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Land use impacts on ground and surface water quality in the Bertrand Creek watershed (Township of Langley,… Solano, Maria Gabriela 2006

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L A N D U S E I M P A C T S O N G R O U N D A N D S U R F A C E W A T E R Q U A L I T Y IN T H E B E R T R A N D C R E E K W A T E R S H E D ( T O W N S H I P O F L A N G L E Y , B.C.) by M A R I A G A B R I E L A S O L A N O Lie. in Biology, University of El Sa lvador , 2002 A T H E S I S S U B M I T T E D IN P A R T I A L F U L F I L M E N T O F T H E R E Q U I R E M E N T S F O R T H E D E G R E E O F M A S T E R O F S C I E N C E in T H E F A C U L T Y O F G R A D U A T E S T U D I E S (Resou rce Management and Environmental S tud ies ) T H E U N I V E R S I T Y O F BRIT ISH C O L U M B I A March 2006 © Maria Gabr ie la So lano , 2006 Abstract Bertrand Creek is a small transboundary watershed with mixed land use that provides a good case study to compare the impacts of urban and agricultural activities on water resources. Located in southeastern Langley, it encompasses the city of Aldergrove and an agricultural area that extends from south of Aldergrove to the Canada - US international border. The main goal of this study was to determine land use impacts on water quality. Water samples were analyzed for nutrients and dissolved elements and results were linked to land use through a GIS. Streambed sediments were analyzed for trace metals and bioavailability of metals was measured along Bertrand Creek using the diffusive gradients in thin films (DGT) technique. Land use didn't seem to be correlated to groundwater quality but results indicated that nitrate contamination in the Abbotsford aquifer is a concern. Well depth appeared to have a significant influence in the quality of groundwater and only wells <15 m deep exceeded the drinking water quality guidelines for N 0 3 - N. Surface water analysis indicated high concentrations of nitrate and phosphorus, especially on Howes Creek. Correlation with land use data showed that high concentrations of manganese in surface water and concentrations of copper, lead and zinc in sediments were positively correlated to the extent of impervious surfaces. Nitrate - N concentrations were influenced by agricultural activities particularly during the wet season. It is therefore important that stormwater and agricultural best management practices be exercised, including the increase of riparian buffer areas, improved manure management and storage techniques and the construction of stormwater detention ponds, particularly at sites that receive direct runoff from heavily used roads. Despite the importance of the streams in this watershed to aquatic life there appears to be a significant lack of water quality studies and monitoring. The results of the present study warrant further research in the watershed to ensure a healthy habitat for aquatic life and to protect drinking water sources in rural areas. 11 Table of Contents Abstract ii Table of Contents iii List of Tables vii List of Figures ix Acknowledgements xii Dedication xiii 1 Introduction and Background 1 1.1 Study Area 2 1.1.1 Groundwater Resources 5 1.2 Water Quality Parameters and Indicators 10 1.2.1 Temperature 10 1.2.2 Dissolved Oxygen (DO) 10 1.2.3 Chloride in Surface and Ground Waters 10 1.2.4 Total Suspended Solids (TSS) and Turbidity 11 1.2.5 Total Dissolved Solids (TDS) and Conductivity '. 12 1.2.6 Trace Elements in Water and Sediments 12 1.2.7 Nutrient Pollution 14 1.2.7.1 Nitrogen and the Nitrogen Cycle 14 1.2.7.2 Nitrogen: Sources and Impacts 15 1.2.7.3 Phosphorus: sources and impacts 17 1.2.7.4 Phosphorus and the Phosphorus Cycle 19 2 Goals and Objectives 21 3 Methodology ..-22 3.1 Survey to Private Well Owners 22 3.2 Groundwater Sampling and Analysis 23 3.3 Surface Water Sampling and Analysis 24 3.4 Use of DGTs and Analysis of Bioavailable Trace Metals in Surface Waters 25 3.5 Sediment Sampling and Analysis 26 3.5.1 Particle Size Analysis 27 3.5.2 Trace Metal Analysis in Relation to Wet/Dry Weather Conditions 27 3.5.3 Trace Metal Analysis in Relation to Particle Size 28 3.5.4 Organic Matter Content Analysis 28 3.6 Application of GIS Techniques to Determine Land Use Impacts on Sediment, Surface Water and Groundwater Quality 28 3.7 Data Analysis Methods 29 3.7.1 Groundwater Data Statistical Analysis 30 3.7.2 Surface Water Data Statistical Analysis 30 3.7.3 Sediment Data Statistical Analysis 31 3.7.4 DGT Data Statistical Analysis 31 3.7.5 Relationships between Land Use, Sediment and Water Quality... 31 3.8 Quality Analysis and Quality Control (QA/QC) 32 3.8.1 Groundwater Q A / Q C 32 3.8.2 Surface Water Q A / Q C 32 3.8.3 Sediment Q A / Q C 32 3.8.4 DGT Q A / Q C 32 4 Results 33 4.1 Precipitation and flow data 33 4.2 Groundwater results 35 4.2.1 Groundwater Survey Results 35 4.2.2 Groundwater Quality Results 39 4.2.2.1 Correlations between Groundwater Quality Parameters 41 4.3 Surface water quality results 44 4.3.1 Spatial and Seasonal Variations in Nitrate (N0 3"- N) 45 4.3.2 Spatial and Seasonal Variations in Orthophosphate 47 4.3.3 Spatial and Seasonal Variations in Chloride 48 4.3.4 Spatial and Seasonal Variations in Dissolved Oxygen 49 4.3.5 Spatial and Seasonal Variations in pH 51 4.3.6 Spatial and Seasonal Variations in Specific Conductivity 52 4.3.7 Spatial and Seasonal Variations in Temperature 53 iv 4.3.8 Spatial and Seasonal Variations in Elements in Surface Waters 54 4.3.8.1 Spatial and Seasonal Trends in Calcium (Ca) 55 4.3.8.2 Spatial and Seasonal Trends in Magnesium (Mg) 56 4.3.8.3 Spatial and Seasonal Trends in Iron (Fe) 57 4.3.8.4 Spatial and Seasonal Trends in Manganese (Mn) 58 4.3.8.5 Spatial and Seasonal Trends in Potassium (K) 59 4.3.8.6 Spatial and Seasonal Trends in Sodium (Na) 60 4.3.8.7 Spatial and Seasonal Trends in Zinc (Zn) 61 4.4 DGT results 62 4.4.1 Spatial and seasonal variations in bioavailable metals 62 4.5 Sediment analysis results 63 4.5.1 Particle size distribution 63 4.5.2 Organic matter content 64 4.5.2.1 Trace Elements in Sediments: Differences in Accumulation According to Particle Size 65 4.5.3 Spatial and Seasonal Variations in Sediment Quality 66 4.5.4 Correlations between elements in sediments 79 4.6 Relationships between Land Use, Sediment, Surface and Groundwater Quality 79 4.6.1 Correlations between Land Use Categories and Groundwater Quality 79 4.6.2 Correlations between Land Use Categories and Surface Water Quality 80 4.6.3 Correlations between Land Use Categories and Sediment Quality Parameters.82 4.7 Relationships between Ground and Surface Waters 82 5 Discussion 85 5.1 Groundwater Quality and well owners' perception of water quality 85 5.1.1 Nitrate - N spatial variability and relationship to depth 85 5.1.2 Orthophosphate ;. : 88 5.1.3 Chloride 89 5.1.4 pH 89 5.1.5 Turbidity .' 90 5.1.6 Total Dissolved Solids 90 5.1.7 Dissolved elements : 91 5.2 Land Use Impacts on Groundwater Quality. 92 5.3 Public Perceptions of Groundwater Quality 94 5.4 Surface water quality 97 5.4.1 Nitrate - Nitrogen 98 v 5.4.2 Orthophosphate 99 5.4.3 Chloride : 100 5.4.4 Dissolved Oxygen ; ; 101 5.4.5 pH 103 5.4.6 Specific Conductivity 104 5.4.7 Temperature 105 5.5 Trace Elements in Surface Water and Sediments 105 5.6 Land Use Impacts on Surface Water and Sediment Quality 111 5.6.1 Nutrients in surface waters 111 5.6.2 Trace elements in sediments 111 6 Conclusions and Recommendations 113 6.1 Groundwater quality and well owners' perception of water quality 113 6.2 Surface water quality: nutrients, chloride and chemical parameters 113 6.3 Trace elements in surface water and sediments .114 6.4 Land use impacts on water and sediment quality in the watershed 114 References 116 APPENDICES 126 Appendix A: Groundwater Letters and Survey 127 Appendix B: Groundwater Sampling Results 136 Appendix C: Surface water sampling results 142 Appendix D: Sediment Sampling Results 164 Appendix F: Spearman Rank Correlation Coefficients 178 Appendix G: Photographs of surface water sampling stations and methodology ......186 Appendix H: Geology of the Township of Langley Area 195 v i List of Tables Table 1.1 Suggested definitions for terminology commonly associated with phosphorus transfer from land to water 19 Table 4.1 Participants' perception of groundwater impact on surface waters (N=36) 36 Table 4.2 Number of wells on each aquifer within the study area and number of wells below detection limit for the different water quality parameters 40 Table 4.3. Summary statistics for groundwater quality parameters 40 Table 4.4 Spearman rank correlations for groundwater quality parameters for the dry season 42 Table 4.5. Spearman rank correlations for groundwater quality parameters for the wet season 42 Table 4.6 Significant Mann - Whitney U Test results (a<0.05) for surface water quality parameters 45 Table 4.7. Sites above detection limit for copper 54 Table 4.8. Descriptive statistics for elements in surface water 55 Table 4.9 Particle size distribution results for composite sediment samples collected July 2004 and February 2005 63 Table 4.10 Organic matter content of composite sediment samples 64 Table 4.11 Trace metal accumulation in sediments in relation to particle size 65 Table 4.12 Significant Mann - Whitney U Test results (a<0.05) for sediment quality parameters 67 Table 4.13 Spearman Rank Correlations between land use and groundwater quality parameters during the dry season 79 vii Table 4.14 Percent land use within stream buffers for the seven main categories identified in the Bertrand Creek watershed 80 Table 4.15 Percent land use within stream buffers for the categories used for correlation analysis 81 Table 4.16 Spearman Rank Correlations between surface water quality parameters and land use during the wet season 81 Table 4.17 Spearman Rank Correlations between sediment quality parameters and land use during the dry season 82 Table 5.1 Comparison between nitrate concentrations in groundwater (mg/L N0 3" - N) 86 Table 5.2 Concentrations of natural groundwater components 91 Table 5.3 Canadian Drinking Water Quality aesthetic objectives for dissolved elements in water and % of wells in the study exceeding the objectives 92 Table 5.4 2001 Census of Agriculture Data 92 Table 5.5 N0 3" - N concentrations in surface waters (mg/L) for studies in the Lower Fraser Valley 99 Table 5.6 Chloride concentrations in surface waters (mg/L) 101 Table 5.7 Summary of pH criteria according to the BC approved water quality guidelines ... 103 Table 5.8 Canadian water and sediment quality guidelines and background levels in British Columbia 106 Vll l List of Figures Figure 1.1. Location of the Township of Langley and the Bertrand Creek watershed 3 Figure 1.2. Land use within the Canadian portion of the Bertrand Creek watershed and location of surface water sampling stations 4 Figure 1.3 Aquifers in the Bertrand Creek watershed and nitrate concentrations in relationship to well depth 9 Figure 1.4 The Nitrogen cycle 15 Figure 1.5 The Phosphorus Cycle 20 Figure 4.1 Monthly precipitation in Aldergrove 34 Figure 4.2 Daily Mean Flow for Bertrand Creek 34 Figure 4.3 Daily Mean Flow for Pepin Creek 35 Figure 4.4 Well owners' perception of the quality of their water 35 Figure 4.5 Well owners' perception of the relative importance of different water quality indicators 37 Figure 4.6 Well owners' perception of the relative importance of different land use activities in causing water quality problems 38 Figure 4.7 Well owners' perception of the appropriateness of different groundwater management strategies 39 Figure 4.8 Correlation between N 0 3 - N concentrations and well depths....! 43 Figure 4.9 Number of wells showing high levels of nitrate in relation to depth 43 Figure 4.10 Correlation between P 0 4 - P concentrations and well depths 44 Figure 4.11 Median N0 3" - N concentrations per site in the Bertrand Creek watershed 46 Figure 4.12 Median orthophosphate concentration per site in the Bertrand Creek watershed.. 48 Figure 4.13 Median chloride concentration per site in the Bertrand Creek watershed 49 Figure 4.14 Median dissolved oxygen concentration per site in the Bertrand Creek watershed 50 Figure 4.15 Dissolved oxygen % saturation per site in the Bertrand Creek watershed 50 Figure 4.16 Median pH per site in the Bertrand Creek watershed 51 ix Figure 4.17 Median Specific Conductivity per site 52 Figure 4.18 Median temperature per site 53 Figure 4.19 Median [Ca] per site 55 Figure 4.20 Median [Mg] per site in the Bertrand Creek watershed 56 Figure 4.21 Median [Fe] per site in the Bertrand Creek watershed 57 Figure 4.22 Median [Mn] per site in the Bertrand Creek watershed 58 Figure 4.23 Median [K] per site in the Bertrand Creek watershed 59 Figure 4.24 Median [Na] per site in the Bertrand Creek watershed 60 t Figure 4.25 Median dissolved [Zn] per site in the Bertrand Creek watershed 61 Figure 4.26 Bioavailable concentration of Al and Zn in surface waters for the dry and wet seasons 62 Figure 4.27 Bioavailable concentration of Fe and Mn in surface waters for the dry and wet seasons 63 Figure 4.28 Trace metal accumulation in sediments in relation to particle size 66 Figure 4.29 Spatial and seasonal variations in Al concentrations in sediments 67 Figure 4.30 Spatial and seasonal variations in Ca concentrations in sediments 68 Figure 4.31 Spatial and seasonal variations in Mg concentrations in sediments 69 Figure 4.32 Spatial and seasonal variations in Fe concentrations in sediments 70 Figure 4.33 Spatial and seasonal variations in K concentrations in sediments 71 Figure 4.34 Spatial and seasonal variations in Mn concentrations in sediments 72 Figure 4.35 Spatial and seasonal variations in Cr concentrations in sediments 73 Figure 4.36 Spatial and seasonal variations in Ni concentrations in sediments 74 Figure 4.37 Spatial and seasonal variations in P concentrations in sediments 75 Figure 4.38 Spatial and seasonal variations in Cu concentrations in sediments 76 Figure 4.39 Spatial and seasonal variations in Pb concentrations in sediments 77 Figure 4.40 Spatial and seasonal variations in Zn concentrations in sediments 78 Figure 4.41 Seasonal variations in N0 3" - N concentrations on Bertrand Creek 83 Figure 4.42 Seasonal variations in N0 3" - N concentrations on Pepin and Cave Creeks 84 Figure 4.43 Seasonal variations in N0 3" - N concentrations on Howes Creek 84 Figure 5.1 Well owners' perception of groundwater quality in the Lower Fraser Valley 95 Figure 5.2 % of samples below B C water quality criteria for dissolved oxygen for the protection of aquatic life (all non - buried life Stages) 102 Figure 5.3 % of samples below BC water quality criteria for dissolved oxygen for the protection of aquatic life (all buried embryo/alevin life stages) 102 Figure 5.4 % of samples below BC water quality criteria for pH for irrigation purposes 104 xi Acknowledgements My deepest thanks go to my supervisor, Ken Hall, for all his patience, guidance, support, and advice. I consider myself very fortunate to have had the opportunity to work with such a respectable professional and wonderful person. Thanks for everything. To Hans Schreier for his patience and help, and especially for always taking the time to answer my questions and guide me through my research. Thank you Hans for sharing your knowledge. To Les Lavkulich for his input and recommendations to improve this thesis. Thank you Les for all your support and advice. To Paula Parkinson and Carol Dyck for their valuable help in the lab. A big "thank you" to Jenn MacDonald who has been a real lifesaver. Thanks Jen for all your help with GIS and for sharing with me some of your technical savvy. To Navjot Singh, Gabi Mejia, Ivett Ramos and Andrew Watts not only for their help with pictures, maps and out in the field, but also for making my field trips so much fun! I would like to thank all the students and staff at RMES who have made my time at UBC a wonderful experience. Special thanks go to Lisa Belanger, our graduate secretary, Sandra Brown and Trudy Naugler for all their support and assistance. I would like to thank the Organization of American States (OAS) for providing financial support to carry out my studies and the Canadian Water Network National Centre of Excellence for funding this research. Thanks to all my friends: Gabi and Funswa, Ronnie, Ivett and Sylvita for always cheering me up and never failing to "come to the rescue"... graduate school just wouldn't have been the same without you all. To my friends from afar: Hebert, Efra, Robin, Eileen and Magaly, for always being there for me through the distance; for putting up with all my quirks and most importantly, for always having words of hope and encouragement that never failed to lift my spirits. Most importantly, I'd like to thank my family: Mami, Papi, Cale and QKI for all their love and encouragement. Thank you for always being there for me. xu In loving memory of Papa Cesar December 1926 - March 2006 I would also like to dedicate this thesis to my cousin Estelita, for being such a great example of courage and faith Xlll 1 Introduction and Background Growing urbanization and agricultural intensification can negatively impact the quality of surface and ground waters, especially in vulnerable, unconfined aquifers and in surface watercourses that have little or no riparian buffer zones and receive direct surface runoff. In the Lower Fraser Valley in British Columbia, agriculture and urbanization pose a major stress on the area's water resources since population is rapidly increasing causing urban expansion and because the region is characterized by intensive agriculture that leads to excess use of pesticides, manure and fertilizers. Water courses in urban areas can also be impacted by trace metal contamination associated with vehicular traffic. In agricultural areas, trace metals from feed and additives such as antibiotics and hormones can negatively impact water since they are widely used in intensive livestock operations. There is growing concern on the negative impacts that excess nutrients from agricultural sources and other contaminants can have on water quality and aquatic biota. Excess nutrients from agriculture do not only impact surface waters, but can also get into groundwater through leaching, posing risks to human health when groundwater is used for drinking and other domestic purposes. In rural areas, people often rely solely on private wells for their domestic and drinking water supply, and have very little control over their drinking water quality. According to past surveys and studies, very few people in the rural areas filter, treat or test their well water on a regular basis [Magwood, 2004]. On the other hand, groundwater with high levels of nitrate and phosphate might impact surface water through stream recharge, especially during dry, low-f low periods, thus causing eutrophication problems. The city of Aldergrove is located in the southeastern part of the Township of Langley in B.C. It is a small but rapidly developing city just north of the rural area along the Canada - US international border. Due to this growth trend, the municipality of the Township of Langley needs to expand municipal water services by drilling new wells. Unfortunately, the Aldergrove aquifer is rapidly approaching its sustainable yield on its confined portion, and it is necessary to move towards the semi - confined portion of the aquifer, which is closer to the rural areas and is under the risk of nitrate contamination from agricultural sources [Piteau Associates and Turner Groundwater Consultants, 2003]. 1 There is growing concern that excess nutrients from agriculture are impacting ground and surface water in this area, and although there has been substantial research conducted on other aquifers in the area, such as the Abbotsford-Sumas and the US portion of the Bertrand Creek watershed, the Canadian portion of the watershed and the Aldergrove aquifer have escaped serious attention. It is, therefore, important to assess and monitor surface and ground water quality in this area in order to ensure the safe use of this valuable resource. A large number of measures and parameters of the water column, sediments, and biota can be used to achieve effective assessment and monitoring. These include total suspended solids (TSS) and total dissolved solids (TDS), turbidity, pH, conductivity, temperature, dissolved oxygen (DO), concentrations of inorganic chemicals, nutrients, synthetic organic chemicals, presence of pathogens and concentrations of toxic substances, as well as the structure of the biotic communities of the aquatic ecosystems. However, it is usually not feasible in terms of time, economic and human resources, to monitor all these parameters, and therefore, it is important to choose indicators that are scientifically defendable, reflect the seasonal variability observed in the environment, permit evaluation of historic trends in environmental quality, and measure the resilience of the system to change [Cook, 1994]. 1.1 Study Area The Township of Langley is located in the lower mainland of British Columbia, Canada, and is a member of the Greater Vancouver Regional District (GVRD) (F igure ! 1). Incorporated in 1873, the Township is made up of various communities, including Aldergrove, Brookswood/Fernridge, Fort Langley, Murrayville, Walnut Grove, Willowbrook and Willoughby. The Township occupies 316 square kilometers (122 square miles) and is home to approximately 91,000 residents [Township of Langley, 2005], of which about 20% live in agricultural areas. Approximately 75% of the Township is part of the agricultural land reserve, which accounts for almost 40% of the total agricultural land in the Lower Fraser Valley. The Township of Langley has an estimated 14 watersheds and 15 aquifers, many of which are highly vulnerable to contamination from land use activities because they are mostly unconfined and have rapid recharge times. The Township has been facing different issues related to its water resources, including reducing pollution and balancing development with municipal water supplies [Renton and Lynn, 2004]. 2 Figure 1.1. Location of the Township of Langley and the Bertrand Creek watershed within the Lower Fraser Valley. Adapted from: Golder Associates, 2005. The Bertrand Creek Watershed is located mostly in the southeastern part of the Township of Langley (Figure. 1.1) and partially located in the southwestern portion of the municipality of Abbotsford. The major portion of Bertrand Creek flows south through the city of Aldergrove on the Aldergrove aquifer, and across the border between British Columbia and Washington State on the Abbotsford/Sumas aquifer, where it becomes a tributary of the Nooksack River. Bertrand Creek is one of three streams in the Fraser Valley that flow south into the Nooksack River in Lynden, Whatcom County, Washington. Figure 1.2 presents a land use map of the Canadian portion of the Bertrand Creek watershed. This watershed is one of the few in North America that support populations of Salish sucker (Catostomus sp.) and Nooksack dace (Rhinichthys cataractae); two species on the Canadian and British Columbian Endangered Species List. Historically, Bertrand Creek was home to coho, chum, chinook, sockeye and pink salmon, cutthroat and steelhead trout, and numerous other fish species [BCES, 2004], but due to habitat degradation, there are very few fish left in the creek. 3 Figure 1.2. Land use within the Canadian portion of the Bertrand Creek watershed and location of surface water sampling stations The former BC Ministry of Environment, Lands and Parks reported that in 1992, 34 streams south of the Fraser River and west of Hope, were intensively surveyed for Salish sucker populations, but they were only found in 5 of those 34 streams. Only one specimen was found in Bertrand Creek and only juveniles were found in Cave Creek. Pepin Creek, on the other hand, was the only stream to have a healthy population of juvenile and adult suckers, probably because a portion of its course is through protected park land [BC Ministry of Environment, Lands and Parks, 1993]. For the purpose of this study, Bertrand Creek as well as its tributaries that form part of the watershed, were sampled. Pepin Creek, though it's not one of Bertrand Creek's tributaries, was also sampled, as it is a small, adjacent and transboundary watershed important to wildlife. Only the Canadian portion of the watershed was sampled, since stream and groundwater flow are mainly towards the south. 1.1.1 Groundwater Resources The Bertrand Creek watershed overlies several different aquifers in Southern BC, according to the 2005 Golder Report on Comprehensive Groundwater Modeling for the Township of Langley. These aquifers have been identified as the Abbotsford Aquifer, the Aldergrove AB Aquifer, the Aldergrove Quadra Aquifer, the West of Aldergrove Aquifer, the South of Hopington Aquifer, the Hopington C Aquifer, the Hopington AB Aquifer, the Beaver River Aquifer and the Langley Upland Intertill formation (Figure 1.3). Permeable units identified by Golder Associates retained the aquifer names used by the Environmental Protection Division of the BC Ministry of Environment (formerly the Ministry of Water, Land and Air Protection (MWLAP)). "In almost all cases, permeable units were subdivided into components using letter designations following the name. These letter designations are used in three different ways. In some cases, they represent different geological layers within a single permeable unit [Golder Associates, 2005]." In most other cases, as in the case of the Hopington Aquifer, the letters designate separate permeable units in what had been previously mapped as a single aquifer by the MWLAP. Thus, the Hopington A, B and C are interpreted to be 3 discrete permeable units with limited connection between them. However, the letters have also been used to designate where two separate permeable units have merged into a single unit, as is the case of the West of Aldergrove A and B which merge to form the West of Aldergrove C in the vicinity of Murrayville [Golder Associates, 2005]. Most of these aquifers consist mainly of sand and gravel, which makes them relatively vulnerable to contamination due to these materials' 5 high specific yield (10 - 20%) [Chapman, 1992]. A description of each of the aquifers underlying the Bertrand Creek watershed is presented below. Abbotsford Permeable Units (Abbotsford/Sumas Aquifer): The Abbotsford/Sumas, a largely unconfined aquifer, is an extensive sand and gravel deposit in southwestern BC and northwestern Washington State [Liebscher, et. al., 1992]. It covers approximately 200 km 2 (approximately 100 km 2 on each side of the international border), extends into Washington State and is bounded to the north by upland hills, to the east by the Sumas River, to the south by the Nooksack River and to the west by Bertrand Creek. Regional groundwater flow is generally towards the south, from the uplands towards the Sumas and Nooksack Rivers. Groundwater also flows locally, discharging into Pepin and Fishtrap Creeks and towards the large capacity production wells located along the eastern boundary of the aquifer. Annual recharge in the aquifer occurs through three main mechanisms: direct infiltration from rain or snow melt during the winter, runoff from the clay uplands to the north, and seasonal recharge from Fishtrap Creek [Liebscher, et. al., 1992]. Well yields in the Abbotsford/Sumas aquifer go up to as much as 125 Us and groundwater use is heavy. This is one of the most important aquifers in the entire province because of its productivity, size and heavy and varied use. The Abbotsford/Sumas aquifer is highly vulnerable to contamination from any surface sources. Historic groundwater sampling by Environment Canada and the B.C.Ministry of Environment, Lands and Parks indicate occurrence of elevated levels of nitrate and trace levels of pesticides in the aquifer [Liebscher, ef. al., 1992; Carmichael, ef. al., 1995, Wassenaar, 1995]. According to the aquifer classification system for groundwater management in British Columbia [Kreye, ef. al., 1998], this aquifer is classified as IA (20), which means that it is heavily developed, highly vulnerable and has a high priority for mapping and management. Aldergrove Permeable Units: The Aldergrove aquifer underlies the clay upland northwest of the Abbotsford/Sumas aquifer. It overlies part of the Beaver River aquifer and confined aquifers West and South of Aldergrove. As of 1995, the hydraulic connections between the Aldergrove aquifer and underlying aquifers were not known and the groundwater flow directions had not been mapped extensively. The 1993 Groundwater Mapping and Assessment in BC [Piteau Associates & Turner Groundwater Consultants, 1993], however, indicated that the groundwater flow for the upper Aldergrove aquifer is mostly towards the south. Groundwater use on the Aldergrove aquifer is moderate (reported well yields typically range up to & Us), though several wells exist throughout the 6 aquifer. The clay and stony clay unit overlying this aquifer offer protection from surface sources of contaminants [Carmichael ef. al, 1995]. According to the aquifer classification system for groundwater management in British Columbia [Kreye, ef al, 1998], the Aldergrove aquifer is classified as IIC (14), meaning that it is a moderately developed and a low vulnerability aquifer. It has been assigned a ranking value of 14 (out of a maximum of 21) for priority for mapping and management. The West of Aldergrove aquifer has been classified as IIIC (9), is approximately 22 km 2 in size and moderately productive with a low vulnerability and demand. The South of Aldergrove Aquifer has been classified as IIIC (8), is only 9 km 2 in size, moderately productive with low vulnerability and demand. The more recent report on comprehensive groundwater modeling carried out by Golder Associates (2005) states that "the Aldergrove permeable units form several discrete bodies of primarily glaciomarine outwash sands and gravels within the Fort Langley Formation." According to this report, the Aldergrove aquifer, as previously defined by the Ministry of Environment, has been subdivided into Aldergrove A, Aldergrove B, Aldergrove C and Aldergrove D. The Aldergrove A boundaries are defined within the eastern part of the Township of Langley from 8 t h to 48 t h avenues, and extends as far east as 296 t h street in Abbotsford. Towards the north, the Aldergrove A might be connected with the Aldergrove C, which occurs deeper within the Fort Langley formation and which can be recognized from 48 t h avenue north. It may be locally connected with the underlying Beaver River A north of 64 t h avenue. The Aldergrove B is an apparently isolated body of Fort Langley sand and gravel immediately west of the limits of the Aldergrove A. The Aldergrove D occurs further west and can be recognized north of 72 n d avenue. It may locally be connected with the Hopington B [Golder Associates, 2005]. The South of Aldergrove permeable unit is between 20 and 40 meters in elevation and consists mainly of sand and gravel. It is located in the southeast corner of the Township of Langley between 8 t h and 24 t h avenues and east of 264 t h street. It extends eastward into Abbotsford. It underlies the Aldergrove A and is separated from it by glaciomarine clay and till, although locally the base of Aldergrove A is incised down into the top of the South of Aldergrove and the permeable units are connected [Golder Associates, 2005]. 7 The West of Aldergrove A consists of sands and gravels and is generally between 5 and 15 meters thick. The West of Aldergrove B occurs 20 to 40 meters deeper than the West of Aldergrove A and is generally 5 to 20 meters thick. It can be traced over a large area from 16 t h to 56 t h avenues and 216 t h to 264 t h streets. In the area west of Hopington, the Aldergrove A and B merge to form the West of Aldergrove C, resulting in a permeable unit that is up to 40 meters thick [Golder Associates, 2005]. The Aldergrove Quadra permeable unit is composed of sand and gravel and spreads from the northeast to the southeast corner of the Township between +20 and -20 meters elevation. The permeable unit occurs below till and above a thick interval of silt and clay. Water from this permeable unit has commonly been reported to be brackish in nature [Golder Associates, 2005]. South of Hopington Permeable Units: The South of Hopington Aquifer is classified as IC (11), is 23 km 2 in size, with high demand and low productivity and vulnerability [BC Ministry of Environment]. The Golder Associates' 2005 report links the South of Hopington to the West of Aldergrove permeable units and states that they are a complex of intertill permeable units located in the central part of the Township. According to this report, the base of the Hopington C is incised into the West of Aldergrove A in a large area south of Hopington. The South of Hopington A, which is generally between 10 and 20 meters thick, occurs south of the area where the Hopington C and the South of Aldergrove are merged. Beaver River Permeable Units: Two permeable units of different depths are described by Golder Associates (2005). The shallower one, the Beaver River A, consists of sand and gravel and descends from 40 meters above sea level to 20 meters below sea level. The deeper formation, the Beaver River B is continuous with and equivalent to the South of Murrayville A. It is between 5 and 10 meters thick and extends from 24 t h avenue and 216 t h street to the northeast corner of the Township of Langley. Langley Upland Intertill Permeable Unit: Located in the southwest corner of the Township, it is primarily defined in the vicinity of 24 t h avenue, between 208 t h and 232 n d streets, where it forms a ramp of sand with some gravel up to 10 meters thick, between sea level and -20 meters elevation [Golder Associates, 2005]. 8 Cimiulit - VS htterttationat Borfler Legend w e l l s > 1 0 m g / L N 0 3 - N a n d < 1 5 m d e e p 1 , 5 0 0 • w e l l s < 3 m g / L N 0 3 - N a n d < 1 5 m d e e p • • w e l l s < 3 m g / L N 0 3 - N a n d 1 6 - 2 9 m d e e p + s t r e a m s t a t i o n s •k w e l l s < 3 m g / L N 0 3 - N a n d > 3 0 m d e e p — — s t r e a m s o w e l l s 3 - 1 0 m g / L N 0 3 - N a n d < 1 5 m d e e p I I w a t e r s h e d b o u n d a r y • w e l l s 3 - 1 0 m g / L N 0 3 - N a n d 1 6 - 2 9 m d e e p A b b o t s f o r d A q u i f e r H o p i n g t o n C A q u i f e r S o u t h o f H o p i n g t o n A q u i f e r W e s t o f A l d e r g r o v e A q u i f e r L a n g l e y U p l a n d Intert i l l H o p i n g t o n A B A q u i f e r 1 , 5 0 0 M e t e r s B e a v e r R i v e r A q u i f e r A l d e r g r o v e Q u a d r a A q u i f e r A l d e r g r o v e A B A q u i f e r Figure 1.3 Aquifers in the Bertrand Creek watershed and nitrate concentrations in relationship to well depth (adapted from Golder Associates, 2005) 1.2 Water Quality Parameters and Indicators 1.2.1 Temperature Temperature is one of the most important water quality parameters, since it affects most physical, biological and chemical processes in water bodies. In turn, water temperature can be affected by different factors, such as riparian vegetation, flow rate, paved surfaces, industrial discharge and sewer outflow [Murphy, 2005]. As water temperature increases, so does the rate of chemical reactions and the evaporation and volatilization of substances from the water [Chapman, 1996]. Temperature affects the solubility of gases (including oxygen and C 0 2 ) in water, which typically tends to decrease as temperature increases. Furthermore, increasing temperatures not only reduce the solubility of oxygen in water, but they also increase metabolic rates of aquatic species, increasing the demand for oxygen. Warmer waters also support faster growth rates and can enable some biota (such as algae) to attain significant populations. By affecting the solubility of C 0 2 in water, temperature also affects pH. C 0 2 enters a water body from a variety of sources, including the atmosphere, runoff from land, release from bacteria in the water, and respiration by aquatic organisms. This dissolved C 0 2 forms a weak acid, therefore lowering pH in water [Murphy, 2005]. 1.2.2 Dissolved Oxygen (DO) Monitoring levels of dissolved oxygen in bodies of water is important as oxygen is involved in or influences nearly all chemical and biological processes in water and is essential to all forms of aquatic life, including those organisms responsible for the self - purification processes in natural waters. Oxygen content in water varies with temperature, salinity, turbulence, photosynthetic activity and atmospheric pressure. Waste discharges high in organic matter and nutrients can lead to lower concentrations of DO. DO concentrations below 5 mg/L may adversely affect the survival of biological communities and below 2 mg/L may lead to the death of most fish [Chapman, 1996]. 1.2.3 Chloride in Surface and Ground Waters The Canadian Drinking Water Quality Guidelines set an aesthetic objective of < 250 mg/L for drinking water, since concentrations higher than this might impart undesirable tastes to water and may cause corrosion of pipes in the distribution systems. Sodium chloride is widely used in the production of industrial chemicals such as caustic soda (sodium hydroxide), chlorine, soda ash (sodium carbonate), sodium chlorite, sodium 10 bicarbonate and sodium hypochlorite. Potassium chloride is used in the production of many fertilizers. The presence of chloride in water sources can be attributed to the dissolution of salt deposits, salting of highways for the control of snow and ice, effluents from chemical industries, oil well operations, sewage, irrigation drainage, refuse leachates, volcanic emanations, sea spray and sea water intrusion in coastal areas [Health Canada, 1979a]. The chloride ion has been widely used as a tracer (particularly in the pollution of wells) and is considered a useful indicator of human influence on water quality. 1.2.4 Total Suspended Solids (TSS) and Turbidity The type and concentration of suspended matter controls the turbidity/transparency of water. Suspended matter may consist of silt, clay, fine particles of organic and inorganic matter, soluble organic matter compounds, plankton and other microorganisms. It is common practice to accept, as an operational definition, that particulate matter refers to particles > 0.45 pm and is primarily derived from rock weathering processes and may be further modified by soil -forming processes [Chapman, 1996; Health Canada, 2003]. ln river systems, the concentration of T S S varies dramatically with changes in discharge. Resuspension of fine - grained bottom sediment with increasing discharge is the cause of the major increase in suspended solids. Furthermore, at a given river station, T S S can often be related to turbidity measurements. Thus, turbidity can be used as an indirect measurement of TSS . Turbidity is a measurement of how light scatters through water, and not a measurement of suspended particles themselves. Turbidity should ideally be measured in the field, but if this is not possible, it can be measured in the lab (provided that samples are stored in the dark and for no longer than 24 hours) by means of nephelometry. However, settling during storage and precipitation caused by pH changes can lead to alteration of results [Chapman, 1996]. It is only recently that drinking water quality guidelines are being developed for turbidity. There is an increasing concern with the health implications of high turbidity since suspended matter can contain heavy metals and biocides and can also harbor microorganisms, protecting them from disinfection measures. Recent research has correlated turbidity levels with treated water supplies being contaminated with Giardia spp. and Cryptosporidium spp. Furthermore, turbidity can lead to the increase of Trihalomethanes in treated water when chlorine reacts with the organic material in the water [Health Canada, 2003]. 11 1.2.5 Total Dissolved Solids (TDS) and Conductivity Total Dissolved Solids (particles <0.45 um), on the other hand, can be measured from conductivity (specific conductance) values, by multiplying conductance by a factor commonly between 0.55 and 0.75 (usually 0.67) [Ministry of Environment, Lands and Parks, 1999]. While the conductivity of most freshwater systems ranges between 10 - 1000 uS/cm, it may exceed this top value, especially in polluted waters and those receiving large quantities of land runoff. Therefore, conductivity and TDS can be useful in establishing pollution zones [Chapman, 1996]. Conductivity and TDS are typically higher in groundwater than in surface waters, due to the mineral contribution from geological sources. TDS comprise inorganic salts and small amounts of organic matter that are dissolved in water. Other sources of total dissolved solids include sewage, urban and agricultural runoff and industrial wastewater. The major contributors are usually calcium, magnesium, sodium, potassium, carbonate, bicarbonate, chloride, sulphate and, particularly in groundwater, nitrate [Health Canada, 2003]. Health Canada (2003) also states that TDS concentrations affect palatability of water and some components such as chlorides, magnesium, calcium, sulphates and carbonates can affect corrosion or encrustation in water distribution systems. 1.2.6 Trace Elements in Water and Sediments Essential elements are those necessary to complete an organism's life cycle, are required for a specific physiological function and can't be substituted by another element. These include Nitrogen, phosphorus, potassium, calcium, magnesium, sulfur, boron, chlorine, iron, manganese, zinc, copper, molybdenum, and nickel [Barak, 1999]. Micronutrients are minerals needed in very small amounts by living things. From the above mentioned essential elements, Cl, Fe, B, Mn, Zn, Cu, Mo and Ni can be considered trace elements/micronutrients and N, K , Ca, Mg, P and S can be considered macronutrients [Barak, 1999]. The typical dietary requirement for a trace element is less than 50 ppm, with organisms usually showing a very limited range of tolerance to deviations from the required amount [Pais and Jones, 1997]. Trace elements are present in water in small concentrations, but when these concentrations are higher than normal, there might be some toxic effects. The metabolic function of these elements is varied but commonly related to the enzymatic system, either as a structural part of various enzymes or as catalysts of their functions. A few form minor but essential structural components of specialized compounds such as chlorophyll or hemoglobin [Pais & Jones, 12 1997]. Water and sediment pollution by heavy metals due to human activities is causing serious problems worldwide and this situation is worsened by the lack of natural elimination processes for metals. Due to processes such as adsorption and accumulation, the concentration of metals tends to be higher in sediments than in the water column. Dissolved metals occur in very low concentrations, so it is sometimes better if they are measured in particulate matter, since more than 50% of the total metals present (and up to 99.9%) is usually adsorbed onto suspended particles and sediment particles (mainly clay fraction). However, it is the dissolved fraction of metals that is more likely to cause toxicity problems to aquatic organisms, since it is more readily available. Chelation is the ability of organic compounds to bind metal ions and maintain them in solution. Examples of chelating agents include humic and fulvic acids (present is Dissolved Organic Carbon - DOC) and compounds such as EDTA (ethylenediaminetetraacetic acid) [Chapman, 1996]. These compounds can also slowly release bound metal ions back into the water. Therefore, chelating capacity depends on the content humic/fulvic acids and other ligands as well as on the hardness of water. This implies that the toxicity of trace metals to different aquatic biota species will also vary in relation with water hardness. For example, the toxicity of Cu and Zn is highly variable depending on the concentration of Ca in the water - in general, the higher the concentration of calcium, the lower the toxicity of these two metals. In general, acidification can result in the mobilization of Hg and Cd, both of which are highly toxic and bioaccumulative. The total fraction of metals is defined as that which doesn't filter through a 0.45 pm membrane, while the bioavailable fraction (most readily available for uptake by different aquatic organisms) does pass through such membrane (<0.45 pm) [Brydon, 2004]. The use of Diffusive Gradients in Thin Films (DGTs) constitutes an innovative technique to determine the bioavailable fraction of metals in solution, as they have the capacity to mimic cellular ion exchange mechanisms. DGTs are the first diffusive passive samplers for ions in water that take full advantage of diffusion theory for calculations of time averaged concentrations [Garmo, et. al., 2003]. In the chelex resin used in DGTs, the quantity of cations exchanged is a function of pH, being very low under pH 2, increasing sharply between pH 2 and 4 and reaching a maximum above pH 4. Any metal removed from solution is replaced by an equal amount of the ions originally in the resin [Bio-Rad Laboratories, 2000]. 13 1.2.7 Nutrient Pollution 1.2.7.1 Nitrogen and the Nitrogen Cycle Nitrogen is an essential nutrient for all organisms as it is a main component of proteins and nucleic acids. It is also the most abundant gas in the atmosphere (about 78% by volume). Nitrogen can undergo various transformation processes. These processes are briefly described below and Figure 1.4 presents a schematic summary of nitrogen cycle. • Nitrogen Fixation - Some bacteria {Rhizobium, Bradyrhizobium) and some cyanobacteria and actinomycetes have the ability to convert atmospheric nitrogen (N2) into an organic form of nitrogen [Schreier, et. al., 2001]. The triple bonded dinitrogen molecules are reduced to ammonia via an enzymatic process. Nitrogen fixation by phytoplankton tends to decline as ammonia and nitrate concentrations in the water increase and as the ratio total nitrogemtotal phosphorus in water increases. • Mineralization - Conversion of organic forms of nitrogen to inorganic forms. Bacteria and other organisms decompose organic matter. Part of the nitrogen in organic matter is converted to organic nitrogen in microbial biomass and the rest is released to the environment as ammonia [Boyd, 2000]. • Immobilization - conversion of inorganic forms of nitrogen to organic forms. • Nitrification - the oxidation of ammonia nitrogen to nitrate by chemoautrophic bacteria (Nitrosomonas and Nitrobacter). This process is most rapid at temperatures between 25 to 35°C and at pH between 7 and 8. Some bacteria can carry out the anaerobic oxidation of ammonia, using nitrate as the source of oxygen to oxidize ammonium to nitrogen gas [Boyd, 2000]. • Denitrification - is the reduction of N0 3" to gaseous forms of nitrogen by heterotrophic bacteria and is regulated by the availability of N0 3", carbon sources and anaerobic or low oxygen conditions [Schreier, et. al., 2001]. This process yields 1 mole of OH" for every mole of N0 3", thus contributing to the alkalinity of water. 14 Figure 1.4 The Nitrogen cycle Source: UCAR, 2005 1.2.7.2 Nitrogen: Sources and Impacts Sources of nitrogen to surface waters include atmospheric dry and wet deposition, gaseous exchange at the water's surface, nitrogen fixation, organic matter, lawn and garden fertilizer products carried in runoff, and manure and fertilizers used in excess in agriculture and carried in runoff to receiving waters. Nitrogen, in the form of nitrate mainly, can reach groundwaters through leaching from the soils and from failing septic systems due its high mobility. Because available nitrogen can be a limiting factor in many aquatic ecosystems, plant growth often increases in response to increased nitrogen concentrations. However, the concentration of nitrogen necessary to cause excessive phytoplankton blooms in natural waters is difficult to determine, since many factors apart from concentration influence phytoplankton productivity. Concentrations of 0.1 - 0.75 mg/L of ammonia nitrogen plus nitrate nitrogen in freshwaters have usually been adequate to cause phytoplankton blooms [Boyd, 2000]. 15 One of the most commonly identified contaminants found in groundwater is nitrate ( N 0 3 ) . Nitrate and nitrite ( N 0 2 ) are naturally occurring ions that are ubiquitous in the environment and both are products of the oxidation of nitrogen by microorganisms in plants, soil, or water and, to a lesser extent, by electrical discharges such as lightning [Health Canada, 1992]. Nitrate is the most stable form of oxidized nitrogen but can be reduced by microbial action to nitrite, which is moderately chemically reactive. Nitrates are highly soluble and easily incorporated into local surface and groundwaters. Where found in significant concentrations, they can be used as an indicator of contamination from local land use activities and as a relatively low-cost indicator of point and non point source pollution. Elevated nitrate concentrations in a given area can be a signal of potential groundwater contamination by fecal coliforms, solvents, pesticides and other contaminants [Liebscher, et. al., 1992]. Nitrate has been proposed as a useful indicator for pathogen contamination, especially because high nitrates in water can originate from exposed manure stockpiles, manure soil enhancement, septic effluent discharges (failing septic systems), and applications of manure as well as chemical fertilizers. However, several studies cited by Magwood (2004) have shown that, in general, private wells exceed water quality guidelines for fecal and total coliforms more often than for nitrate. These same studies show very little correlation between wells that exceed levels for both of these parameters. Though a clear linkage between nitrate levels and fecal/total coliforms has not yet been established, measuring nitrate levels in drinking water requires less effort and is less costly than culturing microorganisms. High nitrate levels in surface and groundwater are of concern because of potential nutrient enrichment of waters (especially when rivers carry excess nitrate to the ocean, where it is the limiting nutrient and can cause eutrophication of coastal zones), the economic cost of loss of fertilizer nitrogen, and mainly because of the potential adverse effects on human health [Cook, 1994]. In general, nitrate levels are higher in well water (drinking water supply in rural areas) than in surface water. In an Environment Canada survey of groundwater in the Fraser Valley, B C [Liebscher, et. al., 1992], 60% of the wells (450 samples in 125 locations) were found to have nitrate levels exceeding 10 mg/L N 0 3 " - N, the Maximum Acceptable Concentration (MAC) according to the Guidelines for Canadian Drinking Water Quality (2003). 16 The adverse effects of high levels of nitrate on human health include methaemoglobinaemia (Blue Baby Syndrome), which is probably the most commonly reported toxic effect of the ingestion of nitrate-contaminated water. Methaemoglobinaemia occurs when nitrate is reduced to nitrite in the oral cavity and stomach; nitrite in turn oxidizes the reduced F e + 2 in hemoglobin to F e + 3 . The resulting methaemoglobin (MeHb) is unable to release oxygen to body tissues because of its high dissociation constant. Reduced oxygen transport is noted clinically when MeHb concentrations reach 10% or more. Symptoms include cyanosis, and at concentrations of 80% or more, asphyxia and even death. Babies under 3 months of age are the most susceptible to this disorder, with the exception of pregnant women and people with genetically controlled deficiencies of the enzymes glucose-6-phosphate dehydrogenase or methaemoglobin reductase [Health Canada, 1992]. Other health concerns associated with the ingestion of high levels of nitrate might include potential carcinogenicity. In the human stomach, nitrates can react with compounds such as amides and amines, to form N - nitroso compounds. Some N - nitroso compounds are potent carcinogens in animal species and are therefore probably carcinogenic in humans. However, epidemiological evidence linking intake of nitrate/nitrite with gastric cancer in humans has been equivocal and further research is needed in this area. Other effects might include birth defects and behavioral changes as well as possible changes in perceptual vigilance. All these, however, warrant further studies [Health Canada, 1992]. 1.2.7.3 Phosphorus: sources and impacts Even though there is no established health standard for phosphorus in drinking water, elevated phosphorus levels in surface waters are of concern because they enhance the production of algae and thus, encourage eutrophication (especially in lentic bodies of water). Accelerated eutrophication can significantly limit the use of surface waters for drinking, domestic purposes, industry, recreation or the fishing industry. Eutrophication is characterized by excessive algal growth, which can generate taste and odor problems in drinking water. The ecological consequences of eutrophication include (but are not limited to) anoxia due to algal decomposition and fish kills, and a rapid shift in the species composition of biological communities. Natural sources of phosphorus are mainly the weathering of phosphorus-bearing rocks and the decomposition of organic matter [Chapman, 1996]. Anthropogenic sources of phosphorus to aquatic systems include point-source discharges of urban and industrial wastewater and 17 non point sources from urban and agricultural runoff and erosion where it is mainly applied as a plant nutrient to the land surface as inorganic fertilizer, animal manure or sewage sludge [Cook, 1994]. The BC Ministry of the Environment 1991 objectives for the concentration of total phosphorus in fresh water were set from the perspective of the protection of water bodies from eutrophication. For lakes, the objectives were usually between < 0.010 to < 0.015 mg/L. However, for some lakes the objective was as high as < 0.075 mg/L and no objective for total phosphorus for BC rivers has been set to date. According to Chapman (1996) phosphorus concentrations in most natural surface waters range from 0.005 to 0.02 mg/L P 0 4 - P. In pristine waters, concentrations as low as 0.001 mg/L P 0 4 - P can be found. Average groundwater concentrations are about 0.02 mg/L P 0 4 - P. The presence of phosphorus in groundwater can have significant environmental impacts, since even small additions of this nutrient to surface waters (when groundwater recharges streams or lakes) can increase nutrient loading and eutrophication. McGarrigle, ef. al., (2002) mention that groundwater levels of orthophosphate - P should not exceed 0.03 mg/L when providing baseflow to a river, or 0.02 mg/L total phosphorus if feeding a lake. Phosphorus has low solubility and mobility and is therefore primarily found bound to particulate material. Therefore, in terms of phosphorus transfer, the importance of soil erosion and physical transfer with soil particles from land to water has been highlighted by many different studies [Haygarth, etal., 2005]. Solubilization and detachment mechanisms defined by particle size are the main phosphorus mobilization processes. Table 1.1 provides a reference for key terms and definitions associated with phosphorus transfer from land to water. 18 Table 1.1 Suggested definitions for terminology commonly associated with phosphorus transfer from land to water T E R M Transfer/ transport DEFINITION Generic term that describes phosphorus movement through the land - water continuum. Loss Specific term often used to describe phosphorus "loss" from soil. Source Refers to the raw inputs of phosphorus to the agricultural system, such as fertilizer, feed, mineralized from soil or atmospheric deposition. Mobilization Describes the start of the phosphorus transfer, the process by which phosphorus molecules begin movement from soil. May be solubilization or detachment. Detachment Physical process of mobilization that involves phosphorus attached to soil particles or colloids Solubilization Biological or chemical process of mobilization. Incidental A mobilization process that occurs when rain and runoff interact directly with fresh applications of phosphorus on the soil surface (fertilizers and manure). Delivery Describes the linkage from the spatial and temporal point of mobilization to the point of canalized flow. Impact Describes the biological and ecological effect that results from the presence of phosphorus in running and standing waters Source: Haygarth, et. al., 2005 1.2.7.4 Phosphorus and the Phosphorus Cycle Phosphorus in soils can be organic or inorganic. Organic forms are found in humus and other organic material. This might be released by a mineralization process that involves soil organisms. Organic forms of phosphorus are not absorbed by plants. On the other hand, inorganic phosphorus is negatively charged in most soils and reacts readily with iron, aluminum and calcium to form relatively insoluble substances. The solubility of inorganic phosphorus compounds directly affects the availability for plant growth. Soil phosphorus is most available between pH 6 and 7. Below pH 6, it becomes insoluble in aluminum phosphates and as soils become more acidic (pH below 5), it tends to bind with iron to form iron phosphates. When pH is above 7.3, phosphorus combines with calcium to form calcium phosphates [MSU online soils publication]. 19 The phosphorus cycle is unique when compared to other biogeochemical cycles because it does not include a gaseous phase, though small amounts of phosphoric acid (H 3 P0 4 ) may make their way into the atmosphere contributing in some cases to acid rain. Also, it doesn't include any oxidation/reduction reactions, which predominate in the nitrogen cycle. The largest reservoir of phosphorus is sedimentary rocks and the cycle begins with the introduction of phosphate to soils through the weathering process. Plants then uptake phosphate and it is passed along the food chain. It is then returned to soils by excretion and decomposition. These processes are similar in water. In addition, phosphorus can enter aquatic ecosystems from surface runoff, especially that containing much suspended sediment [Environmental Literacy Council, 2002]. Figure 1.5 shows a schematic representation of the phosphorus cycle. Copyright © Pearson Education. Inc , publishing as Benjamin Cummings Figure 1.5 The Phosphorus Cycle Source: Krempels, university course website 20 2 Goals and Objectives Study Goal The goal of this study is to determine the impacts of urban and agricultural land uses on streambed sediment, ground and surface water quality in the Bertrand Creek Watershed. Objectives To determine the spatial and temporal variability in groundwater quality in the Aldergrove area and surface water quality in the Bertrand Creek watershed, with a main focus on nutrients. To explore private well owners' perception of water quality. To evaluate spatial and temporal variations in the concentration of trace metals in fine-fraction streambed sediments. To determine the bioavailable fraction of trace metals in water in Bertrand Creek by using the Diffusive Gradient in Thin Films technique (DGT). To quantify land use using GIS techniques and determine possible relationships between land use activities and sediment, surface and groundwater quality. 21 3 Methodology This research study comprised four main parts: 1. A survey conducted with selected private well owners in the Aldergrove area to obtain information on groundwater quality/quantity issues and their perceptions on drinking water quality. 2. Analysis of groundwater to determine quality for drinking according to the Canadian Drinking Water Quality Guidelines. 3. Monitoring and analysis of surface waters and streambed sediments to determine spatial and temporal variability of water and sediment quality. 4. Incorporation of land use information available from maps and orthophotos into a GIS, and identification of relationships between land use, sediment quality and water quality through the use of statistical techniques. 3.1 Survey to Private Well Owners Private well owners within the study area were invited to participate in the study through letters, trying to achieve a representative sample across the watershed that took into consideration well - depth and spatial distribution. Three hundred letters of invitation and surveys were distributed randomly in residents' mailboxes, within the following boundaries in the study area: in the Aldergrove or Abbotsford Aquifer areas south of 24 t h Av; east of 248 t h St (Otter Road); west of 288 t h St (Bradner Road) and north of the Canada - USA border. Residents agreeing to participate in the study completed and returned the survey in the postage-paid envelopes provided. The survey used in this study had been previously used in similar studies [Goble, 2005; Magwood, 2004 - adapted from Schreier, et. al., 1996]. The survey aimed at providing information on the conditions of wells (age and depth of wells and number of people served by well), well water uses per household, land uses within 100 m of the wells, well water treatment (if any) and the perception of well owners of their well water quality and quality/quantity problems. 22 Survey responses were used to calculate the percentage of owners who treat their well water for drinking and to explore well owners' perceptions of their water quality and quantity. In return for participating in the study and providing water samples at two different times in the year, participants received the results of the water quality analysis of their wells. Copies of the letter of invitation to participate in the study, the groundwater survey and results letter are included in Appendix A. 3.2 Groundwater Sampling and Analysis In the study, private wells were sampled because this is the most practical way to have a variety of sampling points that are representative of the study area and get a good overview of the water quality, avoiding the costs of creating new infrastructure such as boreholes or monitoring wells [Magwood, 2004] and reducing the labor of sample collection which can increase costs. A study conducted by Erickson (2000) compared the effectiveness of having volunteer well owners sample their own wells for nitrate vs. the efficacy of using a commercial test kit to determine nitrate concentrations and it concluded that the use of volunteer well owners in a monitoring program appears to be feasible, provided people collecting the samples are properly instructed and they follow instructions carefully. However, when well owners are to deliver/mail their samples back, this can take up to 3 days [Liu, et. al., 2004]; period during which denitrification can occur, thus altering the results of the analysis. In order to avoid this problem, samples should be picked up and stored on ice as soon possible after they have been collected, and transported to the laboratory for analysis. Another way to deal with this situation is to provide well owners with sampling bottles containing a preservative. Participating well owners were given notice of the sampling dates by phone and/or e-mail and received a set of acid washed bottle(s) and printed out instructions on how, when and what time to collect their samples. Participants were instructed to run their taps for 5 minutes before filling up the bottles to minimize the influence of water pipes on water quality and were also advised not to leave their samples exposed to direct sunlight or extreme heat. In case of having a filtering system in place, they were asked to collect the sample before filtering. Groundwater sampling took place in early October 2004 (low water table) and mid-February 2005 (high water table) to assess temporal variability in quality. Samples for both sampling events were picked up at each participant's home 1 to 3 hours after collection and transported to UBC's Environmental Engineering Laboratory to be analyzed for nitrate, phosphate and 23 chloride using a Lachat flow injection autoanalyzer. Methods and detection limits used for analysis are as follows: for N0 3 ' - N0 2" the method used was 4500 - N0 3" - I Cadmium Reduction Flow Injection with detection limit of 0.002 mg/L N; for P 0 4 the method was 4500 -P - G Flow Injection Analysis for Orthophosphate, detection limit 0.01 mg/L P and for Chloride analysis the method used was 4500 - Cl - G Mercuric Thiocyanate Flow Injection Analysis with a detection limit of 0.5 mg/L Cl". Samples for nitrate and phosphate analysis were preserved in test tubes using 1 drop of phenyl mercuric acetate and stored in a fridge until analyzed. In the laboratory, a Beckman $ 44 pH meter, a Hach 21 OOP Turbidimeter and a CDM3 (Radiometer Copenhagen) conductivity meter were used to measure pH, turbidity and conductivity respectively. Specific conductivity of the samples was calculated from conductivity. Total Dissolved Solids were, in turn, calculated from specific conductivity values. In addition to nutrients and chlorides, February samples were analyzed for 10 dissolved elements using a Varian Vista-Pro C C D Simultaneous Inductively Coupled Plasma - Atomic Emission Spectrometer (ICP-AES) in the Soils Department Laboratory at UBC. Dissolved elements analyzed and their respective detection limits in mg/L are listed below: 3.3 Surface Water Sampling and Analysis Thirteen sampling stations were selected on Bertrand, Howes, Pepin and Cave Creeks to assess spatial variation on water quality trends. The stations were located as follows: 7 stations on Bertrand Creek (3 on the urban portion of the watershed and the rest on the rural area), 2 stations on Pepin Creek, 3 stations on Howes Creek and 1 on Cave Creek (see Figure 1.2). Of these 13 stations, 3 are located at the Canada - US border: 1 on Bertrand Creek, 1 on Pepin Creek and 1 on Cave Creek. The border station on Bertrand Creek has a seasonal flow gauge operated by Environment Canada, from which flow data was obtained. Streams were monitored for temperature and specific conductivity in the field using a Yellow Springs Instrument Co. (YSI) model #30M/50 Fl meter. Dissolved oxygen was also measured in the field using a YSI model #58 meter. Streams were monitored approximately once a month for a one-year period to assess temporal variability. Grab samples were collected Ca (0.1) Cu (0.05) Fe (0.05) K (0.5) Mg (0.01) Mn (0.005) Na (0.25) Si (0.15) Sr (0.002) Zn (0.01) 24 during each sampling event to monitor pH and turbidity in the Environmental Engineering Lab at UBC, using a Beckman 0> 44 pH meter and a Hach 21 OOP Turbidimeter. Samples for nutrient and chloride analysis were also collected during each sampling trip and filtered in the field using Porex blood and serum filters. Samples were then put in test tubes containing one drop of phenyl mercuric acetate to preserve samples for nitrate analysis and then carried back to the Environmental Engineering Lab (UBC) for analysis on a Lachat flow injection autoanalyzer. The same methods and detection limits as for analysis of nutrients and chlorides in groundwater were used. Water samples for July, August, October and December 2004 and February 2005 were acidified using 0.5 ml H N 0 3 and analyzed for major cations in the soils department laboratory art UBC. Elements analyzed and detection limits are the same as those for groundwater analysis. 3.4 Use of DGTs and Analysis of Bioavailable Trace Metals in Surface Waters DGTs (Diffuse Gradients in Thin Films) were set up at five sampling sites on Bertrand Creek (BCr1, BCr3, BCr4, BCr11 and BCr12) with a duplicate at the last site, twice during the study period (July 2004 and February 2005) to determine the bioavailable fraction of trace metals in water. DGTs were deployed for a period of 3 weeks each time. Field procedures for deployment and retrieval were carried out according to the DGT Research Ltd. instruction manual (2002). A summary is provided below: 1. DGTs were taken out to the field in a cooler and only removed from their original sealed plastic bags until immediately prior to deployment. 2. DGTs were suspended a few inches from the stream bottom (making sure they were not touching the bottom, but completely under water) by using mono filament fishing line and a rock (for added weight) and anchored to a branch, tree, etc on the stream bank. Areas of flowing water, but avoiding excessive turbulence and bubbles, were selected for deployment of the units. 3. Time of deployment and retrieval was recorded to the nearest minute and temperature upon deployment and retrieval was recorded using the YSI conductivity meter. 4. Upon retrieval, DGTs were rinsed with deionized water avoiding touching the surface and placed in individual, labeled plastic bags. They were then placed in a cooler and taken to the Soils Department laboratory. [Smith, 2004] 25 In the laboratory, the devices were opened by inserting a screwdriver into the groove on the side of the DGT units and twisting. The filter and diffusive gel layer were removed using plastic tweezers and the chelex resin gel was placed in acid washed bottles containing 20 ml of 1M H N 0 3 solution. The resins were left in the solution for at least 72 hours prior to the ICP - A E S analysis [Smith, 2004]. A summary of the calculations used to determine DGT measured concentrations, follows [from DGT Research, 2002]: 1. calculate mass of metal in the resin gel (M) M = Ce (V H N o3 + Vgei) / fe where: Ce = [ ] of metals in the 1M H N 0 3 (ug/L) VHNO3 = volume of H N 0 3 added to the resin gel Vgei = volume of resin gel (typically 0.15 ml) fe = elution factor for each metal (typically 0.8) 2. Calculate concentration of the metal measured by the DGT (C D G T ) CDGT = MAg/DtA where: Ag = thickness of the diffusive gel (0.8 mm) + thickness of the filter membrane (typically 0.14 mm) D = diffusion coefficient of metal in the gel (see Table 1, DGT Research, 2000) t = deployment time (in seconds) A = exposure area (3.14 cm 2) 3.5 Sediment Sampling and Analysis Streambed sediment samples were collected twice during the research period (July 2004 and February 2005) to determine any differences in sediment quality between high and low flow conditions. Collection took place at each one of the stream sampling sites (Figure 1.2) using a 2.5 m long wooden pole with an aluminum pot attached at each end (Figure G8) and trying to collect the most surficial layer from the center of the streams. The pots were rinsed with stream water from the sampling station before collecting the sediments. After collection, samples were double-bagged, labeled and placed in a cooler to be transported to the UBC Environmental Engineering Laboratory, where they were stored in a cold room at 4°C until sieving for metal analysis (between 1 and 3 days after collection). Sediments were analyzed for organic matter content, particle size and trace metals in relation to wet/dry weather conditions and proportion accumulated in different sediment fractions. 26 3.5.1 Particle Size Analysis Composite sediment samples (July 2004 + February 2005) were dry sieved by manual agitation to determine grain size distribution [Welch, 1948; Murdoch & Bourbonniere, 1991]. Sieve numbers used were #10 (2.00 mm mesh), #18 (1.00 mm mesh), #60 (250 um), #100 (150 pm) and #230 (63 pm). The > 2 mm fraction was discarded and all other fractions resulting from the analysis were stored in acid washed bottles for ICP trace metal analysis in relation to different particle size and for organic matter content analysis. 3.5.2 Trace Metal Analysis in Relation to Wet/Dry Weather Conditions Sediment samples collected in July 2004 and February 2005 were wet sieved using distilled water and stainless steel sieves numbers 10, 18, 60 and 230, in order to obtain the < 63 urn fraction. The sediment fraction resulting from the sieving procedure was placed in labeled acid washed beakers and oven dried at approximately 60°C. Once dried, samples were disaggregated using acid washed mortars and pestles and stored in acid washed bottles until analysis. The US Environmental Protection Agency method 200.2 (Sample Preparation for Spectrochemical Determination of Total Removable Elements) [US EPA, 1994] was used to prepare samples for ICP-AES analysis. Using this method, 1.000 ± 0.005 g were weighed using a Mettler A C 88 - Delta Range Analytical Balance. The weighed samples were then placed in 150 ml acid washed beaker and 4 ml of 1:1 H N 0 3 a n d 10 ml of 1:4 HCI were added. Beakers were placed in an oven inside a fume hood at 80°C and allowed to reflux for 1 hour. Samples were then allowed to cool and transferred to 100 ml volumetric flasks and diluted to volume using deionized water. Volumetric flasks were sealed using parafilm and samples were mixed by gently turning the flasks upside down and gently turning them right side up again 10 times. Finally samples were filtered into 60 ml acid washed bottles using a Whatman filter #42 and refrigerated until analyzed. All samples were analyzed on the same run using the Varian Vista-Pro C C D Simultaneous ICP-AES in the Soils Department Laboratory at UBC and all results are presented as mg/kg dry weight. 27 3.5.3 Trace Metal Analysis in Relation to Particle Size Two different fractions (<63 um and 2mm - 63 um) resulting from particle size analysis on composite sediment samples were prepared for trace metal analysis using the US E P A Method 200.2 described above. All samples for metal analysis (in relation to weather conditions and accumulation according to fraction size) were analyzed on the same run. Duplicates on random samples, blank controls and a standard reference material from Priority PollutnT™/CLP (Lot No D035 - 540) were also run to test the accuracy of results. 3.5.4 Organic Matter Content Analysis Streambed sediment samples were analyzed for carbon using a Leco CN-2000 Carbon/Nitrogen Analyzer. The analysis was run on a bulk sample and the <63 pm fraction for each sample. 3.6 Application of GIS Techniques to Determine Land Use Impacts on Sediment, Surface Water and Groundwater Quality A spatial database was created using digital maps and orthophotos provided by the Township of Langley. The location of private wells in the study and stream sampling sites was plotted onto a map representing the land use in the watershed using ArcGIS 9.0. It must be noted that, since a significant portion of the watershed is in the Municipality of Abbotsford and the other in the Township of Langley, there are some differences in the quality of the spatial data used. The Township of Langley provided a parcels map with updated land use codes, but for the portion of the watershed located in Abbotsford, the land use map had to be created and digitized from the orthophoto on the municipality's website [http://www.citv.abbotsford.bc.ca/]. In previous studies, Berka (1996) and Addah (2003) concluded that the use of buffers to determine land use impacts on water quality is preferable to the use of contributing areas in watersheds with low topography. Smith (2004), Magwood (2004) and MacDonald (2005) also used buffer analysis to link land use to water quality. Therefore, using the buffer tool in ArcMap®, circular buffers with a 100 m radius were created around each well to calculate the percent land use within each of these. In the case of streams, the buffers created for analysis extended 100 m on each side and 500 m upstream from each sampling station [Smith, 2004]. Five land use categories were created for analysis within well buffers: 28 • Rural residential/hobby farms • Animal operations: includes all livestock, sheep, poultry, pig farms, etc. Pasture and grazing are also considered under this category • Trees and bushes: includes forest-covered and riparian areas • All other agricultural activities: mainly refers to berry plantations and other row crops, vegetables, fruit production, mushroom farms and greenhouse operations • Other, refers mainly to impervious areas such as roads, parkways, commercial establishments or institutions with large parking areas In the case of well buffers, the total area of impervious surfaces within each buffer (mainly roads under the category, "other") was determined as the difference between the total area of the buffer (31,415.93 m 2) and the sum of the areas of all the other land use categories within the buffer. Total area impervious surfaces = 31,415.93 m 2 - X area of all other land use categories For land use analysis within stream buffers, two more categories were added to those described above: "urban residential", which includes single as well as multiple family dwellings and "gravel extraction". For stream buffers, the total impervious surface within each buffer includes roads, parkways and commercial establishments with large parking areas. As roads are typically not digitized in land use maps, road area was estimated from orthophotos by measuring the length and width of each road within individual buffers, using the ArcMap® measuring tool. 3.7 Data Analysis Methods The SPSS for Windows 12.0 software program was used for all statistical analysis. For parameters below detection limit, these values were replaced with half the value of the detection limit. Parameters that were always below detection limit were eliminated from analysis. 29 3.7.1 Groundwater Data Statistical Analysis Groundwater survey data was not statistically analyzed and therefore, only raw data and percentages are presented. Groundwater quality data, with the exception of dissolved elements, which were only measured during the wet season, were split into dry (October 2004) and wet (February 2005) seasons. The Mann-Whitney U Test was used to determine if there were significant differences between these two seasonal sets of data. The Mann-Whitney U Test was run first on all wells regardless of depth, and a second time on shallow wells (< 30 m deep) since deep groundwater is typically not subject to seasonal fluctuations because it takes more than 10 years for surface water to reach deep groundwater [H. Schreier 1, pers. comm., March 20, 2006]. Spearman rank correlation coefficients were calculated to determine if any relationships existed between the different quality parameters. The coefficients were calculated for each seasonal data set separately. Data was also split into different groups based on the location of wells on the different aquifers in the watershed. However, since most of the wells in the study are located on the Abbotsford aquifer, statistical analysis was not feasible. 3.7.2 Surface Water Data Statistical Analysis Surface water quality results were divided into dry (July - September 2004 amd May - June 2005) and wet (October 2004 - April 2005) seasons based on flow and precipitation data. In total, there were 5 sampling events during the dry season and 7 during the wet season. The Mann-Whitney U Test was used to determine any significant differences between seasonal data. In the case of temperature, a Kruskal-Wallis test was used to deal with inherent seasonal fluctuations and determine differences between sites, rather than sampling periods. Data were also split into urban and rural sites and the Mann-Whitney U Test was again used to determine if these two groups were significantly different for any of the parameters monitored. Spearman rank correlation coefficients were used to determine relationships between parameters during the wet and dry seasons analyzed separately. 1 Professor. Institute for Resources, Environment and Sustainability. U B C . 30 Maximum and minimum values for each parameter were calculated for the entire watershed (Appendix C). Median values for each water quality parameter were calculated for the wet and dry seasons to determine spatial and temporal trends and graphs were created to visualize variations. In the graphs, median values are used and error bars represent the 1 s t and 3rd quartiles. Sites have been arranged in the graphs in the upstream to downstream direction for all creeks and split into urban and rural sites for Bertrand Creek in order to better visualize spatial trends. 3.7.3 Sediment Data Statistical Analysis Sediment data was also split into the dry (July 2004) and wet (February 2005) seasons and into urban and rural sites. The Mann-Whitney U Test was used to determine if there existed any significant differences between these groups. Spearman rank correlation analysis was used to determine any relationships between the different elements analyzed in sediments. Wet and dry season values were used to create graphs similar to those created for surface water quality parameters, with sites arranged in the upstream to downstream direction for all creeks and split into urban and rural sites. 3.7.4 DGT Data Statistical Analysis Due to the low number of samples, DGT data was not fit for correlation analysis and thus, only the Mann-Whitney U Test was used to determine significant differences between dry and wet season data and urban vs rural sites. 3.7.5 Relationships between Land Use, Sediment and Water Quality The percent land use calculated within well and stream buffers was used to determine any links with the different water quality indicators through Spearman's rank correlation analysis. In the case of stream buffers, the categories for "urban residential", "gravel extraction", and "rural residential/hobby farms" had too few data points associated with them to perform correlation analysis. Since the category "urban residential" comprises mainly impervious surfaces, it was aggregated to the land use category labeled as "other" to run correlation analysis on S P S S v. 12.0 under a new category labeled "impervious surfaces". Similarly, the categories "rural residential/hobby farm" and "all other agricultural uses" were lumped together to create a new category classified as "other agricultural activities" to perform statistical analysis. The category "gravel extractions" was only present in two stream buffers and was therefore not taken into account for Spearman's rank correlation. 31 3.8 Quality Analysis and Quality Control (QA/QC) All samples analyzed for elements using the ICP-AES were automatically run in triplicate and the concentration value provided for each element was the average of these triplicates. The standard deviation and relative standard deviation (% error) were also provided. These data can be found in Appendix B for groundwater, Appendix C for surface water, Appendix D for sediment samples and Appendix E for DGTs. Accuracy of ICP analysis was determined by measuring a series of standards every ten samples during each run. 3.8.1 Groundwater Q A / Q C For groundwater element analysis (major cations) using ICP-AES and for nutrient and chloride analysis, the standard deviation and coefficient of variation of blind replicates and blanks were used to determine measurement precision. In the case of those groundwater samples that had high concentrations of N 0 3 " - N, the respective well owners were contacted and a second sample was analyzed. Data can be found in Appendix B. 3.8.2 Surface Water Q A / Q C In order to determine intra site variability, water samples were collected in triplicates at two or three randomly selected sites during each sampling event. The standard deviation and coefficient of variation were calculated for replicates to determine precision. Blanks were included in each run to ensure that solutions were not contaminated (Appendix C). 3.8.3 Sediment Q A / Q C Duplicates were collected at selected sites to determine intra site variability and a series of sub samples were used to provide an indication of the precision of the various analytical methods used. Again, the standard deviation and coefficient of variation were calculated to measure precision. Accuracy of trace metal analysis was determined by using Priority PollutnT™/CLP (Lot No D035 - 540) certified standard reference material (Appendix D). 3.8.4 DGT Q A / Q C Duplicate DGTs were deployed in site 12 on Bertrand Creek for both sampling events to determine within site variability and a blank was included during each run to ensure that solutions were not contaminated. These data are presented in Appendix E. 32 4 Results 4.1 Precipitation and flow data Monthly precipitation in Aldergrove for the study period (June 2004 - June 2005) was obtained from the Environment Canada climate station at Abbotsford Airport and is presented in Figure 4.1. Total precipitation for the period was 1808.9 mm with a mean monthly precipitation of 139.14mm, with July (20.4 mm) and November 2004 (281.9 mm) as the driest and wettest months respectively. Based on these data, sampling for the study was divided into two seasons or periods: dry period and wet period. The dry period went from July to September 2004 and May to June 2005 and the wet period from October 2004 to April 2005. It must be noted that February was an unusually dry month within the wet season, with only 74.6 mm of precipitation. Flow data for Bertrand Creek was collected from Environment Canada's hydrometric station at international boundary (08MH152). Flow data for Pepin Creek corresponds to Environment Canada's station 08MH156. Environment Canada's hydrometric stations on Pepin and Bertrand Creeks operate seasonally and thus, flow data for November 2004 - April 2005 are missing. In order to create a hydrograph for both of these creeks, flow data for the Salmon River at 7 2 n d Avenue, Langley (station 08MH090) and Fishtrap Creek at International Boundary (station 08MH153) were used to estimate % increase in flow. Since the Salmon River watershed is somewhat similar to the Bertrand Creek watershed in terms of geographic location, precipitation, elevation and land use, these data were used to calculate percent increase in average monthly flow in Bertrand Creek and plot the hydrograph (Figure 4.2). The same applies to the Pepin Creek and Fishtrap Creek watersheds; however, data for March and April are still missing for the Fishtrap Creek station. The hydrograph for Pepin Creek is presented in Figure 4.3. 33 Monthly Precipitation in Aldergrove 300 n Figure 4.1 Monthly precipitation in Aldergrove Data from the Abbotsford Airport climate station Figure 4.2 Daily Mean Flow for Bertrand Creek 4.2 Groundwater results 4.2.1 Groundwater Survey Results A total of 36 private well owners completed and returned the groundwater survey attached to the letter of invitation to participate in the study. According to the survey, 61.1% of well owners filter or treat their water and the remaining 38.9% neither filter nor treat their groundwater. When asked what their perception of the quality of their well water was, only 8.3% said the quality was poor, 27.8% said it was excellent, 33.3% said it was good and 30.6% said it was moderate. Figure 4.4 presents these results. • Excellent • Good • Moderate • Poor 33.3% Figure 4.4 Well owners' perception of the quality of their water 35 When participants were asked whether they thought an increase in groundwater use was appropriate, only 2.8% (1 respondent) said yes, 8.3% said that a limited use would be appropriate, 16.7% said no and the majority (63.9%) said they needed more information. 8.3% chose not to respond to this question. When asked to what extent they thought groundwater affected local rivers in terms of flow and water quality, the responses were as follows (Table 4.1): Table 4.1 Participants' perception of groundwater impact on surface waters (N=36) Significant Impact Moderate Impact No Impact No Response TOTAL River Flow 16.7% 50.0% 22.2% 11.1% 100% Water Quality 22.2% 44.4% 19.4% 13.9% 99.9% In order to explore participants' perception of risk of the quality of their water, they were presented with a list of 8 measures or characteristics that people might use to "rank" the quality of their water. The responses to these questions showed that people strongly rely on visible measures to form their perceptions on the quality of their drinking water. Participants were asked to assign a value from 1 - 7 (1 least important; 7 most important) to each of the measures according to how important they deemed them to indicate the quality of the water. 52.8% of respondents assigned color and visible abnormalities a value of 7 - most important; smell/taste and amount of visible particulate matter were ranked as 7 by 50% of participants. Cloudiness was also assigned a value of 7 by 47.2% of the respondents. Results are presented in Figure 4.5. 36 > • Rankl • Rank 2 • Rank 3 • Rank 4 • Rank 5 O Rank 6 • Rank 7 B N / R Least Important • Most important Figure 4.5 Well owners' perception of the relative importance of different water quality indicators Similar ly, part icipants were presented with a list of land use activit ies and a s k e d to rank them from 0 to 5 (0 least important - 5 most important) depend ing on how important they thought them to be in caus ing water quality prob lems. 6 1 . 1 % of part icipants ass igned the use of chemica ls in farming a va lue of 5, which might reflect the concern assoc ia ted with the p resence of pest ic ides in groundwater in this a rea . T h e use of ferti l izers in farming and aggregate extraction activit ies were a lso ranked as "most important" (value of 5) by 4 4 . 4 % of respondents . Resu l t s are summar i zed in Figure 4.6. 37 0> IB C o a at CC n a. 100% 80% 60% 40% 20% H 0% 13d S2 g 0) -N E 8.3 11.1 c c — cn — w ,S jo O ) =J F ro £ c E o p ro ro E E E S 8.3 25 h6.7^  5.6 8.3 23. 8.3 8.3 8.3 o 19.^  3.0 16.7 8.3 5^ 6 8.3 o (0 N a> 30.6 _ 19.^  hi . i i i . i 5 l 13.S E a> £2 o o o cn 25 11.1 fc2.3 8.3 CO E u> >. CO U "5. a> L. 13.S 5li 5!6 25 8.3 ro .*—1 CO 3 T3 CO CD n H 4 23 >2.2 8.3 I CD C l i cn i= cn x co a> IN/R BRankO Least important I Rank 1 • Rank 2 • Rank 3 I Rank 4 I Rank 5 Most important Figure 4.6 Well owners' perception of the relative importance of different land use activities in causing water quality problems Finally, well owners were asked to rank 0 to 5 (0 least important - 5 most important) each of 9 groundwater management strategies based on how appropriate they considered them to be. The regulation of the application of manure and fertilizers in agriculture and the use of garden chemicals were considered most appropriate and ranked 5 by 44.4%, 41.7% and 38.9% of respondents respectively. Results are presented in Figure 4.7. 38 fl) (0 c o a. v> fl> or: c ra a . "5 as 100% 80% 60% 40% 20% 0% 38.9 &7.d 11.1 5.6 8.3 8.3 r2T8l [23] H R 22.2 5.6 2~8" MM £7.d 25.q 11.1| 25.q 11.1 i 13.9 s § o = to CD CD C fl) CO C fl> c CD •a «? i 8 co y CO o CD 1 c CO o co jo O 3 C O C L CD CD <-CO o c 3 T 3 CQ O C o o 1 6 . 7 30.9 ^9.4 13.9 11.1 8.3 5l3 11.1 03.3 22.2 8.3 8.3 8.3 0) i , co E CO C L CO c E a) CO " O CZ J O CD -4—' J O C O fl) 27.3 h9.4^  22.2 5.6 2 ^ 8.3 33.3 5.6 8.3 CO 3 X J O L = > — "a o •e to fl) > (0 •e 3 CO 2 IN/R I Rank 0 o Rank 1 • Rank 2 • Rank 3 • Rank 4 I Rank 5 Least important most important Figure 4.7 Well owners' perception of the appropriateness of different groundwater management strategies 4.2.2 Groundwater Quality Results Raw groundwater quality data is presented in Appendix B. The Mann-Whitney U Test results revealed no significant differences between any groundwater quality parameters for the wet and dry seasons except for electric conductivity and therefore, total dissolved solids (TDS) (a < 0.05). However, for correlations between parameters, the two data sets (dry and wet periods) were analyzed separately. Wells were split into groups corresponding to each one of the aquifers in the watershed, based on their spatial location (determined through GIS maps - see Figure 1.3). Table 4.2 presents a summary of the number of wells in each aquifer and the number that were below detection limits for each of the parameters analyzed. The total number of wells for each aquifer may 39 change between the dry and wet seasons because some well owners failed to provide water samples for the February 2005 sampling event (1 well owner on the Abbotsford (A) aquifer, 1 on the Aldergrove Quadra and 1 on the Aldergrove A B aquifer). Table 4.3 presents the summary statistics for the groundwater quality parameters analyzed for both seasons combined. Table 4.2 Number of wells on each aquifer within the study area and number of wells below detection limit for the different water quality parameters * data for the dry season ** data for the wet season I Aquifer Total #of Parameter (# of wells below detection limit/total # of wells sampled) wells N 0 3 - N P 0 4 Cu Fe Mn Zn sampled South of 5 0/5* 1/5* 4/5** 2/5** 2/5** 2/5** Hopington 1/5* 1/5** Abbotsford (A) 27 2/27* 12/27* 18/26** 15/26** 4/26** 3/26** 1/26** 19/26** Aldergrove 6 0/6* 0/6* 3/5** 3/5** 3/5** 2/5** Quadra 0/5** 2/5** Aldergrove A B 2 0/2* 0/2* 1/1** 1/1** 1/1** 0/1** 0/1** 1/1** Table 4.3. Summary statistics for groundwater quality parameters (both seasons combined) Parameter Depth N03" - N P O 4 - P CI pH EC TDS Turbidity (m) (mg/L) (mg/L) (mg/L) (pS/cm) (mg/L) NTU Max 82 24 1.7 357 9.2 2234 1497 447 Min 2 0.0 0.01 0.6 4.4 58 39 0.1 Mean 18 4.0 0.1 23.2 6.7 315 211 10.8 Median 9 2.0 0.01 5.7 6.4 202 135 0.3 1st Quartile 6 0.02 0.01 2.8 6.0 149 100 0.2 3rd Quartile 19 6.1 0.04 9.0 7.6 271 182 0.6 Standard Deviation 20.4 4.9 0.27 59.3 1.0 355 238 61.5 40 Table 4.3 continued Parameter Ca Cu Fe K Mg Mn Na Si Sr Zn (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) Max 45.9 7.2 45.5 13.1 18.7 0.7 246.4 17.8 0.2 1 2 Min 0.2 0.0 0.0 0.7 0.0 0.0 1.9 2.9 0.0 0.0 Mean 15.3 0.3 1.4 3.4 4.8 0.1 31.2 7.1 0.1 0.1 Median 14.0 0.0 0.0 3.0 3.5 0.0 7.1 6.6 0.1 0.0 1st Quartile 8.6 0.0 0.0 1.2 2.1 0.0 5.0. 4.8 0.1 0.0 3rd Quartile 20.6 0.1 0.1 4.8 6.3 0.0 12.7 8.5 0.1 0.0 Standard Deviation 9.1 1.2 7.5 2.6 4.0 0.1 61.0 3.3 0.1 0.2 4.2.2.1 Correlations between Groundwater Quality Parameters Data was split into dry and wet weather for correlation analysis. Parameters analyzed were the same for both seasons, with the exception of major cations that were analyzed only during the wet season. During the dry season, well depth was positively correlated to pH, phosphate, specific conductivity and total dissolved solids (a<0.01) and negatively correlated to nitrate (a<0.01). N 0 3 - N was negatively correlated to all variables (depth, pH, turbidity, specific conductivity, total dissolved solids and phosphate). Phosphate, in turn, was positively correlated to all variables except nitrate. Correlations between groundwater parameters for the dry season are summarized in Table 4.4. During the wet season, the same correlation trends apply for well depth: positively correlated to pH, orthophosphate, specific conductivity and total dissolved solids (a<0.01). In addition, depth was positively correlated to Fe (a<0.05), Na and Si (oc<0.01) and negatively correlated to N 0 3 - N and Cu (a<0.01). Apart from well depth, N 0 3 - N was negatively correlated to phosphate, pH, turbidity, Si , Fe (a<0.01) and Na (a<0.05). As during the dry season, orthophosphate was only negatively correlated to N 0 3 - N (a<0.01). Significant correlations between parameters for this season are summarized in Table 4.5. For all correlations please see Appendix F. In general, cations were positively correlated to each other in two groups. Group I: Ca , Fe, Mg, Mn, Na, Si , Sr and Group II: Cu, Sr, Zn. 41 Table 4.4 Spearman rank correlations for groundwater quality parameters for the dry season ** correlation is significant at the 0.01 level (2 - tailed) * correlation is significant at the 0.05 level (2 - tailed) Parameter Positively correlated to Negatively correlated to Well Depth pH**, specific conductivity**, TDS**, P0 4 ** N 0 3 - N * * PH Well depth**, specific conductivity**, TDS**, P 0 4 - P ** N 0 3 - N** N03-N None Well depth**, pH**, turbidity**, specific conductivity**, TDS**, P0 4 ** PO4-P Well depth**, pH**, turbidity**, specific conductivity**, TDS** N 0 3 - N** Table 4.5. Spearman rank correlations for groundwater quality parameters for the wet season ** correlation is significant at the 0.01 level (2 - tailed) * correlation is significant at the 0.05 level (2 - tailed) Parameter Positively correlated to Negatively correlated to Well depth Fe*, Na**, Si**, pH**, specific conductivity**, TDS**, P 0 4 - P** Cu**, N 0 3 - N** pH well depth**, Fe**, Na**, Si**, specific conductivity**, TDS**, PO4** Cu**, N 0 3 - N** N03-N None well depth**, Fe**, Na*, Si**, pH**, turbidity**, P0 4 ** P04 well depth**, Na**, Si**, pH**, specific conductivity, TDS** N 0 3 - N** Since there seemed to be a strong negative correlation between N 0 3 " - N concentrations and well depth, wells were stratified according to depth in order to visualize whether there is a certain depth below which N 0 3 " - N doesn't seem to influence groundwater quality. Average concentrations for the wet and dry seasons were used. Wells were split into the following categories according to depth in meters: very shallow (< 15 m), shallow ( 1 6 - 2 9 m) and deep (£ 30 m). Results are presented in Figure 4.8 and Figure 4.9 below. 42 30.0 -25.0 - • 20.0 -O) E z 15.0 - • N03 • 10.0 -5.0 -0.0 -• dry season • wet season -i •— « r 10 20 70 80 90 30 40 50 60 well depth (m) Figure 4.8 Correlation between N Q 3 - N concentrations and well depth 10 i 9 8 7 -6 5 4 3 2 1 -0 0-15 16-29 depth (m) I above 3 mg/L N 0 3 - N I above 10 mg/L N 0 3 - N 0 0 30 and over Figure 4.9 Number of wells showing high levels of nitrate in relation to depth 43 Phosphate concentrations were also correlated to depth following the same stratification categories established for correlation with nitrates. Even though phosphate concentrations were generally low and mostly below detection limits, there is a slight tendency of these to increase with depth, possibly due to geological influences. Results are presented in Figure 4.10. 1.8 1.6 1.4 1.2 - i |> 1.0 3 0.8 Q. 0.6 0.4 0.2 0.0 10 20 30 40 50 60 wel l depth (m) • dry season • wet season 70 80 90 Figure 4.10 Correlation between P 0 4 - P concentrations and well depths 4.3 Surface water quality results Table 4.6 presents a summary of significant differences in water quality between urban and rural sites in the watershed. Note that urban sites refer to sites 1, 2 and 3 on Bertrand Creek (BCr1, BCr2, BCr3) in the north end of the watershed. All other sites along Bertrand, Howes and Pepin Creeks are in the rural portion of the watershed. Cave Creek was not included in the analysis since there is only one sampling station on this stream. See Figure 1.2 for the location of stream sampling stations in relation to land use. See Appendix C for complete result tables for surface water parameters. 44 Table 4.6 Significant Mann-Whitney U Test results (a<0.05) for surface water quality parameters Parameter Stream Name Site IDs <or > In comparison to N 0 3 - N Howes Creek HC5, HC6, HC7 > All other stations on all streams Bertrand BCr1, BCr2, BCr3 < Howes Creek (all stations) Creek Bertrand Creek (rural stations) P O 4 - P Howes Creek HC5, HC6, HC7 > All other stations on all streams Bertrand BCr1, BCr2, BCr3 > Bertrand Creek (rural stations) Creek Pepin Creek (all stations) cr Bertrand BCr1, BCr2, BCr3 > All other stations on all streams Creek DO Bertrand BCM, BCr2, BCr3 < Bertrand Creek (rural stations) Creek Mn Bertrand BCM, BCr2, BCr3 > Bertrand Creek (rural stations) Creek Pepin Creek (all sites) 4.3.1 Spatial and Seasonal Variations in Nitrate (N0 3 - N) Concentrations of N 0 3 " - N ranged from 0.03 to 20.93 mg/L with a median of 1.5 mg/L. Both extreme values correspond to the same sampling date (June 2005), but the lowest one corresponds to station 1 on Bertrand Creek (BCr1) and the highest to station 5 on Howes Creek (HC5). Station 5 consistently showed the highest nitrate levels throughout the year, but especially during the summer months. Station 6 on Howes Creek (HC6) had no flow during the summer months (July - September 2004; June 2005) but showed nitrate values comparable to those of Station 5 for the rest of the sampling period. Station 7 on Howes Creek (HC7) had no flow during July and August 2004, but for the rest of the summer months/dry season, it showed relatively low levels of nitrate, increasing during the rainy season. Nitrate concentrations for the dry season were significantly different from those in the wet season. With the exception of station 5 in Howes Creek (HC5) and 4 on Bertrand Creek (BCr4), nitrate concentrations tended to be higher during the rainy months. Figure 4.11 shows median nitrate concentrations per site in the upstream to downstream direction for the wet and dry seasons. The Mann-Whitney U Test was used to determine significant differences between nitrate concentrations in urban and rural sites. Stations 1 (BCr1), 2 (BCr2) and 3 (BCr3) on Bertrand 45 Creek are on the urban portion of the watershed, whereas stations 4 (BCr4), 8 (BCr8), 11 (BCr11) and 12 (BCr12) along this same stream are on the rural area. All stations on Howes and Pepin Creeks are on the rural portion of the watershed (Figure 1.2). Nitrate concentrations during the dry and wet seasons were significantly higher in the rural stations on Bertrand Creek and Howes Creek (HC5, HC6, HC7) compared to the urban stations (a< 0.05), but there was no significant difference between the rural stations on Pepin Creek (PC9, P C 10) and the urban stations on Bertrand Creek. Site IDs upstream • downstream (not to scale) *Median N 0 3 " - N concentration for HC5 = 10.71 mg/L (Ch = 9.44 mg/L, Q 3 = 11.3 mg/L Error bars represent 1 s t and 3 r d quartiles (Q^ Q 3 ) Figure 4.11 Median N 0 3 " - N concentrations per site in the Bertrand Creek watershed 46 4.3.2 Spatial and Seasonal Variations in Orthophosphate For orthophosphate analysis, only sites 8 (BCr8), 11 (BCr11) and 12 (BCr12) on Bertrand Creek were below detection limit (0.01 mg/L P 0 4 - P) on one sampling occasion (August 2004) and site BCr12 again in July 2004. Phosphate concentrations in the watershed ranged from 0.01 to 32.5 mg/L P 0 4 - P with a median of 0.07 mg/L. Site BCr12 presented the lowest median concentration for the dry season (median value of 0.01 mg/L P 0 4 - P) whereas site 9 on Pepin Creek (PC9) had the lowest median concentration for the wet season (0.03 mg/L P 0 4 - P). On the other hand, site HC5 had the highest median concentration for the dry season (5.68 mg/L P 0 4 - P) and site 6 (HC6), also on Howes Creek, had the highest median concentration for the wet season (0.31 mg/L P 0 4 - P). The Mann-Whitney U Test results showed no significant differences in the concentration of phosphate between the wet and dry seasons. However, when urban and rural stations were compared, orthophosphate concentrations on Howes Creek were significantly higher (a < 0.05) than concentrations at all other stations in all other streams. With the exception of those sites on Howes Creek, phosphate concentrations in the urban part of the watershed were significantly higher than at rural stations on Bertrand and Pepin Creeks. Figure 4.12 summarizes the results for orthophosphate in terms of seasonal and spatial variability. Note that the median P 0 4 - P concentration for the dry season for HC5 (5.68 mg/L) is off - scale in the graph. 47 Site IDs upstream • downstream (not to scale) Median P 0 4 concentration for HC5 = 5.68 mg/L ( d = 2.67 mg/L, Q 3 = 6.53 mg/L Error bars represent 1 s t and 3 r d quartiles (Q^ Q 3 ) Figure 4.12 Median orthophosphate concentration per site in the Bertrand Creek watershed 4.3.3 Spatial and Seasonal Variations in Chloride Concentrations of chloride (Cl) in the watershed were between 2.85 - 125.00 mg/L with a median of 10.95 mg/L. The lowest concentration corresponds to station 5 on Howes Creek (December, 2004) and the highest concentration to station 13 on Cave Creek (CC13) for the August 2004 sampling event. Concentrations were significantly higher during the dry months (oc<0.01). Concentrations at the urban stations (BCr1, BCr2, BCr3) were significantly higher than concentrations in the rural sites during both sampling seasons (oc<0.01). Results are presented in Figure 4.13. 48 100 90 -80 70 -ml 60 -O) E 50 o 40 30 -20 10 -0 •dry season —•—wet season o CD CNJ « -2 o o o CD CD CD m o o CD CD O X co O X o X at O CL o CL Site IDs upstream •+• downstream (not to scale) CO O O Error bars represent 1st and 3 r d quartiles (Q 1 t Q3) Figure 4.13 Median chloride concentration per site in the Bertrand Creek watershed 4.3.4 Spatial and Seasonal Variations in Dissolved Oxygen Dissolved oxygen (DO) levels ranged from 0.9 -14.7 mg/L with a median of 9.7 mg/L. Both, the highest and lowest concentrations correspond to the dry period. The highest value corresponds to site 4 on Bertrand Creek (BCr4, June 2005) and the lowest to site 9 on Pepin Creek (PC9, July 2004). The highest and lowest concentrations for the wet season were 13.0 mg/L (BCr12, March 2005) and 2.9 mg/L (HC7, October 2004). The Mann-Whitney U Test showed that dissolved oxygen concentrations were significantly higher during the wet season compared to the dry season. Results also showed that compared to the urban portion of the watershed, DO was significantly higher in rural sites. Figure 4.14 presents these trends. Percent saturation was calculated to correct for temperature effects on dissolved oxygen concentrations. Since the watershed has a flat topography and low elevation, atmospheric pressure was assumed to be standard (1 atm). The effect of salinity was considered negligible and assumed to be 0. Median % saturation values per site in the upstream to downstream direction are shown in Figure 4.15. Percent saturation for all sites for each sampling event can be found in Appendix C. 49 Site IDs upstream • downstream (not to scale) Error bars represent 1 s t and 3rd quartiles (Q 1 : Q 3 ) Figure 4.14 Median dissolved oxygen concentration per site in the Bertrand Creek watershed Site IDs upstream • downstream (not to scale) Error bars represent 1 s t and 3rd quartiles (Q^ Q 3 ) Figure 4.15 Dissolved oxygen % saturation per site in the Bertrand Creek watershed 50 4.3.5 Spatial and Seasonal Variations in pH pH values in the watershed ranged from 5.5 (site HC7 on Howes Creek, June 2005) to 7.7 (sites BCr11 on Bertrand Creek and C C 1 3 on Cave Creek, February 2005) with a median of 7.0 throughout the year. The highest pH for the dry season corresponds to site 10 (PC10) on Pepin Creek (pH = 7.4, May, 2005) and the lowest pH value for the wet period corresponds to HC7 (pH = 6.1, March 2005). Site HC7 constantly showed the lowest pH values, especially during the summer months. Overall, pH was significantly lower during the dry season (<x<0.05). When urban and rural sites were compared, pH was significantly lower at the urban stations on Bertrand Creek than at rural stations along Bertrand and Pepin Creeks during the wet season. Results are presented in Figure 4.16 7.5 6.5 5.5 Urban sites Rural sites • dry season - wet season T- CM CO CO 1— l _ L» L _ 1_ o o o o o ffl ro cn m m o co CM o CO O I CD o X o X CT) o CL o CL Site IDs upstream -•downstream (not to scale) Error bars represent 1st and 3 r d quartiles (Ch, Q3) Figure 4.16 Median pH per site in the Bertrand Creek watershed CO O o 51 4.3.6 Spatial and Seasonal Variations in Specific Conductivity Specific conductivity ranged from 61 (BCr8, December 2004) to 1015 u,S/cm (BCr1, July 2004), with an overall median of 186 u,S/cm. The lowest value for the dry season corresponds to site 3 on Bertrand Creek (BCr3, September 2004) and the highest value for the wet season correspond to site 13 on Cave Creek (CC13, October 2004). Overall, specific conductivity was significantly higher (oc<0.01) during the dry months. There were no significant differences between urban and rural sites for the wet season, but during the dry season, specific conductivity was significantly higher in the urban portion of Bertrand Creek compared to rural stations on Bertrand and Pepin Creeks (oc<0.01). Median values per station on the upstream to downstream direction for the wet and dry season are presented in Figure 4.17. •dry season -wet season L O o CD o o co o a. o 0_ Site IDs upstream •#• downstream (not to scale) Error bars represent 1 s t and 3 r d quartiles (Qi, Q 3) Figure 4.17 Median Specific Conductivity per site I I CO o O 52 4.3.7 Spatial and Seasonal Variations in Temperature Water temperature ranged from 3.8 to 20.6 °C with a median of 10.8 °C throughout the watershed over the seasons. The highest temperatures were recorded in July 2004 on all sites on Bertrand Creek, with the exception of sites 4 (BCr4) and 11 (BCr11), which have good riparian cover. The lowest temperatures were recorded in February 2005 on site 10 on Pepin Creek (PC10) and site 13 on Cave Creek (CC13). Kruskal-Wallis test results showed no significant differences for temperature between any of the sites in the watershed for neither the dry nor wet periods. Similarly, there were no significant differences found when the urban and rural sites were compared using the Mann-Whitney U Test. Seasonal and spatial trends (in the upstream to downstream direction) for temperature are presented in Figure 4.18 Site IDs upstream •downstream (not to scale) Error bars represent 1 s t and 3 r d quartiles (Q 1 : Q 3) Figure 4.18 Median temperature per site 53 4.3.8 Spatial and Seasonal Variations in Elements in Surface Waters The following elements were analyzed in surface waters for 5 sampling events (3 during the dry period and 2 during the wet period - detection limits in mg/L in parentheses): C a (0.1), Cu (0.05), Fe (0.05), K (0.5), Mg (0.01), Mn (0.005), Na (0.25), Si (0.15), Sr (0.002), Zn (0.01). All of the analyzed elements were found above detection limits on all sampling occasions, except for copper (detection limit 0.05 mg/L), which was above the detection limit for only a few sites as shown in Table 4.7. Table 4.7. Sites above detection limit for copper Sampling date SiteJD [Cu] mg/L duly 2004 BCr1 0.07 C C 1 3 0.06 August 2004 BCr1 0.06 BCr2 0.07 PC10 0.05 September 2004 HC5 0.07 December 2004 BCr1 0.06 PC9 0.10 Calcium, magnesium, manganese, sodium, silicon and strontium were found to be significantly different in streams for the wet vs dry seasons. When urban and rural sites on Bertrand Creek were compared using the Mann-Whitney U Test, only potassium was found to be significantly different during the wet season (a<0.01) and iron, manganese and sodium were significantly different between urban and rural sites during the dry season (a<0.01). Descriptive statistics for elements in surface waters are presented in Table 4.8. All concentrations are in mg/L. A brief summary of spatial and seasonal trends for each one of the elements above detection limits follows. Note that station 7 on Howes Creek (HC7) had no flow for 2 of the 3 summer sampling events and thus, a single value for concentration is presented, as opposed to a median value. Station 6 on Howes Creek (HC6) had no flow during any of the summer sampling events and therefore, results are missing in the graphs. 54 Table 4.8. Descriptive statistics for elements in surface water. All concentrations in mg/L Ca Fe K Mg Mn Na Si Sr Zn (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) Median 15.1 0.5 4.0 5.4 0.1 11.5 4.3 0.1 0.0 Max 65.8 10.8 45.9 18.5 2.5 194.2 11.6 0.4 1.4 Min 4.0 0.0 1.2 1.2 0.0 2.4 1.3 0.0 0.0 1st quartile 12.2 0.3 2.8 4.6 0.0 5.4 3.3 0.1 0.0 y" quartile 24.3 0.8 5.2 8.7 0.1 15.7 6.0 0.1 0.1 4.3.8.1 Spatial and Seasonal Trends in Calcium (Ca) Calcium concentrations were highest at station 5 on Howes Creek (HC5) with a median of 35.27 mg/L and lowest at stations BCr1, BCr2 and BCr11. Calcium concentrations were significantly higher (a<0.01) during the dry months. However, there were no significant differences between urban and rural sites. Figure 4.19 presents these results. • dry season • wet season R CN ro t <2 ^ o o o o o •- ^ co co co co CO O O CO CO LO CD I— o o o X X X o> o 2 s CO O O Site IDs upstream "•" downstream (not to scale) Error bars represent 1st and 3r d quartiles (Ch, Q3) Figure 4.19 Median [Ca] per site 55 4.3.8.2 Spatial and Seasonal Trends in Magnesium (Mg) The highest levels of magnesium for the dry season were found at sites BCr1 and BCr2 (median concentrations of 10.4 mg/L and 10.6 mg/L respectively). For the wet season, the highest concentrations were found in Pepin Creek (sites P C 9 and PC10, median concentrations of 6.84 and 6.06 mg/L respectively). Concentrations for the dry season were significantly higher (a<0.01) than for the wet season, but there appeared to be no significant differences between urban and rural sites for neither sampling season. See Figure 4.20 for summary of results. 18 • 16 H 14 12 1 10 E ~ 8 a 2 6 4 2 0 Urban sites Rural sites ir • dry season • wet season o m CN CO O O CO CQ S CO O O CQ CQ T - CN o o CQ CQ uo co r~-O O O X X X co o O «-CO O O Site IDs upstream- -•downstream (not to scale) Error bars represent 1 s t and 3 r d quartiles ( Q t l Q 3 ) Figure 4.20 Median [Mg] per site in the Bertrand Creek watershed 56 4.3.8.3 Spatial and Seasonal Trends in Iron (Fe) Station 7 on Howes Creek had the highest iron concentrations during the summer (median of 10.77 mg/L Fe) and station 9 on Pepin Creek had the highest concentration for the wet season (median of 1.24 mg/L Fe). Iron concentrations for the wet and dry seasons were not significantly different from each other. Nevertheless, iron concentrations were significantly higher at urban stations (BCr1, BCr2, BCr3) on Bertrand Creek, compared to rural stations on Bertrand and Pepin Creeks during the dry period. See Figure 4.21 for a graphic representation of results. Note that HC7 had no flow for 2 of the 3 sampling events in the dry season. Therefore and because the concentration of iron for the one sampling event in which the creek was not dry is one order of magnitude greater than the results for the other sites, this value has been eliminated from the graph below. Site IDs upstream • downstream (not to scale) * Fe concentration for HC7 during the dry season = 10.77 mg/L Error bars represent 1 s t and 3 r d quartiles (Q1, Q3) Figure 4.21 Median [Fe] per site in the Bertrand Creek watershed 57 4.3.8.4 Spatial and Seasonal Trends in Manganese (Mn) Concentrations of manganese were significantly higher during the dry season when compared to concentrations during the wet season (a<0.01) and were also found to be significantly higher at urban sites when compared to rural sites during the dry period (a<0.01). The highest median concentrations of manganese were found at sites BCr1, BCr2 and BCr3 (the urban portion of the watershed) throughout the year, with the exception of site 12 on Bertrand Creek (BCr12), which had the highest median concentration for the wet season, followed by the urban sites. Figure 4.22 presents a graphic summary of these trends. Spatial trends in manganese concentrations in Bertrand Creek during the dry season were similar to those for iron, experiencing a gradual decrease in the downstream direction as the water flows south from the urban to the rural sites. E Urban sites Rural sites CO 1 -o ^ m o CN t o C O LO CO I s -O O O X X I • dry s e a s o n • wet s e a s o n C O O C L O C L Site IDs u p s t r e a m •> d o w n s t r e a m (not to sca le) Error bars represent 1st a n d 3 r d quart i les (Qi, Q 3 ) I co O o F i g u r e 4.22 M e d i a n [Mn] per site in the Bertrand C r e e k w a t e r s h e d 58 4.3.8.5 Spatial and Seasonal Trends in Potassium (K) Site 13 on Cave Creek had the highest concentrations of potassium for both, the dry and wet seasons (medians of 10.51 and 5.69 mg/L respectively). Sites BCr8, PC9 and PC10 had the lowest concentrations for the dry season (2.58, 2.29, 2.87 mg/L median potassium concentrations respectively). There were no significant differences between potassium concentrations for the wet and dry seasons. Sites on the urban portion of the watershed had significantly lower (oc<0.01) concentrations than those in the rural portion during the wet season only. Figure 4.23 presents median concentrations per site for both sampling seasons. Note that the median potassium concentration for HC5 for the dry season is off - scale and is represented in the graph by an asterisk. 14 12 10 3 8 1 E 6 Urban sites Rural sites - dry season - wet season 43.6 IO CD I*-o o o x x x cn O CL o CL Site IDs upstream •+• downstream (not to scale) CO o o "Median [K] for HC5 for the dry season = 43.6 mg/L (Q, = 34.37 mg/L, Q 3 = 44.77 mg/L Error bars represent 1st and 3 r d quartiles (Qi. Q3) Figure 4.23 Median [K] per site in the Bertrand Creek watershed 59 4.3.8.6 Spatial and Seasonal Trends in Sodium (Na) The highest median sodium concentrations correspond to site BCr1 and site 13 on Cave Creek for the dry season (medians of 116.62 and 81.5 mg/L respectively). Concentrations for the dry season were significantly higher (a<0.01) and at least twice those for the wet season. Urban sites also presented a significantly higher concentration than rural sites during the dry season. Sodium followed the same seasonal and spatial trends as chloride (Figure 4.13). See Figure 4.24 for a summary of these results. 180 160 140 120 —I 100 O) E 80 n 60 40 20 0 Urban sites Rural sites oo «-i _ O ^ m o CM T — I— o CO in O X CD o X O X • dry season wet season CT) O H o EL co O O Site IDs upstream downstream (not to scale) Error bars represent 1st and 3 r d quartiles (Ch, Q3) Figure 4.24 Median [Na] per site in the Bertrand Creek watershed 60 4.3.8.7 Spatial and Seasonal Trends in Zinc (Zn) Zinc concentrations were found below detection limits on August 2004 (BCr1, BCr2, BCr3, BCr4), September 2004 (PC9) and February 2005 (BCr11, PC9 , PC10). The highest median concentration for the dry season corresponds to site 5 on Howes Creek (HC5, median Zn concentration of 0.17 mg/L). The highest median concentration for the wet season corresponds to site 11 on Bertrand Creek (0.05 mg/L). There were no significant differences between zinc concentrations for the wet and dry seasons. Similarly, there were no significant differences between urban and rural sites. Figure 4.25 summarizes these variations. Site IDs upstream m CD r~-O O O X I X • dry season • wet season cn O CL o - • downstream (not to scale) Error bars represent 1st and 3 r d quartiles (Q,, Q3) Figure 4.25 Median dissolved [Zn] per site in the Bertrand Creek watershed CO o o 61 4.4 DGT results 4.4.1 Spatial and seasonal variations in bioavailable metals DGT analysis focused only on those metals above detection limits: aluminum, iron, manganese, lead and zinc. However, the concentrations for blanks for lead were always exceptionally high and higher than all the other samples, suggesting some kind of contamination in the laboratory. Therefore, results for lead are not included in this section. The Mann-Whitney U Test showed no significant differences between trace metal bioavailability during the dry vs wet season and only manganese was significantly higher at urban sites when compared to rural sites. Results for bioavailable manganese agree with results for manganese in surface waters, which showed that concentrations were significantly higher in urban sites during the dry season (section 4.3.8.4) Figure 4.26 and Figure 4.27 show DGT results by site per season in the upstream to downstream direction and for urban and rural sites. B C M BCr3 BCr4 BCr11 BCr12 • Al dry season B A I wet season D Z n dry season D Z n wet season Site IDs upstream • downstream (not to scale) Figure 4.26 Bioavailable concentration of Al and Zn in surface waters for the dry and wet seasons 62 cn 400 350 300 250 200 150 100 50 H Urban sites Rural sites BCr1 BCr3 BCr4 BCr11 BCr12 • Fe dry season • Fe wet season n Mn dry season • Mn wet season Site IDs upstream • downstream (not to scale) Figure 4.27 Bioavailable concentration of Fe and Mn in surface waters for the dry and wet seasons 4.5 Sediment analysis results 4.5.1 Particle size distribution Results of particle size analysis for each one of the sampling sites are presented in Table 4.9. Table 4.9 Particle size distribution results for composite sediment samples collected July 2004 and February 2005 (all results in % of dry weight) Creek SiteJD granule very coarse coarse and fine and very Silt and clay sand medium sand fine sand Bertrand BCr1 22.2 15.4 44.5 14.4 3.4 Creek BCr2 10.7 7.8 31.5 38.7 11.3 BCr3 1.7 5.6 71.2 17.5 4.0 BCr4 5.2 13.7 67.7 10.2 3.1 BCr8 47.1 8.8 26.3 13.8 4.0 BCM1 23.7 21.8 37.1 13.8 3.6 B C M 2 12.6 7.5 51.6 25.2 3.1 Howes Creek HC5 20.0 25.9 26.1 17.2 10.7 HC6 8.0 9.1 42.2 27.4 13.3 HC7 7.5 9.1 23.2 32.1 28.1 Pepin Creek P C 9 11.6 28.4 49.5 7.8 2.7 PC10 22.5 11.8 44.7 18.6 2.5 Cave Creek C C 1 3 4.5 13.6 66.1 11.3 4.5 6 3 4.5.2 Organic matter content Composite sediment samples (July 2004 + February 2005) were used for organic matter content analysis. A bulk sample for sediments (< 2 mm), as well as the < 63 pm fraction, were analyzed for organic matter content. The percent carbon in the < 63 pm fraction was always greater than for the bulk samples. Results for each one of the sites are presented as % weight carbon in Table 4.10. Table 4.10 Organic matter content of composite sediment samples. All results as % weight carbon SITEJD BCrl % carbon in bulk sample 1.0 % carbon in <63um fraction 2.2 BCr2 2.2 5.6 BCr3 1.2 4.0 BCr4 0.8 3.6 BCr8 1.9 4.6 BCr11 2.0 4.6 BCr12 0.4 2.8 HC5 2.4 3.1 HC6 2.0 3.5 HC7 14.4 11.1 PC9 2.9 8.5 PC10 1.4 7.4 CC13 0.7 2.5 64 4.5.2.1 Trace Elements in Sediments: Differences in Accumulation According to Particle Size Trace metal analysis was performed on two different sediment fractions to determine the percentage metal accumulation in the different fractions. Approximately 60% of the trace metal concentration was associated with the < 63 pm (silt and clay) fraction, which made up less than 30% of the total sediment fraction and in most cases (in 8 out of the 13 sampled sites) made up less than 4% of the total sediment fraction (Table 4.10). Results are presented in Table 4.11 and Figure 4.28. Table 4.11 Trace metal accumulation in sediments in relation to particle size Particle size ppm Al %AI ppm Cr %Cr ppm Cu %Cu <63 um 17785 61.6 41.7 62.63 30 57.0 2mm - 63um 110723 38.4 24.9 37.4 23 43.0 Total 28858 100 66.6 100 53 100 4.11 continued Particle size ppm Mn %Mn ppm Ni %Ni ppm Zn %Zn <63 um 901 67.5 30.1 56.8 157 63.1 2mm -63um 434 32.5 22.8 43.2 92 36.9 Total 1334 100 52.9 100 248 100 65 % Metal Accumulation in Proportion to Particle Size 100 80 60 4 • <63um • 2mm - < 63um $1-6* .2.6* $7.0* $7.5* J2.50 56.81 Al Cr C u Mn Ni Zn Figure 4.28 Trace metal accumulation in sediments in relation to particle size 4.5.3 Spatial and Seasonal Variations in Sediment Quality Twenty-two elements were analyzed on two occasions (dry season in July 2004 and wet season in February 2005) from samples collected at all sites. Elements analyzed were: Al , As, B, Ba, Ca , Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, P, Pb, Se, Si , Sr, and Zn. Out of all these elements, B, Cd, Mo, and Se were below detection limits for all sites for both sampling events. Arsenic was below detection limits for all sites during both seasons, except for site 7 on Howes Creek (HC7). The only sites below detection limit for Pb were sites 5 and 6 on Howes Creek (HC5 and HC6). HC5 was below detection limit during the dry season only and HC6 during both seasons. Sites HC7 and 10 on Pepin Creek (PC10) were below detection limit for Co during the dry season. The Mann-Whitney U Test was used to compare urban and rural sites in the watershed. Results showed significant differences between these two for the dry season only, with the exception of copper which was significantly higher in urban stations along Bertrand Creek compared to those rural sites on Howes Creek (a < 0.05) during the wet season. During the dry season copper, lead, and zinc (a < 0.05) were significantly higher in the urban portion of the watershed compared to rural sites on Bertrand and Howes Creek. There were no significant differences between any of the rural sites or between urban sites on Bertrand Creek and sites on Pepin Creek. Table 4.12 summarizes significant differences in sediment quality 66 between the different sampling sites in the watershed. Even though the Mann-Whitney U Test showed no significant differences between sediment quality for the dry and wet seasons, the graphs below present element concentrations in sediments for both of these seasons in the upstream to downstream direction. Iron levels were always one order of magnitude higher at site HC7 than at all other sites. A very marked decrease in Cu concentrations can be observed from the urban towards the rural sites on Bertrand Creek in the downstream direction, especially during the dry season. Element Stream Name Site IDs <or > In comparison to Cu, Pb, Zn Bertrand Creek BCr1, BCr2, BCr3 > Howes Creek (all stations) Bertrand Creek (rural stations) Aluminum Concentrations of aluminum in sediments ranged between 9329 and 30129 ppm with a median of 18290 ppm Al . The highest concentration was found at site 5 on Howes Creek (HC5) during the rainy season while the lowest concentration was found at site 7 on that same creek during the dry season. Even though concentrations were not significantly different between urban and rural sites, these seem to show an increase in the downstream direction as Bertrand Creek enters the rural portion of the watershed. Trends are presented in Figure 4.29. E a. Q. 35050 30050 25050 20050 15050 10050 5050 50 Urban Sites Rural Sites —•—dry season —•— wet season \ S 1 1 — i — i — i — • i ! I I I I I I I I I o CO O J co £ O O O co co co CO i - CM O co o o CO CO LO o X CO O X O X CO o O *-CL O CL CO O O Site IDs upstream- -•downstream (not to scale) Figure 4.29 Spatial and seasonal variations in Al concentrations in sediments 67 Calcium Concentrations of calcium seemed to have a slightly decreasing trend in the downstream direction in Bertrand Creek, particularly during the wet season when concentrations were significantly higher (a<0.05) in the urban portion of the stream. Calcium concentrations in sediments in the watershed ranged between 12672 and 3371 ppm with a median concentration of 5175 ppm. Results are presented in Figure 4.30 below. Site IDs upstream • downstream (not to scale) Figure 4.30 Spatial and seasonal variations in C a concentrations in sediments 68 Magnesium Trends in magnesium are similar to those found for potassium. Station 1 on Bertrand Creek showed the highest concentrations, particularly during the wet season. Concentrations throughout the watershed ranged between 2071 and 11,599 ppm, with a median of 6031 ppm. Results are presented in Figure 4.31. Site IDs upstream •downstream (not to scale) Figure 4.31 Spatial and seasonal variations in Mg concentrations in sediments 69 Iron Iron concentrations did not exhibit any particular spatial pattern or seasonal trends, but they were always highest at station 7 on Howes Creek. Concentrations ranged from 16,140 to 195,553 ppm, with a median of 29,927 ppm. The lowest concentrations were found on Pepin Creek, which is characterized by coarse streambed sediments. Variations in iron concentrations in the watershed are presented in Figure 4.32 Site IDs upstream • downstream (not to scale) Figure 4.32 Spatial and seasonal variations in Fe concentrations in sediments Potassium Potassium concentrations ranged between 401 and 2082 ppm with a median of 969 ppm. Overall, they tended to be higher during the wet season. The highest concentrations were found at station 1 on Bertrand Creek. Figure 4.33 shows spatial and seasonal variations in the concentration of potassium in streambed sediments. Site IDs upstream •downstream (not to scale) Figure 4.33 Spatial and seasonal variations in K concentrations in sediments 71 Manganese Manganese concentrations were highest at station 10 on Pepin Creek for both sampling events. Overall, concentrations were found between 434 and 4500 ppm with a median of 1177 ppm. Figure 4.34 presents the variations in manganese concentrations in streambed sediments throughout the watershed. —•— dry season —•— wet season Site IDs upstream •downstream (not to scale) Figure 4.34 Spatial and seasonal variations in Mn concentrations in sediments 72 Chromium Concentrations of chromium in the watershed were between 23 and 80 ppm with a median of 45 ppm. Spatial and seasonal variations are reflected in Figure 4.35. E a a k. o 90 80 70 60 50 40 30 20 10 0 Urban sites Rural sites • • r CN CO S o o o o CD CO CO CO o CD 1— L_ o o 00 CD m CD O O X X O CD O D_ o CL —•—dry season —"—wet season Site IDs upstream • downstream (not to scale) Figure 4.35 Spatial and seasonal variations in Cr concentrations in sediments CO O O 73 Nickel Concentrations of nickel were between 25 and 92 ppm with a median of 36 ppm. Figure 4.36 shows the seasonal and spatial variations in concentrations. Figure 4.36 Spatial and seasonal variations in Ni concentrations in sediments Phosphorus Concentrations of phosphorus were highest in streambed sediments at site 7 on Howes Creek most likely due to the organic nature of these sediments. Concentrations of phosphorus in sediments ranged between 1164 and 17,571 ppm with a median of 1667 ppm. Figure 4.37 below summarizes these results. 21000 • 18000 15000 12000 a. 9000 Q. Urban sites 6000 3000 r- CM o CQ O CQ Rural sites O CQ o CQ OO i_ O CQ O CQ CM "i— i o CQ LO CD I O O O X X X •dry s e a s o n - wet s e a s o n CO O CL O CL CO O O Site IDs u p s t r e a m •> d o w n s t r e a m (not to sca le) F i g u r e 4.37 S p a t i a l a n d s e a s o n a l var iat ions in P c o n c e n t r a t i o n s in s e d i m e n t s 75 Copper Concentrations of copper exhibited a very clear decline in the downstream direction. Concentrations were significantly higher in sediments at the urban stations than at the rural stations. Also, this pattern on Bertrand Creek was more evident during the dry season. Concentrations were between 29 and 81 ppm with a median of 43 ppm. Figure 4.38 shows these results. 76 Lead Lead concentrations were clearly higher in streambed sediments at urban stations. Concentrations were within the range of 21 and 168 ppm with a median of 54 ppm. Station 9 on Pepin Creek had the highest concentration during the wet season. These results are presented in Figure 4.39. Site IDs uDStream •downstream mot to scale) Figure 4.39 Spatial and seasonal variations in Pb concentrations in sediments 77 Zinc Zinc was perhaps the element to exhibit the most clear spatial trends. Concentrations of zinc in streambed sediments were much higher at stations 1, 2 and 3 on the urban portion of Bertrand Creek and experienced a marked decrease in the downstream direction as the creek enters the rural area. Spatial and seasonal fluctuations are presented in Figure 4.40. 78 4.5.4 Correlations between elements in sediments Significant correlation results between elements in sediments for the dry and wet seasons can be found in Appendix D. Overall, there were very few elements negatively correlated (only Na to Mn) to each other, but there was a distinct group of elements that were mostly positively correlated to one another (Al, Co, Cr, K, Mg, Ni) during the wet season. There were no identifiable groups of elements for the dry season. Trace metals associated with urban stations (lead, zinc and copper) were always positively correlated to one another. 4.6 Relationships between Land Use, Sediment, Surface and Groundwater Quality 4.6.1 Correlations between Land Use Categories and Groundwater Quality Figure 1.2 shows land use for the Canadian portion of the Bertrand Creek watershed. Data was again split into the dry and wet seasons for analysis. Percent land use within the five established categories for each of the participating wells can be found in Appendix B. Correlations for the dry season are presented in Table 4.13. For the wet season, no correlations were found except for N 0 3 - N which was negatively correlated with rural residential/hobby farms, and K which was negatively correlated to areas with trees and bushes. Table 4.13 Spearman Rank Correlations between land use and groundwater quality parameters during the dry season ** correlation is significant at the 0.01 level (2 - tailed) * correlation is significant at the 0.05 level (2 - tailed) Land use category Positively correlated to Negatively correlated to Rural residential/hobby farms pH**, specific conductivity*, TDS*, N 0 3 - N * P0 4 ** Animal operations None pH*, P0 4 ** Other None cr* 79 4.6.2 Correlations between Land Use Categories and Surface Water Quality Seven main land use categories were identified within stream buffers. Percent area for each of these categories is presented in Table 4.14. However, the "urban residential "gravel extractions" and "rural residential/hobby farms" categories had too few data points associated with them to perform correlation analysis. Therefore, the category "urban residential", which mainly comprises impervious surfaces, was aggregated to the land use category labeled as "other", and a new category - "impervious surfaces" - was used to try to determine relationships between land use and surface water parameters. The same applies to the "rural residential/hobby farms" category, which was joined with "all other agricultural uses" to create a new category labeled as "other agricultural activities". This last category was used to perform correlation analysis. Since the category "gravel extractions" was only present in two stream buffers and its characteristics are very different to the other types of land use identified in the watershed, it was not possible to create a new category and it was therefore not taken into account for Spearman's rank correlation analysis. The percent land use within each of the categories used for correlation analysis is presented in Table 4.15. Table 4.14 Percent land use within stream buffers for the seven main categories identified in the Bertrand Creek watershed % Land Use SITEJD B C M Urban residential 10.65 Rural residential /hobby farms Animal operation 79.49 Trees & bushes Gravel extraction All other agricultural Other 9.86 BCr2 56.05 — 3.52 2.74 — — 37.69 BCr3 84.5 — — 6.22 — — 9.21 BCr4 — — 49.41 — — 47.82 2.77 BCr8 — — 93.75 — — 2.02 4.24 BCM1 — 0.97 65.68 25.6 — — 7.76 B C M 2 — 0.02 59.91 14.96 — 25.11 — HC5 — — 5.26 4.05 — 90.42 0.27 HC6 — — 41.37 12.8 45.83 — — HC7 — 11.34 83.72 — — 2.34 2.60 PC9 — 1.35 1.40 93.94 1.12 — 2.20 PC10 . . . . — 20.51 79.49 — — — C C 1 3 — — 67.95 28.06 4.00 80 Table 4.15 Percent land use within stream buffers for the categories used for correlation analysis % Land Use SITEJD BCr1 Impervious surfaces 20.51 Other agricultural activities Animal operation 79.49 Trees & bushes BCr2 93.74 — 3.52 2.74 BCr3 93.78 — — 6.22 BCr4 2.77 47.82 49.41 — BCr8 4.24 2.02 93.75 — BCr11 7.76 0.97 65.68 25.6 BCr12 — 25.13 59.91 14.96 HC5 0.27 90.42 5.26 4.05 H C 6 2 — — 41.37 12.8 HC7 2.60 13.68 83.72 — P C 9 3 2.20 1.35 1.40 93.94 PC10 — — 20.51 79.49 C C 1 3 — 4.00 67.95 28.06 Stream quality data was split into the wet and dry seasons for correlation analysis. There were no significant correlations during the dry season and very few for the wet season. Significant correlations for the wet season are summarized in Table 4.16. Surprisingly and despite being the main land use within the watershed, animal operations were not correlated to any surface water quality parameters. Table 4.16 Spearman Rank Correlations between surface water quality parameters and land use during the wet season ** correlation is significant at the 0.01 level (2 - tailed) "correlation is significant at the 0.05 level (2 - tailed ) Land use category Positively correlated to Negatively correlated to Impervious surfaces C\'**, Na* N 0 3 " - N*, pH*, Sr*, K** Other agricultural activities N 0 3 " - N * Animal operations Trees and bushes pH* C P 2 45.83% not presented in table corresponds to gravel extractions 3 1.12% not presented in table corresponds to gravel extractions. 81 4.6.3 Correlations between Land Use Categories and Sediment Quality Parameters The same four categories that were used to explore correlations between land use and surface water quality parameters were used in correlation analysis for sediment quality parameters and land use. Significant correlations for the dry season are presented in Table 4.17. During the wet season, only the trace metals copper and zinc were significantly correlated to impervious surfaces. This relationship between impervious surfaces was consistent during both seasons, but correlations were stronger during the dry season. In addition, Pb was also positively correlated to impervious surfaces during the dry season. Table 4.17 Spearman Rank Correlations between sediment quality parameters and land use during the dry season ** correlation is significant at the 0.01 level (2 - tailed) * correlation is significant at the 0.05 level (2 tailed) L a n d u s e c a t e g o r y P o s i t i v e l y c o r r e l a t e d t o N e g a t i v e l y c o r r e l a t e d t o I m p e r v i o u s s u r f a c e s Ba*, Cu**, Pb**, Zn** O t h e r a g r i c u l t u r a l a c t i v i t i e s Cu* A n i m a l o p e r a t i o n s Trees a n d b u s h e s Ba*, Fe**, P** 4.7 Relationships between Ground and Surface Waters Sites on Cave and Pepin Creeks don't seem to be under significant influence of groundwater and they all exhibited normal seasonal trends for NOy - N, having higher concentrations during the rainy season which suggests nitrates originate from surface runoff. This is also true for most sites on Bertrand Creek, with the exception of site 8 (BCr8) that shows its highest concentration in June and site 4 (BCr4) which exhibits completely the opposite trend: higher nitrate concentrations in the summer. Normally, for surface waters that are not under the influence of groundwater, nitrate concentrations would be higher during the rainy season due to surface runoff and lower during the summer when there is very little input from runoff and higher nutrient uptake by plants. Groundwater influence is particularly evident at site 5 (HC5) on Howes Creek which flows over the Abbotsford aquifer and showed exceptionally high levels of nitrate during the dry season. However, the same does not apply for the other two sites on Howes Creek, since these were dry during the summer, suggesting little or no recharge from groundwater at these points. In the Sumas River watershed, Marshall Creek, which is recharged in the summer by the Abbotsford aquifer, exhibits a similar trend to that of station 5 82 on Howes Creek [Smith, 2004; Berka, 1996]. Figures 4.41 to 4.43 show seasonal nitrate trends in the watershed. Low dissolved oxygen concentrations during the summer can also be indicative of groundwater influence. This however, can also be due to the lack of aeration and low flow during this time of year. Dissolved oxygen concentrations at sites 4 and 8 on Bertrand Creek and site 5 on Howes Creek were not particularly low during the summer, but this might be due to the fact that these stations have significantly good flow even during the driest months in the year. On the other hand, extremely low dissolved oxygen concentrations at station 9 on Pepin Creek during the months of July and August (0.9 and 1.6 mg/L respectively) suggest that there is some groundwater recharge. Besides, streambed sediments at this station are mostly composed of gravel. Groundwater recharge to Pepin Creek had previously been reported by Pearson (2004). In some cases, conductivity might be used as indicator of groundwater influence [Magwood, 2004], but again, this parameter might be correlated to flow and precipitation, since ions of dissolved elements would normally be more concentrated when there is less water in the stream. Conductivity didn't seem to be higher at stations where groundwater seems to be recharging the streams. Figure 4.41 Seasonal variations in N 0 3 " - N concentrations on Bertrand Creek 83 3.0 2.5 ^ 2.0 CO O Z 1.5 1.0 0.5 -i 0.0 c£ c£ c£> Qp cp cp pfc r > C > C> C> *r # j f j f # # # ^ ^ .4? f^ Figure 4.42 Seasonal variations in N 0 3 " - N concentrations on Pepin and Cave Creeks • - H C 5 • - H C 6 A - H C 7 w <f <r & jf <f & rf <f <f *&* & Figure 4.43 Seasonal variations in N 0 3 " - N concentrations on Howes Creek 84 5 Discussion 5.1 Groundwater Quality and well owners' perception of water quality Section 1.1.1 of this study presents a detailed description of the groundwater resources in the Bertrand Creek watershed. In general, most of the aquifers consist mainly of glaciofluvial sand and gravel deposits, which makes them vulnerable to contamination from surface sources and which influences the quality of water, particularly in terms of specific conductivity, chloride and concentrations of dissolved elements. A map of the surficial geology of the Township of Langley is provided in Appendix H. 5.1.1 Nitrate - N spatial variability and relationship to depth The Guidelines for Canadian Drinking Water Quality (GCDWQ) establish the maximum acceptable concentration (MAC) for nitrate - nitrogen to be 10.0 mg/L. Furthermore, other groundwater studies conducted in the Lower Fraser Valley [Magwood, 2004; Schreier, et. al., 1996a; Carmichael ef al., 1995] consider groundwater with nitrate - N concentrations greater than 3.0 mg/L to be potentially under human influences. Nitrate - N concentrations for the present study ranged from below detection limit (< 0.002 mg/L) to 24.0 mg/L with a mean of 4.03 mg/L and a median of 2.02 mg/L. In this context, 17 out of the 40 wells sampled for the study during the dry season had concentrations above 3 mg/L; 14 of these are wells located on the Abbotsford (A) aquifer, 1 is located on the South of Hopington Aquifer, 1 on the Aldergrove Quadra and 1 on the Aldergrove A B aquifer. Only 7 out of the 40 wells sampled during the dry season were above the Canadian Drinking Water Quality guideline of 10 mg/L and all of these were located on the Abbotsford (A) aquifer. Due to the fact that some participants failed to provide samples during the wet season, data is available for 37 wells only for this period. Out of these, 18 had N 0 3 " - N concentrations above 3 mg/L and only 5 (all on the Abbotsford A aquifer) exceeded the 10 mg/L guideline. Results show that nitrate is a main concern in the Abbotsford (A) aquifer. Out of the 40 wells sampled during the dry season, 27 were located on this aquifer, which means that 52% of the wells sampled on this aquifer presented concentrations above 3 mg/L and 26% were above 10 mg/L. During the wet season, 26 of the 37 wells sampled were on Abbotsford (A) aquifer and percentages for this period are similar to those obtained for the dry season; 58% of the wells 85 sampled on the Abbotsford (A) aquifer were above 3 mg/L NOy - N and 20% were above 10 mg/L NOV - N. These results are similar to those from previous studies conducted on the Abbotsford aquifer that show high nitrate contamination [Erickson, 2000; Zerbath, ef. a/., 1998; Carmichael, ef. al, 1995; Wassenaar, 1995; Liebscher, 1992]. Carmichael's study in 1995 found elevated NOy -N values (greater than 10 mg/L) in 3 heavily utilized and highly vulnerable aquifers: the Hopington, the Langley/Brookswood and the Abbotsford/Sumas. Of these three aquifers, the Abbotsford/Sumas had a consistently high mean and median and had the highest percentage of wells (36%) exceeding the drinking water quality guideline of 10 mg/L N 0 3 " - N. Furthermore, 69 % of wells in the Abbotsford aquifer were above 3 mg/L N 0 3 " - N. Table 5.1 presents a summary of the findings of this study and compares them to other studies conducted in the Lower Fraser Valley and elsewhere in North America. Table 5.1 Comparison between nitrate concentrations in groundwater (mg/L N03" - N) Location Bertrand Creek watershed GOBLE 2005 Brookswood Aquifer MAGWOOD 20044 Hatzic Valley ZERBATH, et. al. 19985 Abbotsford Aquifer SCHREIER, ef. al., 1996 Hopington Aquifer WASSENAAR 1995 Abbotsford Aquifer N 40 70 75 36 70 117 Range <0.002 -24.0 0.002 -49.7 0.05-11.96 0.0-43.2 0.01 -48.1 0-151 Mean 3.94 — 0.94 (S) 1.24 (W) 13.47 — — Median 2.24 1.69 0.362 (S) 0.498 (W) — 46 25 t h & 75 t h percentiles 0.022 6.56 — — % > 3 mg/L 42.5% — 16% 92% 30 - 40% — % > 10 mg/L 17.5% 9% 3% 69% 5-13% 54% 4 Mean and median N0 3" - N concentrations for the summer (S) and winter (W) 5 % of samples above 3 andlO mg/L N0 3" - N for Zerbath, et. al. is calculated based on those samples with means above the given concentrations 86 Table 5.1 continued CARMICHAEL ef. al, 1995 LIEBSCHER 19926 ERICKSON 2000 LEVALLOIS ef. al., 19987 LIU, et. al., 2004 Location Fraser Valley Abbotsford Aquifer Sumas-Blaine Aquifer Quebec Portneuf county A B Alabama, U S A N 240 >450 53 71 75 1021 Range <0.02-72.7 <0.01 - 4 2 . 3 0 .012-22 .1 — > 0.1 - 118 Mean 3.29 — 9.95 — 1.5 Median 0.59 — 10.3 — 0.5 25 t h & 75 t h percentiles 0.04 3.13 — — — — % > 3 mg/L 25% — — 19.7% 54.7% — %> 10 mg/L 11% Approx60% 51% 5.6% 13.3% 1.7% It is worth noting that Carmichael's ef. al. study (1995) was conducted throughout the Lower Fraser Valley, and thus, many of the wells sampled (31) were located on unconfined aquifers and had very low nitrate - N levels ranging from < 0.02 - 1.81 mg/L NOy - N. However, the percent of wells with N 0 3 " - N concentrations above 3 mg/L in the Abbotsford/Sumas aquifer was 69%; 40% in the Hopington; 33% in the Langley/Brookswood and 18% in the Nicomen Slough aquifer. These last figures reflect the impact of human activities on water quality in vulnerable aquifers. These results are more in accordance with the ones obtained in this study (42.5% of wells sampled above 3 mg/L NOy - N). Mean nitrate concentrations in the Abbotsford aquifer have shown a notable increase throughout time [Erickson,2000; Zerbath, ef al 1998; Liebscher, 1992] . The results from the present study confirm the fact that the Abbotsford (A) aquifer is one of the most heavily contaminated by nitrates and improving water quality in the aquifer continues to be a priority. This, however, can prove rather challenging since residence time of groundwater in the aquifer 6 Presents data collected between 1955 and 1990 from a large number of wells and piezometers over extended and often irregular time intervals. Meaningful mathematical correlations are difficult to present partly due to to the size of the data base, the irregular sampling frequency, the sampling bias towards highly impacted areas, depth below water table, seasonal fluctuations and changing land use practices. 7 In Levallois's study, two groundwater surveys were conducted. Column A corresponds to the results from wells chosen at random among people drinking tap water in Portneuf County. Column B corresponds to nitrate - N concentrations in wells chosen at random in "hot spot" areas in the county, which are defined as a row where at least 1 well was found above 7 mg/L N0 3" - N 87 is the order of decades and the Abbotsford aquifer does not sustain denitrification [Wassenaar, 1995]. In terms of the relationship between N 0 3 " - N concentrations and depth, there was a clear negative correlation between these two. Shallow wells have long been known to be more susceptible to contamination from surface sources than deeper wells as a result of the high solubility and mobility of nitrate in soils, which accumulates in the root zone as a product of agricultural activities and leaches down into the aquifers. In the case of this study, there were no wells deeper than 15 m that exceeded the Canadian drinking water quality guideline of 10 mg/L NGy - N and only 2 exceeded 3 mg/L NOy - N. Although at varying depths, other studies have also found a general tendency of nitrate concentrations to decrease with increasing well depth [Goble, 2005; Liu, et. al., 2004; Magwood, 2004; Carmichael et. al., 1995; Schreier et. al., 1992;]. 5.1.2 Orthophosphate Although there is no drinking water quality guideline for phosphorus, high concentrations of this nutrient in groundwater are of concern from the perspective of eutrophication of surface waters in those cases where these are impacted by recharge from groundwater sources. Phosphorus has low solubility and low mobility in soils and aquatic systems. In most natural surface waters, phosphorus concentrations range from 0.005 to 0.02 mg/L P 0 4 - P, though concentrations as low as 0.001 mg/L P 0 4 - P can be found in some pristine waters. Average groundwater levels are about 0.02 mg/L P 0 4 - P [Chapman, 1996]. McGarrigle et. al. (2002) cite the Water Pollution Act of 1977 as establishing that groundwater levels should not exceed 0.03 mg/L P - P 0 4 when providing baseflow to a river and 0.02 mg/L total phosphorus if it feeds a lake, in order to prevent eutrophication of surface waters. Often, a concentration of 0.01 mg/L phosphate is used as a standard for the prevention of lake eutrophication. Schreier, et. al., (1996) used a more conservative concentration of 0.1 mg/L orthophosphate to show the extent of the contamination problem in groundwater samples from the Hopington aquifer. Therefore, for the purpose of comparison, this same concentration is used in this study to determine whether orthophosphate levels in groundwater could have a potential deleterious impact on the quality of surface waters in the Bertrand Creek watershed. During the dry season, 9 of the 40 (23%) wells sampled were above 0.1 mg/L P 0 4 , but only 3 of the 37 (8.1%) wells sampled during the wet season exceeded this limit. When compared to Schreier's et. al. results, these figures are relatively low, since about 40% of the wells sampled for their study in the Hopington aquifer were above this concentration. On the Hatzic Island, all 88 the samples taken had results above 0.01 mg/L P 0 4 [Magwood, 2004], which is the concentration considered to be of concern for the eutrophication of lentic bodies of water. In the case of the Bertrand Creek watershed, it is possible that groundwater phosphate concentrations are not causing a notable impact on surface waters, since there was no significant difference between phosphate concentrations in streams between the wet and dry seasons, suggesting that seasonal groundwater recharge of streams has little or no impact. Orthophosphate concentrations in groundwater in this study presented a positive correlation to depth and specific conductivity. These same correlations were found by Magwood (2004) in her study in the Hatzic Valley, and it was suggested that phosphate concentrations in these cases might originate from geological processes. Schreier ef. al., (1996) also found a positive correlation between well depth and phosphate concentrations in the Hopington aquifer. Goble (2005) found the same tendency in the Brookswood aquifer. 5.1.3 Chloride The Canadian Drinking Water Quality Guidelines set an aesthetic objective for chloride of < 250 mg/L mainly because of the undesirable taste it might impart and because it may cause corrosion of distribution systems. In the present study only 2 of the wells sampled during the dry season exceeded this limit. Other studies in the Lower Fraser Valley [Goble, 2005; Schreier ef. al., 1996] haven't found chloride concentrations of concern. Low chloride concentrations are directly related to the geology in the area since most of the sampled wells are located on the Abbotsford aquifer which consists mainly of glaciofluvial sand and gravel deposits from the Sumas Drift formation. 5.1.4 pH An aesthetic objective for pH values in drinking water has been set in the range of 6.5 - 8.5, since corrosion effects may become significant below 6.5 and the frequency of incrustation and scaling problems, as well as progressive decrease in the efficiency of chlorine disinfection processes may be accentuated above pH 8.5 [pH supporting document for Canadian Drinking Water Quality Guidelines, 1979]. pH concentrations in the wells sampled (for both seasons combined) ranged from 4.36 - 9.15 with a mean of 6.73 and a median of 6.44. Out of the 40 wells sampled in the dry season, 20 (50%) were below the pH limit of 6.5 and only 1 (2.5%) was above 8.5. During the wet season, 21 (57%) of the 37 wells sampled were below 6.5 and 2 (5.4%) were above 8.5. Magwood (2004) found that pH was the most commonly exceeded parameter, with 60% of her samples 89 below 6.5. Schreier et. al., (1996) found pH values ranging from 5.8 - 8.7 in the Hopington aquifer. pH values in groundwater samples in this study showed a strong positive correlation to well depth and specific conductivity, which are trends observed in other aquifers as well [Liu, et. al., 2004; Schreier, et. al., 1996]. The connection that exists among well depth, pH and specific conductivity (and therefore Total Dissolved Solids) suggests that pH is influenced by the content of dissolved salts. This is reflective of the leaching processes in soils, since water moving further through the aquifer to greater depths has an increased opportunity of dissolving salts, thus increasing the alkalinity of water [Schreier, et. al, 1996]. 5.1.5 Turbidity In terms of turbidity, the Canadian Drinking Water Quality Guidelines have set different maximum concentrations according to the filtering system. The highest value set is 1.0 NTU, and this will be used for discussing the results of this study. Turbidity in the wells sampled in the study ranged from 0.11 - 447.0 NTU with a median of 0.29 NTU. The highest values (309 NTU for the summer and 447 NTU for the winter) correspond to well 4 on the Abbotsford aquifer. However, these values are considered outliers and are due to site-specific conditions. Furthermore, the well owner also reported the use of a filter to treat his water for drinking. 17.5% of the wells sampled during the dry season exceeded the 1.0 NTU turbidity guideline. 5 of these wells are located on the Abbotsford aquifer, 1 on the Aldergrove Quadra and 1 on the Aldergrove A B aquifer. During the wet season sampling event, 16.2% of the samples exceeded the guideline - 1 on the South of Hopington aquifer, 1 on the Aldergrove Quadra and 4 on the Abbotsford aquifer. Approximately half of the well owners whose water exceeded the guideline for turbidity reported using some kind of filter to treat their water, which supports the results that well owners link water quality to visible abnormalities. 5.1.6 Total Dissolved Solids The Canadian Drinking Water Quality Guidelines set an aesthetic objective of < 500 mg/L total dissolved solids, since at higher levels, excessive hardness, unpalatability, mineral deposition and corrosion may occur. Furthermore, the Canadian Water Quality Guidelines for the Protection of Agricultural Water Uses sets guidelines of 500 - 3,500 mg/L TDS for irrigation and 3,000 mg/L TDS for livestock watering. 4 of the 40 wells sampled in the summer and 3 of the 37 wells sampled in the winter exceeded the drinking water guideline, but none exceeded the guidelines for the protection of water for agricultural purposes. In this area low specific 90 conductivity and total dissolved solids are also reflective of the low pH in waters and the geological characteristics of the region. 5.1.7 Dissolved elements Since groundwater often occurs in association with geological materials containing soluble minerals, higher concentrations of dissolved salts are normally expected in groundwater relative to surface water [Chapman, 1996]. Sources and concentrations of natural groundwater components [Chapman, 1996] are presented in Table 5.2 for the purpose of comparing the results obtained in this study. One of the processes influencing the concentrations of minerals in groundwater is atmospheric precipitation. By dissolving C 0 2 present in soils from the microbial activity a weak carbonic acid solution is produced, which in turn, dissolves minerals in rocks. Since recharge to the aquifers in the study areas is mainly from rainfall (meteoric groundwaters), concentrations of minerals in their water are most likely due to this process. On the other hand, water moving rapidly through an aquifer (those highly permeable and with good drainage), will only remove readily soluble minerals from rocks, due to the short contact time with the rock matrix [Chapman, 1996]. Table 5.2 Concentrations of natural groundwater components Component Concentration in natural water Calcium Usually < 100 mg/L Iron Usually < 0.5 mg/L in fully aerated water; groundwater with pH <8 can contain 10 mg/L; infrequently 50 mg/L may be present Magnesium Usually < 50 mg/L Manganese Groundwater contains > 10 mg/L Potassium Usually < 10 mg/L Silica Ranges between 1 - 30 mg/L, but concentrations of as much as 100 mg/L can occur Sodium Generally < 200 mg/L Source: Chapman, 1996 Median values for dissolved elements for the wells sampled in the watershed are all within the range of the concentrations of natural groundwaters presented in Table 5.2. From the elements analyzed in this study, only Cu, Fe, Mn, Na and Zn have drinking water quality aesthetic objectives associated with them. Aesthetic objectives and the percent of wells 91 that exceed these concentrations in the samples collected in February 2005 are presented in Table 5.3. Table 5.3 Canadian Drinking Water Quality aesthetic objectives for dissolved elements in water and % of wells in the study exceeding the objectives Cu Fe Mn Na Zn Aesthetic objective < 1.0 mg/L < 0.3 mg/L < 0.05 mg/L < 200 mg/L < 5.0 mg/L % of wells exceeding 2.7% 16.2% 16.2% 8 5.4% 0% the objective N = 37 5.2 Land Use Impacts on Groundwater Quality According to data from the 2001 Census of Agriculture from Statistics Canada [in Golder Associates, 2005], the Aldergrove and Abbotsford/Sumas aquifers are among the most heavily developed in terms of agriculture in the Lower Fraser Valley. This information is provided in Table 5.4. Table 5.4 2001 Census of Agriculture Data Item Aquifer Langley/Brookswood Hopington Fort Aldergrove Abbotsford/Sumas Langley No of farms 261 322 41 309 522 Total area of 2,244 3,526 863 2,957 6,772 farms (Ha) Land in crops 1,170 1,322 276 1,187 3,645 (Ha) Use of 103 302 21 178 2,293 irrigation (Ha) Total poultry 1,161,042 905,490 X 1,539,731 3,879,739 Total cattle 2,328 2,551 941 2,360 3,475 and calves Total sheep 697 667 92 543 1,007 and lambs Total pigs 59 725 X 2,785 3,482 Total horses 1,021 861 236 506 728 and ponies X data suppressed to protect confidentiality Source: Golder Associates, 2005 Wells exceeding the aesthetic objective for iron also exceeded the objective for manganese. 92 According to Smith (2004), characteristics of agricultural operations in the Sumas Prairie region have shifted from smaller scale dairy farms towards high-density hog and poultry operations. The number of livestock per hectare of land has also increased dramatically in the area of the Abbotsford aquifer, resulting in greater amounts of manure being produced on a relatively unchanged land base. Wassenaar (1995), through the use of 1 5 N and 1 8 0 isotopes, concluded that nitrate in the Abbotsford aquifer mainly originates from poultry manure. Furthermore, Zerbath, ef. al. (1998) state that spatial distribution of high nitrate concentrations appeared to correlate with agricultural land use patterns. In their study, they analyzed data for the period between 1971 and 1991 and determined that there was a major shift in animal production in the area during this period. They concluded that the increase in the nitrogen surplus in the area was primarily from changes in land use. In particular, the shift from animal production which requires a local land base for crop production and grazing, to animal production where the feed is imported (i.e. shifting from cattle to poultry and hogs and removal of grass, hay and pasture and replacement with small fruit crops). Even though this agricultural trend is also applicable to the land area overlying the Aldergrove aquifer, wells on this aquifer didn't appear to be as impacted by nitrate contamination as those on the Abbotsford, possibly due to the fact that it is a semi - confined aquifer and therefore, less vulnerable. Nevertheless, there were too few wells sampled in the aquifers of the Aldergrove region and thus, further monitoring might be necessary. Land use correlations to groundwater quality parameters for this study found no relationships between NOy - N concentrations and agricultural activities. This might be due to low animal densities in the areas sampled, in which case the effect on nitrate concentrations would be negligible. Yet another possible explanation is the extension of pasture areas in the watershed, which is a highly efficient crop in the removal of nitrogen compared to small fruit crops such as berries [Zerbath ef. al., 1998]. Orthophosphate was positively correlated to rural residential areas and hobby farms. It is likely that phosphorus in this case originates from septic systems, garden fertilizers or domestic products such as detergents. Even though P 0 4 in drinking water is not considered a health hazard, high concentrations in groundwater are of concern for eutrophication if they provide baseflow to a river or feed a lake. 93 5.3 Public Perceptions of Groundwater Quality The survey used to assess well owners' perception of groundwater quality had been previously used in other study in the Lower Fraser Valley [Goble, 2005; Magwood, 2004; Schreier et. al., 1996]. Participation level in the study was considerably low: out of 300 letters of invitation and surveys distributed in the watershed, only 36 people completed the survey, thus consenting to participate in the study. This is due to the participant selection method used where letters were distributed in people's mailboxes with postage-paid envelopes so they could return the completed survey. Many surveys were received blank, possibly because the post office employee picked up the letters before home owners had a chance to read them and return them to IRES, or possibly because residents are not motivated by generic mail that is not personally addressed to them. Furthermore, the low response received didn't allow for the possibility to select participants and ensure a homogenous spatial distribution throughout the watershed or an even distribution of wells according to depth. As previously shown, most of the wells sampled for the study are located in the Abbotsford aquifer and there is a high possibility that well owners were motivated to participate due to the well-known nitrate contamination in this aquifer, thus biasing the results of the study. The methodology employed by Schreier et. al. (1996) and Magwood (2004) to select participants provides a better way to ensure spatial distribution and a significant number of wells in each depth category. Compared to past studies, responses obtained in the Bertrand Creek watershed area are quite similar. Goble (2005) reported that 65% of well owners (N=111) filter or treat their groundwater, compared to 61.1% of people surveyed for this study (N = 36). Participants were also asked what their perception of the quality of their water was. People surveyed for the present study seemed to deem their water of a lower quality than those people surveyed in the Brookswood aquifer [Goble, 2005], Hatzic Valley [Magwood, 2004] or Hopington aquifer [Schreier, et. al., 1996], possibly due to the well documented problem of nitrate contamination in the Abbotsford aquifer. Table 5.1 compares the responses obtained in the different studies on the Lower Fraser Valley 9. 9 Results for Goble, 2005 were estimated from graph. Results for Magwood included an extra category ("fair"), which was joined with "moderate" for comparison purposes. Results from Schreier, et al 1996 were scaled down from 107%, since results provided added up to 107%. 94 When asked whether they thought an increase in groundwater use would be appropriate, results from all the studies are very similar, perhaps reflecting the lack of public knowledge and regulation on groundwater resources in British Columbia. In the Bertrand Creek watershed, 63.9% of respondents said they needed more information in order to answer this question. Results are comparable to 52% in the Hopington aquifer [Schreier, et. al., 1996], 71% in the Hatzic Valley [Magwood, 2004] and 67% in the Brookswood aquifer [Goble, 2005] that had the same response. • Bertrand Creek Watershed • Brookswood aquifer • Hatzic Valley • Hopington aquifer hfcA Excellent Good Moderate Poor Figure 5.1 Well owners' perception of groundwater quality in the Lower Fraser Valley To assess public awareness of ground and surface water interactions, well owners were asked to what extent they thought groundwater affected local rivers in terms of quality and flow. The majority of the people surveyed (44 - 50%) said groundwater had a moderate impact on both, quality of surface waters and flow, indicating that there is some kind of awareness that surface and groundwater are interrelated. However, the percent of people that said that groundwater had a significant impact on surface water (16 - 22%) and those that said it had no impact at all, are comparable (19 - 22%). Also, over 10% of the people surveyed didn't answer this question, which, again, might reflect a lack of knowledge regarding this issue. In Magwood's study (2004), though the majority of the respondents said there was "some impact" from groundwater, a relatively high percentage (25.8%) said there was no impact. These results are similar to those found by Goble (2005), where close to 50% of the respondents opted for "a moderate impact" and only 20% thought there was a significant impact. 95 Magwood (2004) and Goble (2005) found that most people rely on visible parameters and smell/taste to rank the quality of their drinking water. This is not surprising, since not many people test their well water on a regular basis and are therefore unaware of the chemical or microbiological quality of their drinking water. There are other parameters, on the other hand, that are not necessarily harmful to human health, but that might cause people to reject water for drinking or domestic purposes due to the properties they impart to water. Such is the case of iron, which causes the water to have a reddish-brown color, gives water an "irony" (sometimes referred to as "bloody") flavor and can cause staining of clothes and fixtures. Some salts can also cause water to have an undesirable taste. Levallois, ef. a/., 1998 report that out of the 222 people interviewed in their study, 70 rejected regular tap water; 90% of those rejecting regular tap water admitted that was due to its organoleptic properties, rather than health concerns. The results of this study are in support of peoples' sensory ranking of their water quality. Over 50% of respondents said the most important parameters to determine their drinking water quality were visible particulate matter, visible abnormalities, color, smell and taste. A lower importance was assigned to depth of the water table, local newspaper reports and multiple gastrointestinal illness incidents in the community. The survey used in the study also aimed at determining well owners' perceptions of the importance of different land uses on the quality of water. The survey, however, failed to clearly specify whether water quality referred to ground of surface sources, and thus, results are general for both categories. Magwood (2004) found that in the Hatzic Valley, chemicals, manure and fertilizers used in farming, as well as industrial activities, were thought to have the greatest impacts on water quality. These results are consistent with Goble's (2005) and Schreier's ef. al., (1996), as well with the responses obtained for the present study. Chemicals in farming and industrial activities were ranked most important by 61.1% of the participants, followed by aggregate extractions and fertilizers in farming. This might be linked to studies of water quality on the Bertrand Creek area in the United States that have shown alarming presence of highly toxic pesticides (ethylene dibromide - EDB ) in groundwater. Public perception might have been significantly impacted by these findings since the stories received support from the media and they sparked a political battle [Symonds, 2004; Foster, 1999]. However, hobby farms, lawn fertilization, and septic systems failed to receive adequate attention from well owners, reflecting peoples' unawareness of the potential negative impact of these sources to nitrate levels and microbiological quality of water. 96 To assess public perception of the appropriateness of different groundwater management strategies, well owners were presented with a list and asked to rank the strategies from 0 (not appropriate at all) to 5 (most appropriate). Responses to this question reflect people's perception of land use impacts on water quality. The majority said that the most important strategies were restriction of fertilizers in agriculture and manure applications, as well as the restriction of garden chemicals. However, participants were not presented with an option of restriction of chemicals in agriculture and, even though 61.1% said industrial activities had a great impact on water quality, only 27.8% ranked as most appropriate the restriction of industrial development. Schreier ef. al., (1996), on the other hand, found that 51% of participants thought the introduction of municipal sewer systems was a highly appropriate strategy to manage groundwater resources. Even though the groundwater survey has proved a very useful tool in assessing public perception of water quality, some sections were unclear in their wording and others can present difficulties of scale. Whereas most questions use a six-point scale to rank importance of activities or strategies (5 extremely important - 0 not important), others use a seven-point scale reversed (7 not important - 1 extremely important). This might also cause some confusion in responding, since scales should ideally be kept constant throughout a survey to minimize the chance of errors in responses. Furthermore, six or seven point scales can prove difficult to quantify and present results. The results of this study could be used to develop a communication program to inform the general public of the quality of their groundwater resources and how they can contribute to improve its management. 5.4 Surface water quality The surficial geology of the Bertrand Creek watershed is dominated by glaciomarine stony clayey silt and silty sand from the Fort Langley Formation, particularly in the north end (urban portion) and western portion of the watershed. The south-central and eastern portions of the watershed are characterized by outwash sand and gravel deposits containing till lenses and clasts of glaciomarine stony clayey silt from the Sumas Drift formation [Armstrong, J . E., 1980, cited by Golder Associates, 2005]. 97 5.4.1 Nitrate - Nitrogen Background levels of NOy - N in British Columbia are less than 1.0 mg/L. The B C Water Quality Guidelines for nitrogen (1998) establish a limit of 200 mg/L NOy - N for the protection of aquatic life, a maximum of 100 mg/L for livestock watering and the protection of wildlife, a maximum of 30 mg/L for irrigation and a limit of 10 mg/L for recreational purposes. The only guideline exceeded in the watershed is that of 10 mg/L NOy - N for recreational purposes. The Canadian Drinking Water Quality Guidelines, as well as the B C Water Quality Guidelines establish 10 mg/L NOy - N as the maximum allowable concentration in drinking water to protect human health. However, this is not an issue when dealing with surface waters in this area since these are not drinking water sources. Drinking water in the watershed originates mainly from local groundwater sources. According to Boyd (2000) NGy - N concentrations in unpolluted waters are normally below 0.25 mg/L; might be above 1.0 mg/L in polluted waters and in highly polluted waters concentrations ranging from 5 to 10 mg/L are not uncommon. In the Bertrand Creek watershed, nitrate - N concentrations are of concern due to its potential eutrophication effects and the consequent reduction of water quality in these important salmon spawning streams. Station 5 on Howes Creek showed the highest concentration of NOy - N throughout the watershed, but especially during the dry season, which suggests recharge at this point from the contaminated, underlying Abbotsford aquifer. During the month of June, NOy - N concentrations reached 20.93 mg/L, followed by stations 4 (BCr4) and 8 (BCr8) on Bertrand Creek (9.48 and 5.72 mg/L respectively). Other studies in the Lower Fraser Valley have also found higher concentrations of nitrate during low flow conditions suggesting groundwater input [Smith, 2004; Cook, 1994], but neither of these studies found concentrations exceeding 10 mg/L. Addah (2002) and MacDonald (2005) found higher concentrations of nitrate during the wet seasons, but the highest concentrations found by Addah (2002) in the Agassiz/Harrison Hot Springs watershed (1.9 and 1.46 mg/L for the wet and dry seasons respectively) are only comparable to the median nitrate - N concentration found in the Bertrand Creek watershed. Median concentrations for sampling stations in the watershed during the rainy season were normally above 1.0 mg/L which might suggest that compared to other watersheds in the Lower Fraser Valley, the Bertrand Creek watershed has a higher nitrate contamination originating from runoff. Nitrate - N concentrations tended to increase in the downstream direction in Bertrand Creek. This pattern was observable during low and high flow periods and it is most 98 likely due to the fact that the upper sites are located in an urban area, while the downstream sites are located in the rural residential portion of the watershed, which suggests a significant input of nitrogen to surface waters from agricultural runoff. Table 5.5 compares the results of the present study with other similar studies in the Lower Fraser Valley. Table 5.5 N 0 3 " - N concentrations in surface waters (mg/L) for studies in the Lower Fraser Valley Location Bertrand Creek Goble 2005 Brookswood MacDonald 2005 Chilliwack Creek Magwood 2004 Hatzic Valley Smith 2004 Sumas River Range 0 .03 -20 .93 0 .009-8 .1 0.00 - 5.68 0 .00-2 .51 < 0.1 - 9 . 8 5 Mean 2.02 0.75 0.43 Median 1.5 1.56 Table 5.5 continued Addah 2002 Berka 1996 Wernick 1996 Cook 1994 Location Aggasiz/Harrison Hot Springs Sumas River Salmon River Salmon River Range 0 . 0 0 - 3 . 3 4 0 . 0 0 - 7 . 6 0 . 0 0 - 6 . 7 6 < 1 .0 -7 .0 Mean Median 1.3 2.19 5.4.2 Orthophosphate Phosphorus is the limiting nutrient in freshwater ecosystems and therefore, high concentrations are of concern because they indicate the presence of pollution and because of their impacts on eutrophication. In most natural surface waters, phosphorus ranges from 0.005 to 0.02 mg/L P 0 4 - P [Chapman, 1996]. Even though there are no recommended provincial or federal guidelines for the protection of aquatic life in rivers and streams with respect to phosphorus concentrations, the B C Ministry of Environment sets a maximum of 0.01 mg/L for recreation purposes in lakes and a range between 0.005 and 0.015 mg/L total P for the protection of aquatic life in lakes. All streams in the Bertrand Creek watershed exceeded this concentration, which is a significant concern in preserving the quality of water. Of particular concern is site 5 on Howes 99 Creek (HC5), which in the low flow period exhibited concentrations of as much as 32.5 mg/L. Concentrations at this site were significantly higher during the summer compared to the winter, suggesting that the source of phosphorus is not surface runoff, but possibly some direct discharge from a nearby farm. When flow is low there is no significant dilution and thus, concentrations are higher. It is also possible that animal carcasses are illegally being disposed of in the creek adding to the decomposition of organic matter. During one sampling occasion the jaws of some kind of equine were found. No other Lower Fraser Valley water quality study reports concentrations higher to those found in Howes Creek [Goble, 2005; MacDonald 2005; Magwood, 2004; Addah, 2002; Berka, 1996; Wernick, 1996; Cook, 1994]. Station 1 on Bertrand Creek also shows higher P 0 4 - P concentrations during low flow conditions. Concentrations at this site are more than twice as high (0.77 mg/L P 0 4 - P) as those reported by Smith (2004) for her most eutrophic site on Marshall Creek (0.3 mg/L P 0 4 - P). 5.4.3 Chloride The Canadian Environmental Quality Guidelines set a range between 100 - 700 mg/L C l f o r irrigation purposes. According to B C water licensing database, there are 24 licenses on Bertrand Creek, 7 on Pepin Creek, 2 on Cave Creek and none on Howes Creek. All these licenses are mostly for irrigation purposes. Even if the number of licenses seems small, it is customary that many people divert water from streams without a license. Only two of the sites in the watershed were above 100 mg/L CI" during the month of August: site 1 on Bertrand Creek (120 mg/L CI") and 13 on Cave Creek (125 mg/L CI"). Chloride can enter surface waters with the weathering of some sedimentary rocks (mostly rock salt deposits), from industrial and sewage effluents, and agricultural (KCI is extensively used in commercial fertilizers) and road runoff (from the application of salt, usually NaCl , to reduce icing. According to Chapman (1996) chloride concentrations in pristine waters are usually below 10 mg/L. The only sites that were below 10 mg/L CI" throughout the study are those on Pepin Creek. Agricultural sites on Bertrand Creek were normally around 10 mg/L or a bit higher, however urban sites were never below this concentration. Chloride concentrations were typically higher in the urban portion of the watershed, particularly in the dry season, which means that high CI" concentrations in this area are not originating from road runoff. As chloride is often associated with sewage, it is incorporated into assessments as an indication of possible fecal contamination or as a measure of the extent of the dispersion of sewage discharges in water bodies. In a water quality assessment by Swain 100 and Holms (1985), it is reported that the Aldergrove sewage treatment plant discharged to the Fraser River 4,546 m 3/day of secondary domestic sewage following treatment in an activated sludge plant but raw sewage bypasses entered Bertrand Creek. However, since 1998 the Aldergrove area has been serviced by the J .A .M.E.S. sewage treatment plant in Abbotsford, which means that all sewage is pumped east [Dave McCormack, Township of Langley. pers. comm.]. This suggests that the origin of high chloride in this area is linked to the glaciomarine deposits from the Fort Langley formation that predominate in the north end of the watershed. Compared to other studies in the Lower Fraser Valley [Goble, 2005; Smith, 2004; Wernick, 1996; Berka, 1996] chloride concentrations in the Bertrand Creek watershed were the highest. Table 5.6 presents a summary of the range of concentrations found in these studies. Table 5.6 Chloride concentrations in surface waters (mg/L) Goble 2005 Smith 2004 Berka 1996 Wernick 1996 Location Bertrand Creek Brookswood Sumas River Sumas River Salmon River Range 2 . 8 5 - 1 2 5 . 0 5 .53-44.0 < 6 . 0 - 3 8 . 8 1 .2-53 .5 3 . 6 - 3 1 . 6 5.4.4 Dissolved Oxygen The B C water quality criteria for dissolved oxygen for the protection of fresh aquatic life are set at greater than 5.0 mg/L instantaneous minimum for all life stages except other than buried embryo or alevine and greater than 9.0 mg/L for buried life stages. Dissolved oxygen in the Bertrand Creek watershed is of importance for the protection of aquatic life, in particular fish, such as the Nooksack dace (Rhinichthys cataractae) and Salish sucker (Catostomus sp.). Both of these species are listed as endangered in Canada and the United States [Pearson, 2004]. Pearson (2004) concluded that hypoxia is a major threat to Salish sucker populations in this area. Dissolved oxygen throughout the watershed is particularly low in the summer, mostly due to the low flow conditions and lack of aeration during that time of year. Low dissolved oxygen concentrations during the summer months at station 9 on Pepin Creek (PC9) can be attributed to groundwater recharge. During the dry season, between 40 - 60% of all the samples were below 5 mg/L dissolved oxygen and most were below 9 mg/L. This changes dramatically during the winter when almost all the samples (except 2) were above 5 mg/L. Figure 5.2 and Figure 5.3 show the percent of samples during the wet and dry seasons that do not meet B C water quality criteria for dissolved oxygen. 101 Urban sites 70 J 60 -o 'LD 50 -o> E m 40 -o n 30 (0 Q> a. E 20 ra CO «•- 10 -o Agricultural sites & <P 4> Upstream * * L # if 4> f 4 Downstream I dry season I wet season Figure 5.2 % of samples below B C water quality criteria for DO for the protection of aquatic life (all non - buried life stages) ** Stations HC6 and HC7 were mostly dry during the summer months v a O) E CT) o a> a E re w >*-o Urban sites Agricultural sites Upstream <?°oO N Downstream I dry season I wet season Figure 5.3 % of samples below BC water quality criteria for DO for the protection of aquatic life (all buried embryo/alevin life stages) 102 5.4.5 pH Depending on the different water uses, the B C water quality criteria set different ranges for pH. These are summarized in Table 5.7. Table 5.7 Summary of pH criteria according to the B C approved water quality guidelines (1998 edition) Water use Criteria pH units Drinking water supply 6 . 5 - 8 . 5 Fresh water aquatic life 6 . 5 - 9 . 0 Livestock water supply 5 . 0 - 9 . 5 Irrigation water supply 7 . 0 - 8 . 7 Recreational waters 5 . 0 - 9 . 0 Most of the samples taken at different sites throughout the year were within the established criteria. Site 7 on Howes Creek was constantly below the 6.5 criteria for the protection of aquatic life. When it comes to meeting the criteria for irrigation, samples were typically below this level. Low pH of irrigation waters is of concern because it might cause soil acidity. Metal cations, including heavy metals and aluminum become more soluble with decreasing pH, whereas anions (except borate and silicate) are less soluble [Hesterberg, 1998]. Underlying geology and precipitation play key roles in determining pH within a watershed [Smith, 2004]. But it is also known that fertilizers tend to cause soil acidity and therefore, surface runoff, especially in agricultural areas, is expected to affect pH in receiving water bodies. Because pH was only measured for 3 of the 5 sampling events in the summer, Figure 5.4 presents the percentage of samples below pH 7.0 for the whole study, as opposed to divided into dry and wet periods. pH values in the Bertrand Creek watershed are within the normal rainwater pH range in the Fraser Basin of 4.5 - 5.5 [Hall, ef. al. 1991, cited by Wernick, 1996] 103 Upstream • Downstream Figure 5.4 % of samples below B C water quality criteria for pH for irrigation purposes 5.4.6 Specific Conductivity Even though there are no conductivity guidelines for the protection of aquatic life, irrigation or recreational purposes, it is important to measure conductivity as it provides an indication of the concentration of total dissolved solids and major ions and it can also be used to establish pollution zones or the extent of influence of runoff waters. The conductivity of most freshwaters ranges from 10 to 1,000 u.S/cm, but it may exceed 1,000 u.S/cm, especially in polluted waters [Chapman, 1996]. Conductivity readings in the watershed were of no particular concern. They exhibited normal seasonal variability - higher during low flow conditions when the concentration of ions is expected to be higher in the streams and lower during the wet season due to the influence of precipitation and the effect of dilution. Conductivity was highest during the months of July and August 2004 at station 1 on Bertrand Creek, which corresponds with the highest concentrations of chloride. 104 5.4.7 Temperature Temperature is one of the most important parameters to monitor in water quality assessments, as it influences physical, chemical and biological processes. The Bertrand Creek watershed is particularly important to different salmon species, Salish sucker (Catostomus sp.) and Nooksack dace (Rhinichthys cataractae spp.) and extreme variations in temperature can have seriously detrimental effects on the populations of these fish. The B C water quality criteria for temperature for the protection of fish set an optimum range depending on the fish species and the life stage, and advise against exceeding this optimum range by more than 1 degree. Since different species of salmon and other fish are present in the streams in the watershed, the general guideline for "unknown fish distribution" of 19°C (maximum daily temperature) and 12°C (maximum incubation temperature during the spring and fall) will be used. This guideline of 12°C was most commonly exceeded during the months of April, May and September at almost all sites, which signifies problems for the different fish species in the watershed. During the month of May, all sites except site 7 on Howes Creek, had temperatures between 13 and 15.3°C. During the summer (month of July), only sites 1, 2, 8 and 12 on Bertrand Creek had temperatures above 19°C. However, sites 6 and 7 on Howes Creek were completely dry during this time of year. Water temperature in the Bertrand Creek watershed is most commonly affected by riparian cover. 5.5 Trace Elements in Surface Water and Sediments Water quality guidelines have only been developed for four of the elements measured in stream water and four of the elements measured in sediments that were above detection limits [CCME, 2003]. These are summarized in Table 5.8. 105 Table 5.8 Canadian water and sediment quality guidelines and background levels in British Columbia Elements in Ca mg/L Fe mg/L Mn mg/L Zn mg/L water Background levels N/A N/A 0.01 - 17 <0.01 in British Columbia Water quality criteria Aquatic life 0.3 0.03 Irrigation 5.0 0.2 1 .0 -5 .0 Livestock 1,000 < 0 .05 1 0 2 0 1 1 Metals in Cr ppm Cu ppm Pb ppm Zn ppm Sediments 88.7 1 2 Background levels 1 2 - 2 0 6 < 15.0 < 10.0 in British Columbia Interim Sediment 37.3 35.7 35.0 123.0 Quality Guideline Probable Effects 90.0 197 91.3 315.0 Level Iron Most of the water samples taken throughout the watershed exceeded the 0.3 mg/L water quality guideline for the protection of aquatic life. Out of 60 samples taken, 44 (73%) exceeded this guideline, but only site 7 on Howes Creek exceeded the 5.0 mg/L guideline for irrigation purposes. DGT results showed that bioavailable iron was highest at station 3 on Bertrand Creek during the month of July. However, it must be kept in mind that bioavailable metals were only measured along Bertrand Creek and not in the other streams in the watershed. The source of iron in the streams is most likely geological, though iron is also an abundant element in livestock waste [Smith, 2004]. Studies dealing with iron toxicity in aquatic environments are scarce and problems are most likely to arise due to iron deficiencies rather than high levels in water. Even though there is no federal interim sediment quality guideline for iron, sediments rich in iron can be a concern to eutrophication. Iron and phosphorus in bottom sediments are associated and the reduction of F e + 3 to soluble F e + 2 can result in the release of phosphorus [Chapman, 1996]. The provincial sediment quality guidelines set a Lowest Effect Level (LEL) for iron of 21,200 ppm and a Severe Effects Level (SEL) of 43,766 ppm. All sites were above Recommended maximum concentration for livestock drinking water. No toxicity guideline. Peterson, 1999. 1 1 Provincial guideline. Used instead of federal guideline because it is substantially lower. 1 2 Background level for Canada 106 the LEL during both sampling events, with the exception of site 10 on Pepin Creek during the month of July 2004. Site 7 on Howes Creek was below LEL during both seasons, in spite of having the highest concentration of dissolved iron. The S E L was only exceeded by sites 1 on Bertrand Creek (BCr1) and 5 on Howes Creek (HC5) during the wet season. Manganese Manganese is an essential trace element that forms part of the enzyme systems that metabolize proteins and energy in all animals. It is present in almost all organisms and often reduces the hazard posed by other metals. In aquatic environments, manganese toxicity is slight to moderate and is influenced by several factors such as water hardness, salinity, pH and the presence of other contaminants. It preferentially binds to particulate matter, but the soluble species of the metal are considered to be the most toxic as they are readily available for biological reactions [Nagpal, 2001]. Total manganese concentrations in natural fresh waters seldom reach 1.0 mg/L and are usually less than 0.2 mg/L. Seawater typically contains about 0.002 mg/L manganese. The total concentration in fresh surface waters in the coastal region of BC was found to be between 0.01 and 1.7 mg Mn/L. Concentrations decline in the interior of the province with a range of 0.002 to 1.53 mg Mn/L in the Cariboo, Omineca, and the Peace Regions and less than 0.001 to 0.56 mg Mn/L in the Thompson River region [Nagpal, 2001]. Minerals and rocks are perhaps the most significant natural sources of manganese in the aquatic environment. Anthropogenic sources of manganese include mining, sewage and sludge and landfills. In urban environments automobile use, metal and paint industry might be responsible for high concentrations of manganese in water. Manganese is commonly used in the manufacturing of steel and the production of alloys of steel, aluminum and copper. It is also used as an ingredient of alkaline batteries, electrical coils, ceramics, matches, glass, dyes, paints, paint dryers, varnishes and oils, disinfectants and as a gasoline additive. In an agricultural environment, manganese can originate from fertilizers, fungicides and animal foods [Nagpal, 2001]. During the rainy season, no samples were found to be above 0.2 mg Mn/L, possibly due to the effects of dilution. Manganese concentrations were typically higher during the dry season, particularly in the urban sites and seemed to decrease in the downstream direction as the stream enters the rural portion of the watershed. Concentrations on Bertrand Creek were as 107 high as 2.5 mg Mn/L. This is consistent with DGT results that show highest bioavailable levels of manganese were found at this station during the dry season. Chromium There are multiple uses and sources of chromium. Chromium oxide, chromium chloride and chromium sulphate are the most commonly used compounds in Canadian industry. They are mainly used in metal plating and finishing, wood preservation, pigments and paints and leather tanning. In surface runoff, chromium can come from the corrosion of painted surfaces, stainless steel, treated lumber, tar and asphalt as well as automotive tire and brake wear [CCME 1999a]. Even if chromium was not measured in water in the present study, concentrations of chromium in sediment are important since a variety of organisms live in contact with stream sediments and thus, they constitute an important route of exposure. Studies in Canada and other countries indicate that nearly all the Cr in sediments is likely in the C r + 3 form, as opposed to the dominant dissolved form which is C r + 6 [CCME, 1999a]. The Canadian interim sediment quality of 37.3 ppm was exceeded at most sites, with the exception of sites 6 and 7 on Howes Creek during both sampling events and site 12 on Bertrand Creek during the July 2004 sampling event only. However, none of the samples exceeded the P E L of 90 ppm. Copper Copper concentrations in the Bertrand Creek watershed normally exceeded the interim sediment quality guideline of 35.7 ppm with the exception of sites on Howes Creek and Cave Creek. Copper concentrations were highest in the urban portion of the watershed and decreased along Bertrand Creek as it enters the rural portion of the watershed. This trend was more evident during the dry season. This might be due to the accumulation of copper in impervious surfaces that gets flushed into the creek during summer rainfall events [Hall, et. al., 1998] and gets diluted as the stream flows away from urban areas. Concentrations of copper on Pepin Creek were also quite high, particularly at site 9, but they decreased in the downstream direction and were not found above the guideline at site 10 during the dry season. Nevertheless, none of the samples exceeded the probable effects level (PEL) of 197 ppm Cu. The adverse biological effects of copper can include decreased benthic invertebrate diversity, reduced abundance and increased mortality, among others. Organic matter content in sediments can mitigate the toxicity of copper to aquatic life [CCME, 1999c] which means that 108 high copper concentrations are more of a concern in streambed sediments from site 9 on Pepin Creek, due to their low organic matter content. Bioavailable levels of copper measured with DGTs were always below detection limits (0.1 ppm Cu). In agriculture, copper compounds are used as fungicides and to prepare copper fungicidal products, algicides for reservoirs and streams and nutritional supplements in animal feed and fertilizers [Dorsey, ef. al., 2004]. In urban settings, copper has been associated with the use of copper wires and pipes [Brydon, 2004] and corrosion of brake linings from vehicles. Lead Lead is the trace metal posing the greatest threat to aquatic life, followed by copper, zinc and mercury. Even though concentrations of lead in sediments have significantly declined thanks to the restriction on commercial products containing lead and to the elimination of tetra ethyl lead as gasoline additive, trace metal levels in the Brunette River watershed strongly indicate that traffic is a significant source of lead and zinc in this watershed [McCallum & Hall, 1998]. Sediment samples from all the sites in the Bertrand Creek watershed were above the British Columbia background levels for lead (<10.0 ppm Pb). Concentrations were only below detection limit and/or below the interim sediment quality guideline at sites 5 and 6 on Howes Creek (HC5 and HC6, respectively) and 13 on Cave Creek (CC13) during the dry season, and at site HC6 during the rainy season. All other sites exceeded the interim sediment quality guideline. Urban stations always had the highest concentrations of lead with the exception of station 9 on Pepin Creek during the rainy season, which had the highest concentration of all, at 168 ppm. Stations in the urban portion of the watershed (BCr1, BCr2 and BCr3) and station 8 on Bertrand Creek (BCr8) were the only ones to exceed the P E L of 91.3 ppm Pb. As mentioned before, station 8 is perhaps the one with the highest traffic density in the watershed since it is located on Highway 13 (264 t h Street Aldergrove - Bellingham Highway), which has heavy traffic to and from the US - Canada International border. This further confirms that lead in sediments is related to traffic density. Unfortunately, bioavailable concentrations of lead measured with DGTs were discarded from the results of this study due to possible lead contamination in the laboratory. 109 Zinc Even though zinc may bind to particulate matter, soluble species of zinc are considered most toxic since they are.readily available for biological reactions. Dissolved zinc is a better predictor of fish tissue contamination than zinc in sediment or food sources such as invertebrates [BC MoE, 1999]. Fifty percent of all the water samples taken during the study (N=60) exceeded the guideline of 0.03 mg/L for the protection of aquatic life. All the samples taken during the month of July 2004 exceeded the guideline, most likely due to low flow conditions which reduce the effect of dilution. Concentrations of dissolved zinc didn't show any particular seasonal or spatial trends, but the highest concentration was found during the month of August at site 8 on Bertrand Creek, which is just off 264 t h Street (Aldergrove - Bellingham Highway). Zinc can enter aquatic ecosystems from surface runoff or atmospheric deposition. Studies have shown that, in general, summer storms can contribute higher concentrations of contaminants to receiving waters, than winter storms, since summer rainfall events are far more infrequent and more intense than winter rainfall events, thus allowing contaminants to accumulate on impervious surfaces. These accumulated contaminants get flushed at once into surface waters by summer rainfall events [Hall, et. al., 1998]. Bioavailable zinc was not measured at site 8 and DGT results showed that the highest bioavailable concentration (0.4 pg/L) was found at site 11 on Bertrand Creek (BCr11). The interim sediment quality guideline for zinc (123 ppm) was exceeded at most sites for both sampling periods, except sites 7 on Howes Creek and both sites on Pepin Creek (PC9 and PC10) during the dry season. Streambed sediments on Pepin Creek are fairly coarse and don't have a very high organic matter content, which might explain why zinc levels were not very high. The Probable Effects Level (PEL 315 ppm Zn) was only exceeded by sites on the urban portion of the watershed (sites 1, 2 and 3 on Bertrand Creek). Zinc levels in sediments show a very clear decline in the downstream direction on Bertrand Creek, as the stream enters the rural portion of the watershed. In urban areas, roof runoff (from galvanized roof drainage) and street runoff from automobile use have been linked to zinc concentrations [Brydon, 2004]. British Columbia is among the major producers of zinc in Canada. Zinc is also used in much of the metal industry as a rust - resistant coating, in the manufacture of brass and bronze, in the making of automobile tires, dry cell batteries and electrical apparatus. It is also used in hardeners for cement and concrete, in the production of adhesives and as wood preservatives. 110 It is found in many household products including cosmetics, antiseptics, astringents, paints, varnishes, rubber, etc. [MoE 1999]. In agricultural settings, Zn can originate from animal manure, fertilizers, pesticides and fungicides. 5.6 Land Use Impacts on Surface Water and Sediment Quality 5.6.1 Nutrients in surface waters Agricultural activities are well known to be a source of nutrient contamination in surface waters through leaching and runoff. While the specific agricultural activity or crop cover associated with nutrients will vary depending on the characteristics of the region, recent studies in the Lower Fraser Valley have found that agricultural land uses have a direct influence in the concentration of nutrients in rivers and streams [MacDonald, 2005; Smith, 2004; Addah, 2002; Cook, 1996]. MacDonald (2005) found that in the Chilliwack Creek watershed, percent total agricultural and percent total arable land were the best indicators of water pollution from agricultural activities. Furthermore, these indices were good indicators of higher levels of metals in sediments. Smith (2004) states that the intensity of livestock operations (AUE/ha) and the percent of corn cover were the best indicators of water pollution as a result of runoff in the Sumas River watershed and Addah (2002) found that grazing pastures significantly increased nutrient concentrations in watercourses throughout the Agassiz/Harrison Hot Springs watershed. In the present study agricultural activities showed a positive correlation with nitrate - N in surface waters, particularly during the wet season, which suggests runoff from fields. The fact that nutrients didn't seem to be correlated with animal operations might be due to low animal densities in farms, in which case the impact of these would be almost negligible. 5.6.2 Trace elements in sediments As discussed in section 5.5, concentrations of copper, zinc and lead in sediments were always highest at urban stations and stations associated with high traffic density (BCr8). The only strong and significant correlations between sediment quality and land use were those between impervious surfaces and these metals. Lead was only correlated to impervious surfaces during the dry season, and correlations for the other two metals were stronger during the dry season than during the wet season. This might be the result of increased flow which removes the top layer of streambed sediments where metals have accumulated. The percent area of impervious surfaces is a good indicator of trace metals in aquatic environments mainly because of their close link to automobile traffic. Studies in urban watersheds have mapped 111 traffic patterns and found that traffic is a major source of lead and zinc [McCallum & Hall, 1998]. On the other hand, phosphorus in sediments was negatively correlated with areas with vegetative cover. Phosphorus is not a very mobile or soluble element and is therefore usually bound to particulate material. Also due to its limited mobility, phosphorus from manure, fertilizers and other anthropogenic sources accumulates in topsoil. Soil erosion from agricultural fields is an important source of phosphorus to streambed sediments. As surface runoff passes through vegetated areas, many of these particles are allowed to settle, thus reducing the input of particle bound phosphorus to receiving streams. 112 6 Conclusions and Recommendations 6.1 Groundwater quality and well owners' perception of water quality Nitrate - N is perhaps the parameter of greatest concern in groundwater quality due to its potential health impacts. The results of this study further confirm that nitrate contamination in the Abbotsford aquifer continues to be a problem, since water quality of those wells located in this aquifer were the most impacted by nitrates. Nitrate also showed a strong negative correlation with well depth in that the more shallow wells (<15 m deep) were the only ones to exceed the Canadian Drinking Water Quality Guidelines of 10 mg/L NOy - N. The overall perception of well owners of their water quality was that it was good or moderate, which reflects the existing concern with water contamination in the area. Survey results also showed that most people rely on the organoleptic properties of their water to assess its quality. It is recommended that private well owners test their well water not only for chemicals but also for pathogens on a regular basis and at least once every two years. It is necessary to inform private well owners and local stewardship groups of the quality of their water and educate them on what they can do to improve the management of groundwater so they can exert a positive influence in the formulation of policies and regulations to protect the resource. 6.2 Surface water quality: nutrients, chloride and chemical parameters There are no long-term water quality monitoring programs on the Canadian portion of the Bertrand Creek watershed. Due to the importance of the streams in this watershed to aquatic life - particularly to different salmon species, Salish sucker and Nooksack dace - it is recommended that the provincial government conduct a comprehensive water quality assessment in the watershed to ensure provincial water quality guidelines are being met. Site 5 on Howes Creek was by far the one to present the highest levels of nutrients in the watershed. In the case of nitrate, recharge from the Abbotsford aquifer is suspected as a source. Orthophosphate - P levels were also extremely high at this station. However, inputs of phosphorus to this station on Howes Creek could not be determined with certainty during this study. Point source pollution is suspected. Therefore, it is very important that further 113 monitoring of phosphorus concentrations be conducted, mainly because of the risk of eutrophication posed on this salmon bearing stream. 6.3 Trace elements in surface water and sediments Manganese and zinc were the only metals analyzed in surface waters. Both of these were found in higher concentrations in the urban portion of the watershed, suggesting vehicular traffic as the main source. Concentrations of other metals, mainly copper and lead, exceeded the interim sediment quality guidelines. In the case of lead, concentrations exceeded PEL concentrations only at those sites in the urban portion of the watershed and site 8 on Bertrand Creek, which is associated with heavy traffic. The source of these metals is most likely street runoff. Therefore, the implementation of Best Management Practices (BMPs) such as increasing riparian buffer zones, grass buffer strips, grass swales, the use of porous pavement, and the minimization of directly connected impervious areas, are recommended. The construction of stormwater detention ponds, especially at those sites that receive direct runoff from roads, such as site 8 on Bertrand Creek which crosses the Aldergrove - Bellingham highway, can also be highly effective in managing stormwater to reduce the input of contaminants to receiving waters. Monitoring over storm events in flashy streams is also necessary to better define the load of material entering the stream in relation to traffic and total impervious surfaces and to be able to make informed, science-based decisions in selecting the most appropriate BMPs. 6.4 Land use impacts on water and sediment quality in the watershed There were no significant correlations between land use and nitrate - N concentrations in groundwater. However, the influence of agricultural activities on groundwater quality, particularly on the Abbotsford aquifer, has been well documented in other studies. In surface waters, nitrate - N was positively correlated with agricultural activities during the wet season, suggesting surface runoff from fields as the main source. On the other hand, phosphorus in sediments was negatively correlated with vegetative cover during the wet season, indicating that the most likely source is soil erosion from agricultural fields. 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GROUNDWATER SURVEY September 2004 The University of British Columbia is currently working on a comprehensive groundwater study and would greatly appreciate your collaboration in filling in this questionnaire. The completion of this questionnaire is voluntary and your response will remain confidential, but your input would significantly improve our understanding of water quality in the area. Please answer by placing an X in the appropriate box or by filling in the space. 1. How many years have you been using your well? How many people does your well serve? Years People 2. How deep is your well? Feet or Meters 3. Do you drink your well-water? Y E S NO SOMETIMES 4. Do you filter your well-water? Y E S NO If Y E S , what kind of filter do you use? 5. Do you treat your water in any other way? Y E S NO If YES , how do you treat your water?_ 6. Do you drink bottled water at home? ALWAYS O F T E N SOMETIMES NEVER 7. Does your.well provide sufficient water throughout the year? Y E S NO 8. Are you engaged in: (Please place an X in the boxes that best represent the amount of Occupation Full-time Part-time Never Farming / Agriculture Other professional service 9. What is your perception o f the water quality from your wel ? E X C E L L E N T G O O D M O D E R A T E FAIR P O O R 129 10. Do you think an increase in groundwater aquifer use is appropriate? Y E S I I I LIMITED U S E ONLY I I I NEED M O R E INFO NO 11. How important is each of the following activities in causing water quality problems? S T R A T E G Y Extremely important Moderately important Not important Farming (fertilizer) 5 4 3 2 1 0 Farming (manure) 5 4 3 2 1 0 Farming (chemicals) 5 4 3 2 1 0 Hobby farms 5 4 3 2 1 0 Lawn fertilization 5 4 3 2 1 0 Golf course management 5 4 3 2 1 0 Septic systems 5 4 3 2 1 0 Industrial activity 5 4 3 2 1 0 Aggregate Extraction 5 4 3 2 1 0 Other 5 4 3 2 1 0 12. To what extent do you think use of the groundwater aquifer affects the local rivers? River flow Significant impact Moderate impact No impact Water quality Significant impact Moderate impact No impact 13. What type o f management approach do you favor? Voluntary Regulation A Combination 14. How appropriate do you think the following strategies are for managing groundwater resources? S T R A T E G Y Extremely important Moderate Not appropriate Restriction on fertilizer use in agriculture 5 •• 4 3 2 1 0 Restrictions on manure applications 5 4 3 2 1 0 Restrict lawn. & garden use of chemicals 5 4 3 2 1 0 Introduce septic system monitoring.& servicing regulations 5 4 ; 3 2 1 0 Control road runoff 5 • 4 3 2 1 0 Introduction of a municipal sewer system . 5 4 3 2 1 0: Regulate land use 5 4 3 2 1 0 Restrict industrial development 5 4 3 2 1 0 Restrict urban development 5 4 3 2 1 0 Other- • 5 4 3 2 1 0 15. What type of land use activity occurs within 100 meters of your well? 16. Have you had any problems with your well? 130 17. How often do you test your well? (Please Check t he Appropriate Box) Once a Year Every 2 Years Every 3 Years Other Bacteria Chemical 18. Have you had any chemical and bacterial exceedances in your well water? If Y E S , please explain 2 Yes 1 No 19. Do you have a septic system? If Y E S , How close if your septic system to your well (in meters)? Yes No metres 20. When was your septic system installed? 5 year 21. How often do you service your system? (Please circle the correct response) Once/Year Once /2 years Once /3 Years Once/ 5 Years Once /10 years Never 22. How likely is it that you or someone in your family will suffer the effects of Highly likely Likely Very Un ikely Natural Disasters (eg flooding/earthquakes) 5 4 3 2 1 0 Air Quality in the Region 5 4 3 2 1 0 Pesticide Residue in air or water 5 4 3 2 1 0 Downstream Effects of Pollution 5 4 3 2 1 0 Fecal Coliform in Drinking Water 5 4 3 2 1 0 23. How much control do you see yourself as having over any risks posed by the fo lowing: No Control. Some Control Mut Conl ;h roi Natural disasters (eg flooding/earthquakes) 5 4 3 2 1 0 Air quality in the Region 5 4 3 2 1 0 Pesticide residue in air or water 5 4 , 3 2 1 0 Downstream effects of pollution • 5 4. , 3 2 1 0 Fecal Coliform in Drinking Water 5 4 3 2 1 0 131 24. How important are the following as a guide for indicating the quality of your water?: Not Important Very Important Smell/ Taste 7 6 5 4 3 2 1 Cloudiness 7 6 5 4 3 2 .1 Colour 7 6 5 4 3 2 1 Visible Abnormalities (e.g., change in colour) 7 6 5 4 .3 2 1 Depth of Water Table 7 6 5 . 4 3 2 1 Amount of visible particulate matter in a glass of water 7 6 5 4 3 2 1 Local Newspaper reports oh the quality of nearby bodies of water 7 6 5 4 3 2 1 Multiple incidents of gastrointestinal illness in the community 7 6 5 4 3 2 1 Questions 25 to 29 - Circle the answer that you feel is most correct: 25. If you are exposed to even the smallest amount of a water-borne pathogen such as E. coli or Giardia, you are likely to suffer adverse health effects. Strongly Agree Agree Disagree Strongly Disagree 26. Your health will not be negatively affected by pesticides unless you are exposed to a lot of the chemical over a long period of time-Agree Disagree 27. Most water quality risks can be eliminated by a common household filter Agree Disagree 28. People are unnecessarily frightened about very small amounts of contaminants found in groundwater Agree Disagree 29. On the whole, the risks to human health posed by water quality problems are far greater than the risks posed to the local fish, flora and fauna. Agree I Disagree 30. In order to arrive at a sustainable use of the groundwater resources ... A. What do you think you could do as an individual? B. What should the municipality do to improve the situation? 132 Appendix A3: Sample report to well owners on water quality analysis results Participant's name Address Address March 31, 2006 Results of the October 2004 Aldergrove Well Water Study Dear : Thank you for participating in the well water survey. W e appreciate your time and effort. The following results were obtained for the recent well water ana lys is : 0.00442 mg/L of Nitrate-N 0.805 mg/L of Chlor ide 271.2 umhos/cm Conductivity (salt content) 162.72 Total Dissolved So l ids (TDS) 7.65 pH 0.305 mg/L of Phosphate There is no Drinking Water Quality Standard for phosphates, as they are not considered a health concern. Nitrate-N: Va lues greater than 10 mg/L are considered a health concern . 10 mg/L is the National Health Standard. Water with Nitrate-N levels between' 7 and 9.9 mg/L is of concern and is likely impacted by different land use activities (fertilizers, manure, or septic sys tem effluent). Levels below 3 mg/L are of little concern and considered unpolluted water. Chloride: The Guide l ines for Canad ian Drinking Water Quali ty set an aesthetic objective of 250 mg/L for chloride in drinking water. At concentrat ions above the aesthet ic objective, chloride imparts undesirable tastes to water and to beverages prepared from water and may cause corrosion in the distribution sys tem. Conductivity: Water with less than 100 umhos/cm is cons idered to be "soft" water with low salt content. Water with greater than 500.umhos/cm is cons idered to be "hard" water with relatively high salt content. T h e s e measurements are not a health concern but they give us an idea about the source of water, the geological formation and the land use influence. 134 Tota l D i s s o l v e d S o l i d s (TDS) : A n aesthetic objective of 500 mg/L has been establ ished for total d issolved sol ids (TDS) in drinking water. At higher levels, excess ive hardness, unpalatability, mineral deposit ion and corrosion may occur. At low levels, however, T D S contributes to the palatability of water. p H : A n acceptable range for drinking water pH is from 6.5 to 8.5. Corros ion effects may become significant below pH 6.5, and the f requency of incrustation and scal ing problems may be increased above pH 8.5. With increasing pH levels, there is also a progressive dec rease in the efficiency of chlorine disinfection p rocesses . W e hope to do a f o l l o w - u p a n a l y s i s in F e b r u a r y when the groundwater table is high, and we hope you will once again participate. Addit ional tests will be done on selective metals but the data will not be avai lable until the February survey is completed. W e will contact you c loser to the time. Sincerely yours, K e n Ha l l G a b r i e l a S o l a n o Professor M S c Cand ida te I R E S - U B C R M E S - U B C 135 Appendix B: Groundwater Sampling Results Table B1: Q A / Q C results for groundwater samples for nutrient and chloride analysis Table B2. N 0 3 - N, P 0 4 , Cl'and physical parameters raw groundwater data for the dry season Table B3. N 0 3 - N, P 0 4 , Cl'and physical parameters raw groundwater data for the wet season Table B4. Dissolved elements raw data for the wet season Table B5. Percent Land use within well buffers 136 Table B1. QA /QC results for groundwater samples for nutrient and chloride analysis W E L L No Date N 0 3 " - N P 0 4 CI" 1 Oct-04 6.41 O.01 5.58 6.61 <0.01 5.45 Mean 6.510 5.515 Std Dev 0.141 0.092 CV(%) 2.172 1.667 8 2.19 0.018 1.08 2.2 0.017 1.05 Mean 2.795 0.018 1.065 Std Dev 0.007 0.001 0.021 CV(%) 0.322 4.041 1.992 14 Feb-05 0.046 0.01 6.86 0.044 0.01 6.72 0.043 0.01 6.66 Mean 0.044 0.010 6.747 Std Dev 0.002 0.000 0.103 CV(%) 3.446 0.000 1.521 32 1.77 <0.01 8.59 1.79 <0.01 8.57 1.76 <0.01 8.32 Mean 1.773 8.493 Std Dev 0.015 0.150 CV(%) 0.861 1.771 Table B2. N 0 3 - N, P 0 4 , C rand physical parameters raw groundwater data for the dry season October 2004 Welltt Depth N03-N P04 cr pH Turbidity EC TDS (m) (mg/L) (mg/L) (mg/L) (NTUs) 1 7 6.61 <0.01 5.58 6.2 0.23 170 114 2 19 5.58 0.02 6.17 6.6 0.25 173 116 3 18 0.01 0.05 0.64 8.1 0.26 174 117 4 27 < 0.002 0.06 4.76 6.3 309 190 128 5 59 0.01 0.94 0.95 8.8 0.63 461 309 6 17 0.02 0.04 1.29 7.9 0.15 176 118 7 9 11.30 <0.01 8.93 5.6 0.22 202 135 8 5 2.19 0.02 1.08 6.4 0.18 169 114 9 9 2.02 0.01 2.85 6.6 0.21 198 133 10 39 0.01 0.5 2.88 8.2 0.25 246 165 11 0 < 0.002 0.50 2.63 8.3 0.19 252 169 12 24 8.10 0.02 21.6 6.7 0.14 384 258 13 8 1.75 <0.01 3.86 5.9 0.35 115 77 14 0 0.27 0.02 5.68 6.8 2.27 238 160 15 55 0.01 0.40 3.12 7.2 0.19 917 615 16 15 0.02 0.04 6.38 7.7 1.84 264 177 17 6 5.24 0.01 7.16 6.1 0.54 186 125 18 9 0.37 0.03 5.14 7.7 0.5 205 138 19 5 4.30 < 0.01 1.03 6.1 0.35 137 92 20 5 4.80 <0.01 6.31 5.7 0.18 123 83 21 11 4.12 0.04 3.14 6.5 0.45 370 248 22 7 14.80 <0.01 7.52 6.0 0.21 243 163 23 2 4.94 0.01 4.63 6.2 0.25 172 116 24 14 14.50 <0.01 10.10 5.8 0.2 202 136 25 6 < 0.002 <0.01 129 5.4 0.38 481 322 26 82 0.01 1.66 357 8.0 1.12 2234 1497 27 73 < 0.002 0.31 0.81 7.7 0.5 271 182 28 28 < 0.002 0.19 292 7.8 0.61 1548 1037 29 30 < 0.002 0.43 101 7.5 1.02 586 393 30 8 0.5 0.42 97.1 7.5 0.52 597 400 31 3 10.40 < 0.01 8.95 5.3 0.16 157 105 32 3 1.82 0.05 84.6 6.4 4.21 409 274 33 8 0.06 0.01 5.05 5.9 22.6 112 76 34 5 10.00 < 0.01 4.87 5.7 0.12 149 100 35 12 12.50 0.01 5.72 7.5 0.42 393 264 36 12 24.00 < 0.01 28.1 5.4 0.34 402 270 37 4 3.95 <0.01 4.12 6.0 0.27 93 62 38 9 9.93 0.02 8.77 6.1 0.24 186 125 39 55 0.01 416 30.0 7.5 0.8 1083 726 40 5 1.28 <0.01 34.6 5.7 0.24 213 143 138 B3. N 0 3 - N, P 0 4 , Cl 'and physical parameters raw groundwater data for the wet season Well# February 2005 N03-N P 0 4 cr PH EC TDS Turbidity (mg/L) (mg/L) (mg/L) (NTUs) 1 4.91 <0.01 2.70 6.4 142 95 0.29 2 6.06 <0.01 6.52 6.8 163 109 0.38 3 < 0.002 0.02 0.76 8.5 166 111 0.54 4 0.01 <0.01 4.64 6.1 22 148 447 5 0.01 0.99 0.87 9.2 44 298 0.48 6 0.03 <0.01 1.60 8.2 170 114 0.31 7 9.18 <0.01 5.46 6.1 139 93 0.93 8 1.77 <0.01 0.56 6.5 81 54 0.22 9 2.95 < 0.01 2.15 6.4 116 78 0.11 10 < 0.002 0.43 2.75 8.6 242 162 0.26 11 N/A N/A N/A N/A N/A N/A N/A 12 6.73 <0.01 7.55 6.7 213 143 0.22 13 3.72 <0.01 18.50 4.4 133 89 0.24 14 0.01 0.011 6.86 6.8 211 142 0.66 15 < 0.002 0.05 1.60 7.5 891 597 8.94 16 0.02 0.02 6.69 8.1 261 175 1.48 17 7.30 0.01 19.6 6.1 210 141 0.24 18 1.06 0.02 5.90 7.6 176 118 0.18 19 3.40 <0.01 0.72 5.8 58 39 0.24 20 11.80 < 0.01 15.7 5.7 202 135 0.28 21 3.32 0.03 2.05 7.5 336 225 0.54 22 5.58 <0.01 2.82 6.2 120 80 3.6 23 N/A N/A N/A N/A N/A N/A N/A 24 13.30 <0.01 10.40 6.1 202 135 0.27 25 0.08 0.02 35.9 5.97 206 137 2.87 26 N/A N/A N/A N/A N/A N/A N/A 27 0.02 0.15 0.84 8.1 258 173 0.29 28 0.04 0.08 210 8.1 1,336 895 0.41 29 2.02 <0.01 4.23 5.9 115 77 0.18 30 2.07 0.03 5.03 6.2 162 108 0.27 31 8.77 < 0.01 7.85 5.4 143 96 0.14 32 1.77 <0.01 8.59 6.7 123 83 1.14 33 0.30 <0.01 3.66 6.4 73 49 0.58 34 12.60 < 0.01 6.87 5.8 162 108 0.16 35 12.40 <0.01 5.96 7.8 373 250 0.22 36 4.06 <0.01 3.42 5.8 97 65 0.93 37 3.58 < 0.01 5.71 6.1 94 63 0.26 38 11.30 <0.01 13.0 6.5 217 145 0.39 39 < 0.002 4.55 30.4 8.0 994 666 0.79 40 4.32 <0.01 1.35 5.9 124 83 0.2 139 Table B4. Dissolved elements raw data for the wet season Welltt Ca Cu Fe K Mg Mn Na Si Sr Zn 1 13.99 0.08 <0.05 4.62 3.76 < 0.005 4.32 4.25 0.08 0.05 2 16.86 0.13 <0.05 1.03 6.25 < 0.005 5.05 11.72 0.10 0.07 3 20.75 <0.05 0.19 3.13 6.49 0.03 4.36 7.32 0.08 0.02 4 21.09 <0.05 45.52 1.14 8.05 0.70 6.77 8.36 0.12 0.04 5 1.55 <0.05 0.07 4.46 0.92 0.01 104 7.55 0.02 0.02 6 15.33 <0.05 <0.05 3.00 5.53 0.02 12.7 6.40 0.06 0.01 7 13.56 0.05 0.08 4.47 2.88 0.04 6.00 4.88 0.06 0.05 8 8.35 0.14 < 0.05 0.79 2.94 < 0.005 3.64 10.85 0.05 0.04 9 12.52 < 0.05 <0.05 1.62 3.33 < 0.005 4.97 6.62 0.08 0.02 10 3.27 <0.05 0.06 4.11 2.66 0.02 52.3 11.13 0.03 0.01 11 N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A 12 20.55 < 0.05 <0.05 2.88 6.30 < 0.005 11.71 9.27 0.08 0.01 13 12.06 0.08 <0.05 5.01 1.95 < 0.005 3.57 7.49 0.1 0.01 14 5.58 <0.05 0.07 0.93 3.50 0.02 39.72 11.37 0.02 0.01 15 23.45 <0.05 2.46 5.64 18.69 0.23 167 17.84 0.15 0.03 16 28.34 <0.05 0.37 2.74 12.79 0.19 8.45 9.79 0.10 <0.01 17 19.67 0.18 <0.05 1.21 6.46 0.01 9.35 5.37 0.12 0.13 18 20.73 <0.05 <0.05 1.59 6.20 < 0.005 5.70 7.57 0.09 <0.01 19 5.80 0.27 <0.05 0.86 1.46 < 0.005 1.94 4.19 0.04 <0.01 20 15.30 0.49 <0.05 13.06 3.57 0.02 8.16 4.81 0.13 0.04 21 29.76 <0.05 <0.05 5.84 4.44 0.02 36.78 5.44 0.13 0.05 22 10.18 <0.05 0.58 8.52 1.95 0.01 4.42 3.77 0.06 0.02 23 N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A 24 19.46 <0.05 <0.05 1.24 6.53 0.01 8.30 7.67 0.13 0.02 25 15.57 0.06 1.28 1.24 2.11 0.16 19.42 5.19 0.09 0.10 26 N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A 27 0.16 <0.05 <0.05 0.95 0.03 < 0.005 68.2 13.33 0.01 <0.01 28 31.50 <0.05 0.05 5.39 14.07 0.05 241.3 8.50 0.22 0.02 29 12.47 < 0.05 <0.05 2.59 2.13 0.03 5.24 4.55 0.08 0.13 30 16.66 7.23 <0.05 3.11 3.11 0.04 6.68 5.63 0.12 1.24 31 11.01 <0.05 <0.05 4.80 2.48 0.05 7.08 5.42 0.07 < 0.01 32 12.60 <0.05 0.10 0.96 1.42 0.01 9.56 3.01 0.05 < 0.01 33 8.58 <0.05 0.15 0.66 0.85 0.03 5.38 3.19 0.04 0.01 34 16.98 < 0.05 <0.05 0.89 4.06 0.01 5.03 4.79 0.12 <0.01 35 45.90 <0.05 0.12 3.37 12.41 0.05 10.9 6.62 0.17 0.01 36 8.33 0.14 <0.05 5.76 1.41 0.02 3.73 3.54 0.05 0.03 37 8.46 <0.05 0.05 2.96 1.62 < 0.005 4.79 2.85 0.05 0.02 38 23.90 <0.05 <0.05 1.45 6.19 0.03 7.13 6.94 0.13 0.02 39 5.51 <0.05 0.75 5.61 4.55 0.20 246 10.95 0.08 0.02 40 11.92 0.61 <0.05 7.32 2.78 0.01 3.41 3.65 0.06 0.01 Detection limit 0.10 0.05 0.05 0.5 0.01 0.005 0.25 0.15 0.002 0.01 140 Table B5. Percent land use within well buffers Well* Rural Animal Trees All other Other residential/ operations bushes agricultural Hobby farm 1 70.14 29.86 2 58.63 9.58 21.47 10.32 3 30.98 61.39 0.00 7.63 4 14.86 4.62 79.94 0.58 5 16.28 83.13 0.59 6 97.02 2.98 7 8 98.94 87.56 1.06 12.44 9 92.93 7.07 10 1.62 72.58 7.75 18.04 11 5.47 80.67 13.86 12 58.55 41.45 13 91.41 8.59 14 23.27 15.36 61.36 15 98.70 1.30 16 88.35 1.98 9.67 17 2.59 97.41 18 58.40 27.74 13.87 19 97.38 2.62 20 78.38 21.62 21 92.08 7.92 22 93.59 6.41 23 100.00 24 100.00 25 100.00 26 9.98 40.69 27 100.00 28 96.09 3.91 29 19.29 61.98 30 14.26 42.11 12.68 31 70.67 17.84 11.49 32 39.12 5.97 54.91 33 37.82 5.98 56.19 34 98.74 1.11 0.15 35 99.56 0.44 36 100.00 37 99.92 0.08 38 70.21 29.79 39 87.80 12.20 40 100.00 141 Appendix C: Surface water sampling results Table C1: Q A / Q C for surface water samples: nutrients and Cl" Table C2: Q A / Q C for elements in surface water samples Tables C3 - C5: Nutrients and Cl" raw data Tables C6 - C11: Physical parameters raw data Tables C12 - C20: Elements in surface water raw data Table C21: Dissolved Oxygen Percent saturation Table C1. QA/QC results for surface water samples for N0 3" - N, P 0 4 , and CI' Tributary Name (SITEJD) Date N03-N(mg/L) P04(mg/L) Cr(mg/L) Bertrand Creek (BCr1) Jul 22/04 0.85 0.44 N/A 0.84 0.51 N/A Mean 0.85 0.48 Std Dev 0.01 0.05 CV(%) 0.70 9.66 Bertrand Creek (BCr2) Jul 22/04 0.34 0.09 35.26 0.34 0.09 35.18 0.32 0.09 Mean 0.33 0.09 35.22 Std Dev 0.02 0.01 0.057 CV(%) 3.60 2.9 0.161 Bertrand Creek (BCr8) Jul 22/04 1.03 0.03 9.93 0.5 0.03 9.94 Mean 1.01 0.03 9.94 Std Dev 0.02 0.01 0.01 CV(%) 2.17 12.86 0.07 Bertrand Creek (BCr11) Jul 22/04 N/A N/A 8.18 N/A N/A 8.14 Mean 8.16 Std Dev 0.03 CV(%) 0.35 Howes Creek (HC5) Jul 22/04 N/A N/A 27.2 N/A N/A 27.0 Mean 27.1 Std Dev 0.20 CV(%) 0.73 Cave Creek (CC13) Jul 22/04 0.30 0.09 N/A 0.30 0.01 N/A Mean 0.30 0.09 Std Dev 0.01 0.01 CV(%) 2.16 8.53 Bertrand Creek (BCr1) Aug 12/04 0.17 0.77 120 0.15 0.72 118 0.15 0.74 117 Mean 0.16 0.74 118 Std Dev 0.01 0.02 1.53 CV(%) 4.6 3.25 1.29 Bertrand Creek (BCr3) Oct 8/04 0.31 0.09 17.3 0.33 0.10 17.3 0.31 0.08 17.1 Mean 0.32 0.09 17.23 Std Dev 0.01 0.007 0.12 CV(%) 3.51 8.23 0.67 143 Table C1 continued Tributary Name (SITEJD) Date N03-N(mg/L) P04(mg/L) Cr(mg/L) Bertrand Creek (BCr12) Oct 8/04 1.29 0.04 13.90 1.30 0.04 13.90 1.30 0.03 13.90 Mean 1.30 0.04 13.90 Std Dev 0.01 0.01 0.00 CV(%) 0.45 17.09 0.00 Bertrand Creek (BCr3) Oct 27/04 1.19 0.07 15.50 1.28 0.07 15.70 1.14 0.06 15.70 Mean 1.20 0.07 75.63 Std Dev 0.07 0.01 0.72 CV(%) 5.90 7.30 0.74 Howes Creek (HC7) Oct 27/04 1.84 0.07 9.80 1.74 0.07 9.93 1.75 0.07 9.93 Mean 178 0.07 9.89 Std Dev 0.06 0.00 0.08 CV(%) 3.10 3.03 0.76 Bertrand Creek (BCr3) Nov 22/04 1.14 0.05 N/A 1.15 0.05 N/A Mean 175 0.05 Std Dev 0.01 0.00 CV(%) 0.62 5.13 Pepin Creek (PC9) Nov 22/04 1.30 N/A N/A 1.30 N/A N/A Mean 7.30 Std Dev 0.00 CV(%) 0.00 Bertrand Creek (BCr12) Nov 22/04 3.01 0.03 10.10 3.01 0.03 10.10 2.95 0.03 10.10 Mean 2.99 0.03 10.10 Std Dev 0.04 0.00 0.00 CV (%) 1.16 1.13 0.00 Howes Creek (HC5) Dec 10/04 1.72 0.42 2.85 1.69 0.39 3.08 1.68 0.45 2.90 Mean 7.70 0.42 2.94 Std Dev 0.02 0.03 0.12 CV(%) 1.23 6.78 4.11 Howes Creek (HC6) Dec 10/04 2.11 0.42 2.95 2.04 0.43 3.13 2.04 0.42 3.18 Mean 2.06 0.42 3.09 Std Dev 0.04 0.01 0.12 CV(%) 1.96 1.78 3.92 144 Tributary Name (SITEJD) Date N03'-N(mg/L) P04(mg/L) Cr(mg/L) Bertrand Creek (BCr4) Jan 24/04 2.14 0.04 15.10 2.13 0.05 15.10 2.18 0.04 15.00 Mean 2.75 0.04 75.07 Std Dev 0.03 0.01 0.06 CV(%) 1.23 10.78 0.38 Howes Creek (HC7) Jan 24/04 3.88 0.15 7.03 3.97 0.14 7.13 3.96 0.14 7.13 Mean 3.94 0.74 7.10 Std Dev 0.05 0.00 0.06 CV(%) 1.25 1.61 0.81 Cave Creek (CC13) Jan 24/04 2.16 0.15 8.68 2.20 0.15 8.45 2.17 0.14 8.42 Mean 2.18 0.15 8.52 Std Dev 0.02 0.01 0.14 CV(%) 0.96 3.48 1.67 Bertrand Creek (BCr2) Feb 14/04 0.88 0.05 18.70 0.88 0.05 18.60 0.86 N/A 18.80 Mean 0.88 0.05 78.70 Std Dev 0.01 0.00 0.10 CV(%) 1.15 1.82 0.54 Pepin Creek (PC9) Feb 14/04 2.20 0.01 5.51 2.21 0.01 5.56 2.19 0.01 5.73 Mean 2.20 0.07 5.60 Std Dev 0.01 0.00 0.12 CV(%) 0.46 6.35 2.06 . Bertrand Creek (BCr4) Mar 9/05 1.19 0.04 16.20 1.18 0.06 16.20 1.20 0.04 16.30 Mean 7.79 0.05 76.23 Std Dev 0.07 0.07 0.06 CV(%) 0.84 20.66 0.36 Bertrand Creek (BCr11) Mar 9/05 1.30 0.05 14.80 1.33 0.04 14.90 1.32 0.02 15.00 Mean 7.32 0.04 74.90 Std Dev 0.02 0.02 0.70 CV(%) 1.16 48.79 0.67 145 T a b l e C1 c o n t i n u e d Tributary Name (SITEJD) Date N03-N(mg/L) P04(mg/L) Cr(mg/L) Bert rand C r e e k (BCr4 ) A p r 22 /05 1.64 0.05 11.40 1.70 0.06 11.20 1.61 0.06 11.20 Mean 1.65 0.05 11.27 Std Dev 0.05 0.01 0.12 CV(%) 2.78 10.54 1.03 Pep in C r e e k ( P C 9 ) A p r 22 /05 0.70 0.02 4 .69 0.70 0.03 4.64 0.70 0.02 4 .83 Mean 0.70 0.03 4.72 Std Dev 0.00 0.01 0.10 CV(%) 0.25 18.04 2.09 Bert rand C r e e k (BCr1) M a y 20 /05 0.55 0.30 51.70 0.52 0.22 50.60 Mean 0.54 0.26 51.15 Std Dev 0.02 0.06 0.78 CV(%) 3.42 21.55 1.52 H o w e s C r e e k (HC5) M a y 20 /05 4 .67 0.86 11.00 4 .60 0.85 11.00 4.68 0.90 11.00 Mean 4.65 0.87 11.00 Std Dev 0.04 0.03 0.00 CV(%) 0.94 2.85 0.00 H o w e s C r e e k ( H C 7 ) M a y 20 /05 0.79 0.04 11.00 0.73 0.03 11.20 0.78 0.04 11.00 Mean 0.76 0.04 11.07 Std Dev 0.03 0.01 0.12 CV(%) 4.17 19.92 1.04 H o w e s C r e e k ( H C 5 ) J u n 16/05 20 .70 6.51 26 .70 21 .10 6.54 26 .60 21 .00 6.54 26 .20 Mean 20.93 6.53 26.50 Std Dev 0.21 0.02 0.27 CV(%) 0.99 0.27 1.00 Bert rand C r e e k (BCr8) J u n 16/05 5.72 0.02 12.20 5.33 0.02 12.00 5.34 0.03 12.10 Mean 5.46 0.02 72.70 Std Dev 0.22 0.00 0.10 CV(%) 4.07 17.48 0.83 146 Tab le C 2 . Q A / Q C for d isso lved e lements (Detection limits in ppm next to element in column heading) SITEJD Date CaO.l Cu 0.05 FeO.05 K0.5 MgO.Ol Mn 0.005 Na 0.25 Si 0.15 Sr 0.002 Zn 0.01 BCr2 Jul 20/04 27.58 <0.05 0.58 5.10 10.59 0.22 47.08 4.64 0.13 0.11 27.45 <0.05 0.56 5.08 10.57 0.22 46.76 4.60 0.13 0.11 Mean 27.52 N/A 0.57 5.09 10.58 0.22 46.92 4.62 0.13 0.11 Std Dev 0.10 N/A 0.02 0.01 0.01 0.00 0.23 0.03 0.00 0.00 CV(%) 0.35 N/A 2.93 0.28 0.12 1.86 0.48 0.57 0.20 1.69 BCr8 Jul 20/04 24.23 O.05 0.21 4.03 8.34 0.04 12.63 2.58 0.13 0.10 24.74 O.05 0.20 4.13 8.49 0.04 12.76 2.61 0.14 0.09 Mean 24.48 N/A 0.21 4.08 8.41 0.04 12.69 2.59 0.13 0.09 Std Dev 0.37 N/A 0.00 0.07 0.10 0.00 0.09 0.02 0.00 0.01 CV(%) 1.49 N/A 0.66 1.66 1.24 1.70 0.69 0.79 1.17 7.26 BCrl Aug 12/04 21.50 0.06 0.37 6.70 11.00 2.47 194 5.70 0.13 <0.01 25.46 O.05 0.41 6.69 11.09 2.48 191 5.68 0.13 O.01 21.25 0.02 0.33 6.60 10.90 2.40 196 5.64 0.13 <0.01 Mean 22.74 0.04 0.37 6.66 11.00 2.45 194 5.67 0.13 N/A Std Dev 2.36 0.03 0.04 0.06 0.09 0.04 2.11 0.03 0.00 N/A CV(%) 10.39 80.45 10.86 0.87 0.84 1.82 1.09 0.54 1.61 N/A CC13 Aug 12/04 15.15 <0.05 0.69 7.43 6.21 0.28 141 3.29 0.12 <0.01 15.85 <0.05 0.74 7.42 6.22 0.29 133 3.35 0.12 0.01 15.20 O.05 0.71 7.43 6.21 0.28 140 3.35 0.12 0.01 Mean 15.40 N/A 0.71 7.43 6.22 0.28 138 3.33 0.12 0.01 Std Dev 0.39 N/A 0.03 0.01 0.01 0.00 4.86 0.03 0.00 0.00 CV(%) 2.53 N/A 3.80 0.07 0.11 1.36 3.52 1.00 0.45 3.48 HC7 Oct 8/04 18.32 0.07 10.77 7.03 6.55 0.31 17.20 7.59 0.09 0.06 18.58 0.07 10.50 7.03 6.22 0.33 16.98 7.72 0.08 0.04 Mean 18.45 0.07 10.63 7.03 6.38 0.32 17.09 7.66 0.09 0.05 Std Dev 0.18 0.00 0.19 0.00 0.23 0.02 0.15 0.09 0.01 0.01 CV(%) 0.97 1.48 1.79 0.01 3.66 4.84 0.88 1.18 7.97 14.61 Table C2 continued SITE ID Date CaO.l Cu 0.05 Fe 0.05 K0.5 MgO.Ol Mn 0.005 Na 0.25 Si 0.15 Sr 0.002 Zn 0.01 PC10 Oct 8/04 25.15 <0.05 0.42 4.19 8.77 0.30 8.87 7.30 0.12 0.01 25.35 <0.05 0.52 4.34 8.64 0.29 8.92 7.02 0.14 0.01 Mean 25.25 N/A 0.47 4.26 8.70 0.30 8.90 7.16 0.13 0.01 Std Dev 0.14 N/A 0.07 0.11 0.09 0.01 0.03 0.20 0.02 0.00 CV(%) 0.54 N/A 15.26 . 2.48 1.00 2.14 0.39 2.83 12.19 5.56 BCr4 Dec 10/04 7.08 <0.05 0.79 2.63 2.17 0.05 3.45 2.54 0.03 0.04 6.87 <0.05 0.77 2.63 2.23 0.05 3.53 2.54 0.04 0.05 Mean 6.98 N/A 0.78 2.63 2.20 0.05 3.49 2.54 0.04 0.05 Std Dev 0.15 N/A 0.02 0.00 0.04 0.00 0.05 0.00 0.00 0.01 CV(%) 2.15 N/A 1.94 0.11 1.99 2.86 1.52 0.07 12.47 12.82 B C r l l Dec 10/04 8.15 <0.05 0.72 3.84 2.51 0.04 3.79 2.99 0.04 0.10 8.28 <0.05 0.79 3.66 2.39 0.04 3.43 3.02 0.04 0.14 Mean 8.21 N/A 0.76 3.75 2.45 0.04 3.61 3.01 0.04 0.12 Std Dev 0.09 N/A 0.05 0.13 0.08 0.00 0.25 0.02 0.00 0.03 CV(%) 1.10 N/A 6.27 3.45 3.42 0.54 6.94 0.80 0.27 23.67 oo Table C3. Summary Statistics for Surface Water Quality Parameters for the Wet and Dry Seasons SiteJD NO; -N PO4 cr Temperature DO Specific pH Turbidity Conductivity Wet Dry Wet Dry Wet Dry Wet Dry Wet Dry Wet Dry Wet Dry Wet Dry B C r l median 0.31 0.95 0.30 0.09 51.7 18.1 15.1 6.7 4.6 7.9 515 162 6.89 6.66 5.88 4.37 min 0.03 0.19 0.06 0.02 3.13 3.49 11.6 4.3 1.4 5.6 399 66 6.35 6.35 4.85 3.00 max 0.85 1.80 0.77 0.12 120 35.5 19.1 11.7 5.3 10.8 1015 254 7.08 7.37 22.7 39.9 BCr2 median 0.34 0.94 0.10 0.09 35.26 17.2 14.9 7.5 5.3 8.3 365 150 6.96 6.78 7.86 5.00 min 0.14 0.35 0.06 0.05 24.9 3.52 13.0 4.3 2.4 7.2 231 71 6.84 6.23 5.07 3.17 max 0.50 1.20 0.15 0.11 42.3 19.4 19.3 12.7 7.1 10.4 438 250 7.10 7.43 8.28 32.10 BCr3 median 0.44 1.14 0.08 0.06 20.8 15.5 14.7 7.8 7.4 9.7 262 152 6.97 6.91 5.53 5.33 min 0.26 0.59 0.04 0.02 14.62 3.46 13.0 5.0 2.3 9.4 87 74 6.74 6.35 3.97 3.00 max 0.63 1.46 0.09 0.10 31.9 17.3 18.2 12.4 8.6 11.0 359 225 7.09 7.55 18.7 33.7 BCr4 median 3.57 2.04 0.03 0.04 11.4 13.4 13.0 7.9 6.5 10.0 209 170 6.77 6.94 7.77 4.14 min 0.89 1.19 0.01 0.03 8.08 3.14 11.8 4.7 4.1 9.1 183 74 6.75 6.41 4.12 2.13 max 9.48 2.19 0.09 0.11 17.8 16.2 17.5 11.9 14.7 11.3 260 218 6.97 7.52 10.1 33.30 BCr8 median 1.03 2.09 0.03 0.05 12.2 11.8 14.7 8.1 7.1 10.3 218 172 6.77 7.02 5.34 4.87 min 0.04 1.53 0.00 0.04 9.93 3.84 12.3 5.0 3.9 8.6 193 61 6.73 6.59 4.48 2.90 max 5.72 2.69 0.05 0.14 17.0 16.1 20.6 13.1 13.6 11.2 245 217 7.06 7.46 6.06 35.6 B C r l l median 1.26 1.88 0.02 0.05 14.0 10.5 15.0 8.4 9.0 11.9 194 170 6.98 7.20 2.6 5.24 min 0.74 1.30 <0.01 0.03 8.18 3.81 12.4 5.3 5.4 10.9 153 83 6.95 6.82 2.59 2.00 max 1.98 2.51 0.04 0.14 15.4 14.8 18.6 14.5 14.0 12.3 204 . 209 7.25 7.70 7.02 29.9 B C r l 2 median 2.34 2.39 0.01 0.04 13.0 10.1 15.2 8.4 9.8 11.5 180 153 6.94 7.27 2.95 3.22 min 1.29 1.99 <0.01 0.02 9.72 4.46 12.3 5.1 8.5 10.8 165 93 6.86 6.86 1.8 1.00 max 2.73 3.01 0.04 0.17 13.9 14.2 20.0 13.6 14.4 13.0 193 206 7.25 7.69 3.23 45.2 HC5 median 10.71 2.35 5.68 0.31 21.0 7.69 13.9 7.7 11.0 11.0 457 165 6.94 6.96 7.2 7.35 min 4.67 1.72 0.86 0.17 11.0 2.85 12.2 3.9 5.4 9.5 227 62 6.90 6.31 4.48 3.00 max 20.93 8.09 .32.50 1.16 27.24 9.65 17.1 11.8 12.1 12.0 575 264 7.10 7.35 112 58.8 HC6 median 2.97 0.95 0.47 0.31 10.7 6.93 15.3 7.4 13.3 11.1 183 159 7.11 7.19 8.17 5.37 min 2.97 2.11 0.47 0.19 10.7 2.95 15.3 4.8 13.3 10.2 183 79 7.11 6.44 8.17 2.92 max 2.97 6.59 0.47 0.64 10.7 10.80 15.3 13.5 13.3 12.1 183 241 7.11 7.58 8.17 63.2 HC7 median 0.16 2.90 0.05 0.14 11.7 8.84 11.8 8.2 3.8 7.5 173 156 6.24 6.48 61.1 8.45 min 0.08 1.84 0.04 0.04 11.0 4.63 11.8 5.1 1.0 2.9 156 104 5.48 6.11 31.1 4.22 max 0.79 3.93 0.24 0.24 19.2 16.7 11.9 11.6 7.1 10.6 488 196 6.43 7.21 160 40.3 4^  Table C 3 continued SiteJD NO/ -N P04 cr Temperature DO Specific PH Turbidity Conductivity 2.56 1.80 PC9 median 0.65 1.43 0.05 0.03 6.17 5.51 14.5 7.5 4.3 6.6 217 195 6.63 6.92 min 0.43 0.70 0.02 0.01 5.36 3.69 11.8 4.3 0.9 4.9 162 135 6.51 6.64 2.32 1.00 max 1.07 2.20 0.09 0.12 7.57 6.73 18.5 12.1 6.7 9.5 228 213 6.88 7.42 4.14 154.0 PC10 median 0.31 1.52 0.03 0.04 8.13 7.59 14.5 7.8 6.5 10,1 227 206 7.00 7.14 8.85 2.61 min 0.11 0.83 0.02 0.03 5.88 5.15 11.6 3.8 5.1 5.8 176 142 6.45 6.70 4.31 1.00 max 0.70 2.19 0.26 0.16 8.76 8.16 16.9 12.2 11.8 11.2 250 233 7.36 7.63 9.56 7.63 CC13 median 0.30 2.04 0.09 0.14 78.80 10.50 13.5 7.8 8.2 11.3 428 152 7.02 7.31 5.29 3.97. min 0.14 1.06 0.07 0.10 27.30 6.02 12.4 3.8 1.9 10.4 247 110 7.02 6.78 3.54 2.61 max 1.33 2.76 0.29 0.20 125.0 32.70 16.1 12.8 11.4 12.8 710 283 7.32 7.70 38.3 20.90 Table C 4 . N 0 3 " - N (mg/L) raw data Tributary name (Site ID) Jul 20/04 Aug 12/04 Oct 8/04 Oct 27/04 Nov 22/04 Dec 10/04 Jan 24/05 Feb 14/05 Mar 9/05 Apr 22/05 May 20/05 Jun 16/05 Bertrand Creek (BCM) 0.85 0.17 0.31 0.83 1.15 1.02 1.80 0.95 0.82 0,19 0.55 0.03 Bertrand Creek (BCr2) 0.34 0.15 0.42 0.94 1.07 1.08 1.20 0.88 0.64 0.35 0.50 0.14 Bertrand Creek (BCr3) 0.63 0.26 0.31 1.19 1.14 1.19 1.46 1.07 0.65 0.59 0.62 0.44 Bertrand Creek (BCr4) 3.57 3.65 0.89 2.19 2.09 1.30 2.14 2.04 1.19 1.64 2.08 9.48 Bertrand Creek (BCr8) 1.03 0.05 0.93 2.09 2.26 1.86 2.69 2.35 1.53 1.72 1.48 5.72 Bertrand Creek (BCM1) 1.26 1.98 0.74 1.88 2.21 1.81 2.51 2.17 1.30 1.65 1.26 0.86 Bertrand Creek (BCM 2) 2.47 2.34 1.29 2.39 3.01 2.26 2.97 2.74 2.07 1.99 2.05 2.73 Howes Creek (HC5) 10.71 11.30 9.44 8.09 3.52 1.72 2.35 2.21 1.86 3.24 4.67 20.93 Howes Creek (HC6) no flow no flow no flow 6.59 3.90 2.11 2.95 2.75 5.44 2.55 2.97 no flow Howes Creek (HC7) no flow no flow 0.08 1.84 3.26 2.83 3.88 2.90 3.93 2.16 0.79 0.16 Pepin Creek (PC9) 0.43 1.07 0.65 0.73 1.30 1.43 1.62 2.20 1.80 0.70 0.74 0.50 Pepin Creek (PC10) 0.31 0.25 0.44 0.83 1.47 1.52 2.19 1.97 1.65 1.19 0.70 0.11 Cave Creek (CC13) 0.30 0.14 1.33 2.04 2.76 2.20 2.16 1.74 1.09 1.06 1.01 0.22 o Table C5. P 0 4 - P (mg/L) raw data Tributary Name (site ID) Jul 20/04Aug 12/04 Oct 8/04 Oct 27/04 Nov 22/04 Dec 10/04 Jan 24/05 Feb 14/05Mar 9/05Apr 22/05 May 20/05Jun 16/05 3ertrand Creek (BCrl) 0.44 0.77 0.06 0.10 0.07 0.12 0.02 0.06 0.09 0.11 0.30 0.12 Bertrand Creek (BCr2) 0.09 0.10 0.12 0.10 0.07 0.11 0.06 0.05 0.09 0.09 0.15 0.06 Bertrand Creek (BCr3) 0.08 0.08 0.10 0.07 0.05 0.10 0.05 0.03 0.07 0.06 0.07 0.04 Bertrand Creek (BCr4) 0.03 0.02 0.09 0.04 0.05 0.11 0.04 0.03 0.04 0.05 0.06 0.02 Bertrand Creek (BCr8) 0.03 <0.01 0.05 0.04 0.04 0.14 0.07 0.06 0.05 0.05 0.03 0.02 Bertrand Creek (BCrU) 0.02 <0.01 0.04 0.03 0.04 0.14 0.06 0.04 0.05 0.05 0.03 0.02 Bertrand Creek (BCr12) <0.01 <0.01 0.04 0.02 0.04 0.17 0.06 0.04 0.03 0.05 0.02 0.01 Howes Creek (HC5) 2.67 5.68 32.50 1.16 0.31 0.42 0.17 0.18 0.24 0.51 0.86 6.53 Howes Creek (HC6) no flow no flow no flow 0.64 0.22 0.42 0.19 0.23 0.43 0.31 0.47 no flow Howes Creek (HC7) no flow no flow 0.24 0.07 0.09 0.24 0.15 0.14 0.04 0.15 0.04 0.05 Pepin Creek (PC9) 0.08 0.09 0.05 0.04 0.02 0.12 0.03 0.01 0.04 0.02 0.02 0.02 Pepin Creek (PC10) 0.03 0.02 0.05 0.03 0.03 0.13 0.16 0.04 0.04 0.05 0.03 0.26 Cave Creek (CC13) 0.09 0.07 0.29 0.12 0.12 0.20 0.15 0.10 0.14 0.15 0.16 0.07 Table C6. Chloride (mg/L) raw data Tributary Name (site ID) Jul 20/04 Aug 12/04 Oct 8/04 Oct 27/04 Nov 22/04 Dec 10/04 Jan 24/05 Feb 14/05 Mar 9/05 Apr 22/05 May 20/05 Jun 16/05 Bertrand Creek (BCr l ) 76.80 120 3.13 22.80 13.10 3.49 35.50 18.10 21.00 15.80 51.70 46.20 Bertrand Creek (BCr2) 35.26 42.30 24.9 18.70 10.90 3.52 15.60 18.70 19.40 17.20 42.0 33.6 Bertrand Creek (BCr3) 14.62 31.90 17.30 15.50 9.84 3.46 15.90 17.30 16.50 15.40 24.30 20.80 Bertrand Creek (BCr4) 9.14 11.40 11.80 13.40 10.70 3.14 15.10 15.40 16.20 11.40 17.80 8.08 Bertrand Creek (BCr8) 9.93 11.60 13.30 13.20 10.50 3.84 11.80 12.70 16.10 10.50 17.00 12.20 Bertrand Creek (BCr11) 8.18 8.56 15.10 11.70 9.55 3.81 10.30 11.90 14.80 10.50 15.40 14.00 Bertrand Creek (BCr12) 9.72 9.98 13.90 12.70 10.10 4.46 9.89 11.70 14.20 8.68 13.30 13.00 Howes Creek (HC5) 27.24 19.10 21.00 9.65 9.16 2.85 5.61 6.32 8.52 7.69 11.00 26.70 Howes Creek (HC6) no flow no flow no flow 9.30 10.80 2.95 5.45 6.80 9.80 6.93 10.70 no flow Howes Creek (HC7) no flow no flow 19.20 9.80 8.89 4.63 7.13 7.83 16.70 8.84 11.00 11.70 Pepin Creek (PC9) 6.56 6.91 6.77 6.09 6.03 3.73 3.69 5.51 6.73 4.69 5.36 7.57 Pepin Creek (PC10) 8.13 8.47 8.76 8.16 8.00 5.15 5.53 7.78 7.59 6.03 6.97 5.88 Cave Creek (CC13) 96.9 125.00 78.80 32.70 16.60 6.02 8.68 10.50 17.60 9.99 27.30 66.70 Table C7. Temperature (°C) raw data Site ID Jun 2/04 Jul 20/04 Aug 12/04 Oct 8/04 Oct 27/04 Nov 22/04 Dec 10/04 Jan 24/05 Feb 14/05 Mar 9/05 Apr 22/05 May 20/05 Jun 16/05 BCr1 12.5 19.1 16.6 11.6 6.7 5.6 6.0 7.4 4.3 9.8 11.7 13.1 15.1 BCr2 14.1 19.3 18.3 13.0 8.6 6.2 6.3 7.5 4.3 9.9 12.7 13.6 14.9 BCr3 14.4 18.2 17.5 13.0 8.7 6.5 6.5 7.8 5.0 10.1 12.4 13.3 14.7 BCr4 13.6 17.5 17.0 12.5 8.2 6.3 6.6 7.9 4.7 10.1 11.9 13 11.8 BCr8 14.4 20.6 17.7 top 12.3 8.8 6.6 6.7 8.1 5.0 10.4 13.1 14.6 14.7 BCM1 16.0 14.5 18.6 12.4 8.5 6.9 6.9 8.4 5.3 11.0 14.5 15 16.3 B C M 2 15.6 20.0 14.9 12.3 8.6 6.8 6.9 8.4 5.1 10.9 13.6 15.2 15.9 HC5 14.5 17.1 15.5 12.2 8.2 6.7 6.2 7.7 3.9 10.3 11.8 13.4 13.9 HC6 no flow no flow no flow no flow 7.4 6.4 6.4 7.9 4.8 10.9 13.5 15.3 no flow HC7 12.8 no flow no flow 11.8 9.4 7.7 6.6 8.2 5.1 10.0 11.6 11.8 11.9 PC9 14.7 18.5 17.3 11.8 7.5 5.3 6.1 8.0 4.3 9.7 12.1 13.2 14.5 PC10 13.9 16.9 16.0 11.6 7.8 6.1 6.6 8.2 3.8 10.1 12.2 13.1 14.5 CC13 14.1 16.1 15.6 12.4 7.8 6.0 7.2 8.1 3.8 10.6 12.8 13.5 13.4 Table C8. Specific Conductivity (uS/cm) raw data Jun 2/04 Jul 20/04 Aug 12/04 Oct 8/04 Oct 27/04 Nov 22/04 Dec 10/04 Jan 24/05 Feb 14/05 Mar 9/05 Apr 22/05 May 20/05 Jun 16/05 B C M 384 1015 996 515 254 162 66 102 134 219 180 432 399 BCr2 359 438 437 231 250 148 71 125 150 189 196 365 326 BCr3 287 279 359 87 225 148 74 140 152 172 189 262 256 BCr4 275 258 260 183 218 171 74 141 150 175 , 170 209 195 BCr8 236 245 . 236 193 217 172 61 134 140 183 174 208 218 BCM1 213 158 153 204 209 170 83 130 139 180 170 194 202 BCr12 198 175 165 193 206 171 93 134 137 182 153 180 188 HC5 274 506 575 402 264 189 62 115 115 165 182 227 457 HC6 no flow no flow no flow no flow 241 183 79 118 117 226 159 183 no flow HC7 209 no flow no flow 488 196 173 104 128 122 188 156 156 173 PC9 228 228 222 162 213 205 135 150 158 209 195 198 217 PC10 241 250 245 227 233 213 142 150 175 210 206 212 176 CC13 305 555 710 428 283 191 110 121 124 190 152 247 375 4^ . Table C9. Dissolved oxygen (mg/L) SITEJD Jul 20/04 Aug 12/04 Sept/04 Oct 27/04 Nov 22/04 Dec 10/04 Jan 24/05 Feb 14/05 Mar 9/05 Apr 22/05 May 20/05 Jun 16/05 B C M 1.9 1.4 4.6 6.4 8.0 10.1 7.4 10.8 7.9 5.6 5.3 5.1 BCr2 4.2 2.4 7.1 7.3 9.1 10.4 8.3 10.2 8.2 7.2 5.3 5.7 BCr3 4.9 2.3 8.6 9.7 9.8 10.8 9.4 11 9.4 9.4 7.4 7.4 BCr4 4.4 4.1 6.5 10.0 11.2 10.6 9.9 11.3 9.7 9.1 9.8 14.7 BCr8 5.6 3.9 7.1 10.0 8.6 11.2 9.8 11 10.5 10.3 13.6 13.4 B C r U 7.7 5.4 9.0 12.0 12.3 11.4 10.9 11.9 12.1 11.6 13.5 14 BCr12 8.5 9.0 9.8 12.6 11.2 11.5 10.8 11.7 13.0 10.9 14.0 14.4 HC5 5.4 5.4 12.1 10.2 11.0 12.0 11.0 11.7 10.7 9.5 11.0 11.3 HC6 no flow no flow no flow 10.8 11.1 12.1 10.7 11.9 11.6 10.2 13.3 no flow HC7 no flow no flow 1.0 2.9 6.9 9.9 7.5 10.6 7.6 6.9 7.1 3.8 PC9 0.9 1.6 5.6 6.2 7.8 9.5 6.1 9.1 6.6 4.9 6.7 4.3 PC10 6.5 6.3 7.4 10.1 11.2 10.1 5.8 10.9 10.1 9 11.8 5.1 CC13 1.9 3.1 8.2 11.3 12.6 11.3 11.5 12.8 11.1 10.4 11.4 9.6 Ul U l Table C10. pH raw data Tributary Name (site ID) Oct 8/04 Oct 27/04 Nov 22/04 Dec 10/04 Jan 24/05 Feb 14/05 Mar 9/05 Apr 22/05 May 20/05 Jun 16/05 Bertrand Creek (BCM) 6.4 6.7 6.7 6.4 7.1 7.4 6.6 6.6 7.1 6.9 Bertrand Creek (BCr2) 6.8 6.8 6.7 6.2 7.0 7.4 6.6 6.8 7.1 7.0 Bertrand Creek (BCr3) 6.7 6.9 6.9 6.4 7.1 7.6 6.8 6.9 7.1 7.0 Bertrand Creek (BCM) 6.8 6.9 7.0 6.4 7.2 7.5 6.9 6.9 7.0 6.8 Bertrand Creek (BCr8) 6.7 7.2 7.0 6.6 7.1 7.5 7.0 6.9 7.1 6.8 Bertrand Creek (BCM 1) 7.0 7.3 7.1 6.8 7.2 7.7 7.5 7.1 7.3 7.0 Bertrand Creek (BCM 2) 6.9 7.5 7.2 6.9 7.3 7.7 7.7 7.1 7.3 6.9 Howes Creek (HC5) 6.9 6.8 7.0 6.3 7.0 7.4 7.0 6.9 7.1 6.9 Howes Creek (HC6) no flow 7.2 7.2 6.4 7.2 7.6 7.4 7.1 7.1 no flow Howes Creek (HC7) 6.4 6.5 6.5 6.4 6.8 7.2 6.1 6.5 6.2 5.5 Pepin Creek (PC9) 6.6 7.2 6.9 6.6 7.1 7.4 6.8 6.9 6.9 6.5 Pepin Creek (PC10) 7.0 7.5 7.2 6.7 7.0 7.6 7.1 7.1 7.4 6.5 Cave Creek (CC1.3) 7.0 7.3 7.1 6.8 7.4 7.7 7.5 7.2 7.3 7.0 U l ON Table C 1 1 . Turbidity (NTU) raw data Tributary Name (site ID) Oct 8/04 Oct 27/04 Nov 22/04 Dec 10/04 Jan 24/05 =eb 14/05 Vlar9/05 Apr 22/05 May 20/05 Jun 16/05 Bertrand Creek (BCM) 22.7 3.0 3.18 39.9 3.06 6.91 5.41 4.37 5.88 4.85 Bertrand Creek (BCr2) 7.9 5.0 6.73 32.1 4.2 4.88 7.00 3.17 8.28 5.07 Bertrand Creek (BCr3) 18.7 .3.0 7.04 33.7 4.41 5.33 6.33 3.23 5.53 3.97 Bertrand Creek (BCr4) 10.1 3.0 4.85 33.3 4.14 3.93 5.45 2.13 7.77 4.12 Bertrand Creek (BCr8) 6.1 3.0 4.87 35.6 4.64 7.46 5.81 2.9 4.48 5.34 Bertrand Creek (BCr11) 2.6 2.0 3.05 29.9 5.52 7.7 5.24 2.45 7.02 2.59 Bertrand Creek (BCM 2) 1.8 1.0 3.22 45.2 5.6 7.69 2.63 2.19 2.95 3.23 Howes Creek (HC5) 112.0 3.0 10.8 58.8 6.75 7.35 11.7 4.7 7.2 4.48 Howes Creek (HC6) no flow 18.0 2.92 63.2 4.79 7.58 5.37 3.15 8.17 no flow Howes Creek (HC7) 61.1 30.0 8.45 40.3 4.22 7.21 18.3 4.23 31.1 160 Pepin Creek (PC9) 4.1 1.0 1.3 154.0 12.0 7.4 1.80 1.3 2.32 2,56 Pepin Creek (PC10) 8.9 1.0 2.41 4.56 2.61 7.63 2.57 2.94 4.31 9.56 Cave Creek (CC13) . 38.3 3.0 3.57 20.9 3.97 7.7 4.37 2.61 5.29 3.54 U l Table C12. Dissolved calcium (ppm) raw data Tributary Name (site ID) Ju ly 20/04 A u g 12/04 Sept/04 Dec 10/04 Feb 14/04 Bertrand Creek (BCr l ) 24.7 21.5 4.0 5.9 12.7 Bertrand Creek (BCr2) 27.6 33.0 11.1 6.4 12.5 Bertrand Creek (BCr3) 26.1 27.6 9.9 7.3 14.0 Bertrand Creek (BCr4) 27.6 27.9 15.5 7.1 14.3 Bertrand Creek (BCr8) 24.2 20.5 15.1 8.9 14.4 Bertrand Creek (BCM1) 12.4 11.6 16.3 8.2 13.8 Bertrand Creek (BCr12) 14.7 13.5 19.7 8.8 13.6 Howes Creek (HC5) 48.7 65.8 35.3 7.5 13.2 Howes Creek (HC6) no flow no flow no flow 8.1 13.1 Howes Creek (HC7) no flow no flow 18.3 10.6 13.3 Pepin Creek (PC9) 26.7 25.0 23.2 16.9 20.8 Pepin Creek (PC10) 29.1 28.0 25.2 16.9 21.6 Cave Creek (CC13) 17.5 15.1 16.1 10.5 12.9 Table C13. Dissolved iron (ppm) raw data Tributary Name (site ID) Ju ly 20/04 A u g 12/04 Sept/04 Dec 10/04 Feb 14/04 Bertrand Creek (BCr l ) 0.601 0.370 0.916 0.968 0.614 Bertrand Creek (BCr2) 0.582 0.603 0.527 0.737 0.483 Bertrand Creek (BCr3) 0.599 0.798 1.056 0.821 0.542 Bertrand Creek (BCr4) 0.356 0.184 0.696 0.794 0.411 Bertrand Creek (BCr8) 0.206 1.034 0.425 0.736 0.633 Bertrand Creek (BCr11) 0.471 0.448 0.260 0.724 0.436 Bertrand Creek (BCr12) 0.175 0.113 0.339 1.025 0.364 Howes Creek (HC5) 0.217 0.100 0.357 1.019 0.379 Howes Creek (HC6) no flow no flow no flow 1.006 0.271 Howes Creek (HC7) no flow no flow 10.769 0.792 0.784 Pepin Creek (PC9) 0.680 0.464 0.296 2.208 0.268 Pepin Creek (PC10) 0.137 <0.05 0.420 0.225 0.136 Cave Creek (CC13) 1.419 0.689 1.030 0.597 0.295 Table C14. Dissolved potassium (ppm) raw data Tributary Name (site ID) July 20/04 Aug 12/04 Sept/04 Dec 10/04 Feb 14/04 Bertrand Creek (BCM) 4.788 6.703 1.194 2.878 2.752 Bertrand Creek (BCr2) 5.104 7.300 2.778 2.591 2.750 Bertrand Creek (BCr3) 3.488 4.857 2.392 2.512 2.615 Bertrand Creek (BCr4) 3.453 4.834 4.035 2.625 2.963 Bertrand Creek (BCr8) 4.032 7.167 3.652 3.775 3.549 Bertrand Creek ( B C r U ) 2.576 2.580 4.846 3.842 3.779 Bertrand Creek (BCM2) 3.633 3.310 6.222 4.472 4.214 Howes Creek (HC5) 25.147 43.602 45.944 4.035 4.301 Howes Creek (HC6) no flow no flow no flow 4.310 4.509 Howes Creek (HC7) no flow no flow 7.031 4.657 4.073 Pepin Creek (PC9) 1.696 2.285 2.511 3.388 2.394 Pepin Creek (PC10) 2.682 2.868 4.186 5.526 5.586 Cave Creek (CC13) 10.508 7.429 14.583 5.582 5.806 Table C15. Dissolved magnesium (ppm) raw data Tributary Name (site ID) July 20/04 Aug 12/04 Sept/04 Dec 10/04 Feb 14/04 Bertrand Creek (BCM) 10.400 10.997 1.187 2.043 5.003 Bertrand Creek (BCr2) 10.590 13.150 4.440 2.179 4.916 Bertrand Creek (BCr3) 8.709 9.447 3.666 2.306 5.187 Bertrand Creek (BCr4) 9.497 9.707 5.521 2.167 4.986 Bertrand Creek (BCr8) 8.338 7.376 5.353 2.747 4.957 Bertrand Creek (BCr11) 4.796 5.599 5.898 2.509 4.792 Bertrand Creek (BCM2) 5.059 4.693 6.534 2.826 4.652 Howes Creek (HC5) 13.628 18.499 10.048 2.500 4.862 Howes Creek (HC6) no flow no flow no flow 2.692 4.769 Howes Creek (HC7) no flow no flow 6.550 3.612 4.639 Pepin Creek (PC9) 9.668 9.012 8.350 6.334 7.363 Pepin Creek (PC10) 9.721 9.564 8.766 5.147 6.982 Cave Creek (CC13) 6.775 6.211 6.378 2.986 4.241 159 Table C16. Dissolved manganese (ppm) raw data Tributary Name (site ID) Ju ly 20/04 A u g 12/04 Sept/04 Dec 10/04 Feb 14/04 Bertrand Creek (BCr1) 0.386 2.472 0.053 0 033 0 074 Bertrand Creek (BCr2) 0.221 0.584 0.077 0 037 0 064 Bertrand Creek (BCr3) 0.259 0.904 0.155 0 050 0 088 Bertrand Creek (BCr4) 0.069 0.057 0.070 0 049 0 038 Bertrand Creek (BCr8) 0.041 0.212 0.027 0 045 0 040 Bertrand Creek (BCM1) 0.191 0.173 0.013 0 041 0 039 Bertrand Creek (BCr12) 0.022 0.040 0.015 0 084 0 032 Howes Creek (HC5) 0.108 0.042 0.067 0 077 0 065 Howes Creek (HC6) no flow no flow no flow 0 072 0 016 Howes Creek (HC7) no flow no flow 0.310 0 023 0 025 Pepin Creek (PC9) 0.198 0.126 0.020 0 095 0 003 Pepin Creek (PC10) 0.025 0.014 0.303 0 009 0 011 Cave Creek (CC13) 0.543 0.279 0.106 0 039 0 025 Table C17. Dissolved sodium (ppm) raw data Tributary Name (site ID) Ju ly 20/04 A u g 12/04 Sept/04 Dec 10/04 Feb 14/04 Bertrand Creek (BCr1) 116.617 194.242 5.051 3.960 15.630 Bertrand Creek (BCr2) 47.080 46.810 31.689 3.924 16.125 Bertrand Creek (BCr3) 19.503 38.475 20.924 3.974 14.044 Bertrand Creek (BCr4) 11.220 12.786 12.371 3.454 12.205 Bertrand Creek (BCr8) 12.633 13.061 14.240 3.762 9.600 Bertrand Creek (BCr11) 10.491 12.572 16.059 3.787 9.552 Bertrand Creek (BCr12) 12.282 12.727 12.915 4.254 9.404 Howes Creek (HC5) 24.112 15.143 10.894 2.420 5.029 Howes Creek (HC6) no flow no flow no flow 2.545 5.112 Howes Creek (HC7) no flow no flow 17.196 3.412 5.620 Pepin Creek (PC9) 9.172 9.698 6.371 4.273 5.622 Pepin Creek (PC10) 11.806 12.017 . 8.874 4.964 6.891 Cave Creek (CC13) 81.509 142.108 60.942 5.445 8.554 160 Table C18. Dissolved silicon (ppm) raw data Tributary Name (site ID) July 20/04 Aug 12/04 Sept704 Dec 10/04 Feb 14/04 Bertrand Creek (BCM) 5.691 5.697 1.348 2 763 3 886 Bertrand Creek (BCr2) 4.639 5.857 3.273 2 768 3 786 Bertrand Creek (BCr3) 5.510 5.679 2.959 2 760 4 209 Bertrand Creek (BCr4) 6.143 6.732 3.994 2 543 4 349 Bertrand Creek (BCr8) 2.579 6.935 4.092 3 006 4 496 Bertrand Creek (BCM1) 6.080 8.125 3.943 2 988 4 288 Bertrand Creek (BCM2) 2.499 3.283 5.958 3 216 4 350 Howes Creek (HC5) 9.467 11.585 5.019 2 803 4 193 Howes Creek (HC6) no flow no flow no flow 2 883 4 059 Howes Creek (HC7) no flow no flow 7.592 3 639 4 338 Pepin Creek (PC9) 7.679 7.280 7.160 6 257 5 791 Pepin Creek (PC10) 7.934 8.036' 7.304 4 673 4 838 Cave Creek (CC13) 3.449 3.293 4.455 3 049 3 072 Table C19. Dissolved strontium (ppm) raw data Tributary Name (site ID) July 20/04 Aug 12/04 Sept/04 Dec 10/04 Feb 14/04 Bertrand Creek (BCM) 0.126 0.127 0.012 0 032 0 065 Bertrand Creek (BCr2) 0.128 0.167 0.053 0 031 0 064 Bertrand Creek (BCr3) 0.120 0.131 0.046 0 035 0 072 Bertrand Creek (BCr4) 0.137 0.144 0.078 0 033 0 075 Bertrand Creek (BCr8) 0.134 0.132 0.076 0 043 0 076 Bertrand Creek (BCr11) 0.073 0.065 0.087 0 039 0 077 Bertrand Creek (BCM 2) 0.097 0.091 0.112 0 045 0 078 Howes Creek (HC5) 0.250 0.357 0.190 0 037 0 072 Howes Creek (HC6) no flow no flow no flow 0 041 0 072 Howes Creek (HC7) no flow no flow 0.094 0 057 0 073 Pepin Creek (PC9) 0.122 0.116 0.101 0 078 0 096 Pepin Creek (PC10) 0.148 0.143 0.120 0 074 0 104 Cave Creek (CC13) 0.121 0.120 0.120 0 050 0 067 161 Table C20. Dissolved zinc (ppm) raw data [Tributary Name (site ID)July 20/04 A u g 12/04 Sept/04 Dec 10/04 Feb 14/04 Bertrand Creek (BCM) 0.123 <0.01 0.050 0 049 0.021 Bertrand Creek (BCr2) 0.111 <0.01 0.034 0 034 0.017 Bertrand Creek (BCr3) 0.103 < 0.01 0.057 0 035 0.016 Bertrand Creek (BCr4) 0.109 <0.01 0.026 . 0 041 0.011 Bertrand Creek (BCr8) 0.097 1.424 0.030 0 044 0.017 Bertrand Creek (BCM 1) 0.104 0.003 0.011 0 099 <0.01 Bertrand Creek (BCM 2) 0.089 0.007 < 0.01 0 029 0.015 Howes Creek (HC5). 0.203 0.119 0.170 0 033 0.022 Howes Creek (HC6) no flow no flow no flow 0 031 0.010 Howes Creek (HC7) no flow no flow 0.055 0 021 0.010 Pepin Creek (PC9) 0.090 <0.01 <0.01 0 080 <0.01 Pepin Creek (PC10) 0.083 <0.01 0.012 0 048 <0.01 Cave Creek (CC13) 0.104 <0.01 0.062 0 024 0.038 162 Table C 2 1 . Dissolved Oxygen Percent Saturation. All values shown as percentage. Site ID J u n 04 Ju l 04 A u g 04 Sept 04 Oct 04 Nov 04 Dec 04 Jan 05 Feb 05 Mar 05 Apr 05 May 05 J u n 05 BCr1 45 20 14 43 53 64 81 61 82 70 52 50 51 BCr2 48 45 25 67 63 73 84 70 78 73 68 51 57 BCr3 72 52 24 82 84 81 89 79 86 83 87 70 73 BCr4 81 46 42 62 84 90 87 84 88 86 84 93 136 BCr8 93 63 41 66 87 71 92 83 86 93 98 135 133 BCM1 110 76 58 83 104 101 94 92 93 110 115 134 142 B C M 2 117 94 89 91 109 92 95 91 92 118 106 139 146 HC5 81 56 55 112 86 91 96 93 89 95 88 104 110 HC6 no flow no flow no flow no flow 89 89 97 90 93 105 99 132 no flow HC7 33 no flow no flow 9 25 58 82 63 83 67 64 66 35 PC9 37 10 17 52 52 61 76 52 69 58 45 64 43 PC10 86 67 64 69 85 90 83 49 83 89 83 112 51 CC13 88 19 31 76 95 101 93 97 98 101 99 111 91 ON LO Appendix D: Sediment Sampling Results Table D1. Q A / Q C Results for sediment samples Table D2. Certified values and acceptable ranges for Priority PollutnT™ / CLP Lot No. D035 -540 Table D3. Q A / Q C results for reference sediment material Priority PollutnT™ / CLP Lot No. D035 - 540 Table D4. Sediment Analysis raw data for the dry season Table D5. Sediment Analysis raw data for the wet season Table D6. Significant Spearman Rank Correlation coefficients for elements in sediments during the dry season Table D7. Significant Spearman Rank Correlation coefficients for elements in sediments during the wet season 164 Table D1. Q A / Q C Results for sediment samples (ppm x 100) Season Tibutary name (SITEJD) Al Ba Ca Dry Bertrand Creek (BCr8) 225.43 2.08 51.08 224.73 2.08 50.97 Mean 225.08 2.08 51.03 Std Dev 0.50 0.00 0.07 CV(%) 0.22 0.02 0.14 Bertrand Creek (BCM 1) 192.22 1.87 56.32 191.25 1.86 55.80 Mean 191.73 1.86 56.06 Std Dev 0.69 0.00 0.37 CV(%) 0.36 0.14 0.65 Howes Creek (HC5) 197.16 1.44 48.12 196.06 1.43 47.75 Mean 196.61 1.44 47.93 Std Dev 0.77 0.01 0.26 CV(%) 0.39 0.39 0.54 Pepin Creek (PC9) 168.08 1.62 80.09 167.52 1.61 79.56 Mean 167.80 1.62 79.82 Std Dev 0.39 0.01 0.38 CV(%) 0.23 0.47 0.47 Wet Bertrand Creek (BCr3) 185.62 1.69 52.68 182.90 1.66 51.97 Mean 184.26 1.67 52.32 Std Dev 1.93 0.02 0.50 CV(%) 1.05 1.16 0.96 Co Cr 0.14 0.52 0.14 0.52 0.14 0.52 0.00 0.00 0.44 0.02 0.16 0.39 0.16 0.39 0.16 0.39 0.00 0.00 0.23 0.18 0.18 0.41 0.18 0.40 0.18 0.41 0.00 0.00 0.92 0.26 0.14 0.45 0.14 0.45 0.14 0.45 0.00 0.00 0.49 0.37 0.16 0.48 0.15 0.47 0.16 0.48 0.00 0.00 1.68 0.87 Cu Fe 0.40 293.74 0.40 290.99 0.40 292.37 0.00 1.95 0.11 0.67 0.37 250.22 0.33 250.14 0.35 250.18 0.03 0.06 8.76 0.02 0.29 327.60 0.29 326.20 0.29 326.90 0.00 0.99 0.52 0.30 0.53 252.72 0.52 250.95 0.52 251.83 0.01 1.25 1.16 0.50 0.53 358.11 0.55 353.32 0.54 355.72 0.02 3.39 3.55 0.95 K Mg 9.37 59.37 9.59 59.16 9.48 59.27 0.15 0.15 1.62 0.25 10.50 56.54 9.59 56.27 10.05 56.41 0.64 0.19 6.40 0.34 12.02 54.59 12.07 54.47 12.04 54.53 0.03 0.08 0.28 0.15 11.90 71.98 11.68 72.12 11.79 72.05 0.15 0.10 1.29 0.14 9.69 66.38 9.45 65.56 9.57 65.97 0.17 0.58 1.73 0.88 Table D1 continued (ppm x 100) Season Tibutary name (SITEJD) A l B a C a Bertrand Creek (BCr4) 222.58 1.94 47.55 266.47 1.90 46.81 Mean 244.52 1.92 47.18 Std Dev 31.04 0.02 0.52 CV(%) 12.69 1.27 1.11 Bertrand Creek (BCM 2) 235.01 1.51 44.12 235.26 1.49 43.98 Mean 235.14 1.50 44.05 Std Dev 0.18 0.01 0.10 CV(%) 0.08 0.72 0.23 Howes Creek (HC6) 175.19 1.62 44.72 174.49 1.62 44.54 Mean 174.84 1.62 44.63 Std Dev 0.49 0.00 0.12 CV(%) 0.28 0.30 0.28 Howes Creek (HC7) 142.87 5.39 66.75 141.58 5.35 66.25 Mean 142.22 5.37 66.50 Std Dev 0.91 0.03 0.35 CV(%) 0.64 0.64 0.53 Co Cr C u Fe K Mg 0.17 0.62 0.43 358.00 9.13 68.79 0.17 0.61 0.42 351.80 8.83 67.81 0.17 0.62 0.42 354.90 8.98 68.30 0.00 0.01 0.01 4.38 0.21 0.70 0.98 1.02 2.17 1.23 2.30 1.02 0.16 0.51 0.44 369.89 9.58 71.70 0.16 0.51 0.44 368.57 9.50 71.64 0.16 0.51 0.44 369.23 9.54 71.67 0.00 0.00 0.00 0.94 0.06 0.04 0.90 0.32 0.49 0.25 0.59 0.06 0.13 0.36 0.31 261.63 9.86 54.28 0.13 0.36 0.31 261.13 9.65 53.93 0.13 0.36 0.31 261.38 9.75 54.10 0.00 0.00 0.00 0.35 0.15 0.25 0.76 0.28 0.60 0.13 1.57 0.46 0.11 0.31 0.44 1934.39 7.76 37.77 0.11 0.31 0.46 1906.08 7.64 37.42 0.11 0.31 0.45 1920.24 7.70 37.59 0.00 0.00 0.01 20.02 0.09 0.24 0.48 0.18 3.10 1.04 1.17 0.65' Table D1 Continued (ppm x 100) Season Tibutary name (S ITEJD) Mn Na Ni P Pb Si S r Z n Dry Bertrand Creek (BCr8) 7.06 3.99 0.36 16.67 0.76 9.70 0.39 2.49 7.07 4.15 0.36 16.50 0.75 10.15 0.39 2.47 Mean 7.07 4.07 0.36 16.58 0.75 9.93 0.39 2.48 Std Dev 0.01 0.11 0.00 0.12 0.01 0.32 0.00 0.01 CV(%) 0.13 2.71 0.64 0.75 1.62 3.23 0.21 0.49 Bertrand Creek (BCr11) 10.11 4.52 0.46 14.25 0.56 8.01 0.42 2.05 10.05 3.74 0.45 14.20 0.55 7.58 0.42 2.00 Mean 10.08 4.13 0.45 14.23 0.56 7.80 0.42 2.02 Std Dev 0.04 0.55 0.00 0.03 0.00 0.30 0.00 0.03 CV(%) 0.36 13.37 1.06 0.24 0.62 3.87 0.48 1.73 Howes Creek (HC5) 22.84 3.11 0.31 21.71 <0.25 12.08 0.37 1.77 22.38 2.99 0.30 21.57 <0.25 12.07 0.37 1.75 Mean 22.61 3.05 0.30 21.64 N/A 12.07 0.37 7.76 Std Dev 0.32 0.08 0.00 0.09 N/A 0.01 0.00 0.01 CV(%) 1.42 2.63 0.45 0.44 N/A 0.06 0.34 0.72 Pepin Creek (PC9) 4.35 4.46 0.83 12.35 0.48 14.21 0.45 1.04 4.34 4.61 0.81 12.32 0.45 14.14 0.44 0.99 Mean 4.35 4.53 0.82 12.34 0.47 14.18 0.45 1.02 Std Dev 0.01 0.10 0.01 0.02 0.02 0.05 0.00 0.03 CV(%) 0.17 2.29 1.32 0.18 5.27 0.32 0.31 3.03 Wet Bertrand Creek (BCr3) 12.33 5.44 0.35 17.41 1.30 11.36 0.39 3.14 12.17 5.38 0.34 17.17 1.26 11.04 0.38 3.07 Mean 12.25 5.41 0.35 17.29 1.28 11.20 0.38 3.10 Std Dev 0.11 0.04 0.01 0.17 0.03 0.23 0.00 0.04 CV(%) 0.91 0.81 1.76 0.97 2.28 2.03 1.15 1.40 ON <1 Table D1 Continued (ppm x 100) Season Tibutary name (S ITEJD) Mn Na Ni P Pb Si Sr Zn Wet Bertrand Creek (BCr4) 11.39 7.15 0.41 17.05 0.91 7.55 0.43 2.25 11.22 6.59 0.40 16.81 0.89 7.90 0.42 2.21 Mean 11.30 6.87 0.40 16.93 0.90 7.73 0.43 2.23 Std Dev 0.12 0.40 0.00 0.17 0.01 0.25 0.00 0.03 CV(%) 1.06 5.76 0.62 1.01 1.43 3.20 1.11 1.31 Bertrand Creek (BCr12) 12.79 4.30 0.44 12.03 0.46 12.04 0.33 1.14 12.72 4.26 0.44 12.01 0.47 12.01 0.33 1.13 Mean 72.75 4.28 0.44 12.02 0.46 12.03 0.33 1.14 Std Dev 0.05 0.03 0.00 0.02 0.00 0.02 0.00 0.00 CV(%) 0.38 0.59 0.20 0.13 0.44 0.19 0.67 0.15 Howes Creek (HC6) 12.44 2.25 0.32 17.72 <0.25 13.41 0.37 1.77 12.40 2.09 0.32 17.65 0.25 13.10 0.37 1.75 Mean 12.42 2.17 0.32 17.69 N/A 13.26 0.37 1.76 Std Dev 0.03 0.11 0.00 0.05 N/A 0.22 0.00 0.01 CV(%) 0.21 5.13 1.07 0.26 N/A 1.64 0.38 0.76 Howes Creek (HC7) 4.45 5.79 0.26 175.71 0.54 17.05 0.79 1.45 4.41 5.61 0.25 167.06 0.52 17.02 0.79 1.43 Mean 4.43 5.70 0.26 171.38 0.53 17.03 0.79 1.44 Std Dev 0.03 0.13 0.00 6.12 0.01 0.02 0.00 0.01 CV(%) 0.63 2.25 1.44 3.57 2.47 0.13 0.35 0.73 OS. OO Table D2. Certified values and acceptable ranges for Priority PollutnT™ / CLP Lot No. D035 - 540 (ppm) Element Al Certified Value 6,340 Acceptable Range 2,760 - 9,920 Analyzed on Aug 25, 2003 3,322 Analyzed on Aug 25, 2003 2,614 Analyzed on June 14, 2004 4,378 Analyzed on June 14, 2004 3,443 As 192 152-232 190 175 174 173 B 131 98.6-164 141 127 128 129 Ba 417 332 - 502 415 362 379 387 Ca 3,370 2,550-4,190 3,334 3,036 3,131 2,970 Cd 125 101 - 149 136 125 123 124 Co 56.8 45 - 68.7 57.7 53.1 55.1 56.1 Cr 133 103-163 130 117 123 122 Cu 93.9 74.4-113 93.9 84.7 86.7 88.0 Fe 11,600 5,500-17,700 6,378 5,069 8,647 6,700 K 1,890 1,200-2,580 1,387 1,074 1,631 1,397 Mg 2,000 1,410-2,590 1,501 1,260 1,726 1,530 Mn 320 242 - 398 315 283 297 288 Mo 62.9 47.6-78.1 62.2 56.8 59.0 58.6 Na 241 122-360 282 259 421 376 Ni 174 136-211 184 168 169 170 Pb 160 124-196 170 173 153 152 Se 97 69.6-124 97.0 86.5 92.0 89.4 Sr 178 132-224 161 144 152 163 Zn 246 189-303 246 224 234 229 Os Table D3. QA/QC results for reference sediment material Priority PollutnT™ / C L P Lot No. D035 - 540 (units in ppm x 100) A i A s B B a C a C d Co Cr C u Fe K Standard Soil 61.09 1.85 1.42 4.17 34.59 1.33 0.58 1.35 0.97 117.30 18.93 Standard Soil 61.26 1.85 1.42 4.20 34.65 1.34 0.58 1.36 0.96 117.55 18.99 Standard Soil 60.01 1.84 1.42 4.15 34.19 1.34 0.58 1.35 0.98 116.58 19.29 Standard Soil 59.82 1.86 1.43 4.16 34.22 1.35 0.58 1.36 0.99 115.55 18.89 Mean 60.54 1.85 1.42 4.17 34.41 1.34 0.58 1.35 0.98 116.75 19.02 Std Dev 0.73 0.01 0.01 0.02 0.24 0.01 0.00 0.00 0.01 0.90 0.18 CV(%) 1.21 0.36 0.47 0.51 0.70 0.43 0.28 0.27 1.19 0.77 0.96 Table D3 Continued (ppm x 100) / Mg Mn Mo Na Ni P Pb Se Si S r Z n Standard Soil 20.31 3.34 0.64 3.17 1.84 4.59 3.31 0.96 3.94 1.68 2.54 Standard Soil 20.28 3.35 0.64 3.21 1.85 4.61 3.33 0.96 3.99 1.68 2.54 Standard Soil 20.07 3.34 0.64 3.35 1.85 4.64 3.38 0.97 4.15 1.68 2.57 Standard Soil 20.17 3.35 0.64 3.21 1.87 4.59 3.36 1.00 4.06 1.68 2.57 Mean 20.21 3.35 0.64 3.23 1.85 4.61 3.34 0.97 4.04 1.68 2.56 Std Dev 0.11 0.01 0.00 0.08 0.01 0.03 0.03 0.02 0.09 0.00 0.02 CV(%) .0.53 0.20 0.42 2.42 0.57 0.55 0.99 1.74 2.21 0.25 0.80 <1 o Table D4. Sediment Analysis raw data for the dry season (ppm x 100) Site ID Al As B Ba Ca Cd Co Cr Cu Fe K Mg BCM 157.68 <0.25 < 0.1 2.08 59.22 <0.1 0.19 0.44 0.79 432.09 14.06 79.80 BCr2 146.87 <0.25 <0.1 1.76 50.66 <0.1 0.13 0.43 0.60 251.84 9.86 63.66 BCr3 170.08 <0.25 <0.1 1.79 49.52 <0.1 0.16 0.46 0.60 332.15 9.41 60.31 BCr4 186.64 <0.25 <0.1 1.86 57.92 <0.1 0.15 0.46 0.40 299.27 9.65 57.60 BCr8 225.43 < 0.25 < 0.1 2.08 51.08 <0.1 0.14 0.52 0.40 293.74 9.37 59.37 BCM1 192.22 < 0.25 < 0.1 1.87 56.32 <0.1 0.16 0.39 0.37 250.22 10.50 56.54 BCM 2 153.09 <0.25 < 0.1 1.60 52.85 <0.1 0.15 0.32 0.33 269.01 11.41 52.35 HC5 ' 197.16 < 0.25 < 0.1 1.44 48.12 <0.1 0.18 0.41 0.29 327.60 12.02 54.59 HC6 172.45 <0.25 <0.1 1.54 51.75 < 0.1 0.13 0.37 0.31 260.03 11.93 56.72 HC7 93.29 0.29 <0.1 2.37 33.71 < 0.1 <0.1 0.23 0.29 1955.53 4.01 20.71 PC9 168.08 < 0.25 <0.1 1.62 80.09 < 0.1 0.14 0.45 0.53 252.72 11.90 71.98 PC10 122.39 < 0.25 < 0.1 1.59 103.85 <0.1 <0.1 0.59 0.34 161.40 5.00 35.75 CC13 193.83 <0.25 <0.1 1.49 43.36 < 0.1 0.16 0.42 0.30 278.15 11.06 65.63 Table D4 Continued (ppm x 100) Site ID Mn Mo Na Ni P Pb Se Si Sr Zn BCM 18.98 <0.05 10.37 0.47 18.06 1.54 <0.5 13.69 0.42 3.54 BCr2 5.83 < 0.05 8.16 0.92 14.74 1.10 <0.5 14.38 0.35 4.07 BCr3 12.16 < 0.05 5.38 0.36 18.84 1.41 <0.5 14.84 0.36 4.51 BCr4 23.90 < 0.05 4.26 0.35 16.29 0.82 <0.5 12.09 0.41 2.76 BCr8 7.06 < 0.05 3.99 0.36 16.67 0.76 <0.5 9.70 0.39 2.49 BCM1 10.11 < 0.05 4.52 0.46 14.25 0.56 <0.5 8.01 0.42 2.05 BCM 2 21.86 < 0.05 5.40 0.30 14.71 0.45 <0.5 11.24 0.42 1.43 HC5 22.40 < 0.05 3.11 0.31 21.71 <0.25 <0.5 12.08 0.37 1.77 HC6 13.54 < 0.05 2.17 0.33 20.06 <0.25 <0.5 14.02 0.42 1.97 HC7 4.56 < 0.05 3.56 0.29 92.43 0.39 <0.5 29.42 0.37 0.91 PC9 4.35 <0.05 4.46 0.83 12.35 0.48 <0.5 14.21 0.45 1.04 PC10 31.77 <0.05 5.02 0.26 11.64 0.36 <0.5 13.11 0.63 0.71 CC13 10.75 <0.05 9.34 0.50 13.04 0.29 <0.5 9.44 0.35 1.37 Table D5. Sediment Analysis raw data for the wet season (ppm x 100) Site ID Al As B Ba Ca Cd Co Cr Cu Fe K Mg BCM 219.15 <0.25 < 0.1 1.72 69.88 <0.1 0.21 0.56 0.50 494.77 20.82 115.99 BCr2 167.70 <0.25 < 0.1 1.66 52.87 <0.1 0.14 0.47 0.58 287^ 89 10.34 67.19 BCr3 185.62 <0.25 < 0.1 1.69 52.68 <0.1 0.16 0.48 0.53 358.11 9.69 66.38 BCr4 222.58 <0.25 < 0.1 1.94 47.55 <0.1 0.17 0.62 0.43 358.00 9.13 68.79 BCr8 149.83 <0.25 < 0.1 1.77 50.02 <0.1 0.11 0.39 0.42 232.31 7.83 42.58 BCM1 295.94 <0.25 < 0.1 1.90 46.87 < 0.1 0.22 0.52 0.68 437.48 13.60 76.68 BCM 2 235.01 <0.25 <0.1 1.51 44.12 < 0.1 0.16 0.51 0.44 369.89 9.58 71.70 HC5 301.29 <0.25 <0.1 2.15 59.75 < 0.1 0.25 0.62 0.47 450.75 15.45 84.26 HC6 175.19 <0.25 <0.1 1.62 44.72 <0.1 0.13 0.36 0.31 261.63 9.86 54.28 HC7 142.87 0.44 <0.1 5.39 66.75 <0.1 0.11 0.31 0.44 1934.39 7.76 37.77 PC9 160.91 < 0.25 <0.1 1.23 89.43 <0.1 0.13 0.39 0.81 279.94 12.69 75.16 PC10 162.56 < 0.25 <0.1 2.28 126.72 <0.1 0.12 0.79 0.43 247.88 8.46 42.15 CC13 212.16 <0.25 <0.1 1.72 46.45 <0.1 0.15 0.44 0.34 302.32 9.84 68.42 Table D5 Continued Site ID Mn Mo Na Ni P Pb Se Si Sr Zn BCM 8.35 <0.05 5.82 0.61 12.40 0.37 < 0.5 11.40 0.47 2.05 BCr2 8.40 <0.05 6.33 0.36 14.83 1.07 < 0.5 11.57 0.38 3.09 BCr3 12.33 <0.05 5.44 0.35 17.41 1.30 < 0.5 11.36 0.39 3.14 BCr4 11.39 <0.05 7.15 0.41 17.05 0.91 < 0.5 7.55 0.43 2.25 BCr8 7.88 <0.05 5.73 0.26 15.89 1.01 <0.5 14.56 0.36 1.34 BCM1 19.83 <0.05 5.41 0.58 20.30 1.00 <0.5 20.63 0.35 1.49 BCM 2 12.79 <0.05 4.30 0.44 12.03 0.46 <0.5 12.04 0.33 1.14 HC5 21.30 <0.05 3.49 0.52 22.31 0.42 <0.5 15.96 0.45 2.55 HC6 12.44 <0.05 2.25 0.32 17.72 <0.25 <0.5 13.41 0.37 1.77 HC7 4.45 < 0.05 5.79 0.26 175.71 0.54 <0.5 17.05 0.79 1.45 PC9 7.24 < 0.05 10.07 0.36 16.46 1.68 <0.5 21.09 0.49 1.40 PC10 45.00 < 0.05 4.26 0.30 18.00 0.62 <0.5 15.44 0.73 0.95 CC13 11.77 < 0.05 3.76 0.34 13.41 0.43 <0.5 13.73 0.36 1.35 Table D6. Significant Spearman Rank Correlations for Elements in Sediments during the Dry Season ** correlation is significant at the 0.01 level (2 - tailed) * correlation is significant at the 0.05 level (2 tailed) Element Positively correlated to Negatively correlated to Al Co** Si* Ba Pb** None Ca Sr** P* Co Al**, K* None Cr Cu* None Cu Cr*, Mg**, Ni*, Pb**, Zn** None Fe p** None K Co* None Mg Cu**, Ni** None Mn None Ni* Na None None Ni Cu*, Mg** Mn* P Fe** Ca* Pb Ba**, Zn** None Si None Al* Sr Ca**,Pb** None Zn Cu**, Pb** None 173 Table D7. Significant Spearman Rank Correlations for Elements in Sediments during the Wet Season ** correlation is significant at the 0.01 level (2 - tailed) * correlation is significant at the 0.05 level (2 tailed) Element Positively correlated to Negatively correlated to Al Co**, Cr*, K*, Mg**, Mn*, Ni** None Ba P* None Ca Sr** None Co Al** , Cr**, K**, Mg**, Ni** None Cr Al* , Co*, Mn* None Cu Na*, Pb* None Fe Ni* None K Al* , Co** , Mg**, Ni** None Mg Al** , Co** , K**, Ni** None Mn Al*, Cr* Na**, Na Cu* Mn** Ni Al** , Co** , Fe*, K**, Mg** None P Ba* None Pb Cu* , Na* None Si None None Sr C a * * None Zn None None 174 Appendix E. DGT Raw Data Table E1. DGT raw data for the dry season Table E2. DGT raw data for the wet season 175 Table E1. DGT raw data for the wet season Site ID B C M BCr3 BCr4 B C M 1 B C M 2a BcM2b Blank D.L Date of deployment Jul 20/04 Jul 20/04 Jul 20/04 Jul 20/04 Jul 20/04 Jul 20/04 Jul 20/04 Date of retrieval Aug 12/04 Aug 12/04 Aug 12/04 Aug 12/04 Aug 12/04 Aug 12/04 Aug 12/04 Total time (seconds) 1981140 1983480 1981200 1983060 1982520 1982520 1982520 A l 0.057 0.144 0.094 0.062 0.143 < 0.05 <0.05 0.05 A s < 0.2 <0.2 < 0.2 <0.2 < 0.2 <0.2 < 0.2 0.2 B <0.05 <0.05 <0.05 < 0.05 <0.05 <0.05 < 0.05 0.05 Ba < 0.01 < 0.01 < 0.01 <0.01 <0.01 <0.01 <0.01 0.01 C a 5.151 7.350 8.744 6.496 7.382 9.413 0.216 0.1 C d < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 0.025 C o < 0.055 < 0.055 < 0.055 < 0.055 < 0.055 < 0.055 < 0.055 0.055 Cr < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 0.025 C u <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 0.05 Fe 0.139 0.599 0.075 0.100 0.267 0.279 0.138 0.05 K <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.5 Mg 1.085 1.159 1.375 1.207 1.176 1.386 0.053 0.01 Mn 4.647 1.271 0.072 0.339 0.134 0.072 0.092 0.005 Mo <0.05 <0.05 < 0.05 <0.05 <0.05 < 0.05 <0.05 0.05 Na 1.781 0.529 0.386 0.331 0.260 0.312 <0.25 0.25 Ni <0.1 <0.1 <0.1 <0.1 <0.1 < 0.1 <0.1 0.1 P <0.2 <0.2 <0.2 <0.2 <0.2 < 0.2 <0.2 0.2 Pb <0.2 8.634 0.940 0.921 6.380 2.808 9.960 0.2 Se <0.2 <0.2 <0.2 <0.2 < 0.2 <0.2 <0.2 0.2 Si 0.236 0.283 0.201 0.187 0.190 < 0.15 <0.15 0.15 Sr 0.008 0.012 0.017 0.018 0.019 0.025 < 0.002 0.002 Zn 0.059 0.076 0.083 0.424 0.246 0.056 0.055 0.01 176 Table E2. DGT raw data for the wet season Site ID D.L BCr1 BCr3 BCr4 BCM1 BCr12a Bcr12b Blank Date of Feb deployment 14/05 Feb 14/05 Feb 14/05 Feb 14/05 Feb 14/05 Feb 14/05 Feb 14/05 Date of retrieval Mar 9/05 Mar 9/05 Mar 9/05 Mar 9/05 Mar 9/05 Mar 9/05 Mar 9/05 Total time 1971720 (seconds) 1971000 1985340 1975260 1974840 1974480 1974480 Al 0.067 0.076 0.116 0.072 0.179 0.131 0.070 0.05 B < 0.05 < 0.05 <0.05 < 0.05 <0.05 < 0.05 <0.05 0.05 Ba <0.01 < 0.01 < 0.01 <0.01 <0.01 <0.0T <0.0T 0.01 Ca 7.401 6.931 6.662 4.186 6.421 6.135 0.152 0.1 Cd < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 0.025 Cr < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 < 0.025. < 0.025 0.025 Cu <0.05 < 0.05 < 0.05 < 0.05 <0.05 < 0.05 <0.05 0.05 Fe 0.189 0.274 0.276 0.099 0.286 0.348 0.063 0.05 K <0.5 < 0.5 < 0.5 <0.5 < 0.5 < 0.5 <0.5 0.5 Mg 1.219 1.064 1.010 0.755 0.967 0.833 0.030 0.01 Mn 0.204 0.417 0.266 0.036 0.214 0.302 < 0.005 0.005 Na 0.415 0.690 0.474 0.532 1.010 0.376 12.701 0.25 P <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 0.2 Pb < 0.2 5.995 0.364 24.526 69.551 8.671 36.963 0.2 Si <0.15 <0.15 0.166 <0.15 <0.15 < 0.15 <0.15 0.15 Sr 0.020 0.016 0.015 0.014 0.014 0.011 < 0.002 0.002 Zn 0.037 0.043 0.037 0.015 0.035 0.016 < 0.01 0.01 177 Appendix F: Spearman Rank Correlation Coefficients Tables F1 - F2. Spearman rank correlation coefficients for groundwater quality parameters and land use data for the dry and wet seasons Table F3. Spearman rank correlation coefficients for dissolved elements in groundwater and land use data Tables F4 - F5. Spearman rank correlation coefficients for surface water quality parameters and land use data for the wet and dry seasons Tables F6 - F7. Spearman rank correlation coefficients for sediment quality parameters and land use data for the wet and dry seasons 178 Table F1. Spearman rank correlation coefficients for groundwater quality parameters and land use for the dry season. C A T E G O R Y PH Turbidity S p C o n TDS N03-N P 0 4 cr Corr. Coeff. 0.527 0.228 0.346 0.346 -0.385 0.604 0.025 rural residential/hobby farm Sig. (2-tailed) 0.000 0.157 0.029 0.029 0.014 0.000 0.879 N 40 40 40 40 40 39 40 Corr. Coeff -0.395 -0.393 -0.045 -0.045 0.218 -0.486 -0.027 animal operations Sig. (2-tailed) 0.012 0.012 0.784 0.784 0.177 0.002 0.869 N 40 40 40 40 40 39 40 Corr. Coeff 0.122 0.459 0.041 0.041 -0.119 0.237 0.176 trees and bushes Sig. (2-tailed) 0.452 0.003 0.800 0.800 0.466 0.146 0.278 N 40 40 40 40 40 39 40 all other agricultural land Corr. Coeff 0.163 0.333 -0.054 -0.054 -0.069 0.275 -0.003 uses Sig. (2-tailed) 0.314 0.036 0.741 0.741 0.670 0.091 0.985 N 40 40 40 40 40 39 40 Other land uses Corr. Coeff 0.222 -0.246 -0.194 -0.194 -0.101 0.110 -0.343 (impervious surfaces) Sig. (2-tailed) 0.169 0.126 0.229 0.229 0.534 0.504 0.030 N 40 40 40 40 40 39 40 NO Table F2. Spearman rank correlation coefficients for groundwater quality parameters and land use for the wet season C A T E G O R Y PH Turbidity S p C o n TDS NOx P04 C l Corr Coeff 0.240 0.008 0.161 0.161 -0.334 0.119 -0.162 rural Sig. (2-tailed) 0.151 0.961 0.338 0.338 0.043 0.479 0.335 residential/hobby farm N 37 37 37 37 37 37 37 Corr Coeff -0.226 -0.046 -0.06 -0.06 0.247 -0.004 -0.047 Sig. (2-tailed) 0.176 0.784 0.724 0.724 0.140 0.977 0.778 animal operations N Corr Coeff 37 0.059 37 0.034 37 -0.031 37 -0.031 37 -0.072 37 0.025 37 0.169 Sig. (2-tailed) 0.727 0.839 0.851 0.851 0.670 0.882 0.316 trees and bushes N 37 37 37 37 37 37 37 Corr Coeff 0.215 0.107 0.016 0.016 -0.155 -0.024 -0.031 Sig. (2-tailed) 0.200 0.524 0.923 0.923 0.357 0.886 0.853 all other agricultural N Corr Coeff 37 0.126 37 -0.023 37 0.081 37 0.081 37 -0.196 37 0.054 37 -0.092 Sig. (2-tailed) 0.454 0.890 0.630 0.630 0.244 0.747 0.587 other N 37 37 37 37 37 37 37 oo o Table F3. Spearman rank correlation coefficients for dissolved elements in groundwater vs. land use C A T E G O R Y C a C u Fe K Mg Mn Na S i Sr Zn Corr Coeff -0.055 -0.070 0.205 -0.073 0.049 0.145 0.144 0.254 -0.189 0.107 Sig. (2-tailed) 0.748 0.682 0.224 0.667 0.772 0.392 0.395 0.130 0.264 0.527 rural residential/hobby farm N 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 Corr Coeff -0.067 0.025 -0.106 0.206 -0.115 -0.111 -0.055 -0.134 0.046 -0.165 Sig. (2-tailed) 0.694 0.882 0.531 0.221 0.497 0.515 0.747 0.429 0.788 0.328 animal operations N 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 Corr Coeff 0.226 0.130 0.182 -0.389 0.184 0.228 0.008 -0.038 0.138 0.232 Sig. (2-tailed) 0.179 0.443 0.281 0.017 0.275 0.174 0.964 0.825 0.416 0.167 trees and bushes N 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 Corr Coeff -0.011 -0.255 0.042 -0.236 -0.076 0.010 0.012 0.023 -0.124 -0.176 Sig. (2-tailed) 0.947 0.128 0.804 0.160 0.653 0.954 0.944 0.891 0.464 0.299 all other agricultural N 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 Corr Coeff -0.073 0.074 0.025 0.231 0.101 0.081 -0.013 0.319 -0.011 -0.048 Sig. (2-tailed) 0.666 0.662 0.882 0.169 0.552 0.635 0.938 0.054 0.949 0.780 other N 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 37.000 oo Table F4. Spearman rank correlation coefficients for surface water quality parameters vs. land use for the wet season C A T E G O R Y N 0 3 P 0 4 EC PH Cl Temp DO Turbid Corr Coeff -0.635 -0.011 -0.194 -0.641 0.760 -0.066 -0.423 0.306 0.020 0.971 0.525 0.018 0.003 0.830 0.149 0.309 impervious Sig. (2-tailed) 13 13 13 13 13 13 13 13 surfaces N Corr Coeff 0.563 -0.034 0.085 0.192 -0.195 0.499 0.220 0.034 0.045 0.912 0.782 0.529 0.523 0.083 0.469 0.912 all nthpr Sig. (2-tailed) a i I \jLI 1 ^ 1 N 13 13 13 13 13 13 13 13 agricultural Corr Coeff 0.399 0.192 0.080 0.132 0.195 0.404 0.214 0.088 0.177 0.529 0.795 0.668 0.523 0.170 0.482 0.775 Sig. (2-tailed) animal operations N 13 13 13 13 13 13 13 13 Corr Coeff -0.096 -0.390 0.186 0.582 -0.597 -0.017 0.309 -0.510 0.754 0.188 0.543 0.037 0.031 0.956 0.304 0.075 Sig. (2-tailed) trees and bushes N 13 13 13 13 13 13 13 13 oo K 3 Table F5. Spearman rank correlation coefficients for surface water quality parameters vs. land use for the dry season C A T E G O R Y N 0 3 P 0 4 EC PH CI Temp DO NTU Corr Coeff -0.100 0.025 0.273 -0.289 0.354 0.094 -0.389 -0.072 0.744 0.935 0.367 0.338 0.236 0.761 0.189 0.814 impervious Sig. (2-tailed) 13 13 13 13 13 13 13 13 surfaces N Corr Coeff 0.384 -0.277 -0.220 -0.459 -0.006 -0.541 0.156 -0.164 0.195 0.360 0.469 0.115 0.985 0.056 0.612 0.593 all other Sig. (2-tailed) 13 13 13 13 13 13 13 13 agricultural N Corr Coeff -0.242 -0.297 -0.203 -0.231 0.170 -0.052 -0.094 0.011 0.426 0.325 0.505 0.447 0.578 0.865 0.761 0.972 Sig. (2-tailed) animal operations N 13 13 13 13 13 13 13 13 Corr Coeff -0.070 -0.100 -0.056 0.503 -0.248 0.116 0.258 -0.423 0.821 0.744 0.857 0.080 0.414 0.706 0.395 0.149 Sig. (2-tailed) trees and bushes N 13 13 13 13 13 13 13 13 Table F6. Spearman rank correlation coefficients for sediment quality parameters vs. land use for the wet season C A T E G O R Y A l B a C a Co Cr C u Fe K Corr Coeff -0.036 -0.022 0.220 0.209 0.045 0.616 0.245 0.203 impervious Sig. (2-tailed) 0.906 0.942 0.470 0.493 0.885 0.025 0.420 0.505 surfaces N 13 13 13 13 13 13 13 13 Corr Coeff 0.322 0.317 -0.243 0.243 0.079 -0.153 0.333 -0.203 all other Sig. (2-tailed) 0.283 0.292 0.424 0.424 0.797 0.619 0.266 0.505 agricultural N 13 13 13 13 13 13 13 13 Corr Coeff -0.099 0.368 -0.225 -0.170 -0.176 -0.423 0.209 -0.302 Sig. (2-tailed) 0.748 0.216 0.459 0.578 0.566 0.150 0.494 0.316 animal operations N 13 13 13 13 13 13 13 13 Corr Coeff 0.067 -0.320 -0.022 -0.011 0.020 0.095 -0.337 0.189 Sig. (2-tailed) 0.828 0.286 0.942 0.971 0.950 0.758 0.260 0.535 trees and bushes N 13 13 13 13 13 13 13 13 Table F6 continued C A T E G O R Y Mg Mn Na Ni P Pb Si Sr Zn Corr Coeff 0.145 -0.376 0.599 0.262 -0.042 0.527 -0.320 0.059 0.649 impervious Sig. (2-tailed) 0.637 0.205 0.031 0.387 0.892 0.065 0.286 0.849 0.016 surfaces N 13 13 13 13 13 13 13 13 13 Corr Coeff 0.209 -0.028 -0.028 0.113 0.102 -0.153 0.181 -0.085 -0.147 all other Sig. (2-tailed) 0.493 0.927 0.927 0.713 0.741 0.619 0.554 0.783 0.632 agricultural N 13 13 13 13 13 13 13 13 13 Corr Coeff -0.115 -0.313 -0.038 -0.159 -0.132 -0.396 0.099 -0.187 -0.451 Sig. (2-tailed) 0.707 0.297 0.901 0.603 0.668 0.181 0.748 0.541 0.122 animal operations N 13 13 13 13 13 13 13 13 13 Corr Coeff 0.092 0.457 -0.337 -0.014 0.003 0.139 0.454 -0.153 -0.429 Sig. (2-tailed) 0.765 0.117 0.260 0.964 0.993 0.650 0.119 0.617 0.144 trees and bushes N 13 13 13 13 13 13 13 13 13 oo 4i. Table F7. Spearman rank correlation coefficients for sediment quality parameters vs. land use for the dry season C A T E G O R Y Al B a C a Co C r Cu Fe K Corr Coeff -0.003 0.674 -0.061 0.290 0.262 0.724 0.281 -0.173 impervious Sig. (2-tailed) 0.993 0.012 0.842 0.337 0.387 0.005 0.352 0.573 surfaces N 13 13 13 13 13 13 13 13 Corr Coeff 0.345 -0.119 -0.317 0.158 -0.271 -0.571 0.339 0.023 all other Sig. (2-tailed) 0.249 0.699 0.292 0.606 0.370 0.042 0.257 0.942 agricultural N 13 13 13 13 13 13 13 13 Corr Coeff 0.154 0.495 -0.159 0.044 -0.220 -0.258 0.313 -0.148 Sig. (2-tailed) 0.616 0.086 0.603 0.887 0.471 0.394 0.297 0.629 animal operations N 13 13 13 13 13 13 13 13 Corr Coeff -0.045 -0.616 0.312 -0.095 -0.006 -0.159 -0.696 0.162 Sig. (2-tailed) 0.885 0.025 0.299 0.758 0.986 0.604 0.008 0.598 trees and bushes N 13 13 13 13 13 13 13 13 Table F7 continued C A T E G O R Y M g Mn Na Ni P Pb S i Sr Zn Corr Coeff 0.418 -0.343 0.254 0.479 0.251 0.861 0.306 -0.421 0.794 impervious Sig. (2-tailed) 0.155 0.252 0.403 0.098 0.409 0.000 0.309 0.152 0.001 surfaces N 13 13 13 13 13 13 13 13 13 Corr Coeff -0.345 0.130 -0.345 -0.288 0.158 -0.373 -0.379 -0.085 -0.311 all other Sig. (2-tailed) 0.249 0.672 0.249 0.340 0.606 0.209 0.202 0.783 0.301 agricultural N 13 13 13 13 13 13 13 13 13 Corr Coeff -0.137 -0.099 0.000 -0.115 0.154 -0.011 -0.423 -0.038 -0.148 Sig. (2-tailed) 0.655 0.748 1.000 0.707 0.616 0.972 0.150 0.901 0.629 animal operations N 13 13 13 13 13 13 13 13 13 Corr Coeff -0.008 -0.003 0.164 0.067 -0.716 -0.432 -0.217 0.482 -0.524 Sig. (2-tailed) 0.978 0.993 0.592 0.828 0.006 0.141 0.476 0.095 0.066 trees and bushes N 13 13 13 13 13 13 13 13 13 oo Appendix G : Photographs of surface water sampling stations and methodology Figure G1. Urban station 1 on Bertrand Creek during moderate flow conditions Figure G2. Urban station 3 on Bertrand Creek with poor riparian buffer. Figure G3. Measuring conductivity at station 5 on Howes Creek during low flow conditions Figure G4. Station 6 on Howes Creek completely dry during the month of June 2005 Figure G5. Station 7 on Howes Creek showing abundant iron precipitates Figure G6. Measuring dissolved oxygen at station 8 on Bertrand Creek on the Aldergrove -Bellingham highway Figure G7. Station 9 on Pepin Creek with poor riparian buffer to protect the stream from surface runoff Figure G8. Sampling streambed sediments Figure G9. DGT unit deployed in a stream Figure G10. Geese with farm with biosecurity in effect close to station 9 on Pepin Creek Figure G11. Livestock operation next to station 11 on Bertrand Creek Figure G12. Gravel pit in the Abbotsford portion of the Bertrand Creek watershed Figure G13. Filtering water samples for nutrient analysis using Porex blood serum filters Figure G14. Measuring conductivity at station 10 on Pepin Creek at the Canada - US international border Figure G15. Collecting water samples at station 12 on Bertrand Creek at the Canada - U S international border Figure G16. Land use within the watershed: vineyard close to station 5 on Howes Creek 186 Figure G 1 . Urban station 1 on Bertrand Creek during moderate flow conditions Figure G3. Measuring conductivity at station 5 on Howes Creek during low flow conditions. Figure G5. Station 7 on Howes Creek showing abundant iron precipitates. Figure G7. Station 9 on Pepin Creek with poor riparian buffer to protect the stream from surface runoff Figure G10. Geese with farm with biosecurity in effect close to station 9 on Pepin Creek 192 Figure G13. Filtering water samples for nutrient analysis using Porex blood serum filters Figure G14. Measuring conductivity at station 10 on Pepin Creek at the Canada - US international border 193 Figure G15. Collecting water samples at station 12 on Bertrand Creek at the Canada - U S international border Appendix H: Geology of the Township of Langley Area Surficial Geology Legend Q U A T E R N A R Y P O S T GLACIAL SALISH SEDIMENTS S A a Landfill, including sand, gravel, till, crushed stone and refuse SAb -e Bog, swamp, and shallow lake deposits: SAb, lowland peat up to 14 m thick, in part overlying Fb,c; SAc, lowland peat up to 1 m thick underlying Fb (up to 2 m thick); SAd, lowland organic sandy loam to clay loam 15 to 45 m thick overlying SAg and Fd; SAe, upland peat up to 8 m or more thick SAf .g Marine shore sediments (beach deposits); Saf, sand to sandy loam up to 2 m thick overlying estuarine, fossiliferous , fine sand and clayey silt, 10 to 185 m thick (Fe of Lithologic Units and Environment of Deposition); SAg, medium to coarse sand and gravel up to 8 m thick SAh-k Lowland and mountain stream deltaic, channel fill, and overbank sediments: SAh, lowland stream channel fill and overbank sandy loam to clay loam, also organic sediments up to 8 m thick; SAi , mountain stream marine deltaic medium to coarse gravel and minor sand up to 15m or more thick; SAj, mountain stream channel fill sand and gravel up to 8 m thick; SAk, lowland stream channel fill sand to gravel and minor silt and clay up to 5 m thick SAm-p Slope deposits, colluvial sediments deposited by mass wasting processes; SAm, slopewash sand up to 4 m thick, resting on Fc,d and Saj; SAn, slopewash clayey silt and silty clay up to 2 m thick, overlying Sa ; SAo, fan and landslide gravel, sand and rubble, up to 15+ m thick, overlying Fraser River Sediments (Fg,h) and Salish lacustrine deposits (SAq.r); SAp, landslide and fan gravel and rubble up to 10 m thick, overlying Sumas Drift (Sa,c,f)and Fort Langley Sediments An unmapped mantle of gravelly colluvium, 0.5 to 2.0 m thick is widespread throughout the mountainous parts of the map area, especially above 250 m elevation. In many places it is intermixed with glacial ablation till and other glacial sediments. Consequently the areas mapped as bedrock (T and PT) normally do not exhibit rock at the surface in more than 5 percent of the area indicated SAq , s Lacustrine deposits: SAq, silt to clay, normally less than 5 m thick, in places overlying SAr or Fraser River Sediments (probably Fe); SAr, sand to sandy loam, up to 5 m thick, also verlying Fe; SAs , fine sand up to 8 m thick forming beaches and spits North of Vedder Canal both SAq and SAr are intermixed with SAj and Fg; the most abundant unit is the one mapped SAt Eolian deposits: SAt windblown sand, silt, and silt loam 1 to 8 m thick 196 Eolian deposits have been mapped as a separate unit where they are more than 1 m thick. In additioin most pre-Salish Sediments exposed east of 122°25' W are mantled by windblown sand and silt 5 cm to 1 m thick. Included are areas mapped as T and PT up to at least 1000 m elevation F R A S E R RIVER SEDIMENTS Fa-h Deltaic and distributary channel fill sediments overlying and cutting estuarine sediments and overlain in part of the area by overbank sediments: Fa, channel deposits, fine to medium sand and minor silt occurring along present day river channels; Fb, overbank sandy to silt loam up to 2 m thick overlying 15 m or more of Fd; Fc, overbank silty to silt clay loam normally up to 2 m thick overlying 15 m or more of Fd; Fd, deltaic and distributary channel fill (includes tidal flat deposits) sandy to silt loam, 10 to 40 m thick interbedded fine to medium sand and minor silt beds; may contain organic and fossiliferous material; Fe, estuarine fine sand to clayey silt, in places fossiliferous; probably underlies extensive areas in Sumas and Matsqui valleys; thickness may vary from 10 to 150 m; Ff, channel and floodplain sand and gravel, up to 60 m thick, underlying Fd,g,h; may be in p art Sumas outwash (Sa,,j); Fg, channeled deposits (expressed at surface by ridges and swales), silty clay loam, silt loam, silty clay, and minor organic sediments, up to 10 m thick, overlie Ff and Fe; Fh, channeled deposits similar to Fg but coarser textured, sandy loam and loamy sand P L E I S T O C E N E S U M A S DRIFT Sa-e Outwash, ice-contact, and deltaic deposits; Sa , outwash sand and gravel up to 30 m thick; Sb, ice-contact gravel and sand containing till lenses and clasts of glaciomarine stony clayey silt, 2 to 5 m thick overlying FLc,d; Sc, ice-contact gravel and sand containing till lenses and clasts of glaciomarine stony clayey silt, 2 to 5 m thick overlying Flb,e; Sd, ice-contact gravel and sand containing till lenses and clasts of glaciomarine stony clayey silt more than 5 m thick; Se, raised proglacial deltaic gravel and sand up to 40 m thick Sh Glaciolacustrine deposits: Sh, silt, clayey silt, silty clay, and sand, minor gravel 5 to 35 m thick Sf,g Lodgment and minor flow till: Sf, sandy till and substratified drift, 2 to 10 m thick; Sg, sandy till and and substratified drift 0.5 to 2 m thick, in most places overlying Fort Langley glaciomarine sediments (FLc) Sj Advance glaciofluvial deposits: Sj, gravel and sand up to 40 m thick, proglacial channel fill, floodplain, and deltaic sediments probably all included here FORT L A N G L E Y FORMATION FLa -e Glacial and deltaic sediments: FLa, lodgment and flow till with sandy loam matrix containing clasts of FLc; FLb, outwash and ice-contact gravel and sand containing clasts of FLa.c: FLc, glaciomarine stony clayey silt to silty sand 8 to 90 m thick, commonly thinly bedded and containing marine shells; FLd, marine silty clay to fine sand commonly containing marine shells; FLe, proglacial deltaic gravel and sand 197 CAPILANO SEDIMENTS Ca-e Raised marine, deltaic and fluvial deposits; Ca , raised marine beach, spit, bar, and lag veneer, poorly sorted sand to gravel (except in bar deposits) normally less than 1 m thick but up to 8 m thick, mantling older sediments and containing fossil marine shell casts up to 175 m above sea level; Cb, raised beach medium to coarse sand 1 to 5 m thick containing fossil marine shell casts; Cc, raised deltaic and channel fill medium sand to cobble gravel up to 15 thick deposited by proglacial streams and commonly underlain by silt to silty clay loam; Cd, marine and glaciomarine stony (including till-like deposits) to stoneless silt loam to clay loam with minor sand and silt normally less than 3 m thick but up to 30 m thick, containing marine shells. These deposits thicken from west to east. Ce , mainly marine silt loam to clay loam with minor sand, silt and stony glaciomarine material (see Cd), up to 60+ m thick. In many of the upland areas sediments mapped as C c and Cd are mantled by a thin veneer (less than 1 m) of Ca . V A S H O N DRIFT A N D CAPILANO SEDIMENTS VC Glacial drift including: lodgment and minor flow till, lenses and interbeds of substratified glaciofluvial sand to gravel, and lenses and interbeds of glaciolacustrine laminated stony silt; up to 25 m thick but in most places less than 8 m thick (correlates with Va,b); overlain by glaciomarine and marine deposits similar to Cd normally less than 3 m but in places up to 10 m thick. Marine derived lag gravel normally less than 1 m thick containing marine shell casts has been found mantling till and glaciomarine deposits up to 175 m above sea level; above 175 m till is mantled by bouldery gravel that may be in part ablation till, in part colluvium and in part marine shore in origin V A S H O N DRIFT Va,b Till, glaciofluvial, glaciolacustrine, and ice-contact deposits: Va , lodgment till (with sandy loam matrix) and minor flow till containing lenses and interbeds of glaciolacustrine laminated stony silt; Vb, glaciofluvial sandy gravel and gravelly sand outwash and ice-contact deposits P R E - V A S H O N DEPOSITS PVa-h Glacial, nonglacial and glaciomarine sediments: PVa , Quadra fluvial channel fill and floodplain deposits, crossbedded sand containing minor silt and gravel lenses and interbeds; PVb, Quadra (?) glaciofluvial deposits, deltaic and crossbedded sand to gravel (may be in part Vb); PVc, Quadra marine interbedded fine sand to clayey silt believed to be off shore equivalents of PVa , PVd, Coquitlam till, glaciomarine (?) and glaciolacustrine deposits; PVe, Cowichan Head fluvial, organic colluvial and bog and swamp sediments; PVf, Semiahoo till, glaciomarine (?) and glaciolacustrine deposits; PVg, Highbury fluvial and bog and swamp deposits; PVh, Westlynn glaciofluvial sandy gravel 198 UNDIVIDED P R E - V A S H O N DEPOSITS Till, glaciofluvial, glaciolacustrine, fluvial, marine and organic sediments TERTIARY Tertiary bedrock including sandstone, siltstone, shale, conglomerate, and minor volcanic rocks; where bedrock is not at the surface it is overlain by glacial deposits and colluvium PRE-TERTIARY Mesozoic bedrock including granitic and associated types; where bedrock is not at the surface it is overlain by glacial deposits and colluvium 199 S u r f i c i a l G e o l o g y a s D e f i n e d b y t h e G e o l o g i c a l S u r v e y of C a n a d a A d a p t e d from : Go lder Associates, 2005 2 0 0 0 ^ ^ ^ q^_^_^^^^2OQ0 IMn S o l a - 1:110.000 R E F E R E N C E Surficial Geology from Geological Survey of Canada (GSC): Armstrong. J E (10BO). Mission, B C and Armstrong, J E and S R Hicock (1980). New Westminster, B C . Street data from DMTI Spatial Inc., Datum: NAD S3 Projection: U T M Zona 10 Figure H1. Surficial Geology of the Township of Langley Area (adapted from Golder Associates, 2005) 

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