Geology topics

A. Schimmelmann

Publications and source records attributed to A. Schimmelmann.

At least 19 recordsLinked to original sources

USGS2019

Hydrous heating experiments at 130°C yield insights into the occurrence of hydrogen sulfide and light alkanes in natural gas reservoirs

Improved understanding of the origin of produced volatiles from conventional reservoirs and unconventional source rocks is critical for petroleum exploration and production. A series of hydrous heating experiments using two immature Type II siliciclastic source rocks, Pennsylvanian Turner Mine shale (TMS) and Devonian New Albany Shale (NAS), at 130 °C over one to two years were conducted to assess gas generation at low temperature. Elemental sulfur (ES) was added to the NAS samples to evaluate the role of sulfur on thermochemical sulfate reduction (TSR). The produced volatile composition was investigated in situ using Raman spectroscopy at the end of the heating experiments. Results show that the two source rocks yield different types and concentrations of volatiles. Only CH 4 and CO 2 were detected following hydrous heating of the TMS source rock in contrast to CH 4 , C 2 H 6 , C 3 H 8 , and CO 2 which were observed in experiments using NAS. Variations in the produced volatiles are likely the result of compositional differences within the respective source rock organic matter. Experiments involving ES show strong H 2 S signals that are likely due to the formation of H 2 S from the reaction of ES with water at 130 °C. H 2 S signals correlate with a greater relative concentration of CH 4 and CO 2 compared to experiments where ES was not added, on a time-normalized basis. The correlation between the presence of H 2 S and an increase in CH 4 and CO 2 concentration could indicate the occurrence of TSR. Here we propose that H 2 S in siliciclastic shale can be generated in the presence of ES at low temperatures via both disproportionation of ES into H 2 S and SO 4 2– , and TSR. Our findings from this study provide experimental evidence that may aid efforts to interpret the origin of H 2 S in low-temperature sedimentary basins.

Pennsylvania↗

USGS2010

Structural features of a bituminous coal and their changes during low-temperature oxidation and loss of volatiles investigated by advanced solid-state NMR spectroscopy

Quantitative and advanced 13 C solid-state NMR techniques were employed to investigate (i) the chemical structure of a high volatile bituminous coal, as well as (ii) chemical structural changes of this coal after evacuation of adsorbed gases, (iii) during oxidative air exposure at room temperature, and (iv) after oxidative heating in air at 75 ??C. The solid-state NMR techniques employed in this study included quantitative direct polarization/magic angle spinning (DP/MAS) at a high spinning speed of 14 kHz, cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CH, CH 2 , and CH n selection, 13 C chemical shift anisotropy (CSA) filtering, two-dimensional (2D) 1 H- 13 C heteronuclear correlation NMR (HETCOR), and 2D HETCOR with 1 H spin diffusion. With spectral editing techniques, we identified methyl CCH 3 , rigid and mobile methylene CCH 2 C, methine CCH, quaternary C q , aromatic CH, aromatic carbons bonded to alkyls, small-sized condensed aromatic moieties, and aromatic C-O groups. With direct polarization combined with spectral-editing techniques, we quantified 11 different types of functional groups. 1 H- 13 C 2D HETCOR NMR experiments indicated spatial proximity of aromatic and alkyl moieties in cross-linked structures. The proton spin diffusion experiments indicated that the magnetization was not equilibrated at a 1 H spin diffusion time of 5 ms. Therefore, the heterogeneity in spatial distribution of different functional groups should be above 2 nm. Recoupled C-H long-range dipolar dephasing showed that the fraction of large charcoal-like clusters of polycondensed aromatic rings was relatively small. The exposure of this coal to atmospheric oxygen at room temperature for 6 months did not result in obvious chemical structural changes of the coal, whereas heating at 75 ??C in air for 10 days led to oxidation of coal and generated some COO groups. Evacuation removed most volatiles and caused a significant reduction in aliphatic signals in its DP/MAS spectrum. DP/MAS, but not CP/MAS, allowed us to detect the changes during low-temperature oxidation and loss of volatiles. These results demonstrate the applicability of advanced solid-state NMR techniques in chemical characterization of coal. ?? 2010 American Chemical Society.

Conference Paper↗

USGS2010

Chemical and nanometer-scale structure of kerogen and its change during thermal maturation investigated by advanced solid-state 13 C NMR spectroscopy

We have used advanced and quantitative solid-state nuclear magnetic resonance (NMR) techniques to investigate structural changes in a series of type II kerogen samples from the New Albany Shale across a range of maturity (vitrinite reflectance R 0 from 0.29% to 1.27%). Specific functional groups such as CH 3 , CH 2 , alkyl CH, aromatic CH, aromatic C-O, and other nonprotonated aromatics, as well as "oil prone" and "gas prone" carbons, have been quantified by 13 C NMR; atomic H/C and O/C ratios calculated from the NMR data agree with elemental analysis. Relationships between NMR structural parameters and vitrinite reflectance, a proxy for thermal maturity, were evaluated. The aromatic cluster size is probed in terms of the fraction of aromatic carbons that are protonated (???30%) and the average distance of aromatic C from the nearest protons in long-range H-C dephasing, both of which do not increase much with maturation, in spite of a great increase in aromaticity. The aromatic clusters in the most mature sample consist of ???30 carbons, and of ???20 carbons in the least mature samples. Proof of many links between alkyl chains and aromatic rings is provided by short-range and long-range 1 H- 13 C correlation NMR. The alkyl segments provide most H in the samples; even at a carbon aromaticity of 83%, the fraction of aromatic H is only 38%. While aromaticity increases with thermal maturity, most other NMR structural parameters, including the aromatic C-O fractions, decrease. Aromaticity is confirmed as an excellent NMR structural parameter for assessing thermal maturity. In this series of samples, thermal maturation mostly increases aromaticity by reducing the length of the alkyl chains attached to the aromatic cores, not by pronounced growth of the size of the fused aromatic ring clusters. ?? 2010 Elsevier Ltd. All rights reserved.

Geochimica et Cosmochimica Acta↗

USGS2010

Geochemical constraints on the origin and volume of gas in the New Albany Shale (Devonian-Mississippian), eastern Illinois Basin

This study involved analyses of kerogen petrography, gas desorption, geochemistry, microporosity, and mesoporosity of the New Albany Shale (Devonian-Mississippian) in the eastern part of the Illinois Basin. Specifically, detailed core analysis from two locations, one in Owen County, Indiana, and one in Pike County, Indiana, has been conducted. The gas content in the locations studied was primarily dependent on total organic carbon content and the micropore volume of the shales. Gas origin was assessed using stable isotope geochemistry. Measured and modeled vitrinite reflectance values were compared. Depth of burial and formation water salinity dictated different dominant origins of the gas in place in the two locations studied in detail. The shallower Owen County location (415-433 m [1362-1421 ft] deep) contained significant additions of microbial methane, whereas the Pike County location (832-860 m [2730-2822 ft] deep) was characterized exclusively by thermogenic gas. Despite differences in the gas origin, the total gas in both locations was similar, reaching up to 2.1 cm3/g (66 scf/ton). Lower thermogenic gas content in the shallower location (lower maturity and higher loss of gas related to uplift and leakage via relaxed fractures) was compensated for by the additional generation of microbial methane, which was stimulated by an influx of glacial melt water, inducing brine dilution and microbial inoculation. The characteristics of the shale of the Maquoketa Group (Ordovician) in the Pike County location are briefly discussed to provide a comparison to the New Albany Shale. Copyright ??2010. The American Association of Petroleum Geologists. All rights reserved.

American Association of Petroleum Geologists Bulle↗

USGS2009

Nicotine, acetanilide and urea multi-level 2 H-, 13 C- and 15 N-abundance reference materials for continuous-flow isotope ratio mass spectrometry

Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ?? 13 C and ?? 13 N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ?? 2 H nicotine -162 to -45%o, ?? 13 C nicotine -30.05 to +7.72%, ?? 15 N nicotine -6.03 to +33.62%; ?? 15 N acetanilide +1-18 to +40.57%; ?? 13 C urea -34.13 to +11.71%, ?? 15 N urea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ?? 13 N values. Comparative ?? 13 C and ?? 15 N on-line EA-IRMS data from 14 volunteering laboratories document the usefulness and reliability of acetanilides and ureas as EA-IRMS reference materials.

Rapid Communications in Mass Spectrometry↗

USGS2009

Chitin: 'Forgotten' source of nitrogen: From modern chitin to thermally mature kerogen: Lessons from nitrogen isotope ratios

Chitinous biomass represents a major pool of organic nitrogen in living biota and is likely to have contributed some of the fossil organic nitrogen in kerogen. We review the nitrogen isotope biogeochemistry of chitin and present preliminary results suggesting interaction between kerogen and ammonium during thermal maturation. Modern arthropod chitin may shift its nitrogen isotope ratio by a few per mil depending on the chemical method of chitin preparation, mostly because N-containing non-amino-sugar components in chemically complex chitin cannot be removed quantitatively. Acid hydrolysis of chemically complex chitin and subsequent ion-chromatographic purification of the "deacetylated chitin-monomer" D-glucosamine (in hydrochloride form) provides a chemically well-defined, pure amino-sugar substrate for reproducible, high-precision determination of δ 15 N values in chitin. δ 15 N values of chitin exhibited a variability of about one per mil within an individual's exoskeleton. The nitrogen isotope ratio differed between old and new exoskeletons by up to 4 per mil. A strong dietary influence on the δ 15 N value of chitin is indicated by the observation of increasing δ 15 N values of chitin from marine crustaceans with increasing trophic level. Partial biodegradation of exoskeletons does not significantly influence δ 15 N values of remaining, chemically preserved amino sugar in chitin. Diagenesis and increasing thermal maturity of sedimentary organic matter, including chitin-derived nitrogen-rich moieties, result in humic compounds much different from chitin and may significantly change bulk δ 15 N values. Hydrous pyrolysis of immature source rocks at 330°C in contact with 15 N-enriched NH 4 Cl, under conditions of artificial oil generation, demonstrates the abiogenic incorporation of inorganic nitrogen into carbon-bound nitrogen in kerogen. Not all organic nitrogen in natural, thermally mature kerogen is therefore necessarily derived from original organic matter, but may partly result from reaction with ammonium-containing pore waters.

ACS Symposium Series↗

USGS2009

Changes in optical properties, chemistry, and micropore and mesopore characteristics of bituminous coal at the contact with dikes in the Illinois Basin

Changes in high-volatile bituminous coal (Pennsylvanian) near contacts with two volcanic intrusions in Illinois were investigated with respect to optical properties, coal chemistry, and coal pore structure. Vitrinite reflectance (Ro) increases from 0.62% to 5.03% within a distance of 5.5??m from the larger dike, and from 0.63% to 3.71% within 3.3??m from the small dike. Elemental chemistry of the coal shows distinct reductions in hydrogen and nitrogen content close to the intrusions. No trend was observed for total sulfur content, but decreases in sulfate content towards the dikes indicate thermochemical sulfate reduction (TSR). Contact-metamorphism has a dramatic effect on coal porosity, and microporosity in particular. Around the large dike, the micropore volume, after a slight initial increase, progressively decreases from 0.0417??cm3/g in coal situated 4.7??m from the intrusive contact to 0.0126??cm3/g at the contact. Strongly decreasing mesopore and micropore volumes in the altered zone, together with frequent cleat and fracture filling by calcite, indicate deteriorating conditions for both coalbed gas sorption and gas transmissibility. ?? 2008 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2009

Effects of coal storage in air on physical and chemical properties of coal and on gas adsorption

This paper investigates changes in the high-volatile bituminous Lower Block Coal Member from Indiana owing to moisture availability and oxidation in air at ambient pressure and temperature over storage time. Specifically, it investigates changes in chemistry, in surface area, and pore structure, as well as changes in methane and carbon dioxide adsorption capacities. Our results document that the methane adsorption capacity increased by 40%, whereas CO 2 adsorption capacity increased by 18% during a 13-month time period. These changes in adsorption are accompanied by changes in chemistry and surface area of the coal. The observed changes in adsorption capacity indicate that special care must be taken when collecting samples and preserving coals until adsorption characteristics are measured in the laboratory. High-pressure isotherms from partially dried coal samples would likely cause overestimation of gas adsorption capacities, lead to a miscalculation of coal-bed methane prospects, and provide deceptively optimistic prognoses for recovery of coal-bed methane or capture of anthropogenic CO 2 . ?? 2009 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2009

Dike intrusions into bituminous coal, Illinois Basin: H, C, N, O isotopic responses to rapid and brief heating

Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., 2 H/ 1 H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., {single bond}OH, {single bond}COOH, {single bond}NH 2 ). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ???2.5 to ???3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong ?? 13 C kerogen vs. ?? 15 N kerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back-reactions between mobile pyrolysis products from the hot zone as they encounter less hot kerogen. Vein and cell filling carbonate is most abundant in highest rank coals where carbonate ?? 13 C VPDB and ?? 18 O VSMOW values are consistent with thermal generation of 13 C-depleted and 18 O-enriched CO 2 from decarboxylation and pyrolysis of organic matter. Lower background concentrations of 13 C-enriched carbonate in thermally unaffected coal may be linked to 13 C-enrichment in residual CO 2 in the process of CO 2 reduction via microbial methanogenesis. Our compilation and comparison of available organic H, C, N isotopic findings on magmatic intrusions result in re-assessments of majors factors influencing isotopic shifts in kerogen during magmatic heating. (i) Thermally induced shifts in organic ??D values of kerogen are primarily driven by the availability of water or steam. Hydrologic isolation (e.g., near Illinois dikes) results in organic D-depletion in kerogen, whereas more common hydrologic connectivity results in organic D-enrichment. (ii) Shifts in kerogen (or coal) ?? 13 C and ?? 15 N values are typically small and may follow sinusoidal patterns over short distances from magmatic contacts. Laterally limited sampling strategies may thus result in misleading and non-representative data. (iii) Fluid transport of chemically active, mobile carbon and nitrogen species and recombination reactions with kerogen result in isotopic changes in kerogen that are unrelated to the original, autochthonous part of kerogen. ?? 2009 Elsevier Ltd. All rights reserved.

Geochimica et Cosmochimica Acta↗

USGS2008

Diagenetic mineralization in Pennsylvanian coals from Indiana, USA: 13C/12C and 18O/16O implications for cleat origin and coalbed methane generation

Cleats and fractures in southwestern Indiana coal seams are often filled with authigenic kaolinite and/or calcite. Carbon- and oxygen-stable isotope ratios of kaolinite, calcite, and coalbed CO2 were evaluated in combination with measured values and published estimates of ??18O of coalbed paleowaters that had been present at the time of mineralization. ??18Omineral and ??18Owater values jointly constrain the paleotemperature of mineralization. The isotopic evidence and the thermal and tectonic history of this part of the Illinois Basin led to the conclusion that maximum burial and heat-sterilization of coal seams approximately 272??Ma ago was followed by advective heat redistribution and concurrent precipitation of kaolinite in cleats at a burial depth of < 1600??m at ??? 78 ?? 5????C. Post-Paleozoic uplift, the development of a second generation of cleats, and subsequent precipitation of calcite occurred at shallower burial depth between ??? 500 to ??? 1300??m at a lower temperature of 43 ?? 6????C. The available paleowater in coalbeds was likely ocean water and/or tropical meteoric water with a ??18Owater ??? - 1.25??? versus VSMOW. Inoculation of coalbeds with methanogenic CO2-reducing microbes occurred at an even later time, because modern microbially influenced 13C-enriched coalbed CO2 (i.e., the isotopically fractionated residue of microbial CO2 reduction) is out of isotopic equilibrium with 13C-depleted calcite in cleats. ?? 2007 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2008

Variability of geochemical properties in a microbially dominated coalbed gas system from the eastern margin of the Illinois Basin, USA

This study outlines gas characteristics along the southeastern margins of the Illinois Basin and evaluates regional versus local gas variations in Seelyville and Springfield coal beds. Our findings suggest that high permeability and shallow (100-250??m) depths of these Indiana coals allowed inoculation with methanogenic microbial consortia, thus leading to widespread microbial methane generation along the eastern marginal part of the Illinois Basin. Low maturity coals in the Illinois Basin with a vitrinite reflectance Ro ~ 0.6% contain significant amounts of coal gas (~ 3??m3/t, 96??scf/t) with ??? 97??vol.% microbial methane. The amount of coal gas can vary significantly within a coal seam both in a vertical seam section as well as laterally from location to location. Therefore sampling of an entire core section is required for accurate estimates of coal gas reserves. ?? 2008 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2008

Organic nitrogen chemistry during low-grade metamorphism

Most of the organic nitrogen (Norg) on Earth is disseminated in crustal sediments and rocks in the form of fossil nitrogen-containing organic matter. The chemical speciation of fossil Norg within the overall molecular structure of organic matter changes with time and heating during burial. Progressive thermal evolution of organic matter involves phases of enhanced elimination of Norg and ultimately produces graphite containing only traces of nitrogen. Long-term chemical and thermal instability makes the chemical speciation of Norg a valuable tracer to constrain the history of sub-surface metamorphism and to shed light on the subsurface biogeochemical nitrogen cycle and its participating organic and inorganic nitrogen pools. This study documents the evolutionary path of Norg speciation, transformation and elimination before and during metamorphism and advocates the use of X-ray photoelectron spectroscopy (XPS) to monitor changes in Norg speciation as a diagnostic tool for organic metamorphism. Our multidisciplinary evidence from XPS, stable isotopes, traditional quantitative coal analyses, and other analytical approaches shows that at the metamorphic onset Norg is dominantly present as pyrrolic and pyridinic nitrogen. The relative abundance of nitrogen substituting for carbon in condensed, partially aromatic systems (where N is covalently bonded to three C atoms) increases exponentially with increasing metamorphic grade, at the expense of pyridinic and pyrrolic nitrogen. At the same time, much Norg is eliminated without significant nitrogen isotope fractionation. The apparent absence of Rayleigh-type nitrogen isotopic fractionation suggests that direct thermal loss of nitrogen from an organic matrix does not serve as a major pathway for Norg elimination. Instead, we propose that hot H, O-containing fluids or some of their components gradually penetrate into the carbonaceous matrix and eliminate Norg along a progressing reaction front, without causing nitrogen isotope fractionation in the residual Norg in the unreacted core of the carbonaceous matrix. Before the reaction front can reach the core, an increasing part of core Norg chemically stabilizes in the form of nitrogen atoms substituting for carbon in condensed, partially aromatic systems forming graphite-like structural domains with delocalized ??-electron systems (nitrogen atoms substituting for "graphitic" carbon in natural metamorphic organic matter). Thus, this nitrogen species with a conservative isotopic composition is the dominant form of residual nitrogen at higher metamorphic grade. ?? 2007 Elsevier Ltd. All rights reserved.

Geochimica et Cosmochimica Acta↗

USGS2008

Increasing maturity of kerogen type II reflected by alkylbenzene distribution from pyrolysis-gas chromatography-mass spectrometry

A series of Late Devonian to Early Mississippian type II kerogens with vitrinite reflectance values Ro 0.29-2.41% were analyzed using py-GC-MS. In addition, a low maturity kerogen with Ro 0.44% was separated into fractions via density gradient centrifugation, followed by py-GC-MS of the alginite and amorphinite maceral concentrates. Alkylbenzenes and n-alk-1-ene/n-alkane doublets represented the main compound classes identified in all pyrolysates. The pyrolysate from alginite featured 1,2,4-trimethylbenzene and toluene as the two most prominent alkylbenzenes. In contrast, alkylbenzenes in pyrolysates from amorphinite and low maturity bulk kerogens with Ro 0.29-0.63% were dominated by 1,2,3,4-tetramethylbenzene. With increasing thermal maturity, pyrolysates were increasingly dominated by (i) alkylbenzenes with fewer methyl groups, namely by tri- and dimethylbenzenes at medium maturity (Ro 0.69-1.19%), and (ii) by toluene at higher maturity (Ro 1.30-2.41%). With increasing maturity of kerogen type II, the decreasing abundance of highly methyl-substituted alkylbenzenes and the parallel increase in less methyl-substituted alkylbenzenes in flash pyrolysates suggest that demethylation is an important chemical process in the thermal maturation of kerogen type II. ?? 2008 Elsevier Ltd. All rights reserved.

Organic Geochemistry↗

USGS2008

Methane-producing microbial community in a coal bed of the Illinois Basin

A series of molecular and geochemical studies were performed to study microbial, coal bed methane formation in the eastern Illinois Basin. Results suggest that organic matter is biodegraded to simple molecules, such as H 2 and CO2, which fuel methanogenesis and the generation of large coal bed methane reserves. Small-subunit rRNA analysis of both the in situ microbial community and highly purified, methanogenic enrichments indicated that Methanocorpusculum is the dominant genus. Additionally, we characterized this methanogenic microorganism using scanning electron microscopy and distribution of intact polar cell membrane lipids. Phylogenetic studies of coal water samples helped us develop a model of methanogenic biodegradation of macromolecular coal and coal-derived oil by a complex microbial community. Based on enrichments, phylogenetic analyses, and calculated free energies at in situ subsurface conditions for relevant metabolisms (H2-utilizing methanogenesis, acetoclastic methanogenesis, and homoacetogenesis), H 2-utilizing methanogenesis appears to be the dominant terminal process of biodegradation of coal organic matter at this location. Copyright ?? 2008, American Society for Microbiology. All Rights Reserved.

Applied and Environmental Microbiology↗

USGS2007

Chemistry of thermally altered high volatile bituminous coals from southern Indiana

The optical properties and chemical characteristics of two thermally altered Pennsylvanian high volatile bituminous coals, the non-coking Danville Coal Member (Ro = 0.55%) and the coking Lower Block Coal Member (Ro = 0.56%) were investigated with the purpose of understanding differences in their coking behavior. Samples of the coals were heated to temperatures of 275????C, 325????C, 375????C and 425????C, with heating times of up to one hour. Vitrinite reflectance (Ro%) rises with temperature in both coals, with the Lower Block coal exhibiting higher reflectance at 375????C and 425????C compared to the Danville coal. Petrographic changes include the concomitant disappearance of liptinites and development of vesicles in vitrinites in both coals, although neither coal developed anisotropic coke texture. At 375????C, the Lower Block coal exhibits a higher aromatic ratio, higher reflectance, higher carbon content, and lower oxygen content, all of which indicate a greater degree of aromatization at this temperature. The Lower Block coal maintains a higher CH2/CH3 ratio than the Danville coal throughout the heating experiment, indicating that the long-chain unbranched aliphatics contained in Lower Block coal liptinites are more resistant to decomposition. As the Lower Block coal contains significant amounts of liptinite (23.6%), the contribution of aliphatics from these liptinites appears to be the primary cause of its large plastic range and high fluidity. ?? 2006 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2007

Cleats and their relation to geologic lineaments and coalbed methane potential in Pennsylvanian coals in Indiana

Cleats and fractures in Pennsylvanian coals in southwestern Indiana were described, statistically analyzed, and subsequently interpreted in terms of their origin, relation to geologic lineaments, and significance for coal permeability and coalbed gas generation and storage. These cleats can be interpreted as the result of superimposed endogenic and exogenic processes. Endogenic processes are associated with coalification (i.e., matrix dehydration and shrinkage), while exogenic processes are mainly associated with larger-scale phenomena, such as tectonic stress. At least two distinct generations of cleats were identified on the basis of field reconnaissance and microscopic study: a first generation of cleats that developed early on during coalification and a second generation that cuts through the previous one at an angle that mimics the orientation of the present-day stress field. The observed parallelism between early-formed cleats and mapped lineaments suggests a well-established tectonic control during early cleat formation. Authigenic minerals filling early cleats represent the vestiges of once open hydrologic regimes. The second generation of cleats is characterized by less prominent features (i.e., smaller apertures) with a much less pronounced occurrence of authigenic mineralization. Our findings suggest a multistage development of cleats that resulted from tectonic stress regimes that changed orientation during coalification and basin evolution. The coals studied are characterized by a macrocleat distribution similar to that of well-developed coalbed methane basins (e.g., Black Warrior Basin, Alabama). Scatter plots and regression analyses of meso- and microcleats reveal a power-law distribution between spacing and cleat aperture. The same distribution was observed for fractures at microscopic scale. Our observations suggest that microcleats enhance permeability by providing additional paths for migration of gas out of the coal matrix, in addition to providing access for methanogenic bacteria. The abundance, distribution, and orientation of cleats control coal fabric and are crucial features in all stages of coalbed gas operations (i.e., exploration and production). Understanding coal fabric is important for coal gas exploration as it may be related to groundwater migration and the occurrence of methanogenic bacteria, prerequisite to biogenic gas accumulations. Likewise, the distribution of cleats in coal also determines pathways for migration and accumulation of thermogenic gas generated during coalification. ?? 2007 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2007

Characterization of the origin of coalbed gases in southeastern Illinois Basin by compound-specific carbon and hydrogen stable isotope ratios

Coalbed gases and waters from exploratory and production gas wells in the southeastern Illinois Basin were sampled to assess geochemically the origin of coalbed gases, with an emphasis on the Springfield and Seelyville Coal Members that are commercially targeted for coalbed methane production in Indiana. On-line analyses of hydrocarbon gases methane to butanes (C1, C2, C3, n-C4, i-C4) and CO2 yielded gas concentrations, plus ??D and ??13C values. The low thermal maturity of Indiana coals with vitrinite reflectance R0 ??? 0.6% is in agreement with an overwhelmingly biogenic isotopic signature of coalbed gases containing ???96% methane generated via bacterial CO2-reduction. In contrast, thermogenic gas was generated in the stratigraphically equivalent coal beds in western Kentucky's Rough Creek Graben zone where higher maturities of up to R0 ??? 0.8% were reached owing to tectonic and hydrothermal activity. No secondary biogenic methane was observed in more mature western Kentucky coal beds where greater burial depth limits the recharge of meteoric water. Biogenic and thermogenic coalbed gases represent two end-members that are compositionally and isotopically distinct. Microbial biodegradation of thermogenic C2+ hydrocarbon gases in Indiana coal beds preferentially targets C3 and introduces isotope fractionation whereby remaining C3 is enriched in deuterium and 13C.

Organic Geochemistry↗

USGS2006

Carbon isotopic fractionation of CH4 and CO2 during canister desorption of coal

Canister desorption of coal gas from freshly sampled coal is commonly used for exploratory assessment of the coalbed methane (CBM) potential of a basin or prospect, as well as for the sampling of gas for isotopic determination of the gas origin. Compositional and ??13C isotopic time-series of desorbing CBM and carbon dioxide (CO2) over 3-4 months demonstrate considerable compositional and isotopic shifts over time. Non-stationary chemical and isotopic characteristics are due to differences in diffusivity and adsorbance behavior of gas molecules and must be taken into account when attempting to reproducibly sample coal gases. Off-line gas processing on a vacuum line and on-line GC/MS analyses were performed on coal gas samples from the Springfield and Seelyville Coal Members of the Pennsylvanian age that were cored in the SE Illinois Basin in SW Indiana, USA. The coals cover a narrow range of maturity from 0.54% to 0.64% vitrinite reflectance. Methane initially desorbed faster than CO2, resulting in a 50% increase of the CO 2 content in bulk desorbing gas on the 50th day relative to the first day of desorption. After 50 days of desorption, about 90% of all coal gas was desorbed. Over the same time period, ??13C values of incrementally sampled coal gas increased by 2??? and 9???, for CH 4 and CO2, respectively, testifying to the greater retention of 13CH4 and 13CO2 relative to 12CH4 and 12CO2. An isotopic mass balance of the individual, sequentially desorbed and sampled gas amounts yielded weighted mean ??13CCH4 and ??13CCO2 values for characterizing the cumulatively desorbed gas. The overall mean ??13C values were equivalent to ??13C values of gases that desorbed at a time when half of the potentially available gas had been desorbed from coal, corresponding in this study to a time between day 5 and day 12 of canister desorption at 15-18??C. The total expected gas volume and the ???50% midpoint can thus be approximated for a desorbing coal gas sample, based on a dynamic prediction after the first five days of canister desorption. ?? 2005 Elsevier Ltd. All rights reserved.

Organic Geochemistry↗