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Geology of the Devonian black shales of the Appalachian basin

Black shales of Devonian age in the Appalachian basin are a unique rock sequence. The high content of organic matter, which imparts the characteristic lithology, has for years attracted considerable interest in the shales as a possible source of energy. Concurrent with periodic and varied economic exploitations of the black shales are geologic studies. The recent energy shortage prompted the U.S. Department of Energy through the Eastern Gas Shales Project of the Morgantown Energy Technology Center to underwrite a research program to determine the geologic, geochemical, and structural characteristics of the Devonian black shales in order to enhance the recovery of gas from the shales. Geologic studies produced a regional stratigraphic network that correlates the 15-foot sequence in Tennessee with 3,000 feet of interbedded black and gray shales in central New York. The classic Devonian black-shale sequence in New York has been correlated with the Ohio Shale of Ohio and Kentucky and the Chattanooga Shale of Tennessee and southwestern Virginia. Biostratigraphic and lithostratigraphic markers in conjunction with gamma-ray logs facilitated long range correlations within the Appalachian basin and provided a basis for correlations with the black shales of the Illinois and Michigan basins. Areal distribution of selected shale units along with paleocurrent studies, clay mineralogy, and geochemistry suggests variations in the sediment source and transport directions. Current structures, faunal evidence, lithologic variations, and geochemical studies provide evidence to support interpretation of depositional environments. In addition, organic geochemical data combined with stratigraphic and structural characteristics of the shale within the basin allow an evaluation of the resource potential of natural gas in the Devonian shale sequence.

Conference Paper

Geology of the Devonian black shales of the Appalachian Basin

Black shales of Devonian age in the Appalachian Basin are a unique rock sequence. The high content of organic matter, which imparts the characteristic lithology, has for years attracted considerable interest in the shales as a possible source of energy. The recent energy shortage prompted the U.S. Department of Energy through the Eastern Gas Shales Project of the Morgantown Energy Technology Center to underwrite a research program to determine the geologic, geochemical, and structural characteristics of the Devonian black shales in order to enhance the recovery of gas from the shales. Geologic studies by Federal and State agencies and academic institutions produced a regional stratigraphic network that correlates the 15 ft black shale sequence in Tennessee with 3000 ft of interbedded black and gray shales in central New York. These studies correlate the classic Devonian black shale sequence in New York with the Ohio Shale of Ohio and Kentucky and the Chattanooga Shale of Tennessee and southwestern Virginia. Biostratigraphic and lithostratigraphic markers in conjunction with gamma-ray logs facilitated long-range correlations within the Appalachian Basin. Basinwide correlations, including the subsurface rocks, provided a basis for determining the areal distribution and thickness of the important black shale units. The organic carbon content of the dark shales generally increases from east to west across the basin and is sufficient to qualify as a hydrocarbon source rock. Significant structural features that involve the black shale and their hydrocarbon potential are the Rome trough, Kentucky River and Irvine-Paint Creek fault zone, and regional decollements and ramp zones.

Kentucky, Maryland, New York, Ohio, Pennsylvania,

Observed source parameters for dynamic rupture with non-uniform initial stressand relatively high fracture energy

We have conducted dynamic rupture propagation experiments to establish the relations between in-source stress drop, fracture energy and the resulting particle velocity during slip of an unconfined 2 m long laboratory fault at normal stresses between 4 and 8 MPa. To produce high fracture energy in the source we use a rough fault that has a large slip weakening distance. An artifact of the high fracture energy is that the nucleation zone is large such that precursory slip reduces fault strength over a large fraction of the total fault length prior to dynamic rupture, making the initial stress non-uniform. Shear stress, particle velocity, fault slip and acceleration were recorded coseismically at multiple locations along strike and at small fault-normal distances. Stress drop increases weakly with normal stress. Average slip rate depends linearly on the fault strength loss and on static stress drop, both with a nonzero intercept. A minimum fracture energy of 1.8 J/m 2 and a linear slip weakening distance of 33 μm are inferred from the intercept. The large slip weakening distance also affects the average slip rate which is reduced by in-source energy dissipation from on-fault fracture energy. Because of the low normal stress and small per event slip (∼86 μm), no thermal weakening such as melting or pore fluid pressurization occurs in these experiments. Despite the relatively high fracture energy, and the very low heat production, energy partitioning during these laboratory earthquakes is very similar to typical earthquake source properties. The product of fracture energy and fault area is larger than the radiated energy. Seismic efficiency is low at ∼2%. The ratio of apparent stress to static stress drop is ∼27%, consistent with measured overshoot. The fracture efficiency is ∼33%. The static and dynamic stress drops when extrapolated to crustal stresses are 2–7.3 MPa and in the range of typical earthquake stress drops. As the relatively high fracture energy reduces the slip velocities in these experiments, the extrapolated average particle velocities for crustal stresses are 0.18–0.6 m/s. That these experiments are consistent with typical earthquake source properties suggests, albeit indirectly, that thermal weakening mechanisms such as thermal pressurization and melting which lead to near complete stress drops, dominate earthquake source properties only for exceptional events unless crustal stresses are low.

Journal of Structural Geology

Characterization of fly ash from low-sulfur and high-sulfur coal sources: Partitioning of carbon and trace elements with particle size

Fly ash samples were collected in November and December of 1994, from generating units at a Kentucky power station using high- and low-sulfur feed coals. The samples are part of a two-year study of the coal and coal combustion byproducts from the power station. The ashes were wet screened at 100, 200, 325, and 500 mesh (150, 75, 42, and 25 mu m, respectively). The size fractions were then dried, weighed, split for petrographic and chemical analysis, and analyzed for ash yield and carbon content. The low-sulfur ''heavy side'' and ''light side'' ashes each have a similar size distribution in the November samples. In contrast, the December fly ashes showed the trend observed in later months, the light-side ash being finer (over 20 % more ash in the 500 mesh [25 mu m] fraction) than the heavy-side ash. Carbon tended to be concentrated in the coarse fractions in the December samples. The dominance of the 325 mesh (42 mum) fractions in the overall size analysis implies, though, that carbon in the fine sizes may be an important consideration in the utilization of the fly ash. Element partitioning follows several patterns. Volatile elements, such as Zn and As, are enriched in the finer sizes, particularly in fly ashes collected at cooler, light-side electrostatic precipitator (ESP) temperatures. The latter trend is a function of precipitation at the cooler-ESP temperatures and of increasing concentration with the increased surface area of the finest fraction. Mercury concentrations are higher in high-carbon fly ashes, suggesting Hg adsorption on the fly ash carbon. Ni and Cr are associated, in part, with the spinel minerals in the fly ash.

Energy Sources

Contrasting past and current numbers of bears visiting Yellowstone cutthroat trout streams

Spawning cutthroat trout ( Oncorhynchus clarkii bouvieri ) were historically abundant within tributary streams of Yellowstone Lake within Yellowstone National Park and were a highly digestible source of energy and protein for Yellowstone’s grizzly bears ( Ursus arctos ) and black bears ( U. americanus ). The cutthroat trout population has subsequently declined since the introduction of non-native lake trout (Salvelinus namaycush), and in response to effects of drought and whirling disease ( Myxobolus cerebralis ). The trout population, duration of spawning runs, and indices of bear use of spawning streams had declined in some regions of the lake by 1997–2000. We initiated a 3-year study in 2007 to assess whether numbers of spawning fish, black bears, and grizzly bears within and alongside stream corridors had changed since 1997– 2000. We estimated numbers of grizzly bears and black bears by first compiling encounter histories of individual bears visiting 48 hair-snag sites along 35 historically fished streams.We analyzed DNA encounter histories with Pradel-recruitment and Jolly-Seber (POPAN) capture-mark-recapture models. When compared to 1997–2000, the current number of spawning cutthroat trout per stream and the number of streams with cutthroat trout has decreased. We estimated that 48 (95% CI¼42–56) male and 23 (95% CI¼21–27) female grizzly bears visited the historically fished tributary streams during our study. In any 1- year, 46 to 59 independent grizzly bears (8–10% of estimated Greater Yellowstone Ecosystem population) visited these streams. When compared with estimates from the 1997 to 2000 study and adjusted for equal effort, the number of grizzly bears using the stream corridors decreased by 63%. Additionally, the number of black bears decreased between 64% and 84%. We also document an increased proportion of bears of both species visiting front-country (i.e., near human development) streams. With the recovery of cutthroat trout, we suggest bears that still reside within the Lake basin will readily use this high-quality food resource.

Journal of Wildlife Management

Synchrotron radiation determination of elemental concentrations in coal

The variations with depth of the elemental concentrations in vitrinites in a series of vitrites have been determined using radiation from the Cornell high energy synchrotron source. All of the vitrites were selected from a single drill core sample of coal from the Emery coalfield, Utah. The results are compared with similar determinations using the Heidelberg proton microprobe. The advantages and disadvantages of the two techniques are discussed. Results are reported for S, Ca, Ti, Fe, Zn, Br, and Sr. For example, it is found that Fe increases from top to bottom of the coal bed in contrast to S, which decreases from top to bottom of the bed. Other features of the two data sets are also described. ?? 1984.

Nuclear Instruments and Methods in Physics Researc

Lotic freshwater: Rivers

Ecosystems associated with rivers are intricately connected to their entire watershed. The river ecosystem includes the channel of active water flow, floodplain, and riparian and hyporheic zones. This ecosystem is shaped by interactions among the natural flow of water, sediments within the river and entering the river, and large wood regimes within the riparian zone. River integrity describes the ability of a river ecosystem to adjust to changes in these elements and through these adjustments maintain the habitat, disturbance regime, and connectivity necessary to sustain native biotic communities. Riverine food webs conceptualize the coupling between the physical environment and biotic communities and can be used to examine recovery from disturbance, variation in the structure of communities, and sources of energy that fuel metabolism within the ecosystem.

Book chapter

Microbial and chemical factors influencing methane production in laboratory incubations of low-rank subsurface coals

Lignite and subbituminous coals were investigated for their ability to support microbial methane production in laboratory incubations. Results show that naturally-occurring microorganisms associated with the coals produced substantial quantities of methane, although the factors influencing this process were variable among different samples tested. Methanogenic microbes in two coals from the Powder River Basin, Wyoming, USA, produced 140.5-374.6 mL CH 4 /kg ((4.5-12.0 standard cubic feet (scf)/ton) in response to an amendment of H 2 /CO 2 . The addition of high concentrations (5-10 mM) of acetate did not support substantive methane production under the laboratory conditions. However, acetate accumulated in control incubations where methanogenesis was inhibited, indicating that acetate was produced and consumed during the course of methane production. Acetogenesis from H 2 /CO 2 was evident in these incubations and may serve as a competing metabolic mode influencing the cumulative amount of methane produced in coal. Two low-rank (lignite A) coals from Fort Yukon, Alaska, USA, demonstrated a comparable level of methane production (131.1-284.0 mL CH4/kg (4.2-9.1 scf/ton)) in the presence of an inorganic nutrient amendment, indicating that the source of energy and organic carbon was derived from the coal. The concentration of chloroform-extractable organic matter varied by almost three orders of magnitude among all the coals tested, and appeared to be related to methane production potential. These results indicate that substrate availability within the coal matrix and competition between different groups of microorganisms are two factors that may exert a profound influence on methanogenesis in subsurface coal beds.

International Journal of Coal Geology

Morphological and chemical evidence of stromatolitic deposits in the 2.75 Ga Carajás banded iron formation, Brazil

We describe evidence of biogenicity in the morphology and carbon content of well-preserved, Neoarchean samples of banded iron formation (BIF) from Carajás, Brazil. Silica-rich BIF layers contain translucent ellipsoidal or trapezoidal structures (∼5–10 μm diameter) composed of silica, hematite, and kerogen, which are arranged in larger ring-like forms (rosettes). Stable carbon isotope analysis yields a δ 13 C value of −24.5‰ indicating that the contained carbon is likely biogenic. Raman and SEM analyses, as well as wavelength-dispersive X-ray elemental maps, show kerogen inside the rosette forms. Within the iron-rich BIF layers, tubular structures (0.5–5 μm) were observed between hematite granules and blades. Kerogen and kaolinite are present in these structures. Both the rosettes and the tubular structures resemble morphologies that are characteristic of some bacterial species. We hypothesize that the Carajás BIFs originated as biomats formed by one or more species that over time produced large stromatolitic structures. The rosettes and the tubular structures, associated with chert-rich and iron-rich BIF layers, respectively, may represent two different species, or perhaps, two phases of a bacterium life cycle. For example, some modern myxobacteria exhibit similar morphologies in their resting and vegetative stages. Fe(III) precipitation may have occurred by contact of Fe(II) with bacterial slime, leading to oxidation by chemical reactions with exposed polysaccharide hydroxyl and carboxyl groups. The Fe(III) would then have been available for use as a source of energy in a dissimilatory iron reduction type of metabolism. Organic carbon input presumably came from primary producers (not necessarily aerobic) within the local water column, perhaps in shallow-water communities. Alternatively, the carbon may have originated by Fischer–Tropsch synthesis at ocean hydrothermal vents. The observed lateral continuity of BIF layers may perhaps be explained by chemical signaling by the bacteria of favorable or unfavorable environmental conditions, leading to nearly synchronous cell morphogenesis from a vegetative to resting phase and vice versa.

Earth and Planetary Science Letters

Constraints on the composition and thermal structure of Ariel’s icy crust as inferred from its largest observed impact crater

The large graben-like troughs and smooth plains visible on the surface of Ariel are indicative of a period of high heat flow in the Uranian moon's past. High heat flows on icy moons like Ariel can also enable viscous flow that removes impact crater topography, a process called viscous relaxation. Here we use numerical modeling to investigate the conditions necessary to viscously relax Ariel's largest impact crater, Yangoor, which is 80 km in diameter and unusually shallow. If we assume that Ariel's crust consists of non-porous water ice, heat fluxes ≥60 mW m −2 are required to reduce an initially deep Yangoor-like crater to its current observed depth. Lower fluxes are required if a high-porosity (30%), low-conductivity surface layer several kilometers thick is assumed to exist, but in any case, fluxes in excess of 30 mW m −2 are necessary to substantially reduce Yangoor's topography. The inclusion of ammonia dihydrate has a negligible effect on our results despite decreasing the viscosity of Ariel's deep ice. Our results are consistent with previous inferences of high heat fluxes on Ariel, but exceed both expected radiogenic heat fluxes and known equilibrium tidal heat fluxes by an order of magnitude. If Yangoor's shallow depth is the result of tidal heating, then short-lived non-equilibrium tidal dissipation or some other source of energy is required. Notably, although our results do not require the presence of an ocean within Ariel, the thermal conditions necessary to viscously relax Yangoor also imply a relatively thin ice shell (∼10-km thick) if conductive heat transport is assumed.

Icarus

Kinetic study on clogging of a geothermal pumping well triggered by mixing-induced biogeochemical reactions

The sustainability of ground-source geothermal systems can be severely impacted by microbially mediated clogging processes. Biofouling of water wells by hydrous ferric oxide is a widespread problem. Although the mechanisms and critical environmental factors associated with clogging development are widely recognized, effects of mixing processes within the wells and time scales for clogging processes are not well characterized. Here we report insights from a joint hydrological, geochemical, and metagenomics characterization of a geothermal doublet in which hydrous ferric oxide and hydrous manganese oxide deposits had formed as a consequence of mixing shallow groundwater containing dissolved oxygen and nitrate with deeper, anoxic groundwater containing dissolved iron (Fe II ) and manganese (Mn II ). Metagenomics identify distinct bacteria consortia in the pumping well oxic and anoxic zones, including autotrophic iron-oxidizing bacteria. Batch mixing experiments and geochemical kinetics modeling of the associated reactions indicate that Fe II and Mn II oxidation are slow compared to the residence time of water in the pumping well; however, adsorption of Fe II and Mn II by accumulated hydrous ferric oxide and hydrous manganese oxide in the well bore and pump riser provides “infinite” time for surface-catalyzed oxidation and a convenient source of energy for iron-oxidizing bacteria, which colonize the surfaces and also catalyze oxidation. Thus, rapid clogging is caused by mixing-induced redox reactions and is exacerbated by microbial activity on accumulated hydrous oxide surfaces.

Orleans

Geochemical evidence for a magmatic CO 2 degassing event at Mammoth Mountain, California, September-December 1997

Recent time series soil CO 2 concentration data from monitoring stations in the vicinity of Mammoth Mountain, California, reveal strong evidence for a magmatic degassing event during the fall of 1997 lasting more than 2 months. Two sensors at Horseshoe Lake first recorded the episode on September 23, 1997, followed 10 days later by a sensor on the north flank of Mammoth Mountain. Direct degassing from shallow intruding magma seems an implausible cause of the degassing event, since the gas released at Horseshoe Lake continued to be cold and barren of other magmatic gases, except for He. We suggest that an increase in compressional strain on the area south of Mammoth Mountain driven by movement of major fault blocks in Long Valley caldera may have triggered an episode of increased degassing by squeezing additional accumulated CO 2 from a shallow gas reservoir to the surface along faults and other structures where it could be detected by the CO 2 monitoring network. Recharge of the gas reservoir by CO 2 emanating from the deep intrusions that probably triggered deep long-period earthquakes may also have contributed to the degassing event. The nature of CO 2 discharge at the soil-air interface is influenced by the porous character of High Sierra soils and by meteorological processes. Solar insolation is the primary source of energy for the Earth atmosphere and plays a significant role in most diurnal processes at the Earth surface. Data from this study suggest that external forcing due largely to local orographic winds influences the fine structure of the recorded CO 2 signals.

California

Chemical and engineering properties of fired bricks containing 50 weight percent of class F fly ash

The generation of fly ash during coal combustion represents a considerable solid waste disposal problem in the state of Illinois and nationwide. In fact, the majority of the three million tons of fly ash produced from burning Illinois bituminous coals is disposed of in landfills. The purpose of this study was to obtain a preliminary assessment of the technical feasibility of mitigating this solid waste problem by making fired bricks with the large volume of fly ash generated from burning Illinois coals. Test bricks were produced by the extrusion method with increasing amounts (20-50% by weight) of fly ash as a replacement for conventional raw materials. The chemical characteristics and engineering properties of the test bricks produced with and without 50 wt% of fly ash substitutions were analyzed and compared. The properties of the test bricks containing fly ash were at least comparable to, if not better than, those of standard test bricks made without fly ash and met the commercial specifications for fired bricks. The positive results of this study suggest that further study on test bricks with fly ash substitutions of greater than 50wt% is warranted. Successful results could have an important impact in reducing the waste disposal problem related to class F fly ash while providing the brick industry with a new low cost raw material.

Energy Sources

Producing ammonium sulfate from flue gas desulfurization by-products

Emission control technologies using flue gas desulfurization (FGD) have been widely adopted by utilities burning high-sulfur fuels. However, these technologies require additional equipment, greater operating expenses, and increased costs for landfill disposal of the solid by-products produced. The financial burdens would be reduced if successful high-volume commercial applications of the FGD solid by-products were developed. In this study, the technical feasibility of producing ammonium sulfate from FGD residues by allowing it to react with ammonium carbonate in an aqueous solution was preliminarily assessed. Reaction temperatures of 60, 70, and 80??C and residence times of 4 and 6 hours were tested to determine the optimal conversion condition and final product evaluations. High yields (up to 83%) of ammonium sulfate with up to 99% purity were achieved under relatively mild conditions. The optimal conversion condition was observed at 60??C and a 4-hour residence time. The results of this study indicate the technical feasibility of producing ammonium sulfate fertilizer from an FGD by-product. Copyright ?? Taylor & Francis Inc.

Energy Sources

Nature of migrabitumen and their relation to regional thermal maturity, Ouachita Mountains, Oklahoma

Two grahamite and three impsonite localities are within an 82-km-long segment of the Ouachita Mountains of southeastern Oklahoma. Grab samples were collected to study the petrographic and geochemical characteristics of the migrabitumen at the grahamite-impsonite transition and the relation of the migrabitumen to the regional thermal maturity pattern. Maximum and random bitumen reflectance values increased from 0·75 to 1·80% from west to east, consistent with the regional thermal maturation trend. Mean bireflectance values increased from 0·04 to 0·38%. The two grahamite samples are classified at the grahamite-impsonite boundary with conflicting petrographic (bitumen reflectance) and bulk chemical (volatile matter) maturity indicators. The regional maturation trend, based on vitrinite reflectance and bitumen reflectance values, was confirmed by a detailed geochemical investigation of bitumen extracts. Although biomarker analyses were influenced by extensive biodegradation effects, molecular parameters based on the phenanthrenes, dibenzothiophenes, and tricyclic terpanes were identified as useful maturity indicators.

Oklahoma

Arctic insect emergence timing and composition differs across thaw ponds of varying morphology

Freshwater ponds provide habitats for aquatic insects that emerge and subsidize consumers in terrestrial ecosystems. In the Arctic, insects provide an important seasonal source of energy to birds that breed and rear young on the tundra. The abundance and timing of insect emergence from arctic thaw ponds is poorly understood, but understanding these fluxes is important, given the role of insects in food webs and current rates of environmental change at high latitudes. We aimed to evaluate emerging insect communities from thaw ponds with different morphologies, identify environmental covariates influencing insect composition, and describe temporal changes in insect abundance. We collected environmental information and insects that emerged over two growing seasons and examined the phenology and taxonomic composition of insects arising from different pond classes: low centered polygon, small coalescent, large coalescent, and trough ponds. Our findings indicated no differences in the timing of total emergence across ponds of varying morphology. Community dissimilarity was primarily associated with center or margin habitat and variables that differed strongly among pond classes. These insects, which provide important provisions for various species of birds, are likely to experience changes in emergence phenology and composition due to ongoing, rapid warming in the region.

Alaska

Volcanic origin of the eruptive plumes on Io

A quadruple long exposure of Io in eclipse exhibits faint auroral emission from the eruptive plumes. No luminous spots in the vents, predicted by Gold, were observed. Heat from the interior of Io appears to be the predominant source of energy in the plumes.

Science

Thickness and consolidation of deep-sea sediments: A discussion

Hamilton (1959) concluded that in most sediments excess pore-water pressure is equal to zero - that is, the hydrostatic pressure is at atmospheric pressure. This note points out that in terrestrial environments the occurrence of artesian water (excess pore-water pressure) is commonplace and widespread and that such excess pressure is the source of energy for flowing water wells and for many flowing oil wells, "gushers," or "blowouts".

Bulletin of the Geological Society of America