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Palma J. Botterell

Publications and source records attributed to Palma J. Botterell.

12 recordsLinked to original sources

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↗

Avak Creek oil occurrence, North Slope, Alaska: Newly discovered oil seep on Native lands, near village of Utqiagvik

An unknown occurrence of oil was detected near Avak Creek on Native lands on the North Slope of Alaska. Determining the source of oil was imperative for allowing stakeholders (Federal, State, and local government agencies and the landowner, an Alaska Native corporation) to make timely and informed decisions and mount a mitigation response, if required. The regional and local geological framework of the Avak Creek site was constructed using seismic surveys, well data, and basin modeling results, to identify local petroleum systems, map structural geometry and faults, define source rock thermal maturity distributions, and infer likely oil-migration pathways. Molecular hydrocarbon fingerprints (biomarkers, diamondoids, compound-specific isotopes) of the oil were compared to those of local and regional oil seeps, exploration well tests, and produced oils. Biomarker acid distributions characterized the history and extent of petroleum biodegradation. Integrating subsurface and geochemical parameters, the oil is interpreted to be a natural seep generated locally, predominantly from the Brookian Lower Cretaceous Hue Shale/gamma-ray zone, rather than an anthropogenic source of pollution. Results highlight sophisticated analytical technologies used to characterize complex, compositionally altered hydrocarbons. Results also advance our understanding of Brookian source rock distribution, subsurface petroleum migration pathways, and Arctic Alaska petroleum systems.

Alaska↗

Arctic Alaska deepwater organic carbon burial and environmental changes during the late Albian–early Campanian (103–82 Ma)

The middle Cretaceous greenhouse period experienced profound environmental change including episodes of enhanced global burial of organic carbon marked by carbon isotopic excursions (CIEs). However, the role and response of polar regions like the newly formed, partially enclosed Arctic Ocean Basin during middle Cretaceous carbon burial remains enigmatic. We present the first Arctic deepwater CIE record that characterizes conditions offshore of the Alaska margin north of 75°N paleolatitude. Organic carbon isotopes (δ 13 C org ) and 103–82 Ma ash zircon U-Pb dates from the distal Hue Shale record multiple Albian–Campanian CIEs during slow ∼3–15 m/Myr sediment accumulation rates. Average total organic carbon (TOC) increased substantially during large 2–3 ‰ CIEs of the ∼101 Ma Albian-Cenomanian boundary event (from 7 to 18 % TOC) and ∼94 Ma Cenomanian-Turonian boundary event (5 to 10 % TOC). Turonian TOC remained elevated (8–13 %) during high global sea levels and temperatures of the Cretaceous Thermal Maximum, followed by an increase from 7 to 11 % TOC during the ∼90 Ma late Turonian event 1.5 ‰ CIE. Average TOC subsequently decreased in the Coniacian–Campanian, but relative maxima occurred during subtle 0.5–1 ‰ CIEs interpreted as the ∼87 Ma late Coniacian event (increase from 4 to 7 % TOC), ∼85 Ma Horseshoe Bay event (3.5 to 4.5 % TOC), and ∼84 Ma Santonian-Campanian boundary event (3.5 to 5 % TOC). Increases in hydrogen index and productivity proxies (P, Ba, Nd) that accompanied each CIE episode with enhanced TOC suggest a strong link between marine productivity and organic carbon burial at short-term CIE timescales. However, long-term (>5–8 Myr) changes in trace metal redox (Mo, Fe, V) and salinity (B/Ga) proxies suggest shifts in prevailing environmental conditions at timescales longer than the CIEs. Late Albian–middle Turonian marine salinity occurred during euxinic (103–98 Ma) and suboxic (98–90 Ma) conditions with deposition interpreted to have occurred within and beneath an oxygen minimum zone, respectively. In contrast, late Turonian–early Campanian (90–82 Ma) freshening and restricted euxinic basin conditions may signal the start of widespread restriction known to characterize the Paleogene Arctic. Overall, these results highlight that middle Cretaceous Arctic deepwater remained a productive marine carbon sink coupled to the global carbon cycle despite evolving Arctic greenhouse conditions.

Alaska↗

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↗

Geochemical advances in Arctic Alaska oil typing - North Slope oil correlation and charge history

The Arctic Alaska petroleum province is geologically and geochemically complex. Mixed hydrocarbon charge from multiple source rocks and/or levels of thermal maturity is common within an individual oil pool. Biomarker and chemometric statistical analyses were used to correlate twenty-nine oils to five oil families derived from: (1) Triassic Shublik Formation (calcareous organofacies), (2) Triassic Shublik Formation (shaly organofacies), (3) Jurassic Kingak Shale, (4) Cretaceous shale (pebble shale unit and Hue Shale), and (5) Paleogene shale (Canning Formation). Age-diagnostic and source-related oil biomarker parameters establish clear genetic relationships between the normal oil-window components and their putative source designations. However, application of diamondoid analyses reveals mixed-oil accumulations with postmature charge contributions (diamondoid-rich and biomarker-poor) in many oils. Most sampled reservoirs contain a predominant charge derived from a single oil-window source plus a minor contribution from one or more higher maturity source(s). Variations in source organofacies also are recognized in the Shublik, Kingak, and Cretaceous oil families. In some cases, oils from multiple pools within a single field display relatively homogeneous geochemical profiles, suggesting a common source and migration pathway. For example, oil from the significant Pikka discovery is inferred to originate mainly from the calcareous Shublik Formation. In other cases, variability among oils from multiple pools within a single field (e.g., Milne Point, Colville River, and Northstar) likely indicates a more complex source, migration, and charge history. Results may be useful for anticipating the composition of oil charge in stratigraphic traps with low-permeability sandstone reservoirs, where oil gravity and other chemical parameters may influence economic viability.

Alaska↗

High microscale variability in Raman thermal maturity estimates from shale organic matter

Raman spectroscopy has recently received attention as a means to estimate thermal maturity of organic matter in petroleum generating source rocks to complement more traditional approaches such as vitrinite reflectance and programmed pyrolysis. While many studies have observed positive correlations between source rock thermal maturity and Raman spectral parameters, little attention has been given to the degree of variation in the Raman response across individual organic grains, especially for shales or mudrocks with highly dispersed organic matter. Here the spatial variation in Raman estimates of thermal maturity within individual organic grains is assessed from shales from the Boquillas, Marcellus, Niobrara, and Woodford Formations. The thermal maturity parameters extracted from Raman spectra can vary widely across distances of ≤5 μm within the same organic grain. These results illustrate the high degree of chemical heterogeneity inherent to the organic matter within these source rocks. Additionally, the spatial pattern of the Raman parameters, as revealed by 2D Raman mapping, imply that organic matter structure is influenced by associations with mineral surfaces within the surrounding rock matrix. Chemical heterogeneity and matrix effects directly impact the Raman response from these types of materials and thus the extracted thermal maturity estimate. These findings highlight the care which must be adopted when making Raman measurements of organic matter within source rock matrices, especially for samples which feature highly dispersed, heterogeneous organic matter as found in petroliferous mudrocks.

International Journal of Coal Geology↗

Assessment of undiscovered oil and gas resources in the Cretaceous Nanushuk and Torok Formations, Alaska North Slope, and summary of resource potential of the National Petroleum Reserve in Alaska, 2017

The U.S. Geological Survey estimated mean undiscovered, technically recoverable resources of 8.7 billion barrels of oil and 25 trillion cubic feet of natural gas (associated and nonassociated) in conventional accumulations in the Cretaceous Nanushuk and Torok Formations in the National Petroleum Reserve in Alaska, adjacent State and Native lands, and State waters. The estimated undiscovered oil resources in the Nanushuk and Torok Formations are significantly higher than previous estimates, owing primarily to recent, larger than anticipated oil discoveries.

Alaska↗

Transgressive-regressive cycles in the metalliferous, oil-shale-bearing Heath Formation (Upper Mississippian), central Montana

The Upper Mississippian Heath Formation, which accumulated in the Big Snowy Trough of central Montana, has been known for three decades to contain mudrocks highly enriched in Zn, V, Mo, Ni and other metals, and source rocks for oil. The unit has more recently been recognized as a prospective tight oil play. Here we present petrographic, paleontologic, geochemical, and carbon and sulfur isotope data on seven continuous drill cores spanning ≤146 m of immature to marginally mature strata in order to improve understanding of the depositional setting of the Heath. The unit consists of five third-order transgressive-regressive cycles (C1–C5 from bottom to top) that were deposited during a fluctuating climatic regime. Cycles comprise thinly interbedded gray to black mudrock and carbonate strata capped by either coal, implying a humid climate (C1, C3 and C4), or gypsum, implying more arid conditions (C2); the upper part of C5 is not preserved in our study area. Mfs (maximum flooding surfaces) in C1, C2, C4, and C5 lie within black mudrock beds ~0.5–3-m thick with >10% TOC (total organic carbon), type I and type II kerogen (determined by programmed pyrolysis), high contents of Zn, V, Mo, and other metals, relatively low values of δ13CTOC and δ34Spyrite, and a limited-diversity fauna of locally abundant, thin-shelled pelecypods (Dunbarella? sp.). The mfs in C2 is within the Cox Ranch oil shale bed, which is known from previous studies to be metalliferous; new analyses reported here show ≤28 wt % TOC, 5140 ppm Zn, 1910 ppm V, 1590 ppm Mo, and 509 ppm Ni. Strata that contain the mfs of C1, C4, and C5 are shown here for the first time to also have high metal contents, with maximum values of 1030–7340 ppm Zn, 446–1980 ppm V, 72–859 ppm Mo, and 221–452 ppm Ni. Cycle C3, which contains more gray mudrock and carbonate beds than the other cycles, has lower TOC (≤4.2 wt %), lower metals, and mainly type III kerogen. Carbonate beds include normal-marine crinoidal mudstone to packstone and lesser (dolo)mudstone with fenestral fabric, peloids, intraclasts, and a euryhaline fauna. Mid-Chesterian (early Serpukhovian) foraminifers in C3, combined with previously published fossil data, suggest that third-order cycles in the Heath Formation were ~1–2 myr in duration. They formed during a time of active block faulting in the Big Snowy Trough and global cooling linked to Gondwanan glaciation. Tectonic, climatic, and paleogeographic factors shaped the cycles of the Heath Formation. Faunal and geochemical evidence indicate that conditions were most favorable for marine life during C3. Molybdenum concentrations >100 ppm and organic geochemical data suggest euxinic conditions during deposition of the black mudrock in C2, C4, and C5, but the presence of shell beds (1 mm–6-cm thick) within this mudrock requires bottom water with sufficient oxygen to support life, at least periodically. The apparent conflict between the geochemical and paleontologic observations likely reflects the different time scales of these two environmental proxies: 1000s of yrs vs <1–10s of yrs, respectively. Metal- and organic-rich strata in the Heath Formation formed by slow, condensed sedimentation from periodically anoxic or euxinic bottom waters in a marine basin. Fossil data indicate that anoxia was episodic, perhaps seasonal and/or linked to longer-duration climate shifts. On a millennial time scale, metal enrichments in the Heath reflect a balance between primary productivity that was high enough for oxygen to be consumed by sinking organic matter and oxic seawater inflow that was strong enough to maintain a supply of metals without compromising anoxia. Organic-rich mudrock in the Heath shares intriguing lithologic and geochemical similarities with mudrock in other Middle to Upper Paleozoic units such as the Devonian-Mississippian Bakken Formation and Pennsylvanian cyclothems (e.g., Excello Shale).

Montana↗

Extraction of hydrocarbons from high-maturity Marcellus Shale using supercritical carbon dioxide

Shale is now commonly exploited as a hydrocarbon resource. Due to the high degree of geochemical and petrophysical heterogeneity both between shale reservoirs and within a single reservoir, there is a growing need to find more efficient methods of extracting petroleum compounds (crude oil, natural gas, bitumen) from potential source rocks. In this study, supercritical carbon dioxide (CO 2 ) was used to extract n -aliphatic hydrocarbons from ground samples of Marcellus shale. Samples were collected from vertically drilled wells in central and western Pennsylvania, USA, with total organic carbon (TOC) content ranging from 1.5 to 6.2 wt %. Extraction temperature and pressure conditions (80°C and 21.7 MPa, respectively) were chosen to represent approximate in situ reservoir conditions at sample depth (1920–2280 m). Hydrocarbon yield was evaluated as a function of sample matrix particle size (sieve size) over the following size ranges: 1000–500 μm, 250–125 μm, and 63–25 μm. Several methods of shale characterization including Rock-Eval II pyrolysis, organic petrography, Brunauer–Emmett–Teller surface area, and X-ray diffraction analyses were also performed to better understand potential controls on extraction yields. Despite high sample thermal maturity, results show that supercritical CO 2 can liberate diesel-range ( n -C 11 through n -C 21 ) n -aliphatic hydrocarbons. The total quantity of extracted, resolvable n -aliphatic hydrocarbons ranges from approximately 0.3 to 12 mg of hydrocarbon per gram of TOC. Sieve size does have an effect on extraction yield, with highest recovery from the 250–125 μm size fraction. However, the significance of this effect is limited, likely due to the low size ranges of the extracted shale particles. Additional trends in hydrocarbon yield are observed among all samples, regardless of sieve size: 1) yield increases as a function of specific surface area ( r 2 = 0.78); and 2) both yield and surface area increase with increasing TOC content ( r 2 = 0.97 and 0.86, respectively). Given that supercritical CO 2 is able to mobilize residual organic matter present in overmature shales, this study contributes to a better understanding of the extent and potential factors affecting the extraction process.

Pennsylvania↗