Formation resistivity as an indicator of oil generation in black shales

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hester, T.C.; Schmoker, J.W.

1987-08-01

Black, organic-rich shales of Late Devonian-Early Mississippi age are present in many basins of the North American craton and, where mature, have significant economic importance as hydrocarbon source rocks. Examples drawn from the upper and lower shale members of the Bakken Formation, Williston basin, North Dakota, and the Woodford Shale, Anadarko basin, Oklahoma, demonstrate the utility of formation resistivity as a direct in-situ indicator of oil generation in black shales. With the onset of oil generation, nonconductive hydrocarbons begin to replace conductive pore water, and the resistivity of a given black-shale interval increases from low levels associated with thermal immaturitymore » to values approaching infinity. Crossplots of a thermal-maturity index (R/sub 0/ or TTI) versus formation resistivity define two populations representing immature shales and shales that have generated oil. A resistivity of 35 ohm-m marks the boundary between immature and mature source rocks for each of the three shales studied. Thermal maturity-resistivity crossplots make possible a straightforward determination of thermal maturity at the onset of oil generation, and are sufficiently precise to detect subtle differences in source-rock properties. For example, the threshold of oil generation in the upper Bakken shale occurs at R/sub 0/ = 0.43-0.45% (TTI = 10-12). The threshold increases to R/sub 0/ = 0.48-0.51% (TTI = 20-26) in the lower Bakken shale, and to R/sub 0/ = 0.56-0.57% (TTI = 33-48) in the most resistive Woodford interval.« less

Deposition of sedimentary organic matter in black shale facies indicated by the geochemistry and petrography of high-resolution samples, blake nose, western North Atlantic

USGS Publications Warehouse

Barker, C.E.; Pawlewicz, M.; Cobabe, E.A.

2001-01-01

A transect of three holes drilled across the Blake Nose, western North Atlantic Ocean, retrieved cores of black shale facies related to the Albian Oceanic Anoxic Events (OAE) lb and ld. Sedimentary organic matter (SOM) recovered from Ocean Drilling Program Hole 1049A from the eastern end of the transect showed that before black shale facies deposition organic matter preservation was a Type III-IV SOM. Petrography reveals that this SOM is composed mostly of degraded algal debris, amorphous SOM and a minor component of Type III-IV terrestrial SOM, mostly detroinertinite. When black shale facies deposition commenced, the geochemical character of the SOM changed from a relatively oxygen-rich Type III-IV to relatively hydrogen-rich Type II. Petrography, biomarker and organic carbon isotopic data indicate marine and terrestrial SOM sources that do not appear to change during the transition from light-grey calcareous ooze to the black shale facies. Black shale subfacies layers alternate from laminated to homogeneous. Some of the laminated and the poorly laminated to homogeneous layers are organic carbon and hydrogen rich as well, suggesting that at least two SOM depositional processes are influencing the black shale facies. The laminated beds reflect deposition in a low sedimentation rate (6m Ma-1) environment with SOM derived mostly from gravity settling from the overlying water into sometimes dysoxic bottom water. The source of this high hydrogen content SOM is problematic because before black shale deposition, the marine SOM supplied to the site is geochemically a Type III-IV. A clue to the source of the H-rich SOM may be the interlayering of relatively homogeneous ooze layers that have a widely variable SOM content and quality. These relatively thick, sometimes subtly graded, sediment layers are thought to be deposited from a Type II SOM-enriched sediment suspension generated by turbidities or direct turbidite deposition.

Preliminary Results from Outcrop-Based Spectral Gamma-Ray Measurements on the Lower Silurian Longmaxi Shale, in Chongqing and Its Adjacent Areas

NASA Astrophysics Data System (ADS)

Zou, C.; Nie, X.; Qiao, L.; Pan, L.; Hou, S.

2013-12-01

The Longmaxi Shale in the Lower Silurian has been recognized as a favorable target of shale gas exploration in Sichuan basin, China. One important feature of shale gas reservoirs is of high total organic carbon (TOC). Many studies have shown that the spectral gamma-ray measurements are positively correlated to the TOC contents. In this study, the spectral gamma ray responses of five shale outcrop profiles are measured in Chongqing and its adjacent areas, Sichuan basin. Three of the five profiles are located in Qijiang, Qianjiang and Changning in Chongqing, and the other two are located in Qilong and Houtan in Guizhou. The main lithologies of the profiles include mainly black shale, gray shale and silty shale. The spectral gamma-ray measurements provide the contents of potassium (K), uranium (U), and thorium (Th). The result of the five profiles shows that the K and Th contents of gray shale are close to the ones of black shale, while the U contents in the black shale are significantly higher than that in the other rocks. The TOC contents are estimated by using the outcrop-based measurements with an empirical formula. The result shows that the TOC contents are the highest in black shale of Changning profile. It indicates that there is a most promising exploration potential for shale gas in this area. In the future, the outcrop data will be used to construct detailed lithofacies profiles and establish relationships between lithofacies both in outcrop and the subsurface gamma-ray logs. Acknowledgment: We acknowledge the financial support of the National Natural Science Foundation of China (41274185) and the Fundamental Research Funds for the Central Universities.

Irradiation of organic matter by uranium decay in the Alum Shale, Sweden

NASA Astrophysics Data System (ADS)

Lewan, M. D.; Buchardt, B.

1989-06-01

The Alum Shale of Sweden contains black shales with anomalously high uranium concentrations in excess of 100 ppm. Syngenetic or early diagenetic origin of this uranium indicates that organic matter within these shales has been irradiated by decaying uranium for approximately 500 Ma. Radiation-induced polymerization of alkanes through a free-radical cross-linking mechanism appears to be responsible for major alterations within the irradiated organic matter. Specific radiation-induced alterations include generation of condensate-like oils at reduced yields from hydrous pyrolysis experiments, decrease in atomic H/C ratios of kerogens, decrease in bitumen/organic-carbon ratios, and a relative increase in low-molecular weight triaromatic steroid hydrocarbons. Conversely, stable carbon isotopes of kerogens, reflectance of vitrinite-like macerais, oil-generation kinetics, and isomerization of 20R to 20S αα C 29-steranes were not affected by radiation. The radiation dosage needed to cause the alterations observed in the Alum Shale has been estimated to be in excess of 10 5 Mrads with respect to organic carbon. This value is used to estimate the potential for radiation damage to thermally immature organic matter in black shales through the geological rock record. High potential for radiation damage is not likely in Cenozoic and Mesozoic black shales but becomes more likely in lower Paleozoic and Precambrian black shales.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Negus-De Wys, J.; Dixon, J. M.; Evans, M. A.

This document consists of the following papers: inorganic geochemistry studies of the Eastern Kentucky Gas Field; lithology studies of upper Devonian well cuttings in the Eastern Kentucky Gas Field; possible effects of plate tectonics on the Appalachian Devonian black shale production in eastern Kentucky; preliminary depositional model for upper Devonian Huron age organic black shale in the Eastern Kentucky Gas Field; the anatomy of a large Devonian black shale gas field; the Cottageville (Mount Alto) Gas Field, Jackson County, West Virginia: a case study of Devonian shale gas production; the Eastern Kentucky Gas Field: a geological study of the relationshipsmore » of Ohio Shale gas occurrences to structure, stratigraphy, lithology, and inorganic geochemical parameters; and a statistical analysis of geochemical data for the Eastern Kentucky Gas Field.« less

Activity concentrations of 238U and 226Ra in two European black shales and their experimentally-derived leachates.

PubMed

Wilke, Franziska D H; Schettler, Georg; Vieth-Hillebrand, Andrea; Kühn, Michael; Rothe, Heike

2018-05-18

The production of gas from unconventional resources became an important position in the world energy economics. In 2012, the European Commission's Joint Research Centre estimate 16 trillion cubic meters (Tcm) of technically recoverable shale gas in Europe. Taking into account that the exploitation of unconventional gas can be accompanied by serious health risks due to the release of toxic chemical components and natural occurring radionuclides into the return flow water and their near-surface accumulation in secondary precipitates, we investigated the release of U, Th and Ra from black shales by interaction with drilling fluids containing additives that are commonly employed for shale gas exploitation. We performed leaching tests at elevated temperatures and pressures with an Alum black shale from Bornholm, Denmark and a Posidonia black shale from Lower Saxony, Germany. The Alum shale is a carbonate free black shale with pyrite and barite, containing 74.4 μg/g U. The Posidonia shales is a calcareous shale with pyrite but without detectable amounts of barite containing 3.6 μg/g U. Pyrite oxidized during the tests forming sulfuric acid which lowered the pH on values between 2 and 3 of the extraction fluid from the Alum shale favoring a release of U from the Alum shale to the fluid during the short-term and in the beginning of the long-term experiments. The activity concentration of 238 U is as high as 23.9 mBq/ml in the fluid for those experiments. The release of U and Th into the fluid is almost independent of pressure. The amount of uranium in the European shales is similar to that of the Marcellus Shale in the United States but the daughter product of 238 U, the 226 Ra activity concentrations in the experimentally derived leachates from the European shales are quite low in comparison to that found in industrially derived flowback fluids from the Marcellus shale. This difference could mainly be due to missing Cl in the reaction fluid used in our experiments and a lower fluid to solid ratio in the industrial plays than in the experiments due to subsequent fracking and minute cracks from which Ra can easily be released. Copyright © 2018 Elsevier Ltd. All rights reserved.

Comparison of organic geochemistry and metal enrichment in two black shales: Cambrian Alum Shale of Sweden and Devonian Chattanooga Shale of United States

USGS Publications Warehouse

Leventhal, J.S.

1991-01-01

In most black shales, such as the Chattanooga Shale and related shales of the eastern interior United States, increased metal and metalloid contents are generally related to increased organic carbon content, decreased sedimentation rate, organic matter type, or position in the basin. In areas where the stratigraphic equivalents of the Chattanooga Shale are deeply buried and and the organic material is thermally mature, metal contents are essentially the same as in unheated areas and correlate with organic C or S contents. This paradigm does not hold for the Cambrian Alum Shale Formation of Sweden where increased metal content does not necessarily correlate with organic matter content nor is metal enrichment necessarily related to land derived humic material because this organic matter is all of marine source. In southcentral Sweden the elements U, Mo, V, Ni, Zn, Cd and Pb are all enriched relative to average black shales but only U and Mo correlate to organic matter content. Tectonically disturbed and metamorphosed allochthonous samples of Alum Shale on the Caledonian front in western Sweden have even higher amounts for some metals (V, Ni, Zn and Ba) relative to the autochthonous shales in this area and those in southern Sweden. ?? 1991 Springer-Verlag.

Rhenium and osmium isotopes in black shales and Ni-Mo-PGE-rich sulfide layers, Yukon Territory, Canada, and Hunan and Guizhou provinces, China

USGS Publications Warehouse

Horan, M.F.; Morgan, J.W.; Grauch, R.I.; Coveney, R.M.; Murowchick, J.B.; Hulbert, L.J.

1994-01-01

Rhenium and osmium abundances and osmium isotopic compositions were determined by negative thermal ionization mass spectrometry for samples of Devonian black shale and an associated Ni-enriched sulfide layer from the Yukon Territory, Canada. The same composition information was also obtained for samples of early Cambrian Ni-Mo-rich sulfide layers hosted in black shale in Guizhou and Hunan provinces, China. This study was undertaken to constrain the origin of the PGE enrichment in the sulfide layers. Samples of the Ni sulfide layer from the Yukon Territory are highly enriched in Re, Os, and other PGE, with distinctly higher Re/192Os but similar Pt/Re, compared to the black shale host. Re-Os isotopic data of the black shale and the sulfide layer are approximately isochronous, and the data plot close to reference isochrons which bracket the depositional age of the enclosing shales. Samples of the Chinese sulfide layers are also highly enriched in Re, Os, and the other PGE. Re/192Os are lower than in the Yukon sulfide layer. Re-Os isotopic data for the sulfide layers lie near a reference isochron with an age of 560 Ma, similar to the depositional age of the black shale host. The osmium isotopic data suggest that Re and PGE enrichment of the brecciated sulfide layers in both the Yukon Territory and in southern China may have occurred near the time of sediment deposition or during early diagenesis, during the middle to late Devonian and early Cambrian, respectively. ?? 1994.

The provenance of low-calcic black shales

NASA Astrophysics Data System (ADS)

Quinby-Hunt, M. S.; Wilde, P.

1991-04-01

The elemental concentration of sedimentary rocks depends on the varying reactivity of each element as it goes from the source through weathering, deposition, diagenesis, lithification, and even low rank metamorphism. However, non-reactive components of detrital particles ideally are characteristic of the original igneous source and thus are useful in provenance studies. To determine the source of detrital granitic and volcanic components of low-calcic (<1% CaCO3) marine black shales, the concentrations of apparently non-reactive (i.e. unaffected by diagenetic, redox and/or low-rank metamorphic processes) trace elements were examined using standard trace element discrimination diagrams developed for igneous rocks. The chemical data was obtained by neutron activation analyses of about 200 stratigraphically well-documented black shale samples from the Cambrian through the Jurassic. A La-Th-Sc ternary diagram distinguishes among contributions from the upper and bulk continental crust and the oceanic crust (Taylor and McLennan 1985). All the low-calcic black shales cluster within the region of the upper crust. Th-Hf-Co ternary diagrams also are commonly used to distinguish among the upper and bulk continental crust and the oceanic crust (Taylor and McLennan 1985). As Co is redox sensitive in black shale environments, it was necessary to substitute an immobile element (i.e. example Rb) in the diagram. With this substitution of black shales all cluster in the region of the upper continental crust. To determine the provenance of the granitic component (Pearce et al. 1984), plots of Ta vs Yb and Rb vs Yb + Ta shows a cluster at the junction of the boundaries separating the volcanic arc granite (VAG), syn-collision granite (syn-COLG), and within-plate granite (WPG) fields. The majority fall within the VAG field. There are no occurrences of ocean ridge granite (ORG). The minimal contribution of basalts to marine black shales is confirmed by the ternary Wood diagram Th-Hf/3-Ta (Wood et al. 1979). The black shales plot in a cluster in a high Th region outside the various basalt fields, which suggests contribution from the continental crust.

Self-cementing properties of oil shale solid heat carrier retorting residue.

PubMed

Talviste, Peeter; Sedman, Annette; Mõtlep, Riho; Kirsimäe, Kalle

2013-06-01

Oil shale-type organic-rich sedimentary rocks can be pyrolysed to produce shale oil. The pyrolysis of oil shale using solid heat carrier (SHC) technology is accompanied by large amount of environmentally hazardous solid residue-black ash-which needs to be properly landfilled. Usage of oil shale is growing worldwide, and the employment of large SHC retorts increases the amount of black ash type of waste, but little is known about its physical and chemical properties. The objectives of this research were to study the composition and self-cementing properties of black ash by simulating different disposal strategies in order to find the most appropriate landfilling method. Three disposal methods were simulated in laboratory experiment: hydraulic disposal with and without grain size separation, and dry dumping of moist residue. Black ash exhibited good self-cementing properties with maximum compressive strength values of >6 MPa after 90 days. About 80% of strength was gained in 30 days. However, the coarse fraction (>125 µm) did not exhibit any cementation, thus the hydraulic disposal with grain size separation should be avoided. The study showed that self-cementing properties of black ash are governed by the hydration of secondary calcium silicates (e.g. belite), calcite and hydrocalumite.

The carpenter fork bed, a new - and older - Black-shale unit at the base of the New Albany shale in central Kentucky: Characterization and significance

USGS Publications Warehouse

Barnett, S.F.; Ettensohn, F.R.; Norby, R.D.

1996-01-01

Black shales previously interpreted to be Late Devonian cave-fill or slide deposits are shown to be much older Middle Devonian black shales only preserved locally in Middle Devonian grabens and structural lows in central Kentucky. This newly recognized - and older -black-shale unit occurs at the base of the New Albany Shale and is named the Carpenter Fork Bed of the Portwood Member of the New Albany Shale after its only known exposure on Carpenter Fork in Boyle County, central Kentucky; two other occurrences are known from core holes in east-central Kentucky. Based on stratigraphic position and conodont biostratigraphy, the unit is Middle Devonian (Givetian: probably Middle to Upper P. varcus Zone) in age and occurs at a position represented by an unconformity atop the Middle Devonian Boyle Dolostone and its equivalents elsewhere on the outcrop belt. Based on its presence as isolated clasts in the overlying Duffin Bed of the Portwood Member, the former distribution of the unit was probably much more widespread - perhaps occurring throughout western parts of the Rome trough. Carpenter Fork black shales apparently represent an episode of subsidence or sea-level rise coincident with inception of the third tectophase of the Acadian orogeny. Deposition, however, was soon interrupted by reactivation of several fault zones in central Kentucky, perhaps in response to bulge migration accompanying start of the tectophase. As a result, much of central Kentucky was uplifted and tilted, and the Carpenter Fork Bed was largely eroded from the top of the Boyle, except in a few structural lows like the Carpenter Fork graben where a nearly complete record of Middle to early Late Devonian deposition is preserved.

Uranium in the Upper Cambrian black shale of Sweden

USGS Publications Warehouse

McKelvey, Vincent Ellis

1955-01-01

The Peltura zone of the Upper Cambrian black shales of Sweden contains about 0.02 percent uranium. Maximum amounts are present in rocks deposited in an embayment in the sea and in rocks in or closely adjacent to that part of the vertical sequence that contains maximum amounts of distillable oil, total organic matter, pyrite, and a black highly uraniferous kerogen called "kolm". Available data suggest that the precipitation of uranium is favored by a low redox potential and that the uranium in the shale matrix may be in fine-grained kolm.

Investigating Rare Earth Element Systematics in the Marcellus Shale

NASA Astrophysics Data System (ADS)

Yang, J.; Torres, M. E.; Kim, J. H.; Verba, C.

2014-12-01

The lanthanide series of elements (the 14 rare earth elements, REEs) have similar chemical properties and respond to different chemical and physical processes in the natural environment by developing unique patterns in their concentration distribution when normalized to an average shale REE content. The interpretation of the REE content in a gas-bearing black shale deposited in a marine environment must therefore take into account the paleoredox conditions of deposition as well as any diagenetic remobilization and authigenic mineral formation. We analyzed 15 samples from a core of the Marcellus Shale (Whipkey ST1, Greene Co., PA) for REEs, TOC, gas-producing potential, trace metal content, and carbon isotopes of organic matter in order to determine the REE systematics of a black shale currently undergoing shale gas development. We also conducted a series of sequential leaching experiments targeting the phosphatic fractions in order to evaluate the dominant host phase of REEs in a black shale. Knowledge of the REE system in the Marcellus black shale will allow us to evaluate potential REE release and behavior during hydraulic fracturing operations. Total REE content of the Whipkey ST1 core ranged from 65-185 μg/g and we observed three distinct REE shale-normalized patterns: middle-REE enrichment (MREE/MREE* ~2) with heavy-REE enrichment (HREE/LREE ~1.8-2), flat patterns, and a linear enrichment towards the heavy-REE (HREE/LREE ~1.5-2.5). The MREE enrichment occurred in the high carbonate samples of the Stafford Member overlying the Marcellus Formation. The HREE enrichment occurred in the Union Springs Member of the Marcellus Formation, corresponding to a high TOC peak (TOC ~4.6-6.2 wt%) and moderate carbonate levels (CaCO3 ~4-53 wt%). Results from the sequential leaching experiments suggest that the dominant host of the REEs is the organic fraction of the black shale and that the detrital and authigenic fractions have characteristic MREE enrichments. We present our conclusions on the impact of depositional setting and diagenetic remobilization and authigenic mineral formation on the REE system in the Marcellus Shale.

Thorium/U systematics of Precambrian deep-sea pelagic balck shales: implications for redox state of the early atmosphere

NASA Astrophysics Data System (ADS)

Jia, Y.; McCulloch, M.; Charlotte, A.

2003-12-01

To address the question of the redox state of the Precambrian atmosphere-hydrosphere system via sediments requires measurement of redox sensitive trace elements, and inter-element ratios, in deep water black shales with a chemical sedimentary "hydrogenic" component. This approach is endorsed by recent progress in research of redox-sensitive trace metals records in late Proterozoic and Phanerozoic sedimentary rocks, which has provided important clues to how the redox state of depositional environments has changed over time. Many conventional studies, in contrast, have been on first cycle volcanogenic turbidites with a minimal hydrogenic input (Taylor and McLennan, 1995). Accordingly, we have analyzed the redox-sensitive, trace element compositions of the 2.1 Ga black shales in Birimian Blet, West Africa, and the 2.7 Ga Archean counterparts in Timmins, Canada, Tati Belt, Botswana, and Kanowna District, Western Australia. These pyrite-bearing black shales, which were originally argillaceous sediments containing organic matter and low in thermal maturity, were primarily deposited in the deep-sea pelagic environments. Th/U ratios are lower in the Proterozoic shales (0.38-0.82, average 0.67), and Archean shales (0.47-3.65, average 2.43) relative to "conventional" Archean upper crust (3.8), PAAS (4.7), or average upper continental crust (3.8). Calculated U concentrations from hydrogenic component are between 0.90 and 2.45 in the Proterozoic shales, and range from 0.06 to 0.96 for the Archean black shales. Given the conservative behavior of Th in the sedimentary cycle, variably low Th/U ratios in these Precambrian black shales signify that U6+, soluble in oxidized surface waters, was reduced to insoluble U4+ in reducing bottom waters, as in the contemporary Black Sea. The results are consistent with a locally to globally oxidized atmosphere-shallow hydrosphere pre-2.0 Ga. Taylor, S.R., and McLennan, S.C., 1995. The geochemical evolution of the continental crust: Reviews of Geophysics, v. 33. p. 241-265.

Isotopically Light Organic Carbon in Phanerozoic Black Shales: Diagenetic, Source, or Environmental Signal?

NASA Astrophysics Data System (ADS)

Meyers, P. A.

2011-12-01

A curious depletion of 13C in the organic matter of marine black shales has been widely recognized ever since the advent of carbon isotope measurements half a century ago. Paleozoic and Mesozoic black shales commonly have del13C values between -29 and -26 permil, whereas modern marine organic matter has values between -22 and -18 permil. The black shale values mimic those of continental organic matter, yet sedimentary settings and Rock-Eval results indicate that the organic matter is marine in origin. This presentation will overview and discuss hypotheses to explain the isotopically light values of the black shales. First, the preferential removal of isotopically heavier organic matter components such as carbohydrates by diagenesis will be examined and shown to be wanting. Second, the possible oxidation of isotopically light methane released from clathrates that would have altered the DIC pool available to phytoplankton will be considered and also be found unlikely. A third possibility - that greater concentrations of CO2 in the greenhouse atmospheres that corresponded with deposition of many black shales allowed greater discrimination against 13C during photosynthesis - will be evaluated from del13C values of bulk carbon and of algal and land-plant biomarker molecules. Finally, the possibility that stronger stratification of the surface ocean may have magnified photic zone recycling of organic matter and reincorporation of its isotopically light carbon into fresh biomass will be considered. Although the fourth possibility is contrary to the conditions of vertical mixing of nutrients that exist in modern upwelling systems and that are responsible for their high productivity, it is consistent with the strongly stratified conditions that accompanied the high productivity that produced the Pliocene-Pleistocene sapropels of the Mediterranean Sea. Because the sapropels and most Phanerozic black shales share del15N values near 0 permil, nitrogen fixation evidently was important to most of these carbon-rich sequences, implying that well-developed surface stratification was central to their formation. On this basis, the 13C-depletion common to most Phanerozoic black shales is evidence of periods of high productivity over large areas of poorly mixed ancient oceans and constitutes an isotopic signal and an environmental scenario very different to what is known in the modern ocean.

Late Devonian shale deposition based on known and predicted occurrence of Foerstia in Michigan basin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matthews, R.D.

The fossil Foerstia (Protosalvinia) marks a time zone within Late Devonian shale sequences in the eastern US. Its recent discovery in Michigan has led to more accurate correlations among the three large eastern basins. Subdivisions of the Devonian-Mississippi shale sequence in Michigan based on gamma-ray correlations reveal an idealized black shale geometry common to other eastern black shales, such as the Sunbury of Michigan and Ohio, the Clegg Creek of Indiana, the Dunkirk of Pennsylvania and New York, and the lower Huron of Ohio and West Virginia. In Michigan, Foerstia occurs at a stratigraphic position postulated to mark a majormore » change in depositional conditions and source areas. This position strengthens the physical and paleontologic evidence for a formal division of the Antrim. Isopach maps of the shale sequence above and below Foerstia show a relatively uniform and continuous black shale deposit (units 1A, 1B, and 1C) below Foerstia. This deposit is unlike the wedge of sediment found above Foerstia, which is composed of a western facies (Ellsworth) and an eastern facies (upper Antrim) that should be combined in a single stratigraphic unit conforming to Forgotson's concept of a format.« less

Gold and platinum in shales with evidence against extraterrestrial sources of metals

USGS Publications Warehouse

Coveney, R.M.; Murowchick, J.B.; Grauch, R.I.; Glascock, M.D.; Denison, J.R.

1992-01-01

Few black shales contain concentrations of precious metals higher than average continental crust (i.e. ???5 ppb Au). Yet Au and Pt alloys have been reported from the Kupferschiefer in Poland. Moreover, thin sulfide beds in certain Chinese and Canadian shales contain several hundred ppb Au, Pd and Pt and average ???4% Mo and ???2.5% Ni in an association that is difficult to explain. Volcanic and non-volcanic exhalations, hydrothermal epigenesis involving either igneous or sedex fluids, biogenic processes and low-temperature secondary enrichment are among the possible factors involved in deriving Ni, PGE and Au for black shales and sulfide beds in black shales. Extraterrestrial sources have been invoked in some cases (e.g., the Cambrian of China). However, available data on abundances of PGE indicate relatively low values for Ir (<0.02-2 ppb) in comparison with amounts for other PGE (up to 700 ppb Pt and 1255 ppb Pd). These data and high contents for Mo are not consistent with extraterrestrial sources of metals for Chinese shales and Ni-Mo-sulfide beds. Data are less complete for the U.S. shales, but nevertheless are suggestive of earthly origins for PGE. ?? 1992.

Multiple Controls on the Paleoenvironment of the Early Cambrian Marine Black Shales in the Sichuan Basin, SW China: Geochemical and Organic Carbon Isotopic Evidence

NASA Astrophysics Data System (ADS)

Wang, S.; Zhang, G.; Dong, D.; Wang, Y.

2016-12-01

In order to understand the paleoenvironment of the Early Cambrian black shale deposition in the western part of the Yangtze Block, geochemical and organic carbon isotopic studies have been performed on two wells that have drilled through the Qiongzhusi Formation in the central and southeastern parts of Sichuan Basin. It shows that the lowest part of the Qiongzhusi Formation has high TOC abundance, while the middle and upper parts display relative low TOC content. Redox-sensitive element (Mo) and trace elemental redox indices (e.g., Ni/Co, V/Cr, U/Th and V/(V+Ni)) suggest that the high-TOC layers were deposited under anoxic conditions, whereas the low-TOC layers under relatively dysoxic/oxic conditions. The relationship of the enrichment factors of Mo and U further shows a transition from suboxic low-TOC layers to euxinic high-TOC layers. On the basis of the Mo-TOC relationship, the Qiongzhusi Formation black shales were deposited in a basin under moderately restricted conditions. Organic carbon isotopes display temporal variations in the Qiongzhusi Formation, with a positive excursion of δ13Corg values in the lower part and a continuous positive shift in the middle and upper parts. All these geochemical and isotopic criteria indicate a paleoenvironmental change from bottom anoxic to middle and upper dysoxic/oxic conditions for the Qiongzhusi Formation black shales. The correlation of organic carbon isotopic data for the Lower Cambrian black shales in different regions of the Yangtze Block shows consistent positive excursion of δ13Corg values in the lower part for each section. This excursion can be ascribed to the widespread Early Cambrian transgression in the Yangtze Block, under which black shales were deposited.

The hyper-enrichment of V and Zn in black shales of the Late Devonian-Early Mississippian Bakken Formation (USA)

USGS Publications Warehouse

Scott, Clinton T.; Slack, John F.; Kelley, Karen Duttweiler

2017-01-01

Black shales of the Late Devonian to Early Mississippian Bakken Formation are characterized by high concentrations of organic carbon and the hyper-enrichment (> 500 to 1000s of mg/kg) of V and Zn. Deposition of black shales resulted from shallow seafloor depths that promoted rapid development of euxinic conditions. Vanadium hyper-enrichments, which are unknown in modern environments, are likely the result of very high levels of dissolved H2S (~ 10 mM) in bottom waters or sediments. Because modern hyper-enrichments of Zn are documented only in Framvaren Fjord (Norway), it is likely that the biogeochemical trigger responsible for Zn hyper-enrichment in Framvaren Fjord was also present in the Bakken basin. With Framvaren Fjord as an analogue, we propose a causal link between the activity of phototrophic sulfide oxidizing bacteria, related to the development of photic-zone euxinia, and the hyper-enrichment of Zn in black shales of the Bakken Formation.

Paleoceanographic Inferences from Carbon and Nitrogen Isotopic Compositions of Cenomanian Black Shales from DSDP/ODP Sites 367, 530, 603, 641, 1257-1261, and 1276 in the Atlantic Ocean

NASA Astrophysics Data System (ADS)

Yum, J.; Meyers, P. A.; Bernasconi, S. M.; Arnaboldi, M.

2005-12-01

The mid-Cretaceous (Cenomanian- Turonian) was characterized as a peak global greenhouse period with highest sea level, highest CO2 concentration in atmosphere and low thermal gradients from the poles to the equator. The depositional environment of the organic-carbon-rich black shales that typify this period remains an open question. A total of 180 Cenomanian- Turonian core samples were selected from multiple ODP and DSDP sites in the Atlantic Ocean: 530 (Cape Basin), 603 (Hatteras Rise), 641 (Galicia Bank), 1257-1261 (Demerara Rise), 1276 (Newfoundland Basin). Total organic carbon and nitrogen concentrations and isotopic compositions were measured to investigate variations in the proto-Atlantic Ocean paleoceanographic conditions that contributed to the origin of the black shales for this period. These new data were combined with existing data from Sites 367 (Senegal Rise), 530, and 603. Both the black shales and the organic-carbon-poor background sediments (less than 1 percent) have carbon isotope values between -29 to -22 permil. The C/N ratios of the background sediments are low (less than 20) compared to those of the black shales (20-40). Nitrogen isotope values range from 0 to 4 permil in the background samples. All black shales have similarly low nitrogen isotope values that range between -4 to 0 permil. These exceptionally low values are inferred to reflect the productivity of blue green algae and cyanobacteria under strongly surface stratified oceanic conditions. Although carbon isotope and C/N values of black shales show almost similar patterns at each location, there are site-specific shifts in these data that could be related to the amount of continental run off and/or the effect of latitude. Our multi-site comparison suggests that specially stratified depositional environments that could produce and accumulate the abnormally high carbon concentrations in sediments occurred throughout the proto-Atlantic ocean during the mid-Cretaceous. However, regional factors affected the amount and origin of organic matter delivered to each location.

The Oxidative Metabolism of Fossil Hydrocarbons and Sulfide Minerals by the Lithobiontic Microbial Community Inhabiting Deep Subterrestrial Kupferschiefer Black Shale.

PubMed

Włodarczyk, Agnieszka; Lirski, Maciej; Fogtman, Anna; Koblowska, Marta; Bidziński, Grzegorz; Matlakowska, Renata

2018-01-01

Black shales are one of the largest reservoirs of fossil organic carbon and inorganic reduced sulfur on Earth. It is assumed that microorganisms play an important role in the transformations of these sedimentary rocks and contribute to the return of organic carbon and inorganic sulfur to the global geochemical cycles. An outcrop of deep subterrestrial ~256-million-year-old Kupferschiefer black shale was studied to define the metabolic processes of the deep biosphere important in transformations of organic carbon and inorganic reduced sulfur compounds. This outcrop was created during mining activity 12 years ago and since then it has been exposed to the activity of oxygen and microorganisms. The microbial processes were described based on metagenome and metaproteome studies as well as on the geochemistry of the rock. The microorganisms inhabiting the subterrestrial black shale were dominated by bacterial genera such as Pseudomonas, Limnobacter, Yonghaparkia, Thiobacillus, Bradyrhizobium , and Sulfuricaulis . This study on black shale was the first to detect archaea and fungi, represented by Nitrososphaera and Aspergillus genera, respectively. The enzymatic oxidation of fossil aliphatic and aromatic hydrocarbons was mediated mostly by chemoorganotrophic bacteria, but also by archaea and fungi. The dissimilative enzymatic oxidation of primary reduced sulfur compounds was performed by chemolithotrophic bacteria. The geochemical consequences of microbial activity were the oxidation and dehydrogenation of kerogen, as well as oxidation of sulfide minerals.

Selected annotated bibliography of the geology and occurrence of uranium-bearing marine black shales in the United States

USGS Publications Warehouse

Fix, Carolyn E.

1956-01-01

The bibliography consists of annotations or abstracts of selected reports that pertain to the geology and occurrence of uranium in marine black shales and their metamorphic equivalents in the United States. Only those reports that were available to the public prior to June 30, 1956, are included. Most of the reports may be consulted in the larger public, university, or scientific libraries. A few reports that have been released to the public in open file may be consulted at designated offices of the Geological Survey. An effort has been made to include only those references to shales whose uranium is believed to be of syngenetic origin and whose major source of radioactivity is uranium. Many general papers on the geology of uranium deposits refer to marine black shales, and some of these general papers have been included.

On the origin of a phosphate enriched interval in the Chattanooga Shale (Upper Devonian) of Tennessee-A combined sedimentologic, petrographic, and geochemical study

NASA Astrophysics Data System (ADS)

Li, Yifan; Schieber, Juergen

2015-11-01

The Devonian Chattanooga Shale contains an uppermost black shale interval with dispersed phosphate nodules. This interval extends from Tennessee to correlative strata in Kentucky, Indiana, and Ohio and represents a significant period of marine phosphate fixation during the Late Devonian of North America. It overlies black shales that lack phosphate nodules but otherwise look very similar in outcrop. The purpose of this study is to examine what sets these two shales apart and what this difference tells us about the sedimentary history of the uppermost Chattanooga Shale. In thin section, the lower black shales (PBS) show pyrite enriched laminae and compositional banding. The overlying phosphatic black shales (PhBS) are characterized by phosbioclasts, have a general banded to homogenized texture with reworked layers, and show well defined horizons of phosphate nodules that are reworked and transported. In the PhBS, up to 8000 particles of P-debris per cm2 occur in reworked beds, whereas the background black shale shows between 37-88 particles per cm2. In the PBS, the shale matrix contains between 8-16 phosphatic particles per cm2. The shale matrix in the PhBS contains 5.6% inertinite, whereas just 1% inertinite occurs in the PBS. The shale matrix in both units is characterized by flat REE patterns (shale-normalized), whereas Phosbioclast-rich layers in the PhBS show high concentrations of REEs and enrichment of MREEs. Negative Ce-anomalies are common to all samples, but are best developed in association with Phosbioclasts. Redox-sensitive elements (Co, U, Mo) are more strongly enriched in the PBS when compared to the PhBS. Trace elements associated with organic matter (Cu, Zn, Cd, Ni) show an inverse trend of enrichment. Deposited atop a sequence boundary that separates the two shale units, the PhBS unit represents a transgressive systems tract and probably was deposited in shallower water than the underlying PBS interval. The higher phosphate content in the PhBS is interpreted as the result of a combination of lower sedimentation rates with reworking/winnowing episodes. Three types of phosphatic beds that reflect different degrees of reworking intensity are observed. Strong negative Ce anomalies and abundant secondary marcasite formation in the PhBS suggests improved aeration of the water column, and improved downward diffusion of oxygen into the sediment. The associated oxidation of previously formed pyrite resulted in a lowering of pore water pH and forced dissolution of biogenic phosphate. Phosphate dissolution was followed by formation of secondary marcasite and phosphate. Repeated, episodic reworking caused repetitive cycles of phosphatic dissolution and reprecipitation, enriching MREEs in reprecipitated apatite. A generally "deeper" seated redox boundary favored P-remineralization within the sediment matrix, and multiple repeats of this process in combination with wave and current reworking at the seabed led to the formation of larger phosphatic aggregates and concentration of phosphate nodules in discrete horizons.

Empirically assessing the potential release of rare earth elements from black shale under simulated hydraulic fracturing conditions

DOE PAGES

Yang, Jon; Verba, Circe; Torres, Marta; ...

2018-02-01

Rare earth elements (REEs) are economically important to modern society and the rapid growth of technologies dependent on REEs has placed considerable economic pressure on their sourcing. This study addresses whether REEs could be released as a byproduct of natural gas extraction from a series of experiments that were designed to simulate hydraulic fracturing of black shale under various pressure (25 and 27.5 MPa) and temperature (50, 90, 130 °C) conditions. The dissolved REEs in the reacted fluids displayed no propensity for the REEs to be released from black shale under high pressure and temperature conditions, a result that ismore » consistent across the different types of fluids investigated. Overall, there was a net loss of REEs from the fluid. These changes in dissolved REEs were greatest at the moment the fluids first contacted the shale and before the high temperature and high pressure conditions were imposed, although the magnitude of these changes (10 -4 μg/g) were small compared to the magnitude of the total REE content present in the solid shale samples (10 2 μg/g). These results highlight the variability and complexity of hydraulic fracturing systems and indicate that REE may not serve as robust tracers for fracturing fluid-shale reactions. Additionally, the results suggest that significant quantities of REEs may not be byproducts of hydraulically fractured shales.« less

Empirically assessing the potential release of rare earth elements from black shale under simulated hydraulic fracturing conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Jon; Verba, Circe; Torres, Marta

Rare earth elements (REEs) are economically important to modern society and the rapid growth of technologies dependent on REEs has placed considerable economic pressure on their sourcing. This study addresses whether REEs could be released as a byproduct of natural gas extraction from a series of experiments that were designed to simulate hydraulic fracturing of black shale under various pressure (25 and 27.5 MPa) and temperature (50, 90, 130 °C) conditions. The dissolved REEs in the reacted fluids displayed no propensity for the REEs to be released from black shale under high pressure and temperature conditions, a result that ismore » consistent across the different types of fluids investigated. Overall, there was a net loss of REEs from the fluid. These changes in dissolved REEs were greatest at the moment the fluids first contacted the shale and before the high temperature and high pressure conditions were imposed, although the magnitude of these changes (10 -4 μg/g) were small compared to the magnitude of the total REE content present in the solid shale samples (10 2 μg/g). These results highlight the variability and complexity of hydraulic fracturing systems and indicate that REE may not serve as robust tracers for fracturing fluid-shale reactions. Additionally, the results suggest that significant quantities of REEs may not be byproducts of hydraulically fractured shales.« less

Hydrocarbon potential of Upper Devonian black shale, eastern Kentucky

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnston, I.M.; Frankie, W.T.; Moody, J.R.

The gas-producing Upper Devonian black shales of eastern Kentucky represent cycles of organic units alternating with less-organic units that were dominated by an influx of clastics from a northeastern source. This pattern of sedimentation is typical throughout the southern Appalachian basin in areas basinal to, yet still influenced by, the Catskill delta to the northwest. These black shales, which thin westward onto the Cincinnati arch, dip eastward into the Appalachian basin. To evaluate the future gas potential of Devonian shale, a data base has been compiled, consisting of specific geologic and engineering information from 5920 Devonian shale wells in Letcher,more » Knott, Floyd, Martin, and Pike Counties, Kentucky. The first successful gas completion in eastern Kentucky was drilled in Martin County in 1901. Comparison of initial open-flow potential (IP) and long-term production data for these wells demonstrates that higher IP values generally indicate wells of higher production potential. Areas of higher IP are aligned linearly, and these lineaments are interpreted to be related to fracture systems within the Devonian shale. These fractures may be basement influenced. Temperature log analyses indicate that the greatest number of natural gas shows occur in the lower Huron Member of the Ohio Shale. Using both the temperature log to indicate gas shows and the gamma-ray log to determine the producing unit is a workable method for selecting the interval for treatment.« less

Trace- and rare-earth element geochemistry and Pb-Pb dating of black shales and intercalated Ni-Mo-PGE-Au sulfide ores in Lower Cambrian strata, Yangtze Platform, South China

NASA Astrophysics Data System (ADS)

Jiang, Shao-Yong; Chen, Yong-Quan; Ling, Hong-Fei; Yang, Jing-Hong; Feng, Hong-Zhen; Ni, Pei

2006-08-01

The Lower Cambrian black shale sequence of the Niutitang Formation in the Yangtze Platform, South China, hosts an extreme metal-enriched sulfide ore bed that shows >10,000 times enrichment in Mo, Ni, Se, Re, Os, As, Hg, and Sb and >1,000 times enrichment in Ag, Au, Pt, and Pd, when compared to average upper continental crust. We report in this paper trace- and rare-earth-element concentrations and Pb-Pb isotope dating for the Ni-Mo-PGE-Au sulfide ores and their host black shales. Both the sulfide ores and their host black shales show similar trace-element distribution patterns with pronounced depletion in Th, Nb, Hf, Zr, and Ti, and extreme enrichment in U, Ni, Mo, and V compared to average upper crust. The high-field-strength elements, such as Zr, Hf, Nb, Ta, Sc, Th, rare-earth elements, Rb, and Ga, show significant inter-element correlations and may have been derived mainly from terrigenous sources. The redox sensitive elements, such as V, Ni, Mo, U, and Mn; base metals, such as Cu, Zn, and Pb; and Sr and Ba may have been derived from mixing of seawater and venting hydrothermal sources. The chondrite-normalized REE patterns, positive Eu and Y anomalies, and high Y/Ho ratios for the Ni-Mo-PGE-Au sulfide ores are also suggestive for their submarine hydrothermal-exhalative origin. A stepwise acid-leaching Pb-Pb isotope analytical technique has been employed for the Niutitang black shales and the Ni-Mo-PGE-Au sulfide ores, and two Pb-Pb isochron ages have been obtained for the black shales (531±24 Ma) and for the Ni-Mo-PGE-Au sulfide ores (521±54 Ma), respectively, which are identical and overlap within uncertainty, and are in good agreement with previously obtained ages for presumed age-equivalent strata.

Trace elements reconnaissance investigations in New Mexico and adjoining states in 1951

USGS Publications Warehouse

Bachman, George O.; Read, Charles B.

1952-01-01

In the summer and fall of 1951, a reconnaissance search was made in New Mexico and adjacent states for uranium in coal and carbonaceous shale, chiefly of Mesozoic age, and black marine shale of Paleozoic age. Tertiary volcanic rocks, considered to be a possible source for uranium in the coal and associated rocks, were examined where the volcanic rocks were near coal-bearing strata. Uranium in possibly commercial amounts was found at La Ventana Mesa, Sandoval County, New Mexico. Slightly uranifeous coal and carbonaceous shale were found near San Ysidro, Sandoval County, and on Beautiful Mountain, San Juan County, all in New Mexico, and at Keams Canyon, Navajo County, and near Tuba City, Coconino County, in Arizona. Except for La Ventana deposit, none appeared to be of economic importance at the time this report was written, but additional reconnaissance investigations have been underway this field season, in the area where the deposits occur. Marine black shale of Sevonian age was examined in Otero and Socorro Counties, New Mexico and Gila County, Arizona. Mississippian black shale in Socorro County and Pennsylvanian black shale in Taos County, New Mexico were also tested. Equivalent uranium content of samples of these shales did not exceed 0.004 percent. Rhyolitic tuff from the Mount Taylor region is slightly radioactive as is the Bandelier tuff in the Nacimiento region and in the Jemez Plateau. Volcanic rocks in plugs and dikes in the northern Chuska Mountains and to the north in New Mexico as well as in northeastern Arizona and southeastern Utah are slightly radioactive. Coal and carbonaceous rocks in the vicinity of these and similar intrusions are being examined.

How lithology and climate affect REE mobility and fractionation along a shale weathering transect of the Susquehanna Shale Hills Critical Zone Observatory

NASA Astrophysics Data System (ADS)

Ma, L.; Jin, L.; Dere, A. L.; White, T.; Mathur, R.; Brantley, S. L.

2012-12-01

Shale weathering is an important process in global elemental cycles. Accompanied by the transformation of bedrock into regolith, many elements including rare earth elements (REE) are mobilized primarily by chemical weathering in the Critical Zone. Then, REE are subsequently transported from the vadose zone to streams, with eventual deposition in the oceans. REE have been identified as crucial and strategic natural resources; and discovery of new REE deposits will be facilitated by understanding global REE cycles. At present, the mechanisms and environmental factors controlling release, transport, and deposition of REE - the sources and sinks - at Earth's surface remain unclear. Here, we present a systematic study of soils, stream sediments, stream waters, soil water and bedrock in six small watersheds that are developed on shale bedrock in the eastern USA to constrain the mobility and fractionation of REE during early stages of chemical weathering. The selected watersheds are part of the shale transect established by the Susquehanna Shale Hills Observatory (SSHO) and are well suited to investigate weathering on shales of different compositions or within different climate regimes but on the same shale unit. Our REE study from SSHO, a small gray shale watershed in central Pennsylvania, shows that up to 65% of the REE (relative to parent bedrock) is depleted in the acidic and organic-rich soils due to chemical leaching. Both weathering soil profiles and natural waters show a preferential removal of middle REE (MREE: Sm to Dy) relative to light REE (La to Nd) and heavy REE (Ho to Lu) during shale weathering, due to preferential release of MREE from a phosphate phase (rhabdophane). Strong positive Ce anomalies observed in the regolith and stream sediments point to the fractionation and preferential precipitation of Ce as compared to other REE, in the generally oxidizing conditions of the surface environments. One watershed developed on the Marcellus black shale in Pennsylvania allows comparison of behaviors of REE in the organic-rich vs. organic-poor end members under the same climate conditions. Our study shows that black shale bedrock has much higher REE contents compared to the Rose Hill gray shale. The presence of reactive phases such as organic matter, carbonates and sulfides in black shale and their alteration greatly enhance the release of REE and other metals to surface environments. This observation suggests that weathering of black shale is thus of particular importance in the global REE cycles, in addition to other heavy metals that impact the health of terrestrial and aquatic ecosystems. Finally, our ongoing investigation of four more gray shale watersheds in Virginia, Tennessee, Alabama, and Puerto Rico will allow for a comparison of shale weathering along a climosequence. Such a systematic study will evaluate the control of air temperature and precipitation on REE release from gray shale weathering in eastern USA.

A New Oceanic Anoxic Event 2 record from the Central North Atlantic at South East Newfoundland Ridge, IODP Expedition 342, Newfoundland Drifts

NASA Astrophysics Data System (ADS)

Junium, C. K.; Bornemann, A.; Bown, P. R.; Friedrich, O.; Moriya, K.; Kirtland Turner, S.; Whiteside, J. H.

2013-12-01

The recovery of Cretaceous, Cenomanian-Turonian black shales deposited during Oceanic Anoxic Event 2 (OAE 2) at Site U1407, South East Newfoundland Ridge (SENR), was an unexpected but fortuitous discovery that fills a gap in the pelagic Tethyan and North Atlantic geologic records. Drilling operations recovered the OAE sequence in all three holes drilled at Site U1407 defined initially on the basis of lithology and calcareous nannofossil biostratigraphy and confirmed by carbon isotope stratigraphy post-expedition. The SENR OAE 2 sequence is a classic chalk sequence punctuated by a prominent black band. Prior to OAE 2, greenish white pelagic carbonate is interrupted by thin, 2 to 5 cm thick organic-rich, gray calcareous clays. A sharp transition from greenish-white chalk to carbonate-poor sediments marks the occurrence of the organic carbon-rich black band. Within the black band are finely laminated to massive, pyritic black shales and laminated gray clays that are relatively organic carbon-lean, free of preserved benthic foraminifera and rich in radiolarians. Finely laminated greenish-gray marls overlay the black band and grade into approximately 1 meter of greenish white chalks with common 1cm chert layers and nodules. The remainder of the Turonian sequence is characterized by a notable transition to pink chalks. The thickness of the black band ranges from 15-40 cm between Holes A through C. The differences in the thickness of beds between Holes is due in part to drilling disturbances and mass wasting indicated by slump features in the overlying Turonian strata. Core scanning XRF and carbon isotopes can help resolve the nature of these differences and inform future sampling and study. Carbonate and organic carbon isotopes reveal that the δ13C excursion marking the initiation of OAE 2 is below the base of the black band. At U1407A the δ13C rise is immediately below (3 cm) the black shale, with δ13C maxima in the black band. At U1407C the initial δ13C rise is below the black shale by 60 cm, in the underlying chalk. The temporal transience of TOC-enrichment is typical of OAE 2 sequences, particularly in the Tethyan realm (Gubbio, Italy; Ferriby, UK; Tarfaya, Morocco; Wunsorf, Germany), but the mechanism is unknown. In many ways, Site U1407 bears the distinct characteristics of the Tethyan region. Prior to the OAE, there are several black and dark gray bands interbedded with carbonate-rich (>80 wt. %), greenish white chalks. The color progression of white to black to pink through the OAE at U1407 is similar to C-T boundary sequences from the Umbria-Marche basin of Italy. The greenish white to pink nannofossil chalks are reminiscent of the Scaglia Bianca/Rossa limestones that bound the Bonarelli horizon. Associated lithologies include the presence of radiolarian sands interbedded with the black shales and cherts. This stratigraphic progression is similar to the Italian sequences, but the δ13C stratigraphy indicates that the excursion leads black shale deposition and in this sense is more similar to shallow continental records from the UK, USA and mainland Europe. This new δ13C record can be used to correlate SENR with other OAE 2 sections, allowing us to better understand possible mechanisms for the temporal transience of the black shales and paleoceanographic change during OAE2.

Effects of acid-volatile sulfide on metal bioavailability and toxicity to midge (Chironomus tentans) larvae in black shale sediments

USGS Publications Warehouse

Ogendi, G.M.; Brumbaugh, W.G.; Hannigan, R.E.; Farris, J.L.

2007-01-01

Metal bioavailability and toxicity to aquatic organisms are greatly affected by variables such as pH, hardness, organic matter, and sediment acid-volatile sulfide (AVS). Sediment AVS, which reduces metal bioavailability and toxicity by binding and immobilizing metals as insoluble sulfides, has been studied intensely in recent years. Few studies, however, have determined the spatial variability of AVS and its interaction with simultaneously extracted metals (SEM) in sediments containing elevated concentrations of metals resulting from natural geochemical processes, such as weathering of black shales. We collected four sediment samples from each of four headwater bedrock streams in northcentral Arkansa (USA; three black shale-draining streams and one limestone-draining stream). We conducted 10-d acute whole-sediment toxicity tests using the midge Chironomus tentans and performed analyses for AVS, total metals, SEMs, and organic carbon. Most of the sediments from shale-draining streams had similar total metal and SEM concentrations but considerable differences in organic carbon and AVS. Zinc was the leading contributor to the SEM molar sum, averaging between 68 and 74%, whereas lead and cadmium contributed less than 3%. The AVS concentration was very low in all but two samples from one of the shale streams, and the sum of the SEM concentrations was in molar excess of AVS for all shale stream sediments. No significant differences in mean AVS concentrations between sediments collected from shale-draining or limestone-draining sites were noted (p > 0.05). Midge survival and growth in black shale-derived sediments were significantly less (p < 0.001) than that of limestone-derived sediments. On the whole, either SEM alone or SEM-AVS explained the total variation in midge survival and growth about equally well. However, survival and growth were significantly greater (p < 0.05) in the two sediment samples that contained measurable AVS compared with the two sediments from the same stream that contained negligible AVS. ?? 2007 SETAC.

Oil-source correlations between the Mississippian Heath Shales and the reservoired oils in the Pennsylvanian Tyler Sands, Montana

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cole, G.A.; Drozd, R.J.; Daniel, J.A.

The Mississippi Heath Formation exposed in Fergus County, central Montana, is comprised predominantly of nearshore, marine, black, calcareous shales and carbonates with minor anhydrite and coal beds. The black shales and limestones have been considered as sources for shale oil via Fischer Assay and pyrolysis analysis. These shales are potential source units for the oils reservoired in the overlying Pennsylvanian Tyler Formation sands located 50 mi (80 km) to the east of the Fergus County Heath sediment studied. Heath Formation rocks from core holes were selectively sampled in 2-ft increments and analyzed for their source rock characteristics. Analyses include percentmore » total organic carbon (%TOC), Rock-Eval pyrolysis, pyrolysis-gas chromatography, and characterization of the total soluble extracts using carbon isotopes and gas chromatography-mass Spectrometry. Results indicated that the Heath was an excellent potential source unit that contained oil-prone, organic-rich (maximum of 17.6% TOC), calcareous, black shale intervals. The Heath and Tyler formations also contained intervals dominated by gas-prone, organic-rich shales of terrestrial origin. Three oils from the Tyler Formation sands in Musselshell and Rosebud counties were characterized by similar methods as the extracts. The oils were normally mature, moderate API gravity, moderate sulfur, low asphaltene crudes. Oil to source correlations between the Heath shale extracts and the oils indicated the Heath was an excellent candidate source rock for the Tyler reservoired oils. Conclusions were based on excellent matches between the carbon isotopes of the oils and the kerogen-kerogen pyrolyzates, and from the biomarkers.« less

Thermal maturity and petroleum kitchen areas of Liassic Black Shales (Lower Jurassic) in the central Upper Rhine Graben, Germany

NASA Astrophysics Data System (ADS)

Böcker, Johannes; Littke, Ralf

2016-03-01

In the central Upper Rhine Graben (URG), several major oil fields have been sourced by Liassic Black Shales. In particular, the Posidonia Shale (Lias ɛ, Lower Toarcian) acts as excellent and most prominent source rock in the central URG. This study is the first comprehensive synthesis of Liassic maturity data in the URG area and SW Germany. The thermal maturity of the Liassic Black Shales has been analysed by vitrinite reflectance (VRr) measurements, which have been verified with T max and spore coloration index (SCI) data. In outcrops and shallow wells (<600 m), the Liassic Black Shales reached maturities equivalent to the very early or early oil window (ca. 0.50-0.60 % VRr). This maturity is found in Liassic outcrops and shallow wells in the entire URG area and surrounding Swabian Jura Mountains. Maximum temperatures of the Posidonia Shale before graben formation are in the order of 80-90 °C. These values were likely reached during Late Cretaceous times due to significant Upper Jurassic and minor Cretaceous deposition and influenced by higher heat flows of the beginning rift event at about 70 Ma. In this regard, the consistent regional maturity data (VRr, T max, SCI) of 0.5-0.6 % VRr for the Posidonia Shale close to surface suggest a major burial-controlled maturation before graben formation. These consistent maturity data for Liassic outcrops and shallow wells imply no significant oil generation and expulsion from the Posidonia Shale before formation of the URG. A detailed VRr map has been created using VRr values of 31 wells and outcrops with a structure map of the Posidonia Shale as reference map for a depth-dependent gridding operation. Highest maturity levels occur in the area of the Rastatt Trough (ca. 1.5 % VRr) and along the graben axis with partly very high VRr gradients (e.g. well Scheibenhardt 2). In these deep graben areas, the maximum temperatures which were reached during upper Oligocene to Miocene times greatly exceed those during the Cretaceous.

Distribution of naturally occurring radionuclides (U, Th) in Timahdit black shale (Morocco).

PubMed

Galindo, C; Mougin, L; Fakhi, S; Nourreddine, A; Lamghari, A; Hannache, H

2007-01-01

Attention has been focused recently on the use of Moroccan black oil shale as the raw material for production of a new type of adsorbent and its application to U and Th removal from contaminated wastewaters. The purpose of the present work is to provide a better understanding of the composition and structure of this shale and to determine its natural content in uranium and thorium. A black shale collected from Timahdit (Morocco) was analyzed by powder X-ray diffraction and SEM techniques. It was found that calcite, dolomite, quartz and clays constitute the main composition of the inorganic matrix. Pyrite crystals are also present. A selective leaching procedure, followed by radiochemical purification and alpha-counting, was performed to assess the distribution of naturally occurring radionuclides. Leaching results indicate that 238U, 235U, 234U, 232Th, 230Th and 228Th have multiple modes of occurrence in the shale. U is interpreted to have been concentrated under anaerobic conditions. An integrated isotopic approach showed the preferential mobilization of uranium carried by humic acids to carbonate and apatite phases. Th is partitioned between silicate minerals and pyrite.

Hydrothermal, biogenic, and seawater components in metalliferous black shales of the Brooks Range, Alaska: Synsedimentary metal enrichment in a carbonate ramp setting

USGS Publications Warehouse

Slack, John F.; Selby, David; Dumoulin, Julie A.

2015-01-01

Trace element and Os isotope data for Lisburne Group metalliferous black shales of Middle Mississippian (early Chesterian) age in the Brooks Range of northern Alaska suggest that metals were sourced chiefly from local seawater (including biogenic detritus) but also from externally derived hydrothermal fluids. These black shales are interbedded with phosphorites and limestones in sequences 3 to 35 m thick; deposition occurred mainly on a carbonate ramp during intermittent upwelling under varying redox conditions, from suboxic to anoxic to sulfidic. Deposition of the black shales at ~335 Ma was broadly contemporaneous with sulfide mineralization in the Red Dog and Drenchwater Zn-Pb-Ag deposits, which formed in a distal marginal basin.Relative to the composition of average black shale, the metalliferous black shales (n = 29) display large average enrichment factors (>10) for Zn (10.1), Cd (11.0), and Ag (20.1). Small enrichments (>2–<10) are shown by V, Cr, Ni, Cu, Mo, Pd, Pt, U, Se, Y, and all rare earth elements except Ce, Nd, and Sm. A detailed stratigraphic profile over 23 m in the Skimo Creek area (central Brooks Range) indicates that samples from at and near the top of the section, which accumulated during a period of major upwelling and is broadly correlative with the stratigraphic levels of the Red Dog and Drenchwater Zn-Pb-Ag deposits, have the highest Zn/TOC (total organic carbon), Cu/TOC, and Tl/TOC ratios for calculated marine fractions (no detrital component) of these three metals.Average authigenic (detrital-free) contents of Mo, V, U, Ni, Cu, Cd, Pb, Ge, Re, Se, As, Sb, Tl, Pd, and Au show enrichment factors of 4.3 × 103 to 1.2 × 106 relative to modern seawater. Such moderate enrichments, which are common in other metalliferous black shales, suggest wholly marine sources (seawater and biogenic material) for these metals, given similar trends for enrichment factors in organic-rich sediments of modern upwelling zones on the Namibian, Peruvian, and Chilean shelves. The largest enrichment factors for Zn and Ag are much higher (1.4 × 107 and 2.9 × 107, respectively), consistent with an appreciable hydrothermal component. Other metals such as Cu, Pb, and Tl that are concentrated in several black shale samples, and are locally abundant in the Red Dog and Drenchwater Zn-Pb-Ag deposits, may have a partly hydrothermal origin but this cannot be fully established with the available data. Enrichments in Cr (up to 7.8 × 106) are attributed to marine and not hydrothermal processes. The presence in some samples of large enrichments in Eu (up to 6.1 × 107) relative to modern seawater and of small positive Eu anomalies (Eu/Eu* up to 1.12) are considered unrelated to hydrothermal activity, instead being linked to early diagenetic processes within sulfidic pore fluids.Initial Os isotope ratios (187Os/188Os) calculated for a paleontologically based depositional age of 335 Ma reveal moderately unradiogenic values of 0.24 to 0.88 for four samples of metalliferous black shale. A proxy for the ratio of coeval early Chesterian seawater is provided by initial (187Os/188Os)335 Ma ratios of four unaltered black shales of the coeval Kuna Formation that average 1.08, nearly identical to the initial ratio of 1.06 for modern seawater. Evaluation of possible sources of unradiogenic Os in the metalliferous black shales suggests that the most likely source was mafic igneous rocks that were leached by externally derived hydrothermal fluids. This unradiogenic Os is interpreted to have been leached by deeply circulating hydrothermal fluids in the Kuna basin, followed by venting of the fluids into overlying seawater.We propose that metal-bearing hydrothermal fluids that formed Zn-Pb-Ag deposits such as Red Dog or Drenchwater vented into seawater in a marginal basin, were carried by upwelling currents onto the margins of a shallow-water carbonate platform, and were then deposited in organic-rich muds, together with seawater- and biogenically derived components, by syngenetic sedimentary processes. Metal concentration in the black shales was promoted by high biologic productivity, sorption onto organic matter, diffusion across redox boundaries, a low sedimentation rate, and availability of H2S in bottom waters and pore fluids.

The Eagle Ford Shale, Texas: an initial insight into Late Cretaceous organic-rich mudrock palaeoenvironments

NASA Astrophysics Data System (ADS)

Forshaw, Joline; Jarvis, Ian; Trabucho-Alexandre, João; Tocher, Bruce; Pearce, Martin

2014-05-01

The hypothesised reduction of oxygen within the oceans during the Cretaceous is believed to have led to extended intervals of regional anoxia in bottom waters, resulting in increased preservation of organic matter and the deposition of black shales. Episodes of more widespread anoxia, and even euxinia, in both bottom and surface waters are associated with widespread black shale deposition during Ocean Anoxic Events (OAEs). The most extensive Late Cretaceous OAE, which occurred ~ 94 Ma during Cenomanian-Turonian boundary times, and was particularly well developed in the proto-North Atlantic and Tethyan regions, lasted for around 500 kyr (OAE2). Although the causes of this and other events are still hotly debated, research is taking place internationally to produce a global picture of the causes and consequences of Cretaceous OAEs. Understanding OAEs will enable a better interpretation of the climate fluctuations that ensued, and their association with the widespread deposition of black shales, rising temperatures, increased pCO2, enhanced weathering, and increased nutrient fluxes. The Eagle Ford Formation, of Cenomanian - Turonian age, is a major shale gas play in SW and NE Texas, extending over an area of more than 45,000 km2. The formation, which consists predominantly of black shales (organic-rich calcareous mudstones), was deposited during an extended period of relative tectonic quiescence in the northern Gulf Coast of the Mexico Basin, bordered by reefs along the continental shelf. The area offers an opportunity to study the effects of OAE2 in an organic-rich shelf setting. The high degree of organic matter preservation in the formation has produced excellent oil and gas source rocks. Vast areas of petroleum-rich shales are now being exploited in the Southern States of the US for shale gas, and the Eagle Ford Shale is fast becoming one of the countries largest producers of gas, oil and condensate. The Eagle Ford Shale stratigraphy is complex and heterogeneous, making further study essential before these resources can be fully developed. Therefore, a thorough understanding of the subsurface sediments within a coherent stratigraphic framework is required before exploitation can be optimimised. Here, we present initial palynological data (dinoflagellate cyst abundance), in conjunction with geochemistry, from material obtained from the Maverick Basin in the southwestern area of Eagle Ford Shale deposition. Results are presented as part of a wider study of the Eagle Ford Shale, utilising both core and outcrop material, that is using dinoflagellate cysts and chemostratigraphy to develop an improved stratigraphic framework and to reconstruct depositional palaeoenvironments in the basin.

Shale Gas characteristics of Permian black shales (Ecca group, Eastern Cape, South Africa)

NASA Astrophysics Data System (ADS)

Geel, Claire; Booth, Peter; Schulz, Hans-Martin; Horsfield, Brian; de Wit, Maarten

2013-04-01

This study involves a comprehensive and detailed lithological, sedimentalogical, structural and geochemical description of the lower Ecca Group in the Eastern Cape, South Africa. The Ecca group hosts a ~ 245 million year old organic-rich black shale, which has recently been the focus of interest of petroleum companies worldwide. The shale was deposited under anoxic conditions in a setting which formed as a consequence of retro-arc foreland basin development related to the Cape Fold Belt. This sedimentary/tectonic environment provided the conditions for deeply buried black shales to reach maturity levels for development in the gas window. The investigation site is called the Greystone Area and is situated north of Wolwefontein en route to Jansenville. The area has outcrops of the Dwyka, the Ecca and the lower Beaufort Groups. The outcrops were mapped extensively and the data was used in conjunction with GIS software to produce a detailed geological map. North-south cross sections were drawn to give indication of bed thicknesses and formation depths. Using the field work, data two boreholes were accurately sited on the northern limb of a shallow easterly plunging syncline. The first borehole reached 100m and the second was drilled to 292m depth (100m percussion and 192m core). The second borehole was drilled 200m south of the first, to penetrate the formations at a greater depth and to avoid surface weathering. Fresh core from the upper Dwyka Group, the Prince Albert Formation, the Whitehill Formation, Collingham Formation and part of the Ripon Formation were successfully extracted and a detailed stratigraphic log has been drawn up. The core was sampled during extraction and the samples were immediately sent to the GFZ in Potsdam, Germany, for geochemical analyses. As suspected the black shales of the the Whitehill Formation are high in organic carbon and have an average TOC value of 4.5%, whereas the Prince Albert and Collingham Formation are below 1%. Tmax values and the evolution of organic material to bitumen characterise these sediments as overmature. The HI and OI results reveal that the Collingham and Whitehill sediments are type II kerogen and the Prince Albert is type III kerogen sediment. XRD data shows major rock forming minerals of the black shales to be quartz, illite, muscovite and chlorite with some plagioclase and large amounts of accessory pyrite. Average meso-and macro-porosity of these black shales is 1.5% and SEM images confirm that these sediments are tightly packed. The samples are highly affected by the Cape Fold Belt due to its location so far south and is unlikely to hold gas at this position, however this ongoing investigation will give greater insight to the gas potential of these black shales which are found more north of the region. At the GFZ open system pyrolyses and thermovaporization analyses are still underway.

Geochemistry of approximately 1.9 Ga sedimentary rocks from northeastern Labrador, Canada

NASA Technical Reports Server (NTRS)

Hayashi, K. I.; Fujisawa, H.; Holland, H. D.; Ohmoto, H.

1997-01-01

Fifty-eight rock chips from fifteen samples of sedimentary rocks from the Ramah Group (approximately 1.9 Ga) in northeastern Labrador, Canada, were analyzed for major and minor elements, including C and S, to elucidate weathering processes on the Earth's surface about 1.9 Ga ago. The samples come from the Rowsell Harbour, Reddick Bight, and Nullataktok Formations. Two rock series, graywackes-gray shales of the Rowsell Harbour, Reddick Bight and Nullataktok Formations, and black shales of the Nullataktok Formation, are distinguishable on the basis of lithology, mineralogy, and major and trace element chemistry. The black shales show lower concentrations than the graywackes-gray shales in TiO2 (0.3-0.7 wt% vs. 0.7-1.8 wt%), Al2O3 (9.5-20.1 wt% vs. 13.0-25.0 wt%), and sigma Fe (<1 wt% vs. 3.8-13.9 wt% as FeO). Contents of Zr, Th, U, Nb, Ce, Y, Rb, Y, Co, and Ni are also lower in the black shales. The source rocks for the Ramah Group sediments were probably Archean gneisses with compositions similar to those in Labrador and western Greenland. The major element chemistry of source rocks for the Ramah Group sedimentary rocks was estimated from the Al2O3/TiO2 ratios of the sedimentary rocks and the relationship between the major element contents (e.g., SiO2 wt%) and Al2O3/TiO2 ratios of the Archean gneisses. This approach is justified, because the Al/Ti ratios of shales generally retain their source rock values; however, the Zr/Al, Zr/Ti, and Cr/Ni ratios fractionate during the transport of sediments. The measured SiO2 contents of shales in the Ramah Group are generally higher than the estimated SiO2 contents of source rocks by approximately 5 wt%. This correction may also have to be applied when estimating average crustal compositions from shales. Two provenances were recognized for the Ramah Group sediments. Provenance I was comprised mostly of rocks of bimodal compositions, one with SiO2 contents approximately 45 wt% and the other approximately 65 wt%, and was the source for most sedimentary rocks of the Ramah Group, except for black shales of the Nullataktok Formation. The black shales were apparently derived from Provenance II that was comprised mostly of felsic rocks with SiO2 contents approximately 65 wt%. Comparing the compositions of the Ramah Group sedimentary rocks and their source rocks, we have recognized that several major elements, especially Ca and Mg, were lost almost entirely from the source rocks during weathering and sedimentation. Sodium and potassium were also leached almost entirely during the weathering of the source rocks. However, significant amounts of Na were added to the black shales and K to all the rock types during diagenesis and/or regional metamorphism. The intensity of weathering of source rocks for the Ramah Group sediments was much higher than that of typical Phanerozoic sediments, possibly because of a higher PCO2 in the Proterozoic atmosphere. Compared to the source rock values, the Fe3+/Ti ratios of many of the graywackes and gray shales of the Ramah Group are higher, the Fe2+/Ti ratios are lower, and the sigma Fe/Ti ratios are the same. Such characteristics of the Fe geochemistry indicate that these sedimentary rocks are comprised of soils formed by weathering of source rocks under an oxygen-rich atmosphere. The atmosphere about 1.9 Ga was, therefore, oxygen rich. Typical black shales of Phanerozoic age exhibit positive correlations between the organic C contents and the concentrations of S, U, and Mo, because these elements are enriched in oxygenated seawater and are removed from seawater by organic matter in sediments. However, such correlations are not found in the Ramah Group sediments. Black shales of the Ramah Group contain 1.7-2.8 wt% organic C, but are extremely depleted in sigma Fe (<1 wt% as FeO), S (<0.3 wt%), U (approximately l ppm), Mo (<5 ppm), Ni (<2 ppm), and Co (approximately 0 ppm). This lack of correlation, however, does not imply that the approximately 1.9 Ga atmosphere-ocean system was anoxic. Depletion of these elements from the Ramah Group sediments may have occurred during diagenesis.

The geological and microbiological controls on the enrichment of Se and Te in sedimentary rocks

NASA Astrophysics Data System (ADS)

Bullock, Liam; Parnell, John; Armstrong, Joseph; Boyce, Adrian; Perez, Magali

2017-04-01

Selenium (Se) and tellurium (Te) have become elements of high interest, mainly due to their photovoltaic and photoconductive properties, and can contaminate local soils and groundwater systems during mobilisation. Due to their economic and environmental significance, it is important to understand the processes that lead to Se- and Te-enrichment in sediments. The distribution of Se and Te in sedimentary environments is primarily a function of redox conditions, and may be transported and concentrated by the movement of reduced fluids through oxidised strata. Se and Te concentrations have been measured in a suite of late Neoproterozoic Gwna Group black shales (UK) and uranium red bed (roll-front) samples (USA). Due to the chemical affinity of Se and sulphur (S), variations in the S isotopic composition of pyrite have also been measured in order to provide insights into their origin. Scanning electron microscopy of pyrite in the black shales shows abundant inclusions of the lead selenide mineral clausthalite. The data for the black shale samples show marked enrichment in Te and Se relative to crustal mean and several hundreds of other samples processed through our laboratory. While Se levels in sulphidic black shales are typically below 5 ppm, the measured values of up to 116 ppm are remarkable. The Se enrichment in roll-fronts (up to 168 ppm) is restricted to a narrow band of alteration at the interface between the barren oxidised core, and the highly mineralised reduced nose of the front. Te is depleted in roll-fronts with respect to the continental crust and other geological settings and deposits. S isotope compositions for pyrite in both the black shales and roll-fronts are very light and indicate precipitation by microbial sulphate reduction, suggesting that Se was microbially sequestered. Results show that Gwna Group black shales and U.S roll-front deposits contain marked elemental enrichments (particularly Se content). In Gwna Group black shales, Se and Te were sequestered out of seawater into pyritic shales at a higher rate than into crusts. Se enrichment in roll-fronts relates to the initial mobilisation of trace elements in oxidised conditions, and later precipitation downgradient in reduced conditions. Results highlight the potential for sedimentary types of Se- and Te-bearing deposits. The enrichment of elements of high value for future technologies in sedimentary rocks deserve careful assessment for potential future resources, and should be monitored during exploration and mobilisation due to the potential contamination effects. This work forms part of the NERC-funded 'Security of Supply of Mineral Resources' project, which aims to detail the science needed to sustain the security of supply of strategic minerals in a changing environment.

Mesoarchean Banded Iron Formation sequences in Dixon Island-Cleaverville Formation, Pilbara Australia: Oxygenic signal from DXCL project

NASA Astrophysics Data System (ADS)

Kiyokawa, S.; Ito, T.; Ikehara, M.; Yamaguchi, K. E.; Naraoka, H.; Onoue, T.; Horie, K.; Sakamoto, R.; Aihara, Y.; Miki, T.

2013-12-01

The 3.2-3.1 Ga Dixon island-Cleaverville formations are well-preserved Banded Iron Formation (BIF) within hydrothermal oceanic sequence at oceanic island arc setting (Kiyokawa et al., 2002, 2006, 2012). The stratigraphy of the Dixon Island (3195+15Ma) -Cleaverville (3108+13Ma) formations shows the well preserved environmental condition at the Mesoarchean ocean floor. The stratigraphy of these formations are formed about volcano-sedimentary sequences with hydrothermal chert, black shale and banded iron formation to the top. Based on the scientific drilling of DXCL project at 2007 and 2011, detail lithology between BIF sequence was clearly understood. Four drilling holes had been done at coastal sites; the Dixon Island Formation is DX site (100m) and the Cleaverville Formation is CL2 (40m), CL1 (60m) and CL3 (200m) sites and from stratigraphic bottom to top. Coarsening and thickening upward black shale-BIF sequences are well preserved of the stratigraphy form the core samples. The Dixon Island Formation consists komatiite-rhyolite sequences with many hydrothermal veins and very fine laminated cherty rocks above them. The Cleaverville Formation contains black shale, fragments-bearing pyroclastic beds, white chert, greenish shale and BIF. The CL3 core, which drilled through BIF, shows siderite-chert beds above black shale identified before magnetite lamination bed. U-Pb SHRIMP data of the tuff in lower Dixon Island Formation is 3195+15 Ma and the pyroclastic sequence below the Cleaverville BIF is 3108+13 Ma. Sedimentation rate of these sequence is 2-8 cm/ 1000year. The hole section of the organic carbon rich black shales below BIF are similar amount of organic content and 13C isotope (around -30per mill). There are very weak sulfur MIF signal (less 0.2%) in these black shale sequence. Our result show that thick organic rich sediments may be triggered to form iron rich siderite and magnetite iron beds. The stratigraphy in this sequence quite resemble to other Iron formation (eg. Hamersley BIF). So we investigate that the Cleaverville iron formation, which is one of the best well known Mesoarchean iron formation, was already started cyanobacteria oxygen production system to used pre-syn iron sedimentation at anoxic oceanic condition.

The Devonian Marcellus Shale and Millboro Shale

USGS Publications Warehouse

Soeder, Daniel J.; Enomoto, Catherine B.; Chermak, John A.

2014-01-01

The recent development of unconventional oil and natural gas resources in the United States builds upon many decades of research, which included resource assessment and the development of well completion and extraction technology. The Eastern Gas Shales Project, funded by the U.S. Department of Energy in the 1980s, investigated the gas potential of organic-rich, Devonian black shales in the Appalachian, Michigan, and Illinois basins. One of these eastern shales is the Middle Devonian Marcellus Shale, which has been extensively developed for natural gas and natural gas liquids since 2007. The Marcellus is one of the basal units in a thick Devonian shale sedimentary sequence in the Appalachian basin. The Marcellus rests on the Onondaga Limestone throughout most of the basin, or on the time-equivalent Needmore Shale in the southeastern parts of the basin. Another basal unit, the Huntersville Chert, underlies the Marcellus in the southern part of the basin. The Devonian section is compressed to the south, and the Marcellus Shale, along with several overlying units, grades into the age-equivalent Millboro Shale in Virginia. The Marcellus-Millboro interval is far from a uniform slab of black rock. This field trip will examine a number of natural and engineered exposures in the vicinity of the West Virginia–Virginia state line, where participants will have the opportunity to view a variety of sedimentary facies within the shale itself, sedimentary structures, tectonic structures, fossils, overlying and underlying formations, volcaniclastic ash beds, and to view a basaltic intrusion.

Zooplankton fecal pellets link fossil fuel and phosphate deposits

USGS Publications Warehouse

Porter, K.G.; Robbins, E.I.

1981-01-01

Fossil zooplankton fecal pellets found in thinly bedded marine and lacustrine black shales associated with phosphate, oil, and coal deposits, link the deposition of organic matter and biologically associated minerals with planktonic ecosystems. The black shales were probably formed in the anoxic basins of coastal marine waters, inland seas, and rift valley lakes where high productivity was supported by runoff, upwelling, and outwelling. Copyright ?? 1981 AAAS.

Germanium and uranium in coalified wood bom upper Devonian black shale

USGS Publications Warehouse

Breger, I.A.; Schopf, J.M.

1955-01-01

Microscopic study of black, vitreous, carbonaceous material occurring in the Chattanooga shale in Tennessee and in the Cleveland member of the Ohio shale in Ohio has revealed coalified woody plant tissue. Some samples have shown sufficient detail to be identified with the genus Cauixylon. Similar material has been reported in the literature as "bituminous" or "asphaltic" stringers. Spectrographic analyses of the ash from the coalified wood have shown unusually high percentages of germanium, uranium, vanadium, and nickel. The inverse relationship between uranium and germanium in the ash and the ash content of various samples shows an association of these elements with the organic constituents of the coal. On the basis of geochemical considerations, it seems most probable that the wood or coalified wood was germanium-bearing at the time logs or woody fragmenta were floated into the basins of deposition of the Chattanooga shale and the Cleveland member of the Ohio shale. Once within the marine environment, the material probably absorbed uranium with the formation of organo-uranium compounds such as exist in coals. It is suggested that a more systematic search for germaniferous coals in the vicinity of the Chattanooga shale and the Cleveland member of the Ohio shale might be rewarding. ?? 1955.

Thermal maturity map of Devonian shale in the Illinois, Michigan, and Appalachian basins of North America

USGS Publications Warehouse

East, Joseph A.; Swezey, Christopher S.; Repetski, John E.; Hayba, Daniel O.

2012-01-01

Much of the oil and gas in the Illinois, Michigan, and Appalachian basins of eastern North America is thought to be derived from Devonian shale that is within these basins (for example, Milici and others, 2003; Swezey, 2002, 2008, 2009; Swezey and others, 2005, 2007). As the Devonian strata were buried by younger sediments, the Devonian shale was subjected to great temperature and pressure, and in some areas the shale crossed a thermal maturity threshold and began to generate oil. With increasing burial (increasing temperature and pressure), some of this oil-generating shale crossed another thermal maturity threshold and began to generate natural gas. Knowledge of the thermal maturity of the Devonian shale is therefore useful for predicting the occurrence and the spatial distribution of oil and gas within these three basins. This publication presents a thermal maturity map of Devonian shale in the Illinois, Michigan, and Appalachian basins. The map shows outlines of the three basins (dashed black lines) and an outline of Devonian shale (solid black lines). The basin outlines are compiled from Thomas and others (1989) and Swezey (2008, 2009). The outline of Devonian shale is a compilation from Freeman (1978), Thomas and others (1989), de Witt and others (1993), Dart (1995), Nicholson and others (2004), Dicken and others (2005a,b), and Stoeser and others (2005).

Physical and chemical characterization of Devonian gas shale. Quarterly status report, October 1-December 31, 1978

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zielinski, R.E.; Nance, S.W.

On shale samples from the WV-6 (Monongalia County, West Virginia) well, mean total gas yield was 80.4 ft/sup 3//ton. Mean hydrocarbon gas yield was 5.7 ft/sup 3//ton, 7% of total yield. Methane was the major hydrocarbon component and carbon dioxide the major nonhydrocarbon component. Oil yield was negligible. Clay minerals and organic matter were the dominant phases of the shale. Illite averages 76% of the total clay mineral content. This is detrital illite. Permeation of methane, parallel to the bedding direction for select samples from WV-5 (Mason County, West Virginia) well ranges from 10/sup -4/ to 10/sup -12/ darcys. Themore » permeability of these shales is affected by orgaic carbon content, density, particle orientation, depositional facies, etc. Preliminary studies of Devonian shale methane sorption rates suggest that these rates may be affected by shale porosity, as well as absorption and adsorption processes. An experimental system was designed to effectively simulate sorption of methane at natural reservoir conditions. The bulk density and color of select shales from Illinois, Appalachian and Michigan Basins suggest a general trend of decreasing density with increasing organic content. Black and grayish black shales have organic contents which normally exceed 1.0 wt %. Medium dark gray and gray shales generally have organic contents less than 1.0 wt %.« less

The Northern Gulf of Mexico During OAE2 and the Relationship Between Water Depth and Black Shale Development

NASA Astrophysics Data System (ADS)

Lowery, Christopher M.; Cunningham, Robert; Barrie, Craig D.; Bralower, Timothy; Snedden, John W.

2017-12-01

Despite their name, Oceanic Anoxic Events (OAEs) are not periods of uniform anoxia and black shale deposition in ancient oceans. Shelf environments account for the majority of productivity and organic carbon burial in the modern ocean, and this was likely true in the Cretaceous as well. However, it is unlikely that the mechanisms for such an increase were uniform across all shelf environments. Some, like the northwest margin of Africa, were characterized by strong upwelling, but what might drive enhanced productivity on shelves not geographically suited for upwelling? To address this, we use micropaleontology, carbon isotopes, and sedimentology to present the first record of Oceanic Anoxic Event 2 (OAE2) from the northern Gulf of Mexico shelf. Here OAE2 occurred during the deposition of the well-oxygenated, inner neritic/lower estuarine Lower Tuscaloosa Sandstone. The overlying organic-rich oxygen-poor Marine Tuscaloosa Shale is entirely Turonian in age. We trace organic matter enrichment from the Spinks Core into the deepwater Gulf of Mexico, where wireline log calculations and public geochemical data indicate organic enrichment and anoxia throughout the Cenomanian-Turonian boundary interval. Redox change and organic matter preservation across the Gulf of Mexico shelf were driven by sea level rise prior to the early Turonian highstand, which caused the advection of nutrient-rich, oxygen-poor waters onto the shelf. This results in organic matter mass accumulation rates 1-2 orders of magnitude lower than upwelling sites like the NW African margin, but it likely occurred over a much larger geographic area, suggesting that sea level rise was an important component of the overall increase in carbon burial during OAE2.

A review of the organic geochemistry of shales

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ho, P.C.; Meyer, R.E.

1987-06-01

Shale formations have been suggested as a potential site for a high level nuclear waste repository. As a first step in the study of the possible interaction of nuclides with the organic components of the shales, literature on the identification of organic compounds from various shales of the continent of the United States has been reviewed. The Green River shale of the Cenozoic era is the most studied shale followed by the Pierre shale of the Mesozoic era and the Devonian black shale of the Paleozoic era. Organic compounds that have been identified from these shales are hydrocarbons, fatty acids,more » fatty alcohols, steranes, terpanes, carotenes, carbohydrates, amino acids, and porphyrins. However, these organic compounds constitute only a small fraction of the organics in shales and the majority of the organic compounds in shales are still unidentified.« less

New Advances in Re-Os Geochronology of Organic-rich Sedimentary Rocks.

NASA Astrophysics Data System (ADS)

Creaser, R. A.; Selby, D.; Kendall, B. S.

2003-12-01

Geochronology using 187Re-187Os is applicable to limited rock and mineral matrices, but one valuable application is the determination of depositional ages for organic-rich clastic sedimentary rocks like black shales. Clastic sedimentary rocks, in most cases, do not yield depositional ages using other radioactive isotope methods, but host much of Earth's fossil record upon which the relative geological timescale is based. As such, Re-Os dating of black shales has potentially wide application in timescale calibration studies and basin analysis, if sufficiently high precision and accuracy could be achieved. This goal requires detailed, systematic studies and evaluation of factors like standard compound stoichiometry, geologic effects, and the 187Re decay constant. Ongoing studies have resulted in an improved understanding of the abilities, limitations and systematics of the Re-Os geochronometer in black shales. First-order knowledge of the effects of processes like hydrocarbon maturation and low-grade metamorphism is now established. Hydrocarbon maturation does not impact the ability of the Re-Os geochronometer to determine depositional ages from black shales. The Re-Os age determined for the Exshaw Fm of western Canada is accurate within 2σ analytical uncertainty of the known age of the unit (U-Pb monazite from ash, conodont biostratigraphy). This suggests that the large improvement in precision attained for Re-Os dating of black shales by Cohen et al (ESPL 1999) over the pioneering work of Ravizza & Turekian (GCA 1989), relates to advances in analytical methodologies and sampling strategies, rather than a lack of disturbance by hydrocarbon maturation. We have found that a significant reduction in isochron scatter can be achieved by using an alternate dissolution medium, which preferentially attacks organic matter in which Re and Os are largely concentrated. This likely results from a more limited release of detrital Os and Re held in silicate materials during dissolution, compared with the inverse aqua regia medium used for Carius tube analysis. Using these "organic-selective" dissolution techniques, precise depositional ages have now been obtained from samples with very low TOC contents ( ˜0.5%), meaning that a greater range of clastic sedimentary rocks is amenable for Re-Os age dating. Well-fitted Re-Os isochrons of plausible geological age have also been determined from low-TOC shales subjected to chlorite-grade regional metamorphism. These results further illustrate the wide, but currently underutilized, potential of the Re-Os geochronometer in shales. The precision of age data attainable by the Re-Os system directly from black shales can be better than +/- 1% uncertainty (2σ , derived from isochron regression analysis), and the derived ages are demonstrably accurate.

Evidence for the potential influence of chemocline fluctuations on the Frasnian-Famennian Biotic Crisis in the Illinois and Appalachian Basins

NASA Astrophysics Data System (ADS)

Uveges, B. T.; Junium, C. K.; Boyer, D.; Cohen, P.; Day, J. E.

2017-12-01

The Frasnian-Famennian Biotic Crisis (FFBC) is among the `Big Five' mass extinctions in ecological severity, and was particularly devastating to shallow water tropical faunas and reefs. The FFBC is associated with two organic rich black shale beds collectively known as the Lower and Upper Kellwasser Events(KWEs). Sedimentary N and C isotopes offer insight into the biogeochemical processing of nutrients, and therefore the oceanographic conditions in a basin. In particular, biological production within and around the chemocline can impart a distinct signature to the particulate organic matter (POM) preserved in sediments. Here we present bulk δ15N and δ13Corg isotope data from the Late Devonian Appalachian, and Illinois Basins (AB and IB), with a focus on intervals encompassing the KWEs. Broadly, δ15N values were depleted (-1.0 to +4.0‰), and are consistent with other intervals of black shale deposition, such as OAEs, with the IB being generally more enriched. In both the IB and AB, black shales were 15N depleted compared to the interbedded grey shales on average by 2.3 and 1.0‰ respectively. Organic carbon isotopes exhibit the broad, positive excursions that are typical of the KWEs globally ( 3.5‰ from background). Superimposed over the increase in δ13Corg are sharp decreases in δ13Corg, to as low as -30‰, found at the base of the black shale beds in the both basins. In the context of the pattern of δ15N, this suggests that the mobility of the chemocline and the degree of stratification exert a primary control on both δ15N and δ13Corg. Chemocline movement, or alternatively chemocline collapse, would lead to greater areal extent/upwelling of low oxygen deep waters, rich in isotopically depleted remineralized nutrients (DIN and DIC), leading to the production and eventual preservation of depleted POM in the black shales. Applying this model to the KWEs, which saw more expansive deposits of anoxic facies, we propose that the black shales associated with the KWEs, and thus the FFBC, were the result of exacerbated chemocline fluctuations already inherent to the basin system. The resultant influx of low oxygen, high nutrient water would have not only placed stress on shallow water organisms, but may have also induced eutrophication through spurred primary productivity of organic matter, compounding the the severity of the event.

New insights on the Karoo shale gas potential from borehole KZF-1 (Western Cape, South Africa)

NASA Astrophysics Data System (ADS)

Campbell, Stuart A.; Götz, Annette E.; Montenari, Michael

2016-04-01

A study on world shale reserves conducted by the Energy Information Agency (EIA) in 2013 concluded that there could be as much as 390 Tcf recoverable reserves of shale gas in the southern and south-western parts of the Karoo Basin. This would make it the 8th-largest shale gas resource in the world. However, the true extent and commercial viability is still unknown, due to the lack of exploration drilling and modern 3D seismic. Within the framework of the Karoo Research Initiative (KARIN), two deep boreholes were drilled in the Eastern and Western Cape provinces of South Africa. Here we report on new core material from borehole KZF-1 (Western Cape) which intersected the Permian black shales of the Ecca Group, the Whitehill Formation being the main target formation for future shale gas production. To determine the original source potential for shale gas we investigated the sedimentary environments in which the potential source rocks formed, addressing the research question of how much sedimentary organic matter the shales contained when they originally formed. Palynofacies indicates marginal marine conditions of a stratified basin setting with low marine phytoplankton percentages (acritarchs, prasinophytes), good AOM preservation, high terrestrial input, and a high spores:bisaccates ratio (kerogen type III). Stratigraphically, a deepening-upward trend is observed. Laterally, the basin configuration seems to be much more complex than previously assumed. Furthermore, palynological data confirms the correlation of marine black shales of the Prince Albert and Whitehill formations in the southern and south-western parts of the Karoo Basin with the terrestrial coals of the Vryheid Formation in the north-eastern part of the basin. TOC values (1-6%) classify the Karoo black shales as promising shale gas resources, especially with regard to the high thermal maturity (Ro >3). The recently drilled deep boreholes in the southern and south-western Karoo Basin, the first since the SOEKOR exploration programmes of the 1960's and 1970's, provide new core material to determine the likely current potential for retention of shale gas with regard to the structural and thermal history of the basin. Thus, the KARIN research program will produce a valuable data set for future unconventional gas exploration and production in South Africa.

Thermal maturity patterns (conodont color alteration index and vitrinite reflectance) in Upper Ordovician and Devonian rocks of the Appalachian basin: a major revision of USGS Map I-917-E using new subsurface collections: Chapter F.1 in Coal and petroleum resources in the Appalachian basin: distribution, geologic framework, and geochemical character

USGS Publications Warehouse

Repetski, John E.; Ryder, Robert T.; Weary, David J.; Harris, Anita G.; Trippi, Michael H.; Ruppert, Leslie F.; Ryder, Robert T.

2014-01-01

The conodont color alteration index (CAI) introduced by Epstein and others (1977) and Harris and others (1978) is an important criterion for estimating the thermal maturity of Ordovician to Mississippian rocks in the Appalachian basin. Consequently, the CAI isograd maps of Harris and others (1978) are commonly used by geologists to characterize the thermal and burial history of the Appalachian basin and to better understand the origin and distribution of oil and gas resources in the basin. The main objectives of this report are to present revised CAI isograd maps for Ordovician and Devonian rocks in the Appalachian basin and to interpret the geologic and petroleum resource implications of these maps. The CAI isograd maps presented herein complement, and in some areas replace, the CAI-based isograd maps of Harris and others (1978) for the Appalachian basin. The CAI data presented in this report were derived almost entirely from subsurface samples, whereas the CAI data used by Harris and others (1978) were derived almost entirely from outcrop samples. Because of the different sampling methods, there is little geographic overlap of the two data sets. The new data set is mostly from the Allegheny Plateau structural province and most of the data set of Harris and others (1978) is from the Valley and Ridge structural province, east of the Allegheny structural front (fig. 1). Vitrinite reflectance, based on dispersed vitrinite in Devonian black shale, is another important parameter for estimating the thermal maturity in pre-Pennsylvanian-age rocks of the Appalachian basin (Streib, 1981; Cole and others, 1987; Gerlach and Cercone, 1993; Rimmer and others, 1993; Curtis and Faure, 1997). This chapter also presents a revised percent vitrinite reflectance (%R0) isograd map based on dispersed vitrinite recovered from selected Devonian black shales. The Devonian black shales used for the vitrinite studies reported herein also were analyzed by RockEval pyrolysis and total organic carbon (TOC) content in weight percent. Although the RockEval and TOC data are included in this chapter (table 1), they are not shown on the maps. The revised CAI isograd and percent vitrinite reflectance isograd maps cover all or parts of Kentucky, New York, Ohio, Pennsylvania, Virginia, and West Virginia (fig. 1), and the following three stratigraphic intervals: Upper Ordovician carbonate rocks, Lower and Middle Devonian carbonate rocks, and Middle and Upper Devonian black shales. These stratigraphic intervals were chosen for the following reasons: (1) they represent target reservoirs for much of the oil and gas exploration in the Appalachian basin; (2) they are stratigraphically near probable source rocks for most of the oil and gas; (3) they include geologic formations that are nearly continuous across the basin; (4) they contain abundant carbonate grainstone-packstone intervals, which give a reasonable to good probability of recovery of conodont elements from small samples of drill cuttings; and (5) the Middle and Upper Devonian black shale contains large amounts of organic matter for RockEval, TOC, and dispersed vitrinite analyses. Thermal maturity patterns of the Upper Ordovician Trenton Limestone are of particular interest here, because they closely approximate the thermal maturity patterns in the overlying Upper Ordovician Utica Shale, which is the probable source rock for oil and gas in the Upper Cambrian Rose Run Sandstone (sandstone), Upper Cambrian and Lower Ordovician Knox Group (Dolomite), Lower and Middle Ordovician Beekmantown Group (dolomite or Dolomite), Upper Ordovician Trenton and Black River Limestones, and Lower Silurian Clinton/Medina sandstone (Cole and others, 1987; Jenden and others, 1993; Laughrey and Baldassare, 1998; Ryder and others, 1998; Ryder and Zagorski, 2003). The thermal maturity patterns of the Lower Devonian Helderberg Limestone (Group), Middle Devonian Onondaga Limestone, and Middle Devonian Marcellus Shale-Upper Devonian Rhine street Shale Member-Upper Devonian Ohio Shale are of interest, because they closely approximate the thermal maturity patterns in the Marcellus Shale, Upper Devonian Rhinestreet Shale Member, and Upper Devonian Huron Member of the Ohio Shale, which are the most important source rocks for oil and gas in the Appalachian basin (de Witt and Milici, 1989; Klemme and Ulmishek, 1991). The Marcellus, Rhinestreet, and Huron units are black-shale source rocks for oil and (or) gas in the Lower Devonian Oriskany Sandstone, the Upper Devonian sandstones, the Middle and Upper Devonian black shales, and the Upper Devonian-Lower Mississippian(?) Berea Sandstone (Patchen and others, 1992; Roen and Kepferle, 1993; Laughrey and Baldassare, 1998).

Germanium and uranium in coalified wood from Upper Devonian black shale

USGS Publications Warehouse

Breger, Irving A.; Schopf, James M.

1954-01-01

Microscopic study of black, vitreous, carbonaceous material occurring in the Chattanooga shale in Tennessee and in the Cleveland member of the Ohio shale in Ohio has revealed coalified woody plant tissue. Some samples have shown sufficient detail to be identified with the genus Callixylon. Similar material has been reported in the literature as "bituminous" or "asphaltic" stringers. Spectrographic analyses of the ash from the coalified wood have shown unusually high percentages of germanium, uranium, vanadium, and nickel. The inverse relationship between uranium and germanium in the ash and the ash content of various samples shows an association of these elements with the organic constituents of the coal. On the basis of geochemical considerations, it seems most probable that the wood or coalified wood was germanium-bearing at the time logs or woody fragments were floated into the basins of deposition of the Chattanooga shale and the Cleveland member of the Ohio shale. Once within the marine environment, the material probably absorbed uranium with the formation of organo-uranium compounds such as have been found to exist in coals. It is suggested that a more systematic search for germaniferous coals in the vicinity of the Chattanooga shale and the Cleveland member of the Ohio shale might be rewarding.

Continuously increasing δ98Mo values in Neoarchean black shales and iron formations from the Hamersley Basin

NASA Astrophysics Data System (ADS)

Kurzweil, Florian; Wille, Martin; Schoenberg, Ronny; Taubald, Heinrich; Van Kranendonk, Martin J.

2015-09-01

We present Mo-, C- and O-isotope data from black shales, carbonate- and oxide facies iron formations from the Hamersley Group, Western Australia, that range in age from 2.6 to 2.5 billion years. The data show a continuous increase from near crustal δ98Mo values of around 0.50‰ for the oldest Marra Mamba and Wittenoom formations towards higher values of up to 1.51‰ for the youngest sample of the Brockman Iron Formation. Thereby, the trend in increasing δ98Mo values is portrayed by both carbonate facies iron formations and black shales. Considering the positive correlation between Mo concentration and total organic carbon, we argue that this uniformity is best explained by molybdate adsorption onto organic matter in carbonate iron formations and scavenging of thiomolybdate onto sulfurized organic matter in black shales. A temporal increase in the seawater δ98Mo over the period 2.6-2.5 Ga is observed assuming an overall low Mo isotope fractionation during both Mo removal processes. Oxide facies iron formations show lowest Mo concentrations, lowest total organic carbon and slightly lower δ98Mo compared to nearly contemporaneous black shales. This may indicate that in iron formation settings with very low organic matter burial rates, the preferential adsorption of light Mo isotopes onto Fe-(oxyhydr)oxides becomes more relevant. A similar Mo-isotope pattern was previously found in contemporaneous black shales and carbonates of the Griqualand West Basin, South Africa. The consistent and concomitant increase in δ98Mo after 2.54 billion years ago suggests a more homogenous distribution of seawater molybdate with uniform isotopic composition in various depositional settings within the Hamersley Basin and the Griqualand West Basin. The modeling of the oceanic Mo inventory in relation to the Mo in- and outflux suggests that the long-term build-up of an isotopically heavy seawater Mo reservoir requires a sedimentary sink for isotopically light Mo. The search for this sink (i.e. adsorption onto Mn-oxides in well oxygenated surface oceans and/or subaerial environments or incomplete thiomolybdate formation in weakly sulfidic settings) remains debated, but its relevance becomes more important closer to the Great Oxidation Event and is probably related to already weakly oxidizing conditions even prior to the 2.5 Ga "whiff of oxygen".

Bentonite deposits of the northern Black Hills district, Wyoming, Montana, and South Dakota

USGS Publications Warehouse

Knechtel, Maxwell M.; Patterson, Sam H.

1962-01-01

The northern Black Hills bentonite mining district includes parts of Crook County, Wyo., Carter County, Mont., and Butte County, S. Dak. Within this district, many beds of bentonite occur interspersed with sedimentary strata of Cretaceous age that have an average total thickness of about 3,000 feet and consist chiefly of marine shale, marl, and argillaceous sandstone. The bentonite beds occur in formations ranging upward from the Newcastle sandstone to the lower part of the Mitten black shale member of the Pierre shale. Tertiary (?) and Quaternary deposits of gravel, sand, and silt are present on extensive terraces, and deposits of such materials also extend along stream courses in all parts of the district. The overall geologic structure of the district is that of a broad northwestward- plunging anticline, in which the strata dip gently toward the northeast, north, and northwest. The overall structure is interrupted, however, by several subordinate folds which bring the bentonite beds to the surface repeatedly, so that large resources of bentonite are present under light overburden. The northern Black Hills district is an important source of commercial gel-forming sodium-type bentonite. During the period 1941-56 more than 5 million tons of raw bentonite was mined, most of which came from the Clay Spur bed near the top of the Mowry shale; a few thousand tons was mined from bed A in the Newcastle sandstone. Calcium-type bentonite occurs in bed B in the Mowry shale and in bed I at the base of the Mitten black shale member. Seven other beds are sufficiently thick and continuous to warrant consideration as prospective sources of bentonite for industrial use. Most of the bentonite produced is sold for use (a) as an ingredient of drilling mud; (b) for preparing metallurgical molding sand of superior dry strength; and (c) for the bonding material used in pelletizing taconite iron ore of the Lake Superior region. The results of drilling-mud and foundry-sand bonding-clay tests of several hundred samples, as well as analyses of selected samples, chiefly by X-ray, differential thermal, base exchange and spectrographic methods, are included in this report.

Installation Restoration Program Records Search for 158 Tactical Fighter Group, Vermont Air National Guard, Burlington International Airport.

DTIC Science & Technology

1983-09-01

cold winters. Coldest temperatures ir. winter months are caused by high pressure systems which move rapidly dohn from central Canada cr Hudson Eay... dolomitic marble; or sand (30 to 60 feet), Glacial till (30 to 50 feet), and bedrock. The materials occurring above the bedrock in the vicinity of the...Trenton Group Iberville formation Noncalcareous black shale interbedded with 1000 dolomite . Stony point formation Predominantly calcareous black shale

Graphite Black shale of Vendas de Ceira, Coimbra, Portugal

NASA Astrophysics Data System (ADS)

Quinta-Ferreira, Mário; Silva, Daniela; Coelho, Nuno; Gomes, Ruben; Santos, Ana; Piedade, Aldina

2017-04-01

The graphite black shale of Vendas de Ceira located in south of Coimbra (Portugal), caused serious instability problems in recent road excavation slopes. The problems increased with the rain, transforming shales into a dark mud that acquires a metallic hue when dried. The black shales are attributed to the Devonian or eventually, to the Silurian. At the base of the slope is observed graphite black shale and on the topbrown schist. Samples were collected during the slope excavation works. Undisturbed and less altered materials were selected. Further, sampling was made difficult as the graphite shale was covered by a thick layer of reinforced concrete, which was used to stabilize the excavated surfaces. The mineralogy is mainly constituted by quartz, muscovite, ilite, ilmenite and feldspar without the presence of expansive minerals. The organic matter content is 0.3 to 0.4%. The durability evaluated by the Slake Durability Test varies from very low (Id2 of 6% for sample A) to high (98% for sample C). The grain size distribution of the shale particles, was determined after disaggregation with water, which allowed verifying that sample A has 37% of fines (5% of clay and 32% of silt) and 63% of sand, while sample C has only 14% of fines (2% clay and 12% silt) and 86% sand, showing that the decrease in particle size contributes to reduce durability. The unconfined linear expansion confirms the higher expandability (13.4%) for sample A, reducing to 12.1% for sample B and 10.5% for sample C. Due the shale material degradated with water, mercury porosimetry was used. While the dry weight of the three samples does not change significantly, around 26 kN/m3, the porosity is much higher in sample A with 7.9% of pores, reducing to 1.4% in sample C. The pores size vary between 0.06 to 0.26 microns, does not seem to have any significant influence in the shale behaviour. In order to have a comparison term, a porosity test was carried out on the low weatherable brown shale, which is quite abundant at the site. The main difference to the graphite shale is the high porosity of the brown shale with 14.7% and the low volume weight of 23 kN/m3, evidencing the distinct characteristics of the graphite schists. The maximum strength was evaluated by the Schmidt hammer, as the point load test could not be performed as the rock was very soft. The maximum estimated values on dry samples were 32 MPa for sample A and 85 MPa for sample C. The results show a singular material characterized by significant heterogeneity. It can be concluded that for the graphite schists the smaller particle size and higher porosity make the soft rock extremely weatherable when decompressed and exposed to water, as a result of high capillary tension and reduced cohesion. They also exhibit high expansion and an enormous degradation of the rock presenting a behaviour close to a soil. The graphite black schist is a highly weatherable soft rock, without expansive minerals, with small pores, in which the porosity, low strength and low cohesion allow their rapid degradation when decompressed and exposed to the action of Water.

Late Paleozoic SEDEX deposits in South China formed in a carbonate platform at the northern margin of Gondwana

NASA Astrophysics Data System (ADS)

Qiu, Wenhong Johnson; Zhou, Mei-Fu; Liu, Zerui Ray

2018-05-01

SEDEX sulfide deposits hosted in black shale and carbonate are common in the South China Block. The Dajiangping pyrite deposit is the largest of these deposits and is made up of stratiform orebodies hosted in black shales. Sandstone interlayered with stratiform orebodies contains detrital zircon grains with the youngest ages of 429 Ma. Pyrite from the orebodies has a Re-Os isochron age of 389 ± 62 Ma, indicative of formation of the hosting strata and syngenetic pyrite ores in the mid-late Devonian. The hosting strata is a transgression sequence in a passive margin and composed of carbonaceous limestone in the lower part and black shales in the upper part. The ore-hosting black shales have high TOC (total organic carbon), Mo, As, Pb, Zn and Cd, indicating an anoxic-euxinic deep basin origin. The high redox proxies, V/(V + Ni) > 0.6 and V/Cr > 1, and the positive correlations of TOC with Mo and V in black shales are also consistent with an anoxic depositional environment. The Dajiangping deposit is located close to the NE-trending Wuchuan-Sihui fault, which was active during the Devonian. The mid-late Devonian mineralization age and the anoxic-euxinic deep basinal condition of this deposit thus imply that the formation of this deposit was causally linked to hydrothermal fluid exhalation in an anoxic fault-bounded basin that developed in a carbonate platform of the South China Block. The regional distribution of many Devonian, stratiform, carbonaceous sediment-hosted sulfide deposits along the NE-trending fault-bounded basins in South China, similar to the Dajiangping deposit, indicates that these deposits formed at a basin developed in the passive margin setting of the South China Block during the Devonian. This environment was caused by the break-up and northward migration of the South China Block from Gandwana.

Reconstruction of the Paleoproterozoic deeper ocean environment: Preliminary Report of the Ghana Birimian Greenstone Belt Drilling Project (GHB)

NASA Astrophysics Data System (ADS)

Kiyokawa, S.; Yoshimaru, S.; Miki, T.; Sakai, S.; Ikehara, M.; Yamaguchi, K. E.; Ito, T.; Onoue, T.; Takehara, M.; Tetteh, G. M.; Nyame, F. K.

2016-12-01

The Paleoproterozoic Era are one of the most rapid environmental change when the earth surface environment was affected by formation of continents and increasing atmospheric oxygen levels. Major oxidation of Great Oxidation Event (GOE) are reported this ages (eg. Holland, 2006; Condie, 2001; Lyons et al., 2014). The nature of deep sea environments at this time have not been clearly identified and oceanic sediments are mostly involved in subduction. The Paleoproterozoic Birimian Greenstone Belt is an ophiolitic volcaniclastic sequence in Ghana, with depositional age of over 2.3-2.2 Ga (Petersson et al., 2016). Detail research was conducted of the Ashanti (Axim-Konongo) Belt of the Birimian Greenstone Belt along the coast near Cape Three Points area. Very thick volcaniclastic and organic-rich sedimentary rocks, which we now refer to as the Cape Three Points Group, crop out in the lower part of the Birimian Greenstone Belt. Stratigraphically, three unit identified; the lower portion contains thick vesicular volcaniclastic rocks, the middle portion is made up of laminated volcaniclastics and black shale, and the upper portion dominated by fine laminated volcaniclastics with more black shale sequence. Continuous core drilling from Dec 3-12th 2015 of the upper part of the sequence intersected saprolite to a depth of 30m and fresh, well preserved stratigraphy with graded bedding and lamination to a depth of 195m. Half cut cores show well laminated organic rich black shale and relative carbonate rich layers with very fine pyrite grains. SHRIMP age data from a porphyry intrusion into this sequence indicate an age of 2250 Ma. Carbon isotope analysis shows δ13C = -43 to -37‰ for black shale with the very light isotope values for cyanobacterial signature.The fining-upward sequences, well laminated bed and black shales and REE data suggest this sequence situated partly silent stagnant with volcanic activity ocean floor environment around an oceanic island arc condition.

A Column Experiment To Determine Black Shale Degradation And Colonization By Means of δ13C and 14C Analysis Of Phospholipid Fatty Acids And DNA Extraction

NASA Astrophysics Data System (ADS)

Seifert, A.; Gleixner, G.

2008-12-01

We investigated the degradation of black shale organic matter by microbial communities. We inoculated two columns respectively, with the fungi Schizophyllum commune, the gram-positive bacterium Pseudomonas putida and the gram-negative bacteria Streptomyces griseus and Streptomyces chartreusis. These microorganisms are known to degrade a wide variety of organic macromolecules. Additionally, we had two sets of control columns. To one set the same nutrient solution was added as to the inoculated columns and to the other set only sterile deionised water was supplied. All columns contained 1.5 kg of freshly crushed not autoclaved black shale material with a particle size of 0.63-2 mm. The columns were incubated at 28° C and 60% humidity in the dark. The aim was to investigate, which microorganisms live on black shales and if these microorganisms are able to degrade ancient organic matter. We used compound specific stable isotope measurement techniques and compound specific 14C-dating methods. After 183 days PLFAs were extracted from the columns to investigate the microbial community, furthermore we extracted on one hand total-DNA of column material and on the other hand DNA from pure cultures isolates which grew on Kinks-agar B, Starch-casein-nitrate-agar (SCN) and on complete-yeast-medium-agar (CYM). According to the PLFA analysis bacteria dominated in the columns, whereas in pure cultures more fungi were isolated. A principal component analysis revealed differences between the columns in accordance with the inoculation, but it seems that the inoculated microorganisms were replaced by the natural population. For AMS measurements palmitic acid (C 16:0) was re-isolated from total-PLFA-extract with a preparative fraction collector (PFC). Preliminary results of the study revealed that microorganisms are able to degrade black shale material and that PLFA analysis are useful methods to be combined with analysis of stable isotope and 14C measurements to study microbial degradation processes.

Milankovitch climate cyclicity and its effect on relative sea level changes and organic carbon storage, Late Cretaceous black shales of Colombia and Venezuela

DOE Office of Scientific and Technical Information (OSTI.GOV)

Villamil, T.; Kauffman, E.G.

1993-02-01

The Late Cretaceous Villeta Group and La Luna Formation shows remarkable depositional cyclicity attributable to Milankovitch climate cycles. Each 30-60 cm thick hemicycle is composed of a basal gray shale, a medial black, organic-rich shale, and an upper gray shale with a dense argillaceous limestone cap. Fourier time-series analysis revealed peak frequencies of 500, 100, and 31 ka (blending 21 and 42 ka data). ThiS cyclicity reflects possibly wet cooler (shale) to dry, possibly warm (limestone) climatic changes and their influence on relative sea level, sedimentation rates/patterns, productivity, water chemistry and stratification. Wet/cool hemicycles may produce slight lowering of sealevel,more » increased rates of clay sedimentation, diminished carbonate production, water stratification, increased productivity among noncalcareous marine plankton, and increased Corg production and storage. Dry/warm hemicycles may produce a slight rise in sealevel, and return to normal marine conditions with low Corg storage. Source rock quality may depend upon the predominance of wet over dry climatic phases. Differences between climate-forced cyclicity and random facies repetition, are shown by contrasting observed lithological patterns and geochemical signals with litho- and chemostratigraphy generated from random models. Accomodation space plots (Fischer plots) for cyclically interbedded black shale-pelagic limestone sequences, allowed prediction of facies behavior, shoreline architecture, and quantitative analysis of relative sea level. The synchroneity of Milankovitch cycles and changes in hemicycle stacking patterns, were tested against a new high-resolution event-chronostratigraphic and biostratigraphic framework for NW South America. Geochemical spikes and hemicycle stacking patterns occur consistently throughout the sections measured, supporting the correlation potential of cyclostratigraphy.« less

Cretaceous sedimentation in the outer Eastern Carpathians: Implications for the facies model reconstruction of the Moldavide Basin

NASA Astrophysics Data System (ADS)

Roban, R. D.; Krézsek, C.; Melinte-Dobrinescu, M. C.

2017-06-01

The mid Cretaceous is characterized by high eustatic sea-levels with widespread oxic conditions that made possible the occurrence of globally correlated Oceanic Red Beds. However, very often, these eustatic signals have been overprinted by local tectonics, which in turn resulted in Lower Cretaceous closed and anoxic basins, as in the Eastern Carpathians. There, the black shale to red bed transition occurs in the latest Albian up to the early Cenomanian. Although earlier studies discussed the large-scale basin configuration, no detailed petrography and sedimentology study has been performed in the Eastern Carpathians. This paper describes the Hauterivian to Turonian lithofacies and interprets the depositional settings based on their sedimentological features. The studied sections crop out only in tectonic half windows of the Eastern Carpathians, part of the Vrancea Nappe. The lithofacies comprises black shales interbedded with siderites and sandstones, calcarenites, marls, radiolarites and red shales. The siliciclastic muddy lithofacies in general reflects accumulation by suspension settling of pelagites and hemipelagites in anoxic (black shale) to dysoxic (dark gray and gray to green shales) and oxic (red shales) conditions. The radiolarites alternate with siliceous shales and are considered as evidence of climate changes. The sandstones represent mostly low and high-density turbidite currents in deep-marine lobes, as well as channel/levee systems. The source area is an eastern one, e.g., the Eastern Carpathians Foreland, given the abundance of low grade metamorphic clasts. The Hauterivian - lower Albian sediments are interpreted as deep-marine, linear and multiple sourced mud dominated systems deposited in a mainly anoxic to dysoxic basin. The anoxic conditions existed in the early to late Albian, but sedimentation changed to a higher energy mud/sand-dominated submarine channels and levees. This coarsening upwards tendency is interpreted as the effect of the Aptian to Albian compressional tectonics of the Carpathians. The deepening of the Moldavide Basin from the Cenomanian is most probably linked to a significant sea-level rise.

High resolution biogeochemistry in the Upper Cenomanian black shales of the Umbria-Marche Basin (central Italy)

NASA Astrophysics Data System (ADS)

Bombardiere, L.; Farrimond, P.; Tyson, R. V.; Forster, A.; Sinninghe-Damsté, J.

2003-04-01

The uppermost Cenomanian "anoxic event" (i.e. OAE2) in the Umbria-Marche Basin is recorded by a 0.7-1.2 metre thick interval (the Bonarelli Level) consisting of black, organic-rich laminated mudstones ("black shales"), radiolarian layers and grey-greenish, organic-poor claystones. The occurrence of the radiolarian layers and the organic-poor claystones defines three lithological sub-units which can be correlated at basin scale. In addition, a number of thin black shales ("Bonarelli precursors") has been observed in the limestones underlying the Bonarelli Level; their occurrence appears to be tuned with Milankovitch cycles. This study investigates palaeoproductivity and preservation in the Bonarelli Level and in the precursors using a high resolution molecular biomarker analysis. The onset of the Bonarelli deposition (i.e. the lower sub-unit) is characterized by a drastic increase in the relative abundance of compounds associated with algal precursors (e.g. steranes and phytane). Equally, the same interval shows an increase in the biomarker proxies related to the intensity of oxygen depletion (e.g. homohopane index). The other two Bonarelli sub-units also reflect fluctuations in oxic-anoxic conditions and palaeoproductivity. As the molecular compounds thought to reflect qualitative changes in palaeoproductivity and anoxia do not exhibit any significant differencies between the precursor black shales and the Bonarelli Level, the palaeoenvironmental conditions leading to organic-rich sediments were presumably similar. The results from the Italian sites have been compared with two other OAE2 localities, both characterized by proximal depositional settings: Oued Bahloul (Tunisia) and Tarfaya (Morocco). This work is supported by the European Community's Improving Human Potential Programme under contract HPRN-CT-1999-00055, C/T-NET.

Installation Restoration Program. Phase I. Records Search, Hancock Field, New York.

DTIC Science & Technology

1982-07-01

purplish red, red, gray, green or black shale (major fraction) and shaly dolomite (minor fraction). The unit is poorly stra- tified and reaches a... fractured and jointed locally. At Hancock Field, the Vernon is typically overlain by a thin layer of glacial till. Test borings advanced at the Semi...the consolidated rock aquifer, composed of shales and dolomitic shales of the previously described Vernon Formation. Water is contained in this unit

Mineralogy and Geochemistry of Vanadium-Bearing Black Shales at Zhangcun and Zhengfang, Eastern Jiangxi Province, China

NASA Astrophysics Data System (ADS)

Long, H.; Long, H.; Nekvasil, H.; Liu, Y.

2001-12-01

As a member of Hetang Formation, lower Cambrian, the Zhangcun-Zhengfang vanadium-bearing black shales are spread in the sea basin outside of the Ancient Jiangnan Island Arc. The composition of black shales is silicalite + siltstone + detrital carbonate. A large amount of hyalophane has been discovered in the shales and the hyalophane-rich rock is the major type of vanadium-host rock. The barium content in the hyalophane is up to 18.91%. The vanadium mainly exists in vanadiferous illite and several Ti-V oxides, possibly including a new mineral. The chemical formula of this kind of Ti-V oxide is V2O3¡nTiO2, n=4¡ª9, according to the electronic microprobe studies. The micro X-ray diffraction studies show the new mineral may be triclinic. The shales are rich in Ba, K, V and contain only trace Na and Mn while all the compositions of the shales except carbonate have a low content of Mg and Ca. According to the authors¡_ study, V obviously has a relationship with Ba and Se, which are from the volcano or hydrothermal activities, and the basic elements Cr, Co, Ni, Ti and Fe. It may present that they are from the same source. Thus, it seems that they are not from the ¡rnormal¡_ sedimentary environment and may be from the hydrothermal deposition. The REE models show that silicalite may be the hydrothermal deposit that does not mix with seawater while the REE models of hyalopahne-rich rock is similar to some modern hydrothermal deposits in the seafloor. The subtle negative anomaly of Yb may reflect the REE model of basalt in the seafloor. The geology and geochemistry of the shales indicate that the shales may be of hydrothermal genesis. Silicalite may be the typical ¡r pure¡_ hydrothermal sediment and hyalophane-rich rock may be the product of hydrothermal activity while the hydrothermal fluid passes the continent source material in the sedimentary process. V, Ti, Ba and Si may be from the volcanic rock in the seafloor and the Al and K may be from the continent.

Use of arsenic and REE in black shales as potential environmental tracers in hydraulic fracturing operations

NASA Astrophysics Data System (ADS)

Yang, J.; Torres, M. E.; Haley, B. A.; McKay, J. L.; Algeo, T. J.; Hakala, A.; Joseph, C.; Edenborn, H. M.

2013-12-01

Black shales commonly targeted for shale gas development were deposited under low oxygen concentrations, and typically contain high As levels. The depositional environment governs its solid-phase association in the sediment, which in turn will influence degree of remobilization during hydraulic fracturing. Organic carbon (OC), trace element (TE) and REE distributions have been used as tracers for assessing deep water redox conditions at the time of deposition in the Midcontinent Sea of North America (Algeo and Heckel, 2008), during large-scale oceanic anoxic events (e.g., Bunte, 2009) and in modern OC-rich sediments underlying coastal upwelling areas (e.g., Brumsack, 2006). We will present REE and As data from a collection of six different locations in the continental US (Kansas, Iowa, Oklahoma, Kentucky, North Dakota and Pennsylvania), ranging in age from Devonian to Upper Pennsylvanian, and from a Cretaceous black shale drilled on the Demerara Rise during ODP Leg 207. We interpret our data in light of the depositional framework previously developed for these locations based on OC and TE patterns, to document the mechanisms leading to REE and As accumulation, and explore their potential use as environmental proxies and their diagenetic remobilization during burial, as part of our future goal to develop a predictive evaluation of arsenic release from shales and transport with flowback waters. Total REE abundance (ΣREE) ranged from 35 to 420 ppm in an organic rich sample from Stark shale, KS. PAAS-normalized REE concentrations ranged from 0.5 to 7, with the highest enrichments observed in the MREE (Sm to Ho). Neither the ΣREE nor the MREE enrichments correlated with OC concentrations or postulated depositional redox conditions, suggesting a principal association with aluminosilicates and selective REE fractionation during diagenesis. In the anoxic reducing environments in which black shales were deposited, sulfide minerals such as FeS2 trap aqueous arsenic in the crystal lattice, but As is also known to bind to the charged surfaces of clay minerals. Our arsenic concentration data show that the highest abundances (up to 70 ppm) are found in sediments with the highest total sulfur concentration (to 2.6 ppm), but there was no clear correlation with organic carbon or aluminosilicate content. We compare our results with preliminary data from a series of flowback waters sampled from ten producing wells in Pennsylvania and from high-pressure high-temperature experimental leaching of Marcellus shale samples.

The case for metamorphic base metal mineralization: pyrite chemical, Cu and S isotope data from the Cu-Zn deposit at Kupferberg in Bavaria, Germany

NASA Astrophysics Data System (ADS)

Höhn, S.; Frimmel, H. E.; Debaille, V.; Pašava, J.; Kuulmann, L.; Debouge, W.

2017-12-01

The stratiform Cu-Zn sulfide deposit at Kupferberg in Germany represents Bavaria's largest historic base metal producer. The deposit is hosted by Early Paleozoic volcano-sedimentary strata at the margin of a high-grade allochthonous metamorphic complex. The present paper reports on the first Cu and S isotope data as well as trace element analyses of pyrite from this unusual deposit. The new data point to syn-orogenic mineralization that was driven by metamorphic fluids during nappe emplacement. Primary Cu ore occurs as texturally late chalcopyrite within stratiform laminated pyrite in black shale in two different tectonostratigraphic units of very low and low metamorphic grade, respectively, that were juxtaposed during the Variscan orogeny. Trace element contents of different pyrite types suggest the presence of at least one hydrothermal pyrite generation (mean Co/Ni = 35), with the other pyrite types being syn-sedimentary/early diagenetic (mean Co/Ni = 3.7). Copper isotope analyses yielded a narrow δ65Cu range of -0.26 to 0.36‰ for all ore types suggesting a hypogene origin for the principal chalcopyrite mineralization. The ore lenses in the two different tectonostratigraphic units differ with regard to their δ34S values, but little difference exists between poorly and strongly mineralized domains within a given locality. A genetic model is proposed in which syn-sedimentary/early diagenetic pyrite with subordinate chalcopyrite and sphalerite formed in black shale beds in the two different stratigraphic units, followed by late-tectonic strata-internal, hydrothermal mobilization of Fe, Cu, and Zn during syn-orogenic thrusting, which concentrated especially Cu to ore grade. In agreement with this model, Cu distribution in stream sediments in this region shows distinct enrichments bound to the margin of the allochthonous complex. Thus, Kupferberg can be considered a rare example of a syn-orogenic Cu deposit with the Cu probably being derived from syn-sedimentary/early diagenetic pyrite contained in Early Paleozoic shale units.

Distribution and variation of the inorganic fraction of Devonian to Bashkirian black shales in the north-western part of the Dniepr-Donets Basin, Ukraine

NASA Astrophysics Data System (ADS)

Wegerer, Eva; Sachsenhofer, Reinhard; Misch, David; Aust, Nicolai

2016-04-01

Mineralogical data of 112 core samples from 12 wells are used to investigate lateral and vertical variations in the lithofacies of Devonian to Bashkirian black shales in the north-western part of the Dniepr-Donets-Basin. Sulphur and carbonate contents as well as organic geochemical parameters, including TOC and Hydrogen Index have been determined on the same sample set within the frame of an earlier study (Sachsenhofer et al. 2010). This allows the correlation of inorganic and organic composition of the black shales. Aims of the study are to distinguish between detrital and authigenic minerals, to relate the lithofacies of the black shales with the tectono-stratigraphic sequences of the Dniepr-Donets Basin, to contribute to the reconstruction of the depositional environment and to relate diagenetic processes with the thermal history of the basin. Mineral compositions were determined primarily using XRD-measurements applying several measurement procedures, e.g. chemical and temperature treatment, and specific standards. Major differences exist in the mineralogical composition of the black shales. For example, clay mineral contents range from less than 20 to more than 80 Vol%. Kaolinite contents are significantly higher in rocks with a Tournaisian or Early Visean age than in any other stratigraphic unit. This is also true for two Lower Visean coal samples from the shallow north-westernmost part of the basin. Chlorite contents reach maxima in uppermost Visean and overlying rocks. Quartz contents are often high in Upper Visean rocks and reach maxima in Bashkirian units. Feldspar-rich rocks are observed in Devonian sediments from the north-western part of the study area and may reflect the proximity to a sediment source. Carbonate contents are typically low, but reach very high values in some Tournaisian, Lower Visean and Serpukhovian samples. Pyrite contents reach maxima along the basin axis in Tournaisian and Visean rocks reflecting anoxic conditions. Mixed layer minerals are dominated by illite. Their presence in samples from depth exceeding 5 km reflects the low thermal overprint of Paleozoic rocks in the north-western Dniepr-Donets-Basin.

Chemical analysis and geochemical associations in Devonian black shale core samples from Martin County, Kentucky; Carroll and Washington counties, Ohio; Wise County, Virginia; and Overton County, Tennessee

USGS Publications Warehouse

Leventhal, Joel S.

1979-01-01

Core samples from Devonian shales from five localities in the Appalachian Basin have been analyzed for major, minor, and trace constituents. The contents of major elements are rather similar; however, the minor constituents, organic C, S, PO4, and CO3, show variations by a factor of 10. Trace elements Mo, Ni, Cu, V, Co, U, Zn, Hg, As, and Mn show variations that can be related graphically and statistically to the minor constituents. Down-hole plots show the relationships most clearly. Mn is associated with CO3 content, the other trace elements are strongly Controlled by organic C. Amounts of organic C are generally in the range of 3-6 percent, and S is in the range of 2-5 percent. Trace-element amounts show the following general ranges (ppm, parts per million)- Co, 20-40; Cu,40-70; U, 10-40; As, 20-40, V, 150-300; Ni, 80-150; high values are as much as twice these values. The organic C was probably the concentrating agent, whereas the organic C and sulfide S created an environment for preservation or immobilization of trace elements. Closely spaced samples showing an abrupt transition in color from black to gray and gray to black shale show similar effects of trace-element changes, that is, black shale contains enhanced amounts of organic C and trace elements. Ratios of trace elements to organic C or sulfide S were relatively constant even though deposition rates varied from 10 to 300 meters in 5 million years.

13C Nuclear magnetic resonance studies of kerogen from Cretaceous black shales thermally altered by basaltic intrusions and laboratory simulations

USGS Publications Warehouse

Dennis, L.W.; Maciel, G.E.; Hatcher, P.G.; Simoneit, B.R.T.

1982-01-01

Cretaceous black shales from DSDP Leg 41, Site 368 in the Eastern Atlantic Ocean were thermally altered during the Miocene by an intrusive basalt. The sediments overlying and underlying the intrusive body were subjected to high temperatures (up to ~ 500??C) and, as a result, their kerogen was significantly altered. The extent of this alteration has been determined by examination by means of 13C nuclear magnetic resonance, using cross polarization/magic-angle spinning (CP/MAS). Results indicate that the kerogen becomes progressively more aromatic in the vicinity of the intrusive body. Laboratory heating experiments, simulating the thermal effects of the basaltic intrusion, produced similar results on unaltered shale from the drill core. The 13C CP/MAS results appear to provide a good measure of thermal alteration. ?? 1982.

Process for oil shale retorting using gravity-driven solids flow and solid-solid heat exchange

DOEpatents

Lewis, A.E.; Braun, R.L.; Mallon, R.G.; Walton, O.R.

1983-09-21

A cascading bed retorting process and apparatus are disclosed in which cold raw crushed shale enters at the middle of a retort column into a mixer stage where it is rapidly mixed with hot recycled shale and thereby heated to pyrolysis temperature. The heated mixture then passes through a pyrolyzer stage where it resides for a sufficient time for complete pyrolysis to occur. The spent shale from the pyrolyzer is recirculated through a burner stage where the residual char is burned to heat the shale which then enters the mixer stage.

Process for oil shale retorting using gravity-driven solids flow and solid-solid heat exchange

DOEpatents

Lewis, Arthur E.; Braun, Robert L.; Mallon, Richard G.; Walton, Otis R.

1986-01-01

A cascading bed retorting process and apparatus in which cold raw crushed shale enters at the middle of a retort column into a mixer stage where it is rapidly mixed with hot recycled shale and thereby heated to pyrolysis temperature. The heated mixture then passes through a pyrolyzer stage where it resides for a sufficient time for complete pyrolysis to occur. The spent shale from the pyrolyzer is recirculated through a burner stage where the residual char is burned to heat the shale which then enters the mixer stage.

A non-zircon Hf isotope record in Archean black shales from the Pilbara craton confirms changing crustal dynamics ca. 3 Ga ago.

PubMed

Nebel-Jacobsen, Yona; Nebel, Oliver; Wille, Martin; Cawood, Peter A

2018-01-17

Plate tectonics and associated subduction are unique to the Earth. Studies of Archean rocks show significant changes in composition and structural style around 3.0 to 2.5 Ga that are related to changing tectonic regime, possibly associated with the onset of subduction. Whole rock Hf isotope systematics of black shales from the Australian Pilbara craton, selected to exclude detrital zircon components, are employed to evaluate the evolution of the Archean crust. This approach avoids limitations of Hf-in-zircon analyses, which only provide input from rocks of sufficient Zr-concentration, and therefore usually represent domains that already underwent a degree of differentiation. In this study, we demonstrate the applicability of this method through analysis of shales that range in age from 3.5 to 2.8 Ga, and serve as representatives of their crustal sources through time. Their Hf isotopic compositions show a trend from strongly positive εHf initial values for the oldest samples, to strongly negative values for the younger samples, indicating a shift from juvenile to differentiated material. These results confirm a significant change in the character of the source region of the black shales by 3 Ga, consistent with models invoking a change in global dynamics from crustal growth towards crustal reworking around this time.

Assessment of undiscovered oil and gas resources of the Ordovician Utica Shale of the Appalachian Basin Province, 2012

USGS Publications Warehouse

Kirschbaum, Mark A.; Schenk, Christopher J.; Cook, Troy A.; Ryder, Robert T.; Charpentier, Ronald R.; Klett, Timothy R.; Gaswirth, Stephanie B.; Tennyson, Marilyn E.; Whidden, Katherine J.

2012-01-01

The U.S. Geological Survey assessed unconventional oil and gas resources of the Upper Ordovician Utica Shale and adjacent units in the Appalachian Basin Province. The assessment covers parts of Maryland, New York, Ohio, Pennsylvania, Virginia, and West Virginia. The geologic concept is that black shale of the Utica Shale and adjacent units generated hydrocarbons from Type II organic material in areas that are thermally mature for oil and gas. The source rocks generated petroleum that migrated into adjacent units, but also retained significant hydrocarbons within the matrix and adsorbed to organic matter of the shale. These are potentially technically recoverable resources that can be exploited by using horizontal drilling combined with hydraulic fracturing techniques.

Preliminary stratigraphic cross section showing radioactive zones in the Devonian dark shales in the eastern part of the Appalachian Basin

USGS Publications Warehouse

West, Mareta N.

1978-01-01

The U.S. Geological Survey (USGS), in a cooperative agreement with the U.S. Department of Energy (DOE), is participating in the Eastern Gas Shales Project. The purpose of the DOE project is to increase the production of natural gas from eastern United States shales in petroliferous basins through improved exploration and extraction techniques. The USGS participation includes stratigraphic studies which will contribute to the characterization and appraisal of the natural gas resources of Devonian shale in the Appalachian basin.This cross section differs from others in this series partly because many of the shales in the eastern part of the basin are less radioactive than those farther west and because in this area shales that may be gas-productive are not necessarily highly radioactive and black.

Molybdenum Enrichment in the 3.2 Ga old Black Shales Recovered by Dixon Island-Cleaverville Drilling Project (DXCL-DP) in Northwestern Pilbara, Western Australia

NASA Astrophysics Data System (ADS)

Yamaguchi, K. E.; Kiyokawa, S.; Naraoka, H.; Ikehara, M.; Ito, T.; Suganuma, Y.; Sakamoto, R.; Hosoi, K.

2010-12-01

To obtain drillcores of Mesoarchean black shales with negligible modern weathering, we conducted continental drilling at Cleaverville coast in Pilbara, Western Australia. We recovered 3.2Ga sulfidic black shales of the Cleaverville Group from three drillholes (~200m in total), namely DX, CL1, and CL2. Information on the geology of the drilling site has been reported [1, 2]. Here we report the discovery of Mo enrichment in the 3.2Ga DXCL-DP black shales. We analyzed total chemical compositions of forty black shale samples from drillcore DX and fifty-six of those from CL1 and CL2. Molybdenum concentrations for DX samples ranged from 0.3 to 12.9ppm (Avg±1σ= 1.8±1.9ppm), and those for CL1 and CL2 (combined) ranged from 0.8 to 3.3ppm (Avg±1σ= 1.4±0.4ppm). The highest concentration of Mo occurs in Corg-rich sample, and is comparable to that of the contemporaneous Fig Tree Group in South Africa [3, 4]. The highest concentration of Mo in the DXCL-DP samples, ~13ppm, is lower than that found in the 2.5 Ga Mt. McRae Shale of the Hamersley Group, Western Australia (maximums are ~17ppm [5], and ~40ppm [6]). However, it is much higher, by thirteen times, than the average Mo concentration in the Phanerozoic shales (1ppm [7]). No significant enrichment of Mo was expected to occur in the before-GOE black shales if pO2 was as low as <10-6 PAL. Sulfur isotope analysis revealed, based on the variable δ34S values (-1.9 ~ +26.8‰), that bacterial sulfate reduction was so extensive in the 3.2Ga deep marine environments that sulfate utilization by sulfate-reducers was near completion [8]. Production of bacteriogenic sulfide would have enhanced fixation of dissolved Mo into sulfide minerals in sediments. This is rather a common process occurring in oxygen-depleted environments in the modern ocean ([9]). A combined enrichment of Mo, Corg, and S, together with high δ34S values for a sedimentary formation may be used as a strong evidence for operation of modern-day style sedimentary Mo enrichment. This further implies that oxygenation of the atmosphere and (at least the surface) oceans was significant during deposition of the sediments, ~800Ma earlier than commonly thought ([10]). Operation of present-day style geochemical cycle of Mo in the Mesoarchean surface environments suggests early evolution of atmosphere, oceans, and microbial biosphere. References: [1] Kiyokawa et al, 2006, GSAB 118: 3-22. [2] Yamaguchi et al, 2009, Sci. Drill. 7: 34-37. [3] Yamaguchi, 2002, Ph.D. dissertation, Penn State Univ. [4] Yamaguchi & Ohmoto, 2002, GSA Abstract [5] Naraoka et al, 2001, 4th Int'l Archaean Symp., Perth. [6] Anbar et al, 2007, Science 317: 1903-1906. [7] Vine & Tourtelot, 1970, Econ. Geol. 65: 253-272. [8] Sakamoto et al, 2010, Fall AGU Mtg. [9] Morford & Emerson, 1999, GCA 63: 1735-1750. [10] Bekker et al, 2004, Nature 427: 117-120.

The Architecture and Frictional Properties of Faults in Shale

NASA Astrophysics Data System (ADS)

De Paola, N.; Imber, J.; Murray, R.; Holdsworth, R.

2015-12-01

The geometry of brittle fault zones in shale rocks, as well as their frictional properties at reservoir conditions, are still poorly understood. Nevertheless, these factors may control the very low recovery factors (25% for gas and 5% for oil) obtained during fracking operations. Extensional brittle fault zones (maximum displacement < 3 m) cut exhumed oil mature black shales in the Cleveland Basin (UK). Fault cores up to 50 cm wide accommodated most of the displacement, and are defined by a stair-step geometry. Their internal architecture is characterised by four distinct fault rock domains: foliated gouges; breccias; hydraulic breccias; and a slip zone up to 20 mm thick, composed of a fine-grained black gouge. Hydraulic breccias are located within dilational jogs with aperture of up to 20 cm. Brittle fracturing and cataclastic flow are the dominant deformation mechanisms in the fault core of shale faults. Velocity-step and slide-hold-slide experiments at sub-seismic slip rates (microns/s) were performed in a rotary shear apparatus under dry, water and brine-saturated conditions, for displacements of up to 46 cm. Both the protolith shale and the slip zone black gouge display shear localization, velocity strengthening behaviour and negative healing rates, suggesting that slow, stable sliding faulting should occur within the protolith rocks and slip zone gouges. Experiments at seismic speed (1.3 m/s), performed on the same materials under dry conditions, show that after initial friction values of 0.5-0.55, friction decreases to steady-state values of 0.1-0.15 within the first 10 mm of slip. Contrastingly, water/brine saturated gouge mixtures, exhibit almost instantaneous attainment of very low steady-state sliding friction (0.1), suggesting that seismic ruptures may efficiently propagate in the slip zone of fluid-saturated shale faults. Stable sliding in faults in shale can cause slow fault/fracture propagation, affecting the rate at which new fracture areas are created and, hence, limiting oil and gas production during reservoir stimulation. However, fluid saturated conditions can favour seismic slip propagation, with fast and efficient creation of new fracture areas. These processes are very effective at dilational jogs, where fluid circulation may be enhanced, facilitating oil and gas production.

Cretaceous planktic foraminiferal biostratigraphy of the Calera Limestone, Northern California, USA

USGS Publications Warehouse

Sliter, W.V.

1999-01-01

The Calera Limestone is the largest, most stratigraphically extensive limestone unit of oceanic character included in the Franciscan Complex of northern California. The aim of this paper is to place the Calera Limestone at its type locality (Rockaway Beach, Pacifica) in a high-resolution biostratigraphy utilizing planktic foraminifers studied in thin section. A section, about 110 m-thick, was measured from the middle thrust slice exposed by quarrying on the southwest side of Calera Hill at Pacifica Quarry. Lithologically, the section is divided in two units; a lower unit with 73 m of black to dark-grey limestone, black chert and tuff, and an upper unit with 36.8 m of light-grey limestone and medium-grey chert. Two prominent black-shale layers rich in organic carbon occur 11 m below the top of the lower black unit and at the boundary with overlying light-grey unit, yielding a total organic content (TOC) of 4.7% and 1.8% t.w., respectively. The fossiliferous Calera Limestone section measured at Pacifica Quarry, from the lower black shale, contains eleven zones and three subzones that span approximately 26 m.y. from the early Aptian to the late Cenomanian. The zones indentified range from the Globigerinelloides blowi Zone to the Dicarinella algeriana Subzone of the Rotalipora cushmani Zone. Within this biostratigraphic interval, the Ticinella bejaouaensis and Hedbergella planispira Zones at the Aptian/Albian boundary are missing as are the Rotalipora subticinensis Subzone of the Biticinella breggiensis Zone and the overlying Rotalipora ticinensis Zone in the late Albian owing both to low-angle thrust faulting and to unconformities. The abundance and preservation of planktic foraminifers are poor in the lower part and improve only within the upper G. algerianus Zone. The faunal relationship indicate that the lower black shale occurs in the upper part of the G. blowi Zone and correlates with the Selli Event recognized at global scale in the early Aptian. The upper black shale occurs at or near the boundary between the G. ferreolensis and G. algerianus Zone in the late Aptian. This black layer, or Thalmann Event as named here, seems to represent the sedimentary expression, at the scale of Permanente Terrane, of a global perturbation of the carbon cycle.

Vitrinite equivalent reflectance of Silurian black shales from the Holy Cross Mountains, Poland

NASA Astrophysics Data System (ADS)

Smolarek, Justyna; Marynowski, Leszek; Spunda, Karol; Trela, Wiesław

2014-12-01

A number of independent methods have been used to measure the thermal maturity of Silurian rocks from the Holy Cross Mountains in Poland. Black shales are characterized by diverse TOC values varying from 0.24-7.85%. Having calculated vitrinite equivalent reflectance using three different formulas, we propose that the most applicable values for the Silurian rocks are those based on Schmidt et al. (2015) equation. Based on this formula, the values range from % 0.71 VReqvVLR (the vitrinite equivalent reflectance of the vitrinite-like macerals) to % 1.96 VReqvVLR. Alternative, complementary methods including Rock Eval pyrolysis and parameters based on organic compounds (CPI, Pr/n-C17, Ph/n-C18, MPI1, and MDR) from extracts did not prove adequate as universal thermal maturity indicators. We have confirmed previous suggestions that Llandovery shales are the most likely Silurian source rocks for the generation of hydrocarbons in the HCM.

Fracture patterns and their origin in the upper Devonian Antrim Shale gas reservoir of the Michigan basin; a review

USGS Publications Warehouse

Ryder, Robert T.

1996-01-01

INTRODUCTION: Black shale members of the Upper Devonian Antrim Shale are both the source and reservoir for a regional gas accumulation that presently extends across parts of six counties in the northern part of the Michigan basin (fig. 1). Natural fractures are considered by most petroleum geologists and oil and gas operators who work the Michigan basin to be a necessary condition for commercial gas production in the Antrim Shale. Fractures provide the conduits for free gas and associated water to flow to the borehole through the black shale which, otherwise, has a low matrix permeability. Moreover, the fractures assist in the release of gas adsorbed on mineral and(or) organic matter in the shale (Curtis, 1992). Depths to the gas-producing intervals (Norwood and Lachine Members) generally range from 1,200 to 1,800 ft (Oil and Gas Journal, 1994). Locally, wells that produce gas from the accumulation are as deep as 2,200 (Oil and Gas Journal, 1994). Even though natural fractures are an important control on Antrim Shale gas production, most wells require stimulation by hydraulic fracturing to attain commercial production rates (Kelly, 1992). In the U.S. Geological Survey's National Assessment of United States oil and gas, Dolton (1995) estimates that, at a mean value, 4.45 trillion cubic feet (TCF) of gas are recoverable as additions to already discovered quantities from the Antrim Shale in the productive area of the northern Michigan trend. Dolton (1995) also suggests that undiscovered Antrim Shale gas accumulations exist in other parts of the Michigan basin. The character, distribution, and origin of natural fractures in the Antrim Shale gas accumulation have been studied recently by academia and industry. The intent of these investigations is to: 1) predict 'sweet spots', prior to drilling, in the existing gas-producing trend, 2) improve production practices in the existing trend, 3) predict analogous fracture-controlled gas accumulations in other parts of the Michigan basin, and 4) improve estimates of the recoverable gas in the Antrim Shale gas plays (Dolton, 1995). This review of published literature on the characteristics of Antrim Shale fractures, their origin, and their controls on gas production will help to define objectives and goals in future U.S. Geological Survey studies of Antrim Shale gas resources.

Mesozoic black shales, source mixing and carbon isotopes

NASA Astrophysics Data System (ADS)

Suan, Guillaume

2016-04-01

Over the last decades, considerable attention has been devoted to the paleoenvironmental and biogeochemical significance of Mesozoic black shales. Black shale-bearing successions indeed often display marked changes in the organic carbon isotope composition (δ13Corg), which have been commonly interpreted as evidence for dramatic perturbations of global carbon budgets and CO2 levels. Arguably the majority of these studies have discarded some more "local" explanations when interpreting δ13Corg profiles, most often because comparable profiles occur on geographically large and distant areas. Based on newly acquired data and selected examples from the literature, I will show that the changing contribution of organic components with distinct δ13C signatures exerts a major but overlooked influence of Mesozoic δ13Corg profiles. Such a bias occurs across a wide spectrum of sedimentological settings and ages, as shown by the good correlation between δ13Corg values and proxies of kerogen proportions (such as rock-eval, biomarker, palynofacies and palynological data) recorded in Mesozoic marginal to deep marine successions of Triassic, Jurassic and Cretaceous age. In most of these successions, labile, 12C-enriched amorphous organic matter of marine origin dominates strata deposited under anoxic conditions, while oxidation-resistant, 13C-rich terrestrial particles dominate strata deposited under well-oxygenated conditions. This influence is further illustrated by weathering profiles of Toarcian (Lower Jurassic) black shales from France, where weathered areas dominated by refractory organic matter show dramatic 13C-enrichment (and decreased total organic carbon and pyrite contents) compared to non-weathered portions of the same horizon. The implications of these results for chemostratigraphic correlations and pCO2 reconstructions of Mesozoic will be discussed, as well as strategies to overcome this major bias.

Evolution of Early Paleoproterozoic Ocean Chemistry as Recorded by Black Shales

NASA Astrophysics Data System (ADS)

Scott, C.; Bekker, A.; Lyons, T. W.; Planavsky, N. J.; Wing, B. A.

2010-12-01

In recent years, Precambrian biogeochemists have focused largely on the abundance, speciation and isotopic composition of major and trace elements preserved in organic carbon-rich black shales in order to track the co-evolution of ocean chemistry and life on Earth. Despite the fact that the period from 2.5 to 2.0 Ga hosted major events in Earth’s history, such as the Great Oxidation Event (GOE), an era of global glaciations, a massive and long-lived carbon isotope excursion and the end to banded iron formation (BIF) deposition, each with the potential to directly alter global biogeochemical cycles, it is perhaps best known for its unknowns. In order to help close this gap in our understanding of the evolution of Precambrian ocean chemistry we present a detailed biogeochemical study of Paleoproterozoic black shales deposited between 2.5 and 2.0 Ga. Our study integrates Fe speciation, trace metal chemistry and C, S and N isotope analyses to provide a thorough characterization of marine biogeochemical cycles as they responded to the GOE and set the stage for the demise of BIFs at ca. 1.8 Ga. Our data reveal an ocean that was both surprising similar to, and demonstrably different from, Archean and later Proterozoic oceans. Of particular interest, we find that ferruginous and euxinic conditions co-existed during this period and that sea water trace metal inventories fluctuated dramatically in conjunction with major carbon isotope excursions. By comparing our Paleoproterozoic contribution with recent biogeochemical studies of other Precambrian black shales we can begin to track first order changes in ocean chemistry without the major time gaps that have plagued previous attempts.

Lithofacies, age, depositional setting, and geochemistry of the Otuk Formation in the Red Dog District, northwestern Alaska

USGS Publications Warehouse

Dumoulin, Julie A.; Burruss, Robert A.; Blome, Charles D.

2013-01-01

Complete penetration of the Otuk Formation in a continuous drill core (diamond-drill hole, DDH 927) from the Red Dog District illuminates the facies, age, depositional environment, source rock potential, and isotope stratigraphy of this unit in northwestern Alaska. The section, in the Wolverine Creek plate of the Endicott Mountains Allochthon (EMA), is ~82 meters (m) thick and appears structurally uncomplicated. Bedding dips are generally low and thicknesses recorded are close to true thicknesses. Preliminary synthesis of sedimentologic, paleontologic, and isotopic data suggests that the Otuk succession in DDH 927 is a largely complete, albeit condensed, marine Triassic section in conformable contact with marine Permian and Jurassic strata. The Otuk Formation in DDH 927 gradationally overlies gray siliceous mudstone of the Siksikpuk Formation (Permian, based on regional correlations) and underlies black organic-rich mudstone of the Kingak(?) Shale (Jurassic?, based on regional correlations). The informal shale, chert, and limestone members of the Otuk are recognized in DDH 927, but the Jurassic Blankenship Member is absent. The lower (shale) member consists of 28 m of black to light gray, silty shale with as much as 6.9 weight percent total organic carbon (TOC). Thin limy layers near the base of this member contain bivalve fragments (Claraia sp.?) consistent with an Early Triassic (Griesbachian-early Smithian) age. Gray radiolarian chert dominates the middle member (25 m thick) and yields radiolarians of Middle Triassic (Anisian and Ladinian) and Late Triassic (Carnian-late middle Norian) ages. Black to light gray silty shale, like that in the lower member, forms interbeds that range from a few millimeters to 7 centimeters in thickness through much of the middle member. A distinctive, 2.4-m-thick interval of black shale and calcareous radiolarite ~17 m above the base of the member has as much as 9.8 weight percent TOC, and a 1.9-m-thick interval of limy to cherty mudstone immediately above this contains radiolarians, foraminifers, conodonts, and halobiid bivalve fragments. The upper (limestone) member (29 m thick) is lime mudstone with monotid bivalves and late Norian radiolarians, overlain by gray chert that contains Rhaetian (latest Triassic) radiolarians; Rhaetian strata have not previously been documented in the Otuk. Rare gray to black shale interbeds in the upper member have as much as 3.4 weight percent TOC. At least 35 m of black mudstone overlies the limestone member; these strata lack interbeds of oil shale and chert that are characteristic of the Blankenship, and instead they resemble the Kingak Shale. Vitrinite reflectance values (2.45 and 2.47 percent Ro) from two samples of black shale in the chert member indicate that these rocks reached a high level of thermal maturity within the dry gas window. Regional correlations indicate that lithofacies in the Otuk Formation vary with both structural and geographic position. For example, the shale member of the Otuk in the Wolverine Creek plate includes more limy layers and less barite (as blades, nodules, and lenses) than equivalent strata in the structurally higher Red Dog plate of the EMA, but it has fewer limy layers than the shale member in the EMA ~450 kilometers (km) to the east at Tiglukpuk Creek. The limestone member of the Otuk is thicker in the Wolverine Creek plate than in the Red Dog plate and differs from this member in EMA sections to the east in containing an upper cherty interval that lacks monotids; a similar interval is seen at the top of the Otuk Formation ~125 km to the west (Lisburne Peninsula). Our observations are consistent with the interpretations of previous researchers that Otuk facies become more distal in higher structural positions and that within a given structural level more distal facies occur to the west. Recent paleogeographic reconstructions indicate that the Otuk accumulated at a relatively high paleolatitude with a bivalve fauna typical of the Boreal realm. A suite of δ13Corg (carbon isotopic composition of carbon) data (n=38) from the upper Siksikpuk Formation through the Otuk Formation and into the Kingak(?) Shale in DDH 927 shows a pattern of positive and negative excursions similar to those reported elsewhere in Triassic strata. In particular, a distinct negative excursion at the base of the Otuk (from ‒23.8 to ‒31.3‰ (permil, or parts per thousand)) likely correlates with a pronounced excursion that marks the Permian-Triassic boundary at many localities worldwide. Another feature of the Otuk δ13Corg record that may correlate globally is a series of negative and positive excursions in the lower member. At the top of the Otuk in DDH 927, the δ13Corg values are extremely low and may correlate with a negative excursion that is widely observed at the Triassic-Jurassic boundary.

Systematic Investigation of REE Mobility and Fractionation During Continental Shale Weathering Along a Climate Gradient

NASA Astrophysics Data System (ADS)

Jin, L.; Ma, L.; Dere, A. L. D.; White, T.; Brantley, S. L.

2014-12-01

Rare earth elements (REE) have been identified as strategic natural resources and their demand in the United States is increasing rapidly. REE are relatively abundant in the Earth's crust, but REE deposits with minable concentrations are uncommon. One recent study has pointed to the deep-sea REE-rich muds in the Pacific Ocean as a new potential resource, related to adsorption and concentration of REE from seawater by hydrothermal iron-oxyhydroxides and phillipsite (Kato et al., 2010). Finding new REE deposits will be facilitated by understanding global REE cycles: during the transformation of bedrock into soils, REEs are leached into natural waters and transported to oceans. At present, the mechanisms and factors controlling release, transport, and deposition of REE - the sources and sinks - at Earth's surface remain unclear. Here, we systematically studied soil profiles and bedrock in seven watersheds developed on shale bedrock along a climate transect in the eastern USA, Puerto Rico and Wales to constrain the mobility and fractionation of REE during chemical weathering processes. In addition, one site on black shale (Marcellus) bedrock was included to compare behaviors of REEs in organic-rich vs. organic-poor shale end members under the same environmental conditions. Our investigation focused on: 1) the concentration of REEs in gray and black shales and the release rates of REE during shale weathering, 2) the biogeochemical and hydrological conditions (such as redox, dissolved organic carbon, and pH) that dictate the mobility and fractionation of REEs in surface and subsurface environments, and 3) the retention of dissolved REEs on soils, especially onto secondary Fe/Al oxyhydroxides and phosphate mineral phases. This systematic study sheds light on the geochemical behaviors and environmental pathways of REEs during shale weathering along a climosequence.

Study of hydrocarbon production from the Devonian shale in Letcher, Knott, Floyd, Martin, and Pike Counties, eastern Kentucky annual technical report, July 1, 1984-June 30, 1985

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frankie, W.T.

The Kentucky Geological Survey (KGS) at the University of Kentucky is conducting a 2-year research project funded by the Gas Research Institute (GRI) to study hydrocarbon production from the Devonian shale in eastern Kentucky. Objectives are to develop an understanding of relationships between stratigraphy and hydrocarbon production, create a data base, and prepare geologic reports for each county in the study area. Data were compiled from the KGS, GRI Eastern Gas Data System (EGDS), U. S. Department of Energy (DOE), and industry. Research for Letcher County was completed and 270 Devonian wells were entered into the KGS computer data base.more » Devonian black-shale units were correlated using gamma-ray logs. Structure and isopach maps, and stratigraphic cross sections have been constructed. An isopotential map defining areas of equal initial gas production has been prepared. Statistics for Letcher County have been run on the data base using Datatrieve software package. Statistical analyses focused on different types of formation treatments and the resulting production. Temperature logs were used to detect gas-producing intervals within the Mississippian-Devonian black-shale sequence. The results of the research provide the petroleum industry with a valuable tool for gas exploration in the Devonian shales.« less

Secular distribution of highly metalliferous black shales corresponds with peaks in past atmosphere oxygenation

NASA Astrophysics Data System (ADS)

Johnson, Sean C.; Large, Ross R.; Coveney, Raymond M.; Kelley, Karen D.; Slack, John F.; Steadman, Jeffrey A.; Gregory, Daniel D.; Sack, Patrick J.; Meffre, Sebastien

2017-08-01

Highly metalliferous black shales (HMBS) are enriched in organic carbon and a suite of metals, including Ni, Se, Mo, Ag, Au, Zn, Cu, Pb, V, As, Sb, Se, P, Cr, and U ± PGE, compared to common black shales, and are distributed at particular times through Earth history. They constitute an important future source of metals. HMBS are relatively thin units within thicker packages of regionally extensive, continental margin or intra-continental marine shales that are rich in organic matter and bio-essential trace elements. Accumulation and preservation of black shales, and the metals contained within them, usually require low-oxygen or euxinic bottom waters. However, whole-rock redox proxies, particularly Mo, suggest that HMBS may have formed during periods of elevated atmosphere pO2. This interpretation is supported by high levels of nutrient trace elements within these rocks and secular patterns of Se and Se/Co ratios in sedimentary pyrite through Earth history, with peaks occurring in the middle Paleoproterozoic, Early Cambrian to Early Ordovician, Middle Devonian, Middle to late Carboniferous, Middle Permian, and Middle to Late Cretaceous, all corresponding with time periods of HMBS deposition. This counter-intuitive relationship of strongly anoxic to euxinic, localized seafloor conditions forming under an atmosphere of peak oxygen concentrations is proposed as key to the genesis of HMBS. The secular peaks and shoulders of enriched Se in sedimentary pyrite through time correlate with periods of tectonic plate collision, which resulted in high nutrient supply to the oceans and consequently maximum productivity accompanying severe drawdown into seafloor muds of C, S, P, and nutrient trace metals. The focused burial of C and S over extensive areas of the seafloor, during these anoxic to euxinic periods, likely resulted in an O2 increase in the atmosphere, causing short-lived peaks in pO2 that coincide with the deposition of HMBS. As metals become scarce, particularly Mo, Ni, Se, Ag, and U, the geological times of these narrow HMBS horizons will become a future focus for exploration.

Geology of parts of the Johnny Gulch quadrangle, Montana

USGS Publications Warehouse

Freeman, Val L.

1954-01-01

An area of about 35 square miles, situated about 30 miles southeast of Helena, Montana, was mapped during the summer of 1952 at a scale of l:24, 000. The area includes a part of the eastern foothills of the Elkhorn Mountains, and is underlain by sedimentary mad volcanic rocks of Cretaceous age that were intruded during late Cretaceous or early Tertiary time by several types of igneous rocks. The oldest rocks in the map area are the nonmarine sandstone, shale, and limestone of the Kootenai formation. These are overlain disconformably by the black shale siltstone, sandstone, and siliceous mudstone of the Colorado group that is subdivided into three map units; a lower black shale unit composed of black shale and silty shale with a basal clean sandstone, all of probable marine origin; a middle siliceous unit composed of sandstone, siltstone, and siliceous mudstone of both marine and nonmarine origin; and an upper black unit composed of black shale of marine origin. Conformably above the Colorado group are crystal lithic turfs of the Slim Sam formation; in places theme grade into and in other places are unconformably overlain by the Elkhorn Mountains volcanics composed of crystal tuff, breccia, flows, and bedded tuff of andesitic composition. The rocks of the Elkhorn Mountains volcanics and older formations have been intruded by diorite porphyry and related rocks and by hornblende quartz monzonite. The diorite porphyry and related rocks include hornblende diorite porphyry, hornblende augite diorite porphyry, augite diorite porphyry, and basalt. Resting with marked unconformity upon older rocks are volcanic sedimentary rocks of early Tertiary age that are locally overlain by thin rhyolite flows. Late Tertiary and Quaternary fans overlie the rhyolite flows. Alluvium, talus, and other mantle are present in small amounts in many parts of the area. The sedimentary rocks of the area mapped form a part of the east flank of a major anticline. A major north-south syncline to the north of map area is believed to have been deflected to the east of the area because of the rigidity of large irregular plutons of diorite porphyry. The location of the plutons may have been controlled by the initiation of the major syncline, by a postulated pre-intrusive fault, or by both. Most of the small-scale structural features are related to the emplacement of the plutons. During emplacement the intruded sediments yielded either by faulting or by folding; the deeper rocks failed by faulting and the shallower rocks failed by folding. The area contains deposits of gold, silver, copper, lead, and zinc, none of which are currently being mined; and a deposit of magnetite which is being mined for use in cement.

Inventory and evaluation of potential oil shale development in Kansas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Angino, E.; Berg, J.; Dellwig, L.

The University of Kansas Center for Research, Inc. was commissioned by the Kansas Energy Office and the US Department of Energy to conduct a review of certain oil shales in Kansas. The purpose of the study focused on making an inventory and assessing those oil shales in close stratigraphic proximity to coal beds close to the surface and containing significant reserves. The idea was to assess the feasibility of using coal as an economic window to aid in making oil shales economically recoverable. Based on this as a criterion and the work of Runnels, et al., (Runnels, R.T., Kulstead, R.O.,more » McDuffee, C. and Schleicher, J.A., 1952, Oil Shale in Kansas, Kansas Geological Survey Bulletin, No. 96, Part 3.) five eastern Kansas black shale units were selected for study and their areal distribution mapped. The volume of recoverable oil shale in each unit was calculated and translated to reserves. The report concludes that in all probability, extraction of oil shale for shale oil is not feasible at this time due to the cost of extraction, transportation and processing. The report recommends that additional studies be undertaken to provide a more comprehensive and detailed assessment of Kansas oil shales as a potential fuel resource. 49 references, 4 tables.« less

Depositional setting and geochemistry of phosphorites and metalliferous black shales in the Carboniferous-Permian Lisburne Group, Northern Alaska

USGS Publications Warehouse

Dumoulin, Julie A.; Slack, John F.; Whalen, Michael T.; Harris, Anita G.

2011-01-01

Phosphatic rocks are distributed widely in the Lisburne Group, a mainly Carboniferous carbonate succession that occurs throughout northern Alaska. New sedimentologic, paleontologic, and geochemical data presented here constrain the geographic and stratigraphic extent of these strata and their depositional and paleogeographic settings. Our findings support models that propose very high oxygen contents of the Permo-Carboniferous atmosphere and oceans, and those that suggest enhanced phosphogenesis in iron-limited sediments; our data also have implications for Carboniferous paleogeography of the Arctic. Lisburne Group phosphorites range from granular to nodular, are interbedded with black shale and lime mudstone rich in radiolarians and sponge spicules, and accumulated primarily in suboxic outer- to middle-ramp environments. Age constraints from conodonts, foraminifers, and goniatite cephalopods indicate that most are middle Late Mississippian (early Chesterian; early late Visean). Phosphorites form 2- to 40-cm-thick beds of sand- to pebble-sized phosphatic peloids, coated grains, and (or) bioclasts cemented by carbonate, silica, or phosphate that occur through an interval =12 m thick. High gamma-ray response through this interval suggests strongly condensed facies related to sediment starvation and development of phosphatic hardgrounds. Phosphorite textures, such as unconformity-bounded coated grains, record multiple episodes of phosphogenesis and sedimentary reworking. Sharp bed bases and local grading indicate considerable redeposition of phosphatic material into deeper water by storms and (or) gravity flows. Lisburne Group phosphorites contain up to 37 weight percent P2O5, 7.6 weight percent F, 1,030 ppm Y, 517 ppm La, and 166 ppm U. Shale-normalized rare earth element (REE) plots show uniformly large negative Ce anomalies Ce/Ce*=0.11 + or - 0.03) that are interpreted to reflect phosphate deposition in seawater that was greatly depleted in Ce due to increased oxygenation of the atmosphere and oceans during the Carboniferous evolution of large vascular land plants. Black shales within the phosphorite sections have up to 20.2 weight percent Corg and are potential petroleum source rocks. Locally, these strata also are metalliferous, with up to 1,690 ppm Cr, 2,831 ppm V, 551 ppm Ni, 4,670 ppm Zn, 312 ppm Cu, 43.5 ppm Ag, and 12.3 ppm Tl; concentrations of these metals covary broadly with Corg, suggesting coupled redox variations. Calculated marine fractions (MF) of Cr, V, and Mo, used to evaluate the paleoredox state of the bottom waters, show generally high CrMF/MoMF and VMF/MoMF ratios that indicate deposition of the black shales under suboxic denitrifying conditions; Re/Mo ratios also plot mainly within the suboxic field and support this interpretation. Predominantly seawater and biogenic sources are indicated for Cr, V, Mo, Zn, Cd, Ni, and Cu in the black shales, with an additional hydrothermal contribution inferred for Zn, Cd, Ag, and Tl in some samples. Lisburne Group phosphorites formed in the Ikpikpuk Basin and along both sides of the mud- and chert-rich Kuna Basin, which hosts giant massive sulfide and barite deposits of the Red Dog district. Lisburne Group phosphatic strata are coeval with these deposits and formed in response to a nutrient-rich upwelling regime. Phosphate deposition occurred mainly in suboxic bottom waters based on data for paleoredox proxies (Cr, V, Mo, Re) within contemporaneous black shales. Recent global reconstructions are consistent with Carboniferous upwelling in northern Alaska, but differ in the type of upwelling expected (zonal versus meridional). Paleoenvironmental data suggest that meridional upwelling may better explain phosphorite deposition in the Lisburne Group.

In search of a Silurian Total Petroleum System in the Appalachian Basin of New York, Ohio, Pennsylvania, and West Virginia

USGS Publications Warehouse

Ryder, Robert T.; Swezey, Christopher S.; Trippi, Michael H.; Lentz, Erika E.; Avary, K. Lee; Harper, John A.; Kappel, William M.; Rea, Ronald G.

2007-01-01

This report provides an evaluation of the source rock potential of Silurian strata in the U.S. portion of the northern Appalachian Basin, using new TOC and RockEval data. The study area consists of all or parts of New York, Ohio, Pennsylvania, and West Virginia. The stratigraphic intervals that were sampled for this study are as follows: 1) the Lower Silurian Cabot Head Shale, Rochester Shale, and Rose Hill Formation; 2) the Lower and Upper Silurian McKenzie Limestone, Lockport Dolomite, and Eramosa Member of the Lockport Group; and 3) the Upper Silurian Wills Creek Formation, Tonoloway Limestone, Salina Group, and Bass Islands Dolomite. These Silurian stratigraphic intervals were chosen because they are cited in previous publications as potential source rocks, they are easily identified and relatively continuous across the basin, and they contain beds of dark gray to black shale and (or) black argillaceous limestone and dolomite.

Is air pollution causing landslides in China?

NASA Astrophysics Data System (ADS)

Zhang, Ming; McSaveney, Mauri J.

2018-01-01

Air pollution in China often exceeds "unhealthy" levels, but Chinese air is not only a threat from being breathed: the pollutants may also be causing fatal landslides. Very acid rain from severe air pollution falls widely in southwest China, where coal is a major energy source. We discuss where acid rain may provide an unsuspected link between mining and the fatal 2009 Jiweishan landslide in southwest China; it may have reduced the strength of a thin, calcareous, black sapropelic shale in Jiweishan Mountain by removing cementing carbonate minerals and sapropel matrix. Mining beneath the potential slide mass may not have directly triggered the landslide, but collapse of abandoned adits drained a perched aquifer above a regional black-shale aquiclude. Inflow of acid, oxygenated water and nutrients into the aquiclude may have accelerated the reduction of strength of the weakest rocks and consequently led to rapid sliding of a large rock mass on a layer of weathered shale left composed largely of soft, and slippery talc.

Two-brine model of the genesis of strata-bound Zechstein deposits (Kupferschiefer type), Poland

NASA Astrophysics Data System (ADS)

Kucha, H.; Pawlikowski, M.

1986-01-01

These Kupferschiefer deposits were probably formed as a result of a mixing of two brines. The upper cold brine (UCB) is an unmineralized brine rich in Na, Ca, Cl and SO4, with a pH>7 and originating from evaporites overlying the metal-bearing Zechstein rocks. The lower hot brine (LHB) rich in Mg, K, Cl, SO4 and CO3 with a pH<=7 formed in sediments in the central part of the Zechstein basin at a depth of 7,000 m. This brine was subjected to heating and upward convection toward the Fore-Sudetic monocline along the bottom of the Z1 carbonates. During its migration, it caused albitization, serpentinization and leaching of the primary metal deposits in rocks underlying the Zechstein becoming enriched in heavy metals. The mineralization process, being a result of the mixing of the two brines (UCB and LHB), and catalytic oxidation of the organic matter of the black shale were initiated at shallow depths in the area of the Fore-Sudetic monocline. The boundary of the two brines generally overlapped the strike of the black shale. Parts of the deposit with shale-free host rock suggest that the action of two brines alone was capable of producing economic concentrations of Cu, Pb and Zn. Where the boundary of the two brines overlaps the autooxidation zone (the black shale bottom) and also coincides with γ radiation of thucholite, concentrations of noble metals result. The characteristic vertical distribution of the triplet Cu→Pb→Zn from the bottom upward is universal in the Kupferschiefer environment.

Ultraviolet laser-induced lateral photovoltaic response in anisotropic black shale

NASA Astrophysics Data System (ADS)

Miao, Xinyang; Zhu, Jing; Zhao, Kun; Yue, Wenzheng

2017-12-01

The anisotropy of shale has significant impact on oil and gas exploration and engineering. In this paper, a-248 nm ultraviolet laser was employed to assess the anisotropic lateral photovoltaic (LPV) response of shale. Anisotropic angle-depending voltage signals were observed with different peak amplitudes ( V p) and decay times. We employed exponential models to explain the charge carrier transport in horizontal and vertical directions. Dependences of the laser-induced LPV on the laser spot position were observed. Owing to the Dember effect and the layered structure of shale, V p shows an approximately linear dependence with the laser-irradiated position for the 0° shale sample but nonlinearity for the 45° and 90° ones. The results demonstrate that the laser-induced voltage method is very sensitive to the structure of materials, and thus has a great potential in oil and gas reservoir characterization.

Geochemical and isotopic evidence for paleoredox conditions during deposition of the Devonian-Mississippian New Albany Shale, southern Indiana

NASA Technical Reports Server (NTRS)

Beier, J. A.; Hayes, J. M.

1989-01-01

The upper part of the New Albany Shale is divided into three members. In ascending order, these are (1) the Morgan Trail Member, a laminated brownish-black shale; (2) the Camp Run Member, an interbedded brownish-black and greenish-gray shale; and (3) the Clegg Creek Member, also a laminated brownish-black shale. The Morgan Trail and Camp Run Members contain 5% to 6% total organic carbon (TOC) and 2% sulfide sulfur. Isotopic composition of sulfide in these members ranges from -5.0% to -20.0%. C/S plots indicate linear relationships between abundances of these elements, with a zero intercept characteristic of sediments deposited in a non-euxinic marine environment. Formation of diagenetic pyrite was carbon limited in these members. The Clegg Creek Member contains 10% to 15% TOC and 2% to 6% sulfide sulfur. Isotopic compositions of sulfide range from -5.0% to -40%. The most negative values occur in the uppermost Clegg Creek Member and are characteristic of syngenetic pyrite, formed within an anoxic water column. Abundances of carbon and sulfur are greater and uncorrelated in this member, consistent with deposition in as euxinic environment. In addition, DOP (degree of pyritization) values suggest that formation of pyrite was generally iron limited throughout Clegg Creek deposition, but sulfur isotopes indicate that syngenetic (water-column) pyrite becomes an important component in the sediment only in the upper part of the member. At the top of the Clegg Creek Member, a zone of phosphate nodules and trace-metal enrichment coincides with maximal TOC values. During euxinic deposition, phosphate and trace metals accumulated below the chemocline because of limited vertical circulation in the water column. Increased productivity would have resulted in an increased flux of particulate organic matter to the sediment, providing an effective sink for trace metals in the water column. Phosphate and trace metals released from organic matter during early diagenesis resulted in precipitation of metal-rich phosphate nodules.

Palaeoredox conditions and sequence stratigraphy of the Cretaceous storm-dominated, mixed siliciclastic-carbonate ramp in the Eastern Cordillera Basin (Colombia): Evidence from sedimentary geochemical proxies and facies analysis

NASA Astrophysics Data System (ADS)

Rivera, Huber A.; Le Roux, Jacobus P.; Sánchez, L. Katherine; Mariño-Martínez, Jorge E.; Salazar, Christian; Barragán, J. Carolina

2018-10-01

The Cretaceous black shales of Colombia are among the most important successions in the north of South America and have attracted the attention of many geoscientists and exploration companies over the last few decades, because of their high hydrocarbon potential and the presence of emerald deposits. However, many uncertainties still remain with regard to their tectonic setting, sequence stratigraphy, depositional environments, palaeoxygenation conditions, and organic matter preservation. In order to develop a more integrated picture of these different processes and conditions, we conducted a detailed sedimentological, inorganic geochemical (U, V, Ni, Zn, Mn, Fe, Ti, Mo, Cu, Cr, Cd, Ba) and sequence stratigraphic analysis of the Cretaceous black shales in the Magdalena-Tablazo Sub-Basin (Eastern Cordillera Basin) of Colombia. Eleven lithofacies and five lithofacies associations of a storm-dominated, siliciclastic-carbonate ramp were identified, which range from basin to shallow inner ramp environments. These facies were grouped into six third-order stratigraphic sequences showing high-order cycles of marine transgression with constrained regressive pulses during the late Valanginian to early Coniacian. The black shales succession represents deposition under anoxic bottom water with some intervals representing dysoxic-suboxic conditions. The evolution of the sedimentary environments and their palaeoxygenation history reflect tectonic and eustatic sea-level controls that 1) produced a variable orientation and position of the coastline throughout the Cretaceous; 2) conditioned the low-gradient ramp geometry (<0.3°) and 3) modified the oxygenation conditions in the Magdalena-Tablazo Sub-Basin. An improved understanding of the sedimentary setting during deposition of the Cretaceous black shales in the Magdalena-Tablazo Sub-Basin assists in highlighting the interplay between the mechanism of sedimentation and continuum anoxic conditions prevailing in a basin, as well the important role of nutrient input from continental runoff as a trigger of high productivity and extended anoxia conditions.

Western Greece unconventional hydrocarbon potential from oil shale and shale gas reservoirs

NASA Astrophysics Data System (ADS)

Karakitsios, Vasileios; Agiadi, Konstantina

2013-04-01

It is clear that we are gradually running out of new sedimentary basins to explore for conventional oil and gas and that the reserves of conventional oil, which can be produced cheaply, are limited. This is the reason why several major oil companies invest in what are often called unconventional hydrocarbons: mainly oil shales, heavy oil, tar sand and shale gas. In western Greece exist important oil and gas shale reservoirs which must be added to its hydrocarbon potential1,2. Regarding oil shales, Western Greece presents significant underground immature, or close to the early maturation stage, source rocks with black shale composition. These source rock oils may be produced by applying an in-situ conversion process (ICP). A modern technology, yet unproven at a commercial scale, is the thermally conductive in-situ conversion technology, developed by Shell3. Since most of western Greece source rocks are black shales with high organic content, those, which are immature or close to the maturity limit have sufficient thickness and are located below 1500 meters depth, may be converted artificially by in situ pyrolysis. In western Greece, there are several extensive areas with these characteristics, which may be subject of exploitation in the future2. Shale gas reservoirs in Western Greece are quite possibly present in all areas where shales occur below the ground-water level, with significant extent and organic matter content greater than 1%, and during their geological history, were found under conditions corresponding to the gas window (generally at depths over 5,000 to 6,000m). Western Greece contains argillaceous source rocks, found within the gas window, from which shale gas may be produced and consequently these rocks represent exploitable shale gas reservoirs. Considering the inevitable increase in crude oil prices, it is expected that at some point soon Western Greece shales will most probably be targeted. Exploration for conventional petroleum reservoirs, through the interpretation of seismic profiles and the surface geological data, will simultaneously provide the subsurface geometry of the unconventional reservoirs. Their exploitation should follow that of conventional hydrocarbons, in order to benefit from the anticipated technological advances, eliminating environmental repercussions. As a realistic approach, the environmental consequences of the oil shale and shale gas exploitation to the natural environment of western Greece, which holds other very significant natural resources, should be delved into as early as possible. References 1Karakitsios V. & Rigakis N. 2007. Evolution and Petroleum Potential of Western Greece. J.Petroleum Geology, v. 30, no. 3, p. 197-218. 2Karakitsios V. 2013. Western Greece and Ionian Sea petroleum systems. AAPG Bulletin, in press. 3Bartis J.T., Latourrette T., Dixon L., Peterson D.J., Cecchine G. 2005. Oil Shale Development in the United States: Prospect and Policy Issues. Prepared for the National Energy Tech. Lab. of the U.S. Dept Energy. RAND Corporation, 65 p.

Experimental Investigation of Mechanical Properties of Black Shales after CO₂-Water-Rock Interaction.

PubMed

Lyu, Qiao; Ranjith, Pathegama Gamage; Long, Xinping; Ji, Bin

2016-08-06

The effects of CO₂-water-rock interactions on the mechanical properties of shale are essential for estimating the possibility of sequestrating CO₂ in shale reservoirs. In this study, uniaxial compressive strength (UCS) tests together with an acoustic emission (AE) system and SEM and EDS analysis were performed to investigate the mechanical properties and microstructural changes of black shales with different saturation times (10 days, 20 days and 30 days) in water dissoluted with gaseous/super-critical CO₂. According to the experimental results, the values of UCS, Young's modulus and brittleness index decrease gradually with increasing saturation time in water with gaseous/super-critical CO₂. Compared to samples without saturation, 30-day saturation causes reductions of 56.43% in UCS and 54.21% in Young's modulus for gaseous saturated samples, and 66.05% in UCS and 56.32% in Young's modulus for super-critical saturated samples, respectively. The brittleness index also decreases drastically from 84.3% for samples without saturation to 50.9% for samples saturated in water with gaseous CO₂, to 47.9% for samples saturated in water with super-critical carbon dioxide (SC-CO₂). SC-CO₂ causes a greater reduction of shale's mechanical properties. The crack propagation results obtained from the AE system show that longer saturation time produces higher peak cumulative AE energy. SEM images show that many pores occur when shale samples are saturated in water with gaseous/super-critical CO₂. The EDS results show that CO₂-water-rock interactions increase the percentages of C and Fe and decrease the percentages of Al and K on the surface of saturated samples when compared to samples without saturation.

Transient episodes of mild environmental oxygenation and oxidative continental weathering during the late Archean

PubMed Central

Kendall, Brian; Creaser, Robert A.; Reinhard, Christopher T.; Lyons, Timothy W.; Anbar, Ariel D.

2015-01-01

It is not known whether environmental O2 levels increased in a linear fashion or fluctuated dynamically between the evolution of oxygenic photosynthesis and the later Great Oxidation Event. New rhenium-osmium isotope data from the late Archean Mount McRae Shale, Western Australia, reveal a transient episode of oxidative continental weathering more than 50 million years before the onset of the Great Oxidation Event. A depositional age of 2495 ± 14 million years and an initial 187Os/188Os of 0.34 ± 0.19 were obtained for rhenium- and molybdenum-rich black shales. The initial 187Os/188Os is higher than the mantle/extraterrestrial value of 0.11, pointing to mild environmental oxygenation and oxidative mobilization of rhenium, molybdenum, and radiogenic osmium from the upper continental crust and to contemporaneous transport of these metals to seawater. By contrast, stratigraphically overlying black shales are rhenium- and molybdenum-poor and have a mantle-like initial 187Os/188Os of 0.06 ± 0.09, indicating a reduced continental flux of rhenium, molybdenum, and osmium to seawater because of a drop in environmental O2 levels. Transient oxygenation events, like the one captured by the Mount McRae Shale, probably separated intervals of less oxygenated conditions during the late Archean. PMID:26702438

Geology and total petroleum systems of the Paradox Basin, Utah, Colorado, New Mexico, and Arizona

USGS Publications Warehouse

Whidden, Katherine J.; Lillis, Paul G.; Anna, Lawrence O.; Pearson, Krystal M.; Dubiel, Russell F.

2014-01-01

The most studied source intervals are the Pennsylvanian black shales that were deposited during relative high stands in an otherwise evaporitic basin. These black shales are the source for most of the discovered hydrocarbons in the Paradox Basin. A second oil type can be traced to either a Mississippian or Permian source rock to the west, and therefore requires long-distance migration to explain its presence in the basin. Upper Cretaceous continental to nearshore-marine sandstones are interbedded with coal beds that have recognized coalbed methane potential. Precambrian and Devonian TPSs are considered hypothetical, as both are known to have organic-rich intervals, but no discovered hydrocarbons have been definitively typed back to either of these units.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barron, L.S.; Ettensohn, F.R.

The Devonian-Mississippian black-shale sequence is one of the most prominent and well-known stratigraphic horizons in the Paleozoic of the United States, yet the paleontology and its paleoecologic and paleoenvironmental implications are poorly known. This is in larger part related to the scarcity of fossils preserved in the shale - in terms of both diversity and abundance. Nonetheless, that biota which is preserved is well-known and much described, but there is little synthesis of this data. The first step in such a synthesis is the compilation of an inclusive bibliography such as this one. This bibliography contains 1193 entries covering allmore » the major works dealing with Devonian-Mississippian black-shale paleontology and paleoecology in North America. Articles dealing with areas of peripheral interest, such as paleogeography, paleoclimatology, ocean circulation and chemistry, and modern analogues, are also cited. In the index, the various genera, taxonomic groups, and other general topics are cross-referenced to the cited articles. It is hoped that this compilation will aid in the synthesis of paleontologic and paleoecologic data toward a better understanding of these unique rocks and their role as a source of energy.« less

Chlorophyll Diagenesis in the Water Column and Sediments of the Black Sea

DTIC Science & Technology

1993-02-01

R., Daley R. J., and McNeely R. N. (1977) Composition and stratigraphy of the fossil phorbin derivatives of Little Round Lake, Ontario. Limnol...and Albrecht P. (1987), Isotopic compositions and probable origins of organic molecules in the Eocene Messel shale, Nature 329, 48-51. Honjo S. and...bacteriopetroporphyrins in oil shale. J. Chem. Soc., Chem. Commun. 1985, 200-201. Ocampo R., Callot H. J., and Albrecht P. (1989) Different isotope compositions of C

Pyrolysis gas chromatography-mass spectrometry to characterize organic matter and its relationship to uranium content of Appalachian Devonian black shales

USGS Publications Warehouse

Leventhal, J.S.

1981-01-01

Gas Chromatographic analysis of volatile products formed by stepwise pyrolysis of black shales can be used to characterize the kerogen by relating it to separated, identified precursors such as land-derived vitrinite and marine-source Tasmanites. Analysis of a Tasmanites sample shows exclusively n-alkane and -alkene pyrolysis products, whereas a vitrinite sample shows a predominance of one- and two-ring substituted aromatics. For core samples from northern Tennessee and for a suite of outcrop samples from eastern Kentucky, the organic matter type and the U content (<10-120ppm) show variations that are related to precursor organic materials. The samples that show a high vitrinite component in their pyrolysis products are also those samples with high contents of U. ?? 1981.

Gas shale/oil shale

USGS Publications Warehouse

Fishman, N.S.; Bereskin, S.R.; Bowker, K.A.; Cardott, B.J.; Chidsey, T.C.; Dubiel, R.F.; Enomoto, C.B.; Harrison, W.B.; Jarvie, D.M.; Jenkins, C.L.; LeFever, J.A.; Li, Peng; McCracken, J.N.; Morgan, C.D.; Nordeng, S.H.; Nyahay, R.E.; Schamel, Steven; Sumner, R.L.; Wray, L.L.

2011-01-01

The production of natural gas from shales continues to increase in North America, and shale gas exploration is on the rise in other parts of the world since the previous report by this committee was published by American Association of Petroleum Geologists, Energy Minerals Division (2009). For the United States, the volume of proved reserves of natural gas increased 11% from 2008 to 2009, the increase driven largely by shale gas development (Energy Information Administration 2010c). Furthermore, shales have increasingly become targets of exploration for oil and condensate as well as gas, which has served to greatly expand their significance as ‘‘unconventional’’ petroleum reservoirs.This report provides information about specific shales across North America and Europe from which gas (biogenic or thermogenic), oil, or natural gas liquids are produced or is actively being explored. The intent is to reflect the recently expanded mission of the Energy Minerals Division (EMD) Gas Shales Committee to serve as a single point of access to technical information on shales regardless of the type of hydrocarbon produced from them. The contents of this report were drawn largely from contributions by numerous members of the EMD Gas Shales Advisory Committee, with much of the data being available from public websites such as state or provincial geological surveys or other public institutions. Shales from which gas or oil is being produced in the United States are listed in alphabetical order by shale name. Information for Canada is presented by province, whereas for Europe, it is presented by country.

Dissolution of cemented fractures in gas bearing shales in the context of CO2 sequestration

NASA Astrophysics Data System (ADS)

Kwiatkowski, Kamil; Szymczak, Piotr

2016-04-01

Carbon dioxide has a stronger binding than methane to the organic matter contained in the matrix of shale rocks [1]. Thus, the injection of CO2 into shale formation may enhance the production rate and total amount of produced methane, and simultaneously permanently store pumped CO2. Carbon dioxide can be injected during the initial fracking stage as CO2 based hydraulic fracturing, and/or later, as a part of enhanced gas recovery (EGR) [2]. Economic and environmental benefits makes CO2 sequestration in shales potentially very for industrial-scale operation [3]. However, the effective process requires large area of fracture-matrix interface, where CO2 and CH4 can be exchanged. Usually natural fractures, existing in shale formation, are preferentially reactivated during hydraulic fracturing, thus they considerably contribute to the flow paths in the resulting fracture system [4]. Unfortunately, very often these natural fractures are sealed by calcite [5]. Consequently the layer of calcite coating surfaces impedes exchange of gases, both CO2 and CH4, between shale matrix and fracture. In this communication we address the question whether carbonic acid, formed when CO2 is mixed with brine, is able to effectively dissolve a calcite layer present in the natural fractures. We investigate numerically fluid flow and dissolution of calcite coating in natural shale fractures, with CO2-brine mixture as a reactive fluid. Moreover, we discuss the differences between slow dissolution (driven by carbonic acid) and fast dissolution (driven by stronger hydrochloric acid) of calcite layer. We compare an impact of the flow rate and geometry of the fracture on the parameters of practical importance: available surface area, morphology of dissolution front, time scale of the dissolution, and the penetration length. We investigate whether the dissolution is sufficiently non-uniform to retain the fracture permeability, even in the absence of the proppant. The sizes of analysed fractures varying from 0.2 x 0.2 m2 up to 4 x 4 m2, together with discussion of a further upscaling, make the study relevant to the industrial applications. While the results of this study should be applicable to different shale formations throughout the world, we discuss them in the context of preparation to gas-production from Pomeranian shale basin, located in the northern Poland. [1] Mosher, K., He, J., Liu, Y., Rupp, E., & Wilcox, J. Molecular simulation of methane adsorption in micro-and mesoporous carbons with applications to coal and gas shale systems. International Journal of Coal Geology, 109, 36-44 (2013) [2] Grieser, W. V., Wheaton, W. E., Magness, W. D., Blauch, M. E., & Loghry, R, "Surface Reactive Fluid's Effect on Shale." Proceedings of the Production and Operations Symposium, 31 March-3 April 2007, Oklahoma City (SPE-106815-MS) [3] Tao, Z. and Clarens, A., Estimating the carbon sequestration capacity of shale formations using methane production rates, Environmental Science and Technology, 47, 11318-11325 (2013). [4] Zhang, X., Jeffrey, R. G., & Thiercelin, M. (2009). Mechanics of fluid-driven fracture growth in naturally fractured reservoirs with simple network geometries. Journal of Geophysical Research: Solid Earth, 114, B12406 (2009) [5] Gale, J.F., Laubach, S.E., Olson, J.E., Eichhubl, P., Fall, A. Natural fractures in shale: A review and new observations. AAPG Bulletin 98(11):2165-2216 (2014)

High-resolution stratigraphic analyses of Permian-Triassic core material recovered in central Spitsbergen

NASA Astrophysics Data System (ADS)

Sleveland, Arve; Planke, Sverre; Zuchuat, Valentin; Franeck, Franziska; Svensen, Henrik; Midtkandal, Ivar; Hammer, Øyvind; Twitchett, Richard; Deltadalen Study Group

2017-04-01

The Siberian Traps voluminous igneous activity is considered a likely trigger for the Permian-Triassic global extinction event. However, documented evidence of the Siberian Traps environmental effects decreases away from the centre of volcanic activity in north-central Russia. Previous research on the Permian-Triassic boundary (PTB) mostly relies on field observations, and resolution has thus depended on outcrop quality. This study reports on two 90 m cored sedimentary successions intersecting the PTB in Deltadalen, Svalbard, providing high-quality material to a comprehensive documentation of the stratigraphic interval. Sequence stratigraphic concepts are utilised to help constrain the Permian-Triassic basin development models in Svalbard and the high-Arctic region. The cored sections are calibrated with outcrop data from near the drill site. One core has been systematically described and scanned using 500-μm and 200-μm resolution XRF, hyperspectral imagery and microfocus CT (latter only on selected core sections). The base of both cores represents the upper 15 m of the Permian Kapp Starostin Formation, which is dominated by green glauconitic sandstones with spiculitic cherts, and exhibit various degrees of bioturbation. The Kapp Starostin Formation is in turn sharply overlain by 2 m of heavily reworked sand- and mudstones, extensively bioturbated, representing the base of the lower Triassic Vikinghøgda Formation. These bioturbated units are conformably overlain by 9 m of ash-bearing laminated black shale where signs of biological activity both on micro- and macro-scale are limited, and is thus interpreted to have recorded the Permian-Triassic extinction interval. Descriptive sedimentology and sequence stratigraphic concepts reveal the onset of relative sea level rise at the Vikinghøgda Formation base. The disappearance of bioturbation and extensive presence of pyrite in the overlying laminated black shale of the Vikinghøgda Formation suggest near anoxic conditions. The maximum flooding surface is recorded 6 m above the base of the Vikinghøgda Formation, in the middle of the laminated black shale and indicates that the lower ash-layers are tied to igneous activity at a time of relatively high sea level. The remaining succession above the laminated black shale is an overall aggradational interval of interbedded clay- and siltstones of the Vikinghøgda Formation, marking the return of biological activity at its base. The Vikinghøgda Formation includes 18 preserved zircon-bearing ash-layers, providing an opportunity for accurate U/Pb dating. Detailed cyclostratigraphic analyses of the laminated black shale suggest a sedimentation rate of approximately 0.5 cm/kyr, and provides thus, together with the U/Pb zircon ages, a great tool for high-resolution documentation of the PTB interval.

A modern vs. Permian black shale - the hydrography, primary productivity, and water-column chemistry of deposition

USGS Publications Warehouse

Piper, D.Z.; Perkins, R.B.

2004-01-01

The sediment currently accumulating in the Cariaco Basin, on the continental shelf of Venezuela, has an elevated organic-carbon content of approximately 5%; is accumulating under O2-depleted bottom-water conditions (SO42- reduction); is composed dominantly of foraminiferal calcite, diatomaceous silica, clay, and silt; and is dark greenish gray in color. Upon lithification, it will become a black shale. Recent studies have established the hydrography of the basin and the level of primary productivity and bottom-water redox conditions. These properties are used to model accumulation rates of Cd, Cr, Cu, Mo, Ni, V, and Zn on the seafloor. The model rates agree closely with measured rates for the uppermost surface sediment.The model is applied to the Meade Peak Phosphatic Shale Member of the Phosphoria Formation, a phosphate deposit of Permian age in the northwest United States. It too has all of the requisite properties of a black shale. Although the deposit is a world-class phosphorite, it is composed mostly of phosphatic mudstone and siltstone, chert, limestone, and dolomite. It has organic-carbon concentrations of up to 15%, is strongly enriched in several trace elements above a terrigenous contribution and is black. The trace-element accumulation defines a mean primary productivity in the photic zone of the Phosphoria Basin as moderate, at 500 g m-2 year-1 organic carbon, comparable to primary productivity in the Cariaco Basin. The source of nutrient-enriched water that was imported into the Phosphoria Basin, upwelled into the photic zone, and supported primary productivity was an O2 minimum zone of the open ocean. The depth range over which the water was imported would have been between approximately 100 and 600 m. The mean residence time of bottom water in the basin was approximately 4 years vs. 100 years in the Cariaco Basin. The bottom water was O2 depleted, but it was denitrifying, or NO3- reducing, rather than SO42- reducing. Published by Elsevier B.V.

Experimental investigation on the fracture behaviour of black shale by acoustic emission monitoring and CT image analysis during uniaxial compression

NASA Astrophysics Data System (ADS)

Wang, Y.; Li, C. H.; Hu, Y. Z.

2018-04-01

Plenty of mechanical experiments have been done to investigate the deformation and failure characteristics of shale; however, the anisotropic failure mechanism has not been well studied. Here, laboratory Uniaxial Compressive Strength tests on cylindrical shale samples obtained by drilling at different inclinations to bedding plane were performed. The failure behaviours of the shale samples were studied by real-time acoustic emission (AE) monitoring and post-test X-ray computer tomography (CT) analysis. The experimental results suggest that the pronounced bedding planes of shale have a great influence on the mechanical properties and AE patterns. The AE counts and AE cumulative energy release curves clearly demonstrate different morphology, and the `U'-shaped curve relationship between the AE counts, AE cumulative energy release and bedding inclination was first documented. The post-test CT image analysis shows the crack patterns via 2-D image reconstructions, an index of stimulated fracture density is defined to represent the anisotropic failure mode of shale. What is more, the most striking finding is that the AE monitoring results are in good agreement with the CT analysis. The structural difference in the shale sample is the controlling factor resulting in the anisotropy of AE patterns. The pronounced bedding structure in the shale formation results in an anisotropy of elasticity, strength and AE information from which the changes in strength dominate the entire failure pattern of the shale samples.

Hydraulic fracturing offers view of microbial life in the deep terrestrial subsurface.

PubMed

Mouser, Paula J; Borton, Mikayla; Darrah, Thomas H; Hartsock, Angela; Wrighton, Kelly C

2016-11-01

Horizontal drilling and hydraulic fracturing are increasingly used for recovering energy resources in black shales across the globe. Although newly drilled wells are providing access to rocks and fluids from kilometer depths to study the deep biosphere, we have much to learn about microbial ecology of shales before and after 'fracking'. Recent studies provide a framework for considering how engineering activities alter this rock-hosted ecosystem. We first provide data on the geochemical environment and microbial habitability in pristine shales. Next, we summarize data showing the same pattern across fractured shales: diverse assemblages of microbes are introduced into the subsurface, eventually converging to a low diversity, halotolerant, bacterial and archaeal community. Data we synthesized show that the shale microbial community predictably shifts in response to temporal changes in geochemistry, favoring conservation of key microorganisms regardless of inputs, shale location or operators. We identified factors that constrain diversity in the shale and inhibit biodegradation at the surface, including salinity, biocides, substrates and redox. Continued research in this engineered ecosystem is required to assess additive biodegradability, quantify infrastructure biocorrosion, treat wastewaters that return to the surface and potentially enhance energy production through in situ methanogenesis. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Experimental Investigation of Mechanical Properties of Black Shales after CO2-Water-Rock Interaction

PubMed Central

Lyu, Qiao; Ranjith, Pathegama Gamage; Long, Xinping; Ji, Bin

2016-01-01

The effects of CO2-water-rock interactions on the mechanical properties of shale are essential for estimating the possibility of sequestrating CO2 in shale reservoirs. In this study, uniaxial compressive strength (UCS) tests together with an acoustic emission (AE) system and SEM and EDS analysis were performed to investigate the mechanical properties and microstructural changes of black shales with different saturation times (10 days, 20 days and 30 days) in water dissoluted with gaseous/super-critical CO2. According to the experimental results, the values of UCS, Young’s modulus and brittleness index decrease gradually with increasing saturation time in water with gaseous/super-critical CO2. Compared to samples without saturation, 30-day saturation causes reductions of 56.43% in UCS and 54.21% in Young’s modulus for gaseous saturated samples, and 66.05% in UCS and 56.32% in Young’s modulus for super-critical saturated samples, respectively. The brittleness index also decreases drastically from 84.3% for samples without saturation to 50.9% for samples saturated in water with gaseous CO2, to 47.9% for samples saturated in water with super-critical carbon dioxide (SC-CO2). SC-CO2 causes a greater reduction of shale’s mechanical properties. The crack propagation results obtained from the AE system show that longer saturation time produces higher peak cumulative AE energy. SEM images show that many pores occur when shale samples are saturated in water with gaseous/super-critical CO2. The EDS results show that CO2-water-rock interactions increase the percentages of C and Fe and decrease the percentages of Al and K on the surface of saturated samples when compared to samples without saturation. PMID:28773784

Constraints on Upward Migration of Hydraulic Fracturing Fluid and Brine

PubMed Central

Flewelling, Samuel A; Sharma, Manu

2014-01-01

Recent increases in the use of hydraulic fracturing (HF) to aid extraction of oil and gas from black shales have raised concerns regarding potential environmental effects associated with predictions of upward migration of HF fluid and brine. Some recent studies have suggested that such upward migration can be large and that timescales for migration can be as short as a few years. In this article, we discuss the physical constraints on upward fluid migration from black shales (e.g., the Marcellus, Bakken, and Eagle Ford) to shallow aquifers, taking into account the potential changes to the subsurface brought about by HF. Our review of the literature indicates that HF affects a very limited portion of the entire thickness of the overlying bedrock and therefore, is unable to create direct hydraulic communication between black shales and shallow aquifers via induced fractures. As a result, upward migration of HF fluid and brine is controlled by preexisting hydraulic gradients and bedrock permeability. We show that in cases where there is an upward gradient, permeability is low, upward flow rates are low, and mean travel times are long (often >106 years). Consequently, the recently proposed rapid upward migration of brine and HF fluid, predicted to occur as a result of increased HF activity, does not appear to be physically plausible. Unrealistically high estimates of upward flow are the result of invalid assumptions about HF and the hydrogeology of sedimentary basins. PMID:23895673

Determination of factors responsible for the bioweathering of copper minerals from organic-rich copper-bearing Kupferschiefer black shale.

PubMed

Włodarczyk, Agnieszka; Szymańska, Agata; Skłodowska, Aleksandra; Matlakowska, Renata

2016-04-01

The aim of this study was to investigate the bioweathering of copper minerals present in the alkaline, copper-bearing and organic-rich Kupferschiefer black shale through the action of a consortium of indigenous lithobiontic, heterotrophic, neutrophilic bacteria isolated from this sedimentary rock. The involvement of microorganisms in the direct/enzymatic bioweathering of fossil organic matter of the rock was confirmed. As a result of bacterial activity, a spectrum of various organic compounds such as urea and phosphoric acid tributyl ester were released from the rock. These compounds indirectly act on the copper minerals occurring in the rock and cause them to weather. This process was reflected in the mobilization of copper, iron and sulfur and in changes in the appearance of copper minerals observed under reflected light. The potential role of identified enzymes in biodegradation of fossil organic matter and role of organic compounds released from black shale as a result of this process in copper minerals weathering was discussed. The presented results provide a new insight into the role of chemical compounds released by bacteria during fossil organic matter bioweathering potentially important in the cycling of copper and iron deposited in the sedimentary rock. The originality of the described phenomenon lies in the fact that the bioweathering of fossil organic matter and, consequently, of copper minerals occur simultaneously in the same environment, without any additional sources of energy, electrons and carbon. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reconstruction of paleoenvironment recorded in the Ediacaran Lantain black shales

NASA Astrophysics Data System (ADS)

Liu, Y. H.; Lee, D. C.; You, C. F.; Zhou, C.

2016-12-01

The Ediacaran period (635-542 Ma) was a critical time in the history of life and Earth, during which profound changes in complex megascopic life and probably ocean oxygenation occurred. A growing evidence demonstrates that the Early Ediacaran ocean was not simply a largely anoxic basin as previous thought. Pulsed oxidation or a multilayered water column had been proposed to explain the presence of Lantain macrofossils. To verify these models, in-situ isotopic analysis becomes critical in identifying the isotopic signatures of authigenic minerals, and to avoid mixing in the signals from detrital and diagenetic phases. In this study, samples from Lantain Member II, a 40 m thick black shale unit containing macrofossils and overlaying the cap carbonate, were analyzed, including one sample from the lower part of Member II and six samples from upper part of Member II. Abundant xenotimes were overgrown on the detrital zircon grains during early diagenesis in all the samples. This authigenic phosphate mineral provides the best constraint of depositional age. In addition, framboidal pyrites and microbial mats are alternatively present on the top of Member II, where layered barites are found in one sample, supporting the model of frequent changes of redox conditions. Preliminary results show that the depositional age of barite-bearing black shale is > 520 Ma. In this study, we will combine the in-situ U-Pb xenotime dating and sulfur isotopes in barite and pyrite to discuss the evolution of redox conditions in the Ediacaran ocean.

Early jointing in coal and black shale: Evidence for an Appalachian-wide stress field as a prelude to the Alleghanian orogeny

DOE Office of Scientific and Technical Information (OSTI.GOV)

Engelder, T.; Whitaker, A.

2006-07-15

Early ENE-striking joints (present coordinates) within both Pennsylvanian coal and Devonian black shale of the Central and Southern Appalachians reflect an approximately rectilinear stress field with a dimension > 1500 km. This Appalachian-wide stress field (AWSF) dates from the time of joint propagation, when both the coal and shale were buried to the oil window during the 10-15 m.y. period straddling the Pennsylvanian-Permian boundary. The AWSF was generated during the final assembly of Pangea as a consequence of plate-boundary tractions arising from late-stage oblique convergence, where maximum horizontal stress, S-H, of the AWSF was parallel to the direction of closuremore » between Gondwana and Laurentia. After closure, the AWSF persisted during dextral slip of peri-Gondwanan microcontinents, when SH appears to have crosscut plate-scale trans-current faults at around 30{sup o}. Following > 10 m.y. of dextral slip during tightening of Gondwana against Laurentia, the AWSF was disrupted by local stress fields associated with thrusting on master basement decollements to produce the local orocline-shaped Alleghanian map pattern seen today.« less

Horizontal drilling potential of the Cane Creek Shale, Paradox Formation, Utah

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morgan, C.D.; Chidsey, T.C.

1991-06-01

The Cane Creek shale of the Pennsylvanian Paradox Formation is a well-defined target for horizontal drilling. This unit is naturally fractures and consists of organic-rich marine shale with interbedded dolomitic siltstone and anhydrite. Six fields have produced oil from the Cane Creek shale in the Paradox basin fold-and-fault belt. The regional structural trend is north-northwest with productive fractures occurring along the crest and flanks of both the larger and more subtle smaller anticlines. The Long Canyon, Cane Creek, Bartlett Flat, and Shafer Canyon fields are located on large anticlines, while Lion Mesa and Wilson Canyon fields produce from subtle structuralmore » noses. The Cane Creek shale is similar to the highly productive Bakken Shale in the Williston basin. Both are (1) proven producers of high-gravity oil, (2) highly fractured organic-rich source rocks, (3) overpressured, (4) regionally extensive, and (5) solution-gas driven with little or no associated water. Even though all production from the Cane Creek shale has been from conventional vertical wells, the Long Canyon 1 well has produced nearly 1 million bbl of high-gravity, low-sulfur oil. Horizontal drilling may result in the development of new fields, enhance recovery in producing fields, and revive production in abandoned fields. In addition, several other regionally extensive organic-rich shale beds occur in the Paradox Formation. The Gothic and Chimney Rock shales for example, offer additional potential lying above the Cane Creek shale.« less

Characterization of Unconventional Reservoirs: CO2 Induced Petrophysics

NASA Astrophysics Data System (ADS)

Verba, C.; Goral, J.; Washburn, A.; Crandall, D.; Moore, J.

2017-12-01

As concerns about human-driven CO2 emissions grow, it is critical to develop economically and environmentally effective strategies to mitigate impacts associated with fossil energy. Geologic carbon storage (GCS) is a potentially promising technique which involves the injection of captured CO2 into subsurface formations. Unconventional shale formations are attractive targets for GCS while concurrently improving gas recovery. However, shales are inherently heterogeneous, and minor differences can impact the ability of the shale to effectively adsorb and store CO2. Understanding GCS capacity from such endemic heterogeneities is further complicated by the complex geochemical processes which can dynamically alter shale petrophysics. We investigated the size distribution, connectivity, and type (intraparticle, interparticle, and organic) of pores in shale; the mineralogy of cores from unconventional shale (e.g. Bakken); and the changes to these properties under simulated GCS conditions. Electron microscopy and dual beam focused ion beam scanning electron microscopy were used to reconstruct 2D/3D digital matrix and pore structures. Comparison of pre and post-reacted samples gives insights into CO2-shale interactions - such as the mechanism of CO2 sorption in shales- intended for enhanced oil recovery and GCS initiatives. These comparisons also show how geochemical processes proceed differently across shales based on their initial diagenesis. Results show that most shale pore sizes fall within meso-macro pore classification (> 2 nm), but have variable porosity and organic content. The formation of secondary minerals (calcite, gypsum, and halite) may play a role in the infilling of fractures and pore spaces in the shale, which may reduce permeability and inhibit the flow of fluids.

Mechanism of molybdenum removal from the sea and its concentration in black shales: EXAFS evidence

USGS Publications Warehouse

Helz, G.R.; Miller, C.V.; Charnock, J.M.; Mosselmans, J.F.W.; Pattrick, R.A.D.; Garner, C.D.; Vaughan, D.J.

1996-01-01

Molybdenum K-edge EXAFS (extended X-ray absorption fine structure) spectra yield new structural information about the chemical environment of Mo in high-Mo black shales and sediments. Two spectral types are found. The less common one, associated with Mo ores developed in shale in China, is that of a MoS2 phase, possibly X-ray amorphous jordisite. The other, associated with Cretaceous deep sea sediments and with other black shales, is characterized by short Mo-O distances (1.69-1.71 A??), by Mo-S distances of 2.30-2.38 A??, and in some cases by second shell Mo and Fe interactions, which suggests that some Mo resides in transition metal-rich phases. EXAFS spectra of synthetic amorphous materials, prepared by scavenging Mo from HS solutions with Fe(II), FeOOH, and humic acid, suggest that the second spectral type arises from Mo present chiefly in two forms. One is a compact, Mo-Fe-S "cubane" type compound with Mo-S distances of ???2.36 A?? and Mo-Fe distances of ???2.66 A??, while the other is probably an organic form containing some Mo-O double bonds (???1.69 A??). Laboratory products, that were prepared by scavenging dissolved Mo from sulfidic solutions with humic acid, yield spectra quite similar to the second spectral type observed in shales and sediments, including unexpected indications of Mo-Fe interactions. Molybdenum L-edge spectra indicate that the mean oxidation state in the sediments and shales lies between IV and VI. This work demonstrates the merit of EXAFS for obtaining structural information on natural materials containing X-ray amorphous components which defeat conventional mineralogical characterization. The implications of these findings regarding Mo scavenging from sulfidic natural waters are considered. We introduce the concept of a geochemical switch, in which HS- transforms the marine behavior of Mo from that of a conservative element to that of a particle reactive element. The action point of the HS- switch is calculated to be, aHS- = 10-3.6 - 10-4.3. When aHS- approaches the action point, Mo becomes reactive to particles containing transition metals (e.g., Fe). We conjecture that thiols, including humic-bound thiol groups, also switch Mo behavior. In contrast to previous ideas, our model for Mo scavenging deemphasizes the role of reduction from Mo(VI) to Mo(V) as the initial step in scavenging; instead, we emphasize the ease with which Mo forms covalent bonds to transition metals and organic molecules via S bridges.

Time-dependent deformation of gas shales - role of rock framework versus reservoir fluids

NASA Astrophysics Data System (ADS)

Hol, Sander; Zoback, Mark

2013-04-01

Hydraulic fracturing operations are generally performed to achieve a fast, drastic increase of permeability and production rates. Although modeling of the underlying short-term mechanical response has proven successful via conventional geomechanical approaches, predicting long-term behavior is still challenging as the formation interacts physically and chemically with the fluids present in-situ. Recent experimental work has shown that shale samples subjected to a change in effective stress deform in a time-dependent manner ("creep"). Although the magnitude and nature of this behavior is strongly related to the composition and texture of the sample, also the choice of fluid used in the experiments affects the total strain response - strongly adsorbing fluids result in more, recoverable creep. The processes underlying time-dependent deformation of shales under in-situ stresses, and the long-term impact on reservoir performance, are at present poorly understood. In this contribution, we report triaxial mechanical tests, and theoretical/thermodynamic modeling work with the aim to identify and describe the main mechanisms that control time-dependent deformation of gas shales. In particular, we focus on the role of the shale solid framework versus the type and pressure of the present pore fluid. Our experiments were mainly performed on Eagle Ford Shale samples. The samples were subjected to cycles of loading and unloading, first in the dry state, and then again after equilibrating them with (adsorbing) CO2 and (non-adsorbing) He at fluid pressures of 4 MPa. Stresses were chosen close to those persisting under in-situ conditions. The results of our tests demonstrate that likely two main types of deformation mechanisms operate that relate to a) the presence of microfractures as a dominating feature in the solid framework of the shale, and b) the adsorbing potential of fluids present in the nanoscale voids of the shale. To explain the role of adsorption in the observed compaction creep, we postulate a serial coupling between 1) stress-driven desorption of the fluid species, 2) diffusion of the desorbed species out of the solid, and 3) consequent shrinkage. We propose a model in which the total shrinkage of the solid (Step 3) that is measured as bulk compaction, is driven by a change in stress state (Step 1), and evolves in time controlled by the diffusion characteristics of the system (Step 2). Our experimental and modeling study shows that both the nature of the solid framework of the shale, as well as the type and pressure of pore fluids affect the long-term in-situ mechanical behavior of gas shale reservoirs.

Organic content of Devonian shale in western Appalachian basin.

USGS Publications Warehouse

Schmoker, J.W.

1980-01-01

In the organic-rich facies of the Devonian shale in the western part of the Appalachian basin, the distribution of organic matter provides an indirect measure of both gas in place and the capacity of the shale to supply gas to permeable pathways.The boundary between organic-rich ('black') and organic-poor ('gray') facies is defined here as 2% organic content by volume. The thickness of organic-rich facies ranges from 200ft in central Kentucky to 1000ft along the Kentucky-West Virginia border. The average content of the organic-rich facies increases from 5% by volume on the edge to 16% in central Kentucky. The net thickness of organic matter in the organic-rich facies shows the amount of organic material in the shale, and is the most fundamental of the organic-content characterizations. Net thickness of organic matter ranges between 20 and 80ft (6.1 and 24.4m) within the mapped area.-from Author

Stratigraphic and palaeoenvironmental summary of the south-east Georgia Embayment: a correlation of exploratory wells

USGS Publications Warehouse

Poppe, L.J.; Popenoe, P.; Poag, C.W.; Swift, B.A.

1995-01-01

A Continental Offshore Stratigraphic Test (COST) well and six exploratory wells have been drilled in the south-east Georgia embayment. The oldest rocks penetrated are weakly metamorphosed Lower Ordovician quartz arenites and Silurian shales and argillites in the Transco 1005-1 well and Upper Devonian argillites in the COST GE-1 well. The Palaeozoic strata are unconformably overlain by interbedded non-marine Jurassic sandstones and shales and marginal marine Lower Cretaceous rocks. Together, these rocks are stratigraphically equivalent to the onshore Fort Pierce and Cotton Valley(?) Formations and rocks of the Lower Cretaceous Comanchean Provincial Series. The Upper Cretaceous part of the section is composed mainly of neritic calcareous shales and shaley limestones stratigraphically equivalent to the primarily marginal marine facies of the onshore Atkinson, Cape Fear and Middendorf Formations and Black Creek Group, and to limestones and shales of the Lawson Limestone and Peedee Formations. Cenozoic strata are also described. -from Authors

Comparative study of Se oxyanions retention on three argillaceous rocks: Upper Toarcian (Tournemire, France), Black Shales (Tournemire, France) and Opalinus Clay (Mont Terri, Switzerland).

PubMed

Frasca, B; Savoye, S; Wittebroodt, C; Leupin, O X; Michelot, J-L

2014-01-01

A comparative study of selenium oxyanion sorption was carried out by means of batch sorption experiments on three argillaceous rocks that differ in their mineralogical compositions and textural properties. The results show no selenate (Se(VI)) sorption onto the argillaceous rocks after 60 days, but clear sorption of selenite (Se(IV)), the extent being closely related to the initial Se(IV) concentration. At the lowest concentration ([Se(IV)]eq < 10(-8) mol L(-1)), the ranking of rock affinity for Se(IV) is Black Shales > Opalinus Clay (OPA) > Upper Toarcian, with Rd values of 910 ± 70, 600 ± 65 and 470 ± 70 mL g(-1) respectively. The Se(IV) sorption isotherms acquired for the three argillaceous rocks can be reproduced well by means of Langmuir formalism, particularly with a two-site Langmuir model. The comparison of the Se(IV) sorption isotherms obtained for these three rocks led to identification of pyrite associated with natural organic matter (NOM) as one of the main phases involved in selenium retention. While the desorption results suggested a significant Se(IV) reduction in the Upper Toarcian samples, the reversible sorption shown on the Black Shales and OPA samples was correlated with a sulfate increase, symptomatic of surface oxidation of pyrite which could limit the Se(IV) reduction in favor of sorption. Copyright © 2013 Elsevier Ltd. All rights reserved.

Arsenic transformation and mobilization from minerals by the arsenite oxidizing strain WAO

USGS Publications Warehouse

Rhine, E.D.; Onesios, K.M.; Serfes, M.E.; Reinfelder, J.R.; Young, L.Y.

2008-01-01

Analysis of arsenic concentrations in New Jersey well water from the Newark Basin showed up to 15% of the wells exceed 10 ??g L-1, with a maximum of 215 ??g L-1. In some geologic settings in the basin, this mobile arsenic could be from the weathering of pyrite (FeS2) found in black shale that contains up to 4% arsenic by weight. We hypothesized that under oxic conditions at circumneutral pH, the microbially mediated oxidation of sulfide in the pyrite lattice would lead to the release of pyrite-bound arsenic. Moreover, the oxidation of aqueous As(III) to As(V) by aerobic microorganisms could further enhance arsenic mobilization from the solid phase. Enrichment cultures under aerobic, As(III)-oxidizing conditions were established under circumneutral pH with weathered black shale from the Newark Basin as the inoculum source. Strain WAO, an autotrophic inorganic-sulfur and As(III)-oxidizer, was isolated and phylogenetically and physiologically characterized. Arsenic mobilization studies from arsenopyrite (FeAsS) mineral, conducted with strain WAO at circumneutral pH, showed microbially enhanced mobilization of arsenic and complete oxidation of released arsenic and sulfur to stoichiometric amounts of arsenate and sulfate. In addition, WAO preferentially colonized pyrite on the surface of arsenic-bearing, black shale thick sections. These findings support the hypothesis that microorganisms can directly mobilize and transform arsenic bound in mineral form at circumneutral pH and suggest that the microbial mobilization of arsenic into groundwater may be important in other arsenic-impacted aquifers. ?? 2008 American Chemical Society.

Record of the Late Devonian Hangenberg global positive carbon-isotope excursion in an epeiric sea setting: Carbonate production, organic-carbon burial and paleoceanography during the late Famennian

USGS Publications Warehouse

Cramer, Bradley D.; Saltzman, Matthew R.; Day, J.E.; Witzke, B.J.

2008-01-01

Latest Famennian marine carbonates from the mid-continent of North America were examined to investigate the Late Devonian (very late Famennian) Hangenberg positive carbon-isotope (??13 Ccarb) excursion. This global shift in the ?? 13C of marine waters began during the late Famennian Hangenberg Extinction Event that occurred during the Middle Siphonodella praesulcata conodont zone. The post-extinction recovery interval spans the Upper S. praesulcata Zone immediately below the Devonian-Carboniferous boundary. Positive excursions in ?? 13 Ccarb are often attributed to the widespread deposition of organic-rich black shales in epeiric sea settings. The Hangenberg ??13 Ccarb excursion documented in the Louisiana Limestone in this study shows the opposite trend, with peak ??13 Ccarb values corresponding to carbonate production in the U.S. mid-continent during the highstand phase of the very late Famennian post-glacial sea level rise. Our data indicate that the interval of widespread black shale deposition (Hangenberg Black Shale) predates the peak isotope values of the Hangenberg ??13 Ccarb excursion and that peak values of the Hangenberg excursion in Missouri are not coincident with and cannot be accounted for by high Corg burial in epeiric seas. We suggest instead that sequestration and burial of Corg in the deep oceans drove the peak interval of the ??13Ccarb excursion, as a result of a change in the site of deep water formation to low-latitude epeiric seas as the global climate shifted between cold and warm states.

The Stratigraphy and Lithofacies of the Paleoproterozoic Volcaniclastic Sequences in the Cape Three Points Area- Akodda section of the Southern in Ashanti Belt in the Birimian of southwest Ghana

NASA Astrophysics Data System (ADS)

Yoshimaru, S.; Kiyokawa, S.; Ito, T.; Ikehara, M.; Nyame, F. K.; Tetteh, G. M.

2015-12-01

The Paleoproterozoic Era is thought to have experienced one of the most significant changes in earth's environment during earth history. Early continents started to diverge and collide accompanied by first major oxidation of the atmosphere-oceanic system known as the Great Oxidation Environment (GOE). Due to their well-preserved oceanic sedimentary sequences, Paleoproterozoic belts are usually good targets for studies on the history of earth's past environment. In addition, these belts provide great help to understand the nature of the Paleoproterozoic deeper oceanic environments. Birimian greenstone belt in southwestern Ghana is likely to have made up of subduction of oceanic basin to form a volcanic island arc. Birimian rocks are separated by nonconformity from the Tarkwaian Group which is a younger paleoplacer deposit (Perrouty et al., 2012). The Birimian is made up of island-arc volcanic rocks; foreland basin made up of shale, sandstone, quartzite and turbidities derived from 2.17 Ga granite intrusions during Birimian volcanism. In this study, we focused on the coastal area around Cape Three Points at the southernmost part of the Ashanti (Axim-Konongo) belt in Ghana. In the eastern part of the area, excellently preserved Paleoprotorozoic deeper oceanic sedimentary sequences extensively outcrop for over 4km stretch. This volcano-sedimentary sequence has been affected by greenschist facies metamorphism. Structurally, this region preserves S1 cleavage and asymmetrical synform with west vergence and S0 younging to the east. Provisional stratigraphy is very continuous up to more than 2000m thick and, in addition, suggests at least four different fining upward sequences in the area to the east and west of Atwepo, west of Kwetakora and Akodda. These sub-sequences are mainly composed of volcaniclasitc, sandstone, black shale and rare volcanics such as pillow basalt or massive volcanic lava. In other words, this continuous sequence suggests distal submarine volcaniclastic rocks in an oceanic island arc around the West African Craton. Preliminary δ13C analysis gave values of -23.7~ -36.5 ‰ for black shale occupying the middle to upper part of the whole section. The very light carbon isotope ratios suggest deposition of the black shale under highly euxinic conditions like today's Black sea.

Biomarker Evidence From Demerara Rise for Surface and Deep Water Redox Conditions in the mid Cretaceous Western Equatorial Atlantic

NASA Astrophysics Data System (ADS)

Beckmann, B.; Hofmann, P.; Schouten, S.; Sinninghe Damsté, J. S.; Wagner, T.

2006-12-01

Oceanic Anoxic Events (OAEs) provide deep insights into rapid climate change and atmosphere-land ocean interactions during an extremely warm mode of the Earth system. We present results from ODP Leg 207 at Demerara Rise deposited in the western tropical Atlantic during transition from the Turonian OAE 2 to the Santonian OAE 3. Molecular markers in organic matter-rich black shale identify the composition of primary producers and provide detailed information on the oxygenation state of surface and deep waters. This information is relevant to infer the dynamics and controls of sedimentation leading to black shale in the tropical Atlantic. Bulk organic geochemical data suggest the dominance of lipid-rich marine organic matter throughout the study section. Biomarkers from the aliphatic fraction instead reveal variable contributions of e.g., archaea, diatoms, and dinoflagellates supporting changes in the community of primary producers that thrived in the oxic part of the photic zone in response to changing environmental conditions similar to modern high productive areas along continental margins. Also comparable to modern high productive areas the sea floor remained generally oxygen-depleted throughout the Turonian to Santonian as supported by elevated lycopane contents along with an enrichment of redox-sensitive elements and documented by persistent high TOC concentrations (1 to 14%). Isorenieratane derivates indicative of photic zone euxinia (PZE) were only detected in low abundances in the lowest part of the study section. This observation contrasts biomarker records from the eastern low latitude Atlantic where PZE was a temporal feature determining black shale formation. The new biomarker data from Leg 207 support progressive weakening of upwelling intensity along with oxygenation of surface and possibly mid waters from the upper Coniacian on. Different from black shale sites in many semi-sheltered sub-basins along the Equatorial Atlantic, Demerara Rise was fully exposed to open marine currents throughout the mid-Cretaceous. Increasing ocean circulation along with the widening of the Equatorial Atlantic probably had a significant effect on shallow ocean oxygenation off tropical S-America. Notably deep ocean oxygenation was decoupled from these processes posing the general question what maintained anoxia at the sea floor over millions of years in the aftermath of OAE 2 at Demerara Rise.

Uranium Isotope Compositions of Mid-Proterozoic Organic-rich Mudrocks: Evidence for an Episode of Increased Ocean Oxygenation at ca. 1.36 Ga and Evaluation of the Effect of Post-Depositional Hydrothermal Fluid Flow

NASA Astrophysics Data System (ADS)

Kendall, B.; Yang, S.; Lu, X.; Zhang, F.; Zheng, W.

2016-12-01

The U isotope system represents a relatively new paleoredox proxy that can help trace the evolution of global ocean redox chemistry, but has rarely been applied to the Mid-Proterozoic. We report U isotope data for marine black shales of the early Mesoproterozoic Velkerri Formation (Roper Group) and late Paleoproterozoic Wollogorang Formation (Tawallah Group) from the McArthur Basin, Northern Australia. An average authigenic δ238U of 0.13 ± 0.04‰ (1SD; relative to standard CRM145) was obtained for six euxinic shales from a 1 m interval that previously yielded a precise Re-Os depositional age of 1361 ± 21 Ma. After correcting for a U isotope fractionation of 0.60-0.85‰ between seawater and open-ocean euxinic sediments, we infer that coeval global seawater had a δ238U of -0.47‰ to -0.72‰, which is 0.1-0.3‰ lighter than modern seawater (-0.40 ± 0.03‰). A U isotope mass-balance model suggests that anoxic marine environments accounted for 25-50% of the global oceanic U sink at 1.36 Ga, which is 3-7 times greater than today. The model suggests that a significant proportion, potentially even a majority, of the seafloor was not covered by anoxic waters. Hence, we infer that a significant extent of the ocean floor was covered by O2-bearing waters at 1.36 Ga. The O2 concentrations of those waters were not necessarily high, and a large expanse of weakly to mildly oxygenated deep waters is consistent with the U isotope data. Uranium isotope data from a 1 m interval in the lower Velkerri Formation, deposited at 1417 ± 29 Ma based on Re-Os geochronology, yield a greater estimate for the extent of ocean anoxia. Hence, the upper Velkerri Formation may capture a transient episode of increased ocean oxygenation. Previous Re-Os isotope data from black shales of the ca. 1.73 Ga Paleoproterozoic Wollogorang Formation yielded an erroneously young date of 1359 ± 150 Ma because hydrothermal fluids percolated through the Tawallah Group rocks at ca. 1640 Ma. Higher δ238U is observed in samples closer to the base of the black shale unit where the greatest extent of open-system Re-Os isotope behavior was observed. Hence, post-depositional hydrothermal fluid flow can overprint the depositional δ238U of black shales and lead to erroneous interpretations of global ocean paleoredox conditions.

The variation of molybdenum isotopes within the weathering system of the black shales

NASA Astrophysics Data System (ADS)

Jianming, Z.

2016-12-01

Jian-Ming Zhu 1,2, De-Can Tan 2, Liang Liang 2, Wang Jing21 State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Beijing, 100083, China 2 State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang, 550002, China Molybdenum (Mo) stable isotopes have been developed as a tracer to indicate the evolution of the atmospheric and oceanic oxygenation related with continent weathering, and to reveal the extent of ancient oceanic euxinia. Molybdenum isotopic variation within the weathering system of basalts has been studied, and was presented the whole trend with heavier isotopes preferentially removed during weathering processes. However, there are few researches to study the variation of Mo isotopes during black shale weathering, especiall on the behavoir of Mo isotopes within the perfect shales' profiles. Here, the weathering profiles of Mo and selenium(Se)-rich carbonaceous rocks in Enshi southwest Hubei Province were selected. The Mo isotopes was measured on Nu Plasma II's MC-ICP-MS using 97Mo-100Mo double spike, and δ98/95Mo was reported relative to NIST 3134. A comprehensive set of Mo isotopic composition and concentration data from the unweathered, weakly and intensely weathered rocks were collected. The δ98/95Mo in fresh shales (220±248 mg/kg Mo, 1SD, n=41) from Shadi and Yutangba drill cores varies from 0.41‰ to 0.99‰ with an average of 0.67±0.16‰, while the strongly weathered shales (19.9±5.8 mg/kg Mo, 1SD, n=5) from Shadi profiles are isotopically heavier with average δ98/95Mo values of 1.03±0.10‰ (1SD, n=5). The Locally altered shales exposed in a quarry at Yutangba are highly enriched in Mo, varing from 31 to 2377 mg/kg with an average of 428 ±605mg/kg (1SD, n=24), approximately 2 times greater than that in fresh shales samples. These rocks are presented a significant variation in δ98/95Mo values varing from -0.24 ‰ to -3.99 ‰ with average -1.67±1.57‰, showing the extremely negative δ98/95Mo values existed in natural samples. This suggested that Mo isotopes can be fractionated during shales weathering processes, with lighter isotopes preferentially removed. This finding is in contrast to the previous knowledge from basalt weathering, and requires further study.

The astronomical rhythm of Late-Devonian climate change (Kowala section, Holy Cross Mountains, Poland)

NASA Astrophysics Data System (ADS)

De Vleeschouwer, David; Rakociński, Michał; Racki, Grzegorz; Bond, David P. G.; Sobień, Katarzyna; Claeys, Philippe

2013-03-01

Rhythmical alternations between limestone and shales or marls characterize the famous Kowala section, Holy Cross Mountains, Poland. Two intervals of this section were studied for evidence of orbital cyclostratigraphy. The oldest interval spans the Frasnian-Famennian boundary, deposited under one of the hottest greenhouse climates of the Phanerozoic. The youngest interval encompasses the Devonian-Carboniferous (D-C) boundary, a pivotal moment in Earth's climatic history that saw a transition from greenhouse to icehouse. For the Frasnian-Famennian sequence, lithological variations are consistent with 405-kyr and 100-kyr eccentricity forcing and a cyclostratigraphic floating time-scale is presented. The interpretation of observed lithological rhythms as eccentricity cycles is confirmed by amplitude modulation patterns in agreement with astronomical theory and by the recognition of precession cycles in high-resolution stable isotope records. The resulting relative time-scale suggests that ˜800 kyr separate the Lower and Upper Kellwasser Events (LKE and UKE, respectively), two periods of anoxia that culminated in massive biodiversity loss at the end of the Frasnian. Th/U and pyrite framboid analyses indicate that during the UKE, oxygen levels remained low for 400 kyr and δ13Corg measurements demonstrate that more than 600 kyr elapsed before the carbon cycle reached a steady state after a +3‰ UKE excursion. The Famennian-Tournaisian (D-C) interval also reveals eccentricity and precession-related lithological variations. Precession-related alternations clearly demonstrate grouping into 100-kyr bundles. The Famennian part of this interval is characterized by several distinctive anoxic black shales, including the Annulata, Dasberg and Hangenberg shales. Our high-resolution cyclostratigraphic framework indicates that those shales were deposited at 2.2 and 2.4 Myr intervals respectively. These durations strongly suggest a link between the long-period (˜2.4 Myr) eccentricity cycle and the development of the Annulata, Dasberg and Hangenberg anoxic shales. It is assumed that these black shales form under transgressive conditions, when extremely high eccentricity promoted the collapse of small continental ice-sheets at the most austral latitudes of western Gondwana.

An overview on source rocks and the petroleum system of the central Upper Rhine Graben

NASA Astrophysics Data System (ADS)

Böcker, Johannes; Littke, Ralf; Forster, Astrid

2017-03-01

The petroleum system of the Upper Rhine Graben (URG) comprises multiple reservoir rocks and four major oil families, which are represented by four distinct source rock intervals. Based on geochemical analyses of new oil samples and as a review of chemical parameter of former oil fields, numerous new oil-source rock correlations were obtained. The asymmetric graben resulted in complex migration pathways with several mixed oils as well as migration from source rocks into significantly older stratigraphic units. Oldest oils originated from Liassic black shales with the Posidonia Shale as main source rock (oil family C). Bituminous shales of the Arietenkalk-Fm. (Lias α) show also significant source rock potential representing the second major source rock interval of the Liassic sequence. Within the Tertiary sequence several source rock intervals occur. Early Tertiary coaly shales generated high wax oils that accumulated in several Tertiary as well as Mesozoic reservoirs (oil family B). The Rupelian Fish Shale acted as important source rock, especially in the northern URG (oil family D). Furthermore, early mature oils from the evaporitic-salinar Corbicula- and Lower Hydrobienschichten occur especially in the area of the Heidelberg-Mannheim-Graben (oil family A). An overview on potential source rocks in the URG is presented including the first detailed geochemical source rock characterization of Middle Eocene sediments (equivalents to the Bouxwiller-Fm.). At the base of this formation a partly very prominent sapropelic coal layer or coaly shale occurs. TOC values of 20-32 % (cuttings) and Hydrogen Index (HI) values up to 640-760 mg HC/g TOC indicate an extraordinary high source rock potential, but a highly variable lateral distribution in terms of thickness and source rock facies is also supposed. First bulk kinetic data of the sapropelic Middle Eocene coal and a coaly layer of the `Lymnäenmergel' are presented and indicate oil-prone organic matter characterized by low activation energies. These sediments are considered as most important source rocks of numerous high wax oils (oil family B) in addition to the coaly source rocks from the (Lower) Pechelbronn-Schichten (Late Eocene). Migration pathways are significantly influenced by the early graben evolution. A major erosion period occurred during the latest Cretaceous. The uplift center was located in the northern URG area, resulting in SSE dipping Mesozoic strata in the central URG. During Middle Eocene times a second uplift center in the Eifel area resulted in SW-NE-directed shore lines in the central URG and contemporaneous south-southeastern depocenters during marine transgression from the south. This structural setting resulted in a major NNW-NW-directed and topography-driven migration pattern for expelled Liassic oil in the fractured Mesozoic subcrop below sealing Dogger α clays and basal Tertiary marls.

Horizontal slip along Alleghanian joints of the Appalachian plateau: evidence showing that mild penetrative strain does little to change the pristine appearance of early joints

NASA Astrophysics Data System (ADS)

Engelder, Terry; Haith, Benjamin F.; Younes, Amgad

2001-07-01

Some Alleghanian joints in black shales of the Geneseo and Middlesex Formations of the Catskill Delta complex, Finger Lakes district, New York, slipped horizontally up to 8 cm. Horizontal slip is measured by the offset of ENE-striking joints. Alleghanian joints striking 330-350° display a right-lateral slip with an average value of 1.9 cm, while joints striking 004-010° slip in the left-lateral sense with an average value of 1.3 cm. The maximum horizontal stress (SH) driving this slip falls between 350° and 004°, the orientation of local Alleghanian layer-parallel shortening as indicated by both disjunctive and pencil cleavage. By commonality of orientation, we infer that slip on Alleghanian joints is driven contemporaneously with layer-parallel shortening. If so, the offset ENE-striking joints predate the Alleghanian stress field. These observations mean that both pre-Alleghanian and early Alleghanian joints persist through a period of penetrative strain.

Pyrite framboid diameter distribution in the Lower Oligocene black shales of the Vrancea Nappe as an indicator of changes in redox conditions, Eastern Outer Carpathians, Romania

NASA Astrophysics Data System (ADS)

Wendorff, Małgorzata; Marynowski, Leszek; Rospondek, Mariusz

2016-04-01

Studies of recent and ancient sediments revealed that the diameter distribution of pyrite framboids may be reliably used to characterise oxygen-restricted environments and distinguish ancient euxinic conditions (water column hydrogen sulphide bearing thus oxygen-free) from anoxic, non-sulfidic or dysoxic (oxygen-poor) conditions. Such diagnoses are of great importance when reconstructing palaeoenvironments in ancient basins and the processes of source rocks formation. During Oligocene to early Miocene time an extensive accumulation of organic matter (OM)-rich sediments occurred in the entire Paratethys including the Carpathian Foredeep, which was closed forming fold-thrust belt of the Outer Carpathians. These OM-rich black shales are represented by so-called Menilite shales, widely considered as hydrocarbon source rocks, which constitute as well a detailed archive for palaeoenvironmental changes. The purpose of this preliminary study is to characterise the depositional environment of the Lower Oligocene black shales basing on the pyrite framboid diameter distribution. Five samples of finely laminated black shales were selected from the Nechit section outcropping in the Bistrica half-window of the Vrancea Nappe in the Eastern Outer Carpathians, E Romania. At least 100 framboid diameters were measured on polished blocks using scanning electron microscope in a back-scattered electron mode. Framboids from four samples starting from the lowermost part of the section exhibit a narrow range of diameters from 1.0 to 11.5 μm; mean value ranges from 3.65 to 4.85 μm. Small-sized framboids (< 6 μm) account for 70% up to 91% of all framboids, while large framboids (>10 μm) are absent or rare (max. 2%). Within the sample from the uppermost part of the section framboids reveal more variable sizes, 2 - 25 μm, with mean value of 6.63 μm. Small framboids are still numerous (54%), however the amount of framboids >10 μm increases to 15%. The domination of small framboids with narrow size range in analysed samples, as well as lamination of rocks, suggest domination of anoxic / euxinic conditions during sedimentation of the Menilite shales. The transition into dysoxic bottom-water conditions can be evidenced by increased amount of larger framboids (up to 25 μm) in the upper part of the section. It has been concluded that framboids growing at interface of oxic/euxinic water column are in general smaller and less variable in size than framboids from sediments overlained by oxic or dysoxic water column. In the presented case, the prevalence of small framboids indicates that the water column euxinia could have developed, at least temporarily, during the deposition. Although the euxinia did not reached the photic zone as it reconstructed based on the occurrence of isorenieratane and its derivatives, e.g. C19 aryl isoprenoid in equivalent rocks from many locations of the Outer Carpathians. These biomarkers are derived from carotenoids biosynthesised by the photosynthetic green sulphur bacteria (Chlorobiaceae), anaerobic organisms requiring light and hydrogen sulphide for growth.

Effect of thermal maturity on remobilization of molybdenum in black shales

NASA Astrophysics Data System (ADS)

Ardakani, Omid H.; Chappaz, Anthony; Sanei, Hamed; Mayer, Bernhard

2016-09-01

Molybdenum (Mo) concentrations in sedimentary records have been widely used as a method to assess paleo-redox conditions prevailing in the ancient oceans. However, the potential effects of post-depositional processes, such as thermal maturity and burial diagenesis, on Mo concentrations in organic-rich shales have not been addressed, compromising its use as a redox proxy. This study investigates the distribution and speciation of Mo at various thermal maturities in the Upper Ordovician Utica Shale from southern Quebec, Canada. Samples display maturities ranging from the peak oil window (VRo ∼ 1%) to the dry gas zone (VRo ∼ 2%). While our data show a significant correlation between total organic carbon (TOC) and Mo (R2 = 0.40, n = 28, P < 0.0003) at lower thermal maturity, this correlation gradually deteriorates with increasing thermal maturity. Intervals within the thermally overmature section of the Utica Shale that contain elevated Mo levels (20-81 ppm) show petrographic and sulfur isotopic evidence of thermochemical sulfate reduction (TSR) along with formation of recrystallized pyrite. X-ray Absorption Fine Structure spectroscopy (XAFS) was used to determine Mo speciation in samples from intervals with elevated Mo contents (>30 ppm). Our results show the presence of two Mo species: molybdenite Mo(IV)S2 (39 ± 5%) and Mo(VI)-Organic Matter (61 ± 5%). This new evidence suggests that at higher thermal maturities, TSR causes sulfate reduction coupled with oxidation of organic matter (OM). This process is associated with H2S generation and pyrite formation and recrystallization. This in turn leads to the remobilization of Mo and co-precipitation of molybdenite with TSR-derived carbonates in the porous intervals. This could lead to alteration of the initial sedimentary signature of Mo in the affected intervals, hence challenging its use as a paleo-redox proxy in overmature black shales.

Studies on geological background and source of fluorine in drinking water in the North China Plate fluorosis areas

USGS Publications Warehouse

Luo, K.; Feng, F.; Li, H.; Chou, C.-L.; Feng, Z.; Yunshe, D.

2008-01-01

Endemic fluorosis in northern China is usually produced by high fluorine (F) content in drinking water. Thirty-one samples of drinking waters, mainly well waters and nearly 200 samples of rocks, loess, and coal were analyzed for F content using the combustion hydrolysis-fluoride-ion selective electrode (ISE) method. The geologic cross sections of two well-known fluorosis basins were studied. The solubility of F in different rock types collected from fluorosis areas was determined. Results showed that areas of endemic fluorosis in northern China are located in coal-bearing basins which are comprised of three stratagraphic portions. The lowest portion is Precambrian granitic rocks or Cambrian-Ordovician carbonates. The middle portion consists of Permo-Carboniferous or Jurassic coal-bearing sequences. The upper portion is 0-400 m Pleistocene loess. Flourine content in the Precambrian granite-gneiss contained (a) 1090-1460 ppm, in the Cambrian-Ordovician limestone and dolomite, (b) 52-133 ppm, in black shales and coal gob of Permo-Carboniferous coal-bearing strata, (c) 200-700 ppm, and (d) Pleistocene loess 454-542 ppm. The solubility of F in black shales of coal-bearing sequences was higher than in Precambrian granitic rocks, and both were more soluble than loess. F solubility from Precambrian granitic rocks was moderate, but Precambrian granitic rocks have high F content and thus contribute an appreciable amount of ion to the shallow groundwater (well water). Varying F content in shallow groundwater is controlled by geological conditions. The sources of F in the shallow groundwater from fluorosis areas in northern China are mainly derived from black shales of coal-bearing sequences and Precambrian granitic basement in the basins of northern China. ?? 2008 Taylor & Francis.

Contourite drifts on early passive margins as an indicator of established lithospheric breakup

NASA Astrophysics Data System (ADS)

Soares, Duarte M.; Alves, Tiago M.; Terrinha, Pedro

2014-09-01

The Albian-Cenomanian breakup sequence (BS) offshore Northwest Iberia is mapped, described and characterised for the first time in terms of its seismic and depositional facies. The interpreted dataset comprises a large grid of regional (2D) seismic-reflection profiles, complemented by Industry and ODP/DSDP borehole data. Within the BS are observed distinct seismic facies that reflect the presence of: (a) black shales and fine-grained turbidites, (b) mass-transport deposits (MTDs) and coarse-grained turbidites, and (c) contourite drifts. Borehole data show that these depositional systems developed as mixed carbonate-siliciclastic sediments proximally, and as organic-carbon-rich mudstones (black shales) distally on the Northwest Iberia margin. MTDs and turbidites tend to occur on the continental slope, frequently in association with large-scale olistostromes. Distally, these change into interbedded fine-grained turbidites and black shales showing widespread evidence of deep-water current activity towards the top of the BS. Current activity is expressed by intra-BS erosional surfaces and sediment drifts. The results in this paper are important as they demonstrate that contourite drifts are ubiquitous features in the study area after Aptian-Albian lithospheric breakup. Therefore, we interpret the recognition of contourite drifts in Northwest Iberia as having significant palaeogeographic implications. Contourite drifts materialise the onset of important deep-water circulation marking the establishment of oceanic gateways between two fully separated continental margins. As a corollary, we postulate the generation of deep-water geostrophic currents to have had significant impact on North Atlantic climate and ocean circulation during the Albian-Cenomanian, with the record of such impacts being preserved in the contourite drifts analysed in this work.

Selenium speciation in Lower Cambrian Se-enriched strata in South China and its geological implications

NASA Astrophysics Data System (ADS)

Fan, Haifeng; Wen, Hanjie; Hu, Ruizhong; Zhao, Hui

2011-12-01

To understand the impact of Selenium (Se) into the biogeochemical cycle and implications for palaeo-redox environment, a sequential extraction method was utilized for samples including black shales, cherts, a Ni-Mo-Se sulfide layer, K-bentonite and phosphorite from Lower Cambrian Se-enriched strata in southern China. Seven species (water-soluble, phosphate exchangeable, base-soluble, acetic acid-soluble, sulfide/selenide associated, residual Se) and different oxidation states (selenate Se(VI), selenite Se(IV), organic Se, Se (0) and mineral Se(-II)) were determinated in this study. We found that the Ni-Mo-Se sulfide layer contained a significantly greater amount of Se(-II) associated with sulfides/selenides than those in host black shales and cherts. Furthermore, a positive correlation between the degree of sulfidation of iron (DOS) and the percentage of the sulfide/selenide-associated Se(-II) was observed for samples, which suggests the proportion of sulfide/selenide-associated Se(-II) could serve as a proxy for palaeo-redox conditions. In addition, the higher percentage of Se(IV) in K-bentonite and phosphorite was found and possibly attributed to the adsorption of Se by clay minerals, iron hydroxide surfaces and organic particles. Based on the negative correlations between the percentage of Se(IV) and that of Se(-II) in samples, we propose that the K-bentonite has been altered under the acid oxic conditions, and the most of black shale (and cherts) and the Ni-Mo-Se sulfide layer formed under the anoxic and euxinic environments, respectively. Concerning Se accumulation in the Ni-Mo-Se sulfide layer, the major mechanism can be described by (1) biotic and abiotic adsorption and further dissimilatory reduction from oxidized Se(VI) and Se(IV) to Se(-II), through elemental Se, (2) contribution of hydrothermal fluid with mineral Se(-II).

The Molybdenum Isotope System as a Tracer of Slab Input in Subduction Zones: An Example From Martinique, Lesser Antilles Arc

NASA Astrophysics Data System (ADS)

Gaschnig, Richard M.; Reinhard, Christopher T.; Planavsky, Noah J.; Wang, Xiangli; Asael, Dan; Chauvel, Catherine

2017-12-01

Molybdenum isotopes are fractionated by Earth-surface processes and may provide a tracer for the recycling of crustal material into the mantle. Here, we examined the Mo isotope composition of arc lavas from Martinique in the Lesser Antilles arc, along with Cretaceous and Cenozoic Deep Sea Drilling Project sediments representing potential sedimentary inputs into the subduction zone. Mo stable isotope composition (defined as δ98Mo in ‰ deviation from the NIST 3134 standard) in lavas older than ˜7 million years (Ma) exhibits a narrow range similar to and slightly higher than MORB, whereas those younger than ˜7 Ma show a much greater range and extend to unusually low δ98Mo values. Sediments from DSDP Leg 78A, Site 543 have uniformly low δ98Mo values whereas Leg 14, Site 144 contains both sediments with isotopically light Mo and Mo-enriched black shales with isotopically heavy Mo. When coupled with published radiogenic isotope data, Mo isotope systematics of the lavas can be explained through binary mixing between a MORB-like end-member and different sedimentary compositions identified in the DSDP cores. The lavas older than ˜7 Ma were influenced by incorporation of isotopically heavy black shales into the mantle wedge. The younger lavas are the product of mixing isotopically light sedimentary material into the mantle wedge. The change in Mo isotope composition of the lavas at ˜7 Ma is interpreted to reflect the removal of the Cretaceous black shale component due to the arrival of younger ocean crust where the age-equivalent Cretaceous sediments were deposited in shallower oxic waters. Isotopic fractionation of Mo during its removal from the slab is not required to explain the observed systematics in this system.

Water Use by Texas Oil and Gas Industry: A Look towards the Future

NASA Astrophysics Data System (ADS)

Nicot, J.; Ritter, S. M.; Hebel, A. K.

2009-12-01

The Barnett Shale gas play, located in North Texas, has seen a relatively quick growth in the past decade with the development of new “frac” (aka, fracture stimulation) technologies needed to create pathways to produce gas from the very low permeability shales. This technology uses a large amount of fresh water (millions of gallons in a day or two on average) to develop a gas well. Now operators are taking aim at other shale gas plays in Texas including the Haynesville, Woodford, and Pearsall-Eagle Ford shales and at other tight formation such as the Bossier Sand. These promising gas plays are likely to be developed at an even steeper growth rate. There are currently over 12,000 wells producing gas from the Barnett Shale with many more likely to be drilled in the next couple of decades as the play expands out of its core area. Despite the recent gas price slump, thousands more wells may be drilled across the state to access the gas resource in the next few years. As an example, a typical vertical and horizontal well completion in the Barnett Shale consumes approximately 1.2 and 3.0 to 3.5 millions gallons of fresh water, respectively. This could raise some concerns among local communities and other surface water and groundwater stakeholders. We present a preliminary analysis of future water use by the Texas oil and gas industry and compare it to projections of total water use, including municipal use and irrigation. Maps showing large increase in total number of well completions in the Barnett Shale (black dots) from 1998 to 2008. Operators avoided the DFW metro area (center right on the map) until recently. Also shown are the structural limits of the Barnett Shale on its eastern boundaries.

Trace-element budgets in the Ohio/Sunbury shales of Kentucky: Constraints on ocean circulation and primary productivity in the Devonian-Mississippian Appalachian Basin

USGS Publications Warehouse

Perkins, R.B.; Piper, D.Z.; Mason, C.E.

2008-01-01

The hydrography of the Appalachian Basin in late Devonian-early Mississippian time is modeled based on the geochemistry of black shales and constrained by others' paleogeographic reconstructions. The model supports a robust exchange of basin bottom water with the open ocean, with residence times of less than forty years during deposition of the Cleveland Shale Member of the Ohio Shale. This is counter to previous interpretations of these carbon-rich units having accumulated under a stratified and stagnant water column, i.e., with a strongly restricted bottom bottom-water circulation. A robust circulation of bottom waters is further consistent with the palaeoclimatology, whereby eastern trade-winds drove upwelling and arid conditions limited terrestrial inputs of siliciclastic sediment, fresh waters, and riverine nutrients. The model suggests that primary productivity was high (~ 2??g C m- 2 d- 1), although no higher than in select locations in the ocean today. The flux of organic carbon settling through the water column and its deposition on the sea floor was similar to fluxes found in modern marine environments. Calculations based on the average accumulation rate of the marine fraction of Ni suggest the flux of organic carbon settling out of the water column was approximately 9% of primary productivity, versus an accumulation rate (burial) of organic carbon of 0.5% of primary productivity. Trace-element ratios of V:Mo and Cr:Mo in the marine sediment fraction indicate that bottom waters shifted from predominantly anoxic (sulfate reducing) during deposition of the Huron Shale Member of the Ohio Shale to predominantly suboxic (nitrate reducing) during deposition of the Cleveland Shale Member and the Sunbury Shale, but with anoxic conditions occurring intermittently throughout this period. ?? 2008 Elsevier B.V.

Re-Os Geochronology Pins Age and Os Isotope Composition of Middle Triassic Black Shales and Seawater, Barents Sea and Spitsbergen (Svalbard)

NASA Astrophysics Data System (ADS)

Xu, G.; Hannah, J. L.; Bingen, B.; Stein, H. J.; Yang, G.; Zimmerman, A.; Weitschat, W.; Weiss, H. M.

2008-12-01

Absolute age control throughout the Triassic is extraordinarily sparse. Two "golden spikes" have been added recently (http://www.stratigraphy.org/cheu.pdf) within the otherwise unconstrained Triassic, but ages of stage boundaries remain controversial. Here we report two Re-Os isochrons for Anisian (Middle Triassic) black shales from outcrop in western Svalbard and drill core from the Svalis Dome about 600 km to the SE in the Barents Sea. Black shales of the Blanknuten Member, Botneheia Formation, from the type section at Botneheia, western Spitsbergen (Svalbard), have total organic carbon (TOC) contents of 2.6 to 6.0 wt%. Rock-Eval data suggest moderately mature (Tmax = 440-450° C) Type II-III kerogens (Hydrogen Index (HI) = 232-311 mg HC/g TOC). Re-Os data yield a well-constrained Model 3 age of 241 Ma and initial 187Os/188Os (Osi) of 0.83 (MSWD = 16, n = 6). Samples of the possibly correlative Steinkobbe Formation from IKU core hole 7323/07-U-04 into the Svalis Dome in the Barents Sea (at about 73°30'N, 23°15'E) have TOC contents of 1.4 to 2.4%. Rock-Eval data suggest immature (Tmax = 410-430°) Type II-III kerogens (HI = 246-294 mg HC/g TOC). Re-Os data yield a precise Model 1 age of 239 Ma and Osi of 0.776 (MSWD = 0.2, n = 5). The sampled section of Blanknuten shale underlies a distinctive Frechitas (formerly Ptychites) layer, and is therefore assumed to be middle Anisian. The Steinkobbe core was sampled at 99-100 m, just above the Olenekian-Anisian transition. It is therefore assumed to be lower Anisian. The two isochron ages overlap within uncertainty, and fall within constraints provided by biozones and the current ICS-approved stage boundary ages. The Re-Os ages support the correlation of the Botneheia and Steinkobbe formations. The nearly identical Osi ratios suggest regional homogeneity of seawater and provide new information for the Os seawater curve, marking a relatively high 187Os/188Os ratio during profound ocean anoxia in the Middle Triassic.

Properties of Silurian shales from the Barrandian Basin, Czech Republic

NASA Astrophysics Data System (ADS)

Weishauptová, Zuzana; Přibyl, Oldřich; Sýkorová, Ivana

2017-04-01

Although shale gas-bearing deposits have a markedly lower gas content than coal deposits, great attention has recently been paid to shale gas as a new potential source of fossil energy. Shale gas extraction is considered to be quite economical, despite the lower sorption capacity of shales, which is only about 10% of coal sorption capacities The selection of a suitable locality for extracting shale gas requires the sorption capacity of the shale to be determined. The sorption capacity is determined in the laboratory by measuring the amount of methane absorbed in a shale specimen at a pressure and a temperature corresponding to in situ conditions, using high pressure sorption. According to the principles of reversibility of adsorption/desorption, this amount should be roughly related to the amount of gas released by forced degassing. High pressure methane sorption isotherms were measured on seven representative samples of Silurian shales from the Barrandian Basin, Czech Republic. Excess sorption measurements were performed at a temperature of 45oC and at pressures up to 15 MPa on dry samples, using a manometric method. Experimental methane high-pressure isotherms were fitted to a modified Langmuir equation. The maximum measured excess sorption parameter and the Langmuir sorption capacity parameter were used to study the effect of TOC content, organic maturity, inorganic components and porosity on the methane sorption capacity. The studied shale samples with random reflectance of graptolite 0.56 to 1.76% had a very low TOC content and dominant mineral fractions. Illite was the prevailing clay mineral. The sample porosity ranged from 4.6 to 18.8%. In most samples, the micropore volumes were markedly lower than the meso- and macropore volumes. In the Silurian black shales, the occurrence of fractures parallel with the original sedimentary bending was highly significant. A greater proportion of fragments of carbonaceous particles of graptolites and bitumens in the Barrandian Silurian shales had a smooth surface without pores. No relation has been proven between TOC-normalized excess sorption capacities or the TOC-normalized Langmuir sorption capacities and thermal maturation of the shales. The methane sorption capacities of shale samples show a positive correlation with TOC and a positive correlation with the clay content. The highest sorption capacity was observed in shale samples with the highest percentage of micropores, indicating that the micropore volume in the organic matter and clay minerals is a principal factor affecting the sorption capacity of the shale samples.

Mineral Reactions in Shale Gas Reservoirs: Barite Scale Formation from Reusing Produced Water As Hydraulic Fracturing Fluid.

PubMed

Paukert Vankeuren, Amelia N; Hakala, J Alexandra; Jarvis, Karl; Moore, Johnathan E

2017-08-15

Hydraulic fracturing for gas production is now ubiquitous in shale plays, but relatively little is known about shale-hydraulic fracturing fluid (HFF) reactions within the reservoir. To investigate reactions during the shut-in period of hydraulic fracturing, experiments were conducted flowing different HFFs through fractured Marcellus shale cores at reservoir temperature and pressure (66 °C, 20 MPa) for one week. Results indicate HFFs with hydrochloric acid cause substantial dissolution of carbonate minerals, as expected, increasing effective fracture volume (fracture volume + near-fracture matrix porosity) by 56-65%. HFFs with reused produced water composition cause precipitation of secondary minerals, particularly barite, decreasing effective fracture volume by 1-3%. Barite precipitation occurs despite the presence of antiscalants in experiments with and without shale contact and is driven in part by addition of dissolved sulfate from the decomposition of persulfate breakers in HFF at reservoir conditions. The overall effect of mineral changes on the reservoir has yet to be quantified, but the significant amount of barite scale formed by HFFs with reused produced water composition could reduce effective fracture volume. Further study is required to extrapolate experimental results to reservoir-scale and to explore the effect that mineral changes from HFF interaction with shale might have on gas production.

Thermally-driven Coupled THM Processes in Shales

NASA Astrophysics Data System (ADS)

Rutqvist, J.

2017-12-01

Temperature changes can trigger strongly coupled thermal-hydrological-mechanical (THM) processes in shales that are important to a number of subsurface energy applications, including geologic nuclear waste disposal and hydrocarbon extraction. These coupled processes include (1) direct pore-volume couplings, by thermal expansion of trapped pore-fluid that triggers instantaneous two-way couplings between pore fluid pressure and mechanical deformation, and (2) indirect couplings in terms of property changes, such as changes in mechanical stiffness, strength, and permeability. Direct pore-volume couplings have been studied in situ during borehole heating experiments in shale (or clay stone) formations at Mont Terri and Bure underground research laboratories in Switzerland and France. Typically, the temperature changes are accompanied with a rapid increase in pore pressure followed by a slower decrease towards initial (pre-heating) pore pressure. Coupled THM modeling of these heater tests shows that the pore pressure increases because the thermal expansion coefficient of the fluid is much higher than that of the porous clay stone. Such thermal pressurization induces fluid flow away from the pressurized area towards areas of lower pressure. The rate of pressure increase and magnitude of peak pressure depends on the rate of heating, pore-compressibility, and permeability of the shale. Modeling as well as laboratory experiments have shown that if the pore pressure increase is sufficiently large it could lead to fracturing of the shale or shear slip along pre-existing bedding planes. Another set of data and observations have been collected associated with studies related to concentrated heating and cooling of oil-shales and shale-gas formations. Heating may be used to enhance production from tight oil-shale, whereas thermal stimulation has been attempted for enhanced shale-gas extraction. Laboratory experiments on shale have shown that strength and elastic deformation modulus decreases with temperature while the rate creep deformations increase with temperature. Such temperature dependency also affects the well stability and zonal sealing across shale layers.

Petrophysical Properties of Cody, Mowry, Shell Creek, and Thermopolis Shales, Bighorn Basin, Wyoming

NASA Astrophysics Data System (ADS)

Nelson, P. H.

2013-12-01

The petrophysical properties of four shale formations are documented from well-log responses in 23 wells in the Bighorn Basin in Wyoming. Depths of the examined shales range from 4,771 to 20,594 ft. The four formations are the Thermopolis Shale (T), the Shell Creek Shale (SC), the Mowry Shale (M), and the lower part of the Cody Shale (C), all of Cretaceous age. These four shales lie within a 4,000-ft, moderately overpressured, gas-rich vertical interval in which the sonic velocity of most rocks is less than that of an interpolated trendline representing a normal increase of velocity with depth. Sonic velocity, resistivity, neutron, caliper, and gamma-ray values were determined from well logs at discrete intervals in each of the four shales in 23 wells. Sonic velocity in all four shales increases with depth to a present-day depth of about 10,000 ft; below this depth, sonic velocity remains relatively unchanged. Velocity (V), resistivity (R), neutron porosity (N), and hole diameter (D) in the four shales vary such that: VM > VC > VSC > VT, RM > RC > RSC > RT, NT > NSC ≈ NC > NM, and DT > DC ≈ DSC > DM. These orderings can be partially understood on the basis of rock compositions. The Mowry Shale is highly siliceous and by inference comparatively low in clay content, resulting in high sonic velocity, high resistivity, low neutron porosity, and minimal borehole enlargement. The Thermopolis Shale, by contrast, is a black fissile shale with very little silt--its high clay content causes low velocity, low resistivity, high neutron response, and results in the greatest borehole enlargement. The properties of the Shell Creek and lower Cody Shales are intermediate to the Mowry and Thermopolis Shales. The sonic velocities of all four shales are less than that of an interpolated trendline that is tied to velocities in shales above and below the interval of moderate overpressure. The reduction in velocity varies among the four shales, such that the amount of offset (O) from the trendline is OT > OSC > OC > OM, that is, the velocity in the Mowry Shale is reduced the least and the velocity in the Thermopolis Shale is reduced the most. Velocity reductions are attributed to increases in pore pressure during burial, caused by the generation and retention of gas, with lithology playing a key role in the amount of reduction. Sonic velocity in the four shale units remains low to the present day, after uplift and erosion of as much as 6,500 ft in the deeper part of the basin and consequent possible reduction from maximum pore pressures reached when strata were more deeply buried. A model combining burial history, the decrease of effective stress with increasing pore pressure, and Bower's model for the dependence of sonic velocity on effective stress is proposed to explain the persistence of low velocity in shale units. Interruptions to compaction gradients associated with gas occurrences and overpressure are observed in correlative strata in other basins in Wyoming, so the general results for shales in the Bighorn Basin established in this paper should be applicable elsewhere.

Controls on porphyrin concentrations of Pennsylvanian organic-rich shales, Western U.S.A.

USGS Publications Warehouse

Clayton, J.L.; Michael, G.E.

1990-01-01

Organic-rich black shales of Middle Pennsylvanian (Desmoinesian) age occur over much of the central U.S. and as far west as the northern Denver and southeastern Powder River basins. Total organic carbon contents (Corg) are commonly greater than 10 wt %. Porphyrin concentrations (vanadyl + nickel) are as high as 40000 ppm relative to extractable bitumen. In bulk, the organic matter contained in the shales is mostly type II and III (Rock-Eval hydrogen indexes 200-400 mg of hydrocarbons/g of Corg). The finding of high porphyrin concentrations in type III organic matter is unusual but can be explained by a depositional model wherein high preservation of primary organic production (water column photosynthesis) is combined with substantial input of allochthonous organic matter. The allochthonous organic matter (low porphyrin concentration) may come from erosion during advance of the sea across the area or from fluvial transport from shore.

Theoretical modeling of rhenium isotope fractionation, natural variations across a black shale weathering profile, and potential as a paleoredox proxy

NASA Astrophysics Data System (ADS)

Miller, Christian A.; Peucker-Ehrenbrink, Bernhard; Schauble, Edwin A.

2015-11-01

We present the first data documenting environmental variations in the isotope composition of Re, and the first theoretical models of equilibrium Re isotope fractionation factors. Variations of δ187Re at modern surface temperatures are predicted to be ‰ level for redox (ReVII ⇌ ReIV) and perrhenate thiolation reactions (ReVIIO4- ⇌ReVIIOXS4-X- ⇌ReVII S4-). Nuclear volume fractionations are calculated to be smaller than mass dependent effects. Values of δ187Re from New Albany Shale samples presented in this work and in a previous study show a range of 0.8‰ over a stratigraphic interval of ∼20 m. The magnitude of variation is consistent with theoretical predictions and may provide evidence for changing δ187Re of seawater in the geologic past. A -0.3‰ change in δ187Re across a 14 m horizontal black shale weathering profile is accompanied by a hundred-fold decrease in Re concentration and a 75% decrease in organic carbon associated with the transition from reducing to oxic weathering environment. We attribute decreasing δ187Re to the loss of organically bound Re component (δ187Re = -0.28‰). The Re isotope composition of the complementary detrital silicate fraction varies from -0.59 to -1.5‰, depending on the choice of silicate Re concentration.

Chemostratigraphical Characterisation of the Lower Silurian Formigoso Formation: A Case Study from Aralla (Cantabrian Mountains, Province Leon, NW Spain)

NASA Astrophysics Data System (ADS)

Ferriday, T.; Montenari, M.

2012-04-01

The Silurian black shale deposits of the peri-Gondwanan region are one of the most important Palaeozoic source rocks for hydrocarbons world-wide. Despite intensive research, questions regarding the genesis and the palaeoenvironmental and palaeogeographic factors controlling the deposition of these shales are a matter of ongoing debate. The area investigated lies within the Cantabria-Asturias Arc of Northern Spain in the autonomous region of Castilla y León. The Cantabrian Arc formed as a result of the collision between Gondwana and Laurussia during the formation of the supercontinent Pangea and has been divided into five major tectonostratigraphic units. The 'Folds and Nappes' unit is of particular interest, especially the contained Somiedo-Corecillas thrust system, as here the best preserved Formigoso-sections and exposures can be found. This study focuses on the deposition of the L-Silurian black shales of the Formigoso Formation (Fm) within the Somiedo-Corecillas thrust system at Aralla, approximately 10km east-southeast of San Emiliano. A high resolution geochemical analysis of major and trace elements has been utilised on a 25cm scale throughout the section. A total of 241 samples were prepared and analysed using a NITON XL3t X-ray fluorescence instrument. The data obtained have provided new insights into the sedimentation patterns and the prevailing environmental conditions during deposition of the Formigoso Fm. Initial results show prominent regular cycles within the concentrations of red/ox-sensitive chemical elements, starting from the very onset of the anoxic black shales; these repetitions become less apparent towards to top of the formation. Eight cyclic pulses are clearly evident in the concentrations of the elements Uranium (U), Thorium (Th), Vanadium (V) and Chromium (Cr) and apparent in Rubidium (Rb), Zinc (Zn), Copper (Cu), Nickel (Ni), Titanium (Ti), Sulphur (S) and Barium (Ba). The cyclic behaviour of U4+ between 'Anoxia'-U enriched (18ppm)- and 'Dysoxia' -U depleted (8ppm)-, is here interpreted as the result of regular perturbations of the overlying oxygen-depleted water column during deposition, leading to rhythmic oxygenation of the bottom-water masses. These regular perturbations are seen here as the result of a complex interplay between orbital-forced sea-level changes and tectonically induced subsidence; the latter, a result of the widening Rheic Ocean. The basal black shales of the Formigoso Fm represent a duration of approx. 4 Myrs, spanning from the Aeronian/Telychian boundary (436Ma) to the mid-Telychian Monoclimacis Graptolite Zone (~ 432Ma). Therefore, each single cycle seem to represent approximately 500 kyr. This consistent cyclic signal is tentatively interpreted to represent the dynamic sedimentological response to the Earth's 413ka eccentricity. The cyclic geochemical patterns observed within the Lower Silurian Formigoso Fm shall be used for future stratigraphic correlations on an intrabasinal and interbasinal scale for the peri-Gondwanan margins.

Contaminants from Cretaceous Black Shale Part 1: Natural weathering processes controlling contaminant cycling in Mancos Shale, southwestern United States, with emphasis on salinity and selenium

USGS Publications Warehouse

Tuttle, Michele L.W.; Fahy, Juli W.; Elliott, John G.; Grauch, Richard I.; Stillings, Lisa L.

2013-01-01

Soils derived from black shale can accumulate high concentrations of elements of environmental concern, especially in regions with semiarid to arid climates. One such region is the Colorado River basin in the southwestern United States where contaminants pose a threat to agriculture, municipal water supplies, endangered aquatic species, and water-quality commitments to Mexico. Exposures of Cretaceous Mancos Shale (MS) in the upper basin are a major contributor of salinity and selenium in the Colorado River. Here, we examine the roles of geology, climate, and alluviation on contaminant cycling (emphasis on salinity and Se) during weathering of MS in a Colorado River tributary watershed. Stage I (incipient weathering) began perhaps as long ago as 20 ka when lowering of groundwater resulted in oxidation of pyrite and organic matter. This process formed gypsum and soluble organic matter that persist in the unsaturated, weathered shale today. Enrichment of Se observed in laterally persistent ferric oxide layers likely is due to selenite adsorption onto the oxides that formed during fluctuating redox conditions at the water table. Stage II weathering (pedogenesis) is marked by a significant decrease in bulk density and increase in porosity as shale disaggregates to soil. Rainfall dissolves calcite and thenardite (Na2SO4) at the surface, infiltrates to about 1 m, and precipitates gypsum during evaporation. Gypsum formation (estimated 390 kg m−2) enriches soil moisture in Na and residual SO4. Transpiration of this moisture to the surface or exposure of subsurface soil (slumping) produces more thenardite. Most Se remains in the soil as selenite adsorbed to ferric oxides, however, some oxidizes to selenate and, during wetter conditions is transported with soil moisture to depths below 3 m. Coupled with little rainfall, relatively insoluble gypsum, and the translocation of soluble Se downward, MS landscapes will be a significant nonpoint source of salinity and Se to the Colorado River well into the future. Other trace elements weathering from MS that are often of environmental concern include U and Mo, which mimic Se in their behavior; As, Co, Cr, Cu, Ni, and Pb, which show little redistribution; and Cd, Sb, V, and Zn, which accumulate in Stage I shale, but are lost to varying degrees from upper soil intervals. None of these trace elements have been reported previously as contaminants in the study area.

Palaeoecology and sedimentology of the dysaerobic Bedford fauna (late Devonian), Ohio and Kentucky (USA)

USGS Publications Warehouse

Pashin, J.C.; Ettensohn, F.R.

1992-01-01

Oxygen-deficient biofacies models rely on lithologic and paleontologic attributes to identify distinctive biofacies interpreted to reflect levels of oxygenation in anaerobic, dysaerobic, and aerobic parts of a stratified water column. This study of the Bedford fauna from the Bedford Shale of Ohio and Kentucky and from adjacent black-shale units reports faunal distributions different from those predicted by the accepted models. This study suggests that, although oxygenation was an important factor that determined the taxonomic makeup of the fauna, bacterially mediated nutrient recycling and substrate characteristics were more important than oxygenation in determining faunal distribution in the dysaerobic zone. ?? 1992.

Modified Lipid Extraction Methods for Deep Subsurface Shale

PubMed Central

Akondi, Rawlings N.; Trexler, Ryan V.; Pfiffner, Susan M.; Mouser, Paula J.; Sharma, Shikha

2017-01-01

Growing interest in the utilization of black shales for hydrocarbon development and environmental applications has spurred investigations of microbial functional diversity in the deep subsurface shale ecosystem. Lipid biomarker analyses including phospholipid fatty acids (PLFAs) and diglyceride fatty acids (DGFAs) represent sensitive tools for estimating biomass and characterizing the diversity of microbial communities. However, complex shale matrix properties create immense challenges for microbial lipid extraction procedures. Here, we test three different lipid extraction methods: modified Bligh and Dyer (mBD), Folch (FOL), and microwave assisted extraction (MAE), to examine their ability in the recovery and reproducibility of lipid biomarkers in deeply buried shales. The lipid biomarkers were analyzed as fatty acid methyl esters (FAMEs) with the GC-MS, and the average PL-FAME yield ranged from 67 to 400 pmol/g, while the average DG-FAME yield ranged from 600 to 3,000 pmol/g. The biomarker yields in the intact phospholipid Bligh and Dyer treatment (mBD + Phos + POPC), the Folch, the Bligh and Dyer citrate buffer (mBD-Cit), and the MAE treatments were all relatively higher and statistically similar compared to the other extraction treatments for both PLFAs and DGFAs. The biomarker yields were however highly variable within replicates for most extraction treatments, although the mBD + Phos + POPC treatment had relatively better reproducibility in the consistent fatty acid profiles. This variability across treatments which is associated with the highly complex nature of deeply buried shale matrix, further necessitates customized methodological developments for the improvement of lipid biomarker recovery. PMID:28790998

Evolution of volcanically-induced palaeoenvironmental changes leading to the onset of OAE1a (early Aptian, Cretaceous)

NASA Astrophysics Data System (ADS)

Keller, Christina E.; Hochuli, Peter A.; Giorgioni, Martino; Garcia, Therese I.; Bernasconi, Stefano M.; Weissert, Helmut

2010-05-01

During the Cretaceous, several major volcanic events occurred that initiated climate warming, altered marine circulation and increased marine productivity, which in turn often resulted in the widespread black shale deposits of the Oceanic Anoxic Events (OAE). In the sediments underlying the early Aptian OAE1a black shales, a prominent negative carbon isotope excursion is recorded. Its origin had long been controversial (e.g. Arthur, 2000; Jahren et al., 2001) before recent studies attributed it to the Ontong Java volcanism (Méhay et al., 2009; Tejada et al., 2009). Therefore the negative C-isotope excursion covers the interval between the time, when volcanic activity became important enough to be recorded in the C-isotope composition of the oceans to the onset of widespread anoxic conditions (OAE1a). We chose this interval at the locality of Pusiano (N-Italy) to study the effect of a volcanically-induced increase in pCO2 on the marine palaeoenvironment and to observe the evolving palaeoenvironmental conditions that finally led to OAE1a. The Pusiano section (Maiolica Formation) was deposited at the southern continental margin of the alpine Tethys Ocean and has been bio- and magnetostratigraphically dated by Channell et al. (1995). We selected 18 samples from 12 black shale horizons for palynofacies analyses. Palynofacies assemblages consist of several types of particulate organic matter, providing information on the origin of the organic matter (terrestrial/marine) and conditions during deposition (oxic/anoxic). We then linked the palynofacies results to high-resolution inorganic and organic C-isotope values and total organic carbon content measurements. The pelagic Pusiano section consists of repeated limestone-black shale couplets, which are interpreted to be the result of changes in oxygenation of bottom waters. Towards the end of the negative C-isotope excursion we observe enhanced preservation of the fragile amorphous organic matter resulting in increased total organic carbon values in the black shale as well as in the limestone intervals. This shows how a rising pCO2 triggered changes in climate and oceanography and resulted in an increasing oxygen-deficiency of the bottom waters that persisted even during the 'limestone intervals' before oxygen-depletion finally became a global phenomenon. References: Arthur, M.A., 2000, Volcanic contributions to the carbon and sulfur geochemical cycles and global change, in Sigurdsson, H., Houghton, B., McNutt, S.R., Rymer, H., and Stix, J., eds., Encyclopedia of Volcanoes, Academic Press, p. 1045-1056. Channell, J.E.T., Cecca, F., and Erba, E., 1995, Correlations of Hauterivian and Barremian (Early Cretaceous) stage boundaries to polarity chrons: Earth and Planetary Science Letters, v. 134, p. 125-140. Jahren, A.H., Arens, N.C., Sarmiento, G., Guerrero, J., and Amundson, R., 2001, Terrestrial record of methane hydrate dissociation in the Early Cretaceous: Geology, v. 29, p. 159-162. Méhay, S., Keller, C.E., Bernasconi, S.M., Weissert, H., Erba, E., Bottini, C., and Hochuli, P.A., 2009, A volcanic CO2 pulse triggered the Cretaceous Oceanic Anoxic Event 1a and a biocalcification crisis: Geology, v. 37, p. 819-822. Tejada, M.L.G., Suzuki, K., Junichiro, K., Rodolfo, C., J., M.J., Naohiko, O., Tatsuhiko, S., and Yoshiyuki, T., 2009, Ontong Java Plateau eruption as a trigger for the early Aptian oceanic anoxic event: Geology, v. 37, p. 855-858.

Shale across Scales from the Depths of Sedimentary Basins to Soil and Water at Earth's Surface

NASA Astrophysics Data System (ADS)

Brantley, S. L.; Gu, X.

2017-12-01

Shale has become highly important on the world stage because it can host natural gas. In addition, shale is now targeted as a formation that can host repositories for disposal of radioactive waste. This newly recognized importance of shale has driven increased research into the nature of this unusual material. Much of this research incorporates characterization tools that probe shale at scales from nanometers to millimeters. Many of the talks in this Union session discuss these techniques and how scientists use them to understand how they impact the flow of fluids at larger scales. Another research avenue targets how material properties affect soil formation on this lithology and how water quality is affected in sedimentary basins where shale gas resources are under development. For example, minerals in shale are dominated by clays aligned along bedding. As the shales are exhumed and exposed at the surface during weathering, bedding planes open and fractures and microfractures form, allowing outfluxes or influxes of fluids. These phenomena result in specific patterns of fluid flow and, eventually, soil formation and landscape development. Specifically, in the Marcellus Formation gas play - the largest shale gas play in the U.S.A. - exposures of the shale at the surface result in deep oxidation of pyrite and organic matter, deep dissolution of carbonates, and relatively shallow alteration of clays. Micron-sized particles are also lost from all depths above the oxidation front. These characteristics result in deeply weathered and quickly eroded landscapes, and may also be related to patterns in water quality in shale gas plays. For example, across the entire Marcellus shale gas play in Pennsylvania, the single most common water quality issue is contamination by natural gas. This contamination is rare and is observed to be more prevalent in certain areas. These areas are likely related to shale material properties and geological structure. Specifically, natural gas moves along opening bedding planes as well as through faults and other larger scale geologic structures within basins. Understanding how shale acts as a material at all depths from that of fracking to that of the forest will enhance our ability to power our societal needs, dispose of our wastes, and sustain our water and soil resources.

Influence of Composition and Deformation Conditions on the Strength and Brittleness of Shale Rock

NASA Astrophysics Data System (ADS)

Rybacki, E.; Reinicke, A.; Meier, T.; Makasi, M.; Dresen, G. H.

2015-12-01

Stimulation of shale gas reservoirs by hydraulic fracturing operations aims to increase the production rate by increasing the rock surface connected to the borehole. Prospective shales are often believed to display high strength and brittleness to decrease the breakdown pressure required to (re-) initiate a fracture as well as slow healing of natural and hydraulically induced fractures to increase the lifetime of the fracture network. Laboratory deformation tests were performed on several, mainly European black shales with different mineralogical composition, porosity and maturity at ambient and elevated pressures and temperatures. Mechanical properties such as compressive strength and elastic moduli strongly depend on shale composition, porosity, water content, structural anisotropy, and on pressure (P) and temperature (T) conditions, but less on strain rate. We observed a transition from brittle to semibrittle deformation at high P-T conditions, in particular for high porosity shales. At given P-T conditions, the variation of compressive strength and Young's modulus with composition can be roughly estimated from the volumetric proportion of all components including organic matter and pores. We determined also brittleness index values based on pre-failure deformation behavior, Young's modulus and bulk composition. At low P-T conditions, where samples showed pronounced post-failure weakening, brittleness may be empirically estimated from bulk composition or Young's modulus. Similar to strength, at given P-T conditions, brittleness depends on the fraction of all components and not the amount of a specific component, e.g. clays, alone. Beside strength and brittleness, knowledge of the long term creep properties of shales is required to estimate in-situ stress anisotropy and the healing of (propped) hydraulic fractures.

Constraining the thermal structure beneath Lusi: insights from temperature record in erupted clasts

NASA Astrophysics Data System (ADS)

Malvoisin, Benjamin; Mazzini, Adriano; Miller, Stephen

2016-04-01

Sedimentary units beneath Lusi from surface to depth are the Pucangan formation, the Upper Kalibeng formation where shales and then volcanoclastic clasts are found, the Kujung-Propuh-Tuban formation composed of carbonates and the Ngimbang formation composed of shales. Water and gas geochemistry as well as surface deformation indicate that Lusi is a hydrothermal system rooted at >4 km depth. However, the thermal structure beneath Lusi is still poorly constrained whereas it has first-order impacts on the physical and chemical processes observed during the eruption. In the framework of the Lusi Lab project (ERC grant n° 308126) and of a project of the Swiss National Science Foundation (n°160050) we studied erupted clasts collected at the crater site to determine their source and temperature record. Three types of clasts were studied based on morphological and mineralogical basis. The first type is limestones mainly composed of Ca- and Fe-bearing carbonates. The clasts of the second type are light grey shales (LGS) containing carbonaceous matter, illite/smectite mixture, plagioclase and quartz. The third type is also a shale with a black colour containing hydrocarbons (black shales, BS) and with the additional presence of Na-rich plagioclase, biotite and chlorite. The presence of these latter minerals indicates hydrothermal activity at relatively high temperature. Better constraints on temperature were obtained by using both Raman spectroscopic carbonaceous material thermometry (RSCM) and chlorite geothermometry. Temperatures below 200°C were determined for the LGS with RSCM. BS recorded two temperatures. The first one, around 170°C, is rather consistent with an extrapolation of the geothermal gradient measured before the eruption up to 4,000 m depth. Combined with mineralogical observations, this suggests that BS originate from the Ngimbang formation. The second recorded higher temperature around 250°C indicates heating, probably through interaction with high temperature hydrothermal fluids. Calculations performed for such a heating indicate that associated clay dehydration is sufficient to provide the water released during the eruption and that heating-induced overpressure could favor fluid ascent. These results confirm the hydrothermal scenario in which Lusi eruption is fed by high temperature fluid circulation from the neighboring Arjuno-Welirang volcanic complex.

Dissolved methane in New York groundwater, 1999-2011

USGS Publications Warehouse

Kappel, William M.; Nystrom, Elizabeth A.

2012-01-01

New York State is underlain by numerous bedrock formations of Cambrian to Devonian age that produce natural gas and to a lesser extent oil. The first commercial gas well in the United States was dug in the early 1820s in Fredonia, south of Buffalo, New York, and produced methane from Devonian-age black shale. Methane naturally discharges to the land surface at some locations in New York. At Chestnut Ridge County Park in Erie County, just south of Buffalo, N.Y., several surface seeps of natural gas occur from Devonian black shale, including one behind a waterfall. Methane occurs locally in the groundwater of New York; as a result, it may be present in drinking-water wells, in the water produced from those wells, and in the associated water-supply systems (Eltschlager and others, 2001). The natural gas in low-permeability bedrock formations has not been accessible by traditional extraction techniques, which have been used to tap more permeable sandstone and carbonate bedrock reservoirs. However, newly developed techniques involving horizontal drilling and high-volume hydraulic fracturing have made it possible to extract previously inaccessible natural gas from low-permeability bedrock such as the Marcellus and Utica Shales. The use of hydraulic fracturing to release natural gas from these shale formations has raised concerns with water-well owners and water-resource managers across the Marcellus and Utica Shale region (West Virginia, Pennsylvania, New York and parts of several other adjoining States). Molofsky and others (2011) documented the widespread natural occurrence of methane in drinking-water wells in Susquehanna County, Pennsylvania. In the same county, Osborn and others (2011) identified elevated methane concentrations in selected drinking-water wells in the vicinity of Marcellus gas-development activities, although pre-development samples were not available for comparison. In order to manage water resources in areas of gas-well drilling and hydraulic fracturing in New York, the natural occurrence of methane in the State's aquifers needs to be documented. This brief report presents a compilation of data on dissolved methane concentrations in the groundwater of New York available from the U.S. Geological Survey (USGS) National Water Information System (NWIS) (http://waterdata.usgs.gov/nwis).

Spectroscopic geochemical study of vanadiferous marine sediments of the Gibellini claims, southern Fish Creek Range, Eureka County, Nevada

USGS Publications Warehouse

Böhlke, J.K.; Radtke, A.S.; Heropoulos, Chris; Lamothe, P.J.

1981-01-01

Samples of cuttings from three drill holes in the Gibellini claims were analyzed by emission spectroscopic techniques for a large suite of major and trace elements. Unoxidized siliceous "black shale" from drill hole NGA 7 is strongly enriched in Cd, Mo, Sb, Se, V, and Zn, and also contains relatively high concentrations of As, Ba, Cu, Ni, and Tl compared with nonmetalliferous shales. Analyses of 103 samples plotted against depth in drill holes NGA, NG31, and NGA7, and selected XRD data, show the following: 1. Groups of elements with distinct distribution patterns define most of major mineralogic components of the rocks. The "normal shale" component, which includes several detrital and authigenic phases, is indicated by covariations among Ti, Al, Fe, Na, Mg, K, B, Be, Co, Cr, Ga, La, Sc, Sr, and Zr. The shale component is diluted by varying amounts of the following minerals (and associated elements): silica (Si); dolomite (Mg, Ca, Mn, Sr); apatite (Ca, Be, Cr, La, Sr, Y); barite (Ba, Sr); sphalerite (Zn, Cd, Fe?); smithsonite (Cd, Co, Mn, Ni, Zn); bianchite (Cd, Ni, Zn) ; and bokite (V). Pyrite, gypsum, and jarosite were also identified.2. The highly siliceous kerogenous metalliferous Gibellini facies is underlain by argillaceous and (or) dolomitic rocks. The transition zone deduced from the chemical data is not well defined in all instances, but probably represents the bottom of the black shale deposit. 3. Oxidation has reached to variable depths up to at least 150 ft, and has caused profound changes in the distributions of the enriched metals. Molybdenum, Se, and V have been partially removed from the upper parts of the sections and are concentrated near or slightly above the base of the Gibellini facies. Cadmium, Ni, and Zn have been strongly leached and now occur at or below the base of the Gibellini facies. The variable depth of oxidation, the redistribution and separation of the metals, and the complex mineralogy of the deposit may make development of the claim complicated.

Making Knowledge from Numbers : The Shale Network as an Honest Broker for Evaluating and Educating about the Impacts of Hydraulic Fracturing in the Marcellus Shale Region

NASA Astrophysics Data System (ADS)

Pollak, J.; Brantley, S.; Williams, J.; Dykhoff, S.; Brazil, L. I.

2015-12-01

The Marcellus Shale Network is an NSF-funded project that investigates the impacts of hydraulic fracturing for shale gas development on water resources in and around the state of Pennsylvania. It is a collaborative effort that aims to be an honest broker in the shale gas conversation by involving multiple entities (including universities, government agencies, industry groups, nonprofits, etc.) to collect, analyze, and disseminate data that describe the past and current conditions of water in the Marcellus shale region. A critical component of this project has been to engage multiple types of stakeholders - academia, government agencies, industry, and citizen science groups - in annual workshops to present and discuss how to ensure the integrity of water resources in light of the challenges that natural gas extraction can present. Each workshop has included a hands-on activity that allows participants to access water quality data using the tools provided by the CUAHSI Water Data Center. One of these tools is HydroDesktop, which is an open source GIS application that can be used in formal and informal education settings as a geoscience research tool. In addition to being a GIS, HydroDesktop accesses CUAHSI's large catalog of water data thus enabling students, professional researchers, and citizen scientists to discover data that can expand the understanding of water quality issues in one's local environment and beyond. This presentation will highlight the goals of the Shale Network project and the stakeholders involved in addition to how cyberinfrastructure is being used to create a democratic, data-driven conversation about the relationship between energy production from shale gas and our water resources.

Vanadium

USGS Publications Warehouse

Kelley, Karen D.; Scott, Clinton T.; Polyak, Désirée E.; Kimball, Bryn E.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Vanadium is used primarily in the production of steel alloys; as a catalyst for the chemical industry; in the making of ceramics, glasses, and pigments; and in vanadium redox-flow batteries (VRBs) for large-scale storage of electricity. World vanadium resources in 2012 were estimated to be 63 million metric tons, which include about 14 million metric tons of reserves. The majority of the vanadium produced in 2012 was from China, Russia, and South Africa.Vanadium is extracted from several different types of mineral deposits and from fossil fuels. These deposits include vanadiferous titanomagnetite (VTM) deposits, sandstone-hosted vanadium (with or without uranium) deposits (SSV deposits), and vanadium-rich black shales. VTM deposits are the principal source of vanadium and consist of magmatic accumulations of ilmenite and magnetite containing 0.2 to 1 weight percent vanadium pentoxide (V2O5). SSV deposits are another important source; these deposits have average ore grades that range from 0.1 to greater than 1 weight percent V2O5. The United States has been and is currently the main producer of vanadium from SSV deposits, particularly those on the Colorado Plateau. Vanadium-rich black shales occur in marine successions that were deposited in epeiric (inland) seas and on continental margins. Concentrations in these shales regularly exceed 0.18 weight percent V2O5 and can be as high as 1.7 weight percent V2O5. Small amounts of vanadium have been produced from the Alum Shale in Sweden and from ferrophosphorus slag generated during the reduction of phosphate to elemental phosphorus in ore from shales of the Phosphoria Formation in Idaho and Wyoming. Because vanadium enrichment occurs in beds that are typically only a few meters thick, most of the vanadiferous black shales are not currently economic, although they may become an important resource in the future. Significant amounts of vanadium are recovered as byproducts of petroleum refining, and processing of coal, tar sands, and oil shales may be important future sources.Vanadium occurs in one of four oxidation states in nature: +2, +3, +4, and +5. The V3+ ion has an octahedral radius that is almost identical to that of (Fe3+) and (Al3+) and, therefore, it substitutes in ferromagnesian minerals. During weathering, much of the vanadium may partition into newly formed clay minerals, and it either remains in the +3 valence state or oxidizes to the +4 valence state, both of which are relatively insoluble. If erosion is insignificant but chemical leaching is intense, the residual material may be enriched in vanadium, as are some bauxites and laterites. During the weathering of igneous, residual, or sedimentary rocks, some vanadium oxidizes to the +5 valence state, especially in the intensive oxidizing conditions that are characteristic of arid climates.The average contents of vanadium in the environment are as follows: soils [10 to 500 parts per million (ppm)]; streams and rivers [0.2 to 2.9 parts per billion (ppb)]; and coastal seawater (0.3 to 2.8 ppb). Concentrations of vanadium in soils (548 to 7,160 ppm) collected near vanadium mines in China, the Czech Republic, and South Africa are many times greater than natural concentrations in soils. Additionally, if deposits contain sulfide minerals such as chalcocite, pyrite, and sphalerite, high levels of acidity may be present if sulfide dissolution is not balanced by the presence of acid-neutralizing carbonate minerals. Some of the vanadium-bearing deposit types, particularly some SSV and black-shale deposits, contain appreciable amounts of carbonate minerals, which lowers the acid-generation potential.Vanadium is a micronutrient with a postulated requirement for humans of less than 10 micrograms per day, which can be met through dietary intake. Primary and secondary drinking water regulations for vanadium are not currently in place in the United States. Vanadium toxicity is thought to result from an intake of more than 10 to 20 milligrams per day. Vanadium is essential for some biological processes and organisms. For example, some nitrogen-fixing bacteria require vanadium for producing enzymes necessary to convert nitrogen from the atmosphere into ammonia, which is a more biologically accessible form of nitrogen.

Organic matter from the Bunte Breccia of the Ries Crater, southern Germany: investigating possible thermal effects of the impact

NASA Astrophysics Data System (ADS)

Hofmann, P.; Leythaeuser, D.; Schwark, L.

2001-07-01

In order to determine thermal effects of the Ries impact, southern Germany, on organic matter in its ejecta blanket, the maturity of organic matter of Posidonia Shale components from the Bunte Breccia at Harburg and Gundelsheim is compared with the maturity of organic matter of a reference section of Posidonia Shale outside the impact site at Hesselberg. Three black shale samples from the Bunte Breccia were identified as corresponding to the organic matter-rich Posidonia Shale based on the molecular composition of extractable organic matter. They show n-alkane patterns with a maximum of n-C 17, a predominance of odd over even n-alkanes in the range from n-C 26 to n-C 35, a dominance of unsaturated sterenes over steranes and monoaromatic over triaromatic steroids, and contain isorenieratene. The maturity of the organic matter from the Bunte Breccia samples corresponds to 0.32-0.35% random vitrinite reflectance ( Rr) and a spectral red/green quotient ( Q) of 0.32-0.34. The organic matter from the Bunte Breccia is more mature than the Posidonia Shale sample from the reference site Hesselberg (0.25% Rr; 0.21 for Q). The thermal overprint is presumed to be too high to be explained by differences in the burial history prior to the impact alone and is, therefore, attributed to processes related to the displacement of the Bunte Breccia.

Tin-polymetallic sulfide deposits in the eastern part of the Dachang tin field (South China) and the role of black shales in their origin

NASA Astrophysics Data System (ADS)

Pašava, Jan; Kříbek, Bohdan; Dobeš, Petr; Vavřín, Ivan; Žák, Karel; Delian, Fan; Tao, Zhang; Boiron, Marie-Christine

2003-01-01

The Dafulou and Huile vein and stratabound cassiterite-sulfide deposits and sheeted ore veins at the Kangma cassiterite-sulfide deposit are located in the eastern part of the Dachang tin field. These deposits are hosted in a sedimentary sequence containing significant concentrations of organic matter in the form of Lower Devonian calcareous black shales and hornfels. These rocks together with the younger intrusion of Longxianggai granite (91±2 Ma) actively participated in the formation of Sn-polymetallic deposits. The following three major stages have been distinguished in stratiform and vein-type orebodies at Dafulou, Huile and Kangma: stage I (cassiterite, pyrrhotite, arsenopyrite, tourmaline, carbonate), stage II - main sulfide stage (quartz, cassiterite, arsenopyrite, pyrrhotite, sphalerite, stannite, pyrite, carbonates) and stage III (native Bi, galena, electrum, sulfosalts). Stage IV (post-ore), recognized at Huile is represented by barren carbonates and zeolites. Whole rock geochemistry has revealed that at Dafulou, Bi and Cu correlate strongly with S, whereas V and Pb correlate well with Corg (organic carbon). The similar distribution patterns of selected elements in average slightly mineralized low-Ca black shales indicate a fluid composition similar for all deposits studied. Studies of graphitization of the organic matter in black shales adjacent to orebodies indicate that d(002) and FWHM (full width in half maximum)/peak height values gradually decrease in the following sequence: Dafulou deposit → Kangma deposit → Huile deposit. The pyrolysate of wall rocks at the Dafulou deposit is relatively enriched in asphaltenes and maltenes (55.6-72.0% of the pyrolysate) comparable with pyrolysate obtained from more distal black shales (19.2-28.5%). Typical GC-MS spectra of pyrolysate from distal black shales are dominated by alkanes in the n-C15 to n-C25 range, aromatic molecules being represented mostly by alkyl-naphthalenes. In contrast, only traces of aliphatic hydrocarbons in the n-C14 to n-C18 range and elemental sulfur were identified in pyrolysates from pyrrhotitized wall rocks. The earliest fluid inclusions of the studied system occur in the quartz-tourmaline-cassiterite assemblage of stage I at Dafulou. These inclusions are H2O-CO2-CH4-rich, with 10 to 20 vol% of aqueous phase. P-T conditions of the trapping of inclusions are estimated to be up to 400 °C and 1.3 to 2.0 kbar (between 5.0 and 7.5 km under lithostatic pressure). In contrast, the presence of a low density gaseous CO2-CH4 phase indicates relatively low pressures during the formation of the breccia-type quartz-calcite-cassiterite-sulfide mineralization (stage II), when P-T conditions probably reached approx. 380 to 400 °C and 0.6 kbar (up to 6 km under hydrostatic pressure). Fluid inclusion data and oxygen isotope thermometry indicate that cassiterite-sulfide ores of the main sulfide stage (stage II) formed from aqueous-carbonic fluid (CO2/CH4 =≈10) at temperatures of up to 390 °C at Dafulou and in a temperature range of 250 to 360 °C at Huile and 260 to 370 °C at Kangma. The δ34S values of sulfides from Dafulou range mostly between -1 and -6‰, whereas sulfides from the Kangma and Huile deposits are characterized by more negative δ34S values (between -8 and -11‰, and between -9 and -12‰, respectively). These data suggest that bacteriogenic sulfides of black shales were a dominant source of reduced sulfur for epigenetic (vein and replacement) mineralization. Oxygen isotopic compositions of five quartz-cassiterite pairs from Dafulou and Huile show a relatively narrow range of calculated oxygen isotope temperatures (250-320 °C, using the equation of Alderton 1989) and high δ18Ofluid values between +8 and +10‰ (SMOW), which are in agreement with fluid derivation from and/or high temperature equilibration with the Longxianggai granite. The carbon and oxygen isotope composition of carbonates reflects variable carbon sources. Stage I calcite is characterized by narrow ranges of δ13C (-7.0 to -9.5‰ PDB) and δ18O (+15.0 to +17.5‰ SMOW). This calcite shows ubiquitous deformation, evidenced by intense development of twins. Fluid compositions calculated at 330 °C for the Dafulou and Huile deposits and at 270-300 °C for the Kangma deposit (δ18Ofluid between +10.0 and +11.5‰ SMOW, δ13Cfluid between -5.5 and -7.5‰ PDB), agree with fluid derivation from and/or equilibration with the peraluminous, high-δ18O Longxianggai granite and suggest a significant influence of contact metasedimentary sequences (carbon derived from decomposition and/or alteration of organic matter of calcareous black shales). The δ13 C values of organic matter from the Lower to Upper Devonian host rocks at the Dafulou deposit (-24.0 and -28.0‰) fit with a marine origin from algae. However, organic matter adjacent to the host rock-ore contact displays a slight enrichment in 13C. The organic carbon from the Huile and Kangma deposits is even more 13C enriched (-24.6 to -23.5‰). The most heavy δ13 C values (-16.5‰) were detected in hornfels sampled at the contact of the Upper Devonian sediments with the Longxianggai granite. The δ13C data broadly correlate with the degree of structural ordering (degree of graphitization) of organic matter, which indicates that both variables are related to thermal overprint.

Investigation of water-soluble organic matter extracted from shales during leaching experiments

NASA Astrophysics Data System (ADS)

Zhu, Yaling; Vieth-Hillebrand, Andrea; Wilke, Franziska D. H.; Horsfield, Brian

2017-04-01

The huge volumes and unknown composition of flowback and produced waters cause major public concerns about the environmental and social compatibility of hydraulic fracturing and the exploitation of gas from unconventional reservoirs. Flowback and produced waters contain not only residues of fracking additives but also chemical species that are dissolved from the shales themselves during fluid-rock interaction. Knowledge of the composition, size and structure of dissolved organic carbon (DOC) as well as the main controls on the release of DOC are a prerequisite for a better understanding of these interactions and its effects on composition of flowback and produced water. Black shales from four different geological settings and covering a maturity range Ro = 0.3-2.6% were extracted with deionized water. The DOC yields were found to decrease rapidly with increasing diagenesis and remain low throughout catagenesis. Four DOC fractions have been qualitatively and quantitatively characterized using size-exclusion chromatography. The concentrations of individual low molecular weight organic acids (LMWOA) decrease with increasing maturity of the samples except for acetate extracted from the overmature Posidonia shale, which was influenced by hydrothermal brines. The oxygen content of the shale organic matter also shows a significant influence on the release of organic acids, which is indicated by the positive trend between oxygen index (OI) and the concentrations of formate and acetate. Based on our experiments, both the properties of the organic matter source and the thermal maturation progress of the shale organic matter significantly influence the amount and quality of extracted organic compounds during the leaching experiments.

Arkansas River and Tributaries Arkansas and Oklahoma. Toad Suck Ferry Lock and Dam, Conway Water Supply Foundation Report.

DTIC Science & Technology

1983-06-01

NUMBER CORE BOXES NASH IS ELEV....ION GROUND WATER 6 DIRECTION OF HOLE 3-.. E VETa DATE OLE 5/30/78 5/31/ 7’ 1,7 UtmATJON o TOP 5 OLE / 7 THICKNESS OF...JUN 83 UNCLASSIFIED F/G 13/13 NL mommmmommm 0 I~lmlIIIImEE mhEgEBhEEBhIEE E Eg //EEE n-EEEElgEl- E .II 1.0 II1 l w20 1111.25 111111’.4 1II1.6 MICROCOPY...Kerr Arkansas River Navigation System. e dam was founded on a thick shale layer of the Atoka Formation. Locally, the shale was gray to black, hard to

Black shale source rocks and oil generation in the Cambrian and Ordovician of the central Appalachian Basin, USA

USGS Publications Warehouse

Ryder, R.T.; Burruss, R.C.; Hatch, J.R.

1998-01-01

Nearly 600 million bbl of oil (MMBO) and 1 to 1.5 trillion ft3 (tcf) of gas have been produced from Cambrian and Ordovician reservoirs (carbonate and sandstone) in the Ohio part of the Appalachian basin and on adjoining arches in Ohio, Indiana, and Ontario, Canada. Most of the oil and gas is concentrated in the giant Lima-Indiana field on the Findlay and Kankakee arches and in small fields distributed along the Knox unconformity. Based on new geochemical analyses of oils, potential source rocks, bitumen extracts, and previously published geochemical data, we conclude that the oils in both groups of fields originated from Middle and Upper Ordovician blcak shale (Utica and Antes shales) in the Appalachian basin. Moroever, we suggest that approximately 300 MMBO and many trillions of cubic feet of gas in the Lower Silurian Clinton sands of eastern Ohio originated in the same source rocks. Oils from the Cambrian and Ordovician reservoirs have similar saturated hydrocarbon compositions, biomarker distributions, and carbon isotope signatures. Regional variations in the oils are attributed to differences in thermal maturation rather than to differences in source. Total organic carbon content, genetic potential, regional extent, and bitument extract geochemistry identify the balck shale of the Utica and Antes shales as the most plausible source of the oils. Other Cambrian and Ordovician shale and carbonate units, such as the Wells Creek formation, which rests on the Knox unconformity, and the Rome Formation and Conasauga Group in the Rome trough, are considered to be only local petroleum sources. Tmax, CAI, and pyrolysis yields from drill-hole cuttings and core indicate that the Utica Shale in eastern and central Ohio is mature with respect to oil generation. Burial, thermal, and hydrocarbon-generation history models suggest that much of the oil was generated from the Utica-Antes source in the late Paleozoic during the Alleghanian orogeny. A pervasive fracture network controlled by basement tectonics aided in the distribution of oil from the source to the trap. This fracture network permitted oil to move laterally and stratigraphically downsection through eastward-dipping, impermeable carbonate sequences to carrier zones such as the Middle Ordovician Knox unconformity, and to reservoirs such as porous dolomite in the Middle Ordovician Trenton Limestone in the Lima-Indiana field. Some of the oil and gas from the Utica-Antes source escaped vertically through a partially fractured, leaky Upper Ordovician shale seal into widespread Lower Silurian sandstone reservoirs.Nearly 600 million bbl of oil (MMBO) and 1 to 1.5 trillion ft3 (tcf) of gas have been produced from Cambrian and Ordovician reservoirs (carbonate and sandstone) in the Ohio part of the Appalachian basin and on adjoining arches in Ohio, Indiana, and Ontario, Canada. Most of the oil and gas is concentrated in the giant Lima-Indiana field on the Findlay and Kankakee arches and in small fields distributed along the Knox unconformity. Based on new geochemical analyses of oils, potential source rocks, bitumen extracts, and previously published geochemical data, we conclude that the oils in both groups of fields originated from Middle and Upper Ordovician black shale (Utica and Antes shales) in the Appalachian basin. Moreover, we suggest that approximately 300 MMBO and many trillions of cubic feet of gas in the Lower Silurian Clinton sands of eastern Ohio originated in these same source rocks.

Paleozoic sedimentary rocks in the Red Dog Zn-Pb-Ag district and vicinity, western Brooks Range, Alaska: provenance, deposition, and metallogenic significance

USGS Publications Warehouse

Slack, John F.; Dumoulin, Julie A.; Schmidt, J.M.; Young, L.E.; Rombach, Cameron

2004-01-01

The distribution and composition of Paleozoic strata in the western Brooks Range may have played a fundamental role in Zn-Pb mineralization of the Red Dog district. In our model, deposition and early lithification of biogenic chert and bedded siliceous rocks in the upper part of the Kuna Formation served as a regional hydrologic seal, acting as a cap rock to heat and hydrothermal fluids during Late Mississippian base-metal mineralization. Equally important was the iron-poor composition of black shales of the Kuna Formation (i.e., low Fe/Ti ratios), which limited synsedimentary pyrite formation in precursor sediments, resulting in significant H2S production in pore waters through the interaction of aqueous sulfate with abundant organic matter. This H2S may have been critical to the subsurface deposition of the huge quantities of Zn and Pb in the district. On the basis of this model, we propose that low Fe/Ti and S/C ratios in black shale sequences are potential basin-scale exploration guides for giant sediment-hosted, stratiform Zn-Pb-Ag deposits.

From carbonate platform to euxinic sea - the collapse of an Early/Middle Devonian reef, Cantabrian Mountains (Spain)

NASA Astrophysics Data System (ADS)

Loevezijn, Gerard B. S. van; Raven, J. G. M.

2017-12-01

The Santa Lucía Formation represents the major phase in Devonian reef development of the Cantabrian Zone (Cantabrian Mountains, northwest Spain). In the present study the transition from the carbonate platform deposits of the Santa Lucía Formation to the overlying euxinic basinal deposits of the Huergas Formation is described. These transitional strata are connected to the Basal Choteč Event and represent a condensed sedimentation of micritic dark-grey and black limestones with an upward increase of dark shale intercalations with iron mineralisation surfaces and storm-induced brachiopod coquinas. The transitional beds are grouped into a new unit, the Cabornera Bed, which consists of limestone, limestone-shale and shale facies associations, representing a sediment-starved euxinic offshore area just below the storm wave base. Four stages in reef decline can be recognised: a reef stage, an oxygen-depleted, nutrient-rich stage, a siliciclastic-influx stage and a pelagic-siliciclastic stage. Additional geochemical and geophysical investigations are needed to verify the results presented herein.

Nature and regional significance of unconformities associated with the Middle Ordovician Hagan K-bentonite complex in the North American midcontinent

USGS Publications Warehouse

Kolata, Dennis R.; Huff, W.D.; Bergstrom, Stig M.

1998-01-01

Stratal patterns of the Middle Ordovician Hagan K-bentonite complex and associated rocks show that the Black River-Trenton unconformity in the North American midcontinent formed through the complex interplay of eustasy, sediment accumulation rates, siliciclastic influx, bathymetry, seawater chemistry, and perhaps local tectonic uplift. The unconformity is diachronous and is an amalgamated surface that resulted from local late Turinian lowstand exposure followed by regional early Chatfieldian transgressive drowning and sediment starvation. The duration of the unconformity is greatest in southern Wisconsin, northern Illinois, and northern Indiana, where the Deicke and Millbrig K-bentonite Beds converge at the unconformity. On the basis of published isotopic ages for the Deicke and Millbrig beds, it is possible that in these regions erosion and non-deposition spanned a period of as much as 3.2 m.y. Two broad coeval depositional settings are recognized within the North American midcontinent during early Chatfieldian time. 1) An inner shelf, subtidal facies of fossiliferous shale (Spechts Ferry Shale Member and Ion Shale Member of the Decorah Formation) and argillaceous lime mudstone and skeletal wackestone (Guttenberg and Kings Lake Limestone Members) extended from the Canadian shield and Transcontinental arch southeastward through Minnesota, Wisconsin, Iowa, and Missouri. 2) A seaward, relatively deep subtidal, sediment-starved, middle shelf extended eastward from the Mississippi Valley region to the Taconian foreland basins in the central and southern Appalachians and southward through the pericratonic Arkoma and Black Warrior basins. In the inner shelf region, the Black River-Trenton unconformity is a composite of at least two prominent hardground omission surfaces, one at the top of the Castlewood and Carimona Limestone Members and the other at the top of the Guttenberg and Kings Lake Limestone Members, both merging to a single surface in the middle shelf region. The inner and middle shelves redeveloped later in approximately the same regions during Devonian and Mississippian time.

The Application of 238U/235U as a Redox-Proxy for Past Ocean Chemistry

NASA Astrophysics Data System (ADS)

Andersen, M. B.; Westermann, S.; Bahniuk, A.; Vasconcelos, C.; McKenzie, J. A.; Föllmi, K. B.; Vance, D.

2014-12-01

The recent discovery of significant variation in 238U/235U caused by redox change at the surface Earth has led to its use to extract information on the oxygenation state of ancient oceans from marine sediments [e.g. 1]. Recent studies have focused on improving the understanding of the 238U/235U signature in modern marine carbonates [2] and black shales [3] to improve the robustness of this tracer. To further advance its use we have focused on improving our understanding of 238U/235U systematics in modern dolomite, another commonly occurring rock-type in the geological record, before turning to 238U/235U signatures in ancient sediments. The measured dolomite samples, precipitated in modern environments of coastal hypersaline lagoons in Brazil, all exhibit 238U/235U values that deviate from the seawater composition [3]. Observed values are both lighter (ca. 130 ppm; as also observed in dolomite from tidal-ponds on Bahamas [2]) and heavier (50-180 ppm). These distinct 238U/235U values for different dolomite-precipitates likely attest to the particular formation style, as well as early diagenetic processes. We use such modern settings to discuss the utility of 238U/235U in ancient sediments, the singularity of any observed 238U/235U signal, its relation to global ocean chemistry and potential diagenetic overprinting. These constraints are then used to evaluate a well-preserved marine carbonate section [4] and published black shale 238U/235U data [1], both deposited during the Oceanic Anoxic Event 2 (93 Ma). We discuss the capabilities of both the carbonate and black shale section for retaining information on the 238U/235U composition in the ocean during OAE 2. [1] Montoya-Pino et al. (2010) Geology, 38, 315-318 [2] Romaniello et al. (2013) 362, 305-316 [3] Andersen et al. (2014) EPSL, 400, 184-194 [4] Westermann et al. (2010) Cret. Res., 31, 500-514

Sources of osmium to the modern oceans: New evidence from the 190Pt-186Os system

USGS Publications Warehouse

McDaniel, D.K.; Walker, R.J.; Hemming, S.R.; Horan, M.F.; Becker, H.; Grauch, R.I.

2004-01-01

High precision Os isotope analysis of young marine manganese nodules indicate that whereas the composition of modern seawater is radiogenic with respect to 187Os/188Os, it has 186Os/188Os that is within uncertainty of the chondritic value. Marine Mn nodule compositions thus indicate that the average continental source of Os to modern seawater had long-term high Re/Os compared to Pt/Os. Analyses of loess and freshwater Mn nodules support existing evidence that average upper continental crust (UCC) has resolvably suprachondritic 186Os/188Os, as well as radiogenic 187Os/188Os. Modeling the composition of seawater as a two-component mixture of oceanic/cosmic Os with chondritic Os compositions and continentally-derived Os demonstrates that, insofar as estimates for the composition of average UCC are accurate, congruently weathered average UCC cannot be the sole continental source of Os to seawater. Our analysis of four Cambrian black shales confirm that organic-rich sediments can have 187Os/188Os ratios that are much higher than average UCC, but 186Os/188Os compositions that are generally between those of chondrites and average-UCC. Preferential weathering of black shales can result in dissolved Os discharged to the ocean basins that has a much lower 186Os/188Os than does average upper crust. Modeling the available data demonstrates that augmentation of estimated average UCC compositions with less than 0.1% additional black shale and 1.4% additional ultramafic rock can produce a continental end-member Os isotopic composition that satisfies the requirements imposed by the marine Mn nodule data. The interplay of these two sources provides a mechanism by which the 187Os/188Os of seawater can change as sources and weathering conditions change, yet seawater 186Os/188Os varies only minimally. ?? 2004 Elsevier Ltd.

Two-Stage Fracturing Wastewater Management in Shale Gas Development

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xiaodong; Sun, Alexander Y.; Duncan, Ian J.

Here, management of shale gas wastewater treatment, disposal, and reuse has become a significant environmental challenge, driven by an ongoing boom in development of U.S. shale gas reservoirs. Systems-analysis based decision support is helpful for effective management of wastewater, and provision of cost-effective decision alternatives from a whole-system perspective. Uncertainties are inherent in many modeling parameters, affecting the generated decisions. In order to effectively deal with the recourse issue in decision making, in this work a two-stage stochastic fracturing wastewater management model, named TSWM, is developed to provide decision support for wastewater management planning in shale plays. Using the TSWMmore » model, probabilistic and nonprobabilistic uncertainties are effectively handled. The TSWM model provides flexibility in generating shale gas wastewater management strategies, in which the first-stage decision predefined by decision makers before uncertainties are unfolded is corrected in the second stage to achieve the whole-system’s optimality. Application of the TSWM model to a comprehensive synthetic example demonstrates its practical applicability and feasibility. Optimal results are generated for allowable wastewater quantities, excess wastewater, and capacity expansions of hazardous wastewater treatment plants to achieve the minimized total system cost. The obtained interval solutions encompass both optimistic and conservative decisions. Trade-offs between economic and environmental objectives are made depending on decision makers’ knowledge and judgment, as well as site-specific information. In conclusion, the proposed model is helpful in forming informed decisions for wastewater management associated with shale gas development.« less

Two-Stage Fracturing Wastewater Management in Shale Gas Development

DOE PAGES

Zhang, Xiaodong; Sun, Alexander Y.; Duncan, Ian J.; ...

2017-01-19

Here, management of shale gas wastewater treatment, disposal, and reuse has become a significant environmental challenge, driven by an ongoing boom in development of U.S. shale gas reservoirs. Systems-analysis based decision support is helpful for effective management of wastewater, and provision of cost-effective decision alternatives from a whole-system perspective. Uncertainties are inherent in many modeling parameters, affecting the generated decisions. In order to effectively deal with the recourse issue in decision making, in this work a two-stage stochastic fracturing wastewater management model, named TSWM, is developed to provide decision support for wastewater management planning in shale plays. Using the TSWMmore » model, probabilistic and nonprobabilistic uncertainties are effectively handled. The TSWM model provides flexibility in generating shale gas wastewater management strategies, in which the first-stage decision predefined by decision makers before uncertainties are unfolded is corrected in the second stage to achieve the whole-system’s optimality. Application of the TSWM model to a comprehensive synthetic example demonstrates its practical applicability and feasibility. Optimal results are generated for allowable wastewater quantities, excess wastewater, and capacity expansions of hazardous wastewater treatment plants to achieve the minimized total system cost. The obtained interval solutions encompass both optimistic and conservative decisions. Trade-offs between economic and environmental objectives are made depending on decision makers’ knowledge and judgment, as well as site-specific information. In conclusion, the proposed model is helpful in forming informed decisions for wastewater management associated with shale gas development.« less

Miocene shale tectonics in the Moroccan margin (Alboran Sea)

NASA Astrophysics Data System (ADS)

Do Couto, D.; El Abbassi, M.; Ammar, A.; Gorini, C.; Estrada, F.; Letouzey, J.; Smit, J.; Jolivet, L.; Jabour, H.

2011-12-01

The Betic (Southern Spain) and Rif (Morocco) mountains form an arcuate belt that represents the westernmost termination of the peri-mediterranean Alpine mountain chain. The Miocene Alboran Basin and its subbasins is located in the hinterland of the Betic-Rif belt. It is considered to be a back-arc basin that developed during the coeval westward motion of the Alboran domain and the extensional collapse of previously thickened crust of the Betic-Rif belt. The Western Alboran Basin (WAB) is the major sedimentary depocenter with a sediment thickness in excess of 10 km, it is bordered by the Gibraltar arc, the volcanic Djibouti mounts and the Alboran ridge. Part of the WAB is affected by shale tectonics and associated mud volcanism. High-quality 2D seismic profiles acquired on the Moroccan margin of the Alboran Basin during the last decade reveal the multiple history of the basin. This study deals with the analysis of a number of these seismic profiles that are located along and orthogonal to the Moroccan margin. Seismic stratigraphy is calibrated from industrial wells. We focus on the interactions between the gravity-driven tectonic processes and the sedimentation in the basin. Our seismic interpretation confirms that the formation of the WAB began in the Early Miocene (Aquitanian - Burdigalian). The fast subsidence of the basin floor coeval to massive sedimentation induced the undercompaction of early miocene shales during their deposition. Downslope migration of these fine-grained sediments initiated during the deposition of the Langhian siliciclastics. This gravity-driven system was accompanied by continuous basement subsidence and induced disharmonic deformation in Mid Miocene units (i.e. not related to basement deformation). The development of shale-cored anticlines and thrusts in the deep basin is the result of compressive deformation at the front of the gravity-driven system and lasted for ca. 15 Ma. The compressive front has been re-activated by strong siliciclastic deposition, such as in the Serravalian-Tortonian period or more recently during the Quaternary contourites deposition. The Messinian dessication of the Mediterranean Sea and the following catastrophic Pliocene reflooding caused or enhanced re-activation of the deformation.

Paleo-ocean environments before and after the Ordovician glaciation and the correlation with heterogeneous marine black shale: a stratigraphic case study of Wufeng-Longmaxi formation in Fuling, Sichuan basin, SW China

NASA Astrophysics Data System (ADS)

Lu, Yangbo; Hao, Fang; Lu, Yongchao

2017-04-01

The discovery of Fuling gas field in the Sichuan basin led China shale gas exploration to an unprecedented boom. The most important shale gas plays are the upper Ordovician Wufeng formation and Lower Silurian Longmaxi formation which demonstrate intriguing characteristics which are comprising of stable regional distribution, high abundance of organic matter, high thermal maturity and high brittle mineral content etc. As the Ordovician-Silurian transition was a critical interval in Earth's history marked by dramatic climatic, oceanic, and biological turnovers; these two advantageous organic rich shale deposited before and after Hirnantian glaciation are showing differences in many aspects. In this study, the stratigraphy and lithofacies within the stratigraphy framework of the upper Ordovician Wufeng formation and Lower Silurian Longmaxi formation in Fuling were quantitatively analyzed based on outcrops, cores, well logs data, and geochemical proxies. A total of three third-order sequences were divided based on the recognition of four third-order boundaries. The Wufeng Formation is equivalent to a third-order sequence and is subdivided into a transgressive system tract (TST) (black shale of lower Wufeng Formation) and a highstand system tract (HST) (Guanyinqiao Member of upper Wufeng Formation). Long-1 Member is equivalent to a third-order sequence and is subdivided into a TST, an early highstand system tract (EHST) and a late highstand system tract (LHST); Long-2 and Long-3 Member are combined to be one third-order sequence and is subdivided into a lowstand system tract (LST), a TST and a HST. Sequence development and sedimentary environment characteristics were analyzed within each system tract unit. TOC% was correlated to V/Cr and EF-Ni respectively within each system tract unit, suggesting paleoproductivity and water redox condition are the main controlling factors of organic enrichment and its preservation. The heterogeneity in shale lithofacies throughout the stratigraphic frame work reflects the vertical evolution of the paleo-climate and paleo-ocean environment across the Ordovician-Silurian transition. We suggest that the high primary productivity of Wufeng formation was due to the boom of diatom triggered by large scale coverage of volcanic ash before Hirnantian glaciation. Marine anoxia may have been a kill mechanism that cause the mass extinction of marine macro-organism during the glacial period. And the up sequence TOC deterioration of Longmaxi formation is likely subjected to influence of ocean bottom flow and slow recovery of marine organism after the glaciation.

The architecture and frictional properties of faults in shale

NASA Astrophysics Data System (ADS)

De Paola, Nicola; Murray, Rosanne; Stillings, Mark; Imber, Jonathan; Holdsworth, Robert

2015-04-01

The geometry of brittle fault zones and associated fracture patterns in shale rocks, as well as their frictional properties at reservoir conditions, are still poorly understood. Nevertheless, these factors may control the very low recovery factors (25% for gas and 5% for oil) obtained during fracking operations. Extensional brittle fault zones (maximum displacement ≤ 3 m) cut exhumed oil mature black shales in the Cleveland Basin (UK). Fault cores up to 50 cm wide accommodated most of the displacement, and are defined by a stair-step geometry, controlled by the reactivation of en-echelon, pre-existing joints in the protolith. Cores typically show a poorly developed damage zone, up to 25 cm wide, and sharp contact with the protolith rocks. Their internal architecture is characterised by four distinct fault rock domains: foliated gouges; breccias; hydraulic breccias; and a slip zone up to 20 mm thick, composed of a fine-grained black gouge. Hydraulic breccias are located within dilational jogs with aperture of up to 20 cm, composed of angular clasts of reworked fault and protolith rock, dispersed within a sparry calcite cement. Velocity-step and slide-hold-slide experiments at sub-seismic slip rates (microns/s) were performed in a rotary shear apparatus under dry, water and brine-saturated conditions, for displacements of up to 46 cm. Both the protolith shale and the slip zone black gouge display shear localization, velocity strengthening behaviour and negative healing rates. Experiments at seismic slip rates (1.3 m/s), performed on the same materials under dry conditions, show that after initial friction values of 0.5-0.55, friction decreases to steady-state values of 0.1-0.15 within the first 10 mm of slip. Contrastingly, water/brine saturated gouge mixtures, exhibit almost instantaneous attainment of very low steady-state sliding friction (0.1). Our field observations show that brittle fracturing and cataclastic flow are the dominant deformation mechanisms in the fault core of shale faults, where slip localization may lead to the development of a thin slip zone made of very fine-grained gouges. The velocity-strengthening behaviour and negative healing rates observed during our laboratory experiments, suggest that slow, stable sliding faulting should take place within the protolith rocks and slip zone gouges. This behaviour will cause slow fault/fracture propagation, affecting the rate at which new fracture areas are created and, hence, limiting oil and gas production during reservoir stimulation. During slipping events, fluid circulation may be very effective along the fault zone at dilational jogs - where oil and gas production should be facilitated by the creation of large fracture areas - and rather restricted in the adjacent areas of the protolith, due to the lack of a well-developed damage zone and the low permeability of the matrix and slip zone gouge. Finally, our experiments performed at seismic slip rates show that seismic ruptures may still be able to propagate in a very efficient way within the slip zone of fluid-saturated shale faults, due to the attainment of instantaneous weakening.

Investigating GHGs and VOCs emissions from a shale gas industry in Germany and the UK

NASA Astrophysics Data System (ADS)

Cremonese, L.; Weger, L.; Denier Van Der Gon, H.; Bartels, M. P.; Butler, T. M.

2017-12-01

The shale gas and shale oil production boom experienced in the US led the country to a significant reduction of foreign fuel imports and an increase in domestic energy security. Several European countries are considering to extract domestic shale gas reserves that might serve as a bridge in the transition to renewables. Nevertheless, the generation of shale gas leads to emissions of CH4 and pollutants such as PM, NOx and VOCs, which in turn impact local and regional air quality and climate. Results from numerous studies investigating greenhouse gas and pollutant emissions from shale oil and shale gas extraction in North America can help in estimating the impact of such industrial activity elsewhere, when local regulations are taken into consideration. In order to investigate the extent of emissions and their distribution from a potential shale gas industry in Germany and the United Kingdom, we develop three drilling scenarios compatible with desired national gas outputs based on available geological information on potential productivity ranges of the reservoirs. Subsequently we assign activity data and emissions factors to wells under development, as well as to producing wells (from activities at the well site up until processing plants) to enable emissions quantification. We then define emissions scenarios to explore different shale gas development pathways: 1) implementation of "high-technology" devices and recovery practices (low emissions); 2) implementation of "low-technology" devices and recovery practices (high emissions), and 3) intermediate scenarios reflecting assumptions on local and national settings, or extremely high emission events (e.g. super-emitters); all with high and low boundaries of confidence driven by uncertainties. A comparison of these unconventional gas production scenarios to conventional natural gas production in Germany and the United Kingdom is also planned. The aim of this work is to highlight important variables and their ranges, to promote discussion and communication of potential impacts, and to construct possible visions for a future shale gas development in the two study countries. In a follow-up study, the impact of pollutant emissions from these scenarios on air quality will be explored using the Weather Research and Forecasting model with chemistry (WRF-Chem) model.

The Frasnian-Famennian boundary (Upper Devonian) within the Hanover-Dunkirk transition, northern Appalachian basin, western New York state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Over, D.J.

In western New York State interbedded pyritic silty green and dark grey shales and siltstone of the Hanover Member, Java Formation, West Falls Group, are overlain by thick pyritic dark grey-black shale of the Dunkirk Member of the Canadaway formation. The dark shales in the upper Hanover and Dunkirk contain a diverse and well preserved conodont fauna which allows precise placement of the Frasnian-Famennian boundary at several described sections. At Pt. Gratiot, in far western New York State, the contact between the Hanover and Dunkirk is disconformable. The Frasnian-Famennian boundary is marked by a pyritic lag deposit at the basemore » of the Dunkirk which contains Palmatolepis triangularis and Pa. subperlobata. The underlying upper Hanover is characterized by Pa. bogartensis , Pa. cf. Pa. rhenana, Pa. winchelli, and Ancyrognathus (asymmetricus/calvini) Eastward, in the direction of the paleo-source area, the Frasnian-Famennian boundary is within the upper Hanover Member. At Irish Gulf the boundary is recognized within a 10 cm thick laminated pyritic dark grey shale bed 3.0 m below the base of the Dunkirk. Palmatolepis triangularis and Pa. subperlobata occur below a conodont-rich lag layer in the upper 2 cm of the bed. Palmatolepis bogartensis , Pa. cf. Pa. rhenana, Ancyrodella curvata, and Icriodus alternatus occur in the underlying 8 cm. Palmatolepis triangularis and Pa. winchelli occur in an underlying dark shale bed separated from the boundary bed by a hummocky cross-bedded siltstone layer.« less

Sedimentology of SPICE (Steptoean positive carbon isotope excursion): A high-resolution trace fossil and microfabric analysis of the middle to late Cambrian Alum Shale Formation, southern Sweden

USGS Publications Warehouse

Egenhoff, Sven; Fishman, Neil; Ahlberg, Per; Maletz, Jorg; Jackson, Allison; Kolte, Ketki; Lowers, Heather; Mackie, James; Newby, Warren; Petrowsky, Matthew

2015-01-01

The Cambrian Alum Shale Formation in the Andrarum-3 core from Scania, southern Sweden, consists of black siliciclastic mudstone with minor carbonate intercalations. Four facies comprise three siliciclastic mudstones and one fine-grained carbonate. The facies reflect deposition along a transect from deep ramp to basin on a Cambrian shelf. The three mudstone facies contain abundant clay clasts and laterally variable siltstone laminae. Bed-load transport processes seem to have dominated deposition on this deep shelf. These sedimentary rocks record mainly event deposition, and only relatively few, thin laminae probably resulted from suspension settling. The Alum Shale Formation deep shelf did not show a bioturbation gradient, but fecal strings are common and Planolites burrows are rare in all mudstone facies. Evidence for biotic colonization indicates that this mudstone environment was not persistently anoxic, but rather was most likely intermittently dysoxic. The Alum Shale Formation in the Andrarum-3 core shows an overall decrease of grain size, preserved energy indicators, and carbonate content upsection interpreted to reflect a deepening upward. The succession can also be divided into four small-scale fining-upward cycles that represent deepening, and four overlying coarsening-upward cycles that represent upward shallowing.

Productivity Contribution of Paleozoic Woodlands to the Formation of Shale-Hosted Massive Sulfide Deposits in the Iberian Pyrite Belt (Tharsis, Spain)

NASA Astrophysics Data System (ADS)

Fernández-Remolar, David C.; Harir, Mourad; Carrizo, Daniel; Schmitt-Kopplin, Philippe; Amils, Ricardo

2018-03-01

The geological materials produced during catastrophic and destructive events are an essential source of paleobiological knowledge. The paleobiological information recorded by such events can be rich in information on the size, diversity, and structure of paleocommunities. In this regard, the geobiological study of late Devonian organic matter sampled in Tharsis (Iberian Pyrite Belt) provided some new insights into a Paleozoic woodland community, which was recorded as massive sulfides and black shale deposits affected by a catastrophic event. Sample analysis using TOF-SIMS (Time of Flight Secondary Ion Mass Spectrometer), and complemented by GC/MS (Gas Chromatrograph/Mass Spectrometer) identified organic compounds showing a very distinct distribution in the rock. While phytochemical compounds occur homogeneously in the sample matrix that is composed of black shale, the microbial-derived organics are more abundant in the sulfide nodules. The cooccurrence of sulfur bacteria compounds and the overwhelming presence of phytochemicals provide support for the hypothesis that the formation of the massive sulfides resulted from a high rate of vegetal debris production and its oxidation through sulfate reduction under suboxic to anoxic conditions. A continuous supply of iron from hydrothermal activity coupled with microbial activity was strictly necessary to produce this massive orebody. A rough estimate of the woodland biomass was made possible by accounting for the microbial sulfur production activity recorded in the metallic sulfide. As a result, the biomass size of the late Devonian woodland community was comparable to modern woodlands like the Amazon or Congo rainforests.

Lower Cody Shale (Niobrara equivalent) in the Bighorn Basin, Wyoming and Montana: thickness, distribution, and source rock potential

USGS Publications Warehouse

Finn, Thomas M.

2014-01-01

The lower shaly member of the Cody Shale in the Bighorn Basin, Wyoming and Montana is Coniacian to Santonian in age and is equivalent to the upper part of the Carlile Shale and basal part of the Niobrara Formation in the Powder River Basin to the east. The lower Cody ranges in thickness from 700 to 1,200 feet and underlies much of the central part of the basin. It is composed of gray to black shale, calcareous shale, bentonite, and minor amounts of siltstone and sandstone. Sixty-six samples, collected from well cuttings, from the lower Cody Shale were analyzed using Rock-Eval and total organic carbon analysis to determine the source rock potential. Total organic carbon content averages 2.28 weight percent for the Carlile equivalent interval and reaches a maximum of nearly 5 weight percent. The Niobrara equivalent interval averages about 1.5 weight percent and reaches a maximum of over 3 weight percent, indicating that both intervals are good to excellent source rocks. S2 values from pyrolysis analysis also indicate that both intervals have a good to excellent source rock potential. Plots of hydrogen index versus oxygen index, hydrogen index versus Tmax, and S2/S3 ratios indicate that organic matter contains both Type II and Type III kerogen capable of generating oil and gas. Maps showing the distribution of kerogen types and organic richness for the lower shaly member of the Cody Shale show that it is more organic-rich and more oil-prone in the eastern and southeastern parts of the basin. Thermal maturity based on vitrinite reflectance (Ro) ranges from 0.60–0.80 percent Ro around the margins of the basin, increasing to greater than 2.0 percent Ro in the deepest part of the basin, indicates that the lower Cody is mature to overmature with respect to hydrocarbon generation.

Crack deflection in brittle media with heterogeneous interfaces and its application in shale fracking

NASA Astrophysics Data System (ADS)

Zeng, Xiaguang; Wei, Yujie

Driven by the rapid progress in exploiting unconventional energy resources such as shale gas, there is growing interest in hydraulic fracture of brittle yet heterogeneous shales. In particular, how hydraulic cracks interact with natural weak zones in sedimentary rocks to form permeable cracking networks is of significance in engineering practice. Such a process is typically influenced by crack deflection, material anisotropy, crack-surface friction, crustal stresses, and so on. In this work, we extend the He-Hutchinson theory (He and Hutchinson, 1989) to give the closed-form formulae of the strain energy release rate of a hydraulic crack with arbitrary angles with respect to the crustal stress. The critical conditions in which the hydraulic crack deflects into weak interfaces and exhibits a dependence on crack-surface friction and crustal stress anisotropy are given in explicit formulae. We reveal analytically that, with increasing pressure, hydraulic fracture in shales may sequentially undergo friction locking, mode II fracture, and mixed mode fracture. Mode II fracture dominates the hydraulic fracturing process and the impinging angle between the hydraulic crack and the weak interface is the determining factor that accounts for crack deflection; the lower friction coefficient between cracked planes and the greater crustal stress difference favor hydraulic fracturing. In addition to shale fracking, the analytical solution of crack deflection could be used in failure analysis of other brittle media.

Geology and mineral deposits of the Carlile quadrangle, Crook County, Wyoming

USGS Publications Warehouse

Bergendahl, M.H.; Davis, R.E.; Izett, G.A.

1961-01-01

The Carlile quadrangle-is along the northwestern flank of the Black Hills uplift in Crook County, Wyo. The area-is primarily one of canyons and divides that are a result of downcutting by the Belle Fourche River and its tributaries through an alternating succession of sandstone, siltstone, and mudstone or shale beds. The present topography is also influenced by the regional structure, as reflected by the beds that dip gently westward and by the local structural features such as anticlines, domes, synclines, basins, and terraces, which are superimposed upon the regional setting. Rocks exposed include shale and thin limestone and sandstone beds belonging to the Redwater shale member of the Sundance formation and to the Morrison formation, both of Late Jurassic age; sandstone, siltstone, and mudstone of the Lakota and Fall River formations of Early Cretaceous age; and shale and sandstone of the Skull Creek shale, Newcastle sandstone, and Mowry shale, also of Early Cretaceous age. In the southwestern part of the quadrangle rocks of the Upper Cretaceous series are exposed. These include the Belle Fourche shale, Greenhorn formation, and Carlile shale. Gravel terraces, landslide debris, and stream alluvium comprise the surficial deposits. The Lakota and Fall River formations, which make up the Iriyan Kara group, contain uranium deposits locally in the northern Black Hills. These formations were informally subdivided in order to show clearly the vertical and lateral distribution of the sandstone, siltstone, and mudstone facies within them.The Lakota was subdivided into a sandstone unit and an overlying mudstone unit; the Fall River was subdivided, in ascending order, into a siltstone unit, a mudstone unit, a sandstone unit, and an upper unit. The lithologic character of the Lakota changes abruptly locally, and the units are quite inconsistent with respect to composition, thickness, and extent. This is in contrast to a notable consistency in the lithologic character and thickness among all the Fall River units, with the exception of the upper unit. Petrographic studies on selected samples of units from both formations show differences in composition between Lakota and Fall River rocks.The Carlile quadrangle lies immediately east of the monocline that marks the outer limit of the Black Hills uplift, and the rocks in this area have a regional dip of less than 2° outward from the center of the uplift. Superimposed upon the regional uplift are many subordinate structural features anticlines, synclines, domes, basins, and terraces which locally modify the regional features. The most pronounced of these subordinate structural features are the doubly-plunging Pine Ridge, Oil Butte, and Dakota Divide anticlines, and the Eggie Creek syncline. Stress throughout the area was relieved almost entirely through folding; only a few small nearly vertical normal faults were found within the quadrangle.Uranium has been mined from the Carlile deposit, owned by the Homestake Mining Co. The ore minerals, carnotite and tyuyamnuite occur in a sandstone lens that is enclosed within relatively impermeable clayey beds in the mudstone unit of the Lakota formation. The ore also includes unidentified black vanadium minerals and possibly coffinite. Uranium minerals are more abundant in and adjacent to thicker carbonaceous and silty seams in the sandstone lens. A mixture of fine-grained calcium carbonate and calcium sulfate fills the interstices between detrital quartz grains in mineralized sandstone. Selenium and arsenic are more abundant in samples that are high in uranium. Drilling on Thorn Divide about 1 mile west of the Carlile mine has roughly outlined concentrations of a sooty black uranium mineral associated with pyrite In two stratigraphic intervals of the Lakota formation. One is in the same sandstone lens that contains the ore at the Carlile mine; the other is in conglomeratic sandstone near the base of the Lakota. These deposits are relatively deep, and no mining has been attempted. The mineralogy of the Carlile deposits and the lithologic features of the sandstone host rock suggest that uranium and vanadium were transported in the high-valent state by carbonate or sulfate solutions, were extracted from solution by organic material, and were reduced to low-valent states to form an original assemblage of oxides and silicates. These primary minerals were oxidized in place, and the present carnotite-tyuyamunite assemblage was formed. In general, radioactivity analyses correspond fairly closely with chemical analyses of uranium, thus it is believed that only minor solution and migration of uranium has occurred since the present suite of oxidized minerals was formed. The factors responsible for ore localization are not clear, but probably a combination of three lithologic and structural elements contributed to provide a favorable environment for precipitating uranium from aqueous solutions: abundant carbonaceous material or pyrite in a thin, permeable sandstone enclosed within relatively thick impermeable clays; local structural basins; and a regional structural setting involving a broad syncline between two anticlines. The structural features controlled the regional flow of ground water and the lithologic features controlled the local rate of flow and provided the proper chemical environment for uranium deposition. Bentonite has been mined from an opencut in the Mowry shale in the southwest part of the quadrangle. A bentonite bed in the Newcastle sandstone also seems to be of minable thickness and quality. Exploration for petroleum has been unsuccessful within the quadrangle; however, some wells that yielded oil were recently drilled on small anticlines to the west and southeast. It is possible that similar structural features in the Carlile area, that were previously overlooked, may be equally productive.

A Reactive Transport Model for Marcellus Shale Weathering

NASA Astrophysics Data System (ADS)

Li, L.; Heidari, P.; Jin, L.; Williams, J.; Brantley, S.

2017-12-01

Shale formations account for 25% of the land surface globally. One of the most productive shale-gas formations is the Marcellus, a black shale that is rich in organic matter and pyrite. As a first step toward understanding how Marcellus shale interacts with water, we developed a reactive transport model to simulate shale weathering under ambient temperature and pressure conditions, constrained by soil chemistry and water data. The simulation was carried out for 10,000 years, assuming bedrock weathering and soil genesis began right after the last glacial maximum. Results indicate weathering was initiated by pyrite dissolution for the first 1,000 years, leading to low pH and enhanced dissolution of chlorite and precipitation of iron hydroxides. After pyrite depletion, chlorite dissolved slowly, primarily facilitated by the presence of CO2 and organic acids, forming vermiculite as a secondary mineral. A sensitivity analysis indicated that the most important controls on weathering include the presence of reactive gases (CO2 and O2), specific surface area, and flow velocity of infiltrating meteoric water. The soil chemistry and mineralogy data could not be reproduced without including the reactive gases. For example, pyrite remained in the soil even after 10,000 years if O2 was not continuously present in the soil column; likewise, chlorite remained abundant and porosity remained small with the presence of soil CO2. The field observations were only simulated successfully when the specific surface areas of the reactive minerals were 1-3 orders of magnitude smaller than surface area values measured for powdered minerals, reflecting the lack of accessibility of fluids to mineral surfaces and potential surface coating. An increase in the water infiltration rate enhanced weathering by removing dissolution products and maintaining far-from-equilibrium conditions. We conclude that availability of reactive surface area and transport of H2O and gases are the most important factors affecting chemical weathering of the Marcellus shale in the shallow subsurface. This study documents the utility of reactive transport modeling for complex subsurface processes. Such modelling could be extended to understand interactions between injected fluids and Marcellus shale gas reservoirs at higher temperature and pressure.

Benthic foraminiferal fauna as a tool to indicate the Toarcian Oceanic Anoxic Event in homogeneous Ammonitico Rosso series of Bakonycsernye (Transdanubian Hungary)

NASA Astrophysics Data System (ADS)

Zsiborás, Gábor; Görög, Ágnes

2017-04-01

In the last decades, since the Toarcian Oceanic Anoxic Event (T-OAE, ˜182 Ma) recognized, several studies was dealing with the effect of it on the foraminiferal faunas from black shales and marls of the epicontinental region. Only a few work was made from the Tethyan oceanic basin region (Monaco et al., 1994; Nini et al., 1995; Pettinelli et al., 1997) characterized by occurrence of black shales between the "Lower Posidonia Shale" and the Ammonitico Rosso. However, the black shale is absent in some Tehyan sections substituted by red or grey marls. Only Reolid et al. (2015) focused on foraminifera from this kind of successions, from the Betic Cordillera, where the T-OAE was not detected. From the section of Tű zkövesárok of Bakonycsernye, Transdanubian Central Range, Hungary, Monostori in Galácz et al. (2008) based on the Bairdidae dominated ostracod fauna indicated suboxic environment at the Pliensbachian/Toarcian boundary. Thus the aim of our study was to give paleoecological interpretation of the foraminiferal fauna of this 2 m thick Ammonitico Rosso sequence. Foraminifers were extracted from six red nodular, slightly argillaceous limestone (Tű zkövesárok Limestone) samples from the Pliensbachian part (Emaciatum Zone) and one sample from the Toarcian part (Tenuicostatum Zone) which begins with a hardground and following by red marl (Kisgerecse Marl). The washing residues of the lower four samples contains foraminifers, sponge spicules, radiolarians and echinodermata parts (crinoids and holothurians). The upper two Pliensbachian samples include more foraminifers, however, other groups are absent. The Toarcian sample contains crinoids and less foraminifers (30%). Overall 68 taxa were identified, 54 on species, 14 on generic level. The most of the specimens have calcitic tests, in the Pliensbachian, agglutinated forms are 7-24% of the fauna, however, they are absent in the Toarcian. Upwards to the Pliensbachian/Toarcian boundary, the diversity of the fauna rapidly increased. Above the boundary, the number of species decreased to the 40% of the Pliensbachian maximum diversity. Sorting the specimens by morphological features is a tool for the paleoecological evaluation. In the Pliensbachian assemblages, the biconvex groups (Lenticulina) are dominant, however, elongated (Nodosaria and Eoguttulina) and flattened (Planularia) groups are dominant in the Toarcian. This morphological changing indicates the decreasing of seawater oxygen level and current energy in the lowermost Toarcian. It does not show anoxia but can be suboxia caused by abrupt deepening. The previous results of the ostracod studies indicated the same events. The Pliensbachian/Toarcian boundary section of Tű zkövesárok include a similar foraminiferal fauna to other Tethyan successions Spoleto and Umbria-Marche Apennines (Central Italy), Ionian Basin (Greece); and epicontinental sequences e. g., Lusitanian Basin (Portugal) which all have black shale layers in the Early Toarcian. In contrast, the Betic section with very similar lithology to Bakonycsernye provided a totally different fauna with dominance of agglutinated forms and without significant diversity changes at the boundary. The studied boundary section is the first Ammonitico Rosso sequence which foraminiferal fauna indicated the environmental changes caused by the T-OAE in the deep basin of the Tethyan Realm. The Research was supported by the Hantken Foundation.

Bacterial Paleontology and Studies of Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Gerasimenko, L. M.; Hoover, Richard B.; Rozanov, Alexei Y.; Zhegallo, E. A.; Zhmur, S. I.

1999-01-01

The study of the fossilization processes of modern cyanobacteria provides insights needed to recognize bacterial microfossils. The fossilization of cyanobacteria is discussed and images of recent and fossil bacteria and cyanobacteria from the Early Proterozoic to Neogene carbonaceous rocks (kerites, shungites, and black shales) and phosphorites are provided. These are compared with biomorphic microstructures and possible microfossils encountered in-situ in carbonaceous meteorites.

The 2.1 Ga old Francevillian biota: biogenicity, taphonomy and biodiversity.

PubMed

El Albani, Abderrazak; Bengtson, Stefan; Canfield, Donald E; Riboulleau, Armelle; Rollion Bard, Claire; Macchiarelli, Roberto; Ngombi Pemba, Lauriss; Hammarlund, Emma; Meunier, Alain; Moubiya Mouele, Idalina; Benzerara, Karim; Bernard, Sylvain; Boulvais, Philippe; Chaussidon, Marc; Cesari, Christian; Fontaine, Claude; Chi-Fru, Ernest; Garcia Ruiz, Juan Manuel; Gauthier-Lafaye, François; Mazurier, Arnaud; Pierson-Wickmann, Anne Catherine; Rouxel, Olivier; Trentesaux, Alain; Vecoli, Marco; Versteegh, Gerard J M; White, Lee; Whitehouse, Martin; Bekker, Andrey

2014-01-01

The Paleoproterozoic Era witnessed crucial steps in the evolution of Earth's surface environments following the first appreciable rise of free atmospheric oxygen concentrations ∼2.3 to 2.1 Ga ago, and concomitant shallow ocean oxygenation. While most sedimentary successions deposited during this time interval have experienced thermal overprinting from burial diagenesis and metamorphism, the ca. 2.1 Ga black shales of the Francevillian B Formation (FB2) cropping out in southeastern Gabon have not. The Francevillian Formation contains centimeter-sized structures interpreted as organized and spatially discrete populations of colonial organisms living in an oxygenated marine ecosystem. Here, new material from the FB2 black shales is presented and analyzed to further explore its biogenicity and taphonomy. Our extended record comprises variably sized, shaped, and structured pyritized macrofossils of lobate, elongated, and rod-shaped morphologies as well as abundant non-pyritized disk-shaped macrofossils and organic-walled acritarchs. Combined microtomography, geochemistry, and sedimentary analysis suggest a biota fossilized during early diagenesis. The emergence of this biota follows a rise in atmospheric oxygen, which is consistent with the idea that surface oxygenation allowed the evolution and ecological expansion of complex megascopic life.

Assessment of Appalachian Basin Oil and Gas Resources: Utica-Lower Paleozoic Total Petroleum System

USGS Publications Warehouse

Ryder, Robert T.

2008-01-01

The Utica-Lower Paleozoic Total Petroleum System (TPS) is an important TPS identified in the 2002 U.S. Geological Survey (USGS) assessment of undiscovered, technically recoverable oil and gas resources in the Appalachian basin province (Milici and others, 2003). The TPS is named for the Upper Ordovician Utica Shale, which is the primary source rock, and for multiple lower Paleozoic sandstone and carbonate units that are the important reservoirs. Upper Cambrian through Upper Silurian petroleum-bearing strata that constitute the Utica-Lower Paleozoic TPS thicken eastward from about 2,700 ft at the western margin of the Appalachian basin to about 12,000 ft at the thrust-faulted eastern margin of the Appalachian basin. The Utica-Lower Paleozoic TPS covers approximately 170,000 mi2 of the Appalachian basin from northeastern Tennessee to southeastern New York and from central Ohio to eastern West Virginia. The boundary of the TPS is defined by the following geologic features: (1) the northern boundary (from central Ontario to northeastern New York) extends along the outcrop limit of the Utica Shale-Trenton Limestone; (2) the northeastern boundary (from southeastern New York, through southeastern Pennsylvania-western Maryland-easternmost West Virginia, to northern Virginia) extends along the eastern limit of the Utica Shale-Trenton Limestone in the thrust-faulted eastern margin of the Appalachian basin; (3) the southeastern boundary (from west-central and southwestern Virginia to eastern Tennessee) extends along the eastern limit of the Trenton Limestone in the thrust-faulted eastern margin of the Appalachian basin; (4) the southwestern boundary (from eastern Tennessee, through eastern Kentucky, to southwestern Ohio) extends along the approximate facies change from the Trenton Limestone with thin black shale interbeds (on the east) to the equivalent Lexington Limestone without black shale interbeds (on the west); (5) the northern part of the boundary in southwestern Ohio to the Indiana border extends along an arbitrary boundary between the Utica Shale of the Appalachian basin and the Utica Shale of the Sebree trough (Kolata and others, 2001); and (6) the northwestern boundary (from east-central Indiana, through northwesternmost Ohio and southeasternmost Michigan, to central Ontario) extends along the approximate southeastern boundary of the Michigan Basin. Although the Utica-Lower Paleozoic TPS extends into northwestern Ohio, southeastern Michigan, and northeastern Indiana, these areas have been assigned to the Michigan Basin (Swezey and others, 2005) and are outside the scope of this report. Furthermore, although the northern part of the Utica-Lower Paleozoic TPS extends across the Great Lakes (Lake Erie and Lake Ontario) into southern Ontario, Canada, only the undiscovered oil and gas resources in the U.S. waters of the Great Lakes have been included in the USGS assessment of the Utica-Lower Paleozoic TPS. This TPS is similar to the Point Pleasant-Brassfield petroleum system previously identified by Drozd and Cole (1994) in the Ohio part of the Appalachian basin.

Neutralisation of an acidic pit lake by alkaline waste products.

PubMed

Allard, Bert; Bäckström, Mattias; Karlsson, Stefan; Grawunder, Anja

2014-01-01

A former open pit where black shale (alum shale) was excavated during 1942-1965 has been water filled since 1966. The water chemistry was dominated by calcium and sulphate and had a pH of 3.2-3.4 until 1997-1998, when pH was gradually increasing. This was due to the intrusion of leachates from alkaline cement waste deposited close to the lake. A stable pH of around 7.5 was obtained after 6-7 years. The chemistry of the pit lake has changed due to the neutralisation. Concentrations of some dissolved metals, notably zinc and nickel, have gone down, as a result of adsorption/co-precipitation on solid phases (most likely iron and aluminium hydroxides), while other metals, notably uranium and molybdenum, are present at elevated levels. Uranium concentration is reaching a minimum of around pH 6.5 and is increasing at higher pH, which may indicate a formation of neutral and anionic uranyl carbonate species at high pH (and total carbonate levels around 1 mM). Weathering of the water-exposed shale is still in progress.

The radioisotopically constrained Viséan onset of turbidites in the Moravian-Silesian part of the Rhenohercynian foreland basin (Central European Variscides)

NASA Astrophysics Data System (ADS)

Jirásek, Jakub; Otava, Jiří; Matýsek, Dalibor; Sivek, Martin; Schmitz, Mark D.

2018-03-01

The Březina Formation represents the initiation of siliciclastic flysch turbidite sedimentation at the eastern margin of Bohemian Massif or within the Rhenohercynian foreland basin. Its deposition started after drowning of the Devonian carbonate platform during Viséan (Mississippian) times, resulting in a significant interval of black siliceous shale and variegated fossiliferous shale deposition in a starved basin. Near the top of the Březina Formation an acidic volcanoclastic layer (tuff) of rhyolitic composition has been dated with high precision U-Pb zircon chemical abrasion isotope dilution method at 337.73 ± 0.16 Ma. This new radiometric age correlates with the previously inferred stratigraphic age of the locality and the current calibration of the Early Carboniferous geologic time scale. Shales of the Březina Formation pass gradually upwards into the siliciclastics of the Rozstání Formation of the Drahany culm facies. Thus our new age offers one of the few available radioisotopic constraints on the time of onset of siliciclastic flysch turbidites in the Rhenohercynian foreland basin of the European Variscides.

Assessing the utility of FIB-SEM images for shale digital rock physics

NASA Astrophysics Data System (ADS)

Kelly, Shaina; El-Sobky, Hesham; Torres-Verdín, Carlos; Balhoff, Matthew T.

2016-09-01

Shales and other unconventional or low permeability (tight) reservoirs house vast quantities of hydrocarbons, often demonstrate considerable water uptake, and are potential repositories for fluid sequestration. The pore-scale topology and fluid transport mechanisms within these nanoporous sedimentary rocks remain to be fully understood. Image-informed pore-scale models are useful tools for studying porous media: a debated question in shale pore-scale petrophysics is whether there is a representative elementary volume (REV) for shale models? Furthermore, if an REV exists, how does it differ among petrophysical properties? We obtain three dimensional (3D) models of the topology of microscale shale volumes from image analysis of focused ion beam-scanning electron microscope (FIB-SEM) image stacks and investigate the utility of these models as a potential REV for shale. The scope of data used in this work includes multiple local groups of neighboring FIB-SEM images of different microscale sizes, corresponding core-scale (milli- and centimeters) laboratory data, and, for comparison, series of two-dimensional (2D) cross sections from broad ion beam SEM images (BIB-SEM), which capture a larger microscale field of view than the FIB-SEM images; this array of data is larger than the majority of investigations with FIB-SEM-derived microscale models of shale. Properties such as porosity, organic matter content, and pore connectivity are extracted from each model. Assessments of permeability with single phase, pressure-driven flow simulations are performed in the connected pore space of the models using the lattice-Boltzmann method. Calculated petrophysical properties are compared to those of neighboring FIB-SEM images and to core-scale measurements of the sample associated with the FIB-SEM sites. Results indicate that FIB-SEM images below ∼5000 μm3 volume (the largest volume analyzed) are not a suitable REV for shale permeability and pore-scale networks; i.e. field of view is compromised at the expense of detailed, but often unconnected, nanopore morphology. Further, we find that it is necessary to acquire several local FIB-SEM or BIB-SEM images and correlate their extracted geometric properties to improve the likelihood of achieving representative values of porosity and organic matter volume. Our work indicates that FIB-SEM images of microscale volumes of shale are a qualitative tool for petrophysical and transport analysis. Finally, we offer alternatives for quantitative pore-scale assessments of shale.

Geological Setting of Diamond Drilling for the Archean Biosphere Drilling Project, Pilbara Craton, Western Australia

NASA Astrophysics Data System (ADS)

Hickman, A.

2004-12-01

The Archean Biosphere Drilling Project (ABDP) is a collaborative international research project conducting systematic (bio)geochemical investigations to improve our understanding of the biosphere of the early Earth. The Pilbara Craton of Western Australia, which includes exceptionally well preserved 3.52 to 2.70 Ga sedimentary sequences, was selected for an innovative sampling program commencing in 2003. To avoid near-surface alteration and contamination effects, sampling was by diamond drilling to depths of between 150 and 300 m, and was located at sites where the target lithologies were least deformed and had lowest metamorphic grade (below 300°C). The first of five successful drilling sites (Jasper Deposit) targeted red, white and black chert in the 3.46 Ga Marble Bar Chert Member. This chert marks the top of a thick mafic-felsic volcanic cycle, the third of four such cycles formed by mantle plumes between 3.52 and 3.43 Ga. The geological setting was a volcanic plateau founded on 3.72 to 3.60 Ga sialic crust (isotopic evidence). The second hole (Salgash) was sited on the basal section of the fourth cycle, and sampled sulfidic (Cu-Zn-Fe), carbon-rich shale and sandstone units separated by flows of peridotite. The third hole (Eastern Creek) was sited on the margin of a moderately deep-water rift basin, the 2.95 to 2.91 Ga Mosquito Creek Basin. This is dominated by turbidites, but the sandstones and carbon-rich shales intersected at the drilling site were deposited in shallower water. The fourth and fifth holes, located 300 km apart, sampled 2.77 to 2.76 Ga continental formations of the Fortescue Group; both holes included black shales.

Active Microbial Methane Production and Organic Matter Degradation in a Devonian Black Shale

NASA Astrophysics Data System (ADS)

Martini, A. M.; Petsch, S. T.; Nuesslein, K.; McIntosh, J. C.

2003-12-01

Microorganisms employ many novel strategies to derive energy and obtain nutrients, and in doing so alter the chemistry of their environments in ways that are significant for formation and transformation of geologic materials. One such strategy is natural gas generation in sedimentary basins. Previous research has shown that stable isotopic signatures of CH4, CO2 and H2O in formation waters of gas-producing black shales indicate a microbial origin for several economically viable natural gas reserves. However, these signatures leave several intriguing issues unaddressed, including the identity of the organisms and their metabolic roles and impacts on mineral, isotopic and biomarker signatures. We hypothesize that the extreme reducing conditions required for sedimentary basin methanogenesis are simply the end product of a cascade of microbial processes, initiated by anaerobic respiration of shale organic matter through NO3, SO4 and/or Fe(III) reduction, secondary processing of anaerobe biomass by fermentative organisms yielding volatile fatty acids and H2, and ultimately CO2 reduction and/or acetate fermentation to produce CH4. This research holds importance for the several aspects of the geochemical carbon cycle. It describes anaerobic hydrocarbon degradation leading to methanogenesis in a sedimentary basin; in many instances this activity has generated economically viable reserves of natural gas. It also provides a benchmark detailing how post-depositional microbial activity in rocks may confound and overprint ancient biosignatures. Interpretation of past environmental conditions depends on molecular and isotopic signatures contained in ancient sedimentary rocks, separated from signatures of metabolically similar modern microbiota living in sedimentary basins. In addition, this research sheds light on an unrecognized and thus unconstrained source of reduced gases to Earth's atmosphere, important for understanding the rates and controls on carbon cycling through geologic time.

Two separate outflows in the dual supermassive black hole system NGC 6240

NASA Astrophysics Data System (ADS)

Müller-Sánchez, F.; Nevin, R.; Comerford, J. M.; Davies, R. I.; Privon, G. C.; Treister, E.

2018-04-01

Theoretical models and numerical simulations have established a framework of galaxy evolution in which galaxies merge and create dual supermassive black holes (with separations of one to ten kiloparsecs), which eventually sink into the centre of the merger remnant, emit gravitational waves and coalesce. The merger also triggers star formation and supermassive black hole growth, and gas outflows regulate the stellar content1-3. Although this theoretical picture is supported by recent observations of starburst-driven and supermassive black hole-driven outflows4-6, it remains unclear how these outflows interact with the interstellar medium. Furthermore, the relative contributions of star formation and black hole activity to galactic feedback remain unknown7-9. Here we report observations of dual outflows in the central region of the prototypical merger NGC 6240. We find a black-hole-driven outflow of [O iii] to the northeast and a starburst-driven outflow of Hα to the northwest. The orientations and positions of the outflows allow us to isolate them spatially and study their properties independently. We estimate mass outflow rates of 10 and 75 solar masses per year for the Hα bubble and the [O iii] cone, respectively. Their combined mass outflow is comparable to the star formation rate10, suggesting that negative feedback on star formation is occurring.

Two separate outflows in the dual supermassive black hole system NGC 6240.

PubMed

Müller-Sánchez, F; Nevin, R; Comerford, J M; Davies, R I; Privon, G C; Treister, E

2018-04-01

Theoretical models and numerical simulations have established a framework of galaxy evolution in which galaxies merge and create dual supermassive black holes (with separations of one to ten kiloparsecs), which eventually sink into the centre of the merger remnant, emit gravitational waves and coalesce. The merger also triggers star formation and supermassive black hole growth, and gas outflows regulate the stellar content 1-3 . Although this theoretical picture is supported by recent observations of starburst-driven and supermassive black hole-driven outflows 4-6 , it remains unclear how these outflows interact with the interstellar medium. Furthermore, the relative contributions of star formation and black hole activity to galactic feedback remain unknown 7-9 . Here we report observations of dual outflows in the central region of the prototypical merger NGC 6240. We find a black-hole-driven outflow of [O III] to the northeast and a starburst-driven outflow of Hα to the northwest. The orientations and positions of the outflows allow us to isolate them spatially and study their properties independently. We estimate mass outflow rates of 10 and 75 solar masses per year for the Hα bubble and the [O III] cone, respectively. Their combined mass outflow is comparable to the star formation rate 10 , suggesting that negative feedback on star formation is occurring.

Heterogeneity of shales in different scales and its implications to laboratory analyses - examples from sedimentology and organic geochemistry study of the Lower Paleozoic shales from shale gas exploration well located in the Baltic Basin, Poland.

NASA Astrophysics Data System (ADS)

Roszkowska-Remin, Joanna; Janas, Marcin

2017-04-01

We present the litho-sedimentological, organic geochemical results and organic porosity estimation of the Ordovician and Silurian shales in the SeqWell (shale gas exploration well located in the Pomerania region, Poland). The most perspective black and bituminous shales of the Upper Ordovician and the Lower Silurian may seem to be homogeneous. However, our results reveal that these shales show heterogeneity at different scales (m to mm). For example, in most cases the decrease of TOC content in the m scale is related to pyroclastic rock intercalations and "dark bioturbations" with no color difference when compared with surrounding sediments. While in cm scale heterogeneity is related to bioturbations, density of organic-rich laminas, or abundance of carbonates and pyrite. Without a detailed sedimentological study of polished core surfaces and Rock-Eval analyses those observations are rather invisible. The correct interpretation of results requires the understanding of rock's heterogeneity in different scales. It has a critical importance for laboratory tests applied on few cm long samples, especially if the results are to be extrapolated to wider intervals. Therefore in ShaleSeq project, a detailed sedimentological core logging and analysis of geochemical parameters of perspective formations in m to mm scale was performed for the first time. The results show good correlation between bioturbation index (BI) and organic geochemical indicators like organic carbon content (TOC) or oxic deposition conditions indicator (oxygen index - OI) leading to the assumption that environmental conditions may have played a crucial role in organic carbon preservation. The geochemical analyses of 12 samples showed that even within the few cm long sections shale can be really diversified. Eight out of twelve analyzed samples were considered geochemically mostly homogeneous, whilst four of them showed evident heterogeneity. Concluding, the sampling should be preceded by detailed sedimentological study, as it allows to control if the chosen samples are representative for wider intervals and give opportunity to place the laboratory results in the wider context. An attempt to estimate organic porosity using Rock-Eval data was based on Marathon Oil company study of the Polish Lower Paleozoic shales. The results of this study and suggested equations were used to calculate hypothetical organic porosity of the most perspective shales in the SeqWell. Calculated organic porosities in % bulk volume of rock suggested that organic porosity for Upper Ordovician and Lower Silurian shales in SeqWell may be at the level of 0,1-2,9% in bulk volume of rock. These results would suggest that organic porosity doesn't play a major role in total porosity system in these shales at the certain thermal maturity level. The hypothetical organic porosity values were not validated by the microscopic study though. Our study are part of the ShaleSeq Project co-funded by Norway Grants of the Polish-Norwegian Research Programme operated by the National Centre for Research and Development.

Analyzing Solutions High in Total Dissolved Solids for Rare Earth Elements (REEs) Using Cation Exchange and Online Pre-Concentration with the seaFAST2 Unit; NETL-TRS-7-2017; NETL Technical Report Series; U.S. Department of Energy, National Energy Technology Laboratory: Albany, OR, 2017; p 32

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, J.; Torres, M.; Verba, C.

The accurate quantification of the rare earth element (REE) dissolved concentrations in natural waters are often inhibited by their low abundances in relation to other dissolved constituents such as alkali, alkaline earth elements, and dissolved solids. The high abundance of these constituents can suppress the overall analytical signal as well as create isobaric interferences on the REEs during analysis. Waters associated with natural gas operations on black shale plays are characterized by high salinities and high total dissolved solids (TDS) contents >150,000 mg/L. Methods used to isolate and quantify dissolved REEs in seawater were adapted in order to develop themore » capability of analyzing REEs in waters that are high in TDS. First, a synthetic fluid based on geochemical modelling of natural brine formation fluids was created within the Marcellus black shale with a TDS loading of 153,000 mg/L. To this solution, 1,000 ng/mL of REE standards was added based on preliminary analyses of experimental fluids reacted at high pressure and temperature with Marcellus black shale. These synthetic fluids were then run at three different dilution levels of 10, 100, and 1,000–fold dilutions through cation exchange columns using AG50-X8 exchange resin from Eichrom Industries. The eluent from the cation columns were then sent through a seaFAST2 unit directly connected to an inductively coupled plasma mass spectrometer (ICP-MS) to analyze the REEs. Percent recoveries of the REEs ranged from 80–110% and fell within error for the external reference standard used and no signal suppression or isobaric interferences on the REEs were observed. These results demonstrate that a combined use of cation exchange columns and seaFAST2 instrumentation are effective in accurately quantifying the dissolved REEs in fluids that are >150,000 mg/L in TDS and have Ba:Eu ratios in excess of 380,000.« less

High Resolution Biostratigraphy and the Origin of the Basal Cambrian Bedded Chert from the Aksu Area (Tarim Block, Northwestern China)

NASA Astrophysics Data System (ADS)

Wang, Z.; Liu, H.; Dong, L.

2017-12-01

The early Cambrian Yurtus Formation in the Aksu area (Tarim block, northwestern China) consists of two lithostratigraphic units, lower black shale with interbedded chert unit and upper siltstone/carbonate unit. This time period represents the most important Proterozoic- Phanerozoic transition in earth's history. In recent years, the black shale has been confirmed to have high hydrocarbon generation potential. However, the depositional environment of the Yurtus Formation remains controversial and the biostratigraphic constrains are rather poor. The chert that is interbedded with black shale in the Yurtus Formation provides an exceptional taphonomic window to capture the diversity of the early Cambrian microfossils. Meanwhile, the origin of the bedded chert would give us some insight into the environmental background when the source rock was deposited. Therefore, in this research, we focus on the chert in the lower Yurtus formation and our purpose is to establish high resolution biostratigraphic framework and to better understand the depositional environment of the source rock. We investigated 4 sections in the Tarim basin: Kungaikuotan, Sugaite, Kule, and Yurtus VI. Abundant acritarch fossils have been identified, including Heliosphaeridium ampliatum, Yurtusia uniformis, and Comasphaeridium annulare. The tubular fossil Megathrix longus is also very common in this formation. In addition, two new types of specimens have been discovered, sheet-like encrolled fossils ( 0.5 mm in size) and regular spindle-like double layered microfossils ( 10μm in diameter). All of these fossils have constant occurrences in the studied sections, and can be well correlated with those yielded from the equivalent interval in South China. The biostratigraphic work suggests the source rock in the lower unit of the Yurtus Formation could be correlated with the Meishucunian small shelly fossil assemblage I and II. The Gemenium/Silicon ratio of the Yurtus chert is less than 1μmol/mol, suggesting the primary Si source is from normal sea water instead of hydrothermal fluids. The sea water origin and petrological evidence also indicate that the chert is unlikely mainly from the replacement of carbonate. This recognition fundamentally challenges the previous interpretation of the depositional environment.

A marine biogeochemical perspective on black shale deposition

NASA Astrophysics Data System (ADS)

Piper, D. Z.; Calvert, S. E.

2009-06-01

Deposition of marine black shales has commonly been interpreted as having involved a high level of marine phytoplankton production that promoted high settling rates of organic matter through the water column and high burial fluxes on the seafloor or anoxic (sulfidic) water-column conditions that led to high levels of preservation of deposited organic matter, or a combination of the two processes. Here we review the hydrography and the budgets of trace metals and phytoplankton nutrients in two modern marine basins that have permanently anoxic bottom waters. This information is then used to hindcast the hydrography and biogeochemical conditions of deposition of a black shale of Late Jurassic age (the Kimmeridge Clay Formation, Yorkshire, England) from its trace metal and organic carbon content. Comparison of the modern and Jurassic sediment compositions reveals that the rate of photic zone primary productivity in the Kimmeridge Sea, based on the accumulation rate of the marine fraction of Ni, was as high as 840 g organic carbon m - 2 yr -1. This high level was possibly tied to the maximum rise of sea level during the Late Jurassic that flooded this and other continents sufficiently to allow major open-ocean boundary currents to penetrate into epeiric seas. Sites of intense upwelling of nutrient-enriched seawater would have been transferred from the continental margins, their present location, onto the continents. This global flooding event was likely responsible for deposition of organic matter-enriched sediments in other marine basins of this age, several of which today host major petroleum source rocks. Bottom-water redox conditions in the Kimmeridge Sea, deduced from the V:Mo ratio in the marine fraction of the Kimmeridge Clay Formation, varied from oxic to anoxic, but were predominantly suboxic, or denitrifying. A high settling flux of organic matter, a result of the high primary productivity, supported a high rate of bacterial respiration that led to the depletion of O 2 in the bottom water. A high rate of burial of labile organic matter, albeit a low percentage of primary productivity, in turn promoted anoxic conditions in the sediment pore waters that enhanced retention of trace metals deposited from the water column.

Constraints on the timing of Marinoan ``Snowball Earth'' glaciation by 187Re-187Os dating of a Neoproterozoic, post-glacial black shale in Western Canada

NASA Astrophysics Data System (ADS)

Kendall, Brian S.; Creaser, Robert A.; Ross, Gerald M.; Selby, David

2004-06-01

New Re-Os isotopic data were obtained from chlorite-grade black shales from the upper Old Fort Point Formation (Windermere Supergroup), a post-glacial Neoproterozoic marker horizon in western Canada. A Re-Os isochron date of 634±57 Ma (MSWD=65, n=5) was determined using the conventional inverse aqua regia digestion medium. However, dissolution of the same samples with a new CrO 3-H 2SO 4 dissolution technique [Chem. Geol. 200 (2003) 225] yielded a much more precise date of 607.8±4.7 Ma (MSWD=1.2). Both dates are in agreement with existing U-Pb age constraints that bracket the Old Fort Point Formation between ˜685 and ˜570 Ma. The distinctive Re-Os systematics recorded by the two analytical protocols is explained by dissolution of a variably radiogenic, detrital Os component by the aqua regia method. In contrast, the CrO 3-H 2SO 4 technique minimizes this detrital component by selectively dissolving organic matter that is dominated by hydrogenous (seawater) Re and Os. The date of 607.8±4.7 Ma is thus interpreted as the depositional age for the upper Old Fort Point Formation providing a minimum age constraint for the timing of the second Windermere glaciation in western Canada. This ice age is correlative with the Marinoan (˜620-600 Ma) ice age and older than the ˜580-Ma Gaskiers glaciation of northeastern North America. The new Re-Os age determined from the CrO 3-H 2SO 4 digestion technique thus provides further support to a growing body of evidence for a global Marinoan glacial episode. Such an interpretation would not be discernable from the imprecise Re-Os date obtained with the aqua regia protocol. These results also indicate the potential for Re-Os radiometric dating of black shales that was not previously recognized. Importantly, neither chlorite-grade metamorphism nor the low organic content (TOC <1%) of the Old Fort Point Formation precluded the determination of a precise Re-Os depositional age using the CrO 3-H 2SO 4 analytical protocol.

Direct evidence for organic carbon preservation as clay-organic nanocomposites in a Devonian black shale; from deposition to diagenesis

NASA Astrophysics Data System (ADS)

Kennedy, Martin John; Löhr, Stefan Carlos; Fraser, Samuel Alex; Baruch, Elizabeth Teresa

2014-02-01

The burial of marine sourced organic carbon (OC) in continental margin sediments is most commonly linked to oceanographic regulation of bottom-water oxygenation (anoxia) and/or biological productivity. Here we show an additional influence in the Devonian Woodford Shale, in which OC occurs as nanometer intercalations with specific phyllosilicate minerals (mixed-layer illite/smectite) that we term organo-mineral nanocomposites. High resolution transmission electron microscopic (HRTEM) images provide direct evidence of this nano-scale relationship. While discrete micron-scale organic particles, such as Tasmanites algal cysts, are present in some lamina, a strong relation between total organic carbon (TOC) and mineral surface area (MSA) over a range of 15% TOC indicate that the dominant association of organic carbon is with mineral surfaces and not as discrete pelagic grains, consistent with HRTEM images of nanocomposites. Where periods of oxygenation are indicated by bioturbation, this relationship is modified by a shift to lower OC loading on mineral surfaces and reduced MSA variability likely resulting from biological mixing and homogenization of the sediment, oxidative burn down of OC and/or stripping of OC from minerals in animal guts. The TOC-MSA relationship extends across a range of burial depths and thermal maturities into the oil window and persists through partial illitization. Where illitization occurs, the loss of mineral surface area associated with the collapse of smectite interlayer space results in a systematic increase in TOC:MSA and reorganization of organic carbon and clays into nano-scale aggregates. While the Woodford Shale is representative of black shale deposits commonly thought to record heightened marine productivity and/or anoxia, our results point to the importance of high surface area clay minerals for OC enrichment. Given that the vast majority of these clay minerals are formed in soils before being transported to continental margin settings, their mineralogy and attendant preservative potential is primarily a function of continental climate and provenance making these deposits a sensitive recorder of land as well as oceanographic change.

Milankovitch Cyclicity in the Eocene Green River Formation of Colorado and Wyoming

NASA Astrophysics Data System (ADS)

Machlus, M.; Olsen, P. E.; Christie-Blick, N.; Hemming, S. R.

2001-12-01

The Eocene Green River Formation is a classic example of cyclic lacustrine sediments. Following Bradley (1929, U.S.G.S. Prof. Paper 158-E), many descriptive studies suggested precession and eccentricity as the probable climatic forcing to produce the cyclic pattern. Here we report spectral analysis results that confirm this hypothesis. Furthermore, we have identified the presence of a surprisingly large amplitude obliquity cycle, the long-period eccentricity cycle (400 k.y.) and the long period modulators of obliquity. Spectral analyses of data from Colorado were undertaken on an outcrop section and core data using two different proxies for lake depth. In a section measured in the west Piceance Creek basin, three lithologies (ranks) were used as a proxy for relative water depth, from relatively shallow to deep water: laminated marlstones; microlaminated, light-colored oil-shales; and microlaminated black oil shales. A multi-tapered spectrum of the 190-m-thick record in the depth domain shows significant peaks at periods of 2.1, 3.4, 12 and 39 m. These are interpreted as the precession, obliquity and eccentricity cycles. The precession cycle confirms Bradley's independent estimate of 2.4 m per 20 k.y. cycle, based on varve counts at the same location. A high-amplitude, continuous 3.4 m (obliquity) cycle exists in the evolutive spectrum of this record. A second spectral analysis of an oil-shale-yield record was made on a 530 m core near the basin depocenter. This record includes the time-equivalent of the outcrop section, spans a longer interval of time, and has a higher sedimentation rate. Peaks are found at 5, 10, 25 and 79 m. Again, the probable obliquity peak, at 10 m, is continuous along the record. Initial tuning of this record to a 39.9 k.y. cosine wave improves the resolution of the precession, short and long eccentricity cycles. Spectral analysis of oil shale yield and sonic velocity data of cores from the Green River basin, Wyoming, gives similar results. Spectral peaks at 6, 13, 31 and 122 m appear mainly in the Tipton and the Wilkins Peak members. The correlation between oil shale yield, lithology and relative water depth was examined in the upper part of the Wilkins Peak Member and the Lower part of the Laney Member. The succession from microlaminated black oil shale to laminated micrite corresponds with documented lateral changes in facies from deep to shallow environments, thus confirming the use of these facies as relative water-depth proxies. Furthermore, the upsection record of oil shale yields correlates with these facies, with higher yields corresponding to deeper water facies. This correlation supports the use of the oil shale yield record as a proxy for short-term lake-level changes, and therefore a proxy for climate. The spectral analysis results from both basins show the importance of the obliquity cycle in these continental records. This cycle cannot be identified by cycle-counting, and therefore was not previously recognized. Earlier published attempts at spectral analysis of short records from the Piceance Creek and Uinta basins misinterpreted the observed cycles. This is the first time both the obliquity cycle and the long-term eccentricity cycle have been identified in the Green River and Piceance Creek basins.

Faunal and erosional events in the Eastern Tethyan Sea across the K/T boundary

NASA Technical Reports Server (NTRS)

Keller, G.; Benjamini, C.

1988-01-01

A regional pattern of three closely spaced erosional events at and above the K/T boundary was determined from six Cretaceous/Tertiary boundary sections in the Negev of Israel. The sections were collected from locations throughout the central and northern Negev. All sections are lithologically similar. The Maastrichtian consists of a sequence of limestone beds intercalated with thin marly beds. In some sections, the last limestone bed is followed by 1 to 2 m of calcareous marls grading upwards into several meters of grey shale. In other sections the limestone bed is followed directly by grey shale with the contact containing particles of limestone and marl. A 5 to 20 cm thick dark grey organic-rich clay layer is present about 1.5 to 2.5 m above the base of the grey shale. The grey shale grades upwards into increasingly carbonate rich marls. No unconformities are apparent in field outcrops. During field collection the dark grey clay layer was believed to represent the K/T boundary clay. Microfossil analysis however identified the boundary at the base of the grey shale. The black shale represents a low productivity anoxic event similar to, but younger than, the K/T boundary clay in other K/T boundary sections. High resolution planktic foraminiferal and carbonate analysis of these sections (at 5 to 10 cm intervals) yield surprising results. The K/T boundary is marked by an erosional event which removed part or all of the uppermost Maastrichtian marls above the last limestone bed. Percent carbonate data for four Negev sections are illustrated and show the regional similarities in carbonate sedimentation. Faunal and carbonate data from the Negev sections thus show three closely spaced short erosional events at the K/T boundary and within the first 50,000 to 100,000 years of the Danian. These K/T boundary erosional events may represent global climatic or paleoceanographic events.

Potential Repercussions Associated with Halanaerobium Colonization of Hydraulically Fractured Shales

NASA Astrophysics Data System (ADS)

Booker, A. E.; Borton, M.; Daly, R. A.; Nicora, C.; Welch, S.; Dusane, D.; Johnston, M.; Sharma, S.; Mouser, P. J.; Cole, D. R.; Lipton, M. S.; Wrighton, K. C.; Wilkins, M.

2017-12-01

Hydraulic fracturing of black shale formations has greatly increased U.S. oil and natural gas recovery. Bacterial Halanaerobium strains become the dominant microbial community member in produced fluids from many fractured shales, regardless of their geographic location. Halanaerobium is not native to the subsurface, but is inadvertently introduced during the drilling and fracturing process. The accumulation of biomass in pipelines and reservoirs is detrimental due to possible well souring, microbially-induced corrosion, and pore clogging. Here, we used Halanaerobium strains isolated from a hydraulically fractured well in the Utica Shale, proteogenomics, isotopic and geochemical field observations, and laboratory growth experiments to identify detrimental effects associated with Halanaerobium growth. Analysis of Halanaerobium isolate genomes and reconstructed genomes from metagenomic datasets revealed the conserved presence of rhodanese-like proteins and anaerobic sulfite reductase complexes that can convert thiosulfate to sulfide. Furthermore, laboratory growth curves confirmed the capability of Halanaerobium to grow across a wide range of pressures (14-7000 PSI). Shotgun proteomic measurements were used to track the higher abundance of rhodanese and anaerobic sulfite reductase enzymes present when thiosulfate was available in the growth media. This technique also identified a higher abundance of proteins associated with the production of extracellular polymeric substances when Halanaerobium was grown under increasing pressures. Halanaerobium culture based assays identified thiosulfate-dependent sulfide production, while pressure incubations revealed higher cellular attachment to quartz surfaces. Increased production of sulfide and organic acids during stationary growth phase suggests that fermentative Halanaerobium use thiosulfate to remove excess reductant, aiding in NAD+ recovery. Additionally, the increased cellular attachment to surfaces under pressure indicates Halanaerobium has the capability of forming cellular clusters that could clog the shale fracture network and limit natural gas recovery. These findings bring awareness to the detrimental effects that could arise from Halanaerobium growth in hydraulically fractured shales throughout the U.S.

Stratigraphic and palaeoenvironmental summary of the south-east Georgia embayment: a correlation of exploratory wells

USGS Publications Warehouse

Poppe, Lawrence J.; Popenoe, Peter; Poag, C. Wylie; Swift, B. Ann

1995-01-01

A Continental Offshore Stratigraphic Test (COST) well and six exploratory wells have been drilled in the south-east Georgia embayment. The oldest rocks penetrated are weakly metamorphosed Lower Ordovician quartz arenites and Silurian shales and argillites in the Transco 1005-1 well and Upper Devonian argillites in the COST GE-1 well. These marine strata, which are equivalent to the Tippecanoe sequence in Florida, underlie the post-rift unconformity and represent part of a disjunct fragment of Gondwana that was sutured to the North American craton during the late Palaeozoic Alleghanian orogeny. The Palaeozoic strata are unconformably overlain by interbedded non-marine Jurassic (Bajocian and younger) sandstones and shales and marginal marine Lower Cretaceous sandstones, calcareous shales and carbonates, which contain scattered beds of coal and evaporite. Together, these rocks are stratigraphically equivalent to the onshore Fort Pierce and Cotton Valley(?) Formations and rocks of the Lower Cretaceous Comanchean Provincial Series. The abundance of carbonates and evaporites in this interval, which reflects marine influences within the embayment, increases upwards, eastwards and southwards. The Upper Cretaceous part of the section is composed mainly of neritic calcareous shales and shaley limestones stratigraphically equivalent to the primarily marginal marine facies of the onshore Atkinson, Cape Fear and Middendorf Formations and Black Creek Group, and to limestones and shales of the Lawson Limestone and Peedee Formations. Cenozoic strata are primarily semiconsolidated marine carbonates. Palaeocene to middle Eocene strata are commonly cherty; middle Miocene to Pliocene strata are massive and locally phosphatic and glauconitic; Quaternary sediments are dominated by unconsolidated carbonate sands. The effects of eustatic changes and shifts in the palaeocirculation are recorded in the Upper Cretaceous and Tertiary strata.

Exposure to dust and particle-associated 1-nitropyrene of drivers of diesel-powered equipment in underground mining.

PubMed

Scheepers, P T J; Micka, V; Muzyka, V; Anzion, R; Dahmann, D; Poole, J; Bos, R P

2003-07-01

A field study was conducted in two mines in order to determine the most suitable strategy for ambient exposure assessment in the framework of a European study aimed at validation of biological monitoring approaches for diesel exhaust (BIOMODEM). Exposure to dust and particle-associated 1-nitropyrene (1-NP) was studied in 20 miners of black coal by the long wall method (Czech Republic) and in 20 workers in oil shale mining by the room and pillar method (Estonia). The study in the oil shale mine was extended to include 100 workers in a second phase (main study). In each mine half of the study population worked underground as drivers of diesel-powered trains (black coal) and excavators (oil shale). The other half consisted of workers occupied in various non-diesel production assignments. Exposure to diesel exhaust was studied by measurement of inhalable and respirable dust at fixed locations and by personal air sampling of respirable dust. The ratio of geometric mean inhalable to respirable dust concentration was approximately two to one. The underground/surface ratio of respirable dust concentrations measured at fixed locations and in the breathing zones of the workers was 2-fold or greater. Respirable dust was 2- to 3-fold higher in the breathing zone than at fixed sampling locations. The 1-NP content in these dust fractions was determined by gas chromatography-mass spectrometry/mass spectrometry and ranged from 0.003 to 42.2 ng/m(3) in the breathing zones of the workers. In mine dust no 1-NP was detected. In both mines 1-NP was observed to be primarily associated with respirable particles. The 1-NP concentrations were also higher underground than on the surface (2- to 3-fold in the coal mine and 10-fold or more in the oil shale mine). Concentrations of 1-NP in the breathing zones were also higher than at fixed sites (2.5-fold in the coal mine and 10-fold in the oil shale mine). For individual exposure assessment personal air sampling is preferred over air sampling at fixed sites. This study also suggests that particle-associated 1-NP much better reflects the ambient exposure to diesel exhaust particles than dust concentrations. Therefore, measurement of particle-associated 1-NP is preferred over measurement of dust concentrations by gravimetry, when linking ambient exposure to biomonitoring outcomes such as protein and DNA adducts and excretion of urinary metabolites of genotoxic substances.

Long-term oceanic changes prior the end-Triassic mass extinction

NASA Astrophysics Data System (ADS)

Clémence, Marie-Emilie; Mette, Wolfgang; Thibault, Nicolas; Korte, Christoph

2014-05-01

A number of potential causes and kill mechanisms have been proposed for the end-Triassic mass extinction such as palaeoclimatic and sea-level variations, massive volcanism and ocean acidification. Recent analysis of the stomatal index and density of fossil leaves and geochemical research on pedogenic carbonate nodules are suggestive of rising atmospheric CO2 concentration and fluctuating climate in the Rhaetian. It seems therefore probable that the end-Triassic event was preceded by large climatic fluctuations and environmental perturbations in the Rhaetian which might have partly affected the composition and diversity of the terrestrial and marine biota prior to the end-Triassic interval. The Northern Calcareous Alps (NCA) has long been favored for the study of the Rhaetian, since the GSSP of the Triassic/Jurassic (T/J) boundary and other important T/J sections are situated in this region. However, the most famous Rhaetian sections in the NCA are composed of carbonates from the Koessen Formation and were situated in a large isolated intraplatform Basin (the Eiberg Basin), bordered to the south-east by a well-developed coral reef in the NW of the Tethys border. Several Rhaetian sections composed of marls and shales of the Zlambach Formation were deposited at the same time on the other side of this reef, in the oceanic Halstatt Basin, which was in direct connection to the Tethys. Here, we present new results on sedimentology, stable isotope and trace element analysis of both intraplatform and oceanic basin deposits in the NCA. Intraplatform Rhaetian sections from the Koessen Formation bear a few minor intervals of shales with enrichments in organic matter, some of which are associated to carbon isotopic excursions. Oceanic sections from the Hallstatt Basin are characterized at the base by very cyclic marl-limestone alternations. Higher up in the section, sediments progressively turn into pure shale deposits and the top of the Formation is characterized by organic-rich, laminated black shales. This interval of black shales is associated with a 2 per mil negative carbon isotopic excursion and a strong warming as suggested by fluctuations in oxygen isotopes. Forthcoming geochemical and paleontological analysis on these two Formations should help us : (1) better constrain the stratigraphy of the Rhaetian in the NCA by correlating geochemical and climatic events that took place both in the intraplaform (Eiberg) and oceanic (Hallstatt) Basin, (2) decipher localized vs large Tethyan anoxic events and associated carbon-cycle perturbations and (3) constrain the possible influence of Rhaetian climatic perturbations on the biota before the end-Triassic mass extinction.

Major and trace elements in Mahogany zone oil shale in two cores from the Green River Formation, piceance basin, Colorado

USGS Publications Warehouse

Tuttle, M.L.; Dean, W.E.; Parduhn, N.L.

1983-01-01

The Parachute Creek Member of the lacustrine Green River Formation contains thick sequences of rich oil-shale. The richest sequence and the richest oil-shale bed occurring in the member are called the Mahogany zone and the Mahogany bed, respectively, and were deposited in ancient Lake Uinta. The name "Mahogany" is derived from the red-brown color imparted to the rock by its rich-kerogen content. Geochemical abundance and distribution of eight major and 18 trace elements were determined in the Mahogany zone sampled from two cores, U. S. Geological Survey core hole CR-2 and U. S. Bureau of Mines core hole O1-A (Figure 1). The oil shale from core hole CR-2 was deposited nearer the margin of Lake Uinta than oil shale from core hole O1-A. The major- and trace-element chemistry of the Mahogany zone from each of these two cores is compared using elemental abundances and Q-mode factor modeling. The results of chemical analyses of 44 CR-2 Mahogany samples and 76 O1-A Mahogany samples are summarized in Figure 2. The average geochemical abundances for shale (1) and black shale (2) are also plotted on Figure 2 for comparison. The elemental abundances in the samples from the two cores are similar for the majority of elements. Differences at the 95% probability level are higher concentrations of Ca, Cu, La, Ni, Sc and Zr in the samples from core hole CR-2 compared to samples from core hole O1-A and higher concentrations of As and Sr in samples from core hole O1-A compared to samples from core hole CR-2. These differences presumably reflect slight differences in depositional conditions or source material at the two sites. The Mahogany oil shale from the two cores has lower concentrations of most trace metals and higher concentrations of carbonate-related elements (Ca, Mg, Sr and Na) compared to the average shale and black shale. During deposition of the Mahogany oil shale, large quantities of carbonates were precipitated resulting in the enrichment of carbonate-related elements and dilution of most trace elements as pointed out in several previous studies. Q-mode factor modeling is a statistical method used to group samples on the basis of compositional similarities. Factor end-member samples are chosen by the model. All other sample compositions are represented by varying proportions of the factor end-members and grouped as to their highest proportion. The compositional similarities defined by the Q-mode model are helpful in understanding processes controlling multi-element distributions. The models for each core are essentially identical. A four-factor model explains 70% of the variance in the CR-2 data and 64% of the O1-A data (the average correlation coefficients are 0. 84 and 0. 80, respectively). Increasing the number of factors above 4 results in the addition of unique instead of common factors. Table I groups the elements based on high factor-loading scores (the amount of influence each element has in defining the model factors). Similar elemental associations are found in both cores. Elemental abundances are plotted as a function of core depth using a five-point weighted moving average of the original data to smooth the curve (Figure 3 and 4). The plots are grouped according to the four factors defined by the Q-mode models and show similar distributions for elements within the same factor. Factor 1 samples are rich in most trace metals. High oil yield and the presence of illite characterize the end-member samples for this factor (3, 4) suggesting that adsorption of metals onto clay particles or organic matter is controlling the distribution of the metals. Precipitation of some metals as sulfides is possible (5). Factor 2 samples are high in elements commonly associated with minerals of detrital or volcanogenic origin. Altered tuff beds and lenses are prevalent within the Mahogany zone. The CR-2 end-member samples for this factor contain analcime (3) which is an alteration product within the tuff beds of the Green River Formation. Th

Separation and Precipitation of Nickel from Acidic Sulfate Leaching Solution of Molybdenum-Nickel Black Shale by Potassium Nickel Sulfate Hexahydrate Crystallization

NASA Astrophysics Data System (ADS)

Deng, Zhigan; Wei, Chang; Fan, Gang; Li, Xingbin; Li, Minting; Li, Cunxiong

2018-02-01

Nickel was separated and precipitated with potassium nickel sulfate hexahydrate [K2Ni(SO4)2·6H2O] from acidic sulfate solution, a leach solution from molybdenum-nickel black shale. The effects of the potassium sulfate (K2SO4) concentration, crystallization temperature, solution pH, and crystallization time on nickel(II) recovery and iron(III) precipitation were investigated, revealing that nickel and iron were separated effectively. The optimum parameters were K2SO4 concentration of 200 g/L, crystallization temperature of 10°C, solution pH of 0.5, and crystallization time of 24 h. Under these conditions, 97.6% nickel(II) was recovered as K2Ni(SO4)2·6H2O crystals while only 2.0% of the total iron(III) was precipitated. After recrystallization, 98.4% pure K2Ni(SO4)2·6H2O crystals were obtained in the solids. The mother liquor was purified by hydrolysis-precipitation followed by cooling, and more than 99.0% K2SO4 could be crystallized. A process flowsheet was developed to separate iron(III) and nickel(II) from acidic-sulfate solution.

Methane, Black Carbon, and Ethane Emissions from Natural Gas Flares in the Bakken Shale, North Dakota.

PubMed

Gvakharia, Alexander; Kort, Eric A; Brandt, Adam; Peischl, Jeff; Ryerson, Thomas B; Schwarz, Joshua P; Smith, Mackenzie L; Sweeney, Colm

2017-05-02

Incomplete combustion during flaring can lead to production of black carbon (BC) and loss of methane and other pollutants to the atmosphere, impacting climate and air quality. However, few studies have measured flare efficiency in a real-world setting. We use airborne data of plume samples from 37 unique flares in the Bakken region of North Dakota in May 2014 to calculate emission factors for BC, methane, ethane, and combustion efficiency for methane and ethane. We find no clear relationship between emission factors and aircraft-level wind speed or between methane and BC emission factors. Observed median combustion efficiencies for methane and ethane are close to expected values for typical flares according to the US EPA (98%). However, we find that the efficiency distribution is skewed, exhibiting log-normal behavior. This suggests incomplete combustion from flares contributes almost 1/5 of the total field emissions of methane and ethane measured in the Bakken shale, more than double the expected value if 98% efficiency was representative. BC emission factors also have a skewed distribution, but we find lower emission values than previous studies. The direct observation for the first time of a heavy-tail emissions distribution from flares suggests the need to consider skewed distributions when assessing flare impacts globally.

Levelling and merging of two discrete national-scale geochemical databases: A case study showing the surficial expression of metalliferous black shales

USGS Publications Warehouse

Smith, Steven M.; Neilson, Ryan T.; Giles, Stuart A.

2015-01-01

Government-sponsored, national-scale, soil and sediment geochemical databases are used to estimate regional and local background concentrations for environmental issues, identify possible anthropogenic contamination, estimate mineral endowment, explore for new mineral deposits, evaluate nutrient levels for agriculture, and establish concentration relationships with human or animal health. Because of these different uses, it is difficult for any single database to accommodate all the needs of each client. Smith et al. (2013, p. 168) reviewed six national-scale soil and sediment geochemical databases for the United States (U.S.) and, for each, evaluated “its appropriateness as a national-scale geochemical database and its usefulness for national-scale geochemical mapping.” Each of the evaluated databases has strengths and weaknesses that were listed in that review.Two of these U.S. national-scale geochemical databases are similar in their sample media and collection protocols but have different strengths—primarily sampling density and analytical consistency. This project was implemented to determine whether those databases could be merged to produce a combined dataset that could be used for mineral resource assessments. The utility of the merged database was tested to see whether mapped distributions could identify metalliferous black shales at a national scale.

Breccia pipes in the Karoo Basin, South Africa, as conduits for metamorphic gases to the Early Jurassic atmosphere

NASA Astrophysics Data System (ADS)

Silkoset, Petter; Svensen, Henrik; Planke, Sverre

2014-05-01

The Toarcian (Early Jurassic) event was manifested by globally elevated temperatures and anoxic ocean conditions that particularly affected shallow marine taxa. The event coincided with the emplacement of the vast Karoo-Ferrar Large Igneous Province. Among the suggestions for trigger mechanisms for the climatic perturbation is metamorphic methane generation from black shale around the sills in the Karoo Basin, South Africa. The sill emplacement provides a mechanism for voluminous in-situ production and emission of greenhouse gases, and establishes a distinct link between basin-trapped and atmospheric carbon. In the lower stratigraphic levels of the Karoo Basin, black shales are metamorphosed around sills and the sediments are cut by a large number of pipe structures with metamorphic haloes. The pipes are vertical, cylindrical structures that contain brecciated and baked sediments with variable input of magmatic material. Here, we present borehole, petrographic, geochemical and field data from breccia pipes and contact aureoles based on field campaigns over a number of years (2004-2014). The metamorphism around the pipes show equivalent metamorphic grade as the sediments around nearby sills, suggesting a more prominent phreatomagmatic component than previously thought. The stratigraphic position of pipes and the breccia characteristics strengthens the hypothesis of a key role in the Toarcian carbon isotope excursion.

Marine sulfur cycle constrained from isotope analysis of different forms of sulfur in the 3.2 Ga black shale (DXCL-DP) from Pilbara, Australia

NASA Astrophysics Data System (ADS)

Kobayashi, Y.; Yamaguchi, K. E.; Sakamoto, R.; Naraoka, H.; Kiyokawa, S.; Ikehara, M.; Ito, T.

2012-12-01

Co-evolution of early life and surface environment has been one of the most important events on Earth. Rise of atmospheric oxygen, or as known as GOE (Great Oxidation Event: e.g., Holland, 1994), has been widely believed to have occurred at around 2.4 billion years ago. But geological and geochemical evidence suggest possibility of much earlier (by hundreds of millions of years) existence of oxic atmosphere and oceans. In order to further investigate the mystery of biological and environmental evolution, we conducted continental drilling in northwestern Pilbara, Western. Australia, to obtain 3.2 billion-years-old least-metamorphosed drillcore black shale samples (DXCL-DP:Dixon Island - Cleaverville Drilling Project; Yamaguchi et al., 2009). Preliminary stable isotope analyses using these samples suggested that photosynthetic organisms produced organic matter (Hosoi et al., 2011), nitrogen fixing bacteria were intermittently active (Yamada et al., 2011), and sulfate-reducing bacteria were active in environment with a limited supply of sulfate (Sakamoto et al., 2011) in the 3.2 Ga ocean. Bulk S isotope compositions could only provide limited information on the biogeochemical cycling of sedimentary S, because it is normally present as different facies (acid-volatile sulfur: AVS, pyrite: FeS2, sulfate, organic sulfur: Sorg, and elemental sulfur: S0) that depend on physicochemical and biological conditions. Therefore, abundance and isotope ratios of these species possess very useful information on oceanic and diagenetic conditions such as redox state and microbiological activity. In order to constrain biogeochemical cycling of S in the 3.2 Ga ocean, we conducted sequential extraction analysis using the DXCL-DP black shales to obtain different S-bearing species and S isotopic analysis. Average S contents for each form of S-bearing species were: ΣS = 2.56 wt.%, AVS = 0.02 wt.%, pyrite = 1.61 wt.%, and sulfate = 0.57 wt%. Relationship between amounts of pyrite-S and organic C suggest presence of syngenetic pyrite (formed in water column) as well as diagenetic pyrite. Average S isotope compositions are: pyrite = 12.3±6.3 ‰, sulfate = 17.3 ± 7.1 ‰, and difference between them are up to as high as 16.8 ‰. These results show that depositional environment was probably close to the modern Black Sea, where sulfate-reducing bacteria are active in anaerobic water mass in semi-closed deep basin, with a limited supply of sulfate from the oxic surface ocean.

The use of hydroxyacids as geochemical indicators

NASA Technical Reports Server (NTRS)

Cardoso, J. N.; Eglinton, G.

1983-01-01

The distributions of hydroxyacids in a variety of recent and ancient sediments have been determined by gas chromatography-mass spectrometry. A lacustrine sediment (Rostherne Mere, U.K.) and two marine situations (Cariaco Trench, Black Sea) were analyzed as examples of recent depositional environments. Beta-hydroxyacids occurred in all of the recent sediments, consistent with their presumed microbial origin, whereas di- and trihydroxyacids were present in the sediments with a significant higher plant input (Black Sea and Rostherne Mere sediments). The two ancient (Eocene) sediments examined, viz, the Greene River (U.S.) and Messel (Germany) oil shales, contained only trace amounts of hydroxyacids. These results provide evidence that hydroxyacids are in general not well preserved over geological time.

Diagenetic variation at the lamina scale in lacustrine organic-rich shales: Implications for hydrocarbon migration and accumulation

NASA Astrophysics Data System (ADS)

Liang, Chao; Cao, Yingchang; Liu, Keyu; Jiang, Zaixing; Wu, Jing; Hao, Fang

2018-05-01

Lacustrine carbonate-rich shales are well developed within the Mesozoic-Cenozoic strata of the Bohai Bay Basin (BBB) of eastern China and across southeast Asia. Developing an understanding of the diagenesis of these shales is essential to research on mass balance, diagenetic fluid transport and exchange, and organic-inorganic interactions in black shales. This study investigates the origin and distribution of authigenic minerals and their diagenetic characteristics, processes, and pathways at the scale of lacustrine laminae within the Es4s-Es3x shale sequence of the BBB. The research presented in this study is based on thin sections, field emission scanning electron microscope (FESEM) and SEM-catholuminescence (CL) observations of well core samples combined with the use of X-ray diffraction (XRD), energy dispersive spectroscopy, electron microprobe analysis, and carbon and oxygen isotope analyses performed using a laser microprobe mass spectrometer. The dominant lithofacies within the Es4s-Es3x sequence are a laminated calcareous shale (LCS-1) and a laminated clay shale (LCS-2). The results of this study show that calcite recrystallization1 is the overarching diagenetic process affecting the LCS-1, related to acid generation from organic matter (OM) thermal evolution. This evolutionary transition is the key factor driving the diagenesis of this lithofacies, while the transformation of clay minerals is the main diagenetic attribute of the LCS-2. Diagenetic differences occur within different laminae and at variable locations within the same lamina level, controlled by variations in mineral composition and the properties of laminae interfaces. The diagenetic fluid migration scale is vertical and responses (dissolution and replacement) are limited to individual laminae, between zero and 100 μm in width. In contrast, the dominant migration pathway for diagenetic fluid is lateral, along the abrupt interfaces between laminae boundaries, which leads to the vertical transmission of diagenetic responses. The recrystallization boundaries between calcite laminae act as the main migration pathways for the expulsion of hydrocarbons from these carbonate-rich lacustrine shales. However, because the interaction between diagenetic fluids and the shales themselves is limited to the scale of individual lamina, this system is normally closed. The occurrence of abnormal pressure fractures can open the diagenetic system, however, and cause interactions to occur throughout laminae; in particular, the closed-open (C-O) diagenetic process at this scale is critical to this shale interval. Multi-scale C-O systems are ubiquitous and episodic ranging from the scale of laminae to the whole basin. Observations show that such small-scale systems are often superimposed onto larger ones to constitute the complex diagenetic system seen within the BBB combining fluid transport, material and energy exchange, and solid-liquid and organic-inorganic interactions.

Arbitrage with fractional Gaussian processes

NASA Astrophysics Data System (ADS)

Zhang, Xili; Xiao, Weilin

2017-04-01

While the arbitrage opportunity in the Black-Scholes model driven by fractional Brownian motion has a long history, the arbitrage strategy in the Black-Scholes model driven by general fractional Gaussian processes is in its infancy. The development of stochastic calculus with respect to fractional Gaussian processes allowed us to study such models. In this paper, following the idea of Shiryaev (1998), an arbitrage strategy is constructed for the Black-Scholes model driven by fractional Gaussian processes, when the stochastic integral is interpreted in the Riemann-Stieltjes sense. Arbitrage opportunities in some fractional Gaussian processes, including fractional Brownian motion, sub-fractional Brownian motion, bi-fractional Brownian motion, weighted-fractional Brownian motion and tempered fractional Brownian motion, are also investigated.

A 6,000-year sedimentary molecular record of chemocline excursions in the Black Sea

NASA Technical Reports Server (NTRS)

Sinninghe Damste, J. S.; Wakeham, S. G.; Kohnen, M. E.; Hayes, J. M.; de Leeuw, J. W.

1993-01-01

The Black Sea is the world's largest anoxic basin; it is also a contemporary analogue of the environment in which carbonaceous shales and petroleum source beds formed. Recently, Repeta et al. reported that anoxygenic photosynthesis may be an important component of carbon cycling in the present Black Sea, owing to a shoaling of the chemocline and consequent penetration of the photic zone by anaerobic waters in the past few decades. It has been suggested that this was due to an anthropogenic decrease in freshwater input to the Black Sea, although natural causes were not ruled out. Here we report the distributions of sequestered photosynthetic pigments in eight core samples of sediments from the Black Sea ranging in age from zero to 6,200 years before the present. Our results show that photosynthetic green sulphur bacteria (Chlorobiaceae [correction of Clorobiaceae]) have been active in the Black Sea for substantial periods of time in the past. This finding indicates that the penetration of the photic zone by anaerobic waters is not a recent phenomenon, and suggests that natural causes for shoaling of the chemocline are more likely than anthropogenic ones.

Spatial and Temporal Variations of the Indidura Formation (Cenomanian-Turonian) in Northeastern Mexico, Coahuila State

NASA Astrophysics Data System (ADS)

Duque-Botero, F.; Maurrasse, F. J.

2002-12-01

Rock sequences of Cenomanian-Turonian age commonly assigned to the Indidura Formation in northeastern Mexico, Coahuila State, are shown to include distinct facies indicative of significant spatial variability over the carbonate platform of that region. The type section at Las Delicias is characterized by very-pale orange (10YR8/2) bedded biocalcirudites (10-30 cm thick), without internal structures, and comprises fossil assemblages rich in epifaunal groups, as well as nektonic and planktic taxa. Total inorganic carbon (TIC) varies between 48 % and 94 %, with fluctuation in total organic carbon (TOC) between 0.73 % and 1.58 %. The section at la Casita Canyon, farther southeast, consists of pale yellowish brown (10YR6/2) interbedded biocalcilutites and olive gray (5Y3/2) shales between 3 and 30 cm thick. They also show no apparent original internal structures, and allochems consist essentially of sparse fragments of planktonic foraminifera and radiolarian. TIC content varies between 0.84 % and 59.3 %, whereas TOC changes between 0.17 % and 5.85 %. In contrast, in the Parras Mountains, located south of La Delicias and northwest of la Casita, the succession occurs under a characteristic sequence showing interbeds of light olive gray (5Y6/1) and brownish black to olive black (5YR2/1 - 5Y2/1) shales and marly biocalcilutites 30 to 100 cm thick. They display distinct internal structures arranged in nearly even parallel varve-like dual lamina (<3 mm thick). Few planktonic foraminifera are present, but epifaunal remains are absent, except for occasional rare pelecypods (Inoceramus) that occur intermittently. Laminae from either the shales or limestone facies show that they are formed by differences associated with varying abundance of micro spheres and "micro-ooids", interpreted to be of cyanobacterial origin. TIC content varies from 43 % to 78.3 %, while TOC content remains relatively high with values between 7.35 % and 24.39 %, but more consistently higher than 20 %. Assuming that these facies are coeval, microfacies studies of these rocks as well as acid etched polished rocks, and scanning electron microscope examination (secondary and backscatter imaging) further substantiate these spatial differences. TOC-rich black shales in the Parras region further document unique paleoceanographic conditions, which was also characterized by oxygenation of oceanic waters less effective than usual. These unique paleoceanographic conditions imply that oxygenation of oceanic waters remained apparently less effective than usual throughout the sequence. Temporal distribution of the epifauna and carbon/carbonate variations in the Parras region suggest the effects of strong dysoxic/anoxic bottom conditions on the biota with rhythmical production and disappearance of cyanobacterial mats which remained dominant throughout.

Fire severity mediates climate-driven shifts in understorey community composition of black spruce stands of interior Alaska

Treesearch

Emily L. Bernhardt; Teresa N. Hollingsworth; F. Stuart Chapin

2011-01-01

Question: How do pre-fire conditions (community composition and environmental characteristics) and climate-driven disturbance characteristics (fire severity) affect post-fire community composition in black spruce stands? Location: Northern boreal forest, interior Alaska. Methods: We compared plant community composition and environmental stand characteristics in 14...

The stratigraphy of the southern Pab Range, Pakistan

NASA Astrophysics Data System (ADS)

White, H. J.

The Cretaceous strata exposed in the southern Pab Range, southeast Baluchistan, Pakistan is investigated. It records the precollision deposition history of the Indo-Pakistani continental shelf. The strata comprise two depositional successions, namely, The Early to Late Cretaceous Sembar-Goru-Parh sequence and the Maestrichtian Mughal Kot-Pab sequence. The former began with deposition of black shales on the continental slope (Sembar Formation), succeeded by calcareous shale, marl and micstone of outer shelf origin (Goru Formation), and ended with inner shelf platform carbonates (Parh Limestone). These deep to shallow water lithofacies prograted westward over the continental shelf of the north-advancing Subcontinent. The Mughal Kot-Pab propagation contains the first significant influx of terrigenous sand reaching the western portion of the continental shelf. Deposition environments in the Mughal Kot Formation include inner shelf, prodelta, delta front and distributary channel. A thick succession of shoreface cycles comprises the Pab sandstone.

A Tale of Two Regions: Landscape Ecological Planning for Shale Gas Energy Futures

NASA Astrophysics Data System (ADS)

Murtha, T., Jr.; Schroth, O.; Orland, B.; Goldberg, L.; Mazurczyk, T.

2015-12-01

As we increasingly embrace deep shale gas deposits to meet global energy demands new and dispersed local and regional policy and planning challenges emerge. Even in regions with long histories of energy extraction, such as coal, shale gas and the infrastructure needed to produce the gas and transport it to market offers uniquely complex transformations in land use and landcover not previously experienced. These transformations are fast paced, dispersed and can overwhelm local and regional planning and regulatory processes. Coupled to these transformations is a structural confounding factor. While extraction and testing are carried out locally, regulation and decision-making is multilayered, often influenced by national and international factors. Using a geodesign framework, this paper applies a set of geospatial landscape ecological planning tools in two shale gas settings. First, we describe and detail a series of ongoing studies and tools that we have developed for communities in the Marcellus Shale region of the eastern United States, specifically the northern tier of Pennsylvania. Second, we apply a subset of these tools to potential gas development areas of the Fylde region in Lancashire, United Kingdom. For the past five years we have tested, applied and refined a set of place based and data driven geospatial models for forecasting, envisioning, analyzing and evaluating shale gas activities in northern Pennsylvania. These models are continuously compared to important landscape ecological planning challenges and priorities in the region, e.g. visual and cultural resource preservation. Adapting and applying these tools to a different landscape allow us to not only isolate and define important regulatory and policy exigencies in each specific setting, but also to develop and refine these models for broader application. As we continue to explore increasingly complex energy solutions globally, we need an equally complex comparative set of landscape ecological planning tools to inform policy, design and regional planning. Adapting tools and techniques developed in Pennsylvania where shale gas extraction is ongoing to Lancashire, where industry is still in the exploratory phase offers a key opportunity to test and refine more generalizable models.

Regional and Detailed Survey for Radon Activities in Soil-Gas and Groundwater in the Okchon Zone, Korea

NASA Astrophysics Data System (ADS)

Je, H.-K.; Chon, H.-T.

2012-04-01

The Okchon zone in Korea provides a typical example of natural geological materials enriched in potentially toxic elements including uranium which is parent nuclide for radon gas. For the purpose of radon radioactivity risk assessment, making the map of radon risk grade from Okchon zone, regional and detailed field surveys were carried out during 3 years. The study area is located in the central part of Korea, called the Okchon zone (about 5,100 km2), which occur in a 80km wide, northeast-trending belt that extends across the Korean Peninsula. The Okchon zone is underlain by metasedimentary rocks of unknown age that are composed mainly of black slate, phyllite, shale, and limestone. The three research areas (defined as Boeun, Chungju, and Nonsan) for detailed survey were selected from the results of regional survey. Results of detailed radon survey indicated a wide range of radon activities for soil-gases (148-1,843 pCi/L) and ground waters (23-5,540 pCi/L). About 15 percent of soil-gas samples exceeded 1,000 pCi/L and 84 percent of ground water samples exceeded the MCL (maximum contaminant level) of drinking water, 300 pCi/L, which proposed by U.S. Environmental Protection Agency in 1999. For detailed survey, radon activities of soil-gas and ground water were classified as bedrock geology, based on 1/50,000 geological map and field research. For soil-gas measurements, mean values of radon activity from black slate-shale (789 pCi/L) were highest among the other base rocks. And for groundwater measurements, mean value of radon activities were decreased in the order of granite (1,345 pCi/L) > black shale-slate (915 pCi/L) > metasediments (617 pCi/L). Result of indoor radon measurement from detailed survey areas showed that about 50% of houses exceeded the indoor guideline, 4 pCi/L. For the radon risk assessment in indoor environment showed that probability of lung cancer risk from the houses located on the granite base rock (3.0×10-2) was highest among the other base rocks. Finally, the maps of radon risk grade from detailed survey areas were developed by the application of field data and statistical simulation.

A reactive transport model for Marcellus shale weathering

NASA Astrophysics Data System (ADS)

Heidari, Peyman; Li, Li; Jin, Lixin; Williams, Jennifer Z.; Brantley, Susan L.

2017-11-01

Shale formations account for 25% of the land surface globally and contribute a large proportion of the natural gas used in the United States. One of the most productive shale-gas formations is the Marcellus, a black shale that is rich in organic matter and pyrite. As a first step toward understanding how Marcellus shale interacts with water in the surface or deep subsurface, we developed a reactive transport model to simulate shale weathering under ambient temperature and pressure conditions, constrained by soil and water chemistry data. The simulation was carried out for 10,000 years since deglaciation, assuming bedrock weathering and soil genesis began after the last glacial maximum. Results indicate weathering was initiated by pyrite dissolution for the first 1000 years, leading to low pH and enhanced dissolution of chlorite and precipitation of iron hydroxides. After pyrite depletion, chlorite dissolved slowly, primarily facilitated by the presence of CO2 and organic acids, forming vermiculite as a secondary mineral. A sensitivity analysis indicated that the most important controls on weathering include the presence of reactive gases (CO2 and O2), specific surface area, and flow velocity of infiltrating meteoric water. The soil chemistry and mineralogy data could not be reproduced without including the reactive gases. For example, pyrite remained in the soil even after 10,000 years if O2 was not continuously present in the soil column; likewise, chlorite remained abundant and porosity remained small if CO2 was not present in the soil gas. The field observations were only simulated successfully when the modeled specific surface areas of the reactive minerals were 1-3 orders of magnitude smaller than surface area values measured for powdered minerals. Small surface areas could be consistent with the lack of accessibility of some fluids to mineral surfaces due to surface coatings. In addition, some mineral surface is likely interacting only with equilibrated pore fluids. An increase in the water infiltration rate enhanced weathering by removing dissolution products and maintaining far-from-equilibrium conditions. We conclude from these observations that availability of reactive surface area and transport of H2O and gases are the most important factors affecting rates of Marcellus shale weathering of the in the shallow subsurface. This weathering study documents the utility of reactive transport modeling for complex subsurface processes. Such modelling could be extended to understand interactions between injected fluids and Marcellus shale gas reservoirs at higher temperature, pressure, and salinity conditions.

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

USGS Publications Warehouse

Tuttle, M.L.W.; Breit, G.N.; Goldhaber, M.B.

2009-01-01

During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies. Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.

Coupled heat and fluid flow modeling of the Carboniferous Kuna Basin, Alaska: Implications for the genesis of the Red Dog Pb-Zn-Ag-Ba ore district

USGS Publications Warehouse

Garven, G.; Raffensperger, Jeff P.; Dumoulin, Julie A.; Bradley, D.A.; Young, L.E.; Kelley, K.D.; Leach, D.L.

2003-01-01

The Red Dog deposit is a giant 175 Mton (16% Zn, 5% Pb), shale-hosted Pb-Zn-Ag-Ba ore district situated in the Carboniferous Kuna Basin, Western Brooks Range, Alaska. These SEDEX-type ores are thought to have formed in calcareous turbidites and black mudstone at elevated sub-seafloor temperatures (120-150??C) within a hydrogeologic framework of submarine convection that was structurally organized by large normal faults. The theory for modeling brine migration and heat transport in the Kuna Basin is discussed with application to evaluating flow patterns and heat transport in faulted rift basins and the effects of buoyancy-driven free convection on reactive flow and ore genesis. Finite element simulations show that hydrothermal fluid was discharged into the Red Dog subbasin during a period of basin-wide crustal heat flow of 150-160 mW/m2. Basinal brines circulated to depths as great as 1-3 km along multiple normal faults flowed laterally through thick clastic aquifers acquiring metals and heat, and then rapidly ascended a single discharge fault zone at rates ??? 5 m/year to mix with seafloor sulfur and precipitate massive sulfide ores. ?? 2003 Elsevier Science B.V. All rights reserved.

The rise of fire: Fossil charcoal in late Devonian marine shales as an indicator of expanding terrestrial ecosystems, fire, and atmospheric change

USGS Publications Warehouse

Rimmer, Susan M.; Hawkins, Sarah J.; Scott, Andrew C.; Cressler, Walter L.

2015-01-01

Fossil charcoal provides direct evidence for fire events that, in turn, have implications for the evolution of both terrestrial ecosystems and the atmosphere. Most of the ancient charcoal record is known from terrestrial or nearshore environments and indicates the earliest occurrences of fire in the Late Silurian. However, despite the rise in available fuel through the Devonian as vascular land plants became larger and trees and forests evolved, charcoal occurrences are very sparse until the Early Mississippian where extensive charcoal suggests well-established fire systems. We present data from the latest Devonian and Early Mississippian of North America from terrestrial and marine rocks indicating that fire became more widespread and significant at this time. This increase may be a function of rising O2 levels and the occurrence of fire itself may have contributed to this rise through positive feedback. Recent atmospheric modeling suggests an O2 low during the Middle Devonian (around 17.5%), with O2 rising steadily through the Late Devonian and Early Mississippian (to 21–22%) that allowed for widespread burning for the first time. In Devonian-Mississippian marine black shales, fossil charcoal (inertinite) steadily increases up-section suggesting the rise of widespread fire systems. There is a concomitant increase in the amount of vitrinite (preserved woody and other plant tissues) that also suggests increased sources of terrestrial organic matter. Even as end Devonian glaciation was experienced, fossil charcoal continued to be a source of organic matter being introduced into the Devonian oceans. Scanning electron and reflectance microscopy of charcoal from Late Devonian terrestrial sites indicate that the fires were moderately hot (typically 500–600 °C) and burnt mainly surface vegetation dominated by herbaceous zygopterid ferns and lycopsids, rather than being produced by forest crown fires. The occurrence and relative abundance of fossil charcoal in marine black shales are significant in that these shales may provide a more continuous record of fire than is preserved in terrestrial environments. Our data support the idea that major fires are not seen in the fossil record until there is both sufficient and connected fuel and a high enough atmospheric O2 content for it to burn.

Reconstruction of the Paleoenvironment of the Early Cambrian Yurtus Black Shale in the Tarim Basin, Northwestern China, and Its Control on Organic Matter Accumulation

NASA Astrophysics Data System (ADS)

Li, J.; Ding, W.; Dong, L.

2017-12-01

The black shale in the early Cambrian Yurtus Formation (>521 Ma) in the Tarim basin, northwestern China, is characterized by its high TOC value (up to 16%) andgreat lateral continuity. It has been proven to be high-quality hydrocarbon source rocks. Abundant phytoplanktons and small shelly fossils have been reported from the lower Yurtus chert. However, recent biomarker discovery of aryl isoprenoid hydrocarbons suggests the existence of green sulfur bacteria, which indicates that the water column was stratified and the photic zone was prevailingly euxinic. These seemingly contradictory observations hamper our further understanding of the paleoenvironment in which the Yurtus shale was deposited and its control on the accumulation of organic matter. In this study, we systematically collected samples from the Yurtus Formation at the Kungaikuotan Section, and measured the organic carbon and nitrogen isotopic compositions and the content of trace element Barium (Ba). The strong negative excursions of nitrogen isotope ( -13‰) in the lower and upper parts of the Yurtus Formation are likely attributed to the biological activity of green and purple sulfur bacteria, which is consistent with our organic carbon isotope data as well as previous biomarker discovery. As green sulfur bacteria can only live in euxinic photic zone, it may indicate that the water column above this euxinic zone contains prolific organic matters which consume all the dissolved oxidants in surface ocean. It is well accepted that Ba flux can be used as an indicator for surface ocean primary productivity. Significant increase of barium content (from <100 to 2000 ppm) is observed at the same horizon as where the negative excursion of δ15Norg occurs, suggesting the substantive organic matter in the early Cambrian surface ocean mainly result from extremely high primary productivity. The abundant phytoplankton fossil record from this time period also supports this interpretation. In summary, high TOC in the Yurtus shale may derive from the extremely high primary productivity of phytoplanktons. Organic matter consumes all the dissolved oxidants in the water and generates the euxinic zone, which facilitates the accumulation and preservation of the surplus organic matter. This study also shed light on the ecology of the surface ocean before Cambrian Explosion.

CO2 Driven Mineral Transformations in Fractured Reservoir

NASA Astrophysics Data System (ADS)

Schaef, T.

2015-12-01

Engineering fracture systems in low permeable formations to increase energy production, accelerate heat extraction, or to enhance injectivity for storing anthropogenic CO2, is a challenging endeavor. To complicate matters, caprocks, essential components of subsurface reservoirs, need to maintain their sealing integrity in this modified subsurface system. Supercritical CO2 (scCO2), a proposed non-aqueous based working fluid, is capable of driving mineral transformations in fracture environments. Water dissolution in scCO2 significantly impacts the reactivity of this fluid, largely due to the development of thin adsorbed H2O films on the surfaces of exposed rocks and minerals. Adsorbed H2O films are geochemically complex microenvironments that host mineral dissolution and precipitation processes that could be tailored to influence overall formation permeability. Furthermore, manipulating the composition of injected CO2 (e.g., moisture content and/or reactive gases such as O2, NOx, or SOx) could stimulate targeted mineral transformations that enhance or sustain reservoir performance. PNNL has developed specialized experimental techniques that can be used to characterize chemical reactions occurring between minerals and pressurized gases. For example, hydration of a natural shale sample (Woodford Shale) has been characterized by an in situ infrared spectroscopic technique as water partitions from the scCO2 onto the shale. Mineral dissolution and carbonate precipitation reactions were tracked by monitoring changes of Si-O and C-O stretching bands, respectively Structural changes indicated expandable clays in the shale such as montmorillonite are intercalated with scCO2, a process not observed with the non-expandable kaolinite component. Extreme scale ab initio molecular dynamics simulations were used in conjunction with model mineral systems to identify the driving force and mechanism of water films. They showed that the film nucleation and formation on minerals is driven by both enthalpic and entropic requirements. Collectively, the synergy between laboratory observations, state-of-the-art atomistic simulations and reservoir modeling has generated important insights for the design and engineering of subsurface reservoirs for CO2 storage and energy extraction.

Late-stage sulfides and sulfarsenides in Lower Cambrian black shale (stone coal) from the Huangjiawan mine, Guizhou Province, People's Republic of China

USGS Publications Warehouse

Belkin, H.E.; Luo, K.

2008-01-01

The Ni-Mo Huangjiawan mine, Guizhou Province, People's Republic of China, occurs in Lower Cambrian black shale (stone coal) in an area where other mines have recently extracted ore from the same horizon. Detailed electron microprobe (EMPA) and scanning electron microscope (SEM) analyses of representative thin sections have revealed a complex assemblage of sulfides and sulfarsenides. Early sulfidic and phosphatic nodules and host matrix have been lithified, somewhat fractured, and then mineralized with later-stage sulfides and sulfarsenides. Gersdorffite, millerite, polydymite, pyrite, sphalerite, chalcopyrite, galena, and clausthalite have been recognized. EMPA data are given for the major phases. Pyrite trace-element distributions and coeval Ni-, As-sulfides indicate that in the main ore layer, the last sulfide deposition was Ni-As-Co-rich. Mo and V deposition were early in the petrogenesis of these rocks. The assemblages gersdorffite-millerite-polydymite (pyrite) and millerite-gersdorffite (pyrite) and the composition of gersdorffite indicate a formation temperature of between 200?? and 300??C suggesting that the last solutions to infiltrate and mineralize the samples were related to hydrothermal processes. Environmentally sensitive elements such as As, Cd, and Se are hosted by sulfides and sulfarsenides and are the main source of these elements to residual soil. Crops grown on them are enriched in these elements, and they may be hazardous for animal and human consumption. ?? Springer-Verlag 2007.

Fundamental Study of Disposition and Release of Methane in a Shale Gas Reservoir

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yifeng; Xiong, Yongliang; Criscenti, Louise J.

The recent boom in shale gas production through hydrofracturing has reshaped the energy production landscape in the United States. Wellbore production rates vary greatly among the wells within a single field and decline rapidly with time, thus bring up a serious concern with the sustainability of shale gas production. Shale gas production starts with creating a fracture network by injecting a pressurized fluid in a wellbore. The induced fractures are then held open by proppant particles. During production, gas releases from the mudstone matrix, migrates to nearby fractures, and ultimately reaches a production wellbore. Given the relatively high permeability ofmore » the induced fractures, gas release and migration in low-permeability shale matrix is likely to be a limiting step for long-term wellbore production. Therefore, a clear understanding of the underlying mechanisms of methane disposition and release in shale matrix is crucial for the development of new technologies to maximize gas production and recovery. Shale is a natural nanocomposite material with distinct characteristics of nanometer-scale pore sizes, extremely low permeability, high clay contents, significant amounts of organic carbon, and large spatial heterogeneities. Our work has shown that nanopore confinement plays an important role in methane disposition and release in shale matrix. Using molecular simulations, we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~ 30 - 47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. The long-term production decline appears controlled by the second stage of gas release. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3 - 35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. We have successfully established experimental capabilities for measuring gas sorption and desorption on shale and model materials under a wide range of physical and chemical conditions. Both low and high pressure measurements show significant sorption of CH 4 and CO 2 onto clays, implying that methane adsorbed on clay minerals could contribute a significant portion of gas-in-place in an unconventional reservoir. We have also studied the potential impact of the interaction of shale with hydrofracking fluid on gas sorption. We have found that the CH 4-CO 2 sorption capacity for the reacted sample is systematically lower (by a factor of ~2) than that for the unreacted (raw) sample. This difference in sorption capacity may result from a mineralogical or surface chemistry change of the shale sample induced by fluid-rock interaction. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs.« less

Geochemical Analysis for Sedimentary Emerald Mineralization in Western Emerald belt, Colombia

NASA Astrophysics Data System (ADS)

Nino Vasquez, Gabriel Felipe; Song, Sheng-Rong

2017-04-01

1Gabriel Felipe Nino Vasquez and 1Sheng-Rong Song 1Department of Geosciences, National Taiwan University Colombia hosts a large quantity of mineral resources due to its complex tectonic arrangement, and emerald deposits are one of the most representatives for the country. Emeralds in Colombia occur mainly in black shale, and are located in eastern Andes Cordillera with two parallel belts separated by approximately 130 Km: the Western belt (WB) and the Eastern belt (EB). The geological, mineralogical and tectonic features from these belts are quite similar (Buenaventura 2002). Previous researchers concluded that emeralds in Colombia came from hydrothermal sedimentary processes without any magmatic influence, and suggested that the source of Cr, V and Be (which are important components of the beryl) was the host rock. According to their results, the process which allowed the shale to release these cations was the metasomatism (albitization and carbonization), which was resulted from the interaction between the rocks and the alkaline brines. Fractures and fault planes originated by these tectonic movements were fulfilled by enriched fluids, which they allowed emeralds and the other minerals precipitation with decreasing alkalinity and pressure (Giuliani et al. 1994). However, there were several pitfalls of conclusions drawn from previous researches. Firstly, Cr and V were widely distributed and come from mafic and ultramafic rocks, and Be was mostly found in pegmatites, finding these elements in sedimentary rocks suggest that probably the ultramafic rocks occurred not far from the deposits. Secondly, there was an inconsistency in the estimated temperatures of emeralds formation, i.e. temperature of hydrothermal sedimentary deposits was only 200° C, while laboratory analysis showed that the formation of emeralds was higher than 300° C. Therefore, there might still be an allocthonus influence on emerald formation that significantly increases the temperature. This research is going to contribute information in order to clarify these inconsistencies, We have done the O and C isotopes in calcite and S isotope in pyrite and shale from different mines along the (WB) in order to determine the main fluid source of the mineralization. Selected samples will also be analyzed with EDS, RAMAN and ICP-MS methods to obtain the exact compositions of elements with extremely low concentrations in host rock, metazomatized host rock and mineralization (productive and not productive veins); the main purpose is to measure how strong were the fluid-rock interaction to leach elements out from the black shale. Thin sections from the altered shale and vein have been analyzed with the purpose of identify paragenesis and microstructures in the mineralization. Finally, we would like to gather the results from different sectors and compare it with the previous studies.

Geochemical simulation of fluid rock interactions to predict flowback water compostions during hydraulic fracturing

NASA Astrophysics Data System (ADS)

Kühn, Michael; Vieth-Hillebrand, Andrea; Wilke, Franziska D. H.

2017-04-01

Black shales are a heterogeneous mixture of minerals, organic matter and formation water and little is actually known about the fluid-rock interactions during hydraulic fracturing and their effects on composition of flowback and produced water. Geochemical simulations have been performed based on the analyses of "real" flowback water samples and artificial stimulation fluids from lab experiments with the aim to set up a chemical process model for shale gas reservoirs. Prediction of flowback water compositions for potential or already chosen sites requires validated and parameterized geochemical models. For the software "Geochemist's Workbench" (GWB) data bases are adapted and amended based on a literature review. Evaluation of the system has been performed in comparison with the results from laboratory experiments. Parameterization was done in regard to field data provided. Finally, reaction path models are applied for quantitative information about the mobility of compounds in specific settings. Our work leads to quantitative estimates of reservoir compounds in the flowback based on calibrations by laboratory experiments. Such information is crucial for the assessment of environmental impacts as well as to estimate human- and ecotoxicological effects of the flowback waters from a variety of natural gas shales. With a comprehensive knowledge about potential composition and mobility of flowback water, selection of water treatment techniques will become easier.

A reconnaissance for uranium in carbonaceous rocks in southwestern Colorado and parts of New Mexico

USGS Publications Warehouse

Baltz, Elmer H.

1955-01-01

Coal and carbonaceous shale of the Dakota formation of Cretaceous age were examined for radioactivity in the Colorado Plateau of southwestern Colorado and northwestern New l1exico during the summer of 1953. Older and younger sedimentary rocks and some igneous rocks also were examined, but in less detail, Weak radioactivity was detected at many places but no new deposits of apparent economic importance were discovered. The highest radioactivity of carbonaceous rocks was detected in black shale, siltstone, and sandstone of the Paradox member of the Hermosa formation of Pennsylvanian age. A sample collected from this member at the Bald Eagle prospect in Gypsum Valley, San Higuel County, Colo. contains 0.10. percent uranium. Carbonaceous rocks were investigated at several localities on the Las Vegas Plateau and the Canadian Escarpment in Harding and San Miguel Counties, northeastern New Mexico. Carbonaceous sandstone and siltstone in the middle sandstone member of the Chinle formation of Triassic age contain uranium at a prospect of the Hunt Oil Company southwest of Sabinoso in northeastern San Miguel County, N. Mex. A channel sample across 3.2 feet of mineralized rocks at this locality contains 0.22 percent uranium. Weak radioactivity was detected at two localities in carbonaceous shale of the Dakota and Purgatoire formations of Cretaceous age.

A Guide to Fundraising at Historically Black Colleges and Universities: An All Campus Approach

ERIC Educational Resources Information Center

Gasman, Marybeth; Bowman, Nelson, III

2011-01-01

"A Guide to Fundraising at Historically Black Colleges and Universities" is a comprehensive, research-based work that brings the best practices and expertise of seminal professionals to the larger Black college environment and beyond. Drawing on data-driven advice from interviews with successful Black college fundraisers and private sector…

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

NASA Astrophysics Data System (ADS)

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

2016-06-01

Despite massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix-a limiting step in shale gas extraction. Using molecular simulations, we here show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30-47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3-35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.

Hydraulic fracturing fluid migration in the subsurface: A review and expanded modeling results

NASA Astrophysics Data System (ADS)

Birdsell, Daniel T.; Rajaram, Harihar; Dempsey, David; Viswanathan, Hari S.

2015-09-01

Understanding the transport of hydraulic fracturing (HF) fluid that is injected into the deep subsurface for shale gas extraction is important to ensure that shallow drinking water aquifers are not contaminated. Topographically driven flow, overpressured shale reservoirs, permeable pathways such as faults or leaky wellbores, the increased formation pressure due to HF fluid injection, and the density contrast of the HF fluid to the surrounding brine can encourage upward HF fluid migration. In contrast, the very low shale permeability and capillary imbibition of water into partially saturated shale may sequester much of the HF fluid, and well production will remove HF fluid from the subsurface. We review the literature on important aspects of HF fluid migration. Single-phase flow and transport simulations are performed to quantify how much HF fluid is removed via the wellbore with flowback and produced water, how much reaches overlying aquifers, and how much is permanently sequestered by capillary imbibition, which is treated as a sink term based on a semianalytical, one-dimensional solution for two-phase flow. These simulations include all of the important aspects of HF fluid migration identified in the literature review and are performed in five stages to faithfully represent the typical operation of a hydraulically fractured well. No fracturing fluid reaches the aquifer without a permeable pathway. In the presence of a permeable pathway, 10 times more fracturing fluid reaches the aquifer if well production and capillary imbibition are not included in the model.

Geophysical Investigation of the Raton Basin.

DTIC Science & Technology

1982-05-01

17. DISTRIBUTION STATEMENT (of the abetrect entered in Block 20, If different from Report) LYNN E . WOLAVER J Dean for Research and IS. SUPPLEMENTARY...NOTES i Professional Development APPROVED FOR PUBLIC RELEASE: IAW AFR 7 .,# R . - E 0. TECHNOLOGY (ATC) 2 2 JUN 1982 WRiGHT-PATTRSON AFB, OH 45433 19...which are dominated by thick grey I to black strata, predominate to the north. In fact, this shale which 4 ’d E N w ERa NEW MEXICO 0 SANTA FE 0

Supermassive black holes do not correlate with galaxy disks or pseudobulges.

PubMed

Kormendy, John; Bender, R; Cornell, M E

2011-01-20

The masses of supermassive black holes are known to correlate with the properties of the bulge components of their host galaxies. In contrast, they seem not to correlate with galaxy disks. Disk-grown 'pseudobulges' are intermediate in properties between bulges and disks; it has been unclear whether they do or do not correlate with black holes in the same way that bulges do. At stake in this issue are conclusions about which parts of galaxies coevolve with black holes, possibly by being regulated by energy feedback from black holes. Here we report pseudobulge classifications for galaxies with dynamically detected black holes and combine them with recent measurements of velocity dispersions in the biggest bulgeless galaxies. These data confirm that black holes do not correlate with disks and show that they correlate little or not at all with pseudobulges. We suggest that there are two different modes of black-hole feeding. Black holes in bulges grow rapidly to high masses when mergers drive gas infall that feeds quasar-like events. In contrast, small black holes in bulgeless galaxies and in galaxies with pseudobulges grow as low-level Seyfert galaxies. Growth of the former is driven by global processes, so the biggest black holes coevolve with bulges, but growth of the latter is driven locally and stochastically, and they do not coevolve with disks and pseudobulges.

Assessment of Appalachian basin oil and gas resources: Utica-Lower Paleozoic Total Petroleum System: Chapter G.10 in Coal and petroleum resources in the Appalachian basin: distribution, geologic framework, and geochemical character

USGS Publications Warehouse

Ryder, Robert T.; Ruppert, Leslie F.; Ryder, Robert T.

2014-01-01

Both conventional oil and gas resources and continuous (unconventional) gas resources are present in the UticaLower Paleozoic TPS. Conventional oil and gas resources in the Utica-Lower Paleozoic TPS were assessed by the U.S. Geological Survey (USGS) in 2002 in the following assessment units (AU): (1) the Lower Paleozoic Carbonates in Thrust Belt AU, (2) the Knox Unconformity AU, (3) the Black River-Trenton Hydrothermal Dolomite AU, and (4) the Lockport Dolomite AU. The total estimated undiscovered oil and gas resources for these four AUs, at a mean value, was about 46 million barrels of oil (MMBO) and about 3 trillion cubic feet of gas (TCFG), respectively. In contrast, continuous (unconventional) gas resources in the TPS were assessed by the USGS in 2002 in four AUs associated with the “Clinton” sandstone, Medina sandstone, Medina Group sandstones, Tuscarora Sandstone, and sandstones in the Queenston Shale. The total estimated undiscovered gas for these four AUs, at a mean value, was about 26.8 TCFG. A hypothetical Utica Shale AU for oil(?) and continuous gas is identified in this report. In 2012, the Utica Shale was recognized by the USGS as a continuous AU and was assessed by Kirschbaum and others (2012).

Evaluating a groundwater supply contamination incident attributed to Marcellus Shale gas development

PubMed Central

Llewellyn, Garth T.; Dorman, Frank; Westland, J. L.; Yoxtheimer, D.; Grieve, Paul; Sowers, Todd; Humston-Fulmer, E.; Brantley, Susan L.

2015-01-01

High-volume hydraulic fracturing (HVHF) has revolutionized the oil and gas industry worldwide but has been accompanied by highly controversial incidents of reported water contamination. For example, groundwater contamination by stray natural gas and spillage of brine and other gas drilling-related fluids is known to occur. However, contamination of shallow potable aquifers by HVHF at depth has never been fully documented. We investigated a case where Marcellus Shale gas wells in Pennsylvania caused inundation of natural gas and foam in initially potable groundwater used by several households. With comprehensive 2D gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-TOFMS), an unresolved complex mixture of organic compounds was identified in the aquifer. Similar signatures were also observed in flowback from Marcellus Shale gas wells. A compound identified in flowback, 2-n-Butoxyethanol, was also positively identified in one of the foaming drinking water wells at nanogram-per-liter concentrations. The most likely explanation of the incident is that stray natural gas and drilling or HF compounds were driven ∼1–3 km along shallow to intermediate depth fractures to the aquifer used as a potable water source. Part of the problem may have been wastewaters from a pit leak reported at the nearest gas well pad—the only nearby pad where wells were hydraulically fractured before the contamination incident. If samples of drilling, pit, and HVHF fluids had been available, GCxGC-TOFMS might have fingerprinted the contamination source. Such evaluations would contribute significantly to better management practices as the shale gas industry expands worldwide. PMID:25941400

Evaluating a groundwater supply contamination incident attributed to Marcellus Shale gas development.

PubMed

Llewellyn, Garth T; Dorman, Frank; Westland, J L; Yoxtheimer, D; Grieve, Paul; Sowers, Todd; Humston-Fulmer, E; Brantley, Susan L

2015-05-19

High-volume hydraulic fracturing (HVHF) has revolutionized the oil and gas industry worldwide but has been accompanied by highly controversial incidents of reported water contamination. For example, groundwater contamination by stray natural gas and spillage of brine and other gas drilling-related fluids is known to occur. However, contamination of shallow potable aquifers by HVHF at depth has never been fully documented. We investigated a case where Marcellus Shale gas wells in Pennsylvania caused inundation of natural gas and foam in initially potable groundwater used by several households. With comprehensive 2D gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-TOFMS), an unresolved complex mixture of organic compounds was identified in the aquifer. Similar signatures were also observed in flowback from Marcellus Shale gas wells. A compound identified in flowback, 2-n-Butoxyethanol, was also positively identified in one of the foaming drinking water wells at nanogram-per-liter concentrations. The most likely explanation of the incident is that stray natural gas and drilling or HF compounds were driven ∼ 1-3 km along shallow to intermediate depth fractures to the aquifer used as a potable water source. Part of the problem may have been wastewaters from a pit leak reported at the nearest gas well pad-the only nearby pad where wells were hydraulically fractured before the contamination incident. If samples of drilling, pit, and HVHF fluids had been available, GCxGC-TOFMS might have fingerprinted the contamination source. Such evaluations would contribute significantly to better management practices as the shale gas industry expands worldwide.

The Merger-Free Growth of Galaxies and Supermassive Black Holes

NASA Astrophysics Data System (ADS)

Simmons, Brooke; Smethurst, Rebecca; Lintott, Chris; Martin, Garreth; Kaviraj, Sugata; Devriendt, Julien; Galaxy Zoo Team

2018-01-01

There is now clear evidence that the merger-driven pathway to black hole and galaxy growth is only half the story. Merger-free evolution contributes roughly equally to the overall growth of black holes in the Universe and is also responsible for a significant amount of galaxy growth over cosmic time. A recent study examining the growth of black holes in unambiguously disk-dominated galaxies shows these black holes reach quasar-like luminosities and black hole masses typical of those hosted in bulge-dominated and elliptical galaxies with major mergers in their evolutionary histories. However, while there appears to be no correlation between the size of the black hole and upper limits on the host galaxy bulges, the fitted correlation between black hole mass and total galaxy stellar mass in these merger-free systems is fully consistent with the canonical relationship based on merger-driven systems. There is further evidence via comparison between observed populations and cosmological simulations confirming that bulgeless systems are generally consistent with having merger-free histories. If bulgeless and disk-dominated galaxies are indeed signatures of systems with no violent mergers in their formation histories, the same correlation between black hole and galaxy in these systems versus that seen in elliptical galaxy samples indicates the black hole-galaxy connection must originate with a process more fundamental than the dynamical configuration of a galaxy's stars.

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

In spite of the massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Here we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases, and we usemore » molecular simulations to demonstrate it. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Finally, our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.« less

A new nanocomposite forward osmosis membrane custom-designed for treating shale gas wastewater

PubMed Central

Qin, Detao; Liu, Zhaoyang; Delai Sun, Darren; Song, Xiaoxiao; Bai, Hongwei

2015-01-01

Managing the wastewater discharged from oil and shale gas fields is a big challenge, because this kind of wastewater is normally polluted by high contents of both oils and salts. Conventional pressure-driven membranes experience little success for treating this wastewater because of either severe membrane fouling or incapability of desalination. In this study, we designed a new nanocomposite forward osmosis (FO) membrane for accomplishing simultaneous oil/water separation and desalination. This nanocomposite FO membrane is composed of an oil-repelling and salt-rejecting hydrogel selective layer on top of a graphene oxide (GO) nanosheets infused polymeric support layer. The hydrogel selective layer demonstrates strong underwater oleophobicity that leads to superior anti-fouling capability under various oil/water emulsions, and the infused GO in support layer can significantly mitigate internal concentration polarization (ICP) through reducing FO membrane structural parameter by as much as 20%. Compared with commercial FO membrane, this new FO membrane demonstrates more than three times higher water flux, higher removals for oil and salts (>99.9% for oil and >99.7% for multivalent ions) and significantly lower fouling tendency when investigated with simulated shale gas wastewater. These combined merits will endorse this new FO membrane with wide applications in treating highly saline and oily wastewaters. PMID:26416014

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

PubMed Central

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

2016-01-01

Despite massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Using molecular simulations, we here show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release. PMID:27306967

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

DOE PAGES

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

2016-06-16

In spite of the massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Here we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases, and we usemore » molecular simulations to demonstrate it. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Finally, our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.« less

Still Flies in Buttermilk: Black Male Faculty, Critical Race Theory, and Composite Counterstorytelling

ERIC Educational Resources Information Center

Griffin, Rachel Alicia; Ward, LaCharles; Phillips, Amanda R.

2014-01-01

Driven by critical race theory, this essay employs composite counterstorytelling to narrate the experiences of black male faculty on traditionally white campuses. Situated at the intersections of race and gender, our composite counterstory is richly informed by 11 interviews with black male faculty alongside critical race scholarship that…

Lower Cretaceous dinoflagellate cyst and acritarch stratigraphy of the Cismon APTICORE (Southern Alps, Italy).

PubMed

Torricelli

2000-02-01

A pelagic sedimentary succession, virtually complete from the Upper Hauterivian to the Upper Aptian and unconformably overlain by the Middle-Upper Albian p.p., was continuously cored in the Belluno Basin (southern Alps, NE Italy) as part of the APTICORE Program. APTICORE at Cismon Valley penetrated 131.8m of limestones, marls and black shales, with 100% recovery of good quality cored material.One hundred and forty-six samples recovered from the marl and shale beds of the Cismon core were processed and analyzed for palynomorphs. Most of them yielded relatively rich and fairly well preserved assemblages of marine and terrestrially-derived palynomorphs.The results of a qualitative study of dinoflagellate cysts and acritarchs are presented and discussed. The distributions of 150 taxa are tabulated against the chronostratigraphy independently established on the basis of original litho-, bio-, chemo-, magnetostratigraphic investigations and of correlations with extensively studied sections outcropping in the vicinity of the Cismon drill site.The acritarch Pinocchiodinium erbae gen. et sp. nov. is described. Due to its distinctive morphology and extremely constant occurrence also in the black shales of the Selli Level, it is proposed as a marker species for the Aptian sediments of the Tethys.The dinoflagellate cysts Kallosphaeridium dolomiticum sp. nov. and Nexosispinum hesperus brevispinosum subsp. nov. are described from the Upper Hauterivian. Additional taxonomic remarks are made about other dinoflagellate cyst species, including the emendations of Tanyosphaeridium magneticum Davies 1983 and Bourkidinium granulatum Morgan 1975.The biostratigraphic value of selected taxa is discussed and compared with data known both from the Tethyan and Boreal realms. In particular, the extinction of Bourkidinium granulatum emend. is proposed as the best dinoflagellate cyst event for the delimitation of the Hauterivian-Barremian boundary in the Northern Hemisphere. The first appearance datums of Prolixosphaeridium parvispinum and Odontochitina operculata, and the slightly younger last appearance datum of Nexosispinum vetusculum are confirmed as useful biohorizons for recognition of the lower part of the Upper Barremian and hence for the approximation of the Lower-Upper Barremian boundary. The last occurrences of Rhynchodiniopsis aptiana and Phoberocysta neocomica are calibrated in the basal Aptian.

Estimation Criteria for Rock Brittleness Based on Energy Analysis During the Rupturing Process

NASA Astrophysics Data System (ADS)

Ai, Chi; Zhang, Jun; Li, Yu-wei; Zeng, Jia; Yang, Xin-liang; Wang, Ji-gang

2016-12-01

Brittleness is one of the most important mechanical properties of rock: it plays a significant role in evaluating the risk of rock bursts and in analysis of borehole-wall stability during shale gas development. Brittleness is also a critical parameter in the design of hydraulic fracturing. However, there is still no widely accepted definition of the concept of brittleness in rock mechanics. Although many criteria have been proposed to characterize rock brittleness, their applicability and reliability have yet to be verified. In this paper, the brittleness of rock under compression is defined as the ability of a rock to accumulate elastic energy during the pre-peak stage and to self-sustain fracture propagation in the post-peak stage. This ability is related to three types of energy: fracture energy, post-peak released energy and pre-peak dissipation energy. New brittleness evaluation indices B 1 and B 2 are proposed based on the stress-strain curve from the viewpoint of energy. The new indices can describe the entire transition of rock from absolute plasticity to absolute brittleness. In addition, the brittle characteristics reflected by other brittleness indices can be described, and the calculation results of B 1 and B 2 are continuous and monotonic. Triaxial compression tests on different types of rock were carried out under different confining pressures. Based on B 1 and B 2, the brittleness of different rocks shows different trends with rising confining pressure. The brittleness of red sandstone decreases with increasing confining pressure, whereas for black shale it initially increases and then decreases in a certain range of confining pressure. Granite displays a constant increasing trend. The brittleness anisotropy of black shale is discussed. The smaller the angle between the loading direction and the bedding plane, the greater the brittleness. The calculation B 1 and B 2 requires experimental data, and the values of these two indices represent only relative brittleness under certain conditions. In field operations, both the relative brittleness and the brittleness obtained from seismic data or mineral composition should be considered to gain a more comprehensive knowledge of the brittleness of rock material.

Reconstructed Oceanic Sedimentary Sequence in the Cape Three Points Area, Southern Axim-Konongo (Ashanti) Greenstone Belt in the Paleoproterozoic Birimian of Ghana.

NASA Astrophysics Data System (ADS)

Kiyokawa, S.; Ito, T.; Frank, N. K.; George, T. M.

2014-12-01

The Birimian greenstone belt likely formed through collision between the West African and Congo Cratons ~2.2 Ga. Accreted greenstone belts that formed through collision especially during the Palaeoproterozoic are usually not only good targets for preservation of oceanic sedimentary sequences but also greatly help understand the nature of the Paleoproterozoic deeper oceanic environments. In this study, we focused on the coastal area around Cape Three Points at the southernmost part of the Axim-Konongo (Ashanti) greenstone belt in Ghana where excellently preserved Paleoprotrozoic deeper oceanic sedimentary sequences extensively outcrop. The Birimian greenstone belt in both the Birimian rock (partly Sefwi Group) and Ashanti belts are separated from the Tarkwaian Group which is a paleoplacer deposit (Perrouty et al., 2012). The Birimian rock was identified as volcanic rich greenstone belt; Kumasi Group is foreland basin with shale and sandstone, quartzite and turbidite derived from 2.1 Ga granite in the Birimian; Tarkwaian Group is composed of coarse detrital sedimentary rocks deposited along a strike-slip fault in the Birimian. In the eastern part of the Cape Three Point area, over 4km long of volcanic-sedimentary sequence outcrops and is affected by greenschist facies metamorphism. Four demarcated zones along the coast as Kutike, Atwepo, Kwtakor and Akodaa zones. The boundaries of each zone were not observed, but each zone displays a well preserved and continuous sedimentary sequence. Structurally, this region is west vergent structure and younging direction to the East. Kutike zone exhibits synform structure with S0 younging direction. Provisional stratigraphic columns in all the zones total about 500m thick. Kutike, Atwepo zones (> 200m thick) have coarsening upward characteristics from black shale to bedded volcanic sandstone. Kwtakor zone (> 150m) is the thickest volcaniclastic sequence and has fining upward sections. Akodaa zone (> 150m) consists of finer bed of volcaniclastics with black shales and has fining upward character. This continuous sequence indicate distal portion of submarine volcaniclastic section in an oceanic island arc between the West African and Congo Cratons.

Multi-decadal storminess fluctuations of Black Sea due to North Atlantic Oscillation

NASA Astrophysics Data System (ADS)

Kuznetsov, Sergey; Saprykina, Yana; Grigorieva, Victoria; Aydoǧan, Berna; Aydoǧan, Burak

2017-04-01

Storminess variability is of key importance for many marine applications, naval and coastal engineering. Studying the evolution of this phenomenon along with large scale atmospheric patterns and being able to predict them is crucial for in the context of rising sea level due to climate change what make the low-lying coasts in the Black Sea to become increasingly vulnerable to marine hazards. The aim of this work is to clarify the trends, statistics and reasons of variations of storminess in dependence of such climatic characteristic as NAO (North Atlantic Oscillation Index). The analysis of Black Sea storminess activity was performed on the base of visual wave observations (Voluntary Observing Ship or VOS) for the period 1970-2011. Annual means and maximum heights of wind-driven seas and swell waves averaging over whole Black Sea area were investigated separately. The both wind-driven seas and swell demonstrate the decreasing in heights about 10% the same as their periods for the chosen time frame. Parametric spectral analysis was performed. The periods of wave height fluctuations for wind-driven seas and swell were shown to coincide with each other and with periods of low frequency fluctuation of NOA: 14 and 4 year respectively. Correlation coefficients of wave height and NOA were 0.3 for swell and 0.4 for wind-driven sea. Nonlinear regularities of NAO fluctuations were investigated using wavelet and spavlet (spectra of modules of wavelet coefficients) analyses. Their influence on variability of storminess in Black Sea is discussed. The reported study was funded by RFBR (project No. 16-55-76002 ERA_a) and by TUBITAK (project No. 116M061) in frame of BS STEMA project.

Sulfide Generation by Dominant Halanaerobium Microorganisms in Hydraulically Fractured Shales

PubMed Central

Booker, Anne E.; Borton, Mikayla A.; Daly, Rebecca A.; Welch, Susan A.; Nicora, Carrie D.; Hoyt, David W.; Wilson, Travis; Purvine, Samuel O.; Wolfe, Richard A.; Sharma, Shikha; Mouser, Paula J.; Cole, David R.; Lipton, Mary S.; Wrighton, Kelly C.

2017-01-01

ABSTRACT Hydraulic fracturing of black shale formations has greatly increased United States oil and natural gas recovery. However, the accumulation of biomass in subsurface reservoirs and pipelines is detrimental because of possible well souring, microbially induced corrosion, and pore clogging. Temporal sampling of produced fluids from a well in the Utica Shale revealed the dominance of Halanaerobium strains within the in situ microbial community and the potential for these microorganisms to catalyze thiosulfate-dependent sulfidogenesis. From these field data, we investigated biogenic sulfide production catalyzed by a Halanaerobium strain isolated from the produced fluids using proteogenomics and laboratory growth experiments. Analysis of Halanaerobium isolate genomes and reconstructed genomes from metagenomic data sets revealed the conserved presence of rhodanese-like proteins and anaerobic sulfite reductase complexes capable of converting thiosulfate to sulfide. Shotgun proteomics measurements using a Halanaerobium isolate verified that these proteins were more abundant when thiosulfate was present in the growth medium, and culture-based assays identified thiosulfate-dependent sulfide production by the same isolate. Increased production of sulfide and organic acids during the stationary growth phase suggests that fermentative Halanaerobium uses thiosulfate to remove excess reductant. These findings emphasize the potential detrimental effects that could arise from thiosulfate-reducing microorganisms in hydraulically fractured shales, which are undetected by current industry-wide corrosion diagnostics. IMPORTANCE Although thousands of wells in deep shale formations across the United States have been hydraulically fractured for oil and gas recovery, the impact of microbial metabolism within these environments is poorly understood. Our research demonstrates that dominant microbial populations in these subsurface ecosystems contain the conserved capacity for the reduction of thiosulfate to sulfide and that this process is likely occurring in the environment. Sulfide generation (also known as “souring”) is considered deleterious in the oil and gas industry because of both toxicity issues and impacts on corrosion of the subsurface infrastructure. Critically, the capacity for sulfide generation via reduction of sulfate was not detected in our data sets. Given that current industry wellhead tests for sulfidogenesis target canonical sulfate-reducing microorganisms, these data suggest that new approaches to the detection of sulfide-producing microorganisms may be necessary. PMID:28685163

Sulfide Generation by Dominant Halanaerobium Microorganisms in Hydraulically Fractured Shales

DOE Office of Scientific and Technical Information (OSTI.GOV)

Booker, Anne E.; Borton, Mikayla A.; Daly, Rebecca A.

ABSTRACT Hydraulic fracturing of black shale formations has greatly increased United States oil and natural gas recovery. However, the accumulation of biomass in subsurface reservoirs and pipelines is detrimental because of possible well souring, microbially induced corrosion, and pore clogging. Temporal sampling of produced fluids from a well in the Utica Shale revealed the dominance ofHalanaerobiumstrains within thein situmicrobial community and the potential for these microorganisms to catalyze thiosulfate-dependent sulfidogenesis. From these field data, we investigated biogenic sulfide production catalyzed by aHalanaerobiumstrain isolated from the produced fluids using proteogenomics and laboratory growth experiments. Analysis ofHalanaerobiumisolate genomes and reconstructed genomes frommore » metagenomic data sets revealed the conserved presence of rhodanese-like proteins and anaerobic sulfite reductase complexes capable of converting thiosulfate to sulfide. Shotgun proteomics measurements using aHalanaerobiumisolate verified that these proteins were more abundant when thiosulfate was present in the growth medium, and culture-based assays identified thiosulfate-dependent sulfide production by the same isolate. Increased production of sulfide and organic acids during the stationary growth phase suggests that fermentativeHalanaerobiumuses thiosulfate to remove excess reductant. These findings emphasize the potential detrimental effects that could arise from thiosulfate-reducing microorganisms in hydraulically fractured shales, which are undetected by current industry-wide corrosion diagnostics. IMPORTANCEAlthough thousands of wells in deep shale formations across the United States have been hydraulically fractured for oil and gas recovery, the impact of microbial metabolism within these environments is poorly understood. Our research demonstrates that dominant microbial populations in these subsurface ecosystems contain the conserved capacity for the reduction of thiosulfate to sulfide and that this process is likely occurring in the environment. Sulfide generation (also known as “souring”) is considered deleterious in the oil and gas industry because of both toxicity issues and impacts on corrosion of the subsurface infrastructure. Critically, the capacity for sulfide generation via reduction of sulfate was not detected in our data sets. Given that current industry wellhead tests for sulfidogenesis target canonical sulfate-reducing microorganisms, these data suggest that new approaches to the detection of sulfide-producing microorganisms may be necessary.« less

Reactivity of Dazomet, a Hydraulic Fracturing Additive: Hydrolysis and Interaction with Pyrite

NASA Astrophysics Data System (ADS)

Consolazio, N.; Lowry, G. V.; Karamalidis, A.; Hakala, A.

2015-12-01

The Marcellus Shale is currently the largest shale gas formation in play across the world. The low-permeability formation requires hydraulic fracturing to be produced. In this process, millions of gallons of water are blended with chemical additives and pumped into each well to fracture the reservoir rock. Although additives account for less than 2% of the fracking fluid mixture, they amount to hundreds of tons per frack job. The environmental properties of some of these additives have been studied, but their behavior under downhole conditions is not widely reported in the peer-reviewed literature. These compounds and their reaction products may return to the surface as produced or waste water. In the event of a spill or release, this water has the potential to contaminate surface soil and water. Of these additives, biocides may present a formidable challenge to water quality. Biocides are toxic compounds (by design), typically added to the Marcellus Shale to control bacteria in the well. An assessment of the most frequently used biocides indicated a need to study the chemical dazomet under reservoir conditions. The Marcellus Shale contains significant deposits of pyrite. This is a ubiquitous mineral within black shales that is known to react with organic compounds in both oxic and anoxic settings. Thus, the objective of our study was to determine the effect of pyrite on the hydrolysis of dazomet. Liquid chromatography-triple quadrupole mass spectrometry (LC-QQQ) was used to calculate the loss rate of aqueous dazomet. Gas chromatography-mass spectrometry (GC-MS) was used to identify the reaction products. Our experiments show that in water, dazomet rapidly hydrolyses in water to form organic and inorganic transformation products. This reaction rate was unaffected when performed under anoxic conditions. However, with pyrite we found an appreciable increase in the removal rate of dazomet. This was accompanied by a corresponding change in the distribution of observed reaction products. Our results indicate the need to determine specific mineral-additive interactions to evaluate the potential risks of chemical use in hydraulic fracturing.

Tertiary geology and oil-shale resources of the Piceance Creek basin between the Colorado and White Rivers, northwestern Colorado

USGS Publications Warehouse

Donnell, John R.

1961-01-01

The area of the Piceance Creek basin between the Colorado and White Rivers includes approximately 1,600 square miles and is characterized by an extensive plateau that rises 1,000 to more than 4,000 feet above the surrounding lowlands. Relief is greatest in Naval Oil-Shale Reserves Nos. 1 and 3 near the south margin of the area, where the spectacular Roan Cliffs tower above the valley of the Colorado River. The oldest rocks exposed in the mapped area are sandstone, shale, and coal beds of the Mesaverde group of Late Cretaceous age, which crop out along the east margin of the area. Overlying the Mesaverde is an unnamed sequence of dark-colored sandstone and shale, Paleocene in age. The Ohio Creek conglomerate, composed of black and red chert and quartzite pebbles in a white sandstone matrix, is probably the basal unit in the Paleocene sequence. The Wasatch formation of early Eocene age overlies the Paleocene sedimentary rocks. It is composed of brightly colored shale, lenticular beds of sandstone, and a few thin beds of fresh-water limestone. The Kasatch formation interfingers with and is overlain by the Green River formation of middle Eocene age. The Green River formation has been divided into the Douglas Creek, Garden Gulch, Anvil Points, Parachute Creek, and Evacuation Creek members. The basal and uppermost members, the Douglas Creek and Evacuation Creek, respectively, are predominantly sandy units. The two middle members, the Garden Gulch and Parachute Creek, are composed principally of finer clastic rocks. The Anvil Points member is present only on the southeast, east, and northeast margins of the area. It is a nearshore facies composed principally of sandstone and is the equivalent of the Douglas Creek, Garden Gulch, and the lower part of the Parachute Creek members. All of the richer exposed oil-shale beds are found in the Parachute Creek member, which is divided into two oil-shale zones by a series of low-grade oilshale beds. The upper oil-shale zone has several key beds and zones which can be traced throughout most of the mapped area. One of these, the Mahogany ledge or zone, is a group of very rich oil-shale beds at the base of the upper oil-shale zone. Drilling for oil and gas in the northeastern part of the area has revealed rich oil-shale zones in the Garden Gulch member also.Local unconformities within and at the base of the Evacuation Creek member are exposed at several places along Piceance Creek and at one place near the mouth of Yellow Creek; otherwise, the rock sequence is conformable. The mapped area is the major part of a large syncline, modified by numerous smaller structural features. Fractures, probably associated genetically with the minor structural features, are present in the central part of the area. These fractures are high-angle normal faults with small displacement. They occur in pairs with the intervening block downdropped. Two sets of joints are prominent, one trending northwest and the other northeast. The joint systems control the drainage pattern in the south-central part of the area. More than 20,000 feet of sedimentary rocks underlies the area. Many of the formations yield oil or gas in northwestern Colorado, northeastern Utah, and southwestern Wyoming. The Piceance Creek gas field, in which gas occurs in the Douglas Creek member of the Green River formation, is the largest oil or gas field discovered thus far within the area. About 7,000 million barrels of oil is contained in oil shale that yields an average of 45 gallons per ton from a continuous sequence 5 or more feet thick in the Mahogany zone. Oil shale in the Mahogany zone and adjacent beds that yields an average of 30 gallons of oil per ton from a continuous sequence 15 or more feet thick contains about 91,000 million barrels of oil. Similar shale in deeper zones in the northern part of the area, for which detailed estimates have not been prepared, are now known to contain at least an additional 72,000 million barrels of oil. Oil shale in a sequence 15 or more feet thick that yields an average of 25 gallons of oil per ton contains about 154,000 million barrels of oil in the Mahogany zone and adjacent beds; such shale in deeper zones in the northern part of the area probably contains at least an additional 157,000 million barrels of oil, although detailed estimates were not made. Oil shale in a sequence greater than 15 feet thick that yields an average of 15 gallons of oil per ton contains more than 900,000 million barrels of oil. These estimates of the oil content of the deposit do not take into account any loss in mining or processing of the shale.

Uraniferous bitumen nodules in the Talvivaara Ni-Zn-Cu-Co deposit (Finland): influence of metamorphism on uranium mineralization in black shales

NASA Astrophysics Data System (ADS)

Lecomte, Andreï; Cathelineau, Michel; Deloule, Etienne; Brouand, Marc; Peiffert, Chantal; Loukola-Ruskeeniemi, Kirsti; Pohjolainen, Esa; Lahtinen, Hannu

2014-04-01

In the central part of the Fennoscandian Shield, the Talvivaara Ni-Zn-Cu-Co deposit, hosted by Palaeoproterozoic metamorphosed black schists, contains low uranium concentrations ranging from 10 to 30 ppm. The Talvivaara black schists were deposited 2.0-1.9 Ga ago and underwent subsequent metamorphism during the 1.9-1.79 Ga Svecofennian orogeny. Anhedral uraninite crystals rimmed by bitumen constitute the main host of uranium. U-Pb secondary ion mass spectrometry dating indicates that uraninite crystals were formed between 1,878 ± 17 and 1,871 ± 43 Ma, during peak metamorphism. Rare earth element patterns and high Th content (average 6.38 wt%) in disseminated uraninite crystals indicate that U was concentrated during high temperature metamorphism (>400 °C). The formation of bitumen rims around uraninite may be explained by two distinct scenarios: (a) a transport of U coincident with the migration of hydrocarbons or (b) post-metamorphic formation of bitumen rims, through radiolytic polymerization of gaseous hydrocarbons at the contact with uraninite.

Fluid driven fracture mechanics in highly anisotropic shale: a laboratory study with application to hydraulic fracturing

NASA Astrophysics Data System (ADS)

Gehne, Stephan; Benson, Philip; Koor, Nick; Enfield, Mark

2017-04-01

The finding of considerable volumes of hydrocarbon resources within tight sedimentary rock formations in the UK led to focused attention on the fundamental fracture properties of low permeability rock types and hydraulic fracturing. Despite much research in these fields, there remains a scarcity of available experimental data concerning the fracture mechanics of fluid driven fracturing and the fracture properties of anisotropic, low permeability rock types. In this study, hydraulic fracturing is simulated in a controlled laboratory environment to track fracture nucleation (location) and propagation (velocity) in space and time and assess how environmental factors and rock properties influence the fracture process and the developing fracture network. Here we report data on employing fluid overpressure to generate a permeable network of micro tensile fractures in a highly anisotropic shale ( 50% P-wave velocity anisotropy). Experiments are carried out in a triaxial deformation apparatus using cylindrical samples. The bedding planes are orientated either parallel or normal to the major principal stress direction (σ1). A newly developed technique, using a steel guide arrangement to direct pressurised fluid into a sealed section of an axially drilled conduit, allows the pore fluid to contact the rock directly and to initiate tensile fractures from the pre-defined zone inside the sample. Acoustic Emission location is used to record and map the nucleation and development of the micro-fracture network. Indirect tensile strength measurements at atmospheric pressure show a high tensile strength anisotropy ( 60%) of the shale. Depending on the relative bedding orientation within the stress field, we find that fluid induced fractures in the sample propagate in two of the three principal fracture orientations: Divider and Short-Transverse. The fracture progresses parallel to the bedding plane (Short-Transverse orientation) if the bedding plane is aligned (parallel) with the direction of σ1. Conversely, the crack plane develops perpendicular to the bedding plane, if the bedding plane is orientated normal to σ1. Fracture initiation pressures are higher in the Divider orientation ( 24MPa) than in the Short-Transverse orientation ( 14MPa) showing a tensile strength anisotropy ( 42%) comparable to ambient tensile strength results. We then use X-Ray Computed Tomography (CT) 3D-images to evaluate the evolved fracture network in terms of fracture pattern, aperture and post-test water permeability. For both fracture orientations, very fine, axial fractures evolve over the entire length of the sample. For the fracturing in the Divider orientation, it has been observed, that in some cases, secondary fractures are branching of the main fracture. Test data from fluid driven fracturing experiments suggest that fracture pattern, fracture propagation trajectories and fracturing fluid pressure (initiation and propagation pressure) are predominantly controlled by the interaction between the anisotropic mechanical properties of the shale and the anisotropic stress environment. The orientation of inherent rock anisotropy relative to the principal stress directions seems to be the main control on fracture orientation and required fracturing pressure.

Numerical modeling of a long-term in situ chemical osmosis experiment in the Pierre Shale, South Dakota

USGS Publications Warehouse

Garavito, A.M.; Kooi, H.; Neuzil, C.E.

2006-01-01

We have numerically modeled evolving fluid pressures and concentrations from a nine-year in situ osmosis experiment in the Pierre Shale, South Dakota. These data were obtained and recently interpreted by one of us (C.E.N.) as indicating a potentially significant role for chemical osmosis in media like the Pierre Shale. That analysis considered only the final pressure differentials among boreholes that were assumed to represent osmotic equilibrium. For this study, the system evolution was modeled using a recently developed transient model for membrane transport. The model simulates hydraulically and chemically driven fluid and solute transport. The results yield an estimate of the thickness of the water film between the clay platelets b of 40 A??, which corresponds to an osmotic efficiency ?? of 0.21 for the ambient pore water salinity of 3.5 g/l TDS. These values largely confirm the results of the earlier equilibrium analysis. However, the new model analysis provides additional constraints suggesting that intrinsic permeability k = 1.4 ?? 10-19 m2, specific storage Ss = 1.7 ?? 10-5 m-1, and diffusion coefficient D* = 6 ?? 10-11 m2/s. The k value is larger than certain independent estimates which range from 10-21 to 10-20; it may indicate opening of microcracks during the experiments. The fact that the complex transient pressure and concentration behavior for the individual wells could be reproduced quite accurately, and the inferred parameter values appear to be realistic for the Pierre Shale, suggests that the new model is a useful tool for modeling transient coupled flows in groundwater systems. ?? 2005 Elsevier Ltd. All rights reserved.

Mechanistic Processes Controlling Gas Sorption in Shale Reservoirs

NASA Astrophysics Data System (ADS)

Schaef, T.; Loring, J.; Ilton, E. S.; Davidson, C. L.; Owen, T.; Hoyt, D.; Glezakou, V. A.; McGrail, B. P.; Thompson, C.

2014-12-01

Utilization of CO2 to stimulate natural gas production in previously fractured shale-dominated reservoirs where CO2 remains in place for long-term storage may be an attractive new strategy for reducing the cost of managing anthropogenic CO2. A preliminary analysis of capacities and potential revenues in US shale plays suggests nearly 390 tcf in additional gas recovery may be possible via CO2 driven enhanced gas recovery. However, reservoir transmissivity properties, optimum gas recovery rates, and ultimate fate of CO2 vary among reservoirs, potentially increasing operational costs and environmental risks. In this paper, we identify key mechanisms controlling the sorption of CH4 and CO2 onto phyllosilicates and processes occurring in mixed gas systems that have the potential of impacting fluid transfer and CO2 storage in shale dominated formations. Through a unique set of in situ experimental techniques coupled with molecular-level simulations, we identify structural transformations occurring to clay minerals, optimal CO2/CH4 gas exchange conditions, and distinguish between adsorbed and intercalated gases in a mixed gas system. For example, based on in situ measurements with magic angle spinning NMR, intercalation of CO2 within the montmorillonite structure occurs in CH4/CO2 gas mixtures containing low concentrations (<5 mol%) of CO2. A stable montmorillonite structure dominates during exposure to pure CH4 (90 bar), but expands upon titration of small fractions (1-3 mol%) of CO2. Density functional theory was used to quantify the difference in sorption behavior between CO2 and CH4 and indicates complex interactions occurring between hydrated cations, CH4, and CO2. The authors will discuss potential impacts of these experimental results on CO2-based hydrocarbon recovery processes.

The Drenchwater deposit, Alaska: An example of a natural low pH environment resulting from weathering of an undisturbed shale-hosted Zn-Pb-Ag deposit

USGS Publications Warehouse

Graham, G.E.; Kelley, K.D.

2009-01-01

The Drenchwater shale-hosted Zn-Pb-Ag deposit and the immediate vicinity, on the northern flank of the Brooks Range in north-central Alaska, is an ideal example of a naturally low pH system. The two drainages, Drenchwater and False Wager Creeks, which bound the deposit, differ in their acidity and metal contents. Moderately acidic waters with elevated concentrations of metals (pH ??? 4.3, Zn ??? 1400 ??g/L) in the Drenchwater Creek drainage basin are attributed to weathering of an exposed base-metal-rich massive sulfide occurrence. Stream sediment and water chemistry data collected from False Wager Creek suggest that an unexposed base-metal sulfide occurrence may account for the lower pH (2.7-3.1) and very metal-rich waters (up to 2600 ??g/L Zn, ??? 260 ??g/L Cu and ???89 ??g/L Tl) collected at least 2 km upstream of known mineralized exposures. These more acidic conditions produce jarosite, schwertmannite and Fe-hydroxides commonly associated with acid-mine drainage. The high metal concentrations in some water samples from both streams naturally exceed Alaska state regulatory limits for freshwater aquatic life, affirming the importance of establishing base-line conditions in the event of human land development. The studies at the Drenchwater deposit demonstrate that poor water quality can be generated through entirely natural weathering of base-metal occurrences, and, possibly unmineralized black shale.

Thermal maturity of Jurassic shales from the Newark Basin, U.S.A.: influence of hydrothermal fluids and implications to basin modeling

USGS Publications Warehouse

Walters, C.C.; Kotra, R.K.

1990-01-01

Organic geochemical investigations were conducted on a series of cores that systematically sampled the uppermost Jurassic strata from the northern Newark Basin. Each sedimentary unit consists of fluvial red sandstones and siltstones with cyclic deposits of interbedded black lacustrine shales and gray deltaic siltstones. In a suite of organic-rich shales from the Boonton, Towaco and Feltville Formations, organic maturation parameters were used to determine aspects of the thermal history of the Newark Basin. Comparisons of model calculations and measured maturities support39 Ar/40 Ar-geochronometer studies that indicate a hydrothermal event occurred ???175 Ma ago. An increase in the regional geothermal gradient to ???7.5??C/100 m for ???5 Ma best conforms to the organic geochemical observations. Biomarker compounds in Boonton and Towaco strata should have been relatively unaltered by this regional event, but anomalous molecular distributions in the organic-rich rocks may have resulted from localized heating by hydrothermal fluids. The effects of this interaction would be very subtle and may be indistinguishable from variations caused by differences in organic facies. Within this uncertainty, sterane and hopane isomerization and steroid aromatization reactions advanced in the Boonton and Towaco Formation strata primarily because of burial and normal geothermal heating that followed the hydrothermal event. Biomarker kinetic models indicate that ???2400 m of Boonton and post-Boonton strata were eroded after basinal uplift commenced ???50 Ma ago. ?? 1990.

Establishing effective sentinels - Setting the baseline for shale gas

NASA Astrophysics Data System (ADS)

Ward, C.; Worrall, F.

2017-12-01

The UK has a nascent shale gas industry and, unlike the US we have the opportunity to establish structures both physical and regulatory to reassure the public that any impact of a developing shale gas will be .properly licensed, regulated, monitored and, if necessary, mitigated. To assess and indeed demonstrate an impact of any activity, let alone those of shale gas exploitation, it is necessary to show, within a reasonable level of certainty, that the industry has changed a environmental state over and above that which was true without the activity present. The need for demonstrating impact not only means that a baseline needs to be established but that the baseline needs to be robustly established within a statistical and probabilistic framework so that certainty of impact can be demonstrated. A number of technologies have been proposed for monitoring the water quality impacts of shale gas developments, however, to be an effective and robust sentinel of change the parameter should have several properties: it should be a lead indicator and not a lag indicator of change; it should have a high contrast with the normal or background activity; it should show a high specificity for the activity of concern and not be associated with other activities; and it should readily deployed in time and space. By far the greatest difference between the waters arising from a shale gas well pad and surface waters is nothing more than salinity or its associated determinds. The salinity of flowback water and deep formation water can be many times greater than seawater let alone greater than the salinity of most UK surface waters. Therefore, we have built a probabilistic model of the salinity of English surface waters. We have developed a generalised linear model of the existing salinity data available for English surface waters. Generalised linear modelling means that we can use all the existing data, the approach is entirely data driven; it does not require parameterisation; and can include existing factorial and covariate information. The model was developed in a Bayesian hierarchical framework. The model creates a dynamic baseline against which it is possible to assess whether an observation is within that expected for that river under those temporal and hydroclimatic conditions. The model is tested for the Vale of Pickering gasfield.

Graphic correlation across a facies change marking the location of a middle to late Cenomanian ocean front

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fisher, C.G.

1993-03-01

An abrupt lithofacies change between calcareous shale and non-calcareous shale occurs in strata deposited in the mid-Cretaceous Greenhorn Seaway in the extreme southeastern corner of Montana, U.S.A. This strata, north of the Black Hills has previously been miss-correlated due to the extreme difficulty in locating unique continuous marker beds. Supplemental Graphic Correlation techniques of Lucy Edwards, which expand on those of Shaw, were employed in the difficult task of correlating across the Little Missouri River Valley. Precise correlation was necessary in order to interpret the cause of the lithofacies change. Edwards's use of non-unique event marker beds and the side-by-sidemore » graph method proved to be invaluable tools. Precise correlation across the facies change was accomplished using a combination of bentonite beds, calcarenite beds, ammonite species, foraminiferal and calcareous nannofossil assemblages. Supplemental Graphic Correlation techniques allowed the definition of twenty-five time slices and permitted the identification of an ocean front during each of these time slices.« less

Pellet microfossils: Possible evidence for metazoan life in Early Proterozoic time

PubMed Central

Robbins, Eleanora Iberall; Porter, Karen Glaus; Haberyan, Kurt A.

1985-01-01

Microfossils resembling fecal pellets occur in acid-resistant residues and thin sections of Middle Cambrian to Early Proterozoic shale. The cylindrical microfossils average 50 × 110 μm and are the size and shape of fecal pellets produced by microscopic animals today. Pellets occur in dark gray and black rocks that were deposited in the facies that also preserves sulfide minerals and that represent environments analogous to those that preserve fecal pellets today. Rocks containing pellets and algal microfossils range in age from 0.53 to 1.9 gigayears (Gyr) and include Burgess Shale, Greyson and Newland Formations, Rove Formation, and Gunflint Iron-Formation. Similar rock types of Archean age, ranging from 2.68 to 3.8 Gyr, were barren of pellets. If the Proterozoic microfossils are fossilized fecal pellets, they provide evidence of metazoan life and a complex food chain at 1.9 Gyr ago. This occurrence predates macroscopic metazoan body fossils in the Ediacaran System at 0.67 Gyr, animal trace fossils from 0.9 to 1.3 Gyr, and fossils of unicellular eukaryotic plankton at 1.4 Gyr. Images PMID:16593599

Identity and the Role of the State.

ERIC Educational Resources Information Center

Harvey, Luli

1997-01-01

Examples of marginalized nonformal learning in Britain that is driven by a search for alternative value systems include initiatives among Kurdish refugees, Blacks seeking identity through black studies, women sharing their stories, the resurgence of Irish culture, and the green movement. (SK)

Xenon adsorption on geological media and implications for radionuclide signatures

DOE PAGES

Paul, M. J.; Biegalski, S. R.; Haas, D. A.; ...

2018-02-13

Here, the detection of radioactive noble gases is a primary technology for verifying compliance with the pending Comprehensive Nuclear-Test-Ban Treaty. A fundamental challenge in applying this technology for detecting underground nuclear explosions is estimating the timing and magnitude of the radionuclide signatures. While the primary mechanism for transport is advective transport, either through barometric pumping or thermally driven advection, diffusive transport in the surrounding matrix also plays a secondary role. From the study of primordial noble gas signatures, it is known that xenon has a strong physical adsorption affinity in shale formations. Given the unselective nature of physical adsorption, isothermmore » measurements reported here show that non-trivial amounts of xenon adsorb on a variety of media, in addition to shale. A dual-porosity model is then discussed demonstrating that sorption amplifies the diffusive uptake of an adsorbing matrix from a fracture. This effect may reduce the radioxenon signature down to approximately one-tenth, similar to primordial xenon isotopic signatures.« less

Xenon adsorption on geological media and implications for radionuclide signatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paul, M. J.; Biegalski, S. R.; Haas, D. A.

Here, the detection of radioactive noble gases is a primary technology for verifying compliance with the pending Comprehensive Nuclear-Test-Ban Treaty. A fundamental challenge in applying this technology for detecting underground nuclear explosions is estimating the timing and magnitude of the radionuclide signatures. While the primary mechanism for transport is advective transport, either through barometric pumping or thermally driven advection, diffusive transport in the surrounding matrix also plays a secondary role. From the study of primordial noble gas signatures, it is known that xenon has a strong physical adsorption affinity in shale formations. Given the unselective nature of physical adsorption, isothermmore » measurements reported here show that non-trivial amounts of xenon adsorb on a variety of media, in addition to shale. A dual-porosity model is then discussed demonstrating that sorption amplifies the diffusive uptake of an adsorbing matrix from a fracture. This effect may reduce the radioxenon signature down to approximately one-tenth, similar to primordial xenon isotopic signatures.« less

Xenon adsorption on geological media and implications for radionuclide signatures.

PubMed

Paul, M J; Biegalski, S R; Haas, D A; Jiang, H; Daigle, H; Lowrey, J D

2018-07-01

The detection of radioactive noble gases is a primary technology for verifying compliance with the pending Comprehensive Nuclear-Test-Ban Treaty. A fundamental challenge in applying this technology for detecting underground nuclear explosions is estimating the timing and magnitude of the radionuclide signatures. While the primary mechanism for transport is advective transport, either through barometric pumping or thermally driven advection, diffusive transport in the surrounding matrix also plays a secondary role. From the study of primordial noble gas signatures, it is known that xenon has a strong physical adsorption affinity in shale formations. Given the unselective nature of physical adsorption, isotherm measurements reported here show that non-trivial amounts of xenon adsorb on a variety of media, in addition to shale. A dual-porosity model is then discussed demonstrating that sorption amplifies the diffusive uptake of an adsorbing matrix from a fracture. This effect may reduce the radioxenon signature down to approximately one-tenth, similar to primordial xenon isotopic signatures. Copyright © 2018 Elsevier Ltd. All rights reserved.

Sedimentary manganese metallogenesis in response to the evolution of the Earth system

NASA Astrophysics Data System (ADS)

Roy, Supriya

2006-08-01

The concentration of manganese in solution and its precipitation in inorganic systems are primarily redox-controlled, guided by several Earth processes most of which were tectonically induced. The Early Archean atmosphere-hydrosphere system was extremely O 2-deficient. Thus, the very high mantle heat flux producing superplumes, severe outgassing and high-temperature hydrothermal activity introduced substantial Mn 2+ in anoxic oceans but prevented its precipitation. During the Late Archean, centered at ca. 2.75 Ga, the introduction of Photosystem II and decrease of the oxygen sinks led to a limited buildup of surface O 2-content locally, initiating modest deposition of manganese in shallow basin-margin oxygenated niches (e.g., deposits in India and Brazil). Rapid burial of organic matter, decline of reduced gases from a progressively oxygenated mantle and a net increase in photosynthetic oxygen marked the Archean-Proterozoic transition. Concurrently, a massive drawdown of atmospheric CO 2 owing to increased weathering rates on the tectonically expanded freeboard of the assembled supercontinents caused Paleoproterozoic glaciations (2.45-2.22 Ga). The spectacular sedimentary manganese deposits (at ca. 2.4 Ga) of Transvaal Supergroup, South Africa, were formed by oxidation of hydrothermally derived Mn 2+ transferred from a stratified ocean to the continental shelf by transgression. Episodes of increased burial rate of organic matter during ca. 2.4 and 2.06 Ga are correlatable to ocean stratification and further rise of oxygen in the atmosphere. Black shale-hosted Mn carbonate deposits in the Birimian sequence (ca. 2.3-2.0 Ga), West Africa, its equivalents in South America and those in the Francevillian sequence (ca. 2.2-2.1 Ga), Gabon are correlatable to this period. Tectonically forced doming-up, attenuation and substantial increase in freeboard areas prompted increased silicate weathering and atmospheric CO 2 drawdown causing glaciation on the Neoproterozoic Rodinia supercontinent. Tectonic rifting and mantle outgassing led to deglaciation. Dissolved Mn 2+ and Fe 2+ concentrated earlier in highly saline stagnant seawater below the ice cover were exported to shallow shelves by transgression during deglaciation. During the Sturtian glacial-interglacial event (ca. 750-700 Ma), interstratified Mn oxide and BIF deposits of Damara sequence, Namibia, was formed. The Varangian (≡ Marinoan; ca. 600 Ma) cryogenic event produced Mn oxide and BIF deposits at Urucum, Jacadigo Group, Brazil. The Datangpo interglacial sequence, South China (Liantuo-Nantuo ≡ Varangian event) contains black shale-hosted Mn carbonate deposits. The Early Paleozoic witnessed several glacioeustatic sea level changes producing small Mn carbonate deposits of Tiantaishan (Early Cambrian) and Taojiang (Mid-Ordovician) in black shale sequences, China, and the major Mn oxide-carbonate deposits of Karadzhal-type, Central Kazakhstan (Late Devonian). The Mesozoic period of intense plate movements and volcanism produced greenhouse climate and stratified oceans. During the Early Jurassic OAE, organic-rich sediments host many Mn carbonate deposits in Europe (e.g., Úrkút, Hungary) in black shale sequences. The Late Jurassic giant Mn Carbonate deposit at Molango, Mexico, was also genetically related to sea level change. Mn carbonates were always derived from Mn oxyhydroxides during early diagenesis. Large Mn oxide deposits of Cretaceous age at Groote Eylandt, Australia and Imini-Tasdremt, Morocco, were also formed during transgression-regression in greenhouse climate. The Early Oligocene giant Mn oxide-carbonate deposit of Chiatura (Georgia) and Nikopol (Ukraine) were developed in a similar situation. Thereafter, manganese sedimentation was entirely shifted to the deep seafloor and since ca. 15 Ma B.P. was climatically controlled (glaciation-deglaciation) assisted by oxygenated polar bottom currents (AABW, NADW). The changes in climate and the sea level were mainly tectonically forced.

Something new from something old? Fracking stimulated microbial processes

NASA Astrophysics Data System (ADS)

Wrighton, K. C.; Daly, R. A.; Hoyt, D.; Trexler, R.; McRae, J.; Wilkins, M.; Mouser, P. J.

2015-12-01

Hydraulic fracturing, colloquially known as "fracking", is employed for effective gas and oil recovery in deep shales. This process injects organisms and liquids from the surface into the deep subsurface (~2500 m), exposing microorganisms to high pressures, elevated temperatures, chemical additives, and brine-level salinities. Here we use assembly-based metagenomics to create a metabolic blueprint from an energy-producing Marcellus shale well over a 328-day period. Using this approach we ask the question: What abiotic and biotic factors drive microbial metabolism and thus biogeochemical cycling during natural gas extraction? We found that after 49 days, increased salinity in produced waters corresponded to a shift in the microbial community, with only organisms that encode salinity adaptations detected. We posit that organic compatible solutes, produced by organisms adapting to increased salinity, fuels a methylamine-driven ecosystem in fractured shale. This metabolic network ultimately results in biogenic methane production from members of Methanohalophilus and Methanolobus. Proton NMR validated these genomic hypotheses, with mono-methylamine being highest in the input material, but detected throughout the sampling. Beyond abiotic constraints, our genomic investigations revealed that viruses can be linked to key members of the microbial community, potentially releasing methylamine osmoprotectants and impacting bacterial strain variation. Collectively our results indicate that adaptation to high salinity, metabolism in the absence of oxidized electron acceptors, and viral predation are controlling factors mediating microbial community metabolism during hydraulic fracturing of the deep subsurface.

Tracing redox processes during paleoclimatic changes in the Neoproterozoic: Stable chromium isotopic results from the Arroyo del Soldado Group (Ediacaran, Uruguay)

NASA Astrophysics Data System (ADS)

Frei, R.; Gaucher, C.

2007-12-01

Positive δ13C carbonate values, combined with the occurrence of Fe-rich cherts (oxide-facies BIF) and organic-rich black shales within the late Ediacaran (ca. 580-560 Ma) Yerbal Fm. of the Arroyo del Soldato Group (Uruguay) are compatible with paleoclimatic models which postulate that enhanced bioproductivity due to higher availability of nutrient (P, N, Fe) was essential for controlling Neoproterozoic glaciations. Tracing of associated redox processes (f.e. linked to oxygenation of bottom waters in restricted basins) that might have been responsible for the deposition of Fe-rich cherts (BIFs) is therefore an important tool to better understand the seawater changes during cold-warm periods. Besides the traditionally used Fe and Mo isotopic systems, the redox-sensitive element Cr (Cr(III); Cr(IV)) and its stable isotopes offer another complementary system to trace paleo-redox processes. We have applied Cr stable isotope systematics to a sequence of samples from a late Ediacaran sedimentary sequence in Uruguay, using a 52Cr-54Cr double spike (Schoenberg et al., Chem..Geol., subm.). The middle Yerbal Fm. is dominated by organic-rich, black shales and black dolostones (δ53Cr = -0.05‰), followed by organic-rich cherts (δ53Cr = +1.83 - +4.49 ‰) and BIF (δ53Cr = -0.31 +0.90 ‰) gradually changing into Fe-bearing, organic-rich cherts and shales (δ53Cr = -0.28 - -0.01 ‰), and another sequence with BIF and organic-rich cherts topped by carbonates of the lower Polanco Fm. (δ53Cr = -0.17 to -0.27 ‰). The strongly positively fractionated Cr isotopic signatures in organic-rich and Fe-rich cherts in the Yerbal Fm. may point to significant oxidation processes either directly in the seawater column and/or during early diagenetic processes at the sediment-water interface. While these strongly positive δ53Cr values are the first to be reported from Neoproterozoic sedimentary sequence, the exact nature of the chemical process that produced these anomalies is not yet understood. However, the occurrence of these anomalies in organic-rich and Fe-rich chemical sediments that were deposited in a period following a glacial (Gaskiers?) event is compatible with "Snowball Earth" scenarios whereby impulsive oxidation of the upper seawater was in response to ice cover retraction which allowed booming of the biosphere and concomitant oxidation of accumulated Fe2+ and subsequent precipitation of the Fe-oxyhydroxides to form the "BIF" during such epochs. Schoenberg et al. (subm.) The stable Cr isotope inventory of solid earth reservoirs determined by double-spike MC-ICP-MS. Chemical Geology

Palaeoredox indicators from the organic-rich Messinian early post-evaporitic deposits of the Apennines (Central Italy)

NASA Astrophysics Data System (ADS)

Sampalmieri, G.; Iadanza, A.; Cipollari, P.; Cosentino, D.; Lo Mastro, S.

2009-04-01

Bottom redox conditions in marine and lacustrine ancient basins are often inferred by the occurrence of peculiar sedimentological structures and microfaunal assemblages. The co-occurrence, in such environments, of authigenic uranium, framboidal pyrite, barite and Fe-Mn nodules and encrustations, provides a good constraint for palaeo reconstructions. Authigenic uranium is a common constituent of hydrocarbon source rocks: it forms at the sediment-water interface under oxygen-deficient conditions and accumulates together with organic matter (OM). Its precipitation is triggered by the reduction of the soluble U6+ion in seawater to insoluble U4+. With respect to black shales, uranium content has even been used to estimate the TOC. Also authigenic pyrite forms under anoxic conditions and replaces organic matter: 1) the increase in pyrite content and in organic matter are directly correlated; 2) the size distribution of framboidal pyrite (consistent with sulphate-reducing bacterial activity) is considered a measure of redox conditions within the sediment. Barite is an authigenic mineral related to Corg content, since its organic precipitation is triggered by sulphate-reduction processes occurring in decaying OM-bearing microenvironments. Finally, also Fe-Mn oxyhydroxide are typical indicators of redox conditions. About 6 My ago the Mediterranean Sea underwent a giant event of concentration referred to as Messinian Salinity Crisis, which can be roughly subdivided into an evaporitic and a post evaporitic phase. The post evaporitic phase (p-ev; 5.61-5.33 Ma) developed in a context of humid conditions and can be further distinguished into two steps: p-ev1 (early post evaporitic phase) and p-ev2 (late post evaporitic phase). Previous works focused on pev2, which is interpreted to represent the establishment of brackish water conditions (Lago-Mare biofacies). In other respects, the palaeoenvironment of p-ev1 deposits, mostly represented by resedimented evaporitic deposits or barren laminated sediments, hasn't been thoroughly clarified yet. The aim of the present study, dealing with messinian p-ev1 deposits from Marche and Maiella successions, is to provide more details in the definition of the environment developed during the early post-evaporitic phase. Since the lamination and the absence of benthic fauna suggest the occurrence of anoxic conditions, the following indirect proxies for the detection of organic matter have been investigated: 1) sedimentary fabric and microfacies; 2) framboidal pyrite size distribution; 3) natural radioactivity (authigenic uranium values, Th/U ratios). Natural radioactivity has been achieved through gamma spectrometry, with field and laboratory specific techniques. In the Maccarone section (Marche region), p-ev1 deposits are constituted by: barren greyish shales; laminated black shales interbedded with calcitic and ankeritic horizons; thin intercalations of sandstones. Organic-matter and framboidal pyrite commonly occur. Size analysis of framboids populations yielded a mean diameter of 4÷8 m, typical of disaerobic facies. Microfacies analysis yielded also the presence of crystals aggregates of barite, up to 50 m in size, and of isolated detrital (silicilastic) crystals. Without considering γ-ray values of the volcaniclastic layer (52-65 Cps) occurring within the p-ev1 interval, black shales horizons revealed the maximum natural radioactivity (NRD of about 50 Cps) recorded inthe studied section. Lower γ-activity characterizes the calcitic layers (i.e. "Colombacci") and the ankerites. Field NRD spectra acquired on different lithologies, showed variable contributions of 238U, 232Th and 40K. Both the blue-greyish shales and the black shales are characterized by total NRD related to the three main radioelements: 40K is associated to abundant 238U content (Thppm/Uppm 1). The 238U content is primarily referable to processes of organic matter enrichment (authigenic uranium) and secondarily to the input of detrital grains. In contrast, 40K and 232Th are entirely ascribed to the clastic fraction. P-ev1 deposits from Maiella section consist of thinly-laminated grey-brownish pelites, enclosing carbonatic lenses and interrupted horizons. The pelitic fraction contains Fe-Mn-Ni encrustated micronodules. The carbonate portion is made up of locally brecciated calcitic limestones, associated with calcitic concretions and discontinuous laminae. Traces of organic matter and bitumen have been observed in thin section. Framboidal pyrite occurs both as single element and as aggregate, reaching dimensions up to about 10 m. Barite and celestite occur as well. NRD measurements yielded high values of radioactivity both in carbonates (20-63 Cps) and in terrigenous sediments (21-70 Cps). Limestones NRD-spectra showed a 238U-dominant (5 ppm in content) radioactivity. 238U is totally referable to an authigenic origin, since the γ-activity of limestones is devoid of contributions from 40K and 232Th (proxies for the detritic fraction). In the latest Messinian frame, authigenic uranium, barite, ankerite, Fe-Mn oxyhydroxide and framboidal pyrite indicate strongly palaeoredox conditions (from disaerobic to fully anoxic). In particular, with respect to NRD data, this peculiar environment is confirmed by the Th/U ratio, mostly

Rock Magnetic Cyclostratigraphy of the Mid-Cretaceous Greenhorn Limestone, South-Central Colorado---Influence of Orbitally Induced Climate Variability for Chornostratigraphy

NASA Astrophysics Data System (ADS)

Sellers, T.; Geissman, J. W.; Jackson, J.

2015-12-01

We are testing the hypothesis that depositional processes of the mid-Cretaceous Greenhorn Limestone were influenced by orbitally-driven climate variations using rock magnetic data. Correlation of the data, including anhysteretic remanent magnetization (ARM), magnetic susceptibility, isothermal remanent magnetization in different DC fields to saturation, and hysteresis properties, from three continuously exposed sections of the full Greenhorn Limestone provides detailed spatial distribution for the depositional processes and magnetic mineral climate encoding. The Greenhorn Limestone includes the Lincoln Limestone, Hartland Shale, and the Bridge Creek Limestone members and consists of calcareous shales and limestones representing near maximum depths in the Cretaceous interior seaway. The sections, each about 30 m thick, extend from the upper Graneros Shale, through the Greenhorn Formation, to the lower Carlisle Shale, with samples collected at a two to five cm interval and are located at Badito, CO; north of Redwing, CO; and at the Global boundary Stratotype Section and Point (GSSP) at Lake Pueblo, CO. Our over 1000 samples were hand crushed to granule size pieces and packed into 7cc IODP boxes. Bulk magnetic susceptibility, anhysteretic remanent magnetization (ARM) intensity at different peak AF levels, and isothermal remanent magnetization (IRM) intensity record variations in magnetic mineral concentration and are proxies to determine orbital scale cycles and precise stratigraphic correlation between sections. ARM intensities in a peak field of 100 mT at both sites range between 1.2 x 10-3 and 1.3 x 10-4 A/m and better define periodic variation within the Greenhorn Limestone displaying differences in ferromagnetic mineral content of detrital origin. Magnetic susceptibility, which ranges from 3.5 x 10-2 to 2.86 x 10-3, also shows periodic variation with a strong correlation among the three sections. Saturation IRM at 100 mT ranges from 3.2 x 10-1 to 1.1x 10-2 A/m shows periodic variation with the greatest variability in the Bridge Creek Member. Preliminary spectral analysis of each data set indicates a dominant cyclicity that is of considerably lower frequency than the limestone/shale couplets characteristic of Greenhorn Limestone.

Diversity and role of plasmids in adaptation of bacteria inhabiting the Lubin copper mine in Poland, an environment rich in heavy metals.

PubMed

Dziewit, Lukasz; Pyzik, Adam; Szuplewska, Magdalena; Matlakowska, Renata; Mielnicki, Sebastian; Wibberg, Daniel; Schlüter, Andreas; Pühler, Alfred; Bartosik, Dariusz

2015-01-01

The Lubin underground mine, is one of three mining divisions in the Lubin-Glogow Copper District in Lower Silesia province (Poland). It is the source of polymetallic ore that is rich in copper, silver and several heavy metals. Black shale is also significantly enriched in fossil organic matter in the form of long-chain hydrocarbons, polycyclic aromatic hydrocarbons, organic acids, esters, thiophenes and metalloporphyrins. Biological analyses have revealed that this environment is inhabited by extremophilic bacteria and fungi. Kupfershiefer black shale and samples of water, bottom and mineral sediments from the underground (below 600 m) Lubin mine were taken and 20 bacterial strains were isolated and characterized. All exhibited multi-resistant and hypertolerant phenotypes to heavy metals. We analyzed the plasmidome of these strains in order to evaluate the diversity and role of mobile DNA in adaptation to the harsh conditions of the mine environment. Experimental and bioinformatic analyses of 11 extrachromosomal replicons were performed. Three plasmids, including a broad-host-range replicon containing a Tn3 family transposon, carried genes conferring resistance to arsenic, cadmium, cobalt, mercury and zinc. Functional analysis revealed that the resistance modules exhibit host specificity, i.e., they may increase or decrease tolerance to toxic ions depending on the host strain. The other identified replicons showed diverse features. Among them we identified a catabolic plasmid encoding enzymes involved in the utilization of histidine and vanillate, a putative plasmid-like prophage carrying genes responsible for NAD biosynthesis, and two repABC-type plasmids containing virulence-associated genes. These findings provide an unique molecular insight into the pool of extrachromosomal replicons and highlight their role in the biology and adaptation of extremophilic bacteria inhabiting terrestrial deep subsurface.

Trace fossils from storm-influenced, oxygen-deficient outer shelf: lower Mississippian Price Formation of southern West Virginia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bjerstedt, T.W.

The Price Formation in southern West Virginia was deposited dominantly in an oxygen-deficient, outer shelf environment along a siliciclastic profile from the basin plain to the alluvial plain. An overturned section at Bluefield, West Virginia, exposes the following lithofacies and environments in ascending order: laminated black silt-shales from the basin plain; a sand-rich submarine fan; outer shelf tempestites of hummocky, cross-stratified fine sandstone and completely bioturbated grayish-black, silt-shales; and shoreline sands in transition to thin, dirty coals of the coastal plain and Maccrady red beds of the alluvial plain. Trace fossils are abundant and are best preserved on the solesmore » of hummocky, cross-stratified sandstones. The Zoophycos ichnofacies occurs throughout 80 m of outer shelf deposits, which accumulated above storm wave base. The Zoophycos ichnofacies grades into the nearshore Skolithus ichnofacies with no apparent intervening Cruziana ichnofacies. Most ichnotaxa identified from the outer shelf are fodinichnia or pascichnia. Planar and helical Zoophycos, Helminthopsis, Helminthoida, Sclarituba (neonereites form), and Chondrites are characteristics. In most schemes, the Zoophycos ichnofacies occurs below storm wave base. At Bluefield, it has displaced the Cruziana ichnofacies above storm wave base due to the maintenance of a dysaerobic environment. The abundant organic matter preserved in a density-stratified water column was continually replenished during periods of upwelling. Conditions were extremely favorable for deposit feeders, but inhibiting to suspension feeders that were less tolerant of oxygen stress. The absence of distributary channel sands in the vertical sequence also indicates that offshore environments received no influx of oxygenated waters from the Price delta.« less

Sedimentary exhalative nickel-molybdenum ores in south China

USGS Publications Warehouse

Lott, D.A.; Coveney, R.M.; Murowchick, J.B.; Grauch, R.I.

1999-01-01

Unique bedded Ni-Mo ores hosted by black shales were discovered in localized paleobasins along the Yangzte platform of southern China in 1971. Textural evidence and radiometric dates imply ore formation during sedimentation of black shales that grade into readily combustible beds, termed stone coals, which contain 10 to 15 percent organic carbon. Studies of 427 fluid inclusions indicate extreme variation in hydrothermal brine salinities that were contained by Proterozoic dolostones underlying the ore zone in Hunan and Guizhou. Variations of fluid inclusion salinities, which range from 0.1 to 21.6 wt percent NaCl equiv, are attributed to differences in the compositions of brines in strata underlying the ore bed, complicated by the presence of seawater and dilute fluids that represent condensates of vapors generated by boiling of mineralizing fluids or Cambrian meteoric water. The complex processes of ore deposition led to scattered homogenization temperatures ranging from 100??to 187??C within the Hunan ore zone and from 65??to 183??C within the Guizhou ore zone. While living organisms probably did not directly accumulate metals in situ in sufficient amounts to explain the unusually high grades of the deposits, sulfur isotope ratios indicate that bacteria, now preserved as abundant microfossils, provided sufficient sulfide for the ores by reduction of seawater sulfate. Such microbiota may have depended on vent fluids and transported organic matter for key nutrients and are consistent with a sedex origin for the ores. Vent fluids interacted with organic remains, including rounded fragments of microbial mats that were likely transported to the site of ore deposition by the action of waves and bottom currents prior to replacement by ore minerals.

Geology of the Powder River Basin, Wyoming and Montana, with reference to subsurface disposal of radioactive wastes

USGS Publications Warehouse

Beikman, Helen M.

1962-01-01

The Powder River Basin is a structural and topographic basin occupying an area of about 20,000 square miles in northeastern Wyoming arid southeastern Montana. The Basin is about 230 miles long in a northwest-southeast direction and is about 100 miles wide. It is bounded on three sides by mountains in which rocks of Precambrian age are exposed. The Basin is asymmetrical with a steep west limb adjacent to the Bighorn Mountains and a gentle east limb adjacent to the Black Hills. Sedimentary rocks within the Basin have a maximum thickness of about 18,000 feet and rocks of every geologic period are represented. Paleozoic rocks are about 2,500 feet thick and consist of marine bonate rocks and sandstone; Mesozoic rocks are about 9,500 feet thick and consist of both marine and nonmarine siltstone and sandstone; and Cenozoic rocks are from 4,000 to 6,000 feet thick and consist of coal-bearing sandstone and shale. Radioactive waste could be stored in the pore space of permeable sandstone or in shale where space could be developed. Many such rock units that could be used for storing radioactive wastes are present within the Powder River Basin. Permeable sandstone beds that may be possible reservoirs for storage of radioactive waste are present throughout the Powder River Basin. These include sandstone beds in the Flathead Sandstone and equivalent strata in the Deadwood Formation, the Tensleep Sandstone and equivalent strata in the Minnelusa Formation and the Sundance Formation in rocks of pre-Cretaceous age. However, most of the possible sandstone reservoirs are in rocks of Cretaceous age and include sandstone beds in the Fall River, Lakota, Newcastle, Frontier, Cody, and Mesaverde Formations. Problems of containment of waste such as clogging of pore space and chemical incompatibility would have to be solved before a particular sandstone unit could be selected for waste disposal. Several thick sequences of impermeable shale such as those in the Skull Creek, Mowry, Frontier, Belle Fourche, Cody, Lewis, and Pierre Formations, occur in rocks of Cretaceous age in the Basin. Limited storage space for liquid waste might be developed in impermeable shale by fracturing the shale and space for calcined or fused waste could be developed by mining cavities.

Cu isotopes in marine black shales record the Great Oxidation Event

PubMed Central

Rodríguez, Nathalie P.; Partin, Camille A.; Andersson, Per; Weiss, Dominik J.; El Albani, Abderrazak; Rodushkin, Ilia; Konhauser, Kurt O.

2016-01-01

The oxygenation of the atmosphere ∼2.45–2.32 billion years ago (Ga) is one of the most significant geological events to have affected Earth’s redox history. Our understanding of the timing and processes surrounding this key transition is largely dependent on the development of redox-sensitive proxies, many of which remain unexplored. Here we report a shift from negative to positive copper isotopic compositions (δ65CuERM-AE633) in organic carbon-rich shales spanning the period 2.66–2.08 Ga. We suggest that, before 2.3 Ga, a muted oxidative supply of weathering-derived copper enriched in 65Cu, along with the preferential removal of 65Cu by iron oxides, left seawater and marine biomass depleted in 65Cu but enriched in 63Cu. As banded iron formation deposition waned and continentally sourced Cu became more important, biomass sampled a dissolved Cu reservoir that was progressively less fractionated relative to the continental pool. This evolution toward heavy δ65Cu values coincides with a shift to negative sedimentary δ56Fe values and increased marine sulfate after the Great Oxidation Event (GOE), and is traceable through Phanerozoic shales to modern marine settings, where marine dissolved and sedimentary δ65Cu values are universally positive. Our finding of an important shift in sedimentary Cu isotope compositions across the GOE provides new insights into the Precambrian marine cycling of this critical micronutrient, and demonstrates the proxy potential for sedimentary Cu isotope compositions in the study of biogeochemical cycles and oceanic redox balance in the past. PMID:27091980

Energy Intensity and Greenhouse Gas Emissions from Oil Production in the Eagle Ford Shale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yeh, Sonia; Ghandi, Abbas; Scanlon, Bridget R.

A rapid increase in horizontal drilling and hydraulic fracturing in shale and “tight” formations that began around 2000 has resulted in record increases in oil and natural gas production in the U.S. This study examines energy consumption and greenhouse gas (GHG) emissions from crude oil and natural gas produced from ~8,200 wells in the Eagle Ford Shale in southern Texas from 2009 to 2013. Our system boundary includes processes from primary exploration wells to the refinery entrance gate (henceforth well-to-refinery or WTR). The Eagle Ford includes four distinct production zones—black oil (BO), volatile oil (VO), condensate (C), and dry gasmore » (G) zones—with average monthly gas-to-liquids ratios (thousand cubic feet per barrel—Mcf/bbl) varying from 0.91 in the BO zone to 13.9 in the G zone. Total energy consumed in drilling, extracting, processing, and operating an Eagle Ford well is ~1.5% of the energy content of the produced crude and gas in the BO and VO zones, compared with 2.2% in the C and G zones. On average, the WTR GHG emissions of gasoline, diesel, and jet fuel derived from crude oil produced in the BO and VO zones in the Eagle Ford play are 4.3, 5.0, and 5.1 gCO2e/MJ, respectively. Comparing with other known conventional and unconventional crude production where upstream GHG emissions are in the range 5.9–30 gCO2e/MJ, oil production in the Eagle Ford has lower WTR GHG emissions.« less

Method for rubblizing an oil shale deposit for in situ retorting

DOEpatents

Lewis, Arthur E.

1977-01-01

A method for rubblizing an oil shale deposit that has been formed in alternate horizontal layers of rich and lean shale, including the steps of driving a horizontal tunnel along the lower edge of a rich shale layer of the deposit, sublevel caving by fan drilling and blasting of both rich and lean overlying shale layers at the distal end of the tunnel to rubblize the layers, removing a substantial amount of the accessible rubblized rich shale to permit the overlying rubblized lean shale to drop to tunnel floor level to form a column of lean shale, performing additional sublevel caving of rich and lean shale towards the proximate end of the tunnel, removal of a substantial amount of the additionally rubblized rich shale to allow the overlying rubblized lean shale to drop to tunnel floor level to form another column of rubblized lean shale, similarly performing additional steps of sublevel caving and removal of rich rubble to form additional columns of lean shale rubble in the rich shale rubble in the tunnel, and driving additional horizontal tunnels in the deposit and similarly rubblizing the overlying layers of rich and lean shale and forming columns of rubblized lean shale in the rich, thereby forming an in situ oil shale retort having zones of lean shale that remain permeable to hot retorting fluids in the presence of high rubble pile pressures and high retorting temperatures.

Genesis of the Assif El Mal Zn-Pb (Cu, Ag) vein deposit. An extension-related Mesozoic vein system in the High Atlas of Morocco. Structural, mineralogical, and geochemical evidence

USGS Publications Warehouse

Bouabdellah, M.; Beaudoin, G.; Leach, D.L.; Grandia, F.; Cardellach, E.

2009-01-01

The Assif El Mal Zn-Pb (Cu-Ag) vein system, located in the northern flank of the High Atlas of Marrakech (Morocco), is hosted in a Cambro-Ordovician volcaniclastic and metasedimentary sequence composed of graywacke, siltstone, pelite, and shale interlayered with minor tuff and mudstone. Intrusion of synorogenic to postorogenic Late Hercynian peraluminous granitoids has contact metamorphosed the host rocks giving rise to a metamorphic assemblage of quartz, plagioclase, biotite, muscovite, chlorite, amphibole, chloritoid, and garnet. The Assif El Mal Zn-Pb (Cu-Ag) mineralization forms subvertical veins with ribbon, fault breccia, cockade, comb, and crack and seal textures. Two-phase liquid-vapor fluid inclusions that were trapped during several stages occur in quartz and sphalerite. Primary inclusion fluids exhibit Th mean values ranging from 104??C to 198??C. Final ice-melting temperatures range from -8.1??C to -12.8??C, corresponding to salinities of ???15 wt.% NaCl equiv. Halogen data suggest that the salinity of the ore fluids was largely due to evaporation of seawater. Late secondary fluid inclusions have either Ca-rich, saline (26 wt.% NaCl equiv.), or very dilute (3.5 wt.% NaCl equiv.) compositions and homogenization temperatures ranging from 75??C to 150??C. The ??18O and ??D fluid values suggest an isotopically heterogeneous fluid source involving mixing between connate seawater and black-shale-derived organic waters. Low ??13CVPDB values ranging from -7.5??? to -7.7??? indicate a homogeneous carbon source, possibly organic matter disseminated in black shale hosting the Zn-Pb (Cu-Ag) veins. The calculated ??34SH2S values for reduced sulfur (22.5??? to 24.3???) are most likely from reduction of SO42- in trapped seawater sulfate or evaporite in the host rocks. Reduction of sulfate probably occurred through thermochemical sulfate reduction in which organic matter was oxidized to produce CO2 which ultimately led to precipitation of saddle dolomite with isotopically light carbon. Lead isotope compositions are consistent with fluid-rock interaction that leached metals from the immediate Cambro-Ordovician volcaniclastic and metasedimentary sequence or from the underlying Paleo-Neoproterozoic crustal basement. Geological constraints suggest that the vein system of Assif El Mal formed during the Jurassic opening of the central Atlantic Ocean. ?? Springer-Verlag 2009.

The Early Gulf of Mexico as a Subaerial Basin Below Sea Level (SABSEL) Basin. Evidence from Stratigraphy and Facies of Luanne salt, Norphlet sandstone and Smackover Brown Dense Formations.

NASA Astrophysics Data System (ADS)

Cassidy, M. M.

2016-12-01

Many workers recognize that large salt deposits form in post-rift sag basins which were subaerial and susceptible to rapid flooding from adjacent oceansl. I have termed these basins "subaerial basins below sea level" or "SABSEL" basins. A key marker of SABSEL basins are terrestrial sediments immediately overlain by deepwater sediments with no transition. Desert deposits -including Aeolian dunes- are preserved in the adiabatically heated depression. Dunes are not eroded by transgressing seas but are drowned by rising water as in a bath tub. They maintain their shape. Deepwater marine black shales or limestones drape the dunes. The Southern North sea is an example. Above the original marine shale over the dunes are evaporites. Winds descending into the basin were heated by adiabatic compression providing the very hot air need to allow survival of potassium salts. A similar situation was probably active during the Messinian salinity crisis in the Mediterranean basin, and the opening of the South Atlantic. In the Gulf of Mexico (GOM) a desert is on the Louann salt. Here the sea invaded the lows first to deposit the salt overlying tilted fault blocks of the opening basin, as in the Afar Triangle of Africa. In the GOM entry to the west fed in sea water, then closed. The Norphlet desert formed. Streams carried sands to the basin to be spread by winds where they willed, not limited to sand entry areas. Upon deposition their original weight depressed the salt. Seismic shows depressions in the salt but the dunes are high at the top Norphlet, forming distinctive small "eyes" at the top salt. The 600 foot dunes are draped by deep water dolomitic finely laminated organic rich black/ brown shale, the Brown Dense Facies of the Smackover formation. The lack of reworking of the dunes found by detailed seismic is distinctive of deposition in a SABSEL basin. The overlap of terrestrial sediments by deep water deposition is good evidence of sudden flooding. In summary this vertical succession of facies in the Jurassic can be explained as a SABSEL Basin. Evidence of Norphlet presence exists east of the Mississippi delta and the in Campeche embayment of Mexico. Search for its distinctive seismic signature throughout the Gulf of Mexico should continue, and may yield more large gas deposits.

Looking for the Kellwasser Event in all the wrong places: a multiproxy study of island arc paleoenvironments in the Central Asian Orogenic Belt

NASA Astrophysics Data System (ADS)

Carmichael, S. K.; Wang, Z.; Waters, J. A.; Dombrowski, A. D.; Batchelor, C. J.; Coleman, D. S.; Suttner, T.; Kido, E.

2017-12-01

The Late Devonian Frasnian-Famennian (F-F) boundary at 372 Ma is associated with the Kellwasser Event, an ocean anoxia event that is often associated with positive δ13C excursions and commonly represented by black shales. However, approximately 88% of the studies of the Kellwasser Event are based on sites from deep epicontinental basins and epeiric seas, and most of these sites are located on the Euramerican paleocontinent. In contrast to the positive δ13C excursions found in most basinal study sites, the δ13C signatures in three separate shallow water, island-arc F-F sections in the Junggar Basin in northwestern China (Wulankeshun, Boulongour Reservoir, and Genare) all show negative excursions in the stratigraphic location of the Kellwasser Event [1-3]. The δ18O values in both carbonates and/or conodont apatite likewise show negative excursions within the shallow water facies at each site, but have relatively constant signatures within the deeper water facies. 87Sr/86Sr values range from 0.70636-0.70906 at the base of the Boulongour Reservoir section and 0.70746-0.71383 at the base of the Wulankeshun section but both Sr signaures stabilize with relatively constant values closer to modeled Late Devonian seawater in deeper water and/or offshore facies. The fossil assemblages at the base of the Boulongour and Wulankeshun sections each correspond to euryhaline/brackish conditions, while microtextures in Ti-bearing phases within clastic sediments as well as isotope mixing models suggest submarine groundwater discharge signatures rather than diagenetic alteration. Preliminary framboidal pyrite distributions in these sections also show evidence for sub/dysoxic (rather than euxinic or anoxic) conditions that correspond to the stratigraphic Kellwasser interval. Positive δ13C excursions and the presence of black shales are thus not prerequisites for recognition of the Kellwasser Event, particularly in shallow water paleoenvironments that are not topographically favorable to shale accumulation and may have significant coastal groundwater or surface water inputs. [1] Suttner et al. (2014) J. of Asian Earth Sci. 80, 101-118. [2] Carmichael et al. (2014) Paleo3 399, 394-403. [3] Wang et al. (2016) Paleo3 448, 279-297.

Upper Paleozoic Marine Shale Characteristics and Exploration Prospects in the Northwestern Guizhong Depression, South China

NASA Astrophysics Data System (ADS)

Zhu, Zhenhong; Yao, Genshun; Lou, Zhanghua; Jin, Aimin; Zhu, Rong; Jin, Chong; Chen, Chao

2018-05-01

Multiple sets of organic-rich shales developed in the Upper Paleozoic of the northwestern Guizhong Depression in South China. However, the exploration of these shales is presently at a relatively immature stage. The Upper Paleozoic shales in the northwestern Guizhong Depression, including the Middle Devonian Luofu shale, the Nabiao shale, and the Lower Carboniferous Yanguan shale, were investigated in this study. Mineral composition analysis, organic matter analysis (including total organic carbon (TOC) content, maceral of kerogen and the vitrinite reflection (Ro)), pore characteristic analysis (including porosity and permeability, pore type identification by SEM, and pore size distribution by nitrogen sorption), methane isothermal sorption test were conducted, and the distribution and thickness of the shales were determined, Then the characteristics of the two target shales were illustrated and compared. The results show that the Upper Paleozoic shales have favorable organic matter conditions (mainly moderate to high TOC content, type I and II1 kerogen and high to over maturity), good fracability potential (brittleness index (BI) > 40%), multiple pore types, stable distribution and effective thickness, and good methane sorption capacity. Therefore, the Upper Paleozoic shales in the northern Guizhong Depression have good shale gas potential and exploration prospects. Moreover, the average TOC content, average BI, thickness of the organic-rich shale (TOC > 2.0 wt%) and the shale gas resources of the Middle Devonian shales are better than those of the Lower Carboniferous shale. The Middle Devonian shales have better shale gas potential and exploration prospects than the Lower Carboniferous shales.

New Potential Sources for Black Onaping Carbon

NASA Technical Reports Server (NTRS)

Bunch, T. E.; Becker, L.; Schultz, P. H.; Wolbach, W. S.

1997-01-01

One intriguing and important issue of the Sudbury Structure concerns the source of the relatively large amount of C in the Onaping Formation Black member. This dilemma was recently addressed, and the conclusion was reached that an impactor could not have delivered all of the requisite C. Becker et al. have suggested that much of the C came from the impactor and reported the presence of interstellar He "caged" inside some fullerenes that may have survived the impact. So, conceivably, the C inventory in the Sudbury Structure comes from both target and impactor materials, although the known target rocks have little C. We discuss here the possibility of two terrestrial sources for at least some of the C: (1) impact evaporation/dissociation of C from carbonate target rocks and (2) the presence of heretofore-unrecognized C-rich (up to 26 wt%) siliceous "shale," fragments, which are found in the upper, reworked Black member. Experimental: Hypervelocity impact of a 0.635-diameter Al projectile into dolomite at 5.03 km/s (performed at the Ames Research Center vertical gun range) produced a thin, black layer (= 0.05 mm thick) that partially lined the crater and coated impactor remnants. Scanning electronic microscope (SEM) imagery shows this layer to be spongelike on a submicron scale and Auger spectroscopic analyses yield: 33% C, 22% Mg, 19% 0, and 9% Al (from the projectile). Elemental mapping shows that all of the available 0 is combined with Ca and Mg, Al is not oxidized, and C is in elemental form. Dissociation efficiency of C from CO2 is estimated to be <10% of crater volume. Raman spectroscopy indicates that the C is highly disorganized graphite. Another impact experiment [4] also produced highly disordered graphite from a limestone target (reducing collector), in addition to small amounts of diamond/lonsdaleite/chaoite (oxidizing collector). These experiments confirm the reduction of C from carbonates in impact vapor plumes. Observational: SEM observations and microprobe analyses of small, black shalelike inclusions in the upper Black Onaping indicate high C contents (7-26 wt% avg. = 16%). They contain mostly quartz and carbonaceous matter with small amounts of altered K-feldspar, clays, Fe oxide, and a sulfide. No evidence of shock is seen in quartz, and overall characteristics indicate a natural, lightly metamorphosed carbonaceous shale or mudstone that probably existed as a preimpact rock in the target region and distal fragments washed in during early crater filling. Fragments range in size from tens of microns to cm and increase in abundance in the upper Black toward the Onwatin contact, although their distribution is highly irregular. This increase corresponds to an increase in "organic" C with increasingly negative delta-13 C values and S, together with a decrease in fullerene abundance. In addition, we have found soot in acid-demineralized residues of the Onwatin but not in the Onaping samples. These data could be consistent with impact plume and atmospheric chemical processes, with possible diageneric ovedays. We are analyzing carbonaceous fractions of the Onaping and Onwatin to determine diagnostic C isotopic signatures Analyses by Whitehead et al. on bulk samples revealed no definitive source or processes, although delta-13 C values for "organic" C overlapped those for some meteorites. Discussion: If impact evaporation of Sudbury target carbonates did occur, then where are the carbonates? Distal carbonate (limestone/dolostone) exposures of the Espanola Formation (Huronian Supergroup) are generally thin-bedded, although remnants that partially encompass the Sudbury Crater are variable in thickness and may locally reach 250 m . If a carbonate thickness of 100-200 in existed at the target site, then copious amounts of C could have been reduced by impact processing of carbonates and also C-shale, depending on the efficiency of the processing and the amount of postimpact oxidation. Conclusion: The Sudbury crater offers a unique opportunity to study preserved characteristics of immediate carbonaceous fallback matter and particles of short-term residency in the impact plume as well as dust/aerosols from postimpact atmospheric processing.

Role of upper-most crustal composition in the evolution of the Precambrian ocean-atmosphere system

NASA Astrophysics Data System (ADS)

Large, R. R.; Mukherjee, I.; Zhukova, I.; Corkrey, R.; Stepanov, A.; Danyushevsky, L. V.

2018-04-01

Recent research has emphasized the potential relationships between supercontinent cycles, mountain building, nutrient flux, ocean-atmosphere chemistry and the origin of life. The composition of the Upper-Most Continental Crust (UMCC) also figures prominently in these relationships, and yet little detailed data on each component of this complex relationship has been available for assessment. Here we provide a new set of data on the trace element concentrations, including the Rare Earth Elements (REE), in the matrix of 52 marine black shale formations spread globally through the Archean and Proterozoic. The data support previous studies on the temporal geochemistry of shales, but with some important differences. Results indicate a change in provenance of the black shales (upper-most crustal composition), from more mafic in the Archean prior to 2700 Ma, to more felsic from 2700 to 2200 Ma, followed by a return to mafic compositions from 2200 to 1850 Ma. Around 1850 to 1800 Ma there is a rapid change to uniform felsic compositions, which remained for a billion years to 800 Ma. The shale matrix geochemistry supports the assertion that the average upper-most continental source rocks for the shales changed from a mix of felsic, mafic and ultramafic prior to 2700 Ma to more felsic after 1850 Ma, with an extended transition period between. The return to more mafic UMCC from 2200 to 1850 Ma is supported by the frequency of Large Igneous Provinces (LIPs) and banded iron formations, which suggest a peak in major mantle-connected plume events and associated Fe-rich hydrothermal activity over this period. Support for the change to felsic UMCC around 1850 Ma is provided by previous geological data which shows that felsic magmas, including, A-type granites and K-Th-U-rich granites intruded vast areas of the continental crust, peaking around 1850 Ma and declining to 1000 Ma. The implications of this change in UMCC are far reaching and may go some way to explain the distinct features of the Boring Billion (1800-800 Ma). Firstly, because mafic-ultramafic rocks contain significantly higher levels of the bio-essential nutrient elements (e.g. Fe, P, Ni, Cr, Co, Cu, Se, Mn, Zn) compared with felsic rocks, the flux of macro- and micro-nutrients to the ocean would have decreased significantly post 1850 Ma. This would have contributed to a drop in productivity and a drop in atmosphere O2 as suggested by the marine pyrite proxy. In addition, a change from mafic to felsic dominant composition of the UMCC post 1850 Ma, would have led to a decrease in the erosive flux of Ca and Mg to the ocean, affecting the oceanic carbonate equilibrium and likely contributing to a rise in atmosphere CO2. On this basis, we speculate that the commencement of the middle Proterozoic, commonly known as the Boring Billion period from 1800 to 800 Ma, marks the start of an extended time in Earth's evolution when the UMCC became dominated by felsic rocks, particularly K-U-Th-anorogenic granites. This led to a period of anomalously low concentrations of bio-essential trace elements, but elevated REE, U, Th, Pb, Tl, Rb/Al and K/Na in the oceans.

Sedimentary and petrofacies analyses of the Amasiri Sandstone, southern Benue Trough, Nigeria: Implications for depositional environment and tectonic provenance

NASA Astrophysics Data System (ADS)

Okoro, A. U.; Igwe, E. O.; Nwajide, C. S.

2016-11-01

This study was undertaken to determine the depositional environment, provenance and tectonic setting for the Turonian Amasiri Sandstone, southern Benue Trough, Nigeria, using lithofacies analysis and re-appraisal of petrography of the sandstones. Local stratigraphy and field relationships show a thick succession of shales alternating with elongate/parallel sandstone ridges extending eastwards from Akpoha to Amasiri through Itigidi and Ugep to Apiapum areas. Lithofacies analysis reveals 9 lithofacies suggestive of storm (mass flow) and tidal shelf processes. These include dark grey to black laminated shale/silty mudstones, bioturbated mudstones, coquinoid limestones, very fine-grained bioturbated sandstones with shell hash/debris in places and limestone rip-up clasts, massive and chaotic sandy conglomerate with rip - up clasts, fine to medium-grained, parallel laminated sandstone, hummocky cross-stratified, massive, medium to coarse-grained sandstones, medium to very coarse-grained, planar cross-bedded sandstone, with clay-draped foresets and Ophiomorpha burrows, and coarse-grained trough cross-bedded sandstone. Petrofacies analysis identifies the sandstones as feldspathic and arkosic arenites. Ternary plot of framework mineralogy indicates derivation from an uplifted continental block related to the nearby Oban Massif and Cameroon Basement Complex.

How to model AGN feedback in cosmological simulations?

NASA Astrophysics Data System (ADS)

Sijacki, Debora

2015-08-01

Hydrodynamical cosmological simulations are one of the most powerful tools to study the formation and evolution of galaxies in the fully non-linear regime. Despite several recent successes in simulating Milky Way look-alikes, self-consistent, ab-initio models are still a long way off. In this talk I will review numerical and physical uncertainties plaguing current state-of-the-art cosmological simulations of galaxy formation. I will then discuss which feedback mechanisms are needed to reproduce realistic stellar masses and galaxy morphologies in the present day Universe and argue that the black hole feedback is necessary for the quenching of massive galaxies. I will then demonstrate how black hole - host galaxy scaling relations depend on galaxy morphology and colour, highlighting the implications for the co-evolutionary picture between galaxies and their central black holes. In the second part of the talk I will present a novel method that permits to resolve gas flows around black holes all the way from large cosmological scales to the Bondi radii of black holes themselves. I will demonstrate that with this new numerical technique it is possible to estimate much more accurately gas properties in the vicinity of black holes than has been feasible before in galaxy and cosmological simulations, allowing to track reliably gas angular momentum transport from Mpc to pc scales. Finally, I will also discuss if AGN-driven outflows are more likely to be energy- or momentum-driven and what implications this has for the redshift evolution of black hole - host galaxy scaling relations.

Supported black phosphorus nanosheets as hydrogen-evolving photocatalyst achieving 5.4% energy conversion efficiency at 353 K.

PubMed

Tian, Bin; Tian, Bining; Smith, Bethany; Scott, M C; Hua, Ruinian; Lei, Qin; Tian, Yue

2018-04-11

Solar-driven water splitting using powdered catalysts is considered as the most economical means for hydrogen generation. However, four-electron-driven oxidation half-reaction showing slow kinetics, accompanying with insufficient light absorption and rapid carrier combination in photocatalysts leads to low solar-to-hydrogen energy conversion efficiency. Here, we report amorphous cobalt phosphide (Co-P)-supported black phosphorus nanosheets employed as photocatalysts can simultaneously address these issues. The nanosheets exhibit robust hydrogen evolution from pure water (pH = 6.8) without bias and hole scavengers, achieving an apparent quantum efficiency of 42.55% at 430 nm and energy conversion efficiency of over 5.4% at 353 K. This photocatalytic activity is attributed to extremely efficient utilization of solar energy (~75% of solar energy) by black phosphorus nanosheets and high-carrier separation efficiency by amorphous Co-P. The hybrid material design realizes efficient solar-to-chemical energy conversion in suspension, demonstrating the potential of black phosphorus-based materials as catalysts for solar hydrogen production.

Effects of retorting factors on combustion properties of shale char. 3. Distribution of residual organic matters.

PubMed

Han, Xiangxin; Jiang, Xiumin; Cui, Zhigang; Liu, Jianguo; Yan, Junwei

2010-03-15

Shale char, formed in retort furnaces of oil shale, is classified as a dangerous waste containing several toxic compounds. In order to retort oil shale to produce shale oil as well as treat shale char efficiently and in an environmentally friendly way, a novel kind of comprehensive utilization system was developed to use oil shale for shale oil production, electricity generation (shale char fired) and the extensive application of oil shale ash. For exploring the combustion properties of shale char further, in this paper organic matters within shale chars obtained under different retorting conditions were extracted and identified using a gas chromatography-mass spectrometry (GC-MS) method. Subsequently, the effects of retorting factors, including retorting temperature, residence time, particle size and heating rate, were analyzed in detail. As a result, a retorting condition with a retorting temperature of 460-490 degrees C, residence time of <40 min and a middle particle size was recommended for both keeping nitrogenous organic matters and aromatic hydrocarbons in shale char and improving the yield and quality of shale oil. In addition, shale char obtained under such retorting condition can also be treated efficiently using a circulating fluidized bed technology with fractional combustion. (c) 2009 Elsevier B.V. All rights reserved.

Temporal dynamics of halogenated organic compounds in Marcellus Shale flowback.

PubMed

Luek, Jenna L; Harir, Mourad; Schmitt-Kopplin, Philippe; Mouser, Paula J; Gonsior, Michael

2018-06-01

The chemistry of hydraulic fracturing fluids and wastewaters is complex and is known to vary by operator, geologic formation, and fluid age. A time series of hydraulic fracturing fluids, flowback fluids, and produced waters was collected from two adjacent Marcellus Shale gas wells for organic chemical composition analyses using ultrahigh resolution mass spectrometry. Hierarchical clustering was used to compare and extract ions related to different fluid ages and many halogenated organic molecular ions were identified in flowback fluids and early produced waters based on exact mass. Iodinated organic compounds were the dominant halogen class in these clusters and were nearly undetectable in hydraulic fracturing fluid prior to injection. The iodinated ions increased in flowback and remained elevated after ten months of well production. We suggest that these trends are mainly driven by dissolved organic matter reacting with reactive halogen species formed abiotically through oxidizing chemical additives applied to the well and biotically via iodide-oxidizing bacteria. Understanding the implications of these identified halogenated organic compounds will require future investigation in to their structures and environmental fate. Copyright © 2018 Elsevier Ltd. All rights reserved.

Organic-rich shale lithofacies geophysical prediction: A case study in the fifth organic-matter-rich interval of Paleogene Hetaoyuan Formation, Biyang Depression

NASA Astrophysics Data System (ADS)

Fei, S.; Xinong, X.

2017-12-01

The fifth organic-matter-rich interval (ORI 5) in the He-third Member of the Paleogene Hetaoyuan Formation is believed to be the main exploration target for shale oil in Biyang Depression, eastern China. An important part of successful explorating and producing shale oil is to identify and predict organic-rich shale lithofacies with different reservoir capacities and rock geomechanical properties, which are related to organic matter content and mineral components. In this study, shale lithofacies are defined by core analysis data, well-logging and seismic data, and the spatial-temporal distribution of various lithologies are predicted qualitatively by seismic attribute technology and quantitatively by geostatistical inversion analysis, and the prediction results are confirmed by the logging data and geological background. ORI 5 is present in lacustrine expanding system tract and can be further divided into four parasequence sets based on the analysis of conventional logs, TOC content and wavelet transform. Calcareous shale, dolomitic shale, argillaceous shale, silty shale and muddy siltstone are defined within ORI 5, and can be separated and predicted in regional-scale by root mean square amplitude (RMS) analysis and wave impedance. The results indicate that in the early expansion system tract, dolomitic shale and calcareous shale widely developed in the study area, and argillaceous shale, silty shale, and muddy siltstone only developed in periphery of deep depression. With the lake level rising, argillaceous shale and calcareous shale are well developed, and argillaceous shale interbeded with silty shale or muddy siltstone developed in deep or semi-deep lake. In the late expansion system tract, argillaceous shale is widely deposited in the deepest depression, calcareous shale presented band distribution in the east of the depression. Actual test results indicate that these methods are feasible to predict the spatial distribution of shale lithofacies.

Introduction to special section: China shale gas and shale oil plays

USGS Publications Warehouse

Jiang, Shu; Zeng, Hongliu; Zhang, Jinchuan; Fishman, Neil; Bai, Baojun; Xiao, Xianming; Zhang, Tongwei; Ellis, Geoffrey S.; Li, Xinjing; Richards-McClung, Bryony; Cai, Dongsheng; Ma, Yongsheng

2015-01-01

Even though China shale gas and shale oil exploration is still in an early stage, limited data are already available. We are pleased to have selected eight high-quality papers from fifteen submitted manuscripts for this timely section on the topic of China shale gas and shale oil plays. These selected papers discuss various subject areas including regional geology, resource potentials, integrated and multidisciplinary characterization of China shale reservoirs (geology, geophysics, geochemistry, and petrophysics) China shale property measurement using new techniques, case studies for marine, lacustrine, and transitional shale deposits in China, and hydraulic fracturing. One paper summarizes the regional geology and different tectonic and depositional settings of the major prospective shale oil and gas plays in China. Four papers concentrate on the geology, geochemistry, reservoir characterization, lithologic heterogeneity, and sweet spot identification in the Silurian Longmaxi marine shale in the Sichuan Basin in southwest China, which is currently the primary focus of shale gas exploration in China. One paper discusses the Ordovician Salgan Shale in the Tarim Basin in northwest China, and two papers focus on the reservoir characterization and hydraulic fracturing of Triassic lacustrine shale in the Ordos Basin in northern China. Each paper discusses a specific area.

CORE-BASED INTEGRATED SEDIMENTOLOGIC, STRATIGRAPHIC, AND GEOCHEMICAL ANALYSIS OF THE OIL SHALE BEARING GREEN RIVER FORMATION, UINTA BASIN, UTAH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lauren P. Birgenheier; Michael D. Vanden Berg,

An integrated detailed sedimentologic, stratigraphic, and geochemical study of Utah's Green River Formation has found that Lake Uinta evolved in three phases (1) a freshwater rising lake phase below the Mahogany zone, (2) an anoxic deep lake phase above the base of the Mahogany zone and (3) a hypersaline lake phase within the middle and upper R-8. This long term lake evolution was driven by tectonic basin development and the balance of sediment and water fill with the neighboring basins, as postulated by models developed from the Greater Green River Basin by Carroll and Bohacs (1999). Early Eocene abrupt global-warmingmore » events may have had significant control on deposition through the amount of sediment production and deposition rates, such that lean zones below the Mahogany zone record hyperthermal events and rich zones record periods between hyperthermals. This type of climatic control on short-term and long-term lake evolution and deposition has been previously overlooked. This geologic history contains key points relevant to oil shale development and engineering design including: (1) Stratigraphic changes in oil shale quality and composition are systematic and can be related to spatial and temporal changes in the depositional environment and basin dynamics. (2) The inorganic mineral matrix of oil shale units changes significantly from clay mineral/dolomite dominated to calcite above the base of the Mahogany zone. This variation may result in significant differences in pyrolysis products and geomechanical properties relevant to development and should be incorporated into engineering experiments. (3) This study includes a region in the Uinta Basin that would be highly prospective for application of in-situ production techniques. Stratigraphic targets for in-situ recovery techniques should extend above and below the Mahogany zone and include the upper R-6 and lower R-8.« less

Dual jets from binary black holes.

PubMed

Palenzuela, Carlos; Lehner, Luis; Liebling, Steven L

2010-08-20

The coalescence of supermassive black holes--a natural outcome when galaxies merge--should produce gravitational waves and would likely be associated with energetic electromagnetic events. We have studied the coalescence of such binary black holes within an external magnetic field produced by the expected circumbinary disk surrounding them. Solving the Einstein equations to describe black holes interacting with surrounding plasma, we present numerical evidence for possible jets driven by these systems. Extending the process described by Blandford and Znajek for a single, spinning black hole, the picture that emerges suggests that the electromagnetic field extracts energy from the orbiting black holes, which ultimately merge and settle into the standard Blandford-Znajek scenario. Emissions along these jets could potentially be observable at large distances.

Assessment of potential shale-oil and shale-gas resources in Silurian shales of Jordan, 2014

USGS Publications Warehouse

Schenk, Christopher J.; Pitman, Janet K.; Charpentier, Ronald R.; Klett, Timothy R.; Tennyson, Marilyn E.; Mercier, Tracey J.; Nelson, Philip H.; Brownfield, Michael E.; Pawlewicz, Mark J.; Wandrey, Craig J.

2014-01-01

Using a geology-based assessment methodology, the U.S. Geological Survey estimated means of 11 million barrels of potential shale-oil and 320 billion cubic feet of shale-gas resources in Silurian shales of Jordan.

43 CFR 3935.10 - Accounting records.

Code of Federal Regulations, 2012 CFR

2012-10-01

... processing plant and retort; (3) Mineral products produced and sold; (4) Shale oil products, shale gas, and... mined or processed and of all products including synthetic petroleum, shale oil, shale gas, and shale..., DEPARTMENT OF THE INTERIOR MINERALS MANAGEMENT (3000) MANAGEMENT OF OIL SHALE EXPLORATION AND LEASES...

43 CFR 3935.10 - Accounting records.

Code of Federal Regulations, 2014 CFR

2014-10-01

... processing plant and retort; (3) Mineral products produced and sold; (4) Shale oil products, shale gas, and... mined or processed and of all products including synthetic petroleum, shale oil, shale gas, and shale..., DEPARTMENT OF THE INTERIOR MINERALS MANAGEMENT (3000) MANAGEMENT OF OIL SHALE EXPLORATION AND LEASES...

43 CFR 3935.10 - Accounting records.

Code of Federal Regulations, 2013 CFR

2013-10-01

... processing plant and retort; (3) Mineral products produced and sold; (4) Shale oil products, shale gas, and... mined or processed and of all products including synthetic petroleum, shale oil, shale gas, and shale..., DEPARTMENT OF THE INTERIOR MINERALS MANAGEMENT (3000) MANAGEMENT OF OIL SHALE EXPLORATION AND LEASES...

Multiple strategies to identify HIV-positive black men who have sex with men and transgender women in New York City: a cross-sectional analysis of recruitment results.

PubMed

Franks, Julie; Mannheimer, Sharon B; Hirsch-Moverman, Yael; Hayes-Larson, Eleanor; Colson, Paul W; Ortega, Hugo; El-Sadr, Wafaa M

2018-03-01

Black men who have sex with men and transgender women are at high risk for HIV infection, but are more likely to be unaware of their infection or not in care for diagnosed HIV compared to other races. Respondent driven sampling has been advanced as a method to reach stigmatized and hidden populations for HIV testing. We compared strategies to recruit black, substance-using men who have sex with men and transgender women to identify newly diagnosed HIV infection, or those previously diagnosed but not in care. The STAR (Seek, Test, and Retain) study (ClinicalTrials.gov NCT01790360) used several recruitment strategies to identify black, substance-using men who have sex with men and transgender women with undiagnosed HIV infection or with previously diagnosed HIV infection but who were not in HIV care. Respondent-driven sampling, community-based recruitment and online advertising were used to recruit participants. Incentivized peer referral was integrated into all recruitment strategies. Participants completed interviewer-administered questionnaires and HIV testing. Demographic and HIV risk-related characteristics and recruitment strategy were summarized and stratified by HIV status. Associations were tested using Pearson's chi-squared, Fisher's exact, and Wilcoxon rank sum tests. Factors associated with HIV-positive diagnosis at p < 0.1 were included in a multivariable logistic regression model. From July 2012 through October 2015, the study enrolled 1929 participants; 96.3% men who have sex with men and 3.7% transgender women. Behavioural risk factors included recent condomless anal sex (55.6%) and recent substance use during sex (73.1%). HIV prevalence was 8.7%. In multivariable analysis, significant associations with HIV infection included being transgender; non-Hispanic black; gay/homosexual orientation; not homeless; and less likely to have insufficient income for necessities. Among recruitment strategies, respondent driven sampling was least effective in identifying HIV-positive participants. Integrating multiple recruitment strategies yielded a large sample of black men who have sex with men and transgender women at substantial risk for HIV. Respondent-driven sampling was less effective than other strategies at identifying men who have sex with men and transgender women with HIV. © 2018 The Authors. Journal of the International AIDS Society published by John Wiley & sons Ltd on behalf of the International AIDS Society.

Can Black Hole Relax Unitarily?

NASA Astrophysics Data System (ADS)

Solodukhin, S. N.

2005-03-01

We review the way the BTZ black hole relaxes back to thermal equilibrium after a small perturbation and how it is seen in the boundary (finite volume) CFT. The unitarity requires the relaxation to be quasi-periodic. It is preserved in the CFT but is not obvious in the case of the semiclassical black hole the relaxation of which is driven by complex quasi-normal modes. We discuss two ways of modifying the semiclassical black hole geometry to maintain unitarity: the (fractal) brick wall and the worm-hole modification. In the latter case the entropy comes out correctly as well.

43 CFR 3935.10 - Accounting records.

Code of Federal Regulations, 2011 CFR

2011-10-01

... processing plant and retort; (3) Mineral products produced and sold; (4) Shale oil products, shale gas, and... mined or processed and of all products including synthetic petroleum, shale oil, shale gas, and shale..., DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) MANAGEMENT OF OIL SHALE EXPLORATION AND LEASES Production...

Review of rare earth element concentrations in oil shales of the Eocene Green River Formation

USGS Publications Warehouse

Birdwell, Justin E.

2012-01-01

Concentrations of the lanthanide series or rare earth elements and yttrium were determined for lacustrine oil shale samples from the Eocene Green River Formation in the Piceance Basin of Colorado and the Uinta Basin of Utah. Unprocessed oil shale, post-pyrolysis (spent) shale, and leached shale samples were examined to determine if oil-shale processing to generate oil or the remediation of retorted shale affects rare earth element concentrations. Results for unprocessed Green River oil shale samples were compared to data published in the literature on reference materials, such as chondritic meteorites, the North American shale composite, marine oil shale samples from two sites in northern Tibet, and mined rare earth element ores from the United States and China. The Green River oil shales had lower rare earth element concentrations (66.3 to 141.3 micrograms per gram, μg g-1) than are typical of material in the upper crust (approximately 170 μg g-1) and were also lower in rare earth elements relative to the North American shale composite (approximately 165 μg g-1). Adjusting for dilution of rare earth elements by organic matter does not account for the total difference between the oil shales and other crustal rocks. Europium anomalies for Green River oil shales from the Piceance Basin were slightly lower than those reported for the North American shale composite and upper crust. When compared to ores currently mined for rare earth elements, the concentrations in Green River oil shales are several orders of magnitude lower. Retorting Green River oil shales led to a slight enrichment of rare earth elements due to removal of organic matter. When concentrations in spent and leached samples were normalized to an original rock basis, concentrations were comparable to those of the raw shale, indicating that rare earth elements are conserved in processed oil shales.

Bacterial physiological diversity in the rhizosphere of range plants in response to retorted shale stress. [Agropyron smithii Rydb; Atriplex canescens (Pursh) Nutt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Metzger, W.C.; Klein, D.A.; Redente, E.F.

1986-10-01

Bacterial populations were isolated from the soil-root interface and root-free regions of Agropyron smithii Rydb. and Atriplex canescens (Pursh) Nutt. grown in soil, retorted shale, or soil over shale. Bacteria isolated from retorted shale exhibited a wider range of tolerance to alkalinity and salinity and decreased growth on amino acid substrates compared with bacteria from soil and soil-over-shale environments. Exoenzyme production was only slightly affected by growth medium treatment. Viable bacterial populations were higher in the rhizosphere and rhizoplane of plants grown in retorted shale than in plants grown in soil or soil over shale. In addition, a greater numbermore » of physiological groups of rhizosphere bacteria was observed in retorted shale, compared with soil alone. Two patterns of community similarity were observed in comparisons of bacteria from soil over shale with those from soil and retorted-shale environments. Root-associated populations from soil over shale had a higher proportion of physiological groups in common with those from the soil control than those from the retorted-shale treatment. However, in non-rhizosphere populations, bacterial groups from soil over shale more closely resembled the physiological groups from retorted shale.« less

Multiple sources of selenium in ancient seafloor hydrothermal systems: Compositional and Se, S, and Pb isotopic evidence from volcanic-hosted and volcanic-sediment-hosted massive sulfide deposits of the Finlayson Lake District, Yukon, Canada

NASA Astrophysics Data System (ADS)

Layton-Matthews, Daniel; Leybourne, Matthew I.; Peter, Jan M.; Scott, Steven D.; Cousens, Brian; Eglington, Bruce M.

2013-09-01

Volcanic-hosted massive sulfide (VHMS) and volcanic-sediment-hosted massive sulfide (VSHMS; i.e., hosted by both volcanic and sedimentary rocks) deposits in the Finlayson Lake District, Yukon, Canada, provide a unique opportunity to study the influence of seafloor and sub-seafloor hydrothermal processes on the formation of Se-poor (GP4F VHMS deposit; 7 ppm Se average), intermediate (Kudz Ze Kayah—KZK VHMS deposit; 200 ppm Se average), and Se-enriched (Wolverine VSHMS deposit; 1100 ppm Se average) mineralization. All three deposits are hosted by mid-Paleozoic (˜360-346 Ma) felsic volcanic rocks, but only the Wolverine deposit has voluminous coeval carbonaceous argillites (black shales) in the host rock package. Here we report the first application of Se isotope analyses to ancient seafloor mineralization and use these data, in conjunction with Pb and S isotope analyses, to better understand the source(s) and depositional process(es) of Se within VHMS and VSHMS systems. The wide range of δ82Se (-10.2‰ to 1.3‰, relative to NIST 3149), δ34S (+2.0‰ to +12.8‰ CDT), and elevated Se contents (up to 5865 ppm) within the Wolverine deposit contrast with the narrower range of δ82Se (-3.8‰ to -0.5‰), δ34S (9.8‰ to 13.0‰), and lower Se contents (200 ppm average) of the KZK deposit. The Wolverine and KZK deposits have similar sulfide depositional histories (i.e., deposition at the seafloor, with concomitant zone refining). The Se in the KZK deposit is magmatic (leaching or degassing) in origin, whereas the Wolverine deposit requires an additional large isotopically negative Se source (i.e. ˜-15‰ δ82Se). The negative δ82Se values for the Wolverine deposit are at the extreme light end for measured terrestrial samples, and the lightest observed for hypogene sulfide minerals, but are within calculated equilibrium values of δ82Se relative to NIST 3149 (˜30‰ at 25 °C between SeO4 and Se2-). We propose that the most negative Se isotope values at the Wolverine deposit record the δ82Se of the Se-source, and that the wide range in δ82Se values results from the combined effects of thermal and chemical degradation and Se-loss from the carbonaceous argillite source to a hydrothermal fluid (including magmatic Se i.e., leached and/or magmatic-hydrothermal) with deposition at or near the paleoseafloor. Pristine unaltered black shales show little variation in δ82Se relative to bulk earth; Se accumulation and fractionation to more negative isotopic values is interpreted to have been produced by post-sediment deposition, but pre-ore stage, reduction of seawater Se within the black shales.

Chemical potential driven phase transition of black holes in anti-de Sitter space

NASA Astrophysics Data System (ADS)

Galante, Mario; Giribet, Gaston; Goya, Andrés; Oliva, Julio

2015-11-01

Einstein-Maxwell theory conformally coupled to a scalar field in D dimensions may exhibit a phase transition at low temperature whose end point is an asymptotically anti-de Sitter black hole with a scalar field profile that is regular everywhere outside and on the horizon. This provides a tractable model to study the phase transition of hairy black holes in anti-de Sitter space in which the backreaction on the geometry can be solved analytically.

Brittleness estimation from seismic measurements in unconventional reservoirs: Application to the Barnett shale

NASA Astrophysics Data System (ADS)

Perez Altimar, Roderick

Brittleness is a key characteristic for effective reservoir stimulation and is mainly controlled by mineralogy in unconventional reservoirs. Unfortunately, there is no universally accepted means of predicting brittleness from measures made in wells or from surface seismic data. Brittleness indices (BI) are based on mineralogy, while brittleness average estimations are based on Young's modulus and Poisson's ratio. I evaluate two of the more popular brittleness estimation techniques and apply them to a Barnett Shale seismic survey in order to estimate its geomechanical properties. Using specialized logging tools such as elemental capture tool, density, and P- and S wave sonic logs calibrated to previous core descriptions and laboratory measurements, I create a survey-specific BI template in Young's modulus versus Poisson's ratio or alternatively lambdarho versus murho space. I use this template to predict BI from elastic parameters computed from surface seismic data, providing a continuous estimate of BI estimate in the Barnett Shale survey. Extracting lambdarho-murho values from microseismic event locations, I compute brittleness index from the template and find that most microsemic events occur in the more brittle part of the reservoir. My template is validated through a suite of microseismic experiments that shows most events occurring in brittle zones, fewer events in the ductile shale, and fewer events still in the limestone fracture barriers. Estimated ultimate recovery (EUR) is an estimate of the expected total production of oil and/or gas for the economic life of a well and is widely used in the evaluation of resource play reserves. In the literature it is possible to find several approaches for forecasting purposes and economic analyses. However, the extension to newer infill wells is somewhat challenging because production forecasts in unconventional reservoirs are a function of both completion effectiveness and reservoir quality. For shale gas reservoirs, completion effectiveness is a function not only of the length of the horizontal wells, but also of the number and size of the hydraulic fracture treatments in a multistage completion. These considerations also include the volume of proppant placed, proppant concentration, total perforation length, and number of clusters, while reservoir quality is dependent on properties such as the spatial variations in permeability, porosity, stress, and mechanical properties. I evaluate parametric methods such as multi-linear regression, and compare it to a non-parameteric ACE to better correlate production to engineering attributes for two datasets in the Haynesville Shale play and the Barnett Shale. I find that the parametric methods are useful for an exploratory analysis of the relationship among several variables and are useful to guide the selection of a more sophisticated parametric functional form, when the underlying functional relationship is unknown. Non-parametric regression, on the other hand, is entirely data-driven and does not rely on a pre-specified functional forms. The transformations generated by the ACE algorithm facilitate the identification of appropriate, and possibly meaningful, functional forms.

Theory-Driven Intervention Improves Calcium Intake, Osteoporosis Knowledge, and Self-Efficacy in Community-Dwelling Older Black Adults

ERIC Educational Resources Information Center

Babatunde, Oyinlola T.; Himburg, Susan P.; Newman, Frederick L.; Campa, Adriana; Dixon, Zisca

2011-01-01

Objective: To assess the effectiveness of an osteoporosis education program to improve calcium intake, knowledge, and self-efficacy in community-dwelling older Black adults. Design: Randomized repeated measures experimental design. Setting: Churches and community-based organizations. Participants: Men and women (n = 110) 50 years old and older…

Paleozoic shale gas resources in the Sichuan Basin, China

USGS Publications Warehouse

Potter, Christopher J.

2018-01-01

The Sichuan Basin, China, is commonly considered to contain the world’s most abundant shale gas resources. Although its Paleozoic marine shales share many basic characteristics with successful United States gas shales, numerous geologic uncertainties exist, and Sichuan Basin shale gas production is nascent. Gas retention was likely compromised by the age of the shale reservoirs, multiple uplifts and orogenies, and migration pathways along unconformities. High thermal maturities raise questions about gas storage potential in lower Paleozoic shales. Given these uncertainties, a new look at Sichuan Basin shale gas resources is advantageous. As part of a systematic effort to quantitatively assess continuous oil and gas resources in priority basins worldwide, the US Geological Survey (USGS) completed an assessment of Paleozoic shale gas in the Sichuan Basin in 2015. Three organic-rich marine Paleozoic shale intervals meet the USGS geologic criteria for quantitative assessment of shale gas resources: the lower Cambrian Qiongzhusi Formation, the uppermost Ordovician Wufeng through lowermost Silurian Longmaxi Formations (currently producing shale gas), and the upper Permian Longtan and Dalong Formations. This study defined geologically based assessment units and calculated probabilistic distributions of technically recoverable shale gas resources using the USGS well productivity–based method. For six assessment units evaluated in 2015, the USGS estimated a mean value of 23.9 tcf (677 billion cubic meters) of undiscovered, technically recoverable shale gas. This result is considerably lower than volumes calculated in previous shale gas assessments of the Sichuan Basin, highlighting a need for caution in this geologically challenging setting.

Stratigraphic contrasts and tectonic relationships between Carboniferous successions in the Trans-Alaska Crustal Transect corridor and adjacent areas, northern Alaska

USGS Publications Warehouse

Dumoulin, Julie A.; Watts, K.F.; Harris, A.G.

1997-01-01

The Carboniferous succession along the Trans-Alaska Crustal Transect (TACT) corridor in the Atigun Gorge area of the central Brooks Range consists of the Kayak Shale (Kinderhookian) and the Lisburne Group (Kinderhookian through Chesterian). The Kayak Shale is at least 210 m thick; it is chiefly black, noncalcareous shale with several limestone beds of pelmatozoan-bryozoan packstone and formed in an open-marine setting. The Lisburne Group is a carbonate rock succession about 650 m thick and consists mainly of skeletal packstone, wackestone, and mudstone which contain locally abundant calcispheres, ostracodes, algae, and sponge spicules; it accumulated largely in a shallow water platform environment with restricted circulation. This restriction was probably produced by a coeval belt of skeletal sand shoals recognized 70 km to the west in the Shainin Lake area. Significant and apparently abrupt shifts in the age and lithofacies of Carboniferous strata occur across the central and eastern Brooks Range. These shifts are most marked in a zone roughly coincident with what is interpreted by many workers to be the leading edge of the Endicott Mountains allochthon. Notable lithologic contrasts are also observed, however, between sections in the northern and southern parts of the Endicott Mountains allochthon. This suggests that considerable tectonic shortening has taken place within the allochthon, as well as between it and parautochthonous rocks to the northeast. The Carboniferous section near Mount Doonerak is more similar in age and lithofacies to coeval sections in the central Brooks Range that are considered allochthonous than to parautochthonous sections to the northeast. Copyright 1997 by the American Geophysical Union.

Detrital and oceanic dysoxia influence on OAE2 sediment geochemistry from Tarfaya, SW Morocco

NASA Astrophysics Data System (ADS)

Turgeon, S. C.; Kolonic, S.; Brumsack, H.-J.; Wagner, T.

2003-04-01

The Cretaceous "greenhouse" world's stratigraphic record is punctuated by several important organic-rich intervals representing quasi-global "Oceanic Anoxic Events" (OAEs). This study focuses on sediments from Tarfaya in SW Morocco deposited during the Cenomanian-Turonian Boundary Event (CTBE or OAE2 at 93.5 Ma). These sediments consist of distinctly laminated, carbonate-rich black shales alternating with lighter coloured structureless intervals and sporadic chert lenses. Sediments from three sites representing proximal to distal settings were studied. Samples were analysed for Ctot, Corg, Stot, as well as several major-, minor- and trace elements using XRF and ICP-MS. These sediments are characterised by high Corg, Stot, and CaCO3 contents and consist of a simple two component mixing system ("average shale"-CaCO3). Major element concentrations are low, except for Ca and P, owing in part to the carbonate dilution effect. Most elements plot along "average shale" lines. Elements such as Si, Ti, Fe, K, Rb, and Zr show positive relationships with Al2O3, pointing to homogeneous source area material. Several Al-normalised elements (As, Ba, Cr, Cu, Ni, Sr, U, V, Y, Zn), many of them redox-sensitive or sulphide-residing, are enriched in the sediments indicating an oxygen-depleted environment and potential availability of hydrogen sulfide in the water column at the time of deposition. High Zn concentrations suggest increased submarine volcanism and/or hydrothermal activity during this time interval. High Ba concentrations are possibly indicative of high regional paleoproductivity, which is further supported by the elevated P concentrations hinting at nutrient availability. Basinward trends in the geochemical distribution of some elements are apparent and probably reflect the decreasing influence of terrestrial sediments away from the shoreline.

FTIR absorption indices for thermal maturity in comparison with vitrinite reflectance R0 in type-II kerogens from Devonian black shales

USGS Publications Warehouse

Lis, G.P.; Mastalerz, Maria; Schimmelmann, A.; Lewan, M.D.; Stankiewicz, B.A.

2005-01-01

FTIR absorbance signals in kerogens and macerals were evaluated as indices for thermal maturity. Two sets of naturally matured type-II kerogens from the New Albany Shale (Illinois Basin) and the Exshaw Formation (Western Canada Sedimentary Basin) and kerogens from hydrous pyrolysis artificial maturation of the New Albany Shale were characterized by FTIR. Good correlation was observed between the aromatic/aliphatic absorption ratio and vitrinite reflectance R 0. FTIR parameters are especially valuable for determining the degree of maturity of marine source rocks lacking vitrinite. With increasing maturity, FTIR spectra express four trends: (i) an increase in the absorption of aromatic bands, (ii) a decrease in the absorption of aliphatic bands, (iii) a loss of oxygenated groups (carbonyl and carboxyl), and (iv) an initial decrease in the CH2/CH3 ratio that is not apparent at higher maturity in naturally matured samples, but is observed throughout increasing R0 in artificially matured samples. The difference in the CH2/CH 3 ratio in samples from natural and artificial maturation at higher maturity indicates that short-term artificial maturation at high temperatures is not fully equivalent to slow geologic maturation at lower temperatures. With increasing R0, the (carboxyl + carbonyl)/aromatic carbon ratio generally decreases, except that kerogens from the Exshaw Formation and from hydrous pyrolysis experiments express an intermittent slight increase at medium maturity. FTIR-derived aromaticities correlate well with R0, although some uncertainty is due to the dependence of FTIR parameters on the maceral composition of kerogen whereas R0 is solely dependent on vitrinite. ?? 2005 Elsevier Ltd. All rights reserved.

Factors controlling localization of uranium deposits in the Dakota Sandstone, Gallup and Ambrosia Lake mining districts, McKinley County, New Mexico

USGS Publications Warehouse

Pierson, Charles Thomas; Green, Morris W.

1977-01-01

Geologic studies were made at all of the uranium mines and prospects in the Dakota Sandstone of Early(?) and Late Cretaceous age in the Gallup mining district, McKinley County, New Mexico. Dakota mines in the adjacent Ambrosia Lake mining district were visited briefly for comparative purposes. Mines in the eastern part of the Gallup district, and in the Ambrosia Lake district, are on the Chaco slope of the southern San Juan Basin in strata which dip gently northward toward the central part of the basin. Mines in the western part of the Gallup district are along the Gallup hogback (Nutria monocline) in strata which dip steeply westward into the Gallup sag. Geologic factors which controlled formation of the uranium deposits in the Dakota Sandstone are: (1) a source of uranium, believed to be uranium deposits of the underlying Morrison Formation of Late Jurassic age; (2) the accessibility to the Dakota of uranium-bearing solutions from the Morrison; (3) the presence in the Dakota of permeable sandstone beds overlain by impermeable carbonaceous shale beds; and (4) the occurrence within the permeable Dakota sandstone beds of carbonaceous reducing material as bedding-plane laminae, or as pockets of carbonaceous trash. Most of the Dakota uranium deposits are found in the lower part of the formation in marginal-marine distributary-channel sandstones which were deposited in the backshore environment. However, the Hogback no. 4 (Hyde) Mine (Gallup district) occurs in sandy paludal shale of the backshore environment, and another deposit, the Silver Spur (Ambrosia Lake district), is found in what is interpreted to be a massive beach or barrier-bar sandstone of the foreshore environment in the upper part of the Dakota. The sedimentary depositional environment most favorable for the accumulation of uranium is that of backshore areas lateral to main distributary channels, where levee, splay, and some distributary-channel sandstones intertongue with gray carbonaceous shales and siltstones of the well-drained swamp environment. Deposits of black carbonaceous shale which were formed in the poorly drained swamp deposits of the interfluve area are not favorable host rocks for uranium. The depositional energy levels of the various environments in which the sandstone and shale beds of the Dakota were deposited govern the relative favorability of the strata as uranium host rocks. In the report area, uranium usually occurs in carbonaceous sandstone deposited under low- to medium-energy fluvial conditions within distributary channels. A prerequisite, however, is that such sandstone be overlain by impermeable carbonaceous shale beds. Low- to medium-energy fluvial conditions result in the deposition of sandstone beds having detrital carbonaceous material distributed in laminae or in trash pockets on bedding planes. The carbonaceous laminae and trash pockets provide the necessary reductant to cause precipitation of uranium from solution. High-energy fluvial conditions result in the deposition of sandstones having little or no carbonaceous material included to provide a reductant. Very low energy swampy conditions result in carbonaceous shale deposits, which are generally barren of uranium because of their relative impermeability to migrating uranium-bearing solutions.

Method of operating an oil shale kiln

DOEpatents

Reeves, Adam A.

1978-05-23

Continuously determining the bulk density of raw and retorted oil shale, the specific gravity of the raw oil shale and the richness of the raw oil shale provides accurate means to control process variables of the retorting of oil shale, predicting oil production, determining mining strategy, and aids in controlling shale placement in the kiln for the retorting.

Estimation of Potential Shale Gas Yield Amount and Land Degradation in China by Landcover Distribution regarding Water-Food-Energy and Forest

NASA Astrophysics Data System (ADS)

Kim, N.; Heo, S.; Lim, C. H.; Lee, W. K.

2017-12-01

Shale gas is gain attention due to the tremendous reserves beneath the earth. The two known high reservoirs are located in United States and China. According to U.S Energy Information Administration China have estimated 7,299 trillion cubic feet of recoverable shale gas and placed as world first reservoir. United States had 665 trillion cubic feet for the shale gas reservoir and placed fourth. Unlike the traditional fossil fuel, spatial distribution of shale gas is considered to be widely spread and the reserved amount and location make the resource as energy source for the next generation. United States dramatically increased the shale gas production. For instance, shale gas production composes more than 50% of total natural gas production whereas China and Canada shale gas produce very small amount of the shale gas. According to U.S Energy Information Administration's report, in 2014 United States produced shale gas almost 40 billion cubic feet per day but China only produced 0.25 billion cubic feet per day. Recently, China's policy had changed to decrease the coal powerplants to reduce the air pollution and the energy stress in China is keep increasing. Shale gas produce less air pollution while producing energy and considered to be clean energy source. Considering the situation of China and characteristics of shale gas, soon the demand of shale gas will increase in China. United States invested 71.7 billion dollars in 2013 but it Chinese government is only proceeding fundamental investment due to land degradation, limited water resources, geological location of the reservoirs.In this study, firstly we reviewed the current system and technology of shale gas extraction such as hydraulic Fracturing. Secondly, listed the possible environmental damages, land degradations, and resource demands for the shale gas extraction. Thirdly, invested the potential shale gas extraction amount in China based on the location of shale gas reservoirs and limited resources for the gas extraction. Fourthly, invested the potential land degradation on agricultural, surface water, and forest in developing shale gas extraction scenario. In conclusion, we suggested possible environmental damages and social impacts from shale gas extraction in China.

Talaromyces sayulitensis, Acidiella bohemica and Penicillium citrinum in Brazilian oil shale by-products.

PubMed

de Goes, Kelly C G P; da Silva, Josué J; Lovato, Gisele M; Iamanaka, Beatriz T; Massi, Fernanda P; Andrade, Diva S

2017-12-01

Fine shale particles and retorted shale are waste products generated during the oil shale retorting process. These by-products are small fragments of mined shale rock, are high in silicon and also contain organic matter, micronutrients, hydrocarbons and other elements. The aims of this study were to isolate and to evaluate fungal diversity present in fine shale particles and retorted shale samples collected at the Schist Industrialization Business Unit (Six)-Petrobras in São Mateus do Sul, State of Paraná, Brazil. Combining morphology and internal transcribed spacer (ITS) sequence, a total of seven fungal genera were identified, including Acidiella, Aspergillus, Cladosporium, Ochroconis, Penicillium, Talaromyces and Trichoderma. Acidiella was the most predominant genus found in the samples of fine shale particles, which are a highly acidic substrate (pH 2.4-3.6), while Talaromyces was the main genus in retorted shale (pH 5.20-6.20). Talaromyces sayulitensis was the species most frequently found in retorted shale, and Acidiella bohemica in fine shale particles. The presence of T. sayulitensis, T. diversus and T. stolli in oil shale is described herein for the first time. In conclusion, we have described for the first time a snapshot of the diversity of filamentous fungi colonizing solid oil shale by-products from the Irati Formation in Brazil.

Contact metamorphism of black shales: global carbon cycle and climate perturbations

NASA Astrophysics Data System (ADS)

Aarnes, I.; Svensen, H.; Polteau, S.; Connolly, J. A. D.; Planke, S.

2009-04-01

There is an increasing interest in improving the understanding of past climate changes, as it can lead to a better understanding of future challenges related to global warming and anthropogenic release of greenhouse gases. The formation of Large Igneous Provinces (LIPs) and sill intrusions in volcanic basins correlate with global warming events and mass extinctions, e.g. the Karoo Basin, South Africa (~183 Ma), the Møre and Vøring Basins offshore Norway (~55 Ma), and the Tunguska Basin, Siberia (~252 Ma). The proxy records from these events suggest that rapid release of large amounts of isotopically 13C-depleted greenhouse gases (CO2 and methane) to the atmosphere. Organic matter stored in sedimentary rocks (e.g. black shale) represents a major carbon source. Large volumes of greenhouse gases may form by contact metamorphism of organic-rich sediments around sill intrusions associated with LIPs. The organic-rich Ecca Group forms the base of the Karoo sedimentary succession and contains thousands of degassing pipe structures rooted in contact aureoles around sill intrusions. Numerical and analogue modelling show that these piercement structures form during violent eruptions releasing the overpressure driven by dehydration and devolatilization metamorphic reactions. In this study we evaluate the aureole processes numerically in order to constrain the amount of gases formed in contact aureoles around sill intrusions, and the isotopic composition of those gases. The total organic carbon (TOC) in the shale and the intrusion thickness are the most important parameters controlling the amount of carbon gas that can trigger pipe formation and release into the atmosphere. . We model thermal cracking using a general kinetic approach, while dehydration reactions are modeled under the assumption of thermodynamic equilibrium. The theoretical approach is tested against borehole data from the Karoo Basin in South Africa (geochemical analyses, Rock-Eval pyrolysis, TOC, vitrinite reflectance and stable isotopes). Decreasing TOC content and increasing vitrinite reflectance with decreasing distance to the intrusive contact are signatures of thermogenic hydrocarbon formation. During high temperature metamorphism, formation of carbon gases is preferred over liquid hydrocarbons. However, only limited isotopic fractionation is occurring in the released carbon gases during increasing temperature. Increasing veining towards the contact of a 10 meter sill suggests that hydrocarbon formation in organic-rich aureoles leads to pressure buildup and fracturing of the aureole, even with small volumes. Our numerical model also shows that sill thicknesses in the order of 100 m are necessary to produce the pressure buildup in the contact aureole and subsequent venting. In addition, mineral dehydration and thermal stresses contribute to pore fluid pressure increase. We use our numerical model to predict the amount of fluids produced as response to thin (~10 meter) and thick (~100 meter) sills. The model provides us with important estimates of rate and duration of gas formation. The time-scale of subsurface gas formation is well within the time scale indicated by the proxy data. Results from isotope compositions demonstrate that the 2.8t/m2 of organic carbon escapes the contact aureole during devolatilization processes involving the generation of light carbon gases. The calculated isotopic composition of the carbon released is similar whether using the batch devolatilization or the Rayleigh distillation model, and ranges from the background values to 1-2 permil lighter values with decreasing distance from the contact. The extrapolation of our results to the portion of the sedimentary basin intruded by magma suggests that contact metamorphism of organic-rich sediments triggered a potential release of between 2000 to 10000 Gt of isotopically light carbon gas to the atmosphere. In conclusion, the amount and composition of methane that can be produced and vented from contact aureoles in the Karoo Basin during the Toarcian is within the same order of magnitude as required to explain global carbon isotope excursion and hence global warming.

Reservoir characteristics of coal-shale sedimentary sequence in coal-bearing strata and their implications for the accumulation of unconventional gas

NASA Astrophysics Data System (ADS)

Wang, Yang; Zhu, Yanming; Liu, Yu; Chen, Shangbin

2018-04-01

Shale gas and coalbed methane (CBM) are both considered unconventional natural gas and are becoming increasingly important energy resources. In coal-bearing strata, coal and shale are vertically adjacent as coal and shale are continuously deposited. Research on the reservoir characteristics of coal-shale sedimentary sequences is important for CBM and coal-bearing shale gas exploration. In this study, a total of 71 samples were collected, including coal samples (total organic carbon (TOC) content >40%), carbonaceous shale samples (TOC content: 6%-10%), and shale samples (TOC content <6%). Combining techniques of field emission scanning electron microscopy (FE-SEM), x-ray diffraction, high-pressure mercury intrusion porosimetry, and methane adsorption, experiments were employed to characterize unconventional gas reservoirs in coal-bearing strata. The results indicate that in the coal-shale sedimentary sequence, the proportion of shale is the highest at 74% and that of carbonaceous shale and coal are 14% and 12%, respectively. The porosity of all measured samples demonstrates a good positive relationship with TOC content. Clay and quartz also have a great effect on the porosity of shale samples. According to the FE-SEM image technique, nanoscale pores in the organic matter of coal samples are much more developed compared with shale samples. For shales with low TOC, inorganic minerals provide more pores than organic matter. In addition, TOC content has a positive relationship with methane adsorption capacity, and the adsorption capacity of coal samples is more sensitive than the shale samples to temperature.

Methods for minimizing plastic flow of oil shale during in situ retorting

DOEpatents

Lewis, Arthur E.; Mallon, Richard G.

1978-01-01

In an in situ oil shale retorting process, plastic flow of hot rubblized oil shale is minimized by injecting carbon dioxide and water into spent shale above the retorting zone. These gases react chemically with the mineral constituents of the spent shale to form a cement-like material which binds the individual shale particles together and bonds the consolidated mass to the wall of the retort. This relieves the weight burden borne by the hot shale below the retorting zone and thereby minimizes plastic flow in the hot shale. At least a portion of the required carbon dioxide and water can be supplied by recycled product gases.

Porosity evolution during weathering of Marcellus shale

NASA Astrophysics Data System (ADS)

Gu, X.; Brantley, S.

2017-12-01

Weathering is an important process that continuously converts rock to regolith. Shale weathering is of particular interest because 1) shale covers about 25% of continental land mass; 2) recent development of unconventional shale gas generates large volumes of rock cuttings. When cuttings are exposed at earth's surface, they can release toxic trace elements during weathering. In this study, we investigated the evolution of pore structures and mineral transformation in an outcrop of Marcellus shale - one of the biggest gas shale play in North America - at Frankstown, Pennsylvania. A combination of neutron scattering and imaging was used to characterize the pore structures from nm to mm. The weathering profile of Marcellus shale was also compared to the well-studied Rose Hill shale from the Susquehanna Shale Hills critical zone observatory nearby. This latter shale has a similar mineral composition as Marcellus shale but much lower concentrations of pyrite and OC. The Marcellus shale formation in outcrop overlies a layer of carbonate at 10 m below land surface with low porosity (<3%). All the shale samples above the carbonate layer are almost completely depleted in carbonate, plagioclase, chlorite and pyrite. The porosities in the weathered Marcellus shale are twice as high as in protolith. The pore size distribution exhibits a broad peak for pores of size in the range of 10s of microns, likely due to the loss of OC and/or dissolution of carbonate during weathering. In the nearby Rose Hill shale, the pyrite and carbonate are sharply depleted close to the water table ( 15-20 m at ridgetop); while chlorite and plagioclase are gradually depleted toward the land surface. The greater weathering extent of silicates in the Marcellus shale despite the similarity in climate and erosion rate in these two neighboring locations is attributed to 1) the formation of micron-size pores increases the infiltration rate into weathered Marcellus shale and therefore promotes mineral weathering; 2) the pyrite/carbonate ratio is higher in the Marcellus shale than in Rose Hill shale, and thus excess acidity generated through pyrite oxidation enhances the dissolution of silicates. We seek to use these and other observations to develop a global model for shale weathering that incorporates both mineral composition and porosity change.

Clay mineral continental amplifier for marine carbon sequestration in a greenhouse ocean.

PubMed

Kennedy, Martin J; Wagner, Thomas

2011-06-14

The majority of carbon sequestration at the Earth's surface occurs in marine continental margin settings within fine-grained sediments whose mineral properties are a function of continental climatic conditions. We report very high mineral surface area (MSA) values of 300 and 570 m(2) g in Late Cretaceous black shales from Ocean Drilling Program site 959 of the Deep Ivorian Basin that vary on subcentennial time scales corresponding with abrupt increases from approximately 3 to approximately 18% total organic carbon (TOC). The observed MSA changes with TOC across multiple scales of variability and on a sample-by-sample basis (centimeter scale), provides a rigorous test of a hypothesized influence on organic carbon burial by detrital clay mineral controlled MSA. Changes in TOC also correspond with geochemical and sedimentological evidence for water column anoxia. Bioturbated intervals show a lower organic carbon loading on mineral surface area of 0.1 mg-OC m(-2) when compared to 0.4 mg-OC m(-2) for laminated and sulfidic sediments. Although either anoxia or mineral surface protection may be capable of producing TOC of < 5%, when brought together they produced the very high TOC (10-18%) apparent in these sediments. This nonlinear response in carbon burial resulted from minor precession-driven changes of continental climate influencing clay mineral properties and runoff from the African continent. This study identifies a previously unrecognized land-sea connection among continental weathering, clay mineral production, and anoxia and a nonlinear effect on marine carbon sequestration during the Coniacian-Santonian Oceanic Anoxic Event 3 in the tropical eastern Atlantic.

Mongolian Oil Shale, hosted in Mesozoic Sedimentary Basins

NASA Astrophysics Data System (ADS)

Bat-Orshikh, E.; Lee, I.; Norov, B.; Batsaikhan, M.

2016-12-01

Mongolia contains several Mesozoic sedimentary basins, which filled >2000 m thick non-marine successions. Late Triassic-Middle Jurassic foreland basins were formed under compression tectonic conditions, whereas Late Jurassic-Early Cretaceous rift valleys were formed through extension tectonics. Also, large areas of China were affected by these tectonic events. The sedimentary basins in China host prolific petroleum and oil shale resources. Similarly, Mongolian basins contain hundreds meter thick oil shale as well as oil fields. However, petroleum system and oil shale geology of Mongolia remain not well known due to lack of survey. Mongolian oil shale deposits and occurrences, hosted in Middle Jurassic and Lower Cretaceous units, are classified into thirteen oil shale-bearing basins, of which oil shale resources were estimated to be 787 Bt. Jurassic oil shale has been identified in central Mongolia, while Lower Cretaceous oil shale is distributed in eastern Mongolia. Lithologically, Jurassic and Cretaceous oil shale-bearing units (up to 700 m thick) are similar, composed mainly of alternating beds of oil shale, dolomotic marl, siltstone and sandstone, representing lacustrine facies. Both Jurassic and Cretaceous oil shales are characterized by Type I kerogen with high TOC contents, up to 35.6% and low sulfur contents ranging from 0.1% to 1.5%. Moreover, S2 values of oil shales are up to 146 kg/t. The numbers indicate that the oil shales are high quality, oil prone source rocks. The Tmax values of samples range from 410 to 447, suggesting immature to early oil window maturity levels. PI values are consistent with this interpretation, ranging from 0.01 to 0.03. According to bulk geochemistry data, Jurassic and Cretaceous oil shales are identical, high quality petroleum source rocks. However, previous studies indicate that known oil fields in Eastern Mongolia were originated from Lower Cretaceous oil shales. Thus, further detailed studies on Jurassic oil shale and its petroleum potential are required.

Comparison of formation mechanism of fresh-water and salt-water lacustrine organic-rich shale

NASA Astrophysics Data System (ADS)

Lin, Senhu

2017-04-01

Based on the core and thin section observation, major, trace and rare earth elements test, carbon and oxygen isotopes content analysis and other geochemical methods, a detailed study was performed on formation mechanism of lacustrine organic-rich shale by taking the middle Permian salt-water shale in Zhungaer Basin and upper Triassic fresh-water shale in Ordos Basin as the research target. The results show that, the middle Permian salt-water shale was overall deposited in hot and dry climate. Long-term reductive environment and high biological abundance due to elevated temperature provides favorable conditions for formation and preservation of organic-rich shale. Within certain limits, the hotter climate, the organic-richer shale formed. These organic-rich shale was typically distributed in the area where palaeosalinity is relatively high. However, during the upper Triassic at Ordos Basin, organic-rich shale was formed in warm and moist environment. What's more, if the temperature, salinity or water depth rises, the TOC in shale decreases. In other words, relatively low temperature and salinity, stable lake level and strong reducing conditions benefits organic-rich shale deposits in fresh water. In this sense, looking for high-TOC shale in lacustrine basin needs to follow different rules depends on the palaeoclimate and palaeoenvironment during sedimentary period. There is reason to believe that the some other factors can also have significant impact on formation mechanism of organic-rich shale, which increases the complexity of shale oil and gas prediction.

Geology of uranium in the Chadron area, Nebraska and South Dakota

USGS Publications Warehouse

Dunham, Robert Jacob

1961-01-01

The Chadron area covers 375 square miles about 25 miles southeast of the Black Hills. Recurrent mild tectonic activity and erosion on the Chadron arch, a compound anticlinal uplift of regional extent, exposed 1900 feet of Upper Cretaceous rocks, mostly marine shale containing pyrite and organic matter, and 600 feet of Oligocene and Miocene rocks, mostly terrestrial fine-grained sediment containing volcanic ash. Each Cretaceous formation truncated by the sub-Oligocene unconformity is stained yellow and red, leached, kaolinized, and otherwise altered to depths as great as 55 feet. The composition and profile of the altered material indicate lateritic soil; indirect evidence indicates Eocene(?) age. In a belt through the central part of the area, the Brule formation of Oligocene age is a sequence of bedded gypsum, clay, dolomite, and limestone more than 300 feet thick. Uranium in Cretaceous shale in 58 samples averages 0.002 percent, ten times the average for the earths crust. Association with pyrite and organic matter indicates low valency. The uranium probably is syngenetic or nearly so. Uranium in Eocene(?) soil in 43 samples averages 0.054 percent, ranging up to 1.12 percent. The upper part of the soil is depleted in uranium; enriched masses in the basal part of the soil consist of remnants of bedrock shale and are restricted to the highest reaches of the ancient oxidation-reduction interface. The uranium is probably in the from of a low-valent mineral, perhaps uraninite. Modern weathering of Cretaceous shale is capable of releasing as much as 0.780 ppm uranium to water. Eocene(?) weathering probably caused enrichment of the ancient soil through 1) leaching of Cretaceous shale, 2) downward migration of uranyl complex ions, and 3) reduction of hydrogen sulfide at the water table. Uranium minerals occur in the basal 25 feet of the gypsum facies of the Brule formation at the two localities where the gypsum is carbonaceous; 16 samples average 0.066 percent uranium and range up to 0.43 percent. Elsewhere uranium in dolomite and limestone in the basal 25 feet of the gypsum facies in 10 samples averages 0.007 percent, ranging up to 0.12 percent. Localization of the uranium at the base of the gypsum facies suggests downward moving waters; indirect evidence that the water from which the gypsum was deposited was highly alkaline suggests that the uranium was leached from volcanic ash in Oligocene time.

Assessment of undiscovered shale gas and shale oil resources in the Mississippian Barnett Shale, Bend Arch–Fort Worth Basin Province, North-Central Texas

USGS Publications Warehouse

Marra, Kristen R.; Charpentier, Ronald R.; Schenk, Christopher J.; Lewan, Michael D.; Leathers-Miller, Heidi M.; Klett, Timothy R.; Gaswirth, Stephanie B.; Le, Phuong A.; Mercier, Tracey J.; Pitman, Janet K.; Tennyson, Marilyn E.

2015-12-17

Using a geology-based assessment methodology, the U.S. Geological Survey estimated mean volumes of 53 trillion cubic feet of shale gas, 172 million barrels of shale oil, and 176 million barrels of natural gas liquids in the Barnett Shale of the Bend Arch–Fort Worth Basin Province of Texas.

Pore-Scale Simulation and Sensitivity Analysis of Apparent Gas Permeability in Shale Matrix

PubMed Central

Zhang, Pengwei; Hu, Liming; Meegoda, Jay N.

2017-01-01

Extremely low permeability due to nano-scale pores is a distinctive feature of gas transport in a shale matrix. The permeability of shale depends on pore pressure, porosity, pore throat size and gas type. The pore network model is a practical way to explain the macro flow behavior of porous media from a microscopic point of view. In this research, gas flow in a shale matrix is simulated using a previously developed three-dimensional pore network model that includes typical bimodal pore size distribution, anisotropy and low connectivity of the pore structure in shale. The apparent gas permeability of shale matrix was calculated under different reservoir pressures corresponding to different gas exploitation stages. Results indicate that gas permeability is strongly related to reservoir gas pressure, and hence the apparent permeability is not a unique value during the shale gas exploitation, and simulations suggested that a constant permeability for continuum-scale simulation is not accurate. Hence, the reservoir pressures of different shale gas exploitations should be considered. In addition, a sensitivity analysis was also performed to determine the contributions to apparent permeability of a shale matrix from petro-physical properties of shale such as pore throat size and porosity. Finally, the impact of connectivity of nano-scale pores on shale gas flux was analyzed. These results would provide an insight into understanding nano/micro scale flows of shale gas in the shale matrix. PMID:28772465

Pore-Scale Simulation and Sensitivity Analysis of Apparent Gas Permeability in Shale Matrix.

PubMed

Zhang, Pengwei; Hu, Liming; Meegoda, Jay N

2017-01-25

Extremely low permeability due to nano-scale pores is a distinctive feature of gas transport in a shale matrix. The permeability of shale depends on pore pressure, porosity, pore throat size and gas type. The pore network model is a practical way to explain the macro flow behavior of porous media from a microscopic point of view. In this research, gas flow in a shale matrix is simulated using a previously developed three-dimensional pore network model that includes typical bimodal pore size distribution, anisotropy and low connectivity of the pore structure in shale. The apparent gas permeability of shale matrix was calculated under different reservoir pressures corresponding to different gas exploitation stages. Results indicate that gas permeability is strongly related to reservoir gas pressure, and hence the apparent permeability is not a unique value during the shale gas exploitation, and simulations suggested that a constant permeability for continuum-scale simulation is not accurate. Hence, the reservoir pressures of different shale gas exploitations should be considered. In addition, a sensitivity analysis was also performed to determine the contributions to apparent permeability of a shale matrix from petro-physical properties of shale such as pore throat size and porosity. Finally, the impact of connectivity of nano-scale pores on shale gas flux was analyzed. These results would provide an insight into understanding nano/micro scale flows of shale gas in the shale matrix.

Combuston method of oil shale retorting

DOEpatents

Jones, Jr., John B.; Reeves, Adam A.

1977-08-16

A gravity flow, vertical bed of crushed oil shale having a two level injection of air and a three level injection of non-oxygenous gas and an internal combustion of at least residual carbon on the retorted shale. The injection of air and gas is carefully controlled in relation to the mass flow rate of the shale to control the temperature of pyrolysis zone, producing a maximum conversion of the organic content of the shale to a liquid shale oil. The parameters of the operation provides an economical and highly efficient shale oil production.

Urban Preparation: Young Black Men Moving from Chicago's South Side to Success in Higher Education

ERIC Educational Resources Information Center

Warren, Chezare A.

2017-01-01

Chezare A. Warren chronicles the transition of a cohort of young Black males from Urban Prep Charter Academy for Young Men to their early experiences in higher education. A rich and closely observed account of a mission-driven school and its students, "Urban Preparation" makes a significant contribution to our understanding of how young…

Characterization of oil shale, isolated kerogen, and post-pyrolysis residues using advanced 13 solid-state nuclear magnetic resonance spectroscopy

USGS Publications Warehouse

Cao, Xiaoyan; Birdwell, Justin E.; Chappell, Mark A.; Li, Yuan; Pignatello, Joseph J.; Mao, Jingdong

2013-01-01

Characterization of oil shale kerogen and organic residues remaining in postpyrolysis spent shale is critical to the understanding of the oil generation process and approaches to dealing with issues related to spent shale. The chemical structure of organic matter in raw oil shale and spent shale samples was examined in this study using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Oil shale was collected from Mahogany zone outcrops in the Piceance Basin. Five samples were analyzed: (1) raw oil shale, (2) isolated kerogen, (3) oil shale extracted with chloroform, (4) oil shale retorted in an open system at 500°C to mimic surface retorting, and (5) oil shale retorted in a closed system at 360°C to simulate in-situ retorting. The NMR methods applied included quantitative direct polarization with magic-angle spinning at 13 kHz, cross polarization with total sideband suppression, dipolar dephasing, CHn selection, 13C chemical shift anisotropy filtering, and 1H-13C long-range recoupled dipolar dephasing. The NMR results showed that, relative to the raw oil shale, (1) bitumen extraction and kerogen isolation by demineralization removed some oxygen-containing and alkyl moieties; (2) unpyrolyzed samples had low aromatic condensation; (3) oil shale pyrolysis removed aliphatic moieties, leaving behind residues enriched in aromatic carbon; and (4) oil shale retorted in an open system at 500°C contained larger aromatic clusters and more protonated aromatic moieties than oil shale retorted in a closed system at 360°C, which contained more total aromatic carbon with a wide range of cluster sizes.

Process for oil shale retorting

DOEpatents

Jones, John B.; Kunchal, S. Kumar

1981-10-27

Particulate oil shale is subjected to a pyrolysis with a hot, non-oxygenous gas in a pyrolysis vessel, with the products of the pyrolysis of the shale contained kerogen being withdrawn as an entrained mist of shale oil droplets in a gas for a separation of the liquid from the gas. Hot retorted shale withdrawn from the pyrolysis vessel is treated in a separate container with an oxygenous gas so as to provide combustion of residual carbon retained on the shale, producing a high temperature gas for the production of some steam and for heating the non-oxygenous gas used in the oil shale retorting process in the first vessel. The net energy recovery includes essentially complete recovery of the organic hydrocarbon material in the oil shale as a liquid shale oil, a high BTU gas, and high temperature steam.

Worldwide occurrences of arsenic in ground water

USGS Publications Warehouse

Nordstrom, D. Kirk

2002-01-01

Numerous aquifers worldwide carry soluble arsenic at concentrations greater than the World Health Organization--and U.S. Environmental Protection Agency--recommended drinking water standard of 10 mg per liter. Sources include both natural (black shales, young sediments with low flushing rates, gold mineralization, and geothermal environments) and anthropogenic (mining activities, livestock feed additives, pesticides, and arsenic trioxide wastes and stockpiles). Increased solubility and mobility of arsenic is promoted by high pH (>8.5), competing oxyanions, and reducing conditions. In this Policy Forum, Nordstrom argues that human health risks from arsenic in ground water can be minimized by incorporating hydrogeochemical knowledge into water management decisions and by more careful monitoring for arsenic in geologically high-risk areas.

Review of Emerging Resources: U.S. Shale Gas and Shale Oil Plays

EIA Publications

2011-01-01

To gain a better understanding of the potential U.S. domestic shale gas and shale oil resources, the Energy Information Administration (EIA) commissioned INTEK, Inc. to develop an assessment of onshore lower 48 states technically recoverable shale gas and shale oil resources. This paper briefly describes the scope, methodology, and key results of the report and discusses the key assumptions that underlie the results.

Carbon sequestration in depleted oil shale deposits

DOEpatents

Burnham, Alan K; Carroll, Susan A

2014-12-02

A method and apparatus are described for sequestering carbon dioxide underground by mineralizing the carbon dioxide with coinjected fluids and minerals remaining from the extraction shale oil. In one embodiment, the oil shale of an illite-rich oil shale is heated to pyrolyze the shale underground, and carbon dioxide is provided to the remaining depleted oil shale while at an elevated temperature. Conditions are sufficient to mineralize the carbon dioxide.

Wet separation processes as method to separate limestone and oil shale

NASA Astrophysics Data System (ADS)

Nurme, Martin; Karu, Veiko

2015-04-01

Biggest oil shale industry is located in Estonia. Oil shale usage is mainly for electricity generation, shale oil generation and cement production. All these processes need certain quality oil shale. Oil shale seam have interlayer limestone layers. To use oil shale in production, it is needed to separate oil shale and limestone. A key challenge is find separation process when we can get the best quality for all product types. In oil shale separation typically has been used heavy media separation process. There are tested also different types of separation processes before: wet separation, pneumatic separation. Now oil shale industry moves more to oil production and this needs innovation methods for separation to ensure fuel quality and the changes in quality. The pilot unit test with Allmineral ALLJIG have pointed out that the suitable new innovation way for oil shale separation can be wet separation with gravity, where material by pulsating water forming layers of grains according to their density and subsequently separates the heavy material (limestone) from the stratified material (oil shale)bed. Main aim of this research is to find the suitable separation process for oil shale, that the products have highest quality. The expected results can be used also for developing separation processes for phosphorite rock or all others, where traditional separation processes doesn't work property. This research is part of the study Sustainable and environmentally acceptable Oil shale mining No. 3.2.0501.11-0025 http://mi.ttu.ee/etp and the project B36 Extraction and processing of rock with selective methods - http://mi.ttu.ee/separation; http://mi.ttu.ee/miningwaste/

Water management practices used by Fayetteville shale gas producers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Veil, J. A.

2011-06-03

Water issues continue to play an important role in producing natural gas from shale formations. This report examines water issues relating to shale gas production in the Fayetteville Shale. In particular, the report focuses on how gas producers obtain water supplies used for drilling and hydraulically fracturing wells, how that water is transported to the well sites and stored, and how the wastewater from the wells (flowback and produced water) is managed. Last year, Argonne National Laboratory made a similar evaluation of water issues in the Marcellus Shale (Veil 2010). Gas production in the Marcellus Shale involves at least threemore » states, many oil and gas operators, and multiple wastewater management options. Consequently, Veil (2010) provided extensive information on water. This current study is less complicated for several reasons: (1) gas production in the Fayetteville Shale is somewhat more mature and stable than production in the Marcellus Shale; (2) the Fayetteville Shale underlies a single state (Arkansas); (3) there are only a few gas producers that operate the large majority of the wells in the Fayetteville Shale; (4) much of the water management information relating to the Marcellus Shale also applies to the Fayetteville Shale, therefore, it can be referenced from Veil (2010) rather than being recreated here; and (5) the author has previously published a report on the Fayetteville Shale (Veil 2007) and has helped to develop an informational website on the Fayetteville Shale (Argonne and University of Arkansas 2008), both of these sources, which are relevant to the subject of this report, are cited as references.« less

Black hole shadow in an expanding universe with a cosmological constant

NASA Astrophysics Data System (ADS)

Perlick, Volker; Tsupko, Oleg Yu.; Bisnovatyi-Kogan, Gennady S.

2018-05-01

We analytically investigate the influence of a cosmic expansion on the shadow of the Schwarzschild black hole. We suppose that the expansion is driven by a cosmological constant only and use the Kottler (or Schwarzschild-de Sitter) spacetime as a model for a Schwarzschild black hole embedded in a de Sitter universe. We calculate the angular radius of the shadow for an observer who is comoving with the cosmic expansion. It is found that the angular radius of the shadow shrinks to a nonzero finite value if the comoving observer approaches infinity.

43 CFR 3905.10 - Oil shale lease exchanges.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 43 Public Lands: Interior 2 2014-10-01 2014-10-01 false Oil shale lease exchanges. 3905.10 Section... MANAGEMENT, DEPARTMENT OF THE INTERIOR MINERALS MANAGEMENT (3000) OIL SHALE MANAGEMENT-GENERAL Lease Exchanges § 3905.10 Oil shale lease exchanges. To facilitate the recovery of oil shale, the BLM may consider...

43 CFR 3905.10 - Oil shale lease exchanges.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 43 Public Lands: Interior 2 2013-10-01 2013-10-01 false Oil shale lease exchanges. 3905.10 Section... MANAGEMENT, DEPARTMENT OF THE INTERIOR MINERALS MANAGEMENT (3000) OIL SHALE MANAGEMENT-GENERAL Lease Exchanges § 3905.10 Oil shale lease exchanges. To facilitate the recovery of oil shale, the BLM may consider...

43 CFR 3905.10 - Oil shale lease exchanges.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 43 Public Lands: Interior 2 2012-10-01 2012-10-01 false Oil shale lease exchanges. 3905.10 Section... MANAGEMENT, DEPARTMENT OF THE INTERIOR MINERALS MANAGEMENT (3000) OIL SHALE MANAGEMENT-GENERAL Lease Exchanges § 3905.10 Oil shale lease exchanges. To facilitate the recovery of oil shale, the BLM may consider...

What is shale gas and why is it important?

EIA Publications

2012-01-01

Shale gas refers to natural gas that is trapped within shale formations. Shales are fine-grained sedimentary rocks that can be rich sources of petroleum and natural gas. Over the past decade, the combination of horizontal drilling and hydraulic fracturing has allowed access to large volumes of shale gas that were previously uneconomical to produce. The production of natural gas from shale formations has rejuvenated the natural gas industry in the United States.

Preliminary Stratigraphic Cross Sections of Oil Shale in the Eocene Green River Formation, Uinta Basin, Utah

USGS Publications Warehouse

Dyni, John R.

2008-01-01

Oil shale units in the Eocene Green River Formation are shown on two east-west stratigraphic sections across the Uinta Basin in northeastern Utah. Several units have potential value for recovery of shale oil, especially the Mahogany oil shale zone, which is a high grade oil shale that can be traced across most of the Uinta Basin and into the Piceance Basin in northwestern Colorado. Many thin medium to high grade oil shale beds above the Mahogany zone can also be traced for many miles across the basin. Several units below the Mahogany that have slow velocities on sonic logs may be low grade oil shale. These may have value as a source for shale gas.

Shale Gas Exploration and Development Progress in China and the Way Forward

NASA Astrophysics Data System (ADS)

Chen, Jianghua

2018-02-01

Shale gas exploration in China started late but is progressing very quickly with the strong support from Central Government. China has 21.8 tcm technically recoverable shale gas resources and 764.3 bcm proved shale gas reserve, mainly in marine facies in Sichuan basin. In 2016, overall shale gas production in China is around 7.9 bcm, while it is set to reach 10 bcm in 2017 and 30 bcm in 2020. BP is the only remaining IOC actor in shale gas exploration in China partnering with CNPC in 2 blocks in Sichuan basin. China is encouraging shale gas business both at Central level and at Provincial level through establishing development plan, continuation of subsidies and research funding. Engineering services for shale gas development and infrastructures are developing, while the overall cost and gas marketing conditions will be key factors for the success in shale gas industry.

Organoporosity Evaluation of Shale: A Case Study of the Lower Silurian Longmaxi Shale in Southeast Chongqing, China

PubMed Central

Chen, Fangwen; Lu, Shuangfang; Ding, Xue

2014-01-01

The organopores play an important role in determining total volume of hydrocarbons in shale gas reservoir. The Lower Silurian Longmaxi Shale in southeast Chongqing was selected as a case to confirm the contribution of organopores (microscale and nanoscale pores within organic matters in shale) formed by hydrocarbon generation to total volume of hydrocarbons in shale gas reservoir. Using the material balance principle combined with chemical kinetics methods, an evaluation model of organoporosity for shale gas reservoirs was established. The results indicate that there are four important model parameters to consider when evaluating organoporosity in shale: the original organic carbon (w(TOC0)), the original hydrogen index (I H0), the transformation ratio of generated hydrocarbon (F(R o)), and the organopore correction coefficient (C). The organoporosity of the Lower Silurian Longmaxi Shale in the Py1 well is from 0.20 to 2.76%, and the average value is 1.25%. The organoporosity variation trends and the residual organic carbon of Longmaxi Shale are consistent in section. The residual organic carbon is indicative of the relative levels of organoporosity, while the samples are in the same shale reservoirs with similar buried depths. PMID:25184155

Relative sea level changes during the Cretaceous in Israel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Flexer, A.; Rosenfeld, A.; Lipson-Benitah, S.

1986-11-01

Detailed lithologic, microfaunal, and biometric investigations, using relative abundances, diversity indexes, and duration charts of ostracods and foraminifera, allowed the recognition of sea level changes during the Cretaceous of Israel. Three major transgressive-regressive sedimentation cycles occur on the northwest margins of the Arabian craton. These cycles are the Neocomian-Aptian, which is mostly terrigenous sediments; the Albian-Turonian, which is basin marls and platform carbonates; and the Senonian, which is uniform marly chalks. The cycles are separated by two major regional unconformities, the Aptian-Albian and Turonian-Coniacian boundaries. The sedimentary cycles are related to regional tectonic and volcanic events and eustatic changes. Themore » paleodepth curve illustrates the gradual sea level rise, reaching its maximum during the Late Cretaceous, with conspicuous advances during the late Aptian, late Albian-Cenomanian, early Turonian, early Santonian, and early Campanian. Major lowstands occur at the Aptian-Albian, Cenomanian-Turonian, Turonian-Coniacian, and Campanian-Maastrichtian boundaries. This model for Israel agrees well with other regional and global sea level fluctuations. Four anoxic events (black shales) accompanying transgressions correspond to the Cretaceous oceanic record. They hypothesize the presence of mature oil shales in the present-day eastern Mediterranean basin close to allochthonous reef blocks detached from the Cretaceous platform. 11 figures.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sari, A.; Geze, Y.

The studied area is a lake basin located in Bolu basin in Turkey. In the basin, from Upper Cretaceous to Upper Miocene 3,000-m thickness sediments were deposited. Upper Miocene Himmetoglu formation consisted of sandstone, claystone, and marl. To the middle level of the formation are located coal, bituminous limestone, and bituminous shales. In the basin, there are two coal beds whose thicknesses range from 1 to 13 m. The coals are easily breakable and black in color. In the coal beds exists some bituminous limestone and bituminous shales, and their thicknesses are between 5 and 45 cm. The amount ofmore » organic matter of the bituminous rocks from the Upper Miocene Himmetoglu formation are between 6.83 and 56.34 wt%, and the amount of organic matter of the bituminous limestone from the formation are between 13.58 and 57.16 wt%. These values indicate that these rocks have very good source potential. According to hydrogen index (HI), S2/S3, HI-T{sub max}, and HI-OI (oxygen index) parameters, kerogen types of the bituminous rocks and coals belonging to Upper Miocene Himmetoglu formation are Type I, Type II, and Type III. In accordance with HI, S2/S3, HI-T{sub max}, and HI-OI parameters, the bituminous rocks and coals from the Upper Miocene Himmetoglu formation are mostly immature.« less

The Lamu Basin deepwater fold-and-thrust belt: An example of a margin-scale, gravity-driven thrust belt along the continental passive margin of East Africa

NASA Astrophysics Data System (ADS)

Cruciani, Francesco; Barchi, Massimiliano R.

2016-03-01

In recent decades, advances in seismic processing and acquisition of new data sets have revealed the presence of many deepwater fold-and-thrust belts (DW-FTBs), often developing along continental passive margins. These kinds of tectonic features have been intensively studied, due to their substantial interest. This work presents a regional-scale study of the poorly explored Lamu Basin DW-FTB, a margin-scale, gravity-driven system extending for more than 450 km along the continental passive margin of Kenya and southern Somalia (East Africa). A 2-D seismic data set was analyzed, consisting of both recently acquired high-quality data and old reprocessed seismic profiles, for the first detailed structural and stratigraphic interpretation of this DW-FTB. The system originated over an Early to mid-Cretaceous shale detachment due to a mainly gravity-spreading mechanism. Analysis of synkinematic strata indicates that the DW-FTB was active from the Late Cretaceous to the Early Miocene, but almost all of the deformation occurred before the Late Paleocene. The fold-and-thrust system displays a marked N-S variation in width, the northern portion being more than 150 km wide and the southern portion only a few dozen kilometers wide; this along-strike variation is thought to be related to the complex tectonosedimentary evolution of the continental margin at the Somalia-Kenya boundary, also reflected in the present-day bathymetry. Locally, a series of volcanic edifices stopped the basinward propagation of the DW-FTB. A landward change in the dominant structural style, from asymmetric imbricate thrust sheets to pseudo-symmetric detachment folds, is generally observed, related to the landward thickening of the detached shales.

Petrology, sedimentology and stratigraphic implications of Black Dragon Member of the Triassic Moenkopi Formation, San Rafael Swell, Utah

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chan, M.A.; Ochs, S.

1990-01-01

Deposition was partly controlled by paleotopographic relief of underlying Permian strata. Triassic Black Dragon sediments filled lowlands on an erosion surface (unconformity) cut into the Permian White Rim Sandstone and Kaibab Limestone. The Black Dragon Member consists of four distinct facies containing a wide variety of sedimentary structures that characterize both fluvial and tidal environments. The facies are: (1) a Chert Pebble Conglomerate (CPC) facies, characterized by calcite-cemented channel-fills of nodular and banded chert pebbles; (2) an Interbedded Sandstone, Siltstone, and Shale (SSS) facies, containing oscillation ripples and flaser bedding; (3) a large-scale Trough Cross-Stratified Sandstone (TXS) facies, consisting ofmore » 6.6-13.1 ft (2-4 m) thick sets of fine- to medium-grained sandstone; and (4) an Oolitic and Algal Limestone (OAL) facies, with cross-stratified oolitic beds, fenestral fabric, and laminated algal rip-up clasts. The CPC facies and the TXS facies were deposited by braided streams when the shoreline lay west of the San Rafael Swell. Rivers drained off and eroded localized Permian highlands, located most likely within a 62 mi (100 km) distance to the south and southeast of the study area. The SSS facies which constitutes the bulk of the Black Dragon Member, and the OAL facies are inter- and supratidal deposits formed during relative sea level highstands, when the shoreline lay within or east of the San Rafael Swell. A decrease in continent-derived sand supply and a corresponding increase in carbonate production within the OAL facies characterizes the end of Black Dragon deposition and the gradation into the overlying Sinbad Limestone Member.« less

43 CFR 3905.10 - Oil shale lease exchanges.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 43 Public Lands: Interior 2 2011-10-01 2011-10-01 false Oil shale lease exchanges. 3905.10 Section... MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE MANAGEMENT-GENERAL Lease Exchanges § 3905.10 Oil shale lease exchanges. To facilitate the recovery of oil shale, the BLM may consider land...

Preparation of grout for stabilization of abandoned in-situ oil shale retorts

DOEpatents

Mallon, Richard G.

1982-01-01

A process for the preparation of grout from burned shale by treating the burned shale in steam at approximately 700.degree. C. to maximize the production of the materials alite and larnite. Oil shale removed to the surface during the preparation of an in-situ retort is first retorted on the surface and then the carbon is burned off, leaving burned shale. The burned shale is treated in steam at approximately 700.degree. C. for about 70 minutes. The treated shale is then ground and mixed with water to produce a grout which is pumped into an abandoned, processed in-situ retort, flowing into the void spaces and then bonding up to form a rigid, solidified mass which prevents surface subsidence and leaching of the spent shale by ground water.

Integrated stratigraphy of the Cenomanian-Turonian boundary interval: improving understanding of Oceanic Anoxic Events

NASA Astrophysics Data System (ADS)

Jarvis, Ian

2014-05-01

The Cenomanian-Turonian boundary (CTB) interval ~ 94 Ma represented a period of major global palaeoenvironmental change. Increasingly detailed multidisciplinary studies integrating sedimentological, palaeontological and geochemical data from multiple basins, are enabling the development of refined but complex models that aid understanding of the mechanisms driving changes in ocean productivity and climate. This paper reviews some of the exciting new developments in this field. Facies change characterizes the CTB interval in most areas. In the Chalk seas of northern Europe, a widespead hiatus was followed by the deposition of clay-rich organic-lean beds of the Plenus Marl and its equivalents, and then nodular chalks. In the North Sea basin and its onshore extension in eastern England and northern Germany, black shales of the Black Band (Blodøks Formation, Hasseltal Formation) occur. Similarly, in northern Tethys, a brief interval of black shale accumulation within a predominantly carbonate succession, is exemplified by the Niveau Thomel in the Vocontian Basin (SE France), and the Livello Bonarelli in Italy. Widespread deposition of organic-rich marine sediments during CTB times led to 12C depletion in surface carbon reservoirs (oceans, atmosphere, biosphere), and a large positive global δ13C excursion preserved in marine carbonates and both marine and terrestrial organic matter (Oceanic Anoxic Event 2). Significant biotic turnover characterises the boundary interval, and inter-regional correlation may be achieved at high resolution using integrated biostratigraphy employing macrofossils (ammonites, inoceramid bivalves), microfossils (planktonic foraminifera, dinoflagellate cysts) and calcareous nannofossils. Correlations can be tested against those based on comparison of δ13C profiles - carbon isotope chemostratigraphy, supplemented by oxygen isotope and elemental data. Interpretation of paired carbonate - organic matter δ13C data from multiple CTB sections implicates rising atmospheric pCO2 linked to volcanic outgassing as a major forcing mechanism for palaeoclimate warming and palaeoceanographic change accompanying OAE2. New marine 187Os/188Os isotope stratigraphy further reveals the interaction of volcanism and ocean circulation during OAE2, and provides a further chemostratigraphic tool. Li isotope (δ 7Li) data may be interpreted as evidence that increased silicate weathering promoted by rising pCO2 acted as both a forcing and negative feedback mechanism driving OAE2 history. Neodymium and sulphur isotopes offer further insights into interactions between global biogeochemical cycles and ocean circulation changes.

Method for maximizing shale oil recovery from an underground formation

DOEpatents

Sisemore, Clyde J.

1980-01-01

A method for maximizing shale oil recovery from an underground oil shale formation which has previously been processed by in situ retorting such that there is provided in the formation a column of substantially intact oil shale intervening between adjacent spent retorts, which method includes the steps of back filling the spent retorts with an aqueous slurry of spent shale. The slurry is permitted to harden into a cement-like substance which stabilizes the spent retorts. Shale oil is then recovered from the intervening column of intact oil shale by retorting the column in situ, the stabilized spent retorts providing support for the newly developed retorts.

Nanometer-Scale Pore Characteristics of Lacustrine Shale, Songliao Basin, NE China

PubMed Central

Wang, Min; Yang, Jinxiu; Wang, Zhiwei; Lu, Shuangfang

2015-01-01

In shale, liquid hydrocarbons are accumulated mainly in nanometer-scale pores or fractures, so the pore types and PSDs (pore size distributions) play a major role in the shale oil occurrence (free or absorbed state), amount of oil, and flow features. The pore types and PSDs of marine shale have been well studied; however, research on lacustrine shale is rare, especially for shale in the oil generation window, although lacustrine shale is deposited widely around the world. To investigate the relationship between nanometer-scale pores and oil occurrence in the lacustrine shale, 10 lacustrine shale core samples from Songliao Basin, NE China were analyzed. Analyses of these samples included geochemical measurements, SEM (scanning electron microscope) observations, low pressure CO2 and N2 adsorption, and high-pressure mercury injection experiments. Analysis results indicate that: (1) Pore types in the lacustrine shale include inter-matrix pores, intergranular pores, organic matter pores, and dissolution pores, and these pores are dominated by mesopores and micropores; (2) There is no apparent correlation between pore volumes and clay content, however, a weak negative correlation is present between total pore volume and carbonate content; (3) Pores in lacustrine shale are well developed when the organic matter maturity (Ro) is >1.0% and the pore volume is positively correlated with the TOC (total organic carbon) content. The statistical results suggest that oil in lacustrine shale mainly occurs in pores with diameters larger than 40 nm. However, more research is needed to determine whether this minimum pore diameter for oil occurrence in lacustrine shale is widely applicable. PMID:26285123

Nanometer-Scale Pore Characteristics of Lacustrine Shale, Songliao Basin, NE China.

PubMed

Wang, Min; Yang, Jinxiu; Wang, Zhiwei; Lu, Shuangfang

2015-01-01

In shale, liquid hydrocarbons are accumulated mainly in nanometer-scale pores or fractures, so the pore types and PSDs (pore size distributions) play a major role in the shale oil occurrence (free or absorbed state), amount of oil, and flow features. The pore types and PSDs of marine shale have been well studied; however, research on lacustrine shale is rare, especially for shale in the oil generation window, although lacustrine shale is deposited widely around the world. To investigate the relationship between nanometer-scale pores and oil occurrence in the lacustrine shale, 10 lacustrine shale core samples from Songliao Basin, NE China were analyzed. Analyses of these samples included geochemical measurements, SEM (scanning electron microscope) observations, low pressure CO2 and N2 adsorption, and high-pressure mercury injection experiments. Analysis results indicate that: (1) Pore types in the lacustrine shale include inter-matrix pores, intergranular pores, organic matter pores, and dissolution pores, and these pores are dominated by mesopores and micropores; (2) There is no apparent correlation between pore volumes and clay content, however, a weak negative correlation is present between total pore volume and carbonate content; (3) Pores in lacustrine shale are well developed when the organic matter maturity (Ro) is >1.0% and the pore volume is positively correlated with the TOC (total organic carbon) content. The statistical results suggest that oil in lacustrine shale mainly occurs in pores with diameters larger than 40 nm. However, more research is needed to determine whether this minimum pore diameter for oil occurrence in lacustrine shale is widely applicable.

Map of assessed shale gas in the United States, 2012

USGS Publications Warehouse

,; Biewick, Laura R. H.

2013-01-01

The U.S. Geological Survey has compiled a map of shale-gas assessments in the United States that were completed by 2012 as part of the National Assessment of Oil and Gas Project. Using a geology-based assessment methodology, the U.S. Geological Survey quantitatively estimated potential volumes of undiscovered gas within shale-gas assessment units. These shale-gas assessment units are mapped, and square-mile cells are shown to represent proprietary shale-gas wells. The square-mile cells include gas-producing wells from shale intervals. In some cases, shale-gas formations contain gas in deeper parts of a basin and oil at shallower depths (for example, the Woodford Shale and the Eagle Ford Shale). Because a discussion of shale oil is beyond the scope of this report, only shale-gas assessment units and cells are shown. The map can be printed as a hardcopy map or downloaded for interactive analysis in a Geographic Information System data package using the ArcGIS map document (file extension MXD) and published map file (file extension PMF). Also available is a publications access table with hyperlinks to current U.S. Geological Survey shale gas assessment publications and web pages. Assessment results and geologic reports are available as completed at the U.S. Geological Survey Energy Resources Program Web Site, http://energy.usgs.gov/OilGas/AssessmentsData/NationalOilGasAssessment.aspx. A historical perspective of shale gas activity in the United States is documented and presented in a video clip included as a PowerPoint slideshow.

Postimpact heat conduction and compaction-driven fluid flow in the Chesapeake Bay impact structure based on downhole vitrinite reflectance data, ICDP-USGS Eyreville deep core holes and Cape Charles test holes

USGS Publications Warehouse

Malinconico, M.L.; Sanford, W.E.; Wright, Horton W.J.J.

2009-01-01

Vitrinite reflectance data from the International Continental Scientific Drilling Program (ICDP)-U.S. Geological Survey (USGS) Eyreville deep cores in the centralcrater moat of the Chesapeake Bay impact structure and the Cape Charles test holes on the central uplift show patterns of postimpact maximum-temperature distribution that result from a combination of conductive and advective heat flow. Within the crater-fill sediment-clast breccia sequence at Eyreville, an isoreflectance (-0.44% Ro) section (525-1096 m depth) is higher than modeled background coastal-plain maturity and shows a pattern typical of advective fluid flow. Below an intervening granite slab, a short interval of sediment-clast breccia (1371-1397 m) shows a sharp increase in reflectance (0.47%-0.91% Ro) caused by conductive heat from the underlying suevite (1397-1474 m). Refl ectance data in the uppermost suevite range from 1.2% to 2.1% Ro. However, heat conduction alone is not sufficient to affect the temperature of sediments more than 100 m above the suevite. Thermal modeling of the Eyreville suevite as a 390 ??C cooling sill-like hot rock layer supplemented by compaction- driven vertical fluid flow (0.046 m/a) of cooling suevitic fluids and deeper basement brines (120 ??C) upward through the sediment breccias closely reproduces the measured reflectance data. This scenario would also replace any marine water trapped in the crater fill with more saline brine, similar to that currently in the crater, and it would produce temperatures sufficient to kill microbes in sediment breccias within 450 m above the synimsuevite. A similar downhole maturity pattern is present in the sediment-clast breccia over the central uplift. High-reflectance (5%-9%) black shale and siltstone clasts in the suevite and sediment-clast breccia record a pre-impact (Paleozoic?) metamorphic event. Previously published maturity data in the annular trough indicate no thermal effect there from impact-related processes. ?? 2009 The Geological Society of America.

A link between Late Pliensbachian organic matter preservation and the Spinatum Chronozone icehouse event

NASA Astrophysics Data System (ADS)

Silva, Ricardo L.; Duarte, Luís. V.

2014-05-01

It is recognized today that the "greenhouse" Mesozoic Era includes several short-lived icehouse episodes. One occurred during the Spinatum Chronozone (Late Pliensbachian), which immediately preceded a 2nd-order extinction event and a major carbon cycle perturbation associated to the Early Toarcian Oceanic Anoxic Event. The Lower Jurassic hemipelagic carbonate series of the Lusitanian Basin (Portugal) mark the hinge zone between the Tethyan (Mediterranean) and Boreal (North-European) realms. Here, one of the most obvious features is the organic-rich nature of the majority of the Ibex-Margaritatus chronozones (Pliensbachian) series (Marly-limestones with organic-rich facies member of the Vale das Fontes Formation), capped by a regressive limestone unit of uppermost Margaritatus-lowermost Polymorphum (Toarcian) chronozones (Lemede Formation). The Pliensbachian organic-rich deposition (observed in several locations around the world) is coeval with a positive carbon isotopic excursion recorded in carbonates and organic substrates. For the Lusitanian Basin, evidences points toward the occurrence of brief "hot snaps" prior to the onset of the icehouse interval of Spinatum age. We demonstrate that cooling was preceded by several episodes of organic matter preservation, most likely driven by extreme warming, coupled with high oceanic productivity and stratified (thermally?) epeiric areas. These "hot snaps" allowed the rapid but short-lived expansion of Tethyan ammonites into Boreal domains. They also promoted widespread mucilage and microbial outbreaks preserved in the Lusitanian Basin as black shales, resulting in organic matter deposition and geological carbon storage. So far, the causes for these "hot snaps" remain unclear. This chain of events most likely triggered and/or amplified the Spinatum Chronozone icehouse event, which led to permafrost and/or methane gas hydrates in locations easily disturbed by the subsequent Early Toarcian warming, or/and increased volcanic activity driven by deglaciation. The authors would like to acknowledge the project PTDC/CTE-GIX/098968/2008 (FCT-Portugal and COMPETE-FEDER). Ricardo L. Silva also acknowledges ExxonMobil Canada Proprieties (on behalf of the Sable Offshore Energy Project) for financial support of through the Petroleum Geoscience Research Grant to Dalhousie University (Basin and Reservoir Lab).

Comparative acute toxicity of shale and petroleum derived distillates.

PubMed

Clark, C R; Ferguson, P W; Katchen, M A; Dennis, M W; Craig, D K

1989-12-01

In anticipation of the commercialization of its shale oil retorting and upgrading process, Unocal Corp. conducted a testing program aimed at better defining potential health impacts of a shale industry. Acute toxicity studies using rats and rabbits compared the effects of naphtha, Jet-A, JP-4, diesel and "residual" distillate fractions of both petroleum derived crude oils and hydrotreated shale oil. No differences in the acute oral (greater than 5 g/kg LD50) and dermal (greater than 2 g/kg LD50) toxicities were noted between the shale and petroleum derived distillates and none of the samples were more than mildly irritating to the eyes. Shale and petroleum products caused similar degrees of mild to moderate skin irritation. None of the materials produced sensitization reactions. The LC50 after acute inhalation exposure to Jet-A, shale naphtha, (greater than 5 mg/L) and JP-4 distillate fractions of petroleum and shale oils was greater than 5 mg/L. The LC50 of petroleum naphtha (greater than 4.8 mg/L) and raw shale oil (greater than 3.95 mg/L) also indicated low toxicity. Results demonstrate that shale oil products are of low acute toxicity, mild to moderately irritating and similar to their petroleum counterparts. The results further demonstrate that hydrotreatment reduces the irritancy of raw shale oil.

Shale gas development impacts on surface water quality in Pennsylvania.

PubMed

Olmstead, Sheila M; Muehlenbachs, Lucija A; Shih, Jhih-Shyang; Chu, Ziyan; Krupnick, Alan J

2013-03-26

Concern has been raised in the scientific literature about the environmental implications of extracting natural gas from deep shale formations, and published studies suggest that shale gas development may affect local groundwater quality. The potential for surface water quality degradation has been discussed in prior work, although no empirical analysis of this issue has been published. The potential for large-scale surface water quality degradation has affected regulatory approaches to shale gas development in some US states, despite the dearth of evidence. This paper conducts a large-scale examination of the extent to which shale gas development activities affect surface water quality. Focusing on the Marcellus Shale in Pennsylvania, we estimate the effect of shale gas wells and the release of treated shale gas waste by permitted treatment facilities on observed downstream concentrations of chloride (Cl(-)) and total suspended solids (TSS), controlling for other factors. Results suggest that (i) the treatment of shale gas waste by treatment plants in a watershed raises downstream Cl(-) concentrations but not TSS concentrations, and (ii) the presence of shale gas wells in a watershed raises downstream TSS concentrations but not Cl(-) concentrations. These results can inform future voluntary measures taken by shale gas operators and policy approaches taken by regulators to protect surface water quality as the scale of this economically important activity increases.

Characterising the vertical separation of shale-gas source rocks and aquifers across England and Wales (UK)

NASA Astrophysics Data System (ADS)

Loveless, Sian E.; Bloomfield, John P.; Ward, Robert S.; Hart, Alwyn J.; Davey, Ian R.; Lewis, Melinda A.

2018-03-01

Shale gas is considered by many to have the potential to provide the UK with greater energy security, economic growth and jobs. However, development of a shale gas industry is highly contentious due to environmental concerns including the risk of groundwater pollution. Evidence suggests that the vertical separation between exploited shale units and aquifers is an important factor in the risk to groundwater from shale gas exploitation. A methodology is presented to assess the vertical separation between different pairs of aquifers and shales that are present across England and Wales. The application of the method is then demonstrated for two of these pairs—the Cretaceous Chalk Group aquifer and the Upper Jurassic Kimmeridge Clay Formation, and the Triassic sandstone aquifer and the Carboniferous Bowland Shale Formation. Challenges in defining what might be considered criteria for `safe separation' between a shale gas formation and an overlying aquifer are discussed, in particular with respect to uncertainties in geological properties, aquifer extents and determination of socially acceptable risk levels. Modelled vertical separations suggest that the risk of aquifer contamination from shale exploration will vary greatly between shale-aquifer pairs and between regions and this will need to be considered carefully as part of the risk assessment and management for any shale gas development.

Sedimentary provenance of Maastrichtian oil shales, Central Eastern Desert, Egypt

NASA Astrophysics Data System (ADS)

Fathy, Douaa; Wagreich, Michael; Mohamed, Ramadan S.; Zaki, Rafat

2017-04-01

Maastrichtian oil shales are distributed within the Central Eastern Desert in Egypt. In this study elemental geochemical data have been applied to investigate the probable provenance of the sedimentary detrital material of the Maastrichtian oil shale beds within the Duwi and the Dakhla formations. The Maastrichtian oil shales are characterized by the enrichment in Ca, P, Mo, Ni, Zn, U, Cr and Sr versus post-Archean Australian shales (PAAS). The chondrite-normalized patterns of the Maastrichtian oil shale samples are showing LREE enrichment, HREE depletion, slightly negative Eu anomaly, no obvious Ce anomaly and typical shale-like PAAS-normalized patterns. The total REE well correlated with Si, Al, Fe, K and Ti, suggesting that the REE of the Maastrichtian oil shales are derived from terrigenous source. Chemical weathering indices such as Chemical Index of Alteration (CIA), Chemical Proxy of Alteration (CPA) and Plagioclase Index of Alteration (PIA) indicate moderate to strong chemical weathering. We suggest that the Maastrichtian oil shale is mainly derived from first cycle rocks especially intermediate rocks without any significant inputs from recycled or mature sources. The proposed data illustrated the impact of the parent material composition on evolution of oil shale chemistry. Furthermore, the paleo-tectonic setting of the detrital source rocks for the Maastrichtian oil shale is probably related to Proterozoic continental island arcs

Experimental study of CO2 effect on shale mechanical properties in the processes of complete strain-stress and post-failure tests

NASA Astrophysics Data System (ADS)

Wang, Y.; Ji, J.; Li, M.

2017-12-01

CO2 enhanced shale gas recovery has proved to be one of the most efficient methods to extract shale gas, and represent a mutually beneficial approach to mitigate greenhouse gas emission into the atmosphere. During the processes of most CO2 enhanced shale gas recovery, liquid CO2 is injected into reservoirs, fracturing the shale, making competitive adsorption with shale gas and displacing the shale gas at multi-scale to the production well. Hydraulic and mechanical coupling actions between the shale and fluid media are expected to play important roles in affecting fracture propagation, CO2 adsorption and shale gas desorption, multi-scale fluid flow, plume development, and CO2 storage. In this study, four reservoir shale samples were selected to carry out triaxial compression experiments of complete strain-stress and post failure tests. Two fluid media, CO2 and N2, were used to flow through the samples and produce the pore pressure. All of the above four compression experiments were conducted under the same confining and pore pressures, and loaded the axial pressure with the same loading path. Permeability, strain-stress, and pore volumetric change were measured and recorded over time. The results show that, compared to N2, CO2 appeared to lower the peak strength and elastic modulus of shale samples, and increase the permeability up two to six orders of magnitudes after the sample failure. Furthermore, the shale samples were dilated by CO2 much more than N2, and retained the volume of CO2 2.6 times more than N2. Results from this study indicate that the CO2 can embrittle the shale formation so as to form fracture net easily to enhance the shale gas recovery. Meanwhile, part of the remaining CO2 might be adsorbed on the surface of shale matrix and the rest of the CO2 be in the pore and fracture spaces, implying that CO2 can be effectively geo-stored in the shale formation.

Sedimentary organic matter characterization of the Triassic-Jurassic boundary GSSP at Kuhjoch (Austria)

NASA Astrophysics Data System (ADS)

Ruhl, M.; Veld, H.; Kürschner, W. M.

2010-03-01

The Triassic-Jurassic (T-J) boundary interval coincides with enhanced extinction rates in the marine realm and pronounced changes in terrestrial ecosystems on the continents. It is further marked by distinct negative excursions in the δ13C org and δ13C carb signature that may represent strong perturbations of the global carbon cycle. We present integrated geochemical, stable-isotope and palynological data from the Kuhjoch section, the Global boundary Stratotype Section and Point (GSSP) for the base of the Jurassic (Northern Calcareous Alps, Austria). We show that the initial carbon isotope excursion (CIE), coinciding with the marine extinction interval and the formation of black shales in the western Tethys Eiberg Basin, is marked by only minor changes in kerogen type, which is mainly of terrestrial origin. Increased Total Organic Carbon (TOC) concentrations of 9% at the first half of the initial CIE coincide with Hydrogen Index (HI) values of over 600 mg HC/g TOC. The high correlation (with R2 = 0.93) between HI values and terrestrial Cheirolepidiaceaen conifer pollen suggests a terrestrial source for the hydrogen enriched organic compounds. The lack of major changes in source of the sedimentary organic matter suggests that changes in the δ13C org composition are genuine and represent true disturbances of the global C-cycle. The sudden decrease in total inorganic carbon (TIC) concentrations likely represents the onset of a biocalcification crisis. It coincides with a 4.5‰ negative shift in δ13C org values and possibly corresponds to the onset of CAMP related volcanic activity. The second half of the initial CIE is marked by the dramatic increase of green algae remains in the sediment. The simultaneous increase of the C org/N tot ratio suggests increased marine primary production at the final stage of black shale formation.

Mapping Electrical Structures in the Jarud Basin, Northeast China through Magnetotelluric Sounding

NASA Astrophysics Data System (ADS)

Zhao, W.

2015-12-01

In recent years, China Geological Survey (CGS) has launched 3D geological mapping programs from regional to local scales. The project Deep geological survey at the periphery of the Songliao Basin funded by CGS was implemented from 2012 to 2014. Its main goals are to reveal the tectonic framework of the Jarud Basin (JB) as well as to identify the strata distribution of Permian Linxi Formation by integrating new electromagnetic data with existing geophysical and geological data since black mudstones in the Linxi Formation have shown the potential of shale gas. The study area covered dominantly with Cretaceous-Jurassic igneous rocks with exception of the southeast part is situated in Jarud Banner and Ar Horqin Banner, Inner Mongolia, China. It tectonically lies in the southern Great Khingan Range, western margin of the Songliao Basin, and north of Xar Moron Fault. Over the period of 2012 to 2014, a magnetotelluric survey was carried out at the JB. A total of 926 MT sites with nominal spacing 1 km was acquired in the effective frequency range of 0.01 Hz ~ 300 Hz on six NW and five NE profiles, covering area that exceeds 10, 000 km2. After dimensionality analysis and static shift removal, the nonlinear conjugate algorithm was used to conduct 2D inversion for TM and TE modes. The resistivity models underwent examination using sensitivity tests. The optimal resistivity models revealed numerous large faults, some of which constitute the boundaries of the JB, and modified the tectonic framework. Integrated with well logging and geological mapping data, the strata of Linxi Formation were identified and classified into three depressions: Depressions Arituguri, Gadasu and Wufen. Attention should be paid to Depression Gadasu with area of around 500 km2 since it contains reasonably thick conductive sediments exceeding 4 km in depth which are inferred to be black mudstones pertaining to shale gas.

Do Leached Authigenic Fractions Reflect the Neodymium Seawater Composition?

NASA Astrophysics Data System (ADS)

Pimbert, A.; Gourlan, A. T.; Chauvel, C.

2016-12-01

Leaching of marine sediment is often used to recover past Nd seawater composition and reconstruct past ocean circulation. It is assumed to reliably extract REE from the authigenic fraction of sediment [1]. However, while most studies assume that the recovered signal is that of past seawater, very few report complete isotopic and trace element data that clearly demonstrate it is the case. We present new ɛNd values and REE contents measured on leachates of sediments from two Cretaceous marine sections deposited at shallow water depth (Taghazoute in Morocco) and at greater depth in the Atlantic (DSDP Site 367). REE patterns of leachates vary according to lithology: bell-shaped patterns or positive Ce anomalies for organic-poor samples and seawater-like patterns (negative Ce anomaly, low Nd/Yb ratio) for black shales. ɛNd values also vary: between -5.6 and -9.6 at Taghazoute and between -10 and -8.1 at Site 367. Interestingly, ɛNd values correlate with Ce anomalies for Taghazoute black shales. Samples with the largest Ce negative anomalies have the highest ɛNd while samples with no Ce anomalies have much lower ɛNd. This suggests the presence in the leached material of detritus mixed up with the authigenic fraction for sediments deposited in shallow environment. This confirms the findings made by Huck et al. [2] for fish teeth in a similar environment. In such environment, recovering the pristine seawater signal requires (a) the acquisition of both Nd isotopes and trace element contents, and (b) selection of the only Nd isotopic compositions associated to clear seawater trace element characteristics. For sediments deposited in open-ocean setting (Site 367), no detrital contamination affects leached fractions. The REE patterns vary depending on the nature of authigenic fraction but ɛNd remains constant. Here, ɛNd values can be used to discuss oceanic reconstructions. [1] Martin et al. (2010), Chem. Geol, 269, 414-431. [2] Huck et al. (2016), G3, 17, 679-698.

Analysis of Degree of Similarity among Crude Oils, the Upper and the Lower Crust, Organic Matter, Clays, and Different Caustobioliths by the Content of Their Main and Trace Elements

NASA Astrophysics Data System (ADS)

Rodkin, Mikhail; Punanova, Svetlana

2016-04-01

The goal of this research was to estimate, based on the content of Trace Elements, the level of contribution of the lower and the upper crust as well as the organic matter into ontogenesis of hydrocarbons. The analysis of degree of similarity of the main and trace element (TE) content among the upper and lower continental crust, clays, organic matter, and different caustobioliths (oil, coal, oil-and-black shales) is performed by calculating coefficients of correlation of logarithms of concentrations of a large number of different chemical elements. Different oils from a number of oil bearing provinces in Russia and from the volcanic caldera Uzon (Kamchatka, Russia) were examined. It has been shown that the content of main elements and TEs of coals and oil-and-black shales is better correlated with the chemical composition of the upper crust, while the TE content of oils correlates better with the composition of the lower continental crust. The TE content of oils correlates with the chemical content of living organisms but the correlation in the most cases is weaker than the one with the lower crust. The results of the examination of different samples from the same oil-bearing province were found to be similar. The mean results for different oil-bearing provinces can vary considerably. The results of the examination of young oil from the Uzon volcanic caldera were found to be rather specific and different from the other oils. We also suggest a set of a small number of "characteristic" elements (Cs, Rb, K, U, V, Cr and Ni), which allows to compare the degree of similarity between an oil sample and upper or lower continental crust using only a few chemical elements. Some interpretation of the results is presented.

Recycling and Resistance of Petrogenic Particulate Organic Carbon: Implications from A Chemical Oxidation Method

NASA Astrophysics Data System (ADS)

Zhang, T.; Li, G.; Ji, J.

2013-12-01

Petrogenic particulate organic carbon (OCpetro) represents a small fraction of photosynthetic carbon which escapes pedogenic-petrogenic degradation and gets trapped in the lithosphere. Exhumation and recycling of OCpetro are of significant importance in the global carbon cycle because OCpetro oxidation represents a substantial carbon source to the atmosphere while the re-burial of OCpetro in sediment deposits has no net effect. Though studies have investigated various behaviors of OCpetro in the surface environments (e.g., riverine mobilization, marine deposition, and microbial remineralization), less attention has been paid to the reaction kinetics and structural transformations during OCpetro oxidation. Here we assess the OCpetro-oxidation process based on a chemical oxidation method adopted from soil studies. The employed chemical oxidation method is considered an effective simulation of natural oxidation in highly oxidative environments, and has been widely used in soil studies to isolate the inert soil carbon pool. We applied this chemical method to the OCpetro-enriched black shale samples from the middle-lower Yangtze (Changjiang) basin, China, and performed comprehensive instrumental analyses (element analysis, Fourier transform infrared (FTIR) spectrum, and Raman spectrum). We also conducted step-oxidizing experiments following fixed time series and monitored the reaction process in rigorously controlled lab conditions. In this work, we present our experiment results and discuss the implications for the recycling and properties of OCpetro. Particulate organic carbon concentration of black shale samples before and after oxidation helps to quantify the oxidability of OCpetro and constrain the preservation efficiency of OCpetro during fluvial erosion over large river basin scales. FTIR and Raman analyses reveal clear structural variations on atomic and molecular levels. Results from the step-oxidizing experiments provide detailed information about the reaction kinetics and allow differentiation of different components in OCpetro characterized by distinct reaction rates. All these results lead to a better understanding of OCpetro recycling in the surface environments, and furthermore, the role of OCpetro in the global carbon cycle.

Sedimentologic Expression of the Cretaceous OAEs in a Tropical Epicontinental Sea

NASA Astrophysics Data System (ADS)

Silva-Tamayo, J. C.; Eisenhauer, A.

2015-12-01

The acidification and deoxygention of modern oceans are major environmental concerns to the international community. The effects of ocean acidification and deoxigention in the biogeochemical cycles of modern tropical oceans are poorly constrained mainly due to the lack of empirical and quantitative data. The Cretaceous World witnessed several period of potential ocean acidification and deoxygenation, which resulted from the rapid additions of volcanic derived CO2 to the atmosphere. The effects of ocean acidification and deoxygenation on the Cretaceous biogeochemical cycles are evidenced mainly by major global C-isotope anomalies. These anomalies parallel the occurrence of organic rich black shales as well as major decreases in the deposition of shallow marine carbonates worldwide. Here we use detailed C- and Sr- chemostratigraphy as well as published bioestratigraphic information and volcanic zircon U-Pb ages to precisely constrain the geochemical and sedimentologic expression of the Cretaceous OAES along a tropical epicontinental sea, the La Luna Sea. Our multi-pronged approach allows identifying the occurrence of several of the Cretaceous Oceanic Anoxic Events (OAEs) in carbonate units paleogeographically located along the northern most part of the La Luna Sea, i.e. Weissert-OAE-(Palanz and Rosablanca Formations), Faraoni-(Rosablanca Formation), AOE1a-(Paja and Fomeque Formations, Cogollo Group), OAE1c-(Cogollo Group), OAE2-(Cogollo Group), OAE3-(La Luna Formation). These events are preserved in highly euxinic - organic rich "black shales" successions deposited along the deepest part of the seaway at the Middle Magdalena Valley and Cundinamarca Basin; Weiser-OAE-(Lutitas de Macanal Formation), OAE1a-(Paja Formation, Fomeque Formation), OAE1C-(San Gil Formation). Regional changes in depositional settings and sedimentary facies preserving the different Cretaceous OAEs were likely the result of the combined action of regional changes in paleogeography and tectonic regimes and changes in the physicochemical conditions of the Cretaceous seawater along the tropical La Luna epicontinental seaway.

Sacrificial Protective Coating Materials that can be Regenerated In-Situ to Enable High Performance Membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malati, Peter; Ganguli, Rahul; Mehrotra, Vivek

In the pulp and paper industry, weak black liquor concentration is carried out using energy intensive evaporators. Briefly, after wood digestion, water is evaporated to concentrate weak black liquor to the point where the black liquor can be burned in a recovery boiler, which ultimately leads to the recovery of digestion chemicals. Because it is less energy intensive than heat-driven separation, pressure-driven separation of water from black liquor using membranes could reduce the energy usage by 55 trillion Btu yr -1 and carbon dioxide emissions by more than 11 million metric tons CO 2 per year if the first twomore » evaporators are replaced. However, weak black liquor is a hot, corrosive, and highly fouling feed with organic molecules, colloids, and ions that clog membranes within hours of operation. We have shown that membrane-based concentration of weak black liquor is feasible, but only with our antifouling and anti-clogging technology that is based on a sacrificial Bio-inspired Living Skin concept. This concept is based on a conformal coating that is formed at the membrane surface and within the pores. Weak foulant adhesion dramatically decreases membrane fouling while the superhydrophilicity of the coating increases the water permeability. Moreover, the coating can be completely removed during backflushing, which removes foulants that may irreversibly adhere to the coating over long periods of time. The skin shedding completely regenerates the membrane surface and pores, restoring the original flux. This is followed by in-situ recoating, using the existing membrane plumbing and pumps, which essentially creates a brand new membrane surface.« less

Preparation of grout for stabilization of abandoned in-situ oil shale retorts. [Patent application

DOEpatents

Mallon, R.G.

1979-12-07

A process is described for the preparation of grout from burned shale by treating the burned shale in steam at approximately 700/sup 0/C to maximize the production of the materials alite and larnite. Oil shale removed to the surface during the preparation of an in-situ retort is first retorted on the surface and then the carbon is burned off, leaving burned shale. The burned shale is treated in steam at approximately 700/sup 0/C for about 70 minutes. The treated shale is then ground and mixed with water to produce a grout which is pumped into an abandoned, processed in-situ retort, flowing into the void spaces and then bonding up to form a rigid, solidified mass which prevents surface subsidence and leaching of the spent shale by ground water.

Analysis of the effectiveness of steam retorting of oil shale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacobs, H.R.; Pensel, R.W.; Udell, K.S.

A numerical model is developed to describe the retorting of oil shale using superheated steam. The model describes not only the temperature history of the shale but predicts the evolution of shale oil from kerogen decomposition and the breakdown of the carbonates existing in the shale matrix. The heat transfer coefficients between the water and the shale are determined from experiments utilizing the model to reduce the data. Similarly the model is used with thermogravimetric analysis experiments to develop an improved kinetics expression for kerogen decomposition in a steam environment. Numerical results are presented which indicate the effect of oilmore » shale particle size and steam temperature on oil production.« less

Fractal Characteristics of Continental Shale Pores and its Significance to the Occurrence of Shale Oil in China: a Case Study of Biyang Depression

NASA Astrophysics Data System (ADS)

Li, Jijun; Liu, Zhao; Li, Junqian; Lu, Shuangfang; Zhang, Tongqian; Zhang, Xinwen; Yu, Zhiyuan; Huang, Kaizhan; Shen, Bojian; Ma, Yan; Liu, Jiewen

Samples from seven major exploration wells in Biyang Depression of Henan Oilfield were compared using low-temperature nitrogen adsorption and shale oil adsorption experiments. Comprehensive analysis of pore development, oiliness and shale oil flowability was conducted by combining fractal dimension. The results show that the fractal dimension of shale in Biyang Depression of Henan Oilfield was negatively correlated with the average pore size and positively correlated with the specific surface area. Compared with the large pore, the small pore has great fractal dimension, indicating the pore structure is more complicated. Using S1 and chloroform bitumen A to evaluate the relationship between shale oiliness and pore structure, it was found that the more heterogeneous the shale pore structure, the higher the complexity and the poorer the oiliness. Clay minerals are the main carriers involved in crude oil adsorption, affecting the mobility of shale oil. When the pore complexity of shale was high, the content of micro- and mesopores was high, and the high specific surface area could enhance the adsorption and reduce the mobility of shale oil.

Major paleoceanographic changes recorded in Upper Albian-Lower Cenomanian sediments in the Western Tethys and in the North Atlantic: possible response to intense tectonic activity

NASA Astrophysics Data System (ADS)

Giorgioni, Martino; Weissert, Helmut; Keller, Christina; Bernasconi, Stefano; Hochuli, Peter; Garcia, Therese; Coccioni, Rodolfo; Petrizzo, Maria Rose

2010-05-01

During the mid-Cretaceous intense and widespread volcanism induced a high atmospheric CO2 concentration and, consequently, a very strong greenhouse effect (Bice & Norris, 2002). Opening and closing of oceanic gateways had an impact on paleoceanography (Poulsen et al, 1998; Poulsen et al, 2001). Global temperature and sea level reached the highest levels in the last 120 million years. (e.g. Pucéat et al, 2003; Hay, 2008). In this study we test if tectonically driven changes in oceanic circulation had an impact on Tethyan oceanography as predicted by models (Poulsen et al, 1998; Poulsen et al., 2001). We trace sedimentological changes during the Albian-Cenomanian across the Western Tethys and into the North Atlantic, integrating litho-, bio-, and isotope stratigraphy to obtain a robust correlation between studied sections, from pelagic to coastal settings. Albian sediments display very different facies from one site to the other. Pelagic marls with several black shales alternated to green, white, or red beds (Marne a Fucoidi/Scaglia Variegata Formation) are observed in the southern Tethys. Silty/sandy nodular limestone and marly limestones, with hiatuses and condensed intervals, (Garschella Formation) were deposited along the northern Tethyan shelf. Black shales and bioturbated marls are present in cycles, with several hiatuses, in the North Atlantic. These heterogeneous sediments became gradually replaced by more homogeneous and carbonate-rich facies between the Late Albian and the Early Cenomanian. These new facies consist of white, sometimes reddish, micritic limestones, rich in planktonic foraminifera. This sedimentation pattern is dominant in Upper Cretaceous successions, both in deep basins and on shelves. This change in sedimentation happened gradually in an East-West extending trend. It is first observed in the southern Tethys, then along the northern Tethys, and finally in the North Atlantic. We interpret the described change in sedimentation as due to a gradual turn of the oceanic circulation happening on the million of year time frame, which is probably related to one or more of the opening and closing of oceanic gateways during the mid-Cretaceous. References: Bice K. L. & Norris R. D. - Possible atmospheric CO2 extremes of the Middle Cretaceous (late Albian-Turonian) - Paleoceanography, vol. 17, n. 4, 2002 Hay W. - Evolving ideas about the Cretaceous climate and ocean circulation - Cretaceous Research, vol. 29, pp. 725-753, 2008 Poulsen C. J., Barron E., Arthur M. A., Peterson W. H. - Response of the mid-Cretaceous global oceanic circulation to tectonic and CO2 forcings - Paleoceanography, vol 16, n. 6, pp. 576-592, December 2001 Poulsen C. J., Seidov D., Barron E. J., Peterson W. H. - The impact of paleogeographic evolution on the surface oceanic circulation and the marine environment within the mid-Cretaceous Tethys - Paleoceanography, vol. 13, n. 5, pp. 546-559, 1998 Pucéat E., Lecuyer C., Sheppard S. M. F., Dromart G., Reboulet S., Grandjean P. - Thermal evolution of Cretaceous Tethyan marine waters inferred from oxygen isotope composition of fish tooth enamels - Paleoceanography, vol. 18, n. 2, 2003

Mid-Cenomanian Event I (MCE I, 96 Ma): elemental and osmium isotope evidence for sea level, climate, and palaeocirculation changes in the NW European epicontinental sea

NASA Astrophysics Data System (ADS)

Jarvis, Ian; Roest-Ellis, Sascha; Selby, David

2017-04-01

Cenomanian times (100.5-93.9 Ma) represent perhaps the best documented episode of eustatic rise in sea level in Earth history and the beginning of the Late Mesozoic thermal maximum, driving global expansion of epicontinental seas and the onset of widespread pelagic and hemipelagic carbonate (chalk) deposition. Significant changes occurred in global stable-isotope records, including two prominent perturbations of the carbon cycle -Mid-Cenomanian Event I (MCEI; 96.5-96.2 Ma) and Oceanic Anoxic Event 2 (OAE2; 94.5-93.8 Ma). OAE2 was marked by the widespread deposition of black shales in the deep ocean and epicontinental seas, and a global positive carbon stable-isotope excursion of 2.0 - 2.5‰ δ13C in marine carbonates. Osmium isotopes and other geochemical data indicate that OAE2 was associated with a major pulse of LIP-associated volcanism, with coincident changes in eustatic sea level, rising atmospheric pCO2 and warming climate, but including a transient phase of global cooling - the Plenus Cold Event. MCEI, by contrast, shows a <1‰ δ13Ccarb excursion, and has no associated black shales in most areas, yet it also displays evidence of two episodes of cooling, comparable to the Plenus Cold Event. MCEI marks a major breakpoint on long-term carbon-isotope profiles, from relatively constant to very slowly rising δ13C values through the Lower Cenomanian, to a trend of generally increasing δ13C values through the Middle and Upper Cenomanian. This represents a significant long-term change in the global carbon cycle starting with MCEI. Here, we present new high-resolution major- (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, P) and trace-element (Ba, Cr, Re, Os, Sr, Zr) data and 187Os/188Os isotope results for MCEI from an English Chalk reference section at Folkestone. Our results are compared to published δ13Ccarb, δ18Ocarb, δ13Corg stable isotope and neodymium isotope ɛNd(t) data from the same section. Elemental proxies (Mn, Ti/Al, Zr/Al, Si/Al) define key sequence stratigraphic surfaces, providing a basis for refining relative sea-level curves. Cyclical small-scale transgressive events within the mid-Cenomanian TST of depositional sequence Ce IV are accompanied by coupled increases in ɛNd(t) and decreases in 187Os/188Os ratios. Osi ratios of 0.8 - 0.9 prior to MCEI, peak at 1.2 in the lower peak of the isotope excursion, coincident an influx of boreal fauna and the lowest ɛNd(t) values in the section (<-10), and show a stepped fall thereafter. Highly unradiogenic Osi values of ≤ 0.2 occur immediately above MCEI, in an interval of high ɛNd(t). These geochemical data are interpreted to represent cyclical changes in water mass sources and distribution in the Chalk sea, driven by sea-level and climate change. The remarkably low Osi values recorded following MCEI indicate a dominance of hydrothermal/mantle-like sourced Os in southern England waters at that time.

The Description of Shale Reservoir Pore Structure Based on Method of Moments Estimation

PubMed Central

Li, Wenjie; Wang, Changcheng; Shi, Zejin; Wei, Yi; Zhou, Huailai; Deng, Kun

2016-01-01

Shale has been considered as good gas reservoir due to its abundant interior nanoscale pores. Thus, the study of the pore structure of shale is of great significance for the evaluation and development of shale oil and gas. To date, the most widely used approaches for studying the shale pore structure include image analysis, radiation and fluid invasion methods. The detailed pore structures can be studied intuitively by image analysis and radiation methods, but the results obtained are quite sensitive to sample preparation, equipment performance and experimental operation. In contrast, the fluid invasion method can be used to obtain information on pore size distribution and pore structure, but the relative simple parameters derived cannot be used to evaluate the pore structure of shale comprehensively and quantitatively. To characterize the nanoscale pore structure of shale reservoir more effectively and expand the current research techniques, we proposed a new method based on gas adsorption experimental data and the method of moments to describe the pore structure parameters of shale reservoir. Combined with the geological mixture empirical distribution and the method of moments estimation principle, the new method calculates the characteristic parameters of shale, including the mean pore size (x¯), standard deviation (σ), skewness (Sk) and variation coefficient (c). These values are found by reconstructing the grouping intervals of observation values and optimizing algorithms for eigenvalues. This approach assures a more effective description of the characteristics of nanoscale pore structures. Finally, the new method has been applied to analyze the Yanchang shale in the Ordos Basin (China) and Longmaxi shale from the Sichuan Basin (China). The results obtained well reveal the pore characteristics of shale, indicating the feasibility of this new method in the study of the pore structure of shale reservoir. PMID:26992168

The Description of Shale Reservoir Pore Structure Based on Method of Moments Estimation.

PubMed

Li, Wenjie; Wang, Changcheng; Shi, Zejin; Wei, Yi; Zhou, Huailai; Deng, Kun

2016-01-01

Shale has been considered as good gas reservoir due to its abundant interior nanoscale pores. Thus, the study of the pore structure of shale is of great significance for the evaluation and development of shale oil and gas. To date, the most widely used approaches for studying the shale pore structure include image analysis, radiation and fluid invasion methods. The detailed pore structures can be studied intuitively by image analysis and radiation methods, but the results obtained are quite sensitive to sample preparation, equipment performance and experimental operation. In contrast, the fluid invasion method can be used to obtain information on pore size distribution and pore structure, but the relative simple parameters derived cannot be used to evaluate the pore structure of shale comprehensively and quantitatively. To characterize the nanoscale pore structure of shale reservoir more effectively and expand the current research techniques, we proposed a new method based on gas adsorption experimental data and the method of moments to describe the pore structure parameters of shale reservoir. Combined with the geological mixture empirical distribution and the method of moments estimation principle, the new method calculates the characteristic parameters of shale, including the mean pore size (mean), standard deviation (σ), skewness (Sk) and variation coefficient (c). These values are found by reconstructing the grouping intervals of observation values and optimizing algorithms for eigenvalues. This approach assures a more effective description of the characteristics of nanoscale pore structures. Finally, the new method has been applied to analyze the Yanchang shale in the Ordos Basin (China) and Longmaxi shale from the Sichuan Basin (China). The results obtained well reveal the pore characteristics of shale, indicating the feasibility of this new method in the study of the pore structure of shale reservoir.

Study of Cetane Properties of ATJ Blends Based on World Survey of Jet Fuels

DTIC Science & Technology

2016-01-28

49.84 N/A N/A N/A 46.92 N/A N/A N/A 12 (100% Syn.) 1 57.79 N/A N/A N/A 53.48 N/A N/A N/A a - Conventional petroleum based jet fuel; b - Oil Shale ...Australia (% Nitrogen content unknown) c - Oil Shale , Australia (Low Nitrogen); d - Oil Shale , Australia (High Nitrogen) U/A – Unavailable in PQIS...fuel b - Oil Shale , Australia (% Nitrogen content unknown) c - Oil Shale , Australia (Low Nitrogen) d - Oil Shale , Australia (High Nitrogen) U/A

Solar retorting of oil shale

DOEpatents

Gregg, David W.

1983-01-01

An apparatus and method for retorting oil shale using solar radiation. Oil shale is introduced into a first retorting chamber having a solar focus zone. There the oil shale is exposed to solar radiation and rapidly brought to a predetermined retorting temperature. Once the shale has reached this temperature, it is removed from the solar focus zone and transferred to a second retorting chamber where it is heated. In a second chamber, the oil shale is maintained at the retorting temperature, without direct exposure to solar radiation, until the retorting is complete.

Protein kinase CK2 modulates IL-6 expression in inflammatory breast cancer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Drygin, Denis, E-mail: ddrygin@cylenepharma.com; Ho, Caroline B.; Omori, Mayuko

Highlights: Black-Right-Pointing-Pointer We examine the potential cross-talk between CK2 and IL-6. Black-Right-Pointing-Pointer Inhibition of CK2 by siRNA or CX-4945 inhibits expression of IL-6 in models of IBC. Black-Right-Pointing-Pointer Treatment of IBC patient in the clinic with CX-4945 reduces her IL-6 plasma levels. Black-Right-Pointing-Pointer We demonstrate that CK2 is a potential therapeutic target for IL-6 driven diseases. -- Abstract: Inflammatory breast cancer is driven by pro-angiogenic and pro-inflammatory cytokines. One of them Interleukin-6 (IL-6) is implicated in cancer cell proliferation and survival, and promotes angiogenesis, inflammation and metastasis. While IL-6 has been shown to be upregulated by several oncogenes, the mechanismmore » behind this phenomenon is not well characterized. Here we demonstrate that the pleotropic Serine/Threonine kinase CK2 is implicated in the regulation of IL-6 expression in a model of inflammatory breast cancer. We used siRNAs targeted toward CK2 and a selective small molecule inhibitor of CK2, CX-4945, to inhibit the expression and thus suppress the secretion of IL-6 in in vitro as well as in vivo models. Moreover, we report that in a clinical trial, CX-4945 was able to dramatically reduce IL-6 levels in plasma of an inflammatory breast cancer patient. Our data shed a new light on the regulation of IL-6 expression and position CX-4945 and potentially other inhibitors of CK2, for the treatment of IL-6-driven cancers and possibly other diseases where IL-6 is instrumental, including rheumatoid arthritis.« less

Momentum-driven Winds from Radiatively Efficient Black Hole Accretion and Their Impact on Galaxies

NASA Astrophysics Data System (ADS)

Brennan, Ryan; Choi, Ena; Somerville, Rachel S.; Hirschmann, Michaela; Naab, Thorsten; Ostriker, Jeremiah P.

2018-06-01

We explore the effect of momentum-driven winds representing radiation-pressure-driven outflows from accretion onto supermassive black holes in a set of numerical hydrodynamical simulations. We explore two matched sets of cosmological zoom-in runs of 24 halos with masses ∼1012.0–1013.4 M ⊙ run with two different feedback models. Our “NoAGN” model includes stellar feedback via UV heating, stellar winds and supernovae, photoelectric heating, and cosmic X-ray background heating from a metagalactic background. Our fiducial “MrAGN” model is identical except that it also includes a model for black hole seeding and accretion, as well as heating and momentum injection associated with the radiation from black hole accretion. Our MrAGN model launches galactic outflows, which result in both “ejective” feedback—the outflows themselves that drive gas out of galaxies—and “preventative” feedback, which suppresses the inflow of new and recycling gas. As much as 80% of outflowing galactic gas can be expelled, and accretion can be suppressed by as much as a factor of 30 in the MrAGN runs when compared with the NoAGN runs. The histories of NoAGN galaxies are recycling dominated, with ∼70% of material that leaves the galaxy eventually returning, and the majority of outflowing gas reaccretes on 1 Gyr timescales without AGN feedback. Outflowing gas in the MrAGN runs has a higher characteristic velocity (500–1000 km s‑1 versus 100–300 km s‑1 for outflowing NoAGN gas) and travels as far as a few megaparsecs. Only ∼10% of ejected material is reaccreted in the MrAGN galaxies.

Discussion on upper limit of maturity for marine shale gas accumulation

NASA Astrophysics Data System (ADS)

Huang, Jinliang; Dong, Dazhong; Zhang, Chenchen; Wang, Yuman; Li, Xinjing; Wang, Shufang

2017-04-01

The sedimentary formations of marine shale in China are widely distributed and are characterized by old age, early hydrocarbon-generation and high thermal evolution degree, strong tectonic deformation and reformation and poor preservation conditions. Therefore whether commercial shale gas reservoirs can be formed is a critical issue to be studied. The previous studies showed that the upper threshold of maturity (Ro%) for the gas generation of marine source rocks is 3.0%. Based on comparative studies of marine shale gas exploration practices at home and abroad and reservoir experimental analysis results, we proposed in this paper that the upper threshold of maturity (Ro%) for marine shale gas accumulation is 3.5%. And the main proofs are as follows: (1) There is still certain commercial production in the area with the higher than 3.0% in Marcellus and Woodford marine shale gas plays in North America; (2) The Ro of the Silurian Longmaxi shale in the Sichuan Basin in China is between 2.5% and 3.3%. However, the significant breakthrough has been made in shale gas exploration and the production exceeds 7 billion m3 in 2016; (3) The TOC of the Cambrian Qiongzhusi organic-rich shale in Changning Region in the Sichuan Basin ranges 2% to 7.1% and the Ro is greater than 3.5%. And the resistivity logging of organic-rich shale appears low-ultra low resistivity and inversion of Rt curve. It's suggested that the organic matters in Qiongzhusi organic-rich shale occurs partial carbonization which leads to stronger conductivity; (4) Thermal simulation experiments showed that the specific surface of shale increases with Ro. And the specific surface and adsorptive capacity both reach maximum when the Ro is 3.5%; (5) The analysis of physical properties and SEM images of shale reservoirs indicated that when Ro is higher than 3.5%, the dominant pores of Qiongzhusi shale are micro-pores while the organic pores are relatively poor-developed, and the average porosity is less than 2%.

Morbidity survey of US oil shale workers employed during 1948-1969

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rom, W.N.; Krueger, G.; Zone, J.

The health status of 325 oil shale workers employed at the Anvil Points, Colorado, demonstration facility from 1948 to 1969 was evaluated. As a comparison population, 323 Utah coal miners frequency matched for age were studied. The prevalence of respiratory symptoms among oil shale workers who smoked were similar to the coal miners who smoked, although nonsmoking oil shale workers had fewer symptoms compared to nonsmoking coal workers. Four cases of skin cancers were found on the oil shale workers and eight cases in the controls. Similar numbers of nevi, telangiectasiae, possible pitch warts, pigment changes (solar/senile lentigo), and papillomatamore » (seborrheic keratoses and skin tags) were seen in both groups, while actinic keratoses were more frequent in the oil shale workers. The prevalence of actinic keratoses was significantly associated with oil shale work after allowing for age, sun exposure, and other exposures. The prevalence of pulmonary cytology metaplasia was associated with years of production work in oil shale among both smokers and ex-smokers. More of the oil shale workers had atypical cells in the urine, but the excess mostly found among ex-smokers. Although these workers had short-term and limited oil shale exposure work exposure, the authors recommend that medical surveillance of oil shale workers consider the skin, respiratory, and urinary systems for special observation.« less

Duvernay shale lithofacies distribution analysis in the West Canadian Sedimentary Basin

NASA Astrophysics Data System (ADS)

Zhu, Houqin; Kong, Xiangwen; Long, Huashan; Huai, Yinchao

2018-02-01

In the West Canadian Sedimentary Basin (WCSB), Duvernay shale is considered to contribute most of the Canadian shale gas reserve and production. According to global shale gas exploration and development practice, reservoir property and well completion quality are the two key factors determining the shale gas economics. The two key factors are strongly depending on shale lithofacies. On the basis of inorganic mineralogy theory, all available thin section, X-ray diffraction, scanning electron microscope (SEM), energy dispersive spectrometer (EDS) data were used to assist lithofacies analysis. Gamma ray (GR), acoustic (AC), bulk density (RHOB), neutron porosity (NPHI) and photoelectric absorption cross-section index (PE) were selected for log response analysis of various minerals. Reservoir representative equation was created constrained by quantitative core analysis results, and matrix mineral percentage of quartz, carbonate, feldspar and pyrite were calculated to classify shale lithofacies. Considering the horizontal continuity of seismic data, rock physics model was built, and acoustic impedance integrated with core data and log data was used to predict the horizontal distribution of different lithofacies. The results indicate that: (1) nine lithofacies can be categorized in Duvernay shale, (2) the horizontal distribution of different lithofacies is quite diversified, siliceous shale mainly occurs in Simonette area, calcareous shale is prone to develop in the vicinity of reef, while calcareous-siliceous shale dominates in Willesdon Green area.

Shale gas development impacts on surface water quality in Pennsylvania

PubMed Central

Olmstead, Sheila M.; Muehlenbachs, Lucija A.; Shih, Jhih-Shyang; Chu, Ziyan; Krupnick, Alan J.

2013-01-01

Concern has been raised in the scientific literature about the environmental implications of extracting natural gas from deep shale formations, and published studies suggest that shale gas development may affect local groundwater quality. The potential for surface water quality degradation has been discussed in prior work, although no empirical analysis of this issue has been published. The potential for large-scale surface water quality degradation has affected regulatory approaches to shale gas development in some US states, despite the dearth of evidence. This paper conducts a large-scale examination of the extent to which shale gas development activities affect surface water quality. Focusing on the Marcellus Shale in Pennsylvania, we estimate the effect of shale gas wells and the release of treated shale gas waste by permitted treatment facilities on observed downstream concentrations of chloride (Cl−) and total suspended solids (TSS), controlling for other factors. Results suggest that (i) the treatment of shale gas waste by treatment plants in a watershed raises downstream Cl− concentrations but not TSS concentrations, and (ii) the presence of shale gas wells in a watershed raises downstream TSS concentrations but not Cl− concentrations. These results can inform future voluntary measures taken by shale gas operators and policy approaches taken by regulators to protect surface water quality as the scale of this economically important activity increases. PMID:23479604

EVALUATION OF THE EFFECTS OF WEATHERING ON A 50-YEAR OLD RETORTED OIL-SHALE WASTE PILE, RULISON EXPERIMENTAL RETORT, COLORADO.

USGS Publications Warehouse

Tuttle, Michele L.W.; Dean, Walter E.; Ackerman, Daniel J.; ,

1985-01-01

An oil-shale mine and experimental retort were operated near Rulison, Colorado by the U. S. Bureau of Mines from 1926 to 1929. Samples from seven drill cores from a retorted oil-shale waste pile were analyzed to determine 1) the chemical and mineral composition of the retorted oil shale and 2) variations in the composition that could be attributed to weathering. Unweathered, freshly-mined samples of oil shale from the Mahogany zone of the Green River Formation and slope wash collected away from the waste pile were also analyzed for comparison. The waste pile is composed of oil shale retorted under either low-temperature (400-500 degree C) or high-temperature (750 degree C) conditions. The results of the analyses show that the spent shale within the waste pile contains higher concentrations of most elements relative to unretorted oil shale.

Research continues on Julia Creek shale oil project

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1986-09-01

CSR Limited and the CSIRO Division of Mineral Engineering in Australia are working jointly on the development of a new retorting process for Julia Creek oil shale. This paper describes the retorting process which integrates a fluid bed combustor with a retort in which heat is transferred from hot shale ash to cold raw shale. The upgrading of shale oil into transport fuels is also described.

Investigating the Potential Impacts of Energy Production in the Marcellus Shale Region Using the Shale Network Database

NASA Astrophysics Data System (ADS)

Brantley, S.; Pollak, J.

2016-12-01

The Shale Network's extensive database of water quality observations in the Marcellus Shale region enables educational experiences about the potential impacts of resource extraction and energy production with real data. Through tools that are open source and free to use, interested parties can access and analyze the very same data that the Shale Network team has used in peer-reviewed publications about the potential impacts of hydraulic fracturing on water. The development of the Shale Network database has been made possible through efforts led by an academic team and involving numerous individuals from government agencies, citizen science organizations, and private industry. With these tools and data, the Shale Network team has engaged high school students, university undergraduate and graduate students, as well as citizens so that all can discover how energy production impacts the Marcellus Shale region, which includes Pennsylvania and other nearby states. This presentation will describe these data tools, how the Shale Network has used them in educational settings, and the resources available to learn more.

Reconnaissance of ground-water resources in the Eastern Coal Field Region, Kentucky

USGS Publications Warehouse

Price, William E.; Mull, D.S.; Kilburn, Chabot

1962-01-01

In the Eastern Coal Field region of Kentucky, water is obtained from consolidated sedimentary rocks ranging in age from Devonian to Pennsylvanian and from unconsolidated sediments of Quaternary age. About 95 percent of the area is underlain by shale, sandstone, and coal of Pennsylvanian age. Principal factors governing the availability of water in the region are depth, topographic location, and the lithology of the aquifer penetrated. In general, the yield of the well increases as the depth increases. Wells drilled in topographic lows, such as valleys, are likely to yield more water than wells drilled on topographic highs, such as hills. Sand and gravel, present in thick beds in the alluvium along the Ohio River, form the most productive aquifer in the Eastern Coal Field. Of the consolidated rocks in the region sandstone strata are the best aquifers chiefly because joints, openings along bedding planes, and intergranular pore spaces are best developed in them. Shale also supplies water to many wells in the region, chiefly from joints and openings along bedding planes. Coal constitutes a very small part of the sedimentary section, but it yields water from fractures to many wells. Limestone yields water readily from solution cavities developed along joint and bedding-plane openings. The availability of water in different parts of the region was determined chiefly by analyzing well data collected during the reconnaissance. The resulting water-availability maps, published as hydrologic investigations atlases (Price and others, 1961 a, b; Kilburn and others, 1961) were designed to be used in conjunction with this report. The maps were constructed by dividing the region into 5 physiographic areas, into 10 subareas based chiefly on lithologic facies, and, in the case of the Kanawha section, into 2 quality-of-water areas. The 5 physiographic areas are the Knobs, Mississippian Plateau, Cumberland Plateau section, Kanawha section, and Cumberland Mountain section. The 10 subareas are as follows: 1. The Chattanooga shale. This black shale yields only enough water for a minimum domestic supply-100 to 500 gpd (gallons per day). 2. Mississippian-Devonian rocks exposed along Pine Mountain. These rocks consist of shale, limestone, and sandstone. The limestone yields water to springs, and faulted limestone and sandstone lying below drainage may yield several hundred gallons per minute to wells. 3. Mississippian rocks exposed along the western margin of the region. These rocks consist of thick limestone underlain by shale. The limestone yields enough water for a modern domestic supply (more than 500 gpd) , and discharges as much as 100 gpm (gallons per minute) to springs. The shale yields only enough water for a minimum domestic supply. 4. Subarea 1 of the Lee formation of Pennsylvanian age. The thin shaly rocks of this subarea generally yield only enough water for a minimum domestic supply. 5. Subarea 2 of the Lee formation of Pennsylvanian age. This subarea is predominantly underlain by massive sandstones; it generally yields enough water for a modern domestic supply, and in some places, enough water for small public and industrial supplies. 6. Subarea 1 of the Breathitt and Conemaugh formations of Pennsylvanian age. Rocks in this subarea contain more shale than sandstone. Wells in this subarea range from adequate for a minimum domestic supply to adequate for a modern domestic supply. 7. Subarea 2 of the Breathitt formation of Pennsylvanian age and undifferentiated post-Lee Pennsylvanian rocks. Wells in this subarea yield enough water for a modern domestic supply, and in many places, enough water for small public and industrial supplies. 8. Alluvium along the Ohio River. Mostly composed of glacial outwash sand and gravel, the alluvium is reported to yield as much as 360 gpm to wells. 9. Alluvium along the Big Sandy River and lower reaches of its Tug and Levisa Forks. Where consisting mostly of sand,

Application of petroleum demulsification technology to shale oil emulsions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robertson, R.E.

1983-01-01

Demulsification, the process of emulsion separation, of water-in-oil shale oil emulsions produced by several methods was accomplished using commercial chemical demulsifiers which are used typically for petroleum demulsification. The shale oil emulsions were produced from Green River shale by one in situ and three different above-ground retorts, an in situ high pressure/high temperature steam process, and by washing both retort-produced and hydrotreated shale oils.

Combustion heater for oil shale

DOEpatents

Mallon, R.; Walton, O.; Lewis, A.E.; Braun, R.

1983-09-21

A combustion heater for oil shale heats particles of spent oil shale containing unburned char by burning the char. A delayed fall is produced by flowing the shale particles down through a stack of downwardly sloped overlapping baffles alternately extending from opposite sides of a vertical column. The delayed fall and flow reversal occurring in passing from each baffle to the next increase the residence time and increase the contact of the oil shale particles with combustion supporting gas flowed across the column to heat the shale to about 650 to 700/sup 0/C for use as a process heat source.

Combustion heater for oil shale

DOEpatents

Mallon, Richard G.; Walton, Otis R.; Lewis, Arthur E.; Braun, Robert L.

1985-01-01

A combustion heater for oil shale heats particles of spent oil shale containing unburned char by burning the char. A delayed fall is produced by flowing the shale particles down through a stack of downwardly sloped overlapping baffles alternately extending from opposite sides of a vertical column. The delayed fall and flow reversal occurring in passing from each baffle to the next increase the residence time and increase the contact of the oil shale particles with combustion supporting gas flowed across the column to heat the shale to about 650.degree.-700.degree. C. for use as a process heat source.

Effect of retorted-oil shale leachate on a blue-green alga (Anabaena flos-aquae)

USGS Publications Warehouse

McKnight, Diane M.; Pereira, Wilfred E.; Rostad, Colleen E.; Stiles, Eric A.

1983-01-01

In the event of the development of the large oil shale reserves of Colorado, Utah, and Wyoming, one of the main environmental concerns will be disposal of retorted-oil shale which will be generated in greater volume than the original volume oI the mined oil shale. Investigators have found that leachates of retorted-oil shale are alkaline and have large concentrations of dissolved solids, molybdenum, boron, and fluoride (STOLLENWERK & RUNNELS 1981). STOLLENWERK & RUNNELS (1981) concluded that drainage from waste shale piles could have deleterious effects on the water quality of streams in northwestern Colorado.

Mineral-Resource Assessment of Northern Nye County, Nevada - A Progress Report

USGS Publications Warehouse

Ludington, Steve; John, David A.; Muntean, John L.; Hanson, Andrew D.; Castor, Stephen B.; Henry, Christopher D.; Wintzer, Niki; Cline, Jean S.; Simon, Adam C.

2009-01-01

The U.S. Geological Survey (USGS), University of Nevada, Las Vegas (UNLV), and Nevada Bureau of Mines and Geology (NBMG), which is a part of the University of Nevada, Reno (UNR), have completed the first year of data collection and analysis in preparation for a new mineral- and energy-resource assessment of northern Nye County, Nevada. This report provides information about work completed before October 1, 2009. Existing data are being compiled, including geology, geochemistry, geophysics, and mineral-deposit information. Field studies are underway, which are primarily designed to address issues raised during the review of existing information. In addition, new geochemical studies are in progress, including reanalyzing existing stream-sediment samples with modern methods, and analyzing metalliferous black shales.

Constraining the rate of oceanic deoxygenation leading up to a Cretaceous Oceanic Anoxic Event (OAE-2: ~94 Ma)

PubMed Central

Ostrander, Chadlin M.; Owens, Jeremy D.; Nielsen, Sune G.

2017-01-01

The rates of marine deoxygenation leading to Cretaceous Oceanic Anoxic Events are poorly recognized and constrained. If increases in primary productivity are the primary driver of these episodes, progressive oxygen loss from global waters should predate enhanced carbon burial in underlying sediments—the diagnostic Oceanic Anoxic Event relic. Thallium isotope analysis of organic-rich black shales from Demerara Rise across Oceanic Anoxic Event 2 reveals evidence of expanded sediment-water interface deoxygenation ~43 ± 11 thousand years before the globally recognized carbon cycle perturbation. This evidence for rapid oxygen loss leading to an extreme ancient climatic event has timely implications for the modern ocean, which is already experiencing large-scale deoxygenation. PMID:28808684

Eastern Devonian shales: Organic geochemical studies, past and present

USGS Publications Warehouse

Breger, I.A.; Hatcher, P.G.; Romankiw, L.A.; Miknis, F.P.

1983-01-01

The Eastern Devonian shales are represented by a sequence of sediments extending from New York state, south to the northern regions of Georgia and Alabama, and west into Ohio and to the Michigan and Ilinois Basins. Correlatives are known in Texas. The shale is regionally known by a number of names: Chattanooga, Dunkirk, Rhinestreet, Huron, Antrim, Ohio, Woodford, etc. These shales, other than those in Texas, have elicited much interest because they have been a source of unassociated natural gas. It is of particular interest, however, that most of these shales have no associated crude oil, in spite of the fact that they have some of the characteristics normally attributed to source beds. This paper addresses some of the organic geochemical aspects of the kerogen in these shales, in relation to their oil generating potential. Past organic geochemical studies on Eastern Devonian shales will be reviewed. Recent solid state 13C NMR studies on the nature of the organic matter in Eastern Devonian shales show that Eastern Devonian shales contain a larger fraction of aromatic carbon in their chemical composition. Thus, despite their high organic matter contents, their potential as a petroleum source rock is low, because the kerogen in these shales is of a "coaly" nature and hence more prone to producing natural gas.

Eastern Devonian shales: Organic geochemical studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berger, I.A.; Hatchner, P.G.; Miknis, F.P.

The Eastern Devonian shales are represented by a sequence of sediments extending from New York state, south to the northern regions of Georgia and Alabama, and west into Ohio and to the Michigan and Illinois Basins. Correlatives are known in Texas. The shale is regionally known by a number of names: Chattanooga, Dunkirk, Rhinestreet, Huron, Antrim, Ohio, Woodford, etc. These shales, other than those in Texas, have elicited much interest because they have been a source of unassociated natural gas. It is of particular interest, however, that most of these shales have no associated crude oil, in spite of themore » fact that they have some of the characteristics normally attributed to source beds. This paper addresses some of the organic geochemical aspects of the kerogen in these shales, in relation to their oil generating potential. Past organic geochemical studies on Eastern Devonian shales are reviewed. Recent solid state /sup 13/C NMR studies on the nature of the organic matter in Eastern Devonian shales show that Eastern Devonian shales contain a larger fraction of aromatic carbon in their chemical composition. Thus, despite their high organic matter contents, their potential as a petroleum source rock is low, because the kerogen in these shales is of a ''coaly'' nature and hence more prone to producing natural gas.« less

A Model To Estimate Carbon Dioxide Injectivity and Storage Capacity for Geological Sequestration in Shale Gas Wells.

PubMed

Edwards, Ryan W J; Celia, Michael A; Bandilla, Karl W; Doster, Florian; Kanno, Cynthia M

2015-08-04

Recent studies suggest the possibility of CO2 sequestration in depleted shale gas formations, motivated by large storage capacity estimates in these formations. Questions remain regarding the dynamic response and practicality of injection of large amounts of CO2 into shale gas wells. A two-component (CO2 and CH4) model of gas flow in a shale gas formation including adsorption effects provides the basis to investigate the dynamics of CO2 injection. History-matching of gas production data allows for formation parameter estimation. Application to three shale gas-producing regions shows that CO2 can only be injected at low rates into individual wells and that individual well capacity is relatively small, despite significant capacity variation between shale plays. The estimated total capacity of an average Marcellus Shale well in Pennsylvania is 0.5 million metric tonnes (Mt) of CO2, compared with 0.15 Mt in an average Barnett Shale well. Applying the individual well estimates to the total number of existing and permitted planned wells (as of March, 2015) in each play yields a current estimated capacity of 7200-9600 Mt in the Marcellus Shale in Pennsylvania and 2100-3100 Mt in the Barnett Shale.

Organic geochemistry: Effects of organic components of shales on adsorption: Progress report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ho, P.C.

1988-11-01

The Sedimentary Rock Program at the Oak Ridge National Laboratory is investigating shale to determine its potential suitability as a host rock for the disposal of high-level radioactive wastes (HLW). The selected shales are Upper Dowelltown, Pierre, Green River Formation, and two Conasauga (Nolichucky and Pumpkin Valley) Shales, which represent mineralogical and compositional extremes of shales in the United States. According to mineralogical studies, the first three shales contain 5 to 13 wt % of organic matter, and the two Conasauga Shales only contain trace amounts (2 wt %) of organic matter. Soxhlet extraction with chloroform and a mixture ofmore » chloroform and methanol can remove 0.07 to 5.9 wt % of the total organic matter from these shales. Preliminary analysis if these organic extracts reveals the existence of organic carboxylic acids and hydrocarbons in these samples. Adsorption of elements such as Cs(I), Sr(II) and Tc(VII) on the organic-extracted Upper Dowelltown, Pierre, green River Formation and Pumpkin Valley Shales in synthetic groundwaters (simulating groundwaters in the Conasauga Shales) and in 0.03-M NaHCO/sub 3/ solution indicates interaction between each of the three elements and the organic-extractable bitumen. 28 refs., 8 figs., 10 tabs.« less

Detection of cretaceous incised-valley shale for resource play, Miano gas field, SW Pakistan: Spectral decomposition using continuous wavelet transform

NASA Astrophysics Data System (ADS)

Naseer, Muhammad Tayyab; Asim, Shazia

2017-10-01

Unconventional resource shales can play a critical role in economic growth throughout the world. The hydrocarbon potential of faults/fractured shales is the most significant challenge for unconventional prospect generation. The continuous wavelet transforms (CWT) of spectral decomposition (SD) technology is applied for shale gas prospects on high-resolution 3D seismic data from the Miano area in the Indus platform, SW Pakistan. Schmoker' technique reveals high-quality shales with total organic carbon (TOC) of 9.2% distributed in the western regions. The seismic amplitude, root-mean-square (RMS), and most positive curvature attributes show limited ability to resolve the prospective fractured shale components. The CWT is used to identify the hydrocarbon-bearing faulted/fractured compartments encased within the non-hydrocarbon bearing shale units. The hydrocarbon-bearing shales experience higher amplitudes (4694 dB and 3439 dB) than the non-reservoir shales (3290 dB). Cross plots between sweetness, 22 Hz spectral decomposition, and the seismic amplitudes are found more effective tools than the conventional seismic attribute mapping for discriminating the seal and reservoir elements within the incised-valley petroleum system. Rock physics distinguish the productive sediments from the non-productive sediments, suggesting the potential for future shale play exploration.

Filling a SMBH accretion disk atmosphere at small and intermediate radii

NASA Astrophysics Data System (ADS)

Karas, Vladimir; Czerny, Bozena; Kunneriath, Devaky

2017-08-01

The medium above an accretion disk is highly diluted and hot. An efficient mechanism to deliver particles and dust grains is an open question; apparently, different processes must be in operation. We discuss an interplay of two different scenarios, where the material is elevated from the plane of an equatorial accretion disk into a corona near a supermassive black hole: (i) an electromagnetically induced transport, which can be driven by magnetic field of stars passing across an accretion disk (Karas et al., 2017); and (ii) radiatively driven acceleration by radiation emerging from the disk (Czerny et al 2015), which can launch a dusty wind near above the dust sublimation radius. The former process can operate in the vicinity of a supermassive black hole (SMBH) surrounded by a dense nuclear star-cluster. The latter process involves the effect of radiation pressure from various sources - stars, accretion disc, and the central accreting SMBH; it can help filling the Broad-Line Region against the vertical component of the black hole gravitational attraction and the accretion disk self-gravity at radius about a few $\\times 10^3 R_g$.

Mineralogical characterization of selected shales in support of nuclear waste repository studies: Progress report, October 1987--September 1988

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, S. Y.; Hyder, L. K.; Baxter, P. M.

1989-07-01

One objective of the Sedimentary Rock Program at the Oak Ridge National Laboratory has been to examine end-member shales to develop a data base that will aid in evaluations if shales are ever considered as a repository host rock. Five end-member shales were selected for comprehensive characterization: the Chattanooga Shale from Fentress County, Tennessee; the Pierre Shale from Gregory County, South Dakota; the Green River Formation from Garfield County, Colorado; and the Nolichucky Shale and Pumpkin Valley Shale from Roane County, Tennessee. Detailed micromorphological and mineralogical characterizations of the shales were completed by Lee et al. (1987) in ORNL/TM-10567. Thismore » report is a supplemental characterization study that was necessary because second batches of the shale samples were needed for additional studies. Selected physical, chemical, and mineralogical properties were determined for the second batches; and their properties were compared with the results from the first batches. Physical characterization indicated that the second-batch and first-batch samples had a noticeable difference in apparent-size distributions but had similar primary-particle-size distributions. There were some differences in chemical composition between the batches, but these differences were not considered important in comparison with the differences among the end-member shales. The results of x-ray diffraction analyses showed that the second batches had mineralogical compositions very similar to the first batches. 9 refs., 9 figs., 4 tabs.« less

The flux of radionuclides in flowback fluid from shale gas exploitation.

PubMed

Almond, S; Clancy, S A; Davies, R J; Worrall, F

2014-11-01

This study considers the flux of radioactivity in flowback fluid from shale gas development in three areas: the Carboniferous, Bowland Shale, UK; the Silurian Shale, Poland; and the Carboniferous Barnett Shale, USA. The radioactive flux from these basins was estimated, given estimates of the number of wells developed or to be developed, the flowback volume per well and the concentration of K (potassium) and Ra (radium) in the flowback water. For comparative purposes, the range of concentration was itself considered within four scenarios for the concentration range of radioactive measured in each shale gas basin, the groundwater of the each shale gas basin, global groundwater and local surface water. The study found that (i) for the Barnett Shale and the Silurian Shale, Poland, the 1 % exceedance flux in flowback water was between seven and eight times that would be expected from local groundwater. However, for the Bowland Shale, UK, the 1 % exceedance flux (the flux that would only be expected to be exceeded 1 % of the time, i.e. a reasonable worst case scenario) in flowback water was 500 times that expected from local groundwater. (ii) In no scenario was the 1 % exceedance exposure greater than 1 mSv-the allowable annual exposure allowed for in the UK. (iii) The radioactive flux of per energy produced was lower for shale gas than for conventional oil and gas production, nuclear power production and electricity generated through burning coal.

Accelerated weathering of tough shales : final report.

DOT National Transportation Integrated Search

1977-01-01

The purpose of this study was to find or develop a test that would identify a very tough but relatively rapid weathering type of shale that has caused problems when used in embankments as rock. Eight shales, including the problem shale, were collecte...

43 CFR 3900.5 - Information collection.

Code of Federal Regulations, 2011 CFR

2011-10-01

... MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE MANAGEMENT-GENERAL Oil Shale... information. (b) Respondents are oil shale lessees and operators. The requirement to respond to the... extent and specific characteristics of the Federal oil shale resource. The BLM will use the information...

Direct Observation of Accretion onto a Hypernova's Newly Formed Black Hole

NASA Astrophysics Data System (ADS)

Milisavljevic, Dan

2017-09-01

Models of energetic core-collapse supernovae and long-duration gamma-ray bursts often invoke engine-driven scenarios associated with the formation of compact objects that input energy into the explosion. To date, only indirect evidence of black holes or magnetars formed in these events exists from observations obtained when the explosions are most luminous. Here we request a modest 15 ks Chandra pilot observation of the exceptionally important nearby hypernova SN2002ap to test models that predict X-ray emission associated with its remnant black hole to be detectable after 15 yr of ejecta expansion. Direct observation a newly formed "baby" black hole would be a landmark discovery capable of opening up new ways to investigate fundamental aspects of the core collapse process.

Black Hole Formation in Randall-Sundrum II Braneworlds.

PubMed

Wang, Daoyan; Choptuik, Matthew W

2016-07-01

We present the first numerical study of the full dynamics of a braneworld scenario, working within the framework of the single brane model of Randall and Sundrum. In particular, we study the process of gravitational collapse driven by a massless scalar field which is confined to the brane. Imposing spherical symmetry on the brane, we show that the evolutions of sufficiently strong initial configurations of the scalar field result in black holes that have finite extension into the bulk. Furthermore, we find preliminary evidence that the black holes generated form a unique sequence, irrespective of the details of the initial data. The black hole solutions we obtain from dynamical evolutions are consistent with those previously computed from a static vacuum ansatz.

Microstructural and mineralogical characterization of selected shales in support of nuclear waste repository studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, S.Y.; Hyder, L.K.; Alley, P.D.

1988-01-01

Five shales were examined as part of the Sedimentary Rock Program evaluation of this medium as a potential host for a US civilian nuclear waste repository. The units selected for characterization were the Chattanooga Shale from Fentress County, Tennessee; the Pierre Shale from Gregory County, South Dakota; the Green River Formation from Garfield County, Colorado; and the Nolichucky Shale and Pumpkin Valley Shale from Roane County, Tennessee. The micromorphology and structure of the shales were examined by petrographic, scanning electron, and high-resolution transmission electron microscopy. Chemical and mineralogical compositions were studied through the use of energy-dispersive x-ray, neutron activation, atomicmore » absorption, thermal, and x-ray diffraction analysis techniques. 18 refs., 12 figs., 2 tabs.« less

Potential restrictions for CO2 sequestration sites due to shale and tight gas production.

PubMed

Elliot, T R; Celia, M A

2012-04-03

Carbon capture and geological sequestration is the only available technology that both allows continued use of fossil fuels in the power sector and reduces significantly the associated CO(2) emissions. Geological sequestration requires a deep permeable geological formation into which captured CO(2)can be injected, and an overlying impermeable formation, called a caprock, that keeps the buoyant CO(2) within the injection formation. Shale formations typically have very low permeability and are considered to be good caprock formations. Production of natural gas from shale and other tight formations involves fracturing the shale with the explicit objective to greatly increase the permeability of the shale. As such, shale gas production is in direct conflict with the use of shale formations as a caprock barrier to CO(2) migration. We have examined the locations in the United States where deep saline aquifers, suitable for CO(2) sequestration, exist, as well as the locations of gas production from shale and other tight formations. While estimated sequestration capacity for CO(2) sequestration in deep saline aquifers is large, up to 80% of that capacity has areal overlap with potential shale-gas production regions and, therefore, could be adversely affected by shale and tight gas production. Analysis of stationary sources of CO(2) shows a similar effect: about two-thirds of the total emissions from these sources are located within 20 miles of a deep saline aquifer, but shale and tight gas production could affect up to 85% of these sources. These analyses indicate that colocation of deep saline aquifers with shale and tight gas production could significantly affect the sequestration capacity for CCS operations. This suggests that a more comprehensive management strategy for subsurface resource utilization should be developed.

Palynology, geochemistry and Re-Os age of the Lower-Middle Pennsylvanian stage boundary, central Appalachian basin, USA

NASA Astrophysics Data System (ADS)

Geboy, N.; Tripathy, G. R.; Ruppert, L. F.; Eble, C. F.; Blake, B. M.; Hannah, J. L.; Stein, H. J.

2014-12-01

The central Appalachian basin (CAB) in the eastern United States contains complicated sedimentary sequences often with thin and discontinuous strata. As an economically important coal-producing region, the basin's architectural framework and depositional history are important to understand. Typically, eustatic marine incursions, marked with black shale deposits, are used for basin-wide correlation. The Betsie Shale Member of the Kanawha Formation represents one of these relatively thick and laterally extensive marine zones. This study examines the palynoflora of the Matewan coalbed, which conformably underlies the Betsie, in the context of a new Re-Os date for the Betsie Shale Member and additional geochemical measures. At its base, the Matewan contains abundant lycopsid tree spores, indicative of a submerged, flooded paleomire. Upsection, biodiversity increases to include small fern and calamite spores as well as cordaite pollen. Combined with an observed increase of inertinite, the diversification of palynoflora suggests surficial peat exposure and drying out of the paleomire. A S-rich (28 wt. %) shaley parting separates these lower and upper benches of the Matewan and may represent an initial marine pulse prior to the glacioeustatic incursion that ultimately flooded the Matewan and deposited the overlying Betsie Shale. The Betsie is organic-rich (3.05 - 4.89 wt. % TOC) with Re and Os content ranging from 320 - 1,200 ppb and 1.5 - 5.3 ppb, respectively. The highly enriched Re values result in notably high parent:daughter ratios (187Re/188Os = 3,644 - 5,737). The Re-Os isotopic data yield a Model 1 age of 323 ± 7.8 Ma (n = 7; MSWD = 0.63) with evidence that the true age lies closer to the younger end of the uncertainty. This age is consistent with previous paleontologic-based interpretations but represents the first directly measured radiometric date for the Betsie. An absolute age for the Betsie is a critical result, as the member is correlated with units in Wales and Germany and therefore has implications across the Carboniferous Euramerican Belt. Further, the Betsie has been interpreted to represent the Lower-Middle Pennsylvanian stage boundary in North America, making this directly measured age an important marker not only within the CAB but also for refinement of the Carboniferous timescale.

The Supercritical CO2 Huff-n-puff Experiment of Shale Oil Utilizing Isopropanol

NASA Astrophysics Data System (ADS)

Shang, Shengxiang; Dong, Mingzhe; Gong, Houjian

2018-01-01

In this study, the supercritical CO2 huff-n-puff experiment of shale oil has been investigated. Experimental data shows that the addition of isopropanol can greatly improve the recovery of shale oil. And this provides a new way to improve the recovery of shale oil. In this paper, it is also tried to analyze the influencing factor of isopropanol on the recovery of shale oil by analyzing the MMP.

Sedimentology and stratigraphy of the Kanayut Conglomerate, central and western Brooks Range, Alaska; report of 1981 field season

USGS Publications Warehouse

Nilsen, T.H.; Moore, T.E.

1982-01-01

The Upper Devonian and Lower Mississippian(?) Kanayut Conglomerate forms a major stratigraphic unit along the crest of the Brooks Range of northern Alaska. It crops out for an east-west distance of about 900 km and a north-south distance of about 65 km. The Kanayut is wholly allochthonous and has probably been transported northward on a series of thrust plates. The Kanayut is as thick as 2,600 m in the east-central Brooks Range. It thins and fines to the south and west. The Kanayut forms the middle part of the allochthonous sequence of the Endicott Group, an Upper Devonian and Mississippian clastic sequence underlain by platform limestones of the Baird Group and overlain by platform limestone, carbonaceous shale, and black chert of the Lisburne Group. The Kanayut overlies the marine Upper Devonian Noatak Sandstone or, where it is missing, the marine Upper Devonian Hunt Fork Shale. It is overlain by the marine Mississippian Kayak Shale. The Kanayut Conglomerate forms the fluvial part of a large, coarse-grained delta that prograded to the southwest in Late Devonian time and retreated in Early Mississippian time. Four sections of the Kanayut Conglomerate in the central Brooks Range and five in the western Brooks Range were measured in 1981. The sections from the western Brooks Range document the presence of fluvial cycles in the Kanayut as far west as the shores of the Chukchi Sea. The Kanayut in this area is generally finer grained than it is in the central and eastern Brooks Range, having a maximum clast size of 3 cm. It is probably about 300 m thick. The upper and lower contacts of the Kanayut are gradational. The lower Kanayut contains calcareous, marine-influenced sandstone within channel deposits, and the upper Kanayut contains probable marine interdistributary-bay shale sequences. The members of the Kanayut Conglomerate cannot be differentiated in this region. In the central Brooks Range, sections of the Kanayut Conglomerate at Siavlat Mountain and Kakivilak Creek are typically organized into fining-upward fluvial cycles. The maximum clast size is about 3 cm in this area. The Kanayut in this region is 200-500 m thick and can be divided into the Ear Peak, Shainin Lake, and Stuver Members. The upper contact of the Kanayut with the Kayak Shale is very gradational at Kakivilak Creek and very abrupt at Siavlat Mountain. Paleocurrents from fluvial strata of the Kanayut indicate sediment transport toward the west and south in both the western and central Brooks Range. The maximum clast size distribution generally indicates westward fining from the Shainin Lake region.

Microstructural investigation of a locally mirror-like surface collected at 4 km depth in a Pomeranian shale sample

NASA Astrophysics Data System (ADS)

Pluymakers, Anne; Renard, Francois

2016-04-01

The presence of shiny sliding surfaces, or mirror surfaces, is sometimes thought to have been caused by slip at seismic velocities. Many fault mirrors reported so far are described to occur in carbonate-rich rocks. Here we present microstructural data on a mirror-like slip surface in the Pomeranian shale, recovered from approximately 4 km depth. The accommodated sliding of this fault is probably small, not more than one or two centimeter. The Pomeranian shale is a dark-grey to black shale, composed of 40-60% illite plus mica, 1-10% organic matter, 10% chlorite, and 10 % carbonates plus minor amounts of K-feldspar, plagioclase and kaolinite. In this sample, the surface is optically smooth with striations and some patches that reflect light. Observations using a Hitachi TM3000 (table-top) SEM show that the striations are omnipresent, though more prominent in the carbonate patches (determined using EDS analysis). The smooth surface is locally covered by granular material with a grain size up to 10 μm. This is shown to consist of a mixture of elements and thus likely locally derived fault gouge. The clay-rich parts of the smooth surface are equidimensional grains, with sub-micron grain sizes, whereas in the unperturbed part of the shale core the individual clay platelets are easy to distinguish, with lengths up to 10 μm. The striated calcite-rich patches appear as single grains with sizes up to several millimeters, though they occasionally are smeared out in a direction parallel to the striations. We have analyzed surface roughness at magnifications of 2.5x to 100x using a standard White Light Interferometer, parallel and perpendicular to slip. At low magnifications, 2.5x and 5x, Hurst exponents were anomalously low, around 0.1 to 0.2, interpreted to be related to a lack of sufficient resolution to pick up the striations. At higher magnification the Hurst exponent is 0.34 to 0.43 parallel to the striation, and 0.44 to 0.61 perpendicular to the striation. This relatively low Hurst exponent suggests that this surface has not experienced high strains, even though it locally exhibits mirror-like properties. As such, this data supports the notion that the formation of shiny surfaces is related to grain size reduction, but does not necessarily indicate major slip events. Additionally, the more strongly visible striation in the carbonate-rich parts indicates that some mineralogies are more prone to the formation of striations than others. A full interpretation of this sample is of course complicated by its small size, but these data suggest that when examining fault mirrors and the presence of striations spatial difference in mineralogy need to be taken into account.

Assessment of potential unconventional lacustrine shale-oil and shale-gas resources, Phitsanulok Basin, Thailand, 2014

USGS Publications Warehouse

Schenk, Christopher J.; Charpentier, Ronald R.; Klett, Timothy R.; Mercier, Tracey J.; Tennyson, Marilyn E.; Pitman, Janet K.; Brownfield, Michael E.

2014-01-01

Using a geology-based assessment methodology, the U.S. Geological Survey assessed potential technically recoverable mean resources of 53 million barrels of shale oil and 320 billion cubic feet of shale gas in the Phitsanulok Basin, onshore Thailand.

Clay mineral continental amplifier for marine carbon sequestration in a greenhouse ocean

PubMed Central

Kennedy, Martin J.; Wagner, Thomas

2011-01-01

The majority of carbon sequestration at the Earth’s surface occurs in marine continental margin settings within fine-grained sediments whose mineral properties are a function of continental climatic conditions. We report very high mineral surface area (MSA) values of 300 and 570 m2 g in Late Cretaceous black shales from Ocean Drilling Program site 959 of the Deep Ivorian Basin that vary on subcentennial time scales corresponding with abrupt increases from approximately 3 to approximately 18% total organic carbon (TOC). The observed MSA changes with TOC across multiple scales of variability and on a sample-by-sample basis (centimeter scale), provides a rigorous test of a hypothesized influence on organic carbon burial by detrital clay mineral controlled MSA. Changes in TOC also correspond with geochemical and sedimentological evidence for water column anoxia. Bioturbated intervals show a lower organic carbon loading on mineral surface area of 0.1 mg-OC m-2 when compared to 0.4 mg-OC m-2 for laminated and sulfidic sediments. Although either anoxia or mineral surface protection may be capable of producing TOC of < 5%, when brought together they produced the very high TOC (10–18%) apparent in these sediments. This nonlinear response in carbon burial resulted from minor precession-driven changes of continental climate influencing clay mineral properties and runoff from the African continent. This study identifies a previously unrecognized land–sea connection among continental weathering, clay mineral production, and anoxia and a nonlinear effect on marine carbon sequestration during the Coniacian-Santonian Oceanic Anoxic Event 3 in the tropical eastern Atlantic. PMID:21576498

Microbial communities and organic biomarkers in a Proterozoic-analog sinkhole.

PubMed

Hamilton, T L; Welander, P V; Albrecht, H L; Fulton, J M; Schaperdoth, I; Bird, L R; Summons, R E; Freeman, K H; Macalady, J L

2017-11-01

Little Salt Spring (Sarasota County, FL, USA) is a sinkhole with groundwater vents at ~77 m depth. The entire water column experiences sulfidic (~50 μM) conditions seasonally, resulting in a system poised between oxic and sulfidic conditions. Red pinnacle mats occupy the sediment-water interface in the sunlit upper basin of the sinkhole, and yielded 16S rRNA gene clones affiliated with Cyanobacteria, Chlorobi, and sulfate-reducing clades of Deltaproteobacteria. Nine bacteriochlorophyll e homologues and isorenieratene indicate contributions from Chlorobi, and abundant chlorophyll a and pheophytin a are consistent with the presence of Cyanobacteria. The red pinnacle mat contains hopanoids, including 2-methyl structures that have been interpreted as biomarkers for Cyanobacteria. A single sequence of hpnP, the gene required for methylation of hopanoids at the C-2 position, was recovered in both DNA and cDNA libraries from the red pinnacle mat. The hpnP sequence was most closely related to cyanobacterial hpnP sequences, implying that Cyanobacteria are a source of 2-methyl hopanoids present in the mat. The mats are capable of light-dependent primary productivity as evidenced by 13 C-bicarbonate photoassimilation. We also observed 13 C-bicarbonate photoassimilation in the presence of DCMU, an inhibitor of electron transfer to Photosystem II. Our results indicate that the mats carry out light-driven primary production in the absence of oxygen production-a mechanism that may have delayed the oxygenation of the Earth's oceans and atmosphere during the Proterozoic Eon. Furthermore, our observations of the production of 2-methyl hopanoids by Cyanobacteria under conditions of low oxygen and low light are consistent with the recovery of these structures from ancient black shales as well as their paucity in modern marine environments. © 2017 The Authors. Geobiology Published by John Wiley & Sons Ltd.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Handford, C.R.

Exploration is increasingly dependent upon obtaining credible stratigraphic interpretations of seismic data. With respect to carbonate platforms, two of the most important seismic-imaging and interpretation problems are (1) distinguishing between lowstand unconformities and drowning unconformities, and (2) recognizing paleokarst reservoirs. Lowstand unconformities vs. drowning unconformities. Many contend that onlapping wedges of strata above sequence boundaries but below the previous shelf break comprise the lowstand systems tract. An alternative view is that onlapping wedges do not record sea level falls, but instead chronicle sea level rises and platform demise. A Mississippian carbonate ramp exposed along the southern margin of North Americamore » is flanked by a siliciclastic lowstand wedge and overlain by a drowning succession of black shales. This dual history of lowstand exposure and drowning formed two baselap surfaces, which lie so close to each other on the shelf that seismic dissemination is almost impossible. The paradox is that although the ramp was terminated by drowning, the visible seismic baselap was due to low-stand exposure. Numerous large fields around the world produce from carbonate reservoirs with a moderate to strong paleokarst overprint. Their discoveries, however, were structurally driven and rarely based upon predrill knowledge of paleokarst systems. In fact, there has been little effort to determine how to recognize paleocave systems in seismic reflection data. To narrow this gap, the sedimentary fill and stratal geometries of modern cave systems were examined and modeled seismically. The models show a passage from continuous reflections in the undisturbed country rock to discontinuous reflections inclined toward the cavern core. Velocity pull-ups and pull-downs are significant where velocity and density contrasts between the country rock and collapsed chamber are important.« less

Comparison of Pore Fractal Characteristics Between Marine and Continental Shales

NASA Astrophysics Data System (ADS)

Liu, Jun; Yao, Yanbin; Liu, Dameng; Cai, Yidong; Cai, Jianchao

Fractal characterization offers a quantitative evaluation on the heterogeneity of pore structure which greatly affects gas adsorption and transportation in shales. To compare the fractal characteristics between marine and continental shales, nine samples from the Lower Silurian Longmaxi formation in the Sichuan basin and nine from the Middle Jurassic Dameigou formation in the Qaidam basin were collected. Reservoir properties and fractal dimensions were characterized for all the collected samples. In this study, fractal dimensions were originated from the Frenkel-Halsey-Hill (FHH) model with N2 adsorption data. Compared to continental shale, marine shale has greater values of quartz content, porosity, specific surface area and total pore volume but lower level of clay minerals content, permeability, average pore diameter and methane adsorption capacity. The quartz in marine shale is mostly associated with biogenic origin, while that in continental shale is mainly due to terrigenous debris. The N2 adsorption-desorption isotherms exhibit that marine shale has fewer inkbottle-shaped pores but more plate-like and slit-shaped pores than continental shale. Two fractal dimensions (D1 and D2) were obtained at P/Po of 0-0.5 and 0.5-1. The dimension D2 is commonly greater than D1, suggesting that larger pores (diameter >˜ 4nm) have more complex structures than small pores (diameter <˜ 4nm). The fractal dimensions (both D1 and D2) positively correlate to clay minerals content, specific surface area and methane adsorption capacity, but have negative relationships with porosity, permeability and average pore diameter. The fractal dimensions increase proportionally with the increasing quartz content in marine shale but have no obvious correlation with that in continental shale. The dimension D1 is correlative to the TOC content and permeability of marine shale at a similar degree with dimension D2, while the dimension D1 is more sensitive to those of continental shale than dimension D2. Compared with dimension D2, for two shales, dimension D1 is better associated with the content of clay minerals but has worse correlations with the specific surface area and average pore diameter.

Potentiometric surface of the Minnekahta Aquifer in the Black Hills area, South Dakota

USGS Publications Warehouse

Strobel, Michael L.; Galloway, Joel M.; Hamade, Ghaith R.; Jarrell, Gregory J.

2000-01-01

This map is a product of the Black Hills Hydrology Study, which was initiated in 1990 to assess the quantity, quality, and distribution of surface water and ground water in the Black Hills area of South Dakota (Driscoll, 1992). This long-term study is a cooperative effort between the U.S. Geological Survey (USGS), the South Dakota Department of Environment and Natural Resources, and the West Dakota Water Development District, which represents various local and county cooperators. This map is part of a series of 1:100,000-scale maps for the study. The maps include a hydrogeologic map, structure-contour maps (altitudes of the tops of formations) for five formations that contain major aquifers in the study area, and potentiometric maps for these five major aquifers (the Inyan Kara, Minnekahta, Minnelusa, Madison, and Deadwood aquifers).The study area consists of the topographically defined Black Hills and adjacent areas located in western South Dakota. The Black Hills area is an elongated, dome-shaped feature, about 125 miles long and 60 miles wide, which was uplifted during the Laramide orogeny (Feldman and Heimlich, 1980). The oldest geologic units in the study area are Precambrian metamorphic and igneous rocks, which are exposed in the central core of the Black Hills. Surrounding the Precambrian core is a layered series of sedimentary rocks including limestones, sandstones, and shales that are exposed in roughly concentric rings around the uplifted flanks of the Black Hills. The bedrock sedimentary units typically dip away from the uplifted Black Hills at angles that approach or exceed 10 degrees near the outcrops, and decrease with distance from the uplift. Many of the sedimentary units contain aquifers, both within and beyond the study area. Recharge to these aquifers occurs from infiltration of precipitation upon the outcrops and, in some cases, from infiltration of streamflow (Hortness and Driscoll, 1998). Artesian conditions generally exist within these aquifers where an upper confining layer is present. Flowing wells and springs that originate from the confined aquifers are common around the periphery of the Black Hills.The purpose of this map is to show the potentiometric surface of the Minnekahta aquifer within the study area. The map provides a tool for evaluating ground-water flow directions and hydraulic gradients in the Minnekahta aquifer.

Potentiometric surface of the Inyan Kara Aquifer in the Black Hills area, South Dakota

USGS Publications Warehouse

Strobel, Michael L.; Galloway, Joel M.; Hamade, Ghaith R.; Jarrell, Gregory J.

2000-01-01

This map is a product of the Black Hills Hydrology Study, which was initiated in 1990 to assess the quantity, quality, and distribution of surface water and ground water in the Black Hills area of South Dakota (Driscoll, 1992). This long-term study is a cooperative effort between the U.S. Geological Survey (USGS), the South Dakota Department of Environment and Natural Resources, and the West Dakota Water Development District, which represents various local and county cooperators. This map is part of a series of 1:100,000-scale maps for the study. The maps include a hydrogeologic map, structure-contour maps (altitudes of the tops of formations) for five formations that contain major aquifers in the study area, and potentiometric maps for these five major aquifers (the Inyan Kara, Minnekahta, Minnelusa, Madison, and Deadwood aquifers).The study area consists of the topographically defined Black Hills and adjacent areas located in western South Dakota. The Black Hills area is an elongated, dome-shaped feature, about 125 miles long and 60 miles wide, which was uplifted during the Laramide orogeny (Feldman and Heimlich, 1980). The oldest geologic units in the study area are Precambrian metamorphic and igneous rocks, which are exposed in the central core of the Black Hills. Surrounding the Precambrian core is a layered series of sedimentary rocks including limestones, sandstones, and shales that are exposed in roughly concentric rings around the uplifted flanks of the Black Hills. The bedrock sedimentary units typically dip away from the uplifted Black Hills at angles that approach or exceed 10 degrees near the outcrops, and decrease with distance from the uplift. Many of the sedimentary units contain aquifers, both within and beyond the study area. Recharge to these aquifers occurs from infiltration of precipitation upon the outcrops and, in some cases, from infiltration of streamflow (Hortness and Driscoll, 1998). Artesian conditions generally exist within these aquifers where an upper confining layer is present. Flowing wells and springs that originate from the confined aquifers are common around the periphery of the Black Hills.The purpose of this map is to show the potentiometric surface of the Inyan Kara aquifer within the study area. The map provides a tool for evaluating ground-water flow directions and hydraulic gradients in the Inyan Kara aquifer.

Potentiometric surface of the Deadwood Aquifer in the Black Hills area, South Dakota

USGS Publications Warehouse

Strobel, Michael L.; Galloway, Joel M.; Hamade, Ghaith R.; Jarrell, Gregory J.

2000-01-01

This map is a product of the Black Hills Hydrology Study, which was initiated in 1990 to assess the quantity, quality, and distribution of surface water and ground water in the Black Hills area of South Dakota (Driscoll, 1992). This long-term study is a cooperative effort between the U.S. Geological Survey (USGS), the South Dakota Department of Environment and Natural Resources, and the West Dakota Water Development District, which represents various local and county cooperators. This map is part of a series of 1:100,000-scale maps for the study. The maps include a hydrogeologic map, structure-contour maps (altitudes of the tops of formations) for five formations that contain major aquifers in the study area, and potentiometric maps for these five major aquifers (the Inyan Kara, Minnekahta, Minnelusa, Madison, and Deadwood aquifers).The study area consists of the topographically defined Black Hills and adjacent areas located in western South Dakota. The Black Hills area is an elongated, dome-shaped feature, about 125 miles long and 60 miles wide, which was uplifted during the Laramide orogeny (Feldman and Heimlich, 1980). The oldest geologic units in the study area are Precambrian metamorphic and igneous rocks, which are exposed in the central core of the Black Hills. Surrounding the Precambrian core is a layered series of sedimentary rocks including limestones, sandstones, and shales that are exposed in roughly concentric rings around the uplifted flanks of the Black Hills. The bedrock sedimentary units typically dip away from the uplifted Black Hills at angles that approach or exceed 10 degrees near the outcrops, and decrease with distance from the uplift. Many of the sedimentary units contain aquifers, both within and beyond the study area. Recharge to these aquifers occurs from infiltration of precipitation upon the outcrops and, in some cases, from infiltration of streamflow (Hortness and Driscoll, 1998). Artesian conditions generally exist within these aquifers where an upper confining layer is present. Flowing wells and springs that originate from the confined aquifers are common around the periphery of the Black Hills.The purpose of this map is to show the potentiometric surface of the Deadwood aquifer within the study area. The map provides a tool for evaluating ground-water flow directions and hydraulic gradients in the Deadwood aquifer.

Potentiometric surface of the Minnelusa Aquifer in the Black Hills area, South Dakota

USGS Publications Warehouse

Strobel, Michael L.; Galloway, Joel M.; Hamade, Ghaith R.; Jarrell, Gregory J.

2000-01-01

This map is a product of the Black Hills Hydrology Study, which was initiated in 1990 to assess the quantity, quality, and distribution of surface water and ground water in the Black Hills area of South Dakota (Driscoll, 1992). This long-term study is a cooperative effort between the U.S. Geological Survey (USGS), the South Dakota Department of Environment and Natural Resources, and the West Dakota Water Development District, which represents various local and county cooperators. This map is part of a series of 1:100,000-scale maps for the study. The maps include a hydrogeologic map, structure-contour maps (altitudes of the tops of formations) for five formations that contain major aquifers in the study area, and potentiometric maps for these five major aquifers (the Inyan Kara, Minnekahta, Minnelusa, Madison, and Deadwood aquifers).The study area consists of the topographically defined Black Hills and adjacent areas located in western South Dakota. The Black Hills area is an elongated, dome-shaped feature, about 125 miles long and 60 miles wide, which was uplifted during the Laramide orogeny (Feldman and Heimlich, 1980). The oldest geologic units in the study area are Precambrian metamorphic and igneous rocks, which are exposed in the central core of the Black Hills. Surrounding the Precambrian core is a layered series of sedimentary rocks including limestones, sandstones, and shales that are exposed in roughly concentric rings around the uplifted flanks of the Black Hills. The bedrock sedimentary units typically dip away from the uplifted Black Hills at angles that approach or exceed 10 degrees near the outcrops, and decrease with distance from the uplift. Many of the sedimentary units contain aquifers, both within and beyond the study area. Recharge to these aquifers occurs from infiltration of precipitation upon the outcrops and, in some cases, from infiltration of streamflow (Hortness and Driscoll, 1998). Artesian conditions generally exist within these aquifers where an upper confining layer is present. Flowing wells and springs that originate from the confined aquifers are common around the periphery of the Black Hills.The purpose of this map is to show the potentiometric surface of the Minnelusa aquifer within the study area. The map provides a tool for evaluating ground-water flow directions and hydraulic gradients in the Minnelusa aquifer.

Potentiometric surface of the Madison Aquifer in the Black Hills area, South Dakota

USGS Publications Warehouse

Strobel, Michael L.; Galloway, Joel M.; Hamade, Ghaith R.; Jarrell, Gregory L.

2000-01-01

This map is a product of the Black Hills Hydrology Study, which was initiated in 1990 to assess the quantity, quality, and distribution of surface water and ground water in the Black Hills area of South Dakota (Driscoll, 1992). This long-term study is a cooperative effort between the U.S. Geological Survey (USGS), the South Dakota Department of Environment and Natural Resources, and the West Dakota Water Development District, which represents various local and county cooperators. This map is part of a series of 1:100,000-scale maps for the study. The maps include a hydrogeologic map, structure-contour maps (altitudes of the tops of formations) for five formations that contain major aquifers in the study area, and potentiometric maps for these five major aquifers (the Inyan Kara, Minnekahta, Minnelusa, Madison, and Deadwood aquifers).The study area consists of the topographically defined Black Hills and adjacent areas located in western South Dakota. The Black Hills area is an elongated, dome-shaped feature, about 125 miles long and 60 miles wide, which was uplifted during the Laramide orogeny (Feldman and Heimlich, 1980). The oldest geologic units in the study area are Precambrian metamorphic and igneous rocks, which are exposed in the central core of the Black Hills. Surrounding the Precambrian core is a layered series of sedimentary rocks including limestones, sandstones, and shales that are exposed in roughly concentric rings around the uplifted flanks of the Black Hills. The bedrock sedimentary units typically dip away from the uplifted Black Hills at angles that approach or exceed 10 degrees near the outcrops, and decrease with distance from the uplift. Many of the sedimentary units contain aquifers, both within and beyond the study area. Recharge to these aquifers occurs from infiltration of precipitation upon the outcrops and, in some cases, from infiltration of streamflow (Hortness and Driscoll, 1998). Artesian conditions generally exist within these aquifers where an upper confining layer is present. Flowing wells and springs that originate from the confined aquifers are common around the periphery of the Black Hills.The purpose of this map is to show the potentiometric surface of the Madison aquifer within the study area. The map provides a tool for evaluating ground-water flow directions and hydraulic gradients in the Madison aquifer.

Making the Case for the Outlier: Researcher Reflections of an African-American Female Deputy Superintendent Who Decided to Close the Achievement Gap

ERIC Educational Resources Information Center

Beard, Karen Stansberry

2012-01-01

This article presents researcher reflections of a case study of a Black female deputy superintendent who made the value-driven decision to close the achievement gap in her district. I posit that she is an outlier because she is Black and female in a predominantly white male field of practice, she effectively closed the achievement gap through her…

Shale Gas Well, Hydraulic Fracturing, and Formation Data to Support Modeling of Gas and Water Flow in Shale Formations

NASA Astrophysics Data System (ADS)

Edwards, Ryan W. J.; Celia, Michael A.

2018-04-01

The potential for shale gas development and hydraulic fracturing to cause subsurface water contamination has prompted a number of modeling studies to assess the risk. A significant impediment for conducting robust modeling is the lack of comprehensive publicly available information and data about the properties of shale formations, shale wells, the process of hydraulic fracturing, and properties of the hydraulic fractures. We have collated a substantial amount of these data that are relevant for modeling multiphase flow of water and gas in shale gas formations. We summarize these data and their sources in tabulated form.

Characterization of raw and burnt oil shale from Dotternhausen: Petrographical and mineralogical evolution with temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thiéry, Vincent, E-mail: vincent.thiery@mines-douai.fr; Université de Lille; Bourdot, Alexandra, E-mail: alexandra.bourdot@gmail.com

The Toarcian Posidonia shale from Dotternhausen, Germany, is quarried and burnt in a fluidized bed reactor to produce electricity. The combustion residue, namely burnt oil shale (BOS), is used in the adjacent cement work as an additive in blended cements. The starting material is a typical laminated oil shale with an organic matter content ranging from 6 to 18%. Mineral matter consists principally of quartz, feldspar, pyrite and clays. After calcination in the range, the resulting product, burnt oil shale, keeps the macroscopic layered texture however with different mineralogy (anhydrite, lime, iron oxides) and the formation of an amorphous phase.more » This one, studied under STEM, reveals a typical texture of incipient partial melting due to a long retention time (ca. 30 min) and quenching. An in-situ high temperature X-ray diffraction (HTXRD) allowed studying precisely the mineralogical changes associated with the temperature increase. - Highlights: • We present oil shale/burnt oil shale characterization. • The Posidonia Shale is burnt in a fluidized bed. • Mineralogical evolution with temperature is complex. • The burnt oil shale is used in composite cements.« less

Familial Influences on Poverty Among Young Children in Black Immigrant, U.S.-born Black, and Nonblack Immigrant Families

PubMed Central

Thomas, Kevin J. A.

2014-01-01

This study examines how familial contexts affect poverty disparities between the children of immigrant and U.S.-born blacks, and among black and nonblack children of immigrants. Despite lower gross child poverty rates in immigrant than in U.S.-born black families, accounting for differences in family structure reveals that child poverty risks among blacks are highest in single-parent black immigrant families. In addition, within two-parent immigrant families, child poverty declines associated with increasing assimilation are greater than the respective declines in single-parent families. The heads of black immigrant households have more schooling than those of native-black households. However, increased schooling has a weaker negative association with child poverty among the former than among the latter. In terms of racial disparities among the children of immigrants, poverty rates are higher among black than nonblack children. This black disadvantage is, however, driven by the outcomes of first-generation children of African and Hispanic-black immigrants. The results also show that although children in refugee families face elevated poverty risks, these risks are higher among black than among nonblack children of refugees. In addition, the poverty-reducing impact associated with having an English-proficient household head is about three times lower among black children of immigrants than among non-Hispanic white children of immigrants. PMID:21491186

43 CFR 3930.10 - General performance standards.

Code of Federal Regulations, 2011 CFR

2011-10-01

... MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) MANAGEMENT OF OIL SHALE EXPLORATION AND LEASES Management of Oil Shale Exploration Licenses and Leases § 3930.10 General performance standards. The operator... adversely affect the recovery of shale oil or other minerals producible under an oil shale lease during...

A multi-scale micromechanics framework for shale using the nano-tools

NASA Astrophysics Data System (ADS)

Ortega, J.; Ulm, F.; Abousleiman, Y.

2009-12-01

The successful prediction of poroelastic properties of fine-grained rocks such as shale continues to be a formidable challenge for the geophysics community. The highly heterogeneous nature of shale in terms of its compositional and microstructural features translates into a complex anisotropic behavior observed at macroscopic length scales. The recent application of instrumented indentation for the mechanical characterization of shale has revealed the granular response and intrinsic anisotropy of its porous clay phase at nanometer length scales [1-2]. This discovered mechanical behavior at the grain scale has been incorporated into the development of a multi-scale, micromechanics model for shale poroelasticity [3]. The only inputs to the model are two volumetric parameters synthesizing the mineralogy and porosity information of a shale sample. The model is meticulously calibrated and validated, as displayed in Fig. 1, with independent data sets of anisotropic elasticity obtained from nanoindentation experiments and standard laboratory acoustic measurements for shale specimens with and without organic content. The treatment of the elastic anisotropy corresponding to the porous clay fabric, as sensed by nanoindentation, delineates the contribution of the intrinsic anisotropy in shale to its overall anisotropy observed at macroscales. Furthermore, the proposed poroelastic formulation provides access to intrinsic rock parameters such as Biot pore pressure coefficients that are of importance for problems of flow in porous media. In addition, the model becomes a useful tool in geophysics applications for the prediction of shale acoustic properties from material-specific information such as porosity, mineralogy, and density measurements. References: [1] Ulm, F.-J., Abousleiman, Y. (2006) ‘The nanogranular nature of shale.’ Acta Geot. 1(2), 77-88. [2] Bobko, C., Ulm, F.-J. (2008) ‘The nano-mechanical morphology of shale.’ Mech. Mat. 40(4-5), 318-337. [3] Ortega, J. A., Ulm, F.-J., Abousleiman, Y. (2009) ‘The nanogranular acoustic signature of shale.’ Geophysics 74(3), D65-D84. Fig. 1. Comparisons between predicted and experimental elasticity obtained from nanoindentation experiments (left) and acoustic measurements (right) for shale with and without organic content (hollow and solid data points). Nanoindentation elasticity of the porous clay in shale is presented as a function of the clay packing density (one minus the nanoporosity). The x-1, x-3 directions correspond to parallel and normal-to-bedding plane properties, respectively. All nanoindentation data and acoustic measurements for organic-rich shale from [2-3]. Acoustic measurements for organic-free shale were gathered from literature sources compiled in [3].

Very Broad [O III] λλ4959, 5007 Emission from the NGC 4472 Globular Cluster RZ 2109 and Implications for the Mass of Its Black Hole X-Ray Source

NASA Astrophysics Data System (ADS)

Zepf, Stephen E.; Stern, Daniel; Maccarone, Thomas J.; Kundu, Arunav; Kamionkowski, Marc; Rhode, Katherine L.; Salzer, John J.; Ciardullo, Robin; Gronwall, Caryl

2008-08-01

We present Keck LRIS spectroscopy of the black hole-hosting globular cluster RZ 2109 in the Virgo elliptical galaxy NGC 4472. We find that this object has extraordinarily broad [O III] λ5007 and [O III] λ4959 emission lines, with velocity widths of approximately 2000 km s-1. This result has significant implications for the nature of this accreting black hole system and the mass of the globular cluster black hole. We show that the broad [O III] λ5007 emission must arise from material driven at high velocity from the black hole system. This is because the volume available near the black hole is too small by many orders of magnitude to have enough [O III]-emitting atoms to account for the observed L([O III] λ5007) at high velocities, even if this volume is filled with oxygen at the critical density for [O III] λ5007. The Balmer emission is also weak, indicating the observed [O III] is not due to shocks. We therefore conclude that the [O III] λλ4959, 5007 is produced by photoionization of material driven across the cluster. The only known way to drive significant material at high velocity is for a system accreting mass near or above its Eddington limit, which indicates a stellar-mass black hole. Since it is dynamically implausible to form an accreting stellar-mass black hole system in a globular cluster with an intermediate-mass black hole (IMBH), it appears this massive globular cluster does not have an IMBH. We discuss further tests of this conclusion, and its implications for the MBH - Mstellar and MBH - σ relations. Based on observations made at the W. M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California, and the National Aeronautics and Space Administration. The Observatory was made possible by the generous financial support of the W. M. Keck Foundation.

Colorado oil shale: the current status, October 1979

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1979-01-01

A general background to oil shale and the potential impacts of its development is given. A map containing the names and locations of current oil shale holdings is included. The history, geography, archaeology, ecology, water resources, air quality, energy resources, land use, sociology, transportation, and electric power for the state of Colorado are discussed. The Colorado Joint Review Process Stages I, II, and III-oil shale are explained. Projected shale oil production capacity to 1990 is presented. (DC)

Process concept of retorting of Julia Creek oil shale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sitnai, O.

1984-06-01

A process is proposed for the above ground retorting of the Julia Creek oil shale in Queensland. The oil shale characteristics, process description, chemical reactions of the oil shale components, and the effects of variable and operating conditions on process performance are discussed. The process contains a fluidized bed combustor which performs both as a combustor of the spent shales and as a heat carrier generator for the pyrolysis step. 12 references, 5 figures, 5 tables.

Water and mineral relations of Atriplex canescens and A. cuneata on saline processed oil shale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Richardson, S.G.

1979-01-01

Growth, mineral uptake and water relations of Atriplex canescens and A. cuneata, both native to the arid oil shale region of northeastern Utah, were studied in the greenhouse and laboratory as affected by various salinity levels and specific ions in processed oil shale. Salinity of the shale was manipulated by moistening leached processed oil shale to near field capacity (20% H/sub 2/O by weight) with solutions of shale leachate, sodium sulfate, magnesium sulfate or sodium chloride at equiosmotic concentrations ranging from 0 to -30 bars. Although shale salinity did not affect osmotic adjustment, zero turgor points of A. canescens becamemore » more negative with reductions in shale moisture percentage. Differences in plant growth due to differet ions in the soil solution could not be explained by effects on osmotic adjustment. However, greater growth of A. canescens in Na/sub 2/SO/sub 4/ treated than MgSO/sub 4/ treated leached shale was associated with greater leaf succulence, greater lamina lengths and lamina widths and lower diffusive leaf resistances. Potassium added to leached and unleached processed oil shale increased shoot and root biomass production, shoot/root ratio, leaf K content, and water use efficiency of a sodium-excluding Atriplex canescens biotype but did not increase growth of a sodium-accumulating biotype.« less

Study on the microwave catalytic pyrolysis characteristics and energy consumption analysis of oil shale

NASA Astrophysics Data System (ADS)

Chen, Chunxiang; Cheng, Zheng; Xu, Qing; Qin, Songheng

2018-04-01

In order to explore the high-efficient utilization of oil shale, the effects of different microwave powers and different kinds of catalysts (metal oxides and metal salts) on the temperature characteristics and product yield towards the oil shale are investigated by microwave catalytic pyrolysis. The results show that the effect of microwave power on the heating and pyrolysis rates of oil shale is significant, and the maximum output of shale oil is 5.1% when the microwave power is 1500W; CaO has a certain effect on the temperature rise of oil shale, and MgO and CuO have a certain degree of inhibition, but the addition of three kinds of metal oxidation is beneficial to increase the shale oil production; From the perspective of unit power consumption and gas production, the catalytic effect order of three kinds of metal oxides is MgO> CaO> CuO; The addition of three kinds of metal salts is favorable for the increase of pyrolysis temperature of oil shale, after adding 5% ZnCl2, the unit power consumption of shale oil and pyrolysis gas increases by 62.60% and 81.96% respectively. After adding 5% NaH2PO3, the unit power consumption of shale oil increases by 64.64%, and reduces by 9.56% by adding 5% MgCl2.

Water use for Shale-gas production in Texas, U.S.

PubMed

Nicot, Jean-Philippe; Scanlon, Bridget R

2012-03-20

Shale-gas production using hydraulic fracturing of mostly horizontal wells has led to considerable controversy over water-resource and environmental impacts. The study objective was to quantify net water use for shale-gas production using data from Texas, which is the dominant producer of shale gas in the U.S. with a focus on three major plays: the Barnett Shale (~15,000 wells, mid-2011), Texas-Haynesville Shale (390 wells), and Eagle Ford Shale (1040 wells). Past water use was estimated from well-completion data, and future water use was extrapolated from past water use constrained by shale-gas resources. Cumulative water use in the Barnett totaled 145 Mm(3) (2000-mid-2011). Annual water use represents ~9% of water use in Dallas (population 1.3 million). Water use in younger (2008-mid-2011) plays, although less (6.5 Mm(3) Texas-Haynesville, 18 Mm(3) Eagle Ford), is increasing rapidly. Water use for shale gas is <1% of statewide water withdrawals; however, local impacts vary with water availability and competing demands. Projections of cumulative net water use during the next 50 years in all shale plays total ~4350 Mm(3), peaking at 145 Mm(3) in the mid-2020s and decreasing to 23 Mm(3) in 2060. Current freshwater use may shift to brackish water to reduce competition with other users.

Field and Lab-Based Microbiological Investigations of the Marcellus Shale

NASA Astrophysics Data System (ADS)

Wishart, J. R.; Neumann, K.; Edenborn, H. M.; Hakala, A.; Yang, J.; Torres, M. E.; Colwell, F. S.

2013-12-01

The recent exploration of shales for natural gas resources has provided the opportunity to study their subsurface geochemistry and microbiology. Evidence indicates that shale environments are marked by extreme conditions such as high temperature and pressure, low porosity, permeability and connectivity, and the presence of heavy metals and radionuclides. It has been postulated that many of these shales are naturally sterile due to the high pressure and temperature conditions under which they were formed. However, it has been shown in the Antrim and New Albany shales that microbial communities do exist in these environments. Here we review geochemical and microbiological evidence for the possible habitation of the Marcellus shale by microorganisms and compare these conditions to other shales in the U.S. Furthermore, we describe the development of sampling and analysis techniques used to evaluate microbial communities present in the Marcellus shale and associated hydraulic fracturing fluid. Sampling techniques thus far have consisted of collecting flowback fluids from wells and water impoundments and collecting core material from previous drilling expeditions. Furthermore, DNA extraction was performed on Marcellus shale sub-core with a MoBio PowerSoil kit to determine its efficiency. Assessment of the Marcellus shale indicates that it has low porosity and permeability that are not conducive to dense microbial populations; however, moderate temperatures and a natural fracture network may support a microbial community especially in zones where the Marcellus intersects more porous geologic formations. Also, hydraulic fracturing extends this fracture network providing more environments where microbial communities can exist. Previous research which collected flowback fluids has revealed a diverse microbial community that may be derived from hydrofrac fluid production or from the subsurface. DNA extraction from 10 g samples of Marcellus shale sub-core were unsuccessful even when samples were spiked with 8x108 cells/g of shale. This indicated that constituents of shale such as high levels of carbonates, humic acids and metals likely inhibited components of the PowerSoil kit. Future research is focused on refining sample collection and analyses to gain a full understanding of the microbiology of the Marcellus shale and associated flowback fluids. This includes the development of an in situ osmosampler, which will collect temporally relevant fluid and colonized substrate samples. The design of the osmosampler for hydraulic fracturing wells is being adapted from those used to sample marine environments. Furthermore, incubation experiments are underway to study interactions between microbial communities associated with hydraulic fracturing fluid and Marcellus shale samples. In conclusion, evidence suggests that the Marcellus shale is a possible component of the subsurface biosphere. Future studies will be valuable in determining the microbial community structure and function in relation to the geochemistry of the Marcellus shale and its future development as a natural gas resource.

Solar heated oil shale pyrolysis process

NASA Technical Reports Server (NTRS)

Qader, S. A. (Inventor)

1985-01-01

An improved system for recovery of a liquid hydrocarbon fuel from oil shale is presented. The oil shale pyrolysis system is composed of a retort reactor for receiving a bed of oil shale particules which are heated to pyrolyis temperature by means of a recycled solar heated gas stream. The gas stream is separated from the recovered shale oil and a portion of the gas stream is rapidly heated to pyrolysis temperature by passing it through an efficient solar heater. Steam, oxygen, air or other oxidizing gases can be injected into the recycle gas before or after the recycle gas is heated to pyrolysis temperature and thus raise the temperature before it enters the retort reactor. The use of solar thermal heat to preheat the recycle gas and optionally the steam before introducing it into the bed of shale, increases the yield of shale oil.

Assessment of potential shale gas and shale oil resources of the Norte Basin, Uruguay, 2011

USGS Publications Warehouse

Schenk, Christopher J.; Kirschbaum, Mark A.; Charpentier, Ronald R.; Cook, Troy; Klett, Timothy R.; Gautier, Donald L.; Pollastro, Richard M.; Weaver, Jean N.; Brownfield, Michael

2011-01-01

Using a performance-based geological assessment methodology, the U.S. Geological Survey estimated mean volumes of 13.4 trillion cubic feet of potential technically recoverable shale gas and 0.5 billion barrels of technically recoverable shale oil resources in the Norte Basin of Uruguay.

World Shale Gas Resources: An Initial Assessment of 14 Regions Outside the United States

EIA Publications

2011-01-01

The Energy Information Administration sponsored Advanced Resources International, Inc., to assess 48 gas shale basins in 32 countries, containing almost 70 shale gas formations. This effort has culminated in the report: World Shale Gas Resources: An Initial Assessment of 14 Regions Outside the United States.

CONTROL OF SULFUR EMISSIONS FROM OIL SHALE RETORTING USING SPEND SHALE ABSORPTION

EPA Science Inventory

The paper gives results of a detailed engineering evaluation of the potential for using an absorption on spent shale process (ASSP) for controlling sulfur emissions from oil shale plants. The evaluation analyzes the potential effectiveness and cost of absorbing SO2 on combusted s...

Rapid gas development in the Fayetteville shale basin, Arkansas

EPA Science Inventory

Advances in drilling and extraction of natural gas have resulted in rapid expansion of wells in shale basins. The rate of gas well installation in the Fayetteville shale is 774 wells a year since 2005 with thousands more planned. The Fayetteville shale covers 23,000 km2 although ...

Oil shale extraction using super-critical extraction

NASA Technical Reports Server (NTRS)

Compton, L. E. (Inventor)

1983-01-01

Significant improvement in oil shale extraction under supercritical conditions is provided by extracting the shale at a temperature below 400 C, such as from about 250 C to about 350 C, with a solvent having a Hildebrand solubility parameter within 1 to 2 Hb of the solubility parameter for oil shale bitumen.

Tridimensional modelling and resource estimation of the mining waste piles of São Domingos mine, Iberian Pyrite Belt, Portugal

NASA Astrophysics Data System (ADS)

Vieira, Alexandre; Matos, João; Lopes, Luis; Martins, Ruben

2016-04-01

Located in the Iberian Pyrite Belt (IPB) northern sector, near the Portuguese/Spanish border, the outcropping São Domingos deposit was mined since Roman time. Between 1854 and 1966 the Mason & Barry Company developed open pit excavation until 120 m depth and underground mining until 420 m depth. The São Domingos subvertical deposit is associated with felsic volcanics and black shales of the IPB Volcano-Sedimentary Complex and is represented by massive sulphide and stockwork ore (py, cpy, sph, ga, tt, aspy) and related supergene enrichment ore (hematite gossan and covellite/chalcocite). Different mine waste classes were mapped around the old open pit: gossan (W1), felsic volcanic and shales (W2), shales (W3) and mining waste landfill (W4). Using the LNEG (Portuguese Geological Survey) CONASA database (company historical mining waste characterization based on 162 shafts and 160 reverse circulation boreholes), a methodology for tridimensional modelling mining waste pile was followed, and a new mining waste resource is presented. Considering some constraints to waste removal, such as the Mina de São Domingos village proximity of the wastes, the industrial and archaeological patrimony (e.g., mining infrastructures, roman galleries), different resource scenarios were considered: unconditioned resources (total estimates) and conditioned resources (only the volumes without removal constraints considered). Using block modelling (SURPAC software) a mineral inferred resource of 2.38 Mt @ 0.77 g/t Au and 8.26 g/t Ag is estimated in unconditioned volumes of waste. Considering all evaluated wastes, including village areas, an inferred resource of 4.0 Mt @ 0.64 g/t Au and 7.30 g/t Ag is presented, corresponding to a total metal content of 82,878 oz t Au and 955,753 oz t Ag. Keywords. São Domingos mine, mining waste resources, mining waste pile modelling, Iberian Pyrite Belt, Portugal

Uranium isotopes as a potential global-ocean redox proxy: a test from the Upper Pennsylvanian Hushpuckney Shale (Kansas, U.S.A.)

NASA Astrophysics Data System (ADS)

Herrmann, A. D.; Algeo, T. J.; Gordon, G. W.; Anbar, A. D.

2015-12-01

Uranium (U) isotope variation in marine sediments has been proposed as a proxy for changes in average global-ocean redox conditions. Here, we investigate U isotope variation in the black shale (BS) member of the Hushpuckney Shale (Swope Formation) at two sites ~400 km apart within the Late Paleozoic Midcontinent Sea (LPMS) of North America, with the goal of testing whether sediment δ238U records a global-ocean redox signal or local environmental influences. Our results document a spatial gradient of at least 0.25‰ in δ238U within the LPMS, demonstrating that local (probably redox) controls have overprinted any global U-isotope signal. Furthermore, the pattern of stratigraphic variation in δ238U in both study cores, with low values (‒0.4 to ‒0.2‰) at the base and top and peak values (+0.4 to +0.65‰) in the middle of the BS, is inconsistent with dominance of a global-ocean redox signal because (1) the middle of the BS was deposited at maximum eustatic highstand when euxinic conditions existed most widely within the LPMS and coeval epicontinental seas, and (2) more extensive euxinia should have shifted global-ocean seawater δ238U to lower values based on mass-balance principles. On the other hand, the observed δ238U pattern is consistent with a dominant local redox control, with larger U-isotope fractionations associated with more reducing bottom waters. We therefore conclude that U was not removed quantitatively to euxinic facies of the LPMS, and that sediment U-isotope compositions were controlled mainly by local redox and hydrographic factors. Our results imply that U-isotope signals from epicontinental-sea sections must be vetted carefully through analysis of high-resolution datasets at multiple sites in order to validate their potential use as a global-seawater redox proxy.

Racial bias is associated with ingroup death rate for Blacks and Whites: Insights from Project Implicit.

PubMed

Leitner, Jordan B; Hehman, Eric; Ayduk, Ozlem; Mendoza-Denton, Rodolfo

2016-10-20

Research suggests that, among Whites, racial bias predicts negative ingroup health outcomes. However, little is known about whether racial bias predicts ingroup health outcomes among minority populations. The aim of the current research was to understand whether racial bias predicts negative ingroup health outcomes for Blacks. We compiled racial bias responses from 250,665 Blacks and 1,391,632 Whites to generate county-level estimates of Blacks' and Whites' implicit and explicit biases towards each other. We then examined the degree to which these biases predicted ingroup death rate from circulatory-related diseases. In counties where Blacks harbored more implicit bias towards Whites, Blacks died at a higher rate. Additionally, consistent with previous research, in counties where Whites harbored more explicit bias towards Blacks, Whites died at a higher rate. These links between racial bias and ingroup death rate were independent of county-level socio-demographic characteristics, and racial biases from the outgroup in the same county. Findings indicate that racial bias is related to negative ingroup health outcomes for both Blacks and Whites, though this relationship is driven by implicit bias for Blacks, and explicit bias for Whites. Copyright © 2016 Elsevier Ltd. All rights reserved.

Apparatus for oil shale retorting

DOEpatents

Lewis, Arthur E.; Braun, Robert L.; Mallon, Richard G.; Walton, Otis R.

1986-01-01

A cascading bed retorting process and apparatus in which cold raw crushed shale enters at the middle of a retort column into a mixer stage where it is rapidly mixed with hot recycled shale and thereby heated to pyrolysis temperature. The heated mixture then passes through a pyrolyzer stage where it resides for a sufficient time for complete pyrolysis to occur. The spent shale from the pyrolyzer is recirculated through a burner stage where the residual char is burned to heat the shale which then enters the mixer stage.

World Shale Resource Assessments

EIA Publications

2015-01-01

Four countries: Chad, Kazakhstan, Oman and the United Arab Emirates (UAE) have been added to report “Technically Recoverable Shale Oil and Shale Gas Resources.” The report provides an estimate of shale resources in selected basins around the world. The new chapters cover shale basins from the Sub-Saharan Africa region, represented by Chad; the Caspian region, represented by Kazakhstan; and the Middle East region, represented by Oman and the United Arab Emirates (UAE) and are available as supplemental chapters to the 2013 report.

D/H ratios and hydrogen exchangeability of type-II kerogens with increasing thermal maturity

USGS Publications Warehouse

Lis, G.P.; Schimmelmann, A.; Mastalerz, Maria

2006-01-01

Stable isotope ratios of non-exchangeable hydrogen (??Dn) and of carbon were measured in type-II kerogens from two suites of Late Devonian to Early Mississippian black shale, one from the New Albany Shale (Illinois Basin) and the other from the Exshaw Formation (Alberta Basin). The largely marine-derived organic matter had similar original stable isotope ratios, but today the suites of kerogens express gradients in thermal maturity that have altered their chemical and isotopic compositions. In both suites, ??D n values increase with maturation up to a vitrinite reflectance of Ro 1.5%, then level out. Increasing ??Dn values suggest isotopic exchange of organic hydrogen with water-derived deuterium and/or preferential loss of 1H-enriched chemical moieties from kerogen during maturation. The resulting changes in ??Dn values are altering the original hydrogen isotopic paleoenvironmental signal in kerogen, albeit in a systematic fashion. The specific D/H response of each kerogen suite through maturation correlates with H/C elemental ratio and can therefore be corrected to yield paleoenvironmentally relevant information for a calibrated system. With increasing thermal maturity, the abundance of hydrogen in the kerogen that is isotopically exchangeable with water hydrogen (expressed as Hex, in % of total hydrogen) first decreases to reach a minimum at Ro ??? 0.8-1.1%, followed by a substantial increase at higher thermal maturity. ?? 2005 Elsevier Ltd. All rights reserved.

Organic metamorphism in the Lower Mississippian-Upper Devonian Bakken shales. Part 1: Rock-Eval pyrolysis and vitrinite reflectance.

USGS Publications Warehouse

Price, L.C.; Daws, T.; Pawlewicz, M.

1986-01-01

The Williston basin is an intracratonic basin extending across parts of several states, principally North Dakota, on the US/Canadian frontier. A sequence of up to 16 000 ft of Phanerozoic rocks exists in the basin; the Bakken formation is a relatively thin clastic unit composed of three members, of which the middle one is a black shale. Both core chip and cutting chip samples from a series of widely-distributed well locations were taken for laboratory analysis. Pyrolysis data showed 'wide variations' in maturity indices in samples from equivalent depths at different well locations. This suggests that a number of different palaeoheat-flow regimes have existed in the basin, resulting in the optimization of hydrocarbon formation processes at varying depths at different localities. The vitrinite reflectance profiles presented illustrate the expected trend of linearly-increasing maturity with depth to around 6500 ft. Between 6700 and 10 000 ft, however, this trend is interrupted by two 'reversals'. It is suggested that these reversals are due to suppression of the vitrinite reflectance values in samples with high concentrations of H-rich organic matter, and that they may therefore be associated with transitions from 'terrestrial-derived' to marine-depositional conditions. Consequently, the precise identification of the thresholds of intense hydrocarbon generation within the basin is problematic.-J.M.H.

Outflow-driven Transients from the Birth of Binary Black Holes. II. Primary-induced Accretion Transients

NASA Astrophysics Data System (ADS)

Kimura, Shigeo S.; Murase, Kohta; Mészáros, Peter

2017-12-01

We discuss the electromagnetic radiation from newborn binary black holes (BBHs). As a consequence of the evolution of massive stellar binaries, a binary consisting of a primary black hole (BH) and a secondary Wolf–Rayet star is expected as a BBH progenitor system. We investigate optical transients from the birth of BBHs powered by the Bondi–Hoyle–Lyttleton accretion onto the primary BH, which occur ∼1–10 Gyr earlier than gravitational-wave signals at the BH–BH merger. When the secondary massive star collapses into a BH, it may eject a fraction of its outer material and may form a disk around the primary BH and induces a powerful disk wind. These primary-induced winds can lead to optical transients with a kinetic energy of ∼1047–3 × 1048 erg, an ejecta velocity of 108–109 cm s‑1, a duration of a few days, and an absolute magnitude ranging from about ‑11 to ‑14. The light curves and late-time spectra of these transients are distinctive from those of ordinary supernovae, and detection of this type of transient is possible by future optical transient surveys if the event rate of this transient is comparable to the merger rate of BBHs. This paper focuses on the emissions from disk-driven transients induced by the primary BH, different from Paper I, which focuses on wind-driven transients from the tidally locked secondary massive star.

FIELD STUDIES ON USBM AND TOSCO II RETORTED OIL SHALES: VEGETATION, MOISTURE, SALINITY, AND RUNOFF, 1977-1980

EPA Science Inventory

Field studies were initiated in 1973 to investigate the vegetative stabilization of processed oil shales and to follow moisture and soluble salt movement within the soil/shale profile. Research plots with two types of retorted shales (TOSCO II and USBM) with leaching and soil cov...

18 CFR 270.303 - Natural gas produced from Devonian shale.

Code of Federal Regulations, 2013 CFR

2013-04-01

... from Devonian shale. A person seeking a determination that natural gas is produced from Devonian shale... 18 Conservation of Power and Water Resources 1 2013-04-01 2013-04-01 false Natural gas produced from Devonian shale. 270.303 Section 270.303 Conservation of Power and Water Resources FEDERAL ENERGY...

18 CFR 270.303 - Natural gas produced from Devonian shale.

Code of Federal Regulations, 2012 CFR

2012-04-01

... from Devonian shale. A person seeking a determination that natural gas is produced from Devonian shale... 18 Conservation of Power and Water Resources 1 2012-04-01 2012-04-01 false Natural gas produced from Devonian shale. 270.303 Section 270.303 Conservation of Power and Water Resources FEDERAL ENERGY...

18 CFR 270.303 - Natural gas produced from Devonian shale.

Code of Federal Regulations, 2014 CFR

2014-04-01

... from Devonian shale. A person seeking a determination that natural gas is produced from Devonian shale... 18 Conservation of Power and Water Resources 1 2014-04-01 2014-04-01 false Natural gas produced from Devonian shale. 270.303 Section 270.303 Conservation of Power and Water Resources FEDERAL ENERGY...

Life Cycle Water Consumption for Shale Gas and Conventional Natural Gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, Corrie E.; Horner, Robert M.; Harto, Christopher B.

2013-10-15

Shale gas production represents a large potential source of natural gas for the nation. The scale and rapid growth in shale gas development underscore the need to better understand its environmental implications, including water consumption. This study estimates the water consumed over the life cycle of conventional and shale gas production, accounting for the different stages of production and for flowback water reuse (in the case of shale gas). This study finds that shale gas consumes more water over its life cycle (13–37 L/GJ) than conventional natural gas consumes (9.3–9.6 L/GJ). However, when used as a transportation fuel, shale gasmore » consumes significantly less water than other transportation fuels. When used for electricity generation, the combustion of shale gas adds incrementally to the overall water consumption compared to conventional natural gas. The impact of fuel production, however, is small relative to that of power plant operations. The type of power plant where the natural gas is utilized is far more important than the source of the natural gas.« less

Life cycle water consumption for shale gas and conventional natural gas.

PubMed

Clark, Corrie E; Horner, Robert M; Harto, Christopher B

2013-10-15

Shale gas production represents a large potential source of natural gas for the nation. The scale and rapid growth in shale gas development underscore the need to better understand its environmental implications, including water consumption. This study estimates the water consumed over the life cycle of conventional and shale gas production, accounting for the different stages of production and for flowback water reuse (in the case of shale gas). This study finds that shale gas consumes more water over its life cycle (13-37 L/GJ) than conventional natural gas consumes (9.3-9.6 L/GJ). However, when used as a transportation fuel, shale gas consumes significantly less water than other transportation fuels. When used for electricity generation, the combustion of shale gas adds incrementally to the overall water consumption compared to conventional natural gas. The impact of fuel production, however, is small relative to that of power plant operations. The type of power plant where the natural gas is utilized is far more important than the source of the natural gas.

Water Resources and Natural Gas Production from the Marcellus Shale

USGS Publications Warehouse

Soeder, Daniel J.; Kappel, William M.

2009-01-01

The Marcellus Shale is a sedimentary rock formation deposited over 350 million years ago in a shallow inland sea located in the eastern United States where the present-day Appalachian Mountains now stand (de Witt and others, 1993). This shale contains significant quantities of natural gas. New developments in drilling technology, along with higher wellhead prices, have made the Marcellus Shale an important natural gas resource. The Marcellus Shale extends from southern New York across Pennsylvania, and into western Maryland, West Virginia, and eastern Ohio (fig. 1). The production of commercial quantities of gas from this shale requires large volumes of water to drill and hydraulically fracture the rock. This water must be recovered from the well and disposed of before the gas can flow. Concerns about the availability of water supplies needed for gas production, and questions about wastewater disposal have been raised by water-resource agencies and citizens throughout the Marcellus Shale gas development region. This Fact Sheet explains the basics of Marcellus Shale gas production, with the intent of helping the reader better understand the framework of the water-resource questions and concerns.

Removing heavy metals from wastewaters with use of shales accompanying the coal beds.

PubMed

Jabłońska, Beata; Siedlecka, Ewa

2015-05-15

A possibility of using clay waste rocks (shales) from coal mines in the removal of heavy metals from industrial wastewaters is considered in this paper. Raw and calcined (600 °C) shales accompanying the coal beds in two Polish coal mines were examined with respect to their adsorptive capabilities for Pb, Ni and Cu ions. The mineralogical composition of the shales was determined and the TG/DTG analysis was carried out. The granulometric compositions of raw and calcined shales were compared. Tests of adsorption for various Pb(II), Ni(II) and Cu(II) concentrations were conducted and the pH before and after adsorption was analyzed. The results indicate that the shales from both coal mines differ in adsorptive capabilities for particular metal ions. The calcination improved the adsorptive capabilities for lead, but worsened them for nickel. The examined shales have good adsorptive capabilities, and could be used as inexpensive adsorbents of heavy metal ions, especially in the regions where resources of shale are easy accessible in the form of spoil tips. Copyright © 2015 Elsevier Ltd. All rights reserved.

Updated methodology for nuclear magnetic resonance characterization of shales

NASA Astrophysics Data System (ADS)

Washburn, Kathryn E.; Birdwell, Justin E.

2013-08-01

Unconventional petroleum resources, particularly in shales, are expected to play an increasingly important role in the world's energy portfolio in the coming years. Nuclear magnetic resonance (NMR), particularly at low-field, provides important information in the evaluation of shale resources. Most of the low-field NMR analyses performed on shale samples rely heavily on standard T1 and T2 measurements. We present a new approach using solid echoes in the measurement of T1 and T1-T2 correlations that addresses some of the challenges encountered when making NMR measurements on shale samples compared to conventional reservoir rocks. Combining these techniques with standard T1 and T2 measurements provides a more complete assessment of the hydrogen-bearing constituents (e.g., bitumen, kerogen, clay-bound water) in shale samples. These methods are applied to immature and pyrolyzed oil shale samples to examine the solid and highly viscous organic phases present during the petroleum generation process. The solid echo measurements produce additional signal in the oil shale samples compared to the standard methodologies, indicating the presence of components undergoing homonuclear dipolar coupling. The results presented here include the first low-field NMR measurements performed on kerogen as well as detailed NMR analysis of highly viscous thermally generated bitumen present in pyrolyzed oil shale.

Methanogenic archaea in marcellus shale: a possible mechanism for enhanced gas recovery in unconventional shale resources.

PubMed

Tucker, Yael Tarlovsky; Kotcon, James; Mroz, Thomas

2015-06-02

Marcellus Shale occurs at depths of 1.5-2.5 km (5000 to 8000 feet) where most geologists generally assume that thermogenic processes are the only source of natural gas. However, methanogens in produced fluids and isotopic signatures of biogenic methane in this deep shale have recently been discovered. This study explores whether those methanogens are indigenous to the shale or are introduced during drilling and hydraulic fracturing. DNA was extracted from Marcellus Shale core samples, preinjected fluids, and produced fluids and was analyzed using Miseq sequencing of 16s rRNA genes. Methanogens present in shale cores were similar to methanogens in produced fluids. No methanogens were detected in injected fluids, suggesting that this is an unlikely source and that they may be native to the shale itself. Bench-top methane production tests of shale core and produced fluids suggest that these organisms are alive and active under simulated reservoir conditions. Growth conditions designed to simulate the hydrofracture processes indicated somewhat increased methane production; however, fluids alone produced relatively little methane. Together, these results suggest that some biogenic methane may be produced in these wells and that hydrofracture fluids currently used to stimulate gas recovery could stimulate methanogens and their rate of producing methane.

A novel energy-efficient pyrolysis process: self-pyrolysis of oil shale triggered by topochemical heat in a horizontal fixed bed.

PubMed

Sun, You-Hong; Bai, Feng-Tian; Lü, Xiao-Shu; Li, Qiang; Liu, Yu-Min; Guo, Ming-Yi; Guo, Wei; Liu, Bao-Chang

2015-02-06

This paper proposes a novel energy-efficient oil shale pyrolysis process triggered by a topochemical reaction that can be applied in horizontal oil shale formations. The process starts by feeding preheated air to oil shale to initiate a topochemical reaction and the onset of self-pyrolysis. As the temperature in the virgin oil shale increases (to 250-300°C), the hot air can be replaced by ambient-temperature air, allowing heat to be released by internal topochemical reactions to complete the pyrolysis. The propagation of fronts formed in this process, the temperature evolution, and the reaction mechanism of oil shale pyrolysis in porous media are discussed and compared with those in a traditional oxygen-free process. The results show that the self-pyrolysis of oil shale can be achieved with the proposed method without any need for external heat. The results also verify that fractured oil shale may be more suitable for underground retorting. Moreover, the gas and liquid products from this method were characterised, and a highly instrumented experimental device designed specifically for this process is described. This study can serve as a reference for new ideas on oil shale in situ pyrolysis processes.

A Novel Energy-Efficient Pyrolysis Process: Self-pyrolysis of Oil Shale Triggered by Topochemical Heat in a Horizontal Fixed Bed

PubMed Central

Sun, You-Hong; Bai, Feng-Tian; Lü, Xiao-Shu; Li, Qiang; Liu, Yu-Min; Guo, Ming-Yi; Guo, Wei; Liu, Bao-Chang

2015-01-01

This paper proposes a novel energy-efficient oil shale pyrolysis process triggered by a topochemical reaction that can be applied in horizontal oil shale formations. The process starts by feeding preheated air to oil shale to initiate a topochemical reaction and the onset of self-pyrolysis. As the temperature in the virgin oil shale increases (to 250–300°C), the hot air can be replaced by ambient-temperature air, allowing heat to be released by internal topochemical reactions to complete the pyrolysis. The propagation of fronts formed in this process, the temperature evolution, and the reaction mechanism of oil shale pyrolysis in porous media are discussed and compared with those in a traditional oxygen-free process. The results show that the self-pyrolysis of oil shale can be achieved with the proposed method without any need for external heat. The results also verify that fractured oil shale may be more suitable for underground retorting. Moreover, the gas and liquid products from this method were characterised, and a highly instrumented experimental device designed specifically for this process is described. This study can serve as a reference for new ideas on oil shale in situ pyrolysis processes. PMID:25656294

Shale Gas in Europe: pragmatic perspectives and actions

NASA Astrophysics Data System (ADS)

Hübner, A.; Horsfield, B.; Kapp, I.

2012-10-01

Natural gas will continue to play a key role in the EU's energy mix in the coming years, with unconventional gas' role increasing in importance as new resources are exploited worldwide. As far as Europe's own shale gas resources are concerned, it is especially the public's perception and level of acceptance that will make or break shale gas in the near-term. Both the pros and cons need to be discussed based on factual argument rather than speculation. Research organizations such as ours (GFZ German Research Centre for Geosciences) have an active and defining role to play in remedying this deficiency. As far as science and technology developments are concerned, the project "Gas Shales in Europe" (GASH) and the shale gas activities of "GeoEnergie" (GeoEn) are the first major initiatives in Europe focused on shale gas. Basic and applied geoscientific research is conducted to understand the fundamental nature and interdependencies of the processes leading to shale gas formation. When it comes to knowledge transfer, the perceived and real risks associated with shale gas exploitation need immediate evaluation in Europe using scientific analysis. To proactively target these issues, the GFZ and partners are launching the European sustainable Operating Practices (E-SOP) Initiative for Unconventional Resources. The web-based Shale Gas Information Platform (SHIP) brings these issues into the public domain.

Updated methodology for nuclear magnetic resonance characterization of shales

USGS Publications Warehouse

Washburn, Kathryn E.; Birdwell, Justin E.

2013-01-01

Unconventional petroleum resources, particularly in shales, are expected to play an increasingly important role in the world’s energy portfolio in the coming years. Nuclear magnetic resonance (NMR), particularly at low-field, provides important information in the evaluation of shale resources. Most of the low-field NMR analyses performed on shale samples rely heavily on standard T1 and T2 measurements. We present a new approach using solid echoes in the measurement of T1 and T1–T2 correlations that addresses some of the challenges encountered when making NMR measurements on shale samples compared to conventional reservoir rocks. Combining these techniques with standard T1 and T2 measurements provides a more complete assessment of the hydrogen-bearing constituents (e.g., bitumen, kerogen, clay-bound water) in shale samples. These methods are applied to immature and pyrolyzed oil shale samples to examine the solid and highly viscous organic phases present during the petroleum generation process. The solid echo measurements produce additional signal in the oil shale samples compared to the standard methodologies, indicating the presence of components undergoing homonuclear dipolar coupling. The results presented here include the first low-field NMR measurements performed on kerogen as well as detailed NMR analysis of highly viscous thermally generated bitumen present in pyrolyzed oil shale.

Shale characterization in mass transport complex as a potential source rock: An example from onshore West Java Basin, Indonesia

NASA Astrophysics Data System (ADS)

Nugraha, A. M. S.; Widiarti, R.; Kusumah, E. P.

2017-12-01

This study describes a deep-water slump facies shale of the Early Miocene Jatiluhur/Cibulakan Formation to understand its potential as a source rock in an active tectonic region, the onshore West Java. The formation is equivalent with the Gumai Formation, which has been well-known as another prolific source rock besides the Oligocene Talang Akar Formation in North West Java Basin, Indonesia. The equivalent shale formation is expected to have same potential source rock towards the onshore of Central Java. The shale samples were taken onshore, 150 km away from the basin. The shale must be rich of organic matter, have good quality of kerogen, and thermally matured to be categorized as a potential source rock. Investigations from petrography, X-Ray diffractions (XRD), and backscattered electron show heterogeneous mineralogy in the shales. The mineralogy consists of clay minerals, minor quartz, muscovite, calcite, chlorite, clinopyroxene, and other weathered minerals. This composition makes the shale more brittle. Scanning Electron Microscope (SEM) analysis indicate secondary porosities and microstructures. Total Organic Carbon (TOC) shows 0.8-1.1 wt%, compared to the basinal shale 1.5-8 wt%. The shale properties from this outcropped formation indicate a good potential source rock that can be found in the subsurface area with better quality and maturity.

Geology of the Devonian Marcellus Shale--Valley and Ridge province, Virginia and West Virginia--a field trip guidebook for the American Association of Petroleum Geologists Eastern Section Meeting, September 28-29, 2011

USGS Publications Warehouse

Enomoto, Catherine B.; Coleman, James L.; Haynes, John T.; Whitmeyer, Steven J.; McDowell, Ronald R.; Lewis, J. Eric; Spear, Tyler P.; Swezey, Christopher S.

2012-01-01

Detailed and reconnaissance field mapping and the results of geochemical and mineralogical analyses of outcrop samples indicate that the Devonian shales of the Broadtop Synclinorium from central Virginia to southern Pennsylvania have an organic content sufficiently high and a thermal maturity sufficiently moderate to be considered for a shale gas play. The organically rich Middle Devonian Marcellus Shale is present throughout most of the synclinorium, being absent only where it has been eroded from the crests of anticlines. Geochemical analyses of outcrop and well samples indicate that hydrocarbons have been generated and expelled from the kerogen originally in place in the shale. The mineralogical characteristics of the Marcellus Shale samples from the Broadtop Synclinorium are slightly different from the averages of samples from New York, Pennsylvania, northeast Ohio, and northern West Virginia. The Middle Devonian shale interval is moderately to heavily fractured in all areas, but in some areas substantial fault shearing has removed a regular "cleat" system of fractures. Conventional anticlinal gas fields in the study area that are productive from the Lower Devonian Oriskany Sandstone suggest that a continuous shale gas system may be in place within the Marcellus Shale interval at least in a portion of the synclinorium. Third-order intraformational deformation is evident within the Marcellus shale exposures. Correlations between outcrops and geophysical logs from exploration wells nearby will be examined by field trip attendees.

Overpressure generation by load transfer following shale framework weakening due to smectite diagenesis

USGS Publications Warehouse

Lahann, R.W.; Swarbrick, R.E.

2011-01-01

Basin model studies which have addressed the importance of smectite conversion to illite as a source of overpressure in the Gulf of Mexico have principally relied on a single-shale compaction model and treated the smectite reaction as only a fluid-source term. Recent fluid pressure interpretation and shale petrology studies indicate that conversion of bound water to mobile water, dissolution of load-bearing grains, and increased preferred orientation change the compaction properties of the shale. This results in substantial changes in effective stress and fluid pressure. The resulting fluid pressure can be 1500-3000psi higher than pressures interpreted from models based on shallow compaction trends. Shale diagenesis changes the mineralogy, volume, and orientation of the load-bearing grains in the shale as well as the volume of bound water. This process creates a weaker (more compactable) grain framework. When these changes occur without fluid export from the shale, some of the stress is transferred from the grains onto the fluid. Observed relationships between shale density and calculated effective stress in Gulf of Mexico shelf wells confirm these changes in shale properties with depth. Further, the density-effective stress changes cannot be explained by fluid-expansion or fluid-source processes or by prediagenesis compaction, but are consistent with a dynamic diagenetic modification of the shale mineralogy, texture, and compaction properties during burial. These findings support the incorporation of diagenetic modification of compaction properties as part of the fluid pressure interpretation process. ?? 2011 Blackwell Publishing Ltd.

Prediction of shale prospectivity from seismically-derived reservoir and completion qualities: Application to a shale-gas field, Horn River Basin, Canada

NASA Astrophysics Data System (ADS)

Mo, Cheol Hoon; Lee, Gwang H.; Jeoung, Taek Ju; Ko, Kyung Nam; Kim, Ki Soo; Park, Kyung-sick; Shin, Chang Hoon

2018-04-01

Prospective shale plays require a combination of good reservoir and completion qualities. Total organic carbon (TOC) is an important reservoir quality and brittleness is the most critical condition for completion quality. We analyzed seismically-derived brittleness and TOC to investigate the prospectivity of the Horn River Group shale (the Muskwa, Otter Park, Evie shales) of a shale-gas field in the western Horn River Basin, British Columbia, Canada. We used the λρ-μρ brittleness template, constructed from the mineralogy-based brittleness index (MBI) and elastic logs from two wells, to convert the λρ and μρ volumes from prestack seismic inversion to the volume for the brittleness petrotypes (most brittle, intermediate, and least brittle). The probability maps of the most brittle petrotype for the three shales were generated from Bayesian classification, based on the λρ-μρ template. The relationship between TOC and P-wave and S-wave velocity ratio (VP/VS) at the wells allowed the conversion of the VP/VS volume from prestack inversion to the TOC volume, which in turn was used to construct the TOC maps for the three shales. Increased TOC is correlated with high brittleness, contrasting with the commonly-held understanding. Therefore, the prospectivity of the shales in the study area can be represented by high brittleness and increased TOC. We propose a shale prospectivity index (SPI), computed by the arithmetic average of the normalized probability of the most brittle petrotype and the normalized TOC. The higher SPI corresponds to higher production rates in the Muskwa and Evie shales. The areas of the highest SPI have not been fully tested. The future drilling should be focused on these areas to increase the economic viability of the field.

Modeling of gas generation from the Barnett Shale, Fort Worth Basin, Texas

USGS Publications Warehouse

Hill, R.J.; Zhang, E.; Katz, B.J.; Tang, Y.

2007-01-01

The generative gas potential of the Mississippian Barnett Shale in the Fort Worth Basin, Texas, was quantitatively evaluated by sealed gold-tube pyrolysis. Kinetic parameters for gas generation and vitrinite reflectance (Ro) changes were calculated from pyrolysis data and the results used to estimate the amount of gas generated from the Barnett Shale at geologic heating rates. Using derived kinetics for Ro evolution and gas generation, quantities of hydrocarbon gas generated at Ro ??? 1.1% are about 230 L/t (7.4 scf/t) and increase to more that 5800 L/t (186 scf/t) at Ro ??? 2.0% for a sample with an initial total organic carbon content of 5.5% and Ro = 0.44%. The volume of shale gas generated will depend on the organic richness, thickness, and thermal maturity of the shale and also the amount of petroleum that is retained in the shale during migration. Gas that is reservoired in shales appears to be generated from the cracking of kerogen and petroleum that is retained in shales, and that cracking of the retained petroleum starts by Ro ??? 1.1%. This result suggests that the cracking of petroleum retained in source rocks occurs at rates that are faster than what is predicted for conventional siliciclastic and carbonate reservoirs, and that contact of retained petroleum with kerogen and shale mineralogy may be a critical factor in shale-gas generation. Shale-gas systems, together with overburden, can be considered complete petroleum systems, although the processes of petroleum migration, accumulation, and trap formation are different from what is defined for conventional petroleum systems. Copyright ?? 2007. The American Association of Petroleum Geologists. All rights reserved.

Compaction history of Upper Cretaceous shale (Al-Khod Formation) and its relationship to plate margin tectonics, Arabian Plate, Sultanate of Oman

NASA Astrophysics Data System (ADS)

AL-Sarmi, Musaab; Mattern, Frank; Scharf, Andreas; Pracejus, Bernhard; Al-Mamari, Amira; Al-Hinaai, Al-Shima

2017-04-01

Conglomerates of the late Cretaceous Al-Khod Formation have been intruded by older shale of the same formation along faults, which were opened/widened by extension, thus, resulting in shale dike formation. Following intrusion the shale was behaving plastically as its fissility follows the contact contours of the conglomeratic host rock and as stoped sandstone blocks are floating within the shale. Vertical calcite veins were ptygmatically folded with subhorizontal fold axial planes. All these aspects show that the shale contained a high water content in the beginning. The ptygmatically folded calcite veins display vertical shortening amounts of 40 % corresponding to 35 % to 45 % of water loss during compaction. Incalculable numbers of calcite veins of different orientations and thicknesses within the conglomerate along the shale contact indicate that the fluid was expelled from the shale into the conglomerate host rock under high pressure (overpressure?). Shale dyke formation took place after the late Cretaceous obduction of the Semail Ophiolite, before the deposition of early Tertiary carbonate rocks, and during the latest Cretaceous doming of the Saih Hatat area which was caused by deformation and slab breakoff, likely associated with gravitational collapse and elastic rebound. Shale intrusion was followed by deposition of 100 to 200 m thick sediments of the upper part of Al-Khod Formation, leading to compaction and water loss. The shale retained much of its water during the uppermost Cretaceous-late Paleocene stratigraphic hiatus as this interval is marked by erosion and a reduction of overburden, which was probably due to the elastic rebound. Folding of calcite veins together with a high amount of water loss was a consequence of compaction caused by the overburden of 1000 m thick shallow marine limestones which were deposited from the Eocene to Oligocene.

4D synchrotron X-ray imaging to understand porosity development in shales during exposure to hydraulic fracturing fluid

NASA Astrophysics Data System (ADS)

Kiss, A. M.; Bargar, J.; Kohli, A. H.; Harrison, A. L.; Jew, A. D.; Lim, J. H.; Liu, Y.; Maher, K.; Zoback, M. D.; Brown, G. E.

2016-12-01

Unconventional (shale) reservoirs have emerged as the most important source of petroleum resources in the United States and represent a two-fold decrease in greenhouse gas emissions compared to coal. Despite recent progress, hydraulic fracturing operations present substantial technical, economic, and environmental challenges, including inefficient recovery, wastewater production and disposal, contaminant and greenhouse gas pollution, and induced seismicity. A relatively unexplored facet of hydraulic fracturing operations is the fluid-rock interface, where hydraulic fracturing fluid (HFF) contacts shale along faults and fractures. Widely used, water-based fracturing fluids contain oxidants and acid, which react strongly with shale minerals. Consequently, fluid injection and soaking induces a host of fluid-rock interactions, most notably the dissolution of carbonates and sulfides, producing enhanced or "secondary" porosity networks, as well as mineral precipitation. The competition between these mechanisms determines how HFF affects reactive surface area and permeability of the shale matrix. The resultant microstructural and chemical changes may also create capillary barriers that can trap hydrocarbons and water. A mechanistic understanding of the microstructure and chemistry of the shale-HFF interface is needed to design new methodologies and fracturing fluids. Shales were imaged using synchrotron micro-X-ray computed tomography before, during, and after exposure to HFF to characterize changes to the initial 3D structure. CT reconstructions reveal how the secondary porosity networks advance into the shale matrix. Shale samples span a range of lithologies from siliceous to calcareous to organic-rich. By testing shales of different lithologies, we have obtained insights into the mineralogic controls on secondary pore network development and the morphologies at the shale-HFF interface and the ultimate composition of produced water from different facies. These results show that mineral texture is a major control over secondary porosity network morphology.

Introduction: energy and the subsurface.

PubMed

Christov, Ivan C; Viswanathan, Hari S

2016-10-13

This theme issue covers topics at the forefront of scientific research on energy and the subsurface, ranging from carbon dioxide (CO2) sequestration to the recovery of unconventional shale oil and gas resources through hydraulic fracturing. As such, the goal of this theme issue is to have an impact on the scientific community, broadly, by providing a self-contained collection of articles contributing to and reviewing the state-of-the-art of the field. This collection of articles could be used, for example, to set the next generation of research directions, while also being useful as a self-study guide for those interested in entering the field. Review articles are included on the topics of hydraulic fracturing as a multiscale problem, numerical modelling of hydraulic fracture propagation, the role of computational sciences in the upstream oil and gas industry and chemohydrodynamic patterns in porous media. Complementing the reviews is a set of original research papers covering growth models for branched hydraulic crack systems, fluid-driven crack propagation in elastic matrices, elastic and inelastic deformation of fluid-saturated rock, reaction front propagation in fracture matrices, the effects of rock mineralogy and pore structure on stress-dependent permeability of shales, topographic viscous fingering and plume dynamics in porous media convection.This article is part of the themed issue 'Energy and the subsurface'. © 2016 The Author(s).

Introduction: energy and the subsurface

PubMed Central

Viswanathan, Hari S.

2016-01-01

This theme issue covers topics at the forefront of scientific research on energy and the subsurface, ranging from carbon dioxide (CO2) sequestration to the recovery of unconventional shale oil and gas resources through hydraulic fracturing. As such, the goal of this theme issue is to have an impact on the scientific community, broadly, by providing a self-contained collection of articles contributing to and reviewing the state-of-the-art of the field. This collection of articles could be used, for example, to set the next generation of research directions, while also being useful as a self-study guide for those interested in entering the field. Review articles are included on the topics of hydraulic fracturing as a multiscale problem, numerical modelling of hydraulic fracture propagation, the role of computational sciences in the upstream oil and gas industry and chemohydrodynamic patterns in porous media. Complementing the reviews is a set of original research papers covering growth models for branched hydraulic crack systems, fluid-driven crack propagation in elastic matrices, elastic and inelastic deformation of fluid-saturated rock, reaction front propagation in fracture matrices, the effects of rock mineralogy and pore structure on stress-dependent permeability of shales, topographic viscous fingering and plume dynamics in porous media convection. This article is part of the themed issue ‘Energy and the subsurface’. PMID:27597784

The pore structure and fractal characteristics of shales with low thermal maturity from the Yuqia Coalfield, northern Qaidam Basin, northwestern China

NASA Astrophysics Data System (ADS)

Hou, Haihai; Shao, Longyi; Li, Yonghong; Li, Zhen; Zhang, Wenlong; Wen, Huaijun

2018-03-01

The continental shales from the Middle Jurassic Shimengou Formation of the northern Qaidam Basin, northwestern China, have been investigated in recent years because of their shale gas potential. In this study, a total of twenty-two shale samples were collected from the YQ-1 borehole in the Yuqia Coalfield, northern Qaidam Basin. The total organic carbon (TOC) contents, pore structure parameters, and fractal characteristics of the samples were investigated using TOC analysis, low-temperature nitrogen adsorption experiments, and fractal analysis. The results show that the average pore size of the Shimengou shales varied from 8.149 nm to 20.635 nm with a mean value of 10.74 nm, which is considered mesopore-sized. The pores of the shales are mainly inkbottle- and slit-shaped. The sedimentary environment plays an essential role in controlling the TOC contents of the low maturity shales, with the TOC values of shales from deep to semi-deep lake facies (mean: 5.23%) being notably higher than those of the shore-shallow lake facies (mean: 0.65%). The fractal dimensions range from 2.4639 to 2.6857 with a mean of 2.6122, higher than those of marine shales, which indicates that the pore surface was rougher and the pore structure more complex in these continental shales. The fractal dimensions increase with increasing total pore volume and total specific surface area, and with decreasing average pore size. With increasing TOC contents in shales, the fractal dimensions increase first and then decrease, with the highest value occurring at 2% of TOC content, which is in accordance with the trends between the TOC and both total specific surface area and total pore volume. The pore structure complexity and pore surface roughness of these low-maturity shales would be controlled by the combined effects of both sedimentary environments and the TOC contents.

Selling 'Fracking': Legitimation of High Speed Oil and Gas Extraction in the Marcellus Shale Region

NASA Astrophysics Data System (ADS)

Matz, Jacob R.

The advent of horizontal hydraulic fracture drilling, or 'fracking,' a technology used to access oil and natural gas deposits, has allowed for the extraction of deep, unconventional shale gas and oil deposits in various shale seams throughout the United States and world. One such shale seam, the Marcellus shale, extends from New York State, across Pennsylvania, and throughout West Virginia, where shale gas development has significantly increased within the last decade. This boom has created a massive amount of economic activity surrounding the energy industry, creating jobs for workers, income from leases and royalties for landowners, and profits for energy conglomerates. However, this bounty comes with risks to environmental and public health, and has led to divisive community polarization over the issue in the Marcellus shale region. In the face of potential environmental and social disruption, and a great deal of controversy surrounding 'fracking,' the oil and gas industry has had to undertake a myriad of public relations campaigns and initiatives to legitimize their extraction efforts in the Marcellus shale region, and to project the oil and gas industry in a positive light to residents, policy makers, and landowners. This thesis describes one such public relations initiative, the Energy in Depth Northeast Marcellus Initiative. Through qualitative content analysis of Energy in Depth's online web material, this thesis examines the ways in which the oil and gas industry narrates the shale gas boom in the Marcellus shale region, and the ways in which the industry frames the discourse surrounding natural gas development. Through the use of environmental imagery, appeals to scientific reason, and appeals to patriotism, the oil and gas industry uses Energy in Depth to frame the shale gas extraction process in a positive way, all the while framing those who question or oppose the processes of shale gas extraction as irrational obstructionists.

Spatial and stratigraphic distribution of water in oil shale of the Green River Formation using Fischer Assay, Piceance Basin, northwestern Colorado

USGS Publications Warehouse

Johnson, Ronald C.; Mercier, Tracey J.; Brownfield, Michael E.

2014-01-01

The spatial and stratigraphic distribution of water in oil shale of the Eocene Green River Formation in the Piceance Basin of northwestern Colorado was studied in detail using some 321,000 Fischer assay analyses in the U.S. Geological Survey oil-shale database. The oil-shale section was subdivided into 17 roughly time-stratigraphic intervals, and the distribution of water in each interval was assessed separately. This study was conducted in part to determine whether water produced during retorting of oil shale could provide a significant amount of the water needed for an oil-shale industry. Recent estimates of water requirements vary from 1 to 10 barrels of water per barrel of oil produced, depending on the type of retort process used. Sources of water in Green River oil shale include (1) free water within clay minerals; (2) water from the hydrated minerals nahcolite (NaHCO3), dawsonite (NaAl(OH)2CO3), and analcime (NaAlSi2O6.H20); and (3) minor water produced from the breakdown of organic matter in oil shale during retorting. The amounts represented by each of these sources vary both stratigraphically and areally within the basin. Clay is the most important source of water in the lower part of the oil-shale interval and in many basin-margin areas. Nahcolite and dawsonite are the dominant sources of water in the oil-shale and saline-mineral depocenter, and analcime is important in the upper part of the formation. Organic matter does not appear to be a major source of water. The ratio of water to oil generated with retorting is significantly less than 1:1 for most areas of the basin and for most stratigraphic intervals; thus water within oil shale can provide only a fraction of the water needed for an oil-shale industry.

Spatial and stratigraphic distribution of water in oil shale of the Green River Formation using Fischer assay, Piceance Basin, northwestern Colorado

USGS Publications Warehouse

Johnson, Ronald C.; Mercier, Tracey J.; Brownfield, Michael E.

2014-01-01

The spatial and stratigraphic distribution of water in oil shale of the Eocene Green River Formation in the Piceance Basin of northwestern Colorado was studied in detail using some 321,000 Fischer assay analyses in the U.S. Geological Survey oil-shale database. The oil-shale section was subdivided into 17 roughly time-stratigraphic intervals, and the distribution of water in each interval was assessed separately. This study was conducted in part to determine whether water produced during retorting of oil shale could provide a significant amount of the water needed for an oil-shale industry. Recent estimates of water requirements vary from 1 to 10 barrels of water per barrel of oil produced, depending on the type of retort process used. Sources of water in Green River oil shale include (1) free water within clay minerals; (2) water from the hydrated minerals nahcolite (NaHCO3), dawsonite (NaAl(OH)2CO3), and analcime (NaAlSi2O6.H20); and (3) minor water produced from the breakdown of organic matter in oil shale during retorting. The amounts represented by each of these sources vary both stratigraphically and areally within the basin. Clay is the most important source of water in the lower part of the oil-shale interval and in many basin-margin areas. Nahcolite and dawsonite are the dominant sources of water in the oil-shale and saline-mineral depocenter, and analcime is important in the upper part of the formation. Organic matter does not appear to be a major source of water. The ratio of water to oil generated with retorting is significantly less than 1:1 for most areas of the basin and for most stratigraphic intervals; thus water within oil shale can provide only a fraction of the water needed for an oil-shale industry.

Investigation of the physico-chemical and mechanical properties of hard brittle shales from the Shahejie Formation in the Nanpu Sag, northern China

NASA Astrophysics Data System (ADS)

Xiangjun, Liu; Jian, Xiong; Lixi, Liang; Yi, Ding

2017-06-01

With increasing demand for energy and advances in exploration and development technologies, more attention is being devoted to exploration and development of deep oil and gas reservoirs. The Nanpu Sag contains huge reserves in deep oil and gas reservoirs and is a promising area. In this paper, the physico-chemical and mechanical properties of hard brittle shales from the Shahejie Formation in the Nanpu Sag in the Bohai Bay Basin of northern China were investigated using a variety of methods, including x-ray diffraction analysis, cation exchange capacity (CEC) analysis, contact angle measurements, scanning electron microscope observations, immersion experiments, ultrasonic testing and mechanical testing. The effects of the physico-chemical properties of the shales on wellbore instability were observed, and the effects of hydration of the shales on wellbore instability were also examined. The results show that the major mineral constituents of the investigated shales are quartz and clay minerals. The clay mineral contents range from 25.33% to 52.03%, and the quartz contents range from 20.03% to 46.45%. The clay minerals do not include montmorillonite, but large amounts of mixed-layer illite/smectite were observed. The CEC values of the shales range from 90 to 210 mmol kg-1, indicating that the shales are partly hydrated. The wettability of the shales is strongly water-wetted, indicating that water would enter the shales due to the capillary effect. Hydration of hard brittle shales can generate cracks, leading to changes in microstructure and increases in the acoustic value, which could generate damage in the shales and reduce their strength. With increasing hydration time, the shale hydration effect gradually becomes stronger, causing an increase in the range of the acoustic travel time and decreases in the ranges of cohesion and internal friction angles. For the hard brittle shales of the Nanpu Sag, drilling fluid systems should aim to enhance sealing ability, decrease drilling fluid filter loss and increase the amount of clay-hydration inhibitor used.

Probing the Magnetic Field Structure in Sgr A* on Black Hole Horizon Scales with Polarized Radiative Transfer Simulations

NASA Astrophysics Data System (ADS)

Gold, Roman; McKinney, Jonathan C.; Johnson, Michael D.; Doeleman, Sheperd S.

2017-03-01

Magnetic fields are believed to drive accretion and relativistic jets in black hole accretion systems, but the magnetic field structure that controls these phenomena remains uncertain. We perform general relativistic (GR) polarized radiative transfer of time-dependent three-dimensional GR magnetohydrodynamical simulations to model thermal synchrotron emission from the Galactic Center source Sagittarius A* (Sgr A*). We compare our results to new polarimetry measurements by the Event Horizon Telescope (EHT) and show how polarization in the visibility (Fourier) domain distinguishes and constrains accretion flow models with different magnetic field structures. These include models with small-scale fields in disks driven by the magnetorotational instability as well as models with large-scale ordered fields in magnetically arrested disks. We also consider different electron temperature and jet mass-loading prescriptions that control the brightness of the disk, funnel-wall jet, and Blandford-Znajek-driven funnel jet. Our comparisons between the simulations and observations favor models with ordered magnetic fields near the black hole event horizon in Sgr A*, though both disk- and jet-dominated emission can satisfactorily explain most of the current EHT data. We also discuss how the black hole shadow can be filled-in by jet emission or mimicked by the absence of funnel jet emission. We show that stronger model constraints should be possible with upcoming circular polarization and higher frequency (349 GHz) measurements.

Predicted bulk composition of petroleum generated by Lower Cretaceous Wealden black shales, Lower Saxony Basin, Germany

NASA Astrophysics Data System (ADS)

Ziegs, Volker; Mahlstedt, Nicolaj; Bruns, Benjamin; Horsfield, Brian

2015-09-01

The Berriasian Wealden Shale provides the favourable situation of possessing immature to overmature source rock intervals due to differential subsidence within the Lower Saxony Basin. Hydrocarbon generation kinetics and petroleum physical properties have been investigated on four immature Wealden Shale samples situated in different depth intervals and following the PhaseKinetics approach of di Primio and Horsfield (AAPG Bull 90(7):1031-1058, 2006). Kinetic parameters and phase prediction were applied to a thermally calibrated 1D model of the geodynamic evolution at the location of an overmature well. The immature source rocks of all depth intervals comprise kerogen type I being derived from the lacustrine algae Botryococcus braunii. Bulk kinetics of the lower three depth intervals (sample 2-4) can be described by one single activation energy E a, typical for homogeneous, lacustrine organic matter (OM), whereas sample 1 from the uppermost interval shows a slightly broader E a distribution which hints to a more heterogeneous, less stable OM, but still of lacustrine origin. Predicted physical properties of the generated petroleum fluids are characteristic of variably waxy, black oil possessing GOR's below 100 Sm3/Sm3 and saturations pressures below 150 bar. Petroleum fluids from the more heterogeneous OM-containing sample 1 can always be described by slightly higher values. Based on the occurrence of paraffinic, free hydrocarbons in the uppermost horizon of the overmature well and gas/condensate in the lower 3 depth intervals, two scenarios have been discussed. From the first and least realistic scenario assuming no expulsion from the source rock, it can be deduced that phase separation in the course of uplift can only have occurred in the uppermost interval containing the slightly less stable OM but not in the lower intervals being composed of a more stable OM. Therefore and taking secondary cracking into account, all depth intervals should contain gas/condensate. The free hydrocarbons in the upper horizon are interpreted as impregnation from migrated hydrocarbons. The second scenario assumes nearly complete expulsion due to fracturing by the so-called generation overpressure (Mann et al. in Petroleum and basin evolution. Springer, Berlin, 1997). The expelled petroleum might migrate into lower pressurised source rock horizons and reach bubble-point pressures leading to the exsolution of gas and "precipitation" of very high molecular weight bitumen unable to migrate. Subsequent burial of the latter in the course of the basin evolution would lead to secondary cracking and remaining pyrobitumen explaining the high amounts of pyrobitumen in the overmature well Ex-B and relatively enhanced TOC contents at such high maturity levels.

Mo isotope record of shales points to deep ocean oxygenation in the early Paleoproterozoic

NASA Astrophysics Data System (ADS)

Asael, Dan; Scott, Clint; Rouxel, Olivier; Poulton, Simon; Lyons, Timothy; Javaux, Emmanuelle; Bekker, Andrey

2014-05-01

Two steps in Earth's surface oxidation lie at either end of the Proterozoic Eon. The first step, known as the Great Oxidation Event (GOE), occurred at ca. 2.32 Ga (1), when atmospheric oxygen first exceeded 0.001% of present atmospheric levels (2). The second step, occurred at ca. 0.58 Ga, resulting in the pervasive oxygenation of the deep oceans, a feature that persisted through most of the Phanerozoic (3). The conventional model envisions two progressive and unidirectional increases in free oxygen. However, recent studies have challenged this simplistic view of the GOE (4, 5). A dramatic increase and decline in Earth oxidation state between 2.3 and 2.0 Ga is now well supported (6-9) and raises the question of how well-oxygenated the Earth surface was in the immediate aftermath of the GOE. In order to constrain the response of the deep oceans to the GOE, we present a study of Mo isotope composition and Mo concentration from three key early Paleoproterozoic black shale units with ages ranging from 2.32 to 2.06 Ga. Our results suggest high and unstable surface oxygen levels at 2.32 Ga, leading to an abrupt increase in Mo supply to the still globally anoxic ocean, and producing extreme seawater Mo isotopic enrichments in these black shales. We thus infer a period of significant Mo isotopic Rayleigh effects and non-steady state behaviour of the Mo oceanic system at the beginning of the GOE. Between 2.2-2.1 Ga, we observe smaller Mo isotopic variations and estimate the δ98Mo of seawater to be 1.42 ± 0.27 ‰W conclude that oxygen levels must have stabilized at a relatively high level and that the deep oceans were oxygenated for the first time in Earth's history. By ca. 2.06 Ga, immediately after the Lomagundi Event, the Mo isotopic composition decreased dramatically to δ98MoSW = 0.80 ± 0.21 o reflecting the end of deep ocean oxygenation and the return of largely anoxic deep oceans. References: [1] A. Bekker et al., 2004, Nature 427, 117-20. [2] A. Pavlov and J. Kasting, 2002, Astrobiology 2, 27-41. [3] C. Scott et al., 2008, Nature 452, 456-9. [4] C. Goldblatt et al., 2006, Nature 443, 683-6. [5] L. Kump et al., 2011, Science 334, 1694-6. [6] A. Bekker and D. Holland, 2012, Earth Planet. Sci. Lett. 317-318, 295-304. [7] N. Planavsky et al., 2012, Proc. Natl. Acad. Sci. U. S. A. 109, 18300-5. [8] C. Partin et al., 2013, Chem. Geol. 362, 82-90. [9] C. Scott et al., 2014, Earth Planet. Sci. Lett. 389, 95-104.

Last hired, first fired? Black-white unemployment and the business cycle.

PubMed

Couch, Kenneth A; Fairlie, Robert

2010-02-01

Studies have tested the claim that blacks are the last hired during periods of economic growth and the first fired in recessions by examining the movement of relative unemployment rates over the business cycle. Any conclusion drawn from this type of analysis must be viewed as tentative because cyclical movements in the underlying transitions into and out of unemployment are not examined. Using Current Population Survey data matched across adjacent months from 1989-2004, this article provides the first detailed examination of labor market transitions for prime-age black and white men to test the last hired, first fired hypothesis. Considerable evidence is presented that blacks are the first fired as the business cycle weakens. However no evidence is found that blacks are the last hired. Instead, blacks appear to be initially hired from the ranks of the unemployed early in the business cycle and later are drawn from nonparticipation. The narrowing of the racial unemployment gap near the peak of the business cycle is driven by a reduction in the rate of job loss for blacks rather than increases in hiring.

Last Hired, First Fired? Black-White Unemployment and the Business Cycle

PubMed Central

COUCH, KENNETH A.; FAIRLIE, ROBERT

2010-01-01

Studies have tested the claim that blacks are the last hired during periods of economic growth and the first fired in recessions by examining the movement of relative unemployment rates over the business cycle. Any conclusion drawn from this type of analysis must be viewed as tentative because cyclical movements in the underlying transitions into and out of unemployment are not examined. Using Current Population Survey data matched across adjacent months from 1989–2004, this article provides the first detailed examination of labor market transitions for prime-age black and white men to test the last hired, first fired hypothesis. Considerable evidence is presented that blacks are the first fired as the business cycle weakens. However, no evidence is found that blacks are the last hired. Instead, blacks appear to be initially hired from the ranks of the unemployed early in the business cycle and later are drawn from nonparticipation. The narrowing of the racial unemployment gap near the peak of the business cycle is driven by a reduction in the rate of job loss for blacks rather than increases in hiring. PMID:20355692

A Concept of the Differentially Driven Three Wheeled Robot

NASA Astrophysics Data System (ADS)

Kelemen, M.; Colville, D. J.; Kelemenová, T.; Virgala, I.; Miková, L.

2013-08-01

The paper deals with the concept of a differentially driven three wheeled robot. The main task for the robot is to follow the navigation black line on white ground. The robot also contains anti-collision sensors for avoiding obstacles on track. Students learn how to deal with signals from sensors and how to control DC motors. Students work with the controller and develop the locomotion algorithm and can attend a competition

Electrically Driven Photonic Crystal Nanocavity Devices

DTIC Science & Technology

2012-01-01

material, here gallium arsenide and indium arsenide self- assembled quantum dots (QDs). QDs are preferred for the gain medium because they can have...blue points ) and 150 K (green points ). The black lines are linear fits to the above threshold output power of the lasers, which are used to find the...SHAMBAT et al.: ELECTRICALLY DRIVEN PHOTONIC CRYSTAL NANOCAVITY DEVICES 1707 Fig. 13. (a) Tilted SEM picture of a fabricated triple cavity device. The in

Acceleration of black hole universe

NASA Astrophysics Data System (ADS)

Zhang, T. X.; Frederick, C.

2014-01-01

Recently, Zhang slightly modified the standard big bang theory and developed a new cosmological model called black hole universe, which is consistent with Mach's principle, governed by Einstein's general theory of relativity, and able to explain all observations of the universe. Previous studies accounted for the origin, structure, evolution, expansion, and cosmic microwave background radiation of the black hole universe, which grew from a star-like black hole with several solar masses through a supermassive black hole with billions of solar masses to the present state with hundred billion-trillions of solar masses by accreting ambient matter and merging with other black holes. This paper investigates acceleration of the black hole universe and provides an alternative explanation for the redshift and luminosity distance measurements of type Ia supernovae. The results indicate that the black hole universe accelerates its expansion when it accretes the ambient matter in an increasing rate. In other words, i.e., when the second-order derivative of the mass of the black hole universe with respect to the time is positive . For a constant deceleration parameter , we can perfectly explain the type Ia supernova measurements with the reduced chi-square to be very close to unity, χ red˜1.0012. The expansion and acceleration of black hole universe are driven by external energy.

Where to Focus Efforts to Reduce the Black-White Disparity In Stroke Mortality: Incidence vs. Case-Fatality?

PubMed Central

Howard, George; Moy, Claudia S.; Howard, Virginia J.; McClure, Leslie A.; Kleindorfer, Dawn O.; Kissela, Brett M.; Judd, Suzanne E.; Unverzagt, Fredrick W.; Soliman, Elsayed Z.; Safford, Monika M.; Cushman, Mary; Flaherty, Matthew L.; Wadley, Virginia G.

2016-01-01

Background and Purpose At age 45, Blacks have a stroke mortality approximately 3-times greater than their White counterparts, with a declining disparity at older ages. We assess whether this Black-White disparity in stroke mortality is attributable to a Black-White disparity in stroke incidence versus a disparity in case-fatality. Methods We first assess if Black-White differences in stroke mortality within 29,681 participants in the REasons for Geographic And Racial Differences in Stroke (REGARDS) cohort reflect national Black-White differences in stroke mortality, and then assess the degree to which Black-White differences in stroke incidence or 30-day case-fatality after stroke contribute to the disparities in stroke mortality. Results The pattern of stroke mortality within the study mirrors the national pattern, with the Black-to-White hazard ratio of approximately 4.0 at age 45 decreasing to approximately 1.0 at age 85. The pattern of Black-to-White disparities in stroke incidence shows a similar pattern, but no evidence of a corresponding disparity in stroke case-fatality. Discussion These findings show that the Black-White differences in stroke mortality are largely driven by differences in stroke incidence, with case fatality playing at most a minor role. Therefore to reduce the Black-White disparity in stroke mortality, interventions need to focus on prevention of stroke in Blacks. PMID:27256672