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Geochemistry in the hyporheic zone of the lower Fraser River Roschinski, Tilman Gordon 2007

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Geochemistry In The Hyporheic Zone Of The Lower Fraser River by Tilman Gordon Roschinski B.Sc, The University of British Columbia, 2004 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in The Faculty of Graduate Studies (Geological Sciences) THE UNIVERSITY OF BRITISH COLUMBIA August 2007 © Tilman Gordon Roschinski 2007 Abstract The geochemistry of the hyporheic zone was investigated to reduction-oxidation (redox) conditions across the hyporheic zone as groundwater and river water mix in the shallow sediments of the lower Fraser River, a large, tidally influenced 9 t h order river. The site selected for study is located at the trailing edge of a post-glacial river delta deposit near Vancouver, British Columbia approximately 30 km upstream from the mouth of the river. Pore water samples were collected with a drive-point profiler while sediment cores were collected with a freeze-shoe corer. Difficulties encountered with the freeze-shoe corer led to the development of a novel tool: a liquid nitrogen-cooled freeze corer capable of sampling undisturbed sediments in a deep river environment. Selective single-step chemical extraction procedures were used to analyze sediment samples for secondary iron mineral precipitates that commonly form in the hyporheic zone where iron-rich anaerobic groundwater mixes with oxygen-rich surface water. Results of sediment analyses show a significant amount of iron in the sediments, but no distinct peak accumulations indicative of secondary iron mineral precipitates and no accumulation of iron oxyhydroxides on the hyporheic zone sediments, suggesting that oxygen does not enter the hyporheic zone in significant concentrations. It is hypothesized that oxidation of dissolved organic carbon and methane could remove oxygen and therefore maintain reduced ferrous iron in solution. X-ray diffraction detected the presence of iron-bearing chlorite and a magnetic separation found concentrations of magnetite. The presence of these minerals is thought to be the cause for the high concentrations of iron in the sediments by chemical extraction. Though no significant amounts of oxygen from river water is thought to enter the hyporheic zone sediments, chloride concentration profiles indicate that river water does mix with groundwater in the hyporheic zone. Where the river sediments are silt-dominated, river water appears to penetrate to less than one meter depth, whereas in sand-dominated sediments river water penetrates to at least 1 to 1.5 meters depth. Table of Contents Abstract '.• ii Table of Contents iv List of Figures vii Acknowledgements ix 1. Introduction 1 1.1 Purpose of Research 2 1.2 Thesis Outline 2 2. Literature Review 4 2.1 Previous Hyporheic Zone Studies 4 2.2 Review of Extraction Methods 6 3. Site Description 9 . 3 . 1 Previous Research and History of the Site 9 3.2 Geology and Hydrogeology at the Site 11 3.3 Geochemistry 13 4. Methods 15 4.1 Sample Collection 15 4.1.1 Sediment Core Collection 16 4.1.1.1 2005 Cores 16 4.1.1.2 Summer 2006 Cores 18 4.1.2 Simultaneous Core and Pore Water Collection 19 4.1.3 Water Sample Collection 23 4.2 Sample Analyses 25 4.2.1 Water Samples 25 4.2.2 Sediment Analyses 27 4.2.2.1 Sediment Extractions 27 4.2.2.2 Scanning Electron Microscopy 28 4.2.2.3 Rietveld X-Ray Diffraction 28 5. Results and Discussion 30 5.1 Sediment Stratigraphy and Groundwater Flow 30 5.1.1 Rietveld X-Ray Diffraction and Scanning Electron Microscopy 32 5.2 Results of Water Analyses 33 5.2.1 Organics 33 5.2.2 Conservative Tracer Concentrations 35 5.2.3 Redox Sensitive Species Concentrations 36 5.2.4 Geochemical Modelling 37 5.3 Results of Sediment Extractions 38 5.3.1 Speciation of Iron Extracts 38 5.3.2 Results of Total Iron Concentrations 39 6. Conclusions 41 6.1 Depth of the Hyporheic Zone 41 6.2 Iron Accumulation and Redox Conditions 41 7. Summary 45 References 80 Appendix A - Results of Chemical Analyses of Water Samples 86 Appendix B - Results of Selective Extractions of Sediment Samples 97 Appendix C - Lab Procedures for Iron Sediment Extractions 110 Appendix D - Analysis Procedure for PAH Analyses of Water Samples 117 Appendix F - PhreeqC Geochemical Modelling Input File 119 v List of Tables Table 1: Types of water samples collected 47 Table 2: Sediment extractions used in this study 47 Table 3: Core logs for core C1-05 and C3-05 48 Table 4: Core logs for cores C2-05, C1-06, C2-06, C4-06 49 Table 5: Core log for core C12-06 50 Table 6: Percentage of minerals identified by Rietveld XRD analysis 50 Table 7: Saturation indices for water samples 51 Table 8: Statistics of iron concentrations of 1M CaCI 2 extractions 52 Table 9: Statistics of iron concentrations of 0.75 M HCI extractions 52 Table 10: Statistics of iron concentrations of 5M HCI extractions 52 vi List of Figures Figure 1: Map of Western Canada with the Fraser River drainage basin outlined 53 Figure 2: Map of the Lower Mainland with arrow pointing to field site 54 Figure 3: Aerial photo of field site showing location of cross-section and hyporheic zone 55 Figure 4: Cross-section of geology with hyporheic zone showing 56 Figure 5: Cross-section showing aquifer hydrogeology 57 Figure 6: Photograph of boat used for sampling at the field site 58 Figure 7: Schematic of boat with sampling gear deployed 59 Figure 8: Photograph of core barrel with freeze-shoe sampler 60 Figure 9: Schematic of freeze-shoe corer 60 Figure 10: Aerial photo of filed site showing sampling locations 61 Figure 11: Cross-section of field site showing sampling locations 62 Figure 12: Annotated photograph of the Phleger corer 63 Figure 13: Schematic of freeze-corer as deployed from boat 64 Figure 14: Schematic of freeze-corer tool 64 Figure 15a, b, c: Photographs showing sampling assembly being lifted into place 65 Figure 16: Photograph of liquid nitrogen tank connected to sampling assembly 66 Figure 17: Photograph of frozen sediment core being retrieved 66 Figure 18: Close-up photograph of frozen sediment core 67 Figure 19: Schematic of pore water profiling gear 68 Figure 20: Photograph of pore water profiling gear on the boat 69 Figure 21: SEM picture of iron sulphide mineral 70 Figure 22: SEM picture of amorphous iron mineral coating 70 Figure 23: Pore water profiles of P6-05, P22-05 and P23-05 showing contaminant, iron and methane concentrations 71 Figure 24: Statistical graphs correlating methane and iron concentration vs. contaminant concentration 72 v i i Figure 25: Pore water profiles showing concentrations of chloride and iron 73 Figure 26: Pore water profiles showing concentrations of dissolved oxygen, sulphate, methane and conductivity 74 Figure 27: Graphs showing ferrous iron concentrations in 2005 sediment cores C1-05, C2-05, C3-05 75 Figure 28: Graphs showing total iron concentrations in 2005 sediment cores C1-05, C2-05, C3-05 76 Figure 29: Graphs showing total iron concentrations in 2006 sediment cores C1-06, C2-06, C4-06 77 Figure 30: Graphs showing total iron concentrations in 2006 sediment core C12-06 78 Figure 31: Graph and data showing results of timed sediment extraction 79 viii Acknowledgements I would like to thank my supervisors Dr. Roger Beckie and Dr. Leslie Smith for their useful advice, guidance and encouragement. Their expertise has guided my work throughout. It was especially helpful to have two good-natured supervisors always readily available for questions. I also appreciate the help I received from my fellow grad students in the hydro-group who have willingly assisted with my work in the field and supported me through friendship in the office. I especially would like to thank Mario Bianchin for the organization of much of the field work and Kellyann Ross for help with the field work. I am also grateful to the governments of Canada and British Columbia for providing funding for my research, letting me study here and administering the country and the province in such a way as to provide for a peaceful and agreeable living environment. ix 1. I n t r o d u c t i o n The accidental release of contaminants into aquifers that ultimately discharge into rivers is of increasing concern as industrial developments are frequently located close to major river systems (Westbrook 2005). It has long been observed that groundwater discharging into a river mixes with the surface water in the shallow sediments of the river, termed the hyporheic zone. While various definitions exist for the hyporheic zone (Schwoerbel 1961, White 1993), for this study it is defined as the subsurface zone beneath the body of water in which groundwater and surface water mix. Groundwater and surface water usually have distinctly different chemical signatures (e.g. Benner et al. 1995, Arntzen et al. 2006, Kalbus et al. 2006, in review), which leads to chemical reactions that, along with biological processes, can have an impact on the degradation and attenuation of contaminants discharging through the hyporheic zone into a surface water body (Nagorski and Moore 1999, Conant et al. 2004). The chemical reactions can produce quantities of chemical species in the pore water not found in either groundwater or surface water (Schindler and Krabbenhoft 1998). Due to anaerobic, reducing conditions found in many aquifers, groundwater is often rich in ferrous iron, whereas river waters tend to be well-oxygenated and therefore oxidizing. The mixing of these two waters in the hyporheic zone may lead to the rapid oxidation of ferrous iron to low-solubility ferric iron oxyhydroxides, which then precipitate out of solution. These oxyhydroxides are sometimes found on hyporheic zone sediments as secondary mineral precipites (Benner et al. 1995, Charette and Sholkovitz 2002, Conant et al. 2004, Gan et al. 2006) and are an indicator for the depth of surface water penetration. 1 1.1 Purpose of Research This study examines the chemical changes in the hyporheic zone of a large, tidally influenced river with particular emphasis on the changes in the reduction-oxidation (redox) geochemistry as anaerobic groundwater, high in dissolved solids mixes, with the oxic river water. Due to the high levels of ferrous iron found in the aquifer in this study, it is expected that the dominant chemical reaction in the hyporheic zone will be iron oxidation that leaves iron oxyhydroxide precipitates on the sediments in the hyporheic zone, thus giving an indication of the penetration of the oxic river water. The thesis will address the following questions: What are the redox conditions in the hyporheic zone? How far below the riverbed does the hyporheic zone extend? How do the redox conditions change across the redox zone, going from anaerobic groundwater at one end to the aerobic river water at the other end? Do tidal and seasonal river stage fluctuations affect the precipitation reactions? Does the mobility of riverbed sediments flush the area of iron precipitates? 1.2 Thesis Outline To study the hyporheic zone, separate pore water profiles and sediment cores were obtained both in the hyporheic zone and in the deep aquifer (for comparison). Pore water samples were analyzed for dissolved metals and common anions as well as organics. Sediment cores were analyzed using a selective chemical dissolution (extraction) technique to assess the amount of iron minerals bound to the sediment surface. Unfavourable field conditions initially prevented the collection of the uppermost sediments. Thus a freeze-coring technique developed for sampling of stream sediments was adapted to the deep river environment and used to freeze a volume of hyporheic zone aquifer material. 2 Results of chemical analyses are presented as depth profiles and an interpretation is made as to the nature of the hyporheic zone in a large tidally influenced river. 2. Literature Review While the hyporheic zone is most often studied in the context of streams, the shallow sediments of all surface water bodies are subject to interaction of groundwater and surface water and therefore may exhibit similar geochemical patterns. Thus what is defined as the hyporheic zone in this study is sometimes also referred to as the 'groundwater - surface water interface' elsewhere. 2.1 Previous Hyporheic Zone Studies The following is a review of several published research studies investigating the geochemistry of shallow surface water body sediments. a) Benner et al. (1995) investigated the hyporheic zone of a creek passing through an area covered in mine tailings to assess dissolved metals attenuation across the hyporheic zone as minerals precipitate due to changing redox conditions as groundwater discharges into the creek. Instead of sampling the hyporheic zone sediments directly, bead columns were inserted into the creek bed to a depth of 140 cm and allowed to collect mineral coatings over a period of 6 and 15 weeks. Sections of the bead columns were then subjected to an aqua regia digest, which was analyzed for metal concentrations. Additionally, hyporheic pore water samples were collected and analyzed for dissolved metals and oxygen. Results show high accumulations of metals on the bead columns up to a depth of 20 cm with some accumulations found to a depth of 80 cm. Iron concentrations reach up to 0.25 ug/g iron over 15 weeks. Pore water shows a significant increase in dissolved metals at approximately 80 cm depth. This research suggests that the hyporheic zone acts as a significant sink for dissolved metals of waters discharging to the surface. It also gives an indication of the approximate depth of a hyporheic zone. 4 b) Researchers Matthew Charette and Edward Sholkovitz investigated the hyporheic zone of an estuary, trying to find iron precipitates - acting as a source or sink for nutrients and metals - that they hypothesized to form in the shallow sediments where groundwater and sea water mix (Charette and Sholkovitz 2002, 2006, Charette et al. 2005). Groundwater discharges into the estuary in a 25 m wide band and contains elevated levels of ferrous iron. Sediment cores reaching to a depth of up to 2.6 m were collected with a vibracoring technique and analyzed for mineral-bound metals including iron using selective chemical extractions. The sediments cores exhibited visible iron oxide staining and concentrations of iron up to 7600 ug/g dry sediment at a depth of 1.7 m. Significant accumulations of iron oxides were found up to the deepest sampled interval at 2.6 m. Peak iron concentrations correlate with peaks in phosphorus and thorium, suggesting sorption onto the iron oxides. Pore water samples were collected separately, showing a plume of dissolved iron and manganese that disappears within 1-2 m of the estuary bed, reinforcing the hypothesis that iron and manganese are removed in the hyporheic zone by precipitation. This research shows that iron oxide precipitates in significant concentrations are clearly visible on sediments and gives an estimate of the concentration range that may be found. Iron oxide coatings appear to be deposited over several metres depth, perhaps due to continuous tidal fluctuations influencing the depth of surface water penetration. c) Gan et al. (2005) studied the discharge of contaminated groundwater from a landfill site into a creek to trace arsenic originating in the aquifer and bound to iron oxyhydroxides. Hyporheic zone sediment cores were taken with a hand auger and a freeze-corer and analysed for arsenic and iron on a cm-scale resolution using sequential chemical extractions. A limited amount of separate 5 pore water samples was also taken and analyzed for dissolved oxygen and electric conductivity. Results showed that the highest concentrations of iron were found in the shallowest sediments (uppermost 10 cm), where iron oxides reached typical concentrations of several hundred thousand ug/g and a maximum of approximately 450,000 ug/g dry sediment, with significant accumulations still found at the deepest sampled interval of 30 cm depth. Arsenic concentrations correlated well with iron oxide accumulations, which were attributed to sorption processes. Pore water dissolved oxygen concentrations stayed below 1mg/L even in the shallowest sampled interval at 15 cm depth. Additionally, bead columns were inserted into the hyporheic zone sediments to a depth of 16 cm for 29 days resulting in accumulations of up to 7000 ug/g within that time. The 450,000 ug iron/g dry sediment define a likely upper bound for iron oxide accumulation on hyporheic zone sediments. The freeze-core technique is demonstrated to allow for fine-scale resolution sampling of surface sediments. 2.2 Review of Extraction Methods For this investigation the oxidation state of iron bound to the sediments is of interest as it is a redox-sensitive species with a fast kinetic conversion from ferrous to ferric iron. The redox state of the sediment grain surface is the most interesting to evaluate because it is in direct contact with the groundwater. The objective of the analyses in this study is to determine if the amount of iron precipitated onto the sediments differs with depth. A high amount of precipitated ferric iron would indicate a mixing of anoxic groundwater high in dissolved iron with oxic river water and thus delineate the hyporheic zone (Charette and Sholkovitz 2002). Besides determining the amount of total iron precipitated, an attempt was also made to quantify the relative amounts of ferrous and ferric iron present on the sediment grains. 6 Selective chemical extractions of soil and sediment samples have long been used to dissolve metal oxide coatings and in particular iron and manganese oxide coatings on sediments (Tessier et al. 1979, Lovley and Phillips 1987, Heron et al. 1994). Extractions are a technique by which a corrosive chemical solution is mixed with a known amount of sediment and various mineral and in particular secondary mineral precipitates bound to the sediment are thus dissolved into solution, which is then analyzed. Sediment extractions can quantify different fractions of the minerals that are bound to the surface of sediment grains by using chemical solutions of increasing strength (Christensen et al. 2000 and references therein). The selective dissolutions generally attempt to dissolve increasingly more closely bound minerals, approximately defined as: a) dissolved metals and those bound to ion-exchange sites, b) amorphous hydrous oxides, c) crystalline oxides, d) sulphide minerals, and f) total secondary minerals (e.g. Tessier etal. 1979, Lovley and Phillips 1987, Heron etal. 1994, Hall et al. 1996, Poulton and Raiswell 2005). However, the compositions of both the matrix minerals and the secondary mineral precipitates as well as the purpose of the extractions vary considerably, so that no single extraction protocol can encompass all variables (Hall et al. 1996, Amirbahman et al. 1998, Hyacinthe et al. 2006). Thus to date no standard extraction protocol has been proposed. It is difficult to use selective extractions to quantify the amount of one particular mineral phase as some extractions cause partial dissolution of a mineral phase (Heron et al. 1994, Tuccillo et al. 1999). For example the extraction of crystalline F e C 0 3 also causes the partial dissolution of amorphous iron sulphides. Therefore extraction methods used in this study are operationally defined. Three single-step extraction methods, modified from Heron et al. (1994) were deemed suitable for this study due to their simplicity and proven application by other researchers (Lendvay et al. 1998, Kennedy et al. 1999, Tucillo et al. 1999, van Breukelen et al. 2003). 7 a) 24-hour 1M CaCI 2 extraction. A magnesium or calcium chloride solution has been shown to define the dissolved and exchangeable ion fraction (Heron et al. 1994, Heron and Christensen 1995, Hall et al. 1996). b) 24-h 0.75 M HCI extraction. 0.5M or 1.0M hydrochloric acid extractions have been used to dissolve amorphous and weakly crystalline iron oxyhydroxides (Lovley and Phillips 1987, Heron and Christensen 1995, Hall et al. 1996). This is the most significant extraction for this study as it will quantify the amount of amorphous iron oxyhydroxides precipitated onto sediments in the hyporheic zone. c) 21-day 5M HCI extraction. Strong (5-12M) hydrochloric acid extractions have been shown to extract most crystalline iron oxides and some iron sulphide minerals, thereby dissolving the majority of iron minerals chemically available in the aquifer materials (Heron and Christensen 1995, Hall et al. 1996, Tuccillo et al. 1999). 8 3. Site Description The area of investigation is located in the lower Fraser River in a reach that is affected by significant tidal fluctuations. Sea water does not intrude into this part of the river, even at times of low flow during high tides. The Fraser River is a 9 t h order river and has average and peak flows of approximately 3500 m 3/s and 10,000 m 3/s, respectively. Its drainage basin (Figure 1) encompasses 228,000 km 2 . The site selected for investigation is located at the trailing edge of a post-glacial river delta deposit in Coquitlam, British Columbia approximately 30 km upstream from the mouth of the river (Figure 2). The site selected for study has been the focus of previous scientific and environmental investigations after subsurface creosote contamination and a contaminant plume had been identified there. The subaqueous hyporheic sediment interface is located in a groundwater discharge zone at the leading edge of a creosote plume (Figures 4 and 5), approximately 100 metres off the north shore of the Fraser River in 10-12 metre deep water (Figure 3). 3.1 Previous Research and History of the Site An industrial wood-preserving facility is located approximately 200 metres on shore from the study location. Operations have been ongoing since 1929 and creosote is known to have been used extensively at the site until the 1980's (Golder 1997). Creosote entered the subsurface likely as spills and leaks from storage containers and pipes. After the discovery of extensive creosote contamination in the 1980's and the mapping of a creosote contaminant plume in the 1990's, the operators installed a pumping system to reverse the local hydraulic gradient to prevent subsurface flow of the contaminant and contaminated groundwater beneath neighbouring properties and into the Fraser River (Golder 1999). 9 Following is a list and brief summary of all known significant scientific investigations that have been conducted at the research site after 1996 and prior to this study. A summary of investigations prior to 1996 can be found in Appendix I of Golder's 1997 Environmental Site Assessment Report. - Golder Associates Ltd., Environmental Site Assessment Report (1997) The environmental consultant Golder Associates Ltd. conducted extensive investigations of soil and groundwater conditions in and around the contamination source. This report includes soil and groundwater chemical analyses on land as well as an assessment of flow conditions. - Golder Associates Ltd., Addendum to Environmental Site Assessment Report (1998) This addendum contains corrections and additional work completed since the first report, including photographs. - Tom Anthony, University of Waterloo Master of Science Thesis (1998) Anthony studied the natural anaerobic in-situ attenuation of creosote and pentachlorophenol at the site. The thesis contains pore water chemistry from the aquifer and a detailed 1996 map of the contaminant plume. - Golder Associates Ltd. Site Management Plan (1999) This report summarizes all aqueous chemistry, hydrogeologic and hydrologic information to 1999 and recommended the extension of a network of groundwater pumping wells to capture separate phase contaminant and the entire contaminant plume. - Luis Lesser, University of Waterloo Master of Science Thesis (2000) The thesis includes the results of additional geochemistry sampling and a microcosm experiment that provided evidence of anaerobic degradation of naphthalene as found in the aquifer at the site. 10 - Mario Bianchin, University of British Columbia Master of Science Thesis (2001) The author conducted an in-situ degradation experiment of radio-labelled naphthalene that confirmed anaerobic degradation of naphthalene at the site. The thesis includes a 1999 map of the contaminant plume, which is similar in extent and location the contaminant plume mapped by Anthony. - Christine Bishop, University of British Columbia Master of Science Thesis (2003) The study maps the off-shore component of the contaminant plume and found a reduction in naphthalene concentrations from previous work. Indane and benzothiphene were identified as significant components of the off-shore plume. Detailed geochemical analyses of pore water and sediment samples were performed. Computer modelling showed that the contaminant plume is not fully captured by on-shore pumping wells. 3.2 Geology and Hydrogeology at the Site The area is at the trailing edge of a contemporary river delta that began forming after the last period of glaciation had ended at the beginning of the Holocene epoch. The stratigraphy is indicated in Figure 4 and is as follows: At the base approximately 30 m below sea level the fluvial sands are confined by silt-dominated marine deltaic deposits that act as an aquitard (not depicted in Figure 4). Overlying these sediments are the Fraser River Sands, a fluvial deltaic deposit of sand with discontinuous interbedded finer and coarse-grained lenses. The Fraser River Sands are between 20 and 30 m thick at the site and act as an aquifer locally and regionally. Pump tests performed indicated a hydraulic conductivity of 5 x 10~4 m/s (Golder 1997). The aquifer is confined above by a deposit of fluvial silt, of varying in thickness from 1 to 10 metres and grading into the underlying sands. This gradational interbedded contact ranges in thickness from 1.5 to 10 metres. The hydraulic conductivity of the silts has been measured at 5 x 10"7 m/s (Golder 1997). 11 On land overlying the silt is a 1-4 metre thick layer of fill that has been placed as the land was developed within the last century. Its hydraulic conductivity is estimated at 1 x 10~4 m/s (Golder 1997). Groundwater flow locally is typical of a gaining river in that it is generally from north - where the land surface rises above river level - to south, discharging into the river through the sandy aquifer (Figure 5). Flow in the aquifer is horizontal, except beneath the river, where the groundwater discharges upwards into the river (Bishop 2003). A chemically distinct regional groundwater flows underneath the local flow regime and discharges into the river south of the study area (Figure 5). A net hydraulic gradient of 6x10" 4 towards the river was observed. However, the gradient reverses at times with tidal fluctuations of the river level and seasonally when the river stage rises substantially during the annual freshet (Anthony 1998). This temporary reversal in gradient causes the river to temporarily recharge the sandy aquifer, allowing groundwater and river water to mix in the shallow sediments. Precipitation in the area is low in the summer during the annual freshet and high in the winter when the river stage is low, which leads to a higher volume of groundwater discharge in the winter. The natural hydraulic gradient has been reduced by a pumping well that was installed to capture free phase creosote and prevent the flow of the contaminant plume towards the river. The pumping well is located on land 125 metres north of the shoreline in the area of maximum contaminant concentration. The pumping rate was 16m 3/hourfrom 1996 to 1999 and has been 27m 3/hour since then. However, computer modelling results show that contaminated groundwater continues to discharge into the river, but with an increase in residence time allowing contaminants more time to degrade in situ (Bishop 2003). 12 3.3 Geochemistry A considerable amount of liquid phase creosote has entered the subsurface on an industrial property located upgradient from the site. It is present as a non-aqueous phase liquid (NAPL) up to a maximum depth of about 20 metres below mean river level. An approximately 200 metre wide plume of dissolved polycyclic aromatic hydrocarbons, mainly consisting of naphthalene, extends downgradient and discharges into the river as shown in Figure 5. The concentrations of contaminants in the plume have significantly declined over time on-shore (Anthony 1998, Roschinski 2004) and offshore (Bianchin 2001, Bishop 2003). The sediments in the floodplain of the lower Fraser River are deltaic fluvial and therefore have been deposited rapidly enough to allow for the inclusion of organic material. The decay of this organic material creates a reducing, anaerobic subsurface environment. Not surprisingly, the aquifer has been found to contain no appreciable amount of oxygen within and outside of the contaminant plume (Anthony 1998, Bianchin 2001). Concentrations of sulphide and manganese (Mn2+) are also insignificant. Methanogenesis and the reductive dissolution of iron oxyhydroxides were found to be the main redox-determining process in the deep aquifer in the centre of the off-shore component of the contaminant plume (Bianchin 2001). Dissolved iron concentrations are high ranging between 20 and over 100 mg/L, , and methane concentrations up to about 20 mg/L have been observed (Anthony 1998, Lesser 2000, Bianchin 2001, Bishop 2003). Bishop (2003) found acetate concentrations averaging 20 uM (0.94 mg/L) and concluded from it that "methanogenic conditions with limited Fe(lll) reduction exist within the aquifer". During previous profiling events, groundwaters were found to have a pH of between 5.6 and 7.4, with the majority of the measurements around pH 6.5. In distinction from the local groundwater, the deep groundwater contains higher concentrations of dissolved metals and chloride. Chloride concentrations in the 13 local groundwater are in the 10s of mg/L, whereas in the regional groundwat concentrations are two orders of magnitude higher. 4. M e t h o d s 4.1 Sample Collection Sediment cores and pore water profiles were obtained from the hyporheic zone with modified drill core equipment using a 21-metre long commercial salmon fishing boat as a working platform (Figures 6 and 7). Previous workers recovered sediment core and groundwater profiles in shallow sediments using similar equipment (Fischer et al. 2005, Charette and Sholkovitz 2006). The location of the groundwater discharge zone on the riverbed was inferred from the creosote contaminant plume described in Anthony (1998), Bianchin (2001), and Bishop (2003). Using the contaminant concentrations as a tracer of groundwater flow, the discharge zone was inferred to be at the sediment-river interface where the highest contaminant concentrations had been mapped. The work posed a considerable challenge as the river bottom is covered with sunken logs and wood chips, which made it difficult to accurately determine the vertical position of the sampling points. It was also difficult to predetermine accurately the horizontal location of the sample collection points in part due to the inability to see to depth, and in part due to the swift river currents, which pushed the sampling gear several meters downriver (Figure 7). The position of the sampling points on the river was determined by measuring the distance to two reference locations on shore with a Bushnell Laser Rangefinder Yardage Pro 500, which is specified as accurate within one metre. During sampling work, the boat was held in place by a minimum of 6 anchoring lines. A depth profile perpendicular to the shoreline was obtained at low tide on May 20 t h 2004, between 17:45 and 18:00, using a pre-marked rope with a weight attached to the bottom to measure water depth and a laser range finder to measure distance to a near-shore municipal sign marking a Greater Vancouver Regional District storm sewer outflow. This depth profile was used to draw the riverbed in Figures 4, 5 and 11. 15 4.1.1 Sediment Core Collection A preliminary investigation recovered several core samples in 2004, but an ownership claim and preservation difficulties prevented analysis of the majority of the sediment cores. Therefore a new attempt to collect core samples was made during the summer of 2005 using a freeze-shoe corer. Difficulties with the collection of sediments at the riverbed using the freeze-shoe corer led to the development of a new tool and its deployment in December 2006. 4.1.1.1 2005 Cores Cores were collected between June 27th and July 8 t h 2005 during freshet (approximate discharge 6000 m3/s) with the freeze-shoe method developed by Murphy and Herkelrath (1996) and modified by Bianchin (unpublished). The freeze-shoe attaches to the bottom of the coring equipment and is connected to the surface with a stainless steel line which allows for the injection of liquid carbon dioxide around the bottom of the sediment core (Figures 8 and 9). The rapid expansion of the carbon dioxide causes the bottom of the sediment column it surrounds to freeze, thereby preventing loose sediment from sliding and falling out of the coring tool during recovery. Five-foot steel drill rod casings, internal rods, core barrel and the freeze shoe were assembled horizontally on deck of the boat, lifted with a winch attached to a boom and fastened to the railing of the fishing boat with a custom-built steel bracket (Figure 9). As the assembly was lowered into the water and advanced into the ground, additional casings and internal rods were connected as necessary. Using a pneumatic hammer, the entire assembly was driven to the depth of the top of the core; then one additional section of casing was attached and hammered down while the internal rods were held back by securing a steel cable to them, causing the freeze shoe and core barrel to advance over a sediment core. The bottom of the core was frozen by injecting liquid carbon dioxide for about 15 minutes through the freeze shoe. After the injection of liquid carbon 16 dioxide the entire assembly, including the sediment, was pulled out of the riverbed and lifted onto the deck of the boat. The vigorous shaking and pulling required to loosen the core liner from the freeze shoe caused the pore water to drain from the sediment sample as the core liner and core were removed from the casing. The lined cores were either kept intact or cut into 30 cm sections. The ends of each section were sealed with end caps and wax or Parafilm under constant flow of nitrogen to maintain anaerobic conditions. The cores were kept cool and brought into the lab within two days of collection. During core collection it was difficult to measure the depth to the river bottom for the following reasons: (1) the weight of the coring rods made the equipment slump into the ground before hammering commenced and (2) once hammering started, the corer would sometimes slip and free fall up to one metre to another "bottom". Hence the uncertainty in the vertical position of a core could be as large as one metre. This made it particularly difficult to locate the position of the sediment - water interface, where changes in redox geochemistry were expected to be the greatest. Hyporheic zone cores were retrieved at location C1-05 from 0.2 to 1.5 m and 3.2 to 4.3 m depth, at location C2-05 from 0.7 to 1.9 m and 2.3 to 3.9 m depth. For an end-member comparison of sediments conditions a core was also retrieved in the deep part of the aquifer at location C3-05 from 10.1 to 11.5 m and 11.8 to 13.2 m depth, as shown in Figures 10 and 11. The depth of samples was measured from the deepest point with respect to the river bottom that the corer was driven to and then measured upwards. For example, at C3-05 the corer was driven to 13.2 m depth, the core frozen, brought to surface and a 1.4 m long section of core was recovered. Thus the top of that core was taken to be at 13.2 - 1.4 = 11.8 m depth below riverbed. 17 For storage purposes the core was immediately processed into sections in the lab. A Coy Vinyl Anaerobic Glovebox, Type B was prepared and filled with a gas mixture of 10% hydrogen, 5% carbon dioxide and 85% nitrogen. In this atmosphere a palladium catalyst - attached to a fan box to keep a constant gas flow through the catalyst - controls the oxygen level by reacting any oxygen with hydrogen. With this method it is possible to keep the oxygen level to less than 5 ppm (Coy 2007). The intact cores were cut with a hack saw into 30 cm sections which were then placed into the glovebox where the core sections were further cut into 10 cm sections while still in the core liner. The sediments that had come into contact with the saw were discarded and samples were carefully scooped out of the centre of the sections with a clean stainless steel spatula and placed into pre-labelled 50 ml flat top polypropylene centrifuge tubes. 4.1.1.2 Summer 2006 Cores The difficulties in determining the river bottom depth and the relatively large error in the sampling depths of the cores led to consideration of other approaches to sampling. After all previous efforts to obtain samples from the shallowest sediments, the uppermost sediments in direct contact with the river had still not been sampled. Accordingly, professional divers were contracted to inspect and manually collect cores from the river bottom at the suspected zone of groundwater discharge. A team of professional divers was hired from Subsea Enterprises Inc. (Vancouver, British Columbia) to collect sediment core on April 21 s t 2006 from the uppermost sediments of the hyporheic zone, the section that could not be reliably recovered during the 2005 sampling season. A slide-hammer was attached to a 1 Vz inch outer diameter (OD) Phleger corer (Figure 12) that was used underwater by the diving team. The core liner is a 13/8 inch diameter and 65 cm long polycarbonate tube. Due to the high suspended sediment load in the river, the visibility at the bottom of the river was zero and the divers could only rely upon feel through heavy rubber gloves to determine the texture of the river bottom. A diver covered an area of approximately 50m2 of the river bottom and 18 made several attempts to collect core with the Phelger corer, each time driving the entire length of corer into the riverbed, but ultimately the diving team could only recover one 15 cm section of core from the location of C1-05. At another location, C2-06 the divers encountered some sediment breaks in the wood cover, but also recovered only a 15 cm section. At C4-06, a sandbank about 25 metres from C2-06 the divers recovered a 60 cm section of medium to coarse-grained sand. The sampling locations are shown in Figures 10 and 11. It became difficult to remove the core liner from the corer when sand grains became wedged between the corer and the core liner, and in the process all but the 60 cm section of core were inadvertently exposed to the atmosphere for several hours. The cores were taken to the lab the same day, immediately frozen and processed at room temperature the next day. As previously, the cores were cut into 10 cm sections inside the glovebox. The samples were carefully scooped out of the centre of the sections with plastic spoons and placed into pre-labelled 50 ml plug seal polypropylene centrifuge tubes. Because of slippage of core in the core liner, the error in the vertical location of the sediment cores is estimated at 5 centimetres. 4.1.2 Simultaneous Core and Pore Water Collection As a result of the difficulty experienced in matching the depths of the pore water samples with the sediment sample depths, a methodology was developed to collect a frozen sediment core to yield coincident sediment and pore water samples. Stream, lake and riverbed samples have been successfully collected by various freezing methods (e.g. Carling and Reader 1981, Stocker and Williams 1972, Miskimmin et al. 1996, Moser et al. 2003). Initially, a shallow-water freeze-tube design cooled by evaporating liquid carbon dioxide - as described by Carling (1981) - was adapted to the deep river environment and a prototype constructed. For this design, liquid pressurized carbon dioxide is released through small orifices from an inner probe which is contained within a standpipe that is inserted into the sediments. The depressurization leads to rapid cooling such that pore water and sediments freeze onto the standpipe. However, after numerous preliminary tests the prototype system did not appear to provide the cooling capacity required to freeze a sufficiently large radius of sediment in less than one hour. The carbon dioxide cooling method was abandoned for a method utilizing liquid nitrogen, which remains liquid under atmospheric conditions and is therefore more easily deployable. Liquid nitrogen at -196°C also has the lowest temperature among all readily available coolants. The extra cooling capacity allows one to successfully freeze sediment and overwhelm any unexpected heat sources. While numerous freeze corers utilizing liquid nitrogen have been designed for collection of streambed sediments (e.g. Hill 1999, Stockerand Williams 1972, Wagner et al. 2003), none of them were judged suitable for adaptation to river environment with its deep, fast-flowing water. A modification of the freeze-corer design presented in Hofmann et al. (2000), however, appeared robust enough to meet the following conditions: - equipment can be lifted onto a 22m fishing boat - equipment can yield to the stresses imposed by swift water flow in a tidally influenced river (i.e. both directions of flow) without failure - the liquid nitrogen delivery system can be isolated from the river water - equipment is robust enough to withstand hammering forces as the freeze corer is inserted into the river bottom - the length of the delivery system and casing is variable to suit varying water depths, but at least suitable for 12m water depth. A design that met these conditions was developed and its application is presented below. 20 Individual samples are obtained by freezing saturated sediment to a hollow-chambered steel casing, called the freeze pipe, driven into the riverbed. Liquid nitrogen is delivered into and exits the chamber via two 13 mm copper pipes that extend to the surface. The copper pipes are protected from contact with river water by a waterproof extension of the steel casing. Liquid nitrogen in direct contact with the freeze pipe results in rapid cooling and freezing of pore water and sediment surrounding the steel casing (Figure 13). A 5.7 cm outer diameter, 75 cm long steel drill rod casing was used as a freeze pipe to contain the liquid nitrogen (Figure 14). The freeze pipe was sealed below the internal threads creating a chamber for the liquid nitrogen to flux through. The internal threads connect the freeze pipe to 5 foot sections of steel casing. A steel tip aids insertion into the sediments and a stopper plate sets a maximum insertion limit at the point where the chamber terminates. Two standard copper pipe sections (outer diameter 13 mm) were welded into the seal to serve as in- and outflow for the liquid nitrogen (Figure 14). It is important for the copper pipes to extend approximately 10-15 cm past the threads and for one of the copper pipes connecting to the freeze chamber to be at least 4 cm longer than the other to accommodate the union fittings along the length of pipe. The copper pipe extensions then connect to 4 foot 11.5 inch copper pipe sections with Swagelok unions. Styrofoam spacers are duct taped between the twin copper pipes and on the outside of them. After each of the two copper sections is attached, a 5-foot steel drill rod casing is slid over the copper pipes and threaded into the previous section. This required a tight alignment of the nuts on the union. To prevent water from entering the drill rod casings and freezing to the copper pipes, the section joints have to withstand the water pressure at sampling depth. For this purpose the joint sections were carefully taped with one layer of premium quality duct tape, followed by two layers of electrical tape and two layers of duct tape, alternating, whereby the end of the existing layer was always overlapped by the following layer. 21 After several sections were assembled, a custom-made steel bracket was attached to the rods and the entire apparatus lifted over the side of the fishing boat (Figures 15a, b, c). While the assembly was incrementally lowered into the river, copper pipe and casings were attached until the tip of the freeze rod reached the river bottom. The assembly was then hammered into the river sediments with a pneumatic hammer until the stopper plate prevented further insertion. The nitrogen inflow pipe was connected to a 6-foot cryogenic hose that is attached to a 230 litre liquid nitrogen container pressurized to 230 psi (Figure 16). Thermal contraction of the 12 m of copper pipe upon cooling is minimal. The valve of the liquid nitrogen tank was opened almost entirely. The tank emptied in 25 minutes, after which the hose was disconnected and the assembly - including the frozen sediment block - pulled from the riverbed with the boat's winch. The 5-foot sections were disassembled individually until the assembly was short enough to be lifted into the deck of the boat in its entirety. This process lasted 10 minutes during which the flow of river water melted sediments frozen to the core. A frozen core of 60 cm length was lifted onto the boat at approximately 3pm on December 21 s t, 2006 (Figures 17 and 18). The frozen sediment core was placed on doubly folded polyethylene vapour barrier plastic sheeting to prevent contamination of the sediments from dirt and rust on the deck of the boat. The core was gradually shattered into pieces with a sledgehammer. The sediment core was protected from iron contamination by the sledge hammer by an unbreakable 2 mm thick polycarbonate plastic barrier that was placed on top of the core before each hammer strike. After each successful break, the core was measured and the broken piece labelled as to its depth from the top of the core and placed into a large Ziploc EasyZipper storage bag. The bags were kept in a cooler filled with dry ice until delivery to the laboratory. 22 In the lab the bags containing sediment blocks were divided into six 10 cm intervals, starting from the top. Each 10-cm sediment interval was handled separately. The frozen sediment pieces, each measuring approximately 0.5 to 1 litre in volume, were placed in an anaerobic glove box each on a separate plastic plate and thawed under the exclusion of oxygen to prevent ferrous iron in the pore water from oxidizing and precipitating out of solution, thereby distorting dissolved iron concentration. As the sediment pieces were thawing, the outside layer that was subject to contamination was removed with a plastic spoon. The sediment was slowly drained of its liquid by placing the plate on an angle and collecting the pooling water into a separate container. Water-saturated sediment was placed in a centrifuge tube and centrifuged at 625 rpm for several minutes to separate water from the sediment. Dissolved ferrous iron was measured immediately and the remainder of the water samples were preserved as described in section 4.2.1 and sent off to an analytical lab while the sediment was subjected to extractions as described in section 4.2.3. This method of collection provided the most accurate vertical core location of all methods tried during the course of this investigation. Due to measurement error during segmentation of the core the error in the vertical location of the 10-cm segments is estimated at 2 centimetres. 4.1.3 Water Sample Collection Pore water samples gathered in 2005 were collected within 1-2 metres of the core samples with a Waterloo Drive Point Profiler (WDPP). Each profile required between 4 and 21 hours of sampling, so that individual profiling points were collected at various stages in the tide cycle. Hence, the pore water data do not represent synchronous distributions of the measured parameters. The W D P P system (Pitkin et al. 1999), which was developed at the University of Waterloo, enables the collection of discrete pore water samples from specific depths, thereby permitting the construction of a detailed vertical characterisation at a given location. The W D P P consists of a profiler tip that is connected to 5-foot • 23 lengths of 1% inch internal diameter (ID) 1% inch OD AW rods. The profiler tip is fashioned with six 6 mm diameter screened ports. Each port is connected to a sealed central reservoir, which is connected to V* inch OD polyethylene tubing that runs internally through the entire length of the AW rod assembly. At ground surface, the tubing was connected with Swagelok fittings to a sampling manifold containing two 40 ml glass sampling bottles. The sampling manifold connected to a Geotech Geopump 2 (600 rpm) bi-directional, variable speed peristaltic pump, and then through a 500 ml flow-through cell which also acted as a purge container. Figures 19 and 20 show the set-up. The WDPP was assembled horizontally on the deck of the boat, lifted with a winch attached to a boom and fastened to the railing of the boat with a custom-built steel bracket. The assembly was lowered into the water and when the profiler touched the river bottom, the rods were pulled up several centimetres and a river water sample was taken. As with the core collection, it was difficult to accurately determine the location of the river bottom with the profiler. The profiler tip and AW rod assembly were advanced into the river sediments with a pneumatic hammer to sampling intervals typically separated by 30 cm. As the assembly was advanced, distilled de-ionised water was pumped down through the internal tubing system in order to prevent the ports from clogging. Once the profiler tip was advanced to the desired depth, the direction of the peristaltic pump was reversed and groundwater was drawn up through the tubing and the flow through cell at rate of 0.1- 0.2 litres per minute. The flow through cell was equipped with a pH probe that was recalibrated daily and connected to either an Orion 250A or a 250A+ pH meter, and an Orion model 115 or Hach Senslon electrical conductivity meter and probe. When a purge volume equal to three times the tubing volume had been pumped, the pH, temperature and electrical conductivity of the groundwater were monitored, and once stable, the corresponding values were recorded. The flow rate, with the pump running at full speed, was measured to provide a relative estimate of the hydraulic conductivity of the sediments at each depth. 24 In 2005, dissolved oxygen (DO), total iron, ferrous iron (Fe 2 +), nitrate (N03~) were analyzed in the field using Hach AccuVac vials. Samples were also collected for laboratory analyses such as concentrations of dissolved cations, dissolved anions, dissolved organic carbon, concentrations of arsenic and polycyclic aromatic hydrocarbons (PAHs). The samples were extracted from the polyethylene tubing through a 3-way valve with a 60 ml syringe, thereby minimising oxidation of the sample prior to filtration. The samples to be tested for dissolved cations were filtered with disposable 30 mm diameter 0.45 um cellulose acetate syringe filters. Samples for cation analysis were acidified to a pH less than 2. Water was collected into 500 ml brown glass containers sealed with Teflon septa for analysis of dissolved methane. After all other samples had been collected, the 40 ml glass sampling bottles were removed from the sampling manifold, capped with a screw cap containing Teflon-coated silicon septa and labelled for PAH analysis. Pore water samples from 2005 were collected between June 23 r d and July 8 t h. See Table 1 for an overview of the water samples collected. All samples were kept cool until delivery to an analytical lab within three days. In 2006, samples were collected with the same WDPP system, but no samples were analyzed for nitrate in the field. Also no samples were collected for analysis of dissolved methane. Ferrous and total iron was measured in the field with the Ferrozine method as described by Lovley and Phillips (1987). Additionally, samples were also collected for determination of alkalinity. 4.2 Sample Analyses 4.2.1 Water Samples In the 2005 sampling season, river and groundwater samples were analyzed immediately for DO, N O 3 " , total iron and Fe 2 + . For DO, a 20ml container was filled with sample from the bottom of the container directly out of the pumping system. A snap-off vial from a CHEMets low range oxygen test kit K-7501 was then used to determine the approximate concentration of DO. Measuring DO in a Hach 25 DR/2400 spectrophotometer using Hach AccuVac low range DO ampoules was also attempted but failed to provide reasonable results likely due to contamination with atmospheric oxygen. N0 3 " was measured colorimetrically with Hach AccuVac NitraVer 5 ampoules in a spectrophotometer, but repeated testing showed significantly different concentrations for the standard solution prepared in the lab and thus results were deemed unreliable. Samples were filtered through 30mm diameter 0.45um cellulose acetate syringe filter and similarly Hach AccuVac ampoules were used to determine total iron and ferrous iron concentrations. In the 2006 sampling season, river and groundwater samples were filtered as previously and analyzed immediately for Fe 2 + and alkalinity. Fe 2 + was analyzed with the Ferrozine method described in Section 4.2.2. For alkalinity, a filtered 25 ml sample of water was titrated with 0.1 M sulphuric acid to beyond the inflection point. The pH was recorded after the addition of each aliquot of acid and the alkalinity later determined with the Gran method (Gran 1952). For both the 2005 and 2006 pore waters, river and groundwater samples were submitted to ALS Environmental analytical laboratory (Vancouver, British Columbia) for analysis of dissolved cations, anions, and arsenic. Additionally, unfiltered water samples from profile P3-06 were analyzed for total iron. Appendix A contains complete results of the analysis reports. PAH samples were analyzed at UBC's microbiology laboratory. Dichloromethane was added to the samples to extract the PAHs. The samples were then vaporized in a gas chromatograph and analyzed with a mass spectrometer as described in Appendix D. 26 4.2.2 Sediment Analyses 4.2.2.1 Sediment Extractions Reagents for the extraction procedures were prepared and subsequently de-aired by bubbling nitrogen gas through the solutions before transfer to the anaerobic chamber. In the anaerobic chamber, each wet sediment sample was thoroughly mixed for homogenization and removed from the centrifuge tube that they were stored with the end of a white plastic spoon. Between one and five grams of sediment were weighted on a precision balance and then transferred to another pre-labelled centrifuge tube and the extraction solution added. The filled centrifuge tubes were removed from the chamber and placed on a shaker table for the duration of the extraction period. For most sample depths, duplicate samples were analyzed and where an anomalous result was found, analyses were repeated thus leading to triplicate and quadruplicate results for some sample depths. An overview of the extractions is given in Table 2. Samples underwent partial digestion by calcium chloride, weak and strong hydrochloric acid solutions. These increasingly more aggressive solutions permitted the quantification of progressively more closely bound mineral phases on the surface of the sediment grains. After the indicated extraction time, samples were centrifuged and filtered through a 0.45 urn syringe filter and analyzed with the Ferrozine method for total iron with the Hach method 8147 (Hach 2002) and ferrous iron as described by Lovley and Phillips (1987) both times using a Hach DR/2400 spectrophotometer. Ferric iron was calculated as the difference between total and ferrous iron. The error from dilution of the samples, the variability of the sampling vials and accuracy of the instrument adds up to less than three percent. An in-depth description of the procedures is presented in Appendix C. 27 4.2.2.2 Scanning Electron Microscopy Scanning electron microscopy is a qualitative method of analysis, whereby a finely focussed electron beam is pointed at small material samples, producing a high-resolution image of the sample surface. The method also allows for the determination of elements on the surface of the sediment samples. Several samples that were collected in 2004 from the aquifer were viewed under the microscope to look for signs of secondary mineral accumulation. A Philips XL-30 Scanning Electron Microscope (SEM), equipped with a Princeton Gamma-Tech Energy Dispersive X-ray Spectrometer system was used to qualitatively analyze select sediment samples. Samples from several different depths were dried in the anaerobic glovebox and a small amount of grains, typically less than 0.5 grams was placed on a sample mount. The mounts were removed from the glovebox, a graphite coating applied and then transferred to the vacuum chamber of the S E M . Thus exposure to atmospheric conditions after drying occurred for less than one hour. 4.2.2.3 Rietveld X-Ray Diffraction Powdered X-ray diffraction is a non-destructive analytical technique, whereby a powdered mineral sample is moved through an X-ray beam at various angles. The crystallographic structure of each mineral produces a characteristic pattern of refractions of varying intensities at specific refraction angles allowing for the identification of a suite of minerals present in the sample. Since amorphous mineral do not refract X-rays in an ordered pattern, it is not possible to identify them with this method. A Rietveld analysis of the refraction pattern allows for an estimate of the relative abundances of each mineral, accurate to within several percent. Nine anaerobically dried sediment samples from representative sections of core collected in 2005 were analyzed for their mineralogical composition. Samples were ground under anhydrous ethanol in a McCrone micronising mill for 7 minutes to reduce grain size and to ensure homogenization. The samples were 28 set to dry under a fume hood for 24 hours, and then mounted in a back-loading aluminum cavity holder described by Raudsepp and Pani (2003). Preferred orientation of inequant crystallites was minimized by covering the top of the cavity with a sheet of ground glass and loading powdered samples against the roughened surface. X-ray powder diffraction data were collected on a Siemens D5000 0-2G diffractometer with a Vantec detector using a step size of 0.04° 20 and counting time of 0.8s/step over a range of 3-80° 2G. The normal-focus cobalt X-ray tube was operated at 35 kV and 40 mA. Rietveld refinements were done with Rietveld refinement software Topas Version 3 (Bruker A X S 2004) using the fundamental parameters approach (Cheary and Coelho 1992). 29 5. R e s u l t s a n d D i s c u s s i o n In this chapter the stratigraphic and geochemical character of the aquifer in and near the hyporheic zone is presented and a comparison is made with the geochemistry of the deep aquifer. This will give us an understanding of the chemical processes unique to the hyporheic zone and allow for an insight into the complex biogeochemical interactions that result from the mixing of surface water and groundwater. 5.1 Sediment Stratigraphy and Groundwater Flow The cross-sectional profile of the riverbed (Figure 4) obtained in 2004 shows the riverbed morphology. From the shore to a distance of 35 m the riverbed dips at an angle of 19 degrees to the centre of the channel. From a distance of 35 m to 90 m from the shore the riverbed remains relatively level. From a distance of 90 to 100 m from shore there is a steep slope with an angle of 22 degrees. This second slope is the area previous workers identified as a discharge zone of the contaminant plume (Anthony 1998, Bianchin 2001). It is therefore also regarded as a local groundwater discharge zone. The morphology of the site as surveyed does not agree with the illustrations in previous publications (Golder 1997, Anthony 1998, Bianchin 2001, Bishop 2003). This discrepancy may in part be due to shifting riverbed morphology, but the is most likely due to different methodologies employed to survey the riverbed as the riverbed morphology did not dramatically change over the time of this study. In fact, in 2004, 2005 and 2006, the slope from 90 to 100 m distance described above was located at the same distance from shore. It is therefore the firm belief of this author that the riverbed profile presented in this study represents a true and more accurate depiction of the riverbed morphology at the field site. The material recovered in cores C1-05, C2-05 and C3-05 (see Tables 3 and 4) confirms the findings by Golder (1997) that the sediments in the area consist of a confining silt layer that grades into the underlying sandy aquifer. It is also evident 30 from the sediment record that the shallow sediments (Tables 3, 4, 5) contain an overabundance of organic matter, between 5 and 80 percent, which is far in excess of typical aquifer organic carbon content. The sediment interface in direct contact with the river at and near the second slope consists of a variety of materials. Information about the material comes from an oral report by the divers, sediment cores C1-05 and C-12-06, and sediment recovered during failed coring attempts. The divers employed in April 2006 searched an area of about 50 m 2 in the immediate vicinity of core C1-05. They could not find any loose sediment bed. Instead, they reported the river bottom to be "like a solid matt of wood". The sediment they did find was saltating sand grains and sand trapped in interstices of the "matrix of logs". The findings coincide with the material recovered from an unsuccessful coring attempt in which a piece of log - overlain by approximately 10 centimetres of woodchips and some silt - plugged the coring instrument. The divers found that the wood cover decreased downslope with patches of sand detected in the vicinity of core C2-05. The core C12-06 recovered in late December 2006 consists of wood debris interlayered with silty fine sand and medium-grained sand (Figure 18). The upper 30 cm of core - a volume of approximately 2300 cm 3 - was inhabited by five or six light green bivalves of 1.5 cm width. Core C1-05 shows 60 cm of silty material at the top. In summary, the material on the riverbed at 90 m distance consists of silt and wood debris, material that has a lower hydraulic conductivity than sand, while further downslope the material is sandier, at least in the summer months during high flow. Core C12-06 consists of relatively impermeable silty material, but was recovered during the winter when flows are low. Thus it appears that local groundwater discharges into the river at approximately 92 m to 100 m distance during the summer months. The following scenario is conceivable: During the 31 winter months finer material of lower permeability settles on the river bed and as a result of this and the higher discharge, the area over which groundwater discharges increases. When the finer material gets washed away by higher summer flows, the hyporheic sediments are washed away together with any secondary mineral precipitates, leaving little evidence of their former presence. 5.1.1 Rietveld X-Ray Diffraction and Scanning Electron Microscopy Scanning electron microscopy revealed a single iron sulphide crystal approximately 10 pm in length found on sediment from a depth of 1.2 m below the riverbed (Figure 21). The crystal is too large to have been formed by magnetotactic or dissimilatory iron-reducing bacteria, which can produce greigite ( F e 2 + F e 3 + S 4 ) particles on the order of 100 to 1000 nm in size (Hesse and Stolz 1999). This suggests that the crystal may be a remnant of the rocks that make up the Fraser River sediments. Amorphous iron mineral coatings, as shown in Figure 22, were found in several samples, confirming the presence of secondary iron mineral precipitates. Since it is not possible to detect carbon or oxygen with the S E M , these mineral are assumed to be either iron oxides or iron carbonates. In the X-ray diffraction analyses all sediment samples analyzed exhibited very similar 20 refraction patterns, indicating a similar mineralogical composition. In fact, the same minerals were identified in all nine samples (Table 6). The mineralogy of the sediments reflects the geological makeup of the Fraser River catchment basin that is largely underlain by granitic rock. Iron-bearing minerals found in the samples are chlorite with an average abundance of 6.5% and hornblende, with an average abundance of less than 2%. Additionally, magnetite was extracted from sediment samples by a magnetic separation and found to have an abundance of approximately 1%. The reductive dissolution of these minerals could explain the high iron concentrations found in the aquifer. 32 Ankerite was identified as the carbonate mineral present in the aquifer material with low concentrations of generally less than one percent. No evidence of other carbonate minerals typically encountered in aquifer sediments such as calcite or siderite was found, but may be present as an amorphous phase that is not detectable by X-ray diffraction. The error of the Rietveld analysis is in the range of several percent. Therefore the exact percentage of minerals with an abundance of less than 5 percent cannot be determined accurately. 5.2 Results of Water Analyses 5.2.1 Organics Indane is the pollutant with the highest concentrations in the off-shore contaminant plume, followed by benzothiophene and naphthalene (see Figure 23). This agrees with previous observations reported by Bishop (2003). Naphthalene concentrations appear to have been significantly attenuated since the last observations in 2003. However, it is difficult to compare values directly as the morphology of the site as surveyed does not agree with the illustrations in previous publications. Complete results of the water analyses are available in Appendix A. Profiles of the contaminants are compared with concentrations of iron and methane in Figure 23. Bishop (2003) had concluded that degradation of organic matter in this aquifer is accomplished by methanogenesis with limited Fe(lll) reduction. Fe(lll) could originate from iron-bearing minerals such as chlorite and magnetite. In fact, Kostka and Nealson (1995) present evidence for the reductive dissolution of magnetite. The simultaneous analysis of the groundwater samples for both organic contaminants and inorganic constituents allows for a direct comparison in this study. Dissolved iron and methane concentrations increase in the groundwater by the following degradation reactions with organic matter, represented here by the generic organic compound CH 2 0 : 2 F e 3 0 4 + C H 2 0 + 11 H + = 6 Fe 2 + + 6 H 2 0 + C 0 2 + OH" (1) 33 2 H 2 + C H 2 0 + C 0 2 C H 4 + H 2 0 + C 0 2 (2) Both reductive dissolution of iron (Lovley et al. 1990, Albrechtsen and Christensen 1994, Kostka and Nealson 1995) and methanogenesis (Grossman et al. 1989) are microbially enhanced in aquifers. The profile for P6-05 (Figure 23) shows high concentrations of indane, benzothiophene and iron between depths of 1-3 metres. Methane concentrations are high but do not follow this trend and stay between 11 and 15 mg/L throughout the profile. Profile P22-05 (Figure 23) shows highest concentrations of indane and iron between 1.5 and 3 metres depth, whereas methane does not follow that pattern. For comparison, profile P23-05 (Figure 23) in the centre of the off-shore contaminant plume shows a very similar trend, where indane, benzothiophene, naphthalene and iron concentrations peak together at depths of 9 -13 metres, whereas methane concentrations range between 7 and 12 mg/L with a slight decrease in concentration in the centre of the contaminant plume. Thus in the profiles that creosote-derived contaminants were detected, there appears to be a correlation between dissolved iron and contaminant concentrations. In fact, a statistical analysis shows that there is a strong relationship between dissolved iron and indane concentrations with an r2 value of 0.67, while there is no significant correlation between methane and indane concentrations (Figure 24). This perhaps is an indication that the organic matter buried in the aquifer degrades through methanogenesis, while the dissolved organic contaminants, which are more readily available to microbial decomposition, are degraded via iron reduction. The rapid degradation of organic matter and associated reductive dissolution of iron(lll) appears to elevate concentrations of dissolved iron in the local groundwater to levels observed in the deep groundwater. 34 5.2.2 Conservative Tracer Concentrations Chloride is generally accepted to be unreactive and is therefore useful as a tracer of groundwater flow, especially at this research site, where deeper groundwater contains significantly higher concentrations of chloride than the river water. Chloride concentrations are linearly correlated with conductivity measurements with an r2 value of 0.95. Chloride concentration in the local groundwater are between 3 and 20 mg/L as seen in profiles P23-05 and P6-05, whereas groundwater profiles P22-05 and P3-06 taken further towards the centre of the channel show concentrations up to 1600 mg/L suggesting the existence of a deeper, much more saline groundwater (Figure 25). In profile P6-05 between depth of 3.5 and 4.5 m there is a sharp increase in chloride concentrations suggesting a mixing of local and deep groundwaters (Figure 25). Mixing of river water and groundwater in the hyporheic zone can be observed in profile P3-06, where chloride concentrations are low to a depth of 0.9 m and then increase rapidly with depth, suggesting that river water penetrates the sediments to a depth of 0.9 m and then mixes with groundwater to a depth of at least 1.8 m. The profile was taken during falling mid-tide. In profile P22-05, chloride concentrations increase gradually with depth, perhaps due to mixing of local groundwater with deep, chloride-rich groundwater and chloride-free river water causing the intermediate concentrations. The most detailed profile in the hyporheic zone P12-06 shows low concentrations of up to 20 mg/L of chloride in an area where deep saline groundwater is thought to discharge. This either indicates that river water has penetrated the entire length of the 60 cm long profile or that local groundwater flow has reached further into the channel. 35 5.2.3 Redox Sensitive Species Concentrations Dissolved oxygen concentrations in the river water ranged between 5 and 7.5 mg/L, while oxygen in all pore water samples were zero or below one mg/L, with the shallowest sample taken at 70 cm depth (Figure 26). Due to the high amount of ferrous iron present in all pore water samples it is assumed that dissolved oxygen concentrations in the pore waters are minimal. Sulphate concentrations range between 4.7 and 8 mg/L in the river water samples and near zero in the groundwater samples. In the most detailed hyporheic zone profile, P12-06, concentrations of sulphate decline to groundwater concentration levels within 25 cm of the surface. Iron concentrations in the same profile increase to a depth of 25 cm and remain stable (Figure 26). The decrease and increase of sulphate and iron, respectively over this short interval may be due to mixing with river water rather than a chemical reduction of the species as is indicated by the fact that ferrous iron concentrations measured in the field closely correspond to iron concentrations later measured in the lab, suggesting that there is no ferric iron in the hyporheic zone. In profile P6-05 a decrease in iron concentrations within 1.3 m of the surface is observed, implying that river water may penetrate to this depth. Similarly, in profile P22-05, the highest concentration of iron is found at 1.5 m depth. For profiles P3-06 and P12-06, ferrous iron concentrations were measured in the field. It is found that the concentrations closely match values of iron obtained from lab analysis of iron, even at the shallowest sampled intervals in profile P12-06, where a reaction with oxygen might be expected to produce ferric iron. Based on these results it is reasonable to assume that all pore water iron at this site is ferrous iron. Additionally, for profile P3-06, unfiltered water samples were analyzed for iron to test if colloidal iron oxyhydroxides are present in the pore water. All results closely match with values of ferrous iron. However, the shallowest sampled 36 interval for this analysis was 0.9 m and therefore the presence of colloidal iron closer to the surface water interface cannot be ruled out. 5.2.4 Geochemical Modelling The chemical composition of the pore and river water samples that were collected was entered into the PhreeqC computer code to obtain the saturation indexes for minerals likely to influence pore water composition: dolomite, calcite, rhodochrosite, siderite, and ankerite. Charge balance errors were generally below 10 percent (Table 7). Alkalinity for the 2005 samples was estimated through the charge balance error and therefore no charge balance errors for those samples are available. The PhreeqC input file for the model is presented in Appendix E. Ankerite had been found in the sediments using Rietveld X-ray diffraction; however, its thermodynamic properties are not contained in the databases delivered with the program. In fact, ankerite has not been observed in its pure composition CaFe(C03)2 (Xu et al. 2004 and references therein), which complicates the calculation of its properties. Xu et al. (2004) and Xu (2007) calculated thermodynamic properties of a solid solution member of ankerite CaFe0.7Mg0.3(CO3)2. This data was used to calculate the saturation index for ankerite. The pore waters in profiles P3-06 and P22-05 were found to be saturated with respect to ankerite (Table 7), while pore waters in all other profiles are undersaturated with respect to ankerite. The thermodynamic data for ankerite remains untested, but the dissolution of ankerite may be the reason for the high values of iron found in some of the water samples. Calcite and dolomite were found to be undersaturated in the pore waters modelled. Dissolution rates are assumed to be moderately slow because mussel shells were found at approximately 1 meter depth in the vicinity of profile P6-05. 37 The shells, made up of calcite or aragonite, were 30-40% dissolved with a soft, powdery surface indicative of a chemical dissolution process. The saturation indexes for rhodochrosite are in pore waters are close to zero, indicating that it is at or close to saturation. Siderite is calculated as supersaturated in all but one of the pore waters, indicating a general tendency to precipitate and suggesting that it may be present as a secondary mineral precipitate (Table 6). It should be noted that the calculations of saturation indexes with PhreeqC are approximations of complex non-equilibrium conditions and that a positive saturation index does not indicate a mineral is actually precipitated as kinetic reactions may be slow. In fact, Wersin et al. 1991 found that siderite precipitates out of supersaturated waters at an exceedingly slow rate. The profiles for saturation indices are relatively uniform with depth even in the shallowest samples where a rapid change in geochemical conditions is expected, suggesting no remarkable changes with depth in redox conditions of the pore waters. 5.3 Results of Sediment Extractions 5.3.1 Speciation of Iron Extracts While many of the extraction solutions were analyzed immediately after the end of the extraction period, some of the extraction solutions were stored up to a month before analysis of ferrous iron as it was assumed that iron species remain stable in a low pH environment (To et al. 1999). The amount of ferrous iron in the 24-h 0.75 M HCI extraction is 3000-4000 ug/g for the 2005 sediment samples, but in the stronger 21-d 5M HCI extractions ferrous iron concentrations are considerably lower at 100-200 ug/g (Figure 27), when they would be expected to exhibit concentrations as least as high as those found in the 0.75M HCI extractions. In fact in other 5M HCI extractions, the concentrations reach up to 15,000 ug/g (Figure 31). Therefore the validity of the speciation analyses is 38 doubtful. The extractions tubes were filled under the exclusion of oxygen and closed, but then placed on a shaker table under atmospheric conditions. It is conceivable that oxygen could have diffused through the polyethylene tube walls and reacted with the ferrous iron during the 21-day extraction period. Later undocumented tests revealed that - contrary to other researchers' findings (Pehkonen 1995) - ferrous iron concentrations in all tested samples dropped several orders of magnitude within hours of exposing the samples to the atmosphere in an apparent oxidation reaction. Because there is no record for which samples were analyzed immediately and which were stored for some time after the extraction time ended, only total iron concentrations are considered in this thesis. 5.3.2 Results of Total Iron Concentrations In total, sediment cores from seven separate locations were analyzed as described in section 3.2.3. A map of the locations is shown in Figure 10, while a cross-section of the core locations is given in Figure 11. None of the sediments exhibited visible iron oxide staining, but when the wet sediments were removed from the coring tubes and left exposed to air, a highly visible coating of light yellowish brown to dark reddish brown rust developed on the sediments. This is further evidence that pore waters are anoxic up to the sediment surface in contact with river water and that dissolved oxygen in the river water does not reach even the shallow sediments. Minimum, maximum, median and mean values for all extractions are presented in Tables 8, 9 and 10. Iron concentrations for the calcium chloride extractions range between 100 and 500 ug of iron per gram of sediment (ug/g) with a peak value of 1366 ug/g. A test extraction with a pure water solution determined that the contribution of iron from pore water to the calcium chloride extraction values is between 10 and 25 per cent. For the 0.75 M HCI extractions values range between 4000 and 7000 ug/g and the 5 M HCI extractions show concentrations ranging between 17,000 to 39 23,000 ug/g with a peak value of 37,000 ug/g (Figures 28 - 30). Concentration values for all extractions can be found in Appendix B. A timed extraction was performed to ensure that the 21-day interval chosen for the 5M HCI extraction was sufficient to dissolve most of the iron minerals bound to the sediment. Figure 31 shows that more than 80 per cent of the total dissolution occurs within 3 days and the values level off after 11 days. The highest variability in iron concentrations is found in the deep aquifer core C3-05. While the variability in the deep aquifer cannot be explained with certainty, the high variability found in the shallow part of core C1-05 may be due to disturbance of the sediments through anthropogenic activity. Some of the analyses could have been affected by iron from tools or structures buried in the sediment as the area was industrially developed. Only the calcium chloride extractions in core C12-06 (Figure 30) exhibited a distinct increase of iron with depth. At all other locations, the depth profile was uniform and did not exhibit a distinct peak in iron concentrations as found by other researchers investigating hyporheic zone sediments (Benner et al. 1995, Charette et al. 2005, Gan et al. 2006). 40 6. C o n c l u s i o n s 6.1 Depth of the Hyporheic Zone The results of sediment extractions do not reveal a distinct peak of iron accumulation in the depth profile and can therefore not be an indicator the depth of surface water penetration as initially hypothesized. However, some of the pore water profiles give an insight into the depth of penetration of river water. In profile P6-05 the conductivity values are relatively constant in the groundwater up to the shallowest sampled interval at 70 cm depth, while in profile P12-06 sulphate and iron concentrations take on groundwater character at a depth of 25 cm. These two profiles were obtained at sites with significant silt and wood debris which cause that part of the hyporheic zone to have a relatively low hydraulic conductivity and therefore the penetration of river water appears to be limited to less than one meter. Profiles P22-05 and P3-06 were collected in area assumed to consist of largely sandy material. Profile P22-05 shows its highest iron concentrations at the shallowest sampled interval of 1.5 m, while in profile P3-06 chloride concentrations indicate a mixing of river and groundwater between depths of 0.9 and 1.8 meters, leading to the conclusion that at these sites the river water penetrates the sediments to depths of at least 1 to 1.5 meters. 6.2 Iron Accumulation and Redox Conditions The pore water data show that while iron concentrations in the aquifer are high, the iron is exclusively ferrous iron. Furthermore, all sediments cores collected lack evidence of iron oxyhydroxide precipitation. No orange or brown staining of the sediments was visible in any of the sediment cores collected, but when wet sediments were exposed to the atmosphere a highly visible layer of iron oxyhydroxides formed. 41 These findings contrast with the work of other researchers. Charette et al. (2005) performed chemical extractions on estuarine hyporheic sediment cores visibly stained with iron oxyhydroxides and obtained iron values of 4000-7000 ug/g iron, which compare to sediment iron concentrations of 4000-7000 ug/g iron obtained by the 0.75 M HCI extraction in this study. Benner et al. (1995) and Gan et al. (2005) reported iron oxyhydroxide on hyporheic zone sediments to a depth of 80 and a minimum of 30 cm, respectively. It appears plausible that the hyporheic zone sediments lack an iron oxyhydroxide coating because they precipitate out in the hyporheic zone as colloidal iron particles that are subsequently transported by advective groundwater flow out into the river. However, the values of unfiltered iron in pore water samples of profile P3-06 closely match ferrous iron concentrations. Furthermore, unlike during the field work of Charette et al. (2005), no colloidal iron particles were ever observed during sampling of pore waters. Therefore this hypothesis seems an unlikely explanation of the lack of iron oxyhydroxides. Dissolved ferrous iron is present in significant concentrations at all depths including the shallowest sampled intervals (Figure 25). It is well-documented that ferrous iron is oxidized in a fast kinetic reaction with a half-life of 20 minutes in an oxygen-rich (10mg/L) environment (Liang et al. 1993). Liang et al. (1993) also found that the half-life of ferrous iron increased to 40 hours when the concentration of oxygen was reduced to 0.02 mg/L. Therefore it is conceivable that while dissolved ferrous iron does not coexist with significant amounts of dissolved oxygen, small amounts of oxygen in the shallow aquifer persist under complex non-equilibrium conditions when temporary recharge of the aquifer supplies oxygenated river water during high tide and partially depletes oxygen at low tide during the 12.67-hour tide cycle. To estimate the potential precipitation of the amount of iron oxyhydroxides in the hyporheic zone, one can perform a calculation to that extend based on the available data. Assuming the following parameters: 42 Iron in groundwater: 40 mg/L (average value) Flow velocity: 100m/year (estimated by Bianchin 2001) Porosity: 0.25 Density of sediments: 2.75g/cm3 Depth of hyporheic zone: 1 m A hypothetical volume of aquifer of one cubic metre (1m x 1m x 1m) would contain 10,000 mg of dissolved iron and 2000 kg of sediment, resulting in an average of 5 ug iron per gram of sediment. If all the dissolved iron precipitated as iron oxyhydroxide in the hyporheic zone, this would result in an average accumulation of iron on the sediments of 500 ug/g per year. At the research site of Charette et al. (2005), a similar calculation can be performed with the same assumptions, except that the hyporheic zone extends to 2 m depth and that the concentration of iron in the pore water is 3 mg/L. This results in an average accumulation rate of iron on the sediments of 18 ug/g per year. However, while at the research site of Charette et al. (2005) significant accumulations of iron oxyhydroxides were found in the hyporheic zone, none were found in this study. In fact, dissolved iron in this study persists in the aquifer at less than 10 cm depth as seen in profile P12-06. This leads to the conclusion that oxygen from the river water does not penetrate the aquifer to any significant depth and that redox conditions in the hyporheic zone are reducing. It is likely that iron oxyhydroxides precipitate out either in the first few centimetres of sediment or as the groundwater discharges into the river and that the precipitates are washed away either in the river current or by the current's reworking of the sediment interface. While river water penetrates the shallow sediments, the dissolved oxygen it holds is removed in the upper few centimetres of the hyporheic zone. The large amount of organic material in the shallow sediments probably creates strongly reducing 43 conditions that are capable of rapidly reducing the oxygen as the river water enters the sediments. Possible reaction mechanisms are the oxidation of dissolved methane and dissolved organic carbon as groundwater and river water mix. Despite the high values of iron found on the sediments in this study, it appears that none of the sediment-bound iron is in the form of iron oxyhydroxides. However, both magnetite and chlorite have been found in the sediments. Both minerals incorporate significant amounts of iron in their mineral structure. Based on their relative abundances in the sediment, the complete dissolution of these two minerals would lead to iron concentration values of between 16,000 and 20,000 ug/g, depending on the iron content of the chlorite. Since iron concentrations in the 5M HCI extractions range between 18,000 and 23,000 ug/g, it is possible that all of the acid-extractable iron is caused by the dissolution of these iron-bearing minerals. It is therefore recommended that all chemical sediment extractions are accompanied by a mineralogical analysis of the sediments. For the most complete study of metal accumulation on sediment, and to easily distinguish between primary and secondary mineralization, it is favourable to amend the collection of native sediment with the in-situ placement of bead columns as carried out by Gan et al. (2005). 44 7 . S u m m a r y This research project represents the first attempt to thoroughly characterize the geochemistry of the hyporheic zone of a large river. A key component was the collection of pore water and sediment sample from the hyporheic zone. Pore waters were sampled with a Waterloo Drive-Point Profiler, while sediments were collected with a freeze-shoe corer. Difficulties with the freeze-shoe corer led to the development of a freeze corer cooled by liquid nitrogen. This sampling tool represents a novel technique for sediment sampling in the hyporheic zone of large rivers. A summary of the results is presented in point form. 1. The river bottom at the site consisted of interlayered sand, silt with between one and eighty percent wood debris, becoming increasingly more sandy towards the center of the river channel. 2. The sediments collected in this study were not observed to contain any iron oxyhydroxides that were hypothesized to form in the hyporheic zone when oxygen-rich river water mixes with iron-rich groundwater. Therefore it appears that oxygen does not penetrate into the hyporheic zone and is sequestered in the upper few centimetres of sediment. Large amounts of organic carbon in the shallow sediments and dissolved methane in the pore water probably create a highly reducing environment capable of reducing the dissolved oxygen as river water enters the hyporheic zone. 3. Large amounts of iron were found in the sediments. Iron-bearing minerals chlorite and magnetite are present in the sediment in sufficient quantity to cause the concentrations of iron found in the sediments during sediment extractions. It is therefore recommended that in the future all chemical sediment extractions are accompanied by a mineralogical analysis of the sediments. 4. Concentrations of iron extracted from sediments are largely uniform with depth and do not peak in the hyporheic zone sediments as other researchers have 45 found. Iron concentrations for the calcium chloride extractions range between 100 and 500 ug of iron per gram of sediment (ug/g)- For the 0.75 M HCI extractions values range between 4000 and 7000 ug/g and the 5 M HCI extractions show concentrations ranging between 18,000 to 23,000 ug/g. 5. Though no significant amounts of oxygen from river water penetrates into the sediments, river water does mix with groundwater in the hyporheic zone as evidenced by chloride concentration profiles. Where the river sediments are silt-dominated, the hyporheic zone extends to less than one meter depth, whereas in sand-dominated river sediments the hyporheic zone extends to depths of at least 1 to 1.5 meters. 46 Analysis Container Method/Notes P6-05 P22-05 P23-05 P3-06 P12-06 Anions 60 ml polyethylene bottle Bottle filled Yes Yes Yes Yes Yes Cations 60 ml polyethylene bottle Filtered (0.45 micron), preserved with acid to less than pH2 Yes Yes Yes Yes Yes PAHs 40 ml glass with Tefon-septum in screw cap Bottles filled with minimal or no head space Yes Yes Yes Yes No Methane 500 ml brown glass bottle Bottles filled with minimal or no head space Yes Yes Yes No No DOC 250 ml brown glass bottle Preserved with HCI Yes No Yes No No Table 1 - Water samples taken for analysis. Reagent Duration Target phase 1 M CaCI2 24 hours Pore water and exchangeable fraction 0.75 M HCI 24 hours Amorphous and weakly crystalline minerals 5.0 M HCI 21 days Total crystalline minerals bound to surface Table 2 - Single-step extractions used in sample analysis (Heron and Christensen 1995) 47 C1-05 medium depth [m] Description 0.25 silty sand with visible mica 0.35 silty sand with visible mica and some wood chips 0.45 silty sand mixed with 5-10% wood matter 0.56 silty sand mixed with 60% wood matter 0.66 silty sand 0.76 silty sand 0.86 pebbly sand (pebbles 1-3 mm) 0.96 pebbly sand (pebbles 1mm to 1cm) 1.06 pebbly sand (pebbles 1mm to 1cm) and clam shells 1.17 pebbly sand (pebbles 1mm to 1cm) and clam shells 1.27 dark grey coarse sand 1.37 dark prey coarse sand 1.47 dark qrey coarse sand 3.19 3.25 dark grey coarse sand 3.35 dark qrey coarse sand 3.45 dark grey coarse sand and thin slice of plant matter 3.56 dark grey coarse sand 3.66 dark grey coarse sand 3.76 dark grey coarse sand 3.86 dark grey coarse sand 3.96 dark qrey coarse sand 4.06 black medium to coarse grained sand 4.17 black medium to coarse qrained sand 4.27 black medium to coarse grained sand C3-05 medium depth [m] Description 10.14 0.2cm pebbles mixed with coarse sand 10.26 0.2cm pebbles mixed with coarse sand 10.36 coarse sand with 1mm to 1cm pebbles 10.46 coarse sand with 1mm to 1cm pebbles 10.57 coarse homogeneous sand 10.67 coarse homogeneous sand 10.77 coarse sand with clay as small scale (10cm) heterogeneity 10.87 coarse sand with clay as small scale (10cm) heterogeneity 10.97 silt with wood debris 11.07 silt with wood debris 11.18 medium to fine qrained sand with visible mica 11.28 medium qrained sand 11.38 medium qrained sand with some silt 11.48 medium qrained sand with some silt 11.87 coarse sand and empty air-filled space with water movinq about 11.99 medium to coarse grained dark grey homogeneous sand 12.09 medium to coarse grained dark grey homogeneous sand 12.19 medium to coarse grained sand with ~1cm clay blobs 12.29 pebbles, coarse sand, clay and wood debris mix 12.40 silt to fine sand with -10% wood matter and frequent clay blobs 12.50 silt to fine sand with -10% wood matter and frequent clay blobs 12.60 silt to fine sand with ~10% wood matter and frequent clay blobs 12.70 medium to coarse qrained homoqeneous sand with visible white mica 12.80 medium to coarse qrained homoqeneous sand with visible white mica 12.90 medium to coarse qrained homoqeneous sand with visible white mica 13.00 medium to coarse qrained homoqeneous sand with visible white mica 13.11 medium to coarse qrained homoqeneous sand with visible white mica Table 3 - Core logs for cores C1-05 and C3-05. Depth indicated is the medium depth of a 10 cm interval. 48 C 2 - 0 5 medium depth [m] Description 0.71 medium grained dark qrey/black homogeneous sand with visible white mica 0.81 medium grained dark qrey/black homogeneous sand with visible white mica 0.91 medium grained dark qrey/black homoqeneous sand with visible white mica 1.02 medium qrained dark qrey/black homogeneous sand with visible white mica 1.12 medium grained dark qrey/black homoqeneous sand with visible white mica 1.22 medium qrained dark qrey/black homogeneous sand with visible white mica 1.32 medium qrained dark qrey/black homoqeneous sand with visible white mica 1.42 medium qrained dark qrey/black homogeneous sand with visible white mica 1.52 medium grained dark qrey/black homogeneous sand with visible white mica 1.63 medium qrained dark qrey/black homogeneous sand with visible white mica 1.73 medium qrained dark qrey/black homoqeneous sand with visible white mica 1.83 medium qrained dark qrey/black homoqeneous sand with visible white mica 1.93 medium grained dark qrey/black homogeneous sand with visible white mica 2.34 medium qrained dark qrey/black homoqeneous sand with visible white mica 2.46 medium qrained dark qrey/black homogeneous sand with visible white mica 2.57 medium qrained dark qrey/black homogeneous sand with visible white mica 2.67 medium qrained dark qrey/black homoqeneous sand with visible white mica 2.77 coarse grained sand with up to 5mm diameter pebbles 2.87 coarse qrained sand with up to 5mm diameter pebbles 2.97 medium grained dark qrey/black homogeneous sand with visible white mica 3.07 coarse to medium qrained sand with 1.5cm pebbles interspersed 3.18 medium grained dark grey/black homoqeneous sand with visible white mica 3.28 medium qrained dark qrey/black homoqeneous sand with visible white mica 3.38 medium grained dark qrey/black homoqeneous sand with visible white mica 3.48 medium grained dark qrey/black homoqeneous sand with visible white mica 3.58 medium grained dark qrey/black homoqeneous sand with visible white mica C 1 - 0 6 0.03 wood debris with some fine silt (up to 20%) 0.11 silt with some wood debris (up to 15%) C 2 - 0 6 0.03 qravel and coarse sand 0.10 coarse sand C 4 - 0 6 0.04 pebbles and coarse sand 0.13 medium to coarse-qrained dark sand 0.23 medium to coarse-qrained dark sand 0.33 medium-qrained sand 0.43 medium-qrained sand 0.53 medium-qrained sand Table 4 - Core logs for cores C2-05, C1-06, C2-06 and C4-06. Depth indicated is the medium depth of a 10 cm interval. 49 C12-06 medium depth [m] Description 0.05 A mixture of areas of sand, fine sand and silt mixed with wood debris and chuncks of wood up to 20 cm in length. Also gravel and subangular pebbles and 1.5cm wide bivalves 0.15 A mixture of areas of sand, fine sand and silt mixed with small wood debris. The odd pebble. Fewer bivalves 0.25 A mixture of silty fine sand and wood debris chunks, some clearly cut pieces similar to that used for house construction. One bivalve. More silt than above. 0.35 Fine silty sand mixed with medium-grained sand and wood debris 0.45 Fine silty sand mixed with medium-grained sand and wood debris 0.55 Fine silty sand mixed with medium-grained sand and wood chips. Very bottom is 3 cm of wood chips. Table 5 - core log for core C12-06. Depth indicated is the medium depth of a 10 cm interval Depth Mineral 1.2 m 1.7 m 2.1 m 2.2 m 3.5 m 10.5 m 12.5 m 12.6 m Albite 32.44 39.19 33.55 34.88 34.20 35.28 32.26 31.91 Ankerite 0.79 1.10 0.70 0.39 1.10 0.61 0.95 0.65 Chlorite 6.55 5.59 8.27 6.96 6.82 6.74 6.70 5.29 Muscovite 1.86 1.91 2.22 2.67 2.29 2.00 3.86 2.50 Quartz 57.36 51.05 53.46 53.08 54.13 54.36 54.65 58.16 Hornblende 0.99 1.16 1.80 2.03 1.47 1.01 1.58 1.49 Table 6 - Percentages of minerals in sediment samples as modeled with Topas 3. Note that the iron-bearing minerals, chlorite and hornblende, generally make up less than 10% of the total. 50 Sample depth (m) SI Calcite SI Dolomite SI Siderite SI Rhodochrosite SI Ankerite Charge balance P6-05 -01 0 -1.3223 -3.1626 -0.0246 -1.0131 -1.9232 n/a P 6 - 0 5 - 0 2 0.69 -2.1067 -4.5348 0.2666 -0.7595 -2.6801 n/a P 6 - 0 5 - 0 3 0.99 -2.0203 -4.2409 0.4249 -0.6673 -2.4207 n/a P 6 - 0 5 - 0 4 1.30 -1.619 -3.3998 0.8537 -0.2401 -1.5872 n/a P 6 - 0 5 - 0 5 1.60 - 2 . 3 3 9 -4.8583 0.1092 -0.9739 -3.0499 n/a P6-05-06 1.91 -2.0392 -4.2579 0.3578 -0.7127 -2.486 n/a P6-05-07 2.21 -2.2751 -4.7957 0.0269 -1.0112 -3.0441 n/a P6-05-08 2.51 -1.8702 -4.0457 0.2933 -0.7157 -2.3491 n/a P6-05-09 2.82 -2.1923 -4.7383 -0.1162 -1.0888 -3.0691 n/a P6-05 - 1 0 3.12 -1.6143 -3.5919 0.3468 -0.5909 -1.9964 n/a P6-05-11 3.43 -0.9526 -2.271 0.917 0.0016 -0.7379 n/a P6-05-12 3.73 -1.4797 -3.3183 0.3817 -0.5255 -1.7957 n/a P 6 - 0 5 - 1 3 4.04 -0.801 -1.947 0.9877 0.0818 -0.485 n/a P6-05 - 1 4 4.34 -0.5479 -1.4353 1.1604 0.2829 -0.0335 n/a P6-05 - 1 5 4.65 -1.223 -2.7814 0.5541 -0.2949 -1.3343 n/a n/a n/a P 2 2 - 0 5 - 1 3 0 -1.2464 -3.046 -1.2086 -1.5543 -2.6639 n/a P22-05- 8 1.52 -0.2525 -0.9938 1.2075 0.6302 0.3387 n/a P22 -05^ 2.74 -0.3385 -1.1641 0.9548 0.6593 0.0506 n/a P22-05-1 3.05 -0.1053 -0.6437 1.1062 0.8558 0.4759 n/a P22-05- 2 3.35 -0.2188 -0.6586 0.8245 0.5423 0.1947 n/a P 2 2 - 0 5 - 3 3.66 -0.2851 -0.3093 0.5458 0.087 0.0581 n/a n/a n/a P23-05-1 0 -0.9531 -2.5597 -1.0545 -1.3131 -2.2048 n/a P23-05- 6 7.32 -1.6039 -3.2549 0.6501 -0.6933 -1.6758 n/a P23-05- 7 7.62 -1.5421 -3.1332 0.7441 -0.62 -1.5301 n/a P23-05- 8 7.92 -1.3807 -2.7858 0.9694 -0.4008 -1.1552 n/a P23-05- 9 8.23 -1.3205 -2.6672 1.0486 -0.311 -1.022 n/a P23-05-10 8.53 -1.8505 -3.7249 0.548 -0.7953 -2.0609 n/a P23-05-11 9.14 -1.271 -2.5658 1.1541 -0.1989 -0.8831 n/a P 2 3 - 0 5 - 13 10.67 -1.2163 -2.5642 1.3484 -0.0224 -0.7084 n/a P23-05- 14 10.97 -1.2127 -2.5691 1.3518 . 0.0332 -0.7049 n/a P23-05- 15 11.58 -1.2042 -2.6161 1.3096 0.0275 -0.7427 n/a P23-05- 1 6 11.89 -1.1797 -2.5377 1.3066 0.0989 -0.7041 n/a P23-05-17 12.5 -0.9044 -2.0078 1.253 0.3892 -0.3899 n/a P23-05-18 12.8 -0.6212 -1.4445 1.3406 0.3428 0.0386 n/a P23-05-19 13.41 -0.6183 -1.4956 0.991 -0.2844 -0.2194 n/a P23-05- 20 14.02 0.0372 -0.248 1.6049 0.263 1.0434 n/a P3-06-R 0 -1.4584 -3.3617 -1.3342 -2.0896 -2.9949 1.26% P 3 - 0 6 - 0 3 0.91 -1.0229 -2.2238 1.3561 0.2925 -0.4655 -6.49% P 3 - 0 6 - 0 4 1.22 -0.5536 -1.3783 1.6395 0.6504 0.315 -4.61% P3-06-05 1.52 -0.2806 -0.9772 1.6114 0.7594 0.6068 -5.02% P3-06-06 1.83 -0.0023 -0.4733 1.6576 0.8925 0.9851 -6.99% P12-06-1 0.05 -1.335 -3.2733 0.023 -0.0285 -1.932 10.70% P12-06-2 0.15 -1.166 -2.9608 0.6485 0.1268 -1.2821 2.85% P12-06-3 0.25 -1.3587 -3.2475 0.7252 -0.075 -1.4493 5.34% P12-06-4 0.35 -1.3788 -3.2398 0.7522 -0.0669 -1.4422 6.16% P12-06-5 0.45 -1.3984 -3.2575 0.7371 -0.0999 -1.4718 7.19% P12-06-6 0.55 -1.5163 -3.4731 0.6966 -0.2159 -1.6473 13.83% Table 7 - Saturation indeces of selected minerals in water samples as calculated with PhreeqC. Note: 0 m depth indicates river water. 51 Core Minimum Maximum Median Mean C1-05 96 1366 266 338 C2- 05 108 274 165 171 C3- 05 84 596 195 225 C1-06 586 1194 - -C2-06 65 179 - -C4-06 50 225 196 168 C12-06 trending data Table 8 - CaC12 extraction values in u.g Fe/g dry sediment Core Minimum Maximum Median Mean C1-05 2759 6704 4885 4660 C2- 05 4834 6369 5621 5637 C3- 05 2980 11433 5816 6516 C1-06 586 1194 - -C2-06 65 179 - -C4-06 2676 6798 5935 5414 C12-06 6667 23179 8664 9706 Table 9 - 0.75 M HCI extraction values in u.g Fe/g dry sediment Core Minimum Maximum Median Mean C1-05 13911 41557 17907 18742 C2- 05 16828 19771 18582 18455 C3- 05 9260 33828 18946 19341 C1-06 13849 20690 - -C2-06 21600 30654 - -C4-06 18596 37582 20498 22147 C12-06 19792 30571 22770 24048 Table 10 - 5 M HCI extraction values in jag Fe/g dry sediment Figure 1 - Map of Western Canada. The Fraser River drainage basin is outlined in dark grey. 53 Pacific Ocean • f 1 White Rock TST1 NI Figure 2 - Map of the Lower Mainland showing the field site on the Fraser River. 54 Figure 3 - Aerial photo of field site showing location of the cross-section and the hyporheic zone. Cross - Section A > 0) > o a. a 5 0 -5 -10 -15 -20 -25 i i i i | ! I I | I I | I A' : > ^ - S i l t soil and fill : Interbedded z silt and sand River : Sand with occasional : silt interbeds Hyporheic interface under investigation 0 20 1.6 x Vertical Exaggeration 40 60 80 Distance (m) 100 120 Approximate contact between stratigraphic units riverbed approximate extent of hyporheic zone Figure 4 - Cross-section showing site stratigraphy and hyporheic interface A Aquifer Hydrogeology local flow "i 1 i | r 0 1.6 x Vertical Exaggeration 20 40 60 80 Distance (m) A River 4 regional flow 1 1 r 100 120 approximate contact between stratigraphic units — approximate extent of contaminant plume riverbed approximate extent of hyporheic zone Figure 5 - Cross-section showing aquifer hydrogeology Figure 6 - The boat used for sampling anchored at the field site. Figure 7 - Side view schematic of boat with sampling gear deployed. retracted insertion piston Core barrel Sediment core Core liner' Frozen sediment plug C02 line Freeze-shoe Figure 9 - Schematic of freeze-shoe corer. Figure 10 - Map view of sampling locations relative to the cross-section. A > 0) > o n a a 5 0 -5 -10 -15 -20 -25 0 Core and Profiling Locations C3-04, P23-05 20 1.6 x Vertical Exaggeration n 1 1 1 r C1-04, C1-05, P6-05, C1-06 C2-05, P22-05, C2-06 i 1 —r "i r i r 40 60 80 Distance (m) 100 P3-06 C4-06 1 r A' 120 approximate contact between stratigraphic units — approximate extent of contaminant plume riverbed approximate extent of hyporheic zone Figure 11 - Cross-section showing core and profiling locations. Prefix ' C indicates core and prefix 'P ' indicates a pore water profile. Slide hammer Coupling / I iwith pressure -elease valve Core barrel Tip with core catcher Figure 12: Phleger corer with slide hammer used by the divers. A core catcher inside the tip prevents sediment from falling out while a pressure release valve at the top allows excess water to escape. 63 STEEL BRACKET LIQUID NITROGEN AW DRILL ROD -CASING BOAT ON 4^ Figure 13 - Schematic of freeze-corer as deployed from boat. COPPER PIPES (13mm diameter) STOPPER PLATE STYRAFOAM SPACERS NON-WELD UNION WELDED SEAL EVAPORATION CHAMBER INSERTION TIP Figure 14 - Schematic of freeze corer a) b) c) Figure 15 - Freeze-corer assembly lifted into place, a) freeze corer with drill rod casings and steel bracket attached is picked up from the deck of the boat, b) the assembly is turned into vertical position and lifted over side of the boat, c) the assembly is lowered into the water and attached to the boat with the steel bracket. Figure 18 - Close-up of frozen sediment core. Tape measure indicates a length of 23 inches. 67 5.5 m Pneumatic hammer Sampling manifold \ / River Level Profiling tip Figure 19 - Rear view schematic of pore water profiling gear deployed from boat. 68 Figure 20 - Pore water sampling gear on deck of the boat. From left to right: Sampling manifold, peristaltic pump and flow-through cell. 69 Figure 22. Amorphous iron mineral coating on sediment grain Figure 23 - Concentration profiles showing depth versus contaminants, dissolved iron and methane concentrations. Figure 24 - Statistical graphs correlating iron and methane versus indane concentrations. 72 P6-05 Concentration of iron species (mg/L) 0 10 20 30 40 50 60 O p — H 1 1 1 1 1 5 J , , , , 1 . 0 50 100 150 200 250 Concentration of Chloride (mg/L) | — • — Chloride Iron"] P3-06 Concentration of iron species (mg/L) 0 20 40 60 80 100 2-I , , , , , 1 0 200 400 600 800 1000 1200 Concentration of chloride (mg/L) —*—Chloride - - a - - Iron —o— Unfiltered Iron —B— Ferrous Iron 0.1 e" ^ 0.2 CD € CD I 0.3 o CD XI t 0.4 CD a 0.5 P22-05 Concentration of iron (mg/L) 10 20 30 40 —I 1 1 500 1000 1500 Concentration of chloride (mg/L) —*—Chloride --U-- Iron I P12-06 50 10 20 30 40 Concentration of ions (mg/L) - Chloride - - O- - Iron -Has— Ferrous Iron I 50 P23-05 Concentration of iron (mg/L) 20 40 60 D 4o _ V-d P •n 2 4 6 Concentration of chloride (mg/L) -Chloride - -a - - Iron Figure 25 - Concentrations of chloride and iron in pore water profiles. 0 m depth represents river water sample. PL 24-h CaCI2 Fe2+ Depth Profiles 2005 24-h 0.75 M HCI 21-d 5 M HCI C1-05 C1 CaCI extractions S 2 •c 12. r j t - r 1. 200 400 600 800 1000 1200 ug of Fe2+ per g of sediment C1 0.5M HCI extractions 1.5 ii s 2 lowri 2.5 £ 3 •8 3.5 4 4.5 V* « 1 r 2000 4000 6000 6000 10000 12000 ug of Fe2+ per g of sediment C1 5M HCI extractions W-50 100 150 200 250 ug of Fe2+ per g of sediment C2-05 C2 CaCI extractions C2 0.5M HCI extractions C2 SM HCI extractions 0.: ¥ S 1. i f c l ^ M I I l • • i i i l l l l l s 15 s " 2.5 £ ' 3 3.5 0 0.5 • J river bed [m] 0 UI till!! river bed [m] 0 UI )th below )th below |:3:iMI "S 3 3.5 4 -• BP • 0 200 400 600 800 1000 1200 ug of Fe2+ per g of sediment 0 2000 4000 6000 8000 10000 12000 ug of Fe2+ per g of sediment 0 50 100 150 200 250 ug of Fe2+ per g of sediment C3-05 C3 CaCI extractions C3 0.5M HCI extractions C3 5M HCI extractions 11.5 12 ; 12.5 13 13.5 m 11. 1: . 12. 1 13. 10.5 ' 11 • * •jyj 4'.o t o o t o o 1 ug of Fe2+ per g of sediment 0 2000 4000 6000 8000 10000 12000 ug of Fe2+ per g of sediment 50 100 150 200 250 ug of Fe2+ per g of sediment Figure 27 - Ferrous iron concentrations on 2005 sediment samples in ug/g. 75 C1-05 C2-05 C3-05 24-h CaCI2 Fe Total Depth Profiles 2005 24-h 0.75 M HCI 21-d 5 M HCI C1 CaCI extractions ug of FeTot per g of sediment C2 CaCI extractions s » 2 *> 2.5 G o-•= 3 3.5 • 500 1000 1500 ug of FeTot per g of sediment C3 CaCI extractions 10 10.5 I 1 1 S 11.5 500 1000 1500 ug of FeTot per g of sediment C1 0.5M HCI extractions ^ 1.5 1 2 •c I" fi 3 3.5 ug of FeTot per g of sediment C2 0.5M HCI extractions _ 1 ug of FeTot per g of sediment C3 0.5M HCI extractions . 12.5 13 13.5 ug of FeTot per g of sediment C1 5M HCI extractions U 2 I 3 3.5 10000 20000 30000 40000 50000 ug of FeTot per g of sediment C2 SM HCI extractions 7 0 10000 20000 30000 4 > w - . ' . J O ug of FeTot per g of sediment C3 SM HCI extractions ug of FeTot per g of sediment Figure 28 - Total iron concentrations on 2005 sediment samples in ug/g. 76 Fe Total Depth Profiles 2006 24-h CaCI2 24-h 0.75 M HCI 21-d 5 M HCI C1-06 C1-06 FeTot CaCI2 0 0.05 0.1 0.15 0.2 £ 0.25 0.3 0.35 0.4 0.45 0.5 500 1000 ug of FeTot per g or sediment C1-06 FeTot 0.5 HCI 0 0.05 0.1 0.15 0.2 £ 0.25 a. V •a 0.3 0.35 0.4 0.45 0.5 2000 4000 6000 8000 10000 12000 ug of FeTot per g of sediment C1-06 FeTot 5M HCI 0.1 0.15 _ 0.2 E. £ 0 25 * 03 0 35 04 1.4. 0.5 iiiliiiiiiiii illfiililiii iliillSillliii lliiiiiPII • • • H I JIBS!!!!!! 5000 10000 15000 20000 25000 ug Fe per gram of sediment C2-06 C2-06 FeTot CaCI2 C2-06 FeTot 0.5 HCI C2-06 FeTot SM HCI 0.05 0.1 0.15 „ 0-2 £ 0.25 5 0.3 0.35 0.4 0.45 0.5 IKlliflilSllli • H B H 9 £ MNHHilll 0 0.05 0.1 0.15 0.2 £ 0.25 a. 0.3 0.35 0.4 0.45 0.5 0 0.05 0.1 0.15 0.2 £ 0 25 a. •a 0.3 0.35 0.4 0.45 0.5 0 50 100 150 ug of FeTot per g of sediment 2000 4000 6000 8000 10000 12000 ug of FeTot per g of sediment 10000 20000 30000 ug of Fe per g of sediment C 4 - 0 6 C4-06 FeTot CaCI2 C4-06 FeTot 0.5 HCI C4-06 FeTot SM HCI 0 0.1 0.2 0.3 0.4 £ 0.5 0.6 0.7 0.8 0.9 50 100 150 200 ug of FeTot per g of sediment 2000 4000 6000 S000 10000 12000 ug of FeTot per g of sediment 10000 20000 30000 ug of Fe per g of sediment Figure 29 - Total iron concentrations in summer 2006 sediment samples in ug/g. 77 Fe Total Depth Profiles December 2006 Dec 06 1MCaCI2 FeTot 0 0 . 1 0 . 2 £ 0 . 3 -Q . CD T3 0 . 4 0 . 5 0 . 6 500 1000 1500 ug FeTot / gram sed 0 0 . 1 0 . 2 0 . 3 0 . 4 0 . 5 0 . 6 Dec 06 0.5M FeTot IHIl^ itlillll H IMKii^flHHi •usil iililiiilll liliiiiiiii |i|i§l| IB l l i l ( l l l l l i i l 0 5000 10000 15000 20000 25000 ug FeTot / gram sed Dec 06 5M FeTot 0 0 . 1 0 . 2 0 . 3 0 . 4 0 . 5 0 . 6 0 10000 20000 30000 40000 50000 ug FeTot / gram sed Figure 30 - Total iron concentrations in the December 2006 sediment core C12-06 in ug/g. 78 Time series for C2-11.3 days after start weight of seds (g) dry sed mass (g) weight of soln (g) ml of soln cone mg/L mg total of Fe in solution mg/g ug/g FeTot 0 0 0 0 0 3 1.63 1.30 29.49 27.00 751.25 20.29 15.56 15557 5 1.07 0.85 28.84 26.41 562.5 14.85 17.44 17435 7 1.21 0.96 28.79 26.36 653.75 17.23 17.87 17868 11 1.24 0.99 28.36 25.97 726 18.85 18.95 18950 15 1.35 1.08 28.89 26.45 770 20.37 18.91 18905 Extraction Time Series for C2-11.3 20000 c 18000 0) E 16000 '•5 a> in 14000 O) "5 12000 ti-ro 3 10000 C O 8000 ra 6000 c a> o 4000 c o o 2000 0 * , , , , , , , 1 0 2 4 6 8 10 12 14 16 time (days) Figure 31 - Graph and data showing results of timed sediment extraction. The extraction was done in 5 separate tubes and interrupted after the specified time and then immediately tested for Fe2+ . R e f e r e n c e s Albrechtsen, H.J., Christensen, T.H. 1994. Evidence for microbial iron reduction in a landfill leachate-polluted aquifer (Vejen, Denmark). Applied and Environmental Microbiology 60 (11): 3920 - 3925. Amirbahman, A., Schonenberger, R., Johnson, C.A., Sigg, L. 1998. Aqueous-and solid-phase biogeochemistry of a calcareous aquifer system downgradient from a municipal solid waste landfill (Winterthur, Switzerland). . Environmental Science and Technology 32 (13): 1933 - 1940. Anthony, T. 1998. An investigation of the natural attenuation of a dissolved creosote and a pentachlorophenol plume. Master of Science Thesis. The University of Waterloo, Waterloo, Ontario. Arntzen, E.V., Geist, D.R., Dresel P.E. 2006. Effects of fluctuating river flow on groundwater/surface water mixing in the hyporheic zone of a regulated, large cobble bed river. River Research and Applications 22 (8): 937 - 946. Benner, S.G., Smart, E.W., Moore, J.N. 1995. Metal behavior during surface-groundwater interaction, Silver Bow Creek, Montana. Environmental Science and Technology 29 (7): 1789 - 1795. Bianchin, M. 2001. A field investigation into the fate and transport of naphthalene in a tidally forced anaerobic aquifer. Master of Science Thesis. The University of British Columbia, Vancouver, British Columbia. Bishop, C. 2003. Field sampling and modelling of creosote-derived contamination in a tidally forced aquifer. Master of Science Thesis. The University of British Columbia, Vancouver, British Columbia Boulton, A.J., Foster, J.G. 1998. Effects of buried leaf litter and vertical hydrologic exchange on hyporheic water chemistry and fauna in a gravel-bed river in northern New South Wales, Australia. Freshwater Biology 40 (2): 229 -243. Bruker AXS. 2004. Topas V. 3.0: General Profile and Structure Analysis Software for Powder Diffraction Data. Bruker AXS, Germany. Carling, P.A., Reader, N.A. 1981. A freeze-sampling technique suitable for coarse river bed-material. Sedimentary Geology 29 (2-3): 233 - 239. Carling, P.A. 1981. Freeze-sampling coarse river gravels. British Geomorphological Research Group, Technical Bulletin 29: 19 - 29. 80 Charette, M.A., Sholkovitz, E.R. 2002. Oxidative precipitation of groundwater-derived ferrous iron in the subterranean estuary of a coastal bay. Geophysical Research Letters 29 (10): Art. No. 1444. Charette, M.A., Sholkovitz, E.R., Hansel, C M . 2005. Trace element cycling in a subterranean estuary: Part 1. Geochemistry of the permeable sediments. Geochimica et Cosmochimica Acta 69 (8): 2095 - 2109. Charette, M.A., Sholkovitz, E.R. 2006. Trace element cycling in a subterranean estuary: Part 2. Geochemistry of the pore water. Geochimica et Cosmochimica Acta 70 (4): 811 -826 . Cheary, R.W. and Coelho, A.A. 1992. A fundamental parameters approach to X-ray line-profile fitting. Journal of Applied Crystallography 25: 109 -121. Christensen, T.H., Bjerg, P.L., Banwart, S.A., Jakobsen, R., Heron, G., Albrechtsen, H.J. 2000. Characterization of redox conditions in groundwater contaminant plumes. Journal of Contaminant Hydrology 45 (3-4): 165 - 241. Church, M. 2007. Personal communication as interview conducted while looking at photographs of sediment core. Conant, B., Cherry, J.A., Gillham R.W. 2004. A PCE groundwater plume discharging to a river: influence of the streambed and near-river zone on contaminant distributions. Journal of Contaminant Hydrology 73 (1-4): 249 - 279. Coy Laboratories. 2007. http://www.coylab.com/guide.htm as accessed on May 17 2007. Fischer, H., Kloep, F., Wilzcek, S., Pusch M.T. 2005. A river's liver - microbial processes within the hyporheic zone of a large lowland river. Biogeochemistry 76 (2): 349-371. Fuller, C C , Harvey, J.W. 2000. Reactive uptake of trace metals in the hyporheic zone of a mining-contaminated stream, Pinal Creek, Arizona. Environmental Science and Technology 34 (7): 1150 -1155. Gan, P., Yu, R., Smets, B.F., MacKay, A.A. 2006. Sampling methods to determine the spatial gradients and flux of arsenic at a groundwater seepage zone. Environmental Toxicology and Chemistry 25 (6): 1487 - 1495. Gandy, C.J., Smith, J.W.N., Jarvis, A.P. 2007. Attenuation of mining-derived pollutants in the hyporheic zone: A review. Science of the Total Environment 373 (2-3): 435 - 446. Gibert, J. , Marmonier, P., Vanek, V., Plenet, S. 1995. Hydrological exchange and sediment characteristics in a riverbank: Relationship between heavy metals and 81 invertebrate community structure. Canadian Journal of Fisheries and Aquatic Sciences 52 (10): 2084-2097. Golder Associates Limited. 1997. Environmental Site Assessment Report, 25 Braid Street Site, Coquitlam, British Columbia. Report number 962-1877. Golder Associates Limited. 1998. Addendum to: Environmental Site Assessment Report, 25 Braid Street Site, Coquitlam, British Columbia. Report number 982-1830. Golder Associates Limited. 1999. Site Management Plan, 25 Braid Street Site, Coquitlam, B.C. Report number 982-1830. Gran, G. 1952. Determination of the equivalence point in potentiometric titration. Part II. The Analyst 77: 661- 671. Grossman, E.L., Coffman, B.K., Fritz, S.J., Wada, H. 1989. Bacterial production of methane and its influence on groundwater chemistry in east-central Texas aquifers. Geology 17 (6): 495-499. Hach Company. 2002. DR/2400 Spectrophotometer Procedure Manual. Loveland, Colorado. Hall, G.E.M., Vaive, J.E., Beer, R., Hoashi, M. 1996. Selective leaches revisited, with emphasis on the amorphous Fe oxyhydroxide phase extraction. Journal of Geochemical Exploration 56 (1): 59 - 78. Heron, G., Crouzet, C , Bourg, A.C.M., Christensen, T.H. 1994. Speciation of Fe(ll) and Fe(lll) in contaminated aquifer sediments using chemical-extraction techniques. Environmental Science and Technology 28 (9): 1698 - 1705. Heron, G., Christensen, T.H. 1995. Impact of sediment-bound iron on redox buffering in a landfill leachate polluted aquifer (Vejen, Denmark). Environmental Science and Technology 29 (1): 187 - 192. Hill, M.T.R. 1999. A freeze-corer for simultaneous sampling of benthic macroinvertebrates and bed sediment from shallow streams. Hydrobiologia 412: 213-215. Hofmann, B.A., Sego, D.C., Robertson, P.K. 2000. In situ ground freezing to obtain undisturbed samples of loose sand. Journal of Geotechnical and Geoenvironmental Engineering 126 (11): 979 - 989. Huettel, M., Ziebis, W., Forster, S., Luther III, G.W. 1998. Advective transport affecting metal and nutrient distributions and interfacial fluxes in permeable sediments. Geochimica et Cosmochimica Acta 62 (4): 613 - 631. 82 Hyacinthe, C , Bonneville, S., Van Cappellen P. 2006. Reactive iron(lll) in sediments: Chemical versus microbial extractions. Geochimica et Cosmochimica Acta 70 (16): 4166-4180. Kalbus, E., Reinstorf, F., Schirmer, M. 2006. Measuring methods for groundwater - surface water interactions: a review. Hydrology and Earth System Sciences 10 (6): 873 - 887. Kennedy, L.G., Everett, J.W., Dewers, T., Pickins, W., Edwards, D. 1999. Application of mineral iron and sulfide analysis to evaluate natural attenuation at fuel contaminated site. Journal of Environmental Engineering 125 (1): 47 - 56. Kostka, J.E., Nealson, K.H. 1995. Dissolution and Reduction of Magnetite by Bacteria. Environmental Science and Technology 29 (10): 2535 - 2540. Lendvay, J.M., Sauck, W.A., McCormick, M.L., Barcelona, M.J., Kampbell, D.H., Wilson, J.T., Adriaens, P. 1998. Geophysical characterization, redox zonation, and contaminant distribution at a groundwater surface water interface. Water Resources Research 34 (12): 3545 - 3559. Lesser, L.E. 2000. Laboratory and field evidence of anaerobic biodegradation of naphthalene. Master of Science Thesis. The University of Waterloo, Waterloo, Ontario. Liang, LY., McNabb, J.A., Paulk, J.M., Gu, BH., McCarthy, J.F. 1993. Kinetics of Fe(ll) oxygenation at low partial-pressure of oxygen in the presence of natural organic-matter. Environmental Science and Technology 27 (9): 1864 - 1870. Lovley, D.R., Phillips, E.J.P. 1987. Rapid assay for microbially reducible ferric iron in aquatic sediments. Applied and Environmental Microbiology 53 (7): 1536 -1540. Lovley, D.R., Chapelle, F.H., Phillips, E.J.P. 1990. Fe(lll)-reducing bacteria in deeply buried sediments of the Atlantic Coastal Plain. Geology 18 (10): 954 -957. Miller, M.P., McKnight, D.M., Cory, R.M., Williams, M.W., Runkel, R.L. 2006. Hyporheic exchange and fulvic acid redox reactions in an alpine stream/wetland ecosystem, Colorado front range. Environmental Science and Technology 40 (19): 5943-5949. Miskimmin, B.M., Curtis, P.J., Schindler, D.W., Lafaut, N. 1996. A new hammer-driven freeze corer. Journal of Paleolimnology 15 (3): 265 - 269. Moser, D.P., Fredrickson, J.K., Geist, D.R., Arntzen, E.V., Peacock, A.D., Li, S.W., Spadoni, T., McKinley, J.P. 2003. Biogeochemical processes and microbial characteristics across groundwater - surface water boundaries of the Hanford 83 Reach of the Columbia River. Environmental Science and Technology 37 (22): 5127-5134. Murphy, F., Herkelrath, W.N. 1996. A sample-freezing drive shoe for a wire line piston core sampler. Ground Water Monitoring and Remediation 16 (3): 86 - 90. Nagorski, S.A., Moore, J.N. 1999. Arsenic mobilization in the hyporheic zone of a contaminated stream. Water Resources Research 35 (11): 3441 - 3450. Pehkonen, S. 1995. Determination of the oxidation states of iron in natural waters - a review. Analyst (Cambridge, UK). Volume 120, p. 2655 - 2663. Pitkin, S.E., Cherry, J.A., Ingleton, R.A., Broholm, M. 1999. Field demonstrations using the Waterloo ground water profiler. Ground Water Monitoring and Remediation 19 (2): 122 - 131. Poulton, S.W., Raiswell, R. 2005. Chemical and physical characteristics of iron oxides in riverine and glacial meltwater sediments. Chemical Geology 218 (3-4): 203-221 . Raudsepp, M., and Pani, E. 2003. Application of Rietveld analysis to environmental mineralogy. In Environmental Mineralogy of Mine Wastes (Jambor, J.L., Blowes, D.W., and Ritchie, A.I.M., Eds.), Mineralogical Association of Canada Short Course 31: 165-180. Roschinski, T.G. 2004. An in situ desorption experiment using a push-pull methodology: A feasibility study in a naphthalene contaminated aquifer. Bachelor of Science Thesis. The Department of Earth and Ocean Sciences at the University of British Columbia, Vancouver, British Columbia. Schwoerbel, J . 1961. Ueberdie Lebensbedingungen und die Besiedlung des hyporheischen Lebensraumes. Archivfuer Hydrobiologie Supplement 25: 182 -214. Stocker, Z.S.J., Williams, D.D. 1972. A freezing core method for describing the vertical distribution of sediments in a streambed. Limnology and Oceanography 17(1): 136-138. Tessier, A. Campbell, P.G.C., Bisson, M. 1979. Sequential extraction procedure for the speciation of particulate trace metals. Analytical Chemistry 51 (7): 844 -851. To, T.B., Nordstrom, D.K., Cunningham, K.M., Ball, J.W., McCleskey, R.B. 1999. New method for the direct determination of dissolved Fe(lll) concentration in acid mine waters. Environmental Science and Technology 33 (5): 807 - 813. 84 Tuccillo, M.E., Cozzarelli, I.M., Herman, J.S. 1999. Iron reduction in the sediments of a hydrocarbon-contaminated aquifer. Applied Geochemistry 14 (5): 655 - 667. van Breukelen, B.M., Roling, W.F.M., Groen, J. , Griffioen, J. , van Verseveld, H.W. 2003. Biogeochemistry and isotope geochemistry of a landfill leachate plume. Journal of Contaminant Hydrology 65 (3-4): 245 - 268. Vervier, P., Roques, L, Baker, M.A., Garabetian, F., Auriol, P. 2002. Biodegradation of dissolved free simple carbohydrates in surface, hyporheic and riparian waters of a large river. Archiv fuer Hydrobiologie 153 (4): 595 - 604. Wagner, F., Zimmermann-Timm, H., Schbnborn, W. 2003. The Bottom Sampler - a new technique for sampling bed sediments in streams and lakes. Hydrobiologia 505: 73 - 76. Wersin, P., Hohene.r P., Giovanoli, R., Stumm, W. 1991. Early Diagenetic Influences on Iron Transformations in a Fresh-Water Lake Sediment. Chemical Geology 90 (3-4): 233 - 252. Westbrook, S.J., Rayner, J.L., Davis, G.B., Clement, T.P., Bjerg, P.L., Fisher, S.J. 2005. Interaction between shallow groundwater, saline surface water and contaminant discharge at a seasonally and tidally forced estuarine boundary. Journal of Hydrology 302 (1-4): 255 - 269. White, D.S., 1993. Perspectives on defining and delineating hyporheic zones. Journal of the North American Benthological Society 12 (1): 61 — 69. Williams, D.D. 1989. Towards a biological and chemical definition of the hyporheic zone in 2 Canadian rivers. Freshwater Biology 22 (2): 189 - 208. Xu, TF., Apps, J.A., Pruess, K. 2004. Numerical simulation of C02 disposal by mineral trapping in deep aquifers. Applied Geochemistry 19 (6): 917 - 936. Xu, TF. 2007. Personal communication by e-mail. 85 A p p e n d i x A Results of Chemical Analysis of Water Sampl PAH and Methane Data Sample Depth (m) Indane (ppb) Benzothiopene (ppb) Naphthalene (ppb) Methane mg/L P6-05-FB P6-05-01 0.00 0.00 0.00 0.00 0.01 P6-05-02 0.69 36.54 0.00 0.00 13.09 P6-05-03 0.99 33.63 4.73 0.00 10.78 P6-05-04 1.30 77.78 6.18 0.00 13.05 P6-05-05 1.60 79.08 5.41 0.00 14.08 P6-05-06 1.91 58.09 0.00 0.00 14.52 P6-05-07 2.21 39.11 0.00 0.00 14.96 P6-05-08 2.51 19.61 0.00 0.00 14.36 P6-05-09 2.82 15.29 0.00 0.00 P6-05-10 3.12 9.62 0.00 0.00 14.32 P6-05-11 3.43 5.24 0.00 0.00 11.40 P6-05-12 3.73 4.11 0.00 0.00 11.17 P6-05-13 4.04 3.58 0.00 0.00 11.42 P6-05-14 4.34 3.21 0.00 0.00 12.99 P6-05-15 4.65 3.24 0.00 0.00 13.80 P22-05- 13 0 8.00 0.00 1.06 0.12 P22-05- 8 1.52 28.28 0.00 7.54 10.57 P22-05-4 2.74 33.29 0.00 8.37 P22-05-1 3.05 30.52 0.00 7.44 19.35 P22-05-2 3.35 22.27 0.00 4.69 P22-05- 3 3.66 18.44 0.00 3.65 19.96 P23-05- FB 11.59 2.08 0.00 P23-05- 1 0 6.02 0.61 0.00 0.07 P23-05- 6 7.32 7.23 3.16 0.00 8.12 P23-05- 7 7.62 31.12 13.94 0.47 11.12 P23-05- 8 7.92 33.10 13.05 0.48 10.25 P23-05- 9 8.23 40.84 12.30 0.60 11.40 P23-05- 10 8.53 45.93 11.87 0.59 10.90 P23-05- 11 9.14 160.96 33.80 1.86 10.82 P23-05- 13 10.67 378.70 81.90 41.91 6.39 P23-05- 14 10.97 385.28 80.21 19.96 7.05 P23-05- 15 11.58 477.23 63.76 10.95 6.64 P23-05- 16 11.89 640.51 62.30 34.05 7.28 P23-05- 17 12.5 230.23 34.96 7.59 P23-05- 18 12.8 275.46 28.81 3.93 P23-05- 19 13.41 263.30 17.26 3.21 10.26 P23-05- 20 14.02 142.84 10.54 1.62 11.06 P3-06-R 0 0.00 0.00 0.00 -P3-06-03 0.91 0.00 0.00 0.00 -P3-06-04 1.22 0.00 0.00 0.00 -P3-06-05 1.52 0.00 0.00 0.00 -P3-06-06 1.83 0.00 0.00 0.00 -87 Conductivity and pH Field Data seawater 47.2 sample depth (m) pH Conductivity Temperature Cl/Ca ratio (uS/cm) (°C) in flow-through P6-05-FB 0.51 P6-05-01 0.00 7.67 104.4 23.6 0.06 P6-05-02 0.69 6.33 401 28.1 0.45 P6-05-03 0.99 6.12 382 26.2 0.44 P6-05-04 1.30 6.18 392 25.3 0.28 P6-05-05 1.60 6.18 400 25 1.09 P6-05-06 1.91 6.24 419 23.8 0.79 P6-05-07 2.21 6.29 430 21.4 0.59 P6-05-08 2.51 6.31 440 19.3 0.56 P6-05-09 2.82 6.36 457 19.5 0.36 P6-05-10 3.12 6.37 464 17.5 0.20 P6-05-11 3.43 7.07 475 15.3 0.51 P6-05-12 3.73 7.14 519 15.8 1.46 P6-05-13 4.04 7.15 629 16.2 1.66 P6-05-14 4.34 7.07 866 16.8 1.67 P6-05-15 4.65 7.03 1281 18.4 . 3.15 P22-05- 13 0 7.63 95.8 22.6 0.05 P22-05- 8 1.52 6.81 2230 24 2.46 P22-05-4 2.74 7.06 2000 20 5.31 P22-05-1 3.05 7.03 3600 19.2 5.41 P22-05- 2 3.35 7.3 5100 21.3 10.00 P22-05- 3 3.66 7.67 5700 20.3 59.55 P23-05- FB 6.44 53.4 15.3 0.81 P23-05-1 0 7.1 88.9 14.8 0.07 P23-05- 6 7.32 6.65 309 15.4 0.20 P23-05- 7 7.62 6.34 369 15.4 0.13 P23-05- 8 7.92 6.54 396 15.4 0.14 P23-05- 9 8.23 6.6 372 15.4 0.14 P23-05- 10 8.53 6.58 387 15.5 0.27 P23-05- 11 9.14 6.6 408 16.3 0.14 P23-05-13 10.67 6.54 531 16.8 0.15 P23-05-14 10.97 6.52 533 17.2 0.15 P23-05-15 11.58 6.47 559 17.8 0.15 P23-05- 16 11.89 6.46 535 18.4 0.15 P23-05- 17 12.5 6.52 624 20.2 0.08 P23-05-18 12.8 6.63 657 18.7 0.09 P23-05-19 13.41 6.59 634 18 0.08 P23-05- 20 14.02 7.25 691 17.1 0.08 P3-06-R 0 7.2 97.1 0.13 P3-06-03 0.91 6.57 466 11.8 0.42 P3-06-04 1.22 6.72 861 11.7 1.93 P3-06-05 1.52 6.75 1966 12.8 3.51 P3-06-06 1.83 6.85 3470 5.05 P12-06-0/10 0.05 - 408 - 0.44 P12-06-10/20 0.15 - 524 - 0.18 P12-06-20/30 0.25 - 464 - 0.20 P12-06-30/40 0.35 - 479 - 0.38 P12-06-40/50 0.45 - 470 - 0.16 P12-06-50/60 0.55 - 415 - 0.22 Pore Water Lab Analyses for P12-06 Cations, Anions in mg/L Sample ID TR-0710-a TR-10/20-a TR-20/30-a TR-30/40-a TR-40/50-a TR-50/60-a CANTEST ID 702080169 702080171 702080172 702080173 702120140 702120144 Date Sampled N/A N/A N/A N/A Parameter Alkalinity mg/L CaC03 119 185 160 158 159 132 depth (m) 0.05 0.15 0.25 0.35 0.45 0.55 Dissolved Anions Fluoride F - - - - - -Chloride CI 24.5 10 8.05 14.5 5.82 7.14 Bromide Br - - - - - -Sulphate S04 8.19 3.83 0.98 < 0.5 0.58 0.82 Dissolved Metals Aluminum Al 0.023 0.017 0.025 0.017 0.045 0.05 Antimony Sb < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 Arsenic As 0.009 0.016 0.018 0.019 0.03 0.024 Barium Ba 0.11 0.11 0.099 0.11 0.1 0.086 Beryllium Be < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 Bismuth Bi < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 Boron B < 0.05 0.07 0.14 0.19 0.24 0.22 Cadmium Cd < 0.0002 < 0.0002 < 0.0002 < 0.0002 < 0.0002 < 0.0002 Calcium Ca 55.2 54.5 39.5 38.5 36.2 32.9 Chromium Cr < 0.001 < 0.001 < 0.001 < 0.001 0.001 0.001 Cobalt Co 0.004 0.002 0.001 0.004 0.005 0.004 Copper Cu 0.002 0.001 < 0.001 < 0.001 0.003 0.002 Iron Fe 8.3 25 33 35.7 34 36 Lead Pb < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 Lithium Li 0.002 0.002 0.003 0.003 0.004 0.004 Magnesium Mg 10 9.32 8.48 9.23 9.12 8.68 Manganese Mn 3.78 3.84 2.67 2.77 2.53 2.25 Molybdenum Mo 0.0021 0.0021 0.0015 0.0017 0.0013 0.0012 Nickel Ni 0.007 0.004 0.002 0.009 0.01 0.008 Phosphorus P 0.2 0.2 0.3 0.2 0.2 0.4 Potassium K 3.6 3.7 4.8 5.8 6.7 6.5 Selenium Se 0.002 0.002 < 0.001 < 0.001 < 0.001 < 0.001 Silicon Si 6 8.7 11.2 12.2 16.7 13.3 Silver Ag < 0.00025 < 0.00025 < 0.00025 < 0.00025 < 0.00025 < 0.00025 Sodium Na 7.67 5.99 6.48 8.22 8.36 8.48 Strontium Sr 0.31 0.27 0.19 0.19 0.17 0.16 Tellurium Te < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 Thallium TI < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 < 0.0001 Thorium Th < 0.0005 < 0.0005 < 0.0005 < 0.0005 < 0.0005 < 0.0005 Tin Sn < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 Titanium Ti < 0.001 0.002 0:002 0.002 0.007 0.005 Uranium U 0.0008 < 0.0005 < 0.0005 < 0.0005 < 0.0006 < 0.0007 Vanadium V < 0.001 0.002 0.002 0.002 0.002 0.002 Zinc Zn < 0.005 < 0.005 < 0.005 0.007 < 0.005 < 0.005 Zirconium Zr < 0.01 < 0.01 < 0.01 <0.01 < 0.01 < 0.01 89 Pore Water Analyses for P3-06 Cations, Anions in mg/L Sample ID P3-06-R P3-06-03 P3-06-04 P3-06-05 P3-06-06 Date Sampled 4/21/2006 4/21/2006 4/21/2006 4/21/2006 4/21/2006 Time Sampled ALS Sample ID 1 2 3 4 5 Nature Water Water Water Water Water depth (m) 0 0.91 1.22 1.52 1.83 Dissolved Anions Bromide Br <0.050 <0.050 0.406 1.68 3.27 Chloride CI 1.78 14.0 136 544 1010 Fluoride F 0.036 0.052 0.060 <0.10 <0.10 Sulphate S04 5.99 <0.50 <0.50 3.0 <2.5 Nutrients Nitrate Nitrogen 0.164 0.0097 <0.0050 <0.025 0.027 Nitrite Nitrogen 0.0017 <0.0010 <0.0010 <0.0050 <0.0050 Total Metals Iron T-Fe 1.13 62.2 86.5 90.1 74.7 Dissolved Metals Aluminum D-AI <0.20 <0.20 <0.20 <0.20 <0.20 Antimony D-Sb <0.20 <0.20 <0.20 <0.20 <0.20 Arsenic D-As 0.00025 0.00900 0.00935 0.00965 0.0126 Barium D-Ba 0.014 0.044 0.091 0.278 0.407 Beryllium D-Be <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 Bismuth D-Bi <0.20 <0.20 <0.20 <0.20 <0.20 Boron D-B <0.10 0.19 0.21 0.25 0.38 Cadmium D-Cd <0.010 <0.010 <0.010 <0.010 <0.010 Calcium D-Ca 13.9 33.7 70.4 155 200 Chromium D-Cr <0.010 <0.010 <0.010 <0.010 <0.010 Cobalt D-Co <0.010 <0.010 <0.010 <0.010 <0.010 Copper D-Cu <0.010 <0.010 <0.010 0.015 <0.010 Iron D-Fe 0.114 62.4 85.7 90.1 71.7 Lead D-Pb <0.050 <0.050 <0.050 <0.050 <0.050 Lithium D-Li <0.010 <0.010 <0.010 <0.010 <0.010 Maqnesium D-Mg 3.63 16.3 27.4 42.9 48.8 Manganese D-Mn 0.0105 2.76 4.55 6.65 6.56 Molybdenum D-Mo <0.030 <0.030 <0.030 <0.030 <0.030 Nickel D-Ni <0.050 <0.050 <0.050 <0.050 <0.050 Phosphorus D-P <0.30 <0.30 <0.30 <0.30 <0.30 Potassium D-K <2.0 4.0 7.3 18.3 31.1 Selenium D-Se <0.20 <0.20 <0.20 <0.20 <0.20 Silicon D-Si 2.76 17.9 19.1 17.6 17.6 Silver D-Ag <0.010 <0.010 <0.010 <0.010 <0.010 Sodium D-Na 2.9 6.1 16.1 110 342 Strontium D-Sr 0.0702 0.145 0.286 0.636 0.946 Thallium D-TI <0.20 <0.20 <0.20 <0.20 <0.20 Tin D-Sn <0.030 <0.030 <0.030 <0.030 <0.030 Titanium D-Ti <0.010 <0.010 <0.010 <0.010 <0.010 Vanadium D-V <0.030 <0.030 <0.030 <0.030 <0.030 Zinc D-Zn 0.132 0.0977 0.182 0.0750 0.0325 Pore Water Lab Analyses for P23-05 Cations, Anions in mg/L Sample ID P23-05-16 P23-05- 17 P23-05- 18 P23-05- 19 P23-05- 20 Date Sampled Time Sampled ALS Sample ID 11 12 13 14 15 Nature Water Water Water Water Water depth (m) 11.89 12.5 12.8 13.41 14.02 Dissolved Anions Bromide Br <0.050 <0.050 <0.050 <0.050 <0.050 Chloride Cl 4.38 3.69 5.49 5.41 6.3 Fluoride F 0.032 0.027 0.03 0.027 0.026 Sulphate S04 <0.50 <0.50 <0.50 <0.50 <0.50 Nutrients Nitrate Nitrogen <0.10 <0.10 <0.10 <0.10 <0.10 Nitrite Nitrogen <0.10 <0.10 <0.10 <0.10 <0.10 Dissolved Metals Aluminum D-AI <0.20 <0.20 <0.20 <0.20 <0.20 Antimony D-Sb <0.20 O.20 <0.20 <0.20 <0.20 Arsenic D-As <0.20 <0.20 <0.20 <0.20 <0.20 Barium D-Ba 0.047 0.043 0.038 0.034 0.03 Beryllium D-Be <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 Bismuth D-Bi <0.20 <0.20 <0.20 <0.20 <0.20 Boron D-B <0.10 0.11 0.12 0.11 <0.10 Cadmium D-Cd <0.010 <0.010 <0.010 <0.010 <0.010 Calcium D-Ca 30.2 47.1 62.5 71.5 74.2 Chromium D-Cr <0.010 <0.010 <0.010 <0.010 <0.010 Cobalt D-Co <0.010 <0.010 <0.010 <0.010 <0.010 Copper D-Cu <0.010 <0.010 <0.010 <0.010 <0.010. Iron D-Fe 71.5 53.1 46.6 23.4 22.4 Lead D-Pb <0.050 <0.050 <0.050 <0.050 <0.050 Lithium D-Li <0.010 <0.010 <0.010 <0.010 <0.010 Magnesium D-Mg 14.6 21.7 28.6 28.7 25.7 Manganese D-Mn 2.26 3.71 2.4 0.635 0.558 Molybdenum D-Mo <0.030 <0.030 <0.030 <0.030 <0.030 Nickel D-Ni <0.050 <0.050 <0.050 <0.050 <0.050 Phosphorus D-P <0.30 <0.30 <0.30 <0.30 <0.30 Potassium D-K 2.1 <2.0 2.2 <2.0 <2.0 Selenium D-Se <0.20 <0.20 <0.20 <0.20 <0.20 Silicon D-Si 18.9 22.4 25.2 25.3 22.5 Silver D-Ag <0.010 <0.010 <0.010 <0.010 <0.010 Sodium D-Na 19.4 10.3 10.1 10.5 8.5 Strontium D-Sr 0.202 0.225 0.273 0.292 0.281 Thallium D-TI <0.20 <0.20 <0.20 <0.20 <0.20 Tin D-Sn <0.030 <0.030 <0.030 <0.030 <0.030 Titanium D-Ti <0.010 <0.010 <0.010 <0.010 <0.010 Vanadium D-V <0.030 <0.030 <0.030 <0.030 <0.030 Zinc D-Zn 0.0215 0.0133 0.0176 0.0313 0.0184 91 Pore Water Lab Analyses for P23-05 Cations, Anions in mg/L Sample ID P23-05-10 P23-05-11 P23-05- 13 P23-05-14 P23-05- 15 Date Sampled Time Sampled ALS Sample ID 6 7 8 9 10 Nature Water Water Water Water Water depth (m) 8.53 9.14 10.67 10.97 11.58 Dissolved Anions Bromide Br <0.050 <0.050 <0.050 <0.050 <0.050 Chloride Cl 2.97 3.04 3.62 3.8 4.37 Fluoride F 0.034 0.029 0.037 0.037 0.034 Sulphate S04 <0.50 <0.50 <0.50 <0.50 <0.50 Nutrients Nitrate Nitrogen <0.10 <0.10 <0.10 <0.10 <0.10 Nitrite Nitrogen <0.10 <0.10 <0.10 <0.10 <0.10 Dissolved Metals Aluminum D-AI <0.20 <0.20 <0.20 <0.20 <0.20 Antimony D-Sb <0.20 <0.20 <0.20 <0.20 <0.20 Arsenic D-As <0.20 <0.20 <0.20 <0.20 <0.20 Barium D-Ba 0.044 0.086 0.066 0.046 0.039 Beryllium D-Be <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 Bismuth D-Bi <0.20 <0.20 <0.20 <0.20 <0.20 Boron D-B <0.10 0.11 <0.10 <0.10 <0.10 Cadmium D-Cd <0.010 <0.010 <0.010 <0.010 <0.010 Calcium D-Ca 11.1 21.9 24.9 25.8 29 Chromium D-Cr <0.010 <0.010 O.010 <0.010 <0.010 Cobalt D-Co <0.010 <0.010 <0.010 <0.010 <0.010 Copper D-Cu <0.010 <0.010 <0.010 <0.010 <0.010 Iron D-Fe 18.3 42.8 69.3 72.1 72.4 Lead D-Pb <0.050 <0.050 <0.050 <0.050 <0.050 Lithium D-Li <0.010 <0.010 <0.010 <0.010 <0.010 Magnesium D-Mg 7.65 15.1 13.4 13.5 13.1 Manganese D-Mn 0.428 0.975 1.51 1.77 1.93 Molybdenum D-Mo <0.030 <0.030 <0.030 <0.030 <0.030 Nickel D-Ni <0.050 <0.050 O.050 <0.050 <0.050 Phosphorus D-P <0.30 <0.30 <0.30 <0.30 <0.30 Potassium D-K <2.0 <2.0 <2.0 <2.0 2 Selenium D-Se <0.20 <0.20 <0.20 <0.20 <0.20 Silicon D-Si 9.18 17.9 16.9 17.2 17.3 Silver D-Ag <0.010 <0.010 <0.010 <0.010 <0.010 Sodium D-Na 8.9 17.7 18 17.8 16.7 Strontium D-Sr 0.0612 0.128 0.15 0.162 0.182 Thallium D-TI <0.20 <0.20 <0.20 <0.20 <0.20 Tin D-Sn <0.030 <0.030 <0.030 <0.030 <0.030 Titanium D-Ti <0.010 <0.010 <0.010 <0.010 <0.010 Vanadium D-V <0.030 <0.030 <0.030 <0.030 <0.030 Zinc D-Zn 0.0071 0.0092 0.0077 0.0138 0.027 92 Pore Water Lab Analyses for P23-05 Cations, Anions in mg/L Sample ID P23-05- FB P23-05-1 P23-05- 6 P23-05- 7 P23-05- 8 P23-05- 9 Date Sampled Time Sampled ALS Sample ID 1 2 21 3 4 5 Nature Water Water Water Water Water Water depth (m) - 0 7.32 7.62 7.92 8.23 Dissolved Anions Bromide Br <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 Chloride CI 4.76 0.8 2.94 2.95 2.87 3.02 Fluoride F 0.03 0.028 0.042 0.048 0.04 0.038 Sulphate S04 2.96 6.09 <0.50 <0.50 <0.50 <0.50 Nutrients Nitrate Nitrogen <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 Nitrite Nitrogen <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 Dissolved Metals Aluminum D-AI <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Antimony D-Sb <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Arsenic D-As <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Barium D-Ba <0.010 <0.010 0.049 0.077 0.076 0.077 Beryllium D-Be <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 Bismuth D-Bi <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Boron D-B <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 Cadmium D-Cd <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Calcium D-Ca 5.87 11.6 14.6 22.9 21.2 21 Chromium D-Cr <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Cobalt D-Co <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Copper D-Cu 0.022 <0.010 <0.010 <0.010 <0.010 <0.010 Iron D-Fe 0.222 0.072 17.6 31.9 34.2 35.5 Lead D-Pb <0.050 <0.050 <0.050 <0.050 <0.,050 <0.050 Lithium D-Li <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Magnesium D-Mg 0.35 1.88 9.54 14.9 14.6 14.4 Manganese D-Mn 0.0215 0.0212 0.412 0.704 0.748 0.797 Molybdenum D-Mo <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 Nickel D-Ni <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 Phosphorus D-P <0.30 <0.30 <0.30 <0.30 <0.30 <0.30 Potassium D-K <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 Selenium D-Se <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Silicon D-Si 0.923 1.5 13.1 19.2 17.5 18.2 Silver D-Ag <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Sodium D-Na 3.8 <2.0 10.2 16.2 15.7 16.6 Strontium D-Sr 0.0171 0.0488 0.0708 0.11 0.108 0.11 Thallium D-TI <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Tin D-Sn <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 Titanium D-Ti <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Vanadium D-V <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 Zinc D-Zn 0.0455 0.0078 0.0543 0.0252 0.0123 0.0148 93 Pore Water Lab Analyses for P22-05 Cations, Anions in mg/L Sample ID P22-05-1 P22-05- 2 P22-05- 3 P22-05-4 P22-05-8 P22-05-13 Date Sampled Time Sampled ALS Sample ID 16 17 18 25 19 20 Nature Water Water Water Water Water Water depth (m) 3.05 3.35 3.66 2.74 1.52 0 Dissolved Anions Bromide Br 3.3 3.8 4.2 2.74 1.27 <0.050 Chloride Cl 1250 1430 1590 955 462 0.61 Fluoride F <0.40 <0.40 <0.40 <0.10 <0.10 0.028 Sulphate S04 <10 <10 <10 <2.5 <2.5 5.60 Nutrients Nitrate Nitroge <2.0 <2.0 <2.0 <0.50 <0.50 <0.10 Nitrite Nitrogen <2.0 <2.0 <2.0 <0.50 <0.50 <0.10 Dissolved Metals Aluminum D-AI <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Antimony D-Sb <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Arsenic D-As <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Barium D-Ba 0.584 0.416 0.133 0.408 0.184 0.010 Beryllium D-Be O.0050 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 Bismuth D-Bi <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Boron D-B 0.44 0.57 0.36 0.27 0.16 <0.10 Cadmium D-Cd <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Calcium D-Ca 231 143 26.7 180 188 11.7 Chromium D-Cr <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Cobalt D-Co <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Copper D-Cu <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Iron D-Fe 25.4 10.3 1.35 22.8 38.2 0.078 Lead D-Pb <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 Lithium D-Li 0.017 <0.010 <0.010 0.014 0.012 <0.010 Magnesium D-Mg 60.8 61.3 34.9 42.0 44.0 2.38 Manganese D-Mn 7.72 2.95 0.278 6.21 5.32 0.0188 Molybdenum D-Mo <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 Nickel D-Ni <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 Phosphorus D-P 0.36 0.68 0.66 0.32 <0.30 <0.30 Potassium D-K 42.1 37.1 15.7 31.0 17.3 <2.0 Selenium D-Se <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Silicon D-Si 20.3 15.5 5.74 15.1 19.0 2.04 Silver D-Ag <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Sodium D-Na 533 616 343 329 63.6 <2.0 Strontium D-Sr 1.49 1.15 0.368 1.07 0.781 0.0620 Thallium D-TI <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Tin D-Sn <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 Titanium D-Ti <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Vanadium D-V <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 Zinc D-Zn 0.0588 0.0221 0.0073 0.0456 0.0421 0.0062 94 Pore Water Lab Analyses for P6-05 Cations, Anions in mg/L Sample ID P6-05-08 P6-05-09 P6-05-10 P6-05-11 P6-05-12 P6-05-13 P6-05-14 P6-05-15 Date Sampled 6/23/2005 6/23/2005 6/23/2005 6/24/2005 6/24/2005 6/24/2005 6/24/2005 6/24/2005 Time Sampled 20:00 20:34 21:00 7:06 7:39 8:05 8:34 8:54 ALS Sample ID 9 10 11 12 13 14 15 16 Nature Water Water Water Water Water Water Water Water Depth (ft) 8.25 9.25 10.25 11.25 12.25 13.25 14.25 15.25 Depth (m) 2.51 2.82 3.12 3.43 3.73 4.04 4.34 4.65 Dissolved Anions Bromide Br <0.050 <0.050 <0.050 <0.050 0.075 0.184 0.284 0.608 Chloride Cl 11.4 4.83 5.18 14.1 24.8 66.4 104 210 Fluoride F 0.028 0.025 0.025 0.028 0.029 0.029 0.028 0.029 Sulphate S04 <0.50 <0.50 <0.50 <0.50 <0.50 <0.50 <0.50 <0.50 Nutrients Nitrate Nitrogen N <0.10 O.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 Nitrite Nitrogen N <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 Dissolved Metals Aluminum D-AI <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Antimony D-Sb <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Arsenic D-As 0.00442 0.00246 0.00418 0.00409 0.00249 0.00484 0.00673 0.00640 Barium D-Ba 0.016 <0.010 0.019 0.017 0.010 0.025 0.040 0.050 Beryllium D-Be <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 O.0050 Bismuth D-Bi <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Boron D-B <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 Cadmium D-Cd <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Calcium D-Ca 20.2 13.4 26.5 27.5 17.0 39.9 62.3 66.7 Chromium D-Cr <0.010 O.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Cobalt D-Co <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Copper D-Cu <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Iron D-Fe 19.3 9.98 16.3 13.6 7.56 16.0 21.7 23.8 Lead D-Pb <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 Lithium D-Li <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Magnesium D-Mg 7.28 4.32 8.36 8.62 5.41 13.1 20.7 22.3 Manganese D-Mn 0.971 0.548 0.965 0.869 0.490 1.05 1.52 1.77 Molybdenum D-Mo <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 Nickel D-Ni <0.050 O.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 Phosphorus D-P <0.30 <0.30 <0.30 <0.30 <0.30 <0.30 <0.30 O.30 Potassium D-K <2.0 <2.0 <2.0 <2.0 <2.0 2.1 3.1 3.9 Selenium D-Se <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Silicon D-Si 7.99 4.69 8.48 8.54 4.89 9.85 11.9 10.3 Silver D-Ag <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Sodium D-Na 3.2 <2.0 3.1 2.8 <2.0 3.8 5.7 9.9 Strontium D-Sr 0.0790 0.0492 0.0939 0.0953 0.0578 0.137 0.207 0.246 Thallium D-TI <0.20 <0.20 <0.20 O.20 <0.20 <0.20 <0.20 O.20 Tin D-Sn <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 Titanium D-Ti <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Vanadium D-V <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 O.030 Zinc D-Zn 0.0526 0.0113 0.0303 0.0118 0.0060 0.0256 0.012 0.0289 95 Pore Water Lab Analyses for P6-05 Cations, Anions in mg/L Sample ID P6-05-FB P6-05-01 P6-05-02 P6-05-03 P6-05-04 P6-05-05 P6-05-06 P6-05-07 Date Sampled 6/23/2005 6/23/2005 6/23/2005 6/23/2005 6/23/2005 6/23/2005 6/23/2005 6/23/2005 Time Sampled 11:01 - 12:00 14:42 15:50 16:30 17:40 18:14 18:53 ALS Sample ID 1 2 3 4 5 6 7 8 Nature Water Water Water Water Water Water Water Water Depth (ft) - -1 2.25 3.25 4.25 5.25 6.25 7.25 Depth (m) - -0.30 0.69 0.99 1.30 1.60 1.91 2.21 Dissolved Anions Bromide Br <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 Chloride CI 3.75 0.57 5.85 7.58 7.19 12.9 12.5 6.96 Fluoride F 0.040 0.030 0.034 0.035 0.031 0.033 0.029 0.023 Sulphate S04 4.66 6.23 <0.50 O.50 <0.50 <0.50 <0.50 <0.50 Nutrients Nitrate Nitroqen N 0.16 0.12 0.11 2.53 <0.10 <0.10 0.42 <0.10 Nitrite Nitroqen N <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 Dissolved Metals Aluminum D-AI <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Antimony D-Sb <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Arsenic D-As <0.00020 0.00045 0.00466 0.00936 0.00950 0.00388 0.00447 0.00284 Barium D-Ba <0.010 <0.010 0.025 0.035 0.036 0.014 0.017 0.012 Beryllium D-Be <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 <0.0050 Bismuth D-Bi <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Boron D-B <0.10 <0.10 <0.10 <0.10 0.14 <0.10 <0.10 <0.10 Cadmium D-Cd <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Calcium D-Ca 7.42 10.2 13.1 17.4 25.7 11.8 15.8 11.7 Chromium D-Cr <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Cobalt D-Co <0.010 <0.010 <0.010 <0.010 O.010 <0.010 <0.010 <0.010 Copper D-Cu 0.035 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Iron D-Fe 0.292 1.23 19.9 32.9 55.9 21.1 25.9 14.8 Lead D-Pb <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 Lithium D-Li O.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Magnesium D-Mg 0.30 2.25 4.55 7.99 12.9 5.67 7.61 4.84 Manganese D-Mn 0.0227 0.0674 0.964 1.36 2.29 0.896 1.13 0.698 Molybdenum D-Mo <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 Nickel D-Ni <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 Phosphorus D-P <0.30 <0.30 <0.30 <0.30 O.30 <0.30 <0.30 <0.30 Potassium D-K <2.0 <2.0 <2.0 <2.0 2.9 <2.0 <2.0 <2.0 Selenium D-Se <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 Silicon D-Si 0.720 1.70 5.32 11.0 17.6 7.15 8.17 5.38 Silver D-Ag <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Sodium D-Na 3.6 <2.0 3.7 7.1 9.4 3.6 4.2 2.2 Strontium D-Sr 0.0220 0.0507 0.0569 0.0857 0.128 0.0548 0.0719 0.0492 Thallium D-TI <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 O.20 Tin D-Sn <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 Titanium D-Ti <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 Vanadium D-V <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 <0.030 Zinc D-Zn 0.253 0.0337 0.0822 0.504 0.0934 0.0177 0.0282 0.0249 96 A p p e n d i x B Results of Selective Extractions of Sediment Sampl Sediment Extraction Data for C1-06, C2-06, C4-06 and C12-06 Total iron - 5.0 M HCI Extraction 2006 sed weight (g) soln weight (g) cone mg/L dry/wet ratio dry sed mass (g) ml of soln mg total of Fe mg/g Mg/g FeTot depth (m) assumed C2-06-02 0"-2"a 2.5064 30.8451 2176 0.8 2.00512 28.2464 61.4642 30.6536 30654 0.0254 C2-06-02 0"-2"b 1.6798 29.7895 1228 0.8 1.34384 27.2798 33.4995 24.9282 24928 0.0254 C2-06-02 2"-6"a 1.5618 29.7448 1031 0.8 1.24944 27.2388 28.0832 22.4767 22477 0.1016 C2-06-02 2"-6"b 2.0695 32.1411 1215 0.8 1.6556 29.4332 35.7614 21.6003 21600 0.1016 C4-06-03 0"-3"a 1.4763 29.8086 1626 0.8 1.18104 27.2973 44.3853 37.5816 37582 0.0381 C4-06-03 0"-3"b 1.0213 31.0831 746 0.8 0.81704 28.4644 21.2344 25.9895 25989 0.0381 C4-06-03 3"-7"a 1.7401 30.6386 958 0.8 1.39208 28.0573 26.8789 19.3085 19308 0.127 C4-06-03 3"-7"b 1.4572 29.1558 853 0.8 1.16576 26.6995 22.7746 19.5363 19536 0.127 C4-06-03 7"-11"a 1.3101 30.5067 769 0.8 1.04808 27.9365 21.4832 20.4977 20498 0.2286 C4-06-03 7"-11"b 1.8645 29.687 1124 0.8 1.4916 27.1859 30.5569 20.4860 20486 0.2286 C4-06-03 11"-1'3"a 1.3830 30.6323 860 0.8 1.1064 28.0516 24.1243 21.8044 21804 0.3302 C4-06-03 11"-1'3"b 1.7671 29.7799 1113 0.8 1.41368 27.2710 30.3526 21.4706 21471, 0.3302 C4-06-03 1'3"-1'7"a 1.6148 30.2989 953 0.8 1.29184 27.7462 26.4422 20.4686 20469 0.4318 C4-06-03 1'3"-1'7"b 1.2277 29.8321 737 0.8 0.98216 27.3188 20.1339 20.4996 20500 0.4318 C4-06-03 17"-1'11"a 2.1733 30.675 1151 0.8 1.73864 28.0907 32.3323 18.5963 18596 0.5334 C4-06-03 17"-ri1"b 1.5930 29.4408 923 0.8 1.2744 26.9604 24.8845 19.5264 19526 0.5334 C1-06-01 0"- 2.5"a 1.3210 29.4889 771 0.8 1.0568 27.0045 20.8205 19.7014 19701 0.03175 C1-06-01 0"- 2.5"b 1.4245 29.9731 575 0.8 1.1396 27.4479 15.7825 13.8492 13849 0.03175 C1-06-01 2.5" - 6"a 1.6079 28.6054 1016 0.8 1.28632 26.1954 26.6145 20.6905 20690 0.1143 C1-06-01 2.5" - 6"b 2.2983 29.593 1337 0.8 1.83864 27.0998 36.2325 19.7061 19706 0.1143 oo C12-06 sed weight [gl soln weight [gl measured mq/L actual cone. mg/L dry/wet ratio dry sed mass fql ml of soln mq total in soln mq Fe/q sed depth fml 0-10 qa 1.7433 31.9918 0.954856361 954.8564 0.8122 1.4160 29.3503 28.0253 19.7920 19792 0.05 0-10 qb 1.3166 31.0874 0.889192886 889.1929 0.8122 1.0694 28.5206 25.3603 23.7144 23714 0.05 10-20 ga 1.0203 33.7446 0.625626995 625.6270 0.8730 0.8907 30.9583 19.3684 21.7446 21745 0.15 10-20 gb 1.8718 32.0709 1.01869585 1697.8265 0.8730 1.6341 29.4228 49.9549, 30.5707 30571 0.15 20-30 sa 0.7916 32.4718 0.47879617 478.7962 0.8128 0.6434 29.7906 14.2636 22.1687 22169 0.25 20-30 sb 1.2389 33.3564 0.744186047 744.1860 0.8128 1.0070 30.6022 22.7737 22.6159 22616 0.25 30-40 qa 0.7847 33.1507 0.466940264 466.9403 0.7948 0.6237 30.4135 14.2013 22.7697 22770 0.35 30-40 qb 0.9873 35.9574 0.530779754 530.7798 0.7948 0.7847 32.9884 17.5096 22.3131 22313 0.35 40-50 sa 0.8963 33.9525 0.581851345 581.8513 0.7271 0.6517 31.1491 18.1241 27.8090 27809 0.45 40-50 sb 1.4843 31.9903 1.049703602 1049.7036 0.7271 1.0793 29.3489 30.8076 28.5442 28544 0.45 50-60 qa 0.7838 34.0665 0.433196534 433.1965 0.7235 0.5671 31.2537 13.5390 23.8754 23875 0.55 50-60 qb 0.8777 32.5721 0.481532148 481.5321 0.7235 0.6350 29.8827 14.3895 22.6604 22660 0.55 Sediment Extraction Data for C3-05 Total iron - 5.0 M HCI Extraction sed weight soln weight (g) remarks cone mq/L dry /wet ratio dry sed mass (g) ml of soln mg total of Fe mg/g Mg/g FeTot depth (m) C3-33.5a 1.9293 28.8167 1471.25 0.9217 1.7783 26.3889 38.8247 21.8327 21833 10.26 C3-33.5b 1.3057 28.7289 1200 0.9217 1.2035 26.3085 31.5702 26.2321 26232 10.26 C3-33.10a 2.6037 28.8844 3117.5 0.9362 2.4376 26.4509 82.4607 33.8282 33828 10.36 C3-33.10b 2.2297 28.3710 2485 0.9362 2.0875 25.9808 64.5622 30.9282 30928 10.36 C3-34.2a 1.8412 27.1122 1518.75 0.9266 1.7060 24.8280 37.7076 22.1026 22103 10.46 C3-34.2b 2.7620 28.1018 2147.5 0.9266 2.5592 25.7342 55.2643 21.5942 21594 10.46 C3-34.6a 1.7574 27.4656 oxidized 1142.5 0.8793 1.5454 25.1516 28.7358 18.5948 18595 10.57 C3-34.6b 1.0549 28.6006 oxidized 650 0.8793 0.9276 26.1910 17.0242 18.3524 18352 10.57 C3-34.10a 1.2773 29.1368 812.5 0.8946 1.1427 26.6821 21.6792 18.9722 18972 10.67 C3-34.10b 1.0624 26.4402 748.75 0.8946 0.9504 24.2126 18.1292 19.0748 19075 10.67 C3-35.2a 2.0831 28.7442 763.75 0.9010 1.8769 26.3225 20.1038 10.7113 10711 10.77 C3-35.2b 1.8365 27.8865 600 0.9010 1.6547 25.5371 15.3223 9.2599 9260 10.77 C3-35.6a 10.87 C3-35.6b 10.87 C3-35.10a 1.0385 26.6947 670 0.8293 0.8613 24.4457 16.3786 19.0169 19017 10.97 C3-35.10b 1.0938 28.2694 662.5 0.8293 0.9071 25.8877 17.1506 18.9065 18907 10.97 C3-36.2a 1.0473 28.2231 677.5 0.7963 0.8340 25.8453 17.5102 20.9962 20996 11.07 C3-36.2b 1.1214 27.9567 736.25 0.7963 0.8930 25.6014 18.8490 21.1081 21108 11.07 C3-36.6a 1.0663 28.3108 oxidized 660 0.8524 0.9089 25.9256 17.1109 18.8259 18826 11.18 C3-36.6b 1.1650 27.7772 oxidized 741.25 0.8524 0.9930 25.4370 18.8552 18.9875 18987 11.18 C3-36.10a 1.5325 28.0852 886.25 0.8597 1.3175 25.7190 22.7935 17.3006 17301 11.28 C3-36.10b 1.3378 28.0021 797.5 0.8597 1.1501 25.6429 . 20.4503 17.7811 17781 11.28 C3-37.2a 1.0735 28.8279 822.5 0.8600 0.9232 26.3992 21.7133 23.5204 23520 11.38 C3-37.2b 1.2904 26.7116 1023.75 0.8600 1.1097 24.4612 25.0421 22.5667 22567 11.38 C3-37.6a 1.5883 29.3958 1031.25 0.8444 1.3411 26.9192 27.7605 20.6995 20700 11.48 C3-37.6b 1.6287 27.9004 1167.5 0.8444 1.3752 25.5498 29.8294 21.6905 21691 11.48 C3-38.9a 11.87 C3-38.9b 11.87 C3-39.2a 2.3160 27.5062 1642.5 0.8668 2.0074 25.1888 41.3726 20.6097 20610 11.99 C3-39.2b 1.1961 28.6986 735 0.8668 1.0367 26.2808 19.3164 18.6318 18632 11.99 C3-39.6a 1.3453 28.8500 865 0.8636 1.1618 26.4194 22.8528 19.6695 19669 12.09 C3-39.6b 0.8696 27.9546 568.75 0.8636 0.7510 25.5995 14.5597 19.3868 19387 12.09 C3-39.10a 1.3300 27.5118 oxidized 945 0.8869 1.1795 25.1940 23.8083 20.1845 20185 12.19 C3-39.10b 1.2450 27.3060 oxidized 687.5 0.8869 1.1041 25.0055 17.1913 15.5697 15570 12.19 C3-40.2a 1.3460 28.8923 oxidized 816.25 0.9048 1.2178 26.4582 21.5965 17.7337 17734 12.29 C3-40.2b 1.4193 28.6084 oxidized 722.5 0.9048 1.2841 26.1982 18.9282 14.7400 14740 12.29 C3-40.6a 1.3486 28.9979 793.75 0.8063 1.0874 26.5549 21.0779 19.3841 19384 12.40 C3-40.6b 1.0505 27.7425 648.75 0.8063 0.8470 25.4052 16.4816 19.4584 19458 12.40 C3-40.10a 12.50 C3-40.10b 12.50 C3-41.2a 0.9344 28.2981 602.5 0.8269 0.7726 25.9140 15.6132 20.2083 20208 12.60 C3-41.2b 1.4650 28.3011 808.75 0.8269 1.2113 25.9168 20.9602 17.3033 17303 12.60 C3-41.6a 1.9385 29.3770 1062.5 0.8666 1.6798 26.9020 28.5834 17.0155 17015 12.70 C3-41.6b 1.1219 29.1810 641.25 0.8666 0.9722 26.7225 17.1358 17.6257 17626 12.70 C3-41.10a 1.4781 29.0250 870 0.8533 1.2613 26.5797 23.1243 18.3340 18334 12.80 C3-41.10b 1.1194 28.5890 691.25 0.8533 0.9552 26.1804 18.0972 18.9460 18946 12.80 C3-42.2a 1.3533 27.8181 777.5 0.8753 1.1845 25.4745 19.8064 16.7211 16721 12.90 C3-42.2b 0.9564 28.9170 533.75 0.8753 0.8371 26.4808 14.1341 16.8843 16884 12.90 C3-42.6a 1.0958 29.9472 562.5 0.8286 0.9080 27.4242 15.4261 16.9890 16989 13.00 C3-42.6b 1.4028 27.3795 787.5 0.8286 1.1624 25.0728 19.7448 16.9863 16986 13.00 C3-42.10a 1.2344 28.9265 697.5 0.8519 1.0515 26.4895 18.4764 17.5706 17571 13.11 C3-42.10b 1.2905 27.6483 802.5 0.8519 1.0993 25.3190 20.3185 18.4824 18482 13.11 C3-43.2a 1.4150 28.9250 820 0.8436 1.1937 26.4881 21.7202 18.1959 18196 13.21 C3-43.2b 1.3483 26.1246 897.5 0.8436 1.1374 23.9236 21.4715 18.8773 18877 13.21 99 Sediment Extraction Data for C2-05 Total iron - 5.0 M HCI Extraction sed weight (g) soln weight (g) remar ks cone mg/L dry/wet ratio dry sed mass (g) ml of soln mg total of Fe mg/g pg/g FeTot depth (m) C2-2.2a 1.0335 31.2264 582.50 0.8412 0.8693 28.6481 16.6875 19.1955 19195 0.71 C2-2.2b 1.6358 29.6720 951.25 0.8412 1.3760 27.2220 25.8949 18.8193 18819 0.71 C2-2.6a 1.7336 30.6561 917.50 0.8348 1.4472 28.1249 25.8046 17.8301 17830 0.81 C2-2.6b 1.1054 30.7025 611.25 0.8348 0.9228 28.1674 17.2173 18.6575 18658 0.81 C2-2.10a 1.5974 29.9666 917.50 0.8392 1.3406 27.4923 25.2242 18.8159 18816 0.91 C2-2.10b 1.3178 30.3187 763.75 0.8392 1.1059 27.8153 21.2440 19.2091 19209 0.91 C2-3.2a 1.1351 30.3158 631.25 0.8407 0.9542 27.8127 17.5567 18.3985 18399 1.02 C2-3.2b 1.0500 30.3403 587.50 0.8407 0.8827 27.8351 16.3531 18.5262 18526 1.02 C2-3.6a 1.5417 30.3158 873.75 0.8388 1.2931 27.8127 24.3013 18.7929 18793 1.12 C2-3.6b 0.9248 31.3114 520.00 0.8388 0.7757 28.7261 14.9375 19.2573 19257 1.12 C2-3.10a 1.0585 30.6475 573.75 0.8320 0.8807 28.1170 16.1321 18.3178 18318 1.22 C2-3.10b 1.4583 30.9213 787.50 0.8320 1.2133 28.3682 22.3399 18.4123 18412 1.22 C2-4.2a 1.5567 30.6607 800.00 0.8254 1.2850 28.1291 22.5033 17.5126 17513 1.32 C2-4.2b 1.3538 31.1482 708.75 0.8254 1.1175 28.5763 20.2535 18.1241 18124 1.32 C2-4.6a 1.3452 30.3218 730.00 0.8971 1.2067 27.8182 20.3073 16.8285 16828 1.42 C2-4.6b 0.9912 30.9984 546.25 0.8971 0.8892 28.4389 15.5347 17.4712 17471 1.42 C2^l.10a 1.2055 30.0562 702.50 0.8905 1.0735 27.5745 19.3711 18.0444 18044 1.52 C2^l.10b 0.9768 29.9995 586.25 0.8905 0.8699 27.5225 16.1351 18.5490 18549 1.52 C2-5.2a 1.3434 30.8481 742.50 0.8331 1.1192 28.3010 21.0135 18.7751 18775 1.63 C2-5.2b 1.1400 30.3496 607.50 0.8331 0.9498 27.8437 16.9150 17.8097 17810 1.63 C2-5.6a 1.73 C2-5.6b 1.73 C2-5.10a 1.0247 30.8777 578.75 0.9201 0.9428 28.3282 16.3949 17.3888 17389 1.83 C2-5.10b 1.4441 31.2487 783.75 0.9201 1.3287 28.6685 22.4690 16.9100 16910 1.83 C2-6.2a 1.3054 30.5219 781.25 0.8650 1.1292 28.0017 21.8764 19.3742 19374 1.93 C2-6.2b 1.0740 30.7496 626.25 0.8650 0.9290 28.2106 17.6669 19.0173 19017 1.93 C2-7.5a 1.3052 30.0807 820.00 0.8769 1.1446 27.5970 22.6295 19.7714 19771 2.34 C2-7.5b 1.1307 29.8777 697.50 0.8769 0.9915 27.4107 19.1190 19.2822 19282 2.34 C2-7.11a 0.9936 30.8474 587.50 0.9111 0.9052 28.3004 16.6265 18.3669 18367 2.46 C2-7.11b 1.1306 31.5164 675.00 0.9111 1.0301 28.9141 19.5170 18.9475 18948 2.46 C2-8.3a 1.4444 31.2444 858.75 0.9131 1.3189 28.6646 24.6157 18.6631 18663 2.57 C2-8.3b 1.4315 30.6080 865.00 0.9131 1.3072 28.0807 24.2898 18.5820 18582 2.57 C2-8.7a 1.2811 31.4380 701.25 0.8835 1.1319 28.8422 20.2256 17.8693 17869 2.67 C2-8.7b 1.2846 30.4222 790.00 0.8835 1.1350 27.9103 22.0491 19.4273 19427 2.67 C2-8.11a 1.2497 31.4915 702.50 0.9302 1.1625 28.8913 20.2961 17.4598 17460 2.77 C2-8.11b 1.0066 31.3336 581.25 0.9302 0.9363 28.7464 16.7089 17.8452 17845 2.77 C2-9.3a 1.4385 30.4885 845.00 0.9477 1.3632 27.9711 23.6356 17.3378 17338 2.87 C2-9.3b 1.0693 30.3220 616.25 0.9477 1.0134 27.8183 17.1431 16.9171 16917 2.87 C2-9.7a 1.3322 30.3345 791.25 0.8725 1.1623 27.8298 22.0203 18.9453 18945 2.97 C2-9.7b . 1.3270 30.0914 801.25 0.8725 1.1578 27.6068 22.1199 19.1055 19106 2.97 C2-9.11a 1.4526 30.1483 885.00 0.8952 1.3004 27.6590 24.4782 18.8243 18824 3.07 C2-9.11b 1.3575 30.4925 805.00 0.8952 1.2152 27.9748 22.5197 18.5313 18531 3.07 C2-10.3a 1.2026 30.0088 702.50 0.8508 1.0232 27.5310 19.3405 18.9016 18902 3.18 C2-10.3b 1.4050 30.1823 796.25 0.8508 1.1954 27.6902 22.0483 18.4438 18444 3.18 C2-10.7a 1.0134 30.5457 571.25 0.8474 0.8587 28.0236 16.0085 18.6416 18642 3.28 C2-10.7b 1.5003 30.3155 858.75 0.8474 1.2713 27.8124 23.8839 18.7863 18786 3.28 C2-10.11a 1.0288 30.1069 578.75 0.8536 0.8782 27.6210 15.9857 18.2027 18203 3.38 C2-10.11b 1.1260 30.1196 645.00 0.8536 0.9612 27.6327 17.8231 18.5430 18543 3.38 C2-11.3a 1.0994 30.5548 605.00 0.8465 0.9307 28.0319 16.9593 18.2222 18222 3.48 C2-11.3b 1.0204 30.0208 612.50 0.8465 0.8638 27.5420 16.8695 19.5290 19529 3.48 C2-11.7a 1.0754 30.7000 602.50 0.8397 0.9030 28.1651 16.9695 18.7919 18792 3.58 C2-11.7b 1.1513 30.1811 656.25 0.8397 0.9668 27.6891 18.1710 18.7958 18796 3.58 100 Sediment Extraction Data for C1-05 Total iron - 5.0 M HCI Extraction sed weight (g) soln weight (g) remarks cone mg/L dry/wet ratio dry sed mass (g) ml of soln mg total of Fe mg/g FeTot depth (m) C1-4.4a 1.0179 32.7567 452.50 0.7823 0.7963 30.0520 13.5985 17.0781 17078 0.25 C1-4.4D 0.7823 0.0000 0.0000 0.25 C1-4.8a 0.9987 31.9615 568.75 0.8078 0.8068 29.3225 16.6772 20.6717 20672 0.35 C1-4.8b 0.8078 0.0000 0.35 C1-5.0a 1.4580 32.1715 oxidation 706.25 0.7421 1.0819 29.5151 20.8451 19.2665 19267 0.45 C1-5.0b 1.2008 31.1063 oxidation 626.25 0.7421 0.8911 28.5379 17.8719 20.0566 20057 0.45 C1-5.4a 1.1660 29.3156 oxidation 588.75 0.6519 0.7601 26.8950 15.8345 20.8320 20832 0.56 C1-5.4b 0.9895 30.6903 oxidation 425.00 0.6519 0.6450 28.1562 11.9664 18.5513 18551 0.56 C1-5.8a 1.2415 31.1987 oxidation 572.50 0.7898 0.9805 28.6227 16.3865 16.7116 16712 0.66 C1-5.8b 0.8929 31.7528 oxidation 415.00 0.7898 0.7052 29.1310 12.0894 17.1427 17143 0.66 C1-6.0a 1.0146 30.8535 from unoxidized part 525.00 0.8587 0.8713 28.3060 14.8606 17.0566 17057 0.76 C1-6.0b 1.3577 31.2403 from oxidized part 692.50 0.8587 1.1659 28.6608 19.8476 17.0238 17024 0.76 C1-6.4a 1.4570 31.2683 846.25 0.9504 1.3847 28.6865 24.2760 17.5316 17532 0.86 C1-6.4b 1.7241 29.9348 1142.50 0.9504 1.6385 27.4631 31.3766 19.1491 19149 0.86 C1-6.8a 1.2435 31.1000 soln weight error 741.25 0.9505 1.1820 28.5321 21.1494 17.8929 17893 0.96 C1-6.8b 1.1758 31.0601 883.75 0.9505 1.1176 28.4955 25.1829 22.5320 22532 0.96 C1-7.0a 1.2969 30.1880 858.75 0.9560 1.2399 27.6954 23.7834 19.1825 19182 1.06 C1-7.0b 1.3512 31.4796 1858.75 0.9560 1.2918 28.8804 53.6814 41.5566 41557 1.06 C1-7.4a 1.0696 30.2569 655.00 0.8763 0.9372 27.7586 18.1819 19.3994 19399 1.17 C1-7.4b 1.4381 30.8647 818.75 0.8763 1.2601 28.3162 23.1839 18.3979 18398 1.17 C1-7.8a 1.1403 30.5503 649.50 0.8429 0.9611 28.0278 18.2041 18.9402 18940 1.27 C1-7.8b 1.1910 30.0518 680.00 0.8429 1.0039 27.5705 18.7479 18.6757 18676 1.27 C1-8.0a 1.2380 29.8161 rock 523.75 0.8319 1.0299 27.3542 14.3268 13.9113 13911 1.37 C1-8.0b 1.7523 31.0432 853.75 0.8319 1.4577 28.4800 24.3148 16.6803 16680 1.37 C1-8.4a 1.2903 30.1650 717.50 0.8619 1.1121 27.6743 19.8563 17.8551 17855 1.47 C1-8.4b 0.8619 1.47 C1-10.6a 1.1304 31.0467 557.50 0.8141 0.9203 28.4832 15.8794 17.2555 17255 3.25 C1-10.6b 1.1747 31.8986 581.25 0.8141 0.9563 29.2648 17.0101 17.7872 17787 3.25 C1-10.10a 1.3941 29.6207 721.25 0.7995 1.1146 27.1750 19.5999 17.5840 17584 3.35 C1-10.10b 1.5487 30.3981 762.50 0.7995 1.2383 27.8882 21.2647 17.1731 17173 3.35 C1-11.2a 1.2956 30.2156 663.75 0.8184 1.0603 27.7207 18.3996 17.3526 17353 3.45 C1-11.2b 0.9665 30.2607 507.50 0.8184 0.7910 27.7621 14.0893 17.8120 17812 3.45 C1-11.6a 0.9454 30.1034 513.75 0.8305 0.7851 27.6178 14.1886 18.0719 18072 3.56 C1-11.6b 1.2332 30.7947 612.50 0.8305 1.0241 28.2520 17.3044 16.8966 16897 3.56 C1-11.10a 0.9648 31.0474 500.00 0.8199 0.7911 28.4839 14.2419 18.0037 18004 3.66 C1-11.10b 1.5772 30.8968 803.75 0.8199 1.2932 . 28.3457 22.7828 17.6178 17618 3.66 C1-12.2a 1.0718 30.6742 573.75 0.8225 0.8816 28.1415 16.1462 18.3152 18315 3.76 C1-12.2b 1.8347 30.4266 983.75 0.8225 1.5091 27.9143 27.4607 18.1971 18197 3.76 C1-12.6a 1.3856 30.3032 748.75 0.8326 1.1537 27.8011 20.8161 18.0428 18043 3.86 C1-12.6b 1.2481 30.2200 668.75 0.8326 1.0392 27.7248 18.5409 17.8413 17841 3.86 C1-12.10a 1.0620 31.2991 555.00 0.8278 0.8791 28.7148 15.9367 18.1285 18128 3.96 C1-12.10b 1.1085 30.3325 588.75 0.8278 0.9176 27.8280 16.3837 17.8552 17855 3.96 C1-13.2a 0.9207 30.9300 476.25 0.8197 0.7547 28.3761 13.5141 17.9067 17907 4.06 C1-13.2b 1.1186 30.3152 612.50 0.8197 0.9169 27.8121 17.0349 18.5785 18578 4.06 C1-13.6a 1.2283 30.2214 643.75 0.8179 1.0047 27.7261 17.8486 17.7654 17765 4.17 C1-13.6b 1.3327 31.1847 667.50 0.8179 1.0901 28.6098 19.0971 17.5190 17519 4.17 C1-13.10a 1.2100 29.8970 656.25 0.8179 0.9897 27.4284 17.9999 18.1873 18187 4.27 C1-13.10b 1.4321 30.3088 736.25 0.8179 1.1714 27.8062 20.4723 17.4774 17477 4.27 redone C1-7.0a 1.8798 30.3786 1365.00 0.9560 1.7971 27.8703 38.0429 21.1689 21169 1.06 C1-7.0b 1.3268 30.8557 997.50 0.9560 1.2684 28.3080 28.2372 22.2614 22261 1.06 101 Sediment Extraction Data for C1-06, C2-06, C4-06 and C12-06 Total iron - 0.75 M HCI Extraction 2006 sed weight (g) soln weight (g) cone mg/L dry/wet ratio dry sed mass (g) ml of soln mg total of Fe mg/g ug/g FeTot depth (m) assumed C2-06-02 0"-2"a 2.0544 28.3294 329.25 0.8 1.64352 28.07670961 9.24425664 5.624669393 5624.669393 0.0254 C2-06-02 0"-2"b 1.5979 28.8482 274.5 0.8 1.27832 28.59088206 7.848197126 6.139462049 6139.462049 0.0254 C2-06-02 2"-6"a 2.2305 29.7117 270.75 0.8 1.7844 29.44667988 7.972688578 4.467994047 4467.994047 0.1016 C2-06-02 2"-6"b 1.634 28.7907 228.75 0.8 1.3072 28.53389495 6.527128469 4.993213333 4993.213333 0.1016 C4-06-03 0"-3"a 1.8621 29.6927 174.75 0.8 1.48968 29.42784936 5.142516675 3.452094863 3452.094863 0.0381 C4-06-03 0"-3"b 2.2743 29.415 167 0.8 1.81944 29.15262636 4.868488603 2.675817066 2675.817066 0.0381 C4-06-03 3"-7"a 2.16 29.297 298.5 0.8 1.728 29.03567889 8.667150149 5.015711892 5015.711892 0.127 C4-06-03 3"-7"b 1.5301 30.668 205 0.8 1.22408 30.39444995 6.23086224 5.09024103 5090.24103 0.127 C4-06-03 7"-11"a 1.5129 30.0418 214 0.8 1.21032 29.77383548 6.371600793 5.264393543 5264.393543 0.2286 C4-06-03 7"-11"b 1.4455 31.2563 199.25 0.8 1.1564 30.97750248 6.172267369 5.337484753 5337.484753 0.2286 C4-06-03 11"-1'3"a 1.3217 30.2355 214.75 0.8 1.05736 29.96580773 6.43515721 6.086060765 6086.060765 0.3302 C4-06-03 11"-1'3"b 1.3242 30.7975 224.75 0.8 1.05936 30.52279485 6.859998142 6.47560616 6475.60616 0.3302 C4-06-03 1'3"-17"a 1.2473 30.3817 215.25 0.8 0.99784 30.11070367 6.481328964 6.49535894 6495.35894 0.4318 C4-06-03 1'3"-17"b 1.1707 30.589 210 0.8 0.93656 30.31615461 6.366392468 6.797634394 6797.634394 0.4318 C4-06-03 17"-1'11"a 1.1905 30.7478 198.25 0.8 0.9524 30.47353816 6.04137894 6.34332102 6343.32102 0.5334 C4-06-03 17"-1'11"b 1.3466 30.6822 210.25 0.8 1.07728 30.40852329 6.393392022 . 5.934754216 5934.754216 0.5334 C1-06-01 0"- 2.5"a 1.9752 29.1466 339 0.8 1.58016 28.88662042 9.792564321 6.197197955 6197.197955 0.03175 C1-06-01 0"- 2.5"b 1.7368 28.9922 312.25 0.8 1.38944 28.73359762 8.972065857 6.457325151 6457.325151 0.03175 C1-06-01 2.5" - 6"a 2.1278 30.6825 434 0.8 1.70224 30.40882061 13.19742815 7.75297734 7752.97734 0.1143 C1-06-01 2.5" - 6"b 2.7009 30.7208 548.5 0.8 2.16072 30.44677899 16.70005828 7.72893215 7728.93215 0.1143 C12-06 sed weight [gl soln weight [gl measured mg/L actual cone. mg/L dry/wet ratio dry sed mass [q] ml of soln mg total in soln mg Fe/g sed ug/g depth [m] 0-10 ga 1.7905 29.7643 0.81798084 408.99042 0.812246658 1.454327641 27.30669725 11.16817758 7.67927203 7679.27203 0.05 0-10 gb 1.8179 29.7184 0.722181282 361.0906411 0.812246658 1.4765832 27.26458716 9.844987256 6.667411127 6667.411127 0.05 10-20 ga 1.6028 30.5555 1.156963891 1156.963891 0.87299833 1.399241723 28.03256881 32.43266988 23.178747 23178.747 0.15 10-20 gb 1.0518 30.6533 0.478997789 239.4988946 0.87299833 0.918219643 28.12229358 6.735258226 7.335127576 7335.127576 0.15 20-30 sa 1.0678 30.6576 0.52321297 261.6064849 0.812802151 0.867910137 28.12623853 7.358006396 8.477843595 8477.843595 0.25 20-30 sb 1.6101 30.5888 0.77376566 386.8828298 0.812802151 1.308692744 28.06311927 10.85713899 8.296171158 8296.171158 0.25 30-40 ga 1.0306 30.6151 0.471628592 235.8142962 0.794815552 0.819136908 28.08724771 6.623374551 8.085796753 8085.796753 0.35 30-40 gb 1.1372 30.8889 0.552689757 276.3448784 0.794815552 0.903864246 28.33844037 7.831182857 8.66411399 8664.11399 0.35 40-50 ga 0.8496 32.5314 0.420044215 210.0221076 0.7271411 0.617779079 29.8453211 6.268177239 10.14630869 10146.30869 0.45 40-50 gb 1.0171 30.2732 0.515843773 257.9218865 0.7271411 0.739575213 27.77357798 7.163413628 9.685848715 9685.848715 0.45 50-60 ga 1.1599 30.2378 0.560058954 280.0294768 0.723487412 0.839173049 27.74110092 7.768325975 9.257120431 9257.120431 0.55 50-60 gb 1.1221 30.4546 0.52321297 261.6064849 0.723487412 0.811825225 27.94 7.309285188 9.003520667 9003.520667 0.55 o Sediment Extraction Data for C3-05 Total iron - 0.75 M HCI Extraction weight (g) soln weight (g) remarks cone mg/L dry/wet ratio dry mass (g) ml of soln mg total of Fe mg/g ug/g FeTot depth (m) C3-33.5a 1.4582 30.4628 509 0.9217 1.3441 30.1911 15.3673 11.4335 11433 10.26 C3-33.5b 1.6006 30.4734 362 0.9217 1.4753 30.2016 10.9330 7.4106 7411 10.26 C3-33.10a 2.8626 30.3090 621 0.9362 2.6800 30.0387 18.6540 6.9604 6960 10.36 C3-33.10b 2.1271 30.7155 372.75 0.9362 1.9914 28.1277 10.4846 5.2649 5265 10.36 C3-34.2a 1.7497 31.3118 297 0.9266 1.6212 31.0325 9.2167 5.6849 5685 10.46 C3-34.2b 1.2031 30.6557 194.5 0.9266 1.1148 30.3823 5.9093 5.3010 5301 10.46 C3-34.6a 1.2008 30.4295 oxidized 159.25 0.8793 1.0559 30.1581 4.8027 4.5483 4548 10.57 C3-34.6b 1.1929 30.7877 oxidized 162.5 0.8793 1.0490 28.1939 4.5815 4.3676 4368 10.57 C3-34.10a 1.1951 30.0974 212.5 0.8946 1.0691 29.8289 6.3386 5.9287 5929 10.67 C3-34.10b 1.2852 30.2081 216.5 0.8946 1.1497 29.9387 6.4817 5.6375 5638 10.67 C3-35.2a 1.5406 30.2530 261 0.9010 1.3881 29.9832 7.8256 5,6377 5638 10.77 C3-35.2b 0.9763 30.2542 167 0.9010 0.8796 27.7053 4.6268 5.2598 5260 10.77 C3-35.6a 10.87 C3-35.6b 10.87 C3-35.10a 1.4292 30.4531 296 0.8293 1.1853 30.1815 8.9337 7.5372 7537 10.97 C3-35.10b 1.1440 30.5393 234.5 0.8293 0.9488 27.9664 6.5581 6.9123 6912 10.97 C3-36.2a 1.1935 29.2264 313 0.7963 0.9504 28.9657 9.0663 9.5395 9540 11.07 C3-36.2b 0.8674 29.7260 237.5 0.7963 0.6907 29.4609 6.9970 10.1300 10130 11.07 C3-36.6a 1.0096 29.4603 oxidized 215.5 0.8524 0.8606 29.1975 6.2921 7.3115 7312 11.18 C3-36.6b 1.2840 30.5108 oxidized 258 0.8524 1.0945 27.9403 7.2086 6.5864 6586 11.18 C3-36.10a 1.3776 29.6055 228.5 0.8597 1.1843 29.3414 6.7045 5.6610 5661 11.28 C3-36.10b 1.0083 30.2598 155.5 0.8597 0.8668 29.9899 4.6634 5.3798 5380 11.28 C3-37.2a 1.0391 30.6228 316 0.8600 0.8936 30.3497 9.5905 10.7326 10733 11.38 C3-37.2b 1.1252 30.8435 356.5 0.8600 0.9676 28.2450 10.0693 10.4062 10406 11.38 C3-37.6a 1.0299 29.2556 224.5 0.8444 0.8696 28.9946 6.5093 7.4852 7485 11.48 C3-37.6b 1.5885 29.6871 356.5 0.8444 1.3413 29.4223 10.4890 7.8202 7820 11.48 C3-38.9a 11.87 C3-38.9b 11.87 C3-39.2a 1.1912 30.1163 193 0.8668 1.0325 29.8477 5.7606 5.5793 5579 11.99 C3-39.2b 1.4482 29.4083 250.5 0.8668 1.2553 29.1460 7.3011 5.8164 5816 11.99 C3-39.6a 0.9580 30.0598 153.5 0.8636 0.8274 29.7917 4.5730 5.5273 5527 12.09 C3-39.6b 1.8140 30.2747 298.5 0.8636 1.5666 27.7241 8.2756 5.2825 5282 12.09 C3-39.10a 1.3969 29.6988 oxidized 196 0.8869 1.2389 29.4339 5.7690 4.6567 4657 12.19 C3-39.10b 1.7323 30.5898 oxidized 336.5 0.8869 1.5363 30.3169 10.2017 6.6403 6640 12.19 C3-40.2a 1.2567 29.3491 oxidized 116.5 0.9048 1.1370 29.0873 3.3887 2.9803 2980 12.29 C3-40.2b 1.8191 29.4189 oxidized 320.5 0.9048 1.6459 26.9404 8.6344 5.2461 5246 12.29 C3-40.6a 1.7562 29.9266 387 0.8063 1.4160 29.6597 11.4783 8.1060 8106 12.40 C3-40.6b 1.4756 30.0744 323 0.8063 1.1898 29.8061 9.6274 8.0917 8092 12.40 C3-40.10a 12.50 C3-40.10b 12.50 C3-41.2a 1.0091 30.8124 236 0.8269 0.8344 30.5376 7.2069 8:6374 8637 12.60 C3-41.2b 1.3012 30.2145 305.5 0.8269 1.0759 29.9450 9.1482 8.5028 8503 12.60 C3-41.6a 1.5263 30.2527 246 0.8666 1.3226 29.9829 7.3758 5.5765 5577 12.70 C3-41.6b . 1.8240 29.5765 303.5 0.8666 1.5806 27.0847 8.2202 5.2006 5201 12.70 C3-41.10a 1.5467 29.9917 299.5 0.8533 1.3198 29.7242 8.9024 6.7452 6745 12.80 C3-41.10b 1.5526 30.0700 319.5 0.8533 1.3249 29.8018 9.5217 7.1870 7187 12.80 C3-42.2a 1.5790 30.4994 249.5 0.8753 1.3821 30.2274 7.5417 5:4569 5457 12.90 C3-42.2b 2.2067 29.7692 351.5 0.8753 1.9315 27.2612 9.5823 4.9611 4961 12.90 C3-42.6a 1.7852 30.2842 299 0.8286 1.4793 30.0141 8.9742 6.0667 6067 13.00 C3-42.6b 1.3269 30.1612 220 0.8286 1.0995 29.8922 6.5763 5.9811 5981 13.00 C3-42.10a 1.6270 30.1400 266.5 0.8519 1.3860 29.8712 7.9607 5.7436 5744 13.11 C3-42.10b 0.9568 29.7939 148.5 0.8519 0.8151 27.2838 4.0516 4.9709 4971 13.11 C3-43.2a 1.5506 30.6465 247 0.8436 1.3081 30.3731 7.5022 5.7352 5735 13.21 C3-43.2b 1.6805 29.7582 267.5 0.8436 1.4177 27.2511 7.2897 5.1420 5142 13.21 redone C3-33.5a 2.1687 28.955 342.25 0.9217 1.9989 28.6967 9.8215 4.9133 4913 10.26 C3-33.5b 2.0048 28.7236 358.50 0.9217 1.8479 26.30371 9.4299 5.1031 5103 10.26 103 Sediment Extraction Data for C2-05 Total iron - 0.75 M HCI Extraction sed weight (g) soln weight (g) remar ks cone mg/L dry/wet ratio dry mass (g) ml of soln mg total of Fe mg/g ug/g FeTot depth (m) C2-2.2a 1.3428 31.6771 201.25 0.8412 1.1295 31.3945 6.3182 5.5937 5594 0.71 C2-2.2b 1.5077 30.0400 225.75 0.8412 1.2682 29.7721 6.7210 5.2996 5300 0.71 C2-2.6a 1.5220 29.0559 245.25 0.8348 1.2706 28.7967 7.0624 5.5583 5558 0.81 C2-2.6b 1.7440 30.6305 265.00 0.8348 1.4559 30.3573 8.0447 5.5255 5525 0.81 C2-2.10a 1.2943 30.6574 207.50 0.8392 1.0862 30.3839 6.3047 5.8043 5804 0.91 C2-2.10b 1.2734 30.1113 205.50 0.8392 1.0687 29.8427 6.1327 5.7386 5739 0.91 C2-3.2a 0.9852 30.3195 159.75 0.8407 0.8282 30.0491 4.8003 5.7959 5796 1.02 C2-3.2b 1.3218 30.1207 209.25 0.8407 1.1112 29.8520 6.2465 5.6214 5621 1.02 C2-3.6a 1.1263 30.1336 193.50 0.8388 0.9447 29.8648 5.7788 6.1172 6117 1.12 C2-3.6b 1.0107 30.2272 167.25 0.8388 0.8477 29.9576 5.0104 5.9104 5910 1.12 C2-3.10a 1.4106 30.2710 244.00 0.8320 1.1736 30.0010 7.3202 6.2373 6237 1.22 C2-3.10b 1.0973 31.2671 178.50 0.8320 0.9130 30.9882 5.5314 6.0587 6059 1.22 C2-4.2a 1.2722 30.9622 194.50 0.8254 1.0501 30.6860 5.9684 5.6835 5683 1.32 C2-4.2b 1.2950 30.2039 220.75 0.8254 1.0690 29.9345 6.6080 6.1818 6182 1.32 C2-4.6a 1.7848 30.2176 271.75 0.8971 1.6011 29.9481 8.1384 5.0831 5083 1.42 C2-4.6b 1.0465 30.8791 170.75 0.8971 0.9388 30.6037 5.2256 5.5664 5566 1.42 C2-4.10a 2.1303 29.9688 348.75 0.8905 1.8971 29.7015 10.3584 5.4602 5460 1.52 C2-4.10b 1.1966 30.4299 196.25 0.8905 1.0656 30.1585 5.9186 5.5543 5554 1.52 C2-5.2a 2.7115 30.0352 451.00 0.8331 2.2590 29.7673 13.4250 5.9429 5943 1.63 C2-5.2b 1.2606 29.9621 225.25 0.8331 1.0502 29.6948 6.6888 6.3688 6369 1.63 C2-5.6a 1.73 C2-5.6b 1.73 C2-5.10a 1.3372 30.0392 239.50 0.9201 1.2304 29.7713 7.1302 5.7951 5795 1.83 C2-5.10b 1.8983 30.5273 342.25 0.9201 1.7467 30.2550 10.3548 5.9283 5928 1.83 C2-6.2a 1.6678 30.4984 281.25 0.8650 1.4426 30.2264 8.5012 5.8929 5893 1.93 C2-6.2b 1.2810 30.8638 219.50 0.8650 1.1080 30.5885 6.7142 6.0595 6059 1.93 C2-7.5a 1.6683 30.5317 258.25 0.8769 1.4630 30.2594 7.8145 5.3415 5342 2.34 C2-7.5b 2.0564 31.0373 314.75 0.8769 1.8033 30.7605 9.6819 5.3690 5369 2.34 C2-7.11a 1.7081 29.9150 289.50 0.9111 1.5562 29.6482 8.5831 5.5154 5515 2.46 C2-7.11b 1.5627 29.4583 266.75 0.9111 1.4237 29.1955 7.7879 5.4701 5470 2.46 C2-8.3a 1.5055 31.1766 235.25 0.9131 1.3747 30.8985 7.2689 5.2874 5287 2.57 C2-8.3b 1.5000 29.8752 246.00 0.9131 1.3697 29.6087 7.2837 5.3177 5318 2.57 C2-8.7a 1.5238 29.8726 227.75 0.8835 1.3463 29.6061 6.7428 5.0084 5008 2.67 C2-8.7b 2.0504 29.8526 310.75 0.8835 1.8115 29.5863 9.1939 5.0752 5075 2.67 C2-8.11a 1.5988 29.9259 260.50 0.9302 1.4872 29.6590 7.7262 5.1952 5195 2.77 C2-8.11b 1.4243 30.3692 217.25 0.9302 1.3249 30.0983 6.5389 4.9355 4936 2.77 C2-9.3a 1.2129 30.3603 191.75 0.9477 1.1494 30.0895 5.7697 5.0195 5020 2.87 C2-9.3b 1.7370 30.3243 264.75 0.9477 1.6461 30.0538 7.9567 4.8336 4834 2.87 C2-9.7a 1.1600 30.3664 198.25 0.8725 1.0121 30.0955 5.9664 5.8953 5895 2.97 C2-9.7b 1.4902 29.6840 221.25 0.8725 1.3002 29.4192 6.5090 5.0063 5006 2.97 C2-9.11a 1.6929 30.4428 287.00 0.8952 1.5155 30.1713 8.6592 5.7138 5714 3.07 C2-9.11b 1.1394 30.8705 185.75 0.8952 1.0200 30.5951 5.6830 5.5717 5572 3.07 C2-10.3a 0.9128 30.4456 155.00 0.8508 0.7766 30.1740 4.6770 6.0220 6022 3.18 C2-10.3b 1.7879 29.8058 287.50 0.8508 1.5212 29.5399 8.4927 5.5828 5583 3.18 C2-10.7a 1.5760 29.8704 266.50 0.8474 1.3355 29.6040 7.8895 5.9075 5908 3.28 C2-10.7b 1.4884 20.4966 348.00 0.8474 1.2613 20.3138 7.0692 5.6049 5605 3.28 C2-10.11a 1.4497 30.3388 235.75 0.8536 1.2375 30.0682 7.0886 5.7282 5728 3.38 C2-10.11b 2.0138 30.3734 317.25 0.8536 1.7190 30.1025 9.5500 5.5555 5556 3.38 C2-11.3a 1.6224 30.6098 282.75 0.8465 1.3734 30.3368 8.5777 6.2454 6245 3.48 C2-11.3b 1.1041 30.1877 176.50 0.8465 0.9347 29.9184 5.2806 5.6497 5650 3.48 C2-11.7a 1.8936 28.8358 342.25 0.8397 1.5901 28.5786 9.7810 6.1513 6151 3.58 C2-11.7b 1.1838 30.1843 217.75 0.8397 0.9940 27.6413 6.0189 6.0549 6055 3.58 104 Sediment Extraction Data for C1-05 Total iron - 0.75 M HCI Extraction sed weight (q) soln weight (q) remarks cone mq/L dry/wet ratio dry mass (q) ml of soln mg total of Fe mq/q ug/g FeTot depth (m) C1-4.4a 1.5797 29.8984 207.25 0.7823 1.2357 29.6317 6.1412 4.9697 4970 0.25 C1-4.4b 1.2507 29.6518 169.75 0.7823 0.9784 29.3873 4.9885 5.0988 5099 0.25 C1-4.8a 1.4833 29.5097 209.25 0.8078 1.1982 29.2465 6.1198 5.1074 5107 0.35 C1-4.8b 0.8078 0.35 C1-5.0a 2.2425 28.8476 oxidation 285.25 0.7421 1.6641 28.5903 8.1554 4.9008 4901 0.45 C1-5.0b 1.6893 29.6093 oxidation 245.25 0.7421 1.2536 29.3452 7.1969 5.7411 5741 0.45 C1-5.4a 1.4943 29.3171 oxidation 224.75 0.6519 0.9741 29.0556 6.5302 6.7038 6704 0.56 C1-5.4b 1.2745 29.7673 oxidation 169.75 0.6519 0.8308 29.5018 5.0079 6.0276 6028 0.56 C1-5.8a 1.5932 29.4943 oxidation 195.75 0.7898 1.2583 29.2312 5.7220 4.5473 4547 0.66 C1-5.8b 1.7719 30.1184 oxidation 213.00 0.7898 1.3995 29.8498 6.3580 4.5432 4543 0.66 C1-6.0a 2.4127 31.7917 oxidation 246.25 0.8587 2.0718 31.5081 7.7589 3.7450 3745 0.76 C1-6.0b 2.0421 29.9825 222.00 0.8587 1.7536 29.7151 6.5967 3.7619 3762 0.76 C1-6.4a 3.5946 28.5595 342.00 0.9504 3.4162 28.3048 9.6802 2.8336 2834 0.86 C1-6.4b 1.6640 29.8849 257.75 0.9504 1.5814 29.6183 7.6341 4.8274 4827 0.86 C1-6.8a 2.5774 29.2035 330.00 0.9505 2.4499 28.9430 9.5512 3.8986 3899 0.96 C1-6.8b 0.9505 0.96 C1-7.0a 1.6597 29.0978 227.25 0.9560 1.5867 28.8383 6.5535 4.1303 4130 1.06 C1-7.0b 0.9560 1.06 C1-7.4a 2.8730 29.0228 279.50 0.8763 2.5175 28.7639 8.0395 3.1935 3193 1.17 C1-7.4b 1.9640 30.2643 256.50 0.8763 1.7210 29.9944 7.6936 4.4705 4470 1.17 C1-7.8a 2.4618 29.2092 327.75 0.8429 2.0750 28.9487 9.4879 4.5725 4573 1.27 C1-7.8b 1.5369 31.1080 196.25 0.8429 1.2954 30.8305 6.0505 4.6707 4671 1.27 C1-8.0a 1.8380 28.6991 226.75 0.8319 1.5290 28.4431 6.4495 4.2181 4218 1.37 C1-8.0b 0.8319 1.37 C1-8.4a 1.9620 28.7927 284.25 0.8619 1.6910 28.5359 8.1113 4.7967 4797 1.47 C1-8.4b 1.4823 29.5300 219.75 0.8619 1.2776 29.2666 6.4313 5.0341 5034 1.47 C1-10.6a 1.0471 29.8153 140.75 0.8141 0.8524 29.5494 4.1591 4.8790 4879 3.25 C1-10.6b 1.3024 29.2128 weiqht?? 177.00 0.8141 1.0603 28.9522 5.1245 4.8332 4833 3.25 C1-10.10a 2.2957 29.1055 328.75 0.7995 1.8355 28.8459 9.4831 5.1664 5166 3.35 C1-10.10b 1.2175 29.3622 171.25 0.7995 0.9734 29.1003 4.9834 5.1194 5119 3.35 C1-11.2a 1.0759 29.5042 153.00 0.8184 0.8805 29.2410 4.4739 5.0809 5081 3.45 C1-11.2b 2.0462 28.1733 293.00 0.8184 1.6746 27.9220 8.1811 4.8853 4885 3.45 C1-11.6a 1.2888 29.9586 174.75 0.8305 1.0703 29.6914 5.1886 4.8477 4848 3.56 C1-11.6b 1.0943 29.4335 157.75 0.8305 0.9088 29.1710 4.6017 5.0636 5064 3.56 C1-11.10a 2.4795 29.1947 352.50 0.8199 2.0330 28.9343 10.1993 5.0169 5017 3.66 C1-11.10b 2.5912 28.5231 361.25 0.8199 2.1246 28.2687 10.2121 4.8066 4807 3.66 C1-12.2a 1.6860 29.1728 249.75 0.8225 1.3868 28.9126 7.2209 5.2070 5207 3.76 C1-12.2b 1.7486 29.5075 248.25 0.8225 1.4382 29.2443 7.2599 5.0477 5048 3.76 C1-12.6a 1.4530 29.4098 213.75 0.8326 1.2098 29.1475 6.2303 5.1497 5150 3.86 C1-12.6b 1.7746 28.4265 272.00 0.8326 1.4776 28.1729 7.6630 5.1861 5186 3.86 C1-12.10a 1.7047 28.4931 243.50 0.8278 1.4111 28.2389 6.8762 4.8729 4873 3.96 C1-12.10b 1.9196 28.6302 287.50 0.8278 1.5890 28.3748 8.1578 5.1339 5134 3.96 C1-13.2a 2.0230 29.2857 293.25 0.8197 1.6583 29.0245 8.5114 5.1328 5133 4.06 C1-13.2b 0.8197 4.06 C1-13.6a 0.9946 29.3972 143.25 0.8179 0.8135 29.1350 4.1736 5.1302 5130 4.17 C1-13.6b 1.5449 29.7623 211.00 0.8179 1.2636 29.4968 6.2238 4.9253 4925 4.17 C1-13.10a 1.7202 29.4140 253.50 0.8179 1.4070 29.1516 7.3899 5.2523 5252 4.27 C1-13.10b 1.8180 30.4430 259.50 0.8179 1.4870 30.1715 7.8295 5.2653 5265 4.27 redone C1-6.4a 4.3182 28.5953 442.00 0.9504 4.1039 28.3402 12.5264 3.0523 3052 0.86 C1-6.4b 1.5306 28.9449 159.50 0.9504 1.4546 28.6867 4.5755 3.1455 3145 0.86 C1-6.8a 2.8462 28.3174 266.00 0.9505 2.7054 28.0648 7.4652 2.7593 2759 0.96 C1-6.8b 2.2694 28.8056 256.25 0.9505 2.1572 28.5487 7.3156 3.3913 3391 0.96 C1-7.0a 1.4008 28.5422 243.75 0.9560 1.3392 28.2876 6.8951 5.1487 5149 1.06 C1-7.0b 1.8772 28.5902 274.75 0.9560 1.7946 28.3352 7.7851 4.3380 4338 1.06 C1-8.0a 1.6183 28.9873 193.75 0.8319 1.3462 28.7287 5.5662 4.1347 4135 1.37 C1-8.0b 2.4757 28.7364 281.50 0.8319 2.0595 28.4801 8.0171 3.8928 3893 1.37 105 Sediment Extraction Data for C1-06, C2-06, C4-06 and C12-06 Total iron - 1M CaCI2 Extraction 2006 sed weiqht (q) soln weiqht (q) cone mg/L dry/wet ratio dry sed mass (q) ml of soln mq total of Fe mq/q ug/g FeTot depth (m) assumed C2-06-02 0"-2"a 1.8187 30.2949 9.4 0.8 1.4550 27.7426 0.2608 • 0.1792 179.2354 0.0254 C2-06-02 0"-2"b 2.1061 29.9248 8.95 0.8 1.6849 27.4037 0.2453 0.1456 145.5669 0.0254 C2-06-02 2"-6"a 1.8008 28.8423 4.49 0.8 1.4406 26.4124 0.1186 0.0823 82.3186 0.1016 C2-06-02 2"-6"b 2.3463 30.4059 4.39 0.8 1.8770 27.8442 0.1222 0.0651 65.1218 0.1016 C4-06-03 0"-3"a 2.6958 30.4573 11.2 0.8 2.1566 27.8913 0.3124 0.1448 144.8469 0.0381 C4-06-03 0"-3"b 2.6823 31.5726 10.5 0.8 2.1458 28.9126 0.3036 0.1415 141.4750 0.0381 C4-06-03 3"-7"a 2.6458 29.4895 16.58 0.8 2.1166 27.0050 0.4477 0.2115 211.5350 0.127 C4-06-03 3"-7"b 3.0778 29.4345 17.8 0.8 2.4622 26.9547 0.4798 0.1949 194.8604 0.127 C4-06-03 7"-11"a 2.9683 31.1619 4.19 0.8 2.3746 28.5365 0.1196 0.0504 50.3521 0.2286 C4-06-03 7"-11"b 2.6913 31.5594 4.5 0.8 2.1530 28.9005 0.1301 0.0604 60.4041 0.2286 C4-06-03 11"-1'3"a 2.1394 30.1347 13.93 0.8 1.7115 27.5959 0.3844 0.2246 224.6019 0.3302 C4-06-03 11"-1'3"b 2.3513 29.1743 14.73 0.8 1.8810 26.7164 0.3935 0.2092 209.2100 0.3302 C4-06-03 1'3"-1'7"a 2.1363 29.8656 13.6 0.8 1.7090 27.3495 0.3720 0.2176 217.6383 0.4318 C4-06-03 1'3"-1'7"b 2.5548 30.507 15.23 0.8 2.0438 27.9368 0.4255 0.2082 208.1756 0.4318 C4-06-03 1'7"-1'11"a 3.9654 29.7208 17.7 0.8 3.1723 27.2168 0.4817 0.1519 151.8568 0.5334 C4-06-03 17"-ri1"b 2.277 30.296 12.9 0.8 1.8216 27.7436 0.3579 0.1965 196.4714 0.5334 C1-06-01 0"- 2.5"a 1.6127 29.1779 32.6 0.8 1.2902 26.7197 0.8711 0.6752 675.1580 0.03175 C1-06-01 0"-2.5"b 2.524 28.629 45.15 0.8 2.0192 26.2170 1.1837 0.5862 586.2218 0.03175 C1-06-01 2.5" - 6"a 2.6113 29.974 75.5 0.8 2.0890 27.4487 2.0724 0.9920 992.0242 0.1143 C1-06-01 2.5" - 6"b 4.0048 29.8325 140 0.8 3.2038 27.3191 3.8247 1.1938 1193.7798 0.1143 C12-06 sed weight fql soln weiqht [gl measured mq/L actual cone. mg/L dry/wet ratio dry sed mass [g] ml of soln mg total in soln mq Fe/g sed depth Tml 0-10 ga 4.5576 33.6596 0.3979 99.4842 0.8122 3.7019 30.8238 3.0665 0.8284 828.3542 0.05 0-10 gb 3.1547 30.0657 0.2653 66.3228 0.8122 2.5624 27.5327 1.8260 0.7126 712.6320 0.05 10-20 qa 1.2269 33.2167 0.2358 23.5814 0.8730 1.0711 30.4182 0.7173 0.6697 669.7017 0.15 10-20 qb 1.9659 33.486 0.3169 31.6875 0.8730 1.7162 30.6648 0.9717 0.5662 566.1798 0.15 20-30 sa 1.6033 33.9254 0.3685 36.8460 0.8128 1.3032 31.0672 1.1447 0.8784 878.4011 0.25 20-30 sb 1.8223 32.7038 0.4348 43.4783 0.8128 1.4812 29.9485 1.3021 0.8791 879.1096 0.25 30-40 ga 1.8964 32.5167 0.4127 41.2675 0.7948 1.5073 29.7772 1.2288 0.8153 815.2592 0.35 30-40 gb 1.5518 32.6318 0.4053 40.5306 0.7948 1.2334 29.8826 1.2112 0.9820 981.9721 0.35 40-50 qa 1.2121 32.1443 0.3979 39.7937 0.7271 0.8814 29.4362 1.1714 1.3290 1329.0402 0.45 40-50 qb 1.1038 33.1571 0.3390 33.8983 0.7271 0.8026 30.3636 1.0293 1.2824 1282.3979 0.45 50-60 ga 1.3709 34.1555 0.3979 39.7937 0.7235 0.9918 31.2779 1.2447 1.2549 1254.9175 0.55 50-60 gb 1.7373 31.462 0.5527 55.2690 0.7235 1.2569 28.8114 1.5924 1.2669 1266.8912 0.55 Sediment Extraction Data for C3-05 Total iron -1M CaCI2 Extraction weight of seds (q) weight of soln (g) remarks cone mg/L dry/wet ratio dry mass (q) ml of soln mg total of Fe mg/g ug/g FeTot depth (m) C3-33.1a 3.7732 31.2037 oxidized 14.897 3.0186 28.5748 0.4257 0.1410 141.02 10.14 C3-33.1b 2.9410 32.0504 oxidized 11.281 2.3528 29.3502 0.3311 0.1407 140.73 10.14 C3-33.5a 5.9786 31.1014 42.729 0.9217 5.5106 28.4811 1.2170 0.2208 220.84 10.26 C3-33.5b 4.2612 31.0144 24.732 0.9217 3.9277 28.4015 0.7024 0.1788 178.84 10.26 C3-33.10a 4.1725 31.6094 36.357 0.9362 3.9064 28.9463 1.0524 0.2694 269.41 10.36 C3-33.10b 3.6224 31.0565 24.607 0.9362 3.3914 28.4400 0.6998 0.2064 206.35 10.36 C3-34.2a 4.0951 31.6954 18.532 0.9266 3.7944 29.0251 0.5379 0.1418 141.76 10.46 C3-34.2b 3.1917 31.1161 17.523 0.9266 2.9574 28.4946 0.4993 0.1688 168.84 10.46 C3-34.6a oxidized 0.8793 10.57 C3-34.6b oxidized 0.8793 10.57 C3-34.10a 2.0613 31.8180 14.553 0.8946 1.8440 29.1374 0.4240 0.2299 229.95 10.67 C3-34.10b 2.2878 31.6610 17.725 0.8946 2.0467 28.9936 0.5139 0.2511 251.10 10.67 C3-35.2a 2.6598 32.0467 16.468 0.9010 2.3965 29.3468 0.4833 0.2017 201.66 10.77 C3-35.2b 3.0804 31.2083 18.941 0.9010 2.7754 28.5790 0.5413 0.1950 195.04 10.77 C3-35.6a 10.87 C3-35.6b 10.87 C3-35.10a 2.5299 31.9281 21.283 0.8293 2.0981 29.2382 0.6223 0.2966 296.58 10.97 C3-35.10b 2.7685 31.6939 24.351 0.8293 2.2960 29.0237 0.7068 0.3078 307.82 10.97 C3-36.2a 2.2555 31.5825 19.201 0.7963 1.7961 28.9217 0.5553 0.3092 309.19 11.07 C3-36.2b 1.7304 32.3071 17.328 0.7963 1.3779 29.5853 0.5127 0.3720 372.05 11.07 C3-36.6a 1.9838 31.3741 oxidized 10.765 0.8524 1.6910 28.7309 0.3093 0.1829 182.91 11.18 C3-36.6b 2.3000 31.2803 oxidized 12.354 0.8524 1.9605 28.6450 0.3539 0.1805 180.51 11.18 C3-36.10a 2.8715 31.3137 15.190 0.8597 2.4686 28.6755 0.4356 0.1764 176.45 11.28 C3-36.10b 2.3239 32.1136 14.330 0.8597 1.9979 29.4081 0.4214 0.2109 210.93 11.28 C3-37.2a 3.2992 31.0622 18.600 0.8600 2.8372 28.4452 0.5291 0.1865 186.48 11.38 C3-37.2b 2.9715 31.0328 12.354 0.8600 2.5554 28.4183 0.3511 0.1374 137.39 11.38 C3-37.6a 3.4228 30.1282 18.987 0.8444 2.8901 27.5899 0.5238 0.1813 181.26 11.48 C3-37.6b 1.9397 31.2351 . 9.054 0.8444 1.6378 28.6036 0.2590 0.1581 158.12 11.48 C3-38.9a 11.87 C3-38.9b 11.87 C3-39.2a 2.9918 30.0759 18.536 0.8668 2.5932 27.5420 0.5105 0.1969 196.87 11.99 C3-39.2b 2.8964 30.7652 22.445 0.8668 2.5105 28.1733 0.6323 0.2519 251.88 11.99 C3-39.6a 2.5051 31.6441 18.411 0.8636 2.1635 28.9781 0.5335 0.2466 246.60 12.09 C3-39.6b 2.2952 31.4211 17.532 0.8636 1.9822 28.7739 0.5045 0.2545 254.50 12.09 C3-39.10a 2.9512 29.5900 oxidized 37.598 0.8869 2.6173 27.0971 1.0188 0.3893 389.25 12.19 C3-39.10b 3.3853 31.3058 oxidized 23.803 0.8869 3.0023 28.6683 0.6824 0.2273 227.29 12.19 C3-40.2a . 2.4526 31.4247 oxidized 11.020 0.9048 2.2190 28.7772 0.3171 0.1429 142.91 12.29 C3-40.2b 3.6368 31.5678 oxidized 9.528 0.9048 3.2905 28.9082 0.2754 0.0837 83.71 12.29 C3-40.6a 1.9641 30.5803 31.704 0.8063 1.5837 28.0039 0.8878 0.5606 560.62 12.40 C3-40.6b 1.9681 31.9050 32.374 0.8063 1.5869 29.2170 0.9459 0.5961 596.06 12.40 C3-40.10a 12.50 C3-40.10b 12.50 C3-41.2a 2.4740 30.6462 30.747 0.8269 2.0456 28.0643 0.8629 0.4218 421.82 12.60 C3-41.2b 2.5169 31.3841 25.476 0.8269 2.0811 28.7400 0.7322 0.3518 351.82 12.60 C3-41.6a 3.0052 34.4473 14.139 0.8666 2.6042 31.5451 0.4460 0.1713 171.27 12.70 C3-41.6b 3.0875 31.2056 13.261 0.8666 2.6755 28.5766 0.3790 0.1416 141.64 12.70 C3-41.10a 2.3514 31.4894 10.556 0.8533 2.0065 28.8364 0.3044 0.1517 151.71 12.80 C3-41.10b 3.4287 30.6314 14.311 0.8533 2.9258 28.0507 0.4014 0.1372 137.21 12.80 C3-42.2a 0.8753 12.90 C3-42.2b 0.8753 12.90 C3-42.6a 1.9823 31.0213 11.746 0.8286 1.6426 28.4078 0.3337 0.2031 203.14 13.00 C3-42.6b 2.8078 30.7062 14.488 0.8286 2.3266 28.1192 0.4074 0.1751 175.10 13.00 C3-42.10a 2.8418 31.0774 8.473 0.8519 2.4208 28.4592 0.2411 0.0996 99.61 13.11 C3-42.10b 2.6131 31.1742 12.824 0.8519 2.2260 28.5478 0.3661 0.1645 164.46 13.11 C3-43.2a 2.4931 31.5122 10.923 0.8436 2.1032 28.8573 0.3152 0.1499 149.87 13.21 C3-43.2b 2.4329 31.6386 12.429 0.8436 2.0524 28.9731 0.3601 0.1755 175.46 13.21 pure water extraction C3-34.2W 3.7319 31.2212 3.849 2.9855 31.2212 0.1202 0.0403 40.25 C3-37.2W 2.0956 30.1642 2.515 1.6765 30.1642 0.0759 0.0453 45.25 C3-41.6W 2.9532 30.9004 1.803 2.3626 30.9004 0.0557 0.0236 23.58 107 Sediment Extraction Data for C2-05 Total iron - 1M CaCI2 Extraction weight of seds(g) weight of soln (g) remarks cone mg/L dry/wet ratio dry sed mass (g) ml of soln mg total of Fe mg/g gg/g FeTot depth (m) C2-2.2a 2.1647 31.0764 7.939 0.8412 1.8209 28.4582 0.2259 0.1241 124.08 0.71 C2-2.2b 2.5059 31.1268 8.390 0.8412 2.1079 28.5044 0.2392 0.1135 113.46 0.71 C2-2.6a 3.1120 30.1162 13.956 0.8348 2.5980 27.5789 0.3849 0.1482 148.15 0.81 C2-2.6b 2.3427 31.9210 11.934 0.8348 1.9557 29.2317 0.3489 0.1784 178.37 0.81 C2-2.10a 3.2477 29.4966 16.882 0.8392 2.7255 27.0115 0.4560 0.1673 167.31 0.91 C2-2.10b 2.4586 31.6361 13.668 0.8392 2.0633 28.9708 0.3960 0.1919 .191.91 0.91 C2-3.2a 3.3363 30.9776 15.538 0.8407 2.8047 28.3678 0.4408 0.1572 157.16 1.02 C2-3.2b 3.1962 31.2271 15.471 0.8407 2.6870 28.5962 0.4424 0.1647 164.65 1.02 C2-3.6a 2.0029 30.9141 12.229 0.8388 1.6800 28.3096 0.3462 0.2061 206.08 1.12 C2-3.6b 2.3833 31.6284 11.436 0.8388 1.9990 28.9637 0.3312 0.1657 165.70 1.12 C2-3.10a 3.6984 31.3643 20.093 0.8320 3.0771 28.7219 0.5771 0.1876 187.55 1.22 C2-3.10b 3.8695 30.0623 18.801 0.8320 3.2194 27.5296 0.5176 0.1608 160.77 1.22 C2-4.2a 4.0911 30.0308 16.210 0.8254 3.3770 27.5007 0.4458 0.1320 132.01 1.32 C2-4.2b 2.9414 30.2483 14.383 0.8254 2.4280 27.6999 0.3984 0.1641 164.09 1.32 C2-4.6a 2.2393 31.0213 11.339 0.8971 2.0088 28.4078 0.3221 0.1604 160.35 1.42 C2-4.6b 3.5054 31.2693 14.000 0.8971 3.1445 28.6349 0.4009 0.1275 127.49 1.42 C2-4.10a 2.5452 29.8346 18.329 0.8905 2.2666 27.3211 0.5008 0.2209 220.94 1.52 C2-4.10b 1.8133 30.7207 14.265 0.8905 1.6148 28.1325 0.4013 0.2485 248.52 1.52 C2-5.2a 2.2367 31.2585 13.028 0.8331 1.8635 28.6250 0.3729 0.2001 200.13 1.63 C2-5.2b 2.4664 30.1562 15.148 0.8331 2.0548 27.6156 0.4183 0.2036 203.58 1.63 C2-5.6a 2.3462 32.1163 13.077 0.9201 2.1588 29.4105 0.3846 0.1782 178.16 1.73 C2-5.6b 2.6492 30.5023 14.425 0.9201 2.4376 27.9325 0.4029 0.1653 165.30 1.73 C2-5.10a - - - 1.83 C2-5.10b - - 1.83 C2-6.2a 2.4225 31.7772 13.851 0.8650 2.0954 29.1000 0.4031 0.1924 192.35 1.93 C2-6.2b 2.9378 30.6230 15.201 0.8650 2.5412 28.0430 0.4263 0.1678 167.75 1.93 C2-7.5a 2.4931 30.8071 10.367 0.8769 2.1863 28.2116 0.2925 0.1338 133.78 2.34 C2-7.5b 2.0716 31.1386 9.525 0.8769 1.8166 28.5152 0.2716 0.1495 149.51 2.34 C2-7.11a 2.5811 30.5946 14.328 0.9111 2.3516 28.0170 0.4014 0.1707 170.71 2.46 C2-7.11b 3.3952 30.2775 17.528 0.9111 3.0933 27.7266 0.4860 0.1571 157.11 2.46 C2-8.3a 2.4181 30.3226 15.283 0.9131 2.2081 27.7679 0.4244 0.1922 192.19 2.57 C2-8.3b 2.3952 30.9051 14.111 0.9131 2.1872 28.3014 0.3994 0.1826 182.59 2.57 C2-8.7a 2.1560 31.0884 12.675 0.8835 1.9048 28.4692 0.3608 0.1894 189.44 2.67 C2-8.7b 2.3349 31.4686 13.177 0.8835 2.0629 28.8174 0.3797 0.1841 184.07 2.67 C2-8.11a 2.5959 30.9008 12.320 0.9302 2.4147 28.2974 0.3486 0.1444 144.38 2.77 C2-8.11b 3.1510 30.9100 13.045 0.9302 2.9310 28.3059 0.3692 0.1260 • 125.98 2.77 C2-9.3a 2.3251 31.2984 11.075 0.9477 2.2035 28.6615 0.3174 0.1441 144.06 2.87 C2-9.3b 2.8964 31.1523 13.125 0.9477 2.7449 28.5277 0.3744 0.1364 136.41 2.87 C2-9.7a 2.8292 31.3829 13.725 0.8725 2.4684 28.7389 0.3944 0.1598 159.80 2.97 C2-9.7b 2.2847 31.7360 11.283 0.8725 1.9933 29.0623 0.3279 0.1645 164.50 2.97 C2-9.11a 2.1007 30.0233 18.718 0.8952 1.8805 27.4939 0.5146 0.2737 273.66 3.07 C2-9.11b 2.7818 30.0583 22.625 0.8952 2.4902 27.5259 0.6228 0.2501 250.09 3.07 C2-10.3a 3.0120 30.8654 13.651 0.8508 2.5627 28.2650 0.3858 0.1506 150.56 3.18 C2-10.3b 2.6675 30.7671 13.902 0.8508 2.2696 28.1750 0.3917 0.1726 172.58 3.18 C2-10.7a 2.5557 32.8773 14.046 0.8474 2.1657 30.1074 0.4229 0.1953 195.27 3.28 C2-10.7b 1.9969 29.9405 13.252 0.8474 1.6922 27.4180 0.3633 0.2147 214.72 3.28 C2-10.11a 3.5505 29.7785 15.503 0.8536 3.0308 27.2697 0.4228 0.1395 139.49 3.38 C2-10.11b 4.6640 30.7071 15.271 0.8536 3.9813 28.1201 0.4294 0.1079 107.86 3.38 C2-11.3a 3.6858 30.4404 14.869 0.8465 3.1202 27.8758 0.4145 0.1328 132.84 3.48 C2-11.3b 4.1562 31.0083 17.604 0.8465 3.5184 28.3959 0.4999 0.1421 142.08 3.48 C2-11.7a 2.3961 31.2035 16.352 0.8397 2.0120 28.5746 0.4673 0.2322 232.23 3.58 C2-11.7b 4.3445 30.2111 22.397 0.8397 3.6481 27.6658 0.6196 0.1699 169.85 3.58 pure water extraction C2-3.6W 1.6353 29.4294 2.347 1.3082 29.4294 0.0691 0.0528 52.80 C2-4.6W 2.9805 30.0873 1.292 2.3844 30.0873 0.0389 0.0163 16.30 C2-10.7W 2.2211 29.7663 2.991 1.7769 29.7663 0.0890 0.0501 50.11 108 Sediment Extraction Data for C1-05 Total iron - 1M CaCI2 Extraction sed weight (g) soln weight (g) remarks cone mg/L dry/wet ratio dry mass (g) ml of soln mg total of Fe mg/g ug/g FeTot depth (m) C1-4.4a 4.0170 31.6111 31.4 0.7823 3.1423 28.9479 0.9090 0.2893 289.2667 0.25 C1-4.4b 0.7823 0.25 C1-4.8a 3.0089 30.8392 40.4 0.8078 2.4306 28.2410 1.1409 0.4694 469.3995 0.35 C1-4.8b 0.8078 0.35 C1-5.0a 2.7502 31.4180 oxidation 30.925 0.7421 2.0408 28.7711 0.8897 0.4360 435.9722 0.45 C1-5.0b 4.8950 30.1842 oxidation 49.2 0.7421 3.6324 27.6412 1.3599 0.3744 374.3923 0.45 C1-5.4a 4.0290 32.8256 oxidation 90.9 0.6519 2.6265 30.0601 2.7325 1.0404 1040.3592 0.56 C1-5.4b 0.6519 0.56 C1-5.8a 2.0453 30.5517 oxidation 24.3 0.7898 1.6154 27.9777 0.6799 0.4209 420.8634 0.66 C1-5.8b 2.3665 31.6255 oxidation 21 0.7898 1.8691 28.9611 0.6082 0.3254 325.3919 0.66 C1-6.0a 3.3453 32.0328 oxidation 20.95 0.8587 2.8727 29.3341 0.6145 0.2139 213.9301 0.76 C1-6.0b 0.8587 0.76 C1-6.4a 5.3993 31.3589 20.975 0.9504 5.1314 28.7169 0.6023 0.1174 117.3835 0.86 C1-6.4b 4.2619 31.0453 18.725 0.9504 4.0504 28.4298 0.5323 0.1314 131.4305 0.86 C1-6.8a 4.5503 30.9955 36.3 0.9505 4.3253 28.3842 1.0303 0.2382 238.2157 0.96 C1-6.8b 0.9505 0.96 C1-7.0a 5.2409 31.9375 28.35 0.9560 5.0104 29.2468 0.8291 0.1655 165.4861 1.06 C1-7.0b 0.9560 1.06 C1-7.4a 3.0125 30.2775 20.55 0.8763 2.6397 27.7266 0.5698 0.2159 215.8502 1.17 C1-7.4b 3.2902 31.8953 19 0.8763 2.8830 29.2082 0.5550 0.1925 192.4889 1.17 C1-7.8a 2.5300 30.9633 35.275 0.8429 2.1325 28.3547 1.0002 0.4690 469.0365 1.27 C1-7.8b 4.1364 30.1279 54.65 0.8429 3.4865 27.5897 1.5078 0.4325 432.4635 1.27 C1-8.0a 2.9480 31.1514 38.1 0.8319 2.4524 28.5269 1.0869 0.4432 443.1931 1.37 C1-8.0b 4.2249 30.3604 53.65 0.8319 3.5146 27.8026 1.4916 0.4244 424.4033 1.37 C1-8.4a 4.2539 30.5272 36.35 0.8619 3.6664 27.9553 1.0162 0.2772 277.1625 1.47 C1-8.4b 0.8619 1.47 C1-10.6a 3.1711 31.6341 21.7 0.8141 2.5816 28.9690 0.6286 0.2435 243.5050 3.25 C1-10.6b 3.0876 30.7447 21.775 0.8141 2.5136 28.1545 0.6131 0.2439 243.8990 3.25 C1-10.10a 2.8348 32.5882 22.25 0.7995 2.2666 29.8427 0.6640 0.2930 292.9559 3.35 C1-10.10b 3.6512 30.4902 27.775 0.7995 2.9193 27.9214 0.7755 0.2657 265.6519 3.35 C1 -11.2a 2.6255 31.2826 16.375 0.8184 2.1488 28.6471 0.4691 0.2183 218.3106 3.45 C1-11.2b 2.6677 31.0192 16.3 0.8184 2.1833 28.4059 0.4630 0.2121 212.0723 3.45 C1-11.6a 2.6787 30.9815 21.525 0.8305 2.2246 28.3713 0.6107 0.2745 274.5216 3.56 C1-11.6b 4.8755 29.6708 33.875 0.8305 4.0489 27.1711 0.9204 0.2273 227.3235 3.56 C1-11.10a 3.1097 31.9504 21.025 0.8199 2.5497 29.2586 0.6152 0.2413 241.2687 3.66 C1-11.10b 2.4422 30.2569 19.7 0.8199 2.0024 27.7078 0.5458 0.2726 272.5942 3.66 C1-12.2a 3.0867 30.0925 19 0.8225 2.5389 27.5572 0.5236 0.2062 206.2297 3.76 C1-12.2b 2.6471 29.0593 18.025 0.8225 2.1773 26.6111 0.4797 0.2203 220.3048 3.76 C1-12.6a 2.6591 31.7784 16.15 0.8326 2.2141 29.1011 0.4700 0.2123 212.2712 3.86 C1-12.6b 2.3676 31.3838 16.3 0.8326 1.9714 28.7397 0.4685 0.2376 237.6325 3.86 C1-12.10a 2.4155 31.6340 19.275 0.8278 1.9995 28.9689 0.5584 0.2793 279.2582 3.96 C1-12.10b 3.6738 31.2115 24.175 0.8278 3.0411 28.5820 0.6910 0.2272 227.2114 3.96 C1-13.2a 4.4334 30.6452 24.025 0.8197 3.6341 28.0634 0.6742 0.1855 185.5290 4.06 C1-13.2b 3.6472 30.3456 17.3 0.8197 2.9896 27.7890 0.4807 0.1608 160.8070 4.06 C1-13.6a 3.3694 31.3686 9.25 0.8179 2.7560 28.7258 0.2657 0.0964 96.4133 4.17 C1 -13.6b 0.8179 0.0000 4.17 C1-13.10a 2.7027 29.3872 15.85 0.8179 2.2106 26.9114 0.4265 0.1930 192.9527 4.27 C1-13.10b 2.2891 31.2484 13.375 0.8179 1.8723 28.6158 0.3827 0.2044 204.4175 4.27 redone C1-4.4a1 1.6391 30.7575 21.18 0.7823 1.2822 28.1662 0.5966 0.4653 465.2674 0.25 C1-4.4b1 1.4693 30.0857 22.25 0.7823 1.1494 27.5510 0.6130 0.5333 533.3480 0.25 C1-4.8a1 1.2876 29.7323 17.98 0.8078 1.0401 27.2274 0.4895 0.4707 470.6555 0.35 C1-4.8b1 1.3029 30.4225 17.2 0.8078 1.0525 27.8594 0.4792 0.4553 455.2796 0.35 C1-5.4a1 1.1096 30.8382 35 0.6519 0.7233 28.2401 0.9884 1.3665 1366.4528 0.56 C1-5.4b1 1.2964 30.1119 40.65 0.6519 0.8451 27.5750 1.1209 1.3264 1326.3670 0.56 C1-6.0a1 2.4801 30.0348 23.8 0.8587 2.1297 27.5044 0.6546 0.3074 307.3694 0.76 C1-6.0b1 1.8554 29.9842 21.68 0.8587 1.5933 27.4581 0.5953 0.3736 373.6305 0.76 C1-6.8a1 2.5868 29.8850 28.38 0.9505 2.4589 27.3672 0.7767 0.3159 315.8697 0.96 C1-6.8b1 2.7250 30.1320 27 0.9505 2.5902 27.5934 0.7450 0.2876 287.6275 0.96 C1-7.0a1 2.0423 30.5551 18.35 0.9560 1.9525 27.9809 0.5134 0.2630 262.9745 1.06 C1-7.0b1 1.3972 29.7117 12.15 0.9560 1.3357 27.2085 0.3306 0.2475 247.4905 1.06 C1-13.6a1 2.0525 29.6924 14.9 0.8179 1.6788 27.1908 0.4051 0.2413 241.3243 4.17 C1-13.6b1 2.1813 30.3984 14.73 0.8179 1.7842 27.8374 0.4100 0.2298 229.8215 4.17 109 A p p e n d i x C Lab Procedures for Iron Sediment Extractions 1M CaCI2 extractions: Equipment used: Lab balance: Denver Instrument XP-300 Low Budget balance Precision balance: Mettler Toledo AE 100 electronic analytical balance Repeater pipette: Eppendorf Repeater Pipette model 4780 with a 50 ml combitip Spectrophotometer: Hach DR/2400 Spectrophotometer Centrifuge tube: VWR 50 ml flat top sterile graduated plastic centrifuge tube Enough CaC^ dihydrate (ACS standard) was measured out in an 8 cm diameter plastic weighing dish on a Denver Instrument XP-300 Low Budget balance to constitute 0.5 moles. It was then flushed with distilled and deionized water (DlW) (resitivity = 17.8 MQ, electric conductivity < 0.6 uS cm"1) into a 500 ml graduated cylinder. Nano-pure water was added to the 500 ml mark. The 500 ml were poured into a 2.5L glass bottle and this procedure was repeated until the bottle was filled. Ultra high purity (UHP) nitrogen was bubbled through the solution for about 30 minutes to purge it of oxygen and then checked with Chemets low range dissolved oxygen snap-off vials (K-7501). In a Coy Vinyl Anaerobic Glovebox, Type B, between 2 and 5 g of sediment sample were added to a VWR 50 ml flat top sterile graduated plastic centrifuge tube. A Mettler Toledo AE 100 electronic analytical balance was zeroed with the empty centrifuge placed inside a custom-made Styrofoam and aluminum foil holder before the addition of the sediment and the weight recorded to the fourth decimal. The scale was zeroed again and the 1M CaCI 2 solution added to the 30 ml mark, placed back on the scale and the weight of the solution recorded to the fourth decimal. The screw cap was placed back on to the centrifuge tube and it was set aside. After approximately 3 hours of loading the samples into the centrifuge tubes, the filled centrifuge tubes were removed from the glovebox, labelled in multiple locations and placed inside a 50x30x30 cm cardboard box, which was secured with duct tape on a rotary shaker table that ran for approximately 24 hours at 200 rpm. Pipette: Eppendorf Research Series 2100 Adjustable Volume Pipetters, 10-100 ul and 100-1000 pi Glovebox: Vinyl Anaerobic Glovebox, Type B 111 After the elapsed time, the samples were placed in an antique-style centrifuge with a measured rotational speed of no less than 625 rpm. At the time it was thought to spin at 2000 rpm, and according to Jackson's [1956] formula, a particle cut-off of 25 pm was selected and a rotation time of 25 minutes calculated. The samples were then taken out of the centrifuge, opened, and 1.000 ml of the solution was removed from the top with an Eppendorf Research Series 2100 Adjustable Volume Pipetter (10-100 pi) and diluted to 25 ml using an Eppendorf Reference Adjustable Volume Pipetter (100-1000 pi) as well as an Eppendorf Repeater Pipetter model 4780 with a 50 ml combitip. The solution was then analyzed with the Hach Ferrozine method (method 8147) for total iron in a Hach DR/2400 spectrophotometer [Hach Company 2002]. The leftover water sample was taken out of its centrifuge tube with a 20 ml disposable plastic syringe, so that the sediment remained at the bottom of the tube, It was transferred to another centrifuge tube, acidified with 30 pi of 5M HCI and set aside for later analysis. Jackson, Marion LeRoy. 1956. Soil chemical analysis, advanced course ; a manual of methods useful for instruction and research in soil chemistry, physical chemistry of soils, soil fertility and soil genesis. P 127. Madison, Wisconsin: Department of Soils. Hach Company. 2002. DR/2400 Spectrophotometer Procedure Manual. Catalogue number 59400-22. 112 0.75M HCI extractions: Equipment used: Repeater pipette: Eppendorf Repeater Pipette model 4780 with a 50 ml combitip Pipette: Eppendorf Research Series 2100 Adjustable Volume Pipetters, 10-100 pi and 100-1000 pi Glovebox: Syringe Filter: Coy Vinyl Anaerobic Glovebox, Type B Acrodisc 25mm Syringe Filter with 0.2pm Supor Membrane Spectrophotometer: Hach DR/2400 Spectrophotometer Centrifuge tube: VWR 50 ml flat top sterile graduated plastic centrifuge tube A 500 ml graduated cylinder was filled with some DIW. 31.25 ml of concentrated hydrochloric acid were measured into the cylinder and it was topped up to the 500 ml mark. The solution was poured into a 2.5L glass bottle and the procedure was repeated until the bottle was filled. UHP nitrogen was bubbled through the solution to purge it of oxygen. In a glovebox, between 2 and 5 g of sediment sample was added to a centrifuge tube. The precision balance was zeroed with the empty centrifuge placed inside a custom-made Styrofoam and aluminum foil holder before the addition of the sediment and the weight recorded to the fourth decimal. The scale was then zeroed again and the 0.75M HCI solution added to the 30 ml mark, placed back on the scale and the weight of the solution recorded to the fourth decimal. The screw cap was placed back on to the centrifuge tube and it was set aside. After approximately 2.5 hours of loading the samples into the centrifuge tubes, the filled centrifuge tubes were removed from the glovebox, labelled in multiple locations, placed inside a 50x30x30 cm cardboard box, which was secured with duct tape on a rotary shaker table that ran for approximately 24 hours at about 200 rpm. After the elapsed time, the samples were placed in an antique-style centrifuge with a measured rotational speed of no less than 625 rpm. At the time it was thought to spin at 2000 rpm, and according to Jackson's [1956] formula, a particle cut-off of 25 pm was selected and a rotation time of 25 minutes calculated. 113 The samples were then taken out of the centrifuge, opened, and the water sample was taken out of its centrifuge tube with a 20 ml disposable plastic syringe, so that the sediment remained at the bottom of the tube. The clear solution was then transferred to another centrifuge tube through a 0.2 pm syringe filter. 0.500 or 1.000 ml of the solution was removed with a pipetter and diluted to 25 ml using pipetters and a repeater pipetter. The solution was then analyzed with the Hach Ferrozine method (method 8147) for total iron in a Hach DR/2400 spectrophotometer. 114 5.0M HCI extractions: Equipment used: Repeater pipetter: Eppendorf Repeater Pipetter model 4780 with a 50 ml combitip Pipetter: Eppendorf Research Series 2100 Adjustable Volume Pipetter 10-100 pi and Eppendorf Reference Adjustable Volume Pipetter 100-1000 pi Glovebox: Coy Vinyl Anaerobic Glovebox, Type B Syringe Filter: Acrodisc 25mm Syringe Filter with 0.2pm Supor Membrane Spectrophotometer: Hach DR/2400 Spectrophotometer Centrifuge tube: Fisher Scientific 50 ml plug seal sterile graduated plastic centrifuge tube A 500 ml graduated cylinder was filled to the 192 ml mark with nano-pure water. It was filled to the 400 ml mark with concentrated hydrochloric acid and distilled and deionized water was used to fill the cylinder up to the 500 ml mark. The solution was poured into a 2.5L glass bottle and the procedure was repeated until the bottle was filled. Finally, Ultra High Purity (UHP) nitrogen was bubbled through the solution for 40 minutes to purge it of oxygen. In a glovebox, between 1 and 2 grams of sediment sample was added to a centrifuge tube. The balance was zeroed with the empty centrifuge placed inside a custom-made Styrofoam and aluminum foil holder before the addition of the sediment, and the weight recorded to the fourth decimal. The scale was then zeroed again and the 5M HCI solution added to the 30 ml mark, placed back on the scale, and the weight of the solution recorded to the fourth decimal. The screw cap was placed back on to the tube and it was set aside. After approximately four hours of loading the samples into the centrifuge tubes, the filled tubes were removed from the glovebox, stood in Styrofoam holders and placed inside a 50x30x30 cm cardboard box (see Figure 1). The box was secured with duct tape on a rotary shaker table that ran for 21 days at about 150 rpm. After the elapsed time, the samples were placed in an antique-style centrifuge with a rotational speed of no less than 625 rpm. At the time it was thought to spin 115 at 2000 rpm, and according to Jackson's [1956] formula, a particle cut-off of 25 pm was selected and a rotation time of 25 minutes calculated. The samples were then taken out of the centrifuge, opened, and a water sample was taken out of each centrifuge tube with a 20 ml disposable plastic syringe, while making sure that the sediment remained at the bottom of the tube. The now bright yellow solution was then transferred to another centrifuge tube through a 0.2 pm syringe filter. 20 pi of the solution were removed with an Eppendorf Research Series 2100 Adjustable Volume Pipetter 10-100 pi and diluted to 25 ml using that and a Eppendorf Reference Adjustable Volume Pipetter 100-1000 plas well as an Eppendorf Repeater Pipetter model 4780 with a 50 ml combitip. The solution was then analyzed with the Hach Ferrozine method (method 8147) for iron(ll) in a Hach DR/2400 spectrophotometer. 116 A p p e n d i x D Analysis Procedure for PAH analyses of Water Sampl PAH concentrations in water were determined by Gord Stewart from the UBC microbiology lab using the following methodology: 1. Water samples were collected in 42 mL screw-cap vials, filled to the top. Most vials had a considerable precipitate of ferric oxide. 2. 7.0 mL water was removed from each vial, and the vials weighed. 3. 2.0 mL of dichloromethane with 1.0 ppm each of indane, naphthalene, benzothiophene, 3-fluorotoluene, and 2-fluorobiphenyl was added to each vial. 4. The vials were reweighed to confirm the mass of solvent added, since dichloromethane is difficult to pipette accurately. 5. The vials were shaken at 250 rpm for 2 h and allowed to settle for 60 min. 6. The dichloromethane layer (in the form of dozens of globules coated, with ferric oxide) was removed from the bottom of the vial by pipet, and placed in an 8 mL tube, with a PTFE-faced rubber liner screw-cap. Excess water was removed by pipet, and the tubes centrifuged (2000 x g) for 4 min. The remaining water layer was removed. 1 7. The dichloromethane samples were placed in 2 mL autosampler vials and analysed on an Agilent 6890 gas chromatograph with a 5973N mass selective detector, using a 30 metre HP-5ms column, 250 urn diameter, 0.25 urn film thickness. The carrier gas was helium, at 1.0 mL/min. The inlet temperature was 260C, oven temp started at 40C for 1.0 min, then was ramped at 15C/min to 115C, then 5C/min to 125C, then 20C/min to 220C, then 30C/min to 280C. The transfer line temperature was 280C. The mass spectrometer was run in El mode, scanning 50 - 400 m/z. 8. Analytical standards were run to create standard curves. Extraction standards, using 35 mL water spiked with standards in methanol, were extracted by the same method, to determine extraction efficiency. All calculations used 2-fluorobiphenyl as an internal standard. 118 A p p e n d i x E PhreeqC Geochemical Modelling Input File SOLUTION_SPREAD -temp 11 -pe -2 -units mg/l Description Number pH Br Cl P6-05-01 1 7.67 0 0.57 P6-05-02 2 6.33 0 5.85 P6-05-03 3 6.12 0 7.58 P6-05-04 ,4 6.18 . 0 7.19 P6-05-05 5 6.18 . 0 12.9 P6-05-06 6 6.24 - 0 •12.5 P6-05-07 7 6.29 . 0 6.96 P6-05-08 8 6.31 0 11.4 P6-05-09 9 6.36 0 4.83 P6-05-10 10 6.37 0 5.18 P6-05-11 11 7.07 - 0 14.1 P6-05-12 12 7.14 0.075 24.8 P6-05-13 13 7.15 0.184 66.4 P6-05-14 14 7.07 0.284 104 • P6-05-15 15 7.03 0.608 210 P22-05- 13 16 7.63 0 0.61 P22-05- 8 17 6.81 1.27 462 P22-05-4 18 7.06 2.74 955 P22-05- 1 19 7.03 3.3 1250 P22-05- 2 20 7.3 3.8 1430 P22-05- 3 21 7.67 4.2 1590 P23-05- 1 22 7.1 0 0.8 P23-05- 6 23 6.65 0 2.94 P23-05- 7 24 6.34 0 2.95 P23-05- 8 25 6.54 0 2.87 P23-05- 9 26 6.6 0 3.02 P23-05- 10 27 6.58 0 2.97 P23-05- 11 28 6.6 0 3.04 P23-05- 13 29 6.54 0 3.62 P23-05- 14 30 6.52 0 3.8 P23-05- 15 31 6.47 0 4.37 P23-05- 16 32 6.46 0 4.38 P23-05- 17 33 6.52 0 3.69 P23-05- 18 34 6.63 0 5.49 P23-05- 19 35 6.59 0 5.41 P23-05- 20 36 7.25 0 6.3 P3-06-R 37 7.2 0 1.78 P3-06-03 38 6.57 0 14 P3-06-04 39 6.72 0.406 136 P3-06-05 40 6.75 1.68 544 P3-06-06 41 6.85 3.27 1010 TR-0/10 42 6.4 0 24.5 TR-10/20 43 6.4 0 10 TR-20/30 44 6.4 0 8.05 TR-30/40 45 6.4 0 14.5 TR-40/50 46 6.4 0 5.82 TR-50/60 47 6.4 0 7.14 SELECTED_OUTPUT -file D:\M.Sc. Thesis Data Files\Braid St\P-05w.out -se!ected_out true -solution true -alkalinity true -ionic_strength true -charge_balance true -percent_error true -totals Alkalinity -saturationjndices Calcite Dolomite Siderite Rhodochrostte Ankerite Fe{OH)3(a) F S(6) Ba B Ca 0.03 6.23 0 0 10.2 0.034 0 0.025 0 13.1 0.035 0 0.035 0 17.4 0.031 0 0.036 0.14 25.7 0.033 0 0.014 0 11.8 0.029 0 0.017 0 15.8 0.023 0 0.012 0 11.7 0.028 0 0.016 0 20.2 0.025 0 0 0 13.4 0.025 0 0.019 0 26.5 0.028 0 0.017 0 27.5 0.029 0 0.01 0 17 0.029 0 0.025 0 39.9 0.028 0 0.04 0 62.3 0.029 0 0.05 0 66.7 0.028 5.6 0.01 0 117 0 0 0.184 0.16 188 0 0 0.408 0.27 180 0 0 0.584 0.44 231 0 0 0.416 0.57 143 0 0. 0.133 ' 0.36 26.7 0.028 6.09 0 0 11.6 0.042 0 0.049 0 14.6 0.048 0 0.077 0 22.9 0.04 0 0.076 0 21.2 0.038 0 0.077 0 21 0.034 0 0.044 0 11.1 0.029 0 0.086 0.11 21.9 0.037 0 0.066 0 24.9 0.037 0 0.046 0 25.8 0.034 0 0.039 0 29 0.032 0 0.047 0 30.2 0.027 0 0.043 0.11 47.1 0.03 0 0.038 0.12 62.5 0.027 0 0.034 0.11 71.5 0.026 0 0.03 0 74.2 0.036 5.99 0.014 0 13.9 0.052 0.3 0.044 0.19 33.7 0.06 0.2 0.091 0.21 70.4 0 3 0.278 0.25 155 0 1 0.407 0.38 200 0 8.19 0.11 0.05 55.2 0 3.83 0.11 0.07 54.5 0 0.98 0.099 0.14 39.5 0 0.5 0.11 0.19 38.5 0 0.58 0.1 0.24 36.2 0 0.82 0.086 0.22 32:9 Fe Mg Mn . P K 1.23 2.25 0.0674 0 . 0 19.9 4.55 0.964 0 0 32.9 7.99 1.36 0 0 55.9 12.9 2.29 0 2.9 21.1 5.67 0.896 0 0 25.9 7.61 1.13 0 0 14.8 4.84 .0.698 0 ' 0 •19.3 7.28 0.971 0 0 9.98 4.32 0.548 0 0 16.3 8.36 0.965 0 0 13.6 8.62 0.869 0 0 7.56 5.41 0.49 0 0 16 13.1 1.05 0 2.1 21.7 20.7 1.52 0 3.1 23.8 22.3 1.77 0 3.9 0.078 2.38 0.0188 0 0 • 38.2 44 5.32 0 17.3 22.8 42 6.21 0.32 31 25.4 60.8 772 0.36 42.1 10.3 61.3 2.95 0.68 37.1 1.35 34.9 0.278 0.66 15.7 0.072 1.88 0.0212 0 0 17.6 9.54 0.412 0 0 31.9 14.9 0704 0 0 34.2 14.6 0.748 0 0 35.5 14.4 0.797 0 0 18.3 7.65 0.428 0 0 42.8 15.1 0.975 0 0 69.3 13.4 1.51 0 0 72.1 13.5 1.77 0 0 72.4 13.1 1.93 0 2 71.5 14.6 2.26' 0 2.1 53.1 21.7 3.71 0 0 46.6 28.6 2.4 0 2.2 23.4 28.7 0.635 0 0 22.4 25.7 0.558 0 0 0.114 3.63 0.0105 0 0.1 62.4 16.3 2.76 0 4 85.7 27.4 4.55 0 7.3 90.1 42.9 6.65 0 18.3 71.7 48.8 6.56 0 31.1 8.3 10 3.78 0.2 3.6 25 9.32 3.84 0.2 3.7 33 8.48 2.67 0.3 4.8 35.7 9.23 2.77 0.2 5.8 34 9.12 2.53 0.2 6.7 36 8.68 2.25 0.4 6.5 Na Sr Zn Alkalinity 1.7 0 0.0507 0.0337 28.39985 5.32 3.7 0.0569 0.0822 88.704 11 7.1 0.0857 0.504 143.2515 17.6 9.4 0.128 0.0934 235.7185 7.15 3.6 0.0548 0.0177 81.849 8.17 4.2 0.0719 0.0282 110.737 5.38 2.2 0.0492 0.0249 71.894 7.99 3.2 0.079 0.0526 107.668 4.69 0 0.0492 0.0113 63.2735 8.48 3.1 0.0939 0.0303 130.9885 8.54 2.8 0.0953 0.0118 115.351 4.89 0 0.0578 0.006 43.2903 9.85 3.8 0.137 0.0256 99.696 11.9 5.7 0.207 0.012 150.6155 10.3 9.9 0.246 0.0289 33.1144 2.04 0 0.062 0.0062 32.3881 19 63.6 0.781 0.0421 237.0345 15.1 329 1.07 0.0456 125 20.3 533 1.49 0.0588 200 15.5 616 1.15 0.0221 130 5.74 343 0.368 0.0073 230 1.5 0 0.0488 0.0078 250 13.1 10.2 0.0708 0.0543 125.954 19.2 16.2 0.11 0.0252 207.99 17.5 15.7 0.108 0.0123 205.6435 18.2 16.6 0.11 0.0148 208.443 9.18 8.9 0.0612 0.0071 107.8285 17.9 17.7 0.128 0.0092 229.339 16.9 18 0.15 0.0077 278.0605 17.2 17.8 0.162 0.0138 285.5425 17.3 16.7 0.182 . 0.027 292.173 18.9 19.4 0.202 0.0215 306.353 22.4 10.3 0.225 0.0133 325.9345 25.2 10.1 0.273 0.0176 378.528 25.3 10.5 0.292 0.0313 354.998 22.5 8.5 0.281 0.0184 338.052 2.76 2.9 0.0702 0.132 46.372 17.9 6.1 0.145 0.0977 303.628 19.1 16.1 0.286 0.182 347.792 17.6 110 0.636 0.075 331.23 17.6 342 0.946 0.0325 436.12 6 7.67 0.31 0 137 8.7 5.99 0.27 0 213 11.2 6.48 0.19 0 184 12.2 8.22 0.19 0 182 16.7 8.36 0.17 0 183 13.3 8.48 0.16 0 152 END 

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