other areas of the lake, resulting in the resuspention of particulates or the slumping.

These indications of disturbance within the Newboro Lake and Upper Rideau Lake cores suggest that the associated 210Pb dating profiles may not be as accurate as the Indian Lake Chapter 2. A Paleolimnological Analysis of Total Mercury 21 profile. According to the originally modeled 210Pb dates, the peak THg concentrations occurred in around 1964 and 1993 in Indian Lake, around 1994 in Newboro Lake and around 1942 and 1973 in Upper Rideau Lake. In order to confirm the dating profile, secondary markers are typically used, including 137Cs and the timing of the maximum total lead (Pb) concentration. No evident peak in 137Cs was observed in either of the cores, which may be attributable to the amount of organic content. North American maximum Pb concentrations are known to have occurred between around 1975 and 1985 based on the phase-out of leaded gasoline. Given the close proximity of the lakes to one another and the lack of localized point-sources, the sediment cores should demonstrate simultaneous peak Pb concentrations. The maximum Pb concentration in the Indian Lake core was measured around 1976, while the peak occurred around 1920 in Newboro Lake and around 1942 in Upper Rideau Lake based on the modeled 210Pb dates. In order to correct for this, the maximum Pb concentrations within the Newboro Lake and Upper

Rideau Lake cores were shifted to reflect the timing of the peak concentration within the

Indian Lake core, the effects of which are depicted in Figure 5. As a result, Indian Lake served as the primary study lake for Hg concentrations, while trends in Newboro Lake and Upper Rideau Lake were discussed in relation to Indian Lake. Background concentrations were determined to be those nearest the end of the Canal construction period (circa 1832). The background concentration for the Indian Lake core represents around 1936, while core depths of 18 cm and 29 cm were used for Newboro Lake and

Upper Rideau Lake, respectively.

Mean THg surface sediment concentrations were grouped based on the Canadian Council of Ministers of the Environment (CCME) federal THg interim sediment quality guideline Chapter 2. A Paleolimnological Analysis of Total Mercury 22

(ISQG) of 0.17 µg g-1 and the sediment probable effect level (PEL) of 0.486 µg g-1 (Table

1). Individual surface water samples were grouped based on the federal water quality guideline of 0.026 µg L-1 for THg in freshwater (Table 1). Sample groupings were coded using symbols and then spatially overlaid onto bathymetric maps (TRAK Maps 2005) using ArcGIS. Fish tissue THg concentrations were grouped based on Ontario sport fish consumption restrictions for women of child bearing age and children (0.26 to 0.52 µg g-1) and for the general public (0.61 and 1.84 µg g-1), over which consumption is not advised (OME 2007).

Results

Within the Indian Lake core, there are two identifiable peaks in sediment THg concentrations since the construction of the Canal. The first peak (0.32 µg g-1) occurred around 1957 and the second (0.52 µg g-1) around 1986 (Figure 5). Between those two peaks, the sediment profile depicts a sudden decrease around 1964 (0.18 µg g-1). Overall, the profile corresponds with a rise in sediment THg concentrations since the period of modern industrialization, around 1900, and a subsequent decrease in concentrations since the mid 1980’s. The most recent peak (~1986) was found to have a THg concentration above the federal PEL of 0.486 µg g-1. All intervals measured after approximately 1911 were found to have THg concentrations above the federal ISQG of 0.17 µg g-1. Flux, which is calculated as the sedimentation rate times the THg concentration, is used to compare trends between lakes rather than direct contaminant concentrations, which can be influenced by variations in sediment loads. The sedimentation and THg concentration profiles suggests that when the sedimentation rate was at its lowest measured level in Chapter 2. A Paleolimnological Analysis of Total Mercury 23

Indian Lake, the THg concentration per gram of sediment was the highest, resulting in the highest THg flux to the system within the past two decades (Figures 4,5). Although the

THg concentration has decreased in recent years, the increase in the sedimentation rate has resulted in a slight increase in the THg flux within Indian lake since approximately

2000. Together, this suggests that although the sediment concentration appears to be on the decline, it may actually be diluted by the increased sedimentation. Unfortunately, flux could not be calculated for Newboro Lake and Upper Rideau Lake as it relies on the 210Pb profile calculations.

Neither core from Newboro Lake and Upper Rideau Lake displayed clear dated THg peaks associated with the period of modern industrialization as observed for the Indian

Lake core. Nonetheless, the Upper Rideau Lake profile does show an increase in THg, followed by a peak and a subsequent decrease to present day – similar to the Indian Lake core, though at a smaller scale. The depth of the THg peaks are at 9 and 14-cm and based on the shifted profiles, the peaks occur in proximity to the maximum peak observed in the

Indian Lake core (Figure 5). The more disturbed Newboro Lake core, displays more variability within the THg concentration profile but also depicts a peak concentration at a depth of 3-cm (~2000 based on the Pb shifted peak). Unfortunately, the single-point THg concentration peak was not confirmed by a duplicate sample and should be interpreted with caution. Within Newboro Lake, the greatest magnitude of increase over background concentrations was less than twofold (1.8; unless the single point peak is discounted, in which case the increase is 1.5 times background), compared to the twofold-increase observed for the Upper Rideau Lake core and the fourfold-increase observed for the

Indian Lake core. Three of the analyzed Upper Rideau Lake intervals had concentrations Chapter 2. A Paleolimnological Analysis of Total Mercury 24 above the federal ISQG, though both background and more recent core intervals had concentrations below the guideline value. In comparison, Newboro Lake has consistently had concentrations above the federal ISQG; however, its peak concentration never exceeded the federal PEL.

The spatial distribution of surface THg concentrations in the three lakes was mapped using data from the grab samples, as well as the average sediment THg concentration within the top 5-cm of each core (Figure 6; Appendix B – Table 2). The mean lake-wide surface THg concentrations for Newboro Lake was found to be the highest, at 0.16 + 0.01

µg g-1, followed by Indian Lake at 0.12 + 0.07 µg g-1and then by Upper Rideau Lake at

0.12 + 0.06 µg g-1; however, Upper Rideau Lake was found to have the highest single- sample surface THg concentration at 0.22 µg g-1 (UR-16; Figure 6). Using a student t- test, only the surface THg concentrations between Newboro Lake and Upper Rideau Lake were found to be significantly different (p < 0.05)

Within Indian Lake, the minimum surface sediment THg concentration (0.02 µg g-1) was collected from IL-5 in the shallower waters near the outlet of the Lake at Chaffey’s locks

(Figures 7, 8). The highest surface sediment THg concentration (0.21 µg g-1) was collected from IL-4 in the mid-depth channel leading to Mosquito Lake, connecting

Newboro Lake to Indian Lake. Of the samples analyzed in Indian Lake, three had concentrations that exceeded the federal ISQG, including IL-4 and IL-8 in proximity to one of the islands along the northern shore, and IL-11 in the shallower area near the inflow from Clear Lake and near a marina. Chapter 2. A Paleolimnological Analysis of Total Mercury 25

While an insufficient number of samples were collected from Newboro Lake to infer any clear spatial distribution patterns, it should be noted that out of the four samples analyzed, only one exceeded the federal ISQG, NL-1, in the shallows of the northeast portion of the lake, close to an Ontario Ministry of Natural Resources fish sanctuary.

In comparison, a cluster of four samples (UR-12, UR-13, UR-15 and UR-16) exceeding the federal ISQG were all from the northern portion of the east arm of Upper Rideau

Lake (Figures 6, 8). Each of these samples was collected from 6 to 12-m water depth, and three of the points were within the main navigation channel. The minimum concentration

(0.01 µg g-1) was collected from UR-6, in the shallows along the southern shore of the western arm of the lake.

Early April surface water samples were collected from around the lakeshores and around areas with evident spring runoff. These samples represent concentrations entering the lake systems, rather than current in-lake concentrations. For this reason, these results have been presented separately (Appendix B – Table 4). Within Indian Lake, the highest mean concentrations for surface water was observed in May (0.96 + 0.39 µg L-1).

Concentrations throughout the three other study periods remained relatively consistent in surface waters (means ranging from 0.37 to 1.22 µg L-1). Similar concentrations were measured from Upper Rideau Lake, with June samples having the highest mean concentration (1.17 + 0.29 µg L-1). Higher concentrations were measured from samples collected from Newboro Lake, with June samples having the highest mean concentration

(1.48 + 1.10 µg L-1). Chapter 2. A Paleolimnological Analysis of Total Mercury 26

In 2007, the highest THg concentrations in fish tissue were associated with northern pike

(Esox lucius), smallmouth bass (Micropterus dolomieu), largemouth bass (Micropterus salmoides) and yellow perch (Perca flavescens) (Table 4). The mean THg concentrations for fish captured from Indian Lake ranged between 0.04 and 0.51 µg g-1 wet weight (ww).

Seventeen percent of black crappie (Pomoxis nigromaculatus, n=6), 60% of largemouth bass (n=10), 50% of northern pike (n=4) and 56% of rock bass (Ambloplites rupestris, n=9) captured from Indian Lake in 2007 had tissue [THg] within the consumption restriction limits for women and children (0.26 to 0.52 µg g-1). Overall, 48% of fish captured from Indian Lake had tissues THg concentrations within the range of consumption restrictions for women and children, though none were found to have concentrations within the limits for the general population. In Indian Lake, the highest mean THg concentrations were collected from: largemouth bass (0.31 + 0.13 µg g-1 ww), northern pike (0.29 + 0.10 µg g-1 ww) and rock bass (0.27 + 0.09 µg g-1 ww). Of the fish analyzed, only black crappie demonstrated a strong positive correlation between tissue

THg concentrations and both length and weight (r = 0.92, p < 0.05 and r = 0.93, p < 0.05, respectively), though largemouth bass was also found to have moderately strong positive correlations (r = 0.84 p < 0.05 and r2 = 0.84 p < 0.05, respectively).

The mean concentration from the 66 fish of seven species captured from Newboro Lake in 2007 was 0.22 + 0.17 µg/g ww, with a range between 0.06 and 0.79 µg/g ww (Table

4). Of the fish analyzed, 26% were found to have concentrations within the ranges suggested for consumption restriction for women and children; and four samples were found to exceed the general consumption restriction level of 0.52 µg g-1 ww, all of which were largemouth bass. For Newboro Lake, the three species with the highest mean Chapter 2. A Paleolimnological Analysis of Total Mercury 27 concentrations in 2007 were: largemouth bass (0.44 + 0.20 µg g-1 ww), northern pike

(0.27 + 0.13 µg g-1 ww) and yellow perch (0.26 + 0.10 µg g-1 ww). Of the fish analyzed, only largemouth bass demonstrated a strong positive correlation between tissue THg concentration and both length and weight (r = 0.90 p < 0.0001 and r = 0.90 p < 0.0001, respectively).

The mean THg concentration for the 90 fish from nine species collected from Upper

Rideau Lake in 2007 was 0.23 + 0.29 µg g-1 ww (Table 4). As in Newboro Lake, 26% of fish analyzed were found to have concentrations within the range of consumption restrictions for women and children; and eight samples were found to exceed the general consumption restriction limits. The mean THg tissue concentration for walleye

(Stizostedion Vitreum) was 1.22 + 0.26 µg g-1 ww, well above the consumption restriction for the general public. In addition, two smallmouth bass and two largemouth bass were found to have tissue THg concentrations above 0.52 µg g-1 ww. For Upper Rideau Lake, the three species with the highest mean concentrations in 2007 were: walleye (above), northern pike (0.36 + 0.10 µg g-1 ww) and smallmouth bass (0.29 + 0.21 µg g-1 ww). Of the fish analyzed, largemouth bass and smallmouth bass demonstrated strong positive correlations between tissue THg concentrations and both length and weight (r = 0.90 p <

0.0001 and 0.98 p < 0.0001; r = 0.90 p = 0.002 and r = 0.96 p < 0.0001, respectively). Chapter 2. A Paleolimnological Analysis of Total Mercury 28

Discussion

Changing atmospheric deposition of Hg is the primary attributer to the enrichment of

THg in sediments within the northern hemisphere (Meili 1991; Swain, et al 1992;

Engstrom and Swain 1997). Up to 57% of all Hg supplied to a lake can be directly attributed to atmospherically transported sources (Mierle 1990; Engstrom and Swain

1997; Rossman 1999). While global atmospheric THg pools vary spatially (Pirrone, et al

1996a), it is generally assumed that the enrichment of sediment THg in recent years compared to pre-industrial times should be comparable between regions. Both peak (1.6 to 3.9) and current (1.1 to 2.3) THg enrichment in all three lakes are within the ranges observed in 14 Ontario lakes (1.1 to 3.5; mean of 2.2) by Johnson, et al (1986); 12

Quebec lakes (mean of 2.3) by Lucotte, et al (1995); and 26 Quebec lakes (1.2 to 8.6) by

Ouellet and Jones (1983). Enrichment factors (7 to 24.5) observed in the study lakes remained below what has been observed within Lake Ontario (Pirrone, et al 1998;

Marvin, et al 2002), with its highly developed shores but is comparable to the enrichment

(2.1) observed in eastern Lake Erie (Marvin, et al 2002). In comparison, other studies conducted throughout the U.S. have reported enrichment factors ranging from 0.8 in north-central Wisconsin to 10 in Clear Lake, California (Rada, et al 1989; Swain, et al

1992; Kamman, et al 2005; Engstrom, et al 2007; Sanders, et al 2008). Overall, the sediment THg concentrations within the study lakes lie within the range of concentrations for other inland lakes within the region.

Results from the Indian Lake sediment profile indicate that the sediment THg concentration peaked in the mid-1980’s, above the federal PEL and at roughly five times Chapter 2. A Paleolimnological Analysis of Total Mercury 29 pre-industrial concentrations. Similar peaks were also identified in the cores collected from Newboro Lake and Upper Rideau Lake, though the magnitudes of the peaks were smaller. The precise timing of the peaks vary slightly based on the shifted profiles.

Nonetheless, each of the cores depict a buried maximum THg concentration within the upper layers of the core suggesting that inputs are on the decline.

In 2000, Environment Canada reported (in Howland, et al 2005) that Canada-wide atmospheric Hg emissions decreased by 95% between 1975 and 1983 as a result of increased legislation and operating procedures for chlor-alkali facilities. Subsequently in

2007, it was reported that Hg emissions were reduced by 50% within the north-eastern

U.S. and eastern Canada since 1998 (NESCAUM 2007). Provincially, there was a greater than 50% reduction in emissions from the non-ferrous smelting and refining industry between 1992 and 1993 in Ontario (Ames, et al 1998; EC 2008). If sediment THg profiles are indeed reflective of atmospheric concentrations, Ontario lakes should now display buried sediment THg peaks between the late 1980’s and early 1990’s. Such buried peaks were observed within the three study lakes. The timing of the THg decrease from peak concentrations appears to generally coincide with the initial reduction on a national level

(1975-1983; Figure 5). This trend is comparable to Hg core profiles in most Ontario lakes corresponding to a world-wide decrease in atmospheric concentrations (Engstrom, et al

2007). More recently, it has been suggested that sediment profiles are actually more reflective of local emission reductions, than they are national or regional-scale reductions

(NESCAUM 2007). The time period for the observed decreases in THg concentrations within Indian Lake (and the shifted time periods for Newboro Lake and Upper Rideau

Lake)also coincide with the final closure of various Hg emitting industries by the 1980’s, Chapter 2. A Paleolimnological Analysis of Total Mercury 30 such as a coal gasification plant and battery manufacturing plants in nearby Kingston, ON

(Malroz Engineering 2003). A review of historical land-uses around the three study lakes did not reveal any additional sources which would likely have contributed to the lake- specific timing of the peaks (Appendix A; Lai 2009). While the observed decreases within recently deposited sediments in various lakes throughout Ontario would suggest a reflection of reduced Hg emissions, we were not able to pin-point any lake-specific changes which could explain the observed difference in the magnitude of enrichment among the interconnected lakes.

Elsewhere in Ontario, variations in THg core profiles among lakes from similar regions have been attributed to geological influences, particularly within Precambrian Shield

Lakes (e.g. Wren, et al 1983; Evans 1986; Rasmussen, et al 1998). The steady but relatively high background THg concentrations observed in the Newboro Lake core was originally thought to be due to geological sources. Such relationships can be confirmed based on correlations between surface and pre-colonial sediment THg concentrations

(Rasmussen, et al 1998). In the case of the study lakes, there do not appear to be any such correlations, although there were insufficient data for statistical analysis. In addition, the speculation of geological influence for the Newboro Lake THg concentration trend is not supported by the findings of Kettles (1990) who mapped the geochemistry of glacial sediments in the area, nor Friske, et al (1997) who mapped sediment THg concentrations and found the area around Westport, ON to be in the bottom 5th to 25th percentile for geological Hg deposits in Ontario (with background concentrations between 0.05 and

0.08 µg g-1). Also, the area is primarily underlain by limestone and sandstone, which generally contain naturally low THg concentrations in the range of 0.04 to 0.05 µg g-1 Chapter 2. A Paleolimnological Analysis of Total Mercury 31

(Cannon 1978 in Friske and Coker 1995). While none of the measured background Hg concentrations for the study lakes were as low as those measured in the geological surveys, THg concentrations were only measured up to a depth of 24-cm, which is a minimum of 10-cm above what would be considered geological background. Rasmussen, et al’s (1998) argument for geological inputs was founded on the premise that Hg is susceptible to diagenic remobilization within sediments; however, various studies have since confirmed the integrity of sediment Hg profiles (e.g. Landers, et al 1998; Lockhart, et al 2000; Couillard, et al 2004; Biester, et al 2007). In addition, if there were contributing geological sources, there would likely have been an increase in concentration during the period of Canal construction, which saw substantial disturbances in the area; however, none were observed. Based on the underlain geology of the study area, the recognized integrity of sediment Hg profiles, and the sudden increase in THg concentrations observed within the study cores, a geological source is not considered to be the varying factor between lakes.

One factor which is specific to each of the interconnected lakes is its catchment area.

Watershed influences have been suggested as another potential factor influencing THg distribution patterns within individual lakes (e.g. Engstrom and Swain 1997; French, et al

1999; Grigal 2002; Kamman and Engstrom 2002; Engstrom, et al 2007). Previous studies have found significant correlations between enrichment factors in sediment cores and the ratio of catchment area to lake area, suggesting that watershed contributions are substantial input sources to lake sediments (Evans, et al 1986; Engstrom, et al 2007).

Unfortunately, the number of cores selected for THg analysis (n = 3) does not lend itself to sound statistical analysis. Nonetheless, Indian Lake’s large drainage area-to-lake area Chapter 2. A Paleolimnological Analysis of Total Mercury 32 ratio, three times higher than the other two lakes (Table 3), coupled with the magnitude of the THg peak, suggests that watershed-based contributions may account for some of the variability observed among the lakes.

Recently, Engstrom, et al (2007) conducted a thorough analysis of watershed and land- use based influences for 55 Minnesota lakes. They found that trends in THg flux were more comparable among regions than were THg concentration profiles. Using THg fluxes did not improve the association among profiles for our lakes since sedimentation rates were derived from the 210Pb profiles. Engstrom, et al (2007) also found a rise in sedimentation rates, coupled with a rise in the percentage of organic matter, which was also not the case in our lakes (Figures 4, 5). The authors hypothesized, based on a strong correlation between log-sedimentation rates within recent intervals and THg concentrations, that watershed influences were significant. Using the data from the post-

1990 intervals, our results only show a non-significant negative linear correlation (r2 =

-0.37, p = 0.06). Engstrom, et al (2007) also studied the relationships between THg concentrations and the proportion of categorical land-uses within each of the lake catchment areas. They found that the percent composition of build-up and roads was significantly correlated to THg flux within the Metro lake group, while the percentage of agricultural land and roads was significantly correlated for the south-central lake group.

While this was not quantitatively assessed in this study, visual inspection of recent aerial photographs shows that Upper Rideau Lake is surrounded by the greatest proportion of settlement, agricultural land and major roads (Christie and Smol 1996), followed by

Newboro Lake and lastly Indian Lake. In comparison, Indian Lake, with the highest THg flux, is considered to have the smallest proportion of its catchment area devoted to Chapter 2. A Paleolimnological Analysis of Total Mercury 33 development, roads or agricultural lands. Instead, the area is primarily surrounded by forested areas, which Munthe and Hultberg (2004) found to have almost twice as much atmospherically deposited Hg compared to unforested areas. Interestingly, the regions where Engstrom, et al (2007) found significant correlations between THg concentrations and watershed influences (the Metro and South-central areas of Minnesota) had more than double the enrichment factors observed in these lakes (mean of 9.8 and 5.8, respectively). Their northeast study lakes, which had more comparable enrichment factors to ours (2.0 to 6.7), were not found to have significant correlations. This would suggest that watershed influences may be the primary drivers of high THg concentrations within developed areas but they do not appear to explain the differences between the observed lake profiles.

National, provincial and regional atmospheric emission reductions appear to have resulted in a recent decrease in sediment THg concentrations within the studied Rideau

Lakes; however, they cannot explain the variation in sediment THg profiles. While geological sources and watershed influences were also considered, results suggest that these are also not the driving factors. Evans, et al (1986) suggested that lake water hardness may have influenced THg concentration and enrichments within a

Peterborough, ON lake. The pH of the lake water could also be a factor (e.g. Fjeld et al.

1994 in Landers, et al 1998), as could lake productivity (e.g. Fjeld et al. 1994 in Landers, et al 1998). Forrest, et al (2002) identified a pattern of increased productivity in Upper

Rideau Lake between 1830 and 1970 (based on diatom assemblages), which could have influenced THg concentrations. However, the three interconnected lakes share very similar water chemistry and productivity characteristics (Table 3), and therefore does not Chapter 2. A Paleolimnological Analysis of Total Mercury 34 account for the THg variability in lake sediments. Other studies have found an enrichment in nutrients following Canal construction, likely attributed to the flooding of new areas (e.g. Christie and Smol 1996; Forrest, et al 2002); which could have influenced the THg concentration profiles; however, the timing of the concentration increase does not coincide with this time period. Though encouraging, the decreasing trend in THg concentrations must also be considered in terms of flux, which suggests that the increased sedimentation rate within Indian Lake may be diluting the measured concentrations.

Within Indian Lake, two of the grab samples were found to have THg concentrations that exceeded the ISQG, in addition to the composite sample from the top of the primary core, though no evident spatial distribution pattern was identified (Figures 6, 7). While there were an insufficient number of samples analyzed from Newboro Lake, it should be noted that only the composite sample from the primary core was found to exceed the ISQG. Of the 17 samples analyzed from Upper Rideau Lake, four, all located within the same region in the northeast portion of the lake, exceeded the ISQG. The most likely internal factors affecting the spatial distribution of THg within these lakes are organic matter, grain size and water depth at sampling locations. Mercury is known to have a high affinity for organic matter, which generally consists of smaller particles (Meili 1991;

Swain, et al 1992; Munthe, et al 2007). Correlations between water depth at the sampling location and THg concentrations have also been suggested, implying an association between THg and fine particulates (Smol 2008). For the study lakes, THg in surface samples were only found to be correlated with water depth at sampling locations for

Newboro Lake (r2 = 0.94, p < 0.05) Chapter 2. A Paleolimnological Analysis of Total Mercury 35

While less obvious, the single surface sediment ISQG exceedance in Newboro Lake, collected from the deepest basin of the lake also supports this hypothesis (Figure 6).

Interestingly, this same pattern was not consistently seen in Indian Lake (Figure 7) and was not seen in the larger Upper Rideau Lake (Figure 8). Instead, in Upper Rideau Lake, the pattern appears inversed, where the concentrations are lower at the inflows (the connection with Newboro Lake and around Westport) and higher towards the outflows

(towards Big Rideau Lake). This would suggest that either there is a localized input source located in that area of the lake, or that the islands act as a barrier, slowing the flow of water, thus allowing the deposition of suspended particulates. Interestingly, no exceedances were found from the samples collected from the main basin of the lake. The comparably low concentrations observed around the two sand beaches (URL-3 and URL-

6), with larger sizes particles, further supports the notion that the Hg is associated with the finer particulates. Overall, it is suspected that the differences in magnitudes of enrichment and spatial distribution patterns among the lakes are likely attributable to multiple factors. Though no individual causal influences were identified throughout this study, the inter-relationships between such factors should be further evaluated in the future, particularly within Indian Lake.

Although no clear spatial patterns were identified, results from the cores studied do suggest that THg concentrations are decreasing in recent years within the study lakes, the overall flux to the system may actually be slightly increasing. The question then remains as to how the recent concentration decreases are affecting aquatic organisms? There exists conflicting evidence in the literature regarding the affect of decreased atmospheric

Hg concentrations on aquatic biota. While Hrabik and Watras (2002) found a 30% Chapter 2. A Paleolimnological Analysis of Total Mercury 36 decrease in yellow perch tissue THg concentrations between 1994 and 2000, which they correlated to decreased atmospheric emissions, a study of over 15,000 fish samples in

North-eastern North America found no direct relationship between fish and atmospheric concentrations (Munthe, et al 2007). Similarly, Rose, et al (1999) were unable to find a correlation between largemouth bass, yellow perch or brown bullhead (Ameiurus nebulosus) tissue concentrations and sediment THg concentrations in Massachusetts lakes. In comparison, both largemouth bass and yellow perch tissue concentrations were found to have decreased (roughly 25% and 32%, respectively) between 1999 or 2001 and

2004 in 17 Massachusetts lakes (MDEP 2006) although largemouth bass tissue concentrations displayed significant declines between 1988 and 2000 in the Florida

Everglades (Atkeson, et al 2003).

Within the study lakes, northern pike is the only species that has been consistently monitored over time by the OME. In the late 1970’s, when sediment THg was almost at its peak concentration in Indian Lake, the mean THg tissue concentration for all sampled pike was 0.79 + 0.25 µg g-1 ww (n=15, OME 2007). Between 1979 and the present day, sediment THg concentrations have decreased roughly 35% and the mean pike tissue concentration, irrespective of size, has decreased more than 60%, a statistically significant decrease (p < 0.05). Mean pike tissue concentrations have also decreased in

Newboro Lake since 1978 (by roughly 50%); however, peak sediment THg concentrations were highest around 1988, when mean pike tissue concentrations had already decreased by roughly 40%. Within Upper Rideau Lake, mean pike tissue concentrations have actually increased roughly 4% since the 1970’s and the highest mean pike tissue concentrations were observed when sediment THg concentrations were at one Chapter 2. A Paleolimnological Analysis of Total Mercury 37 of the lowest points since the early 1900’s. While there appears to be a relationship between decreased sediment THg concentrations in Indian Lake and decreased pike tissue concentrations, the same relationship is not evident in the other two study lakes.

Unfortunately, no definitive conclusions can be drawn for fish captured from Indian Lake due to the lack of consistent temporal continuity for fish tissue monitoring and archiving.

Also, no such conclusions can be drawn from the more frequently samples Newboro

Lake or Upper Rideau Lake due to the 210Pb dating profiles.

Overall the THg enrichment to each of the lakes is within the range observed for most other freshwater lakes in the region. Sedimentary records indicate that THg peaked in the mid-1980’s, at concentrations above the federal PEL and roughly five times background concentrations within Indian Lake. Similar trends of a lower magnitude of enrichment were observed in Newboro Lake and Upper Rideau Lake. Within recent decades, sediment THg concentrations appear to have declined within all the study lakes; however, due to a rise in sedimentation rates within Indian Lake, the overall flux of THg may not actually be on the decline. Though only northern pike tissue concentration trends could be examined over time in Indian Lake, results indicate that fish THg concentrations have decreased more than 60% since the late 1970’s, during which time; sediment THg concentrations appear to have decreased 35%. Further research pertaining to sport fish

THg tissue concentration trends is warranted, particularly in parallel with temporal sediment concentrations. Sport fish should continue to be monitored on a regular basis within these highly utilized lakes, particularly within Indian Lake, which has been under surveyed in the past. Although the results are encouraging, there remains a cause for concern in relation to Hg exposure within the study lake, primarily as a result of sport fish Chapter 2. A Paleolimnological Analysis of Total Mercury 38 consumption. Further study of temporal THg concentration trends in Newboro Lake and

Upper Rideau Lake would also enhance the interpretation of results among the study lakes. Additional study of the surface sediments near the islands in the north-eastern bay of Upper Rideau Lake is also merited based on the THg concentrations measured. Chapter 2. A Paleolimnological Analysis of Total Mercury 39

Table 3 Measured geochemical lake characteristics during sampling events

Indian Newboro Upper Rideau

(IL) (NL) (URL)

Lake Area (km2) 2.8 16.1 14.0

Latitude of Primary Core 44o35’25’’N 44o36’57’’N 44o41’15’’N

Longitude of Primary Core 76o19’24’’W 76o19’22’’W 76o20’7’’W

Latitude of Lake Centroid 44o35’39’’N 44o37’35’’N 44o41’6’’N

Longitude of Lake Centroid 76o19’42’’W 76o19’25’’W 76o19’45’’W

Immediate Lake Drainage 97.5 305.0 152.7 Area (km2) Greater Greater Larger Watershed (size) Rideau Lakes Cataraqui Cataraqui (km2) (490) (946) (946) Drainage Area to Lake Area 35.2 18.9 10.9 Ratio

Maximum Lake Depth 25.9 25.3 19.2 (m) Mean Surface Temperature 20.5 22.4 22.1 (oC) a

Mean Surface pH a 8.49 9.00 8.85

Mean Surface Specific 179 200 213 Conductivity (µS cm-1) a Mean Surface Total 0.11 0.12 0.11 Dissolved Solids (g L-1) a Mean Surface Dissolved 9.46 9.51 9.29 Oxygen (mg L-1) a Approximate Depth of Lake 24 23 18 at Core Location (m) Vertical Depth of Core 0.30 0.32 0.37 (m) a – Water quality parameters measured using a Hydrolab multiprobe data sonde. Mean values calculated based on multiple field sampling results obtained between April and August, 2008.

Chapter 2. A Paleolimnological Analysis of Total Mercury 40

Table 4 Summary of total mercury concentrations ([THg]) in sport fish tissue samples

Length Range THg Range (ug g-1 Fish Species Scientific Name N Weight Range (g) (cm) ww) Black Crappie Pomoxis nigromaculatus 6 18.9 to 30.2 106 to 571 0.08 to 0.27 Bluegill Lepomis macrochirus 7 15.3 to 20.2 101 to 184 0.06 to 0.16 Brown Bullhead Ameiurus nebulosus 10 28.5 to 34.2 307 to 572 0.04 to 0.11 Largemouth Bass Micropterus salmoides 10 22.5 to 40.4 169 to 949 0.11 to 0.51 Northern Pike Esox lucius 4 46.5 to 56.9 536 to 1198 0.19 to 0.41 Pumpkinseed Lepomis gibbosus 10 17.5 to 21.3 122 to 219 0.06 to 0.16

Indian Lake Lake Indian Rock Bass Ambloplites rupestris 9 17.6 to 26.5 90 to 380 0.13 to 0.42 Yellow Perch Perca flavescens 1 26.4 225 0.20 Mean Total 57 26.5 328 0.20 Bluegill Lepomis macrochirus 10 15.9 to 21.6 91 to 228 0.06 to 0.25 Brown Bullhead Ameiurus nebulosus 10 25.2 to 30 231 to 437 0.01 to 0.05 Largemouth Bass Micropterus salmoides 14 22.6 to 45.9 155 to 1635 0.11 to 0.79 Northern Pike Esox lucius 4 39.6 to 57.2 354 to 1035 0.17 to 0.43 Pumpkinseed Lepomis gibbosus 9 16.6 to 21.2 97 to 258 0.09 to 0.2 Rock Bass Ambloplites rupestris 10 21 to 29.1 202 to 349 0.13 to 0.32

Newboro Lake Newboro Yellow Perch Perca flavescens 9 23.1 to 28.2 200 to 322 0.17 to 0.48 Mean Total 66 27.1 373 0.22 Bluegill Lepomis macrochirus 10 17.8 to 21.9 153 to 238 0.05 to 0.17 Brown Bullhead Ameiurus nebulosus 9 22.5 to 36.4 160 to 765 0.03 to 0.07 Largemouth Bass Micropterus salmoides 12 18.1 to 46.5 161 to 1729 0.06 to 0.69 Northern Pike Esox lucius 8 49.7 to 71.3 879 to 2296 0.2 to 0.5 Pumpkinseed Lepomis gibbosus 10 16.6 to 24.8 106 to 399 0.04 to 0.13 Rock Bass Ambloplites rupestris 10 17.5 to 27.1 94 to 451 0.1 to 0.44 Smallmouth Bass Micropterus dolomieu 8 24.6 to 46.6 297 to 1644 0.1 to 0.76 Walleye Sander vitreus 5 60.5 to 66.9 2353 to 3799 0.91 to 1.6 Upper Rideau Lake Lake Upper Rideau Yellow Perch Perca flavescens 18 17.1 to 33.3 60 to 551 0.05 to 0.26 Mean Total 90 30.8 595 0.23 Chapter 2. A Paleolimnological Analysis of Total Mercury 41

Figure 2 Detailed bathymetric mapping of study lakes Bathymetric mapping provided TRAK Map Concepts Inc. 2005. Ontario Inland Lakes (TRAK Maps - Canadian Nautical Charts). 36 Digital Maps. Saint-Donat, Québec. Chapter 2. A Paleolimnological Analysis of Total Mercury 42

Figure 3 Sediment sampling locations Mean values for the top 5 cm of the 2008 analyzed core used for comparison to the 2007 grab samples. Sample codes include Indian Lake (IL), Newboro Lake (NL) and Upper Rideau Lake (URL). Numbers refer to sample sites and C denotes core sample locations. Bathymetric mapping provided TRAK Map Concepts Inc. 2005. Ontario Inland Lakes (TRAK Maps - Canadian Nautical Charts). 36 Digital Maps. Saint-Donat, Québec. Chapter 2. A Paleolimnological Analysis of Total Mercury 43

Indian Lake Newboro Lake Upper Rideau Lake Gamma Activities (dpm g-1) Gamma Activities (dpm g-1) Gamma Activities (dpm g-1)

0 20 40 60 80 100 120 0 50 100 150 200 250 300 0 20 40 60 80 0 0 0

5 5 5

10 10 10

15 15 15

20 20 20 Depth of Interval Midpoint (cm) Depth Midpoint of Interval 25 25 25

30 30 30 0 10 20 30 40 50 60 0 10 20 30 40 50 60 0 10 20 30 40 50 60 Loss-on-ignition (%) Loss-on-ignition (%) Loss-on-ignition (%)

210 Pb 137 Cs LOI

Figure 4 Original 210Pb, 137Cs gamma activity and loss-on-ignition profiles Horizontal error bars represent standard deviation. Chapter 2. A Paleolimnological Analysis of Total Mercury 44

Indian Lake Newboro Lake Upper Rideau Lake THg Concentration (µg g-1) THg Concentration (µg g-1) THg Concentration (µg g-1)

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.0 0.1 0.2 0.3 0.4 0.10 0.15 0.20 0.25 0

2000

10 1950 Pb DatePb (years)

210 20 1900 Core (cm) Depth Core Inferred

1850 30

Original THg concentration profile based on core depth (cm) 210 0.00 0.01 0.02 0.03 0.04 0.05 Pb dated THg concentration profile for Indian Lake (years) 210 -2 -1 Sedimentation Rate Pb derived sedimentation rate profile for Indian Lake (g cm yr ) (g cm-2 yr-1) Shifted THg profile based on the timing of the Indian Lake peak total Pb concentration (years)

Figure 5 Original and shifted sediment total mercury (THg) concentration profiles The black triangles represent the THg concentration profile for Indian Lake based on core depth (right axis) while the hollow triangles represent the same profile, based on the 210Pb inferred dates (left axis). The black symbols for the Newboro Lake and Upper Rideau Lake cores represent the THg profiles based on core depth (right axis). The grey symbols for the Newboro Lake and Upper Rideau Lake cores represent the THg profiles based on the shifted 210Pb inferred dates, such that the maximum total lead concentration for each core occurs simultaneously with the peak in Indian Lake around 1979 (Refer to Chapter 2 methods) Chapter 2. A Paleolimnological Analysis of Total Mercury 45

Figure 6 Spatial distribution of surface sediment mercury (Hg) concentrations Sediment samples screened against the federal interim sediment quality guideline (ISQG) of 0.17 µg g-1 and the probable effect level (PEL) of 0.486 µg g-1 set by the Canadian Council of Ministers of the Environment (CCME). Mean concentrations for the top 5cm of sediment cores used in comparison to grab samples. Bathymetric mapping provided TRAK Map Concepts Inc. 2005. Ontario Inland Lakes (TRAK Maps - Canadian Nautical Charts). 36 Digital Maps. Saint-Donat, Québec. Chapter 2. A Paleolimnological Analysis of Total Mercury 46

CCME ISQG

) (0.17) -1

0.10 [THg] (ugg[THg] Surface sediment Surface

Figure 7 Relative surface sediment total mercury concentrations in Indian Lake Light grey bars represent surface sediment total mercury concentrations ([THg]) below the federal interim sediment quality guideline (ISQG) set by the Canadian Council of Ministers of the Environment (CCME) at 0.17 ug g-1. Dark grey bars represent surface sediment [THg] above the ISQG. Bathymetric mapping provided TRAK Map Concepts Inc. 2005. Ontario Inland Lakes (TRAK Maps - Canadian Nautical Charts). 36 Digital Maps. Saint-Donat, Québec. Chapter 2. A Paleolimnological Analysis of Total Mercury 47

CCME ISQG

) (0.17) -1

0.10 [THg] (ugg[THg] Surface sediment Surface

Figure 8 Relative surface sediment total mercury concentrations in Upper Rideau Lake Light grey bars represent surface sediment total mercury concentrations ([THg]) below the federal interim sediment quality guideline (ISQG) set by the Canadian Council of Ministers of the Environment (CCME) at 0.17 ug g-1. Dark grey bars represent surface sediment [THg] above the ISQG. Bathymetric mapping provided TRAK Map Concepts Inc. 2005. Ontario Inland Lakes (TRAK Maps - Canadian Nautical Charts). 36 Digital Maps. Saint-Donat, Québec. Chapter 3. Trace Element Trends within the Rideau River Waterway 48

Chapter 3 - Trace Element Trends within the UNESCO Designated Rideau River Waterway

Abstract

The Rideau River Waterway, a UNESCO designated World Heritage site in eastern

Ontario, is an important recreational and tourist destination. In 2006, a study of metal concentrations found exceedances of federal interim sediment quality guidelines for Cd,

Cu, and Zn, as well as probable effect level sediment exceedances for Pb within the headwater lakes of the Canal. Each of these elements is known to bioaccumulate and/or bioconcentration, which highlights the potential for human health implications, particularly within such a highly utilized recreational system. Utilizing paleolimnological techniques, historical records of 10 elements (As, Cd, Co, Cr, Cu, Ni, K, Pb, Rb, and Zn) were analyzed from chronologically deposited lake sediments collected from three interconnected lakes within the Canal. The objectives of this study were to examine the historical element trends, as preserved in sediments since the construction of the Canal

(ca. 1832), and to consider both watershed and anthropogenic influences which might explain the variations in element trends observed. The core profiles for As, Cd, Cu, Ni,

Pb and Zn depict buried maximum peak concentrations within recent decades and Chapter 3. Trace Element Trends within the Rideau River Waterway 49 subsequent declines towards surface concentrations. Although encouraging, the decreases observed appear to be partially attributable to increased sedimentation rates. In comparing the profiles among the three lakes, it is evident that the concentrations within

Indian Lake sediments are higher, as are the magnitudes of enrichment compared to background (~1836). The similarities between profile trends for specific groups of elements (Cd, Pb, Zn, and Cu, Ni) among lakes suggest that the predominant input source is atmospheric. While no single causal factor could explain the among-lake variations measured, catchment area to lake area ratios and surrounding land-uses qualitatively appear to be influential factors. Overall, concentrations of Cd, Cu, Pb and Zn remain elevated within the study lakes and merit further study.

Introduction

The Rideau River Waterway (Rideau Canal), a United Nations Educational, Scientific and Cultural Organization (UNESCO) designated World Heritage site in eastern Ontario, is an important recreational and tourist destination. Cottaging, boating and fishing are popular activities, and the area is recognized for its unique Canadian cultural heritage.

However, in 2006, several lakes within the southern portion of the system were found to exceed federal guidelines for sediment metal concentrations. Overall, Upper Rideau Lake

(URL) had the highest mean concentrations, followed by Indian Lake (IL). Mean surface sediment concentrations for these two lakes exceeded the federal interim sediment quality guideline (ISQG) for Cd (0.6 µg g-1), Cu (35.7 µg g-1), and Zn (123 µg g-1), while mean concentrations of Pb, exceeded the federal probable effect level (PEL; 91.3 µg g-1) within both lakes (Table 1). Such high sediment metal concentrations were surprising given the Chapter 3. Trace Element Trends within the Rideau River Waterway 50 rural locations of the lakes. A review of land-uses in and around the study area identified a number of historical saw, grist, and woolen mills located along the lakeshores, though they have all since ceased operation (Appendix A; Lai 2009). While natural and local anthropogenic inputs were considered in the historical review, no individual point sources, which could account for the concentrations observed, were identified amongst or in proximity to the cottage-lined shores of these lakes. The high concentrations of metal contaminants measured, in addition to the extensive recreational use (particularly for cottaging) and commercial fisheries operating in the area suggested that there might be a cause for concern.

Technological innovations, coupled with increased policy and legislation, are generally recognized as having resulted in a reduction of industrial emissions of metals within

North America. A number of studies have documented the corresponding historical changes in global atmospheric element concentrations in various matrices (e.g. Boutron, et al 1991; Mahler, et al 2006). In areas where there are no known point sources, any enrichment since the late 19th century is generally attributed to global atmospheric loadings. It has been acknowledged that, even considering the number of studies that have been conducted, there remains very limited data and information concerning the specific transport pathways of trace elements to aquatic systems (Callender 2003). In addition, although numerous studies examine trends over broad spatial areas, seldom do researchers attempt to explain the variations observed between element profiles collected from lakes located within the same region. In this study, we consider three attached lakes, sharing similar physiochemical properties, with varying historical profiles and spatial element distribution patterns. The objectives of this study were to examine the historical Chapter 3. Trace Element Trends within the Rideau River Waterway 51 element trends, as preserved in sediments since the construction of the Canal, and to consider both watershed and anthropogenic influences which might explain the variations in element trends observed between lakes.

Methods and Data Analysis

A description of the study lakes, their underlying geology, and field sediment sampling methods was outlined in Chapter 2. In summary, a core take from the deepest site of each lake was analyzed for paleolimnological trends. In addition, to assess spatial trends, 30 surface grab samples and eight additional cores were collected, with the top 10-cm of each core averaged to represent a surface sample (Appendix B – Table 1). Cores were collected in April, May and August 2008, from Indian Lake, Newboro Lake and Upper

Rideau Lake, respectively and extruded at 1-cm intervals, while grab samples were collected in August and September 2007.

All core intervals and grab samples were analyzed for As, Cd, Co, Cr, Cu, K, Ni, Pb, Rb, and Zn using Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES) in the Analytical Services Unit (ASU), Department of Environmental Studies, Queen’s

University. Dried, ground sediment samples were digested on hot plates using HNO3 and hydrochloric acid (HCl). Digested samples were atomized and introduced to a plasma flame where they were broken up into their respective atoms. The light intensity of each element was then measured at specific wavelengths, unique to each measured parameter.

The Quality Assurance/Quality Control (QA/QC) data, including the measured concentrations for the National Research Council of Canada (NRCC) MESS-3 and SS-2 Chapter 3. Trace Element Trends within the Rideau River Waterway 52

Certified Reference Materials (CRMs) are listed in Appendix B – Table 9. The QA/QC data were all within the acceptable limits for the instrument with three exceptions where results for both CRMs were beyond the range of the control limits. In these cases, the results were discarded and where possible, samples were re-digested and re-analyzed.

The calculated relative standard deviation (RSD) for each measured element, based on sample duplicates are presented in Appendix B – Table 7.

In 2008, 83 surface and depth water samples were collected from the three study lakes and stored in nitric acid (HNO3) cleaned polyethylene bottles.Ultra-trace level clean hand/dirty hand protocols were used (Bloom, et al 1995) and all equipment was acid cleaned between samples. All samples were preserved with 2.5% trace level HNO3 by volume immediately upon return to Queen’s University and stored at 4oC until analyzed.

All water samples were digested using HNO3 and HCl on hot plates followed by ICP-

OES analysis within the ASU lab. All QA/QC data are presented in Appendix B – Tables

8, 10.

Loss-on-ignition (LOI) and 210Pb methods are described in Chapter 2. As previously discussed, the 210Pb profile obtained for Indian Lake is the most accurate and suggests that is it the most reliably dated profile. While there exists a strong linear correlation between the log unsupported 210Pb and cumulative mass for both the Newboro Lake (r2 =

0.90, p < 0.005) and Upper Rideau Lake (r2 = 0.98, p < 0.0001) cores, suggesting that the

210Pb profiles are sound, the peak total Pb profiles do not match the known timing of peak atmospheric Pb (~1975 to 1985), nor the peak observed in Indian Lake (~1979). As summarized by Appleby and Oldfield (1983), less than perfect 210Pb profiles can be Chapter 3. Trace Element Trends within the Rideau River Waterway 53 caused by a number of factors, including: loss of 210Pb at the sediment-water interface

(Koide et al. 1973 in Appleby and Oldfield 1983); mixing of layers (Petit 1974 and

Robbins et al. 1977 in Appleby and Oldfield 1983); slumping (Edgington and Robbins

1977 in Appleby and Oldfield 1983); erosion and/or diagenesis. Binford, et al (1993) further suggest that variations in hydrological regimes, sediment focusing, water depth

(resulting in differences in oxidation-reduction processes) and estimation of supported

210Pb can also influence the dating of profiles. More recently, Brenner, et al (2004) found that 210Pb profiles also be affected by 226Ra inputs (which decay to 210Pb) from groundwater sources and Schottler and Engstrom (2006) found that variations in the rate of 210Pb deposition and transfer to sediments could also affect results from the dating models. Binford, et al (1993) suggest that when a secondary, independent marker is not in agreement with the 210Pb inferred dates, the dates should be regarded as unreliable until either re-analyzed or supported by a subsequent independent marker.

Atmospheric Pb concentrations throughout North America are known to have peaked between the mid-1970’s and mid-1980’s due to the transition to unleaded gasoline

(Crecelius and Piper 1973; Edgington and Robbins 1976; Miller and Friedland 1994;

Schottler and Engstrom 2006). This peak concentration is so distinct in sediment profiles that it has been used to approximate sediment age and is often used as an independent marker (much like 137Cs) for dated profiles (Graney, et al 1995; Siver and Wozniak

2001). In the case of our study, the study lakes are interconnected, suggesting that they should all be receiving the same regional inputs and thus, that peak Pb concentrations should be evident around roughly the same time period. Under this assumption, another approach used in the literature (Yong, et al 2001) is to shift the dating scale on the Chapter 3. Trace Element Trends within the Rideau River Waterway 54

Newboro Lake and Upper Rideau Lake profiles, such that the peak total Pb concentrations are in agreement with the peak in the accurately dated Indian Lake profile

(~1979). Unfortunately, the drawback of this approach is that it assumes a constant sedimentation rate between the time of peak total Pb concentrations and the present, which is not likely the case for these lakes. It also inhibits the calculation of element flux to a system.

The Newboro Lake profile depicts a single point peak in As, Cd, Pb and Zn at a 2-cm core depth (Figure 9). Although the analytical QA/QC was within range, the single data- point peak in the Newboro Lake core profile, which was not confirmed with a duplicate, was excluded from subsequent results and discussion (Figure 10 onward); however, it was not removed from the Hg analysis in Chapter 2 as the peak interval is different and the samples were analyzed using a different instrument. As such, the THg peak is still evident within the Newboro Lake core profile depicted in Figure 12.

Sediment sample groupings were coded using symbols and then spatially overlaid onto bathymetric maps using ArcGIS. Water samples were compared to the federal guideline for the Protection of Aquatic Life, though there are currently only guideline values for As and Cd and the guidelines for Canadian drinking water quality, where applicable (Table

1). Elements were grouped for analysis based on their characteristic associations. As such, Cd, Pb and Zn are typically addressed simultaneously, as are Cu and Ni, while As is presented independently. The remaining elements were grouped based on the similarity in core profile results. Chapter 3. Trace Element Trends within the Rideau River Waterway 55

Results

Cadmium, lead and zinc: Within Indian Lake, the profiles for Cd, Pb and Zn concentrations show slight increases beginning around 1850, and rapid increases beginning between approximately 1920 and 1930. The three element profiles also demonstrate common, identifiable peaks for Cd (4.4 µg g-1), Pb (375.0 µg g-1) and Zn

(418.0 µg g-1) concentrations, occurring around 1979 (Figures 9, 12). The three peak concentrations for Cd, Pb and Zn were all at concentrations above the federal PELs of

3.5, 91.3 and 315 µg g-1, respectively (Table 1). Although concentrations of Pb and Zn appear to have been below the federal ISQGs shortly after Canal construction, the profile for Cd depicts concentrations above the ISQG even before construction. Peak concentrations were 4.9, 17.2 and 4.1 times greater for Cd, Pb and Zn, respectively, than concentrations around 1836, early after Canal construction (ending around 1832). Since the peak, all three profiles demonstrated a decrease in concentration to a subsequent plateau, beginning roughly around the year 2000. In addition, since the peak (~1979), Cd and Zn concentrations have declined to concentrations above the ISQG but below PEL, while Pb concentrations remains above the PEL. The profiles for these three elements in

Indian Lake demonstrate statistically significant, strong correlations among one another

(Appendix B – Table 11).

As previously discussed (Chapter 2), the 210Pb-inferred sedimentation rate first peaked in

Indian Lake around 1957, followed by a decline until 1986 and a subsequent increase to present day (Figure 4). Similar to the THg profile (Chapter 2), the product of sedimentation rates and element concentrations suggests that peak concentrations for all Chapter 3. Trace Element Trends within the Rideau River Waterway 56 three elements in Indian Lake occurred when sedimentation rates were at their lowest since industrialization. Although the concentration of Cd, Pb and Zn per gram of sediment appears to have decreased since the peak, the continued rise in sedimentation rates within recent years may have caused the dilution of the concentration profile (Figure

11).

The profiles for Cd, Pb and Zn in both Newboro Lake and Upper Rideau Lake are quite variable over time, though there are discernable peak concentrations, occurring at similar times within both lakes based on the total Pb shifted profiles (Figure 12). Peak concentrations of Cd (3.4 and 2.6 µg g-1), Pb (280 and 212 µg g-1) and Zn (268 and 244

µg g-1) for Newboro Lake and Upper Rideau Lake, respectively, were up to 45% lower than peak concentrations in Indian Lake. In addition, concentration profiles of these three elements within these two lakes depicted little peak enrichment compared to early post-

Canal construction concentrations. From 1.1 to 1.6 for Newboro Lake (core depth of 18- cm) and 1.0 to 2.1 for Upper Rideau Lake (core depth of 29-cm). In comparison, peak enrichment ranged from 4.1 to 17.2 times above the background (compared to approximately 1836) for Indian Lake.

In Indian Lake, 85% and 54% of surface sediment samples exceeded the federal ISQG for

Cd and Zn, respectively, though none were found to exceed the PEL. Furthermore, 75% of surface samples exceeded the federal ISQG for Pb and 25% exceeded the PEL. As in the core profiles, the spatial distribution of these three elements were strongly correlated in surface sediments (Appendix B – Table 11). While no evident spatial trends were observed within Indian Lake for individual elements, the shallows leading towards Chapter 3. Trace Element Trends within the Rideau River Waterway 57

Mosquito Lake (IL-3), the deepest portion of the lake (IL-C2), and the lake outflow (IL-

5) consistently displayed the highest concentrations of Cd, Pb and Zn within the lake

(Figures 14, 15, 16). Similarly, the sampling locations from Newboro Lake and Upper

Rideau Lake that displayed the highest concentrations of Pb, were also found to have the highest concentrations of Cd and Zn (Figures 14, 15, 16).

None of the locations with the highest THg concentrations in Indian Lake (Chapter 2) were found to have the highest concentrations of Cd, Pb and/or Zn. Instead, locations such as IL-5 (Figure 3), which had the lowest THg concentration, had high concentrations of Cd, Pb and Zn. Newboro Lake and Upper Rideau Lake showed opposing trends. The locations having the highest THg concentrations, also had the highest Cd, Pb and Zn concentrations (NL-1, NL-2, NL-C7, URL-12, URL-13, URL-15 and URL-16) (Figures

14, 15, 16).

Arsenic: Within Indian Lake, the profile for As showed a slight increase in concentration beginning around the period of Canal construction (~1832) and a rapid increase beginning around 1890. The historical profile depicts a distinct peak occurring around

1938 (18.2 µg g-1), followed by a plateau and a sharp decline beginning around 1972

(Figures 9, 12). This As profile depicted a strong, linear correlation with the Indian Lake profiles for Cd (r = 0.92, p < 0.001), Pb (r = 0.79, p < 0.001) and Zn (r2 = 0.87, p <

0.001). The peak As concentration was 7.8 times greater than concentrations around 1840 and was above the federal PEL (17.0 µg g-1). Though concentrations have since declined, concentrations from recently deposited sediments remain around the federal ISQG (5.9

µg g-1). The only exceedance of the federal ISQG for As in Indian Lake was at site IL- Chapter 3. Trace Element Trends within the Rideau River Waterway 58

C2; however, sampling locations which were found to have high concentrations of other elements also approached the ISQG As value.

The As profiles for Newboro Lake and Upper Rideau Lake were variable, though they showed general decreases in concentrations since Canal construction (Figures 9, 12).

Although background concentrations (~1836) were below the federal ISQG within Indian

Lake (2.1 µg g-1), Newboro Lake and Upper Rideau Lake depict background concentrations between 8 and 9 µg g-1 (background being a core depth of 18 and 29-cm, respectively). Arsenic concentrations in Newboro Lake and Upper Rideau Lake demonstrated strong, linear relationships between As, Cd, Pb and Zn profile concentrations (r = 0.75 – 0.99, p < 0.01 and r = 0.82 – 0.97, p < 0.01, respectively), as they were for Indian Lake. Only one sampling location in Newboro Lake (NL-9; Figure

3) was found to have an As concentration above the federal ISQG, which was not one of the sampling locations with the highest surface concentrations of THg, Cd, Pb and/or Zn.

Within Upper Rideau Lake, there were three ISQG exceedances, all at locations with high concentrations of THg, Cd, Pb and Zn. Nonetheless, not all locations in Upper Rideau

Lake which had high THg, Cd, Pb and/or Zn concentrations also had high As concentrations (ex. URL-16) and vis versa (e.g. URL-18).

The other measured elements ( Co, Cr, Cu, K, Ni and Rb) all displayed highly variable trends (Figure 11). Cobalt and Rb concentrations profiles remained quite stable over time within each lake. The Indian Lake Cr and K profiles depict greater magnitudes of change over-time than the Co and Rb concentration profiles and though variable, the general profiles were similar between Newboro Lake and Upper Rideau Lake. Copper and Ni Chapter 3. Trace Element Trends within the Rideau River Waterway 59 displayed gradual increases to peak concentrations in Indian Lake around 1979. Both elements also displayed slight peaks in Newboro Lake around a 20-cm core depth.

Background concentrations were generally highest in Indian Lake, though Cu concentrations were found to be highest in Newboro Lake.

Of these elements, only Cu and Cr had federal ISQGs (37.3 and 35.7 µg g-1, respectively). Copper concentrations in the Indian Lake profile have exceeded the ISQG within Indian Lake since the early 1930’s and has consistently exceeded the guideline within Newboro Lake; however, there were no Cr exceedances measured within the three primary cores. Of the 14 surface sediment samples analyzed from Indian Lake, 21% exceeded the federal ISQG for Cu and none exceeded the PEL. Similarly, 25% of the surface samples collected from Newboro Lake and 22% of those collected from Upper

Rideau Lake exceeded the federal ISQG for Cu but none exceeded the PEL.

Spring runoff samples collected from the lake shores in early April are presented separately from late April samples collected offshore in Appendix B – Table 5.

Concentrations of Cd and Co in both surface and depth water samples from all lakes, were consistently below detection. Element concentrations within surface and depth water sample were very similar between sampling event, at low concentrations, never approaching any federal guideline values. No evident spatial or temporal trends were noted within or between lakes.

Chapter 3. Trace Element Trends within the Rideau River Waterway 60

Discussion

Following the discovery of widespread Pb contamination as a result of leaded gasoline use, a phase out and replacement by unleaded gasoline began in the 1970’s before being entirely banned in Canada by 1992 (Boutron, et al 1991; Mudroch 1993; Outridge 2000;

Gallon, et al 2006). Since that time, lake sediments have consistently demonstrated a decline in surface Pb concentrations (Table 6). In fact, the peak in leaded gasoline use near the end of the 1970’s is so distinctly preserved in lake sediments it can be used as an independent dating marker (Schottler and Engstrom 2006). Measured concentrations in precipitation have also been on the decline throughout North America (Eisenreich et al.

1986 in Mudroch 1993; Kaste, et al 2006). Conversely, the deposit of Cd and Zn particulate on roadways as a result of vehicle wear and tear has been thought to have increased within recent decades and is proposed to be one of the primary input sources to aquatic systems today (e.g. Mahler, et al 2006; Callender 2003; Callender and Rice 2000;

Hjortenkrans, et al 2006; Hjortenkrans, et al 2007)

The Indian Lake sediment profile indicates a sudden rise in Cd, Pb and Zn concentrations beginning around the 1920’s to peak concentrations around 1979, all above federal PELs

(Figures 9, 12). Peaks of a lower magnitude were also observed in the total Pb shifted profiles for the Newboro Lake and Upper Rideau Lake sediment cores. In shifting the Cd,

Pb and Zn profiles based on the timing of the Pb peak concentration in Indian Lake, the profiles observed between the three lakes become quite similar (Figure 12). Chapter 3. Trace Element Trends within the Rideau River Waterway 61

The maximum Indian Lake As concentration was observed around 1938 (Figure 12).

Although it could not be confirmed based on the available data, using the total Pb shifted sediment profiles, the Newboro Lake and Upper Rideau Lake cores may have displayed similar trends Unfortunately, the shifting of the peaks can cause a compression of the time scale and analyzed intervals then only date back to approximately 1941 and 1934 for

Newboro Lake and Upper Rideau Lake, respectively, subsequently inhibiting the identification of any distinct peaks around the same time period as Indian Lake (~ 1938)

(Figure 14).

Results for all lakes indicate little or no enrichment of Co, Cr, K or Rb since the construction of the canal (1832) or the modern industrial revolution beginning towards the end of the 18th century (Figure 11). While the individual profiles exhibit variability over time, the limited magnitude of change within the last century suggests that these elements have not been substantially influenced by anthropogenic inputs. A review of the literature suggests that, for the most part, these elements are not largely distributed atmospherically (Callender 2003; Kemp, et al 1978). As such, no further investigation into potential sources or influential factors was undertaken for these elements. Both Cu and Ni profiles in Indian Lake depict some level of enrichment, peaking around 1979; however, the trends are not as distinct as other elements and the magnitude of the enrichment does not compare to that of other atmospherically deposited elements. In addition, the variability in the Cu and Ni profiles collected from Newboro Lake and

Upper Rideau Lake make interpretation of any relevant trends especially difficult. For this reason, the general trends observed for these two elements in Indian Lake will be Chapter 3. Trace Element Trends within the Rideau River Waterway 62 further discussed in relation to Cd, Pb and Zn but not for Newboro Lake and Upper

Rideau Lake.

In order to appreciate the magnitude of the peak concentrations measured within the study lakes, it would be helpful to compare the results to other similar lakes. A literature review found few published core Cd, Pb and/or Zn profiles for Ontario inland lakes

(Table 6). Unfortunately, direct concentration comparisons can be deceiving as they can be influenced by a number of factors, which will be further discussed below; however, a comparison of the magnitude of enrichment (calculated as the ratio of the peak concentration or accumulation, over background) can be used. Although this approach assumes that there have been no substantial changes in either organic matter or particle size distributions, enrichment factors can generally be used to compare anthropogenic influences among different lakes. In comparing the magnitude of enrichment for specific elements, the importance of the measured concentrations became apparent, particularly for Indian Lake. For instance, the level of Pb enrichment measured in Indian Lake (17.2) was well above the magnitudes observed in all other Canadian lakes, including the Great

Lakes (Table 6). Considering the generally rural location of these lakes, the lack of geological deposits (Chapter 2) and the lack of surrounding industry, such an enrichment ratio was particularly surprising. However, Pb enrichment for Indian Lake is below the levels observed in some north-eastern American state inland lakes (Table 6); though the rationale for the particularly high enrichment ratios was not discussed in any of these studies. The magnitude of enrichment for both Cd and Zn were roughly four times higher in Indian Lake than in the other two connected lakes; however, such ratios were within the general range observed in other North American freshwater lakes (Table 6). Not Chapter 3. Trace Element Trends within the Rideau River Waterway 63 surprisingly, Cu and Ni enrichment ratios were lower than those measured within

Killarney Provincial Park, located in proximity to the Ni belt in the Sudbury region and the Cu deposits around the Bruce Peninsula (Kemp, et al 1978; Belzile, et al 2004).

Nonetheless, it should be noted that there is greater enrichment in Indian Lake compared to Newboro Lake and Upper Rideau Lake (Table 6). Overall, although the enrichment ratios for Cd, Cu, Ni and Zn within Indian Lake were comparable to other Ontario lakes, the enrichment of Pb was particularly high.

The majority of Ontario sediment core studies have depicted a general decreasing trend in trace element concentrations since roughly the 1970’s (Table 6). Indian Lake also exhibited a similar trend for Cd, Cu, Ni, Pb and Zn within the primary core, with all peak concentrations occurring around 1979 (Figure 13). The similarity in the timing of peak sediment Cd, Pb and Zn concentrations throughout Ontario strongly suggests a large- scale, atmospheric contribution. This hypothesis is further supported by the strong, linear association between core Cd, Cu, Ni, Pb and Zn concentrations (Appendix B – Table 11).

The statistical relationships between the Cd, Pb and Zn profiles (Appendix B – Table 11), and then Cu and Ni profiles (Appendix B – Table 11), in combination with the visual profile similarities (Figure 13) suggest that each grouping of elements has predominantly been contributed from the same source. The general similarities in Cd, Pb and Zn trends observed among-lakes, using the peak-shifted profiles (Figure 12), would also suggest a similar source to all three study lakes.

Various large-scale studies, particularly within the United States, have identified similar trends, with buried peak concentrations for Cd, Pb and Zn within lake sediments, which Chapter 3. Trace Element Trends within the Rideau River Waterway 64 have consistently been attributed to atmospheric contributions (e.g. Mahler, et al 2006;

Jeffries and Snyder 1981; Blais and Kalff 1993; Candelone, et al 1995; Chillrud, et al

1999). The similarities in sediment profiles across large geographic areas further supports this theory (Kemp, et al 1978); however, atmospheric contributions do not explain the variations in profiles observed among the interconnected study lakes. Instead, it was hypothesized that among lake variations were likely attributable to localized differences.

There are two primary categories of variables which were thought to explain the differences in concentrations observed within and among lakes. Firstly, differences in sediment, lake and watershed characteristics and secondly, anthropogenic influences within the watershed, including: land-use, vehicular traffic, building materials and recreational activities.

Lake and watershed specific characteristics such as: sedimentation rates, percentage organic matter, focusing factors, catchment area to lake area ratios, particle size distributions, and water depth at sampling locations (e.g. Davis, et al 2006; Hatfield, et al

2008; Forsythe and Marvin 2009; Van Metre and Fuller 2009), have previously aided researchers in explaining observed variations among-lake profiles. Unfortunately, sedimentation rates could not be compared between the study lakes. Given the rural location of all the lakes and their proximity to one another, this factor alone was not thought to be the most influential, particularly given the comparison of enrichment, rather than concentration. Nonetheless, it was hypothesized that sedimentation in combination with other variables may be influencing the measured results. Although relatively stable in profile (Figure 4), the percentage organic matter measured since Canal construction was found to be statistically different among lakes (p < 0.05). Since some elements, for Chapter 3. Trace Element Trends within the Rideau River Waterway 65 example As, generally have a higher affinity for organic matter (Yu, et al 2001; Bilali, et al 2002), the Newboro Lake core, with the highest concentration of organic matter, would have been thought to have the highest measured concentration, assuming similar input sources. Since the Indian Lake core consistently had the highest measured As concentrations, yet an average percentage organic matter lower than Newboro Lake, this factor did not appear to explain the observed among-lake differences for As. A sediment focusing factor refers to the resuspension and movement of fine particulate to the deepest portions of a lake and is predominantly influenced by lake morphology. Assuming that atmospheric contributions are the predominant input source of elements, increased focusing at a coring location could dilute the measured element concentrations (Van

Metre and Fuller 2009). Alternatively, assuming predominant, particulate bound watershed contributions, focusing could increase measured concentrations at a coring site

(Van Metre and Fuller 2009). Given the steep slopes and precipitous drop along the northern shore of Upper Rideau Lake near the coring site (Figures 2, 3), an increased focusing factor was not surprising and may have contributed to slumping. The comparatively higher focusing factor in Upper Rideau Lake, coupled with the consistently lower measured element concentrations could suggest a dilution of predominantly atmospheric inputs. Conversely, Indian Lake, with the medial focusing factor but highest measured concentrations would suggest that this factor is also not the primary difference among lakes.

As previously discussed in Chapter 2, Indian Lake has a considerably larger catchment area to lake area ratio (CA: LA) compared to the other two lakes. While other studies

(e.g. Evans 1986; Engstrom, et al 2007) have found correlations between enrichment Chapter 3. Trace Element Trends within the Rideau River Waterway 66 ratios and CA: LA ratios, an insufficient number of cores were dated and analyzed in this study. Nonetheless, the Indian Lake CA: LA ratio is 1.9 and 3.2 times greater than the ratio for Newboro Lake and Upper Rideau Lake, respectively. If this was the dominant variable among lakes, the peak concentration ratios for Cd, Pb and Zn should then be comparable to the CA: LA ratios. Interestingly, the peak concentration ratios between

Indian Lake and Newboro Lake appear reflective of the CA: LA ratio (ranging from 1.3 to 1.5); however, the ratios between Indian Lake and Upper Rideau Lake only range between 1.7 and 1.8 (though a ratio of 3 would be expected). Since a CA:LA variable assumes predominantly watershed-based inputs, a 2.7-fold higher focusing factor in

Upper Rideau Lake, coupled with a 3.2 fold lower CA:LA ratio should make the concentrations in Upper Rideau Lake comparable to those in Indian Lake, which was not the case. Based on the current results, the variations in element magnitude and enrichment among-lake profiles could not be explained by only considering sedimentation rates, organic matter, or focusing factors. Although each factor may be contributing to the variations observed, the amount of similarities are too small to explain the differences measured between Indian Lake and the other two study lakes. Intuitively, the CA: LA ratio appears to be the most likely influential variable, since the magnitude of the difference between the three lakes is substantial; however, further analysis of additional lakes is required.

With regards to spatial variation within lakes, particle size distribution and water depth at sampling location were further considered. While there was insufficient sample mass remaining from the core samples and an insufficient number of grab samples collected from Newboro Lake, the percent composition by particle size was measured for 10 Indian Chapter 3. Trace Element Trends within the Rideau River Waterway 67

Lake and 13 Upper Rideau Lake grab samples. Superficially, there appears to be a greater percentage of pebble-sized samples collected from Indian Lake; however, this weight is primarily attributed to zebra mussel (Dreissena polymorpha) shells, which were removed as best possible from all samples prior to grinding and chemical analysis. The majority of samples collected from Indian Lake and Upper Rideau Lake consisted of medium (300

µm) to fine-grained (150 µm) sand (Table 5). Within Upper Rideau Lake, As, Cd, Pb and Zn were statistically correlated (p < 0.05) with sediment sample depth but not with particle size and all surface elements were statistically correlated to one another

(Appendix B – Table 12). In comparison, within Indian Lake, only As was found to be strongly associated (p < 0.05) with sample depth and Cu was only strongly correlated with Ni. Although particle size was not associated with depth, there were strong associations between each size fraction within Indian Lake (Appendix B – Table 12).

These results suggest that particle size is not a differentiating factor in relation to element concentrations between Indian Lake and Upper Rideau Lake.

Water depth at sampling locations was determined to be associated with elemental distributions in Upper Rideau Lake but not in Indian Lake. The relationship between depth and element concentrations in the literature has generally been associated with either particle size (which was not corroborated in this study) and/or anoxic conditions

(e.g. Forsythe and Marvin 2009; Powell, et al 2000). Other than the primary core, only

11% of samples from Indian Lake were collected at depths of less than 5 metres, compared to 41% of samples from Upper Rideau Lake. By removing the samples collected at depths greater than 5-m from Upper Rideau Lake, the association between element concentrations and depth was lost (Appendix B – Table 12). These results Chapter 3. Trace Element Trends within the Rideau River Waterway 68 suggest that element concentrations were strongly associated with depths greater than 5- m within Upper Rideau Lake but not within Indian Lake (Appendix B – Table 12). Based on these results, neither particle size, nor water depth at sampling location appear to explain the variation in the measured element concentrations from Indian Lake, though depth explains at least a portion of the variation observed in Upper Rideau Lake

(Appendix B – Table 12). Overall, none of the watershed or lake specific characteristics discretely explain the variation observed within-or among-lake sediment concentrations.

Other attempts to narrow the scope of likely contaminant contributors to lake systems have led to the consideration of anthropogenic influences, such as: distance from industry, urbanization, as well as hunting and fishing activities (e.g. Kemp et al. 1978;

Callendar 2003; Hardison, et al 2004). Such studies, conducted over large, geographic areas, typically identify decreasing concentration gradients associated with decreasing distance from source (Kemp, et al 1978). A review of historical industries located within the Rideau Lakes area was undertaken in 2009 in hopes of identifying metal contributing industries. Although a number of historical saw, grist, and woollen mills were identified in the area (Lai 2009), the approximate dates of opening and closings, based on historical records, do not match the fluxes of elements recorded in the dated Indian Lake core sediments (Figure 13). As previously discussed, though the lakes have likely received industrial inputs via atmospheric deposition, their proximity to one another, in combination with the lack of proximal industries, eliminates the distance-from-source hypothesis. Chapter 3. Trace Element Trends within the Rideau River Waterway 69

Evidence of the significance and quantification of land-use as influential factors to aquatic contaminant burdens appears to be increasing in the literature. Agricultural practices have been examined as possible sources of elements to surrounding environments. Both As and Hg were historically used in the production of a variety of fungicides, insecticides and herbicides until approximately the 1970’s (ATSDR 2007a).

As such, agricultural lands have been thought to be a potential source of contaminants. In a recent study of a rural Mississippi fluvial floodplain, surrounded by agricultural lands historically treated with As, Cooper and Gillespie (2001) found mean surface sediment

As concentrations to be 5.6 µg g-1 (n = 31) comparable to recent concentrations measured in the Indian Lake core (5.9 µg g-1). Although no records of As use on agricultural fields surrounding Indian Lake were found, the sediment core profile depicts a sudden increase in concentrations beginning near the turn of the 20th century, and a drop in concentrations since the 1970’s (Figure 9, 12). The peak As concentration (~ 1940), occurred roughly 10 years after the general transition of cultivated lands to dairy farming in the area (Figure

13). Examination of air photos demonstrates that Upper Rideau Lake currently has the greatest proportion of surrounding agricultural land, predominantly near the south-west portion of the lake, although Newboro Lake is also surrounded by agricultural fields, though to a lesser extent. Using the total Pb shifted peak profiles, the trends in Newboro

Lake and Upper Rideau Lake are quite similar and though more variable, are generally in agreement with the Indian Lake profile (Figure 12). If a portion of any agriculturally- applied As was lost to the aerial environment, the around 1940’s peak could represent a lag in the watershed contributions of localized activities. Again, while the intervals between the concentration trends do not match the CA:LA ratios, the larger catchment, Chapter 3. Trace Element Trends within the Rideau River Waterway 70 draining into the smaller lake area may be responsible for the increased As concentrations observed in Indian Lake, suggesting a potentially important avenue of research.

Due to the historical use of Pb in gasoline and the current use of Cd, Cu and Zn in automotive parts, increased road development, increased vehicular traffic, and population densities have also been studied as potential contaminant sources. Each of the study lakes is almost entirely circled by unpaved country roads, and there are paved highways in proximity to both Newboro Lake and Upper Rideau Lake. The evident rise in Cd, Pb,

Zn, and to a lesser degree Cu, in the Indian Lake profile beginning around the 1920’s corresponds to the first arrival of vehicles in the area. Historical records indicate that the first vehicle arrived in the area around 1907, the first gasoline pump was opened around

1910, and the first two auto dealerships were established around Upper Rideau Lake in

1916 (Appendix A; Lai 2009). This period also coincides with the beginning of motorized pleasure craft use in Ontario (Halseth 1998), which likely contributed to exhaust-related inputs. Although concentrations of Pb have generally decreased in response to the banning of leaded gasoline, concentrations of Cu, Cd and Zn in urban runoff have been shown to increase in relation to increased vehicle use in recent decades

(Callender 2003; Olli and Destouni 2008). Upper Rideau Lake has the greatest total length of roads surrounding its shores. Although Indian Lake is entirely surrounded by roads, due to its limited size, there are fewer meters of road around it compared to Upper

Rideau Lake. In comparison, there remain a number of undeveloped shorelines around

Newboro Lake due to a lack of current road access; however, the lake is bordered by highways near two shores. The period of increased vehicle traffic to the area also corresponds to the increase in seasonal cottage development along the shores of the three Chapter 3. Trace Element Trends within the Rideau River Waterway 71 lakes (Halseth 1998). It is assumed that the majority of cottages developed prior to the

1950’s were constructed of wood, with shingled roofs. Exterior paints and shingles weather and release a variety of elements (Davis, et al 2001) which may have contributed to the concentrations observed within the lakes. Cottage development typically includes the construction of docks and decks, often built of impregnated/pressure-treated wood, which leaches As, Cu, Cd, Pb and Zn (Hingston, et al 2001). Though not quantitatively measured, it appears logical, based on the proximity of roads to the lakes, the increased number of shoreline developments, as well as the agreement between element profiles and the introduction of motorized boats, vehicles and cottages, that at least a portion of the inputs have likely been contributed by such sources. Unfortunately, development- based inputs alone do not help explain the variation in profile concentrations among lakes. Given that Indian Lake has the smallest surface water area of the studied lakes, it is possible that contributions from land-use related sources are amplified in Indian Lake and diluted in Newboro Lake and Upper Rideau Lake. Although only qualitatively assessed, intuitively, these factors appear to have the potential to help explain the variability in magnitudes of enrichment observed among lakes.

Lastly, it has become evident in recent years that hunting and fishing with Pb-based shot and tackle can negatively affect aquatic organisms, although they represent less than 1% of the global Pb production (Scheuhammer and Norris 1996). Spent ammunition and lost tackle can remain intact in aquatic systems for decades (Storgaard Jorgensen and Willems

1987; Lin, et al 1995; Rattner, et al 2008) however, the weathering and subsequent release of Pb can be greatly influenced by acidity, water depth, sediment burial rates, grain size and aerobic conditions (Scheuhammer and Norris 1996). A study of trap and Chapter 3. Trace Element Trends within the Rideau River Waterway 72 skeet ranges over water bodies in the United States found shot densities to be up to 3.7 x

109 hectare-1 within the top 7.5 cm of sediment (Stansley, et al 1992). At such densities, average water Pb concentrations were two orders of magnitude higher than those measured in the Rideau lakes. The average sediment concentrations in the trap and skeet water bodies were an order of magnitude lower than background concentrations measured in Upper Rideau Lake (Stansley, et al 1992), suggesting that such activities are not likely the cause for the high Pb concentrations observed. Mean Pb soil concentrations of up to

54 000 µg g-1 have been reported for land-based shooting ranges (Chen and Daroub 2002;

Chen and Daroub 2002; Manninen and Tanskanen 1993). Locally, all three study lakes are used for recreational waterfowl hunting and fishing, though only Newboro Lake and

Upper Rideau Lake are presently commercially fished. Given the slow decay rate of Pb artefacts in aquatic ecosystems, coupled with the lack of observed artefacts in any of the sediment samples and the limited frequency of recreational hunting compared to range sites, such contributions were considered to be minimal.

In summary, peak concentrations in the late 20th century were all above the federal PELs for Cd, Pb and Zn within the Indian Lake sediment core. Peak concentrations were 4.9,

17.2 and 4.1 times greater for Cd, Pb and Zn, respectively, than concentrations around

1836, early after Canal construction. The ratios of peak to background concentrations for

Cd and Zn were within the range observed for other Canadian lakes; however, the magnitude of enrichment for Pb was especially high. Since the peak, all three concentration profiles have decreased; however, Cd and Zn concentrations presently remain above the ISQG, while the concentration of Pb remains above the PEL. In comparison, peak concentrations of Cd (3.4 and 2.6 µg g-1), Pb (280 and 212 µg g-1) and Chapter 3. Trace Element Trends within the Rideau River Waterway 73

Zn (268 and 244 µg g-1) for Newboro Lake and Upper Rideau Lake, respectively, were up to 45% lower than peak concentrations in Indian Lake. In addition, concentration profiles of these three elements within these two lakes depicted little peak enrichment compared to pre-industrial concentrations. Importantly, though the concentration of these three elements per gram of sediment has decreased in recent years, the simultaneous rise in sedimentation rates within Indian Lake suggests that the concentration profiles are being diluted and may not have decreased as substantially as they appear within Indian

Lake.

The similarity in the timing of peak sediment Cd, Pb and Zn concentrations throughout

Ontario strongly suggests a large-scale, atmospheric contribution. Although the lakes are located within close proximity to one another and are interconnected, they are divided by watershed boundaries. The similarities in profiles between the three study lakes further support the speculation that the contaminants are primarily atmospherically deposited.

Spatially, although sediments from Indian Lake depicted an inverse relationship between

THg, Cd, Pb and Zn concentrations, these four elements were strongly associated within surface sediments from both Upper Rideau Lake and Newboro Lake.

Sediment, lake and watershed characteristics, as well as land-uses within the watershed, were considered as possible influences, affecting the among-lake variations observed.

Although no individual causal factors were identified, it was hypothesized that a combination of influences such as the CA:LA ratios and surrounding land-uses may help explain the magnitude of element enrichment in Indian Lake compared to Newboro Lake and Upper Rideau Lake. Overall, the continued exceedances of federal sediment Chapter 3. Trace Element Trends within the Rideau River Waterway 74 guidelines, especially within Indian Lake are a cause for concern. Although none of the exceeding elements are proven to biomagnify, As, Cd, Pb and Zn are known to bioaccumulate and/or bioconcentration, which could have implications for human health.

None of the watershed-based variables considered indirectly, explain the dissimilarities observed. Although the CA: LA ratio appears to be the variable which best explains the differences observed; however, additional study and quantification are required. With respect to surrounding land-uses, the timing of the introduction of motorized vehicles, boats and initial cottage development in the area overlaps with the period of increased in the sediment element profiles. This time period also coincides with the national rise in vehicle ownership and the boom in industrial processes. Overall, none of the studied variables were found to adequately explain the differences observed, though the list of potential contributors was substantially narrowed. Additional research and quantification of such factors should be undertaken in the future.

Chapter 3. Spatial and Temporal Distributions of Trace Elements 75

Table 5 Comparison of potential influential factors among lakes Newboro Lake Upper Rideau Lake Indian Lake (IL) Potential Factors (NL) (URL) 2005-2006 Sedimentation Rate 390 400 414 (g m-2 yr-1)

Average Sedimentation Rate since the 1970’s 340 + 4 401 + 14 388 + 2 a (g m-2 yr-1)

Percentage of Samples Predominantly Pebble 20% NA 8% (> 4 mm)

Percentage of Samples Predominantly Gravel 0% NA 0% (2 to 2.8 mm)

Percentage of Samples Predominantly Sand 80% NA 92% (63 µm to 1 mm)

Percentage of Samples Predominantly Silt/Clay 0% NA 0% (< 38 µm)

Average Loss-on- ignition (%) Since Canal 43 52 39 Construction

Focusing Factor b 2.66 7.25 1.82

Approximate Depth of Lake at Core Location 18 23 24 (m)

NA – Represents samples with insufficient weight for analysis a – Represents average sedimentation rate since the 1980’s due to dating profile b – Calculated as the ratio of 210Pb burden in the core to the mean atmospheric fallout rate for the Dorset area lakes (1.6 dpm cm-2 year-1) based on the findings of Evans, R.D. 1986. Sources of mercury contamination in the sediments of small headwater lakes in south-central Ontario, Canada. Arch. Environ. Contam. Toxicol. 15(5): 505-512.

Chapter 3. Spatial and Temporal Distributions of Trace Elements 76

Table 6 Literature compilation of trace element enrichment in sediments Enrichment was calculated as the ratio between the measured peak concentration and the measured background concentration. Where possible, values reported by the original authors were used. Alternatively, they were calculated based on the profiles or concentrations presented. An asterix (*) denotes the results which were calculated based on approximations of core profile data. The timing or depths of background represent those established by the author. If no specific background period was described, the bottom of the core profile was used. Lake n Cd Pb Zn Cu Ni Background Year Study Primary Study Lakes

Indian Lake, ON 1 4.9 17.2 4.1 1.4 1.2 1836 This study Newboro Lake, ON 1 1.2 1.6 1.1 1.1 1.1 1832 This study Upper Rideau Lake, ON 1 1.0 2.1 1.4 1.0 0.9 1836 This study

Other Inland Ontario Lakes Acid Lake, ON * 1 5.0 5.0 4.0 2.4 4.9 1905 Belzile et al. 2004 Bell Lake, ON * 1 1.3 6.4 1.4 3.0 3.0 1880 Belzile et al. 2004 Blue Chalk Lake, ON 5 3.0 -- 2.2 -- -- (Depth of 17-20 cm) Evans et al. 1983 Chub Lake, ON 5 3.9 -- 2.6 -- -- (Depth of 17-20 cm) Evans et al. 1983 Clear Lake, ON 4 3.6 -- 2.8 -- -- (Depth of 17-20 cm) Evans et al. 1983 Crosson Lake, ON 4 3.0 -- 1.9 -- -- (Depth of 17-20 cm) Evans et al. 1983 Dickie Lake, ON 8 3.5 -- 2.7 -- -- (Depth of 17-20 cm) Evans et al. 1983 George Lake, ON * 1 4.0 5.5 3.7 2.9 1.8 1888 Belzile et al. 2004 Harp Lake, ON 3 3.0 -- 2.0 -- -- (Depth of 17-20 cm) Evans et al. 1983 Helen Lake, ON * 1 5.0 11.7 2.4 3.1 3.5 1888 Belzile et al. 2004 Heney Lake, ON 5 3.2 -- 2.2 -- -- (Depth of 17-20 cm) Evans et al. 1983 Jerry Lake, ON 5 3.3 -- 2.3 -- -- (Depth of 17-20 cm) Evans et al. 1983 Opeongo Lake, ON * 1 1.0 13.0 1.1 2.0 2.0 (Depth of 39 cm) Nriagu and Wong 1986 Plastic Lake, ON 5 3.5 -- 2.5 -- -- (Depth of 17-20 cm) Evans et al. 1983 Red Chalk Lake, ON 8 2.9 -- 1.9 -- -- (Depth of 17-20 cm) Evans et al. 1983

North American Great Lakes Lake Superior 6 2.9 4.6 0.9 1.9 0.0 1890 Kemp et al. 1978 Lake Superior * 3 ------3.3 -- 1800 Kolak et al. 1998 Lake Huron 6 3.1 5.7 1.7 0.8 1.0 1870 Kemp et al. 1978 Georgian Bay 3 3.2 5.8 1.5 0.8 1.4 Unknown Kemp et al. 1978 Lake Ontario 5 6.2 9.0 4.9 1.9 1.0 Unknown Kemp and Thomas 1976b in Kemp et al. 1978

Chapter 3. Spatial and Temporal Distributions of Trace Elements 77

Table 6 Continued Lake n Cd Pb Zn Cu Ni Background Year Study Lake Ontario * 2 ------2.4 -- 1880 Kolak et al. 1998 Lake Erie * 1 -- 3.3 ------1798 Graney et al. 1995 Lake Michigan * 3 ------1.9 -- 1800 Kolak et al. 1998

Other Canadian Lakes Lake 817, NL * 1 -- 6.0 6.0 15.0 1.6 1800 Rybak et al. 1989 Moose Lake, BC 1 -- 1.2 1.5 1.4 3.2 Pre-1900 Gallagher et al. 2004 Stuart Lake, BC 1 -- 1.4 1.2 1.4 1.3 Pre-1900 Gallagher et al. 2004 Chilko Lake, BC 1 -- 1.5 1.1 1.1 1.6 Pre-1900 Gallagher et al. 2004 Kamloops Lake, BC 1 -- 1.4 1.2 1.1 1.2 Pre-1900 Gallagher et al. 2004 Nicola Lake, BC 1 -- 1.3 1.2 1.2 1.2 Pre-1900 Gallagher et al. 2004 Harrison Lake, BC 1 -- 1.6 1.2 1.2 1.4 Pre-1900 Gallagher et al. 2004 Great Slave Lake, NT * 6 -- 4.3 -- 1.0 1.6 (Depth of 27 cm) Allan 1979

American Inland Lakes Westchester Lagoon, AK* 1 -- 20.0 -- -- 1972 Callender 2003

Sloans Lake, CO * 1 -- 1.5 ------1970 Callender 2003 Black Pond, CT 1 -- 7.6 ------1905 Siver and Wozniak 2001 Coverntry Lake, CT 1 -- 9.5 ------1934 Siver and Wozniak 2001 Crystal Lake, CT 1 -- 9.4 ------1925 Siver and Wozniak 2001 Mashapaug Lake, CT 1 -- 4.7 ------1940 Siver and Wozniak 2001 Mohawk Pond, CT 1 -- 7.3 ------1924 Siver and Wozniak 2001 Norwich Pont, CT 4 -- 15.5 ------1927 Siver and Wozniak 2001 Uncas Pond, CT 4 -- 11.7 ------1952 Siver and Wozniak 2001 Sand Lake, FL * 1 -- 1.7 ------1980 Callender 2003 Berkeley Lake, GA * 1 -- 3.1 4.0 -- -- 1974 (Pb) / 1995 (Zn) Callender 2003 Lakewood Park Lake, GA * 1 -- 1.2 ------1970 Callender 2003 Mystic Lake, MA * 1 -- 2.7 ------1965 Callender 2003 Fishing Creek Reservoir, MD 1 -- 2.0 ------1965 Callender 2003 * Crystal Lake, MI * 1 5.5 23.8 3.5 2.2 -- 1800 Yong et al. 2001 Elk Lake, MI * 1 70.0 60.0 8.0 2.5 -- 1800 Yong et al. 2001

* Enrichment calculated based on approximations of core profile data Chapter 3. Spatial and Temporal Distributions of Trace Elements 78

Table 6 Continued Lake n Cd Pb Zn Cu Ni Background Year Study American Inland Lakes

Gratiot Lake, MI * 1 2.2 23.3 2.1 1.1 -- 1820 Yong et al. 2001 Gull Lake, MI * 1 90.0 72.5 16.0 14.0 -- 1800 Yong et al. 2001 Higgins Lake, MI * 1 5.6 16.3 3.7 2.1 -- 1800 Yong et al. 2001 Littlefield Lake, MI * 1 9.7 59.8 1.1 2.7 -- 1800 Yong et al. 2001 Palmer Lake West, MN * 1 -- 1.5 1.7 -- -- 1980 (Pb) / 1995 (Zn) Callender 2003 Clyde Potts Reservoir, NJ * 1 -- 2.0 ------1975 Callender 2003 Orange Reservoir, NJ * 1 -- 2.8 2.1 -- -- 1975 (Pb) / 1995 (Zn) Callender 2003 Beaver Lake, NH * 1 -- 6.0 5.0 3.0 -- 1882 Davis et al. 2006 Hatch Pond, NH * 1 -- 42.0 7.8 4.4 -- 1830 Davis et al. 2006 Lake of the Clouds, NH 1 > 4.2 4.3 2.7 1.4 -- (Depth of 10-15 cm) Galloway and Likens 1979 Central Park Lake, NY 1 -- 57.0 13.0 -- -- 1870 Chillrud et al. 1999 Honnedaga Lake, NY 1 15 150.0 4.4 20.0 -- (Depth of 32 cm) Galloway and Likens 1979 Woodhull Lake, NY 1 5 10.0 2.6 4.3 -- (Depth of 22 cm) Galloway and Likens 1979 Harris Pond, RI * 1 -- 2.0 ------1970 Callender 2003 Lake Houston West, TX * 1 -- 1.1 ------1975 Callender 2003 Lorance Creek Lake, TX * 1 -- 3.8 3.0 -- -- 1978 (Pb) / 1980 (Zn) Callender 2003 White Rock Lake, TX * 1 -- 8.0 1.7 4.5 1.3 (Variable) Van Metre and Callender 1997 Red Butte Reservoir, UT * 1 -- 1.8 ------1975 Callender 2003 Alake Anne, VA * 1 -- 5.0 ------1972 Callender 2003 Lake Ballinger, WA * 1 -- 5.2 4.1 -- -- 1975 (Pb) / 1995 (Zn) Callender 2003 Lake Washington, WA * 1 -- 2.8 ------1980 Callender 2003 Butternut Lake, WI 1 1.6 2.7 3.4 4.7 1.2 (Depth 25 - 50 cm) Iksandar and Keeney 1974 Crystal Lake, WI * 1 2.1 ------(Depth of 100 cm) Powell et al. 2000 Kegonsa Lake, WI 1 1.9 1.4 1.4 8.2 1.4 (Depth > 50 cm) Iksandar and Keeney 1974 Mary Lake, WI 1 12.0 > 30 1.1 1.3 1.0 (Depth > 50 cm) Iksandar and Keeney 1974 Mendota Lake, WI 1 1.6 5.7 6.7 2.8 1.3 (Depth > 50 cm) Iksandar and Keeney 1974 Minocqua Lake, WI 1 3.3 > 320 2.8 1.1 2.2 (Depth > 50 cm) Iksandar and Keeney 1974 Monona Lake, WI 1 2.2 11.9 6.7 23.2 1.8 (Depth > 50 cm) Iksandar and Keeney 1974 Phillips Lake, WI 1 1.3 5.5 1.0 2.0 1.1 (Depth > 50 cm) Iksandar and Keeney 1974 Tomahawk Lake, MS 1 1.3 2.0 1.2 1.2 1.2 (Depth > 50 cm) Iksandar and Keeney 1974 * Enrichment calculated based on approximations of core profile data Chapter 3. Spatial and Temporal Distributions of Trace Elements 79

Table 6 Continued Lake n Cd Pb Zn Cu Ni Background Year Study Vandercook Lake, WI * 1 3.1 ------(Depth of 100 cm) Powell et al. 2000 Waubesa Lake, WI 1 4.0 2.4 2.7 4.9 1.2 (Depth > 50 cm) Iksandar and Keeney 1974 Winga Lake, WI 1 1.1 2.6 5.5 2.6 1.3 (Depth > 50 cm) Iksandar and Keeney 1974 Various Lakes, Various States 35 5.6 5.5 95.0 3.6 1.5 Variable Mahler et al. 2006

Swedish Inland Lakes Lake Grånästjärn, Sweden 1 3.7 3.8 ------1800 Renberg 1986 Lake Högforstjärn, Sweden 1 2.3 ------1800 Renberg 1986 Lake Kassjön, Sweden 1 4.3 1.8 ------1750 Renberg 1986 Lake Koltjärn, Sweden 1 -- 2.9 ------1750 Renberg 1986 Lake Kroksjön, Sweden 1 8.7 12.7 ------1800 Renberg 1986 Lake Marsbosjön, Sweden 1 -- 2.1 ------1750 Renberg 1986 Lake Sarsjön, Sweden 1 10.0 7.2 ------1750 Renberg 1986 Lake Stensjön, Sweden * 2 4.3 32.0 2.5 4.3 -- 1800 Karlsson et al. 2006 Lake Verkasjön, Sweden * 4 10.0 30.0 20.0 -- -- (Depth of 20 cm) Backtröm et al. 2006 Various, Finland 18 5.1 32.8 6.2 8.7 -- 1800 Verta et al. 1989 Various Stockholm, Sweden 118 16.5 15.0 7.4 12.8 -- 1970 (Cd) / 1975 (Cu & Pb) Sternbeck and Ostlund 2001

Other Global Lakes Taihu Lake, China * 1 -- 1.5 1.3 1.0 1.0 1920 Lui et al. 2006 Lake Dudinghauser, 1 -- 5.5 5.5 3.3 -- 1650 Selig et al. 2007 Germany* Laugh Neagh, Ireland 1 1.7 7.0 3.8 4.7 2.1 Unknown Rippey et al. 1982 Respomuso, Spain 1 70.8 3.0 2.3 5.4 1.6 (Depth of 60 cm) Lavilla et al. 2006 Lake Cadagno, Swiss Alps 1 7.75 27.5 5.1 -- -- (Depth of 25 cm) Birch et al. 1996 * Enrichment calculated based on approximations of core profile data Chapter 3. Spatial and Temporal Distributions of Trace Elements 80

-1 As concentration (µg g-1) Hg concentration (µg g ) 0 5 10 15 20 0.0 0.2 0.4 0.6 0 2000

1950 10

Pb Date (years) 1900 20 210 Core Depth (cm) 1850 30 Inferred

-1 -1 Cd concentration (µg g-1) Pb concentration (µg g ) Zn concentration (µg g ) 0 1 2 3 4 5 0 100 200 300 400 0 100 200 300 400 500 0 2000

1950 10

Pb Date (years) 1900 20 Core Depth (cm) 210

1850 30 Inferred

Indian Lake profile based on 210Pb inferred dates (years) Upper Rideau Lake profile based on core depth (cm) Federal interim sediment quality guideline (ISQ Newboro Lake profile based on core depth (cm) Federal probable effect level (PEL)

Figure 9 Sediment concentration profiles for arsenic (As), cadmium (Cd), mercury (Hg), lead (Pb) and zinc (Zn) Federal guidelines refer to those set by the Canadian Council of Ministers of the Environment (2009) Chapter 3. Spatial and Temporal Distributions of Trace Elements 81

-1 Co concentration (µg g ) Cr concentration (µg g-1) Cu concentration (µg g-1) 0 2 4 6 8 10 12 14 16 0 5 10 15 20 25 30 35 40 0 10 20 30 40 50 0 2000

1950 10

Pb Date (years) DatePb 1900 20 210 Core DepthCore (cm) 1850 30 Inferred

-1 -1 K concentration (µg g ) Ni concentration (µg g ) Rb concentration (µg g-1) 1000 1500 2000 2500 10 15 20 25 30 0 5 10 15 20 25 30 0 2000

10 1950

Pb Date (years) 1900 20 210 Core Depth (cm)Core Depth 1850 30 Inferred

Indian Lake profile based on 210Pb inferred dates (years) Upper Rideau Lake profile based on core depth (cm) Federal interim sediment quality guideline (ISQG) Newboro Lake profile based on core depth (cm)

Figure 10 Sediment concentration profiles for cobalt (Co), chromium (Cr), copper (Cu), potassium (K), nickel (Ni) and rubidium (Rb) Federal guidelines refer to those set by the Canadian Council of Ministers of the Environment (2009) Chapter 3. Spatial and Temporal Distributions of Trace Elements 82

Cd Flux Pb Flux Zn Flux (µg cm-2 yr-1) (µg cm-2 yr-1) (µg cm-2 yr-1)

0.00 0.05 0.10 0.15 0.20 0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14 16

2000

1980

1960

1940

1920 Pb Date (years)

210 1900

1880 Inferred

1860

1840

Indian Lake flux profiles based on 210Pb dates (years)

Figure 11 Sediment cadmium (Cd), lead (Pb) and zinc (Zn) flux profiles for Indian Lake (IL) Flux was calculated as the trace element concentration for a specific interval multiplied by the sedimentation rate for that interval. Chapter 3. Spatial and Temporal Distributions of Trace Elements 83

As concentration (µg g-1) Cd concentration (µg g-1) Cu concentration (µg g-1) 0 5 10 15 20 0 1 2 3 4 5 25 30 35 40 45 50 55 2000 2000

1950 1950 Pb Date (years) 1900 1900 210 Peak Peak (years)

1850 1850 Inferred Shifted Profile Dates Based on theIndian Lake Total Lead on

-1 -1 Ni concentration (µg g ) Pb concentration (µg g ) Zn concentration (µg g-1) 10 15 20 25 30 0 100 200 300 400 0 100 200 300 400 500 2000 2000

1950 1950 Pb Date (years) Pb Date

1900 1900 Peak (years) 210 Shifted Profile Dates Based

1850 1850 theIndian Lake Total Lead on Inferred

Indian Lake profile based on 210Pb inferred dates (years) Upper Rideau Lake shifted profile based on the timing of the Interim sediment quality guideline (ISQG) peak Indian Lake total Pb concentration (years) Probable effect level (PEL) Newboro Lake shifted profile based on the timing of the peak Indian Lake total Pb concentration (years)

Figure 12 Shifted sediment concentration profiles for arsenic (As), cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni) and zinc (Zn) Concentration profiles for Newboro Lake and Upper Rideau Lake were shifted to match the peak lead concentration from the Indian Lake profile. Although helpful in identifying trends, shifting causes the compression of timescales and should be interpreted with caution. Chapter 3. Spatial and Temporal Distributions of Trace Elements 84

Cd concentration(µg g-1) Cu concentration(µg g-1)

0 1 2 3 4 5 0 10 20 30 40 50

2000 2000 Ban of leaded gasoline in fuel

End of commercial traffic on the canal 1950 End of mineral product traffic on the canal 1950 Pb Date(years) Pb Pb Date (years) Dairy farming replacing agriculture 210 210 1900 First cars arrive in the area Fishing-based tourism began 1900 Locks repaired

Inferred Inferred Outboard powered boats start being used Inferred Iron, phosphate and mica mining replaces lumber industry 1850 New grist mill built/ Most prime lumber 1850 in the area already cut

0 100 200 300 400 500 0 5 10 15 20 25 30 Cadmium (Cd) Lead (Pb) Copper (Cu) -1 Pb and Zn concentrations Nickel (Ni) Ni concentration(µg g ) (µg g-1) Zinc (Zn)

Figure 13 Comparison of trace element profiles and historical disturbances around Indian Lake (IL) Cadmium (Cd), lead (Pb), zinc (Zn), copper (Cu) and nickel (Ni) core profiles for Indian Lake, suggesting similar input sources. Historical disturbances and land- uses summarized from Lai (2009) and Appendix A. Chapter 3. Trace Element Trends within the Rideau River Waterway 85

Figure 14 Spatial distributions of surface sediment cadmium (Cd) concentrations Sediment samples screened against the federal interim sediment quality guideline (ISQG) of 0.6 µg g-1 and the probable effect level (PEL) of 3.5 µg g-1 set by the Canadian Council of Ministers of the Environment (CCME). Mean concentrations for the top 5cm of sediment cores used in comparison to grab samples. Bathymetric mapping provided TRAK Map Concepts Inc. 2005. Ontario Inland Lakes (TRAK Maps - Canadian Nautical Charts). 36 Digital Maps. Saint-Donat, Québec. Chapter 3. Trace Element Trends within the Rideau River Waterway 86

Figure 15 Spatial distributions of surface sediment lead (Pb) concentrations Sediment samples screened against the federal interim sediment quality guideline (ISQG) of 35.0 µg g-1 and the probable effect level (PEL) of 91.3 µg g-1 set by the Canadian Council of Ministers of the Environment (CCME). Mean concentrations for the top 5cm of sediment cores used in comparison to grab samples. Bathymetric mapping provided TRAK Map Concepts Inc. 2005. Ontario Inland Lakes (TRAK Maps - Canadian Nautical Charts). 36 Digital Maps. Saint-Donat, Québec. Chapter 3. Trace Element Trends within the Rideau River Waterway 87

Figure 16 Spatial distribution of surface sediment zinc (Zn) concentrations Sediment samples screened against the federal interim sediment quality guideline (ISQG) of 123 µg g-1 and the probable effect level (PEL) of 315 µg g-1 set by the Canadian Council of Ministers of the Environment (CCME). Mean concentrations for the top 5cm of sediment cores used in comparison to grab samples. Bathymetric mapping provided TRAK Map Concepts Inc. 2005. Ontario Inland Lakes (TRAK Maps - Canadian Nautical Charts). 36 Digital Maps. Saint-Donat, Québec. Chapter 4. General Discussion 88

Chapter 4 - General Discussion

Findings and Implications

The Rideau River Waterway, also known as the Rideau Canal, is a constructed navigation channel that links Ottawa to Kingston, Ontario. Opened in 1832, it was designated a

Canadian Heritage Site in 2003 and a United Nations Educational, Scientific and Cultural

Organization World Heritage Site in 2007. South of Smiths Falls, the Canal consists of a series of 14 lakes, connected to one another by dug channels and a series of locks, descending approximately 50-m to Lake Ontario.

Atmospherically emitted mercury (Hg), primarily as a product of the coal-based energy sector and waste incineration, is a global issue due to its potential for long-range transport. Although Hg has been used for millennia, global emissions grew exponentially beginning in the late 18th century. Recognized as a potent bioaccumulating neurotoxin, the widespread distribution of Hg has resulted in the closing of various global fisheries.

Within Ontario, most lake systems now have site specific guidelines restricting human consumption of fish. Recent increases in awareness, policies, regulations and cross- boundary collaborations have resulted in a reduction of Hg emissions by roughly 55% Chapter 4. General Discussion 89 within the north-eastern United States and eastern Canadian provinces (NEIWPCC, et al

2007).

Cadmium (Cd), lead (Pb) and zinc (Zn) are also emitted as by-products of the coal-based energy sector, waste incineration, and burning of fossil fuel combustion. Similarly, they are capable of long-range transport and their global concentrations have also increased exponentially since the period of modern industrialization. Copper (Cu) and nickel (Ni) are generally associated with the ferrous and non-ferrous metal smelting industry; while arsenic (As) is typically associated with chemical processing, such as in wood treatments, herbicides, fungicides and pesticides. While all toxic at high concentrations, unlike Hg, these elements are not recognized to biomagnify.

Utilizing paleolimnological techniques, historical records of these elements were analyzed from chronologically deposited lake sediments. Indian Lake served as the primary study lake based on the depositional integrity of its primary core, while Newboro

Lake and Upper Rideau Lake were used to examine similarities in associated trends.

Indian Lake, though the smallest of the three studied lakes, consistently had the highest overall As, Cd, Cu, Hg, Ni, Pb and Zn concentrations. Sedimentary records indicate that total Hg (THg) peaked in the mid-1980’s, at concentrations above the federal probable effect level (PEL) and roughly five times background concentrations (~1836). Similarly,

Cd, Cu, Ni, Pb and Zn all peaked around 1979 in Indian Lake, at concentrations ranging from 4.1 to 17.2 times background levels. Arsenic peaked around the 1940’s in Indian

Lake, at concentrations above the federal PEL and roughly 11 times background. While Chapter 4. General Discussion 90 peak enrichment ratios from Indian Lake fall within the normal range for most elements within other Ontario lakes, the enrichment of Pb is particularly high.

Overall, the THg enrichment to each of the lakes is within the range observed for most other freshwater lakes in the region. Sediment THg concentrations appear to have declined in recent decades within all lakes; however, the magnitude of the decrease may be over pronounced as a result of dilution from increased sedimentation rates. Results indicate that concentrations of THg in northern pike (Esox lucius) collected from Indian

Lake have decreased more than 60% since the late 1970’s. Although encouraging, there was insufficient data to discern conclusions of general trends in parallel with temporal sediment THg trends.

The agreement between Indian Lake depth profiles for Cd, Pb and Zn and then Cu and Ni suggest that each group of elements is primarily contributed from the same source. The similarity in trends and timing of peak concentrations between Indian Lake and other

Ontario lakes suggests large-scale, atmospheric contributions of elements to the lake. The lead-shifted profiles from Newboro Lake and Upper Rideau Lake also demonstrated parallel trends, consistent with atmospheric sources for all three lakes. The peak concentrations of both As and Hg were distinct from the peak for the other elements, suggesting different contribution sources. What could not be explained by the interpretation of sediment cores alone was the variation in magnitude of peaks and enrichment ratios observed among the interconnected lakes. Chapter 4. General Discussion 91

Following a review of variations in watershed-based characteristics, in addition to differences in localized anthropogenic factors, no individual causal factor was identified which could account for the differences in concentrations observed among the interconnected lakes. It is likely that such variations are the result of multiple factors.

Although it was not confirmed in this study, it is hypothesized that the catchment area to lake area ratios and surrounding land-uses are influential components.

Overall, historically-deposited sediments demonstrated that elemental concentrations have been declining in recent decades. Of the elements measured, recent surface sediment

As, Cd, Cu, Hg and Zn concentrations still remain above the federal interim sediment quality guideline (ISQG) and the concentration of Pb remains above the PEL within

Indian Lake, resulting in continued concern for both human and ecosystem health.

Based on the lack of likely point-sources identified and the similarity in element profiles across Ontario, primary contributions are suspected to be atmospherically derived.

Although long-range atmospheric contributions can only be regulated on a national and international scale, the management of local contributions are also of importance.

Locally, the 2008 results from the sport fish THg analysis will be used by the Ontario

Ministry of Environment (OME) in the development and updating of sport fish consumption restriction guidelines for the three study lakes. Overall, results indicate that there remains concern regarding As, Cd, Cu, Pb, Zn and Hg within all three lakes and particularly within Indian Lake as a result of the high sediment concentrations. The specific areas within the study lakes which have been identified as having higher surface concentrations of specific elements merit further investigation and any potential Chapter 4. General Discussion 92 disturbances in these areas should be limited. The deeper, core profile results indicated that peak element concentrations are currently buried. If left undisturbed, these elements are less likely to be bioavailable and the risk of exposure is reduced, which has important management implications as the navigation channels within the lakes are periodically dredged. Roadways and building materials, located in proximity to the water bodies, were identified as likely contributors to the element burdens in near shore regions. This is important in the consideration of future development and renovations along the waterfronts. Most importantly, the results of this study suggest that the contributions throughout the catchment area, not only along the shorelines, are influencing the water bodies and merit further consideration and management.

Future Research

The current study is the first historical analysis of metals and As concentrations within the lakes of the Rideau Canal. This work has substantiated the importance of the evaluation of atmospheric and watershed element contributions to aquatic systems in rural settings. Additional investigations into the following three areas are merited based on the findings of this research.

Firstly, with regards to sediments, additional grid-based surface samples should be collected and analyzed from each of the lakes. All of the sediment characteristics considered for core samples in the current study should also be considered for any surface samples analyzed. This approach would enable the utilization of GIS-based kriging, which could identify areas of concern for specific elements within each lake (Forsythe, et Chapter 4. General Discussion 93 al 2004; Manion 2007). Kriging may also help identify potential input sources and/or hydrological processes within each of the lakes, which may influence the distribution of particulate bound elements.

Secondly, with regards to potential sources, additional investigation into the influence of specific factors and analysis of sediment geochemistry is merited. GIS-based tools could be used to examine the relationships between land-uses within each of the catchments and sediment element concentrations. Other possible contributors such as the number of septic systems within each catchment should also be considered.

Thirdly, additional research is needed regarding the influence of decreased sediment element concentrations on the uptake and storage of contaminants by aquatic organisms.

Although the results of this study suggest that northern pike (Esox lucius) THg tissue concentrations are on the decline, detailed analysis of multiple species and the lake- specific food web should be undertaken in the future. In addition, further study of parallels between sediment THg concentrations and sport fish tissue concentrations is merited. Given the decreased atmospheric emissions within North America, such research would have important implications on a much larger scale. A number of studies have recently compared current and historical sport fish tissue concentrations across large areas; however, results have been variable, depending on the region (Lathrop, et al 1991;

MassDep 2006; Rasmussen, et al 2007). Identification of a direct link within the same system from decreased atmospheric concentrations, to decreased sediment concentrations, to decreased tissue concentrations in lake-specific predators merits further research. Chapter 4. General Discussion 94

Summary and Conclusions

1. Element concentration profiles preserved in sediments collected from Indian Lake, Newboro Lake and Upper Rideau Lake are generally depicting similar decreasing trends, suggesting a strong influence by atmospheric contributions of contaminants. Although demonstrating similarities in general trends for specific elements, each lake profile depicted unique variations in peak timing and the magnitudes of enrichment since Canal construction. Sediment, lake, watershed and land-use variables were examined; however, no single variable was identified as the causal factor for the dissimilarities observed. It is likely that the variations are attributable to multiple factor, of which watershed characteristics and land-uses qualitatively appeared influential. Differences in watershed characteristics and the potential influence of land-use merit further study. 2. Surface sediment concentrations of As, Cd, Cu, Hg, Pb and Zn remain elevated, above federal guidelines. While sediment profiles depicted buried peak element concentrations, the surface concentrations of As, Cd, Cu, Hg, Pb and Zn remain elevated above federal guidelines for the protection of aquatic health. The concentrations of Pb, particularly within Indian Lake were found to be especially high and a possible cause of concern for both human and ecosystem health. 3. Northern pike (Esox lucius) are responding differently within the study lakes on the Rideau River Waterway. These results further strengthen the necessity for lake specific monitoring and consumption restriction guidelines. Literature Cited 95

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Appendix A - Timeline of Historical Events and Land-uses

Credit: Lai, C. 2009. Exploring anthropogenic factors and sources in relation to environmental contaminants in the Rideau Lakes watershed. Undergraduate Thesis, Bachelor of Science, Queen’s University, Kingston, Ontario.

Appendix A. Timeline of Historical Events and Land-uses 109

Indian Lake

1823 – Grist, saw and carding mills, as well as a distillery built by Samuel Chaffey (Dewar 1983)

1834 – North Crosby area known for its potash (Patterson 2006)

1841 – 24 steamers, three self-propelled barges and 171 unpowered boats regularly using the canal for the commercial transport of goods (Peck 1982)

1842 – 1848 - North Crosby population grew from 97 in 1842 to 247 in 1848 (Patterson 2006)

1844 – Lock house at Chaffey’s constructed (Tullock 1981)

1847 – North Crosby population grew from 811 in 1845 to 1602 (Patterson 2006). Period of peak passenger traffic on the canal (Peck 1982)

1850 – 1890 – Transformation to an agricultural, lumbering and mining area (Bush 1977)

1850s – Phosphate mined in the Rideau Lakes area (Bush 1977). Farm sizes increased (Patterson 2006). Use emphasis shifted from defence to commerce (Peck 1982)

1851 – North Crosby had two grist mills, three saw mills, one tannery, one oat mill, one foundry, three shingle factories, one pail factory, three asheries, one marble works and one cider factory. Population grew to 1785 (Patterson 2006)

1861 – 1875 – Transition to shipment of lumber to the USA, export of iron ore from the region increasing (Bush 1977)

1861 – North Crosby had 16 stone houses, 112 frame houses, 195 log houses and 14 shanties (Patterson 2006).

1870 – New grist mill and house built by Samuel Chaffey (Dewar 1983). Prime lumber in the area already cut (Bush 1977)

1871 – North Crosby’s population reached 2127. Area rapidly changing from wheat and cereal farming to dairy farming (Patterson 2006)

1872 – Construction of the Gananoque and Rideau Railway – which was ceased before completion (Patterson 2006) Appendix A. Timeline of Historical Events and Land-uses 110

1873 – In one year, 34,881 T of coal shipped along the Rideau Canal (Bush 1977)

1880s – Black bass a common attraction for Indian Lake (Dewar 1983). Peak passenger traffic on the Rideau Canal attained (Bush 1977)

1883 – Coal traffic had declined to half what it was in 1873 (Bush 1977)

1885 – Coal traffic along the canal increased from what it was in 1885 (Bush 1977)

1886 – Construction of the Brockville, Westport and Sault St. Marie Railway began (Patterson 2006)

1888 – Coal traffic along the canal increased again from what it was in 1885 (Bush 1977). First train arrived on the Brockville, Westport and Sault St. Marie Railway (Patterson 2006)

1890s – Sawmills in the area closing down. Powered vessels navigating the canal (Bush 1977)

1891 – Locks gave out, temporarily dropping the water level slightly (Tulloch 1981)

1894 – Lockmaster’s house at Chaffey’s rebuilt (Tulloch 1981)

1896 – Only four cottages in North Crosby (Patterson 2006)

1902 – Locks further repaired (Tulloch 1981). Presently 329 farms in North Crosby, 109 dairy farms around Westport and nine operating cheese factories around North Crosby (Patterson 2006)

1903 – Brockville, Westport, Sault St. Marie railway went bankrupt (Patterson 2006)

1905 – Extensive renovations to the Opinicon Hotel (Dewar 1983)

1907 – First vehicles arriving in the area (Dewar 1983)

1913 – First train arrived on the Canadian Northern Railway (Dewar 1983)

1914 – Peak of mineral traffic on the Rideau Canal (Bush 1977)

1925 – Series of small cottages added to the Opinicon Hotel (Dewar 1983) Appendix A. Timeline of Historical Events and Land-uses 111

1930s – Increase in the number of fishermen frequenting the area and increase in cottage development (Patterson 2006)

1931 – Currently 42 cottages in North Crosby (Patterson 2006)

1959 – End of all mineral traffic in the area (Bush 1977)

1961 – All commercial traffic ceased on the Rideau Canal (Bush 1977)

1972 – Parks Canada took over the management of the Rideau Canal (Peck 1982)

1980s – Renovations and additions to the Opinicon Hotel (Dewar 1983)

1983 – Chaffey’s has the largest resort complex on the Rideau Lakes. The population is presently 60 people. Communities includes: summer residences, a few permanent homes, three resort hotels, two marinas, a general store and a community hall (Dewar 1983)

Newboro Lake

1831 – Sawmill constructed by Benjamin Tett (Bush 1977)

1833 – Blockhouse constructed (Tulloch 1981)

1834 – North Crosby area known for its potash (Patterson 2006)

1839 – First school opened in Newboro (Patterson 2006)

1841 – Lead mine opened 10 miles away from the lake (Bush 1977). 24 steamers, three self-propelled barges and 171 unpowered boats regularly using the canal for the commercial transport of goods (Peck 1982)

1842 – 1848 – Growth of Westport and Newboro communities. Saw mills, grist mills, distillery, carding and fulling mills, tannery and shoe making facilities established in the area. North Crosby population grew from 97 in 1842 to 247 in 1848 (Patterson 2006)

1843 – Saw mill built along the shores of Newboro Lake (Patterson 2006)

1846 – Tannery and brewery added near the saw mill built in 1843 (Patterson 2006) Appendix A. Timeline of Historical Events and Land-uses 112

1847 – Mercantile district established in downtown Newboro (Tailor, tinsmith, shoemaker, second tannery and blacksmith shops opened). North Crosby population grew from 811 in 1845 to 1602 (Patterson 2006). Period of peak passenger traffic on the canal (Peck 1982)

1850s – Cut required frequent dredging (Tulloch 1981)

1850 – 1890 – Transformation to an agricultural, lumbering and mining area (Bush 1977)

1850s – Phosphate mined in the Rideau Lakes area (Bush 1977). Farm sizes increased (Patterson 2006). A number of fires occurred in the town (Patterson 2006). Use emphasis shifted from defence to commerce (Peck 1982)

1851 – Outcrop of iron ore discovered on an island in the lake (Chaffey mine) (Bush 1977). North Crosby had two grist mills, three saw mills, one tannery, one oat mill, one foundry, three shingle factories, one pail factory, three asheries, one marble works and one cider factory. Population grew to 1785 (Patterson 2006)

1857 – Construction of the compacted crushed stone road between Newboro and Westport (Patterson 2006)

1858 – In a single year, the Chaffey mine produced 6 000 T of iron ore, all shipped to Pittsburgh (Bush 1977)

1860 – Name changed from Mud Lake to Newboro Lake (Tulloch 1981). Second iron mine (Matthews mine) opened on the north shore of the lake (Bush 1977)

1861 – 1875 – Transition to shipment of lumber to the USA, export of iron ore from the region increasing (Bush 1977)

1861 – North Crosby had 16 stone houses, 112 frame houses, 195 log houses and 14 shanties (Patterson 2006).

1870 – In a single year, the Chaffey mine produced 11 000 T of iron ore, all shipped to Pittsburgh and Cleveland (Bush 1977)

1871 – In a single year, the Matthews mine produced 4 000 T of iron ore, all shipped to Cleveland (Bush 1977). North Crosby’s population reached 2127. Area rapidly changing from wheat and cereal farming to dairy farming (Patterson 2006)

1872 – Construction of the Gananoque and Rideau Railway – which was ceased before completion (Patterson 2006) Appendix A. Timeline of Historical Events and Land-uses 113

1873 – In one year, 3 4881 T of coal shipped along the Rideau Canal (Bush 1977)

1874 – Worst of the Newboro town fires, where 26 buildings were destroyed (Patterson 2006)

1876 – Newboro established as its own village, independent of North or South Crosby, with a population of 300. Rebuilding from fire damage taking place (Patterson 2006)

1880 – Peak passenger traffic on the Rideau Canal attained (Bush 1977)

1883 – Coal traffic had declined to half what it was in 1873 (Bush 1977)

1885 – Coal traffic along the canal increased from what it was in 1885 (Bush 1977)

1886 – Construction of the Brockville, Westport and Sault St. Marie Railway began (Patterson 2006)

1888 – Lock house extensively renovated (Tulloch 1981). Coal traffic along the canal increased again from what it was in 1885 (Bush 1977). First train arrived on the Brockville, Westport and Sault St. Marie Railway (Patterson 2006)

1890s – Cut deepened. Permanent bulkhead constructed at the URL inflow and rock bottom was blasted out to a depth of 18 to 24 inches for a distance of 2200 feet. Remainder of blue clay bottom dredged in 1896 (Tulloch 1981). Sawmills in the area were closing down. Powered vessels began navigating the canal (Bush 1977)

1896 – Only four cottages in North Crosby (Patterson 2006)

1902 – Presently 329 farms in North Crosby, 109 dairy farms around Westport and nine operating cheese factories around North Crosby (Patterson 2006)

1903 – Brockville, Westport, Sault St. Marie railway went bankrupt (Patterson 2006)

1908 – Gas powered boats being built around Newboro Lake (Patterson 2006)

1909 – Repair to the locks (Tulloch 1981)

1910 – Tett sawmill closed down (Bush 1977) Appendix A. Timeline of Historical Events and Land-uses 114

1912 – Steam powered roller mill established in Newboro and the Canning Factory was closed (Patterson 2006)

1914 – Peak of mineral traffic on the Rideau Canal (Bush 1977)

1915 – Sale of alcohol ceased in Westport, causing the closure of the distilleries (Patterson 2006)

1918 – Newboro had electric street lighting, powered by a wind turbine in Bedford Mills (Patterson 2006)

1919 – The entire village of Newboro was supplied with electricity from Tett plant in Bedford Mills (Patterson 2006)

1920s – Old tannery site turned into Poplars resort (Patterson 2006)

1930s – Increase in the number of fishermen frequenting the area and increase in cottage development (Patterson 2006)

1931 – Currently 42 cottages in North Crosby (Patterson 2006)

1933 – New road cut Concession and Bay Streets to Newboro Lake (Patterson 2006)

1935 – Road between Newboro and Westport stabilized (Patterson 2006)

1959 – End of all mineral traffic in the area (Bush 1977)

1961 – All commercial traffic ceased on the Rideau Canal (Bush 1977)

1972 – Parks Canada took over the management of the Rideau Canal (Peck 1982)

Upper Rideau Lake

1834 – North Crosby area known for its potash (Patterson 2006)

1830 – First school built in Westport (Patterson 2006)

1841 – 24 steamers, three self-propelled barges and 171 unpowered boats regularly using the canal for the commercial transport of goods (Peck 1982) Appendix A. Timeline of Historical Events and Land-uses 115

1847 – North Crosby population grew from 811 in 1845 to 1602 (Patterson 2006). Period of peak passenger traffic on the canal (Peck 1982)

1850 – 1890 – Transformation to an agricultural, lumbering and mining area (Bush 1977)

1850s – Phosphate mined in the Rideau Lakes area (Bush 1977). Farm sizes increased (Patterson 2006). Use emphasis shifted from defence to commerce (Peck 1982)

1857 – Construction of the compacted crushed stone road between Newboro and Westport (Patterson 2006)

1861 – 1875 – Transition to shipment of lumber to the USA, export of iron ore from the region increasing (Bush 1977)

1861 – North Crosby had 16 stone houses, 112 frame houses, 195 log houses and 14 shanties (Patterson 2006). Westport establishing itself as an entrepreneurial centre with six general stores, two grocery stores, three hotels, a butcher shop, four boot and shoe stores, two clothiers, two blacksmith shops, a joinery, a tinsmith, a cooper shop, an iron foundry, a carriage manufacture, a sash and blind manufacture, two entertainment houses, three saw mills, a tannery, a carding mill and a woollen mill (Patterson 2006)

1871 – North Crosby’s population reached 2127. Area rapidly changing from wheat and cereal farming to dairy farming (Patterson 2006)

1872 – Construction of the Gananoque and Rideau Railway – which was ceased before completion (Patterson 2006)

1873 – In one year, 3 4881 T of coal shipped along the Rideau Canal (Bush 1977)

1880 – Peak passenger traffic on the Rideau Canal attained (Bush 1977)

1883 – Coal traffic had declined to half what it was in 1873 (Bush 1977) Appendix A. Timeline of Historical Events and Land-uses 116

1885 – Coal traffic along the canal increased from what it was in 1885 (Bush 1977)

1886 – Construction of the Brockville, Westport and Sault St. Marie Railway began (Patterson 2006)

1888 – Coal traffic along the canal increased again from what it was in 1885 (Bush 1977). First train arrived on the Brockville, Westport and Sault St. Marie Railway (Patterson 2006)

1890s – Sawmills in the area closing down. Powered vessels navigating the canal (Bush 1977)

1895 – Subdivision plan filled for 30 lots on the shores of Upper Rideau Lake (Patterson 2006). The Westport Cheese Factory opened (Patterson 2006)

1896 – Only four cottages in North Crosby (Patterson 2006)

1902 – Presently 329 farms in North Crosby, 109 dairy farms around Westport and nine operating cheese factories around North Crosby (Patterson 2006)

1903 – Brockville, Westport, Sault St. Marie railway went bankrupt (Patterson 2006)

1904 – Westport established as an individual village, separate from North or South Crosby (Patterson 2006)

1905 – Woollen mill constructed in Westport. Dam at the Electric Light and Milling Company broke open flooding Mill pond and washing out roads and bridges around Westport (Patterson 2006)

1906 – Buckle company established in Westport. Westport Manufacturing and Plating Company opened in Westport which manufactured electric gas lighters, electrical gas fixtures, electro plating, and casting of malleable work (Patterson 2006)

1907 – Cement sidewalks constructed in Westport (Patterson 2006)

1910 – More cement sidewalks constructed in Westport (Patterson 2006)

1911 – Westport Manufacturing and Plating Company destroyed by fire. New mill and foundry constructed in Westport (Patterson 2006)

1914 – Peak of mineral traffic on the Rideau Canal (Bush 1977) Appendix A. Timeline of Historical Events and Land-uses 117

1915 – Sale of alcohol ceased in Westport, causing the closure of the distilleries (Patterson 2006)

1916 – Two automotive dealerships opened in Westport (Patterson 2006)

1921 – Brockville/Westport railway reopened, providing one gasoline powered train car (Patterson 2006)

1929 – New hotel built to replace the Tweedsmuir in Westport (Dewar 1983). Six cheese factories presently located within Westport (Patterson 2006)

1930s – Increase in the number of fishermen frequenting the area and increase in cottage development (Patterson 2006)

1931 – Currently 42 cottages in North Crosby (Patterson 2006). Westport connected to Ontario Hydro (Patterson 2006)

1935 – Road between Newboro and Westport stabilized (Patterson 2006)

1959 – End of all mineral traffic in the area (Bush 1977)

1961 – All commercial traffic ceased on the Rideau Canal (Bush 1977)

1972 – Parks Canada took over the management of the Rideau Canal (Peck 1982)

Literature Cited

Bush, E.F. 1977. Commercial navigation on the Rideau Canal, 1832 - 1961. National Historic Parks and Sites Branch, Parks Canada, Ottawa, Ontario. pp. 1-525. Dewar, K. 1983. Resort development in the Rideau Lakes region of eastern Ontario, 1826-1955. Master of Art, Department of Geography, Carleton University, Ottawa, Ontario. pp. 1-143. Patterson, N.A. 2006. History of the township of north Crosby and Westport. The Review-Mirror, Westport, Ontario. Peck, M.B. 1982. From war to winterlude: 150 years on the Rideau Canal. Public Archives Canada, Ottawa, Ontario. pp. 1-184. Tullock, J. 1981. The Rideau Canal: Defence, transport, and recreation. Parks Canada, Ottawa, Ontario. pp. 1-228. Appendix B. Supplementary Information 118

Appendix B – Supplementary Information Appendix B Supplementary Information 119

Appendix B - Table 1 Geographical positioning system (GPS) coordinates (NAD83, Zone 18T) of sediment samples

07 Grab Date Latitude Longitude ID Sampled UR1 15-Oct-07 44o40’42” 76o23’37” UR2 15-Oct-07 44o40’6” 76o22’52” UR3 15-Oct-07 44o41’2” 76o22’27” UR4 15-Oct-07 44o40’13” 76o23’4” UR5 15-Oct-07 44o40’60” 76o21’38” UR7 15-Oct-07 44o40’3” 76o19’60” UR8 15-Oct-07 44o39’23” 76o20’17” UR10 15-Oct-07 44o40’12” 76o19’31” UR11 15-Oct-07 44o41’14” 76o20’27” UR12 16-Oct-07 44o41’17” 76o19’19” UR13 16-Oct-07 44o41’17” 76o18’46” UR14 16-Oct-07 44o42’10” 76o17’48” UR15 16-Oct-07 44o42’1” 76o18’19” UR16 16-Oct-07 44o41’35” 76o19’5” UR17 16-Oct-07 44o41’31” 76o19’47” UR18 16-Oct-07 44o40’48” 76o19’30” NL1 26-Oct-07 44o38’12” 76o18’27” NL2 26-Oct-07 44o37’42” 76o19’56” NL3 26-Oct-07 44o37’24” 76o20’3” NL4 26-Oct-07 44o37’29” 76o20’42” IL1 Aug-07 44o35’54” 76o18’42” IL2 Aug-07 44o35’49” 76o19’2” IL3 Aug-07 44o35’57” 76o20’17” IL4 Aug-07 44o35’54” 76o20’54” IL5 Aug-07 44o34’60” 76o19’16” IL6 Aug-07 44o35’14” 76o19’23” IL7 Aug-07 44o35’27” 76o19’52” IL8/IL9 Aug-07 44o35’45” 76o19’32” IL10 Aug-07 44o35’19” 76o19’49” IL11 Aug-07 44o35’47” 76o18’48” 08 Core Date Latitude Longitude ID Sampled URL 1 27-Aug-08 44o41’14” 76o20’7” NL 1 24-Apr-08 44o38’58” 76o18’32” NL 2 24-Apr-08 44o38’48” 76o17’58” NL 3 24-Apr-08 44o38’24” 76o18’20” NL 5 24-Apr-08 44o37’52” 76o19’25” NL 7 24-Apr-08 44o36’56” 76o19’21” NL 8 24-Apr-08 44o37’21” 76o19’43” NL 9 24-Apr-08 44o37’50” 76o19’37” NL 10 24-Apr-08 44o38’32” 76o19’9” IL 1 27-May-08 44o35’36” 76o19’5” IL 2 27-May-08 44o35’25” 76o19’23” * Lost roughly the top 10cm of the core in the field Appendix B Supplementary Information 120

Appendix B - Table 2 Surface sediment total mercury (THg) concentrations

Sample THg Concentration (µg g- Run Date n Name 1) (stdev)

19-Feb-08 IL-1 1 0.03 19-Feb-08 IL-2 1 0.08 19-Feb-08 IL-3 1 0.16 19-Feb-08 IL-4 1 0.21 19-Feb-08 IL-6 1 0.01 19-Feb-08 IL-7 1 0.13 19-Feb-08 IL-8 2 0.18 (+ 0.005) 19-Feb-08 IL-11 1 0.19 28-Oct-08 Core 2 5 0.36 (+ 0.09)

19-Feb-08 NL-1 1 0.17 19-Feb-08 NL-2 1 0.17 19-Feb-08 NL-3 1 0.15 19-Feb-08 NL-4 1 0.16 28-Oct-08 Core 7 5 0.26 (+ 0.05)

20-Feb-08 URL-1 1 0.15 20-Feb-08 URL-2 1 0.13 20-Feb-08 URL-3 1 0.01 20-Feb-08 URL-4 2 0.09 (+ 0.0002) 20-Feb-08 URL-5 1 0.13 20-Feb-08 URL-6 1 0.01 20-Feb-08 URL-7 1 0.10 20-Feb-08 URL-8 1 0.11 20-Feb-08 URL-10 1 0.08 20-Feb-08 URL-11 2 0.12 (+ 0.008) 20-Feb-08 URL-12 2 0.18 (+ 0.003) 20-Feb-08 URL-13 2 0.20 (+ 0.0006) 21-Feb-08 URL-14 2 0.04 (+ 0.0001) 21-Feb-08 URL-15 1 0.17 21-Feb-08 URL-16 1 0.22 21-Feb-08 URL-17 1 0.14 21-Feb-08 URL-18 1 0.14 28-Oct-08 Core 1 4 0.15 (+ 0.003)

Appendix B Supplementary Information 121

Appendix B - Table 3 Sediment total mercury (THg) analysis quality assurance, quality control results Hg Concentration Date Sample Weight (ng) (µg g-1) 28-Oct-08 blk 0.1000 0.0 0.00 28-Oct-08 blk 0.1000 0.0 0.00 28-Oct-08 blk 0.1000 0.2 0.00 28-Oct-08 blk 0.1000 0.0 0.00 29-Oct-08 blk 0.1000 0.0 0.00 29-Oct-08 blk 0.1000 0.0 0.00 29-Oct-08 blk 0.1000 0.0 0.00 29-Oct-08 blk 0.1000 0.0 0.00 29-Oct-08 blk 0.1000 0.3 0.00 29-Oct-08 blk 0.1000 0.0 0.00 25-Nov-08 blk 0.1000 0.4 0.00 25-Nov-08 blk 0.1000 0.1 0.00 25-Nov-08 blk 0.1000 0.2 0.00 25-Nov-08 blk 0.1000 0.1 0.00 25-Nov-08 blk 0.1000 0.2 0.00 25-Nov-08 blk 0.1000 0.0 0.00 25-Nov-08 blk 0.1000 0.1 0.00 25-Nov-08 blk 0.1000 0.0 0.00 25-Nov-08 blk 0.1000 0.1 0.00 25-Nov-08 blk 0.1000 0.0 0.00 28-Oct-08 boat blk 0.1000 0.0 0.00 29-Oct-08 boat blk 0.1000 0.0 0.00 25-Nov-08 boat blk 0.1000 0.0 0.00 28-Oct-08 20 ng qa/qc 0.0200 22.9 1.15 29-Oct-08 20 ng qa/qc 0.0200 23.8 1.19 29-Oct-08 20 ng qa/qc 0.0200 23.9 1.20 29-Oct-08 20 ng qa/qc 0.0200 22.3 1.11 25-Nov-08 20 ng qa/qc 0.0200 18.6 0.93 28-Oct-08 200 ng qa/qc 0.0400 201.1 5.03 29-Oct-08 200 ng qa/qc 0.0400 203.6 5.09 25-Nov-08 200 ng qa/qc 0.0400 184.8 4.62 25-Nov-08 200 ng qa/qc 0.0400 201.3 5.03 28-Oct-08 Mess-3 0.1178 10.7 0.09 28-Oct-08 Mess-3 0.1134 10.2 0.09 29-Oct-08 Mess-3 0.1064 9.7 0.09 29-Oct-08 Mess-3 0.1454 13.7 0.09 25-Nov-08 Mess-3 0.1529 12.7 0.08 25-Nov-08 Mess-3 0.1393 11.6 0.08 Appendix B Supplementary Information 122

Appendix B - Table 3 continued Hg Concentration Date Sample Weight (ng) (µg g-1) Duplicate Samples 29-Oct-08 URL 1-6 0.0874 12.5 0.14 URL 1-6 29-Oct-08 DUP 0.1014 14.9 0.15 28-Oct-08 NL 7-10 0.1116 32.9 0.29 NL 7-10 28-Oct-08 DUP 0.1140 33.8 0.30 28-Oct-08 IL 2-6 0.1041 49.0 0.47 28-Oct-08 IL 2-6 DUP 0.1008 46.6 0.46 25-Nov-08 IL 2-N 0.1200 11.9 0.10 25-Nov-08 IL 2-N DUP 0.1435 15.2 0.11

Appendix B Supplementary Information 123

Appendix B - Table 4 Surface water total mercury (THg) concentration Surface Samples Mean Concentration n -1 Range (pg mL ) (stdev) Spring Runoff Samples Upper Rideau Lake 5 14.43 (11.32) 2.51 - 27.82 Newboro Lake 0 No samples Indian Lake 2 1.60 (0.11) 1.52 - 1.68 Upper Rideau Lake

May 4 0.70 (0.18) 0.46 - 0.88 June 8 1.17 (0.29) 0.49 - 1.43 August 17 0.41 (0.17) 0.26 - 0.888 Newboro Lake April 10 1.10 (0.34) 0.70 - 1.99 May 0 No samples June 20 1.48 (1.10) 0.61 - 4.51 August 9 0.65 (0.41) 0.33 - 1.38 Indian Lake April 5 0.75 (0.09) 0.64 - 0.88 May 7 0.96 (0.39) 0.68 - 1.61 June 5 0.80 (0.23) 0.62 - 1.19 August 7 0.69 (0.34) 0.37 - 1.22 Appendix B Supplementary Information 124

Appendix B - Table 5 Trace element concentrations in surface and depth water samples Mean Surface Water Sample Concentrations [n] (µg mL-1) (stdev) As Cr Cu K Ni Pb Rb Zn Spring Runoff Samples

Upper Rideau Lake [5] 2 (+ 0) [5] 1 (+ 1) [5] 1 (+ 0.4) [5] 1167 (+ 238) [5] 0.2 (+ 0.4) [5] 0.2 (+ 0.4) [5] 0.42 (+ 1) [5] 2 (+ 1) Newboro Lake No samples Indian Lake [2] 2 (+ 0) [2] 1 (+ 1) [2] ND [2] 963 (+ 13) [2] ND [2] ND [2] 1 (+ 1) [2] 2 (+ 1) Upper Rideau Lake

April [2] 4 [2] 2 (+ 1) [2] 8 (+ 1) [2] 1353 (+ 75) [2] 2 (+ 2) [2] ND [2] 1 (+ 1) [2] 3 (+ 1) June [6] 3 (+ 1) [6] 2 (+ 2) [6] 6 (+ 2) [6] 1503 (+ 194) [6] 0.4 (+ 0.2) [6] 1 (+ 1) [6] 2 (+ 0.5) [6] 7 (+ 3) August [16] 3 (+ 1) [16] 2 (+ 1) [16] 5 (+ 1) [16] 1320 (+ 221) [16] 0.4 (+ 1) [16] 1 (+ 0) [16] 1 (+ 1) [16] 4 (+ 1) Newboro Lake April [7] 3 (+ 1) [7] 2 (+ 2) [7] 9 (+ 1) [7] 1172 (+ 39) [7] 1 (+ 1) [7] ND [7] 0.3 (+ 0.5) [7] 4 (+ 1) June [13] 3 (+ 1) [13] 0.4 (+ 1) [13] 5 (+ 2) [13] 866 (+ 374) [13] 1 (+ 0.5) [13] 1 (+ 1) [13] 1 (+ 1) [13] 8 (+ 5) August [8] 3 (+ 1) [8] 3 (+ 2) [8] 6 (+ 1) [8] 619 (+ 378) [8] 1 (+ 1) [8] 3 (+ 5) [8] 1 (+ 1) [8] 8 (+ 4) Indian Lake April [9] 3 (+ 1) [9] 1 (+ 1) [9] 8 (+ 2) [9] 1015 (+ 87) [9] 1 (+ 1) [9] 0.2 (+ 0.4) [9] 1 (+ 1) [9] 3 (+ 2) June [6] 2 (+ 1) [6] 2 (+ 1) [6] 8 (+ 1) [6] 917 (+ 76) [6] 2 (+ 1) [6] 9 (+ 11) [6] 2 (+ 1) [6] 6 (+ 3) August [9] 4 (+ 1) [9] 1 (+ 0.1) [9] 7 (+ 1) [9] 714 (+ 108) [9] 0.5 (+ 0.3) [9] 7 (+ 15) [9] 1 (+ 0.2) [9] 14 (+ 10) Mean Depth Water Sample Concentrations [n] (ng mL-1) (stdev) As Cr Cu K Ni Pb Rb Zn Spring Runoff Samples

Upper Rideau Lake No samples Newboro Lake No samples Indian Lake No samples Upper Rideau Lake

April [1] 3 [1] 1 [1] 10 [1] 1406 [1] 1 [1] 1 [1] 1 [1] 4 June [6] 3 (+ 1) [6] 2 (+ 1) [6] 6 (+ 2) [6] 1602 (+ 196) [6] 1 (+ 0.3) [6] 2 (+ 0.4) [6] 2 (+ 0.3) [6] 8 (+ 5) August [15] 3 (+ 1) [15] 1 (+ 1) [15] 5 (+ 1) [15] 1366 (+ 172) [15] 0.3 (+ 0.5) [15] 1 (+ 1) [15] 1 (+ 1) [15] 4 (+ 2) Newboro Lake April [6] 3 (+ 1) [6] 1 (+ 1) [6] 9 (+ 2) [6] 1569 (+ 342) [6] 1 (+ 1) [6] 0.2 (+ 0.4) [6] 1 (+ 1) [6] 5 (+ 3) June [13] 2 (+ 0.5) [13] 0.4 (+ 1) [13] 5 (+ 2) [13] 873 (+ 235) [13] 2 (+ 4) [13] 2 (+ 6) [13] 1 (+ 1) [13] 7 (+ 3) August [9] 4 (+ 1) [9] 1 (+ 1) [9] 6 (+ 3) [9] 661 (+ 162) [9] 1 (+ 0.5) [9] 1 (+ 0.4) [9] 1 (+ 1) [9] 5 (+ 2) Indian Lake April [11] 3 (+ 1) [11] 0.5 (+ 1) [11] 7 (+ 1) [11] 1007 (+ 135) [11] 0.4 (+ 1) [11] 0.2 (+ 0.4) [11] 1 (+ 1) [11] 3 (+ 1) June [5] 3 (+ 0.4) [5] 2 (+ 1) [5] 10.2 (+ 2) [5] 1054 (+ 193) [5] 1 (+ 1) [5] 20 (+ 40) [5] 3 (+ 1) [5] 6 (+ 2) August [5] 3 (+ 0.3) [5] 1 (+ 0.4) [5] 6 (+ 1) [5] 1028 (+ 246) [5] 0.3 (+ 0.2) [5] 2 (+ 3) [5] 1 (+ 0.1) [5] 5 (+ 3)

Appendix B Supplementary Information 125

Appendix B - Table 6 Surface water total mercury (THg) analysis quality assurance, quality control results (Standards, blanks, Certified Reference Materials and duplicates) Hg QAQC Concentration Hg Worksheet QAQC Concentration Worksheet Label (pg g-1) Number Label (pg g-1) Number WS00000047 Std0.5 0.46 WS00000047 Std25.0 24.10 Std0.5 0.64 Std25.0 23.23 WS00000068 WS00000068 Std0.5 0.37 Std25.0 26.46 WS00000070 WS00000070 Std0.5 0.58 Std25.0 24.51 WS00000072 WS00000072 Std0.5 0.53 Std25.0 22.93 WS00000083 WS00000083 Std0.5 0.54 Std25.0 24.03 WS00000109 WS00000109 Std0.5 0.49 Std25.0 25.27 WS00000113 WS00000113 Std0.5 0.58 Std25.0 23.15 WS00000115 WS00000115 Std0.5 0.59 Std25.0 23.40 WS00000118 WS00000118 Std0.5 0.59 Std25.0 23.06 WS00000084 WS00000084 WS00000047 Std1.0 1.13 WS00000047 Std50 50.75 Std1.0 0.94 Std50 48.69 WS00000068 WS00000068 Std1.0 0.93 Std50 56.83 WS00000070 WS00000070 Std1.0 1.12 Std50 54.76 WS00000072 WS00000072 Std1.0 0.99 Std50 51.66 WS00000083 WS00000083 Std1.0 1.02 Std50 47.95 WS00000109 WS00000109 Std1.0 1.00 Std50 50.01 WS00000113 WS00000113 Std1.0 1.05 Std50 47.39 WS00000115 WS00000115 Std1.0 1.02 Std50 48.63 WS00000118 WS00000118 Std1.0 1.07 Std50 49.60 WS00000084 WS00000084 WS00000047 Std5.0 4.77 WS00000047 Std100 101.40 Std5.0 4.53 Std100 96.69 WS00000068 WS00000068 Std5.0 4.88 Std100 115.49 WS00000070 WS00000070 Std5.0 4.83 Std100 106.45 WS00000072 WS00000072 Std5.0 4.66 Std100 106.24 WS00000083 WS00000083 Std5.0 4.82 Std100 101.86 WS00000109 WS00000109 Std5.0 5.06 Std100 100.28 WS00000113 WS00000113 Std5.0 4.76 Std100 95.53 WS00000115 WS00000115 Std5.0 4.74 Std100 95.21 WS00000118 WS00000118 Std5.0 4.50 Std100 93.93 WS00000084 WS00000084 WS00000047 IPR5.0 5.91 WS00000047 OPR5.0 4.60 IPR5.0 5.79 OPR5.0 4.84 WS00000068 WS00000068 IPR5.0 7.27 OPR5.0 5.74 WS00000070 WS00000070 IPR5.0 6.88 OPR5.0 5.90 WS00000072 WS00000070 IPR5.0 8.33 OPR5.0 5.40 WS00000083 WS00000072 IPR5.0 5.07 OPR5.0 5.76 WS00000109 WS00000083 IPR5.0 4.81 OPR5.0 4.28 WS00000109 WS00000083 Appendix B Supplementary Information 126

Appendix B – Table 6 continued Hg Hg QAQC Concentration QAQC Concentration Worksheet Worksheet Label (pg g-1) Label (pg g-1) Number Number

IPR5.0 6.08 OPR5.0 5.01 WS00000113 WS00000109 IPR5.0 0.20 OPR5.0 5.46 WS00000113 WS00000113 IPR5.0 5.21 OPR5.0 4.68 WS00000115 WS00000115 IPR5.0 4.75 OPR5.0 4.84 WS00000115 WS00000118 IPR5.0 5.37 OPR5.0 5.10 WS00000118 WS00000084 79 (500 IPR5.0 4.65 0.40 WS00000118 WS00000109 SM) 79 (500 IPR5.0 7.49 0.30 WS00000084 WS00000109 SM) DUP 81 (500 Method Blank 2.49 WS00000047 0.16 WS00000113 SM) 81 (500 Method Blank 0.13 2.67 WS00000068 WS00000113 SM) DUP 10 (500 Method Blank 0.03 0.33 WS00000070 WS00000113 LM) 10 (500 Method Blank 0.21 0.24 WS00000072 WS00000113 LM) DUP Method Blank 18.94 39 (250) 2.99 WS00000083 WS00000083 39 (250) Method Blank 0.03 2.47 WS00000109 WS00000083 DUP 0.09 17 (250) 0.61 WS00000113 Method Blank WS00000083 17 (250) 0.10 0.77 WS00000115 Method Blank WS00000083 DUP Method Blank 0.30 1 (250) 0.94 WS00000084 WS00000083 1 (250) 0.23 0.89 WS00000118 MB1 WS00000083 DUP 0.14 4.24 WS00000118 MB2 WS00000109 11 (250) 0.10 1.22 WS00000118 MB3 WS00000113 11 (250) 0.12 1.24 WS00000118 MB4 WS00000109 27 (250) 0.09 0.50 WS00000118 MB5 WS00000113 27 (250) 27 (250) 0.11 0.37 WS00000118 MB6 WS00000113 DUP 66 (500 0.08 6.38 WS00000118 MB7 WS00000115 SM) 66 (500 0.09 6.23 WS00000118 MB8 WS00000115 SM) DUP 75 (500 DORM2 180.14 0.33 WS00000068 WS00000115 SM) 75 (500 CRM 21.31 0.37 WS00000070 WS00000115 SM) DUP 85 (500 DORM 351.64 0.39 WS00000072 WS00000115 SM) 85 (500 CRM 22.28 0.30 WS00000083 WS00000115 SM) DUP CRM 6.49 0.42 WS00000084 WS00000115 3 (500 LM) 3 (500 LM) T-UR-A8-1 1.25 WS00000047 19.08 WS00000115 DUP T-UR-A8-1 1.31 WS00000047 DUP 20.06 WS00000118 3 (500 LM) Appendix B Supplementary Information 127

Appendix B – Table 6 continued Hg Hg QAQC Concentration QAQC Concentration Worksheet Worksheet Label (pg g-1) Label (pg g-1) Number Number 3 (500 LM ) T-I-A8-1 1.29 WS00000047 1.93 WS00000118 DUP WS00000047 T-I-A8-1 DUP 1.42 WS00000084 7 (250) 5.67 S-T-IL-A2 8.89 7 (250) DUP 7.36 WS00000070 WS00000084 S-T-IL-A2 10.04 29 (500) LM 2.72 WS00000070 DUP WS00000084 29 (500) LM 56 1.42 1.58 WS00000072 WS00000084 DUP 56 DUP 1.42 WS00000072 17 0.73 WS00000072 WS00000072 17 DUP 0.62 Appendix B. Supplementary Information 128

Appendix B - Table 7 Sediment element concentration analysis quality assurance, quality control results (duplicates) Relative Relative Relative Relative As Concentration Standard Cd Concentration Standard Co Concentration Standard Cr Concentration Standard Cu Concentration Run Date Sample (µg g-1) Deviation (µg g-1) Deviation (µg g-1) Deviation (µg g-1) Deviation (µg g-1) (%) (%) (%) (%)

14-Jan-08 UR-4 1.6 1.2 20% 0.8 0.7 9% 7.0 6.3 7% 22.4 16.9 20% 15.2 12.8 UR-8-1 1.6 1.5 5% 0.8 0.7 9% 5.5 5.7 3% 17.5 18.7 5% 22.6 23.7 IS-8 3.6 3.3 6% 1.5 2.0 20% 11.6 9.1 17% 44.4 32.2 23% 33.6 28.2 IS-5-2 5.6 6.1 6% 2.9 3.1 5% 9.6 10.0 3% 34.0 33.5 1% 33.1 34.1 14-Dec-07 UR-15 8.4 7.7 6% 2.4 2.2 6% 12.5 11.5 6% 36.4 32.8 7% 41.2 38.2 14-Jan-08 UR-13 9.9 8.8 8% 2.8 2.5 8% 11.7 11.2 3% 33.9 32.0 4% 40.6 38.5 UR-14 0.8 1.5 43% 0.5 0.5 0% 4.5 5.1 9% 14.3 15.6 6% 7.4 9.8 UR-15 7.4 7.6 2% 2.2 2.3 3% 10.9 11.2 2% 31.4 79.1 61% 36.7 46.1 UR-17 3.6 2.5 26% 1.5 1.1 22% 10.7 7.6 24% 32.8 29.1 8% 32.5 23.0 15-Jan-08 IC1-E 2.0 2.5 16% 0.4 0.5 16% 4.0 5.7 25% 14.3 49.4 78% 6.4 11.6 IC1-M 0.6 0.7 11% 0.4 0.5 16% 6.0 7.1 12% 17.8 21.0 12% 10.6 12.9 28-Oct-08 URL 1-7 4.8 4.7 1% 1.1 1.2 6% 6.7 7.0 3% 16.5 16.3 1% 32.1 31.6 URL 1-10 3.8 4.6 13% 1.2 1.5 16% 5.9 7.4 16% 15.4 16.0 3% 28.3 34.0 28-Oct-08 IL 2-K 1.3 1.3 0% 1 0.9 7% 12.8 11.6 7% 31.8 30 4% 34.3 32.6 NL 7-8 3.8 3.9 2% 1.8 1.7 4% 7.84 7.94 1% 17.9 18.2 1% 39.8 40.4 29-Oct-08 IL 2-10 16.0 15.8 1% 3.3 3.3 0% 10.7 10.8 1% 27.2 27.2 0% 38.3 38.7 URL 1-F 9.1 8.4 6% 2.2 2.1 3% 8.0 7.2 8% 22.9 19.8 10% 35.4 33.6 29-Oct-08 URL 1-M 9.4 8.1 11% 2.0 1.6 16% 8.1 6.7 13% 22.3 19.6 9% 31.7 27.1 NL 7-Q 8.6 8.2 3% 2.6 2.5 3% 7.8 7.3 4% 18.0 17.7 1% 38.8 37.5 29-Oct-08 NL 7-E 9.2 7.6 13% 2.8 3.1 7% 7.9 8.5 5% 19.5 21.0 5% 38.5 45.1 NL 7-F 8.2 8.0 2% 3.2 3.1 2% 8.4 8.2 2% 21.0 20.9 0% 44.7 45.3 Appendix B. Supplementary Information 129

Appendix B - Table 7 Continued Relative Relative Relative Relative As Concentration Standard Cd Concentration Standard Co Concentration Standard Cr Concentration Standard Cu Concentration Run Date Sample (µg g-1) Deviation (µg g-1) Deviation (µg g-1) Deviation (µg g-1) Deviation (µg g-1) (%) (%) (%) (%)

30-Oct-08 NL 1-8 2.6 2.7 3% 1.5 1.6 5% 4.6 4.5 1% 23.9 23.8 0% 30.2 32.0 NL 2-3 1.2 1.3 6% 0.9 1.0 7% 3.4 3.4 0% 12.0 11.9 1% 23.1 23.8 30-Oct-08 NL 5-1 0.3 1.5 94% 0.6 0.8 20% 3.7 5.3 25% 46.6 14.6 74% 16.0 33.1 NL 8-1 1.0 0.4 61% 0.7 0.6 11% 4.8 3.3 27% 13.6 51.5 82% 33.4 13.8 30-Oct-08 NL 8-5 0.6 0.3 47% 0.6 0.6 0% 4.5 4.4 2% 12.5 10.9 10% 32.6 29.6 30-Oct-08 IL 1-1 6.6 5.8 9% 1.2 2.2 42% 6.5 7.4 10% 32.8 30.0 6% 36.8 41.7 NL 10-4 0.6 0.4 28% 0.5 0.5 0% 3.8 3.9 2% 10.7 10.1 4% 23.2 27.3 26-Jan-09 URL 1-24 8.1 8.0 1% 1.1 1.0 6% 8.0 8.5 5% 23.3 24.0 2% 26.9 27.4 IL 5-10 6.4 7.0 7% 1.5 1.7 9% 7.7 8.3 6% 21.1 23.9 9% 25.4 28.6 23-Jan-08 IL 4-TOP 11.4 9.6 12% 3.4 3.5 2% 8.9 8.6 3% 23.4 23.6 1% 45.6 41.7 URL 1-22 11.2 9.4 12% 1.2 1.2 3% 8.7 7.9 7% 21.9 20.4 5% 29.0 25.1 15% 9% 8% 14%

Appendix B. Supplementary Information 130

Appendix B - Table 6 Continued Relative Relative Relative Relative Relative Relative K Ni Pb Rb Zn Standard Standard Standard Standard Standard Standard Run Date Sample Concentration Concentration Concentration Concentration Concentration Deviation Deviation Deviation Deviation Deviation Deviation (µg g-1) (µg g-1) (µg g-1) (µg g-1) (µg g-1) (%) (%) (%) (%) (%) (%)

14-Jan-08 UR-4 12% 1401.0 1294.0 6% 12.5 9.8 17% 28.3 23.5 13% 16.2 15.0 5% 82.2 72.1 9% UR-8-1 3% 1107.0 1348.0 14% 10.7 11.3 4% 26.7 27.3 2% 11.2 12.1 5% 74.7 71.7 3% IS-8 12% 2835.0 1653.0 37% 24.7 22.2 8% 69.7 119.0 37% 25.0 16.4 29% 143.0 194.0 21% IS-5-2 2% 1843.0 1946.0 4% 24.7 24.9 1% 166.0 174.0 3% 16.8 17.5 3% 252.0 263.0 3% 14-Dec-07 UR-15 5% 2704.0 2405.0 8% 25.7 23.7 6% 128.0 117.0 6% 22.5 19.3 11% 227.0 208.0 6% 14-Jan-08 UR-13 4% 2846.2 2755.5 2% 24.8 23.4 4% 143.1 139.0 2% 30.4 29.3 3% 235.0 225.3 3% UR-14 20% 921.5 1040.8 9% 6.6 7.0 4% 23.2 27.0 11% 10.0 10.8 5% 55.6 67.5 14% UR-15 16% 2471.3 2385.5 2% 22.6 32.5 25% 120.2 122.9 2% 27.0 26.8 1% 209.4 220.7 4% UR-17 24% 2398.7 1620.2 27% 22.4 17.0 19% 91.0 69.5 19% 26.1 17.9 26% 172.9 128.6 21% 15-Jan-08 IC1-E 41% 687.0 930.0 21% 7.7 15.3 47% 12.2 12.1 1% 6.8 9.5 23% 33.7 45.9 22% IC1-M 14% 1246.0 1369.0 7% 1.6 13.8 112% 4.2 4.8 9% 11.6 13.0 8% 37.7 47.1 16% 28-Oct-08 URL 1-7 1% 1421.0 1543.0 6% 15.5 15.8 1% 67.1 68.2 1% 14.3 15.5 6% 147.0 130.0 9% URL 1-10 13% 1282.0 1520.0 12% 14.1 17.3 14% 95.7 113.0 12% 12.2 16.2 20% 117.0 142.0 14% 28-Oct-08 IL 2-K 4% 2365 2307 2% 20.8 19.5 5% 15.7 14.5 6% 21.3 19.1 8% 119 109 6% NL 7-8 1% 1437 1509 3% 17.6 17.7 0% 129 130 1% 12.3 12 2% 160 160 0% 29-Oct-08 IL 2-10 1% 1764.0 1843.0 3% 22.0 22.2 1% 145.0 149.0 2% 17.7 18.0 1% 286.0 292.0 1% URL 1-F 4% 1520.0 1503.0 1% 21.3 19.3 7% 152.0 142.0 5% 17.9 15.4 11% 218.0 203.0 5% 29-Oct-08 URL 1-M 11% 1787.0 1561.0 10% 19.2 15.5 15% 76.3 63.8 13% 20.2 16.3 15% 168.0 138.0 14% NL 7-Q 2% 1395.0 1363.0 2% 19.5 18.2 5% 118.0 116.0 1% 12.0 11.3 4% 199.0 194.0 2% 29-Oct-08 NL 7-E 11% 1497.0 1450.0 2% 19.7 20.8 4% 114.0 213.0 43% 12.5 11.1 8% 202.0 258.0 17% NL 7-F 1% 1527.0 1423.0 5% 21.1 22.2 4% 203.0 197.0 2% 13.2 11.0 13% 260.0 257.0 1% Appendix B. Supplementary Information 131

Appendix B - Table 7 Continued Relative Relative Relative Relative Relative Relative K Ni Pb Rb Zn Standard Standard Standard Standard Standard Standard Run Date Sample Concentration Concentration Concentration Concentration Concentration Deviation Deviation Deviation Deviation Deviation Deviation (µg g-1) (µg g-1) (µg g-1) (µg g-1) (µg g-1) (%) (%) (%) (%) (%) (%)

30-Oct-08 NL 1-8 4% 1816.0 1791.0 1% 16.6 17.1 2% 92.1 96.4 3% 14.7 13.1 8% 131.0 129.0 1% NL 2-3 2% 1377.0 1343.0 2% 11.9 11.8 1% 27.2 28.3 3% 8.9 7.8 9% 75.5 73.6 2% 30-Oct-08 NL 5-1 49% 832.0 1161.0 23% 11.3 19.6 38% 19.3 19.5 1% 5.5 9.4 37% 50.9 63.1 15% NL 8-1 59% 1005.0 802.0 16% 19.4 9.7 47% 19.2 18.9 1% 8.5 5.1 35% 60.6 44.7 21% 30-Oct-08 NL 8-5 7% 924.0 889.0 3% 19.0 17.3 7% 8.2 6.9 12% 7.9 7.4 5% 47.8 44.5 5% 30-Oct-08 IL 1-1 9% 1537.0 17.7 138% 20.6 23.3 9% 41.1 93.7 55% 14.0 15.4 7% 96.0 172.0 40% NL 10-4 11% 806.0 836.0 3% 16.3 15.7 3% 6.6 6.3 3% 6.3 6.4 1% 40.2 41.1 2% 26-Jan-09 URL 1-24 1% 1546.0 1564.0 1% 17.2 16.2 4% 38.5 39.4 2% 14.5 14.3 1% 95.9 96.4 0% IL 5-10 8% 1305.0 1397.0 5% 15.3 17.1 8% 54.2 61.1 8% 9.0 10.0 7% 123.0 139.0 9% 23-Jan-08 IL 4-TOP 6% 1383.0 1325.0 3% 22.5 22.5 0% 265.0 272.0 2% 12.5 9.6 18% 311.0 309.0 0% URL 1-22 10% 1768.0 1749.0 1% 17.8 16.9 4% 50.1 47.0 5% 19.8 15.1 19% 123.0 110.0 8% 12% 12% 13% 9% 11% 9%

Appendix B. Supplementary Information 132

Appendix B - Table 8 Water element concentration analysis quality assurance, quality control results (duplicates) Relative Relative Relative Relative Relative As Cd Co Cr Cu Batch Standard Standard Standard Standard Standard Run Date Sample Concentration Concentration Concentration Concentration Concentration Number Deviation Deviation Deviation Deviation Deviation (µg g-1) (µg g-1) (µg g-1) (µg g-1) (µg g-1) (%) (%) (%) (%) (%) 29-Apr-08 UR-1 0.002 0.002 0% 0.000 0.000 0% 0.000 0.000 0% 0.001 0.001 0% 0.001 0.001 0%

16-Jul-08 Batch 4 IL-2 DW 0.004 0.004 0% 0.000 0.000 0% 0.000 0.000 0% 0.000 0.000 0% 0.007 0.007 0% 16-Jul-08 Batch 5 IL-A4 SW 0.030 0.030 0% 0.000 0.000 0% 0.000 0.000 0% 0.001 0.001 0% 0.007 0.012 71% Blank 0.003 0.000 141% 0.000 0.000 0% 0.000 0.000 0% 0.001 0.000 100% 0.009 0.000 100%

16-Jul-08 Batch 6 IL-A3 DW 0.002 0.002 0% 0.000 0.000 0% 0.000 0.000 0% 0.000 0.000 0% 0.006 0.007 17% IL-A5 SW 0.002 0.002 0% 0.000 0.000 0% 0.000 0.000 0% 0.000 0.001 0% 0.008 0.008 0%

NL-A2 DW 0.003 0.002 28% 0.000 0.000 0% 0.000 0.000 0% 0.001 0.000 100% 0.010 0.010 0%

Jun-08 (NL33 Batch 7 0.003 0.003 0% 0.000 0.000 0% 0.000 0.000 0% 0.001 0.001 0% 0.006 0.009 50% DW Field Dup) Batch 8 27 (NL129 DW) 0.002 0.002 0% 0.000 0.000 0% 0.000 0.000 0% 0.000 0.000 0% 0.004 0.004 0%

22 (NL33 DW) 0.002 0.002 0% 0.000 0.000 0% 0.000 0.000 0% 0.000 0.000 0% 0.004 0.004 0%

Batch 9 58 (URL113 SW) 0.003 0.004 20% 0.000 0.000 0% 0.000 0.000 0% 0.003 0.001 67% 0.006 0.005 17%

47 (URL28 DW) 0.004 0.003 20% 0.000 0.000 0% 0.000 0.000 0% 0.001 0.000 100% 0.006 0.004 33%

Batch 10 72 (NL51 DW) 0.004 0.003 27% 0.000 0.000 0% 0.000 0.000 0% 0.001 0.001 40% 0.013 0.006 54%

D (IL17 SW) 0.003 0.004 20% 0.000 0.000 0% 0.000 0.000 0% 0.001 0.001 25% 0.006 0.007 11%

Batch 11 126 (NL117 DW) 0.003 0.004 20% 0.000 0.000 0% 0.000 0.000 0% 0.001 0.001 0% 0.005 0.005 0%

54 (URL74 SW) 0.003 0.003 0% 0.000 0.000 0% 0.000 0.000 0% 0.001 0.001 0% 0.005 0.004 20%

20-Feb-09 Batch 12 101 (URL93 SW) 0.003 0.004 20% 0.000 0.000 0% 0.000 0.000 0% 0.001 0.001 0% 0.005 0.006 20% 119 (URL114 0.004 0.002 47% 0.000 0.000 0% 0.000 0.000 0% 0.003 0.001 67% 0.007 0.005 29% DW Field Dup) 25% 0% 0% 24% 30%

Appendix B. Supplementary Information 133

Appendix B - Table 8 Continued Relative Relative Relative Relative Relative K Ni Pb Rb Zn Batch Standard Standard Standard Standard Standard Run Date Sample Concentration Concentration Concentration Concentration Concentration Number Deviation Deviation Deviation Deviation Deviation (µg g-1) (µg g-1) (µg g-1) (µg g-1) (µg g-1) (%) (%) (%) (%) (%) 29-Apr-08 UR-1 1.089 1.078 0.010 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.001 0.000 0.002 0.002 0.000 16-Jul-08 Batch 4 IL-2 DW 1.225 1.231 0.005 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.001 0.000 0.003 0.002 0.333 16-Jul-08 Batch 5 IL-A4 SW 0.888 0.963 0.084 0.001 0.001 0.000 0.000 0.000 0.000 0.001 0.001 0.000 0.003 0.005 0.667 Blank 1.425 0.001 0.999 0.001 0.000 1.000 0.000 0.000 0.000 0.001 0.001 0.000 0.002 0.000 1.000

16-Jul-08 Batch 6 IL-A3 DW 0.975 0.925 0.051 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000 1.000 0.004 0.003 0.250 IL-A5 SW 1.013 0.988 0.025 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000 0.006 0.002 0.667

NL-A2 DW 1.944 1.925 0.010 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000 1.000 0.008 0.003 0.625

Jun-08 (NL33 Batch 7 DW Field Dup) 0.781 0.756 0.032 0.001 0.002 1.000 0.022 0.004 0.818 0.002 0.002 0.000 0.006 0.003 0.500 27 (NL129 Batch 8 DW) 0.900 0.900 0.000 0.000 0.001 0.000 0.000 0.000 0.000 0.001 0.001 0.000 0.008 0.003 0.625 - 22 (NL33 DW) 0.631 0.579 0.082 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000 0.007 0.006 0.143 58 (URL113 Batch 9 SW) 1.603 1.595 0.005 0.000 0.001 0.000 0.002 0.002 0.000 0.002 0.001 0.500 0.013 0.005 0.615 47 (URL28 DW) 1.722 1.164 0.324 0.000 0.000 0.000 0.001 0.002 1.000 0.002 0.000 1.000 0.008 0.009 0.125 Batch 10 72 (NL51 DW) 0.568 0.455 0.200 0.001 0.001 0.500 0.002 0.000 0.833 0.002 0.000 1.118 0.009 0.007 0.233

D (IL17 SW) 0.597 0.695 0.164 0.000 0.001 1.250 0.001 0.003 2.500 0.001 0.001 0.286 0.012 0.026 1.115

126 (NL117 Batch 11 DW) 0.663 0.794 0.198 0.001 0.000 1.000 0.001 0.001 0.000 0.001 0.001 0.000 0.005 0.004 0.200 54 (URL74 SW) 1.031 1.188 0.152 0.000 0.000 0.000 0.001 0.001 0.000 0.000 0.000 0.000 0.003 0.004 0.333 101 (URL93 20-Feb-09 Batch 12 SW) 1.113 1.413 0.270 0.000 0.000 0.000 0.001 0.001 0.000 0.001 0.002 1.000 0.003 0.004 0.333 119 (URL114 DW Field Dup) 1.656 1.181 0.287 0.001 0.000 1.000 0.002 0.002 0.000 0.002 0.002 0.000 0.008 0.006 0.250 0.161 0.319 0.286 0.328 0.445 0.214 0.281 0.313 0.223 0.591 27% 38% 13% 50% 39% Appendix B. Supplementary Information 134

Appendix B - Table 9 Sediment element concentration analysis quality assurance, quality control results (Certified Reference Materials and blanks) Batch 1 - Oct 28, 2008 Batch 2 - Oct 28, 2008 Batch 3 - Oct 29, 2008 Batch 4 - Oct 29, 2008 Element MESS-3 MESS-3 MESS-3 MESS-3 As 16.0 15.2 16.0 15.8 Cd 0.6 0.5 0.5 0.6 Co 11.1 10.4 10.7 10.7 Cr 32.9 28.2 27.8 29.5 Cu 30.2 29.8 32.0 31.6 K 4930.0 4368.0 4358.0 4620.0 Ni 35.3 32.8 35.5 34.2 Pb 17.5 17.3 17.8 18.1 Rb 43.3 35.4 35.8 34.7 Zn 123.0 120.0 121.0 127.0 Batch 5 - Oct 29, 2008 Batch 6 - Oct 30, 2008 Batch 7 - Oct 30, 2008 Batch 8 - Oct 30, 2008 Element MESS-3 MESS-3 MESS-3 MESS-3 As 14.9 15.1 15.7 14.7 Cd 0.6 0.7 0.6 0.7 Co 10.7 10.7 10.6 10.7 Cr 27.9 29.3 27.1 26.2 Cu 30.7 31.1 29.6 31.1 K 3946.0 4345.0 1095.0 4011.0 Ni 33.9 34.9 33.4 34.6 Pb 18.1 19.4 17.8 18.9 Rb 29.8 32.9 32.8 31.2 Zn 123.0 121.0 120.0 121.0 Batch 9 - Oct 30, 2008 Batch 13 - Jan 26, 2009 Batch 14 - Jan 23, 2009 Element MESS-3 MESS-3 MESS-3 As 15.5 16.9 15.3 Cd 0.7 0.5 0.4 Co 11.3 12.6 11.5 Cr 27.8 32.9 28.9 Cu 32.7 35.8 33.8 K 4083.0 4402.0 4541.0 Ni 35.6 35.6 35.8 Pb 20.0 18.5 16.8 Rb 30.7 26.6 25.9 Zn 128.0 131.0 127.0 Batch 1 - Oct 28, 2008 Batch 2 - Oct 28, 2008 Batch 3 - Oct 29, 2008 Batch 4 - Oct 29, 2008 Element SS-2 SS-2 SS-2 SS-2 As 68.4 73.0 65.9 63.4 Cd 1.9 2.0 1.8 2.0 Co 11.9 12.9 11.2 12.0 Cr 35.2 36.3 32.5 35.5 Cu 170.0 196.0 178.0 188.0 K 3895.0 4293.0 3838.0 4225.0 Ni 51.2 55.8 47.3 51.8 Pb 103.0 117.0 104.0 111.0 Rb 36.5 41.1 33.7 35.6 Zn 398.0 450.0 404.0 450.0 All concentrations presented in µg g-1

Appendix B. Supplementary Information 135

Appendix B - Table 9 Continued Batch 5 - Oct 29, 2008 Batch 6 - Oct 30, 2008 Batch 7 - Oct 30, 2008 Batch 8 - Oct 30, 2008 Element SS-2 SS-2 SS-2 SS-2 As 61.4 58.0 88.4 54.5 Cd 2.1 2.0 2.3 2.1 Co 12.4 11.8 14.9 12.1 Cr 37.2 35.9 41.7 35.3 Cu 197.0 185.0 218.0 190.0 K 3995.0 3980.0 4747.0 3927.0 Ni 52.6 49.6 58.7 52.9 Pb 114.0 113.0 130.0 112.0 Rb 34.7 34.4 46.1 36.0 Zn 454.0 428.0 508.0 435.0 Batch 9 - Oct 30, 2008 Batch 13 - Jan 26, 2009 Batch 14 - Jan 23, 2009 Element SS-2 SS-2 SS-2 As 58.0 73.9 80.4 Cd 2.2 2.0 2.1 Co 12.8 14.3 14.3 Cr 37.7 40.1 40.1 Cu 204.0 195.0 192.0 K 4090.0 3924.0 4492.0 Ni 57.1 53.4 56.5 Pb 123.0 123.0 127.0 Rb 35.5 27.2 31.4 Zn 468.0 481.0 493.0 Batch 1 - Oct 28, 2008 Batch 1 - Oct 28, 2008 Batch 2 - Oct 28, 2008 Batch 2 - Oct 28, 2008 Element Blank 1 Blank 2 Blank 3 Blank 4 As -0.1 -0.8 0.0 -0.1 Cd 0.1 0.2 0.1 0.1 Co 0.0 0.0 0.0 0.0 Cr 0.3 0.8 0.5 0.8 Cu 2.8 3.5 2.7 2.6 K 3.3 12.8 15.3 15.9 Ni 0.4 0.3 0.2 0.2 Pb 2.3 3.6 1.7 1.4 Rb 0.0 0.0 -0.1 -0.1 Zn 4.8 3.7 2.2 2.5 Batch 3 - Oct 29, 2008 Batch 3 - Oct 29, 2008 Batch 4 - Oct 29, 2008 Batch 4 - Oct 29, 2008 Element Blank 1 Blank 2 Blank 1 Blank 2 As -0.3 -0.5 -0.4 -0.4 Cd 0.1 0.1 0.1 0.1 Co 0.0 0.0 0.0 0.0 Cr 0.3 0.3 0.3 0.3 Cu 2.5 2.7 3.4 2.7 K 17.0 16.4 18.5 19.8 Ni 0.2 0.3 0.4 0.4 Pb 1.8 1.8 2.4 2.3 Rb 0.0 0.0 -0.1 -0.1 Zn 2.2 2.4 3.0 2.8 All concentrations presented in µg g-1

Appendix B. Supplementary Information 136

Appendix B - Table 9 Continued Batch 5 - Oct 29, 2008 Batch 5 - Oct 29, 2008 Batch 6 - Oct 30, 2008 Batch 6 - Oct 30, 2008 Element Blank 1 Blank 2 Blank 1 Blank 2 As -0.2 -0.2 -0.2 0.1 Cd 0.1 0.2 0.2 0.2 Co 0.0 0.0 0.0 0.0 Cr 0.3 0.3 0.3 0.2 Cu 2.3 3.9 3.5 3.3 K 11.6 11.6 14.3 15.8 Ni 0.6 0.5 0.8 0.6 Pb 1.9 2.8 3.4 3.2 Rb 0.0 -0.1 -0.2 -0.2 Zn 4.2 3.7 3.7 3.2 Batch 7 - Oct 30, 2008 Batch 7 - Oct 30, 2008 Batch 8 - Oct 30, 2008 Batch 8 - Oct 30, 2008 Element Blank 1 Blank 2 Blank 1 Blank 2 As -0.3 -0.3 -0.4 -0.3 Cd 0.2 0.1 0.2 0.2 Co 0.0 0.0 0.0 0.0 Cr 0.1 0.2 0.1 0.1 Cu 3.0 2.0 4.5 3.8 K 20.6 14.2 19.5 19.7 Ni 1.4 1.9 0.9 0.5 Pb 2.3 1.7 3.9 3.3 Rb 0.1 0.0 -0.1 -0.1 Zn 3.9 2.8 5.5 4.2 Batch 9 - Oct 30, 2008 Batch 9 - Oct 30, 2008 Batch 13 - Jan 26, 2009 Batch 13 - Jan 26, 2009 Element Blank 1 Blank 2 Blank 1 Blank 2 As -0.1 -0.2 0.6 0.6 Cd 0.2 0.2 0.0 0.0 Co 0.1 0.1 0.0 0.0 Cr 0.1 0.1 0.0 0.0 Cu 4.5 3.8 3.3 2.5 K 19.1 19.8 9.9 8.4 Ni 0.9 0.5 -0.2 -0.2 Pb 4.1 3.3 0.1 0.1 Rb 0.0 0.1 -0.6 -0.9 Zn 5.5 4.1 0.7 0.6 Batch 14 - Jan 23, 2009 Batch 14 - Jan 23, 2009 Element Blank 1 Blank 2 As -0.4 -0.6 Cd 0.0 0.0 Co 0.0 0.0 Cr 0.3 0.3 Cu 5.0 5.3 K 18.8 16.9 Ni 0.3 0.4 Pb 0.2 0.2 Rb 0.0 0.2 Zn 1.1 1.5 All concentrations presented in µg g-1

Appendix B. Supplementary Information 137

Appendix B - Table 10 Water element concentration analysis quality assurance, quality control results (Blanks and spikes) Batch 3 - Apr 29, 2008 Batch 4 - Jul 16, 2008 Batch 4 - Jul 16, 2008 Batch 5 - Jul 16, 2008 Element Blank Blank 1 Blank 2 Blank 1 As 0.002 0.004 0.004 0.002 Cd 0.000 0.000 0.000 0.000 Co 0.000 0.000 0.000 0.000 Cr 0.000 0.001 0.000 0.000 Cu 0.000 0.008 0.011 0.006 K 0.014 0.008 0.008 0.008 Ni 0.000 0.001 0.000 0.000 Pb 0.000 0.001 0.000 0.000 Rb 0.000 0.000 0.000 0.000 Zn 0.002 0.002 0.003 0.006 Batch 5 - Jul 16, 2008 Batch 5 - Jul 16, 2008 Batch 5 - Jul 16, 2008 Batch 6 - Jul 16, 2008 Element Blank 2 Blank 2 DUP Blank 2 Blank 1 As 0.003 0.000 0.004 0.003 Cd 0.000 0.000 0.000 0.000 Co 0.000 0.000 0.000 0.000 Cr 0.001 0.000 0.001 0.000 Cu 0.009 0.000 0.007 0.008 K 1.425 0.001 0.004 0.006 Ni 0.001 0.000 0.001 0.001 Pb 0.000 0.000 0.001 0.000 Rb 0.001 0.001 -0.001 0.000 Zn 0.002 0.000 0.003 0.003 Element Batch 7 - Aug 20, 2008 Batch 8 - Aug 20, 2008 Batch 9 - Mar 2, 2009 Batch 10 - Mar 3, 2009 Blank 1 Blank 1 Blank 1 Blank 1 As 0.003 0.002 0.003 0.004 Cd 0.000 0.000 0.000 0.000 Co 0.000 0.000 0.000 0.000 Cr 0.001 0.000 0.001 0.001 Cu 0.009 0.003 0.004 0.006 K 0.005 0.002 0.006 0.012 Ni 0.001 0.000 0.001 0.000 Pb 0.001 0.000 0.002 0.006 Rb 0.002 0.000 0.001 0.001 Zn 0.002 0.003 0.007 0.006 Element Batch 10 - Mar 3, 2009 Batch 11 - Feb 23, 2009 Batch 11 - Feb 23, 2009 Batch 12 - Feb 20, 2009 Blank 2 Blank 1 Blank 2 Blank 3 As 0.004 0.004 0.003 0.004 Cd 0.000 0.000 0.000 0.000 Co 0.000 0.000 0.000 0.000 Cr 0.004 0.001 0.001 0.004 Cu 0.006 0.005 0.006 0.005 K 0.005 0.033 0.026 0.009 Ni 0.001 0.000 0.001 0.000 Pb 0.002 0.001 0.001 0.001 Rb -0.001 0.003 0.001 0.001 Zn 0.010 0.004 0.005 0.006 All concentrations presented in µg g-1

Appendix B. Supplementary Information 138

Appendix B - Table 10 Continued Element Batch 3 - Apr 29, 2008 Batch 4 - Jul 16, 2008 Batch 4 - Jul 16, 2008 Batch 5 - Jul 16, 2008 Spike Spike 1 Spike 2 Spike 1 As 0.089 0.106 0.101 0.108 Cd 0.085 0.105 0.099 0.099 Co 0.171 0.204 0.198 0.192 Cr 0.085 0.098 0.098 0.097 Cu 0.171 0.208 0.204 0.201 K 0.065 0.069 0.066 0.062 Ni 0.180 0.200 0.191 0.198 Pb 0.845 1.013 0.956 0.988 Rb 0.013 0.016 0.015 0.015 Zn 0.319 0.388 0.368 0.376 Element Batch 5 - Jul 16, 2008 Batch 6 - Jul 16, 2008 Batch 7 - Aug 20, 2008 Batch 8 - Aug 20, 2008 Spike 2 Spike 1 Spike 1 Spike 1 As 0.107 0.081 0.109 0.100 Cd 0.096 0.071 0.108 0.097 Co 0.190 0.138 0.209 0.186 Cr 0.096 0.070 0.105 0.092 Cu 0.201 0.151 0.223 0.198 K 0.059 0.054 0.068 0.055 Ni 0.196 0.142 0.215 0.191 Pb 0.969 0.706 1.063 0.956 Rb 0.013 0.012 0.034 0.030 Zn 0.364 0.264 0.402 0.366 Element Batch 9 - Mar 2, 2009 Batch 10 - Mar 3, 2009 Batch 10 - Mar 3, 2009 Batch 11 - Feb 23, 2009 Spike 1 Spike 1 Spike 2 Spike 1 As 0.127 0.105 0.089 0.116 Cd 0.118 0.110 0.093 0.115 Co 0.235 0.210 0.181 0.224 Cr 0.114 0.106 0.091 0.116 Cu 0.217 0.216 0.190 0.239 K 0.062 0.077 0.058 0.084 Ni 0.239 0.216 0.184 0.231 Pb 1.154 1.073 0.903 1.175 Rb 0.032 0.028 0.024 0.030 Zn 0.441 0.421 0.348 0.445 Element Batch 11 - Feb 23, 2009 Batch 12 - Feb 20, 2009 Batch 12 - Feb 20, 2009 Batch 12 - Feb 20, 2009 Spike 2 Spike 3 Spike 4 Blank 4 As 0.128 0.128 0.112 0.003 Cd 0.126 0.123 0.130 0.000 Co 0.244 0.239 0.195 0.000 Cr 0.123 0.122 0.118 0.001 Cu 0.243 0.249 0.225 0.005 K 0.092 0.078 0.112 0.016 Ni 0.251 0.245 0.258 0.000 Pb 1.269 1.200 1.163 0.001 Rb 0.032 0.029 0.032 0.001 Zn 0.482 0.471 0.496 0.004 All concentrations presented in µg g-1

Appendix B. Supplementary Information 139

Appendix B - Table 11 Trace element correlations for Indian Lake (IL) sediment samples Indian Lake (IL) Primary Core (IL-C2) Element Arsenic (As) Cadmium (Cd) Cobalt (Co) Chromium (Cr) Copper (Cu) Potassium (K) Nickel (Ni) Lead (Pb) Rubidium (Rb) Zinc (Zn) Arsenic (As) 1.0000 Cadmium (Cd) 0.8577 1.0000 Cobalt (Co) 0.2819 0.3215 1.0000 Chromium (Cr) 0.1643 0.1046 0.3301 1.0000 Copper (Cu) 0.6198 0.8457 0.1546 0.0639 1.0000 Potassium (K) 0.5371 0.5628 0.6752 0.4357 0.3819 1.0000 Nickel (Ni) 0.3113 0.4892 0.0000 0.0053 0.6634 0.0866 1.0000 Lead (Pb) 0.6194 0.8627 0.4141 0.1901 0.8310 0.6892 0.4444 1.0000 Rubidium (Rb) 0.1045 0.1866 0.5591 0.3303 0.1180 0.5358 0.0269 0.3709 1.0000 Zinc (Zn) 0.7468 0.9633 0.3287 0.0936 0.8800 0.5405 0.5547 0.8979 0.2604 1.0000

Indian Lake (IL) Surface Samples Element Arsenic (As) Cadmium (Cd) Cobalt (Co) Chromium (Cr) Copper (Cu) Potassium (K) Nickel (Ni) Lead (Pb) Rubidium (Rb) Zinc (Zn) Arsenic (As) 1.0000 Cadmium (Cd) 0.6214 1.0000 Cobalt (Co) 0.3187 0.1405 1.0000 Chromium (Cr) 0.0614 0.0422 0.7763 1.0000 Copper (Cu) 0.4068 0.3722 0.3210 0.2912 1.0000 Potassium (K) 0.1065 0.0187 0.8828 0.8017 0.1441 1.0000 Nickel (Ni) 0.2942 0.3061 0.5974 0.6862 0.7662 0.4046 1.0000 Lead (Pb) 0.6724 0.8021 0.1867 0.0449 0.3045 0.0316 0.3235 1.0000 Rubidium (Rb) 0.1381 0.0446 0.9080 0.8281 0.2001 0.9176 0.4977 0.0580 1.0000 Zinc (Zn) 0.7921 0.8383 0.3012 0.1441 0.5921 0.0907 0.5193 0.7726 0.1156 1.0000

Values presented as r2 Underline - Indicates a negative correlation Bold - indicates a significant correlation (p < 0.05)

Appendix B. Supplementary Information 140

Appendix B - Table 12 Trace element and potential factor correlations for Indian Lake (IL) and Upper Rideau Lake Values presented as r2. Underline indicates a negative correlation, bold indicates a significant correlation (p < 0.05) Indian Lake (IL) Surface Samples Element Sample Depth (m) % Pebble % Gravel % Sand % Silt/Clay [As] µg g-1 [Cd] µg g-1 [Cu] µg g-1 [Ni] µg g-1 [Pb] µg g-1 [Zn] µg g-1 Sample Depth (m) 1.0000

% Pebble 0.0267 1.0000

% Gravel 0.4290 0.4380 1.0000

% Sand 0.0542 0.9922 0.5160 1.0000

% Silt/Clay 0.0095 0.3511 0.2659 0.3373 1.0000

[As] µg g-1 0.1541 0.1896 0.1104 0.2087 0.0875 1.0000

[Cd] µg g-1 0.1702 0.1089 0.0726 0.1257 0.0701 0.8617 1.0000

[Cu] µg g-1 0.0002 0.0114 0.0598 0.0145 0.0014 0.2425 0.0817 1.0000

[Ni] µg g-1 0.0209 0.0950 0.0965 0.1045 0.0060 0.6762 0.5139 0.7420 1.0000

[Pb] µg g-1 0.2216 0.0519 0.0560 0.0652 0.1563 0.8925 0.9545 0.1182 0.5338 1.0000

[Zn] µg g-1 0.1352 0.0196 0.0258 0.0272 0.1733 0.8580 0.9239 0.2013 0.6410 0.9661 1.0000 Upper Rideau Lake (URL) Surface Samples

Element Sample Depth (m) % Pebble % Gravel % Sand % Silt/Clay [As] µg g-1 [Cd] µg g-1 [Cu] µg g-1 [Ni] µg g-1 [Pb] µg g-1 [Zn] µg g-1 Sample Depth (m) 1.0000

% Pebble 0.0284 1.0000

% Gravel 0.1096 0.0010 1.0000

% Sand 0.0374 0.1230 0.4172 1.0000

% Silt/Clay 0.0455 0.1465 0.0983 0.1682 1.0000

[As] µg g-1 0.7071 0.0591 0.0267 0.0578 0.0597 1.0000

[Cd] µg g-1 0.5194 0.0869 0.0166 0.1285 0.0196 0.9253 1.0000

[Cu] µg g-1 0.2063 0.1149 0.0003 0.2219 0.0016 0.6696 0.8446 1.0000

[Ni] µg g-1 0.2555 0.0204 0.0275 0.1032 0.0013 0.6214 0.8256 0.8102 1.0000

[Pb] µg g-1 0.3628 0.1092 0.0004 0.2120 0.0065 0.7797 0.9035 0.9036 0.7293 1.0000

[Zn] µg g-1 0.4058 0.0939 0.0030 0.1719 0.0031 0.8338 0.9618 0.9218 0.8201 0.9767 1.0000 Upper Rideau Lake (URL) Surface Samples Minus Samples Collected at Depths Greater Than 5 Metres

Element Sample Depth (m) % Pebble % Gravel % Sand % Silt/Clay [As] µg g-1 [Cd] µg g-1 [Cu] µg g-1 [Ni] µg g-1 [Pb] µg g-1 [Zn] µg g-1 Sample Depth (m) 1.0000

% Pebble 0.7154 1.0000

% Gravel 0.3425 0.0404 1.0000

% Sand 0.8921 0.7992 0.3702 1.0000

% Silt/Clay 0.3147 0.0861 0.3866 0.3432 1.0000

[As] µg g-1 0.2995 0.7046 0.0007 0.4232 0.0005 1.0000

[Cd] µg g-1 0.1270 0.6061 0.0235 0.2905 0.0287 0.7739 1.0000

[Cu] µg g-1 0.2064 0.6079 0.0041 0.3965 0.0073 0.8776 0.8997 1.0000

[Ni] µg g-1 0.0000 0.2498 0.1102 0.0653 0.0432 0.3727 0.7845 0.5525 1.0000

[Pb] µg g-1 0.1340 0.4207 0.0249 0.2980 0.0511 0.6566 0.7753 0.9132 0.4683 1.0000

[Zn] µg g-1 0.1191 0.4982 0.0001 0.2742 0.0694 0.7312 0.9158 0.9475 0.6243 0.9946 1.0000