THESIS 3 26 ct This is to certify that the dissertation entitled CHROMIUM SPECIATION AND MOBILITY IN CONTAMINATED SOILS, SAULT STE. MARIE, MI presented by Gary Allen Icopini has been accepted towards fulfillment of the requirements for PhD. degree in Geological Sciences Date [OI/i/fio MS U i: an Affirmative Action/Equal Opportunity Institution 0- 12771 LIBRARY Michigan State University PLACE IN RETURN BOX to remove this checkout from your record. TO AVOID FINES return on or before date due. MAY BE RECALLED with earlier due date if requested. DATE DUE DATE DUE DATE DUE 2007 $5900?) a 7 moo c/CIRCJDatoDuopes-p.“ CHROMIUM SPECIATION AND MOBILITY IN CONTAMINATED SOILS, SAULT STE. MARIE, MI By Gary Allen Icopini A DISSERTATION Submitted to Michigan State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Geological Sciences 2000 ABSTRACT CHROMIUM SPECIATION AND MOBILITY IN CONTAMINATED SOILS, SAULT STE. MARIE, MI By Gary Allen Icopini The fate and mobility of chromium in a wetland area was studied using both field and laboratory techniques. Wetlands have been used as sinks for chromium because in reducing wetland environments chromium will exist as Cr(III) which is a less toxic form of chromium and inorganic Cr(III) solids are very insoluble. However, there is very little information concerning the mobility of chromium in organic rich environments like wetlands. Chromium speciation in the soils was investigated using sequential chemical extractions. Chromium speciation in the aqueous samples was investigated using solid phase extraction resins that removed the cationic, anionic, and hydrophobic organic species from solution. The mobility of chromium in these soils was assessed using intact soil core microcosms. The microcosms were treated with solutions to simulate acid rain deposition and the influx of nitrate and potassium. The speciation work indicated that chromium was associated with both inorganic and organic components of the system. The results from the soil speciation studies showed that the solid phase chromium was primarily extracted by the acidic moderately reducible (MR) and basic oxidizable extractions. These results indicate that the solid forms of chromium in these environments will be either a chromium hydroxide or associated with the soil organic matter, with chromium hydroxide becoming more dominant at higher total concentrations of chromium in the soils. The aqueous phase chromium concentrations in the surface and pore waters at this site are higher than would be predicted by inorganic thermodynamic calculations. No Cr(V I) was observed in these samples. The aqueous chromium in the field samples was found to be slightly correlated with dissolved organic carbon (R2=O.66). The results of the solid phase extraction . performed on the aqueous field samples show that aqueous chromium in field samples exists primarily as an anion in these waters (96%). It is concluded that the solubility and mobility of chromium is controlled, at least in part, by complexation with dissolved organic carbon and that this may be a thermodynamically driven process. Intact soil core microcosms were used to investigate the mobility of chromium in laboratory studies. The data from the microcosm experiments also indicated that the aqueous chromium existed as an organically complexed anion. The results of the microcosm experiments indicate that the solubility of chromium may also be increased if the soils experience periods of cyclic saturation and unsaturation. There also may be an increased solubility of chromium if the degradation of soil organic matter is increased. ACKNOWLEDGMENTS There have been many people that have lent their moral and technical support to the completion of this dissertation. Foremost among these is my wife, Pat, who has always supported and encouraged me. I would also like to acknowledge my advisor, David T. Long, who has been instrumental to the completion of this project and I would also like to thank him for helping to make me a more independent scientist. I would also like to acknowledge the past and present members of my dissertation committee, Michael Velbel, Lina Patino, Michael Klug, and Sharon Anderson, who provided helpful insights and encouragement along the way. I would also like to acknowledge my friends Robert Ellis and Christophe Merlin who were my partners in this endeavor and without whom this project would have been far less enjoyable. I would like to acknowledge the people who I shared the lab with on microcosm days for their patience, chief among these were Jennifer McGuire and Sarah Woodham who were always quick to help when I fell behind. I would also like to acknowledge the numerous people who assisted with various aspects of this project including Terry Marsh, Paul Loconto, Joel Fett, Mathew Harold, Nathan Mellot, Sarah Hayes, Raullie Casteel, Page Vassar, Jeff Vought, Michael Roberts, Jane Matty, and Susan Sipple. This research was funded by a grant from a corporate sponsor who wishes to remain anonymous. iv TABLE OF CONTENTS LIST OF TABLES ........................................................................................................... viii LIST OF FIGURES ......................................................................................................... xiii I. INTRODUCTION ........................................................................................................... 1 1.1 The Problem .................................................................................................................. l 1.2 Approach ....................................................................................................................... 4 H. BACKGROUND ............................................................................................................ 9 2.1 Study Site ...................................................................................................................... 9 2.2 Geochemistry of Chromium ....................................................................................... 10 HI. METHODS ................................................................................................................. 14 3.1 Solid samples ............................................................................................................. 14 3.1.1 — Sample Grid Development, Surveying, and Site Locations ................................. 14 3.1.2 — Sample Collection ................................................................................................. 15 3.1.3 —— Sequential Chemical Extractions .......................................................................... 16 3.1.4 — Total Extractions ................................................................................................... 18 3.1.5 - Solid Phase Organic Carbon Content ................................................................... 19 3.2 Aqueous Samples ........................................................................................................ 20 3.2.1 — Sample Collection ................................................................................................. 20 3.2.2 — Analytical Measurements ...................................................................................... 22 3.2.3 — Solid Phase Extraction Media ............................................................................... 23 3.3 Microcosm Design and Sampling ............................................................................... 27 IV. SPECIATION OF CHROMIUM IN THE SOILS ..................................................... 31 4.1 General Observations .................................................................................................. 31 4.2 Results of the Sequential Extractions ......................................................................... 33 V. AQUEOUS PHASE SPECIATION OF CHROMIUM ............................................... 38 5.1 Pore-Water Data and Thermodynamic Modeling ....................................................... 38 5.2 Chromium and DOC ................................................................................................... 40 5.3 Solid Phase Extraction Data ........................................................................................ 41 VI. SELECTION OF MICROCOSM SITES ................................................................... 46 6.1 Rational ...................................................................................................................... 46 6.2 Statistical Analysis ..................................................................................................... 46 6.2.1 — Factor Analysis ..................................................................................................... 46 6.2.2 — Q-Mode Factor Analysis ....................................................................................... 47 6.2.3 — R-Mode Factor Analysis ....................................................................................... 49 6.2.4 -- Summary of Factor Analyses ............................................................................... 50 6.3 Criteria Used for Selection of Soil Samples .............................................................. 51 VII. ACID RAIN MICROCOSMS ................................................................................... 55 7.1 Rational ...................................................................................................................... 55 7.2 Dissolved Chromium versus DOC Results ................................................................ 56 7.3 Solid Phase Extraction Results .................................................................................. 57 7.4 Changes in pH Over Time ......................................................................................... 58 7.5 Changes in Chromium Concentrations Over Time .................................................... 60 VIII. NUTRIENT MICROCOSMS .................................................................................. 66 8.1 Rational ...................................................................................................................... 66 8.2 Dissolved Chromium versus DOC Results ................................................................ 68 8.3 Solid Phase Extraction Results .................................................................................. 70 8.4 Changes in Nitrate and Sulfate Concentrations over Time ........................................ 70 8.5 Changes in Chromium Concentrations over Time ...................................................... 76 IX. SUMMARY AND CONCLUSIONS ......................................................................... 82 9.1 Summary .................................................................................................................... 82 9.2 Conclusions ................................................................................................................ 87 REFERENCES .................................................................................................................. 89 APPENDICES ................................................................................................................... 99 Appendix A: Sample Location and Soil Core Descriptions .......................................... 100 Appendix B: Sequential Chemical Extraction Procedure .............................................. 112 Appendix C: Field Aqueous Sampling .......................................................................... 116 Appendix D D-l: Sequential Chemical Extraction Data for Chromium ............................................. 119 D-2: Replicate Sample Analysis for Chromium ............................................................. 129 Appendix E: Soil Organic Matter Content ..................................................................... 133 Appendix F F -l: Pore water data for samples taken on 7/26/97 ......................................................... 135 F-2: Pore water data for samples taken on 8/ 13/97 ........................................................ 136 F -3: Pore water data for samples collected 10/8/97 ....................................................... 137 F-4: Pore Water Data Collected on 11/20/97 ................................................................. 138 F-S: Pore water data for samples collected 6/9/98 ......................................................... 139 F -6: Pore water data for samples collected 8/22/98 ....................................................... 140 F-7: Pore water data for samples collected 10/10/98 ..................................................... 141 Appendix G G]: Solid Phase Extraction Data — Chromium ............................................................. 142 G-2: Solid Phase Extraction Data — Manganese ............................................................ 143 Appendix H H-l: Sequential Chemical Extraction Data for Iron ...................................................... 144 H-2: Replicate Sample Analysis for Iron ....................................................................... 154 Appendix I I-1: Sequential Chemical Extraction Data for Copper ................................................... 158 I-2: Replicate Sample Analysis for Copper ................................................................... 169 vi Appendix J J-l: Sequential Chemical Extraction Data for Zinc ....................................................... 173 J-2: Replicate Sample Analysis for Zinc ....................................................................... 185 Appendix K K-l: Sequential Chemical Extraction Data for Manganese ........................................... 189 K-2: Replicate Sample Analysis for Manganese ........................................................... 199 Appendix L: Chemical Compositions of the Treatment Water ..................................... 203 Appendix M ' M-l: Acid Rain Microcosm Data -- pH .......................................................................... 204 M-2: Acid Rain Microcosm Data — Chromium (pg/L) ................................................... 205 M-3: Acid Rain Microcosm Data — Dissolved Organic Carbon (mg/L C) ..................... 206 M-4: Nutrient Microcosm Data — Chromium (pg/L) ...................................................... 207 M-5: Nutrient Microcosm Data - Dissolved Organic Carbon (mg/L C) ........................ 208 M-6: Nutrient Microcosm Data — Nitrate (mg/L NOg') .................................................. 209 M-7: Nutrient Microcosm Data -— Sulfate (mg/L SO42) ................................................. 210 vii LIST OF TABLES Table 1. A summary of selected sequential extraction procedures. ................................. 17 Table 2. Summary of the sequential extraction procedure used in this study (modified after Bezile et al., 1989). ................................................................................... 18 Table 3. Factor scores for the Q-mode factor analysis on the entire soil data base. The red scores indicate the variables important in controlling the five factors. The important variables for each factor are also listed at the bottom of the table. ................... 49 Table 4. Results of R-mode factor analysis on soils fi'om the site with chromium concentrations greater than 100 mg/kg. At the top of the table are the eigenvalues and proportion of the variance explained by each factor. The center of the table shows the loadings of the variables on the factors. The variables that comprise each factor are listed at the bottom of the table. ................................................................ 51 Table 5. A listing of the initially proposed microcosm sites and the rational and criteria associated with their selection. .............................................................................. 52 Table 6. A summary of the physical and chemical characteristics of the sample sites selected for the microcosm work. .............................................................................. 54 Table 7. A summary of the concentration of chromium in the microcosm soils presented in order of decreasing chromium concentrations in the microcosm effluent. .............................................................................................................................. 63 Table 8. Summary comparison of chromium in the effluent from nutrient microcosm experiments. .................................................................................................... 78 Table 9. A summary of the concentration of chromium in the microcosm soils .............. 80 Table A-1. Sample Location and Soil Core Descriptions ............................................. 100 viii Table D-l. Sequential Chemical Extraction Data for Chromium ................................. 119 Table D-2. Replicate Sample Analysis for Chromium ................................................. 129 Table E-l. Soil Organic Matter Content ....................................................................... 133 Table F-l. Pore water data for samples taken on 7/26/97 .............................................. 135 Table F-2. Pore water data for samples taken on 8/13/97 .............................................. 136 Table F-3. Pore water data for samples collected 10/8/97 ............................................. 137 Table F—4. Pore Water Data Collected on 11/20/97 ....................................................... 138 Table F-S. Pore water data for samples collected 6/9/98 ............................................... 139 Table F—6. Pore water data for samples collected 8/22/98 ............................................. 140 Table F-7. Pore water data for samples collected 10/10/98 ........................................... 141 Table G-l. Solid Phase Extraction Data — Chromium ................................................... 142 Table G-2. Solid Phase Extraction Data - Manganese .................................................. 143 Table H-l. Sequential Chemical Extraction Data for Iron ............................................. 144 Table H-2. Replicate Sample Analysis for Iron ............................................................. 154 Table [-1. Sequential Chemical Extraction Data for Copper ......................................... 158 Table I-2. Replicate Sample Analysis for COpper ......................................................... 169 ix Table J-l. Sequential Chemical Extraction Data for Zinc ............................................. 173 Table J-2. Replicate Sample Analysis for Zinc ............................................................. 185 Table K-l. Sequential Chemical Extraction Data for Manganese ................................. 189 Table K-2. Replicate Sample Analysis for Manganese ................................................. 199 Table L-l. Chemical Compositions of the Treatment Water ......................................... 203 Table M-l. Acid Rain Microcosm Data -- pH ............................................................... 204 Table M-2. Acid Rain Microcosm Data — Chromium (pg/L) ........................................ 205 Table M-3. Acid Rain Microcosm Data - Dissolved Organic Carbon (mg/L C) .......... 206 Table M-4. Nutrient Microcosm Data — Chromium (pg/L) ........................................... 207 Table M-5. Nutrient Microcosm Data — Dissolved Organic Carbon (mg/L C) ............. 208 Table M-6. Nutrient Microcosm Data — Nitrate (mg/L NO3') ....................................... 209 Table M-7. Nutrient Microcosm Data — Sulfate (mg/L SO42) ...................................... 210 LIST OF FIGURES Figure l. A map of the study site, showing type of vegetative surface coverings ............. 9 Figure 2. A map of the study site, showing the locations of the sampling sites. ............. 15 Figure 3. Schematic diagram of a “peeper” sampler used to collect pore-water samples ............................................................................................................................... 20 Figure 4. Schematic diagram of a “barrel” sampler used to collect pore-water samples ............................................................................................................................... 21 Figure 5. This diagram shows the design of the intact core microcosms. The red arrows show the flow direction of the water. The entire apparatus was maintained at 14°C in an incubation chamber. All fittings were non-metallic, all caps were Teflon® and the tubing was Tygon.®. ................................................................................ 28 Figure 6. Breakthrough curve for Br tracer test in a soil core from site P25. .................. 29 Figure 7. Frequency histograms of the loglo concentrations of total chromium and organic carbon in the soil. Total chromium concentrations were determined by summing the concentrations of the sequential extractions. .......................................... 31 Figure 8. Correlation of the Loglo concentrations of Cr vs organic carbon in the soil samples. ....................................................................................................................... 32 Figure 9. A summary of the sequential extraction data represented as average percent of Cr extracted in each extraction. The EX and OX2 extraction percentages are to small to appear on most of the pie diagrams ........................................ 34 Figure 10. Concentration of dissolved chromium versus pH in pore waters (blue) and surface waters (brown triangles) at this site. The curve is the theoretical concentration of dissolved chromium in equilibrium with Cr(OH)3 am. ._ ........................... 39 xi Figure 11. Graphical representation of the species computed by PHREEQC for selected water samples that represent the range of pH and chromium concentrations observed at the site. Each cluster represents the aqueous speciation for one sample ........................................................................................... Figure 12a and 12b. Correlation of chromium vs DOC in the surface and pore water at this site. Figure 12b is a subset of the entire data set shown in Figure 12a consisting of those samples with a chromium concentrations greater than 30 ug/L. Figure 13. Correlation of total dissolved chromium versus Crawlex (negatively charged or neutral chromium) in surface water and pore water at the study site. ..... Figure 14. Correlation of total dissolved chromium versus non-hydrophobic chromium in surface water and pore water at the study site. ..................................... Figure 15. Correlation of total dissolved chromium versus anionic chromium in surface water and pore water at the study site. .......................................................... Figure 16. Concentration of non-anionic chromium versus pH in pore waters and surface waters at the study site. The curve is the theoretical concentration of dissolved chromium in equilibrium with Cr(OH)3am. ................................................ Figures 17a and 17b. Correlation of chromium versus DOC in the acid-rain and control microcosm effluent (R2 values for the groups are; K22 = 0.68, N23 = 0.71, P23 = 0.71, J23 = 0.19, 022 = 0.26, J19 = 0.78). The samples are grouped by site and include both the acid rain treated and the control samples from each site. ......... Figure 18. Correlation of total dissolved chromium versus Crawl” (negatively charged or neutral chromium) in the acid rain microcosm effluent water.. ............... Figure 19. Changes in the pH of fluids in the microcosms as function of time. The range of pH values observed in the pore-waters at these sites are represented by the vertical lines to the right of the concentration profiles. .................................. Figure 20. Chromium concentrations in the exchange soutions. ............................. xii ........ 40 ........ 41 ........ 42 ........ 42 ........ 43 ........ 44 ........ 56 ........ 57 ........ 58 ........ 60 Figure 21. This figure is similar to Figure 20, although sample J 19 was not included. Also, the range of chromium concentrations observed in the pore- waters at these sites are represented by the vertical lines to the right of the concentration profiles ......................................................................................................... 61 Figure 22. Correlation of chromium versus DOC in the nutrient microcosm effluents. Figure 223 includes the samples from all three treatrnents (N, N&P, and control) from each site. Figure 22b shows data from the microcosms treated with 90 mg/L nitrate. Figure 22c shows data from the microcosms treated with 25 mg/L nitrate and 2 mg/L phosphate. Figure 22d shows data from the control microcosms treated with the simulated rain solution ......................................................... 68 Figure 23. Correlation of total dissolved chromium versus Crane]ex (negatively charged or neutral chromium) in the effluent water from the nutrient microcosms. ......... 70 Figure 24. Nitrate concentrations in the effluent of the nutrient microcosms over time for the six microcosm sites. The concentration range is not the same for each graph. N represents the microcosms treated with 90 mg/L nitrate. N&P represents the microcosms treated with 25 mg/L nitrate and 2 mg/L phosphate. Control represents the microcosms treated with the simulated rain solution. ................... 72 Figure 25. Sulfate concentrations in the effluent of the nutrient microcosms over time for the six microcosm sites. The concentration range is not the same for each graph. N represents the microcosms treated with 90 mg/L nitrate. N&P represents the microcosms treated with 25 mg/L nitrate and 2 mg/L phosphate. Control represents the microcosms treated with the simulated rain solution. ................... 74 Figure 26. Chromium concentrations in the effluent of the nutrient microcosms over time for the six microcosm sites. The concentration range is not the same for each graph. N represents the microcosms treated with 90 mg/L nitrate. N&P represents the microcosms treated with 25 mg/L nitrate and 2 mg/L phosphate. Control represents the microcosms treated with the simulated rain solution. ................... 77 Figure C l. A schematic diagram showing the ports from which fluid was taken for the various parameters ................................................................................................ 116 Figure C 2. A schematic diagram showing the barrels from which fluid was taken for the various parameters. ..................................................................................... 118 xiii I. INTRODUCTION 1.1 The Problem The purpose of this study was to investigate the fate and mobility of chromium in a wetland area contaminated with tannery waste. This study was part of a larger project that was designed to address two primary goals. The first goal was to define the current state of chromium in the soil and aqueous phases of the site. The second goal was to evaluate the stability of the chromium in the soil and assess the potential for mobilization of chromium from these soils. This project was the result of a collaboration between personnel with the Center for Microbial Ecology and the Geological Sciences Department at Michigan State University. The focus of the study presented here is the geochemical aspects of the project. The biogeochemistry of chromium is complicated by its redox chemistry; in the environment chromium can exist as Cr(III) or Cr(VI) (Rai et al., 1989). Chromium (V1) is known to be toxic, mutagenic, and carcinogenic (Palmer and Puls, 1994) and Cr(V I) is also highly mobile in many soil environments (Rai et al., 1989). However, almost any naturally occurring reductant can reduce Cr(VI) to Cr(III) (Rai et al., 1989; Palmer and Puls, 1994) and chromium in tannery effluent is likely to be in the Cr(IH) form (Walsh and O’Halloran, 1996a; Kotas and Stasicka, 2000). Chromium (III), in comparison to Cr(VI), is relatively immobile within a pH range of 5 to 12 (Sass and Rai 1987) and has a relatively low toxicity (Palmer and Puls, 1994). Chromium (IH) also bonds with organic compounds (James and Barlett, 1983a and b; Walsh and O’Halloran, 1996a and b; Kotas and Stasicka, 2000). The nature of chromium speciation in soil and groundwater environments is complex. Processes that control chromium speciation include redox transformations, precipitation/dissolution reactions, and adsorption/desorption reactions. The environmental chemistry of chromium has received much attention, especially in the last twenty years (Rai et al., 1989; Richard and Bourg 1994; Losi et al., 1994a; Fendorf, 1995; Kotas and Stasicka 2000). This research includes laboratory investigations of the reactivity and mobility of chromium in simple systems with limited components (Rai et al., 1987; Eary and Rai, 1987; Fendorf et al., 1993; Wittebrodt and Palmer, 1996a and b; Buerge and Hug, 1998; Zhang and Bartlett, 1999) and complex systems involving natural materials, such as soils and aquifer material (Bartlett and Kimble, 1976a and b; Bartlett and James, 1979; Bartlett and James, 1983a, b, and c; Zachara et al., 1989; Saleh et al., 1989; Milacic and Stupar, 1995; and Cifuentes et al., 1996). There have also been a number of field-based studies dealing with chromium mobility and reactivity (Davis et al., 1994; Kent et al., 1994; Arrnienta and Quere, 1995; Walsh and O’Halloran, 1996). The majority of the field studies deal with the development of remedial options for Cr(VI) in ground-water environments (Davis and Olsen, 1995; Palmer and Puls, 1994). Common remedial approaches to Cr(VI) contamination involve reducing the chromium to Cr(III) in situ (Hanson et al., 1993; Powell et al., 1995; and Blowes et al., 1997). The rational for this approach is based on the assumption that inorganic Cr(III) solids are very insoluble and Cr(III) is not considered to be toxic (Palmer and Puls, 1994). However, there is very little information concerning the speciation or mobility of chromium in organic rich environments like wetlands. Natural and constructed wetlands have been proposed as treatment options for heavy-metal (including chromium) contaminated water because wetlands have been demonstrated to act as sinks for metals (Makos and I-Irncir, 1995; Polprasert et al., 1996; Scholes et al., 1998; Barbosa and Hvitved-Jacobsen, 1999). However, natural wetlands are often host to complex webs of physical and biogeochemical cycles that may influence metal mobility. An example of one such cycle is the oxidation of Cr(III) to Cr(VI) by manganese oxides in water-surface films as described by Masscheleyn et a1. (1992). In laboratory experiments, they observed the formation of Cr(VI) in stagnant water above wetland sediment. It was suggested that dissolved Cr(III) interacts with manganese in iron and manganese oxide films at the water surface and is oxidized to Cr(VI). The films were assumed to be primarily organic material upon which iron and manganese oxides precipitate as reduced dissolved iron and manganese interacts with oxygen from the atmosphere. The reduced iron and manganese came from the reduction of iron and manganese oxides in the sediment, which subsequently diffuses into the water column. This study demonstrates the need to examine the biogeochemistry of chromium in wetland environments. Mattuck and Nikolaidis (1996) studied the mobility of chromium in a wetland using both field and laboratory methods. This study was similar to the work presented here. Dialysis membrane samplers were used to sample pore water. They reported aqueous chromium concentrations of 0 to 406 ug/L in the pore waters but no Cr(VI). Although they reported relatively high aqueous chromium concentrations, they gave no explanation for these elevated chromium concentrations. Sequential chemical extractions performed on the sediments indicated that 60 to 90% of the chromium was bound in the Fe/Mn-oxide and residual fractions, which was interpreted as sediment bound chromium. However, sodium pyrophosphate, which is not very aggressive (Chao, 1984), was used as the organic matter extractant. According to Chao (1984) sodium pyrophosphate extracts the organic matter by chelating and stripping the metals that bind the organic matter together. A combination of nitric acid and hydrogen peroxide, which oxidizes organic carbon and are often used as organic matter extractants (Chao, 1984; Tessier et al., 1979; Belzile et al., 1989; Schulmeister 1993; and Fielder et al., 1994), was used as the residual extraction. It is possible that much of the chromium that Mattuck and Nikolaidis (1996) have assigned as sediment bound may actually be organically bound chromium released by the residual extraction. Mattuck and Nikolaidis (1996) also performed stirred, batch, leaching experiments to simulate acid rain deposition or acidic groundwater influx. The leaching experiments were conducted at pH 3, 4, and 5. The most chromium was released increased as the pH of the slurry decreased, with the highest chromium concentrations of approximately 20 ug/g at pH 3. They suggest that the mobility of chromium in wetlands is controlled by the formation of relatively insoluble chromium hydroxide solids. This study will add to the understanding of the fate and mobility of chromium in wetland environments. 1.2 Approach The first goal was to define the current state of chromium in the soil and aqueous phases. In order to understand how chromium may become mobile at this site, it was necessary to determine the state of chromium in the soil and aqueous phases that developed over the past fifty years. The primary hypothesis was that chromium is associated with soil organic matter as Cr(III) and that dissolved chromium will be associated with dissolved organic mater. The most likely alternative to this hypothesis is that the chromium sequestered by these soils is in the form of a (Crx,Fel-x)(OH)3 solid, which has a very low solubility (Rai et al., 1989). To test this hypothesis, soil samples were collected from three depths at 80 locations, which spanned the range of chromium concentrations and vegetative types. Selective chemical extractions were used to determine the partitioning of chromium in different environmentally reactive phases of the soil or sediment sample. Selective chemical extractions are designed to target specific solid phases within the sediment (Tessier et al., 1979; Belzile et al., 1989; Yong et al., 1993). Organic carbon, iron and manganese-oxides appear to be the major controls on chromium redox chemistry and mobility, therefore the selective extractions targeted these phases. Along with the selective chemical extractions, pore water samples were collected and a new field sampling procedure was established to further investigate the biogeochemistry of chromium. Solid phase extraction media were used in the field in order to remove anion, cations, and hydrophobic organic compounds from aqueous samples in separate reactions. Solid-phase extractions (SPEs) were developed as separation media for liquid chromatography. Solid-phase extractions have also been used to investigate various aspects of aqueous geochemistry. SPEs have also been used for isolating dissolved organic matter (DOM) (Leenheer, 1981; Mills and Quinn, 1981; Mills et al., 1987) and metal-organic complexes from nattual waters (Mills et al., 1982; Mills and Quinn, 1984; Mills et al., 1987; Mills et al., 1989; Paulson et al., 1994; Elbaz- Poulichet et al., 1994; Martin et al., 1994; Donat et al., 1997). The majority of these workers used Sep-Pak columns (Waters Associates) which are selective for the hydrophobic fraction of DOM. This study also used Sep—Pak columns to perform this separation. SPEs have also been used to remove cations from aqueous environmental samples (Pai and Fang, 1990; Davis et al., 1994; Kaplan et al., 1994). Chelex-100 resin in the sodium form (BIORAD Inc.) was used in this study to remove cations from solution and replace them with sodium. Relatively fewer investigators report the use of anion exchange resins to investigate speciation in environmental samples (Leenheer, 1981; Kaplan et al., 1994). AG anion exchange resins in the fluoride form (BIORAD Inc.) were used in this study to separate anions, in particular organic anions, from the bulk sample. The second goal of the project was to evaluate the stability of the chromium in the soil and assess to the potential for mobilization of chromium from these soils. A secondary hypothesis is that the mobility of chromium in these soils is controlled by the stability of the organic matter to which it is bound. Experiments were conducted in the laboratory using intact soil microcosms to assess mobility. The design and data collection involved in the microcosm experiments were the result of collaboration with the microbiologists working on the project. During these experiments treatment fluids were pumped through a soil core and allowed to react for a period of at least one week. The objective of these experiments was to determine the biogeochemical conditions in which chromium may become mobile. Conditions that were tested included: addition of nutrients (nitrate, phosphate, and potassium), the addition of an alternate terminal electron acceptor (nitrate), and changes in pH. The biogeochemical conditions were monitored during the experiments and total extractions were performed on the soils before the experimentation. The criteria for the selection of treatments was limited to simulating possible events that could occur at this site that may change the mobility of chromium. If the chromium is predominantly present as a (Crx,Fe1-x)(OH)3 species the concentration of chromium in solution will be controlled by the solubility of this solid. The first treatment chosen for the microcosm experiments was the simulation of the acidification of the pore water at the site due to acid rain. An acid rain treatment was chosen because it was thought to be the most likely acidification event at this site. An amount of fluid equivalent to approximately five years of acidic precipitation was pumped through the microcosms during the experiment. Other treatments were developed to further test the hypothesis that the mobility of chromium in these soils is controlled by the stability of the organic matter to which it is bound. If chromium is associated with soil organic matter, the degradation of the organic matter may release chromium to solution as an organically complexed species. Therefore, the amount of chromium in solution would be proportional to the amount of organic matter degraded. The treatments for the second round of microcosm experiments were designed to determine if chromium could be mobilized from the soils by changes in microbial processes. The treatments for the second set of microcosm experiments were designed to simulate the possible addition of nutrients. One of these treatments attempted to maximize the efficiency of the microbial community by altering the redox state to a higher level. In this treatment 90 mg/L nitrate was added to a simulated rain solution. Another treatment attempted to simulate an overall increase in the nutrient level of the pore water. The objective of this treatment was to add nutrients to the system that were lacking and thereby potentially increasing the microbial degradation of organic matter. In this treatment nitrate and phosphate were both added in concentrations of 25 mg/L and 2 mg/L respectively to a simulated rain solution. II. BACKGROUND 2.1 Study Site The study site was in Sault Ste. Marie, MI and borders the St. Mary’s River (Figure l—site map). The site supports abundant plant life and much of the site is considered to be a wetland. The soils and subsurface geology are complex and heterogeneous across the site. The dark, near-surface soils contain abundant organic matter and in some areas the soils have been characterized as peat (Cannelton, 1992). Almost all parts of the site are covered by fill. The fill consists of materials such as scrap leather, hair, bricks, concrete, scrap wood, scrap metal, glass, and cans. The fill was Wooded Wetland Grassy Wetland an Swampy/Cattails f _ Woodland ’f ‘ Grass E Beach 40011 Figure l. A map of the study site, showing type of vegetative surface coverings. 9 deposited on discontinuous layers of sands and gravels, with the predominant texture of a silty sand (Cannelton, 1992). Depth to bedrock, which is reported to be Jacobsville Sandstone, ranges from 30 to 60 feet (Cannelton, 1992). This research was initiated as the result a practical need for scientific information concerning the mobility of chromium at the site. The study site is a wetland that received tannery waste discharge from the late 1890’s until approximately 1958. During the tanning process an acidic Cr(III) solution is used to bind collagen fibers of the skin and make the leather resistant to degradation (O’Flaherty et al., 1958; Walsh and O’Halloran, 1996b). This solution is provided in excess and there is a large amount of waste fluid produced. Today tannery waste is regulated but during the time when the tannery at the site operated there were few regulations and liquid waste was disposed of through pipes and ditches that drained toward the river. As a result of this activity, there are areas at this site which have concentrations of chromium in the soil which exceed 200,000 mg/kg. The primary discharge areas that have the highest concentrations of chromium will be removed. 2.2 Geochemist_ry of Chromium In aqueous environments Cr(III) forms strong complexes with CH and exhibits amphoteric behavior (Baes and Mesmer, 1976). In the pH range of most natural waters (pH 6-8) it exists primarily as a Cr(OH)3 solid (Rai et al., 1989). The solubility of the Cr(OH)3 solid is very low (Baes and Mesmer, 1976) and if Fe3+ is present Cr(III) preferentially forms (Crx,Fe1-x)(OH)3 (Sass and Rai, 1987). The (Crx,Fe1-x)(OH)3 solid is highly insoluble and since iron is present in geologic environments the solubility of Cr(III) in most natural systems is very low (Rai et al., 1989). Chromium (H1) is also 10 known to bind to soil organic matter (Bartlett and Kimble, 1976b; Palmer and Puls, 1994). Likewise, Cr(III) can be complexed by dissolved organic matter, thereby increasing the solubility of Cr(III) in soil environments (James and Bartlett, 1983a,b; Davis et al., 1994; Walsh and O’Halloran, 1994 a and b). Davis et a1. (1994) studied the mobility of chromium and arsenic in an aquifer at a site contaminated by tannery operations similar to the study site. They found aqueous Cr(III) concentrations much higher than expected from equilibrium with solid phases. The increase in solubility was attributed to complexation with dissolved organic matter. Walsh and O’Halloran (1994b) in studying chromium speciation in an estuary receiving tannery effluent also found high Cr(III) concentrations and attributed these concentrations to complexation with dissolved organic matter. Overall however, the solubility of Cr(III) in most natural systems is very low. The redox potential of the Cr(VI)/Cr(III) couple is very high and because of this there are few oxidants present in natural systems that are capable of oxidizing Cr(III) to Cr(VI) (Rai etal., 1989). Dissolved oxygen and manganese oxides (MnOz) are the only two oxidants in the environment that are known to oxidize Cr(III) to Cr(VI) in the pH range of most natural waters (Palmer and Puls, 1994). The oxidation of Cr(III) by dissolved oxygen has been shown to be a very slow reaction (Schroeder and Lee, 1975) and in some studies no oxidation was observed (Eary and Rai, 1987; Bartlett and Kimble, 1976a). Oxidation of Cr(III) to Cr(VI) by Mn-oxides has been demonstrated in a number of studies (Schroeder and Lee, 1975; Bartlett and James, 1979; Takacs, 1988; Eary and Rai, 1987). This reaction is much more rapid than the oxidation Cr(III) by dissolved oxygen and is likely to be more important in groundwater and soil systems. 11 Chromium (VI) exists in aqueous solutions as monomeric ions HzCrO4°, HCrO4', and Cr042', or as the dimeric ion Cr2072' (Palmer and Puls, 1994). Chromium (V1) is relatively more mobile than Cr(III) in subsurface environments. The solubility of Cr(VI) is controlled by the formation of the Ba(Cr,S)O4 solid solution in environments that contain BaSO4 (Rai eta]., 1989). When BaSO4 solids are not present in the system, Cr(VI) solubility will be controlled by adsorption/desorption reactions under acidic to slightly basic conditions (Rai et al., 1989). It has been shown that Cr(VI) is adsorbed by iron oxides, aluminum oxides, and kaolinite (Davis and Leckie, 1980; Zachara et al., 1989; Rai et al., 1989). Adsorption to these solid phases is inversely proportional to pH, adsorption decreases with increasing pH. Under acidic to slightly basic conditions iron oxides are the dominant adsorbents in the environment (Zachara et al., 1989; Rai et al., 1989). Since Cr(VI) is a strong oxidant it can be reduced by many reducing agents found in natural systems. Ferrous iron as aqueous Fe2+ (Eary and Rai, 1988) or derived from oxide or silicate minerals (Eary and Rai, 1989; White and Hochella, 1989) has been shown to rapidly reduce Cr(VI) to Cr(III), which can lead to the formation of a (Crx,Fe1- x)(OH)3 precipitate. Microbial reduction of Cr(VI) to Cr(III) has also been documented (Llovera et al., 1993; Shen and Wang, 1994). Reduction of Cr(VI) by soil organic matter has also been documented (Schroeder and Lee, 1975; Bartlett and Kimble, 1976b). The Cr(III) may hydrolyze and precipitate as a chromium -hydroxide or it may bind to the remaining soil organic matter (Palmer and Puls, 1994). Reduced sulfur is another naturally occurring reducing agent that has been found to reduce Cr(VI) (Smilie et al., 1981; Palmer and Puls, 1994). Rai et a1. (1989) conclude that since ferrous iron and 12 organic matter are ubiquitous in soil and groundwater, Cr(VI) will be reduced to Cr(III) in many natural systems. 13 III. METHODS This chapter is divided into three sections. The first section describes the methods used for collection and analysis of solid samples, which includes soils and sediments. The second section describes the methods used for collection and analysis of liquid samples. The third section describes the experimental design and sampling for the microcosm experiments. Images presented in this dissertation are presented in color. 3.1 Solid samples 3.1.1 - Sample Grid Development, Surveying, and Site Locations The first step in the sampling program was to develop an unbiased sampling grid that covered the entire site. A basic GIS analysis was performed on a preexisting data set (Cannelton, 1992; Cannelton, 1995) to identify possible trends in chromium concentrations across the site, identify areas of data need, and determine the spacing between sampling locations. This analysis led to the development of the sampling grid used in this study. There were several factors considered in the grid development including, sampling from areas that represented the full range of concentrations, and equally spaced sampling locations to reduce sampling bias. An existing local datum was used as the starting point for the grid. The sampling locations were then established by measuring distances with surveying equipment and a 200-ft. steel tape from known positions. Each sampling location was marked with a wooden stake, which could then be used to site other locations. The grid showing labeled sampling locations is illustrated in Figure 2. l4 O U26 Legend $31637 --- igiicde >535 . “3’ ° Soil 3 1 Locat' ' °24 1°” H15 ampe ron IP33 92%. . 0 I Samplrng Intervals 2’} I .622 . 024 ..‘ Below Land Surface «A . . 2‘ , N23 N25,, , 0-05fi 9H, , M20.M22. M24.!fi28.M28 L21 L23 L25' 1.27 1-15 a I’ ‘ K20 K22 K34 ‘(326 K28 ’ \e o o o \ o 3-3.5 a ’ f1: “'2‘ m . ”3 .120 '22 0’ L N M15 ’L‘)‘. .o/ 1 ,.___ ,- 3 &;,a_1.19--nr"l i a", _ ‘ 616 E18 530 i I l l r 0.5 0.7 . 0.9 011 . oi 'ois 017 Die : POOR w 04 ca C8 C10 C12 1 - CIB, ‘ J O O O I 0 :2- ’ '- -~ -- -., - -- -- -- -- 18W twc’ i I , ’ Former Tannery : ’z’ Location I I I I I ,’ I, Figure 2. A map of the study site, showing the locations of the sampling sites. 3.1.2 - Sample Collection Soil cores were collected with an AMSTM stainless steel, split spoon, coring device, with two-inch diameter, plastic core liners to contain the sample. Initially, samples were collected from three depths at each site. Sampling intervals below land surface were 0 to 0.5 feet, 1.0 to 1.5 feet, and 3.0 to 3.5 feet. An AMSTM hand auger was used to remove intervening material between the sampling depths. Some sampling difficulties arose when rocks, wood, or other impenetrable objects were encountered at depth. Thus it was not always possible to obtain three samples at every location. Samples were collected in acid-washed plastic core liners, the ends were capped and taped to eliminate further exposure to the atmosphere, and stored on ice in the field. The 15 sample location and core descriptions are presented in Appendix A. Samples were frozen within 8 hours after collection and stored at approximately —20°C. 3.1.3 - Sequential Chemical Extractions Selective chemical extractions were used to determine the partitioning of chromium in different environmentally reactive phases or hydromorphic phases of the soil or sediment sample. Selective chemical extractions are designed to target specific solid phases within the sediment. Organic carbon, iron and manganese-oxides appear to be the major controls on chromium redox chemistry and mobility, therefore the selective extractions targeted these phases. The use of these methods has been questioned because of the non-specific nature of the extractions and possible post-extraction readsorption occurring between extractions (Gruebel et al., 1988; Rapin et al., 1986; Rauret et al., 1989; and Tipping et al., 1985). However, there appears to be a consensus that these methods can be used to gain useful information concerning metal partitioning within sediments as long as the limitations are recognized (Gephart, 1982, Chao, 1984, Martin et al., 1987, Belzile et al., 1989, Schulmeister, 1993, and Fielder et al., 1994). One approach to the use of selective chemical extractions is to use them in sequence. The chemical extractants are applied to a soil sample in sequence starting with the least aggressive extractant. Upon completion of each reaction, solutions are centrifuged and the supematants extracted for analysis. A summary of selected sequential extraction procedures is presented in Table 1. The hydromorphic fractions generally targeted include exchangeable (metals bound to exchange sites on clays), easily acid soluble (metals associated with carbonates), easily reducible (metals associated with Mn-oxides), moderately reducible (metals associated with Fe-oxides), oxidizable (metals 16 .883 025 “438.55 .833 owaenoxo :3 I Oflmén: .ouaaefieofiégmmoxcomfimc «Z I monaz .. N N :a .02: .23 95:2 :a 52: as, 2 _ 48 a :a 4. .o:.:o~:z 3.5: 83 .oz: 48 5.: :8 .m 2 3 .N 2 :.o .: .a a a: .52: .52: $8 a 95:2 9.5: :2 z 3 e n :a .95: 2 Na 45. a :a a a _o:.:o.:z 5:.:oa:z a 9.542 ”Um: $2 a .52: 45 5.: son .m 2 43 .4 z 3 .m 2 _ .N 2 _ .: .4 23“.: Bow atom 33568 n 4 . 933888 49. m: oz: $8 a 9.5 :z 9.5: :2 n :q 9.5: . 9.4 4.42. 2 Na 45. a :a a a 5:.:o.:z a 9.542 .542 $2 .4 89.. .4 .oz: 49. 5.: :3 .4 2 4.3 .m 2 _ .N 2 _ ._ a 5:42 ....o.:-x 5.59.42 .02: SE .24 a - 42.3%... .N 52: .m :52 2 3 .m 2 8.0 .4 2 no ._ nausea: s :a on :a a8: .3092 .55.: 2 3 3 :a 3:92.: - 82.8-: .oz: 45 - 555:7: ._o:.:o.:z 45. 05.3.5 .4 55: .m 2 :a . 5542 ._ 2 Ed .m 2 3 .~ 88%: .oz: :8 a 05:2 9.5: $3 m :a .95: 55: 2 S 4:4 a :a a e 5:.:o.:z a 3.542 .6»: $2 ._4 E: .n 52: 48 5.: son .4 2 4o.o .m 2 : .N 2 _ ._ a sack. 3262 3262 0338 03¢ women: 550 32463: 0336me b28082 Emmem Eon >233 emanaoxm £553... don—6385 grunge 39:33.4. 3828 no bag... .44 A «Bah. l7 associated with organic matter and sulfides), and residual (metals associated with chemically resistant mineral phases). The procedure used in this study is a modification of the procedure used by Belzile et a1. (1989) with additions to better characterize the organic and possible sulfide mineral phases. The modification consisted of inserting a 5% NaOCl (pH 9.5) extraction between the 0.04M hydroxyamine HCl extraction and the 30% H202 (pH 2) extraction. The NaOCl should dissolve organic carbon and liberate metals associated with it, while having little impact on the sulfide phases present (Papp et al., 1991). The procedure used is listed in Table 2 and a detailed description of the procedure is outlined in Appendix B. Table 2. Summary of the sequential extraction procedure used in this study (modified after Bezile et al., 1989). then add DDW to 25mL Target Extraction Phase Extraction Extraction Substrate Solution* Conditions Exchange Sites Exchangeable 1.0M MgCl2, pH 7 20°C, 1 hour (EX) 10 mL Carbonates Weakly Acid 1.0M NaOAc, pH 5 20° C, 5 hours Soluble (WAS) 10 mL Reactive Fe-Oxides Easily Reducible 0.1M N H2OHHC1 25° C, 5 hours and Mn- Oxides (ER) in 0.1M HNO3 25 mL Crystalline Fe- Moderately 0.04M N H2OHHCL 96° C, 6 hours Oxides Reducible (MR) v/v 25%HOAc20 mL Organic Matter Basic Oxidizable NaOCl, pH 9.5 96° C, 15 min. (OX1) 3 times, 6 mL each then 3.2M NH40AC5 mL 25° C, 1 hour Sulfides Acid Oxidizable 0.02M HNO3, 3 mL 85° C, 5 hours (OX2) 30% H202, pH 2, 8mL then 3.2M NH40Ac, SmL 25° C, 1 hour 3.1.4 - Total Extractions Total extractions were performed on samples taken from the top and bottom of cores used in the microcosm experiments. The total extraction method used in this study 18 was based on that of Hewitt and Reynolds (1990). The extraction was conducted in CEMTM PI‘FE, microwave digestion vessels. The extraction consisted of placing approximately 0.5 g of dry soil in a digestion vessel, adding 10 mL of trace-metal grade nitric acid, and then sealing the vessel before heating in a microwave. The digestion vessels were then allowed to depressurize and then the sample was diluted to 100 mL with distilled-deionized water. 3.1.5 - Solid Phase Organic Carbon Content Organic carbon content of soils was determined by a loss on ignition method. Organic matter content was determined using sub-splits of homogenized soil taken prior to the sequential chemical extractions. The method was modified after a procedure developed by researchers from the Department of Soil Science at the University of Wisconsin, Madison, WI (Shulte et al., 1991). Analyses were done in the Plant and Soil Testing Lab at Michigan State University. 19 3.2 Agueous Samples 3.2.1 - Sample Collection This section provides a brief description of the sample collection approach. A more detailed description of the sampling collection procedures can be found in Appendix C. Sampling of the pore waters was accomplished with two types of dialysis membrane samplers. The first type (Figure 3) is a solid block of acrylic (3’ x 24” x 4 or 6”), called a peeper, in which hollow ports have been drilled. Peepers with two different sizes of ports were used during the sampling. Each port contained approximately 15 or 40 mL of water. The ports on the peeper were filled with de-aerated distilled, deionized water (DDDW). A semi-permeable membrane (0.2 pm pore diameter Biodyne BTM Front View 3-D View Acrylic Sampler Dialysis Membrane :0.0: ‘ , Face Plate 8-8 8 8'- .0.0.‘ ‘0‘0‘ Nylon Screws .gg.\s.mp1./ 3.3 ~ . O. O. Compartments “0‘0“ 0.0 ~o o, .o 0. 0‘0“ 50 ~o om .0 0. 0‘0 50 _o om ,o 0, 0‘0 9090 ‘ ‘3 8‘- 4:51 Figure 3. Schematic diagram of a “peeper” sampler used to collect pore—water samples. 20 nylon membrane, Pall Corp.) was placed across the filled peeper ports (while expelling all gas bubbles) and held in place by an acrylic face plate which was secured with nylon screws. The second type of dialysis membrane sampler (‘barrel’ sampler; Figure 4) was originally designed as a component of a multi-level sampling apparatus for water wells (U .S. Filter/Johnson Screens Corp). A barrel consists of a polyethylene tube (1” diameter x 3” long) with caps that screw onto each end of the tube. Each barrel contained approximately 45 mL of water. The barrel samplers are designed with disposable, nylon, dialysis membranes (0.2 pm), which were fitted in to screw cap ends of the barrel. The barrels were filled with de-aerated distilled, deionized water and capped with the membrane screw caps such that no gas bubbles were present inside the barrel. 3D View End cap Membrane screw cover 0.2 pm nylon filter membrane Side View [flflllflil [Mill Figure 4. Schematic diagram of a “barrel” sampler used to collect pore-water samples. 21 The membrane allows exchange of solutes between the distilled water and the surrounding pore waters of a saturated porous medium (Hesslein, 1976; Carignan et al., 1985; and Tessier et al., 1996). The peepers and barrels were installed below the land surface in saturated areas. The samplers were left in place for at least two weeks to allow biogeochemical equilibration to occur between the sampler and the pore water (Hesslein, 1976; Carignan et al., 1985: Tessier et al., 1996). In order to obtain sufficient fluid for analysis, four to six adjacent peeper ports were sampled to make up one sample. Three barrels bound together constituted one sample when using barrel samplers. Aqueous field sampling was conducted during the summer and fall of 1997 and 1998. During the latest field-sampling season, samples were also taken from the surface waters at the site. The surface water sampled was primarily shallow, standing water less than six inches deep but samples of springs and deeper water were also obtained. The sampling of surface waters was accomplished with a battery operated peristaltic pump, which was used to pump water through a 0.45 pm filter. The filtered water was collected in a l L, acid-washed, polypropylene bottle and filled to allow minimal or no headspace. Splits were then taken from the 1 L bottle for the various analyses that were performed, as described in the following section. 3.2.2 - Analytical Measurements Field measurements that were made included temperature, pH, Eh, 82', Cr(V I), Fe”, and alkalinity. Laboratory measurements included dissolved organic carbon (DOC), NHR, CH4, anions (Cl', Br', N03; N02, 3042'), and metals (Cr, Fe, Ca“, Mg“, Na‘, K", Mn). Eh and pH were determined with electrodes. Sulfide was determined using sulfide vacu-vials (Chemetrics Inc.). Cr(VI) was determined using a 22 diphenylcarbazide colorimetric method (Fishman and Friedman, 1989). Fe(II) was determined using a phenantholine colorimetric method (APHA, 1992). Alkalinity was determined by titration with sulfuric acid (APHA, 1992). Anions were analyzed by capillary electrophoresis (APHA, 1998) using an Applied Biosystems model 270HT capillary electrophoresis instrument. Cations were acidified to below pH 2 with OptimaTM nitric acid and refrigerated until analysis. Cation concentrations in the field samples and the fluids from the total extractions were quantified using inductively coupled plasma mass spectroscopy (lCP-MS; VG-Elemental Plasma Quadl or Micromass Platform). Cation concentrations that were in the high mg/L range and the fluids from the sequential extractions were quantified using atomic absorption spectroscopy (AAS; Perkin—Elmer model 5100PC), depending on concentration and the matrix of the samples. Multiple measurements were taken for each cation analysis (for both AAS and ICP-MS) and all the data satisfied the precision requirement of being within 10% RSD. Methane samples were analyzed by headspace extraction and quantified on a gas chromatograph. DOC samples were frozen immediately on dry ice and analyzed with a TOC 5000 Shimadzu carbon analyzer. 3.2.3 - Solid Phase Extraction Media Chromium speciation was estimated by utilizing three different solid phase extraction resins in the field. Aqueous samples were brought into contact with these resins which removed different dissolved species in the sample. Chelex-lOO resin in the sodium form (BIORAD Inc.) was used to remove cations from solution and replace them with sodium. The reaction was conducted as a batch reaction. Approximately one gram of resin was allowed to react with 8 to 10 mL of sample for at least one hour, as described 23 in the product literature (BIORAD Inc.). The sample was then filtered through an acid- washed, poly-carbonate, 0.4 um nucleopore filter and acidified to a pH less than 2 with OptimaTM nitric acid. The chromium remaining in solution after the reaction should have a negative or neutral charge. One of the main goals for this research was to explore the role organic complexes has on chromium mobility. The anionic exchange resins were selected with the separation of organic molecules in mind, as they are among the suspected complexing agents of chromium. In the pH range of these waters, most of the functional groups on dissolved organic matter will be negatively charged (McBride, 1994). The AG 1 and AG MP resins (BIORAD Inc.) are strong anion exchange resins. AG] and AG MP are essentially the same resin except that AG] is for small molecules (molecular weights less than 2700) and AG MP is for large molecules (molecular weights up to 100,000 and higher). The AG MP resin was deemed necessary because the size of organic molecules could not be determined but was assumed to vary greatly with some being quite large. The resins were loaded into 10 cm glass columns with a 1 cm inner diameter. The lower half (outlet) of the column was filled with the AG] resin and the upper half (inlet) was filled with the AG MP resin. This insured that all sizes of anions could be removed. The AG resins were purchased in the chloride form. The form (indicating the exchange ion that is liberated from a resin upon reaction with sample fluids) can be changed depending on the needs of the application (BIORAD Inc.). Different ions have different affinities for a particular resin. A resin with the most easily replaced ion attached is said to be in the most reactive form. The most reactive form for these resins is the hydroxide form and the most reactive form of the resin was desirable for this study. 24 However, the hydroxide form was undesirable because chromium is a pH sensitive element. The fluoride form is the next most reactive form of the resin. Since fluoride should not influence the pH of the water or the chemistry of chromium, these resins were used in the fluoride form. The form of the resin was changed in two steps (as described in the product literature, BIORAD Inc.). First, the resins were converted from the Cl form to the hydroxide form by slowly (approximately 3 mL/min.) pumping 200 mL of 1.0 M NaOH through the column. Second, the resins were converted to the fluoride form by slowly (approximately 3 mL/min.) pumping 200 mL of 0.85 M NaF through the column. The conversion to the fluoride form was monitored by measuring the pH of the effluent during the process to insure that the pH returned to a neutral value. The volumes of NaOH and N aF solutions used to perform the conversions exceeded the recommended maximum volumes suggested for the conversion of these resins (BIORAD Inc.). Finally, 150 mL of deionized, distilled water (DDW) was passed through the column as rinse and to replace the pore water in the column with DDW. The columns were sealed with parafilmTM and stored upright until their use. The conversion was performed 2-5 days prior to use. Along with being negatively charged, natural DOC may also exist as an uncharged hydrophobic species, which may also be complexed with metals such as chromium (McBride, 1994; Mills et al., 1987; Paulson et al., 1994; Elbaz-Poulichet et al., 1994; Martin et al., 1994; Donat et al., 1997). Sep—PakTM (Waters Associates) columns were used to remove the organic-hydrophobic species from solution, along with the metals bound to them, from the samples. The Sep-Pak columns were conditioned prior to 25 sample processing using the method of Mills et al. (1987). Conditioning consisted of successively rinsing with 10 mL methanol, 10 mL 0.3 mM HCl, 10 mL methanol and then 20 mL of DDW. The columns were then stored in plastic bags until use. The conditioning was performed 2-5 days prior to use. Field sampling using these columns consisted of filling a 60 mL syringe with approximately 70 mL of filtered sample from which split samples were taken for the various treatments. One split was taken as the control (approximately 10 mL), which was bottled and acidified with OptimaTM nitric acid immediately. One split was taken for DOC analysis (approximately 10 mL) and was frozen immediately. One split was added to the Chelex-100 resin (approximately 10 mL) in a batch reaction and allowed to react for at least one hour prior to being refiltered and acidified. The graduated syringe was then used to inject 20 mL of sample into the column containing the AG resin. After the sample was injected into the AG column another 50 mL of DDW was passed through the column as a rinse. Fluid conring from the column was contained in a 100 mL volumetric flask, which was diluted to 100 mL with DDW when the rinse was completed (total dilution of 1:5). The sample was then transferred to a bottle and acidified. The syringe was then used to inject 20 mL of sample into the Sep-Pak column. The sample was then passed through the Sep-Pak resin and diluted by the same procedure as that described above for the AG resin split. 26 3.3 Microcosm Design and Sampling Intact soil-core microcosms have been effectively used in the laboratory to assess the potential for in situ bioremediation (Dolan and McCarty, 1995; EPA, 1989) and are the approved testing procedure of the EPA for the determination of the potential fate and ecological effects of contaminants in terrestrial ecosystems (EPA, 1996). Intact-core microcosms have an advantage over other designs as the sediment core undergoes minimal disruption and does not require the sample to be sieved, repacked or rewetted (EPA, 1996). The complex physical, geochemical, and ecological structure of the soil matrix and associated microbial communities are therefore better preserved for laboratory study. Although the results of microcosm studies are influenced by the nature of the geological material studied and microcosm design, the ability to replicate in the laboratory the geochemical and physical properties of the site coupled with a defined sampling strategy afford many advantages over other methods (Wiedemeier et al., 1995). The design of and data collection involved with the microcosm experiments was the result of a collaborative effort with personnel in the Center for Microbial Ecology at Michigan State University. The design of the intact core microcosm is presented in Figure 5. The intact core was recapped at each end with PVC fittings with o-rings that fit snugly to the interior walls of the core tube and accommodate HDPE -NPT male pipe adapters suitable for connecting Tygon tubing on the outer ends. Sediment removed to make space for the PVC fittings was analyzed for total chromium. The bottoms of the microcosms were fitted with a mesh (polypropylene SpectraMesh, mesh size 1mm) on the interior between the PVC bushing and the soil to retain the soil core. The soil core 27 was held vertically with fluid flow entering the bottom of the microcosm. Treatment solutions were supplied to the microcosm by pumping solution with a peristaltic pump. The effluent was collected from the top for analyses. The microcosm was fitted with a 0.22 pm nylon filter at the inflow to isolate the microbial community within the microcosm; the filter was used to prevent non-native microorganisms from entering the microcosms system; and possibly affecting the experimentation. An inlet purge system was used to flush the inlet tubing of stagnant fluid prior to pumping fluid through the microcosm. Both the treatment solution and the efiluent samples were kept under argon to limit the amount of dissolved oxygen in the treatment fluid and reduce the possibility of oxidation reactions occurring in the sample fluid. All microcosm components were acid washed (10% HCl) prior to assembly to remove trace metals. Gas Excess , l Intact Ar _ '. I Sorl T alv Excess -v e <' t Artificial Figure 5. This diagram shows the design of the intact core microcosms. The red arrows show the flow direction of the water. The entire apparatus was maintained at 14°C in an incubation chamber. All fittings were non-metallic, all caps were Teflondb and the tubing was Tygon.°. 28 A sampling and treatment scheme of non-continuous pumping was devised. A non-continuous pumping scheme was employed because a continuous pumping scheme has the potential of stripping the microbial community from the soil. The physical act of pumping treatment fluids through a microcosm was termed an exchange. The amount of water pumped through a soil core for each exchange was in part determined by the volume of water that an empty core tube could contain (i.e., 250 mL). Since the porosity of the sediments in a core is significantly less than 100%, 250 mL clearly should exceed the amount of water necessary to completely replace the pore waters in the core. However, even with this amount of water, it is well known that because of heterogeneity within soils it is difficult to get complete replacement of water with just a single pore- water exchange. Therefore, the approximate amount of water necessary for pore-water replacement was estimated from a breakthrough curve study. For this study, a bromide tracer (added as KBr) was continuously pumped through a fully assembled microcosm and the effluent was collected in 30 mL aliquots. The Br concentration in the aliquots was determined by Br (mg/L) specific ion electrode. The concentration of bromide in the treatment fluid was 11.4 mg/L. The data are presented in Figure 6 Exchange Vol. (mL) and show that Br begins to reach a Figure 6. Breakthrough curve for Br tracer steady state concentration after test in a soil core from site P25. 29 approximately 250 mL of solution had been pumped through the soil and is nearly at steady state by 500 mL (double the empty core volume). Thus, 500 mL was chosen as the treatment volume for subsequent microcosm studies. As previously stated, the physical act of pumping treatment fluids through a microcosm is termed an exchange. During an exchange, the fluid obtained for the geochemical and microbial analysis was the first 120 mL of effluent from the microcosm. These samples represent the fluid that remained in the cores for the incubation period. The next 130 mL aliquot was saved in order to get enough material to be able to standardize and/or optimize the protocols used for microbial community analysis. The remaining 250 mL of exchange solution was discarded. At this point the addition of the input treatment solution was halted and the microcosm incubated at 13°C for one week or one month. The duration of the incubation periods was determined by logistical and microbial concerns. An exchange could not be conducted every day because that would not allow enough time to prepare for the next exchange. The solution also needed enough time to react with the soil and the microbial community. A one week incubation time was established, because it was thought that this was sufficient time to allow the microbial community to adjust to the treatment and also allow for preparation for the next microcosm exchange. Toward the end of each experiment the incubation time was extended to determine if the duration of the incubation time was influencing the evolution of chromium from the microcosm. 30 IV. SPECIATION OF CHROMIUM IN THE SOILS 4.1 General Observations The distributions of chromium and organic carbon in the soil samples are shown in Figure 7. The log concentrations of total leachable chromium and organic carbon concentrations are presented to allow for a full representation of the entire data sets. Total leachable metal concentrations reported in this section represent a summation of the concentrations from the sequential extraction procedure. The sequential extraction data for chromium are presented in Appendix D. The soil organic carbon concentrations are presented in Appendix E. 15 I 124 F j a , a g 9° a ‘ g: 8‘ 6« 3‘; ‘3 1 33! E :E l J3? 5.5.5} ‘ Sill 3- -- ,wl g i329“ 52:9,; 0 . . Hi: Erasmus. Hall ' 5 6 Log Cr (mg/kg) L08 Organic Carbon (mg/kg) Figure 7. Frequency histograms of the loglo concentrations of total chromium and organic carbon in the soil. Total chromium concentrations were determined by summing the concentrations of the sequential extractions. ' The concentrations of chromium ranged from 1 to 260,000 mg/kg. The distribution of chromium concentrations indicates that there may be several populations. Jeong (1994) found pre-industrial age chromium concentrations in Lake Superior sediments to range from 5080 mg/kg. Based on this information, the population of chromium concentrations from 0 to 100 mg/kg was considered to represent background 31 values for chromium in this area. Therefore, concentrations greater than 100 mg/kg are considered to be the result of human activity. The distribution of soil organic carbon concentrations shows three separate populations. These populations represent different locations or depths from which the samples were collected. Samples from upland areas of the site and deeper samples that consisted primarily of silty sand dominate the population with the lowest concentrations. Samples from upper soil horizons of the upland areas and some samples from the wetland areas define the population between 10,000 and 100,000 mg/kg organic carbon. Those samples with greater than 100,000 mg/kg organic carbon were from the wetland areas. The relationship between organic carbon and chromium in the sediments is shown in Figure 8. There is a positive correlation demonstrating the association of chromium with organic carbon, as might be expected at a former tannery site. The R2 values for the correlation between log organic carbon and log chromium for soils comprising the entire database is 0.65. The R2 for soils that are considered to have background concentrations of chromium is 0.32, while for soils with chromium > 100 mg/L it is 0.71. The \l 0) Figure 8. Correlation of the Logo concentrations of Cr vs organic carbon in the soil samples. h Log Organic Carbon (mg/kg) or (0 Log Cr (mg/kg) 32 correlation for the latter is relatively high which indicates that chromium may be associated with organic matter to a certain extent. However, the scatter in the plot demonstrates that other factors may be influencing chromium speciation in the soils. 4.2 Results of the Sequential Extractions A summary of chromium partitioning or speciation among the various operationally defined sediment phases (see Section 3.1.3) is shown in Figure 9. Very little chromium was found to be associated with the exchangeable (EX) and acid oxidizable (OX2) phases. In terms of the entire data set (Figure 9a), chromium is slightly more associated with the moderately reducible (MR) phase (49.03%) than the basic oxidizable (OX1) phase (41.12%). To a much lesser extent chromium is associated with the easily reducible (ER) and weakly acid soluble (WAS) phases, 6.47% and 3.21%, respectively. The relative amounts of chromium in both the MR and OX1 phases are almost equal (as 44%) in samples with chromium concentrations less than 100 mglkg (Figure 9b). Again, to a much lesser extent chromium is associated with the ER and WAS phases, 7.89% and 4.65%, respectively. For samples with chromium concentrations greater than 100 mglkg (Figure 9c), the MR phase (56.42%) is the most dominant in sequestering chromium. The OX1 phase accounts for 37.48% of chromium concentrations while the ER and WAS phases only account for only a minor portion (< 6% combined). The samples with chromium concentrations greater than 1000 mglkg show an increased dominance of the MR extraction, with 65.45% of total leachable chromium conring from this extraction. The amount of chromium associated with the OX1 33 Total Dataset n = 222 “33.21% £116.47!» oxuuzs mum A Cr > 100 mglkg n = 93 /./-wxs 1.22% / ‘31 4.52% oxr ’ 37.43 a MR56.42% C Cr > 10000 mglkg n = 36 OX2 WAS 0.82% 0X1 22.84 ‘b M R 72.33% Cr < 100 mglkg n = 128 ,fwxs 0.65% ER 7.89% 0x1 43.76% MR 43.67% B Cr >1000 mglkg 0’” , n = °°/—wxso.99% / _,. 145114.551! Cr > 50000 mglkg 9 0“ //w AS 0.431. Figure 9. A summary of the sequential extraction data represented as average percent of Cr extracted in each extraction. The EX and OX2 extraction percentages are too small to appear on most of the pie diagrams. and ER extractions were 28.46% and 4.55%, respectively. The WAS and OX2 extractions accounted for approximately 1.5% of the total leachable chromium. The trend of increasing percentages of chromium leached from MR extraction continues with the subset of samples with concentrations greater than 10,000 mglkg and greater than 50,000 mglkg total chromium. The MR extraction accounted for 72.33% of chromium extracted from samples with greater than 10,000 mglkg chromium and 83.52% of chromium extracted from samples with greater than 50,000 mglkg chromium. The percentage of chromium leached from OX1 extraction also decreased with increasing chromium content to 22.84% for samples greater than 10,000 and 12.89% for samples greater than 10,000 mglkg. The WAS, ER, and OX2 extractions accounted for less than 5% collectively in both cases. The MR and OX1 extractions remove the most chromium from the samples in all cases. The MR extraction removed increasingly more of the total leachable chromium from the samples than the other extractions as the total concentration of chromium increased. The EX, WAS, ER, and OX2 extractions contribute only minor amounts of chromium. The association of chromium with the moderately reducible and oxidizable extractions was expected and has been found in river sediments (Gephart, 1982; Rauret et al., 1989; Lopez-Sanchez et al., 1993; Rezabek, 1988), aquifer material (Asikainen and Nikolaidis, 1994), and black shales (Schulmeister, 1993). Chromium has been shown to strongly associate with organic matter (Krajnc et al., 1995) (the OX1 extraction) and iron oxy-hydroxides (the MR extraction). Past work could not be found which demonstrates that chromium forms sulfide minerals (the OX2 extraction) as a result of environmental contamination. Chromium (111) can be adsorbed to Mn oxides (the ER extraction), but is 35 rapidly oxidized to Cr(VI) and desorbed (Takacs, 1988; Rai et al., 1989). Chromium also does not commonly occupy exchange sites on clay minerals (McBride, 1994). Thus, the sequential extraction data indicate that the two most important phases sequestering chromium in the soils are iron oxides and organic material. Although this interpretation of the results appears to be straight forward, understanding the association of chromium with the MR (and ER) phases is not. The problem is in the nature of the selective chemical extractions. These extractions were designed for oxic systems i.e., systems exposed to oxygen (Tessier, 1979). In these systems, redox sensitive elements such as iron and manganese exist in their oxidized forms and precipitate out from solution as oxy-hydroxides (Baes and Mesmer, 1976). However, under anoxic conditions (lack of oxygen), iron and manganese oxy-hydroxides are thermodynamically unstable. There is debate as to the role of abiotic and biotic processes in the reduction of the oxy-hydroxides, but it is assumed that Fe/Mn oxy- hydroxides do not exist under anoxic conditions. Thus, it is unclear what phase of the sediment the ER and MR extractions are leaching. The geochemical behavior of chromium in aqueous systems affords some insight into this problem and perhaps also to the nature of chromium speciation patterns in the soils at this site. In systems such as those that exist at this site, the abundance of organic matter and lack of manganese oxy-hydroxides [one of the few naturally occurring oxidants that can oxidize Cr(III) to Cr(VI)], are likely to create a biogeochemical environment in which the most common form of chromium will be in the Cr(III) state (Palmer and Puls, 1994). In the pH range of the most natural waters Cr(III) is not very soluble and may precipitate out of solution as Cr(OH)3 and if Fe(III) is present it will 36 preferentially form (Cere1-x)(OH)3 (Bartlett and Kimble, 1976; Palmer and Puls, 1994; Rai et al., 1989). The solubility of these minerals or amorphous compounds increases with decreasing pH and at very low pHs they are very soluble. The pH of the MR extraction solution is less than one. Therefore the chromium that the MR extraction removes from the soil is most likely chromium hydroxide. The presence of these Cr mineral phases was investigated with X-ray diffraction analysis (Ellis, 1999), but no identifiable Cr mineral phases were present, which indicates an amorphous phase. The results of the speciation study indicate that chromium is mainly associated ' with the operationally defined MR and OX1 phases in the soils. The association of chromium with the OX1 phase is consistent with the correlation of chromium with soil organic carbon (Figure 8). The increasing dominance of chromium in the MR extraction with increasing chromium concentrations may indicate that there is a limitation to the amount of chromium that can associate with natural organic matter. Considering the results of the sequential extraction data for chromium, the chemistry of the solutions used in the selective chemical attacks, and knowledge of the biogeochemistry of chromium; it is concluded that the dominant forms of particle-bound chromium in these soils are a Cr(OH)3 mineral/amorphous solid and chromium associated with organic matter. This hypothesis is consistent with observations of chromium in various aquatic (e.g., rivers, lakes) systems (Gephart, 1982; Rezabek, 1988; McKee et al., 1989). 37 V. AQUEOUS PHASE SPECIATION OF CHROMIUM 5.1 Pore-Water Data and Thermodmamic Modeling The geochemical modeling code PHREEQC (Parkhurst, 1995) with the MINTEQ database (Allison et al., 1991) was used to assess the thermodynamic state of the surface- water and pore-water chemistry at the study site (aqueous field data is presented in Appendix F). The thermodynamic data for chromium in the MINTEQ database were updated using recent values from Ball and Nordstrom (1999). Geochemical modeling was used to determine if the solutions were in equilibrium, under saturated, or super saturated with respect to chromium solid (amorphous or mineral) phase(s). The geochemical modeling also computed the aqueous speciation based on the inorganic thermodynamic data. Chromium hydroxides are the most likely inorganic solids that would be present in this environment (Rai et al., 1989; Richard and Bourg, 1991; Palmer and Puls, 1994). The most soluble of these hydroxide forms is Cr(OH).m (Rai et al., 1989). The solubility of chromium in the pore waters was compared to the solubility of Cr(OH).m to determine if the concentration of chromium in solution is controlled by the inorganic chemistry of chromium. The solubility of Cr(OH)mm was determined using PHREEQC by simulating an equilibrium experiment at different pH values in pure water. The data presented here are the results of a simulation with a temperature of 25°C. Simulations were also conducted at lower temperatures (down to 10°C), which resulted in slightly lower 38 predicted equilibrium concentrations, but the differences in concentrations did not exceed 2 percent. The results of the comparison between the pore waters and surface waters chromium concentrations and the solubility of Cr(OH)am are illustrated in Figure 10. The figure shows that most of the samples plot above the solubility curve for Cr(OH),m, which indicates that the dissolved chromium is in excess of equilibrium concentrations with Cr(OH)3.m. Surface-water samples were collected to assess the possibility of Cr(III) oxidation to Cr(VI) in surface waters as described by Masscheleyn et al. (1992). Although the surface samples had the highest concentrations of chromium, Cr(VI) was not detected in any of the field samples. This means that either the solutions are out of thermodynamic equilibrium with respect to Cr(OH)3am or there are forms of dissolved chromium species in solution that were not accounted for in the geochemical modeling. The possibility of the solutions being out of equilibrium was initially investigated by examining the aqueous speciation as predicted by PHREEQC. Figure 10. Concentration of dissolved chromium versus pH in pore waters (blue) and surface Cr(ug/L) § “8‘ § § waters (brown triangles) at this 100 site. The curve is the theoretical 0 concentration of dissolved 5.00 6.00 7.00 3. 0 0 chrormum in equilibrium wrth Cr(OH); .m. pH The dominant inorganic aqueous chromium species as computed by PHREEQC are presented in graphical form in Figure 11 for selected samples. The samples in the figure were chosen because they represent a range of chrorrrium concentrations and pH 39 values observed at the site. The dominant species is pH dependent. At near neutral pH values, Cr(OH)3aqueous is the dominant form of chromium in solution, while at the lower pHs Cr(OH)+2 is the dominant form of chromium . In the pH range of these waters, the thermodynamic models suggest that the dominant inorganic form of chromium will be either positively or neutrally charged. 5.2 Chromium and DOC 350 300 A 250 One Sample Cluster v 3 '7'" a. 150 g D Cr(0H)3 U 100 :Cr(0H)2+ ' I Cr 0H)+ 50 0 § » ( 2 Jr" '7 i ' 549 6.26 6.28 as pH Figure 11. Graphical representation of the species computed by PHREEQC for selected water samples that represent the range of pH and chromium concentrations observed at the site. Each cluster represents the aqueous speciation for one sample. There appears to be a relationship between aqueous chromium concentrations and dissolved organic carbon (DOC) in the field samples. Figure 12a shows a plot of all the aqueous chromium concentrations versus DOC in the field samples. It is not surprising the relationship is not highly correlated when the entire data set is plotted, because of the organic rich nature of the environment from which the samples were taken. It is conceivable that a sample could have high DOC and yet have very little chromium. 40 However a trend seems apparent for the samples with higher chromium concentrations. The samples with chromium concentrations greater than 30 ug/L are shown in Figure 12b. This subset of the data shows a slight correlation between aqueous chromium and DOC with a R2 of 0.66. Although this is not a strong correlation, there does appear to be a correlation between chromium and DOC at higher chromium concentrations. This indicates that DOC may influence the concentrations of chromium in these waters. This relationship was further investigated by using solid phase extraction media to identify aqueous chromium species. 5.3 Solid Phase Extraction Data 70 60 ._ i Y; 01’3"?“ ’39? , 35 O 50 < _ H "7771870147 A 30 3 U 25 E 40 “W * ~ g» 20 5w~~~~~ 1, ~15 U 8 20* o 10 10- ~ 7 Q 5 0 I . v I v 0 O 100 200 300 400 O 200 400 600 A Cr(ug/l) B Cr(ug/l) Figure 12a and 12b. Correlation of chromium vs DOC in the surface and pore water at this site. Figure 12b is a subset of the entire data set shown in Figure 12a consisting of those samples with chromium concentrations greater than 30 ug/L. The first solid-phase-extraction media used was the Chelex-lOO resin, which removes the cations fi'om solution. The chromium remaining in solution after reaction should have a negative or neutral charge. Positively charged chromium species, such as those presented in Figure 1 1, should be removed with this extraction. The results of the solid phase extraction with the Chelex-lOO resin are shown in Figure 13 (data for this and the other solid phase extractions is in Appendix G). Crawlex is the concentration of 41 Creme: (ug/l) 300 200 / .1 L: 1.007x +0.01]:4 o” R2 = 0.997 ‘0 o (I . . a O 100 200 300 Cr (ug/l) Figure 13. Correlation of total dissolved chromium versus CrChdcx (negatively charged or neutral chromium) in surface water and pore water at the study site. chromium in solution after the reaction with the Chelex resin and therefore represents negatively charged or neutral aqueous chromium. Figure 13 clearly shows a one to one relationship (slope of 1.007 with a R2 of 0.997). This indicates that the aqueous chromium in these samples exists as either a negatively charged or neutral species, with little or no cationic chromium. The results of the solid phase extraction with the Sep-Pak resin are shown in Figure 14. This resin removes the hydrophobic fraction of the DOC and metals bound to this fraction. The non-hydrophobic fraction is the concentration of chromium in the effluent from the Sep—Pak column. There is strong relationship (R2 of 0.995) between Cl’ (“S/l) Non-Hydrophobic A-‘NNOO 888888 / / / / [1 i: 0.88x - 0.85 / R2 = 0.995 200 Cr(ug/I) 300 400 42 Figure 14. Correlation of total dissolved chromium versus non- hydrophobic chromium in surface water and pore water at the study site. total aqueous chromium concentrations and the non-hydrophobic form of chromium. The slope of the line is 0.88, which indicates that approximately 12 percent of the aqueous chromium is associated with the hydrOphobic fraction of the DOC. The results of the solid phase extraction with the AG resins are shown in Figure 15. This resin removes the negatively charged species from solution and replaces them with fluoride. The concentration of chromium in the anionic form was estimated by subtracting the concentration of chromium in the column effluent from the concentration of chromium in the control split. There is a strong relationship between chromium and anionic chromium (R2 of 0.995). The slope of the line is 0.96, which indicates that 96 percent of the aqueous chromium exists as an anion. Inorganic anion species of chromium that have been reported in environmental samples include only Cr(VI) species (Rai et al., 1989; Richard and Bourg, 1991; Kotas and Stasicka, 2000), however Cr(VI) was not detected in any of these samples. This indicates that chromium that is behaving as an anion in these waters is not an inorganic species, which suggests that this chromium exists as an anionic Cr(III)-DOC complex. / .- 1 Figure 15. Correlation of total / dissolved chromium versus anionic y = 0953‘ r 3-92 chromium in surface water and pore / R2 = 0.995 water at the study site. 0 100 200 300 Cr (ug/l) Anionic Cr (ug/I) § § § O 43 The possibility of a Cr(III)-DOC complex was further examined by plotting the concentration of chromium remaining in solution after reaction with the AG resins on the same concentration of chromium versus pH as previously shown in Figure 10. This comparison is shown in Figure 16. The surface-water and pore-water data cluster around the solubility curve for Cr(OH)3. This indicates that the non-negatively charged chromium species in solution are very near or below the solubility of Cr(OH)3,m, which suggests that these species are in near equilibrium with chromium hydroxides. A r ‘ 400 E“ \ . . :4 300 Figure 16. Concentration of non- U ; amomc chrormum versus pH m g 1 ’ pore waters and surface waters at ~53 200 3 the study site. The curve is the a: \ l theoretical concentration of 5 100 f dissolved chromium in equilibrium Z 0 _ .5 . ': with Cr(OH)3am. 5 o 7 3 9 pH The results of the solid phase extractions indicate that aqueous chromium exists primarily as an anion in the pore waters and surface waters of this wetland. Since no Cr(VI) was observed in these samples, this anion is most probably a complex of Cr(III) with some form of DOC, which is consistent with the findings of other researchers (Davis et al., 1994; Walsh and O’Halloran, 1996). In the pH range of these waters (near neutral) most of the functional groups on natural dissolved organic matter will have a negative charge (McBride, 1994). This characteristic is consistent with the assumption that the chromium exists as a Cr(III)-DOC complex. Further, the linear relationships of the SPE data and the non-anionic data plotting near the solubility of chromium hydroxide suggests 44 that there may be a thermodynamic control on the solubility of dissolved chromium involving both the dissolution of chromium hydroxide and complexation with dissolved organic carbon. There is an apparent contradiction in the interpretation of the results from the anion extraction and the hydrophobic extraction. The anion extraction indicates that 96 percent of the chromium is associated with an anionic species, however the hydrophobic extraction indicates that 12 percent of the chromium is associated with hydrophobic compounds. The contradiction arises from the fact that these two extractions combined exceed 100 percent, but if one takes into account the nature and complexity of natural organic matter the significance of this contradiction is diminished. It is completely plausible for organic compound to have both a hydrophobic component and a hydrophilic component (anionic). Soap is an example of such a compound (Cram and Cram, 1978). It is likely that all or most of the hydrophobic fraction is also part of the fraction removed by the anionic extraction. Another possibility is that the remaining 4 percent of the anionic extraction may be composed of neutral chromium species not associated with DOC, such as Cr(OH)3. However, the majority of the aqueous chromium exists as an anion, which is most likely a Cr(III)-DOC complex. 45 VI. SELECTION OF MICROCOSM SITES 6.1 Rational The goal of the study was to investigate the fate and mobility of chromium in a complex wetland environment. The nature of the microcosm experiments required that a small subset of sites were used for these experiments and so the variability of the study site had to be reduced to a small group of samples which represent the range of conditions at the site. This chapter describes the process by which sampling sites were chosen for the collection of soil used in the microcosm experiments. At the study site there exists a diverse assemblage of chemical and physical conditions. The sites were chosen primarily because they were representative of the range of biogeochemical and physical conditions present at the study site. The criteria used to select these sites were based on statistical analysis of the sequential extraction data; the sequential extraction data; preliminary pore water data; and physical observations of the sites. 6.2 Statistical Analysis 6.2.1 — Factor Analysis The selection of sites from which microcosm samples were collected was largely based on statistical analysis of the sequential chemical extraction data. Two types of factor analysis were used to identify differences in the sample population. Factor analysis is a multivariate statistical technique that is designed to reduce the number of variables describing the variance of a system. This analysis not only reduces the number of variables that can be used to describe the variance, but combines variables that behave 46 similarly into “factors”. The analysis provides insight to physical, chemical, or biological parameters that control a system. The two types of factor analyses were done for this study were Q-mode and R-mode. The analyses were done using Statistical Analysis System (SASW) on the IBM (30902001 vm/cms) main frame computer at Michigan State University. The techniques follow those outlined by Davis (1986) and are similar to those that we have used previously (Long et al., 1992). 6.2.2 - Q-Mode Factor Analysis The purpose of Q-mode factor analysis is to analyze a data set by dividing samples into groups that are similar in terms of their variables. The samples in this study are the individual soil samples from the entire database. The nine variables considered were Corg, Crwas, CrER, CrMR, CrBox, Fe-r, MnT, Cur, and 2m. The subscript T indicates the total soil concentration, which is the summation of the sequential extraction data for iron, copper, zinc, and manganese (these data are presented in Appendices H through K respectively). The variables were logarithmically transformed prior to analysis to account for their log-normality. The data matrix used for the Q-mode factor analysis had the samples as columns and variables as rows. The matrix was row normalized prior to factor analysis using the methodology given in Davis (1986). Factor scores, which are used to estimate the relative importance of the variables in defining the populations, were calculated via a FORTRAN program (Davis, 1986). The number of factors that can be used to define the data set are interpreted from the relative importance of the eigenvalues describing the data set. Each eigenvalue describes a certain portion of the variance found in the data. The first eigenvalue is the most important in describing the variance. Each successive eigenvalue describes decreasingly less of the variance. One then chooses how 47 many eigenvalues are needed to describe a certain percentage of the variance of the data set. As an example, if the data set had ten variables, then there would be ten eigenvalues describing the variance. Perhaps the first three eigenvalues describe 95% of the data while the remaining seven only 5%. A choice can be made then that of the ten variables, only three are needed to describe the data. These first three eigenvalues become the three new factors describing the data. So the number of variables describing the data set is reduced from ten to three. The choice of the cutoff percentage (95 %), as in the example, is the decision of the investigator. The Q-mode factor analysis revealed five factors that described the data set (>97%). Factors 1 and 2 account for 75% and 17% of the variability. The remaining three factors account for 4%, 2%, and 1%, respectively. The factor scores (Table 3) allow for insight into the variables influencing the individual factors. The relative importance of a variable on a factor was subjectively determined by examining the values of a variable along a row and choosing its highest value(s). Variables that are interpreted to be important in controlling the factors are shown in italics, and a negative sign denotes there is an inverse relationship between the variable and the factor. Thus, the five factors can be described by the variables listed after the factor at the bottom of Table 3. These five factors can now be thought of as sub-populations or end members of the entire data set. The most important population is essentially the one dominated by chromium with an association with iron (factor 1). The other factors show FeT, Mm, and Corg to be important to varying degrees. The association in factor 5 of chromium and Corg is consistent with what we know about the biogeochemistry of chromium and its association with Corg at the site (Figure 8). 48 Table 3. Factor scores for the Q-mode factor analysis on the entire soil data base. The italicized scores indicate the variables important in controlling the five factors. The important variables for each factor are also listed at the bottom of the table. Factor 1 Factor 2 Factor 3 Factor 4 Factor 5 Variable 0.17830 0.05847 -0.06442 0.21 I 15 0.46783 Croat; 0.23424 -0. 19757 -0.21821 -0.02355 -0. 14185 Crwas 0.31321 -0. 15900 -0. 17377 -0. 19729 -0. 18841 CrER 0.47056 0.08799 0.00280 0.06028 -0.2 1961 CrMR 0.41989 0.02340 0.02932 0.14259 0.28045 Crox1 0.48944 0.85147 0.59985 0.10901 0.24556 Fe1~ 0.22847 0.3701 7 0. 16065 -0. 924 77 0.46903 Mnr 0.21 122 0.07678 0.06728 0.09316 0.49842 CuT 0.28486 0.23681 -0. 72595 0.12734 0.26448 ZnT Factor 1 -- FeT, CrMR, Croxn, Crag, ZnT, Crwas Factor 2 -- FeT, MnT, ZnT Factor 3 -— -Zn1~, FeT Factor 4 -- -Mn~r, Crone, Factor 5 -- CUT, Mn'r, Cong, Cl‘ox 1, leT We also experimented with describing the data set with only three factors (>95%) and found similar grouping (i.e., chromium factor, Fe/Mn factor, and Corg factor). These associations were also found for the R-mode analysis as will be discussed in the next section. Five factors for the Q-mode analysis are presented here instead of the three factor model only because the results show slightly more detail in the nature of the data set. The relative importance of a factor in describing a sample (loadings) were calculated using SAS. 6.2.3 - R-Mode Factor Analysis The purpose of R-mode factor analysis is to analyze a data set to divide variables rather than samples into groups that are similar. The samples used for the R-mode analysis were the soil samples that had chromium concentrations greater than 100 mg/L. 49 R-mode analysis was only done on this sub set of the entire database because a) the histogram of total leachable chromium (Figure 7) in the soils indicated that potentially more than one population of data exist, b), R-mode factor analysis is most robust when it is done on single populations, and c) these samples are those of greatest concern from an environmental risk perspective. The eleven variables considered were Corg, Crwas, CrER, CrMR, Cl'Box, Cry, For, MnT, Fewas, FeER, and Pew. The variables were logarithmically transformed prior to analysis to account for their log-normality. The data matrix used for the R-mode factor analysis had the samples as rows and variables as columns. Eigenvalues are used to determine the number of factors that can be used to describe the data set. The results of the R-mode analysis are shown on Table 4. Only four factors were needed to define 100% of the variance of the data. The relative amounts of data variance that are explained by the factors are shown in the Table 4. The relative importance of the variables in characterizing a factor are also shown in Table 4. Using the same method as for the Q-mode analysis, variable associations for a factor were chosen and are shown in italics. The resulting factors are shown at the bottom of the table. 6.2.4 -- Summary of Factor Analyses Both the Q- and R-mode factor analyses give similar associations among the variables. Thus, both types of analyses give similar information that lends internal consistency to this analysis. Both show that factors accounting for a) chromium, b) chromium associations with iron, 0) chromium associations with Corg, and (1) Fean associations needed to be considered in the selection of the samples for microcosm work. 50 Table 4. Results of R-mode factor analysis on soils from the site with chromium concenfiations greater than 100 mglkg. At the top of the table are the eigenvalues and proportion of the variance explained by each factor. The center of the table shows the loadings of the variables on the factors. The variables that comprise each factor are listed at the bottom of the table. Eigenvalue 5.2032 2.3071 0.9609 0.6729 Proportion 0.5712 0.2533 0.1055 0.0739 Cumulative 0.5712 0.8244 0.9299 1.0038 Factor 1 Factor 2 Factor 3 Factor 4 Com 0.1 1020 0.09804 0.01048 0.80894 CI'WAS 0.92122 0.01296 -0.03864 0.05836 Crag 0.90999 0.06141 0.16508 -0.13067 CrMR 0.96324 -0.03619 0.06896 -0.01967 Crox1 0.70413 0.07705 -0.13267 0.42263 Cry 0.93055 -0.00410 0.03029 0.09736 FCWAS 0.2191 1 -0. 15359 0.87103 -0. 14426 Fee}; -0. 13122 0.27324 0.71044 0.23827 Fem 0.1201 1 0.95872 -0.18235 0.01573 Fe—r -0.05622 0.67127 0.35798 0.20560 MnT -0.02807 0.73363 0.00737 -0.49265 Variance explained by each factor eliminating other factors Factor 1 Factor 2 Factor 3 Factor 4 3.071545 1.522758 1.199903 0.821770 Factor 1 -- Crwas, CrER, CrMR, Crox1, Cr-r Factor 2 -- FeMR, Few, Mn—r Factor 3 -- -Fewas, Fem Factor 4 -- CORG, Cl'ox1, 6.3 Criteria Used for Selection of Soil Samples Initially, a preliminary list of criteria for site selection was developed based on the speciation studies and general observations presented in Chapter 4 and factor analysis. The criteria, rationale and proposed sites for the preliminary list are summarized in Table 5. The speciation studies show that the MR phase and OX1 phase are most important in 51 sequestering chromium. Therefore sites were selected that exhibited a dominance in either phase. The general observations indicated that there was an association of chromium and organic matter and therefore sites were chosen that had both high and low organic matter concentrations. Sites were also chosen based on the grouping of samples by the factor analysis. Table 5. A listing of the initially proposed microcosm sites and the rational and criteria associated with their selection. # Criteria Rationale Sites 1 Speciation The speciation studies show that the 123 0-0.5 Cr: MR > BOX MR phase and BOX phase are most or 123 1-15 important in sequestering Cr. This criterion examines the case in which the MR phase is dominant. 2. Speciation Opposite of 1. P25 0-0.5 Cr: BOX > MR or L27: 0-0.5 3. General This examines the effect of high K28: 0-0.5 low Cr; and high amounts of Corg on low concentrations Corg of Cr. This case would be of lower priority for this study 4. General Opposite of 3. 022: 3-3.5 high CrT and low Corg 5. Factor analysis This is the most common association of K22: 0-0.5 high R loadings on factors for the sub data set that factors 1, 2, 3, 4 comprises soils with Cr > 100 mg/L. 6. Factor analysis This is a common association. S26: 005 high R loadings on or .119: 0-0.5 factors 1,2,4 only 7. Factor analysis This is a common association. 022: 3-3.5 high R loadings on or Q26: 0-0.5 factor 3 only 8. Factor analysis This is a common association. K22: 1-1.5 high R loadings on factors 2, 3, 4 only conducted at these sites, along with more detailed field observations. The additional data Once this preliminary list was developed, field sampling of the pore waters was 52 gained from the field work included an estimation of oxidation-reduction state (redox) and possible terminal electron acceptor processes (TEAP) as indicated by various biogeochemical indicators such as Fe”, S2', and CH4 (Lovely and Goodwin, 1988). Also the additional field work provided for a distinction between sites based on the physical conditions at the site such as the saturation history and basic soil characteristics. The results from the pore water analysis (Appendix F) showed that, as expected, various degrees of anoxia exist throughout the study area. All major TEAP variables could be measured to some degree. Some sites had very high amounts of dissolved CH4, Fe”, or 82'. This is suggestive of various types of microbial activity such as methanogenesis, iron reduction, and sulfate reduction. Most sites had negative to very negative Eh measurements, which indicates reducing conditions and is consistent with the anoxia indicated by the TEAP variables. The saturation history became an important observation as a result of the pore water sampling. When a peeper was installed at P25 in June 1997, there was approximately 5 inches of standing water at the surface. However, when the peeper was retrieved from this site three weeks later, there was no longer any surface water and the top ports were partially exposed to air. This caused the oxic conditions in several inches of soil near the surface, as evidenced by red iron oxide coatings on the peeper upon retrieval. Similar changes in saturation were also observed at N23. The history of changing saturation states at these sites created a new criterion for selection. The sites selected for the microcosm studies are listed Table 6, with the criteria used to select them. Only sites with high chromium were chosen for the microcosm experiment because those samples are of the highest environmental concern. Based on 53 logistical constraints, only six sites could be chosen to represent the diversity of the site. Each of the chosen sites represents a group of sites defined by their physical nature or biogeochemistry, which spans the range of possible conditions at the site. Table 6. A summary of the physical and chemical characteristics of the sample sites selected for the microcosm work. Site: Sequential Factor Redox/ Saturation Soil Soils Depth Extraction Analysis TEAP State Organic (ft) (% of MR Matter and OX1) (% OM) 123: MR — 85.8 R loading on highly running 74.4 dark 0-0.5 OX1 - 13.0 factors 1 and anoxic water at brown 4; Q loading high cm, the organic on factor 1 high 82" surface rich P25: MR - 36.7 R loadings on oxic to variable 62.1 dark 0-0.5 OX1 — 62.5 factors 3 and anoxic saturation brown 4; Q loading high N114“, conditions organic on factor 1 high CH4 rich K22: MR - 60.4 R loadings on weakly standing 76.5 dark 0.0.5 OX1 — 37.6 factors 1, 2, 3 anoxic water brown and 4; Q low CHa, organic loading on high 8042’ rich factor 1 119: MR — 79.3 R loadings on No data usually 65.3 dark 0-0.5 OX1 — 19.7 factors 1, 2 dry brown and 4; Q organic loading on rich silty factor 1 sand N23: MR - 51.5 R loadings on anoxic variable 77.3 dark 0-0.5 OX1 — 45.6 factors 3 and very high saturation brown 4; Q loading CHa, very conditions organic on factor 1 high Fe“, rich high Mn'r, high Cr—r 022: MR - 84.8 R loading on anoxic dry at 69.9 grey silty 3-3.5 OX1 — 14.5 factor 3; Q high NHI, surface, sand loadings on high SOaz' wet at factors 1 and depth 2; high Cr;- and low Cor 54 VII. ACID RAIN MICROCOSMS 7.1 Rational The first treatment chosen for the microcosm experiments was the simulation of the acidification of the pore water at the site due to acid rain. One likely source for acid input to the soils at this site is atmospheric precipitation. Acidic conditions may cause the dissolution of chromium hydroxide solids resulting in the possible liberation of chromium to the environment (Rai et al., 1989; Mattuck and Nikolaidis, 1996). The solubility of chromium hydroxide reaches a minimum at pHs between 6 and 11 (Rai et al., 1989). In this pH range, the dominant form of chromium in solution is as the neutrally-charged species, Cr(OH)3.0 (Figure 11). At pHs below 6 Cr(HI) solubility increases rapidly with decreasing pH (Figure 10). Thus, lowering of the pH should liberate chromium from these soils. Soil cores from the six microcosm sites were treated with a synthetic acid rain solution. The composition for the synthetic acid-rain water is listed in Appendix L and was based on published data for acid rain in the northeastern United States (Galloway et al., 1976). The resultant pH of this acid water was 3.86. Duplicate samples from the six microcosm sites were treated with a non-acidic control solution. The control solution was prepared by substituting sodium salts for the acids used in making the artificial-rain solution. Sodium salts with the same counter anion as the acid were used to make the simulated control-rain solution. Both solutions were autoclaved prior to use in an 55 exchange. This chapter presents the results of these microcosm experiments. The data for the microcosm experiments is presented in Appendix M. 7.2 Dissolved Chromium versus DOC Results Similar to the results from the field data, there appears to be a relationship between aqueous chromium concentrations in some of the microcosm samples and dissolved organic carbon (DOC) (Figures 17a and 17b). Figure 17b is an expanded view showing the lower concentration data in Figure 17a. These figures show all of the chromium versus DOC data collected during the six-month experimental period. The data is presented by the site from which the cores were collected and includes data from both the acid rain and the control microcosms. Samples from microcosms 119, P25, N23, and K22 showed strong positive correlations between dissolved chromium and DOC. Samples from microcosms 123 and 022 show very weak correlations between dissolved chromium and DOC. The correlation for the 123 data is strongly influenced by the 123 control microcosm, which had very high concentrations of DOC in the initial samples 70 1 70 60 60 .732; O 50 G 50 .N23 in 40 En 40 P25 E; 30 5 30 .123 8 20 8 20 0022 10 10 o .119 0 0 0 500 1000 1500 0 50 100 150 200 Cr (ug/L) B Cr (ug/L) Figures 17a and 17b. Correlation of chromium versus DOC in the acid-rain and control microcosm effluent (R2 values for the groups are; K22 = 0.68, N23 = 0.71, P23 = 0.71, 123 = 0.19, 022 = 0.26, 119 = 0.78). The samples are grouped by site and include both the acid rain treated and the control samples from each site. 56 from the microcosm (shown in light blue on Figure 17b). The chromium data from 022 microcosms were not highly correlated with DOC. The 022 microcosms consisted primarily of gray, silty sand with very little organic carbon (Table 6; Appendix A) and was significantly different in this respect to the rest of microcosms. The majority of the data indicates that there is an association between chromium and DOC. 7.3 Solid Phase Extraction Results There was not enough fluid in the microcosm samples to use the three resins that were used in the field samples, but the chelex 100 resin was used with the microcosm samples to aid in identifying the aqueous speciation of chromium. The data from the chelex 100 reaction are plotted in Figure 18. Similar to the previous graphs showing chelex data, Cram.“ represents that concentration of chromium remaining in solution after the reaction with chelex resin, which should represent negatively charged or neutral chromium. There is a strong relationship (R2 of 0.98) between total aqueous chromium concentrations and Crawl“. These results indicate that dissolved chromium exists as a negatively charged or neutral species. Since both the chelex and DOC data are similar to 2000 g 1500 V‘ “9358"“ 27023 _. Figure 18. Correlation of :r R = 0'9805/ total dissolved chromium v 1000 e ‘ versus Crew“ (negatively 4%. 0 ° charged or neutral 3’ 500 , ° chromium) in the acid rain microcosm effluent water. 0 sf. , , , 0 500 1000 1500 2000 Cr (ugll) 57 the field data, it can be assumed that the aqueous chromium probably exists as an anionic, chromium-organic complex. 7.4 Changes in 2H Over Time Over the duration of the experiment the pH values approached the pH ranges that were observed in the field samples (Figure 19). The range of pH values in the field samples associated with the sites where cores were taken for the microcosms are also shown as vertical lines to the right of the plot. The first samples were collected differently than the method outlined in section 3.3 and were collected at the end of the initial 500 mL exchange of fluid, which replaced the pore water that was in the core originally. All other samples consisted of the first 120 mL of effluent water coming from the microcosm during an exchange as described in section 3.3. The pHs of the first several exchange solutions are generally higher for each microcosm than they are in the pore water at their respective field sites. The initial high + K22 Acid + N23 Acid P25 Acid + 123 Acid + 022 Acid e 7 119 Acid —l—- K22 Control —+—— N23 Control P25 Control + 123 Control —+—022 Control 77* 119 Control Field Data 0 25 50 75 100 125 150 175 Time (Days) Figure 19. Changes in the pH of fluids in the microcosms as firnction of time. The range of pH values observed in the pore-waters at these sites are represented by the vertical lines to the right of the concentration profiles. 58 pH values may reflect conditions that developed within each microcosm during the holding period between soil collection and the initiation of the experimentation. Also, there is very little difference in the pHs of the microcosm effluent between the acid and control microcosms from the same site. After the second or third week most of the pHs in the pore waters of the microcosms decrease and appear to stabilize at levels near the field measurements. The one exception to these general observations are the 022 microcosms, in which the pH values remain much higher than the field data through the experiment. The cause of the pH behavior in the 022 sample is not clear, but may be related to the composition of the soil (e.g., sandy, low organic matter). The mobilization of chromium from these microcosms is not likely to be the result of acid-driven dissolution. The fact that the acid-rain microcosm pH values were similar to control microcosm pH values indicates the buffering capacity of the soil neutralized the effects of acid rain during the course of the experiment. This was apparent even though the amount of treatment water pumped through the microcosms was the equivalent of approximately 5 years of rain, assuming an average rain fall of 31.5 inches (NOAA, 1993). This calculation was based on the amount of water that would pass the surface of the cylinder and also assumes that all the rain infiltrates flows through soil. It is unlikely that in an actual rain event all of the rain will pass vertically through the soil, for this reason the calculation should be considered as a maximum exposure. If the acid rain simulation had a significant effect on the pore water of the microcosms a much greater decrease of the pH in the exchange water would be expected. Therefore the buffering capacity of the soil exceeds the amount of acid that was applied to the microcosm. 59 7.5 Changes in Chromium Concentrations Over Time In general, chromium concentrations in the microcosm effluent tended to decrease over time as shown in Figure 20 for all the microcosms and in Figure 21 showing those microcosms with lower concentrations of chromium. The range of chromium concentrations in the field samples associated with the sites where cores were taken for the microcosms are also shown in Figure 21 as vertical lines to the right of the plot. Hexavalent chromium was not detected in any of microcosms exchange solutions. The first samples taken for analysis from the microcosm were at the end of the initial exchange of 500 mL. These samples would represent the mostly new fluid in the microcosm, as most of the original fluid would have been flushed out. These data are plotted at time zero on Figures 20 and 21. Each subsequent sample was taken at the beginning of the exchange, as described in the methods section and represents fluid in the microcosm for the previous week or month depending on the incubation period. 1800 —+- K22 Acid 1600 + N23 Acid 1400 . 925 Acid 7% 1200 -.— 123 Acid + 022 Acid 1000 5 300 —.— 119 Acid 5 -+ ~ [(22 Control 600 -—+- N23 Control 400 P25 Control 200 ——+— 123 Control 0 —l— 022 Control 0 2o 50 80 110 140 170 200 ”“7 ‘J ’9 C°mr°l Time (Day-9) Figure 20. Chromium concentrations in the exchange soutions. 60 250 + K22 Acid + N23 Acid 200 . (an--. ._... _ . — . fl..- ”’"" P25 Acid +123 Acid —+— 022 Acid —+— K22 Control —+— N23 Control P25 Control —+—— J23 Control —1— 022 Control [flDam O 20 50 80 110 140 170 L Tirne(Days) Figure 21. This figure is similar to Figure 20, although sample 119 was not included. Also, the vertical lines, to the right of the concentration profiles, represent the ranges of chromium concentrations observed in the pore-waters at these sites. In general, chromium concentration trends in the exchange water are similar for both the acid and control microcosms from a given site. Chromium concentrations in the exchange water of all the microcosms decreased over the time during the initial one week incubation periods. When the incubation period was extended to one month the concentration of chromium increased in all microcosms except the 022 microcosms. This implies that the mechanism causing the release of chromium was allowed to develop more firlly during a month incubation period. The incubation period appears to have a significant influence on the release behavior of chromium. The dissolved chromium concentrations in the microcosm effluents are similar to the measured concentrations in the field pore-water samples (Figure 21). The majority of the chromium concentrations fall within the range of concentrations for the corresponding field pore waters for all sites except 022, which were generally lower than 61 the field concentrations. The site at J 19 was usually unsaturated and therefore pore water was not available for comparison. The acid and control exchange solutions do not appear to mobilize the chromium to dissolved concentrations that are higher than what are normally found in the pore water at the site (Figure 21). This indicates that the simulated acid-rain treatment did not mobilize chromium to a greater extent than the conditions currently at the site and also demonstrates that the microcosms were successful in replicating the conditions observed in the field. Dissolved chromium concentrations in the exchange water from microcosms 119, P25, and N23 are higher than the rest of the microcosms. Sites 119, P25, and N23 are all sites that experience unsaturated field conditions at least part of the year. Site 119 is in a small upland area that is usually unsaturated. The water table is more than 3 feet below the surface at this site. Site P25, and to a lesser extent site N23, are in areas that have an observed history of periods of saturation and unsaturation. The rest of the sites are in areas that are continually saturated with water. Considering only the sites that experience unsaturated field conditions, concentrations in the exchange water are highest in 119 and lowest in N23. 119 site is also experiences unsaturated conditions more than the N23 site, which may suggest that the duration that a site is saturated or unsaturated may have an effect on the mobility of chromium. The amount of chromium released from the microcosms did not appear to be related to the total concentration of chromium in the soil (Table 7). Chromium concentrations were determined on soil removed from the ends of the cores during construction of the microcosms. The totals were determined using the method described in section 3.1.4. The data are arranged on Table 7 in order of decreasing amounts of 62 chromium in the microcosm effluent. In many of the cores there was a large difference in the solid phase chromium concentrations between the top and the bottom. The highest soil concentrations were observed in the microcosms from 119, which also had the highest concentration of chromium in the exchange water. The microcosms from P25 released the second most chromium in the microcosm experiments, but the soils had relatively low chromium concentrations. The microcosms from the K22 sites contain the second highest concentrations of chromium in the soil, but very little chromium was eluted from these microcosms (Figure 21). There appears to be no relationship between the amount of chromium in the effluent and the amount of chromium in the soil of a particular microcosm. Table 7. A summary of the concentration of chromium in the microcosm soils presented in order of decreasing chromium concentrations in the microcosm effluent. Sample Location Cr Cone. Sample Location Cr Conc. in core (mg/kg dry wt.) in core Qng/kg erwt.) 119 Acid Top 15942 K22 Acid Top 12327 Bottom 88877 Bottom 1201 119 Neutral Top 6132 K22 Neutral Top 8430 Bottom 71693 Bottom 1299 P25 Acid Top 6108 123 Acid Top 12135 Bottom 3127 Bottom 54988 P25 Neutral Top 7573 123 Neutral Top 1676 Bottom 2777 Bottom 78188 N23 Acid Top 14298 022 Acid Top 6382 Bottom 21073 Bottom 368 N23 Neutral Top 10673 022 Neutral Top No Sample Bottom 8626 Bottom 5541 One possible explanation for the decreasing chromium concentrations in the microcosm effluent is that chromium is being liberated as a by-product of microbial degradation of the natural organic matter. In this scenario the chromium is bound to 63 organic matter which is being utilized by microorganisms and chromium is released as a Cr(III)-DOC complex by-product of that reaction. The positive correlation of chromium with DOC in the microcosm samples and the solid phase extraction data strongly indicate a connection between chromium and DOC, which supports this theory. This could also account for the trend in chromium concentrations over time in the microcosm effluent. In this situation, the one-week incubation period did not allow enough degradation of organic matter to create high concentrations of a Cr(III)-DOC complex. A one-month incubation did allow for a large amount of Cr(III)-DOC to be produced, which resulted in higher concentrations. This may also explain the observation that the sites that are usually drier release more chromium. Sites that are unsaturated allow for oxygenated conditions. Oxygen respiration is the most efficient metabolic approach to degrade organic matter and therefore Cr(III)-DOC complexes could build up in the soil. These complexes could then be mobilized with the subsequent influx of water. If these complexes existed in the soil prior to the initiation of the experiment they may have been slowly released over the course of the experiment, which would explain the decrease in chromium concentrations over time. Another possible explanation for microcosm data is that chromium is being liberated as a Cr(III)-DOC complex that is the result of a thermodynamic, equilibrium reaction. In this scenario chromium is coming into solution in an effort to reach an equilibrium state with a solid phase, which for chromium in this system would likely be Cr(OH)3.m. This chromium hydroxide may be dissolving to form Cr(OH)x(3’X) aqueous species, as illustrated in Figure 11, that could then react with the dissolved organic matter to form Cr(III)-DOC complexes. The DOC and solid-phase extraction data also support this explanation, which could also account for the trend in chromium concentrations over time in the microcosm effluent. In this situation, the one-week incubation period did not allow enough time for the reaction to proceed toward equilibrium. While a one-month incubation did allow for the react to proceed further, which resulted in higher concentrations. Also, if the final concentration was influenced or determined by the availability of organic ligands produced by microbial activity then this may explain the increased chromium concentrations with the one-month incubation period as a result of increased microbial activity due to the longer incubation period. This process is consistent with the conclusions of a thermodynamically driven equilibrium process controlling the chromium concentrations that was suggested for the field data. It is not possible to determine the exact process by which chromium is entering solution with these data. However, it is apparent that organic ligands play a major role in the solubilization of chromium in these soils. Microorganisms in the soil control the type and abundance of organic ligands in soil pore waters. For these reasons, the second round of microcosm experiments was focused on influencing the microbial processes in the soil cores. 65 VIII. NUTRIENT MICROCOSMS 8.1 Rational The results from the preceding work indicate that a significant portion of the chromium in the soils and pore waters is associated with organic matter. If true, changes in the types or rates of degradation of organic matter could influence chromium behavior at the site. The mobilization of chromium could occur as a by-product of the degradation or an increased availability of ligands in solution which complex with inorganic dissolved chromium. A likely method for disturbing the soil organic matter would be the natural microbial degradation of the soil organic matter. During this process natural plant material is broken down into smaller fragments and eventually converted to carbon dioxide and/or methane. The treatments for the second round of microcosm experiments were designed to increase the degradation of soil organic matter by stimulating the microbial community. The hypothesis was that if the degradation of soil organic matter increased the concentration of chromium would increase in the pore water of the microcosms. One of these treatments attempted to maximize the efficiency of the microbial community by altering the redox state to a higher level. The field data indicated the pore waters were in a reduced (oxygen deficient) state, as expected for an organic rich wetland area, and the microbial degradation of cellulose based plant material is inhibited under reduced conditions (Atlas and Bartha, 1993). Microbial communities use a variety of energy sources or terminal electron acceptors and communities that utilize oxygen as 66 their predominant terminal electron acceptor are the most efficient at degrading soil organic matter because it is the most energetic terminal electron accepting process (Lovley and Goodwin, 1988; Atlas and Bartha, 1993). However, for the purposes of this experiment oxygen could not be used because it has a very low solubility and it was thought that the amount of oxygen that could be injected with the water would be quickly utilized leaving the remainder of the week to develop anoxic conditions again. The next most energetic TEAP is the reduction of nitrate (Lovley and Goodwin, 1988; Atlas and Bartha, 1993; Lovley et al., 1994). Since nitrate is soluble in water, it was added to the artificial rain solution to make a final concentration of 90 mg/L nitrate. Another treatment attempted to stimulate microbial processes by increasing the overall nutrient level of the pore water. The objective of this treatment was to add nutrients to the system that were lacking and thereby increase the microbial potential to degrade the soil organic matter. In this treatment nitrate and phosphate were both added in concentrations of 25 mg/L and 2 mg/L respectively to the simulated rain solution. The third treatment was the artificial rain solution, as a control, that was used in the previous microcosm experiments. Soil cores for these microcosm experiments were collected in the spring of 1998 from the same six locations as the first microcosm experiments. From each site, three soil cores were collected, one core for each treatment, resulting in a total of 18 microcosms. The sampling protocols, microcosm design, and sampling strategies for the microcosms were essentially the same as in the first microcosm experiments. The only differences were that 1) the first sample collected was the first 120 mL of fluid that eluted from the core during the first exchange, and 2) all treatment fluids were de-aerated by 67 bubbling argon gas through the solutions for one hour prior to pumping them into the microcosms. 8.2 Dissolved Chromium versus DOC Results The relationship between aqueous chromium concentrations and DOC appears to be more ambiguous for the nutrient-microcosm samples than either the field or the acid- rain microcosm data. The data are presented on four separate plots (Figures 22 a, b, c, and d). When looking at the entire data (Figure 22a) the data are not highly correlated DOC (mg/L C) Cr (ug/L) l O'\\I CO WAUI COO DOC (mg/L C) 8 .— CO 0 200 400 C Cl' (ug/L) 600 800 C 5 U Q Q 200 400 600 800 B Cr (ug/L) C 5 U Q Q 0 100 200 300 400 500 Cr (ug/L) Figure 22. Correlation of chromium versus DOC in the nutrient microcosm effluents. Figure 22a includes the samples from all three treatments (N, N&P, and control) from each site. Figure 22b shows data from the microcosms treated with 90 mg/L nitrate. Figure 22c shows data from the microcosms treated with 25 mg/L nitrate and 2 mg/L phosphate. Figure 22d shows data fiom the control microcosms treated with the simulated rain solution. 68 (R2=0.25). The poor correlation appears to be primarily the result of a group of samples with high DOC concentrations. However the majority of these data plots in a trend with a slope of between 0.04 and 0.08, which is similar the trends that were observed in the field and acid-microcosm data (Figures 12 and 17). The data for the 90 mg/L nitrate (N) treatment (Figure 22b) shows a very poor correlation (R2=0.051), but a trend similar to the trends observed in the field and acid- microcosm data is still apparent. The data for the 25 mg/L nitrate and 2 mg/L phosphate (N 8:?) treatment (Figure 22c) shows a much better correlation (R2=0.78), which is similar to the field and acid-rain microcosm data. The data for the control treatment (Figure 22d) also shows a much better correlation (R2=0.78), however, the correlation is highly dependant on the samples above 150 mg/L chromium. These samples all come from the 119 control microcosm and have DOC concentrations that are much higher as a group than the rest of the data. The control samples below 20 mg/L chromium (Figure 22d) appear to have a linear trend similar to that of Figure 22c. The treatments were designed to enhance microbial degradation of organic matter and it is likely that this would also impact the concentration and nature of the DOC. This may result in the relationship between dissolved chromium and DOC becoming less clear as seen in the microcosms treated with 90 mg/L nitrate. The relationship may be impacted by a production of ligands faster than the reaction with available chromium can occur. Even though the relationship between chromium and DOC may have become less obvious, all of the figures for the nutrient microcosms show a trend similar to that observed in the field and acid-rain microcosms to a certain extent. By analogy, this 69 indicates there is a relationship between chromium and DOC in the nutrient microcosm samples. 8.3 Solid Phase Extraction Results The chelex 100 resin was also used on the nutrient-microcosm samples to aid in identifying the aqueous speciation of chromium. Similar to the previous graphs showing chelex data (Figures 13 and 19), Cram.“ represents that concentration of chromium remaining in solution after the reaction with chelex resin which should represent negatively charged or neutral chromium. The results of this extraction on the nutrient samples (Figure 23) are similar to previous results using this extraction medium (Figures 13 and 18). The data are highly correlated (R2=0.996) with a slope near one (slope=0.998), which indicate that the dissolved chromium exists as a negatively charged or neutral species and by analogy with the field data is probably a Cr(III)~DOC complex. 700 g) :33 Figure 23. Correlation of 3 400 total dissolved chromium ‘5 versus Creme, (negatively 3 300 charged or neutral CS 200 chromium) in the effluent 100 water from the nutrient O microcosms. 0 100 200 300 400 500 600 700 Cr (ug/L) 8.4 Changes in Nitrate and Sulfate Concentgtions over Time The concentrations of nitrate and sulfate were monitored to assess whether the treatments were affecting microbial processes. Phosphate was also monitored, but the concentrations were consistently too low to quantify. Nitrate and sulfate are both used as terminal electron acceptors by microbes and their concentrations may give an indication 70 of the TEAP conditions of the system (Lovley and Goodwin, 1988; Lovley etal., 1994). Sulfate and nitrate were components of the simulated-rain solution and were present in all the treatment solutions used in the microcosm experiments (Appendix L). The concentrations of nitrate and sulfate in the simulated-rain solution were 2.4 mg/L nitrate and 5.6 mg/L sulfate. Also, nitrate was monitored because it was added to both of the nutrient treatments. The nitrate concentrations from the microcosms treated with 90 mg/L nitrate (N) showed two different trends during first ten weeks of the experiment (Figure 24). The most common trend was that the concentrations tended toward a relatively constant concentration. The microcosms from sites 119, P25, K22 and 022 all showed this trend, with concentrations for the different microcosms ranging between 20 and 40 mg/L. The 119 microcosm core was not saturated with water when collected and the initial sample from that microcosm had a high concentration because it was primarily composed of the incoming treatment water. The other trend consisted of a general increase in concentration from the beginning of the experiment until week ten. The microcosms from sites 123 and N23 showed this trend, with maximum concentrations near 30 mg/L. These trends indicate that nitrate was being utilized by the microbial community to varying degrees in all cores. The concentrations of nitrate decreased dramatically for all microcosms in the last two exchanges for the N treatment microcosms. This may indicate a change in the microbial community to allow for a greater utilization of nitrate that was added. The nitrate concentrations from the microcosms treated with 25 mg/L nitrate and 2 mg/L phosphate (N&P) showed two different trends during first ten weeks of the 71 80 £60 £40 0 Z 20 0 .. 0 20 40 60 80 100120 Time (Days) P25 40 O N03 (mg/L) 8 U) 10 0 0 20 40 60 80 100120 Time (Days) 123 E 6 Z 0 20 40 60 80 100120 Time (Days) + N + N&P + Control O N03 (mg/L) 8 (a) IO 0 0 20 40 60 80 100120 Tirne(Days) N23 40 £30 A g 20 W 6 l 2 IO 31>- 0 .1 0 20 40 60 80100120 Tirne(Days) 022 40 E 20 —<- 6 r 1 z 10 11$? 0-#p%—— 0 20 40 60 80100120 Time (Days) to- N —-— N&P + Coutrofi Figure 24. Nitrate concentrations in the effluent of the nutrient microcosms over time for the six microcosm sites. The concentration range is not the same for each graph N represents the microcosms treated with 90 mg/L nitrate. N&P represents the microcosms treated with 25 mg/L nitrate and 2 mg/ L phosphate. Control represents the microcosms treated with the simulated rain solution. experiment as well (Figure 24). The nitrate concentration trends from microcosms 119, P25, and .123 are all near zero with no concentrations greater than 3 mg/L. This indicates that the microbial community in these microcosms utilized the nitrate almost completely. 72 The concentration trends from microcosms K22, N23, and 022 tend toward constant concentrations ranging in concentration from 8 to 12 mg/L. These trends indicate that the microbial community was utilizing the added nitrate to a certain extent. As with the N treatment, the concentrations of nitrate decreased dramatically for all microcosms in the last two exchanges for the N&P treatment microcosms. This may indicate a change in the microbial community to allow for a greater utilization of nitrate that was added. The concentrations of nitrate in the control microcosms remained near or below the input concentration of 2.4 mg/L for all microcosms (Figure 24). The nitrate data indicates that the microbial community was utilizing the nitrate added to the system. The trends in sulfate concentrations in the amended microcosms may be used to support the indication that nitrate was being utilized by the microbial community. Microbes can get a higher energy yield when using nitrate as a terminal electron acceptor as opposed to sulfate (Lovley and Goodwin, 1988; Atlas and Bartha, 1993). When nitrate reduction is the dominant TEAP sulfate can exist in the pore water at higher concentrations than when sulfate reduction is the dominant TEAP (Lovley and Goodwin, 1988; Lovley et al., 1994). Therefore high concentrations of sulfate may indicate that nitrate reduction is the dominant TEAP. Also, the production of sulfate in the microcosms would not occur if the strongly reducing conditions prevailed. The concentration of sulfate in all of the treatment solutions was 5.6 mg/L (Appendix L). The sulfate concentration trends from microcosms that were treated with 90 mg/L nitrate reduction indicate that nitrate may have been the dominant TEAP in these microcosms (Figure 25). The general trend of sulfate concentrations for these microcosms show a gradual increase in the first ten weeks and then a sharp increase in 73 K22 0 20 40 60 80 100120 } 0 20 40 60 80 100120 Time (Days) i Time (Days) -.__,_.____ _ N23 40 €30 % —-— *~« 520 a 10 «4 ___-,_ 0 l l I l l 0 20 40 60 80 100120 0 20 40 60 80 100120 Time (Days) I _ 022 250 £200 g 150 5100 "’ 50 0 0 20 40 60 80 100 120 0 20 40 60 80 100120 Time (DayS) Time (DayS) [Z—N +N&P +Controfl RN +N&P +Contrbfl ; ‘ _ Figure 25. Sulfate concentrations in the effluent of the nutrient microcosms over time for the six microcosm sites. The concentration range is not the same for each graph. N represents the microcosms treated with 90 mg/L nitrate. N&P represents the microcosms treated with 25 mg/L nitrate and 2 mg/L phosphate. Control represents the microcosms treated with the simulated rain solution. concentration for the last two exchanges. There are two exceptions to this trend. First, concentrations of sulfate in the 119 microcosm initially decrease and level ofl‘ before increasing in the last two exchanges. Second, the last exchange for the N23 microcosm 74 decreased significantly from the previous concentrations and may have been an errant data point. In general however, the elevated sulfate concentrations show that the redox state of these microcosms was at least oxidizing enough to allow for the formation of sulfate. The rapid increase in sulfate in the last two exchanges corresponds well with decrease in nitrate for the same exchanges. Sulfate concentration trends for the first ten weeks were similar in both the N&P and control microcosms. The concentrations were relatively constant with values ranging between 2 and 4 mg/L, except for 022 which were from 8 to 12 mg/L. Concentrations less than 5 indicate that sulfate is being consumed by the microbial community. This indicates that nitrate reduction may not be the dominant TEAP in these microcosms. Concentrations of sulfate in the last two exchanges increased in all of the N&P microcosms, indicating a major shift of the redox state in these microcosms. This corresponds well with the nitrate data, which decreased in these exchanges. Except for the last two exchanges and microcosm 022, sulfate was not forming in these microcosms, which suggests that these microcosms were more reduced than the N microcosms. The nitrate and sulfate data indicate that microbial processes were influenced by the treatments. One of the goals was to produce a higher redox potential (or TEAP) in the N microcosms and it appears that this was achieved. It also appears that the microbial community utilized the nitrate and phosphate in the N &P treatment fluids and therefore the treatment objective for this treatment was also achieved. 75 8.5 Changes in Chromium Concentrations over Time In comparing the trends of chromium concentrations from the acid-rain microcosm experiments to those in the nutrient microcosm experiments, it should be noted that information from the first samples taken are not directly comparable between the two microcosm studies. This is because in the nutrient microcosm experiments the first sample is the first 120 mL of water from the microcosm during the first exchange. In the acid rain microcosms, the first sample was the final 120 mL of water from the microcosm during the first exchange. The nutrient microcosm experiments were conducted for 14 weeks with a normal incubation of one week and a 3-week incubation period between the last two samples. It should also be noted that the first sample for the .119 microcosms consisted primarily of the incoming treatment fluid, because the cores were collected from unsaturated soils. The level of chromium concentrations in the effluent from the nutrient microcosms (Figure 26) is similar to the level of chromium concentrations from acid-rain microcosms (Figures 20 and 21). The relative level of chromium concentrations among the sites was also similar to what was found in the simulated acid rain experiments and followed the order 1 19 > P25 > N23 > 123 2 K22 > 022. In general, the chromium mobilized from the soils increased after the initial exchange and also after the longer incubation period, with the exception of the 022 microcosms (Figure 26). The results of the chromium concentration data from the nutrient microcosms shown in Figure 26 are summarized in Table 8. The chromium concentrations for the nutrient microcosms are compared against the control microcosms and each other for each site. The table also 76 120 100 Cr (ug/l) 8 8 A O 0 20 40 60 80 100120 0 20 40 60 80 100120 .._ Tjnegayi) _ _ _ ___ Time (days) I N23 0 20 40 60 80 100120 0 20 40 60 80 100120 Time (days) Time (days) 022 0 1 r l l 1 o 20 40 60 80 100 120 0 20 40. 60 80 100 120 Time (days) Time (days) +N +N&P +-Controlj 1 i+N +N&P +Controll Figure 26. Chromium concentrations in the effluent of the nutrient microcosms over time for the six microcosm sites. The concentration range is not the same for each graph. N represents the microcosms treated with 90 mg/L nitrate. N&P represents the microcosms treated with 25 mg/L nitrate and 2 mg/L phosphate. Control represents the microcosms treated with the simulated rain solution. 77 includes the change in chromium released after the sample interacted with the treatment solution for the three-week period. Table 8. Summary comparison of chromium in the effluent from nutrient microcosm experiments. Comparison Soil Sampling Site 1 19 P25 N 23 123 022 K22 N vs. Control similar > > > < > N&P vs. Control > similar similar > < < N vs. N&P < > > similar similar > N last sample higher similar higher higher similar higher N&P last sample higher slightly > similar similar similar higher Control last sample higher slightly < similar similar lower higher Explanation: N = treatment with 90 mg/L N03, N&P = 25 mg/L N03 and 2 mg/L P04; similar means N treatment and control or N&P treatment have similar chromium concentrations; > means N treatment chromium values are greater than control or N&P treatment values; < means treatment chromium values are less than control or N&P treatment values. The last three rows depict the change in the concentration of chromium in the effluent after remaining in the microcosm for 3 weeks. The microcosms from site 119 showed the N&P treatment liberated the most chromium, while there was very little difference in the chromium concentration of the effluent between the N and control treatments. Concentrations of chromium in the effluent initially increased from the first samples taken in both treatments and in control samples and then decreased over time. Concentrations of chromium in the effluent increased after the three-week interaction time. The microcosms from sites P25 and N23 show the N&P and control treatments had similar chromium concentrations, while the highest chromium concentrations were from the N treatment microcosms. Concentrations of chromium decreased in samples from the P25 site and little change in chromium concentrations was found after the three- week incubation time. The N23 microcosms had chromium concentrations in both the N 78 and N&P treatment samples and the control samples that increased to relatively constant concentrations. Except of the N treatment, concentrations of chromium in the effluent after the three-week incubation period did not change. Concentrations in the N treatment after this time were higher for the N23 microcosm. The microcosms from 123 show concentrations in the control samples were different from those in the treatment samples. The concentrations and trend of concentrations for chromium in the N and N&P treatments were similar for the 123 microcosms, but higher than those from the control microcosm. In both treatment and control microcosms the chromium concentrations increased to relatively constant values. The concentration of chromium in the N treatment samples was higher after the three- week period. No change was found in the other samples after this period. The N treatment liberated the most chromium at site K22 followed by the control and then the N&P. Concentrations increased to relatively constant values. There were slight increases of chromium in the leachate in all three types of fluids after the three- week interaction period. The microcosms from 022 show that the concentrations and trend of chromium concentrations for the N and N&P treatments were also similar, but lower than those from control. Samples from this site were the only ones to show a decrease in chromium concentrations over time including after the three-week interaction time. These cores were composed of silty sand with very little organic matter and thus were very different compositionally from the rest of the cores, which included large percentage of organic matter. 79 The amount of chromium released from the microcosms does not appear to be related to the amount of chromium in the soil. Table 9 lists the concentration of chromium in soil samples taken from material that was removed from the ends of the microcosm cores during construction. The totals were determined using the method described in section 3.1.4. In many of the cores there was a large difference in the concentrations at the top and those at the bottom of the microcosm core. The highest concentrations were observed in the microcosms from 119, which also had the highest concentration of chromium in the exchange water. However, there are no other apparent relationships between the concentrations in the soil and the amount of chromium released from them, similar to the acid-rain microcosms. Table 9. A summary of the concentration of chromium in the microcosm soils Sample Location Cr Conc. Sample Location ‘ Cr Conc. in core 4mggg dry wt.) in core (m wt. 119 N Top 3067 K22 N Top 9665 Bottom 59957 Bottom 1667 119 N&P Top 3953 K22 N&P Top 8266 Bottom 62348 Bottom 16873 119 Control Top No Sample K22 Control Top 10434 Bottom 84988 Bottom No Sample P25 N Top 5084 123 N Top 21371 Bottom 4780 Bottom 6298 P25 N&P Top 8229 123 N&P Top 6637 Bottom 9395 Bottom 67336 P25 Control Top 2141 J 23 Control Top 9241 Bottom 4802 Bottom 38377 N23 N Top 4865 022 N Top 287 Bottom 9362 Bottom 720 N23 N&P Top 5322 022 N&P Top 564 Bottom 16064 Bottom 927 N23 Control Top 20187 022 Control Top 4107 Bottom 6731 Bottom 1520 80 The hypothesis driving the nutrient amended microcosms was that chromium concentrations in the pore water would increase if the degradation of soil organic matter increased. The additions of an alternative terminal electron acceptor and supplemental nutrients did appear to be utilized by the microbial community and should have allowed for greater degradation of organic matter. However, a clear relationship between the effluent chromium concentrations and the treatments applied is not apparent. The microcosm treatment that released the most chromium was usually a N or N&P treatment. This was true for all sites except 022, which as discussed earlier is composed to silty sand and is compositionally different from the rest of the microcosms. The fact that either the N or N&P treatments released the most chromium supports the hypothesis that increased microbial degradation of the soil organic matter may increase the dissolved chromium in the pore water. The inconsistent behavior may be a function of heterogeneity in the soil composition or microbial communities at each site, which result in different responses. It may also be that the time span or incubation period of these experiments did not allow enough time significantly alter the composition of the dissolved organic carbon. Although the fact that the N or N&P microcosms released the most chromium supports this hypothesis, the results are equivocal and can not be used as a predictive tool due to the lack of consistent trends. 81 IX. SUMMARY AND CONCLUSIONS 9.1 Summagy Chromium appears to be predominantly associated with two phases in these soils. The comparison of chromium and organic matter in the soil indicates that there is an association between chromium and soil organic matter. This is also supported by the sequential extraction data that show chromium is mainly associated with the moderately reducible (MR) and basic oxidizable (OX1) phases in these soils. The association of chromium with the OX1 phase is consistent with the relationship of chromium to organic matter. The proportion of chromium associated with the MR phase increased as the total amount of chromium in the soil increased. The increasing dominance of the MR extraction with increasing chromium concentrations may indicate that there is a limitation to the amount of chromium that can associate with natural organic matter. Considering the results of the sequential extraction data for chromium, the chemistry of the solutions used in the selective chemical attacks, and knowledge of the biogeochemistry of chromium, it is concluded that the dominant forms of chromium in the soils at this wetland are a Cr(OH)3 mineral/amorphous solid and chromium associated with soil organic matter. The concentrations of chromium in the surface and pore waters of this site are usually higher than would be expected by inorganic thermodynamic modeling. There was no measurable Cr(VI) observed in any of the samples collected. There was a positive correlation between chromium and dissolved organic carbon, which suggests that 82 chromium is associated with dissolved organic carbon in these waters. Solid phase extractions performed on the aqueous field samples showed that 96 percent of the chromium acted as anion, 12 percent of the chromium was associated with the hydrophobic organic fraction, and no measurable chromium acted as a cation. The results of the solid phase extractions show that aqueous chromium exists primarily as an anion in these waters. Since no Cr(VI) was observed in these samples, this anion is most probably a complex of chromium with DOC. In the pH range of these waters (near neutral) most of the functional groups on natural dissolved organic matter will have a negative charge. This characteristic supports the assumption that the chromium exists as a Cr(III)-DOC complex. There is an apparent contradiction between the anion and hydrophobic extraction data. The anion extraction indicates that 96 percent of the chromium is associated with an anionic species, however the hydrophobic extraction indicates that 12 percent of the chromium is associated with hydrophobic compounds. The contradiction arises from the fact that these two extractions combined exceed 100 percent, but if one takes into account the nature and complexity of natural organic matter the significance of this contradiction is diminished. It is completely plausible for organic compound to have both a hydrophobic component and a hydrophilic component (anionic). Another possibility is that the remaining 4 percent of the anionic extraction may be composed of neutral chromium species not associated with DOC, such as Cr(OH)3. However, the majority of the aqueous chromium exists as an anion, which is most likely a Cr(III)-DOC complex. The concentrations of chromium and pH values in the exchange water from the control soil samples in the microcosm studies were similar to those found in the native 83 soil pore waters. This indicates that the microcosms for this study reproduced field conditions and therefore it can be assumed that the microcosm experiments were adequate surrogates for field conditions. Chromium in the microcosm exchange water was found to be associated with dissolved organic matter, similar to field observations. Also, there was no measurable chromium that existed as a cation. The concentrations of chromium released from the treatment soils in the microcosm studies were also similar to those found in the soil pore waters. These observations suggest that chromium in the microcosm exchange fluid is behaving similarly to chromium in the field samples and therefore likely to be a Cr(III)- DOC complex. This also indicates that the treatments chosen for this study did not enhance the mobility of chromium above the conditions currently found at the site. The results of the microcosms involving the acid-rain simulations indicate that the buffering capacity of the soil neutralized the acid in the acid-rain solution. Thus, enhanced chromium mobility because of acidification did not take place, during the course of the experiment. The results of the microcosms involving acid rain also indicate that cyclic saturation and unsaturation of the soils may mobilize chromium. There appears to be no relationship between the amount of chromium in the effluent and the amount of chromium in the soil of a particular microcosm. There appears to be a relationship between the saturation history of a site and the amount of chromium released from a microcosm from that site. Microcosms from sites that were normally wet released the least amount of chromium, despite the fact that some cores contained much more chromium than other microcosms that released more chromium. Microcosms from sites that were variably or cyclically saturated released more chromium 84 than those continually saturated. The one site that was continually dry released the most chromium. There are several possible explanations for the behavior of chromium in these waters. One possible explanation for microcosm data is that chromium is being liberated as a by-product of microbial degradation of the natural organic matter. In this scenario the chromium is bound to organic matter which is being utilized by microorganisms and that chromium is released as a Cr(III)-DOC complex as by-product of that reaction. Another possible explanation for microcosm data is that chromium is being liberated as a Cr(III)-DOC complex that is the result of a chemical-equilibrium reaction. In this scenario chromium is coming into solution in effort to reach an equilibrium state. One possible solid phase for chromium would be Cr(OH)3, which may be dissolving to form inorganic species that can be complexed with DOC. The complexation of chromium with DOC would then allow for more Cr(OH)3 to dissolve. Further research is necessary to determine which of these processes are controlling chromium mobility. It is possible that both processes are occurring in these soils. The results of the microcosms involving changes in nutrient concentrations (i.e., phosphorus and nitrogen) indicate that chromium mobility in the soils will be affected by changing nutrient concentrations. However, a clear relationship between the effluent chromium concentrations and the treatments applied is not apparent. The microcosm treatment that released the most chromium was usually an N or N&P treatment. However, the fact that the N or N&P treatments consistently released more chromium supports the hypothesis that increased microbial degradation of the soil organic matter may increase the dissolved chromium in the pore water. The inconsistent behavior may 85 be a function of different limiting conditions or microbial communities at each site, which result in different responses. Although some of the data support this hypothesis, the results are equivocal and can not be used as a predictive tool due to the lack of consistent trends. The effects are complex and somewhat dependent on soil type. The N and the N&P treatments affected the soils differently. In turn, the soils responded differently to the treatment. The treatments did impact the dissolved organic carbon in solution as evidenced by a low correlation between chromium and dissolved organic carbon in the microcosms treated with 90 mg/L nitrate, but some of the data appeared to be correlated to a certain extent. However, chromium concentrations in the microcosm studies were not significantly greater than what was found in the soil pore waters. The release of chromium from the nutrient microcosms was similar to the release observed for the acid-rain microcosms. The relative amounts of chromium leached from the nutrient microcosms were similar to the relative amounts leached found in the acid- rain microcosm. In other words, those soils that tended to leach higher amounts of chromium in the acid-rain simulations were the same soils that leached the higher amounts of chromium the nutrient experiments. Also as in the case of the acid-rain microcosm experiments, the amount of chromium leached was not directly related to the total amount of chromium in the soils. 86 WM Inorganic and organic processes influence the fate and mobility of chromium in wetland environments. The primary hypotheses of this research were that chromium is associated with soil organic matter as Cr(III) and that dissolved chromium will be associated with dissolved organic matter. The results indicate that the solid forms of chromium in these environments will be either a chromium hydroxide or bound to the soil organic matter. Although both chromium hydroxides and soil organic matter appear to sequester chromium, chromium hydroxide is the dominant form at higher concentrations of chromium and so in that respect the hypothesis was not supported as far as the solids are concerned. The dissolved chromium concentrations are higher than would be predicted by inorganic thermodynamic calculations and the dissolved chromium is strongly associated with dissolved organic carbon, which supports the hypothesis. The relationship between chromium and DOC was observed in both the field and laboratory experiments, even though the DOC was not speciated. Aqueous chromium exists as an anion, which is probably a Cr(III)-DOC complex. It appears that the solubility of chromium is controlled by thermodynamic equilibrium processes involving both the solubility of Cr(OH)3am and the availability of organic ligands to complex with chromium. A secondary hypothesis was that the mobility of chromium in these soils is controlled by the stability of the organic matter to which it is bound. This hypothesis was tested with the microcosm experiments and is not strongly supported by the microcosm results or the speciation results. The sequential extraction data indicates that the organically bound chromium is not dominant form of chromium in the soil, which does 87 not support the hypothesis, however a small fraction can have a large influence on solubility. The results of the microcosm experiments show that the solubility of chromium may also be increased if the soils experience periods cyclic saturation and unsaturation. The results of the nutrient amended microcosms were equivocal, but indicated that there also may be an increased solubility of chromium if the degradation of soil organic matter is increased. The microcosm data showed trends in the chromium versus DOC and chromium versus the negatively charged or neutral chromium species that were similar to those observed for the field data. This indicates that the aqueous speciation of chromium in both the field and laboratory data is similar and that the processes controlling the solubility of chromium in both settings is the same. Therefore, it appears that the solubility of chromium is more likely to be controlled by the availability of organic ligands in solution than the stability of the organic matter to which it may be bound. 88 REFERENCES Allison 1.D., D.S. Brown, and KJ. Novo-Gradac. 1991. MINTEOAZ. A geochemicgl, assessment data base and test cases for environmental systems; Version 3.0 user’s manual. Report EPA/600/3-9ll-21. Athens, GA: US. EPA. American Public Health Association (APHA), American Water Works Association (AWWA), Water Pollution Control Federation (WPCF). 1992. Standard Meth_od_s for the examination of water and wastewater, 18th Edition. A.E. Greenberg, L.S. Clesceri, and AD. Eaton (Eds) APHA, AWWA, and WPCF Washington DC. American Public Health Association (APHA), American Water Works Association (AWWA), Water Pollution Control Federation (WPCF). 1998. Standard Methods for the examination of water and wastewager. 20th Edition. L.S. Clesceri A.E. Greenberg, and AD. Eaton (Eds). APHA, AWWA, and WPCF Washington DC. Armienta M.A., and A. Quere. 1995. Hydrogeochemical behavior of chromium in the unsaturated zone and in the aquifer of Leon Valley, Mexico. Water, Air and Soil Pollution, 84: 11-29. Asikainen 1.M. and N .P. Nikolaidis 1994. Sequential extraction of chromium from contaminated aquifer sediments. Ground Water Monitoring and Remediation 14: 1 85-191 . Atlas R.M., and R. Bartha. 1993. Microbial Ecology Fundamentals and Applications. Benjamin/Cummings Publishing Company, New York, 563pp. Baes CF, and RE. Mesmer. 1976. The Hydrolysis of Cations. John Wiley and Sons, New York. Ball 1.W., and Nordstrom D.K. 1991. User’s manual for WATEO4F. with revi_s_;et_l thermodmamic data base and test cases for calculating spgciation of major, trace and redox elements in natural waters. U.S. Geol. Surv., Open-Fine Report 91- 183. Barbosa A.E., and T. Hvitved-Jacobsen. 1999. Highway runoff and potential of removal of heavy metals in an infiltration pond in Portugal. Science of the Total Environment, 235: 151-159. Bartlett R. and 1.M. Kimble. 1976a. Behavior of chromium in soils: 1. Trivalent forms. Journal of Environmental Quality 5: 379-383. 89 Bartlett R. and 1.M. Kimble. 1976b. Behavior of chromium in soils: 1. Hexavalent forms. Journal of Environmental Quality 5: 383—386. Bartlett R. 1. and B. R. James. 1979. Behavior of chromium in soils: III. Oxidation. Journal of Environmental Quality 8: 31-35. Bartlett R. 1. and B. R. James. 1988. Mobility and bioavailability of chromium in soils, In J. O. Nriagu and E. Nieboer, Eds. Chromium in the natural and human environments. New York: Wiley and Sons, pp. 267-303. Belzile N., P. Lecomte, and A. Tessier. 1989. Testing readsorption of trace elements during partial chemical extractions of bottom sediments. Environmental Science and Technology, 23: 1015-1020. Blowes D.W., C.1. Ptacek, and J.L. Jambor. 1997. In-Situ remediation of Cr(VI)- contaminated groundwater using permeable reactive walls: Laboratory Studies. Environmental Science and Technology, 31(12): 3348-3357. Buerge 1.1., and SJ. Hug. 1998. Influence of organic ligands on chromium(VI) reduction by iron(II). Environmental Science and Technology 32: 2092-2099. Cannelton Industries Incorporated. 1995. Preliminary Design Report. Submitted to US. EPA Region V, Report CANN 95-4. Cannelton Industries Incorporated. 1992. Feasibility Study of the Cannelton Industries Site, Sault Ste. Marie, Michigan. Submitted to US. EPA Region V. Carignan, R., F. Rapin, and A. Tessier. 1985 Sediment porewater sampling for metal analysis: A comparison of techniques. Geochimica et Cosmochimica Acta. 49, 2493-2497. Chao T.T. (1984) Use of partial dissolution techniques in geochemical exploration. Journal of Geochemical Exploration 20: 101-135. Cifuentes F. R., W. C. Lindemann, and L. L. Barton. 1996. Chromium sorption and reduction in soil with implications to bioremediation. Soil Science, 161: 233-241. Cram 1.M., and DJ. Cram. 1978. The Essence of Organic Chemist_ry. Addison-Wesley Publishing Company, Reading, MA, 456pp. Davis A., 1.H. Kempton A. Nicholson and B. Yare. 1994. Groundwater transport of arsenic and chromium at a historical tannery. Wobum, Massachusetts, U.S.A. Applied Geochemistry, 9: 569-582. Davis A., and R.L. Olsen. 1995. The geochemistry of chromium migration and remediation in the subsurface. Ground Water, 33(5): 759-768. 90 Davis 1.A. and 1.0. Leckie. 1980. Surface ionization and complexation at the oxide/water interface. 3. Adsorption of anions. Journal of Colliod Interface Science, 74: 32-43. Davis J.C. 1986. flitistics and Data Analysis in Geology, 2'“I Edition. John Wiley and Sons, New York, 646p. Dolan M. E. and P. L. McCarty. 1995. Small-column microcosm for assessing methane- stimulated vinyl chloride transformation in aquifer samples. Environmental Science Technology, 29: 1892-1897. Donat J.R., R.A. Kango, and AS. Gordon. 1997. Evaluation of immobilized metal affinity chromatography (IMAC) for isolation and recovery of strong copper- complexing ligands from marine waters. Marine Chemistry, 57: 1-10. Eary LE. and D. Rai. 1987. Kinetics of chromium(III) oxidation to chromium(VI) by reaction with manganese dioxides. Environmental Science Technology, 21:1187- 1 193. Eary LE. and D. Rai. 1988. Chromate removal from aqueous wastes by reduction with ferrous iron. Environmental Science Technology, 22: 972-977. Eary LE. and D. Raj. 1989. Kinetics of chromate reduction by ferrous ions derived from hematite and biotite as 25°C. American Journal of Science, 289: 180-213. Elbaz-Poulichet F., G. Cauwet, D.M. Guan, D. Faguet, R. Barlow, R.F.C. Mantoura. 1994. C18 Sep-Pak extractable trace metals from the Gulf of Lions. Marine Chemistry, 46: 67-75. Ellis R.J., 1999. Heayy Metal Partitioning in Soils of Variable Texture and Redox Potential: An evaluation of Sequential Chemical Extractions. Master’s Thesis, Michigan State University, 194p. Fendorf S.E., R.J. Zasoski, and R.G. Burau. 1993. Competing metal ion influences on Cr(III) oxidation by B-MnOZ. Soil Science Society of America‘Journal, 57: 1508- 1515. Fendorf SE, 1995. Surface reactions of chromium in soils and waters. Geoderma, 67: 55-71. Fiedler H.D., J.F. Lopez-Sanchez, R. Rubio, G. Rauret, Ph. Quevauviller, A.M. Ure, and H. Muntau. 1994. Study of the stability of extractable trace metal contents in a river sediment using sequential extraction. Analyst 119: 1109-1114. 91 Fishman MS, and LC. Friedman, Eds. 1989. Methods for determination of inorganic substances in water and fluvipl sediments. US. Geological Survey, TWRI Book 5, Chapter A1, 626 pp. Galloway J.N., G.E. Likens, and ES. Edgerton, 1976. Acid precipitation in the northeastern United States: pH and acidity. Science, 194: 722-724 Gephart C]. 1982. Relative immrtance of iron-oxide. manganese-oxide. and organic material on the adsorption of chromium in natural water sediments systems. Master’s Thesis, Michigan State University, 125p. Gruebel K.A., 1.A. Davis, and 1.0. Leckie. 1988. The feasibility of using sequential extraction techniques for arsenic and selenium in soils and sediments. Soil Science Society of America Journal, 52: 390-397. Hanson A.T., B. Dwyer, Z.A. Samani, and D. York. 1993. Remediation of chromium- containing soils by heap leaching: Column study. Journal of Environmental Engineering, 119(5): 825-841. Hesslein RH. 1976. An in situ sampler for close interval pore water studies. Limnology and Oceanograghy, 21: 912-914. Hewitt A.D., and CM. Reynolds. 1990. Dissolution of metals from soils and sediments with a microwave-nitric digestion technique. Atomic Spectroscopy, 11: 187-192. James BR. and R]. Bartlett. 1983a. Behavior of chromium in soils: V. Fate of organically complexed Cr(III) added to soil. Journal of Environmental Quality, 12: 169-172. James BR. and R]. Bartlett. 1983b. Behavior of chromium in soils: VI. Interactions between oxidation-reduction and organic complexation. Journal of Environmental Quality, 12: 173-176. James BR. and R.J. Bartlett. 1983c. Behavior of chromium in soils: VII. Adsorption and reduction of hexavalent forms. Journal of Environmental Quality, 12: 177-181. Jeong S. 1994. Spatial and Temmral Variations of Chromium in Sediments of the Great Lakes. Master’s Thesis, Michigan State University, 103p. Kaplan D.I., P.M. Bertsch, and DC. Adriano. 1994. Facilitated transport of contaminant metals through an acidified aquifer. Ground Water, 33(5): 708-717. Kent D.B., 1.A. Davis, L.C.D. Anderson, and BA. Rea. 1994. Transport of chromium and selemium in the suboxic xone of a shallow aquifer: Influence of redox and adsorption reactions. Water Resources Research, 30(4): 1099-1114. 92 Kotas 1., and Z. Stasicka. 2000. Chromium occurrence in the environment and methods of its speciation. Environmental Pollution, 107: 263-283. Krajnc M., J. Stupar, and S. Milicev. 1995. Characterization of chromium and copper complexes with fulvic acids isolated from soils in Slovenia. The Science of the Total Environment, 159: 23-31. Leenheer 1.A., 1981. Comprehensive approach to preparative isolation and fractionation of dissolved organic carbon from natural waters and wastewaters. Environmental Science and Technology, 15: 578-587. Llovera S., R. Bonet, M.D. Simon-Pujol, F. Congregado. 1993. Chromate reduction by resting cells of Agrobacterium radiobacter BPS-916. Applied and Environmental Microbiology 59: 3516-3518. Long, D.T., N.E. Fegan, W.B. Lyons, M.E. Hines, P.G. Macumber, and A. Giblin, 1992. Geochemistry of acid-brines: Lake Tyrrell, Australia. Chemical Geology, 96: 33- 52. Losi M. E., C. Amrhein, and W. T. Frankenberger, Jr. 1994a. Environmental biochemistry of chromium. Reviews of Environmental Contamination and Toxicology, 136: 91-121. Losi M. E., C. Amrhein, and W. T. Frankenberger, Jr. 1994b. Factors affecting chemical and biological reduction of hexavalent chromium in soil. Reviews of Environmental Contamination and Toxicology, 13: 1727-1735. Lovley D.R., F.H. Chapelle, and LC. Woodward. 1994. Use of dissolved H2 concentrations to determine distribution of microbially catalyzed redox reactions in anoxic groundwater. Environmental Science and Technology 28: 1205-1210. Lovley DR. and S. Goodwin. 1988. Hydrogen concentrations as an indicator of the predominant terminal electron-accepting reactions in aquatic sediments. Geochimica et Cosmochimica Acta 52: 2993-3003. Makos 1.D., and DC. Hmcir. 1995. Chemistry of Cr(VI) in a constructed wetland. Environmental Science and Technology, 29: 2414-2419. Martin 1.M., P. Nirel, and A.J. Thomas. 1987. Sequential extraction techniques: promises and problems. Marine Chemistry 22: 313-341. Martin 1.M., W.W. Huang, Y.Y. Yoon. 1994. Level and fate of trace metals in the lagoon of Venice (Italy). Marine Chemistry 46: 371-386. 93 Masscheleyn P.H., J.H. Pardue, R.D. Delaune, and W.H. Patrick. 1992. Chromium redox chemistry in a lower Mississippi Valley bottomland hardwood wetland. Environmental Science and Technology, 26: 1217-1226. Makos J. D. and D. C. Hrncir. 1995. Chemistry of Cr(VI) in a constructed wetland. Environmental Science and Technology, 29: 2414-2419. Mattuck R., and NR Nikolaidis. 1996. Chromium mobility in fresh water wetlands. Journal of Contaminant Hydrology, 23: 213-232. McBride, MB. 1994. Environmental Chemisg of Soils. Oxford University Press, New York, New York, 406pp. McKee 1.D., T.P. Wilson, D.T. Long, and RM. Owen. 1989. Geochemical partitioning of Pb, Zn, Cu, Fe, and Mn across the sediment-water interface in large lakes. Journal of Great Lakes Research 15(1): 46-5 8. Milacic R., and J. Stupar. 1995. Fractionation and Oxidation of chromium in tannery waste- and sewage-amended soils. Environmental Science and Technology, 29: 506-5 14. Mills G.L. and JG. Quinn. 1981. Isolation of dissolved organic matter and copper organic complexes from estuarine waters using reverse-phase liquid chromatography. Marine Chemistry 10: 93-102. Mills G.L., A.K. Hanson and JG. Quinn. 1982. Chemical studies of copper-organic complexes isolated from estuarine waters using C18 reverse-phase liquid chromatography. Marine Chemistry 11: 355-377. Mills G.L. and JG. Quinn. 1984. Dissolved copper and copper-organic complexes in the N arrasansett Bay Estuary. Marine Chemistry 15: 151-172. Mills G.L., E. McFadden and JG. Quinn. 1987. Chromatographic studies of dissolved organic matter and copper-organic complexes isolated from estuarine waters. Marine Chemistry 20: 313-325. Mills G.L., G.S. Douglas, and JG. Quinn. 1989. Dissolved organic copper isolated by C18 reverse-phase extraction in anoxic basin located in the Pettaquamscutt River Estuary. Marine Chemistry 26: 277-288. NCASI 1985. Groundwater Qualig Data Analysis. National Council of the Pm Industry for Airfiand Stream Improvement. Technical Bulletin No. 462, 197p. NOAA 1993. Local Climatological Data: Annual Summary with Comparative Data, Sault Ste. Marie, MI. National Oceanic and Atmospheric Administration, ISSN 0198-2672. 94 O’Flaherty F., W.T. Roddy, and RM. Lollar. (editors). 1958. The Chemist_ry and Technology of Leather: Volume II--Types Tannages. Rienhold Publishing Corporation, New York. Pai S.-C., T.H. Fang, C.-T.A. Chen, K.-L Jeng,. 1990. A low contamination Chelex-100 technique for shipboard pre-concentration of heavy metals in seawater. Marine Chemistry, 29: 295-306. Palmer CD. and R.W. Puls. 1994. Natural Attenuation of Hexavalent Chromium in Ground Water and Soils. US. EPA, EPA/540/S-94/505. Papp C.S.E., L.H. Filipek, and KS. Smith. 1991. Selectivity and effectiveness of extractants used to release metals associated with organic matter. Applied Geochemistry 6: 349-353. Parkhurst BL. 1995. User’s guide to PREEOC -- a computer proggam for sgciation, reaction-path, advective-transmrt, and inverse geochemical calulations. U.S. Geol. Surv., Water-Resources Investigations Report, 954227. Paulson A.J., H.C. Curl, and J.F. Gendron. 1994. Partitioning of Cu in estuarine waters, 1. Partitioning in a poisoned system. Marine Chemistry 45: 67-80. Polprasert C., N.P. Dan, and N. Thayalakumaran. 1996. Application of constructed wetlands to treat some toxic wastewaters under tropical conditions. Water Science and Technology, 34(11): 165-171. Powell R.M., R.W. Puls, S.K. Hightower, and D.S. Sabatini. 1995. Coupled iron corrosion and chromate reduction: Mechanisms for subsurface remediation. Environmental Science and Technology, 29(8): 1913-1922. Rai D., B.M. Sass, and D.A. Moore. 1987. Chromium(III) hydrolysis constants and solubility of chromium(lII) hydroxide. Inorganic Chemistry, 26: 345-349. Rai D. L. E. Eary, and J. M. Zachara. 1989. Environmental chemistry of chromium. Science of the Total Environment, 89:15-23. Rapin R., A. Tessier, P.G.C. Campbell, and R. Carignan. 1986. Potential artifacts in the determination of metal partitioning in sediments be a sequential extraction procedure. Environmental Science and Technology, 20: 836-840. Rauret G., R. Rubio, and J.F. Lopez-Sanchez. 1989. Optimization to Tessier procedure for metal solid speciation in liver sediments. International Journal of Environmental Analytical Chemistry, 36: 69-83. 95 Rezabek DH. 1988. The chemical behavior of heayy metals at the wager-sediment interface of selected streams in Mg'ne szsed on ternary partitioning diagpa_ms. Master’s Thesis, Michigan State University, 130p. Richard EC, and AC. Bourg. 1994. Aqueous geochemistry of chromium: A review. Water Research, 25: 807-816. Roberts P. V., L. Semprini, G. D. Hopkins, D. Grbic-Galic, P. L McCarty, and M. Reinhard. 1989. In situ aquifer restoration of chlorinated aliphatics by methanotrophic bacteria. EPA Report 600/2-89/033. US. EPA: Washington, DC. Saleh F.Y., T.P. Parkerton, R.V. Lewis, J.H. Huang, and KL. Dickson. 1989. Kinetics of chromium transformations in the environment. Science of the Total Environment, 86: 25-41. Sass B.M. and D. Rai. 1987. Solubility of amorphous chromium(III)-iron(IIl) hydroxide solution solutions. Inorganic Chemistry, 26: 2228-2232. Scholes L., R.B.E. Shutes, D.M. Revitt, M. Forshaw, and D. Purchase. 1998. The treatment of metals in urban runoff by constructed wetlands. Science of the Total Environment, 214: 211-219. Schroeder DC. and GP. Lee. 1975. Potential transformations of chromium in natural waters. Water, Air Soil Pollution, 4: 355-365. Schulmeister MK. 1993. A study of the first transititfl elem_ents as a ggoup in a section of the New Albany Shale (Devonign-Mississippian) of Southern Indiana. Master’s Thesis, Michigan State University, 99p. Shen H. and Y. Wang. 1994. Biological reduction of chromium be E. coli. Journal of Environmental Engineering, 120: 560-572. Shulte, E.E, Kaufman, C., and Peters, J .B. (1991) The influence of sample size and heating time on soil weight loss. Communications in Soils Science and Plant Analysis. 22:159-168. Srnilie R.H., K. Hunter, and M. Loutit. 1981. Reduction of chromium(VI) by bacterially produced hydrogen sulfide in a marine environment. Water Research, 15: 1351- 1354. Takacs MJ. 1988. The oxidation of chromium by ma_ng_anese oxide: the rgture 3&4 controls of the wagon. Master’s Thesis, Michigan State University, 271p. Tessier A.P., G.C. Campbell, and M. Bisson 1979. Sequential extraction procedure for the speciation of particulate trace metals. Analytical Chemistry, 51: 844-850. 96 Tessier A.P., D. Fortin, N. Belzile, R.R. DeVitre, and G.G. Leppard. 1996. Metal sorption to diagenetic iron and manganese oxyhydroxides and associated organic matter: Narrowing the gap between field and laboratory measurements. Geochimica et Cosmochimica Acta 60(3): 387-404. Tipping E., N.B. Hetherington, 1. Hilton, D.W. Thompson, E. Bowles, and J. Hamilton- Taylor. 1985. Artifacts in the use of selective chemical extraction to determine distributions of metals between oxides of manganese and iron. Anal. Chem. 57: 1944-1946. US. EPA. 1996. Ecological effects test guidelines: OPPTS 850.2450 Terrestrial (soil- core) microcosm test. EPA Report 712-C-96-143. US. EPA: Washington, DC. Walsh A.R., and J. O’Halloran. 1996a. Chromium speciation in tannery effluent - I. An assessment of techniques and the role of organic Cr(III) complexes. Water Research, 30(10): 2393-2400. Walsh A.R., and J. O’Halloran. 1996b. Chromium speciation in tannery effluent — II. Speciation in the effluent and in a receiving estuary. Water Research, 30(10): 2393-2400. White AF. and M.F. Hochella. 1989. Electron transfer mechanisms associated with the surface oxidation and dissolution magnetite and ilmentite. Proceedings from the 6th International Symposium on Water-Rock Interaction: 765-768. Wiedemeier T. H., J. T. Wilson, D. H. Kampbell, R. N. Miller, and J. E. Hansen. 1995. Technical protocol for implementing intrinsic remediation with long-terrn monitoring for natural attenuation of fuel contamination dissolved in groundwater. San Antonio, TX: US. Air Force Center for Environmental Excellence. Wittebrodt P. R., and C. D. Palmer. 1996a. Reduction of Cr(VI) in the presence of excesss soil fulvic acid. Environmental Science and Technology 29: 255-263. Wittebrodt P. R., and C. D. Palmer. 1996b. Effect of temperature, ionic strength, background electrolytes, and Fe(II) on the reduction of hexavalent chromium by soil humic substances. Environmental Science and Technology 30: 2470-2477. Yong R.N., R. Galvez-Clouthier, and Y. Phadungchewit. 1993. Selective sequential extraction analysis of heavy-metal retention in soil. Canadian Geotechnical Journal, 30: 834-847. Zachara 1.M., C.C. Ainsworth, C.E. Cowan, and CT. Resch. 1989. Adsorption of chromate by subsurface soil horizons. Soil Science Society of America Journal, 53: 41 8-428. 97 Zhang H., and R.J. Bartlett. 1999. Li ght-induced oxidation of aqueous chromium(III) in the presence of iron (1H). Environmental Science and Technology. 33: 588-594. 98 MES. 99 So an: .83 .2: :38: as: 3:: use: 8235.. emu? a 8:58 2 m use :8 as am: and: 6:8 5:: :8 S 558» E65 >68 :85 o.m-n.~ Ba 5:... 56:. 83 an: 23 :8: 25 so: Ba 5:... :32: ea: :8 as, :5... :8 :32: 83 3-3 6:8 .27. E65 :56 8 x85 noted :2: 60683 a 8 fl 3% 2m 6:3 .05 5H n.m.o.m 6:3 5:: :5 9 .08.. 9 868» 6:8 5:: E65 5w: 55% earn; e5... 5:... use: a»: as: 2.3 6:3 .03 E65 .98: #86 3 E65 :85 o._-n.o 6:3 5:: 865 x59 n.o.o.o :2: 60683 a 8 :35 8 mm 8mm :m 6:8 5:: :3. n.m.o.m es 9 :65 a»: as: 3-2 :38: a»: be: o. :32: in: :3: 2.3 6:8 Duo. E65 :86 :05 E65 7.8 :59 Qde 6:9. 5:: E65 .08: x50 ndéd 8:5 6:8 58 62260 5:80 mm 28 516: 88.: 8:08 8:5 :6 E65 .23 88:8 85m :05 6:3 5:: 8d. n.m.o.m 6:5. ban :8 9 36:8 6:3 3:: 58305 .023 catn— eea 5% o:58 ease: as: 2.3 8965 .50: 06:5 58:65 .03: 9 86% 6:8 5:: E65 Ems o._-w.o Ea 5:... :32: a»: 9 sea» .83 :5 52832: as: 3.3. see: Sousa :5 e825: 8:: 8 as... :8 Edema 23“ 6:3 5:: :8 bed: 8 869% 6:3 .05. E65 8:608 beam o.m-n._ 6:8 5:: 565 58:36 .33— 0:: 6:3. .37. E65 5.855 38% @700 650 683 6:: 808 5:3 6:8 5:: E65 #89 noted 5389588 :23 628 a 8 9825 mm 6:3 5:: E65 8838 58m n.m-o.m Ba :8 :32: 53:2: as: 32 6:8 5:» E65 x56 9 868» 6:3. 5:» E65 8:608 38m 0:: 6:8 3:: E65 8:608 .08.. o. 868w .302 55 6:8 .03 E65 x59 QTnd 6:3 3:: E65 8:608 .32 9 868m .808 .23 6:3 bi E65 85 w.o.o.o 53396:: 55 588 6836.5: mm =8 5 noun—v.98: Goo: .5885 6:33 0388 5 853.38: a cam 100 :8 5::: 05 6:: :38: Q8: 0:”:5a :305 5::: 5:9 :60: 00:: 6:: 6:8 5:: :305 5::: 5:9 E65 5::: 5:6 0: 858m 6::: :305 5:9 6::: 5:: :305 5:9 :8: 606003 : :0 0:60 05 :0 8::9 o—U 9:... 9:: 9:3 8 :5 8m 6:8 5:: :8 5w: 8 86:3 6::: 5:: :305 5:3— 6:8 5:: :305 5::: 0: 868m 6::: 5:: :305 5::: 5:9 :60: 5:3 6::: 5:: :305 5::: 9 868» 6::: 5:: :305 5:9 :8: 5:3 9:: 5:. 98.: :0:: 63:05: :0 069 mu 9:: 5:: :s 2%: 6::: 0:: 5:3 5: :8 5w: 0: :06::w 6::: 5:: :8 5::: 6::: 5:: :305 5::: 5:9 6::: 5:: :305 5::: 0: 858: 6:8 5:: :305 55..— 6::: 5:: :305 5w: 8 :06::m :0508 03: :25: 8 6::: 5:: :305 56.589 82506:: 5»: 5:3 ::0:0.: 600365: 60 6::: 5:: :8 5::: :05 6:8 0:::00 5::: :8 6::: 5:: :305 5::: :09. a: 5:3 :5: s: :2: 8:: 9 88:: 9:: 8:: 5:: 58:: .9: 9282 80:08 850 6003 6:: :60: 6::: 5:: :8 8:508 5::: 5538 80:08 :60: 6::: 5:: :8 5::: 0: 868» 6::: 5:: :305 5:9 350 6003 6:: :60: 6::: 5:: :305 5:9 0:: ::0: 8:: 6:: 808 :80: 5::: 6688? 08:8 53 80:8 600365: :0 :93 8:: :39: :8: 6::: :305 5::: 8:508 0: 869% 6::: 5:: :305 5::: 8:502 6::: 5:: :305 5::: 8:502 :60: 5:3 6::: 5:: 86:9 80:08 :60: 6::: 5:: :305 5:9 80:0: 6003 6::: : 5 880:0 ::8m N80 5:: :305 5::: 5:6 0: :8 5::: 6::: 5:: :8 5::: 9:: 5: :3 :3: :8 6::: :8 5::: : 0:8 868» :305 5:9 8:88: 08:80 .:0 :6— 5:3 :6::: 5:: 0.0855305 5:9 8: 8:83 :9 ::: 6:: 6::: 080: 5:3 :8: :305 5:9 5:: 5:3 :305 5:6 0: 5:: :0 80:3 ::: :305 5»: 0: :06::» :8 560:0 6::: .8830 >8:0:0 5:3 88:00 3:8 48:88 :305 5:9 V. . . . 6 . w. ..‘ .. ., . . . 1:. 1.9.. q..,.:.:.w..mx¢wmfiwwuf a... ,. ...::1.in .1. L..£.,...3J. Q)... \h. aw . .,......1. . 5......1 “1.,—w L . {Viwnwufl‘oml . .. .. 1 .. L .. .LH..:.. ‘ J. .\.W~L...1~.J»,L2 In Ll: :305 8560: ::_:w:: - 0:0 36.00: 60:08 53 6::: 5:: :305 5:9 29 101 I! I . 5 . .6. .,. .. ... ... a. vi ....... 3.... .. ..V‘r_rv. . 4 .. ., v.11 r:‘.. . .lv A: .‘A ,‘i‘ .. x. .:r : , z» 2 $95. ‘ 4.... A E5. sm..._....,... . .. w. 1 , {Muir 1. .i... ,eravumflflne. . .u'. . ...... .fi.’ tknnuogfl mflhflsahflflauhr M., . .u.~. W:.. .I ....r\..fl AF... 1.”.anqmmflbn.r u» ‘ , I! i l 9.8 5:8 56.5 is. o. 985 .853 58¢ 213 no.3 3683 ms 4E5... 9.5 .03 a. 0388 - .65 9... 9.8 Dam 56.5 Ego. :5 x55 m.m.o.n .65 5.3 9.8 5:... :5 5w: 3 89...» 9.8 ban :3 5m: 53% c.m-n.. Eu 5.3 Ba 6.... as. 2 888 23 b... as be... 3.6.. 2.9. a... as an... 3-3 9.8 5:8 :5 852.. 55 89.3 .98 5:... 56.5 in“. 8:65 So. no... ndéd marge? :98 a 5 onto 05 no 895 :Q 9.8 3:8 :5 8:53. n.m.o.m 28 5..“ 5. 5.2.3. 6.3.. Ba 6..“ 52.. 5.2.3. 2.6.. 9.8 5:... :8 .08.... o. 89...» 9.8 .03 565 3.60 QTnd 9.3. 6.... 5,65 .35 3.6... R. 2.3 6..” .5 2...: 02.8 826.8 .9.8 5:... :8 5w: 9 89...» 98 5:8 565 .933 o.m-m._ 9.8 5:8 56.5 .023 “To.— 9.8 .3... 56.5 bus. 555 o. 82.8» 9.8 5:... 565 2.»...— QTnd 9.8 5:... 56.5 fian— ndéd 8.. 2.5 a .3: do... 83% some bin mm :9... 233 oz 8.2: :93 2.83 oz 6.3.. :23 29.8 oz 2.6.. :33 29.8 oz 3.2. 38. 5.3 28 a... 56... .35 3...... .83. 83.5.. as... a s 9.82.0 20 Baggy 3.580 83.85.385.28 5:8 .5... m.m.o.m 23 b... .5... 6.3.. 9.8 5:8 .5... WI... 28 Eu 5. 2 «58.» 28 a...“ 5o... 6.5. .5... 2:85 3-3 9.8 .28 .565 9.3 .59.. 6.530 n.o.c.o 8.... some 5880 EU .35 5.3 9.8 5:8 :3 x95 n.m.o.m 562. 5.3 >50 5.53.8... 9.8 .05 :8 9 mafia.» 9.8 .03 56.5 bmam o.m-n.. 9.8 Dan 565 .983— 979. 9.8 5.8 56.5 .08.: 9.89 QTnd 38. >58 5.3 9.8 5:8 xofim n.o.o.o A.39.. 0:. 5 8. 8mm 20 565 band n.m.o.m . 8 102 000—0..- 0.00.0m 02 0m.0.m .220 3.30 0.0-0.. 005500 9.0 9.8 8.000 565 .003. 0.0.. 9.8 8.000 56.5 0009 0.700 9.8 8.000 56.5 .00... 0. 56.5 0000 00.0.0 000 0000.00 0 00 0»00 0:. .0 0.0 000003 08 .0500 0» 0. 050.... .090... 000003 0 5.. -0N 09: .00 0000... 50.0 .000 565 :5. 0050.. 50.0 5.00 :00.» 50.» 000Q 0N0. 09: 00 0000... $0.0 .000 565 5.3 005:. 50.0 .900 :00.» >0.» 000Q 0.0.. 00... .0 88... .000 0.... :30... 5.3 020... 0% 0... 08.0 0:0 0.00 0.8.0 0% 0.0 08.52» .00 .85... oz .3. 83000008 8.08 .9. 20 580 0.0.0.0 80 8083 0.0 00:0. 0.908 02 0m.0.m .000 005. 9.0 03. 0003.0: 0.03 00.005 .00: 9.0 000.: :5. =8 000.0 06-0. 9.8 8.000 0.5».0 :0... 0.0Q 0.0.. 9.8 8.000 0.0090 :0... 095 0. 700 805.095 9.8 8.000 00.0»..0 :00 000D 00.0.0 0.0.0000. 80.0.0 00030.0: 00 0»0m 3m 00.0 9.0 9.8 80000530500. 0. 00% 05.300.500.- 050... 005. .00... 00.06 .50..» 0. 0.00: 00:. 50.0 00 000.50 0. 0000..» .50..» 0.003 8.000% 0. m0. .380 56.5 0.00 2.0.. .980 :30... 0.00 0.8.0 000:».650 0.00.. :50.» 9.0 9.8 8.000 0. 0000.» 9.8 8.000 56.5 0009 0000 00.0 000003 3Q 00.0 9.0 0:0 :0. 0.000 0. 0000..» 00550.. 9.0 50.0 .000 \3 0.00000... .0000 0m-0.m 8302. 05 00."v 0.0 5.3 .0032. 08.. 0.0-0.. 83%.. 5.3 0.0022. 03.. 2.0.. .0030... .000 .0080... 0.00.. 8035093 9.8 8.000 0305 0009 0.700 80.0.0 00030.0: 5 5.0.000 Ca 05... 0.0 as 00%. 0.00.0 0:3. 0... as 2.0.. 9:. 8.0.0 as 0.3. 0.0-0.. 0.8 0.... as 000. 2.0.. .50..» 9.0 9.8 .000 :0. .00.... 0. 0000..» 9.8 .000 030.5 0.0.00 05... 0.0 5.65 0.00 0.0.0.0 020. 083.5. a. 05500 0.0 9.8 .000 00. 0.0.002 0m.0.m 0.8 0.0 as 03.. 0.0-0.. 9.8 .008 565 5.03. 0.0.. 56.5 00.0.... 0...: »0..00.-.».. 56.5 0.009 0....00 ....._... hrmm ritwufim. 9:. $0... 3W. . 3: 0 And. 0. 3. 0. H .4.-Ruwlmdfl. .vJ—.-»- .‘u. ....__.-_-.__.L-.-_....,0m.: 103 ||.|J . .... r,- _ 1.0..... ....-..u ...-.34.... . . . ......m‘fi ...... 2......L. .EH’LVI rgr 4.13%: hunk.“ .1 .115? How. . ...-.03.. 0.5.5030M1xu. :..-2?. .. .... . -.. D £3. 3...... .11. \r... .... .. :01... ...». ...-...»..0093 313;... .. 0. .- 0.00. :.-; u.- uL-y.t"£4“rrmrlii&§_whh3 1. .... r 0...... 0.0 .8... 0.0.0.0 0...0..... ..s ... 8.0.0.8.... 0.0 ..0 0.... 0..0 ....0 .20 0.00... 0...... ...... .00.. e... 0..00.0 .08.. 0.0.0.0 ...0 000 00.0 :..3 .20 ....000. 00.0.0 ...5 .mNm 0.... 0..00.0 .0890 0.0.0. ...0 000 00.0 ....3 .20 .0000... 40.00. .05 .mm... 0.... 0..00.0 0.00.0 0.0.. 0:0 6:0 hflu 5.3 :0 >500... .38... .00> .mNm 0.5 0:080 .38.“ 6.700 ...0 9.0 00.0 :..3 SO .0000... 40.0.0 .05 .mm... 0.... 0..00.0 0.03. 000.0 .303 0000.00 0.000 ....3 0..0000 0. 0.6 00.... 0.08.0 0 ...... 0.0... 0.0 .8... 0.0.0.0 ...... ... so. .00.... 0.08.0 ...... 0...... 0.0 .8... ... 050 ..0 000 0.08.0 0.0-0.. 050 ..0 000 0.08.0 0...0.. 0000 ...0 .00.» :..-.0080 0.00 00.000 .800. 000 0003 00.00 008 .000 .00.» 00.000.» 0.0. »0.00.» 9.00 0.20 030... 0..0D 000.0 80.0.. ..0 0»00 00 00.030 0000.0 0.0 050 0.0 .... 0.... 0.0-0.0 0...... 0.0 ..s 0.... 0.0-0.. 00.0. 0.0 ..s 0.... 0...0.. 00.0 0.0 .0. 0.... 0..-0.0 ..0: 9.0 .00.; 030.0 000. 0. 0000.» 008 0...... 030... ...00 0000.00 9.0. .0 .00... 00.0.0 ...: 0 .0 00. 0... .0 ......» =0...m .m... 0...... 0.0 ..s 0.0... 0.00.0 0...... 0.0 0... 0.0.. o. 0.0. 0.0 5.6... 0...... 0.0.0.. 050 0.0 .50... 00.... 0...0.. 0.8. .0 so. 5.3 .....0 .56... 0.... .00 300 0.00. »0.00.00. 3.0.00. 0.00».0 .0000000 ....3 008 030... ...09 00.0.0 0»0.. 0 ..0 00. .0 00.0 000003 0... 0.0.08 .03 .008 00. 0.03. 0m.0.m 0...... 0.0 5.. 0...... 0.0.0.. .....0 0.0 =30... ...... 0. ..0.. ..0 .50... .....0 0..-0.0 00.0 000.» .0 0080.0 ....3 008 0.00 030.0. 0.05 000.0 003:0; 00.0 0000 000.0 m... 0...... .0. 0.40.. 2.... 0.0-0.0 05. .0. 0.0.. 3... 800.0 ..0 000.0 .... 0.... 0.0... 0.0-0.. ..0 0...... .0. 0...... 0.0.. 9... 0..00.0 0...... 0.0 ...... 0.... 0.0... 0...0.. 0.0.. 0.0 ..s 08. 0.0... 0. .- 0. 0 008 .000 00. .00... 9.0000. .20 :..3 9.00 .....0 030... ...00 00:00. 5... 00 ... 00.0 000003 00 0»0m 20. 104 0...... a... 5.. .003. 0:... ...... ...... ..s 0.3. ....-n... ......m .0... ..S .00.... o. 0...... :0... 0.5M... :30... :..... b0> mdéd 00... :08 3...... $380 mmm ......m .0.... :... 5.2.0”. n.m.c.m ......m ..S o. .3. .03.. o. 00....» 0...... b... 5.. .3... o. .03..» ......m 0:... ..38m o.m-m.. ...... 2.... ...... .58.. «...... .... .65. .32.. ...... ....-n... ...... 5. o. 3.5% ...... ...... .56... ...... 2...... ...... a... ......» 5.3 ...»... 5.0 .8 0.003 .0330... ...... ...... 5.3 ...m x003 5.2.0”. n.m.c.m ...m .305 o.m-n.. 3.0.0... ...—am... ...—amp... 0....3 ..o 3830 5.3 ...... x005 0...... 0.0200. 00:0... - .02...» 5.3 ...... .805 o. .- n. 0 3.0.0... .238» 0.23 .... 8820 5.3 ......m .0.... .605 n. cé. o 00.. 0?.— .. .00.... «0... :03 3.80 9m :30... ...... $0.0 .0.... ...... 20 00.83% m. mé. m 0.6.... .... 080m o.m-n.. =38. ...... ...... b... ...... .20 09.238 0...... 03.... ...... 080m 9.-.»... .30... b0> .20 v.8 ...... :39... ......Q 2...... 00... >09...» .EEa3m SE .0.... mam .....«m a... 00.88... .605 n.m.c.m .03 - ......m 5:... =30... ...... o. 808w @383... ......m .0... :... ...»... o.m-n.. .03 - ...... b... 5. ...»... 0...... 0.2. 2.. ... .23 - 83...... 5.3 ...... 5. ...... 2... 8...... .... ....n. ....-n... 20 .0 ...... 5.3 .... 23o... €3.3an no.0... 00.... .3me 3.53m 2m .03 4...... b... 5.... find...” ...... ...... s... 0.3.. ...... a... a. .08.. 0...... ...... 2.... b... 5. be... ....-n... 9.8 0:... .0.... ..38m 27o... 00:0. 8 3.0.. 00.... :2... .3080 ONO ......m D... :..... n.m.¢.m 3.. ...... ...... a... o. 8...... ...... ...... 5.. 0.3... ...... ...... 5. be... 2.... ......m. 3...... ...... .0.”... .... ...qu 1...”... ...—.0 :39... .....Q QTnd a d._.¥.s .... ....-.urrf... ......u. 105 2.03 n.m.0.m 0...... ...... .580 0.0.... 00.00 ..003 .23 3.0.0... 0.00».0 030.0 2.0.. .00.. 0.2.8 .0.... 038m 0...0.. ...... ...... .56... 0. ...... a... ..s 0...... ....-n... 2.8 .0... ..0. .00.... .23 2.8 .0... ..0... 0.00».0 030.0 20.. 80> 0.0.0.0 .0080... 00.. 000.0 0000 -....8 £880 .2. 0.003 .0000... 2.0 008 .0... 030.0 2.0.. 08.2.00. n.m.0.m .00.. 03. .0 20.. ..00 002.. 8.0.003 00000. .00. .0 ....8 .0.... ..0... 0.0080 030.0 2.0m. 0.m-n.. ...... 0... .0.. 0.5.0... 5.6... U...... 0...... 2.8 .0... ..0... 0.00».0 030.0 2.0m. 0..-0.0 0000...... .0 .80... 088 ....8 .0... ..0... 0200.0 030.0 2.00. 0.00.0 00.0 2880200003 0 0. 2.0. ..0 own... a. a 0020. 0.908 02 m.m.0.m 2.00.0... 30>...» 030.0 2.0.. 2.0.5.005 06-0.. ..08 08000 ..00 SO .23 ..08 .0.... 030.0 2.0.. 2.032005 0...0.. 20 ...... ...... a... 56... ...... 02.0.8... ....-n... 20 .23 008 .0... 030.0 2.0.. 2.032005 0.0.0.0 0000.. 0. ...00 00.0 0000 >880 0N. ..08 .0... 00. .003. n.m.0.m ...... ...... ..s 0...... 0..-... ...... a... .0. 2...... 2.... 0.8 a... .... 0...... ....-m... ....0. ...... .... ...... o. .... .56... .00 00...... 00.... 08... .00.. 080 .0. ..08 .0.... 00. .00... 2.0 ..003 030.0 2.0m. m.m.0.m .00.. 0.0.. 0.0000 0. ..08 .0... 00. .20 2.0 0.00.. ..0 0.0. .23 ...... 030.0 2.0.. 00> 0.0.0.. .20 ..00 0.00.. ..0 0.0. .23 ...... 030.0 2.0.. 00> n. .0.. .20 ..00 0.00.. .0 0.0. .23 ...0 030.0 2.0.. 00> 0..-0.0 20 ...... 08. ... so. ...... .... .52.. ...... 00> 0.0.0... .... m .303 0...0..... ...... 3.0 .0008 00. .0.... ...... .00... 08.0.2040 ...... ...... 0.26.0 .8... .0003. 0...... 008 08000 200.0282 2.0.. 0. .02.. 000.» .23 ..08 .0.... ..0... .20 030.0 2.0m. 0.0.0.. 83.0.. ...... 050.00.. ......» ....a 80... 08.0 ...... 0.8 0... ...... 20 .58.. U0.0 0...... 002.. .20..» 000.» 2.0 00. .23 2.8 .0... ..0... 0.00».0 030.0 2.0m. 0..-0.0 0.0000 ..000 002.. .23 2.8 .0... ..0... 0.00».0 030.0 .209 000.0 80.0. 0003000.. on. 2.8 0.... 00. .003. m.m.0.m mum . .. .... : .. .. .. L. , .... u... . .. ...}... ....v... Stair-:... . ....-..1 ....h “4......“ .n 2...... ......u....l...\..... .. .. . m. .. w . . .. ... . ,. ..., I _ ...... ...... . _ «J .. . n 31.... ., ...... 0...0.. ... ......» .. ... .....n. a... . ., .... ......ufv. ... . «hm _ . .. 1&1 o . . .. .P l. .r....h.._..\l..... El .1. ..I. Q. «.01.... a. ll. . .4....‘0 .... .. ...-1 .. .. ...h...|. ..r . .. .. . - ...Fl...-.‘...‘ u. ..\._... . VI. . .73.... . o.- r... 0...0..“... ._ .w01.1£.?..1¢.t. .. high... :.....A... .. i. . uk-I 3000000 .0. 0. 0 106 xx . ...... .............-...,- ...-...... ... -..: A q ........H...._-__.... 0...0.--0.90, r......-...-_........_... .... . . ... . 01...... . ......l. 1m...m..1.w!..t{._.n- .... .. ”w: ohfiahn“ngrv-(W-fi.¥$mwfiivm\uqufiyy n..w....\.!.4.-”.. \u*¥.3fl ..."...FW‘WVF.“ UAW-{PWN-Hffi‘ — . a.) . ...w. :..-fl... . ......Fif. - . ..00. .23 ..08 8.000 030.0 2.0.. .00.. ....0... 0..00.0 0.0.. 08. 5.3 ...... 0.08 ...30... .0.... 00> ...... 0..00.0 0..-..0 ..00. .23 ..08 00.000 030.0 2.0.. .00.. .00.. 0.00».0 00.0.0 000...... .0 .0.03 .23 00.0 02.0 280.0 09. ..00. .0... 00... 0m.0.m ...... 0... ..s 32.2. .083 -.. 0.0.0.8. ...... 0.5.... .38.. .0.... .0... 0..-... ..83 05.80.. 5.3 .03 4.82.. 08. ...... .5508 .2... 20 .32.. 2a.. .0... 0.0.. 083 ... 2...... 5.3 .03 0.32.. 08. ...... .5509. ...... 20 .32.. .0.... .0... 0..-..0 .03 000.0... 0.00. ..00 .00....00. 00.. 0.00».0 030.0 2.0.. ......m 00.0.0 .00.. 00.... .23 00.0 2.00.0 ..Gwom 0N0. ...... 0... ..380 ...-0.. .... 00.. 0.0030 030.0 2.0.. .00.. ..00 0003 0.00. .0.... 083 .082 ...-0.. .03 ...00. .23 .... 00... 0.000.0 28.0.0380 2.0.. 00> 0. .-00 .03 ...00. ....3 .... 00.. 0..00.0 28.0.0380 2.0.. 00> 00.0.0 .00.. :08. ..00 ...0000 .23 00.0 30.. NS. ...... ...... 000 ...... ...-0.. 20 0.008.. .8... .0080 0..-... ..003 0.0.. 0003 0..-00 .03 .20 ..00 ..00. .0 ..0. .23 .... 030.0 2.0.. .00> 00.0.0 .00.. ..00 ...0000 0.0.0 5.3 00.0 30.. 09. 0020. 0......8 02 00.0... ...-00.00 .0 200... 0. W0. 0.3. 0... .... .20 ...-0.. ..08 .0... 00. 20.0 8 .000.» ..08 0... 030.0 2.0.. .00.. 00.. 0.00».0 0..-00 20.000 .0200 ..00 .000 .0 0.... 0.0.. 0.0.. 0... 0. .803 ...00. .0... 030.0 2.0.. .00.. 00.. 0.50.0 00.0.0 00.0 0000 280.0 mm. 0020. 0..00.0. 07. 0.00 .... 0.00. .23 .000... 00.. 000.000.. 030.0 0......3. 0.m-0. .... 0.00. ....3 .000... 00.. 00.20000 030.0 2.0.. 0......0... 0.0.. .00 .0... ...... .38.. U0...U .0003. 0..-..0 08.. 0...... ...... 00... .0.... 0.0. .0.. 0...0..... .80 0.0.0.0 ...... 58.... .0 no. 5.3 8... .0083 .0. ..08 0... 00. .23 .0..0.0... 00.. 0..00.0 030.0 2.00 00.0.0 0.0000 ....8 0... 00. ..00. ..00 0 ....0 03. .0 ..003 ...... 00.. 0.00».0 030.0 2.0.. 00> 0.0-0. .... ..00 0..00.0 03...... v...... 00> ...-0.. .... ...... 25.... ...320 U...... 00> 0..-..0 ..00. .0 ..0. .23.... ..0... 0.0090 030.0 ..0. 0. 030.0 2.0.. ...0> 00.0.0 .803 00.00.... ......03. .00.» ...0000 “3.....111. 2.1.3.7.}. ......)714 ...-....“ ...... 107 .20 00:108.. .5 ...... .52.. .30 3.0.0 05.290 2.8 .23 < 3.). 00:8 03:30 02 n.m.c.n 0003 o.m..n._ 00:05 03. 80:00 3 0003 .053 .00... 5F “3.0.. Ba ...... as 08.. 3-3 0.30 .33 .3. bu... .0000... 03. 80:00 .008 .00... 00.: 00390 030.5 Juan 020.06 00.3 0000 330 ONE 200 “53000.. 00.5000 0000000203003... .000. .3... w.m.o.m 0:8 0.0 .5... .36. 000.5000 000000.300 005-200 0.0 03.. ... 0.30 bum 030.5 0.30 .00.. .000 00330 070.. ..3... a... .56... .0.... 00> .0.. 0.330 o. .-2 0.00. 5.3 0.30 00300 .0305 0.30 b0> .00... 0.00».0 00.0.0 .033 00 00:05 00...: .23 0.8.. R..— .00 0305 EM: 0.3 0020 0003 n.m.o.m .000... 00... 9.03000 :30... fian— c.m-m.. ..83 0538.. 9 8......» 0:3 0.0 .3... 2.0.. 2.520 02: 08.08. 5.3 .05... 0.0 .3... 3-2 05.... 0.0 56... 0.30 00.0.0 8... 8083 3.. 0.30 00300 .3 a. m.m.o.m 0.30. 00300 .3. 400.. 03. 3 30.508 50.: 00390 030.5 0.30 b0> 0. 0.035 o.m-m.. .03 .23 0.3 >20 5.3 2.0.508 :0... 0:3»..0 030.5 0.30 b0> 0. 0.003 070.. .03 .50 0.3 .220 .23 2.0.5000 not 00390 0305 x30 .00.. 0. 0.005 c.7nd .03 4:0. 0.3 ~...—0 .005 30.5000. :0... 00330 550.5 x30 b0> 0. 0.005 00.0.0 9.330 a 5 03..» 0.3 £3.30 .00... :35 mm.— 0.3... .93 :30... >23. 0.30. 00.300 .505 0.30 b0> .0003 n.m.¢.m 0.03000 0.3 0.30 00300 :30... .30 E0.» .0003 06-0. .5. .20 o. 28 a... 50 0.0.. 05. 0.0. .5 3-3 0.30 .000. .3. .00... 000 80.000 .0000.» 0.30 b0... :30... 330 00.0.0 000.. 3.80 .23 003 >880 .NA :83. 0.9.30 02 n.m.o.m 0:82 22.9.2 .32. .083 3-0. .83.. .00.. 0:0 0.0.. 30.. .0003 .2 0.30. .000 0305 x30 b0> :00 0:330 070.. ..vsa ......m 5.2.. 00% be, .00 0.50.0 3-3 22. 2.. ... .233 .03.. a... .58.. 0.3.. 00> .00 0.30.0 3.3. 8.. 8083 .5. 0.00. 5.3 0.3.. 00.300 .0305 0.30 .00.. ...0... 00330 n.m.o.m 0.00.. .23 0.30. 00300 .0305 x30 b0> £0... 00330 06-0. emu .3 ... 0...... ......N3 ......0....., an”... 0 Atria... ...... :5... .... . U... .. ..rrfzt. .... _ ......Lm 0.000%... ...$..£m...mwfi wt. , 108 3...... 5.0330 300 0.0.0.0 .00.. 03. 3 0.0.. 05 0. .033 .0030 >50 >3.» 0.30 0. 0003.» 0030 >...0 0305 ...3n. 0.m-n.. ...... 003 .20 .0000. 5.3 0030 >...0 0305 ...3n. n..-0.. ...... 5.3 3.00 0.0 .0.. 0.300 :39... 030 0..-0... .30 5.3 0030 >...0 ..0... 0.03».0 0305 ...3n. 0.0-0.0 30.3 0000 >003.O «NO 0030 >...0 >3.“ ...30 >000... ...0. 05 3 0003 0.00» 2.0.» 0.30 2.... 058 5.3 0.0 3.0 .33 .0... 383 0.0.0:. 0.0.. 05 0. .033 .0003 5.3 0030 00.300 >3.» 0.39 0.0.. 0.30 >3.» 0.30 .838 >552. 0. 0003..» 0.30 >...0 >3.» 0.30 0..-n.0 0.000.. 3 0030 >...0 >3.» 0. 0003..» 0.30 ..0. 3 0030 >...0 ..0... 0.3».0 0305 0.39 0.0-0.0 000.. .9305 3 .0 Z a mm 30.3 000003 37. g 0.0. 058M053... >0 0.00 000.350 .0030 .000 >80 2.0.» .0.. ...... 08... 5.3 3.00 0.0 3.0 o. 0.3 .350 0008 9 003.0 3.30 0.0 .20 3.0.0. 0030 >50 0305->0.» 0. 0003.» ...0 0.000 5.3 20 0305 ..3Q n..-0.. .00 00.00 5.3 20 0305 0.3a 0..-n.0 ...0 0.000 5.3 3.0 030.5 0.39 n.0-0.0 .033 »0.003.0 5.3 30.3 0000 >003.0 37. 000.3. 0.00.30 02 m.m-0.m 0003 0.m-m.. 0050 0003 5.3 20 .050 0.3 0.00. ..0 0.0. 5.3 .00 0305 U.30 >.0> 0.0.. 000.0 0003 5.3 20 .050 003 0.00. .0 0.0. 5.3 ...0 0305 0.30 >.0> 0.6.0 .20 .050 003 0.00. .0 0.0. 5.3 .00 0305 V.30 >.0> n.0-0.0 30.3 000003-0000 .>003.O .NZ 000.3. 0.0030 oz 2.0.» 000.3. 0.0030 - 0030 >...0 .3... 0.m-n.. 00.300. 300 0. 00>0... ...»..05 .0» ..00.=00 005500 5.3 0030 00.300 >3.» 0.3a n..-0.. ...... .56... ...... .0.. 0..00.0 3.0... 0...0.. .008 .00..... ...... ....0 0305 0.30 >.0> ..0... 0.3».0 000.0 003.03 .3 .033 .0000 3 .0 05.0.00» mug. 0003 .0.-000.3. 0.00.30 07. WWO.» 083 .0.-53. 0.3.50 oz 3.0-0.. 0.0.. 05 0. .033 003 0.00. 5.3 0030 0305 ...30 .00.. 0.3».0 n..-0.. 0.0.. 05 0. .033 003 0.00. 5.3 0030 0305 0.30 .00.. 0.3».0 0..-n.0 0.0.. 05 0. .033 003 0.00. 5.3 0.30 0305 0.30 .00.. 0.3».0 00.0.0 003.» .303 3.0330 .0008? 0N2 0030 00.300 03... 0.30 00300 03... 0.0.5 00. .0 00.00 5.3 20 »0.>3000 003 ...0 0305 0.03m. 0.0.5 .00. 0».3. 00.3 3.... »0.>3000 0.3 ...0. 0305 0.30 109 .>3.0 005 0030 005 .0305 3 ..5 ....0 003 0.00. .3030 5.3 030.5 0.30 >.0> 0.m-n.. ...0 003 0.00. .3030 5.3 030.5 0.030 >.0> n. .0.. 5.0 003 0.00. .3030 5.3 030.5 0.030 >.0> 0..-n.0 50 003 0.00. .3030 5.3 030.5 0.030 >.0> 00.0.0 .033 003.00 5.3 00330 .3030 >9. 0030 030.5 ...30 m.m0.m 0030 030.5 ..30 0.m-n.. 0.00 05 .0 0.0005 .3 0030 030.5 ..03 .>3.0 50.. 0.03».0 030.5 ...30 >00 > 0.0.. .0000... ..35 003.03 .>3.0 50.0 0.03».0 030.5 ..30 >.0> 0..-w.0 >3.0 50.0 0.03».0 03005 ...30 >.0> 00.0.0 303 0000 >0003\>003.0 mm”. 00.3. 0.0.030 oz 2.0... 00305 0003 06-..... .0.... .......3. oz 0...0.. 00.305 0003 0..-m.0 ...... .00.... .0.. .0.... .000 0.0.0... 30... .0383 05.. 33 000 m.m.0.m .8. 0.... .. ...... oz .3... 0.0..... .083 .... .20 ...... .3. 5.3 ...... ...... 5.6.0 0.0.0. .20 .050 003 .35 .0 .0. 3 5.3 0030 >...0 030.... 0...0.. 0.00.05 .3 0030 >...0 03. 0. 0003.» 0.30 >...0 50.. 0.03».0 030.0 ...30 0..-0.0 0030 >...0 50.. 0.03».0 0305 0.30 000.0 30.3 0000 >003.0 go 0030 505305.280 00.0... 0030 030.533.» 0. 0003.» .35 003 ...0 00.00 5.3 ..20 »0.>3000 030.5 0.030 >.0> 0.m-n.. ...... ...... .... 0...... ...... .20 0.038.. .06... ...... 00> 0...0.. ...... ...... .0 0...... ...... .20 0538.. .30... ...... 00> 0..-0... ...0 00.00 5.3 .20 »0.>3000 03005 ...30 >.0> 00.0.0 »0.003.0 003 003..» 5.3 .0033m nan. ...... ...... ...... 0... ...... .....0 0.0.0.0 ...... ...... 03.0 ...... 0. ...... .... .0.. ...... ...... ... 8.00.0 ...... 5.3 ...... 0... ...... 0.0.0. o.... 2.. ... .00..; ...... 08.0 0..00.0 ... 0...0... ...... 0.3. ...... ...... 0...... 0...... 0... .3. 9 80.00 .238. ...... ...... 5.3 ...... 0... .0.. 0.50... .30... 0.30 0..-0... 0.00. 003 0.35 5.3 0030 .>...0 50.. 0.03».0 030.5 ..30 0.0.0.0 303 0000 >00300 man. 0...... 0... 3.0 0.0.0.0 0.05 05 0. .033 .0030 >...0 >3.» 0. 0003.» .035 .>...0 50.0 .20 .0305 0.030 >00 > 0.m-n.. ...... 0... ... .233 0.8. ...... 0... 20 .030... ...... 00> 0...... 0.05 05 0. .033 .0.00. 5.3 >...0 .20 .0305 ..030 >.0> . I n ( ... .... .. .. .. r . ...nJ 4. .. . 1.. u .r. :.. i. - s. In... ... Law . .3.I{..A 2...?» (0.1.: .‘ ”0...... ...) r. 0 .. n .0.... .. .. ......n... a... l. .1 ...... J.... .«kd... .1, 7.43%... :.. .... .... v ~fl00308. .—.< ”30,—. 30.05 0...... 0. .033 .0.00. 5.3 >...0 v2.0 .0305 ..30 >.0> 110 20 5?» 93m 8595 fan— n.m.o.m Egon .23 >20 $5385 653. x83 51.3% 95 $.8me 28m :38: x30 o.m-m.~ 38.. can in: .20 mo .2 m .23 v53 .565 #39 07¢.— 33 .20 can .33 .32: 53 9.8 .365 fig 9 28m .365 o.~-n.o v53. 565 2.66 38% 98 3.8» ~23 zones 05 =0 0ND :83 29:3 oZ n.m.o.m coo? o.m-m._ 8:55 02: cop—w 28 >20 23 Hi 2:8 .23 has 93 300.. 332 0:: 8:55 02: 50% 93 >20 Ba :7. 088 5; has 98 808 >382 @466 .62 93 $08 .23 not 253° .27. 5595 x56 bu> mdéd no.8 Ewan a 5 20% .302 >8. :83 29:8 oz m.m.o.m 3.33 303 o.m-m._ 8.83 .23 .3535 25qu no 32 53, :7. 5595 x53 bo> 0:: flats 53 areas “isms mo 82 .23 :7. 550.5 V13 bo> o._-m.o Browne 0:890 mo 32 .23 an .565 x58 bo> mdéd «Pa 5% $30 cum an? 28 2.3 coo? ndéd , “uwfiygwuhhtrflk (a ,. .. . . é _ M ‘ h a........., ( : . g... ‘ ,, . 7. 111 Apgndix B Sequential Chemical Extraction Procedure Soil cores were frozen (—20°C) until just prior to beginning the sequential extraction procedure. After the cores were thawed, they were placed in a glove bag, which was then evacuated and purged twice with N2 (g) or Ar (g) to ensure an inert atmosphere. A Teflon police man was used to transfer about 50 grams of soil from the bottom of each core into acid washed 120mL plastic vials for homogenization. Large objects, such as roots, wood, rocks, and urban waste, were excluded from the material that was homogenized. After homogenization, five grams (i 0.5g) of wet soil were weighed out on an acid washed watch glass for wet weight] dry weight determination. A separate one gram (i 0.2 g) aliquot was placed into an acid washed 30 ml centrifuge tube for sequential chemical extractions. The remaining homogenized soil was saved for organic carbon determination by loss on combustion. Once the weighing was completed in the glove bag the watch glasses were placed in a convection oven for 24 hours at 50°C to dry the soils. Each sequential chemical extraction step began with the addition of a chemical reagent under an inert atmosphere, followed by agitation of the tightly secured centrifuge tubes to completely mix the soil/chemical mixture. Each chemical addition reacts with the soil to strip off the bound metals from targeted solid phases. After each prescribed reaction time the leachate was separated from the soil by centrifugation at 15,000 rpm for 20 minutes. Leachate fluids were siphoned off or decanted into acid washed 30 ml syringes, then filtered through 0.4um acid washed Nucleopore membrane filters into acid washed NalgeneTM polypropylene bottles and acidified to pH< 2 to prevent adsorption to 112 the container walls and precipitation of metals from solution. Samples were stored in a dark 4°C refrigerator until analysis. A copy of the detailed procedure, which was adapted from Matty (1992), is on the following two pages. 113 Procedure for the Sequential Chemical Extraction of Metals (modified from Matty, 1992) From each homogenous sample remove two aliquots. Aliquot 1: place on tared watch glass; dry in oven at 50°C for 24 hours; reweigh and record percent water; perform HN03 microwave digestion. Aliquot 2: place in tared centrifuge tube; perform sequential chemical extractions under N2 using the following procedures: I. Exchangeable Fraction 1. 2. 3. 4. 5. Place 1.0 g wet sediment into acid-washed tared centrifuge tube. To each sample, SRM, and blank, add 10 ml. 1.0M MgClz (pH 7); with wrist action shaker agitate continuously for 1 hour at 20°C. Centrifuge for 20 minutes at 15,000 rpm. Remove leachate with a syringe and filter through 0.4um Nuclepore filter into an acid-washed 8 or 30 mL bottle. Acidify to pH<2 with optima HNO3. Rinse sediment with 10 mL DDW in vortex mixer; centrifuge for 20 minutes at 15,000 revolutions per minute (rpm); remove supernatant and discard. II. Weak-Acid Soluble Fraction 1. $0 To sediment from (I) add 10 mL of 1.0M N aOAc (pH 5 with HOAc) and agitate with shaker for 5 hours at 20°C. Centrifuge for 20 minutes at 15,000 rpm. Remove leachate with a syringe and filter through 0.4um Nuclepore filter into an acid-washed 8 or 30 mL bottle. Acidify to pH<2 with optima HNO3. Rinse sediment with 10 mL DDW in vortex mixer; centrifuge for 20 minutes at 15,000 rpm; remove supernatant and discard. III. Easily Reducible Fraction 1. E" To sediment from (H) add 25 mL of 0.1M NH20H~HC1 in 0.01N HNO3 and agitate in shaker for 0.5 hours at 20°C. Centrifuge for 20 minutes at 15,000 rpm. Remove leachate with a syringe and filter through 0.4um Nuclepore filter into an acid-washed 30 mL bottle. Rinse sediment with 10 mL DDW in vortex mixer; centrifuge for 20 minutes at 15,000 rpm; remove supernatant and discard. 114 IV. Moderately Reducible Fraction 1. To sediment from (III) add 20 mL of 0.04M NH2OH-HC1 in 25% (v/v) HOAc. Place sample in a water bath at 96°C for 6 hours; agitate every 30 minutes. Centrifuge for 20 minutes at 15,000 rpm. Remove leachate with a syringe and filter through 0.4um Nuclepore filter into an acid-washed 30 mL bottle. Rinse sediment with 10 mL DDW in vortex mixer; centrifuge for 20 minutes at 15,000 rpm; remove supernatant and discard. V. Oxidizable Fraction I (not done under N2) 1. >1 To sediment from (IV) add 6 mL of NaOCl (pH 9.5 with HCl just prior to use). Place sample in a water bath at 96°C for 15 minutes. Centrifuge for 20 minutes at 15,000 rpm. Remove leachate with a syringe and filter through 0.4um Nuclepore filter into an acid-washed 30 mL bottle. Repeat steps 1 through 3 two more times (except for the third step of the third addition), using the vortex mixer to resuspend the sample after each addition of NaOCl. Add 5 mL of 3.2M NH40Ac to the solution-sample mixture of the last NaOCl addition. Agitate with shaker for 1 hour at 20°C. Centrifuge for 20 minutes at 15,000 rpm. Remove leachate with a syringe and filter through 0.4um Nuclepore filter into an acid-washed 30 mL bottle. Rinse sediment with 10 mL DDW in vortex mixer; centrifuge for 20 minutes at 15,000 rpm; remove supernatant and discard. VI. Oxidizable Fraction 11 (not done under N2) 1. sew E"? To sediment from (V) add 3 mL of 0.02N HNO3 and 8 mL of 30% H202 (pH 2 with HNO3) in 500 uL aliquots; agitate every 30 minutes for 5 hours in a water bath heated to 85°C; leave caps unscrewed. Place samples in Wrist Action Shaker to cool. Add 5 mL of 3.2M NH40Ac (pH 2 with HNO3). Agitate with shaker for 1 hour at 20°C. Centrifuge for 20 minutes at 15,000 rpm. Remove leachate with a syringe, empty the syringe into an acid-washed 25 mL volumetric flask and dilute up to 25 mL with DDW. Filter the diluted solution through a 0.4um Nuclepore filter. Transfer solution to an acid washed 30 mL bottle. Rinse sediment with 10 mL DDW in vortex mixer; centrifuge for 20 minutes at 15,000 rpm; remove supernatant and discard. 115 APPENDIX C Field Aqueous Sampling The material the peepers and barrels are made from has the capacity to adsorb 02 and therefore needs to be de-oxygenated prior to emplacement in anoxic systems. The de-oxygenation was accomplished by submerging the samplers in DDDW and bubbling with N2 or Argon gas for a minimum of three days. The samplers were maintained in DDDW until they were installed. All components of the samplers, including the dialysis membranes, were acid washed with 10% BC] prior to assembly. The peepers and barrels were installed below the land surface in saturated areas. The samplers were left in place for at least two weeks to allow biogeochemical equilibration to occur between the sampler and the pore water (Hesslein 1976; Carignan et al., 1985: Tessier et a1. 1996). In order to obtain sufficient fluid for analysis, four to six adjacent peeper ports were sampled to make up one sample. An example of the sampling scheme is presented in Figure A2.1. Peeper Sampling Scheme F e2+ Allialrnity Anions Cations I DOC R Figure C l. A schematic diagram showing the ports from which fluid was taken for the various parameters. 116 The sampling of the peepers was conducted in the field at site the where the peeper was installed. The peepers were removed from the ground and the outside of the membranes were rinsed with DDDW. The peeper was then placed on a portable table and samples were taken for the various analyses. Samples were obtained by puncturing the membrane with a plastic pipette tip and withdrawing a sample with a pipettor or a syringe fitted with a plastic pipette tip. Methane samples were collected by simultaneously piercing the nylon mebrane of a sampler and the butyl rubber septum of an evacuated, 30 ml, glass bottle. This allowed the collection of a sample with a headspace that has not come into contact with the air. The most redox sensitive parameters were sampled and/or analyzed first. Aliquots for CH4, NHH, 82', and Fe2+ were taken first. This included preservation or treatment of these redox sensitive parameters. When the redox sensitive parameters were stabilized or preserved, aliquots for cations, anions, pH, alkalinity, and DOC were obtained. Usually the complete sampling was achieved within ten minutes by a team of three to four personnel. After all the samples were obtained, the quantification of those parameters measured in the field was performed. Parameters measured in the field included temperature, pH, Eh, Sz', Cr(VI), Fe”, and alkalinity. Sampling of the barrels required a slightly different approach. Three barrels bound together constituted one sample and a diagram of the sampling scheme is presented in Figure A2.2. When the barrels were removed from the ground they were rinsed off with DDDW. Snap on caps were fitted to the ends of the barrels and they were transported to a central location in an argon filled plastic bag. Transportation to the central location was generally accomplished with in five minutes. Once at the central 117 location, the membranes were punctured and the samples extracted. The barrel from which the redox sensitive samples were taken was processed in an argon filled bag. As with the peepers, the actual splitting of samples for the various parameters generally took less than ten minutes. Barrel Sampling Scheme H28 CH4 Figure C 2. A schematic Redox Sampled diagram showing the barrels under Argon from which fluid was taken for the various parameters. F e2+ Cr6+ DOC Alkalinity, pH NH4 * Anions Chelex Cations 118 :.m B B an; odd mm; odd odd mod de mod 3 3 073mg 56 up do wmd m ~ .0 on; mod mNd 8.0 wad mod us ca @062 m 3mm 3 3 odd vod RA mod 2 .d ddd 2d 8d 3 B STE 5 do; 3 B :.d mod 2: mod 3 3 Had mod 3 B 2.25 mmdm B B owdm do; -- -- -- -- 3d wdd B B md-3 5 mm; B 3 Ed 5d 2d 3d 3 3 odd 5d 3 3 m.m-mmm whm E 3 S; 8d 9: 5d de 8d “Nd mod 3 3 073m and B 3 Ed dad md.m odd 3 3 8d 8d 3 3 mddodm mod 3 B we.» end mod mod 3 3 2d 5d 3 B mddpmm 3.9 B 3 cod mmd PON Ed mud 8d dad mod 3 B mddadm mm: B 3 mod vod Dad Nod Ed 5d mod odd 3 B m.m-m\.m 51 E B vod vod mmd 8.0 d _d cod 3 B B B m. d A Em mm; B 3 d2 8.0 end 8d 3 E wdd 5d 3 3 mddnm mos Up vs OWN dod 31V 2 .0 Up 3 w _ .0 No.0 3 B w.m-mmm 9mm 3 B 2; mod mm.“ cod 3 3 odd 5d 3 B 2-3m dN.m B on :.N odd 3d dd 3 3 add 5d 3 B wddmm 5d 3 B 84 8d md._ mod 3 3 Ed 5d 3 B m.m-mmm dm.m B 3 wN.m mod 2d 5d 3 3 mod cod 3 B WTEm ww.m an to e .N a: .0 mm; 506 fin to bad mod us up mdéomm 5m 3 B E .m S d 92 odd 3 3 dmd mod 3 B mddpmm wm.m us Us and Ed E; 50.0 63 Up mmd mod 3 B wdénmm E E E aaafigaafigfl com com ~58 com ...—cm com ...—8 “alga. ...—8 com ...—8 .33. «NO NNO Sac “NO m2 ”—2 mm Mm m<>> @459 NM NH 938% @2588 8: $2365 -- $2823 323 82865 3 Emma EH95 b3 wucwE .EoEEom 5 83880280 82335 now ABE £838 8282 E 3638 52352.8 wouaomufi .58 SEEP—:0 you San— :caoabxm 3382—0 35:2. om "Va 035,—. 119 3% B B 8.2 a: mm: :.o Ra mod 3: m3 3 3 2-86 m2 2 B 8; So as 36 :.o :3 B B B 3 2-86 :.N B 3 ad 36 mo.“ 3o 36 86 :.o :3 B 3 2-86 42: B B an: :.o :3 :.o So 86 8o mod 3 3 3-86 x: B B m? 8.0 So 36 Ed 86 :.o 8d 3 B 2-me 8..“ B B o: So 93 3.0 mad :3 N8 56 B B 2.50 58 B B 3.3 a; a.“ :.o 98 So m3 So 3 3 8-96 42 B B one So $0 36 mod 8o 3 B B 3 3-80 Sm B B A: 8.0 NS So 26 :3 Ed :3 B 3 2:6 2d 3 3 42 86 Bo 8o 3 3 ed :5 B 3 8-80 2:. B B m: mod NE M; So 86 26 So 3 B 2.8 o? B B a: 8d 93 :.o one 86 ed So 3 3 2:6 02 d B B 3.0 wad mom 2 .o 08 So m8 8d 3 B 3.96 2:. B 3 a2 8.0 mam 2.0 m3 :3 mod :5 B 3 3-80 8a 3 3 3o 36 93 3.0 So So So 8o 3 3 2-30 8a 3 B 3m :8 :.m 2.0 v3 :3 26 So 3 B 238 2.8 B B m; one 8N 3o m: 8o 9% mno B B namtm 93 B B Ea 03 8a 2.0 mg 86 5o 86 B B 2-:5 8.2m B B 2.8: o2. :8 a: :.M: woo NS woo B 3 3-25 N3 3 3 En 26 :.N 5o 48 So 86 8o 3 B 2.85 2.: B B E: 98 MR NE SN 26 one So 3 B 2.35 EN 3 B 8.2 a; mom e3 3N :.o who 3o B B 8.85 m3 3 3 one :3 a2 85 E 3 mod :3 B B 2.25 m; B B 52 mod a2 8.0 Re So m8 8o 3 B 2.35 $.m B 3 84 8o 5.2 So So So 8o 85 B B 2-32m figafiqgflgaflfiaafl com com .58 now ...—am tom ...—8 tom :..8 com ...—8 ulna." ...—8 ass 88 d3 :8 :3 m2 «2 mm mm 9.3 ms.» an E 2.35 120 Nvd up vs ow; mod vmd E d X: vod 3nd mod 3 do w. d -H m H Q 003 B on dmdfi mud woé a d 2N mod dud odd us ca mddflfl 92m we us we; vod M: .N 2d NH .0 Odd 3d 5.0 up 3 madam Odd up 3 wmd Nod mm; 00.0 mad 5d 2 d Nod B 3 mg; 20 wm> m<>> Nm— Nm o—QEam 121 :.N B B 00.0 00.0 02 00.0 00.0 8.0 00.0 00.0 B 3 2-50 00.000 00 00 00.002 00.0 00.000 00.0 :..E 00.0 00.0 00.0 B 00 00.020 00.02 B B 00.0 00.0 :.0 00.0 00.0 00.0 2.0 20.0 B B 0.0-00E 00.00 B B 2.5. 00.0 00.00. 00.0 00.0 20.0 00.0 20.0 00.0 3.0 2-50 02:00 00 00 00.008 00.00 00.0000 00.02 00.200 00.00 00.00 00.0 a: 02.0 00.020 3.0 B B 02 00.0 00.0 00.0 00.0 00.0 00.0 00.0 B B 0.0-0:0 00.: B B 00.0 02.0 00.0 00.0 22 00.0 00.0 00.0 B 3 2-50 00.00 B B 00.2 00.0 00.0 00.0 :.m 2.0 02 2.0 B 3 00.020 00.00 B B 00.00 02 20.: 00.0 00.0 02.0 :1 3.0 B 3 2.00% 00.000 00 B 00.2: 0: 020 00.0 00.: 20.0 00.0 00.0 B 00 0.0008 0.00002 0.00: 0:: 3.030 00.002 0005 00.00: 00.000 02.0 00.000 02.8 B 00 2.55 00.0000 0.0200 00.00 0.00000 00.000 00:00 00.3: 00.00: 00.00 00.000 00.: B 00 00.005 0.0000: 00 B 2.0:: 00.00 82.2 00.200 00.0000 02.: 3.000 00.2 B B 0.0-000m 00.02 E B 00.00 00.2 00.00 02 m: 00.0 :..0 00.0 B 00 2.205 00.02 B B 00.00 00.0 020 002 02 00.0 00.0 3.0 B 00 00.005 00.0 B B 8.2 00.0 2.0 02.0 :0 00.0 8.0 00.0 B 3 0.0-25 00.0 B B :..m 2.0 00.0 00.0 00.0 00.0 :.0 00.0 B 00 2.2.5 03: B B 00.0 00.0 0: 00.0 02 00.0 00.0 00.0 B 3 00.005 00.0 E 00 2.0 00.0 02 00.0 :.N 00.0 00.0 3.0 B B 0.0-005 00.0000 3.0: 00...- 000000 00.00 02.00 00.: 00.02 00.0 00.00 00.0 B B 2.35 00.0-000 00.00 02 02.003 00.00 5.0000 00.02 00.0: 03. 00.3. 00.0 B 3 00.005 0:. B B 00.0 20.0 00.0 00.0 22 00.0 E0 000 B B 0.0-02o 022 B B 02: 00.0 00.00 20.2 20.0 00.0 02 :.0 B B 2-5a 00.50 00.00 3.0 00.3% 00.03 00.0000 00.000 00.0: 00.0 00.00 2.0 B 3 00.005 00.0 B B 02 00.0 00.0 2.0 00.0 00.0 02 2.0 B 3 20-005 agagafiaaflfiagg 03. 03. £8 08 [flawlfl :..8 mmlflflal 08 |:__lal 08 =08 .50... SB 88 :8 :8 m2 :2 mm mm 035 2.3 E E 20.50 122 00.00:. 00 00 00.000: 00:.0 0:.0000 00.00 0.00:: 00:.0 00.0: 00.0 00.0 :0 00.00:: 00.0 B 00 00.: 00.0 00:. 00.0 00.0 00.0 :0 00.0 00 00 0.0.0006 00.0: 00 00 00.0 000 00:. :00 :0 00.0 00.0 00.0 B B 2:006 0:.00 00 00 00.00 0:..: 00.:. 00.: 0:.0 0:.0 :.00 00.0 B 00 00-0006 :0: 00 00 00.: 00.0 :.00 000 00.0 :00 00.0 00.0 00 B 0.0-0006 00:. B 00 :..: 00.0 00.0 0:0 :..0 8.0 00.0 00.0 B 00 0.2006 :0: 00 B :..0 00.0 00.0 00.0 :0: 00.0 00.: 0:.0 00 00 00-0006 0.0.0 00 00 :0.: 00.0 00.0 000 0:..0 00.0 00.0 00.0 B B 0.0-006 0::- 00 00 00.0 :.00 00.0 00.0 :.00 00.0 :00 00.0 B B 0.:-:06 00.00:. B 00 :.00: 00.0 :0.000 00.0 20 ::.0 00.0 00.0 00 00 00.006 00.000 00 00 0:.00 00.: 00.00: 00:. 00.00 :.00 00.0 00.0 00 B 0.0-006 0:..000 00 00 0:0: 00:. :.0.00:. 3.0: 0:.00 :00 00.0 00.0 :0 :00 0.206 0:030 00 00 0009.0 :.0:.0 00.0000: 000:: 0::.0:. 00.00 :000 00.: :00: :0 00.006 00.00 00 00 00.0 00.0 00.00 0:: 00.0 000 00.0 000 00.0 :00 0.0-0:6 00.00 00 B 00.00 00.0 00.00 00.: 00:: 00.0 00.0 :.00 00 00 2:6 020:0 B 00 00.00:. 0:..0: :0.00: 00.00 0.3.00 00.00 000:: :..0 00.: 00.0 0.0-0:.6 00.0 00 00 0:: 000 :..:. 00.0 00.: 00.0 00.: ::.0 00.0 00.0 0.0-0:00 00.0 00 00 00.0 00.0 :.00 00.0 00.0 :.00 :.00 0:.0 00 B 2.20": 00:.0 00 00 00.0 000 :.0.:0 000 00.: 000 :.00 :00 00 00 0.0-0:0": 00:. 00 00 00.0 00.0 00.0 :0 000 :00 00 00 00 3 0.0-00:: 00.0 B 00 0:.: 000 00.0 0:.0 :0: :.00 :.00 00.0 :x: 00 0.20:": 03.00 B 00 :.0.:: 00:. 00.00: 00:. 00.0 00.0 00.0 00.0 B 00 00.00:": 00.0 B 00 :00 00.0 :0: 00.0 :5 B :5 B B 2 0.0-00:: 00.0 00 B 00.0 00.0 00.: 00.0 0:.0 :00 00 00 B 3 0.0-00:”: 00.0 00 B :.00 000 :0 00.0 0:.0 00.0 00 B B :0 0.0-00:": agagflflaflfl-afigflag a :50 08 0:8 :50 0:00 :03 0:8 08 0:8 09- 0:8 08 £8 :35 0:8 008 :08 :08 :2 :2 :0: :0: 0:05 00.3 x: x: 0:00.00 123 00.00: 00 00 00.:.0: 00.0 000:. 0:.0 00.0 00.0 00.0 00.0 0:: 00 0.0-000: 00.0 00 00 00.: 8.0 00.0 00.0 00.0 00.0 00.0 8.0 :x: :x: 0.0-0:.0: 00.0 00 00 :.00 00.0 00.:. 00.0 00.0 00.0 ::.0 00.0 00 00 0.:-::.0: :0.::. 00 00 00.00 00.0 00.:.: :.00 00.: :.00 :.0: 0:.0 B 00 0.0-0:.0: 00.00 00 00 0:..0 00.0 :..0: 000 00.: 00.0 00.0 000 00 00 0.0-000: 00.00:: 000:.0 0:.0 00000:. 000:. ::..00:: 00.00: 00.000 :0: 00.0: 00.:. :.0 000 0.:-:00: 0:..:0:.00 B 00 :0.:000 00.:.0 00.00::0 00.:.00 00.000 :..0 00.0: :00 00.0 00.0 0.0-000: 0000:00 20:. 00.0 000:.00 00.0: 0:..0::.00 0:..00: 0.00: 0:..:: 00.000: 00.:0 00.0 00.0 0.0-000: 00.0000: :0.:0: :0: 000::0 0:.00 :.:.:000 00.00: 00.00:. 00.:. 00.000 00.0: 00.0 00.0 0.:-:00: :.000000 :0.00 :.:.: 8.50 000:: 00.:0000 00.000 :.0.00:. :0 :.:.00 0:.0: 00.:. 0:.0 00.000: 00.0 00 00 00.0 00.0 00.0 00.0 00.0 :00 00 00 00 00 0.0-000: 00.0 00 00 000 :.00 00.:. 00.0 00.0 00.0 00.0 00.0 00 00 0.200: 00.0: 00 00 0:..0 00.0 00.0 00.0 00.0 00.0 000 00.0 00 00 00.0000: 00.:.: B 00 00.0 00.0 00.0 :00 00.0 00.0 00.0 00.0 00 00 000000: 0:.0: E 00 00.0 00.0 0:..0 :00 00.: 00.0 :.00 00.0 00 00 0.0.0000: 00.0 00 00 00.: 00.0 :.:.0 00.0 00.0 00.0 00.0 00.0 0: 00 0.0-0:0: 0000:: 00 00 00.000 8.0 00.:.0:. :.0.0: :0.00 00.0 0:.0: :.0: 00 B 0.:-::0:: :00 00 00 0.0.0 00.0 00.: 8.0 00 00 00 00 00 B 0.0-0:0: 00:0 00 B :.00: 0:.0 :.00 00.0 00.: :00 00.: :.00 00 :5 0.0-00:: 00.00 00 00 00.00 :.0: 00.0: 00.0 00.: 00.0 :.00 00.0 00 00 0.20:: 0:..0:0 00 00 0:..000 :.00 :0.00 :.0.0 :0: 00.0 00.0 00.0 00 00 00.00:: 00.:.000: 00 00 00.:.:. 00.:.: 00.0000 00.000 00.000 00.00 0:..0: :.0: 00 00 0.0-0:: 0.00:.00: 00 00 :0.0000 0:.00 0.0000:.: 00.000: 0.0000 00.00 0:00 00.0 00 00 0.:-:::: 0:800 00 00 00.000: 0000 :..000000 00.0000 0.000: 00.00 :0.:0: 0:.0 00 00 0.0.0:: 0:..00:. 00 00 00.0: ::.:. 00.00: 00.0 00.00: 00.0 00.0 0:..0 00.0 00.0 0.0-00:: 00.00 00 00 00.0: 00.0 00.0: 0:..0 00.0 0:.0 0:..0 00.0 00 00 0.:-:0::: agagadflflagagagg :08 08 0:8 08 :..:em 08 .58 09- 0:8 08 :58 48 :..:a :30:- 0:8 0:8 :08 :08 :2 :2 :0: :0: 04B 03$ :00: :0:: 20800 124 0: .0.: :5 :5 00.0 N: .0 w0.m: :0.0 V0.0 No.0 0:...0 v0.0 :5 :5 0.0-0:03: afimvmw :5 :5 0&0530 0:00: 3.0090 00.50 00.00 mwd 00:00 .30.: :5 :5 0.:-:VNV: 0.0.3.030 :5 :5 0: .w000: 00.: :: N: .00: mm 00.00:0 00.030 00.::0 00.:.0N 0N0 :5 :5 0.0-0:0NV: 00.0 :5 :5 00.0 00.0 w:.0 de 00.0 :00 NN.0 No.0 :5 :5 0.0-mNNv: v0.00oN :5 :5 N005: N00: 00.0N0: 3:0: ww.0:: wad 00:00 N:.0 :5 :5 0.:-:NNv: N0.Vw0:.0 :5 :5 00.0505 00.00 w0.0w§:m £0.00 9:.th 00.: w0.Nmm 00.: :5 :5 0.0-0NNv: N:.0:V :5 :5 00.:.: 0:..0 0:0.wN 0:.: hN: v0.0 0:.: ::.0 :5 :5 0.0-009: :00-0.05:: :5 :5 :0.:000 N090 0N.:V00 000: 20.02 0:.: >0. :0: Nb: :5 :5 0.0-00Nv: 00.0 :5 :5 00.: 00.0 0w: 00.0 00.0 :0.0 :0: .0 :0.0 :5 :5 0.:-:.N: 00.00 :5 :5 90.00 00.: NN.:: Nm.0 00.0 No.0 00.0 00.0 :5 :5 0.0-059. wwN: :5 :5 :w.0 VNd 0.0.0 0N0 0:..0 00.0 0N0 00.0 :5 :5 0.0.0009. h: .: :5 :5 :5 :5 :5 :5 :5 :5 :5 :5 :5 :5 0. : -: 0N:- 0: .00 :5 :5 010:0 0: .: 0:..0 N00 :uN:v ::.0 0:..0 00.0 :5 :5 0.0-00N: 00.0 :5 :5 00.: w0.0 0:00 :00 0w.0 00.0 :.N.0 00.0 :5 :5 0.0-00$. N0.0::bw :5 :5 :0.:00 w0.00 0w.N0mob 00:00 0:.w:N: 0:00: :0.:00 0:.N: :5 :5 0.:-:0N:. 00.0N: m: :5 :5 $0.: :00 00.50 N0.0N0:.m 00.wa 00.NNm :0.N 0N.Nb: 00.N :5 :5 0.0-00N: MN.0N :5 :5 0w.0 ::.0 0b.N: :00 00.: 00.0 0.0.0 00.0 :5 :5 0:-: :N: 00.:.:-w :5 :5 wfiwfim 01:: :0.000 00.0N 50.00 0N.: 0v.:N 0b.: :5 :5 0.0-0:N:. 300NON 05.30 50.:0 0:0: :0N 0N.:.m :.N. :0::0: 00. ::uN 00.0: m 00.0 ::.mwN Nm.w :5 :5 0.0-00:: 00:80::V 0.000N deN 0b.00Nw 00.00: 30.50.0N 00.00:: 00.00: 00.0 00.0:0N 0N8 :5 :5 0.:-:0:: 00.:.:-5N0 00.0N: 30.: 00.0wvo 000:: :NdZ-NV 00.0:0 w:.NwN 0N.m V0.N0: w0.v :5 :5 0.0-000:: 00.5%N0 :N.0w 0.0.: #08500: 0: .wV: :0.wN00v 00.000 hNdQN v0.0 Nv.N0: v0.0 :5 :5 0.0-050:: ww.N0.VNv >080 00.0 0wNVOw 0:.: :: 00:00:00 00.000 VMSNN N:.N 00.0w: wN.v :5 :5 0.0-000::- 20:0 :5 :5 w0é: w0.0 00.N: 50.0 0:.0 ::.0 00.: 0:.0 :5 :5 0.:-:o0N: 00.00 . 3.0 00.:: w0.0 00.N N: .0 0.0.: 0: .0 :5 :5 0.:-:50N: :m.wm :w.0 v0.0: 00.0 00.0 N:.0 0:.: 0:.0 :5 :5 0:-:00N: mewE my: mewE my: mewE my“... 3|:me my: a NEE :00 ::.:00 08 :..:S 000 0:8 :50 0:8 08l0l08 130,—. :NO M: £2 mm: Mm: mdc‘ m<>> NH NW 0:.:—:30 125 :0.0 :5 :5 06.0 No.0 0: .N 00.0 NN.0 :0.0 NN.0 N00 :5 :5 0.0-06$): 00.066 :5 :5 00.550 00.0 00.00 00.0 00.5 00.0 00.6 00.0 :5 :5 0.:-:6N:>: 60.600 :5 :5 00.50N N06 0N65 50.: 50.0: 0N.0 N0.5 :0.0 :5 :5 0.0-06N:): N6.00 :5 :5 :0.5 00.0 00.0: 00.0 60.0 60.0 :N.0: 00.0 :5 :5 0.0-0NN:>: 06.5: :5 :5 00.60 00.: 05.56 00.: Vw.N 00.0 05.N 0:.0 :5 :5 0.:-:NN:>: 00.0w :5 :5 :0.00 06.: 56.6N 50.0 60.: 00.0 05.: 0: .0 :5 :5 0.0-0NNS: 60.:6 :5 :5 :5.0N 00.0 :00: 6N0 00.0 No.0 05.0 60.0 :5 :5 0.:-:0N:): 56:60 :5 :5 VN65N 06.0: 00.0N0 0: .0N 00.:N 05.0 00.0: 06.: :5 :5 0.0-00N:>: 0N.0 :5 :5 N0.N ::.0 N0.N 0: .0 50.0 No.0 0:.0 No.0 :5 :5 0.0-05N: 0N.N6: :5 :5 00.05 56.: 50.00 :N.: 0: .0 00.0 00.N ::.0 :5 :5 0.:-:5N.: 0N.060 :5 :5 N0.000 00.0 5: .00: 00.: 06.: : 00.0 00.0: :N.0 :5 :5 0.0-05N: 05.0Nw :5 :5 0:.006 00.0 50.0: 0 00.6 00.0 0:.0 00.0 0: .0 :5 :5 0.0-000N‘: Nw.500 :5 :5 00.000 0N.0 60.00N :N.0 0: .0 50.0 55.6 ::.0 :5 :5 0.0-050N1: 0:.:5w :5 :5 00660 6N.0 :0.::0 ::6 00.0 0:.0 N00 0:.0 :5 :5 0.0-0:001: 06.:0 :5 :5 00.:5 00.0 0:.0 ::.0 00.0 :0.0 00.0 N00 :5 :5 0.:-:0N..: 00.00 :5 :5 N: .N0 N0: :0.5N 00.: 55.0 6: .0 00.N 0N.0 :5 :5 0.0-00N1: 06.5 :5 :5 00.N 00.0 65.6 NN.0 00.0 00.0 0 0.0 00.0 :5 :5 0.0-00N: 0N.N550 :5 :5 05.00:0 0N.NN :6.006N 00.0: 00.00: N0.: 00.:0 60.0 :5 :5 0.:-:0N1: 50.0w0N :5 :5 00.060N V0.0: 00.000 00.0 00.06 6N.0 00.0: VN.0 :5 :5 0.0-00Nx: 66.56 :5 :5 00.NN :00 :0.5: 00.0 :0.: 50.0 00.0 00.0 :5 5 0.:-::N1: 00.N6 :5 :5 50.0: :00 65.5: 60.0 :66 5: .0 06.0 00.0 :5 :5 0.0-0:N.: N06N :5 :5 0:0: 0N.0 :0.0 00.0 00.0 :0.0 00.0 00.0 :5 :5 0.:-:wNv: 60. :0: :5 :5 0N.50: 00.N 60:50 0: .: 00. : No.0 00.: 00.0 :5 :5 0.0-00Nv: 60.060 :5 :5 00.0N0 5: .0: 0N.0wN 00.0 00.:N 06.0 :00: 00.0 :5 :5 0.0-00Nv: 00665 :5 :5 05.050 56.0 :6.:0: 00.: 06.0: 00.0 :N.0 0N.0 :5 :5 0.:-:0Nv: 50.00 :5 :5 60.0: 00.0 05.0: 06.0 00.N 00.0 50.0 50.0 :5 :5 0.0-00Nv: wme meE NEE mewE AME mewE 1|:VwE meE AWE a meE wmmE AWE :08 08 :.:0m :08 :.:Om :08 :.:Om :08 5:8 :08 :38 10m :58 :50? NNO NNC :NO :NO ME): Mu): mm: Mm: m<>> 3:5 NM: Mm: 0:050 126 :00: 00 00 00.0: 00.0 :0.0 00.0 :.0: :.00 0:..0 :.00 :x: 00 0.0.0000: 0:..00 B B 00.0: 0:..0 00.0 00.0 00.: 00.0 0:..0 00.0 B 00 0.0-0000: :.0.:0 00 00 0:.:: 00.0 :.00 00.0 0:.: :.00 00.0 00.0 00 00 0.0-0000: 00.0:.0: 00 00 :0.:0: 00.0 0:.:: 000:. 0:..00:. 00.0: 00.00 00.0 00 B 0:-:00: :0.0:.000 0:: 00 00.0000 0:.:.0 0:.0:.0:.0 00.0:0 0:..000:. 00.00 00.:.00 :.0.0: 00 00 00.000: :.0.000 00 00 0:..00: 00.0 00.000 00.:.: 00.00 00.0 00.00 :.0: 00 00 0.0-0:.00 00.00:.0 00 00 00.0:00 00.:. 00.0000 00.0:.: 000:. 00.0 :0.00 00.: 00 00 2:6 :0.000:.: 00 00 00.0000 00.00 00.0000 00.00 :.0.00:. 00.0 00.00: 0:.:. 00 3 00.9.8 ::.00:.0 00 B 0:.000 00.0 :.0.:000 00.00 00.0... :..: :0.00 00.0 00 :x: 0.0-0000 :.0.00000 00 00 00.0000 :.0.0:. :0.00000 00.000 000:.0 00.0 :.0.:00 00.:.0 00 00 0:-:0000 :.:..:.0000 00 00 00.0000 00.00 00.0000: 00.000 :0.000 :00 ::.000 00.00 00 00 0:-:0000 00.00000 00 0:: 00.0000 00.:. :0.0:0:0 00.000 00.0:0 0:..0 0:.000 00.:.0 00 00 0:-:0000 :0.00000 :0 00 :0.0000 0:..0:. 00.0:000 00.000 00.00: 0:.: 0:.:.0 :.0: B 00 00.0000 :.:.00 00 00 :.0.0: 00.0 00.:: 0:..0 :00 00.0 B 00 00 00 0.0-0007: 00.00 00 00 :0.00 00.: 00.0: 00.0 00.: 00.0 00.0 00.0 00 B 0:-:00z 00.00 0:: 00 0:..00 0:.: 00.00 :.0: 0:.: 00.0 :0: 00.0 00 00 00-0007: 0:..000 00 00 0:.:.0 00.0 00.00: 00.0 00.0 00.0 00.:. 00.0 00 00 0.0.0007: 00.000 00 00 00.:. 00.: 00.000 00.0 00.0 :00 00.0 00.0 00 00 0:-:002 00000:: 00 00 00.0:00 000:. 0:.0000 00.00 00.000 00.: 00.00: 00.: 00 00 00000:: 00.0000 00.00: 00.0 0:..000: 0:.:0 00.0000 00.00 :0.00: 00.: :0.0:. 0:.: 00 00 2:02 00.:000: 00 E 00.::00 0:..00 00.00:.0 0:.00 00.000 ::.0 00.00: 00.0 :5 00 0.0-0:02 0:..0 00 00 00.0 :.00 00.0 0:.0 00.0 00.0 0:.0 00.0 00 B 0.0-0002 00.:: 00 B 0:.0:. :00 :.0.00 00.: ::.0 0:0 00.:. 00.0 0:: 00 0:-:002 00.:000 00 00 00.000: 00.00 00.000: 00.:0 00.:.0 00.: 00.00 00.: 00 00 0.0.0002 :0:.:.0: 00 00 :.0.000 :00: 00.:00 00.0 00.0: 00.0 :0.0 00.0 00 00 0:-:002 00.000 00 00 00.0:0 :0:: 00.00: 00.0 00.0 0:.0 00.0 00.0 00 00 00-0002 §§%§%§%§§§%§§ leomlflllfi: :50 ::.:00 :50 0:8 08 .58 03- 0:8 40%| 5:8 :50: 0:6 0:0 :03 :08 :2 :2 :: :: 03$ 03$ :0: :0: 0:00:00 127 00.0:.:. 00 00 00.000 00.0: 00.0:00 00.00: 00.00: 00.0 000:. 00.0 :.:.0 :00 0.0-000:: 00000:: B 00 00.000 :.0.00 00.0:.:0: 00.0:.:. :.0.00: 00.:. 00.00 00.0 00.0 00.0 0.200: :.0:.00: 00 00 00.0:0 00.0 :0.:00: 0:.00 00.00 00.0 00.0 00.0 :00 00.0 00.000: 00.00:.0: B 00 00.00:. 0:..0:. :.:.000:.: 00.00: 0:..00: 00.: 00.00 00.: 00.0 00.0 0.:-:00.0 00.0:.00: 00.00:. 00.0 00.0:0:. 00.00 00.0000: 00.000 00.:.:0 :..0 0:..00 00.0 :0:. 0:.0 0.0-000:. 00.0:0 00 :5 00.000 00.0 00.00: 00.: :00 00.0 00.: :.00 00 00 0.2000 00.0000: 00 00 00.0:.00 00.00 00000:. 00.00 00.00: 00.: 00.:. 00.: :.:..0 00.0 0.0-0000 00.000: 00 00 00.00:. 00.0 00.00:: 00.0: :0.:0 00.0 00.00 00.0 B B 0.0-000: 00.:.0000 00 00 0:.0000 :.0.00 0:.00000 0:.00: 00.000 00.: 0:.:0: 00.0 :0: 00.0 0:-:00: 00.:.0000 00 00 00.:.000 0:.0:. 00.:.00: 0:..0:0 :.0.00: 0:.: 00.0: :.00 :.:.: 00.0 00.000: 0:000 00 00 00.0: 00.:. 0:..000 00.0 0:.0 00.0 :00 00.0 00.0 :00 0.0-000: 00.:.000 00 00 00.:00: 00.00 0:.000: 00.00 00.00 00.0 00.00 0:.: 00.0 00.0 0:-:00: :.0.::00: 00 00 00.00:.0 00.00 00.:.000 00.00: 00.:.0: 00.: 0:..00: 00.0 00.0 00.0 00.000: 00.0:.00 00 00 :.:.0 00.0 00.0:.00 0:.00: 0:.0 00.0 :.00 00.0 00 00 00.0000 00.00:.0 00 00 00.:.:: 00.:.0 00.:.:.00 00.00: 00.:00 00.0 00.00: 00.0 0:..0 00.0 0.0-0:.00 :0.0000 00 00 0:.:000 :.:..0:. ::.:00:. 00.00 ::.000 00.:. :0.0:: 00.:. 00.0 0:.0 0.:-:o:.0o 00.0:00 00 00 :0.:000 00.:.:. 00000:. 00.00 0:..000 :.:..0 000:: 00.:. 00.0 00.0 0:-:0:.00 00.0000 00 00 00.:000 00.:.:. 00000:. 00.:.0 00.000 00.0 :0.0:: 00.:. 00.0 0:.0 0:-:0:.00 00.::00 00.0:0 00.0 00.:000: 00.000 00.:000: 00.000 00.0:0 :.0.:: 00.00: 00.0 00.0 0:.0 0.0-0:.00 00.00 00 00 00.0: :00 00.00 00.: :0: :.00 00.: 00.0 B 00 0.0.0000 :0.0000 0:..00 :.00 00.80:. 00.00 00.0000 00.00 :.:.00 00.0 00.00 0:.: 00.: :.00 0:-:000 00.0000: 00 00 0:..00:.0 00.00 00000:. 0:.:. 0:..00 :.:..0 0:.00 00.0 :.:.: 00.0 0.0-0000 agaafidflwfladfliflagaflwflfl :08 08 008 000 0.:00 03- 0.:8 :50 008 :08 0.61%? :0.0:. 0:00: 0:8 :06 ::o :2 :2 :0: :0: 003 00.00 x: x: 20.000 128 00.0 -- 0:..0 000: :.0.0: 00.0 -- 0:0: :00 :x: 00.: :0: 00.0 000 :x: 63. 00.0 B 00.: 00.: 00.0 00.0 B 0:-:0:: 00.0 :x: 00.: :0: 00.0 :00 B 0:-:0:: :0.0 B 00.: 00.: 00.0 00.0 B 0:-:0:: 00.0 -- 00.0 00.0: - :0.00 -- :0: 00.0: :x: 00.0 0:.0 00.0 0:.0 B o>< 00.0 B 00.0 00.0 :x: 00.0 :x: 00-000: 00.0 B 00.0 00.0 :0: 0:.0 :x: 00-000: :00: :x: 00.0 00.0 00.0 00.0 :x: 0.0000: 0:..0: -- 00.00 :.00 -- 00.0 -- :0: 00.:. B 00.0 0:.: :x: 00.0 B 63.. 00.0 B 0:.0 00.: :x: 00.0 :x: 00.000: :00 :x: :.:.0 0:.: B 00.0 00 00-000: 00.0 B 00.0 :0: :x: 00.0 B 00000: 060. I000 0000.04. 000.0 00:00. . __ lama 08 08, 03.. 08.. 03.“. A 00.0. ., . 03. ....30009: :.:.00. 0:6 w :0: :2 . :: w 00:5. :0:... £00.00, 0:05:50 :.0.::: 0:0-0:5: 50:7: 0: V05N :55 00:00:30.: 85: 2:: :0 000032: 63:00:50 300:0: 2:: 08:50:: Q0: 00:90:00 88:30: 35 :o own-:02: 2:: 038:5: O>< 0:05 5:63 .060 0:08:30 0: 00005000000 00:88:: :00 129 3.: «hum ac.§ 8.2 E .2 3.0. 3 Dmm endow? wean 8.2.3 madman 8.53 862 3 O>< cwsbhun 8me 3.23% 84:09. wfimwm vhmfl 3 mdéom: 3.03% 33 $632 Emma? madam 9&2 B , 20-95:. $.80”? 3.3 3.9mm mamvmm Vmsmm 8&3 3 Egg: mad -- 8.2 and 3% 92 -- and 2.3 B 9&2 and 25 mo; 3 O>< 23m 3 8.3 mnfi ofim mo; 3 0732: ohnm B 3.2 8.3 mad no; 3 2-168 Sam 3 3.3 3.2 om.m o: 3 2-303 m~.m -- and 3.0 3.3 -- .. max 3.0 3 Rd mm." :.o B B 03.. RN 3 :.o a; B 3 3 0932"— aaN 3 26 34 Ed 3 B m.m-m£._m 8a 3 3.0 2d Ed 3 B Wméfia modm -- Exam 3.? 3&3 mné -- Om“ mwé B v~.~ mm; mod mfio B 0>< omé B o~.m 84 86 2.0 3 n.m-moan 3.0 3 EN 3 .N mm; :.o B m.m-mnma mad 3 o: o: one Ed 3 m.m-m~ma Ilwflwiflluwflwm: lg... com com com .. . «3:333— :50... 88 mm .2033 130 8.0 -- NS 3.0 m3 «2 2.0 max 3.300 3 02:0 2.88 5.8 «an: 0mm 03.. 2.8? B 033.0 :.:5. 3.08 an: own 2.38 3:00 3 8.5.0 $.an $.03 80: 8.“ 2.30.8 8.88 B 8.50 3.080. 00.0% 03: 03 2.38 08 -- 00.0 8.0 0.0.2 0.0.2 -- 8.0 8.8 B a»: 8.0 3: 3.0 B o>< 5.2 B one 3.0 «S as 3 2-380 8.00 3 $2 8.0 80 $3 3 3-280 $.00 B 2.: 03 a: 03 3 3-38 :.0 -- 00.0 a; m? 00.0 -- 80 2.03.0 B 00.88 $.32 26$ $.30 B 03.. 3.0030 2 808m H.880 00.9.0 028 3 2.380 3.302 3 0203 8.80: :08 :.wow 3 2-308 80008 B 3.82 3.220 8.08 :08 3 2-38 3.2 -- 8.8 8.0 8.0 8.: -- a? 8.000 B 2.8.. 3.8m 00.0 9% B o>< 00.me B 2.0% 8.0: 8.0 86 B 2-8an 00.0% 3 8.03 00.000 2.0 05. B 2-22.0 02$ 3 8.3% 6.5 and Sn 3 2-33 Inflmladfla a w . .ufla. . ,8... 0.8 Ba. Ba 08-. . ..8 83.003. .53. 88 :8 :2 mm N Na, . 205m 131 RN -- ems wwd wag: mix NYE Qmm Q . fl w cod 8.8 :..bm Eng mad 2 .o O>< wodh cod Omfim 34mm m3: wmd :.0 3R? 385m mmfiw cod wbdm mmdm 84 fl 3 .v m fl .9 SFQm 355w 2 Am cod mimm No.wm wmdfi No;u :6 352m ghmgm on. "w cod bmdm G. ; mud“ and 9 .o vaQN 352va no.3. cod cofim oodm 3.2 ow.m Ed SEAR vomeMm 2 .8 cod cmfim wvdm COS and n fl 6 ES. 382% 88%? «Beam, 132 Amiifl Table E-l. Soil Organic Matter Content sample ID . ’3 "3%OM: SampleID' ” ..%OM.. Sample ID ' f,§%.”OM 3. B3aO-0.5 2.2 331-15 5.2 333-35 1.0 350-05 0.8 351-15 0.7 353-35 1.1 370-05 0.6 371-15 0.6 373-35 0.3 3930-05 2.4 391-15 2.8 393-35 0.3 3110-05 NA 3111-15 0.8 3113-35 0.9 3130-05 2.3 31331-15 1.8 3133-35 0.5 3150-05 5.3 3151-15 15.2 3153-35 35.8 3170-05 5.5 3171-15 0.6 3173-35 21.5 C20-05 2.3 C2l-15 0.3 C23-35 0.3 C40-05 2.3 C41-15 1.1 C43-35 0.6 C60-05 0.4 C61-15 1.0 C63-35 0.1 C80-05 4.2 C81-l5 0.7 C83-35 0.9 C100-05 2.1 C101-15 1.3 C103-35 2.0 Cl20—05 2.9 C121-15 0.4 C123-35 0.2 C140-05 5.2 C14l-15 0.3 C143-35 0.4 Cl60-05 1.8 C161-15 NA C163-35 NA D50-05 1.8 D51-15 1.1 D53-35 0.7 D70-05 4.2 D7l-15 0.4 D73-35 0.7 D90-05 3.7 D91 -1 .5 0.7 D9a3—3.5 0.6 D1 10—05 0.7 D11 1-15 0.3 D113-35 0.2 D130-05 3.7 D131-15 0.5 D133-35 0.6 DISC-0.5 2.1 D151-l5 1.8 D153-35 0.8 D170-05 32.1 D171-15 30.6 D173-35 4.3 D190-05 19.2 D191-15 71.0 D193-35 18.8 3140-05 1.9 3141-15 3.5 3143-35 0.4 3160-05 28.2 3161-15 49.8 3163-35 35.8 3180-05 34.5 3181-15 55.7 3183-35 NA 3200-05 2.2 3201-15 1.8 3203-35 NA Fl30—05 1.8 F131-15 0.9 Fl33-35 0.3 F150-05 20.7 F151-15 20.4 F153-35 0.3 3170-05 5.5 F171-15 0.6 31733-35 0.2 3190-05 5.4 F19l-15 1.4 F193-35 0.5 3210-05 0.7 F211-15 0.6 F213-35 0.8 (3140-05 7 (3141-15 4.5 (3143-35 0.6 0160-05 65.8 (3161-15 8 (3163-35 6.4 (3180-05 4.9 (3181-15 0.6 (3183-35 0.3 G200-05 2.8 (3201-15 0.8 (3203-35 0.3 G220-05 1.9 (3221-15 2.3 6223-35 0.4 H150-05 14.8 H151-15 5.9 H153-35 15.8 11170-05 34.2 H171-15 56.7 H173-35 5.8 H190-05 22.9 H191-15 23.1 11193-35 70.2 133 Table E-l. Organic Matter Content (continued) Sample ID 97 .%‘OM I . Sample ID 3 %0Mi . Sample ID "‘70 OM: 11210-05 0.2 H211-15 8.5 H213-35 0.4 H23aO-0.5 2 H231-15 0.5 11233-35 0.2 1200-05 48.9 1201-15 79.4 1203-35 66.6 1220-05 65.3 1221-15 74.5 1223-35 0.4 1240-05 3 1241-15 0.3 1243-35 0.3 1260-05 16.7 126a1-1.5 5.1 1263-35 NA 11930-05 65.3 1191-15 76.3 1193-35 92.1 1210-05 2.6 1211-15 1.2 J213-35 NA 1230-05 74.4 1231-15 70.7 1233-35 0.4 1250-05 23.8 1251-15 96 1253-35 2.3 J270-05 9.6 J271-15 0.5 J273-35 NA K200-05 81.3 K201-15 NA K203-35 3 K220-05 76.5 K221-15 81.7 K223-35 0.2 K240-05 72.2 K241-15 77.7 K243-35 1.1 K260-05 4.7 K261-15 60.3 K263-35 30.1 K280-05 25.8 K281-15 35.8 K28-35 NA L210-05 2.1 L211-15 2.9 L213-35 NA L230-05 77.3 L231-15 86.6 L233-35 1.2 L250-05 2.1 L251-15 76.1 L25a3-3.5 49.5 1270-05 77.5 L271-15 12.8 L273-35 0.3 M200-05 2.7 M201-15 22.2 M203-35 NA M220-05 12.5 M221-15 13.5 M223-35 2.1 M240-05 25.0 M241-15 75.0 M243-35 0.2 M260-05 35.3 M26l-15 50.0 M263-35 NA M280-05 19.3 M281-15 15.2 M283-35 0.6 N210-05 68.4 N211-15 58.0 N213-35 NA N230-05 77.3 N231-15 2.2 N233-35 4.6 N250—05 3.4 N251-15 34.9 N253-35 3.7 0220-05 69.9 02231-15 38.1 0223-35 4.5 0240-05 54.3 0241-15 18.8 0243-35 3.2 P230-05 61.9 P23 1-15 2.1 P23a3-3.5 8.4 P250-05 62.1 P251-15 58.2 P253-35 4.4 240-05 54.4 Q24a1-1.5 25.0 Q243-35 34.4 Q260-05 15.7 Q261-15 NA Q263-35 NA R250-05 51.5 R251-15 17.4 R253-35 2.7 R270-05 37.2 R271-15 59.4 R273-35 51.2 8260-05 35.8 8261-15 66.1 3263-35 NA 1270-05 46.7 T271-15 60.3 T273-35 NA U260-05 1.0 U261-15 5.6 U263-35 3.1 NA - indicates that no sample was taken for that interval 134 Apmndix F Agueous Field Samples Appendix F-l: Pore water data for samples taken on 7/26/97. Two dashes (--) indicates a parameter that was not measured and bd indicates that the amount in the sample was below detection. that the samples were taken on a peeper. Samples with spring or surface in the name were samples collected at the surface. Samples with top or bottom in the name indicate the relative depth .. . , '~; .gramp. .- " . , * as 1160;.) or“ ‘-1Br.' , s03 - N037? FfS’fflg-fj; .‘i Sample; : L? ‘(C) pH‘ . . ..Eh .» "(rig/L)- (m gmggpg _(_m_g/L) ‘;(mg/L).- (mg/15):; .123 top 17.5 6.49 -100.0 202.60 41.60 bd 1.60 bd 1.45 .123 bottom -- 6.85 -l48.0 173.93 39.60 bd 0.70 bd 1.44 K22 top 14.0 6.97 -15.0 324.93 37.40 bd bd bd 0.19 K22 bottom -- 7.06 -22.0 164.37 32.90 bd 6.20 bd 0.19 N23 top 16.5 6.54 -51.0 277.14 19.10 bd 1.70 bd 0.23 N23 bottom -- 6.58 -48.0 244.65 23.70 bd 0.60 bd 0.24 P25 top 17.5 7.32 150.0 91.74 21.00 bd 2.40 0.86 0.21 P25 bottom -- -- -35.0 221.71 19.50 bd bd bd 0.21 - - Doc 91.1.3 NH w Nectar) He? K x N C M: : San-mesa (mg/L) (mg/L) (as/L) '«(mg/Lx- (a. my!» (mg/Li «may J23 top -- 8.67 0.13 1.26 1.20 12.60 21.06 45.50 2.25 123 bottom -- 2.58 0.43 1.32 1.20 12.45 19.91 43.00 3.92 K22 top -- 3.37 0.38 8.32 3.90 14.35 18.46 57.50 2.87 K22 bottom -- 0.31 0.13 3.32 3.00 11.23 19.21 40.00 2.01 N23 top -- 11.61 0.46 47.40 50.00 14.37 14.54 65.50 2.02 N23 bottom -- 20.32 1.30 36.36 34.80 13.50 16.00 58.50 1.67 P25 top -- bd 0.12 7.08 2.15 6.55 14.02 25.50 1.22 P25 bottom -- 12.26 4.11 9.72 9.10 6.72 14.20 30.00 1.36 :7“ .. ca ““0 .:.safiiple.....a :1. ‘ ' 123 top -- J23 bottom -- K22 top -- K22 bottom -- N23 top -- N23 bottom -- P25 top - P25 bottom -- 135 Apfindix F-2 Pore water data for samples taken on 8/13/97. ’.‘-l‘ 1 , . f , ; . Alkalinity v; '~‘ ~ . ~ ' ‘1 3; L -. . 3 . ‘ " Temp. ‘ K g g . as HCO3', C1 1317'? '. ’1 $04 No; f’ 82‘: a! ' ’ 391111118: 1 (C) " . PH?” ~ '3' ‘Eh‘ . (ngL). (mg/L) (mg/L) (mg/Q (NEIL) (mg/L). 122 barrel 7.1 7. 08 -l40 160. 55 -- 0.79 J23 barrel 13.9 6.57 -152 168.20 -- -- -- -- 2.67 K28 barrel 10.4 6.59 -101 179.67 -- -- -- -- 0.44 L27 barrel 11.9 6.81 -52 374.62 -- -- -- -- 0.24 M28 barrel 12.5 6. 41 -45 324.93 -- -- -- -- 0.32 N25 barrel 15.7 6. 6 -71 217.89 -- -- -- -- 0.41 Q26 barrel 13.4 6. 65 -27 237.01 -- -- -- -- 0.17 S26 barrel 14.8 7.5 -10 202.60 -- -- -- -- 0.14 .. 1 1 ;. DOC ' CH. NH; Fe(total) j Fe??? : ' _ K [ Na ’Cagj‘jj" Mg Sample (111%) (111811?) (mafia) (mflLL. 1123/1?) (mg/L) (111844) @Efl') 01181.93. 122 barrel 2. 35 0.27 1.11 1.49 1.43 11.84 19.19 42. 50 2.26 .123 barrel 6.74 11.49 1.52 0.71 0.69 12.48 23.50 47.00 3.70 K28 barrel 5.57 0.13 0.91 5.00 5.02 15.76 22.16 48.00 3.14 L27 barrel 7.09 15.3 1.14 2.63 2.88 31.60 24.39 72.50 1.91 M28 barrel 10.27 31.02 5.07 29.67 30.62 15.44 15.94 59.50 3.85 N25 barrel 7.17 2.43 1.05 5.14 4.80 14.75 19.24 61.00 1.38 Q26 barrel 31.32 16.82 6.11 17.06 17.49 12.32 13.49 58.50 5.54 326 barrel 6.05 4.21 1.45 1.62 1.44 8.05 6.83 57.00 1.57 . i '32:-Caf: ' rs.» C ., 1 Cr =25: Mn Ni: Pb z s“ 122 barrel -- 0.22 2.08 25.12 0.03 3.33 -- -- -- 123 barrel -- 0.21 1.68 1 1.40 0.09 3.99 -- -- -- K28 barrel -- 0.52 0.48 2. 02 0.15 2.70 -- -- - L27 barrel -- 0.48 0.13 3.04 0.51 3.33 -- -- -— M28 barrel -- 0.31 1.10 40. 96 1.20 3.45 -- -- -- N25 barrel -- 0.29 1.22 6.64 0.21 3.09 -- -- -- Q26 barrel -- 1.45 5.17 5.72 3.18 3.11 -- -- -- S26 barrel -- 0.49 0.88 22.60 5.41 1.96 -- -- -- 136 Apmndix F-3 Pore water data for samples collected 10/8/97 . . ,-_. Temp ; , . * fl, asHCO3 Cl: , so. - No3 ;_‘.‘s?*?j‘~}j.Crc......f (Sample. " .(C). . “ "on Buy M): (ing[L) mg/L) (mg/L) (mm tug/Ly 123 top 9.5 6.51 -105 156. 73 48.80 0. 60 bd 1.67 16.43 :23 bottom 9.5 6.7 -125 137.62 48.40 0.80 bd 0.89 40.67 K22 top 9.9 6.76 -l88 210.25 22.20 0.60 bd 0.12 63.69 K22 bottom 9.9 6.99 - 157 129.97 37.40 5.60 bd bd 26.52 N23 1 1 6.24 6 175.84 21.10 0.80 bd bd 96.14 022 1 1.7 7.02 - 160 424.32 1 1.00 1.60 bd 0.46 43.36 925 top 12.4 6.37 19 91.74 31.80 bd bd bd 144.66 925 bottom 12.4 6.15 21 126.15 22.00 bd bd bd 167.90 925 Surf. - -- -- -- 34.80 1.60 1.68 bd 442.05 Q26 barrel 15.2 6.71 -95 137.62 29.30 0.80 bd bd 10.47 U26a 15.90 7.15 95.00 84.10 3.50 3.10 bd bd 3 .70 U26b 7. 52 25.00 137. 62 4.10 3.70 bd bd 4. M31 .Jf DOC TCH. NH. Fe(total) We . K Na'“'-*- Ca Sample (mg/L) (mg/1L) (mglL) (mg/LL (mg/L) (Ea/14)? Lng/D (mg/D Lg/Lla 123 top 1132 3. 01 0.26 0.64 0. 45 4.92 25.00 41.00 13.00 123 bottom 6.47 2.25 0.62 0.84 0.69 3.32 25.00 42.00 12.50 K22 top 8.33 6.34 0.55 3.56 3.41 4.53 14.00 40.00 11.00 K22 bottom 3.35 bd 0.58 3.56 3.31 3.23 20.50 50.00 14.50 N23 14.86 9.86 0.82 11.44 9.54 1.20 13.50 32.50 9.00 022 11.33 19.61 20.42 0.8 0.61 0.39 5.50 135.00 2.50 925 top 26.86 bd 0.86 7.64 9.54 1.95 19.00 26.50 7.50 P25bottom 11.95 4.61 3.20 9.36 10.53 1.41 15.00 25.50 6.50 925 Surf. 27.72 -- -- 16.04 -- 0.37 19.50 30.50 7.00 Q26 barrel 12.45 bd 2.44 11.36 7.96 2.32 12.00 32.50 8.50 U26a 4.07 0.43 bd 0.18 bd 0.54 2. 50 23.00 3.50 U26b 11.30 bd bd 0. 22 bd 1.24 3. 00 40.50 5.00 1336‘ 3 Cf“? .51“. Mn 9. g. 1 Ni 2 ’7" pb 'ftijn-fi 1' Sample ' ~ (pg/L) ' 3 123 top 57.28 0.16 3.0116. 43 70.19 2.14 1.70 2.43 187.61 123 bottom 51.47 0.16 3.36 40.67 32.24 2.39 0.91 12.14 189.41 K22 top 111.90 0.20 5.08 63.69 270.77 1.90 0.03 55.61 161.48 K22 bottom 127.04 0.18 6.54 26.52 395.47 1.99 0.09 93.63 201.89 N23 132.59 0.35 8.53 96.14 402.94 2.67 1.98 150.68 67.88 022 1403.05 0.39 4.40 43.36 270.15 9.78 0.50 162.19 187.82 925 top 62.90 0.85 8.76 144.66 361.96 3.74 1.84 242.62 70.34 925bottom 54.48 1.26 1.70 167.90 302.84 4.67 0.83 217.78 59.31 925 Surf. 109.05 1.77 5.20 442.05 391.70 3.56 2.82 21.71 62.32 Q26barre1 68.18 0.61 2.27 10.47 1410.10 2.32 3.72 14.40 130.39 U26a 32.31 0.42 15.47 3.70 391.28 3.14 1.48 5.63 44.57 U261) 41.09 0.34 4.43 4.31 680.85 2.23 bd 0.79 70.53 137 Apmndix F-4 Pore Water Data Collected on 11/20/97 }. Temp usample. (CL p.39 1" Ufa" ; ' f f ’ 54.116 As: 7 ' . .Eh;41; ‘(mg/L)‘ ”i (mgLL) A. - $021 (mg/L) N03 (mglLl 123 barrel -82 156.73 49. 20 12.94 K22 barrel 2.7 58 141.44 26.30 5.23 N 23barrel 1.8 47 141.44 24.00 0.66 022 barrel 5.6 -17 428.14 12.60 5.72 P25 peeper 13.00 99.39 31.50 bd P25 barrel 1.5 122.33 31.00 bd 1» . j ,'f">‘ 7. '_. "V v ‘ 2.‘ ,1 - 4' . _ . , ampe. . P25 surface . (m 9‘ *7. F9069!) ‘ (mg/L) 1r ‘Fe’f” ' (mg/141 (mglL‘T- ~' 123 barrel 4.81 0.32 0.21 4.16 K22 barrel 4.85 1.98 1.59 4.34 N23barrel 12.36 13.66 12.43 0.69 022 barrel 7.98 1.56 1 .49 0.45 P25 peeper 28.64 33.48 27.19 0.82 P25 barrel 19.11 7.44 7.09 2.72 P25 surface 19.99 12.90 1.29 sari-915*: ' f .' "f R.‘ " " 4 ‘7 ‘__ ‘vw. 7. ‘4 (1 - a» ' .3: . v . . =~'- a- ' ‘ ' ( ‘ «6' n 1 ".3 . . . -' I - ‘v .v‘ ‘\ .1 “ 1123' barrel 48.59 11.86 '__-' Cr 1 t - . . 3 u . , .7 , ,. v Ni f 3‘ r u. , . . ‘ a k . - , ‘ . - ‘ . 1 . 1 ( .517. . 5.35 3.83 73.48 2.11 K22 barrel 1 10.48 3.44 35.88 392.61 1.60 N23barrel 120.04 4.44 124.19 517.20 1.88 022 barrel 990.85 9.16 41.16 404.66 1.72 P25 peeper 106.31 4.31 327.91 592.45 3.31 P25 barrel 56.60 1 .99 122.54 350.16 2.27 P25 surface 90.24 1 .46 314.23 512.15 3.36 138 Agmndix F-S Pore water data for samnles collected 6/9/98 ‘1“ 4' ~ 93% Ju~o -- 1' ‘1 . 4"“ ' 149‘3- -' . .. . . ' u . . 4Q"r..4'l “warm-414...!“ Lu. J) 9, 1..' 5- :..; .I.« ' ' ' I, l r .. -' ’ Temp 113.552.; asHCO3 .‘gCr... 1 -.B‘t‘tf..~ . so. ~ ”No." s’f F‘é— Sample; ((3)82. ap'He; Eh (mgzLL (mg/L): 2"(mg/L) ung/L) t(mg/L)— 2‘ mm K22 11 7.09 ~118 282. 95 44.07 2.60 1.39 57.16 0.024 123 8.3 7.15 50 134.57 49.56 1.41 bd bd 0.036 N23 9.4 6.35 -20 319.18 21.40 bd bd bd 0.107 925 1 1 6.47 25 89.71 24.57 022 7.3 7.22 -77 517.59 13.26 L22 13.5 6.98 40 131.12 3539 surface jiooc Cm" NH3 Fe(t0ta1) Fe“ h. , i; \ ...Sainple .. ' m )L mg/L) (mg/I; (mg/1;); (min) ' . K22 14.53 14.99 16 08 123 1.47 -- -- 0.25 0.14 N23 8.78 -- -- 19.31 22.94 925 13.07 -- —- 4.49 2.19 022 10.20 -- -- 0.51 1.46 L22 9.90 -- -- 1.47 0.88 surface K22 238.25 0.28 0.30 53.83 1397.01 1.54 0.53 3.13 294. 64 123 46.62 0.16 0.82 3.58 1.59 1.19 0.58 7.67 173.35 N23 112.66 0.26 0.13 65.36 404.11 1.08 0.41 3.14 105.21 P25 54.39 0.45 1.09 61.59 308.85 1.25 2.14 22.17 56.45 022 866.56 0.42 0.57 29.32 182.93 6.39 1.67 27.50 278.20 L22 179.02 0.16 0.30 26.42 151.34 1.86 0.85 7.03 134.72 surface 139 Apgendix F-6 Pore water data for samnles collected 8/22/98 . Temp. ... 4 asHCO; Cl Br‘fi '" SO42“ N03" 21‘..asampie.u -ACL . pH... Eb. (mg/L) (mg/g.) (mgLL‘) (mglg (mg/L) , L: H21 spring 8.5 8.3 35.4 140 39.00 14. 54 3.32 122 9“” 15.4 7.13 -54.9 157 26.94 bd 1.05 bd peeper 122 spring 9.3 6.95 232.5 128 38.72 bd 16.42 5.58 bd J 19 P" 14.3 6.85 -252.6 314 65.72 1.41 24.61 bd 5.237 peeper K20 surface 17.3 9.05 179.8 140 36.68 bd 12.01 bd bd K22 surface 13.4 6.35 47.7 126 38.17 bd 6.30 bd 0.077 L21 peeper 16.7 6.13 8.6 156 34.57 bd 5.76 bd 0.731 L21 surface 16.8 6.38 165.8 191 39.49 0.40 2.39 bd bd N23 peeper 15.7 6.37 -38.7 280 26.71 1.12 1.31 bd bd N23 surface 18.4 6.37 130.7 70.7 10.36 bd 1.94 1.13 bd 925 surface 17 6. 68 5.3 174 40. 78 bd 1 2.7 bd bd ‘11 DOC “CH. “ “ NH.) Fe(total) “re" “3; Kg Na " Ca ,7: M‘” I Sample ‘- (mg/L) ‘(mg/L) (mg/L (mgLL) 1mm m‘g/L) (mg/L) (mg/L) ungflaL H21 ering 4. 74 0. 207 0. 79 2.42 20.12 43 27 13. 21 122 9‘1” 18.14 -- -- 34.08 32.86 6.26 13.90 60.12 12.48 peeper 122 sprig 2.47 -- -- 0.202 0.24 2.52 20.01 41.29 13.17 J 19 1:; 15.49 -- -- 0.419 0.32 2.39 34.76 90.24 21.54 K20 surface 15.81 -- -- 0.188 0.14 3.72 24.03 34.96 11.63 K22 surface 7.66 -— -- 1.884 1.75 4.17 19.35 37.93 11.10 L21 peeper 9.62 -- -- 1.055 0.84 2.26 20.10 40.79 12.19 L21 surface 11.77 -- -- 0.418 0.37 3.49 21.56 42.90 13.12 N23 peeper 8.68 -- -- 33.12 43.10 1.83 17.41 52.35 14.13 N23 surface 31.08 -- -- 0.399 0.51 6.43 4.87 19 24 5.43 925 surface 8. 42 0.198 . 20.93 45. 50 Ba 0 ’ Pb ”” . 1‘1 Samnleasmg/L ). L.:‘ ‘: " i. " ’ ‘- 11218311115 64.25 . 122 919° 219 53 19 1 0.28 9 18 596 32 2 24 0 63 185 99 169 87 122 spring 47.12 0.11 1.22 4.35 2.65 0.88 0.29 2.59 166.15 I 19;: 264.43 0.25 0.27 46.05 89.72 1.4 0.32 55.07 150.68 K20 surface 450.89 0.17 0.65 78.79 131.13 0.38 0.74 29.59 104.34 K22 surface 93.68 0.15 0.12 10.59 62.95 0.55 0.17 1.3 161.96 L21peeper 273.58 0.16 0.26 28.03 193.03 0.43 0.39 35.08 175.28 L21 surface 312.24 0.21 0.24 30.02 321.5 0.58 0.34 2.15 153.94 N23 peeper 196.73 0.21 0.17 71.74 405.29 0.97 0.55 116.51 99.13 N23 surface 25.91 0.27 0 8.87 164.45 0.75 0.23 4.64 50.59 925 surface 77.22 0.16 0 4.29 74.89 1.18 0.22 1.4 198.17 140 Aggendix F-7 Pore water data for samgles collected 10/10/98 1:11“- Temp fj];ff’-,}‘ ~ ~ _ Alkalmltyas c1 ‘3” £13er g; 1.3" Sample; 1121.; p11. .1111; Hco,. (mg/j.) (mg) (mg/1.1:... ' “ " " £11.) ml 9“” 8.8 6.51 —87.7 182 23.09 bd bd bd bd peeper "21 9“” 9.6 7.02 -547 184 35.80 bd 8.11 bd bd surface 122 surface 8.9 6.95 -41.7 160 37.58 bd 11.50 bd bd 119 peeper 7.5 6.8 -2003 241 56.72 bd 2.13 5.98 3.937 119 surface 10.1 6.26 -50.6 133 36.51 bd 116.04 bd bd 119 peeper 7.5 6.76 -192.6 261 58.89 bd 4.91 2.62 2.946 K22 surface 7.9 6.43 35.8 118 39.31 bd 15.65 1.63 bd L21 peeper 8.1 6.68 -1433 152 38.00 bd 0.76 bd 1.226 M22 surface 14.5 6.55 2.8 130 39.00 bd 5.81 bd bd N23 peeper 8.1 6.28 -50.6 331 27.46 bd 1.10 bd 0.376 024 surface 6.13 6.13 -l7.3 174 38.65 bd O. 55 bd bd 925 surface 9.7 5. 49 129.3 23.9 57.59 bd 21.25 bd bd f Doc CH; : Nils-‘7 Feaotabzx-Fe“ KT. Na Ca 111 sample -. (mg/L) (”mg-[Luggm . .-1.'ng¢1.).4.2~1 .(mg/Ly; ;_(rng/L) .(rng/L) (mg/L1 (mgQL H21 We 15.80 -- -- 27.68 34.885 3.619 9.359 33.90 7.25 peepeg H21 9"” 62.40 -- -- 9.75 10.873 14.42 13.25 48.99 11.77 surface 122 surface 3.14 -- -- 4.94 5.351 3.804 18.87 42.55 12.41 119 peeper 8.18 -- -- 0.30 0.155 1.741 58.84 71.41 14.80 119 surface 20.81 -- -- 0.47 0.324 4.517 25.88 41.39 27.08 119 peeper 9.29 -- -- 0.32 0.199 1.818 64.08 56.70 12.47 K22 surface 4.40 -- -- 0.50 0.497 2.368 19.50 34.98 10.86 L21peepe_r 11.15 -- -- 1.47 1.491 4.368 21.78 34.03 11.94 M22 surface 5.30 -- -- 0.65 0.613 2.49 15.66 35.32 11.02 N23 peeper 11.83 -- -- 38.25 55.384 1.499 14.75 57.84 15.46 024 surface 9.85 -- -- 4.27 4.541 3.958 20. 65 99.64 29.13 925 surface 18.47 -- -- 1.63 1.540 0.499 23 41 50.88 9. 60 H2133?" 155.26 0.19 0.11 555.83 1.07 0.09 64.24 111.79 “21 9“” 121.70 0.82 3.01 15.61 632.82 1.53 2.29 16.31 154.03 surface 122 surface 80.75 0.21 2.29 1.30 413.43 1.13 0.16 4.01 177.89 119 peeper 106.51 0.20 4.30 48.56 73.02 1.91 0.70 60.02 99.97 119 surface 335.02 0.61 1.25 304.28 100.17 2.71 27.67 613.90 73.37 119 peeper 134.07 0.19 2.87 58.44 61.43 2.21 0.26 31.50 98.52 K22 surface 58.93 0.06 bd 3.74 15.90 0.06 0.19 1.39 151.97 L21peeper 791.85 0.10 0.06 79.95 432.16 0.90 0.21 303.55 106.56 M22 surface 124.61 0.08 bd 11.52 117.20 bd 0.22 0.75 139.75 N23 peeper 210.43 0.36 0.12 107.98 575.42 2.25 0.44 325.13 109.55 024 surface 87.60 0.17 1.65 19.13 215.91 1.22 0.24 8.19 170.89 925 surface 75.55 0.77 2.41 228.71 246.93 1.03 0.94 136.94 49.94 141 Anna-119 Apmndix G -1: Solid Phase Extraction Data — Chromium Chelex Cr is the amount of chromium in solution after reaction with the Chelex resin. Sep-Pak Cr is the amount of chromium in solution after reaction with the Sep-Pak resin. AG Cr is the amount of chromium in solution after reaction with the AG resin. . ’ Sample . Cr Chelex Cr Sep-Pak ‘f AG Cr * 2 (ML) (pg/L) Cr(ug/L) (pg/L) Samples collected on during the 8/98 sampling trip H21 Spring 11.77 10.53 9.75 2.3 122 Pipe 9.7 14.68 6.7 2.35 122 Spring 3.45 3.77 1.8 0.7 J 19 Pit 52.87 53.03 49.25 3.5 K20 Surface 93.03 89.23 84.15 4.35 K22 Surface 13.71 14.74 10.55 1.45 L21 33.07 32.52 27.8 3.4 L21 Surface 35.91 35.59 28.85 0.95 N23 89.49 89.7 59.2 5.6 N23 Surface 3.55 3.75 2.6 1.6 P25 Surface 5.96 6.57 5.25 1.95 Samples collected on during the 10/98 sampling trip H21 Pipe Surface 15.61 13.81 10.8 7.2 H21 Pipe 6.09 5.99 4.3 2.75 122 Surface 1.39 0.94 5 O J 19 Surface 304.28 304.32 264.75 9 J19 Upper 53.94 52.21 52.95 9.4 .119 Lower 39.98 40.82 36.95 1 1.85 K22 Surface 5.49 4.58 3.6 7.05 L21 88.35 90.46 77.3 27.65 M22 Surface 11.52 11.9 9.55 4 N23 130.72 141.75 112.55 14.25 024 Surface 19.13 19.46 14.3 4.8 P25 Surface 228.71 230.78 205.15 12.7 Samples collected on during the 6/98 sampling trip .123 3.58 3.04 K22 53.83 49.03 L21 26.42 27.31 N23 65.36 54.94 022 29.32 31.86 P25 61.59 71.31 142 Apmndix G -2: Solid Phase Extraction Data - Manganese Chelex Mn is the amount of manganese in solution after reaction with the Chelex resin. Sep-Pak Mn is the amount of manganese in solution after reaction with the Sep-Pak resin. AG Mn is the amount of manganese in solution after reaction with the AG resin. Sample . Mn N Chelean Sep-Pak AG Mn . - (us/L) (Hg/L) Mums/L) (pg/L)- Samples collected on during the 8/98 sampling trip H21 Spring 44.81 0.29 44.75 45.95 122 Pipe 648.33 4.32 633.5 649.5 122 Spring 1.57 0.14 1.4 2.65 J 19 Pit 85.17 0.61 89.8 90.6 K20 Surface 143.74 0.6 138.3 150.6 K22 Surface 67.4 0.62 64.25 69.9 L21 291.36 1.64 294.05 290.1 L21 Surface 344.25 1.37 333.45 317.35 N23 512.7 2.88 474.2 538.7 N23 Surface 167.27 1.87 152.05 167.55 P25 Surface 82.28 0.38 76.55 79.95 Samples collected on during the 10/98 sampling trip H21 Pipe Surface 632.82 38.32 617.1 545.65 H21 Pipe 578.25 106.99 561.5 446.05 122 Surface 413.43 31.46 412.55 351.85 J19 Surface 100.17 1.51 97.55 86.45 J 19 Upper 64.65 2.55 65.6 56.1 J 19 Lower 83.14 4.43 89.25 79.35 K22 Surface 15.9 1.77 16.1 22.9 L21 342.41 12.57 338.45 285.3 M22 Surface 117.2 13.6 116.3 104.15 N23 819.87 5.87 847.2 816.7 024 Surface 215.91 11.61 219.65 186.4 P25 Surface 246.93 20.96 247.75 206.95 143 Sex 3 B B 3 2% 2.8 $8 3.: n? a: 2 NS 2.35 “$3 Sm m8 9% OS was. 958 3% 0:: 3m mam B 3 2.85 2.5: B B E B 983 8.8 :4 3: 3m N2 3 3 2-25 682 B B B B 39: 8.8 3a was 9mm 43 B B 2-5m -- B B B B -- -- 58 02 SN 43 B 3 3-25 38 B B B B SB 2% 2m OS 5.2 was 3 B 2-8m 38m B B B 3 :42 ea: n8 ”3 can a; B E 2-8m in: B E B B 4.8% comma S: 3% 3w 3% B B 3.8% 38% B B B 3 28m Eda 3: Now 3 33 B B 3-2% Noam B B B B 33? $.wa on: 3% EN 23 B 3 25am 3% B B B B 38 8.: mam 3d 3m 43 B 3 Sim NS: 3 B B B was 8.2 3.: NS. we SN 3 3 Sim team 3 B B B 32 ow: OS 9:" 4.2 9: B B 3-2m fig 3 B B 2 23m o3: 3m 8N SN :3 B B 2-8m £5 E B E B wows 8% 33 N2 N: o: B B 2-3m 38 B B B B 3% 3.3 SK gm 3 33 B B 2-8m 242 B B B B we: 3% :2 N3. 68 fig 3 B 2-2m 3mm 3 B 2.: $4 0.8m 2.8 32 was EN 3A B B n28 22: B B B B 8me om? 32 NS Sn 9% am woo 2-88 meme 3 B B B 3:: 8.: 32 e: as con 3 woo 2-2mm Snow 3 B B 3 2w: 8% 38 03 man Now 3. go noéamm a a a aagggggggflm ..8 c8 .58 Ev. .58 Eu £8 ..8 .58 Ba .58 we. .58 .35 88 SS :8 58 m2 :2 mm mm 935 9:» E E 29.5 3532: Ho: 83065 -- £2683 323 83065 3 $33 Ems? b3 93.: £5568 E 52352.8 83665 new ABE ecu—:8 8282 E 883% covabaoocoo 8:865 .58 =8. .8 53 5:235 .8555 3.5.. 8 4-: 2.3. J: 5.... < 144 n88 B B E B 3me 83: 32 8.“ SN «3 B 3 3-86 Sam 3 B B B 3.88 332 as: 43 34 3.4 3 3 3-86 33 B B B B 6.38 8.2: 32 8.4 4.6 min B 3 2-86 968 B B B 3 N82 8% 32 43 «.2 o: B 3 3-86 32 B B B B 38 8.8 OS 03 3m #6 B 3 3-96 38 B B B B Ea 2.2 98 SN MEN 3 3 mod n26 4.82 B B B B 3g 8% 22 2.2 34 8.4 3 :3 3-86 3:. B B B B 39. 8.8 6m 86 62 N? B 3 3-86 6:8 3 B B E :52 on? as: 86 3a N8 3 3 2-86 oaam B B B B 33 2.2 «.3 NS 6.2 v2 3 B 336 68$ 3 B B 3 9:8 8.”: 3: 8.4 33 8+ 3 3 3-96 38m 3 B B B ode 8.8 2: N? m: «3 B B n26 33m 3 B B B 928 8.42 3: N3 96 on; B B 3.96 ES 3 E B B 32: 2.: 3a 8.6 2: 8.6 B 3 3-86 35 B B B B :8 8.3- 34 cm: 3 86 B E 636 NS; 3 B B 3 33m 03: 32 mod 3 N3 3 B 336 382 3m 03 3mm 03. 333 2.48 3&8 N34 3% and. 3.; N3 3-26 3% B B B B 32w 8.86 36 6.3 $4 43 B B 2-:6 3me 62 SN 36 w: 3an 8.3 3% 8.8 we 2: B 3 3-36 39.8 B 3 came 43“ 32mm 8.3 63 £6 9: 84 B B 3-66 #88 v.2 Q3 32 N2. :56 932 3% 2.2 6% mam 3_ 6.3 3-36 2&2 3 N3 68 N3 362 83 SR 8.3 S: 8; B 3 3-86 4.32 B B B B 3m: 3% a: 6% 3m 8.” B 3 3-86 3.3 B B B B 36mm $.86 38 3.2 was 63 3 23 2-326 343 B E B 3 688 8.8 3% $2 1: 8.6 3 «3 3-326 8 a a giaagfifiagwm Uflm gm fl.—Ow Em GBOM Em ELOm vow fl.—°m 8m :38 gm €38 .83. «No 85 :8 :5 62 m: 6 6 m3.» 33> 6 66 2.5.6 145 338 B B B 3 33 8.88 3:. 8.2 6.9. 82. B 3 2-86 288 B B B B 2.88 2.86 6.83 8.2 3: 32 B 3 3-86 386 B B B 3 8.9.2 8.8 3.3 33 38 8.8 B 3 3-86 38 B B B B 8.23 8.6. v.8 83 oi. 8.2. 2 33 2-36 688 B B E B 688 8.82 38 8.: 68 3.3 3 83 3-86 Q82. B B B B 3:. 8.8 3: 9.3 3 83 5.6 32 3-26 32: B E B B 36: 8.8 63 8.2 E. 83 3 83 2-:6 ~82 B B B B 386 8.8 33 8.2. 3 83 B 3 3-26 3.8 B B B 3 38 8.8 3.8 8.8 32 82 B B 3.36 38 B B B B 38 8.8 6.8 83 2: 32 B 3 8.386 8.3.6 B B B B v.88 2.8 3.: 8.8 32 8.6 B B 3.36 3.9. B B B B 0.83 8.8 33 82 8.2 83 B 3 2-36 3.32 B B B B 2:: 8.: 22 85. 2_ 86 E 2 3-86 3.8 B E B B 8.3.... 8.8 22 31. 3.8 8.8 B B 236 38 B B B B 3.8 8.8 2w 8.3 8.8 8.8 B B 2.86 3§ B B B B 38 8.6. 8.88 8.2 3.: 8.2 B 3 3-86 688 E B B B 8.88 8.82 68 8.8 68 8.8 B B 3-86 386 B B B B 29: 8.8 3.8 8.3 v.8 8.8 B 3 2-86 33: B B B B 386 8.8 33 3.3. 3 83 B 3 3-86 8.88 36 83 B E 338 8.8 38 8.2 36 82 B 3 3-86 383 B B B B 288 8.36 3: 88 2: v2 3 B 3.66 8.8: B B B B 3.86 8.5. 3... 8.3 33 23 B 3 2.3.66 8.8: E 83 v.8 32 3.88 8.86 38 8.2 2.2 86 B B 3-2.6 38 B B B B 38 8.8 2.2. 32 8.2 x: B 3 3-86 :86 B B B B v.3: 8.3 v.8 8.3 68 38 B 3 2-86 B a a [36636663 38:. a $636.66 a 6.8 com .58 ca £8 .8 £8 Em .58 Ba .58 Em 1......8 32. 88 83 66 66 m: 62 66 6 935 ms: 66 66 2.638 146 mgomfi up up B B v.22 8.3. Hdfl mad Eon N56 3 B 07:?“ mgva fix end B B “.2 fim ends m6; ONE 0: wad B B mdétm YMNOM Nw fimd B B fimmcm 8.02 v.53” CNS 5.3 9.4 3 B m.m-mmE fismm 3 vs ca 3 5mm: 83% 0.6mm ode QB SA 3 B @733 vac?“ 5w“ 9.6 v.62 Nmé ode m code odvo owdfi WE mm; B 3 ndémE Qmag us up Up 3 0.82 Exam Woe VN.N v6 wed B 3 w.m-mmE $83. 3 an E B @603. omdom @ANN 05.x fimm wvd 3 3 m4; mi HHmON vs cs 3 B HBNS oo.ww Qmwm v9: VS. NW». 3 B mdémE Qmwfi up 66 us up v.2 : 2.6m v62 wad w.m~ 9: on 3 W.H-Smm fimwmfi up 66 Up 3 9mm: omdv v.3.m cow o6 H mm; up up ndéONm 6N9: 0.3 wad 3 up mdow 9&2 _.N: wwg odm em: to 66 m4; wfim 08% ~62 S .m B B mwoom owdt mdmfi 02mm 0.9: wvfi 3 we wdéwfim #5me Now 9.6 Up 3 N.3mm on:- hgwmfi mm. 5 Wm: X3. up 3 WmAmSm mdaa @me 3.6 New 3.; méwi oodm MES 9.4m Nun: owd 3 up 0751”“ We: imm 5.4 0mg wad oéwmfi 00.3. Nmmm and WE cad up 3 mdéBM Yam; 3 3 up vs 0.3% 9.6: fiomm Oo.N_ EHN 8d 66 B m.m-m3m 58% 3 Up 3 B van: 8.0va Waco wimm 0.9. wvd up 3 076va 9.32 B 3 B B 933 8.8 0me vwd 02 co; to B md-OEW 0.39. mfiv am; to B v.3 w Omém Wommm Vmwg vdmm 8.5. 3 up m.m-moHQ Bewmo fix» me; 2.2; onm 52.-www- ovgofi Nwwg omdm 0.2: 3.8 Q: who 07;;— mflmmn QmNH we;V oémm was Noamc 9.me Ndwo 2 .NN Wmm Sum to B md-OEQ Ewowm B B B B mdwvm OER: M922 vwdv was wow fin wfio m.m-m:Q mdwmv oém mad mace owdm 6.38 coda Ndow cmdm Wow 9.; NM NNd m4; CD QMNNS rd: wo.m 5.03 Nbfim Encomw OWN-mm 04.86 3.8 QVB 214. c; 2 .o 006:9 méoe B 66 B up 052 9.. S :.NN wow fiwm wed B Up mgr--mwfifl wfl-Vmfi qu—EE mu:— qu—ES flu:— qu—EE NEE qu—Vwfi wI—VME 94me meE wul—NME E com 68 ...—cm vow ...—cm 68 :38 won ...—cm com ...—on 68 ...—cm 36H. NNO «NO HNO GAO m2 m2 Mm— mm m<>> m<>> NH km— 295% 147 388 E 23 3.8 8.2 Q88 8.3 8.82 8.: 32 8.0 B 3 3-86 3.38 B B B B 388 2.86 28 8.2 3.8 8.8 B 3 3-86 386 3 8.3 B B 282 8.8 38 836 Q8 9.8 B 3 2-86 338 B B B B 8.88 8.3 $8 8.2 6.: 82 B 3 3-86 8.82 B B B B 8.82 8.8 23 33 38 82 B 3 3-86 383 B B B B 3.88 8.22 32 8.8 98 83 B 3 2-86 3.88 B B B B 382 2.8 38 8.: 2.8 2.8 3.88 8.2 3-86 886 B E B B 3.82 8.8 2.3 83 2.2 8.2 B 3 3-86 3.82 B B B 3 3.82 2.8 38 8.8 0.8 83 B 3 2-36 3.9.2 3 33 B E 35.6 2.8 32 83 2.2 82 B 3 3-86 382 3 2.0 B B 38 8.8 388 332 8.8: 8.88 3.8 2.2 3-86 0.8:. B B B B 38 8.8 3.88 8.8 2.8 8.8 3 83 2-66 33:. 38 83 8.32 33 3.2.3 88 2.82 83 3.8 2.2 3: 8.2 3-86 :8 B B B B 3:. 8.8 38 8.3 28 8.8 B 3 3-86 6.28 B B B B 38 8.8 332 8.5. 3.8 v2 3 B 2.36 338 B B B B 22.8 8.8 8.2.8 8.3: 5.8 2.3 B B 3-9.6 3.9.8 B B B B 328 8.86 3.: 8.2. 8.9. $6. 3 B 3.28 3.28 B B B B 388 8.86 E: 8.2. 3.8 8.8 B B 2-:8 382 B B B B 6.2.: 8.8 3.8. 83 8.: x: B 3 3-98 238 B B B B 328 8.8 33 33 8.5. 8.2. B 3 3-866 382. B B E B 8.28 8.86 3: 83 I: 8.2 B 3 2.326 3.29. 3 03 2.8 8.3 3.38 8.82 38 3.2 0.8 33 B 3 3-826 8.82 B B B B 22: 8.8 8.8: 2.2. 3.: x: B 3 3-226 Q82 B B B B 2:: 8.8 32 83 3.: 32 B 3 3.666 3.82 B B E B 33.6 8.8 33 33 8.2 83 B 3 3-826 aggggggggggflafim :8 6.8 £8 6.8 .58 c3- 58 #168 6.8 £8.le £8 6.; $6 $6 :6 :6 62 62 66 66 3B 33 x6 86 2658 148 3.2.8 3.8 82 3: 8.8 2.32.3. 2.32 32. 8.2 3.2 8.6 2 23 3-82 333: B B B B 8.82 8.8 838 83 38 33 3.2 2.6 3-2.2 382 B B B B 3.83 8.8 32 33.8 3.8 8.3. 332 83 2.22 8.88 B B B B 3.8: 8.8 338 8.2 3.8 8.3. 8.8 33 3-82 38 B 3 B B 38 8.8 33 83 8.2 8.2 3 8 3-82 8386 2.3. :3. 3.83. 2.3. 38 8.3. 3.88 33 3.8: 83 3.8 83 2-82 2.2.: 3.2 23 B B 338 33 38 33.8 32 33. 8.8 3 ._ 3-82 8.88 388 8.8 3.23 2.3 88 8.3. 2.2.3 8.3. 38 33 8.: 83 3-82 388 32 8.6 38 8.2 382 8.38 338 8.8 38 33 33 23 2-32 33:. 6.8 83 38 8.3. 3.88 8.8 32. 8.8 33 83 B 8 3.82 3.82 B B B B 3.82 8.8 32 8.8 6.2 83 B 3 3-86 328 3.2 83 B B 332 832 3.8 8.: 3: 8.8 3.32 8.2 2-86 3.28 B B B B 3.28 333 38 33.8 32 8.2 B 8 3386 3.88 B B B B 8.82 2.8 38 8.2 3: 8.2 B 8 3-886 3.88 B B B B 2.88 8.83 38 8.: 22 8.2 B 8 3-886 332 B B 8 B 8.82 8.8 33: 83 3.8 333 B 8 3-26 332. 3 83 33: 8.8 8.88 832 32. 83 3.8 8.2 3.3. 83 2-26 333 E B B B 3.83 8.8 3.8 33 3 83 B 8 326 3.832 32 2.2 3: 33 3.88 8.8 8.88 8.2. $2 8.8 33 8.2 3-86 3.28 3.2 83 38 2.2 338 8.86 38 8.2 8.2 83 B 8 2-86 332. 38 82 38 83.3 3.88 832 38 83 2.2 83 3 3 3-86 36. 3 83 B E 38 33.8 3.8: 8.8 338 83: 3.8 82 3-86 386 B B 3.2. 83 838 333 332 33 32 83 B 8 2-86 3.22 B B B B 3.82 33.8 8.83 8.8 8.8 82 B 8 3-86 2.83. 33 23 B B 28 8.8 388 8.8 38 8.2 3 3.3 3-86 33.8 B B B B 3.82 33.8 3.88 8.8 3.8 8.6 B 3 2-86 Mal—mug wW—EE “mwa wmma “Ewe mun—WE “Emma “ml—Ea “mm:— va—HE “mm:— qu—Vwa “mwa 33. 38 .58 38 £8 38 £8 38 seal 38 £8 38 .58 .593 26 26 66 66 22 62 66 26 255 3B 6 26 23.58 149 3.822 2 33.3 B B 333 32.8 22.2.38 2.33 3.33 8.3 3.8 8.2. 3.3-2.82 32.32. 3.822 33.32 3.28 83 3.2.8 832 3.332 2.3.: 3.82 33 38 8.3 2-22.22 3333 2.332 8.3 38 333 3. 2.332. 33.33 338 2.2.8 323 2.2 3. 222. 33.: 3-32.82 338 2.2 33.3 33 33 3. 33 8. 23 3.2.8 2.3 332. 33 3 N 8.3 3.82 332.32 3.8 323 2.2.2.: 832 3. 88 33. 2.8 2.88 2.3.2. 2.82 83 2x2 33 2.2222 382.2. 3.2.32.3 33.8 33232 2.32 3 82.2.2 8. 8 3.322: 2.2.2.2 38 8.3 3.8 83 3.382 2.88 3 :.3 2.3 B 8 2.82 33.8 3.83 332 338 2..: B 3 3-3382 2. 88 333 32.3 3.82 2.3.3 3.2.82 832 3. 82 2 2.3.8 3.32 83 2.22 8. N 3382 m. 32.3 33 33 2.3 322 2.. 83 32.8 3. 2.3 33 2.32 8.3 2.3 2.3 2-82 2 32.2 2.3 32.3 3.8 8.2 8.2.3 8.8 3. 2.8 2.3.3 3.8 2.3 3.33 2.2. 3.3.82 2.2.23 3 2.2.3 B 33.3 3.38 32.8 2.82 32.3 23 33.3 33 2.3 3-82 3.88 3.32 8.3 E 33 3.22 8.2 3.232 33.3 3 2.3 33 33 282 3.3332. 3.8 2.8 2.2.2. 33.2 N. 2.28 8.82 322.3 33.: 33 8.3 3.2. 8.3 3-82 2.2 22 33 B 33 33 3. 83 3332. 3.2.2 2.3 2.3 8.3 33 33 3-82 3.32 8 8. 22 2.2 33 33 3 2.: 8.2 333 8.3 3.332 8.2. 32. 2. .2 2-82 3.82 3. 8 33 2.3 2.3 33:- 33.3 3.83 8.3 2.33 8.2 2.3 32.3 3-82 332 B 33 B 33 8.22.2 8.2.3 3. 38 332 3.8 2.3.2. 3. 32 33.2 2-2 22 2. 328 33 33 33 2.3 338 8. 33 3. 38 8. 2 3.8 8.3 3 2 2.23 3.22 2.. 82. 3.8 8.3 3.8 8.3 3.32 8. 3 3: 2.3 N 8.33 33.2 3 8.3 3-8:. 3 328 N8 83 2.33 32.2 3.88 33. 2.3 2 82.32 33 8 2.82 33.3 33 33 2-23: 3.8232 33 2.32 N. 38 8.2. 328 8.82 2.22.2. 33.3 3.8 2.2..2 3.3 2.3 3-83: 3.88 3.22 32.2 N 83 33 32.333 32.32 3. 82. 2.3.3 2.2.3 8.2 3.3 23 3333: 32.333 3. 82 33.2 3. N8 33 3323 8.82 2.28 32. 32. 32.2 8.3 8.3 3.3-32.3: 383 N 3 32.3 3.8 8.3 3.88 8. 3.8 3.38 8.8 2.32 8.2 33 33 2-2332 2.883 32 8.3 3.32. 82 3.2.28 32.. 38 338 33.8 32 8.2 33 33 2.22232 3.88 3.3 8.3 2.32. 8.2 3.2.83 8 28 3 38 8.8 3.2 32.2 33 33 32.2332 gigaflfififiuflfiglflflgfim 2.8 83 22.23. 2.3. 22.233 2.8 22.28 2.8 22.28 2.3. 22.28 2.3. 22.28 28.8 28 28 6o :8 2:2 222 8.2 .82 33$ 2:» Na 3222 323833 150 3: B 3 B B 3% 8.: v.8 N2 N8 NS. 3 83 3.8a: 2:8 32 ”S 8.23 8.8 odfi 8.5 :82 8.x 2: and 8.2 «no 2-:sz 388 18 a3 3.? 83 fig 2.8 3: 3.2 3: 86 32 8+ 3.8% 8.82 we 85 B 8 $2: 2.8 38 3.: 8.5 88 08 9% 3.8% NE: 3 5o ode 85 n52 2.3 32 8d 0% 8.~ 38 82 his: 3% 3 86 Q? 84 252 8.8 $8 3.8 38 8.2 $3 8.3 2.8% $§ 3 5o 32 Ed 3.8 8.: 38 85 M3 N8 2? q N n78: 8.8: B E B B 8.8: 8.8 38 2.2 Mg m: B E 3.8% 35 B B B B 33 8.8 23 8.2 n8 one B 8 3-83 <82 «d 83 32 84 SE: 8.8 38 2.8 8.8 mg 3 B 2.54 32m $8 84 n8~ mg :8: 8.: 8.8: 8.: «mm 38 B 8 3-23 38? wt 53 38 8.8 ~88 8.2 was 8.: 2m 86 38 2.8 3.8qu Q88 082 3.: 28 £8 32“ 8.8 5.82 3d 3: mg 32 v? 8.383 3va NS 86 38 E8 3% 8.8 3:: N2: 3% 8o 8% $8 2.?qu Q83 New 3o 3%: mg 8:: 8.: 8.82 was a: is <82 8.2 2-83 688 2 mod 3 8 Sam 8.82 33 8.8 E o: B 3 3-83 «.32 E B B B mam: 8.8 S 2 8.: ”.8 3m 3w 8.5 3-23 33: v.8 9% 38m 8N 888 8.8 v.88 was woo w: B 3 2-33 8.2% 8.: “to S: v: 8.82 91: v.32 33 SN 8.0 B 3 8-83 288 3 86 B B imam 8.2: 89 one 8.8 ohm B B 2-:3 wdmov 2 8o 8 3 28m 8.? ”.88 SR 1m «3 B 8 2-23 w.:8 ”.8 3° 29: 8.2 9.88 2.3 «.8: 3.8 32 w? 32 a? 8.282 0.88 v.8 83 3% 88 8.82 8.8 2: 8.2 a: 83 88 N3 3.8g «.88 0.8 84 $8 can ~88 8.? 23 8.8 Ba 8: v.2 86 2.8% 8.28 22 82 3Q 3.8 332 8.8 3m: 8.2 Nam 86 B 2 248m 58% 58 8.0 w.8 83 3me Sand 8.82 8.2 we 84 3 NS 3.83 agfiflafiaflagfigaaa 8v. 88 .58 8m .58 8m 58 8m .58 B... .58 1.43, .58 Ba. 88 $8 :8 :8 m2 :2 mm mm ms: 9;» xm Na 2958 151 6.366 B 8 mm :6 3.8: 8.8 :66 8.66 32 3.: 6.3 88 2-688 N636 B B 3.2 86 28: 66.8 $3 6666 626 82 866 82 2.88 3.88 B B 8 :6 8.8: 66.8 6.36 8.8 6.36m 88 6.: 36 2-38 6.86: mm :6 S 26 6.85 8.: 8.36 86 :66 88 B 8 2-28 6.88 3.5 86 8.8 36 6.23 65.3 28: 8.: m8: :6 B B 86-88 66me 66 66.6 B B 666: 66.3 56:- 88 3.86 26: 8.63 36 2-38 83: in 6:6 8 B 386 62.8 6.63 86 6.8 8.3 2.86 66.: 2-38 6668 n3 :6 6.3.0. 66.6 6.686 8.3 6.8: 3.8 N63 666: $66 66.2 @6638 :8: B B B B 28 63.2 6.666 36.: 8.36 66.: B 8 2-88 3.8 B B 86 36 W68 8.8 3.38 8.8 866 86 B 8 2-368 66:8 3 3 no: 86 6.866 66.8 36: 866 6.86 8.:- B 2 2-368 26.? B 3 m8 86 S83 8.8 6636 8.8 :.:m 668 B 3 2-38 888 EN 86 6.8: 63 233 8.8 6.86 86 6.3 62 B E 96668 668: 3: 86 B B 6.3: 628 6.36 866: 6.: 82 6.3 :3 2.88 6.88 6.8 86 $6: 366 6.86 6666 6.36 3.: 6.8 86 E8 66.: 2-88 6.366 66 :6 B B 66:: 8.8 8.33 82 E: :6: 6.86 63.3 86-88 663: 66 666 B 8 6.666 62.: S8 36 2» 88 3.3: 66.: 2-622 ~68 2 26 B B 8.68 8.2 $6: 82 86 :6 88 8.8 2-52 6686 8.8 86 :62 8: 6866 666: 368 366: 866 2.8 288 66.3 86-682 n83 663 8.8 6.9: 86.: 38 666 $8 63 N8 8: :63 62 2:62 665 3.8 86 N66 66.: 26: 8.8 28: 8.2 32 86 66: 666- 86-682 6.36: 66 86 B B 26: 8.8 23 8.: $6: 666 366 62 2.682 6636 6.: :6 B B 6.66: 6:? 38 636: 5.8 8.: 6.2: 66.8 2.862 26% SN 86 66.: 86 85 626 2666 66.8 6666 3.: 6.86 63.8 3.682 8663 8.3 666 E3 6:- 88: 636: 8.5 86: 66: 86 n8 3.: 2-882 8.88 6.8 8.: 83 :6 263 66.86 6.8: 83 Sm 36 6.8: 68 8.6-8:2 figagagagaga a final. 63. 8“ £8 68 £8 8“ £8 63. £8 68 Fall—48 .58 36,6 88 88 :8 :8 m2 :2 mm mm 3.3 ms: 68 an 2658 152 88: :8 6:6 8 :5 88:8 8.8 668 8: n8: 8.: :.E 8.8 8-88 8.88 :.m :6 B B 8.83: 2.8 6::. 83: :.:b 8.8 88 8.8 2-88 86:: :.m :6 B B 2.66: 8.8 3.8: 3.8 «.8 8.8 B B 06-88 6.8:. N8 86 88 86 :88 8.8 :.Ro: :8 6::: 88 8.8:. 8.6 2.89 88 3: :8 6.68 8.3 8.88 8.8 266: 66.8: 8.8 63.: B 3 86-88 :88 :8: :6 6:8 8.“ $68 8.8 n88 88: n8: :8 668: 8.:N 2-88 :88 8.8 66.: 28 NE :38 8.8: 8:: 3.: :8 8.: B B 86-88 3.88 6.8: :.m: 88 8:: 6.8: 6:8 3:6: 8.: 8.8 88 2.: 8.3 2-88 6:68 6.68 86 8.2 8.: 8:6: 8.: 38 8.8 38 8.8 8.88 62 2-:8 88:8 N8 3.6 E: :6 5.88 8.8 :8: 8.: 3.38 86: 8:: 66.8 8-8:: :8: 6.3 :6 B B 88 8.8 $8 8.8 88 8.: 6.8: 66.: 8-8:: 6.83m 6.: 86 6.8 66.: 38: 8.8 $8 86: n8 N2 38 66.: 2-8:: 88:6 8.8 86 3.8:: 8.8 6.88 8.8 86:8 8.8. 6.68 8.8: 6.8:: 8.8 86-88 3.88 n8 8.: 8.8 8.8 8.88 6::: 6.88 8.8: 8:: 66.8 8 86 86-88 88 :.:2 8.» 38 3.3 38: 6:8 38 8.: 8.8: :.m B 8 8-88 888 :.m: 86 2m 86 88 6:8 88 86: 8:: 3.3 8: 86 2:28 588 66: 26 3.8 86 8.83 86:. 88 86: 6.8 88 n: 86 2-338 :88 6.8 86 :8 86 6.88 86:. 88 8.: 8.8 88 8 :6 2.388 6.88 3.66: :5 868 8.: 6.8:. 8.8 88 8.: 6.8 N2 8 8 86-638 28 8 :6 B B 6.8 6:: 83: 8.3 3.8 88 8:. 38 8-8:: :88 m8 86 B B 6.88 6:8 868: 8.8 :8: 8:: :6:: 8.8 2-8:: :88 2:. 86 :88 88 8.88 66.8 :..63: 86 N8: N2 8.88 8.: 86-88 ggaaflaldflwfladflfladflslldmmlg a com com :58 com :..om com :..—8 gm :..8 com :58 com :58 :56:- 88 :8 :8 :8 as: m2 8: 8 33 ms: 8: 8 295m 153 n3 -- -- 8.8 ::.N 8.: 8.8 8m 3.88 B B 8.88 8.8 8.: 8.: o>< 8.8: B B 8.88 :88 8.8 88 2-32:: 8.83m B B 688” 688 :.E 8.: 2.32m: 8.83m B B :.Rom 8.3a 3.3 mm: 2-82m 3.: -- -- 66.~ 3: 8.:- -- o8 2.8: B B :.:68 2.3: 8.8 B 83.. 8:: B B 9.88 2.3: 88 B 86.68:: 66.88 B B 8.88 3.8: 8.8 3 8-88 :88 B B 8.88 8.8: 8.8 B 268:: 68 -- -- 8.8 :.:.: 8.3 :8 8m 82.: B B 8.8: 626: :8 8.3 o>< 88: B B 868: 6:8: 88 88 86-608 868: B B 8:: 8.3: 8.8 6::. 8-88 8.88 B B 8.8: 8:: 8.8 8.3 86.68:: _ $8.: 88 a : _ :.3. :.8 :.8 :.8 B... :38. :8 :8 m2 8:, .. 154 ::oemvom 82¢ cam-tam Pm—Z 8: 38 Sam 8.38:8: 3:5 on: ::o 8:838 28:88 03:20: 05 82865 Day: .8388 88:8: 35 Mo own-:08 on: 8286:: O>< 883 £303 b3 80868 5 8385280 8:86.: com 88 8.8 8.8 88 R8: 8.:- 8.: am: 8.38 8m: 888 $.88 88:- 88 88 03.. 88:2 8.8 888 8.28 8:3 5% 88 8.8: 8.88 8:: 2.8 3.8% N8:- 38 28 8-88: 888 :8: 88% :88: :.:m 3.3 88 888: n8 :8 :8 m8 3.: R: - a8 88% m8 :..8 8.88 :88 8.: B o>< 888 8w 3.8 3.8% :88 a: B 8.8: 888 8: 8.2V 8.3% $88 :..: B 8-8: 28:: :8 8.2. 888 N88 5.: B 8-8: 88 -- -- 3.: 8.: 38 -- :8 8.8: B 3 88: ~82 8.: B o>< :82 B B 8.2: 88: mm: B 8-3:”: 8.8: B B 5:: 8.8: 8.: B 8-2:". 8.2: B B 883: 8.8 8.: B 8-2:: 98 -- -- m8 8.: :8 -- :8 882 B B 8.8 8.; a: B o>< 8.8 B B 8.8 5.8 3.: B n.m-8a 888 B 3 $88 2.8 8.2 3 8-28 83% B 3 88mm 3.: 8.: B 8.8: ..8 e8 3... 38:8: .59—.1 $8 .288 155 3m 8.?- ofla Em and M2; 5% a? 8.28 8.2 8.: Sana 3.3 ~32 Em o>< 8.38 8.2 3.: 8.88 3.0? 8.22 9.2 2.330 $.28 8.2 9.3” S52 2.3 8.8 and 2.3.3 3.8% 3.8 2.3 3&3 03% 33 an 2.38 mom -- OS» 22. 3a 2.: «v.8 a? 3.3% 93 E 3.2: 058 2.38 $3 o>< 8.9.8 8o 3% 3me 2.23 8.3: .2? 2.882 :.NEN 8o 52 $.32 mg? 2.2 3.8 2.23“ wanna cod 8.0 3.8: M23 8.25 32 2-38 2.3 -- 8.9. 2: :.m 3N -- 8m 8.38 B 38 $.83 $.88 N38 B 92 8.5% B 8.3 $.89. 3.33 8.0% 3 2-38 33% B 3.2 wwéwm $.22 3.8m 3 2-380 38$ 2 8mm 8.39... 8.9.3 2.2m 3 2-38 8.2 9&2 2% 8.: one 3.? who a? 3.8% $.30 2.8m $.23 2.22 3% Rag“ w>< 8.58 3.: 2.38 9.83 3.22 9.: 8.3 3-33 93% $.82 onmmm 3:5: :..-.82 3o: Ema 2-22 8.89. ES 33% 3.33 8.22 3% 2.82 3-33 . $an ‘ Qua 3m 3.. 38:3: .58. 88 2.5% 156 Nmfi -- -- $5 3.2 mmém 3.9 Qmm 3.9% B E 8.3mm ofioacm omémw m: O>< v4 3% B 3 380m 2.2-cm fimmo ad nQvionmSEm ~35 B B 0.3mm wdfim wwhw o; vavaoRSBm ”$me 3 B wwmhm méoom o._ 5 ed bfiozmwonm—ZMm Wmnww B B v.2 3m mécmm 0.02 2 m4 SEQNXKNEMm mASw B B Q33 Wag ficmw v4 woRfiRvonNEN—m 2.3% B 3 2.32m Zoom 2.3 >2 3\m\~vo\.N2Mm Mud—NE mewE ammun— qu—EE «my: «ME—a Infla— ; . com com com 68 c8 . v3- . a8 33:3»— 2ng .53. «NO, nNO M2 mm— m<>> , Km . 157 gm 5: 8.8 26 o? :4 8.? Rd 8.2 3 B -- -- 2.85 to no 92 B B 3 v.0 3 E B B -- -- 2.88 3.8 24 on? Ga 8.8m 8d 8d: 2.0 8.3m who on _ m -- -- 3-85 8a 26 NS 2.0 86 $6 8.8 :4 8.3 B B -- -- 2-2 5 2: 8.0 OS 2 .o 85 E .o one $5 8.8 B B -- -- n2 _ E 3.3 as om? 35 843 86 86 3.2 8%» E B -- -- 3-25 one N8 one B B 33 8.8 B B B B -- -- 3-8m 86 86 as B B :.o o3 one 8.2 w; 8.: -- -- 2-3m 3 S 2 B B 8 q: 3 2K do me -- -- 3-8m N3 86 8m 3 B :8 8.2 So 8.x OS 8.8 -- -- nmém 3o 8o 2: B B B B woo 8.2 v3 8% -- -- Sim 36 NS 86 B 3 3d 84 NS 8.8 B B -- -- 3-2m w? 86 Ba 8.0 2 .2 mg 8.: m8 8% B B -- -- 3-8m 3o 86 8a 3 B :.o owe N3 2.: B B -- -- n38 NS So 8m 2 .o 8.» 2 .o 8.” :.fi 8.? B B -- -- 358 $6 mod 9: mod com 25 8a «.8 9.2 E B -- -- n38 2.: 8o 8; 3.9 8.03 NS com :3 8.2 B B -- -- 2-8m 2 od 5 -- -- no 08 8 3a -- -- -- -- 3-8m Maw:— wu—xwa d»: wéwfi 4%: uth AuliL wing: in: com com ...—8 com ...—8 com ...—8 ‘8 :..8 38. .88 83 58 :5 m2 m2 ; mm mm 938% 35308 8: 332?: -- .8883 323 @3865 3 Emma 3303 D3 938 .anauom E cowabnoocoo 8302:: wow ABE acts—cm 8282 E @8088 5.93888 mouaoEE ...—8 .5 c0 ..8 Sun .333be 33826 =55: w AA 935. 158 Nod aod end mod cod to as >10 8.: de omdm -- -- w.m-mo~0 5N6 wod NYN hmxm 8.53 mod oezv wmd 9a.: hNd ONKN -- -- m. fi 420 a .N 3.0 09m th omfim mmd OWE and owdfi and on .Vm -- -- mdéOHU v0.0 vod ow; 05v 8&2 co; omdw VNd omd 3 B -- -- Wm-me mow Rafi omdc OH .0 oodNN E .o 8.0 Nod 00.0 B B 5 -- W.H-;U mowmom mvdvm oodeN 3.4on 86350 Eamon 8630 N132 H odmvmv 5.2. 8.2mm .. -- mdéwU EA cod 86 mod OVA on; 91:. NNd 2 d us up -- -- m.m-m©0 vwd mod VNM mod 9mm omd OWE mmd 002 B to -- -- 9750 mmd mod om; cod ohm 00.0 cad 0N6 and 3 Us -- -- mdéeo SN 56 omd 3.0 ow; hm; omoo wed onwm B B -- -- Wm-va 34 Ed omd : .o CNS mod 8.0V 36 3.3 up up i -- 07:0 hodm Ed 006 vmd océm de 05.3 wogm oodwwfi to Us -- -- mdévo SN #06 ow; aod 86 Du; o9: 9.6 2.: no as -- -- m.m-mNU Ed up to mod 0mg 55 OH .: omd ONE up to -- -- mAANU cwd 0N.0 0mg. 2 .o oonN mud omfim 2mm 2.3: B B -- -- m.o-omU QNMH vmd 0mgV mm.: 006mm 5N6 omb 91 Emma Us up -- -- m.m-m: m no; 26 Nmfi 5 .o 91. owd 05mm vwd ov.mm B Up -- -- wAA: m omfim OVA oofim 0”: 8. EV Q .N 8.02 and 8.0mm wmd oméw -- -- m.o-o:m mode SM coda mmgw 8.23 him cod: cwd oodmm amd Omfim -- -- m.m-mm~m eqa tho omfim 002 oo.mNm Cod coda Ema 00.00“ cod 00.0w 3 -- méénfim 3.3 end OWE wNA: Goa; mm; 00.5w omfl oodbm cmd 2.4m -- -- mdémfi m win:— wu—hfi Ah: ugh:— du: $.wa 5w: nah:— dwi ugh:— dw: $.wa 4%.: com com :..8 com ...—3. com ...—8 com .58 com ...—8 wow u.- 33. «NO NNO “NO CmO ME ME mm mm mSS w<>> NH NH 29:—am 159 ca; 2.0 Nw.m up 3 9: omdo de 2 .NH 3 Us -- -- w.m-mm~n_ 3.0 00.0 OWN 3 up de 8.8 :.o 86 Up 3 -- -- méémma bod mod mod om A CW? and 05.2 am; 025 B B -- -- 00-029 36 cod cod mmé 8.0m“ wad omfiv Q d cod up 3 -- -- m.m-m~ ~Q 3.x 56 end mm...V 006E mm.m 8.08 mmd oiom cod 2.0 -- -- mg-“ _ ~Q >00 00.0 VON flaw oowom mm; ODS wmd OWVN B B -- -- 00-2 ~Q ms Md 0N v6 fimom N; odm ad mAm Up up -- -- m.m-maQ bow Ed wmd 01m coda 0N6 OF: 3.0 cow us ca -- -- @730 5N6 86 oo; Omé 00.03 ood 00v cod 09mm 3 on i -- m.o-oaQ mwfi 36 9mm mvfi 8. SN om; 8. fl m mad Omém B B -- 3 Wm-an m2: vod om; mmé oodwfi e .o 00.2 Sum om.mmm B 3 -- -- m. H; Nb $4: $6 003 mwé 00.ch omd ON: 3.0 8.0mm $6 OW: -- -- mdénfl nmd cod oo.m vmfi oo.mo~ Nm.m 263 :..o owéa aod ofiw -- -- Wm-me 3 .m B B owé 00.3“ mod eqm Had cow v9 fin -- -- m4; mQ omé E .o wmé mod 8.5mm :6 Guam wad omdv vs 3 -- -- mdémQ 2.: end cod 0N.0 8.1mm wwd Omfim afim eqwg 3 vs -- -- Dodo—U wmé S .o omé 2.0 ow.v mod 862 who ohm: 2 .o owdfi -- -- WWQLU Nm.m bod OWN 3.0 omfim A: .N 8.09 mud Om.wN B B -- -- WTSLU 86m :.o oofim 3.2 860v mwd 863 3d 8.0mm Gd omgm -- -- mddEU find mod VBN wfio Sac .34 A: .5 and 86 B vs -- -- m.m-mNHU 84 506 006 mod 2 .v and oodm mad 2 .3 B B -- -- mAASU Sam 3 .o moan mwé cod: 3 .0 end 56 Omém 3 up -- I @0630 Ema mans a»: Mafia a»: Ema an: “in... a»: ma»... an: wins a»: com com ...—8 com ...—8 com ...—8 $8 .58 v8 ...—8 com ...—8 13°F NNO NNO fiNO “X0 M2 ~52 MM Mm— m<>> w<>> NE NH 29:—am 160 we; 00.0 0w.m v0.0 0m." 0N.0 0w.mc nNd 00.0 00.0 00.0 -- .. mAémE NVA 2.0 0m.n 3.0 00.0 N“ .0 00.0 v0.0 0N.wm 2.0 05.0 -- -- 00-02% 9:. wmd 002 Nmé 00.00N omd 0v.w~ w~.~ 050w B 3 -- -- mgéomm M24: 5.0 0mAN wad 00.0VN 5&0 0w.0m Nwé 8.8m B 3 l I n.000Nm Ma.“ Hm 00.2 00.3.N wwfih 00.002 omfi 00.0: m0.mo 00.0m00 ONE—q 00.83 -- -- @70me dew bmfifi 098m wmfim 00.05. wmd 00.0Nm wfivm 00.000 de 00.0mm -- -- 00-0me vmdm v04 00: MES 8.00m mmd 0m.: owdm 0w40m Sum 26: i -- m.m-m£m 50.5 mmd 00.0.“v 00.2 00.0%.. wmd OWE Ed 00.3V mmd 00.: i -- W.HASm 0”: v0.0 00.: 0&2 00.§ mmd 00 .2 NWN 00.00 mmd 004m -- -- @00on em; m0.0 00.“ 09 3 0mm; 00.0w v00 0&2 B Up -- -- m.m-m3m N04 00.0 3 .m 00 up mad 0a.: wed 0w.m~ B an -- .. méAvfim Ed 3.0 093 mud 00 .Nm NH A 0m.mm 006 00.03 vwd owdb .. -- w.0-03m vwév mm." 00.mv $.VN 00.000 v04 05.; wasfl 00.05% B B n- -- m.m-m3Q w0.m$ owdh 00603 0w.0mv 00.0wwa 010w 00.00: SNm 00.00: and 0053 -- -- W.H-EHQ mime 00.N 0060 5.0m 00.052 wwfi 00.0mm VNfiN 00.0mm B B u- -- 90-02Q 0N4» No.0 00. HN 0N4 00 8? N50 0m.0m NVA 0b.?V VNd 00.0N -- -- m.m-m:Q 00.0w 3 .0 N06 3.4K 00.0NNN m0.h 00.9% owfi 00.02 NMA OM00 -- i m. _ -H S Q defl 05.0 00;“: Know 00.00 mm #53 00.9w NYE 00.00w Gd 0~ .NmN -- .. 900:9 0v.N 2.0 N06 00 to me; 0w.wb 9&0 00.2 0N.0 00.0N .. -- m.m-mm HQ 3.: 0N.0 0m.: wad 0000 @QN 00.02 wow 00.03“ 00.0 0008 -- -- 07300 006 0N.0 0nd owd 0N.mm >04 05w? QNM 000$ cvd 0H .Nv -- -- @0029 max“:— wu—BE AR: ”he Ah: win ...—h: Mia:— dw: aim” a»: win:— a»: com com ...—cm ‘8 ...—em 68 ...—cm 68 .58 wow .58 tom ...—8 13.5. «NC NNC GAO “NO M2 ME MG Mm— m<~$ w<>> NH NH 2ng 161 00.:v ::.0 00.:V 0N.0 0?: 0N4V 00.00: :5 :5 :5 :5 -- -- 0 :-:w :0 mud»: wmd 00.:: :0:: 00.0: m mm: 0N.0m 00.:V 00.00: :5 :5 -- -- 00-0w:0 050: N00 00.8 0:.:”: 00.0w:V m0: 0N.0m ::.0 0:.m :5 :5 -- -- 0m-m0:0 :Vdm mm: 00.:m hmfim 00.0.v0 0w.N 00.00 00.0 00.00: :5 :5 E -- 0:-:0:0 :00 mwd 00m 0N.Vm 00.00m Sim 0N.wN had 00.0: :5 :5 -- -- 00-00:0 50.: V: .0 00m mm.0 00m: N: .0 00.m mo: 00::V :5 :5 -- -- 0m-m¢:0 :0.mN :0.: 00vm W00: 000:“ 00.: 0:.mm 00m 00.0w: :5 :5 -- -- 0:-::0 w:.m: h: .0 00¢ N0.N 0N.mw mv: 0: .5» :00: 00.0mm :5 :5 -- .. 00-030 ww.m m: .o v06 «00 002 cod 00.00: m:.: 003 :5 :5 -- -- 0029.: 00.:V 00.0 00m 00.0 00.:v b: .m 00.00: 3.0 00.0w :5 :5 -- -- 0:-: :Nn: 0v.N N: .0 mm...» :5 :5 00.: 05.3. 00.0 0v.:N :5 :.5 -- 2 000:”: 00..v 50.0 00m :5 :5 Nw.m 00.0: mvd 00.0: mad 00.NN -- -- 0m-m0:m v0: :00 000 00.0 00.0 30 00mm wad 000: :5 :5 3 -- 0:-:0:": N:.0 m: .0 00:» M00 00.0mm :00 00mm mmN 004mm :5 :5 -- -- 00-00:”: :.N 0.0 v: :5 :5 0.: 0.00 00 0.0: :5 :5 -- -- 0m-m>:n: 5&0 00.0 05.: :5 :5 Nvd 000: :5 :5 :5 :5 -- -- 07:5": v0.wm w: .0 00.0 00.: 00.00m :0w 00.0mm N56: 00.02V mm: 0050 3 -- 00-05:": wmfi :00 000 0: .0 0: .v 00m 00.0w: 00.0 00.0w N00 00.0:V -- -- 0m-mm:m 00.:: N00 00.: 00.0 0003 N00 000m V: .5 00.00N v00 0560 i l 0:-: 2n: >03» 0V0 000: mw.mm 00.0w0 00.:” 00.00: 00.:: 00.0mm :5 :5 -- -- 0002": 00m 00.0 0:.m w0.0 0: .m 056 00.0mm :00 00mm :00 00.0w -- -- 0m-mm:n: 938 0508 Ah: win:— AR: 050:. Ah: ugh:— dw: 9:wa a»: win:— in: won :.8 :.:8 :.8 :58 :vom :.:8 :.3. :.:8 :.8 .58 :vom ...—8 :53. NNO NNO :NO :NO MS: MS: mm Mm: m<>> 05$ NE NH 9:08am 162 N3. 88 :.:.: 88 8.: 8.: 8.8: 8.: 8.8 B B -- -- 2-8mm :..: m8 :.: :.:.: M8 :8 E: N.“ 3: B B -- -- 3-82: :2. 88 2.: 28 8+ :3 8.8: $8 8:: B B -- -- 2.2% 8.8 88 8.: 8.2 8.8:. 8.: 8.8: on: 8.8: 3 B -- - 2-5:: 8.: 88 8.: B 3 8.: 8.8: 88 8.: B 3 - -- 3.2g: 2:: 2.: one :.0.:: 8.8: :2: 8.8: 8.8 8.8: B B -- -- 2-8:: 8.8: on: 8.2. 8.8: 8.82 8.2 8.2:- :od. 88: B B -- -- 2-5:: 8.8 8.: 8.8 8.8 8.8: 8.: 8.8: ::.n: 8.8:. B B - -- 2-8:: ::.2 $8 8.2 8.2 8.8: a: 8.9. 8.: 8.2 B B - -- 2-8:: ::.8 8.: 8.: 8.8 8.8: ::.:. 2.2. 8m: 8.2: B B -- -- 2.5: 8.8M 88 8.2 ::.:. 8.2: 8.: 8.8: 8.2: 8.83.: 8.2: 8.23. -- -- 3-8:: 3.8 8.: 8.8 8:: 88% 8.8 ohm 3.: 8.2: B B - -- 2-8:: 8.8 :3 8:: 8.8 8.8:. :2 8.5. 8.2 8.8.: B B -- -- 2-5:: 8.9. 88 8.: 8.2 8.8:. 8+ 8.8: 8:: 8.8:. B B -- -- 3-8:: :3. 88 8.: 8d 8d :.:- 88: as 8.2 B B -- -- 2-88 8.: m3 8.: 2.: 8.9V 38 8.? ::.N 8.8: B B -- -- 2-38 0:.: 88 8.: 8.: 8.8 8.: 8d: :2. 8.8: B B -- -- 2-88 8.: 88 :2 :.o 8:. 2 .N 8.8: :2 8.2 B B -- -- 2-88 8.: 3o 8.: :3 8w 8.: 8.8: :2 8.8 B B - -- 2-58 m: : :.o 8.: $8 8.8 8.0 8.2 88 8.: B B -- -- 8-88 8.: 88 8.: ::.o 8.: :2. 8.8: 88 8.8 B B - -- 2-85 ugh:— wéwfi Aha: win:— Axw: 0::wa Ah: 0::wa aw: 0::qu . in: win:— 1:01 lelall ea .58 c8 .58 c8 .58 v3. aid-Hal .58 :.8 ...—8 :89:- 88 88 58 :xo :2 :2 mm mm was» as; x”: 5: 2:88 163 :.:.:: ::.8 8:8 ::.: 8:.::: ::.:.. 88:: 88 8:: B B -- -- 2-8:: :8.::: 8.: 8:: ::.:: 8:.:::: 8...: 88:: 8:.8: 88:: B B -- -- :8-8::: 8...: :88 :.:.: ::.: 8.8: :..8 8:.8: :2 8:2: 88 88::. -- -- :.:-::Q :.:.::8 8:8 84:: ::.::: 8.88: B 3 9.8 8...: B B -- -- 2-3:: ::.::: 8.: 8:.:: ::.::: 88:8: :8: 82.: 8.: 8:8 3 B -- -- :8-8::: 88: ...8 8:: ::.: 8.8: ::8 82.: 8.: 8:8: 3 B -- - ::-::: :.:.:: ::8 8:: ::.: 88:: 88 88 :.:.: 88: B B -- -- :8-8::: 88:: ::.: 8:: 8.3.. 888. :88 88 ::.:. 8:.:.. B B -- -- ::-::: 8:88 ::.:: 88::. ::.:: 88:3 8:: 88:: ::.:: 88:8: 8.: B -- -- 2-8: :.8 8.: 88: 8:8: 88:: :.: :8: :..: :8: B B -- -- :8-8: 8:: :8 :.: 8.: 8:8 8:: :8 88: :.::: B B - -- 2-8:: 88: 8.: 8.8.. 2.2 88:: ::.: 88:: :..: 8.8: B B -- -- :88: :.:.: ::8 8:... 8:.8 82 : ::.: 88:: ::.: 8:28 B B -- -- :.:-:8: :8... 8:8 :..: 8:.8 8:.:: 8.: 88:: :2 8:.::. B B - -- 2-8:: :..: ::.8 8:: ::.: 8:.8: ::.8 88: 8.: 8.8: B E -- -- :888: ::.: 88 :.:.: 8:8 8:: 3.8 8:.:: ::.8 8:: ::.8 8:.:: -- -- ::-::: 3.8: ::.:. 88:. ::.:: 88:: :..: 8:: ::8 82 B E -- -- ::-::: 8:88: ::.: 8.8 ::.:: 88::: ::.: 8:. :8: 8:: B B -- -- :8-8::: 8:: ::.: 8...: 8.8 8.8:. :.:8 83. :..: 8:: B B -- -- :.:-:8:: 8:: ::.:: 8:.::: 88:: 8.8: 8:8: 8.8: 8:: 88:8 :88 8:8: -- -- 2-8:: 88:: ::.: 8:.:: 8.8: 88:8: 8.8: 88:: ::.:: 88:: 8.: 8:.:: -- -- :8-8:: :8... ::.::... 8:1 :8... 8:1 :8... 8:1 3:... 8:: 3:... :81 3:... a»: 88 88 .58 :5: .58 v8 .58 88 .58 88 .58 88 .58 :58. SS :88 :8 :8 :2 :2 mm mm ms: :35. 8:: x: 28.5.: 164 ::.: 8:8 8:8: 88 8:.:: 88.8 88 ::.: 8:.8: B B -- -- ::-::-S ::.8: :88 8:. 8:.:: 8.8: 8.: 8:8: ::.:: 88:: B B -- -- 2-8:: :.:.:: :88 ::.: :8.:: 8.8:: 8.: 8:.:: 88: 8:: ::.8 8.: -- - :8-8::-: :.:.:. 8:8 ::.: 8:: 8:.:: ::.8 8:.8: 82 8:8 :.:8 8:: -- -- ::-::: ::.::. 8:8 8:8: :.:.: 8.8: ::.:: 888 ::8: 8.8: ::.: 8:.::. -- -- :8-8::-: ::.:: 8:..: 8:8:. 8.:.: 8:..:::. 8.:.: 888:: 88: 8:.::: B B -- -- ::-::: ::.:: 88 8:.:: :.:.:: 8:.:: 8:: 8.8: ::.: 8:: B B -- -- 88::: 8:.:: 8:: ::.:: ::.:: 8:.::: 8:.:.: 8.8:. ::.:. 8.8: 8 B -- -- ::-:::V: :.:.:: 8:8 8:: ::8: 8:.::: :.:.:: 88:: :.:.: 8:.:: B 8 -- -- 2-8:: 88: 88 8:8: ::.8: 8:.::: ::.: 8:: 8:.:: 88:: B B -- - :8-8:: 8.: :8 8.:. ::.8 8:.:: ::8 8:: 8:8 8:.:: ::.8 8:.::. -- -- :.:.::.:V: 88:. 8:: 88: ::.:: 8:8:.: ::.: 8:8: ::.8 8:: B 8 -- -- ::-::: ::.:: 8:: 8:.8: 8:8: 8:88 :8.:: 88:: 9.8: 8.8: 88 8:: -- -- :8-8:.:: :..: :88 8.: ::.8 8:.:: 8:8 88: ::.8 8:8: 88 88 -- -- :.:-:::: 82: ::.8 8.: ::.:: 8:: 8:.:: 88:: ::.: 8:.:8: 8:.8 8:8: -- -- ::-::: :.:.88: ::.:: 88: 8.::: 8:.::: ::.::: 88::. :88: 8:.:.: B B -- -- :8-8::: ::.:. ::.8 82: ::.:. 8:.::: 9.8 88:: :8: 8:.:: E B -- -- :.:-:8:: ::.8: ::.8 8:: ::.:: 8.::: ::.::. 88:: ::.: 8:.::. B B -- -- :8-8:: ::.: :88 8:.8 ::.8 88: ::.: 8:.8 ::.: 8:.::. B B -- -- ::-::: 8:.:: ::.8 8:: 8.: 8.8:. 8:.:: 88:: ::.: 8:.:: B B -- -- :8-8::: 8.: ::8 8:.:. ::.: 8:8: :88 8:.8 :8: 88:. B 8 -- -- :.:-:::: ::.::... 88... AP: 88... 8:1 ::.::... 8:1 :8»... ::.: ::.::... 8:1 3:... 8:1 88 88 .58 IJIB: .58 88 .58 8%! .58 88 .58 88 .58 .58: ::o ::o :8 :5 :2 :2 :: :: ass :25 x: x: ::.::: 165 [ I wde mun-N owNm boAN oo.o:m boo oo.o: NVA ov.w: up 3 I -- W.H-: HNZ NY; NY: wwfi: No.9” oo.oov va oo.vM ow:V O: on Us up i -- nooHNZ find. 5 .o o: .0 Nmo oN.N: No.N oo.oo 3.4 8.3 N:.o oo.o: -- -- m.m-mwNE 5.2 had oN.oN cod 8.5m so owfi: :md oo.oo oNo 8.2 -- -- mAAwNE :wdm who woé: ooNN 869: S .N ohdv no.2 oo-omN Nod om.wN -- -- m.o-owN—Z oo.om N: A c: .2 oo.om oo.oN-v on: o: .wN omfi omow to B -- -- WTENE two:- VwN 8.9. 5.8:. 8.98 3: 9.60 :83 oo.omN ammo omdv -- -- wooeNE woo hoo ovN “5 on Nvo oo.o: omo ooN: B on -- -- 099:3): no.8 no; ow.w mNdm 8.9% $6 onw Nod omNm :5 up -- -- W.H-:VNE How... on: 3.2 0: .0m oo.oNN- we: omfim 36 8.8: cmo on.MN -- -- moovflz wwN :No vow Nod owfim oo.o oo.o :..: oesvo woo ova -- -- m.m-mNN2 min: NN.o wwfi o: .0 oo.obN mVN oo.mw and oofio oo.o ovo -- -- mAéNN—z 93v: oNo 3.6 mod: oo.o:.N wmo ovofi Nm.m cog-:- 2 .o oo.o -- -- m.o-ONN§ mum mmo o: .0 Qum- Omfih ONo omé ::.: ow.mN U:— 3 -- -- mAAoNE mod o: .o ood O: A on. 3. mod ov.wN N: .N o: .E- N: .o oN.o: -- -- w.o-ooN2 :..N. No; vowm w: A Omdv o: .m OOHMN 3o owe: up on -- -- n.m-mnN-H wvfi omo woo . $4.. oo.om Nmo 8.: av: ow.wN to Us -- -- m. : $th meg-m vmo VNJV mnNm oo.owN vwo om.m ww.m omom up on -- -- nook-NA VdN mo :.m YmN om.mwN oo .v. : 9N odN B :5 -- -- m.m-mmN.._ :ofim ::.o ON..v :N. H m 862 mNA owfi: mod on. H m up up -- -- 0:-:qu wmfi 2o wow no: oo.ow wwo om. S: me oo.om on B -- -- woos..— wxxufi win—u AB: $.wa a»: wiwfi at»: 3wa ARI-11 win:— a—xwi Fax»:— Ah: 88 88 .58 88 .58 88 .58 88 .58 v8 .58 v8 .58 Eon. NNO NNO 5:0 3:0 m2 :2 mm— MW m<>> was» NH NH ::.::—am 166 FR 8.2 2.8 3.8 8.05. a: 8.8 3m 8% B B -- -- 2-98 2m 3 2.8 8.8 8.8m 2 N9 3 38 no as -- -- 2-:8 3.8 22 8.8 8.8 8.8: NS 8.82 S.» 859 as 8.: -- -- 3-98 22 2d NE So on: :.o o? :8 8.2 B B - - 2-88 3.? mod 03 8% 8.8 OS 8.2 v3 95 8d 86 -- -- 2-38 8.8 8.2 8.5 ~23 8.on 85 8.9.. an? 8.8 B B -- -- 8-88 22 we n8 8.2 8.92 3 2.8 2 2.8 -- -- -- -- 2-28 8.x 3o 88 :2. 8.08 8d 8.” 5o 8.: B B -- -- 2-3.8 8+2 a2 8.2 8.? 868 8.2 862 3% oo.o? m2 8% - -- 3.8.8 o: as 8.2 RN 8.: go 8.8 Ba 8.8 86 8.2 -- -- 2-98 88 Ed 8.2 $8 8.9% m5. oo.o: aw oo.o: 8o 8.: -- - 2-:8 88 $2 8.2 8:. 8.9;. Now 8.3 88 8.8a 82 2.3 - - 3-98 3.2 mg 8.8 w? 8.2m mi 8.3 :2 8.2“ B B -- - 3-88 2a 2 mi 3% one? we $2 3m 3% 2 we. -- -- 2-88 8.9 8.0 was 8.? 866 oo.o 862 8.2 8.9; ad 9% -- -- 2-88 m3. :3 8: :.N 8.? Ono 8.8 82 2.3 B B -- - 3-82 8.0 MS 82. m: 2.8 mg own a: 8.8 B B -- -- 2-222 2: 8 com 82 8.8 So 8.: mi 8.8 :.o 8.: -- -- 8-82 mom 85 Max 8.2 on? go 8.8 v2 8.8 B B - -- 2-28 88 28 OS 8.0 8.8 Ed 8.8 a: one. B B -- -- 2.82 9.8 a; mi 2.8 8.93 gm 8.8 one 8.8 So 8.x -- -- 8-82 ”is ugh... a»: ”an... a»: wine a»: ”in... a»: «an... a»: ”an... a»: c8 Idiom .58 ca .58 v8 .58 v8 .58 as 58.: ..8 £8 .35 88 88 :8 :5 m2 :2 mm mm 9.3 ms: mm xm n.....Sm 167 I '- mvfi find 0: .m: NVN ohNo moN oo.om :vN owéw :5 :5 -- -- 0.m-m0ND oofi: :0.o ov.:N :wfi oo.oom mvN oo.o:: 0o.m oo.oV: NN.o ovd: -- I m. : -:0N:: :N.m- oN.o N0:- ovo o0.0: woN 869 .v: .N ome ovo O: .wm -- -- m.o-o0ND vo. :0 vwo oo.o 0w.Nv oo-omLV hN: omfi: mmfi: oo.om: vwo oo.m: -- -- 0:-:-NH No.3 :0: vo.VN 0w.:m oo.omm WWO oo.om: mm-:: oo.ow: :.0.o om.0N -- -- moons. mwwv :06 N: .v o0.:.m 8.28 8.0 o: .oh mud omom :5 :5 -- -- m.:-:0Nm 0:.mb 0:.: O06: wNom oo.Omw :.ms oo.oV: 38w: oo.owN :oo ovém -- -- m.o-o0Nm wmom 0w: 0: .NN oo.oN oo.o0N and on.:: «0.5 8:9 :5 :5 -- -- m.m-th~: hmon voN 0:.0: ow.mm oo.omv 0m.m ohdv h: .N. oN.mm :5 :5 -- -- 0:-:th :.NSW Vm: N: d: o: :.v 8.9% 3:: oNéN o0:- ow.mh :5 :5 -- -- m.o-o:.N~: mm.:: 00.o ow.:N :30 oo.o0N vo: owNv mnN oo.oo N: .o om.o: -- -- m.m-mmN~: :.NNN who 00.:: Rum: oo.oov ohm oo.oo 98¢ oo.oo MNo om.:: -- -- 0:-:me: :.N.0w :36 «0.5 91mm oo.o:v wm.0 oo.oo no.0 : oo.on: N:.o omoN -- -- m.o-omN~: oofiw ow:V ovdm: Show oo.oN:N who oo.Nm w0.w: 8.30 :5 :5 -- -- m.o-o0NO 93.: .03»... a»: 9%.: an: 93.: a»: «sue an: 9:»... a»: Bus a»: :.8 :.8 :.:8 3m :.:8 com ...—8 :.8 :.:8 v8 :.:8 :.3 :.:8 :85. NNO 8:0 3:0 5:0 MS: MS: mm: mm: 35> m<>> NM: NH 2956 168 #60 :5 .- hm 0d: .. 3 amm— v.o no .. : .o N.o .. u- no :5 :5 :.o :.o :5 -.- n.:-:om:m mo :5 :5 :.o :.o :5 .. 0.:-:5m:m 0.o no :5 :.o No :5 -- 0.:-:am:m adv :.nN QM: wN: w.o0 0.0m .. 0mm w.N :.o No no :.N N.o .. .vé :5 No no Nam N.o .. 0.o.ouom: w: :.o No no N. : N.o -- noonam :.N :.o No no m: o.o .. mdéaom: o6: o.om .. 000 QM: E .- Owl N.: o.o -- no so ...- -- v: o.o :5 >.o 0.o :5 .. nooomm m: o.o :5 Yo o.o :5 .. n.o-05mm :.: :.o :5 No o.o :5 -- monoamm ”HMS. was: . MARE . “3R5 mafia 8%:- .. g:— .. , g ......h..u...flh.............,, :5» :SOH. :uom NNO :.omuNO Bu 6): tony—mm :.o-mas gunm- ._ ..pmwwww:afiam.wmra EoEBom Sty: 28:3: .59: m: XKN 2am .mouuozmfi 3H5 05 :0 E5350 Eng—Sm 3:58 05 8355: am”: .8388 88:32 85 :o owflozw 05 8.83:: $35 5mg.» EB 52:68 :: 885558 8355: wow 169 o.“ 2: :.:: 3 2 -- -- 0mm Q8 :.o 2 :.N o.o: -- -- EN :.o 2 2 N.:: B -- 2.32 2.8 :.o o.o: 2 2 B -- 2-32: «.8 :.o 2: :.N 8: B -- 2-289 8. 2m 2 cs 3. -- -- 0mm 3. no we we 8 -- -- 3. 8 we 3 2 B -- 2.28 3. no mo 2 :.N B -- 2.228 2. o.o :.o 2 2 B - 2.928 to :.: 2 2 2; -- - 0mm 2 :.o 2 2 mo -- -- 2 :.o :..m 2 mo 3 -- 2-208 2 :.o 2 2 no 3 -- 2-28 2 :.o 2 2 2 B - 2-28 '35.: mama mama ”aha «awe films mam-4 ..., , . w @339:- u8 8.8 858 can: Baum Bums? Bax-m «33am. ; 170 3 2: 2 2 8 28 -- omm 28 2 v.8 2: 32 2 -- 55 2 22 2: «.9. ca -- 2.388 2.8 N.: 2.8 8: :8 2 -- 2-380 22 2 8.8 :8: 22 2 -- 2-380 2 22 E 28 28 - -- 0mm :..8 2 ....8 o.o 2 -- -- 88 no 28 3 8 B -- 2.98.: 2.8 2 28 :.o 2 B -- 2-28.: Sm 8 0.8 no 8 B -- 2-28.: 8. 28 2 2 2 -- -- owm 20 2 8.8 2: :..: -- -- 20 2 we. 2.: 2.: B -- 2.38: 20 2 22 as :.N: B -- 2-22: 0.8 2 Em 2: o.o: 2 -- 2.23: wow-3...: B... 88 @858 can: §.¢m.§m§>. 838 2:85 171 2 .3. 5.5 to S 33 0mm 5.8 3 2m 2. 5.3 ..N . So No es. o.o ..am 3 -- 52.-382mm 5.8 No SN 3 52 ... - Siavoazfi 0.8 a... 2m o.o 3m 3 - 35:385-0- 53 no 5.5m o.o ..Nm 2 -- RESEREE 5.8 No 5.8 5.5 gm 2 -- Etavoazfi m8 no mom E 5.8 3 - 52382% 3 ...m 3 2. 2 2m -- omm 25 we o.om 2 3 no -- 2m o.o o.o. Z 3 a... -- 2.33 25 5... new ..N o.” no -- 2.330 35 ... mom 3 3 to - 2-33 to 25 an E a? - -- 0mm 5.2 3 o.o. o.o 2 -- -- 2. w... 3 3 ..N B -- 2-88.. 2. no o.o. mo 2 B - 2-28.. 5.2 2 5.2 2 .3 B -- 2.98.. ”an... ”an... ”an... «an... “a”... . «a»... ”an... 825.:- caaxo 3.38 33.: ESE §m> 3.5 NH NH oEEam 3582: 8.. 8.8%.: -- .5883 323 8.8%.: 3 Emma 2903 .03 wfiwfi 4.5868 5 nova-5:00:95 8.8%.: no... at»... £2.38 85:82 5 ©8082. coaguooaoo 8.86.: .58 173 aofidm m0? EMH 35.x.» mmH mH.Hwa HQaH dmdm va madm Hm.m exam 3% mddwo md.m ovd add HOH 8d and 3d 3 3 de 3d 3 H5 3”-me mod 3 H5 de Hdd E .n bad awd mod awd add moa wad W.H-Hco mad 3 E ava H Hd add mod owH mod 9: Ed 3 3 wddou SH 3 H5 H5 H5 and mod 9 d 3 8H 2d 3 3 2”-va Hmd B 3 H5 H5 moa 2 d mva add 3 H5 wad Hmd mH-GU Hde B 3 H5 3 oH .w wmd wa.a wdd mod odd dmfi mmd mddvo whm H5 3 3 3 Pa 3 d H H.H 3d $.H de H5 H5 w.m-maU HH.m B B B B Hd.m oHd de H5 H5 H5 H5 H5 mHHaO mmda no.5” m H d dad Hdd ondH Hmd w H .m de dnH 3 d o:- mhd mddau Sana H5 H5 Hm.a mod 0H d m H d aa.H H Had B B B45 oHd man-mt m wad 3 H5 oHd Hdd 8H de de aHd H5 3 3 H5 mH-Z-Hm HH.wHH de mod wad de dem dnH $.95 HEH ~5de whH H.H.mH ma.H wddnHm wnamda dmd H Hd modm vwd avdcm no.5 Edam Euaa wwddm aH .am mesa th m.m-mm H m aadw om.m mH d :.H 8d whmm HmH mndv $1 nmd Pd de odd w.H-Hm H m mvda 3 H5 H5 3 mos mmd om.mH mvd wma aad Hod mmd mddnH m oma H5 H5 H5 3 omd add m H.H 3d mwd add 3 B m.m-mmH m H Hd H5 H5 B B :..n mad H3 3 dvd 3d 3 B @732 m was H5 H5 Had Hod $6 dmd H Hd H5 mod mod 3 B mH-SmHm ha.v H5 3 H5 H5 Ho.m aH d H5 3 had 3d 3 B mH-EmHm dw.w 3 B 345 oH d 23 odd 9: mod 3H 3 d B B mddem mo... 3 H5 H5 3 $.a aH d B 3 3d odd and mod n.m-mH Hm win:— uiufi dun. wiwfi ARE win:— ARE ”..wa ARE ugh... ...—ES, Mama ABE . e8 v8 .58 com .58 tom ...—cm v8 .58 do... .58 . V8 ...—cm . Hagen. NNO aNO HNO HMO m2 m2 mm mm— m<>> W35 unm— Nm 29.—am 174 Ho.»5 3 3 Had Hod B B B B dam mad de mod Wm-m.HmQ mm.m mad Hdd Had Hod dod mod omd Hod mmd vod 95H de Wm-maanH mWa H5 H5 aa.H mod H5 H5 mmd Hod 3d odd 3 H5 WH-HdnH nWaH dd.H vod vHH mod Hva aHd :..m de de aHd Hva mad deoQ dmd H5 H5 aad Hod S d Hod HXH HXH Hvd vod 3 B Wm-mRH Sm aad Hod SH mod and 3d awd mod de vod B B WTZ-Q bmdm hmH mod and mod mWn de ova dad 25m Hmd 3.2 HYH Wd-th mam B B vud mod mH .m 3d B B H Hd Hdd B B Wm-me nWm H5 3 moH 5d 3: add 3 B H Hd Hod B B WH-HmnH 8.2 B 3 mod mdd oWn mad Pa H Hd 2 d Hdd H H.H H Hd Wd-de vaaH H5 3 H5 3 mwm wmd 0mm Ed 3 H5 B 3 W986 odd 3 H5 H5 H5 moa- aHd maH 3d 8.0 de H5 H5 Wm-mvHU aH.w H5 H5 H5 3 mod mod oHH 3d amen de omd mod WH-HvHU 332 3a 8d 3m de oWom ova amaHV mvH wmda vaa Ed 8d WodEU wWo 3 B aa.H mod mna aHd mad mdd dud odd omd bod Wm-maHU mwd H5 H5 de Hdd wmm mvd H5 3 de 3d add add WH-HaHU ems-H B B Sm aHd awdH 95d dWH mod nod odd HEH de WodaHU 2: H5 H5 3 H5 H5 H5 H5 3 Ed odd omd mod Wm-deU moa H5 3 H5 H5 aa.H de 3 H5 HRH H5 Ed Hdd WH-HdHU mvHa wad Hod a©.m Had wm.w hmd H H.a 8d ova Had Ea mad dedHU 9.0 H5 H5 H5 H5 H5 H5 3 B 9.0 Hdd 3 H5 Wm-me 2a 3 H5 H5 H5 mod mod aa.H 3d dud odd oHd Hod WH-HwU Maw... ugh:— dwfi 93.: ARE «yew... dun. ”aw:— Awa «in... dwfi Max»:— E com com ...—8 v8 ...—on v8 ...—3- com :..—cm to... ...—cm _ v37 .58 H83. NNO aNO “NO “NO ME ME mm mm— m<>> ma...» rumm— NH 33an 175 I l mega mdaH mmd aon HWH $.Hw aha wvdb aa.H mw.Hm mHa 3 H5 Wd.dem H Hdnm 3 3 and aH d caav mwd whdaH dm.m aH .maH aim m H .v S d Wm-mon owda H5 H5 mew aHd Had Ed wa.w Ed 3 H5 ww.» Hvd W735 mWwa B B aa.H mod m5. 5: d mw.H H Hmd de 8d mad Hed Wd-oon add 3 B oa.a mod mm.a H Hd oa.H vod aad add m H d Hod Wm-mva ows H5 3 Had Hdd th oHd 86 Ed 3 H5 B 3 W735 ww.aH wad Hod wed mod ads wmd 345 de 3 H5 3 B devaH aan H5 H5 Hm.H mod mod avd acwv mWH 3.5-a Hm.a :d Hdd Wm-maHQ wddmm H5 H5 dadH mad mem awd cm.mmH owa 8.5-o me amaw hm... W785 3.3m 8m aHd mod mad $.me aow mH.HcH ma.m mWwa cos dosmH aw.aH Wd-doHnH 3.x: B B aad Hdd wde Hm.H mw.HH“ 95H Swa ova dWm aad Wm-m5-HnH Wad: B B ow.m :.o Hag-H de waf- ooa oWwH aa.H mWa Ed W7H>HQ 8.me Sd mad dw.va mod 8.5a 3.5- moaaw wH.Ha om.amv awfia aw.Hda mm.aH WodSQ wWH H B B S d Hod an bad wwd mod ma.H» Hvd and 8d Wm-mm HQ wmwa H5 H5 de Hod $2 and wdd wad wdd Hod 3d odd W7HmHQ dWoH H5 H5 dad Hod mom cad de aad vmm omd de mod demHQ dwd H5 H5 ma.H mod vwa de ma.H vod 8d odd mwd 8d Wm-mmHnH m H .w H5 H5 aod mod H H.m had 3 H5 th 8d 9.: E d W7H m HQ naaa 3 3 min aad $.mH mod Ha.a wdd 3 H5 add add WodeQ dam aad Hod 3d mod vod mod mWH odd oo.o cod 3 H5 Wm-mH HQ 95.0 3 3 Ed mod de aad 3 H5 wwd add mmd mod WH-H H HQ as 3 H5 3H mod 36 had hm d add th odd 3 3 W92 HQ 8H 3 H5 H5 H5 B B 3 3 9: odd 3 B Wm-mooQ ”in... 9.3.: ABE ugh... ARE 9:»:— éufi win... ABE “aha. Eu:— wu—BE a»... , . +351 35 4.2m- ..8 Imam.- ..8 ......wl Ham afll .58 Han damn H53. aNO aNO HNO Ono m2 ME mm mm m3.» mas.» NH NM— 93.5% 176 mWwa da.H mdd nww mad aw.Hm 3d aWam haH oHd Hod H5 3 W735 ww.me oH.H mod 26 de Hw.wH Hod nade gm wme 3.0 B 3 W935 Hw.H H B 3 H5 3 woa m H d mwa H Hd HWm oWd B B Wm-mHa-H n: H 3 H5 de Hod ohm 0H d wm.H mod ch cod 3 B W7H HanH aW H m 3 3 Had Hod HWH H aWo S .n wH d st 8d a3. mod deHanH ao.aH 3 H5 3 H5 oaw mH d cod mod cwd Hod B B Wm-maHnH aH.mH 3 B B E wws omd mod add $6 wed omd mod W7HaHnH mH.wwH aa.H 5d mH.a wdd wa.\-H who wada wdd madH w: aa.Hw Hms deoHnH aH-m H5 3 SH cod ww.H Ed H5 H5 mod odd 3 H5 Wm-moanH ems and mod maw Ed ww.H wdd H5 H5 cod odd 3 H5 Wm-m.H>HnH maw Hod add ww.m de ww.m de H5 H5 wo.H odd 3 H5 WWmS-E adda B B $.a H Hd mWw owd H5 3 Had add 3.2 bWH WEN-H.H owwam ww.H cod www Ed dowwH ww.m aa.maH mom aH.am on mw.a oHd deN-Hm mow B B wed mod mad dmd oHH wdd H5 H5 H5 H5 WmmmHnH 3.8 B E afim oHd awfiw Hw.a ow.mH wWo B B aH.H HHd W7HmHnH ww.mmm madH bad wdwdH wdm modH H mw.m 3.3a aad ww.aw mam ww.m mad dem H.H Hos H5 3 8H wod wow ad 3 H5 ma.H oHd ww.H de Wm-mmH.H wow 3 B a: 8d 8H 2 d H H.H wdd B 3 E d Hod W7H mHnH meH aad Hod ww.H odd ow.» wmd haw Ed mod de Hm.H de Wd-de.H ww.H H da.H mod $.H H-od ww.m de cWa S d aw.H oH d mad 8d W7Hoam Hadm ma.H 3d oa.a wod dde and 8.9 hmd 8w omd aow mmd deoam E-Ho wm.a wdd mm.a Ed sta oWd mo.mH Had a:- dmd aaa odd W7Hme max»... 938 ABE ugh... ARE win... ABE win... ABE 9.wa £wa ugh..— ARE , 3.. 35. ...|._8 v8 .58 e8 a .58 afla ..8 .58 H88. aNO aNO HNO HNO m2 m2 mm mm, m4? m3.» NH NH 0:.:—am 177 ew.mem wWa wdd Pa add wWam wmd wwwda ae.H :..edH Ha.a awd add Wm-maHm aw.wdH 9: add eHH de dwea wed ww.mn dw.H B 3 B we WH-HaHHH mm.aH H B 3 aa.H H emd aw.wa awd mWae ww.H ew.aH Had wad 8d Wd-daHm ehHm Hed add aa.w Ed aH.mH HWd wo.mH dwd 3 H5 3 H5 Wm-m\-HH.H aw.mmm H5 H5 wada aHd emde med eadaa aw.a ww.mmH aha medn de WH-H5-HH.H dw.wwm ddd ddd ddw 8d aH.mw me.H mWaeH nea dH.ew hmm wa.m mad deSE ea.a5- aw.H wdd ww.am Pd mWwa bed wada ewd H5 H5 ead Hod Wm-mmHm Hw.H» nmd Hdd wa.HH Hmd an mad mew dH.H th wmd and mod WH-HmHm ww.mmH Hm.a wdd mmmH Hmd :.ma bed eH.am ea.H me.mm aa.H ead Hod Wad-dam ea.mH H5 H5 H5 3 saw dad aad mdd :.w de H5 H5 Wm-maao aw.mH H5 H5 H5 H5 Haw aad owe Had ea.e awd 3 H5 W7HaaO wm. H m H5 3 Had Hod Hw.ma eo.H mWoH nmd wa.H H ed.H aw.w mwd WodaaO ew.w wad Hod 2 .H wdd ee.H wdd H5 3 H Hd Hod ee.H m H d Wm-mdaO wm.a we H5 me de ma.a HHd aH.a wdd Hw.H de B B W7Hda0 3 .aa 2 . H wdd aad Hod wdd H med mw.m H H d mow wmd aa.w mwd dedao eadH B B amh mad mam eHd mH.H wdd emd wdd de Hod Wm-meO aw.mH B B aa.w Cd oo.a de 2d 3 Ed Hod B B WH-HwHO ewem ead Hdd mH.w an :.wa wd.H mHa Hmd He.m Hmd mH.wH Ha.H Wd-deO eesm aw.m H H d one dad aa.aH mwd mwwH awd B B 3 H5 Wm-meHO ew.aa mWH wdd Hm.: awd wo.wm mw.H ew.aa wWo 3 H5 3 3 W7HeHO :.mHe nwa add cmaaH mw.H oo.o ddd 5.me ma 3 3 B B Wo-deHO dWm de add RH 5d 3 3 mam aHd 3 H5 H5 3 Wm-meO mama Maw:— ABE 9:»:— dwfi ugh:— Axwfi 9H5»:— ARE wing Aha “any: JEE- flufllflal ..8 .58 B. ....8 .35 5%. ..8, .58 H3 lawm- HSOH. aNO aNO “NO GAO ME ME mm mm m<>> was» NH - Nu— wH.Ha—am 178 aa.mdm H H.a H Hd wm.H H 2 d ma.Hn who ae.ma E .H ma.mmH wow -- -- deaa: wme 8H wdd th mod wWwa aH.H 86a wad 8w amd me.H add W7HoeaH ahme mWH edd aHd Hod aa.wa am.H we.aa wH.H ae.w dwd ad add W7HeeaH whme me.H wdd wH.H mod wmsa wa.H aHdm aH.H mw.m amd de mod W7HueaH aa.wwe wWwH HWd ma.a» wha aH.eeH was wH.ewa ae.w ww.meH ww.wH whaH th deeaH wH.e H5 3 dad mod dmw aHd wad mod 3 H5 3 B Wm-mwaH aa.w H5 H5 ew.H edd H H.m m H d aH d H5 mad add 3 B W H -HwaH ae.ma H5 3 nWa wdd onH We a:- Had mad 8d eWH aHd dewaH aa.w 3 H5 9 .a 5d 2 .H mod 3 3 8. H add ae.H E d Wm-maaH mw.mdm ews 8d dth aHd am.aeH ww.H dmsHm ma.a H5 H5 H5 H5 W7HaaH eH dwm ew.e add m H .mw Hed ew.waH ae.a aH .ee H ae.a eWa Hmd H5 3 Wd-daaH we.waH H5 3 Saw mmd we.aw mmd wH.mm aad ae.m edd B B Wm-mdaH ww.mHeH awe 5d wa.eH aHd ea.wam Hm.w amamb ews deem eha mH.aeH Hm.w W7HoaH ea.em H ad.aH E d H :2 th B B whOm wwd wm.aH awd B B dedaH mad 3 3 who mod ae.a aH d H Hd 3 H5 3 aha wad Wm-mmaH-H mWe who wdd mm.a de mw.m aad 3 3 B 3 3 H5 W7HmaHH wag-H B 3 who mod wd.mH de eH.m de mwd wdd de wdd WodomaHH dwsH H5 3 ahH Ed Hw.mH med Ha.H wdd eed edd H5 H5 deemam aa.Ha aw.H mod aa.a H Hd mm.m H wed am.H wdd aHd Hdd aed eod deamam has 3 H5 ed.H wdd Ha.e dmd 3 H5 H5 H5 H5 3 Wm-mHaHH ahem H H5 H5 mom H Hmd nmea ahd haem dwd md.aH wo.H am. He mm.m W H -H HaHH th wwd add ew.H add ewd mod 3 Hue wa.H de Hmd mod deHaHH ”in... Maw:— dufi “..wa ABE win... ABE win... ARE 3:»:- dwfi, win... Qua [Ball‘s .58 .58 .58 fig 8... 1&2]de .58 .5. a _ HEP—- .NNO aNO HNC HMO m5 5.4 mm mm m<>> was» NH , Nu 0:.:—«m 179 aa.w wad Hod oad Hod wa.a de an de ao.H Ed 3 H5 Wm-mwavH mhwon mH.a aod ahHm Hmd Hm.Hma wWa wH.mow wHS em.wH amd B B W7HwavH ahewe Ha.mH de ewfiw mad aa.aoa ww.a mwsmm aa.m heem oad ma.a aHd Wo-owavH aH.a H5 H5 Ed Hod wa.H bod aho mod 3 3 B B Wm-maavH ww.me 3 3 wow nod ww.Ha mad wa.mH H ead mm.aw oad 3 3 W7HaavH ew.wwem me.wH aod mm.ae aod wa.wew am.H H H.em5-a eWm eWHa bod B 3 Wo-oaavH ww.m H aad Hod wad Hod oa.e aad was aad who eod 3 H5 Wm-moavH eedan B B aw.H H aod me.mH H bad ww.wmm om.a awde wo.H awd Hod Wo-ooavH new 3 3 H5 H5 wWa aHd wWa aod awd mod B B WH-:-a5 eH.amH wWa wod mw.mH awd me.we mH.a ma.ee wo.a aa.H oHd H5 3 Wo-oN-aH. amaH eho mod aed mod owe wad Hde amd whH Cd 3 H5 Wm-mmah ma.ea mm.a mod 3 B wo.m mod eWoa mad 3 Hue H5 H5 W7HmaH. ww.aoH wmd Hod H5 H5 aada bed wWab Ha.H wha med H5 H5 Wo-onaH. mw.a H5 H5 aHd Hod we.a de H5 H5 3 H5 H5 H5 Wm-mma~ ea.wwma ae.a: Ho.H oa.womw dew oeHaoa mw.aa ahmbma oH.aa bWwwa mad whaH had W7Hma~ ow.mma ww.a eod whom Had ww.aa who HWH H H aed H5 Hue aH.a mod Wo-omaH. wm.w Hue 3 bed mod Ha.e omd wH.H wod H5 Hue emd mod WH-H Ham node ahH eod who mod Ha.mm ww.H ww.a amd H5 H5 whe mWo Wo-oHaH Hm.awh mw.a mod mw.mom Ha.m mwde wo.e we.am wmd H5 Hue wwd Hod Wm-ma: aw.mHm who Hod wm.w bod Bee had ew.HmH wWH Ha.aa aha eadaa awe W7Ha: oWwem wa.aH 2 .o aadH mH .o wa.mm who ea.wH H am.H wm.HwH now nhmma ahe Wo-ooaHH. aa.mH-m 5.:- aod aw.a de om.mm mwd wH.HaH oWH ahmmH nhw emdma mH.w Wooda: ugh:— wéwfi dun. ugh:— dwE ugh:— u—RE ”..wa ARE ”in... ARE Maw:— an... +3.1]... ....o. .5. :..... ..o. :..... .... ....fl. ..o. ....o. mod-.4? H53. NNO aNO HXO HMO M2 M2 mm . mm— m<>> ms.» unm— NH 0:.:—am 180 wH.aa H5 3 B B ww.a wmd ww.wH oWo H5 H5 awd mod W7HaaH>H ao.mw wwd aod H5 3 wa.H H mmd ww.wa wWo H5 H5 wm.w aad Wo-oaaSH 8.9 B 3 H5 3 ma.a wod ahe aHd H5 H5 Hmd Hod WH-Han mw.mH Hue 3 B 3 H we omd wa.w w H .o H5 H5 wm.m aad Wo-oan ww.w B B 3 3 eH.m de ahH eod B 3 H5 3 Wm-mwa-H oe.wa mw.e 2 .o mwd Hod woe H H.o om.wH aad H5 H5 3 3 W H -Hwa-H wa.HoH ea.w wod 3 B ao.wa wad ma.aw wWo H5 HE E B Wo-owa-H mWaoH oo.o oo.o ww.wH mad ee.aa amd aH.He wed H5 3 H5 H5 Wm-moma-H eH.moH oo.o oo.o mw.ma mad wWea omd wH.en awd 3 B 3 H3 Wm-mema-H ww.ea 3 H5 oa.aH de oo.Ha wad ma.ae eed H5 H5 Hue Hue Wm-m..ma-H mWow 3 H5 oa.mH 2 d ow.H H m H.o wadw wwd H5 H5 B B W7H ea-H wH.aH Hue 3 aHd Hod ow.w owd me de 3 B 3 B Wo-oea1H aWw 3 3 H5 H5 Hw.m de ow.a oHd who wo.o de Hod Wm-mma-H aWeaH H5 3 ma.e H H H.o an H 2 .o ee.ae mwd wWeH wad mw.a m H d W7H ma-H aWemH mWH Hod aw.mH aod wadm mad wada mWo whw wod wWwH Had Wo-oma-H ma.aH H3 3 wed mod aw.e mmd ww.a aod 3 H5 aw.a wad W7H Ha-H aw.waH wwd mod wed mod Ha.mm we.a aw.wm eo.a wWeH wWH H5 3 W933 3.on B B wa.w H H.o ewdm ewd amee who 3 H5 H5 B W H -HwavH wadw ww.a mod mH .aH wmd aa.ew wo.H Hue B on B m H .a aod Wo-owavH made mww S .o m H .H mod ww.mH wmd aw.wa wed H5 3 H H.m wH .o Wm-meavH ao.mw mw.e eod mm.H H H H.o eha H H.o oa.ww de B B 3 H5 WH-HeavH Hw.Hm wed aod aw.H mod ma.e ead emda oed aa.a de B 3 Wo-oeavH «in... 95.: ABE ugh... Ah... win... at»... ugh:— a—RE M.,—RE ARE. ”..wa ARE , Ida-flag: ...Ho. .5. aim-Mia .5. ...Ho. Ital :..... H809 NNO NNO “NO “NO m2 H: mm Mm 2.5 m<>> NH NH 0:.:—um 181 H I5 I om.me ma.e eH.o eeda mwd wH.mH wWo ma.wH aWo B H5 H5 H5 Wm-maaO wm.maw ww.e wod mw.Ha mad awdma wo.m mH.wow mm.w meoa ww.m am.aa aWo WH-HoaaO ow.www ohm eod Hho Hod ww.mHa ww.a aa.me ww.m ew.wwH ae.w wWwH mwd W7HeaaO ma.aww ee.e wod Hho Hod Hw.maa oa.a ow.aaw wm.w ww.eoa mm.w wH.aa wWo WH-HmaaO ea.wwH wa.w mod wa.a mod mw.em mWo aWew aad 3 3 mw.wH de Wo-oaaO ao.aH wWo aod B 3 mod Had aa.e oad B B de Hod Wm-mmaz oham aWo Hod mwd Hod whw de ww.Ha wmd B 3 aH.a aod WH-HwaZ medH H5 H5 B 3 now aad em.m de mad aod H3 H5 Wo-omaz oWaH Hed aod H5 H5 mw.m eH.o wH.e aHd mWH aHd mwd mod Wm-mmaz ea.w wad Hod H5 H5 mmH eod wa.m de ao.a de wed mod W7HmaZ aa.mmm H5 H5 wm.e nod mH.Hw Hho wWHma He.H ma.eH omd H5 3 Wo-omaZ ea.aaH ww.m mod ao.mw Hed oH.mm wWo ao.moH em.H H5 H5 Ha.w mad W7HHaZ Ha.Hmm oe.a mod ea.w aod aa.aw Ho.H ww.eoa om.a wa.mH mwd wm.ea mwd Wo-oHa7H wH.w 3 we 3 H5 me E .o em.a wod H5 H5 wa.H H H.o Wm-mwaH>H wWeH am.H mod emd Hod aw.m oHd eadH Had ewd mod 3 H5 WH-HwaH>H ew.wH H ww.m wod Hw.a mod wwdm Hho aa.ae e H.H emH H aWo em.m m H .o Wo-owaH>H Hw.me am.H aod ahH mod ow.wH wmd oa.Hw oed B H5 H5 H5 W7HeaH>H wm.Hw ee.H mod awd Hod ohaa oWo mmdw awd H5 H5 ma.H mod Wo-oeaH>H mw.m mad Hod H5 H5 eo.H mod amd Hod mmH aHd wmd mod Wm-mwaH>H aw.mmH 3 H5 ww.a aod ame owd oa.wa de 3 B ew.w de W7Hwa2 aw.aa aH . H aod aw.w aod tha Hed S .we wad H5 3 H5 Hue Wo-owaH>H oa.w wad Hod H5 H5 mw.m de aw.a aod H5 3 aw.H de Wm-maaE win:— uiwfi ABS 9:»:— waE 9.wa ARE wax»... aw:— uxxwfi dun— wéwfi ARE .5. ..o. :..... .5. ...... .5. ....o. .5. .58 gala-aw.wa H53. NO NO “NO HNO H2 H2 HH HH 2.5 35 NH NH 0385 182 aa.aam oe.e mod aH .aeH Hm.H wo.ww aed wWwaH aad ow.wa ewd we we WH-HwaM whama ow.H aod wo.am ewd wm.ew Ho.H wo.wa mo.H ww.wH ewd we we Wo-owa~H ew.wH wad Hod we we wo.m mH .o wm.w de wwdH awd oo.o oo.o Wm-mma~H wm.am we we we we wada HWo ee.aa aWo aH.a ewd wad Hod W7H mam ma.ewm owd Hod aada mad eo.ww ao.H aw.me eWH aw.mH H Ham em.wm eoH Wo.omam ww.mm we we ow.H eod oWw mmd mWwa mwd aw.wH ew.H we we Wo-oeaO ww.wHa mod wod meaH H H.a eo.wm mwd we.ww ewd HWo aod we we Wm-mwaO me.HaH mw.w wod Hw.e H H.o ea. H n mad aa.ew wed aWH H awd wmd Hod W7HowaO ww.maH wa.H mod oH.a eH.o mH.Hm ead wo.aw mwd eWwH end we we W7HewaO Hw.mmH aw.m wod wm.a m H .o 2 we aad am.am eho meH oWo mad mod WH-H..waO mw.waw ao.aH aH .o E .wa we.H mw.e Ha aa.w ae.www ao.w ow.ww aa.a wm.ew ww.H Wo-owaO wedH we we we we aw.a 2 .o mw.m S .o aH .a S .o wed nod Wm-mmanH wa.on ma.a aod we we ww.aa amd wm.ww owd He.wa Hed we we W7H ma.H am.wem aw.w wod em.wa Hho mw.Ha ewd aa.aaH de aw.aw Hho aw.e H H.o Wo-oma.H wWaa eed aod we we 2 .a mmd aadH Hmd we we ew.H de Wm-momanH ao.aH we we we we em.w amd aodH omd we we Hho mod Wm-mema.H mea E .a eod we we HadH emd wH.H H omd we we we we Wm-mama.H meew ww.m S .o Ha.am ao.H H He H am d ohom mad aa.H S .o mad wod W7H ma.H eH .wowH whaH 2 d wo.wH 2 .o deH m ma.a aH .mae ohw wodem ow.e wo.ww mw.H Wo-oma.H aw.ma aw.a wod we we wa.w aad ae.e aH d mo.w HWo om.H ao.o Wm-mwaO we .H H H eWH mod we we ww.aw mw.H aw. Ha owd aw.w de we we W7HwaO Ha.Hmm ewdH aod 8.... mod 2 .ow mwd mw.aeH ww.H mm.ma aa.H Hme mwd Wo.owaO Mia... $.wa HRS web:— wa8 3.wa ABE ”in... ARE 9:»... ABE ”..wa ABE 1.51... we. .5... [3.1 ....o. w... :..... we. .52 w... aflalws H598 aNO aNO HNC HNO H2 H2 HH HH @435 @455 NH NH 0.956 183 wm.mm awd mod we we eH.oH mwd mw.mH eWo we.w eho we we Wm-meaD ae.mw NWa oo.o we we wa-ma mH.H aw.wm wm.H ma.eH ww.H we we WH-HeaD aw.Hm who mod Hw.e wad ma.w wad we.w aad oWoH Ho.H aH.H H H.o Wo-oeaD wo.awm am.wH 3 .o aadH H H.o mw.ew eoH wm.woa wa.H cm.mw ww.H we we W.H-Hwah. mWoam ma.e oHd oH.n aod Hw.aw aad Hm.ewH am.a mw.mw aw.H wm.we we.a Woowaw wH .ea mw.w wod we we ww.ea wad aw.we NWO we we we we W H -Heam oa.wom aWo Hod wa.w eH.o awde mH.H mH.awH He.a aw.wm ww.H wo.wa Had Wo-oeam HWww ewd Hod wm.w H H.o wa.wH ead mw.em mwd ae.wa who we we Wm-mwa~H ugh... MARE ABE ugh... ABE 9.wa dun. win:— dwfi win... ARE 9:»:— ARE [a we... ...—8 we. ...—8 we. ...—8 we. ...—3. we. .58 we. ...—8 H33- NNO aNO HNO HNO H2 H2 HH HH m<.5 m<.5 NH NH aa.aam 184 a. ma -- -.- a.na .. -- .. 9mm w. m Hwe Hwe we Hwe Hwe awe 0>< he Hwe Hwe we Hwe Hwe Hwe W.H-HomHm he Hwe Hwe he Hwe Hwe Hwe W.H-HemHH am Hwe Hwe a.m Hwe Hwe Hwe WHHumHH NwH -- -- am H.wH .. -- Qmm H .aH Hwe Hwe w.m whw Hwe Hwe 0>< H.wH Hwe Ww we w.m Hwe Hwe Wo-oaam o.H H Hwe Hwe he we Hwe Hwe Woéeam a.H H Hwe Hwe o.e H.m Hwe Hwe Woouam a.wm -- E H .ww .. -- H m.on Hw.m e. 2 Hwe Hwe ww Hwe Hwe mm.w 0>< w. m H Hwe Hwe o.m Hwe Hwe w.aH Woéomm w. m Hwe Hwe Ha Hwe Hwe wH Woéemm H .aH m.m Hwe w.w Hwe Hwe Hwe Woommm Hwflw. . ...w ..w mm.a. am.wem. .885. $89... 8.4.8.835. _. Ha.am. aNO . .58. HS. HH . 9.5 .5. NH ...... aa.aam»... .58.... .25. 2.8.... am... .. wow. .2... .28....2 8.... o... .o 8.3.5.. wa.w..s. 03.28 05 .886... Qmm 83...... 88.38 85 «0 $802. 05 .888... mi. Game 5803 two .8860. ... 89888.8 .886... we. 185 N. -- -- .... ... S. .. a... .... .3 .3 v... a... .... .3 0>< .... ... .3 3.. ..R .... .... 8.3.. .... ... .3 ..R .... .... .... 2-..... a... o. N. 3. .... .... .3 8.3.. o... -- -- ... a... -- -- a... o... .3 .3 ...V. 8.. .3 .3 82 N... .3 .3 a... N. .3 .3 3%.... S. .3 ... .... N. .3 .3 3.3.8 .... ... .... .... ... .3 .3 3.3.8 5... -- -- ...... -- -- -- a... ... .3 .3 N. .3 .3 .3 03.. ... .3 ... ... .3 .3 .3 ...-.8... ... .3 a... ... .3 .3 .3 2-3:". ... .3 ... ... .3 ... .3 ...-3... a... -- -- -- -- -- -- a... ... .3 .3 .3 .3 .3 .3 o>< o. .3 .3 .3 .3 .... .3 ...-.08 N. .3 .3 .3 .3 N. .3 2-38 ... .3 .3 .3 .3 .3 ... ...“... .mfla. gigggg. __ .38 «.8 ....o .... .8 w .35 .8 _ 2.5.1 186 WNH -- .. H.oH Hw.m -- I nHmMH mHN :5 =5 Nd HEOH :5 =3 O>< q Hm :5 H3 Hd o.oH HHXH QH m.m-mommnH Ha.mH =5 :5 Wm o.oH :5 =5 m.m-mnmNnH 9mm N.N :5 NE NH H :5 =3 n.m-mammm wd Nd -- w.m wm.e we.w n H .m H Qmm mdmw m6 H3 ENNN 3.8% NwdaH wo.am O>< imam m6 v. Hm mdmm HH.o.V Omen mNN mH-HoNNO ficwb Hum =5 w.mHN N.:.m Wm: wH.H 07380 n. H mm >6 HE wdmm ...wa Woom N.NN n. H -HmNNO N... .. HawN H.NH aw.w -- -- QmMH m. HoH HHXH «.mH Wmm 3.6m H3 :5 O>< WNOH HH.o fiwH Ema H. Ho :5 HHXH n.m-monN‘H H.moH HHXH v.8 Wow Nam =5 :5 m.m-mnanH wém HHXH QNH 0. Ha QNc :5 =5 wa-m..mN‘H wd -- -- WH wo.wH wm.w we.H Qmm a. H rm =5 :5 w.mm wde H ww.mvH me.mmm O>< Qwom QNH NdH m.mw o.mHH VHVH finmm ndéom: Nfihm N... md mdn m. HNH 5mm H 80mm ndénm: -- H.o v.H H odn 0.3 N.an .. ndémo: 187 ... .... v... a... .... .... ..N a... 5...... v... 8... ...3 a...» R... 8.8 c>< -- -- -- -- -- -- -- 3.335).... .... ... o... .... .... ...... SN 3.5.38.8. ....N N. Z. ..8 .... o.o. .... 85:88.2... ...... ... ...... ...» ...... .... .... 5.8.382... ...... Z .... .3 .... ...... ZN 3.28382... ..R. .3 a... h... a... a... v... 3.835).... ... .... .... .... .... R... -- a... ..R. o... .... v... 8.... Na... .3 03. a... S. ... o... «.... .... .3 ...-.qfid ...... ... ... .... ...... .... .3 ...-330 ...... ... .... a... v... .... .3 ...-.38 #8.... .8 can... 188 2..... 3 3 3 3 ...... 9...... N... ...... 3 3 3 3 ...-...... ...... 3 3 3 3 ...... 8.... ....o. ...... 3 3 3 3 ...-...... .5... 3 3 3 3 ...... 8.... 3 3 3 3 3 3 ...-...... .... 3 3 3 3 ...... ...... 3... .3... 3 3 3 3 ...-:... ...-... 3 3 3 3 3 3 3...... o... ...... ...... 3 3 ...-o... .... 3 3 3 3 ...... 3.... 3 3 3 3 3 3 ...-.... ...... 3 3 3 3 3.... 3.... .... ...... 3 3 3 3 ...-.... 8...... 3 3 3 3 ...... 3... .8...- o... ...... 3.... 3 3 ...-...... 8...... 3 3 3 3 ...... 8... :..... ...... ...... 8.... 3 3 ...-3... 8...... 3 3 3 3 ...... 8... ...... ...... .8... 3.... 3 3 ...-o... a... 3 3 3 3 R... ...... 3 3 3 3 3 3 ...-.... 3... 3 3 3 3 .... ...... ...... 3.... 3 3 3 3 ...-.... ...... 3 3 3 3 ...... ...... ...... 8.... 3 3 3 3 ...-.8 .3... 3 3 3 3 ...... 3.... N... 93... 3 3 3 3 ...-.... ...... 3 3 3 3 ...... 3.... ...... 9...... 3 3 3 3 ...-.... .8... 3 3 3 3 ...... 8.... ...... ...... 3 3 3 3 ...-o... ...... 3 3 3 3 8.... ...... .8. o... 3 3 3 3 ...-.... ...... 3 3 3 3 ...... on... 3 3 3 3 3 3 ...-.... ...... 3 3 3 3 ...... 8.... 8... ...... 3 3 3 3 ...-...... ...... 3 3 3 3 3.... .3... :..... 8.... 3 3 3 3 ...-3... ...... 3 3 3 3 .8... 3.... .... ...... 3 3 3 3 ...-...... ... ... ... agafigaafigfi 3. 3. ....8 3. :..... 3. ....8 .81 .58 [6314.81le ....m 3.... «.8 «.8 ...o ...o .... ...). .8 .8 .35 ...-3 .8 .8 2...... 608.8... .0.. .886... -- 83.0806 320... .886... 3 3...... ...».03 .06. mi... 4:08.60. ... ..o........00..00 .886... 60. d»... 60.3.... 8.2.08. ... 68080.. 8.38.0080 .886... ....o. 08.... .82 ...... San :....088H .8.E0._O 6.2.0.. 0m .H-N 2.39 v— 56:3”:- 189 8.3.. 3 3 3 3 .8... 8.... 88.8 8.... «.... 8...... 3 3 ...-8.0 .... 3 3 3 3 SE 8.... .8. 08.8 3 3 3 3 ...-8.0 .8... 3 3 3 3 ...... 8.... .«S .8... 3 3 3 3 ...-8.0 ...... 3 3 3 3 ...... 8:. ...... 8.... 3 3 3 3 ...-8.0 8... 3 3 3 3 ...: 8.... E... o.o... 3 3 3 3 ...-..0 8...: 3 3 3 3 3.... 8...... 8.... 88... 3 3 3 3 ...-..0 .8... 3 3 3 3 8...... 83... .38 ...... 8.... $8.. 3 3 ...-8.0 ..E 3 3 3 3 ..E 8.8 3 3 3 3 3 3 ...-..0 .8... 3 3 3 3 .8... 8.... ...... 8.... 3 3 3 3 ...-80 .... 3 3 3 3 S... 8:... ...... 8...... 3 3 3 3 ...-30 .....8 3 3 3 3 .8..«. 3... 8...... 8.... 3 3 3 3 ...-...0 o8... 3 3 3 3 ...... on... ...... 8...... 3 3 3 3 ...-...0 ...... 3 3 3 3 88.. 83 3.8 ...... 3 3 3 3 ...-$0 ...... 3 3 3 3 ...... 3.... 3... .8... 3 3 3 3 ...-.8 .....« 3 3 3 3 .8... on... .8... 8:... 3 3 3 3 ...-.8 .8... 3 3 3 3 88... 8...... .8... o... 3 3 3 3 ...-8.0 ...... 3 3 3 3 ...... 8.... 3 3 3 3 3 3 ...-...m 8.... 3 3 3 3 ...... 8.... .8. 8.... 3 3 3 3 ...-:.. ...... 3 3 3 3 .....o. 3.... 3.... ...... .... ...... 3 3 ...-E... 8.... 3 3 3 3 .8... 8... ...... ...... ...... 88... 3 3 .......m .8... 3 3 3 3 8.... 3... .83. 88.. 3.... 3... 3 3 ...-.... .8... 3 3 3 3 :..: 8.... ...... on. ...... ...... 3 3 ...-8.... o...«. 3 3 3 3 ...... 8.... 3 3 3 3 3 3 .......m .8... 3 3 3 3 .8... 8...... ...... on... 3 3 3 3 2-..... ...... 3 3 3 3 8... 838 .8. ...... 3 3 3 3 ...-...... ... a ... afigfigflflafiafl 3. _3. ....o. 3. ...... 3. :..... 3. ....e. 3. £8 3. :..... 3.... «.8 «.8 ..8 ..8 .... .... .... .... .35 .43 .... .... 2...... 190 I I ....8 3 3 3 3 .8... ...... ...... ...... 3 3 3 3 ...-...a ...... 3 3 3 3 8.... 8.... ...... ...... 8... ...... 3 3 ...-...... .8... 3 3 3 3 .8... ...... ...... ...... 3 3 3 3 ...-...n. .8... 3 3 3 3 ...... ...... ...... .8... 3 3 3 3 ...-..8 .8... 3 3 3 3 8...... ...... 8...... ...... ...-.... 8...... 3 3 ...-...... 8...... 3 3 3 3 .... 9...... ...... 8...... 3 3 3 3 ...-...o .8... 3 3 3 3 ...... .3... E... ...... 3 3 3 3 ...-:... ....8 3 3 3 3 ...... ...... ...... ......o 3 3 3 3 ...-...... 8... 3 3 3 3 8... 8.... 3 3 3 3 3 3 ...-.2... .8... 3 3 3 3 .8. 8.... 3 3 3 3 3 3 ...-...... ...... 3 3 3 3 ...... 8.... 3 3 3 3 3 3 ...-...... 8... 3 3 3 3 .8... ...... ...... 88... 3 3 3 3 ...-.8. ...... 3 3 3 3 ...... 8.8... ...... 8.... 3 3 3 3 ...-o... ...... 3 3 3 3 ...... .8... 3 3 3 3 3 3 ...-.8. ...... 3 3 3 3 ...... ...... 8.... 8...... 3 3 3 3 ...-.8. ...... 3 3 3 3 ...... ...... ...... ...... ...... 8.... 3 3 ...-88. ...... 3 3 3 3 ...... ...... 3 3 3 3 3 3 ......n. .8... 3 3 3 3 ....o. ...... 3.... ...... 3 3 3 3 ...-.... ...... 3 3 3 3 «...... ...... ......o. ...... 3 3 3 3 ...-88 ...... 3 3 3 3 ...... ...... ...... ...... ...... ...... 3 3 ...-3.0 8.... 3 3 3 3 3...... ...... :... 8...... 3 3 3 3 ...-....0 ...... 3 3 3 3 3... . ...... ...... o.o... 3 3 3 3 ...-....0 8...... 3 3 3 3 9...... ...... ....8 ...... :..... ...... 3 3 ...-.....0 8.... 3 3 3 3 .8... 8.... ..8... ...... 3 3 3 3 ...-...0 . . . 3 ...-...0 a 3. ‘ 3. ....o. 3. ...... J8 ....e. 3. ....o. 3. ...... 3. 4...... .5... «.8 ..8 ..8 ..8 .2 ...). .... .... .35 ....B .... .... 2...... 191 Illlllll - l .... 3 3 3 3 .... 8... .... .... 3 3 3 3 ..EE ...... 3 3 3 3 ...... om: ...... 8... ...... o... 3 3 ...-..E 8.... 3 3 3 3 ...... 8... ...... o... 3 3 3 3 ...-..E ...... 3 3 3 3 ...... .... .2... .... .... o... 3 3 ...-EE ...... 3 3 3 3 .8... o... ...... o... ...... 8... 3 3 ...-..E .8... 3 3 3 3 ...... .... N... ....o 3 3 3 3 ...-..E N.:: 3 3 3 3 ...... .... o2... .... 3 3 3 3 2-..; E... 3 3 3 3 .... o... a... SS 3 3 3 3 ...-..E ...... 3 3 3 3 ...... 8... 8.... .2: .... ....o 3 3 2-8... ...... 3 3 3 3 ...... ....o .....S .... R... .... 3 3 ......m .... 3 3 3 3 .... .... 3 3 3 3 3 3 2.33 ...... 3 3 3 3 ...... .... .2... .... .... o... 3 3 ...-..E ...... 3 3 3 3 .2. o... ....2 o... ...... .... 3 3 ......m 0...: 3 3 3 3 .... o... ...... o... ...... 8... 3 3 2-3.5 ...... 3 3 3 3 .... o... ...... E... a... 85 3 3 ...-..E ...... 3 3 3 3 ...... om: ...... .... .... 8... 3 3 ...-..E .2..._ 3 3 3 3 ...... .... ...... 8... .... .... 3 3 ..E... a... 3 3 3 3 ...... 8... ...... .... .... .... 3 3 ...-..E 5.... 3 3 3 3 ...... 8.. :..... ...... ....a. .2... 3 3 ...-..5 ...... 3 3 3 3 ...... ....o 3 3 ...... on... 3 3 2-35 ...... 3 3 3 3 ....2 .... ...... oz: 3 3 3 3 ...-..E ...... 3 3 3 3 2..: o... .... o... .... .... 3 3 ...-..5 ...... 3 3 3 3 a... o... ...... o... ...... o... 3 3 ...-Eo ...... 3 3 3 3 .8... .... .....S .... ...... .... 3 3 .....2a ...... 3 3 3 3 ...... 8... ...... .... 3.... 8... 3 3 ...-..E figfigfifiaaflqgflifiaflm 3. 3. ...... 3. ...... 3. ...... 3. ...... 3. 5o. l3.| ...... .3... 88 85 :8 :8 m2 .2 mm mm .35 .43 Na x..— 2.8.. 192 ...... 3 3 3 3 ...... .... ...... .... ...... Q... 3 3 ...-...m ...... 3 3 3 3 ...... .... ...... ..2 3 3 3 3 ...-...o ...... 3 3 3 3 ...... .... ...... .... :... .... 3 3 2-..... ...... 3 3 3 3 ...... .... ...... .... .... .... 3 3 ...-...o ...... 3 3 3 3 ...... .... .... .... 3 3 3 3 ...-...0 ...... 3 3 3 3 ...... ..2 3 3 3 3 3 3 2-..... ...... 3 3 3 3 ...... .... .... .... 3 3 3 3 ...-...o ...... 3 3 3 3 ...... .... .... .... 3 3 3 3 ...-...o ...... 3 3 3 3 ...... .... ...... .... 3 3 3 3 2-..... ...... 3 3 3 3 ...... .... ...... ...... .... .... 3 3 ...-...o ...... 3 3 3 3 .... .... ...... .... ...... .... 3 3 ...-.... ...... 3 3 3 3 ...... .... ...... .... ...... .... 3 3 2-..... R... 3 3 3 3 .... .... ...... .... ...... .... 3 3 ...-...o ...... 3 3 3 3 .... .... .... .... .... .... 3 3 ...-...o ...... 3 3 3 3 ...... .... ...... ..2 ...... .... 3 3 2...... ...... 3 3 3 3 ...... .... ...... .... ...... .... 3 3 ...-...o ...... 3 3 3 3 ...... .... .... .... 3 3 3 3 ...-.... ...... 3 3 3 3 ...... .... ...... .... 3 3 3 3 2-.... ...... 3 3 3 3 ...... .... ...... .... 3 3 3 3 ...-.... ...... 3 3 3 3 ...... .... :... .... 3 3 3 3 ...-...". ...... 3 3 3 3 ...... .... .... .... 3 3 3 3 2-..... ...... 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 3 3 3 ...-...... I??? a aggaaflwfigfiag 3. 3. ...... 3. ...... 3. ...... 3. a... I3.|Ifl._d.ll 3. ...... .5... 88 ....o :.o :8 m2 :2 mm mm ...? .35 x... .... 2&5. 193 I l ...... 3 3 3 3 ...... .... ...... .... ...... .... 3 3 ...-.... ...... 3 3 3 3 ...... .... .... .... 3 3 .... .... ...-.... ...... 3 3 3 3 .... .... .... .... 3 3 3 3 2-.... ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... ...-.... ..2. 3 3 3 3 .... .... .... .... 3 3 3 3 ...-.... .... 3 3 3 3 3 .... .... 3 3 .... .... 2-.... .... 3 3 3 3 3 .... .... 3 3 .... .... ...-.... ...... 3 3 3 3 .... ...... ...... .... 3 3 ...... .... ...-.... ...... 3 3 3 3 ...... .... .... .... 3 3 3 3 2-.... ...... 3 3 3 3 ...... .... .... .... 3 3 3 3 ...-.... ...... 3 3 3 3 ...... .... ...... .... 3 3 3 3 ...-...m ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... 2-..... ...... 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 3 3 ...... .... ...... .... ...... .... 3 3 2-..... ...... 3 3 3 3 ...... .... ...... .... .... .... 3 3 ...-...: ...... 3 3 3 3 ...... .... ...... .... ...... ...... ...... .... ...-...... ......m. 3 3 3 3 ...... .... ...... ...... ...... ...... 3 3 2-..... ........ 3 3 3 3 ...... .... ...... ...... ...... .... 3 3 ...-8... ...... 3 3 3 3 .... .... ...... .... ...... .... 3 3 ...-...: ...... 3 3 3 3 3 ...... .... ...... .... 3 3 2-..... ...... 3 3 3 3 .... .... ...... .... ...... 9.... 3 3 ...-E... ...... 3 3 3 3 ...... .... ...... .... ...... .... 3 3 ...-...m ...... 3 3 3 3 ...... .... ...... ..2 ...... .... 3 3 2-..... agfigadflafigaafigfl Jana ...... 14% ...... ...... final ...... 3. Ia! 3. ...... .5... ...o 88 :.o :8 m2 5.. mm mm 9.3 m...» x... .... 2.5.. 194 ...... 3 3 3 3 .... .... .... .... 3 3 3 3 ...-...v. ...... 3 3 3 3 .... .... .... .... 3 3 ...... .... 2-..... ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... .... ...-.... .... 3 3 3 3 .... .... .... .... 3 3 3 3 ...-.... ..2.. 3 3 3 3 ...... .... ...... .... ...... .... ...... .... 2-..... ...... 3 3 3 3 ...... .... ...... .... 3 3 ...... .... ...-...“. ...... 3 3 3 3 ...... .... ...... .... .... .. .... ...... .... ...-...“. ...... 3 3 3 3 R... .... ...... .... ... .. .... ...... .... ...-.... ... . 3 3 3 3 .... .... .... .... 3 3 3 3 2-.... .... 3 3 3 3 .... .... .... .... 3 3 3 3 ...-.... ...... 3 3 3 3 .... .... ...... ... . 3 3 3 3 ...-.... ...... 3 3 3 3 3 3 .... .... 3 3 ...... .... 2-.... 3...... 3 3 3 3 ...... .... ...... ..... ...... ...... .... .... ...-.... ...... 3 3 3 3 .... .... .... ... .. 3 3 3 3 ...-.... ...... 3 3 3 3 .... .... .... .... . 3 3 3 3 2-. ... .... 3 3 3 3 3 3 .... .... . 3 3 3 3 ...... ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... 2-.... ...... 3 3 3 3 ...... .... ...... .... .... .... ...... .... ...-.... ...... 3 3 3 3 .... .... .... .... 3 3 ...... .... ...-.... ...... 3 3 3 3 ...... .... ...... .... 3 3 3 3 2-..: ...... 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 ...-...: ...... 3 3 3 3 ...... .... :..... .... ...... .... 3 3 2-..... ...... 3 3 3 3 ...... .... ...... ...... ...... .... 3 3 2-..... ...... 3 3 3 3 ... .. .... ...... ...... ...... .... 3 3 ...-...... gagaglaaagfiag a 3. 3. ...... 3.ll:.|..|.1 3. ##3## 3. ...... 3.. 88 88 38 :8 ms. :2 mm mm ...» ms: .... .... 2.8.. 195 H I l .... 3 3 3 3 :... .... .... .... 3 3 3 3 ........>. ...... 3 3 3 3 3 3 .... .... 3 3 ...... ...... 2-..... ...... 3 3 3 3 ...... .... ...... .... .... .... ...... ...... ...-...: ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... ...-...: ...... 3 3 3 3 .... .... .... .... 3 3 ...... .... 2-..... :..... 3 3 3 3 ...... .... .... .... ...... .... ...... ...... ...-...: ...... 3 3 3 3 .... .... ...... .... 3 3 .... .... 2-..... ...... 3 3 3 3 ...... .... ...... .... .... .... .... .... ...-...: ...... 3 3 3 3 ...... .... .... .... 3 3 B... .... ...-.... ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... .... 2-.... ...... 3 3 3 3 .... .... ...... .... ...... .... ...... .... ...-.... ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... ...-.o... ...... 3 3 3 3 ...... .... ...... .... 3 3 ...... .... ...-.3... ...... 3 3 3 3 ...... .... ...... .... 3 3 ...... ..2 ...-...... ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... .... 2-.... ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... .... ...-.... ...... 3 3 3 3 ...... .... .... .... 3 3 .... .... ...-.... ...... 3 3 3 3 ...... ...... ...... .... ...... .... ...... .... 2-.... ...... 3 3 3 3 .... .... ...... ..2 ...... .... ...... .... ...-.... ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... .... 2-.... ...... 3 3 3 3 ...... ...... 2... 8............ ...... 3 3 ...-.... ...... 3 3 3 3 ...... .... ...... .... 3 3 3 3 ...-...... ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... ...-.... ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... .... ...-.... ...... 3 3 3 3 .... .... ...... .... ...... .... ...... .... 2-..... ...... 3 3 3 3 ...... .... ...... ...... ...... .... ...... .... ...-.... §§§§§q§§fl§§§§fl§§ 3. 3. ...... 3. ...... 3. ...... 3. ...... 3. ...... .3. ...... .3... .xo ..8 38 38 5.. E). mm mm was. .55 .... .... 2.3.. 196 ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... ...-...... ...... 3 3 3 3 ...... .... .... .... 3 3 .... .... ...-...... ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... ...-...... ...... 3 3 3 3 .... .... .... .... ...... .... .... .... 2-.... ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... ..2 ...... ...... 3 3 3 3 ...... .... :... .... ...... .... ...... .... ...-...o ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... ...-...o ...... 3 3 3 3 ...... .... ...... .... ...... ...... ...-.... .... ...-...o ...... 3 3 3 3 ...... .... .... .... ...... .... .... .... ...-...o ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... .... 2-....0 ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... ...... 2-....0 ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... .... 2-....0 ...... 3 3 3 3 ...... .... ...... .... 3 3 3 3 ...-...o ...... 3 3 3 3 ...... .... .... .... 3 3 .... .... ...-...z ...... 3 3 3 3 .... .... .... .... 3 3 ...... .... 2-...2 ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... ...-...z ...... 3 3 3 3 .... .... .... .... 3 3 .... .... ...-...z .... 3 3 3 3 .... .... .... .... 3 3 3 3 2-...z ...... 3 3 3 3 ...... .... .... .... 3 3 ...... 9.... ...-...z ...... 3 3 3 3 .... .... .... .... 3 3 ...... ..2 ...-...z ...... 3 3 3 3 .... .... ...... .... ...... .... ...... .... ...-...z ...... 3 3 3 3 ...... .... .... .... 3 3 .... .... ...-...: ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... ...-...: ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... .... ...-...: ...... 3 3 3 3 .... .... .... .... 3 3 ...... .... 2-..... ...... 3 3 3 3 ...... .... ...... .... .... .... ...... ..2 ...-...: 3. I..sz ...... 3. ...... 3. ...... 3. g. 3. ...... [anal-mm. .5... 88 ...o a... as m2 5. mm mm ....» ms; ...... .... 2.3.. 197 ...... 3 3 3 3 .... .... .... .... 3 3 .... .... ...-...: ...... 3 3 3 3 ...... .... .... .... 3 3 .... .... 2-..... ...... 3 3 3 3 .... .... .... .... .... .... .... .... ...-...: ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... ...... 2-..... ...... 3 3 3 3 ...... .... ...... .... ...... .... .... .... ...-.... ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... .... 2..... 8...... 3 3 3 3 ...... .... ...... ...... :..... .... ...... .... ...-.... ...... 3 3 3 3 ...... .... ...... .... 3 3 ...... .... ...-.... Nogwa Us up «5 H5 aw.wm omwd whim. OOH-o up vs mw.m-o0 GSA WTKNM ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... ...-.... ...... 3 3 3 3 .... .... .... .... 3 3 .... .... ...-.... aw.aw up .5 as 3 3.5.2 omwd ma.w 2.6 U9 .5 5%.? Oww-H mAAmNm ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... .... ...-.... $0603 Up Up .5 9. £663 omod ”am.wem tn: www.bVw oomdo gown 03.6 mdéomo ...... 3 3 3 3 ...... .... ...... .... ...... .... ...... .... ...-...o ...... 3 3 3 3 ...... .... ...... .... ...... .... .... .... ...-.... ...... 3 3 3 3 ...... .... ...... .... ...... .... .... .... ...-...... ...... 3 3 3 3 ...... .... ...... .... ...... .... .... .... ...-...... ...... 3 3 3 3 ...... .... ...... .... ...... .... 3 3 ...-...u .... 3 3 3 3 .... .... ..2 .... 3 3 .... .... ...-.... ...... 3 3 3 3 ...... .... .... .... 3 3 ...... .... ...-.... ...... 3 3 3 3 ...... .... ...... .... 3 3 ...... .... ...-.... agafigaflqaaglflflafi 3. 3. =..4..|J.m..l :...m laglluallalwwwl ...... 3. ...... ...... .xo .xo :8 :8 ms. .2 .... .... .... .35 .... .... 2.8.. 198 199 .... -- -- .... R. -- - a... .... - -- .... .... -- -- o>< ...... 3 3 ...... :... 3 3 2...... ...... 3 3 .... ...... 3 3 2...... ...... 3 3 ...... .... 3 3 2...... .... - - .... .... R. -- .... ...... -- -- .... .... .... -- 0>< ...... 3 3 ...... ...... :... 3 ...-.0... ...... 3 3 ...... ...... .... 3 ...-3... ...... 3 3 ...... ...... .... 3 ...-.... ...: -- -- .... .... -- -- .... ...... -- -- .... .... -- -- c>< ...... 3 3 ...... .... 3 3 ...-...m ...... 3 3 ...... :... 3 3 ...-.... ...... 3 3 ...... .... 3 3 ...... . A l ,. ,. . a 3.1.5.. :3. . .3.‘ 3. 3. ; 3._.3.3.;_.3....._..m. ......s .....o a... _ ...... mw.w. .M .1 x... . am.aa. 2.086% .03”. 03......” 992 ._ 33 Sam .0....30. 00.5 05 ..o .8332. Eats... 0350.. 05 .0303... Q9. .29.... 0.8.30. 005 .0 03.83. 05 .8835 O>< 3...... EH03 b3 80.5.0. 5 cougaooco. .0308... v0. a... -- -- 3.. ...: -- -- ... 3... -- -- ...... .... -- -- o>< ...... 3 3 ...... 3 3 3 3...... ...... 3 3 ...... 3 3 3 3.3... ...... 3 3 ...... 2.... 3 3 2...... mm. -- -- .... 8.. ...... -- A... 8.... -- -- on... ...E .... -- 03.. .8... 3 3 8.... ...... ...... 3 2-..... 3...... 3 3 ...... 32.... :... 3 2-3... 8...... 3 3 8.... .8... .8... 3 3-..... ...... -- .. .3. ...N. -- -- a... :.: -- -- 8... .... -- -- .>1 8.... 3 3 ...... ...... 3 3 3-3:". ...... 3 3 ...... .... 3 3 ...-35. .3... 3 3 ...... .... 3 3 ...-..2. NZ -- -- A... 8.. -- -- o>< .... 3 3 ...... .3. 3 3 ...-38 ...... 3 3 ...... 3. 3. . ; A 3. .... ,.:33....&. .88. w .,w _ H _ ,. .Nfl ... ...—.aa... , . 200 .... -- -- no... .... ...... 8.. a... ...... -- - 3.... .... ...... .... o>< ...... 3 3 ...... .8... ...... .... ...-.....o 3.... 3 3 .3... ...... ...... ...... ...-3.... 3.... 3 3 8.... 3.... ...... .5... ...-.....o 8.. -- -- .... .... -- .... .... 9.... -- -- ...... .... -- 8.. .>1 8.... 3 3 3.... .3. 3 ...... ...-...... 2..... 3 3 ...... .3. 3 8... ...-...... ...... 3 3 ...... .... 3 ...... ...-3... .0.. -- - .... 8.. 3... o... .... ...... -- -- .... ...: .... ...... c>< ...... 3 3 8.... ...... .8... .3... ...-....o ...... 3 3 ...... :..... ...... ......- ...-.....o .3... 3 3 .3... 2..... E... ...... ...-....o .... -- .... ...... - 05. .5... 3 ...-...... ...... 3 ...-...... ...... 3 ...-...... 3. 3. ... “33...... 3.... ....o, , _ , , .aa... 201 on; .. -- em.m m...- Z..m -- Qmm ...-mwm -- 360 wm.we awde. -- O>< mmmfiwm 3 wide N192. 12.19 3 SF? 195N155 chads-N B mwmfic wm.w-No. Rub-N: 3 31m?” $8155 R163 3 hem-1o aw.w: ham-we to 353m 335m Smdwm B wmhdc 52.3 101.2. 3 3\1N\N 382mm omodwm B 3010 2.0-mo. own-1: B bah-SN 355m .wa-mum 3 51.5 1%.. 2 Bo. 3 ERR 355m uflwa .wa. . a, g. E ., _.. I34...— g... . ‘ H. . 3.x 3. 3. 3. _ 3. _ 3. . 33...... .aa... , 33H. UmO ”:2 3H 23 NH, .. j ,. 202 Anmndix L Table L-l. Chemical Comwitions of the Treatment Water Compound or Concentration Microcosms Microcosms Element from Galloway et Acidic Conditions ‘Natural’ Conditions al., (1976) (uM) (uM) (uM) H+ (as pH) 3.84 3.86 ** 5.61 ** Na+ 1.2 1.2 135.8 K+ * 0.26 23.3 23.3 Ca+ 6.5 6.5 6.5 Mg2+ 1.5 1.5 1.5 NH4+ 29.4 29.4 29.4 C1' 19.2 19.2 19.2 Br“ * 0.0 142.7 142.7 NO3’ 45.2 45.2 45.2 8042' 58.4 58.4 58.4 * KBr was added to the exchange solution to serve as a tracer. ** These pHs are the average of all pH values for the actual exchange solutions. 203 no.0 5&0 05.0 0&0 55.0 5&0 1&0 m0 05.0 $0 00.0 15.0 05.0 05.0 $0 0.5 35:00 a: 5.5 09w N05 mm.w Sum aa.m Ed 0N.w 0m.w wm.w 5.5 0 fix 3.5 mfiw 50 1~.w 3.280 NNO &0 1&0 3.0 0&0 wm.0 3.0 3.0 5 0&0 8.5 00.0 0&0 00.0 3.0 wm5 05.5 35:00 09. 05.0 05.0 00.0 55.0 3.0 m0.0 00.0 1&0 m&0 5 05.0 5.0 0&0 8.5 00.5 5.5 65:00 08 0.0 0.0 51.0 1&0 1&0 00.0 5.0 0&0 m&0 00.5 00.0 3.0 3.0 8.5 01.5 m05 3950 mNZ 3.0 0.5 005 10.5 -- 8.5 85 m5 005 01.5 0 #5 0&5 01.5 15.5 0&5 0&5 35.80 mg 00.0 3.0 15.0 00.5 0&0 3.0 8.5 3.0 10.0 10.5 1&0 wm.0 5&0 85 N05 _&5 Eo< a: w15 G05 w&5 8.x wmw 00.5 5&5 1.5 10.5 00.5 15 05.5 w05 O55 :.w mm.w Eo< 550 50.0 55.0 50.0 35 S5 M: .5 S .5 N5 0N5 5“ .5 :5 wm5 :5 3.5 15.5 5.5 291. 09. 01.0 10.0 1&0 5.0 m0 1&0 m5.0 5.5 m&0 :5 &0 5&0 1&0 85 N15 0~5 Eo< 0mm :.0 0.0 05.0 00.0 w0.0 w0.0 00.0 15.0 5&0 3.0 5.0 3.0 0&0 3.0 3.5 8.5 Eo< 0N2 5.0 00.0 .80 005 -- 55.0 85 :5 50.5 555 Q5 8.5 35 :5 N15 0N5 261. mg . «En—am #5" 110 N: «w 05 50 N0 00 w1 #1 1m 5N 3 1“ 5 o a man— .08388 Ho: 33 35 83883 a 83205 TV 8:30 03.5 3.5 58096:; 2 it: 204 _.550 0.000 000 &00N ch 0.N5N 0.0wN w.N_0 80 0.000 500 0N0 09: 500 05 5.NOH 75:00 5:. 1H5 N15 NH 0.0N 0N.w~ 004N 05.0N 01.1N 0.0N 5.0N 0N.N1 0_ .00 05N 050 5.50 0N.0~ 65:00 NNO 11.01 N&51 0.50 N000 1&N0 H00 0550 0550 0“ .N0 0000 00.N1 0N.01 0.N1 0.01 0.01 5.NN 35:00 0N0 $5: N55N~ 1N.oo~ 0.00 5.00 H00 01 00.50 0.50 05 00.05 0.02 0.5: 5.N0~ N.0ON 05.00 35.80 0N5 0N.00 01.10 0.N0 8.01 N001 01 05.00 051 0N.51 00.00 05.N5 05.03 0050 0.00 0.No~ 00.01 35:00 0N2 55.10 N151 N&o1 05.00 0040 00.00 00.0N 00 05.10 H00 H50 0N.00 :0 5.00 1.05 00.0N 35:00 NNM #5451 0N.105 1.510 1.550 0.01 511 550 500 500 0N0 505 005 05N~ 500“ 500 5ON Eu< 5: 5" .5 0&5 015 00.0 51.: 0&5 15 05.0 N15 0.: 0.5 N.0H 09.0“ 1.00 ~._N 00.2 20.1. NNO 0 H11 5050 0N.10 N5.5N N5.0N 0150 00.~N 0N.HN 0N.0N 0.0N 1.50 0.00 00.10 051 0.51 540 Eo< 0N0 5.05 0.53 11.05 0N.00 5.05 00.50 _.O0 0000 0150 050 N03 05.92 00400 1.050 ~.00N 0N5w Eo< 0N5 0051 N51 N011 N141 05.01 5N1 01.N0 05N o1 00 0555 fiww 1.03 5.5 150 05.~N Eo< 0N2 1N5N NN.0N 00.3 00.10 5N.0~ 5.00 N0 00.1 00 .: 00.Nfi NAN 0.0N 0o.00 0N.N1 N11 00 01.2 30.1. NNM 2me ~5~ 1: N3 N0 05 50 N0 00 01 #1 10 5N “N 1~ 5 o 3 man— 205 1 0:.: N0.NN 000.: 155.00 050.N~ 050.: 02.2 1N0.5H N005“ 1505~ 0.0N 11.00 10.5N 00.00 -- 35:00 5: -- 101.1 N01 100.0 000.0 _0.1 00.0 NON.1 55.0 00.5 100.5 005.: 00.51 05.2 -- -- 35:00 NNO -- N00.0~ 010.00 NON.0~ :.0 000.5 11N5 N00.00 010.N~ 05.: 0N.0N 5.00 5.00 10.00 10.000 -- 35:00 0N0 -- 50.5 105.0 005.1 0N5.0 NNN.0 050.0 00.5 015.0 000.5 005.:10N.0~ 05.00 10N5~ 00.0N -- 35:00 0N5 -- N500 0N1.0 10.N 51.N N10.N N500 N100 110.0 001.0 05.5 105.5 100.2 50.: N00.1H .. 35:00 0N2 -- 005.5 000.0 000.0 N051 N100 N500 00.0 105.0 5N.5 01.0 00N.0~101.N~ 000.: 5.5N -- 35:00 NNM -- 10.0N 05.00 150.10.150.00 50.50 105.50 00.NN 5.0N 0.00 00.00 00.50 00.5 N0.N0 N100 -- 031.5: -- 00N.1 000.0 11N.1 00N.0 N000 03.1 110.0 000.5 NN0.0~ 005.0 0N 3.50 000.: N05.0~ -- 03< NNO -- 0.1 000.0 55.N N05.N 10.0 NN5.0 00N.1 000.0 000.1 005.0 00N.0 N010 001.: 050.00 -- 03< 0N0 -- 00.1 050.0 N01 000.0 00.0 001.0 3.0 000.0 000.00 1N.: N00.N~ 005.00 1N0.0_ 00050 -- 03.4. 0N5 -- 00.N N50.N 155.N 00A NNOA 000.N 000.0 N50 N00 005 001.0 000.00 N00.: 015.00 -- 03¢. 0N2 I 1N1.1 N1N.1 N500 100.N 110.N 010.N 10~.N N_0.N 55.1 0.0 000.0 5N5 00.5 N5N.0 -- 03¢. NNM flan—am 050 110 N2 N0 05 50 N0 00 01 01 10 5N 0N 1H 5 0 a man— .08302: 3: 83 505 5808805 0 85835 TV 8030 03.5 206 50.05 01.01 05.01 00.01 05.N1 N001 N.N0 N001 N000 0H .00 05.50 01 35:00 NNM 05.50 15.51 5 0.00 10.5N 00.0N 15.5N 05.1N 00.1N 01.5N 51.5N 5A0 NO0N 35:00 0N0 55.51 :.01 01.01 0N.00 15.5N 0.00 N000 15.0N 10.N1 01.02 5.05 55.0 35:00 0NZ 55.05 00.05 01.005 #0000 N51: 00.505 0505 15.00 10.55 50.00 00.515 _0.05 35:00 0N5 N1A01 10.01N 1.00N N.00N 05.55N 0.050 05.050 50.000 05.00 N0.N00 01.000 50.0: 35:00 5: 05.N5 50.00 05.01 00.01 50.01 05.50 N500 00.00 5000 5N 00.00 00.00 35:00 NNO 0N 05.05 00.05 00.N1 5N.1_ 01.05 50.5 00.0_ 1N.NH 05.3 ZN.0H N50 5002 NNM ZN.N0 N500 50.00 50.00 55.N0 H45 000 0N.10 N040 51.00 05.51 05.0N muwz 0NH 05.50 50.00 5.0 0 00.00 10.00 0N.00 15.00 00.00 00.00 00.N1 50.01 10.1N mfiZ 0NZ 5.NN_ 5N.005 05.0: 00.5NH 00.5: 0.02 05.505 05 .1: 55 .05 0.0: 5.N0_ 50.005 5002 0N5 050 50.000 1.000 0N.000 N5.001 05.0N1 00.0N1 0N.001 00.500 05.000 5000 N000 mfiZ 5:. 05.1 50.0 NN.5 50.0 05.5 50.0 NZ 50.1 15.0 00.0 15.0 01.5N LQZ NNO 50.00 N5.55 N5.55 00.505 01.00 50.50 00.00 0N.005 00.15 0N.N0 50.N0 05.01 Z NNM 10.05 05.10 00.00 50.N0 50.10 5NAO 5N.10 51.00 10 50.00 N0.50 00.50 Z 0N0 05.0N 11.005 05.505 05.555 15.505 N0.00H 50.005 01.005 N041“ 05.0: 00.55 55.50 Z 0NZ 15.00_ 5501" 50.005 N5.55 00.505 5N4 ZN 50.005 0512 N055 55.00N 55.1ZN N005 Z 0N5 00.550 00.00N 55.5NN N5.00N 0N.15N 50.010 00.05N 05.50 1N.000 01.000 50.500 55.055 Z 5:. 0.0 50.1 00.1 00.1 N50 05.0 50.1 5.1 N00 5N5 5N5 05 Z NNO 29:00 505 55 10 50 00 01 00 5N NN 15 5 a a man 207 I I 055.0 N001 010 .0 010 .0 100 .0 55.5 105.0 00N.5 005.00 055.5 -- 10.N0 35:00 NNv0 100.5 N05.5 000.5 5N5.0 N000 005.00 00 0.0 00N.5 N0.5 105.00 -- 00.01 35:00 0N0 00N.5 000 .5 15N.5 000.0 00.0 0N0. 00 050.0 150 .0 005.00 N5N.00 -- 0N.0 35:00 0NZ 0N.0 0 050.0 N50 001.0 000.10 05500 101.00 0.N0 01.00 000.00 -- 00.0N 35:00 0N0 N5.000 00.11 00.00 01.00 0.N0 0.05 N505 N0 .N0 0 0.0N0 5.55 -- 1.55 35:00 500. 55.50 N1N0 00N.0 N050 N10.5 N00.00 NON.5 110.5 150.00 10.00 -- 5.N0 35:00 NNO N000 051.0 100.0 0N0.0 500.0 50.0 000.1 100.1 100.5 10N.5 00.1 00.0 n00Z NNv0 101.0 005.0 10 0 .1 05.1 050.1 000.0 0N5.0 15N.0 101.0 000.0 000.0 000 A002 0N0. 000.00 000 .5 0 0N.0 N500 5N.00 150.00 010.0 000.00 000.5 051.50 000 .50 151.50 n00Z 0NZ 00510 105.00 0N. 00 100.00 5N0.NN 50.0N N500 000 .00 000.00 105.0N 05.5N -- A0002 0N5 01.01 N5. 0N 0050N 00.1N 150.N0 05. 0 0 N0.0N 00.10 N100 0.01 N011 300 A002 500 050.0 105.N 000.N 050.1 50N0 N00 00N.0 110.0 105.00 N00.00 N50.5 N100 A000Z NNO N0000 N00.N0 05.10 050.10 050.0N 005.5N 0.0N 00 .0N 0.5N 10.5N 0.51 0.0N0 Z NNM 00.5 111.0 NN50 005.0 00.1 50.0 0N0.0 N550 N000 100.00 00.N0 15.10 Z 0N0 0.0N 10N.00 55.00 000.00 0N.00 105.N0 00.00 050.00 001.50 N5.0N 05.01 00.55 Z 0NZ 055.0 00.0 055.5 000.5 05.2 000.N0 N050 NON.00 N05.N0 15000 10.0N 000.00 Z 0N0 100.1N 000.00 015.00 10N.N0 1000 00N.00 000.00 010.00 N0.0N 10.0N 00.0N 015.10 Z 5:. 50.1 05N.0 005.N 001.1 NN0.0 10N0 000.0 100.1 0 000.00 000.00 00.NN Z NNO Ema—am 500 05 10 50 00 01 00 5N NN 10 5 0 3 man— 208 I I 01.0 05.0 00.0 05.0 05.0 00.0 00.0 00.0 0 0 .0 NN.0 1N0 00 .0 35:00 NNv0 000 11.0 00.0 00.0 00.0 000 00.0 10.0 0N.0 000 N00 000 35:00 0N0 50.0 00.0 00.0 N00 500 N50 0N.0 00.0 05.0 1N0 15.0 00.N 35:00 0NZ 100 00.0 0N.0 00.0 000 000 50.0 0N.0 1N0 00.0 05 05 35:00 0N0 0N.0 05.0 000 05 50.0 10.0 00.0 0N.0 5N0 000 00.0 50.0 35:00 500. 00.0 0N.0 0N.0 00.N 50.0 00.0 50.0 00.0 01.0 00.0 000 N10 35:00 NNO 00.N N00 5500 01.00 10.00 05.10 0000 05.00 05.N0 50.00 05.00 0100 A002 NNv0 NN.0 05 00.N 00.N 00.0 50.0 05.0 00.0 05.N N50 110 00.0 n00Z 0N0 00.N 01.0 50.0 0 00.0 0 00.5 50.5 NN.0 0 10.5 10.5 00.0 0 00.00 0010 A002 0NZ 10.0 05 N50 00.0 N00 010 00.0 50.0 50.0 00.0 11.0 -- A000Z 0N0 10.0 -- 50.0 05 N00 00.0 00.0 00.0 10.0 01.0 00.0 50.00 n0~0Z 500 01.0 01.0 01.5 00.0 01.0 50.1 50.1 05.0 0 51.0 0 0.N0 0N.0 0 01.N0 A0002 NNO 00.0 10.0 15.0N N0.1N 00.NN 00.0N 1N.N0 00.50 01.00 10.5N 05.0N 01.0N Z NNv0 000 00.0N 05.00 00.00 00.00 00.0N 10.00 00.00 01.NN N0.0N 00.5 50.0 Z 0N0 50.0 01.0 N0.5N 00.0N 00.00 50.0N 10.NN 50.0N 10.00 00.00 15.00 10.50 Z 0NZ N0.N 0N.0 15.0N N5.5N 05.5N 00.0N 00.00 00.0N 00.0N 00.1N 00.1N 00 .N0 Z 0N5 11.0 00.5 N001 50.50 05.01 05.00 00.01 10.50 05.00 51.00 00.N0 10.05 Z 500 N0.N NN.0 00.10 05.10 50.00 05.00 05.00 00.N0 00.10 00.N0 01.00 50.00 Z NNO «En—am 500 05 10 50 00 01 00 5N NN 10 5 0 x .009 209 I I . 50.N 00.0 05.0 05.0 10.0 05.0 55.N 00.N 50.N 0N.N 00.N 51.N 35:00 NNv0 00.0 00.0 00.0 0N.N 0N.N 00.N 50.N 50.N 00.N 01.N 00.N 00.0 35:00 0N0. 00.0 05.N 0N1 50.1 00.1 0N.0 N0 .0 05.0 10.0 15.0 00 .1 000 35:00 0NZ 00.N No.0 N50 100 N00 0N.N 00.N 00.N 0N.N N00 000 50.0 35:00 0N5 50.0 50.0 10.N 00.N 01.N 00.N 01.N 5N0 05.0 00.1 50.0 00.10 35:00 500 50.50 00 .5 55.5 00.5 50.0 N0 .5 0N.0 50.5 15.5 000 00.5 00.0N 35:00 NNO 00.00 0100 N01 50.1 15.1 N00 000 00.1 00.1 00.1 00.1 0N.0 n00Z NNv0 001 50.0 N00 N00 00.0 N00 15.0 05.0 05.1 01.1 00.0 50.1 A0002 0N0 00.00 N00 0 00.1 00.1 55.0 00.1 05.0 N10 01.0 50 .1 05.0 00.1 A0002 0NZ 0N.0 00.1 50.N 50.N 10.0 00.0 05.0 01.0 01.0 00.0 0N.0 -- mQZ 0Nn0 05.0 -- N0.N 05.0 00 .N 50.N 01.N 55.N 0N1 05.0 05.00 05.5N A000Z 5: 00.51 00.50 01.00 5N.00 50.N0 50.N0 0000 05.00 05.00 00.N0 00.10 50.50 5002 NNO 00.51 01.N0 000 00 .5 55.1 10.0 0 0.0 11.1 01.1 15.0 10 .0 00.N Z NNv0 00.01 00.50 55.00 05.5 05.00 5N0 0 05.0 0 51.00 5N.00 00.5 N00 55.N Z 0N0 00.N N0.N0 0N.00 00.0 05.5 15.5 No.5 15.0 00.1 00.0 01.N 5N.0 Z 0NZ NN.N00 0N.00 0N.5 N0.5 0N.5 05.0 5N0 50.0 000 N51 00.N 50 .N Z 0N.0 N100 N10N 10.0 000 N00 01.0 000 N0 .5 00.5 05.N0 50.10 00.00 Z 500. 51.0NN 05.00 05.00 00.00 00.00 05.00 00.00 0N.51 05.00 50.0N 00.00 05.0N Z NNO 295mm 500 05 10 50 00 01 00 5N NN 10 5 0 x 00D 210