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Justin E. Birdwell

Publications and source records attributed to Justin E. Birdwell.

At least 37 records · Page 2Linked to original sources
USGS2025

Evaluating the potential of co-located non-petroleum energy resources in the Gulf Coast using play fairwayaAnalysis

Geological resources critical to the energy transition, such as sedimentary geothermal, carbon storage potential, and lithium in brines, commonly struggle for economic feasibility as stand-alone developments but can have greater viability when the potential for more than one of these resources exist within the same reservoir or stacked in different stratigraphic intervals. There may also be instances where development of one resource inhibits development of others and decisions need to be made on how to best prioritize the use of those resources in the subsurface. Subsurface data sets were analyzed and integrated to evaluate the distribution of non-petroleum energy and related resources in the onshore and nearshore U.S. Gulf Coast. Temperature, pressure, brine composition (lithium content), and reservoir quality data for thirty-four depositional units have been compiled and visualized to high-grade areas where multiple resource opportunities likely coexist. For sedimentary geothermal, possible resource areas are defined as low potential (<90°C), moderate potential (90–150°C), and high potential (>150°C). For CO 2 storage, high potential areas exhibit supercritical CO 2 conditions less than 80% of the fracture gradient. Areas with pore pressure between 80% and 100% of the fracture gradient are considered to exhibit moderate potential and areas where the fracture gradient is equal to or greater than 100% are assigned low potential. Lithium resources in brines were defined by lithium concentrations as low potential (<100ppm), moderate potential (100-200ppm), or high potential (>200ppm). Reservoir quality affects the viability of all three of these resources and is evaluated using depositional environment maps of each unit. The resulting play fairway maps can be used for regional scale screening evaluations of these resources and to identify areas of interest where more detailed, prospect-scale studies can be undertaken.

Gulf Coast↗
USGS2024

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

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

Montana, North Dakota↗
USGS2024

Middle-late Holocene paleolimnological changes in central Lake Tanganyika: Integrated evidence from the Kavala Island Ridge (Tanzania)

Middle and Late Holocene sediments have not been extensively sampled in Lake Tanganyika, and much remains unknown about the response of the Rift Valley’s largest lake to major environmental shifts during the Holocene, including the termination of the African Humid Period (AHP). Here, we present an integrated study (sedimentology, mineralogy, and geochemistry) of a radiocarbon-dated sediment core from the Kavala Island Ridge (KIR) that reveals paleoenvironmental variability in Lake Tanganyika since the Middle Holocene with decadal to centennial resolution. Massive blue-gray sandy silts represent sediments deposited during the terminal AHP (~5880–4640 cal yr BP), with detrital particle size, carbon concentrations, light stable isotopes, and mineralogy suggesting an influx of river-borne soil organic matter and weathered clay minerals to the lake at that time. Enhanced by the AHP’s warm and wet conditions, chemical weathering and erosion of Lake Tanganyika’s watershed appears to have promoted considerable nutrient recharge to the lake system. Following a relatively gradual termination of the AHP over the period from ~4640 cal yr BP to ~3680 cal yr BP, laminated and organic carbon-rich sediments began accumulating on the KIR. δ 15 N bulk , C/N, and hydrogen index data suggest high relative primary production from a mix of algae and cyanobacteria, most likely in response to nutrient availability in the water column under a cooler and seasonally dry climate from ~3680 to 1100 cal yr BP. Sediments deposited during the Common Era show considerable variability in magnetic susceptibility, total organic carbon content, carbon isotopes, and C/N, consistent with dynamic hydroclimate conditions that affected the depositional patterns, including substantial changes around the Medieval Climate Anomaly and Little Ice Age. Data from this study highlight the importance of sedimentary records to constrain boundary conditions in hydroclimate and nutrient flux that can inform long-term ecosystem response in Lake Tanganyika.

Kavala Island Ridge, Lake Tanganyika↗
USGS2024

Influence of organic matter thermal maturity on rare earth element distribution: A study of Middle Devonian black shales from the Appalachian Basin, USA

This study focuses on understanding the association of rare earth elements (REE; lanthanides + yttrium + scandium) with organic matter from the Middle Devonian black shales of the Appalachian Basin. Developing a better understanding of the role of organic matter (OM) and thermal maturity in REE partitioning may help improve current geochemical models of REE enrichment in a wide range of black shales. We studied relationships between whole rock REE content and total organic carbon (TOC) and compared the correlations with a suite of global oil shales that contain TOC as high as 60 wt.%. The sequential leaching of the Appalachian shale samples was conducted to evaluate the REE content associated with carbonates, Fe–Mn oxyhydroxides, sulfides, and organics. Finally, the residue from the leaching experiment was analyzed to assess the mineralogical changes and REE extraction efficiency. Our results show that heavier REE (HREE) have a positive correlation with TOC in our Appalachian core samples. However, data from the global oil shales display an opposite trend. We propose that although TOC controls REE enrichment, thermal maturation likely plays a critical role in HREE partitioning into refractory organic phases, such as pyrobitumen. The REE inventory from a core in the Appalachian Basin shows that (1) the total REE ranges between 180 and 270 ppm and the OM-rich samples tend to contain more REE than the calcareous shales; (2) there is a relatively higher abundance of middle REE (MREE) to HREE than lighter REE (LREE); (3) there is a disproportionate increase in Y and Tb with TOC likely due to the rocks being over-mature; and (4) the REE extraction demonstrates that although the OM has higher HREE concentration, the organic leachates contain more LREE, suggesting it is more challenging to extract HREE from OM than using traditional leaching techniques.

Middle Devonian Appalachian Basin↗
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

Assessment of undiscovered, technically recoverable conventional oil and gas resources in the Upper Jurassic Smackover Formation, U.S. Gulf Coast, 2022

Using a geology-based assessment methodology, the U.S. Geological Survey estimated undiscovered, technically recoverable mean resources of 143 million barrels of oil and 1,084 billion cubic feet of natural gas in conventional accumulations for the Upper Jurassic Smackover Formation in the onshore U.S. Gulf Coast region.

Alabama, Arkansas, Florida, Louisiana, Mississippi↗
USGS2024

An integrated perspective of paleoenvironmental change in the Western Interior Seaway before and during OAE-2 reveals how organic-rich mudstones form in dynamic environments

Organic and inorganic geochemistry was integrated with sedimentology from the Eagle Ford Group in the U.S. Geological Survey Gulf Coast-3 drill core to investigate why organic matter enrichment and anoxia predate the Cenomanian–Turonian oceanic anoxic event (OAE-2) at the southern Western Interior Seaway (WIS). The relationship between the degree of organic matter sulfurization and preservation in the southern WIS is comparable to OAE-2 sites outside of the WIS, but enhanced organic matter sulfurization and preservation predated OAE-2, distinguishing the southern WIS from other OAE-2 localities. Persistent euxinia and organic matter sulfurization before and during the mid-Cenomanian event (MCE) facilitated maximum organic matter enrichment and preservation to coincide with extensive lateral sediment transport. The new perspective detailed here reconciles geochemical evidence of depositional euxinia with sedimentological evidence of sediment transport, which informs how organic-rich mudstones form in dynamic environments. After the MCE but before OAE-2, reducing conditions weakened as relative sea-level continued to rise, resulting in an oxygen-depleted environment that was prone to transient euxinia. The extent of organic matter sulfurization, preservation, and enrichment declined as euxinia became intermittent. As maximum sea-level was established during OAE-2, boreal water masses flowed into the southern WIS and unrestricted, oxygenated marine conditions developed, which resulted in degradation of marine organic matter and less organic enrichment. The highest relative contribution of marine bacterial organic matter occurred during the persistently euxinic interval before and during the MCE. The relative input of algal organic matter increased as the depositional conditions became less reducing after the MCE but before OAE-2. Prasinophyte green algae contributed to the consistent dominance of C 28 steranes preceding OAE-2, which is becoming a widely observed feature across the southern and central WIS. A sharp drop in the C 28 sterane relative abundance reflects a decline in the abundance of prasinophytes as oxic depositional conditions developed during OAE-2. Relative abundances of 2-methylhopanes increased during OAE-2, which is a common signature of OAEs, suggesting a modified nitrogen cycle in the offshore southern WIS despite oxic depositional conditions during OAE-2.

Arkansas, Louisiana, Oklahoma, Texas↗
USGS2024

Geologic sources and well integrity impact methane emissions from orphaned and abandoned oil and gas wells

The 160-year history of oil and gas drilling in the United States has left a legacy of unplugged orphaned and abandoned wells, some of which are leaking methane and other hazardous chemicals into the environment. The locations of around 120,000 documented orphaned wells are currently known with the number of undocumented orphaned wells possibly ranging towards a million. The bulk of methane emissions originate from only 10 % of orphaned and abandoned wells, while the remaining wells have undetectable emissions. Understanding the sources of methane emissions from orphaned wells is key to estimating emission rates and prioritizing plugging. In this article, we identify key studies reporting methane emission measurements from orphaned and abandoned wells in the published literature and analyze previously published isotopic methane data to categorize the sources of methane emissions. Three primary geologic sources provide methane to a leaking well that can migrate from geologic formations into or along the wellbore to contaminate groundwater, the surface environment, and the atmosphere. These geologic sources of methane are petroleum (oil and gas) sourced reservoirs, coal seams, and methanogenesis occurring in and around the wellbore. Thermogenic petroleum gas reservoirs are associated with the highest emission rates measured to date. The next highest rates are from coalbed methane sources, while biogenic sources are the lowest based on the publicly available measured emissions data. Well conditions that could potentially enable methane transport include decay of the wellhead and surface infrastructure, wellbore deterioration from corrosive fluids in the subsurface, delamination of the casing and cement, damage from seismicity, and new fracture networks created by hydraulic fracturing of newly drilled neighboring wells. With an understanding of these geologic sources and well conditions, we can (1) better identify areas where high-emitting wells are likely to be present, (2) improve emission rate estimates from orphaned and abandoned wells, and (3) better prioritize wells for plugging.

Science of the Total Environment↗
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

Intramolecular carbon isotope geochemistry of butane isomers from laboratory maturation and Monte-Carlo simulations of kerogen types I, II, and III

Position-specific (PS) carbon isotope compositions of light hydrocarbons such as propane and butane isomers (n-butane and i-butane) can provide a wealth of information on the history of natural gases in the subsurface reservoirs and other environments. For PS carbon isotope analysis of butane isomers, we have established a GC-pyrolysis-GC-isotope ratio mass spectrometry method with demonstrated accuracy. With this method, we analyzed PS δ 13 C values of butane isomers generated from the systematic laboratory pyrolysis experiments of three different kerogen types (I, II, and III) at temperatures of 310–430 °C with corresponding thermal maturity (Easy %R o ) ranging from 0.7 to 3.3. The observed evolution in the abundances of butane isomers can be interpreted and semi-quantitatively modeled based on the abundances of different C C bonds within the kerogens at low maturity and thermal degradation of butane isomers at high maturity. The δ 13 C values at the central sites of both nC 4 and iC 4 were heavier than those at the terminal positions, similar to our previous observations of propane. Their isotopic evolution with the maturity were controlled largely by kinetic isotope effects associated with breaking of different C C bonds during the generation and degradation of butane isomers. Kinetic Monte Carlo (kMC) simulations of n-butane generated from thermal cracking of model kerogens (I, II, and III) and an oil with a series of reactions (homolytic cleavage, β-scission, radical isomerization, H-abstraction, and termination by radical recombination) provided generally consistent results with the experimental observations, although the difference in PS δ 13 C values between the central and terminal positions are somewhat overestimated. On the other hand, the kMC simulation with homolytic cleavage and capping reactions alone produced significant deviations from the experimental results. Re-assessment of very limited data of PS δ 13 C values of natural butanes with our experimental and simulation results show that biodegradation significantly increased δ 13 C values at the central positions, not only of propane, but also of both butane isomers. This study lays a foundation and demonstrates the potential of PS isotope geochemistry of butane isomers to further improve our understanding of the sources, and geochemical and microbial processes of light hydrocarbons in the subsurface and other natural environments.

Geochimica et Cosmochimica Acta↗
USGS2023

Hidden system identification: Basin modeling as a tool for examining sedimentary geothermal resource potential

Three-dimensional (3D) geologic and temperature models have been developed for the onshore U.S. Gulf Coast. The results from these models identify areas of moderate- to high-temperature (90°-150°C and >150°C; respectively) geothermal resources at depths <6 km. This modeling study addresses the fundamental challenge of predicting where opportune temperature and lithology coincide. Unlike traditional geothermal systems with surface expressions of hydrothermal circulation (e.g., hot springs, fumaroles, sinter), sedimentary geothermal systems (SGS) are generally hidden. Historically, simplified efforts to predict subsurface temperatures in sedimentary basins have focused on linear temperature extrapolation that does not consider the variable thermal properties of different lithologies or lithologic changes with depth (e.g., compaction, lithification). Therefore, the need to understand basin architecture and predict temperatures in 3D within SGS is paramount to identifying geothermal resources and determining economic feasibility. Basin modeling software has long been used to characterize the subsurface conditions of sedimentary basins, including temperature, in the pursuit of finding hydrocarbons. This tool can also be adapted to evaluate the potential of geothermal resources in a sedimentary basin by predicting the confluence of desirable temperatures and reservoir lithologies. In this work, PetroMod basin modeling software was used to create a regional geologic model of the onshore U.S. Gulf Coast, covering over 500,000 km 2 calibrated to temperature data from wells. Inputs include structural surfaces from commercial databases, lithology information derived from published literature, and corrected bottom-hole temperatures (BHT) from over 6,000 wells. The resulting 3D geologic model can be used to predict temperatures throughout the basin. Maps were exported showing the depth, depositional unit, and reservoir lithology at which temperatures of 90°C and 150°C were reached, revealing over 400,000 km 2 of moderate- to high-temperature resources at depths <6 km. These maps function as a first-order screening tool to identify areas where low-, moderate-, or high-grade resource potential may exist, based on temperature and if optimal reservoir lithologies or depositional units of interest are present. Depending on the success criteria of a project, the same maps can be exported for any isotherm or incorporate other 1407 Gardner and Birdwell subsurface properties. The methodology employed in this work can be applied in any sedimentary basin with available subsurface data. Further calibration incorporating other data, including pressure and porosity, can expand the utility of basin modeling for geothermal evaluations. Basin modeling is a powerful but underutilized tool for identifying prospective geothermal resources in sedimentary basins.

Conference Paper↗
USGS2022

Geochemistry of the Cretaceous Mowry Shale in the Wind River Basin, Wyoming

The siliceous nature of the Mowry Shale distinguishes it from many of the well-studied organic-rich mudstones of the Cretaceous Western Interior Seaway. Available models of organic enrichment in mudstones rarely incorporate detailed biomarker, bulk organic, inorganic, and mineralogy data. Here, we used these data to evaluate how variations in organic matter source, productivity, dilution, and preservation modulated organic matter accumulation during the deposition of the Mowry Shale, while also demonstrating the benefits of this integrated approach. An organic stable carbon isotope vertical profile for the Mowry Shale is presented to test whether the Mowry Shale was deposited during oceanic anoxic event 1d (OAE 1d), thereby contributing to organic enrichment in the Mowry Shale.

Wyoming↗
USGS2022

Geologic characterization and depositional history of the Uteland Butte member, Green River Formation, southwestern Uinta Basin, Utah

The 15- to 65-m-thick informal Uteland Butte member of the Eocene Green River Formation represents the first widespread transgression of Lake Uinta in the Uinta Basin, Utah. This study assesses the spatial and temporal variation of Uteland Butte member deposits along a 40-km transect in the southwestern margin of the Uinta Basin using detailed measured sections, organic and inorganic geochemical data, and outcrop gamma ray logs. Fourteen lithofacies are identified, which comprise seven facies associations linked to with lacustrine, palustrine, and deltaic depositional settings. Facies associations are traceable laterally across the study area, where five 4- to 12-m-thick depositional cycles are identified. Each shallowing upwards cycle is defined by a >1.5-m-thick basal package of organic-rich, argillaceous laminated mudstone, and is capped by thick packages of bedded carbonate. In the far western study area (Kyune Creek Canyon), thick deposits of organic-rich mudstone are present and represent the most distal outcrop section; time-equivalent strata in the eastern study area (Minnie Maud Creek Canyon) are relatively organic lean with higher silt and clay content, interpreted to represent proximal lake margin deposits influenced by a nearby delta. The outcrop belt is correlated to more distal cores and well logs across the western Uinta Basin. Similar lithological and petrophysical patterns across the western Uinta Basin are used to subdivide stratigraphy into nine laterally contiguous sub-units based on nomenclature from the oil-producing area of the central basin (from base to top: lower Uteland Butte, D Bench, D Shale, C Bench, C Shale, B Bench, B Shale, A Bench, and A Shale). Siliciclastic clay-rich and carbonaterich intervals are correlated across the region and indicate distinct siliciclastic- and carbonate-dominated lake phases during Uteland Butte member deposition. Climate is interpreted to be the dominant driver of these claycarbonate cycles, in which relatively humid periods resulted in increased fluvially derived siliciclastic sediment into the basin (clay-rich periods), and arid periods resulted in evaporative conditions with decreased fluvial sediment input that favor carbonate accumulation. Climatically driven depositional cycles within the Uteland Butte member reflect, to a smaller degree, the larger scale climatically driven depositional cycles observed at the member- and formation levels of Paleocene and Eocene Uinta Basin stratigraphy. Importantly, the Uteland Butte member clay-carbonate cycles showcase how relatively small-scale climate shifts can impact basin-scale lacustrine deposition.

Utah↗
USGS2022

Geochemical studies of the Green River Formation in the Piceance Basin, Colorado: I. Major, minor, and trace elements

The Eocene Green River Formation contains the largest oil shale deposits in the world and is a welldocumented example of a lacustrine depositional system. In addition, mineral resources associated with oil shale in the Piceance Basin nahcolite [NaHCO3] and dawsonite [NaAl(CO3)(OH)2)] are of current and potential economic value, respectively. Detailed geochemical analysis across the basin can aid in the understanding of the depositional environment, sedimentary processes, and water-chemistry evolution in this system. Quantitative geochemical data for Green River oil shale from the Piceance Basin of Colorado were collected by inductively coupled plasma optical emission spectroscopy and mass spectrometry as part of this study. The basin margin is represented by samples from exposures at Douglas Pass (Garfield County) and the basin center area is characterized by core samples from two drilled wells: the Shell 23X-2 and John Savage 24-1 (Rio Blanco County). Major elements and groups of elements are used as proxies for clastic influx (Si, Al, K, Ti), carbonate deposition (Ca, Mg), salinity (Na), paleo-productivity (P), and redox state (Fe, S), respectively. Minor and trace elements reinforce observations based on major elements, including Rb, Zr, Nb for clastic influx and Mn, Sr for carbonate. Trace elements are used to characterize redox conditions (As, Mo, U, V, Co, Ni, Cu, Zn) and salinity (Rb/K, B/Ga). Chemical distinctions between the basin margin and the basin center, in terms of these components and total organic carbon concentrations, support the model of a permanently stratified lake through most of the depositional interval. A primary purpose of the study was to conduct more extensive sampling to confirm conclusions of a previous reconnaissance study. Geochemical data from this study indicates elevated Na around the basin margin occurring earlier than in the deeper basin. Early in the history of Lake Uinta, the salinity may have been elevated first in the shallower marginal waters, due to increased evaporation, which then led to elevated salinity in the basin center through transport of saline density currents. Other indicators of salinity (Rb/K, B/Ga) do not track Na content in intervals where clay minerals are absent due to diagenetic alteration under hypersaline conditions but may be used to indicate the salinities at which authigenic Na-bearing minerals begin to form. Most Na-rich samples show high proportions of clastic constituents (Si, Al, K, Ti) compared to conventional carbonate constituents (Ca, Mg). Redox-sensitive period IV transition metal elements (V, Co, Ni, Cu, Zn) show only local occurrence of significant enrichment relative to average shale abundances. Analysis of Fe/Al ratios for this dataset suggests that the depletion of these elements may be related to source rocks depleted in mafic constituents, with apparent redox-related enrichments subdued by this effect. The basin margin samples reflect generally oxic bottom waters, with some intervals deposited under more reducing, possibly dysoxic to anoxic conditions. The basin center results indicate more reducing conditions, with Mo and U enrichment factors suggesting operation of a particulate shuttle mechanism that scavenged Mo on Fe/Mn-oxyhydroxides that redissolved at depth, with Mo precipitating along with sulfides and/or organic matter at or near the sediment/water interface.

Colorado↗
USGS2022

Geochemical studies of the Green River Formation in the Piceance Basin, Colorado: II. Chemofacies from hierarchical cluster analysis

Hierarchical cluster analysis (HCA) was applied to a geochemical dataset representing the Eocene Green River Formation in the Piceance Basin of Colorado to identify chemofacies in core and outcrop samples from the basin margin and the basin center. The input dataset consisted of inductively coupled plasma optical emission spectroscopy and mass spectrometry and total organic carbon (TOC) content analyses of 186 basin margin outcrop samples and 190 basin center core samples discussed in Part 1 of this study (this volume). TOC values and twenty-five major and trace elements were used as variables to define statistical clusters of samples for the overall dataset, for the two basin center cores, and for each separate core or outcrop dataset by HCA applying Euclidean distance and Ward’s method algorithms. For each dataset, five cluster-defined chemofacies were identified. The chemofacies for each dataset show chemical affinities with five informally defined rock types– mudstone, marlstone, carbonate-rich mudstone, siliciclastic-rich mudstone/siltstone/sandstone, and Na-rich (saline) mudstone, with each showing variations in TOC content and abundance of redox sensitive minor and trace elements. A close relationship between enrichment of redox sensitive elements, particularly As and Mo, and TOC is identified in the basin center. Whereas enrichment factors (relative to average shale) are relatively low for many Period IV (PIV) transition metals, as discussed in Part 1 of this study, their consistent coherence in enrichment or depletion in HCA-defined chemofacies demonstrates the expected relationship between redox state and organic richness. Enrichment in PIV transition metals also shows a correlation to enrichment in elements with affinity for siliciclastic sediment. Enrichment/depletion among several groups of redox indicators is not everywhere consistent, with some chemofacies showing, for example, enrichment of PIV transition metals and depletion of sulfur and arsenic. Early timing of saline conditions in the basin margin is clearly displayed in the chemofacies log display, consistent with observations based on geochemical interpretations of concentrations and elemental ratios discussed in Part 1. Overall, the chemofacies are consistent with major mineralogical units and lake history stages defined in previous work, but provide more detail on the fluctuations in lake chemistry that occurred during deposition of Green River oil shale in the Piceance Basin.

Colorado↗