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Paul C. Hackley

Publications and source records attributed to Paul C. Hackley.

At least 91 records · Page 5Linked to original sources

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↗

Assessment of undiscovered continuous oil and gas resources in the Upper Cretaceous Tuscaloosa marine shale of the U.S. Gulf Coast, 2018

Using a geology-based assessment methodology, the U.S. Geological Survey assessed mean undiscovered, technically recoverable continuous resources of 1.5 billion barrels of oil and 4.6 trillion cubic feet of gas in the Upper Cretaceous Tuscaloosa marine shale in onshore and State waters of Louisiana, Mississippi, Alabama, and Florida in the U.S. Gulf Coast region.

Upper Cretaceous Tuscaloosa Marine Shale↗

Pore-types and pore-network evolution in Upper Devonian-Lower Mississippian Woodford and Mississippian Barnett mudstones: Insights from laboratory thermal maturation and organic petrology

Pore-evolution models from immature organic-matter (OM) -rich Barnett (0.42%R o ) and Woodford (0.49%R o ) mudstones were compared with models previously developed from low-maturity OM-lean Boquillas (Eagle Ford-equivalent) mudstones to investigate whether (1) different mineralogy (siliceous vs. calcareous) exerts different catalytic and sorption effects and influences OM-pore origin and evolution; and (2) different types of macerals show different OM pore evolution history. Laboratory gold-tube pyrolysis, scanning electron microscopy (SEM) and thin-section petrography, organic petrography, and geochemical characterization were used to investigate the role of bulk mineralogy, maceral type, and thermal maturation on OM-pore evolution. Results suggest that mineralogy has little impact on OM-pore development and evolution. Macerals, identified using both SEM (platy OM, particulate OM, organic–mineral admixtures, Tasmanites ) and organic petrology (vitrinite, inertinite, amorphous organic matter [AOM]/bituminite, telalginite [ Leiosphaeridia , Tasmanites ]), do affect the origin and evolution of OM pores owing to differences in chemical compositions, generation kinetics, and activation-energy distributions between Tasmanites , matrix bituminite, and other types of macerals. Leiosphaeridia and Tasmanites in Woodford mudstone samples exhibit a delay in onset and a shorter period of petroleum generation and pore development compared to the matrix bituminite in the Barnett and Woodford mudstone samples. Pre-oil solid bitumen was observed to have migrated into initial primary mineral pore networks at the bitumen generation stage in both Barnett and Woodford samples. At higher levels of thermal maturation, the volume of primary mineral pores decreases and the pore volume composed of modified mineral pores and OM pores becomes greater. Pore evolution and pore-type heterogeneity in these mudstones is a function of the initial mineral pore network, types of kerogen and macerals, and generation kinetics of individual macerals upon thermal maturation.

Oklahoma↗

On the petrographic distinction of bituminite from solid bitumen in immature to early mature source rocks

The oil-prone maceral bituminite (and its equivalents: ‘amorphous organic matter’, ‘sapropelinite’, ‘amorphinite’, etc.) converts to petroleum during thermal maturation of source rocks, resulting in formation of a mobile saturate-rich hydrocarbon and a polar-rich residue of solid bitumen. Evidence of this transition is preserved in immature to early mature source rocks (e.g., Alum, Bakken, Kimmeridge, New Albany, Ohio shales, among many others), where organic petrography reveals a continuum of textures, reflectance, and fluorescence intensity occurring between bituminite and solid bitumen. Bituminite generally is characterized by high(er) intensity fluorescence, low contrast to the inorganic matrix, lower reflectance (compared to solid bitumen), and heterogeneous wispy or ‘schlieren’ textures. In comparison, solid bitumen generally shows lower intensity or no fluorescence compared to bituminite, a distinct contrast to the mineral matrix which usually includes a gray homogeneous surface of low to moderate reflectance, and may possess void-filling, embayment or groundmass textures suggesting evidence of migration or its in situ exsolution. However, these properties may manifest across a continuous spectrum in a sample or in a single microscope field, often making identification inconclusive. Unambiguous identification is further hampered by sample preparation, e.g., mechanical polish may improve homogeneity of larger accumulations, whereas smaller accumulations, or those sheltered by hard minerals, may appear more heterogeneous, leading to identification of the same organic matter as solid bitumen or bituminite, respectively. The disruptive innovation of ion milling in shale sample preparation leads to increased organic reflectance and surface homogeneity, causing bituminite and other oil-prone macerals, e.g., alginite, to develop a gray reflecting surface which is easy to confuse with solid bitumen, especially when obvious void-filling or embayment textures of the latter are absent. Herein we review distinction of solid bitumen from bituminite and alginite in immature to early mature source rocks, providing examples from nine samples illustrated by typical organic petrography images, including samples from hydrous pyrolysis experiments. Based on a review of the literature, we observe an arbitrary reflectance limit of 0.30% in mechanically polished samples seems to differentiate bituminite (<0.30%) from confident identifications of homogeneous solid bitumen (which otherwise lacks obvious void-filling or identifying embayment textures) as individual macerals on a continuous spectrum in immature and early mature source rocks. Future work conducted by governing bodies such as the International Committee for Coal and Organic Petrology (ICCP) should consider interlaboratory studies conducted on multiple immature source rock samples to develop consensus guidelines for bituminite and solid bitumen discrimination.

International Journal of Coal Geology↗

High microscale variability in Raman thermal maturity estimates from shale organic matter

Raman spectroscopy has recently received attention as a means to estimate thermal maturity of organic matter in petroleum generating source rocks to complement more traditional approaches such as vitrinite reflectance and programmed pyrolysis. While many studies have observed positive correlations between source rock thermal maturity and Raman spectral parameters, little attention has been given to the degree of variation in the Raman response across individual organic grains, especially for shales or mudrocks with highly dispersed organic matter. Here the spatial variation in Raman estimates of thermal maturity within individual organic grains is assessed from shales from the Boquillas, Marcellus, Niobrara, and Woodford Formations. The thermal maturity parameters extracted from Raman spectra can vary widely across distances of ≤5 μm within the same organic grain. These results illustrate the high degree of chemical heterogeneity inherent to the organic matter within these source rocks. Additionally, the spatial pattern of the Raman parameters, as revealed by 2D Raman mapping, imply that organic matter structure is influenced by associations with mineral surfaces within the surrounding rock matrix. Chemical heterogeneity and matrix effects directly impact the Raman response from these types of materials and thus the extracted thermal maturity estimate. These findings highlight the care which must be adopted when making Raman measurements of organic matter within source rock matrices, especially for samples which feature highly dispersed, heterogeneous organic matter as found in petroliferous mudrocks.

International Journal of Coal Geology↗

Quantitative evaluation of vitrinite reflectance and atomic O/C in coal using Raman spectroscopy and multivariate analysis

Vitrinite reflectance (VRo) is a standard petrographic method for assessing thermal maturity (rank) of coal. The vitrinite reflectance technique, however, requires significant petrographic experience, can be time-consuming, and may be biased by analyst subjectivity. Correlations between coal rank and Raman spectral properties are a promising alternative that can supplant some of the limitations inherent in the VRo protocol. The traditional peak-fitting methodologies for quantifying metrics from Raman spectra, however, also suffer from analyst subjectivity that can affect correlations between analyte and spectral properties. This research combines high-throughput Raman spectroscopy with multivariate analysis (MVA) to create calibration models for the prediction of coal rank though VRo and atomic O/C ratio. MVA techniques eliminate the ambiguous subjectivity prevalent in peak-fitting methods by evaluating the full Raman spectrum, then identifying the integral vibrational modes for constructing accurate models. Partial least squares (PLS) regression models were developed using Raman spectra and VRo values (0.23–5.23%) for 68 geographically diverse coal samples. The calibration set was validated using one-half of the samples to rigorously assess the model’s predictive accuracy. The root mean standard error of prediction was 0.19 for the VRo model and 0.014 for the atomic O/C model. Both models exhibited linear correlations, with coefficients of determination ( R 2 ) for the validation set of 0.99 (VRo) and 0.93 (atomic O/C), despite the geographic and rank diversity of the samples. This study demonstrates the applicability and power of using PLS models for the prediction of both the VRo and atomic O/C ratio from Raman spectra. The quantitative MVA protocol contained herein provides a Raman alternative to the VRo industry benchmark for coal rank that is not subject to the limitations and subjectivity of peak-fitting methods.

Fuel↗

Using mercury injection pressure analyses to estimate sealing capacity of the Tuscaloosa marine shale in Mississippi, USA: Implications for carbon dioxide sequestration

This work used mercury injection capillary pressure (MICP) analyses of the Tuscaloosa Group in Mississippi, including the Tuscaloosa marine shale (TMS), to assess their efficacy and sealing capacity for geologic carbon dioxide (CO 2 ) sequestration. Tuscaloosa Group porosity and permeability from MICP were evaluated to calculate CO 2 column height retention. TMS and Lower Tuscaloosa shale samples have, respectively, Swanson permeability values less than 0.003 md and 0.00245 md; porosity from 3.86% to 9.86% and 1.34% to 7.96%; median pore throat sizes from 0.00342 to 0.0111 μm and 0.00311 to 0.017 μm; and pore radii from 0.0130 to 0.152 μm and 0.0132 to 0.149 μm. Mercury entry pressures for the TMS and Lower Tuscaloosa range from 4.9 to 57.1 MPa and 5.0 to 56.3 MPa, respectively. Calculated CO 2 column heights that the TMS sample set can retain in the reservoir range from 23 to 255 m when the TMS is near 100% water saturation. Potential top seal leakage is more likely to be influenced by the numerous well penetrations through the confining system of the TMS rather than capillary failure. Results of this study demonstrate desirable sealing capacity of the TMS for geologic CO 2 sequestration in reservoir sandstones of the Lower Tuscaloosa and could provide an analogue to other potential CO 2 sequestration top seals.

Louisiana, Mississippi↗

DDT and related compounds in pore water of shallow sediments on the Palos Verdes Shelf, California, USA

For nearly two and a half decades following World War II, production wastes from the world's largest manufacturer of technical DDT (1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene) were discharged into sewers of Los Angeles County. Following treatment, the wastes were released via a submarine outfall system to nearshore coastal waters where a portion accumulated in shallow sediments of the Palos Verdes Shelf (PVS). An investigation of the pore-water geochemistry of DDT-related compounds (DDX) was undertaken in an effort to understand factors controlling the rate of reductive dechlorination (RDC) of the major DDT degradate, 4,4′-DDE (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene). Equilibrium matrix-solid phase microextraction (matrix-SPMEeq) combined with automated thermal desorption-gas chromatography/mass spectrometry (TDGC/MS) was used to determine freely dissolved concentrations of ten DDX analytes in sediment cores collected from three locations on the PVS (stations 3C, 6C, 8C, which are 7 km, 2 km, and 0 km, respectively, downcurrent from the outfall system). Pore-water concentrations (pM) of the principal DDX compounds involved in RDC were: 3C-DDE: 6.0–24, DDMU (1-chloro-4-[2-chloro-1-(4-chlorophenyl)ethenyl]benzene): 11–160, DDNU (1-chloro-4-[1-(4-chlorophenyl)ethenyl]benzene): 1.8–68; 6C-DDE: 5.6–170, DDMU: 5.6–177, DDNU: 1.7–87; 8CDDE: 27–212, DDMU: 31–403, DDNU: 5.5–89. Variations in the spatial distribution of DDX analytes in pore water reflect several factors including proximity to the outfalls, RDC reaction rates, and natural variability in sedimentation and post-depositional transport processes. A comparison of pore-water data produced using matrix-SPME eq /TD-GC/MS and whole-core squeezing/solvent extraction/liquid injection-GC/MS indicates that the majority of the DDE in the upper sediment column (≤about 10 cm) is associated with dissolved/colloidal organic matter. Below that depth, freely-dissolved DDE predominates. The principal organic geochemical phase controlling sorption of DDE in PVS sediments are residual hydrocarbons, the vast majority of which originated from petroleum refinery wastes. Organic carbon-normalized sediment-water distribution coefficients (KOC) were calculated from solid-phase and pore-water concentrations of DDX and organic carbon. Log K OC values (L/kg) were relatively invariant across the shelf and with depth in the sediment column. Shelf-wide compound-specific coefficients (log K OC ) were: DDE: 7.5 ± 0.11, DDMU: 6.92 ± 0.13, DDNU: 6.37 ± 0.19. The spatial uniformity of K OC means that biological exposure and availability of the DDX compounds can, in principle, be estimated from solid-phase chemical measurements.

California↗

Suppression of vitrinite reflectance by bitumen generated from liptinite during hydrous pyrolysis of artificial source rock

Mean random vitrinite reflectance (R o ) is the most widely accepted method to determine thermal maturity of coal and other sedimentary rocks. However, oil-immersion R o of polished rock or kerogen samples is commonly lower than R o values measured in samples from adjacent vitrinite-rich coals that have undergone the same level of thermal stress. So-called suppressed R o values have also been observed in hydrous pyrolysis experiments designed to simulate petroleum formation. Various hypotheses to explain R o suppression, such as sorption of products generated from liptinite during maturation, diagenetic formation of perhydrous vitrinite or overpressure, remain controversial. To experimentally test for suppression of vitrinite reflectance, artificial rock was prepared using silica and a calcined blend of limestone and clay with various proportions of thermally immature vitrinite-rich Wyodak-Anderson coal and liptinite-rich kerogen isolated from the oil-prone Parachute Creek Member of the Green River Formation. The samples were subjected to hydrous pyrolysis for 72 h. at isothermal temperatures of 300 °C, 330 °C, and 350 °C to simulate burial maturation. Compared to artificial rock that contains only coal, samples with different proportions of oil-prone kerogen show distinct suppression of calibrated R o at 300 °C and 330 °C. The reflectance of solid bitumen generated during heating of the samples is lower than that of the associated vitrinite and does not interfere with the R o measurements. These results provide the first experimental evidence that R o suppression occurs in vitrinite mixed with liptinite-rich kerogen in a rock matrix. Although the precise chemical mechanism for R o suppression by liptinite remains unclear, free radicals generated from solid bitumen and associated volatile products during maturation of liptinite may contribute to termination reactions that slow the aromatization and rearrangement of polyaromatic sheets in vitrinite, thus suppressing R o . This mechanism does not preclude R o suppression that might result from overpressure or differences in redox conditions during diagenesis.

Organic Geochemistry↗

Understanding and distinguishing reflectance measurements of solid bitumen and vitrinite using hydrous pyrolysis: Implications to petroleum assessment

Solid bitumen is a common organic component of thermally mature shales and typically is identified by embayment against euhedral mineral terminations and by groundmass textures. However, because these textures are not always present, solid bitumen can be easily misidentified as vitrinite. Hydrous-pyrolysis experiments (72 hr, 300°C–360°C) on shale and coal samples show that solid-bitumen reflectance ( BR o ) in shales is less responsive to thermal stress than vitrinite reflectance ( R o ) in coal. This effect is most pronounced at lower experimental temperatures (300°C–320°C), whereas reflectance changes are more similar at higher temperatures (340°C–360°C). Neither a “vitrinite-like” maceral nor “suppressed vitrinite” was identified or measured in our sample set; instead, the experiments show that solid bitumen matures slower than vitrinite. The data may explain some reports of “ R o suppression,” particularly at lower thermal maturity ( R o ≤ 1.0%), as a simple case of solid bitumen being mistaken for vitrinite. Further, the experimental results confirm previous empirical observations that R o and BR o are more similar at higher maturities ( R o > 1.0%). It is suggested that R o suppression, commonly reported from upper Paleozoic marine shales of early to midoil window maturity, is a misnomer. This observation has important implications to petroleum exploration models and resource assessment, because it may change interpretations for the timing and spatial locations of kerogen maturation and petroleum generation.

AAPG Bulletin↗

Development of Raman spectroscopy as a thermal maturity proxy in unconventional resource assessment

The objective of this study was to correlate shale hydrous pyrolysis with thermal maturity measurements based on solid bitumen reflectance (BRo) at the U.S. Geological Survey (USGS) and Raman microscopy (RM) at WellDog. In semi-blind Phase I, BRo values of the initial set of 8 samples were withheld prior to RM analysis. As reported previously, a strong correlation was observed between BRo and Raman parameters. For Phase-II, BRo values for the second set of 8 samples were shared before RM. Observations from Phase-II are reported here as well as the ability of RM to correctly order the semi-blind Phase I samples. Immature shale samples from the Bakken (Phase-I) and Duvernay (Phase-II) formations were subjected to hydrous pyrolysis for 72 hours at temperatures from 280°C to 360°C. Rock residues from both series were mounted and polished (ASTM D2797) for analysis of BRo (ASTM D7708) and confocal laser-scanning Raman microscopy. For RM, multiple hyperspectral maps were collected from each sample, resulting in tens of thousands of spectra per sample. Map areas were ~5,000 μm2, with a spectrum collected from every square micrometer. The organic carbon G- (Graphitic-) and D- (Disordered) bands in each Raman spectrum were fit algorithmically to a multi-peak model, yielding a number of diagnostic parameters that correlate with changes occurring in samples as a result of thermal maturation and pyrolysis. Parameters extracted from analysis of Raman spectra were plotted against the previously determined BRo values to determine which Raman parameters best correlate with thermal maturity. Plotting two of the sample-averaged anonymized spectral parameters versus BRo in the Bakken series indicated an exponential trend with strong correlations (R2>0.8) as reported at URTeC in 2017 (MS-2671253). Similar strong relationships occurred in the Duvernay samples with respect to increasing maturity when using Partial Least-Squares analysis.

Conference Paper↗

Nanoscale geochemical and geomechanical characterization of dispersed organic matter in shale by infrared nanoscopy

Solid organic matter (OM) plays an essential role in the generation, migration, storage, and production of hydrocarbons from economically important shale rock formations. Electron microscopy images have documented spatial heterogeneity in the porosity of OM at nanoscale, and bulk spectroscopy measurements have documented large variation in the chemical composition of OM during petroleum generation. However, information regarding the heterogeneity of OM chemical composition at the nanoscale has been lacking. Here we demonstrate the first application of atomic force microscopy-based infrared spectroscopy (AFM-IR) to measure the chemical and mechanical heterogeneity of OM in shale at the nanoscale, orders of magnitude finer than achievable by traditional chemical imaging tools such as infrared microscopy. We present a combination of optical microscopy and AFM-IR imaging to characterize OM heterogeneity in an artificially matured series of New Albany Shales. The results document the evolution of individual organic macerals with maturation, providing a microscopic picture of the heterogeneous process of petroleum generation.

Nature Communications↗

Transgressive-regressive cycles in the metalliferous, oil-shale-bearing Heath Formation (Upper Mississippian), central Montana

The Upper Mississippian Heath Formation, which accumulated in the Big Snowy Trough of central Montana, has been known for three decades to contain mudrocks highly enriched in Zn, V, Mo, Ni and other metals, and source rocks for oil. The unit has more recently been recognized as a prospective tight oil play. Here we present petrographic, paleontologic, geochemical, and carbon and sulfur isotope data on seven continuous drill cores spanning ≤146 m of immature to marginally mature strata in order to improve understanding of the depositional setting of the Heath. The unit consists of five third-order transgressive-regressive cycles (C1–C5 from bottom to top) that were deposited during a fluctuating climatic regime. Cycles comprise thinly interbedded gray to black mudrock and carbonate strata capped by either coal, implying a humid climate (C1, C3 and C4), or gypsum, implying more arid conditions (C2); the upper part of C5 is not preserved in our study area. Mfs (maximum flooding surfaces) in C1, C2, C4, and C5 lie within black mudrock beds ~0.5–3-m thick with >10% TOC (total organic carbon), type I and type II kerogen (determined by programmed pyrolysis), high contents of Zn, V, Mo, and other metals, relatively low values of δ13CTOC and δ34Spyrite, and a limited-diversity fauna of locally abundant, thin-shelled pelecypods (Dunbarella? sp.). The mfs in C2 is within the Cox Ranch oil shale bed, which is known from previous studies to be metalliferous; new analyses reported here show ≤28 wt % TOC, 5140 ppm Zn, 1910 ppm V, 1590 ppm Mo, and 509 ppm Ni. Strata that contain the mfs of C1, C4, and C5 are shown here for the first time to also have high metal contents, with maximum values of 1030–7340 ppm Zn, 446–1980 ppm V, 72–859 ppm Mo, and 221–452 ppm Ni. Cycle C3, which contains more gray mudrock and carbonate beds than the other cycles, has lower TOC (≤4.2 wt %), lower metals, and mainly type III kerogen. Carbonate beds include normal-marine crinoidal mudstone to packstone and lesser (dolo)mudstone with fenestral fabric, peloids, intraclasts, and a euryhaline fauna. Mid-Chesterian (early Serpukhovian) foraminifers in C3, combined with previously published fossil data, suggest that third-order cycles in the Heath Formation were ~1–2 myr in duration. They formed during a time of active block faulting in the Big Snowy Trough and global cooling linked to Gondwanan glaciation. Tectonic, climatic, and paleogeographic factors shaped the cycles of the Heath Formation. Faunal and geochemical evidence indicate that conditions were most favorable for marine life during C3. Molybdenum concentrations >100 ppm and organic geochemical data suggest euxinic conditions during deposition of the black mudrock in C2, C4, and C5, but the presence of shell beds (1 mm–6-cm thick) within this mudrock requires bottom water with sufficient oxygen to support life, at least periodically. The apparent conflict between the geochemical and paleontologic observations likely reflects the different time scales of these two environmental proxies: 1000s of yrs vs <1–10s of yrs, respectively. Metal- and organic-rich strata in the Heath Formation formed by slow, condensed sedimentation from periodically anoxic or euxinic bottom waters in a marine basin. Fossil data indicate that anoxia was episodic, perhaps seasonal and/or linked to longer-duration climate shifts. On a millennial time scale, metal enrichments in the Heath reflect a balance between primary productivity that was high enough for oxygen to be consumed by sinking organic matter and oxic seawater inflow that was strong enough to maintain a supply of metals without compromising anoxia. Organic-rich mudrock in the Heath shares intriguing lithologic and geochemical similarities with mudrock in other Middle to Upper Paleozoic units such as the Devonian-Mississippian Bakken Formation and Pennsylvanian cyclothems (e.g., Excello Shale).

Montana↗

Assessment of thermal maturity trends in Devonian-Mississippian source rocks using Raman spectroscopy: Limitations of peak-fitting method

The thermal maturity of shale is often measured by vitrinite reflectance (VRo). VRo measurements for the Devonian–Mississippian black shale source rocks evaluated herein predicted thermal immaturity in areas where associated reservoir rocks are oil-producing. This limitation of the VRo method led to the current evaluation of Raman spectroscopy as a suitable alternative for developing correlations between thermal maturity and Raman spectra. In this study, Raman spectra of Devonian–Mississippian black shale source rocks were regressed against measured VRo or sample-depth. Attempts were made to develop quantitative correlations of thermal maturity. Using sample-depth as a proxy for thermal maturity is not without limitations as thermal maturity as a function of depth depends on thermal gradient, which can vary through time, subsidence rate, uplift, lack of uplift, and faulting. Correlations between Raman data and vitrinite reflectance or sample-depth were quantified by peak-fitting the spectra. Various peak-fitting procedures were evaluated to determine the effects of the number of peaks and maximum peak widths on correlations between spectral metrics and thermal maturity. Correlations between D-frequency, G-band full width at half maximum (FWHM), and band separation between the G- and D-peaks and thermal maturity provided some degree of linearity throughout most peak-fitting assessments; however, these correlations and those calculated from the G-frequency, D/G FWHM ratio, and D/G peak area ratio also revealed a strong dependence on peak-fitting processes. This dependency on spectral analysis techniques raises questions about the validity of peak-fitting, particularly given the amount of subjective analyst involvement necessary to reconstruct spectra. This research shows how user interpretation and extrapolation affected the comparability of different samples, the accuracy of generated trends, and therefore, the potential of the Raman spectral method to become an industry benchmark as a thermal maturity probe. A Raman method devoid of extensive operator interaction and data manipulation is quintessential for creating a standard method.

Frontiers in Energy Research↗

Utilization of integrated correlative light and electron microscopy (iCLEM) for imaging sedimentary organic matter

We report here a new microscopic technique for imaging and identifying sedimentary organic matter in geologic materials that combines inverted fluorescence microscopy with scanning electron microscopy and allows for sequential imaging of the same region of interest without transferring the sample between instruments. This integrated correlative light and electron microscopy technique is demonstrated with observations from an immature lacustrine oil shale from the Eocene Green River Mahogany Zone and mid‐oil window paralic shale from the Upper Cretaceous Tuscaloosa Group. This technique has the potential to allow for identification and characterization of organic matter in shale hydrocarbon reservoirs that is not possible using either light or electron microscopy alone, and may be applied to understanding the organic matter type and thermal regime in which organic nanoporosity forms, thereby reducing uncertainty in the estimation of undiscovered hydrocarbon resources.

Journal of Microscopy↗

Identification of alginite and bituminite in rocks other than coal. 2006, 2009, and 2011 round robin exercises of the ICCP Identification of Dispersed Organic Matter Working Group

The paper presents results of round robin exercises on photomicrograph-based identification of dispersed organic matter in source rocks that represent a range of marine and lacustrine deposits from worldwide localities and cover a range of thermal maturities. The round robin exercises were conducted by the Identification of Dispersed Organic Matter Working Group (IDOM WG) of the International Committee for Coal and Organic Petrology (ICCP). The round robin exercises aimed to (1) assess the applicability of the established ICCP definitions of bituminite, (2) identify deficiencies and improve the existing nomenclatures, and (3) provide a basis for the revision of the bituminite and alginite definitions in the ICCP Handbook (Taylor et al., 1998). Three round robin exercises performed in 2006, 2009 and 2011 involved 18 participants from research laboratories at universities and within government and industry. Participants were asked to identify macerals on the basis of existing definitions in 129 photomicrographs taken in incident white light and fluorescent mode and also in fluorescence light mode at prolonged (15 min) blue light irradiation. The results indicate that the definition of telalginite permits its positive and satisfactory agreement among the participants. In contrast, the descriptive characteristics of lamalginite referring to film-like appearance (filamentous) and lack of inner or outer structure are insufficient and inadequate to enable an unequivocal discrimination between it and telalginite. Furthermore, based on the amorphous nature of bituminite and lack of adherence to its established description and character (Taylor et al., 1998), the highest discrepancies were observed in its identification. Differentiation of bituminite from a fluorescent groundmass and in some cases from lamalginite proved to be particularly challenging. The findings of these round robin exercises are useful for improving the identification of sedimentary organic matter in source rocks and may be an important foundation for the modification of the ICCP definitions of alginite and bituminite.

International Journal of Coal Geology↗

Organic petrology and micro-spectroscopy of Tasmanites microfossils: Applications to kerogen transformations in the early oil window

The transformation of kerogen to hydrocarbons in the early stages of oil generation is critical for understanding the resource potential of liquid-rich shale plays. Organic petrology commonly is used for visual evaluation of type, quality, and thermal maturity of organic matter, but the relationship of visual petrographic changes to chemical transformations is not well characterized. To improve understanding of these processes, organic-walled microfossils of the unicellular green alga Tasmanites (composed of algaenan) in Upper Devonian Ohio Shale (Huron Member, Appalachian Basin) were analyzed by micro-spectroscopy techniques including micro-Fourier transform infrared (micro-FTIR), X-ray photoelectron (XPS), electron probe microanalysis (EPMA), and fluorescence. Immature to mid-oil window maturation sequences of core and outcrop samples with solid bitumen reflectance (BR) and vitrinite reflectance (VR) values ranging from 0.45 to 0.80 %Ro were used. Hydrous pyrolysis was applied to low-maturity (BR: 0.25–0.39 %Ro) Huron and time-correlative New Albany shale samples to create similar artificial maturation sequences for comparison. Micro-FTIR spectroscopy revealed a decrease in the CH 2 /CH 3 ratio with increasing maturity, indicating Tasmanites aliphatic chains become shorter and more branched. Oxygenated functional groups decreased relative to aliphatic stretching bands and increased aromaticity was noted at the highest maturities. In samples that were pyrolyzed for 72 h at temperatures of 300–320 °C (BR: 0.56–0.68 %Ro), Tasmanites showed similar trends, whereas at pyrolysis temperatures of 340 °C and higher (BR > 1.0 %Ro), Tasmanites was pseudomorphed by accumulations of solid bitumen, carbonate and sulfide. Replacement of Tasmanites by these phases in hydrous pyrolysis experiments ≥340 °C and its absence at higher maturities (peak oil, VR and BR ≥ 0.9 %Ro) in naturally matured samples, as documented in a previous study, implies that a large fraction of the algaenan component of original organic carbon is converted to petroleum during thermal maturation. XPS analysis indicated the molar proportion of aliphatic carbon increases with increasing thermal maturity, accompanied by decreases in oxygenated functional groups and olefinic carbon. EPMA of Tasmanites showed highest concentrations of S, with concentrations of redox-sensitive trace elements U, Mo, Ni and V generally at or below detection limits. Decrease in organic S with increasing thermal maturity may be related to cleavage of Tasmanites at C S linkages; however, this relationship was inconsistent and presence of adjacent or entrained nanoscale silicate or sulfide phases may impact measured trace element concentrations. Fluorescence microscopy and spectroscopy showed a red shift in spectral maxima and decreased emission intensities with increasing maturity, interpreted as due to non-radiative energy loss possibly because of increased aromaticity. Collectively, these results provide new insights into the in situ chemical transformations that accompany petrographic changes as oil-prone kerogen converts to petroleum with thermal advance from immature conditions into the mid-oil window.

Organic Geochemistry↗