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At least 1,513 records · Page 84Linked to original sources
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↗
USGS2026

Lithological control of gas hydrate saturation determined by pressure core analysis in sub-permafrost reservoirs of the Alaska North Slope (HYDRATE 02 Geo Data Well)

Quantitatively degassing pressure cores by controlled depressurization is a key approach to characterizing gas hydrate reservoirs by measuring the gas hydrate saturation (S h ) of sediments. We measured S h for 53 core sections from the Alaska North Slope during the JOGMEC-DOE-USGS Collaborative Gas Hydrate R&D Project in Alaska, from subpermafrost sediments that were later subjected to an extended-duration gas production test. We characterized lithologic influences on S h using physical property core scans (P-wave velocity, gamma ray attenuation density, and X-ray computed tomography) and grain size measurements. Pressure cores were recovered from the Hydrate-02 Geo Data Well (GDW) at the Kuparuk State 7-11-12 site through two hydrate-bearing sand reservoirs, the B1 and D1 sands, and their finer-grained bounding sediments. S h reaches very high values (68 to 91% of the pore space) in silty fine sands within the B1 sand, which also contains two lower P-wave velocity intervals (one measured at 30% S h ) within the main reservoir. S h and grain sizes of the B1 sand are generally higher than the D1 sand, which hosts high S h (53 to 73%) within its sandy silt to silty fine sands. The heterogeneous silty clay to silt “seal” sediments directly overlying both reservoirs have low S h (0 to 13%) even in thin, coarser beds, suggesting minimal methane transport between the reservoir and seal. S h decreases with depth downward toward the base of both the D1 and B1 sands, corresponding to decreasing grain size. These transitions are underlain by silty clay to clayey silt sediments with low S h (<10%), similar to the seal sediments. Slow depressurization was used to estimate a brackish salinity based on the pressure and temperature of the onset of hydrate dissociation for two core sections within the B1 sand. We show that S h increases with median grain size, sand content, and porosity but exhibits some variation within the sand beds that is not directly explained by lithology.

Alaska↗
USGS2026

Depositional environment and diagenetic history of gas hydrate-bearing sediments of the Alaska North Slope (HYDRATE 02 Geo Data Well)

We characterized the lithological, solid-phase geochemical, and rock magnetic properties of sediment cores from subpermafrost strata on the Alaska North Slope collected as part of the U.S. Department of Energy (DOE), the Japan Organization for Metals and Energy Security (JOGMEC), and the U.S. Geological Survey (USGS) Collaborative Gas Hydrate Research and Development (R&D) Project in Alaska. Pressure cores were recovered from the HYDRATE 02 Geo Data Well (GDW) at the Kuparuk State 7-11-12 site through two hydrate-bearing sand reservoirs, the B1 and D1 sands, and their finer-grained bounding sediments. Both the B1 and D1 sands are quartz-rich, chert-bearing, very fine litharenite sands. These submature to immature sands are poorly to moderately sorted and angular with local fine-scale cross-stratification. The B1 sand has larger grains and a lower clay content as compared to the D1 sand. These sands are the upper portions of upward coarsening progradational sequences. The clay- and silt-rich bounding muds exhibit fine-scale wavy and lenticular laminations, suggesting episodic high energy deposition events. Overall, these sediments were deposited in a shoreface to nearshore marine environment during the Paleogene, modulated by changing depositional energy associated with sea level variation. Organic matter δ 13 C and C/N composition of these sediments indicate a source mixture of land plants and freshwater plankton, with possible minor presence of oil within the B1 sand. These sediments contain high and variable total sulfur (TS) content, suggesting porewater conditions influenced by variable salinity over time. Rock magnetic analyses indicate precipitation of greigite in the mud beneath the D1 sand, in the basal C shale overlying the B1 sand, and the mud beneath the B1 sand, likely due to intervals of sulfate limitation during periods of lower Arctic Ocean salinity. Based on pyrite abundance, TS, and δ 34 S-TS composition, the D1 sand and bounding sediments experienced more substantial sulfide precipitation. The unit E basal shale overlying the D1 sand contains a 0.25 m thick pyrite-dominant sand, indicating local bottom water anoxic conditions. X-ray fluorescence scanning and discrete measurements provide additional supporting interpretation of the depositional and diagenetic processes that have occurred at this site and track the relative amount of drilling fluid contamination with barium abundance in the core samples.

Alaska↗
USGS2026

Production of secondary microbial methane from a gas hydrate-bearing reservoir at the HYDRATE P1 Production Test Well (PTW-1) on the Alaskan North Slope

Gas hydrate in the Alaskan North Slope (ANS) is believed to contain as much methane as the known conventional gas accumulations in the Prudhoe Bay field. The JOGMEC-DOE-USGS Collaborative Gas Hydrate R&D Project conducted an extended-duration production test from the sub-permafrost, gas-hydrate saturated B1 sand reservoir (unit B) at the Kuparuk State 7-11-12 Site in the Prudhoe Bay Unit of the ANS. Using compositional and stable isotopic data measured on gas produced from well cuttings and pressure cores collected from the HYDRATE 02 Geo Data Well (GDW), we differentiate primary microbial, secondary microbial, and trace thermogenic gas sources. The upper part of the well contained predominantly primary microbial methane from near the surface to the SV6 stratigraphic horizon at 1133 ft (345.3 m) measured depth (MD). Below that, the gas composition transitioned to a mixture of mostly primary and secondary microbial methane to near the base of ice-bearing permafrost at 1968 ft (599.8 m) MD. With greater depth to 3558 ft (1084.5 m) MD, which includes the D1 sand (unit D), the B1 sand (unit B), and the base of gas hydrate stability at 3113 ft (948.8 m) MD, the gas composition was greater than 98% secondary microbial methane with the remainder being oil-associated thermogenic gas migrated from the deep Sadlerochit Formation. The unit B vertical gas profile derived from degassed pressure cores demonstrated that gas dissolved in the clay-rich sediment intervals bounding the B1 sand reservoir was distinct from dissolved and hydrate-caged gases in the sand-rich hydrate-bearing reservoir. The HYDRATE P1 Production Test Well (PTW-1) targeted and successfully extracted gas dissociated from hydrate gas in the B1 sand for 151 days when using an electrical submersible pump to depressurize the reservoir with subsequent depressurization achieved through the use of a jet pump. Gas produced from PTW-1 was mostly indistinguishable from the gas compositional profile measured through the B1 sand and generally distinct from dissolved gas in the bounding clay-rich sediments, confirming that the upper and lower bounding units limited infiltration into the reservoir during production. Isolation of the bounding units from the reservoir contributed to the unexpectedly high ratio of production gas to water observed during the extended-duration gas hydrate production test at PTW-1.

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 &deg;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

Real-time specific surface area measurements via laser-induced breakdown spectroscopy

From healthcare to cosmetics to environmental science, the specific surface area (SSA) of micro- and mesoporous materials or products can greatly affect their chemical and physical properties. SSA results are also widely used to examine source rocks in conventional and unconventional petroleum resource plays. Despite its importance, current methods to measure SSA are often cumbersome, time-consuming, or require cryogenic consumables (e.g., liquid nitrogen). These methods are not amenable to high-throughput environments, have stringent sample preparation requirements, and are not practical for use in the field. We present a new application of laser-induced breakdown spectroscopy for rapid measurement of SSA. This study evaluates geological samples, specifically organic-rich oil shales, but the approach is expected to be applicable to many other types of materials. The method uses optical emission spectroscopy to examine laser-generated plasma and quantify the amount of argon adsorbed to a sample during an inert gas purge. The technique can accommodate a wide range of sample sizes and geometries and has the potential for field use. These advantages for SSA measurement combined with the simultaneous acquisition of composition information make this a promising new approach for characterizing geologic samples and other materials.

Energy and 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↗
USGS2019

Nanoscale molecular fractionation of organic matter within unconventional petroleum source beds

Fractionation of petroleum during migration through sedimentary rock matrices has been observed across lengths of meters to kilometers. Selective adsorption of specific chemical moieties at mineral surfaces and/or the phase behavior of petroleum during pressure changes typically are invoked to explain this behavior. Such phenomena are of interest as they impact both the quality and recoverability of petroleum resources. Given the current emphasis on unconventional (continuous) resources, there is a need to understand petroleum fractionation occurring during expulsion and migration at the nanometer to micron scale, due to the fine-grained nature of petroliferous mudrocks. Here, organic matter compositional differences observed within kukersites (petroleum source beds containing acritarch Gloeocapsomorpha prisca) and the overlying carbonate reservoir layer from the Ordovician Stonewall Formation are explored using a suite of spectroscopic methods, primarily through atomic force microscopy based infrared spectroscopy (AFM-IR). AFM-IR is capable of providing spatial resolutions approaching 50 nm and allows for assessment of the molecular fingerprint of kukersite organic matter across transition zones from organic-rich ‘source’ layers into neighboring carbonate ‘reservoir’ layers ~150 μm away. Results indicate that organic matter composition begins to vary immediately following expulsion from source layers, with loss of carbonyl groups and a concomitant decrease in alkyl chain-length, as migration distance increases. These chemical transitions correlate with a decrease in fluorescence intensity, increase in solid bitumen reflectance, and increase in Raman aromaticity proxies (D-G band separation) in the organic matter. Our findings are consistent with the retention of polar compounds onto mineral grains during expulsion and migration, following primary cracking and bituminization of the Gloeocapsomorpha prisca kerogen.

Energy and 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↗
USGS2002

Molecular composition and mobility of torbanite precursors: Implications for the structure of coal

Coorongite, a torbanite precursor found in South Australia, and algal residues derived from Botryococcus braunii and other algae have been examined by solid-state 13C NMR techniques. The majority of carbon in these materials is present as (CH2)n. However, variable-temperature studies show that a considerable proportion of the alkyl chains have unusual dipolar-dephasing behavior and are more mobile than in rigid solids. It is suggested that these mobile structures contribute to the so-called "guest phases" in coal. The data are also consistent with a vascular and algal model of coal. ?? 1988 American Chemical Society.

Energy & Fuels↗
USGS2002

Determination of selected elements in whole coal and in coal ash from the eight argonne premium coal samples by atomic absorption spectrometry, atomic emission spectrometry, and ion-selective electrode

Methods for the determination of 24 elements in whole coal and coal ash by inductively coupled argon plasma-atomic emission spectrometry, flame, graphite furnace, and cold vapor atomic absorption spectrometry, and by ion-selective electrode are described. Coal ashes were analyzed in triplicate to determine the precision of the methods. Results of the analyses of NBS Standard Reference Materials 1633, 1633a, 1632a, and 1635 are reported. Accuracy of the methods is determined by comparison of the analysis of standard reference materials to their certified values as well as other values in the literature.

Energy & Fuels↗