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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  th  order river. The site selected for study is located at the trailing edge of a postglacial 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 oxygenrich 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 Purpose of Research 1.2 Thesis Outline  1 2 2  2. Literature Review 2.1 Previous Hyporheic Zone Studies 2.2 Review of Extraction Methods  4 4 6  3. Site Description . 3 . 1 Previous Research and History of the Site 3.2 Geology and Hydrogeology at the Site 3.3 Geochemistry  9 9 11 13  4. Methods 4.1 Sample Collection 4.1.1 Sediment Core Collection 4.1.1.1 2005 Cores 4.1.1.2 Summer 2006 Cores 4.1.2 Simultaneous Core and Pore Water Collection 4.1.3 Water Sample Collection 4.2 Sample Analyses 4.2.1 Water Samples 4.2.2 Sediment Analyses 4.2.2.1 Sediment Extractions 4.2.2.2 Scanning Electron Microscopy 4.2.2.3 Rietveld X-Ray Diffraction  15 15 16 16 18 19 23 25 25 27 27 28 28  5. Results and Discussion 5.1 Sediment Stratigraphy and Groundwater Flow 5.1.1 Rietveld X-Ray Diffraction and Scanning Electron Microscopy 5.2 Results of Water Analyses 5.2.1 Organics 5.2.2 Conservative Tracer Concentrations 5.2.3 Redox Sensitive Species Concentrations 5.2.4 Geochemical Modelling 5.3 Results of Sediment Extractions 5.3.1 Speciation of Iron Extracts  30 30 32 33 33 35 36 37 38 38  5.3.2 Results of Total Iron Concentrations  39  6. Conclusions 6.1 Depth of the Hyporheic Zone 6.2 Iron Accumulation and Redox Conditions  41 41 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 P A H 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 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  2  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  vii  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 C105, C2-05, C3-05  76  Figure 29: Graphs showing total iron concentrations in 2006 sediment cores C106, C2-06, C4-06  77  Figure 30: Graphs showing total iron concentrations in 2006 sediment core C1206  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 hydrogroup 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.  Introduction  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 reductionoxidation (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 also causes the partial dissolution of amorphous iron sulphides. 3  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 extraction. A magnesium or calcium chloride solution has 2  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  th  order river and has average and peak flows of approximately 3500 m /s and 3  10,000 m /s, respectively. Its drainage basin (Figure 1) encompasses 228,000 3  km . The site selected for investigation is located at the trailing edge of a post2  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~ m/s (Golder 1997). 4  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" m/s (Golder 1997). 7  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~ m/s (Golder 1997). 4  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" towards the river was observed. However, the 4  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 /hourfrom 1996 to 1999 and has been 27m /hour since then. 3  3  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 nonaqueous 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 (Mn ) are also insignificant. 2+  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.  Methods  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 2004, between 17:45 and 18:00, using a pre-marked rope with a weight th  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 2005 during freshet th  (approximate discharge 6000 m /s) with the freeze-shoe method developed by 3  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 2006 from st  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 1 / inch diameter and 65 3  8  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 50m of the river bottom and 2  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 hollowchambered 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 , 2006 (Figures 17 and 18). st  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. A s 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 custombuilt 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 ), nitrate (N0 ~) were 2+  3  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 and July 8 . See Table 1 for an overview of the rd  th  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 . For DO, a 20ml container was filled 2+  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 " was measured colorimetrically with Hach AccuVac NitraVer 5 ampoules in a 3  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 F e  2+  and alkalinity. F e  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 deaired 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. A n 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.  Results and  Discussion  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 in the 2  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 - was inhabited by five or 3  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 F e S ) particles on the order of 100 to 1000 nm in size (Hesse and Stolz 2+  3+  4  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 C H 0 : 2  2 F e 0 + C H 0 + 11 H = 6 F e +  3  4  2  2+  + 6 H 0 + C 0 + OH" 2  2  (1) 33  2 H + CH 0 + C 0 2  2  2  CH + H 0 + C 0 4  2  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 r value of 2  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 r value of 0.95. 2  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 P1206, 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 C305. 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.  Conclusions  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/cm  3  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 siltdominated, 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  P605  P2205  P2305  P306  P12-06  Bottle filled  Yes  Yes  Yes  Yes  Yes  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 Tefonseptum 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  Analysis  Container  Method/Notes  Anions  60 ml polyethylene bottle  Cations  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  5.0 M HCI  21 days  Amorphous and weakly crystalline minerals 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 0.35 0.45 0.56 0.66 0.76 0.86 0.96 1.06 1.17 1.27 1.37 1.47  silty sand with visible mica silty sand with visible mica and some wood chips silty sand mixed with 5-10% wood matter silty sand mixed with 60% wood matter silty sand silty sand pebbly sand (pebbles 1-3 mm) pebbly sand (pebbles 1mm to 1cm) pebbly sand (pebbles 1mm to 1cm) and clam shells pebbly sand (pebbles 1mm to 1cm) and clam shells dark grey coarse sand dark prey coarse sand dark qrey coarse sand  3.19 3.25 3.35 3.45 3.56 3.66 3.76 3.86 3.96 4.06 4.17 4.27  dark grey coarse sand dark qrey coarse sand dark grey coarse sand and thin slice of plant matter dark grey coarse sand dark grey coarse sand dark grey coarse sand dark grey coarse sand dark qrey coarse sand black medium to coarse grained sand black medium to coarse qrained sand black medium to coarse grained sand  C3-05 medium depth [m] 10.14 10.26 10.36 10.46 10.57 10.67 10.77 10.87 10.97 11.07 11.18 11.28 11.38 11.48  Description 0.2cm pebbles mixed with coarse sand 0.2cm pebbles mixed with coarse sand coarse sand with 1mm to 1cm pebbles coarse sand with 1mm to 1cm pebbles coarse homogeneous sand coarse homogeneous sand coarse sand with clay as small scale (10cm) heterogeneity coarse sand with clay as small scale (10cm) heterogeneity silt with wood debris silt with wood debris medium to fine qrained sand with visible mica medium qrained sand medium qrained sand with some silt 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 12.19 12.29 12.40 12.50 12.60 12.70 12.80 12.90 13.00 13.11  medium to coarse grained dark grey homogeneous sand medium to coarse grained sand with ~1cm clay blobs pebbles, coarse sand, clay and wood debris mix silt to fine sand with - 1 0 % wood matter and frequent clay blobs silt to fine sand with - 1 0 % wood matter and frequent clay blobs silt to fine sand with ~10% wood matter and frequent clay blobs medium to coarse qrained homoqeneous sand with visible white medium to coarse qrained homoqeneous sand with visible white medium to coarse qrained homoqeneous sand with visible white medium to coarse qrained homoqeneous sand with visible white medium to coarse qrained homoqeneous sand with visible white  mica mica mica mica mica  Table 3 - Core logs for cores C1-05 and C3-05. Depth indicated is the medium depth of a 10 cm interval. 48  C2-05  medium depth [m]  Description  0.71 0.81 0.91 1.02 1.12 1.22 1.32 1.42 1.52 1.63 1.73 1.83 1.93  medium grained dark qrey/black homogeneous sand with visible white mica medium grained dark qrey/black homogeneous sand with visible white mica medium grained dark qrey/black homoqeneous sand with visible white mica medium qrained dark qrey/black homogeneous sand with visible white mica medium grained dark qrey/black homoqeneous sand with visible white mica medium qrained dark qrey/black homogeneous sand with visible white mica medium qrained dark qrey/black homoqeneous sand with visible white mica medium qrained dark qrey/black homogeneous sand with visible white mica medium grained dark qrey/black homogeneous sand with visible white mica medium qrained dark qrey/black homogeneous sand with visible white mica medium qrained dark qrey/black homoqeneous sand with visible white mica medium qrained dark qrey/black homoqeneous sand with visible white mica medium grained dark qrey/black homogeneous sand with visible white mica  2.34 2.46 2.57 2.67 2.77 2.87 2.97 3.07 3.18 3.28 3.38 3.48 3.58  medium qrained dark qrey/black homoqeneous sand with visible white mica medium qrained dark qrey/black homogeneous sand with visible white mica medium qrained dark qrey/black homogeneous sand with visible white mica medium qrained dark qrey/black homoqeneous sand with visible white mica coarse grained sand with up to 5mm diameter pebbles coarse qrained sand with up to 5mm diameter pebbles medium grained dark qrey/black homogeneous sand with visible white mica coarse to medium qrained sand with 1.5cm pebbles interspersed medium grained dark grey/black homoqeneous sand with visible white mica medium qrained dark qrey/black homoqeneous sand with visible white mica medium grained dark qrey/black homoqeneous sand with visible white mica medium grained dark qrey/black homoqeneous sand with visible white mica medium grained dark qrey/black homoqeneous sand with visible white mica  0.03 0.11  wood debris with some fine silt (up to 20%) silt with some wood debris (up to 15%)  0.03 0.10  qravel and coarse sand coarse sand  0.04 0.13 0.23 0.33 0.43 0.53  pebbles and coarse sand medium to coarse-qrained dark sand medium to coarse-qrained dark sand medium-qrained sand medium-qrained sand medium-qrained sand  C1-06  C2-06  C4-06  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 Albite Ankerite Chlorite Muscovite Quartz Hornblende  1.2 m 1.7 m 2.1 m 2.2 m 3.5 m 10.5 m 32.44 39.19 33.55 34.88 34.20 35.28 1.10 0.61 0.70 0.39 0.79 1.10 6.82 6.74 6.96 8.27 6.55 5.59 2.67 2.29 2.00 2.22 1.91 1.86 57.36 51.05 53.46 53.08 54.13 54.36 1.47 1.01 1.80 2.03 0.99 1.16  12.5 m 32.26 0.95 6.70 3.86 54.65 1.58  12.6 m 31.91 0.65 5.29 2.50 58.16 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  P6-05-02  0.69  -2.1067  -4.5348  0.2666  -0.7595  -2.6801  n/a  P6-05-03  0.99  -2.0203  -4.2409  0.4249  -0.6673  -2.4207  n/a  P6-05-04  1.30  -1.619  -3.3998  0.8537  -0.2401  -1.5872  n/a  P6-05-05  1.60  -2.339  -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  P6-05-10  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  P6-05-13  4.04  -0.801  -1.947  0.9877  0.0818  -0.485  n/a  P6-05-14  4.34  -0.5479  -1.4353  1.1604  0.2829  -0.0335  n/a  P6-05-15  4.65  -1.223  -2.7814  0.5541  -0.2949  -1.3343  n/a n/a n/a  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  P22-05- 3  3.66  -0.2851  -0.3093  0.5458  0.087  0.0581  n/a  P22-05-13  n/a n/a 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  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  P23-05-1  P23-05-  0  -1.4584  -3.3617  -1.3342  -2.0896  -2.9949  1.26%  P3-06-03  0.91  -1.0229  -2.2238  1.3561  0.2925  -0.4655  -6.49%  P3-06-04  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%  P3-06-R  Table 7 - Saturation indeces of selected minerals in water samples as calculated with PhreeqC. Note: 0 m depth indicates river water.  51  Core  C1-05 C2- 05 C3- 05 C1-06 C2-06 C4-06 C12-06  Minimum  96 108 84 586 65 50  Maximum  Median  1366 266 274 165 195 596 1194 179 196 225 trending data  Mean  338 171 225 168  Table 8 - CaC12 extraction values in u.g Fe/g dry sediment  Core  C1-05 C2- 05 C3- 05 C1-06 C2-06 C4-06 C12-06  Minimum  2759 4834 2980 586 65 2676 6667  Maximum  Median  6704 6369 11433 1194 179 6798 23179  4885 5621 5816 -  5935 8664  Mean  4660 5637 6516 5414 9706  Table 9 - 0.75 M HCI extraction values in u.g Fe/g dry sediment  Core  C1-05 C2- 05 C3- 05 C1-06 C2-06 C4-06 C12-06  Minimum  13911 16828 9260 13849 21600 18596 19792  Maximum  41557 19771 33828 20690 30654 37582 30571  Median  Mean  17907 18582 18946  18742 18455 19341  -  -  20498 22770  22147 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  • TST  1  1  White Rock  f 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'  A  5 > 0)  0 -5  >  o  a. a  : : z  > ^ - S i l t soil and fill Interbedded silt and sand  River  -10 -15  :  :  S a n d with occasional silt interbeds  Hyporheic interface under investigation  -20 -25  i  i  i  0  i  20  |  !  40  1.6 x Vertical Exaggeration Approximate contact between stratigraphic units  I  I  |  I  I  |  60  80  I  100  120  Distance (m) riverbed approximate extent of hyporheic zone  Figure 4 - Cross-section showing site stratigraphy and hyporheic interface  Aquifer Hydrogeology  A  A  River  local flow  "i  0  20  |  80  r  1  100  r  1  120  Distance (m)  approximate contact between stratigraphic units —  i  60  40  1.6 x Vertical Exaggeration  1  regional flow  4  approximate extent of contaminant plume  Figure 5 - Cross-section showing aquifer hydrogeology  riverbed approximate extent of hyporheic zone  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 C02 line Core barrel  Sediment core Core liner'  Frozen sediment plug  Freeze-shoe  Figure 9 - Schematic of freeze-shoe corer.  Figure 10 - Map view of sampling locations relative to the cross-section.  Core and Profiling Locations  A 5 >  0)  >  o n  a a  C1-04, C1-05, P6-05, C1-06  C3-04, P23-05  0  A'  C2-05, P22-05, C2-06  -5  P3-06 C4-06  -10 -15 -20 -25  n  0  1  20  1  1  i  r  40  1.6 x Vertical Exaggeration approximate contact between stratigraphic units — approximate extent of contaminant plume  1  —r  r  "i  60  80  i  r  1  100  r  120  Distance (m) 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  COPPER PIPES (13mm diameter)  STYRAFOAM SPACERS  NON-WELD UNION  BOAT  AW DRILL ROD CASING  STOPPER PLATE  WELDED SEAL  EVAPORATION CHAMBER  INSERTION TIP  ON  4^  Figure 13 - Schematic of freeze-corer as deployed from boat.  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  Concentration of iron (mg/L)  20  30  40  50  60  1  1  1  1  1  O p — H  P23-05  P22-05  10  —I  20  30  1  1  Concentration of iron (mg/L) 40  50  20  D  _  40  60  4o  V-d  P  •n  J  ,  ,  ,  ,  . 0  50  100  150  200  5  1 250  500  | — • — Chloride  1000  2  1500  Iron"]  6  -Chloride - - a - - Iron  —*—Chloride --U-- Iron I  P3-06  4  Concentration of chloride (mg/L)  Concentration of chloride (mg/L)  Concentration of Chloride (mg/L)  P12-06  Concentration of iron species (mg/L) 0  20  40  60  80  100  Figure 25 - Concentrations of chloride and iron in pore water profiles. 0 m depth represents river water sample.  0.1  e" ^  0.2  CD  €  CD  I  0.3  o  CD XI  t  0.4  CD  a  0.5  2-I 0  ,  ,  ,  ,  ,  1  200  400  600  800  1000  1200  Concentration of chloride (mg/L) —*—Chloride - - a - - Iron —o— Unfiltered Iron —B— Ferrous Iron  10  20  30  40  Concentration of ions (mg/L) - Chloride - - O- - Iron -Has— Ferrous Iron I  50  PL  Fe2+ Depth Profiles 2005 24-h CaCI2  21-d 5 M HCI  24-h 0.75 M HCI C1 0.5M HCI extractions  C1 CaCI extractions  r  V* «  jt-r  C1 5M HCI extractions  1  1.5  C1-05  ii s  lowri  S 2 •c 12.  £  •8  1.  2 2.5  r  3 3.5 4  200  400  600  800  4.5  1000 1200  W50  2000 4000 6000 6000 10000 12000  ug of Fe2+ per g of sediment  150  200  250  C2 SM HCI extractions  C2 0.5M HCI extractions  C2 CaCI extractions  100  ug of Fe2+ per g of sediment  ug of Fe2+ per g of sediment  0 0.5 •  i f c l ^ M I I l  " 2.5 £ '  "S  s  J  15  s  3.5  •• 0  3  200  400  600  800  1000 1200  0  :  50  C3 0.5M HCI extractions  C3-05  150  200  250  C3 5M HCI extractions  •*  10.5 '  m  100  ug of Fe2+ per g of sediment  ug of Fe2+ per g of sediment  C3 CaCI extractions  •  BP  4 0  2000 4000 6000 8000 10000 12000  ug of Fe2+ per g of sediment  |:3 iMI 3 3.5  •  iiilllll  till!! UI  C2-05  S 1.  0  ¥  )th below river bed [m]  0.:  11  11.  11.5  1:  12  . 12.  ; 12.5  1  13  13.  13.5  •jyj 4'.o t o o  too 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  Fe Total Depth Profiles 2005 24-h CaCI2  21-d 5 M HCI  24-h 0.75 M HCI  C1 5M HCI extractions  C1 0.5M HCI extractions  C1 CaCI extractions  ^  C1-05  1.5  1  2  U  2  •c  I" fi  I  3 3.5  3  3.5  10000 ug of FeTot per g of sediment  ug of FeTot per g of sediment  •  C2-05  _  30000  40000  50000  C2 SM HCI extractions  C2 0.5M HCI extractions  C2 CaCI extractions  20000  ug of FeTot per g of sediment  7  1  s »  2  *> 2.5 G o•=  3 3.5 500  1000  1500  0  ug of FeTot per g of sediment  ug of FeTot per g of sediment  C3 0.5M HCI extractions  C3 CaCI extractions  10000  20000  30000  4>w  -.'.JO  ug of FeTot per g of sediment  C3 SM HCI extractions  10  10.5  I C3-05  1 1  S 11.5  . 12.5  13  13.5 500  1000  ug of FeTot per g of sediment  1500 ug of FeTot per g of sediment  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 C1-06 FeTot 0.5 HCI  C1-06 FeTot CaCI2  C1-06  £  0  0  0.05  0.05  0.1  0.1  0.1  0.15  0.15  0.2  0.2  _ 0.2 E.  0.25 0.3  £ 0.25 a. V •a 0.3  0.35  0.35  0.4  0.4  0.45  0.45  £ 0 25 *  1000  04  0.1  6000  0.5  8000 10000 12000  IKlliflilSllli • H B H 9 £ MNHHilll  0-2  £ 0.25  £  a.  0  0 0.05  0.1  0.1  0.15  0.15  0.2  0.2  0.25  £ 0 25  0.3  0.35  0.35  a. •a  0.3 0.35  0.4  0.4  0.4  0.45  0.45  0.45  0.5  0.5  0.5 0  50  100  150  2000  4000  6000  8000 10000 12000  ug of FeTot per g of sediment  ug of FeTot per g of sediment  C4-06 FeTot 0.5 HCI  C4-06 FeTot CaCI2  10000 15000 20000 25000  C2-06 FeTot SM HCI  0.05  0.3  5000  ug Fe per gram of sediment  C2-06 FeTot 0.5 HCI  0.15  5  4000  ug of FeTot per g of sediment  ug of FeTot per g or sediment  0.05  03  1.4. 2000  C2-06 FeTot CaCI2  iiiliiiiiiiii illfiililiii iliillSillliii lliiiiiPII • • • H I JIBS!!!!!!  0 35  0.5 500  „  C1-06 FeTot 5M HCI  0.15  0.5  C2-06  21-d 5 M HCI  10000  20000  30000  ug of Fe per g of sediment  C4-06 FeTot SM HCI  0 0.1 0.2 0.3 0.4 C 4 - 0 6  £  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 0.5M FeTot  Dec 06 1MCaCI2 FeTot  £  Dec 06 5M FeTot  0  0  0  0.1  0.1  0.1  0 . 2  0 . 2  0 . 3 -  0 . 3  Q. CD T3  0 . 4 0 . 4  IMKii^flHHi  IHIl^itlillll H  •usil iililiiilll liliiiiiiii |i|i§l| IB  0 . 5 0 . 5  0 . 6  500  1000  ug FeTot / gram sed  1500  (llllliil  0 . 6  0  5000  10000  llil  15000 20000 25000  ug FeTot / gram sed  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 0 3 5 7 11 15  ug/g FeTot 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 0 0 0 0 751.25 20.29 15.56 15557 27.00 29.49 1.63 1.30 14.85 17.44 17435 562.5 28.84 26.41 0.85 1.07 17.23 17.87 17868 653.75 28.79 26.36 0.96 1.21 18.85 18.95 18950 726 25.97 0.99 28.36 1.24 20.37 18.91 18905 770 26.45 1.08 28.89 1.35  Extraction Time Series for C2-11.3  20000 c 0)  18000  E 16000 '•a5> in 14000 O)  "5 12000 tiro 10000 3 C O  8000  ra 6000 c  a>  4000  o  2000  o c o  0* 0  , 2  , 4  , 6  , 8  , 10  , 12  , 14  1  16  time (days)  Figure 31 - Graph and data showing results of timed sediment extraction. 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Personal communication by e-mail.  85  Appendix  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 P6-05-02 P6-05-03 P6-05-04 P6-05-05 P6-05-06 P6-05-07 P6-05-08 P6-05-09 P6-05-10 P6-05-11 P6-05-12 P6-05-13 P6-05-14 P6-05-15  0.00 0.69 0.99 1.30 1.60 1.91 2.21 2.51 2.82 3.12 3.43 3.73 4.04 4.34 4.65  0.00 36.54 33.63 77.78 79.08 58.09 39.11 19.61 15.29 9.62 5.24 4.11 3.58 3.21 3.24  0.00 0.00 4.73 6.18 5.41 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00  0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00  0.01 13.09 10.78 13.05 14.08 14.52 14.96 14.36  P22-05- 13 P22-05- 8 P22-05-4 P22-05-1 P22-05-2 P22-05- 3  0 1.52 2.74 3.05 3.35 3.66  8.00 28.28 33.29 30.52 22.27 18.44  0.00 0.00 0.00 0.00 0.00 0.00  1.06 7.54 8.37 7.44 4.69 3.65  0.12 10.57  P23-05- FB P23-05- 1 P23-05- 6 P23-05- 7 P23-05- 8 P23-05- 9 P23-05- 10 P23-05- 11 P23-05- 13 P23-05- 14 P23-05- 15 P23-05- 16 P23-05- 17 P23-05- 18 P23-05- 19 P23-05- 20  0 7.32 7.62 7.92 8.23 8.53 9.14 10.67 10.97 11.58 11.89 12.5 12.8 13.41 14.02  11.59 6.02 7.23 31.12 33.10 40.84 45.93 160.96 378.70 385.28 477.23 640.51 230.23 275.46 263.30 142.84  2.08 0.61 3.16 13.94 13.05 12.30 11.87 33.80 81.90 80.21 63.76 62.30 34.96 28.81 17.26 10.54  0.00 0.00 0.00 0.47 0.48 0.60 0.59 1.86 41.91 19.96 10.95 34.05 7.59 3.93 3.21 1.62  P3-06-R P3-06-03 P3-06-04 P3-06-05 P3-06-06  0 0.91 1.22 1.52 1.83  0.00 0.00 0.00 0.00 0.00  0.00 0.00 0.00 0.00 0.00  0.00 0.00 0.00 0.00 0.00  14.32 11.40 11.17 11.42 12.99 13.80  19.35 19.96  0.07 8.12 11.12 10.25 11.40 10.90 10.82 6.39 7.05 6.64 7.28  10.26 11.06  -  87  Conductivity and pH Field Data  sample  depth (m) pH  seawater 47.2  Conductivity  Temperature  (uS/cm)  (°C) in flow-through  Cl/Ca ratio  P6-05-FB P6-05-01 P6-05-02 P6-05-03 P6-05-04 P6-05-05 P6-05-06 P6-05-07 P6-05-08 P6-05-09 P6-05-10 P6-05-11 P6-05-12 P6-05-13 P6-05-14 P6-05-15  0.00 0.69 0.99 1.30 1.60 1.91 2.21 2.51 2.82 3.12 3.43 3.73 4.04 4.34 4.65  7.67 6.33 6.12 6.18 6.18 6.24 6.29 6.31 6.36 6.37 7.07 7.14 7.15 7.07 7.03  104.4 401 382 392 400 419 430 440 457 464 475 519 629 866 1281  23.6 28.1 26.2 25.3 25 23.8 21.4 19.3 19.5 17.5 15.3 15.8 16.2 16.8 18.4  0.51 0.06 0.45 0.44 0.28 1.09 0.79 0.59 0.56 0.36 0.20 0.51 1.46 1.66 1.67 . 3.15  P22-05- 13 P22-05- 8 P22-05-4 P22-05-1 P22-05- 2 P22-05- 3  0 1.52 2.74 3.05 3.35 3.66  7.63 6.81 7.06 7.03 7.3 7.67  95.8 2230 2000 3600 5100 5700  22.6 24 20 19.2 21.3 20.3  0.05 2.46 5.31 5.41 10.00 59.55  P23-05- FB P23-05-1 P23-05- 6 P23-05- 7 P23-05- 8 P23-05- 9 P23-05- 10 P23-05- 11 P23-05-13 P23-05-14 P23-05-15 P23-05- 16 P23-05- 17 P23-05-18 P23-05-19 P23-05- 20  0 7.32 7.62 7.92 8.23 8.53 9.14 10.67 10.97 11.58 11.89 12.5 12.8 13.41 14.02  6.44 7.1 6.65 6.34 6.54 6.6 6.58 6.6 6.54 6.52 6.47 6.46 6.52 6.63 6.59 7.25  53.4 88.9 309 369 396 372 387 408 531 533 559 535 624 657 634 691  15.3 14.8 15.4 15.4 15.4 15.4 15.5 16.3 16.8 17.2 17.8 18.4 20.2 18.7 18 17.1  0.81 0.07 0.20 0.13 0.14 0.14 0.27 0.14 0.15 0.15 0.15 0.15 0.08 0.09 0.08 0.08  P3-06-R P3-06-03 P3-06-04 P3-06-05 P3-06-06  0 0.91 1.22 1.52 1.83  7.2 6.57 6.72 6.75 6.85  97.1 466 861 1966 3470  11.8 11.7 12.8  0.13 0.42 1.93 3.51 5.05  P12-06-0/10 P12-06-10/20 P12-06-20/30 P12-06-30/40 P12-06-40/50 P12-06-50/60  0.05 0.15 0.25 0.35 0.45 0.55  -  408 524 464 479 470 415  -  -  -  -  0.44 0.18 0.20 0.38 0.16 0.22  Pore Water Lab Analyses for P12-06 Cations, Anions in mg/L Sample ID CANTEST ID Date Sampled Parameter Alkalinity mg/L C a C 0 3 depth (m) Dissolved Anions Fluoride F Chloride CI Bromide Br Sulphate S 0 4 Dissolved Metals Aluminum Al Antimony Sb Arsenic As Barium Ba Beryllium Be Bismuth Bi Boron B Cadmium Cd Calcium Ca Chromium Cr Cobalt Co Copper Cu Iron Fe Lead Pb Lithium Li Magnesium Mg Manganese Mn Molybdenum Mo Nickel Ni Phosphorus P Potassium K Selenium Se Silicon Si Silver Ag Sodium Na Strontium Sr Tellurium Te Thallium TI Thorium Th Tin Sn Titanium Ti Uranium U Vanadium V Zinc Zn Zirconium Zr  TR-10/20-a TR-20/30-a TR-30/40-a TR-40/50-a TR-50/60-a TR-0710-a 702080169 702080171 702080172 702080173 702120140 702120144 N/A N/A N/A N/A  -  24.5  -  160 0.25  185 0.15  119 0.05  -  -  -  8.19  3.83  0.023 < 0.001 0.009 0.11 < 0.001 < 0.001 < 0.05 < 0.0002 55.2 < 0.001 0.004 0.002 8.3 < 0.001 0.002 10 3.78 0.0021 0.007 0.2 3.6 0.002 6 < 0.00025 7.67 0.31 < 0.001 < 0.0001 < 0.0005 < 0.001 < 0.001 0.0008 < 0.001 < 0.005 < 0.01  0.017 < 0.001 0.016 0.11 < 0.001 < 0.001 0.07 < 0.0002 54.5 < 0.001 0.002 0.001 25 < 0.001 0.002 9.32 3.84 0.0021 0.004 0.2 3.7 0.002 8.7 < 0.00025 5.99 0.27 < 0.001 < 0.0001 < 0.0005 < 0.001 0.002 < 0.0005 0.002 < 0.005 < 0.01  -  8.05  10  0.017 < 0.001 0.019 0.11 < 0.001 < 0.001 0.19 < 0.0002 38.5 < 0.001 0.004 < 0.001 35.7 < 0.001 0.003 9.23 2.77 0.0017 0.009 0.2 5.8 < 0.001 12.2 < 0.00025 8.22 0.19 < 0.001 < 0.0001 < 0.0005 < 0.001 0.002 0:002 < 0.0005 < 0.0005 0.002 0.002 0.007 < 0.005 <0.01 < 0.01  0.025 < 0.001 0.018 0.099 < 0.001 < 0.001 0.14 < 0.0002 39.5 < 0.001 0.001 < 0.001 33 < 0.001 0.003 8.48 2.67 0.0015 0.002 0.3 4.8 < 0.001 11.2 < 0.00025 6.48 0.19 < 0.001 < 0.0001 < 0.0005 < 0.001  7.14  5.82  14.5  0.98 < 0.5  132 0.55  159 0.45  158 0.35  -  0.58  0.82  0.045 < 0.001 0.03 0.1 < 0.001 < 0.001 0.24 < 0.0002 36.2 0.001 0.005 0.003 34 < 0.001 0.004 9.12 2.53 0.0013 0.01 0.2 6.7 < 0.001 16.7 < 0.00025 8.36 0.17 < 0.001 < 0.0001 < 0.0005 < 0.001 0.007 < 0.0006 0.002 < 0.005 < 0.01  0.05 < 0.001 0.024 0.086 < 0.001 < 0.001 0.22 < 0.0002 32.9 0.001 0.004 0.002 36 < 0.001 0.004 8.68 2.25 0.0012 0.008 0.4 6.5 < 0.001 13.3 < 0.00025 8.48 0.16 < 0.001 < 0.0001 < 0.0005 < 0.001 0.005 < 0.0007 0.002 < 0.005 < 0.01  89  Pore Water Analyses for P3-06 Cations, Anions in mg/L P3-06-R 4/21/2006  P3-06-03 4/21/2006  P3-06-04 4/21/2006  P3-06-05 4/21/2006  P3-06-06 4/21/2006  1 Water 0  2 Water 0.91  3 Water 1.22  4 Water 1.52  5 Water 1.83  Dissolved Anions Bromide Br Chloride CI Fluoride F Sulphate S04  <0.050 1.78 0.036 5.99  <0.050 14.0 0.052 <0.50  0.406 136 0.060 <0.50  1.68 544 <0.10 3.0  3.27 1010 <0.10 <2.5  Nutrients Nitrate Nitrogen Nitrite Nitrogen  0.164 0.0017  0.0097 <0.0010  <0.0050 <0.0010  <0.025 <0.0050  0.027 <0.0050  Total Metals Iron T-Fe  1.13  62.2  86.5  90.1  74.7  Dissolved Metals Aluminum D-AI Antimony D-Sb Arsenic D-As Barium D-Ba Beryllium D-Be Bismuth D-Bi Boron D-B Cadmium D-Cd Calcium D-Ca Chromium D-Cr Cobalt D-Co Copper D-Cu Iron D-Fe Lead D-Pb Lithium D-Li Maqnesium D-Mg Manganese D-Mn Molybdenum D-Mo Nickel D-Ni Phosphorus D-P Potassium D-K Selenium D-Se Silicon D-Si Silver D-Ag Sodium D-Na Strontium D-Sr Thallium D-TI Tin D-Sn Titanium D-Ti Vanadium D-V Zinc D-Zn  <0.20 <0.20 0.00025 0.014 <0.0050 <0.20 <0.10 <0.010 13.9 <0.010 <0.010 <0.010 0.114 <0.050 <0.010 3.63 0.0105 <0.030 <0.050 <0.30 <2.0 <0.20 2.76 <0.010 2.9 0.0702 <0.20 <0.030 <0.010 <0.030 0.132  <0.20 <0.20 0.00900 0.044 <0.0050 <0.20 0.19 <0.010 33.7 <0.010 <0.010 <0.010 62.4 <0.050 <0.010 16.3 2.76 <0.030 <0.050 <0.30 4.0 <0.20 17.9 <0.010 6.1 0.145 <0.20 <0.030 <0.010 <0.030 0.0977  <0.20 <0.20 0.00935 0.091 <0.0050 <0.20 0.21 <0.010 70.4 <0.010 <0.010 <0.010 85.7 <0.050 <0.010 27.4 4.55 <0.030 <0.050 <0.30 7.3 <0.20 19.1 <0.010 16.1 0.286 <0.20 <0.030 <0.010 <0.030 0.182  <0.20 <0.20 0.00965 0.278 <0.0050 <0.20 0.25 <0.010 155 <0.010 <0.010 0.015 90.1 <0.050 <0.010 42.9 6.65 <0.030 <0.050 <0.30 18.3 <0.20 17.6 <0.010 110 0.636 <0.20 <0.030 <0.010 <0.030 0.0750  <0.20 <0.20 0.0126 0.407 <0.0050 <0.20 0.38 <0.010 200 <0.010 <0.010 <0.010 71.7 <0.050 <0.010 48.8 6.56 <0.030 <0.050 <0.30 31.1 <0.20 17.6 <0.010 342 0.946 <0.20 <0.030 <0.010 <0.030 0.0325  Sample ID Date Sampled Time Sampled ALS Sample ID Nature depth (m)  Pore Water Lab Analyses for P23-05 Cations, Anions in mg/L Sample ID Date Sampled Time Sampled ALS Sample ID Nature depth (m) Dissolved Anions Bromide Br Chloride Cl Fluoride F Sulphate S04 Nutrients Nitrate Nitrogen Nitrite Nitrogen Dissolved Metals Aluminum D-AI Antimony D-Sb Arsenic D-As Barium D-Ba Beryllium D-Be Bismuth D-Bi Boron D-B Cadmium D-Cd Calcium D-Ca Chromium D-Cr Cobalt D-Co Copper D-Cu Iron D-Fe Lead D-Pb Lithium D-Li Magnesium D-Mg Manganese D-Mn Molybdenum D-Mo Nickel D-Ni Phosphorus D-P Potassium D-K Selenium D-Se Silicon D-Si Silver D-Ag Sodium D-Na Strontium D-Sr Thallium D-TI Tin D-Sn Titanium D-Ti Vanadium D-V Zinc D-Zn  P23-05-16  P23-05- 17  P23-05- 18  12  11  P23-05- 19  P23-05- 20  15  14  13  Water 11.89  Water 12.5  Water 12.8  Water 13.41  Water 14.02  <0.050  <0.050  <0.050  <0.050  <0.050 5.41 0.027  5.49 0.03  3.69 0.027  4.38 0.032  6.3 0.026  <0.50  <0.50  <0.50  <0.50  <0.50  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.20 <0.20 <0.20  <0.20 O.20 <0.20  <0.20 <0.20 <0.20  <0.20 <0.20 <0.20  <0.20 <0.20 <0.20  0.047 <0.0050 <0.20 <0.10 <0.010 30.2 <0.010 <0.010 <0.010 71.5 <0.050 <0.010 14.6 2.26 <0.030 <0.050 <0.30 2.1 <0.20 18.9 <0.010 19.4 0.202 <0.20 <0.030 <0.010 <0.030 0.0215  0.043 <0.0050 <0.20 0.11 <0.010 47.1 <0.010 <0.010 <0.010 53.1 <0.050 <0.010 21.7 3.71 <0.030 <0.050 <0.30 <2.0 <0.20 22.4 <0.010 10.3 0.225 <0.20 <0.030 <0.010 <0.030 0.0133  0.038 <0.0050 <0.20 0.12 <0.010 62.5 <0.010 <0.010 <0.010 46.6 <0.050 <0.010 28.6 2.4 <0.030 <0.050 <0.30 2.2 <0.20 25.2 <0.010 10.1 0.273 <0.20 <0.030 <0.010 <0.030 0.0176  0.034 <0.0050 <0.20 0.11 <0.010 71.5 <0.010 <0.010 <0.010 23.4 <0.050 <0.010 28.7 0.635 <0.030 <0.050 <0.30 <2.0 <0.20 25.3 <0.010 10.5 0.292 <0.20 <0.030 <0.010 <0.030 0.0313  0.03 <0.0050 <0.20 <0.10 <0.010 74.2 <0.010 <0.010 <0.010. 22.4 <0.050 <0.010 25.7 0.558 <0.030 <0.050 <0.30 <2.0 <0.20 22.5 <0.010 8.5 0.281 <0.20 <0.030 <0.010 <0.030 0.0184  91  Pore Water Lab Analyses for P23-05 Cations, Anions in mg/L Sample ID Date Sampled Time Sampled ALS Sample ID Nature depth (m) Dissolved Anions Bromide Br Chloride Cl Fluoride F Sulphate S04 Nutrients Nitrate Nitrogen Nitrite Nitrogen Dissolved Metals Aluminum D-AI Antimony D-Sb Arsenic D-As Barium D-Ba Beryllium D-Be Bismuth D-Bi Boron D-B Cadmium D-Cd Calcium D-Ca Chromium D-Cr Cobalt D-Co Copper D-Cu Iron D-Fe Lead D-Pb Lithium D-Li Magnesium D-Mg Manganese D-Mn Molybdenum D-Mo Nickel D-Ni Phosphorus D-P Potassium D-K Selenium D-Se Silicon D-Si Silver D-Ag Sodium D-Na Strontium D-Sr Thallium D-TI Tin D-Sn Titanium D-Ti Vanadium D-V Zinc D-Zn  P23-05-10  7  6 Water 9.14  Water 8.53  <0.050  8  10  9 Water 11.58  <0.050  <0.050  <0.050 3.62 0.037  3.04 0.029  P23-05- 15  Water 10.97  Water 10.67  <0.050 2.97 0.034  P23-05-14  P23-05- 13  P23-05-11  4.37 0.034  3.8 0.037  <0.50  <0.50  <0.50  <0.50  <0.50  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.20 <0.20 <0.20  <0.20 <0.20 <0.20  <0.20 <0.20 <0.20  <0.20 <0.20 <0.20  <0.20 <0.20 <0.20  0.044 <0.0050 <0.20 <0.10 <0.010 11.1 <0.010 <0.010 <0.010 18.3 <0.050 <0.010 7.65 0.428 <0.030 <0.050 <0.30 <2.0 <0.20 9.18 <0.010 8.9 0.0612 <0.20 <0.030 <0.010 <0.030 0.0071  0.086 <0.0050 <0.20 0.11 <0.010 21.9 <0.010 <0.010 <0.010 42.8 <0.050 <0.010 15.1 0.975 <0.030 <0.050 <0.30 <2.0 <0.20 17.9 <0.010 17.7 0.128 <0.20 <0.030 <0.010 <0.030 0.0092  0.066 <0.0050 <0.20 <0.10 <0.010 24.9 O.010 <0.010 <0.010 69.3 <0.050 <0.010 13.4 1.51 <0.030 O.050 <0.30 <2.0 <0.20 16.9 <0.010 18 0.15 <0.20 <0.030 <0.010 <0.030 0.0077  0.046 <0.0050 <0.20 <0.10 <0.010 25.8 <0.010 <0.010 <0.010 72.1 <0.050 <0.010 13.5 1.77 <0.030 <0.050 <0.30 <2.0 <0.20 17.2 <0.010 17.8 0.162 <0.20 <0.030 <0.010 <0.030 0.0138  0.039 <0.0050 <0.20 <0.10 <0.010 29 <0.010 <0.010 <0.010 72.4 <0.050 <0.010 13.1 1.93 <0.030 <0.050 <0.30 2 <0.20 17.3 <0.010 16.7 0.182 <0.20 <0.030 <0.010 <0.030 0.027  92  Pore Water Lab Analyses for P23-05 Cations, Anions in mg/L Sample ID Date Sampled Time Sampled ALS Sample ID Nature depth (m) Dissolved Anions Bromide Br Chloride CI Fluoride F Sulphate S04 Nutrients Nitrate Nitrogen Nitrite Nitrogen Dissolved Metals Aluminum D-AI Antimony D-Sb Arsenic D-As Barium D-Ba Beryllium D-Be Bismuth D-Bi Boron D-B Cadmium D-Cd Calcium D-Ca Chromium D-Cr Cobalt D-Co Copper D-Cu Iron D-Fe Lead D-Pb Lithium D-Li Magnesium D-Mg Manganese D-Mn Molybdenum D-Mo Nickel D-Ni Phosphorus D-P Potassium D-K Selenium D-Se Silicon D-Si Silver D-Ag Sodium D-Na Strontium D-Sr Thallium D-TI Tin D-Sn Titanium D-Ti Vanadium D-V Zinc D-Zn  P23-05-1  P23-05- FB  1 Water -  P23-05- 6  <0.050  21  2 Water 0  P23-05- 7  Water 7.32  P23-05- 9  P23-05- 8  4  3 Water 7.62  Water 7.92  5 Water 8.23  <0.050 <0.050 <0.050 <0.050 2.87 3.02 2.94 2.95 0.8 0.04 0.038 0.042 0.048 0.028 <0.50 <0.50 <0.50 6.09 <0.50  <0.050 4.76 0.03 2.96  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.20 <0.20 <0.20 <0.010 <0.0050 <0.20 <0.10 <0.010  <0.20 <0.20 <0.20 <0.010 <0.0050 <0.20 <0.10 <0.010 11.6 <0.010 <0.010 <0.010 0.072 <0.050 <0.010 1.88 0.0212 <0.030 <0.050 <0.30 <2.0 <0.20 1.5 <0.010 <2.0 0.0488 <0.20 <0.030 <0.010 <0.030 0.0078  <0.20 <0.20 <0.20  <0.20 <0.20 <0.20  <0.20 <0.20 <0.20  <0.20 <0.20 <0.20  0.049 <0.0050 <0.20 <0.10 <0.010 14.6 <0.010 <0.010 <0.010 17.6 <0.050 <0.010 9.54 0.412 <0.030 <0.050 <0.30 <2.0 <0.20 13.1 <0.010 10.2 0.0708 <0.20 <0.030 <0.010 <0.030 0.0543  0.077 <0.0050 <0.20 <0.10 <0.010 22.9 <0.010 <0.010 <0.010 31.9 <0.050 <0.010 14.9 0.704 <0.030 <0.050 <0.30 <2.0 <0.20 19.2 <0.010 16.2 0.11 <0.20 <0.030 <0.010 <0.030 0.0252  0.076 <0.0050 <0.20 <0.10 <0.010 21.2 <0.010 <0.010 <0.010 34.2 <0.,050 <0.010 14.6 0.748 <0.030 <0.050 <0.30 <2.0 <0.20 17.5 <0.010 15.7 0.108 <0.20 <0.030 <0.010 <0.030 0.0123  0.077 <0.0050 <0.20 <0.10 <0.010 21 <0.010 <0.010 <0.010 35.5 <0.050 <0.010 14.4 0.797 <0.030 <0.050 <0.30 <2.0 <0.20 18.2 <0.010 16.6 0.11 <0.20 <0.030 <0.010 <0.030 0.0148  5.87 <0.010 <0.010 0.022 0.222 <0.050 <0.010 0.35 0.0215 <0.030 <0.050 <0.30 <2.0 <0.20 0.923 <0.010 3.8 0.0171 <0.20 <0.030 <0.010 <0.030 0.0455  93  Pore Water Lab Analyses for P22-05 Cations, Anions in mg/L P22-05-1 P22-05- 2 P22-05- 3 P22-05-4 P22-05-8 P22-05-13  Sample ID Date Sampled Time Sampled ALS Sample ID Nature depth (m)  16 Water 3.05  17 Water 3.35  18 Water 3.66  25 Water 2.74  19 Water 1.52  20 Water 0  Dissolved Anions Bromide Br Chloride Cl Fluoride F Sulphate S04  3.3 1250 <0.40 <10  3.8 1430 <0.40 <10  4.2 1590 <0.40 <10  2.74 955 <0.10 <2.5  1.27 462 <0.10 <2.5  <0.050 0.61 0.028 5.60  Nutrients Nitrate Nitroge Nitrite Nitrogen  <2.0 <2.0  <2.0 <2.0  <2.0 <2.0  <0.50 <0.50  <0.50 <0.50  <0.10 <0.10  Dissolved Metals Aluminum D-AI Antimony D-Sb Arsenic D-As Barium D-Ba Beryllium D-Be Bismuth D-Bi Boron D-B Cadmium D-Cd Calcium D-Ca Chromium D-Cr Cobalt D-Co Copper D-Cu Iron D-Fe Lead D-Pb Lithium D-Li Magnesium D-Mg Manganese D-Mn Molybdenum D-Mo Nickel D-Ni Phosphorus D-P Potassium D-K Selenium D-Se Silicon D-Si Silver D-Ag Sodium D-Na Strontium D-Sr Thallium D-TI Tin D-Sn Titanium D-Ti Vanadium D-V Zinc D-Zn  <0.20 <0.20 <0.20 0.584 O.0050 <0.20 0.44 <0.010 231 <0.010 <0.010 <0.010 25.4 <0.050 0.017 60.8 7.72 <0.030 <0.050 0.36 42.1 <0.20 20.3 <0.010 533 1.49 <0.20 <0.030 <0.010 <0.030 0.0588  <0.20 <0.20 <0.20 0.416 <0.0050 <0.20 0.57 <0.010 143 <0.010 <0.010 <0.010 10.3 <0.050 <0.010 61.3 2.95 <0.030 <0.050 0.68 37.1 <0.20 15.5 <0.010 616 1.15 <0.20 <0.030 <0.010 <0.030 0.0221  <0.20 <0.20 <0.20 0.133 <0.0050 <0.20 0.36 <0.010 26.7 <0.010 <0.010 <0.010 1.35 <0.050 <0.010 34.9 0.278 <0.030 <0.050 0.66 15.7 <0.20 5.74 <0.010 343 0.368 <0.20 <0.030 <0.010 <0.030 0.0073  <0.20 <0.20 <0.20 0.408 <0.0050 <0.20 0.27 <0.010 180 <0.010 <0.010 <0.010 22.8 <0.050 0.014 42.0 6.21 <0.030 <0.050 0.32 31.0 <0.20 15.1 <0.010 329 1.07 <0.20 <0.030 <0.010 <0.030 0.0456  <0.20 <0.20 <0.20 0.184 <0.0050 <0.20 0.16 <0.010 188 <0.010 <0.010 <0.010 38.2 <0.050 0.012 44.0 5.32 <0.030 <0.050 <0.30 17.3 <0.20 19.0 <0.010 63.6 0.781 <0.20 <0.030 <0.010 <0.030 0.0421  <0.20 <0.20 <0.20 0.010 <0.0050 <0.20 <0.10 <0.010 11.7 <0.010 <0.010 <0.010 0.078 <0.050 <0.010 2.38 0.0188 <0.030 <0.050 <0.30 <2.0 <0.20 2.04 <0.010 <2.0 0.0620 <0.20 <0.030 <0.010 <0.030 0.0062  94  Pore Water Lab Analyses for P6-05 Cations, Anions in mg/L Sample ID Date Sampled Time Sampled ALS Sample ID Nature Depth (ft) Depth (m)  P6-05-08 6/23/2005 20:00 9 Water 8.25 2.51  P6-05-09 6/23/2005 20:34 10 Water 9.25 2.82  P6-05-10 6/23/2005 21:00 11 Water 10.25 3.12  P6-05-11 6/24/2005 7:06 12 Water 11.25 3.43  P6-05-12 6/24/2005 7:39 13 Water 12.25 3.73  P6-05-13 6/24/2005 8:05 14 Water 13.25 4.04  P6-05-14 6/24/2005 8:34 15 Water 14.25 4.34  P6-05-15 6/24/2005 8:54 16 Water 15.25 4.65  Dissolved Anions Bromide Br Chloride Cl Fluoride F Sulphate S04  <0.050 11.4 0.028 <0.50  <0.050 4.83 0.025 <0.50  <0.050 5.18 0.025 <0.50  <0.050 14.1 0.028 <0.50  0.075 24.8 0.029 <0.50  0.184 66.4 0.029 <0.50  0.284 104 0.028 <0.50  0.608 210 0.029 <0.50  Nutrients Nitrate Nitrogen N Nitrite Nitrogen N  <0.10 <0.10  O.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  <0.10 <0.10  Dissolved Metals Aluminum D-AI Antimony D-Sb Arsenic D-As Barium D-Ba Beryllium D-Be Bismuth D-Bi Boron D-B Cadmium D-Cd Calcium D-Ca Chromium D-Cr Cobalt D-Co Copper D-Cu Iron D-Fe Lead D-Pb Lithium D-Li Magnesium D-Mg Manganese D-Mn Molybdenum D-Mo Nickel D-Ni Phosphorus D-P Potassium D-K Selenium D-Se Silicon D-Si Silver D-Ag Sodium D-Na Strontium D-Sr Thallium D-TI Tin D-Sn Titanium D-Ti Vanadium D-V Zinc D-Zn  <0.20 <0.20 0.00442 0.016 <0.0050 <0.20 <0.10 <0.010 20.2 <0.010 <0.010 <0.010 19.3 <0.050 <0.010 7.28 0.971 <0.030 <0.050 <0.30 <2.0 <0.20 7.99 <0.010 3.2 0.0790 <0.20 <0.030 <0.010 <0.030 0.0526  <0.20 <0.20 0.00246 <0.010 <0.0050 <0.20 <0.10 <0.010 13.4 O.010 <0.010 <0.010 9.98 <0.050 <0.010 4.32 0.548 <0.030 O.050 <0.30 <2.0 <0.20 4.69 <0.010 <2.0 0.0492 <0.20 <0.030 <0.010 <0.030 0.0113  <0.20 <0.20 0.00418 0.019 <0.0050 <0.20 <0.10 <0.010 26.5 <0.010 <0.010 <0.010 16.3 <0.050 <0.010 8.36 0.965 <0.030 <0.050 <0.30 <2.0 <0.20 8.48 <0.010 3.1 0.0939 <0.20 <0.030 <0.010 <0.030 0.0303  <0.20 <0.20 0.00409 0.017 <0.0050 <0.20 <0.10 <0.010 27.5 <0.010 <0.010 <0.010 13.6 <0.050 <0.010 8.62 0.869 <0.030 <0.050 <0.30 <2.0 <0.20 8.54 <0.010 2.8 0.0953 O.20 <0.030 <0.010 <0.030 0.0118  <0.20 <0.20 0.00249 0.010 <0.0050 <0.20 <0.10 <0.010 17.0 <0.010 <0.010 <0.010 7.56 <0.050 <0.010 5.41 0.490 <0.030 <0.050 <0.30 <2.0 <0.20 4.89 <0.010 <2.0 0.0578 <0.20 <0.030 <0.010 <0.030 0.0060  <0.20 <0.20 0.00484 0.025 <0.0050 <0.20 <0.10 <0.010 39.9 <0.010 <0.010 <0.010 16.0 <0.050 <0.010 13.1 1.05 <0.030 <0.050 <0.30 2.1 <0.20 9.85 <0.010 3.8 0.137 <0.20 <0.030 <0.010 <0.030 0.0256  <0.20 <0.20 0.00673 0.040 <0.0050 <0.20 <0.10 <0.010 62.3 <0.010 <0.010 <0.010 21.7 <0.050 <0.010 20.7 1.52 <0.030 <0.050 <0.30 3.1 <0.20 11.9 <0.010 5.7 0.207 <0.20 <0.030 <0.010 <0.030 0.012  <0.20 <0.20 0.00640 0.050 O.0050 <0.20 <0.10 <0.010 66.7 <0.010 <0.010 <0.010 23.8 <0.050 <0.010 22.3 1.77 <0.030 <0.050 O.30 3.9 <0.20 10.3 <0.010 9.9 0.246 O.20 <0.030 <0.010 O.030 0.0289  95  Pore Water Lab Analyses for P6-05 Cations, Anions in mg/L Sample ID Date Sampled Time Sampled ALS Sample ID Nature Depth (ft) Depth (m)  P6-05-FB 6/23/2005 11:01 1 Water -  P6-05-01 6/23/2005 12:00 2 Water -1 -0.30  P6-05-02 6/23/2005 14:42 3 Water 2.25 0.69  P6-05-03 6/23/2005 15:50 4 Water 3.25 0.99  P6-05-04 6/23/2005 16:30 5 Water 4.25 1.30  P6-05-05 6/23/2005 17:40 6 Water 5.25 1.60  P6-05-06 6/23/2005 18:14 7 Water 6.25 1.91  P6-05-07 6/23/2005 18:53 8 Water 7.25 2.21  Dissolved Anions Bromide Br Chloride CI Fluoride F Sulphate S04  <0.050 3.75 0.040 4.66  <0.050 0.57 0.030 6.23  <0.050 5.85 0.034 <0.50  <0.050 7.58 0.035 O.50  <0.050 7.19 0.031 <0.50  <0.050 12.9 0.033 <0.50  <0.050 12.5 0.029 <0.50  <0.050 6.96 0.023 <0.50  Nutrients Nitrate Nitroqen N Nitrite Nitroqen N  0.16 <0.10  0.12 <0.10  0.11 <0.10  2.53 <0.10  <0.10 <0.10  <0.10 <0.10  0.42 <0.10  <0.10 <0.10  Dissolved Metals Aluminum D-AI Antimony D-Sb Arsenic D-As Barium D-Ba Beryllium D-Be Bismuth D-Bi Boron D-B Cadmium D-Cd Calcium D-Ca Chromium D-Cr Cobalt D-Co Copper D-Cu Iron D-Fe Lead D-Pb Lithium D-Li Magnesium D-Mg Manganese D-Mn Molybdenum D-Mo Nickel D-Ni Phosphorus D-P Potassium D-K Selenium D-Se Silicon D-Si Silver D-Ag Sodium D-Na Strontium D-Sr Thallium D-TI Tin D-Sn Titanium D-Ti Vanadium D-V Zinc D-Zn  <0.20 <0.20 <0.00020 <0.010 <0.0050 <0.20 <0.10 <0.010 7.42 <0.010 <0.010 0.035 0.292 <0.050 O.010 0.30 0.0227 <0.030 <0.050 <0.30 <2.0 <0.20 0.720 <0.010 3.6 0.0220 <0.20 <0.030 <0.010 <0.030 0.253  <0.20 <0.20 0.00045 <0.010 <0.0050 <0.20 <0.10 <0.010 10.2 <0.010 <0.010 <0.010 1.23 <0.050 <0.010 2.25 0.0674 <0.030 <0.050 <0.30 <2.0 <0.20 1.70 <0.010 <2.0 0.0507 <0.20 <0.030 <0.010 <0.030 0.0337  <0.20 <0.20 0.00466 0.025 <0.0050 <0.20 <0.10 <0.010 13.1 <0.010 <0.010 <0.010 19.9 <0.050 <0.010 4.55 0.964 <0.030 <0.050 <0.30 <2.0 <0.20 5.32 <0.010 3.7 0.0569 <0.20 <0.030 <0.010 <0.030 0.0822  <0.20 <0.20 0.00936 0.035 <0.0050 <0.20 <0.10 <0.010 17.4 <0.010 <0.010 <0.010 32.9 <0.050 <0.010 7.99 1.36 <0.030 <0.050 <0.30 <2.0 <0.20 11.0 <0.010 7.1 0.0857 <0.20 <0.030 <0.010 <0.030 0.504  <0.20 <0.20 0.00950 0.036 <0.0050 <0.20 0.14 <0.010 25.7 <0.010 O.010 <0.010 55.9 <0.050 <0.010 12.9 2.29 <0.030 <0.050 O.30 2.9 <0.20 17.6 <0.010 9.4 0.128 <0.20 <0.030 <0.010 <0.030 0.0934  <0.20 <0.20 0.00388 0.014 <0.0050 <0.20 <0.10 <0.010 11.8 <0.010 <0.010 <0.010 21.1 <0.050 <0.010 5.67 0.896 <0.030 <0.050 <0.30 <2.0 <0.20 7.15 <0.010 3.6 0.0548 <0.20 <0.030 <0.010 <0.030 0.0177  <0.20 <0.20 0.00447 0.017 <0.0050 <0.20 <0.10 <0.010 15.8 <0.010 <0.010 <0.010 25.9 <0.050 <0.010 7.61 1.13 <0.030 <0.050 <0.30 <2.0 <0.20 8.17 <0.010 4.2 0.0719 <0.20 <0.030 <0.010 <0.030 0.0282  <0.20 <0.20 0.00284 0.012 <0.0050 <0.20 <0.10 <0.010 11.7 <0.010 <0.010 <0.010 14.8 <0.050 <0.010 4.84 0.698 <0.030 <0.050 <0.30 <2.0 <0.20 5.38 <0.010 2.2 0.0492 O.20 <0.030 <0.010 <0.030 0.0249  96  Appendix  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 sed weight (g)  2006  C2-06-02 C2-06-02 C2-06-02 C2-06-02 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C1-06-01 C1-06-01 C1-06-01 C1-06-01  soln weight (g)  dry/wet ratio assumed  cone mg/L  dry sed mass (g)  ml of soln  mg total of Fe  Mg/g FeTot  mg/g  depth (m)  30.6536 24.9282 22.4767 21.6003 37.5816 25.9895 19.3085 19.5363 20.4977 20.4860 21.8044 21.4706 20.4686 20.4996 18.5963 19.5264 19.7014 13.8492 20.6905 19.7061  30654 24928 22477 21600 37582 25989 19308 19536 20498 20486 21804 21471, 20469 20500 18596 19526 19701 13849 20690 19706  0.0254 0.0254 0.1016 0.1016 0.0381 0.0381 0.127 0.127 0.2286 0.2286 0.3302 0.3302 0.4318 0.4318 0.5334 0.5334 0.03175 0.03175 0.1143 0.1143  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 19.7920 1.4160 29.3503 28.0253 954.8564 0.8122 0.954856361 1.7433 31.9918 23.7144 0.8122 1.0694 28.5206 25.3603 889.1929 31.0874 0.889192886 1.3166  19792 23714  depth fml 0.05 0.05  0"-2"a 0"-2"b 2"-6"a 2"-6"b 0"-3"a 0"-3"b 3"-7"a 3"-7"b 7"-11"a 7"-11"b 11"-1'3"a 11"-1'3"b 1'3"-1'7"a 1'3"-1'7"b 17"-1'11"a 17"-ri1"b 0"- 2.5"a 0"- 2.5"b 2.5" - 6"a 2.5" - 6"b  2.5064 1.6798 1.5618 2.0695 1.4763 1.0213 1.7401 1.4572 1.3101 1.8645 1.3830 1.7671 1.6148 1.2277 2.1733 1.5930 1.3210 1.4245 1.6079 2.2983  30.8451 29.7895 29.7448 32.1411 29.8086 31.0831 30.6386 29.1558 30.5067 29.687 30.6323 29.7799 30.2989 29.8321 30.675 29.4408 29.4889 29.9731 28.6054 29.593  2176 1228 1031 1215 1626 746 958 853 769 1124 860 1113 953 737 1151 923 771 575 1016 1337  0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8  2.00512 1.34384 1.24944 1.6556 1.18104 0.81704 1.39208 1.16576 1.04808 1.4916 1.1064 1.41368 1.29184 0.98216 1.73864 1.2744 1.0568 1.1396 1.28632 1.83864  28.2464 27.2798 27.2388 29.4332 27.2973 28.4644 28.0573 26.6995 27.9365 27.1859 28.0516 27.2710 27.7462 27.3188 28.0907 26.9604 27.0045 27.4479 26.1954 27.0998  61.4642 33.4995 28.0832 35.7614 44.3853 21.2344 26.8789 22.7746 21.4832 30.5569 24.1243 30.3526 26.4422 20.1339 32.3323 24.8845 20.8205 15.7825 26.6145 36.2325  C12-06  0-10 qa 0-10 qb 10-20 ga 10-20 gb  1.0203 1.8718  33.7446 32.0709  0.625626995 1.01869585  625.6270 1697.8265  0.8730 0.8730  0.8907 1.6341  30.9583 29.4228  19.3684 49.9549,  21.7446 30.5707  21745 30571  0.15 0.15  20-30 sa 20-30 sb  0.7916 1.2389  32.4718 33.3564  0.47879617 0.744186047  478.7962 744.1860  0.8128 0.8128  0.6434 1.0070  29.7906 30.6022  14.2636 22.7737  22.1687 22.6159  22169 22616  0.25 0.25  30-40 qa 30-40 qb  0.7847 0.9873  33.1507 35.9574  0.466940264 0.530779754  466.9403 530.7798  0.7948 0.7948  0.6237 0.7847  30.4135 32.9884  14.2013 17.5096  22.7697 22.3131  22770 22313  0.35 0.35  40-50 sa 40-50 sb  0.8963 1.4843  33.9525 31.9903  0.581851345 1.049703602  581.8513 1049.7036  0.7271 0.7271  0.6517 1.0793  31.1491 29.3489  18.1241 30.8076  27.8090 28.5442  27809 28544  0.45 0.45  oo 50-60 qa  0.7838 0.8777  34.0665 32.5721  0.433196534 0.481532148  433.1965 481.5321  0.7235 0.7235  0.5671 0.6350  31.2537 29.8827  13.5390 14.3895  23.8754 22.6604  23875 22660  0.55 0.55  50-60 qb  Sediment Extraction Data for C3-05 Total iron - 5.0 M HCI Extraction  C3-33.5a C3-33.5b C3-33.10a C3-33.10b C3-34.2a C3-34.2b C3-34.6a C3-34.6b C3-34.10a C3-34.10b C3-35.2a C3-35.2b C3-35.6a C3-35.6b C3-35.10a C3-35.10b C3-36.2a C3-36.2b C3-36.6a C3-36.6b C3-36.10a C3-36.10b C3-37.2a C3-37.2b C3-37.6a C3-37.6b C3-38.9a C3-38.9b C3-39.2a C3-39.2b C3-39.6a C3-39.6b C3-39.10a C3-39.10b C3-40.2a C3-40.2b C3-40.6a C3-40.6b C3-40.10a C3-40.10b C3-41.2a C3-41.2b C3-41.6a C3-41.6b C3-41.10a C3-41.10b C3-42.2a C3-42.2b C3-42.6a C3-42.6b C3-42.10a C3-42.10b C3-43.2a C3-43.2b  soln sed weight weight (g) remarks 1.9293 28.8167 1.3057 28.7289 2.6037 28.8844 2.2297 28.3710 1.8412 27.1122 2.7620 28.1018 1.7574 27.4656 oxidized 1.0549 28.6006 oxidized 1.2773 29.1368 1.0624 26.4402 2.0831 28.7442 1.8365 27.8865  1.0385 1.0938 1.0473 1.1214 1.0663 1.1650 1.5325 1.3378 1.0735 1.2904 1.5883 1.6287  26.6947 28.2694 28.2231 27.9567 28.3108 oxidized 27.7772 oxidized 28.0852 28.0021 28.8279 26.7116 29.3958 27.9004  2.3160 1.1961 1.3453 0.8696 1.3300 1.2450 1.3460 1.4193 1.3486 1.0505  27.5062 28.6986 28.8500 27.9546 27.5118 27.3060 28.8923 28.6084 28.9979 27.7425  0.9344 1.4650 1.9385 1.1219 1.4781 1.1194 1.3533 0.9564 1.0958 1.4028 1.2344 1.2905 1.4150 1.3483  28.2981 28.3011 29.3770 29.1810 29.0250 28.5890 27.8181 28.9170 29.9472 27.3795 28.9265 27.6483 28.9250 26.1246  oxidized oxidized oxidized oxidized  depth mg total dry /wet dry sed cone Mg/g (m) mg/g mq/L ratio mass (g) ml of soln of Fe FeTot 10.26 21833 26.3889 38.8247 21.8327 0.9217 1.7783 1471.25 26232 10.26 26.3085 31.5702 26.2321 0.9217 1.2035 1200 33828 10.36 0.9362 2.4376 26.4509 82.4607 33.8282 3117.5 30928 10.36 25.9808 64.5622 30.9282 0.9362 2.0875 2485 22103 10.46 24.8280 37.7076 22.1026 1518.75 0.9266 1.7060 21594 10.46 25.7342 55.2643 21.5942 2.5592 2147.5 0.9266 10.57 18.5948 18595 1.5454 25.1516 28.7358 0.8793 1142.5 18.3524 18352 10.57 0.8793 0.9276 26.1910 17.0242 650 18.9722 18972 10.67 26.6821 21.6792 0.8946 1.1427 812.5 10.67 19.0748 19075 0.9504 24.2126 18.1292 748.75 0.8946 10.77 10711 26.3225 20.1038 10.7113 0.9010 1.8769 763.75 10.77 25.5371 15.3223 9.2599 9260 1.6547 600 0.9010 10.87 10.87 19017 10.97 24.4457 16.3786 19.0169 0.8613 670 0.8293 10.97 18.9065 18907 0.9071 25.8877 17.1506 0.8293 662.5 11.07 20996 25.8453 17.5102 20.9962 677.5 0.7963 0.8340 11.07 21108 25.6014 18.8490 21.1081 0.8930 736.25 0.7963 18826 11.18 0.8524 0.9089 25.9256 17.1109 18.8259 660 18987 11.18 18.9875 0.8524 0.9930 25.4370 18.8552 741.25 17301 11.28 0.8597 1.3175 25.7190 22.7935 17.3006 886.25 11.28 17781 25.6429 . 20.4503 17.7811 0.8597 1.1501 797.5 11.38 23520 0.9232 26.3992 21.7133 23.5204 822.5 0.8600 22567 11.38 22.5667 1.1097 24.4612 25.0421 1023.75 0.8600 20700 11.48 26.9192 27.7605 20.6995 0.8444 1.3411 1031.25 11.48 21691 1.3752 25.5498 29.8294 21.6905 0.8444 1167.5 11.87 11.87 11.99 20610 2.0074 25.1888 41.3726 20.6097 1642.5 0.8668 18632 11.99 18.6318 1.0367 26.2808 19.3164 0.8668 735 19669 12.09 26.4194 22.8528 19.6695 1.1618 865 0.8636 19387 12.09 25.5995 14.5597 19.3868 0.7510 568.75 0.8636 12.19 20185 1.1795 25.1940 23.8083 20.1845 0.8869 945 12.19 15.5697 15570 25.0055 17.1913 1.1041 687.5 0.8869 17734 12.29 26.4582 21.5965 17.7337 1.2178 816.25 0.9048 14740 12.29 14.7400 1.2841 26.1982 18.9282 0.9048 722.5 19.3841 19384 12.40 1.0874 26.5549 21.0779 0.8063 793.75 12.40 19458 25.4052 16.4816 19.4584 0.8470 648.75 0.8063 12.50 12.50 12.60 20208 0.7726 25.9140 15.6132 20.2083 0.8269 602.5 17303 12.60 17.3033 25.9168 20.9602 1.2113 808.75 0.8269 12.70 17015 17.0155 1.6798 26.9020 28.5834 0.8666 1062.5 17.6257 17626 12.70 0.9722 26.7225 17.1358 0.8666 641.25 18334 12.80 26.5797 23.1243 18.3340 1.2613 0.8533 870 18946 12.80 18.9460 26.1804 18.0972 0.9552 0.8533 691.25 16.7211 16721 12.90 25.4745 19.8064 0.8753 1.1845 777.5 16884 12.90 16.8843 26.4808 14.1341 0.8371 0.8753 533.75 16989 13.00 16.9890 27.4242 15.4261 0.9080 0.8286 562.5 16986 13.00 16.9863 1.1624 25.0728 19.7448 787.5 0.8286 17.5706 17571 13.11 26.4895 18.4764 1.0515 697.5 0.8519 18482 13.11 25.3190 20.3185 18.4824 1.0993 0.8519 802.5 18196 13.21 18.1959 26.4881 21.7202 1.1937 0.8436 820 18877 13.21 23.9236 21.4715 18.8773 1.1374 0.8436 897.5  99  Sediment Extraction Data for C2-05 Total iron - 5.0 M HCI Extraction  C2-2.2a C2-2.2b C2-2.6a C2-2.6b C2-2.10a C2-2.10b C2-3.2a C2-3.2b C2-3.6a C2-3.6b C2-3.10a C2-3.10b C2-4.2a C2-4.2b C2-4.6a C2-4.6b C2^l.10a C2^l.10b C2-5.2a C2-5.2b C2-5.6a C2-5.6b C2-5.10a C2-5.10b C2-6.2a C2-6.2b  C2-7.5a C2-7.5b C2-7.11a C2-7.11b C2-8.3a C2-8.3b C2-8.7a C2-8.7b C2-8.11a C2-8.11b C2-9.3a C2-9.3b C2-9.7a C2-9.7b . C2-9.11a C2-9.11b C2-10.3a C2-10.3b C2-10.7a C2-10.7b C2-10.11a C2-10.11b C2-11.3a C2-11.3b C2-11.7a C2-11.7b  depth mg total of dry/wet dry sed sed soln weight remar cone pg/g (m) ratio mass (g) ml of soln Fe mg/g FeTot ks mg/L weight (g) (g) 0.71 19195 28.6481 16.6875 19.1955 31.2264 582.50 0.8412 0.8693 1.0335 0.71 25.8949 18.8193 18819 27.2220 951.25 0.8412 1.3760 1.6358 29.6720 0.81 28.1249 25.8046 17.8301 17830 1.4472 30.6561 1.7336 917.50 0.8348 18658 0.81 28.1674 17.2173 18.6575 0.9228 1.1054 30.7025 611.25 0.8348 18816 0.91 25.2242 18.8159 1.3406 27.4923 1.5974 29.9666 917.50 0.8392 19209 0.91 27.8153 21.2440 19.2091 1.1059 1.3178 30.3187 763.75 0.8392 18399 1.02 27.8127 17.5567 18.3985 0.9542 30.3158 631.25 0.8407 1.1351 18526 1.02 16.3531 18.5262 0.8827 27.8351 30.3403 587.50 0.8407 1.0500 18793 1.12 27.8127 24.3013 18.7929 1.2931 30.3158 873.75 0.8388 1.5417 19257 1.12 14.9375 19.2573 0.7757 28.7261 31.3114 520.00 0.8388 0.9248 1.22 18318 28.1170 16.1321 18.3178 0.8807 30.6475 573.75 0.8320 1.0585 1.22 18412 28.3682 22.3399 18.4123 1.2133 30.9213 787.50 0.8320 1.4583 1.32 17513 28.1291 22.5033 17.5126 1.2850 30.6607 800.00 0.8254 1.5567 18124 1.32 28.5763 20.2535 18.1241 1.1175 31.1482 708.75 0.8254 1.3538 1.42 16828 27.8182 20.3073 16.8285 1.2067 30.3218 730.00 0.8971 1.3452 1.42 15.5347 17.4712 17471 0.8892 28.4389 30.9984 546.25 0.8971 0.9912 18044 1.52 19.3711 18.0444 27.5745 30.0562 702.50 0.8905 1.0735 1.2055 18549 1.52 16.1351 18.5490 27.5225 586.25 0.8905 0.8699 0.9768 29.9995 1.63 18775 1.1192 28.3010 21.0135 18.7751 742.50 0.8331 1.3434 30.8481 17810 1.63 27.8437 16.9150 17.8097 0.9498 30.3496 607.50 0.8331 1.1400 1.73 1.73 1.83 16.3949 17.3888 17389 28.3282 0.9428 1.0247 30.8777 578.75 0.9201 16910 1.83 22.4690 16.9100 1.3287 28.6685 31.2487 783.75 0.9201 1.4441 19374 21.8764 19.3742 1.93 28.0017 1.1292 30.5219 781.25 0.8650 1.3054 1.93 19017 28.2106 17.6669 19.0173 0.9290 626.25 0.8650 1.0740 30.7496  1.3052 1.1307 0.9936 1.1306 1.4444 1.4315 1.2811 1.2846 1.2497 1.0066 1.4385 1.0693 1.3322 1.3270 1.4526 1.3575 1.2026 1.4050 1.0134 1.5003 1.0288 1.1260 1.0994 1.0204 1.0754 1.1513  30.0807 29.8777 30.8474 31.5164 31.2444 30.6080 31.4380 30.4222 31.4915 31.3336 30.4885 30.3220 30.3345 30.0914 30.1483 30.4925 30.0088 30.1823 30.5457 30.3155 30.1069 30.1196 30.5548 30.0208 30.7000 30.1811  820.00 697.50 587.50 675.00 858.75 865.00 701.25 790.00 702.50 581.25 845.00 616.25 791.25 801.25 885.00 805.00 702.50 796.25 571.25 858.75 578.75 645.00 605.00 612.50 602.50 656.25  0.8769 0.8769 0.9111 0.9111 0.9131 0.9131 0.8835 0.8835 0.9302 0.9302 0.9477 0.9477 0.8725 0.8725 0.8952 0.8952 0.8508 0.8508 0.8474 0.8474 0.8536 0.8536 0.8465 0.8465 0.8397 0.8397  1.1446 0.9915 0.9052 1.0301 1.3189 1.3072 1.1319 1.1350 1.1625 0.9363 1.3632 1.0134 1.1623 1.1578 1.3004 1.2152 1.0232 1.1954 0.8587 1.2713 0.8782 0.9612 0.9307 0.8638 0.9030 0.9668  27.5970 27.4107 28.3004 28.9141 28.6646 28.0807 28.8422 27.9103 28.8913 28.7464 27.9711 27.8183 27.8298 27.6068 27.6590 27.9748 27.5310 27.6902 28.0236 27.8124 27.6210 27.6327 28.0319 27.5420 28.1651 27.6891  22.6295 19.1190 16.6265 19.5170 24.6157 24.2898 20.2256 22.0491 20.2961 16.7089 23.6356 17.1431 22.0203 22.1199 24.4782 22.5197 19.3405 22.0483 16.0085 23.8839 15.9857 17.8231 16.9593 16.8695 16.9695 18.1710  19.7714 19.2822 18.3669 18.9475 18.6631 18.5820 17.8693 19.4273 17.4598 17.8452 17.3378 16.9171 18.9453 19.1055 18.8243 18.5313 18.9016 18.4438 18.6416 18.7863 18.2027 18.5430 18.2222 19.5290 18.7919 18.7958  19771 19282 18367 18948 18663 18582 17869 19427 17460 17845 17338 16917 18945 19106 18824 18531 18902 18444 18642 18786 18203 18543 18222 19529 18792 18796  100  2.34 2.34 2.46 2.46 2.57 2.57 2.67 2.67 2.77 2.77 2.87 2.87 2.97 2.97 3.07 3.07 3.18 3.18 3.28 3.28 3.38 3.38 3.48 3.48 3.58 3.58  Sediment Extraction Data for C1-05 Total iron - 5.0 M HCI Extraction sed weight soln weight remarks (g) (g)  cone mg/L  dry/wet dry sed ratio mass (g)  ml of soln  mg total of Fe mg/g  FeTot  depth (m)  13.5985 0.0000 16.6772  17.0781  17078  20.6717  20672  1.0819 0.8911 0.7601 0.6450 0.9805 0.7052  30.0520 0.0000 29.3225 0.0000 29.5151 28.5379 26.8950 28.1562 28.6227 29.1310  20.8451 17.8719 15.8345 11.9664 16.3865 12.0894  19.2665 20.0566 20.8320 18.5513 16.7116 17.1427  19267 20057 20832 18551 16712 17143  0.25 0.25 0.35 0.35 0.45 0.45 0.56 0.56 0.66 0.66  525.00 0.8587  0.8713  28.3060  14.8606  17.0566  17057  0.76  1.3577 1.4570 1.7241  31.2403 from oxidized part 692.50 0.8587 846.25 0.9504 31.2683 1142.50 0.9504 29.9348  1.1659 1.3847 1.6385  28.6608 28.6865 27.4631  19.8476 24.2760 31.3766  17.0238 17.5316 19.1491  17024 17532 19149  0.76 0.86 0.86  C1-6.8a C1-6.8b C1-7.0a C1-7.0b C1-7.4a C1-7.4b C1-7.8a C1-7.8b C1-8.0a C1-8.0b C1-8.4a C1-8.4b  1.2435 1.1758 1.2969 1.3512 1.0696 1.4381 1.1403 1.1910 1.2380 1.7523 1.2903  31.1000 soln weight error 31.0601 30.1880 31.4796 30.2569 30.8647 30.5503 30.0518 29.8161 rock 31.0432 30.1650  C1-10.6a C1-10.6b C1-10.10a C1-10.10b C1-11.2a C1-11.2b C1-11.6a C1-11.6b C1-11.10a C1-11.10b C1-12.2a C1-12.2b C1-12.6a C1-12.6b C1-12.10a C1-12.10b C1-13.2a C1-13.2b C1-13.6a C1-13.6b C1-13.10a C1-13.10b  1.1304 1.1747 1.3941 1.5487 1.2956 0.9665 0.9454 1.2332 0.9648 1.5772 1.0718 1.8347 1.3856 1.2481 1.0620 1.1085 0.9207 1.1186 1.2283 1.3327 1.2100 1.4321  redone C1-7.0a C1-7.0b  1.8798 1.3268  1.0179  32.7567  C1-4.8a C1-4.8b C1-5.0a C1-5.0b C1-5.4a C1-5.4b C1-5.8a C1-5.8b  0.9987  31.9615  1.4580 1.2008 1.1660 0.9895 1.2415 0.8929  32.1715 31.1063 29.3156 30.6903 31.1987 31.7528  C1-6.0a  1.0146  oxidation oxidation oxidation oxidation oxidation oxidation from unoxidized 30.8535 part  C1-6.0b C1-6.4a C1-6.4b  C1-4.4a C1-4.4D  452.50 0.7823 0.7823 568.75 0.8078 0.8078 706.25 0.7421 626.25 0.7421 588.75 0.6519 425.00 0.6519 572.50 0.7898 415.00 0.7898  0.7963 0.8068  741.25 883.75 858.75 1858.75 655.00 818.75 649.50 680.00 523.75 853.75 717.50  0.9505 0.9505 0.9560 0.9560 0.8763 0.8763 0.8429 0.8429 0.8319 0.8319 0.8619 0.8619  1.1820 1.1176 1.2399 1.2918 0.9372 1.2601 0.9611 1.0039 1.0299 1.4577 1.1121  28.5321 28.4955 27.6954 28.8804 27.7586 28.3162 28.0278 27.5705 27.3542 28.4800 27.6743  21.1494 25.1829 23.7834 53.6814 18.1819 23.1839 18.2041 18.7479 14.3268 24.3148 19.8563  17.8929 22.5320 19.1825 41.5566 19.3994 18.3979 18.9402 18.6757 13.9113 16.6803 17.8551  17893 22532 19182 41557 19399 18398 18940 18676 13911 16680 17855  0.96 0.96 1.06 1.06 1.17 1.17 1.27 1.27 1.37 1.37 1.47 1.47  31.0467 31.8986 29.6207 30.3981 30.2156 30.2607 30.1034 30.7947 31.0474 30.8968 30.6742 30.4266 30.3032 30.2200 31.2991 30.3325 30.9300 30.3152 30.2214 31.1847 29.8970 30.3088  557.50 581.25 721.25 762.50 663.75 507.50 513.75 612.50 500.00 803.75 573.75 983.75 748.75 668.75 555.00 588.75 476.25 612.50 643.75 667.50 656.25 736.25  0.8141 0.8141 0.7995 0.7995 0.8184 0.8184 0.8305 0.8305 0.8199 0.8199 0.8225 0.8225 0.8326 0.8326 0.8278 0.8278 0.8197 0.8197 0.8179 0.8179 0.8179 0.8179  0.9203 0.9563 1.1146 1.2383 1.0603 0.7910 0.7851 1.0241 0.7911 1.2932 . 0.8816 1.5091 1.1537 1.0392 0.8791 0.9176 0.7547 0.9169 1.0047 1.0901 0.9897 1.1714  28.4832 29.2648 27.1750 27.8882 27.7207 27.7621 27.6178 28.2520 28.4839 28.3457 28.1415 27.9143 27.8011 27.7248 28.7148 27.8280 28.3761 27.8121 27.7261 28.6098 27.4284 27.8062  15.8794 17.0101 19.5999 21.2647 18.3996 14.0893 14.1886 17.3044 14.2419 22.7828 16.1462 27.4607 20.8161 18.5409 15.9367 16.3837 13.5141 17.0349 17.8486 19.0971 17.9999 20.4723  17.2555 17.7872 17.5840 17.1731 17.3526 17.8120 18.0719 16.8966 18.0037 17.6178 18.3152 18.1971 18.0428 17.8413 18.1285 17.8552 17.9067 18.5785 17.7654 17.5190 18.1873 17.4774  17255 17787 17584 17173 17353 17812 18072 16897 18004 17618 18315 18197 18043 17841 18128 17855 17907 18578 17765 17519 18187 17477  3.25 3.25 3.35 3.35 3.45 3.45 3.56 3.56 3.66 3.66 3.76 3.76 3.86 3.86 3.96 3.96 4.06 4.06 4.17 4.17 4.27 4.27  30.3786 30.8557  1365.00 997.50  0.9560 0.9560  1.7971 1.2684  27.8703 28.3080  38.0429 28.2372  21.1689 22.2614  21169 22261  1.06 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) C2-06-02 C2-06-02 C2-06-02 C2-06-02 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C1-06-01 C1-06-01 C1-06-01 C1-06-01  2.0544 1.5979 2.2305 1.634  0"-2"a 0"-2"b 2"-6"a 2"-6"b 0"-3"a  1.8621 2.2743 2.16  0"-3"b 3"-7"a  1.5301 1.5129 1.4455  3"-7"b 7"-11"a 7"-11"b 11"-1'3"a 11"-1'3"b 1'3"-17"a 1'3"-17"b 17"-1'11"a 17"-1'11"b 0"- 2.5"a 0"- 2.5"b 2.5" - 6"a 2.5" - 6"b  1.3217 1.3242 1.2473 1.1707 1.1905 1.3466 1.9752 1.7368 2.1278 2.7009  soln weight (g) 28.3294 28.8482 29.7117 28.7907 29.6927 29.415 29.297 30.668 30.0418 31.2563 30.2355 30.7975 30.3817 30.589 30.7478 30.6822 29.1466 28.9922 30.6825 30.7208  dry sed mass (g)  dry/wet ratio assumed  cone mg/L 329.25 274.5 270.75 228.75 174.75  0.8  167 298.5  0.8 0.8 0.8  205 214 199.25 214.75 224.75 215.25 210 198.25 210.25 339 312.25 434 548.5  0.8 0.8 0.8 0.8  1.64352 1.27832 1.7844 1.3072 1.48968 1.81944 1.728  0.8 0.8  1.22408 1.21032 1.1564  0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8  1.05736 1.05936 0.99784 0.93656 0.9524 1.07728 1.58016 1.38944 1.70224 2.16072  ml of soln  mg total of Fe  mg/g  ug/g FeTot  depth (m)  5624.669393 6139.462049 4467.994047 4993.213333  0.0254 0.0254 0.1016 0.1016  3452.094863 2675.817066  0.0381 0.0381  5.015711892 5.09024103 5.264393543  5015.711892 5090.24103 5264.393543  0.127 0.127 0.2286  5.337484753 6.086060765 6.47560616 6.49535894 6.797634394  5337.484753 6086.060765 6475.60616 6495.35894  0.2286 0.3302 0.3302 0.4318  6797.634394 6343.32102 5934.754216 6197.197955 6457.325151 7752.97734 7728.93215  0.4318 0.5334 0.5334 0.03175 0.03175 0.1143 0.1143  28.07670961 28.59088206 29.44667988  9.24425664 7.848197126 7.972688578  5.624669393 6.139462049 4.467994047  28.53389495 29.42784936 29.15262636  6.527128469 5.142516675 4.868488603  4.993213333 3.452094863 2.675817066  29.03567889 30.39444995 29.77383548  8.667150149 6.23086224 6.371600793  30.97750248 29.96580773 30.52279485 30.11070367  6.172267369 6.43515721 6.859998142 6.481328964  30.31615461 30.47353816 30.40852329 28.88662042 28.73359762 30.40882061 30.44677899  6.366392468 6.04137894 6.393392022 9.792564321 8.972065857 13.19742815 16.70005828  6.34332102 . 5.934754216 6.197197955 6.457325151 7.75297734 7.72893215  C12-06  0-10 ga 0-10 gb  0.87299833 0.87299833  1.399241723 0.918219643  28.03256881  32.43266988  28.12229358  6.735258226  23.178747 7.335127576  23178.747 7335.127576  0.15  239.4988946 261.6064849 386.8828298  0.812802151 0.812802151  0.867910137 1.308692744  28.12623853 28.06311927  7.358006396 10.85713899  8.477843595 8.296171158  8477.843595 8296.171158  0.25  235.8142962 276.3448784  0.794815552 0.794815552  0.819136908 0.903864246  28.08724771 28.33844037  6.623374551 7.831182857  8.085796753 8.66411399  8085.796753  0.35  0.552689757  8664.11399  0.35  32.5314 30.2732  0.420044215 0.515843773  210.0221076 257.9218865  0.7271411 0.7271411  0.617779079 0.739575213  29.8453211 27.77357798  6.268177239 7.163413628  10.14630869 9.685848715  10146.30869 9685.848715  0.45 0.45  30.2378 30.4546  0.560058954 0.52321297  280.0294768 261.6064849  0.723487412 0.723487412  0.839173049 0.811825225  27.74110092 27.94  7.768325975 7.309285188  9.257120431 9.003520667  9257.120431 9003.520667  0.55 0.55  10-20 gb  1.6028 1.0518  30.5555 30.6533  1.156963891 0.478997789  20-30 sa 20-30 sb  1.0678 1.6101  30.6576 30.5888  0.52321297  30-40 ga  1.0306 1.1372  30.6151 30.8889  0.471628592  30-40 gb 40-50 ga 40-50 gb  0.8496 1.0171  50-60 ga 50-60 gb  1.1599 1.1221  10-20 ga  o  depth [m] ug/g mg total in soln mg Fe/g sed ml of soln dry sed mass [q] dry/wet ratio actual cone. mg/L measured mg/L soln weight [gl sed weight [gl 7679.27203 0.05 7.67927203 11.16817758 27.30669725 0.812246658 1.454327641 408.99042 29.7643 0.81798084 1.7905 6667.411127 0.05 6.667411127 9.844987256 27.26458716 0.812246658 1.4765832 361.0906411 0.722181282 1.8179 29.7184  0.77376566  1156.963891  0.15  0.25  Sediment Extraction Data for C3-05 Total iron - 0.75 M HCI Extraction  C3-33.5a C3-33.5b C3-33.10a C3-33.10b C3-34.2a C3-34.2b C3-34.6a C3-34.6b C3-34.10a C3-34.10b C3-35.2a C3-35.2b C3-35.6a C3-35.6b C3-35.10a C3-35.10b C3-36.2a C3-36.2b C3-36.6a C3-36.6b C3-36.10a C3-36.10b C3-37.2a C3-37.2b C3-37.6a C3-37.6b C3-38.9a C3-38.9b C3-39.2a C3-39.2b C3-39.6a C3-39.6b C3-39.10a C3-39.10b C3-40.2a C3-40.2b C3-40.6a C3-40.6b C3-40.10a C3-40.10b C3-41.2a C3-41.2b C3-41.6a C3-41.6b . C3-41.10a C3-41.10b C3-42.2a C3-42.2b C3-42.6a C3-42.6b C3-42.10a C3-42.10b C3-43.2a C3-43.2b redone C3-33.5a C3-33.5b  1.4292 1.1440 1.1935 0.8674 1.0096 1.2840 1.3776 1.0083 1.0391 1.1252 1.0299 1.5885  30.4531 30.5393 29.2264 29.7260 29.4603 oxidized 30.5108 oxidized 29.6055 30.2598 30.6228 30.8435 29.2556 29.6871  1.1912 1.4482 0.9580 1.8140 1.3969 1.7323 1.2567 1.8191 1.7562 1.4756  30.1163 29.4083 30.0598 30.2747 29.6988 30.5898 29.3491 29.4189 29.9266 30.0744  1.0091 1.3012 1.5263 1.8240 1.5467 1.5526 1.5790 2.2067 1.7852 1.3269 1.6270 0.9568 1.5506 1.6805  30.8124 30.2145 30.2527 29.5765 29.9917 30.0700 30.4994 29.7692 30.2842 30.1612 30.1400 29.7939 30.6465 29.7582  depth mg total of dry/wet dry mass ug/g (m) mg/g ml of soln Fe FeTot ratio (g) 1.3441 30.1911 15.3673 11.4335 11433 10.26 509 0.9217 7411 10.26 10.9330 7.4106 362 0.9217 1.4753 30.2016 6.9604 30.0387 18.6540 6960 10.36 0.9362 2.6800 621 28.1277 10.4846 5.2649 5265 10.36 1.9914 372.75 0.9362 9.2167 5.6849 5685 10.46 1.6212 31.0325 297 0.9266 5.3010 5301 10.46 30.3823 5.9093 0.9266 1.1148 194.5 10.57 4.8027 4.5483 4548 1.0559 30.1581 159.25 0.8793 4368 10.57 4.5815 4.3676 1.0490 28.1939 162.5 0.8793 5.9287 5929 10.67 6.3386 1.0691 29.8289 212.5 0.8946 5638 10.67 29.9387 6.4817 5.6375 1.1497 216.5 0.8946 7.8256 5,6377 5638 10.77 1.3881 29.9832 261 0.9010 4.6268 5.2598 5260 10.77 0.8796 27.7053 167 0.9010 10.87 10.87 7537 10.97 8.9337 7.5372 30.1815 296 0.8293 1.1853 6912 10.97 6.9123 0.9488 27.9664 6.5581 234.5 0.8293 9.5395 9540 11.07 0.9504 28.9657 9.0663 313 0.7963 0.6907 29.4609 6.9970 10.1300 10130 11.07 0.7963 237.5 7.3115 7312 11.18 29.1975 6.2921 0.8524 0.8606 215.5 6.5864 6586 11.18 0.8524 1.0945 27.9403 7.2086 258 5.6610 5661 11.28 29.3414 6.7045 0.8597 1.1843 228.5 4.6634 5.3798 5380 11.28 29.9899 0.8597 0.8668 155.5 9.5905 10.7326 10733 11.38 0.8936 30.3497 316 0.8600 0.9676 28.2450 10.0693 10.4062 10406 11.38 0.8600 356.5 6.5093 7.4852 7485 11.48 0.8696 28.9946 224.5 0.8444 7.8202 7820 11.48 10.4890 1.3413 29.4223 356.5 0.8444 11.87 11.87 5.5793 5579 11.99 29.8477 5.7606 0.8668 1.0325 193 5.8164 5816 11.99 7.3011 1.2553 29.1460 250.5 0.8668 5527 12.09 4.5730 5.5273 0.8274 29.7917 0.8636 153.5 5.2825 5282 12.09 27.7241 8.2756 1.5666 298.5 0.8636 12.19 4.6567 4657 29.4339 5.7690 1.2389 196 0.8869 6640 12.19 10.2017 6.6403 1.5363 30.3169 0.8869 336.5 2980 12.29 3.3887 2.9803 29.0873 0.9048 1.1370 116.5 8.6344 5246 12.29 26.9404 5.2461 1.6459 320.5 0.9048 8106 12.40 29.6597 11.4783 8.1060 1.4160 387 0.8063 8.0917 8092 12.40 9.6274 29.8061 0.8063 1.1898 323 12.50 12.50 8:6374 8637 12.60 7.2069 0.8344 30.5376 0.8269 236 8503 12.60 9.1482 8.5028 29.9450 0.8269 1.0759 305.5 5577 12.70 7.3758 5.5765 29.9829 1.3226 246 0.8666 5.2006 5201 12.70 27.0847 8.2202 1.5806 0.8666 303.5 6.7452 6745 12.80 8.9024 29.7242 1.3198 299.5 0.8533 7187 12.80 9.5217 7.1870 1.3249 29.8018 0.8533 319.5 5457 12.90 7.5417 5:4569 30.2274 1.3821 249.5 0.8753 4.9611 4961 12.90 27.2612 9.5823 1.9315 0.8753 351.5 6067 13.00 8.9742 6.0667 30.0141 1.4793 299 0.8286 5981 13.00 6.5763 5.9811 29.8922 1.0995 220 0.8286 5744 13.11 7.9607 5.7436 29.8712 1.3860 266.5 0.8519 4971 13.11 4.9709 4.0516 27.2838 0.8151 148.5 0.8519 5.7352 5735 13.21 7.5022 30.3731 1.3081 247 0.8436 5142 13.21 7.2897 5.1420 27.2511 1.4177 0.8436 267.5  2.1687 2.0048  28.955 28.7236  342.25 358.50  weight soln weight (g) remarks (g) 1.4582 30.4628 1.6006 30.4734 2.8626 30.3090 2.1271 30.7155 1.7497 31.3118 1.2031 30.6557 1.2008 30.4295 oxidized 1.1929 30.7877 oxidized 1.1951 30.0974 1.2852 30.2081 1.5406 30.2530 0.9763 30.2542  oxidized oxidized oxidized oxidized  cone mg/L  0.9217 0.9217  1.9989 1.8479  28.6967 26.30371  9.8215 9.4299  4.9133 5.1031  4913 5103  103  10.26 10.26  Sediment Extraction Data for C2-05 Total iron - 0.75 M HCI Extraction  C2-2.2a C2-2.2b C2-2.6a C2-2.6b C2-2.10a C2-2.10b C2-3.2a C2-3.2b C2-3.6a C2-3.6b C2-3.10a C2-3.10b C2-4.2a C2-4.2b C2-4.6a C2-4.6b C2-4.10a C2-4.10b C2-5.2a C2-5.2b C2-5.6a C2-5.6b C2-5.10a C2-5.10b C2-6.2a C2-6.2b  C2-7.5a C2-7.5b C2-7.11a C2-7.11b C2-8.3a C2-8.3b C2-8.7a C2-8.7b C2-8.11a C2-8.11b C2-9.3a C2-9.3b C2-9.7a C2-9.7b C2-9.11a C2-9.11b C2-10.3a C2-10.3b C2-10.7a C2-10.7b C2-10.11a C2-10.11b C2-11.3a C2-11.3b C2-11.7a C2-11.7b  depth mg total of dry/wet dry mass soln weight remar sed ug/g mg/g (m) ml of soln Fe FeTot ks cone mg/L ratio weight (g) (g) (g) 5594 0.71 6.3182 5.5937 31.3945 0.8412 1.1295 31.6771 201.25 1.3428 0.71 5300 29.7721 6.7210 5.2996 0.8412 1.2682 225.75 1.5077 30.0400 7.0624 5.5583 5558 0.81 1.2706 28.7967 0.8348 29.0559 245.25 1.5220 5525 0.81 8.0447 5.5255 30.3573 0.8348 1.4559 265.00 1.7440 30.6305 5804 0.91 6.3047 5.8043 30.3839 0.8392 1.0862 30.6574 207.50 1.2943 0.91 6.1327 5.7386 5739 29.8427 0.8392 1.0687 205.50 1.2734 30.1113 1.02 5796 30.0491 4.8003 5.7959 0.8407 0.8282 159.75 0.9852 30.3195 5621 1.02 6.2465 5.6214 1.1112 29.8520 0.8407 30.1207 209.25 1.3218 6117 1.12 5.7788 6.1172 0.9447 29.8648 193.50 0.8388 30.1336 1.1263 1.12 5.0104 5.9104 5910 29.9576 0.8388 0.8477 30.2272 167.25 1.0107 6237 1.22 7.3202 6.2373 30.0010 0.8320 1.1736 30.2710 244.00 1.4106 1.22 5.5314 6.0587 6059 30.9882 0.9130 31.2671 178.50 0.8320 1.0973 1.32 5.9684 5.6835 5683 30.6860 0.8254 1.0501 30.9622 194.50 1.2722 6182 1.32 29.9345 6.6080 6.1818 0.8254 1.0690 30.2039 220.75 1.2950 1.42 8.1384 5.0831 5083 29.9481 0.8971 1.6011 30.2176 271.75 1.7848 5566 1.42 30.6037 5.2256 5.5664 0.9388 0.8971 30.8791 170.75 1.0465 1.52 10.3584 5.4602 5460 29.7015 1.8971 348.75 0.8905 29.9688 2.1303 5554 1.52 5.9186 5.5543 30.1585 0.8905 1.0656 196.25 1.1966 30.4299 5943 1.63 13.4250 5.9429 2.2590 29.7673 0.8331 30.0352 451.00 2.7115 6369 1.63 6.6888 6.3688 1.0502 29.6948 0.8331 29.9621 225.25 1.2606 1.73 1.73 1.83 7.1302 5.7951 5795 1.2304 29.7713 239.50 0.9201 1.3372 30.0392 5928 1.83 10.3548 5.9283 1.7467 30.2550 342.25 0.9201 30.5273 1.8983 5893 1.93 30.2264 8.5012 5.8929 1.4426 0.8650 30.4984 281.25 1.6678 1.93 6.7142 6.0595 6059 30.5885 1.1080 219.50 0.8650 30.8638 1.2810  1.6683 2.0564 1.7081 1.5627 1.5055 1.5000 1.5238 2.0504 1.5988 1.4243 1.2129 1.7370 1.1600 1.4902 1.6929 1.1394 0.9128 1.7879 1.5760 1.4884 1.4497 2.0138 1.6224 1.1041 1.8936 1.1838  30.5317 31.0373 29.9150 29.4583 31.1766 29.8752 29.8726 29.8526 29.9259 30.3692 30.3603 30.3243 30.3664 29.6840 30.4428 30.8705 30.4456 29.8058 29.8704 20.4966 30.3388 30.3734 30.6098 30.1877 28.8358 30.1843  258.25 314.75 289.50 266.75 235.25 246.00 227.75 310.75 260.50 217.25 191.75 264.75 198.25 221.25 287.00 185.75 155.00 287.50 266.50 348.00 235.75 317.25 282.75 176.50 342.25 217.75  0.8769 0.8769 0.9111 0.9111 0.9131 0.9131 0.8835 0.8835 0.9302 0.9302 0.9477 0.9477 0.8725 0.8725 0.8952 0.8952 0.8508 0.8508 0.8474 0.8474 0.8536 0.8536 0.8465 0.8465 0.8397 0.8397  1.4630 1.8033 1.5562 1.4237 1.3747 1.3697 1.3463 1.8115 1.4872 1.3249 1.1494 1.6461 1.0121 1.3002 1.5155 1.0200 0.7766 1.5212 1.3355 1.2613 1.2375 1.7190 1.3734 0.9347 1.5901 0.9940  30.2594 30.7605 29.6482 29.1955 30.8985 29.6087 29.6061 29.5863 29.6590 30.0983 30.0895 30.0538 30.0955 29.4192 30.1713 30.5951 30.1740 29.5399 29.6040 20.3138 30.0682 30.1025 30.3368 29.9184 28.5786 27.6413  7.8145 9.6819 8.5831 7.7879 7.2689 7.2837 6.7428 9.1939 7.7262 6.5389 5.7697 7.9567 5.9664 6.5090 8.6592 5.6830 4.6770 8.4927 7.8895 7.0692 7.0886 9.5500 8.5777 5.2806 9.7810 6.0189  5.3415 5.3690 5.5154 5.4701 5.2874 5.3177 5.0084 5.0752 5.1952 4.9355 5.0195 4.8336 5.8953 5.0063 5.7138 5.5717 6.0220 5.5828 5.9075 5.6049 5.7282 5.5555 6.2454 5.6497 6.1513 6.0549  5342 5369 5515 5470 5287 5318 5008 5075 5195 4936 5020 4834 5895 5006 5714 5572 6022 5583 5908 5605 5728 5556 6245 5650 6151 6055  104  2.34 2.34 2.46 2.46 2.57 2.57 2.67 2.67 2.77 2.77 2.87 2.87 2.97 2.97 3.07 3.07 3.18 3.18 3.28 3.28 3.38 3.38 3.48 3.48 3.58 3.58  Sediment Extraction Data for C1-05 Total iron - 0.75 M HCI Extraction sed weight soln weight (q) remarks (q) C1-4.4a C1-4.4b C1-4.8a C1-4.8b C1-5.0a C1-5.0b C1-5.4a C1-5.4b C1-5.8a C1-5.8b C1-6.0a C1-6.0b C1-6.4a C1-6.4b C1-6.8a C1-6.8b C1-7.0a C1-7.0b C1-7.4a C1-7.4b C1-7.8a C1-7.8b C1-8.0a C1-8.0b C1-8.4a C1-8.4b C1-10.6a C1-10.6b C1-10.10a C1-10.10b C1-11.2a C1-11.2b C1-11.6a C1-11.6b C1-11.10a C1-11.10b C1-12.2a C1-12.2b C1-12.6a C1-12.6b C1-12.10a C1-12.10b C1-13.2a C1-13.2b C1-13.6a C1-13.6b C1-13.10a C1-13.10b redone C1-6.4a C1-6.4b C1-6.8a C1-6.8b C1-7.0a C1-7.0b C1-8.0a C1-8.0b  dry/wet cone mq/L ratio  ml of soln  mg total of Fe  mq/q  ug/g FeTot  depth (m)  0.7823 0.7823 0.8078 0.8078 0.7421 0.7421 0.6519 0.6519 0.7898 0.7898 0.8587 0.8587 0.9504 0.9504 0.9505 0.9505 0.9560 0.9560 0.8763 0.8763 0.8429 0.8429 0.8319 0.8319 0.8619 0.8619  1.2357 0.9784 1.1982  29.6317 29.3873 29.2465  6.1412 4.9885 6.1198  4.9697 5.0988 5.1074  4970 5099 5107  1.6641 1.2536 0.9741 0.8308 1.2583 1.3995 2.0718 1.7536 3.4162 1.5814 2.4499  28.5903 29.3452 29.0556 29.5018 29.2312 29.8498 31.5081 29.7151 28.3048 29.6183 28.9430  8.1554 7.1969 6.5302 5.0079 5.7220 6.3580 7.7589 6.5967 9.6802 7.6341 9.5512  4.9008 5.7411 6.7038 6.0276 4.5473 4.5432 3.7450 3.7619 2.8336 4.8274 3.8986  4901 5741 6704 6028 4547 4543 3745 3762 2834 4827 3899  1.5867  28.8383  6.5535  4.1303  4130  2.5175 1.7210 2.0750 1.2954 1.5290  28.7639 29.9944 28.9487 30.8305 28.4431  8.0395 7.6936 9.4879 6.0505 6.4495  3.1935 4.4705 4.5725 4.6707 4.2181  3193 4470 4573 4671 4218  1.6910 1.2776  28.5359 29.2666  8.1113 6.4313  4.7967 5.0341  4797 5034  0.8524 1.0603 1.8355 0.9734 0.8805 1.6746 1.0703 0.9088 2.0330 2.1246 1.3868 1.4382 1.2098 1.4776 1.4111 1.5890 1.6583  29.5494 28.9522 28.8459 29.1003 29.2410 27.9220 29.6914 29.1710 28.9343 28.2687 28.9126 29.2443 29.1475 28.1729 28.2389 28.3748 29.0245  4.1591 5.1245 9.4831 4.9834 4.4739 8.1811 5.1886 4.6017 10.1993 10.2121 7.2209 7.2599 6.2303 7.6630 6.8762 8.1578 8.5114  4.8790 4.8332 5.1664 5.1194 5.0809 4.8853 4.8477 5.0636 5.0169 4.8066 5.2070 5.0477 5.1497 5.1861 4.8729 5.1339 5.1328  4879 4833 5166 5119 5081 4885 4848 5064 5017 4807 5207 5048 5150 5186 4873 5134 5133  143.25 211.00 253.50 259.50  0.8141 0.8141 0.7995 0.7995 0.8184 0.8184 0.8305 0.8305 0.8199 0.8199 0.8225 0.8225 0.8326 0.8326 0.8278 0.8278 0.8197 0.8197 0.8179 0.8179 0.8179 0.8179  0.8135 1.2636 1.4070 1.4870  29.1350 29.4968 29.1516 30.1715  4.1736 6.2238 7.3899 7.8295  5.1302 4.9253 5.2523 5.2653  5130 4925 5252 5265  3.25 3.25 3.35 3.35 3.45 3.45 3.56 3.56 3.66 3.66 3.76 3.76 3.86 3.86 3.96 3.96 4.06 4.06 4.17 4.17 4.27 4.27  442.00 159.50 266.00 256.25 243.75 274.75 193.75 281.50  0.9504 0.9504 0.9505 0.9505 0.9560 0.9560 0.8319 0.8319  4.1039 1.4546 2.7054 2.1572 1.3392 1.7946 1.3462 2.0595  28.3402 28.6867 28.0648 28.5487 28.2876 28.3352 28.7287 28.4801  12.5264 4.5755 7.4652 7.3156 6.8951 7.7851 5.5662 8.0171  3.0523 3.1455 2.7593 3.3913 5.1487 4.3380 4.1347 3.8928  3052 3145 2759 3391 5149 4338 4135 3893  0.86 0.86 0.96 0.96 1.06 1.06 1.37 1.37  1.5797 1.2507 1.4833  29.8984 29.6518 29.5097  207.25 169.75 209.25  2.2425 1.6893 1.4943 1.2745 1.5932 1.7719 2.4127 2.0421 3.5946 1.6640 2.5774  28.8476 29.6093 29.3171 29.7673 29.4943 30.1184 31.7917 29.9825 28.5595 29.8849 29.2035  1.6597  29.0978  227.25  2.8730 1.9640 2.4618 1.5369 1.8380  29.0228 30.2643 29.2092 31.1080 28.6991  279.50 256.50 327.75 196.25 226.75  1.9620 1.4823  28.7927 29.5300  284.25 219.75  1.0471 1.3024 2.2957 1.2175 1.0759 2.0462 1.2888 1.0943 2.4795 2.5912 1.6860 1.7486 1.4530 1.7746 1.7047 1.9196 2.0230  29.8153 29.2128 weiqht?? 29.1055 29.3622 29.5042 28.1733 29.9586 29.4335 29.1947 28.5231 29.1728 29.5075 29.4098 28.4265 28.4931 28.6302 29.2857  140.75 177.00 328.75 171.25 153.00 293.00 174.75 157.75 352.50 361.25 249.75 248.25 213.75 272.00 243.50 287.50 293.25  0.9946 1.5449 1.7202 1.8180  29.3972 29.7623 29.4140 30.4430  4.3182 1.5306 2.8462 2.2694 1.4008 1.8772 1.6183 2.4757  28.5953 28.9449 28.3174 28.8056 28.5422 28.5902 28.9873 28.7364  oxidation oxidation oxidation oxidation oxidation oxidation oxidation  dry mass (q)  285.25 245.25 224.75 169.75 195.75 213.00 246.25 222.00 342.00 257.75 330.00  105  0.25 0.25 0.35 0.35 0.45 0.45 0.56 0.56 0.66 0.66 0.76 0.76 0.86 0.86 0.96 0.96 1.06 1.06 1.17 1.17 1.27 1.27 1.37 1.37 1.47 1.47  Sediment Extraction Data for C1-06, C2-06, C4-06 and C12-06 Total iron - 1M CaCI2 Extraction 2006 sed weiqht (q) C2-06-02 C2-06-02 C2-06-02 C2-06-02 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C4-06-03 C1-06-01 C1-06-01 C1-06-01 C1-06-01 C12-06 0-10 ga 0-10 gb  0"-2"a 0"-2"b 2"-6"a 2"-6"b 0"-3"a 0"-3"b 3"-7"a 3"-7"b 7"-11"a 7"-11"b 11"-1'3"a 11"-1'3"b 1'3"-1'7"a 1'3"-1'7"b 1'7"-1'11"a 17"-ri1"b 0"- 2.5"a 0"-2.5"b 2.5" - 6"a 2.5" - 6"b  1.8187 2.1061 1.8008 2.3463 2.6958 2.6823 2.6458 3.0778 2.9683 2.6913 2.1394 2.3513 2.1363 2.5548 3.9654 2.277 1.6127 2.524 2.6113 4.0048  soln weiqht (q) 30.2949 29.9248 28.8423 30.4059 30.4573 31.5726 29.4895 29.4345 31.1619 31.5594 30.1347 29.1743 29.8656 30.507 29.7208 30.296 29.1779 28.629 29.974 29.8325  cone mg/L  mq/q ug/g FeTot depth (m) dry/wet ratio dry sed mass (q) ml of soln mq total of Fe assumed 0.2608 • 0.1792 179.2354 0.0254 1.4550 27.7426 9.4 0.8 27.4037 0.2453 0.1456 145.5669 0.0254 0.8 1.6849 8.95 26.4124 0.1186 0.0823 82.3186 0.1016 4.49 0.8 1.4406 27.8442 0.1222 0.0651 65.1218 0.1016 1.8770 4.39 0.8 0.3124 0.1448 144.8469 0.0381 2.1566 27.8913 11.2 0.8 28.9126 0.3036 0.1415 141.4750 0.0381 2.1458 10.5 0.8 27.0050 0.4477 0.2115 211.5350 0.127 0.8 2.1166 16.58 2.4622 26.9547 0.4798 0.1949 194.8604 0.127 17.8 0.8 28.5365 0.1196 0.0504 50.3521 0.2286 0.8 2.3746 4.19 0.1301 0.0604 60.4041 0.2286 28.9005 0.8 2.1530 4.5 0.3844 0.2246 224.6019 0.3302 1.7115 27.5959 13.93 0.8 26.7164 0.3935 0.2092 209.2100 0.3302 1.8810 14.73 0.8 27.3495 0.3720 0.2176 217.6383 0.4318 0.8 1.7090 13.6 2.0438 27.9368 0.4255 0.2082 208.1756 0.4318 15.23 0.8 27.2168 0.4817 0.1519 151.8568 0.5334 3.1723 17.7 0.8 1.8216 27.7436 0.3579 0.1965 196.4714 0.5334 12.9 0.8 1.2902 26.7197 0.8711 0.6752 675.1580 0.03175 0.8 32.6 1.1837 0.5862 586.2218 0.03175 2.0192 26.2170 45.15 0.8 27.4487 2.0724 0.9920 992.0242 0.1143 0.8 2.0890 75.5 27.3191 3.8247 1.1938 1193.7798 0.1143 0.8 3.2038 140  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 0.8284 30.8238 3.0665 0.8122 3.7019 99.4842 0.3979 33.6596 4.5576 2.5624 27.5327 1.8260 0.7126 0.8122 0.2653 66.3228 30.0657 3.1547  828.3542 712.6320  depth Tml 0.05 0.05  10-20 qa 10-20 qb  1.2269 1.9659  33.2167 33.486  0.2358 0.3169  23.5814 31.6875  0.8730 0.8730  1.0711 1.7162  30.4182 30.6648  0.7173 0.9717  0.6697 0.5662  669.7017 566.1798  0.15 0.15  20-30 sa 20-30 sb  1.6033 1.8223  33.9254 32.7038  0.3685 0.4348  36.8460 43.4783  0.8128 0.8128  1.3032 1.4812  31.0672 29.9485  1.1447 1.3021  0.8784 0.8791  878.4011 879.1096  0.25 0.25  30-40 ga 30-40 gb  1.8964 1.5518  32.5167 32.6318  0.4127 0.4053  41.2675 40.5306  0.7948 0.7948  1.5073 1.2334  29.7772 29.8826  1.2288 1.2112  0.8153 0.9820  815.2592 981.9721  0.35 0.35  40-50 qa 40-50 qb  1.2121 1.1038  32.1443 33.1571  0.3979 0.3390  39.7937 33.8983  0.7271 0.7271  0.8814 0.8026  29.4362 30.3636  1.1714 1.0293  1.3290 1.2824  1329.0402 1282.3979  0.45 0.45  50-60 ga 50-60 gb  1.3709 1.7373  34.1555 31.462  0.3979 0.5527  39.7937 55.2690  0.7235 0.7235  0.9918 1.2569  31.2779 28.8114  1.2447 1.5924  1.2549 1.2669  1254.9175 1266.8912  0.55 0.55  Sediment Extraction Data for C3-05 Total iron -1M CaCI2 Extraction weight of C3-33.1a C3-33.1b C3-33.5a C3-33.5b  weight of soln (g) seds (q) remarks 3.7732 31.2037 oxidized 32.0504 oxidized 2.9410 31.1014 5.9786 4.2612  31.0144 31.6094  C3-33.10a C3-33.10b  4.1725 3.6224  C3-34.2a  4.0951  31.0565 31.6954  C3-34.2b  3.1917  31.1161  C3-34.6a C3-34.6b C3-34.10a C3-34.10b C3-35.2a C3-35.2b  dry/wet cone mg/L ratio 14.897 0.9217  24.732 36.357 24.607  0.9217 0.9362 0.9362  18.532  0.9266 0.9266  17.523 oxidized oxidized  2.0613 2.2878 2.6598 3.0804  14.553 17.725 16.468 18.941  31.8180 31.6610 32.0467 31.2083  ml of soln  (q) 3.0186  11.281 42.729  0.8793 0.8793 0.8946 0.8946 0.9010 0.9010  mg total of  dry mass  2.3528 5.5106 3.9277  28.5748 29.3502 28.4811  3.9064 3.3914  28.4015 28.9463 28.4400  3.7944  Fe  depth (m) mg/g ug/g FeTot 10.14 0.1410 141.02 10.14 0.3311 0.1407 140.73 0.2208 220.84 10.26 1.2170 178.84 0.7024 0.1788 10.26 0.4257  0.2694 0.2064  269.41  10.36  0.6998  1.0524  206.35  10.36  29.0251  0.5379  0.1418  2.9574  28.4946  0.4993  0.1688  141.76 168.84  10.46 10.46 10.57  1.8440 2.0467 2.3965 2.7754  29.1374 28.9936 29.3468 28.5790  0.4240 0.5139 0.4833 0.5413  0.2299 0.2511 0.2017 0.1950  229.95 251.10 201.66 195.04  C3-35.6a C3-35.6b C3-35.10a C3-35.10b C3-36.2a C3-36.2b C3-36.6a C3-36.6b  2.5299 2.7685  31.9281  21.283  31.6939  2.2555 1.7304  31.5825 32.3071 31.3741 oxidized 31.2803 oxidized  24.351 19.201 17.328 10.765 12.354  1.9838 2.3000 2.8715  2.0981 2.2960  29.2382 29.0237  0.7963 0.7963 0.8524 0.8524  1.7961 1.3779 1.6910 1.9605  28.9217 29.5853 28.7309 28.6450  2.4686 1.9979 2.8372 2.5554  28.6755  0.3093 0.3539 0.4356  0.1764  176.45  11.28  29.4081 28.4452 28.4183  0.4214 0.5291 0.3511  0.2109 0.1865 0.1374  210.93 186.48  11.28 11.38 11.38  2.8901 1.6378  27.5899 28.6036  0.5238 0.2590  0.1813 0.1581  181.26 158.12  2.5932  27.5420 28.1733  0.5105 0.6323 0.5335  0.1969 0.2519 0.2466 0.2545  196.87  31.3137  15.190  0.8597  2.3239 3.2992  32.1136 31.0622  2.9715  C3-37.6a  3.4228 1.9397  31.0328 30.1282  14.330 18.600 12.354  0.8597 0.8600 0.8600 0.8444  C3-37.6b C3-38.9a C3-38.9b C3-39.2a C3-39.2b  2.9918 2.8964  31.2351  18.987 . 9.054  30.0759 30.7652 31.6441  18.536 22.445 18.411  0.8668 0.8668 0.8636  31.4211  17.532 37.598 23.803 11.020  0.8636 0.8869 0.8869 0.9048 0.9048 0.8063  C3-39.6a C3-39.6b  2.5051 2.2952  C3-39.10a C3-39.10b C3-40.2a . C3-40.2b C3-40.6a  2.9512 3.3853 2.4526 3.6368 1.9641  29.5900 31.3058 31.4247 31.5678 30.5803  C3-40.6b  1.9681  31.9050  oxidized oxidized oxidized oxidized  9.528 31.704 32.374  0.8444  0.8063  2.5105 2.1635 1.9822 2.6173 3.0023 2.2190 3.2905 1.5837  28.9781 28.7739 27.0971 28.6683 28.7772 28.9082 28.0039  1.5869  29.2170  0.7068 0.5553 0.5127  0.5045 1.0188 0.6824 0.3171 0.2754 0.8878 0.9459  0.2966 0.3078 0.3092 0.3720 0.1829 0.1805  0.3893 0.2273 0.1429 0.0837 0.5606 0.5961  296.58 307.82 309.19 372.05 182.91 180.51  10.87 10.87 10.97  0.8293 0.8293  C3-36.10b C3-37.2a C3-37.2b  C3-36.10a  0.6223  10.57 10.67 10.67 10.77 10.77  137.39  251.88 246.60 254.50 389.25 227.29 142.91 83.71 560.62 596.06  10.97 11.07 11.07 11.18 11.18  11.48 11.48 11.87 11.87 11.99 11.99 12.09 12.09 12.19 12.19 12.29 12.29 12.40 12.40 12.50  C3-40.10a C3-40.10b C3-41.2a C3-41.2b  2.4740 2.5169  30.6462 31.3841  30.747 25.476  0.8269 0.8269  2.0456 2.0811  28.0643 28.7400  0.8629 0.7322  0.4218 0.3518  421.82 351.82  12.50 12.60 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 C3-41.10a C3-41.10b  3.0875 2.3514 3.4287  31.2056 31.4894 30.6314  13.261 10.556 14.311  0.8666  2.6755 2.0065 2.9258  28.5766 28.8364 28.0507  0.3790 0.3044 0.4014  0.1416 0.1517 0.1372  141.64 151.71 137.21  12.70 12.80 12.80  0.8533 0.8533  C3-42.2a  0.8753  C3-42.2b  0.8753  13.11  0.3601  0.1755  175.46  13.11 13.21 13.21  31.2212  0.1202 0.0759 0.0557  0.0403 0.0453  40.25  30.1642 30.9004  0.0236  23.58  0.2411  28.5478  0.3661 0.3152  3.849  2.9855  2.515 1.803  1.6765 2.3626  31.5122 31.6386  10.923 12.429  C3-34.2W  3.7319  31.2212  C3-37.2W C3-41.6W  2.0956 2.9532  30.1642  C3-43.2a C3-43.2b  99.61 164.46 149.87  28.4592  2.2260 2.1032 2.0524  2.4931 2.4329  2.6131  0.1645 0.1499  2.4208  0.8519 0.8436 0.8436  12.824  2.8418  C3-42.10b  0.0996  0.8519  8.473  31.1742  C3-42.10a  13.00 13.00  0.2031 0.1751  31.0774  2.8078  31.0213 30.7062  175.10  2.3266  0.3337 0.4074  14.488  1.9823  12.90 28.4078 28.1192  0.8286 0.8286  C3-42.6a C3-42.6b  12.90  11.746  1.6426  28.8573 28.9731  203.14  pure water extraction  30.9004  45.25  107  Sediment Extraction Data for C2-05 Total iron - 1M CaCI2 Extraction mg total of dry sed weight of gg/g FeTot depth (m) ml of soln Fe mg/g seds(g) soln (g) remarks cone mg/L dry/wet ratio mass (g) 0.71 28.4582 0.2259 0.1241 124.08 0.8412 1.8209 2.1647 31.0764 7.939 0.71 28.5044 0.2392 0.1135 113.46 0.8412 2.1079 2.5059 31.1268 8.390 0.1482 148.15 0.81 27.5789 0.3849 30.1162 13.956 0.8348 2.5980 3.1120 0.1784 178.37 0.81 29.2317 0.3489 11.934 0.8348 1.9557 2.3427 31.9210 0.91 0.4560 0.1673 167.31 16.882 0.8392 2.7255 27.0115 3.2477 29.4966 0.91 0.3960 0.1919 .191.91 0.8392 28.9708 13.668 2.0633 2.4586 31.6361 1.02 0.4408 0.1572 157.16 0.8407 2.8047 28.3678 15.538 3.3363 30.9776  weight of C2-2.2a C2-2.2b C2-2.6a C2-2.6b C2-2.10a C2-2.10b C2-3.2a  0.1647  164.65  0.2061 0.1657 0.1876 0.1608 0.1320 0.1641  206.08 165.70 187.55 160.77 132.01 164.09  0.3221  0.1604  160.35  1.42  0.4009 0.5008  0.1275 0.2209 0.2485  127.49 220.94 248.52  1.42  C2-3.2b  3.1962  31.2271  15.471  0.8407  2.6870  28.5962  C2-3.6a C2-3.6b C2-3.10a C2-3.10b C2-4.2a C2-4.2b  2.0029  30.9141 31.6284 31.3643 30.0623 30.0308 30.2483  12.229  0.8388  11.436 20.093 18.801 16.210 14.383  0.8388 0.8320 0.8320 0.8254 0.8254  1.6800 1.9990 3.0771 3.2194 3.3770 2.4280  28.3096 28.9637 28.7219 27.5296 27.5007 27.6999  C2-4.6a  2.2393 3.5054 2.5452  31.0213 31.2693 29.8346 30.7207  11.339  0.8971  2.0088  14.000 18.329 14.265  0.8971 0.8905  3.1445 2.2666 1.6148  28.4078 28.6349 27.3211  31.2585  13.028 15.148 13.077 14.425  0.4013 0.3729  2.3833 3.6984 3.8695 4.0911 2.9414  C2-4.6b C2-4.10a C2-4.10b  1.8133 2.2367  C2-5.2a C2-5.2b C2-5.6a C2-5.6b C2-5.10a C2-5.10b C2-6.2a C2-6.2b  -  2.4664 2.3462 2.6492  -  30.1562 32.1163 30.5023  0.4424 0.3462 0.3312 0.5771 0.5176 0.4458 0.3984  1.02 1.12 1.12 1.22 1.22 1.32 1.32  1.52 1.52  1.8635  28.1325 28.6250  1.63  2.0548 2.1588 2.4376  27.6156 29.4105 27.9325  0.4183 0.3846 0.4029  0.2001 0.2036 0.1782 0.1653  200.13  0.8331 0.9201 0.9201  203.58 178.16 165.30  1.63 1.73 1.73 1.83 1.83 1.93 1.93  0.8905 0.8331  -  2.4225 2.9378  31.7772 30.6230  13.851 15.201  0.8650 0.8650  2.0954 2.5412  29.1000 28.0430  0.4031 0.4263  0.1924 0.1678  192.35 167.75  C2-7.5a C2-7.5b C2-7.11a C2-7.11b  2.4931 2.0716  30.8071 31.1386 30.5946 30.2775  10.367 9.525 14.328  0.8769 0.8769 0.9111 0.9111  2.1863 1.8166  28.2116 28.5152  0.1571 0.1922  28.3059 28.6615  0.4860 0.4244 0.3994 0.3608 0.3797 0.3486 0.3692 0.3174  133.78 149.51 170.71 157.11  2.4181 2.3952  28.0170 27.7266 27.7679 28.3014 28.4692 28.8174 28.2974  0.1338 0.1495 0.1707  C2-8.3a C2-8.3b C2-8.7a C2-8.7b C2-8.11a  2.3516 3.0933 2.2081 2.1872  0.2925 0.2716 0.4014  28.5277  0.3744  0.1260 0.1441 0.1364  28.7389 29.0623  0.3944  0.1598  159.80  0.3279 0.5146  0.1645 0.2737  164.50 273.66  0.6228  0.2501  250.09  3.07  0.3858 0.3917  0.1506  150.56  3.18  0.1726  3.18  0.4229  0.1953 0.2147  172.58 195.27  C2-8.11b C2-9.3a C2-9.3b C2-9.7a C2-9.7b C2-9.11a  2.5811 3.3952  2.1560 2.3349 2.5959 3.1510  30.3226 30.9051 31.0884 31.4686 30.9008 30.9100 31.2984  17.528 15.283 14.111 12.675 13.177 12.320  0.9131 0.9131 0.8835 0.8835 0.9302  1.9048 2.0629 2.4147 2.9310  13.045 11.075  0.9302 0.9477  31.1523  13.125  0.9477  2.8292 2.2847  31.3829 31.7360  13.725 11.283  0.8725  2.1007  18.718 22.625  0.8725 0.8952 0.8952  1.8805 2.4902  2.3251 2.8964  2.2035 2.7449 2.4684 1.9933  27.4939  C2-9.11b C2-10.3a  2.7818  30.0233 30.0583  3.0120  30.8654  13.651  0.8508  2.5627  27.5259 28.2650  C2-10.3b  30.7671  13.902  C2-10.7a  2.6675 2.5557  32.8773  2.2696 2.1657  28.1750 30.1074  C2-10.7b  1.9969  29.9405  14.046 13.252  0.8508 0.8474 0.8474  1.6922  0.3633  C2-10.11a  3.5505  3.0308  4.6640  15.503 15.271  0.8536  C2-10.11b  29.7785 30.7071  27.4180 27.2697  0.8536  28.1201  0.4294  C2-11.3a C2-11.3b  3.6858 4.1562  30.4404 31.0083  14.869 17.604  C2-11.7a  2.3961  16.352  2.0120  27.8758 28.3959 28.5746  C2-11.7b  4.3445  31.2035 30.2111  0.8465 0.8465 0.8397  3.9813 3.1202 3.5184  22.397  0.8397  3.6481  0.1826 0.1894 0.1841 0.1444 •  192.19 182.59 189.44 184.07 144.38 125.98 144.06 136.41  C2-4.6W C2-10.7W  1.6353 2.9805 2.2211  29.4294 30.0873 29.7663  2.347 1.292 2.991  2.46 2.46 2.57 2.57 2.67 2.67 2.77 2.77 2.87 2.87 2.97 2.97 3.07  214.72  3.28 3.28  0.1395 0.1079  139.49  3.38  107.86  3.38  0.4145  0.1328  0.4999 0.4673  0.1421 0.2322  132.84 142.08 232.23  3.48 3.48 3.58  27.6658  0.6196  0.1699  169.85  3.58  1.3082  29.4294  0.0691  30.0873 29.7663  0.0389 0.0890  0.0528 0.0163 0.0501  52.80  2.3844 1.7769  0.4228  pure water extraction C2-3.6W  2.34 2.34  16.30 50.11  108  Sediment Extraction Data for C1-05 Total iron - 1M CaCI2 Extraction sed weight (g) C1-4.4a  4.0170  cone  soln weight remarks  (g) 31.6111  ml of soln  dry/wet ratio (g)  31.4  0.7823  Fe  mg/g  depth (m)  ug/g FeTot  3.1423  28.9479  0.9090  0.2893  289.2667  2.4306  28.2410  1.1409  0.4694  469.3995  3.0089  30.8392  40.4  0.8078  0.35  2.0408  28.7711  0.8897  0.4360  435.9722  0.45  0.35  0.8078  C1-4.8b  0.25 0.25  0.7823  C1-4.4b C1-4.8a  mg total of  dry mass  mg/L  C1-5.0a  2.7502  31.4180 oxidation  30.925  0.7421  C1-5.0b  4.8950  0.7421  3.6324  27.6412  1.3599  0.3744  90.9  2.6265  30.0601  2.7325  1.0404  C1-5.4b C1-5.8a C1-5.8b  0.6519 0.6519  374.3923 1040.3592  0.45  4.0290  30.1842 oxidation 32.8256 oxidation  49.2  C1-5.4a  2.0453 2.3665  30.5517 oxidation 31.6255 oxidation  24.3 21  1.6154  0.4209 0.3254  420.8634 325.3919  3.3453  32.0328 oxidation  20.95  27.9777 28.9611 29.3341  0.6799 0.6082  C1-6.0a  0.7898 0.7898 0.8587  0.6145  0.2139  213.9301  0.66 0.66 0.76  0.6023  117.3835  0.86  0.5323  0.1174 0.1314  0.86  1.06  C1-6.4b C1-6.8a  5.3993 4.2619  31.3589  4.5503  31.0453 30.9955  5.2409  31.9375  20.975 18.725  0.9504  5.1314  0.9504  4.0504  28.7169 28.4298  36.3  0.9505 0.9505  4.3253  28.3842  1.0303  0.2382  131.4305 238.2157  28.35  0.9560  5.0104  29.2468  0.8291  0.1655  165.4861  20.55  0.9560 0.8763 0.8763  2.6397  0.5698 0.5550  0.2159  2.8830  27.7266 29.2082  0.1925  215.8502 192.4889  0.8429  2.1325  28.3547  1.0002  0.4690  469.0365  1.27  27.5897  1.5078  28.5269  432.4635 443.1931  1.27 1.37  27.8026 27.9553  1.0869 1.4916  0.4325 0.4432 0.4244 0.2772  424.4033 277.1625  1.37 1.47  C1-6.8b C1-7.0a C1-7.0b C1-7.4a  0.76  0.8587  C1-6.0b C1-6.4a  1.8691 2.8727  C1-7.4b  3.0125 3.2902  30.2775 31.8953  C1-7.8a  2.5300  30.9633  19 35.275  C1-7.8b  4.1364 2.9480  54.65 38.1  0.8429  C1-8.0a C1-8.0b  30.1279 31.1514  0.8319  3.4865 2.4524  53.65 36.35  0.8319 0.8619  3.5146 3.6664  4.2249  30.3604  C1-8.4a C1-8.4b  4.2539  30.5272  C1-10.6a  3.1711  C1-10.6b C1-10.10a C1-10.10b  3.0876  31.6341 30.7447  2.8348 3.6512  32.5882 30.4902  C1 -11.2a  2.6255  31.2826  C1-11.2b  2.6677 2.6787  31.0192  C1-11.10a  4.8755 3.1097  C1-11.10b  1.0162  0.6286 0.6131  0.2435  21.7  0.8141  2.5816  28.9690  0.8141  2.5136  0.7995 0.7995  2.2666 2.9193  28.1545 29.8427 27.9214  0.6640 0.7755  0.8184  2.1488  28.6471  0.4691  16.3 21.525  0.8184  2.1833  28.4059  0.8305  28.3713  0.4630 0.6107  29.6708 31.9504  33.875  0.8305  2.2246 4.0489  27.1711  0.9204  0.2273  21.025  0.8199  30.2569  19.7  0.8199  29.2586 27.7078  0.6152  2.4422  2.5497 2.0024  C1-12.2a  3.0867  30.0925  19  0.8225  2.5389  C1-12.2b  2.6471  29.0593  0.8225  C1-12.6a  31.7784  0.8326  2.1773 2.2141  C1-12.6b  2.6591 2.3676  18.025 16.15  31.3838  16.3  0.8326  C1-12.10a  2.4155  31.6340  19.275  C1-12.10b  3.6738  C1-13.2a  4.4334  31.2115 30.6452  C1-13.2b  3.6472  C1-13.6a  3.3694  C1-11.6b  0.96 0.96 1.06 1.17 1.17  1.47  0.8619  21.775 22.25  C1-11.6a  0.56 0.56  0.2439 0.2930 0.2657  243.5050 243.8990 292.9559 265.6519  3.25 3.25 3.35  218.3106  3.35 3.45  212.0723 274.5216  3.45 3.56  227.3235 241.2687  3.56  0.2413  0.5458  0.2726  272.5942  3.66  27.5572  0.5236  0.2062  206.2297  3.76  26.6111  0.4797  0.2203  3.76  0.4700  0.2123  1.9714  29.1011 28.7397  220.3048 212.2712  0.4685  0.2376  237.6325  3.86  0.8278  1.9995  28.9689  0.5584  0.2793  279.2582  3.96  24.175  0.8278  28.5820  227.2114  3.96  0.8197  28.0634  0.6910 0.6742  0.2272  24.025  3.0411 3.6341  0.1855  185.5290  4.06  30.3456  17.3  0.8197  2.9896  27.7890  0.4807  0.1608  160.8070  4.06  31.3686  9.25  0.8179  2.7560  28.7258  0.2657  0.0964  96.4133  4.17  0.8179  0.0000 0.1930  192.9527  4.27  0.2044  204.4175  4.27  30.9815  27.775 16.375  C1 -13.6b  0.2183 0.2121 0.2745  3.66  3.86  4.17  15.85  0.8179  2.2106  26.9114  2.2891  29.3872 31.2484  13.375  0.8179  1.8723  28.6158  0.4265 0.3827  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  0.6130  0.5333  1.2876  29.7323  17.98  1.0401  1.3029  30.4225  17.2  1.0525  0.4895 0.4792  0.4707  C1-4.8b1  0.8078 0.8078  533.3480 470.6555  0.25  C1-4.8a1  27.5510 27.2274 27.8594  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 1.8554  30.0348 29.9842  23.8 21.68  0.8587  2.1297  27.5044  0.6546  0.3074  307.3694  0.76  0.8587  1.5933  29.8850  2.7250  30.1320  28.38 27  0.9505 0.9505  2.4589 2.5902  0.7450  0.3159 0.2876  373.6305 315.8697  0.76  2.5868  0.5953 0.7767  0.3736  C1-6.8a1 C1-6.8b1  27.4581 27.3672 27.5934  C1-7.0a1  2.0423  30.5551  18.35  0.9560  0.5134  1.3972  29.7117  12.15  0.9560  1.9525 1.3357  27.9809  C1-7.0b1  27.2085  0.3306  C1-13.6a1  2.0525  29.6924  14.9  0.8179  C1-13.6b1  2.1813  30.3984  14.73  0.8179  1.6788 1.7842  27.1908 27.8374  0.4051 0.4100  C1-13.10a  2.7027  C1-13.10b redone  C1-6.0b1  0.35  287.6275  0.96 0.96  0.2630  262.9745  1.06  0.2475  247.4905  0.2413  241.3243  1.06 4.17  0.2298  229.8215  4.17  109  Appendix  C  Lab Procedures for Iron Sediment Extractions  1M CaCI extractions: 2  Equipment used: Lab balance:  Denver Instrument XP-300 Low Budget balance  Precision balance: Mettler Toledo AE 100 electronic analytical balance Repeater pipette: combitip  Eppendorf Repeater Pipette model 4780 with a 50 ml  Pipette:  Eppendorf Research Series 2100 Adjustable Volume Pipetters, 10-100 ul and 100-1000 pi  Glovebox:  Vinyl Anaerobic Glovebox, Type B  Spectrophotometer: Hach DR/2400 Spectrophotometer Centrifuge tube:  VWR 50 ml flat top sterile graduated plastic centrifuge tube  Enough C a C ^ 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" ) 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). 1  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 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. 2  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.  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: combitip  Eppendorf Repeater Pipette model 4780 with a 50 ml  Pipette:  Eppendorf Research Series 2100 Adjustable Volume Pipetters, 10-100 pi and 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:  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  Appendix  D  Analysis Procedure for P A H 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. 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. 1  118  Appendix  E  PhreeqC Geochemical Modelling Input File  SOLUTION_SPREAD -temp 11 -pe -2 -units mg/l Description P6-05-01 P6-05-02 P6-05-03 P6-05-04 P6-05-05 P6-05-06 P6-05-07 P6-05-08 P6-05-09 P6-05-10 P6-05-11 P6-05-12 P6-05-13 P6-05-14 • P6-05-15 P22-05- 13 P22-05- 8 P22-05-4 P22-05- 1 P22-05- 2 P22-05- 3 P23-05- 1 P23-05- 6 P23-05- 7 P23-05- 8 P23-05- 9 P23-05- 10 P23-05- 11 P23-05- 13 P23-05- 14 P23-05- 15 P23-05- 16 P23-05- 17 P23-05- 18 P23-05- 19 P23-05- 20 P3-06-R P3-06-03 P3-06-04 P3-06-05 P3-06-06 TR-0/10 TR-10/20 TR-20/30 TR-30/40 TR-40/50 TR-50/60  Number 1 2 3 ,4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47  Br  pH 7.67 6.33 6.12 6.18 6.18 6.24 6.29 6.31 6.36 6.37 7.07 7.14 7.15 7.07 7.03 7.63 6.81 7.06 7.03 7.3 7.67 7.1 6.65 6.34 6.54 6.6 6.58 6.6 6.54 6.52 6.47 6.46 6.52 6.63 6.59 7.25 7.2 6.57 6.72 6.75 6.85 6.4 6.4 6.4 6.4 6.4 6.4  F  Cl 0 0 0 . 0 . 0 - 0 . 0 0 0 0 0 0.075 0.184 0.284 0.608 0 1.27 2.74 3.3 3.8 4.2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.406 1.68 3.27 0 0 0 0 0 0  0.57 5.85 7.58 7.19 12.9 •12.5 6.96 11.4 4.83 5.18 14.1 24.8 66.4 104 210 0.61 462 955 1250 1430 1590 0.8 2.94 2.95 2.87 3.02 2.97 3.04 3.62 3.8 4.37 4.38 3.69 5.49 5.41 6.3 1.78 14 136 544 1010 24.5 10 8.05 14.5 5.82 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) END  S(6) 0.03 0.034 0.035 0.031 0.033 0.029 0.023 0.028 0.025 0.025 0.028 0.029 0.029 0.028 0.029 0.028 0 0 0 0 0 0.028 0.042 0.048 0.04 0.038 0.034 0.029 0.037 0.037 0.034 0.032 0.027 0.03 0.027 0.026 0.036 0.052 0.06 0 0 0 0 0 0 0 0  Ba 6.23 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5.6 0 0 0 0 0. 6.09 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5.99 0.3 0.2 3 1 8.19 3.83 0.98 0.5 0.58 0.82  0 0.025 0.035 0.036 0.014 0.017 0.012 0.016 0 0.019 0.017 0.01 0.025 0.04 0.05 0.01 0.184 0.408 0.584 0.416 0.133 0 0.049 0.077 0.076 0.077 0.044 0.086 0.066 0.046 0.039 0.047 0.043 0.038 0.034 0.03 0.014 0.044 0.091 0.278 0.407 0.11 0.11 0.099 0.11 0.1 0.086  B  '  Fe  Ca 0 0 0 0.14 0 0 0 0 0 0 0 0 0 0 0 0 0.16 0.27 0.44 0.57 0.36 0 0 0 0 0 0 0.11 0 0 0 0 0.11 0.12 0.11 0 0 0.19 0.21 0.25 0.38 0.05 0.07 0.14 0.19 0.24 0.22  10.2 13.1 17.4 25.7 11.8 15.8 11.7 20.2 13.4 26.5 27.5 17 39.9 62.3 66.7 117 188 180 231 143 26.7 11.6 14.6 22.9 21.2 21 11.1 21.9 24.9 25.8 29 30.2 47.1 62.5 71.5 74.2 13.9 33.7 70.4 155 200 55.2 54.5 39.5 38.5 36.2 32:9  1.23 19.9 32.9 55.9 21.1 25.9 14.8 •19.3 9.98 16.3 13.6 7.56 16 21.7 23.8 0.078 • 38.2 22.8 25.4 10.3 1.35 0.072 17.6 31.9 34.2 35.5 18.3 42.8 69.3 72.1 72.4 71.5 53.1 46.6 23.4 22.4 0.114 62.4 85.7 90.1 71.7 8.3 25 33 35.7 34 36  Mg 2.25 4.55 7.99 12.9 5.67 7.61 4.84 7.28 4.32 8.36 8.62 5.41 13.1 20.7 22.3 2.38 44 42 60.8 61.3 34.9 1.88 9.54 14.9 14.6 14.4 7.65 15.1 13.4 13.5 13.1 14.6 21.7 28.6 28.7 25.7 3.63 16.3 27.4 42.9 48.8 10 9.32 8.48 9.23 9.12 8.68  Mn . 0.0674 0.964 1.36 2.29 0.896 1.13 .0.698 0.971 0.548 0.965 0.869 0.49 1.05 1.52 1.77 0.0188 5.32 6.21 772 2.95 0.278 0.0212 0.412 0704 0.748 0.797 0.428 0.975 1.51 1.77 1.93 2.26' 3.71 2.4 0.635 0.558 0.0105 2.76 4.55 6.65 6.56 3.78 3.84 2.67 2.77 2.53 2.25  P  Na  K 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.32 0.36 0.68 0.66 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.2 0.2 0.3 0.2 0.2 0.4  '  . 0 0 0 2.9 0 0 0 0 0 0 0 0 2.1 3.1 3.9 0 17.3 31 42.1 37.1 15.7 0 0 0 0 0 0 0 0 0 2 2.1 0 2.2 0 0 0.1 4 7.3 18.3 31.1 3.6 3.7 4.8 5.8 6.7 6.5  1.7 5.32 11 17.6 7.15 8.17 5.38 7.99 4.69 8.48 8.54 4.89 9.85 11.9 10.3 2.04 19 15.1 20.3 15.5 5.74 1.5 13.1 19.2 17.5 18.2 9.18 17.9 16.9 17.2 17.3 18.9 22.4 25.2 25.3 22.5 2.76 17.9 19.1 17.6 17.6 6 8.7 11.2 12.2 16.7 13.3  0 3.7 7.1 9.4 3.6 4.2 2.2 3.2 0 3.1 2.8 0 3.8 5.7 9.9 0 63.6 329 533 616 343 0 10.2 16.2 15.7 16.6 8.9 17.7 18 17.8 16.7 19.4 10.3 10.1 10.5 8.5 2.9 6.1 16.1 110 342 7.67 5.99 6.48 8.22 8.36 8.48  Sr Zn Alkalinity 0.0337 28.39985 0.0507 0.0822 88.704 0.0569 0.0857 0.504 143.2515 0.128 0.0934 235.7185 0.0548 0.0177 81.849 0.0719 0.0282 110.737 0.0492 0.0249 71.894 107.668 0.079 0.0526 0.0113 63.2735 0.0492 0.0939 0.0303 130.9885 115.351 0.0953 0.0118 0.0578 0.006 43.2903 0.137 0.0256 99.696 0.207 0.012 150.6155 33.1144 0.246 0.0289 0.062 0.0062 32.3881 0.781 0.0421 237.0345 125 1.07 0.0456 1.49 200 0.0588 1.15 0.0221 130 230 0.368 0.0073 0.0488 0.0078 250 125.954 0.0708 0.0543 0.11 0.0252 207.99 0.108 0.0123 205.6435 0.11 0.0148 208.443 0.0071 107.8285 0.0612 0.128 0.0092 229.339 0.15 0.0077 278.0605 0.0138 285.5425 0.162 0.182 . 0.027 292.173 0.202 0.0215 306.353 0.0133 325.9345 0.225 0.273 0.0176 378.528 0.0313 354.998 0.292 0.281 0.0184 338.052 46.372 0.0702 0.132 0.145 0.0977 303.628 0.286 0.182 347.792 0.636 0.075 331.23 436.12 0.946 0.0325 0.31 0 137 0.27 0 213 0.19 0 184 0.19 0 182 0.17 0 183 0.16 0 152  

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