Geology topics

Leslie F. Ruppert

Publications and source records attributed to Leslie F. Ruppert.

At least 19 recordsLinked to original sources

USGS2026

Neutron scattering reveals fractionation of natural gas mixtures in unconventional petroleum reservoir pores: Perspectives on energy resource recovery and storage

In unconventional petroleum reservoirs hydrocarbon fluids are hosted by both mineral and organic matter pores. These pores can have diameters that range from microns to less than a single nanometer and, for unconventional reservoirs, there is evidence that small pores ( <20 nm diameter) may constitute a large proportion of the available space. Understanding subsurface volumes and how fluids behave in them can be helpful for predicting hydrocarbon production and storage in the subsurface. One area with knowledge gaps regarding hydrocarbon behavior in small pores is the possibility for mixtures to fractionate (i.e., unmix) based on pore size or pore type. Mixture fractionation as a function of pore size could impact recovery of hydrocarbons, drive compositional shifts during production, and limit fluid storage within candidate reservoirs. To investigate natural gas fractionation in small geologic pores, we applied total neutron scattering to probe methane-ethane mixtures at reservoir pressures (up to ≈30 MPa) and temperature (60°C) within a sample from the Upper Cretaceous Niobrara Formation. Neutron scattering data reveal only minor fractionation occurs between methane and ethane in 20-nm diameter sample mesopores. Increased fractionation is observed for sample micropores, with up to 72% (±1% at 1-sigma) methane found in 2 nm diameter pores following injection of a 50%-50% methane-ethane mixture. These data provide rarely available direct experimental observations of hydrocarbon mixture behavior under nanoconfinement in a sample from an important unconventional petroleum reservoir. Our results are discussed in the context of evaluating hydrocarbon resources in unconventional reservoir meso- and micropores, reconciling observed gas composition changes during production, and more broadly, understanding subsurface pore volumes within an energy storage framework.

Fuel↗

USGS2025

Stories in stone: The geoheritage significance of U.S. National Park Service stratotypes

The U.S. National Park Service stratotype inventory has systematically documented hundreds of published stratotypes across the country that represent a quintessential component of America’s geoheritage and possess significant scientific, educational, cultural, historic, and aesthetic values. As valuable geologic reference standards, stratotypes record intervals of Earth history relating to our nation’s unique geologic evolution, biological progression, cultural traditions, historical narratives, and stunning landforms. However, the general lack of awareness and knowledge regarding the scope, significance, distribution, and scale of stratotypes can result in these resources being overlooked. Consequently, stratotypes may inadvertently experience accidental alteration, damage, or destruction through both natural and anthropogenic processes. As with many American geoheritage sites, stratotypes lack specific recognition through legislation, policies, or other management strategies to ensure their preservation and protection. Through education and outreach, we hope to inform, increase awareness, and engage the public about these internationally and nationally significant geologic reference sites, unite various geoheritage communities, and promote their preservation for future generations.

Geoheritage↗

USGS2025

U.S. Geological Survey geoheritage sites of the nation: Broadening the relevance of geologic mapping through the intersection of geology and society

Geoheritage lies at the intersection of geology and society (NASEM 2021). It is a value-laden term applied to geologically significant features and landforms to highlight the scientific, educational, cultural, economic, and aesthetic values that society places on them (Brilha 2018, GSA 2017, NPS and AGI 2015). The U.S. Geological Survey (USGS) National Cooperative Geologic Mapping Program (NCGMP) proposed the development of a geoheritage geospatial product (GGP) to broaden the relevance of geologic mapping to stakeholders within the scientific community and the public (Shelton et al. 2022). To accomplish this, the USGS Geoheritage Sites of the Nation project was initiated to design the GGP and build a geoheritage site inventory to showcase geodiversity and natural heritage throughout the United States and its territories to accompany the seamless 2D and 3D geologic map and model being developed by the NCGMP and its partners (DeVera et al. 2022). The GGP serves as an educational and outreach tool to 1) raise awareness of significant geologic sites, 2) communicate the role of geology in our natural heritage, and 3) increase accessibility and relevance of geologic mapping and geoscience topics more broadly to the public (DeVera et al. 2023b).

Conference Paper↗

USGS2023

Divisions of geologic time—Major chronostratigraphic and geochronologic units

Introduction Effective communication in the geosciences requires consistent use of stratigraphic nomenclature, especially divisions of geologic time. A geologic time scale is composed of standard stratigraphic divisions that are based on rock sequences and is calibrated in years (Harland and others, 1982). Over the years, the development of new dating methods and the refinement of previous ones have stimulated revisions to geologic time scales. Since the mid-1990s, geologists from the U.S. Geological Survey (USGS), State geological surveys, academia, and other organizations have sought a consistent time scale that can be used in communicating ages of geologic units in the United States. Many international debates have occurred over the names and boundaries of units, and various time scales have been used by the geoscience community in years past (for example, U.S. Geological Survey Geologic Names Committee [USGS GNC], 2007, 2010, 2018). However, the numerical ages assigned to geochronologic units frequently change as the science of stratigraphy moves forward. Once ratified, changes in numerical ages are recorded by the International Commission on Stratigraphy (ICS) on their website ( https://stratigraphy.org/chart ). In addition, such advances in stratigraphy and changes in geochronology require that any time scale be periodically updated. Therefore, the time scale presented in this report (hereafter referred to as “Divisions of Geologic Time”) is dynamic, and it is modified as needed to include accepted changes of unit names and boundary age estimates (USGS GNC, 2007, 2010, 2018).

Professional Paper↗

USGS2023

Broadening the perspectives of sedimentary organic matter analysis to understand Earth system response to change

This paper broadens the description of sedimentary organic matter from the conventional use of coal petrography to include palynological and geochemical sedimentary organic matter. Palynological sedimentary organic matter includes all chemically resistant organic microfossils, such as pollen and spores, dinocysts, microforaminifera (chitinoid-like linings of foraminifera), microscopic algae, charcoal, palynodebris, acritarchs, chitinozoans, and scolecodonts. Geochemical sedimentary organic matter includes organic biomarkers, lipids, and photosynthetic pigments. We provide examples of the use of palynological and geochemical analysis of sedimentary organic matter to understand patterns and impacts of changing climate, fire regimes, hydrologic extremes, water quality, and land change on terrestrial and marine systems through geologic time to provide a long-term perspective to evaluate anthropogenic impacts on the Earth as well as to support forensics investigations.

International Journal of Coal Geology↗

USGS2023

Methane pore accessibility, densification, and accommodation by organic matter in the Niobrara Formation at wet-gas thermal maturity conditions

Petroleum within unconventional source-rock reservoirs is hosted in organic matter and mineral pore space as well as in voids and microfractures. Recent work has shown that for source-rock reservoirs in the dry gas window, significant portions of methane (CH 4 ), the main component of petroleum at elevated maturities, can be stored within fine (<5 nm) organic matter porosity. However, within reservoirs at lower thermal maturities (e.g., peak oil or wet-gas conditions), the distribution and behavior of CH 4 and the higher alkanes that comprise gas condensates across pore sizes is unclear, especially for pores with diameters <50 nm. Understanding CH 4 distribution within these settings provides insight for petroleum generation, movement, and recoverability, ultimately enabling increased accuracy of estimated ultimate recovery. Here wide Q-range total neutron scattering was used to evaluate perdeuterated methane (CD 4 ) behavior at reservoir pressures (200–750 bar) and temperature (60 °C) in a sample at the late oil/wet gas thermal maturity stage from the Late Cretaceous Niobrara Formation, an active petroleum producing formation within the Denver-Julesburg Basin, U.S. Neutron scattering data show that mesopores within the Niobrara Formation sample exhibit mass fractal scattering, similar to previously measured U.S. marine shale samples. In the presence of CD 4 , scattering intensities between Q = 0.02–0.1 Å −1 (corresponding to nominal pore diameters from 25 to 5 nm, respectively) decrease with increased pressure up to 750 bar where at least 80% of all pores with ~25 nm diameters are CD 4 accessible. In contrast, between Q = 0.1–1 Å −1 (corresponding to nominal pore diameters from 5 to 0.5 nm, respectively), scattering intensity initially increased at the lowest CD 4 pressure tested (200 bar) before decreasing with increasing pressure. These signal fluctuations with CD 4 pressure are interpreted to arise from the creation of pores with diameters <5 nm, likely through deformation of solid bitumen by supercritical CD 4 , and/or the incorporation of CD 4 within sample organic matter. This new porosity represents an increase of at least ~8% in available pore volume within the sample, although the majority of these pores do not persist following removal of CD 4 . Additionally, there is strong evidence for densification of CD 4 within the sample indicated by a shift in the CD 4 intermolecular scattering peak to higher Q-values compared to bulk CD 4 . These results provide insight into fluid properties within source-rock reservoirs at late oil/wet gas thermal maturities, especially as they relate to organic porosity interconnectivity, and are discussed with perspective toward pressure management of gas condensate wells.

Colorado, Kansas, Nebraska, Wyoming↗

USGS2022

In situ enhancement and isotopic labeling of biogenic coalbed methane

Subsurface microbial (biogenic) methane production is an important part of the global carbon cycle that has resulted in natural gas accumulations in many coal beds worldwide. Laboratory studies suggest that complex carbon-containing nutrients (e.g., yeast or algae extract) can stimulate methane production, yet the effectiveness of these nutrients within coal beds is unknown. Here, we use downhole monitoring methods in combination with deuterated water (D 2 O) and a 200-liter injection of 0.1% yeast extract (YE) to stimulate and isotopically label newly generated methane. A total dissolved gas pressure sensor enabled real-time gas measurements (641 days preinjection and for 478 days postinjection). Downhole samples, collected with subsurface environmental samplers, indicate that methane increased 132% above preinjection levels based on isotopic labeling from D 2 O, 108% based on pressure readings, and 183% based on methane measurements 266 days postinjection. Demonstrating that YE enhances biogenic coalbed methane production in situ using multiple novel measurement methods has immediate implications for other field-scale biogenic methane investigations, including in situ methods to detect and track microbial activities related to the methanogenic turnover of recalcitrant carbon in the subsurface.

Montana↗

USGS2021

Coking coal of the United States—Modern and historical coking coal mining locations and chemical, rheological, petrographic, and other data from modern samples

Coking coal, or metallurgical coal, has been produced in the United States for nearly 200 years. Coking coal is primarily used in the production of coke for use in the steel industry, and for other uses (for example, foundries, blacksmithing, heating buildings, and brewing). Currently, U.S. coking coal is produced in Alabama, Arkansas, Pennsylvania, Virginia , and West Virginia. Historically, coking coal has also been produced in 15 other states (Alaska, Colorado, Georgia, Illinois, Indiana, Kentucky, Maryland, Montana, New Mexico, Ohio, Oklahoma, Tennessee, Utah, Washington, and Wyoming), but currently is not. Coals from the Appalachian, Arkoma, and Illinois basins are Pennsylvanian in age, while coals in Alaska, Colorado, Montana, New Mexico, Utah, Washington, and Wyoming range in age from Early Cretaceous through Eocene. This Open-File Report presents the geographic locations of current and historical coking coal deposits of the United States, with additional information about recent and historical mining and exploration activities. Chemical, rheological, petrographic, and other criteria for evaluating the coking potential of coals are discussed, and historical data for coking coals in the United States are presented. In addition, new coking coal samples from Alabama, Arkansas, Kentucky, and Oklahoma were collected and analyzed for this report, and the data are presented in multiple tables, including proximate and ultimate analyses; calorific value; sulfur forms; major-, minor-, and trace-element abundances; Free-Swelling Index; Gieseler Plastometer analyses; American Society for Testing and Materials (ASTM) dilatation; coal petrography; and predicted values of Coal Stability Factor and Coal Strength after Reaction with CO 2 (pCSF and pCSR, respectively). Data from previously analyzed coking coal samples in Kentucky, Pennsylvania, Virginia, and West Virginia were supplied by three companies, including results from all the tests listed above, plus oxidation, Hardgrove Grindability Index, and ash fusion (in a reducing environment) temperatures are also presented in tables in the report. Geographic Information System (GIS) data compiled for this project are available for download for public and private utilization and may be used to create maps for a variety of energy resource studies. These GIS data are in shapefile format, and metadata files are included describing all GIS processing. Additional geographic information about coking coal areas of the United States are also presented in tabular format in the report, including the following: names of coal basins, fields, regions, districts, and areas; coal beds or zones; geographic locations including States, counties, towns, rivers, mountains, etc.; stratigraphic hierarchy and age of the coal-bearing interval; coking characteristics including sulfur content, ash yield, volatile matter, moisture, calorific value, and Free-Swelling Index; coal rank; names of coal mines and coal-mining companies; current and past mining activity; and references for reports about the coal.

Open-File Report↗

USGS2021

Insights on the characteristics and sources of gas from an underground coal mine using compositional data analysis

Coal mine gas originates from the gas emission zone (GEZ) of the mine, as well as the longwall face and pillars. Gas emissions are controlled directly at the sources using horizontal or vertical boreholes drilled from surface or from the entries in advance of mining, or it is captured from the fractured and caved zones (gob) using ventholes during mining. The rest of the gas, especially that gas that originates from the longwall face and caved zone, mixes with the ventilation air and travels through bleeder and return entries before being exhausted to atmosphere from air shafts. Although the gas associated with mining mostly focuses on methane, the gas is not pure methane but is a mixture (where both the components and their quantities vary depending on the sampling location). Understanding the evolution of the composition of the gas from source to different sampling and evaluation points in mines using proper statistical analysis and interpretation methods can lead to better designed degasification and ventilation systems and the selection of the most adequate utilization method for generating energy from the gas. In this work, we present the results of compositional data analysis (CoDa) of gases sampled at different locations in a longwall mine operating in Pennsylvanian coal-bearing strata in the Northern Appalachian coal basin. Sampling locations were from accessible parts of the bleeder entries, returns, bleeder evaluation points and shafts within the mine, and also from gob gas ventholes (GGV) and coal degasification boreholes drilled in the panel areas. In addition, desorbed gas samples from seams that are important for the mine were included in the analyses for comparison. The compositional data analysis showed that the gas composition shifts based on the sampling location, putting in-mine and pure coalbed gases on the opposite ends. Removal of air from the samples did not change this observation suggesting that oxygen is depleted especially for in-mine samples, which is due to oxidation. Results also suggested that desorbed gas samples may not represent the composition of the coal seam gas.

International Journal of Coal Geology↗

USGS2020

Repetitive sampling and control threshold improve 16S rRNA results from produced waters associated with hydraulically fractured shales

Sequencing microbial DNA from deep subsurface environments is complicated by a number of issues ranging from contamination to non-reproducible results. Many samples obtained from these environments - which are of great interest due to the potential to stimulate microbial methane generation - contain low biomass. Therefore, samples from these environments are difficult to study as sequencing results can be easily impacted by contamination. In this case, the low amount of sample biomass may be effectively swamped by the contaminating DNA and generate misleading results. Additionally, performing field work in these environments can be difficult, as researchers generally have limited access to and time on site. Therefore, optimizing a sampling plan to produce the best results while collecting the greatest number of samples over a short period of time is ideal. This study aimed to recommend an adequate sampling plan for field researchers obtaining microbial biomass for 16S rRNA gene sequencing, applicable specifically to oil and gas-producing environments. Forty-nine different samples were collected by filtering specific volumes of produced water from a hydraulically fractured well producing from the Niobrara Shale. Water was collected in two different sampling events 24 hours apart. Four to five samples were collected from 11 specific volumes. These samples along with eight different blanks were submitted for analysis. DNA was extracted from each sample, and quantitative polymerase chain reaction (qPCR) and 16S rRNA Illumina MiSeq gene sequencing were performed to determine relative concentrations of biomass and microbial community composition, respectively. The qPCR results varied across sampled volumes, while no discernible trend correlated contamination to volume of water filtered. This suggests that collecting a larger volume of sample may not result in larger biomass concentrations or better representation of a sampled environment. Researchers could prioritize collecting many low volume samples over few high-volume samples. Our results suggest that there also may be variability in the concentration of microbial communities present in produced waters over short (i.e., hours) time scales, which warrants further investigation. Submission of multiple blanks is also vital to determining how contamination or low biomass effects may influence a sample set collected from an unknown environment.

Montana, Wyoming, Colorado, New Mexico, Texas, Okl↗

USGS2020

Exploring methane behavior in Marcellus Shale micropores via contrast matching neutron scattering

Petroleum in shale reservoirs is hosted in organic matter and mineral pores as well as in natural fractures and voids. For thermally mature plays, e.g., the Marcellus Shale, methane and other light alkane gases are thought to be primarily contained in organic matter pores with radii ≦50 nm. Thus, in order to understand natural gas occurrence, transport, storage, and recoverability within unconventional reservoirs at the dry-gas stage of thermal maturity, it is critical to characterize the associated organic matter porosity across length scales from 50 nm down to the angstrom level. We utilized wide Q-range neutron total scattering to characterize deuterated methane (CD 4 ) adsorption at 60ºC up to the zero average contrast (ZAC) pressure (~60 MPa) within two mineralogically different samples collected from the same producing interval from the Middle Devonian Marcellus Shale. The neutron scattering approach used here provides structural information from the inter-atomic regime up to a nominal pore radius of ~12.5 nm and, by reaching the CD 4 ZAC pressure (~60 MPa), it is possible to examine the distribution of open versus closed pores within this pore size range in the samples. Our results indicate that ~10% of the largest pores measured are closed to CD 4 for a quartz-rich sample whereas up to 25% of pores with a nominal radius of ~12.5 nm are inaccessible within a sample with an equivalent proportion of quartz, carbonate, and clay. As pore size decreases, accessibility also decreases; all pores with radii ~0.5 nm are effectively closed to CD 4 in both samples. Additionally, up to ~4.5× more CD 4 is adsorbed within the quartz-rich sample at 60 MPa and we see no evidence for densification of CD 4 within the shale pores. These findings suggest that, for shale samples within the dry-gas window, (i) nanometer-scale porosity is primarily located within organic matter, (ii) the amount of available nano-porosity can vary widely over meter scales, and (iii) mineralogy plays a secondary role in dictating methane behavior within these systems.

West Virginia↗

USGS2020

Impacts of mineralogical variation on CO2 behavior in small pores from producing intervals of the Marcellus Shale: Results from neutron scattering

The Near and InterMediate Range Order Diffractometer (NIMROD) was used to examine the potential impact of shale mineralogy on CO 2 behavior within micropores. Two samples with varying mineral compositions were obtained from producing intervals in the dry gas window in the Middle Devonian Marcellus Shale. One of the samples contained relatively high amounts of quartz and clay and low carbonate, the other contained relatively equal amounts of quartz, carbonate, and clay. The samples were probed with CO 2 at subcritical pressures (20–50 bar) and temperature (22 °C) and characterized over a neutron scattering vector ( Q ) range of 0.02 < Q < 50 Å –1 . This Q range provides information from the atomistic length-scale up to pore radii of 10 nm. Mineralogy variations between the samples did not affect scattering ratios over the entire Q range accessible with the NIMROD. Q values for the minimum scattering ratios of both samples at similar pressures are remarkably similar, particularly for Q < ∼0.09 Å –1 , and maximum scattering ratios are similar in both samples suggesting that mineral pores are so uncommon in the pore sizes examined that they cannot be resolved due to the overwhelming amounts of organic pores in these samples. Overall, these findings suggest that mineralogical variations have little effect on CO 2 behavior within organic matter-hosted shale micropores at high thermal maturities and they lend support to the assertion that CO 2 cannot be stored in the vast surface areas of micropores in organic material in shale formations. In addition, CO 2 enhanced oil recovery (EOR) is unlikely to displace petroleum from some of the smaller mesopores (2.5 to ∼3.5 nm) and all of the micropores because they are effectively closed to CO 2 . amples were probed with CO2 at subcritical pressures (20 50 bar) and temperature (22 oC) and characterized over a neutron scattering vector (Q) range of 0.02 < Q < 50 -1. This Q range provides information on nominal pore size radii of around 10 0.5 nm. Mineralogy variations between the samples did not affect scattering ratios over the entire Q range accessible with the NIMROD. Q values for the minimum scattering ratios of both samples at similar pressures are statistically indistinguishable and maximum scattering ratios are similar in both samples suggesting that mineral pores are either absent or are so uncommon that they cannot be resolved due to the overwhelming amounts of organic pores in these samples. Overall, these findings suggest that mineralogical variations have little effect on CO2 behavior within organic matter-hosted shale micropores at high thermal maturities and they lend support to the assertion that CO2 cannot be stored in the vast surface areas of micropores (<2.5 nm) in shale formations. In addition, CO2 enhanced oil recovery (EOR) is unlikely to displace petroleum from some of the smaller mesopores (2.5 10 nm) and all of the micropores because they are effectively closed to CO2.

Energy & Fuels↗

USGS2019

Self-organizing maps for compositional data: coal combustion products of a Wyoming power plant

A self-organizing map (SOM) is a non-linear projection of a D-dimensional data set, where the distance among observations is approximately preserved on to a lower dimensional space. The SOM arranges multivariate data based on their similarity to each other by allowing pattern recognition leading to easier interpretation of higher dimensional data. The SOM algorithm allows for selection of different map topologies, distances and parameters, which determine how the data will be organized on the map. In the particular case of compositional data (such as elemental, mineralogical, or maceral abundance), the sample space is governed by Aitchison geometry and extra steps are required prior to their SOM analysis. Following the principle of working on log-ratio coordinates, the simplicial operations and the Aitchison distance, which are appropriate elements for the SOM, are presented. With this structure developed, a SOM using Aitchison geometry is applied to properly interpret elemental data from combustion products (bottom ash, fly ash, and economizer fly ash) in a Wyoming coal-fired power plant. Results from this effort provide knowledge about the differences between the ash composition in the coal combustion process.

Stochastic Environmental Research and Risk Assessm↗

USGS2018

Compositional data analysis of coal combustion products with an application to a Wyoming power plant

A mathematically sound approach for summarizing chemical analyses of feed coal and all its combustion products (bottom ash, economizer fly ash, and fly ash) is presented. The nature of the data requires the application of compositional techniques when conducting statistical analysis, techniques that have not been applied before to the study of partitioning of elements between the coal that enters the boiler and the associated coal combustion products. A collection of descriptive and inferential compositional techniques was used to analyze the coal combustion products from a Wyoming power plant burning Paleocene Wyodak–Anderson coal. The significance of the fluctuation in ash composition is determined by using a Hotelling’s T -squared test and bootstrapping. Tree displays allow for visualization of the progressive effect of filters in removal of chemical species based on their geochemical composition. Results indicate that, in general, as the suspended combustion products entrained in the flue gases move closer to the stack, chemical species are removed from the combustion gas, starting with minerals associated with elements having the lowest volatility.

Mathematical Geosciences↗

USGS2018

Cadmium isotope fractionation during coal combustion: Insights from two U.S. coal-fired power plants

Coal combustion, one of the principal energy sources of electricity in the United States, produces over 100 million tons of coal combustion products (CCPs) per year in the U.S. The reuse and disposal of CCPs has the potential to release toxic trace elements, including cadmium (Cd), into the environment. In this study, we investigated CCPs, including bottom ash (BA), economizer fly ash (EFA), and fly ash (FA), as well as feed coal (FC) and pulverized coal (PC) collected from two U.S. coal-fired power plants in New Mexico and Ohio with different coal supplies. The New Mexico plant uses high volatile C bituminous, low-sulfur coals mined from the San Juan Basin (Cretaceous Fruitland Formation) and the Ohio plant uses high volatile A bituminous, high-sulfur central Appalachian Basin coals (Upper Pennsylvanian Monongahela Formation). Mineralogical and elemental analysis showed that these CCP samples consist of ∼70% amorphous Al-Si-rich glasses and ∼30% mineral phases of quartz (SiO 2 ) and mullite (Ai 6 Si 2 O 13 ). The Cd isotope compositions (δ 114 Cd, normalized to NIST Cd standard 3108) of FA and EFA samples (ranging from −0.51 to +0.47‰) are distinctively heavier than those of BA samples (−0.75 to −0.52‰) in both power plants. We interpret this Cd isotope difference as a result of Cd condensation from the gas phase during flue gas cooling, instead of evaporation of Cd phase during coal combustion. Cd condensation is the main process to generate the isotopically heavy Cd signatures that preferentially partition on the fine FA particles. We also investigated Cd isotope compositions in different leachate products from a series of batch-leaching experiments with these CCPs, using diluted acetic acid, hydroxyl ammonium chloride, hydrogen peroxide followed by ammonium acetate, and 5% nitric acid, as a possible means to identify CCP-released Cd in the environment. Unusually and significantly heavier Cd isotope compositions were observed in each leachate of FA samples (+1.10 to +7.09‰), which fall far outside from the range of Cd isotope ratios observed in natural soils and rocks, but less so for the EFA samples (−0.43 to +1.18‰). Such an observation is consistent with the interpretation that isotopically heavy Cd preferentially partitions on the fine FA particles after coal combustion and is readily to be released during these leaching experiments. This study demonstrates that high-temperature coal combustion can lead to a very large degree of fractionation of Cd isotopes that can be used as a unique tracer for identifying anthropogenic metal inputs in the environment. The major Cd isotope fractionation process occurs as the Cd gas phase condenses on fine FA particles during the flue gas cooling stage after coal combustion.

New Mexico, Ohio↗

USGS2018

Nanometre-sized pores in coal: Variations between coal basins and coal origin

We have used small angle neutron scattering (SANS) to investigate the differences in methane and hexane penetration in pores in bituminous coal samples from the U.S., Canada, South Africa, and China, and maceral concentrates from Australian coals. This work is an extension of previous work that showed consistent differences between the extent of penetration by methane into 10–20 nm size pores in inertinite in bituminous coals from Australia, North America and Poland. In this study we have confirmed that there are differences in the response of inertinite to methane and hexane penetration in coals sourced from different coal basins. Inertinite in Permian Australian coals generally has relatively high numbers of pores in the 2.5–250 nm size range and the pores are highly penetrable by methane and hexane; coals sourced from Western Canada had similar penetrability to these Australian coals. However, the penetrability of methane and hexane into inertinite from the Australian Illawarra Coal Measures (also Permian) is substantially less than that of the other Australian coals; there are about 80% fewer 12 nm pores in Illawarra inertinite compared to the other Australian coals examined. The inertinite in coals sourced from South Africa and China had accessibility intermediate between the Illawarra coals and the other Australian coals. The extent of hexane penetration was 10–20% less than CD 4 penetration into the same coal and this difference was most pronounced in the 5–50 nm pore size range. Hexane and methane penetrability into the coals showed similar trends with inertinite content. The observed variations in inertinite porosity between coals from different coal regions and coal basins may explain why previous studies differ in their observations of the relationships between gas sorption behavior, permeability, porosity, and maceral composition. These variations are not simply a demarcation between Northern and Southern Hemisphere coals.

International Journal of Coal Geology↗

USGS2018

Porosity of the Marcellus Shale: A contrast matching small-angle neutron scattering study

Neutron scattering techniques were used to determine the effect of mineral matter on the accessibility of water and toluene to pores in the Devonian Marcellus Shale. Three Marcellus Shale samples, representing quartz-rich, clay-rich, and carbonate-rich facies, were examined using contrast matching small-angle neutron scattering (CM-SANS) at ambient pressure and temperature. Contrast matching compositions of H 2 O, D 2 O and toluene, deuterated toluene were used to probe open and closed pores of these three shale samples. Results show that although the mean pore radius was approximately the same for all three samples, the fractal dimension of the quartz-rich sample was higher than for the clay-rich and carbonate-rich samples, indicating different pore size distributions among the samples. The number density of pores was highest in the clay-rich sample and lowest in the quartz-rich sample. Contrast matching with water and toluene mixtures shows that the accessibility of pores to water and toluene also varied among the samples. In general, water accessed approximately 70–80% of the larger pores (>80 nm radius) in all three samples. At smaller pore sizes (~5–80 nm radius), the fraction of accessible pores decreases. The lowest accessibility to both fluids is at pore throat size of ~25 nm radii with the quartz-rich sample exhibiting lower accessibility than the clay- and carbonate-rich samples. The mechanism for this behaviour is unclear, but because the mineralogy of the three samples varies, it is likely that the inaccessible pores in this size range are associated with organics and not a specific mineral within the samples. At even smaller pore sizes (~<2.5 nm radius), in all samples, the fraction of accessible pores to water increases again to approximately 70–80%. Accessibility to toluene generally follows that of water; however, in the smallest pores (~<2.5 nm radius), accessibility to toluene decreases, especially in the clay-rich sample which contains about 30% more closed pores than the quartz- and carbonate-rich samples. Results from this study show that mineralogy of producing intervals within a shale reservoir can affect accessibility of pores to water and toluene and these mineralogic differences may affect hydrocarbon storage and production and hydraulic fracturing characteristics

International Journal of Coal Geology↗

USGS2017

Neutron scattering measurements of carbon dioxide adsorption in pores within the Marcellus Shale: Implications for sequestration

Shale is an increasingly viable source of natural gas and a potential candidate for geologic CO 2 sequestration. Understanding the gas adsorption behavior on shale is necessary for the design of optimal gas recovery and sequestration projects. In the present study neutron diffraction and small-angle neutron scattering measurements of adsorbed CO 2 in Marcellus Shale samples were conducted on the Near and InterMediate Range Order Diffractometer (NIMROD) at the ISIS Pulsed Neutron and Muon Source, STFC Rutherford Appleton Laboratory along an adsorption isotherm of 22 °C and pressures of 25 and 40 bar. Additional measurements were conducted at approximately 22 and 60 °C at the same pressures on the General-Purpose Small-Angle Neutron Scattering (GP-SANS) instrument at Oak Ridge National Laboratory. The structures investigated (pores) for CO 2 adsorption range in size from Å level to ∼50 nm. The results indicate that, using the conditions investigated densification or condensation effects occurred in all accessible pores. The data suggest that at 22 °C the CO 2 has liquid-like properties when confined in pores of around 1 nm radius at pressures as low as 25 bar. Many of the 2.5 nm pores, 70% of 2 nm pores, most of the <1 nm pores, and all pores <0.25 nm, are inaccessible or closed to CO 2 , suggesting that despite the vast numbers of micropores in shale, the micropores will be unavailable for storage for geologic CO 2 sequestration.

Environmental Science & Technology↗