Stephen G. Osborn

Methane contamination of drinking water accompanying gas-well drilling and hydraulic fracturing

Directional drilling and hydraulic-fracturing technologies are dramatically increasing natural-gas extraction. In aquifers overlying the Marcellus and Utica shale formations of northeastern Pennsylvania and upstate New York, we document systematic evidence for methane contamination of drinking water associated with shale-gas extraction. In active gas-extraction areas (one or more gas wells within 1 km), average and maximum methane concentrations in drinking-water wells increased with proximity to the nearest gas well and were 19.2 and 64 mg CH4 L-1 (n = 26), a potential explosion hazard; in contrast, dissolved methane samples in neighboring nonextraction sites (no gas wells within 1 km) within similar geologic formations and hydrogeologic regimes averaged only 1.1 mg L-1 (P < 0.05; n = 34). Average δ13C-CH4 values of dissolved methane in shallow groundwater were significantly less negative for active than for nonactive sites (-37 ± 7‰ and -54 ± 11‰, respectively; P < 0.0001). These δ13C-CH4 data, coupled with the ratios of methane-to-higher-chain hydrocarbons, and δ2H-CH4 values, are consistent with deeper thermogenic methane sources such as the Marcellus and Utica shales at the active sites and matched gas geochemistry from gas wells nearby. In contrast, lower-concentration samples from shallow groundwater at nonactive sites had isotopic signatures reflecting a more biogenic or mixed biogenic/thermogenic methane source. We found no evidence for contamination of drinking-water samples with deep saline brines or fracturing fluids. We conclude that greater stewardship, data, and—possibly—regulation are needed to ensure the sustainable future of shale-gas extraction and to improve public confidence in its use.

Increased stray gas abundance in a subset of drinking water wells near Marcellus shale gas extraction

Horizontal drilling and hydraulic fracturing are transforming energy production, but their potential environmental effects remain controversial. We analyzed 141 drinking water wells across the Appalachian Plateaus physiographic province of northeastern Pennsylvania, examining natural gas concentrations and isotopic signatures with proximity to shale gas wells. Methane was detected in 82% of drinking water samples, with average concentrations six times higher for homes <1 km from natural gas wells (P = 0.0006). Ethane was 23 times higher in homes <1 km from gas wells (P = 0.0013); propane was detected in 10 water wells, all within approximately 1 km distance (P = 0.01). Of three factors previously proposed to influence gas concentrations in shallow groundwater (distances to gas wells, valley bottoms, and the Appalachian Structural Front, a proxy for tectonic deformation), distance to gas wells was highly significant for methane concentrations (P = 0.007; multiple regression), whereas distances to valley bottoms and the Appalachian Structural Front were not significant (P = 0.27 and P = 0.11, respectively). Distance to gas wells was also the most significant factor for Pearson and Spearman correlation analyses (P < 0.01). For ethane concentrations, distance to gas wells was the only statistically significant factor (P < 0.005). Isotopic signatures (δ13C-CH4, δ13C-C2H6, and δ2H-CH4), hydrocarbon ratios (methane to ethane and propane), and the ratio of the noble gas 4He to CH4 in groundwater were characteristic of a thermally postmature Marcellus-like source in some cases. Overall, our data suggest that some homeowners living <1 km from gas wells have drinking water contaminated with stray gases.

Geochemical evidence for possible natural migration of Marcellus Formation brine to shallow aquifers in Pennsylvania

The debate surrounding the safety of shale gas development in the Appalachian Basin has generated increased awareness of drinking water quality in rural communities. Concerns include the potential for migration of stray gas, metal-rich formation brines, and hydraulic fracturing and/or flowback fluids to drinking water aquifers. A critical question common to these environmental risks is the hydraulic connectivity between the shale gas formations and the overlying shallow drinking water aquifers. We present geochemical evidence from northeastern Pennsylvania showing that pathways, unrelated to recent drilling activities, exist in some locations between deep underlying formations and shallow drinking water aquifers. Integration of chemical data (Br, Cl, Na, Ba, Sr, and Li) and isotopic ratios (87Sr/86Sr, 2H/H, 18O/16O, and 228Ra/226Ra) from this and previous studies in 426 shallow groundwater samples and 83 northern Appalachian brine samples suggest that mixing relationships between shallow ground water and a deep formation brine causes groundwater salinization in some locations. The strong geochemical fingerprint in the salinized (Cl > 20 mg/L) groundwater sampled from the Alluvium, Catskill, and Lock Haven aquifers suggests possible migration of Marcellus brine through naturally occurring pathways. The occurrences of saline water do not correlate with the location of shale-gas wells and are consistent with reported data before rapid shale-gas development in the region; however, the presence of these fluids suggests conductive pathways and specific geostructural and/or hydrodynamic regimes in northeastern Pennsylvania that are at increased risk for contamination of shallow drinking water resources, particularly by fugitive gases, because of natural hydraulic connections to deeper formations.

Coupled hydrology and biogeochemistry of Paleocene–Eocene coal beds, northern Gulf of Mexico

Thirty-six formation waters, gas, and microbial samples were collected and analyzed from natural gas and oil wells producing from the Paleocene to Eocene Wilcox Group coal beds and adjacent sandstones in north-central Louisiana, USA, to investigate the role hydrology plays on the generation and distribution of microbial methane. Major ion chemistry and Cl−Br relations of Wilcox Group formation waters suggest mixing of freshwater with halite-derived brines. High alkalinities (up to 47.8 meq/L), no detectable SO4, and elevated δ13C values of dissolved inorganic carbon (up to 20.5‰ Vienna Peedee belemnite [VPDB]) and CO2 (up to 17.67‰ VPDB) in the Wilcox Group coals and adjacent sandstones indicate the dominance of microbial methanogenesis. The δ13C and δD values of CH4, and carbon isotope fractionation of CO2 and CH4, suggest CO2 reduction is the major methanogenic pathway. Geochemical indicators for methanogenesis drop off significantly at chloride concentrations above ∼1.7 mol/L, suggesting that high salinities inhibit microbial activity at depths greater than ∼1.6 km. Formation waters in the Wilcox Group contain up to 1.6% modern carbon (A14C) to at least 1690 m depth; the covariance of δD values of co-produced H2O and CH4 indicate that the microbial methane was generated in situ with these Late Pleistocene or younger waters. The most enriched carbon isotope values for dissolved inorganic carbon (DIC) and CO2, and highest alkalinities, were detected in Wilcox Group sandstone reservoirs that were CO2 flooded in the 1980s for enhanced oil recovery, leading to the intriguing hypothesis that CO2 sequestration may actually enhance methanogenesis in organic-rich formations.

Iodine-129, 87Sr/86Sr, and trace elemental geochemistry of northern Appalachian Basin brines: Evidence for basinal-scale fluid migration and clay mineral diagenesis

Evidence for basin scale brine migration and clay mineral diagenesis in the northern Appalachian Basin was investigated using elemental and isotope (129I/I, 87Sr/86Sr) geochemistry of formation waters collected from the Middle to Upper Devonian section of the northern basin margin in western New York, northwest Pennsylvania, and eastern Kentucky. One sample from each of the Mississippian Berea sandstone and the Silurian Medina sandstone were analyzed for comparison. Measured iodine ratios range between 28 to 1,890 × 10−15 and are anomalously high compared to cosmogenic iodine sourced from Devonian age organic matter. Iodine-129 in the waters was largely derived from fissiogenic sources, the spontaneous fission of 238U to produce 129I, with estimated 129I/I values up to 270 × 10−15, which occur locally in the organic-rich shales. There are three water samples that have values of 490 × 10−15, 860 × 10−15, and 1,890 × 10−15, which are above the range for local fissiogenic 129I and may be accounted for by topographically driven, basin scale fluid flow through a regionally high fissiogenic source. Relatively large uranium occurrences lie along the structural front of the Appalachian Basin in the Blue Ridge Province and are situated within hypothesized flow paths parallel to the main compressional direction of the Alleghanian orogeny. Estimated 129I/I values for these uranium occurrences are in excess of 55,000 × 10−15. The strontium isotope composition and Sr concentration of brines display a mixing trend between a highly radiogenic end-member (0.7210) with low Sr (51 mg/L) and a non-radiogenic (0.7100), high Sr (4789 mg/L) end-member. Potassium and boron concentrations are notably depleted relative to evaporated Paleozoic seawater, the hypothesized source of Appalachian Basin brines. The K/Rb values of formation waters are depleted relative to seawater values, but in some cases are well above values indicative of water-rock reactions. The Sr isotopic composition, K and B depletion, and intermediate K/Rb ratios are consistent with smectite diagenesis and paleo-temperatures that are likely greater than approximately 150 °C. These temperatures may be high given the burial history of the study area and support the flow of formation waters from deeper within the basin. The combined isotopic and elemental results of formation waters provide compelling evidence for basin scale fluid migration in the northern Appalachian Basin and are consistent with previously published evidence documented from the rock record, including clay mineral diagenesis and ore deposition.

Reply to Saba and Orzechowski and Schon: Methane contamination of drinking water accompanying gas-well drilling and hydraulic fracturing.

Two letters by Saba and Orzechowski (1) and Schon (2) address our research linking elevated methane and ethane concentrations to shale-gas drilling and hydraulic fracturing (3). We respond briefly here and point readers to a supplementary document for more details (4).

Reply to Davies: Hydraulic fracturing remains a possible mechanism for observed methane contamination of drinking water

Davies (1) agrees that methane contamination of drinking water has occurred in aquifers overlying the Marcellus formation but asserts that we prematurely ascribed its cause to hydraulic fracturing (2). We respond briefly, noting that we carefully avoided ascribing any mechanism and suggested some additional research (2) for the important need that Davies (1) identifies—to understand the mechanism of contamination better. Comments about sampling procedures and methane seeps are in refs. 3 and 4.