No abstract

This study places constraints on the source and transport mechanisms of methane found in groundwater within the Barnett Shale footprint in Texas using dissolved noble gases, with particular emphasis on Kr andXe. Dissolved methane concentrations are positively correlated with crustal He,Ne, and Ar and suggest that noble gases and methane originate from common sedimentary strata, likely the Strawn Group. In contrast to most samples, four water wells with the highest dissolved methane concentrations unequivocally show strong depletion of all atmospheric noble gases (Ne, Ar,Kr, Xe) with respect to air-saturated water (ASW). This is consistent with predicted noble gas concentrations in a water phase in contact with a gas phase with initial ASW composition at 18 °C-25 °C and it suggests an in situ, highly localized gas source. All of these four water wells tap into the Strawn Group and it is likely that small gas accumulations known to be present in the shallow subsurface were reached. Additionally, lack of correlation ofKr/Ar and Xe/Ar fractionation levels along with He/Ne with distance to the nearest gas production wells does not support the notion that methane present in these groundwaters migrated from nearby production wells either conventional or using hydraulic fracturing techniques.

Records of past topography connect Earth's deep interior to the surface, reflecting the distribution of heat and mass, past crustal structure, and plate interactions. Many tectonic reconstructions of the North American Cordillera suggest the presence of an Altiplano-like plateau in the location of the modern Basin and Range, with conflicting timing and mechanisms for the onset of surface-lowering extension and orogen collapse. Here we show, through a paleotopographic profile, that from the Eocene to the Oligocene a high, broad orogen stretched across Nevada, with a distinct crest that divided a continuous westward-draining slope extending to central California from an internally drained eastern Nevada plateau. This paleo-orogen maintained demonstrably higher-than-modern elevations, reaching 3500 m in the late Oligocene. Despite the long-term high gravitational potential energy of the crust supporting this topography, surfacelowering extension did not occur until the transition to a transform margin changed the external kinematic framework of the system. Maximum surface lowering was spatially decoupled from brittle upper crustal extension, requiring a large component of mid-crustal flow.

Understanding the source of dissolved methane in drinking-water aquifers is critical for assessing potential contributions from hydraulic fracturing in shale plays. Shallow groundwater in the Texas portion of the Haynesville Shale area (13,000 km ) was sampled (70 samples) for methane and other dissolved light alkanes. Most samples were derived from the fresh water bearing Wilcox formations and show little methane except in a localized cluster of 12 water wells (17% of total) in a approximately 30 × 30 km area in Southern Panola County with dissolved methane concentrations less than 10 mg/L. This zone of elevated methane is spatially associated with the termination of an active fault system affecting the entire sedimentary section, including the Haynesville Shale at a depth more than 3.5 km, and with shallow lignite seams of Lower Wilcox age at a depth of 100 to 230 m. The lignite spatial extension overlaps with the cluster. Gas wetness and methane isotope compositions suggest a mixed microbial and thermogenic origin with contribution from lignite beds and from deep thermogenic reservoirs that produce condensate in most of the cluster area. The pathway for methane from the lignite and deeper reservoirs is then provided by the fault system.

A method for the removal of siderite from geological samples to determine organic carbon isotope compositions using elemental analysis isotope ratio mass spectrometry is presented which includes calculations for % organic carbon in samples that contain diagenetic carbonate. The proposed method employs in situ acidification of geological samples with 6 N HCl and silver capsule sample holders and was tested on modern peach leaf samples (NIST 1547) and ancient lacustrine samples from Valles Caldera, New Mexico. The in situ acidification technique eliminates potential errors associated with the removal of soluble organic material using standard acid decanting techniques and allows for removal of the less soluble siderite, which is not efficiently removed using vapor acidification techniques.