CHEMICAL AND ISOTOPIC CHARACTERIZATION OF SHALLOW GROUNDWATER FROM SELECTED MONITORING WELLS IN ALBERTA: Part I: 2006-2007 Alberta Environment ISBN: 978-0-7785-8509-1 (Printed Edition) ISBN: 978-0-7785-8510-7 (On-line Edition) Disclaimer This document is an independent report requested by, and prepared for, Alberta Environment. The authors are solely responsible for the interpretations of data and statements made within this report. The report does not necessarily reflect endorsement by, or the policies of Alberta Environment. Reproduction and Availability This report and its contents may be reproduced in whole, or in part, provided that this title page is included with such reproduction and/or appropriate acknowledgements are provided to the authors and sponsors of this project. 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Reproduction of this publication, in whole or in part, regardless of purpose, requires the prior written permission of Alberta Environment. © H er Majesty the Queen in right of the Province of Alberta, 2009 CHEMICAL AND ISOTOPIC CHARACTERIZATION OF SHALLOW GROUNDWATER FROM SELECTED MONITORING WELLS IN ALBERTA: Part I: 2006-2007 Prepared for: Alberta Environment 4th Floor, Oxbridge Place Edmonton, Alberta, Canada T5K 2J6 Prepared by: Katrina Cheung and Bernhard Mayer Applied Geochemistry Group Department of Geology & G eophysics University of Calgary March 31st, 2007 ( I ( SUMMARY Forty groundwater samples were obtained from shallow aquifers in Alberta for chemical and isotopic analyses in order to assess the current quality of Alberta’s groundwater, and establish a b aseline against which future impacts on groundwater can be evaluated. In addition, one groundwater well was selected for a q uality control test and was repeatedly sampled for dissolved and free gas. The obtained water and gas samples were returned to the laboratory and submitted to various facilities for specialized chemical and isotopic analyses. Results from this study indicate that: • Most groundwaters are of the Na-HCC>3 or Na-HC03-SC>4 type. Sodium (Na) concentrations were often above the aesthetic objective outlined by the Guidelines for Canadian Drinking Water Quality (Health Canada, 2006). A f ew samples were characterized by very low sulphate concentrations indicating active bacterial sulphate reduction in the aquifer. • Metal and trace element concentrations in most groundwater samples did not exceed any MAC or AO guidelines published by Health Canada (2006) with only few exceptions for Fe (3), F ( 1 1), Mn (8), A1 (2), Ba (1), Hg (1), and Se (3). • Concentrations of arsenic and chromium appear to be generally below drinking water guidelines. • Concentrations of benzene and ethylbenzene were generally below the detection limit. Toluene was detected in 1 8 o f the 40 samples, but only one sample exceeded the aesthetic objective outlined in the Guidelines for Canadian Drinking Water Quality (Health Canada, 2006). • Analytical problems were encountered during determination of phenol and volatile organic acid (VOA) concentrations and hence a conclusive interpretation of the obtained results for these compounds is currently not possible. • Polycyclic aromatic hydrocarbons (PAH’s) in most groundwater samples were below the detection limit. • Several groundwater samples showed traces of sulphide suggesting that bacterial sulphate reduction had occurred. • Oxygen and hydrogen isotope ratios indicate that the groundwater is of meteoric origin but that significant evaporation had occurred during the recharge process. • Sulphur and oxygen isotope ratios of dissolved sulphate indicate that oxidation of sulphide minerals such as pyrite is a major source of sulphate in g roundwater. • Only 3 g roundwater samples had sufficient nitrate for isotope analysis. Nitrogen and oxygen isotope ratios of the nitrate suggested an agricultural or waste water source in two of the three cases. • The carbon isotope ratios of methane in free gas varied between -84 and -60 %o, suggesting a p redominately biogenic source of the methane. Carbon isotope ratios of free ethane gas ranged from -66 to -44 %o in the groundwater samples, with the exception of the Warner 215 well with a 8 13C value of ethane of -36.1 %o. Preliminary methodological tests revealed excellent integrity of various gas storage containers over a p eriod of 10 days, little variability of gas concentration and isotope ratios throughout a sampling day, and satisfying agreement between carbon isotope ratio measurements Chemical and Isotopic Characterization of Shallow Groundwater from Selected Monitoring Wells in Alberta v on dissolved and free gas for several samples. Further improvements are, however, required before concentration and isotope measurements on dissolved gases can become a r eliable routine tool in baseline water well testing, specifically for samples with low gas contents. After this initial 4-month project, it a ppears that the chosen parameters are highly effective in assessing the status quo of groundwater quality in Alberta and that the sampling and analytical methodology was for the most part effective. Analytical problems that were encountered during phenol and volatile organic acid (VOA) analyses must be addressed in future monitoring efforts. It is currently unclear whether As and Cr speciation will yield reliable results due to the low total As and Cr concentrations in most aquifers. To improve the reliability of the obtained results and facilitate data processing, it i s recommended that the analyses be carried out in fewer, but highly reliable contract laboratories. Due to the increasing demand on water resources in Alberta it is highly recommended to expand this initial groundwater quality monitoring program to other Alberta Environment wells in the near future with as many water quality parameters as possible. Priority should be given to obtaining baseline water quality data from existing wells that have not been sampled recently. Thereafter, it i s desirable to repeat this water quality monitoring program across the province in regular intervals. Re-sampling of individual wells is also recommended for sites where specific water quality problems have been detected. There are still unresolved questions regarding the extent of temporal (e.g. seasonal) variability of concentrations and isotope ratios of naturally occurring dissolved and free gas in aquifers in Alberta. A s ystematic study assessing the seasonal variability of concentrations and isotope ratios of dissolved and free methane, higher alkanes, and CO2 in selected groundwater wells completed in a variety of hydrogeological settings is recommended. It is important that such a study makes an attempt to distinguish between uncertainties introduced by the sampling techniques and natural variations in the concentrations and isotope ratios of dissolved and free gases. This will help to establish further background data against which future impacts, or the lack thereof, of the coalbed methane industry in the province can be tested. The determination of the chemical and isotopic composition of groundwater from these 40 monitoring wells constitutes an important first step in assessing the status quo of Alberta’s groundwater quality, providing a b aseline against which future change in g roundwater quality can be evaluated. Continued support for this initiative beyond the initial 4-month start-up phase will yield further insights into the fundamental geochemical processes determining groundwater quality in Alberta, natural and anthropogenic impacts on groundwater quality, and the sources and natural variability of dissolved and free gas in Alberta’s groundwater dependent upon geological and hydrogeological settings. It is highly recommended that this program be expanded to include the remaining Alberta Environment monitoring wells in the near future. Chemical and Isotopic Characterization of Shallow Groundwater from Selected Monitoring Wells in Alberta vi TABLE OF CONTENTS SUMMARY.. v LIST OF TABLES... ix LIST OF FIGURES x ACKNOWLEDGEMENTS.... xi 1.0 INTRODUCTION 1 2.0 STUDY AREA 2 2.1 Geology 3 2.1.1 Scollard Formation 3 2.1.2 Horseshoe Canyon Formation 4 2.1.3 Belly River Group 4 2.2 Hydrogeology 4 2.2.1 Scollard-Paskapoo Aquifer 4 2.2.2 Horseshoe Canyon Aquifer 4 2.2.3 Brazeau-Belly River Aquifer 5 3.0 METHODS 6 3.1 Major Ion Chemistry 7 3.2 Trace Elements 7 3.3 Arsenic and Chromium Speciation 7 3.4 Benzene, Toluene, Ethylbenzene, and Xylenes (BTEX) 8 3.5 Phenols 8 3.6 Volatile Organic Acids (as Acetic) 8 3.7 Polycyclic Aromatic Hydrocarbons (PAH) 8 3.8 Sulphide Concentrations 8 3.9 Silica 9 3.10 Stable Isotopes 9 3.10.1 Oxygen and Hydrogen 9 3.10.2 Sulphur 9 3.10.3 Carbon 9 3.10.4 Nitrogen 9 3.11 Gas Composition 10 3.11.1 Dissolved Gas 10 3.11.2 Free Gas 10 3.12 Geochemical Modeling 10 3.13 Quality Control Test 10 4.0 RESULTS AND DISCUSSION 12 4.1 Chemical and Isotopic Composition of Groundwater.... 12 4.1.1 Field Parameters... 12 4.1.2 Major Ion Chemistry 12 4.1.3 Trace Elements 23 4.1.4 Arsenic and Chromium Speciation.. 23 4.1.5 Benzene, Toluene, Ethylbenzene, and Xylenes (BTEX)....... 4 1 Chemical and Isotopic Characterization of Shallow Groundwater from Selected Monitoring Wells in Alberta vii 4.1.6 Phenols 41 4. 1 .7 Volatile Organic Acids (as Acetic) 43 4. 1 .8 Polycyclic Aromatic Hydrocarbons (PAH) 43 4. 1 .9 Sulphide Concentrations 45 4.1.10 Silica 45 4.1.11 Stable Isotopes 56 4.1.11.1 Oxygen and Hydrogen 56 4.1.11.2 Sulphate 57 4.1.11.3 Carbon 57 4.1.1 1.4 Nitrate 57 4.1.12 Gas Composition 57 4.1.12.1 Dissolved Gas 57 4.1.12.2 Free Gas 57 4.1.13 Geochemical Modeling 67 4.2.1 Free versus Dissolved Gas 67 4.2.2 Reproducibility and Natural Variability 68 4.2.2. 1 Dissolved Gas 68 4.2.2.2 Free Gas 68 4.2.3 Storage Containers 68 5.0 CONCLUSIONS 71 6.0 LITERATURE CITED 73 APPENDIX A - L ist of Wells Sampled 76 4 . 2 Methodologic al Tests 67 Chemical and Isotopic Characterization of Shallow Groundwater from Selected Monitoring Wells in Alberta viii LIST OF TABLES Table 1 Field parameters for groundwater samples in Alberta, Canada 15 Table 2 Major cation and anion concentrations of groundwater samples in Alberta, Canada 19 Table 3 Elemental composition of groundwater samples in Alberta, Canada 24 Table 4 Chromium speciation in groundwater samples in Alberta, Canada 40 Table 5 Benzene, toluene, ethylbenzene and xylene concentrations in groundwater samples in Alberta, Canada 42 Table 6 Volatile organic acids (as acetic acid) and phenols in groundwater samples in Alberta, Canada 44 Table 7 Polycyclic aromatic hydrocarbons in groundwater samples from Alberta, Canada 46 Table 8 Sulphide concentrations for groundwater samples from Alberta, Canada 54 Table 9 Silica concentrations for groundwater samples from Alberta, Canada 55 Table 10 Stable isotope ratios of oxygen and hydrogen in water, sulphur and oxygen of sulphate, carbon isotope ratios of dissolved inorganic carbon (DIC), and nitrogen in nitrate 59 Table 11 Stable isotopes of carbon in methane, ethane and carbon dioxide in dissolved gas 61 Table 12 Stable isotopes of carbon in methane, ethane and carbon dioxide in free gas .... 63 Table 13 Saturation indices for anhydrite, aragonite, calcite, dolomite, and gypsum in 40 groundwater samples from Alberta, Canada 65 Table 14 Stable isotope ratios of carbon in methane, ethane and carbon dioxide in free gas from the Warner 215 well, sampled repeatedly over a p eriod of 3 h ours 69 Table 15 Carbon isotope ratios of methane in four different storage containers repeatedly analyzed over a p eriod of ten days 70 Chemical and Isotopic Characterization of Shallow Groundwater from Selected Monitoring Wells in Alberta ix LIST OF FIGURES Figure 1: Map of Alberta showing the location of groundwater sampling sites with respect to the major coal bearing units (after Beaton, 2003). The Scollard formation contains the Ardley coal zone 2 Figure 2: Basin scale stratigraphy and hydrostratigraphy of the Alberta Basin from the Cretaceous to the Tertiary (after Bachu, 1997) 3 Figure 3: Piper plot showing the percent composition of major ions in groundwater (in meq/L) samples from 40 wells in Alberta 13 Figure 4: Schoeller Plot of the major ions in groundwater samples in 40 wells in Alberta. Groundwater samples in red contain low concentrations of sulphate compared to chloride (meq/L). These samples may be affected by bacterial sulphate reduction 14 Figure 5: Plot of 518Oh2o vs. 5DH2o from water in samples from Alberta, Canada and its relation to the Local Meteoric Water Line (LMWL) (Peng et al., 2004) 56 Chemical and Isotopic Characterization of Shallow Groundwater from Selected Monitoring Wells in Alberta x