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Justin E. Birdwell

Publications and source records attributed to Justin E. Birdwell.

108 records · Page 6Linked to original sources
USGS2014

Application of binomial-edited CPMG to shale characterization

Unconventional shale resources may contain a significant amount of hydrogen in organic solids such as kerogen, but it is not possible to directly detect these solids with many NMR systems. Binomial-edited pulse sequences capitalize on magnetization transfer between solids, semi-solids, and liquids to provide an indirect method of detecting solid organic materials in shales. When the organic solids can be directly measured, binomial-editing helps distinguish between different phases. We applied a binomial-edited CPMG pulse sequence to a range of natural and experimentally-altered shale samples. The most substantial signal loss is seen in shales rich in organic solids while fluids associated with inorganic pores seem essentially unaffected. This suggests that binomial-editing is a potential method for determining fluid locations, solid organic content, and kerogen–bitumen discrimination.

Journal of Magnetic Resonance↗
USGS2014

Simultaneous Gaussian and exponential inversion for improved analysis of shales by NMR relaxometry

Nuclear magnetic resonance (NMR) relaxometry is commonly used to provide lithology-independent porosity and pore-size estimates for petroleum resource evaluation based on fluid-phase signals. However in shales, substantial hydrogen content is associated with solid and fluid signals and both may be detected. Depending on the motional regime, the signal from the solids may be best described using either exponential or Gaussian decay functions. When the inverse Laplace transform, the standard method for analysis of NMR relaxometry results, is applied to data containing Gaussian decays, this can lead to physically unrealistic responses such as signal or porosity overcall and relaxation times that are too short to be determined using the applied instrument settings. We apply a new simultaneous Gaussian-Exponential (SGE) inversion method to simulated data and measured results obtained on a variety of oil shale samples. The SGE inversion produces more physically realistic results than the inverse Laplace transform and displays more consistent relaxation behavior at high magnetic field strengths. Residuals for the SGE inversion are consistently lower than for the inverse Laplace method and signal overcall at short T2 times is mitigated. Beyond geological samples, the method can also be applied in other fields where the sample relaxation consists of both Gaussian and exponential decays, for example in material, medical and food sciences.

Journal of Magnetic Resonance↗
USGS2014

Differentiation of pre-existing trapped methane from thermogenic methane in an igneous-intruded coal by hydrous pyrolysis

So as to better understand how the gas generation potential of coal changes with increasing rank, same-seam samples of bituminous coal from the Illinois Basin that were naturally matured to varying degrees by the intrusion of an igneous dike were subjected to hydrous pyrolysis (HP) conditions of 360 °C for 72 h. The accumulated methane in the reactor headspace was analyzed for δ 13 C and δ2H, and mol percent composition. Maximum methane production (9.7 mg/g TOC) occurred in the most immature samples (0.5 %R o ), waning to minimal methane values at 2.44 %Ro (0.67 mg/g TOC), and rebounding to 3.6 mg/g TOC methane in the most mature sample (6.76 %R o ). Methane from coal with the highest initial thermal maturity (6.76 %R o ) shows no isotopic dependence on the reactor water and has a microbial δ 13 C value of −61‰. However, methane from coal of minimal initial thermal maturity (0.5 %R o ) shows hydrogen isotopic dependence on the reaction water and has a δ 13 C value of −37‰. The gas released from coals under hydrous pyrolysis conditions represents a quantifiable mixture of ancient (270 Ma) methane (likely microbial) that was generated in situ and trapped within the rock during the rapid heating by the dike, and modern (laboratory) thermogenic methane that was generated from the indigenous organic matter due to thermal maturation induced by hydrous pyrolysis conditions. These findings provide an analytical framework for better assessment of natural gas sources and for differentiating generated gas from pre-existing trapped gas in coals of various ranks.

Organic Geochemistry↗
USGS2014

In-place oil shale resources in the saline-mineral and saline-leached intervals, Parachute Creek Member of the Green River Formation, Piceance Basin, Colorado

A recent U.S. Geological Survey analysis of the Green River Formation of the Piceance Basin in western Colorado shows that about 920 and 352 billion barrels of oil are potentially recoverable from oil shale resources using oil-yield cutoffs of 15 and 25 gallons per ton (GPT), respectively. This represents most of the high-grade oil shale in the United States. Much of this rich oil shale is found in the dolomitic Parachute Creek Member of the Green River Formation and is associated with the saline minerals nahcolite and halite, or in the interval where these minerals have been leached by groundwater. The remaining high-grade resource is located primarily in the underlying illitic Garden Gulch Member of the Green River Formation. Of the 352 billion barrels of potentially recoverable oil resources in high-grade (≥25 GPT) oil shale, the relative proportions present in the illitic interval, non-saline R-2 zone, saline-mineral interval, leached interval (excluding leached Mahogany zone), and Mahogany zone were 3.1, 4.5, 36.6, 23.9, and 29.9 percent of the total, respectively. Only 2 percent of high-grade oil shale is present in marginal areas where saline minerals were never deposited.

Colorado↗
USGS2013

A new laboratory approach to shale analysis using NMR relaxometry

Low-field nuclear magnetic resonance (LF-NMR) relaxometry is a non-invasive technique commonly used to assess hydrogen-bearing fluids in petroleum reservoir rocks. Measurements made using LF-NMR provide information on rock porosity, pore-size distributions, and in some cases, fluid types and saturations (Timur, 1967; Kenyon et al., 1986; Straley et al., 1994; Brown, 2001; Jackson, 2001; Kleinberg, 2001; Hurlimann et al., 2002). Recent improvements in LF-NMR instrument electronics have made it possible to apply methods used to measure pore fluids to assess highly viscous and even solid organic phases within reservoir rocks. T 1 and T 2 relaxation responses behave very differently in solids and liquids; therefore the relationship between these two modes of relaxation can be used to differentiate organic phases in rock samples or to characterize extracted organic materials. Using T 1 -T 2 correlation data, organic components present in shales, such as kerogen and bitumen, can be examined in laboratory relaxometry measurements. In addition, implementation of a solid-echo pulse sequence to refocus T 2 relaxation caused by homonuclear dipolar coupling during correlation measurements allows for improved resolution of solid-phase protons. LF-NMR measurements of T 1 and T 2 relaxation time distributions were carried out on raw oil shale samples from the Eocene Green River Formation and pyrolyzed samples of these shales processed by hydrous pyrolysis and techniques meant to mimic surface and in-situ retorting. Samples processed using the In Situ Simulator approach ranged from bitumen and early oil generation through to depletion of petroleum generating potential. The standard T 1 -T 2 correlation plots revealed distinct peaks representative of solid- and liquid-like organic phases; results on the pyrolyzed shales reflect changes that occurred during thermal processing. The solid-echo T 1 and T 2 measurements were used to improve assessment of the solid organic phases, specifically kerogen, thermally degraded kerogen, and char. Integrated peak areas from the LF-NMR results representative of kerogen and bitumen were found to be well correlated with S1 and S2 parameters from Rock-Eval programmed pyrolysis. This study demonstrates that LFNMR relaxometry can provide a wide range of information on shales and other reservoir rocks that goes well beyond porosity and pore-fluid analysis.

Conference Paper↗
USGS2013

Geochemical changes and fracture development in Woodford Shale cores following hydrous pyrolysis under uniaxial confinement

A uniaxial confinement clamp was used on Woodford Shale cores in hydrous pyrolysis experiments to study fracture development during thermal maturation. The clamp simulates overburden in that it prevents cores from expanding perpendicular to bedding fabric during the volume-increasing reactions associated with petroleum generation. Cores were cut from a slab of immature Woodford Shale and subjected to hydrous pyrolysis under confinement at 300, 330, and 365 °C for 72 hours to induce thermal maturities ranging from early bitumen to maximum expelled-oil generation. Two additional cores were used as experimental controls: (1) a confined core was saturated with water by heating it to 100 °C under hydrous pyrolysis conditions for 72 hours to use for characterization of the original rock, and (2) an unconfined core was heated at 365 °C for 72 hours to evaluate the effects of confinement on petroleum generation and expulsion. X-ray computed tomography (X-CT) imaging and other analyses identified five distinct beds within the cored interval. Using a tentative classification system, beds 1, 2, and 3 are described as dolomitic marlstone (DM) with total organic carbon (TOC) contents of 7.7, 5.8, and 7.7 wt. %, respectively; bed 4 is a cherty quartzose claystone (CQC) with TOC content of 5.5 wt. %; and bed 5 is a quartzose claystone with TOC content of 10.9 wt. %. Bed samples all had similar Rock-Eval hydrogen indices (600 ± 46 mg S2/g-TOC) and Tmax values (433 ± 2 °C), demonstrating organic matter uniformity and low thermal maturity. The X-CT scan of the core heated to 100 °C showed preexisting fractures that were nearly perpendicular to the bedding fabric primarily in the low-TOC DM bed 2 and CQC bed 4. Heating led to enhancement of preexisting fractures in the confined cores with the greatest enhancement occurring in CQC bed 4. The fractures increased in size and intensity with temperature. This is attributed to the internal pressure generated by volume-increasing reactions during the conversion of kerogen to bitumen and bitumen to oil and gas. The unconfined core heated to 365 °C showed no enhanced fracturing and its X-CT-scan resembled that of the 100 °C confined core. Comparison of the oil and gas yields from the confined and unconfined cores heated to 365 °C showed no significant differences, indicating that product expulsion is not inhibited by the procedure used in this study. These results also indicate that fracturing during thermal maturation is driven primarily by the enhancement of existing fractures.

Conference Paper↗
USGS2013

Changes in porosity and organic matter phase distribution monitored by NMR relaxometry following hydrous pyrolysis under uniaxial confinement

Artificial maturation methods are used to induce changes in source rock thermal maturity without the uncertainties that arise when comparing natural samples from a particular basin that often represent different levels of maturation and different lithofacies. A novel uniaxial confinement clamp was used on Woodford Shale cores in hydrous pyrolysis experiments to limit sample expansion by simulating the effect of overburden present during thermal maturation in natural systems. These samples were then subjected to X-ray computed tomography (X-CT) imaging and low-field nuclear magnetic resonance (LF-NMR) relaxometry measurements. LF-NMR relaxometry is a noninvasive technique commonly used to measure porosity and pore-size distributions in fluid-filled porous media, but may also measure hydrogen present in hydrogen-bearing organic solids. Standard T 1 and T 2 relaxation distributions were determined and two dimensional T 1 -T 2 correlation measurements were performed on the Woodford Shale cores. The T 1 -T 2 correlations facilitate resolution of organic phases in the system. The changes observed in NMR-relaxation times correspond to bitumen and lighter hydrocarbon production that occur as source rock organic matter matures. The LF-NMR porosities of the core samples at maximum oil generation are significantly higher than porosities measured by other methods. This discrepancy likely arises from the measurement of highly viscous organic constituents in addition to fluid-filled porosity. An unconfined sample showed shorter relaxation times and lower porosity. This difference is attributed to the lack of fractures observed in the unconfined sample by X-CT.

Conference Paper↗
USGS2013

Application of uniaxial confining-core clamp with hydrous pyrolysis in petrophysical and geochemical studies of source rocks at various thermal maturities

Understanding changes in petrophysical and geochemical parameters during source rock thermal maturation is a critical component in evaluating source-rock petroleum accumulations. Natural core data are preferred, but obtaining cores that represent the same facies of a source rock at different thermal maturities is seldom possible. An alternative approach is to induce thermal maturity changes by laboratory pyrolysis on aliquots of a source-rock sample of a given facies of interest. Hydrous pyrolysis is an effective way to induce thermal maturity on source-rock cores and provide expelled oils that are similar in composition to natural crude oils. However, net-volume increases during bitumen and oil generation result in expanded cores due to opening of bedding-plane partings. Although meaningful geochemical measurements on expanded, recovered cores are possible, the utility of the core for measuring petrophysical properties relevant to natural subsurface cores is not suitable. This problem created during hydrous pyrolysis is alleviated by using a stainless steel uniaxial confinement clamp on rock cores cut perpendicular to bedding fabric. The clamp prevents expansion just as overburden does during natural petroleum formation in the subsurface. As a result, intact cores can be recovered at various thermal maturities for the measurement of petrophysical properties as well as for geochemical analyses. This approach has been applied to 1.7-inch diameter cores taken perpendicular to the bedding fabric of a 2.3- to 2.4-inch thick slab of Mahogany oil shale from the Eocene Green River Formation. Cores were subjected to hydrous pyrolysis at 360 °C for 72 h, which represents near maximum oil generation. One core was heated unconfined and the other was heated in the uniaxial confinement clamp. The unconfined core developed open tensile fractures parallel to the bedding fabric that result in a 38 % vertical expansion of the core. These open fractures did not occur in the confined core, but short, discontinuous vertical fractures on the core periphery occurred as a result of lateral expansion.

Conference Paper↗
USGS2013

Updated methodology for nuclear magnetic resonance characterization of shales

Unconventional petroleum resources, particularly in shales, are expected to play an increasingly important role in the world’s energy portfolio in the coming years. Nuclear magnetic resonance (NMR), particularly at low-field, provides important information in the evaluation of shale resources. Most of the low-field NMR analyses performed on shale samples rely heavily on standard T 1 and T 2 measurements. We present a new approach using solid echoes in the measurement of T 1 and T 1 –T 2 correlations that addresses some of the challenges encountered when making NMR measurements on shale samples compared to conventional reservoir rocks. Combining these techniques with standard T 1 and T 2 measurements provides a more complete assessment of the hydrogen-bearing constituents (e.g., bitumen, kerogen, clay-bound water) in shale samples. These methods are applied to immature and pyrolyzed oil shale samples to examine the solid and highly viscous organic phases present during the petroleum generation process. The solid echo measurements produce additional signal in the oil shale samples compared to the standard methodologies, indicating the presence of components undergoing homonuclear dipolar coupling. The results presented here include the first low-field NMR measurements performed on kerogen as well as detailed NMR analysis of highly viscous thermally generated bitumen present in pyrolyzed oil shale.

Journal of Magnetic Resonance↗
USGS2013

Multivariate analysis of ATR-FTIR spectra for assessment of oil shale organic geochemical properties

In this study, attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FTIR) was coupled with partial least squares regression (PLSR) analysis to relate spectral data to parameters from total organic carbon (TOC) analysis and programmed pyrolysis to assess the feasibility of developing predictive models to estimate important organic geochemical parameters. The advantage of ATR-FTIR over traditional analytical methods is that source rocks can be analyzed in the laboratory or field in seconds, facilitating more rapid and thorough screening than would be possible using other tools. ATR-FTIR spectra, TOC concentrations and Rock–Eval parameters were measured for a set of oil shales from deposits around the world and several pyrolyzed oil shale samples. PLSR models were developed to predict the measured geochemical parameters from infrared spectra. Application of the resulting models to a set of test spectra excluded from the training set generated accurate predictions of TOC and most Rock–Eval parameters. The critical region of the infrared spectrum for assessing S1, S2, Hydrogen Index and TOC consisted of aliphatic organic moieties (2800–3000 cm −1 ) and the models generated a better correlation with measured values of TOC and S2 than did integrated aliphatic peak areas. The results suggest that combining ATR-FTIR with PLSR is a reliable approach for estimating useful geochemical parameters of oil shales that is faster and requires less sample preparation than current screening methods.

Organic Geochemistry↗
USGS2013

Characterization of oil shale, isolated kerogen, and post-pyrolysis residues using advanced 13 solid-state nuclear magnetic resonance spectroscopy

Characterization of oil shale kerogen and organic residues remaining in postpyrolysis spent shale is critical to the understanding of the oil generation process and approaches to dealing with issues related to spent shale. The chemical structure of organic matter in raw oil shale and spent shale samples was examined in this study using advanced solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy. Oil shale was collected from Mahogany zone outcrops in the Piceance Basin. Five samples were analyzed: (1) raw oil shale, (2) isolated kerogen, (3) oil shale extracted with chloroform, (4) oil shale retorted in an open system at 500°C to mimic surface retorting, and (5) oil shale retorted in a closed system at 360°C to simulate in-situ retorting. The NMR methods applied included quantitative direct polarization with magic-angle spinning at 13 kHz, cross polarization with total sideband suppression, dipolar dephasing, CH n selection, 13 C chemical shift anisotropy filtering, and 1 H- 13 C long-range recoupled dipolar dephasing. The NMR results showed that, relative to the raw oil shale, (1) bitumen extraction and kerogen isolation by demineralization removed some oxygen-containing and alkyl moieties; (2) unpyrolyzed samples had low aromatic condensation; (3) oil shale pyrolysis removed aliphatic moieties, leaving behind residues enriched in aromatic carbon; and (4) oil shale retorted in an open system at 500°C contained larger aromatic clusters and more protonated aromatic moieties than oil shale retorted in a closed system at 360°C, which contained more total aromatic carbon with a wide range of cluster sizes.

American Association of Petroleum Geologists Bulle↗
USGS2013

In-place oil shale resources examined by grade in the major basins of the Green River Formation, Colorado, Utah, and Wyoming

Using a geology-based assessment methodology, the U.S. Geological Survey estimated a total of 4.285 trillion barrels of oil in-place in the oil shale of the three principal basins of the Eocene Green River Formation. Using oil shale cutoffs of potentially viable (15 gallons per ton) and high grade (25 gallons per ton), it is estimated that between 353 billion and 1.146 trillion barrels of the in-place resource have a high potential for development.

Colorado;Utah;Wyoming↗
USGS2013

NMR measurement of oil shale magnetic relaxation at high magnetic field

Nuclear magnetic resonance (NMR) at low field is used extensively to provide porosity and pore-size distributions in reservoir rocks. For unconventional resources, due to low porosity and permeability of the samples, much of the signal exists at very short T 2 relaxation times. In addition, the organic content of many shales will also produce signal at short relaxation times. Despite recent improvements in low-field technology, limitations still exist that make it difficult to account for all hydrogen-rich constituents in very tight rocks, such as shales. The short pulses and dead times along with stronger gradients available when using high-field NMR equipment provides a more complete measurement of hydrogen-bearing phases due to the ability to probe shorter T 2 relaxation times (<10 -5 sec) than can be examined using low-field equipment. Access to these shorter T 2 times allows for confirmation of partially resolved peaks observed in low-field NMR data that have been attributed to solid organic phases in oil shales. High-field (300 MHz or 7 T) NMR measurements of spin-spin T 2 and spin-lattice T 1 magnetic relaxation of raw and artificially matured oil shales have potential to provide data complementary to low field (2 MHz or 0.05T) measurements. Measurements of high-field T 2 and T 1 -T 2 correlations are presented. These data can be interpreted in terms of organic matter phases and mineral-bound water known to be present in the shale samples, as confirmed by Fourier transform infrared spectroscopy, and show distributions of hydrogen-bearing phases present in the shales that are similar to those observed in low field measurements.

Conference Paper↗
USGS2013

Low-field nuclear magnetic resonance characterization of organic content in shales

Low-field nuclear magnetic resonance (LF-NMR) relaxometry is a non-invasive technique commonly used to assess hydrogen-bearing fluids in petroleum reservoir rocks. Longitudinal T 1 and transverse T 2 relaxation time measurements made using LF-NMR on conventional reservoir systems provides information on rock porosity, pore size distributions, and fluid types and saturations in some cases. Recent improvements in LF-SNMR instrument electronics have made it possible to apply these methods to assess highly viscous and even solid organic phases within reservoir rocks. T 1 and T 2 relaxation responses behave very differently in solids and liquids, therefore the relationship between these two modes of relaxation can be used to differentiate organic phases in rock samples or to characterize extracted organic materials. Using T 1 -T 2 correlation data, organic components present in shales, such as kerogen and bitumen, can be examined in laboratory relaxometry measurements. In addition, implementation of a solid-echo pulse sequence to refocus some types of T 2 relaxation during correlation measurements allows for improved resolution of solid phase photons. LF-NMR measurements of T 1 and T 2 relaxation time correlations were carried out on raw oil shale samples from resources around the world. These shales vary widely in mineralogy, total organic carbon (TOC) content and kerogen type. NMR results were correlcated with Leco TOC and geochemical data obtained from Rock-Eval. There is excellent correlation between NMR data and programmed pyrolysis parameters, particularly TOC and S2, and predictive capability is also good. To better understand the NMR response, the 2D NMR spectra were compared to similar NMR measurements made using high-field (HF) NMR equipment.

Conference Paper↗
USGS2012

Comparing Laser Desorption Ionization and Atmospheric Pressure Photoionization Coupled to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry To Characterize Shale Oils at the Molecular Level

Laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to analyze shale oils. Previous work showed that LDI is a sensitive ionization technique for assessing aromatic nitrogen compounds, and oils generated from Green River Formation oil shales are well-documented as being rich in nitrogen. The data presented here demonstrate that LDI is effective in ionizing high-double-bond-equivalent (DBE) compounds and, therefore, is a suitable method for characterizing compounds with condensed structures. Additionally, LDI generates radical cations and protonated ions concurrently, the distribution of which depends upon the molecular structures and elemental compositions, and the basicity of compounds is closely related to the generation of protonated ions. This study demonstrates that LDI FT-ICR MS is an effective ionization technique for use in the study of shale oils at the molecular level. To the best of our knowledge, this is the first time that LDI FT-ICR MS has been applied to shale oils.

Energy & Fuels↗
USGS2012

Molecular characterization and comparison of shale oils generated by different pyrolysis methods

Shale oils generated using different laboratory pyrolysis methods have been studied using standard oil characterization methods as well as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI) and atmospheric photoionization (APPI) to assess differences in molecular composition. The pyrolysis oils were generated from samples of the Mahogany zone oil shale of the Eocene Green River Formation collected from outcrops in the Piceance Basin, Colorado, using three pyrolysis systems under conditions relevant to surface and in situ retorting approaches. Significant variations were observed in the shale oils, particularly the degree of conjugation of the constituent molecules and the distribution of nitrogen-containing compound classes. Comparison of FT-ICR MS results to other oil characteristics, such as specific gravity; saturate, aromatic, resin, asphaltene (SARA) distribution; and carbon number distribution determined by gas chromatography, indicated correspondence between higher average double bond equivalence (DBE) values and increasing asphaltene content. The results show that, based on the shale oil DBE distributions, highly conjugated species are enriched in samples produced under low pressure, high temperature conditions, and under high pressure, moderate temperature conditions in the presence of water. We also report, for the first time in any petroleum-like substance, the presence of N 4 class compounds based on FT-ICR MS data. Using double bond equivalence and carbon number distributions, structures for the N 4 class and other nitrogen-containing compounds are proposed.

Energy & Fuels↗
USGS2012

Review of rare earth element concentrations in oil shales of the Eocene Green River Formation

Concentrations of the lanthanide series or rare earth elements and yttrium were determined for lacustrine oil shale samples from the Eocene Green River Formation in the Piceance Basin of Colorado and the Uinta Basin of Utah. Unprocessed oil shale, post-pyrolysis (spent) shale, and leached shale samples were examined to determine if oil-shale processing to generate oil or the remediation of retorted shale affects rare earth element concentrations. Results for unprocessed Green River oil shale samples were compared to data published in the literature on reference materials, such as chondritic meteorites, the North American shale composite, marine oil shale samples from two sites in northern Tibet, and mined rare earth element ores from the United States and China. The Green River oil shales had lower rare earth element concentrations (66.3 to 141.3 micrograms per gram, &mu;g g -1 ) than are typical of material in the upper crust (approximately 170 &mu;g g -1 ) and were also lower in rare earth elements relative to the North American shale composite (approximately 165 &mu;g g -1 ). Adjusting for dilution of rare earth elements by organic matter does not account for the total difference between the oil shales and other crustal rocks. Europium anomalies for Green River oil shales from the Piceance Basin were slightly lower than those reported for the North American shale composite and upper crust. When compared to ores currently mined for rare earth elements, the concentrations in Green River oil shales are several orders of magnitude lower. Retorting Green River oil shales led to a slight enrichment of rare earth elements due to removal of organic matter. When concentrations in spent and leached samples were normalized to an original rock basis, concentrations were comparable to those of the raw shale, indicating that rare earth elements are conserved in processed oil shales.

Utah;Colorado;Wyoming↗