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The trace and rare earth elements (REE) analyses were conducted on samples collected from a 30 m core of the Marcellus Shale obtained from Greene County, southwestern Pennsylvania. Our results suggest that organic matter enrichment trends in the Marcellus Shale can be directly linked with the Acadian Orogeny. The Acadian Orogeny has been recognized as a main sediment source for the Marcellus Shale. Synthesis of tectonic history and recent ash bed geochronology, reveals that deposition of the organic carbon-rich (OR) zone (characterized by TOC >4%; located between 2393 m and 2406.5 m core depth) in the studied Marcellus Shale core was coincident with tectonically active and magmatic quiescent period of the Acadian orogeny (ca. 395–380 Ma). This time period also corresponds to the highest rate of mountain building in the Acadian Orogeny. The light rare earth (LREE) and selected trace elemental (e.g., Ta, Cs) composition of the OR zone sediments is similar to that of the bulk continental crust, supporting the lack of magmatic activity in the source area (i.e. Acadian Orogeny). In contrast, subsequent deposition of the organic carbon-poor (OP) sediments (characterized by TOC <4%; located between 2376 m and 2393 m core depth) in the upper Marcellus Shale occurred synchronously with a magmatic active phase (ca. 380–370 Ma) during the Acadian orogeny. The OP zone sediments have LREE and trace elemental composition similar to the average of the upper continental crust, suggesting intrusion of granodiorite rocks during a magmatic active period of Acadian Orogeny. The temporal and geochemical correlation between the Acadian orogenesis and the Marcellus deposition provide evidence for the role of tectonism in the enrichment of organic matter in the Marcellus Shale. [ABSTRACT FROM AUTHOR]

Geochemical, isotopic and petrographic analyses were performed on a 30-m core of the Marcellus Shale obtained from Greene County, Pennsylvania, to understand the dominant controls on organic matter deposition in the black shale study units. Our study suggests that the regeneration of nutrients, such as nitrogen (N) and phosphorous (P), may have played a key role in the formation of organic carbon (OC)-rich intervals in the Marcellus Shale. The decomposition of organic matter is likely to have released N and P into the water column, and the episodic upward mixing of these nutrient-enriched waters enhanced primary production. The ratios of C org /N bulk and C org /P tot are significantly higher in the OC-rich zone of the core (i.e., defined as TOC > 4% and located between 2393 and 2406.5 m depth). The high C org /P tot and C org /N bulk ratios of the preserved organic matter may reflect the release of N and P by microbial processes, indicating the recycling of nutrients during deposition of the OC-rich interval. In addition, our data show a positive relationships between the C org /P tot and C org /N bulk ratios and the organic carbon content, which indicate that the recycled nutrients may have promoted primary productivity, resulting in higher OC accumulation in some intervals. The geochemical and stable isotopic results also suggest that the alternating redox conditions in the water mass were favorable for nutrient regeneration. Highly variable trace metal concentrations (e.g., U, Mo, and V) in the OC-rich zone and a wide range of δ 15 N and δ 34 S pyr values towards the top of the OC-rich zone suggest fluctuations between anoxic and suboxic water conditions. Finally, sedimentary features and agglutinated benthic foraminifera in the OC-rich zone support the existence of short-term fluctuations between suboxic and anoxic conditions near the sediment–water interface. Multiple lines of evidence suggest that nutrient regeneration due to alternating redox conditions may have played an important role in the formation of OC-rich intervals in the Marcellus Shale. [ABSTRACT FROM AUTHOR]

The Middle Devonian age Marcellus Shale contains one of the largest shale gas plays in North America. Hydrocarbon production in the eastern part of the play is mostly “dry gas,” consisting of essentially pure methane. Production of natural gas liquids (condensate) increases toward the west, which is the area currently, being targeted by developers. Two Marcellus Shale cores from West Virginia were analyzed to compare the isotopic and geochemical characteristics of a liquids-prone well (WV-7) in Wetzel County with a gas-prone well (WV-6) in Monongalia County. The contrasts between the cores indicate that the conditions of the Marcellus Shale deposition were different between the two sites. The dominant organic matter preserved in each core is isotopically different; δ 13 C org values are lighter on average in WV-6 compared with WV-7. A possible explanation is that a larger fraction of terrestrial organic matter was preserved in the WV-6 core, whereas WV-7 may contain a greater percentage of marine organic matter. Clastic-influx proxies (e.g. Ti/Al, Ca/Al and Mg/Al) also suggest that the WV-6 core site received a higher siliciclastic input compared to WV-7, consistent with a more proximal location to dry land and the delivery of greater amounts of terrestrial organic matter. Depleted δ 13 C carb values, low concentrations of redox sensitive elements (e.g. V, Cr, Ni and U), and high variability δ 15 N values in the WV-6 core all suggest the presence of higher dissolved oxygen concentration and short term shifts in an oxic/anoxic boundary near the sediment–water interface during deposition. These lines of evidence indicate that the depositional conditions were favorable for the accumulation of predominantly gas-prone Type III kerogen in the Marcellus Shale at the WV-6 site. In contrast, the Marcellus Shale at the WV-7 site was deposited in a more distal area that received a low terrestrial sediment supply, organic matter primarily derived from marine algae, and bottom water conditions that were dominantly anoxic. Such conditions were favorable for the accumulation of Type II kerogen that has a greater capacity to generate liquid hydrocarbons. Differences between the liquids-prone and gas-prone parts of the Marcellus Shale play have been largely ascribed to depth-of-burial and thermal maturation history; this study indicates that depositional environment and sedimentary facies may have played significant roles as well. [ABSTRACT FROM AUTHOR]

Water samples were collected from 50 streams in an area of accelerating shale gas development in the eastern U.S.A. The geochemical/isotopic characteristics show no correlation with the five categories of Marcellus Shale production. The sub-watersheds with the greatest density of Marcellus Shale development have also undergone extensive coal mining. Hence, geochemical/isotopic compositions were used to understand sources of salinity and effects of coal mining and shale gas development in the area. The data indicates that while some streams appear to be impacted by mine drainage; none appear to have received sustained contribution from deep brines or produced waters associated with shale gas production. However, it is important to note that our interpretations are based on one time synoptic base flow sampling of a few sampling stations and hence do account potential intermittent changes in chemistry that may result from major/minor spills or specific mine discharges on the surface water chemistry. [ABSTRACT FROM AUTHOR]

Water and gas samples were collected from (1) nine shallow groundwater aquifers overlying Marcellus Shale in north-central West Virginia before active shale gas drilling, (2) wells producing gas from Upper Devonian sands and Middle Devonian Marcellus Shale in southwestern Pennsylvania, (3) coal-mine water discharges in southwestern Pennsylvania, and (4) streams in southwestern Pennsylvania and north-central West Virginia. Our preliminary results demonstrate that the oxygen and hydrogen isotope composition of water, carbon isotope composition of dissolved inorganic carbon, and carbon and hydrogen isotope compositions of methane in Upper Devonian sands and Marcellus Shale are very different compared with shallow groundwater aquifers, coal-mine waters, and stream waters of the region. Therefore, spatiotemporal stable isotope monitoring of the different sources of water before, during, and after hydraulic fracturing can be used to identify migrations of fluids and gas from deep formations that are coincident with shale gas drilling. [ABSTRACT FROM AUTHOR]

Development of unconventional shale gas wells can generate significant quantities of drilling waste, including trace metal-rich black shale from the lateral portion of the drillhole. We carried out sequential extractions on 15 samples of dry-drilled cuttings and core material from the gas-producing Middle Devonian Marcellus Shale and surrounding units to identify the host phases and evaluate the mobility of selected trace elements during cuttings disposal. Maximum whole rock concentrations of uranium (U), arsenic (As), and barium (Ba) were 47, 90, and 3333 mg kg −1 , respectively. Sequential chemical extractions suggest that although silicate minerals are the primary host for U, as much as 20% can be present in carbonate minerals. Up to 74% of the Ba in shale was extracted from exchangeable sites in the shale, while As is primarily associated with organic matter and sulfide minerals that could be mobilized by oxidation. For comparison, U and As concentrations were also measured in 43 produced water samples returned from Marcellus Shale gas wells. Low U concentrations in produced water (<0.084–3.26 μg L −1 ) are consistent with low-oxygen conditions in the wellbore, in which U would be in its reduced, immobile form. Arsenic was below detection in all produced water samples, which is also consistent with reducing conditions in the wellbore minimizing oxidation of As-bearing sulfide minerals. Geochemical modeling to determine mobility under surface storage and disposal conditions indicates that oxidation and/or dissolution of U-bearing minerals in drill cuttings would likely be followed by immobilization of U in secondary minerals such as schoepite, uranophane, and soddyite, or uraninite as conditions become more reducing. Oxidative dissolution of arsenic containing sulfides could release soluble As in arsenate form under oxic acidic conditions. The degree to which the As is subsequently immobilized depends on the redox conditions along the landfill flow path. The results suggest that proper management of drill cuttings can minimize mobilization of these metals by monitoring and controlling Eh, pH and dissolved constituents in landfill leachates. [ABSTRACT FROM AUTHOR]