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Review and update of the applications of organic petrology: Part 1, geological applications

Organic petrology developed as coal petrology at the beginning of the 20th century dedicated mainly to the study of coals because of their utilization in industry. Coal petrology was then considered a branch of coal science. Later, with the development of specialized nomenclature, classification of coal components, and the standardization and improvement of analytical (microscopical) methods, this discipline expanded in interests and name, becoming organic petrology. Organic petrology carries a broader context, being as well a tool applied in the study of dispersed organic matter in sedimentary rocks due to its importance in exploration for fossil fuel resources. At present, organic petrology is a discipline widely recognized for its role in fundamental and applied research with respect to both coal utilization and in geosciences. Throughout the 20th century several important monographs have been published on the discipline of organic petrology, including “Stach's textbook of coal petrology” (1st edition 1935, 2nd 1975, 3rd 1982), updated as the more general “Organic petrology” by Taylor et al. (1998). More recently, the text “Applied coal petrology: the role of petrology in coal utilization” was published by Suárez-Ruiz and Crelling (2008). This review is the first in a two-part review series that describes and updates the role of organic petrology in geosciences. A second part complementing this one and focused on the applications of organic petrology to other scientific fields will follow.

International Journal of Coal Geology

A paleolatitude approach to assessing surface temperature history for use in burial heating models

Calculations using heat flow theory as well as case histories show that over geologic time scales (10 6 years), changes in mean annual surface temperature (T s ) on the order of 10°C penetrate kilometers deep into the crust. Thus, burial heating models of sedimentary basins, which typically span kilometers in depth and persist over geological time frames, should consider T s history to increase their accuracy. In any case, T s history becomes important when it changes enough to be detected by a thermal maturation index like vitrinite reflectance, a parameter widely used to constrain burial heating models. Assessment of the general temperature conditions leading to petroleum generation indicates that changes in T s as small as 6°C can be detected by vitrinite reflectance measurements. This low temperature threshold indicates that oil and gas windows can be significantly influenced by T s history. A review of paleoclimatic factors suggests the significant and geologically resolvable factors affecting T s history are paleolatitude, long-term changes between cool and warm geological periods (climate mode), the degree to which a basin is removed from the sea (geographic isolation), and elevation or depth relative to sea level. Case studies using geologically realistic data ranges or different methods of estimating T s in a burial heating model indicate a significant impact of Ts when: (1) continental drift, subduction, tectonism and erosion significantly change paleolatitude, paleoaltitude, or paleogeography; (2) strata are at, or near, maximum burial, and changes in T s directly influence maximum burial temperature; and (3), when a significant change in T s occurs near the opening or closing of the oil or gas windows causing petroleum generation to begin or cease. Case studies show that during the burial heating and petroleum generation phase of basin development changes in climate mode alone can influence T s by about 15°C. At present, T s changes from the poles to the equator by about 50°C. Thus, in extreme cases, continental drift alone can seemingly produce T s changes on the order of 50°C over a time frame of 107 years.

International Journal of Coal Geology

Relative importance of physical and economic factors in Appalachian coalbed gas assessment

In the 1995 National Assessment of Oil and Gas Resources prepared by the U.S. Geological Survey, only 20% of the assessed technically recoverable Appalachian Province coalbed gas resources were economic. Physical and economic variables are examined to explain the disparity between economic and technically recoverable coalbed gas. The Anticline and Syncline plays of the Northern Appalachian Basin, which account for 77% of the assessed technically recoverable coalbed gas, are not economic. Analysis shows marginal reductions in costs or rate of return will not turn these plays into commercial successes. Physical parameters that determine ultimate well recoverability and the rate of gas recovery are primary reasons the Northern Appalachian Basin plays are non-commercial. If the application of new well stimulation technology could offset slow gas desorption rates, Appalachian Province economic gas could increase to more then 70% of the technically recoverable gas. Similarly, if operators are able to develop strategies to selectively drill plays by avoiding dry holes and non-commercial occurrences, the economic fraction of technically recoverable gas could increase to over half.In the 1995 National Assessment of Oil and Gas Resources prepared by the U.S. Geological Survey, only 20% of the assessed technically recoverable Appalachian Province coalbed gas resources were economic. Physical and economic variables are examined to explain the disparity between economic and technically recoverable coalbed gas. The Anticline and Syncline plays of the Northern Appalachian Basin, which account for 77% of the assessed technically recoverable coalbed gas, are not economic. Analysis shows marginal reductions in costs or rate of return will not turn these plays into commercial successes. Physical parameters that determine ultimate well recoverability and the rate of gas recovery are primary reasons the Northern Appalachian Basin plays are non-commercial. If the application of new well stimulation technology could offset slow gas desorption rates, Appalachian Province economic gas could increase to more then 70% of the technically recoverable gas. Similarly, if operators are able to develop strategies to selectively drill plays by avoiding dry holes and non-commercial occurrences, the economic fraction of technically recoverable gas could increase to over half.

International Journal of Coal Geology

A geostatistical approach to predicting sulfur content in the Pittsburgh coal bed

The US Geological Survey (USGS) is completing a national assessment of coal resources in the five top coal-producing regions in the US. Point-located data provide measurements on coal thickness and sulfur content. The sample data and their geologic interpretation represent the most regionally complete and up-to-date assessment of what is known about top-producing US coal beds. The sample data are analyzed using a combination of geologic and Geographic Information System (GIS) models to estimate tonnages and qualities of the coal beds. Traditionally, GIS practitioners use contouring to represent geographical patterns of "similar" data values. The tonnage and grade of coal resources are then assessed by using the contour lines as references for interpolation. An assessment taken to this point is only indicative of resource quantity and quality. Data users may benefit from a statistical approach that would allow them to better understand the uncertainty and limitations of the sample data. To develop a quantitative approach, geostatistics were applied to the data on coal sulfur content from samples taken in the Pittsburgh coal bed (located in the eastern US, in the southwestern part of the state of Pennsylvania, and in adjoining areas in the states of Ohio and West Virginia). Geostatistical methods that account for regional and local trends were applied to blocks 2.7 mi (4.3 km) on a side. The data and geostatistics support conclusions concerning the average sulfur content and its degree of reliability at regional- and economic-block scale over the large, contiguous part of the Pittsburgh outcrop, but not to a mine scale. To validate the method, a comparison was made with the sulfur contents in sample data taken from 53 coal mines located in the study area. The comparison showed a high degree of similarity between the sulfur content in the mine samples and the sulfur content represented by the geostatistically derived contours. Published by Elsevier Science B.V.

International Journal of Coal Geology

Paleoslumps in coal-bearing strata of the Breathitt Group (Pennsylvanian), Eastern Kentucky Coal Field, U.S.A

The benefits of geologic analysis for roof-control studies and hazard prediction in coal mines are well documented. Numerous case studies have illustrated the importance of recognizing geologic features such as paleochannels, coal riders, and kettlebottoms in mine roofs. Relatively understudied features, in terms of mining, are paleoslumps .Paleoslumps represent ancient movement and rotation of semi-consolidated sediment. Because bedding in paleoslumps is deformed or inclined, these features cause instability in mine roofs, haul roads, surface highwalls, and other excavations. Various types of paleoslumps above coals in the Eastern Kentucky Coal Field were studied in order to aid in their recognition and prediction in mines. The paleoslumps studied all showed characteristic slump-deformation features, although some differences in magnitude of deformation and overall slump size were noted. Coals beneath slumps often exhibited folding, reverse displacements, truncation, clastic dikes, and locally increased thickness. Slumps are inferred to have been triggered by a wide range of mechanisms, such as loading of water-saturated sediment on rigid substrates, synsedimentary faulting, and over-pressurization of channel margin and bar slopes. Analysis of paleoslumps in underground mines, where paleoslumps are viewed from beneath rather than in profile is difficult, since characteristic bed rotation may not be conspicuous. Sudden increases in bed-dip angle inferred from changes in rock type or bedding contacts in the roof; occurrence of bounding, polished rotation surfaces; or roof irregularity and occurrence of loading features may indicate the presence of paleoslumps. Another key to recognition may be the sudden appearance of over-thickened coal, which can occur because of slump-created paleotopography, synsedimentary faults, and slump-generated overthrusting. In addition, steeply inclined, folded, or transported coal marginal to paleoslumps can create apparent increases in coal thickness in cores. Although thick coals are obviously a target of exploration, anomalously thick coals may actually indicate adjacent paleoslumps accompanied by hazardous roof conditions and loss of seam thickness.

International Journal of Coal Geology

Geologic history of natural coal-bed fires, Powder River basin, USA

Coal-bed fires ignited by natural processes have baked and fused overlying sediments to form clinker, a hard red or varicolored rock, through much of the northern Great Plains of the United States (USA). The gently dipping coal beds in the region burn when regional downwasting brings them above the local water table. The resulting clinker forms a rim along the exposed edge of the coal bed in an ongoing process through geologic time. The resistant clinker is left capping buttes and ridges after the softer unbaked strata erode away. Clinker outcrops cover more than 4100 km2 in the Powder River basin (PRB), which lies in Wyoming (WY) and Montana (MT). The clinker in place records tens of billions of tons of coal that have burned, releasing gases into the atmosphere. The amount of clinker that has eroded away was at least an order of magnitude greater than the clinker that remains in place. Fission-track and uranium-thorium/ helium ages of detrital zircon crystals in clinker, and paleomagnetic ages of clinker, show that coal beds have burned naturally during at least the past 4 million years (Ma). The oldest in-place clinker that has been dated, collected from a high, isolated, clinker-capped ridge, has a fission track age of 2.8??0.6 Ma. Evidence of erosion and downcutting is also preserved by clinker clasts in gravel terraces. One clinker boulder in a terrace 360 m above the Yellowstone River has a fission track age of 4.0??0.7 Ma. Coal-bed fires are caused by lightning, wildfires, spontaneous combustion, or human activity on coal outcrops and in mines. Miners, government agencies, and ranchers have extinguished thousands of coal bed fires, but natural ignition continues where fresh coal has access to air. At any given time, hundreds of fires, mostly small, are burning. In the Powder River basin, the total amount of coal burned by natural fires in the last 2 Ma is one to two orders of magnitude greater than the total amount of coal removed by mining in the past century. However, current annual rates of coal mining are three to four orders of magnitude greater than estimated prehistoric annual rates of coal consumption by natural fires. ?? 2004 Published by Elsevier B.V.

International Journal of Coal Geology

Hydrogeochemistry and coal-associated bacterial populations from a methanogenic coal bed

Biogenic coalbed methane (CBM), a microbially-generated source of natural gas trapped within coal beds, is an important energy resource in many countries. Specific bacterial populations and enzymes involved in coal degradation, the potential rate-limiting step of CBM formation, are relatively unknown. The U.S. Geological Survey (USGS) has established a field site, (Birney test site), in an undeveloped area of the Powder River Basin (PRB), with four wells completed in the Flowers-Goodale coal bed, one in the overlying sandstone formation, and four in overlying and underlying coal beds (Knoblach, Nance, and Terret). The nine wells were positioned to characterize the hydraulic conductivity of the Flowers-Goodale coal bed and were selectively cored to investigate the hydrogeochemistry and microbiology associated with CBM production at the Birney test site. Aquifer-test results indicated the Flowers-Goodale coal bed, in a zone from about 112 to 120 m below land surface at the test site, had very low hydraulic conductivity (0.005 m/d) compared to other PRB coal beds examined. Consistent with microbial methanogenesis, groundwater in the coal bed and overlying sandstone contain dissolved methane (46 mg/L average) with low δ 13 C values (−67‰ average), high alkalinity values (22 meq/kg average), relatively positive δ 13 C-DIC values (4‰ average), and no detectable higher chain hydrocarbons, NO 3 − , or SO 4 2− . Bioassay methane production was greatest at the upper interface of the Flowers-Goodale coal bed near the overlying sandstone. Pyrotag analysis identified Aeribacillus as a dominant in situ bacterial community member in the coal near the sandstone and statistical analysis indicated Actinobacteria predominated coal core samples compared to claystone or sandstone cores. These bacteria, which previously have been correlated with hydrocarbon-containing environments such as oil reservoirs, have demonstrated the ability to produce biosurfactants to break down hydrocarbons. Identifying microorganisms involved in coal degradation and the hydrogeochemical conditions that promote their activity is crucial to understanding and improving in situ CBM production.

Montana, Wyoming

The geology and palynology of lower and Middle Pennsylvanian strata in the Western Kentucky Coal Field

The Western Kentucky Coal Field is the southern tip of the Eastern Interior, or Illinois Basin. Pennsylvanian rocks in this area, which include conglomerate, sandstone, shale, limestone and coal, were deposited primarily in coastal-deltaic settings at a time when western Kentucky was located close to the equator. This paper discusses temporal changes in regional sedimentation patterns and coal-forming floras of Lower and Middle Pennsylvanian strata in the Western Kentucky Coal Field. Lower Pennsylvanian strata of the Caseyville Formation are characterized by paleovalley-filling sedimentation patterns and extabasinal quartz pebbles. Caseyville Formation coals are characterized thin and discontinuous and were strongly influenced by subsidence within underlying paleovalleys, and the dissected lower Pennsylvanian paleotopography. Caseyville coals are commonly dominated by Lycospora, but can also have variable palynofloras, which probably reflects variable edaphic conditions and edge effects within small, patchy paleomires. Tradewater Formation strata show increased marine influences and tidal-estuarine sedimentation, especially in the middle and upper parts. Coal beds in the lower part of the Tradewater typically are thin and discontinuous, although some economically important beds are present. Coals become thicker, more abundant and more laterally persistent towards the top of the formation. Palynologically, lower and middle Tradewater Formation coals are dominated by Lycospora, but begin to show increased amounts of tree fern spores. Middle and upper Tradewater coals are thicker and more continuous, and contain high percentages of tree fern spores. In addition, cordaite pollen is locally abundant in this interval. Carbondale and Shelburn (Desmoinesian) strata are much more laterally continuous, and occur within classic cyclothems that can be traced across the coal field. Cyclothems have long been interpreted as being eustatically driven, and glacio-eustacy controlled not only sedimentation but also the formation of Desmoinesian paleomires. Palynologically, Carbondale and Shelburn coals are either dominated by Lycospora or have heterogeneous palynofloras. Palynologic and coal-quality data suggest that hydrologic base level may have been the primary control on Desmoinesian paleomires, rather than paleoclimate, as the coals display rheotrophic, rather than ombrotrophic characteristics. ?? 2001 Elsevier Science B.V. All rights reserved.

International Journal of Coal Geology

Biogenic origin of coalbed gas in the northern Gulf of Mexico Coastal Plain, U.S.A

New coal-gas exploration and production in northern Louisiana and south-central Mississippi, Gulf of Mexico Basin, is focused on the Wilcox Group (Paleocene–Eocene), where the depth to targeted subbituminous C to high volatile C bituminous coal beds ranges from 300 to 1680 m, and individual coal beds have a maximum thickness of about 6 m. Total gas content (generally excluding residual gas) of the coal beds ranges from less than 0.37 cm 3 /g (as-analyzed or raw basis; 1.2 cm 3 /g, dry, ash free basis, daf) at depths less than 400 m, to greater than 7.3 cm 3 /g (as-analyzed basis; 8.76 cm 3 /g, daf) in deeper (> 1,500 m) parts of the basin. About 20 Wilcox coal-gas wells in northern Louisiana produce from 200 to 6485 m 3 of gas/day and cumulative gas production from these wells is approximately 25 million m 3 (as of December, 2006). U.S. Geological Survey assessment of undiscovered, technically recoverable gas resources in the Gulf of Mexico Coastal Plain, including northern and south-central Mississippi, indicates that coal beds of the Wilcox Group contain an estimated mean total 109.3 million m 3 (3.86 trillion ft 3 ) of producible natural gas. To determine the origin of the Wilcox Group coal gases in northern Louisiana, samples of gas, water, and oil were collected from Wilcox coal and sandstone reservoirs and from under- and overlying Late Cretaceous and Eocene carbonate and sandstone reservoirs. Isotopic data from Wilcox coal-gas samples have an average δ 13 C CH4 value of − 62.6‰ VPDB (relative to Vienna Peedee Belemnite) and an average δ D CH4 value of − 199.9‰ VSMOW (relative to Vienna Standard Mean Ocean Water). Values of δ 13 C CO2 range from − 25.4 to 3.42‰ VPDB. Produced Wilcox saline water collected from oil, conventional gas, and coalbed gas wells have δ D H2O values that range from − 27.3 to − 18.0‰ VSMOW. These data suggest that the coal gases primarily are generated in saline formation water by bacterial reduction of CO 2 . Shallow (< 150 m) Wilcox coal beds containing freshwater have little or no biogenic gas. Molecular and isotopic analyses of gas samples collected from conventional gas and oil wells suggests that both biogenic and thermogenic gases are present in and adjacent to the Wilcox intervals that contain biogenic coal gases. Oil, probably sourced from thermally mature, down-structural-dip parts of the Wilcox Group, is produced from sandstones within the coal-bearing interval. Gas chromatograms of C 10+ saturated hydrocarbons from Wilcox oils show a depletion of n -alkanes probably resulting from biodegradation of the oil. Isotopic composition of the gases associated with the oils is of mixed themogenic and biogenic origin (average δ 13 C CH4 = − 44.4‰ VPDB, and average δ D CH4 = − 182.4‰ VSMOW).

International Journal of Coal Geology

Scanning electron microscopic evaluation of broad ion beam milling effects to sedimentary organic matter: Sputter-induced artifacts or naturally occurring porosity?

Research examining organic-matter hosted porosity has significantly increased during the last decade due to greater focus on understanding hydrocarbon migration and storage in source-rock reservoirs, and technological advances in scanning electron microscopy (SEM) capabilities. The examination of nanometer-scale organic-matter hosted porosity by SEM requires the preparation of exceptionally flat geologic samples beyond the abilities of traditional mechanical polishing, which can deform or otherwise obscure organic surfaces. To meet this demand, broad ion beam (BIB) milling was introduced as a sample preparation technique for SEM petrographic analysis of geologic samples. As with any sample preparation technique, there can be unintended consequences. In this study, we examined the development of nanometer-scale sputter-induced voids caused by BIB milling of thermoset plastic binder material [poly(methyl methacrylate), PMMA] used for the mounting of geologic samples, and artifact sputter-induced voids in the organic matter of Green River Formation and Kimmeridge Clay Formation source rocks. Development of artifact sputter-induced voids was evaluated in relation to variations in the slope of the sample examination surface (0.0–4.9% slope), effectively varying the angle of ion incidence. The results indicate that only minor variations in the angle of ion incidence can generate sputter-induced voids in both PMMA (10.0–386.2 nm diameter sputter-induced voids) and sample sedimentary organic matter (solid bitumen; 12.2–103.6 nm diameter sputter-induced voids). Overall, average artifact pore diameters increased with increasing ion incidence angle within PMMA. Although sputter-induced voids within solid bitumen in the Green River Formation sample were only found in limited extent, the size of these void artifacts falls within the same size range as naturally occurring meso-macroporosity. That is, the pore-like artifacts could easily be misconstrued as naturally developed organic porosity, which is a major concern for SEM-based porosity evaluation methods. This study describes the factors that contribute to the creation of artifact sputter-induced voids, their distinguishing characteristics, and best practices for avoiding the creation of ion-induced artifacts.

International Journal of Coal Geology

Minor element distribution in iron disulfides in coal: a geochemical review

Electron beam microanalysis of coal samples in U.S. Geological Survey (USGS) labs confirms that As is the most abundant minor constituent in Fe disulfides in coal and that Se, Ni, and other minor constituents are present less commonly and at lower concentrations than those for As. In nearly all cases, Hg occurs in Fe disulfides in coal at concentrations below detection by electron beam instruments. Its presence is shown by laser ablation ICP-MS, by selective leaching studies of bulk coal, and by correlation with Fe disulfide proxies such as total Fe and pyritic sulfur. Multiple generations of Fe disulfides are present in coal. These commonly show grain-to-grain and within-grain minor- or trace element compositional variation that is a function of the early diagenetic, coalification, and post-coalification history of the coal. Framboidal pyrite is almost always the earliest Fe disulfide generation, as shown by overgrowths of later Fe disulfides which may include pyrite or marcasite. Cleat- (or vein) pyrite (or marcasite) is typically the latest Fe disulfide generation, as shown by cross-cutting relations. Cleat pyrite forms by fluid migration within a coal basin and consequently may be enriched in elements such as As by deposition from compaction-driven fluids, metal enriched basinal brines or hydrothermal fluids. In some cases, framboidal pyrite shows preferential Ni enrichment with respect to co-occurring pyrite forms. This is consistent with bacterial complexing of metals in anoxic sediments and derivation of framboidal pyrite from greigite (Fe 3 S 4 ), an Fe monosulfide precursor to framboidal pyrite having the thio-spinel structure which accommodates transition metals. Elements such as As, Se, and Sb substitute for S in the pyrite structure whereas metals, including transition metals, Hg and Pb, are thought to substitute for Fe. Understanding the distribution of minor and trace elements in Fe disulfides in coal has important implications for their availability to the environment through coal mining and use, as well as for potential reduction by coal preparation, and for delineating diagenetic compositional changes throughout and after coal formation.

International Journal of Coal Geology

Coal resources of the Sonda coal field, Sindh Province, Pakistan

Approximately 4.7 billion t of original coal resources, ranging from lignite A to subbituminous C in rank, are estimated to be present in the Sonda coal field. These resources occur in 10 coal zones in the Bara Formation of Paleocene age. The Bara Formation does not out crop in the area covered by this report. Thin discontinuous coal beds also occur in the Sonhari Member of the Laki Formation, of Paleocene and Eocene age, but they are unimportant as a resource of the Sonda coal field. The coal resource assessment was based on 56 exploratory drill holes that were completed in the Sonda field between April 1986 and February 1988. The Sonda coal field is split into two, roughly equal, areas by the southwestward flowing Indus River, a major barrier to the logistics of communications between the two halves. As a result the two halves, called the Sonda East and Sonda West areas, were evaluated at different times by slightlydifferent techniques; but, because the geology is consistent between the two areas, the results of both evaluations have been summarized in this report. The resource estimates for the Sonda East area, approximately 1,700 million t, were based on the thickest coal bed in each zone at each drill hole. This method gives a conservative estimate of the total amount of coal in the Sonda East area. The resource estimates for the Sonda West area, approximately 3,000 million t, were based on cumulative coal bed thicknesses within each coal zone, resulting in a more liberal estimate. In both cases, minimum parameters for qualifying coal were a thickness of 30 cm or greater and no more than 50% ash; partings thicker than 1 cm were excluded. The three most important coal zones in the Sonda field are the Inayatabad, the Middle Sonda and the Lower Sonda. Together, these three coal zones contain 50% of the total resources. Isopachs were constructed for the thickest coal beds in these three coal zones and indicate large variations in thickness over relatively small distances. Coal beds in the Sonda coal field were difficult to correlate because of poor core recovery in some intervals and abrupt lateral thinning and thickening. Most coal zones are separated by 5–10 m of interburden, although in some places the interburden between zones is over 100 m thick. More closely spaced drill holes should clarify and significantly improve coal zone correlations in the Bara Formation. Coal resources in the Sonda coal field were calculated for three reliability categories; measured, indicated, and inferred. The most reliable estimates are those for the measured category. Measured coal resources are approximately 91 million t, or about 2% of the total resource; indicated resources are 681 million t, or about 14% of the total; and inferred resources, the least reliable resource category, are 3,931 million t, or 84% of the total resources. The distribution of resources by reliability category is due to the relatively wide spacing (approximately 5 km) between core holes. Analyses of 90 coal samples, on an as-received basis, indicate average ash and sulfur contents of 13.7% and 3.6%, respectively, and a range in rank from lignite A to subbituminous C. Calorific values for these samples range from 6,000 to 8,000 Btu/lb (1 Btu = 1055J; 1 lb = 4536 kg).

International Journal of Coal Geology

Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana

Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur (< 1%) Danville Coal Member of the Dugger Formation and the other is the high-sulfur (> 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in ??34S for sulfur species within and between the low-sulfur and high-sulfur coal. The ??34S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the ??34S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the ??34S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of ??34S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in ??34S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition. The ??34S values for fly ash from the high-sulfur Springfield coal (averaging 9.7???) are greatly enriched in 34S relative to those in the parent coal (averaging 2.2???). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the ??34S values for fly-ash samples from the low-sulfur Danville coal average 10.2???, only slightly enriched in 34S relative to those from the parent coal (average 7.5???). The ??34S values for bulk S determined directly from the fly-ash samples show close correspondence with the ??34S values for SO4- 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion. ?? 2007 Elsevier B.V. All rights reserved.

International Journal of Coal Geology

Organic petrology of the Aptian-age section in the downdip Mississippi Interior Salt Basin, Mississippi, USA: Observations and preliminary implications for thermal maturation history

This study identifies a thermal maturity anomaly within the downdip Mississippi Interior Salt Basin (MISB) of southern Mississippi, USA, through examination of bitumen reflectance data from Aptian-age strata (Sligo Formation, Pine Island Shale, James Limestone, and Rodessa Formation). U.S. Geological Survey (USGS) reconnaissance investigations conducted in 2011–2012 examined Aptian-age thermal maturity trends across the onshore northern Gulf of Mexico region and indicated that the section in the downdip MISB is approaching the wet gas/condensate window (R o ~1.2%). A focused study in 2012–2013 used 6 whole core, one sidewall core, and 49 high-graded cutting samples (depth range of 13,000–16,500 ft [3962.4–5029.2 m] below surface) collected from 15 downdip MISB wells for mineralogy, fluid inclusion, organic geochemistry, and organic petrographic analysis. Based on native solid bitumen reflectance (R o generally > 0.8%; interpreted to be post-oil indigenous bitumens matured in situ), R o values increase regionally across the MISB from the southeast to the northwest. Thermal maturity in the eastern half of the basin (R o range 1.0 to 1.25%) appears to be related to present-day burial depth and shows a gradual increase with respect to depth. To the west, thermal maturity continues to increase even as the Aptian section shallows structurally on the Adams County High (R o range 1.4 to > 1.8%). After evaluating the possible thermal agents responsible for increasing maturity at shallower depths (i.e., igneous activity, proximity to salt, variations in regional heat flux, and uplift), we tentatively propose that either greater paleoheat flow or deeper burial coupled with uplift in the western part of the MISB could be responsible for the thermal maturity anomaly. Further research and additional data are needed to determine the cause(s) of the thermal anomaly.

International Journal of Coal Geology

Evaluating aromatization of solid bitumen generated in the presence and absence of water: Implications for solid bitumen reflectance as a thermal proxy

Geological models for petroleum generation suggest thermal conversion of oil-prone sedimentary organic matter in the presence of water promotes increased liquid saturate yield, whereas absence of water causes formation of an aromatic, cross-linked solid bitumen residue. To test the influence of hydrogen from water, organic-rich (22 wt% total organic carbon , TOC) mudrock samples from the Eocene lacustrine Green River Formation Mahogany zone oil shale were pyrolyzed under hydrous and anhydrous conditions in closed system batch reactors at temperatures between 300 and 370 °C for 72 h. Pre- and post-pyrolysis samples were characterized using petrographic approaches including optical microscopy , reflectance, Raman spectroscopy , and scanning electron and transmission electron microscopy to quantify differences in relative appearance, abundance, and composition of solid bitumen newly generated during the pyrolysis experiments. Petrographic analyses were supplemented by geochemical screening measurements (TOC content and programmed temperature pyrolysis). Results show post-hydrous pyrolysis residues contain lower TOC, are comprised of solid bitumen with greater aromaticity , and have textures indicative of lower viscosities, relative to anhydrous residues from the same temperature pyrolysis conditions. These observations suggest solid bitumen forming from thermal conversion of oil-prone sedimentary organic matter under anhydrous conditions may be less aromatic, although more cross-linked, than solid bitumen forming under hydrous conditions at the same time-temperature combination. To explain these results, we suggest that a radical disproportionation mechanism is favored in the presence of hydrogen donated from water, and that this disproportionation promotes aromatization in the solid residue with concomitant expulsion of saturated hydrocarbons.

International Journal of Coal Geology

Sample mounting for organic petrology: No thermal effects from transient exposure to elevated temperatures

For sample mounting, organic petrology laboratories typically use cold-setting epoxy-resin (e.g., 40 °C, used by Oklahoma Geological Survey, OGS) or heat-setting thermoplastic (e.g., 180 °C, used by U.S. Geological Survey, USGS). Previous workers have suggested a systematic huminite/vitrinite reflectance (VR o ) increase was associated with the thermoplastic preparation process, relative to epoxy mounting, which was possibly attributed to moisture loss from organic matter due to the transient high temperatures of plastic mounting. In this study, we evaluated thermal effects to low thermal maturity organic matter from transient exposure to elevated temperatures. A subbituminous coal sample was subjected to long-term (4 to 38 weeks) exposure to temperatures of 85 to 120 °C and afterward evaluated by multiple approaches to test thermal advance [elemental analyses, Rock-Eval pyrolysis, Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), pyrolysis gas chromatography, and petrographic analyses, including huminite/vitrinite reflectance and spectral fluorescence], all of which showed no detectable systematic (statistically insignificant) changes between the original sample and its heat-treated products. We also compared huminite/vitrinite reflectance of six low thermal maturity samples (those most likely to react to transient heating) mounted via both cold-setting epoxy-resin and heat-setting thermoplastic. Results indicate measured VR o of a sample prepared by one mounting process was within the standard deviation of reflectance for the same sample prepared via the other process. Moreover, VR o results were not systematically higher in thermoplastic mounts. Contrary to previous work, these results suggest thermoplastic mounting or other transient exposure to elevated temperatures does not impact thermal maturity estimates from reflectance measurement for low thermal maturity organic samples. Furthermore, the average interlaboratory difference in measured VR o (between OGS and USGS) for the same sample prepared by either epoxy-resin or thermoplastic mounting was 0.038%, about double the average difference between VR o for the same sample prepared via epoxy-resin versus thermoplastic in a single laboratory (0.024%). This result indicates interlaboratory variability impacts VR o measurement reproducibility to the extent that systematic differences could not be observed between thermoplastic and cold-setting sample preparation approaches, even if such differences were present.

International Journal of Coal Geology

The geology, botany and chemistry of selected peat-forming environments from temperate and tropical latitudes

Peat has been studied in several geologic settings: (1) glaciated terrain in cold temperate Maine and Minnesota, U.S.A.; (2) an island in the Atlantic Ocean off the coast of Maine, where sea level is rising; (3) the warm temperate U.S. Atlantic and Gulf Coastal Plains, where sea level has changed often; and (4) the tropical coast of Sarawak, Malaysia, and the tropical delta of the Batang Hari River, Sumatra, Indonesia. Most of these deposits are domed (ombrotrophic or partly ombrotrophic) bogs in which peat accumulation continued above the surface of the surrounding soil. However, the bogs of the U.S. Atlantic and Gulf Coastal Plains are comparatively not as domed, and many have almost level surfaces. In some bogs, aquatic or semi-aquatic plant materials accumulated, replaced water in the depressions, and formed a surface on which marsh or swamp vegetation could subsequently live, die, and accumulate. In others, the plant materials accumulated initially on level silt or sand surfaces supporting marshes or swamps. As the peat dome formed, plants growing on it changed from luxuriant ones near the base of the dome, where nutrients were brought into the bog by surface and ground water, to stunted ones at the top of the dome, where the raised bogs are fed by nutrient-poor precipitation. The physical and chemical changes that take place in the sequence of environments from the pond stage of deposit development, through the grassy marsh stage, through the forested swamp stage, and finally through the heath dome stage can be measured in terms of acidity and ash, volatile matter, carbon, hydrogen, nitrogen, sulfur and oxygen contents, as well as in the kind and distribution of trace elements. The organic and inorganic contents of the deposits relate to geomorphology, and geomorphology relates to their settings. As models of coal formation, some domed peat deposits may help in solving problems of distribution and character of ancient coal beds. But clearly not all peat deposits are precursors of coal. Most Holocene peat deposits are subject to destruction by erosion, fire and decomposition through microbial and chemical oxidation before burial. The best environments for coal precursors have biomass accumulation, a continuously rising water table within the mass, and minimum influx of clay and silt until preservation by burial. The most suitable settings for future economic coal deposits are domed bogs that accumulate thick, widespread peat having low ash and low sulfur contents. The ombrotrophic peat deposits of tropical Sarawak and Sumatra are thick and extensive, contain low-ash and low-sulfur peat, and have high heating values. They are considered to be the best tropical coal analogs because of their extent and chances of preservation; the base of the peat is below adjacent river levels, and chemical and structural conditions are favorable for accumulation.

International Journal of Coal Geology

Petrographic maturity parameters of a Devonian shale maturation series, Appalachian Basin, USA. ICCP Thermal Indices Working Group interlaboratory exercise

This paper presents results of an interlaboratory exercise on organic matter optical maturity parameters using a natural maturation series comprised by three Devonian shale samples (Huron Member, Ohio Shale) from the Appalachian Basin, USA. This work was conducted by the Thermal Indices Working Group of the International Committee for Coal and Organic Petrology (ICCP) Commission II (Geological Applications of Organic Petrology). This study aimed to compare: 1. maturation predicted by different types of petrographic parameters (vitrinite reflectance and spectral fluorescence of telalginite), 2. reproducibility of the results for these maturation parameters obtained by different laboratories, and 3. improvements in the spectral fluorescence measurement obtained using modern detection systems in comparison with the results from historical round robin exercises. Mean random vitrinite reflectance measurements presented the highest level of reproducibility (group standard deviation 0.05) for low maturity and reproducibility diminished with increasing maturation (group standard deviation 0.12). Corrected fluorescence spectra, provided by 14 participants, showed a fair to good correspondence. Standard deviation of the mean values for spectral parameters was lowest for the low maturity sample but was also fairly low for higher maturity samples. A significant improvement in the reproducibility of corrected spectral fluorescence curves was obtained in the current exercise compared to a previous investigation of Toarcian organic matter spectra in a maturation series from the Paris Basin. This improvement is demonstrated by lower values of standard deviation and is interpreted to reflect better performance of newer photo-optical measuring systems. Fluorescence parameters measured here are in good agreement with vitrinite reflectance values for the least mature shale but indicate higher maturity than shown by vitrinite reflectance for the two more mature shales. This red shift in λ max beyond 0.65% vitrinite reflectance was also observed in studies of Devonian shale in other basins, suggesting that the accepted correlation for these two petrographic thermal maturity parameters needs to be re-evaluated. A good linear correlation between λ max and T max for this maturation series was observed and λ max 600 nm corresponds to T max of 440 °C. Nevertheless if a larger set of Devonian samples is included, the correlation is polynomial with a jump in λ max ranging from 540 to 570 nm. Up to 440 °C of T max , the λ max , mostly, reaches up to 500 nm; beyond a T max of 440 °C, λ max is in the range of 580–600 nm. This relationship places the “red shift” when the onset of the oil window is reached at T max of 440 °C. Moreover, the correlation between HI and λ max (r 2 = 0.70) shows a striking inflection and decrease in HI above a λ max of 600 nm, coincident with the approximate onset of hydrocarbon generation in these rocks.

International Journal of Coal Geology