Origin, distribution and hydrogeochemical controls on methane occurrences in shallow aquifers, southwestern Ontario, Canada

Natural gas reservoirs in organic-rich shales in the Appalachian and Michigan basins in the United States are currently being produced via hydraulic fracturing. Stratigraphically-equivalent shales occur in the Canadian portion of the basins in southwestern Ontario with anecdotal evidence of gas shows, yet there has been no commercial shale gas production to date. To provide baseline data in the case of future environmental issues related to hydraulic fracturing and shale gas production, such as leakage of natural gas, saline water, and/or hydraulic fracturing fluids, and to evaluate hydrogeochemical controls on natural gas accumulations in shallow groundwater in general, this study investigates the origin and distribution of natural gas and brine in shallow aquifers across southwestern Ontario. An extensive geochemical database of major ion and trace metal chemistry and methane concentrations of 1010 groundwater samples from shallow, domestic wells in bedrock and overburden aquifers throughout southwestern Ontario was utilized. In addition, select wells (n = 36) were resampled for detailed dissolved gas composition, delta C-13 of CH4, C-2, C-3, and CO2, and delta D of CH4. Dissolved gases in groundwater from bedrock and overburden wells were composed primarily of CH4 (29.7-98.6 mol% of total gas volume), N-2 (0.8-66.2 mol%), Ar + O-2 (0.2-3.4 mol%), and CO2 (0-1.2 mol%). Ethane was detected, but only in low concentrations (<0.041 mol%), and no other higher chain hydrocarbons were present, except for one well in overburden overlying the Dundee Formation, which contained 0.81 mol% ethane and 0.21 mol% propane. The highest methane concentrations (30 to > 100 in situ % saturation) were found in bedrock wells completed in the Upper Devonian Kettle Point Formation, Middle Devonian Hamilton Group and Dundee Formation, and in surficial aquifers overlying these organic-rich shale-bearing formations, indicating that bedrock geology is the primary control on methane occurrences. A few (n = 40) samples showed Na-Cl-Br evidence of brine mixing with dilute groundwater, however only one of these samples contained high (>60 in situ % saturation) CH4. The relatively low delta C-13 values of CH4 (-89.9% to -57.3%), covariance of delta D values of CH4 and H2O, positive correlation between delta C-13 values of CH4 and CO2, and lack of higher chain hydrocarbons (C3+) in all but one dissolved gas sample indicates that the methane in groundwater throughout the study area is primarily microbial in origin. The presence or absence of alternative electron acceptors (e. g. dissolved oxygen, Fe, NO3, SO4), in addition to organic substrates, controls the occurrence of microbial CH4 in shallow aquifers. Microbial methane has likely been accumulating in the study area, since at least the Late Pleistocene to the present, as indicated by the co-variance and range of delta D values of CH4 (-314% to -263%) and associated groundwater (-19% to -6% delta D-H2O). (C) 2014 Elsevier Ltd. All rights reserved.