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Regional groundwater monitoring in the Athabasca region of Alberta, Canada, provides information on groundwater quality and geochemical changes over time, including data useful for evaluating potential impacts of industrial activity such as oil sands mining and in situ operations. Data collected from over 5000 wells from the 1950s to 2014, including 161 wells from government’s monitoring network, were used to develop and apply bootstrap techniques for the detection of changes in groundwater geochemistry over time and at specific points in time. Increasing temporal anomalies were identified in Cl, TDS, B, and naphthenic acids in the McMurray formation across 2003 and 2008, while decreasing anomalies were found for SO4. Temporal variance for 15 indicators was quantified for a smooth bootstrap approach to arrive at stable values representative of the most recent samples taken from wells in the study area. Stable values revealed sampling bias in the Devonian, Grand Rapids, Empress, Channel Beverly, and Muriel Lake formations suggesting expansion of sampling may be necessary. Although temporal anomalies were found in the McMurray formation, sampling bias was not identified. The entropy and relative magnitude of time series were evaluated to identify candidate wells for continued observations, which consist of wells with low measurements and low entropy that are near active industry lease boundaries. Temporal anomalies, stable values, and entropy were combined into type-well information to provide plots for visual inspection and interpretation. Stable values are useful for regional mapping, for detecting future changes and trends, and for identifying areas of interest warranting further investigation.

Development of unconventional energy resources such as shale gas and coalbed methane has generated some public concern with regard to the protection of groundwater and surface water resources from leakage of stray gas from the deep subsurface. In terms of environmental impact to and risk assessment of shallow groundwater resources, the ultimate challenge is to distinguish: (a) natural in-situ production of biogenic methane, (b) biogenic or thermogenic methane migration into shallow aquifers due to natural causes, and (c) thermogenic methane migration from deep sources due to human activities associated with the exploitation of conventional or unconventional oil and gas resources. This study combines aqueous and gas (dissolved and free) geochemical and isotope data from 372 groundwater samples obtained from 186 monitoring wells of the provincial Groundwater Observation Well Network (GOWN) in Alberta (Canada), a province with a long record of conventional and unconventional hydrocarbon exploration. We investigated whether methane occurring in shallow groundwater formed in-situ, or whether it migrated into the shallow aquifers from elsewhere in the stratigraphic column. It was found that methane is ubiquitous in groundwater in Alberta and is predominantly of biogenic origin. The highest concentrations of biogenic methane (> 0.01 mM or > 0.2 mg/L), characterized by δ13CCH4 values < –55 ‰, occurred in anoxic Na-Cl, Na-HCO3 and Na-HCO3-Cl type groundwaters with negligible concentrations of nitrate and sulfate suggesting that methane was formed in-situ under methanogenic conditions for 39.1 % of the samples. In only a few cases (3.7 %) was methane of biogenic origin found in more oxidizing shallow aquifer portions suggesting limited upward migration from deeper methanogenic aquifers. 14.1 % of the samples contained methane with δ13CCH4 values > –54 ‰, potentially suggesting a thermogenic origin, but aqueous and isotope geochemistry data revealed that the elevated δ13CCH4 values were caused by microbial oxidation of biogenic methane or post-sampling degradation of low CH4 content samples rather than migration of deep thermogenic gas. A significant number of samples (39.2 %) contained methane with predominantly biogenic C isotope ratios (δ13CCH4 < –55 ‰) accompanied by elevated concentrations of ethane and sometimes trace concentrations of propane. These gases observed in 28.1 % of the samples, bearing both biogenic (δ13C) and thermogenic (presence of C3) characteristics, are most likely derived from shallow coal seams that are prevalent in the Cretaceous Horseshoe Canyon and neighboring formations in which some of the groundwater wells are completed. The remaining 3.7 % of samples were not assigned because of conflicting parameters in the datasets or between replicates samples. Hence, despite quite variable gas concentrations and a wide range of δ13CCH4 values in baseline groundwater samples, we found no conclusive evidence for deep thermogenic gas migration into shallow aquifers either naturally or via anthropogenically-induced pathways in this baseline groundwater survey. This study shows that the combined interpretation of aqueous geochemistry data in concert with chemical and isotopic compositions of dissolved and/or free gas can yield unprecedented insights into formation and potential migration of methane in shallow groundwater. This enables the assessment of cross-formational methane migration and provides an understanding of alkane gas sources and pathways necessary for a stringent baseline definition in the context of current and future unconventional hydrocarbon exploration and exploitation.

Development of unconventional energy resources such as shale gas and coalbed methane has generated some public concern with regard to the protection of groundwater and surface water resources from leakage of stray gas from the deep subsurface. In terms of environmental impact to and risk assessment of shallow groundwater resources, the ultimate challenge is to distinguish (a) natural in situ production of biogenic methane, (b) biogenic or thermogenic methane migration into shallow aquifers due to natural causes, and (c) thermogenic methane migration from deep sources due to human activities associated with the exploitation of conventional or unconventional oil and gas resources. This study combines aqueous and gas (dissolved and free) geochemical and isotope data from 372 groundwater samples obtained from 186 monitoring wells of the provincial Groundwater Observation Well Network (GOWN) in Alberta (Canada), a province with a long record of conventional and unconventional hydrocarbon exploration. We investigated whether methane occurring in shallow groundwater formed in situ, or whether it migrated into the shallow aquifers from elsewhere in the stratigraphic column. It was found that methane is ubiquitous in groundwater in Alberta and is predominantly of biogenic origin. The highest concentrations of biogenic methane (> 0.01 mM or > 0.2 mgL−1), characterized by δ13CCH4 values 3, and Na-HCO3-Cl type groundwaters with negligible concentrations of nitrate and sulfate suggesting that methane was formed in situ under methanogenic conditions for 39.1 % of the samples. In only a few cases (3.7 %) was methane of biogenic origin found in more oxidizing shallow aquifer portions suggesting limited upward migration from deeper methanogenic aquifers. Of the samples, 14.1 % contained methane with δ13CCH4 values > −54 ‰, potentially suggesting a thermogenic origin, but aqueous and isotope geochemistry data revealed that the elevated δ13CCH4 values were caused by microbial oxidation of biogenic methane or post-sampling degradation of low CH4 content samples rather than migration of deep thermogenic gas. A significant number of samples (39.2 %) contained methane with predominantly biogenic C isotope ratios (δ13CCH4 δ13C) and thermogenic (presence of C3) characteristics, are most likely derived from shallow coal seams that are prevalent in the Cretaceous Horseshoe Canyon and neighboring formations in which some of the groundwater wells are completed. The remaining 3.7 % of samples were not assigned because of conflicting parameters in the data sets or between replicates samples. Hence, despite quite variable gas concentrations and a wide range of δ13CCH4 values in baseline groundwater samples, we found no conclusive evidence for deep thermogenic gas migration into shallow aquifers either naturally or via anthropogenically induced pathways in this baseline groundwater survey. This study shows that the combined interpretation of aqueous geochemistry data in concert with chemical and isotopic compositions of dissolved and/or free gas can yield unprecedented insights into formation and potential migration of methane in shallow groundwater. This enables the assessment of cross-formational methane migration and provides an understanding of alkane gas sources and pathways necessary for a stringent baseline definition in the context of current and future unconventional hydrocarbon exploration and exploitation.