Ohio Shale Research Articles

Organic matter enrichment in basin periphery: A case study of Wufeng-Longmaxi shale, Marcellus shale, and Ohio shale

Our study investigates organic matter (OM) enrichment at the peripheries of marine basins, contrasting with prior research focused on central regions. We analyze three shale formations at three distinct deposition sites: the Marcellus (M) shale near an orogenic belt, and the Wufeng-Longmaxi (WL) shale, the Ohio (O) shale adjacent to a forebulge uplift. By examining factors such as redox conditions, clastic input, paleoproductivity, sedimentary facies and geological activities, we identify that the OM enrichment in shale (M shale) near the orogen resulted from significant inputs of river detritus and semi-deep shelf environment. Additionally, local enrichment is primarily influenced by volcanic ash sedimentation. The shale (O shale) at the distal end of the forebulge shows high OM concentration due to its stable deep-water shelf environment. Local enrichment in this area is caused by sediment re-sedimentation and glaciation. Similarly, the shale (WL shale) at the proximal end also exhibits a high OM concentration due to its stable deep-water shelf environment. In this case, volcanic ash deposition and transgression are responsible for the local enrichment. Our findings reveal how paleogeography and geological activities impact OM enrichment in basin peripheries, while also offering insights into evaluating shale gas reservoirs.

Hydrocarbon Potential and Reservoir Characteristics of Lacustrine Shale: A Case of Lower Jurassic in the Western Qaidam Basin, NW China

The Lower Jurassic lacustrine shale is well developed in the western Qaidam Basin and characterized by significant thickness and continuous distribution. Previous investigations have indicated its substantial potential as a shale gas resource. Based on experiments of organic carbon content, vitrinite reflectance, rock-eval pyrolysis, X-ray diffraction, and low-temperature nitrogen adsorption, the hydrocarbon potential and reservoir characteristics of Lower Jurassic lacustrine shale in the western Qaidam Basin were systematically analyzed. The results show that the total organic carbon (TOC) content ranges from 1.71% to 4.49%, with an average of 2.98%. The kerogen belongs to type II–III. The vitrinite reflectance (Ro) ranges from 1.05% to 1.95%, with an average of 1.62%, indicating that the kerogen has reached the high thermal maturity stage (gas window). The maximum pyrolysis peak temperature (Tmax) ranges from 408 °C to 580 °C, with an average of 498.38 °C, further supporting the high thermal maturity of the kerogen. The content of brittle minerals, including quartz, feldspar, pyrite, and carbonate, ranges from 21% to 44% (averaging 32.54%), which is comparable to shale minerals found in American Ohio shale. The pore structure of the shale is predominantly characterized by open parallel plate slit pores and inclined slit pores. The pore diameter distribution curve can be divided into two types, including unimodal distribution and bimodal distribution. Micropores and mesopores contribute significantly to the specific surface area, and mesopores account for the highest proportion of pore volume. The thermal evolution degree has a direct impact on pore development of shale reservoirs. The micropore, mesopore, macropore, and total pore volumes of lacustrine shale in the study area show a negative correlation with TOC content, indicating that the organic matter within the shale is probably still in the first pyrolysis stage. However, no significant correlation is observed between pore volume and clay mineral content or between pore volume and brittle mineral content due to the complex interplay of several geological factors. These findings contribute to a better understanding of the lacustrine shale gas resource potential and can guide future exploration and exploitation efforts. In addition, the systematic analysis of reservoir characteristics serves as a foundation for the introduction and exploration of new shale fracturing technologies, which is of great significance for reducing the consumption of water resources and mitigating potential geo-disasters.

Some vertebrate types (Chondrichthyes, Actinopterygii, Sarcopterygii, and Tetrapoda) from two Paleozoic Lagerstätten of Ohio, U.S.A.

ABSTRACT The type specimens of eight Paleozoic vertebrate species from Ohio, U.S.A., originally described by J. S. Newberry and subsequently reposited in the Orton Geological Museum, are reviewed and illustrated photographically. They include four actinopterygian fish species from the Linton Konservat-Lagerstätte (Upper Freeport Coal; Carboniferous) in Jefferson County, Ohio, described in 1857 under the basionyms Mecolepis corrugatus (now Haplolepis corrugata), M. insculptus (synonymized as Parahaplolepis tuberculata), M. lineatus (now Pyritocephalus lineatus), and M. ovoideus (now Microhaplolepis ovoidea). One actinopterygian species, Eurylepis striolatus, a junior synonym of Haplolepis corrugata, was described in 1873 from the Linton deposit; and one chondrichthyan species, Orthacanthus gracilis, now replaced as Orthacanthus adamas Babcock, 2024, was first described by Newberry in 1875 from Linton. Lectotypes are designated from the syntypic series of M. insculptus and O. adamas. A tooth from the Linton Lagerstätte, originally described as a fish in 1857 under the basionym Rhizodus lancifer, is the holotype of the tetrapod (anthracosaur) Anthracosaurus lancifer. One Devonian sarcopterygian fish species, Onychodus ortoni, was described in 1889 from the Ohio Shale, Huron Shale Member, a Konservat-Lagerstätte occurring in Franklin County, Ohio.

Mapping ancient sedimentary organic matter molecular structure at nanoscales using optical photothermal infrared spectroscopy

Elucidating the molecular structure of sedimentary organic matter (SOM) is key to understanding petroleum generation processes, as well as ancient sedimentary environments. SOM structure is primarily controlled by biogenic source material (e.g., marine vs. terrigenous), depositional conditions, and subsurface thermal history. Additional factors, e.g., strain, may also impact the molecular structure of SOM. Multiple spatially resolved approaches exist for in situ evaluation of SOM, including Raman and infrared spectroscopies, as well as mass spectrometric methods. While these methods have enabled increased understanding of the occurrence and distribution of SOM functional groups, they suffer from disadvantages including low spatial resolution (infrared spectroscopy), limited molecular information (Raman spectroscopy), and sample destruction (mass spectrometric methods). Recent technological advances have resulted in infrared spectrometers capable of breaking the Abbe diffraction limit, greatly increasing the spatial resolutions accessible for an infrared measurement.Here we utilize optical photothermal infrared spectroscopy (O-PTIR) to record maps of functional group distributions at 500 nm spatial resolution in Tasmanites (algal microfossils) from the Upper Devonian Ohio Shale. These data allow for discrimination between Tasmanites, adjacent SOM, and fine-grained minerals. Additionally, functional group distributions within Tasmanites were found to be generally homogenous, although slight variations exist between the body and fold apices (zones of greatest deformation) which may indicate strain-induced chemical reactions. The data presented here represent the first application of O-PTIR to study SOM, highlighting the promise of this analytical approach for future studies evaluating the molecular composition of geologic materials at sub-micron scales.

Evidence for Possible Late Paleozoic Alleghenian Deformation Structures in the Devonian Rocks of Erie County, Ohio, USA

Partially exposed bedrock beneath Pleistocene glacial till in Erie County (north-central Ohio) displays unusual structural deformation in the Devonian Berea Sandstone, Bedford Shale, and Ohio Shale. These folded and faulted units are exposed in creeks as anticlines and synclines. Past studies of this area proposed Pleistocene ice movement and soft-sediment deformation during the Late Paleozoic as the deformation mechanisms, but these hypotheses cannot explain the extent of layer displacement or the contradiction between the southwest travel direction of the ice sheet and the structural sense of motion on the folded units. A new interpretation using field data and constructing geologic profiles explains the development of these structures. This study investigated 17 anticlines that trend in different directions. Four of these anticlines are tightly folded with steep or overturned flanks and thrust-faulted Ohio Shale in their cores. Structural analysis of these folds shows that the incompetent shaly units of the Plum Brook–Ohio–Bedford and competent Berea Sandstone were folded above the Delaware–Niagara carbonates as a result of the compressional stress during the Late Paleozoic. Development of these tight or overturned folds, and change in trend of the anticlines, is caused by unusual stratigraphic thickness variations in the Berea and Bedford units. Preserved and undeformed fine sedimentary structures, and sharply faulted beds, in the Berea and Bedford indicate that soft-sediment deformation was not the cause of the regional structural deformation. Finally, the absence of physical features of glacially deformed bedrock demonstrates that Pleistocene glacial ice shove was not the cause of deformed bedrock units in the study area.

Taxonomy and diversity of slit‐band gastropods (Order Pleurotomariida) and some slit bearing Caenogastropoda from the Pennsylvanian of the USA

AbstractPleurotomariida have the longest fossil record among living gastropods and are diverse and abundant in the middle and upper Palaeozoic. Its traditional classification is based on adult shell characters. The early shell morphology has been largely unknown. We describe exceptionally well‐preserved Pleurotomariida from the Pennsylvanian marine shales of Texas, Oklahoma, Kansas and Ohio. In total, 38 species representing 19 genera are described, including 10 new species, one new genus and one new subgenus:Eirlysella buckhornensisgen. et sp. nov.,Shansiella(Oklahomaella)globilineatasubgen. et sp. nov.,Phymatopleura girtyi,Phymatopleura conica,Worthenia(Yochelsonospira)kuesi,Dictyotomaria turrisbabel,Paragoniozona yanceyi,Spiroscala shwedagoniformis,Peruvispira oklahomaensis,Baylea tenera. Replacement names areParagoniozona ornatanom. nov. (forPleurotomaria asperaGirty),Spiroscala quasipulchranom. nov. (forEuconospira pulchraBatten). The early ontogenetic shells including protoconchs and early teleoconchs are reported in detail for the first time for most taxa. Most species have a protoconch of one whorl as that of living Vetigastropoda. Planktotrophic protoconchs (multi‐whorled larval shells with sinusigera) are reported forPlatyzonaandPeruvispira; they are therefore placed in the family Goniasmatidae (Caenogastropoda). Repaired shell scars were found in juvenile Pleurotomariida specimens (c. 1 mm), suggesting exposure to predation from an early stage of ontogeny. Pleurotomariida are strongly dominant in surface samples of the Finis Shale (Texas) but in bulk samples using fine mesh‐sizes, dominance is much less pronounced, indicating a change in clade proportion depending on sampling method. The taxonomic richness and abundance of Pleurotomariida seen in these Carboniferous shales have not been reported from post‐Triassic formations.

Berea Sandstone: New developments in a mature oil and gas play, eastern Kentucky and Ohio

With development dating from the 1800s, the Devonian Berea Sandstone has a long history of oil and gas development in the Appalachian Basin. A new phase of development began in northeastern Kentucky in 2011 with production of high-gravity oil from horizontal wells at depths less than 2200 ft (<671 m). Oil production in areas previously unproductive or primarily gas productive was unexpected because thermal-maturity measures, such as vitrinite reflectance, suggested source rocks should be immature. Moreover, downdip the Berea Sandstone appeared to produce primarily gas within the oil window. Organic petrography and geochemical analyses were conducted on source rocks overlying (Sunbury Shale) and underlying (Ohio Shale) the Berea Sandstone and produced oil and gas from the Berea Sandstone and Ohio Shale. Samples were collected from southernmost Ohio to southeastern Kentucky along a northwest-to-southeast transect representing increased burial depth. Geochemistry results suggest the Sunbury or Ohio Shales could be sources of oil reservoired in the Berea Sandstone. Migration is necessary to account for oil in the updip parts of the play. Vitrinite reflectance measurements suggest, however, the area mature for oil is larger compared to previous assessments. Consequently, less migration is needed to account for the distribution of oil production. Gas chemistry reflects the thermal-maturity effect of regional dip with additional influence from local structures. Stratigraphic analysis of the Berea Sandstone in core and outcrop shows it to be primarily a siltstone with lateral facies changes, different bedding types, and diagenesis producing a complex reservoir.

Molecular and isotopic gas composition of the Devonian Berea Sandstone and implications for gas evolution, eastern Kentucky

Since 2011, the Devonian Berea Sandstone in northeastern Kentucky has produced oil where thermal maturity studies indicate that likely source rocks, namely, the Devonian Ohio Shale and Mississippian Sunbury Shale, are thermally immature. Downdip, where source rocks are mature for oil, the Berea Sandstone and Ohio Shale primarily produce gas. To investigate this thermal maturity discordancy, the molecular and isotopic composition of gases from the Berea Sandstone (oil associated) and Ohio Shale (nonassociated) were analyzed to understand the gas generation and migration history. Collected along a northwest-southeast transect in eastern Kentucky, samples range from 1079 to 4602 ft, respectively. All are wet gases with a thermogenic origin (δ13C-CH4 e −53.5‰ to −46.1‰). This is mostly consistent with a reevaluation of thermal maturity in a companion study that expands the area mature for oil. Gas migration is required, however, in updip parts of the Berea play where vitrinite reflectance (VRo) values are less than 0.6%. Southeast regional dip exerts a first-order influence on thermal maturity as gases become drier and isotopically heavier downdip. Correlation of δ13C values for heavier hydrocarbon gases in a natural gas plot with VRo contour spacing demonstrates the influence of nearby source rock thermal maturity on gas composition. Downdip, migration of oil and the attendant increase in permeability relative to gas may account for the dominance of gas production in the Ohio Shale. Migration along with basin uplift after the Alleghany orogeny may have contributed to development of a gas phase that exsolved from oil.

Organic petrology and geochemistry of the Sunbury and Ohio Shales in eastern Kentucky and southeastern Ohio

As part of a study to determine the origin of oil and gas in the Berea Sandstone in northeastern Kentucky and southeastern Ohio, 158 samples of organic-rich shale from the Upper Devonian Olentangy and Ohio Shales and the Lower Mississippian Sunbury Shale, collectively referred to as the “black shale,” were collected and analyzed from 12 cores. The samples were analyzed for total organic carbon (TOC) content, organic petrography, and programmed pyrolysis. Previously acquired analytical data for 11 samples from 2 additional wells in eastern Kentucky were also used. Most of the samples were organic rich (>5 wt. % TOC), high in sulfur (>2.0 wt. %), and dominated by liptinite macerals. The vitrinite reflectance (VRo) and equivalent vitrinite reflectance (VReq) values, calculated from bitumen reflectance (BRo) measurements, were found to be in close agreement. The calculated reflectance values from programmed pyrolysis temperature at which the maximum release of hydrocarbons occurs (Tmax) showed better agreement with measured VRo after Tmax was corrected for excessive hydrogen index values for several samples. Thermal maturation parameters were found to increase in a northwest–southeast direction, paralleling an increase in black shale thickness and depth of burial. The thermal maturity proxies indicate the northwestern part of the study area to be more thermally mature than previously indicated. Geochemical and biomarker data from Berea oils indicate migration of oil from more thermally mature to less thermally mature areas. As such, the occurrence of petroleum liquids in the Berea Sandstone cannot be predicted directly from conventional thermal maturity proxies (Tmax, VRo, and BRo) because these methods do not account for migrated petroleum.

From source to sink: Glacially eroded, Late Devonian algal “cysts” (Tasmanites) delivered to the Gulf of Mexico during the Last Glacial Maximum

Abstract The source of reworked Devonian algal “cysts” in last glacial maximum (LGM) sediment in the Gulf of Mexico is traced to their host black shales, which ring the southwestern Great Lakes. The source-to-sink pathway includes intermediate storage in fine-grained LGM glacial lacustrine sediment and till. The “cysts” are pelagic chlorophyllous algae (Tasmanites and Leiosphaeridia), collectively referred to herein as tasmanitids. Radiocarbon dates of syndepositional Gulf of Mexico foraminifera, derived from accelerator mass spectrometry, bracket the Gulf of Mexico sediment age with common tasmanitids from 28.5 ± 0.6–17.8 ± 0.2 cal kyr B.P. Approximately 1400 km north of the Gulf of Mexico, tasmanitids are abundant in Upper Devonian black shales (New Albany, Antrim, and Ohio Shales) that ring the Michigan, Illinois, and Appalachian intracratonic basins. Tasmanitids were eroded from bedrock and incorporated in glacial sediment dating from ca. 28.0–17.6 cal kyr B.P. by the Lake Michigan, and Huron-Erie lobes of the Laurentide Ice Sheet. The physical characteristics of tasmanitids are ideal for long-distance transport as suspended sediment (density: 1.1–1.3 g/cc, size ranging from 63 µm to 300 µm), and these sand-sized tasmanitids traveled with the silt-clay fraction. Thus, the source-to-sink journey of tasmanitids was initiated by subglacial erosion by water or friction, sequestering in till or glaciolacustrine sediment, re-entrainment and suspension in meltwater, and final delivery in meltwater plumes to the Gulf of Mexico. River routes included the Mississippi, Illinois, Ohio, Wabash, Kaskaskia, and many of their tributaries. Reworked Devonian tasmanitids are a previously unrecognized link between their occurrence in deep-water deposits of the Gulf of Mexico and the late Wisconsin glacial history of the Upper Mississippi Valley. We propose that tracking occurrences of tasmanitid concentrations from the source area to sink, along with adjunct proxies such as clay minerals, will facilitate a more refined analysis of the timing and duration of megafloods. This study also demonstrates that isotopically dead carbon, from reworked Devonian tasmanitid “cysts,” can contaminate radiocarbon dating of LGM bulk sediment samples toward older ages.

Assessing the thermal maturity of black shales using vitrinite reflectance: Insights from Devonian black shales in the eastern United States

Thermal maturity of source rocks indicated by vitrinite reflectance (Ro) is an important and reliable parameter to determine the petroleum potential of sedimentary basins. Originally, Ro was used to characterize the degree of coalification of coals and thus works well for coal seams, but it has limitations when used to determine the thermal maturity of black shale successions. A suite of six coal-shale pairs from the Upper Devonian black shale formations in the eastern United States (New Albany Shale, Ohio Shale, Dunkirk Shale, and Rhinestreet Shale) was selected to study the applicability of Ro in assessing the thermal maturity of black shale successions. The results show that vitrinite in the studied coal samples is dominated by collotelinite, whereas vitrinite in black shales occurs as small dispersed particles (~5 μm) in the mineral matrix. When comparing the size and morphology of dispersed vitrinite particles in shales and collotelinite fragments in coals, vitrinite in shales and adjacent coals should have the same origin. The measured mean random Ro of vitrinite in coals ranges from 0.51–0.68%, and is 0.04–0.11% (average 0.07%) lower than that of dispersed vitrinite particles in enclosing shales. This observation contrasts with previously reported Ro suppression in liptinite-rich black shales. A high standard deviation of Ro measurements indicates a highly heterogeneous nature of vitrinite in black shales.Three mechanisms can be envisioned to contribute to the higher Ro of dispersed vitrinite particles in black shales relative to enclosed coals. First, small vitrinite particles may become more oxidized because small particles are more frequently suspended during transport to the site of deposition and reworking of bottom sediments after deposition than large pieces of driftwood that will turn into enclosed coal lenses during burial diagenesis. Second, misidentification of zooclast (e.g., chitinozoan) fragments as vitrinite due to loss of diagnostic morphology. Third, various macerals in the vitrinite group (e.g., corpogelinite and collotelinite) may have had different original reflectance values. Based on the petrographic characteristics of vitrinite and vitrinite-like particles, caution should be applied when using the Ro values of dispersed vitrinite and vitrinite-like particles in black shales as indicators of thermal maturity.

The oldest fossil axiid (Decapoda: Pleocyemata: Axiidea), from the Late Devonian (Famennian) Chagrin Shale Member of the Ohio Shale, USA

Abstract Discovery of a single specimen of a nearly complete cephalothorax and pleon of a new arthropod from the Late Devonian (Famennian) Chagrin Shale Member of the Ohio Shale Formation in Lake County, northeastern Ohio, USA documents the oldest known representative of the Axiidea. The specimen documents a new genus and species, Devonoaxius garlandi, and extends the range of the infraorder from the Jurassic into the Late Devonian. This range extension was predicted by a recent phylogenetic analysis. The addition of this axiid brings to four the number of arthropod genera in the Chagrin Shale Member, two of which represent the oldest members of their lineage.

Application of Raman Spectroscopy as Thermal Maturity Probe in Shale Petroleum Systems: Insights from Natural and Artificial Maturation Series

Raman spectroscopy was studied as a thermal maturity probe in a series of Upper Devonian Ohio Shale samples from the Appalachian Basin spanning from immature to dry gas conditions. Raman spectroscopy also was applied to samples spanning a similar thermal range created from 72-h hydrous pyrolysis (HP) experiments of the Ohio Shale at temperatures from 300 to 360 °C and isothermal HP experiments lasting up to 100 days of similar Devonian–Mississippian New Albany Shale. Raman spectra were treated by automated evaluation software based on iterative and simultaneous modeling of signal and baseline functions to decrease subjectivity. Spectra show robust correlation to measured solid bitumen reflectance (BRo) values and were therefore used to construct logarithmic regression relationships for calculation of BRo equivalent values. Raman spectra show considerable differences between natural samples and HP residues with similar measured BRo values, indicating as-yet undetermined differences in carbon chemistry. We ...

A stable and productive marine microbial community was sustained through the end-Devonian Hangenberg Crisis within the Cleveland Shale of the Appalachian Basin, United States.

The end-Devonian Hangenberg Crisis constituted one of the greatest ecological and environmental perturbations of the Paleozoic Era. To date, however, it has been difficult to precisely constrain the occurrence of the Hangenberg Crisis in the Appalachian Basin of the United States and thus to directly assess the effects of this crisis on marine microbial communities and paleoenvironmental conditions. Here, we integrate organic and inorganic chemostratigraphic records compiled from two discrete outcrop locations to characterize the onset and paleoenvironmental transitions associated with the Hangenberg Crisis within the Cleveland Shale member of the Ohio Shale. The upper Cleveland Shale records both positive carbon (δ13 Corg ) and nitrogen (δ15 Ntotal ) isotopic excursions, and replenished trace metal inventories with links to eustatic rise. These dual but apparently temporally offset isotope excursions may be useful for stratigraphic correlation with other productive end-Devonian epeiric marine locations. Deposition of the black shale succession occurred locally beneath a redox-stratified water column with euxinic zones, with signs of strengthening denitrification during the Hangenberg Crisis interval, but with an otherwise stable and algal-rich marine microbial community structure sustained in the surface mixed layer as ascertained by lipid biomarker assemblages. Discernible trace fossil signals in some horizons suggest, however, that bioturbation and seafloor oxygenation occurred episodically throughout this succession and highlight that geochemical proxies often fail to capture these rapid and sporadic redox fluctuations in ancient black shales. The paleoenvironmental conditions, source biota, and accumulations of black shale are consistent with expressions of the Hangenberg Crisis globally, suggesting this event is likely captured within the uppermost strata of the Cleveland Shale in North America.

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.

Organic petrology and micro-spectroscopy of Tasmanites microfossils: Applications to kerogen transformations in the early oil window

The transformation of kerogen to hydrocarbons in the early stages of oil generation is critical for understanding the resource potential of liquid-rich shale plays. Organic petrology commonly is used for visual evaluation of type, quality, and thermal maturity of organic matter, but the relationship of visual petrographic changes to chemical transformations is not well characterized. To improve understanding of these processes, organic-walled microfossils of the unicellular green alga Tasmanites (composed of algaenan) in Upper Devonian Ohio Shale (Huron Member, Appalachian Basin) were analyzed by micro-spectroscopy techniques including micro-Fourier transform infrared (micro-FTIR), X-ray photoelectron (XPS), electron probe microanalysis (EPMA), and fluorescence. Immature to mid-oil window maturation sequences of core and outcrop samples with solid bitumen reflectance (BR) and vitrinite reflectance (VR) values ranging from 0.45 to 0.80%Ro were used. Hydrous pyrolysis was applied to low-maturity (BR: 0.25–0.39%Ro) Huron and time-correlative New Albany shale samples to create similar artificial maturation sequences for comparison. Micro-FTIR spectroscopy revealed a decrease in the CH2/CH3 ratio with increasing maturity, indicating Tasmanites aliphatic chains become shorter and more branched. Oxygenated functional groups decreased relative to aliphatic stretching bands and increased aromaticity was noted at the highest maturities. In samples that were pyrolyzed for 72h at temperatures of 300–320°C (BR: 0.56–0.68%Ro), Tasmanites showed similar trends, whereas at pyrolysis temperatures of 340°C and higher (BR>1.0%Ro), Tasmanites was pseudomorphed by accumulations of solid bitumen, carbonate and sulfide. Replacement of Tasmanites by these phases in hydrous pyrolysis experiments ≥340°C and its absence at higher maturities (peak oil, VR and BR≥0.9%Ro) in naturally matured samples, as documented in a previous study, implies that a large fraction of the algaenan component of original organic carbon is converted to petroleum during thermal maturation. XPS analysis indicated the molar proportion of aliphatic carbon increases with increasing thermal maturity, accompanied by decreases in oxygenated functional groups and olefinic carbon. EPMA of Tasmanites showed highest concentrations of S, with concentrations of redox-sensitive trace elements U, Mo, Ni and V generally at or below detection limits. Decrease in organic S with increasing thermal maturity may be related to cleavage of Tasmanites at CS linkages; however, this relationship was inconsistent and presence of adjacent or entrained nanoscale silicate or sulfide phases may impact measured trace element concentrations. Fluorescence microscopy and spectroscopy showed a red shift in spectral maxima and decreased emission intensities with increasing maturity, interpreted as due to non-radiative energy loss possibly because of increased aromaticity. Collectively, these results provide new insights into the in situ chemical transformations that accompany petrographic changes as oil-prone kerogen converts to petroleum with thermal advance from immature conditions into the mid-oil window.

Geological characteristics and gas potential analysis of the Biluocuo oil shale in the southern Qiangtang Basin, China

ABSTRACTShale gas exploration in the Qinghai–Tibet area has lagged behind as compared to the other regions of China, and no shale gas reservoir has been discovered till yet. The analysis of the geological and reservoir characteristics of the Biluocuo oil shale samples from the southern Qiangtang Basin indicates the following findings. The oil shale has a high organic matter content, and the average mass fraction of organic carbon is 4.62%. Additionally, the organic matter is type II. The thermal evolution of organic matter has reached from a low to a high mature stage, and the porosity and permeability are 1.25% and 0.0102 mD, respectively. The rocks are highly brittle, and the primary mineral components are calcite and quartz, whose average contents are 58% and 22%, respectively. Moreover, the rock has a high adsorption capacity. Furthermore, a comparison with the five major shale gas systems in North America found the following. The Biluocuo oil shale is similar to the Barnett shale and Ohio shale, particularly to the Barnett shale. This comprehensive analysis indicates that the Biluocuo oil shale has considerable gas potential and is a key formation for shale gas exploration in the Qinghai–Tibet area.

Protosalvinia revisited, new evidence for a land plant affinity

The Upper Devonian Protosalvinia phytoclasts from Ohio Shale and its host rock were analyzed using GC/MS, GC-ir/MS, in situ FTIR and pyrolysis–GC/MS, in order to determine its chemical composition and to discuss the taxonomic position of this enigmatic fossil. Based on molecular ratios, the maturity of the organic matter present in the phytoclasts and rocks is comparable to a bituminous rank coal. Diagenetic products of Chlorobiaceae carotenoids were observed in the hosting rocks of Protosalvinia, indicating that anoxia prevailed during the sedimentary deposition. The soluble organic matter of phytoclasts shows land-derived biomarkers including long chain n-alkanes with a slight odd/even predominance and bicyclic sesquiterpenes with eudesmane skeletons. The carbon isotopic composition of n-alkanes is consistent with a land plant origin. The macromolecular fraction of Protosalvinia consists of a condensed aromatic network. The pyrolysis products of the phytoclasts show polycyclic aromatic hydrocarbons commonly observed in coals, including naphthalenes, phenanthrenes and dibenzofurans. Based on what is known about the thermal evolution of organic matter, these components could derive from demethylation and condensation of phenylpropanoids or polysaccharides present in the original structure of Protosalvinia. The former components are exclusively metabolized by land plants.

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 λmax 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 λmax and Tmax for this maturation series was observed and λmax 600nm corresponds to Tmax of 440°C. Nevertheless if a larger set of Devonian samples is included, the correlation is polynomial with a jump in λmax ranging from 540 to 570nm. Up to 440°C of Tmax, the λmax, mostly, reaches up to 500nm; beyond a Tmax of 440°C, λmax is in the range of 580–600nm. This relationship places the “red shift” when the onset of the oil window is reached at Tmax of 440°C. Moreover, the correlation between HI and λmax (r2=0.70) shows a striking inflection and decrease in HI above a λmax of 600nm, coincident with the approximate onset of hydrocarbon generation in these rocks.

The contested landscape of unconventional energy development: a report from Ohio's shale gas country

Portions of Ohio are experiencing a surge in the development of unconventional sources of natural gas and other fossil fuels using controversial hydraulic fracturing technologies. Natural gas has been celebrated as a clean-burning bridge fuel capable of leading our society beyond its dependence on fossil fuels, a key to energy independence, and a critical catalyst for regional economic recovery. But serious concerns have been raised about possible detrimental impacts on public health and safety, water and air quality, and environmental integrity. Informed by a landscape studies perspective that encourages careful consideration of how people conceive of the world around them, this paper examines how Ohioans' understandings of the environment are being transformed as a result of shale gas extraction. Based on ongoing participant–observation research and open-ended interviews with grassroots anti-fracking activists, nonprofit organization affiliates, and government agents as well as a review of publicly available corporate responsibility statements, it surveys emergent themes in citizens' perspectives—including legacy, way of life, disempowerment, vulnerability, displacement, and prosperity—in order to explore what the contested landscape of unconventional energy development can reveal about the diverse and dynamic ways in which contemporary citizens comprehend the natural environment and their relationships to it. It suggests that responses to energy development are being contoured not only by culturally constituted ways of imagining ideal human–environment interactions but also by the broader sociopolitical structures that ultimately determine whose perspectives are prioritized and which policies are implemented.