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At least 361 records · Page 20Linked to original sources
USGS2017

Mercury and trace element distribution in density separates of a South African Highveld (#4) coal: Implications for mercury reduction and preparation of export coal

Eight density separates of Permian Highveld (#4) coal were investigated for partitioning of Hg and trace elements. The separates include float fractions obtained in heavy media having densities of 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 g/cm 3 , and the sink fraction for 2.0 g/cm 3 . Bulk analysis of the separates shows strong (R 2 ≥ 0.80) positive correlations between pyritic sulfur and mercury, and between ash yield and both pyritic sulfur and mercury. Laser ablation (LA) ICP-MS analysis of individual pyrite grains in the separates confirms association of Hg and As with pyrite as indicated by bulk analysis. Other elements detected in pyrite by LA-ICP-MS include Mn, Co, Ni, Tl, and Pb. Results for the separates allow prediction of Hg, trace elements, and ash yields expected in specific South African coal products. These range from 0.06 ppm Hg and an ash yield of 11.5% ash for the export fraction to 0.47 ppm Hg and an ash yield of 60.9% for the discard (stone) fraction (dry basis). Results show pronounced differences expected between coal used for domestic power generation and coal which is exported.

International Journal of Coal Geology↗
USGS2016

Notes on the origin of copromacrinite based on nitrogen functionalities and δ13C and δ15N determined on samples from the Peach Orchard coal bed, southern Magoffin County, Kentucky

This paper represents the first attempt to show, by means other than just petrographic ones, that one type of macrinite, herein designated copromacrinite, may result from macrofauna feces. For that purpose a combination of coal petrography, X-ray photoelectron spectroscopy, and elemental-analysis continuous-flow isotope ratio mass spectrometry methods were used to determine nitrogen functionalities and δ 13 C and δ 15 N compositions in 1) vitrinite-rich, 2) fusinite + semifusinite-rich, and 3) macrinite-rich (with a possible coprolitic origin) samples of the high volatile A bituminous Peach Orchard coal (Bolsovian; Middle Pennsylvanian) from Magoffin County, Kentucky. There were no significant differences between pyridinic-N and quaternary-N abundance in the three samples, however, pyrrolic-N was higher (~ 54%) in the macrinite-rich sample than in the other two samples (~ 38%). The data suggest that pyridinic-N and quaternary-N are independent of maceral group composition and that pyrrolic-N is dependent on maceral composition (fusinite + semifusinite versus macrinite). δ 13 C values obtained for bulk and demineralized coal of the vitrinite- and fusinite + semifusinite-rich samples are similar with δ 13 C values of − 24.80 ± 0.01‰ VPDB and − 24.61 ± 0.09‰ VPDB for bulk samples and − 24.81 ± 0.07‰ VPDB and − 24.52 ± 0.04‰ VPDB for demineralized samples. These values are within the expected range for vitrinite-rich samples and the slightly higher δ 13 C value of the fusinite + semifusinite-rich sample is expected as δ 13 C values for inertinite are higher than for vitrinite. However, there was a significant shift to a lower δ 13 C value (− 26.80 ± 0.01‰ VPDB for the bulk sample value) for the macrinite-rich sample. Because the samples are basically isorank, and δ 13 C (and δ 15 N) shifts do not occur during maturation until anthracite rank, the difference may be related to the presence or composition of the macrinite within the sample which lacks heat-effect indicators, such as devolatilization vacuoles and distorted pores. δ 15 N values are also similar for bulk and demineralized coal of the vitrinite- and fusinite + semifusinite-rich samples, and the bulk values were heavier in this samples (3.07 ± 0.03‰ Air and 2.92 ± 0.10‰ Air, respectively), and much lighter (− 2.83 ± 0.09‰ Air) for the macrinite-rich sample. The study of Peach Orchard coal samples using reflected-light microscopy, isotopic composition, and nitrogen-forms analyses revealed that the macrinite-rich sample contains macrinite with coprolitic features (e.g. oxidation rind, mix of undigested palynomorphs, frequent and randomly located funginite, agglutination pulp of semifusinite reflectance, internal lack of bedding fabric, and suggestion of structures resulting from intestines and stomach walls), more pyrrolic-N (~ 16%), and lower δ 13 C (~ 2‰ VPDB) and δ 15 N (~ 4‰ Air) values than the vitrinite and semifusinite + fusinite rich samples. These findings suggest that the maceral macrinite has multiple origins based on petrography and measurable chemical differences between the macrinite, vitrinite, and semifusinite + fusinite fractions within the coal. Assuming that copromacrinite observed is an excretion then the anomalies observed may result from the symbiotic relations between the macrofauna (e.g. cockroaches) and microbiota during the digestive processes, and the nitrogen balance mechanisms inside macrofauna body.

Kentucky↗
USGS2016

Calorific value and compositional ultimate analysis with a case study of a Texas lignite

Measurements to determine coal quality as fuel include proximate analysis, ultimate analysis and calorific value. The latter is an attribute taking non-negative real values, so a simple transformation is sufficient for its spatial modeling applying geostatistics. The analyses, however, involve proportions that follow the properties of compositional data, thus requiring special preprocessing for an adequate modeling already described in a previous publication for the case of proximate analysis data. 1 Here we model the results of calorific value and ultimate analysis. We propose to use two different binary partitions, one per analysis, map the corresponding isometric logratio transformations, and backtransform the results. The methodology is illustrated using the same coal bed in the previous paper modeling proximate analysis data. Results are summarized using probability maps that, in the case of this deposit, show a prominent channel crossing the deposit and separating the best quality coal from that of lower quality.

International Journal of Coal Geology↗
USGS2016

Organic petrology and geochemistry of mudrocks from the lacustrine Lucaogou Formation, Santanghu Basin, northwest China: Application to lake basin evolution

Exploration for tight oil in the frontier Santanghu Basin of northwest China has resulted in recent commercial discoveries sourced from the lacustrine Upper Permian Lucaogou Formation, already considered a “world class source rock” in the Junggar Basin to the west. Here we apply an integrated analytical program to carbonate-dominated mudrocks from the Lucaogou Formation in Santanghu Basin to document the nature of organic matter (OM) in the context of an evolving lake system. The organic-rich samples (TOC 2.8–11.4 wt%; n = 10) were widely spaced from an ~ 200 m cored section, interpreted from textural and mineralogical evidence to document transition from a lower under-filled to an overlying balanced-filled lake. Organic matter is dominated by moderate to strongly fluorescent amorphous material with Type I geochemical signature (HI values 510–755; n = 10) occurring in a continuum from lamellar stringers, 10–20 μm thick, some ≥ 1 mm in length (possible microbial mat; preserved only in lower under-filled section) to finely-disseminated amorphous groundmass intimately intermixed with mineral matrix. Biomarkers for methanotrophs and photosynthetic cyanobacteria indicate a complex microbial consortium. A unicellular prasinophyte green alga(?), similar to Tasmanites in marine rocks, is present as discrete flattened discs 50–100 μm in diameter. Type III OM including vitrinite (some fluorescent) and inertinite also is abundant. Solid bitumen, indicating local kerogen conversion, fills voids and occurs throughout the cored section. Vitrinite reflectance values are 0.47–0.58%, consistent with strong OM fluorescence but may be “suppressed”. Other proxies, e.g., biomarker parameters, indicate the Lucaogou Formation is in the early oil window at this location. On average, slightly more amorphous OM and telalginite are present in the lower section, consistent with a shallow, stratified, saline environment with low sediment dilution. More inertinite is present in the upper section, indicating greater terrestrial influx and consistent with higher quartz and plagioclase content (dominantly authigenic chalcedony and albite). Laminated mudstones in the upper section indicate anoxia prevented bioturbation from benthic grazing, also indicating stratified water column conditions. A decrease upsection in authigenic dolomite with reciprocal increase of ankerite/siderite is consistent with decreasing salinity, as is an overall decrease in gammacerane index values. These observations suggest evolution from a shallow, stratified evaporative (saline) setting to a deeper, stratified freshwater basin with higher water input during Lucaogou deposition. The evolution from an under-filled to balance-filled lake in Santanghu Basin is similar to Lucaogou deposition in Junggar Basin, suggesting similar tectonic and climatic controls. Paleoclimate interpretations from other researchers in this area suggested an evolution from semi-arid to humid conditions during the Roadian; we interpret that the evolution from an under-filled to balanced-filled lake seen in our data is in response to climate change, and may represent increased groundwater delivery to the Santanghu Basin.

International Journal of Coal Geology↗
USGS2016

Comparison of geochemical data obtained using four brine sampling methods at the SECARB Phase III Anthropogenic Test CO2 injection site, Citronelle Oil Field, Alabama

The chemical composition of formation water and associated gases from the lower Cretaceous Paluxy Formation was determined using four different sampling methods at a characterization well in the Citronelle Oil Field, Alabama, as part of the Southeast Regional Carbon Sequestration Partnership (SECARB) Phase III Anthropogenic Test, which is an integrated carbon capture and storage project. In this study, formation water and gas samples were obtained from well D-9-8 #2 at Citronelle using gas lift, electric submersible pump, U-tube, and a downhole vacuum sampler (VS) and subjected to both field and laboratory analyses. Field chemical analyses included electrical conductivity, dissolved sulfide concentration, alkalinity, and pH; laboratory analyses included major, minor and trace elements, dissolved carbon, volatile fatty acids, free and dissolved gas species. The formation water obtained from this well is a Na–Ca–Cl-type brine with a salinity of about 200,000 mg/L total dissolved solids. Differences were evident between sampling methodologies, particularly in pH, Fe and alkalinity. There was little gas in samples, and gas composition results were strongly influenced by sampling methods. The results of the comparison demonstrate the difficulty and importance of preserving volatile analytes in samples, with the VS and U-tube system performing most favorably in this aspect.

International Journal of Coal Geology↗
USGS2016

Application of organic petrography in North American shale petroleum systems: A review

Organic petrography via incident light microscopy has broad application to shale petroleum systems, including delineation of thermal maturity windows and determination of organo-facies. Incident light microscopy allows practitioners the ability to identify various types of organic components and demonstrates that solid bitumen is the dominant organic matter occurring in shale plays of peak oil and gas window thermal maturity, whereas oil-prone Type I/II kerogens have converted to hydrocarbons and are not present. High magnification SEM observation of an interconnected organic porosity occurring in the solid bitumen of thermally mature shale reservoirs has enabled major advances in our understanding of hydrocarbon migration and storage in shale, but suffers from inability to confirm the type of organic matter present. Herein we review organic petrography applications in the North American shale plays through discussion of incident light photographic examples. In the first part of the manuscript we provide basic practical information on the measurement of organic reflectance and outline fluorescence microscopy and other petrographic approaches to the determination of thermal maturity. In the second half of the paper we discuss applications of organic petrography and SEM in all of the major shale petroleum systems in North America including tight oil plays such as the Bakken, Eagle Ford and Niobrara, and shale gas and condensate plays including the Barnett, Duvernay, Haynesville-Bossier, Marcellus, Utica, and Woodford, among others. Our review suggests systematic research employing correlative high resolution imaging techniques and in situ geochemical probing is needed to better document hydrocarbon storage, migration and wettability properties of solid bitumen at the pressure and temperature conditions of shale reservoirs.

International Journal of Coal Geology↗
USGS2017

Enhanced coal-dependent methanogenesis coupled with algal biofuels: Potential water recycle and carbon capture

Many coal beds contain microbial communities that can convert coal to natural gas (coalbed methane). Native microorganisms were obtained from Powder River Basin (PRB) coal seams with a diffusive microbial sampler placed downhole and used as an inoculum for enrichments with different nutrients to investigate microbially-enhanced coalbed methane production (MECoM). Coal-dependent methanogenesis more than doubled when yeast extract (YE) and several less complex components (proteins and amino acids) were added to the laboratory microcosms. Stimulated coal-dependent methanogenesis with peptone was 86% of that with YE while glutamate-stimulated activity was 65% of that with YE, and a vitamin mix had only 33% of the YE stimulated activity. For field application of MECoM, there is interest in identifying cost-effective alternatives to YE and other expensive nutrients. In laboratory studies, adding algal extract (AE) with lipids removed stimulated coal-dependent methanogenesis and the activity was 60% of that with YE at 27 d and almost 90% of YE activity at 1406 d. Analysis of British Thermal Unit (BTU) content of coal (a measure of potential energy yield) from long-term incubations indicated > 99.5% of BTU content remained after coalbed methane (CBM) stimulation with either AE or YE. Thus, the coal resource remains largely unchanged following stimulated microbial methane production. Algal CBM stimulation could lead to technologies that utilize coupled biological systems (photosynthesis and methane production) that sustainably enhance CBM production and generate algal biofuels while also sequestering carbon dioxide (CO 2 ).

International Journal of Coal Geology↗
USGS2017

Leaching of trace elements from Pittsburgh coal mill rejects compared with coal combustion products from a coal-fired power plant in Ohio, USA

We investigated the leachability of elements from mill rejects from the high-sulfur, bituminous Upper Pennsylvanian Pittsburgh coal, using the synthetic groundwater leaching procedure (SGLP), long-term leaching (LTL), and the U.S. Environmental Protection Agency's (EPA's) toxicity characteristic leaching procedure (TCLP), and compared their leaching behavior with that of three coal combustion products (CCPs)—bottom ash, economizer fly ash , and fly ash—from the same coal. None of the environmentally hazardous Resource Conservation and Recovery Act of 1976 (RCRA) metals analyzed in the leachates from the mill rejects or the CCPs exceeded U.S. EPA toxicity characteristics (As, Ba, Cd, Cr, Hg, Pb, and Se). Most trace elements leached the least from mill rejects and bottom ash and leached the most from fly ash. The elements Ca, Co, Mg, Mn, and Sr, however, were more concentrated in mill reject leachates than CCP leachates. Most trace elements increased in concentration with increasing SGLP and LTL leaching duration, but As and V decreased in concentration with time in mill reject leachates, suggesting sorption or precipitation of these elements was occurring.

Ohio↗
USGS2017

Identification of alginite and bituminite in rocks other than coal. 2006, 2009, and 2011 round robin exercises of the ICCP Identification of Dispersed Organic Matter Working Group

The paper presents results of round robin exercises on photomicrograph-based identification of dispersed organic matter in source rocks that represent a range of marine and lacustrine deposits from worldwide localities and cover a range of thermal maturities. The round robin exercises were conducted by the Identification of Dispersed Organic Matter Working Group (IDOM WG) of the International Committee for Coal and Organic Petrology (ICCP). The round robin exercises aimed to (1) assess the applicability of the established ICCP definitions of bituminite, (2) identify deficiencies and improve the existing nomenclatures, and (3) provide a basis for the revision of the bituminite and alginite definitions in the ICCP Handbook (Taylor et al., 1998). Three round robin exercises performed in 2006, 2009 and 2011 involved 18 participants from research laboratories at universities and within government and industry. Participants were asked to identify macerals on the basis of existing definitions in 129 photomicrographs taken in incident white light and fluorescent mode and also in fluorescence light mode at prolonged (15 min) blue light irradiation. The results indicate that the definition of telalginite permits its positive and satisfactory agreement among the participants. In contrast, the descriptive characteristics of lamalginite referring to film-like appearance (filamentous) and lack of inner or outer structure are insufficient and inadequate to enable an unequivocal discrimination between it and telalginite. Furthermore, based on the amorphous nature of bituminite and lack of adherence to its established description and character (Taylor et al., 1998), the highest discrepancies were observed in its identification. Differentiation of bituminite from a fluorescent groundmass and in some cases from lamalginite proved to be particularly challenging. The findings of these round robin exercises are useful for improving the identification of sedimentary organic matter in source rocks and may be an important foundation for the modification of the ICCP definitions of alginite and bituminite.

International Journal of Coal Geology↗
USGS2018

Pore-types and pore-network evolution in Upper Devonian-Lower Mississippian Woodford and Mississippian Barnett mudstones: Insights from laboratory thermal maturation and organic petrology

Pore-evolution models from immature organic-matter (OM) -rich Barnett (0.42%R o ) and Woodford (0.49%R o ) mudstones were compared with models previously developed from low-maturity OM-lean Boquillas (Eagle Ford-equivalent) mudstones to investigate whether (1) different mineralogy (siliceous vs. calcareous) exerts different catalytic and sorption effects and influences OM-pore origin and evolution; and (2) different types of macerals show different OM pore evolution history. Laboratory gold-tube pyrolysis, scanning electron microscopy (SEM) and thin-section petrography, organic petrography, and geochemical characterization were used to investigate the role of bulk mineralogy, maceral type, and thermal maturation on OM-pore evolution. Results suggest that mineralogy has little impact on OM-pore development and evolution. Macerals, identified using both SEM (platy OM, particulate OM, organic–mineral admixtures, Tasmanites ) and organic petrology (vitrinite, inertinite, amorphous organic matter [AOM]/bituminite, telalginite [ Leiosphaeridia , Tasmanites ]), do affect the origin and evolution of OM pores owing to differences in chemical compositions, generation kinetics, and activation-energy distributions between Tasmanites , matrix bituminite, and other types of macerals. Leiosphaeridia and Tasmanites in Woodford mudstone samples exhibit a delay in onset and a shorter period of petroleum generation and pore development compared to the matrix bituminite in the Barnett and Woodford mudstone samples. Pre-oil solid bitumen was observed to have migrated into initial primary mineral pore networks at the bitumen generation stage in both Barnett and Woodford samples. At higher levels of thermal maturation, the volume of primary mineral pores decreases and the pore volume composed of modified mineral pores and OM pores becomes greater. Pore evolution and pore-type heterogeneity in these mudstones is a function of the initial mineral pore network, types of kerogen and macerals, and generation kinetics of individual macerals upon thermal maturation.

Oklahoma↗
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↗
USGS2018

On the petrographic distinction of bituminite from solid bitumen in immature to early mature source rocks

The oil-prone maceral bituminite (and its equivalents: ‘amorphous organic matter’, ‘sapropelinite’, ‘amorphinite’, etc.) converts to petroleum during thermal maturation of source rocks, resulting in formation of a mobile saturate-rich hydrocarbon and a polar-rich residue of solid bitumen. Evidence of this transition is preserved in immature to early mature source rocks (e.g., Alum, Bakken, Kimmeridge, New Albany, Ohio shales, among many others), where organic petrography reveals a continuum of textures, reflectance, and fluorescence intensity occurring between bituminite and solid bitumen. Bituminite generally is characterized by high(er) intensity fluorescence, low contrast to the inorganic matrix, lower reflectance (compared to solid bitumen), and heterogeneous wispy or ‘schlieren’ textures. In comparison, solid bitumen generally shows lower intensity or no fluorescence compared to bituminite, a distinct contrast to the mineral matrix which usually includes a gray homogeneous surface of low to moderate reflectance, and may possess void-filling, embayment or groundmass textures suggesting evidence of migration or its in situ exsolution. However, these properties may manifest across a continuous spectrum in a sample or in a single microscope field, often making identification inconclusive. Unambiguous identification is further hampered by sample preparation, e.g., mechanical polish may improve homogeneity of larger accumulations, whereas smaller accumulations, or those sheltered by hard minerals, may appear more heterogeneous, leading to identification of the same organic matter as solid bitumen or bituminite, respectively. The disruptive innovation of ion milling in shale sample preparation leads to increased organic reflectance and surface homogeneity, causing bituminite and other oil-prone macerals, e.g., alginite, to develop a gray reflecting surface which is easy to confuse with solid bitumen, especially when obvious void-filling or embayment textures of the latter are absent. Herein we review distinction of solid bitumen from bituminite and alginite in immature to early mature source rocks, providing examples from nine samples illustrated by typical organic petrography images, including samples from hydrous pyrolysis experiments. Based on a review of the literature, we observe an arbitrary reflectance limit of 0.30% in mechanically polished samples seems to differentiate bituminite (<0.30%) from confident identifications of homogeneous solid bitumen (which otherwise lacks obvious void-filling or identifying embayment textures) as individual macerals on a continuous spectrum in immature and early mature source rocks. Future work conducted by governing bodies such as the International Committee for Coal and Organic Petrology (ICCP) should consider interlaboratory studies conducted on multiple immature source rock samples to develop consensus guidelines for bituminite and solid bitumen discrimination.

International Journal of Coal Geology↗
USGS2018

Gas emissions, tars, and secondary minerals at the Ruth Mullins and Tiptop coal mine fires

Both the Tiptop and Ruth Mullins coal fires, Kentucky, were reinvestigated in 2009 and 2010. The Tiptop fire was not as active in 2009 and may have been on the path to burning out at the time of the 2009 visit. The Ruth Mullins coal mine fire, Perry County, Kentucky, has been the subject of several field investigations, including November 2009–February 2010 investigations in which we measured gas emissions, collected minerals and tars, and characterized the nature of the fire. Vents exhibiting the greatest gas flux (>100,000 mg/s/m 2 ) are those with the largest amount of condensate minerals and tars. Vents with moderate gas flux (10,000–100,000 mg/s/m 2 ) are less likely to contain condensate minerals, but are collocated with tars, and vents with the lowest flux (<10,000 mg/s/m 2 ) generally lack both minerals and tars. Aliphatic hydrocarbons present in the gases include C1-C9 compounds, and aromatics include BTEX compounds. Diffuse-CO 2 emissions are concentrated along the fracture zones overlying abandoned mine works. The area of peak diffuse flux corresponds to the trend of the collapsed portal that forms vent 5. The greatest vent emissions were also recorded at vent 5. The snow-melt zone mapped in January 2010 overlies the areas of peak diffuse-CO 2 emissions measured in November; together they delineate the zone of active combustion. Comparison of greenhouse gas emissions from the two sources shows that vent emissions exceed diffuse emissions. The highly fractured, quartz-cemented roof rock funnels the majority of emissions toward the vents. Significant decreases are seen in estimates of yearly greenhouse emissions based on data gathered from November 2009 to February 2010, with estimates from November significantly exceeding any previously published estimates. For example, September 2009 estimates from vent 3 alone indicated that 19 ± 7.5 T CO 2 /yr were emitted while the November 2009 estimates were 1800 ± 690 T/yr. Barometric pressure was lower in November than September. This implies that there are many factors influencing the seasonal variations in fire emissions and that more frequent monitoring will be necessary to derive accurate estimates of coal fires' contribution to the carbon budget.

Kentucky↗
USGS2018

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

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

International Journal of Coal Geology↗
USGS2019

Reflectance increase from broad beam ion milling of coals and organic-rich shales due to increased surface flatness

Broad ion beam (BIB) milling is useful in organic petrology because it can yield flat sample surfaces and avert the ‘smearing’ of organic matter (OM) that results from traditional mechanical polishing. This potentially makes BIB especially useful in the study of nano-porosity, where even minor mechanical disruption of the sample surface distorts the sample characteristic of interest—the pore structure. However, several studies have observed an OM reflectance increase after BIB milling, concluding that ion milling may cause thermal alteration to OM surfaces. To better understand ion milling effects on organic matter, coal (subbituminous, high volatile bituminous, medium volatile bituminous, anthracite) and shale [Bakken Formation, Ohio Shale-Huron Member (5), Kimmeridge Clay Formation, Alum Shale, New Albany Shale] samples were prepared using traditional mechanical polishing methods. Reflectance measurements (% Ro) were gathered on all maceral types present before BIB milling, followed by re-measurement of OM reflectance at the same locations after milling. Most OM increased in reflectance after BIB milling, with some exceptions in high maturity samples. Liptinite macerals in both coal and shale samples showed the greatest percent reflectance increase on average (+133%; n=338), followed by solid bitumen (+49%; n=313), vitrinite (+26%; n=413), and inertinite (+9%; n=220). Despite the increases to OM reflectance caused by BIB milling, no evidence was found for kerogen conversion (e.g., change in maceral abundances), or for migration of newly generated petroleum (e.g., pseudomorphic replacement of kerogen by solid bitumen). Such changes occur when samples are thermally altered from immature conditions into the oil window (e.g., by hydrous pyrolysis), and, if the increases in OM reflectance were thermally driven (by BIB milling), they should have been observed in the above experiments. Herein, we also used atomic force microscopy to document a decrease in surface roughness of correlative locations of OM on pre- and post-ion milled samples. This improved surface polish caused by BIB milling appears to be the root cause of increased OM reflectance, as no other supporting evidence of thermal alteration could be found. That is, the fraction of light formerly lost to oblique scatter in diffuse reflectance from a mechanically polished surface is converted to specular reflectance after BIB ion milling. Thus the light leaves the surface at a near normal angle and returns to the detector, resulting in increased OM reflectance.

International Journal of Coal Geology↗
USGS2019

Application of electron microscopy TEM and SEM for analysis of coals, organic-rich shales and carbonaceous matter

This paper provides a brief summary of the history, development and variety of applications of electron microscopy techniques to analyze coals, organic-rich shales, and carbonaceous materials. General construction and principles of operation of transmitted (TEM) and scanning electron microscope (SEM) are outlined, along with guidance on specimen preparation, and a brief overview of published TEM and SEM applications related to coal, shales, and carbonaceous materials. This work was accepted as the chapter 18.2 of International Committee for Coal and Organic Petrology Methods Handbook at the ICCP Plenary Session on September 27, 2018 in Brisbane (Australia).

International Journal of Coal Geology↗
USGS2020

Fluorescence spectroscopy of ancient sedimentary organic matter via confocal laser scanning microscopy (CLSM)

Fluorescence spectroscopy via confocal laser scanning microscopy (CLSM) was used to analyze ancient sedimentary organic matter, including Tasmanites microfossils in Devonian shale and Gloecapsomorpha prisca ( G. prisca ) in Ordovician kukersite from North American basins. We examined fluorescence emission as a function of excitation laser wavelength, sample orientation, and with respect to location within individual organic entities and in transects across bedded organic matter. Results from spectral scans of the same field of view in Tasmanites with different laser lines showed progressive red-shift in emission maxima with longer excitation wavelengths. This result indicates steady-state Tasmanites fluorescence emission is an overlapping combination of emission from multiple fluorophore functions. Stokes shift decreased with increasing excitation wavelength, further suggesting the presence of multiple fluorophore functions with different S 1 → S 0 transition energies. This observation also indicates that at longer excitation wavelengths, less absorbed light energy is dissipated via collisional transfer than at shorter excitation wavelengths and may suggest fewer polar functions are preferentially absorbing. Confirming earlier results, emission spectra observed from high fluorescence intensity regions (fold apices) in individual Tasmanites are blue-shifted relative to emission from other locations in the same microfossil. We suggest high intensity emission is from photoselective alignment of polarized excitation with the fluorophore absorption and emission transition moment. The blue shift observed in regions of high intensity emission may be due to relative absence or realignment of polar species, e.g., bridging ether or ester functions, although variations in O abundance could not be confirmed with preliminary time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis. Tasmanites occurring in consolidated sediments are flattened from original spherical morphology and, in optical microscopy, this burial deformation results in generally parallel extinction (strain-influenced) and positive elongation. The deformation also induces fluorescence anisotropy observed as variations in emission wavelength when individual Tasmanites are measured from their long axis parallel to bedding, whereas this effect is absent in bedding-normal view. Transects from G. prisca -rich source layers into adjacent reservoir layers show decrease in fluorescence intensity and spectral red-shift (increase in full-width half-maximum with increasing red portion of the half-width). These results may suggest an increase in fluorescence quenching across the source-to-reservoir transition zone, consistent with an increase in aromaticity following petroleum expulsion and migration. These observations are supported by increasing reflectance values measured across similar micro-scale transects. Our results highlight the applicability of CLSM as a broad and under-utilized approach for the characterization of sedimentary organic matter and are discussed with perspective toward petroleum processes and thermal indices research.

International Journal of Coal Geology↗
USGS2020

A two-stage step-wise framework for fast optimization of well placement in coalbed methane reservoirs

Coalbed methane (CBM) has emerged as a clean energy resource in the global energy mix, especially in countries such as Australia, China, India and the USA. The economical and successful development of CBM requires a thorough evaluation and optimization of well placement prior to field-scale exploitation. This paper presents a two-stage, step-wise optimization framework to obtain the optimal placement of wells for large-scale development of CBM reservoirs. In the first stage, an optimal uniform well pattern is obtained by optimizing well pattern description parameters with the particle swarm optimization (PSO) algorithm. Subsequently, the location and status (active/inactive) of each well are perturbed and optimized within the patterns through the integration of the generalized pattern search (GPS) algorithm and a quality map (QM) representing the production potential. This framework was tested in a synthetic anthracite CBM reservoir in the Qinshui basin (with high gas content and low permeability) and a real field high volatile bituminous reservoir in the Illinois basin (with low gas content and high permeability). The results show that: (i) significant variations in the net present value (NPV) exist with respect to different uniform well patterns (even for cases where the total number of wells are identical), the optima of which can be efficiently determined by the PSO within 100 numerical simulation runs; (ii) the optimization of well perturbations by the GPS results in a more noticeable improvement in NPVs for the synthetic (12.3%) than for the real field model (4.6%); (iii) for the low permeable synthetic model with narrow optimal well spacings (320 m × 200 m), the contribution of the optimization of well perturbation to the NPV increment is heavily dependent on the uniform well placement solution; (iv) for the high permeable real field model with large optimal well spacings (1300 m × 1300 m), the initial uniform well placement has a very minor effect on the subsequent well perturbation solutions in terms of NPV; (v) the proposed framework significantly outperforms the conventional well-by-well concatenation procedure in terms of computational efficiency, robustness and optimal criteria set for production potential.

International Journal of Coal Geology↗