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At least 379 records · Page 21Linked to original sources
USGS2020

Examination of inertinite within immature Eagle Ford Shale at the nanometer-scale using atomic force microscopy-based infrared spectroscopy

The nanoscale molecular composition of sedimentary organic matter is challenging to characterize in situ given the limited tools available that can adequately interrogate its complex chemical structure. This is a particularly relevant issue in source rocks, as kerogen composition will strongly impact its reactivity and so is critical to understanding petroleum generation processes during catagenesis. The recent advent of tip-enhanced analytical methods, such as atomic force microscopy-based infrared spectroscopy (AFM-IR), has allowed for the major compositional features of kerogen and other types of in situ organic matter to be elucidated at spatial resolutions at or below 50 nm. Here AFM-IR was applied to examine inertinite, an important organic matter type, present in a thermally immature Eagle Ford calcareous mudstone. The data show that the nanoscale molecular composition of the examined inertinite is (i) less heterogeneous than solid bitumen in more thermally mature Eagle Ford samples and (ii) more hydrogen- and oxygen-rich than inertinite examined in the New Albany Shale.

Texas↗
USGS2021

A review of spatially resolved techniques and applications of organic petrography in shale petroleum systems

This review examines new techniques and applications of organic petrography in source-rock reservoir petroleum systems that have occurred along with development of the global ‘shale revolution’ in energy resources. The review is limited to techniques and instrumentation that provide spatially resolved information, typically at or below microscales, for dispersed organic matter occurring in situ in samples of shale and mudrock. A brief summary of ion beam sample preparation is followed by discussion of the most common analytical techniques and applications. Advantages and limitations of each technique, including requisite sample preparation, types of information generated [e.g., molecular or elemental (isotopic) abundance], sensitivity, and resolution are discussed. In a few cases, techniques not yet applied to organic petrology of shale or mudrock are described (e.g., X-ray photoelectron spectroscopy imaging), in anticipation of near-term future application. The most common in situ techniques applied for characterization of organic matter in shale and mudrock include optical (including fluorescence) and electron microscopies, Raman, fluorescence, and infrared spectroscopies, and surficial measurements via force microscopy. Techniques that show growing application to organic petrography of shale include tip-enhanced photothermal infrared spectroscopy, mass spectrometry imaging, and synchrotron-based spectroscopies, among others. It is anticipated that the future of dispersed organic matter petrography will hold continued development of integrated instrument techniques (e.g., simultaneous or sequential correlative microscopies and/or spectroscopies of the same location), increased instrumental resolution, increased use of multiscale and multimodal organic petrography investigations, and three-dimensional imaging and chemical speciation mapping applications via multiple analytical approaches.

International Journal of Coal Geology↗
USGS2021

Single-well production history matching and geostatistical modeling as proxy to multi-well reservoir simulation for evaluating dynamic reservoir properties of coal seams

Reservoir properties of coal seams such as gas and water effective permeabilities and gas content, as well as spatial distributions thereof, affect the success of gas production and CO 2 -enhanced gas recovery (EGR) with simultaneous CO 2 sequestration. These properties change during production and injection operations due to variations in reservoir pressure, matrix shrinkage/swelling, and water saturation and are therefore referred to as dynamic properties. Predicting distribution of such important reservoir properties and how they evolve during production, or injection, at unsampled locations can be particularly important for field development and project economics. In this work, dynamic properties of Black Creek coal seam of Black Warrior Basin, Alabama were mapped using pointwise results from single-well production history matching of 45 wells and classical geostatistics . It is explored if this approach can be a proxy, with its limitations, to multi-well reservoir simulation. For this purpose, a reservoir model was built using available reservoir, well and production data to compare its results with those of the geostatistical maps for the same properties. Despite the expected local discrepancies due to differences between the two approaches, the results showed similar patterns and global distributions. Specific results showed that despite long-time operation of the wells in this area, there were still areas with high gas content and low gas effective permeability within the modeled time interval that might have benefited from further development using additional wells.

Alabama↗
USGS2021

Insights on the characteristics and sources of gas from an underground coal mine using compositional data analysis

Coal mine gas originates from the gas emission zone (GEZ) of the mine, as well as the longwall face and pillars. Gas emissions are controlled directly at the sources using horizontal or vertical boreholes drilled from surface or from the entries in advance of mining, or it is captured from the fractured and caved zones (gob) using ventholes during mining. The rest of the gas, especially that gas that originates from the longwall face and caved zone, mixes with the ventilation air and travels through bleeder and return entries before being exhausted to atmosphere from air shafts. Although the gas associated with mining mostly focuses on methane, the gas is not pure methane but is a mixture (where both the components and their quantities vary depending on the sampling location). Understanding the evolution of the composition of the gas from source to different sampling and evaluation points in mines using proper statistical analysis and interpretation methods can lead to better designed degasification and ventilation systems and the selection of the most adequate utilization method for generating energy from the gas. In this work, we present the results of compositional data analysis (CoDa) of gases sampled at different locations in a longwall mine operating in Pennsylvanian coal-bearing strata in the Northern Appalachian coal basin. Sampling locations were from accessible parts of the bleeder entries, returns, bleeder evaluation points and shafts within the mine, and also from gob gas ventholes (GGV) and coal degasification boreholes drilled in the panel areas. In addition, desorbed gas samples from seams that are important for the mine were included in the analyses for comparison. The compositional data analysis showed that the gas composition shifts based on the sampling location, putting in-mine and pure coalbed gases on the opposite ends. Removal of air from the samples did not change this observation suggesting that oxygen is depleted especially for in-mine samples, which is due to oxidation. Results also suggested that desorbed gas samples may not represent the composition of the coal seam gas.

International Journal of Coal Geology↗
USGS2021

Relating Tmax and hydrogen index to vitrinite and solid bitumen reflectance in hydrous pyrolysis residues: Comparisons to natural thermal indices

Vitrinite reflectance (VR o ; %) generally is considered the most reliable technique to determine the thermal maturity of sedimentary rocks. However, it is a time-consuming process to collect reflectance (R o ; %) measurements and is subjective to the interpretation of each trained technician, who must be able to discern between vitrinite and solid bitumen and other organic matter types. Inadvertent misidentification of solid bitumen for vitrinite can lead to reports of ‘suppressed’ VR o , especially at lower thermal maturities (< 1.0% R o ). Programmed pyrolysis data, such as T max and hydrogen index (HI), are comparatively inexpensive and more time-efficient to obtain than R o data and are determined by instrument settings, rather than by operator decision, and are therefore independent of operator-based training or experience bias. This study uses hydrous pyrolysis (HP) residues from various coals and shales to relate measured VR o and solid bitumen reflectance (BR o ; %) values to their respective T max and HI values and determines whether these relationships can be used as a proxy to calculate R o in naturally matured samples. Although the estimation of R o is not always accurate, the results demonstrate that relational equations for shales and coals derived from the T max and HI data of HP residues can effectively calculate R o in natural series. Approximately 60% of calculated R o from T max and 83% of calculated R o from HI relational equations are within interlaboratory reproducibility limits (± 0.2% shale BR o ; ± 0.06% coal VR o ) when compared to their respective measured R o values from natural series. Variables that may affect accuracy of the applied relational equations include variable sedimentary organic matter composition of samples, differences of maturation reaction kinetics of the sedimentary organic matter in experimental versus natural settings, and decreasing reliability of all thermal proxy measurements at higher maturities.

International Journal of Coal Geology↗
USGS2021

Compositional evolution of organic matter in Boquillas Shale across a thermal gradient at the single particle level

The molecular composition of petroliferous organic matter and its compositional evolution throughout thermal maturation provides insight for understanding petroleum generation. This information is critical for understanding hydrocarbon resources in unconventional reservoirs, as source rock organic matter is highly dispersed, in contact with the surrounding mineral matrix, and may occur as multiple organic matter maceral types. Here, Raman spectroscopy and optical microscopy approaches were applied to a marginally mature (vitrinite reflectance ~0.5%) sample of the Late Cretaceous Boquillas Shale before and after hydrous pyrolysis (HP) at 300 °C and 330 °C for 72 h. This analytical approach allowed for correlative examination of micro-scale changes in organic matter compositional properties (e.g., aromaticity) for a variety of organic matter macerals across a thermal gradient (from marginally mature into the late oil/wet gas window) at the single particle level. Results indicate that while the examined amorphous organic matter, solid bitumen, and vitrinite particles exhibit different aromatic signatures in the unheated shale, they effectively progress along a similar trend through composition space with thermal maturation. Examined inertinite fragments were generally insensitive to the applied thermal stress, reinforcing the idea that reservoir temperature may be secondary for dictating the molecular composition of inertinite. Additional analysis of Raman spectra for individual organic matter macerals was performed using multivariate curve resolution (MCR) and correlation of standard Raman and reflectance-derived thermal maturity proxies against MCR parameters shows consistent trends. This trend suggests that MCR may be a fast and statistically robust method for extracting compositional information from Raman spectra of sedimentary organic matter, and can be used to construct thermal maturity relationships. These findings inform our understanding of how different petroliferous organic matter maceral types evolve throughout thermal reactions and further demonstrate that Raman spectroscopy combined with petrographic analysis can provide complementary estimates of organic matter composition and thermal maturity.

International Journal of Coal Geology↗
USGS2022

Characterization of bituminite in Kimmeridge Clay by confocal laser scanning and atomic force microscopy

This work investigates bituminite (amorphous sedimentary organic matter) in Upper Jurassic Kimmeridge Clay source rock via confocal laser scanning microscopy (CLSM) and atomic force microscopy (AFM). These petrographic tools were used to provide better understanding of the nature of bituminite, which has been historically difficult to identify and differentiate from similar organic matter types in source rocks. As part of an International Committee for Coal and Organic Petrology (ICCP) working group, an immature (0.42% vitrinite reflectance), organic-rich (44.1 wt% total organic carbon content) sample of Kimmeridge Clay was distributed to multiple laboratories for CLSM characterization. The primary observations from CLSM imaging and spectroscopy include: 1) the interpreted presence of Botryococcus algae as a contributor to bituminite precursors; 2) color red-shift of sulfide reflectance and bituminite auto-fluorescence from below the sample surface; 3) positive alteration of bituminite from laser-induced photo-oxidation of the sample surface, including fluorescence blue-shift; 4) fluorescence blue-shift associated to higher fluorescence intensity regions in bituminite indicative of compositional (fluorophore) differences; 5) the need for fluorescence spectroscopy standardization as applied via CLSM; and 6) the suitability of CLSM fluorescence spectroscopy to predict solid bitumen reflectance from bituminite spectral emission via calibration to an extant dataset. Secondary CLSM observations include detection of reflected laser light from highly reflective inclusions in bituminite, including sulfides and fusinite, and radiolytic alteration of bituminite caused by substitution of U for Fe in sulfides. Findings from AFM include the observation that surface roughening or surface flattening of bituminite are induced by differential broad ion beam (BIB) milling and are dependent on the location and scale of AFM topology measurement. This result highlights our still limited understanding of the effects of BIB milling on sedimentary organic matter and indicates the need for further research before this technique can be advanced as a standard practice in petrographic sample preparation. Collectively, the results of this study illustrate the general applicability and versatility of AFM and CLSM as tools for organic petrology research, specifically for better understanding of the nature and properties of the bituminite maceral.

Kimmeridge↗
USGS2022

Maturation study of vitrinite in carbonaceous shales and coals: Insights from hydrous pyrolysis

The presence of vitrinite in sedimentary rocks of post-Silurian age allows its reflectance to be used to estimate the thermal maturation of organic matter in petroleum systems. Increasing reflectance of vitrinite, which is primarily driven by aromaticity, depends primarily on the time and temperature attributes of its evolutionary pathway. This study evaluated carbonaceous shales proximal to coal measures and coal samples via isothermal hydrous pyrolysis (HP) to compare differences in the maturation pathways of vitrinite. Sample residues were analysed via vitrinite reflectance (VRo), geochemical screening tests (organic carbon and programmed temperature pyrolysis), and infrared spectroscopy. The study included samples from Indian and North American basins, to observe differences in vitrinite evolution with respect to enclosing mineral matrix, starting degree of aromaticity, organic matter types, stratigraphic age, and depositional environment. The organic content of HP residues shows an intuitive response to the thermal stress of HP, e.g., a general depletion of total organic carbon (TOC) content, pyrolyzate (S2), and hydrogen index with increasing HP temperature. Infrared proxies including C-factor and CH2/CH3 generally decrease with increasing thermal maturity indicating loss of O via CO2 generation and the thermal cracking of aliphatic organic matter. Tmax, production index (PI), and VRo show intuitive increasing values with respect to HP temperature. The least mature sample (0.48 ± 0.05% VRo) generally experienced the maximum change in these parameters during maturation, whereas the most mature sample (0.99 ± 0.06% VRo) generally showed the least change. This observation is consistent with higher kinetic barriers to reaction in more aromatic vitrinite which contains higher bond dissociation energies. Devolatilization of vitrinite during HP causes formation of gas evacuation vacuoles and contraction cracks in the vitrinite grains of both coal and carbonaceous shale. Similarities in vitrinite response to HP between coal and carbonaceous shale suggest that thermal evolution of the vitrinite maceral is principally controlled by inherent rate-limiting kinetic parameters related to its molecular structure. Whereas, the stratigraphic age, sedimentary environment, surrounding organic matter, lithology, and catalysis by mineral composition have less effect. To further improve our understanding of vitrinite aromatization and kinetic parameters, future studies of vitrinite reflectance thermal evolution with temperature should include coal and carbonaceous shale from the same stratigraphic section and extant woody tissue from modern vascular plants.

International Journal of Coal Geology↗
USGS2022

Machine learning and data augmentation approach for identification of rare earth element potential in Indiana Coals, USA

Rare earth elements and yttrium (REYs) are critical elements and valuable commodities due to their limited availability and high demand in a wide range of applications and especially in high-technology products. The increased demand and geopolitical pressures motivate the search for alternative sources of REYs, and coal, coal waste, and coal ash are considered as new sources for these critical elements. This research evaluates the REY potential of coals from Indiana (USA). However, although coal data revealed REY potential, it suffered from sparse samples with complete REY measurements. Therefore, we explore the applicability of machine learning (ML) models and data augmentation techniques to demonstrate their applicability to evaluate REY potential in Indiana, and other areas in coal basins, using selected coal parameters (Al2O3, Fe2O3, C, Ash, S, P, Mo, Zn, and As contents) as covariates (indicators). Due to the relatively small sample size with complete REY data in the Indiana Coal Database, two data augmentation techniques (Random Over-Sampling Examples and Synthetic Minority Over-Sampling Technique) were used. Four machine learning algorithms (linear discriminate analysis, support vector machine, random forest, and artificial neural networks) were applied for modeling REY potential as a classification problem. The results show that application of Synthetic Minority Over-Sampling Technique prior to development of the support vector machine (SVM) models generated the best REY classification with an accuracy of 95%. The encouraging results based on Indiana coal data may suggest that a similar approach can be used for other coal basins for screening the locations with REY potential. Those locations then can be targeted for more detailed geochemical surveys to identify most promising areas and evaluate overall REY resources.

Indiana↗
USGS2022

Relating systematic compositional variability to the textural occurrence of solid bitumen in shales

This study presents Raman spectroscopic data paired with scanning electron microscopy (SEM) images to assess solid bitumen composition as a function of solid bitumen texture and association with minerals. A series of hydrous pyrolysis experiments (1–103 days, 300–370 °C) using a low maturity (0.25% solid bitumen reflectance, BR o ), high total organic carbon [(TOC), 14.0 wt%] New Albany Shale sample as the starting material yielded pyrolysis residues designed to evaluate the evolution of solid bitumen aromaticity with increasing temperature and heating duration. Solid bitumen was analyzed by Raman spectroscopy wherein point data were collected from accumulations that ranged in size and degree of association with the mineral matrix. Raman spectroscopy results show that with increasing temperature and experimental duration, solid bitumen aromaticity increases and compositional variability decreases. With regards to texture and composition, coarser-grained solid bitumen (>1.3 μm from nearest mineral grain) has consistently higher, but less variable aromaticity than thinner, wispy solid bitumen which is more intimately associated with the mineral matrix. Collocated scanning electron microscope images were used to provide qualitative assessments of porosity hosted by the organic matter. These paired data sets suggest that solid bitumen porosity development and molecular composition are linked, and these parameters are related to the textural relationships of the organic matter within the whole rock. These results are discussed with perspective towards understanding how rock fabric and texture can influence organic matter evolution during thermal maturation of organic-rich marine shales and inform our broader understanding of these important energy resources.

International Journal of Coal Geology↗
USGS2022

Pore systems and organic petrology of cretaceous Mowry and Niobrara source-rock reservoirs, Powder River Basin, Wyoming, USA

The Powder River Basin (PRB) is a world-class oil province, in large part thanks to contributions from premier source rocks, Cretaceous Mowry and Niobrara shales. Both formations are also unconventional reservoirs. A critical aspect of evaluating production potential and finding sweet spots is the nature of the pore systems in these fine-grained source-rock reservoirs. Variation by stratigraphic interval is important for selecting optimum target zones for horizontal wells. Understanding variation in pore type, size, and connectivity and relationships with mineralogy and fabric help in determining prospectivity in different parts of the basin. Deciphering controls on pore-system development helps predict intervals and locations of optimum reservoir quality. Imaging of Niobrara and Mowry samples from a range of thermal maturities provided observations and data on pore systems, organic matter (OM) types and associations with mineralogy and fabric, wettability, and microporosity associated with both diagenetic and detrital clays. Imaging techniques included scanning electron microscopy, organic petrography and correlative scanning electron microscopy, and mapping of mineralogy through energy dispersive spectroscopy. Mean solid bitumen (BR o ) and vitrinite reflectance (VR o ) values indicate all samples are in the oil window with values ranging from 0.52 to 1.15%. Organic fluorescence is prominent in amorphous OM, solid bitumen and some vitrinite in the early oil window. The fluorescence is extinguished at higher thermal maturity. Carbonate pellets (in Niobrara) mainly contain migrated solid bitumen and residual live oil and little or no terrigenous OM (vitrinite and inertinite). However, terrigenous OM is common in siliceous/argillaceous laminae in both formations, where it occurs with amorphous OM, some of which has converted in situ to a solid bitumen petroleum residue. One key finding is the widespread presence of migrated OM at very early oil window maturity. Distribution of such OM and associated wettability alteration is fabric-controlled, at all levels of thermal maturity studied. Clay morphology and abundance and supporting rigid mineral grain framework strongly influence pore development, preservation, and connectivity in both formations. Carbonate content is a good proxy for reservoir quality in Niobrara intervals due to association of porous solid bitumen with calcareous fecal pellets. High recrystallized microquartz content is associated with the best reservoir intervals in the Mowry.

Wyoming↗
USGS2022

Bulk and intramolecular carbon isotopic compositions of hydrocarbon gases from laboratory pyrolysis of oil shale of the Green River Formation: Implications for isotope structures of kerogens

Evaluation of intramolecular isotope distributions within organic compounds can provide important insights into gas formation processes and structural properties of gas-generating precursors, such as kerogen, bitumen, and oil, in natural reservoirs. Until recently, little has been known about the intramolecular isotope distributions within kerogens. In this study, we conducted systematic pyrolysis experiments of gas generation from a lacustrine oil shale of the Eocene Green River Formation under hydrous and anhydrous conditions (equivalent maturity or Easy %R o : 0.76 to 3.27 at 310 to 480 °C for 3 to 50 days), measuring gas yields and compositions, as well as bulk and position-specific (PS) carbon isotope compositions. Gas generation processes were investigated in combination with kinetic Monte Carlo (kMC) simulations on a model Type I kerogen based on the chemical structures of oil shale of the Green River Formation. The comparison of our experimental results with kMC modelling indicates a series of β-scission, radical isomerization, and recombination reactions better represent the bulk isotope compositions of propane in the pyrolysis of the oil shale of the Green River Formation, but the ΔC c-t (= δ 13 C cen – δ 13 C ter ) values of propane at Easy %R o > 1.5 can be better simulated by a simple combination of propyl groups with H radicals. Combining our previous works on marine shale of the Woodford Formation and Springfield Coal Member of the Carbondale Formation, PS carbon isotopes of propane indicate that in the lacustrine shales of the Green River Formation and the marine Woodford Shale, propane is sourced from C C bond cleavage, while C O bond cracking generates propane from coal at the initial kerogen cracking stage. At high maturity, the differences of late-stage propane production among the source rocks lead to the different bulk and PS C kinetic isotope effects of propane. Our findings suggest that the δ 13 C at the terminal position of propane precursors is likely up to 3.6‰ higher than at the central position in the Green River kerogen, while they are similar in the marine shale of Woodford Formation. In addition, the δ 13 C at the central position of propyl groups attached to heteroatom compounds is relatively more positive in the Springfield Coal Member of the Carbondale Formation than in Green River kerogen. A comparison of intramolecular C isotopes of propyl groups in the kerogens with their bulk δ 13 C, based on the PS δ 13 C of early-generated propane, contributes to our understanding of heterogeneities of isotopic structures of sedimentary organic matter.

International Journal of Coal Geology↗
USGS2023

Interlaboratory study: Testing reproducibility of solid biofuels component identification using reflected light microscopy

Considering global market trends and concerns about climate change and sustainability, increased biomass use for energy is expected to continue. As more diverse materials are being utilized to manufacture solid biomass fuels, it is critical to implement quality assessment methods to analyze these fuels thoroughly. One such method is reflected light microscopy (RLM), which has the potential to complement and enhance current standard testing, leading to improving fuel quality assessment and, ultimately, preventing avoidable air pollution. An interlaboratory study (ILS) was conducted to test the reproducibility of biomass fuels component identification using a reflected light microscopy technique. The exercise was conducted on thirty photomicrographs showing biomass and various undesired components (like plastics or mineral matter), which were purposely added (by the ILS organizers) to contaminate wood pellets and charcoal-based grilling fuels. Forty-six participants had various levels of difficulty identifying the marked components, and as a result, the percentage of correct answers ranged from 52.2 to 94.4%. Among the most difficult components to distinguish were petroleum products and inorganic matter. Various reasons led to the misidentification, including insufficient morphological descriptions of the components provided to participants, ambiguities of the nomenclature, limitations of the analytical and exercise method, and insufficient experience of the participants. Overall, the results indicate that RLM has the potential to enhance the quality assessment of biomass fuels. However, they also demonstrate that the petrographic classification used in this exercise requires further refinement before it can be standardized. While a new simplified classification of solid biomass fuels components was created as an outcome of this study, future research is necessary to refine the nomenclature, develop a microscopic morphological description of the components, and verify the accuracy of component identification with a follow-up ILS.

International Journal of Coal Geology↗
USGS2023

Methane pore accessibility, densification, and accommodation by organic matter in the Niobrara Formation at wet-gas thermal maturity conditions

Petroleum within unconventional source-rock reservoirs is hosted in organic matter and mineral pore space as well as in voids and microfractures. Recent work has shown that for source-rock reservoirs in the dry gas window, significant portions of methane (CH 4 ), the main component of petroleum at elevated maturities, can be stored within fine (<5 nm) organic matter porosity. However, within reservoirs at lower thermal maturities (e.g., peak oil or wet-gas conditions), the distribution and behavior of CH 4 and the higher alkanes that comprise gas condensates across pore sizes is unclear, especially for pores with diameters <50 nm. Understanding CH 4 distribution within these settings provides insight for petroleum generation, movement, and recoverability, ultimately enabling increased accuracy of estimated ultimate recovery. Here wide Q-range total neutron scattering was used to evaluate perdeuterated methane (CD 4 ) behavior at reservoir pressures (200–750 bar) and temperature (60 °C) in a sample at the late oil/wet gas thermal maturity stage from the Late Cretaceous Niobrara Formation, an active petroleum producing formation within the Denver-Julesburg Basin, U.S. Neutron scattering data show that mesopores within the Niobrara Formation sample exhibit mass fractal scattering, similar to previously measured U.S. marine shale samples. In the presence of CD 4 , scattering intensities between Q = 0.02–0.1 Å −1 (corresponding to nominal pore diameters from 25 to 5 nm, respectively) decrease with increased pressure up to 750 bar where at least 80% of all pores with ~25 nm diameters are CD 4 accessible. In contrast, between Q = 0.1–1 Å −1 (corresponding to nominal pore diameters from 5 to 0.5 nm, respectively), scattering intensity initially increased at the lowest CD 4 pressure tested (200 bar) before decreasing with increasing pressure. These signal fluctuations with CD 4 pressure are interpreted to arise from the creation of pores with diameters <5 nm, likely through deformation of solid bitumen by supercritical CD 4 , and/or the incorporation of CD 4 within sample organic matter. This new porosity represents an increase of at least ~8% in available pore volume within the sample, although the majority of these pores do not persist following removal of CD 4 . Additionally, there is strong evidence for densification of CD 4 within the sample indicated by a shift in the CD 4 intermolecular scattering peak to higher Q-values compared to bulk CD 4 . These results provide insight into fluid properties within source-rock reservoirs at late oil/wet gas thermal maturities, especially as they relate to organic porosity interconnectivity, and are discussed with perspective toward pressure management of gas condensate wells.

Colorado, Kansas, Nebraska, Wyoming↗
USGS2023

Evaluation of portable Raman spectroscopic analysis for source-rock thermal maturity assessments on bulk crushed rock

This study presents a simplified method and empirical relationships for determining organic matter thermal maturity using a portable Raman system equipped with a 785 nm laser, for analysis of crushed, whole-rock samples. Suites of rocks represented by shale and coal samples with various mineralogical composition, thermal maturity, and total organic carbon (TOC) were used to test the method and build correlations between Raman band separation (RBS) values and traditional thermal maturity indicators, organic matter reflectance (Ro), and programmed temperature pyrolysis (Tmax) values. A set of disparate shale samples, where both vitrinite and solid bitumen reflectance values were reported, have Ro values that range from 0.40 to 4.62%. Above 3.35% Ro, the corresponding RBS values plateau at ∼290 cm−1, thus correlations were evaluated with a linear regression (R2 = 0.96) between 0.40 and 3.35% Ro. Shale samples with Ro < 2% and Tmax < 551 were also used to correlate Tmax and RBS, yielding a linear correlation with an R2 of 0.94. For the coal data set, Ro values range from 1.21 to 4.08% and correlated RBS values plateau at ∼250 cm−1 above Ro = 3.0%, suggesting its correlative application below this maturity level. Several sample preparation methods were tested on cuttings material and standard deviation values for RBS were minimized by washing, drying, and hand crushing the material to pass through a 40-mesh sieve, although less preparation can still yield reliable results. The high degrees of correlation between whole-rock RBS data and two thermal maturity indicators demonstrate the utility of this approach for generating source rock thermal maturity data from minimally processed, whole-rock samples which could easily be applied in field or laboratory settings.

International Journal of Coal Geology↗
USGS2024

Structure and morphology of chars and activated carbons obtained from thermal treatment of coal and biomass origin materials, including their wastes: Results from the ICCP Microscopy of Carbon Materials Working Group

This paper describes the evaluation of petrographic textures in char and activated carbon derived from coal, coal by-products and biomass, formed during carbonization and activation processes. This work represents the results of interlaboratory exercises from 2016 to 2022 of the Microscopy of Carbon Materials Working Group in Commission III of the International Committee for Coal and Organic Petrology. The interlaboratory exercises were run on photomicrograph samples. For textural characterization of carbon materials, the existing American Society for Testing and Materials (ASTM) classification system for metallurgical coke was applied. Morphological differences were evaluated in 29 carbon material types, including 22 char samples, and 7 activated carbon (AC) samples obtained experimentally using conventional direct/indirect and microwave heating technologies. This approach gives an extended view on the identification of microporous carbons, and how a certain heat treatment develops a certain optical texture and structure in a raw material. The requested evaluation of carbon materials was related to their porosity, origin, extent, and characteristics, which are particular to each carbon material type. Because carbon matrices can form a wide range of optical textures during heat treatment it is important to demonstrate which carbon occurrences will have a crucial role in industrial applications dominated by adsorption phenomena. The interlaboratory exercises included 17 participants from 14 laboratories. Four sets of digital black and white and colour photomicrographs were distributed, which in total comprised 184 fields of different types of carbon material. The results were evaluated based on four levels: (i) optical texture (isotropic/anisotropic), (ii) optical type and size (punctiform, mosaic, fiber, ribbon, domain), iii) morphology (porous, non-porous/massive), and (iv) particle origin (precursor type). The statistical method applied to evaluate the results was based on “raw agreement indices”. Comparative analyses of the average values of the level of overall agreement showed homogeneity in the results, the mean value was 89%, with a minimum value of 87% and a maximum value of 91% for those who participated in at least three out of four exercises.

International Journal of Coal Geology↗
USGS2024

Decoding paleomire conditions of Paleogene superhigh-organic-sulfur coals

Superhigh-organic‑sulfur (SHOS) coals (coals with organic sulfur content >4 wt%) are unique coal deposits found at a few notable locations in the world. Specific peat accumulation and preservation conditions must be met to form SHOS coals. Organic sulfur is a major constituent of such coals, and it may have various sources depending on the prevailing paleomire conditions. Understanding such paleomire conditions sheds light on the formation mechanisms of SHOS coals. This investigation decodes the paleomire conditions of the Paleogene SHOS coals from Meghalaya, India, using sulfur isotopic compositions ( δ 34 S) of organic sulfur ( δ 34 S OS ) and pyritic sulfur ( δ 34 S Py ) along with organic petrography, pyrite morphology and trace element ratios. Thirty coal samples were collected from the Jaintia Hills in the east, Khasi Hills in the middle, and Garo Hills in the west of Meghalaya. The organic sulfur content in the Garo, Khasi, and Jaintia coals varies from 1.0 to 3.3 wt%, 1.4 to 13.8 wt%, and 1.0 to 7.2 wt%, respectively. Further, after separation from pyritic sulfur and sulfate sulfur phases, the organic sulfur content ranges from 54.4 to 69.2%, 63.8 to 79.9%, and 59.3 to 73.8%, in the Garo, Khasi, and Jaintia Hills, respectively, suggesting the SHOS nature of these coal samples. The δ 34 S Py varies from −29.3 ‰ to +5.7 ‰, −21.3 ‰ to +27.3 ‰, and −12.1 ‰ to −4.3 ‰, in the Jaintia, Khasi, and Garo Hills, respectively, while the δ 34 S OS fluctuates from −4.6 ‰ to +3.7 ‰, −9.3 ‰ to +7.8 ‰, and − 9.0 ‰ to −5.0 ‰, respectively. The δ 34 S values of pyrite and organic sulfur (OS) in Jaintia coals are 34 S depleted compared to seawater sulfate (+22 ‰), leading to fractionations in the range of −51.3 ‰ to −16.3 ‰ (mean − 31.6 ‰) and − 26.6 ‰ to −18.3 ‰ (mean − 23.1 ‰) for pyritic and organic sulfur (OS), respectively. Pyrite in Khasi coals show a relatively heavier δ 34 S composition averaging at −20.5 ‰, whereas organic sulfur (OS) isotope compositions range from −31.3 ‰ to −14.2 ‰ with a mean of −22.6 ‰. Pyrite and OS in the Garo coals are depleted compared to seawater sulfate. Isotope variations in the Jaintia, Khasi, and Garo coals indicate microbial sulfate reduction (MSR) of seawater sulfate. Large isotopic fractionations between Eocene seawater sulfate and pyritic sulfur ( Δ 34 S SO4Eocene – pyrite = up to −51.3 ‰; mean − 31.6 ‰) in Jaintia coals indicate their possible formation in the water column/near the sediment-seawater interface (open system) and also hint toward dissimilatory sulfate reduction pathways that prevailed under anoxic redox conditions. However, mean values of Δ 34 S SO4Eocene – pyrite (−20.5 ‰) in the Khasi coals imply pyrite formation deeper in the sediments (more closed system) under dysoxic conditions. The dominance of OS over pyritic sulfur, framboidal pyrite, and its microcrystal size distributions in Jaintia coals may suggest syngenetic pyrite formation in open water reducing/anoxic conditions under paralic environments. Elevated Sr/Ba and U/Th values in these coals further confirm the anoxic conditions. Nevertheless, the presence of euhedral pyrite with the alleviated pyrite framboids in the Khasi coals and their complete absence in the Garo coals may suggest dysoxic-suboxic and suboxic-oxic depositional conditions, respectively. The isotopic signatures of the Garo coals suggest sulfur contribution from the parent paleobiota and MSR under a freshwater-oxic environment. Insignificant fractionations between δ 34 S Py and δ 34 S OS indicate limited iron and sulfate availability for additional sulfur cycling and disproportionation reactions, typical of oxic conditions. The absence of framboidal pyrite, elevated sulfate concentration, and mean Sr/Ba and U/Th values of 0.5 and 0.3, respectively, further suggest the freshwater peat deposition in the Garo Hills under limnotelmatic to telmatic freshwater conditions. Moreover, high inertinite content (I mmf = 9.77–33.16 vol%), possibly induced by atmospheric peat exposure, supports the interpretation of suboxic-oxic paleomire conditions in Garo Hills. Gradually decreasing mineral matter content from Jaintia (mean 13.6 vol%) to Garo coals (mean 7.4 vol%) additionally projects a transition from mesotrophic brackish to freshwater limnotelmatic environment, complementing the shift in the paleomire condition from eastern (Jaintia) to western (Garo) Meghalayan Hills.

International Journal of Coal Geology↗
USGS2024

The petrology of dispersed organic matter in sedimentary rocks: Review and update

Organic petrology developed from coal petrology, and, in the 1960s, it began to be applied to the study of dispersed organic matter (DOM) in sedimentary rocks other than coal. Over the last few decades, the petrology of DOM has been used to characterize organic matter in sedimentary basins with an emphasis on fossil fuel resource exploration. Today, due to the global research shift on topics related to climate, organic petrology has expanded into new application areas, such as geothermal exploration, biological carbon storage (biochar), disposal, and management of radioactive waste. From the publication of the International Handbook of Coal Petrology (mid-20th century) to the present day, a large number of standards, books, and articles have been published as a result of the work of organic petrographers and petrologists around the world and efforts of the International Committee for Coal and Organic Petrology (ICCP) and The Society for Organic Petrology (TSOP) to promote the study of organic petrology. The current fundamentals and standards of organic petrology provide the international scientific community with well-informed guidance and recommendations to promote in-depth research. However, this information is currently widely scattered, leading to discrepancies in methodology and terminology. Therefore, this paper aims to present a comprehensive review of the main analytical standard test methods and techniques currently used in the petrology of DOM under reflected white light and UV and blue-light excitation, and to provide an efficient and well-defined reference guide. Furthermore, considering the important role of the ICCP in the development of organic petrology since the 1950s, a brief review of the ongoing activities of ICCP dealing with DOM is also presented.

International Journal of Coal Geology↗