Geology topics

Martha Stokes

Publications and source records attributed to Martha Stokes.

10 recordsLinked to original sources

USGS2026

Evidence for a biological origin of uranium-rich carbon masses within the Ediacaran Salt Range Formation of Pakistan

Thucholites are unique organic structures found in igneous and sedimentary rocks composed of a U-C-rich interior enclosed by an organic outer shell. Their formation and occurrence have perplexed scientists for over 100 years. Typically, thucholites are sparse in sedimentary rocks but where found in abundance, they may be the result of rapid paleoecological disruptions, e.g., volcanic ashfall. Here, we evaluated thucholites from the Ediacaran Salt Range Formation of the Indus Basin in Pakistan using field emission scanning electron microscopy (FESEM) and nanoscale secondary ion mass spectroscopy (NanoSIMS) to propose a two-stage mechanism for thucholite development. NanoSIMS results suggest organic matter in thucholite cores formed by biological fractionation (represented by the presence of lighter 13 C/ 12 C and 34 S/ 32 S) while the outer organic mantle formed via radiolysis-induced polymerization. FESEM elemental analysis confirms compositional differences between the two thucholite components (core and mantle), further implying their contrasting origins. Dimensional comparison of thucholite cores and their U-bearing mineral morphologies to ancient and modern U-biomineralized microbes suggests that the thucholite cores formed from metal-biological interactions. The presence of volcanogenic biotite, alkali feldspar, and clay spherules (interpreted as devitrified volcanic glass) with thucholite suggests that the thucholite cores in the Salt Range Formation are biological responses to rapid paleoenvironmental change from volcanic eruption which preserved the fossilized morphologies of Proterozoic microorganisms.

Salt Range↗

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↗

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

Synergy between geology and geophysics in graphite mineral resource assessment

Graphite is designated as a critical mineral by the U.S. Government due to its essential role in modern technology and its vulnerability to supply chain disruption. To evaluate domestic graphite resources, the U.S. Geological Survey (USGS) conducted two airborne electromagnetic (AEM) surveys as part of the Earth Mapping Resources Initiative (Earth MRI) over prospective areas in the southern Appalachians of Alabama and the Seward Peninsula of Alaska. These surveys aimed to refine areas of interest by revealing subsurface electrical resistivity patterns indicative of graphite-bearing rocks. The results of the AEM surveys were integrated with existing geological knowledge and supplemented by field observations to assess the likelihood of undiscovered resources in these regions. This multidisciplinary approach combined geophysical techniques with traditional geological methods, enhancing the understanding of graphite potential in areas that may have been previously overlooked. The findings from this initiative are expected to contribute significantly to the ongoing efforts to secure a reliable domestic supply of graphite, thereby reducing import reliance and supporting national interests in mineral resource management.

Conference Paper↗

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

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↗

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↗

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↗

USGS2023

Mapping ancient sedimentary organic matter molecular structure at nanoscales using optical photothermal infrared spectroscopy

Elucidating the molecular structure of sedimentary organic matter (SOM) is key to understanding petroleum generation processes, as well as ancient sedimentary environments. SOM structure is primarily controlled by biogenic source material (e.g., marine vs. terrigenous), depositional conditions, and subsurface thermal history. Additional factors, e.g., strain, may also impact the molecular structure of SOM. Multiple spatially resolved approaches exist for in situ evaluation of SOM, including Raman and infrared spectroscopies, as well as mass spectrometric methods. While these methods have enabled increased understanding of the occurrence and distribution of SOM functional groups, they suffer from disadvantages including low spatial resolution (infrared spectroscopy), limited molecular information (Raman spectroscopy), and sample destruction (mass spectrometric methods). Recent technological advances have resulted in infrared spectrometers capable of breaking the Abbe diffraction limit, greatly increasing the spatial resolutions accessible for an infrared measurement. Here we utilize optical photothermal infrared spectroscopy (O-PTIR) to record maps of functional group distributions at 500 nm spatial resolution in Tasmanites (algal microfossils) from the Upper Devonian Ohio Shale. These data allow for discrimination between Tasmanites , adjacent SOM, and fine-grained minerals. Additionally, functional group distributions within Tasmanites were found to be generally homogenous, although slight variations exist between the body and fold apices (zones of greatest deformation) which may indicate strain-induced chemical reactions. The data presented here represent the first application of O-PTIR to study SOM, highlighting the promise of this analytical approach for future studies evaluating the molecular composition of geologic materials at sub-micron scales.

Organic Geochemistry↗

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↗