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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Pore characterization of the Marcellus Shale by nitrogen adsorption and prediction of its gas storage capacity

In a shale gas reservoir, pore characterization is an important factor used to determine gas storage capacity. However, the nanometer (nm)-scale pore system in shale is difficult to explore by traditional optical, scanning electron microscopy, or even nuclear magnetic resonance well logging. We have investigated the pore structure and storage capacity of the Marcellus Shale through integration of petrophysical analysis from laboratory and well-logging data and nitrogen adsorption. The isotherm of Marcellus Shale is a composite isotherm, which has features of type I, type II, and type IV isotherms with type H4 of the hysteresis loop, suggesting slit-like pores developed in the Marcellus Shale. Quantitative analysis of pore volumes from the nitrogen adsorption indicates that density porosity may be more properly used to approximate the shale porosity and estimate the shale gas volume. In addition, the specific surface area, micropore, and mesopore volumes have a positive relationship with the kerogen volume and total organic content (TOC). By using the Langmuir and Brunauer-Emmet-Teller models, the simulated result indicates that the higher adsorbed quantity of the Marcellus Shale could be the result of the increase of micropore volume contributed, by the increase of kerogen or TOC content. The proposed equations rapidly compute TOC, a key parameter to predict gas storage capacity in overmature shale such as the Marcellus Shale.

Geochemistry & Geophysics↗
DOE OSTI2017

Geochemical and multi-isotopic ( 87 Sr/ 86 Sr, 143 Nd/ 144 Nd, 238 U/ 235 U) perspectives of sediment sources, depositional conditions, and diagenesis of the Marcellus Shale, Appalachian Basin, USA

Here, we investigate sediment sources, depositional conditions and diagenetic processes affecting the Middle Devonian Marcellus Shale in the Appalachian Basin, eastern USA, a major target of natural gas exploration. Multiple proxies, including trace metal contents, rare earth elements (REE), the Sm-Nd and Rb-Sr isotope systems, and U isotopes were applied to whole rock digestions and sequentially extracted fractions of the Marcellus shale and adjacent units from two locations in the Appalachian Basin. The narrow range of εNd values (from –7.8 to –6.4 at 390 Ma) is consistent with derivation of the clastic sedimentary component of the Marcellus Shale from a well-mixed source of fluvial and eolian material of the Grenville orogenic belt, and indicate minimal post-depositional alteration of the Sm-Nd system. While silicate minerals host >80% of the REE in the shale, data from sequentially extracted fractions reflect post-depositional modifications at the mineralogical scale, which is not observed in whole rock REE patterns.

58 GEOSCIENCES↗
DOE OSTI2015

Rare earth element geochemistry of outcrop and core samples from the Marcellus Shale

In this paper, we studied the geochemistry of the rare earth elements (REE) in eleven outcrop samples and six, depth-interval samples of a core from the Marcellus Shale. The REE are classically applied analytes for investigating depositional environments and inferring geochemical processes, making them of interest as potential, naturally occurring indicators of fluid sources as well as indicators of geochemical processes in solid waste disposal. However, little is known of the REE occurrence in the Marcellus Shale or its produced waters, and this study represents one of the first, thorough characterizations of the REE in the Marcellus Shale. In these samples, the abundance of REE and the fractionation of REE profiles were correlated with different mineral components of the shale. Namely, samples with a larger clay component were inferred to have higher absolute concentrations of REE but have less distinctive patterns. Conversely, samples with larger carbonate fractions exhibited a greater degree of fractionation, albeit with lower total abundance. Further study is necessary to determine release mechanisms, as well as REE fate-and-transport, however these results have implications for future brine and solid waste management applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Preliminary effects of Marcellus shale drilling on Louisiana waterthrush in West Virginia

Preliminary effects of Marcellus shale drilling on Louisiana Waterthrush in West Virginia Page 1 of 1 Doug Becker and James Sheehan, WV Cooperative Fish and Wildlife Research Unit, West Virginia Univ., Morgantown, WV 26506, USA; Petra Bohall Wood, U.S. Geological Survey, WV Cooperative Fish and Wildlife Research Unit, West Virginia Univ., Morgantown, WV 26506, USA; Harry Edenborn, National Energy Technology Laboratory, U.S. Department of Energy, Pittsburgh, PA 15236, USA. Spurred by technological advances and high energy prices, extraction of natural gas from Marcellus shale is increasing in the Appalachian Region. Because little is known about effects on wildlife populations, we studied immediate impacts of oil and gas CO&G) extraction on demographics and relative abundance of Louisiana Waterthrush'CLOWA), a riparian obligate species, to establish a baseline for potential future changes. Annually in 2008-2010, we conducted point counts, monitored Mayfield nesting success, spotted-mapped territories, and measured habitat quality using the EPA Rapid Bioassessment protocol for high gradient streams and a LOWA Habitat Suitability Index CHSI) on a 4,100 ha study area in northern West Virginia. On 11 streams, the stream length affected by O&G activities was 0-58%. Relative abundance, territory denSity, and nest success varied annually but were not significantly different across years. Success did not differ between impacted and unimpacted nests, but territory density had minimal correlation with percent of stream impacted by O&G activities. Impacted nests had lower HSI values in 2010 and lower EPA indices in 2009. High site fidelity could mask the immediate impacts of habitat disturbance from drilling as we measured return rates of 57%. All returning individuals were on the same stream they were banded and 88% were within 250 m of their territory from the previous year. We also observed a spatial shift in LOWA territories, perhaps in response to drilling activities. Preliminary results identified few differences at low habitat disturbance levels but highlight the need for continued monitoring with increasing disturbance. file:

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2015

Numerical simulations of vertical growth of hydraulic fractures and brine migration in geological formations above the Marcellus shale

One of the critical environmental questions about hydraulic fracturing in shales is the potential for contamination of ground and surface water. There are two specific concerns arising from hydraulic treatments: 1) whether hydraulic fractures extend upward through overlying strata to reach overlying aquifers containing drinking water, and 2) whether injected fluids push native fluids upward into these overlying aquifers. In this work, the extent of likely fracture growth through overlying layers during hydraulic treatment of the Marcellus shale was estimated using a hydraulic fracture model. A wide range of material and fluid flow properties in a multi-layered geologic model was considered. The model was based on conditions and characteristics applicable to the Marcellus shale in that part of the Appalachian basin within southwestern Pennsylvania. Predictions of vertical termination frequencies for hydraulic fractures were used in a multi-layer model of the strata and natural fractures for studying brine migration through the natural and induced fracture network. NFFLOW, the software for explicitly modeling flow within networks of fractures, was utilized to compute transient flow rates according to the schedule of injected fluid during hydraulic fracturing. To aid our analysis, the modeled sequence of geologic strata was capped with a fictitious unfractured, but moderately-permeable layer, which serves as a monitoring zone. The analysis assumes one well lateral was placed in the middle of the Marcellus shale with hydraulic fractures penetrating layers in the model. The newly-developed geomechanical module within NFFLOW was used to represent stress-sensitivity of the fractures. This allows the opening and closing of fracture apertures with changes in fluid pressures within fracture segments. Pressure increases in the formations overlying the Tully limestone, indicating fluid flow, was observed due to the hydraulic stimulation; and the impact of these increased pressures on brine migration towards the surface was considered.

03 NATURAL GAS↗
DOE OSTI2024

Estimates of lithium mass yields from produced water sourced from the Devonian-aged Marcellus Shale

Abstract Decarbonatization initiatives have rapidly increased the demand for lithium. This study uses public waste compliance reports and Monte Carlo approaches to estimate total lithium mass yields from produced water (PW) sourced from the Marcellus Shale in Pennsylvania (PA). Statewide, Marcellus Shale PW has substantial extractable lithium, however, concentrations, production volumes and extraction efficiencies vary between the northeast and southwest operating zones. Annual estimates suggest statewide lithium mass yields of approximately 1160 (95% CI 1140–1180) metric tons (mt) per year. Production decline curve analysis on PW volumes reveal cumulative volumetric disparities between the northeast (median = 2.89 X 10 7 L/10-year) and southwest (median = 5.56 × 10 7 L/10-year) regions of the state, influencing lithium yield estimates of individual wells in southwest [2.90 (95% CI 2.80–2.99) mt/10-year] and northeast [1.96 (CI 1.86–2.07) mt/10-year] PA. Moreover, Mg/Li mass ratios vary regionally, where NE PA are low Mg/Li fluids, having a median Mg/Li mass ratio of 5.39 (IQR, 2.66–7.26) and SW PA PW is higher with a median Mg/Li mass ratio of 17.8 (IQR, 14.3–20.7). These estimates indicate substantial lithium yields from Marcellus PW, though regional variability in chemistry and production may impact recovery efficiencies.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Use of Tracer Elements for Estimating Community Exposure to Marcellus Shale Development Operations

Since 2009, unconventional natural gas development (UNGD) has significantly increased in Appalachia’s Marcellus Shale formation. Elevations of fine particulate matter <2.5 µm (PM2.5), have been documented in areas surrounding drilling operations during well stimulation. Furthermore, many communities are experiencing increased industrial activities and probable UNGD air pollutant exposures. Recent studies have associated UNGD emissions with health effects based on distances from well pads. In this study, PM2.5 filter samples were collected on an active gas well pad in Morgantown, West Virginia, and three locations downwind during hydraulic stimulation. Fine particulate samples were analyzed for major and trace elements. An experimental source identification model was developed to determine which elements appeared to be traceable downwind of the UNGD site and whether these elements corresponded to PM2.5 measurements. Results suggest that 1) magnesium may be useful for detecting the reach of UNGD point source emissions, 2) complex surface topographic and meteorological conditions in the Marcellus Shale region could be modeled and confounding sources discounted, and 3) well pad emissions may be measurable at distances of at least 7 km. If shown to be more widely applicable, future tracer studies could enhance epidemiological studies showing health effects of UNGD-associated emissions at ≥15 km.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2011

An Integrated Water Treatment Technology Solution for Sustainable Water Resource Management in the Marcellus Shale

This Final Scientific/ Technical Report submitted with respect to Project DE-FE0000833 titled 'An Integrated Water Treatment Technology Solution for Sustainable Water Resource Management in the Marcellus Shale' in support of final reporting requirements. This final report contains a compilation of previous reports with the most current data in order to produce one final complete document. The goal of this research was to provide an integrated approach aimed at addressing the increasing water resource challenges between natural gas production and other water stakeholders in shale gas basins. The objective was to demonstrate that the AltelaRain{reg_sign} technology could be successfully deployed in the Marcellus Shale Basin to treat frac flow-back water. That objective has been successfully met.

03 NATURAL GAS↗
DOE OSTI2021

Discovery of Gold Nanoparticles in Marcellus Shale

A high density of gold (Au) nanoparticles has been observed on the surfaces of the coexisting opal nanospheres in kerogen-bearing shales from the Marcellus Formation. Our analyses of the Au nanoparticles and associated minerals indicate that this represents a new formation type of colloidal gold nanoparticles. Additionally, the opal nanospheres are a new kind of natural opal-A that is characteristic of the mesoporous texture formed through oil-in-water emulsion processes. High-resolution transmission electron microscopy (TEM) combined with energy-dispersive X-ray spectroscopy analysis directly reveals spherical gold nanoparticles and gold nanorods associated with mesoporous opal nanospheres. Our newly found textures indicate that opal nanospheres may have facilitated the co-precipitation of pure gold nanoparticles in organic-bearing, reduced environments. Furthermore, our TEM observations provide distinct images of the initial phase of colloidal gold and silica, which may contribute to the formation of Au deposits involving "invisible" gold, secondary supergene enrichments, or high-grade gold accumulations. Finally, the discovery of Au nanoparticles in hydrocarbon-rich shale formations such as Marcellus (which contains 0.6-4.1 wt % gold/opal) suggests a potential for co-production of both gas/oil and gold-two valuable commodities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Malignant human cell transformation of Marcellus Shale gas drilling flow back water

The rapid development of high-volume horizontal hydraulic fracturing for mining natural gas from shale has posed potential impacts on human health and biodiversity. The produced flow back waters after hydraulic stimulation are known to carry high levels of saline and total dissolved solids. To understand the toxicity and potential carcinogenic effects of these wastewaters, flow back waters from five Marcellus hydraulic fracturing oil and gas wells were analyzed. The physicochemical nature of these samples was analyzed by inductively coupled plasma mass spectrometry and scanning electron microscopy/energy dispersive X-ray spectroscopy. A cytotoxicity study using colony formation as the endpoint was carried out to define the LC{sub 50} values of test samples using human bronchial epithelial cells (BEAS-2B). The BEAS-2B cell transformation assay was employed to assess the carcinogenic potential of the samples. Barium and strontium were among the most abundant metals in these samples and the same metals were found to be elevated in BEAS-2B cells after long-term treatment. BEAS-2B cells treated for 6 weeks with flow back waters produced colony formation in soft agar that was concentration dependent. In addition, flow back water-transformed BEAS-2B cells show better migration capability when compared to control cells. This study provides information needed to assess the potential health impact of post-hydraulic fracturing flow back waters from Marcellus Shale natural gas mining. - Highlights: • This is the first report of potential cytotoxicity and transforming activity of Marcellus shale gas mining flow back to mammalian cells. • Barium and Strontium were elevated in flow back water exposed cells. • Flow back water malignantly transformed cells and formed tumor in athymic nude mice. • Flow back transformed cells exhibited altered transcriptome with dysregulated cell migration pathway and adherent junction pathway.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Fe Oxidation and Species Distribution at the Rock–Fluid Interface of Marcellus Shale Reacted with Hydraulic Fracturing Fluid

Hydraulic fracturing of shale reservoirs resulted in significant opportunity for increased oil and gas production in the United States. Rock-fluid interactions can cause mineral dissolution and precipitation reactions that lead to permeability changes in the shale matrix, which ultimately may affect transport pathways and hydrocarbon production. Understanding the distribution of secondary precipitates, such as barite and Fe(III) (hydro)oxides, and cation leaching at the rock-fluid interface is an important step to further investigate how these geochemical processes can change permeability and transport pathways. In this study, thin sections of the fracture-matrix interface were made from reacted Marcellus shale cores. The thin sections were characterized using synchrotron X-ray fluorescence imaging and synchrotron X-ray absorption spectroscopy. Fe species with different oxidation states were identified in the maps, together with barite and Ca distribution. The results show that ferrihydrite, as newly formed Fe(III)-bearing precipitates, aligned well with the border of the Ca (e.g., calcite) leaching region in the reaction front. Some Fe-containing clay also dissolved, but the dissolution region for the clay was not as deep as the calcite. Further, the reaction front is about three times deeper in the direction parallel to the shale bedding than that perpendicular to the bedding. The Ca leaching region can be an index for reaction front detection for Marcellus shale. Reactive transport modeling was conducted and the predicted Ca leaching boarder align well with ferrihydrite precipitation, consistent with the experimental observation. The carbonate mineral dissolution can be crucial to promote fluid access into the shale matrix. Together with our previous study on the shale reactive surface, this follow-up study showed similar Ca leaching region and Fe(III) precipitates distribution in the reaction front regardless of barite precipitation on the surface, indicating that the barite coatings on the surface may not pose a significant impact on reactive transport at the shale-fluid interface.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2015

Comparative study of microfacies variation in two samples from the Chittenango member, Marcellus shale subgroup, western New York state, USA

This study demonstrates the significant lithologic variations that occur within the two shale samples from the Chittenango member of the Marcellus shale formation from western New York State in terms of mineralogical composition, type of lamination, pyrite occurrences and fossil content using thin section detailed description and field emission Scanning electron microscope (FESEM) with energy dispersive X-Ray Spectrum (EDX). This study is classified samples as laminated clayshale and fossiliferous carbonaceous shale. The most important detrital constituents of these shales are the clay mineral illite and chlorite, quartz, organic matter, carbonate mineral, and pyrite. The laminated clayshale has a lower amount of quartz and carbonate minerals than fossiliferous carbonaceous shale while it has a higher amount of clay minerals (chlorite and illite) and organic matter. FESEM analysis confirms the presence of chlorite and illite. The fossil content in the laminated clayshale is much lower than the fossiliferous carbonaceous shale. This can provide greater insights about variations in the depositional and environmental factors that influenced its deposition. This result can be compiled with the sufficient data to be helpful for designing the horizontal wells and placement of hydraulic fracturing in shale gas exploration and production.

58 GEOSCIENCES↗
DOE OSTI2021

Marcellus Shale Energy and Environment Laboratory (MSEEL) (Final Report)

The objective of the Marcellus Shale Energy and Environment Laboratory (MSEEL) was to provide a long-term field site to develop and validate new knowledge and technology to improve recovery efficiency and minimize environmental implications of unconventional resource development. MSEEL initiated in October 2014 and completed in September 2021. Total project value was $\$29,765,067$, support from the US Department of energy totaled $\$16,608,355$ with a cost share of $\$13,156,712$ primarily from Northeast Natural Energy. This report in a departure from previous reports summarizes the overarching results and outlines the approach taken. We cover two recent efforts in machine learning and reservoir characterization and simulation. Numerous quarterly reports, public presentations and numerous external publications cover specific results by subtopic and in detail. Publications are listed in the Appendix.

03 NATURAL GAS↗
DOE OSTI2020

Learnings from the Marcellus Shale Energy and Environmental Lab (MSEEL) Using Fiber Optic Tools and Geomechanical Modeling

The study focuses on the MIP and Boggess pads of the MSEEL (Marcellus Shale Energy and Environmental Laboratory), a public-private partnership with a mandate to publicly release data for scientists and engineers to engage with. Multiple diagnostic tools are used to characterize the formation and monitor fracture treatment and propagation. Geomechanical modeling is used to understand the insitu stresses, microseismic to describe half-lengths and heights, and fiber optics to characterize offset well. Fracture Driven Interactions (FDI’s) and interstage communication. Recent publications covering the MSEEL MIP-3H and MIP-5H wells are reviewed and discussed. A preview of the findings from the Boggess pad (first production in November 2019) is also shared here

03 NATURAL GAS↗
DOE OSTI2017

Predominance and metabolic potential of Halanaerobium spp. in produced water from hydraulically fractured Marcellus Shale wells

Here, microbial activity in the produced water from hydraulically fractured oil and gas wells may potentially interfere with hydrocarbon production and cause damage to the well and surface infrastructure via corrosion, sulfide release, and fouling. In this study, we surveyed the microbial abundance and community structure of produced water sampled from 42 Marcellus Shale wells in southwestern Pennsylvania (well age ranged from 150 to 1,846 days) to better understand the microbial diversity of produced water. We sequenced the V4 region of the 16S rRNA gene to assess taxonomy and utilized quantitative PCR (qPCR) to evaluate the microbial abundance across all 42 produced water samples. Bacteria of the order Halanaerobiales were found to be the most abundant organisms in the majority of the produced water samples, emphasizing their previously suggested role in hydraulic fracturing-related microbial activity. Statistical analyses identified correlations between well age and biocide formulation and the microbial community, in particular, the relative abundance of Halanaerobiales . We further investigated the role of members of the order Halanaerobiales in produced water by reconstructing and annotating a Halanaerobium draft genome (named MDAL1), using shotgun metagenomic sequencing and metagenomic binning. The recovered draft genome was found to be closely related to the species H. congolense, an oil field isolate, and Halanaerobium sp. strain T82-1, also recovered from hydraulic fracturing produced water. Reconstruction of metabolic pathways revealed Halanaerobium sp. strain MDAL1 to have the potential for acid production, thiosulfate reduction, and biofilm formation, suggesting it to have the ability to contribute to corrosion, souring, and biofouling events in the hydraulic fracturing infrastructure.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2012

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{sub Sr}{sup SW} = +13.8 to +41.6, where ε{sub Sr}{sup SW} is the deviation of the {sup 87}Sr/{sup 86}Sr ratio from that of seawater in parts per 10{sup 4}); 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.

03 NATURAL GAS↗
DOE OSTI2012

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.

58 GEOSCIENCES↗
DOE OSTI2017

Environmental flows in the context of unconventional natural gas development in the Marcellus Shale

Quantitative flow-ecology relationships are needed to evaluate how water withdrawals for unconventional natural gas development may impact aquatic ecosystems. Addressing this need, we studied current patterns of hydrologic alteration in the Marcellus Shale region and related the estimated flow alteration to fish community measures. We then used these empirical flow-ecology relationships to evaluate alternative surface water withdrawals and environmental flow rules. Reduced high-flow magnitude, dampened rates of change, and increased low-flow magnitudes were apparent regionally, but changes in many of the flow metrics likely to be sensitive to withdrawals also showed substantial regional variation. Fish community measures were significantly related to flow alteration, including declines in species richness with diminished annual runoff, winter low-flow, and summer median-flow. In addition, the relative abundance of intolerant taxa decreased with reduced winter high-flow and increased flow constancy, while fluvial specialist species decreased with reduced winter and annual flows. Stream size strongly mediated both the impact of withdrawal scenarios and the protection afforded by environmental flow standards. Under the most intense withdrawal scenario, 75% of reference headwaters and creeks (drainage areas <99 km 2 ) experienced at least 78% reduction in summer flow, whereas little change was predicted for larger rivers. Moreover, the least intense withdrawal scenario still reduced summer flows by at least 21% for 50% of headwaters and creeks. The observed 90th quantile flow-ecology relationships indicate that such alteration could reduce species richness by 23% or more. Seasonally varying environmental flow standards and high fixed minimum flows protected the most streams from hydrologic alteration, but common minimum flow standards left numerous locations vulnerable to substantial flow alteration. This study clarifies how additional water demands in the region may adversely affect freshwater biological integrity. Furthermore, the results make clear that policies to limit or prevent water withdrawals from smaller streams can reduce the risk of ecosystem impairment.

54 ENVIRONMENTAL SCIENCES↗