Hydrocarbon-Rich Groundwater above Shale-Gas Formations: A Karoo Basin Case Study.

Horizontal drilling and hydraulic fracturing have enhanced unconventional hydrocarbon recovery but raised environmental concerns related to water quality. Because most basins targeted for shale-gas development in the USA have histories of both active and legacy petroleum extraction, confusion about the hydrogeological context of naturally occurring methane in shallow aquifers overlying shales remains. The Karoo Basin, located in South Africa, provides a near-pristine setting to evaluate these processes, without a history of conventional or unconventional energy extraction. We conducted a comprehensive pre-industrial evaluation of water quality and gas geochemistry in 22 groundwater samples across the Karoo Basin, including dissolved ions, water isotopes, hydrocarbon molecular and isotopic composition, and noble gases. Methane-rich samples were associated with high-salinity, NaCl-type groundwater and elevated levels of ethane, 4 He, and other noble gases produced by radioactive decay. This endmember displayed less negative δ13 C-CH4 and evidence of mixing between thermogenic natural gases and hydrogenotrophic methane. Atmospheric noble gases in the methane-rich samples record a history of fractionation during gas-phase migration from source rocks to shallow aquifers. Conversely, methane-poor samples have a paucity of ethane and 4 He, near saturation levels of atmospheric noble gases, and more negative δ13 C-CH4 ; methane in these samples is biogenic and produced by a mixture of hydrogenotrophic and acetoclastic sources. These geochemical observations are consistent with other basins targeted for unconventional energy extraction in the USA and contribute to a growing data base of naturally occurring methane in shallow aquifers globally, which provide a framework for evaluating environmental concerns related to unconventional energy development (e.g., stray gas).

Pre-drill Groundwater Geochemistry in the Karoo Basin, South Africa.

Enhanced production of unconventional hydrocarbons in the United States has driven interest in natural gas development globally, but simultaneously raised concerns regarding water quantity and quality impacts associated with hydrocarbon extraction. We conducted a pre-development assessment of groundwater geochemistry in the critically water-restricted Karoo Basin, South Africa. Twenty-two springs and groundwater samples were analyzed for major dissolved ions, trace elements, water stable isotopes, strontium and boron isotopes, hydrocarbons and helium composition. The data revealed three end-members: a deep, saline groundwater with a sodium-chloride composition, an old, deep freshwater with a sodium-bicarbonate-chloride composition and a shallow, calcium-bicarbonate freshwater. In a few cases, we identified direct mixing of the deep saline water and shallow groundwater. Stable water isotopes indicate that the shallow groundwater was controlled by evaporation in arid conditions, while the saline waters were diluted by apparently fossil meteoric water originated under wetter climatic conditions. These geochemical and isotopic data, in combination with elevated helium levels, suggest that exogenous fluids are the source of the saline groundwater and originated from remnant seawater prior to dilution by old meteoric water combined with further modification by water-rock interactions. Samples with elevated methane concentrations (>14 ccSTP/kg) were strongly associated with the sodium-chloride water located near dolerite intrusions, which likely provide a preferential pathway for vertical migration of deeply sourced hydrocarbon-rich saline waters to the surface. This pre-drill evaluation indicates that the natural migration of methane- and salt-rich waters provides a source of geogenic contamination to shallow aquifers prior to shale gas development in the Karoo Basin.