Geology topics

Javin J. Hatcherian

Publications and source records attributed to Javin J. Hatcherian.

At least 19 recordsLinked to original sources

USGS2026

Sedimentological and geochemical characterization of lacustrine deposits of the Babouri-Figuil basin, northern Cameroon: Implications for source rocks distribution and petroleum exploration

The West and Central African Rift System (WCARS) refers to the series of Cretaceous rift basins where commercial hydrocarbon accumulations have been discovered. Some of the WCARS frontier basins are currently being investigated to increase our understanding of these basins in light of new commercial discoveries. The present study was performed in the Babouri-Figuil Basin (BFB), which is genetically related to the WCARS and constitutes an area of interest in terms of petroleum prospecting, where the distribution of petroleum source rocks and potential targets for petroleum exploration across the entire basin is poorly understood. For the current study, an integrated facies analysis along with organic and inorganic geochemical techniques were applied to the basin's Cretaceous deposits with the aim of reconstructing the paleodepositional environment, assessing factors that triggered the input of organic matter, and providing a spatial overview of the organic matter accumulation in the basin based on outcrop samples. An alluvial fan-lacustrine-braided river system is inferred from the facies analysis of the stratigraphic sequence consisting of conglomerate, sandstone, siltstone, limestone, marlstone, and claystone. Bulk analysis of organic matter reveals that black shale and massive claystone are the main prospective petroleum source rocks in the basin. Inorganic geochemical analyses reveal the influence of anoxic conditions, moderate to high primary productivity, and low terrigenous inputs in organic matter enrichment. The formations rich in organic matter are predominantly concentrated in the western and eastern parts of the basin which may represent areas with depressions, characterized by high accommodation space. In terms of the regional context of the WCARS rift basins, typical hydrocarbon exploration in the BFB may target basal-conglomerate, sandstone beds situated directly above or/and interbedded with the Lower Cretaceous source rocks, and the Upper Cretaceous sandstone beds. Basement rocks (granite, granodiorite, and gneisses) and oil shale deposits may represent potential unconventional hydrocarbon exploration. The current integrated study provides an insight that should guide future hydrocarbon exploration campaigns in the basin.

Babouri-Figuil basin↗

USGS2025

Assessment of undiscovered conventional and continuous oil and gas resources in the Escondido, Olmos, and San Miguel Formations of the Western Gulf Basin Province, U.S. Gulf Coast region, 2023

Using a geology-based assessment methodology, the U.S. Geological Survey estimated undiscovered, technically recoverable mean resources of 5 million barrels of oil and 25 billion cubic feet of gas in conventional reservoirs and 361 million barrels of oil and 10,978 billion cubic feet of gas in continuous reservoirs in the Western Gulf Basin Province of the U.S. Gulf Coast region.

Texas↗

USGS2025

Evaluation of solid bitumen created from marine oil shale bituminite under hydrous and anhydrous pyrolysis conditions

To test the influence of environmental conditions on aromaticity of solid bitumen generated during petroleum generation, four organic-rich (26–36 wt% total organic carbon) oil shale samples collected from the Neoproterozoic–Lower Cambrian restricted marine Salt Range Formation in the upper Indus Basin, Pakistan, were pyrolyzed under hydrous and anhydrous conditions. Experiments used closed system batch reactors at subcritical water temperatures between 300 and 370°C for 72 h. Thermal conversion of bituminite in the Salt Range oil shales created a newly formed solid bitumen, similar to previous observations from experiments on the Eocene lacustrine Green River Formation Mahogany zone oil shale. Newly formed solid bitumen in the Salt Range Formation oil shales generally has higher reflectance (R o ) in hydrous residues compared to anhydrous experiments subjected to the same time-temperature conditions, also similar to prior observations. This finding supports the hypothesis that radical disproportionation is favored in the presence of hydrogen contributed by water, promoting aromatization in the solid bitumen residue with concomitant increased expulsion of saturated hydrocarbons. Indigenous solid bitumen (and vitrinite in a comparison sample) also shows higher reflectance values in hydrous versus anhydrous residues, indicating that additional aromatization in the presence of exogenous hydrogen occurs both in newly formed organic matter and in organic matter that is present throughout the experiment. Despite similarities in their bulk rock geochemical screening parameters, R o evolution shows different trajectories amongst the four Salt Range oil shales, suggesting as-yet undetermined differences in kinetic properties which are probably related to differences in a priori chemical composition. These results have implications for the use of solid bitumen reflectance (BR o ) as a thermal proxy, suggesting BR o values and appearance could vary as a function of the concentration of water. Variation in water concentration may be present at the reservoir or formation scale, but may also be present at a much finer scale in tight oil shales where permeability is several orders of magnitude lower than conventional reservoirs. Therefore, local variations in the presence of water potentially could explain substantial variation in BR o values and appearance in closely spaced source rock samples and even within an individual microscope field.

Journal of Analytical and Applied Pyrolysis↗

USGS2025

Reaction kinetics and accelerant effects of sulfides in early mature hydrocarbon generation using hydrous pyrolysis

Hydrocarbon generation in organic-rich sediments is influenced by the molecular organic composition and relative abundance of associated minerals. Certain mineral-derived elements act as catalysts and reaction intermediaries, facilitating early-stage hydrocarbon formation in potential source rocks. This study investigated the role of sulfur contributed from pyrite as an accelerant in thermal reaction, focusing on its effects on early maturation and consequent hydrocarbon generation from gilsonite (low-sulfur solid petroleum). Hydrous pyrolysis (HP) experiments were conducted on mixtures of gilsonite and pyrite in varying ratios (1:0.1, 1:0.5, 1:1, 1:2, and 1:10 w/w gilsonite:pyrite) at 320, 350, and 370 °C for 72 h. Untreated and thermally altered residues were analyzed using solid bitumen reflectance (BR o , %), total organic carbon (TOC) content, programmed temperature pyrolysis, scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), and X-ray diffraction (XRD) to evaluate the potential accelerant role of pyritic sulfur in hydrocarbon formation. The results show HP residues at 320 and 350 °C with greater pyrite concentrations had higher BR o , while reflectance values were similar in the 370 °C residues, regardless of pyrite concentration, suggesting enhanced reaction at lower thermal conditions. Increasing pyrite content systematically decreased hydrogen index (HI) values while increasing the transformation ratio (TR) and production index (PI), indicating enhanced conversion of organic matter to hydrocarbons with increasing pyrite concentrations. Gas yields increased with pyrite addition, particularly at 350 °C, confirming secondary cracking effects. However, gas production stabilized or declined at higher pyrite loadings (1:10), suggesting alternative reaction pathways such as coke formation. Our data indicate the presence of pyrite lowers the activation energy for thermal cracking, shifting peak experimental hydrocarbon generation temperatures downward by 20–30 °C, with the most pronounced accelerant effects observed at moderate pyrite concentrations (1:0.5 and 1:1). The thermodynamic framework reveals that pyrite stability is influenced by experimental conditions, with pyrrhotite formation favored in the presence of gilsonite due to reduced oxygen fugacity. Pyrite transformation to pyrrhotite, as observed through XRD, SEM-EDS, and predicted by thermodynamic data, further supports the accelerant role of S, as pyrrhotite exhibits a higher hydrogen transfer potential, promoting early oil generation. These findings highlight the importance of pyrite in modulating hydrocarbon generation pathways in organic-rich systems.

Journal of Analytical and Applied Pyrolysis↗

USGS2024

Atlas of microscopic images of biochar using reflected light microscopy in biochar characterization

Derived through the thermochemical conversion of biomass, biochar is a carbon-rich substance recognized for its significance in environmental applications and sustainable agriculture. As interest in its utilization continues to rise, it becomes crucial to comprehend how the source material and pyrolysis parameters influence the properties of biochar and, consequently, to research the suitability of various analytical methods for characterizing it. Despite the current utilization of numerous physical and chemical methods, the untapped potential of reflected light microscopy warrants further exploration. While a few recent studies suggest a correlation between certain microscopic characteristics and selected physical and chemical properties of biochar, the data are limited and difficult to compare. This is primarily due to variations in the types of original biomass used and lack of information about pyrolysis conditions. Moreover, because only a limited number of photographs taken under a reflected light microscope are publicly available to-date, it is difficult to evaluate morphological differences between various biochars and other organic materials such as inertinites from coal, charcoal, etc. To address limited availability of publicly available data, this “Atlas of Microscopic Images of Biochar” presents a collection of more than 300 images contributed by researchers from Poland, the United States, Canada, Australia, Brazil, and Denmark. These photomicrographs capture optical characteristics of a diverse array of biochar, demonstrating its unique morphological and structural features. This visual documentation can serve as a valuable resource for researchers, industry professionals, educators, and enthusiasts interested in investigating the complexities of biochar forms.

Indiana Journal of Earth Sciences↗

USGS2024

Spatial distribution of API gravity and gas/oil ratios for petroleum accumulations in Upper Cretaceous strata of the San Miguel, Olmos, and Escondido Formations of the south Texas Maverick Basin—Implications for petroleum migration and charge history

The Maverick Basin of south Texas is currently undergoing active exploration and production of gas and oil from tight sandstone reservoirs. The most productive tight sandstones in the basin are in the Upper Cretaceous San Miguel, Olmos, and Escondido Formations. These units are second only to the Eagle Ford Shale in terms of cumulative production volumes. The structural history of the Maverick Basin, from rifting to subsidence to exhumation, has had a profound effect on the characteristics of these reservoirs and the petroleum resources contained therein. This U.S. Geological Survey review of the production history of these strata reflects a recent shift from conventional production to horizontal drilling (unconventional) that exploits low permeability reservoirs in previously overlooked areas of existing oil and gas fields in southern Texas, typically outside of established field boundaries. To investigate the physical properties of the Maverick Basin hydrocarbon accumulations, this case study compiled American Petroleum Institute (API) gravity measurements and calculated cumulative gas/oil ratios (GOR) for thousands of producing wells from the San Miguel, Olmos, and Escondido Formations. Maps were generated from the compiled well production data to show the spatial heterogeneity of API gravity and GOR values for the three formations within the Maverick Basin and immediately outside the basin to the northeast. Within the Maverick Basin, the spatial patterns of API gravity values indicate lighter oils downdip towards the southern basin edge. GOR values indicative of wet and dry gases within the basin are seen interspersed, with values that correspond to black and heavy oils. Differences in the spatial patterns of the petroleum properties within the Maverick Basin are interpreted as effects of Eocene basin inversion caused by Laramide orogenic deformation, and the resulting reservoir exhumation of basin strata. East of the Maverick Basin, spatial distributions of API gravity and GOR values show progressively heavier oils updip to the northwest, grading to dry gases downdip to the southeast, which correlates to the oil and gas windows of the underlying Eagle Ford Shale. Correlation of API gravity and GOR values from the San Miguel, Olmos, and Escondido Formations with thermal maturity data from the Eagle Ford Shale suggests that the Eagle Ford Shale is the petroleum source, and that petroleum migration was approximately vertical for areas to the east of the Maverick Basin. The discontinuity of API gravity and GOR properties within the Maverick Basin implies a complex petroleum charge history, possibly involving the remigration of petroleum and the addition of petroleum from other source intervals in Mexico, to the southwest. Depressurization of exhumed, overpressured reservoirs of the San Miguel, Olmos, and Escondido Formations can explain the intermittent occurrence of gas production throughout the southern Maverick Basin by exsolution of gas from formation brines and the resulting dry gas flushing of hydrocarbon-charged reservoirs. The introduction of dry gas through flushing can, in turn, explain why the patterns of API gravity and GOR values are so dissimilar in the Maverick Basin. This process has implications for possible future production of unconventional resources from undiscovered tight-gas reservoirs in strata of the San Miguel, Olmos, and Escondido Formations, and a different approach to petroleum exploration may be needed in the Maverick Basin relative to exploration techniques applied in other basins within the northern Gulf of Mexico.

Texas↗

USGS2024

Novel insights about petroleum systems from source and reservoir rock characterization, Cretaceous Deposits, Babouri-Figuil Basin, Northern Cameroon

The Babouri-Figuil Basin (BFB) is a frontier basin for petroleum in Cameroon. It belongs to the series of Cretaceous rift basins of the West and Central Rift System (WCARS), the origin of which is related to the opening of the South Atlantic. Within the same rift system, commercial hydrocarbon accumulations have been discovered in Chad, Sudan, Niger and, more recently, in Nigeria (Gongola Basin). The study of the geology of the BFB just recently received considerable attention, mainly because of its presumed hydrocarbon potential. In the pursuit of researching possible petroleum systems in the BFB, the current study provides a first look into the characterization of source and reservoir rock and its integration into a 2D lithostratigraphic model. The study was solely based on outcrop samples. Black shale and massive claystone are good to excellent hydrocarbon source rocks [e.g., up to 38 wt% total organic carbon (TOC), up to 943 mg/g hydrogen index, up to 85 m thickness, up to 20–30 km lateral extension], with moderate to high values of extractable organic matter (e.g., >10,000 ppm). Calcareous claystone, on the other hand, are poor source rocks [e.g., <0.20 wt% TOC]. The samples are thermally immature, except for those located close to volcanic intrusion at Golombe that have reached the threshold for oil generation (Tmax >435 °C, production index >0.1). The petrographic analysis of sandstone revealed that they are fine-grained to coarse-grained, poorly to moderately sorted, texturally and compositionally immature to submature, subarkosic to arkosic arenites. The main diagenetic processes that affected sandstones are as follows: moderate to intense compaction characterized by the development of long, concavo-convex, and sutured contacts between grains; cementation through calcite, iron oxide, and quartz cements; alteration of mica and feldspar grains; partial to complete dissolution of feldspar, mica, amphibole grains, and calcite cement; and the replacement of feldspar and mica grains by clay minerals. Alteration and dissolution increase the porosity of sandstone through the creation of secondary pores. However, mechanical compaction through the development of a pseudomatrix and cementation as pore-filling materials have significantly reduced the quality of sandstone beds as conventional petroleum reservoirs. Hence, the best reservoir-quality sandstones in the basin are generally located in the upper portion of the basin in terms of its lithostratigraphic model. They are the cleanest sandstones with the smallest amount of cement and the lowest ductile grain content (pseudomatrix), with a thickness that varies from 3 m to 120 m and a lateral extension of 20 km. The lithostratigraphic model of the basin is characterized by an extensive lacustrine environment that provided a thick sequence of organic-rich formations; sand deposited as extensive reservoirs sandwiched between shale/claystone beds; the development of stratigraphic traps through lateral facies change; and the widespread deposition of lacustrine and floodplain claystone that provide regional seals. The similarities between the Babouri-Figuil Basin and proven petroleum systems in other WCARS rift basins suggest that the basin may host at least one petroleum system where actively generating source rocks are present.

Babouri-Figuil Basin↗

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↗

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

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↗

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

Evaluating aromatization of solid bitumen generated in the presence and absence of water: Implications for solid bitumen reflectance as a thermal proxy

Geological models for petroleum generation suggest thermal conversion of oil-prone sedimentary organic matter in the presence of water promotes increased liquid saturate yield, whereas absence of water causes formation of an aromatic, cross-linked solid bitumen residue. To test the influence of hydrogen from water, organic-rich (22 wt% total organic carbon , TOC) mudrock samples from the Eocene lacustrine Green River Formation Mahogany zone oil shale were pyrolyzed under hydrous and anhydrous conditions in closed system batch reactors at temperatures between 300 and 370 °C for 72 h. Pre- and post-pyrolysis samples were characterized using petrographic approaches including optical microscopy , reflectance, Raman spectroscopy , and scanning electron and transmission electron microscopy to quantify differences in relative appearance, abundance, and composition of solid bitumen newly generated during the pyrolysis experiments. Petrographic analyses were supplemented by geochemical screening measurements (TOC content and programmed temperature pyrolysis). Results show post-hydrous pyrolysis residues contain lower TOC, are comprised of solid bitumen with greater aromaticity , and have textures indicative of lower viscosities, relative to anhydrous residues from the same temperature pyrolysis conditions. These observations suggest solid bitumen forming from thermal conversion of oil-prone sedimentary organic matter under anhydrous conditions may be less aromatic, although more cross-linked, than solid bitumen forming under hydrous conditions at the same time-temperature combination. To explain these results, we suggest that a radical disproportionation mechanism is favored in the presence of hydrogen donated from water, and that this disproportionation promotes aromatization in the solid residue with concomitant expulsion of saturated hydrocarbons.

International Journal of Coal Geology↗

USGS2022

Identification of thermal maturity-relevant organic matter in Shale Working Group Report 2021

The Identification of Thermal Maturity-Relevant Organic Matter in Shale Working Group of the ICCP was established in 2008 to provide guidelines for identifying and measuring the reflectance of the population of dispersed organic matter that is relevant to thermal maturity determination. Information products published by the working group include ASTM D7708 Standard Test Method for Microscopical Determination of the Reflectance of Vitrinite Dispersed in Sedimentary Rocks (ASTM, 2014) and two interlaboratory studies (ILS) to determine precision statistics for this ASTM test method (Hackley et al., 2015, 2020). Poor reproducibility of solid bitumen and vitrinite reflectance measurements in the second ILS (Hackley et al., 2020) suggested that further work is required to standardize the identification of thermal maturity-relevant dispersed organic matter for reproducible reflectance measurements. Thus, at the 2019 ICCP meeting in The Hague, Netherlands, the working group decided to pursue additional ILS via image-based approaches to improve reproducibility.

ICCP News↗

USGS2021

New insights into organic matter accumulation from high-resolution geochemical analysis of a black shale: Middle and Upper Devonian Horn River Group, Canada

Organic matter (OM) accumulation in organic matter-rich mudstones, or black shales, is generally recognized to be controlled by combinations of bioproductivity, preservation, and dilution. However, specific triggers of OM deposition in these formations are commonly difficult to identify with geochemical proxies, in part because of feedbacks that cause geochemical proxies for these controls to vary synchronously. This apparent synchronicity is partly a function of sample spacing, commonly at decimeter to meter intervals, which may represent longer periods of time than is required for the development of feedbacks. Higher resolution data sets may be required to fully interpret OM accumulation. This study applies a novel combination of technologies to develop a high-resolution geochemical data set, integrating energy-dispersive X-ray fluorescence (EDXRF) and infrared imagery analyses, to record proxies for redox conditions, bioproductivity, and clastic and carbonate dilution in millimeter-resolution profiles of 133 core slabs from the Middle and Upper Devonian Horn River shale in the Western Canada Sedimentary Basin, which provides decadal-scale temporal resolution. A comparison to a more coarsely sampled data set from the same core results in substantially different interpretations of variations in bioproductivity, redox, and dilution proxies. Stratigraphic distributions of organic matter accumulation patterns (bioproductivity-control, siliciclastic/carbonate-dilution, and redox conditions-control) show that organic enrichment events were highly varied during deposition of the shale and were closely related to second- and third-order sea-level changes. High-resolution profiles indicate that bioproductivity was the predominant trigger for organic matter accumulation in a second-order highstand, particularly during deposition of third-order transgressive systems tracts. Organic matter accumulation was largely controlled by dilution from either carbonate or clastic sediments in a second-order lowstand. Bioproductivity-redox feedbacks developed on timescales of decades to centuries.

British Columbia, Northwest Territories↗

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↗

USGS2021

Hydrous pyrolysis of New Albany Shale: A study examining maturation changes and porosity development

The characterization of nanoscale organic structures has improved our understanding of porosity development within source-rock reservoirs, but research linking organic porosity evolution to thermal maturity has generated conflicting results. To better understand this connection, an immature (0.25% solid bitumen reflectance; BR o ) sample of the New Albany Shale was used in four isothermal hydrous pyrolysis (HP) experiment sequences at 300°, 320°, 340°, and 370°C, with residues collected periodically for a maximum of 103 days. The HP residues, along with the original immature sample and two naturally matured (1.49 and 1.56% BR o ) New Albany Shale samples were analyzed for organic petrology, total organic carbon (TOC) content, and organic porosity evaluation using correlative light and electron microscopy (CLEM). All of the HP series increased in thermal maturity with increasing duration of pyrolysis, though reflectance for each series plateaued within 25 days of maturation. Initially, TOC in the HP residues decreases (from 14.24 wt. %) with increasing thermal maturity until ∼1.0% BR o where TOC remains at ∼9–10 wt. % for all remaining residues. Qualitative CLEM observations within the 50–100 day 300° and 340°C HP sequences (0.95–1.70% BR o ), and the naturally matured samples, develop organic porosity in smaller (<5 μm in diameter), void-filling solid bitumen that occurs in spaces between clays and other fine-grained minerals. The 370°C HP residues developed significant organic porosity, relative to the other HP temperature series in all solid bitumen accumulations regardless of size. Overall, the study indicates that temperature and duration of artificial maturation play an important role in the abundance of pores in the HP residues. This work expands on our understanding of the conditions needed for the generation and development of organic porosity in the New Albany Shale and potentially in other marine source-rock petroleum systems.

Illinois, Indiana↗

USGS2020

Nanoscale molecular composition of solid bitumen from the Eagle Ford Group across a natural thermal maturity gradient

Microscopic solid bitumen is a petrographically defined secondary organic matter residue produced during petroleum generation and subsequent oil transformation. The presence of solid bitumen impacts many reservoir properties including porosity, permeability, and hydrocarbon generation and storage, among others. Furthermore, solid bitumen reflectance is an important parameter for assessing the thermal maturity of formations with little to no vitrinite. While the molecular composition of solid bitumen will strongly impact associated parameters such as the development of organic matter porosity, hydrocarbon generation, and optical reflectance, assessing the molecular composition of solid bitumen in situ within shale reservoirs can be challenging due to the small grain sizes (often ≤1 μm in diameter) and the inherent heterogeneity of shale formations. Here we employ the recently developed atomic force microscopy based infrared spectroscopy (AFM-IR) technique to investigate solid bitumen molecular composition in situ within shale samples from the Late Cretaceous Eagle Ford Group. These samples possess sulfur-rich type II kerogens that span a natural thermal maturity gradient from early oil generation to the dry gas window. The application of AFM-IR allows for the rapid collection of thousands of compositional measurements from solid bitumen with ∼50 nm resolution. Our results indicate that (i) solid bitumen from the lower Eagle Ford displays both intra- and intergranular variation in the relative abundance of CH 2 , C═C, and C═O moieties present; (ii) this molecular variation tends to, but does not always, decrease with an increase in thermal maturity; and (iii) the solid bitumen composition between samples, from an atomic ratio perspective, is more similar than analysis of bulk kerogen isolates would indicate. These findings are discussed with perspective toward understanding the impact of thermal stress on the composition of secondary organic matter within the Eagle Ford Shale and highlight the growing awareness that organic matter heterogeneity within petroliferous mudrocks extends down to the nanoscale regime.

Energy and Fuels↗

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↗