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94 records · Page 6Linked to original sources

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↗

Confocal laser-scanning microscopy (CLSM)-based thermal maturity of Tasmanites and progress in standardization of fluorescence microspectrometry

Evaluation of thermal maturity in vitrinite-free or vitrinite-deficient sediments via fluorescence microspectrometry can provide relevant information related to petroleum exploration and thermal history assessment. However, variation in spectral fluorescence properties of alginite macerals with increasing thermal maturity is largely underexplored. Here, authors of this study have applied confocal laser-scanning microscopy (CLSM) in conjunction with fluorescence microspectrometry to a maturity series of marine Upper Devonian Tasmanites algae from the Ohio Shale (Huron Member) and a single sample from the Marcellus Formation of the Appalachian Basin. Spectral fluorescence properties of Tasmanites were evaluated in relation to orientation, measurement location, and the number of measurements per sample, and were compared to published literature. Emission spectra of Tasmanites from continuous wave laser excitation (405 nm) were acquired from sections perpendicular and parallel to bedding and at different positions within individual Tasmanites bodies. The results showed a progressive red-shift in emission maxima (λ max ) in a large sample sized maturity series ( N = 19), e.g., 493 to 578 nm for the perpendicular section at middle position. Further, blue-shifted apex and mineral-adjacent positions within sections perpendicular to bedding were observed, with the latter being reported here for the first time. While blue-shift at apex positions can be attributed to mechanical deformation-induced reorientation of photoselected fluorophores, the blue-shifted mineral-adjacent positions could result from strain loading and development of a plastic deformation region at the mineral contact zone with Tasmanites . A decrease in standard deviation with increasing number of measured emission maxima is well-observed, and 15 to 20 individual measurements per sample appears sufficient for low standard deviation and coefficient of variance. CLSM-derived thermal maturity parameters indicated that a moderate positive correlation of red/green quotient (Q 650/500 ; R 2 = 0.67) with solid bitumen reflectance (BR o in %) exists. For reproducible results, the determination of λ max and Q 650/500 should be conducted exclusively in the middle position at perpendicular and parallel sections of the polished whole-rock pellets, where the lowest standard deviation in measurement was observed. These results strengthen the suitability and relevance of the CLSM technique in thermal maturity studies of dispersed organic matter (DOM) and contribute to the standardization of fluorescence microspectrometry methods in organic petrology investigation.

Kentucky, Ohio, Virginia, West Virginia↗

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↗

A review of Arbuckle Group strata in Kansas from a sedimentologic perspective: Insights for future research from past and recent studies

Arbuckle Group and equivalent-age rocks (Cambrian and Lower Ordovician) represent an important record of sediment deposition in the history of the North American continent and they contain important accumulations of hydrocarbons (oil and gas) and base metal deposits. This is true for Kansas as well where Arbuckle strata account for approximately 40% of the volume of produced petroleum and known reserves. However, in comparison to their counterparts in other areas, such as the Ellenburger and Knox, Arbuckle rocks in Kansas remain relatively understudied, especially with respect to sedimentology and diagenesis. The Arbuckle is present in the subsurface in most of Kansas and is absent only in areas of northeastern and northwestern Kansas, and over ancient uplifts and buried Precambrian highs. Arbuckle rocks thicken from north to south and are up to 1,390 feet in the southeastern corner of Kansas. Arbuckle Group and equivalent-age rocks from Kansas and surrounding areas are similar, consisting of platform deposits dominated by ramp-type subtidal to peritidal carbonates (mostly dolomitized) which can be subdivided into cycles, less than 0.5 m to 40 m thick, based on facies type and depositional patterns. Recent studies from central Kansas show that major depositional facies consist of coarse-grained packstones/ grainstones, fine-grained packstones/wackestones/mudstones, stromatolites-thrombolites, intraclastic conglomerate and breccia, and shale. In addition, secondary features include dolomitization, breccia, fracture, and conglomerate related to early subaerial exposure and later karst, burial or structural processes, silicification, and local mineralization. Arbuckle and equivalent strata in the Midcontinent were affected by prolonged subaerial exposure that began immediately after Arbuckle deposition, forming the sub-Tippecanoe to sub-Absaroka unconformity. Favorable reservoir qualities generally are thought to be related directly to basement structural elements and karstic features from the post-Arbuckle subaerial exposure event. Although most production in Kansas is from the top of the Arbuckle, some early and recent studies indicate that the Arbuckle is not a simple homogeneous reservoir, that complex vertical and lateral heterogeneities exist including both nonporous and porous horizons in the formation, and that high probability exist of locating additional oil with improved reservoir characterization. Although fracture and vuggy porosity contribute importantly to the production of Arbuckle strata, recent observations indicate a significant amount of porosity (about 50%) in many cores is controlled by depositional facies and dolomitization. Studies of Arbuckle and equivalent-age strata from other areas indicate that Arbuckle strata and diagenetic processes are complex and that porosity/permeability patterns are related to a number of processes. These studies underscore the importance of continued study of Arbuckle rocks in Kansas for improved reservoir characterization. Ongoing and future geologic studies of Arbuckle rocks in Kansas are being directed toward: (1) Continued sedimentologic, stratigraphic, and sequence stratigraphic analyses incorporating core, well log, and seismic data; (2) petrophysical studies. Initial studies indicate that core plug petrophysical properties are controlled by matrix grain size and that upscalling from plug to whole-core and drill-stem test data can identify and quantify the relative contribution of karstic, fracture and matrix porosity and permeability: (3) Regional and local structural analyses and mapping of the upper Arbuckle surface to provide more details on the contribution of structural features and karst paleogeomorphology to reservoir character; and (4) diagenetic and geochemical studies focusing especially on the timing of, and processes associated with, dolomitization and karstification events and their contributions to creating or occluding porosity.

The Compass: Earth Science Journal of Sigma Gamma ↗