Abstract
Abstract. 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 < −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. 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 < −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 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.
Highlights
Development of unconventional energy resources, such as shale gas and coalbed methane, is often accompanied by concerns of some landowners and parts of the public that shallow groundwater could be affected by leakage of stray gas from the deep subsurface
This is consistent with the observations made in groundwater baseline studies of McIntosh et al (2014) and Hamilton et al (2015) in southwestern Ontario (Canada), Molofsky et al (2013) in Susquehanna County, and McPhillips et al (2014) in Chenango County. In these studies, elevated methane concentrations in groundwater were predominantly found in sodium chloride (Na-Cl) or sodium bicarbonate (Na-HCO3) water types, while calcium bicarbonate (Ca-HCO3) type groundwater had typically very low methane concentrations or no methane at all
Taking into account the hydrochemical conditions in methane-bearing aquifers allows for a refined analysis of methane sources and a differentiation between biogenic in situ production of methane within aquifers vs. migration of biogenic or thermogenic gases into the aquifer
Summary
Development of unconventional energy resources, such as shale gas and coalbed methane, is often accompanied by concerns of some landowners and parts of the public that shallow groundwater could be affected by leakage of stray gas from the deep subsurface. In the last 5 years, an increasing number of publications have addressed the questions of occurrence and sources of methane in shallow groundwater in natural gas producing regions (Osborn et al, 2011a, b; Warner et al, 2013; Darrah et al, 2012, 2014; Jackson et al, 2013; Molofsky et al, 2013; Siegel et al, 2015; Vengosh et al, 2013; Brantley et al, 2014; Baldassare et al, 2014; McPhilips et al, 2014; McIntosh et al, 2014; Vidic et al, 2013; Hamilton et al, 2015) These studies have contributed a wealth of baseline data for gas occurrences in shallow groundwater in many regions of North America. Where thermogenic gas was found in shallow groundwater, it is not always clear to what extent this occurred inadvertently as a result of human activities or due to natural flowpaths
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