Geology topics

Aaron M. Jubb

Publications and source records attributed to Aaron M. Jubb.

At least 19 recordsLinked to original sources

USGS2026

Microfocus X-ray computed tomography to evaluate ostracode shell density and other metrics for monitoring ocean acidification in the Arctic Ocean

Ocean acidification (OA) poses a significant threat to the ability of marine calcifying organisms—such as mollusks, corals, crustaceans, and plankton—to form and maintain their calcium carbonate-based shells. While some species show greater sensitivity to OA than others, the impacts on benthic marine calcifiers remain inadequately understood. This study investigates the shell density, weight, and thickness of the ostracode species Paracyprideis pseudopunctillata (subphylum Crustacea), which inhabits the continental shelves of the Arctic Ocean. Using microfocus X-ray computed tomography (microXCT) scans, we generated detailed morphometric measurements of specimens collected from both surface and down-core sediment samples to assess variations in shell properties over time. To our knowledge, this is the first study to examine the natural variability of ostracode shell characteristics in a specific region over an extended time period. For each specimen, we calculated a CT number, an index of relative calcium carbonate density, using a previously published equation. Our findings show that most living specimens of P. pseudopunctillata in the Beaufort Sea showed no overt signs of OA-related shell compromise or degradation. Shell density remained consistent between 1969 and 2018 CE, with consistent CT numbers suggesting that corrosive bottom waters are not a persistent feature in this area of the Beaufort Sea continental shelf. This is supported by a timeseries of discrete pH and carbonate saturation measurements. To help quantify diagenetic impacts on ostracode shells, we compared this calibration dataset with measurements of well-preserved adult specimens from downcore intervals of a box core (MR22, MT1, 1-29 cm) and a multicore (HLY1302 MC29, 25-35 cm), both collected from the same location, representing 2018 to 1955 CE and 1953 to 1925 CE, respectively. The CT numbers from these specimens were also consistent, which confirmed the preservation state of most specimens. However, several specimens had low CT numbers, and these shells show surficial evidence of post-mortem diagenesis. We aimed to quantify the extent of diagenesis, which has important implications for paleoenvironmental reconstructions. These findings provide important baseline data for understanding the variability of modern ostracode shell density of fossil and alive-collected specimens.

Deep Sea Research Part II: Topical Studies in Ocea↗

USGS2026

Neutron scattering reveals fractionation of natural gas mixtures in unconventional petroleum reservoir pores: Perspectives on energy resource recovery and storage

In unconventional petroleum reservoirs hydrocarbon fluids are hosted by both mineral and organic matter pores. These pores can have diameters that range from microns to less than a single nanometer and, for unconventional reservoirs, there is evidence that small pores ( <20 nm diameter) may constitute a large proportion of the available space. Understanding subsurface volumes and how fluids behave in them can be helpful for predicting hydrocarbon production and storage in the subsurface. One area with knowledge gaps regarding hydrocarbon behavior in small pores is the possibility for mixtures to fractionate (i.e., unmix) based on pore size or pore type. Mixture fractionation as a function of pore size could impact recovery of hydrocarbons, drive compositional shifts during production, and limit fluid storage within candidate reservoirs. To investigate natural gas fractionation in small geologic pores, we applied total neutron scattering to probe methane-ethane mixtures at reservoir pressures (up to ≈30 MPa) and temperature (60°C) within a sample from the Upper Cretaceous Niobrara Formation. Neutron scattering data reveal only minor fractionation occurs between methane and ethane in 20-nm diameter sample mesopores. Increased fractionation is observed for sample micropores, with up to 72% (±1% at 1-sigma) methane found in 2 nm diameter pores following injection of a 50%-50% methane-ethane mixture. These data provide rarely available direct experimental observations of hydrocarbon mixture behavior under nanoconfinement in a sample from an important unconventional petroleum reservoir. Our results are discussed in the context of evaluating hydrocarbon resources in unconventional reservoir meso- and micropores, reconciling observed gas composition changes during production, and more broadly, understanding subsurface pore volumes within an energy storage framework.

Fuel↗

USGS2026

Geochemical geodatabase of sedimentary strata (coal, coal-adjacent rocks, tuffaceous oil shale, phosphate-rich rocks) and produced water in the Uinta region, Utah and Colorado

The Geochemical Geodatabase of Sedimentary Strata (Coal, Coal-adjacent Rocks, Tuffaceous Oil Shale, Phosphate-rich Rocks) and Produced Water in the Uinta Region, Utah and Colorado, consists of compiled datasets acquired as part of the Carbon Ore, Rare Earth, and Critical Mineral (CORE-CM) Uinta Region assessment funded by the U.S. Department of Energy (DEFE0032046, 2021–2024; Birgenheier et al., 2024). The CORE-CM assessment focused on providing comprehensive geological and geochemical characterization of current and prospective sedimentary-hosted resources including coal, oil shale, phosphatic limestone, and produced water from oil and gas targets present in eastern Utah and northwestern Colorado (Figure 1). This Data Series includes a geodatabase that consists of analytical geochemical data collected September 2021 through December 2024 via portable X-ray fluorescence (pXRF), and laboratory measured analyses produced by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectroscopy (ICP-OES). The coal-related geochemical data are derived primarily from the Cretaceous Blackhawk Formation and Ferron Sandstone of Utah, and the Mesaverde Group of Colorado. Additional non-coal resources assessed include oil shale-bearing strata of the Eocene upper Green River Formation (Utah and Colorado), phosphate-rich limestone of the Permian Park City Formation (Utah) and produced water from oil and gas-bearing strata of the Eocene Green River and Wasatch Formations (Uinta Basin) and the Pennsylvanian Paradox Formation (Paradox Basin) (Table 1). The CORE-CM assessment included a wide range of lithologies present in the coal, oil shale, and phosphate geologic resource systems whether or not the specific lithology has current economic value. Geochemical analyses of produced water from oil and gas wells focused on current and emerging hydrocarbon targets in the central Uinta Basin and northern Paradox Basin. A total of 13,092 geochemical analyses from these geologic systems is provided in the included geodatabase. A series of coal quality data (e.g., composition and maceral analyses) is also included in the database and was digitized from archived coal samples from the Utah Geological Survey (Appendix A).

Colorado, Utah↗

USGS2026

Per- and polyfluoroalkyl substances in waters associated with oil and gas development in the Denver Basin

Use of per- and polyfluoroalkyl substances (PFAS) in the petroleum industry could be a cause for concern due to the large volumes of produced water (PW) generated during oil and gas extraction, the reuse of these wastes in water-stressed regions, and adverse health outcomes related to PFAS exposures. However, PW PFAS characterization is nearly absent in the literature, and hydraulic fracturing (HF) chemical disclosures often omit the identities of additives as proprietary. Here we evaluate PFAS in PW samples from three petroleum wells in the Denver Basin during their first year of production. Total concentrations of targeted PFAS (Σ 40 PFAS) were < 35 ng/L in PW samples, with short-chain PFAS like perfluorobutanoic acid persisting throughout the sampled duration. Analysis of freshwater inputs for hydraulic fracturing (Σ 40 PFAS ~ 113 ng/L) and mixed fracture fluid (Σ 40 PFAS ~ 69 ng/L) indicated much of the targeted PFAS content was derived from the input water, and not from HF additives, however samples subjected to oxidation indicated the presence of PFAS precursors that would not be detected by targeted analysis. This study highlights that while PFAS content is low in the studied PWs, the potential for redistribution of PFAS in the environment may be a consideration for reuse applications.

Colorado, Nebraska, Wyoming↗

USGS2026

Release and recapture: Limited carbon mobilization in sediment adjacent to Central Atlantic Magmatic Province sills, Florida, USA

Large Igneous Provinces (LIPs) are associated with dramatic changes to the Earth system; their rapid release of carbon may initiate catastrophic climatic changes causing mass extinction. This carbon release is often associated with volcanic emissions, yet metamorphic carbon production is poorly constrained. Metamorphic carbon devolatilization occurs as intrusions interact with host sediment, potentially releasing substantial sedimentary carbon. While this process has been modeled, few studies use an observational approach. Here, we apply geochemical analysis, petrographic analysis, Raman spectroscopy, vitrinite reflectance, and thermodynamic modeling to understand carbon devolatilization in sediment adjacent to Central Atlantic Magmatic Province basaltic intrusions using two boreholes that penetrate the Florida basement. We find geochemical and petrographic evidence for CO 2 release from carbonates below a 10 m thick sill, with upward fluid transport and recapture of mobilized CO 2 at the top of the sill. Ultimately, we estimate 220 mols/m 2 to 9900 mols/m 2 of carbon were mobilized from sedimentary carbonate. Uncertainties in the extent of re‑carbonation suggest that anywhere from 0 mols/m 2 to 7100 mols/m 2 may have escaped to the surface. We find little evidence of organic carbon mobility, due partly to the increased activity of CO 2 from carbonate devolatilization. Discrepancies between measured temperatures and 1D thermal models suggest complexities in heat transport through aqueous pore fluid flow and short (hundred to thousand year) heating timescales. These results highlight that further field-based study can help clarify the roles that heating timescales, fluid flow, sediment chemistry, and other factors play in releasing and capturing carbon during LIP emplacement.

Florida↗

USGS2026

Lithium brine potential of North Dakota: Results from the 2025 sampling program

Lithium (Li), classified as a critical mineral and key in energy storage applications because of its high energy density, faces unprecedented demand. This has driven interest in unconventional sources of Li, especially brines from sedimentary basins. Accordingly, the spatial distribution of basinal brinehosted Li resources across North America is becoming better defined, including the Williston Basin underlying Saskatchewan, Canada. This has led to growing investment and exploration by industry throughout the 2020s; however, despite this interest, the Li potential of basinal brines of the Williston Basin in North Dakota remain underexplored. This work presents the results from the 2025 joint brine sampling campaign between the North Dakota Geological Survey, the United States Geological Survey (USGS), and The University of Texas at Austin. Twenty-seven fluid samples were collected from producing oil and water source wells from eight stratigraphic intervals across western North Dakota and analyzed for major cation and anion concentrations. Similar to southeastern Saskatchewan, the highest Li concentrations were identified in the Devonian Duperow Formation, with concentrations up to 179 mg/L being observed in a well commingled between the Duperow and Red River Formations. Some samples from the overlying Birdbear Formation exceeded 75 mg/L, whereas Li concentrations were lower in the Madison Group (33-44 mg/L) and the Three Forks (50 mg/L), Dawson Bay (43 mg/L), Winnipegosis (23 mg/L), and Red River (40.0 mg/L) Formations. This work indicates Li resource potential exists across the Williston Basin and advances our understanding of the Li distribution in basinal brines which could provide a new domestic source of this critical mineral.

North Dakota↗

USGS2025

Nanometer-scale relationships between sedimentary organic matter molecular composition, fluorescence, cathodoluminescence, and reflectance: The importance of oxygen content at low thermal maturities

Molecular characterization of sedimentary organic matter (SOM), termed macerals, is a common goal when seeking to understand petroleum generation as well as other geologic processes in deep time. However, unambiguous measurement of discrete macerals is challenging due to the small size of organic particles in sedimentary rocks, the proximity of different organic matter types to one another, mineral-organic matter interactions, and maceral mixing that occurs during SOM isolation prior to ex situ analysis. The recent advent of infrared spectrometers capable of nanometer-scale resolution and the application of these technologies to geologic samples has enabled advances in rapid, in situ molecular characterization of SOM allowing for insights into paleoenvironmental processes, such as organic matter productivity and preservation, among others. Here we employ one such technology, optical photothermal infrared (OPTIR) spectroscopy, to map SOM functional group distributions at 500-nm resolution in a sample from the Lower Cretaceous Sunniland Limestone of the South Florida Basin. Examined fields of view include occurrences of amorphous organic matter (AOM), inertinite, micrinite, solid bitumen, telalginite, and vitrinite. OPTIR data from these macerals are compared against traditional organic petrographic data from the same organic grains including fluorescence intensity and white light reflectance as well as against cathodoluminescence response, an emerging organic petrographic approach. Maceral oxygen content (using carbonyl functional group abundance as a proxy) is observed to vary widely between maceral types but correlates strongly with fluorescence and cathodoluminescence intensity as well as against reflectance. These findings highlight the important role that oxygen content plays in determining the optical properties of SOM and further demonstrate the ability of OPTIR to discriminate subtle molecular differences between SOM types.

Organic Geochemistry↗

USGS2024

Lithium resource in the Smackover Formation brines of Southern Arkansas

Lithium-rich brine deposits occur throughout the United States, including in the Smackover Formation. The concentration of lithium in Smackover Formation brines was predicted across southern Arkansas by using a machine-learning model that incorporated lithium concentration data and geologic information. Between 5.1 and 19.0 million metric tons of lithium are calculated to be present in the brines of the Smackover Formation in southern Arkansas. The range in possible total lithium reflects the uncertainty in machine-learning predictions of lithium concentrations and the range of Smackover Formation porosity. This estimate quantifies the in-place lithium resource and does not consider the technological and economic feasibility of extracting the lithium from the brines.

Arkansas↗

USGS2024

Ion exchange processes for CO2 mineralization using industrial waste streams: Pilot plant demonstration and life cycle assessment

An attractive technique for removing CO 2 from the environment is sequestration within stable carbonate solids (e. g., calcite). However, continuous addition of alkalinity is required to achieve favorable conditions for carbonate precipitation (pH>8) from aqueous streams containing dissolved CO 2 (pH<4.5) and Ca 2+ ions. In this study, a pH-swing process using ion exchange was demonstrated to process 300 L of produced water brine per day for CO 2 mineralization. Proton titration capacities were quantified for aqueous streams in equilibrium with gas streams at various concentrations of CO 2 (pCO 2 =0.03–0.20 atm) and at various flow rates (0.5–2.0 L min −1 ). Energy intensities for the process were determined to be between 30 and 65 kWh per tonne of CO 2 sequestered depending on the composition of the brine stream. A life cycle assessment was performed to analyze the net carbon emissions of the technology which indicated a net CO 2 reduction for pCO 2 ≥0.12 atm (−0.06–−0.39 kg CO 2 e per kg precipitated CaCO 3 ) utilizing calcium-rich brines. The results from this study indicate the ion exchange process can be used as a scalable method to provide alkalinity necessary for the capture and storage of CO 2 in Ca-rich waste streams.

Chemistry Select↗

USGS2024

Insights into glendonite formation from the upper Oligocene Sagavanirktok Formation, North Slope, Alaska

The type locality for the upper Oligocene Nuwok Member of the Sagavanirktok Formation (Carter Creek, North Slope, Alaska, USA) contains abundant occurrence of glendonite, a pseudomorph after the calcium carbonate mineral ikaite, which typically forms in the shallow subsurface of cold marine sediments. The region during the time of Nuwok Member deposition was located at a high latitude, similar to today, and the study site is characterized by sands and silty muds interpreted here to have been deposited in coastal and shelfal marine environments. Isotopic (Sr) and biostratigraphic (foraminifera) evidence presented here refine the depositional age of the outcrop to approximately 24 Ma. Glendonites occur in two basic forms: radial clusters, commonly centered around a single larger primary crystal ( approx. 10 cm; Type A) and larger single blades generally without accessory crystals (approx. 15–25 cm; Type B). Microscopic examination revealed a sequence of multiple types of replacive calcite that formed as a direct result of ikaite transformation: Type 1 rhombohedral crystals characterized by microporous and inclusion-rich cores and concentric zones, Type 2A, composed of clear calcite that overgrew and augmented Type 1 crystals, and inclusion-rich, microcrystalline Type 2B, which formed a matrix surrounding the rhombs and commonly dominates the outer rims of glendonite specimens. Type 3 calcite precipitated as fibrous, botryoidal epitaxial cement atop previous phases and is not ikaite-derived. These phases are distributed in similar ways in all examined specimens and are consistent with several previously described glendonite occurrences around the world, despite differing diagenetic and geologic histories. Stable isotope evidence (δ13C and δ18O) suggests sourcing of glendonite carbon from both organic and methanogenic sources. Glendonites of the Nuwok Member can therefore assist in the determination of a more comprehensive ikaite transformation model, improving our understanding of glendonite formation and the sedimentological and environmental context of their occurrence. Oligocene glendonites are uncommon globally; the well-preserved occurrence described here can allow future studies to better reconstruct Arctic environmental conditions and paleoclimates during this time.

Alaska↗

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↗

USGS2024

Deformation-induced graphitization and muscovite recrystallization in a ductile fault zone

A suite of slate samples collected along a 2 km transect crossing the Lishan fault in central Taiwan were evaluated to assess the role of ductile deformation in natural graphitization at lower greenschist facies metamorphic conditions. The process of natural aromatization, or graphitization, of an organic precursor is well established as a thermally driven process; however, experimental studies have shown that the energy provided by deformation can substantially reduce the activation energy required for graphitization. This study provides a natural example of deformation-induced graphitization. A strain gradient approaching the Lishan fault was established by scanning electron microscope imaging and X-ray diffraction analysis of phyllosilicates and quartz that showed an increase in the strength of slaty cleavage development via dissolution-precipitation processes. Thermal conditions were constrained to be near isothermal using calcite-dolomite geothermometry. Raman spectroscopic results from carbonaceous material, including D1-full width-at-half-maximum (FWHM), G-FWHM, Raman band separation (RBS), and a lesser-known vibrational mode B 2g -FWHM, showed robust linear trends across the same sampling transect. However, the G-FWHM parameter showed a trend opposite of that expected from thermally driven graphitization. The Raman results are interpreted to reflect a strain-driven reduction in graphite crystallite size (decrease in G-FWHM) but improvement in structural ordering in individual coherent domains. A multiple linear regression with an R 2 value of 0.92 predicts the graphite D1-FWHM values from the XRD-derived ratio of muscovite populations and muscovite microstrain, demonstrating the concomitant recrystallization of silicates and carbonaceous material across the strain gradient, despite the disparate processes accommodating the deformation. This study demonstrates the role of deformation in natural graphitization and provides a new perspective on the use of graphite as a geothermometer in strongly deformed greenschist facies rocks.

Journal of Metamorphic Geology↗

USGS2024

Evaluation of coal mine drainage and associated precipitates for radium and rare earth element concentrations

Coal mine drainage (CMD) and associated metal-rich precipitates have recently been proposed as unconventional sources of rare earth elements (REEs). However, the potential occurrence of radium (Ra), a known carcinogen, with the REE-bearing phases has not been investigated. We hypothesized that Ra may occur in solids that are precipitated from CMD as a “radiobarite” solid solution ((Ba,Sr,Ra)SO 4 ) and/or adsorbed with hydrous metal oxides. REEs have been documented to sorb or co-precipitate with iron (Fe), manganese (Mn), and aluminum (Al) oxyhydroxide in CMD solids. Likewise, Ra has been documented to sorb to hydrous Fe and Mn oxides especially where sulfate (SO 4 ) and/or barium (Ba) concentrations are insufficient to precipitate radiobarite. Thus, we conducted the first-ever survey of Ra concentrations in corresponding CMD water and solid samples in the United States. Samples were analyzed from 4 untreated and 9 treated CMD sites in both the bituminous and anthracite coal regions of Pennsylvania across a range of pH and SO 4 concentrations. The dissolved Ra in CMD was relatively low (<0.5 Bq/L), consistent with radiobarite solubility; however, CMD solids were largely composed of amorphous Fe, Al, and Mn oxyhydroxide and silicate minerals. Ra was associated with Mn-enriched CMD solids, upwards of 875 Bq/kg. Total REE + yttrium (Y) content in the CMD solids was enriched upwards of 3600 mg/kg and was significantly correlated with Al content. These preliminary results suggest that REE extraction may target Al-rich solids to avoid Ra in Mn-rich solids.

Pennsylvania↗

USGS2024

Deep syntectonic burial of the Anthracite belt, Eastern Pennsylvania

Fluid inclusion microthermometry and Raman spectroscopy of fluid inclusions in quartz veins from the Pennsylvanian rocks of the Anthracite belt, eastern Pennsylvania support a deep burial model of coalification in favor of focused orogenic hot fluid flow. High-temperature (250 to 255 °C) trapping of CH 4 ± CO 2 saturated aqueous fluids and CH 4 ± CO 2 inclusions indicate fluid trapping at depths of 11.5 to 13.4 km under a cover of Pennsylvanian to Permian(?) syntectonic load. In the folded rocks to the south of the Anthracite belt, CH 4 ± CO 2 fluid inclusions indicate a sediment load that was up to 16.3 km thick. Re -equilibrated aqueous fluid inclusions from veins in Silurian through Devonian rocks give the same range of trapping conditions but a wide range of fluid salinities suggesting that folding, fracturing, and meteoric recharge resulted in the intermixing of fluids from throughout the stratigraphic succession.

Pennsylvania↗

USGS2024

Produced water geochemistry from hydraulically stimulated Niobrara Formation petroleum wells: Origin of salinity and temporal perspectives on treatment and reuse

Produced water (i.e., a mixture of returned injection fluids and geologic formation brines) represents the largest volumetric waste stream associated with petroleum production in the United States. As such, produced water has been the focus of intense study with emphasis on understanding the geologic origin of the fluids, environmental impacts of unintended or intentional release, disposal concerns, and their commodity (e.g., lithium) potential. However, produced water geochemistry from many active petroleum plays remain poorly constrained leading to knowledge gaps associated with the origin of brine salinity and parameters (e.g., radium levels) that can impact treatment, disposal, and possible reuse. Here we evaluate the major ion geochemistry, radium concentrations, and stable water isotope composition of ~120 produced water samples collected from 17 producing unconventional petroleum wells in Weld County, Colorado from the Late Cretaceous Niobrara Formation. This sample set encompasses eight produced water time series from four new wells across production days 0 to ~365 and from four established wells across production days ~1000 to ~1700. Additionally, produced water from nine other established Niobrara Formation wells were sampled at discrete time points ranging from day 458 to day 2256, as well as hydraulic fracturing input fluids. These results expand the available Niobrara Formation produced water geochemical data, previously limited to few wells sampled within the first year of production, allowing for the heterogeneity of major ions and radium to be evaluated. Furthermore, we explore the geochemical relationships between major ion ratios and stable water isotope composition to understand the origin of salinity in Niobrara Formation brines from the Denver-Julesburg Basin. These findings are discussed with perspective toward potential treatment and reuse of Niobrara produced water prior to disposal.

Colorado, Nebraska, Wyoming↗

USGS2024

Evaluation of the lithium resource in the Smackover Formation brines of southern Arkansas using machine learning

Global demand for lithium, the primary component of lithium-ion batteries, greatly exceeds known supplies, and this imbalance is expected to increase as the world transitions away from fossil fuel energy sources. High concentrations of lithium in brines have been observed in the Smackover Formation in southern Arkansas (>400 milligrams per liter). We used published and newly collected brine lithium concentration data to train a random forest machine-learning model using geologic, geochemical, and temperature explanatory variables and create a map of predicted lithium concentrations in Smackover Formation brines across southern Arkansas. Using these predicted lithium maps with reservoir parameters and geologic information, we calculated that there are 5.1 to 19 million tons of lithium in Smackover Formation brines in southern Arkansas, which represents 35 to 136% of the current US lithium resource estimate. Based on these calculations, in 2022, 5000 tons of dissolved lithium were brought to the surface within brines as waste streams of the oil, gas, and bromine industries.

Arkansas↗

USGS2023

Thermal evolution of graptolite and solid bitumen properties at high maturity under natural and artificial conditions

To refine the use of graptolite and solid bitumen as thermal proxies at overmature conditions, we evaluated their evolution via Raman and infrared (IR) spectroscopies, reflectance, and geochemical screening using high-temperature pyrolysis experiments in comparison to naturally matured samples. Naturally matured samples included marine shales from the overmature Upper Ordovician Wufeng-Lower Silurian Longmaxi Formations (herein referred to as Wufeng-Longmaxi) of the Sichuan Basin, China. Immature samples for pyrolysis experiments included Mesoproterozoic (Ectasian) Xiamaling marine shale from Hebei, China (graptolite absent) and graptolite-bearing Ordovician (Tremadocian) Alum marine shale from Grönhögen, Sweden. Pyrolysis experiments at 360 °C for 10 days and 27 days (hydrous conditions), and 450 °C 3 days, 550 °C 3 days, and 550 °C 10 days (all anhydrous) created Xiamaling and Alum residues with solid bitumen and graptolite, respectively, of similar and higher maturity compared to the naturally matured Wufeng-Longmaxi samples. Compositional proxies from IR spectroscopy were inconclusive. Raman spectral properties including Raman band separation (RBS) and the full-width at half-maximum of the G-band (G-FWHM) exhibited robust positive and inverse relationships with increasing reflectance in pyrolysis residues, respectively. RBS values were systematically lower in artificially matured samples versus naturally matured samples with equivalent reflectance values, whereas G-FWHM values were systematically higher. This observation indicates that the limited duration or low internal reactor pressure of pyrolysis experiments is insufficient to allow alignment or ordering of aromatic carbon arrays in both organic matter types, relative to natural maturation occurring at geologic time scales. Reflectance of graptolite was typically higher than co-occurring solid bitumen in Wufeng-Longmaxi samples and the untreated Alum sample, suggesting inherently higher aromaticity. However, aromaticity in pyrolysis residues was systematically higher in solid bitumen compared to graptolite with equivalent reflectance values, indicating a higher kinetic barrier to molecular rearrangement in graptolite versus solid bitumen. These data further clarify differences in the molecular evolution of sedimentary organic matter in natural versus analogue laboratory environments and distinguish the properties of individual organic matter types in response to thermal stress.

International Journal of Coal Geology↗

USGS2023

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

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

Colorado, Kansas, Nebraska, Wyoming↗