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Since naturally occurring methane and saline groundwater are nearly ubiquitous in many sedimentary basins, delineating the effects of anthropogenic contamination sources is a major challenge for evaluating the impact of unconventional shale gas development on water quality. This study investigates the geochemical variations of groundwater and surface water before, during, and after hydraulic fracturing and in relation to various geospatial parameters in an area of shale gas development in northwestern West Virginia, United States. To our knowledge, we are the first to report a broadly integrated study of various geochemical techniques designed to apportion natural and anthropogenic sources of natural gas and salt contaminants both before and after drilling. These measurements include inorganic geochemistry (major cations and anions), stable isotopes of select inorganic constituents including strontium (87 Sr/ 86 Sr), boron (δ 11 B), lithium (δ 7 Li), and carbon (δ 13 C-DIC), select hydrocarbon molecular (methane, ethane, propane, butane, and pentane) and isotopic tracers (δ 13 C-CH 4 , δ 13 CC 2 H 6), tritium (3 H), and noble gas elemental and isotopic composition (He, Ne, Ar) in 112 drinking-water wells, with repeat testing in 33 of the wells (total samples=145). In a subset of wells (n=20), we investigated the variations in water quality before and after the installation of nearby (<1 km) shale-gas wells. Methane occurred above 1 ccSTP/L in 37% of the groundwater samples and in 79% of the samples with elevated salinity (chloride >50 mg/L). The integrated geochemical data indicate that the saline groundwater originated via naturally occurring processes, presumably from the migration of deeper methane-rich brines that have interacted extensively with coal lithologies. These observations were consistent with the lack of changes in water quality observed in drinkingwater wells following the installation of nearby shale-gas wells. In contrast to groundwater samples that showed no evidence of anthropogenic contamination, the chemistry and isotope ratios of surface waters near known spills or leaks occurring at disposal sites (n=8) mimicked the composition of the Marcellus flowback fluids, and show direct evidence for impact on surface water by fluids accidentally released from nearby shale-gas well pads and oil and gas wastewater disposal sites. Overall this study presents a comprehensive geochemical framework that can be

While coalbed methane (CBM) is a significant source of natural gas production globally, uncertainties regarding the proportions of biogenic and thermogenic natural gas in CBM reservoirs still remain. We integrate major gases, hydrocarbon composition, hydrocarbon stable isotopes and noble gases in fluids from 20 producing CBM wells to more accurately constrain the genetic source of natural gases in the eastern Illinois Basin, USA. Previous studies have indicated primarily biogenic production of methane (>99.6%) with negligible contributions from thermogenic natural gases. However, by integrating noble gases, we identify quantifiable (up to 19.2%) contributions of exogenous thermogenic gas in produced gases from the Seelyville and Springfield coal seams. Thermogenic gases are distinguished by a positive relationship between methane, ethane and helium-4, lower C1/C2+, heavier δ13C-CH4, more radiogenic noble gases (4He, 21Ne*, 40Ar*), and lower abundances of atmospherically derived gases (20Ne, 36Ar). Biogenic gases displayed lighter δ13C-CH4, higher C1/C2+, higher levels of atmospheric gases and lower abundances of radiogenic noble gases. Our data suggest that natural gases from a deeper, exogenous thermogenic source likely migrated to the Pennsylvanian-aged coals at an unknown time and later mixed with biogenic methane diluting the geochemical signature of the thermogenic methane within the Springfield and Seelyville coal seams.

Significance Our regional-scale geochemical dataset ( 3 He/ 4 He) resolves the geometry of the continental collision between India and Asia. Geophysical images have led to contradictory interpretations that India directly underthrusts Tibet as a horizontal plate or India subducts steeply into the mantle. Helium transits from mantle depths to the surface within a few millennia, such that the ratio of mantle-derived 3 He to dominantly crust-derived 4 He provides a snapshot of the subsurface. 3 He/ 4 He data from 225 geothermal springs across a >1,000-km-wide region of southern Tibet define a sharp boundary subparallel to the surface suture between India and Asia, just north of the Himalaya, delineating the northern limit of India at ∼80-km depth. The India–Asia collision resembles oceanic subduction with an asthenospheric mantle wedge.

Environmental concerns regarding the potential for drinking water contamination in shallow aquifers have accompanied unconventional energy development in the northern Appalachian Basin. These activities have also raised several critical questions about the hydrogeological parameters that control the naturally occurring presence and migration of hydrocarbon gases in shallow aquifers within petroliferous basins. To interrogate these factors, we analyzed the noble gas, dissolved ion, and hydrocarbon gas (molecular and isotopic composition) geochemistry of 98 groundwater samples from south-central New York. All samples were collected ≫1km from unconventional drilling activities and sample locations were intentionally targeted based on their proximity to various types of documented fault systems. In agreement with studies from other petroliferous basins, our results show significant correlations between elevated levels of radiogenic [ He], thermogenic [CH ], and dissolved ions (e.g., Cl, Br, Sr, Ba). In combination, our data suggest that faults have facilitated the transport of exogenous hydrocarbon-rich brines from Devonian source rocks into overlying Upper Devonian aquifer lithologies over geologic time. These data conflict with previous reports, which conclude that hydrodynamic focusing regulates the occurrence of methane and salt in shallow aquifers and leads to elevated levels of these species in restricted flow zones within valley bottoms. Instead, our data suggest that faults in Paleozoic rocks play a fundamental role in gas and brine transport from depth, regulate the distribution of their occurrence in shallow aquifers, and influence the geochemistry of shallow groundwater in this petroliferous basin.