Geology topics

Brett J. Valentine

Publications and source records attributed to Brett J. Valentine.

At least 19 recordsLinked to original sources

USGS2025

Chemostratigraphy of the Cretaceous Hue Shale in Arctic Alaska: Exploring paleoceanographic controls on trace element enrichment, organic matter accumulation, and source-rock evolution

We document chemostratigraphy in an outcrop of late Albian to early Campanian (∼103–82 Ma) marine source rocks to better understand paleoenvironmental controls on trace element (TE) enrichment and organic matter accumulation in the distal Colville foreland basin of Arctic Alaska and how those drivers are linked to arc volcanism and successions of Cretaceous oceanographic and climatic biogeochemical events. This unique, 113-m-thick section of Cretaceous Hue Shale deposited during a series of previously undocumented Arctic Cretaceous oceanic anoxic events (Lease et al., 2024) is the only known exposure of thermally immature (0.48–0.52% R o , random vitrinite reflectance) Hue Shale in Arctic Alaska. Strata comprise mainly clay-rich mudstone with elevated total organic carbon (TOC) and hydrogen index values reaching 26.3 wt% (mean = 7.5 wt%) and 689 mg hydrocarbon (HC)/g TOC (mean = 385 mg HC/g TOC), respectively. Maceral composition consists predominantly of fluorescent amorphous organic matter, with abundant brightly fluorescent alginite, including Tasmanites , acritarchs, and Leiosphaeridia . Discrete layers of volcanic ash (preserved as bentonite) are present throughout the section and provide quantitative age control based on U–Pb dates. Chemostratigraphic trends are investigated to advance our understanding of local oceanographic conditions and controls on stratigraphic and temporal heterogeneity of Brookian source rocks. Concurrent sedimentary enrichment in Mo, U, V, Pb, and Cu across the Albian–Cenomanian boundary of the exposed basal gamma-ray zone, may reflect anoxic to euxinic benthic redox conditions favoring organic matter accumulation and preservation. Fluctuating degrees of anoxia-euxinia are inferred throughout the overlying Hue Shale succession, reflected by varying patterns of TE enrichment and TE–TOC covariation. Elevated C org /P molar ratios (>250) across most of the section, with several values exceeding 690, signify that enhanced biological productivity is sustained throughout deposition. Enhanced productivity, recorded by both C org /P and excess Ba, also parallels increases in source rock richness (elevated TOC and S 2 values) during the late Albian–early Cenomanian and late Cenomanian – Turonian. Enhanced productivity and variations in oceanic circulation/stratification likely both drove changes in benthic redox conditions that favored organic carbon accumulation and preservation. Increased continental arc volcanism (e.g., Okhotsk–Chukotka volcanic belt) and High Arctic Large Igneous Province magmatic eruptions throughout the Cretaceous, inferred to have influenced nutrient cycling and local aqueous nutrient availability, also have been invoked as potential drivers of organic carbon burial and source-rock development across the sedimentary sequence. Results presented here document the organic-rich and oil-prone source-rock quality of the Hue Shale in the distal part of the Colville foreland basin and bolster the potential for a Cretaceous petroleum system beneath the eastern North Slope.

Alaska↗

USGS2025

Relating systematic molecular and textural properties of graptolite pyrolyzed via gold tube hydrous pyrolysis: Implications for thermal proxies in lower Paleozoic marine shales

A series of gold tube pyrolysis experiments (72 h, 300–550 °C, 50 MPa) conducted on a graptolite-rich lower Paleozoic marine shale generated pyrolysis residues for a comprehensive evaluation of the molecular and structural variability of three types of graptolite periderm. Organic petrology, Raman spectroscopy, and field emission scanning electron microscopy (FE-SEM) with energy dispersive spectroscopy (EDS) were combined to evaluate the thermal evolution process. The three types of graptolite periderm, namely granular, non-granular, and nodular graptolite, were analyzed by Raman spectroscopy wherein point measurements were obtained after the maceral was identified and the location verified by organic petrology. Distinct thermal evolution pathways among non-granular, granular, and nodular graptolite periderms were recorded. The evolution patterns of the Raman parameters, particularly D1 and G bands, highlight the differences in geochemical composition of the graptolite periderm types and the alteration of molecular structure with increasing thermal maturity. Raman parameters D1 (position of the D1 peak), G-FWHM (full width at half maximum of the G peak), and ratios D1-FWHM/G-FWHM (full width at half maximum of the D1 peak ratioed to G-FWHM) and A D1 /A G (ratio of D1 and G peak intensities) showed effectiveness in assessing thermal maturity. Bireflectance with increasing gold tube pyrolysis temperature followed a hierarchy: non-granular > granular > nodular, reflecting different molecular alignment intensities. Qualitative FE-SEM evaluation showed that fine-grained mineral inclusions (primarily Fe-sulfide as determined via EDS) were associated with the graptolite populations, with granular graptolite containing greater amounts of coarser-grained (e.g., ∼300–1400 nm) mineral inclusions relative to non-granular and nodular graptolite, which contain finer-grained (e.g., ∼100–200 nm) inclusions difficult to resolve with optical microscopy. These findings are investigated to highlight the mechanisms that drive organic matter evolution within graptolite during thermal maturation, as well as to explore some of the limitations of using spectroscopic parameters as thermal maturity proxies.

International Journal of Coal Geology↗

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↗

USGS2024

Insights on using solid bitumen reflectance as a thermal maturity proxy in the Bakken Formation, Williston Basin, USA

To further refine the use of solid bitumen reflectance (BR o in %) as a measurement of thermal maturity in source-rock reservoirs, we examined its relationship to other thermal proxies in the Bakken Formation. Comparisons included criteria from programmed temperature pyrolysis, gas chromatography (GC), and Fourier transform infrared (FTIR) spectroscopy. Thirty-two organic-rich samples from the lower and upper shale members of the Devonian–Lower Carboniferous Bakken Formation were collected from eight cores across the Williston Basin, USA, at depths (∼7575–11,330 ft) representing immature through post peak oil/early condensate thermal maturity conditions based on proximity to current hydrocarbon production. Unmodified BR o values were correlated to programmed temperature pyrolysis parameters (hydrogen index, production index, and T max ), normal hydrocarbon and isoprenoid analysis of extractable organic matter (pristane/ n -C 17 and phytane/ n -C 18 ) from GC analysis, and peak ratios from FTIR spectroscopy (branching ratio and A -factor). Strong correlations between unmodified BR o values (not corrected to a vitrinite reflectance equivalent, VR e ) and other thermal proxies suggest that BR o can be used as a direct thermal proxy in marine Paleozoic source-rock reservoirs where vitrinite is rare or absent. Moreover, an apparent overestimation of VR e at the lowest thermal maturity investigated herein may argue against the application of BR o conversion to VR e in the Bakken Formation. Solvent extraction caused a consistent decrease in BR o when average post-extraction values from a given well were compared to BR o prior to extraction, although the decrease in mean value was not statistically significant. These results are discussed in the context of advocating for the use of unmodified BR o values as a best practice for thermal maturity determination in Paleozoic marine source-rock reservoirs.

Montana, North Dakota↗

USGS2024

Cathodoluminescence differentiates sedimentary organic matter types

High-resolution scanning electron microscopy (SEM) visualization of sedimentary organic matter is widely utilized in the geosciences for evaluating microscale rock properties relevant to depositional environment, diagenesis, and the processes of fluid generation, transport, and storage. However, despite thousands of studies which have incorporated SEM methods, the inability of SEM to differentiate sedimentary organic matter types has hampered the pace of scientific advancement. In this study, we show that SEM-cathodoluminescence (CL) properties can be used to identify and characterize sedimentary organic matter at low thermal maturity conditions. Eleven varied mudstone samples with a broad array of sedimentary organic matter types, ranging from the Paleoproterozoic to Eocene in age, were investigated. Sedimentary organic matter fluorescence intensity and CL intensity showed an almost one-to-one correspondence, with certain exceptions in three samples potentially related to radiolytic alteration. Therefore, because CL emission can be used as a proxy for fluorescence emission from sedimentary organic matter, CL emission during SEM visualization can be used to differentiate fluorescent from non-fluorescent sedimentary organic matter. This result will allow CL to be used as a visual means to quickly differentiate sedimentary organic matter types without employing correlative optical microscopy and could be widely and rapidly adapted for SEM-based studies in the geosciences.

Scientific Reports↗

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

Scanning electron microscopic evaluation of broad ion beam milling effects to sedimentary organic matter: Sputter-induced artifacts or naturally occurring porosity?

Research examining organic-matter hosted porosity has significantly increased during the last decade due to greater focus on understanding hydrocarbon migration and storage in source-rock reservoirs, and technological advances in scanning electron microscopy (SEM) capabilities. The examination of nanometer-scale organic-matter hosted porosity by SEM requires the preparation of exceptionally flat geologic samples beyond the abilities of traditional mechanical polishing, which can deform or otherwise obscure organic surfaces. To meet this demand, broad ion beam (BIB) milling was introduced as a sample preparation technique for SEM petrographic analysis of geologic samples. As with any sample preparation technique, there can be unintended consequences. In this study, we examined the development of nanometer-scale sputter-induced voids caused by BIB milling of thermoset plastic binder material [poly(methyl methacrylate), PMMA] used for the mounting of geologic samples, and artifact sputter-induced voids in the organic matter of Green River Formation and Kimmeridge Clay Formation source rocks. Development of artifact sputter-induced voids was evaluated in relation to variations in the slope of the sample examination surface (0.0–4.9% slope), effectively varying the angle of ion incidence. The results indicate that only minor variations in the angle of ion incidence can generate sputter-induced voids in both PMMA (10.0–386.2 nm diameter sputter-induced voids) and sample sedimentary organic matter (solid bitumen; 12.2–103.6 nm diameter sputter-induced voids). Overall, average artifact pore diameters increased with increasing ion incidence angle within PMMA. Although sputter-induced voids within solid bitumen in the Green River Formation sample were only found in limited extent, the size of these void artifacts falls within the same size range as naturally occurring meso-macroporosity. That is, the pore-like artifacts could easily be misconstrued as naturally developed organic porosity, which is a major concern for SEM-based porosity evaluation methods. This study describes the factors that contribute to the creation of artifact sputter-induced voids, their distinguishing characteristics, and best practices for avoiding the creation of ion-induced artifacts.

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

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

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

International Journal of Coal Geology↗

USGS2022

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

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

Wyoming↗

USGS2022

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

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

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

International Journal of Coal Geology↗

USGS2021

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↗

USGS2021

Organic petrographic evaluation of carbonaceous material in sediments of the Kinnickinnic River, Milwaukee, WI, U.S.A.

This study examines the use of organic petrology techniques to quantify the amount of coal and carbonaceous combustion by-products (i.e., coke, coal tar/pitch, cenospheres) in sediments taken from the Kinnickinnic River adjacent to the former site of the Milwaukee Solvay Coke and Gas Company. These materials are of concern as contaminants like polycyclic aromatic hydrocarbons (PAHs) are known to readily adsorb to coal and combustion byproducts. Kinnickinnic River sediment samples (n = 36) ranging in depth (1–11 ft.) were collected from eight core locations to quantify and characterize carbonaceous material in the sediments. To determine the amount (vol%) of organic particulates, U.S. Geological Survey (USGS) modified the existing ASTM D2799 using the following categories: coal, coke, coal tar/pitch, inertinite organics, plant material, cenospheres, and mineral matter. Coal fragments were subdivided by rank using vitrinite reflectance (R o , %) and organic components were further subdivided into the size fractions of coarse (250–1000 μm), fine (63–250 μm), and very fine (<63 μm). Of the 36 samples analyzed, concentrations of coal, coke, and coal tar/pitch ranged from 0 to 18.2 vol%, 0 to 32.0 vol%, and 0 to 2.6 vol%, respectively, with the highest concentrations occurring near point sources (e.g. discharge pipe and coal unloading operations). Samples that were furthest upstream and downstream from the Solvay site exhibited a marked decrease in particulate organics, with exception of one upstream location which had 19.8 vol% coke. Overall, the modified ASTM method provided a means to quantify the abundance of carbonaceous material present in the sediments. Petrography and total PAH concentrations did not provide a clear correlation to organic matter type or size fraction but the samples with the highest vol% organic matter in each core generally corresponded to the sample with the highest bulk PAH content.

Wisconsin↗

USGS2020

Investigating the effects of broad ion beam milling to sedimentary organic matter: Surface flattening or heat-induced aromatization and condensation?

Previous work has proposed transfer of kinetic heat energy from low-energy broad ion beam (BIB) milling causes thermal alteration of sedimentary organic matter, resulting in increases of organic matter reflectance. Whereas, other studies have suggested the organic matter reflectance increase from BIB milling is due to decreased surface roughness. To test if reflectance increases to sedimentary organic matter (vitrinite) caused by BIB milling were related to molecular aromatization and condensation, Raman and Fourier transform infrared (FTIR) spectroscopies were used to evaluate potential compositional changes in the same vitrinite locations pre- and post-BIB milling. The same locations also were examined by atomic force microscopy (AFM) to determine topographic changes caused by BIB milling (as quantified by the areal root-mean-square roughness parameter S q ). Samples consisted of four medium volatile bituminous coals. A non-aggressive BIB milling approach was used with conditions of 5 min, 4 keV, 15°incline, 360° rotation at 25 rpm and 100% focus (1.5 kV discharge; ∼100 μA). This gentle BIB milling caused vitrinite reflectance (VR o ) increases of 12 to 36% of the original values determined optically before milling (average 26% increase). When molecular proxies from FTIR (A- and C-factor, branching ratio) were plotted against each other for the same vitrinite locations pre- and post-milling, mean data points for each sample generally lie within error of a 1:1 line. Likewise, mean Raman thermal proxy [full-width half maximum of G-band (G-FWHM), Raman band separation (RBS) and D1/G band intensity ratio] values were similar for pre- and post-milled locations, also plotting within error of a 1:1 line. AFM confirms the majority (24 of 36) of pre- and post-ion milled surface pairs were smoother (lower S q values) after BIB milling. These results are interpreted to indicate VR o increase induced by the gentle BIB milling conditions used in this study is an effect of decreased diffuse reflectance due to flatter surfaces, causing more photons to reflect directly back to the detector. Little evidence was observed for molecular aromatization and condensation of vitrinite molecules following BIB milling (with the conditions used). The presence of milling-induced artifacts, including differential milling effects dependent on location and the development of self-organized patterned structures, indicate much work remains in standardization of BIB milling before its promulgation as a routine sample preparation technique for organic petrography. These results provide better understanding of anthropogenic-induced changes to geological samples caused by the now widespread adoption of BIB milling as a disruptive innovation in sample preparation.

Fuel↗

USGS2020

Organic petrography of Leonardian (Wolfcamp A) mudrocks and carbonates, Midland Basin, Texas: The fate of oil-prone sedimentary organic matter in the oil window

To better understand evolution of oil-prone sedimentary organic matter to petroleum and expulsion from source rock, we evaluated organic petrographic features of Leonardian Wolfcamp A repetitive siliceous and calcareous mudrock and fine-grained carbonate lithofacies cycles occurring in the R. Ricker #1 core from Reagan County, Midland Basin, Texas. The objectives of the petrographic investigation were to estimate thermal maturity, identify organic matter types and abundances, and identify the presence or absence of migrated hydrocarbons in organic-lean carbonate layers. An integrated analytical program included geochemical screening [total organic carbon (TOC) content by LECO, programmed pyrolysis by hydrocarbon analyzer with kinetics (HAWK) including analysis of solvent-extracted samples], X-ray diffraction mineralogy, organic petrography, scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) including correlative light and electron microscopy (CLEM), and micro-Fourier transform infrared spectroscopy (μ-FTIR) analyses of solid bitumen. The data indicate all samples are early to middle oil window thermal maturity with solid bitumen reflectance (BR o ) values of 0.55–0.86% and T max of 440–455 °C. Organic matter is predominantly solid bitumen (as identified by optical microscopy) in all lithofacies with minor contributions from inertinite. Solid bitumen abundance decreases from siliceous mudrock (TOC >3.0 wt%) to calcareous mudrock (TOC 1.0 to 3.0 wt%) to fine-grained carbonate (TOC <1.0 wt%) lithofacies. Interpretations of petrographic data suggest siliceous and calcareous mudrocks are source rock lithofacies and contain solid bitumen (with petroleum generation potential) that is residual (what remains) from conversion of an original Type II sedimentary organic matter. In turn, fine-grained carbonates are interpreted as reservoir lithofacies which contained little or no original oil-prone sedimentary organic matter and at present-day contain only a minor component of migrated solid petroleum sourced from adjacent siliceous and calcareous mudrock lithofacies. This work helps to document petroleum generation and migration processes, improve unconventional reservoir characterization and better define areas of oil window thermal maturity in an area critical to United States hydrocarbon production.

Texas↗

USGS2020

Testing reproducibility of vitrinite and solid bitumen reflectance measurements in North American unconventional source-rock reservoir petroleum systems

An interlaboratory study (ILS) was conducted to test reproducibility of vitrinite and solid bitumen reflectance measurements in six mudrock samples from United States unconventional source-rock reservoir petroleum systems. Samples selected from the Marcellus, Haynesville, Eagle Ford, Barnett, Bakken and Woodford are representative of resource plays currently under exploitation in North America. All samples are from marine depositional environments, are thermally mature (T max >445 °C) and have moderate to high organic matter content (2.9–11.6 wt% TOC). Their organic matter is dominated by solid bitumen, which contains intraparticle nano-porosity. Visual evaluation of organic nano-porosity (pore sizes < 100 nm) via SEM suggests that intraparticle organic nano-pores are most abundant in dry gas maturity samples and less abundant at lower wet gas/condensate and peak oil maturities. Samples were distributed to ILS participants in forty laboratories in the Americas, Europe, Africa and Australia; thirty-seven independent sets of results were received. Mean vitrinite reflectance (VR o ) values from all ILS participants range from 0.90 to 1.83% whereas mean solid bitumen reflectance (BR o ) values range from 0.85 to 2.04% (no outlying values excluded), confirming the thermally mature nature of all six samples. Using multiple statistical approaches to eliminate outlying values, we evaluated reproducibility limit R, the maximum difference between valid mean reflectance results obtained on the same sample by different operators in different laboratories using different instruments. Removal of outlying values where the individual signed multiple of standard deviation was >1.0 produced lowest R values, generally ≤0.5% (absolute reflectance), similar to a prior ILS for similar samples. Other traditional approaches to outlier removal (outside mean ± 1.5*interquartile range and outside F10 to F90 percentile range) also produced similar R values. Standard deviation values < 0.15*(VR o or BR o ) reduce R and should be a requirement of dispersed organic matter reflectance analysis. After outlier removal, R values were 0.1%–0.2% for peak oil thermal maturity, about 0.3% for wet gas/condensate maturity and 0.4%–0.5% for dry gas maturity. That is, these R values represent the uncertainty (in absolute reflectance) that users of vitrinite and solid bitumen reflectance data should assign to any one individual reported mean reflectance value from a similar thermal maturity mudrock sample. R values of this magnitude indicate a need for further standardization of reflectance measurement of dispersed organic matter. Furthermore, these R values quantify realistic interlaboratory measurement dispersion for a difficult but critically important analytical technique necessary for thermal maturity determination in the source-rock reservoirs of unconventional petroleum systems.

Marine and Petroleum Geology↗