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Paul C. Hackley

Publications and source records attributed to Paul C. Hackley.

9 recordsLinked to original sources

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

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

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

Babouri-Figuil basin

Using peak geometry and shifts in the x-ray spectrum of carbon from electron probe microanalysis to determine thermal maturity of organic matter

During the burial of mudstones, the associated organic matter undergoes gradual thermal maturation, a key process that can influence the reactivity of organic matter during catagenesis, the formation of hydrocarbon deposits and the chemical weathering of mudstones. Conventional methods for assessing the thermal maturity of organic matter often fail to reflect the geochemical heterogeneity between individual organic phases in mudstone samples. Here, we report an alternative, non-destructive, surficial and micro-scale (analytical spot size of ~ 300 nm with about 4 μm diffusion depth for micrometre-size organic grains) method to evaluate the thermal maturity of organic matter in mudstones using the carbon K α X-ray spectrum measured by field emission-electron probe microanalyser (FE-EPMA). Using this method, we observed correlations between parameter values derived from FE-EPMA spectra, including the peak position, the peak area and the intra-sample heterogeneity of these measurements, and independently measured vitrinite/solid bitumen reflectance for a suite of mudstones, representing different age, geological context and burial depth. With the increased values in peak area and position, we identified an increase in the carbon mass fraction of organic matter and the mean nominal oxidation state of carbon approaching zero. These trends, which are consistent with aromatisation and graphitisation, provide the rationale for using FE-EPMA to estimate the thermal maturity of organic matter. To explore some of these trends in more detail, we employed time-of-flight secondary ionisation mass spectrometry, X-ray photoelectron spectroscopy and optical reflectance measurements on a subset of samples.

Geostandards and Geoanalytical Research

Integrated stratigraphic and geochemical analysis of organic-rich intervals of the Lewis Shale in the eastern Washakie Basin, Wyoming

Geological studies in the Cretaceous Western Interior Seaway (KWIS) in North America reveal highly variable sedimentological conditions on its western shore caused by rapidly changing sea level and detrital input during the seaway’s closure. Here we examine a 601-foot (183 meters) continuous core through the lower part of the Maastrichtian Lewis Shale in the eastern Washakie Basin, Wyoming, through integrating stratigraphic and geochemical analyses to better understand organic matter deposition and preservation during the final marine transgression within the seaway. The core penetrates eight organic-rich flooding intervals (F1-F8) and a regional condensed section, informally known as the Asquith marker. The lower portions of the core record sediment input from a southern source, likely the Sierra Madre/Park Ranges, while the upper part records sediment input from a northern source, likely the Granite Mountains. This provenance transition is supported by regional stratigraphic analysis and changes in bulk mineral and trace metal composition. The Asquith marker and early flooding surfaces are enriched in oil-prone, marine organic matter deposited under dysoxic to euxinic conditions, whereas younger flooding surfaces show increased terrigenous input and poorer preservation conditions. The Asquith marker is identified as a prime oil-prone source rock. Although younger flooding surfaces also exhibit favorable source-rock properties, their generative potential is reduced due to increased clastic and terrigenous organic matter deposition caused by regression. These results emphasize the importance of sediment source variability, organic matter preservation, and changing redox conditions to provide insight into the sediment provenance and petroleum potential of the Lewis Shale in the context of the final transgression within the KWIS.

Colorado, Wyoming

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

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

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

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

Kentucky, Ohio, Virginia, West Virginia

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

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

Journal of Analytical and Applied Pyrolysis

Component identification of solid biomass fuels using reflected light microscopy: Interlaboratory study 2

As nations transition toward sustainable energy systems , biomass has become a vital component of global energy portfolios. Derived from organic materials such as wood, agricultural residues, forestry byproducts, and organic waste, biomass is a renewable energy source with significant environmental and economic benefits. Responsible biomass energy production can improve waste management, reduce emissions of greenhouse gases, and mitigate environmental pollution. However, as the diversity of biomass-derived fuels increases, robust quality assessment methods are essential to ensure their efficiency, safety, and minimal environmental impact. Reflected light microscopy (RLM) is one such technique with the potential to complement conventional physico-chemical analyses by enabling a rapid identification of material constituents and impurities. To refine this methodology and evaluate the reproducibility of solid biomass component identification using RLM, an interlaboratory study (ILS) was conducted. The study involved the recognition of 58 components across 45 photomicrographs, with the participation of 65 scientists and students from 25 countries. The participants faced high difficulty identifying some of the marked components, and as a result, the percentage of correct answers ranged from 19.0 % to 98.3 %, with an average correct identification rate of 62.7 %. The most challenging aspects of the identification process included distinguishing between woody and non-woody (agro) biomass, accurately identifying petroleum-derived materials, and differentiating agro biomass from inorganic matter. The results suggest that while RLM is an important tool for characterizing solid biomass, further development of methodology guidelines and training are necessary to enhance its effectiveness. Future research should prioritize preparing detailed, image-rich, microscopic morphological descriptions of biomass fuel components, which could improve the accuracy and reliability of using RLM in biomass fuel characterization.

International Journal of Coal Geology