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2009 The geochemistry of shallow groundwater and produced fluids associated with coalbed methane (CBM) exploration in Alberta, Canada

Cheung, Katrina

Cheung, K. (2009). The geochemistry of shallow groundwater and produced fluids associated with coalbed methane (CBM) exploration in Alberta, Canada (Unpublished master's thesis). University of Calgary, Calgary, AB. doi:10.11575/PRISM/17926 http://hdl.handle.net/1880/47626 master thesis

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The Geochemistry of Shallow Groundwater and Produced Fluids Associated with

Coalbed Methane (CBM) Exploration in Alberta, Canada

by

Katrina Cheung

A THESIS

SUBMITTED TO THE FACULTY OF GRADUATE STUDIES

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE

DEGREE OF MASTER OF SCIENCE

DEPARTMENT OF GEOSCIENCE

CALGARY, ALBERTA

SEPTEMBER, 2009

© Katrina Cheung 2009 The author of this thesis has granted the University of Calgary a non-exclusive license to reproduce and distribute copies of this thesis to users of the University of Calgary Archives.

Copyright remains with the author.

Theses and dissertations available in the University of Calgary Institutional Repository are solely for the purpose of private study and research. They may not be copied or reproduced, except as permitted by copyright laws, without written authority of the copyright owner. Any commercial use or re-publication is strictly prohibited.

The original Partial Copyright License attesting to these terms and signed by the author of this thesis may be found in the original print version of the thesis, held by the University of Calgary Archives.

Please contact the University of Calgary Archives for further information: E-mail: [email protected] Telephone: (403) 220-7271 Website: http://archives.ucalgary.ca ABSTRACT

The production of coalbed methane (CBM) represents a vital new source of natural gas supply in Western Canada. There are, however, concerns over potential negative environmental impacts on shallow groundwater resources in the hypothetical case that leakage of fluids or gases from CBM operations occurs. In order to address these concerns, it is important to create a baseline study to characterize groundwater, produced fluids and coal and to determine the source of gas in shallow groundwater. The major ion and isotope geochemistry for produced fluids from two major coal deposits in Western Canada (the Mannville Formation and the Horseshoe Canyon/Belly River Group) was compared to that of shallow groundwater in this region. A detailed analysis of the trace element and rare earth element (REE) concentrations provided additional insights on the depositional environment, redox conditions, and water-rock interactions affecting the produced fluids and SGW of the study area.

The isotopic composition of methane and ethane as well as δ18O values of water and total dissolved solids of the fluids were sufficiently distinct in shallow groundwater and the produced fluids from the Horseshoe Canyon/Belly River

Group and the Mannville Formation that they may serve as tracers for potential contamination of shallow groundwater with produced fluids or gases. Rare earth elements in shallow groundwater and Horseshoe Canyon/Belly River Group produced fluids were similar, suggesting that rare earth elements are not a suitable parameter to monitor potential contamination of shallow groundwater with CBM fluids from the Horseshoe Canyon/Belly River Group.

iii ACKNOWLEDGEMENTS

First and foremost, I would like to thank Dr. Bernhard Mayer for allowing me to work on this project under his supervision and for answering all of my questions!

I would also like to extend a huge thank you to Dr. Fariborz Goodarzi for encouraging me to continue with my education and for also giving me the opportunity to work on this project.

This project would not have been possible without the help of Don Jones and his crew at Alberta Environment. Thank you so much for all of your help with sampling and for all of your wonderful insight on this topic. A huge thank you to

Michael Nightingale, Maurice Shevalier, and all of the friendly people in the Isotope

Science Laboratory at the University of Calgary for helping me analyze my samples quickly and efficiently. Also, an extended thank you to Michael for having answered my millions of questions about anything and everything as I would wheel into his office! Thanks to Trevor Hirsche for being great company whenever I needed to go out into the field. To all of the students in the Applied Geochemistry

Group: thanks for the wonderful chats and coffee breaks!

I would also like to thank those that I have had the opportunity to work and collaborate with at the Geological Survey - Dr. Hamed Sanei for keeping me on track and for being a great friend, and Julito Reyes for being an entertaining office mate, friend, and mentor. Thank you to Dr. Lavern Stasiuk and Dr. Judith Potter for introducing me to the wonderful world of organic petrology.

And lastly to my family, thanks for all of your support and for putting up with me during this whirlwind adventure!

iv TABLE OF CONTENTS

ABSTRACT...... iii ACKNOWLEDGEMENTS ...... iv TABLE OF CONTENTS ...... v LIST OF TABLES...... ix LIST OF FIGURES...... xii

CHAPTER ONE: INTRODUCTION ...... 1 1.1 Background Information ...... 2 1.2 Objectives and Thesis Organization ...... 11

CHAPTER TWO: STUDY AREA ...... 14 2.1 Regional Climate and Groundwater Recharge...... 15 2.2 Geological Framework ...... 16 2.2.1 Tectonic Setting...... 16 2.2.2 Manville Formation ...... 19 2.2.3 Belly River Group ...... 19 2.2.4 Horseshoe Canyon Formation...... 21 2.2.5 Scollard Formation ...... 22 2.2.6 Quaternary Sediments...... 22 2.2.7 Hydrogeology ...... 23 2.2.7.1 Mannville Aquifer ...... 23 2.2.7.2 Brazeau-Belly River Aquifer...... 25 2.2.7.3 Horseshoe Canyon Aquifer...... 25 2.2.7.4 Scollard-Paskapoo Aquifer ...... 26 2.3 Gas Production...... 26 2.3.1 Mannville Formation ...... 26 2.3.2 Horseshoe Canyon Formation and Belly River Group...... 27 2.3.3 Scollard Formation ...... 29

CHAPTER 3: METHODS...... 30 3.1 Sampling Locations...... 30 3.2 Produced Fluids and Shallow Groundwater...... 30

v 3.2.1 Field Methodology ...... 30 3.2.2 Laboratory Methodology...... 32 3.2.2.1 Alkalinity and Electrical Conductivity...... 32 3.2.2.2 Major Ion Chemistry...... 32 3.2.2.3 Trace Element Analysis ...... 33 3.2.2.4 Arsenic and Chromium Speciation...... 33 3.2.2.5 Benzene, Toluene, Ethylbenzene, Xylenes (BTEX) ...... 34 3.2.2.6 Phenols...... 35 3.2.2.7 Volatile Organic Acids (as Acetic)...... 35 3.2.2.8 Polycyclic Aromatic Hydrocarbons (PAH)...... 36 3.2.2.9 Isotopic Analyses...... 37 3.2.2.9.1 Oxygen and Hydrogen...... 37 3.2.2.9.2 Carbon...... 38 3.2.2.9.3 Sulfur...... 38 3.2.2.9.4 Dissolved Gas ...... 39 3.2.2.9.5 Free Gas ...... 39 3.2.2.10 Gas Composition ...... 39 3.2.2.10.1 Dissolved Gas ...... 39 3.2.2.10.2 Free Gas ...... 39 3.3 Coal...... 40 3.3.1 Laboratory Preparation...... 40 3.3.2 Trace Element Analysis...... 40 3.3.3 Sulfur Isotope Analysis ...... 41 3.4 Geochemical Modeling...... 41 3.5 Quality Control and Natural Variability Test...... 41

CHAPTER 4: GEOCHEMISTRY AND S ISOTOPIC COMPOSITION OF COAL 43 4.1 Introduction...... 43 4.2 Background Information ...... 43 4.2.1 Coalification...... 43 4.2.2 Microlithotypes...... 49 4.2.2.1 Maceral Groups ...... 49

vi 4.2.3 Gas Generation ...... 53 4.2.3.1 Bacterial Methane...... 53 4.2.3.2 Thermogenic Methane...... 54 4.2.3.3 Gas Sorption...... 55 4.2.3.4 Gas Composition ...... 56 4.3 Results and Discussion ...... 57 4.3.1 Depositional Environment and Maceral Composition ...... 57 4.3.1.1 Mannville Formation ...... 58 4.3.1.2 Belly River Group...... 59 4.3.1.3 Horseshoe Canyon Formation...... 59 4.3.1.4 Scollard Formation...... 60 4.3.2 Trace Elements in Coal ...... 61 4.3.3 Rare Earth Elements in Coal ...... 67 4.3.4 Sulfur Isotopes in Coal ...... 70 4.4 Summary ...... 73

CHAPTER 5: MAJOR ION AND ISOTOPE GEOCHEMISTRY OF PRODUCED FLUIDS AND SHALLOW GROUNDWATER ...... 75 5.1 Introduction...... 75 5.2 Results...... 75 5.2.1 Chemical Composition of Fluids ...... 75 5.2.2 Oxygen and Hydrogen Isotopes ...... 87 5.2.3 Isotopic Composition of Dissolved Inorganic Carbon ...... 87 5.2.4 Isotopic Composition of Sulfate ...... 87 5.2.5 Concentration and Isotopic Composition of Dissolved and Free Gas ...... 91 5.3 Discussion ...... 96 5.3.1 Isotopic composition of the water samples ...... 96 5.3.2 Water types ...... 99 5.3.3 Redox State...... 104 5.3.4 Bacterial Sulfate Reduction ...... 107 5.3.5 Isotopic Signature of Coalbed Gas ...... 109

vii 5.4 Summary ...... 119

CHAPTER 6: TRACE ELEMENT AND RARE EARTH ELEMENT GEOCHEMISTRY...... 122 6.1 Introduction...... 122 6.2 Results and Discussion ...... 122 6.2.1 Geochemistry and Depositional Environment...... 122 6.2.2 Trace Elements ...... 129 6.2.3 Water-Rock Interaction using REEs as a Tracer ...... 135 6.3 Summary ...... 139

CHAPTER 7: CONCLUSIONS AND FUTURE WORK...... 142

REFERENCES...... 146

APPENDIX: A...... 163

APPENDIX: B...... 173

viii LIST OF TABLES

Table 4.1a: Concentrations of selected trace elements in coal from the Scollard Formation...... 63

Table 4.1b: Concentrations of selected trace elements in coal from the Horseshoe Canyon Formation...... 63

Table 4.1c: Concentrations of selected trace elements coal from the Mannville Formation...... 64

Table 4.2: Rare earth element concentrations (ppm) for coals from the Mannville Formation and the HSCN/BRG and from Shallow Groundwater...... 68

Table 4.3a: Content and isotope ratios of total sulfur in coal from the Scollard Formation...... 72

Table 4.3b: Content and isotope ratios of total sulfur in coal from the HSCN Formation...... 72

Table 4.3c: Content and isotope ratios of total sulfur in coal from the Mannville Formation...... 73

Table 5.1a: Chemical parameters for shallow groundwater in Alberta, Canada ...... 78

Table 5.1a (continued): Chemical parameters for shallow groundwater in Alberta, Canada ...... 79

Table 5.1b: Chemical parameters for HSCN/BRG produced fluids in Alberta, Canada ...... 80

Table 5.1b (continued): Chemical parameters for HSCN/BRG produced fluids in Alberta, Canada ...... 81

Table 5.1c: Chemical parameters for Mannville produced fluids in Alberta, Canada.... 82

ix Table 5.1c (continued): Chemical parameters for Mannville produced fluids in Alberta, Canada ...... 83

Table 5.2a: Saturation indices for siderite, calcite, goethite, and hematite in shallow groundwater samples...... 84

Table 5.2b: Saturation indices for siderite, calcite, goethite, and hematite in HSCN/BRG produced fluid samples...... 85

Table 5.2c: Saturation indices for siderite, calcite, goethite, and hematite in Mannville produced fluid samples...... 86

Table 5.3a: Oxygen, hydrogen, dissolved inorganic carbon, and sulfate isotopic compositions for SGW...... 88

Table 5.3b: Oxygen, hydrogen, dissolved inorganic carbon, and sulfate isotopic compositions for HSCN/BRG produced fluids...... 89

Table 5.3c: Oxygen, hydrogen, dissolved inorganic carbon, and sulfate isotopic compositions for Mannville produced fluids...... 90

Table 5.4a: Concentration and isotopic composition of free gas in SGW. The isotopic composition of methane was only recorded for samples that contained >1 vol. % of methane...... 93

Table 5.4b: Concentration and isotopic composition of dissolved gas in HSCN/BRG produced fluids. The isotopic composition of methane was only recorded for samples that contained >1 vol. % of methane...... 94

Table 5.4c: Concentration and isotopic composition of dissolved gas in Mannville produced fluids. The isotopic composition of methane was only recorded for samples that contained >1 vol. % of methane...... 95

Table 6.1: Ranges and average values of selected chemical and isotopic parameters for produced fluids and SGW...... 125

x Table 6.2a: Concentrations of selected trace elements in Mannville Formation fluids. Samples in bold are above the Maximum Allowable Concentrations (MAC) and samples in bold and underlined are above the Aesthetic Objective (AO) for drinking water guidelines (Health Canada, 2008)...... 131

Table 6.2b: Concentrations of selected trace elements in Horseshoe Canyon/Belly River Group swabbing fluids. Samples in bold are above the Maximum Allowable Concentrations (MAC) and samples in bold and underlined are above the Aesthetic Objective (AO) for drinking water guidelines (Health Canada, 2008)...... 132

Table 6.2c: Concentrations of selected trace elements in SGW. Samples in bold are above the Maximum Allowable Concentrations (MAC) and samples in bold and underlined are above the Aesthetic Objective (AO) for drinking water guidelines (Health Canada, 2008)...... 133

Table 6.3: Rare earth element concentrations for produced fluids from the Mannville Formation and the HSCN/BRG and from Shallow Groundwater...... 136

Table A.1: Full trace element analysis for SGW samples...... 163

Table A.2: Full trace element analysis for HSCN/BRG produced fluid samples...... 166

Table A.3: Full trace element analysis for Mannville produced fluid samples...... 170

Table B.1: Full trace element analysis for coal samples. IMS denotes analysis by inductively coupled mass spectrometer by ACME Laboratories, and NAA denotes analysis by neutron activation...... 173

xi LIST OF FIGURES

Figure 2.1: Map of Alberta showing the location of produced fluids and SGW sampling sites with respect to the major coal bearing units...... 14

Figure 2.2: Basin scale stratigraphy and hydrostratigraphy of the Alberta Basin from the Cretaceous to the Tertiary (after Bachu, 1999)...... 17

Figure 2.3: Distribution of coal by rank in Alberta (Beaton et al., 2006)...... 18

Figure 2.4: Stratigraphy of the Lower Cretaceous strata in the Western Canada Sedimentary Basin (after McLean, 1977; Christopher, 1984; Hayes et al., 1994; Wadsworth et al., 2002)...... 20

Figure 2.5: Stratigraphy of the Upper Cretaceous strata in the Western Canada Sedimentary Basin (after Bachu and Michael, 2003)...... 21

Figure 2.6: Flow systems and patterns in the Alberta Basin (Modified from Bachu, 1999)...... 24

Figure 4.1: Coal maturation, rank and other associated parameters. Modified from Taylor et al. (1998) and Bustin (2001). Vit Ro % refers to the vitrinite reflectance of the vitrinite macerals and DAF % refers to the amount of dry and ash-free coal...... 45

Figure 4.2: Van Krevelen (H/C vs. O/C) diagram showing the evolution of coal from diagenesis to metagenesis. This diagram shows the compositional evolution for two different coal types. The upper curve represents a sapropelic coal, which is rich in liptinites, such as alginate or sporinite. The lower curve represents a humic coal which is vitrinite rich (modified from Tissot and Welte, 1984; Levine, 1993; Taylor et al., 1998)...... 48

Figure 4.3: A basic classification scheme used after the 1994 International Committee for Coal and Organic Petrology for bituminous coals: 1Huminite Classification, after Sýkoravá et al., 2005; 2Vitrinite Classification, after ICCP 1998; 3Inertinite Classification, after ICCP 2001...... 50

xii Figure 4.4: Trace elements in coal normalized to the Earth’s crust (Mason and Moore, 1982) for coal from the (a) Mannville; (b) HSCN; (c) Scollard Formations. Values recorded above the red line show enrichment and values below the red line show depletion of the element compared to the Earth’s crust...... 66

Figure 4.5: Rare earth elements in coal normalized to the Post Archean Australian Shale (PAAS) (Taylor and McLennan, 1985) for coal from the (a) Mannville; (b) HSCN; (c) Scollard Formations. Values recorded above the red line show enrichment and values below the red line show depletion of the element compared to PAAS...... 69

18 2 Figure 5.1: Plot of δ OH2O vs. δ HH2O for produced fluids from the Mannville Group and HSCN/BRG and for shallow groundwater in Alberta, Canada and its relation to the Local Meteoric Water Line (LMWL) (Peng et al., 2004)...... 97

18 Figure 5.2: Plot of δ OH2O vs. TDS (mg/L) for produced fluids from the Mannville Group and HSCN/BRG and for shallow groundwater in Alberta, Canada..... 99

Figure 5.3: Schoeller diagrams illustrating the composition of a) SGW where samples shown as dashed red lines exhibit a similar chemical composition to HSCN/BRG waters; b) produced fluids from the HSCN/BRG; c) produced fluids from the Mannville Group...... 100

+ - Figure 5.4: a) A plot of Na and HCO3 showing a positive linear correlation in SGW and produced fluids from the HSCN/BRG. No correlation is visible in the Mannville produced fluids; b) A plot of Na+ and Cl- showing no correlation in SGW and a positive linear correlation in produced fluids from the HSCN/BRG and the Mannville. Inset figures include Mannville produced fluids, where the main figures focus on the SGW and HSCN/BRG produced fluids. The locations of the latter samples are enclosed by the red boxes in the inset figures...... 101

34 18 Figure 5.5: δ Ssulfate vs δ Osulfate for SGW...... 102

Figure 5.6: A boxplot showing the various concentrations of a) NO3, Mn, Fe, and SO4 in mg/L, and b) CH4 in vol % available in free gas in SGW and dissolved gas in produced fluids from the HSCN/BRG and the Mannville. The maximum sulfate concentration recorded for SGW (1010 mg/L) has not been included in this figure...... 106

xiii Figure 6.1: Piper plot showing the relative distribution of major ions (in meq/L) in Mannville and HSCN/BRG produced fluids and SGW in Alberta...... 124

34 2- Figure 6.2: δ Ssulfate values versus SO4 concentrations (mg/L) for HSCN/BRG 34 2­ produced fluids and SGW; elevated δ Ssulfate values and low SO4 concentrations indicate the occurrence of BSR...... 126

Figure 6.4: Crossplot showing pH versus the total dissolved rare earth elements (ΣREEs; μg/L) in Mannville and HSCN/BRG produced fluids and SGW. Compared to Mannville fluids, HSCN/BRG and SGW water samples are depleted in REEs while having higher pH values...... 137

Figure 6.5: ΣREEs (μg/L) vs. Eu* plot for Mannville and HSCN/BRG produced fluids and SGW. The Mannville produced fluids have a more positive Eu anomaly relative to the HSCN/BRG and SGW...... 138

xiv 1

CHAPTER ONE: INTRODUCTION

The production of coalbed methane (CBM) from shallow coals is a relatively new industry in Alberta (Canada) and represents a vital new source of natural gas supply in North America (Beaton et al., 2002; Beaton, 2003; Beaton et al., 2006).

The exploration of unconventional gas has increased rapidly since 2000 due to the expected decline of conventional gas reserves in Alberta (Langenberg et al., 2006).

By the end of 2006 a total of 10,723 CBM wells had been drilled and of these wells,

6,905 have been producing (Energy Resource Conservation Board (ERCB), 2007).

According to the Alberta Geological Survey (2005), there may be up to 14 trillion cubic meters (TCM) of CBM in Alberta, but it is unclear how much gas can be recovered economically (Alberta Geological Survey, 2005; Beaton et al., 2006).

There are significant environmental concerns related to potential negative impacts of CBM production on shallow groundwater (SGW) resources, as typified by CBM-producing areas in the United States, such as the Powder River Basin.

These include the disposal of saline produced waters (Clark et al., 2001; McBeth et al., 2003; Patz et al., 2004; Ganjegunte et al., 2005), leakage of produced gases into shallow aquifers as a result of improper cementing of the drill casing

(Beckstrom and Boyer, 1993) or fracturing, and potential drawdown of groundwater in shallow aquifers (Chafin et al., 1996).

Currently, the impact of the emerging CBM industry on SGW in Alberta is unknown because few studies have investigated the baseline chemical composition of SGW (Fitzgerald et al., 2001) and of coal-bearing aquifers (Lemay,

2003; Lemay and Konhauser, 2006; Klassen, 2007) in the province. In addition, 2 some of the shallow groundwater in Alberta is known to be naturally gas- containing. The source of this gas in shallow groundwater, however, is unclear.

The Energy Resource Conservation Board (ERCB) passed a directive in May

2006, which mandated for the testing of SGW wells in Alberta that are within a 600­ to 800-m radius of where companies want to drill new or complete or recomplete

CBM wells (ERCB, 2006). A detailed baseline geochemical analysis of produced fluids and SGW is an essential first step to facilitate the assessment of potential impacts, or the lack thereof, of CBM operations on shallow groundwater and to determine the source of gas in shallow groundwater.

1.1 Background Information

Coalbed methane (CBM) refers to an unconventional natural gas found in coal seams (Creedy and Tilley, 2003; Miyazaki, 2005). The natural gas is relatively clean burning fuel that forms in coalbed aquifers due to biological and/or geological processes that occur over millions of years (Creedy and Tilley, 2003; Patz et al.,

2006). The need for new alternative sources of energy has led to the exploration and exploitation of natural gases such as CBM.

In the 18th century, new technology was created to allow miners to drill into coalbeds to extract the coal. During this process methane was released into the atmosphere and was perceived as a hazard, due to its explosive nature (Camp et al., 1992). One example is the methane explosion in Nova Scotia in 1992, which killed a total of twenty six miners (Rightmire, 1984; Bachu and Michael, 2003).

Coalbed methane exploration began in the 1960’s in the United States (Camp et al., 1992). The U.S. Bureau of Mines investigated why methane was being 3 released by the coal seams and began improving the ventilation in underground mines by developing methods to extract the methane (Camp et al., 1992). By the

1970’s, pilot projects were implemented to extract the natural gas from coal. The first large scale coalbed degasification project was led by the U.S. Steel Corp. and the United States Bureau of Mines (USBM) at the Oak Grove Mine in Alabama. It was not until 1981 that the extracted methane was captured and sold to a natural gas pipeline company.

Over the past 20 years the CBM industry has grown significantly in the world

(McBeth et al., 2003; Beaton et al., 2006). Not only has CBM exploration been useful as an alternative energy source, but it has also helped to decrease the risk of methane being released uncontrolled into the atmosphere (Creedy and Tilley,

2003). The majority of the worlds CBM resources are found in Asia, North America and Europe (Landis and Weaver, 1993; Murray, 1996). Coal resources are generally found in sedimentary basins and provinces. There are at least 3000 coal basins or deposits throughout the world (Landis and Weaver, 1993; Murray, 1996).

Coal seams constitute good sources and reservoir rocks for CBM, as they are rich in organic matter and contain cleats and fractures, which can retain the gas (Levine

1993; Rice 1993; Faraj et al., 1996). According to Rightmire (1984) the amount of gas held in coal is a function of depth, the rank of coal, and the hydrogeologic environment of the area. At present, coalbed methane exploration is being carried out by a number of countries including the United States, Australia, Canada, and most recently China.

In order to retrieve CBM from coalbeds, the beds must be dewatered. This process lowers the reservoir pressure allowing the gas to desorb from the coal 4 matrix and move more freely through the seam (Lemay, 2003; Hinaman, 2005;

Orem et al., 2007). The gas flows towards the wellbore where it is captured at the surface. Dewatering CBM wells produces significant amounts of water to be disposed of and induces drawdown of the water table within the coal (Lemay,

2003). Fluid from CBM wells is typically called “produced water/fluids” or product water (Orem et al., 2007). Large quantities of produced fluids are put into holding ponds where the fluids can evaporate, storage structures, or discharged into nearby natural drainages (Orem et al., 2007). Only recently has industry commenced to re-inject produced fluids into deeper aquifers (Bachu and Michael,

2003; Pashin, 2007).

Recently, there have been environmental concerns regarding whether the production of CBM is negatively affecting the quality of shallow groundwater within the vicinity of CBM wells. This issue has been evident in CBM producing areas in the United States, such as in the Powder River Basin. The Powder River Basin in

Wyoming and Montana has been exploited for CBM for approximately 20 years and is at the forefront of CBM development in North America (Choate et al., 1984;

De Bruin et al., 2000; Reddy et al., 2001; Patz et al., 2006; Petzet, 2007).

According to Rice (1997), there is more than 19.8 trillion cubic meters (TCM) of coalbed methane gas in place in the United States, and of that over 2.8 TCM is economically recoverable. The Powder River Basin contains the largest reserves estimated at up to 790 billion m3 of economically recoverable CBM; 20 % of total

CBM production in the USA (DeBruin et al., 2000; Orem et al., 2007). Recently there have been a lot of negative environmental and societal implications regarding the production of CBM in the area. In 2006, water production from CBM 5 exploration averaged 1.8 million barrels/day for the first 10 months (Petzet, 2007).

The disposal of produced fluids has affected the quality of soils in the Powder River

Basin. High sodium absorption ratios (SAR) for some of these produced fluids have turned dry soil into a hardpan, which prevents water from infiltrating to crop roots (Petzet, 2007).

Alberta contains some of the most prolific coal and oil reserves in North

America. Coal seams have been studied and exploited for years for their mining potential and have recently been studied for their CBM potential. Alberta’s variable geology and vast coal fields have allowed for the exploration of CBM since the late

1980’s and have been studied extensively by Rottenfusser et al. (1991),

Langenberg et al. (2002), Beaton (2003), Chen et al. (2005), and Beaton et al.

(2006). In 2001, approximately 81 % of the gas produced in the Western Canada

Sedimentary Basin was from Alberta, 15 % from British Columbia, and 3 % from

Saskatchewan (National Energy Board, 2002). IHS Energy, a company that provides information and consulting services for oil and gas, reports that in 2003 natural gas production in Alberta increased by 3.4 % compared to the previous year (2002), and has exceeded 3 trillion cubic meters (TCM). The IHS Energy report (2005) also recorded that by the end of 2003 just under 30 % (approximately

82 TCM) of the discovered natural gas resources in the world had been produced.

The major coal-bearing formations in the prairies are the Scollard, Horseshoe

Canyon (HSCN), Belly River, and the Mannville Formation (youngest to oldest), where most of the drilling and CBM production is within a 300 km corridor between

Calgary and Edmonton (Squarek and Dawson, 2006). Even though 90 % of CBM comes from dry coals in Alberta (Squarek and Dawson, 2006) there are still 6 concerns regarding the effects of dewatering on aquifer sustainability and the effects that the produced fluids may have on various disposal receptors (Lemay,

2003). The water quality of produced fluids is a concern for irrigation, livestock watering and re-injection (Lemay, 2003). Because CBM is still fairly new in

Canada, the provincial government and other stakeholders are trying to better understand the effects of CBM production on groundwater in order to protect SGW resources in Alberta. The use of various techniques such as major ion geochemistry, stable isotopes, trace elements, and rare earth elements can help to characterize the SGW, produced fluids, and coal to better understand their potential interaction.

In order to fully characterize the water samples it is necessary to understand their major ion geochemistry. Groundwater is usually of meteoric origin and as the water infiltrates though the soil zone it reacts with organic and inorganic matter, which changes the water’s chemical composition. The major ions in groundwater strongly depend on the type of weathering reactions occurring in the water- unsaturated and saturated zones. Determining the water type gives insight into potential rock-water interactions that have occurred.

Stable isotope techniques constitute a powerful tool for identifying the sources of water and its dissolved constituents (Kendall and McDonnell, 1998;

Aggarwal et al., 2005) and the biogeochemical history of gases such as methane in groundwater systems (Rowe and Muehlenbachs, 1999a; Rowe and

Muehlenbachs, 1999b; Whiticar, 1999; Aravena et al., 2003; Niemann et al., 2005).

There have been few studies on the isotopic composition of coal-bearing aquifers

(Lemay, 2003; Aravena et al., 2003; Harrison et al., 2006a and b) and shallow 7 groundwater in Alberta (Peng et al., 2004). Hydrogen and oxygen isotopes have been analyzed in precipitation (Peng et al., 2004), surface water (Hendry, 1988;

Rock and Mayer, 2007), groundwater (Lemay, 2003), and produced fluids (Hitchon and Friedman, 1969; Harrison et al., 2006a and b) in Alberta. The isotopic compositions of hydrogen and oxygen were analyzed in produced fluids from CBM operations to help determine the origin of the fluids and whether there is any mixing occurring between formations (Hitchon and Friedman, 1969; Harrison et al.,

2006a and b). The analysis of sulfur isotopes can help determine the source of sulfate used in bacterial sulfate reduction and to identify pyrite oxidation (Cody et al., 1999; Balci et al., 2007). Whiticar (1999), Aravena et al. (2003), and Harrison et al. (2006a and b) used carbon isotopes in dissolved inorganic carbon, carbon and hydrogen isotopes in CH4, and other higher alkanes to distinguish between the various methanogenic pathways responsible for methane production. More recently, scientists have been studying the relationship between 2H in water and 2H in methane from coal-bearing aquifers (Aravena et al., 2003; Martini et al., 2003;

Harrison et al., 2006a). Variation of sulfur isotopes in pyrite and organic sulfur in coal may provide insight into the potential depositional environment of the coal and the availability of sulfate and iron (Spiker et al., 1994).

Trace elements can also be used to determine potential rock water interactions between coal and shallow groundwater. Most trace elements come from plants that formed the coal and from the surrounding environment and can therefore also give insight about the origins of the coal and on the conditions of coalification. Swaine and Goodarzi (1995) have extensively analyzed trace elements in coal. The authors have characterized the trace elements based on 8 their degree of environmental concern. Huggins et al. (1996), and Goodarzi and

Huggins (2001) have also analyzed the mode of occurrence of arsenic and chromium in subbituminous coals from the western U.S. and Canada. The authors investigated the different concentrations of each species (As3+,5+ and Cr3+,6+) to determine the potential human impact that arsenic and chromium may have. Trace elements and major elements vary in concentrations within a single coal seam

(Gluskoter et al., 1977; Rimer and Davis, 1986; Pollock et al., 2000), between different seams containing coal-bearing sequences (Harvey et al., 1983; Van der

Flier-Keller and Fyfe, 1985; Karner et al., 1986; Goodarzi and Van der Flier-Keller,

1989) and between coal basins (Glick and Davis, 1984; Harvey and Ruch, 1986;

Van der Flier-Keller and Fyfe, 1985). The depositional environment of coals as well as the type of organic matter deposited can greatly affect the trace elements found in coal as well as the concentrations in the associated produced fluids and shallow groundwater.

Trace elements have the potential to become mobilized in water. The concentrations of these elements and their oxidation state in water determines their toxicity (such as As3+,5+ and Cr3+,6+). When coal is in contact with shallow groundwater, it is possible for trace elements in the coal to become soluble and interact with the shallow groundwater, which if consumed, could impact human health. There have been only a few large-scale systematic studies investigating the trace metals of shallow groundwater (Fitzgerald et al., 2001) and coal-bearing aquifers (Lemay, 2003; Lemay and Konhauser, 2006).

Rare Earth Elements (REEs), otherwise known as the Lanthanide group have been used for decades as geochemical tracers. The group ranges from 9 lanthanum (atomic number 57) to lutetium (atomic number 71). REEs have similar physicochemical properties. Rare earth elements have been mainly used to study geochemical reactions in rocks (Henderson, 1984; Brookins, 1989), surface waters

(Worrall and Pearson, 2001a; Verplanck et al., 2001, 2004), and to study origins of groundwater (Lee et al., 2003; Olías, 2005) and coal forming processes (Palmer et al., 1990; Van der Flier-Keller and Goodarzi, 1992; Pollock et al., 2000).

The cosmic abundance of REEs, as a function of their atomic number or the inverse of their ionic radii, shows a distinct “sawtooth pattern”, which can be removed by normalizing to the REE’s abundances in chondrites or shales

(Boynton, 1984). Normalizing REE concentrations in water and coal samples to those in chondrites has been widely used and the resulting pattern of chondrite- normalized REEs may provide insight into the fractionation of elements during various geochemical processes and makes REEs useful natural tracers in the geosphere (Henderson, 1984; Taylor and McClennan, 1988; Birk and White, 1991;

Worrall and Pearson, 2001a and b; Lee et al., 2003). Normalized REE abundances in coals to those in shales have also been used as the mineral matter in coal should be similar to that in shale (Palmer et al., 1990; Birk and White,

1991).

Total rare earth elements (∑REE) include the sum of the elements ranging from La to Lu, which can then be split into light rare earth elements (LREE; from La to Eu) and heavy rare earth elements (HREE; from Gd to Lu). Rare earth elements react to form complexes quickly, have similar ionic radii and have a preferred valence state of M(III) (Brookins, 1989). Cerium (Ce) and europium (Eu) are the only elements within this group that have the ability to hold different valence states. 10

During oxidation, cerium changes to Ce(IV) and during reduction europium changes to Eu(II) (Lee et al., 2003; Olías, 2005). The variable oxidation state of these elements can be used to determine the past redox conditions, and hence the geochemical origin of various materials (Lee et al., 2003; Olías, 2005). Positive anomalies may also suggest that a secondary process, such as weathering, may have occurred (Lee et al., 2003).

Goldschmidt (1954) was one of the first to study REEs in coals and since then, few studies have been completed on this subject (Eskenazy, 1978; Palmer et al., 1990; Birk and White, 1991; Van der Flier-Keller and Goodarzi, 1992; Pollock et al., 2000). Based on studies by Fu et al. (2004), the REEs in coal may reveal information about the original plant type, as soil-grown plants can carry different

REE signatures compared to peat vegetation or algae. Rare earth elements are predominantly associated with inorganic matter with minor amounts associated with organic matter (Eskanazy, 1978; Goodarzi and Van der Flier-Keller, 1989;

Palmer et al., 1990; Birk and White, 1991; Van der Flier-Keller, 1993;

Mukhopadhyay et al., 1998; Pollock et all., 2000). According to Eskenazy (1978), the coal-forming process can cause REE differentiation. In coal, Eu, Tb, Sm, Ce anomalies, as well as LREE and HREE depletions suggest fractionation (Pollock et al., 2000). Palmer et al. (1986) suggested that there is a relationship between the rank of coal and the relative amounts of trace elements and REEs in vitrinite concentrates, as coals can have different adsorptive properties based on their rank and plant origin.

In natural aqueous solutions, REEs behave conservatively as they are relatively non-reactive during rock-water interactions (Lee et al., 2003). Analytical 11 developments in the past few decades have enabled the detection of REEs in aqueous solutions. Worrall and Pearson (2001a and b) have studied rare earth element fingerprinting in acidic groundwaters in Northwood, United Kingdom that are in contact with coal-bearing strata from the Durham basin. By studying the

REE’s in groundwater, Worrall and Pearson were able to understand the rock- water interactions and geochemical processes that have occurred as well as the evolution of the acid mine discharges. Therefore, REEs can be used as a tool to trace the movement of water in subsurface environments (Brookins, 1989).

1.2 Objectives and Thesis Organization

To address environmental concerns pertaining to the potential interaction between produced fluids and gases with shallow groundwater in a scientifically sound manner, it is essential that the geochemical and isotopic compositions of shallow groundwater and produced waters and gases in CBM producing regions of

Alberta are thoroughly known. The objective of this project is to create a baseline study to characterize shallow groundwater, produced fluids, and coal, and to determine potential sources of gas in shallow groundwater by using various techniques such as major ion geochemistry, stable isotopes, trace elements, and rare earth elements. This thesis is a collection of papers, which have been submitted for publication, that address the above goals. Study area and methods are described in detail in Chapters 2 and 3.

Chapter 4 discusses the depositional environment and maceral composition of coal. The depositional environment may influence the chemical composition of the coal, which may affect the chemical composition of produced fluids and shallow 12 groundwater in contact with these coals. Analysis of the rare earth elements in coal can also help to distinguish the extent of the interaction between coal and fluids within the aquifers. Lastly, the sulfur isotope composition of the coal may help determine whether bacterial sulfate reduction (BSR) in the formations is influenced by sulfate from coal or sulfate derived sources.

Chapter 5 has been submitted to Applied Geochemistry. The objective of this chapter is to present comprehensive baseline geochemical analyses of produced fluids and gases from two coal deposits and shallow groundwater to evaluate key geochemical differences that may be subsequently used to infer potential mixing. The chapter summarizes the major ion geochemistry and stable isotope compositions of the produced fluids and shallow groundwater to determine redox state, the occurrence of bacterial sulfate reduction, and the type of gas that occurs in dissolved or free gas form. The ultimate goal is to identify parameters that are suitable for identifying leakage of fluids or gases from CBM producing horizons into shallow groundwater.

Chapter 6 has been published in the International Journal of Coal Geology

(Cheung et al., 2009). The objective of this paper was to asses how the depositional environment, redox conditions, and water-rock interactions influence the trace element and rare earth element distributions in the produced fluids and shallow groundwater of the study area. This chapter also discusses whether rare earth elements can be used to indicate a potential contamination of shallow groundwater from CBM fluids.

In the two manuscripts submitted (Chapter 5) or published (Chapter 6) in peer-reviewed international journals, I was the lead author responsible for sample 13 analyses, data compilation and interpretations. The shallow groundwater and gas data collected was compared to produced fluid data collected by Patrick Klassen between October 2004 and May 2005. I was also responsible for writing and submitting the manuscripts. 14

CHAPTER TWO: STUDY AREA

This study was conducted in Central Alberta, Canada, focusing mainly on produced fluids and shallow groundwater between Calgary (51°6' N, 114°1' W,

1084.1 masl) and Edmonton (53°19' N, 113°34' W, 723.3 masl) (Figure 2.1).

Figure 2.1: Map of Alberta showing the location of produced fluids and SGW sampling sites with respect to the major coal bearing units. 15

2.1 Regional Climate and Groundwater Recharge

The climate in south-central Alberta is comprised of cold winters and warm summers (Environment Canada, 2008). Between 1971 and 2000, the average monthly temperature in Calgary ranged from -8.9oC in January to 16.2oC in July and in Edmonton the temperature ranged from -13.5oC in January to 15.9oC in July

(Environment Canada, 2008). Average annual precipitation is 413 mm in Calgary and 483 mm in Edmonton (Environment Canada, 2008). More than 70 % of annual precipitation occurs as rain predominantly between May and August, with less than 30 % of the precipitation falling as snow. Annual potential evapotranspiration in south-central Alberta is greater than 500 mm which generally exceeds precipitation in the area resulting in semi-arid climate conditions (Bothe and Abraham, 1993; Fennell and Bentley, 1998).

The topography of south-central Alberta ranges from low to moderate relief and is broad rolling prairie land in which numerous small depressions exist. In these zones depression-focussed groundwater recharge occurs after snowmelt and summer rainstorms (Fennell and Bentley, 1998; Hayashi et al., 1998; van der

Kamp et al., 2003). On average, however, groundwater recharge in the southern

Alberta Plains does not exceed 10 mm/year (Hayashi, personal communication

2009). The clay-rich sediments in the vicinity of these depressions can hold the snowmelt water after the snowmelt period, but evapotranspiration in the area can be so high that the depression can potentially dry up by late fall (Hayashi et al.,

1998). 16

2.2 Geological Framework

2.2.1 Tectonic Setting

The Western Canada Sedimentary Basin is a wedge composed of supracrustal rocks that overlie Precambrian crystalline bedrock that was assembled by 1.78 billion years (Price, 1994; Lemieux, 2000). At present, the majority of Alberta, and parts of British Columbia, Manitoba, Saskatchewan, and the Northwest Territories make up the Western Canada Sedimentary Basin

(National Energy Board, 2002). The basin formed due to episodes of subsidence and sediment accumulation beginning during the Late Proterozoic (Price, 1994).

The Late Proterozoic to Late Jurassic was a time of continental rifting that formed a passive margin, where the sediment source was from the northeast on the North

American Craton (Price, 1994). The foreland basin then formed during the Late

Jurassic to Early Eocene by the accretion of oceanic terranes that occurred following subduction. During this phase, subsidence of the foreland basin occurred due to the weight of the displaced supracrustal rocks and the main source of sediment was from the southwest and was due to the uplift of oceanic terranes and erosion (Price, 1994). Major subsidence of the foreland basin occurred between the Early Cretaceous and the Paleocene.

The Alberta Foreland Basin is dominated by marine shales. Within this succession there are six clastic wedges that thin to the east: Fernie-Kootenay,

Mannville, Dunvegan, Belly River, Edmonton, and Paskapoo (Cant and Stockmal,

1989; Harrison et al., 2006a; b). The Mannville, Belly River, Edmonton, and

Paskapoo clastic wedges are the major coal-bearing formations of interest for this study (Figure 2.2). The Upper Cretaceous coal zones that formed east of the

18

Figure 2.3: Distribution of coal by rank in Alberta (Beaton et al., 2006). 19

2.2.2 Manville Formation

The Lower Cretaceous clastic wedge of the Mannville Group strata contains the oldest Cretaceous rocks in the Western Canada Sedimentary Basin. The

Mannville strata were deposited during a time of significant basin subsidence and overlie a major unconformity. The Mannville Group can be divided into the Lower,

Middle, and Upper Mannville (Figure 2.4) (Ricketts, 1989). The Lower Mannville comprises non-marine shale and sandstone deposits. This unit varies in thickness throughout the Western Canada Sedimentary Basin (Ricketts, 1989). The deposition of the Lower Mannville was terminated by a marine transgression, which allowed for the deposition of marine shales and sandstones in the Middle

Mannville. This transgression pushed the shoreline south and the depositional environment progressed from fluvial to lacustrine marine (Wadsworth et al., 2002).

Clastic wedges interrupted the transgression in Southern Alberta, which is where coal developed above beach and coastal plain deposits (Ricketts, 1989; Beaton,

2003). The Upper Mannville is considered to be a prograding clastic wedge that consists of transgressive/regressive cycles, which resulted in basal shales overlain by deltaic sandstones (Ricketts, 1989; Beaton, 2003).

2.2.3 Belly River Group

The Belly River Group (BRG) consists of clay, silt, and sand and was deposited in a primarily non-marine environment. The deposition of the BRG occurred during the withdrawal of the Pakowki Sea in the Campanian (Bustin and

Smith, 1993). The BRG underlies the Bearpaw Formation and can be divided into two lithological units (Figure 2.5). The lower unit is the Foremost Formation, which

22 fed by river(s) into the shallow and warm epicontinental Bearpaw Sea. The coals in this formation were caused by the Bearpaw marine transgressions and regressions (Chen et al., 2005). Bentonite beds in the HSCN vary in thickness and can be up to 13.5 m thick (Lerbekmo, 2002). The HSCN sandstone overlies the bentonite beds and a marine sandstone is found below it (Lerbekmo, 2002).

2.2.5 Scollard Formation

The Scollard Formation is part of the Edmonton Group and is separated into the upper and lower members by the Cretaceous-Tertiary (K-T) boundary (Figure

2.5) (Sweet and Braman, 1992). This formation consists of non-marine thick sandstone and siltstone interbedded with mudstone, shale, and coal (Beaton,

2003; Harrison et al., 2006a; b), deposited in a fluvial setting. The upper members contain the Ardley Coal Zone, which is thicker towards the west because the coal zone is protected by the input of clastic sediments from river systems running parallel to the mountain front (Harrison et al., 2006a; b; Beaton, 2003).

2.2.6 Quaternary Sediments

Sediments deposited during the Quaternary are poorly consolidated and are of glacial, fluvial, lacustrine, aeolian and organic origin (Dawson et al., 1994). The majority of the sediment is till (glacial diamicton) and was deposited by the

Laurentide glaciers (Fenton et al., 1994). Sediment that was deposited during nonglacial intervals is mainly lacustrine and fluvial in origin and consists of clay and gravel (Fenton et al., 1994). The fine grained tills act as aquitards that confine coarser grained sediment that form aquifers. The Laurentide glaciers advanced 23 over the plains at least five times creating ice sheets that were up to 3km thick

(Peltier, 1994; Clark et al., 1996; Grasby and Chen 2005), which in turn led to the deposition of glacial and nonglacial units (Fenton et al., 1994). The units deposited are rich in igneous and metamorphic rock fragments, as well as carbonate fragments.

2.2.7 Hydrogeology

According to Bachu (1999), the flow systems in the Alberta Basin have developed due to: 1) erosional rebound and 2) topography-driven flow (Figure 2.6).

Aquifers of interest for this study are the Mannville, the Brazeau-Belly River, the

Horseshoe Canyon, and the Scollard-Paskapoo aquifers.

2.2.7.1 Mannville Aquifer

The Mannville aquifer covers most of central and southern Alberta. It overlies an unconformity, which may allow for communication with other aquifers at their erosional boundaries (Anfort et al., 2001). In southern Alberta, the entire

Mannville Group forms a single aquifer that is confined by the overlying Colorado

Group; in the north, the Mannville aquifer is confined to only the Lower Mannville.

The water flow within this aquifer is towards a low in hydraulic head to the north

(Figure 2.6) (Anfort et al., 2001). This hydraulic low is above a Devonian high, where the aquifer is relatively thin. This allows water to flow into the underlying

Grosmont aquifer. Water generally flows through permeable sandstones within the

Mannville Formation. Water in the southwest flows updip in a northeastward direction, whereas water in the southeast flows northwest (Figure 2.6) (Anfort et al.,

25

2.2.7.2 Brazeau-Belly River Aquifer

Based on studies by Michael et al. (2000), the flow in the Brazeau-Belly

River aquifer is topography driven. The formation water within this aquifer is characterized by relatively high TDS values in topographic highs and relatively low

TDS values in areas where the Brazeau crops out (Michael et al., 2000). The water flows updip along the Lea Park aquitard and mixes with fresh meteoric waters. The Brazeau-Belly River aquifer and the Scollard-Paskapoo aquifer are in direct contact with one another northeast of the deformation front due to the absence of the Battle Formation (Michael et al., 2000).

2.2.7.3 Horseshoe Canyon Aquifer

Flow in the HSCN aquifer is topography driven in the northern and southern areas of Alberta (Bachu and Michael, 2003). Recharge occurs in the southwest and in the north-northwest and discharge occurs at lower elevations along river valleys. Within the central region of the HSCN formation, the flow is driven inward due to erosional rebound of the underlying Bearpaw shale (Bachu and Michael,

2003). Here, the aquifer is unable to recharge, which suggests a low-permeability barrier between this area and the recharge areas in the southwest and north- northwest (Bachu and Michael, 2003). The interbedded shales and the bentonite beds in the HSCN formation act as aquitards and do not allow for recharge to occur in some areas in the HSCN aquifer (Hamblin, 2004). Therefore, the aquifer is considered to be comparably dry relative to the Scollard-Paskapoo aquifer. 26

2.2.7.4 Scollard-Paskapoo Aquifer

The Scollard-Paskapoo aquifer is found at the top of the Upper Cretaceous-

Tertiary succession (Fig. 2.2). It is a shallow aquifer system with topography driven flow. Recharge areas are at high elevations and discharge areas are to the east-northeast (Parks and Tóth, 1995; Bachu, 1999; Bachu and Michael, 2003;

Harrison et al., 2006a; b). The top of the Paskapoo aquifer is a target for freshwater supply and can yield from 6.5 m3/day to 325 m3/day (Harrison et al.,

2006a; b). Groundwater in the Scollard-Paskapoo aquifer is mainly fresh with total dissolved solids (TDS) concentrations of less than 2000 mg/L (Harrison et al.,

2006a; b).

2.3 Gas Production

The coalbed methane potential in the Alberta Plains and the Foothills has been researched extensively by Beaton et al. (2003 and 2006), Langenberg et al.

(2002) and Rottenfusser et al. (1991). Overall, the Mannville Formation appears to have the highest amount of gas-in-place.

2.3.1 Mannville Formation

Coals from the Mannville Formation fall within the oil, wet gas and condensate window based on their rank, suggesting that these coals have the ability to generate oil and wet gas (Mukhopadhyay and Rullkötter, 1994).

According to Zuber et al. (1996), the permeability of coal seams decreases with burial depth, which has been a major challenge in gas production. Coal seams deeper than 1500 m are considered to be not economical due to their low 27 permeability. Due to the lack of permeability in deeper Mannville coals, shallower coals (<1500 m depth) are currently being targeted for CBM through horizontal drilling (Squarek and Dawson, 2006). These coals are able to retain high gas contents and are thick.

The gas-in-place calculations for the Mannville Coal Zone shows that areas that have >4 m in net coal thickness may contain between 142 and 283 x 106 m3/1.6 km2 (1.6 km2 is the equivalent to 1 section), of gas (Beaton et al., 2006;

Gentzis et al., 2008). The Mannville Coal Zone encompasses a large area that extends from the Alberta-British Columbia border to east-central Alberta and from south of Grande Prairie to Twp.10, Rge.30, W4M. The Mannville Coal Zone contains large areas where the net coal is greater than 6m and has a high potential for CBM at 320 TCF, which is more than all of the coals in Canada (ERCB, 2006;

Beaton et al., 2006; Squarek and Dawson, 2006).

2.3.2 Horseshoe Canyon Formation and Belly River Group

In order to achieve economic production rates, operators usually commingle gas flow from multiple coal seams in the wellbore (Squarek and Dawson, 2006).

Therefore, when productive HSCN coals overlie the BR coals the BR coals are also exploited. In areas where the BR is not overlain by the HSCN, the BR coals are not drilled for CBM as these coal seams are thin and discontinuous (Squarek and Dawson, 2006). Factors that suggest that CBM production is favourable in the

HSCN include seam thickness, lateral continuity, coal rank and vitrinite content, brackish water content, permeability and the presence of fractures (Hamblin,

2004). Production over recent years has been on the HSCN and Belly River coals, 28 due to the abundance of thick laterally extensive coal seams. However, gas production per well in the HSCN/BRG is low (Squarek and Dawson, 2006).

Gas-in-place for the Carbon-Thompson Coal Zone is generally low at <28 x

106 m3/1.6 km2, as the coalbeds are thin (<2 m) with local pods that are 3-4 m thick. However, there are two areas in Alberta (one northwest of Calgary and the other west of Edmonton) that have elevated gas concentrations from 28 x 106 m3/1.6 km2 to 42 x 106 m3/1.6 km2 (Beaton et al., 2006). Due to the discontinuity and variable thickness of the Daly-Weaver Coal Zone, it is currently not a target for

CBM exploration. The Drumheller Coal Zone is undergoing CBM development and was the first coal zone in Alberta to be explored for natural gas. The Drumheller

Coal Zone is vast, spanning an area of approximately 1.28 x 105 km2, and contains thick and continuous coalbeds (Chen et al., 2005; Beaton et al., 2006). The rank of the coals in the Drumheller Coal Zone is sub-bituminous B and increases towards the west and north to high volatile bituminous B (Chen et al., 2005). This suggests that more biogenic gas is produced in the southeast (downdip) compared to the northwest where more oil and wet gas can be found (Mukhopadhyay and

Rullkötter, 1994). Gas-in-place calculations show that the minimum gas-in-place in this coal zone is 57 x 106 m3/1.6 km2 and in areas where the coal seam is thicker, the gas-in-place can exceed 85 x 106 m3/1.6 km2 (Beaton et al., 2006). The overall

CBM potential in the Drumheller Coal Zone is 38 trillion cubic feet (Beaton et al.,

2006). Gas-in-place concentrations for coal zones within the Belly River Group is approximately 14 x 106 m3/1.6 km2, but some areas have been recorded to have between 21 and 28 x 106 m3/1.6 km2 of gas-in-place (Beaton et al., 2006). 29

2.3.3 Scollard Formation

There currently is controversy regarding the production of CBM from the

Ardley Coal Zone due to the presence of fresh water resources within the main coal seams. The majority of the CBM production in the Ardley is found in the

Edson-Pine Creek area and the Pembina area (Beaton et al., 2006). In these two regions gas-in-place concentrations are generally greater than 113 X 106 m3/1.6 km2 and can be as high as 170-22 x 106 m3/1.6 km2 (Beaton et al., 2006). The net coal in these two areas is slightly greater than the surrounding areas. Ardley coals are well cleated with 2 cm spacing the face cleats and butt cleat spacing of 5 cm

(Beaton et al., 2002). Spacing between the cleats allows for natural gas to flow through the cleat system. In the west the spacing between the cleats has become infilled with minerals (mainly calcite), which decreases the ability for gas to flow through the coal seams (Beaton et al., 2002). The high inertinite content in this coal increases the porosity in the coal seam and allows for gas to be stored. The

Ardley coal zone is considered to have the highest potential for producing gas due to its high permeability, rank, petrological composition, and depth (Bachu and

Michael, 2003). 30

CHAPTER 3: METHODS

3.1 Sampling Locations

For this study, produced fluids from the Mannville Formation were collected from the Central Alberta Plains and swabbing fluids from the HSCN/BRG were collected from the Central and Southern Alberta Plains (Fig. 2.1). The SGW samples were collected from monitoring wells accessing shallow aquifers in the

Central and Southern Plains of Alberta (Fig. 2.1). The majority of the groundwater wells that were sampled are in contact with coal-bearing aquifers, such as the

Mannville, Brazeau-Belly River, HSCN, and Scollard-Paskapoo aquifers.

This study focuses on the geochemistry and isotopic composition of co­ mingled fluid samples collected from the HSCN/BRG and the Mannville Formation, as well as shallow groundwater. The methods chosen allow for the samples to be preserved in a manner to limit the reactions that may occur when the samples are exposed to atmospheric conditions, or reactions that may occur over a length of time while the samples are being stored.

3.2 Produced Fluids and Shallow Groundwater

3.2.1 Field Methodology

Forty-six co-mingled fluid samples from the Horseshoe Canyon and the

Belly River Group were obtained during well swabbing. Swabbing is a procedure where borehole water is removed to increase the flow of methane in the well bore.

Seventeen produced fluid samples from the Mannville Formation were collected at the well head and the remaining 7 were collected from holding tanks. Duplicate 31 samples were taken to determine the accuracy and reproducibility of the methods in this study. Samples were collected in clean 9-litre Nalgene® carboys.

The shallow groundwater (SGW) samples were collected from 42 wells with the assistance of Don Jones and his co-workers at Alberta Environment. Most of the wells were completed within the HSCN/BRG and/or the Scollard Formation and were collected using a bladder pump. The bladder pump ran until the water quality parameters were stable for at least 15 minutes before sampling. Two travel blanks and triplicate samples were submitted for analysis to determine the accuracy and reproducibility of the methods used in this study.

The obtained water and gas samples were preserved (where necessary), subdivided into different sample containers, and sent to various laboratories for determination of more than 95 chemical and isotopic parameters per water sample.

The analyzed parameters included major ions, metals, trace elements, isotopic ratios of water and dissolved constitutents, and chemical and isotopic compositions of dissolved gases. Free gas samples were also collected from SGW in an attempt to understand natural processes and potential anthropogenic influences impacting the quality of groundwater in Alberta. The pH and temperature were measured in the field using an Orion® model 290A. Unflitered samples were collected for alkalinity, electrical conductivity, dissolved gas, and sulfide concentrations. The water collected was then filtered using a 45 µm Millipore filter and filtration unit. An inert “nitrogen induced” gas supply was connected to the filtration chamber.

Filtered samples were then collected for the remaining analyses. 32

3.2.2 Laboratory Methodology

3.2.2.1 Alkalinity and Electrical Conductivity

Unfiltered water samples were collected in 125 mL flint glass bottles with zero head space. The bottles were sealed with a cone seal and cap. The alkalinity

- (expressed as HCO3 ) for the produced fluid samples was later analyzed at the

University of Calgary using an Orion® 960 Autotitrator. Electrical conductivity was also measured in house. The SGW samples were analyzed by Maxxam Analytics

Inc. for their alkalinity and electrical conductivity. The detection limit for alkalinity is

1 mg/L and 2µS/cm for electrical conductivity.

3.2.2.2 Major Ion Chemistry

A filtered sample from each produced fluid and groundwater well was collected in 250 mL Nalgene® bottles and acidified to a pH < 2 with Omni-Trace nitric acid from Fisher Scientific for cation analysis. Filtered and un-acidified produced fluid and groundwater samples were collected from each well to be analyzed for major anions. Analyses for the produced fluids were conducted in the

Applied Geochemistry Group, Department of Geoscience, at the University of

Calgary. Atomic Absorption spectrometry on a Perkin Elmer AAnalyst 100 spectrophotometer was used to determine cation concentrations. Anion concentrations were determined on a column suppression liquid chromatograph

(All-Tech). Anion concentrations for SGW were conducted by Maxxam Analytics

Inc. (Calgary). Methods used to determine anion concentrations in the groundwater samples included titration for bicarbonate, ion chromatography for nitrate, and automated colourimetry for chloride and sulfate. The detection limit for 33 bicarbonate, chloride and sulfate is 0.5 mg/L, and for nitrate 0.003 mg/L. The cation concentrations for SGW were derived from trace element analysis conducted by Becquerel Laboratories. The laboratory used an ICP-MS to determine elemental concentrations in the SGW. The detection limits were as follows: for manganese 0.05 ppb, for iron 10 ppb, and for calcium, potassium, sodium, and magnesium 50 ppb.

3.2.2.3 Trace Element Analysis

A filtered sample from each groundwater well was collected in a 125 mL

Nalgene® bottle and acidified to pH < 2 with Omni-Trace nitric acid from Fisher

Scientific for the analysis of 70 elements (eg. As, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb,

Sb, Se, V, and Zn). Trace element analysis for the produced fluids was conducted by Acme Laboratories (Vancouver). Trace elements in the SGW samples were conducted by Becquerel Laboratories (Ontario) using inductively coupled mass spectrometry (ICP-MS). The solution samples were diluted to below 0.1% of total dissolved solids before analysis. The detection limits ranged from 0.01 ppb for elements such as cesium, europium and rubidium to 0.5 ppb for elements such as arsenic and chromium. A complete list of trace element data is provided in

Appendix A.

3.2.2.4 Arsenic and Chromium Speciation

An unfiltered groundwater sample from each well was collected in a 250 mL plastic bottle and acidified with 5 mL of 20% nitric acid for analysis of the water’s arsenic speciation (As3+ and As5+). A filtered groundwater sample from each well 34 was also collected in three 40 mL amber vials for total chromium, hexavalent chromium (Cr6+) and trivalent chromium (Cr3+) determinations. The samples were sent to ALS Laboratories in Edmonton, Alberta, for analysis. The analysis for arsenic speciation was done by AAS – Hydride following the APHA 3114 C method. The detection limit for this analytical method is 0.05 µg/L. After all samples were analyzed for arsenic speciation, ALS Laboratories informed us that they had provided incorrect information regarding groundwater collection and preservation methods, therefore As speciation data from this analysis will not be recorded in this thesis. Hexavalent chromium was analyzed using ion chromatography, and total chromium was analyzed using ICP-OES. The detection limit for this analytical method is 0.001 mg/L. Trivalent chromium was determined by calculating the difference between total chromium and hexavalent chromium.

The detection limit for this method is 0.005 mg/L. The results for chromium speciation were compared to total chromium from the trace element analysis. The sum of chromium species was not similar to the concentration of total chromium, suggesting that there was analytical error. Due to poor chromium speciation results, this data will also not be discussed in this thesis.

3.2.2.5 Benzene, Toluene, Ethylbenzene, Xylenes (BTEX)

Benzene, toluene, ethylbenzene, and xylene concentrations were analyzed in produced fluids by AGAT Laboratories (Calgary) using a gas chromatograph coupled with a mass spectrometer (detection limit of 0.001 mg/L). The produced fluids were filtered and collected in 150 mL amber glass bottles with a teflon seal.

Unfiltered shallow groundwater samples were also collected in 40 mL amber vials 35 preloaded with 5 mL of 20 % nitric acid. The samples were sent to ALS

Laboratories in Calgary for analysis. Analytical methods followed the EPA

5030/805 and 8260 guidelines and analysis was conducted by GC-MS/FID. The detection limit for these analyses is 0.0005 mg/L. Due to the difference in collection method between the shallow groundwater and the produced fluids and due to the generally low concentrations of BTEX found within the shallow groundwater, this data will not be presented in this thesis.

3.2.2.6 Phenols

Groundwater from each well was collected in a 30 mL amber bottle for analysis of phenols. The samples were then acidified to pH < 2 using nitric acid.

The bottles were sent to ALS Laboratories (Calgary). The samples were analyzed using automated colourimetry following the EPA 9066 procedure. The detection limit for phenols is 0.002 mg/L. Phenols were not analyzed in the produced fluids.

One of the blanks analyzed in this study showed a phenol concentration of

0.004 mg/L, suggesting that very low phenol concentrations must be evaluated critically, and that a re-evaluation of the sampling and analytical procedures used in this study is required before further conclusions can be drawn. Therefore, phenol concentrations will not be further discussed in this thesis.

3.2.2.7 Volatile Organic Acids (as Acetic)

Unfiltered groundwater samples were collected in 500 mL amber bottles for analyses of volatile organic acids. The majority of the samples were sent to ALS

Laboratories in Thunder Bay, Ontario. The concentration of organic acids was 36 determined by distillation/titration following the APHA 5560 C guidelines. The detection limit is 7 mg/L. Towards the end of the project ALS Laboratories changed their service lab and samples were sent to Waterloo, Ontario. This lab analyzed the samples using the same technique, but the detection limit was lowered significantly to 0.3 mg/L. Produced fluids were not analyzed for organic acids.

There was considerable variation between the results of triplicate samples and the blank samples tested positive for VOA, indicating that the VOA method used in this study was not very reliable. Recent analysis of a different set of sampling equipment blanks by the Alberta Research Council (ARC) indicated that the sampling method likely did not bias the results, since field methods have not changed since this study. A re-evaluation of the analytical techniques used in this study is therefore required before further conclusions can be drawn.

3.2.2.8 Polycyclic Aromatic Hydrocarbons (PAH)

Unfiltered groundwater samples were collected in 500 mL amber bottles for analysis of polyaromatic hydrocarbons. The samples were sent to Bodycote –

Norwest Laboratories (Calgary). The laboratory followed methods recommended by the US EPA and analysis was conducted by gas chromatography/mass spectrometry. The detection limit for PAHs is 0.01 µg/L, with the exception of fluoranthene and pyrene. The detection limit for these PAHs is 0.02 µg/L. Most of the shallow groundwater samples had PAH concentrations below the detection limit and produced fluids were not analyzed for PAHs. According to Health Canada

(2008), benzo[a]pyrene is the only PAH that has a maximum allowable concentration (MAC) (0.01 μg/L). The guidelines for all other PAHs have been 37 archived, as Health Canada (2008) has proposed that these PAHs are not found in

Canadian drinking water supplies, and thus do not pose a threat to human health, or that they are covered by other categories in the Drinking Water Quality

Guidelines. For these reasons the PAH data for shallow groundwater will not be further discussed in this thesis.

3.2.2.9 Isotopic Analyses

Hydrogen, oxygen, carbon and sulfur isotope analyses were conducted using gas source isotope ratio mass spectrometry. Stable isotope values are reported on a delta (δ) scale in permil or parts per thousand (‰). The isotopic composition is defined as:

⎡ Rsample ⎤ δ (‰) = ⎢ −1⎥ ×1000 ⎣Rreference ⎦

In this equation, R is the ratio of heavy isotope to light isotope (generally for the two most abundant isotopes of an element). Positive and negative δ values indicate that the sample is either enriched or depleted in the heavier isotope with respect to the reference material.

3.2.2.9.1 Oxygen and Hydrogen

Samples for hydrogen and oxygen isotope ratio determinations were collected in 15 mL plastic vacu-tubes. The samples were analyzed in the Isotope

Science Laboratory at the University of Calgary using dual inlet isotope ratio mass 38 spectrometry. Oxygen isotopic measurements were conducted as outlined by

Epstein and Mayeda (1953) and hydrogen isotopic measurements were conducted as outlined by Donelly et al. (2001). Oxygen and hydrogen isotope ratios are

18 reported using the delta (δ) notation (e.g. δ Owater and δDwater) in per mil (‰)

18 relative to V-SMOW. Uncertainty for δDwater is better than ±2.0 ‰ and for δ Owater is ±0.2 ‰.

3.2.2.9.2 Carbon

Samples for carbon isotope analyses on dissolved inorganic carbon (DIC) were collected in 15 mL plastic vacu-tubes that had been preloaded with ammonical strontium chloride. The resulting strontium carbonate samples were analyzed for carbon isotope ratios in the Isotope Science Laboratory at the

University of Calgary using CO2 gas released by phosphoric acid treatment

13 followed by dual inlet isotope ratio mass spectrometry. δ CDIC values are recorded

13 in per mil (‰) relative to V-PDB. Uncertainty for δ CDIC is ±0.2 ‰.

3.2.2.9.3 Sulfur

Samples for sulfur isotope ratio determinations on dissolved sulfate were collected in 500 mL plastic Nalgene® bottles. Sulfate was converted to barium sulfate (BaSO4) and subsequently to SO2. The sulfur isotope ratios were determined in the Isotope Science Laboratory at the University of Calgary, using continuous flow isotope ratio mass spectrometry. δ34S values are reported in per mil (‰) relative to Vienna Canyon Diablo Troilite (V-CDT). Uncertainty for δ34S is

±0.5 ‰. 39

3.2.2.9.4 Dissolved Gas

Dissolved gas samples from produced fluids and SGW were collected and stored in 125 mL serum bottles with crimp tops. The samples were analyzed using a gas chromatography combustion system coupled in continuous flow mode to an isotope ratio mass spectrometer (GCC-IRMS). Gas was injected manually into the

GC once the gas had equilibrated with the generated head space within the glass containers. δ13C values are recorded in per mil (‰) relative to V-PDB. Accuracy

13 13 13 and precision for δ CCH4, δ CC2H6 and δ CCO2 is better than ±0.5 ‰.

3.2.2.9.5 Free Gas

Methane, ethane (where available) and CO2 in free gas from the SGW wells were collected using a gas-water separator and were transferred into canisters or

Tedlar bags in the field. The samples were analyzed for their isotopic composition

13 13 13 (δ CCH4, δ CC2H6 and δ CCO2) using GC-C-IRMS by the Isotope Science

Laboratory at the University of Calgary. δ13C values are recorded in per mil (‰)

13 13 13 relative to V-PDB. Accuracy and precision for δ CCH4, δ CC2H6 and δ CCO2 is better than ±0.5 ‰.

3.2.2.10 Gas Composition

3.2.2.10.1 Dissolved Gas

Dissolved gases from produced fluid samples were analyzed at the

University of Calgary for their gas composition using the equilibrium headspace technique and a gas chromatograph.

3.2.2.10.2 Free Gas 40

Methane, ethane (where available) and CO2 in free gas were collected using a flow through sampler and were transferred into canisters or Tedlar bags in the field. The Alberta Research Council Environmental Monitoring group (Vegreville) determined gas compositional data using gas chromatography. Gas compositional data are reported in vol % in the gas phase, meaning that they are a measure of the relative abundance of each gas relative to the total volume of gas in the sample, rather than the amount of each gas per litre of water pumped.

3.3 Coal

3.3.1 Laboratory Preparation

In order to prepare the coal to be analyzed for trace elements and sulfur isotope ratios, the coals were ground into a fine powder using a mortar and pestle.

3.3.2 Trace Element Analysis

Elemental analyses were conducted by inductively coupled mass spectrometer by ACME Laboratories. Samples were dried at 60 oC and pulverized prior to acid digestion. Approximately 0.25 g of each sample was weighed into teflon test tubes, where the samples were then mixed with a 10 mL aliquot of an acid solution (2:2:1:1 of H2O-HF-HClO4-HNO3). The test tubes were placed on a hot plate and heated until the samples were dry. A 4 mL aliquot of 50 % HCl was then added to the remaining residue and heated in a microwave. Once the solutions had cooled the samples were transferred into polypropylene test-tubes and analyzed for various elements. ACME Laboratories uses a Perkin Elmer Elan

6000 ICP mass spectrometer. Twenty-five of the elements were analyzed by 41 neutron activation conducted by Becquerel Laboratories (Ontario). For a complete list of elements analyzed by each technique see Appendix B.

3.3.3 Sulfur Isotope Analysis

Isotope analyses on total sulfur in coal were conducted at the University of

2- Calgary. Total sulfur in the coals was converted to SO4 by Parr bomb oxidation.

2- The obtained SO4 was quantitatively converted to BaSO4 by the addition of 0.5 M

BaCl2 solution. The BaSO4 was filtered, dried and subsequently converted to SO2 in an elemental analyzer coupled to an IRMS for sulfur isotope ratio measurements. The δ34S values for total sulfur are reported relative to CDT and have a reproducibility of ± 0.3‰.

3.4 Geochemical Modeling

Standard geochemical models in the modeling program Aquachem v5.1 were used to calculate saturation indices (SI) for a number of different minerals.

This reveals whether groundwater is under-saturated, in equilibrium, or over­ saturated with respect to selected minerals commonly found in the aquifer matrix.

3.5 Quality Control and Natural Variability Test

A quality control (QC) test was carried out on March 13, 2007, to determine the variability of the gas composition and isotope ratios along with the reproducibility of analytical procedures. The test was conducted at the Warner 215 well (KC21), since its groundwater contained free gas with high methane concentrations. According to the drilling reports the well was drilled through a coal 42 seam. The well is located southeast of Lethbridge and is 98 m deep, which suggests that it most likely interacts with the Belly River group. Thirteen dissolved gas and free gas samples were collected over a span of approximately three hours. One free gas and one dissolved gas sample were taken approximately every 15 minutes. Travel blanks were also collected throughout the sampling period to assure quality control. There was little fluctuation between the concentration and isotopic values of the methane and ethane in this aquifer over the 3 hour sampling period. The lack of variability also suggests that the analytical techniques are fairly accurate. 43

CHAPTER 4: GEOCHEMISTRY AND S ISOTOPIC COMPOSITION OF COAL

4.1 Introduction

This chapter describes the depositional environment and maceral composition of coals from the Mannville, HSCN/BRG, and Scollard formations.

Trace element and rare earth element analyses of the coal were conducted to determine whether the coal deposited in these formations have potentially influenced the chemical composition of produced fluids and SGW within the coal- bearing aquifers. In order to fully understand whether bacterial sulfate reduction

(BSR) occurs in these three formations it is important to determine the potential sources of sulfate that could influence BSR. Isotope analysis of sulfur in the coals has been used to determine whether or not coal is a major source of sulfate in these aquifers.

4.2 Background Information

4.2.1 Coalification

Coal is considered to be any deposit that is comprised of more than 50 % organic matter by weight or 70 % by volume (Bustin et al., 1985). It originates as animal and vegetal debris such as remnants of algae, micro-organisms and phyto- and zoo plankton, highly degraded remnants of higher plants, and less degraded remnants of higher plants that have fossilized. Coal is comprised of three main maceral groups: liptinite, vitrinite and inertinite. The basic principal behind coalification is that as coal rank increases, the organic material loses oxygen and hydrogen continuously (during maturation) until it has a carbon content greater 44 than 90 % (Flaig, 1968). The organic material accumulates and is then compacted, hardened, chemically altered, and altered by heat and pressure over millions of years and undergoes the three main stages of coal maturation: 1) diagenesis, 2) catagenesis, 3) metagenesis (Figure 4.1) (Taylor et al., 1998).

Peatification and dehydration of the material occurs during diagenesis, during catagenesis the hydrogen content of the material dereases, and lastly anthracitization occurs during metagenesis (Tissot and Welte, 1984; Taylor et al.,

1998).

The diagenetic stage refers to post-depositional modification of the material, where biochemical reactions and physical processes metabolize the hydrolysable and nitrogen-rich substances of a plant. The preservation of organic matter during diagenesis is dependant on climate, the development of flora, tectonic and paleogeographic factors, as well as environments of deposition (Taylor et al.,

1998). The two main processes during diagenesis are peatification and humification. Peatification occurs in a body of stagnant water where peat near the peat surface and to a depth of approximately 0.5 m undergoes oxidation and fermentation (Taylor et al., 1998). During this process, the volume of peat is reduced, its chemistry is modified, and the content of carbon increases rapidly with depth as the moisture content decreases. Lignin-rich and tannin-rich woods become more concentrated in the organic material during peatification, as they are more difficult to break down compared to the cellulose-rich material. As depth increases, the aerobic microbial activity decreases, and anaerobic activity increases, causing the fermentation of cellulose and lower fatty acids. Under high

46 temperature aerobic conditions, there is an increase in bacterial activity and humification occurs. Humification is the formation of humic substances from the lignin and cellulose of cell walls. This process is not depth dependent, but proceeds faster under oxic conditions, alkaline environments, and high peat temperatures, and hence is dependent on the conditions in which deposition occurs. Marine influenced or calcium-rich coals are usually deposited in neutral to alkaline environments, which allows bacteria to structurally decompose the peat.

The availability of oxygen is important in order for humic substances to form from lignin through oxidation. Products of humification include humic gels and carbon- rich lignin (Teichmüller, 1982). Non-humifiable constituents of peat are liptinite and intertinite macerals. Humifiable constituents are vitrinite macerals. Once the debris has undergone humification it is possible for it to then undergo gelification, where the cellulose is removed from woody tissues. The atomic ratios H/C and

O/C decrease during biochemical gelification and the aromaticity increases (Figure

4.2).

As peat converts to lignite there is a loss of water from the organic structure and the peat becomes hard and well compacted (Figure 4.1). This suggests that lignites are generally less porous and have a lower moisture content compared to peat. There is a decrease in oxygen content and volatile matter and an increase in carbon content in lignite (Figure 4.1 and 4.2). The aromacity of huminites and liptinites increases in the liptinites and there is selective preservation of plant polymers (Van Krevelen, 1961).

The catagenic and metagenic stages are mainly dominated by abiogenic chemical reactions such as depolymerisation, polymerization, and cracking (Van 47

Krevelen, 1961; Techmüller, 1982). During catagenesis, the coal rank increases as the temperature of the rock increases with depth, and purely thermochemical processes occur (Figure 4.1). The hydrogen, oxygen, and nitrogen contents in these coals decreases rapidly as the residual organic matter increases (Figure

4.2). Bituminization is a phase that occurs during this stage and is where the composition of the molecular phase of the coal is transformed from a water- dominated system to a bitumen-dominated system (Teichmüller, 1982; Taylor et al., 1998). Petroleum-like substances are generated from liptinites and perhydrous vitrinites in the coal (Taylor et al., 1998). This phase is evident on a microscopic level by the presence of secondary fluorescing macerals and fluorescing vitrinite, and the formation of micrinite (Techmüller, 1982). Overall, bituminization allows for the generation and entrapment of hydrocarbons, the depolymerization of the matrix and an increase in hydrogen bonding. Bituminous coals range from high-volatile C bituminous to low-volatile bituminous. As lignite converts to bituminous coals, vitrinitization occurs where huminite macerals are converted to vitrinite macerals.

Coal changes colour from brown to black during this process and becomes harder and brighter. Microscopically, the coal becomes denser. During vitrinitization there is a consistent loss of macroporosity and moisture content.

Thermal degradation/cracking and repolymerization of the molecular components of coal occur during debituminization. Debituminization is when all the properties that developed during bituminization are reversed. During this phase there is a decrease in the H/C atomic ratio as low molecular weight hydrocarbons, such as methane, are expelled (Figure 4.2). This process occurs between medium and low-volatile bituminous coals. Therefore the fluorescing properties disappear

49

Once debituminization has taken place, the last stage of coalification, metagenesis occurs. Metagenesis is mainly related to the molecular re­ arrangement of coals, which results in an increase in carbon and the loss of hydrogen contents. During this phase, aromatic carbon structures are able to coalesce and expand from two dimensionally ordered structures to three- dimensionally ordered structures. The vitrinite reflectance of an anthracite increases as well as the density, structural anisotropy and hardness (Figure 4.1).

Anthracites are known to have very high methane sorption capacities, because of the regular spacing between the carbon atoms (Goodarzi and Murchison, 1972).

By this stage, the carbon content in the coals is nearly 100 %.

During coalification, different types of coal will start out with different concentrations of elements, such as C, N, O, and H, but as the rank of these coals increases they gradually become increasingly homogeneous. Humic coals are generally relatively enriched in oxygen and depleted in hydrogen compared to sapropelic coals (Figure 4.2). The classification chart shows that the vitrinite reflectance, volatile matter, carbon content, moisture content, and zones of hydrocarbon generation and destruction are dependant on the rank of the coal/the maturation processes that the coal has undergone (Figure 4.1). Coal rank ranges from peat to anthracite where the higher the rank the more mature the coal is.

4.2.2 Microlithotypes

4.2.2.1 Maceral Groups

There are three main macerals that make up coal: liptinite, vitrinite, and inertinite. Each maceral is formed due to the preferential preservation of various

51

Liptinite macerals are hydrogen-rich plant remains such as resins, waxes, fats, and spores from aquatic and terrestrial vegetation. The liptinite macerals recorded in coal and shale samples include alginite, sporinite, cutinite, and resinite

(Taylor et al., 1998; Bustin et al., 1985).

Vitrinite macerals are the most abundant macerals in coals and are comprised of woody tissues, roots, stems, leaves and bark from trees that are composed of cellulose and lignin. Vitrinite in coals is due to the anaerobic preservation of lingo-cellulosic material in swamps, which occurs during peatification (Sýkoravá et al., 2005; ICCP, 1998; Bustin et al., 1985). Vitrinite can occur in coal as telovitrinite, detrivitrinite, and gelovitrinite. Telovitrinite has preserved cell structures which become less visible as the rank of the coal increases. Coal containing large amounts of telovitrinite suggest that the coal was preserved under low-pH conditions within forested peatlands or bogs (ICCP, 1998).

Inertinite macerals have a high carbon content and low oxygen and hydrogen contents. The carbon content of this maceral group can vary depending on the geochemical processes that the maceral may have undergone during deposition (ICCP, 2001). The inertinite macerals observed in the samples for this study consist of fusinite, semifusinite, macrinite, micrinite, and inertodetrinite.

During wild fires, fusinitization forms charcoal and allows for the decarboxylation of plant tissues (Taylor et al., 1998). The structure of portions of cell walls may be preserved as fusinite (Bustin et al., 1985; Taylor et al., 1998; ICCP, 2001). The structure of semifusinite is between that of vitrinite and fusinite. It forms during the peat formation stage due to dehydration, humification, redox processes, and wildfires. Macrinite occurs as an amorphous matrix and contains no cell structure. 52

This maceral forms from the humic matrix substances that have undergone dehydration and redox processes. Micrinite also contains no cell structure and consists of small grains of inertinite. It is considered to be a secondary maceral and forms during coalification and could potentially be used as a tracer for biogenic gas (Shibaoka, 1978). Inertodetrinite is fine fragments (less than 10 μm) of inertinite (ICCP, 2001). The degree of preservation of cell structures in inertinite macerals varies depending on the depositional history of the macerals. Teichmüller

(1973 and 1975) has stated that the presence of two coal consituents, micrinite and exudatinite could indicate petroleum generation, as the formation of these two macerals may coincide with the same stage of diagenesis in which petroleum is formed in source rocks. Micrinite is considered to be a porous secondary maceral, which has formed due to oxidation processes either during the peat-forming process (Theissen and Sprunk, 1936; Spackman and Barghoorn, 1966; Shibaoka,

1978 & 1983) or during later diagenesis (Teichmüller 1973 and 1975). This submaceral is common in inertinite rich coals and is most likely liptinitic or vitrinitic in origin. The occurrence of micrinite in coal may suggest that the coal has undergone the biogenic decomposition necessary to create biogenic methane.

Vitrinite reflectance can be used to measure the maturity of organic matter and to determine whether or not it has the ability to generate hydrocarbons. The reflectivity of single grains of vitrinite from coal is measured under a microscope and is given in units of reflectance, %Ro. The reflectance of vitrinite is analyzed rather than the reflectance of inertinite and liptinite, because vitrinite is the most common component in coal and is not prone to oil and gas formation. Vitrinite macerals become increasingly reflective as coal rank increases. The difference in 53 the reflectivity of liptinite, inertinite, and vitrinite decreases with rank, which can make it difficult to differentiate between the three maceral groups.

4.2.3 Gas Generation

During the maturation of coals, methane can be formed by the cracking of higher hydrocarbons. Gas generation within coal seams may occur via two mechanisms (Rice, 1993; Whiticar, 1999): (i) bacterial generation of methane

(methanogenesis) and (ii) thermogenic gas generation through thermal maturation of the coal. Gas is stored within coal zones as (1) free gas within the cleats, (2) absorbed into and adsorbed onto the surface of coal particles, micropores, and cleats, and (3) dissolved gas in the water within the coal seam (Bachu and

Michael, 2003; Yee et al., 1993). Petrological and geochemical methods can be used to determine the likely gas production processes within coal zones (Taylor et al., 1998). Hydrogen-rich liptinite and vitrinite macerals have the ability to generate liquid hydrocarbons, suggesting that coals with high concentrations of these components can be a source rock for oil and wet gas. Wet gas contains a significant portion of heavier hydrocarbons (ethane, propane, butane, etc) compared to dry gas (Rice, 1993; Mukhopadhyay and Hatcher, 1993).

4.2.3.1 Bacterial Methane

The formation of bacterial methane is related to the decomposition of organic matter by microorganisms and can occur through two different pathways: by the reduction of organic material (e.g. acetate) or by the reduction of carbon dioxide (Rice, 1993; Taylor et al., 1998). In order for biogenic gas to form the 54 following requirements must be met: rapid sedimentation, an anoxic environment, low sulfate concentrations, abundant organic matter, low temperatures, and adequate pore space (Rice and Claypool, 1981; Zhang and Chen, 1985; Rice,

1992; Rice, 1993). Early stage biogenic gas can be generated during early burial in low-rank coals (peat to subbituminous) (Rice, 1993). This gas is usually produced via CO2 reduction (Rice, 1993). Late-stage biogenic gas can also be generated in coals that have already undergone thermogenesis and is usually due to active groundwater systems providing nutrients for bacterial growth. During this stage, carbon dioxide produced by fermentation is reduced. Generation of late- stage methane can occur in coal of any rank provided that all of the requirements for gas production are met (Rice, 1993). Coals with vitrinite reflectance values between 0.15 and 0.4 % are considered to be suitable for biogenic methane formation, while coals with vitrinite reflectance values between 0.4 and 1.0 % are within the oil and wet gas window (Figure 4.1).

4.2.3.2 Thermogenic Methane

Thermogenic methane is generated at high pressures during coalification beginning at rock temperatures of approximately 80 oC. Methane generation becomes significant at a temperature of 110 oC (Taylor et al., 1998). During this stage of coalification, the coals become enriched in carbon and large amounts of volatile matter enriched in hydrogen and oxygen are released (Rice, 1993). The coal rank facilitating thermogenic methane generation is between sub-bituminous and bituminous coal, where most methane generation begins in medium-volatile bituminous coal and is highest in low-volatile bituminous coal and anthracite stages 55

(Rice, 1993; Taylor et al., 1998). Even though coals such as anthracite have the ability to generate large quantities of methane, these coals lack the porosity to retain the gas. The onset of thermogenic gas starts at in the oil and wet gas generating window at a vitrinite reflectance value of 0.6 % (Gentzies et al., 2008).

Coals with vitrinite reflectance values between 1.0 and 2.0 % are considered to be within the thermogenic gas generating window (Figure 4.1). Most coals with vitrinite reflectance above 2 % will have most likely lost the porosity necessary to store the gas.

4.2.3.3 Gas Sorption

Gas sorption in coals has been discussed in detail by Selden (1934),

Gunther (1965), Jolly et al. (1968), Vinokurova (1978), and Yee et al. (1993). Coal is microporous and has a large internal surface area in which gas has the ability to hold on in a condensed or liquid-like phase. The sorption capacity of coals is mainly a function of coal maturity, where the capacity increases with pressure and temperature until the saturation limit (relative to the coals sorption capacity) has been reached. The presence of mineral matter in coal can limit the coals sorption capacity as it does not contribute to gas sorption (Gunther, 1965; Yee et al., 1993).

Selden (1934) shows that the presence of moisture in the coals can reduce the gas sorption capacity as water can block some of the methane sorption sites in the coal. Studies have shown that as rank increases the sorption capacity of the coal increases as well (Selden, 1934; Yee et al., 1993). By analyzing the petrological characteristics of coal it is possible to determine the ability for coal to sorb gas.

Coals that are high in inertinite can sorb more methane than vitrinite-rich coals 56

(Crossdale et al., 1998). This is due to the porous nature of inertinite macerals.

The amount of gas-in-place in the coal seams in Alberta is related to the distribution of coal, with regards to depth, rank, quality, water saturation, and net coal thickness (Bachu and Michael, 2003; Beaton et al., 2006). The permeability of a coal is dependent on the cleat density, width, and orientation, which can also affect the ability to extract natural gas (Gentzis et al., 2008; Bachu and Michael,

2003). The development of cleats as well the density of the coal is dependent on the coal rank and type. The cleating of a coal can be the limiting factor in its ecomonic potential for CBM production.

4.2.3.4 Gas Composition

Coalbed gas consists of hydrocarbons (C1 to C4), where methane is the major component. Carbon dioxide, a small percentage of nitrogen, hydrogen, oxygen, and helium are also present (Rice, 1993; Clayton, 1998). The composition of coalbed gas consists of C1 to C4 hydrocarbons in variable quantities where C2+ can vary from 0 to 70 % (Rice, 1993; Clayton, 1998). The “dryness” of the gas

(C1/C2+) relates to the proportion of methane (CH4) and higher hydrocarbons and depends on the mechanism in which gas was generated, the elemental composition of macerals, the thermal maturity of the coal, and the ability for a higher alkane gases to be retained in the coal matrix (Clayton, 1998). Gas that contains a high percentage of methane compared to higher alkanes is considered to be “dry gas”. Thermogenic gas generally has a much lower gas dryness parameter compared to biogenic gas, suggesting that there is a higher concentration of higher hydrocarbon gases present in the coal (Rice, 1993). The 57 presence of significant amounts of higher hydrocarbons in biogenic gas suggests that late-stage biogenic gas was generated, where thermogenic generated hydrocarbons have already been produced (Rice, 1993).

4.3 Results and Discussion

The composition of coal in Alberta may be influencing the chemical composition of associated produced fluids and SGW in Alberta. It is important to understand the depositional environment and composition of the coal in order to better classify whether the coal may be potentially contaminating the fluids. Also, analyzing the S isotope composition in coal will help determine if the coal is a major source of sulfate for formation water or shallow groundwater or if the fluids may be in contact with other sulfate sources.

4.3.1 Depositional Environment and Maceral Composition

The maceral composition and vitrinite reflectance of coal can give insight on the potential for gas production and retention. For example, vitrinite-rich coals usually have a greater adsorption capacity compared to inertinite-rich coals, as vitrinite-rich coals have a greater surface area and are highly microporous compared to the latter (Crosdale et al., 1998). However, inertinite-rich coals have a greater total pore volume and generally exhibit high initial gas emission rates compared to vitrinite-rich coals (Crosdale et al., 1998). The presence of secondary macerals, such as micrinite and exsudatinite suggests that the gas produced is most likely biogenic. Vitrinite reflectance helps to determine the rank of coal. With increasing rank, the likelihood of coal to produce thermogenic gas increases. 58

4.3.1.1 Mannville Formation

The thickness of the coals in the Mannville Formation ranges from 2 - 12 m

(Beaton, 2003). These coals were deposited in an upper to lower deltaic environment. Coals in the central and northern Foothills of Alberta were deposited in a coastal plain and are thick and extensive, but become thinner as the depositional environment changes to fluvial (Beaton, 2003). The Mannville coals range in rank from subbituminous to semi-anthracite, but in the central Alberta

Plains they are of high volatile C/B to medium volatile bituminous rank. The vitrinite reflectance for coals of this rank ranges from 0.4 to 2.5 %. Gentzis et al.

(2008) analyzed Mannville coals within a similar area to where the produced fluids for this study were collected. The authors state that the vitrinite reflectance for these areas range from 0.51 to 0.71 %, suggesting that these coals are part of the oil and wet gas window and will produce thermogenic gas.

The dominant maceral in Mannville coals is vitrinite with an average of

79 %, followed by inertinite with an average of 7 % and liptinite with an average of

5 % (Goodarzi et al., 1994). The majority of the vitrinite in the coals fluoresce, which suggests that the macerals formed under anaerobic conditions (Teichmüller,

1982; Gentzis et al., 2008). Liptinite consists mainly of primary macerals such as sporinite, cutinite, resinite and secondary macerals i.e. exsudatinite and bituminite

(Goodarzi et al., 1994). Exsudatinite is a major component of liptinite, and is considered to be a petroleum-like substance that begins to form at the beginning of the bituminization process. This secondary maceral is found in the Mannville coals and suggests that these coals have potential for biogenic hydrocarbon generation.

The high concentration of vitrinite in the Mannville coals also suggests that these 59 coals have a large affinity to adsorb gas. The ability for the Mannville coals to desorb gas may be lower than coals that have greater inertinite content.

4.3.1.2 Belly River Group

Coals within the BRG range in thickness from 1 to 3 m. The coal rank ranges from subbituminous C to high volatile (Beaton, 2003). These coals have vitrinite reflectance values between 0.4 % and 1.0 % and fall within the oil and wet gas generation window as wells as the start of major thermogenic gas generation.

Few studies have been completed on the composition of coal from the Belly River.

Bustin and Smith (1993) report that Belly River coal is vitrinite rich (75 - 90 %) and contains minor amounts of inertinite (5 - 15 %) and liptinite (3 - 10 %) (Bustin and

Smith, 1993). Vitrinite-rich coals more effectively adsorb methane compared to inertinite-rich coals (Crossdale et al., 1998). However, inertinite macerals may increase the porosity of the coal, thus enhancing gas flow (Crossdale et al., 1998).

4.3.1.3 Horseshoe Canyon Formation

There are three main coal zones in the Horseshoe Canyon Formation; the

Carbon-Thompson Coal Zone, the Daly-Weaver Coal Zone, and the Drumheller

Coal Zone (Beaton, 2003). Coal seams in this formation are relatively discontinuous. The Drumheller coal zone is the majority with a thickness of more than 4 m and spans an area of approximately 1.28 x 105 km2 (Chen et al., 2005;

Beaton et al., 2006). These coals are commonly deposited in a deltaic setting

(Bustin et al., 1983; Beaton et al., 2006). Coals in the Daly-Weaver Zone are thinner as they were deposited in an alluvial plain setting. Coals from the Carbon­ 60

Thompson Coal Zone are also thin (<2 m) and discontinuous, but laterally persistent with local pods that are 3 to 4 m thick. These coal beds are related to a back-barrier depositional environment (Bustin et al., 1983). The rank of the coal increases from east to west from subbituminous to high volatile C bituminous with vitrinite reflectance ranging from approximately 0.5 to 0.65 % (Beaton, 2003). Gas generation falls within the oil and wet gas generation window.

The coal seams in the Horseshoe Canyon Formation were deposited in mildly brackish conditions and are uniformly rich in vitrinite (Gentzis et al., 1990;

Goodarzi, 2005). In general, coal seams from this formation have inertinite contents of approximately 14 % (Gentzis et al., 1990). Coal from the HSCN has a low content of well preserved fusinite (3 to 4 %) (Goodarzi, 2005). The fusinite may be related to the depositional environment of the coal. Plants that grow in fresh water environments are more susceptible to forest fires and oxidation, which allows for fusinite to be preserved in coal. Based on the maceral type found in coals from the HSCN, the abundance of vitrinite suggests that this coal has an affinity to adsorb methane. The inertinite present in the coal will increase the porosity, thus increasing the coals ability to desorb gas, but this increase is most likely much greater in coal from the Belly River Group.

4.3.1.4 Scollard Formation

This formation contains the thickest net coal accumulations in the Plains, with coal forming in freshwater environments. In the interior plains, the Ardley coalbeds are laterally extensive, which characterizes limnic coals, due to depositional factors (Harrison et al., 2006a). There are two areas in the Ardley 61 coal zone where the net coal is greater than the surrounding areas: Edson-Pine creek area and the Pembina area. The coals are sub-bituminous C to high volatile

B/A bituminous in rank with vitrinite reflectance values that fall within the oil and wet gas window (0.4 % and 0.75 % V Ro) (Harrison et al., 2006a). The reflectance of these coals increases from the Interior Plains to the Foothills (Harrison et al.,

2006a).

The coals from the Scollard Formation were deposited in freshwater environments and have high inertinite contents of up to 44 %, where 9 to 15 % of the inertinite is the submaceral fusinite (Goodarzi, 1985; 2006). More significantly, the inertinite group macerals include thermally altered macerals that most likely formed at high temperatures (Goodarzi, 1985). The blend of coal prepared from a coal seam from the Scollard Formation was dominated by vitrinite and inertinite

(Goodarzi, 2005). The high inertinite content in the Scollard coals increases desorption of gas in the coal while the vitrinite macerals increases its adsorption potential. The thick coal trends within the Ardley coal zones are also favourable for gas generation.

4.3.2 Trace Elements in Coal

Coals are known to contain most elements in the periodic table and these elements can be associated with organic and inorganic matter in the coal (Swaine and Goodarzi, 1995). During the interaction between coal and produced fluids during coalbed methane exploration there is potential for some of these elements to negatively influence the quality of the fluids. 62

Trace element concentrations in coal from the Mannville, HSCN, and

Scollard Formations of environmental concern are listed in Tables 4.1a-c.

Concentrations of trace elements were normalized based on average values of elements in the Earth’s crust in order to better understand the source of trace elements (Mason and Moore, 1982) (Figures 4.4a-c).

Coal from the Scollard has average concentrations of As (3.4 ppm), Co (3.4 ppm), Cr (6.0 ppm), Mo (1.9 ppm), Sb (0.6 ppm), Se (0.5 ppm), V (12.2 ppm), and

Zn (9.3 ppm). Average trace element concentrations in coal from the HSCN for the same suite of elements are: 2.2 ppm (As), 4.3 ppm (Co), 20.5 ppm (Cr), 1.0 ppm

(Mo), 0.3 ppm (Sb), 0.7 ppm (Se), 31.3 ppm (V), and 16.3 ppm (Zn), respectively.

Trace element concentrations in coal from the Mannville are much higher than those from the HSCN and the Scollard with average values at: 5.6 ppm (As), 5.3 ppm (Co), 41.6 ppm (Cr), 1.8 ppm (Mo), 4.4 ppm (Sb), 1.3 ppm (Se), 150 ppm (V), and 56.2 ppm (Zn), respectively. Trace elements in coal from the Mannville have the greatest variability in concentration. Concentrations for the elements from all three coal types overlap, suggesting that elemental variability between the coals is insignificant.

The Mannville coals have high positive Sb and Se anomalies, and most of the coals are enriched in As compared to the Earth’s crust (Figure 4.4a). Arsenic and selenium in coals is usually associated with epigenetic pyrite, which infills cleats and fractures in the coal (Swaine and Goodarzi, 1995). Coals from the

Mannville are generally deposited in brackish environments where the formation of pyrite is plentiful and will result in high sulfur concentrations (Swaine and Goodarzi,

1995). 63

Table 4.1a: Concentrations of selected trace elements in coal from the Scollard Formation.

As Co Cr Mo Sb Se V Zn Sample I.D. ppm ppm ppm ppm ppm ppm ppm ppm KC-C21 3.9 1.7 9 1.3 0.84 0.5 19 19.6 KC-C22 1.9 4.5 9 0.8 0.41 0.2 18 11.3 KC-C23 1.6 4.2 n.d. 1.4 0.13 n.d. 2 2.0 KC-C24 2.3 3.2 2 1.8 0.42 0.4 5 3.5 KC-C25 3.6 3.8 3 2.0 0.50 0.5 8 6.0 KC-C26 2.2 3.1 25 1.5 0.66 0.5 35 9.0 KC-C27 1.8 1.3 n.d. 1.1 0.49 0.2 4 9.1 KC-C28 9.3 5.9 6 5.2 1.31 1.1 15 10.9 KC-C29 4.8 2.8 2 1.7 0.33 0.6 5 16.5 KC-C30 2.5 3.8 7 2.5 0.78 0.5 11 5.2 Average 3.4 3.4 6 1.9 0.59 0.5 12 9.3 Min 1.6 1.3 1 0.8 0.13 0.1 2 2.0 Max 9.3 5.9 25 5.2 1.31 1.1 35 19.6 Standard Deviation 2.3 1.4 7 1.2 0.33 0.3 10 5.6

Table 4.1b: Concentrations of selected trace elements in coal from the Horseshoe Canyon Formation.

As Co Cr Mo Sb Se V Zn Sample I.D. ppm ppm ppm ppm ppm ppm ppm ppm KC-C01 1.6 4.2 5 2.0 0.15 0.4 8 5.7 KC-C02 1.9 3.4 44 0.8 0.46 1.1 61 21.7 KC-C03 2.4 4.9 n.d. 1.5 0.17 0.6 3 4.5 KC-C04 3.0 4.1 51 0.7 0.73 1.2 71 42.9 KC-C05 2.5 3.5 13 0.8 0.33 1.0 19 16.8 KC-C06 2.0 3.6 3 1.1 0.21 0.7 7 3.3 KC-C07 2.7 3.5 82 0.7 0.66 0.5 128 60.7 KC-C08 2.3 4.8 3 1.0 0.35 0.7 6 2.9 KC-C09 1.3 3.8 n.d. 0.8 0.06 0.2 3 1.6 KC-C10 2.0 7.6 5 1.0 0.14 0.4 7 3.3 Average 2.2 4.3 20 1.0 0.33 0.7 31 16.3 Min 1.3 3.4 1 0.7 0.06 0.2 3 1.6 Max 3.0 7.6 82 2.0 0.73 1.2 128 60.7 Standard Deviation 0.5 1.3 28 0.4 0.23 0.3 42 20.3 64

Table 4.1c: Concentrations of selected trace elements coal from the Mannville Formation.

As Co Cr Mo Sb Se V Zn Sample I.D. ppm ppm ppm ppm ppm ppm ppm ppm KC-C11 2.4 9.5 27 1.3 9.08 0.4 83 44.0 KC-C12 0.2 3.0 4 2.4 0.16 0.1 9 3.1 KC-C13 3.7 3.8 6 2.1 0.20 0.5 14 7.6 KC-C14 1.3 2.0 5 1.5 0.19 0.5 8 7.1 KC-C15 11.3 2.2 27 1.3 3.01 1.0 85 9.0 KC-C16 5.0 5.9 74 0.8 3.84 2.3 130 138.3 KC-C17 22.2 11.1 122 2.5 7.20 4.4 334 157.9 KC-C18 7.5 3.9 118 3.9 2.65 3.0 292 162.2 KC-C19 0.1 0.9 2 0.6 0.45 0.1 5 1.7 KC-C20 2.0 10.8 31 1.4 17.30 0.3 540 30.6 Average 5.6 5.3 42 1.8 4.41 1.3 150 56.2 Min 0.1 0.9 2 0.6 0.16 0.1 5 1.7 Max 22.2 11.1 122 3.9 17.30 4.4 540 162.2 Standard Deviation 6.8 3.8 46 1.0 5.48 1.5 181 68.2

High concentrations of selenium may also be associated with the organic matter in coal. The occurrence of Sb in the coal is also associated with the formation of pyrite and other accessory sulfide minerals. The HSCN and Scollard coals are enriched in Sb and Se, with some HSCN samples showing enrichment in Cr

(Figures 4.4b and c). Arsenic is also enriched in both coals, but As concentrations are lower in the HSCN compared to the Scollard and Mannville coals (Table 4.1a­ c). Overall, coals from the Mannville, HSCN, and Scollard formations appear to be enriched in some trace elements of environmental concern. Concentrations of As,

Sb, Se, and Cr in most coals recorded by Swaine (1990) are similar to concentrations found in coal from the Mannville, HSCN, and Scollard. Swaine

(1990) records As concentrations between 0.5 to 80 ppm, Sb concentrations between 0.05 to 10 ppm, Se concentrations between 0.2 to 10 ppm, and Cr concentrations between 0.5 to 60 ppm. If elements such as As, Sb, Se, and Cr are 65 high in the produced fluids associated with these coals, it is possible that the elemental composition of the coal may have affected the composition of the produced fluids through rock-water interaction.

67

4.3.3 Rare Earth Elements in Coal

It was previously suggested that the coal-forming process is also a process that causes rare earth element differentiation (Eskanazy, 1978). Shale normalized

REE patterns can help determine the enrichment of elements as compared to the surrounding formations. Rare earth elements in coal samples from the Mannville,

HSCN, and Scollard Formations were normalized to the Post Archean Australian

Shale (PAAS) using values determined by Taylor and McLennan (1988). Rare earth element values are listed in Table 4.2.

All of the coal samples are depleted in most if not all REE’s compared to

PAAS (Figure 4.5). The trend for coals from the Scollard Formation show the least variation in REEs between samples, whereas the Mannville shows the greatest amount of variation in REEs normalized to PAAS. REE concentrations are slightly higher in the Mannville coals compared to coals from the HSCN and Scollard.

Minor Eu and Tb anomalies are evident in the Mannville coals, but not in the HSCN or Scollard (Figure 4.5). The presence of Eu anomalies is often attributed to the source area (Pollock et al., 2000). The small Eu anomaly in the Mannville coals is most likely associated with reducing, marine-influenced conditions. Overall, if Eu and Tb anomalies are evident in the produced fluids associated with these coals, it is possible that rock-water interaction may have occurred. 68

Table 4.2: Rare earth element concentrations (ppm) for coals from the Mannville Formation and the HSCN/BRG and from Shallow Groundwater.

Horseshoe Canyon Scollard Mannville Parameters Formation/ Belly Formation Formation River Group La 12 ± 5.8 10 ± 6.0 15 ± 14 Ce 22 ± 10 19 ± 12 24 ± 21 Pr 2.3 ± 0.9 1.6 ± 0.96 2.4 ± 2.0 Nd 8.9 ± 4.2 7.3 ± 4.9 10 ± 9.3 Sm 1.8 ± 0.78 1.5 ± 0.93 2.2 ± 2.0 Eu 0.40 ± 0.19 0.37 ± 0.22 0.59 ± 0.53 Gd 1.6 ± 0.65 1.2 ± 0.64 1.9 ± 1.6 Tb 0.27 ± 0.11 0.22 ± 0.08 0.36 ± 0.32 Dy 1.6 ± 0.71 1.3 ± 0.52 1.8 ± 1.4 Ho 0.32 ± 0.15 0.27 ± 0.08 0.34 ± 0.27 Er 0.96 ± 0.39 0.79 ± 0.22 0.97 ± 0.65 Tm 0.12 ± 0.08 0.09 ± 0.05 0.12 ± 0.09 Yb 0.95 ± 0.39 0.88 ± 0.25 1.4 ± 1.0 Lu 0.16 ± 0.06 0.15 ± 0.04 0.24 ± 0.18 Yb 9.2 ± 3.9 7.1 ± 2.0 9.1 ± 6.6 ΣREE 62 52 71

70

4.3.4 Sulfur Isotopes in Coal

Coal from the Mannville Formation has the highest total sulfur content of

0.48 % (n=10), followed by the HSCN with 0.33 % (n=10) and the Scollard with

0.24 % (n=10). Based on gravimetric data, sulfur content in coal from the Scollard,

HSCN, and Mannville Formation is mainly organic, however, the coal does have an inorganic component (approximately 7% in the Scollard, 14 % in the HSCN, and 20

34 34 % in the Mannville). δ Stotal values were similar to δ Sorganic values, therefore only

34 δ Stotal values are reported (Tables 4.3a-c). Samples that contained enough

34 34 inorganic sulfur to be analyzed for δ S were more depleted in Stotal. Coal from

34 the HSCN/BRG and the Scollard had δ Stotal values ranging from +4.1 to +6.7 ‰

34 and -0.4 to +4.5 ‰, respectively (Tables 4.3a-b). δ Stotal values in coal from the

Mannville have the largest range from -11.5 to +6.2 ‰.

Coal from the Scollard Formation was deposited in a fresh water depositional setting, which suggests that it was deposited in a “sulfate starved” environment relative to the Mannville. This fresh water coal is more enriched in 34S relative to some of the samples from the Mannville, which could be due to the lack of sulfate available in the coal to undergo bacterial sulfate reduction. The Scollard-

Paskapoo Aquifer is also overlain by Tertiary and Quaternary sediments. These sediments are poorly consolidated glacial, fluvial, lacustrine, aeolian, and organic in origin, which enables sulfate rich groundwater to penetrate into the coal zone

(Dawson et al., 1994).

Coal from the HSCN formed in a brackish water, deltaic setting. The

Horseshoe Canyon Formation is in contact with the underlying Belly River

Formation, which is characterized as being brackish due to its high TDS values. 71

The location in which these specific wells have been drilled is overlain by the fine grained tuffaceous mudstone in the Battle Formation, which is overlain by thick sandstone. These beds limit the supply of sulfate that may potentially interact with

34 the coal (Spiker et al., 1994). The enrichment of Ssulfate in the HSCN coals is most likely related to bacterial sulfate reduction.

The wide variation in isotopic values in Mannville coals could be due to the depositional environment and biogeochemical diversity of the coals. In the southeast, the Mannville formation is overlain by the Basal Colorado Sandstone and in central Alberta the Mannville formation is overlain by the Joli Fou, which is a marine shale interbedded with sandstone. The sandstone would allow for more interaction to occur with the coal unit, and the marine shale would allow for a constant source of sulfate. The brackish depositional environment of the Mannville coals allows for a greater inorganic component compared to coal from the HSCN

34 and Scollard. More negative δ Stotal values are most likely related to the formation of sulfide minerals, such as pyrite in the cleats of the coals, which has typically negative δ34S values (Gentzis et al., 2008). 72

Table 4.3a: Content and isotope ratios of total sulfur in coal from the Scollard Formation.

δ34S Total Sulphur Sample (‰) (%) KC-C21 1.6 0.10 KC-C22 3.2 0.12 KC-C23 1.8 0.14 KC-C24 2.5 0.24 KC-C25 -0.4 0.41 KC-C26 3.2 0.23 KC-C27 4.5 0.09 KC-C28 1.4 0.45 KC-C29 0.9 0.37 KC-C30 4.3 0.29 Average 2.3 0.24 Min -0.4 0.09 Max 4.5 0.45 Standard Deviation 1.5 0.13

Table 4.3b: Content and isotope ratios of total sulfur in coal from the HSCN Formation.

δ34S Total Sulphur Sample (‰) (%) KC-C1 4.7 0.40 KC-C2 6.1 0.18 KC-C3 5.1 0.54 KC-C4 5.7 0.20 KC-C5 6.7 0.36 KC-C6 6.2 0.36 KC-C7 4.1 0.05 KC-C8 6.3 0.44 KC-C9 6.7 0.37 KC-C10 5.9 0.39 Average 5.7 0.33 Min 4.1 0.05 Max 6.7 0.54 Standard Deviation 0.9 0.14 73

Table 4.3c: Content and isotope ratios of total sulfur in coal from the Mannville Formation.

δ34S Total Sulphur Sample (‰) (%) KC-C11 -11.5 0.81 KC-C12 6.0 0.49 KC-C13 -1.6 0.58 KC-C14 6.2 0.52 KC-C15 1.4 0.91 KC-C16 -1.2 0.09 KC-C17 4.2 0.31 KC-C18 2.9 0.28 KC-C19 -2.2 0.34 KC-C20 -1.9 0.51 Average 0.2 0.48 Min -11.5 0.09 Max 6.2 0.91 Standard Deviation 5.2 0.25

4.4 Summary

The depositional environment of coal can affect the proportions of macerals, which can then influence the coals potential to sorb gas during gas generation.

Coals from the Mannville and HSCN are mainly vitrinite rich and therefore have a greater affinity to adsorb gas compared to inertinite rich coals. Mannville coals also contain petroleum-like secondary macerals such as exsudatinite and bituminite. The presence of these macerals suggests that Mannville coals have the potential to generate biogenic hydrocarbons. The vitrinite reflectance of the

Mannville coals suggests that the coals fall within the dry and wet gas generation window as well as the thermogenic gas generation window. Belly River, HSCN, and Scollard coals fall within the oil and wet gas generation window and Belly River coals also fall in the start of thermogenic gas generation. Belly River and Scollard 74 coals are vitrinite rich, but contain more inertinite compared to Mannville and

HSCN coals. Inertinite macerals allow for gas to flow freely throughout the coals.

Trace elements, rare earth elements, and S isotopes of coal can also help determine how much rock-water interaction has occurred between the coal and its associated fluids. If the associated fluids appear to be enriched in the same elements of environmental concern compared to their associated coals, it is possible that the coals have contributed to the fluids chemical composition. Overall coal in Alberta appears to be enriched in As, Sb, and Se, with the Mannville coals having the greatest enrichment compared to PAAS. Rare earth elements in coal appear to be depleted compared to PAAS. Mannville coals the highest total sulfur

34 content (0.48 %) as well as the greatest δ Stotal range from -11.5 to +6.2 ‰.

The negative values in these samples are most likely attributed to the brackish environment in which the coals were deposited, where the formation of pyrite is plentiful. Coal from the HSCN/BRG and the Scollard contained a lower inorganic

34 sulfur component compared to the Mannville and had δ Stotal values ranging from

+4.1 to +6.7 ‰ and -0.4 to +4.5 ‰, respectively. If the coal have similar S isotope values to the associated fluids, it is possible that the coal is a main source of sulfur in produced fluids. However, if the produced fluids have undergone some bacterial sulfate reduction, the original S isotope signal may have not been preserved. 75

CHAPTER 5: MAJOR ION AND ISOTOPE GEOCHEMISTRY OF PRODUCED

FLUIDS AND SHALLOW GROUNDWATER

5.1 Introduction

The objective of this chapter is to evaluate whether shallow groundwater and produced fluids and gases from coalbed methane exploration are chemically or isotopically distinct. This chapter discusses the chemical composition of the produced fluids and SGW, the redox conditions, and isotopic compositions of water, dissolved constituents and gases in order to elucidate processes that influence water and gas geochemistry.

5.2 Results

5.2.1 Chemical Composition of Fluids

The chemical characteristics of the produced fluids and shallow groundwater are summarized in Tables 5.1a-c. In order to determine various statistical paramaters (such as mean, min and max), half the detection limit was recorded for samples that had concentrations below the detection limit (Grunsky,

2000). The SGW samples were obtained from wells with perforations between 6.2 m and 157.4 m below surface (Table 5.1a). The temperatures of the shallow groundwater collected ranged from 3.6 oC to 9.8 oC, pH varied from 6.8 to 9.2 and electrical conductivity ranged from 606 to 3,558 μS/cm (Table 5.1a) with one sample with 7,065 μS/cm exceeding Alberta’s freshwater limit (4,000 mg/L). Total dissolved solids averaged 1,037 ± 714 mg/L with a range from 360 to 2,630 mg/L with one sample having a significantly higher TDS value of 4,300 mg/L (Table 76

5.1a). Sodium was the dominant cation in all SGW samples with an average concentration of 378 mg/L followed by Ca>Mg>K (average concentrations of 25 mg/L, 8 mg/L, and 2 mg/L, respectively). The dominant anion for most of the SGW samples was HCO3 with an average concentration of 735 mg/L followed by SO4 and Cl with average concentrations of 171 mg/L and 77 mg/L, respectively. Few groundwater samples had detectable nitrate with concentrations typically not exceeding 1 mg/L. Average concentrations of F, Br, Si, Ba, Sr, Li, Mn, and Fe were comparatively low (1.2 mg/L, 1.1 mg/L, 4.8 mg/L, 0.1 mg/L, 0.4 mg/L, 0.1, mg/L,

0.04 mg/L, and 0.5 mg/L, respectively). Saturation index (SI) calculations revealed that most SGW samples were in equilibrium with calcite, undersaturated with respect to siderite, and supersaturated with respect to goethite and hematite (Table

5.2a).

Swabbing fluids from the HSCN/BRG were obtained from depths ranging from 312.8 m to 492.5 m below surface and have typical in-situ temperatures ranging from 5.3 oC to 13 oC (Lemay, 2003) (Table 5.1b). The 46 fluid samples obtained from the HSCN/BRG wells were characterized by pH values between 6.8 and 11.4 (average 8.3) and had electrical conductivities ranging from 5,600 to

12,600 μS/cm (Table 5.1b). Total dissolved solids were on average 5,427 ± 3,497 mg/L and varied from 470 mg/L to 15,000 mg/L. Bicarbonate was the predominant anion with average concentrations of 2,600 mg/L, followed by Cl (average 925 mg/L) and SO4 (average 48 mg/L). The predominant cation was Na with average concentrations of 1756 mg/L, followed by K, Ca and Mg (44 mg/L, 34 mg/L, and

5.8 mg/L, respectively). Nitrate and F were not detectable and average concentrations of Br (5.8 mg/L), Si (6.6 mg/L), Ba (1.3 mg/L), Sr (1.3 mg/L), Li (0.3 77 mg/L), Mn (0.2 mg/L), and Fe (0.8 mg/L) were generally low in the HSCN/BRG waters. Based on SI data, the HSCN/BRG produced fluids data are undersaturated with respect to siderite and halite and supersaturated with respect to calcite, goethite, and hematite (Table 5.2b).

Produced fluids from the Mannville Formation were obtained from depths between 701.5 m and 1076.2 m below surface and have temperatures between

25oC to 45oC (Cody et al., 1999). In the 24 obtained samples the pH ranged between 6.3 to 7.5, electrical conductivity varied between 50 to 113 mS/cm and total dissolved solids (TDS) averaged 74,491 ± 15,550 mg/L with a range from

31,100 mg/L to 89,000 mg/L (Table 5.1c). Chloride was the dominant anion with average concentrations of 44,000 mg/L followed by HCO3 (615 mg/L). Sodium was the dominant cation (average concentration 27,000 mg/L) followed by Ca>Mg>K with average concentrations of 1879 mg/L, 607 mg/L, 461 mg/L, respectively

(Table 5.1c). Sulfate concentrations were negligible (typically <15 mg/L), no nitrate was detected, and average fluorine concentrations were 0.84 mg/L. Average concentrations of Br, Si, Ba, Sr, Mn, and Fe were 5.8 mg/L, 20 mg/L, 150 mg/L,

244 mg/L, 0.8 mg/L, and 25 mg/L, respectively. Produced fluids from the Mannville

Formation were supersaturated with respect to calcite, siderite, goethite, and hematite (Table 5.2c). 78

Table 5.1a: Chemical parameters for shallow groundwater in Alberta, Canada

Field Electrical Production Measured pH Conductivity HCO - F- Cl- Br- NO - SO 2­ Sample I.D. Depth 3 3 4 Temperature @ 22.8Cْ ( °C) (mS/cm) (m) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) KC7-1 7.5 8.6 873 68.3 554 1.28 9.3 0.06 n.d. n.d. KC8-1 6.6 7.2 1082 63.0 415 0.52 14.5 0.19 n.d. 239 KC9-1 7.8 8.4 1385 46.3 513 1.43 44.1 0.28 n.d. 223 KC10-1 9.8 8.0 1496 94.5 930 0.90 36.0 0.16 n.d. 49 KC11-1 6.6 7.5 3558 32.8 1250 0.24 16.2 0.06 n.d. 1010 KC20-1 8.8 9.0 1062 157.4 572 6.16 47.3 0.26 0.07 1 KC21-1 8.6 8.4 2245 95.4 1010 0.94 95.1 1.72 0.15 231 KC22-1 8.4 7.7 7065 115.8 2040 0.35 1530.0 29.38 0.01 1 KC23-1 7.6 8.1 1166 128.0 684 4.10 19.0 0.16 0.26 41 KC24-1 5.2 8.5 1245 22.1 663 0.98 1.0 0.03 n.d. 147 KC25-1 8.2 8.5 1180 77.1 733 2.07 10.6 0.22 0.01 n.d. KC26-1 6.8 7.7 1851 48.4 1250 0.51 25.8 0.23 0.02 39 KC27-1 5.4 9.0 869 34.3 499 2.24 9.8 0.04 0.01 14 KC28-1 5.8 7.9 1221 36.0 633 0.20 1.4 0.03 n.d. 187 KC29-1 6.6 8.4 1032 58.7 598 2.38 37.3 0.23 n.d. n.d. KC30-1 5.0 7.1 1266 49.7 636 0.23 3.4 0.03 n.d. 210 KC31-1 7.8 9.2 746 109.9 462 2.51 10.2 0.07 0.01 1 KC34-1 8.2 9.2 1040 30.5 534 2.15 3.7 0.04 n.d. 24 KC35-1 5.2 7.7 2696 6.2 965 0.73 37.4 0.09 n.d. 618 KC36-1 7.4 8.5 1317 57.2 848 1.66 11.9 0.16 n.d. 5 KC39-1 6.7 7.9 1772 41.3 847 0.44 4.0 0.07 0.01 310 KC40-1 7.0 7.2 1758 26.9 711 0.21 4.6 0.13 n.d. 499 KC41-1 6.8 6.9 998 45.3 679 0.09 1.6 0.03 n.d. 51 KC42-1 5.4 7.5 2514 75.8 1750 0.24 170.0 1.49 n.d. 1 KC43-1 6.1 7.0 979 39.3 543 0.11 3.9 0.06 n.d. 129 KC44-1 6.6 8.5 896 93.9 605 0.98 10.6 0.11 n.d. 1 KC45-1 3.6 7.5 606 37.4 407 0.29 3.6 0.12 0.86 26 KC46-1 6.6 7.5 2042 46.7 631 0.54 4.2 0.09 0.01 609 KC47-1 6.2 7.6 1990 129.5 634 0.52 8.4 0.09 0.03 618 KC48-1 7.4 7.7 921 34.5 589 0.75 3.9 0.06 3.36 77 KC49-1 9.2 9.1 934 37.1 424 3.95 2.5 0.04 0.02 125 KC50-1 8.9 8.4 - 61.0 661 1.86 17.5 0.05 0.34 161 KC51-1 8.6 8.2 2590 44.8 1050 0.99 7.7 0.03 0.00 568 KC52-1 6.7 8.3 1628 41.3 798 0.48 83.6 0.51 0.01 111 KC53-1 8.4 7.6 1078 20.0 497 0.16 2.2 0.04 0.01 224 KC54-1 8.0 8.5 1218 13.1 722 3.73 48.6 0.16 n.d. 29 KC55-1 6.2 8.9 1193 35.9 617 0.45 2.6 0.03 n.d. 121 KC56-1 8.6 6.8 1131 30.2 650 0.11 1.4 0.06 n.d. 150 KC57-1 8.8 8.9 655 45.0 371 0.84 11.3 0.07 0.01 4 KC58-1 6.7 8.7 2969 128.1 433 1.41 741.0 7.32 n.d. 1 Average 7.1 8.1 1597 59.0 735 1.24 77.4 1.10 0.13 185 Minimum 3.6 6.8 606 6.2 371 0.09 1.0 0.03 0.00 1 Maximum 9.8 9.2 7065 157.4 2040 6.16 1530.0 29.38 3.36 1010 Standard Deviation 1.4 0.7 1126 36.2 343 1.33 263.5 4.73 0.54 235 79

Table 5.1a (continued): Chemical parameters for shallow groundwater in Alberta, Canada

Total Dissolved Si4+ Ba2+ Sr3+ Li+ Na+ Ca2+ Mg2+ Mn2+ Fe2+ K+ Sample I.D. Solids (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) KC7-1 3.4 0.03 0.03 0.05 231 2.2 0.2 0.00 0.04 0.56 545 KC8-1 3.2 0.02 0.29 0.02 217 39.0 16.3 0.26 0.42 2.02 711 KC9-1 3.0 0.01 0.09 0.03 359 4.5 0.6 0.01 0.04 0.87 892 KC10-1 3.5 0.05 0.09 0.09 396 3.8 0.4 0.01 0.06 0.88 956 KC11-1 4.4 0.00 0.48 0.39 989 26.6 2.6 0.02 0.32 1.95 2630 KC20-1 5.9 0.02 0.07 0.03 292 3.3 0.2 0.00 0.35 0.77 627 KC21-1 3.4 0.14 0.19 0.03 573 3.1 0.8 0.00 n.d. 1.39 1473 KC22-1 4.5 1.19 1.65 0.11 1820 12.1 5.3 0.00 0.26 3.78 4300 KC23-1 3.1 0.09 0.07 0.03 317 2.1 0.6 0.00 n.d. 0.82 719 KC24-1 3.5 0.01 0.06 0.05 340 2.9 0.5 0.01 0.02 0.72 796 KC25-1 3.6 0.07 0.05 0.05 339 2.6 0.2 0.00 0.05 0.68 701 KC26-1 9.4 0.15 0.09 0.10 515 5.7 0.6 0.00 0.04 2.13 1160 KC27-1 3.0 0.03 0.03 0.02 252 0.9 0.2 0.00 n.d. 0.48 548 KC28-1 4.3 0.02 0.25 0.04 319 19.2 6.9 0.03 0.06 1.26 818 KC29-1 3.8 0.05 0.04 0.03 285 1.9 0.2 0.00 0.02 0.60 608 KC30-1 5.5 0.02 1.67 0.06 233 73.5 25.7 0.06 0.36 2.92 820 KC31-1 3.2 0.02 0.03 0.02 207 1.2 0.1 0.00 0.05 0.56 485 KC34-1 1.6 0.19 0.06 0.04 264 1.5 0.5 0.00 0.01 1.06 645 KC35-1 4.1 0.01 0.50 0.08 630 13.6 4.6 0.02 0.24 2.15 1840 KC36-1 3.4 0.07 0.06 0.07 348 2.8 0.2 0.00 0.02 0.67 843 KC39-1 8.8 0.01 0.16 0.10 432 16.5 1.9 0.01 n.d. 1.77 1210 KC40-1 6.7 0.02 1.44 0.10 192 194.7 45.7 0.41 5.23 2.87 1290 KC41-1 9.0 0.05 1.07 0.10 148 62.4 23.2 0.16 0.75 3.15 659 KC42-1 11.9 0.23 0.16 0.29 706 13.4 1.4 0.01 0.09 5.98 1830 KC43-1 7.6 0.05 1.21 0.08 95 111.4 23.4 0.26 1.61 4.69 657 KC44-1 4.2 0.03 0.03 0.05 240 2.4 0.3 0.02 0.21 0.84 570 KC45-1 8.0 0.11 0.60 0.03 34 48.7 41.2 0.01 n.d. 4.48 360 KC46-1 3.8 0.01 0.81 0.08 452 33.7 11.0 0.05 0.57 3.74 1460 KC47-1 3.5 0.01 0.80 0.07 444 33.6 11.0 0.05 0.28 3.63 1490 KC48-1 3.0 0.03 0.47 0.03 214 26.5 13.0 0.02 0.03 2.50 630 KC49-1 3.0 0.02 0.04 0.03 238 1.9 0.2 0.00 0.01 0.58 599 KC50-1 4.1 0.01 0.26 0.08 648 10.6 1.2 0.02 0.09 1.31 843 KC51-1 3.1 0.03 0.07 0.03 335 3.3 0.4 0.00 n.d. 0.79 1750 KC52-1 3.8 0.09 0.08 0.10 399 4.5 0.4 0.01 0.04 0.77 990 KC53-1 8.7 0.03 0.90 0.10 106 112.9 32.9 0.08 3.38 4.47 720 KC54-1 3.7 0.20 0.08 0.04 319 5.9 1.5 0.02 1.04 1.33 761 KC55-1 3.5 0.02 0.06 0.08 309 2.4 0.6 0.00 0.03 2.18 819 KC56-1 9.7 0.02 0.80 0.20 93 137.9 43.0 0.21 2.10 2.46 726 KC57-1 3.6 0.03 0.04 0.02 165 2.4 0.4 0.00 0.02 0.96 412 KC58-1 3.7 0.07 0.13 0.05 635 2.8 1.0 0.01 0.05 2.37 1590 Average 4.8 0.08 0.38 0.07 378 26.3 8.0 0.04 0.45 1.93 1037 Minimum 1.6 0.00 0.03 0.02 34 0.9 0.1 0.00 0.01 0.48 360 Maximum 11.9 1.19 1.67 0.39 1820 194.7 45.7 0.41 5.23 5.98 4300 Standard Deviation 2.4 0.19 0.47 0.07 302 43.2 13.1 0.09 1.02 1.40 714 80

Table 5.1b: Chemical parameters for HSCN/BRG produced fluids in Alberta, Canada

Field Electrical Production Measured pH Conductivity HCO - F- Cl- Br- NO - SO 2­ Sample I.D. Depth 3 3 4 Temperature @ 22.8Cْ ( °C) (mS/cm) (m) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) PKB1-5 - 8.2 2.7 419.8 949 n.d. 341 1.4 n.d. 10.8 PKB2-5 - 9.0 6.5 415.1 2610 n.d. 1057 2.9 n.d. 36.2 PKB3-5 - 8.8 5.5 408.5 1233 n.d. 1202 4.3 n.d. 20.8 PKB4-5 - 8.5 8.2 403.1 3529 n.d. 1296 5.4 n.d. 16.8 PKB5-5 - 7.6 9.5 414.0 3766 n.d. 1643 14.0 n.d. 11.3 PKB6-5 - 8.4 5.7 389.8 1211 n.d. 1183 3.5 n.d. 55.6 PKB7-5 - 8.6 3.0 401.3 638 n.d. 560 2.1 n.d. 3.4 PKB8-5 - 8.4 6.2 431.5 632 n.d. 1295 3.3 n.d. 52.1 PKB1-6 10.0 9.2 4.4 470.5 1405 n.d. 835 5.6 n.d. 95.2 PKB2-6 10.1 7.9 4.6 429.9 972 n.d. 885 5.8 n.d. 120.5 PKB3-6 10.6 7.5 3.4 439.8 675 n.d. 718 6.4 n.d. 4.8 PKB4-6 - 7.7 12.6 414.0 8864 n.d. 1040 9.2 n.d. 24.5 PKB5-6 - 8.0 2.1 394.5 1313 n.d. 159 4.7 n.d. 30.4 PKB6-6 10.3 7.3 1.6 415.8 808 n.d. 143 4.7 n.d. 47.3 PKB7-6 9.6 7.5 4.1 395.3 1892 n.d. 492 4.2 n.d. 24.0 PKB8-6 8.5 7.2 3.0 451.5 782 n.d. 534 4.3 n.d. 44.9 PKB9-6 10.6 7.7 6.0 480.8 2545 n.d. 813 4.9 n.d. 3.3 PKB10-6 10.5 6.8 4.7 491.0 603 n.d. 1203 6.0 n.d. 5.5 PKB11-6 8.2 6.8 4.2 440.5 1199 n.d. 811 5.4 n.d. 7.4 PKB12-6 9.5 8.3 6.4 356.9 2838 n.d. 1111 4.3 n.d. 260.0 PKB13-6 7.0 7.1 0.7 492.0 197 n.d. 88 4.2 n.d. 21.2 PKB14-6 9.4 8.7 3.6 475.5 706 n.d. 796 5.5 n.d. 13.4 PKB1-7 9.8 9.1 7.3 413.8 4414 n.d. 1122 7.6 n.d. 13.4 PKB2-7 13.8 7.7 9.8 426.0 5919 n.d. 1036 5.9 n.d. 55.0 PKB3-7 13.4 8.6 8.5 424.1 3765 n.d. 1308 7.2 n.d. 55.1 PKB4-7 13.3 8.6 8.0 420.4 3489 n.d. 1218 6.1 n.d. 207.8 PKB5-7 12.9 8.0 8.3 425.1 3931 n.d. 1137 7.5 n.d. 39.5 PKB6-7 11.4 8.5 7.0 421.5 2598 n.d. 1201 6.9 n.d. 38.4 PKB7-7 11.6 8.4 9.3 408.0 4782 n.d. 1182 8.1 n.d. 32.8 PKB8-7 13.4 8.5 11.0 417.1 6375 n.d. 1243 9.6 n.d. 40.2 PKB9-7 9.4 8.6 10.9 406.2 5603 n.d. 1429 8.4 n.d. 58.3 PKB10-7 12.6 8.5 7.1 415.6 3126 n.d. 1005 7.8 n.d. 37.0 PKB11-7 9.5 8.7 8.8 407.2 3485 n.d. 1458 6.8 n.d. 152.8 PKB12-7 8.6 8.7 5.1 405.9 1023 n.d. 1147 6.3 n.d. 4.2 PKB13-7 9.6 10.1 10.3 417.3 4691 n.d. 1654 8.2 n.d. 67.0 PKB14-7 9.0 9.2 5.8 426.3 2625 n.d. 743 5.0 n.d. 16.7 PKB15-7 8.4 11.2 10.0 492.5 6040 n.d. 1045 8.6 n.d. 72.3 PKB16-7 9.2 8.8 4.4 404.6 1311 n.d. 812 5.1 n.d. 6.0 PKB17-7 11.9 8.3 6.4 417.3 2652 n.d. 945 5.7 n.d. 27.2 PKB18-7 10.6 8.1 4.7 408.5 705 n.d. 1104 5.6 n.d. 9.5 PKB1-8 7.2 7.5 11.3 324.0 6106 n.d. 1700 8.7 n.d. 156.7 PKB2-8 8.4 7.3 1.4 336.5 520 n.d. 121 2.8 n.d. 51.3 PKB3-8 9.1 9.8 2.4 312.8 1268 n.d. 230 4.5 n.d. 38.9 PKB4-8 8.0 7.9 8.7 315.0 4541 n.d. 1307 10.2 n.d. 37.3 PKB5-8 7.3 8.6 0.6 316.3 360 n.d. 36 0.4 n.d. 14.2 PKB6-8 8.7 8.0 1.7 315.0 770 n.d. 184 1.4 n.d. 51.7 Average 10.0 8.3 6.0 411.0 2597 0.03 925 5.8 - 47.7 Minimum 7.0 6.8 0.6 312.8 197 0.03 36 0.4 - 3.3 Maximum 13.8 11.2 12.6 492.5 8864 0.03 1700 14.0 - 260.0 Standard Deviation 1.8 0.8 3.1 45.2 2051 0.00 444 2.6 - 53.5 81

Table 5.1b (continued): Chemical parameters for HSCN/BRG produced fluids in Alberta, Canada

Total Dissolved Si4+ Ba2+ Sr3+ Li+ Na+ Ca2+ Mg2+ Mn2+ Fe2+ K+ Sample I.D. Solids (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) PKB1-5 8.2 0.48 0.48 0.16 642 13.2 2.0 0.10 1.17 42.8 2013 PKB2-5 3.5 0.72 0.84 0.39 1879 20.8 4.6 n.d. 0.24 65.8 5682 PKB3-5 8.7 0.56 0.62 0.26 1354 13.3 3.0 0.08 0.23 32.5 3874 PKB4-5 5.9 3.49 2.41 0.39 2389 51.8 9.4 0.20 0.26 52.8 7363 PKB5-5 8.9 2.41 4.02 0.48 2839 77.91 6.10 .28 0.274 3.1 8427 PKB6-5 7.8 0.45 0.53 0.26 1480 8.7 3.2 n.d. 0.24 46.5 4001 PKB7-5 5.1 0.55 0.35 0.14 580 6.4 1.8 0.06 0.26 24.7 1823 PKB8-5 3.3 0.49 0.41 0.28 1279 6.5 3.3 n.d. 0.21 45.0 3321 PKB1-6 8.1 0.52 0.31 0.18 1169 6.8 1.4 n.d. 0.25 21.0 3548 PKB2-6 4.7 0.52 0.44 0.17 1179 12.4 3.0 0.06 0.25 21.0 3205 PKB3-6 5.4 0.58 0.38 0.12 815 11.0 1.7 0.12 0.26 25.2 2264 PKB4-6 7.6 4.58 8.04 0.73 4420 279.9 35.0 1.09 10.10 32.6 14738 PKB5-6 6.3 0.87 1.47 0.11 534 54.1 4.5 0.14 0.28 12.9 2122 PKB6-6 9.8 0.49 0.72 0.09 379 30.0 4.8 0.14 0.26 18.4 1447 PKB7-6 10.6 1.22 1.14 0.18 1155 31.4 3.8 0.28 0.30 19.3 3635 PKB8-6 6.7 0.69 0.33 0.10 778 7.4 1.3 n.d. 0.26 9.4 2168 PKB9-6 4.4 1.35 0.60 0.22 1725 12.2 3.6 0.08 0.27 80.6 5194 PKB10-6 6.2 1.30 0.65 0.16 1180 14.7 2.2 0.13 0.26 8.9 3031 PKB11-6 4.0 1.08 0.54 0.13 1091 8.9 1.6 0.11 0.30 17.4 3148 PKB12-6 28.4 0.58 0.27 0.16 1803 12.1 7.9 n.d. 0.33 30.5 6096 PKB13-6 2.4 0.65 0.42 0.05 124 22.2 2.1 0.13 0.31 6.6 469 PKB14-6 2.9 0.77 0.32 0.14 911 5.1 1.2 n.d. 0.30 20.0 2462 PKB1-7 4.9 2.48 1.66 0.33 2270 33.3 6.9 n.d. 0.34 26.2 7903 PKB2-7 3.4 3.30 3.91 0.52 3288 76.9 15.0 0.40 2.40 60.5 10470 PKB3-7 5.5 1.29 1.36 0.37 2587 19.5 5.9 0.08 0.40 62.9 7819 PKB4-7 5.8 0.96 1.20 0.33 2323 14.6 6.2 0.06 1.38 57.0 7332 PKB5-7 6.9 2.73 2.15 0.50 2568 49.7 7.3 0.14 0.37 48.5 7802 PKB6-7 5.0 1.23 1.04 0.36 1944 18.9 4.3 0.09 0.33 58.1 5878 PKB7-7 7.8 1.49 1.05 0.45 2970 15.2 5.5 n.d. 0.36 76.7 9084 PKB8-7 3.0 2.20 2.06 0.55 3749 23.9 8.5 0.05 0.61 86.2 11544 PKB9-7 3.7 1.82 1.68 0.58 3499 22.7 7.6 n.d. 0.43 103.6 10740 PKB10-7 5.1 1.21 0.95 0.35 2086 13.2 4.2 n.d. 0.40 56.2 6343 PKB11-7 6.0 1.20 1.19 0.36 2600 17.6 5.2 n.d. 0.37 71.9 7806 PKB12-7 7.5 1.68 0.88 0.19 1298 17.9 3.3 n.d. 0.33 12.6 3523 PKB13-7 6.9 1.55 1.60 0.46 3133 12.3 4.1 n.d. 0.41 79.8 9660 PKB14-7 6.5 2.22 1.38 0.27 1642 29.4 5.8 0.09 0.34 34.2 5112 PKB15-7 6.6 1.03 0.93 0.35 3301 5.8 1.7 n.d. 0.41 85.6 10570 PKB16-7 7.6 1.25 0.70 0.18 1168 11.3 2.5 n.d. 0.33 18.2 3344 PKB17-7 8.0 1.53 1.35 0.26 1832 24.3 5.6 0.11 0.33 33.1 5537 PKB18-7 7.0 0.66 0.53 0.20 1180 12.0 2.3 0.07 0.83 19.7 3048 PKB1-8 7.9 1.00 4.24 0.82 3662 222.4 20.3 0.74 7.29 100.1 11998 PKB2-8 5.3 0.22 0.26 0.10 271 27.0 4.8 0.18 0.40 53.1 1057 PKB3-8 7.5 0.16 0.21 0.16 597 15.8 2.2 n.d. 0.33 113.5 2278 PKB4-8 5.5 2.58 3.48 0.56 2661 117.6 14.1 0.71 1.09 48.1 8751 PKB5-8 3.3 0.30 0.27 0.06 97 12.6 1.5 n.d. 0.35 22.3 548 PKB6-8 9.4 0.43 0.71 0.12 341 59.9 4.3 0.21 0.31 23.4 1446 Average 6.6 1.28 1.31 0.29 1756 34.3 5.8 0.15 0.80 44.1 5427 Minimum 2.4 0.16 0.21 0.05 97 5.1 1.2 0.05 0.21 6.6 469 Maximum 28.4 4.58 8.04 0.82 4420 279.9 35.0 1.09 10.10 113.5 14738 Standard Deviation 3.8 0.95 1.44 0.18 1093 52.2 6.0 0.20 1.77 27.7 3497 82

Table 5.1c: Chemical parameters for Mannville produced fluids in Alberta, Canada

Field Electrical Production Measured pH Conductivity HCO - F- Cl- Br- NO - SO 2­ Sample I.D. Depth 3 3 4 Temperature @ 22.8Cْ ( °C) (mS/cm) (m) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) PKB1 6.7 7.3 112.9 1056.8 692.8 0.94 50538 203 n.d. 13.5 PKB2 6.3 7.2 111.9 1051.8 735.7 0.99 51711 201 n.d. 9.6 PKB3 6.3 7.2 112.3 1064.3 742.0 1.04 52215 202 n.d. 13.6 PKB4 9.5 6.8 113.1 1053.3 704.6 0.93 52161 197 n.d. 10.6 PKB5 12.4 7.1 112.6 1067.0 544.9 0.80 51718 180 n.d. 14.8 PKB6 6.9 7.1 112.0 1070.8 592.5 0.69 51249 182 n.d. 8.2 PKB7 10.6 7.1 111.7 1066.4 555.6 0.79 51655 180 n.d. 11.8 PKB8 15.7 7.0 112.7 1070.2 522.7 0.82 52364 188 n.d. 12.3 PKB9 10.0 7.1 111.4 1076.3 566.5 0.76 51322 192 n.d. 11.0 PKB1-1 7.4 7.3 104.2 905.0 296.7 0.89 46813 168 n.d. 8.3 PKB2-1 2.6 7.2 103.6 859.8 331.3 0.72 46202 152 n.d. 9.8 PKB3-1 9.8 7.4 102.5 829.0 263.9 0.69 45512 131 n.d. 8.5 PKB4-1 7.4 7.4 102.7 899.0 237.6 0.97 45584 153 n.d. 8.7 PKB5-1 15.3 7.5 105.7 914.8 307.1 0.84 48199 166 n.d. 13.3 PKB1-4 11.5 7.2 96.2 701.5 140.7 0.61 40751 143 n.d. 9.0 PKB2-4 13.2 7.2 102.3 725.5 99.0 0.55 44791 135 n.d. 9.3 PKB3-4 15.6 6.3 105.0 908.2 1336.0 1.03 45682 155 n.d. 10.3 PKB4-4 18.5 6.7 101.1 922.7 1119.0 0.73 44106 142 n.d. 10.2 PKB5-4 18.6 7.2 50.0 886.5 1646.0 0.86 16967 39 n.d. 80.2 PKB1-9 10.7 6.9 61.6 953.6 442.3 0.84 28210 61 n.d. 9.8 PKB2-9 13.1 7.2 64.1 957.4 824.9 0.85 29312 52 n.d. 11.4 PKB3-9 14.7 6.6 70.4 936.2 689.6 1.43 33027 59 n.d. 13.3 PKB4-9 6.5 6.7 73.8 898.4 976.9 0.61 34722 57 n.d. 8.9 PKB5-9 19.1 6.7 74.8 1060.8 380.4 0.82 36469 89 n.d. 13.0 Average 11.2 7.1 97.0 955.6 614.5 0.84 43803 143 0.00 13.7 Minimum 2.6 6.3 50.0 701.5 99.0 0.55 16967 39 0.00 8.2 Maximum 19.1 7.5 113.1 1076.3 1646.0 1.43 52364 203 0.00 80.2 Standard Deviation 4.5 0.3 19.5 110.2 373.0 0.18 9413 54 0.00 14.3 83

Table 5.1c (continued): Chemical parameters for Mannville produced fluids in Alberta, Canada

Total Dissolved Si4+ Ba2+ Sr3+ Li+ Na+ Ca2+ Mg2+ Mn2+ Fe2+ K+ Sample I.D. Solids (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) PKB1 6.9 161 312 5.5 31941 2457 711 0.91 17.6 210 87271 PKB2 19.1 213 290 4.9 31158 2166 690 0.82 28.8 303 87532 PKB3 19.7 165 286 5.9 31437 2335 690 1.00 33.2 232 88378 PKB4 19.0 191 365 5.4 32013 2356 704 0.85 18.5 209 88956 PKB5 21.9 153 285 8.9 31329 2441 607 0.75 21.7 313 87640 PKB6 20.3 189 286 8.0 31149 2401 618 0.88 16.4 286 87006 PKB7 20.3 152 255 8.9 30888 2411 623 0.73 28.0 308 87098 PKB8 18.6 160 282 8.7 31140 2502 640 0.86 23.2 434 88296 PKB9 20.2 155 273 7.6 31122 2332 620 0.82 19.8 324 86967 PKB1-1 18.2 139 264 5.4 28467 1445 622 0.35 14.2 173 78436 PKB2-1 14.2 143 255 7.0 28215 1712 701 0.60 31.6 194 77968 PKB3-1 13.1 125 245 6.9 27504 1844 767 0.88 53.5 171 76646 PKB4-1 20.7 147 275 5.3 28599 1481 600 0.38 18.8 167 77297 PKB5-1 15.0 113 262 7.8 29394 1668 679 0.35 8.8 259 81093 PKB1-4 13.7 82 254 4.4 24714 1823 722 0.86 10.8 79 68750 PKB2-4 15.7 110 249 5.0 25767 2956 896 1.72 17.8 180 75233 PKB3-4 25.7 164 253 5.5 28710 1594 770 0.79 7.4 204 78919 PKB4-4 20.2 108 221 7.1 26064 2641 919 0.93 25.1 183 75567 PKB5-4 17.3 63 36 4.7 11511 380 225 0.16 0.2 143 31113 PKB1-9 24.9 135 145 3.7 17620 711 268 0.33 5.3 66 47703 PKB2-9 26.9 181 164 4.2 17290 1034 293 0.96 52.0 216 49462 PKB3-9 26.6 176 180 4.7 18870 1418 372 1.32 61.0 2605 57505 PKB4-9 28.9 166 178 4.2 19570 1534 387 1.66 64.4 3659 61359 PKB5-9 21.4 203 236 3.7 22110 1466 441 0.91 19.2 137 61590 Average 19.5 150 244 6.0 26524 1879 607 0.83 24.9 461 74491 Minimum 6.9 63 36 3.7 11511 380 225 0.16 0.2 66 31113 Maximum 28.9 213 365 8.9 32013 2956 919 1.72 64.4 3659 88956 Standard Deviation 5.0 36 66 1.7 5735 639 185 0.37 17.1 841 15550 84

Table 5.2a: Saturation indices for siderite, calcite, goethite, and hematite in shallow groundwater samples.

Sample I.D. Calcite Siderite Goethite Hematite KC7-1 0.07 -3.15 7.42 16.82 KC8-1 -0.21 -0.16 7.74 17.47 KC9-1 0.05 -2.71 7.41 16.81 KC10-1 -0.10 -1.46 7.65 17.29 KC11-1 0.08 -0.01 7.88 17.74 KC20-1 0.56 -3.21 8.20 18.38 KC21-1 0.13 - - - KC22-1 0.21 -0.08 8.08 18.14 KC23-1 -0.35 - - - KC24-1 0.11 -3.24 7.05 16.09 KC25-1 0.13 -2.75 7.50 16.98 KC26-1 -0.14 -0.99 7.36 16.71 KC27-1 -0.05 - - - KC28-1 0.29 -1.42 7.58 17.15 KC29-1 -0.14 -2.97 7.18 16.35 KC30-1 0.07 -0.19 7.21 16.40 KC31-1 0.17 -4.49 7.26 16.51 KC34-1 0.30 -5.09 6.69 15.37 KC35-1 -0.03 -0.33 8.09 18.16 KC36-1 0.21 -3.13 7.03 16.04 KC39-1 0.30 - - - KC40-1 0.55 1.01 8.59 19.16 KC41-1 -0.13 0.00 6.92 15.83 KC42-1 0.17 -0.44 7.46 16.90 KC43-1 0.09 0.33 7.54 17.07 KC44-1 0.00 -1.99 8.17 18.32 KC45-1 0.21 - - - KC46-1 0.06 0.02 8.32 18.62 KC47-1 0.11 -0.33 8.08 18.15 KC48-1 0.24 -1.37 7.24 16.46 KC49-1 0.20 -4.89 6.69 15.37 KC50-1 0.50 -2.21 7.82 17.62 KC51-1 -0.08 - - - KC52-1 0.19 -2.37 7.46 16.91 KC53-1 0.66 0.68 9.21 20.41 KC54-1 0.47 -1.40 8.84 19.67 KC55-1 0.32 -3.96 7.17 16.33 KC56-1 0.11 0.37 7.24 16.47 KC57-1 0.24 -4.26 7.09 16.17 KC58-1 0.01 -3.25 7.49 16.97

Samples are supersaturated Samples are undersaturated 85

Table 5.2b: Saturation indices for siderite, calcite, goethite, and hematite in HSCN/BRG produced fluid samples.

Sample I.D. Calcite Siderite Goethite Hematite PKB1-5 0.54 -0.49 8.93 19.84 PKB2-5 1.59 -2.82 8.02 18.03 PKB3-5 1.07 -2.51 8.11 18.20 PKB4-5 1.72 -1.40 8.24 18.46 PKB5-5 1.10 0.15 7.91 17.82 PKB6-5 0.59 -1.66 8.22 18.43 PKB7-5 0.44 -2.18 8.22 18.43 PKB8-5 0.23 -2.02 8.15 18.29 PKB1-6 1.06 -3.42 7.97 17.92 PKB2-6 0.19 -0.66 8.22 18.43 PKB3-6 -0.33 -0.26 7.97 17.92 PKB4-6 1.91 1.89 9.43 20.84 PKB5-6 1.12 -0.65 8.30 18.58 PKB6-6 0.03 -0.14 7.60 17.18 PKB7-6 0.47 0.11 7.90 17.79 PKB8-6 -0.70 -0.21 7.43 16.85 PKB9-6 0.32 0.02 8.10 18.18 PKB10-6 -0.99 -0.64 6.25 14.48 PKB11-6 -0.93 -0.40 6.19 14.36 PKB12-6 0.85 -0.88 8.37 18.73 PKB13-6 -0.78 -0.53 7.39 16.77 PKB14-6 0.45 -2.40 8.25 18.49 PKB1-7 1.92 -2.73 8.13 18.24 PKB2-7 1.33 1.16 8.96 19.90 PKB3-7 1.35 -1.33 8.40 18.79 PKB4-7 1.24 -0.93 8.93 19.85 PKB5-7 1.25 -0.04 8.38 18.74 PKB6-7 1.19 -1.35 8.35 18.68 PKB7-7 1.12 -0.75 8.40 18.79 PKB8-7 1.45 -0.64 8.62 19.23 PKB9-7 1.52 -1.26 8.43 18.84 PKB10-7 1.13 -1.31 8.42 18.82 PKB11-7 1.35 -1.67 8.34 18.67 PKB12-7 1.12 -2.32 8.28 18.55 PKB13-7 1.65 -5.92 7.43 16.84 PKB14-7 1.83 -3.17 8.07 18.13 PKB15-7 1.37 -10.20 6.33 14.64 PKB16-7 1.04 -2.31 8.27 18.52 PKB17-7 1.17 -0.94 8.37 18.72 PKB18-7 0.24 -0.60 8.78 19.54 PKB1-8 1.51 1.67 8.93 19.84 PKB2-8 -0.22 -0.08 7.74 17.47 PKB3-8 1.65 -5.09 7.68 17.35 PKB4-8 1.60 0.56 8.81 19.60 PKB5-8 0.71 -2.42 8.35 18.68 PKB6-8 1.02 -0.90 8.35 18.69

Samples are supersaturated Samples are undersaturated 86

Table 5.2c: Saturation indices for siderite, calcite, goethite, and hematite in Mannville produced fluid samples.

Sample I.D. Calcite Siderite Goethite Hematite PKB1 1.27 1.05 9.01 20.04 PKB2 1.24 1.28 9.20 20.40 PKB3 1.23 1.31 9.14 20.30 PKB4 0.82 0.67 7.71 17.44 PKB5 0.98 0.88 8.56 19.14 PKB6 1.05 0.83 8.56 19.13 PKB7 1.02 1.04 8.79 19.59 PKB8 0.91 0.83 8.40 18.82 PKB9 0.97 0.85 8.50 19.00 PKB1-1 0.72 0.67 9.04 20.09 PKB2-1 0.73 0.97 9.14 20.29 PKB3-1 0.90 1.25 10.03 22.07 PKB4-1 0.77 0.76 9.58 21.17 PKB5-1 0.97 0.55 9.31 20.63 PKB1-4 0.40 0.17 8.71 19.43 PKB2-4 0.43 0.19 8.92 19.85 PKB3-4 0.43 0.06 5.80 13.61 PKB4-4 0.93 0.89 7.52 17.04 PKB5-4 0.85 -0.50 6.88 15.75 PKB1-9 0.28 0.23 7.69 17.39 PKB2-9 0.92 1.64 9.31 20.62 PKB3-9 0.43 1.11 7.77 17.54 PKB4-9 0.63 1.28 7.85 17.70 PKB5-9 0.28 0.44 7.57 17.15

Samples are supersaturated Samples are undersaturated 87

5.2.2 Oxygen and Hydrogen Isotopes

Oxygen and hydrogen isotope ratios for shallow groundwater were characterized by δ18O values ranging from -15.1 to -21.4 ‰ and δ 2H values varying from -126.7 to -170.7 ‰ (Table 5.3a) with only one exception (KC-22: δ 18O

= -8.7 ‰ and δ 2H = -96.3 ‰). Waters from the HSCN/BRG were characterized by large variations in δ18O values ranging from +5.2 to -13.4 ‰ and δ 2H values varying between +8.5 and -112.9 ‰ (Table 5.3b). Produced fluids from the

Mannville Group are characterized by δ18O values ranging from -5.5 to -11.2 ‰ and the δ 2H values varying from -83.2 to -106.1 ‰.

5.2.3 Isotopic Composition of Dissolved Inorganic Carbon

13 A wide range δ CDIC values was observed for dissolved inorganic carbon

13 (DIC) (Tables 5.3a-c). The shallow groundwater had δ CDIC values ranging from

13 -20.0 to +21.2 ‰ (Table 5.3a). δ CDIC values for HSCN/BRG waters ranged from

-15.5 to +4.4 ‰ and the Mannville waters ranged from -14.9 to +14.8 ‰ (Table

5.3b and c).

5.2.4 Isotopic Composition of Sulfate

34 A wide range of δ Ssulfate values was observed in shallow groundwater ranging from -26.6 to +34.3 ‰ (Table 5.3a). Oxygen isotope ratios of sulfate from

34 SGW varied from -13.3 to 7.7 ‰. The δ Ssulfate values for waters from the

HSCN/BRG had a more narrow range compared to SGW ranging from +6.7 to

+33.8 ‰ (Table 5.3b). Waters from the Mannville formation did not contain enough sulfate for isotope analyses. 88

Table 5.3a: Oxygen, hydrogen, dissolved inorganic carbon, and sulfate isotopic compositions for SGW.

δ18O δD δ34S δ18O δ13C Sample I.D. H2O H2O sulphate sulphate DIC (‰)( ‰)( ‰)( ‰)( ‰) KC7-1 -18.4 -150.7 14.0 - -6.3 KC8-1 -21.4 -170.7 -3.5 0.0 -15.8 KC9-1 -20.6 -166.2 4.1 2.2 -16.3 KC10-1 -19.0 -149.4 5.6 1.5 -12.9 KC11-1 -19.6 -161.0 2.1 -2.1 -6.1 KC20-1 -15.1 -126.9 -3.7 - 4.3 KC21-1 -18.7 -149.7 5.5 1.8 -19.1 KC22-1 -8.7 -96.3 - - 21.2 KC23-1 -16.8 -135.4 -16.1 -8.0 -4.5 KC24-1 -18.4 -152.0 -2.1 -2.5 -12.6 KC25-1 -17.4 -141.6 -3.7 -12.4 -3.7 KC26-1 -18.0 -147.6 34.3 6.8 -20.0 KC27-1 -19.6 -155.4 20.8 3.5 -11.6 KC28-1 -17.9 -146.0 -11.9 -5.1 -14.8 KC29-1 -16.0 -129.4 -1.3 - 6.5 KC30-1 -18.5 -152.3 -6.9 -0.6 -14.5 KC31-1 -17.4 -139.4 -4.3 - -8.1 KC34-1 -18.7 -148.8 14.5 -0.1 -11.5 KC35-1 -18.9 -149.7 -5.0 -9.6 -10.8 KC36-1 -20.1 -161.8 0.4 0.3 -19.4 KC39-1 -18.9 -151.1 -7.4 -0.3 -15.7 KC40-1 -19.0 -155.1 -10.3 -2.0 -18.4 KC41-1 -18.1 -143.5 -0.7 1.0 -13.1 KC42-1 -16.4 -131.7 -3.0 - 4.7 KC43-1 -20.3 -158.7 -5.3 -10.3 -13.7 KC44-1 -19.5 -150.4 - - -1.7 KC45-1 -18.3 -142.9 0.7 -6.8 -10.7 KC46-1 -20.3 -158.2 -10.7 -7.0 -9.7 KC47-1 -20.2 -161.0 -10.7 -7.0 -9.6 KC48-1 -18.3 -143.4 -12.1 -8.6 -11.8 KC49-1 -17.7 -140.7 0.6 2.5 -8.5 KC50-1 -18.9 -146.6 -26.6 -13.3 -9.9 KC51-1 -18.6 -145.3 3.7 1.2 -14.6 KC52-1 -20.1 -161.2 -9.3 -1.4 -12.3 KC53-1 -17.7 -144.8 -8.6 -2.8 -14.6 KC54-1 -17.3 -136.5 0.1 0.6 -15.7 KC55-1 -19.6 -152.5 -6.5 -3.2 -10.4 KC56-1 -18.4 -141.8 -6.7 -8.4 -13.3 KC57-1 -17.9 -141.1 16.6 7.7 -9.4 KC58-1 -16.5 -124.5 - - -1.5 Average -18.3 -146.5 -1.4 -2.6 -9.6 Minimum -21.4 -170.7 -26.6 -13.3 -20.0 Maximum -8.7 -96.3 34.3 7.7 21.2 Standard Deviation 2.1 13.2 11.0 5.3 8.1 89

Table 5.3b: Oxygen, hydrogen, dissolved inorganic carbon, and sulfate isotopic compositions for HSCN/BRG produced fluids.

δ18O δD δ34S δ18O δ13C Sample I.D. H2O H2O sulphate sulphate DIC (‰) (‰) (‰) (‰) (‰) PKB1-5 -1.7 -23.4 11.1 - -7.9 PKB2-5 -7.2 -72.4 - - -7.9 PKB3-5 -11.5 -101.1 11.7 - -8.7 PKB4-5 -10.5 -97.6 12.1 - -10.3 PKB5-5 -9.5 -90.6 10.7 - -8.5 PKB6-5 -10.3 -96.5 12.8 - -10.2 PKB7-5 -13.4 -112.9 12.2 - 4.4 PKB8-5 -10.6 -95.6 11.6 - -10.1 PKB1-6 -10.1 -96.6 18.2 - -11.3 PKB2-6 -4.3 -48.4 16.8 - -9.5 PKB3-6 1.9 2.9 16.3 - -9.7 PKB4-6 -4.8 -58.3 12.2 - -9.1 PKB5-6 -3.8 -52.1 8.6 - -9.5 PKB6-6 -0.1 -28.6 11.1 - -10.9 PKB7-6 0.0 -18.3 33.8 - -10.0 PKB8-6 2.6 -2.6 16.0 - -7.5 PKB9-6 1.5 -1.3 10.7 - -6.3 PKB10-6 -11.1 -102.4 11.7 - 0.3 PKB11-6 3.3 -4.0 26.0 - -6.3 PKB12-6 -10.1 -100.3 16.1 - -6.7 PKB13-6 -0.6 -30.9 12.7 - -10.3 PKB14-6 -4.0 -52.7 19.9 - -9.0 PKB1-7 1.7 -22.6 10.6 - -7.5 PKB2-7 -9.0 -86.8 9.8 - -9.3 PKB3-7 -11.0 -103.5 9.0 - -7.7 PKB4-7 -10.0 -95.8 6.7 - -8.6 PKB5-7 -8.7 -82.3 11.9 - -7.4 PKB6-7 -11.1 -101.5 10.3 - -5.9 PKB7-7 -7.5 -80.3 18.5 - -10.7 PKB8-7 -10.2 -99.5 11.1 - -8.4 PKB9-7 -10.1 -97.2 11.9 - -5.6 PKB10-7 -11.0 -89.8 10.5 - -8.8 PKB11-7 -8.0 -80.4 9.4 - -7.5 PKB12-7 -11.5 -100.7 13.4 - 2.2 PKB13-7 -0.2 -29.9 12.7 - -13.1 PKB14-7 5.2 8.5 12.4 - -7.2 PKB15-7 -3.0 -53.0 10.9 - -15.5 PKB16-7 -10.8 -98.4 12.2 - -6.7 PKB17-7 -10.6 -98.5 12.7 - -10.7 PKB18-7 -9.3 -88.3 12.2 - -12.4 PKB1-8 -4.9 -61.1 11.3 - -12.2 PKB2-8 -5.0 -58.8 15.3 - -12.4 PKB3-8 -3.4 -48.2 11.1 - -10.3 PKB4-8 -4.5 -57.5 9.8 - -13.1 PKB5-8 -5.7 -65.2 8.7 - -11.7 PKB6-8 -4.1 -42.4 11.7 - -13.2 Average -6.6 -65.6 13.0 - -8.7 Minimum -13.4 -112.9 6.7 - -15.5 Maximum 5.2 8.5 33.8 - 4.4 Standard Deviation 6.5 35.2 4.6 - 3.7 90

Table 5.3c: Oxygen, hydrogen, dissolved inorganic carbon, and sulfate isotopic compositions for Mannville produced fluids.

δ18O δD δ34S δ18O δ13C Sample I.D. H2O H2O sulphate sulphate DIC (‰) (‰) (‰) (‰) (‰) PKB1 -5.9 -85.0 - - -6.0 PKB2 -6.0 -84.8 - - -7.0 PKB3 -5.6 -83.2 - - -7.3 PKB4 -5.6 -85.6 - - -6.5 PKB5 -5.7 -85.3 - - -4.0 PKB6 -5.7 -85.1 - - -3.9 PKB7 -6.0 -85.2 - - -3.5 PKB8 -5.5 -83.8 - - -6.4 PKB9 -5.8 -85.5 - - -4.2 PKB1-1 -7.2 -88.5 - - 0.5 PKB2-1 -7.4 -88.2 - - -1.1 PKB3-1 -8.2 -92.9 - - 0.8 PKB4-1 -7.2 -86.8 - - -2.5 PKB5-1 -7.2 -87.8 - - 2.7 PKB1-4 -9.7 -99.9 - - -7.9 PKB2-4 -8.7 -95.0 - - -12.8 PKB3-4 -6.9 -90.9 - - -12.0 PKB4-4 -7.1 -87.6 - - -14.9 PKB5-4 -11.2 -106.1 - - -10.4 PKB1-9 -7.9 -101.1 - - 14.8 PKB2-9 -8.7 -104.2 - - 10.1 PKB3-9 -8.4 -99.9 - - 6.6 PKB4-9 -9.2 -104.4 - - 10.3 PKB5-9 -7.5 -98.5 - - 10.3 Average -7.3 -91.5 - - -2.3 Minimum -11.2 -106.1 - - -14.9 Maximum -5.5 -83.2 - - 14.8 Standard Deviation 1.5 7.6 - - 8.0 91

5.2.5 Concentration and Isotopic Composition of Dissolved and Free Gas

Free gas samples were collected from shallow groundwater wells, where possible, and the δ13C values for methane, ethane and carbon dioxide, as well as

δ2H values for methane are summarized in Table 5.4a. Isotopic data was only recorded for samples with methane concentrations > 1 vol %. Free gas from the shallow groundwater contained from 0 to 95 vol % methane with δ13C values ranging from -60.4 to -83.9 ‰ (Table 5.4a). Only 10 out of the 40 samples contained enough ethane for isotopic analysis with values ranging from -36.1 to

2 -65.9 ‰. The shallow groundwater samples were also analyzed for their δ HCH4

2 values in the free gas. Most δ HCH4 values ranged from -277.3 to -336.2 ‰. The

δ13C values of methane, ethane, propane, butane, pentane, and carbon dioxide from dissolved gas in CBM production fluids within the Mannville Group and the

HSCN/BRG are listed in Tables 5.4b and c. Isotopic data were only recorded for samples that contained methane concentrations > 1 vol %. Dissolved methane from the HSCN/BRG had δ13C values between -40.4 and -56.9 ‰ with concentrations ranging from 1 to 78 vol % (Table 5.4b). δ13C values ranged from

-28.6 to -41.7 ‰ for ethane and -28.0 to -33.5 ‰ for propane. Only two samples contained sufficient concentrations of butane for δ13C analysis yielding values of

-39.0 and -45.0 ‰. Two samples also contained enough pentane for isotopic analysis having values of -25.9 and -26.9 ‰. Dissolved hydrocarbon gas from the

Mannville Group was characterized by δ13C values ranging from -44.3 to -57.4 ‰ for methane, -21.8 to -31.8 ‰ for ethane, and -25.0 to -28.3 ‰ for propane (Table

5.4c). A few samples contained sufficient concentrations of butane for isotope analysis yielding δ13C values between -20.8 and -27.5 ‰. No pentane was 92 detected in the dissolved gas. Concentrations of methane ranged from 2 to 62 vol

% (Table 5.4c). 93

Table 5.4a: Concentration and isotopic composition of free gas in SGW. The isotopic composition of methane was only recorded for samples that contained >1 vol. % of methane.

δ13C CH δ13C C H δ13C C H δ13C C H δ13C C H δ13C CO δD αCO -CH f- 1 Sample I.D. CH4 4 C2 2 6 C3H8 3 8 C4H10 4 10 C5H12 5 12 CO2 2 CH4 2 4 (‰) (vol %) (‰) (vol %) (‰) (vol %) (‰) (vol %) (‰) (vol %) (‰) (vol %) (‰) (%) KC7-1 -76.9 56.0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -15.8 0.15 - 1.07 - KC8-1 n.d. 0.1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -15.8 0.15 - - - KC9-1 n.d. 0.1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -23.6 0.07 - - - KC10-1 -69.7 28.0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -22.9 0.49 -296.0 1.05 100.0 KC11-1 n.d. 0.04 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -14.2 2.31 - - - KC20-1 -66.9 86.8 -50.2 0.04 n.d. n.d. n.d. n.d. n.d. n.d. -10.1 0.05 -277.3 1.06 100.0 KC21-1 -77.7 53.9 -36.1 0.03 n.d. n.d. n.d. n.d. n.d. n.d. -27.3 0.22 -295.9 1.05 100.0 KC22-1 ------KC23-1 -81.6 84.3 -55.7 0.03 n.d. n.d. n.d. n.d. n.d. n.d. -13.5 0.07 -295.5 1.07 99.9 KC24-1 n.d. 0.1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -14.4 0.15 - - - KC25-1 -73.8 71.6 -44.0 0.03 n.d. n.d. n.d. n.d. n.d. n.d. -12.8 0.11 -304.3 1.07 97.7 KC26-1 -81.3 42.6 n.d. 0.01 n.d. n.d. n.d. n.d. n.d. n.d. -27.3 0.57 -305.0 1.06 100.0 KC27-1 -70.3 29.5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -16.4 0.05 -281.9 1.06 100.0 KC28-1 n.d. 0.02 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -18.5 0.41 - 1.05 - KC29-1 -60.4 88.3 -49.5 0.07 n.d. n.d. n.d. n.d. n.d. n.d. -7.6 0.06 -283.4 1.06 100.0 KC30-1 ------n.d.- ---- KC31-1 -61.0 87.1 n.d. 0.003 n.d. n.d. n.d. 0.13 n.d. n.d. -15.3 0.03 -279.3 1.05 100.0 KC34-1 ------KC35-1 ------KC36-1 -71.4 27.3 -48.0 0.08 n.d. n.d. n.d. 0.16 n.d. n.d. -26.0 0.15 -279.3 1.05 100.0 KC39-1 n.d. 0.6 n.d. 0.001 n.d. n.d. n.d. 0.17 n.d. n.d. -22.4 0.77 - - - KC40-1 ------KC41-1 n.d. 0.04 n.d. 0.001 n.d. n.d. n.d. n.d. n.d. n.d. -19.1 4.48 - - - KC42-1 -70.8 91.6 -55.1 0.54 n.d. n.d. n.d. n.d. n.d. n.d. -3.3 2.64 -309.5 1.07 85.2 KC43-1 n.d. 0.01 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -20.4 3.84 - - - KC44-1 -73.5 73.6 -57.6 0.02 n.d. n.d. n.d. 0.06 n.d. n.d. -11.3 0.15 -316.9 1.07 93.7 KC45-1 n.d. 0.3 n.d. n.d. n.d. n.d. n.d. 0.19 n.d. n.d. -19.1 1.28 -336.2 1.05 - KC46-1 n.d. 0.2 n.d. n.d. n.d. n.d. n.d. 0.20 n.d. n.d. -18.2 1.13 - - - KC47-1 n.d. 0.2 n.d. n.d. n.d. n.d. n.d. 0.18 n.d. n.d. -18.2 1.36 - - - KC48-1 ------0.18- --20.11.20 - -- KC49-1 ------KC50-1 ------KC51-1 ------KC52-1 n.d. 0.1 n.d. n.a. n.d. n.d. n.d. 0.29 n.d. n.d. -20.7 0.26 - - - KC53-1 ------KC54-1 -83.9 18.5 -45.6 0.0003 n.d. n.d. n.d. 0.28 n.d. n.d. -24.5 0.20 - 1.06 - KC55-1 ------n.d.- ---- KC56-1 n.d. 0.02 n.d. 0.0003 n.d. 0.30 n.d. n.d. n.d. n.d. -20.6 6.15 - - - KC57-1 -75.4 24.2 n.d. 0.004 n.d. n.d. n.d. 0.27 n.d. n.d. -16.6 0.03 - 1.06 - KC58-1 -71.6 94.9 -65.9 0.02 n.d. n.d. n.d. n.d. n.d. n..d. -9.6 0.05 - 1.07 - Average -72.9 33 -50.8 0.03 - 0.01 - 0.07 - - -17.5 0.95 -297.0 1.06 98.0 Minimum -83.9 0.0 -65.9 0.00 - 0.00 - 0.00 - - -27.3 0.03 -336.2 1.05 85.2 Maximum -60.4 95 -36.1 0.54 - 0.30 - 0.29 - - -3.3 6.15 -277.3 1.07 100.0 Standard Deviation 6.7 37 8.3 0.10 - 0.05 - 0.10 - - 5.8 1.50 17.4 0.01 4.5 93 94

Table 5.4b: Concentration and isotopic composition of dissolved gas in HSCN/BRG produced fluids. The isotopic composition of methane was only recorded for samples that contained >1 vol. % of methane.

δ13C CH δ13C C H δ13C C H δ13C C H δ13C C H δ13C CO αCO -CH Sample I.D. CH4 4 C2 2 6 C3H8 3 8 C4H10 4 10 C5H12 5 12 CO2 2 2 4 (‰) (vol %) (‰) (vol %) (‰) (vol %) (‰) (vol %) (‰) (vol %) (‰) (vol %) PKB1-5 n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. - PKB2-5 -41.9 6.4 n.d. 0.14 n.d. 0.12 n.d. n.d. n.d. n.d. -16.1 0.42 1.03 PKB3-5 -51.5 37.1 -33.1 4.16 n.d. 2.78 n.d. 87.9 n.d. 0.9 -16.6 0.73 1.04 PKB4-5 -51.8 37.8 -34.1 1.12 n.d. 0.18 n.d. n.d. n.d. n.d. -17.3 1.79 1.04 PKB5-5 -42.6 16.4 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -18.3 5.41 1.03 PKB6-5 -40.4 7.0 -28.6 0.06 -29.8 n.d. n.d. n.d. n.d. n.d. -20.1 1.21 1.02 PKB7-5 -41.0 29.4 -33.9 2.14 n.d. 0.21 n.d. n.d. n.d. n.d. -2.5 2.87 1.04 PKB8-5 -53.2 0.7 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. -17.4 0.46 1.04 PKB1-6 -56.3 61.8 -34.8 0.44 -28.7 0.04 -45.0 n.d. n.d. n.d. -17.6 0.57 1.04 PKB2-6 -55.5 54.9 -35.6 0.35 -28.6 n.d. n.d. n.d. n.d. n.d. -17.4 1.72 1.04 PKB3-6 -55.7 6.5 -36.2 0.52 -28.0 0.10 n.d. n.d. n.d. n.d. -13.5 6.73 1.04 PKB4-6 -55.7 64.3 -35.5 0.49 -29.1 n.d. n.d. n.d. n.d. n.d. 9.9 3.67 1.07 PKB5-6 -56.5 11.4 -37.3 0.08 -29.3 n.d. n.d. n.d. n.d. n.d. -19.1 1.20 1.04 PKB6-6 -55.9 8.5 -35.7 0.06 -29.3 0.02 n.d. n.d. n.d. n.d. -18.6 0.34 1.04 PKB7-6 -55.8 7.9 -36.2 0.06 -29.7 n.d. n.d. n.d. n.d. n.d. -18.4 0.59 1.04 PKB8-6 -55.9 6.3 -35.7 0.04 -29.8 n.d. n.d. n.d. n.d. n.d. -10.3 0.52 1.05 PKB9-6 -55.2 65.3 -35.6 0.52 -29.3 0.09 n.d. n.d. n.d. n.d. -16.1 0.72 1.04 PKB10-6 -55.4 26.8 -34.2 0.18 -29.9 n.d. n.d. n.d. n.d. n.d. 5.8 4.58 1.06 PKB11-6 -55.7 56.7 -35.3 0.43 -29.1 0.08 n.d. n.d. n.d. n.d. -11.9 1.29 1.05 PKB12-6 -55.3 51.9 -35.7 0.45 -30.9 n.d. n.d. n.d. n.d. n.d. -10.9 1.69 1.05 PKB13-6 -56.9 61.8 -36.8 0.34 -30.1 n.d. n.d. n.d. n.d. n.d. -15.8 0.48 1.04 PKB14-6 -54.9 23.3 -36.3 0.17 -29.9 0.04 n.d. n.d. n.d. n.d. -16.8 0.33 1.04 PKB1-7 -54.8 47.2 -38.3 0.30 -29.0 n.d. n.d. n.d. n.d. n.d. -15.5 2.96 1.04 PKB2-7 -54.7 65.3 -36.8 0.79 -28.8 0.19 n.d. n.d. n.d. n.d. -17.1 2.73 1.04 PKB3-7 -55.2 12.4 -36.7 0.24 -30.8 n.d. n.d. n.d. n.d. n.d. -16.0 1.39 1.04 PKB4-7 -55.7 75.6 -37.5 0.56 -28.8 0.06 n.d. n.d. n.d. n.d. -16.1 1.65 1.04 PKB5-7 -55.8 11.8 -35.6 0.06 -29.5 n.d. n.d. n.d. n.d. n.d. -16.5 3.51 1.04 PKB6-7 -55.5 64.5 -36.8 0.35 -29.5 0.06 n.d. n.d. n.d. n.d. -15.9 0.89 1.04 PKB7-7 -55.2 42.6 -36.9 0.22 -29.0 n.d. n.d. n.d. n.d. n.d. -18.8 1.06 1.04 PKB8-7 -54.7 12.6 -36.3 0.07 -28.7 n.d. -39.0 n.d. n.d. n.d. 2.8 2.30 1.06 PKB9-7 -54.2 33.1 -36.4 0.16 -29.5 n.d. n.d. n.d. n.d. n.d. -15.4 0.79 1.04 PKB10-7 -54.2 3.0 -36.2 0.04 -28.4 n.d. n.d. n.d. n.d. n.d. -18.4 0.91 1.04 PKB11-7 -55.6 22.2 -36.5 0.12 -28.2 n.d. n.d. n.d. n.d. n.d. -16.5 0.59 1.04 PKB12-7 -54.7 72.0 -36.8 0.38 -29.2 0.03 n.d. n.d. n.d. n.d. -5.8 0.68 1.05 PKB13-7 -55.9 72.3 -36.2 0.40 -28.4 0.04 n.d. n.d. n.d. n.d. n.d. 0.38 - PKB14-7 -56.4 71.9 -36.3 0.35 -29.0 n.d. n.d. n.d. n.d. n.d. -15.3 0.30 1.04 PKB15-7 -56.1 53.1 -36.7 0.49 -28.8 0.05 n.d. n.d. n.d. n.d. n.d. 3.76 - PKB16-7 -54.9 65.9 -35.8 0.36 -29.6 n.d. n.d. n.d. n.d. n.d. -15.0 0.57 1.04 PKB17-7 -54.6 62.7 -34.9 0.35 -29.3 n.d. n.d. n.d. n.d. n.d. -19.6 0.74 1.04 PKB18-7 -54.8 65.7 -35.2 0.35 -29.0 n.d. n.d. n.d. n.d. n.d. -16.9 0.87 1.04 PKB1-8 -55.7 58.9 -40.6 0.51 n.d. 0.23 n.d. n.d. n.d. n.d. -22.1 0.97 1.04 PKB2-8 -55.5 77.7 -41.2 0.52 -30.0 0.10 n.d. n.d. n.d. n.d. -20.6 1.33 1.04 PKB3-8 -55.6 11.3 -41.4 n.d. -30.2 n.d. n.d. n.d. -25.9 n.d. -16.8 0.44 1.04 PKB4-8 -55.4 77.5 -41.4 0.49 -30.9 0.07 n.d. n.d. -26.9 n.d. -14.8 0.48 1.04 PKB5-8 -54.4 9.4 -40.7 0.04 -33.5 n.d. n.d. n.d. n.d. n.d. n.d. 0.20 - PKB6-8 -56.5 29.0 -41.7 0.16 -29.2 n.d. n.d. n.d. n.d. n.d. -25.3 1.53 1.03 Average -54.0 39.1 -36.5 0.4 -29.4 0.1 -42.0 2.0 -26.4 0.0 -14.6 1.5 1.04 Minimum -56.9 0.7 -41.7 0.0 -33.5 0.0 -45.0 0.0 -26.9 0.0 -25.3 0.2 1.02 Maximum -40.4 77.7 -28.6 4.2 -28.0 2.8 -39.0 87.9 -25.9 0.9 9.9 6.7 1.07 Standard deviation 4.1 25.9 2.4 0.7 1.0 0.4 4.2 13.1 0.7 0.1 7.0 1.5 0.01 94 95

Table 5.4c: Concentration and isotopic composition of dissolved gas in Mannville produced fluids. The isotopic composition of methane was only recorded for samples that contained >1 vol. % of methane.

δ13C CH δ13C C H δ13C C H δ13C C H δ13C C H δ13C αCO -CH Sample I.D. CH4 4 C2 2 6 C3H8 3 8 C4H10 4 10 C5H12 5 12 CO2 2 4 (‰) (vol %) (‰) (vol %) (‰) (vol %) (‰) (vol %) (‰) (vol %) (‰) PKB1 -47.6 61.2 -29.1 6.90 -25.9 4.33 n.d. 4.26 n.d. 1.4 -14.5 1.03 PKB2 -44.4 47.7 -28.9 3.07 -25.6 1.19 n.d. 0.96 n.d. n.d. -13.7 1.03 PKB3 -47.9 6.7 -29.0 0.44 -25.9 n.d. n.d. n.d. n.d. n.d. -13.7 1.04 PKB4 -47.4 4.3 -27.7 0.05 -25.1 n.d. n.d. n.d. n.d. n.d. -14.4 1.03 PKB5 -49.1 4.4 -30.0 0.48 -27.5 n.d. n.d. n.d. n.d. n.d. -10.6 1.04 PKB6 -49.0 2.6 -29.7 0.28 -27.5 n.d. n.d. n.d. n.d. n.d. -12.1 1.04 PKB7 -48.6 61.6 -30.6 8.78 -28.1 5.73 n.d. 5.76 n.d. 1.8 -12.1 1.04 PKB8 -47.0 46.7 -30.2 3.24 -28.2 0.88 n.d. 0.35 n.d. n.d. -12.3 1.04 PKB9 -48.2 43.6 -28.9 2.06 -27.1 0.43 n.d. n.d. n.d. n.d. -14.7 1.04 PKB1-1 -49.7 42.9 -30.3 1.65 -28.1 0.27 n.d. n.d. n.d. n.d. -6.9 1.05 PKB2-1 -50.8 38.5 -29.6 1.12 -27.0 0.19 n.d. n.d. n.d. n.d. -6.2 1.05 PKB3-1 -48.9 2.3 -29.6 0.09 -27.9 n.d. -27.5 n.d. n.d. n.d. -5.2 1.05 PKB4-1 -51.7 45.1 -31.0 0.23 -28.3 0.03 n.d. n.d. n.d. n.d. -7.9 1.05 PKB5-1 -52.0 14.8 -29.7 0.33 -27.6 n.d. n.d. n.d. n.d. n.d. -3.4 1.05 PKB1-4 -53.4 34.8 -21.8 1.03 n.d. 0.11 n.d. n.d. n.d. n.d. -13.4 1.04 PKB2-4 -53.7 2.8 -24.4 0.05 -25.0 n.d. n.d. n.d. n.d. n.d. -18.7 1.04 PKB3-4 -51.7 6.6 -30.8 0.00 -27.0 n.d. -26.2 n.d. n.d. n.d. -17.6 1.04 PKB4-4 -57.4 8.3 -29.0 0.05 -27.0 n.d. n.d. n.d. n.d. n.d. -17.9 1.04 PKB5-4 -57.4 39.6 -31.8 0.86 -28.2 0.11 n.d. n.d. n.d. n.d. -17.3 1.04 PKB1-9 -44.3 44.6 -28.8 1.46 -28.2 0.21 n.d. n.d. n.d. n.d. 8.7 1.06 PKB2-9 -44.6 60.3 -27.4 1.90 -25.8 0.23 -25.4 n.d. n.d. n.d. 3.2 1.05 PKB3-9 -46.4 12.0 -28.2 0.27 -25.4 n.d. n.d. n.d. n.d. n.d. 0.1 1.05 PKB4-9 -45.4 60.4 -27.4 3.22 -26.2 0.29 -20.8 n.d. n.d. n.d. 4.9 1.05 PKB5-9 -47.8 50.7 -27.0 0.82 -26.1 0.06 n.d. n.d. n.d. n.d. 8.6 1.06 Average -49.4 30.9 -28.8 1.60 -26.9 0.58 -25.0 0.47 - 0.1 -8.6 1.04 Maximum -44.3 61.6 -21.8 8.78 -25.0 5.73 -20.8 5.76 - 1.8 8.7 1.06 Minimum -57.4 2.3 -31.8 0.00 -28.3 0.00 -27.5 0.00 - 0.0 -18.7 1.03 Standard deviation 3.6 22.3 2.1 2.2 1.1 1.4 2.9 1.4 - 0.5 8.4 0.01 95 96

5.3 Discussion

5.3.1 Isotopic composition of the water samples

Figure 5.1 displays the isotopic composition of all water samples with respect to the local meteoric water line (LMWL) established by Peng et al. (2004):

2 18 2 δ Hwater = 7.68 δ Owater – 0.21 (R = 0.96)

The LMWL characterizes the isotopic composition of meteoric water in southern Alberta and has an amount-weighted average δ18O value of -17.9 ‰ and an average δ2H value of -136.1 ‰ (Peng et al., 2004).

Shallow groundwater and produced fluids from the HSCN/BRG and

Mannville Formations have distinct δ2H and δ18O values (Figure 5.1). δ2H and

δ18O values for all but one shallow groundwater sample ranged between -120 ‰ and -170 ‰ and between -15 ‰ and -21. The values plot close to the LMWL with a linear regression of δ2H and δ18O values yielding a slope of 7.4 indicating a meteoric origin and little evaporation during recharge (Clark and Fritz, 1997). Only one shallow groundwater (KC22) sample deviated from this trend, displaying elevated δ2H and δ18O values falling off the LMWL, which indicates the influence of deeper formation water likely from the Belly River formation (Figure 5.1).

Formation fluids from the Ardley coal zone in the Pembina-Warburg area in Central

Alberta collected by Harrison et al. (2006a) had δ18O and δ2H values of -14 ‰ and

-115 ‰ with a slope similar to that of the LMWL. Shallow groundwater collected from the Scollard and Paskapoo aquifers had similar average δ18O and δ2H values

(-18.3±2.1 ‰ and -146±10 ‰, respectively, slope of the δ2H vs. δ18O regression

98

Produced fluids from the HSCN/BRG had δ2H values ranging from -65 to

-112 ‰ and δ18O values varying between +5 to -14 ‰. The isotopic composition of produced fluids from the HSCN/BRG displays a slope of 7.0 intersecting the LMWL at -18.4 ‰ (δ18O) and -141.6 ‰ (δ2H). Shallow groundwater collected from the

HSCN/BRG formations had average δ18O and δ2H values of -18.5 ‰ and

-147.3 ‰, respectively, indicating that the produced fluids from the HSCN/BRG are of a similar meteoric origin to SGW samples collected from the HSCN/BRG.

Subsequently, the samples have been significantly affected by evaporation, mixing with formation water, and/or potential rock-water interactions.

The Mannville group produced fluids are also characterized by elevated

δ2H and δ18O values falling on a regression line with a slope of 4.5 that intersects the LMWL at δ18O and δ2H values of -18.4 ‰ and -141.5 ‰, respectively. This is indicative of mixing of meteoric water with low δ2H and δ18O values and formation water with elevated δ2H and δ18O values. Because of their distinct δ2H and δ18O values (Figure 5.1), shallow groundwater and produced fluids from the HSCN/BRG formation and the Mannville group can be distinguished based on their isotopic compositions. This becomes particularly apparent if the δ18O values are plotted versus total dissolved solids (Figure 5.2). However, fluids from the Ardley coal zone and shallow groundwater from the Scollard and Paskapoo aquifers are not isotopically distinct.

103

HSCN formation (Beaton, 2003). Elevated concentrations of Na could also be related to the interaction between the HSCN/BRG waters and the bentonite beds that are known to have a high cation exchange capacity (Ross and Hendricks,

1945). Bentonite can only form where Mg is available from rocks or water sources

(Ross and Hendricks, 1945) and hence ion exchange likely also explains the low

Mg concentrations in HSCN/BRG waters. There was also a positive correlation between Na and Cl (correlation coefficient of 0.78) concentrations suggesting increasing mixing with saline water (Figure 5.4b). Sulfate concentrations were

34 comparatively low (Figure 5.3b) with an average of 47.7 mg/L and δ Ssulfate values were generally higher than +5 ‰ indicating bacterial (dissimilatory) sulfate reduction (see section 5.3.4).

Mannville produced fluids are saline Na-Cl type waters (Figure 5.3c). A lack of correlation between Na and HCO3 (correlation coefficient of -0.36) as well as the positive correlation between Na and Cl (correlation coefficient of 0.99) (Figures

5.4a and b) suggest that this water has interacted with saline fluids. Hydrologic flow within the Mannville Group is confined to the Lower Mannville in the north and the entire Mannville Group forms a single aquifer in the south (Bachu, 1999; Anfort et al., 2001). The Lower Mannville is comprised of non-marine shale and sandstones and the Upper Mannville is influenced more by marine deposits due to transgressive/regressive cycles. The Mannville group also overlies an erosional boundary and there may also be mixing with lower more saline aquifers occurring.

The interaction between the marine deposits in the Mannville group and the produced fluids as well as deeper and more saline aquifers may influence the 104 formation of these Na-Cl water types. Sulfate concentrations were negligible suggesting that bacterial (dissimilatory) sulfate reduction had occurred.

5.3.3 Redox State

In assessing the redox state it must be kept in mind that several shallow groundwater wells had screened intervals exceeding 10 m and that the produced fluids were in part swabbing fluids from wells comingled over several coal zones interlayered with sandstone units. Nevertheless, water chemistry parameters were used to classify the redox environment in different zones using principles described in Berner (1981) and Apello & Postma (2005). Oxic water contains significant amounts of dissolved oxygen and occasionally nitrate, whereas post-oxic water contains neither dissolved oxygen nor nitrate. Post-oxic waters are further subdivided into non-sulfidic waters, where manganese and iron act as the dominant oxidizing agents, and sulfidic waters where sulfate is reduced to H2S via bacterial (dissimilatory) sulfate reduction (BSR). The final and most reducing stage of this redox ladder is the methanic stage where methanogenic bacteria produce

CH4 either by fermentation of acetate or reduction of CO2.

Average concentrations of DO, NO3, Mn, Fe, SO4, and CH4 are summarized in Figure 5.6. Five shallow groundwater samples contained more than 0.1 mg/L nitrate. Sixteen shallow groundwater samples were characterized by negligible dissolved oxygen and nitrate contents but had sulfate concentrations > 40 mg/L indicating a post-oxic but not yet sulfidic redox environment. Nitrate concentrations in the SGW could derive from agriculture or sewage discharge. One method to determine the source of nitrate within the SGW would be to analyze the isotopic 105 value of N in nitrate. Most of the SGW samples had such a low concentration of nitrate that these isotopic values could not be obtained. High sulfate concentrations in the SGW suggest that pyrite oxidation by nitrate reduction could have occurred based on the following reactions (Appelo and Postma, 2005):

- + 2+ 2- 5FeS2 + 14NO3 + 4H Æ 7N2 + 5Fe + 10SO4 + 2H2O

and

2+ - + 5Fe + NO3 + 7H2O Æ 5FeOOH + ½N2 + 9H

Even though the concentration of nitrate within the SGW seems somewhat insignificant, most samples that contain nitrate appear to have less iron present.

Similarly, these same samples have a lower concentration of sulfate, suggesting that the reduction of nitrate has not yet occurred via pyrite oxidation.

Iron can be found in aquifer sediments in the form of iron oxides, which coat quartz and feldspar grains. Iron bearing silicates can also be present as well as iron-oxide minerals (such as magnetite and ilmenite). The dissolution of iron bearing silicates and iron rich minerals can release Fe2+ into the groundwater, and in turn, potentially precipitate oxyhydroxides if the groundwater comes into contact with atmospheric oxygen. Goethite and hematite are both oversaturated in the

SGW samples (Table 5.2a), suggesting potential contact with atmospheric oxygen¸ which has lowered the concentration of Fe in the SGW. Bacterial sulfate reduction may also be contributing to low Fe concentrations in SGW.

Fifteen shallow groundwater samples had sulfate concentrations below 40 mg/L and methane in free gas exceeding 18.5 % v. The depth of the screen for

107 nitrate and dissolved manganese, had negligible sulfate concentrations, but elevated Fe concentrations and dissolved methane contents. This suggests a highly reducing methanic redox environment.

In the Mannville and HSCN/BRG samples, iron and manganese compounds could potentially be reduced by organic matter (organic carbon) or BTEX, which releases iron and bicarbonate, iron, and manganese into the water. Once this reaction has occurred, siderite can precipitate. Only calcite is oversaturated in most HSCN/BRG waters and siderite appears to be mainly undersaturated (Table

5.2b). On the other hand, siderite is present within the cleats of Mannville coals while there is little calcite (Gentzis et al., 2008). Based on the saturation indices listed in Table 5.2c, both siderite and calcite could potentially precipitate as the waters are oversaturated with these mineral phases in the Mannville formation.

The Mannville waters do contain higher concentrations of iron, which suggests that the rate at which the dissolution of sulfide minerals occurs is greater than the rate at which siderite may precipitate within these aquifers.

5.3.4 Bacterial Sulfate Reduction

In reducing environments, anaerobic bacteria utilize the available dissolved sulfate to oxidize organic matter (such as hydrocarbons, amino acids, carbohydrates, and fatty acids) during the process of bacterial (dissimilatory) sulfate reduction (BSR) (Fauville et al., 2004; Langmuir, 1997):

2- + SO4 + CH4 + 2H Æ H2S + CO2 + 2H2O 108

There are three main conditions that must be met in order for BSR to occur:

(1) there must be a source of sulfate in order for it to be used as an electron acceptor; (2) there must be sufficient amounts of organic matter available that can be used by sulfate reducing bacteria; (3) there must be sulfate reducing bacteria at the site of sulfate reduction. Stable isotope techniques can be used to determine the occurrence of BSR in a system, since sulfate reducing bacteria preferentially utilizes the light 32S isotope and hence the remaining dissolved sulfate becomes enriched in the heavier 34S isotope (Spiker et al., 1994; Harrison & Thode 1957).

The majority of the SGW had high sulfate concentrations (> 40 mg/L; Fig.

5.3a) and the isotopic composition of sulfate suggested pyrite oxidation as the most likely source of sulfate (Figs. 5.5, 5.7). However, four SGW samples were characterized by elevated δ34S and δ18O values of sulfate (Fig. 5.5) in concert with sulfate concentrations < 40 mg/L (Fig. 5.7), suggesting that these samples were affected by BSR. SGW samples that had low sulfate concentrations also contained

13 methane in free gas ranging from 18.5 to 53.9 vol % with δ Cmethane values characteristic for biogenic gas (Table 5.4a). There is little evidence that suggests that the coals associated with the SGW are a source or sink for sulfur compounds in the groundwater.

Produced fluids obtained from the HSCN/BRG had comparatively low sulfate concentrations ranging from 3.3 to 260 mg/L combined with elevated

34 δ Ssulfate values ranging from +6.7 to +33.8 ‰ (Figure 5.7) indicating that bacterial sulfate reduction was occurring. Sulfate concentrations in the produced waters from the Mannville formation were too low for stable isotope analysis likely as a result of bacterial sulfate reduction. Previous studies of produced fluids from the

110 isotope techniques can be used to determine the geochemical source and history of gases such as methane in groundwater and formation water systems. Methane that has been generated through biogenic methanogenesis pathways tends to be strongly isotopically enriched in 12C and has δ13C values between -110‰ and circa

-50‰ (e.g. Whiticar, 1999; Aravena et al., 2003). Thermogenically generated methane tends to be slightly more enriched in 13C relative to biogenic methane with

δ13C values of less than -50‰ to -20‰ (Whiticar, 1999; Aravena et al., 2003).

Based on studies by Whiticar (1999) and Rowe and Muehlenbachs (1999b), it is however difficult to distinguish between thermogenic and biogenically produced gas with δ13C values between -50‰ and -60‰ using carbon isotope data alone.

The comparatively low average δ13C values of methane (-72.1 ± 6.8 ‰) and ethane (-50.8 ± 8.3 ‰) in free gas from SGW (Table 5.4a) are consistent with a biogenic origin of these hydrocarbon gases. The δ13C and δ2H values for SGW

(n=13) were plotted using the Whiticar et al. (1986) and Whiticar (1999) compositional fields in order to determine the potential sources of methane (Figure

5.8) The SGW samples mainly plot within the mix and transition area located between the methyl-type fermentation and bacterial CO2 reduction fields. In order to further investigate the predominant methane formation processes, δ13C values

2 of CO2 and DIC and δ H values of methane were evaluated.

13 13 δ CCO2 values are plotted versus δ CCH4 values in Figure 5.9. Typical carbon isotope fractionation factors (αCO2-CH4) for CO2 reduction vary between 1.09 and 1.06 (e.g. Gorody, 2006). The αCO2-CH4 values observed for SGW ranged between 1.05 and 1.07 suggesting that CO2 reduction was the predominant biogenic methane formation process for several SGW samples. This interpretation 111 is supported by the hydrogen isotope composition of methane (Table 5.4a).

According to Whiticar (1999) hydrogen used to form methane via the CO2 reduction pathway is mainly derived from water, whereas in the methyl-type fermentation pathway the hydrogen is derived from both water and metabolized methyl substrates (Whiticar, 1999; Aravena et al., 2003). Based on studies by

Aravena et al. (2003) and Harrison et al. (2006a) the expected range of δ 2H values for biogenic methane due to CO2 reduction is described by the following relationship:

2 2 δ HCH4 = δ HH2O – (160 ± 10) ‰

2 The δ Hmethane values of free gas in SGW ranged from -336.2 to -277.3 ‰

2 while δ Hgroundwater values varied between -170.7 to -96.3 ‰. Figure 5.10 reveals that the majority of the free gas samples from SGW fall within or near this window

2 2 with an average difference between δ Hgroundwater and δ Hmethane values of approximately 150 ‰, suggesting that CO2 reduction is the main process of biogenic methane formation. The δ13C values of dissolved inorganic carbon plotted versus those of methane in SGW (Figure 5.11) also suggest that methanogenesis in SGW predominantly occurred via the CO2 reduction pathway with some samples potentially influenced by acetate fermentation.

116 constant. The authors also suggest that 100 % of hydrogen in methane formed via

CO2 reduction derives from formation water, whereas only 25 % of the hydrogen in methane formed via acetate fermentation is from formation water. The relative fraction of methane produced from acetate fermentation is expressed as:

2 2 f = (δ HH20 - δ HCH4 – 160 ‰) 2 (0.857 x δ HH20 + 233)

Based on the δ2H values for methane and water in SGW, the fraction of methane produced via CO2 reduction in the free gas samples (n = 12) obtained from SGW varied between 85.2 and 100 % with an average of 98 ± 4 % (Table

5.4a).

There appears to be no correlation between the concentration of methane present in the SGW samples and the formation in which these wells were completed, suggesting that there must be another parameter involved that governs the occurrence of methane in shallow groundwater. SGW with high concentrations of methane was obtained from wells that had completion depths ranging from 49 m to 223 m. Most of the other shallow groundwater wells have been completed at shallower depths, suggesting that the depth of the wells and hence the redox environment are the key drivers for methane occurrence in shallow groundwater.

Dissolved hydrocarbon gases from the HSCN/BRG had average δ13C values of -54.0 ± 4.1 ‰ for methane, -36.5 ± 2.4 ‰ for ethane and -29.4 ± 1.0 ‰ for propane (Table 5.4b). The δ13C values of methane and ethane as well as the presence of higher alkanes in these samples (Figure 5.12) suggest a mixture of

119

Dissolved hydrocarbon gas from the Mannville Formation had the highest average δ13C values of -49.4 ± 3.6 ‰ for methane, -28.8 ± 2.1 ‰ for ethane and

-26.9 ± 1.1 ‰ for propane (Table 5.4c). The presence of propane in several samples suggests that the Mannville produced fluids contain a significant thermogenic gas component (Figure 5.12). Some of the samples from the

Mannville Formation had δ13C values similar to those of the HSCN/BRG (-53.4 to

-57.4 ‰) suggesting an overprint of late-stage biogenic methane in some coals that have already undergone thermogenesis (Rice, 1993). This late-stage biogenic methane results in more negative δ13C values than would be expect with the presence of heavier hydrocarbons (Rice, 1993). The thick Mannville coalbeds are older and generally are of a higher rank than the HSCN/BRG coals and are subjected to a greater overburden (Figure 5.13). Thermogenic gas generally dominates in coals of higher rank that have undergone a high degree of thermal

13 maturation (Taylor et al., 1998). The enrichment of CDIC for most produced fluids

13 from the Mannville and HSCN/BRG (Figure 5.12) with δ CDIC values of up to

+15 ‰ suggests that methanogenesis is occurring in the formation (e.g. Sharma &

Frost, 2008). The biogenic gas component in the Mannville and HSCN/BRG was mainly formed via acetate fermentation since αCO2-CH4 values between 1.02 and

1.07 (Figure 5.10) are characteristic for methyl-type fermentation processes (see also Figures 5.11 and 5.12).

5.4 Summary

This study has generated detailed baseline data characterizing fluids and gases obtained from shallow groundwater wells, and from CBM wells producing 120 from the Horseshoe Canyon/Belly River group and the Mannville formation revealing significant differences in chemical and isotopic compositions. Shallow groundwater had the lowest average total dissolved solids (1037 mg/L). Most samples belonged to the Na-HCO3-SO4 water type and average sulfate concentrations of 185 mg/L were recorded. The Horseshoe Canyon/Belly River

Group swabbing fluids had higher average TDS (5427 mg/L) and a Na-HCO3 water type. The comparatively low average sulfate concentrations (47.7 mg/L) were due to the occurrence of bacterial (dissimilatory) sulfate reduction. The produced fluids from the Mannville Formation had the highest average TDS contents of 74,500 mg/L, a Na-Cl water type, and the lowest redox state with negligible sulfate concentrations and elevated iron concentrations. Shallow groundwater and produced fluids from the HSCN/BRG formation and the Mannville group had distinct δ2H and δ18O values and plotting δ18O values versus total dissolved solids was found to be an effective approach to distinguish the waters. Methane was found in several shallow groundwater samples and its average δ13C (-72.1 ±

6.8 ‰) and δ2H values (-297 ± 17) indicated a biogenic origin predominantly from

13 CO2 reduction. Dissolved gases from the HSCN/BRG with average δ C values of methane of -54.0 ± 4.1 ‰ and ethane of -36.5 ± 2.4 ‰ and traces of higher alkanes suggest a mixture of predominantly biogenic and some thermogenic gas.

Dissolved hydrocarbon gas from the Mannville Formation had the highest average

δ13C values of -49.4 ± 3.6 ‰ for methane, -28.8 ± 2.1 ‰ for ethane and

-26.9 ± 1.1 ‰ for propane. The presence of higher alkanes suggests that the

Mannville produced fluids contain an appreciable thermogenic gas component. The biogenic gas component in the HSCN/BRG and the Mannville Formation was 121

mainly formed via acetate fermentation since αCO2-CH4 values between 1.02 and

1.07 are characteristic for methyl-type fermentation processes.

δ18O values of the fluids in concert with total dissolved solids, and the isotopic composition of methane and ethane are sufficiently distinct in shallow groundwater and produced fluids from HSCN/BRG and the Mannville Formation that they may serve as tracers for potential contamination of shallow groundwater with produced fluids or gases. 122

CHAPTER 6: TRACE ELEMENT AND RARE EARTH ELEMENT

GEOCHEMISTRY

6.1 Introduction

This chapter provides a brief description of the geochemistry and a detailed discussion of trace element and rare earth element (REE) concentrations of the produced fluids from two major coal deposits in western Canada, the Mannville

Formation and the Horseshoe Canyon/Belly River Group (HSCN/BRG), and shallow groundwater in this region. This section evaluates how the depositional environment, redox conditions, and water-rock interactions influence the trace element and rare earth element distributions in the produced fluids and SGW of the study area. In addition, the dissolved constituents and the trace metal content of the produced waters and SGW will be compared to freshwater guidelines (Health

Canada, 2008). Rare earth element distributions of the produced fluids and SGW will be compared to determine whether REEs can be used to monitor potential contamination of SGW with CBM fluids.

6.2 Results and Discussion

6.2.1 Geochemistry and Depositional Environment

An in-depth discussion of variabilities of major ion concentrations and isotope ratios of fluids and gases from the Mannville Group, the HSCN/BRG and

SGW is provided elsewhere (see Chapter 5). Here, ranges and average values for geochemical parameters are discussed briefly in an attempt to describe the 123 geochemical environment that could influence trace element and rare earth element concentrations in the fluids.

The relative distribution of major cations and anions for the collected produced fluids and the SGW are summarized in a Piper diagram in Figure 6.1 and a summary of geochemical parameters is provided in Table 6.1. Mannville waters are Na-Cl type (Figure 6.1) with TDS values ranging from 31,100 to 89,000 mg/L

(average 74,500 mg/L). The B content of the Mannville produced fluids ranges from 6 to 31 mg/L (Table 6.1). Such elevated B contents are attributed to the brackish/marine depositional environment of the Mannville Group (Banerjee and

Goodarzi, 1990). The samples are characterized by pH values ranging from 6.3 to

7.5 and contain negligible sulfate. Higher concentrations of iron were observed in the Mannville fluids compared to HSCN/BRG fluids and shallow groundwater

(Table 6.1). According to Gentzis et al. (2008) siderite is present within the cleats of Mannville coals, while there is little calcite. Hence, siderite dissolution is a potential cause for the elevated iron concentrations in Mannville fluids. The

HSCN/BRG swabbing fluids were of a Na-HCO3 and Na-Cl type (Figure 6.1) with

TDS values ranging from 469 to 14,700 mg/L, with an average of 5,430 mg/L.

Moderate B concentrations (0.05 to 1.27 mg/L) suggest that the strata have been partially influenced by brackish waters at the time of deposition (Dawson et al.,

1989; Smith, 1989; Swaine and Goodarzi, 1995; Goodarzi, 2005). The pH of

HSCN/BRG produced fluid is more neutral to basic (6.8 to 11.2) relative to fluid samples from the Mannville Formation. HSCN/BRG fluids are low in sulfate and have low iron concentrations compared to Mannville fluids (Table 6.1). The SGW

125 strata in which the water flows were deposited in a moderately fresh water environment. Sulfate concentrations range from 0.5 to 1010 mg/L with the majority of the samples exceeding 100 mg/L. δ34S values of sulfate below +10 ‰ in concert with high sulfate concentrations (Figure 6.2) in the SGW are generally due to oxidation of sulfide minerals and potentially the mineralization of organo-sulfur compounds present in the overlying Laurentide tills (Van Stempvoort et al., 1994;

Fennell and Bentley, 1998; see Chapter 5).

Table 6.1: Ranges and average values of selected chemical and isotopic parameters for produced fluids and SGW.

Horseshoe Canyon Formation/ Parameters Mannville Formation Shallow Groundwater Belly River Group

Water Type Na-Cl Na-HCO3 Na-HCO3 to Na-HCO3-SO4 pH 6.3 - 7.5 6.8 - 11.2 6.8 - 9.2 TDS (mg/L) 31,100 - 89,000 469 - 14,700 360 - 2630, 4300 Concentrations of Major Ions Calcium (mg/L) 379.7 - 2956 5.1 - 279.9 0.95 - 194.7 Sodium (mg/L) 11511 - 32013 97.3 - 4420 34.1 - 1820.2 Magnesium (mg/L) 225 - 918.9 1.2 - 35.0 0.11 - 45.8 Boron (mg/L) 6 - 31 0.05 - 1.27 0.13 - 1.4 Iron (mg/L) 3 - 63 0.001 - 16.38 0.02 - 0.42 Chloride (mg/L) 16967 - 52364 35.7 - 1700 1 - 1530 Bicarbonate (mg/L) 99 - 1646 197 - 8864 371 - 2040 Sulphate (mg/L) 8.18 - 80.6 3.34 - 260.0 0.5 - 1010 Ca2+/SO42- (Molar Ratio) 11.4 - 758.5 0.1 - 27.4 0.01 - 58.1 Isotopic Composition of Water δ18OH2O (‰) -11.2 to -5.5 -13.4 to +5.2 -21.4 to -8.7 δDH2O (‰) -106.1 to -83.2 -11.9 to +8.5 -170.7 to -96.3 Isotopic Composition of Dissolved Constituents 34 δ Ssulphate (‰) - +6.7 to +33.8 -26.6 to +34.3 13 δ CDIC (‰) -14.8 to +14.9 -15.5 to + 4.4 -20.0 to +21.2 Isotopic Composition of Gases 13 δ Cmethane (‰) -49.4 ± 3.6 (n=24) -54.0 ± 4.1 (n=45) -67.5 ± 9.4 (n=29) 13 δ Cethane (‰) -28.8 ± 2.1 (n=24) -36.5 ± 2.4 (n=42) -47.9 ± 4.9 (n=10) 13 δ Cpropane (‰) -26.9 ± 1.1 (n=23) -29.4 ± 1.0 (n=38) Not Detected

127 sulfate reducing bacteria preferentially use the light 32S isotope, the remaining dissolved sulfate becomes enriched in 34S as sulfate concentration decrease due

2+ 2- to BSR. HSCN/BRG samples have Ca /SO4 molar ratios ranging from 0.1 to

2+ 2- 27.4 (Table 6.1) and most of the samples have a Ca /SO4 ratio >> 1. High

2+ 2- 34 Ca /SO4 molar ratios in concert with elevated δ S values suggest that bacterial

(dissimilatory) sulfate reduction (BSR) must have lowered the sulfate concentrations significantly. Sulfate concentrations in the Mannville waters were

2+ 2- insufficient for stable isotope analysis, but very high Ca /SO4 molar ratios (Table

6.1) for the Mannville fluids indicate a strong depletion of dissolved sulfate relative to Ca2+, in all likelihood also due to BSR. This indicates that highly reducing conditions prevail in the Mannville fluids in most of the HSCN/BRG swabbing fluids and some shallow groundwater samples. Sulfidic redox conditions are a pre­ requisite for methanogenesis to occur.

Shallow groundwater that contained low sulfate concentrations also contained free gas with methane contents ranging from 167,000 ppmv to 960,000 ppmv. Gas generation in reducing subsurface environments may occur via two mechanisms (Rice, 1993; Whiticar, 1999): (i) Bacterial generation of methane

(methanogenesis) by the reduction of organic material (e.g. acetate) or by the reduction of carbon dioxide; and (ii) thermogenic gas generation through thermal maturation e.g. of coal. Stable isotope techniques can be used to elucidate the formation process for gases such as methane in groundwater and formation water systems. Methane that has been generated through biogenic methanogenesis pathways tends to be strongly enriched in 12C and has δ13C between -110 ‰ and circa -50 ‰ (Whiticar, 1999). Thermogenically generated methane tends to be 128 slightly more enriched in 13C relative to biogenic methane with δ13C values often ranging from less than -50 ‰ up to -20 ‰ (Whiticar, 1999). However, based on studies by Whiticar (1999) and Rowe and Muehlenbachs (1999), it is difficult to distinguish between thermogenic and biogenically produced gas with δ13C values between -50 ‰ and -60 ‰ using carbon isotope data alone.

The average δ13C values of methane, ethane, and propane from dissolved

(CBM production fluids) and free hydrocarbon gas samples (shallow groundwater) are summarized in Table 6.1. The carbon isotope values for methane and ethane are distinct between the three water types. Dissolved hydrocarbon gas from the

Mannville Formation has the highest average δ13C values of -49.4 ± 3.6 ‰ (n=24) for methane, -28.8 ± 2.1 ‰ (n=24) for ethane and -26.9 ± 1.1 ‰ (n=23) for propane. These carbon isotope values and the presence of propane in the samples suggest that the Mannville produced fluids contain a thermogenic gas component. The Mannville coals can be up to 4-m thick and are fairly extensive.

These coals are older and generally are of a higher rank than the HSCN/BRG coals and have been subjected to a greater overburden. Thermogenic gas generally dominates in coals of higher rank that have undergone a high degree of thermal maturation (Taylor et al., 1998).

Dissolved hydrocarbon gases from the HSCN/BRG were characterized by more negative average δ13C values of -54.0 ± 4.1 ‰ (n=45) for methane, -36.5 ±

2.4 ‰ (n=42) for ethane, and -29.4 ± 1.0 ‰ (n=38) for propane (Table 6.1). The more negative δ13C values of methane and ethane from the HSCN/BRG suggest a higher proportion of biogenic gas, but the presence of propane in many

HSCN/BRG fluids suggests that there is also a presumably small thermogenic gas 129 component. Methane and ethane for free gases in SGW have even lower average

δ13C values of -67.5 ± 9.4 ‰ (n=29) and -47.9 ± 4.9 ‰ (n=10), respectively, compared to that of the produced fluids (Table 6.1). This, and the fact that no higher alkanes were present, is indicative of a biogenic origin for the dissolved and free gases in the SGW in the region.

6.2.2 Trace Elements

Trace element concentrations were determined and compared to national drinking water guidelines (Health Canada, 2008) to assess whether the waters contain high concentrations of elements that could affect human health in the hypothetical case that CBM production fluids impact shallow groundwater used for drinking water purposes. The concentrations were then compared to concentrations of trace elements in coal that were normalized based on average values of elements in the Earth’s crust in order to better understand the source of the trace elements (Mason and Moore, 1982). Elements of environmental concern include: As, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se, V, and Zn (Tables 6.2a, b, and c). All of the Mannville waters contained concentrations of As and Se that exceeded drinking water guidelines (5 μg/L and 10 μg/L, respectively) (Health

Canada, 2008) (Table 6.2a). High concentrations of As in the Mannville fluids are likely caused by decomposition of pyrite (Cody et al., 1999; Gentzis and Goodarzi,

1998) and it is possible that Se is derived from the same process since Se may occur as solid solution in pyrite. Coals from the Mannville also appear to have high positive Sb and Se anomalies, and most of the coals appear to also be enriched in

As (Figure 4.4a). As stated in Chapter 4, high concentrations of Se and As are 130 found in Mannville coals, therefore it is highly likely that the interaction between fluids and the coals may have influenced the As and Se concentrations in the produced fluids. Two samples contained concentrations of Cd above the maximum allowable concentration (5 μg/L) reported in the drinking water guidelines

(Health Canada, 2008). According to Hitchon et al. (1999) the maximum concentration of cadmium found in formation waters from the Alberta Basin is 760

μg/L. The maximum Cd concentration observed in Mannville waters is 11.8 μg/L

(Table 6.2a). Cadmium is mainly associated with sphalerite (ZnS) in coal, but can also be found in clays, carbonates, and other sulfide minerals such as pyrite

(Gluskoter and Lindahl, 1973; Kirsch et al., 1980; Swaine, 1990; Finkelman, 1995).

Hence, cadmium could be derived from the dissolution of CdCO3, desorption from mineral surfaces, or dissolution of sulfide minerals (Lemay, 2003). Three samples contain elevated Hg concentrations above the drinking water guidelines. The

HSCN/BRG produced fluids had As concentrations below the drinking water guideline of 5 μg/L with the exception of 8 samples (PKB12-6, PKB13-7, PKB1-8,

KC1-1, KC2-1, KC15-1, KC37-1, KC38-1), whereas the majority of the waters contained Se concentrations above drinking water guidelines (a maximum allowable concentration of 10 μg/L) (Table 6.2b). In contrast, only two SGW samples contained As concentrations (7.5-10.5 μg/L) above the guideline, and only three groundwater samples contained Se concentrations (12.4-70.1 μg/L) above the guideline (Table 6.2c). The HSCN and Scollard coals discussed in Chapter 4 are enriched in Sb and Se, with some HSCN samples showing enrichment in Cs.

Arsenic was enriched in both coals, but values were lower in the HSCN compared to the Scollard and Mannville coals. These high concentrations of As and Se in the 131

Table 6.2a: Concentrations of selected trace elements in Mannville Formation fluids. Samples in bold are above the Maximum Allowable Concentrations (MAC) for drinking water guidelines (Health Canada, 2008).

As Cd Co Cr Cu Hg Mo Ni Pb Sb Se V Zn Sample (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) PKB1 135.6 n.d. 4.2 n.d. 287.3 n.d. n.d. n.d. n.d. n.d. 1100.6 154.0 57.6 PKB2 139.0 n.d. 6.1 n.d. 298.3 10.1 n.d. n.d. n.d. n.d. 1142.0 176.5 106.9 PKB3 143.4 n.d. 4.1 n.d. 290.2 n.d. n.d. n.d. 13.2 n.d. 1266.5 187.8 101.4 PKB4 151.7 n.d. 3.9 n.d. 303.0 n.d. n.d. n.d. 14.3 n.d. 1248.7 200.6 81.6 PKB5 147.9 n.d. 3.1 n.d. 807.5 n.d. n.d. n.d. 32.5 n.d. 1196.2 204.0 1461.7 PKB6 157.4 n.d. 2.8 n.d. 333.2 n.d. n.d. n.d. 19.9 n.d. 1219.2 196.9 338.0 PKB7 164.7 n.d. 3.7 n.d. 359.5 n.d. n.d. n.d. n.d. n.d. 1269.1 205.4 223.8 PKB8 155.9 8.1 3.4 n.d. 388.7 n.d. n.d. n.d. 57.4 n.d. 1270.4 219.1 406.9 PKB9 155.1 n.d. 4.2 n.d. 343.7 n.d. n.d. n.d. 21.4 n.d. 1213.9 214.5 151.2 PKB1-1 144.8 n.d. 3.0 n.d. 352.7 n.d. n.d. n.d. n.d. n.d. 1112.5 199.7 408.5 PKB2-1 146.9 n.d. 4.3 n.d. 339.7 n.d. n.d. n.d. 12.9 n.d. 1118.9 210.5 190.7 PKB3-1 139.6 11.8 3.6 n.d. 298.5 n.d. n.d. n.d. n.d. n.d. 948.8 192.2 132.9 PKB4-1 139.5 n.d. 3.8 n.d. 366.0 n.d. n.d. n.d. n.d. n.d. 1146.6 187.3 180.1 PKB5-1 155.0 n.d. 2.2 n.d. 339.7 n.d. n.d. n.d. 13.8 n.d. 1231.5 198.9 338.9 PKB1-4 127.7 n.d. 4.5 n.d. 255.1 n.d. n.d. n.d. n.d. n.d. 945.5 156.5 125.7 PKB2-4 156.6 n.d. 3.6 n.d. 277.3 n.d. n.d. n.d. n.d. n.d. 989.9 177.7 81.6 PKB3-4 135.1 n.d. n.d. n.d. 294.0 n.d. n.d. n.d. n.d. n.d. 1053.1 179.3 72.1 PKB4-4 152.6 n.d. 4.4 n.d. 284.3 n.d. n.d. n.d. 15.2 n.d. 1090.5 170.9 88.6 PKB5-4 55.1 n.d. n.d. n.d. 147.4 n.d. n.d. n.d. n.d. n.d. 407.5 73.5 25.0 PKB01-9 125.2 n.d. 2.3 22.7 109.7 n.d. 2.7 n.d. 92.1 0.6 459.5 209.6 2609.8 PKB02-9 122.2 n.d. 1.8 23.4 85.8 n.d. 7.1 n.d. 14.9 0.6 380.6 236.0 74.7 PKB03-9 140.9 n.d. 2.4 19.9 95.5 0.5 1.8 n.d. 24.5 0.8 432.6 249.4 100.9 PKB04-9 153.6 0.1 3.2 18.7 87.8 1.0 1.9 n.d. 43.9 0.7 396.1 264.7 200.5 PKB05-9 157.8 n.d. 2.9 17.2 97.9 3.0 1.0 n.d. 32.6 0.2 550.2 290.1 868.2 131 132

Table 6.2b: Concentrations of selected trace elements in Horseshoe Canyon/Belly River Group swabbing fluids. Samples in bold are above the Maximum Allowable Concentrations (MAC) and samples in bold and underlined are above the Aesthetic Objective (AO) for drinking water guidelines (Health Canada, 2008).

As Cd Co Cr Cu Hg Mo Ni Pb Sb Se V Zn Sample (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) PKB1-5 1.3 0.73 0.23 1.8 6.8 n.d. 34.4 1.1 2.9 0.17 11 0.7 394.3 PKB2-5 3 0.77 0.21 6.4 40 n.d. 448.4 0.2 52.2 2.43 28 1.8 311.1 PKB3-5 3.2 0.56 0.39 4.1 22.4 n.d. 24 0.3 16.5 1.64 33.7 2.6 320.6 PKB4-5 4.2 0.91 0.47 9.1 102.7 n.d. 30 0.4 22.1 0.93 40.4 2.4 939.1 PKB5-5 5 0.43 0.98 9.4 29 1.3 17.4 7 2.2 0.52 84 3.5 4320.5 PKB6-5 3.3 0.41 0.19 4 96.7 n.d. 74.4 2 22.4 2.13 27.6 2.3 449.8 PKB7-5 n.d. n.d. 0.02 n.d. 14.9 n.d. 1 0.2 0.7 0.14 1.4 n.d. 40.5 PKB8-5 3.1 0.35 0.13 2.7 67.2 n.d. 60.7 1.2 9.5 1.26 32.5 2.8 440.8 PKB1-6 3.6 0.5 0.05 148.7 18 n.d. 39.6 0.5 13.5 1.43 19.7 2.2 154.6 PKB2-6 3.4 15.3 0.43 26.5 12.5 n.d. 91.9 2.2 8.2 1.84 18.4 1.9 345.8 PKB3-6 n.d. 0.1 0.04 1.2 0.9 n.d. 3 0.2 0.3 n.d. 2.2 0.2 71.9 PKB4-6 3.6 5.13 0.54 23.9 41.6 0.3 5.8 n.d. 2.9 0.36 40.8 2 5638.5 PKB5-6 0.6 76.74 0.24 4.5 5.8 n.d. 6.5 0.5 5.8 0.6 6.3 0.3 608.9 PKB6-6 0.5 1.73 0.27 2 3.5 n.d. 16.4 3.1 13.6 0.72 6.5 0.2 990.3 PKB7-6 1.3 2.64 0.31 11.4 11.7 n.d. 14.5 1 2.7 1.33 8.5 0.7 2070.9 PKB8-6 n.d. 0.06 0.02 n.d. 0.9 n.d. 7.1 0.3 0.3 0.16 1 n.d. 38.9 PKB9-6 2 0.4 0.17 6.3 15.5 n.d. 27.6 n.d. 3.8 0.45 22.9 1.2 292.4 PKB10-6 3.3 0.39 0.3 20.9 11.7 n.d. 12 1.7 2.6 0.53 35 2.1 852 PKB11-6 1.7 0.52 0.42 6.2 10.6 n.d. 36.3 4.1 3 1 18 1.4 589.5 PKB12-6 13.4 0.1 0.49 4.8 19.4 n.d. 263.3 6.3 58.4 5.26 21.5 4.1 631 PKB13-6 n.d. 0.08 0.07 1 3.2 n.d. 10.2 0.4 6.2 0.39 2.3 0.2 392 PKB14-6 1.8 0.45 0.18 5.5 9.9 n.d. 70.3 0.5 17.2 0.74 17.7 1.2 131.3 PKB1-7 3.8 0.35 1.46 8.1 37.5 n.d. 28 0.8 13.1 1.52 37.4 2.2 96.5 PKB2-7 3.3 0.26 1.21 15.6 442.2 n.d. 7.4 n.d. 5.4 0.56 22 1.9 463 PKB3-7 4.7 0.29 0.62 10.2 111.2 n.d. 52 0.2 10.1 1.65 30.2 2.5 474.7 PKB4-7 3.3 0.28 5.96 8.5 1447.5 n.d. 38.7 13.1 13.8 1.28 24.7 2.3 37.1 PKB5-7 2.9 0.51 0.55 9.5 29.1 n.d. 22 n.d. 1.9 1.1 29.5 2 1012.3 PKB6-7 2.8 0.29 0.42 7 51.4 n.d. 28.1 1.5 17.8 1.4 28.1 1.9 913.6 PKB7-7 2.8 0.25 0.57 10 27.3 n.d. 54.9 2.8 34 1.11 34.6 2.1 862 PKB8-7 4.1 0.46 0.55 47.8 66.3 n.d. 97.5 2.6 98.4 0.99 46.4 2.5 1704 PKB9-7 3.6 0.56 0.43 19 44.2 n.d. 101.1 0.4 16.7 1.12 40.5 2.4 859 PKB10-7 2.8 0.37 0.58 30.6 32.2 n.d. 63.1 1.8 31.4 0.92 33.3 1.7 983.8 PKB11-7 3.4 0.27 9.78 12.6 53.8 n.d. 36.2 n.d. 33.9 1.13 36.2 2.5 1066.1 PKB12-7 2.3 0.24 0.29 5.1 26.1 n.d. 11.4 n.d. 3.9 0.53 29.8 2.1 216 PKB13-7 6 n.d. 0.56 9.7 260.8 n.d. 104.2 3.2 6.1 1.33 45.7 3.2 58.7 PKB14-7 2.3 n.d. 0.21 7.8 39.8 0.1 9.2 n.d. 1.8 0.6 19.2 1.6 59 PKB15-7 3.1 n.d. 0.31 13.3 107.6 n.d. 132.2 0.9 11.2 0.54 40.2 2.5 52.5 PKB16-7 2.7 0.26 0.16 43.5 23.1 0.6 10.8 0.1 5.2 0.6 21.6 2 266.8 PKB17-7 2.8 n.d. 0.59 21.6 19.8 n.d. 35.3 1.8 4 1.21 26.5 2.1 1148.7 PKB18-7 2.4 n.d. 0.17 8.2 13.7 0.3 8 0.3 1.1 0.84 29.9 2.2 188.3 PKB1-8 5.1 1.07 1.35 17.6 42.6 n.d. 60.2 n.d. 4 0.56 58.6 3.5 3090.6 PKB2-8 n.d. n.d. 0.24 2 2.5 n.d. 16.7 2 0.4 0.67 16.5 0.3 521.9 PKB3-8 1.2 n.d. 0.07 3.7 5.3 n.d. 22.9 0.7 0.6 1.22 26.2 0.7 8.9 PKB4-8 3.8 n.d. 1.23 16.8 25 0.5 27.9 1.9 1.4 0.51 66.3 2.5 1987.3 PKB5-8 0.8 n.d. 0.02 1.4 4.7 n.d. 6.3 0.1 5.7 0.41 2.4 n.d. 180 PKB6-8 0.6 n.d. 0.54 2 3.3 n.d. 18.4 6.7 1.9 0.85 8.9 0.4 485.5 KC1-1 10 n.d. 0.26 n.d. 3.1 13.8 2.1 n.d. n.d. n.d. 129.6 15.5 67.9 KC2-1 6.4 n.d. 0.21 n.d. 3.1 8.6 101.3 n.d. 3.3 0.82 74.8 11.5 103.2 KC3-1 n.d. 0.51 n.d. n.d. 4 7.6 30.7 n.d. 3.1 n.d. 31.4 7.2 40.8 KC4-1 n.d. 0.81 0.33 13.5 11 3.2 15.1 n.d. 3.2 n.d. 20 8 122.2 KC12-1 2.3 0.16 0.12 0.8 4.2 0.1 15.6 1.2 1.9 0.81 6.2 3.5 42.4 KC13-1 1.2 0.13 0.21 0.5 4.2 0.1 12.4 1.4 1.8 0.46 2.5 1.9 38.7 KC14-1 n.d. 0.44 0.33 n.d. 2.9 0.1 2.4 2.6 1.5 0.23 n.d. 0.5 706 KC15-1 5.4 n.d. 0.61 n.d. 22.6 n.d. 9.7 82.2 2.6 0.61 13.8 11.6 60.3 KC16-1 n.d. n.d. n.d. 10.9 6.4 n.d. 39.6 3.2 5.9 2.44 11 5.4 114.7 KC17-1 0.5 0.06 0.2 2.6 1 n.d. 11.9 3.2 1.8 0.87 1.5 0.7 214.8 KC37-1 6.6 n.d. 0.23 20.9 5.7 n.d. 3.6 n.d. n.d. n.d. 108.9 7.6 398.5 KC38-1 6.1 n.d. n.d. 17.5 4.3 n.d. 12 2.2 35.3 1.67 108.8 6.4 200.3 133

Table 6.2c: Concentrations of selected trace elements in SGW. Samples in bold are above the Maximum Allowable Concentrations (MAC) for drinking water guidelines (Health Canada, 2008).

As Cd Co Cr Cu Hg Mo Ni Pb Sb Se V Zn Sample (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) (μg/L) KC5-1 0.6 0.15 0.19 1.7 1.5 0.3 5.9 n.d. 0.4 n.d. 0.6 0.3 40.6 KC6-1 10.5 0.07 0.21 1 1 0.1 16 n.d. 0.2 0.2 0.5 0.2 12.6 KC7-1 n.d. 0.15 0.02 n.d. n.d. n.d. 0.8 n.d. n.d. n.d. n.d. n.d. 6.7 KC8-1 n.d. 0.17 0.23 n.d. 0.3 0.1 7.3 0.3 n.d. 0.11 0.5 n.d. 11.8 KC9-1 n.d. n.d. 0.04 n.d. 0.3 0.1 4.9 n.d. n.d. n.d. 0.7 0.2 n.d. KC10-1 2.2 n.d. 0.2 0.6 1.5 n.d. 1.3 0.6 0.3 0.17 0.5 0.4 8.2 KC11-1 n.d. n.d. n.d. n.d. 1.4 n.d. n.d. n.d. 2.2 n.d. n.d. n.d. n.d. KC20-1 0.8 n.d. 0.05 68.9 3.7 0.1 31 2.5 0.2 1.53 1 0.5 n.d. KC21-1 n.d. n.d. 0.15 3.1 0.3 0.1 0.4 n.d. 0.1 0.08 4.1 0.6 n.d. KC22-1 7.5 n.d. n.d. 5.4 n.d. 8.2 1n .d.1 .4n .d.70 .1 14.4 10.9 KC23-1 n.d. n.d. 0.04 n.d. 0.6 0.3 2.9 0.6 0.1 n.d. n.d. 0.3 7.9 KC24-1 n.d. n.d. n.d. 0.6 0.2 0.2 2.2 n.d. n.d. n.d. n.d. n.d. n.d. KC25-1 n.d. n.d. 0.08 1.5 0.1 0.1 3 n.d. n.d. n.d. 0.5 n.d. 0.9 KC26-1 0.7 n.d. 0.22 3.1 0.2 n.d. 0.5 n.d. n.d. n.d. 0.6 0.2 n.d. KC27-1 n.d. n.d. n.d. 0.5 0.1 n.d. 5.6 n.d. n.d. n.d. n.d. n.d. 0.6 KC28-1 0.5 0.18 0.02 0.6 0.3 n.d. 1.9 0.6 0.1 0.07 n.d. n.d. 12.1 KC29-1 n.d. n.d. 0.14 1 0.1 n.d. 18.6 0.4 0.1 n.d. 0.6 0.4 1.6 KC30-1 n.d. n.d. n.d. 1 0.3 n.d. 0.7 n.d. n.d. n.d. n.d. n.d. 0.8 KC31-1 n.d. n.d. 0.22 3.6 0.7 n.d. 3 0.7 0.4 0.08 n.d. 0.4 2.9 KC34-1 0.9 n.d. 0.02 7.2 0.2 0.2 17.7 1.5 0.1 2.3 n.d. n.d. 0.9 KC35-1 n.d. n.d. 0.04 15.5 1.9 n.d. 3.3 n.d. n.d. 0.1 0.9 0.2 1.2 KC36-1 n.d. n.d. 0.1 12.1 0.3 n.d. 1.8 n.d. n.d. n.d. 2.3 n.d. n.d. KC39-1 n.d. n.d. 0.05 14.6 1.6 0.1 0.9 0.3 0.2 n.d. 0.5 0.2 5.5 KC40-1 2.9 n.d. 0.49 12.6 1.9 n.d. 1.4 n.d. n.d. n.d. 1 n.d. 2.6 KC41-1 n.d. n.d. 0.05 13.3 5.4 n.d. n.d. n.d. 0.3 n.d. n.d. n.d. 13 KC42-1 1.7 n.d. 0.1 45.3 0.3 n.d. n.d. 0.4 n.d. n.d. 12.4 0.9 7.4 KC43-1 3.5 n.d. 0.69 12.9 0.8 0.1 0.9 1.3 n.d. n.d. 0.5 n.d. 5.1 KC44-1 n.d. n.d. 0.08 14.6 0.2 n.d. 8.3 0.5 0.1 n.d. 0.9 n.d. 0.6 KC45-1 n.d. n.d. 0.06 8.8 0.4 n.d. 3.7 n.d. n.d. n.d. 6.5 n.d. 1.9 KC46-1 3.3 n.d. 0.05 14 2.2 n.d. 7.3 n.d. n.d. n.d. 0.8 n.d. 1.3 KC47-1 3.6 n.d. 0.05 13.2 2.5 n.d. 7.1 n.d. n.d. n.d. 0.6 n.d. 1.1 KC48-1 n.d. n.d. 0.05 14 0.6 n.d. 5.7 n.d. n.d. 0.2 5.7 n.d. 1.5 KC49-1 n.d. n.d. 0.02 9.6 0.4 n.d. 4.1 n.d. n.d. n.d. n.d. n.d. n.d. KC50-1 n.d. n.d. 0.03 26.8 1.9 n.d. 1 n.d. n.d. n.d. n.d. n.d. 0.9 KC51-1 1.4 n.d. n.d. 15.1 0.7 n.d. 60.2 0.2 n.d. 0.18 n.d. n.d. 1 KC52-1 0.5 n.d. 0.09 22.1 0.4 n.d. 5 0.2 n.d. n.d. 4 0.2 n.d. KC53-1 4.8 n.d. 0.09 14.7 1.2 n.d. 4.8 n.d. n.d. n.d. 0.5 n.d. 0.6 KC54-1 n.d. n.d. 0.17 17.7 0.3 n.d. 15 0.6 0.1 n.d. 2.2 0.6 2 KC55-1 n.d. n.d. 0.12 18.7 0.6 n.d. 1.6 0.3 0.2 n.d. 0.6 n.d. n.d.

KC56-1 n.d. n.d. 0.2 23.2 0.9 n.d. 0.3 n.d. n.d. n.d. 0.6 n.d. 2.2 133 KC57-1 n.d. n.d. 0.03 10.5 0.1 n.d. 2.2 n.d. n.d. n.d. 0.7 n.d. n.d. KC58-1 3.9 n.d. 0.07 11.7 n.d. 0.5 1 n.d. n.d. n.d. 57.4 4n .d. 134

produced fluids and SGW are most likely associated with the coal, as explained above. Cadmium concentrations in the HSCN/BRG fluids were on average higher than Cd concentrations in the Mannville fluids, although only three samples exceeded drinking water guidelines (Health Canada, 2008). Cadmium concentrations may be higher in the HSCN/BRG fluids compared to the Mannville due to the higher influence of carbonate (incl. CdCO3) dissolution as indicated by higher alkalinity values (Table 6.1). Mannville produced waters are supersaturated in carbonates, such as calcite, which also suggests the potential for carbonate dissolution to occur (Table 5.2c). Cadmium concentrations in SGW were either below the detection limit or were detected in concentrations below drinking water guidelines (Health Canada, 2008). More than half of the Mannville waters contained Pb concentrations above drinking water guidelines (10 μg/L), whereas fewer than half of the HSCN/BRG waters and none of the SGW contained elevated concentrations of Pb (Mannville: < 10 to 92.1 μg/L; HSCN/BRG: < 1 to 98.4 μg/L;

SGW: <0.1 to 2.2 μg/L) (Tables 6.2a, b, and c). With only few exceptions listed in

Tables 6.2a-c, concentrations of the other trace elements of interest in the water samples were either not detectable or below drinking water guidelines.

Overall, the Mannville waters were from two to 70 times more concentrated in some trace elements relative to the HSCN/BRG waters and five to 300 times more concentrated in trace elements relative to the SGW. With respect to trace elements, the SGW exhibits similar geochemical characteristics to produced water from the HSCN/BRG. The lower concentrations of dissolved trace elements in the

HSCN/BRG fluids and SGW compared to the Mannville fluids may be partially due 135 to higher pH, which results in co-precipitation of dissolved trace elements, ferric iron, and calcite (Appelo and Postma, 2005). Coals deposited in brackish or marine environments generally contain higher sulfur contents with some sulfur occurring as syngenetic pyrite compared to coals deposited in a more freshwater environments (Banerjee and Goodarzi, 1990; Cohen et al., 1984, Chapter 4).

Decomposition of these pyrites is a likely cause for the high concentrations of some trace elements such as As and Se in the Mannville fluids. In contrast, a less marine depositional environment of the HSCN coals in concert with higher pH values may be responsible for the lower trace element concentrations in the

HSCN/BRG fluids.

6.2.3 Water-Rock Interaction using REEs as a Tracer

Rare earth elements have primarily been used to study geochemical reactions in rocks (Henderson, 1984; Brookins, 1989); the origin of, and rock-water interactions in, surface waters (Worrall and Pearson, 2001a; Verplanck et al., 2001,

2004); and groundwater (Banner et al., 1989; Smedley, 1991; Johannesson et al.,

1997, 1999; Lee et al., 2003; Olías, 2005). The resulting pattern of chondrite- normalized REEs may provide insight into the fractionation of elements during various geochemical processes and makes REEs a useful natural tracer in the geosphere (Henderson, 1984; Taylor and McClennan, 1988).

The average concentrations of REEs in the Mannville and HSCN/BRG produced fluids and shallow groundwater are summarized in Table 6.3. The results show elevated concentrations of total dissolved REEs (ΣREEs) in the Mannville produced fluids relative to those of the HSCN/BRG and SGW (Table 6.3). The pH 136 values of the Mannville produced fluids are slightly below neutral and are generally more acidic than fluids from the HSCN/BRG and SGW (Figure 6.4). It is well documented that the REEs tend to remain dissolved in more acidic conditions

(Smedley, 1991; Banks et al., 1999; Janssen and Verweij, 2003; Verplanck et al.,

2004). The dissolution of organic acids released from the coal strata, combined with limited buffering due to the absence of calcite within the cleats of the Mannville coals (Gentzis et al., 2008) contribute to a slightly acidic pH in the Mannville produced fluids facilitating increased dissolution of REEs.

Table 6.3: Rare earth element concentrations for produced fluids from the Mannville Formation and the HSCN/BRG and from Shallow Groundwater.

Horseshoe Canyon Formation/ Parameters Mannville Formation Belly River Group Shallow Groundwater La (µg/L) 2.51 ± 0.81 0.04 ± 0.04 0.08 ± 0.24 Ce (µg/L) 0.41 ± 0.17 0.02 ± 0.03 0.15 ± 0.51 Pr (µg/L) 0.40 ± 0.20 0.02 ± 0.02 0.03 ± 0.07 Nd (µg/L) 0.51 ± 0.32 0.49 ± 3.32 0.13 ± 0.36 Sm (µg/L) 1.20 ± 0.40 0.03 ± 0.03 0.03 ± 0.06 Eu (µg/L) 13.17 ± 8.93 0.01 ± 0.02 0.01 ± 0.02 Gd (µg/L) 2.77 ± 0.93 0.03 ± 0.03 0.02 ± 0.05 Tb (µg/L) 0.40 ± 0.20 0.01 ± 0.02 0.01 ± 0.01 Dy (µg/L) 0.40 ± 0.20 0.01 ± 0.02 0.02 ± 0.04 Ho (µg/L) 0.40 ± 0.20 0.01 ± 0.02 0.01 ± 0.01 Er (µg/L) 0.40 ± 0.21 0.01 ± 0.02 0.01 ± 0.02 Tm (µg/L) 0.40 ± 0.20 0.01 ± 0.02 0.01 ± 0.01 Yb (µg/L) 2.78 ± 1.63 0.01 ± 0.02 0.01 ± 0.01 Lu (µg/L) 0.45 ± 0.10 0.01 ± 0.02 0.01 ± 0.01 Y (µg/L) 2.79 ± 0.67 0.02 ± 0.02 0.09 ± 0.20 ΣREE (µg/L) 29 ± 11 0.74 ± 3.32 0.61 ± 1.52 Ce anomaly 0.11 ± 0.05 0.20 ± 0.21 0.47 ± 0.41 Eu anomaly 20 ± 8.2 1.39 ± 0.68 1.98 ± 0.83

(La/Lu)N 0.63 ± 0.35 0.50 ± 0.48 1.03 ± 2.77 ΣREE/Y 208 ± 106 266 ± 377 97 ± 78 ΣHREE/Y 56 ± 38 147 ± 79 67 ± 54 ΣLREE/ΣHREE 3.19 ± 2.50 1.76 ± 9.44 0.68 ± 0.74

(La/Gd)N 0.78 ± .19 1.82 ± 2.82 1.28 ± 0.92

(Yb/Gd)N 1.18 ± 0.39 0.81 ± 0.67 1.13 ± 0.54

139

Alberta), and a mixed-layer clay (Keller et al., 1991). Bentonite beds are generally composed of montmorillonite, biotite, cristobalite, oligoclase-andesine plagioclase, quartz, and low K-feldspar, while trace amounts of siderite, barite, zircon, apatite, and marcasite have also been found (Scafe, 1973). The Eu depletion suggests that the produced fluids have interacted with the carbonates in the overlying till and possibly the bentonites thereby influencing the geochemical composition of the

HSCN/BRG produced fluids (Chapter 5). Rare earth elements in SGW show a similar distribution to that of the HSCN/BRG (Figure 6.5). Most of the groundwater samples come from the HSCN/BRG aquifers and the Scollard-Paskapoo aquifers, and therefore will carry a similar REEs signature to these aquifers.

6.3 Summary

The Mannville produced fluids sampled for this study are a saline Na-Cl water type and contain high concentrations of trace elements and REEs. High boron concentrations in the produced fluids suggest a brackish/marine depositional environment. The HSCN/BRG produced fluids are a Na-HCO3 water type and have lower TDS, trace element and REEs concentrations with respect to the

Mannville produced fluids. These swabbing fluids have interacted more with carbonate-rich material, which allows for intense buffering reactions to occur and results in a higher pH compared to the Mannville produced fluids. Shallow groundwaters are predominantly of a Na-HCO3-SO4 type and are typically freshwaters. Many shallow groundwater samples were characterized by elevated sulfate concentrations. In contrast, a few shallow groundwater samples, many

HSCN/BRG and all Mannville fluids were characterized by low sulfate 140 concentrations often with elevated δ34S values. This indicates that bacterial

(dissimilatory) sulfate reduction had occurred making the redox environment suitable for methanogenesis. The δ13C values of methane and ethane of dissolved gas and the presence of propane from the Mannville produced fluids revealed a thermogenic gas component. Dissolved gas from the HSCN/BRG is predominantly biogenic, but the presence of traces of propane in some samples suggests that there is also a minor thermogenic gas component dissolved in the fluids. Carbon isotope values of methane and ethane of free gas from SGW suggests biogenic formation processes. The concentrations of some trace elements such as As and

Se in the Mannville fluids exceeded drinking water guidelines, but contamination of shallow groundwater with Mannville production fluids is highly unlikely due to geological barriers (e.g. Colorado Group). Also, the risk of trace metal contamination of shallow groundwater with CBM fluids from the HSCN/BRG is low because of their comparatively low trace metal contents. Rock-water interaction between the coal-bearing strata and the fluids most likely influenced the elevated concentrations of As, Se, and Sb in the waters. High concentrations of REEs, the positive Eu anomaly, and the pH of produced fluids from the Mannville Formation are evidence for water-rock interaction with a silicate system containing minerals such as plagioclase. Positive Eu anomalies in the produced fluids are also evident in the coals from the Mannville formation, suggesting that the coals have influenced the chemistry of the produced fluids. Lower concentrations of REEs,

Eu, and neutral to slightly basic pH in the HSCN/BRG produced fluids and SGW are evidence for interaction with a carbonate-rich system. The SGW displays a 141 similar pattern to the HSCN/BRG, suggesting that REEs are not a suitable parameter for monitoring potential contamination of shallow groundwater with CBM fluids from the HSCN/BRG. Fluids from the CBM producing Mannville Formation, the HSCN/BRG, and from shallow aquifers are sufficiently distinct in several other geochemical and isotopic parameters that potential cross-contamination should be identifiable by a suitable geochemical monitoring program. 142

CHAPTER 7: CONCLUSIONS AND FUTURE WORK

The objective of this thesis was to create a baseline study to facilitate the assessment of potential geochemical impacts of CBM operations on shallow groundwater. Geochemical and isotopic parameters were assessed to identify the sources and biogeochemical history of produced fluids and gases in shallow groundwater. Parameters that may be suitable for identifying potential leakage of fluids or gases into shallow aquifers were also assessed.

In Chapter 4, it was established that the maceral composition of coal is dependant on the depositional environment and can have an effect on the ability for the coal to produce, sorb and emit hydrocarbons. Coal rank also affects the sorption capacity, where coals of a higher rank have the ability to sorb hydrocarbons more readily, but are less able to retain the gas due to poor porosity.

The type of gas generated in coal-bearing aquifers is also dependant on coal rank, where lower rank coals generate biogenic gas and higher rank coals have a greater affinity to generation thermogenic gas. Chapter 4 also concludes that trace elements, rare-earth elements and S isotopes of coal can help determine the extent of rock-water interaction may be occurring between the coal and associated fluids. The sulfur content of coal is dependant on the depositional environment, where coal deposited in brackish water environments may have a greater inorganic

S component. The Mannville coals had a higher S content compared to the HSCN and Scollard coals and larger range of δ34S values, as this coal was deposited in a brackish water environment and had a greater inorganic S component compared to coal from the HSCN and Scollard Formations. 143

Shallow groundwater and produced fluids from the Mannville and

HSCN/BRG exhibit significant differences in chemical and isotopic compositions, as detailed in Chapter 5. It was found that the Mannville produced fluids are saline of a Na-Cl type water while, the HSCN/BRG are a Na-HCO3 water type, and the

SGW samples are typically freshwater of a Na-HCO3-SO4 type. Low sulfate concentrations in concert with elevated δ34S values in the Mannville, many of the

HSCN/BRG, and some of the SGW suggest that BSR is occurring. Dissolved and free gas from shallow groundwater and produced fluids from the Mannville and the

HSCN/BRG are chemically and isotopically distinct. Produced fluids from the

Mannville contain higher alkanes and have δ13C values that are higher compared to the HSCN/BRG and shallow groundwater, suggesting that the Mannville fluids contain a thermogenic gas component. This is in agreement with the coal rank and vitrinite reflectance value for coal from the Mannville formation. Dissolved gas in produced fluids from the HSCN/BRG is biogenic with some thermogenic gas, based on isotopic data and the lower concentration of higher alkanes. The rank and vitrinite reflectance of coal from the HSCN and Belly River also suggest a greater biogenic component. Methane in shallow groundwater is mainly biogenic based on isotopic data. Most of the shallow groundwater wells have been completed in the Scollard Formation. Coals from the Scollard Formation fall within the biogenic gas generating window.

Chapter 6 indicates that most trace element concentrations in the

HSCN/BRG produced fluids and SGW are low, therefore the risk of trace metal contamination of SGW is also low. Some trace element concentrations in the

Mannville exceed the drinking water guidelines, but the potential contamination of 144

SGW from the Mannville waters is unlikely due to geological barriers. Trace elements in the produced fluids and SGW are enriched in similar elements to coal associated with the fluids, suggesting that rock-water interaction between the coal and produced fluids has occurred. High REE concentrations and positive Eu anomalies in the Mannville produced fluids suggests that rock-water interaction with a silicate system. Produced fluids from the Mannville Formation also exhibit a similar Eu anomaly to the coal associated with it suggesting that the REE concentration in the fluids may have been affected by the coal. Lower REE concentrations and negative Eu anomalies suggest that the HSCN/BRG produced fluids and SGW have interacted with a carbonate-rich system.

This study confirms that produced fluids from the Mannville and HSCN/BRG and shallow groundwater are isotopically distinct. δ18O values of the fluids and total dissolved solids concentrations as well as the isotopic composition of methane and ethane can effectively be used as a tracer to monitor potential contamination of shallow groundwater. In contrast, REE concentrations in the

Mannville and HSCN/BRG produced fluids and shallow groundwater are not a suitable parameter for monitoring potential contamination. However, REE and trace element trends can be used to determine potential rock-water interaction in the produced fluids and shallow groundwater.

It would be beneficial to next quantify the concentration of dissolved organics (such as PAH and BTEX) in shallow groundwater and produced fluids to fully understand the potential environmental impacts of CBM production.

According to studies by Orem et al. (1999) groundwater can leach toxic organic compounds from low rank, high volatile coals. This can lead to human 145 environmental impacts if a population is exposed to high concentrations of these organic compounds in shallow groundwater over an extended period of time.

Revisiting shallow groundwater wells on a regular basis is also a necessity to properly monitor any negative effects on shallow groundwater by the CBM industry.

Shallow groundwater wells being monitored should also be in proximity to CBM activity. Future work should also include the collection and analysis of free gas samples from the coalbed methane producing wells. This would also allow for a better understanding of the origin of the gas; a better characterization of variables in the geochemical and isotopic composition of produced gas. 146

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APPENDIX: A

Table A.1: Full trace element analysis for SGW samples.

Sample I.D. Ag Al As Au B Ba Be Bi Br Ca Cd Ce Cl Co Cr Cs Cu Dy Er Eu Fe Ga Gd Ge Hf Hg Ho In Ir ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppm ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb KC5-1 n.d. 12 0.6 n.d. 341 126.79 n.d. n.d. 176 5030 0.15 0.02 17 0.19 1.7 0.08 1.5 n.d. n.d. n.d. 63 n.d. 0.01 n.d. n.d. 0.3 n.d. n.d. 0.16 KC6-1 n.d. 2 10.5 n.d. 194 30.82 n.d. n.d. 123 24709 0.07 0.01 8 0.21 1 0.01 1 n.d. n.d. n.d. 556 n.d. n.d. n.d. n.d. 0.1 n.d. n.d. n.d. KC7-1 n.d. 5 n.d. n.d. 374 29 n.d. n.d. 64 2165 0.15 n.d. 8 0.02 n.d. 0.09 n.d. n.d. n.d. n.d. 41 n.d. n.d. 0.06 n.d. n.d. n.d. n.d. n.d. KC8-1 n.d. 1 n.d. n.d. 180 15 n.d. n.d. 187 39017 0.17 n.d. 11 0.23 n.d. 0.03 0.3 n.d. n.d. n.d. 424 n.d. n.d. 0.17 n.d. 0.1 n.d. n.d. n.d. KC9-1 n.d. 4 n.d. n.d. 163 10 n.d. n.d. 279 4506 n.d. n.d. 34 0.04 n.d. 0.04 0.3 n.d. n.d. n.d. 37 n.d. n.d. 1.17 n.d. 0.1 n.d. n.d. n.d. KC10-1 n.d. 8 2.2 n.d. 286 49 n.d. n.d. 160 3842 n.d. 0.02 29 0.2 0.6 0.09 1.5 n.d. n.d. n.d. 63 n.d. n.d. 0.61 n.d. n.d. n.d. n.d. n.d. KC11-1 n.d. 79 n.d. n.d. 410 5 n.d. n.d. 57 26597 n.d. n.d. 14 n.d. n.d. 0.25 1.4 n.d. n.d. n.d. 318 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. KC20-1 n.d. 7 0.8 n.d. 614 23 n.d. n.d. 264 3310 n.d. 0.07 53 0.05 69 0.03 3.7 0.01 n.d. n.d. 347 0.27 0.01 0.19 n.d. 0.1 n.d. n.d. 0.65 KC21-1 n.d. 2 n.d. n.d. 544 143 n.d. n.d. 1717 3053 n.d. n.d. 72 0.15 3.1 0.04 0.3 n.d. n.d. n.d. n.d. n.d. n.d. 0.16 n.d. 0.1 n.d. n.d. n.d. KC22-1 n.d. 13 7.5 n.d. 1403 1186 n.d. n.d. 29375 12118 n.d. n.d. 1273 n.d. 5.4 0.16 n.d. n.d. n.d. n.d. 255 n.d. n.d. 1.05 n.d. 8.2 n.d. n.d. n.d. KC23-1 n.d. 5 n.d. n.d. 204 87 n.d. n.d. 157 2056 n.d. n.d. 22 0.04 n.d. 0.03 0.6 n.d. n.d. n.d. n.d. n.d. n.d. 0.92 n.d. 0.3 n.d. n.d. n.d. KC24-1 n.d. 1 n.d. n.d. 312 12 n.d. n.d. 27 2909 n.d. n.d. 3 n.d. 0.6 0.02 0.2 n.d. n.d. n.d. 17 n.d. n.d. n.d. n.d. 0.2 n.d. n.d. n.d. KC25-1 n.d. 5 n.d. n.d. 260 73 n.d. n.d. 220 2555 n.d. n.d. 9 0.08 1.5 0.05 0.1 n.d. n.d. n.d. 47 n.d. n.d. 0.49 n.d. 0.1 n.d. n.d. n.d. KC26-1 n.d. 1 0.7 n.d. 126 149 n.d. n.d. 230 5749 n.d. n.d. 20 0.22 3.1 0.08 0.2 n.d. n.d. n.d. 43 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. KC27-1 n.d. 4 n.d. n.d. 255 29 n.d. n.d. 44 946 n.d. n.d. 9 n.d. 0.5 0.04 0.1 n.d. n.d. n.d. n.d. 0.1 n.d. 1.37 n.d. n.d. n.d. n.d. n.d. KC28-1 n.d. 1 0.5 n.d. 200 19 0.06 n.d. 29 19176 0.18 n.d. 1 0.02 0.6 0.05 0.3 0.01 n.d. n.d. 56 n.d. n.d. 0.1 n.d. n.d. n.d. n.d. n.d. KC29-1 n.d. 1 n.d. n.d. 282 54 n.d. n.d. 230 1885 n.d. 0.9 30 0.14 1.0 0.04 0.1 0.1 0.04 0.01 22 0.11 0.11 0.91 n.d. n.d. 0.01 n.d. n.d. KC30-1 n.d. n.d. n.d. n.d. 244 24 n.d. n.d. 33 73525 n.d. n.d. 3 n.d. 1.0 0.15 0.3 n.d. n.d. n.d. 359 n.d. n.d. 0.09 n.d. n.d. n.d. n.d. n.d. KC31-1 n.d. 12 n.d. n.d. 362 17 0 n.d. 66 1240 n.d. 3.09 7 0.22 3.6 0.0 0.7 0.22 0.11 0.08 46 0.1 0.32 0.29 n.d. n.d. 0.04 n.d. n.d. KC34-1 n.d. 4 0.9 0.1 158 190 n.d. n.d. 42 1507 n.d. n.d. 3 0.02 7.2 n.d. 0.2 n.d. n.d. n.d. 13 n.d. 0.01 0.66 n.d. 0.2 n.d. n.d. n.d. KC35-1 n.d. 1 n.d. n.d. 281 7 n.d. n.d. 87 13611 n.d. 0.01 38 0.04 15.5 0.0 1.9 0.01 0.01 n.d. 241 n.d. n.d. 0.09 n.d. n.d. n.d. n.d. n.d. KC36-1 n.d. 1 n.d. n.d. 282 70 n.d. n.d. 159 2800 n.d. 0.01 10 0.1 12.1 0.1 0.3 n.d. 0.01 n.d. 16 n.d. n.d. 1.52 n.d. n.d. n.d. n.d. n.d. KC39-1 n.d. 1 n.d. n.d. 245 11 0.18 n.d. 69 16474 n.d. 0.01 6 0.05 14.6 0.1 1.6 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.1 n.d. n.d. n.d. KC40-1 n.d. n.d. 2.9 n.d. 75 25 n.d. n.d. 128 194658 n.d. 0.07 4 0.49 12.6 0.01 1.9 n.d. n.d. n.d. 5226 n.d. 0.01 0.07 n.d. n.d. n.d. n.d. n.d. KC41-1 n.d. n.d. n.d. n.d. 412 53 n.d. n.d. 31 62353 n.d. n.d. 1 0.05 13.3 0.1 5.4 n.d. n.d. n.d. 745 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. KC42-1 n.d. n.d. 1.7 n.d. 288 229 n.d. n.d. 1485 13391 n.d. n.d. 161 0.1 45.3 0.18 0.3 n.d. n.d. 0.01 89 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. KC43-1 n.d. n.d. 3.5 n.d. 114 47 0.22 n.d. 58 111360 n.d. 0.01 3 0.69 12.9 0.11 0.8 0.01 n.d. n.d. 1611 n.d. 0.01 0.27 n.d. 0.1 n.d. n.d. n.d. KC44-1 n.d. 2 n.d. n.d. 216 30 0.21 n.d. 112 2436 n.d. 0.09 10 0.08 14.6 0.02 0.2 0.01 0.01 n.d. 213 n.d. 0.01 n.d. n.d. n.d. n.d. n.d. n.d. KC45-1 n.d. 2.0 n.d. n.d. 29.0 108 0.1 n.d. 116.0 48686 n.d. n.d. 3.0 0.1 8.8 n.d. 0.4 n.d. n.d. 0.0 n.d. n.d. n.d. 0.1 n.d. n.d. n.d. n.d. n.d. KC46-1 n.d. 1.0 3.3 n.d. 213.0 8 0.1 n.d. 92.0 33698 n.d. n.d. 4.0 0.1 14.0 0.0 2.2 n.d. n.d. n.d. 567.0 n.d. 0.0 0.1 n.d. n.d. n.d. n.d. n.d. KC47-1 n.d. 1.0 3.6 n.d. 206.0 6 n.d. n.d. 90.0 33593 n.d. n.d. 4.0 0.1 13.2 0.0 2.5 n.d. n.d. n.d. 277.0 n.d. n.d. 0.1 n.d. n.d. n.d. n.d. n.d. KC48-1 n.d. n.d. n.d. n.d. 123.0 29 0.1 n.d. 61.0 26479 n.d. n.d. 3.0 0.1 14.0 n.d. 0.6 n.d. n.d. n.d. 31.0 n.d. 0.0 0.1 n.d. n.d. n.d. n.d. n.d. KC49-1 n.d. 5.0 n.d. n.d. 362.0 17 0.1 n.d. 37.0 1859 n.d. 0.0 1.0 0.0 9.6 0.0 0.4 n.d. n.d. n.d. 11.0 n.d. n.d. 0.9 n.d. n.d. n.d. n.d. n.d. KC50-1 n.d. n.d. n.d. n.d. 336.0 7 n.d. n.d. 52.0 10601 n.d. n.d. 5.0 0.0 26.8 0.1 1.9 n.d. 0.0 n.d. 94.0 n.d. n.d. 0.8 n.d. n.d. n.d. n.d. n.d. KC51-1 n.d. 1.0 1.4 n.d. 203.0 32 n.d. n.d. 26.0 3319 n.d. n.d. 13.0 n.d. 15.1 0.0 0.7 n.d. n.d. n.d. n.d. n.d. n.d. 0.4 n.d. n.d. n.d. n.d. n.d. KC52-1 n.d. n.d. 0.5 n.d. 327.0 91 0.1 n.d. 514.0 4450 n.d. n.d. 69.0 0.1 22.1 0.0 0.4 n.d. n.d. 0.0 41.0 n.d. n.d. 0.8 n.d. n.d. n.d. n.d. n.d. KC53-1 n.d. n.d. 4.8 n.d. 205.0 32 0.2 n.d. 41.0 112915 n.d. 0.0 2.0 0.1 14.7 n.d. 1.2 n.d. n.d. n.d. 3380.0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. KC54-1 n.d. 322.0 n.d. n.d. 161.0 197 0.2 n.d. 156.0 5878 n.d. 0.6 41.0 0.2 17.7 0.0 0.3 0.1 0.0 0.0 1036.0 0.1 0.1 6.5 0.0 n.d. 0.0 n.d. n.d. KC55-1 n.d. 6 n.d. n.d. 862 16 n.d. n.d. 27 2387 n.d. 0.96 1 0.12 18.7 0.03 0.6 0.09 0.05 0.03 29 n.d. 0.13 0.08 n.d. n.d. 0.02 n.d. n.d. KC56-1 n.d. n.d. n.d. n.d. 24 20 n.d. n.d. 63 137863 n.d. 0.02 n.d. 0.2 23.2 0.1 0.9 0.01 0.01 n.d. 2096 n.d. 0.01 0.12 n.d. n.d. n.d. n.d. n.d. KC57-1 n.d. 2 n.d. n.d. 1050 33 n.d. n.d. 70 2390 n.d. 0.34 6 0.03 10.5 0.01 0.1 0.04 0.02 0.01 24 n.d. 0.05 0.46 n.d. n.d. 0.01 n.d. n.d. KC58-1 n.d. 2 3.9 0.14 1815 72 n.d. n.d. 7316 2800 n.d. n.d. 707 0.07 11.7 0.11 n.d. n.d. n.d. n.d. 50 n.d. n.d. n.d. n.d. 0.5 n.d. n.d. n.d. 163 164

Sample I.D. K La Li Lu Mg Mn Mo Na Nb Nd Ni Os P Pb Pd Pr Pt Rb Re Rh Ru S ppb ppb ppb ppb ppb ppb ppb ppm ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppm KC5-1 1205 0.01 40.7 n.d. 609 7.84 5.9 451.102 n.d. 0.01 n.d. n.d. 201 0.4 0.2 n.d. n.d. 1.95 n.d. 0.55 0.27 4 KC6-1 3087 0.01 37.2 n.d. 6609 77.81 16 463.875 n.d. 0.01 n.d. n.d. 57 0.2 n.d. n.d. n.d. 1.09 0.01 0.01 n.d. 53 KC7-1 562 n.d. 55 n.d. 186 4.0 0.8 231 n.d. n.d. n.d. n.d. 320 n.d. n.d. n.d. n.d. 1.3 n.d. n.d. n.d. 1 KC8-1 2023 n.d. 20 n.d. 16261 257 7.3 217 n.d. n.d. 0.3 n.d. n.d. n.d. n.d. n.d. n.d. 0.5 0.04 n.d. n.d. 95 KC9-1 873 n.d. 28 n.d. 641 9.5 4.9 359 n.d. n.d. n.d. n.d. 29 n.d. n.d. n.d. n.d. 0.7 n.d. n.d. n.d. 105 KC10-1 882 0.01 92 n.d. 437 10.4 1.3 396 n.d. 0.01 0.6 n.d. 89 0.3 0.2 n.d. n.d. 1.5 n.d. n.d. n.d. 22 KC11-1 1951 n.d. 390 n.d. 2596 21.7 n.d. 989 n.d. n.d. n.d. n.d. n.d. 2.2 n.d. n.d. n.d. 5.7 n.d. n.d. n.d. 438 KC20-1 773 0.04 27 n.d. 236 1.5 31 292 0.03 0.04 2.5 n.d. 26 0.2 n.d. 0.01 n.d. 0.8 n.d. n.d. n.d. 2 KC21-1 1390 n.d. 28 n.d. 814 1.2 0.4 573 0.01 0.03 n.d. n.d. 66 0.1 n.d. n.d. n.d. 1.4 n.d. n.d. n.d. 108 KC22-1 3775 n.d. 112 n.d. 5283 2.8 1.0 1820 n.d. 1.58 n.d. n.d. n.d. 1.4 n.d. n.d. n.d. 3.8 n.d. n.d. n.d. n.d. KC23-1 815 n.d. 28 n.d. 566 2.4 2.9 317 0.01 0.07 0.6 n.d. 98 0.1 n.d. n.d. n.d. 0.7 n.d. n.d. n.d. 13 KC24-1 716 n.d. 49 n.d. 488 5.3 2.2 340 n.d. 0.03 n.d. n.d. 57 n.d. n.d. n.d. n.d. 0.6 n.d. n.d. n.d. 63 KC25-1 676 n.d. 50 n.d. 193 3.5 3.0 339 n.d. 0.01 n.d. n.d. 127 n.d. 0.2 n.d. n.d. 1.5 n.d. n.d. n.d. n.d. KC26-1 2125 n.d. 99 n.d. 581 4.2 0.5 515 n.d. n.d. n.d. n.d. 252 n.d. 0.2 n.d. n.d. 8.5 n.d. n.d. n.d. 12 KC27-1 482 n.d. 17 n.d. 232 0.5 5.6 252 n.d. n.d. n.d. n.d. 63 n.d. n.d. n.d. n.d. 0.7 n.d. n.d. n.d. 5 KC28-1 1257 n.d. 36 n.d. 6908 31.1 1.9 319 n.d. 0.01 0.6 n.d. n.d. 0.1 n.d. n.d. n.d. 1.4 n.d. n.d. n.d. 79 KC29-1 597 0.4 30 n.d. 159 2.8 18.6 285 0.01 0.53 0.4 n.d. 139 0.1 n.d. 0.13 n.d. 1.1 n.d. n.d. n.d. n.d. KC30-1 2924 0.01 61 n.d. 25673 58.6 0.7 233 n.d. 0.01 n.d. n.d. 28 n.d. n.d. n.d. n.d. 4.3 n.d. n.d. n.d. 91 KC31-1 557 1.43 17.1 0 111 4.74 3.0 207 n.a. 1.72 0.7 n.d. 196 0.4 n.d. 0.4 n.d. 0.76 n.d. n.d. n.d. 1 KC34-1 1063 n.d. 40.4 n.d. 482 1.8 17.7 264 n.a. n.d. 1.5 n.d. 53 0.1 n.d. n.d. n.d. 0.6 n.d. n.d. n.d. 6 KC35-1 2151 n.d. 83.1 n.d. 4609 22.03 3.3 630 n.a. 0.01 n.d. n.d. 20 n.d. n.d. n.d. n.d. 1.3 0.1 n.d. n.d. 204 KC36-1 665 n.d. 69.5 n.d. 213 3.54 1.8 348 n.a. n.d. n.d. n.d. 99 n.d. n.d. n.d. n.d. 1.17 n.d. n.d. n.d. 20 KC39-1 1772 0.01 98 n.d. 1905 10.7 0.9 432 n.a. n.d. 0.3 n.d. 127 0.2 n.d. n.d. n.d. 4.0 n.d. n.d. n.d. 109 KC40-1 2869 0.01 104 n.d. 45746 414.9 1.4 192 n.a. 0.02 n.d. n.d. 34 n.d. n.d. n.d. n.d. 4.0 n.d. n.d. n.d. 156 KC41-1 3152 n.d. 96 n.d. 23183 156.3 n.d. 148 n.a. 0.01 n.d. n.d. 26 0.3 n.d. n.d. 0.01 4.6 n.d. 0.01 n.d. 18 KC42-1 5981 n.d. 288 n.d. 1379 6.6 n.d. 706 n.a. 0.02 0.4 n.d. 297 n.d. n.d. n.d. n.d. 16.4 n.d. n.d. n.d. 1 KC43-1 4690 0.01 82 n.d. 23351 255.6 0.9 95 n.a. 0.02 1.3 n.d. 27 n.d. n.d. n.d. n.d. 6.6 0.06 0.01 n.d. 47 KC44-1 838 0.04 46 n.d. 321 16.7 8.3 240 n.a. 0.05 0.5 n.d. 202 0.1 n.d. 0.01 n.d. 1.5 n.d. n.d. n.d. n.d. KC45-1 4479.0 n.d. 27.7 n.d. 41158.0 9.7 3.7 34 n.a. 0.0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.2 0.0 n.d. n.d. 9.0 KC46-1 3738.0 n.d. 81.5 n.d. 11022.0 50.8 7.3 452 n.a. 0.0 n.d. n.d. 29.0 n.d. 0.2 n.d. 0.0 2.3 n.d. n.d. n.d. 238.0 KC47-1 3633.0 n.d. 70.6 n.d. 11002.0 47.9 7.1 444 n.a. 0.0 n.d. n.d. 29.0 n.d. n.d. n.d. 0.0 2.2 n.d. n.d. n.d. 216.0 KC48-1 2496.0 n.d. 26.8 n.d. 12998.0 18.2 5.7 214 n.a. 0.0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.5 0.2 n.d. n.d. 27.0 KC49-1 579.0 n.d. 27.4 n.d. 204.0 4.7 4.1 238 n.a. n.d. n.d. n.d. 55.0 n.d. n.d. n.d. n.d. 0.5 n.d. n.d. n.d. 37.0 KC50-1 1309.0 n.d. 81.1 n.d. 1247.0 20.3 1.0 648 n.a. n.d. n.d. n.d. 37.0 n.d. n.d. n.d. n.d. 1.4 n.d. n.d. n.d. 182.0 KC51-1 787.0 n.d. 31.4 n.d. 361.0 3.5 60.2 335 n.a. n.d. 0.2 n.d. 37.0 n.d. n.d. n.d. n.d. 0.5 0.1 n.d. n.d. 45.0 KC52-1 774.0 n.d. 98.3 n.d. 377.0 9.7 5.0 399 n.a. 0.0 0.2 n.d. 56.0 n.d. n.d. n.d. n.d. 1.3 n.d. n.d. n.d. 36.0 KC53-1 4472.0 n.d. 102.6 n.d. 32883.0 81.6 4.8 106 n.a. n.d. n.d. n.d. 33.0 n.d. n.d. n.d. n.d. 1.3 n.d. n.d. n.d. 81.0 KC54-1 1331.0 0.3 41.8 n.d. 1477.0 17.0 15.0 319 n.a. 0.3 0.6 n.d. 90.0 0.1 n.d. 0.1 n.d. 0.9 n.d. n.d. n.d. 22.0 KC55-1 2175 0.5 78.1 0.01 628 2.28 1.6 309 n.a. 0.51 0.3 n.d. 203 0.2 n.d. 0.12 n.d. 2.01 n.d. n.d. n.d. 41 KC56-1 2456 0.01 204.1 n.d. 43033 205.68 0.3 93 n.a. 0.02 n.d. n.d. n.d.0 n.d. n.d. n.d. n.d. 6.28 n.d. n.d. n.d. 56

KC57-1 963 0.18 23.3 n.d. 350 1.89 2.2 165 n.a. 0.17 n.d. n.d. 457 n.d. n.d. 0.05 n.d. 0.88 n.d. n.d. n.d. 2 164 KC58-1 2367 n.d. 50.5 n.d. 957 5.5 1 635 n.a. 0.08 n.d. n.d. 152 n.d. n.d. n.d. n.d. 2.71 n.d. n.d. n.d. n.d. 165

Sample I.D. Sb Sc Se Si Sm Sn Sr Ta Tb Te Th Ti Tl Tm U V W Y Yb Zn Zr ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb KC5-1 n.d. 1 0.6 4857 n.d. n.d. 130.31 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.47 0.3 0.3 0.01 n.d. 40.6 0.05 KC6-1 0.2 2 0.5 8440 n.d. n.d. 339.62 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 11.54 0.2 0.06 0.03 n.d. 12.6 0.15 KC7-1 n.d. 1 n.d. 3424 n.d. n.d. 31 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.2 0.01 n.d. 6.70 0.05 KC8-1 0.11 1 0.5 3187 n.d. n.d. 295 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 3.2 n.d. 0.22 0.01 n.d. 11.80 n.d. KC9-1 n.d. 1 0.7 3026 n.d. n.d. 90 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.11 0.2 0.28 0.01 n.d. n.d. 0.04 KC10-1 0.17 1 0.5 3529 n.d. n.d. 89 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.09 0.4 0.12 0.02 n.d. 8.20 0.42 KC11-1 n.d. n.d. n.d. 4377 n.d. n.d. 485 n.d. n.d. n.d. n.d. n.d.0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.74 KC20-1 1.53 2 1 5906 n.d. 0.08 75 0.02 n.d. n.d. n.d. n.d. n.d. n.d. 0.25 0.5 2.1 0.03 n.d. n.d. 0.11 KC21-1 0.08 1 4.1 3360 n.d. n.d. 191 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.02 0.6 0.29 0.01 n.d. n.d. 0.03 KC22-1 n.d. n.d. 70.1 4451 n.d. n.d. 1652 n.d. n.d. n.d. n.d. n.d.0 n.d. n.d. n.d. 14.4 0.24 n.d. n.d. 10.90 4.52 KC23-1 n.d. 1 n.d. 3115 n.d. n.d. 71 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.05 0.3 0.91 0.02 n.d. 7.90 0.12 KC24-1 n.d. 1 n.d. 3490 n.d. 0.16 63 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.04 n.d. 0.97 0.02 n.d. n.d. 0.11 KC25-1 n.d. 1 0.5 3618 n.d. n.d. 50 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.6 0.03 0.01 0.90 0.13 KC26-1 n.d. 2 0.6 9443 n.d. n.d. 94 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.02 0.2 0.03 0.01 n.d. n.d. n.d. KC27-1 n.d. 1 n.d. 3025 n.d. n.d. 32 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.05 n.d. 0.65 0.02 n.d. 0.60 0.02 KC28-1 0.07 1 n.d. 4333 n.d. n.d. 253 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.33 n.d. 0.05 0.05 0.01 12.10 0.23 KC29-1 n.d. 1 0.6 3808 0.12 n.d. 41 n.d. 0.02 n.d. 0.21 n.d. n.d. n.d. 0.03 0.4 0.36 0.44 0.03 1.60 0.08 KC30-1 n.d. 1 n.d. 5539 n.d. n.d. 1670 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.05 n.d. 0.04 0.02 n.d. 0.80 0.12 KC31-1 0.08 1 n.d. 3197 0.35 n.d. 26.33 n.d. 0.04 n.d. 1.2 19 n.d. 0.02 0.14 0.4 1.21 1.14 0.07 2.9 0.33 KC34-1 2.3 1 n.d. 1620 n.d. 0.11 56.14 n.d. n.d. n.d. 0.07 n.d. n.d. n.d. 0.45 n.d. 0.24 0.01 n.d. 0.9 0.06 KC35-1 0.1 1 0.9 4126 n.d. n.d. 504.81 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.13 0.2 0.12 0.03 n.d. 1.2 0.36 KC36-1 n.d. 1 2.3 3417 n.d. 0.14 56.04 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.02 n.d. 0.29 0.05 n.d. n.d. 0.28 KC39-1 n.d. 2 0.5 8814 n.d. n.d. 161 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.12 0.2 0.2 0.01 0.01 5.50 0.03 KC40-1 n.d. 2 1 6697 n.d. n.d. 1439 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.46 n.d. 0.05 0.06 0.01 2.60 0.09 KC41-1 n.d. 3 n.d. 8970 n.d. n.d. 1068 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.03 0.02 n.d. 13.00 n.d. KC42-1 n.d. 4 12.4 11925 n.d. 0.09 157 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.9 0.02 0.02 n.d. 7.40 0.31 KC43-1 n.d. 2 0.5 7564 n.d. n.d. 1213 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.12 n.d. 0.03 0.07 0.01 5.10 0.11 KC44-1 n.d. 1 0.9 4162 n.d. 0.12 32 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.02 n.d. 0.09 0.04 n.d. 0.60 0.04 KC45-1 n.d. 2.0 6.5 8038.0 n.d. n.d. 596.4 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 6.4 n.d. 0.1 0.0 n.d. 1.9 n.d. KC46-1 n.d. 1.0 0.8 3778.0 n.d. 0.2 808.4 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.1 n.d. 0.0 0.0 n.d. 1.3 0.1 KC47-1 n.d. 1.0 0.6 3455.0 n.d. n.d. 795.9 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.1 n.d. 0.0 0.0 n.d. 1.1 0.1 KC48-1 0.2 1.0 5.7 3041.0 n.d. 0.1 468.0 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 4.2 n.d. n.d. 0.0 n.d. 1.5 n.d. KC49-1 n.d. 1.0 n.d. 2989.0 n.d. n.d. 38.1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.1 n.d. 1.2 0.0 n.d. n.d. 0.0 KC50-1 n.d. 2.0 n.d. 4075.0 n.d. n.d. 256.5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.3 n.d. 0.1 0.0 n.d. 0.9 0.6 KC51-1 0.2 1.0 n.d. 3071.0 n.d. n.d. 69.8 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.7 n.d. 0.1 0.0 n.d. 1.0 0.1 KC52-1 n.d. 2.0 4.0 3780.0 n.d. n.d. 82.9 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.1 0.2 0.1 0.1 0.0 n.d. 0.4 KC53-1 n.d. 3.0 0.5 8722.0 n.d. n.d. 898.4 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.3 n.d. n.d. 0.0 n.d. 0.6 0.0 KC54-1 n.d. 1.0 2.2 3661.0 0.1 n.d. 80.5 n.d. 0.0 n.d. 0.1 n.d. n.d. n.d. 0.2 0.6 0.3 0.3 0.0 2.0 0.4 KC55-1 n.d. 1 0.6 3535 0.11 n.d. 55.15 n.d. 0.02 0.06 0.26 53 n.d. 0.01 0.65 n.d. 0.15 0.48 0.04 n.d. 0.98 KC56-1 n.d. 3 0.6 9674 n.d. n.d. 795.88 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.11 n.d. 0.07 0.11 0.01 2.20 0.29

KC57-1 n.d. 1 0.7 3621 0.05 n.d. 37.39 n.d. 0.01 n.d. n.d. 22 n.d. n.d. 0.04 n.d. 0.28 0.17 0.01 n.d. 0.35 165 KC58-1 n.d. 1 57.4 3722 n.d. n.d. 132.39 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 4 0.28 0.02 n.d. n.d. 0.02 166

Table A.2: Full trace element analysis for HSCN/BRG produced fluid samples.

Ag Al As Au B Ba Be Bi Br Ca Cd Ce Cl Co Cr Cs Cu Dy Er Eu Fe Sample I.D. ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppm ppb ppb ppb ppb ppb ppb ppb ppb PKB1-5 1.23 12 1.3 0.34 397 219 n.d. n.d. 1929 13957 0.73 0.04 356 0.23 1.8 0.29 6.8 0.03 0.02 0.01 1081 PKB2-5 1.54 20 3.0 n.d. 756 307 0.13 n.d. 4717 21530 0.77 0.02 1105 0.21 6.4 0.25 40.0 0.01 n.d. n.d. 40 PKB3-5 1.51 16 3.2 n.d. 674 245 n.d. n.d. 6106 14460 0.56 0.01 1210 0.39 4.1 0.14 22.4 n.d. n.d. n.d. 35 PKB4-5 0.74 16 4.2 n.d. 509 1774 0.12 n.d. 7634 53740 0.91 0.01 1353 0.47 9.1 0.36 103 0.01 0.01 n.d. n.d. PKB5-5 1.70 5 5.0 n.d. 860 1178 n.d. 0.10 16614 80532 0.43 0.01 1645 0.98 9.4 0.34 29.0 0.01 0.01 n.d. 37 PKB6-5 0.31 13 3.3 n.d. 702 109 n.d. n.d. 5094 6464 0.41 0.01 1194 0.19 4.0 0.27 96.7 n.d. n.d. n.d. 35 PKB7-5 n.d. 1 n.d. n.d. 45 22 n.d. n.d. 294 632 n.d. n.d. 55 0.02 n.d. 0.01 14.9 n.d. n.d. n.d. n.d. PKB8-5 0.30 14 3.1 n.d. 747 110 n.d. n.d. 5738 5767 0.35 n.d. 1302 0.13 2.7 0.16 67.2 n.d. 0.01 n.d. 19 PKB1-6 0.07 8 3.6 n.d. 1272 203 n.d. n.d. 3233 7703 0.50 0.01 814 0.05 148.7 0.37 18.0 0.01 n.d. n.d. n.d. PKB2-6 n.d. 16 3.4 n.d. 849 201 0.11 n.d. 3471 13116 15.30 0.02 875 0.43 26.5 0.15 12.5 0.01 n.d. n.d. 30 PKB3-6 n.d. 1 n.d. n.d. 45 23 n.d. n.d. 396 1159 0.10 n.d. 70 0.04 1.2 0.03 0.9 n.d. n.d. n.d. n.d. PKB4-6 0.22 17 3.6 n.d. 516 4967 n.d. n.d. 7288 272727 5.13 0.02 1113 0.54 23.9 0.30 41.6 0.01 n.d. n.d. 9112 PKB5-6 n.d. 9 0.6 n.d. 318 383 n.d. n.d. 1175 50303 76.74 0.01 172 0.24 4.5 0.10 5.8 n.d. n.d. n.d. 48 PKB6-6 n.d. 3 0.5 n.d. 421 141 n.d. n.d. 1180 28685 1.73 n.d. 145 0.27 2.0 0.07 3.5 n.d. n.d. n.d. n.d. PKB7-6 n.d. 8 1.3 n.d. 773 524 n.d. n.d. 1540 32181 2.64 n.d. 482 0.31 11.4 0.13 11.7 0.01 n.d. n.d. 58 PKB8-6 n.d. 1 n.d. n.d. 63 19 n.d. n.d. 180 753 0.06 n.d. 50 0.02 n.d. 0.01 0.9 n.d. n.d. n.d. n.d. PKB9-6 n.d. 18 2.0 n.d. 502 514 n.d. n.d. 4589 12678 0.40 n.d. 753 0.17 6.3 0.32 15.5 n.d. n.d. n.d. 62 PKB10-6 0.15 8 3.3 n.d. 503 528 0.22 n.d. 6987 15510 0.39 n.d. 1156 0.30 20.9 0.05 11.7 0.01 n.d. n.d. 37 PKB11-6 n.d. 8 1.7 n.d. 613 350 0.22 n.d. 3199 9954 0.52 n.d. 764 0.42 6.2 0.09 10.6 0.01 n.d. n.d. 48 PKB12-6 n.d. 14 13.4 n.d. 860 43 n.d. n.d. 3987 12426 0.10 n.d. 1096 0.49 4.8 0.39 19.4 n.d. 0.01 n.d. 43 PKB13-6 n.d. 2 n.d. n.d. 247 96 n.d. n.d. 399 23144 0.08 n.d. 83 0.07 1.0 0.10 3.2 n.d. n.d. n.d. n.d. PKB14-6 n.d. 14 1.8 n.d. 481 120 0.08 n.d. 3412 5331 0.45 0.01 742 0.18 5.5 0.13 9.9 n.d. n.d. n.d. 62 PKB1-7 0.11 19 3.8 n.d. 422 1248 0.08 n.d. 6810 33837 0.35 n.d. 1091 1.46 8.1 0.10 37.5 0.01 0.01 n.d. 58 PKB2-7 n.d. 6 3.3 n.d. 480 1743 0.07 n.d. 4610 74267 0.26 n.d. 1044 1.21 15.6 0.21 442 n.d. n.d. n.d. 1830 PKB3-7 n.d. 15 4.7 n.d. 558 475 0.21 n.d. 5993 19554 0.29 n.d. 1274 0.62 10.2 0.94 111 0.01 n.d. n.d. 146 PKB4-7 n.d. 13 3.3 n.d. 702 267 n.d. n.d. 4659 15176 0.28 0.01 1196 5.96 8.5 0.09 1448 n.d. n.d. n.d. 966 PKB5-7 0.09 8 2.9 n.d. 673 1320 0.07 n.d. 5782 47300 0.51 n.d. 1127 0.55 9.5 0.20 29.1 n.d. n.d. n.d. 105 PKB6-7 n.d. 11 2.8 n.d. 706 410 0.20 n.d. 5442 19239 0.29 n.d. 1181 0.42 7.0 0.59 51.4 n.d. n.d. n.d. 74 PKB7-7 n.d. 13 2.8 n.d. 1085 548 0.06 n.d. 6949 14789 0.25 n.d. 1180 0.57 10.0 0.48 27.3 0.02 n.d. n.d. 62 PKB8-7 0.08 23 4.1 n.d. 726 944 n.d. n.d. 8445 22948 0.46 n.d. 1258 0.55 47.8 0.67 66.3 0.01 n.d. n.d. 845 PKB9-7 0.12 18 3.6 n.d. 838 701 0.06 n.d. 7591 22576 0.56 n.d. 1382 0.43 19.0 0.54 44.2 0.01 n.d. n.d. 127 PKB10-7 0.06 14 2.8 n.d. 643 352 n.d. n.d. 6162 13453 0.37 n.d. 999 0.58 30.6 0.29 32.2 0.01 n.d. n.d. 108 PKB11-7 n.d. 17 3.4 n.d. 694 331 n.d. n.d. 6972 17842 0.27 0.01 1366 9.78 12.6 0.83 53.8 n.d. n.d. n.d. 66 PKB12-7 n.d. 13 2.3 n.d. 441 713 n.d. n.d. 5783 18321 0.24 n.d. 1091 0.29 5.1 0.08 26.1 0.01 n.d. n.d. 35 PKB13-7 2.33 20 6.0 0.20 419 439 0.13 n.d. 9291 10648 n.d. 0.02 1512 0.56 9.7 0.69 261 n.d. 0.01 n.d. 72 PKB14-7 1.02 20 2.3 0.07 313 912 0.12 n.d. 3966 25312 n.d. n.d. 681 0.21 7.8 0.13 39.8 n.d. n.d. n.d. 36 PKB15-7 0.84 94 3.1 n.d. 745 177 n.d. n.d. 8794 5403 n.d. n.d. 1075 0.31 13.3 0.45 108 n.d. 0.01 n.d. 93 PKB16-7 0.55 14 2.7 n.d. 405 333 0.11 n.d. 4482 10532 0.26 n.d. 744 0.16 43.5 0.05 23.1 n.d. 0.01 n.d. 57 PKB17-7 0.54 10 2.8 n.d. 570 817 n.d. n.d. 5881 21898 n.d. n.d. 975 0.59 21.6 0.17 19.8 0.01 0.01 n.d. 33 PKB18-7 0.57 9 2.4 n.d. 465 338 n.d. n.d. 5996 10884 n.d. n.d. 1036 0.17 8.2 0.07 13.7 n.d. n.d. n.d. 743 PKB1-8 0.92 6 5.1 n.d. 936 457 n.d. n.d. 12249 187660 1.07 0.01 1667 1.35 17.6 0.38 42.6 n.d. n.d. n.d. 5860 PKB2-8 n.d. 3 n.d. n.d. 433 72 n.d. n.d. 3192 24163 n.d. n.d. 143 0.24 2.0 0.18 2.5 n.d. n.d. n.d. 78 PKB3-8 0.06 200 1.2 n.d. 338 31 n.d. n.d. 5566 14161 n.d. n.d. 253 0.07 3.7 0.17 5.3 n.d. n.d. n.d. 24 PKB4-8 0.29 8 3.8 n.d. 517 1274 n.d. n.d. 13945 106267 n.d. n.d. 1306 1.23 16.8 0.43 25.0 n.d. n.d. n.d. 598 PKB5-8 n.d. 3 0.8 n.d. 89 143 n.d. n.d. 502 12509 n.d. n.d. 47 0.02 1.4 0.15 4.7 n.d. n.d. n.d. 17 PKB6-8 n.d. 5 0.6 n.d. 487 205 n.d. n.d. 1831 52408 n.d. n.d. 199 0.54 2.0 0.23 3.3 n.d. n.d. n.d. n.d. KC1-1 n.d. 54 10 0.96 1081 4446.28 n.d. n.d. 43243 65056 n.d. 0.13 4353 0.26 n.d. 0.84 3.1 n.d. n.d. n.d. 16383 KC2-1 n.d. 43 6.4 n.d. 394 411.44 n.d. n.d. 23271 5364 n.d. n.d. 2566 0.21 n.d. 0.42 3.1 n.d. n.d. n.d. n.d. KC3-1 n.d. 27 n.d. n.d. 444 109.47 n.d. n.d. 9252 7249 0.51 n.d. 1235 n.d. n.d. 0.37 4 n.d. n.d. n.d. 692 KC4-1 n.d. 31 n.d. n.d. 381 1425.38 n.d. n.d. 6003 26946 0.81 0.15 1536 0.33 13.5 0.43 11 n.d. n.d. n.d. 434 KC5-1 n.d. 12 0.6 n.d. 341 126.79 n.d. n.d. 176 5030 0.15 0.02 17 0.19 1.7 0.08 1.5 n.d. n.d. n.d. 63 KC6-1 n.d. 2 10.5 n.d. 194 30.82 n.d. n.d. 123 24709 0.07 0.01 8 0.21 1 0.01 1 n.d. n.d. n.d. 556 KC12-1 n.d. 28 2.3 0.08 750 68.87 n.d. n.d. 2538 6124 0.16 0.02 446 0.12 0.8 0.11 4.2 n.d. n.d. n.d. 123 KC13-1 n.d. 57 1.2 n.d. 516 59.36 n.d. n.d. 998 2799 0.13 0.05 165 0.21 0.5 0.14 4.2 n.d. n.d. n.d. 152 KC14-1 n.d. 24 n.d. n.d. 100 188.73 n.d. n.d. 133 11721 0.44 0.05 32 0.33 n.d. 0.12 2.9 n.d. n.d. n.d. 90 KC15-1 n.d. 50 5.4 n.d. 303 457.23 n.d. n.d. 6370 22830 n.d. n.d. 966 0.61 n.d. 0.17 22.6 n.d. n.d. n.d. 1510 KC16-1 n.d. 63 n.d. n.d. 952 926.27 n.d. n.d. 5022 15545 n.d. n.d. 511 n.d. 10.9 0.23 6.4 n.d. n.d. n.d. 157 KC17-1 n.d. 12 0.5 n.d. 172 372.91 n.d. n.d. 658 18832 0.06 n.d. 91 0.2 2.6 0.09 1 n.d. n.d. n.d. 20 KC37-1 n.d. n.d. 6.6 n.d. 468 1116.1 1.13 n.d. 14609 39459 n.d. n.d. 1274 0.23 20.9 0.19 5.7 n.d. n.d. n.d. n.d. KC38-1 n.d. n.d. 6.1 n.d. 922 1672.84 n.d. n.d. 15076 50077 n.d. n.d. 1056 n.d. 17.5 0.19 4.3 n.d. n.d. n.d. n.d. 167

Ga Gd Ge Hf Hg Ho In Ir K LaL iL uM gM nM o Sample I.D. ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb PKB1-5 n.d. 0.03 0.31 n.d. n.d. 0.02 n.d. n.d. 35771 0.22 125 0.01 1904 167 34.4 PKB2-5 n.d. 0.05 0.22 n.d. n.d. 0.01 n.d. n.d. 62133 0.15 336 0.01 4032 27 448 PKB3-5 0.06 0.07 0.20 n.d. n.d. n.d. 0.01 n.d. 31632 0.05 197 0.01 2651 68 24.0 PKB4-5 n.d. 0.07 0.24 n.d. n.d. 0.01 n.d. n.d. 47853 0.09 305 n.d. 9248 188 30.0 PKB5-5 n.d. 0.10 0.13 n.d. 1.3 0.01 n.d. n.d. 39355 0.05 361 n.d. 15986 270 17.4 PKB6-5 n.d. 0.04 0.14 n.d. n.d. n.d. n.d. n.d. 44505 0.03 179 0.01 2381 12 74.4 PKB7-5 n.d. 0.01 n.d. n.d. n.d. n.d. n.d. n.d. 2089 n.d. 8.9 n.d. 155 4.8 1.0 PKB8-5 n.d. 0.05 0.12 n.d. n.d. n.d. n.d. n.d. 43945 0.02 205 n.d. 2813 16 60.7 PKB1-6 n.d. 0.08 0.27 n.d. n.d. n.d. n.d. n.d. 15975 0.02 148 n.d. 1215 20 39.6 PKB2-6 n.d. 0.10 0.14 n.d. n.d. n.d. n.d. n.d. 16419 0.03 156 n.d. 2926 87 91.9 PKB3-6 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 2217 n.d. 11 n.d. 169 15 3.0 PKB4-6 n.d. 0.11 0.20 n.d. 0.3 0.01 n.d. n.d. 24779 0.10 554 n.d. 30542 1045 5.8 PKB5-6 n.d. 0.01 0.12 n.d. n.d. n.d. n.d. n.d. 9195 0.01 70 n.d. 3867 148 6.5 PKB6-6 n.d. n.d. 0.21 n.d. n.d. n.d. n.d. n.d. 13214 n.d. 66 n.d. 4009 163 16.4 PKB7-6 n.d. 0.02 0.33 n.d. n.d. n.d. n.d. n.d. 13758 0.01 138 n.d. 3326 320 14.5 PKB8-6 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 684 n.d. 8.0 n.d. 117 7.6 7.1 PKB9-6 n.d. 0.01 0.23 n.d. n.d. n.d. n.d. n.d. 65648 0.04 168 n.d. 3089 112 27.6 PKB10-6 n.d. 0.04 0.09 n.d. n.d. 0.01 0.01 n.d. 6154 0.02 119 n.d. 1791 177 12.0 PKB11-6 n.d. 0.02 0.27 n.d. n.d. n.d. n.d. n.d. 12479 0.01 102 n.d. 1487 134 36.3 PKB12-6 n.d. 0.05 0.48 n.d. n.d. n.d. n.d. n.d. 24692 0.03 110 n.d. 7728 47 263 PKB13-6 n.d. 0.01 0.43 n.d. n.d. n.d. n.d. n.d. 5935 0.01 36 n.d. 1772 149 10.2 PKB14-6 n.d. 0.03 0.17 n.d. n.d. n.d. n.d. n.d. 14298 0.01 112 n.d. 969 13 70.3 PKB1-7 0.20 0.10 0.20 n.d. n.d. n.d. n.d. n.d. 17752 0.03 252 n.d. 5879 47 28.0 PKB2-7 n.d. 0.02 0.53 n.d. n.d. n.d. n.d. n.d. 45673 0.05 352 n.d. 13963 408 7.4 PKB3-7 0.14 0.05 0.34 n.d. n.d. n.d. n.d. n.d. 48377 0.02 251 n.d. 4990 101 52.0 PKB4-7 n.d. n.d. 0.57 n.d. n.d. n.d. n.d. n.d. 46034 0.03 229 n.d. 5548 79 38.7 PKB5-7 n.d. 0.03 0.14 n.d. n.d. n.d. n.d. n.d. 38239 0.04 350 n.d. 6353 171 22.0 PKB6-7 n.d. n.d. 0.12 n.d. n.d. n.d. n.d. n.d. 47364 0.02 242 n.d. 3549 123 28.1 PKB7-7 0.10 0.02 0.09 n.d. n.d. 0.01 n.d. n.d. 59772 0.02 285 n.d. 4747 70 54.9 PKB8-7 0.27 0.02 0.09 n.d. n.d. n.d. n.d. n.d. 65122 0.04 363 n.d. 7346 94 97.5 PKB9-7 0.27 n.d. 0.24 n.d. n.d. n.d. n.d. n.d. 77400 0.02 378 n.d. 6321 78 101 PKB10-7 0.22 n.d. 0.17 n.d. n.d. n.d. n.d. n.d. 44517 0.02 225 n.d. 3585 73 63.1 PKB11-7 0.22 n.d. 0.38 n.d. n.d. n.d. n.d. n.d. 54997 0.03 248 n.d. 4402 73 36.2 PKB12-7 n.d. n.d. 0.18 n.d. n.d. n.d. 0.01 n.d. 8466 0.02 121 n.d. 2942 63 11.4 PKB13-7 0.31 n.d. 0.30 n.d. n.d. 0.01 n.d. n.d. 69146 0.12 356 0.01 3459 16 104 PKB14-7 0.09 0.01 0.22 n.d. 0.1 n.d. n.d. n.d. 26733 0.04 202 0.01 5423 116 9.2 PKB15-7 0.76 n.d. 0.15 n.d. n.d. n.d. n.d. n.d. 74812 0.03 245 n.d. 1421 3.4 132 PKB16-7 n.d. 0.03 0.18 n.d. 0.6 0.01 n.d. n.d. 14437 0.02 125 n.d. 2357 74 10.8 PKB17-7 0.06 0.04 0.12 n.d. n.d. n.d. n.d. n.d. 28480 0.03 176 n.d. 5169 145 35.3 PKB18-7 n.d. 0.01 0.19 n.d. 0.3 n.d. n.d. n.d. 15501 0.01 132 n.d. 2170 109 8.0 PKB1-8 n.d. 0.05 0.23 n.d. n.d. n.d. n.d. n.d. 88214 0.02 533 n.d. 21154 750 60.2 PKB2-8 n.d. n.d. 0.10 n.d. n.d. n.d. n.d. n.d. 48975 0.01 51 n.d. 4364 224 16.7 PKB3-8 1.35 n.d. 0.14 n.d. n.d. n.d. n.d. n.d. 116142 0.01 82 n.d. 1798 10 22.9 PKB4-8 n.d. 0.04 0.18 n.d. 0.5 n.d. n.d. n.d. 40770 0.02 343 n.d. 14550 732 27.9 PKB5-8 n.d. n.d. 1.43 n.d. n.d. n.d. n.d. n.d. 20095 0.01 26 n.d. 1430 48 6.3 PKB6-8 0.13 0.01 0.15 n.d. n.d. n.d. n.d. n.d. 19738 0.01 61 n.d. 3890 252 18.4 KC1-1 n.d. n.d. n.d. n.d. 13.8 n.d. n.d. n.d. 8874 0.1 267.4 n.d. 9384 412.52 2.1 KC2-1 n.d. n.d. n.d. n.d. 8.6 n.d. n.d. n.d. 9967 n.d. 294.2 n.d. 1330 2.62 101.3 KC3-1 n.d. n.d. n.d. n.d. 7.6 n.d. n.d. n.d. 38267 n.d. 177.5 n.d. 1435 154.43 30.7 KC4-1 n.d. n.d. 1.6 n.d. 3.2 n.d. n.d. n.d. 17805 n.d. 319.4 n.d. 5472 102.2 15.1 KC5-1 n.d. 0.01 n.d. n.d. 0.3 n.d. n.d. 0.16 1205 0.01 40.7 n.d. 609 7.84 5.9 KC6-1 n.d. n.d. n.d. n.d. 0.1 n.d. n.d. n.d. 3087 0.01 37.2 n.d. 6609 77.81 16 KC12-1 0.08 n.d. 0.51 n.d. 0.1 n.d. n.d. 0.07 4975 0.01 71.9 n.d. 923 27.23 15.6 KC13-1 0.26 n.d. 0.21 0.01 0.1 n.d. n.d. 0.12 3759 0.02 30.2 n.d. 304 21.99 12.4 KC14-1 n.d. 0.01 0.39 0.01 0.1 n.d. n.d. 0.06 1618 0.02 10.6 n.d. 721 293.24 2.4 KC15-1 n.d. n.d. n.d. 0.1 n.d. n.d. n.d. n.d. 4715 n.d. 178.9 n.d. 2943 200.01 9.7 KC16-1 n.d. n.d. n.d. 0.1 n.d. n.d. n.d. n.d. 21527 n.d. 285.2 n.d. 10895 21.43 39.6 KC17-1 n.d. n.d. 0.14 0.01 n.d. n.d. n.d. n.d. 5785 n.d. 91.1 n.d. 2718 93.52 11.9 KC37-1 n.d. n.d. n.d. 0.1 n.d. n.d. n.d. n.d. 6916 n.d. 312.1 n.d. 4413 112.64 3.6 KC38-1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 29430 n.d. 376.9 n.d. 9136 69.8 12 168

Na Nb Nd Ni Os P Pb Pd Pr Pt Rb Re Rh Ru S Sb Sample I.D. ppm ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppm ppb PKB1-5 608 n.d. 0.02 1.1 n.d. 115 2.9 n.d. 0.04 0.01 28 n.d. n.d. n.d. 6 0.17 PKB2-5 1823 0.02 0.01 0.2 n.d. 60 52.2 n.d. 0.02 n.d. 87 0.03 n.d. n.d. 16 2.43 PKB3-5 1312 0.01 0.04 0.3 n.d. 76 16.5 n.d. 0.02 0.01 49 0.01 n.d. n.d. 10 1.64 PKB4-5 2250 0.01 0.03 0.4 n.d. 53 22.1 n.d. 0.01 0.01 93 0.01 n.d. n.d. 11 0.93 PKB5-5 2699 0.02 0.20 7.0 n.d. 70 2.2 0.3 0.01 0.01 42 n.d. n.d. n.d. 9 0.52 PKB6-5 1422 0.03 0.05 2.0 n.d. 72 22.4 0.2 0.01 0.01 68 0.02 n.d. n.d. 23 2.13 PKB7-5 66.6 n.d. n.d. 0.2 n.d. n.d. 0.7 n.d. n.d. n.d. 1 n.d. n.d. n.d. n.d. 0.14 PKB8-5 1556 0.02 0.03 1.2 n.d. 61 9.5 n.d. 0.01 n.d. 65 0.01 n.d. n.d. 21 1.26 PKB1-6 1103 n.d. 0.02 0.5 n.d. 117 13.5 n.d. 0.02 0.01 25 0.03 n.d. n.d. 35 1.43 PKB2-6 1125 n.d. 0.01 2.2 n.d. 69 8.2 0.2 0.02 0.02 22 0.03 n.d. n.d. 40 1.84 PKB3-6 72.5 n.d. n.d. 0.2 n.d. n.d. 0.3 n.d. n.d. n.d. 2 n.d. n.d. n.d. n.d. n.d. PKB4-6 4124 0.01 0.08 n.d. n.d. 96 2.9 0.6 0.01 0.01 53 n.d. n.d. n.d. 17 0.36 PKB5-6 470 0.01 0.01 0.5 n.d. 283 5.8 0.2 n.d. n.d. 22 n.d. n.d. n.d. 14 0.60 PKB6-6 328 n.d. n.d. 3.1 n.d. 29 13.6 n.d. n.d. n.d. 24 0.01 n.d. n.d. 15 0.72 PKB7-6 1092 0.01 0.02 1.0 n.d. 51 2.7 0.4 0.01 0.01 16 0.02 n.d. n.d. 13 1.33 PKB8-6 68.6 n.d. n.d. 0.3 n.d. n.d. 0.3 n.d. n.d. n.d. 1 n.d. n.d. n.d. 2 0.16 PKB9-6 1614 n.d. 0.05 n.d. n.d. 241 3.8 0.3 0.01 0.01 51 0.01 n.d. n.d. 6 0.45 PKB10-6 1082 0.01 0.04 1.7 n.d. 58 2.6 0.2 0.01 0.01 10 0.01 n.d. n.d. 7 0.53 PKB11-6 1014 n.d. 0.02 4.1 n.d. 50 3.0 0.3 0.01 0.02 21 0.01 n.d. n.d. 9 1.00 PKB12-6 1637 0.03 0.03 6.3 n.d. 5902 58.4 0.2 0.01 n.d. 32 0.02 n.d. n.d. 83 5.26 PKB13-6 96.8 n.d. n.d. 0.4 n.d. 260 6.2 n.d. n.d. n.d. 17 n.d. n.d. n.d. 15 0.39 PKB14-6 780 n.d. 0.02 0.5 n.d. 663 17.2 0.2 0.02 0.03 31 0.02 n.d. n.d. 12 0.74 PKB1-7 2081 n.d. 0.06 0.8 n.d. 552 13.1 0.6 0.01 n.d. 41 n.d. n.d. n.d. 11 1.52 PKB2-7 2932 0.04 0.07 n.d. n.d. 429 5.4 0.6 n.d. 0.02 122 0.01 n.d. n.d. 28 0.56 PKB3-7 2389 0.07 0.06 0.2 n.d. 347 10.1 0.3 0.01 0.02 116 0.02 n.d. n.d. 25 1.65 PKB4-7 2121 0.04 25.34 13.1 n.d. 329 13.8 0.4 0.01 0.01 75 0.05 n.d. n.d. 65 1.28 PKB5-7 2389 n.d. 0.06 n.d. n.d. 248 1.9 0.5 n.d. 0.01 75 0.02 n.d. n.d. 20 1.10 PKB6-7 1888 0.03 0.05 1.5 n.d. 212 17.8 0.6 0.01 n.d. 96 0.03 n.d. n.d. 20 1.40 PKB7-7 2738 0.04 0.04 2.8 n.d. 190 34.0 n.d. n.d. n.d. 95 0.02 n.d. n.d. 18 1.11 PKB8-7 3413 0.02 0.06 2.6 n.d. 243 98.4 0.4 0.02 0.01 140 0.02 n.d. n.d. 22 0.99 PKB9-7 3201 0.03 0.05 0.4 n.d. 196 16.7 0.4 0.01 0.01 173 0.02 n.d. n.d. 26 1.12 PKB10-7 1905 0.01 0.04 1.8 n.d. 188 31.4 0.4 0.01 0.01 105 0.01 n.d. n.d. 20 0.92 PKB11-7 2345 0.04 0.05 n.d. n.d. 377 33.9 0.4 n.d. 0.01 124 0.01 n.d. n.d. 51 1.13 PKB12-7 1197 0.01 0.03 n.d. n.d. 127 3.9 0.3 0.01 n.d. 13 0.02 n.d. n.d. 8 0.53 PKB13-7 2966 0.02 0.06 3.2 n.d. 50 6.1 0.4 0.01 0.01 148 0.02 n.d. n.d. 29 1.33 PKB14-7 1540 n.d. 0.02 n.d. n.d. 34 1.8 0.5 0.01 0.01 53 0.01 n.d. n.d. 12 0.60 PKB15-7 2961 n.d. 0.05 0.9 n.d. 64 11.2 0.3 0.01 0.01 139 0.01 n.d. n.d. 33 0.54 PKB16-7 1120 0.01 0.03 n.d. n.d. 47 5.2 n.d. 0.02 0.01 21 n.d. n.d. n.d. 8 0.60 PKB17-7 1688 0.02 0.04 1.8 n.d. 40 4.0 n.d. 0.01 n.d. 43 n.d. n.d. n.d. 18 1.21 PKB18-7 1145 0.01 0.05 0.3 n.d. 33 1.1 0.3 0.01 n.d. 21 n.d. n.d. n.d. 8 0.84 PKB1-8 3313 0.03 0.09 n.d. n.d. 62 4.0 0.3 0.01 0.01 158 0.03 n.d. n.d. 61 0.56 PKB2-8 237 n.d. n.d. 2.0 n.d. 83 0.4 n.d. n.d. n.d. 27 0.01 n.d. n.d. 20 0.67 PKB3-8 509 0.01 0.01 0.7 n.d. 108 0.6 n.d. n.d. n.d. 59 0.05 n.d. n.d. 16 1.22 PKB4-8 2480 n.d. 0.08 1.9 n.d. 219 1.4 0.4 0.01 n.d. 46 0.01 n.d. n.d. 21 0.51 PKB5-8 71.9 n.d. n.d. n.d. n.d. 48 5.7 n.d. n.d. n.d. 11 n.d. n.d. n.d. 11 0.41 PKB6-8 314 n.d. 0.01 6.7 n.d. 98 1.9 n.d. n.d. n.d. 25 n.d. n.d. n.d. 18 0.85 KC1-1 2965 n.d. 0.54 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 11.9 n.d. 0.21 n.d. 14 n.d. KC2-1 1927 n.d. 0.11 n.d. n.d. n.d. 3.3 n.d. n.d. n.d. 24.1 n.d. 3.27 1.67 16 0.82 KC3-1 1286 n.d. n.d. n.d. n.d. n.d. 3.1 n.d. n.d. n.d. 25.3 n.d. 1.07 0.53 25 n.d. KC4-1 2182 n.d. n.d. n.d. n.d. n.d. 3.2 n.d. n.d. n.d. 32.6 n.d. 5.08 2.59 41 n.d. KC5-1 451 n.d. 0.01 n.d. n.d. 201 0.4 0.2 n.d. n.d. 1.95 n.d. 0.55 0.27 4 n.d. KC6-1 464 n.d. 0.01 n.d. n.d. 57 0.2 n.d. n.d. n.d. 1.09 0.01 0.01 n.d. 53 0.2 KC12-1 592 0.03 0.04 1.2 n.d. 40 1.9 0.4 n.d. n.d. 6.58 n.d. n.d. n.d. 4 0.81 KC13-1 277 0.01 0.05 1.4 n.d. n.d. 1.8 n.d. n.d. n.d. 5.53 n.d. n.d. n.d. 6 0.46 KC14-1 47.3 n.d. 0.04 2.6 n.d. n.d. 1.5 n.d. 0.01 n.d. 3.41 n.d. n.d. n.d. 1 0.23 KC15-1 1129 n.d. n.d. 82.2 n.d. n.d. 2.6 n.d. n.d. n.d. 7.41 n.d. n.d. n.d. n.d. 0.61 KC16-1 1953 n.d. 0.2 3.2 n.d. n.d. 5.9 n.d. n.d. n.d. 34.9 n.d. n.d. n.d. n.d. 2.44 KC17-1 289 n.d. 0.02 3.2 n.d. 99 1.8 n.d. n.d. n.d. 9.67 n.d. n.d. n.d. 2 0.87 KC37-1 1575 n.d. 0.12 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 13.6 n.d. n.d. n.d. n.d. n.d. KC38-1 2448 n.d. 0.14 2.2 n.d. n.d. 35.3 n.d. n.d. n.d. 40.5 n.d. n.d. n.d. n.d. 1.67 169

Sc Se Si Sm Sn Sr Ta Tb Te Th Ti Tl Tm U V WY Y bZ n Zr Sample I.D. ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb PKB1-5 n.d. 11.0 1090 0.02 n.d. 349 n.d. 0.02 n.d. 0.18 n.d. n.d. 0.01 n.d. 0.7 17 0.06 0.01 394 n.d. PKB2-5 n.d. 28.0 1364 0.03 n.d. 670 n.d. 0.01 n.d. 0.10 n.d. 0.09 n.d. n.d. 1.8 763 0.03 n.d. 311 0.02 PKB3-5 n.d. 33.7 1749 n.d. n.d. 493 n.d. n.d. n.d. n.d. n.d. 0.03 n.d. n.d. 2.6 92 0.01 0.02 321 0.02 PKB4-5 4 40.4 1730 0.02 n.d. 2043 n.d. n.d. n.d. n.d. n.d. 0.03 n.d. n.d. 2.4 83 0.05 n.d. 939 n.d. PKB5-5 n.d. 84.0 1489 0.03 n.d. 3420 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.04 3.5 14 0.06 0.01 4321 0.11 PKB6-5 n.d. 27.6 879 n.d. n.d. 299 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.05 2.3 265 0.01 0.02 450 0.48 PKB7-5 n.d. 1.4 151 n.d. n.d. 24 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 49 n.d. n.d. 41 0.02 PKB8-5 n.d. 32.5 760 n.d. n.d. 294 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.02 2.8 98 0.01 0.01 441 0.52 PKB1-6 3 19.7 4416 n.d. n.d. 226 n.d. n.d. n.d. n.d. n.d. 0.02 n.d. 0.02 2.2 242 0.02 n.d. 155 0.02 PKB2-6 n.d. 18.4 3102 0.02 n.d. 366 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.02 1.9 79 0.02 n.d. 346 0.05 PKB3-6 n.d. 2.2 141 n.d. n.d. 29 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.2 10 n.d. n.d. 72 n.d. PKB4-6 n.d. 40.8 2957 0.03 n.d. 6882 0.04 n.d. 0.14 n.d. n.d. n.d. n.d. n.d. 2.0 4 0.09 0.03 5639 0.02 PKB5-6 n.d. 6.3 1184 n.d. n.d. 1291 n.d. n.d. n.d. n.d. n.d. 0.07 n.d. n.d. 0.3 101 0.02 n.d. 609 n.d. PKB6-6 n.d. 6.5 1579 n.d. n.d. 602 n.d. n.d. n.d. n.d. n.d. 0.02 n.d. n.d. 0.2 286 0.01 n.d. 990 n.d. PKB7-6 n.d. 8.5 5159 n.d. n.d. 968 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.7 556 0.01 n.d. 2071 n.d. PKB8-6 n.d. 1.0 313 n.d. n.d. 21 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 20 n.d. n.d. 39 n.d. PKB9-6 n.d. 22.9 2551 n.d. n.d. 455 n.d. n.d. 0.08 n.d. n.d. n.d. n.d. n.d. 1.2 169 0.03 0.01 292 0.04 PKB10-6 n.d. 35.0 2997 n.d. 0.81 536 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 2.1 21 0.01 n.d. 852 n.d. PKB11-6 n.d. 18.0 2011 n.d. n.d. 418 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.4 172 0.01 n.d. 590 n.d. PKB12-6 n.d. 21.5 #### n.d. n.d. 118 n.d. n.d. n.d. n.d. 18 n.d. n.d. 0.14 4.1 625 0.04 0.01 631 0.48 PKB13-6 n.d. 2.3 464 n.d. n.d. 295 n.d. n.d. n.d. n.d. n.d. 0.14 n.d. n.d. 0.2 33 n.d. n.d. 392 n.d. PKB14-6 n.d. 17.7 903 n.d. n.d. 179 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.2 304 0.01 n.d. 131 n.d. PKB1-7 n.d. 37.4 877 0.02 n.d. 1370 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 2.2 131 0.01 n.d. 97 n.d. PKB2-7 n.d. 22.0 1451 n.d. n.d. 3248 n.d. n.d. 0.14 n.d. n.d. n.d. n.d. 0.02 1.9 6 0.04 n.d. 463 0.03 PKB3-7 n.d. 30.2 2428 n.d. n.d. 1083 n.d. n.d. 0.11 n.d. n.d. n.d. n.d. 0.02 2.5 210 0.02 n.d. 475 0.09 PKB4-7 n.d. 24.7 2920 n.d. 0.08 930 n.d. n.d. 0.25 n.d. n.d. n.d. n.d. 0.08 2.3 11 0.03 0.01 37 0.13 PKB5-7 n.d. 29.5 2902 n.d. n.d. 1780 n.d. n.d. 0.12 n.d. n.d. n.d. n.d. n.d. 2.0 113 n.d. n.d. 1012 n.d. PKB6-7 3 28.1 2411 n.d. n.d. 797 n.d. n.d. 0.18 n.d. n.d. n.d. n.d. n.d. 1.9 125 0.02 n.d. 914 0.05 PKB7-7 n.d. 34.6 2820 n.d. n.d. 805 n.d. n.d. 0.22 n.d. n.d. n.d. n.d. n.d. 2.1 197 n.d. n.d. 862 0.10 PKB8-7 2 46.4 2188 0.02 n.d. 1570 0.02 n.d. 0.09 n.d. n.d. n.d. n.d. n.d. 2.5 192 0.01 n.d. 1704 0.06 PKB9-7 n.d. 40.5 2371 n.d. n.d. 1295 0.02 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 2.4 203 0.01 n.d. 859 0.05 PKB10-7 n.d. 33.3 2041 n.d. n.d. 753 n.d. n.d. 0.12 n.d. n.d. n.d. n.d. 0.02 1.7 117 0.01 n.d. 984 0.04 PKB11-7 n.d. 36.2 2736 n.d. n.d. 885 n.d. n.d. 0.14 n.d. n.d. n.d. n.d. n.d. 2.5 290 0.01 n.d. 1066 0.34 PKB12-7 n.d. 29.8 1850 0.02 n.d. 691 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 2.1 36 0.01 n.d. 216 n.d. PKB13-7 n.d. 45.7 784 0.02 0.06 1217 n.d. 0.01 0.11 0.06 n.d. 0.06 n.d. n.d. 3.2 408 0.04 0.01 59 n.d. PKB14-7 n.d. 19.2 688 0.02 n.d. 1146 n.d. n.d. 0.14 n.d. n.d. 0.02 n.d. n.d. 1.6 73 0.02 0.03 59 n.d. PKB15-7 n.d. 40.2 519 0.03 n.d. 669 n.d. n.d. 0.20 n.d. n.d. 0.05 n.d. n.d. 2.5 240 0.01 n.d. 53 0.02 PKB16-7 3 21.6 2596 n.d. n.d. 515 n.d. n.d. 0.17 n.d. n.d. n.d. n.d. n.d. 2.0 31 0.01 0.01 267 n.d. PKB17-7 n.d. 26.5 2293 n.d. n.d. 1125 n.d. n.d. 0.15 n.d. n.d. 0.01 n.d. n.d. 2.1 39 0.01 0.01 1149 0.02 PKB18-7 4 29.9 2554 n.d. n.d. 453 n.d. n.d. 0.13 n.d. n.d. n.d. n.d. n.d. 2.2 16 n.d. n.d. 188 0.03 PKB1-8 12 58.6 2338 n.d. 0.10 3507 0.02 n.d. 0.08 n.d. n.d. n.d. n.d. n.d. 3.5 1602 0.04 0.01 3091 0.02 PKB2-8 1 16.5 2714 n.d. n.d. 163 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.3 179 n.d. n.d. 522 n.d. PKB3-8 1 26.2 1235 n.d. n.d. 116 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.04 0.7 2621 n.d. n.d. 9 n.d. PKB4-8 n.d. 66.3 2314 0.02 n.d. 3038 n.d. n.d. 0.07 n.d. n.d. n.d. n.d. n.d. 2.5 66 0.04 0.01 1987 n.d. PKB5-8 n.d. 2.4 154 n.d. 0.11 170 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 46 n.d. n.d. 180 n.d. PKB6-8 n.d. 8.9 1680 n.d. n.d. 562 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.4 44 n.d. n.d. 486 n.d. KC1-1 n.d. 129.6 4961 n.d. n.d. 3847 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 15.5 2.33 n.d. n.d. 67.9 n.d. KC2-1 n.d. 74.8 267 n.d. n.d. 634 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 11.5 161 n.d. n.d. 103 n.d. KC3-1 n.d. 31.4 2351 n.d. n.d. 196 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 7.2 10.8 n.d. n.d. 40.8 n.d. KC4-1 n.d. 20 1579 n.d. n.d. 1367 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 8 11.5 n.d. n.d. 122 n.d. KC5-1 1 0.6 4857 n.d. n.d. 130 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.47 0.3 0.3 0.01 n.d. 40.6 0.05 KC6-1 2 0.5 8440 n.d. n.d. 340 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 11.5 0.2 0.06 0.03 n.d. 12.6 0.15 KC12-1 1 6.2 5687 n.d. 0.08 124 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.06 3.5 18.8 0.01 n.d. 42.4 0.04 KC13-1 1 2.5 3478 n.d. n.d. 55.4 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.13 1.9 8.2 0.01 n.d. 38.7 0.03 KC14-1 n.d. n.d. 704 n.d. 0.1 133 n.d. n.d. n.d. n.d. n.d. 0.01 n.d. n.d. 0.5 2.12 0.01 n.d. 706 n.d. KC15-1 n.d. 13.8 2476 n.d. n.d. 455 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 11.6 13.5 n.d. n.d. 60.3 n.d. KC16-1 n.d. 11 578 n.d. n.d. 1326 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 5.4 94.8 n.d. n.d. 115 n.d. KC17-1 n.d. 1.5 415 n.d. n.d. 463 n.d. n.d. n.d. n.d. n.d. 0.02 n.d. n.d. 0.7 213 0.01 n.d. 215 n.d. KC37-1 n.d. 108.9 3382 n.d. n.d. 965 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 7.6 25.5 n.d. n.d. 399 n.d. KC38-1 n.d. 108.8 696 n.d. n.d. 1752 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 6.4 78.1 n.d. n.d. 200 n.d. 170

Table A.3: Full trace element analysis for Mannville produced fluid samples.

Ag Al As Au B Ba Be Bi Br Ca Cd Ce Cl Co Cr Cs Cu Dy Er Eu Fe Ga Gd Ge Hf Hg Ho In Ir Sample I.D. ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppm ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb PKB1 35 119 136 n.d. 7889.0 146303 n.d. n.d. 222457 2485427 n.d. n.d. 5242.50 4 n.d. 28 287 n.d. n.d. 3 22145 n.d. 2 n.d. n.d. n.d. n.d. n.d. n.d. PKB2 17 n.d. 139 n.d. 7267.0 189075 n.d. n.d. 229178 2356220 n.d. n.d. 5205.90 6 n.d. 18 298 n.d. n.d. 9 30877 n.d. 3 n.d. n.d. n.d. n.d. n.d. n.d. PKB3 9 n.d. 143 n.d. 7386.0 148613 n.d. n.d. 229479 2535110 n.d. n.d. 5212.70 4 n.d. 31 290 n.d. n.d. 9 34636 n.d. 3 n.d. n.d. n.d. n.d. n.d. n.d. PKB4 5 n.d. 152 n.d. 7796.0 166085 n.d. n.d. 233997 2673246 n.d. n.d. 5384.60 4 n.d. 27 303 n.d. n.d. 9 24821 n.d. 3 n.d. n.d. n.d. n.d. n.d. n.d. PKB5 n.d. 225 148 n.d. 8256.0 132902 n.d. n.d. 224943 2759451 n.d. n.d. 5438.80 3 n.d. 42 808 n.d. n.d. 11 23285 n.d. 2 n.d. n.d. n.d. n.d. n.d. n.d. PKB6 n.d. 649 157 n.d. 8021.0 165736 n.d. n.d. 228389 2741679 n.d. n.d. 5420.90 3 n.d. 34 333 n.d. n.d. 10 21726 n.d. 3 n.d. n.d. n.d. n.d. n.d. n.d. PKB7 n.d. 378 165 n.d. 7858.0 141017 n.d. n.d. 230031 2848566 n.d. n.d. 5524.20 4 n.d. 44 360 n.d. n.d. 11 29046 n.d. 2 n.d. n.d. n.d. n.d. n.d. n.d. PKB8 n.d. 316 156 n.d. 8084.0 148739 n.d. n.d. 222241 2901990 8 n.d. 5514.60 3 n.d. 47 389 n.d. n.d. 12 29122 n.d. 4 n.d. n.d. n.d. n.d. n.d. n.d. PKB9 n.d. 114 155 n.d. 7176.0 161507 n.d. n.d. 221741 2723683 n.d. n.d. 5453.20 4 n.d. 38 344 n.d. n.d. 15 26093 n.d. 3 n.d. n.d. n.d. n.d. n.d. n.d. PKB1-1 n.d. n.d. 145 n.d. 6873.0 150551 n.d. n.d. 199568 1713880 n.d. n.d. 4945.50 3 n.d. 21 353 n.d. n.d. 10 18572 n.d. 3 n.d. n.d. n.d. n.d. n.d. n.d. PKB2-1 n.d. 1125 147 n.d. 7778.0 151154 n.d. n.d. 197421 1911905 n.d. n.d. 4910.10 4 n.d. 21 340 n.d. n.d. 14 38453 n.d. 3 n.d. n.d. n.d. n.d. n.d. n.d. PKB3-1 n.d. 115 140 n.d. 6903.0 135522 n.d. n.d. 166079 2060177 12 n.d. 4786.30 4 n.d. 18 299 n.d. n.d. 11 63054 n.d. 3 n.d. n.d. n.d. n.d. n.d. n.d. PKB4-1 n.d. 806 140 n.d. 6877.0 143490 n.d. n.d. 197688 1608182 n.d. n.d. 4710.30 4 n.d. 18 366 n.d. n.d. 12 21812 n.d. 2 n.d. n.d. n.d. n.d. n.d. n.d. PKB5-1 n.d. 457 155 n.d. 8146.0 107795 n.d. n.d. 207210 1881415 n.d. n.d. 4966.20 2 n.d. 29 340 n.d. n.d. 8 14919 n.d. 2 n.d. n.d. n.d. n.d. n.d. n.d. PKB1-4 n.d. n.d. 128 n.d. 6002.0 69432 n.d. n.d. 158817 2098852 n.d. n.d. 4352.00 4 n.d. 3 255 n.d. n.d. 4 18252 n.d. 2 n.d. n.d. n.d. n.d. n.d. n.d. PKB2-4 n.d. n.d. 157 n.d. 6747.0 96683 n.d. n.d. 165606 3192393 n.d. n.d. 4814.20 4 n.d. 5 277 n.d. n.d. 7 31398 n.d. 2 n.d. n.d. n.d. n.d. n.d. n.d. PKB3-4 n.d. n.d. 135 n.d. 8494.0 144997 n.d. n.d. 186996 1815473 n.d. n.d. 4816.40 n.d. n.d. 19 294 n.d. n.d. 12 14438 n.d. 3 n.d. n.d. n.d. n.d. n.d. n.d. PKB4-4 n.d. n.d. 153 n.d. 6754.0 86265 n.d. n.d. 182950 2829512 n.d. n.d. 4566.20 4 n.d. 10 284 n.d. n.d. 8 35892 n.d. 1 n.d. n.d. n.d. n.d. n.d. n.d. PKB5-4 n.d. 123 55 n.d. 9100.0 3116.2 n.d. n.d. 67389 428054 n.d. n.d. 1785.90 n.d. n.d. 11 147 n.d. n.d. n.d. 2584 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. PKB01-9 44.3 308 125 0.33 8455 156756 1.55 0.72 105923 788644 n.d. 0.15 34307 2.32 22.7 19.2 110 0.02 n.d. 21.0 10089 0.20 4.0 0.7 n.d. n.d. n.d. 0.01 n.d. PKB02-9 14.7 72 122 n.d. 16552 191403 n.d. 0.46 103464 988748 n.d. 0.07 38274 1.79 23.4 21.3 85.8 n.d. n.d. 30.7 51270 0.08 4.3 1.6 n.d. n.d. n.d. n.d. n.d. PKB03-9 7.8 165 141 n.d. 18862 170666 n.d. 0.22 120089 1244790 n.d. 0.10 42450 2.43 19.9 36.4 95.5 0.05 n.d. 27.5 56645 n.d. 3.8 5.2 n.d. 0.5 0.02 0.02 n.d. PKB04-9 6.4 1289 154 n.d. 30559 154681 n.d. 0.39 114219 1304141 0.11 0.04 44853 3.19 18.7 36.8 87.8 0.03 n.d. 25.4 57747 n.d. 3.3 2.0 n.d. 1.0 n.d. 0.04 n.d. PKB05-9 2.4 108 158 n.d. 12261 215105 1.51 0.44 153243 1219139 n.d. 0.07 44847 2.92 17.2 20.1 97.9 n.d. n.d. 37.0 23117 n.d. 4.3 0.4 n.d. 3.0 n.d. n.d. n.d. 170 171

K LaL iL uM gM nM oN aN bNd Ni Os P P bPd Pr Pt Rb Re Rh Ru S Sample I.D. ppb ppb ppb ppb ppb ppb ppb ppm ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppm PKB1 207457 3 5822.7 n.d. 610 1022 n.d. 2862.70 n.d. n.d. n.d. n.d. 2650.0 n.d. n.d. n.d. n.d. 318 n.d. n.d. n.d. n.d. PKB2 298510 3 4872.8 n.d. 626 940 n.d. 2844.28 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 252 n.d. n.d. n.d. n.d. PKB3 226830 3 5814.5 n.d. 624 1216 n.d. 2898.06 n.d. n.d. n.d. n.d. 6378.0 13 n.d. n.d. n.d. 351 n.d. n.d. n.d. n.d. PKB4 212988 3 5264.9 n.d. 666 1092 n.d. 2981.66 n.d. n.d. n.d. n.d. 3617.0 14 n.d. n.d. n.d. 330 n.d. 2 n.d. n.d. PKB5 318919 3 7169.0 n.d. 580 897 n.d. 2992.39 n.d. n.d. n.d. n.d. 4787.0 33 n.d. n.d. n.d. 529 n.d. 1 n.d. 113 PKB6 290504 4 6513.1 n.d. 581 1202 n.d. 2937.30 n.d. n.d. n.d. n.d. 5852.0 20 n.d. n.d. n.d. 471 n.d. 1 n.d. n.d. PKB7 319403 2 6644.9 n.d. 601 994 n.d. 3025.97 n.d. n.d. n.d. n.d. 3691.0 n.d. n.d. n.d. n.d. 542 n.d. 3 n.d. 102 PKB8 436674 3 6601.1 n.d. 587 1177 n.d. 3106.77 n.d. n.d. n.d. n.d. 3817.0 57 n.d. n.d. n.d. 585 n.d. 2 n.d. n.d. PKB9 324969 3 5603.2 n.d. 542 1122 n.d. 2663.48 n.d. n.d. n.d. n.d. 4883.0 21 n.d. n.d. n.d. 482 n.d. 3 n.d. 101 PKB1-1 187830 3 4181.5 n.d. 592 363 n.d. 2653.14 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 276 n.d. 3 n.d. 104 PKB2-1 197158 3 4688.4 n.d. 662 742 n.d. 2724.48 n.d. n.d. n.d. n.d. n.d. 13 n.d. n.d. n.d. 308 n.d. 2 n.d. n.d. PKB3-1 174636 3 4489.9 n.d. 718 1141 n.d. 2510.05 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 263 n.d. 3 n.d. n.d. PKB4-1 159878 2 3772.8 n.d. 548 386 n.d. 2591.00 n.d. n.d. n.d. n.d. 13037.0 n.d. n.d. n.d. n.d. 263 n.d. 2 n.d. n.d. PKB5-1 253482 2 5103.0 n.d. 642 350 n.d. 2820.44 n.d. n.d. n.d. n.d. 2891.0 14 n.d. n.d. n.d. 420 n.d. 3 n.d. n.d. PKB1-4 97688 n.d. 3537.6 n.d. 685 1148 n.d. 2254.87 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 89 n.d. 3 n.d. n.d. PKB2-4 201604 2 4157.4 n.d. 849 2751 n.d. 2480.63 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 109 n.d. 4 n.d. n.d. PKB3-4 213470 3 4276.0 n.d. 703 940 n.d. 2766.77 n.d. n.d. n.d. n.d. 2310.0 n.d. n.d. n.d. n.d. 315 n.d. 4 n.d. n.d. PKB4-4 197865 1 4864.7 n.d. 872 1246 n.d. 2590.30 n.d. n.d. n.d. n.d. n.d. 15 n.d. n.d. n.d. 238 n.d. 4 n.d. n.d. PKB5-4 165796 n.d. 3424.3 n.d. 244 116 n.d. 1133.13 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 236 n.d. n.d. n.d. 104 PKB01-9 104992 2.7 4059.4 0.2 268748 280 2.7 1.89E+01 0.74 n.d. n.d. n.d. 1359 92.1 0.2 0.02 0.07 126 0.05 n.d. n.d. 19 PKB02-9 2780165 3.0 3996.3 0.3 286113 933 7.1 1.78E+01 0.26 0.14 n.d. n.d. 1660 14.9 0.8 0.02 0.07 363 n.d. 0.20 0.13 n.d. PKB03-9 3704410 3.0 4095.5 0.2 335247 1189 1.8 1.98E+01 0.20 n.d. n.d. n.d. 1617 24.5 0.6 0.02 n.d. 480 n.d. 0.89 0.43 n.d. PKB04-9 4234829 2.6 3818.9 0.3 342218 1508 1.9 1.95E+01 0.24 0.20 n.d. n.d. 1607 43.9 0.4 0.05 n.d. 560 0.03 0.68 0.93 n.d. PKB05-9 122630 3.7 3133.6 0.4 368135 791 1.0 2.33E+01 0.31 0.12 n.d. n.d. 1356 32.6 n.d. 0.01 n.d. 128 0.03 1.56 0.36 n.d. 171 172

Sb Sc Se Si Sm Sn Sr Ta Tb Te Th Ti Tl Tm U V W Y Yb Zn Zr Sample I.D. ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb ppb PKB1 n.d. n.d. 1101 9329.0 n.d. n.d. 245 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 154 n.d. 3 2 58 n.d. PKB2 n.d. n.d. 1142 9197.0 n.d. n.d. 253 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 177 n.d. 3 3 107 n.d. PKB3 n.d. n.d. 1267 9799.0 n.d. n.d. 241 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 188 n.d. 4 2 101 n.d. PKB4 n.d. n.d. 1249 10915.0 n.d. n.d. 258 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 201 n.d. 3 2 82 n.d. PKB5 n.d. n.d. 1196 13040.0 n.d. n.d. 242 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 204 n.d. 3 2 1462 n.d. PKB6 n.d. n.d. 1219 10194.0 n.d. n.d. 250 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 197 n.d. 3 2 338 n.d. PKB7 n.d. n.d. 1269 12820.0 n.d. n.d. 244 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 205 n.d. 3 2 224 n.d. PKB8 n.d. n.d. 1270 10496.0 n.d. n.d. 251 n.d. n.d. 8 n.d. n.d. n.d. n.d. n.d. 219 n.d. 3 3 407 n.d. PKB9 n.d. n.d. 1214 12056.0 n.d. n.d. 247 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 215 n.d. 3 3 151 n.d. PKB1-1 n.d. n.d. 1113 11296.0 n.d. n.d. 247 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 200 n.d. 4 2 409 n.d. PKB2-1 n.d. n.d. 1119 9729.0 n.d. n.d. 245 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 211 n.d. 3 2 191 n.d. PKB3-1 n.d. n.d. 949 8110.0 n.d. n.d. 224 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 192 n.d. 3 2 133 n.d. PKB4-1 n.d. n.d. 1147 12331.0 n.d. n.d. 244 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 187 n.d. 3 2 180 n.d. PKB5-1 n.d. n.d. 1232 10557.0 n.d. n.d. 245 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 199 n.d. 3 2 339 n.d. PKB1-4 n.d. n.d. 946 5914.0 n.d. n.d. 229 n.d. n.d. 7 n.d. n.d. n.d. n.d. n.d. 157 6 2 n.d. 126 n.d. PKB2-4 n.d. n.d. 990 6022.0 n.d. n.d. 226 n.d. n.d. 6 n.d. n.d. n.d. n.d. n.d. 178 3 3 2 82 n.d. PKB3-4 n.d. n.d. 1053 10835.0 n.d. n.d. 231 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 179 5 3 2 72 n.d. PKB4-4 n.d. n.d. 1091 9528.0 n.d. n.d. 208 n.d. n.d. 12 n.d. n.d. n.d. n.d. n.d. 171 7 2 2 89 n.d. PKB5-4 n.d. n.d. 408 12043.0 n.d. n.d. 36 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 74 3 n.d. n.d. -50 n.d. PKB01-9 0.57 n.d. 460 10256 1.77 1.45 135169.1 0.14 0.01 9.0 n.d. 15 n.d. n.d. 0.36 210 n.d. 2.1 4.3 2610 n.d. PKB02-9 0.62 n.d. 381 7862 1.78 0.78 139707.5 0.02 n.d. 14.2 n.d. 16 n.d. 0.01 0.21 236 1.73 2.6 5.6 75 n.d. PKB03-9 0.80 n.d. 433 10325 1.81 0.72 152663.2 n.d. n.d. 15.4 n.d. 19 n.d. 0.05 0.21 249 n.d. 2.1 6.1 101 0.03 PKB04-9 0.72 36 396 10492 2.18 0.94 149902.5 n.d. 0.01 14.1 n.d. 12 n.d. 0.06 0.13 265 n.d. 2.1 5.1 201 n.d. PKB05-9 0.24 19 550 7984 2.19 0.47 185282.2 0.04 n.d. 12.0 n.d. 15 n.d. n.d. 0.19 290 n.d. 3.1 7.0 868 n.d. 172 173

APPENDIX: B

Table B.1: Full trace element analysis for coal samples. IMS denotes analysis by inductively coupled mass spectrometer by ACME Laboratories, and NAA denotes analysis by neutron activation.

IMS IMS NAA NAA NAA IMS IMS NAA IMS IMS NAA NAA NAA NAA IMS IMS Ag Al As Au Ba Be Bi Br Ca Cd Ce Co Cr Cs Cu Dy ppb % ppm ppb ppm ppm ppm ppm % ppm ppm ppm ppm ppm ppm ppm KC-C01 37 0.64 1.6 n.d. 198 n.d. n.d. 0.6 0.57 0.1 4.67 4.18 4.9 0.5 2.7 0.8 KC-C02 149 4.46 1.9 2 391 n.d. 0.17 0.7 0.38 0.35 25.4 3.39 43.5 5.5 18.4 1.4 KC-C03 45 0.29 2.4 n.d. 255 1 n.d. 0.6 0.52 0.06 10 4.87 n.d. n.d. 1.9 1.4 KC-C04 170 5.09 3.0 n.d. 449 n.d. 0.13 0.5 0.4 0.62 41.1 4.08 50.7 5.8 18.6 2.2 KC-C05 116 1.90 2.5 n.d. 327 n.d. 0.13 0.7 0.54 0.39 25.9 3.45 12.6 0.9 10.5 2.1 KC-C06 62 1.33 2.0 n.d. 616 n.d. 0.1 0.7 0.52 0.14 11.4 3.55 2.8 0.2 5.5 1.1 KC-C07 203 8.87 2.7 5 550 n.d. 0.32 n.d. 0.28 0.24 31.6 3.47 81.5 11.5 43.1 0.9 KC-C08 55 0.86 2.3 n.d. 525 n.d. 0.06 0.9 0.56 0.08 21 4.82 3.1 n.d. 2.3 1.6 KC-C09 n.d. 0.35 1.3 n.d. 218 n.d. n.d. 1.0 0.51 0.04 9.43 3.79 n.d. n.d. 1.5 0.9 KC-C10 45 0.71 2.0 n.d. 235 n.d. 0.06 0.8 0.42 0.09 7.58 7.63 4.7 0.2 3.7 0.8 KC-C11 198 1.39 2.4 n.d. 160 2 0.04 3.5 0.27 0.51 7.65 9.5 27.4 0.5 16.8 1.5 KC-C12 34 0.76 0.2 n.d. 165 n.d. n.d. 1.4 0.07 0.09 4.21 2.96 3.9 n.d. 9.2 0.4 KC-C13 55 0.96 3.7 n.d. 250 n.d. 0.05 1.6 0.06 0.08 4.7 3.84 5.8 n.d. 9.9 0.5 KC-C14 59 1.38 1.3 n.d. 316 n.d. n.d. 1.6 0.77 0.1 26 2.02 4.6 n.d. 6.9 2.9 KC-C15 231 1.62 11.3 n.d. 320 3 n.d. 1.8 0.44 0.16 12.7 2.16 26.8 2.8 4.2 1.3 KC-C16 671 5.16 5.0 9 733 2 0.13 n.d. 0.48 4.94 53.3 5.91 73.6 4.3 28.5 5 KC-C17 730 5.20 22.2 6 1340 2 0.25 1.0 0.61 3.4 54.9 11.1 122 6.9 40.5 2.1 KC-C18 620 5.91 7.5 n.d. 1900 2 0.24 0.6 0.24 1.98 52.2 3.94 118 11.2 30.9 0.8 KC-C19 n.d. 0.42 n.d. n.d. 83 n.d. n.d. 2.2 0.03 n.d. 21.9 0.85 2.4 0.1 2.5 0.7 KC-C20 259 1.05 2.0 n.d. 337 3 0.04 2.4 0.35 1.66 5.01 10.8 31.4 0.8 51.9 2.3 KC-C21 237 6.60 3.9 n.d. 982 1 0.32 8.9 1.27 0.31 41.1 1.65 9.1 5.4 8.9 1.9 KC-C22 71 2.10 1.9 n.d. 314 n.d. 0.09 9.7 1.16 0.15 18.8 4.49 8.9 1.6 6.4 1.5 KC-C23 28 0.41 1.6 n.d. 162 n.d. n.d. 11.5 1.02 0.05 7.07 4.21 n.d. n.d. 1.3 0.7 KC-C24 74 1.09 2.3 n.d. 239 n.d. 0.12 5.0 1.23 0.14 20.1 3.24 1.6 0.3 3.5 1.1 KC-C25 93 1.43 3.6 n.d. 254 1 0.12 6.1 1.16 0.13 20.1 3.82 3.1 n.d. 7.5 1.6 KC-C26 88 2.51 2.2 n.d. 425 n.d. 0.16 19.2 1.22 0.22 30.1 3.13 25.2 2.9 17.3 1.6 KC-C27 82 1.35 1.8 n.d. 228 n.d. 0.14 7.9 1.39 0.1 11.9 1.25 n.d. n.d. 3.1 0.9 KC-C28 118 1.39 9.3 n.d. 270 2 0.2 6.7 1.39 0.11 30.1 5.87 6.4 n.d. 7.3 3.3 KC-C29 102 2.00 4.8 n.d. 449 n.d. 0.15 6.5 1.17 0.1 26.9 2.82 2.2 n.d. 7.5 1.6 KC-C30 114 1.31 2.5 n.d. 379 n.d. 0.11 6.5 1.21 0.11 11.9 3.83 6.9 0.4 10.7 1.5 KC-C31 30 0.40 1.5 n.d. 145 n.d. n.d. 9.9 0.99 0.05 7.39 4.06 n.d. 0.1 1.0 0.6 173 174

IMS NAA NAA IMS IMS IMS NAA NAA IMS IMS NAA IMS NAA IMS NAA IMS Er Eu Fe Ga Gd Ge Hf Hg Ho In Ir K La Li Lu Mg ppm ppm % ppm ppm ppm ppm ppm ppm ppm ppb % ppm ppm ppm % KC-C01 0.6 0.17 0.28 1.7 0.7 n.d. 0.52 n.d. 0.2 n.d. n.d. 0.07 2.6 5.7 0.12 0.06 KC-C02 0.8 0.41 0.73 11.9 1.4 n.d. 2.89 n.d. 0.3 n.d. n.d. 0.85 14.0 31.2 0.17 0.19 KC-C03 1.0 0.25 0.26 0.7 1.1 n.d. 0.59 n.d. 0.3 n.d. n.d. 0.08 6.5 7.4 0.18 0.04 KC-C04 1.1 0.81 0.98 12.3 2.4 n.d. 3.30 0.19 0.4 n.d. n.d. 0.89 20.6 35.0 0.19 0.24 KC-C05 1.1 0.58 0.29 5.3 2.3 n.d. 1.89 n.d. 0.4 n.d. n.d. 0.40 11.8 12.1 0.16 0.07 KC-C06 0.7 0.21 0.21 3.6 0.9 n.d. 1.09 n.d. 0.2 n.d. n.d. 0.05 6.9 9.4 0.12 0.06 KC-C07 0.6 0.53 1.88 23.9 0.9 n.d. 3.71 n.d. 0.2 n.d. n.d. 1.87 18.4 47.4 0.22 0.52 KC-C08 0.9 0.39 0.23 1.8 1.3 n.d. 1.12 n.d. 0.3 n.d. n.d. 0.03 11.3 7.5 0.13 0.04 KC-C09 0.6 0.18 0.18 0.7 0.8 n.d. 0.44 n.d. 0.2 n.d. n.d. n.d. 5.1 2.6 0.10 0.03 KC-C10 0.5 0.13 0.23 2.1 0.6 n.d. 0.75 n.d. 0.2 n.d. n.d. 0.03 5.3 4.7 0.12 0.04 KC-C11 1.0 0.40 0.92 12.9 1.5 n.d. 0.57 n.d. 0.3 n.d. n.d. 0.32 4.0 7.2 0.14 0.22 KC-C12 0.2 0.15 0.45 1.8 0.4 n.d. 0.65 n.d. n.d. n.d. n.d. n.d. 1.5 8.8 0.05 0.06 KC-C13 0.3 0.17 0.50 2.5 0.5 n.d. 0.88 0.37 n.d. n.d. n.d. n.d. 2.1 11.5 0.08 0.06 KC-C14 1.6 0.58 0.47 2.1 2.6 n.d. 1.28 0.15 0.6 n.d. n.d. 0.05 14.5 15.2 0.21 0.07 KC-C15 1.0 0.41 2.69 7.0 1.1 n.d. 4.99 n.d. 0.3 n.d. n.d. 0.49 8.0 13.2 0.26 0.58 KC-C16 2.2 1.88 0.37 9.4 5.9 1.1 9.66 n.d. 0.9 n.d. n.d. 2.11 31.6 29.9 0.65 0.26 KC-C17 1.0 1.09 0.59 14.4 2.6 n.d. 7.69 0.17 0.4 n.d. n.d. 1.64 35.0 35.4 0.37 0.47 KC-C18 0.5 0.63 0.62 17.5 1.6 n.d. 7.63 n.d. 0.2 n.d. n.d. 2.07 33.2 124 0.32 0.33 KC-C19 0.4 0.22 0.02 2.0 0.8 n.d. 0.38 n.d. 0.1 n.d. n.d. n.d. 16.2 4.3 0.07 n.d. KC-C20 1.5 0.39 0.32 19.3 1.5 n.d. 1.34 0.10 0.5 n.d. n.d. 0.25 2.8 6.0 0.27 0.12 KC-C21 1.0 0.67 1.04 23.0 2.1 n.d. 5.13 n.d. 0.4 n.d. n.d. 0.49 22.6 30.5 0.20 0.63 KC-C22 0.9 0.44 0.53 4.9 1.6 n.d. 1.27 n.d. 0.3 n.d. n.d. 0.25 9.8 6.6 0.16 0.14 KC-C23 0.6 0.18 0.40 1.2 0.8 n.d. 0.49 n.d. 0.2 n.d. n.d. n.d. 3.6 1.8 0.09 0.07 KC-C24 0.7 0.32 0.28 2.5 1.2 n.d. 1.31 n.d. 0.2 n.d. n.d. n.d. 11.2 4.5 0.11 0.15 KC-C25 1.1 0.34 0.28 3.6 1.5 n.d. 1.39 n.d. 0.3 n.d. n.d. n.d. 11.3 5.4 0.17 0.16 KC-C26 1.1 0.50 0.56 6.3 1.8 n.d. 1.47 n.d. 0.3 n.d. n.d. 0.62 16.2 11.3 0.22 0.26 KC-C27 0.5 0.16 0.33 3.4 0.8 n.d. 1.26 n.d. 0.2 n.d. n.d. n.d. 6.7 5.4 0.07 0.08 KC-C28 1.9 0.74 0.43 4.3 3.0 n.d. 2.30 0.29 0.7 n.d. n.d. 0.03 16.5 5.4 0.29 0.11 KC-C29 0.9 0.40 0.42 4.9 1.5 n.d. 1.90 n.d. 0.3 n.d. n.d. n.d. 15.7 9.7 0.14 0.22 KC-C30 0.9 0.24 0.39 3.5 1.3 n.d. 1.95 n.d. 0.3 n.d. n.d. 0.05 6.0 7.7 0.19 0.24

KC-C31 0.5 0.15 0.37 1.1 0.8 n.d. 0.43 n.d. 0.2 n.d. n.d. n.d. 3.7 1.6 0.09 0.07 174 175

IMS IMS NAA IMS NAA IMS IMS IMS IMS IMS IMS IMS NAA NAA IMS NAA Mn Mo Na Nb Nd Ni P Pb Pr Rb Re S Sb Sc Se Sm ppm ppm % ppm ppm ppm % ppm ppm ppm ppm % ppm ppm ppm ppm KC-C01 59 2.0 0.54 2.0 1.30 8.8 0.002 2.4 0.5 3.6 1 0.45 0.15 2.4 0.4 0.53 KC-C02 27 0.8 0.30 6.9 9.07 9.2 0.007 9.2 2.1 35.8 n.d. 0.23 0.46 7.5 1.1 1.80 KC-C03 28 1.5 0.75 1.5 3.64 8.5 0.015 1.8 1.1 3.5 n.d. 0.54 0.17 2.4 0.6 0.80 KC-C04 28 0.7 0.46 7.1 16.5 16.9 0.013 9.2 3.3 38.0 1 0.23 0.73 9.5 1.2 3.31 KC-C05 23 0.8 0.27 3.8 12.4 9.8 0.027 7.3 3 9.3 n.d. 0.39 0.33 4.6 1.0 2.42 KC-C06 25 1.1 0.36 3.0 4.59 7.6 0.029 5.2 1.2 2.0 1 0.46 0.21 2.5 0.7 0.84 KC-C07 49 0.7 0.45 11.6 11.1 11.9 0.014 12.5 1.1 56.4 n.d. 0.12 0.66 15.7 0.5 2.19 KC-C08 25 1.0 0.27 2.6 6.96 7.9 0.056 3.7 2.1 1.0 1 0.37 0.35 3.3 0.7 1.55 KC-C09 20 0.8 0.27 0.9 4.33 13.9 0.032 1.5 1.1 0.2 n.d. 0.33 0.06 0.9 0.2 0.86 KC-C10 17 1.0 0.30 1.7 2.77 12.5 0.008 3.5 0.7 1.2 2 0.29 0.14 1.8 0.4 0.57 KC-C11 141 1.3 0.078 6.8 4.60 50.4 0.036 5.3 1.4 11.9 3 0.22 9.08 5.5 0.4 1.08 KC-C12 56 2.4 0.011 0.8 2.88 8.4 0.008 1.2 0.4 n.d. n.d. n.d. 0.16 1.4 n.d. 0.60 KC-C13 13 2.1 0.012 1.4 2.20 15.3 0.006 3.8 0.6 0.6 n.d. n.d. 0.20 1.8 0.5 0.61 KC-C14 22 1.5 0.014 0.7 11.2 8.1 0.361 1.2 3.2 1.4 1 0.05 0.19 1.9 0.5 2.65 KC-C15 111 1.3 0.023 10.9 4.10 9.5 0.013 2.7 1.6 22.7 2 0.46 3.01 10.9 1.0 1.09 KC-C16 15 0.8 0.062 7.3 26.4 15.1 0.175 12.2 6.6 70.3 3 0.06 3.84 9.7 2.3 6.48 KC-C17 26 2.5 0.081 15.7 23.5 106.1 0.131 21.2 4.5 55.8 10 0.13 7.20 6.6 4.4 4.31 KC-C18 14 3.9 0.082 10.8 20.3 25.5 0.091 15.7 3 77.0 7 0.12 2.65 7.0 3.0 3.30 KC-C19 n.d. 0.6 0.009 1.0 7.68 3.8 0.017 2.5 2.2 0.3 2 n.d. 0.45 0.9 n.d. 1.13 KC-C20 79 1.4 0.071 58.3 3.60 61.0 0.007 6.5 0.8 9.7 3 0.29 17.30 12.6 0.3 1.04 KC-C21 71 1.3 0.15 15.9 15.7 5.4 0.010 15.5 2.8 9.9 n.d. 0.12 0.84 7.3 0.5 2.94 KC-C22 91 0.8 0.045 2.5 8.60 6.1 0.004 4.3 2.2 13.7 n.d. 0.16 0.41 2.3 0.2 1.86 KC-C23 52 1.4 0.010 1.2 2.96 3.5 0.003 2.9 0.9 n.d. n.d. 0.21 0.13 0.5 n.d. 0.80 KC-C24 76 1.8 0.032 2.9 7.33 4.3 0.006 6.9 2.2 1.0 n.d. 0.31 0.42 1.2 0.4 1.36 KC-C25 90 2.0 0.087 3.7 8.33 5.5 0.004 7.3 2.3 0.5 2 0.38 0.50 1.7 0.5 1.63 KC-C26 93 1.5 0.092 4.6 12.2 4.6 0.004 8.9 3.1 32.5 3 0.26 0.66 4.9 0.5 2.35 KC-C27 72 1.1 0.017 2.9 4.42 5.5 0.006 4.9 1.3 0.5 n.d. 0.14 0.49 1.5 0.2 0.93 KC-C28 119 5.2 0.028 7.2 13.6 11.8 0.006 10.3 3.7 1.5 4 0.49 1.31 2.7 1.1 3.02 KC-C29 61 1.7 0.14 3.9 10.5 4.6 0.003 29.5 3.1 0.8 n.d. 0.37 0.33 1.7 0.6 1.83 KC-C30 137 2.5 0.020 4.5 4.99 5.3 0.002 12.9 1.4 2.7 3 0.31 0.78 3.1 0.5 1.17

KC-C31 47 1.4 0.010 1.2 3.61 3.9 0.003 3.2 0.8 n.d. 1 0.15 0.11 0.5 n.d. 0.78 175 176

IMS IMS NAA NAA IMS NAA IMS IMS IMS NAA IMS IMS IMS NAA IMS IMS Sn Sr Ta Tb Te Th Ti Tl Tm U V W Y Yb Zn Zr ppm ppm ppm ppm ppm ppm % ppm ppm ppm ppm ppm ppm ppm ppm ppm KC-C01 0.2 105 0.06 0.13 n.d. 0.72 0.031 0.1 n.d. 0.63 8.0 0.6 5.7 0.66 5.7 19 KC-C02 1.1 88 0.59 0.22 n.d. 5.67 0.263 0.4 0.1 2.09 61.0 0.7 6.7 1.03 21.7 71 KC-C03 n.d. 125 0.05 0.16 n.d. 0.53 0.011 n.d. 0.1 0.35 3.0 0.6 8.7 0.98 4.5 29 KC-C04 1.1 107 0.55 0.35 n.d. 6.48 0.282 0.5 0.1 2.83 71.0 0.8 7.8 1.17 42.9 85 KC-C05 0.8 124 0.29 0.28 n.d. 3.77 0.087 0.2 0.2 1.46 19.0 0.4 10.7 1.01 16.8 63 KC-C06 0.5 141 0.19 0.13 n.d. 3.02 0.051 n.d. 0.1 0.92 7.0 0.5 7.0 0.68 3.3 37 KC-C07 2.0 87 0.84 0.30 n.d. 7.36 0.506 0.9 n.d. 2.59 128 1.2 3.2 1.26 60.7 72 KC-C08 0.2 196 0.11 0.27 n.d. 1.69 0.023 n.d. 0.1 0.84 6.0 0.4 8.7 0.80 2.9 37 KC-C09 n.d. 155 0.03 0.16 n.d. 0.50 0.01 n.d. n.d. 0.50 3.0 0.2 6.6 0.55 1.6 14 KC-C10 0.3 77 0.13 0.15 n.d. 1.42 0.036 n.d. n.d. 0.53 7.0 0.4 6.3 0.61 3.3 15 KC-C11 0.2 40 0.08 0.25 n.d. 0.59 0.068 0.2 0.1 0.97 83.0 0.2 9.1 0.77 44.0 56 KC-C12 0.1 68 0.08 n.d. n.d. 1.02 0.029 0.2 n.d. 0.54 9.0 n.d. 2.2 0.29 3.1 10 KC-C13 0.2 84 0.10 n.d. n.d. 1.06 0.042 0.5 n.d. 0.58 14.0 0.1 3.0 0.41 7.6 17 KC-C14 0.1 312 0.08 0.42 0.1 0.85 0.023 0.4 0.2 0.41 8.0 0.8 15.6 1.33 7.1 35 KC-C15 0.6 38 0.35 0.29 0.2 1.95 0.118 0.9 0.1 1.51 85.0 0.6 9.3 1.37 9.0 138 KC-C16 1.1 130 0.76 1.14 n.d. 8.88 0.197 1.0 0.3 4.73 130 0.6 23.3 3.69 138 45 KC-C17 1.8 180 1.01 0.55 0.1 8.32 0.321 1.6 0.1 4.50 334 0.8 8.7 2.11 158 127 KC-C18 1.9 210 0.92 0.42 n.d. 6.88 0.302 1.5 n.d. 2.51 292 0.8 3.1 1.87 162 77 KC-C19 0.1 79 0.03 0.14 n.d. 0.41 0.018 n.d. n.d. 0.36 5.0 0.7 4.8 0.46 1.7 8 KC-C20 0.3 71 0.18 0.31 n.d. 0.66 0.114 n.d. 0.2 5.03 540 3.4 11.8 1.50 30.6 99 KC-C21 3.4 232 1.42 0.34 n.d. 10.90 0.26 0.2 0.1 4.99 19.0 1.3 7.2 1.30 19.6 141 KC-C22 0.5 138 0.23 0.35 0.2 2.69 0.073 0.1 0.1 1.08 18.0 0.3 9.2 0.90 11.3 28 KC-C23 0.2 108 0.09 0.13 0.2 0.88 0.012 n.d. n.d. 0.46 2.0 0.2 6.4 0.50 2.0 15 KC-C24 0.6 113 0.17 0.17 0.2 2.97 0.041 n.d. 0.1 1.36 5.0 0.9 7.0 0.66 3.5 37 KC-C25 0.6 119 0.28 0.22 0.2 4.22 0.04 n.d. 0.1 1.65 8.0 0.7 10.1 0.98 6.0 44 KC-C26 1.0 95 0.31 0.21 0.2 4.43 0.099 0.2 0.2 1.37 35.0 0.5 10.5 1.17 9.0 35 KC-C27 0.6 153 0.20 0.19 0.3 2.78 0.031 n.d. n.d. 1.37 4.0 0.5 4.8 0.45 9.1 38 KC-C28 0.9 127 0.31 0.49 0.3 6.59 0.058 1.2 0.3 3.39 15.0 2.1 19.0 1.75 10.9 67 KC-C29 0.7 136 0.34 0.30 0.2 5.98 0.051 n.d. 0.1 1.82 5.0 0.7 9.6 0.86 16.5 51 KC-C30 0.4 73 0.18 0.26 0.3 2.99 0.039 n.d. 0.1 1.70 11.0 0.8 8.2 0.96 5.2 75

KC-C31 0.2 105 0.08 0.12 0.2 0.94 0.011 n.d. n.d. 0.48 2.0 0.2 5.9 0.48 0.9 14 176