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

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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.


Applied Geochemistry



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Geology & Environmental Geosciences



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