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Evaluation of trace metal distributions (arsenic, cadmium, lead) and lead sources in sediments from a… Ikehata, Mariko 2013

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   Evaluation of trace metal distributions (arsenic, cadmium, lead) and lead sources in sediments from a sound and an inlet on the west coast of Vancouver Island,  British Columbia by Mariko Ikehata  A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF  MASTER OF SCIENCE in THE FACULTY OF GRADUATE AND POSTDOCTORAL STUDIES (Geological Science) THE UNIVERSITY OF BRITISH COLUMBIA  (Vancouver)   December, 2013  ? Mariko Ikehata, 2013   ii Abstract Barkley Sound and Alberni Inlet, located on the west coast of Vancouver Island, British Columbia, are home to economically important oyster farms. The headwaters of Alberni Inlet are proximal to the city of Port Alberni, where industrial activities (e.g., paper mills, recycling plants) release significant quantities of heavy metals into Alberni Inlet annually. The distribution of As, Cd, and Pb and Pb isotopic composition of Pb were studied in surface and cored sediments collected downstream from the paper mill using quadrupole and multi collector inductively coupled plasma mass spectroscopy (Q-ICP-MS, MC-ICP-MS).  Surface and core sediment concentrations of As, Cd and Pb generally decrease downstream from Port Alberni, with the exception of a Pb spike observed in Barkley Sound. Alberni Inlet and Barkley Sound display ranges of 3.8-24 and 3.5-21.6 ppm for As, from 0.03-0.87 and 0.2-1.1 ppm for Cd, and 4.1-18 and 2.9-24.2 ppm for Pb, respectively. Scavenging of dissolved metals is observed at the distance of 10-25 km downstream from Port Alberni. Based on comparison to Sediment Quality Guidelines, the environmental impact of trace metals in the sediment on bottom dwelling organism is low.  Major elements compositions determined using Aluminum as an elemental normalizer indicated that the sediment corresponds to a source predominantly from Vancouver Island bedrock. The isotopic composition for surface sediment ranges from 1.17020 to 1.21602 for 206Pb/207Pb, and 2.0397 to 2.0835 for 208Pb/206Pb. In core samples, the range is from 1.16571 to 1.19109 for 206Pb/207Pb and 2.06883 to 2.08533 for 208Pb/206Pb. Lead isotope fingerprinting indicates that sediments derived from Vancouver Island were contaminated with trace metals by a source displaying the Pb isotopic signature of the Sullivan Ore, the primary anthropogenic Pb source for British Columbia. This is consistent with paper mill effluent from Port Alberni. iii Sediments from the lower inlet and Barkley Sound also show a contribution from Chinese loess. Other human activities are most likely responsible for the spike in Pb concentrations in Barkley Sound. This study demonstrates that the combination of trace metal analysis and high precision Pb isotopic data are effective tools for monitoring anthropogenic input into the environment.  iv Preface The author with the help of The Pacific Centre for Isotopic and Geochemical Research (PCIGR) staff carried out all the analytical procedure and research. My supervisor Dominique Weis and mentor Alyssa Shiel provided research advice, help for interpretation of data, and edited the thesis.   v Table of contents Abstract .......................................................................................................................................... ii?Preface ........................................................................................................................................... iv?Table of contents ............................................................................................................................v?List of tables.................................................................................................................................. ix?List of figures .................................................................................................................................. x?Acknowledgements ..................................................................................................................... xii?Chapter  1: Introduction .......................................................................................................... 1?1.1? Introduction .................................................................................................................... 1?1.1.1? Characteristics and geology of the studied area ...................................................... 2?1.1.2? The bathymetry of Alberni Inlet and Barkley Sound .............................................. 7?1.1.3? History of the Port Alberni pulp and paper mill ..................................................... 8?1.1.3.1? Trace element pollution source and control ..................................................... 8?1.1.4? Arsenic, cadmium and lead toxicology ................................................................... 9?1.1.4.1? Arsenic ............................................................................................................. 9?1.1.4.2? Cadmium ........................................................................................................ 10?1.1.4.3? Lead ................................................................................................................ 10?1.1.5? Pb isotope compositions use as an environment tracer ......................................... 11?1.1.6? Major element use to establish provenance and contamination of marine sediments ........................................................................................................................... 12?1.2? Overview of the thesis ................................................................................................. 13?vi Chapter  2: Evaluation of measurement limits of detection, quantification and linearity and sensitivity for trace elements and rare earth element using quadrupole inductively coupled plasma mass spectrometry ....................................................................................... 14?2.1? Introduction .................................................................................................................. 14?2.2? Experimental ................................................................................................................ 18?2.2.1? Reagents and standards ......................................................................................... 19?2.3? Result and discussion ................................................................................................... 20?2.3.1? Trace element (TE) ............................................................................................... 20?2.3.2? Rare earth elements (REE) .................................................................................... 21?2.3.3? Arsenic, cadmium, lead ......................................................................................... 22?2.4? Conclusions .................................................................................................................. 29?Chapter  3: Potential arsenic, cadmium and lead input into the marine bottom sediments of Alberni Inlet and Barkley Sound from the paper mill .................................................... 30?3.1? Introduction .................................................................................................................. 30?3.2? Experimental method ................................................................................................... 36?3.2.1? Sample materials and collection ........................................................................... 36?3.2.2? Sample preparation ............................................................................................... 38?3.2.2.1? Reagents ......................................................................................................... 38?3.2.2.2? Sample digestion ............................................................................................ 38?3.2.2.3? Anion exchange chromatography .................................................................. 38?3.2.3? Analytical technique ............................................................................................. 39?3.2.3.1? Major element analysis .................................................................................. 39?3.2.3.2? Trace element analysis ................................................................................... 39?vii 3.2.3.3? Pb isotope analysis ......................................................................................... 40?3.2.3.4? Carbon and nitrogen analysis ......................................................................... 41?3.3? Result ........................................................................................................................... 42?3.3.1? Surface sediments ................................................................................................. 42?3.3.1.1? Major elements ............................................................................................... 42?3.3.1.2? Carbon and nitrogen ....................................................................................... 42?3.3.1.3? Trace element concentration .......................................................................... 50?3.3.1.4? Pb isotope ....................................................................................................... 55?3.3.2? Core sediment ....................................................................................................... 58?3.3.2.1? Major element ................................................................................................ 58?3.3.2.2? Carbon and nitrogen ....................................................................................... 62?3.3.2.3? Trace element concentration .......................................................................... 64?3.3.2.4? Pb isotope ....................................................................................................... 66?3.4? Discussion .................................................................................................................... 70?3.4.1? Composition of the sediment in Alberni Inlet and Barkley Sound ....................... 70?3.4.1.1? Major element ................................................................................................ 70?3.4.1.2? Carbon-nitrogen ............................................................................................. 71?3.4.2? Concentration and Pb isotopic signature in upper inlet vs. lower Alberni Inlet and Barkley Sound ................................................................................................................... 73?3.4.3? Pb input from Vancouver Island and Chinese loess in Barkley Sound ................ 80?3.4.4? Explaining concentration change in core sample by disturbances related to the Alaska tsunami in 1964 using sedimentation rate in Barkley Sound basins ..................... 86?3.5? Conclusions .................................................................................................................. 88?viii Chapter  4: Conclusion ........................................................................................................... 90?4.1? Summary and conclusions ........................................................................................... 90?4.2? Suggestions for future research .................................................................................... 92?References .....................................................................................................................................94?Appendices ..................................................................................................................................107? ix List of tables Table 2.1. Figure of merit for trace elements in no gas mode. ..................................................... 23?Table 2.2. Figure of merit for trace elements in He mode. ........................................................... 24?Table 2.3. Figure of merit for rare earth elements in no gas mode. .............................................. 25?Table 2.4. Figure of merit for rare earth elements in He gas mode. ............................................. 26?Table 2.5. Figure of merit for As, Cd, Pb in no gas mode. ........................................................... 27?Table 2.6. Figure of merit for  As, Cd, Pb in He gas mode. ......................................................... 28?Table 3.1. Annual mass of metals discharged to the water from the pulp mill. ........................... 34?Table 3.2. Surface sediment locations and result of trace element concentrations ....................... 44?Table 3.3. Major element oxide (wt. %) abundances in surface sediment grab samples. ............ 45?Table 3.4 Major element oxide (wt. %) abundances in surface sediment renormalized to 100 % after subtraction of loss of ignition value (LOI). .......................................................................... 46?Table 3.5. Carbon and nitrogen contents in surface sediment. ..................................................... 48?Table 3.6. Pb isotopic ratio for surface sediment of the measured value. .................................... 57?Table 3.7. Sample location, trace element concentrations data for core sediment samples. ........ 59?Table 3.8. Major element oxide abundances (wt. %) for sediment core samples. ........................ 60?Table 3.9. Major element oxide data (wt. %) for core samples, renormalized value. .................. 61?Table 3.10. Carbon and nitrogen (wt. %) contents in core sediment. ........................................... 63?Table 3.11. Isotopic ratio for core sediment of the measured value. ............................................ 67?Table 3.12. Potential adverse effect values. .................................................................................. 78?Table 3.13. Trace metal concentrations in sediments from different locations and the Earth?s crust. .............................................................................................................................................. 79?Table 3.14. Modeling the 13% Chinese loess input into the Barkley Sound ................................ 85?x  List of figures Figure 1.1. Map of Vancouver Island. ............................................................................................ 4?Figure 1.2. Map of Barkley Sound and Alberni Inlet. .................................................................... 5?Figure 1.3. Geological map of Alberni Inlet and Barkley Sound. .................................................. 6?Figure 2.1. Traditional calibration curve. ..................................................................................... 17?Figure 3.1. Annual mass of metals discharged to the water from the pulp mill. .......................... 35?Figure 3.2. Map of sediment sampling locations of Alberni Inlet and Barkley Sound. ............... 37?Figure 3.3. Major element concentration in wt. % to aluminum oxide in wt. % ratio vs. distance (km) from Port Alberni for surface sediment. .............................................................................. 47?Figure 3.4. Carbon-nitrogen ratio vs. distance from Port Alberni for surface sediment. ............. 49?Figure 3.5. Map of three transects. ............................................................................................... 50?Figure 3.6. Arsenic concentrations vs. distance form Port Alberni Mill. ..................................... 52?Figure 3.7. Cadmium concentration vs. distance form Port Alberni Mill. ................................... 52?Figure 3.8. Lead concentration vs. distance form Port Alberni Mill. ........................................... 54?Figure 3.9. 208Pb/207Pb vs. 206Pb/207Pb isotopic ratios. .................................................................. 56?Figure 3.10. Concentration plot showing the depth profile of core sediment. .............................. 65?Figure 3.11. Plot for 206Pb/207Pb vs. 208Pb/206Pb for core samples. ............................................... 68?Figure 3.12. Pb isotope evolution vs. the depth for core samples. ............................................... 69?Figure 3.13. Major element in wt. % against Al2O3. .................................................................... 72?Figure 3.14. Plot of 208Pb/206Pb vs. 206Pb/207Pb diagram for Pb samples for sediment from this study compared to Vancouver Island geologic samples, Chinese loess, and the anthropogenic endmembers (Sullivan Ore). ......................................................................................................... 82?xi Figure 3.15. 208Pb/204Pb vs. 206Pb/204Pb for sediment from this study compared to local geologic samples, Chinese loess, and anthropogenic endmembers (Sullivan Ore). .................................... 83?Figure 3.16. 208Pb/206Pb vs. 208Pb/207Pb showing lower inlet and Barkley sound sediments as a mixture of three end-members: anthropogenic Pb, Vancouver Island basement rocks, and Chinese loess. ................................................................................................................................ 84?   xii Acknowledgements    There are number of precious people who I would like to express my appreciation for their support and encouragements to complete this thesis. First, I thank my supervisor Dominique Weis for her constant support and opportunity to work on this project. Her understanding and care for students and being available for questions and scientific discussions anytime were greatly appreciated during this study. I am also thankful to her for the state of the art facility she has provided and the chocolates from all over the Europe. I thank Alyssa Shiel who helped guide me during the early stage of this thesis and provided ideas for this project. I am grateful to have her continuous support for scientific questions, discussion and encouragement after her move to Illinois. Her contribution to this thesis with scientific writing and comments were extremely helpful. I also thank my committee members, Roger Francois who always had thought-provoking questions and constructive comments to improve this study and allowing me to use his lab facilities for sample preparation, Jane Barling who trained me for the use of MC-ICP-MS and gave me encouragements, Ken Hall with his comments and enthusiasm for the pulp and paper mill stud, and Tara Ivanochko as an external examiner and making exciting scientific comments for this thesis.   I owe particular thanks to Maureen Soon, who volunteered a lot of time for preparations, analysis and help whenever asked and Steve (Stephen) Calvert who provided me great suggestions and interpretation of major elements in sediment data. I especially want to thank Vivian Lai for her assistance with the Agilent 7700x quadrupole ICP-MS. I thank for the amazing group of researchers and staff at PCIGR, Rich Friedman, Vivian Lai, Bruno Kieffer, Cecilia Li, Kathy Gordon, and Liyan Xing for their tremendous support. Emily Mullen and xiii Corey Wall are also thanked for their help and comment on this manuscript, geological interpretation of the data and being available for questions and scientific suggestions. I also thank James Scoates with his helpful comments about Vancouver Island geology with respect to my data and suggestions to improve my presentations, Chris Payne for helping and organization for sediment sampling and Robie Macdonald (Fisheries and Oceans Canada) for providing the sediment data in Barkley Sound.   I am thankful for my family and friends for their support and thoughts throughout this journey. I dedicate my work to my parents, Chieko and Hiroshi, and my brother, Kosuke. I especially thankful to their support throughout my years of education and great understanding through this process ( ??????????? ). I thank my officemates in 305, especially Ines Nobre Silva, Elispeth Barnes, Marion Carpentier, Ana?s Fourny, and Gary Schudel who gave me helpful feedbacks and kept encouraging me during my journey to pursuit this education. I?d like to thank my friends in Vancouver, Pam Kalas, Aram Goodwin, Maja Krzic, Elisabeth Hehenberger, Erik Kerasiotis, Julia Gustavsen and Maric Tse who provided me great support and encouragement with coffee and delicious food. Many of my stressed and difficult times are resolved by them and I am very thankful them being there for me. I?d like to extend my gratitude to friends outside of Canada, Amy, Ayumi and Akiko, who send me frequent encouragements via emails and phone calls.    1 Chapter  1: Introduction  1.1 Introduction Trace metal contamination from industrial pollution into the environment represents one of the concerns to humans and natural ecosystems due to its direct and indirect effects on to our health. Water contamination causes devastating problems within the food chain to organisms in the water, which may harm humans through biomagnification. As a result of pollutants input, the bottom sediments in the ocean or rivers contamination by trace metals has been a major concern, and numerous studies have been conducted since 1980?s (Riedel et al., 1987; Windom et al., 1989; Gray and Eppinger, 2012). Monitoring the input of these contaminants to the environment and understanding their distribution will help to identify the potential effects of industrial activities on the ecosystems. Some metals, such as iron (Fe), zinc (Zn), and manganese (Mn), are also essential micronutrients for humans. However, Arsenic (As), cadmium (Cd), and lead (Pb) are highly toxic and at high concentrations can be fatal to organisms or at least stressful in the receiving environment and some of the metals are strictly monitored and regulated. For example, the guidelines for Canadian Drinking Water Quality recommend the Maximum Acceptable Concentration (MAC) are 0.005 ppm (As and Cd) and 0.010 ppm (Pb) (Health Canada, 2012).   Pulp and paper mills are one of the largest producers of wastewater. The combined annual production of wastewater from pulp and paper mills in Canada and the U.S. is roughly 81.4 million tones, which exceeds the annual flow of the Colorado River (Laws, 2000). Through the use of strong acid during pulp processing, trace metals are leached out from the industrial machineries into the outflow wastewater. As a result, aquatic organisms that live in these environments (e.g. shellfish) can acquire high concentrations of these toxicants and can directly 2 affect humans through consumption of these organisms. In addition, the cumulative effects from pollutions in sediments are on aquatic biota, salmon fisheries and humans through bioaccumulation in the benthic organisms in the sediment. Arsenic, Cd, and Pb are the main trace metals discharged from a pulp, paper and paperboard mill located in Port Alberni, British Columbia, Canada (Environment Canada, 2013). Suspended particulates containing trace metals from wastewater are deposited into the bottom sediments. Therefore, variations in metal concentrations in sediment can provide an important record of contamination levels (de Groot et al., 1976; Baptista Neto, 2000).   1.1.1 Characteristics and geology of the studied area Alberni Inlet and Barkley Sound are located on the west coast of Vancouver Island, along the northern part of the Cascadia subduction zone in British Columbia, Canada (Figure 1.1). The Alberni Inlet is a glacially widened fjord that forms a narrow, steep channel through a mountainous terrain. The inlet extends approximately 45 km to the northeast of Barkley Sound, which consists of: the Loudoun Channel, Imperial Eagle Channel, Trevor Channel, and Junction Passage. Alberni Inlet splits into Trevor Channel and Junction Passage, which connects to Imperial Eagle Channel (Figure 1.2). Barkley Sound is roughly 24 km wide and 20 km long and Trevor Channel and Imperial Eagle Channel connect to the Pacific Ocean. This area is well known for commercial and recreational fishing of Sockeye, Chinook, Coho salmon and halibut as well as shellfish and farmed oysters. It is also an important transportation route for the local economy with respect to logging industries. The Somass River supplies water to the head of Alberni Inlet, where there is a pulp and paper mill that discharges industrial effluent into the headwaters. The mill is considered a point source into the inlet and environmental contamination 3 by effluent from the mill has been studied for more than five decades (Alderdice and Brett, 1957; Levings, 1980; Hagen et al., 1997).  The geology of Vancouver Island consists mainly of the accreted terrane Wrangellia, which extends from southwestern British Columbia to Alaska along the western margin of North America (Mathews and Monger, 2005). Wrangellia includes the characteristic flood basalts of the Triassic Karmutsen Formation as well as other Paleozoic to Tertiary volcanic, plutonic and sedimentary rocks. The terrestrial basement rock types are called Westcoast crystalline complex (WCC), Bonanza Group, Karmutsen Formation and Island Intrusions as a part of Wrangellia (Figure 1.3) (Greene et al., 2009; Andrew and Godwin 1988; Jones et al., 1977; DeBari et al., 1999). Wrangellia was welded to the western margin of North America between the Jurassic and Cretaceous period due to ongoing subduction (Mathews and Monger, 2005). Carter (1973) described the bathymetry and sediment distribution in the vicinity of Barkley Sound and Alberni Inlet. Sedimentation in this area was influenced by glacial activity during the Pleistocene and is responsible for most of the sediments on the continental shelves in this area (Carter, 1973).   4   Figure 1.1. Map of Vancouver Island. The location of Port Alberni and Barkley Sound (in red square).     5  Figure 1.2. Map of Barkley Sound and Alberni Inlet.    6   Figure 1.3. Geological map of Alberni Inlet and Barkley Sound. Modified from Geoscience Map 2005-3 of Geology of British Columbia by British Columbia Geological Survey, Ministry of Energy, Mines and Petroleum Resources Mining and mineral Division.    49 ? 15?49 ? 00?48 ? 45?125 ? 00?125 ? 15?IJBnmu   VaEMJgdBonanza GroupKarmutsen FormationIsland IntrusionsPJg Westcoast Crystalline ComplexBarkleySound7  1.1.2 The bathymetry of Alberni Inlet and Barkley Sound Alberni Inlet and Barkley Sound meet adjacent to the continental shelf of the western Vancouver coast. Alberni Inlet topography is characterized by three sills, which divide the inlet system into three basins and connect it way to Trevor Channel and Junction Passage in Barkley Sound (Waldichuk, 1957). In Barkley Sound, there are two basins (depth of 205 m and 235 m) and sills at the mouth of each channel, Loudoun Channel, Imperial Eagle Channel, Trevor Channel and each sill has depth of 46, 112 and 77 m, respectively (Hourston, 1959; Carter, 1973). From the northeast of Barkley Sound, Junction Passage allows water circulation between Alberni Inlet and Pacific Ocean at the depth of 85 m and Trevor Channel provides an intermediate water exchange regularly at the water depth of 36 m (Hourston, 1959). These basins and sills prevent detritus deposition onto the continental shelf and this special oceanographic setting traps water-column pollutants in the inner shelf, which contains the evidence of pollution in the Barkley Sound (Syvitski and Shaw, 1995; Carter, 1973). The oxygen level in the upper Alberni Inlet (0 km to 18 km from Port Alberni) is between 2 ? 3 ml/l at the depth of 10 ?100 m and less than 2 ml/l at the depth150 m or deeper. There are some seasonal variations of water temperature and oxygen content in the upper inlet, whereas no seasonal variation was reported in the lower inlet (18 ? 40 km) at oxygen content of 1 ? 2 ml/l (Pickard, 1963).  The sedimentation rate in Bamfield and Alberni Inlet has not been studied in detail. Previously, the tidal marsh and sedimentology study of the Barkley Sound basins using 210Pb and 137Cs dating suggested sedimentation rates of 0.3 cm year-1 (Clague et al., 1994) and 0.07 cm year-1 (Townley, 1999).  8 1.1.3 History of the Port Alberni pulp and paper mill  The pulp and paper mill industry is one of the biggest industries of the North American economy and an increasing demand has led to expansion over the past 70 years. As the industry has grown, problems have arisen with impacts to the natural environment such as overexploitation of forests and water contamination from wastewater. In the 1890?s the first pulp and paper mill in British Columbia (B.C.) was built in Port Alberni. After a short period of closure, a sulfite pulp mill was constructed in the inlet in 1938, taking advantage of access to deep-sea shipping through the inlet and allowing for efficient disposal of effluent into the Pacific Ocean by the Somass River (Keeling, 2007).   1.1.3.1 Trace element pollution source and control  Transformation of the pulp to paper requires multiple steps of treatments with concentrated acid and base chemicals that break down the cellulose and a complex compound called lignin, which plays an important role in the cell wall of wood tissue (Ali and Sreekrishnan, 2001; Pokhrel and Viraraghavan, 2004). These industries certainly release trace metals (As, Cd, Pb) into the wastewater through strong acid corrosion of the machinery, and the extent of their removal during the primary and secondary sewage treatment is unresolved. In addition, concentrating significant amounts of raw material into one-location results in the accumulation of the trace elements in surrounding area (Leivisk? et al., 2009). Besides the trace elements in the effluent, pulp and paper mills are known to be a toxic source of wastewater due to the high production of dissolved organics (DO) and suspended solid (SS). Therefore, suffocation of fish, destruction of benthic communities and anoxia occurs in the aquatic community and increase of biological oxygen demand (BOD) (Colodey and Wells, 1992; Laws, 2000). The contamination 9 from the mill have been monitored for protection of the ecosystem by Environment Canada since 1987 and the effects on fish and fish habitat have been monitored by an Environmental Effects Monitoring program (EEM) since 1971 (Keeling, 2007; Environment Canada, 2013). Most recently, the environmental monitoring focus on the paper mill has shifted to dioxins and furans because of the toxicity of these two groups of chemical compounds and the improvement of sewage system for dissolved organics and SS, which as resulted in limited publications related to the toxicity of trace elements from the paper and pulp mill effluent is limited (Leivisk? et al., 2009; Skipperud et al., 1998; Colodey and Wells, 1992).   1.1.4 Arsenic, cadmium and lead toxicology 1.1.4.1 Arsenic Arsenic (As) studies in the environment have increased due to its health effects on humans as a carcinogen (Laws, 2000). It is known to be naturally high in drinking water and some recent studies in Bangladesh have identified humans who have been diagnosed with severe toxicity effects such as skin pigmentation changes, kidney disease, gastrointestinal symptoms, anemia and liver disease (USEPA, 1998; Chowdhury et al., 1999; Hall, 2002). Arsenic exposure to humans is mainly caused by the use of plastic toys, candles and fabrics since As is used as a pigment in these products. Industrial pollution such as mining and ore deposit releases large amount of As into the environment (Hughes et al., 2011). High purity As is still used in semiconductors (ATSDR, 2007).    10 1.1.4.2 Cadmium Cadmium (Cd) is known as a highly toxic metal for the human liver (Baba et al., 2013) and its emission to the environment is mainly a result of the use of Ni-Cd batteries and pigments (Laws, 2000). In 1995, Itai-Itai (pain-pain in Japanese) disease was reported in Japan as one of the biggest human exposures of cadmium from mining industrial water pollution. The contamination spread to rice paddies located downstream and consumption of this rice led to Cd poisoning to the residents in this area (Kasuya et al.,1992). Symptoms included severe pain in the back, joints and lower abdomen, and multiple bone fractures just from coughing which was led by Ca loss from bones (Yamagata and Shigematsu, 1970; Nogawa, 1980; Baba et al., 2013).   1.1.4.3 Lead Lead (Pb) is one of the heavy metals that is widely distributed in the Earth?s crust and its natural concentration level ranges widely among different rocks, soils and sediments. The average concentration of Pb in the Earth?s crust is 14.8 ppm (Wedepohl, 1995) and upper continental crust is 20 ppm (Taylor and McLennan, 1985). The world ore production of Pb dates back more than 5000 years (Callender, 2003; Laws, 2000). One of the major sources of Pb pollution was caused by the use of leaded gasoline that started in the1920?s and banned in 1990?s in Canada (Nriagu, 1990; Laws, 2000). As a consequence, atmospheric Pb input increased and exposure was 500 times higher in 1979 than in pre-industrial times (Ericson et al., 1979). In Vancouver, British Columbia, Burnaby lake core sediments indicated an increase in Pb input into the environment during the 1920?s and recorded the highest exposure in 1970?s (McCallum and Hall, 1998). Human exposure can be caused by inhalation and ingestion of contaminated food and water. Pb is mostly known as a neurotoxin, but in addition it can also cause anemia and 11 damage to the kidneys and reproduction system (Laws, 2000; Needleman, 2004). Recently, child exposure has been one of the greatest concerns due to the effect of prenatal exposure to Pb on neurodevelopment in the child  (Ris et al., 2004) leading to cognitive deficits and behavioral disorders (Yorifuji et al., 2011; Nigg et al., 2010). Learning difficulties and school failure have been reported from long-term Pb exposure (Needleman, 2004). In addition, some publications suggest that Itai-Itai disease in Japan might be a result of Pb poisoning with the possible input of Pb from industrial wastewater (Yamagata and Shigematsu, 1970).   1.1.5 Pb isotope compositions use as an environment tracer Pb is a widespread element and occurs naturally in soils, plants, rocks, water, and atmospheric particles. Mining and smelting industrial products containing Pb are considered to be anthropogenic Pb as opposed to natural occurring Pb. In addition, ice/sediment cores, peat bogs, coral and trees archive the environmental record and their Pb isotope compositions have been studied to investigate historical variability trends (Biscaye et al., 1997; Shotyk et al., 1998; Bindler et al., 2004). The isotopic composition of Pb has been used in environmental investigations as a tracer to pinpoint the source and transport pathway of contaminants (e.g., Grousset and Biscaye, 2005; Simonetti et al., 2003). There are four naturally occurring lead isotopes: 204Pb, 206Pb 207Pb, and 208Pb. The lead isotopes 206Pb, 207Pb, 208Pb are the stable products of radioactive decay from 238U, 235U, and 232Th (respectively) while 204Pb is the least abundant stable Pb isotope and is the only non-radiogenic Pb isotope. The abundances of the other Pb isotopes are variable depending on the origin of an ore body and age of the deposit (Cheng and Hu, 2013; Mil-Homens et al., 2013).   12 Lead released into the environment by industrial processes retains the Pb isotopic composition of the original ore, which is a result of radioactive decay of the parent isotopes 238U, 235U, and 232Th in the ore over geological timescales (Ault et al., 1970). This means that Pb isotope ratios can be used to ?fingerprint? the source or to identify mixing of multiple Pb sources (Chang and Hu, 2010). By comparing the isotopic composition with archived data, Pb isotope fingerprinting can discriminate between natural and anthropogenic Pb pollution sources.   1.1.6 Major element use to establish provenance and contamination of marine sediments Transportation of terrestrial materials from shore erosion and deposition of anthropogenic and atmospheric constituents is reflected in chemical composition of the sediments (Burdige, 2006). Major element analysis provides information of the provenance of the lithogenic fraction of marine sediments (Calvert and Pedersen, 2007) and aluminum (Al) is one of the major elements of crustal rocks (bulk upper crust and shales have similar Al concentration as most common sedimentary rocks). In addition, Al is not significantly affected by anthropogenic sources, Al2O3 (for chemical analysis Al is analyzed as oxide) has been used as elemental normalizer and the element/Al2O3 ratio provides qualitative information on anthropogenic sources of other elements to marine sediments (Van der Weijden, 2002). (Windom et al., 1989; Calvert and Pedersen, 2007) Total Carbon (TC) represents the sum of organic carbon (OC) (i.e., natural organic matter, organic chemical compound) and inorganic carbon (IC) (i.e., carbon dioxide). OC to total nitrogen (TN) ratio can discriminate the organic matter basis from the terrestrial or marine input into the sediment composition. Normally high OC/ TN ratios (> 20) indicate the terrestrial input 13 such as vascular plant debris and lower ratio (<10) explains the marine input such as planktons in the sediment (Elser et al., 2000; McKay et al., 2004).  1.2 Overview of the thesis The motivation of this thesis is to determine the environmental impact on Alberni Inlet and Barkley Sound, British Columbia, Canada, from a point source pulp and paper mill located at the headwater in Port Alberni. Concentration data for As, Cd, and Pb, and Pb isotopic compositions were used for this study. In chapter 2, the instrumental configuration of the Agilent 7700x quadrupole inductively coupled plasma mass spectrometer was studied to optimize the analysis of trace element (TE) and rare earth element (REE) analysis. As a result, figures of merit were constructed for each element. Arsenic, cadmium and lead concentration analysis were used in Chapter 3 and other elemental data were archived for future studies.  In Chapter 3, As, Cd, and Pb concentrations and Pb isotopic compositions were used to determine the distribution of anthropogenic Pb in the sediments and to trace the contamination from a pulp and paper mill into the Alberni Inlet and Barkley Sound. These elements indicated that contaminants from the mill are transported into the Alberni Inlet but not into Barkley Sound. The source for Pb in Barkley Sound is distinct from the pulp and paper mill. Major element chemistry was also performed to aid in the investigation of sediment source in this area.   Chapter 4 summarizes the results and discusses the implications of this study. It also provides some suggestions for future studies.   14 Chapter  2: Evaluation of measurement limits of detection, quantification and linearity and sensitivity for trace elements and rare earth element using quadrupole inductively coupled plasma mass spectrometry  2.1 Introduction Analytical technique selection must consider the advantages and limitations of each method available. Further, this information is needed to accurately represent and discuss analytical results. In this study, the Agilent 7700x quadrupole inductively coupled plasma mass spectrometer (ICP-MS) was evaluated for trace element (TE) and rare earth element (REE) analysis. Performance characteristics of the instrument, known as figures of merit (FOM), are evaluated using concentration measurement and different analytical set ups.  Calibration curves (Figure 2.1) are important figures used to validate the analytical method. They provide important information for quantitative concentration measurement analysis by ICP-MS called figures of merit (FOM) (Skoog, 2004) and include;  ? Accuracy  ? Precision ? Limit of detection (LOD) ? Limit of quantification (LOQ) ? Limit of linearity (LOL) ? Dynamic range ? Sensitivity   15 These FOM vary from instrument to instrument, depend on the analytical routine and will vary among analyte. Accuracy is expressed as an absolute error or relative percent error. Precision is the reproducibility of the measurement and represents how measured values are close to each other. Precision is usually expressed as a standard deviation (SD or ?).  The International Union of Pure and Applied Chemistry (IUPAC) defines the limit of detection (LOD) (Figure 2.1) as ?the lowest concentration level that can be determined to be statistically different from an analytical blank? (Long and Winefordner, 1983), where:  Limit of detection = blank mean + (3 ? standard deviation of the blank)   When the blank signal follows normal distribution curve, the calculated LOD is at the 99.86 % of confidence level (Long and Winefordner, 1983).  The lowest concentration at which the blank measurement can be statistically distinguished from the true sample signal is called the limit of quantification (LOQ) (MacDugall et al., 1980) (Figure 2.1), where:  Limit of quantification = blank mean + (10 ? Standard deviation of the blank)  This value is used to demonstrate that the sample measurement is not a random fluctuation of the blank. In which case, LOQ can be used to compare different instruments or methods when quantification is required to validate the methods such as, survey measurement, screen, quality control, legally required monitoring, or evidence for possible violation of a legal limit in environmental samples (MacDougall et al., 1980).  16  Limit of linearity (LOL) can be found by producing a calibration curve where the line becomes no longer linear (Figure 2.1). In most of the analytical set up, LOL is not observed because running high concentration standard can harm the instrument by saturating the ion collector of the ICP-MS.  The slopes of the calibration curve characterize the sensitivity of the instrument and its set up. Fifield and Kealey (2000) defined ?the change in the response from an analyte relative to a small variation in the amount being determined?. The sensitivity is the slope of the calibration curve and where the curve is linear between LOD to LOL is called dynamic range.    17    Figure 2.1. Traditional calibration curve.  Example of calibration curve to visualize the limit of detection, limit of quantification, limit of linearity and sensitivity (modified from Mitra, 2003).     18  2.2 Experimental The following elements were analyzed to determine the FOM for Agilent 7700x quadrupole inductive couple plasma mass spectrometer.  ?Trace Element (TE) He Gas mode       Li, As, Rb, Sr, Y, Cd, Ba, Hf, Pb, Th, U ?TE no Gas mode       Cu, Zn, As, Sr, Cd, Ba, Pb, U ?REE He Gas mode       Lanthanides ?REE no Gas mode       Lanthanides The Agilent 7700x Inductively Coupled Plasma Mass Spectrometry (quadruple ICP-MS) has been used in many environment research studies, for trace metal analysis of biological tissues and of natural water analysis (Fatoki et al., 2012; Sakaguchi et al., 2012). This is a relatively new instrument from the Agilent 7700 series and incorporates the third generation of octopole reaction systems (ORS3) to remove interferences in complex matrices by providing different gas modes (i.e., He gas and non-gas modes). With the combination of He gas mode and ORS3 system, the polyatomic interferences, such as 75As and 40Ar35Cl+ (Agilent Technologies, 2005; Wilbur, 2009) can be removed. The He gas mode allows the separation of polyatomic and monoatomic ions by differences in physical size. He molecules interrupt larger polyatomic ions, which causes energy loss by collision while smaller monoatomic analyte ions is not affected. This process prevents the entrance of polyatomic ions in to the mass analyzer by decreasing the energy of polyatomic ions and only allows the analyte to be introduced into the quadrupole. The 19 use of He mode collision cell in the quadruple system with ORS3 removes polyatomic interference and makes the instrument able to measure 75As without polyatomic interference (Caughlin, 2010).  Stetzenbach et al. (1994) determined trace element and REE detection limits for groundwater by quadrupole ICP-MS and reported in the lowest detection limit of 8 ppt for Pb in ground water. Today, the detection limit for quadrupole has dropped to 1.3 ppt for Pb using the Agilent 7700 ICP-MS, and 2.29 ppt  High-Resolution (HR) ICP-MS (Wilbur, 2005; Thermo, 2005). Furthermore, for some of the elements the detection limits are better with the quadruple ICP-MS than with the (HR)-ICP-MS. In addition, the cost of (HR)-ICP-MS is significantly higher, by a factor 3 or 4, than that of the quadrupole ICP-MS.  For the collision cell, it was set up for both helium (He) gas mode and no gas mode (RF power 1550 W, RF matching 1.8 V, sample depth 4.6 mm, carrier gas flow of 1.03 L min-1). The quartz double-pass spray chamber and a borosilicate micromist glass nebulizer (Agilent, USA) were used for sample introduction. All work was carried out at the Pacific Centre for Isotopic and Geochemical Research (PCIGR), University of British Columbia. The instrument is housed in a Class 10,000 clean laboratory. All the standard and sample preparation were performed in Class 1000 clean laboratory and solution preparation was in Class 100 laminar flow hood prior to the instrumental analysis.   2.2.1 Reagents and standards Single element standard solutions (1000 ppm) for each element were obtained from Inorganic Ventures (USA) and a multi-element solution standard solution (100 ppm) was obtained form Custom Grade (Canada).  20 For the calibration analysis, serial dilution was performed leading to a concentration range of 7.555 x 10-4 ppm to 2.882 ppm for calibration curve with 1% v/v HNO3 internal standard solution by weight. Three internal standards were used: 10 ppb of indium (In), 10 ppb of bismuth (Bi) and 40 ppb of selenium (Se) as an internal standard by weight for a stock solution. Blank solution was made 1% v/v HNO3 with the internal solution.  All the plastic ware were washed with 50% v/v HCl for three days at ~ 80 ?C and 50 % v/v HNO3 for three days at ~80 ?C and were then rinsed with 18.2 m? deionized water.   After the collection of data, for each element, a calibration curve was produced by plotting the ion counts of the standard to the concentration of each element and using least squares regression (R2) to find the equation of the best-fit line with the intercept to be at zero. Based on the calibration curve, each value for FOM was calculated. As, Cd, and Pb calibration curves were generated on three different days. In contrast, the REE and other elements (including the REE) were analyzed during one analytical session.  2.3 Result and discussion The FOM for all elements in no gas mode and He gas mode are presented in Table 2.1, 2.2, 2.3 and 2.4. ND indicates the Limit of linearity (LOL) was not detected at a concentration of 2.5 ppm or higher for both no gas and He gas modes. Each analysis was comprised of 1 measurement of 5 scans of the samples in both no gas and He gas modes.   2.3.1 Trace element (TE) Table 2.1 presents is the LOD and LOQ for lithium (Li), rubidium (Rb), strontium (Sr), Yttrium (Y), barium (Ba), hafnium (Hf), thorium (Th) and uranium (U) for no gas mode. High 21 LOD and LOQ were observed in yttrium (Y). Previous study of detection limits for Y (Jenner et al., 1990; Zhang and Nozaki, 1996) has not identified any possible interference during ICP-MS analysis or significantly higher LOD/LOQ difference compare to the other TE or REE elements. Possible contamination was considered by the use of glass nebulizer and water system in the lab, however the internal laboratory blank analysis data showed no contamination of Y from the nebulizer or the water. This concluded there was no apparent source of Y that explains the relatively high LOD/LOQ as compared to other elements under study.  Since ORS3 system removes some of the ions entering the mass analyzer, comparing He gas mode (Table 2.2) and no gas mode for TE, some of the elements showed a decrease in the sensitivity using He.   2.3.2 Rare earth elements (REE)  Tables 2.3 and 2.4 present the elemental concentrations of REE in He gas and no gas mode. Higher LOD and LOQ were reported in He gas mode as compared to the no gas mode. This corresponds to the amount of analyte in the sample reduced by the separation of polyatomic ions by He. Therefore, measurement of REE in He mode requires the use of higher concentrations. However, higher concentrations may be associated with an increase in matrix effects and result in a decrease in sensitivity or potentially an excess of LOL. Therefore, it is important to monitor the counts of the element when sample concentration is unknown. Alternatively, no gas mode provides higher LOL (1.31 ppm) with high sensitivity, which gives a wide dynamic range in the calibration curve. This suggests this mode is suitable for samples of unknown concentration to determine the dilution factors for your initial analysis of samples.   22 2.3.3 Arsenic, cadmium, lead  FOM for arsenic (As), cadmium (Cd), and lead (Pb) are presented in Tables 2.5 and 2.6 for no gas and He gas modes, respectively. The highest concentration that was run during this experiment was 50 ppb and the linearity remained R2 = 99.9%, therefore the LOL was not observed during this experiment. As a result, the dynamic range for no gas mode was determined as: As 229 ppt to 50 ppb, Cd 24.6 ppt to 50 ppb and Pb 5.03 ppt to 50 ppb. For no gas mode; As 496 ppt to 50 ppb, Cd 1.66 ppt to 50 ppb and Pb 4.06 ppt to 50ppb. Given the dynamic range of each element, LOD was high for As in no gas mode and He gas mode comparing to the other two elements. Because of the polyatomic interference of 75As and 40Ar35Cl+ for As analysis, He gas mode is suitable for this dissertation and confirm the range of concentration for As analysis in sample solution is 496 ppt to 50 ppb with He gas mode.    23   Table 2.1. Figure of merit for trace elements in no gas mode. Limit of Detection (LOD), Limit of Quantification (LOQ), Limit of Linearity (LOL) and Sensitivity shown in the table. ND represents not detected where the LOL was not observed during this experiment.  24   Table 2.2. Figure of merit for trace elements in He mode. Limit of Detection (LOD), Limit of Quantification (LOQ), Limit of Linearity (LOL) and Sensitivity shown in the table. ND represents not detected where the LOL was not observed during this experiment.    25   Table 2.3. Figure of merit for rare earth elements in no gas mode. Limit of Detection (LOD), Limit of Quantification (LOQ), Limit of Linearity (LOL) and Sensitivity shown in the table. ND represents not detected where the LOL was not observed during this experiment.  26   Table 2.4. Figure of merit for rare earth elements in He gas mode. Limit of Detection (LOD), Limit of Quantification (LOQ), Limit of Linearity (LOL) and Sensitivity shown in the table. ND represents not detected where the LOL was not observed during this experiment.   27   Table 2.5. Figure of merit for As, Cd, Pb in no gas mode. Limit of Detection (LOD), Limit of Quantification (LOQ), Limit of Linearity (LOL) and Sensitivity shown in the table. ND represents not detected where the LOL was not observed during this experiment.  28   Table 2.6. Figure of merit for  As, Cd, Pb in He gas mode. Limit of Detection (LOD), Limit of Quantification (LOQ), Limit of Linearity (LOL) and Sensitivity shown in the table. ND represents not detected where the LOL was not observed during this experiment.29  2.4 Conclusions This study was performed to determine and document the figure of merit (FOM) of REE element and other elements of the interest (As, Cd, Pd) for this MSc thesis. This investigation of the dynamic range concludes: 1. Trace element dynamic range for no gas mode presented a wide range (ppt to ppm level) with a good sensitivity. The cause for higher Y LOD/LOQ is unresolved after elimination sources of possible contaminations.  Use of He gas mode resulted in a decrease in the sensitivity of one order of magnitude for some of the elements (Ba and Sr). This suggests the He molecules are separating the analyte from polyatomic interferences before introduction to the mass analyzer.  2. Rare earth element dynamic range for no gas mode was 21.5 ppt to 0.141 ppm and He gas mode was 5.46 ppt to 1.31 ppm. The sensitivity difference was not significant between He gas and no gas modes for REE, however, the polyatomic interferences of REE oxides (Jenner et al.,1990) requires He gas mode for REE concentration analysis. 3. Due to the polyatomic interference for As, He gas mode is essential for the analysis of this element. Dynamic range for this study is presented in Table 2.6. Day 2 analysis presented low sensitivity and high LOD/LOQ and the data from this was reanalyzed on a different day. 30 Chapter  3: Potential arsenic, cadmium and lead input into the marine bottom sediments of Alberni Inlet and Barkley Sound from the paper mill  3.1 Introduction Urban and industrial areas produce heavy metals, pathogens, and urban oil runoffs that lead to environmental problems such as aquatic pollution. Examples of industrial activities that produce pollutants are mining, pulping, oil production and recycling (Gray and Eppinger, 2012; Colody and Wells, 1992). Evidence of metal pollution is pervasive, having been identified in environmental samples from even the most remote regions; e.g., in snow from the eastern Arctic Ocean (Mart, 1983), ice cores from Greenland (Hong et al., 1994) and corals from the Atlantic and Pacific oceans (Guzm?n and Jim?nez, 1992). Heavy metals are introduced into aquatic systems by human activities and are incorporated into environmental samples (e.g., ice cores, corals and sediments) that can be utilized as natural archives of environmental metal contamination and it is important to study heavy metal contaminations because of their toxicity to living organisms (Yang and Rose, 2005). Since Pb is immobile in the natural environment, surface and core sediment can be used to reconstruct the history of coastal metal contamination from local human and industrial activities (Adekola and Eletta, 2007; Br?nvall et al., 2001). A paper mill located in Port Alberni, British Columbia, releases effluent high in trace metals (e.g., arsenic (As), cadmium (Cd), and lead (Pb); Keeling, 2007; Environment Canada, 2013) into the headwaters of Alberni Inlet. Alberni Inlet supplies freshwater to Barkley Sound, which is home to several oyster farms (Shiel et al., 2012) and salmon fisheries. Barkley Sound is located on the west coast of Vancouver Island, British Columbia (B.C.) and consists of Imperial Eagle Channel, Trevor Channel and Junction Passage links the two channels and connects 31 Alberni Inlet to Barkley Sound). Alberni Inlet may carry metal contamination into Barkley Sound from Port Alberni. Due to the uncontrolled wastewater production since the installation of the mill in 1890?s, serious pollution was discovered in 1950?s when a classification system for the evaluation of pollution threats from effluent disposal was to the marine environment (Keeling, 2007). Despite the fact that research has been conducted on organic contaminants and oxygen concentrations related to the pulp mill discharges and their effects in the aquatic environment (Colodey and Wells, 1992; Pokhrel and Viraraghavan, 2004), there are few studies on trace metals in the effluent and possible impacts on water quality which the record of heavy metal levels in the effluent in Alberni Inlet only goes back to 2003 (Table 3.1 and Figure 3.1) (Keeling, 2007; Environment Canada, 2013). Environmental studies that include concentrations and isotope ratios of heavy metals have become more prevalent in the last two decades due to the development of multi-element analysis by inductivity coupled plasma mass spectrometry (ICP-MS). Recently, a study of heavy metal concentrations in industrial wastewater indicated elevated concentrations in soil and suggested that sediment and water run off were affected by the contaminant in the soil (Gray and Eppinger, 2012). Due to the establishment of numerical Sediment Quality Guidelines (SQGs) by Long et al. (1995) and MacDonald et al. (2000), contaminant concentrations in the sediments have become more quantitatively comparable in terms of biological effects. SQG values can be used to determine the potential toxicity of sediment, and in combination with Pb isotopic analysis, provide information on the pollution of sediment. Pb isotope fingerprinting allows the identification of Pb sources as a result and it has been used in a large number of environmental studies to trace Pb contaminations; e.g., atmospheric transport of Pb from East Asia can be identified from its Pb isotopic composition (Cheng and Hu, 2010; Simonetti et al., 2004). 32 Recently, a range of well-constructed Pb isotopic compositions have become available for different natural and anthropogenic Pb sources including Pb ores, leaded gasoline, atmospheric aerosols and sea water, which pin-point the source of Pb contamination more accurately (Flega and Patterson, 1983; Weiss et al., 1999; Weiss et al., 2007; Cheng and Hu, 2010; Tyszka et al., 2012).  The focus of this study is to determine the concentrations of As, Cd, and Pb in the sediment from Alberni Inlet and Barkley Sound, and its relationship to the pulp and paper mill in Port Alberni. In addition, lead isotopic compositions were used to identify the source of Pb in the sediments. Also major element data were use to determine the source of sediment in Alberni Inlet and Barkley Sound. While metals such as cobalt (Co), iron (Fe), manganese (Mn), and zinc (Zn) are essential nutrients for humans, elements such as arsenic (As), cadmium (Cd), mercury (Hg), and lead (Pb) have no beneficial effects in humans (Chang, 1996). Arsenic, Cd and Pb concentrations were determined since significant releases of these elements are expected from pulp and paper mill operations in Port Alberni (Environment Canada, 2013). The concentration of metals in sediments was expected to decrease with increasing distance from Port Alberni to the western side of Barkley Sound due to dilution and scavenging by particles to the sediment. However, Pb, Cd, and Pb may have additional anthropogenic and natural sources, such as emissions associated with recreational boating traffic in Barkley Sound (Mikulic et al., 2004; Smedley and Kinniburgh, 2002).  Heavy metals in Barkley Sound sediments were studied to investigate the possible contamination sources and the sediment concentrations were determined to quantify the relative importance of metal pollution throughout Barkley Sound. In the case of Pb, the isotopic ratios 206Pb/207Pb, 208Pb/206Pb, 206Pb/204Pb, and 208Pb/204Pb were compared with other Pb source 33 (fingerprinting technique) and the relative contributions of natural and anthropogenic Pb sources were determined  (Cheng and Hu, 2010; Andrew and Godwin, 1989; Choi et al., 2007; Sangster et al., 2000).   34  ?? ? ???? ? ???? ? ???? ??? ? ????? ? ?? ? ?? ??? ? ? ? ?? ? ? ??? ?? ? ? ?? ? ? ??? ?? ? ? ?? ? ? ??? ?? ? ? ?? ? ? ??? ?? ?? ? ?? ? ?? ??? ?? ?? ? ?? ? ?? ??? ?? ? ? ?? ? ?? ??? ? ?? ? ? ? ? ??? ? ? ? ? ? ? ? Table 3.1. Annual mass of metals discharged to the water from the pulp mill. Data is provided from National Pollutant Release Inventory (Environment Canada, 2013), Environment Canada to represent the annual change of the trace element input into the Alberni Inlet. 35   Figure 3.1. Annual mass of metals discharged to the water from the pulp mill. Showing the annual mass shift of metals by year from the pulp mill in Port Alberni. Data is provided from National Pollutant Release Inventory (Environment Canada, 2013), Environment Canada. In 2009, production of the mill was reduced resulting the swage treatment was no longer required. As a result, the increase of metal discharge was increased to the water.    36  3.2 Experimental method 3.2.1 Sample materials and collection In February 2011 and July 2012, 21 surface-grab samples and 5 core samples were collected from Alberni Inlet and Barkley Sound, Vancouver Island, British Columbia. Alberni Inlet samples were collected along the inlet. In Barkley Sound, samples were collected along a northeast-southwest transect across Trevor Channel and Imperial Eagle Channel (Figure 3.2) by using Ponar type grab sampler. Grab sediment samples consist of 10 to 15 cm (50 to 80 years) of the surface sediment at water depths of 26 m to 270 m (Table 3.2). One sample was collected per site with some duplicate samples. The grab samples were stored at room temperature in acid-washed plastic cups onboard and stored in refrigerator until freeze-dried for processing and analysis. Core samples were collected using the lightweight gravity corer described by Pedersen et al. (1985). Sediment cores (30 to 50 cm) were subdivided into subsamples by depth at 2 cm intervals for the first 10 cm below the seafloor and at 5 cm intervals to the bottom of the cores. Bottom layers were not used for analysis because of possible contamination from the core catching device at the bottom of the core to stop the sample sliding our form the core during sample collection. 37    Figure 3.2. Map of sediment sampling locations of Alberni Inlet and Barkley Sound.  Map of Alberni Inlet and Barkley Sound (Imperial Eagle Channel and Trevor Channel) on the west coast of Vancouver Island. Sample locations are indicated in ? (black) for surface sediment (site numbers indicated) and core samples are indicated by ? (orange) with core site numbers indicated.   Port AlberniPaci!c OceanN 49.0N 50.0N48.0W 125.05W 125.20 W 124.505 km68910717 181911 1216 15413204223232Trevor ChannelImperial Eagle ChannelAlberni InletCore 1 and 2Core 6Core 4Core 538  3.2.2 Sample preparation All samples were freeze-dried for a week, homogenized, and stored for digestion at University of British Columbia.  3.2.2.1 Reagents All laboratory equipment and labware were washed in ~2% Extran? 300 (Merck KGaA, Germany) solution for 3 days. This was followed by 3-day wash in analytical grade 50% HCl (~ 6 M) wash and then 50% environmental grade HNO3 (~ 8 M).  Savillex? PFA vials used for collection of Pb were also cleaned individually with ~6 M sub-boiled HCl additionally.    3.2.2.2 Sample digestion The digestion method of Graney et al. (1995) was followed with some modifications.  Following homogenization of the freeze-dried sediment samples, 30 to 50 mg of material was weighted into Savillex? PFA vials. Digestion was accomplished in three steps: (1) 3 mL sub-boiled HCl (~ 6 M) and 1 mL sub-boiled HNO3 (~ 15 M); (2) 1 mL sub-boiled HNO3 and 2 mL sub-boiled HF (~29 M); and (3) 1.2 mL sub-boiled HNO3 (~15 M) and 0.4 mL of H2O2. In each step, samples were capped and placed on a hotplate at 130 ?C for 2-3 days, then dried down prior to concentration measurement and Pb isotopic analysis by anion exchange chromatograph.  3.2.2.3 Anion exchange chromatography  The Pb ion exchange chromatography method of Strelow and Toerien (1996) method was followed with some modifications reported in Weis et al. (2006). Digested sample were dissolved in 0.5 M HBr and loaded onto the columns with AG1-X8 (mesh size 100-200) resin from Bio-Rad Laboratories, Inc. In HBr the resin absorbs Pb ions (Pb2+ and Pb3+) while releasing other elements. The fraction was then eluted by 6 M sub-boiled HCl into acid washed Savillex? 39 PFA vials, dried down to drive off any traces of eluent, and stored for isotopic analysis. Prior to isotopic analysis, samples were re-dissolved in 1 mL 0.05 M sub boiled HNO3.   3.2.3 Analytical technique 3.2.3.1 Major element analysis Major element analyses were carried out at Activation Laboratories Ltd. (Actlabs) in Ancaster, Ontario. The analytical method is available from the Actlabs web site (http:// www.actlabs.com) and it is outlined in Norrish and Hutton (1969). Briefly, the sample was mixed with combination of lithium metaborate and lithium tetraborate with lithium bromide and fused in a Pt crucible. The fusion disks made in this process were analyzed on a Panalytical Axions Advanced wavelength dispersive XRF instrument. Resulting data and detection limits are presented in Table 3.3. In order to characterize the nature of the lithogenous material deposited into the Alberni Inlet and Barkley Sound, the geological compositions of Vancouver Island and local bedrock geology (West Crystalline Complex (WCC), Island Intrusions, Bonanza Group, and Karmutsen Formation) were compared (De Bari et al., 1999; Greene et al., 2009). These comparisons are made with Al2O3 and major element concentrations since there are only minor variations of Al2O3 in all igneous and most metamorphic rocks as well as in soils formed from such substrates (Calvert and Pedersen, 2007).   3.2.3.2 Trace element analysis  An Agilent 7700x Quadruple ICP-MS (Agilent USA) was used to determine the concentration of the As, Cd, and Pb. Instrument settings are described in Chapter 2. Analytical errors were quantified through repeated measurements of stream sediment reference (STSD-2) 40 from Canadian Certified Reference Materials Project (CANMET Mining and Mineral Science Laboratories) which represented similar matrix with the samples. Replicate analysis of STSD-2 during the analysis yielded mean ?2 ? values of As = 42.7 ? 3.1 ppm, Cd = 0.72 ? 0.02 ppm and Pb = 59.0 ? 2.9 ppm (n=7). Mid-range calibration solutions (100 ppb As, Cd, Pb) were analyzed every seven samples and sample concentrations were detected within the dynamic range of the calibration curve. During the concentration analysis, internal standards were added at 10 ppb of indium (In), 10 ppb of bismuth (Bi) and 40 ppb of selenium (Se) to the samples to correct for changes in matrix, sample up take rate, and accumulation of the samples on sample cone. The samples were run above the detection limit (Chapter 2) in multiple days and the relative standard deviation (RSD) for five analyses of the same sample solution was 1 ? 3 % (As), 1 ? 6 % (Cd) and 0.2 ? 1 % (Pb) for each element concentration > 25 ppb. Certified Reference Material PACS-2 (National Research Council Canada) was used to determine the trace element concentration in the sediment.  3.2.3.3 Pb isotope analysis Pb isotopic analysis was performed on a Nu plasma MC-ICP-MS (Nu 021) and a Nu Plasma II MC-ICP-MS (Nu 214) (Nu Instruments Ltd, UK) with sample introduction by DSN 100 (Nu Instruments, UK) membrane desolvator. Analyses were carried out in Class 10,000 clean labs at the Pacific Centre for Isotopic and Geochemical Research (PCIGR), UBC. Lead isotopes analysis procedures by MC-ICP-MS at PCIGR are outlined in Weis et al. (2006) and Barling and Weis (2008). All standard and sample solutions were prepared with 0.05 M sub-boiled HNO3. All solutions were prepared at a constant Pb/Tl ratio of 4:1. Due to isobaric interference 204Hg in MC-ICP-MS (White et al., 2000), 202Hg was monitored and the natural 202Hg/204Hg ratio of 4.350 (de Laeter et al., 2003) was used to correct 204Pb. During the analysis, 41 the ion intensity for 208Pb ranged from 1.8 to 4.8 V. At the beginning of analysis, NIST SRM 981 Pb standard was analyzed until measured Pb isotope ratios stabilize (? 5 analyses). Thereafter, the standard was re-analyzed every two samples. Measured Pb ratios were corrected to the triple spike Pb isotope ratios of Galer and Abouchami (1998) using a sample-standard-bracketing (SSB) procedure (sample/ ((standardbefore + standardafter )/2)) ? 1) ? 100 (%)) modified after White et al. (2000) and Albar?de and Beard (2004). Replicate analyses of NIST SRM 981 over the course of this study yielded in-run mean ?2 ? values of 206Pb/207Pb = 1.09304 ? 4 (37 ppm), 208Pb/206Pb = 2.16730 ? 14 (66 ppm), 208Pb/204Pb = 36.720 ? 75 (205 ppm), 207Pb/204Pb = 15.5005 ? 27 (179 ppm), and 206Pb/204Pb = 16.9428 ? 28 (170 ppm) [n =68]. The ppm value in parenthesis represents the external precision of the analysis, where: External precision = 2 Standard deviation / Average value of isotope ratio ? 1,000,000   3.2.3.4 Carbon and nitrogen analysis Inorganic carbon contents were determined at the University of British Columbia by CO2 coulometer, Model CM5014 CO2 (UIC INC., USA) with an acidification module. Sample aliquots of 0.3 to 0.5 g were weighted into test tubes and acidified using by sulfuric acid. Reproducibility for replicate measurements was between 1.7 and 5.0 % (details provided in Table 3.5).  Total carbon (TC) and nitrogen contents (N) were analyzed by elemental analyzer ratio MICRO cube (Elementar Americas, Inc. USA). Sample aliquots of 20 to 35 mg were weighted into a tin foil evaporating cups and placed into a carousel. Reproducibility for replicate measurements was better than 1 % and organic carbon value were determined by subtraction of inorganic carbon from total carbon value.  42 3.3 Result 3.3.1 Surface sediments  3.3.1.1 Major elements  Surface sediment major element results are presented in Table 3.1. Due to relatively high loss on ignition (LOI) values, major element abundances are also reported after renormalization to 100% after subtraction of LOI values (Tables 3.3 and 3.4, respectively). Silica concentrations range from 57.3 to 63.3 wt. %. The most noteworthy features of the major elements in these samples are relatively high MgO (2.09 ? 4.61 wt %) and Fe2O3 (6.54 ? 9.34 wt %), which lead to relatively high ratios of Fe2O3 and MgO to Al2O3 (Figure 3.3) compared to Upper Continental Curst (UCC) and Post-Archean Average Shale (PAAS). Manganese (MnO) content ranges from 0.058 - 0.124 wt. % and Ca ranges 2.66 ? 8.26 wt. % where the highest content are observed at the closet to the Pacific Ocean (site 7, Figure. 3.3). Potassium, Ti, P, Cr, and V contents variation is minimal but significant among samples.  SiO2/Al2O3 ratios increase (3.56-4.69) and MgO/Al2O3 ratios (0.15-0.29) decrease towards the Pacific Ocean (Figure 3.3). Fe2O3/ Al2O3 ratios, which can be associated with ferromanganese mineral contents, range from 0.45 to 0.60. Fe2O3/Al2O3 and MgO/Al2O3 ratios are higher than the values for UCC and PAAS (Taylor and McLennan., 1985) (Figure 3.3). CaO/Al2O3 ratios are similar to UCC and the northern Cascadia Basin (ODP146 ? sites 888 and 1027, Carpentier et al., 2013) except at 68 km, where CaO/Al2O3 is significantly higher (Figure 3.3). 3.3.1.2 Carbon and nitrogen  Carbon and nitrogen contents of surface sediments are listed in Table 3.5. The total carbon (TC) ranges from 0.75 to 9.43 wt. % with the lowest and highest value at 66 km and 5 km, respectively. The organic carbon (OC) ranges from 0.24 to 9.42 wt % and the lowest and 43 highest locations are the same as TC. Inorganic carbon (IC) ranges between below the detection limit to 0.35 wt. %; the lowest and highest values are at 1.3 km and 17 km, respectively. Total nitrogen (TN) values range from 0.04 to 0.40 %. To provide proxy information for identifying biological activity, OC measurement are calculated to carbon-nitrogen ratio and presented in Table 3.5. The ratio range widely (6.0 to 31.4); the highest ratio occurs 5 km downstream from Port Alberni and the lowest at 66 km, closest to the Pacific Ocean.   44   Site Sample Depth (m) Distance from Latitude (N) Longitude (W) [As] [Cd] [Pb] Port Alberni (km) (ppm) (ppm) (ppm) 24 9.1 0 49?14.222 124?49.492 9.3 0.23 6.9 2 23 1 49?13.475 124?49.346 14 0.75 13 23 35 3 49?12.691 124?49.280 15 0.81 9.2 3 86 5 49?11.303 124?49.010 18 0.76 10 22 122 13 49?09.519 124?48.175 23 0.52 9.2 4 133 14 49?09.005 124?48.980 24 0.69 13 20 293 25 49?03.089 124?51.114 16 0.87 18 13 334 33 48?59.851 124?53.255 10 0.39 14 14 113 41 48?58.942 124?59.426 10 0.29 8.6 15 183 45 48?57.093 125?01.483 8.3 0.44 7.5 16 183 46 48?56.835 125?01.892 14 0.43 15 12 160 48 48?57.524 125?03.307 11 0.4 7.4 19 162 50 48?54.636 125?02.897 14 0.5 16 11 99 51 48?58.100 125?05.602 11 0.36 15 10 95 54 48?56.868 125?07.576 12 0.36 18 17 150 55 48?53.094 125?05.833 16 0.48 16 18 81 57 48?53.356 125?02.277 6.2 0.4 4.9 9 87 59 48?54.457 125?09.133 10 0.25 15 8 103 60 48?55.129 125?11.708 12 0.39 18 7 33 66 48?49.352 125?11.081 3.8 0.03 4.1  Table 3.2. Surface sediment locations and result of trace element concentrations Distance from Port Alberni (km), sample depth (m), sample locations, and concentrations (dry wt. ppm) are presented in this table.    45   Site 2 4 7 8 10 12 14 17 24 Distance from Port Alberni (km)  1 14 66 60 54 48 41 55 0 Analyte Symbol Detection Limit          SiO2 0.01 53.1 44.6 59.4 53.1 51.61 53.2 54.8 48.7 49.5 Al2O3 0.01 13.21 12.51 12.66 12.95 12.44 13.79 12.95 12.03 11.63 Fe2O3* 0.01 6.97 7.26 5.83 6.24 6.11 7.09 7.28 6.08 6.12 MnO 0.001 0.075 0.078 0.116 0.052 0.048 0.094 0.088 0.055 0.066 MgO 0.01 2.98 3.58 1.96 2.62 2.62 3.25 3.29 2.71 2.71 CaO 0.01 2.98 2.8 7.75 2.25 2.55 3.72 4.81 3.12 2.85 Na2O 0.01 4.00 4.54 3.61 4.45 4.82 4.04 3.78 5.18 4.86 K2O 0.01 1.14 1.25 1.25 1.90 2.03 1.87 1.23 1.97 1.24 TiO2 0.01 0.95 0.87 1.02 0.80 0.76 0.76 0.94 0.67 0.81 P2O5 0.01 0.18 0.24 0.14 0.27 0.20 0.21 0.20 0.22 0.15 Cr2O3 0.01 0.02 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.02 V2O5 0.003 0.034 0.039 0.026 0.021 0.021 0.028 0.031 0.021 0.029 LOI  14.63 22.87 5.53 16.04 17.05 12.36 11.11 19.96 20.43 Total 0.01 100.3 100.6 99.32 100.7 100.3 100.4 100.5 100.8 100.4  Table 3.3. Major element oxide (wt. %) abundances in surface sediment grab samples. Analyses were performed at Activation Laboratory. Fe2O3* is total ion, which includes both iron species. LOI is loss-on-ignition. Significant figures based on the 2 ? defined by duplicate analysis. The calculated RSD of replicates and duplicates was less than 3% and the reference material recovery was ? 6%. Lower limit of detection limits were less than 0.01 wt. %.46  Site 2 4 7 8 10 12 14 17 24 Distance from Port Alberni (km) 1 14 66 60 54 48 41 55 0 Analyte Symbol          SiO2 62.0 57.3 63.3 62.8 62.0 60.4 61.3 61.6 60.3 Al2O3 15.42 16.09 13.50 15.30 14.94 15.66 14.49 13.74 14.88 Fe2O3* 8.14 9.34 6.22 7.37 7.34 8.05 8.14 6.54 7.52 MnO 0.088 0.100 0.124 0.061 0.058 0.107 0.098 0.066 0.068 MgO 3.48 4.61 2.09 3.09 3.15 3.69 3.68 3.41 3.35 CaO 3.48 3.60 8.26 2.66 3.06 4.23 5.38 3.42 3.86 Na2O 4.67 5.84 3.85 5.26 5.79 4.59 4.23 7.48 6.41 K2O 1.33 1.61 1.33 2.24 2.44 2.12 1.38 2.75 2.44 TiO2 1.11 1.12 1.09 0.94 0.91 0.86 1.05 0.77 0.83 P2O5 0.21 0.31 0.15 0.32 0.24 0.24 0.22 0.21 0.27 Cr2O3 0.02 0.03 0.02 0.01 0.01 0.01 0.01 0.01 0.01 V2O5 0.040 0.050 0.028 0.025 0.025 0.032 0.035 0.027 0.026  Table 3.4 Major element oxide (wt. %) abundances in surface sediment renormalized to 100 % after subtraction of loss of ignition value (LOI). Abundance in core sediment renormalized to 100% after subtraction of loss of ignition value (LOI). *Represents the total oxide for both iron species.   47    Figure 3.3. Major element concentration in wt. % to aluminum oxide in wt. % ratio vs. distance (km) from Port Alberni for surface sediment.  Distance from Port Alberni mill versus major element/Al ratio plotted along with upper continental crust (UCC), PAAS, and Cascadia Basin (ODP146-Site 888) (Taylor and McClennan, 1985; Carpentier et al., 2013).   48   Site # Distance (km) TC (wt. %) IC (wt. %) OC (wt. %) TN (wt. %) OC/TN 24 0 6.56 0.02 6.55 0.23 28.5 2 1.3 4.27 N/D 4.27 0.19 22.5 23 3 5.30 0.01 5.29 0.21 25.2 3 5 9.43 0.02 9.42 0.30 31.4 22 13 7.74 0.01 7.73 0.32 24.2 4 14 7.47 0.03 7.44 0.33 22.5 20 25 5.42 0.10 5.31 0.37 14.4 13 33 4.30 0.25 4.05 0.34 11.9 14 41 2.40 0.22 2.18 0.19 11.5 15 45 2.30 0.27 2.69 0.30 9.0 16 46 3.87 0.35 3.52 0.40 8.8 12 48 1.49 0.27 1.22 0.14 8.7 19 50 3.93 0.25 3.69 0.38 9.7 11 51 3.75 0.30 3.45 0.38 9.1 10 54 3.06 0.23 2.83 0.32 8.8 17 55 3.93 0.35 3.58 0.39 9.2 18 57 1.78 0.12 1.66 0.13 12.8 9 59 2.83 0.22 2.61 0.30 8.7 8 60 3.05 0.20 2.85 0.33 8.6 6 65 2.44 0.15 2.29 0.24 9.5 7 66 0.75 0.50 0.24 0.04 6.0  Table 3.5. Carbon and nitrogen contents in surface sediment. Total carbon (TC), inorganic carbon (IC), organic carbon (OC) and total nitrogen (TN) content are presented in this table (wt. %).  IC value was calculated by subtracted of OC from TC. TC and TN were analyzed by element analyzer (RSD = 0.92 for TC, 0.40 for TN) and IOC was analyzed by CO2 coulometer (RSD = 2.2 to 5.6 %).    49  Figure 3.4. Carbon-nitrogen ratio vs. distance from Port Alberni for surface sediment.  Distance from Port Alberni mill versus C/N ratio plotted along with terrestrial input value and marine input value (Elser et al. 2000; McKay et al. 2004). This is representing the high input of terrestrial OC in the upper inlet and marine OC at the mouth of Barkley Sound.      50  3.3.1.3 Trace element concentration  Surface sediment trace element concentrations are reported following subdivided into three northeast-southwest transects based on sample locations (Figure 3.5): Alberni Inlet (Transect 1), Trevor Channel or eastern Barkley Sound (Transect 2), and Imperial Eagle Channel (Transect 3) of western Barkley Sound.  In general, a decrease in the concentrations of As and Cd is observed in sediments along the studied transects, from Alberni Inlet (northeast Barkley Sound) to the opening of Barkley Sound into the Pacific Ocean (southwest Barkley Sound) (Figures, 3.6, 3.7).   Figure 3.5. Map of three transects. Map of Alberni Inlet and Barkley Sound indicating the three different transects discussed in the text. Transect 1 represents Alberni inlet, transect 2 is Trevor Channel and transect 3 is Imperial Eagle Channel Port AlberniPaci!c OceanN 49.0N 50.0N48.0W 125.05W 125.20 W 124.505 km68 910717 181911 1216 15413204223232Trevor ChannelImperial Eagle ChannelAlberni InletTransect 1Transect 2Transect 351 3.3.1.3.1 Arsenic  Concentrations of arsenic in the sediments range from 3.8 to 24 ppm (Table 3.2). Concentrations of As are highest in the upper inlet and generally decrease towards the Pacific Ocean (Figure 3.6). In Transect 1, concentrations increase from distance zero to 14 km, followed by a decrease from 14 km up to 47 km where Alberni Inlet meets Trevor Channel and Imperial Eagle Channel. The highest concentration (24 ppm) is at 14 km downstream from the paper mill. For Transect 2, the concentration increases from 10 to 15 ppm between 47 to 55 km and decreases to 3.8 ppm downstream from 55 km. Transect 3 displays minor changes in concentration and overall values are consistent with the concentration at the end of the Transect 1.  3.3.1.3.2 Cadmium  Cadmium concentrations in surface sediment range from 0.04 to 0.97 ppm (Table 3.2). The highest concentrations are 0.97 ppm at 14 km in Transect 1 and 0.94 ppm at 3 km in Transect 1(Figure 3.7). In the upper (northern) part of Transect 1, Cd concentrations are relatively high (0.78 ppm), expect at 13 km where Cd decreases by about half. In lower part of the inlet, (after 33 km), the concentration drops to 0.3 ppm and then increases to 0.45 ppm. In Transect 2, Cd concentrations increase slightly at the beginning, but decrease closer to the Pacific Ocean. Between the end of the Transect 1 at 41 km and the beginning of Transect 2 at 50 km, concentrations increase from 0.29 ppm to 0.50 ppm, whereas, the concentrations remain consistent in Transect 3.   Overall, Cd concentrations in Alberni Inlet decrease towards to the end of inlet and in Trevor Channel. However, this trend is not pronounced in transect 3, Imperial Eagle Channel.  52   Figure 3.6. Arsenic concentrations vs. distance form Port Alberni Mill.  Transect locations are shown in Figure 3.5.     Figure 3.7. Cadmium concentration vs. distance form Port Alberni Mill. Transect locations are shown in Figure 3.5.    53 3.3.1.3.3 Lead  Lead concentrations in surface sediment range from 4.1 ppm to 18 ppm (Table 3.2). The highest concentration (18 ppm) occurs in three different locations: Transect 1 at 20 km and Transect 3 at 54 km and 60 km (Figure 3.8). In the upper inlet, there is a peak in the Pb concentration at 1 km, followed by a decrease between 3 km to 13 km, then an increase to 18 ppm 25 km away from the mill. Subsequently, the Pb concentration decreases to 7.5 ppm at the end of transect 1 and increases sharply to more than 16 ppm in transect 2 and 3. Transect 2 shows a concentration increase from 46 km to 55 km (7.5 to 16 ppm) and then decreases to 4.9 ppm at 57 km. Pb concentrations continue to decrease at the end of the Transect 2, close to the continental shelf of Vancouver Island. In Transect 3, Pb concentrations increase at the beginning and then remain consistently high concentration (15 -18 ppm) to the end. Overall, a Pb concentration decrease is observed in Alberni Inlet towards the ocean but there are elevated concentrations in the Barkley Sound. 54    Figure 3.8. Lead concentration vs. distance form Port Alberni Mill. Transect locations are shown in Figure 3.5.  55 3.3.1.4 Pb isotope  Pb isotope ratios range from 1.17020 to 1.21602 for 206Pb/207Pb, 2.03967 to 2.08348 for 208Pb/206Pb, 37.586 to 38.754 for 208Pb/204Pb and 18.1489 to 19.0001 for 206Pb/204Pb (Table 3.6). In Figure.3.9 208Pb/206Pb and 206Pb/207Pb values of surface samples are plotted with two endmembers as a comparison to the most radiogenic and least radiogenic in the Earth System. As a definition, the high 206Pb/207Pb and low 208Pb/206Pb value means more radiogenic and vice-versa for least radiogenic ratio. Sullivan mine ore in Canada, (mean calculated by Sangster et al., 2000, references within) which considered as anthropogenic lead value and the Northern Cascadian basin sediment (ODP 146-Site 888, Carpentier et al., in-prep) as a natural source. Most of the Alberni Inlet sediments are relatively less radiogenic in 206Pb/207Pb ratio with several of the sites overlapping with Northern Cascadia sediment.  56    Figure 3.9. 208Pb/207Pb vs. 206Pb/207Pb isotopic ratios.  208Pb/207Pb vs. 206Pb/207Pb showing Pb isotopic ratios for surface sediments analyzed in this study, compared to two endmembers, an anthropogenic source (Sullivan mine ore, Canada, Sangster et al., 2000) and a natural source, Northern Cascadian basin sediment, (ODP 146-Site 888, (Carpentier et al., in prep). Highway dust represents a mixture of anthropogenic and natural lead (Preciado et al., 2007). For samples analyzed in this study, 2SE error bars and reproducibility of SRM 981 are smaller than the symbol size.  57      Site Distance from Port Alberni (km) 206Pb/207Pb 208Pb/206Pb     208Pb/204Pb     206Pb/204Pb   Mean Error (2SE) Mean Error (2SE) Mean Error (2SE) Mean Error (2SE) 24 0 1.18621 2 2.06397 4 38.190 3 18.5027 12 2 1 1.17020 2 2.08132 4 37.586 2 18.2387 8 23 3 1.16498 2 2.08700 4 37.877 2 18.1489 10 3 5 1.16970 2 2.08143 5 37.945 4 18.2299 15 22 13 1.18069 2 2.06951 4 38.095 3 18.4077 17 4 14 1.17880 2 2.07424 4 38.140 2 18.3877 8 20 25 1.17233 2 2.08348 5 38.083 3 18.2781 14 13 33 1.17987 2 2.07654 4 38.226 4 18.4079 18 14 41 1.17931 2 2.07723 2 38.205 4 18.3919 18 15 45 1.21263 2 2.04856 4 38.831 3 18.9550 12 16 46 1.18460 2 2.07404 4 38.338 3 18.4849 14 12 48 1.21602 2 2.03967 5 38.754 3 19.0001 14 19 50 1.18185 1 2.07537 4 38.260 2 18.4349 13 11 51 1.18483 2 2.07369 4 38.344 3 18.4906 11 10 54 1.18555 2 2.07332 4 38.358 2 18.5008 12 17 55 1.18089 2 2.07654 4 38.255 3 18.4222 10 18 57 1.20688 2 2.04306 6 38.474 3 18.8312 11 9 59 1.18693 2 2.07190 5 38.380 3 18.5244 11 8 60 1.18602 2 2.07307 4 38.373 2 18.5105 11 7 66 1.21304 2 2.03967 4 38.610 3 18.9300 16  Table 3.6. Pb isotopic ratio for surface sediment of the measured value. 2SE values (twice the standard errors) apply to the last digit(s) of the measured ratio.   58 3.3.2 Core sediment 3.3.2.1 Major element  Major element analyses are presented in Tables 3.8 and 3.9 (renormalized to 100 %). Renormalized silica concentrations (in wt. % SiO2) range from 62.2 to 62.3 % (site 1), 61.9 to 62.2 % (site 2), 63.1 to 64.2 % (site 4), 59.5 to 60.5 % (site 5) and 62.2 to 62.3 % (site 6). For the other major elements, there are no significant differences within the same core sample by depth. Al2O3 ranges from 14.71 to 15.38 % and Fe2O3*ranges from 6.83 to 8.33 wt. % in all core samples. Most noteworthy is core 2, which displays a range of CaO (3.21 ? 4.00 wt. %). Na2O also shows variations with core depth: cores 4 and 6 have higher Na2O at the 3 cm depth samples. MgO and CaO ranges from 2.95 to 3.60 wt. % and 2.99 to 4.59 wt. %, respectively in all core samples, which represents significant difference between cores. Quality control was addressed through the use of reference materials, in-house-standard, analytical replicates, and analytical blanks. The calculated RSD of replicates and duplicates was less than 3% and the reference material recovery was ? 6%. Lower limit of detection limits were less than 0.01 wt. %.  59  Core Site N W Distance form Port Alberni (km) Core depth (cm) As Cd Pb 1 49 13.458 124 49.448 1 1 14.3 0.6 11.8         3 9.8 0.7 12.8         7 12.2 0.9 14.4         1 14.4 0.8 13.2 2 49 13.480 124 49.443 1 3 11.7 0.8 12.5         7 13.1 0.7 11.1         11 13.1 0.8 12.3         15 12.5 0.7 10.8         19 3.5 0.2 2.9         27.5 4.9 0.3 4.1         30 12.6 0.6 9.9 4 48 50.875 125 08.830 63 1 8.1 0.3 12.4         3 8.0 0.5 12.7         7 11.2 0.4 14.4         11 10.3 0.4 13.0         19.5 11.2 0.5 15.1         34.5 10.0 0.5 15.1 5 48 51.993 125 14.637 67 1 7.3 0.2 11.7         3.5 7.2 0.2 12.7         8 7.8 0.2 13.2         13 10.1 0.3 14.8         21.5 8.3 0.2 14.6 6 48 58.390 124 59.995 40 1 11.2 0.4 14.4         3 11.3 0.4 15.0         7 11.1 0.5 15.8         11 12.7 0.5 16.1         19.5 20.3 1.1 24.2         24.5 21.6 0.7 23.5         34.5 17.9 0.8 19.2  Table 3.7. Sample location, trace element concentrations data for core sediment samples. Distance from Port Alberni (km), sample locations, and concentrations (ppm) are presented in this table. (As: 2? = 0.9 ppm, Cd: 2? = 0.03 ppm, Pb: 2? =0.1 ppm  60  Core Site 1 2 4 5 6 Core Depth (cm) 1 3 7 3 19 27.5 19.5 34.5 1 3.5 21.5 3 19.5 34.5 Analyte Symbol Detection Limit                SiO2 0.01 53.0 52.7 53.1 52.5 54.1 54.0 50.3 52.6 54.6 54.2 56.2 47.1 48.5 49.0  Al2O3 0.01 12.80 12.93 13.12 13.04 13.18 13.39 12.18 12.66 12.7 12.87 13.07 11.65 12.29 12.44  Fe2O3* 0.01 6.93 6.78 6.97 6.88 7.29 7.17 5.63 5.94 5.82 5.82 6.02 5.85 6.17 6.46  MnO 0.001 0.070 0.072 0.072 0.071 0.081 0.078 0.055 0.057 0.056 0.054 0.051 0.066 0.054 0.061  MgO 0.01 2.93 2.89 2.96 2.97 3.15 3.03 2.63 2.56 2.55 2.53 2.48 2.78 2.77 2.76  CaO 0.01 2.74 2.89 2.75 2.72 3.5 3.06 3.79 3.67 2.77 2.7 2.62 3.06 2.8 2.61  Na2O 0.01 4.18 4.06 3.93 4.1 3.73 3.78 4.98 4.2 4.89 4.81 4.25 5.63 5.03 4.76  K2O 0.01 1.18 1.2 1.16 1.21 1.07 1.14 1.93 1.88 1.91 1.91 1.83 2.05 1.99 1.96  TiO2 0.01 0.91 0.92 0.93 0.93 1 0.98 0.73 0.74 0.8 0.8 0.82 0.67 0.71 0.72  P2O5 0.01 0.23 0.21 0.2 0.21 0.27 0.17 0.24 0.21 0.25 0.22 0.19 0.27 0.22 0.2  Cr2O3 0.01 0.02 0.02 0.02 0.02 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02  V2O5 0.003 0.032 0.033 0.031 0.032 0.034 0.035 0.021 0.021 0.021 0.022 0.019 0.024 0.023 0.025  LOI  15.52 15.87 15.48 15.76 13.21 13.62 17.91 16.05 14.29 13.82 13.11 21.42 19.98 19.77  Total  100.6 100.6 100.8 100.4 100.7 100.5 100.4 100.6 100.6 99.78 100.6 100.6 100.5 100.7  Table 3.8. Major element oxide abundances (wt. %) for sediment core samples. Analyses were performed at Activation Laboratory. Fe2O3* is total iron, which includes Fe2+ and Fe3+. LOI is loss-on-ignition.     61  Core Site 1 2 4 5 6 Core Depth (cm)  1 3 7 3 19 1 3 7 3 19 1 3 7 3 Analyte Symbol                SiO2 62.29 62.23 62.27 62.03 61.86 62.19 61.01 62.18 63.21 63.08 64.20 59.51 60.22 60.48  Al2O3 15.04 15.26 15.38 15.41 15.06 15.41 14.77 14.97 14.71 14.97 14.71 14.71 15.26 15.37  Fe2O3* 8.15 8.00 8.17 8.13 8.33 8.25 6.83 7.03 6.74 6.77 6.88 7.39 7.66 7.98  MnO 0.08 0.08 0.08 0.08 0.09 0.09 0.07 0.07 0.07 0.06 0.06 0.08 0.07 0.08  MgO 3.44 3.41 3.47 3.51 3.60 3.49 3.19 3.03 2.95 2.94 2.83 3.51 3.44 3.41  CaO 3.22 3.41 3.22 3.21 4.00 3.52 4.59 4.34 3.21 3.14 2.99 3.86 3.48 3.23  Na2O 4.91 4.79 4.61 4.84 4.26 4.35 6.04 4.94 5.67 5.60 4.86 7.11 6.25 5.88  K2O 1.39 1.42 1.36 1.43 1.22 1.31 2.34 2.22 2.21 2.22 2.09 2.59 2.47 2.42  TiO2 1.07 1.09 1.09 1.10 1.14 1.13 0.88 0.88 0.93 0.93 0.94 0.85 0.88 0.89  P2O5 0.27 0.25 0.23 0.25 0.31 0.20 0.29 0.25 0.29 0.26 0.22 0.34 0.27 0.25  Cr2O3 0.02 0.02 0.02 0.02 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02  V2O5 0.04 0.04 0.04 0.04 0.04 0.04 0.03 0.03 0.02 0.03 0.02 0.0 0.03 0.03  Table 3.9. Major element oxide data (wt. %) for core samples, renormalized value.  Abundance in core sediment renormalized to 100% after subtraction of loss-on-ignition value (LOI). 62  3.3.2.2 Carbon and nitrogen  Carbon and nitrogen data for core samples are presented in Table 3.10. Total carbon values are dominated by organic carbon and low inorganic carbon contents are observed in Core 1 and core 2 profiles relative to cores 4, 5 and 6. Therefore the upper inlet has higher OC contents than the lower inlet and Barkley Sound. Significantly, in core 2, at 7 cm, the OC content is over 6 wt. % whereas the rest of the core is 4 to wt. 5 %. Nitrogen values consistently decrease with depth for all core samples only very small increments. OC/TN ratios are similar and low in Core 4, 5, 6 and relatively high in core 1, and 2. Overall, upper inlet core and lower inlet/ Barkley Sound can be discriminated by C-N value.   63   Core # Core depth (cm) %total C Inorg C Org C %total N Org C/N 1 1 4.52 0.01 4.51 0.21 21.5  3 4.81 0.07 4.74 0.23 20.6  7 4.91 0.01 4.90 0.21 23.3 2 1 5.01 0.02 4.99 0.21 23.8  3 4.94 0.01 4.93 0.21 23.5  7 6.28 0.03 6.25 0.19 32.9  11 4.39 0.01 4.38 0.18 24.3  15 4.07 0.02 4.04 0.16 25.3  19 4.07 0.01 4.06 0.16 25.4  27.5 4.34 0.02 4.31 0.16 27.0 4 1 3.76 0.32 3.43 0.36 9.6  3 4.02 0.38 3.64 0.35 10.4  7 3.61 0.38 3.23 0.33 9.8  11 3.54 0.38 3.16 0.32 9.9  19.5 3.69 0.39 3.30 0.33 10.0  34.5 3.76 0.37 3.39 0.31 10.9 5 1 2.73 0.17 2.56 0.25 10.2  3.5 2.62 0.15 2.47 0.24 10.3  8 2.72 0.16 2.56 0.24 10.7  13 2.84 0.14 2.70 0.23 11.7  21.5 2.59 0.14 2.45 0.22 11.1 6 1 4.26 0.30 3.96 0.43 9.2  3 4.55 0.31 4.24 0.43 9.9  7 4.32 0.36 3.96 0.41 9.7  11 4.70 0.29 4.41 0.42 10.5  19.5 4.38 0.28 4.09 0.40 10.3  24.5 4.37 0.29 4.08 0.39 10.5  34.5 4.32 0.19 4.13 0.39 10.6  Table 3.10. Carbon and nitrogen (wt. %) contents in core sediment. Total carbon (TC), Inorganic Carbon (IOC), Organic Carbon (OC) and Total Nitrogen (TN) content are presented in this table.  IC values are calculated by subtraction of OC from TC. Elemental analyzer was used for TC and TN (RSD = 0.92 % for TC, 0.40 % for TN) and IC was analyzed by CO2 coulometer (RSD = 2.2 to 5.6 %).    64  3.3.2.3 Trace element concentration  Arsenic, cadmium and lead concentrations for the core samples are presented in Table 3.7 and Figure 3.10 displays the evolution of the concentration as a function of core depth. 3.3.2.3.1 Arsenic Most of the samples have higher As concentration than upper continental crust (UCC) (Figure 3.10). There is a sharp increase of concentration in core 6 at depths of 11 cm to 25 cm, and a decrease in core 2 at the same depth. Core samples from the upper inlet (cores 1 and 2) display high concentrations at the surface and decrease with depth, whereas the other core samples display lower concentrations at the surface that increase with core depth.  3.3.2.3.2 Cadmium Cadmium concentrations range from 0.2 to 1.1 ppm in core samples, higher than UCC. Cores 4 and 5 are relatively homogeneous in concentration whereas core 2 and 6 display a sharp decrease and increase respectively at the range of 11 cm to 25 cm. These variations are consistent with As depth variations Figure 3.10.   3.3.2.3.3 Lead Concentrations of lead range from 4.1 ppm to 23.5 ppm typically lower than UCC and post-Archean average Australian Shale (PAAS) (20 ppm) from Taylor and McClennan (1985). Most of the core samples are within the range of Pb concentrations (2.76 to 11.7 ppm) determined for Vancouver Island rocks (DeBari et al., 1999). Cores 4 and 5 show constant concentration with depth. Cores 2 and 6 display a sharp decrease and increase respectively at 11 cm to 25 cm. These anomalies are similar to those observed in As and Cd.   65   Figure 3.10. Concentration plot showing the depth profile of core sediment.  Core sample depths are presented with a comparison to Upper Continental Curst (UCC) value.  UCC value is from Rudnick and Gao, 2003 which is an average of published data between 1889 to 1998. As 2? = 1.0, Cd 2?=0.02, Pb 2?=1.0.   66  3.3.2.4 Pb isotope  The Pb isotope ratios in core samples range from 1.16571 to 1.19109 for 206Pb/207Pb, 2.06883 to 2.08533 for 208Pb/206Pb, 37.874 to 38.492 for 208Pb/204Pb and 18.1619 to 18.5959 for 206Pb/204Pb (Table 3.11). Figure 3.12 shows the isotopic ratios as a function of core depth. For 208Pb/206Pb, cores 1 and 2 become more radiogenic with depth. In contrast, core 4,5 and 6 are less radiogenic at greater depth. Core 1 at 3 cm is the least radiogenic of all samples in all the Pb ratios. Core 5 at a depth of 3.5 cm is the most radiogenic sample in 206Pb/207Pb and 208Pb/206Pb, while samples from 3.5 cm and 8 cm depth from the same core 5 were the most radiogenic 208Pb/204Pb and 206Pb/204Pb. In Figure 3.11, a 208Pb/206Pb vs. 206Pb/207Pb plot shows that the isotope ratios of the core samples are comparable to the surface sediment samples. 67  Core Site Distance form Port Alberni (km) Core depth (cm) 206Pb/ 207Pb  2SE 208Pb/ 206Pb 2SE  208Pb/ 204Pb  2SE 206Pb/ 204Pb 2SE  1 1 1 1.16781 2 2.08377 4 37.925 3 18.2006 11     3 1.16571 2 2.08533 4 37.874 2 18.1619 10     7 1.16972 2 2.08173 5 37.948 3 18.2284 11     1 1.16918 2 2.08235 4 37.951 3 18.2246 12 2 1 3 1.17025 2 2.08118 4 37.962 3 18.2407 13     7 1.16983 2 2.08140 4 37.940 3 18.2292 12     11 1.17004 2 2.08129 4 37.951 3 18.2349 13     15 1.17180 2 2.07935 4 37.978 5 18.2644 10     19 1.17055 2 2.08114 5 37.965 4 18.2427 14     27.5 1.17118 2 2.08024 5 37.972 4 18.2536 12 4 63 1 1.18125 2 2.07342 4 38.187 4 18.4175 14     3 1.18684 2 2.07133 5 38.371 3 18.5245 12     7 1.18585 2 2.07207 4 38.343 4 18.5043 15     11 1.18634 2 2.07170 4 38.357 3 18.5144 13     19.5 1.18499 2 2.07273 5 38.335 3 18.4942 12     34.5 1.18345 2 2.07413 5 38.305 3 18.4679 11 5 67 1 1.19109 2 2.06883 4 38.467 3 18.5934 10     3.5 1.19109 2 2.06887 4 38.473 3 18.5959 13     8 1.19066 2 2.07034 4 38.492 2 18.5919 10     13 1.18951 2 2.06858 4 38.419 3 18.5725 10     21.5 1.18737 2 2.07126 4 38.392 2 18.5354 9 6 40 1 1.18251 2 2.07609 4 38.310 3 18.4528 13     3 1.18251 2 2.07609 4 38.319 3 18.4646 12     7 1.18322 2 2.07503 5 38.306 3 18.4604 11     11 1.18322 2 2.07503 5 38.294 2 18.4508 12     19.5 1.17953 2 2.07771 5 38.232 3 18.4013 12     24.5 1.17631 2 2.08152 4 38.194 3 18.3480 12     34.5 1.17643 2 2.08227 6 38.204 3 18.3464 12  Table 3.11. Isotopic ratio for core sediment of the measured value. Pb isotopic compositions of core sediment samples. 2SE values (twice the standard error) apply to the last digit(s) of the measured value.   68    Figure 3.11. Plot for 206Pb/207Pb vs. 208Pb/206Pb for core samples.  Core sample isotope ratios compared to surface sediment of Alberni Inlet (Figure 3.9) and Northern Cascadia basin (ODP 146-Site 888) (Carpentier et al., in prep). Standard errors (2se) are smaller than the symbol size. Reproducibility of NBS 981 Pb standard is presented as an error bar in the top right corner (206Pb/207Pb error is smaller than symbol size).  69   Figure 3.12. Pb isotope evolution vs. the depth for core samples. The isotopic ratios for 206Pb/207Pb and 208Pb/206Pb are shown with core depth. Higher ratio of 206Pb/207Pb and lower 208Pb/206Pb represents more radiogenic and natural signature in these systems. 70  3.4 Discussion 3.4.1 Composition of the sediment in Alberni Inlet and Barkley Sound 3.4.1.1 Major element  The narrow range of Al2O3 concentrations in the sediment (13 ? 16 wt. %) matches the range of Al2O3 concentrations in the Karmutsen Formation 13 -16 % (Greene et al., 2009). This may suggest an Al2O3 input from Karmutsen Formation basalt into the Alberni/Barkley sediment (Figure 3.13). The modern deposit in this area is the mixture of Karmutsen Formation (forms Vancouver Island) and Bonanza Arc (WCC, Island Intrusions, Bonanza Group) since Alberni/Barkley samples are intermediate in composition between these groups (Figure 3.13), the later being closer in composition to UCC. Alberni/ Barkley sediments are noticeably different in composition from PAAS due to the presence of higher quartz (SiO2), lower ferromagnesian minerals and higher soil illite (K2O) in shales.  In addition, SiO2 vs. Al2O3 diagram (Figure 3.13) represents Alberni Inlet/ Barkley Sound silica dilution of Bonanza Arc samples which may suggests silica input from diatoms. Overall compositional variability of SiO2, MgO, Fe2O3, and K2O indicates the mixing of the two sources, Karmutsen Formation and local rocks from the Bonanza Arc system (WCC, Island intrusions, and Bonanza Arc) in the sediment in this study area. Calcium contents have occasionally high contents due to the presence of benthic shell fragments (visible in the bulk material). Mg-Fe bearing minerals (pyroxene, amphibole, hornblende) in igneous rocks are unstable on earth surfaces and easily weathered and carried to the ocean, as a result, Mg and Fe become enriched in the sediment. The higher concentration of Na2O in some sediment suggests the contribution of sea salt in the dried sediments, which probably results from not having washed the sediment before analysis. Carter (1972) studied the bathymetry of Alberni Inlet and Barkley Sound and  71 defined the bottom sediments in this area as mostly being silt and clay. Silt and clay contain lots of heavy minerals, and that account for the high TiO2 concentration in sediment due to the weathering of Ti bearing minerals, such as rutile (TiO2), sphene (CaTiSiO5) and ilmenite (FeTiO3) (Raman and Jackson, 1965; Tieh et al., 1973), which explains high TiO2 input in Alberni Inlet and Barkley Sound (Figure 3.13).   3.4.1.2 Carbon-nitrogen  Elser et al. (2000) and McKay et al. (2004) indicated the importance of OC and TN ratios to discriminate the organic matter (>20) based on terrestrial input and marine input (<10). The organic material in the sediments of Alberni Inlet and Barkley Sound are a result of mixing with significant contributions from marine phytoplankton, terrestrial (vascular plant detritus and soil) and paper mill effluent (Figure 3.4). This interpretation applies to Alberni Inlet and Barkley Sound. Comparison of Alberni Inlet/ Barkley Sound OC/TN ratios (10-31, Table 3.5) to those found off Vancouver Island, the Columbia River basin and the Washington margin (Prahl et al., 1994; McKay et al., 2004) reveals that there is a significant terrestrial contribution to the organic matter fraction in Alberni Inlet (0- 41 km from Port Alberni). This suggests the input of terrestrial organic matter in to Alberni Inlet and, possibly, to effluents from the local paper mill in Port Alberni where a OC/ TN ratio in sediment around the mill was reported as 15 to 30, within 1 km from the outfall of the mill (Hatfield, 2010). Hence, effluents from the paper mill may heavily impact Alberni Inlet sediments (Figure 3.4). In addition, the silica dilution that was represented in major element results (Figure 3.13) might be associated with silica (SiO2) input from diatoms in the marine organic matter in Barkley Sound (Figure 3.4).     72    Figure 3.13. Major element in wt. % against Al2O3. Plots demonstrate that Alberni Inlet and Bamfield sediments are mixtures of Karmutsen Formation (AG VI) and Bonanza Arc source rocks. Bonanza Arc data is from DeBari et al. (1999) and Karmutsen Formation data is from Greene et al. (2009). VI, Vancouver Island; PAAS, Post-Archean Average Shale; UCC, Upper continental crust.    73 3.4.2 Concentration and Pb isotopic signature in upper inlet vs. lower Alberni Inlet and Barkley Sound  Sediment metal concentrations can reveal the presence of pollutants and an anthropogenically modified ecosystem. The relationships between trace metal concentrations (As, Cd, Pb) in the sediment and biological effects (i.e., sediment-dwelling organisms) have been examined by over 150 publications studying the toxicities of various chemicals. The results of these studies have been used to establish numerical sediment quality guidelines (SQGs), which includes TEC (threshold effect concentration) and PEC (probable effect concentration) (MacDonald et al., 2000; Long et al., 1995). The TEC is the value below which harmful effects are unlikely to be observed, where as harmful effects are likely above the PEC value. Alberni Inlet and Barkley Sound sediment trace metal concentration results are presented in Table 3.2 along with a the summary of the TEC and PEC values (Table 3.12). Table 3.13 also provides trace sediment concentrations from estuaries around the world. The values in Table 3.13 are among the highest concentrations measured in urban estuaries (Meador et al., 2005). Transect 3 (Imperial Eagle Channel) displays lower concentrations (< 10 ppm) in As than other locations in the inlet and transect 2. However the As concentrations in most Alberni Inlet sediments (10 to 24 ppm) are higher than in many estuaries located around the world (13 to 14 ppm) (Table 3.13) and higher than the TEC (9.79 ppm) (Table 3.12). This indicates the As in sediments in Alberni Inlet could have negative impacts on local biological organisms. The Cd concentration (0.03 to 0.87 ppm) is generally lower in most estuaries, but all sediments in the Alberni Inlet and Barkley Sounds have higher Cd than oceanic and deep-sea clays, implying that at least some Cd input into Alberni Inlet and Barkley Sound is anthropogenic. However, Barkley Sound and Alberni Inlet sediment have Cd concentrations  74 lower than TEC, indicating a low probability for Cd toxicity to benthic organisms. Pb concentrations (4.1 to 18 ppm) are slightly lower than the TEC value, indicating that the potential for Pb toxicity in the area is also low (Figure 3.13). The total Pb measured in Alberni Inlet is lower than what might be expected, considering that the Pb input to the inlet from the paper mill effluent is an order of magnitude higher than the inputs of As and Cd. This implies that some Pb may dissolve into the water as Pb4+ rather than remaining in a solid state as Pb2+ in bottom sediments.  In the three trace elements concentration vs. distance from the Port Alberni presented in Figures 3.6, 3.7, and 3.8 (As, Cd, and Pb), concentrations increase to a maximum about halfway along the inlet and then gradually decrease towards the end. The increase in concentrations in the upper inlet is associated with input from the paper mill effluent. It is likely that the highest values occur where suspended particulates from the paper mill reach the bottom of the water column. At the end of the inlet, the concentrations of As, Cd, and Pb are similar to those measured at the head of the inlet which reflect the background concentrations in the sediment.  For Cd and Pb, there was an abrupt decrease in concentration 14 km away from the paper mill, which is followed by an abrupt increase (Figure 3.6, 3.7, 3.8) This can be explained by Cd and Pb behavior that are similar to each other in sediments during diagenesis, and most likely because both elements occur as complexes with chloride and as ligands in organic compounds (Salomons et al. 1998). For Cd, the local enrichment observed may be explained by human activities around the site e.g., Cd is used in boat paint and as a plastic stabilizer (Young et al., 1979, Lemen et al., 1976), and Barkley Sound is one of the most highly utilized as a recreational area.   75 The surface sediment can be influenced by the geochemistry of trace metals in the sediment and the remineralization processes of organic matter precipitating or adsorbing the bottom water, which are primary controlled by redox reactions in response to the decomposition of organic matter (Burdige, 2006). In Barkley Sound, there is an anoxic zone called Sarita Hole (~208 m) in Trevor Channel, where sediment samples were not collected and concentration data is not available in this study. Oxic and anoxic marine environment can vary by the redox potential of the each element. Arsenic?s oxidation state can be affected by the presence of Fe(III)-oxide in the anoxic zone. (Calvert and Pedersen, 2007; Widerlund and Ingri, 1995 ). Arsenic also has a complicated process of depositional migration in sediment. Cd does not change its valance as a function of the prevailing redox potential (Calvert and Pedersen, 2007). However, Cd concentrations can be readily affected by environmental factors such as salinity and pH (e.g., high presence of H2S). In addition, under certain environmental conditions Cd mobility in seawater changes rapidly and can influence the concentrations in surface sediment on short timescales (Ei Tun et al., 2009). Anoxic and oxic conditions play important roles in concentration analysis, which might influence the concentrations of As, Cd and Pb in the sediment. This suggests that the migration process of As, Cd and Pb at the surface of sediment interacting with the bottom water may influence the interpretation of concentrations in sediments.  In Barkley Sound, sediment from transect 3 (Empire Channel) has lower concentrations of As and Cd than transect 2 (Trevor Channel). Linder (2010) and Doe (1952) studied the water circulation in the Barkley Sound and concluded that water from Alberni Inlet circulates out mainly through Junction Passage to Imperial Eagle Channel and that Trevor Channel receives less water input from Alberni Inlet. This supports the inference that the relatively low As and Cd concentration in transect 3 are not the result of Port Alberni Inlet paper mill activities, and that  76 trace metals from the paper mill remain in the Alberni Inlet. Pb isotopic ratios provide a test of this hypothesis. The relative importance of anthropogenic vs. natural sources of Pb can be determined using the Pb isotope ?fingerprinting? technique (Chow et al., 1975; Simonetti et al., 2003; Cheng and Hu, 2010). In Alberni Inlet/ Barkley Sound, 206Pb/207Pb ratios in sediments become higher and 208Pb/206Pb become lower with increasing distance from Port Alberni. This suggests that the contribution of anthropogenic Pb decreases away from Port Alberni. However, the two most elevated concentrations of total Pb was observed in the upper inlet and Barkley sound. This suggests two possible explanations: (1) Two distinct sources contribute Pb to the upper inlet and Barkley Sound. (2) The elevated Pb in Barkley Sound is a result of Pb carried downstream from the first reservoir in the upper inlet. In a Pb-Pb isotope diagram (Figures 3.14, 3.15), data from this study are compared to other sediment and terrestrial rocks from Vancouver Island and modern anthropogenic Pb sources. The isotopic end members on this plot are natural Pb (e.g. Cascadia basin) and Sullivan Ore (most anthropogenic). The isotopic ratios of sediment from upper Alberni Inlet plot along a linear array between Sullivan Ore and Karmutsen basalt group on Vancouver Island. The compositions of the upper inlet sediments are therefore consistent with mixing between Karmutsen basalt and contamination from anthropogenic Pb. However, samples from the lower inlet and Barkley Sound (indicated as ?lower inlet? in Figure. 3.14, 3.15) define a linear array with a slightly lower slope than the upper inlet, which implies the contributions of the different Pb source in this area.  On 208Pb/206Pb vs. 206Pb/204Pb plots (Figure 3.9), Barkley Sound sediments fall within the linear array defined by three end-members: Karmutsen basalt, BC road dust which represents the Pb in gasoline (Preciado et al., 2007), and sediments drilled in the Cascadian basin in the  77 northern Pacific (Carpentier et al., in prep). The Barkley Sound sediments are therefore interpreted as representing a mixture of these three Pb sources. Sediment from the most distal site in Trevor Channel (site 7, 12, 15 and 18. Plotted in Figure 3.9) have an isotopic composition closer to that of the Cascadian basin, reflecting less anthropogenic input. This study therefore suggests that anthropogenic activities and industrial inputs from Port Alberni significantly contribute to the high total Pb concentrations in upper Alberni Inlet sediments. In contrast, anthropogenic sources other than the industrial effluent from Port Alberni (e.g., emissions associated with gasoline from boat traffic) make significant contributions of Pb to the lower inlet and to Barkley Sound.   78          Incidence of Toxicity (%) * Element TEC PEC <TEC TEC-PEC >PEC Arsenic 9.79 33.0 25.9** 57.6 76.9 Cadmium 0.99 4.98 19.6 44.6 93.7 Lead 35.8 128 18.4 53.6 89.6  Table 3.12. Potential adverse effect values.  TEC (threshold effect concentration) represents the value below which harmful effects are unlikely to be observed. PEC (probable effect concentration) represents the values above which harmful effects are likely to be observed. Values are given in ppm (dry wt). * Incidence of toxicity is defined in MacDonald et al. (2000). **i.e., 25.9 % of samples were identified as being toxic to one or more sediment dwelling organisms.   79    As (ppm) ? Cd (ppm) ? Pb (ppm) ? References Sediment Gulf of Venice, Italy     5-84  Donazzolo et al. (1981) Weser Estuary, Germany     25-142  Shoer et al. (1982) Belfast Inner Lough, UK     52-207  Smith and Orford (1989) Ganges Estuary, India     12-115  Turekian and Wedephohi (1961) Nakhu bay, Alaska   1.3  43 9 Meador et al. (1998) Skagway, Alaska     52 13 Meador et al. (1998) Elliot Bay, Alaska   1.3  67 22 Meador et al. (1998) Hunters Point, California (CA)   25 20 39 11 Meador et al. (1998) Oakland, CA 13 0.3   44 2 Meador et al. (1998) Oakland east, CA 14 0.8   99 10 Meador et al. (1998) Santa Monica, CA 43 20 4.6 3.6   Meador et al. (1998) San Diego, CA 13 1.2 1.6  73 32 Meador et al (1998)  Stream sediment   1.57 1.27 51 28 Callender (2003) and references therein.  Lake sediment   0.6  22  Callender (2003)  Deep sea Clay   0.4  80  Li (2000)  Oceanic sediment   0.05  0.03  Drever 1997  Average Crust 1.5  0.098  20  Taylor and McClennan 1985  Average Alberni Inlet 17 5 0.66 0.22 11.3 2.4 This study  Average Barkley Sound 11 3 0.36 0.12 12.2 5.0 This study  Table 3.13. Trace metal concentrations in sediments from different locations and the Earth?s crust. This table represents the concentrations of As, Cd, and Pb in different sample locations from other published data and this study (Units are ppm dry weight).  80  3.4.3 Pb input from Vancouver Island and Chinese loess in Barkley Sound  The isotopic compositions of Barkley Sound sediment show that the elevated concentration of trace metals is not only due to industrial wastewater input, but also reflects natural sources. In 208Pb/206Pb vs. 206Pb/207Pb and 208Pb/204Pb vs. 206Pb/204Pb diagrams (Figure 3.14 and 3.15), samples from the lower inlet and Barkley Sound (indicated as ?lower inlet?) form a linear array that is distinct from the linear array formed by upper inlet samples. As shown in Figure 3.14 and 3.15, upper inlet samples lie on a mixing line between two sources: the Sullivan Ore, which represents a primary anthropogenic source of Pb in Western Canada (leaded gasoline) (Simonetti et al., 2003; Shiel et al., 2013) that is released by the Port Alberni paper mill, and basement rocks form Vancouver Island. Increases in 206Pb/207Pb and 206Pb/204Pb in sediment with increasing distance from Port Alberni show that natural Pb contributions become more important away from Port Alberni. However, the distal site in Trevor Channel, where the Alberni Inlet ends, has less anthropogenic Pb input, which might be related to geological protection and oceanic current.   In contrast to the upper inlet, sediments from the lower inlet and Barkley Sound do not form linear arrays with Sullivan Ore and Vancouver Island (Figure 3.16). Jickells et al. (2005), McKendry et al. (2007) and VanCuren (2002) have shown that Asian dust is transported to North America and the Pacific Ocean. Input of Chinese loess into the lower inlet and Barkley Sound has Pb isotope ratios that can account for why the lower inlet sediments are shifted towards to high 208Pb/206Pb values for a given 206Pb/207Pb ratio. In addition, the results indicate that the 206Pb/207Pb and 206Pb/204Pb ratio of sediment increase with increasing distance from Port Alberni. This suggests the relative importance of natural contributions with increasing distance from Port  81 Alberni with the exception of the sediment from the most distal site in Trevor Channel where the Alberni Inlet ends. The Chinese loess input into Barkley Sound is documented into the elevated Pb concentrations; Gallet et al. (1996) reported that Chinese loess have Pb concentration of approximately 21 ppm, which is close to the values of Barkley Sound sediment (Table 3.2 and Figure 3.8). These results suggest that the Pb isotope signature in Barkley Sound is a mixture of anthropogenic, Chinese loess and Vancouver Island sources, and Chinese loess but no significant input of Chinese loess into Alberni Inlet.  Mixing calculations show that a mixture of ~ 13 % average Chinese loess and ~87 % upper inlet sediment provides a good match for the Al2O3 concentrations and Pb isotope ratio of lower inlet and Barkley Sound sediment. Concentrations of Al2O3, Fe2O3, CaO and Ti are significantly lower in Chinese loess { Al2O3 (6.8-7.2 wt. %), Fe2O3 (3.5-3.7 wt. %), CaO (4.8-7.8 wt. %) and TiO2 (0.42-0.44 wt. %)} (Liang et al., 2013) than in Barkley Sound sediments, but Pb concentrations are higher than most Barkley Sound sediments, confirming that addition of Pb to lower inlet sediments can significantly change Pb ratios without a major effect on major elements. Since upper inlet sediments are themselves a combination of anthropogenic Pb and natural Pb from Vancouver Island basement rocks, the Pb isotope signature of sediment in Barkley Sound is a mixture of these sources: BC primary anthropogenic, Chinese loess and Vancouver Island.     82    Figure 3.14. Plot of 208Pb/206Pb vs. 206Pb/207Pb diagram for Pb samples for sediment from this study compared to Vancouver Island geologic samples, Chinese loess, and the anthropogenic endmembers (Sullivan Ore). ?Upper Inlet? Samples are from Alberni Inlet and ?Lower Inlet? samples are from Barkley Sound. Black lines indicate the two linear trends defined by the upper and lower inlet. The upper inlet trend intersects with Vancouver Island geologic samples and Cascadia basin sediment samples, but the lower inlet trend has a different slope. Inset shows same data on an expanded scale to show how the upper inlet samples lie on a trend between Sullivan Ore and Vancouver Island geologic samples. Geologic samples from Vancouver Island are from Schoen Lake (Greene et al., 2009), Karmutsen Volcanic Whole Rock (Vol WR) and Sicker group (Andrew and Godwin, 1989). Chinese Loess is from Choi et al. (2007) and Jones et al. (2000). ODP data are Cascadia basin sediments from sites 888 and 1027 (Carpentier et al., in prep). Sullivan Ore is from Sangster et al. (2000).   83   Figure 3.15. 208Pb/204Pb vs. 206Pb/204Pb for sediment from this study compared to local geologic samples, Chinese loess, and anthropogenic endmembers (Sullivan Ore). ?Upper Inlet? Samples are from Alberni Inlet and ?Lower Inlet? samples are from Barkley Sound. Black lines indicate the two linear trends defined by the upper and lower inlet. The upper inlet trend intersects with Vancouver Island geologic samples and Cascadia basin sediment samples, but the lower inlet trend has a different slope. Inset shows same data on an expanded scale to show how the upper inlet samples lie on a trend between Sullivan Ore and Vancouver Island geologic samples. Geologic samples from Vancouver Island are from Schoen Lake (Greene et al., 2009), Karmutsen Volcanic Whole Rock (Vol WR) and Sicker group (Andrew and Godwin, 1989). Chinese Loess is from Choi et al. (2007) and Jones et al. (2000). ODP data are Cascadia basin sediments from sites 888 and 1027 (Carpentier et al., in prep). Sullivan Ore is from Sangster et al. (2000).    84    Figure 3.16. 208Pb/206Pb vs. 208Pb/207Pb showing lower inlet and Barkley sound sediments as a mixture of three end-members: anthropogenic Pb, Vancouver Island basement rocks, and Chinese loess. Lower inlet and Barkley Sound samples are indicated by the red field, upper inlet sediments by the dark blue field, basement rocks in the orange field (labeled ?sediment source?), and Chinese loess in the light blue field. Large black arrow points in the direction of Sullivan Ore, which represents anthropogenic lead. Data sources given in Figure 3.14 and 3.15.       85    Most radiogenic Upper inlet sediment sample (Site 24)  Average Chinese loess*   Mixture of 13 % Loess 87 % Upper Inlet Sediment  Most radiogenic Lower Inlet Sediment Sample (Site 9)  Al2O3 concentration (wt %)  14.88  6.84 (5.75-8.59)  12.94  **12.77  (12.03-13.79)  [Pb] (ppm)  6.9  21 (20-23)  8.7  15  208Pb/206Pb  2.06397  2.0887  2.07169  2.07190  Table 3.14. Modeling the 13% Chinese loess input into the Barkley Sound The Al2O3 concentrations and isotopic ratios of the most radiogenic site from the upper inlet (first column) and lower inlet (last column) were used as end-member and target compositions, respectively. *Chinese loess represents the data from Yellow Sea sediments with Al2O3 (wt %) from Yang et al. (2003) and Pb concentration from Gallet et al. (1996) and references therein. Pb isotopic composition is from Choi et al. (2007) and Jones et al. (2000). **The average value of all Barkley Sound sediment samples in this study (Site 7.8.10.12.14. and 17).    86  3.4.4 Explaining concentration change in core sample by disturbances related to the Alaska tsunami in 1964 using sedimentation rate in Barkley Sound basins The core sediment results did not indicate a significant difference comparing to the surface sediment (50 to 80 years) result, certain depth of the core sample concentration represented a noteworthy increase and decrease. The average from these values yields a sedimentation rate of 0.18 cm year-1 in the Alberni Inlet and Barkley Sound and using this value helps to understand the sudden decrease of concentration of trace metals in Core 6 (Distance from the mill: 40 km) and increase in Core 2 (Distance from the mill: 1 km). The depth where there is a sudden change in concentration of trace elements (Figure 3.10) occurs (11 ? 25 cm) has a calculated age of approximately 30 to 70 years, i.e. corresponding to the arrival of the 1964 Alaska tsunami in Port Alberni. The isotopic composition in the core samples also documents an abrupt chance in core 6 and slight composition change in cores 4 and 5, which are both located in Barkley Sound. Clague et al. (1994) studied a sand sheet in Port Alberni by using 137Cs dating and concluded that the Alaska tsunami deposited the sand layer in Port Alberni tidal mud in 1964. Based on this, it is possible that the sediment core samples concentration can present the massive movement of water and sediment into the inlet from the Pacific Ocean by the Alaska tsunami, which might account for the anomalies observed in cores 2 and 6.  The depletion of concentration at Site 2 (Figure 3.10) is the result of dilution by sand that was carried by the tsunami from the Pacific Ocean and deposited in the upper inlet. Alternatively, suspended sediment in the upper inlet was carried by the down stream after the tsunami and deposited at lower inlet at Core 6 causing an increase in concentration. This only demonstrates the effectiveness of calculating the approximate age of sediment by using sedimentation rates  87 that were presented in Clague et al. (1994) and Townley (1999) as sedimentation rate in Barkley Sound to indicate some possible occurrence in sediment by Alaska tsunami.  88  3.5 Conclusions To assess the impact of the paper mill downstream, we investigated the distribution of trace metals in Alberni Inlet and Barkley Sound focusing on As, Cd, and Pb concentration and Pb isotopes and reached the following conclusions:  1. The high concentrations of As, Cd, and Pb in the Alberni Inlet indicates that the deposition of suspended element occurs at a distance of 10 to 25 km from Port Alberni in the Alberni Inlet. Within this inlet, the concentration progressively decreases and suggests that the paper mill in Port Alberni is responsible for elevated As, Cd, and Pb concentrations in the sediments at the headwater to the end of the Alberni Inlet. Lead isotopic signatures support this observation, which a mixing trend between anthropogenic and natural Pb in the Alberni Inlet. 2. The Pb isotopic signature identifies the mixing of anthropogenic Pb from pulp and paper mill located at the head of the Alberni Inlet and Vancouver Island Pb compositions within the Alberni Inlet. In the Alberni Inlet, Vancouver Island Pb seems to be the primary source and a dilution of the Pb isotopic signature occurs due to input of anthropogenic Pb. In Barkley Sound, an additional input by Chinese loess is observed in the sediment.  3. Major element/Al2O3 ratio and Al2O3 (wt %) trends document the terrestrial input of Karmutsen basalt from Vancouver Island into Alberni Inlet and Barkley Sound. This is also supported by the C/N ratio, which is used to discriminate the two different possible sources of carbon, terrestrial vs. marine, in Alberni Inlet and Barkley Sound. Major element indicates the mixing of the two sources of sediment (Karmutsen Formation and  89 Bonanza Arc system) and C/N ratio suggests the high terrestrial organic input into Alberni inlet. 4.  Core sediment sample concentrations show an abrupt change in the water column at a depth corresponding to the 1964 due to the Alaska tsunami, when massive sand layers were carried upwards into the sound.  90 Chapter  4: Conclusion 4.1 Summary and conclusions Alberni Inlet and Barkley Sound are located downstream from the city of Port Alberni on Vancouver Island, British Columbia. This study has quantified the relative contribution of anthropogenic contamination into Alberni Inlet and Barkley Sound using major elements, environmentally monitored trace metal (As, Cd, and Pb) concentrations and Pb isotopic composition in sediment. Major element data indicate that the major source of Barkley Sound and Alberni Inlet sediments is Vancouver Island bedrock. However Pb isotope ratios of sediment samples document that two additional sources contribute to Alberni Inlet and Barkley Sound, anthropogenic input from the paper mill at Port Alberni and natural input form wind-blown Chinese Loess. The results of this study lend support to the effectiveness of Pb isotopic fingerprinting in tracing environmental pollution. Lead isotopic compositions of sediments from the upper Alberni Inlet and Lower Alberni Inlet define two distinct linear arrays in 208Pb/206Pb vs. 206Pb/207Pb and 208Pb/204Pb vs. 206Pb/204Pb diagrams. Upper inlet sediments form an array extending between two sources, Vancouver Island bedrock samples and an anthropogenic source approaching the composition of the Sullivan Ore. The paper mill located at the headwater seems to be the primary source of anthropogenic input into the Alberni Inlet. Samples with greatest anthropogenic contributions are correlated with the highest concentrations of As, Cd, and Pb. In contrast to the upper inlet, sediments of the lower inlet have Pb isotope ratios that are shifted to slightly higher 208Pb/206Pb values by a small amount of input from a third source, Chinese loess. Relatively high concentrations of Pb were also identified in Barkley Sound, but Pb isotopes point to an unknown source rather than the Port Alberni paper mill, possibly boat traffic and human activities, which are widespread in this area.   91 Natural archives such as sediment cores, tree rings and peat deposits are an important source of information on the evolution of Pb source (using the isotope fingerprinting technique) through time. Knowledge of the Pb isotopic ratios of pre-anthropogenic, natural and newer anthropogenic sources are critical for understanding the evolutions of Pb contamination into the environment (Savard et al., 2006). In this study, a historical disruption in trace metal concentration is observed at one level within sediment core samples. Based upon sedimentation rates, this level is estimated to be the same age as the historical Alaskan tsunami in 1964. This study demonstrates the effectiveness of using Pb isotopes in conjunction with trace metal concentrations to provide a better understanding of the contaminant pathways into the environment.   Although, monitoring of trace elements in wastewater from the Port Alberni paper mill began about a decade ago, no case of environmental contamination has been publicized since the paper mill began operating. In all samples examined in this study, the concentration of As, Cd, and Pb are lower than the probable effect concentrations, indicating that the primary concern for human and biota exposure from Alberni Inlet and Barkley Sound sediment is low (MacDonald et al., 2000; Long et al., 1995). However, the arsenic concentration is higher than the Sediment Quality Guidelines (SQGs) threshold effect concentration and could potentially have some effect on benthic organisms bottom at the present concentration. Therefore, monitoring trace metal concentrations in the sediment and the effect on the organisms are recommended.  The improvement in ICP-MS techniques and the growing archive of isotopic compositions for trace metals in environment has contributed to a high number of publications in elements other than As, Cd and Pb. A thorough investigation of the ICP-MS limitations, in regard to the element of interested, emphasizes the importance of instrumental set ups and  92 knowledge of the dynamic range of concentration analysis in obtaining high quality data. The future of ICP-MS may provide more precise and accurate analytical data by providing better detection limits and minimizing oxide interferences in trace element studies.  4.2 Suggestions for future research The study of trace element concentrations analysis and Pb isotope fingerprinting in Alberni Inlet and Barkley Sound sediments can be extended into the following future research:   (1) Determination of trace element concentrations in water samples. Elements that are deposited within effluent from the paper mill can be dissolved in the river and inlet water instead of scavenging onto the bottom sediment. For example, determining the quantities of dissolved trace metals in the water will provide constraints about the flux of trace element into the sediment.  (2) The speciation of As and understanding of diagenesis in the sediment. Since arsenic is a monoisotopic element, it cannot be utilized for isotopic fingerprinting. However the study of Zheng et al. (2003) has used high-performance liquid chromatography (HPLC) with ICP-MS to determine the speciation of As (V) and As (III) in organic compound, which can provide more insight on terrestrial input from inorganic and organic compounds. Such information might reveal a reason for why only the As concentrations are above the SQGs probable effect concentration in this study.  (3) Measurement of Cd isotopic compositions in Barkley Sound and Alberni Inlet, and comparison to the isotopic compositions in the oysters from Barkley Sound (Shiel et al., 2012). This would allow for a better knowledge on how Cd circulates in the  93 Alberni Inlet and Barkley Sound; the Pb isotopic data only suggest that oysters were highly contaminated with an anthropogenic source. The Cd isotopic composition can be incorporated with trace element concentrations and SQGs concentrations to determine potential health concerns associated with human consumption of oysters from Barkley Sound.  (4) Dating the core samples by using 210Pb and 137Cs. In the present study, ages were estimated for samples from sediment cores by applying average literature sedimentation rates. However, sedimentation rates specific to Alberni Inlet and Barkley Sound are not known, leading to potentially large uncertainties in our age estimates. Accurate age date for the samples from this study could be determined using 210Pb and 137Cs, which would provide better understanding of the abrupt concentration change in the core samples and would contribute useful information for future research in Alberni Inlet and Barkley Sound.    94 References  Adekola, F. A., & Eletta, O. A. A. (2007). A study of heavy metal pollution of Asa River, Ilorin. Nigeria; trace metal monitoring and geochemistry. Environmental monitoring and assessment, 125(1-3), 157-163.  Agilent Technologies. (2005). ICP-MS inductively Coupled Plasma Mass Spectrometry, Primer, Agilent Technologies, Inc. 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Prenatal exposure to lead and cognitive deficit in 7-and 14-year-old children in the presence of concomitant exposure to similar molar concentration of methylmercury. Neurotoxicology and teratology, 33(2), 205-211.  Young, D. R., Alexander, G. V., & McDermott-Ehrlich, D. (1979). Vessel-related contamination of southern California harbors by copper and other metals. Marine Pollution Bulletin, 10, 50-5  Zheng, J., Hintelmann, H., Dimock, B., & Dzurko, M. S. (2003). Speciation of arsenic in water, sediment, and plants of the Moira watershed, Canada, using HPLC coupled to high resolution ICP?MS. Analytical and bioanalytical chemistry, 377(1), 14-24.  Zhang, J., Nozaki, Y. (1996) Rare earth elements and yttrium in seawater: ICP-MS determinations in the East Caroline, Coral Sea, and South Fuji basins of the western South Pacific Ocean, Geochimica et Cosmochimica Acta, 60, 4631-4644.   106           Appendices  107  Appendices  Appendix A  Supplementary samples from Fraser River  Introduction The Fraser River is one of the largest rivers in British Columbia at 1370 km in length and discharging approximately 217,000 km2 of water into the Pacific Ocean. The headwater is located near Jasper, Alberta in the Rocky Mountains, and only passes through one lake (Moose Lake) along its course to the Strait of Georgia (Thomson, 1981; Cameron and Hattori, 1996). There have been multi efforts to maintain the preservation of Fraser River resulting little disturbance (i.e., hydroelectric dam) to control the water flow to the Pacific Ocean. This means that the suspended material and water represents the glacial sediment from the Rocky Mountains and is of high interest to characterize the geochemical composition of the terrestrial input of sediment into the North-East of Pacific Ocean. While there are no anthropogenic disturbances distal to the Fraser River, the industrial input and wastewater input significantly increases once the water reaches Grater Vancouver (NPRI Environmental Canada, 2011).   The initial propose of this project was to understand and demonstrate sample preparation for lead (Pb), strontium (Sr), neodymium (Nd), and hafnium (Hf) isotopic analysis in water and suspended materials from the Fraser River. Furthermore, we intended to study palaeoceanography with an extension of previous studied data from Cameron and Hattori, (1996) to quantify the suspended material that fed the sediment into the Strait of Georgia.     108 Sample selection  Sampling was done on July 5th, 2010, by Drew Snauffer and Olivier Menard, and March 24th, 2011 by Mariko Ikehata and Drew Snauffer along the north arm of Fraser River by the Go-Flo water sampler for trace metal analysis (Appendix B and Appendix C). 20 L samples were taken per site and transferred into a jerry-can with a minimum contamination of metals. The focus of sampling in 2011 was comparing seasonal change in the water sample and obtain some samples form the location where river water meets the Strait of Georgia. After sampling, the water was transferred to University of British Columbia (UBC) and refrigerated at 4 ?C until further processing.   Sample preparation and analytical methods  All water samples were filtered with 47 mm 0.8 ?M Versapor 800 filter gravitationally into 20 L cubitainer in pre-weighed milk crate and acidified by concentrated HCl (40-50 ml) to a pH ~2 to store for further analysis. Approximately 1 L of water sample was separated for concentration analysis and the rest was refrigerated. After the filtration process, some of the suspended material that sank to the bottom of the container was recovered in a 50 ml centrifuge tube and centrifuged. The supernatant was discarded and the suspended materials was dried and used for further analysis. Suspended material and filtered sediments were analyzed for trace element (TE) and rear earth element (REE) concentration as well as Pb-Nd isotopic composition.   Experimental work was carried out in a metal free Class 1000 clean laboratory at the Pacific Centre for Isotopic and Geochemical Research (PCIGR), UBC. The sample preparation of sediment for concentration analysis and isotopic analysis are indicated in Section 3.2.2. Nd chromatographic purification and analysis followed the method described in Weis et al. (2006).  109 Nu Plasma (Nu 021; Nu Instruments, UK) multi-collector inductively coupled plasma mass Spectrometer (MC-ICP-MS) was used for Hf and Nd isotopic analysis. Agilent 7700x Quadrupole ICPMS was used for concentration analysis at the PCIGR and the analytical settings are presented in Chapter 2 and Chapter 3.   Results and discussion  Primary result presented in this study suggests high concentration of environmental monitored elements (Cd, Cu, Zn, Cr, Pb) in the suspended material and filtered material matter (Appendix A.7). This may be due to the wastewater treatment plant (primary treatment) located on Iona Island at the end of Fraser River, causing sample contamination. In addition, the number of industrial waste sources into the lower Fraser River is significantly high (Environment Canada, 2011) from the industrial and commercial shipping, which also contributes to the contamination of river water and sediment. Further studies are necessary to indicate the source of contamination in this area in order to understand the composition of Fraser River from the headwater and discriminate anthropogenic input. Since the area where samples were obtained is contaminated, it is hard to determine the natural composition of upper Fraser River water.   Recommendations for future work The study of Fraser River water has many possible avenues for further research. In terms on the initial purpose (understanding the palaeoceanography of Fraser River to the Pacific Ocean) of these samples, it is necessary to obtain the samples from further up stream, where the industrial input and wastewater contributions are negligible. This also opens the possibility for an  110 environmental study in the lower Fraser River to understand and determine the source for the contamination of high environmental trace elements and its effect on the environment.   A. References Cameron, E. M., & Hattori, K. (1997). Strontium and neodynium isotope ratios in the Fraser River, British Columbia: a riverine transect across the Cordilleran orogen. Chemical geology, 137(3), 243-253.  Thomson, R. E. (1981). Oceanography of the British Columbia coast (Vol. 56, p. 291). Sidney, BC: Department of Fisheries and Oceans.  Weis, D., Kieffer, B., Maerschalk, C., Barling, J., De Jong, J., Williams, G. A., Hanano, D., Pretorius, W., Mattielli, N., Scoates, J.S., Goolaerts, A., Friedman, R. M., Mahoney, J. B. (2006). High-precision isotopic characterization of USGS reference materials by TIMS and MC-ICP-MS. Geochemistry Geophysics Geosystems, 7, Q08006, doi: 10.1029/2006GC001283    111  A.1 Sample data for July 5th, 2010 Jerry-can number latitude Longitude Depth (m) Salinity (ppt) Temperature (?C)  Time distance from first sample (m) 10 49?11.832N 122?54.521W 2 to 3 0 14.3 9:15 0 11 49?11.208N 122?59.681W 2 to 3 0 14 9:30 6253.17 12 49?12.280N 123?03.535W 2 to 3 0 14.1 9:45 11338.61 13 49?12.884N 123?09.975W 2 to 3 0 14.3 10:13 19209 14 49?14.962N 123?15.736W 2 to 3 4.5 14.9 10:54 27179.18 19 49?15.010N 123?15.829W 2 to 3 3.8 14.9 12:05 27325.74 15 49?15.189N 123?16.117W 2 to 3 7.2 15.4 11:03 27803.12 16 49?15.460N 123?16.495W 2 to 3 7 15.9 11:15 28480.65 17 49?15.663N 123?16.818W 2 to 3 8.8 15.1 11:30 29017.15 18 49?15.671N 123?17.318W 2 to 3 12.6 16 11:45 29624 8 49?15.671N 123?17.318W 2 to 3 12.4 16 11:50 29624 9 49?15.010N 123?15.829W 6 to 7 22.4 14.8 12:15 27325.74    112  A.2 Sample data for March 24th, 2011 Jerry-can number Latitude Longitude depth (m) Salinity (ppt) Temperature (?C) Time distance from first sample (m) 1 49?15.487N 123?17.437 2 26 7.5 9:45 0 2 49?15.487N 123?17.437 2 26 7.5 9:45 0 3 49?15.138N 123?15.971  25.4 7.3 10:21 1860 4 49?13.372N 123?12.594  22.6 7.2 10:41 7100 5 49?12.971N 123?10.963 16.5 19.2 6.9 10:57 2140 6 49?12.768N 123?07.437 7.8 2 6.7 11:13 10600 7 49?12.064N 123?05.611 5 7 6.5 11:36 14200 8 49?11.856N 122?54.247 2 3.2 6.2 11:48 16300 9 49?12.023N 122?54.337 0.1 0.1 5.4 12:20 31500 10 49?12.010N 122?58.467 0.1 0.1 5.4 12:27 31500 11 49?10.792N 123?58.467 0.1 0.1 5.8 12:43 25700 12 49?12.888N 123?10.388 8 16 6.9 13:11 10000 13 49?13.008N 123?11.095 9.7 17 7 13:25 9000   113  A.3 REE concentration for suspended material in ppm. ??????? ?? ?? ?? ?? ?? ?? ?? ? ? ? ? ? ? ? ?? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ? ? ? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ???????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????    114   A.4 REE concentration of suspended material normalized to PAAS. ??????? ?? ?? ?? ?? ?? ?? ?? ? ? ? ? ? ? ? ???? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? ????? ?????    115  A.5 Trace element concentration in suspended material in ppm ??????? ?? ?? ?? ?? ?? ? ? ? ? ? ? ? ?????? ????? ????? ????? ????? ????? ????? ????? ????? ??????????? ????? ???? ????? ???? ????? ????? ????? ???? ??????????? ???? ???? ???? ???? ???? ???? ???? ???? ????????? ???? ???? ???? ???? ???? ???? ???? ???? ????????? ????? ???? ????? ???? ???? ???? ???? ???? ?????????? ????? ????? ????? ????? ????? ????? ????? ????? ??????????? ???? ???? ???? ???? ???? ???? ???? ???? ?????????? ???? ???? ???? ???? ???? ???? ???? ???? ?????????? ???? ???? ???? ???? ???? ???? ???? ???? ???????? ???? ???? ????? ???? ???? ???? ????? ????? ??????????? ????? ????? ????? ????? ????? ????? ????? ????? ??????????? ????? ????? ????? ????? ????? ????? ????? ????? ?????????? ????? ????? ????? ????? ????? ????? ????? ????? ?????????? ????? ????? ????? ????? ????? ????? ????? ????? ??????????? ????? ????? ? ? ? ????? ????? ????? ????? ????? ?????????? ?????? ?????? ?????? ?????? ?????? ?????? ?????? ?????? ??????????? ?????? ????? ?????? ????? ????? ????? ????? ????? ??????????? ?????? ?????? ?????? ?????? ?????? ?????? ?????? ?????? ??????????? ?????? ????? ?????? ?????? ?????? ?????? ?????? ? ? ? ??????   116  A.6 Environmentally monitored trace element concentration in suspended material in ppm ??????? ?? ?? ?? ?? ?? ? ? ? ? ? ? ? ?? ? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ????? ????? ????? ????? ????? ????? ????? ????? ?????? ? ?????? ?????? ?????? ?????? ?????? ?????? ?????? ?????? ??????? ? ????? ????? ????? ????? ????? ????? ????? ????? ????? A.7 Pb concentration in suspended material in ppm  ?? ?? ?? ?? ?? ?? ?? ? ? ? ? ? ? ? ???? ? ??? ? ?? ? ?? ? ?? ? ?? ? ??? ? ?? ? ?? ? ?? ? ??? ?   117  A.8 Pb isotope ratio for suspended material     208Pb/204Pb 2 SE 207Pb/204Pb 2 SE 206Pb/204Pb 2 SE 208Pb/206Pb 2 SE 206Pb/207Pb 2 SE Suspended material 1  37.434 3 15.5705 10 17.7000 8 2.1150 5 1.13677 2 3  37.863 2 15.5983 7 18.0703 8 2.0953 4 1.15849 2 4  37.952 2 15.6032 6 18.1771 7 2.0879 4 1.16495 1 5  38.046 2 15.6081 8 18.2699 9 2.0825 4 1.17054 2 6  38.192 2 15.6157 8 18.4353 9 2.0716 4 1.18058 1 7  37.867 4 15.5938 12 18.1278 10 2.0889 9 1.16982 3 8  37.959 2 15.5994 7 18.2257 7 2.0828 3 1.16838 1 9  38.283 2 15.6192 8 18.5666 8 2.0619 4 1.18868 2 10  37.890 2 10.6743 7 17.0458 8 1.6473 4 1.17255 2 11  38.133 2 13.3695 8 17.0622 9 1.9422 4 1.18753 1 12  38.116 2 15.6132 7 18.3479 8 2.0774 3 1.17514 1 13  37.942 2 15.5977 9 18.1836 10 2.0866 4 1.16578 2 7 Duplicate  37.861 2 15.5941 6 18.1208 7 2.0894 5 1.16202 1 9 Duplicate  38.291 2 20.6617 9 17.0736 10 2.5302 3 1.19968 1 10 Duplicate  37.902 2 15.5928 8 18.1859 8 2.0841 4 1.16629 1 12 Duplicate  38.066 3 15.6075 9 18.3106 9 2.0789 4 1.17321 2 8 Replicate  37.997 2 15.6023 9 18.2705 10 2.0797 4 1.17103 2 10 Replicate  37.922 2 15.5945 7 18.2033 8 2.0833 4 1.17469 1      10 Replicate 2 37.922 2 15.5945 7 18.2033 8 2.0833 4 1.17469 1     118 A.9 Pb isotope ration for filtered particulates  ? ? 208Pb/204Pb 2 SE 207Pb/204Pb 2 SE 206Pb/204Pb 2 SE 208Pb/206Pb 2 SE 206Pb/207Pb 2 SE ????????????? ?????? ? ??????? ?? ???????? ?? ???????? ?? ??????? ?? ???????? ???? ? ??????? ?? ???????? ?? ???????? ?? ??????? ?? ???????? ???? ? ??????? ?? ???????? ?? ???????? ?? ??????? ?? ???????? ???? ? ??????? ?? ???????? ?? ???????? ?? ??????? ?? ???????? ??? ? ? ??????? ?? ???????? ? ? ???????? ? ? ??????? ? ? ???????? ??? ? ? ??????? ?? ???????? ?? ???????? ? ? ??????? ?? ???????? ??? ? ? ??????? ?? ???????? ?? ???????? ?? ??????? ?? ???????? ?????????????? ? ??????? ?? ???????? ?? ???????? ?? ??????? ?? ???????? ?????????????? ? ??????? ?? ???????? ?? ???????? ?? ??????? ?? ???????? ??    119 A.10 Nd isotope ratio for suspended material and filtered particulates  Site # 143Nd/144Nd 2SE Suspended material 3 0.512186 4  4 0.512245 3  5 0.512377 3  6 0.512494 3  7 0.512568 3  8 0.512620 3  9 0.512605 3  10 0.512679 3  11 0.512575 2  12 0.512424 3  13 0.512506 3 Replicate   0  4 0.512322 3  7 0.512546 3  8 0.512631 3  9 0.512560 3  11 0.512570 3  12 0.512358 3  13 0.512513 3 Duplicate 5 0.512437 3  7 0.512518 4  10 0.512637 4 Filtered particulates     6 0.512641 5  7 0.512679 3  12 0.512544 4 Duplicate 6 0.512653 4  7 0.512650 4  12 0.512678 3  120  Appendix B   Calculating anthropogenic input into the Barkley Sound The modeled % of anthropogenic Pb in total concentration is presented by using calculation;  Sample Al3O2 (ppm) x Site 7 Pb (ppm)/ Site7 Al3O2 (ppm) = Natural Pb (ppm) Anthropogenic Pb (ppm) = Total Pb (ppm) ? Natural Pb (ppm)  The % value was calculated by assuming the lowest Pb concentration site 7, furthest from Port Alberni, contains no anthropogenic Pb in total concentration. Nature of Al2O3 input was used to quantify the anthropogenic Pb since its behavior of Al2O3 that only sourced from natural input to the sediment. The % input of anthropogenic suggests the domination of its input in the Barkley Sound and this is even higher value compare to the upper inlet value.  B.1 The calculate value of anthropogenic Pb (%) in the sediment It suggests the high input is high in the upper inlet and lower inlet. However, the lower inlet cannot be indicated as anthropogenic Pb since the Pb isotope suggests the Chinese loess input.   

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