Geochemical and Strontium Isotope Characterization of Produced Waters from Marcellus Shale Natural Gas Extraction

Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ∼375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (εSr SW = +13.8 to +41.6, where εSr SW is the deviation of the 87Sr/86Sr ratio from that of seawater in parts per 104); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters

Isotopic evidence of enhanced carbonate dissolution at a coal mine drainage site in Allegheny County, Pennsylvania, USA

18 O SO4 isotopic signatures of the mine drainage and the presence of presumptive SO 4 -reducing bacteria suggest that SO 4 reduction activity also contributes C depleted in 13 C isotope to the total DIC pool. With distance downstream from the mine portal, C isotope signatures in the drainage increased , accompanied by decreased total DIC concentrations and increased pH. These data are consistent with H 2 SO 4 dissolution of carbonate rocks, enhanced by cation exchange, and C release to the atmosphere via CO 2 outgassing

Isotopic evidence of enhanced carbonate dissolution at a coal mine drainage site in Allegheny County, Pennsylvania, USA

18 O SO4 isotopic signatures of the mine drainage and the presence of presumptive SO 4 -reducing bacteria suggest that SO 4 reduction activity also contributes C depleted in 13 C isotope to the total DIC pool. With distance downstream from the mine portal, C isotope signatures in the drainage increased , accompanied by decreased total DIC concentrations and increased pH. These data are consistent with H 2 SO 4 dissolution of carbonate rocks, enhanced by cation exchange, and C release to the atmosphere via CO 2 outgassing

Geochemical and Strontium Isotope Characterization of Produced Waters from Marcellus Shale Natural Gas Extraction

Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ∼375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (εSr SW = +13.8 to +41.6, where εSr SW is the deviation of the 87Sr/86Sr ratio from that of seawater in parts per 104); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters

Isotopic evidence of enhanced carbonate dissolution at a coal mine drainage site in Allegheny County, Pennsylvania, USA

Stable isotopes were used to determine the sources and fate of dissolved inorganic C (DIC) in the circumneutral pH drainage from an abandoned bituminous coal mine in western Pennsylvania. The C isotope signatures of DIC (δ{sup 13}C{sub DIC}) were intermediate between local carbonate and organic C sources, but were higher than those of contemporaneous Pennsylvanian age groundwaters in the region. This suggests a significant contribution of C enriched in {sup 13}C due to enhanced carbonate dissolution associated with the release of H{sub 2}SO{sub 4} from pyrite oxidation. The Sr isotopic signature of the drainage was similar to other regional mine waters associated with the same coal seam and reflected contributions from limestone dissolution and cation exchange with clay minerals. The relatively high δ{sup 34}S{sub SO4} and δ{sup 18}O{sub SO4} isotopic signatures of the mine drainage and the presence of presumptive SO{sub 4}-reducing bacteria suggest that SO{sub 4} reduction activity also contributes C depleted in {sup 13}C isotope to the total DIC pool. With distance downstream from the mine portal, C isotope signatures in the drainage increased, accompanied by decreased total DIC concentrations and increased pH. These data are consistent with H{sub 2}SO{sub 4} dissolution of carbonate rocks, enhanced by cation exchange, and C release to the atmosphere via CO{sub 2} outgassing

Origin of Brines, Salts and Carbonate from Shales of the Marcellus Formation: Evidence from Geochemical and Sr Isotope Study of Sequentially Extracted Fluids

Fluids co-produced with methane from hydraulically fractured organic-rich shales of the Marcellus Formation (USA) are characterized by high total dissolved solids (TDS), including elevated levels of Ba, Sr and Br. To investigate the source and geologic history of these high-TDS fluids and their dissolved constituents, we carried out a series of sequential extraction experiments on dry-drilled cuttings extracted within, below and above the Marcellus Shale from a well in Tioga County, New York State. The experiments were designed to extract (1) water soluble components, (2) exchangeable cations, (3) carbonate minerals, and (4) hydrochloric acid-soluble constituents. The geochemistry of the resultant leachates highlights the different geochemical reservoirs for extractable elements within the shale; notably, Na and Br were largely water-soluble, while Ba was extracted primarily from exchangeable sites, and Ca and Sr were found both in exchangeable sites and carbonate. Strontium isotope ratios measured on the leachates indicate that each of the element reservoirs has a distinct value. Measured Sr-87/Sr-86 ratios in the water soluble component are similar to those of Marcellus produced water, while the ion exchange reservoir yields lower ratios, and carbonate Sr is lower still, approaching Devonian-Silurian seawater values. Despite the isotopic similarity of water leachates and produced water, the total water chemistry argues against generation of produced water by interaction of hydraulic fracturing fluid with dry shale. The high-TDS produced water is most likely trapped formation water (within and/or adjacent to the shale) that is released by hydraulic fracturing. The formation water was affected by multiple processes, possibly including basin scale, tectonically-driven fluid flow. Significant chemical and isotopic differences between Marcellus Shale produced water and overlying Upper Devonian/Lower Mississippian produced waters suggests a hydrologic barrier has been maintained in parts of the Appalachian Basin since the late Paleozoic. (C) 2015 Elsevier Ltd. All rights reserved

Geochemical and Strontium Isotope Characterization of Produced Waters from Marcellus Shale Natural Gas Extraction

Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ∼375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (ε_Sr^SW = +13.8 to +41.6, where ε_Sr^SW is the deviation of the ⁸⁷Sr/⁸⁶Sr ratio from that of seawater in parts per 10⁴); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters

Strontium Isotopes Test Long-Term Zonal Isolation of Injected and Marcellus Formation Water after Hydraulic Fracturing

One concern regarding unconventional hydrocarbon production from organic-rich shale is that hydraulic fracture stimulation could create pathways that allow injected fluids and deep brines from the target formation or adjacent units to migrate upward into shallow drinking water aquifers. This study presents Sr isotope and geochemical data from a well-constrained site in Greene County, Pennsylvania, in which samples were collected before and after hydraulic fracturing of the Middle Devonian Marcellus Shale. Results spanning a 15-month period indicated no significant migration of Marcellus-derived fluids into Upper Devonian/Lower Mississippian units located 900–1200 m above the lateral Marcellus boreholes or into groundwater sampled at a spring near the site. Monitoring the Sr isotope ratio of water from legacy oil and gas wells or drinking water wells can provide a sensitive early warning of upward brine migration for many years after well stimulation