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A field investigation into the fate and transport of naphthalene in a tidally forced anaerobic aquifer Bianchin, Mario 2001

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A F I E L D I N V E S T I G A T I O N I N T O T H E F A T E A N D T R A N S P O R T O F N A P H T H A L E N E I N A T I D A L L Y F O R C E D A N A E R O B I C A Q U I F E R by Mario Bianchin B.Sc , Simon Fraser University, 1998 THESIS SUBMITTED IN PARTIAL FULFILLMENT OF T H E REQUIREMENTS FOR T H E D E G R E E OF MASTER OF SCIENCE in the Department of Earth and Ocean Sciences We accept this thesis as conforming to the required standard UNIVERSITY OF BRITISH COLUMBIA 2001 © Mario Bianchin 2001 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of The University of British Columbia Vancouver, Canada Date A b s t r a c t The objective of this research is to investigate the fate and transport of naphthalene in a tidally influenced aquifer. Biodegradation, sorption, dispersion, dilution and physical removal of sediments by scour may all contribute to naphthalene loss in a sub-fluvial aquifer. A multiple-line of evidence approach was pursued to investigate processes responsible for natural attenuation of naphthalene. This research included the following studies: (1) bathymetric survey (2) contaminant plume characterization offshore using the Waterloo Drive Point Profiler (3) onshore tracer test and, (4) reactive tracer test offshore using 1 4 C -naphthalene. Over the course of a year, the riverbed appears to be in quasi-equilibrium. Sediment transport occurs continuously as migrating dunes and secularly as scour and deposition during a freshet-flood wave event. Any appreciable amount of sediment scoured away is "new" sediment deposited temporarily during the freshet-flood wave. The study was limited in that it did not address interannual variability of riverbed changes. Also, surveys were too infrequent to conclusively state if contaminated sediments of the aquifer are scoured away to any appreciable extent. Results of the onshore tracer study suggest that dispersion in the upland portion of the aquifer does not appear enhanced by tidal forcing. Further, bromide tracer plume transport offshore suggests that dispersion and or dilution did very little to reduce bromide concentrations over the 230 day study period. The immobility of the offshore bromide plume confirmed the presence of a "low flow" zone associated with onshore pumping operating since 1995. ii Profiling of the contaminant plume offshore confirmed the presence of a large anaerobic plume consisting mainly of naphthalene. The plume was at least 200m in width and could be as wide as 300m, consistent with profiling conducted onshore in 1997. During both the 1997 and 1999 profiling events the offshore portion of the plume existed in a zone of low groundwater flow due to hydraulic containment. This suggests that in this zone offshore a state of quasi-equilibrium may exist between competing fate and transport processes, namely, degradation, advective transport from the source area and desorption of naphthalene from sediments. Results of the offshore reactive tracer study confirmed that anaerobic degradation is occurring with the mineralization of 1 4 C -naphthalene to 1 4 C-CC»2. Regression analyses of the 1 4 C-CC»2 data yielded a rate of C O 2 production of 3E-9 mmol 1 4 C / L » d a y . The distribution of radionuclides among C H 4 and C O 2 fractions was considered to estimate half-life values for naphthalene ranging from 0.72 to 2.9 years. Assuming no fractionation of radionuclides, a half-life for naphthalene under the site conditions was 1.72 years. Migration of the 1 4C-naphthalene plume with respect to that of the bromide plume revealed that retardation of naphthalene is fairly low at R = 1.7. In summary, results of this research indicate that anaerobic degradation plays a significant role in the fate and transport of naphthalene in this portion of the sub-fluvial aquifer. iii Table o f C o n t e n t s Abstract ii List of Figures vi List of Tables ix Acknowledgments xi Chapter One: Introduction 1 Study Approach and Objective 4 Chapter Two: Site Description 6 Chapter Three: Methods .' 18 Bathymetric Surveys 18 Contaminant Plume Characterization 20 Onshore Tracer Study 23 B r Tracer 24 Injection Characteristics 25 Injection and Monitoring Procedures 26 Reactive tracer test; offshore 29 1 4C-naphthalene Tracer 30 Injection and Monitoring Procedures 33 Groundwater Sample Analysis 34 Chapter Four: Results and Discussion 58 Riverbed Stability 58 Contaminant Plume Characterization 61 Organics 61 Inorganics 63 Dispersion and Groundwater Velocity; Onshore Tracer Study....65 Biodegradation; Offshore Tracer Study 71 iv Chapter 5: Summary and Conclusions 96 References 99 Appendix A: Approvals and Permits 104 Appendix B: 1 4C-Naphthalene Supplier Specifications 124 Appendix C: University of Waterloo Analytical Methodologies 126 Appendix D: Method for Bromide Analysis 135 Appendix E: Bathymetric Survey Contour and Post Plots 149 Appendix F: Offshore Profiling Organic Data 157 Appendix G: Offshore Profiling Inorganic Data 165 Appendix H: Offshore Profiles of Inorganics 172 Appendix I: Onshore Bromide Results and ASL Analytical Reports 177 Appendix J : Offshore Bromide Results 192 Appendix K: Offshore 1 4C-Activity Results 209 v L i s t o f F i g u r e s Figure 1: Site Map (modified from Anthony, 1998) 13 Figure 2: Hydrograph of Fraser River. Discharge at Hope station for A: 1998 - 1999 and B: 1999-2000 14 Figure 3: Gradients measured at site 15 Figure 4: Cross-section of Naphthalene distribution 16 Figure 5: Naphthalene, C02 and electron acceptors along plume core : 17 Figure 6: Schematic of bathymetry equipment setup 37 Figure 7a: Waterloo Drive Point Profiler Setup 38 Figure 7b: Photo of Profiler Tip Designed at UBC with modified harrimering head 39 Figure 8: View of Seiner and on-deck setup of WDPP 40 Figure 9: Operation of the WDPP 41 Figure 10: Location of injection points (figure modified from Anthony 1998) 42 Figure 11: Onshore injection interval (figure modified from Anthony 1998) 43 Figure 12a: Schematic of Injection System 44 Figure 12b: Picture of Injection system 45 Figure 13: Picture of injection and monitoring wells 46 Figure 14: Picture of custom made sampling rig involved in grouting profiling holes 47 Figure 15: Picture of modified AW coupling 48 Figure 16: Orientation of monitoring wells and additional profiling points 49 v l Figure 17: Bromide distribution 39 days after injection 50 Figure 18: Transect A-A': Injection location with respect to naphthalene distribution in cross section 51 Figure 19: Schematic of Naphthalene-benzene-UL-14C undergoing methanogenic degradation to carbon dioxide and methane 52 Figure 20a: Offshore groundwater extraction/injection setup 53 Figure 20b: Injection system set up on deck 53 Figure 21: Determining location offshore by triangulation 54 Figure 22: Plan view of all offshore profiling points (Offshore tracer study only) 55 Figure 23: Cross view plot of all offshore profiling points (Offshore tracer study only) 56 Figure 24: Plot of bromide concentration by Direct measurement (Field) vs Known addition (Lab) 57 Figure 25: 3D representation of river bed in Sapperton Channel offshore of site 81 Figure 26: River bed profile along A-A' transect over 7 surveys 82 Figure 27: River bed profile along B-B' transect over 7 surveys 83 Figure 28: River bed profile along A-A' transect pre- and post freshet. 84 Figure 29: River bed profile along A-A' transect pre- and post freshet. 85 Figure 30: A-A' cross section of naphthalene A: Anthony (1998) B: this study 86 Figure 31: B-B' cross section of naphthalene 87 Figure 32: Breakthrough curves at MW1 88 Figure 33: Breakthrough curves at MW2 89 Figure 34: 3DADE Analysis of Breakthrough curve at MW1-3 90 Figure 35: 3DADE Analysis of Breakthrough curve at MW1-3 91 vii Figure 36: 3DADE Analysis of Breakthrough curve at MW2-1 92 Figure 37: Snapshots of bromide and 1 4C-naphthalene distributions offshore 93 Figure 38: Bromide vs 1 4C-total in groundwater 94 Figure 39: Bromide vs 1 4C-total in groundwater 95 viii L i s t o f Tables Table 1: Aquifer Property Estimates 11 Table 2: Chemical and physical properties of Creosote 12 Table 3: Bromide concentration of extracted and injected groundwater for the onshore tracer test 78 Table 4: Characteristics of injected groundwater for the offshore tracer 79 Table 5: Summary of 1 4C-Activity analyses on groundwater samples 80 ix Eva, meine kleine Schildkroete X A c k n o w l e d g m e n t s I owe many thanks to Dr. Roger Beckie for giving me the opportunity to work with him on a project of this magnitude and significance. It provided experience in many aspects of project management but, more importantly an understanding of fate and transport processes in a tidally-forced aquifer. I'm also grateful for the assistance, guidance and support provided by Dr. Les Smith throughout this project. This research was made possible through financing by Domtar Inc., Natural Sciences and Engineering Research Council of Canada, Science Council of British Columbia Graduate Research Engineering And Technology (GREAT) Scholarship and sponsorship from Guy Patrick of Golder Associates Ltd. I would like to recognize Glenn Budden and the Crew of the Ocean Venture. Your professionalism in combination with a constant sense of humility made working in the field an enjoyable and rewarding experience. Many thanks! I would like to thank all my fellow graduate students especially Justin, Craig, Petros, Sean, Rina, and Peter, as well as, the many undergraduates who participated in the research. xi C h a p t e r One : I n t r o d u c t i o n Creosote contamination of groundwater and soil occurs at up to 800 wood-preserving facilities in North America [Environment Canada 1993; USEPA 1992], and up to seven sites along the Fraser River in the greater Vancouver region [Environment Canada 1996]. Creosote is a complex mixture of hydrocarbons derived from coal-tar distillation. It consists of approximately 85% polycyclic aromatic hydrocarbons (PAHs), 10% monocyclic aromatic hydrocarbons (MAHs) such as BTEX (Benzene, Toluene, Ethyl-benzene and Xylene), and 5% N-, S-, and O-heterocyclics (Mueller et al. 1989). These organic compounds have been found to be toxic to aquatic life at low concentrations (1 p-g/L naphthalene and 0.3 mg/L Benzene)(BC Environment 1994, C C M E 1995). Consequently, creosote-derived contaminated groundwater discharging to aquatic systems has become a focal point for environmental investigations and legal action by both the provincial and federal governments [Environment Canada 1996]. Research has provided insight into the mobility, fate and persistence of creosote in groundwater (Mueller et al. 1989, Fowler et al. 1993, Anthony 1998, King and Barker 1999, King et al. 1999). It was found that historic creosote plumes evolve to a point where slower moving components such as naphthalene become the dominant and significant contaminant. Generally speaking, as a creosote plume evolves 1 components with lower distribution coefficients (Kd), being more mobile, are more easily transported out of the source zone by advection. The more mobile fractions dominate the plume front and undergo biodegradation under aerobic conditions. In time, oxygen levels within the plume become depleted within the plume and biodegradation at the plume fringes and the dissolution of the compound at the source zone become the rate controlling factors in its evolution (Fowler et al. 1993). Less mobile components such as naphthalene lag behind the plume front existing under anaerobic conditions. Under anaerobic conditions they are persistent and become the significant contaminant. The evolution of a creosote plume to naphthalene dominance under anaerobic conditions presents a difficult problem in terms of site remediation. To some degree all of the compounds making up creosote are biodegradable under the right environmental conditions (Mueller 1989). However, anaerobic degradation of naphthalene has only been documented under nitrate- (Mihelcic and Luthy 1988, Durant et al. 1995) and sulphate- reducing conditions (Thierrin et al. 1995, Coates et al. 1997). To the knowledge of the author, no studies have been able to clearly demonstrate biodegradation under methanogenic conditions. Howard et al. (1991) lists a range of naphthalene degradation rates as half-life (ti/2) under anaerobic conditions from a low of 25 days to a high of 258 days. 2 Biodegradation is only one of a few possible fate and transport processes that may contribute to the natural attenuation or "reduction in concentration" of contaminants in groundwater (Wiedemeier et al. 1999. p. 2). Other processes include dilution, dispersion, sorption, volatilization and abiotic transformations. The effects of tidal forcing complicate the determination of groundwater flow directions and contaminant transport and requires more quantitative approaches for proper characterization (Marquis and Smith 1994). Oscillating groundwater flows, as a result of tidal forcing on an aquifer, may lead to significant dilution (recharge by river) of contaminants (Wiedemeier et al. 1999, p. 151). The mixing of two distinct water types through influx of river water at the aquifer-river interface (hyporheic zone) will lead to a change in redox chemistry (Vroblesky and Chapelle 1994) and act as a 'biological filter' (Gilbert et al. 1997). In addition, oscillating groundwater flow leads to longer flow paths and greater spread of the contaminants longitudinally, and transversely leading to subsequent concentration reduction (Unger 1996, Yim and Mohsen 1992). The partitioning of contaminants from aqueous to solid phase reduces the contaminant concentrations in groundwater only temporarily. It may appear permanent if the rate of desorption is sufficiently low. The slow exchange from solid to aqueous phase may 3 mask degradation (shrinking of plume) in terms of plume stability assessment. Indeed, attributing the reduction in concentration to the responsible processes in an environment, such as an aquifer under tidal forcing, where four or more processes maybe significant contributors provides an intriguing investigative challenge. Study Approach and Objective The objective of this research is to investigate the fate and transport of naphthalene in a tidally influenced aquifer. The site is the focus of several consulting reports, the first in 1980, and the Master's Thesis research of University of Waterloo student Tom Anthony in 1998. A number of questions emerge from previous research conducted at the site (Anthony 1998), specifically: 1. Was the center of the plume offshore mapped, an assumption made in his reactive transport model? 2. Is naphthalene being degraded, and what are the degradative processes responsible for the observed mass loss? 3. Evaluate abiotic processes such as sorption and tidally-enhanced dispersion and dilution so that their contributions to attenuating naphthalene may be better understood. 4. Are the contaminant levels at the river bed interface affected by secular sediment scour and deposition? This thesis is organized as follows. Chapter Two provides a description of the study site and summarizes aquifer and groundwater 4 contamination characteristics from previous research. Chapter Three provides a detailed description of each of the methods used. A discussion of the findings of each research component is provided in Chapter Four. Conclusion and summary of the key research findings follows in Chapter Five. Chapters are formatted such that tables and figures referred to are located at the end. 5 C h a p t e r T w o : S i t e D e s c r i p t i o n Information contained in this chapter has been summarized from other reports including site investigation reports by Golder Associates (2000, 1998, 1997) and the M.Sc. Thesis by Anthony (1998). Detailed information maybe obtained by referring these reports directly. The study site is located along the Fraser River adjacent to an operating wood-preservation facility located in the City of Coquitlam. Wood-preserving operations have taken place at this site since the late 1920s, and the site became the focus of environment investigations in 1981 [Golder 1997]. One benefit resulting from the many investigations is the establishment of a well-characterized and well-instrumented site suitable for conducting detailed scientific research (Figure 1). The geology consists of an ancient tertiary bedrock basin filled with unconsolidated glaciofluvial sediments. The stratigraphy of the sediments underlying the site were determined from borehole investigations and cone penetrometer test (CPTs) and are reported by Golder Associates Limited (1997). Four units represent the stratigraphy of the site, from top to bottom these units are: 1. Near-surface fill deposits; thin veneer of gravel and silt fill 1 to 2m thick 6 2. Fine-grained native over-bank deposits; fine-grained native silty and clayey horizon with an average thickness of 4.4m with a maximum depth of l m below mean sea level (msl) 3. Fraser River sands; main sandy unit (approximately 25 m thick) referred to as the Fraser River Sands, the upper portion of which consists of laterally continuous and variably silty fine-grained sands. This unit forms the main aquifer body. 4. Pre-Fraser river sands: dense silty and gravelly deposit of Pleistocene age. The Fraser River bounds the site to the south and by the New Westminster uplands to the north and northeast. Flow within the Fraser Sands Aquifer is horizontal, and on an annual basis, its direction is south toward the Fraser River. A local groundwater flow system exists in the near-surface fill deposits. Recharge of this system is through precipitation and therefore produces downward gradients with small seasonal fluxes to surface water bodies. Near-surface silty deposits separate the shallow system from the confined groundwater system. Recharge of the Fraser Sands aquifer is from precipitation in the New Westminster highland with discharge to the Fraser River. A regional flow system exists in the tertiary bed rock unit below the Fraser Sands aquifer. 7 The Fraser River is a nival-flow regime dominated by annual snowmelt runoff (freshet). River stage increases in April and returns to pre-flood levels by August (Figure 2). Tides also influence the water levels of the river. Diurnal water stage fluctuates about 2m at the site. The salt-wedge associated with upriver flow of seawater, however, reaches only as far as Annacis Island, located approximately 6 km down river from the site. Groundwater flow directions based on gradients were found to change on time scales as short as hours and as long as seasons as a result of tidal forcing and river stage, respectively [Golder Associates Limited, 1998]. Average monthly gradients were determined through 25 hour filtering (Serfes, 1991) of hydraulic head readings at three monitoring wells located on site (Figure 3). The monitoring wells are located within the influence of a pumping well operating on site. The function of the pumping well is to contain the aqueous phase plume and prevent offshore migration (Figure 1). Gradients ranged from -6x10 s to 4 x l 0 4 m / m for the period of March 1998 to December 1998. Throughout most of the year, groundwater flows were north to south toward the Fraser River at a velocity ranging from 67 m up to 200 m per year. Higher velocities are associated with the high-conductivity zone in the lower 8 to 10 m of the aquifer. During spring freshet, high-river stage flows may reverse the direction of groundwater flow for a period of 8 approximately 4 weeks. Aquifer properties were derived from aquifer pumping tests and tidal analyses. Estimates of hydraulic conductivity, storativity and velocity are presented in Table 1. Environmental investigations have revealed soil and groundwater contamination with creosote-derived polycyclic aromatic hydrocarbons (PAHs), monocyclic aromatic hydrocarbons (MAHs) and chlorinated phenols (CPs). Table 2 provides a list of the main PAHs components making up creosote along with their physical and chemical properties. Dense non-aqueous-phase liquid (DNAPL) exists in the aquifer beneath the processing area to a depth of 22 m. It is believed to be the source for a large anaerobic naphthalene plume extending 200 m south with the last 95m of the plume existing directly underneath the river. (Anthony, 1998). Figure 4 shows the distribution of naphthalene found by Anthony in the fall of 1997. Naphthalene concentrations decrease with increasing distance towards the discharge zone (riverbed). Anthony (1998) conducted an evaluation of the offshore naphthalene distribution through reactive transport modeling. Despite incorporating high values of dispersivity and a reasonable value of naphthalene retardation, he was only able to achieve a good fit of the model to field data when degradation was included. A decay rate with ti/2 = 1 year beginning at the shoreline provided the best fit. 9 Inorganic chemistry of the groundwater reveals two distinct groundwater types (Anthony, 1998), that is, plume groundwater and regional groundwater discharging further offshore. Chloride concentrations delineate the two groundwater types (Figure 4). Anthony conducted an electron acceptor mass balance of plume water offshore. Results suggest that there is sufficient C H 4 (21.4 mg/L) and Fe 2 + (63 mg/L) to account for the estimated mass loss of 14 mg/L of naphthalene from source zone to river discharge point. 17.5 mg/L or 293 mg/L of C H 4 and Fe 2 + , respectively, need to be present in groundwater to account for the mass loss. A plot of naphthalene, and electron acceptors (Fe 2 +, CHU and C O 2 ) along travel path to discharge zone (Figure 5) indicates that some combination of iron reduction and methanogenesis is likely the terminal electron accepting process acting offshore. Golder [1997] found no contamination in the hyporheic zone (in both river bottom sediments and groundwater) and river water (immediately above the sediment surface) within the suspected groundwater discharge area. 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Discharge at Hope station for A: 1998 - 1999 and B: 1999-2000 (source: Environment Canada). CO E? « o 8000 1-Aug 27-Jul 12000 14 LO (LU) }U3!pej£) 3j|nejpA|-| G B B J O A V vD 1 (rs - l l l ) U01IBA913 C h a p t e r Th ree : M e t h o d s To investigate those processes responsible for natural attenuation of naphthalene a multiple line of evidence approach was pursued (Wiedemeier et al. 1994). This chapter provides a description of the methods of investigation used in this thesis. The methods are: 1. Bathymetric surveys using sounder and differential global positioning system 2. Contaminant plume characterization using the Waterloo Drive Point Profiler (WDPP) 3. Onshore tracer test 4. Reactive tracer test; offshore 5. Groundwater sample analyses Bathymetric Surveys The bathymetry method used in this study is similar to that used by the United States Geological Survey (USGS) to map out sedimentation in aquatic systems (Wilson et al. 1996, Baker and Morlock 1996). The bathymetry of the Sapperton Channel area (offshore of Braid Street) was surveyed using a boat-mounted echosounder (Marintek SEAMAX) and a mobile hand-held Micrologic Global Positioning System (GPS) Model ML-250 operating in differential mode (Figure 6). The echosounder measures river depth by emitting ultrasonic sound waves or pulses from its transmitter called "pings". Objects in water i.e., fish or riverbed, due to the density contrast with water, reflect the pings, which, in turn, are picked up by the receiver. Sound waves are 18 then converted by the receiver into an electrical signal. The electrical signal is then used to determine the distance of objects from the echosounder based on a velocity of sound in water at 4945 feet per second and, the time from when a ping was emitted to when it was received. Instrument accuracy for the echosounder was approximately 10 - 20 cm (Marintek, pers. comms. 2000). Boat positioning on the river was determined using a DGPS. GPS data was differentially corrected in real-time by correcting satellite data with reference data broadcast from the Canadian Coast Guard (CCG) beacon in Richmond, British Columbia. Instrument accuracy for the DGPS unit was approximately 2 to 5 m. DGPS data was recorded as Universal Transverse Mercator (UTM) units; Northing and Easting with units of meters. Continuous time-tagged river stage readings were recorded using a pressure transducer (In Situ TROLL 2000 model) installed on a navigation beacon with known geodetic datum approximately 1 km up-river of Braid Street. These water level readings were used to correct sounder data for tidal effect and provide absolute readings of river elevation. Both DGPS and sounder readings were simultaneously downloaded to a portable computer and time-tagged facilitating data management. The boat was navigated along transects i.e., path for which the echosounder collected data, parallel to shore, as well as perpendicular to 19 the shore. Transects spanned the entire width of Sapperton Channel and the entire length of the Braid Street site. In total, seven bathymetric surveys were conducted during the 1998-1999 water year (September -August) saddling the freshet period that typically began in April and ended in August (See Figure 4 for hydrograph of Fraser River). Contour maps of the Sapperton Channel area were generated for each survey using SURFER v.6 (contouring software developed by Golden Software 1994). Contours were drawn based on a regularly spaced data set called a grid file. Grid files were created using the kriging option of surfer. The linear variogram model of the kriging method was used with a vertical scale factor of one (as recommended by Golden Software). This geostatistical method assigns depth values on grid nodes based on a linear interpolation between irregularly spaced observed (field data) points (Golden Software 1994). Contaminant Plume Characterization The location and distribution of dissolved creosote contaminants in the aquifer underneath the river was determined using the Waterloo Drive Point Profiler (WDPP)[Anthony 1998, Pitken et al. 1994]. The WDPP, developed at the University of Waterloo, was designed to collect groundwater samples at discrete depths in a single hole. To gain approval to conduct any work on the Fraser River, the research proposal was subject to an Environmental Screening under the 20 Fraser River Environmental Management Plan (FREMP). In addition, a permit from the governing authority, the Fraser River Harbour Commission (FRHC), was required for temporary work on the Fraser River. A copy of the permits are provided in Appendix A. Figures 7a and b show the components and set up of the profiler and sample manifold assembly. The stainless steel profiler tip, consisting of screened ports is connected to 1 %" AW drive rods. The ports of the profiler tip lead to a common internal reservoir which, in turn, is connected to 1/8" I.D. Teflon internal tubing that ran inside the AW rod to a manifold. The manifold assembly consisted of a 3-way valve, pressure gauge, two sampling heads (60 ml hypovials), and a bi-directional variable speed peristaltic pump (approx. 1.3 L/min capacity). Sorption of contaminants onto the surface of the sample delivery system was kept to a minimum with the use of stainless steel, Teflon® and glass components. The only exception to the system was the use of rubber O-rings used for sealing the sampling heads. O-rings were removed and replaced after each sampling point. Offshore profiling was conducted using the WDPP from a 70-foot seiner (Figure 8) with five-point anchoring capability. Five-foot lengths of AW rod were continually added as the profiler was advanced to greater depths by use of a pneumatic hammer suspended from the ship's 25-ton boom. 21 As the profiler was advanced, deionized water (D.I.) water was pumped through the internal sample delivery system (Figure 9). This kept ports from clogging with sediment and prevented the downward transport of sediment particles to the next sampling interval. Pumping Dl water also purged the system of groundwater remaining from the previous sampling point. As the desired sampling depth was approached the direction of flow on the pump was reversed and water was pumped up from the aquifer through the manifold and into a waste container. Pumping to waste continued until approximately 2 to 3 sample delivery system volumes were purged (a few hundred milliliters), at which point, sample bottles containing the newly collected sample are removed from the sampling head. Subsequently, new vials were replaced at the sampling head, the entire sampling system was rinsed with methanol to remove sorbed organic contaminants and the procedure was repeated for additional sampling intervals. The approximate location of each sampling point offshore was determined by physically measuring the distance from the profiler to reference points on shore or to nearby dolphins by using a survey chain. The approximate depth of each sampling interval was determined by recording the depth of profiler penetration into the riverbed from the top of the drill rod guide bracket. Absolute elevations of the sampling intervals were determined by recording changes in river elevation using a 22 pressure sensor fixed to a navigation beacon (known datum) and subtracting recorded depth of profiler at a specified time. For the initial plume characterization in May 1999, a total of 6 offshore sampling locations with 7 to 10 sampling depths were sampled (See figure 10 for profiling point locations). A 40ml and/or 60ml sample was collected at each sampling interval for PAH, benzene, toluene, ethylbenzene and xylene (BTEX), and trimethylbenzene (TMB) analysis. 40ml samples for inorganic analysis were collected at two or three intervals at each sampling point. Samples for organic analyses were preserved with 10% sodium azide (NaNs) solution. Samples for cation analyses were filtered and preserved with nitric acid (HNO3) to pH 2. Equipment blanks and duplicates were also collected at each sampling point. Onshore Tracer Study The purpose of the onshore tracer study was to assess groundwater flow directions, velocities and dispersion in an area unaffected by on-site pumping. In addition, the study was used to rehearse tracer test implementation and sampling in preparation for the offshore tracer study. A pulse-type natural gradient tracer test was conducted, involving the injection of a 5000L slug of groundwater spiked with bromide (Br). Its fate and movement was monitored as it migrated passively under natural groundwater - flow conditions away from the 23 point of injection towards the river. Monitoring took the form of collecting and analyzing groundwater samples. Approval for the injection of bromide was required under provisions of the British Columbia Waste Management Act. Copies of all approvals are provided in Appendix A. The onshore tracer test took place at the site in an uncontaminated, inland portion of the aquifer (see Figure 10), outside of the capture zone of the pumping well. The conditions at this part of the site would be similar to those that existed in the contaminant plume area before pumping began. To minimize monitoring effort and expense, the tracer was injected into the upper portion of the Fraser Sands Aquifer 10 -11m below ground surface (Figure 11). B r Tracer B r was used to detect the presence of the pulse-injectate and track its migration under natural groundwater flow conditions. B r , as a tracer, exhibits the properties desired of a conservative tracer namely: • background levels at the site were less than 0.05 mg/L • it is biologically stable • Generally not lost due to precipitation, absorption, or adsorption (Davis et al 1985). As a conservative tracer, B r should travel with the same velocity and direction of groundwater with no interaction with aquifer material. The bromide concentration was measured using an Ion Selective 24 Electrode (ISE). The ISE could be used in the field, uncalibrated, to give an estimate of bromide concentrations. In the lab, the water samples and standard solutions were brought to uniform laboratory temperature prior to analysis (discussed later in more detail). In addition to B r , Deuterium ( D 2 O ) was added as a conservative tracer. However, with its lower detection limit and associated higher analytical costs it served principally as a backup in the event B r concentrations fell below the detection limit of the ISE, and it was felt that additional data was required. Consequently, analysis for deuterium was never conducted. Injection Characteristics A desired characteristic of the injection was to produce a tracer pulse large enough to detect and track the mass over distance and time with an anticipated dilution of 100 to 1000 times (assessed by modeling using 3D ADE). However, the pulse had to be small enough to make attempts at monitoring both feasible and affordable [Mackay et al. 1983]. Based on the above considerations it was decided that a pulse approximately l m thick and 5m diameter was satisfactory. Consideration of the method detection limit (MDL) of 0.4 mg/L for bromide analysis using an ISE and dilution by lOOOx required an initial pulse-injectate concentration (Co) of 400 mg/L. Likewise, the Co for D 2 O was 60 mg/L. Thus, injecting through a single l m drive-point well with an assumed 25 porosity of 0.25, the required volume for the tracer pulse was found to be 5000L. Injection and Monitoring Procedures A schematic of the injection system used for both the onshore and offshore tracer study (discussed later) is shown in Figure 12a (photograph of system on site Figures 12b). The injection well consisted of a Johnson® Stainless Steel Drive Well Point (2" O.D., 36" long with No. 8 slot or 0.008" or 0.20 mm slot opening) fitted with a disposable aluminum shield and modified coupling for connecting to AW drill rod (Figure 13). Low density polyethylene (LDPE) tubing [1/2" x 5/8"] was used to connect the well point to the peristaltic pump. The well point was driven to a depth of approximately 12 m and was subsequently withdrawn by approximately l m to expose the screen at an interval of 10 to 11 m. The well was driven to depth using a custom made sampling rig developed at UBC (Figure 14). The main components of the injection system include a sampling port with sampling manifold connected to the main extraction/injection line, variable speed peristaltic pump, dewatering pump with 2" discharge, flowmeters for measuring groundwater extraction/injection and tracer stock solution flow rates, reservoir for stock tracer solution, argon gas, and a 5000 L polyethylene tank. 26 Water samples were collected from the dewatering pumping to determine if groundwater was being exposed to oxygen during extraction. Dissolved oxygen was found to be non-detectable in the pump discharge while extracting groundwater. To ensure oxygen free conditions during extraction, temporary storage and injection of groundwater was conducted under a vapor space of Argon gas (Rugge et al. 1999). Before filling the 5000L tank with groundwater, the entire system was purged of oxygen. All water lines were purged with groundwater extracted from the injection well. Groundwater was then pumped into the 5000L tank after two volumes of headspace vapor was purged with Argon. While groundwater was extracted, a concentrated solution of bromide and deuterated water was drawn from the tracer stock reservoir and pumped into the extraction line using a peristaltic pump at a rate of 10/5000 of the extraction rate. An extraction rate lOL/min through a V2" I.D. tube should have easily produced sufficient turbulence (calculated Reynolds number Re = 92800) to assume that mixing of groundwater and the concentrated tracer solution was thorough. Once the 5000L tank was filled pumping was reversed and the tracer solution was injected into the aquifer. To determine the initial concentration and homogeneity of the tracer solution, the injection water was sampled periodically at the well injection header. 27 Migration of the tracer was monitored by groundwater sampling using novel multilevel monitoring wells (MW) and the WDPP. Single-hole drive-point MW were designed and developed at UBC as an inexpensive alternative to conventional multilevels, which require expensive auguring and backfilling for installation. The multilevel samplers were constructed by machining a 1 cm diameter port, similar to those on the profiler tip, on the side of an AW coupling and fitting it with a screen. A second hole was drilled down the length of the coupling intersecting the port. A short piece of 1/8" O.D. stainless steel tubing was silver-soldered into the drilled-out hole so that 1/8" O.D. (5/64" LD.) semi-rigid LDPE tubing can be connected via compression fitting (Figure 15). Each MW consisted of six sampling ports with a vertical separation of 0.305m (Figure 13). The spacing between ports was adequate to ensure that each port would draw sample from separate and distinct zones within the aquifer. For instance, a single purge volume for each sampling port is about 50 ml (for 15 m of 5/64" LD. LDPE tubing). Therefore, the total purge volume is 150 ml, which equates to a sphere with less than 5 cm radius in sandy media with a porosity of 0.25. Two multilevel samplers were installed parallel to the groundwater flow direction screened across the same vertical horizon as the injection well. Monitoring well 1 (MW1) was installed 5.43 m down gradient of the injection well (Figure 16). Results of the bromide breakthrough at the 28 first fence and additional profiling aided in determining the expected tracer migration path (Figure 17). The direction of groundwater flow was determined by aligning the centre of the bromide plume with the injection well and interpolating the line down gradient. MW2 was then installed 13.91 m down gradient in line with the expected flow path of the plume (Figure 16). Groundwater samples from each port of MW1 and MW2 were collected using a peristaltic pump. The lines to each port were purged by about 50 ml (3 purge volumes) prior to collecting a sample. Ground water samples were then analyzed for bromide under laboratory conditions at UBC. Reactive tracer test; offshore The objective of the offshore tracer test was to determine if naphthalene, the principal contaminant in the portion of the aquifer under the river, is degrading naturally. A direct approach to assessing biodegradation of naphthalene in-situ is to inject a radioisotope of naphthalene into the aquifer and monitor the production of radiolabeled by-products, specifically radiolabeled C O 2 . The radiation released by the radiolabeled naphthalene allows one to distinguish the tracer and tracer degradation products from their in-situ counterparts. Specifically, if radiolabeled degradation products such as C O 2 are detected, then they must come from the degradation of the radiolabeled naphthalene tracer. 29 Approval to inject 1 4C-naphthalene was obtained by the Atomic Energy and Control Board of Canada (See Appendix A). 5000L of groundwater were extracted in the same manner as during the onshore tracer test. The groundwater was amended with Br-and the radiolabeled naphthalene and injected into the contaminated portion of the aquifer under the river where Anthony (1998) suspected mass loss of naphthalene (see Figure 10). Figure 18 shows the location of the injection interval in cross section. This tracer study took advantage of zones of groundwater stagnation or slow flow as a result of a pumping well operating onsite (see Chapter One). Injecting into an area of very low groundwater flow provided longer tracer residence time accommodating the slow anaerobic biodegradation rate of naphthalene. It also facilitated the tracking of the tracer by restricting its migration. 14C-naphthalene Tracer The artificial injection of a radio-labeled substance as a tracer in a hydrogeologic application has for the most part ceased in many countries including the United States (Davis et al. 1985). As a rare and novel application, it is therefore valuable to provide a discussion on radioactivity so that its application as a reactive tracer in this study is clearly understood. 30 The radioisotope of naphthalene injected in this study was NAPHTHALENE-BENZENE-UL- 1 4 C (abbreviated as 1 4C-naphthalene) supplied by Sigma-Aldrich Canada Ltd (Figure 19). A copy of the supplier specifications for the 1 4C-naphthalene used is provided in Appendix B. 1 4C-naphthalene is a radioisotope of naphthalene, i.e. it contains radionuclides of carbon (specifically carbon 14) in its atomic makeup. The 1 4C-naphthalene injected in this study consists of a benzene ring entirely made up of six 1 4C-radionuclides. Each 1 4C-radionuclide contains six protons and eight neutrons in its nuclei with a mass number of 14. As a result the 1 4 C-nuclei forms a beta-unstable radioactive atom that undergoes radioactive decay. Radioactive decay is a process where an element undergoes transmutation at the atomic level to form a different element. In the case of 1 4 C , radioactive decay involves the conversion of a neutron into a proton and the emission of a beta-particle ((T) otherwise known as an electron (equation 1). The resulting element is a stable isotope of Nitrogen (N). Streams of beta particles are referred to as beta radiation. 14 14 C • ^ N + P" + antineutrino (1) 6 7 It was assumed that the radioisotope of naphthalene would undergo the same biological, chemical and physical processes that the 31 in-situ naphthalene experiences. A crucial property of the 1 4 C -radionuclide to this study is that it is considered conservative, since it decays radioactively very slowly, with a half-life of 5730 years. The 1 4 C -naphthalene molecule may undergo various physical and chemical reactions i.e., sorption onto solid material, biodegradation, production and volatilization of CO2 and CH4, volatilization of the gases, and/or precipitation of CO2 as a carbonate mineral. However, the radioactivity associated with the 1 4 C will be essentially conserved and can be accounted for by sampling the various material phases. Another distinguishing property of a radioisotope tracer is the very low level of detection limit using a Liquid Scintillation Counter (LSC). LSCs can detect radioactivity at the level of disintegrations per minute and should easily detect the anticipated low levels of 14C-CC>2 produced. Concerns on preferential degradation of 1 2 C - 1 2 C over 1 2 C - 1 4 C bonds, and likewise, 1 4 C - 1 4 C bonds was addressed by selecting a radioisotope of naphthalene dominated by 1 4 C atoms, thus reducing the number of 1 2 C - 1 2 C bonds per 1 4C-naphthalene molecule. Systeme International (SI) Units of activity is the becquerel (Bq) which is defined as one atomic nuclear transformation per second (disintegration per second). In this paper, radioactivity is expressed in terms of microcurie per litre of groundwater (uCi/L) where l u C i is equivalent to 2.2 x 106 disintegrations per minute (dpm). 32 In addition to 1 4C-naphthalene, KBr and D2O were also injected for the same reasons discussed in the section on the onshore tracer study. Injection and Monitoring Procedures The extraction and injection system proposed for the offshore test was identical to that used for the onshore test. Likewise, 5000 L of extracted groundwater was spiked with 2 kg of bromide (from KBr), 300 g of deuterated water (D2O), and 12.8 mg 1 4 C naphthalene (5mCi). Concentration of the tracers in solution were approximately 400 mg/L B r , 60 ppm deuterium, and (1 uCi/L) 1 4C-naphthalene. The addition of 1 4C-naphthalene increased the naphthalene concentration in groundwater by approximately 0.26%. The drive-point well was installed temporarily, screened between 14m to 15m below sediment interface, only long enough to permit the extraction and injection of the groundwater and tracers (approximately 10 to 12 hours). The Waterloo profiler was then used to sample the plume after injection. All offshore operations were conducted aboard a seiner large enough to support all injection apparatus and capable of multi-point anchoring (Figure 20a, b). Groundwater sampling positions offshore were quickly and easily determined by triangulation using two known points on the river (dolphins for anchoring log booms, see Figure 21). A water gauge was 33 constructed to monitor fluctuations in river stage due to tides. Coupled with approximate indications of bromide concentrations by use of the ISE, this method facilitated real time mapping of the tracer plume. Groundwater samples distributed in space were withdrawn during four sampling rounds. Sampling rounds increased from three to four days at the beginning expanding to seven days for the fourth and final round. Figures 22 and 23 demonstrate the sampling effort for the offshore tracer study. Samples were collected under oxygen-free conditions through use of the sampling manifold [described in the section on Contaminant Plume Characterization], and analyzed at UW for 1 4C-total, 1 4C-napththalene and 1 4 C - C 0 2 . Br-, pH, Iron (Fe) and dissolved oxygen (DO) were also measured in the field using methods described in the section on Groundwater Analysis. Groundwater Sample Analysis All inorganic [except bromide], organic and radioactive analyses were conducted at the University of Waterloo. Details of each methodology conducted by the University of Waterloo is provided in Appendix C. DO was measured in the field as per American Society for Testing and Materials (ASTM) Method D5543-94 using CHEMets® K-7501 (0-1 ppm DO range). High concentrations of ferrous and ferric iron (Fe 2 + and Fe 3 + , respectively) may have and interfered with the CHEMetrics method 34 and caused higher DO readings than anticipated. As a result, some DO analyses were conducted using the DO HACH Test Kit (Model OX-2P). Another check on DO levels in groundwater was the use of the CHEMets® K-6010 Iron Kit which measures total and soluble iron. The presence of iron (assuming Fe 2 + ionic species predominating) indicated groundwater void of oxygen. Acid buffering capacity of the groundwater (alkalinity) was measured in the field using ASTM Method D 1067-92; Test Method B -Electro me trie or color-change titration. Approximately 5 drops of Bromocresol Green-Methoyl Red Indicator were added to a 25 ml sample of groundwater discharged to an erelenmeyer flask using an Eppendorf 0-50 ml Repeater Pipette 4780. 0.0IN HC1 (titrant) was accurately added to the sample by micro pipette until a color change marked an end point. pH was also measured in the field using a Model 91-56 ORION Combination Electrode. Bromide was measured in the field using an Orion Combination Sure-flow Bromide Electrode (Model 9635BN) in combination with a Fisher Scientific voltmeter (accumet portable AP25). Used in the Direct Measurement Technique (see detailed discussion of write up in Appendix D), bromide concentrations were biased high, which was satisfactory for real time determinations in the field (see Figure 24). Direct measurement readings are sensitive to temperature and to interference due to the 35 presence of polycyclic aromatic hydrocarbons (PAHs) (see discussion in Appendix D). Therefore, samples were collected in the field and analyzed under controlled laboratory conditions by the known addition method. 36 Figure 6: Schematic of bathymetry equipment setup. 37 Figure 7a: Waterloo Drive Point Profiler Setup Sampling Manifold Assembly Peristaltic Pump valve J Sampling Pressure head and guage vials • Stainless steel tubing Waste or Dl water container — AW Drill Rod bod \ / ~ " Stainless steel profiler tip 38 Figure 7b: Photo of Profiler Tip Designed at UBC with modified hammering head. 39 Figure 8: View of Seiner and on-deck setup of W D P P Figure 9: Operation of the WDPP DEIONIZED WATER PURGE WATER RIVER BED v Injection of deionized water during advancing of profiler preventing clogging of ports and purging of internal tubing Collection of groundwater sample from desired depth 41 Figure 12b: Picture of Injection system 45 Figure 13: Picture of injection and monitoring wells Figure 14: Picture of custom made sampling rig involved in grouting profiling holes. 47 Figure 15: Picture of modified AW coupling 48 CO •4-1 ti • i H o ft W> ti s 0 a l - H a o •o cd •O ti cd co l - H ti • | H h O 4-) • IH ti o o ti o X o a. a. v 60 CM + oo a. i o Q_ i a. a. a. TT t-~ 1 -CO O CO t O CO 5 T- CN CO Q. Q. Q. S Q. Q. Q. i i i i i i i T - T - CN r- o o o — m in co oo i>- oo HI 5 i o Q w - J c o CD O c ? o °-.S 8 •5 .•2 ^ E 'S "c ~ i + CQ t— ca X ti • i H o iH CU & (ui) SIXB-A Figure 19: Schematic of Naphthalene-benzene-UL-14C undergoing methanogenic degradation to carbon dioxide and methane Naphthalene-Benzene-UL-14C Carbon dioxide Methane A A w # C14 radionuclide # C12 O Oxygen 9 Hydrogen 52 Figure 20a: Offshore groundwater extraction/injection setup Figure 21: Determining location offshore by triangulation. 54 Figure 22: Plan view of all offshore profiling points (Offshore tracer study only) Injection Wel l • <§) X „ X<> X * X + • • * * x+x x • A a „ -P* <a + ° \ * + °x a X + * • + Sampling round 1 O Sampling round 2 X Sampling round 3 • Sampling round 4 8 9 10 11 12 13 14 15 16 17 18 19 20 Distance along river (m) 55 >» o >» •c - 4 - 1 09 I H 4 ) O CTJ I H • 4 - 1 V I H o O CO a • * H o a w a • I H l - H o I H a. I H o fl o « * H o — T- CM CO •j <b <h * • • + + + + + + • X • X • G X P D X X X CD • • • • • • • • • D + • • • • • • • » • • c o »-O c O ~ 'E Cl ~ E CO co 13 "C C C O O O) o c c c o C CO ID Cl Cl E E CO CO CO CO Q.I E CO CO + • ++ ax+ + ++• a-0 <> • o o £ + $ * of* n++ + x • x + + + x x • • • • • xa-x> xo •4 x • + x> + » *<> X • x% Qn - r nx-FiK • x • on o •x-B x+ + + ++ ++ + • EX + + • • • EX + • + • + X CO CN CO > ro c o CO CD O c CO •*-> W G vD L O CD > co co o I H o • • CO « N 4) I H 5 • I H CD h- 00 o CM CM CM CM lO (3i)epoe6 LU) UO|IBA9|3 •8 c o a & o a > fa •*-» a 9) u CO at a> o CO u Q >> a o • i H rt u 4 J e V CJ a 0 o • i H a o h o I - H tN 4) fa • • O O CM O 00 o C D O O O) E CQ 8 .12 ra LO o oo o CD O ~ CN ra 4 o o CM O O O O O 00 o o CO o o o o CM uidd [jg] sisA|euv P|9!d C h a p t e r F o u r : R e s u l t s a n d D i s c u s s i o n Riverbed Stability Seven surveys were conducted over the span of one year to evaluate riverbed stability (August 1999 to July 2000). Contour and post plots of each survey are provided in Appendix E . This section provides a brief discussion of general riverbed morphology followed by an evaluation of changes to riverbed elevation as evidence of secular scouring and deposition. A three-dimensional depiction of the riverbed is presented in Figure 25. Closer to shore the river bed elevation was approximately 5 m (geodetic). A relatively steep slope occurs a short distance from shoreline where the riverbed elevation ranges from 10 to 12m geodetic. The riverbed rises gradually from its lowest elevation at the center of the channel to a sandbar to the south. To assess changes in riverbed elevation through a water year, two-dimensional profiles of riverbed elevation were plotted and compared, along two transects parallel to river for each survey. Transects A-A' and B-B 1 run parallel to shore at 5452400 N and 5452350 N, respectively (see Figure 25 for coordinates relative to bed). Profiles for the seven surveys for the two transects are presented in Figure 26 and 27. 58 Upon review of the profiles, several important characteristics of the riverbed are observed. Two-dimensional bed-forms ranging from 0.5m to 2m in height and 20m to 100m in length are apparent. Morphologically, they are similar in appearance to dunes observed by Kostaschuk and MacDonald (1988) in the Steveston Channel; a downstream section of the Lower Fraser River. Dunes are a type of bed form created from bed-material in motion correlated to a fluid velocity (Knighton 1984, p. 52). A significant drop in elevation is shown along transect A-A' as recorded during the October 28 survey. This change in river bed elevation (apparent scour) is localized as changes of similar magnitude are not observed in other parts of the channel in any of the other surveys. It appears as though this area was subsequently in-filled with sediments after the October 28 survey. River flows from September to March are relatively stable and do not provide an explanation for the observed localized scour. The highest bed elevation was observed between the March 22 and June 4 surveys followed by October. Bed elevation drops from October to March when it reaches its minimum elevation during the rising limb of the Fraser River hydrograph (see Figure 2 Section 2 p. 11). It returns to pre-flood elevation during the falling limb as seen by the profile representing the bed on July 20. These changes in bed elevation along 59 Transects A-A' and B-B' with respect to river stage are presented in Figures 28 and 29, respectively. Bed-material transport is a function of the transporting capacity of river flow (Knighton 1984, p. 71). Typically with sand-bed streams the channel is scoured at high discharges on the rising stage and filled to pre-flood levels on the falling stage (Leopold et al. 1964). However, bed-material load transport varies from section to section of channel through a flood wave (Andrews 1979). Results of this study suggests that bed-material load transport proceeded in a wavelike process and was responsible for the temporary increase in riverbed elevation (Meade 1985). Sediment supply and seasonal tidal drawdown on river stage are responsible for the wavelike transport of sediments through the channel (Church pers. comms. 2001). During freshet the tidal draw down is less severe while tidal draw down is otherwise high resulting in larger velocities. Correspondingly, sediment load (input) is highest prior to peak river discharge (McClean et al. 1999). Thus, the channel fills on the rise of freshet when sand input is highest and scours after peak discharge when sand input is much lower and tidal draw down is larger. Changes to the riverbed at two different scales are apparent. Firstly, in the form of dunes migrating along the channel and, secondly as secular scour and deposition. Over the course of a year, the riverbed 60 appears to be in quasi-equilibrium regarding elevation changes. This study is limited in the sense that it was conducted over one year and did not address interannual variability. Likewise, the surveys were likely too infrequent to clearly state that the river was not scoured beyond the level observed. Contaminant Plume Characterization Organics PAH, BTEX and chlorophenol results of the detailed sampling program conducted offshore are tabulated in Appendix F. Naphthalene was the dominant PAH observed and constitutes the majority of the plume mass. Profiles of naphthalene distribution perpendicular (north -south: A-A' transect) and parallel (east-west: B-B') to shoreline are represented by cross sections in Figures 30 and 31, respectively. Naphthalene distribution perpendicular to shore observed by Anthony (1998) in the fall of 1997, for purposes of comparison only, is also shown in Figure 30. The observations of naphthalene distribution are fairly similar to what Anthony observed in 1997. Based only on three sampling points R13, R12 and R8, naphthalene distribution along A-A' reaffirms the presence of a naphthalene plume extending outward towards the Fraser 61 River. Since sampling was restricted to points closer to shore there is no information regarding discharge of PAHs to river. Offshore sampling captured neither the eastern nor the western (upriver or down-river) margins of the plume (Figure 31). This cross section is compiled based on the naphthalene concentrations found at depth from 4 profiling points. Based on the cross section it appears that the plume is likely greater than 200 m wide. A distinct core exists appearing to be slightly up river of the A-A' transect with the highest concentration being 3674 ug/L. This core area coincides with the deep DNAPL zone observed beneath the treatment facility upland. The regularly shaped plume would suggest, that at the scale of observation, the aquifer is rather homogeneous. Both offshore sampling episodes conducted in 1997 and 1999 were done with groundwater flow under the influence of a pump and treatment system operating since 1995 (Golder, 1999). Onshore pumping, as designed, contained onshore contamination, specifically the NAPL in the intermediate to deep zones of the aquifer (Golder, 1999). The pumping rate was approximately 16 m 3 / h r from 1995 to 1997. Only later in the fall of 1999 was a new higher capacity pumping well (27 m 3/hr) brought online. An effect of onsite pumping is the creation of zones of low groundwater flow or stagnation offshore. Under the influence of the 62 pump and treat system, the offshore portion of the plume was, for the most part, isolated from its upland source zone. Naphthalene profiles for the 1997 and 1999 sampling events reveal nearly identical plumes (Figure 30). With containment of onshore contamination, naphthalene concentrations should decrease if natural attenuation is occurring. Under the existing groundwater flow conditions two likely fate and transport scenarios could explain the 'apparent' stability of the offshore naphthalene plume. Firstly, the rate of naphthalene desorption is similar to the rate of biodegradation and dispersion combined. Secondly, neither biodegradation or desorption is occurring and naphthalene levels are maintained in the absence of fate and transport processes. Results of the offshore tracer test (discussed in more detail later in this section) confirm that groundwater offshore is either stagnant or low in flow. 'Open-looped' hysteresis appropriately describes adsorption -desorption kinetics of naphthalene with sediments (Kan et al., 1994). That is, rates of desorption are typically lower than rates of adsorption. Therefore, despite the adsorption information provided by Anthony (1998) the issue of desorption can not be addressed without additional data, specifically leachate analyses on core samples of sediments collected from the sub-fluvial portion of the aquifer. Inorganics 63 Samples for inorganic analyses were collected at infrequent intervals at the offshore profiling points. Results have been tabulated and are presented in Appendix G. Cross sections parallel to shoreline (B-B1) for the main inorganic species are presented in Appendix H. Results are similar to those observed by Anthony (1998). While the groundwater is believed to be anoxic, O 2 contamination from field procedures may explain detection in samples. Sampling from the discharge of the peristaltic pump and, interference of high iron (Fe3+) with reagents in the Chemits Dissolve Oxygen (DO) kit (ASTM, 1995), are the probable causes. Nonetheless, it is unlikely that any appreciable amounts of DO, i.e., greater than 0.5 ppm, would exist in the presence of Fe 2 + . S O 4 2 " , H 2 S , N O 2 2 " , and M n + 2 concentrations were also found at relatively low levels indicating that they are likely not involved in electron transfer (Chapelle et al,. 1995). NO3- values are higher than expected and likely due to contamination in the field with nitric acid. Anthony (1998) reported NO3- values within the plume water as being non-detectable. The presence of Fe 2 + and C H 4 (as observed by Anthony, 1998) suggests that the terminal electron accepting process (TEAP) maybe a combination of iron reduction and methanogenesis. Recall Figure 5 in Section 2: Site Description, where Fe 2 + , C H 4 and C O 2 levels are shown to increase with a corresponding decrease in naphthalene along the flow path from source zone to offshore. A screening protocol to evaluate the 64 degradative potential of naphthalene under anaerobic conditions is recommended by Sufflita et al., (1997). In this case, CO2 levels, observed at the discharge point, are compared to values predicted by the redox equation (2) given by Symon and Buswell (as seen in Sufflita el al., 1997). CioH 8 + 8H2O —» 6CH4 + 4 C 0 2 ' (2) CioH 8 + 48 Fe(OH)3(s) <-> 960H- + 28 H2O + 48 Fe 2 + + 10CO 2 (3) Iron reduction follows the path outlined by equation 3 indicating that the reaction is acid consuming represented by higher pH levels. The reaction involving methanogenesis is acid producing leading to lower pH levels. It's of value to note at this point that pH of the plume water offshore ranged from pH 5.6 - 7.2. Under methanogenic or iron reducing conditions 19.2 or 48 mg CO2 /L would be produced, respectively. CO2 as high as 187 mg/L was found near the discharge point beneath the river. Indeed, the higher CO2 levels found at the discharge point may also include CO2 production from degradation of less persistent components of creosote and other organic contaminants in groundwater. Dispersion and Groundwater Velocity; Onshore Tracer Study The onshore tracer study began on February 8 with the extraction of 5000L of groundwater at an average rate of 12 L/min. Injection of spiked groundwater occurred at an average rate of 13L/min. The 65 inorganic chemistry of extracted and injected groundwater are summarized in Table 3. The background and injected bromide concentration was found to be less than 0.5 mg/L and 370 mg/L, respectively. Groundwater samples at monitoring well 1 (MW1) were collected prior to and immediately after injection followed with regular sampling every two days. Sampling at MW2 began on March 27 once an initial estimate of groundwater flow direction and velocity were obtained. Results of bromide analyses are tabulated in Appendix I. Break through curves (BTC) for both MW1 and MW2 are shown in Figure 32 and 33, respectively. BTCs are shown for each of the 6 sampling ports on the monitoring wells. The highest bromide concentration observed during this test was 6 6 % of the injected concentration (O.66C0) or 251 mg/L at MW1-2 and 0.24Co or 91 mg/L at MW2-1. The average groundwater velocity {v) at each sampling interval was determined by using equation 4. Where t is the time it took for the center of mass of the bromide plume to travel the distance (x) from injection well to MW. The center of mass being represented by the peak bromide concentration. v = x/t (4) 6 6 Variations in groundwater velocities provide an indication of the heterogeneity of that portion of the aquifer. At MW1 average groundwater velocities decrease with increasing depth from a maximum value of 68.5 m/yr to approximately 33 m/yr at MW1-3 and MW1-1, respectively. A similar pattern is observed at MW2. Average groundwater velocities also decrease with increasing depth from 50.7 m/yr to 31.7 m/yr at MW2-4 and MW2-1, respectively. Groundwater gradients during this time of study were affected by freshet and decreased from 4 x 10 4 to 1 x 10~4 in February (t = 0 days) and July (t = 200 days), respectively (see Figure 3 in Chapter Two). To obtain estimates of dispersivity from the breakthrough curves a three dimensional advection dispersion (3D ADE) model was applied. 3DADE is a Fortran program developed by Leij and Bradford (1994) encompassing an analytical solution to the three dimensional advection dispersion equation. 3DADE is applicable to rather simple transport scenarios where conditions include steady state unidirectional flow in homogenous media with uniform transport and flow properties. 3DADE was used in inverse form, that is, by fitting a selected analytical solution to bromide BTCs. BTCs at MW1-3 and MW2-1 were modeled since it is assumed that the centerline of the bromide plume passed through these ports. Bromide values perpendicular to the flow path (PI, P2, P3 and P12 @ 11.2 67 m.b.g.s; see Figure 17 in Chapter Three) were used to estimate horizontal transverse dispersion (Dy) at MW1-3. The fitted BTC for MW1-3 and transverse points are shown in Figures 34 and 35, respectively. The fitted BTC for MW2-1 is shown in Figure 36. Source zone (initial conditions) configurations, transport parameter estimates (model output), and goodness of fit values are also shown on the charts. Initial conditions were set up to approximate an instantaneous slug of 5000L (injected volume) of bromide solution equivalent to 20m 3 (4.5m x 4.5m x lm) in porous media with porosity of 0.25 assumed. Results of the 3DADE inverse modeling fit observed data very well for both curves and have corresponding low mean square errors (MSE) values of 0.003 and R 2 values near unity. Mechanical dispersion is related to the mean groundwater velocity through equation (4) (Domenico and Schwartz, 1990, p. 221.). Where at and am and am are longitudinal, transverse-horizontal and transverse-vertical dispersivities of the medium, respectively. Dl = ccl • v Drh = am • v and Dtv = arv • v (5) The au am and am estimated from MW1-3 is 0.04m, 0.007m and 0.001m, respectively. Likewise, values for au am and am at MW2-1 were found to be slightly higher 0.1m, 0.01m and 0.08m, respectively. With 68 the exception of the results of MW2-1, relative values of longitudinal dispersivity to transverse dispersivity agree with other field experiments in that ah>arh>arv, where > represents an order of magnitude (Gelhar et al., 1992). The same relationship holds true for the results of MW2-1 with the exception of aru being nearly equal in value to at. However, results of MW2-1 represent the best fit obtained while maintaining the initial conditions applied to modeling MW1-3. Values of (XL for both MW1-3 and MW2-1 agree with trends in dispersivity values documented by Gelhar et al., (1992) in their critical review of field experiments. Results of this study, for the scale studied, i.e. 15m appear in the lower part of the range discussed by Gelhar et al., (1992). Results of this test suggest that at this area of the site dispersion was not found to be enhanced by tidal forcing. The effects of tidal forcing on the plume is spatially variable. An inverse relationship exists between velocity and distance to groundwater-river interface according to equation 6 (Todd, 1959). h(x,t) - hoexp(- xfi)sin Equation 6 describes the response of head values in a homogeneous, isotropic confined aquifer, to tides at a boundary i.e., the aquifer river interface. h(x,t) is the head value at a distance x from the In xp to (6) 69 river at time t, ho is the tidal amplitude at river and to is the period of a complete tidal cycle. Thus, the greatest gradients are experienced nearer the aquifer-river interface. Dispersion coefficients change accordingly with changing velocities (see equation 5). The effect of tides have been shown to significantly reduce contaminant concentrations discharging to tidally-forced rivers due to dilution as a result of enhanced dispersion and influx of river water (Yim and Mohsen, 1992; Unger, 1996). Under similar hydraulic and aquifer properties and with a constant source input upland, Unger (1996) demonstrated through 2-dimensional modeling that, contaminant levels maybe affected up to 70 m inland from the aquifer-river interface. At this site the tracer test was conducted approximately 120 to 140m from the interface or, 45 to 65m from the shoreline. Dispersivity values derived from this study characterize transport conditions upland and, at a smaller scale than that of the plume. These values, therefore, do not apply to the offshore zone where attenuation is suspect of occurring. The offshore test was conducted in a zone of low groundwater flow and the resulting small groundwater velocities would make the effect of dispersion small and dispersivity difficult to determine. Recharge of the aquifer by the river act to reduce contaminant levels discharging to the river but, this process is likely occurring further 70 offshore within close proximity to the interface as suggested by the offshore tracer test. Biodegradation; Offshore Tracer Study The offshore tracer study took place over a 230-day period beginning on February 22 and ending with a final sampling round on October 10, 2000. Each groundwater sample was analyzed for bromide, and activity as 1 4C-total, 1 4C-naphthalene and 1 4 C - C 0 2 . 1 4C-total refers to the activity of the raw groundwater sample whereas, 1 4C-naphthalene and 1 4 C - C 0 2 represents activity associated the extracted organic phase (assumed to be all naphthalene) and remnant aqueous phase (assumed to be all CO2) of a groundwater sample, respectively. Analytical results of all samples collected are tabulated in Appendix J . 1 4C-activity analyses were conducted at the University of Waterloo. The methodology for 1 4C-activity analyses was modified with subsequent sampling rounds to correct for unknown interference associated with the scintillation cocktail and sample preservative (NaOH). Results considered reliable have been duly noted as '3' in summary tables (Appendix J) and for this discussion, reference is made to these results only. Characteristics of the injected groundwater are summarized in Table 4. Table 5 summarizes those monitoring results considered reliable. Corrections were applied to account for method uncertainties. Background activity was addressed by subtracting blank values from 71 1 4C-total, 1 4C-naphthalene and 1 4 C - C 0 2 results. 1 4C-naphthalene results were further corrected for extraction efficiency, and 14C-CC>2 results were corrected for trap efficiency and naphthalene carryover to the CO2 trap. Analyses to determine extraction and CO2 trap efficiency, and naphthalene carryover were conducted by Lesser (2000) and results are summarized in the Appendix C: Analytical methods. The average activity of the injected tracer was found to be 0.49 u C i / L , approximately one-half of the anticipated activity. The unaccounted 1 4C-naphthalene maybe attributed to partitioning to the headspace within the suppliers vial itself (lost when vials were open) and sorption onto injection system components (tanks and tubing). 14C-CC>2 levels indicate that precautions to maintain anaerobic conditions during injection were effective and that background levels of 14C-total activity are negligible. Maximum bromide and 1 4C-naphthalene observed are presented in plan view for the four sampling episodes in Figure 37. Bromide levels remained at nearly 90% of the injected concentration for the first 115 days. The presence of large boulders or logs on the river bed restricted the sampling effort during the last sampling round (t=230 days). It is believed that the highest bromide concentrations probably existed under these areas. Migration of the tracer plume was minimal and suggests that the area of injection was a zone of low groundwater flow, a 72 characteristic of groundwater flow fields under pumping conditions. Consequently, little dilution of the tracer plume occurred. Any appreciable migration of the tracer plume was observed only during the first 48 days. The migration of the plume during this time period may be attributed to reduced pumping operations and higher groundwater gradients (see Figure 3 in Chapter 2). Gradients were noticeably higher for 35 days from March 2 (8 days after injection) to April 6 (time of sampling round) with an average gradient of approximately 3.6E-4. These higher gradients likely account for the migration of the bromide plume during this time frame only. Assuming steady unidirectional flow (for 35 days only) and that the center of plume depicted in Figure 37 (t=48 days) represents the center of mass, the average groundwater velocity estimated was 62 m/yr. The velocity appears reasonable for this zone of the aquifer considering the lower gradients produced by onshore pumping operations. The highest activity level for 1 4C-total and naphthalene was observed during the first sampling round (t=48 days) at 0.1593 LiCi/L and 0.1575 LiCi/L, respectively. These values correspond to about 32% of the total activity injected. A plot of bromide vs. 1 4C-total reveals that sinks exist for 1 4C-constituents (Figure 38). The loss of 1 4C-total from solution, is represented by the departure of 1 4C-total/bromide ratios from the 1:1 line. Several sinks are expected to be contributing to the loss, 73 namely, the sorbing of 1 4C-naphthalene to solids, volatilization of 1 4 C -CH4 and 1 4C-CC»2 and perhaps the incorporation of 1 4C-CC»2 in a carbonate mineral. An attempt is made to quantify the sorption of 1 4 C -naphthalene to solids however, there is insufficient data to assess loss of 1 4 C - C H 4 and 1 4 C - C 0 2 by volatilization or 1 4 C - C 0 2 to precipitation. Maximum bromide and 1 4C-naphthalene levels did not coincide indicating different rates of migration. At t=48 days, 1 4C-naphthalene appears to be retarded with respect to bromide. Assuming steady unidirectional flow and that the highest bromide and 1 4C-naphthalene values observed represent the centers of mass for the bromide and 1 4 C -naphthalene plumes, respectively, retardation of 1 4C-naphthalene was calculated according to equation 7. Rf=v/vc (7) The retardation factor (Rf ) is an expression of the ratio of the average groundwater velocity (v) to the average 1 4C-naphthalene velocity (contaminant velocity vc) (Freeze and Cherry, 1979 p. 404). For the time period t=0 days to t=48 days Rf was found to be 1.7. Anthony (1998), based on Freundlich partitioning coefficients obtained from his isotherm study derived values of retardation (Rkf) ranging from 2.5 to 5.3 for naphthalene concentrations ranging from 10,000 to 1,000 ug/L, 74 respectively. Results of this test are within an order of magnitude with respect to Anthonys values and would suggest that the aquifer make up offshore is similar to the that upland. A sample mass balance check was applied to assess inconsistencies in the 1 4C-data. According to equation 8, 1 4C-total activity measured should equal the sum of all of 1 4C-constituents, that is, naphthalene, CH4 and CO2. 1 4C-total = 1 4C-naphthalene + 1 4 C - C 0 2 + 1 4 C - C H 4 (8) Any 1 4 C-CH4 present in samples contributes to the 1 4C-total count however, it was likely lost to atmosphere during analyses for 1 4 C -naphthalene and CO2 (Lesser, 2000). There was no specific technique applied to trap 1 4 C-CHU. In this case the sum of constituents should add up to less than 100% of the measured 1 4C-total. Where the majority of 1 4 C-CH4 is lost to atmosphere during sampling or partitioned to headspace in vials prior to the 1 4C-total count then 1 4 C-CH4 drops out of equation (8). In this case the sum of constituents should add up to 100% of 1 4C-total, barring any analytical error. The sum of 14C-CC»2 and 1 4C-naphthalene for all samples where 1 4 C - C 0 2 was detected range from 53% to 107% of their respective 1 4 C -total activity. Samples were either at or below 100% of 1 4C-total 75 measured. 1 4C-naphthalene recoveries for three samples RT11-7, RT76-3 and RT77-5 appear somewhat lower than expected and are attributed to analytical error as the integrity of vial seals were in question (Marianne VanderGrient, 2000, pers. comms.) Excluding the results of the three samples discussed above, it would appear that none or very little 1 4 C-CH4 made up the 1 4C-total activity measured. Measurable amounts of 1 4 C - C 0 2 were detected from samples collected from each of the four sampling rounds spanning 230 days (Figure 39). A statistically significant increase in 1 4 C - C 0 2 occurred over the 115 days since in injection. The highest 1 4 C - C 0 2 activity detected was 0.0044 uCi /L at 115 days (sample RT28-2). The lower values observed during the final sampling round are more representative of the tracer plume fringe than the core area were higher levels were expected. Thus, these lower values are excluded from the regression analyses. Regression analysis of the data provides a 14C-CC>2 production rate of 3E-5 |aCi/L»day. The specific activity for each of the six radionuclides making up the radioisotope is 5.22 mCi/mmol 1 4 C . Thus 1 4 C - C 0 2 production occurs at a rate of 5.75E-9 mmol 1 4 C - C 0 2 /L»day . A half-life for 1 4C-naphthalene at this site is calculated based on the following assumptions: • degradation occurs under methanogenic conditions (Equation 2) • 1 4 C - C 0 2 production rate of 3E-5 uCi/day, 76 • dilution of 14C-CC»2 is corrected using associated bromide data (a factor of 5.3 times dilution was applied based on an initial injection concentration of 370 mg/L and a corresponding sample concentration of 70 mg/L). Distribution of radionuclides among the CO2 and CH4 fractions is unknown thus, three scenarios based on fractionation were considered to calculate a half-life. The three scenarios are as follows: fastest, most probable and slowest represented by 1 mole, 2.3 moles and 4 moles of 14C-CC>2 produced for each mole of 1 4C-naphthalene degraded, respectively. The half-life (ti/2) calculated for each scenario from fastest to slowest are as follows: 0.72, 1.72 and 2.9 years, respectively. A better estimate for a degradation rate would be possible if 1 4 C -CH4 data were available to constrain fractionation. In addition, the presence of 1 4 C-CH4 in groundwater samples would confirm anaerobic degradation of naphthalene, more specifically under methanogenic conditions. From microcosm tests (not amended) Lesser (1999) estimates the half-life of naphthalene to be 2.31 years, in good agreement with the field-based estimates. In addition, reactive transport modeling of the creosote plume by Anthony (1998) yielded a half-life of 1 year. 77 Table 3: Bromide concentration of extracted and injected groundwater for the onshore tracer test. Sample ID UBC* ASL** mg/L mg/L Extracted GW ON-X-2 1 < 0.5 Injected GW ON-INJ-1 373 394 ON-INJ-2 375 ON-INJ-3 380 ON-INJ-4 382 395 ON-INJ-5 378 ON-INJ-6 380 Average (INJ) 378 395 *Analyses conducted at UBC by know addition technique using an ion selective electrode ** Split samples sent to Analytical Service Laboratories (ASL), Vancouver, B.C. 78 Table 4: Characteristics of injected groundwater for the offshore tracer. Sample ID Bromide UBC* ASL** mg/L mg/L 1 4C-total LiCi/L 1 4C-Naphthalene nCi/L i 4 C - C 0 2 LiCi/L Extracted GW OFF-EXT-1 OFF-EXT-3 0.5 0.5 < 0.5 Injected GW OFF-INJ-1 OFF-INJ-2 OFF-INJ-3 OFF-INJ-4 OFF-INJ-5 OFF-INJ-6 388 368 371 365 0.5559 0.4144 0.5596 0.4087 < 0.0005 < 0.0005 Average (INJ) 373 0.4852 0.4842 < 0.0005 *Analyses conducted at UBC by know addition technique using an ion selective electrode ** Split samples sent to Analytical Service Laboratories (ASL), Vancouver, B.C. 79 co o> | H C H a CO u CO - M cd I a ? o I N W> a o CO CO 0 9 > > I - H rt a a < i O rt a a CO in cd <u fl <u 13 xi o o & 2 o O 6 CD fl CD Cd X! +J XI a cd i a cd +-> o 6 fi cd (73 cd +J o +J I O CO O, CD Cut) J cd \ CD O CO O, CO O CN VD N O O O O VD O i-H VD VD vD CO CO 6 /—» CO /—\ CO LO u i-H oo i -H oo w .—1 LO LO VD O CO CT> VD LO t> VO CN CN t^-o O O o o O O o o o o o o O O o O o O O o o o o o o O o o O o O o o o o o o o o o o o o o o o o o o o i—I CO t>- LO ^  vO vO IN H H H <t oi n o o o o o o o o o o o o o o d d d d d d d LO CO CO o --i CN o o o O O O O O O o o o o c ^ c N L O o o ^ - ^ - c s i r > - i > c o ^ l O t O i O ^ O t O O N C N O O O r - H T - i O O O O O O O O O O O o o o o o o o o o o o o o d d d d d d d d d d d d d O ^ n o O t M N v D v O C ^ c O N ( M N r M C O O l C O ^ C O C M ^ H ^ O O O v D O ^ O O C N C O O O - H o o q o o q q o o q d d d d d d d d o d d CM <fr • i CO o o O O C S W O ^ ^ O O O ^ H M O ^ -C N H O J H O O O H O H O O O o o o o o o o o o o o o o o o o o o o o o o o o o o d d d d d d d d d d d d d L O L O 1 - ' O O C M C N V D C O V D L O V O O O |<McoLoo<tf-Loor>-CNvOLoai 1 - C O O N H m o \ ( N t O O O - I O O O O O O O O O O O i d d d d d d d d d d d d CO I> CO CM CM CO CM CO LO i -H i—i CO CO l>- 00 00 6 6 vD r> i-H i-H CM CM CN CM CM vD r> r> E- E- E- E- E- E- E- E- E-Qi Qi Oi Qi Qi Qi Qi oi Qi Qi Qi -a t CD 03 X! O 3 A CD 03 CD l-i a CD U 03 CD Id > <D X O CQ o 00 o in 4) I H a L O 00 (onapoaB ui) uoijBAeig Figure 30: A-A' cross section of naphthalene A: Anthony (1998) B: this study. fP3 R1 Fill/silt/clay 3* kR1 pR12 E -10 c 0 ra > 9 ) U J -20 -i -30 Dense silty/sand/gravel -60 I -40 I -20 0 20 Distance (m) •"A/D „ • • • " * » O T O . . • .3B74-' ' 57.••••• • Wi 11 •WO •R3 4 • A/D: 60 80 100 Sampling point from 1997 (Anthony, 1998) Sampling point from 1999 sampling event | 5000+ f j 500-5000 fj 50 - 500 fj 5- 50 Naphthalene (ug/L) 86 Figure 32: Breakthrough curves at MW1 O O O C o (0 3_ + - » c o o c o o 0 " D E o i _ CQ •a <D N 75 E 1.0 0.5 0.0 1.0 i 0.5 0.0 1.0 0.5 0.0 1.0 0.5 0.0 M W 1 - 6 Elevation = 10.72 m b.g.s M W 1 - 5 Elevation = 11.02 m b.g.s MW1-4 Elevation = 11.33 m b.g.s M W 1 - 3 Elevation = 11.63 m b.g.s 1.0 0.5 H 0.0 1.0 0.5 0.0 M W 1 - 2 Elevation = 11.94 m b.g.s •••• MW1-1 Elevation = 12.24 m b.g.s 0.0 20.0 40.0 60.0 80.0 100.0 T i m e (days) 88 Figure 33: Breakthrough curves at MW2 0.20 0.10 0.00 MW2-6 Elevation = 10.72 m b.g.s 0.20 0.10 0.00 MW2-5 Elevation = 11.02 m b.g.s o o o c o '+-> CO CD O c o o CD 7 3 E o m T 3 CU N 75 E 0.20 -I 0.10 0.00 MW2-4 Elevation = 11.33 m b.g.s 0.20 0.10 0.00 MW2-3 Elevation = 11.63 m b.g.s 0.20 -I 0.10 0.00 MW2-2 Elevation = 11.94 m b.g.s 0.20 0.10 0.00 Elevation = 12.24 0 50 100 150 200 Time (days) 250 8 9 o LO CM o LO CNJ (l /!On) ^IAROB zOO-OPV C h a p t e r 5: S u m m a r y a n d C o n c l u s i o n s This research focussed on answering questions that emerged from previous work conducted at the site, that is what, if any, are the abiotic and biotic processes contributing to the attenuation of naphthalene in an anaerobic tidally-influenced aquifer. Bathymetric surveys of the river bed in the Sapperton Channel area revealed bed-material transport of sediments in the form of migrating dunes and secular deposition and scouring. Dunes about 0.5 to 2m in height and 20 to 100m in length observed suggest that sediments are in a constant state of flux. Over the course of a year, the riverbed appears to be in quasi-equilibrium regarding elevation changes. The riverbed increases in elevation by approximately 2 - 3m during the rising limb of the freshet flood wave and returns to its preflood elevation during the falling limb. Results would suggest that scouring of the riverbed did not occur at a level to remove any appreciable amount of contaminated sediments. The study was limiting in that it did not address interannual variability of riverbed changes and, surveys were likely too infrequent to clearly state that the river wasn't scoured to any appreciable extent. Profiling confirmed the presence of an anaerobic plume at least 200m wide existing in that portion of the aquifer beneath the Fraser River. Naphthalene distributions extending outward from the shoreline 96 were very similar to the profile of 1997 by Anthony (1998). Results of the offshore tracer suggest that a low groundwater flow zone exists offshore. The similarities in plumes suggest that, in this zone offshore, a state of quasi-equilibrium may exist between competing fate and transport processes. Namely, degradation, slow advective transport from the source area and desorption of naphthalene from sediments. Decreasing concentrations toward the discharge zone render the later fate and transport scenario improbable. More probable is that degradative processes are spatially variable moving from anaerobic to aerobic in nature towards the aquifer - river interface. The natural gradient tracer test (onshore) provided valuable information on groundwater velocities, directions and dispersion. Average groundwater velocities ranged from 32 to 69 m/yr. This value agrees well with modeling predictions by Golder Associates (1998) for the upper portion of the aquifer. Groundwater flow was generally toward the river slightly angled toward downstream. Inverse modeling of break through curves using 3DADE provided estimates of longitudinal, transverse horizontal and transverse vertical dispersivities of 0.04 - 0.1 m, 0.007 -0.01 m and 0.001 - 0.08m, respectively. Longitudinal dispersion appears to be unaffected by tidal influencing and fall within anticipated ranges of reliable estimates from other natural gradient tracer studies for the scale studied. A novel methodology for the determination of in situ degradation in a subfluvial aquifer was successfully conducted using radio-labeled 97 naphthalene. Degradation of naphthalene was confirmed by the detection of 14C-CC>2 from the mineralization of 1 4C-naphthalene. Regression analyses of the 1 4 C - C 0 2 data yielded a 1 4 C - C 0 2 production rate of 5.75E-9 mmol 1 4 C - C 0 2 /L»day. Distribution of radionuclides among CH4 and CO2 fractions and dilution of 1 4 C-CC»2 was considered to estimate half-life values for naphthalene ranging from 0.72 to 2.9 years. Under the assumption of no fractionation, a half-life for naphthalene of 1.72 years was found. The behavior of the bromide plume offshore confirmed the existence of a low groundwater flow zone verifying capture zone model predictions by Golder Associates based estimates of aquifer properties derived from aquifer-pump tests. It also indicates that dilution or dispersion does not affect concentrations 30 to 40m from the aquifer-river interface. An estimate of Rf for 1 4C-naphthalene of 1.7 was calculated based on the contrast in transport between the bromide and 1 4C-naphthalene plumes. Sorption and desorption, although small, are significant processes in the attenuation of naphthalene offshore. In summary, results of this research suggests that anaerobic degradation and desorption are, in part, controlling the fate and transport of naphthalene. Aerobic biodegradation and dilution of naphthalene within the hyporheic zone may contribute significantly to reducing the flux to the Fraser River. 98 References Andrews, E.D. 1979. Scour and fill in a stream channel, East Fork River, Western Wyoming. United States Geological Survey Professional Paper 1117. Anthony, T. 1998. An Investigation of the Natural Attenuation of a Dissolved Creosote and a Pentachlorophenol Plume. M.Sc. Thesis. University of Waterloo, Ontario, Canada ASTM, 1995. D 5543-94 Standard test methods for low-level dissolved oxygen in water. 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Personal communications. McClean, D.G. , M. Church, and B. Tassone. 1999. Sediment transport along Lower Fraser River 1. Measurements and Hydraulic Computations. Water Resources Research 35(8):2533-2548. Meade, R.H. 1985. Wavelike movement of bedload sediment, East Fork River, Wyoming. Environmental Geological Water Science. 7(4):215-225. Mihelcic, J.R. and R.G. Luthy, 1988. Degradation of polycyclic aromatic hydrocarbon compounds under various redox conditions in soil-water systems. Applied Environmental Microbilogy 54(5): 1182-1187. Montgomery, J . H . , 1996. Groundwater Chemicals Desk Reference - 2 n d Edition. Lewis Publishers, Boca Raton, Florida. Mueller, J . G . , P.J. Chapman, and P.H. Pritchard, 1989. Creosote contaminated sites - their potential for bio-remediation^ Environmental Science and Technology 23(10): 1197-1201. Norecol, Dames and Moore, 1994. Further Investigation of Canfor Site South of the BNR Line, New Westminster, B.C. Report # 11665-015-312 - February, 1994. 101 Pitken, S., R.A. Ingleton and J.A. Cherry. 1994. Use of a drive point sampling device for detailed characterization of a PCE plume in a sand aquifer at a dry cleaning facility, National Groundwater Association Eight National Outdoor Action Conference on Aquifer Restoration, Groundwater Monitoring and Geophysical Methods, Minneapolis. Rugge, K., P.L. Bjerg, J.K. Pedersen, H. Mosbaek and T.H. Christensen. 1999. An anaerobic field injection experiment in a landfill leachate plume, Grindsted, Denmark 1. Experimental setup, tracer movement, and fate of aromatic and chlorinated compounds. Water Resources Research 35(4): 1231-1246. Serfes, M.E . 1991 Determining the hydraulic gradient of groundwater affected by tidal fluctuations. Ground Water 29(4):549-555. Sufflita, J . M . , K.L. Londry and G.A. Ulrich. 1997. Determination of Anaerobic Biodegradation Activity. As seen in Manual of Environmental Microbiology, ASM Press, Washington, D.C. Thierrin J . , G.B. Davis and C. Barber, 1995. A Ground-Water Tracer Test with Deuterated Compounds for Monitoring In Situ Biodegradation and Retardation of Aromatic Hydrocarbons. Ground Water. 33(3):469-475. Todd, D.K. 1959. Ground Water Hydrology, John Wiley 86 Sons, London. United States Environmental Protection Agency, 1992. Contaminants and remedial options at wood preserving sites. Office of Research and Development, Washington, D . C , EPA/600/R-92/182. Unger, B. 199x. Two-Dimensional Simulation of Contaminant Transport in a Tidally Influenced Aquifer with a High Hydraulic Conductivity and Low Regional Gradient. Major Paper Requirement for M.Sc. (non-thesis). VanderGriendt, M. 2000. Personal Communications. Vroblesky, D.A., and Chapelle, F., 1994. Temporal and spatial changes of terminal electron-accepting processes in a petroleum hydrocarbon-contaminated aquifer and the significance for contaminant biodegradation. Water Resources Research 30(5): 1561 -1570. Wilson, J .T. , S.E. Morlock and N.T. Baker. 1996. Bathymetric Surveys of Morse and Geist Reservoirs in Central Indiana Made with Acoustic Doppler Current Profiler and Global Positioning System, Water-Resources Investigations, USGS Report # 97-4099 Wiedemeier, T .H. , H.S. Rifai, C .J . Newell and J.T. Wilson. 1999. Natural Attenuation of Fuels and Chlorinated Solvents in the Subsurface. John Wiley 8s Sons, New York. 102 Wiedemeier, T.H. , Wilson, J.T. , Kampbell, D.H. and Miller, R.N. 1994. Proposed Air Force guidelines for successfully supporting the intrinsic remediation (natural attenuation) option at fuel hydrocarbon contaminated sites In: Proceedings of the Eighth national outdoor action conference and exposition; aquifer remediation/ ground water monitoring/geophysical methods. Ground Water Management. 18; 159-174. Yim, C S . and M.F.N. Mohsen. 1992. Simulation of Tidal Effect on Contaminant Transport in Porous Media. Ground Water 30(1):78-86. 103 A p p e n d i x A : A p p r o v a l s a n d P e r m i t s 104 FRASER -1P0RT email: fraserport@frpa.com www.fraserportauthority.com File: (022)D-10*03 June 23,1999 Mr. Mario Bianchin c/o University of British Columbia, Dept. of Earth and Ocean Sciences, S T A T E M E N T 6339 Stores Road, Vancouver, B.C. V6T 1Z4 Dear Mr. Bianchin: Re: Construction Approval - Lease - .79 ha (1.951 ac) fronting a portion of Pel. A, R.P. 449, Lot 16, Gp.l, N.W.D. The Fraser River Port Authority has reviewed and approved the above noted application, subject to the conditions set out herein. The Port Authority's review of the plans has been to determine the type of construction, location of the works and impact on navigation. The Port Authority has not approved any Geotechnical, Architectural or Engineering aspects of the project. Your application has also been referred to the Fraser River Estuary Management Program (FREMP) for review. As a result of this review, you are required to comply with the conditions outlined in the enclosed letter from the Environmental Review Committee (ERC) dated May 5, 1999. The environmental recommendations, contained herein are valid until August 1, 2000. After this date the above recommendations will be VOID, no longer valid. If the subject works have not been SUBSTANTIALLY COMPLETED by that time, a new approval will be required. This will ensure that the proposed works will conform to current habitat management policy and guidelines. It is your responsibility to ensure the plans, specifications and inspections comply with all applicable Federal, Provincial and Municipal requirements. You are also required to comply with all regulations made by insurance underwriters, governing your occupation of said premises. Canada T/Hirntar Jxir FREMP CPR# 99O7F072 OS/09/99, p a g e 2 1 . T h e p r o j e c t s h a l l b e a s d e s c r i b e d i n t h i s l e t t e r , t h e s u b j e c t FREMP a p p l i c a t i o n a n d t h e r e p o r t t i l l e d , " F a t e a n d T r a n s p o r t o f C r e o s o t e - D e r i v e d C a r t a m L n a t i o n i n G r o u n d w a t e r D i s c h a r g i n g i n t o a T i d a l l y F o r c e d R i v e r - P r o p o s a l t o C o n d u c t T w o T r a c e r S t u d i e s t o E v a l u a t e I n t r i n s i c B i o d e g r a d a t i o n o f C r c o a o t e - D e r i v e d C o r r t a n r i h a n t s " . 2 . D o m t a r I n c . m u s t e n s u r e t h a t a l l w o r k a s s o c i a t e d w i t h t h e s u b j e c t p r o j e c t c o m p l i e s w i t h t h e requirements o f t h e Fisheries Act a n d a n y o t h e r a p p l i c a b l e l a w s a n d r e g u l a t i o n . 3 . T h e r e i s t o b e N O d i s t u r b a n c e t o t h e riparian v e g e t a t i o n l o c a t e d a t t h e s u b j e c t s h e . 4. T h e p r o j e c t m u s t b e c o m p H p r i s o a s t o m i r u m i z e t h e r e l e a s e o f s i l t s e d i m e n t o r s e d i m e n t - l a d e n w a t e r i n t o a n y w a t e r c o u r s e o r w a t e r b o d y . 5 . T h e p r o j e c t m u s t b e u n d e r t a k e n a n d c o m p l e t e d i n s u c h a m a n n e r s o a s t o p r e v e n t t h e r e l e a s e o f s u b s t a n c e s d e l e t e r i o u s t o fish a n d o t h e r a q u a t i c l i f e ( i n c l u d i n g , b u t n o t l i m i t e d to, d e b r i s , g a s o l i n e , o i l , g r e a s e , e t c . ) o n t o t h e u p l a n d a n d / o r i n t e r d d a l foreshore o f o r i n t o a n y w a t e r c o u r s e . F u r t h e r m o r e , a l l w a s t e m a t e r i a l s r e q u i r i n g d i s p o s a l m u s t b e d i s p o s e d o f a t a n a u t h o r i z e d u p l a n d d i s p o s a l s i t e . 6 . W a t e r - b a s e d m a c h i n e r y o r e q u i p m e n t ( e . g . , b a r g e s , e t c . ) m u s t b e l o c a t e d a n d firmly m o o r e d m d e e p w a t e r , t a r e n o u g h a f l s h o r c t o p r e v e n t a n y g r o u n d i n g o n t h e f o r e s h o r e o r b e d o f t h e F r a s e r R i v e r . T h e o n l y e x c e p t i o n t o t h i s c o n d i t i o n i s t h a t u s e m a y b e m a d e o f v e r t i c a l s p u d s t o h o l d b a r g e ( s ) i n p l a c e . 7 . L a n d - b a s e d e q u i p m e n t o r m a c h i n e r y m u s t o p e r a t e from t h e u p l a n d . L a n d - b a s e d e q u i p m e n t o r m a c h i n e r y s h a l l N O T o p e r a t e from w i t h i n t h e l n t e r t i d a l a r e a o f t h e F r a s e r R i v e r . 8 . T h e F i e l d S u p e r v i s o r , D F O C o n s e r v a t i o n a n d P r o t e c t i o n , F r a s e r V a l l e y W e s t ( t e l . 6 0 4 - 6 0 7 - 4 1 5 0 o r r a x 6 0 4 - 6 0 7 - 4 1 9 9 ) , a n d B r i a n N a i t o D F O H a b i t a t M a n a g e m e n t ( t e l . 6 0 4 - 6 6 6 - 8 1 9 0 o r f a x 6 0 4 - 6 6 6 - 6 6 2 7 ) a r e to b e n o t i f i e d a t l e a s t five ( 3 ) d a y s j j r i o r to d » e s t a r t o f t h e p r o p o s e d w 9 . I t i s u n d e r s t o o d t h a t b y p r o c e e d i n g w i t h t h e p r o j e c t , D o m t a r I n c . a n d / o r i t s a g e n t s a n c V o r c o n t r a c t o r s s h a l l h a v e i n d i c a t e d t h a t t h e y u n d e r s t a n d a n d h a v e a g r e e d t o t h e foregoing c o r x h t i o a s . I n t h i s r e g a r d , a c o p y o f t h e E R C l e t t e r o f a d v i c e r e g a r d i n g t h i s p r o j e c t i s t o b e p r o v i d e d t o a n y c o n t r a c t o r s ) p r i o r t o w o r k c o m m e n c i n g . I n a d d i t i o n , a c o p y o f t h e E R C l e t t e r o f a d v i c e i s t o b e r e t a i n e d o n s i t e a t a l l t i m e s w h e n t h e p r o j e c t i s u n d e r w a y . T h e a b o v e r e c o m m e n d a t i o n s a r e v a l i d u n t i l D e c e m b e r 2 , 2 0 0 0 . A f t e r t h a t d a t e t h e a b o v e r e c o m m e n d a t i o n s w i l l b e v o i d , n o l o n g e r v a l i d . I f t h e s u b j e c t w o r k s h a v e n o t b e e n s u b s t a n t i a l l y c o m p l e t e u b y t h a t t i m e , a n e w a p p l i c a t i o n f o r r e v i e w w i l l b e r e q u i r e d . T h i s w i l l e n s u r e t h a t t h e p r o p o s e d w o r k s w i l l c o n f o r m t o c u r r e n t e n v i r o n m e n t a l m a n a g e m c a t p o l i c y , g u i d e l i n e s a n d l e g i s l a t i o n P l e a s e n o t e t h a t t h i s l e t t e r o f a d v i c e s h o u l d n o t b e t a k e n t o i m p l y a p p r o v a l o f t h e s u b j e c t w o r k s i n a c c o r d a n c e w i t h t h e h a b i t a t p r o t e c t i o n p r o v i s i o n s o f t h e Fisheries Act o r a n y o t h e r f e d e r a l o r p r o v i n c i a l l e g i s l a t i o n . I f h a r m f u l a l t e r a t i o n , d i s r u p t i o n o r d e s t r u c t i o n o f f i s h h a b i t a t o c c u r s a s a r e s u l t o f a c h a n g e i n t h e p l a n s f o r t h e s u b j e c t p r o p o s e d w o r k s , o r f a i l u r e to i m p l e m e n t t h e a d d i t i o n a l m e a s u r e s s p e c i f i e d a b o v e , c o n t r a v e n t i o n o f s u b s e c t i o n 3 5 ( 2 ) o f t h e Fisheries Act c o u l d o c c u r . T h e a b o v e c o m m e n t s a n d r e c o m m e n d a t i o n s a r e b a s e d s o l e l y u p o n c o n s i d e r a t i o n b y t h e E R C m e m b e r e n v i r o n m e n t a l a g e n c i e s o f t h e p o t e n t i a l e n v i r o n m e n t a l i s s u e s a s s o c i a t e d w i t h m i s p r o j e c t I t i s p o s s i b l e m a x t h e E R C m a y s u b s e q u e n t l y b e m a d e a w a r e o f l e g i t i m a t e e n v i r o n m e n t a l o r o t h e r c o n c e r n s h e l d b y o m e n . A n y s u c h M<y|i*fa«*J c o m m e n t s m a t m a y b e r e c e i v e d w i l l b e f b t w a r u ^ d t o y o u f o r y o u r a p p r o p r i a t e c o n s i d e r a t i o n . A l l rKM - e n v i r o n n i e n t a l i s s u e s , i n c l u d i n g z o n i n g a n d n e c e s s a r y p e r m i t t i n g , m u s t b e a d d r e s s e d d i r e c t l y w i t h t h e r e s p o n s i b l e a u t h o r i t i e s . 1*1 Atomic Energy Control Board Commission de contr6le de I'energie atomique 09-04974-00 RADIOISOTOPE LICENCE PERMIS DE RADIO-ISOTOPE Licence Number Numero de I) LICENSEE The Atomic Energy Control Board issues t h i s l i c e n c e to: U n i v e r s i t y of B r i t i s h Columbia Suite 50 - 2075 Wesbrook Mall Vancouver, BC V6T 1Z1 he r e i n a f t e r «the l i c e n s e e * . II) PERIOD This l i c e n c e i s v a l i d from: December 30 1999 to November 30 2000. I l l ) LICENSED ACTIVITY This l i c e n c e i s issued f o r the POSSESSION, IMPORTATION and USE of the radio a c t i v e prescribed substance or the device containing the radio a c t i v e p r e s c r ibed substance described i n Section IV f o r : tracer studies (858) IV) RADIOACTIVE PRESCRIBED SUBSTANCE ITEM DESCRIPTION Carbon 14 POSSESSION LIMIT UNSEALED SOURCES 400 MBg MAXIMUM ACTIVITY SEALED SOURCES n/a Bq = bec q u e r e l kBq GBq = g i g a b e c q u e r e l TBq g = gram kg SQ = scheduled q u a n t i t y k i l o b e c q u e r e l MBq t e r a b e c q u e r e l PBq ki l o g r a m Mg TYPE OF DEVICE n/a megabecquerel p e t a b e c q u e r e l megagram. The amount of r a d i o a c t i v i t y f o r the r a d i o a c t i v e p r e s c r i b e d substance o r substances r e f e r r e d t o i n each item, s h a l l not exceed the p o s s e s s i o n l i m i t f o r un s e a l e d sources, o r the maximum a c t i v i t y p e r s e a l e d source o r d e v i c e i n accordance w i t h the p r o v i s i o n s of the above t a b l e . «Sealed Source* means a r a d i o a c t i v e p r e s c r i b e d substance i n a capsule that i s s e a l e d o r i n a cover to which the substance i s bonded, where the c a p s u l e o r cover i s s t r o n g enough t o prevent con t a c t w ith and d i s p e r s i o n o f the r a d i o a c t i v e p r e s c r i b e d substance under the c o n d i t i o n s of use f o r which the c a p s u l e o r cover i s designed. When a devi c e i s l i s t e d o p p o s i t e a r a d i o a c t i v e p r e s c r i b e d substance, the s a i d substance i s t o be used o n l y i n t h a t d e v i c e . V) LOCATION Subject to the c o n d i t i o n s o f t h i s l i c e n c e , the r a d i o a c t i v e p r e s c r i b e d substance(s) may be used a t : Domtar Research S i t e 25 B r a i d S t r e e t Coquitlam, BC VI) CONDITIONS In a d d i t i o n to the Atomic Energy C o n t r o l R e g u l a t i o n s and the Tr a n s p o r t Packaging of R a d i o a c t i v e M a t e r i a l s R e g u l a t i o n s , the l i c e n s e e s h a l l comply w i t h the f o l l o w i n g c o n d i t i o n s : 1. Environmental M i t i g a t i o n The l i c e n s e d a c t i v i t y s h a l l be conducted i n accordance w i t h the l e t t e r i s s u e d by D. Hasselmann o f the F r a s e r R i v e r E s t u a r y Management' Program to Domtar Inc., dated September 8, 1999. 2. S t a f f T r a i n i n g The l i c e n s e e s h a l l ensure t h a t o n l y persons p r o p e r l y t r a i n e d t o work Licensee's Copy - O r i g i n a l .../ 2 AEC8 53 Rev. 1979/GCEA 53 Rev 1979 1*1 Atomic Energy Commission de controle Control Board de I'energie atomique 09-04974• RADIOISOTOPE PERMIS DE Licence Number LICENCE RADIO-ISOTOPE Numero de permis Page 2 with rad i o a c t i v e prescribed substances and informed of the hazards involved are permitted to work with r a d i o a c t i v e p r e s c r i b e d substances or operate devices containing r a d i o a c t i v e p r e s c r i b e d substances. (565-2) 3. Storage When i n storage, r a d i o a c t i v e prescribed substances or devices containing r a d i o a c t i v e prescribed substances s h a l l be stored i n an area, room, or enclosure that: (a) i s a c c e s s i b l e only to personnel authorized by the l i c e n s e e ; (b) has a f f i x e d to i t s e x t e r i o r a c l e a r l y v i s i b l e and l e g i b l e r a d i a t i o n warning sign, and the name or job t i t l e and phone number of a 24 hour contact i n case of emergency; (c) does not have, at any occupied l o c a t i o n outside the area, room or enclosure, a dose rate that exceeds 2.5 fiSv/h. (575-2) 4. Licence Posting This l i c e n c e , or a copy thereof, s h a l l be conspicuously posted at a l l s p e c i f i c l o c a t i o n s l i s t e d i n Section V and s h a l l be a v a i l a b l e a t a l l other loc a t i o n s where the r a d i o a c t i v e p r e s c r i b e d substances l i s t e d i n Section IV are used or stored. (573-1) 5. Operation N o t i f i c a t i o n The licensee s h a l l n o t i f y the AECB i n w r i t i n g w i t h i n 30 days, of the l o c a t i o n of any land, base(s) of operations, or premises the l i c e n s e e occupies, where the l i c e n s e e uses or stores r a d i o a c t i v e p r e s c r i b e d substances f o r more than 90 consecutive days. The l i c e n s e e s h a l l n o t i f y the AECB i n w r i t i n g , within 30 days, when the use or storage of a l l r a d i o a c t i v e prescribed substances at such l o c a t i o n s i s discontinued. (300-4) 6. Operation N o t i f i c a t i o n Upon request, the l i c e n s e e s h a l l n o t i f y the AECB i n accordance with the request of the time, date and l o c a t i o n of each l i c e n s e d a c t i v i t y as soon as they have been e s t a b l i s h e d . Notwithstanding t h i s requirement, the l i c e n s e e s h a l l n o t i f y the AECB of any proposed l i c e n s e d a c t i v i t y i n which more than 1000 scheduled q u a n t i t i e s of a r a d i o a c t i v e p r e s c r i b e d substance with a h a l f - l i f e g reater than 10 days w i l l be released to the environment. (28-1) 7. Storage N o t i f i c a t i o n Upon request from the AECB the l i c e n s e e s h a l l n o t i f y the AECB of the storage s i t e l o c a t i o n of each r a d i o a c t i v e p r e s c r i b e d substance. (298-1) 8. Record Requirements The l i c e n s e e s h a l l ensure a that a copy of the f o l l o w i n g documentation, s p e c i f i c to each l o c a t i o n where r a d i o a c t i v e p r e s c r i b e d substances are used and stored f o r more than 90 consecutive days are maintained at that l o c a t i o n : (a) an inventory of r a d i o a c t i v e p r e s c r i b e d substances; (b) the names of a l l persons involved i n the use and handling of r a d i o a c t i v e p r e s c r i b e d substances; (c) f u l l p a r t i c u l a r s of d i s p o s a l , whether by s a l e or otherwise, of any r a d i o a c t i v e p r e s c r i b e d substances; (d) records to show the dose of i o n i z i n g r a d i a t i o n r e c e i v e d by any person as a r e s u l t of the use of r a d i o a c t i v e p r e s c r i b e d substances, i f applicable,-(e) a l i s t of Atomic Radiation Workers at the l o c a t i o n , i f a p p l i c a b l e ; (f) the operating and emergency procedures, and any s p e c i a l procedures r e l a t e d to dose c o n t r o l ; (g) records of dose r a t e and contamination surveys, i f a p p l i c a b l e ; (h) leak t e s t r e s u l t s . The c o n t i n u i t y of consecutive days i s not broken during o f f s i t e use or o f f s i t e temporary storage. (350-2) Licensee's Copy - O r i g i n a l . . . / AEC8 53 Rev 1979/CCEA 53 Rev 1979 I l - O 1+1 Atomic Energy Commission de controle Control Board de I'energie atomique 09-04974 RADIOISOTOPE PERMIS DE Licence Number LICENCE RADIO-ISOTOPE Numero de permis Page 3 9. Operation Report A written report must be submitted to the AECB with i n 60 days of an operation using more than 1000 scheduled q u a n t i t i e s of a r a d i o a c t i v e prescribed substance with a h a l f l i f e greater than 10 days. The report should include: (a) date and l o c a t i o n of job, (b) a c t i v i t y (becquerels) and chemical form of the r a d i o a c t i v e prescribed substance used, (c) company f o r which the work was done, (d) name(s) of individual<s) who handled the r a d i o a c t i v e p r e s c r i b e d substance, (e) dosimetry r e s u l t s f o r involved personnel (include badge readings and bioassay r e s u l t s ) , (f) any incidents or unusual occurrences, (g) d i s p o s i t i o n of unused r a d i o a c t i v e p r e s c r i b e d substance, (h) f o r t r a c i n g operations: (i) the average s p e c i f i c a c t i v i t y of r a d i o a c t i v e p r e s c r i b e d substance entering and le a v i n g the system under t e s t , and ( i i ) the fate of the r a d i o a c t i v e p r e s c r i b e d substance. (102-1) 10. Contamination Meter Requirements The licensee s h a l l make a v a i l a b l e at a l l times at the l o c a t i o n where radio a c t i v e p r e s c r i b e d substances are handled or stored, a p r o p e r l y functioning contamination meter capable of d e t e c t i n g r a d i o a c t i v e contamination at the c r i t e r i a s p e c i f i e d i n t h i s l i c e n c e . (572-1) 11. Exposure Monitoring The l i c e n s e e s h a l l ensure that persons are monitored f o r r a d i a t i o n exposure from the l i c e n s e e ' s possession or use of r a d i o a c t i v e prescribed substances i n accordance with the AECB Regulatory Document R-91, "Monitoring and Dose Recording f o r the I n d i v i d u a l " . S p e c i f i c a l l y , i f monitoring i s required i t s h a l l be performed as follows: (a) Measurement of external doses of r a d i a t i o n s h a l l be by means of a personal dosimeter (i) s u pplied by an agency approved by the AECB ( i i ) s u i t a b l e f o r the type of r a d i a t i o n exposure ( i i i ) worn i n the manner and f o r the duration s p e c i f i e d by the s u p p l i e r such that the dose recorded i s i n d i c a t i v e of the external dose received by the wearer. (b) Determination of the uptake of (i) iodine-125 and iodine-131 s h a l l be i n accordance with the AECB Regulatory Guide R-58 "Bioassay Requirements f o r 1-125 and 1-131 i n Medical, Teaching and Research I n s t i t u t i o n s " and ( i i ) other r a d i o n u c l i d e s s h a l l be by means of bioassay methods approved by the AECB. (46-2) 12. Exposure Reporting Where the l i c e n s e e becomes aware of a dosimetry r e s u l t f o r a person exceeding any l i m i t i n Schedule II of the Atomic Energy Control Regulations f o r that person, the l i c e n s e e s h a l l inform the AECB within 24 hours and the person promptly. The l i c e n s e e s h a l l i n vestigate the causes and circumstances c o n t r i b u t i n g to that dosimetry r e s u l t and s h a l l provide a wr i t t e n report on the i n v e s t i g a t i o n and c o r r e c t i v e actions to the AECB w i t h i n ten days. (567-1) 13. Personal Contamination C r i t e r i a Personal p r o t e c t i v e equipment and c l o t h i n g used during work with unsealed sources s h a l l be considered to be contaminated u n t i l monitored, and decontaminated where necessary. The l i c e n s e e s h a l l ensure that personal p r o t e c t i v e equipment and c l o t h i n g i s not used i f : (a) the l e v e l s of non-fixed beta-gamma contamination exceed 0.5 Bq/cm2 averaged over an area not exceeding 100cm2, or (b) the dose rate due to f i x e d beta-gamma contamination exceeds 2.5 Licensee's Copy - O r i g i n a l AECB 53 Rev. 1979/CCEA 53 Rev 1979 1*1 Atomic Energy Commission de contrdle Control Board de I'energie atomique 09-04974-00 RADIOISOTOPE PERMIS DE Licence Number LICENCE RADIO-ISOTOPE Numero de permis Page 4 fiSv/h on contact. (376-1) 14. Contamination C r i t e r i a The licensee s h a l l ensure that: (a) on a l l normally a c c e s s i b l e working surfaces i n any area, room or enclosure where a r a d i o a c t i v e prescribed substance i s used or stored, non-fixed contamination does not exceed 5 Bq/cm2 of substances that emit only beta or gamma r a d i a t i o n or 0.5 Bq/cm2 of substances that emit alpha r a d i a t i o n averaged over an area not exceeding 100cm2, (b) on a l l other surfaces, and p r i o r to decommissioning any area, room or enclosure where a r a d i o a c t i v e p r e s c r i b e d substance has been used or stored, non-fixed contamination does not exceed 0.5 Bq/cm2 of substances that emit only beta or gamma r a d i a t i o n or 0.05 Bq/cm2 of substances that emit alpha r a d i a t i o n averaged over an area not exceeding 100 cm2, (c) the dose rate due to contamination does not exceed 0.5 /iSv/h at 0.S metre from any surface, (d) records of a l l measurements s h a l l be maintained f o r a l e a s t three years. Any other maximum contamination c r i t e r i a w i l l r e quire s p e c i f i c w r i t t e n approval of the AECB. (571-2) 15. Disposal Subject to any other c o n d i t i o n of t h i s l i c e n c e r e s p e c t i n g the disposal of s p e c i f i c r a d i o a c t i v e p r e s c r i b e d substances, a l l r a d i o a c t i v e p r e s c r i b e d substances s h a l l be disposed of by: (a) making p r i o r arrangements and returning to the s u p p l i e r , or (b) making p r i o r arrangements and sending t o Atomic Energy of Canada Limited or (c) making p r i o r arrangements and sending to a f a c i l i t y possessing an appropriate AECB Prescribed Substance Licence or a Waste F a c i l i t y Operating Licence, or (d) release through the municipal garbage system provided the radi o a c t i v e p r e s c r ibed substance(s) i s i n the s o l i d form, i s uniformly d i s t r i b u t e d i n the waste, and that the concentration i s l e s s than 1 scheduled quantity per kilogram of waste m a t e r i a l or (e) release through the municipal sewage system provided the rad i o a c t i v e p r e s c r i b e d substance(s) i s water s o l u b l e and that the concentration i n the sewer at the property l i n e f o r the f a c i l i t y i s l e s s than 0.01 scheduled quantity per l i t r e of e f f l u e n t based upon a y e a r l y average, or (f) release to the atmosphere provided the r a d i o a c t i v e p r e s c r i b e d substance(s) i s i n the form of a vapour or gas and that the concentration at the p o i n t of release i s l e s s than 0.001 scheduled quantity per cubic metre of a i r when averaged over a 1-week period. Any other waste d i s p o s a l method w i l l require s p e c i f i c w r i t t e n approval of the AECB. (576-1) 16. Transfer The l i c e n s e e s h a l l not t r a n s f e r any r a d i o a c t i v e p r e s c r i b e d substances procured under the au t h o r i t y of t h i s l i c e n c e to any person who i s pr o h i b i t e d pursuant to the Atomic Energy Control Regulations from possessing such r a d i o a c t i v e p r e s c r i b e d substances. (574-1) 17. Internal A u t h o r i z a t i o n To c o n t r o l the l i c e n s e d a c t i v i t y , the li c e n s e e s h a l l : (a) maintain a system of wr i t t e n i n t e r n a l a u t h o r i z a t i o n , (b) ensure the radioisotopes are used i n accordance with the i n t e r n a l a u thorization, (c) post the i n t e r n a l a u t h o r i z a t i o n i n or near each designated laboratory and storage l o c a t i o n , Each i n t e r n a l a u t h o r i z a t i o n s h a l l : (a) s p e c i f y the purpose of the au t h o r i z a t i o n , (b) only apply to persons under the a u t h o r i t y of the l i c e n s e e and s h a l l name those persons, (c) i d e n t i f y radioisotopes by quantity and form, and any appropriated Licensee's Copy - O r i g i n a l . .. AECB 53 Rev 1979/CCEA 53 Rev 1979 A p p e n d i x B : C -Naph tha lene S u p p l i e r S p e c i f i c a t i o n s 124 I S I G M A 11542 Fort Mims Dr. Saint Louis, Missouri 63146 USA Telephone 800-325-4581 • (314) 771-5765 Fax (314) 569-0682 KR O D N A M E : O T N U M B E R : P R O D N U M B E R : J V N A L Y S T : K ) A T E : N A P H T H A L E N E - B E N Z E N E - U L - 1 4 C 0 4 8 H 9 4 6 0 / 6 1 N 7 3 9 4 - 1 4 C 0 2 7 B D 9 / 3 / 9 9 8 : 5 1 : 1 1 P M I n j V o l u m e : 8 . 0 0 u l * * * * * M E T H O D F O R N 7 3 9 4 N A P H T H A L E N E - B E N Z E N E - U L - 1 4 C * * * * * I C o l u m n : C o l u m n T e m p : • F l o w R a t e : Jfobi l P h a s e : I I e t e c t i o n : S u p e l c o D i s c o v e r y C 1 8 , 2 5 0 x 2 . 1 m m , 5 m i c r o n 3 5 ° C 0 . 3 m l / m i n A = 0 . 1 % P h o s p h o r i c A c i d ( V / V ) i n W a t e r B = A c e t o n i t r i l e 5 0 % A F o r 1 0 m i n u t e s t o 0 % A o v e r 1 5 m i n u t e s , h o l d f o r 1 0 m i n u t e s R a d i o c h e m i c a l Wc i f i c A c t i v i t y e c u l a r W e i g h t c e n t r a t i o n * * * * * P R O D U C T I N F O R M A T I O N * * * * * 3 1 . 3 m C i / m m o l S t o r a g e T e m p 1 2 8 . 2 P a c k a g i n g 1 . 0 m C i / m l i n M e t h a n o l s o l u t i o n 2 - 8 ° C S e a l e d A m p u l e I AUC1 A, Kadiochemical (09UJ99-2W/-I0UI.U) mAU-700-600 500 400 300 200 100 r-cao 00 T-r-m o -P e a k R e t T i m e W i d t h A r e a H e i g h t A r e a # [ m i n ] [ m i n ] [ m A U * s ] [ m A U ] % 1 3 . 0 5 7 0 . 2 1 7 1 7 . 8 9 1 1 . 1 5 4 0 . 0 7 7 2 3 . 7 0 3 0 . 5 2 6 1 2 6 . 4 5 9 2 . 9 1 4 0 . 5 4 6 3 4 . 5 2 5 0 . 5 0 4 7 5 . 1 0 2 1 . 8 1 2 0 . 3 2 4 4 1 1 . 5 1 2 0 . 4 7 8 2 . 2 7 9 e 4 7 4 3 . 2 8 2 9 8 . 4 0 3 5 2 4 . 5 8 8 0 . 4 1 8 7 2 . 3 9 5 2 . 1 4 6 0 , 3 1 3 6 2 6 . 0 4 1 0 . 2 7 0 2 2 . 9 0 0 1 . 0 8 5 0 . 0 9 9 7 2 6 . 7 9 1 0 . 4 4 9 5 5 . 0 9 4 1 . 4 8 5 0 . 2 3 8 20 mini I Sigma is a Member of the Sigma-Aldrich Family P r o v i d i n g Biochemicals and Reagents for Life Science Research. A p p e n d i x C : U n i v e r s i t y o f Wa te r loo A n a l y t i c a l M e t h o d o l o g i e s 126 ORGANIC GEOCHEMISTRY LABORATORY DEPARTMENT OF EARTH SCIENCES Telephone: 519 888 4567 ext. 5180 / 6370 (written by Marianne Vandergreit) VOLATILE AND SEMI VOLATILE AROMATIC HYDROCARBON ANALYSIS (BENZENE, TOLUENE, EHTYLBENZENE, p+m-XYLENE, o-XYLENE, TRIMETHYLBENZENES (1,3,5; 1,2,4 AND 1,2,3), NAPHTHALENE, INDOLE+2-METHYL NAPHTHA, 1-METHYL NAPHTHALENE, BIPHENYL, ACENAPHTHYLENE, ACENAPHTHENE, DIBENZOFURAN, FLUORENE, PHENANTHRENE, ANTHRACENE, CARBAZOLE, FLUORANTHENE, PYRENE, BENZO (a) ANTHRACENE, CHRYSENE, BENZO (b+k) FLUORANTHENE, BENZO (a) PYRENE, INDENO (1,2,3,cd) PYRENE and DIBENZO (a,h) ANTHRACENE, AND BENZO (g.h.i) PERYLENE) INTRODUCTION: A gas chromatographic technique is described to determine volatile aromatic components of gasoline and some polycyclic aromatic components of creosote, in groundwater samples (the components are listed above). Typically, these compounds are determined by purge and trap or exhaustive extraction techniques. However, because the hydrogeologist may require many analyses to define the shape, movement and attenuation of a trace contaminant plume, purge and trap methods are too time consuming to use on a routine basis. Separatory funnel or continuous solvent extraction techniques are not only slow and labour intensive but can also suffer from volatilization losses. The methodology presented here was derived from an extraction previously described by Henderson et. al.(1976). The technique required that the partitioning of the analyte be at equilibrium between the two phases, as opposed to being exhaustively extracted from the water. APPARATUS: Aqueous groundwater samples and methanolic standards are extracted in 18 ml crimp-top hypovials with Teflon® -faced silicone septa. The determinations are performed on a gas chromatograph equipped with a splitless injection port, a 0.25mm X 30M glass DB5 capillary column with a film thickness of 0.25um and a flame ionization detector. The chromatographic conditions are as follows: injection port temperature, 275°C; initial column temperature, 35°C; initial time, 0.5 min.; heating rate, 15°C/min.; final temperature, 300°C; final time, 10.0 min.; detector temperature, 325°C; column flow rate, 3 ml/min helium. PROCEDURE: \)SAMPLE BOTTLE PREPARATION. Bottles and other glassware are soaked in a commercial alkaline cleaning solution for several hours, then rinsed with deionized water, dilute nitric acid, and more deionized water. The bottles are then baked overnight at 110°C \\)SAMPLE COLLECTION AND HANDLING. Each 18 ml hypovial sample bottle is filled without headspace, quickly crimp sealed with a Teflon septa and then stored at 4°C until extracted (7-14 day time limit). Prior to capping, sodium azide (200ul of a 10 % solution) may be added to the sample bottle as a preservative, if analysis will not occur with 7days. To solvent extract a sample (or standard), the septum cap of the vial is quickly removed and 2.0 ml of water is removed with a syringe. This is followed by the addition of l 1.0 ml of dichloromethane, containing the internal standards m-fluorotoluene and 2-fluorobiphenyl. The vial is quickly resealed and agitated on its side at maximum speed (350 rpm) on a platform shaker for 15 min. After shaking, the vial is inverted and the phases are allowed to separate for 10 to 30 minutes. Approximately 0.7ml of the dichloromethane phase is removed from the inverted vial with a syringe (through the septum) and placed in a sealed autosampler vial for injection into the gas chromatograph. \\\)QUALITY CONTROL. Samples and standards are equilibrated to room temperature (approx. 22°C) before extraction. A calibration is made in internal standard mode and standards are run in triplicate at four different levels (or more) covering the expected sample range. A multiple point linear regression is performed to determine linearity and slope of the calibration curve. Standards are prepared by spiking water with a concentrated methanolic stock standard, and are extracted in the same manner as samples. Three methanolic stock standards are used, each an order of magnitude above the other. The methanolic stock standard is prepared gravimetrically, injecting the various pure compounds through a septum into one 60 ml aliquot of methanol, or are purchased commercially. Matrix spikes are performed by spiking a known amount of mid-range standard into a duplicate field sample and then calculating the amount recovered after extraction. Reagent water blanks are run on a daily basis. The methanolic stock standards are stored in a freezer when not in use and are replaced when accuracy becomes unacceptable. Method Detection Limit Aug 4,1999 Units are ug/L (ppb) N Xo X S MDL benzene toluene ethylbenzene p+m-xylene o-xylene 1,3,5-trimethylbenzene 1,2,4-trimethylbenzene 1,2,3-trimethylbenzene naphthalene indole+2-methyl naphthalene 1 -methyl naphthalene biphenyl acenaphthylene acenaphthene dibenzofuran fluorene phenanthrene anthracene carbazole fluoranthene pyrene B(A)anthracene chrysene 9 9 9 9 9 9 9 9 9 9 9 9 9 9 8 9 9 9 8 9 9 8 8 23.91 22.55 22.82 45.64 23.64 23.64 23.36 24.72 15.69 31.25 15.69 30.44 15.69 15.63 15.46 15.69 15.69 15.69 16.87 15.69 15.63 15.63 15.69 28.82 27.91 25.34 49.56 25.66 26.05 25.28 26.18 16.93 24.67 16.89 33.07 17.00 19.21 14.89 18.14 17.69 16.12 13.44 18.82 19.26 10.91 22.42 1.29 3.72 3.53 10.22 1.26 3.64 1.99 5.76 1.03 3.00 0.84 2.43 0.85 2.45 0.86 2.49 1.50 4.34 1.61 4.66 0.93 2.68 1.66 4.80 0.92 2.67 0.78 2.27 0.89 2.68 0.92 2.67 2.23 6.45 1.25 3.63 1.58 4.74 1.79 5.17 1.49 4.30 1.09 3.26 2.10 6.30 2 B(b+k)fluoranthene 8 31.25 16.88 6.71 20 11 B(a)pyrene 8 15.69 10.29 8.14 24 40 indeno(1)2,3,c,d)pyrene+dibenzo(a,h)anthracene 9 62.63 >62 63 benzo(g,h,i)perylene 9 31.38 >3L38 N= Sample Size Xo = True Value of Standard X = Average Calculated Value of Standards S = Standard Deviation MDL = Method Detection Limit ND = Not Detected LITERATURE CITED. Henderson, J.E., G.R. Peyton and W.H. Glaze (1976). A convenient liquid-liquid extraction method for the determination of halomethanes in water at the parts-per-billion level. IN: Identification and analysis of organic pollutants in water. Keith, L.H. ed. Ann Arbor Science Publishers Inc., Ann Arbor, Ml. 3 Analytical procedures of inorganic constituents (written by Tracy Fowler) Solutions Analyt ical Lab University of Waterloo Department of Earth Science Methods of Analysis Anions (bromide, chloride, fluoride, nitrate, nitrite, phosphate, sulphate, iodide) The anions are analyzed using a Dionex A S 3 or A S 4 A anion exchange column. The utilization of a Dionex Micro Membrane Suppressor Column increases stability. The instrument used is either a Dionex System 2000 ion chromatograph or a Waters Ion Chromatograph utilizing a WISP 71 OB sampler, a model 745 Data Module, a model 510 pump and a model 430 Conductivity detector. The method of detection for both systems is conductivity. The samples are filtered (0.45|i) and kept at 4 ° C until analyzed. The instruments are operated using manufacturers' specifications. The results are reported as milligrams per litre. A daily run of twenty to fifty samples contains 10 to 20 in-house standards. A setpoint standard is also run at least twice during the run in order to maintain in-house standard quality. The samples are rerun if the setpoint standard does not come within five percent of the stated value. Charge balances are done on all samples where possible Alkalinity The alkalinity is measured by titrating the sample to a pH of 4.3 with a calibrated standard acid (H2SO4). A Metrohm auto-titration unit performed the analysis. The total alkalinity is reported as ppm HCO3. Cations The cations are analyzed using a Thermo Jerrell A s h IRIS plasma spectrometer (ICP). The instrument conditions are set using manufacturer's specifications. The samples are filtered (0.45u) and acidified to a pH of 2 with nitric acid. The samples are stored at 4 ° C until they are analyzed. The in-house standards are commercially available and are compared to standards prepared by the Solutions Analytical Lab. The standards are checked every ten samples to monitor drift. The samples are run in duplicate. A setpoint standard is also analyzed twice during a run of fifty samples. This assures the day to day quality of our in-4 1 "SO I house standards. The run is repeated if the in-house standards are not within five percent of the actual va lue. 5 I . »M 2.4 Tracer study with C-naphthalene 2.4.1 Description Bianchin ( thesis, in progress) performed a tracer s tudy using radiolabelled naphtha lene ( 1 4 C) on the portion of the plume beneath the river at the studied site. T h e p u r p o s e of the tracer test w a s to determine if naphthalene w a s degrading under anaerob ic condi t ions by analyzing for radiolabelled CO2, a probable by -product Of naphtha lene biodegradat ion. A full descr ipt ion of the f ie ldwork by Bianchin c a n be found in appendix C . 2.4.2 Analytical methods A method was developed to separate and analyse 1 4C-naphthalene and 14C02 based on the work by Rugge et al. (1999). Samples were collected in completely filled 60 ml hypovials sealed with Teflon coated septa and aluminium crimps. The samples were preserved with 10 M NaOH at a rate of 10 uL per 1ml of sample, and kept cold (stored in coolers with ice packers) until further analyses at the University of Waterloo. Samples for total radioactivity (naphthalene and any biodegradation products) were analysed by adding 5ml of groundwater to 10 ml of scintillation cocktail (EcoLume, ICN). The vials were stored in the dark for 48 hours and then quantified using a scintillation counter (Canberra Packard, Model 2100TR). Samples for 1 4C-naphthalene and 14C02 were prepared by extracting 10 ml of groundwater with 1ml of pentane and shaken by 15min. After extraction, 500 u.L of pentane were transferred to 10 ml of scintillation fluid, stored in the dark for 48 hours and then counted for 1 4C-naphthalene activity. For CO2 radioactivity, 5 ml of the groundwater left from the pentane extraction were transferred to a vial containing 1 ml of 1M HCL. The vial was placed in an outer vial containing 1ml of 1.25 M NaOH to trap the expelled CO2. The system was closed with a pressure cap and a teflon coated septum. After 24 hours the contents of the outer vial were mixed with 10 ml of scintillation fluid, stored in the dark for 48 hours and then counted. 2.4.3 Radioactivity units A scintillation counter is used to determine the radioactivity of a sample. The units reported by the scintillation counter are either C P M (counts per minute) or DPM (disintegrations per minute). C P M units are related to the amount of radioactivity that the scintillation counter detects in the sample. Since the counter is not 100% efficient, it must me calibrated with standard of known radioactivity. DPM units take into account the counter efficiency. The radioactivity unit in the SI units system is the Currie (Ci, 1uCi = 2.22E + 6DPM). In water samples it is common to report the amount of radioactivity per volume of sample (e.g. jaCi/L, DPM/5ml). To obtain the radioactivity attributed to radiolabeled naphthalene and/or byproducts, in water samples, background radioactivity from blank samples must be subtracted. 2.4.4 Efficiency of analytical technique The efficiency in the recovery of naphthalene by pentane extraction was calculated using radiolabeled naphthalene from the University of Waterloo laboratories. The stock was preserved to avoid any biodegradation using Na-azide at a rate of 1 uL per 1 ml of sample. The 1 4 C-naphthalene stock was analysed in the same way the field samples were treated. The results show that the naphthalene extraction efficiency is 9 9 % (Table 2.4). The possibility of 1 4C-naphthalene carryover to the NaOH trap was quantified. Since any radioactivity found in the NaOH trap would be attributed to 14C02 it had to be ensured that • 1 4 C-naphthalene would not be carried over to the trap. The naphthalene carryover was calculated by analysing the 1 4C-naphthalene stock in the same way that the field samples were treated. The results show that a small percentage of 1 4C-naphthalene (<0.6%) is 1 transferred to the NaOH trap. Therefore any radioactivity in the NaOH trap of less than 10 D P M above background levels is not reliable (Table 2.5) The efficiency of the CO2 trapping system was quantified using radiolabeled NaCOa from the University of Waterloo laboratories. It was calculated by transferring radiolabeled NaC03 into the trapping system. The system was treated as it was done for the field samples, and the radioactivity in the NaOH trap was related to the radioactivity of the stock. The results show that the recovery efficiency is, in average, 8 7 % (Table 2.6). 7 Table 2.6 NaOH trap efficiency Sample N a C 0 3 std. N a C 0 3 -back NaOH trap NaOH-back Efficency (DPM) (DPM) (DPM) (DPM) E-1 7,606.79 7,513.99 6,058.37 5,782.28 77 .0% E-2 3,950.13 3,857.33 3,439.85 3,163,76 82 .0% E-3 1,891.45 1,798.65 1,670.17 1,394.08 7 7 . 5 % E-4 1,046.67 953.87 1,062.77 786.68 8 2 . 5 % E-5 191.34 98.54 377.20 101.11 102.6% E-6 165.92 73.12 349.31 73.22 100 .1% Blank-1 92.80 276.09 Average: 8 6 . 9 % Efficency = (NaOH-back) / (NaCO 2 -back) Table 2.4 Naphthalene extraction efficiency Sample Total Tot-back Naphthalene Naph-back Naph/Tot (DPM) (DPM) (DPM) (DPM) Naph. Stock (1) 1,535.49 1,468.93 1,771.10 1,719.41 117 .1% Naph. Stock(2) 1,898.73 1,832.17 1,569.41 1,517.72 8 2 . 8 % Naph. Stock(3) 1,480.82 1,414.26 1,682.71 1,631.02 115 .3% Naph. Stock (4) 1,735.06 1,668.50 1,634.28 1,582.59 9 4 . 9 % Naph. Stock (5) 1,812.98 1,746.42 1,615.48 1,563.79 8 9 . 5 % Naph. Stock (6) 1,716.23 1,649.67 1,604.85 1,553.16 9 4 . 2 % A v g . background 66.57 51.69 Average: 9 8 . 9 6 % Table 2.5 Naphthalene carryover Sample Date Total Tot-back Naphthalene Naph-back Naph/Tot analysed (DPM) (DPM) (DPM) (DPM) Naph. Stock (1) June/12/00 1,657.58 1,591.02 1,624.47 1,572.78 9 8 . 9 % Naph. Stock (2) June/12/00 1,748.41 1,681.85 1,585.39 1,533.70 9 1 . 2 % A v g . background 66.57 51.69 Naph. Stock(3) June/05/00 1,535.49 1,466.46 1,771.10 1,718.14 117 .2% Naph. Stock (4) June/05/00 1,898.73 1,829.70 1,569.41 1,516.45 8 2 . 9 % A v g . background 69.03 52.96 Sample NaOH trap NaOH-back NaOH/Tot Naph + NaOH (DPM) (DPM) (% of total) i Naph. Stock (1) 66.12 10.00 0.6% 9 9 . 8 % Naph. Stock (2) 60.75 4.63 0.3% 9 1 . 7 % A v g . background 56.13 Naph. Stock (3) 64.75 4.83 0.3% 117.6% Naph. Stock (4) 65.38 5.46 0.3% 8 3 . 3 % A v g . background 59.92 \5<Y A p p e n d i x D : M e t h o d for B r o m i d e A n a l y s i s 135 M e t h o d o l o g y F o r B r o m i d e A n a l y s i s U s i n g a C o m b i n a t i o n Ion S e l e c t i v e E l e c t r o d e (ISE) Scope This method covers the determination of bromide in groundwater samp les col lected from the Fraser S a n d s aquifer beneath the Domtar site in Coqui t lam. The groundwater chemistry is highly variable at the site primarily due to the presence of varying concentrations of polycycl ic aromatic hydrocarbons (PAHs) (see graph at end of document). Matrix interference has been observed in-lab with groundwater samples containing P A H s . Cho ice of technique for determining Bromide concentrat ions in groundwater samples must take into consideration matrix interference and potential analytical error. Therefore, two techniques are proposed for measur ing bromide as part of the schedu led onshore and offshore tracer studies. The two analytical techniques are (1) Direct Measurement [proposed field technique] and (2) Known Addition [proposed laboratory technique]. What follows is a detailed description of the methodology including: • required equipment and reagents, • bromide probe handling and preparation, • Method of Direct Measurement • Method of Known Addit ion, and • Quality Assurance/Qual i ty Control ( Q A / Q C ) procedures. Referenced Documents The Amer ican Society for Test ing and Materials, Standard Test Method for Bromide Ion in Water [D 1246-88], Annua l Book of A S T M Standards, Vo l . 11 .01 ,1988 . Standard Methods for the Examinat ion of Water and Wastewater , 20 Edit ion, 1998. Bromide Electrode Instruction Manua l ; Mode l 9635 lonplus Ser ies Bromide Electrode, Orion Resea rch , Inc. 1997. 136 Equipment and Reagent Requirements Table 1: Equipment and Reagent Requirements Equipment Reagents Orion Combinat ion sure-flow Bromide electrode Distilled Water F isher Scientific. Accumet meter 0.1 M Bromide Stock Solution Magnet ic plate stirrer Standard solutions (1000 ppm, 100 ppm ) Magnet ic stir bar Ionic Strength Adjuster (ISA) 25.0 ml volumetric pipettes Reference filling solution: Optimum Results D Two Ependorf pipettors; one set for delivery of 500 ul and the other set for multiples of 1000 ul. 24+ 50ml plastic beakers or suitable plastic vesse ls 1000 ml and 100 ml volumetric flask Preparation of Bromide Solutions Standard solutions will be prepared using Potass ium Bromide (KBr ) Certif ied A . C . S . grade. K B r F . W . 119.01 g/mole. For a 0.1 M solution of B r 1:1 stochiometry therefore, 1 mole of Br" requires 119.01 g of K B r weigh out 11.9 g of K B r into a tarred weigh dish. Record weight of K B r in research book (provided) A d d weighed K B r to a c lean 1L volumetric flask and add about 300 ml of H 2 0 137 Mix solution by swirling flask until the K B r is completely d issolved, then Top off to a total vo lume of 1L For Br- Standard solutions Example Calculat ions For a 1000mgBr/L M M = M 2 V 2 where = stock solution concentration, = volume of stock solution needed to make up 1 L of a 1000 ppm solution, M 2 = desired concentration i.e. 1000 mg/L and V 2 = final vo lume of standard solution (1L) 0.1 mole B r / L x 79.904 g B r /mole B r = 7.9904 g B r / L 7.9904 g B r / L x V , = 1 g B r / L x 1L V , = 0.1252 L Therefore, 125.2 ml of the 0.1 M of the Br- stock solution is added to a 1L volumetric flask. Handling and Checking Performance of the Orion Sure-flow Combination Bromide Electrode Prepare electrode for use as descr ibe on pages 6 to 7 of instruction manual . The probe should be checked to ensure proper sensitivity (i.e. slope). The probe is operating properly when a slope o f - 5 4 to - 6 0 mV/decade (1 log cycle) is obtained from a plot of electrode potential (mV) vs bromide concentrat ion. This can be done rather quickly with use of only two solutions that are an order of magnitude in difference. Instructions are as follows: • A d d 100 ml of distilled water to a 150 ml beaker 138 • A d d 2ml of ISA solution (Fisher Scientific brand Cat No . 13-620-823) • Pipet 1 ml of the 0.1 M Br- solution to the 100ml of water • Record temperature of solution. • Immerse probe into the diluted solution and record reading b e c o m e s stable, record the amount of time it takes to reach stability and standardize the time for each reading. • Pipet 10 ml of 0.1 M Br- solution into the s a m e beaker and take another reading • The difference between the two readings should be somewhere between - 5 4 to - 6 0 mV. • Compa re results of test with s lope values listed in Table 7 (p. 44 of Instruction Manual) . If s lope does not fall into this range then check Troubleshooting sect ion of Instruction manual . Measuring Techniques Prior to conducting any measurements using the ISE, review the section on General Laboratory Practice measuring hints provided in the instructions manual (p.10). Direct Measurement Method Scope The Direct Measurement method is applicable to waters whose bromide concentration is greater than 1 mg/L, and for measur ing a large number of samples . It is not a suitable method where matrix interference is known to occur (solutions with ionic strength greater than 0.1 M or, in this c a s e organics). The concentration of samples is determined by compar ison to standards or a calibration curve prepared on a semi- log graph. U s e of this 'field' method is to obtain approximate real-time concentrations of bromide in groundwater samples . Note: Analysis of matrix spiked samples representative of background groundwater samples resulted in a percent recovery of +/- 5%. Although matrix intederence is expected to have little effect on bromide analysis of samples collected from the onshore tracer study, deviations of field values from true values will reflect sensitivity of probe to temperature. Matrix intederence was noted with samples containing PAHs. Thus, all samples will undergo bromide analysis under controlled laboratory conditions. Procedure The Accume t meter can be operated either in the millivolt (mV) mode or ISE mode where output is in units of choice (ppm). If operated in m V mode a calibration curve must be generated by measur ing two 139 standards that bracket concentration of samples (for our purposes 1 to 1000 ppm is sufficient). In mV mode, the calibration curve should be prepared on semi-log graph paper. Use of ISE mode will require the use of two standards similar to that of the mV mode however, the meter stores the slope value to memory and outputs bromide concentration directly in units of choice (ppm) and measurements on samples can be made directly without use of a calibration curve. If standards are poorly prepared and the resulting slope value is outside the slope range specifications then the meter will not calibrate. Probe calibration should be checked on a daily basis to ensure standard integrity and probe performance. 1. Calibrate meter/probe; using standards that bracket expected concentration range of samples i.e., 10 to 500 ppm. Standards are measured in the same way as samples (described below). 2. Place a known volume of standard (sample) in a beaker with stir bar 3. Add ISA in 50:1 ratio (sample:ISA); smaller sample sizes will conserve reagents 4. Stir at constant rate using magnetic plate stirrer (or by hand in field) and read meter after 40 seconds (standardized time for each measurement). Known Addition The known addition method is applicable to waters whose bromide concentration is greater than 0.4 mg/L. This method is suitable to water that has a complicated background matrix or is high in ionic strength (ionic strength >0.1 M). Procedure 1. Ensure probe is in good operation condition; obtain slope value and record on log sheet. 2. Set meter to read millivolts 3. Measure out 25.0 ml of sample using a volumetric pipette into a 50ml beaker and add 0.5 ml (500 ul) of ISA using an Ependorf pipette. Record volumes on log sheet. 4. Place beaker on magnetic plate stirrer (place paper towel or cardboard between beaker and plate to insulate sample from heat created by plate stirrer) add stir bar and begin stirring sample at a low setting, (standardize this setting by marking dial with marker). 140 5. R inse off probe and wipe c lean with kim-wipe t issue and immerse in beaker containing sample and ISA. Al low reading to stabil ize (wait 40 seconds) . Then record millivolt reading. 6. A d d a known amount of bromide standard to the sample (using a dedicated variable volume Ependorf pipette) s o that the amount of standard added will at least double the initial concentration. Record vo lume and concentration of standard added. The addition of standard should be based either on measured concentrations in the field or on initial concentrations in lab. Care should be taken in the addition so that the volume of addition does not exceed 10% sample volume (2.5ml). To prevent against dilution effects use highest concentration standard solutions. See chart below for determining volume and concentration of standard to add. 7. Rep lace bromide probe in solution and take a final reading of the millivolt output after 40 seconds and record the value on the log sheet. 8. Us ing the prepared excel spreadsheet input all va lues recorded on log sheet and determine the concentration of bromide in the sample. Table 2: Volumes and standard concentrations for known addition method based on range of sample concentration Sample Concentration (ppm) Concentration of Addition (ppm) Volume of Addition (ml) < 10 ppm 1000 1 < 100 ppm 7990 (0.1 M stock) 1 < 400 ppm 7990 (0.1 M stock) 2.5 Quality Assurance and Quality Control (QA/QC) Scope Quantify method detection limits, accuracy and precision. 141 Method Detection Limit (MDL) *for the determination of the M D L use all equipment and reagent that would be used for the analysis of samples . Procedure 1. Prepare 8 x 100 ml standards that are 5 to 10 t imes the probable or expected detection limit for the test (for a 0.4 ppm limit prepare standards at around 2 ppm) 2. P lace 2 ml of 100 ppm standard solution into a 100 ml volumetric f lask and dilute with distilled water to 100 ml. 3. U s e a 25 ml aliquot for each of the standards and place into a 50 ml beaker, (use 25 ml volumetric pipette to transfer aliquot). 4. A d d 500 ul of ISA to each standard using the Eppendorf pipette 5. Ana l yze each standard prepared using the Known Addition method (preferably over a 3 day period), include all sample processing steps in the determination 6. Record the appropriate readings on the provided log sheet. 7. Calculate the standard deviation for the set of standards ana lyzed. 8. Calculate M D L using the method descr ibed below M D L = [ t n . 1 , a = 0 .01]x [S] Where , [t n-i> a = 0.01] = student t's value for x number of degrees of f reedom at the 9 9 % conf idence level. Values for student t distribution can be obtained from a table of one-sided t distribution or use TDIST function in Excel. See Table 3 for Student t values. S = standard deviation of the replicate ana lyses 142 Quality Assurance/Quality Control Accu racy and precision will be monitored using control charts. Accu racy of measurements will be monitored by plotting % Recovery of measured Laboratory-fortified matrix ( L F M ) samples with time (Date). % Recovery is determined as follows: % recovery = [ (LFM sample result - sample result)/known L F M added concentration] x 1 0 0 % The accuracy chart includes upper and lower warning levels (WL) and upper and lower control levels (CL) set at +/- 2 S and +/- 3 S , respectively. Prec is ion of bromide ana lyses will be monitored using a control chart plotting a range of duplicates against time (Date). The chart will consist of only upper warning and upper control limits. The standard deviation of the method is converted to the range. A perfect agreement between replicates or duplicates results in a difference of zero represented by the base line. W L , C L and R are determined as follows: R m = D 2 S C L = Rm +/- 3S (R ) = D 4 R m W L = R „ +/- 2S (R ) = R™ +/- 2 / 3 ( D 4 R m - R m ) Where , Rm = mean range S = standard deviation of the method (determined from M D L analysis) D 2 = factor to convert S to the range (1/128 for duplicates, as given in Table 1020:1; S td . Me thods , p. 1 -9) S (R ) = standard deviation of the range, and D 4 = factor to convert mean range to 3S(R) (3.267 for dupl icates, as given in Tab le 1020:1; Std . Method, p. 1-9). Therefore, to use the above mentioned control charts, additional ana lyses will be required. Additional samples included L F M (at least one per batch (day) or on a 5 % bas is ; 1 per 20 samples) and duplicates of standards (again, at least one per batch (day) or on a 5 % basis). In addition, reagent 143 blanks should be conducted to assess/moni tor for contamination. Ana l yze a blank after the daily calibration standard and after dealing with concentrated samples . Table 3: Student's Values at te 99% Confidence Level Number of Degree of T (n-1) 7 fi 3 1 4 3 8 7 9 QQft Q ft 9 8 Q 7 i n Q 9 891 11 i n 9. 7 f i 4 i f i m 9 fin.^ 91 9 n 9 5 9 8 9 f i 9.5 9 4 8 5 31 3 n 9 4 5 7 o c Q C 9 3fiQ 144 Bromide probe calibration curve 18/11/99 Bromide concentration (ppm) 1 10 100 1000 40 _i , , 1 -160 J I —*— Distilled - ± - M W 9 6 - 4 d [non-PAH contaminated] _ * _ D T - 5 [PAH-contaminated] Graph showing bromide calibration curve using three different types of water. Groundwater collected from the uncontaminated portion of the aquifer provided a near identical curve to that where distilled water was used. PAH contaminated groundwater appears to have an effect on Br results. 145 Bromide Quality Assurance/Quality Control Data Determination of MDL for Bromide (Known Addition) MDL = [tn-1,a= 0.01 x[S] Date Anlayzed 10 ppm std. Samples (mg/L) 1 Mar 2000 9ti 8.8 3 Mar 2000 9.4 9.6 6 Mar 2000 9.1 8.6 6 Mar 2000 9.4 Standard Deviation [S] = 0.4 MDL = 1.2 Sample Splits with Analytical Services Laboratories Sample ID UBC Results A S L Result Difference (mg/L) (mg/L) % ON-EXT-2 1 0.5 -50 ON-INJ-1 373 394 +6 ON-INJ-2 375 ON-INJ-3 380 ON-INJ-4 382 395 +3 ON-INJ-5 378 ON-INJ-6 380 OFF-EXT-1 0.5 OFF-EXT-2 0.5 <0.5 OFF-INJ-2 388 372 -4 OFF-INJ-3 368 OFF-INJ-5 371 OFF-INJ-6 365 363 -1 146 w .2 " C a> cn or a • • • • : i I. • • • • • * • • 0 0 - 6 n v - Z OO-inr-83 OO-inr-81-h OO-inr-8 0 0 - u n r - 8 2 OO-unr-81. 00 -un r -8 00-AB|/\I-63 00-Ae|Aj-6 L 00-AB | / \ | -6 OO-JdV-63 OO-Jdv-61-00 -JdV-6 00-Je|A|-oe 00-JBIAI-02 00-JBIAI-0U 0 0 - q 9 d - 6 3 oo-q3d-6i-oo-qsd-6 oo-uer-oe C\| O CO CO -<fr "l/6w 'sa}BO!|dna jo aBue^j <N > o u a> a: C <D U a> Q. t i (9 . C o In c re a> o ro i_ 3 U u < • • • • 4* V • * 00-6nv-9l. 00-f3nv-9 00-|nr-Z3 oo-inr-zi. oo-inr-z 00-unr-Z3 OO-unr-zi. OO-unr-z 00 -Ae | / \ | -93 OO-ABIAI-91. 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X o X J CD > U N U, Q rt to CU O A p p e n d i x H : Offshore Prof i l e s o f I no rgan i c s 172 Dissolved Oxygen • 13 Dissolved Oxygen (mg/L) using HACH method (1.4) Dissolved Oxygen (mg/L) using CHEMets ampule kit Nitrate • N03-2(mg/L) 173 Manganese R12* R1HI Iron o i R91 R12* R1-K1 R1Q1 River 0 2 ^ * 82 2 ^^^^^^^ -10 -15 -20 -25 4 Sand with Silt Lenses • 43.3 (10) 83.4 5 ug naphthalene/L contour Den se/si Ity /sa nd/g ravel --10 -15 -20 -25 -100 -80 -60 -40 -20 0 20 40 60 80 100 120 140 160 180 200 • Fe (mg/L) (>10) Fe (mg/L) determined by CHEMets field kit 174 Sulfate • S O ; 3 (mg/L) Bicarbonate -100 -80 -60 -40 -20 0 20 40 60 80 100 120 140 160 180 200 • 163 HC03 (mg/L) determined in field (55) HC03 (mg/L) determined in lab 175 Calcium Chloride • CI" (mg/L) 176 A p p e n d i x I: O n s h o r e B r o m i d e R e s u l t s a n d A S L A n a l y t i c a l R e p o r t s 177 Bromide Concentration for extracted and injected groundwater Sample ID [Br] Extraction (mg/L) ON-X-2 1 Injection ON-INJ-1 373 ON-INJ-2 375 ON-INJ-3 380 ON-INJ-4 382 ON-INJ-5 378 ON-INJ-6 380 178 Bromide Concentration at Monitoring Well 1 Sampling Ports Date Time MW1-1 MW1-2 MW1-3 MW1-4 MW1-5 MW1-6 2/8/00 21:30 1.3 1.0 1.8 1.1 1.3 0.8 2/10/00 9:00 1.0 0.7 1.3 (1.2) 1.2 2.1 1.4 2/16/00 9:45 0.7 0.8 1.0 (1.0) 1.0 1.0 0.9 2/18/00 9:00 0.5 0.4 (0.5) 0.5 0.5 0.4 0.5 2/20/00 8:30 0.4 0.5 (0.5) 1.3 0.5 0.5 0.5 2/20/00 15:00 0.5 0.3 8.7 0.7 0.5 0.5 2/24/00 9:30 0.6 0.7 26.4 2.4 0.6 0.5 2/26/00 10:30 0.6 0.7 63.1 5.9 0.6 0.6 2/27/00 8:45 0.6 (0.6) 0.6 92.3 9.1 0.6 0.7 2/29/00 11:30 0.6 0.7 131.9 (131.2) 13.1 0.7 0.6 3/2/00 8:45 0.7 0.7 200.3 24.2 0.7 (0.7) 0.6 3/4/00 10:00 0.7 0.7 200.5 38.3 0.7 (0.5) 0.6 3/5/00 7:45 0.8 0.7 198.0 (199.2) 49.5 0.8 0.8 3/7/00 10:00 0.8 0.8 191.4 53.8 (53.8) 0.7 0.6 3/13/00 11:30 0.7 1.2 183.1 33.0 0.6 0.5 3/14/00 8:00 N/A 3.5 176.4 N/A N/A N/A 3/14/00 9:00 N/A 26.3 185.4 N/A N/A N/A 3/14/00 10:00 N/A 84.0 175.3 N/A N/A N/A 3/14/00 11:00 N/A 107.9 178.6 N/A N/A N/A 3/14/00 12:00 N/A 234.0 178.6 N/A N/A N/A 3/14/00 13:00 N/A 250.8 175.3 N/A N/A N/A 3/14/00 14:00 N/A 124.8 177.5 N/A N/A N/A 3/14/00 15:00 N/A 77.4 177.5 N/A N/A N/A 3/14/00 16:00 N/A 100.5 176.4 N/A N/A N/A 3/15/00 13:45 0.7 44.6 167.3 26.1 (26.0) 0.7 0.6 3/16/00 14:30 0.8 74.2 151.4 20.3 0.6 0.6 3/18/00 15:30 65.4 72.3 123.4 15.6 0.1 0.1 3/19/00 11:20 0.8 75.3 103.5 11.0 0.8 0.6 3/21/00 18:00 1.4 86.9 52.7 5.2 0.7 0.6 3/23/00 16:30 4.4 83.7 30.0 3.8 0.7 0.7 3/27/00 13:00 16.2 97.9 17.1 2.9 1.0 0.9 3/30/00 16:00 57.0 121.5 9.6 2.3 0.8 0.7 4/1/00 10:45 102.6 39.6 10.2 2.6 0.9 0.7 4/12/00 11:30 71.1 38.4 4.5 1.3 1.0 0.7 4/14/00 11:15 58.7 33.2 3.8 1.0 1.1 0.9 4/17/00 10:15 28.5 22.8 30.9 9.8 6.8 9.8 4/20/00 19:10 14.4 16.9 3.2 2.0 1.2 1.1 4/24/00 13:00 4.9 9.0 3.2 1.5 1.7 1.4 4/26/00 13:00 3.1 6.4 3.8 1.5 1.3 1.4 4/28/00 12:30 2.9 1.0 3.7 1.8 1.4 1.5 5/1/00 13:00 2.3 5.4 3.4 1.9 1.5 1.5 5/3/00 12:30 1.8 7.0 4.3 2.1 2.1 2.4 5/5/00 10:00 2.1 6.3 3.8 2.2 1.7 1.9 5/8/00 10:15 1.3 3.7 1.8 1.3 1.2 1.3 5/10/00 13:45 1.3 3.1 5.6 2.3 2.0 1.3 (0.9) (0.5) results of duplicate samples are shown in parenthesis 179 Bromide Concentration at Monitoring Well 1 Sampling Ports Date Time MW2-1 MW2-2 MW2-3 MW2-4 MW2-5 MW2-6 3/27/00 13:00 0.873 0.499 0.64 3/31/00 15:30 0.6 0.702 0.722 0.779 0.669 0.734 4/1/00 10:45 0.7 0.876 0.876 0.886 0.848 0.821 4/12/00 11:30 1.3 1.351 1.111 1.244 1.12 0.989 4/14/00 11:15 1.3 1.138 1.483 1.22 1.314 1.259 4/17/00 10:15 2.0 1.418 0.916 1.362 1.916 1.121 4/20/00 19:10 1.1 1.586 1.567 1.657 1.209 1.233 4/24/00 13:00 2.7 1.894 1.686 2.456 2.572 1.637 4/26/00 13:00 1.3 1.714 1.243 3.156 2.848 2.487 4/28/00 12:30 1.5 1.434 1.417 3.767 3.096 1.516 5/1/00 13:00 1.7 1.682 2.996 5.613 3.815 2.521 5/3/00 0:30 2.1 1.84 2.045 4.582 3.638 1.718 5/5/00 10:00 2.2 1.746 3.828 6.461 4.37 1.591 5/8/00 10:15 1.5 1.563 1.455 4.401 2.844 1.699 5/10/00 13:45 2.7 2.247 5.254 8.4 6.124 3.245 5/12/00 10:00 1.9 2.505 2.852 7.137 3.668 2.165 5/15/00 10:15 1.5 1.769 3.851 7.591 3.758 1.734 5/17/00 12:30 2.4 2.598 5.65 11.34 4.441 2.684 5/19/00 12:45 2.0 2.795 6.415 10.61 4.838 3.522 5/24/00 12:30 1.9 2.716 6.758 10.31 3.539 1.613 5/26/00 13:00 2.0 2.727 8.464 8.531 3.137 2.503 5/29/00 12:45 2.9 5.514 11.99 11.16 4.501 3.583 5/31/00 12:15 7.0 11.71 18.58 11.71 5.165 3.176 6/2/00 10:00 6.0 10.78 16.17 8.615 3.163 2.015 6/5/00 13:00 7.7 11.41 17.05 8.684 3.085 2.099 6/7/00 15:20 12.9 24.34 23.54 7.229 3.698 2.996 6/21/00 10:10 35.1 48.33 24.24 5.089 2.152 2.424 6/23/00 13:30 45.4 62.21 25.15 4.599 2.562 2.24 6/26/00 13:00 59.7 51.67 24.13 3.847 2.46 2.267 7/7/00 12:15 90.1 (96.6) 63.64 15.38 2.383 1.641 1.728 7/9/00 10:45 67.9 64.28 11.43 1.835 1.406 1.486 7/12/00 10:00 80.5 61.55 11.31 1.202 1.05 1.084 7/14/00 10:00 77.9 (87) 59.33 11.4 1.333 1.137 1.137 7/17/00 10:15 76.7 (85.8) 59.06 (60.4) 10.11 1.296 1.231 1.301 7/19/00 10:15 77.1 57.62 8.635 1.018 1.076 1.085 7/21/00 10:00 72.4 55.3 8.43 1.129 1.01 0.978 7/24/00 10:00 90.6 51.66 6.384 1.304 1.116 1.199 7/26/00 13:30 68.5 46.53 6.998 0.875 0.784 0.865 7/28/00 13:30 65.4 42.24 5.901 0.831 0.781 0.903 7/31/00 16:00 53.0 41.69 4.817 0.774 0.866 0.636 8/2/00 11:00 55.8 36.18 4.43 0.92 0.683 0.771 8/4/00 14:00 58.5 32.87 3.922 1.167 0.895 0.887 8/11/00 14:00 45.9 25.42 (19.9) 0.32 1.09 1.094 0.95 8/14/00 12:15 56.7 20.12 2.101 N/A N/A N/A 8/16/00 8:00 49.0 19.55 1.668 N/A N/A N/A 8/18/00 10:15 50.5 21.14 1.456 N/A N/A N/A 180 Bromide Concentration at Monitoring Well 1 Sampling Ports Date Time MW2-1 MW2-2 MW2-3 MW2-4 MW2-5 MW2-6 8/21/00 12:15 44.6 (42.4) 17.93 1.139 N/A N/A N/A 8/23/00 12:15 41.5 15.1 0.951 (0.9) N/A N/A N/A 8/25/00 12:45 37.9 12.69 0.942 N/A N/A N/A 8/28/00 13:00 29.4 13.01 0.784 N/A N/A N/A 8/30/00 12:30 35.1 10.51 0.718 N/A N/A N/A 9/1/00 8:00 31.7 9.596 0.661 N/A N/A N/A 9/6/00 12:45 28.4 8.069 0.635 N/A N/A N/A 181 Coordinates Relative to Injection Point Br X Y Z Hole ID mg/L m m mbg P1-13/3-1 0.6 5.43 -0.8 -10.1 P1-13/3-2 5.1 5.43 -0.8 -10.4 P1-13/3-3 2.0 5.43 -0.8 -10.7 P1-13/3-4 22.1 5.43 -0.8 -11.0 P1-13/3-5 180.6 5.43 -0.8 -11.3 P1-13/3-6 18.9 5.43 -0.8 -11.6 P1-13/3-7 3.6 5.43 -0.8 -11.9 P1-13/3-8 0.9 5.43 -0.8 -12.2 P2-14/3/-1 0.5 5.43 -1.77 -10.1 P2-14/3/-2 8.1 5.43 -1.77 -10.4 P2-14/3/-3 12.8 5.43 -1.77 -10.7 P2-14/3/-4 73.0 5.43 -1.77 -11.0 P2-14/3/-5 113.3 5.43 -1.77 -11.3 P2-14/3/-6 0.7 5.43 -1.77 -11.6 P2-14/3/-7 0.7 5.43 -1.77 -11.9 P3-15/3-1 0.5 5.43 -2.79 -10.1 P3-15/3-2 0.5 5.43 -2.79 -10.4 P3-15/3-3 0.5 5.43 -2.79 -10.7 P3-15/3-4 79.6 5.43 -2.79 -11.0 P3-15/3-5 4.1 5.43 -2.79 -11.3 P3-15/3-6 0.5 5.43 -2.79 -11.6 P4-16/3-1 0.6 5.43 1.02 -10.1 P4-16/3-2 0.7 5.43 1.02 -10.4 P4-16/3-3 0.7 5.43 1.02 -10.7 P4-16/3-4 10.3 5.43 1.02 -11.0 P4-16/3-5 52.0 5.43 1.02 -11.3 P4-16/3-6 0.7 5.43 1.02 -11.6 P4-16/3-7 0.6 5.43 1.02 -11.9 P5-16/3-1 0.6 5.43 2.04 -10.1 P5-16/3-2 0.6 5.43 2.04 -10.4 P5-16/3-3 0.6 5.43 2.04 -10.7 P5-16/3-4 20.4 5.43 2.04 -11.0 P5-16/3-5 51.0 5.43 2.04 -11.3 P5-16/3-6 0.7 5.43 2.04 -11.6 P5-16/3-7 0.6 5.43 2.04 -11.9 P6-17/3-1 0.5 5.43 3.07 -10.1 P6-17/3-2 0.5 5.43 3.07 -10.4 P6-17/3-3 0.5 5.43 3.07 -10.7 P6-17/3-4 0.6 5.43 3.07 -11.0 P6-17/3-5 0.6 5.43 3.07 -11.3 P6-17/3-6 0.7 5.43 3.07 -11.6 P6-17/3-7 0.7 5.43 3.07 -11.9 P7-20/3-1 0.6 8.88 -1.21 -10.1 P7-20/3-2 0.6 8.88 -1.21 -10.4 P7-20/3-3 0.7 8.88 -1.21 -10.7 Coordinates Relative to Injection Point Br X Y Z Hole ID mg/L m m mbg P7-20/3-4 2.3 8.88 -1.21 -11.0 P7-20/3-5 107.3 8.88 -1.21 -11.3 P7-20/3-6 1.0 8.88 -1.21 -11.6 P7-20/3-7 0.3 8.88 -1.21 -11.9 P8-21/3-1 0.7 12.81 -1.73 -10.1 P8-21/3-2 0.8 12.81 -1.73 -10.4 P8-21/3-3 0.8 12.81 -1.73 -10.7 P8-21/3-4 0.8 12.81 -1.73 -11.0 P8-21/3-5 0.9 12.81 -1.73 -11.3 P8-21/3-6 0.8 12.81 -1.73 -11.6 P8-21/3-7 0.1 12.81 -1.73 -11.9 P9-21/3-1 0.6 11.08 -1.45 -10.1 P9-21/3-2 0.7 11.08 -1.45 -10.4 P9-21/3-3 0.7 11.08 -1.45 -10.7 P9-21/3-4 0.8 11.08 -1.45 -11.0 P9-21/3-5 0.8 11.08 -1.45 -11.3 P9-21/3-6 0.6 11.08 -1.45 -11.6 P10-23/3-1 0.6 8.88 -2.39 -10.1 P10-23/3-2 0.5 8.88 -2.39 -10.4 P10-23/3-3 0.6 8.88 -2.39 -10.7 P10-23/3-4 30.6 8.88 -2.39 -11.0 P10-23/3-5 13.1 8.88 -2.39 -11.3 P10-23/3-6 0.6 8.88 -2.39 -11.6 P10-23/3-7 0.6 8.88 -2.39 -11.9 P11-23/3-1 0.6 8.88 -0.16 -10.1 P11-23/3-2 0.7 8.88 -0.16 -10.4 P11-23/3-3 0.7 8.88 -0.16 -10.7 P11-23/3-4 34.2 8.88 -0.16 -11.0 P11-23/3-5 2.4 8.88 -0.16 -11.3 P11-23/3-6 0.9 8.88 -0.16 -11.6 P12-23/3-1 0.7 5.43 -4.44 -10.1 P12-23/3-2 0.6 5.43 -4.44 -10.4 P12-23/3-3 0.6 5.43 -4.44 -10.7 P12-23/3-4 0.6 5.43 -4.44 -11.0 P12-23/3-5 0.7 5.43 -4.44 -11.3 P12-23/3-6 0.7 5.43 -4.44 -11.6 P12-23/3-7 0.6 5.43 -4.44 -11.9 1 8 3 R E M A R K S File No. L6055 The detection limits for some of the Dissolved Anions and Nutrients have been increased for the samples identified as "ON-INJ-1" and "OFF-INJ-2" due to sample matrix interferences. The detection limits for some of the metals have been increased for the samples identified as "OFF-INJ-2" and "OFF-EXT-3" due to the presence of unknown concentrations of sulphuric acid. ^ 15-Page 1 R E S U L T S O F ANALYSIS - Water File No. L6055 Sample ID ON-INJ-1 ON-INJ-4 OFF-INJ- OFF-INJ- ON-X-2 Sample Date 00 02 08 00 02 08 00 02 22 00 02 22 00 02 08 ASL ID 1 2 3 4 5 Dissolved A n i o n s _ Bromide Br 394 395 372 363 <0.5 Chloride C l 14 - <10 - 11.9 Fluoride F <0.4 - <0.4 - <0.02 Sulphate S04 <20 - <20 - <1 Nutrients Nitrate Nitrogen N <0.1 - <0.1 - <0 .00£ Nitrite Nitrogen N 0.08 - 0.08 - 0.008 Remarks regarding the analyses appear at the beginning of this report. Results are expressed as milligrams per litre except where noted. < = Less than the detection limit indicated. Page 2 \<rbh RESULTS OF ANALYSIS - Water File No. L6055 Sample ID O F F - E X T -Sample Date 00 02 21 ASL ID b Dissolved A n i o n s ' _ Bromide Br < 0 - 5 Chloride CI 5-8 Fluoride F < 0 0 2 Sulphate S04 <l Nutrients _ _ ^ n n n = Nitrate Nitrogen N n m n Nitrite Nitrogen N 0.0 i u Remarks regarding the analyses appear at the beginning of this report. Results are expressed as milligrams per litre except where noted. < = Less than the detection limit indicated. Page 3 l SI-/I5(i RESULTS OF ANALYSIS - Water File No. L6055 Sample ID ON-INJ-1 OFF-INJ-2 ON-X-2 O F F - E X T -3 Sample Date ASL ID 00 02 08 J 00 02 22 3 00 02 08 5 00 02 21 6 Dissolved Metals Aluminum D - A l Antimony D-Sb Arsenic D-As Barium D - B a Beryllium D-Be <0.2 <0.2 <0.2 0.09 <0.005 <1 <1 <1 0.08 <0.03 <0.2 <0.2 <0.2 0.08 <0.005 <1 <1 <1 0.08 <0.03 Bismuth Boron eadmium Calcium Chromium D - B i D - B D - C d D - C a D - C r <0.1 0.2 <0.01 25.4 <0.01 <0.5 <0.5 <0.05 25.1 <0.05 <0.1 0.1 <0.01 25.9 <0.01 <0.5 <0.5 <0.05 26.2 <0.05 Cobalt Copper Iron Lead Lithium D-Co D - C u D-Fe D-Pb D - L i <0.01 0.01 40.9 <0.05 <0.01 <0.05 <0.05 67.3 <0.3 <0.05 <0.01 <0.01 43.9 <0.05 <0.01 <0.05 <0.05 74.4 <0.3 <0.05 Magnesium Manganese Molybdenum Nickel Phosphorus D-Mg D - M n D-Mo D-Ni D-P 15.3 0.689 <0.03 <0.05 <0.3 15.1 1.49 <0.2 <0.3 <2 15.8 0.716 <0.03 <0.05 <0.3 15.7 1.55 <0.2 <0.3 <2 Potassium Selenium Silicon Silver Sodium D - K D-Se D-Si D-Ag D-Na 196 <0.2 20.2 <0.01 11 194 <1 18.8 <0.05 14 <2 <0.2 20.7 <0.01 12 <10 <1 19.9 <0.05 14 Strontium Thallium Tin Titanium Vanadium D-Sr D-Tl D-Sn D-Ti D-V 0.127 <0.2 <0.03 <0.01 <0.03 0.16 <1 <0.2 <0.05 <0.2 0.127 <0.2 <0.03 <0.01 <0.03 0.17 <1 <0.2 <0.05 <0.2 Zinc D-Zn 0.052 0.04 0.025 <0.03 Remarks regarding the analyses appear at the beginning of this report. Results are expressed as milligrams per litre except where noted. < = Less than the detection limit indicated. Page 4 l & £ > Appendix 1 - QUALITY CONTROL - Replicates File No. L6055 W a t e r OFF-EXT- OFF-EXT-00 02 21 QC # 193714 Dissolved Anions Bromide Br ~ _ Chloride Cl <0-5 <0.5 Fluoride F b - a __ 5 7 Sulphate S04 < J 0 2 <002 Nutrients Nitrate Nitrogen M „ _ Nitrite Nitrogen S <°-°° 5 <0-005 0.010 0.008 Remarks regarding the analyses appear at the beginning of this report. Results are expressed as milligrams per litre except where noted. < = Less than the detection limit indicated. Page 5 ]gft Appendix 1 - QUALITY CONTROL - Replicates File No. L6055 OFF-EXT- OFF-EXT-00 02 21 Q C # 193714 Dissolved Metals Aluminum D - A l Antimony D-Sb Arsenic D-As Barium D - B a Beryllium D-Be <1 <1 <1 0.08 <0.03 <1 <1 <1 0.08 <0.03 Bismuth Boron Cadmium Calcium Chromium D - B i D - B D - C d D - C a D - C r <0.5 <0.5 <0.05 26.2 <0.05 <0.5 <0.5 <0.05 25.9 <0.05 Cobalt Copper Iron Lead Lithium D-Co D - C u D-Fe D-Pb D - L i <0.05 <0.05 74.4 <0.3 <0.05 <0.05 <0.05 73.8 <0.3 <0.05 Magnesium Manganese Molybdenum Nickel Phosphorus D-Mg D - M n D-Mo D-Ni D-P 15.7 1.55 <0.2 <0.3 <2 15.5 1.54 <0.2 <0.3 <2 Potassium Selenium Silicon Silver Sodium D - K D-Se D-Si D-Ag D-Na <10 <1 19.9 <0.05 14 <10 <1 19.7 <0.05 14 Strontium Thallium Tin Titanium Vanadium D-Sr D-Tl D-Sn D-Ti D-V 0.17 <1 <0.2 <0.05 <0.2 0.17 <1 <0.2 <0.05 <0.2 Zinc D-Zn <0.03 <0.03 Remarks regarding the analyses appear at the beginning of this report. Results are expressed as milligrams per litre except where noted. < = Less than the detection limit indicated. Page 6 \<D o Appendix 2 - METHODOLOGY File No. L6055 Outlines of the methodologies utilized for the analysis of the samples submitted are as follows: Dissolved Anions in Water by Ion Chromatography This analysis is carried out using procedures adapted from APHA Method 4110 "Determination of Anions by Ion Chromatography" and EPA Method 300.0 "Deterrnination of Inorganic Anions by Ion Chromatography". Anions are determined by fUtering the sample through a 0.45 micron membrane filter and injecting the filtrate onto a dionex ionpac AG12A ion exchange column with a carbonate-bicarbonate eluent stream. Anions deterrnined by this method include: bromide, chloride, fluoride, nitrate, nitrite and sulphate. Recommended Holding Time: Sample: 28 days (bromide, chloride, fluoride, sulphate) Sample: 2 days (nitrate, nitrite) Reference: APHA and EPA For more detail see ASL "Collection & Sampling Guide" Metals in Water This analysis is carried out using procedures adapted from "Standard Methods for the Examination of Water and Wastewater" 20th Edition 1998 published by the American Public Health Association, and with procedures adapted from 'Test Methods for Evaluating Solid Waste" SW-846 published by the United States Environmental Protection Agency (EPA). The procedures may involve preliiriinary sample treatment by acid digestion, using either hotplate or microwave oven, or filtration (EPA Method 3005A). Instrumental analysis is by atomic absorption/emission spectrophotometry (EPA Method 7000 series), inductively coupled plasma - optical emission spectrophotometry (EPA Method 601 OB), and/or inductively coupled plasma -mass spectrometry (EPA Method 6020). Recommended Holding Time: Sample: 6 months Reference: EPA For more detail see: ASL "Collection & Sampling Guide" End of Report Page 7 |^ | A p p e n d i x J : Offshore B r o m i d e R e s u l t s "7 192 Table F1: Offshore Extracted Groundwater and Injectate Characteristics Date Collected Sample I.D. Bromide (mg/L) Lab Splits * (mg/L) 02/21/00 OFF-EXT-1 0.5 — 02/21/00 OFF-EXT-3 0.5 < 0.5 02/22/00 OFF-INJ-2 388 372 02/22/00 OFF-INJ-3 368 — 02/22/00 OFF-INJ-5 371 ~ 02/22/00 OFF-INJ-6 365 363 average (INJ) 373 368 OFF-EXT=OFFSHORE EXTRACTION SAMPLE OFF-INJ=OFFSHORE INJECTATE SAMPLE * lab splits analyzed by Analytical Laboratory Services. See lab reports following bromide tables in Appendix F. 193 Table F2a: Bromide Concentrations of First Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 4/7/00 RT3-3 13.70 -9.50 -14.50 0.7 4/7/00 RT3-4 13.70 -9.50 -14.81 0.7 4/7/00 RT3-5 13.70 -9.50 -15.09 0.8 4/7/00 RT3-6 13.70 -9.50 -15.39 0.7 4/7/00 RT3-7 13.70 -9.50 -15.65 0.8 4/7/00 RT3-8 13.70 -9.50 -15.93 0.8 4/8/00 RT4-1 13.40 -16.75 -13.69 0.7 4/8/00 RT4-3 13.40 -16.75 -14.91 0.7 4/8/00 RT4-4 13.40 -16.75 -15.21 7.0 4/8/00 RT4-5 13.40 -16.75 -15.52 10.4 4/8/00 RT4-6 13.40 -16.75 -15.82 94.0 4/8/00 RT4-7 13.40 -16.75 -16.13 19.1 4/8/00 RT4-8 13.40 -16.75 -16.43 5.3 4/8/00 RT4-9 13.40 -16.75 -16.71 9.8 4/8/00 RT5-4 12.00 -19.45 -15.21 6.6 4/8/00 RT5-5 12.00 -19.45 -15.57 0.8 4/8/00 RT5-6 12.00 -19.45 -15.82 0.8 4/8/00 RT5-7 12.00 -19.45 -16.13 0.8 4/8/00 RT5-8 12.00 -19.45 -16.43 0.8 4/8/00 RT5-9 12.00 -19.45 -16.74 0.9 4/8/00 RT5-10 12.00 -19.45 -17.02 0.9 4/8/00 RT5-11 12.00 -19.45 -17.35 0.9 4/8/00 RT6-3 12.25 -18.10 -14.78 0.6 4/8/00 RT6-6 12.25 -18.10 -15.60 0.7 4/8/00 RT6-7 12.25 -18.10 -16.10 0.9 4/8/00 RT6-8 12.25 -18.10 -16.38 2.8 4/8/00 RT6-9 12.25 -18.10 -16.59 11.1 4/8/00 RT6-10 12.25 -18.10 -16.97 1.5 4/8/00 RT6-11 12.25 -18.10 -15.72 0.9 4/9/00 RT7-2 13.55 -14.50 -13.11 0.7 4/9/00 RT7-4 13.45 -14.50 -14.33 0.6 4/9/00 RT7-5 13.45 -14.50 -15.54 106.8 4/9/00 RT7-6 13.45 -14.50 -15.85 185.0 4/9/00 RT7-7 13.45 -14.50 -16.28 61.9 4/9/00 RT7-8 13.45 -14.50 -16.66 1.2 1 9 4 Table F2a: Bromide Concentrations of First Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 4/9/00 RT8-2 13.55 -11.85 -15.21 0.7 4/9/00 RT8-3 13.55 -11.85 -15.88 1.7 4/9/00 RT8-4 13.55 -11.85 -17.70 0.8 4/9/00 RT9-1 12.80 -12.90 -14.63 4.2 4/9/00 RT9-2 12.80 -12.90 -14.96 13.5 4/9/00 RT9-3 12.80 -12.90 -15.29 2.9 4/9/00 RT9-4 12.80 -12.90 -15.57 108.0 4/9/00 RT9-5 12.80 -12.90 -15.88 289.5 4/9/00 RT9-6 12.80 -12.90 -16.15 270.4 4/9/00 RT9-7 12.80 -12.90 -16.46 189.9 4/9/00 RT9-8 12.80 -12.90 -16.69 66.3 4/9/00 RT9-9 12.80 -12.90 -16.92 28.6 4/9/00 RT9-10 12.80 -12.90 -17.20 2.3 4/10/00 RT10-0 10.00 -13.50 -15.21 104.6 4/10/00 RT10-1 10.00 -13.50 -15.47 71.8 4/10/00 RT10-2 10.00 -13.50 -15.77 32.4 4/10/00 RT10-3 10.00 -13.50 -16.38 1.3 4/10/00 RT10-4 10.00 -13.50 -16.38 0.6 4/10/00 RT11-1 12.00 -14.65 -14.96 0.8 4/10/00 RT11-2 12.00 -14.65 -15.24 69.5 4/10/00 RT11-3 12.00 -14.65 -15.57 215.9 4/10/00 RT11-4 12.00 -14.65 -15.90 301.1 4/10/00 RT11-5 12.00 -14.65 -16.21 350.1 4/10/00 RT11-6 12.00 -14.65 -16.48 310.6 4/10/00 RT11-7 12.00 -14.65 -16.79 281.4 4/10/00 RT11-8 12.00 -14.65 -17.45 1.8 4/10/00 RT11-9 12.00 -14.65 -17.73 1.2 4/10/00 RT12-1 9.60 -18.35 -15.57 0.9 4/10/00 RT12-2 9.60 -18.35 -15.90 0.9 4/10/00 RT12-3 9.60 -18.35 -16.18 0.9 4/10/00 RT12-4 9.60 -18.35 -17.07 1.0 195 Table F3a: Bromide Concentrations of Second Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 5/7/00 RT13-1 11.00 -14.70 -15.95 10.3 5/7/00 RT13-2 11.00 -14.70 -17.20 1.6 5/7/00 RT14-1 10.00 -19.80 -14.02 1.9 5/7/00 RT14-2 10.00 -19.80 -14.61 1.9 5/7/00 RT14-3 10.00 -19.80 -15.44 2.1 5/7/00 RT14-4 10.00 -19.80 -16.05 1.6 5/7/00 RT14-5 10.00 -19.80 -16.64 1.6 5/7/00 RT14-6 10.00 -19.80 -17.22 1.6 5/7/00 RT14-7 10.00 -19.80 -17.81 2.0 5/8/00 RT15-1 9.80 -16.60 -13.08 1.4 5/8/00 RT15-2 9.80 -16.60 -13.64 2.0 5/8/00 RT15-3 9.80 -16.60 -14.26 1.5 5/8/00 RT15-4 9.80 -16.60 -14.86 3.2 5/8/00 RT15-5 9.80 -16.60 -15.16 7.4 5/8/00 RT15-6 9.80 -16.60 -15.75 12.5 5/8/00 RT15-7 9.80 -16.60 -16.38 55.5 5/8/00 RT15-8 9.80 -16.60 -16.74 3.4 5/8/00 RT16-1 9.40 -17.70 -14.02 1.6 5/8/00 RT16-2 9.40 -17.70 -14.66 2.0 5/8/00 RT16-3 9.40 -17.70 -15.27 1.7 5/8/00 RT16-4 9.40 -17.70 -15.57 2.1 5/8/00 RT16-5 9.40 -17.70 -15.90 2.1 5/8/00 RT16-6 9.40 -17.70 -16.18 2.3 5/8/00 RT16-7 9.40 -17.70 -16.48 1.6 5/8/00 RT16-8 9.40 -17.70 -17.09 1.2 5/8/00 RT16-9 9.40 -17.70 -17.70 1.3 5/8/00 RT17-1 8.20 -15.65 -14.63 0.7 5/8/00 RT17-2 8.20 -15.65 -15.24 0.9 5/8/00 RT17-3 8.20 -15.65 -15.85 1.1 5/8/00 RT17-4 8.20 -15.65 -16.15 1.3 5/8/00 RT17-5 8.20 -15.65 -16.46 1.0 5/8/00 RT17-6 8.20 -15.65 -17.07 1.2 5/8/00 RT17-7 8.20 -15.65 -17.68 1.2 5/8/00 RT18-1 11.50 -16.50 -14.63 0.9 5/8/00 RT18-2 11.50 -16.50 -15.24 2.1 196 Table F3a: Bromide Concentrations of Second Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 5/8/00 RT18-3 11.50 -16.50 -15.52 45.6 5/8/00 RT18-4 11.50 -16.50 -15.82 224.1 5/8/00 RT18-5 11.50 -16.50 -16.10 169.1 5/8/00 RT18-6 11.50 -16.50 -16.69 175.2 5/8/00 RT18-7 11.50 -16.50 -17.30 82.2 5/8/00 RT18-8 11.50 -16.50 -17.88 3.9 5/9/00 RT19-1 12.80 -16.60 -14.63 1.0 5/9/00 RT19-2 12.80 -16.60 -15.21 17.5 5/9/00 RT19-3 12.80 -16.60 -15.82 244.6 5/9/00 RT19-4 12.80 -16.60 -16.48 121.7 5/9/00 RT19-5 12.80 -16.60 -17.07 3.2 5/9/00 RT19-6 12.80 -16.60 -17.70 1.4 5/9/00 RT20-1 14.80 -16.30 -14.66 1.4 5/9/00 RT20-2 14.80 -16.30 -15.24 1.3 5/9/00 RT20-3 14.80 -16.30 -15.90 1.4 5/9/00 RT20-4 14.80 -16.30 -16.48 1.6 5/9/00 RT20-5 14.80 -16.30 -16.79 1.6 5/9/00 RT21-1 11.50 -17.50 -14.63 1.2 5/9/00 RT21-2 11.50 -17.50 -15.21 38.4 5/9/00 RT21-3 11.50 -17.50 -15.85 3.1 5/9/00 RT21-4 11.50 -17.50 -16.48 7.0 5/9/00 RT21-5 11.50 -17.50 -17.09 1.3 5/9/00 RT22-1 12.00 -15.50 -14.66 1.2 5/9/00 RT22-2 12.00 -15.50 -15.29 7.5 5/9/00 RT22-3 12.00 -15.50 -15.88 239.7 5/9/00 RT22-4 12.00 -15.50 -16.48 332.8 5/9/00 RT22-5 12.00 -15.50 -17.09 124.3 5/9/00 RT22-6 12.00 -15.50 -17.68 3.9 5/9/00 RT22-7 12.00 -15.50 -18.29 1.4 5/9/00 RT23-1 12.85 -14.30 -14.61 1.7 5/9/00 RT23-2 12.85 -14.30 -15.19 27.5 5/9/00 RT23-3 12.85 -14.30 -15.77 117.2 5/9/00 RT23-4 12.85 -14.30 -16.41 317.6 5/9/00 RT23-5 12.85 -14.30 -16.99 267.3 5/9/00 RT23-6 12.85 -14.30 -17.60 13.7 197 Table F3a: Bromide Concentrations of Second Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 5/9/00 RT23-7 12.85 -14.30 -18.21 1.7 5/10/00 RT24-1 13.85 -11.45 -14.63 1.0 5/10/00 RT24-2 13.85 -11.45 -15.75 1.7 5/10/00 RT24-3 13.85 -11.45 -15.39 1.3 5/10/00 RT24-4 13.85 -11.45 -16.61 1.2 5/10/00 RT24-5 13.85 -11.45 -17.78 1.6 5/10/00 RT25-1 13.60 -15.30 -14.61 1.1 5/10/00 RT25-2 13.60 -15.30 -15.19 2.7 5/10/00 RT25-3 13.60 -15.30 -15.80 139.0 5/10/00 RT25-4 13.60 -15.30 -15.52 189.0 5/10/00 RT25-5 13.60 -15.30 -17.02 2.1 5/10/00 RT25-6 13.60 -15.30 -16.97 1.6 5/10/00 RT26-1 11.30 -12.75 -14.66 1.3 5/10/00 RT26-2 11.30 -12.75 -15.27 3.2 5/10/00 RT26-3 11.30 -12.75 -15.85 137.5 5/10/00 RT26-4 11.30 -12.75 -16.54 108.9 5/10/00 RT26-5 11.30 -12.75 -17.17 2.9 5/10/00 RT26-6 11.30 -12.75 -17.78 1.2 198 Table F4a: Bromide Concentrations of Third Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth interval (m) (m) (m.s.l) (mg/L) 6/12/00 RT27-1 13.00 -14.15 -15.57 4.1 6/12/00 RT27-2 13.00 -14.15 -16.05 55.2 6/12/00 RT27-3 13.00 -14.15 -16.61 304.4 6/12/00 RT27-4 13.00 -14.15 -17.22 25.2 6/12/00 RT27-5 13.00 -14.15 -17.81 1.5 6/13/00 RT28-1 12.30 -12.90 -15.33 2.5 6/13/00 RT28-2 12.30 -12.90 -15.96 70.1 6/13/00 RT28-3 12.30 -12.90 -16.54 64.8 6/13/00 RT28-4 12.30 -12.90 -17.07 37.5 6/13/00 RT28-5 12.30 -12.90 -17.70 1.6 6/13/00 RT28-6 12.30 -12.90 -18.26 0.7 6/13/00 RT29-1 10.40 -12.70 -15.23 0.8 6/13/00 RT29-2 10.40 -12.70 -15.85 0.9 6/13/00 RT29-3 10.40 -12.70 -16.54 1.0 6/13/00 RT29-4 10.40 -12.70 -17.07 1.1 6/13/00 RT29-5 10.40 -12.70 -17.71 1.1 6/13/00 RT30-1 16.50 -13.00 -14.88 1.2 6/13/00 RT30-2 16.50 -13.00 -15.16 1.3 6/13/00 RT30-3 16.50 -13.00 -15.75 1.4 6/13/00 RT30-4 16.50 -13.00 -16.36 1.2 6/13/00 RT30-5 16.50 -13.00 -16.97 1.5 6/13/00 RT30-6 16.50 -13.00 -17.51 1.3 6/13/00 RT31-1 13.40 -12.90 -15.11 2.7 6/13/00 RT31-2 13.40 -12.90 -15.70 5.3 6/13/00 RT31-3 13.40 -12.90 -16.28 9.1 6/13/00 RT31-4 13.40 -12.90 -16.89 11.3 6/13/00 RT31-5 13.40 -12.90 -17.53 1.6 6/14/00 RT32-1 11.75 -12.10 -15.27 1.7 6/14/00 RT32-2 11.75 -12.10 -15.88 55.5 6/14/00 RT32-3 11.75 -12.10 -16.47 161.6 6/14/00 RT32-4 11.75 -12.10 -17.15 157.0 6/14/00 RT32-5 11.75 -12.10 -17.79 1.8 6/14/00 RT32-6 11.75 -12.10 -18.40 2.2 6/14/00 RT33-1 9.90 -11.60 -14.73 1.2 6/14/00 RT33-2 9.90 -11.60 -15.01 1.2 1 9 9 Table F4a: Bromide Concentrations of Third Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 6/14/00 RT33-3 9.90 -11.60 -15.49 1.2 6/14/00 RT33-4 9.90 -11.60 -16.18 1.3 6/14/00 RT34-1 13.50 -11.30 -15.19 1.5 6/14/00 RT34-2 13.50 -11.30 -15.75 1.3 6/14/00 RT34-3 13.50 -11.30 -16.36 1.1 6/14/00 RT34-4 13.50 -11.30 -16.92 2.7 6/14/00 RT34-5 13.50 -11.30 -17.53 1.1 6/14/00 RT34-6 13.50 -11.30 -18.11 1.1 6/14/00 RT35-1 15.90 -11.35 -15.19 1.0 6/14/00 RT35-2 15.90 -11.35 -15.75 1.1 6/14/00 RT35-3 15.90 -11.35 -16.36 1.2 6/14/00 RT35-5 15.90 -11.35 -16.92 1.7 6/14/00 RT35-6 15.90 -11.35 -17.50 1.4 6/14/00 RT36-1 12.05 -10.60 -15.11 1.6 6/14/00 RT36-2 12.05 -10.60 -15.77 1.2 6/14/00 RT36-3 12.05 -10.60 -16.46 1.3 6/14/00 RT36-4 12.05 -10.60 -17.09 1.4 6/14/00 RT36-5 12.05 -10.60 -16.26 0.9 6/15/00 RT37-1 12.35 -15.30 -16.26 19.6 6/15/00 RT37-2 12.35 -15.30 -15.16 14.1 6/15/00 RT37-3 12.35 -15.30 -15.80 22.5 6/15/00 RT37-4 12.35 -15.30 -17.04 180.0 6/15/00 RT37-5 12.35 -15.30 -17.63 287.0 6/15/00 RT37-6 12.35 -15.30 -18.26 24.7 6/15/00 RT37-7 12.35 -15.30 -18.90 2.3 6/15/00 RT37-8 12.35 -15.30 -19.51 1.6 6/15/00 RT38-1 11.30 -15.20 -14.99 1.9 6/15/00 RT38-2 11.30 -15.20 -15.62 11.4 6/15/00 RT38-3 11.30 -15.20 -16.28 9.9 6/15/00 RT38-4 11.30 -15.20 -16.87 25.8 6/15/00 RT38-5 11.30 -15.20 -17.50 1.9 6/15/00 RT38-6 11.30 -15.20 -18.08 1.5 6/15/00 RT39-1 9.20 -15.00 -15.21 1.1 6/15/00 RT39-3 9.20 -15.00 -16.43 1.3 6/15/00 RT39-4 9.20 -15.00 -16.99 1.3 200 Table F4a: Bromide Concentrations of Third Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 6/15/00 RT39-5 9.20 -15.00 -17.60 1.4 6/15/00 RT40-1 13.70 -15.40 -15.21 21.3 6/15/00 RT40-2 13.70 -15.40 -15.80 67.9 6/15/00 RT40-3 13.70 -15.40 -16.38 222.7 6/15/00 RT40-4 13.70 -15.40 -17.02 147.2 6/15/00 RT40-5 13.70 -15.40 -17.58 349.4 6/15/00 RT40-6 13.70 -15.40 -18.16 13.6 6/15/00 RT40-7 13.70 -15.40 -18.77 1.9 6/15/00 RT41-1 15.85 -15.50 -15.24 1.2 6/15/00 RT41-2 15.85 -15.50 -15.82 1.2 6/15/00 RT41-3 15.85 -15.50 -16.43 1.2 6/15/00 RT41-4 15.85 -15.50 -17.04 1.3 6/15/00 RT41-5 15.85 -15.50 -17.83 1.5 6/15/00 RT41-6 15.85 -15.50 -18.44 1.7 6/16/00 RT42-1 14.00 -16.95 -15.29 10.8 6/16/00 RT42-2 14.00 -16.95 -15.88 88.9 6/16/00 RT42-3 14.00 -16.95 -16.54 179.1 6/16/00 RT42-4 14.00 -16.95 -17.17 68.5 6/16/00 RT42-5 14.00 -16.95 -17.81 2.5 6/16/00 RT42-6 14.00 -16.95 -18.42 1.5 6/16/00 RT43-1 9.25 -16.50 -15.42 1.2 6/16/00 RT43-2 9.25 -16.50 -15.88 1.6 6/16/00 RT43-3 9.25 -16.50 -16.48 1.6 6/16/00 RT43-4 9.25 -16.50 -17.09 1.8 6/16/00 RT43-5 9.25 -16.50 -17.73 0.6 6/16/00 RT43-6 9.25 -16.50 -18.29 1.8 6/16/00 RT44-1 12.15 -19.25 -15.21 7.4 6/16/00 RT44-2 12.15 -19.25 -15.80 0.1 6/16/00 RT44-3 12.15 -19.25 -16.36 7.8 6/16/00 RT44-4 12.15 -19.25 -16.99 3.1 6/16/00 RT44-5 12.15 -19.25 -17.58 2.0 6/16/00 RT44-6 12.15 -19.25 -18.24 1.9 6/16/00 RT45-1 13.45 -18.00 -15.29 1.4 6/16/00 RT45-2 13.45 -18.00 -15.90 1.5 6/16/00 RT45-3 13.45 -18.00 -16.48 1.1 2 0 1 Table F4a: Bromide Concentrations of Third Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 6/16/00 RT45-4 13.45 -18.00 -17.09 1.4 6/16/00 RT45-5 13.45 -18.00 -17.70 1.4 6/16/00 RT45-6 13.45 -18.00 -18.29 1.3 6/16/00 RT46-1 11.35 -17.60 -15.27 3.4 6/16/00 RT46-2 11.35 -17.60 -15.85 79.1 6/16/00 RT46-3 11.35 -17.60 -16.46 102.7 6/16/00 RT46-4 11.35 -17.60 -17.09 69.1 6/16/00 RT46-5 11.35 -17.60 -17.68 183.6 6/16/00 RT46-6 11.35 -17.60 -18.24 5.5 6/16/00 RT46-7 11.35 -17.60 -18.90 1.7 6/17/00 RT47-1 9.65 -17.90 -15.24 6.7 6/17/00 RT47-2 9.65 -17.90 -15.88 8.4 6/17/00 RT47-3 9.65 -17.90 -16.48 104.3 6/17/00 RT47-4 9.65 -17.90 -17.12 0.5 6/17/00 RT47-5 9.65 -17.90 -17.63 1.6 6/17/00 RT47-6 9.65 -17.90 -18.42 1.8 6/17/00 RT47-7 9.65 -17.90 -19.00 1.8 6/17/00 RT48-1 15.65 -18.45 -15.27 1.1 6/17/00 RT48-2 15.65 -18.45 -15.90 1.2 6/17/00 RT48-3 15.65 -18.45 -16.54 1.2 6/17/00 RT48-4 15.65 -18.45 -17.15 1.5 6/17/00 RT48-5 15.65 -18.45 -17.75 1.5 6/17/00 RT48-6 15.65 -18.45 -18.36 1.4 6/17/00 RT49-1 8.40 -18.70 -15.24 1.1 6/17/00 RT49-2 8.40 -18.70 -15.88 1.2 6/17/00 RT49-3 8.40 -18.70 -16.51 1.2 6/17/00 RT49-4 8.40 -18.70 -17.09 1.2 6/17/00 RT49-5 8.40 -18.70 -17.65 1.5 6/17/00 RT49-6 8.40 -18.70 -18.31 1.6 6/17/00 RT50-1 13.70 -9.50 -15.24 1.1 6/17/00 RT50-2 13.70 -9.50 -15.80 1.4 6/17/00 RT50-3 13.70 -9.50 -16.46 1.6 6/17/00 RT50-4 13.70 -9.50 -17.02 1.7 6/17/00 RT50-5 13.70 -9.50 -17.60 1.6 Table F5: Bromide Concentrations of Fourth Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 10/4/00 RT51-1 13.70 -9.50 -14.2 1 10/4/00 RT51-2 13.70 -9.50 -14.8 1 10/4/00 RT51-3 13.70 -9.50 -15.5 1 10/4/00 RT51-4 13.70 -9.50 -16.6 2 10/4/00 RT52-1 10.30 -9.65 -13.7 1 10/4/00 RT52-2 10.30 -9.65 -14.1 1 10/4/00 RT52-3 10.30 -9.65 -14.7 1 10/4/00 RT52-4 10.30 -9.65 -15.1 1 10/4/00 RT52-5 10.30 -9.65 -15.6 1 10/4/00 RT53-1 11.90 -15.20 -13.9 1 10/4/00 RT53-2 11.90 -15.20 -14.8 7 10/4/00 RT53-2 11.90 -15.20 -14.8 8 10/4/00 RT53-3 11.90 -15.20 -15.4 19 10/4/00 RT53-4 11.90 -15.20 -16.1 91 10/4/00 RT53-5 11.90 -15.20 -16.7 111 10/4/00 RT53-6 11.90 -15.20 -17.2 113 10/4/00 RT53-7 11.90 -15.20 -18.7 3 10/5/00 RT54-1 14.00 -15.30 -14.6 4 10/5/00 RT54-2 14.00 -15.30 -15.2 23 10/5/00 RT54-3 14.00 -15.30 -15.8 72 10/5/00 RT54-4 14.00 -15.30 -16.9 62 10/5/00 RT54-5 14.00 -15.30 -17.6 1 10/5/00 RT54-5 14.00 -15.30 -17.6 1 10/5/00 RT55-1 10.40 -15.10 -14.5 2 10/5/00 RT55-2 10.40 -15.10 -15.1 3 10/5/00 RT55-3 10.40 -15.10 -15.8 48 10/5/00 RT55-4 10.40 -15.10 -16.4 86 10/5/00 RT55-5 10.40 -15.10 -17.0 40 10/5/00 RT55-6 10.40 -15.10 -17.7 83 10/5/00 RT55-7 10.40 -15.10 -18.3 2 10/5/00 RT56-1 7.90 -15.00 -14.2 1 10/5/00 RT56-2 7.90 -15.00 -14.8 1 10/5/00 RT56-3 7.90 -15.00 -15.5 1 10/5/00 RT56-3 7.90 -15.00 -15.5 1 10/5/00 RT56-4 7.90 -15.00 -16.2 1 203 Table F5: Bromide Concentrations of Fourth Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 10/5/00 RT56-5 7.90 -15.00 -16.8 1 10/5/00 RT56-6 7.90 -15.00 -17.5 1 10/5/00 RT57-1 11.00 -20.70 -14.9 1 10/5/00 RT57-2 11.00 -20.70 -15.6 1 10/5/00 RT57-3 11.00 -20.70 -16.3 1 10/5/00 RT57-4 11.00 -20.70 -16.9 1 10/6/00 RT58-1 15.40 -12.00 -14.9 2 10/6/00 RT58-2 15.40 -12.00 -15.5 1 10/6/00 RT58-3 15.40 -12.00 -16.2 11 10/6/00 RT58-4 15.40 -12.00 -16.9 24 10/6/00 RT58-5 15.40 -12.00 -17.4 1 10/6/00 RT58-6 15.40 -12.00 -18.1 1 10/6/00 RT59-1 9.80 -11.80 -14.6 1 10/6/00 RT59-2 9.80 -11.80 -15.2 1 10/6/00 RT59-3 9.80 -11.80 -15.9 1 10/6/00 RT59-4 9.80 -11.80 -16.5 1 10/6/00 RT59-5 9.80 -11.80 -17.1 1 10/6/00 RT60-1 9.40 -13.70 -14.5 1 10/6/00 RT60-2 9.40 -13.70 -15.2 2 10/6/00 RT60-3 9.40 -13.70 -15.8 60 10/6/00 RT60-4 9.40 -13.70 -16.5 126 10/6/00 RT60-5 9.40 -13.70 -17.1 109 10/6/00 RT60-5 9.40 -13.70 -17.1 110 10/6/00 RT60-6 9.40 -13.70 -17.8 192 10/6/00 RT60-7 9.40 -13.70 -18.4 203 10/6/00 RT60-8 9.40 -13.70 -19.1 10 10/6/00 RT60-9 9.40 -13.70 -19.6 2 10/6/00 RT61-1 10.00 -13.60 -14.3 0 10/6/00 RT61-2 10.00 -13.60 -15.2 6 10/6/00 RT61-3 10.00 -13.60 -15.8 45 10/6/00 RT61-5. 10.00 -13.60 -17.0 146 10/6/00 RT61-6 10.00 -13.60 -17.6 6 10/6/00 RT61-7 10.00 -13.60 -18.2 0 10/6/00 RT62-1 12.40 -13.70 -14.6 1 10/6/00 RT62-2 12.40 -13.70 -15.2 3 204 Table F5: Bromide Concentrations of Fourth Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 10/6/00 RT62-3 12.40 -13.70 -15.8 4 10/6/00 RT62-4 12.40 -13.70 -16.4 105 10/6/00 RT62-4 12.40 -13.70 -16.4 149 10/6/00 RT62-5 12.40 -13.70 -17.1 76 10/6/00 RT62-6 12.40 -13.70 -17.8 3 10/7/00 RT64-1 6.80 -13.60 -14.7 1 10/7/00 RT64-2 6.80 -13.60 -15.3 1 10/7/00 RT64-3 6.80 -13.60 -16.0 1 10/7/00 RT64-4 6.80 -13.60 -16.7 1 10/7/00 RT64-5 6.80 -13.60 -17.3 1 10/7/00 RT64-6 6.80 -13.60 -18.0 1 10/7/00 RT65-1 9.30 -17.20 -15.0 2 10/7/00 RT65-2 9.30 -17.20 -15.6 2 10/7/00 RT65-3 9.30 -17.20 -16.2 13 10/7/00 RT65-4 9.30 -17.20 -16.8 14 10/7/00 RT65-5 9.30 -17.20 -17.6 3 10/7/00 RT65-6 9.30 -17.20 -18.2 4 10/7/00 RT65-7 9.30 -17.20 -19.1 2 10/7/00 RT66-1 11.50 -16.50 -14.8 1 10/7/00 RT66-2 11.50 -16.50 -15.4 1 10/7/00 RT66-3 11.50 -16.50 -16.1 2 10/7/00 RT66-4 11.50 -16.50 -16.7 5 10/7/00 RT66-5 11.50 -16.50 -17.3 1 10/7/00 RT66-6 11.50 -16.50 -18.0 1 10/7/00 RT67-1 7.90 -17.70 -14.8 1 10/7/00 RT67-2 7.90 -17.70 -15.4 1 10/7/00 RT67-3 7.90 -17.70 -16.1 1 10/7/00 RT67-4 7.90 -17.70 -16.8 1 10/7/00 RT67-5 7.90 -17.70 -17.5 1 10/7/00 RT67-6 7.90 -17.70 -18.1 1 10/7/00 RT67-7 7.90 -17.70 -18.8 2 10/7/00 RT68-1 15.40 -17.70 -14.7 1 10/7/00 RT68-2 15.40 -17.70 -15.3 1 10/7/00 RT68-3 15.40 -17.70 -16.0 1 10/7/00 RT68-4 15.40 -17.70 -16.7 9 205 Table F5: Bromide Concentrations of Fourth Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 10/7/00 RT68-5 15.40 -17.70 -15.7 1 10/7/00 RT68-6 15.40 -17.70 -16.4 1 10/8/00 RT69-1 13.20 -17.40 -13.6 1 10/8/00 RT69-2 13.20 -17.40 -14.3 1 10/8/00 RT69-3 13.20 -17.40 -14.9 1 10/8/00 RT69-4 13.20 -17.40 -15.5 1 10/8/00 RT69-5 13.20 -17.40 -16.1 1 10/8/00 RT69-6 13.20 -17.40 -16.7 23 10/8/00 RT69-7 13.20 -17.40 -17.3 1 10/8/00 RT69-8 13.20 -17.40 -17.9 1 10/8/00 RT70-1 15.00 -15.30 -13.8 1 10/8/00 RT70-2 15.00 -15.30 -14.4 1 10/8/00 RT70-3 15.00 -15.30 -15.0 1 10/8/00 RT70-4 15.00 -15.30 -15.6 1 10/8/00 RT70-5 15.00 -15.30 -16.0 14 10/8/00 RT70-6 15.00 -15.30 -16.6 88 10/8/00 RT70-7 15.00 -15.30 -17.2 3 10/8/00 RT71-1 16.40 -15.40 -14.1 1 10/8/00 RT71-2 16.40 -15.40 -14.7 1 10/8/00 RT71-3 16.40 -15.40 -15.4 1 10/8/00 RT71-4 16.40 -15.40 -16.0 1 10/8/00 RT71-5 16.40 -15.40 -16.7 19 10/8/00 RT71-6 16.40 -15.40 -17.3 0 10/8/00 RT71-7 16.40 -15.40 -17.9 0 10/8/00 RT71-8 16.40 -15.40 -18.5 0 10/8/00 RT72-1 9.40 -13.70 -13.7 0 10/8/00 RT72-2 9.40 -13.70 -14.6 0 10/8/00 RT72-3 9.40 -13.70 -15.2 0 10/8/00 RT72-4 9.40 -13.70 -15.8 0 10/8/00 RT72-5 9.40 -13.70 -16.5 0 10/8/00 RT72-6 9.40 -13.70 -17.2 0 10/8/00 RT72-7 9.40 -13.70 -17.7 0 10/8/00 RT72-8 9.40 -13.70 -18.3 0 10/9/00 RT73-1 9.60 -12.90 -14.7 0 10/9/00 RT73-2 9.60 -12.90 -15.3 0 206 Table F5: Bromide Concentrations of Fourth Profiling Cruise Date Collected Sample I.D. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 10/9/00 RT73-3 9.60 -12.90 -15.8 0 10/9/00 RT73-4 9.60 -12.90 -16.5 0 10/9/00 RT73-5 9.60 -12.90 -17.2 0 10/9/00 RT73-6 9.60 -12.90 -17.8 0 10/9/00 RT73-7 9.60 -12.90 -18.3 0 10/9/00 RT74-1 9.80 -14.20 -14.8 1 10/9/00 RT74-2 9.80 -14.20 -15.4 33 10/9/00 RT74-3 9.80 -14.20 -16.1 68 10/9/00 RT74-4 9.80 -14.20 -16.7 116 10/9/00 RT74-4 9.80 -14.20 -17.3 120 10/9/00 RT74-5 9.80 -14.20 -18.0 29 10/9/00 RT74-6 9.80 -14.20 -18.3 23 10/9/00 RT74-7 9.80 -14.20 -19.5 1 10/9/00 RT74-9 9.80 -14.20 -20.2 14 10/9/00 RT74-10 9.80 -14.20 -20.8 0 10/9/00 RT75-1 9.40 -14.70 -14.7 0 10/9/00 RT75-2 9.40 -14.70 -15.3 1 10/9/00 RT75-3 9.40 -14.70 -15.9 25 10/9/00 RT75-4 9.40 -14.70 -16.6 29 10/9/00 RT75-5 9.40 -14.70 -15.7 23 10/9/00 RT75-6 9.40 -14.70 -17.8 1 10/9/00 RT75-7 9.40 -14.70 -18.3 0 10/9/00 RT76-1 11.20 -14.80 -14.9 0 10/9/00 RT76-2 11.20 -14.80 -15.6 1 10/9/00 RT76-3 11.20 -14.80 -16.3 51 10/9/00 RT76-4 11.20 -14.80 -17.0 N/A 10/9/00 RT76-5 11.20 -14.80 -17.6 214 10/9/00 RT76-5 11.20 -14.80 -17.6 245 10/9/00 RT76-6 11.20 -14.80 -18.4 38 10/9/00 RT76-7 11.20 -14.80 -19.2 1 10/10/00 RT76-8 11.20 -14.80 -19.9 0 10/10/00 RT77-1 12.90 -14.60 -14.7 0 10/10/00 RT77-2 12.90 -14.60 -15.3 25 10/10/00 RT77-3 12.90 -14.60 -16.0 10 10/10/00 RT77-4 12.90 -14.60 -16.5 64 207 Table F5: Bromide Concentrations of Fourth Profiling Cruise Date Collected Sample LD. X Y Z Bromide Point-depth (m) (m) (m.s.l) (mg/L) 10/10/00 RT77-5 12.90 -14.60 -17.1 174 10/10/00 RT77-6 12.90 -14.60 -17.8 201 10/10/00 RT77-7 12.90 -14.60 -18.4 18 10/10/00 RT77-8 12.90 -14.60 -19.3 0 10/10/00 RT78-1 13.00 -15.80 -14.3 0 10/10/00 RT78-2 13.00 -15.80 -14.9 0 10/10/00 RT78-3 13.00 -15.80 -15.6 5 10/10/00 RT78-4 13.00 -15.80 -16.2 84 10/10/00 RT78-5 13.00 -15.80 -16.8 107 10/10/00 RT78-6 13.00 -15.80 -17.5 132 10/10/00 RT78-7 13.00 -15.80 -18.1 103 10/10/00 RT78-8 13.00 -15.80 -18.7 9 10/10/00 RT78-9 13.00 -15.80 -19.4 0 10/10/00 RT79-1 10.70 -15.70 -14.7 0 10/10/00 RT79-2 10.70 -15.70 -15.3 13 10/10/00 RT79-2 10.70 -15.70 -15.3 12 10/10/00 RT79-3 10.70 -15.70 -15.6 76 10/10/00 RT79-4 10.70 -15.70 -16.5 74 10/10/00 RT79-5 10.70 -15.70 -17.1 27 10/10/00 RT79-6 10.70 -15.70 -17.8 180 10/10/00 RT79-7 10.70 -15.70 -18.3 37 10/10/00 RT79-8 10.70 -15.70 -18.9 10 10/10/00 RT79-9 10.70 -15.70 -19.7 15 208 A p p e n d i x K : Offshore 1 4 C - A c t i v i t y R e s u l t s 209 o CC g TJ CO CC o o o CO g T J CO rr CL CO o CO g T J CO DC o TJ ^ co O CD tO ^ 0 O > => < co Q 0 co 0 O > 3 < co Q CO co 0 O > ^ < T J CO 1 co r; CO CO O Notes 0 CL E CO 00 T J T J E E O) CM CM ^ 3 ! ^ ^ ^ S ; S ; ^ o 8 o 0 0 0 . 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CL CL * CL CL < i CL 9-A 9-A 9-A 9-A 9-A 9-A 9-A 9-A 9-A O 9-A OJ CJ CJ OJ CQ CO I h-DC QL TJ CO • r--CD • I— DC p- DC DC C L 3 in CD TJ ^ ^ i n i - i -A h h P DC DC DC oo CM X o co CD i : T - CO _c r-CL DC CO Z a. Q ^ 9 H CD DC DC CD I CD I-CM OJ * co co 1 O o CO o CO DC CM o o CL CO o co o T3 CO DC lo o 3 N Q. E CO CO CO o CD ff =d CO ^ co O < o CO g CO DC co Q CO < co g CD ff d CO ^ CD O > 3 < •£ >• E es — CO X E T3 CD 3 O CO CD Q 1 O Notes _CD Q . E co co co co co 0 0 0 O O O O O O o d d LO I - O ) LO LO O O O O O O O o d d co i - o T-o o 1 - 00 O O CM T-O O O O d d d d I— N CO CM TJ- CM CD O O LO T t O O T- T-d d 0 d f- CM TJ- CM O O CO CD O O CM O O O O O O O O O 1 - 1 - o oo CO CD O Tl-1 - O LO CM O O 1 - T -0 0 0 0 CO V— (1 ^ 3 o 1 3 5 J? co % o H Q . CO X J O 1 5 CO II O -S* « 8 =• 3 _ ; CO » i •s > 5 1 .* o « z • ° o CD O) > 2 _; 9> Q « O ± = CD .g CD S CO CO CO £ « 5? 3 8 ° CD S CD CD CO CO CD -»—• g 'E o CO -t—• o g-lo CD CO o CD > CO CO CD CO CO > .Si > 01 CO o > o a> GO CL E Q. co CO CO CD o . 0 c 'E o CO CD E •a 3 c o o co" o g-lo CD ° to co M .g C L 3 o r: 00 T t 32 o 3 T3 CO g ^ CD CO N C >> CO cO CD CO CO CD CD i _ g 0) N >< co c CO t n CO 3 <o • T3 ^ c CD E c > I c o ~ 0 1.1 * CO o CO s co co CD ^ CD o co "o o re § -a § 5 o « c CO CO J O Z «= X) o 5= CO CO CD 0 § 8 2 11 9- to _ i E a> ro * ; • CO — v CO 1— CM > o CO o T J CO DC CM o o •4—' > o CO g T3 CO DC si CL CO > O CO g T O CO DC "co -I—' o I-"a ^ co O CD ff d co CD O > 3 < T O co O CD ff d CO CD O > => < T O r=: co O CD ff d CO ^ CD O > 3 < i2 N o o O O c o c QL E CO CO X E CD CD ft o Notes q a> C L E CO CO T O TO E E o> co co co T f o o o << o o o o 5; o o o o z d o d o T f C D o o ^ ^ - $ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ O O Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z o o T f O O O O O O O O d d d d LO i - OO Tf CVJ LO LO O < - CM CM ~ ~ ~ -2: o o Z O O d d < C < < < < < < < < < < < < L O C O •>- O i - C D C O C D O O - ^ C 0 C M T - < : < : < o o o o o o o z z z d> o d> d> ei d> ci a V co co i -00 O CM O O O O O O o d d z z z z z z z z z z z CO N N CO Tf Tf CO o o O O O o d d C O C M C O 00 C M OO C M i -L O Tl- C M i -T - 1 - O o d d d Q a Q d V V V CM CO Tf -Is-o LO o d d CM CM CM ™ < c < < < < < < < < < < o d z z z z oo CM Tf CM CD oo OO oo co oo I s - CO LO o CM o O CO CD o LO co i — Tf o T— o < f 1— T— < r CM O o O CM o o o o o o o o o o o o o O o O o o o o z z z o o o o o o o z o o z z o d d d d d d d d d d d d d d d d d oo o oo co o o I s - CO CO LO Tf CM co Tf CM o co CD o Tf o CJ) _ i _ j _ i oo CM oo I s - Tf 1— LO _ i I s - Tf _J _ j co I s - ^— o LO CM CM o • • LO Tf oo o o o o ' co 1— t • ^ • o o O o o o Q Q Q o o o o o o Q o o Q Q o d d d d d d d V V V d d d d d d d V d d V V d I s - 00 CO LO o oo CM CM CM 00 I s - o CM Tf I s - oo Tf O) CM co LO oo oo Tf I s - Tf oo LO LO LO LO cb LO CD LO LO LO co LO CD LO LO CO I 1 1 1 l — I 1 1 1 1 1 1 1 1 co LO LO I s - I s - I s - CD LO LO CD LO co CO CO CO 00 Tf LO LO Tf Tf Tf CD CD CD CD I s-' Tf Tf LO LO CM 1 1 1 1 1 1 • 1 1 1 • • I 1 1 oo o o q q q oo LO LO 00 LO oo oo CO CD CO CM CM CM OJ 1 CM CM CM co CO >> >< >> >> >* >< >^  >* (Ti. >* > s /"rt co CO CO CO CO CO co co co co CO CO CO 1 1 1 • oo • O) • 1 • • I s -I 00 00 1 oo 1 CO 1 oo 1 CJ) 1 O) o o o CO CO CO CO CO CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM O T J CD CO 1 •? O 0 0 CO CM -5 I— 5 DC 5 a »- o iS o g CO —: a. co co T J " o o — Q o Tf -i— CM DQ O CM CM CO CO CO CO CM CM T - T - -r-I— I— I— I— I— DC DC DC DC DC ff X o co z CD 5 a CO Tf CO Tf CO Tf CO Tf Tf LfO ob ob oo CO co LCO LO ci) T— T— 1— CM CM CM CM CM CM H H 1— 1- 1- 1- 1- 1- H 1— DC DC X X X X X X X X X O CO CD x: C L crt T f CM > o CO o T J CO DC tN O O > o co o TJ CO DC si CL CO o CO o TJ CO DC "co •4—• o H T J ^ CO O CO b3 O < T J rs, CO o CD CO ^ aj O > 3 < TJ ^ CO o CD CO ^ CD O > ZJ < CO 2 N CO g T J O O o TJ o OJ c Q . E CO CO >• E X E TJ CD I CD o CO CD O Notes o. E co CO T J T J E E < < < < < < < < < < < < < < < < < ° 5; o z q o S: ^ ^ S; ^  ^ z z z z z z Q V ^ ^ S: 5: z z z z <c <c < < < c < c < < < < < < < < < < < < < < < <: 5t <: < Q V ^ S: ^  ^ z z z z < <: z z <: z <c < < C O CM <-o z o co o 8 «: d z CM CD <r o 5: o z <:<:<<< <c <c < < < 9 T 3 O o « ~ <c <c < < < •sr co •sr 0 0 •sr CO •sr CO CO <: <: <: <: <: 0 0 0 0 0 0 <: 0 0 <: <: <: 0 0 0 0 <: 0 0 < 0 0 < 0 0 <: z z z z z z 0 0 0 z 0 z z z 0 0 z 0 z z 0 z 0 z d d d d d d d d d r - cn CO •sr co CM CD LO co _i _l _l _i _l 0 T— _i CO _i _i _i •sr m _i •st _i _i 0 _i in _i 0 0 Q Q Q Q Q 0 0 O O O O ci 0 0 Q Q Ci CM 0 0 0 ci O Q Q 0 0 Q 0 0 c i d V V V V V d d d V d V V V d d V d V V d V d V LO 0 0 0 CM CM 0 CM 0 0 0 0 0 0 0 CM •sr cn CM 0 CO LO CO 0 CO •sl- 0 0 •sr 0 0 LO in 0 LO 1 1"-' q co 1 0 LO LO CD 0 LO 0 ed 0 LO CD 0 CD 0 LO LO 0 CO q 1 1 1 1 1 1 1 • 1 • • d 0 O 0 0 0 0 0 0 0 0 0 0 0 0 0 0 O 0 O O 0 LO in I-- r»- CO CO LO LO LO LO CO CO LO LO in in m co co co co co r -•sr •sT ^r CO CO CO CO CO CD CO CD 1 ^ LO LO LO •sr •sr iri LO iri CM CM o o 0 0 0 0 m m i n m o o 0 0 0 0 CM CM 0 0 0 0 0 0 i n m 0 0 0 0 o co o o co co • I - T - C M C M C M C M C M C 0 C O C 0 C O C 0 0 3 C O C O C O C O C O C O P 3 C O C O C O C O B T- CM m r -C0 I— I— I— I— I— I— I— I— c M C M C M C O o o m i n m c o C M C M C M C M C M C M C M C M C M C M C M H t t CO CO CD -t—' ZJ C "E o 5 H _ J CO ® - i 2 x ^ o c CO iS Z •° o CD > CJ) > CO _ ; 5 c i « O 5 CD 5= CJ) CJ) 2 .g CD O CO w CO ™ 0 c CD CD CD CO CD CO cfl CO o > o 0 "5 Q_ J Z E °-co Z cz o o CO o H— w •*—• O ZJ CT "TO CD CO o = CD % £ CO fD i? ^  T J T J 0 ) CD CD I 8 ° CO O eo 5 CO CO TJ .t= 3 o CO CO CO moo-srinmcom-srmco-srm-srmco-sr -srm co CM i r l r i r i r i r r i L t Q r L t D C i r o c i r L t i r i r D C L r a i r r i r D C i r CZ Z3 o . 0 d "E o CO CD E T J CD c r> o o eo o o n CT "cO CD ° « .9 Q -0 0 •sr ZJ TJ ^ "° CD CO N C >> co co CD CO ! i £Z CD i -— i - O SZ CJ) •_ g CO cfl CO c CD CO ZJ TJ c CD E E - = o ° E cz o CO o w 2 _>v CD co "CJ co ro o *-CD CO eo .iii n 01 » co CO CD a V 10 CM •sr * CD CO ' 3 I O ;> +J o CO g TJ co DC OJ O O > o CO g TJ co DC Q. CO > +-» O CO g TJ co DC o CO CD CO c TJ L o o o TJ C L E Cfl CO TJ ^ CO O CD c ? ^ CD O > 3 < TJ ^ 0 0 O CD co ^ a5 O > 3 < TJ ^ CO o CD CO CD O > 3 < N 1 > £ CD ~ CJ) c X E TJ CD CD fi CO CD Q 1 O Notes 0 ) C L E CO CO co LO CO LO CM CM 0 0 0 O 0 0 0 0 0 O 0 0 0 0 0 O 0 0 d 0 0 d d 0 CO •sr •sr CO 0 0 r~ CO •sr •sr 0 •sr •sr 0 0 0 0 0 0 0 0 0 0 0 0 d 0 0 0 0 0 •sr •sr r~ •sr CM CM •sr 0 0 CM CM 0 0 0 0 0 T — 0 0 0 0 0 O 0 0 d 0 0 d 0 0 CO CD r~. •sr •sr 0 0 CO CM CM •sr •sr •sr 0 0 CO CO 0 0 0 0 0 1— 0 0 d d d 0 0 0 0 0 O CM CM CM 0 co LO 0 0 1— in 0 CO CM CO CO co CO <*• 0 i— 0 0 O O T— 0 1^. 0 •sr 1— O 0 ^— O T— O O 0 O 0 0 O O O O O 0 O 0 0 O O 0 0 O O O O 0 O 0 z 0 O O O O O O 0 O 0 0 O O 0 0 O O O O 0 O 0 0 d d d O d O d O 0 0 O d d d d d d d d d d CM CO CO CD 0 0 m CM CM CM in m •sr CO CM CM 0 0 0 CM 0 0 •sr _ i LO 0 CM CO lO 1 0 CO 0 CO 0 0 •sr CM CM 0 CD •sr CO 0 0 CO 0 m CJ) •sr •sr O 0 CO CO 0 CD CO 0 0 0 CM O CM 0 0 0 0 0 Q 0 0 0 O 0 O 0 0 O 0 0 0 0 0 O 0 0 0 0 0 0 V 0 0 d d d d d d d d d d 0 d 0 d d 0 0 0 d d m co 0 LO CM CO •sr 0 0 0 LO m co CO co 0 0 0 0 CD 0 0 0 co CM CD m 0 r- CM •sr 1— r>- co co r- CM CM q co iri iri co co iri CO iri co CO l< iri CO CO iri CO CO 0 1 1 T— 1 • 1 1 1 1 1 1 1 1 1 1 1 1 1 • O) CM O) •sr CM CM CM CD CD CD CD CD co co •sr CO co CM CM •sr CM 1 0 •sr •sr •sr c\i c\i CM CM CM CM CM I - * 0 iri i r i 1 • 1 1 1 • • • • 1 I 1 1 1 1 1 • 1 1 1 co 0 co r>- 0 0 0 CO CO co •sr •sr 0 0 0 0 LO LO CD •sr CO CM CO CM co co co co CM CM CM CO CO y— T - ' CO co LO CM CM c c c c c c c c c c c c c c c c c c c C 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 - p —3 —3 - p - p ~i - p - p - p - p - p - p - p - p - p - p - p - p - p - p co CM co iri CM CM CM co co co co co •sr •sr •sr •sr •sr •sr LO iri , — CO CO CO CO CO CO CO OJ OJ OJ OJ OJ OJ O) 01 OJ OJ CM OJ OJ OJ OJ OJ CO 0 0 CM I 1-DC DC DC DC O o I— co X D. < z X o < i S c M C O - s T C M C O - s r C M C O C O - s r C M C O C O C M - ^ C O —. ti Q 0 0 0 0 CM CM 0 0 1-CM CO •>- CM co co in co N co CO CO CO CO D C C C D C D C D C D C D C D C D C C C D C D C D C D C D C D C C O T -C M > o co o TO CO DC OJ O O ;> o ca g TO co CC sz Q. CO > o CO g TO CO DC "CO o CL E CO CO CO O CD co CD O > 3 < 53 o CD • f i d CD O > 3 < ~o Z^ CO O CD CD O > 3 < <2 N ^ co E TO i o o O „ v > E (5 ~~~ CO X E 7 3 CD I co CO CD O Notes 0) CL E CO CO n N n c o i n n n N ' * c o n c o w L n n c o o N n O O O O O O O O O O O O O O O O T - O O O O O O O O O O O O O O O O O O C O O O o o o o o o o o o o o o o o o o o o o d d d d d d d d d d d d d d d d d d d O T C O O O O O O O T - O O O O O O C O L O L O O T t O O O O O O O O O O O O O O C M O O o o o o o o o o o o o o o o o o o o o d d d d d d d d d d d d d d d d d d d n o n c o c o o c o m t o c o o o c o ^ o i o • v t c o ^ c q c o c q ^ o q ^ c q c q q c o g o q ^ d u i i f l i r i w u i c d i i i i i O N i o i o i r i ^ i r i c d O L O no L O in Is- CJO CO L O LO CO o cd oo cd co co co oo L O Is-S N N N CO Oti L O L O L O oo coo oo co CM LO Tt Tt Tt CM CO T- T~ T— Is- Is- Is- Is-LO CO co CO cd T — T — 1— c 3 ~3 C C C 3 3 3 ~i —} —y c 3 -3 c 3 c c 3 3 —> —i L O L O i o c o c o c o c o c o c o c o i s - i s - i s - r s - r s - r s -c \ j c \ j c \ j c \ i o j c \ i c M c \ i c \ j c \ j c \ j c \ i c g o j e j c \ j c v j O CNJ C O C M C O C M C M C T J O T ^ C M C O C M L O C O C O CO Tt Tt Tt Tt I— h- H I— (— IT DC DC DC DC DC C O C M C O L O C M C M C M C Q C M C O • • i i i i i i i • co co Is- oo oi o o Tt Tt Tt Tt Tt LO LO I— I— I— I— I— I— I— CXI CC CC QC OC CC CC Tt Tf I- h-cc OC o o S co-l -or X o < —; z Q Is-o o o oo o o d CM CM o o CO CO CM o d CO CO CO CO Tt CO 0 0 < f O O O O < f o o 9 ; o o o o < ; o o z o o o o z d o d o d o oo CO co CO LO Tf o Is- _ i coo Is- i— co _ i LO • CO CM o T - • o o Q o O o O Q d d V d d d d V LO CM co Tt Is- Tt CD o co CM oo LO o LO i— CO i CO i 1^ 1 LO i co 1 Is-: i cd 1 LO i LO LO LO o o o o o T— T— i— oo oo O) Is- q Tf 1 Tf 1 Tf 1 CM CM 1 CM 1 Cvj i CO • o o o o o o o o o o o CO CO CO Tf LO CO CO CO CM CM CM d CO c c c c cz c c c 3 3 3 3 3 3 3 3 —3 ~3 —> —3 —> —> —> CM CM CM co co ch co co CO CO CO CO CO CO CO CO CM cp Tt CM cp Tf CO C\l 1^ Is!- CO CO CO C50 d CM CM CM CM CM CM CM co h- 1- \— \— H H h- h-X X CC CC X X X X C N > o CO o X J CO DC o o > o co g X J co DC .c CL CO o CO g X J CO DC "cc o CO CO XJ co O CD CD O > 3 < X J 55 O CD CO ^ CD O > 3 < CO O CD c ? ^ CD O > 3 < I N ? co E c XJ o o O _ .-o > E O ~~ DJ C x E X J CD .2 O CO CD O Notes 0 CL E CO CO m •sr CO CO CO 00 CO 00 CO 00 o o < o o o o o o o o o o o o o <: o o <: o o < <: o o <C < <c o z z o o z o o o o o z o z z o z z z z z z z o z z z z d d d d d d d d d d d CO 00 •sr CO -sr 00 CD CO o CO co T — _ i _ i m 00 _j CM in o o o _i CO _ i _ i CM _ i _ i _j _j _j _J _ i i— _ i _ i _ i _J o o d d CM o o o d CM o o o o o o o o o d o o d d •sr o d d d d d d d o o d d d d d V V d d V d d d d d V d V V d V V V V V V V d V V V V o 00 00 in in CO CD CD CD oo co o co co oo o oo LO CO oo oo o oo o CM 00 T— CO CO 00 i— CM CM •sr CO •sr 00 oo co •sr oo •sr CO 00 CD 00 CO iri CO iri iri CO CD CD iri CD CO CD iri CO iri iri iri CO iri CD r^ iri iri iri iri o o o o o o o i n m o j o j c n i - i - n c i c o c o C M C M C M C M C M ' T ^ T ^ T ^ T ^ I I S ^ i q i D n w q ^ i n q i n n q c q i q c q f f i i n s ' d i r i i r i i r i i r i i r i i n w i n i n m s i D o i c o N N S N c o c O j j 1 T ' ' 1 ' T"~ ' ' ' ' ' T i o •sr O •sr O •sr m r~ m r~ o in o LO o CD O CD CD y- •sr CO CM r- CD o 00 CM in •sr •sr •sr •sr 1^ CO CO co co co iri iri iri oJ CM CM CD co iri 4 CD CM co" CD iri CO CO c cz cz CZ CZ CZ CZ CZ CZ CZ CZ CZ CZ c CZ CZ CZ CZ CZ c CZ c CZ CZ CZ CZ CZ CZ 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 ~p -p -p -p -p -p -p -p -p -p -p -p —3 ~p - p —3 -p ~D - p - p —3 -p -p - p -p - p -p -p CO CO CO 4 4 4 4 4 4 4 4 4 iri iri iri iri iri CO CO CO CO CO CD CO ri- 1^- r^ - ri-CO CO CO CO CO CO CO CO co CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO C0 co CO CO CM co CQ CM •si" CO CM CO CO CO CM CO CO CO CM CO CM CM CM cp CM CO LO CM CM CM CM yL CM CM CM 4 4 4 iri CD co CO CD O y— CM CO 4 iri CO CO CO 00 CD O CO CO 00 CO CO CO CO 00 CO CO CO 00 co CO CO •sr •sr •sr •sr •sr •sr •sr •sr •sr •sr •sr •sr LO 1- h- H I- 1- r- 1- I- r- I- I- 1- 1- I- r- I- 1- (- r- 1- 1- 1- h- h- l - h- 1- 1— DC DC DC DC oc tr DC DC cc DC DC DC DC CC DC DC oc DC DC DC DC DC DC DC DC DC DC DC CO CN \> o ca g T J ca DC O o > o ca g T J ca DC Q. ca > o ca g T J ca DC "ca o T J ^ CO O CD co r^ s <5 O > 3 < T J co O cu CD O > 3 < T J ."^ CO O CD c?s! (D O > 3 < iB N i i ca E c -T J k O o O _ ^ > E O) c C L E ca co X E T J CD i cu r; J » E O -=H Notes J D C L E CO CO <: <: z z Q D V V LO LO oo oi c d c d 3 3 -p -p CO CO 9 o LO LO -r- T J o s eg ° o n CO CO UJ CD 3 C 'E o 5 •§ _: cn • - i . * o JS z •° o CD ^ OJ > CO _; | Q 0 3 o 5 CD s= cj) co i— = 0) • i 3 > O CO u 5 •= D) C c 3 o o CO o **— CO o 3 g-"ca CD 13 o J2 So CD TJ -o O t i CD CD D) C "° CD ca N c ca co T J <= C 3 O .CJ c E o T— 1 o H— CO CD E -t-» o T J 3 C 3 O CJ co cn 3 -*—1 o O 3 .£= g-CO Tf- "co CD o ••-» CO CD g c "5. T3 3 O T J .G CO i C Q) ' N >, CO CO C/) c 0) ca 3 T J o o CD o o c CD CD CD • ° - i CD > > CO ca CD -C 3 <!? CO c CO c o 9 o > CD CO > c CD CO CD - £ O 3 co JS T J c 0) CO C L X: E Q-— O C/J — CO CO co c CO CO 1 I i i CO o « J2 _>< CD CO T J CO co CO CO CD T J c 3 m P II CO Z M= CO _l 0 5 /-I • £ L J CO y o LO CO co ' 3 o > o co o T J CO cr OJ o o o co g T J CO CC CL CO o CO g T J co DC "co o T J CO g o CO ^ CD O < T J ^ CO o CD CO CD O > z> < T J ^ CO o CD CO CD O > ZJ < CD INI • I £ T J O O O _ ^ > E <5 CJ) c C L E CO CO X E T J CO 2 t3 CO CD Q 1 O Notes 0) Q . E co CO CM O O O d LO o o o o o o 0 co CD o o r-o o < o o 5; o o z 0 d LO -si- . CD co — i O O Q o o u 0 0 v CM o o o d co o o d co o o o o o o o o d co CM o o •sr o o o co o o d LO CD •sr •sr co O 0 0 0 0 O 0 0 0 0 O 0 0 0 0 d d d d d CD LO co 00 CD LO co CM CT) CD 0 0 0 0 0 0 0 0 0 0 d d d d d •sr o o o 00 o o o d 00 CD o o r--O) co o •sr -sr CD co uo o o 1 - o o 0 0 0 0 0 0 0 0 0 0 d d d c i d CO _ - § co o o § o 0 0 ^ 0 LO T- CO T - CM LO o - -o o CM CM LO 00 co ^ eq T - 00 LO 00 N N W C O C O C O C O C O O O C O N c o c o r - ^ - s r - s r - s f - s r - s T L O L O L O I I I I I I I I I I c r i c o o i ^ ^ ^ ^ ^ ^ ' - ? t j t 5 t 3 B t j t j ^ ^ ^ ^ « 0 0 0 0 0 0 9 9 9 9 9 c o c o r ^ c j S d ) d ) 0 0 0 0 0 OTP3WO0COCOCOCOCOCOCOC0 • s r C D C D C O - s T L O L O C O L t l C D C O o o LO CD co CO CD CO CO N N N I— . DC DC DC <r DC DC DC DC DC 00 CO CT) r>. r^ -1— I— H DC DC O O H CO X < X O CD 11 —. Q Q 

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