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At least 37 records · Page 2Linked to original sources
USGS2021

Organo-facies and mineral effects on sorption capacity of low-maturity Permian Barakar shales from the Auranga Basin, Jharkhand, India

Shales associated with the Lower Permian (Barakar Formation) sediments of the Auranga Coalfield, India, occur in the immature–early mature stage. The sorption capacity of Barakar shale samples has been studied through high-pressure methane (CH 4 ) adsorption and low-pressure N 2 gas adsorption (LPN 2 GA) methods, supported with proximate analyses, programmed pyrolysis, optical petrography, and with energy-dispersive spectroscopy, X-ray diffraction, and inductively coupled plasma mass spectrometry. The sorption capacity is a function of the organic and inorganic constituents present in the shale samples. The methane sorption capacity (MSC) and Langmuir volume of the shale samples vary from 0.217 to 0.314 and 0.315 to 0.429 mmol/g rock, respectively. The BET-calculated surface area of the studied shales varies from 8.12 to 30.36 m 2 /g. The sorption capacities show the importance of the total organic content (TOC) through weak but positive correlations with MSC ( r 2 = 0.45) and S 1 values (mg hydrocarbons/g rock from programmed pyrolysis; r 2 = 0.40). Moreover, apparent inverse relationships were observed between MSC and clay mineral abundances, suggesting that individual clay mineral types may influence MSC, although more work is needed. The TOC-normalized MSC (MSC*) of shale samples shows a positive trend with quartz plus clay mineral content and ash yield of r 2 = 0.64 for both. In addition, MSC* shows a negative logarithmic relationship with S 1 + S 2 ( r 2 = 0.63) and a positive linear relationship with TOC-normalized total organic matter (TOM*) ( r 2 = 0.88, when 5 low TOM* samples are excluded) indicating complex relationships possibly including bitumen retention in the sample pore spaces. The micropore study of the samples through LPN 2 GA, applying Dubinin–Radushkevich, Dubinin–Astakhov, and density functional theory models, shows the dominance of micro-mesopore concentrations in the shale matrix of ∼2 nm pore diameter. However, these pores might be present as blind or closed pores. The presence of thorium and zirconium is reflective of terrigenous detrital matter, i.e., moderately to strongly recycled sediments. The fluviatile facies of deposited shales in the Auranga Coalfield are noted by the significant presence of kaolinite (32.5–78.3%), which suggests the importance of its effect on the sorption capacity of proximal terrigenous shales.

Jharkhand↗
USGS2022

Virtual special issue of recent advances on gas hydrates scientific drilling in Alaska

Gas hydrate refers to a non-stoichiometric clathrate that forms spontaneously in the natural environment whenever sufficient quantities of gases of appropriate size (most commonly methane) interact with abundant water under specific conditions of temperature and pressure. (1,2) Such conditions occur wherever the shallow geothermal gradient has been suppressed by either deepwater or thick permafrost, allowing for relatively low temperatures to coexist with elevated pressures. The volume of gas hydrate on Earth is difficult to constrain, (3) but it is sufficient that gas hydrate is a meaningful potential component of (1) the long-term natural cycling of carbon, (2) the nearer term environmental changes in response to warming climates, (4) and (3) future energy supply systems. Since the initial recognition of gas hydrate as an abundant component in nature in the late 1960s, a series of scientific drilling expeditions conducted by both the Integrated Ocean Discovery Program (and successors) and national research and development programs in Canada, Japan, China, the United States, South Korea, and others (5) have explored the occurrence and nature of gas hydrates. In particular, the desire for expanded energy supply options to support the economic development and energy security for nations around the globe is currently motivating a broad range of laboratory and numerical simulation studies in support of an ongoing series of field-based scientific tests of the potential commercial viability of gas extraction from natural gas hydrate deposits. (6)

Journal of Energy & Fuels↗
USGS2024

Examining water and proppant demand, and produced water production, associated with petroleum resource development in the Eagle Ford Group, Texas

More than 20,000 horizontal wells have been drilled and hydraulically fractured in the Eagle Ford Group since the discovery well in 2008, but a considerable amount of undiscovered petroleum remains. Recently, drilled wells have been hydraulically fractured with an average of nearly 13 million gallons of water and 16 million lb of sand, yielding a million or more gallons of produced water. To inform future petroleum development in the Eagle Ford, the U.S. Geological Survey (USGS) conducted a water and proppant assessment using a geology-based approach that builds on the 2018 USGS assessment of undiscovered technically recoverable petroleum. Using probabilistic input values and a Monte Carlo simulation, we determined that production of the remaining undiscovered technically recoverable oil and gas in the Eagle Ford Group would require approximately 687,565 Mgal (millions of gallons) of water and 839,702,000,000 lb of proppant (both are mean values of output distributions). This possible future petroleum production would also include 176,817 Mgal (mean value) of produced formation water. On average, oil wells require water volumes that are approximately twice the volume of oil that will be produced, and Eagle Ford gas wells require approximately 5.21 Mgal of water per billion cubic feet of gas (bcfg). Produced formation water volumes are approximately 60% of the produced oil volume and, for gas wells, will yield approximately 1 Mgal formation water per bcfg. Understanding the water and proppant requirements associated with petroleum exploration and the resulting volume of produced water can inform decisions regarding the future of Eagle Ford development.

Texas↗
USGS2015

Detailed description of oil shale organic and mineralogical heterogeneity via fourier transform infrared mircoscopy

Mineralogical and geochemical information on reservoir and source rocks is necessary to assess and produce from petroleum systems. The standard methods in the petroleum industry for obtaining these properties are bulk measurements on homogenized, generally crushed, and pulverized rock samples and can take from hours to days to perform. New methods using Fourier transform infrared (FTIR) spectroscopy have been developed to more rapidly obtain information on mineralogy and geochemistry. However, these methods are also typically performed on bulk, homogenized samples. We present a new approach to rock sample characterization incorporating multivariate analysis and FTIR microscopy to provide non-destructive, spatially resolved mineralogy and geochemistry on whole rock samples. We are able to predict bulk mineralogy and organic carbon content within the same margin of error as standard characterization techniques, including X-ray diffraction (XRD) and total organic carbon (TOC) analysis. Validation of the method was performed using two oil shale samples from the Green River Formation in the Piceance Basin with differing sedimentary structures. One sample represents laminated Green River oil shales, and the other is representative of oil shale breccia. The FTIR microscopy results on the oil shales agree with XRD and LECO TOC data from the homogenized samples but also give additional detail regarding sample heterogeneity by providing information on the distribution of mineral phases and organic content. While measurements for this study were performed on oil shales, the method could also be applied to other geological samples, such as other mudrocks, complex carbonates, and soils.

Energy & Fuels↗
USGS2015

Extraction of hydrocarbons from high-maturity Marcellus Shale using supercritical carbon dioxide

Shale is now commonly exploited as a hydrocarbon resource. Due to the high degree of geochemical and petrophysical heterogeneity both between shale reservoirs and within a single reservoir, there is a growing need to find more efficient methods of extracting petroleum compounds (crude oil, natural gas, bitumen) from potential source rocks. In this study, supercritical carbon dioxide (CO 2 ) was used to extract n -aliphatic hydrocarbons from ground samples of Marcellus shale. Samples were collected from vertically drilled wells in central and western Pennsylvania, USA, with total organic carbon (TOC) content ranging from 1.5 to 6.2 wt %. Extraction temperature and pressure conditions (80°C and 21.7 MPa, respectively) were chosen to represent approximate in situ reservoir conditions at sample depth (1920–2280 m). Hydrocarbon yield was evaluated as a function of sample matrix particle size (sieve size) over the following size ranges: 1000–500 μm, 250–125 μm, and 63–25 μm. Several methods of shale characterization including Rock-Eval II pyrolysis, organic petrography, Brunauer–Emmett–Teller surface area, and X-ray diffraction analyses were also performed to better understand potential controls on extraction yields. Despite high sample thermal maturity, results show that supercritical CO 2 can liberate diesel-range ( n -C 11 through n -C 21 ) n -aliphatic hydrocarbons. The total quantity of extracted, resolvable n -aliphatic hydrocarbons ranges from approximately 0.3 to 12 mg of hydrocarbon per gram of TOC. Sieve size does have an effect on extraction yield, with highest recovery from the 250–125 μm size fraction. However, the significance of this effect is limited, likely due to the low size ranges of the extracted shale particles. Additional trends in hydrocarbon yield are observed among all samples, regardless of sieve size: 1) yield increases as a function of specific surface area ( r 2 = 0.78); and 2) both yield and surface area increase with increasing TOC content ( r 2 = 0.97 and 0.86, respectively). Given that supercritical CO 2 is able to mobilize residual organic matter present in overmature shales, this study contributes to a better understanding of the extent and potential factors affecting the extraction process.

Pennsylvania↗
USGS2026

Consolidation and permeability of the B1 and D1 gas hydrate bearing sands and associated seal sediments of the extended-duration gas production test site on the Alaska North Slope

Gas hydrate, a solid combination of gas (mostly methane in nature) and water molecules stable at low temperatures and elevated pressures, occurs naturally in marine and permafrost-associated environments. Gas hydrate reservoirs, such as those in the Alaska North Slope, have been considered potential energy resources for gas production. To understand the petrophysical and geo-mechanical characteristics of the reservoir, core samples retrieved from the site of the JOGMEC-DOE-USGS collaborative gas hydrate R&D project have been analyzed in the laboratory for their hydraulic and mechanical properties. This paper focuses on both seal and reservoir samples associated with the B1 and D1 sands, which are evaluated for index properties (including porosity, grain size distribution, liquid and plastic limits, specific surface area, and specific gravity), consolidation, permeability, and water retention. Furthermore, the reservoir core samples were tested with pore-filling, laboratory-grown tetrahydrofuran hydrate, in order to assess reservoir behavior during gas production from hydrates. Under simulated in situ stress conditions, the seal and hydrate-free reservoir cores had a permeability anisotropy ratio of k h / k v = 3.0–5.0, and k h / k v = 2.4–3.0 for the reservoir tetrahydrofuran hydrate-bearing cores. The data suggest that depressurizing the reservoir to induce hydrate dissociation alters the reservoir effective permeability in three ways: permeabilities decrease due to porosity lost (e.g., the initial reservoir thickness can decrease by up to 5% upon 7 MPa depressurization), permeability increases due to the loss of solid hydrate in the pore space, and permeability anisotropy k h / k v decreases in response to the evolving pore-space geometry. We show that given the simulated in situ gas hydrate saturations (i.e., S h = 32% in core 7P-2E and S h = 21% in core 20P-4), gas production from the dissociation of tetrahydrofuran hydrate in the two tested cores results in a net increase in effective permeability and a decrease in k h / k v . This study highlights the importance of investigating seal and reservoir sediments and the impacts of depressurization on the porosity and permeability responses during production.

Alaska↗
USGS2026

Permeability and compressibility of “seal” sediment overlying the B1 sand gas hydrate reservoir: Hydrate 02 Geo Data Well, Prudhoe Bay unit, Alaska North Slope

An important element in evaluating the viability of extracting methane from a gas hydrate-bearing reservoir is establishing the effectiveness of the overlying bounding sediment as a seal to prevent gas loss, to enable effective depressurization, and to prevent fluid from entering the reservoir during production. This laboratory study presents results for index properties (e.g., grain density, grain size, and liquid limit), compressibility and swelling indices, and permeability measurements on sediment overlying the gas hydrate-bearing reservoir that was the target of the recent JOGMEC-DOE-USGS collaborative gas hydrate production testing project on the Alaska North Slope (ANS). Sediment analyzed in this study was collected during pressure coring operations in the HYDRATE 02 Geo Data Well (GDW). The ∼6.1 m sediment interval recovered in Cores 13P and 14P (878.74–884.88 m measured depth, MD) exhibited heterogeneous sedimentologic characteristics at the centimeter scale, with sediments ranging from clay to thin silty-sand lithologies. Permeability measurements and index-property correlations indicate the interval’s overall in situ vertical permeability ranges from 0.2 to 3.6 microdarcy (μD). Results for compressibility ( C C = 0.255 ± 0.02) and swelling index ( C S = 0.04 ± 0.01) are consistent with estimates based on mineralogy and liquid limit correlations. Based on the measured compressibility, the ∼3 MPa increase in effective stress during the stable phase of depressurization-induced production is anticipated to have imposed 2.43 cm of compaction per meter in the reservoir overburden, reducing permeability by ∼36%. The overburden sediment’s low in situ permeability (3 to 4 orders of magnitude below permeabilities measured in the gas hydrate-bearing part of the B1 sand (unit B)) suggests the B1 sand′s overburden provides an effective seal. Such a seal promotes efficient production by limiting fluid flow into the reservoir during depressurization-induced gas hydrate dissociation.

Alaska↗
USGS2026

Strength, stiffness, and Poisson’s ratio measurements for cements used in the well completions for the extended-duration gas production test on the Alaskan North Slope

As part of an extended-duration production test from a natural gas hydrate reservoir on the Alaska North Slope, a suite of optical-fiber sensors was encased in the completion cement to provide stable downhole monitoring around each of the four project wells. How the sensors respond to changes in the reservoir over time depends in part on properties of the LiteCRETE, ArcticCem, or Tuned Light cement in which each sensor is encased, and on how well the cement bonded to the well casing, sensors, and sediment formation. Here, we report on physical properties of the cements (compressive and tensile strength, stiffness, and Poisson’s ratio), on the downhole distribution of the cements used in each well, and on the cement bond quality. Physical property measurements are presented for cements sampled during the completion activities for the three wells completed in 2022–2023. Samples were cured while being submerged in water at 2–4 °C, then tested at intervals from ∼30 days to more than one year. After an initial period of rapid increase, cement strengths largely stabilized around 120 days in all cases, meaning that cements in all wells reached their nominal strength plateau four months or more before the production test began. Calculations based on recorded volumes of pumped cement show the subpermafrost, main hole portion of each well is encased only in the higher-density “tail” cement used in that well. Downhole cement evaluation logs from two wells demonstrate how the presence of sensors and other hardware outside the casing interferes with the cement evaluation assessment. Nonetheless, the cement evaluations indicate a generally good bond with the formation and sensors over the gas hydrate reservoir intervals.

Alaska↗
USGS2026

Oil in the Alaska North Slope gas hydrate reservoir: Micro-CT and flow simulation insights into permeability

Gas hydrate-bearing sands on the Alaska North Slope (ANS) host minor volumes of crude oil whose impact on formation permeability has never been quantified relative to a gas hydrate reservoir system. Here, we combine in situ pressure-core microcomputed-tomography (μ-CT), thermogravimetric analysis (TGA), gas-chromatography–mass-spectrometry (GC–MS), scanning-electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), and Stokes-flow simulation to (i) quantify oil saturation, (ii) infer its source, and (iii) evaluate its influence on permeability after gas-hydrate dissociation. μ-CT and SEM-EDS imaging identify the host sediment as silty, with some grain-coating clay present. Eight representative 300 3 -voxel subvolumes extracted from a preserved pressure core (Core 15P-3c, from the B1 sand (unit B), HYDRATE 02 Geo Data Well (GDW), 886.96–887.29 m measured depth, MD) exhibit porosities of 0.34–0.37 and an average oil saturation of 0.09 ± 0.03, in comparison to an independent TGA-based estimate of 0.16. GC-MS fingerprints obtained from an adjacent depressurized core (Core 17P-1, 891.37–891.44 m MD), together with oil pore habit revealed by μ-CT, suggest that the oil is partly native but also includes contributions from mineral oil-based drilling fluid contamination. Further analysis of oil–porewater interactions and flushing tests confirms that native oil saturation in the analyzed samples ranges from 0.04 to 0.08 with an average of approximately 0.06, and the oil is highly immobile. Flow simulations demonstrate that the native oil saturation of ≈0.06 reduces permeability by approximately 50% due to both pore blockage and increased flow-path tortuosity. These findings reveal the potential presence of native oil within the ANS gas hydrate reservoir and suggest that future simulation models may need to account for its impact on permeability to improve long-term performance predictions of gas and water production.

Alaska↗
USGS2016

Sulfur species in source rock bitumen before and after hydrous pyrolysis determined by X-ray absorption near-edge structure

The sulfur speciation of source rock bitumen (chloroform-extractable organic matter in sedimentary rocks) was examined using sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy for a suite of 11 source rocks from around the world. Sulfur speciation was determined for both the native bitumen in thermally immature rocks and the bitumen produced by thermal maturation of kerogen via hydrous pyrolysis (360 °C for 72 h) and retained within the rock matrix. In this study, the immature bitumens had higher sulfur concentrations than those extracted from samples after hydrous pyrolysis. In addition, dramatic and systematic evolution of the bitumen sulfur moiety distributions following artificial thermal maturation was observed consistently for all samples. Specifically, sulfoxide sulfur (sulfur double bonded to oxygen) is abundant in all immature bitumen samples but decreases substantially following hydrous pyrolysis. The loss in sulfoxide sulfur is associated with a relative increase in the fraction of thiophene sulfur (sulfur bonded to aromatic carbon) to the extent that thiophene is the dominant sulfur form in all post-pyrolysis bitumen samples. This suggests that sulfur moiety distributions might be used for estimating thermal maturity in source rocks based on the character of the extractable organic matter.

Energy & Fuels↗
USGS2016

The Iġnik Sikumi Field Experiment, Alaska North Slope: Design, operations, and implications for CO 2 −CH 4 exchange in gas hydrate reservoirs

The Iġnik Sikumi Gas Hydrate Exchange Field Experiment was conducted by ConocoPhillips in partnership with the U.S. Department of Energy, the Japan Oil, Gas and Metals National Corporation, and the U.S. Geological Survey within the Prudhoe Bay Unit on the Alaska North Slope during 2011 and 2012. The primary goals of the program were to (1) determine the feasibility of gas injection into hydrate-bearing sand reservoirs and (2) observe reservoir response upon subsequent flowback in order to assess the potential for CO 2 exchange for CH 4 in naturally occurring gas hydrate reservoirs. Initial modeling determined that no feasible means of injection of pure CO 2 was likely, given the presence of free water in the reservoir. Laboratory and numerical modeling studies indicated that the injection of a mixture of CO 2 and N 2 offered the best potential for gas injection and exchange. The test featured the following primary operational phases: (1) injection of a gaseous phase mixture of CO 2 , N 2 , and chemical tracers; (2) flowback conducted at downhole pressures above the stability threshold for native CH 4 hydrate; and (3) an extended (30-days) flowback at pressures near, and then below, the stability threshold of native CH 4 hydrate. The test findings indicate that the formation of a range of mixed-gas hydrates resulted in a net exchange of CO 2 for CH 4 in the reservoir, although the complexity of the subsurface environment renders the nature, extent, and efficiency of the exchange reaction uncertain. The next steps in the evaluation of exchange technology should feature multiple well applications; however, such field test programs will require extensive preparatory experimental and numerical modeling studies and will likely be a secondary priority to further field testing of production through depressurization. Additional insights gained from the field program include the following: (1) gas hydrate destabilization is self-limiting, dispelling any notion of the potential for uncontrolled destabilization; (2) gas hydrate test wells must be carefully designed to enable rapid remediation of wellbore blockages that will occur during any cessation in operations; (3) sand production during hydrate production likely can be managed through standard engineering controls; and (4) reservoir heat exchange during depressurization was more favorable than expected—mitigating concerns for near-wellbore freezing and enabling consideration of more aggressive pressure reduction.

Energy & Fuels↗
USGS2017

Extension of the analytical window for characterizing aromatic compounds in oils using a comprehensive suite of high-resolution mass spectrometry techniques and double bond equivalence versus carbon number plot

In this study, comprehensive two-dimensional (2D) gas chromatography–mass spectrometry (GC–MS), atmospheric pressure photoionization (APPI) quadrupole-Orbitrap mass spectrometry (MS), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) were used to study the aromatic fractions of crude oil and oil shale pyrolysates (shale oils). The collected data were compared and combined in the double bond equivalence (DBE) versus carbon number plot to obtain a more complete understanding of the composition of the oil fractions. The numbers of peaks observed by each technique followed the order 2D GC–MS < Orbitrap MS < FT-ICR MS. The class distributions observed by Orbitrap MS and FT-ICR MS were similar to each other but different from that observed by 2D GC–MS. The DBE and carbon number distributions of the 2D GC–MS and Orbitrap MS data were similar for crude oil aromatics. The FT-ICR MS plots of DBE and carbon number showed an extended range of higher values relative to the other methods. For the aromatic fraction of an oil shale pyrolysate generated by the Fischer assay, only a few nitrogen-containing compounds were observed by 2D GC–MS but a large number of these compounds were detected by Orbitrap MS and FT-ICR MS. This comparison clearly shows that the data obtained from these three techniques can be combined to more completely characterize oil composition. The data obtained by Orbitrap MS and FT-ICR MS agreed well with one another, and the combined DBE versus carbon number plot provided more complete coverage of compounds present in the fractions. In addition, the chemical structure information provided by 2D GC–MS could be matched with the chemical formulas in the DBE versus carbon number plots, providing information not available in ultrahigh-resolution MS results. It was therefore concluded that the combination of 2D GC–MS, Orbitrap MS, and FT-ICR MS in the DBE versus carbon number space facilitates structural assignment of heavy oil components.

Energy & Fuels↗
USGS2018

Biogenic coal-to-methane conversion efficiency decreases after repeated organic amendment

Addition of organic amendments to coal-containing systems can increase the rate and extent of biogenic methane production for 60–80 days before production slows or stops. Understanding the effect of repeated amendment additions on the rate and extent of enhanced coal-dependent methane production is important if biological coal-to-methane conversion is to be enhanced on a commercial scale. Microalgal biomass was added at a concentration of 0.1 g/L to microcosms with and without coal on days 0, 76, and 117. Rates of methane production were enhanced after the initial amendment but coal-containing treatments produced successively decreasing amounts of methane with each amendment. During the first amendment period, 113% of carbon added as amendment was recovered as methane, whereas in the second and third amendment periods, 39% and 32% of carbon added as amendment was recovered as methane, respectively. Additionally, algae-amended coal treatments produced ∼38% more methane than unamended coal treatments and ∼180% more methane than amended coal-free treatments after one amendment. However, a second amendment addition resulted in only an ∼25% increase in methane production for coal versus noncoal treatments and a third amendment addition resulted in similar methane production in both coal and noncoal treatments. Successive amendment additions appeared to result in a shift from coal-to-methane conversion to amendment-to-methane conversion. The reported results indicate that a better understanding is needed of the potential impacts and efficiencies of repeated stimulation for enhanced coal-to-methane conversion.

Energy & Fuels↗
USGS2018

Investigation into the effect of heteroatom content on kerogen structure using advanced 13C solid-state nuclear magnetic resonance spectroscopy

To elucidate how different extreme heteroatom concentrations in oil shale kerogen may present and contribute to various structural features, three shale samples, containing kerogen with high oxygen content, low heteroatom content, and high sulfur content, were analyzed using advanced 13 C solid-state nuclear magnetic resonance (NMR) techniques, including multiple cross-polarization/magic angle spinning (multiCP/MAS), dipolar dephasing (multiCP/DD), and 2D 1 H– 13 C heteronuclear correlation (2D HETCOR). We found that oxygen in Estonian kukersite was present mostly in aromatic C–O structures and that nonprotonated aromatic carbons bonded to oxygen and alkyl chains led to more diverse aromatic signal distributions and structures in the kukersite organic matter than were observed in the other shales. The low-heteroatom kerogen present in Australian Glen Davis torbanite had the simplest structural pattern and the lowest aromaticity, despite having a lower atomic H/C ratio than the kerogens present in the other shales. The organic sulfur-rich Ghareb marinite from Jordan contained the highest aromaticity and most diverse alkyl structures among the three shales. 2D HETCOR with 1 H spin diffusion showed that the structural heterogeneity of the Glen Davis kerogen was <1 nm, indicating the preservation of structures present in precursor organic matter. Like previous NMR studies of shales and kerogens, this analysis of organic matter in whole shale samples with unusual heteroatom content demonstrates that structural characteristics in organic matter are not necessarily captured by kerogen typing based solely on elemental ratios (H/C, O/C) or programmed pyrolysis parameters and that NMR provides deeper insights into kerogen structure.

Energy & Fuels↗
USGS2018

Application of Raman spectroscopy as thermal maturity probe in shale petroleum systems: Insights from natural and artificial maturation series

Raman spectroscopy was studied as a thermal maturity probe in a series of Upper Devonian Ohio Shale samples from the Appalachian Basin spanning from immature to dry gas conditions. Raman spectroscopy also was applied to samples spanning a similar thermal range created from 72-h hydrous pyrolysis (HP) experiments of the Ohio Shale at temperatures from 300 to 360 °C and isothermal HP experiments lasting up to 100 days of similar Devonian–Mississippian New Albany Shale. Raman spectra were treated by automated evaluation software based on iterative and simultaneous modeling of signal and baseline functions to decrease subjectivity. Spectra show robust correlation to measured solid bitumen reflectance (BR o ) values and were therefore used to construct logarithmic regression relationships for calculation of BR o equivalent values. Raman spectra show considerable differences between natural samples and HP residues with similar measured BR o values, indicating as-yet undetermined differences in carbon chemistry. We speculate this result may be due to differences in the sampling interactions of Raman vs reflectance measurements, and the incomplete nature of maturation reactions in the time-limited hydrous pyrolysis residues. Samples used in this study are similar in organic assemblage (dominantly solid bitumen) to other commonly exploited North American shale petroleum systems, i.e., Bakken, Barnett, Duvernay, Fayetteville, and Woodford shales. Therefore, results presented herein may be broadly applicable to other important shale plays. However, caution is suggested and Raman spectroscopy as a thermal probe may need individual calibration in each shale play due to differences in solid bitumen carbon chemistry.

Energy & Fuels↗
USGS2019

Experimental study on the impact of thermal maturity on shale microstructures using hydrous pyrolysis

Hydrous pyrolysis was applied to four low-maturity aliquots from the Utica, Excello, Monterey, and Niobrara Shale Formations in North America to create artificial maturation sequences, which could be used to study the impact of maturation on geochemical and microstructural properties. Modified Rock-Eval pyrolysis, reflectance, organic petrology, and Fourier transform infrared spectroscopy (FTIR) were employed to analyze their geochemical properties, while gas adsorption (CO 2 and N 2 ) was used to characterize their pore structures (pores < 200 nm). Organic petrography using white and blue light (fluorescence) before and after hydrous pyrolysis showed that amorphous organic matter cracked into solid bitumen, oil, and gas during hydrous pyrolysis. A reduction of the CH 2 /CH 3 ratio in hydrous pyrolysis residues was observed from FTIR analysis. Rock-Eval pyrolysis showed that kerogens in the four samples were dissimilar, and hydrous pyrolysis residues showed smaller hydrogen index and Sh2 values than starting materials. Results from CO 2 and N 2 gas adsorption analysis showed that pore structures (micropore volume, micropore surface area, meso-macropore volume, and meso-macropore surface area) changed significantly during hydrous pyrolysis. However, changes in pore structure were dissimilar among the four samples, which was attributed to different activation energies of organic matter. A thermodynamic fractal model showed a decrease in fractal dimensions of Utica, Monterey, and Excello after hydrous pyrolysis, indicating a decrease in surface roughness. The pore size heterogeneity in the Utica sample increased as hydrous pyrolysis temperature increased, whereas the pore size heterogeneity distributions in the Monterey and Excello decreased based on the N 2 adsorption data.

Energy & Fuels↗
USGS2020

Impacts of mineralogical variation on CO2 behavior in small pores from producing intervals of the Marcellus Shale: Results from neutron scattering

The Near and InterMediate Range Order Diffractometer (NIMROD) was used to examine the potential impact of shale mineralogy on CO 2 behavior within micropores. Two samples with varying mineral compositions were obtained from producing intervals in the dry gas window in the Middle Devonian Marcellus Shale. One of the samples contained relatively high amounts of quartz and clay and low carbonate, the other contained relatively equal amounts of quartz, carbonate, and clay. The samples were probed with CO 2 at subcritical pressures (20–50 bar) and temperature (22 °C) and characterized over a neutron scattering vector ( Q ) range of 0.02 < Q < 50 Å –1 . This Q range provides information from the atomistic length-scale up to pore radii of 10 nm. Mineralogy variations between the samples did not affect scattering ratios over the entire Q range accessible with the NIMROD. Q values for the minimum scattering ratios of both samples at similar pressures are remarkably similar, particularly for Q < ∼0.09 Å –1 , and maximum scattering ratios are similar in both samples suggesting that mineral pores are so uncommon in the pore sizes examined that they cannot be resolved due to the overwhelming amounts of organic pores in these samples. Overall, these findings suggest that mineralogical variations have little effect on CO 2 behavior within organic matter-hosted shale micropores at high thermal maturities and they lend support to the assertion that CO 2 cannot be stored in the vast surface areas of micropores in organic material in shale formations. In addition, CO 2 enhanced oil recovery (EOR) is unlikely to displace petroleum from some of the smaller mesopores (2.5 to ∼3.5 nm) and all of the micropores because they are effectively closed to CO 2 . amples were probed with CO2 at subcritical pressures (20 50 bar) and temperature (22 oC) and characterized over a neutron scattering vector (Q) range of 0.02 < Q < 50 -1. This Q range provides information on nominal pore size radii of around 10 0.5 nm. Mineralogy variations between the samples did not affect scattering ratios over the entire Q range accessible with the NIMROD. Q values for the minimum scattering ratios of both samples at similar pressures are statistically indistinguishable and maximum scattering ratios are similar in both samples suggesting that mineral pores are either absent or are so uncommon that they cannot be resolved due to the overwhelming amounts of organic pores in these samples. Overall, these findings suggest that mineralogical variations have little effect on CO2 behavior within organic matter-hosted shale micropores at high thermal maturities and they lend support to the assertion that CO2 cannot be stored in the vast surface areas of micropores (<2.5 nm) in shale formations. In addition, CO2 enhanced oil recovery (EOR) is unlikely to displace petroleum from some of the smaller mesopores (2.5 10 nm) and all of the micropores because they are effectively closed to CO2.

Energy & Fuels↗
USGS2002

Dipolar-dephasing 13C NMR studies of decomposed wood and coalified xylem tissue: Evidence for chemical structural changes associated with defunctionalization of lignin structural units during coalification

A series of decomposed and coalified gymnosperm woods was examined by conventional solid-state 13C nuclear magnetic resonance (NMR) and by dipolar-dephasing NMR techniques. The results of these NMR studies for a histologically related series of samples provide clues as to the nature of codification reactions that lead to the defunctionalization of lignin-derived aromatic structures. These reactions sequentially involve the following: (1) loss of methoxyl carbons from guaiacyl structural units with replacement by hydroxyls and increased condensation; (2) loss of hydroxyls or aryl ethers with replacement by hydrogen as rank increases from lignin to high-volatile bituminous coal; (3) loss of alkyl groups with continued replacement by hydrogen. The dipolar-dephasing data show that the early stages of coalification in samples examined (lignin to lignite) involve a decreasing degree of protonation on aromatic rings and suggest that condensation is significant during coalification at this early stage. An increasing degree of protonation on aromatic rings is observed as the rank of the sample increases from lignite to anthracite.

Energy & Fuels↗