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Sample records for carbonaceous shale samples

  1. Organic petrology of subbituminous carbonaceous shale samples from Chalaw, Kabul Province, Afghanistan: Considerations for paleoenvironment and energy resource potential

    Energy Technology Data Exchange (ETDEWEB)

    Hackley, Paul C.; SanFilipo, John R. [U.S. Geological Survey, MS 956 National Center, Reston VA, 20192 (United States); Azizi, Gul Pacha [Afghanistan Geological Survey, Macroryan Square, Kabul (Afghanistan); Davis, Philip A. [U.S. Geological Survey, 520 N. Park Avenue, Tucson AZ, 85719 (United States); Starratt, Scott W. [U.S. Geological Survey, MS 910, 345 Middlefield Rd, Menlo Park CA, 94025 (United States)

    2010-04-01

    Neogene (?) subbituminous carbonaceous shale deposits from Chalaw, Afghanistan, were investigated through organic petrology techniques and standard coal analyses to determine paleoenvironment and potential for resource utilization. The Chalaw deposit, approximately 30 km southeast of Kabul, currently is exploited for brick making and domestic heating and cooking. Three multiple-bench channel samples of the mined bed at Chalaw were collected and evaluated. The presence of significant huminite (ranging from 0.2 to 59.0 vol.%, mineral-inclusive basis) is suggestive of a terrestrial lignin-rich precursor plant material. Measured reflectance values of 0.38-0.55% indicate subbituminous rank. This rank suggests burial depths of approximately 1500 m and maximum temperatures of approximately 50 C. Structured liptinite macerals generally are absent except for some fluorescing morphologies interpreted to be poorly-preserved root cork suberinite. Sponge spicule bioliths including gemmoscleres and megascleres are common. These petrographic observations, in addition to high mineral matter content (33 to > 95 vol.%), medium to high sulfur content (2.1-11.5 wt.%, dry basis; db), and the presence of common gastropod? shell fragments and an aragonite-needle chalk bed are consistent with, but not directly indicative of, a marginal marine or estuarine mangrove depositional environment. However, additional data are necessary to confirm this hypothesis and deposition in a freshwater environment cannot be ruled out at this time. Commercial-scale development and utilization of the Chalaw deposit as a thermal fuel resource may be possible using a fluidized bed combustion system which could accept the low-quality mine product currently produced. Samples examined herein contain high-ash yield (45-90 wt.%, db), high total moisture content (17-39 wt.%), low calorific value (980-6860 Btu/lb, m,mmf), and have poor agglomerating properties (FSI = 0), consistent with fuels utilized in fluidized

  2. Organic petrology of subbituminous carbonaceous shale samples from Chalaw, Kabul Province, Afghanistan: Considerations for paleoenvironment and energy resource potential

    Science.gov (United States)

    Hackley, P.C.; SanFilipo, J.R.; Azizi, G.P.; Davis, P.A.; Starratt, S.W.

    2010-01-01

    Neogene (?) subbituminous carbonaceous shale deposits from Chalaw, Afghanistan, were investigated through organic petrology techniques and standard coal analyses to determine paleoenvironment and potential for resource utilization. The Chalaw deposit, approximately 30. km southeast of Kabul, currently is exploited for brick making and domestic heating and cooking. Three multiple-bench channel samples of the mined bed at Chalaw were collected and evaluated. The presence of significant huminite (ranging from 0.2 to 59.0. vol.%, mineral-inclusive basis) is suggestive of a terrestrial lignin-rich precursor plant material. Measured reflectance values of 0.38-0.55% indicate subbituminous rank. This rank suggests burial depths of approximately 1500. m and maximum temperatures of approximately 50. ??C. Structured liptinite macerals generally are absent except for some fluorescing morphologies interpreted to be poorly-preserved root cork suberinite. Sponge spicule bioliths including gemmoscleres and megascleres are common. These petrographic observations, in addition to high mineral matter content (33 to >95 vol%), medium to high sulfur content (2.1-11.5. wt.%, dry basis; db), and the presence of common gastropod? shell fragments and an aragonite-needle chalk bed are consistent with, but not directly indicative of, a marginal marine or estuarine mangrove depositional environment. However, additional data are necessary to confirm this hypothesis and deposition in a freshwater environment cannot be ruled out at this time.Commercial-scale development and utilization of the Chalaw deposit as a thermal fuel resource may be possible using a fluidized bed combustion system which could accept the low-quality mine product currently produced. Samples examined herein contain high-ash yield (45-90. wt.%, db), high total moisture content (17-39. wt.%), low calorific value (980-6860. Btu/lb, m,mmf), and have poor agglomerating properties (FSI=0), consistent with fuels utilized in

  3. Raman spectroscopy of selected carbonaceous samples

    Energy Technology Data Exchange (ETDEWEB)

    Kwiecinska, Barbara [University of Science and Technology-AGH, Faculty of Geology, Geophysics and Environmental Protection, Krakow (Poland); Suarez-Ruiz, Isabel [Instituto Nacional del Carbon, (INCAR-CSIC), Oviedo (Spain); Paluszkiewicz, Czeslawa [University of Science and Technology-AGH, Faculty of Materials Science and Technology, Krakow (Poland); Rodriques, Sandra [Universidade do Porto, Faculdade de Ciencias, Dept. de Geologia (Portugal)

    2010-12-01

    This paper presents the results of Raman spectra measured on carbonaceous materials ranging from greenschist facies to granulite-facies graphite (Anchimetamorphism and Epimetamorphism zones). Raman spectroscopy has come to be regarded as a more appropriate tool than X-ray diffraction for study of highly ordered carbon materials, including chondritic matter, soot, polycyclic aromatic hydrocarbons and evolved coal samples. This work demonstrates the usefulness of the Raman spectroscopy analysis in determining internal crystallographic structure (disordered lattice, heterogeneity). Moreover, this methodology permits the detection of differences within the meta-anthracite rank, semi-graphite and graphite stages for the samples included in this study. In the first order Raman spectra, the bands located near to c.a. 1350 cm{sup -1} (defects and disorder mode A{sub 1g}) and 1580 cm{sup -1} (in plane E{sub 2g} zone - centre mode) contribute to the characterization and determination of the degree of structural evolution and graphitization of the carbonaceous samples. The data from Raman spectroscopy were compared with parameters obtained by means of structural, chemical and optical microscopic analysis carried out on the same carbonaceous samples. The results revealed some positive and significant relationships, although the use of reflectance as a parameter for following the increase in structural order in natural graphitized samples was subject to limitations. (author)

  4. Results of core drilling for uranium-bearing carbonaceous shale and lignite in the Goose Creek district, Cassia County, Idaho

    Science.gov (United States)

    Mapel, William J.; Hail, William J.

    1954-01-01

    Thirteen core holes, totaling 2,023 feet, were drilled during the fall of 1953 to explore the grade and extent of uranium-bearing beds of carbonaceous shale and lignite in the east-central part of the Goose Creek district, Cassia County, Idaho. The beds tested are interbedded with volcanic ash, bentonite, greenish-gray shale, sandstone, and conglomerate in two fairly well defined zones in the lower part of the Salt Lake formation of lower Pliocene age. Nine holes penetrated carbonaceous shale beds in the Barrett zone, and one hole penetrated carbonaceous shale and lignite beds in zone B, 160 feet stratigraphically below the Barrett zone. The highest concentration of uranium found by drilling is 0.10 percent in the upper part of a 4-foot bed of carbonaceous shale and lignite in zone B. The grade of carbonaceous shale beds in the Barrett zone ranges from 0.044 percent to less than 0.003 percent uranium. Inferred reserves in the district are estimated to be 790,000 tons in beds 1 foot or more thick containing an average of 0.014 percent or 120 tons of uranium.

  5. The hydrocarbon potential, thermal maturity, sequence stratigraphic setting and depositional palaeoenvironment of carbonaceous shale and lignite successions of Panandhro, northwestern Kutch Basin, Gujarat, Western India

    Science.gov (United States)

    Sahay, Vinay

    2011-03-01

    The objective of the present paper is to provide geochemical and palynological data to characterize lignites and carbonaceous shales from Panandhro, northwestern Kutch Basin, Gujarat, Western India, in terms of their hydrocarbon potential, thermal maturity, sequence stratigraphic settings and depositional palaeoenvironment. The samples, collected in Panandhro lignite mine, belong to Naredi Formation of Late Paleocene-Early Eocene age. The geochemical results are based on proximate analysis, ultimate analysis, X-ray diffraction and Rock-Eval py-rolysis analyses, whereas palynological data include palynofossil composition and thermal alteration index (TAI). The TOC, hydrogen index (HI), cracked hydrocarbon (S2), bitumen index (BI), quality index (QI), and the total genetic potential (S1+S2) values indicate that the studied lignites and carbonaceous shales have good source rock potential. The organic matter is predominantly of type II and type II/III kerogen, which has potential to generate oil as well as gas. Thermal maturity determined from thermal alteration index (TAI), Tmax and production index (PI) indicates that the organic matter is immature, and in the diagenesis stage of organic matter transformation. The deposition of the studied carbonaceous shales and lignites took place in palaeoenvironments varying from brackish mangrove to freshwater swamp. This study indicates that the proportion of ferns, palms, volatile matter content, S/C, H/C ratios, as well as the presence of siderite and quartz can be used as an indicator of accommodation trends in the coal depositional system. The Panandhro carbonaceous shales and lignites were deposited during the lowstand systems tract with many cycles of small magnitude trangressive-regressive phases. Thus, the geochemistry and ecological palynology are useful not only for the investigation of coal quality and origin, but also to infer accommodation space settings of the mire. This can be gainfully utilized in the coal

  6. Comparative study of microfacies variation in two samples from the Chittenango member, Marcellus shale subgroup, western New York state, USA

    Energy Technology Data Exchange (ETDEWEB)

    Balulla, Shama, E-mail: shamamohammed77@outlook.com; Padmanabhan, E., E-mail: eswaran-padmanabhan@petronas.com.my [Department of Geoscience, Faculty of Geosciencs and Petroleum Engineering Universiti Teknologi PETRONAS, Tronoh (Malaysia); Over, Jeffrey, E-mail: over@geneseo.edu [Department of geological sciences, Geneseo, NY (United States)

    2015-07-22

    This study demonstrates the significant lithologic variations that occur within the two shale samples from the Chittenango member of the Marcellus shale formation from western New York State in terms of mineralogical composition, type of lamination, pyrite occurrences and fossil content using thin section detailed description and field emission Scanning electron microscope (FESEM) with energy dispersive X-Ray Spectrum (EDX). This study is classified samples as laminated clayshale and fossiliferous carbonaceous shale. The most important detrital constituents of these shales are the clay mineral illite and chlorite, quartz, organic matter, carbonate mineral, and pyrite. The laminated clayshale has a lower amount of quartz and carbonate minerals than fossiliferous carbonaceous shale while it has a higher amount of clay minerals (chlorite and illite) and organic matter. FESEM analysis confirms the presence of chlorite and illite. The fossil content in the laminated clayshale is much lower than the fossiliferous carbonaceous shale. This can provide greater insights about variations in the depositional and environmental factors that influenced its deposition. This result can be compiled with the sufficient data to be helpful for designing the horizontal wells and placement of hydraulic fracturing in shale gas exploration and production.

  7. Uranium-bearing coal and carbonaceous shale in La Ventana Mesa area, Sandoval County, New Mexico

    Science.gov (United States)

    Vine, James D.; Bachman, George O.; Read, Charles B.; Moore, George W.

    1953-01-01

    Uranium-bearing coal, carboanceous shale, and carboaceous sandstone of Upper Cretaceous age occur on and adjacent to La Ventana Mesa, Sandoval County, New Mexico.  The geologic features of the uranium deposits are described and a hypothesis for the origin and control of the uranium deposits are described and a hypothesis for the origin and control of the uranium deposits is given.  On the basis of recent sampling and analyses the uranium content in coal is found to be as much as 0.62 percent, whereas the coal ash has a uranium content that is as much as 1.34 percent.

  8. Artifact free denuder method for sampling of carbonaceous aerosols

    Science.gov (United States)

    Mikuška, P.; Vecera, Z.; Broškovicová, A.

    2003-04-01

    Over the past decade, a growing attention has been focused on the carbonaceous aerosols. Although they may account for 30--60% of the total fine aerosol mass, their concentration and formation mechanisms are not well understood, particularly in comparison with major fine particle inorganic species. The deficiency in knowledge of carbonaceous aerosols results from their complexity and because of problems associated with their collection. Conventional sampling techniques of the carbonaceous aerosols, which utilize filters/backup adsorbents suffer from sampling artefacts. Positive artifacts are mainly due to adsorption of gas-phase organic compounds by the filter material or by the already collected particles, whereas negative artifacts arise from the volatilisation of already collected organic compounds from the filter. Furthermore, in the course of the sampling, the composition of the collected organic compounds may be modified by oxidants (O_3, NO_2, PAN, peroxides) that are present in the air passing through the sampler. It is clear that new, artifact free, method for sampling of carbonaceous aerosols is needed. A combination of a diffusion denuder and a filter in series is very promising in this respect. The denuder is expected to collect gaseous oxidants and gas-phase organic compounds from sample air stream prior to collection of aerosol particles on filters, and eliminate thus both positive and negative sampling artifacts for carbonaceous aerosols. This combination is subject of the presentation. Several designs of diffusion denuders (cylindrical, annular, parallel plate, multi-channel) in combination with various types of wall coatings (dry, liquid) were examined. Special attention was given to preservation of the long-term collection efficiency. Different adsorbents (activated charcoal, molecular sieve, porous polymers) and sorbents coated with various chemical reagents (KI, Na_2SO_3, MnO_2, ascorbic acid) or chromatographic stationary phases (silicon oils

  9. Measurement of carbonaceous aerosol with different sampling configurations and frequencies

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    Y. Cheng

    2015-03-01

    Full Text Available Carbonaceous aerosol in Beijing, China was measured with different sampling configurations (denuded vs. un-denuded and frequencies (24 vs. 48 h averaged. Our results suggest that the negative sampling artifact of a bare quartz filter could be remarkably enhanced due to the uptake of water vapor by the filter medium, indicating that the positive sampling artifact tends to be underestimated under high humidity conditions. It was also observed that the analytical artifact (i.e., the underestimation of elemental carbon by the operationally defined value of the thermal-optical method was more apparent for the low frequency samples such that their elemental carbon (EC concentrations were about 15% lower than the reference values measured by the high-frequency, denuded filters. Moreover, EC results of the low frequency samples were found to exhibit a stronger dependence on the charring correction method. In addition, optical attenuation (ATN of EC was retrieved from the carbon analyzer, and the low frequency samples were shown to be more significantly biased by the shadowing effect.

  10. Functional Group Compositions of Carbonaceous Materials of Hayabusa-Returned Samples

    Science.gov (United States)

    Yabuta, H.; Uesugi, M.; Naraoka, H.; Ito, M.; Kilcoyne, D.; Sandford, S. A.; Kitajima, F.; Mita, H.; Takano, Y.; Yada, T.; Karouji, Y.; Ishibashi, Y.; Okada, T.; Abe, M.

    2014-09-01

    We have analyzed the functional group compositions of the carbonaceous materials of Hayabusa-returned samples by STXM-XANES, in order to identify whether the materials are terrestrial or extraterrestrial.

  11. Multiscale study for stochastic characterization of shale samples

    Science.gov (United States)

    Tahmasebi, Pejman; Javadpour, Farzam; Sahimi, Muhammad; Piri, Mohammad

    2016-03-01

    Characterization of shale reservoirs, which are typically of low permeability, is very difficult because of the presence of multiscale structures. While three-dimensional (3D) imaging can be an ultimate solution for revealing important complexities of such reservoirs, acquiring such images is costly and time consuming. On the other hand, high-quality 2D images, which are widely available, also reveal useful information about shales' pore connectivity and size. Most of the current modeling methods that are based on 2D images use limited and insufficient extracted information. One remedy to the shortcoming is direct use of qualitative images, a concept that we introduce in this paper. We demonstrate that higher-order statistics (as opposed to the traditional two-point statistics, such as variograms) are necessary for developing an accurate model of shales, and describe an efficient method for using 2D images that is capable of utilizing qualitative and physical information within an image and generating stochastic realizations of shales. We then further refine the model by describing and utilizing several techniques, including an iterative framework, for removing some possible artifacts and better pattern reproduction. Next, we introduce a new histogram-matching algorithm that accounts for concealed nanostructures in shale samples. We also present two new multiresolution and multiscale approaches for dealing with distinct pore structures that are common in shale reservoirs. In the multiresolution method, the original high-quality image is upscaled in a pyramid-like manner in order to achieve more accurate global and long-range structures. The multiscale approach integrates two images, each containing diverse pore networks - the nano- and microscale pores - using a high-resolution image representing small-scale pores and, at the same time, reconstructing large pores using a low-quality image. Eventually, the results are integrated to generate a 3D model. The methods

  12. Measurement of carbonaceous aerosol with different sampling configurations and frequencies

    Science.gov (United States)

    Cheng, Y.; He, K.-B.

    2015-07-01

    A common approach for measuring the mass of organic carbon (OC) and elemental carbon (EC) in airborne particulate matter involves collection on a quartz fiber filter and subsequent thermal-optical analysis. Although having been widely used in aerosol studies and in PM2.5 (fine particulate matter) chemical speciation monitoring networks in particular, this measurement approach is prone to several types of artifacts, such as the positive sampling artifact caused by the adsorption of gaseous organic compounds onto the quartz filter, the negative sampling artifact due to the evaporation of OC from the collected particles and the analytical artifact in the thermal-optical determination of OC and EC (which is strongly associated with the transformation of OC into char OC and typically results in an underestimation of EC). The presence of these artifacts introduces substantial uncertainties to observational data on OC and EC and consequently limits our ability to evaluate OC and EC estimations in air quality models. In this study, the influence of sampling frequency on the measurement of OC and EC was investigated based on PM2.5 samples collected in Beijing, China. Our results suggest that the negative sampling artifact of a bare quartz filter could be remarkably enhanced due to the uptake of water vapor by the filter medium. We also demonstrate that increasing sampling duration does not necessarily reduce the impact of positive sampling artifact, although it will enhance the analytical artifact. Due to the effect of the analytical artifact, EC concentrations of 48 h averaged samples were about 15 % lower than results from 24 h averaged ones. In addition, it was found that with the increase of sampling duration, EC results exhibited a stronger dependence on the charring correction method and, meanwhile, optical attenuation (ATN) of EC (retrieved from the carbon analyzer) was more significantly biased by the shadowing effect. Results from this study will be useful for the

  13. Correlating Mineralogy and Amino Acid Contents of Milligram-Scale Murchison Carbonaceous Chondrite Samples

    Science.gov (United States)

    Burton, Aaron, S.; Berger, Eve L.; Locke, Darren R.; Elsila, Jamie E.; Glavin, Daniel P.; Dworkin, Jason P.

    2015-01-01

    Amino acids, the building blocks of proteins, have been found to be indigenous in most of the carbonaceous chondrite groups. The abundances of amino acids, as well as their structural, enantiomeric and isotopic compositions differ significantly among meteorites of different groups and petrologic types. This suggests that there is a link between parent-body conditions, mineralogy and the synthesis and preservation of amino acids (and likely other organic molecules). However, elucidating specific causes for the observed differences in amino acid composition has proven extremely challenging because samples analyzed for amino acids are typically much larger ((is) approximately 100 mg powders) than the scale at which meteorite heterogeneity is observed (sub mm-scale differences, (is) approximately 1-mg or smaller samples). Thus, the effects of differences in mineralogy on amino acid abundances could not be easily discerned. Recent advances in the sensitivity of instrumentation have made possible the analysis of smaller samples for amino acids, enabling a new approach to investigate the link between mineralogical con-text and amino acid compositions/abundances in meteorites. Through coordinated mineral separation, mineral characterization and highly sensitive amino acid analyses, we have performed preliminary investigations into the relationship between meteorite mineralogy and amino acid composition. By linking amino acid data to mineralogy, we have started to identify amino acid-bearing mineral phases in different carbonaceous meteorites. The methodology and results of analyses performed on the Murchison meteorite are presented here.

  14. Selenium in Paleozoic stone coal (carbonaceous shale) as a significant source of environmental contamination in rural southern China

    Science.gov (United States)

    Belkin, H. E.; Luo, K.

    2012-04-01

    Selenium occurs in high concentrations (typically > 10 and up to 700 ppm) in organic-rich Paleozoic shales and cherts (called "stone coal" - shíméi), in southern China. Stone coals are black shales that formed in anoxic to euxinic environments and typically contain high concentrations of organic carbon, are enriched in various metals such as V, Mo, Pb, As, Cr, Ni, Se, etc., and are distinguished from "humic" coal in the Chinese literature. We have examined stone coal from Shaanxi, Hubei, and Guizhou Provinces, People's Republic of China and have focused our study on the mode of occurrence of Se and other elements (e.g. As, Pb, etc.) hazardous to human health. Scanning electron microscope, energy-dispersive analysis and electron microprobe wave-length dispersive spectroscopy were used to identify and determine the composition of host phases observed in the stone coals. Native selenium, Se-bearing pyrite and other sulfides are the hosts for Se, although we cannot preclude an organic or clay-mineral association. Stone coals are an important source of fuel (reserves over 1 billion tonnes), both domestically and in small industry, in some rural parts of southern China and present significant environmental problems for the indigenous population. The stone coals create three main environmental problems related to Se pollution. First, the residual soils formed on stone coal are enriched in Se and other metals contained in the stone coals and, depending on the speciation and bioavailability of the metals, may enrich crops and vegetation grown on them. Second, weathering and leaching of the stone coal contaminates the local ground water and/or surface waters with Se and other metals. Third, the local population uses the stone coal as a source of fuel, which releases the more volatile elements (Se and As) into the atmosphere in the homes. The ash will be extremely enriched with the balance of the heavy metal suite. Disposal of the ash on agricultural lands or near water

  15. Distilling solid carbonaceous materials

    Energy Technology Data Exchange (ETDEWEB)

    Ainscow, J.W.H.

    1928-11-19

    Carbonaceous materials such as coal or oil shale are distilled by being passed in a continuous stream through a retort heated externally and at temperatures increasing from the inlet to the outlet end, the distillates being taken off through openings in the retort wall.

  16. Rare earth element geochemistry of outcrop and core samples from the Marcellus Shale.

    Science.gov (United States)

    Noack, Clinton W; Jain, Jinesh C; Stegmeier, John; Hakala, J Alexandra; Karamalidis, Athanasios K

    2015-01-01

    In this work, the geochemistry of the rare earth elements (REE) was studied in eleven outcrop samples and six, depth-interval samples of a core from the Marcellus Shale. The REE are classically applied analytes for investigating depositional environments and inferring geochemical processes, making them of interest as potential, naturally occurring indicators of fluid sources as well as indicators of geochemical processes in solid waste disposal. However, little is known of the REE occurrence in the Marcellus Shale or its produced waters, and this study represents one of the first, thorough characterizations of the REE in the Marcellus Shale. In these samples, the abundance of REE and the fractionation of REE profiles were correlated with different mineral components of the shale. Namely, samples with a larger clay component were inferred to have higher absolute concentrations of REE but have less distinctive patterns. Conversely, samples with larger carbonate fractions exhibited a greater degree of fractionation, albeit with lower total abundance. Further study is necessary to determine release mechanisms, as well as REE fate-and-transport, however these results have implications for future brine and solid waste management applications.

  17. Bacterial Paleontology and Studies of Carbonaceous Chondrites

    Science.gov (United States)

    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.

  18. The characterisation of carbonaceous fly-ash particles from major European fossil-fuel types and applications to environmental samples

    Science.gov (United States)

    Rose, N. L.; Juggins, S.; Watt, J.

    This paper describes the development of a technique to characterise carbonaceous fly-ash particles produced from five major European fuel-types (coal, oil, brown coal, peat and oil shale) using individual particle chemistries derived from energy dispersive spectroscopy as part of the EU COPERNICUS funded FLAME project. The final classification employed an hierarchy of quadratic discriminant functions such that 80% of the particles could be allocated to the correct fuel-type. The technique was then applied to particles extracted from the surface sediments of 196 lakes across four countries (UK, Estonia, Czech Republic and Ireland) so that the spatial distribution of impacts from these fuel sources could be determined. Spatial trends in fuel-type showed good agreement with known emission sources but absolute percentages were low in all countries due to high allocations to the "coal" fuel-type. It is thought that these high coal values are due to mineral particles surviving the acid pre-treatment. However, the results can still be used to determine sources of pollutant deposition. The technique is applicable to particles extracted from any depositional sink including, atmospheric collectors, building stone crusts, leaves and soils.

  19. Properties of Silurian shales from the Barrandian Basin, Czech Republic

    Science.gov (United States)

    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

  20. UV to far-IR reflectance spectra of carbonaceous chondrites. I. Implications for remote characterization of dark primitive asteroids targeted by sample-return missions

    CERN Document Server

    Trigo-Rodriguez, Josep M; Llorca, Jordi; Fornasier, Sonia; Barucci, Maria A; Belskaya, Irina; Martins, Zita; Rivkin, Andy S; Dotto, Elisabetta; Madiedo, José M; Alonso-Azcárate, Jacinto

    2013-01-01

    We analyze here a wide sample of carbonaceous chondrites from historic falls (e.g. Allende, Cold Bokkeveld, Kainsaz, Leoville, Murchison, Murray and Orgueil), and from NASA Antarctic collection in order to get clues on the role of aqueous alteration in promoting the reflectance spectra diversity evidenced in the most primitive chondrite groups. We particularly focus in the identification of spectral features and behavior that can be used to remotely identify primitive carbonaceous asteroids. The selected meteorite specimens are a sample large enough to exemplify how laboratory reflectance spectra of rare groups of carbonaceous chondrites exhibit distinctive features that can be used to remotely characterize the spectra of primitive asteroids. Our spectra cover the full electromagnetic spectrum from 0.2 to 25 microns by using two spectrometers. First one is a UV-NIR spectrometer that covers the 0.2 to 2 microns window, while the second one is an Attenuated Total Reflectance IR spectrometer covering the 2 to 25...

  1. Pressurized fluidized-bed hydroretorting of eastern oil shales. Volume 4, Task 5, Operation of PFH on beneficiated shale, Task 6, Environmental data and mitigation analyses and Task 7, Sample procurement, preparation, and characterization: Final report, September 1987--May 1991

    Energy Technology Data Exchange (ETDEWEB)

    1992-03-01

    The objective of Task 5 (Operation of Pressurized Fluidized-Bed Hydro-Retorting (PFH) on Beneficiated Shale) was to modify the PFH process to facilitate its use for fine-sized, beneficiated Eastern shales. This task was divided into 3 subtasks: Non-Reactive Testing, Reactive Testing, and Data Analysis and Correlations. The potential environment impacts of PFH processing of oil shale must be assessed throughout the development program to ensure that the appropriate technologies are in place to mitigate any adverse effects. The overall objectives of Task 6 (Environmental Data and Mitigation Analyses) were to obtain environmental data relating to PFH and shale beneficiation and to analyze the potential environmental impacts of the integrated PFH process. The task was divided into the following four subtasks. Characterization of Processed Shales (IGT), 6.2. Water Availability and Treatment Studies, 6.3. Heavy Metals Removal and 6.4. PFH Systems Analysis. The objective of Task 7 (Sample Procurement, Preparation, and Characterization) was to procure, prepare, and characterize raw and beneficiated bulk samples of Eastern oil shale for all of the experimental tasks in the program. Accomplishments for these tasks are presented.

  2. Biological and biomedical (14)C-accelerator mass spectrometry and graphitization of carbonaceous samples.

    Science.gov (United States)

    Chung, Ill-Min; Kim, Seung-Hyun

    2013-06-21

    Accelerator mass spectrometry (AMS) is the ultimate technique for measuring rare isotopes in small samples. Biological and biomedical applications of (14)C-AMS (bio-(14)C-AMS) commenced in the early 1990s and are now widely used in many research fields including pharmacology, toxicology, food, and nutrition. For accurate, precise, and reproducible bio-(14)C-AMS analysis, the graphitization step in sample preparation is the most critical step. So, various sample preparation methods for a process called graphitization have been reported for specific applications. Catalytic graphitization using either a flame-sealed borosilicate tube or a septa-sealed vial is a popular sample preparation method for bio-(14)C-AMS. In this review, we introduce the AMS system, especially for bio-(14)C-AMS. In addition, we also review the graphitization method for bio-(14)C-AMS to promote further understanding and improvement of sample preparation for this technique. Examples of catalytic graphitization methods over the past two decades are described.

  3. Accelerator mass spectrometry targets of submilligram carbonaceous samples using the high-throughput Zn reduction method.

    Science.gov (United States)

    Kim, Seung-Hyun; Kelly, Peter B; Clifford, Andrew J

    2009-07-15

    The high-throughput Zn reduction method was developed and optimized for various biological/biomedical accelerator mass spectrometry (AMS) applications of mg of C size samples. However, high levels of background carbon from the high-throughput Zn reduction method were not suitable for sub-mg of C size samples in environmental, geochronology, and biological/biomedical AMS applications. This study investigated the effect of background carbon mass (mc) and background 14C level (Fc) from the high-throughput Zn reduction method. Background mc was 0.011 mg of C and background Fc was 1.5445. Background subtraction, two-component mixing, and expanded formulas were used for background correction. All three formulas accurately corrected for backgrounds to 0.025 mg of C in the aerosol standard (NIST SRM 1648a). Only the background subtraction and the two-component mixing formulas accurately corrected for backgrounds to 0.1 mg of C in the IAEA-C6 and -C7 standards. After the background corrections, our high-throughput Zn reduction method was suitable for biological (diet)/biomedical (drug) and environmental (fine particulate matter) applications of sub-mg of C samples (> or = 0.1 mg of C) in keeping with a balance between throughput (270 samples/day/analyst) and sensitivity/accuracy/precision of AMS measurement. The development of a high-throughput method for examination of > or = 0.1 mg of C size samples opens up a range of applications for 14C AMS studies. While other methods do exist for > or = 0.1 mg of C size samples, the low throughput has made them cost prohibitive for many applications.

  4. Evidence of Microfossils in Carbonaceous Chondrites

    Science.gov (United States)

    Hoover, Richard B.; Rozanov, Alexei Y.; Zhmur, S. I.; Gorlenko, V. M.

    1998-01-01

    Investigations have been carried out on freshly broken, internal surfaces of the Murchison, Efremovka and Orgueil carbonaceous chondrites using Scanning Electron Microscopes (SEM) in Russia and the Environmental Scanning Electron Microscope (ESEM) in the United States. These independent studies on different samples of the meteorites have resulted in the detection of numerous spherical and ellipsoidal bodies (some with spikes) similar to the forms of uncertain biogenicity that were designated "organized elements" by prior researchers. We have also encountered numerous complex biomorphic microstructures in these carbonaceous chondrites. Many of these complex bodies exhibit diverse characteristics reminiscent of microfossils of cyanobacteria such as we have investigated in ancient phosphorites and high carbon rocks (e.g. oil shales). Energy Dispersive Spectroscopy (EDS) analysis and 2D elemental maps shows enhanced carbon content in the bodies superimposed upon the elemental distributions characteristic of the chondritic matrix. The size, distribution, composition, and indications of cell walls, reproductive and life cycle developmental stages of these bodies are strongly suggestive of biology' These bodies appear to be mineralized and embedded within the meteorite matrix, and can not be attributed to recent surface contamination effects. Consequently, we have interpreted these in-situ microstructures to represent the lithified remains of prokaryotes and filamentous cyanobacteria. We also detected in Orgueil microstructures morphologically similar to fibrous kerite crystals. We present images of many biomorphic microstructures and possible microfossils found in the Murchison, Efremovka, and Orgueil chondrites and compare these forms with known microfossils from the Cambrian phosphate-rich rocks (phosphorites) of Khubsugul, Northern Mongolia.

  5. Acritarchs in carbonaceous meteorites and terrestrial rocks

    Science.gov (United States)

    Rozanov, Alexei Y.; Hoover, Richard B.

    2013-10-01

    Acritarchs are a group of organic-walled, acid-resistant microfossils of uncertain or unknown origin. Some are thought to represent the cysts or resting stages of unicellular protists (possibly dinoflagellates), chrysophytes (green algae) or other planktonic eukaryotic algae. Acritarchs are found throughout the geologic column extending back as far at 3.2 Ga. The presence of large sphaeromorphs in the Archaean provides evidence that the eukaryotic lineage extends much farther back in time than previously thought possible. Acritarchs are abundant in the Paleoproterozoic shales (1.9-1.6 Ga) of the former Soviet Union and they have been extensively used for the investigation of Proterozoic and Paleozoic biostratigraphy and paleoenvironmental parameters. Scanning Electron Microscope studies have revealed the fossilized remains of organic-walled microfossils of unknown origin and exhibiting characteristics of acritarchs in a variety of carbonaceous meteorites. In many cases, these remains are black or brown in color and have Carbon/Oxygen ratios suggesting they have been diagenetically converted into kerogen. It is not feasible that the fossilized remains of organicwalled microfossils such as acritarchs represent biological contaminant that invaded and became embedded in the rock matrix of carbonaceous meteorites within the short time periods of their residence on Earth. Consequently, these groups of microfossils are considered to provide an additional line for the existence of indigenous extraterrestrial microbial remains in meteorites. This paper presents a brief review of acritarchs in terrestrial rocks and provides images of a number of similar morphotypes of uncertain origin found in freshly fractured samples of carbonaceous meteorites.

  6. Oil shale commercialization study

    Energy Technology Data Exchange (ETDEWEB)

    Warner, M.M.

    1981-09-01

    Ninety four possible oil shale sections in southern Idaho were located and chemically analyzed. Sixty-two of these shales show good promise of possible oil and probable gas potential. Sixty of the potential oil and gas shales represent the Succor Creek Formation of Miocene age in southwestern Idaho. Two of the shales represent Cretaceous formations in eastern Idaho, which should be further investigated to determine their realistic value and areal extent. Samples of the older Mesozonic and paleozoic sections show promise but have not been chemically analyzed and will need greater attention to determine their potential. Geothermal resources are of high potential in Idaho and are important to oil shale prospects. Geothermal conditions raise the geothermal gradient and act as maturing agents to oil shale. They also might be used in the retorting and refining processes. Oil shales at the surface, which appear to have good oil or gas potential should have much higher potential at depth where the geothermal gradient is high. Samples from deep petroleum exploration wells indicate that the succor Creek shales have undergone considerable maturation with depth of burial and should produce gas and possibly oil. Most of Idaho's shales that have been analyzed have a greater potential for gas than for oil but some oil potential is indicated. The Miocene shales of the Succor Creek Formation should be considered as gas and possibly oil source material for the future when technology has been perfectes. 11 refs.

  7. Total lead (Pb) concentration in oil shale ash samples based on correlation to isotope Pb-210 gamma-spectrometric measurements

    Energy Technology Data Exchange (ETDEWEB)

    Vaasma, T.; Kiisk, M.; Tkaczyk, A.H. [University of Tartu (Estonia); Bitjukova, L. [Tallinn University of Technology (Estonia)

    2014-07-01

    Estonian oil shale consists of organic matter and mineral material and contains various amounts of heavy metals as well as natural radionuclides (from the U-238 and Th-232 series and K-40). Previous research has shown that burning oil shale in the large power plants causes these radionuclides to become enriched in different ash fractions and be partially emitted to the atmosphere via fly ash and flue gases. The activity concentrations (Bq/kg) of these nuclides in different oil shale ash fractions vary significantly. This is influenced by the boiler parameters and combustion conditions - prevailing temperatures, pressure, ash circulating mechanisms, fly ash particle size, chemical composition of ash and coexistence of macro and micro components. As with radionuclides, various heavy metals remain concentrated in the ash fractions and are released to the atmosphere (over 20 tons of Pb per year from Estonian oil shale power plants). Lead is a heavy metal with toxic influence on the nervous system, reproductive system and different organs in human body. Depending on the exposure pathways, lead could pose a long term health hazard. Ash samples are highly heterogeneous and exhibit great variability in composition and particle size. Determining the lead concentration in ash samples by modern methods like inductively coupled plasma mass spectroscopy (ICP-MS), flame atomic absorption spectrometry (FAAS), graphite furnace atomic absorption spectroscopy (GFAAS) and other techniques often requires time consuming, multistage and complex chemical sample preparation. The list of possible methods to use is lengthy, but it is a challenge to choose a suitable one to meet measurement needs and practical considerations. The detection limits, capital costs and maintenance expenses vary between the instruments. This work presents the development of an alternative measurement technique for our oil shale ash samples. Oil shale ash was collected from different boilers using pulverized fuel

  8. Sampling designs for geochemical baseline studies in the Colorado oil shale region: a manual for practical application

    Energy Technology Data Exchange (ETDEWEB)

    Klusman, R. W.; Ringrose, C. D.; Candito, R. J.; Zuccaro, B.; Rutherford, D. W.; Dean, W. E.

    1980-06-01

    This manual presents a rationale for sampling designs, and results of geochemical baseline studies in the Colorado portion of the oil-shale region. The program consists of a systematic trace element study of soils, stream sediments, and plants carried out in a way to be conservative of human and financial resources and yield maximum information. Extension of this approach to other parameters, other locations, and to environmental baseline studies in general is a primary objective. A baseline for any geochemical parameter can be defined as the concentration of that parameter in a given medium such as soil, the range of its concentration, and the geographic scale of variability. In air quality studies, and to a lesser extent for plants, the temporal scale of variability must also be considered. In studies of soil, the temporal variablility does not become a factor until such time that a study is deemed necessary to evaluate whether or not there have been changes in baseline levels as a result of development. The manual is divided into five major parts. The first is a suggested sampling protocol which is presented in an outline form for guiding baseline studies in this area. The second section is background information on the physical features of the area of study, trace elements of significance occurring in oil shale, and the sample media used in these studies. The third section is concerned primarily with sampling design and its application to the geochemical studies of the oil shale region. The last sections, in the form of appendices, provide actual data and illustrate in a systematic manner, the calculations performed to obtain the various summary data. The last segment of the appendices is a more academic discussion of the geochemistry of trace elements and the parameters of importance influencing their behavior in natural systems.

  9. Shale gas reservoir characteristics of Ordovician-Silurian formations in the central Yangtze area, China

    Science.gov (United States)

    Shan, Chang'an; Zhang, Tingshan; Wei, Yong; Zhang, Zhao

    2016-07-01

    The characteristics of a shale gas reservoir and the potential of a shale gas resource of Ordovician-Silurian age in the north of the central Yangtze area were determined. Core samples from three wells in the study area were subjected to thin-section examination, scanning electron microscopy, nuclear magnetic resonance testing, X-ray diffraction mineral analysis, total organic carbon (TOC) testing, maturity testing, gas-bearing analysis, and gas component and isothermal adsorption experiments. A favorable segment of the gas shale reservoir was found in both the Wufeng Formation and the lower part of the Longmaxi Formation; these formations were formed from the late Katian to early Rhuddanian. The high-quality shale layers in wells J1, J2, and J3 featured thicknesses of 54.88 m, 48.49 m, and 52.00 m, respectively, and mainly comprised carbonaceous and siliceous shales. Clay and brittle minerals showed average contents of 37.5% and 62.5% (48.9% quartz), respectively. The shale exhibited type II1 kerogens with a vitrinite reflectance ranging from 1.94% to 3.51%. TOC contents of 0.22%-6.05% (average, 2.39%) were also observed. The reservoir spaces mainly included micropores and microfractures and were characterized by low porosity and permeability. Well J3 showed generally high gas contents, i.e., 1.12-3.16 m3/t (average 2.15 m3/t), and its gas was primarily methane. The relatively thick black shale reservoir featured high TOC content, high organic material maturity, high brittle mineral content, high gas content, low porosity, and low permeability. Shale gas adsorption was positively correlated with TOC content and organic maturity, weakly positive correlated with quartz content, and weakly negatively correlated with clay content. Therefore, the Wufeng and Longmaxi formations in the north of the central Yangtze area have a good potential for shale gas exploration.

  10. Shale gas reservoir characteristics of Ordovician-Silurian formations in the central Yangtze area, China

    Science.gov (United States)

    Shan, Chang'an; Zhang, Tingshan; Wei, Yong; Zhang, Zhao

    2017-03-01

    The characteristics of a shale gas reservoir and the potential of a shale gas resource of Ordovician-Silurian age in the north of the central Yangtze area were determined. Core samples from three wells in the study area were subjected to thin-section examination, scanning electron microscopy, nuclear magnetic resonance testing, X-ray diffraction mineral analysis, total organic carbon (TOC) testing, maturity testing, gas-bearing analysis, and gas component and isothermal adsorption experiments. A favorable segment of the gas shale reservoir was found in both the Wufeng Formation and the lower part of the Longmaxi Formation; these formations were formed from the late Katian to early Rhuddanian. The high-quality shale layers in wells J1, J2, and J3 featured thicknesses of 54.88 m, 48.49 m, and 52.00 m, respectively, and mainly comprised carbonaceous and siliceous shales. Clay and brittle minerals showed average contents of 37.5% and 62.5% (48.9% quartz), respectively. The shale exhibited type II1 kerogens with a vitrinite reflectance ranging from 1.94% to 3.51%. TOC contents of 0.22%-6.05% (average, 2.39%) were also observed. The reservoir spaces mainly included micropores and microfractures and were characterized by low porosity and permeability. Well J3 showed generally high gas contents, i.e., 1.12-3.16 m3/t (average 2.15 m3/t), and its gas was primarily methane. The relatively thick black shale reservoir featured high TOC content, high organic material maturity, high brittle mineral content, high gas content, low porosity, and low permeability. Shale gas adsorption was positively correlated with TOC content and organic maturity, weakly positive correlated with quartz content, and weakly negatively correlated with clay content. Therefore, the Wufeng and Longmaxi formations in the north of the central Yangtze area have a good potential for shale gas exploration.

  11. The effect of deformation on two-phase flow through proppant-packed fractured shale samples: A micro-scale experimental investigation

    Science.gov (United States)

    Arshadi, Maziar; Zolfaghari, Arsalan; Piri, Mohammad; Al-Muntasheri, Ghaithan A.; Sayed, Mohammed

    2017-07-01

    We present the results of an extensive micro-scale experimental investigation of two-phase flow through miniature, fractured reservoir shale samples that contained different packings of proppant grains. We investigated permeability reduction in the samples by conducting experiments under a wide range of net confining pressures. Three different proppant grain distributions in three individual fractured shale samples were studied: i) multi-layer, ii) uniform mono-layer, and iii) non-uniform mono-layer. We performed oil-displacing-brine (drainage) and brine-displacing-oil (imbibition) flow experiments in the proppant packs under net confining pressures ranging from 200 to 6000 psi. The flow experiments were performed using a state-of-the-art miniature core-flooding apparatus integrated with a high-resolution, X-ray microtomography system. We visualized fluid occupancies, proppant embedment, and shale deformation under different flow and stress conditions. We examined deformation of pore space within the proppant packs and its impact on permeability and residual trapping, proppant embedment due to changes in net confining stress, shale surface deformation, and disintegration of proppant grains at high stress conditions. In particular, geometrical deformation and two-phase flow effects within the proppant pack impacting hydraulic conductivity of the medium were probed. A significant reduction in effective oil permeability at irreducible water saturation was observed due to increase in confining pressure. We propose different mechanisms responsible for the observed permeability reduction in different fracture packings. Samples with dissimilar proppant grain distributions showed significantly different proppant embedment behavior. Thinner proppant layer increased embedment significantly and lowered the onset confining pressure of embedment. As confining stress was increased, small embedments caused the surface of the shale to fracture. The produced shale fragments were

  12. Microstructural investigation of a locally mirror-like surface collected at 4 km depth in a Pomeranian shale sample

    Science.gov (United States)

    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

  13. Radon-222 content of natural gas samples from Upper and Middle Devonian sandstone and shale reservoirs in Pennsylvania—preliminary data

    Science.gov (United States)

    Rowan, E.L.; Kraemer, T.F.

    2012-01-01

    Samples of natural gas were collected as part of a study of formation water chemistry in oil and gas reservoirs in the Appalachian Basin. Nineteen samples (plus two duplicates) were collected from 11 wells producing gas from Upper Devonian sandstones and the Middle Devonian Marcellus Shale in Pennsylvania. The samples were collected from valves located between the wellhead and the gas-water separator. Analyses of the radon content of the gas indicated 222Rn (radon-222) activities ranging from 1 to 79 picocuries per liter (pCi/L) with an overall median of 37 pCi/L. The radon activities of the Upper Devonian sandstone samples overlap to a large degree with the activities of the Marcellus Shale samples.

  14. Search for Fluid Inclusions in a Carbonaceous Chondrite Using a New X-Ray Micro-Tomography Technique Combined with FIB Sampling

    Science.gov (United States)

    Tsuchiyama, A.; Miyake, A.; Zolensky, M. E.; Uesugi, K.; Nakano, T.; Takeuchi, A.; Suzuki, Y.; Yoshida, K.

    2014-01-01

    Early solar system aqueous fluids are preserved in some H chondrites as aqueous fluid inclusions in halite (e.g., [1]). Although potential fluid inclusions are also expected in carbonaceous chondrites [2], they have not been surely confirmed. In order to search for these fluid inclusions, we have developped a new X-ray micro-tomography technique combined with FIB sampling and applied this techniqu to a carbanaceous chondrite. Experimental: A polished thin section of Sutter's Mill meteorite (CM) was observed with an optical microscope and FE-SEM (JEOL 7001F) for chosing mineral grains of carbonates (mainly calcite) and sulfides (FeS and ZnS) 20-50 microns in typical size, which may have aqueous fluid inclusions. Then, a "house" similar to a cube with a roof (20-30 microns in size) is sampled from the mineral grain by using FIB (FEI Quanta 200 3DS). Then, the house was atached to a thin W-needle by FIB and imaged by a SR-based imaging microtomography system with a Fresnel zone plate at beamline BL47XU, SPring-8, Japan. One sample was imaged at two X-ray energies, 7 and 8 keV, to identify mineral phases (dual-enegy microtomography: [3]). The size of voxel (pixel in 3D) was 50-80 nm, which gave the effective spatial resolution of approx. 200 nm. A terrestrial quartz sample with an aqueous fluid inclusion with a bubble was also examined as a test sample by the same method. Results and discussion: A fluid inclusion of 5-8 microns in quartz was clearly identified in a CT image. A bubble of approx. 4 microns was also identified as refraction contrast although the X-ray absorption difference between fluid and bubble is small. Volumes of the fluid and bubble were obtained from the 3D CT images. Fourteen grains of calcite, two grains of iron sulfide and one grain of (Zn,Fe)S were examined. Ten calcite, one iron sulfide and one (Zn,Fe)S grains have inclusions >1 micron in size (the maximum: approx. 5 microns). The shapes are spherical or irregular. Tiny inclusions (sample as

  15. Trace-element and multi-isotope geochemistry of Late-Archean black shales in the Carajas iron-ore district, Brazil

    DEFF Research Database (Denmark)

    Cabral, A. R.; Creaser, R. A.; Naegler, T.

    2013-01-01

    The 250-300-m-thick Carajas Formation in the Carajas mineral province, northern Brazil, consists of banded iron formation (including giant high-grade iron-ore deposits) and minor black shale, overlying a thick pile (2-3 km) of about 2.75-Ga-old metabasalt. Carbonaceous shale with pyrite-and locally...... pyrrhotite-rich patches from drillcore of the Serra Sul exploration project has up to 29 ppm Mo; iron-speciation analysis indicates essentially ferruginous and for some samples likely euxinic depositional conditions. Positive delta S-34-isotope ratios of TRIS are between +0.3 to +10.7 parts per thousand...

  16. Deflating the shale gas potential of South Africa's Main Karoo basin

    Directory of Open Access Journals (Sweden)

    Michiel O. de Kock

    2017-09-01

    Full Text Available The Main Karoo basin has been identified as a potential source of shale gas (i.e. natural gas that can be extracted via the process of hydraulic stimulation or ‘fracking’. Current resource estimates of 0.4–11x109 m3 (13–390 Tcf are speculatively based on carbonaceous shale thickness, area, depth, thermal maturity and, most of all, the total organic carbon content of specifically the Ecca Group’s Whitehill Formation with a thickness of more than 30 m. These estimates were made without any measurements on the actual available gas content of the shale. Such measurements were recently conducted on samples from two boreholes and are reported here. These measurements indicate that there is little to no desorbed and residual gas, despite high total organic carbon values. In addition, vitrinite reflectance and illite crystallinity of unweathered shale material reveal the Ecca Group to be metamorphosed and overmature. Organic carbon in the shale is largely unbound to hydrogen, and little hydrocarbon generation potential remains. These findings led to the conclusion that the lowest of the existing resource estimates, namely 0.4x109 m3 (13 Tcf, may be the most realistic. However, such low estimates still represent a large resource with developmental potential for the South African petroleum industry. To be economically viable, the resource would be required to be confined to a small, well-delineated ‘sweet spot’ area in the vast southern area of the basin. It is acknowledged that the drill cores we investigated fall outside of currently identified sweet spots and these areas should be targets for further scientific drilling projects. Significance: This is the first report of direct measurements of the actual gas contents of southern Karoo basin shales. The findings reveal carbon content of shales to be dominated by overmature organic matter. The results demonstrate a much reduced potential shale gas resource presented by the Whitehill

  17. XCT quantified: a multiscale roughness study of fractures and veins in Pomeranian shale on samples collected at 4 km depth

    Science.gov (United States)

    Pluymakers, Anne; Renard, Francois

    2016-04-01

    In low-permeability rocks, such as shale, fractures are an important control on permeability, where the formation permeability will be a combination of matrix permeability plus that of the natural and induced fractures. We obtained shale samples from borehole material, originating at 4 km depth in the Polish Pomeranian basin. They consist of 40-60% illite plus mica, 1-10% organic matter, 10% chlorite, 10% carbonates, plus minor amounts of K-feldspar, plagioclase and kaolinite. There are many bedding-parallel fractures present in the retrieved core material, as well as bedding-parallel carbonate-rich veins. The existence and origin of these fractures at depth is debated, as they could have formed as well during drilling plus exhumation of the borehole samples. However, vein formation occurs at depth, and as such the topography of the vein-rock interface is preserved even upon sample extraction. We have imaged 4 samples in 3D using X-ray microtomography performed on a laboratory tomograph. One sample was also analyzed on the beamline ID19 at the European Synchrotron Radiation Facility, with final voxel spatial sizes ranging between 0.6-26 micrometers, thus allowing a multi-scale analysis of fractures and veins. The shape and aperture of the fractures and veins have been extracted in 3D. Fluid flow is controlled by fracture aperture plus the surface roughness of the fracture wall. Hence, fracture and vein roughness plus their spatial scaling properties are characterized using the Hurst exponent H. At low resolution (11-26 μm per voxel) there is a small difference in Hurst exponents parallel or perpendicular to the bedding, but on average veins exhibit H = 0.47, and cracks H = 0.35. Thus, veins exhibit more texture than cracks. This may be related to a different aperture mechanism, or to a characteristic 'grain size' present in the vein fill material. The sample scanned at multiple resolutions showed that an increase in resolution leads to an increase in the Hurst

  18. Enrichment of {sup 210}Po and {sup 210}Pb in ash samples from oil shale-fired power plants in Estonia

    Energy Technology Data Exchange (ETDEWEB)

    Ozden, B. [University of Tartu, Institute of Physics/Ege University, Institute of Nuclear Sciences (Estonia); Vaasma, T.; Kiisk, M.; Suursoo, S.; Tkaczyk, A.H. [University of Tartu,Institute of Physics (Estonia)

    2014-07-01

    Energy production in Estonia is largely dependent on the oil shale industry. Oil shale is a fossil fuel typically characterized by relatively high mineral composition, modest organic fraction (varying between 10 and 65%), high ash content (usually 45% to 50%), and average lower heating value of 8.4 MJ/kg{sup -1}. Oil shale-fired power plants account for 85% of Estonian electricity production and produce up to 6 million tons of oil shale ash annually. This ash contains elevated amounts of natural radionuclides (from the {sup 238}U and {sup 232}Th series and {sup 40}K), which were bound to oil shale during its formation. These radionuclides become enriched in ash fractions during the combustion process and are partially emitted to the atmosphere via fly ash and flue gases. Oil shale-fired electricity production is foreseen to remain a dominant trend in Estonia, suggesting that the radionuclide emissions to the atmosphere will continue in the future. The natural radionuclides {sup 210}Po and {sup 210}Pb, with half-lives of 138 days and 22.3 years respectively, originate from the radioactive decay of radionuclides of {sup 238}U series present in the earth's crust. These radionuclides are also built up artificially in the environment due to waste discharge from phosphate, oil, and gas industries, combustion of fossil fuels and other energy production as technically enhanced natural radionuclides. There are few studies on oil shale power plants influence on the levels of natural radioactivity in the surrounding areas. Realo, et al. reported that the annual doses from fly ash depositions over a 30 year period are in the range 90 - 200 μSv a{sup -1}. A study previously initiated by the University of Tartu, Institute of Physics (IPh) evaluated enrichment in the activity concentrations of {sup 238}U, {sup 226}Ra, {sup 210}Pb, {sup 232}Th, {sup 228}Ra and {sup 40}K in ash samples collected from Eesti Power Plant's circulating fluidized bed (CFB) boiler. According

  19. Oil Shale

    Science.gov (United States)

    Birdwell, Justin E.

    2017-01-01

    Oil shales are fine-grained sedimentary rocks formed in many different depositional environments (terrestrial, lacustrine, marine) containing large quantities of thermally immature organic matter in the forms of kerogen and bitumen. If defined from an economic standpoint, a rock containing a sufficient concentration of oil-prone kerogen to generate economic quantities of synthetic crude oil upon heating to high temperatures (350–600 °C) in the absence of oxygen (pyrolysis) can be considered an oil shale.

  20. A combined FE-SEM/EDS and μ-IR analysis of Carbonaceous Chondrites, analogue of the next returned asteroid samples

    Science.gov (United States)

    Dirri, Fabrizio; Palomba, Ernesto; Ferrari, Marco; Longobardo, Andrea; Rotundi, Alessandra

    2016-10-01

    A combined method for the analysis of extraterrestrial samples returned by spacecrafts foresees two different analytical techniques: Field Emission-Scanning Electron Microscope with Energy Dispersive Spectroscopy (FE-SEM/EDS) and Infrared μ-spectroscopy (μ-IR). These are non-destructive analytical techniques that allow obtaining mineral and organic information of the samples: μ-IR spectroscopy is able to provide thermal maps of selected area, whereas FE-SEM/EDS microscopy provides information on sample morphology and chemical composition. The combined results provide a complete overview of the sample mineralogy.In the past, different types of analysis were performed in order to characterise returned asteroid and cometary samples, and meteorites [e.g. 1,2,3]. Waiting for the analyses of the samples to be returned from primitive asteroids targets by Hayabusa 2 and Osiris Rex missions [4,5], we applied the combined FE-SEM/EDS and μ-IR techniques to Carbonaceous Chondrites (CC) meteorites as possible analogues. In particular, we selected 3 samples: Murchinson (CM2 group), characterised by small chondrules and refractory inclusions [6]; Orgueil (CI1 group) characterised by the absence of chondrules and refractory inclusion and with a high degree of hydration [7]; NWA2086 (CV3 group) with considerable amount of large mm-size chondrules, many surrounded by igneous rims [8]. A preliminary analysis was performed on the samples using a Stereo Microscope (Leica M205c) equipped with a digital camera in order to select regions of the samples showing a significant mineralogical heterogeneity.[1] Rotundi, A. et al., Meteorit. & Planet. Scie.,49,4,550-575,2014[2] Matrajt, G. et al.,A&A,416,3,983-990,2004[3] Naraoka, H. et al.,Geochem. J.,46,1,61-72,2012[4] Chasley, R. et al.,Icarus,235,5-22,2014[5] Yoshikawa, M. et al., 47th LPSC Abs,2016[6] Cronin, J.R. and Chang, S.,The Chemistry of Life's Origins, 416,209-258,1993[7] Tomeoka K. and Buseck P.R., Geochimica et Cosmochimica

  1. Improved measurement of carbonaceous aerosol: evaluation of the sampling artifacts and inter-comparison of the thermal-optical analysis methods

    Directory of Open Access Journals (Sweden)

    Y. Cheng

    2010-09-01

    Full Text Available The sampling artifacts (both positive and negative and the influence of thermal-optical methods (both charring correction method and the peak inert mode temperature on the split of organic carbon (OC and elemental carbon (EC were evaluated in Beijing. The positive sampling artifact constituted 10% and 23% of OC concentration determined by the bare quartz filter during winter and summer, respectively. For summer samples, the adsorbed gaseous organics were found to continuously evolve off the filter during the whole inert mode when analyzed by the IMPROVE-A temperature protocol. This may be due to the oxidation of the adsorbed organics during sampling (reaction artifact which would increase their thermal stability. The backup quartz approach was evaluated by a denuder-based method for assessing the positive artifact. The quartz-quartz (QBQ in series method was demonstrated to be reliable, since all of the OC collected by QBQ was from originally gaseous organics. Negative artifact that could be adsorbed by quartz filter was negligible. When the activated carbon impregnated glass fiber (CIG filter was used as the denuded backup filter, the denuder efficiency for removing gaseous organics that could be adsorbed by the CIG filter was only about 30%. EC values were found to differ by a factor of about two depending on the charring correction method. Influence of the peak inert mode temperature was evaluated based on the summer samples. The EC value was found to continuously decrease with the peak inert mode temperature. Premature evolution of light absorbing carbon began when the peak inert mode temperature was increased from 580 to 650 °C; when further increased to 800 °C, the OC and EC split frequently occurred in the He mode, and the last OC peak was characterized by the overlapping of two separate peaks. The discrepancy between EC values defined by different temperature protocols was larger for Beijing carbonaceous aerosol compared with North

  2. Terminology of carbonaceous materials

    Energy Technology Data Exchange (ETDEWEB)

    Bagrov, G.N.; Nagornyi, V.G.; Ostrovskii, V.S.

    1986-07-01

    The need is discussed to standardize definition of carbonaceous material. Terms related to carbonaceous materials and their products are selected and analyzed. Diagramatic representation is given of relationships between carbonaceous materials. Carbon has two forms of structure, cubic and hexagonal, characterized by sp/sup 3/-hybrid groups of atoms forming spatial system of tetrahedral bonds. Hexagonal form of carbon is represented by natural materials such as graphite, shungite, anthracite and a number of artificial materials obtained during thermal treatment of organic substances at temperatures above carbonization temperature. 4 references.

  3. Denitrification in marine shales in northeastern Colorado

    Science.gov (United States)

    McMahon, P.B.; Böhlke, J.K.; Bruce, B.W.

    1999-01-01

    Parts of the South Platte River alluvial aquifer in northeastern Colorado are underlain by the Pierre Shale, a marine deposit of Late Cretaceous age that is water in the aquifer is contaminated with NO3/-, and the shale contains abundant potential electron donors for denitrification in the forms of organic carbon and sulfide minerals. Nested piezometers were sampled, pore water was squeezed from cores of shale, and an injection test was conducted to determine if denitrification in the shale was a sink for alluvial NO3/- and to measure denitrification rates in the shale. Measured values of NO3/-, N2, NH4/+, ??15[NO3/-], ??15N[N2], and ??15N[NH4/+] in the alluvial and shale pore water indicated that denitrification in the shale was a sink for alluvial NO3/-. Chemical gradients, reaction rate constants, and hydraulic head data indicated that denitrification in the shale was limited by the slow rate of NO3/- transport (possibly by diffusion) into the shale. The apparent in situ first-order rate constant for denitrification in the shale based on diffusion calculations was of the order of 0.04-0.4 yr-1, whereas the potential rate constant in the shale based on injection tests was of the order of 60 yr-1. Chemical data and mass balance calculations indicate that organic carbon was the primary electron donor for denitrification in the shale during the injection test, and ferrous iron was a minor electron donor in the process. Flux calculations for the conditions encountered at the site indicate that denitrification in the shale could remove only a small fraction of the annual agricultural NO3/- input to the alluvial aquifer. However, the relatively large potential first-order rate constant for denitrification in the shale indicated that the percentage of NO3/- uptake by the shale could be considerably larger in areas where NO3/- is transported more rapidly into the shale by advection.

  4. 某低品位含钼钒碳质页岩型铀矿石浸出工艺研究%Study on the uranium and molybdenum and vanadium extraction technology for a low grade carbonaceous shale type uranium ore

    Institute of Scientific and Technical Information of China (English)

    周根茂; 曾毅君; 武翠莲; 贾秀敏; 王亮; 孟舒

    2012-01-01

    The processing technologies for extracting uranium and molybdenum and vanadium from a carbonaceous shale type uranium ore which contains vanadium and molybdenum were studied. The research results show that the ore is a polymetal associated uranium ore difficult to leaching. Uranium and molybdenum and vanadium in the ore were not synchronously extracted by H2SO4 or Na2CO3 leaching directly. With high-pressure leaching or acid curing, the contents of uranium and molybdenum in the residue were reduced to 0. 01% and 0. 02% respectively, and the vanadium leaching rate was over 50%.%对某含钼、钒碳质页岩型铀矿石开展铀、钼、钒综合提取工艺试验.研究结果表明:该铀矿石属于难浸出的多金属矿石,直接采用硫酸或碳酸钠浸出时,均不能实现铀、钼、钒的综合提取;采用加压酸浸或拌酸熟化搅拌浸出时,矿石中铀、钼、钒3种元素均可获得比较满意的浸出效果,渣中铀品位可降至0.01%左右,钼品位可降至0.02%以下,钒的浸出率达50%以上.

  5. Stratigraphy, sedimentology and bulk organic geochemistry of black shales from the Proterozoic Vindhyan Supergroup (central India)

    Indian Academy of Sciences (India)

    S Banerjee; S Dutta; S Paikaray; U Mann

    2006-02-01

    Four organic-rich shale units of the Proterozoic Vindhyan sedimentary succession have been scanned to reveal their origin and hydrocarbon potential.The wavy-crinkly nature of the carbonaceous laminae is suggestive of a microbial mat origin of the shales.These shales are thus different from Phanerozoic black shales which typically exhibit planar laminae.The hydrocarbon potential of the black shale units has been evaluated by Rock-Eval pyrolysis.Total organic carbon content of many of the shales exceeds 1%.The mean _max for the black shales translate to a vitrinite re flectance range of 2.05 –2.40%Rm based on standard conversion techniques.These shales have reached the catagenetic stage near the beginning of anthracite formation.

  6. Characterization of Carbonaceous Material from the Sudbury Impact Structure Using Raman Microspectroscopy

    Science.gov (United States)

    Wright, A. J.; Parnell, J.; Ames, D. E.

    2008-03-01

    Samples from the 1.85 Ga Sudbury impact structure have been analyzed using Raman microspectroscopy in order to characterize the carbonaceous material and to investigate the relationship between the carbonaceous strata associated with the structure.

  7. Mechanism for Burgess Shale-type preservation.

    Science.gov (United States)

    Gaines, Robert R; Hammarlund, Emma U; Hou, Xianguang; Qi, Changshi; Gabbott, Sarah E; Zhao, Yuanlong; Peng, Jin; Canfield, Donald E

    2012-04-03

    Exceptionally preserved fossil biotas of the Burgess Shale and a handful of other similar Cambrian deposits provide rare but critical insights into the early diversification of animals. The extraordinary preservation of labile tissues in these geographically widespread but temporally restricted soft-bodied fossil assemblages has remained enigmatic since Walcott's initial discovery in 1909. Here, we demonstrate the mechanism of Burgess Shale-type preservation using sedimentologic and geochemical data from the Chengjiang, Burgess Shale, and five other principal Burgess Shale-type deposits. Sulfur isotope evidence from sedimentary pyrites reveals that the exquisite fossilization of organic remains as carbonaceous compressions resulted from early inhibition of microbial activity in the sediments by means of oxidant deprivation. Low sulfate concentrations in the global ocean and low-oxygen bottom water conditions at the sites of deposition resulted in reduced oxidant availability. Subsequently, rapid entombment of fossils in fine-grained sediments and early sealing of sediments by pervasive carbonate cements at bed tops restricted oxidant flux into the sediments. A permeability barrier, provided by bed-capping cements that were emplaced at the seafloor, is a feature that is shared among Burgess Shale-type deposits, and resulted from the unusually high alkalinity of Cambrian oceans. Thus, Burgess Shale-type preservation of soft-bodied fossil assemblages worldwide was promoted by unique aspects of early Paleozoic seawater chemistry that strongly impacted sediment diagenesis, providing a fundamentally unique record of the immediate aftermath of the "Cambrian explosion."

  8. Recalcitrant Carbonaceous Material: A Source of Electron Donors for Anaerobic Microbial Metabolisms in the Subsurface?

    Science.gov (United States)

    Nixon, S. L.; Montgomery, W.; Sephton, M. A.; Cockell, C. S.

    2014-12-01

    More than 90% of organic material on Earth resides in sedimentary rocks in the form of kerogens; fossilized organic matter formed through selective preservation of high molecular weight biopolymers under anoxic conditions. Despite its prevalence in the subsurface, the extent to which this material supports microbial metabolisms is unknown. Whilst aerobic microorganisms are known to derive energy from kerogens within shales, utilization in anaerobic microbial metabolisms that proliferate in the terrestrial subsurface, such as microbial iron reduction, has yet to be demonstrated. Data are presented from microbial growth experiments in which kerogens and shales were supplied as the sole electron donor source for microbial iron reduction by an enrichment culture. Four well-characterized kerogens samples (representative of Types I-IV, classified by starting material), and two shale samples, were assessed. Organic analysis was carried out to investigate major compound classes present in each starting material. Parallel experiments were conducted to test inhibition of microbial iron reduction in the presence of each material when the culture was supplied with a full redox couple. The results demonstrate that iron-reducing microorganisms in this culture were unable to use kerogens and shales as a source of electron donors for energy acquisition, despite the presence of compound classes known to support this metabolism. Furthermore, the presence of these materials was found to inhibit microbial iron reduction to varying degrees, with some samples leading to complete inhibition. These results suggest that recalcitrant carbonaceous material in the terrestrial subsurface is not available for microbial iron reduction and similar metabolisms, such as sulphate-reduction. Further research is needed to investigate the inhibition exerted by these materials, and to assess whether these findings apply to other microbial consortia. These results may have significant implications for

  9. Carbonaceous Chondrite Thin Section Preparation

    Science.gov (United States)

    Harrington, R.; Righter, K.

    2017-01-01

    Carbonaceous chondrite meteorites have long posed a challenge for thin section makers. The variability in sample hardness among the different types, and sometimes within individual sections, creates the need for an adaptable approach at each step of the thin section making process. This poster will share some of the procedural adjustments that have proven to be successful at the NASA JSC Meteorite Thin Section Laboratory. These adjustments are modifications of preparation methods that have been in use for decades and therefore do not require investment in new technology or materials.

  10. Organic Chemistry of Carbonaceous Meteorites

    Science.gov (United States)

    Cronin, John R.

    2001-01-01

    Chiral and carbon-isotopic analyses of isovaline have been carried out on numerous samples of the Murchison and one sample of the Murray carbonaceous chondrite. The isovaline was found to be heterogeneous with regard to enantiomeric excess (ee) both between samples and within a single Murchison sample. L-Excesses ranging from 0 to 15% were observed. The isovaline delta(sup 13) C was found to be about +18%. No evidence was obtained suggesting terrestrial contamination in the more abundant L-enantiomer. A correlation was observed between isovaline (also alpha - aminoisobutyric acid) concentration and PCP content of five CM chondrites. It is suggested that isovaline, along with other meteoritic a-methyl amino acids with ee, are of presolar origin. The possible formation of ee in extraterrestrial amino acids by exposure to circularly polarized light or by magnetochiral photochemistry is discussed. Key words: Murchison meteorite, Murray meteorite, amino acids, isovaline, chirality, carbon isotopes, PCP.

  11. Chemistry of oil shale

    Energy Technology Data Exchange (ETDEWEB)

    Iida, T.

    1974-01-01

    A review with several references covers the formation, distribution, and mining of oil shales of Fu-Shun colliery; retorting furnaces for oil shale; refining of crude shale oils; and components of oil from Fu-Shun oil shales including pyrolle, matrine, fatty acid anilides, 2,4,5-trimethylpyrrole, and middle-layer bases.

  12. An NMR study on shale wettability

    Energy Technology Data Exchange (ETDEWEB)

    Odusina, Elijah; Sondergeld, Carl; Rai, Chandra [University of Oklahoma (United States)

    2011-07-01

    In recent years, the importance of shales as unconventional gas resources has grown significantly. It is therefore important to reach a better understanding of their petrophysical properties. One of the important rock properties that is directly linked to successful hydrocarbon recovery is wettability. This paper presents a study on shale wettability using nuclear magnetic resonance (NMR) to monitor sequential imbibition of brine and oil. Due to the presence of mineralogical variations, low permeability and viscosity, and complex pore structure, the interpretation of wettability using conventional approaches becomes complex. Samples that included 21 core plugs from the Eagle Ford shale, 12 from the Barnett, 11 from the Floyd, and 10 from the Woodford shale were analyzed. The NMR study confirmed the water-wet behavior of Berea sandstone. From the study, it was seen that the Woodford shale showed more affinity for dodecane than did the other shales.

  13. High efficiency shale oil recovery

    Energy Technology Data Exchange (ETDEWEB)

    Adams, D.C.

    1993-04-22

    The overall project objective is to demonstrate the high efficiency of the Adams Counter-Current shale oil recovery process. The efficiency will first be demonstrated on a small scale, in the current phase, after which the demonstration will be extended to the operation of a small pilot plant. Thus the immediate project objective is to obtain data on oil shale retorting operations in a small batch rotary kiln that will be representative of operations in the proposed continuous process pilot plant. Although an oil shale batch sample is sealed in the batch kiln from the start until the end of the run, the process conditions for the batch are the same as the conditions that an element of oil shale would encounter in a continuous process kiln. Similar chemical and physical conditions (heating, mixing, pyrolysis, oxidation) exist in both systems.The two most important data objectives in this phase of the project are to demonstrate (1) that the heat recovery projected for this project is reasonable and (2) that an oil shale kiln will run well and not plug up due to sticking and agglomeration. The following was completed this quarter. (1) Twelve pyrolysis runs were made on five different oil shales. All of the runs exhibited a complete absence of any plugging, tendency. Heat transfer for Green River oil shale in the rotary kiln was 84.6 Btu/hr/ft[sup 2]/[degrees]F, and this will provide for ample heat exchange in the Adams kiln. (2) One retorted residue sample was oxidized at 1000[degrees]F. Preliminary indications are that the ash of this run appears to have been completely oxidized. (3) Further minor equipment repairs and improvements were required during the course of the several runs.

  14. Analysis of Devonian Black Shales in Kentucky for Potential Carbon Dioxide Sequestration and Enhanced Natural Gas Production

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall; Cortland F. Eble; James A. Drahovzal; R. Marc Bustin

    2005-09-30

    Carbonaceous (black) Devonian gas shales underlie approximately two-thirds of Kentucky. In these shales, natural gas occurs in the intergranular and fracture porosity and is adsorbed on clay and kerogen surfaces. This is analogous to methane storage in coal beds, where CO2 is preferentially adsorbed, displacing methane. Black shales may similarly desorb methane in the presence of CO2. Drill cuttings from the Kentucky Geological Survey Well Sample and Core Library were sampled to determine both CO2 and CH4 adsorption isotherms. Sidewall core samples were acquired to investigate CO2 displacement of methane. An elemental capture spectroscopy log was acquired to investigate possible correlations between adsorption capacity and mineralogy. Average random vitrinite reflectance data range from 0.78 to 1.59 (upper oil to wet gas and condensate hydrocarbon maturity range). Total organic content determined from acid-washed samples ranges from 0.69 to 14 percent. CO2 adsorption capacities at 400 psi range from a low of 14 scf/ton in less organic-rich zones to more than 136 scf/ton in the more organic-rich zones. There is a direct linear correlation between measured total organic carbon content and the adsorptive capacity of the shale; CO2 adsorption capacity increases with increasing organic carbon content. Initial volumetric estimates based on these data indicate a CO2 sequestration capacity of as much as 28 billion tons total in the deeper and thicker parts of the Devonian shales in Kentucky. In the Big Sandy Gas Field area of eastern Kentucky, calculations using the net thickness of shale with 4 percent or greater total organic carbon, indicate that 6.8 billion tonnes of CO2 could be sequestered in the five county area. Discounting the uncertainties in reservoir volume and injection efficiency, these results indicate that the black shales of Kentucky are a potentially large geologic sink for CO2. Moreover, the extensive occurrence of gas shales in Paleozoic and Mesozoic

  15. The Xiamaling oil shale generated through Rhodophyta over 800 Ma ago

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A suit of oil shales, predominated by black argillaceous silicalite and finely laminated black-brown shale, has been discovered in a set of carbonaceous-siliceous mudstone formations (350 m in thickness) in the third member of Xiamaling Formation of the Upper Proterozoic Qingbaikou Series (900―873 MaBP), Xiahuayuan, Hebei Province, China. The oil shale, combustible with strong bitumen odour, has su- per-high TOC contents ranging from 21.4% to 22.9%, bitumen “A” contents from 0.58% to 0.88% and oil length from 5.29% to 10.57%. The ultrathin section observation of the shale and the identification of its kerogen demonstrate that its hydrocarbon-generative parent material is mainly benthonic Rhodophyta whose specific tetrasporangia are legible and abundant. It is rarely reported in the literature that such a hydrocarbon-generative parent material, composed mainly of Rhodophyta and with extraordinarily high contents of TOC and bitumen “A”, developed into a set of high-quality source rocks. The extracts of the oil shale are characteristic of richness in 17α(H)-diahopanes and n-alkyl tricyclic terpenoids but low in steranes. Such a biomarker feature is obviously different from that of the extracts from other Proterozoic marine carbonate source rocks of the studied area. Since the biological constitution of this oil shale is rather simple, it is clear that these biomarkers most likely represent to certain extent the specific mo- lecular constitutions of the benthonic Rhodophyta identified in the ultrathin sections of the samples. Studies on its lithologic association and depositional sequences suggest that this suit of the carbona- ceous-siliceous mudstone formation, which contains oil shales, was probably developed in an under- compensation deep-bay environment when a maximum transgression occurred during the formation of the third member of Xiamaling Formation. The high concentration of SiO2 in this organic-rich rock and the positive correlation between TOC

  16. The Xiamaling oil shale generated through Rhodophyta over 800 Ma ago

    Institute of Scientific and Technical Information of China (English)

    ZHANG ShuiChang; ZHANG BaoMin; BIAN LiZeng; JIN ZhiJun; WANG DaRui; CHEN JianFa

    2007-01-01

    A suit of oil shales, predominated by black argillaceous silicalite and finely laminated black-brown shale, has been discovered in a set of carbonaceous-siliceous mudstone formations(350 m in thickness)in the third member of Xiamaling Formation of the Upper Proterozoic Qingbaikou Series(900-873 MaBP), Xiahuayuan, Hebei Province, China. The oil shale, combustible with strong bitumen odour, has super-high TOC contents ranging from 21.4%to 22.9%,bitumen"A"contents from 0.58%to 0.88%and oil length from 5.29%to 10.57%.The ultrathin section observation of the shale and the identification of its kerogen demonstrate that its hydrocarbon-generative parent material is mainly benthonic Rhodophyta whose specific tetrasporangia are legible and abundant. It is rarely reported in the literature that such a hydrocarbon-generative parent material, composed mainly of Rhodophyta and with extraordinarily high contents of TOC and bitumen "A", developed into a set of high-quality source rocks. The extracts of the oil shale are characteristic of richness in 17α(H)-diahopanes and n-alkyl tricyclic terpenoids but low in steranes. Such a biomarker feature is obviously different from that of the extracts from other Proterozoic marine carbonate source rocks of the studied area. Since the biological constitution of this oil shale is rather simple, it is clear that these biomarkers most likely represent to certain extent the specific molecular constitutions of the benthonic Rhodophyta identified in the ultrathin sections of the samples. Studies on its lithologic association and depositional sequences suggest that this suit of the carbonsceous-siliceous mudstone formation, which contains oil shales, was probably developed in an undercompensation deep-bay environment when a maximum transgression occurred during the formation of the third member of Xiamaling Formation. The high concentration of SiO2 in this organic-rich rock and the positive correlation between TOC and some trace elements such as

  17. Carbonaceous film coating

    Science.gov (United States)

    Maya, Leon

    1989-01-01

    A method of making a carbonaceous film comprising heating tris(1,3,2-benzodiazaborolo)borazine or dodecahydro tris[1,3,2]diazaborine[1,2-a:1'2'-c:1"2"-e]borazine in an inert atmosphere in the presence of a substrate to a temperature at which the borazine compound decomposes, and the decomposition products deposit onto the substrate to form a thin, tenacious, highly reflective conductive coating having a narrow band gap which is susceptible of modification and a relatively low coefficient of friction.

  18. Developments in Oil Shale

    Science.gov (United States)

    2008-11-17

    demonstration (RD&D). The ongoing program will confirm whether an economically significant shale oil volume can be extracted under current operating...Petroleum Trade, [http://www.eia.doe.gov/emeu/mer/pdf/pages/sec1_15.pdf]. 2 Oil sands yield a bitumen substantially heavier most crude oils and shale oil. 3...hydrocarbon products that can be extracted from the shale. The most promising oil shales occur in the Green River formation that underlies 16,000 square

  19. THE PELLETS APPLICATION IN LABORATORY RESEARCHING OF INHIBITIVE MUD/SHALE INTERACTION

    Directory of Open Access Journals (Sweden)

    Borivoje Pašić

    2012-12-01

    Full Text Available Wellbore instability appears to be a serious problem during drilling process through shale. Shales instability cause basically comes out of its mineralogical composition (especially clay minerals content and physico-chemical properties. Many research activities about shale instability causes and shale properties (affecting shale behavior during interaction with water phase of different drilling muds definition have been carried out by now. In these laboratory tests were used original shales samples given by coring process or collecting shale cuttings from shale shakers, and different shale samples from outcrop. From this reason is very difficult compare laboratory tests results given by different authors. Possible solution is use artificial shale samples (pellets with exact mineralogical composition, enabling extensive laboratory tests and tests results comparison. In this paper presented laboratory tests of pellets swelling in inhibitive muds (the paper is published in Croatian.

  20. Extraterrestrial Nucleobases in Carbonaceous Chondrites

    Science.gov (United States)

    Martins, Z.; Botta, O.; Fogel, M.; Sephton, M.; Glavin, D.; Watson, J.; Dworkin, J.; Schwartz, A.; Ehrenfreund, P.

    Nucleobases in Carbonaceous Chondrites Z. Martins (1), O. Botta (2), M. L. Fogel (3), M. A. Sephton (4), D. P. Glavin (2), J. S. Watson (5), J. P. Dworkin (2), A. W. Schwartz (6) and P. Ehrenfreund (1,6). (1) Astrobiology Laboratory, Leiden Institute of Chemistry, Leiden, The Netherlands, (2) NASA Goddard Space Flight Center, Goddard Center for Astrobiology, Greenbelt, MD, USA, (3) GL, Carnegie Institution of Washington, Washington DC, USA, (4) Impacts and Astromaterials Research Centre, Department of Earth Science and Engineering, South Kensington Campus, Imperial College, London, UK, (5) Planetary and Space Sciences Research Institute, The Open University, Walton Hall, Milton Keynes, UK, (6) Radboud University Nijmegen, Nijmegen, The Netherlands. E-mail: z.martins@chem.leidenuniv.nl/Phone:+31715274440 Nucleobases are crucial compounds in terrestrial biochemistry, because they are key components of DNA and RNA. Carbonaceous meteorites have been analyzed for nucleobases by different research groups [1-5]. However, significant quantitative and qualitative differences were observed, leading to the controversial about the origin of these nucleobases. In order to establish the origin of these compounds in carbonaceous chondrites and to assess the plausibility of their exogenous delivery to the early Earth, we have performed formic acid extraction of samples of the Murchison meteorite [6], followed by an extensive purification procedure, analysis and quantification by high-performance liquid chromatography with UV absorption detection and gas chromatography-mass spectrometry. Our results were qualitatively consistent with previous results [3, 4], but showed significant quantitative differences. Compound specific carbon isotope values were obtained, using gas chromatography-combustion- isotope ratio mass spectrometry. A soil sample collected in the proximity of the Murchison meteorite fall site was subjected to the same extraction, purification and analysis procedure

  1. Optimisation of sample preparation protocols for measurement of PGE and Re-Os in organic-rich shales by isotope dilution ICP-MS

    Science.gov (United States)

    Rammensee, Philipp; Aulbach, Sonja; Gudelius, Dominik; Brey, Gerhard

    2013-04-01

    Platinum-group elements (PGE) and Re-Os isotopes, which are variably redox-sensitive and fluid-soluble, have potential as proxies for the oxygenation of the atmosphere and oceans (e.g. [1]). However, analysis of these elements in organic rich shales (ORS) is challenging due to abundances of chromatography is necessary to minimise the effects of interfering elements, but presents its own challenges. We are in the process of conducting variations of acid digestion and column chromatographic protocols on reference sample SDO-1 (Devonian Ohio Shale, USGS). We aim to identify the optimum protocol to investigate PGE-Re-Os systematics of ORS that were sampled as part of the Barberton Drilling Project BARB5 drill core, in order to constrain the changes in detrital and hydrogenous contributions to the sediment with time, to assess the extent of euxinity in the sedimentary basin and to look for evidence of transient "whiffs of oxygen" [1]. The following digestion methods were tested: (1) 4h acid digestion in High Pressure Asher (HPA) apparatus with reverse aqua regia at 300°C and 130 bar (only this digestion allows extraction of volatilised Os in CHCl3 followed by HBr); (2) 3h reverse aqua regia digestion in centrifuge vials on hotplate at 80°C; (3) 48h reverse aqua regia digestion in closed Teflon beakers on hotplate at 140°C followed by a HF/HNO3 digestion step; (4) 48h HF/HNO3 digestion of ashed sample powder in closed Teflon beaker at 140°C on hotplate followed by an aqua regia digestion step. Column chromatographic approaches to decrease the concentrations of interfering elements (Y, Zr, Mo, Cd, Hf, Hg) include the use of cation- and anion resins, and variations of the molarity and composition of the eluent. Preliminary results show that digestion method (1) leaves behind small amounts of presumably PGE-free silica gel; (2) yields consistently higher Re concentrations with an expectedly large amount of solid residue; (3) produces an insoluble sludge; (4) allows

  2. Effects of organic wastes on water quality from processing of oil shale from the Green River Formation, Colorado, Utah, and Wyoming

    Science.gov (United States)

    Leenheer, J.A.; Noyes, T.I.

    1986-01-01

    A series of investigations were conducted during a 6-year research project to determine the nature and effects of organic wastes from processing of Green River Formation oil shale on water quality. Fifty percent of the organic compounds in two retort wastewaters were identified as various aromatic amines, mono- and dicarboxylic acids phenols, amides, alcohols, ketones, nitriles, and hydroxypyridines. Spent shales with carbonaceous coatings were found to have good sorbent properties for organic constituents of retort wastewaters. However, soils sampled adjacent to an in situ retort had only fair sorbent properties for organic constituents or retort wastewater, and application of retort wastewater caused disruption of soil structure characteristics and extracted soil organic matter constituents. Microbiological degradation of organic solutes in retort wastewaters was found to occur preferentially in hydrocarbons and fatty acid groups of compounds. Aromatic amines did not degrade and they inhibited bacterial growth where their concentrations were significant. Ammonia, aromatic amines, and thiocyanate persisted in groundwater contaminated by in situ oil shale retorting, but thiosulfate was quantitatively degraded one year after the burn. Thiocyanate was found to be the best conservative tracer for retort water discharged into groundwater. Natural organic solutes, isolated from groundwater in contact with Green River Formation oil shale and from the White River near Rangely, Colorado, were readily distinguished from organic constituents in retort wastewaters by molecular weight and chemical characteristic differences. (USGS)

  3. Quantifying porosity, compressibility and permeability in Shale

    DEFF Research Database (Denmark)

    Mbia, Ernest Ncha; Fabricius, Ida Lykke; Frykman, Peter

    (XRD) of shale samples show about 50% silt and high content of kaolinite in the clay fraction when compared with offshore samples from the Central Graben. Porosity measurements from helium porosimetry-mercury immersion (HPMI), mercury injection capillary pressure (MICP) and nuclear magnetic resonance...... (NMR) show that, the MICP porosity is 9-10% points lower than HPMI and NMR porosity. Compressibility result shows that deep shale is stiffer in situ than normally assumed in geotechnical modelling and that static compressibility corresponds with dynamic one only at the begining of unloading stress...... strain data. We found that Kozeny's modelled permeability fall in the same order of magnitude with measured permeability for shale rich in kaolinite but overestimates permeability by two to three orders of magnitudes for shale with high content of smectite. The empirical Yang and Aplin model gives good...

  4. Common clay and shale

    Science.gov (United States)

    Virta, R.L.

    2011-01-01

    The article discusses the latest developments in the global common clay and shale industry, particularly in the U.S. It claims that common clay and shale is mainly used in the manufacture of heavy clay products like brick, flue tile and sewer pipe. The main producing states in the U.S. include North Carolina, New York and Oklahoma. Among the firms that manufacture clay and shale-based products are Mid America Brick & Structural Clay Products LLC and Boral USA.

  5. Microfossils in Carbonaceous Meteorites

    Science.gov (United States)

    Hoover, Richard B.

    2009-01-01

    Microfossils of large filamentous trichomic prokaryotes have been detected during in-situ investigations of carbonaceous meteorites. This research has been carried out using the Field Emission Scanning Electron Microscope (FESEM) to examine freshly fractured interior surfaces of the meteorites. The images obtained reveal that many of these remains are embedded in the meteorite rock matrix. Energy Dispersive X-Ray Spectroscopy (EDS) studies establish that the filamentous microstructures have elemental compositions consistent with the meteorite matrix, but are often encased within carbon-rich electron transparent sheath-like structures infilled with magnesium sulfate. This is consistent with the taphonomic modes of fossilization of cyanobacteria and sulphur bacteria, since the life habits and processes of these microorganisms frequently result in distinctive chemical biosignatures associated with the properties of their cell-walls, trichomes, and the extracellular polymeric substances (EPS) of the sheath. In this paper the evidence for biogenicity presented includes detailed morphological and morphometric data consistent with known characteristics of uniseriate and multiseriate cyanobacteria. Evidence for indigeneity includes the embedded nature of the fossils and elemental compositions inconsistent with modern biocontaminants.

  6. Gasification of carbonaceous solids

    Science.gov (United States)

    Coates, Ralph L.

    1976-10-26

    A process and apparatus for converting coal and other carbonaceous solids to an intermediate heating value fuel gas or to a synthesis gas. A stream of entrained pulverized coal is fed into the combustion stage of a three-stage gasifier along with a mixture of oxygen and steam at selected pressure and temperature. The products of the combustion stage pass into the second or quench stage where they are partially cooled and further reacted with water and/or steam. Ash is solidified into small particles and the formation of soot is suppressed by water/steam injections in the quench stage. The design of the quench stage prevents slag from solidifying on the walls. The products from the quench stage pass directly into a heat recovery stage where the products pass through the tube, or tubes, of a single-pass, shell and tube heat exchanger and steam is generated on the shell side and utilized for steam feed requirements of the process.

  7. Distillation of carbonaceous material

    Energy Technology Data Exchange (ETDEWEB)

    Ainscow, J.W.H.

    1936-10-03

    To recover hydrocarbon products by distillation of carbonaceous material in a plurality of horizontal zones maintained at different temperatures, a retort has a plurality of superimposed (3) retort chambers, the uppermost being in communication at one end with a hopper and at the other end through coupled junction not shown with one end of the next lower chamber, whose opposite end communicates with lowermost chamber, the other end of which has a sealed discharge passage, tank, and conveyor not shown. Each retort chamber has stirring and conveying means consisting of helical blades (2) attached to radial arms on shaft mounted in water cooled bearings and driven through suitably mounted sprocket wheels and chains not shown. Each retort chamber has a gas dome, with pyrometer tube, and off-take connected to a common main opening into a dust eliminator which in turn connects with a plurality of vertical condensation towers of known construction, maintained at different temperatures by means of steam from a superheater not shown situated in one retort chamber. The retort heating gases pass from the furnace via zig-zag, (three) baffles under and around each retort chamber to a flue not shown.

  8. Carbonaceous preservation of Cambrian hexactinellid sponge spicules.

    Science.gov (United States)

    Harvey, Thomas H P

    2010-12-23

    Early fossil sponges offer a direct window onto the evolutionary emergence of animals, but insights are limited by the paucity of characters preserved in the conventional fossil record. Here, a new preservational mode for sponge spicules is reported from the lower Cambrian Forteau Formation (Newfoundland, Canada), prompting a re-examination of proposed homologies and sponge inter-relationships. The spicules occur as wholly carbonaceous films, and are interpreted as the remains of robust organic spicule sheaths. Comparable sheaths are restricted among living taxa to calcarean sponges, although the symmetries of the fossil spicules are characteristic of hexactinellid sponges. A similar extinct character combination has been documented in the Burgess Shale fossil Eiffelia. Interpreting the shared characters as homologous implies complex patterns of spicule evolution, but an alternative interpretation as convergent autapomorphies is more parsimonious. In light of the mutually exclusive distributions of these same characters among the crown groups, this result suggests that sponges exhibited an early episode of disparity expansion followed by comparatively constrained evolution, a pattern shared with many other metazoans but obscured by the conventional fossil record of sponges.

  9. Research on the Eco-Geochemical Effects of Black Shales in Pingli County, Shaanxi

    Institute of Scientific and Technical Information of China (English)

    方维萱; 兀鹏武; 黄转莹

    2001-01-01

    This paper presents the results of eco-geochemical research on black rock series en riched in metallic elements in Pingli County, Shaanxi Province, which lies at the northern mar gin of the Yangtze Platform. There is a suite of bone coal-bearing black carbonaceous rocks in the Cambrian Donghe Formation throughout the region. Soils in Pingli contain high metallic el ements derived from the bone coal and carbonaceous rocks. Edible plants growing in the soils contain high Se, Cu and Mo. Two case studies are documented. One is a black shale area with bone coal and Se enrichment, and the other is a black shale area with bone coal mine and cop per mineralization. Eco-geochemical effects of metallic element-rich black shales on plants are reported in this paper.

  10. Cementing Properties of Oil Shale Ash

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The oil crisis has prompted renewed interest in direct burning of oil shale as an alternative energy source.A major problem in this process is the large portion of ash produced.The cementing properties of this ash were investigated to determine its applicability as a building material.By means of XRD, IR, NMR and ICP, we have studied the effects of burning temperature on the reactivity of ash.Maximum reactivity was obtained with ash samples produced at 700 °C to 900 °C.In this range, the strength of oil-shale-based material, with properties similar to cement, which is composed of oil shale and several other kinds of solid wastes, can achieve the standard of 42.5# cement.Our study has provided an experimental foundation and theoretical base for a massive utilization of oil shale.

  11. Helium release during shale deformation: Experimental validation

    Science.gov (United States)

    Bauer, Stephen J.; Gardner, W. Payton; Heath, Jason E.

    2016-07-01

    This work describes initial experimental results of helium tracer release monitoring during deformation of shale. Naturally occurring radiogenic 4He is present in high concentration in most shales. During rock deformation, accumulated helium could be released as fractures are created and new transport pathways are created. We present the results of an experimental study in which confined reservoir shale samples, cored parallel and perpendicular to bedding, which were initially saturated with helium to simulate reservoir conditions, are subjected to triaxial compressive deformation. During the deformation experiment, differential stress, axial, and radial strains are systematically tracked. Release of helium is dynamically measured using a helium mass spectrometer leak detector. Helium released during deformation is observable at the laboratory scale and the release is tightly coupled to the shale deformation. These first measurements of dynamic helium release from rocks undergoing deformation show that helium provides information on the evolution of microstructure as a function of changes in stress and strain.

  12. Thermal analytical investigation of biopolymers and humic- and carbonaceous-based soil and sediment organic matter

    Energy Technology Data Exchange (ETDEWEB)

    Lu Zhang; Eugene J. LeBoeuf; Baoshan Xing [Vanderbilt University, Nashville, TN (United States). Department of Civil and Environmental Engineering

    2007-07-15

    Improved understanding of the physical, chemical, and thermodynamic properties of soil and sediment organic matter (SOM) is crucial in elucidating sorption mechanisms of hydrophobic organic compounds (HOCs) in soils and sediments. In this study, several thermoanalytical techniques, including thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), temperature-modulated differential scanning calorimetry (TMDSC), and thermal mechanical analysis (TMA) were applied to 13 different organic materials (three woods, two humic acids, three kerogens, and five black carbons) representing a spectrum of diagenetic and/or thermal histories. Samples included Pocahontas No. 3 bituminous coal. Second-order thermal transition temperatures (T{sub t}) were identified in most materials, where the highest observed T{sub t} values (typically characterized as glass transition temperatures (T{sub g})) were shown to closely relate to chemical characteristics of the organic samples as influenced by diagenetic or thermal alteration. Results further suggest a positive correlation between glass transition temperature and a defined diagenetic/thermal index, where humic-based SOM (e.g., humic and fulvic acids) possess lower transition temperatures than more 'mature' carbonaceous-based SOM (i.e., kerogens and black carbons). The observed higher thermal transition temperature of aliphatic-rich Green River shale kerogen (about 120{sup o}C) relative to that of aromatic-rich humic acids suggests that a sole correlation of aromaticity to thermal transition temperature may be inappropriate. 55 refs., 2 figs., 1 tab.

  13. CARBONACEOUS MATTER PRECURSORS AND METAMORPHIC CONDITIONS IN THERMALLY PROCESSED CHONDRITES

    Science.gov (United States)

    Quirico, E.; Montagnac, G.; Rouzaud, J.; Bonal, L.; Bourot-Denise, M.; Duber, S.; Reynard, B.

    2009-12-01

    Unravelling the origin of carbonaceous matter in pristine chondrites requires the understanding of the effect of post-accretion processes. In chondrites of petrologic type 3, thermal metamorphism modified to various extents the composition and structure of carbonaceous matter. Interestingly, this process controls the degree of structural order of carbonaceous matter, and clues on the thermal history of the parent body may be recovered from the physico-chemical study of carbonaceous matter. Following this framework, geothermometers based on Raman spectrometry of carbonaceous matter and covering a wide range of temperatures (100-650 °C) have been developed over recent years, both on terrestrial rocks and chondrites. While Raman data have been largely interpreted in terms of temperature, they are also the fingerprint of certain metamorphic conditions, especially in the low temperature range relevant to poorly ordered carbonaceous matter. This study investigates the Raman spectra of two series of chondritic carbonaceous matter and coal samples formed from different precursors and under different metamorphic conditions. The Raman spectra of Polyaromatic Carbonaceous Matter (PCM) from 42 chondrites and 27 coal samples, measured with visible (514 nm) and ultra-violet (244 nm) excitation wavelengths, are analyzed. The Raman spectra of low rank coals and chondrites of petrologic types 1 and 2, which contain the more disordered PCM, reflect the distinct carbon structures of their precursors. The 514 nm Raman spectra of high rank coals and chondrites of petrologic type 3 exhibit continuous and systematic spectral differences reflecting different carbon structures present during the metamorphism event. They result from differences in the chemical structures of the precursors concerning for instance the reticulation of polyaromatic units or an abundance of ether functional groups, or possibly from a lack of carbonization processes to efficiently expel oxygen heteroatoms, due

  14. Physical and Chemical Characterization of Carbonaceous Aerosols in Korea

    Science.gov (United States)

    Choung, S.; Jin, J. S.; Hwang, G. S.; Jang, K. S.; Han, W. S.; OH, J.; Kwon, Y.

    2014-12-01

    Atmospheric aerosols have been recently paid attention more in environmental research due to their negative effects on air quality, public health, and climate change. The aerosols contain approximately >20-50% carbonaceous components such as organic carbon (OC) and black carbon (BC) (or elemental carbon [EC]) derived from organic compounds, biomass burning, and incomplete combustion of fossil fuels. The physical, chemical, and biological properties of atmospheric aerosols are strongly dependent on the carbonaceous components. In particular, the BC could significantly affect the regional air quality in the northeastern Asia, because China is one of the foremost BC emission country in the world. Previous studies have mainly focused on the quantification and source identification for carbonaceous aerosols. However, understanding of physical and chemical properties for the carbonaceous aerosols related to environmental contamination and toxicity was still incomplete due to analytical difficulties. This study is addressed to evaluate the contribution of carbonaceous aerosols to air pollution through the surface, mass spectroscopic, and electron microscopic analyses, and determination of chemical composition and structure using the air particulate matter (PM2.5 and >PM2.5) samples.

  15. Characterization of nitrogen compound types in hydrotreated Paraho shale oil

    Energy Technology Data Exchange (ETDEWEB)

    Holmes, S.A.; Latham, D.R.

    1980-10-01

    Results from the separation and characterization of nitrogen compound types in hydrotreated Paraho shale oil samples were obtained. Two samples of Paraho shale oil were hydrotreated by Chevron Research Company such that one sample contained about 0.05 wt. percent nitrogen and the other sample contained about 0.10 wt. percent nitrogen. A separation method concentrate specific nitrogen compound types was developed. Characterization of the nitrogen types was accomplished by infrared spectroscopy, mass spectrometry, potentiometric titration, and elemental analysis. The distribution of nitrogen compound types in both samples and in the Paraho crude shale oil is compared.

  16. RESEARCH PROGRESS AND SIGNIFICANCE OF THE CAMBRIAN SMALL CARBONACEOUS FOSSILS (SCFs)%寒武系小碳化石(SCFs)的研究进展及意义

    Institute of Scientific and Technical Information of China (English)

    李向峰; 毛颖颜; 林日白

    2013-01-01

    所谓SCFs (Small Carbonaceous Fossils),可译为“小碳化石”,其大小跨越了传统的微观与宏观界线(以肉眼可见与否为标准),是一个特定化石群体的统称.它的实质含义,是指通过氢氟酸(HF)等无机酸浸泡泥岩/页岩样品后经过滤、浓缩而获得的一类体积微小的有机碳质薄膜化石,包括后生动物残片、丝状藻/菌类碎片、疑源类等类型.在小碳化石概念被正式提出之前,国外学者曾先后用有机质壁微体化石(Organic-walled microfossils)、碳质微体化石(Carbonaceous microfossils)与布尔吉斯页岩型微体化石(Burgess Shale-type microfossils)来表述此类化石.目前在国际上,与布尔吉斯页岩型(BST)化石库和奥斯坦(Orsten)型化石库一样,小碳化石已经成为寒武纪古生物学及生物埋藏学等领域研究的一个重要的新窗口;同时,通过三类特异埋藏化石的对比研究,实现优势互补,从而能够更好地阐述早期生物的演化与多样性.%The term "SCFs" stands for Small Carbonaceous Fossils,which defines a special group of fossils,with size ranges across the conventional boundary between microscopic and macroscopic views.SCFs are also known as "organic-walled microfossils","carbonaceous microfossils",and/or "Burgess Shale type microfossils".Due to more findings worldwide SCFs is now becoming a new important window for Cambrian palaeontological and taphonomical studies because it can bridge the preservation gaps between Cambrian Lagerst(a)tten,including Burgess Shale-type (BST)macrofossils and Orsten-type fossils.SCFs were recovered through a series of procedures as followed:macerate each sample of mudstone/shale with hydrofluoric acid (HF) until it disaggregated,dilute the solution to neutrality,filter the sample through a sieve and then concentrate the residues.Concentrated residues can be picked for SCFs,including metazoan fragments,filamental algae/fungi and acritarchs.Furthermore,SCFs combined with

  17. Chattanooga Shale conference

    Energy Technology Data Exchange (ETDEWEB)

    1979-11-01

    Seven papers are included, relating to the exploitation of the uranium contained in shales. One of these papers discusses the IGT Hytort process, and was previously abstracted. Separate abstracts were prepared for the remaining six papers. (DLC)

  18. Power from oil shale

    Energy Technology Data Exchange (ETDEWEB)

    Yerushalmi, J.; Wohlfarth, A.; Schwartz, M.; Luria, S.

    1988-02-01

    The possibilities for burning oil shale directly to generate a substantial fraction of Israel's electric power are to be investigated by means of a demonstration plant. The plant incorporates a fluidized bed reactor in which combustion tests have shown Israeli oil-shale will burn with high carbon utilization and without the need for supplementary fuel. Sulphur dioxide emissions are nearly all absorbed by the limestone that makes up about 50% of the shale. The design is for co-generation, supplying low pressure process steam for a chemical plant and electricity to the grid. Economic evaluation suggests that oil shale power generation in Israel could in the future be at least competitive with coal and under some circumstances have a cost advantage.

  19. Characterization and beneficiation of the Egyptian black shale for possible extraction of organic matter

    Institute of Scientific and Technical Information of China (English)

    Abd El-Rahiem F.H.; Hassan M.S.; Selim K.A.; Abdel-Khalek N.A

    2014-01-01

    The present paper focuses on obtaining concentrate enriched with organic matter that could be suitable for a retorting process from black shale; this is black shale from the Safaga area on the Red Sea Coast. X-ray diffraction and optical polarising microscope are used in evaluating black shale minerals. Attrition scrubbing and flotation were conducted for enrichment of organic matter in the black shale sample. Mineralogical studies revealed that black shale samples contain bituminous calcareous clay stone, quartz, apatite and pyrite. Rabah mine black shale contains 28% organic matter. The results of the different separation techniques indicate that attrition and flotation techniques successively enriched the organic matter in the black shale. The organic matter could be enriched in the black shale and obtained a concen-trate with 59%assaying and 85%recovery.

  20. Petrographical properties of shales from Campos Basin

    Energy Technology Data Exchange (ETDEWEB)

    Rabe, Claudio; Araujo, Ewerton M.P.; Fontoura, Sergio A.B. da [Pontificia Univ. Catolica do Rio de Janeiro, RJ (Brazil). Dept. de Engenharia Civil. Grupo de Tecnologia e Engenharia de Petroleo (GTEP)

    2004-07-01

    This paper presents a petrographical characterization of shales from Albacora, Marlim and Marlim Sul fields (offshore Campos Basin, Brazil). The characterization program included petrography analysis of thin section of undisturbed shale samples, scanning electron microscope (SEM) images and energy dispersive spectrometry (EDS) analysis. The tests were realized with the purpose of obtaining information to observe the nature of the rock microstructure. From the results presented herein, the shales can be described as silty and calciferous. The description of the thin sections indicated that all the shale samples are very similar from the compositional and textural point of view. The samples are rich in clay minerals, that show small size grains and seem homogeneous, and carbonatic cement. The samples are constituted by calcite, quartz, kaolinite, smecite, illite, illite/smectite, kaolinite/illite/smectite, feldspar, plagioclase, dolomite, chlorite and pyrite. The samples showed a great amount of calcium, resultant from the microfossils, that covers partially the clay minerals. Pyrite is also observed as small grains disperse throughout the sample with form of agglomerated pyrite framboids, cubo-octahedral and octahedral crystals. The EDS show the presence of picks of Si, Al, Mg, K and Na particles, indicating the presence of clay minerals, calcite, pyrite and chlorite. (author)

  1. Giant dendritic carbonaceous particles in Soweto aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Wentzel, M.; Annegarn, H.J.; Helas, G.; Weinbruch, S.; Balogh, A.G.; Sithole, J.S. [Max Planck Institute of Chemistry, Mainz (Germany). Biogeochemistry Dept.

    1999-03-01

    Gravimetric analyses of aerosol filter samples from Soweto, southwest of Johannesburg, have revealed an anomalous mass-size distribution. Instead of the coal fire generated aerosol forming sub-micron aerosols as expected, most of the mass of the winter smoke is in particles greater than 3{mu}m aerodynamic diameter. A high-resolution scanning electron microscope was used to examine coarse and fine-mode aerosol fractions from two contrasting sites in the conurbation. Unanticipated giant carbonaceous conglomerates (10-100 {mu}m diameter), which comprise the bulk of the aerosol mass on the filters examined, were found. The outer shape of the conglomerates tends towards spherical, rather than the branched, chain-like structures of high-temperature soot. Internal structure varies from highly dendritic with 20-nm-wide branches, through a coarser sponge-like structure to an almost solid `melted toffee` irregular surface. Possible modes of formation of these conglomerates are discussed in terms of condensation aerosols conglomeration, and subsequent partial melting or solvent condensation. The occurrence of the giant carbonaceous conglomerates as a general feature of the Soweto winter atmosphere explains the anomalous size-mass distribution results from bulk filter analyses.

  2. Multi-wavelength characterization of carbonaceous aerosol

    Science.gov (United States)

    Massabò, Dario; Caponi, Lorenzo; Chiara Bove, Maria; Piazzalunga, Andrea; Valli, Gianluigi; Vecchi, Roberta; Prati, Paolo

    2014-05-01

    Carbonaceous aerosol is a major component of the urban PM. It mainly consists of organic carbon (OC) and elemental carbon (EC) although a minor fraction of carbonate carbon could be also present. Elemental carbon is mainly found in the finer PM fractions (PM2.5 and PM1) and it is strongly light absorbing. When determined by optical methods, it is usually called black carbon (BC). The two quantities, EC and BC, even if both related to the refractory components of carbonaceous aerosols, do not exactly define the same PM component (Bond and Bergstrom, 2006; and references therein). Moreover, another fraction of light-absorbing carbon exists which is not black and it is generally called brown carbon (Andreae and Gelencsér, 2006). We introduce a simple, fully automatic, multi-wavelength and non-destructive optical system, actually a Multi-Wavelength Absorbance Analyzer, MWAA, to measure off-line the light absorption in Particulate Matter (PM) collected on filters and hence to derive the black and brown carbon content in the PM This gives the opportunity to measure in the same sample the concentration of total PM by gravimetric analysis, black and brown carbon, metals by, for instance, X Ray Fluorescence, and finally ions by Ion Chromatography. Up to 16 samples can be analyzed in sequence and in an automatic and controlled way within a few hours. The filter absorbance measured by MWAA was successfully validated both against a MAAP, Multi Angle Absorption Photometer (Petzold and Schönlinner, 2004), and the polar photometer of the University of Milan. The measurement of sample absorbance at three wavelengths gives the possibility to apportion different sources of carbonaceous PM, for instance fossil fuels and wood combustion. This can be done following the so called "aethalometer method" (Sandradewi et al., 2008;) but with some significant upgrades that will be discussed together the results of field campaigns in rural and urban sites. Andreae, M.O, and Gelencsér, A

  3. Multivariate analysis relating oil shale geochemical properties to NMR relaxometry

    Science.gov (United States)

    Birdwell, Justin E.; Washburn, Kathryn E.

    2015-01-01

    Low-field nuclear magnetic resonance (NMR) relaxometry has been used to provide insight into shale composition by separating relaxation responses from the various hydrogen-bearing phases present in shales in a noninvasive way. Previous low-field NMR work using solid-echo methods provided qualitative information on organic constituents associated with raw and pyrolyzed oil shale samples, but uncertainty in the interpretation of longitudinal-transverse (T1–T2) relaxometry correlation results indicated further study was required. Qualitative confirmation of peaks attributed to kerogen in oil shale was achieved by comparing T1–T2 correlation measurements made on oil shale samples to measurements made on kerogen isolated from those shales. Quantitative relationships between T1–T2 correlation data and organic geochemical properties of raw and pyrolyzed oil shales were determined using partial least-squares regression (PLSR). Relaxometry results were also compared to infrared spectra, and the results not only provided further confidence in the organic matter peak interpretations but also confirmed attribution of T1–T2 peaks to clay hydroxyls. In addition, PLSR analysis was applied to correlate relaxometry data to trace element concentrations with good success. The results of this work show that NMR relaxometry measurements using the solid-echo approach produce T1–T2 peak distributions that correlate well with geochemical properties of raw and pyrolyzed oil shales.

  4. Carbonaceous Matter in Growing Nanoparticles

    Science.gov (United States)

    Johnston, M. V.; Stangl, C. M.; Horan, A. J.

    2015-12-01

    Atmospheric nanoparticles constitute the greatest portion of ambient aerosol loading by number. A major source of atmospheric nanoparticles is new particle formation (NPF), a gas to particle conversion process whereby clusters nucleate from gas phase precursors to form clusters on the order of one or a few nanometers and then grow rapidly to climatically relevant sizes. A substantial fraction of cloud condensation nuclei (CCN) are thought to arise from NPF. In order to better predict the frequency, growth rates, and climatic impacts of NPF, knowledge of the chemical mechanisms by which nucleated nanoparticles grow is needed. The two main contributors to particle growth are (neutralized) sulfate and carbonaceous matter. Particle growth by sulfuric acid condensation is generally well understood, though uncertainty remains about the extent of base neutralization and the relative roles of ammonia and amines. Much less is known about carbonaceous matter, and field measurements suggest that nitrogen-containing species are important. In this presentation, recent work by our group will be described that uses a combination of ambient measurements, laboratory experiments and computational work to study carbonaceous matter in growing nanoparticles. These studies span a range of particle sizes from the initial adsorption of molecules onto a nanometer-size ammonium bisulfate seed cluster to reactions in particles that are large enough to support condensed-phase chemistry.

  5. Methods of ultimate carbonaceous BOD determination

    Science.gov (United States)

    Stamer, J.K.; McKenzie, S.W.; Cherry, R.N.

    1979-01-01

    Studies were conducted to provide an accurate and practical technique for determining the concentration of ultimate carbonaceous biochemical oxygen demand and the rate at which this demand is exerted. The three methods evaluated were carbon derived, nitrification adjusted, and nitrification inhibited. The studies indicate that comparable concentrations and reaction rates can be determined from either non-nitrified samples using no chemical nitrifying inhibitor, or from partially nitrified samples using the chemical inhibitors, 1-allyl-2 thiourea or nitrapyrin, and that the combined use of time-series analysis and Lee's graphical method provide a reliable and accurate technique for determining ultimate biochemical oxygen demand concentration and reaction rate in 5 to 7 days.

  6. Trace elements in oil shale. Progress report, 1979-1980

    Energy Technology Data Exchange (ETDEWEB)

    Chappell, W R

    1980-01-01

    The purpose of this research program is to understand the potential impact of an oil shale industry on environmental levels of trace contaminants in the region. The program involves a comprehensive study of the sources, release mechanisms, transport, fate, and effects of toxic trace chemicals, principally the trace elements, in an oil shale industry. The overall objective of the program is to evaluate the environmental and health consequences of the release of toxic trace elements by shale and oil production and use. The baseline geochemical survey shows that stable trace elements maps can be constructed for numerous elements and that the trends observed are related to geologic and climatic factors. Shale retorted by above-ground processes tends to be very homogeneous (both in space and in time) in trace element content. Leachate studies show that significant amounts of B, F, and Mo are released from retorted shales and while B and Mo are rapidly flushed out, F is not. On the other hand, As, Se, and most other trace elements are not present in significant quantities. Significant amounts of F and B are also found in leachates of raw shales. Very large concentrations of reduced sulfur species are found in leachates of processed shale. Very high levels of B and Mo are taken up in some plants growing on processed shale with and without soil cover. There is a tendency for some trace elements to associate with specific organic fractions, indicating that organic chelation or complexation may play an important role. Many of the so-called standard methods for analyzing trace elements in oil shale-related materials are inadequate. A sampling manual is being written for the environmental scientist and practicing engineer. A new combination of methods is developed for separating the minerals in oil shale into different density fractions. Microbial investigations have tentatively identified the existence of thiobacilli in oil shale materials such as leachates. (DC)

  7. Local CO2-induced swelling of shales

    Science.gov (United States)

    Pluymakers, Anne; Dysthe, Dag Kristian

    2017-04-01

    In heterogeneous shale rocks, CO2 adsorbs more strongly to organic matter than to the other components. CO2-induced swelling of organic matter has been shown in coal, which is pure carbon. The heterogeneity of the shale matrix makes an interesting case study. Can local swelling through adsorption of CO2 to organic matter induce strain in the surrounding shale matrix? Can fractures close due to CO2-induced swelling of clays and organic matter? We have developed a new generation of microfluidic high pressure cells (up to 100 bar), which can be used to study flow and adsorption phenomena at the microscale in natural geo-materials. The devices contain one transparent side and a shale sample on the other side. The shale used is the Pomeranian shale, extracted from 4 km depth in Poland. This formation is a potential target of a combined CO2-storage and gas extraction project. To answer the first question, we place the pressure cell under a Veeco NT1100 Interferometer, operated in Vertical Scanning Interferometry mode and equipped with a Through Transmissive Media objective. This allows for observation of local swelling or organic matter with nanometer vertical resolution and micrometer lateral resolution. We expose the sample to CO2 atmospheres at different pressures. Comparison of the interferometry data and using SEM-EDS maps plus optical microscopy delivers local swelling maps where we can distinguish swelling of different mineralogies. Preliminary results indicate minor local swelling of organic matter, where the total amount is both time- and pressure-dependent.

  8. A new Burgess Shale-type deposit from the Ediacaran of western Mongolia

    OpenAIRE

    Dornbos, Stephen Q.; Tatsuo Oji; Akihiro Kanayama; Sersmaa Gonchigdorj

    2016-01-01

    Preservation of soft-bodied organisms is exceedingly rare in the fossil record. One way that such fossils are preserved is as carbonaceous compressions in fined-grained marine sedimentary rocks. These deposits of exceptional preservation are known as Burgess Shale-type (BST) deposits. During the Cambrian Period, BST deposits are more common and provide a crucial view of early animal evolution. The earliest definitive fossil evidence for macroscopic animal-grade organisms is found in the prece...

  9. Fullerenes in asphaltenes and other carbonaceous materials: natural constituents or laser artifacts.

    Science.gov (United States)

    Santos, Vanessa G; Fasciotti, Maíra; Pudenzi, Marcos A; Klitzke, Clécio F; Nascimento, Heliara L; Pereira, Rosana C L; Bastos, Wagner L; Eberlin, Marcos N

    2016-04-25

    The presence of fullerenes as natural constituents of carbonaceous materials or their formation as laser artifacts during laser desorption ionization (LDI) mass spectrometry (MS) analysis is reinvestigated and reviewed. The results using asphaltene samples with varying composition as well as standard polycyclic aromatic hydrocarbons (PAH) and fullerene samples as models have demonstrated that indeed Cn ring fullerenes are not natural constituents but they are formed as common and often as predominant artifacts upon laser radiation, and a series of incorrect assignments based on LDI-MS data of several carbonaceous materials seems unfortunately to have been made. When the present results are evaluated also in the light of the vast literature on LDI-MS of carbonaceous materials, the formation of fullerene artifacts seems particularly common for LDI-MS analysis of asphaltenes and other carbonaceous samples with considerably high levels of PAH and varies according to the type of laser used, and the intensity of the laser beam.

  10. Organic analysis of the Antarctic carbonaceous chondrites

    Science.gov (United States)

    Kotra, R. K.; Shimoyama, A.; Ponnamperuma, C.; Hare, P. E.; Yanai, K.

    1981-01-01

    Thus far, organic analysis of carbonaceous chondrites has proven the only fruitful means of examining complex organic matter of extraterrestrial origin. The present paper presents the results of organic analysis of two Antarctic meteorites, Allan Hills (77306) and Yamato (74662), which may be considered free from terrestrial contamination. Ion-exchange chromatography, gas chromatography and mass spectrometery of meteorite samples reveal the presence in Yamato of 15 and in Allan Hills of 20 protein and nonprotein amino acids, the most abundant of which are glycine and alanine. Abundances of the D and L enantiomers of each amino acid are also found to be nearly equal. Data thus indicate an abiotic extraterrestrial origin for the matter, and confirm a lack of terrestrial contamination.

  11. Contribution to the study of shale stability while drilling

    Energy Technology Data Exchange (ETDEWEB)

    Azzouz, S.R.

    1983-11-01

    Shale drilling requires the development of drilling muds preventing shale hydration. Laboratory tests on excavation parameters such as capillary adsorption, swelling and swelling pressure show that some protective agents can limit hydratation and rock desintegration. Inhibiting power of these products is determined by an apparatus designed to study the dynamic action of a fluid on a core. Erosion kinetics of a sample placed in a fluid flow is followed by a photoelectric cell. This test shows that potassium carbonate and polyacrylamide are particularly adapted for shale stabilization.

  12. Carbonaceous species in atmospheric aerosols from the Krakow area (Malopolska District: carbonaceous species dry deposition analysis

    Directory of Open Access Journals (Sweden)

    Szramowiat Katarzyna

    2016-01-01

    Full Text Available Organic and elemental carbon content in PM10 was studied at three sites in Malopolska District representing the city centre (Krakow, rural/residential (Bialka and residential/industrial environments (Krakow. The PM10 samples were collected during the winter time study. The highest concentrations of carbonaceous species were observed in Skawina (36.9 μg·m-3 of OC and 9.6 μg·m-3 of EC. The lowest OC and EC concentrations were reported in Krakow (15.2 μg·m-3 and 3.9 μg·m-3, respectively. The highest concentration of carbonaceous species and the highest wind velocities in Skawina influenced the highest values of the dry deposition fluxes. Correlations between OC, EC and chemical constituents and meteorological parameters suggest that a Krakow was influenced by local emission sources and temperature inversion occurrence; b Bialka was under the influence of local emission sources and long-range transport of particles; c Skawina was impacted by local emission sources.

  13. Combustion characteristics of Daqing oil shale and oil shale semi-cokes

    Institute of Scientific and Technical Information of China (English)

    MIAO Zhen-yong; WU Guo-guang; LI Ping; ZHAO Na; WANG Pan-cheng; MENG Xian-liang

    2009-01-01

    Thermo-gravimetric-analysis (TGA) was used to analyze the combustion characteristics of an oil shale and semi-cokes prepared from it. The effect of prior pyrolysis and TGA heating rate on the combustion process was studied. Prior pyrolysis affects the initial temperature of mass loss and the ignition temperature. The ignition temperature increases as the volatile content of the sample decreases. TG/DTG curves obtained at different heating rates show that heating rate has little effect on ignition temperature. But the peak of combustion shifts to higher temperatures as the heating rate is increased. The Coats-Redfern integration method was employed to find the combustion-reaction kinetic parameters for the burning of oil shale and oil shale semi-coke.

  14. Carbonaceous aerosols in Norwegian urban areas

    Directory of Open Access Journals (Sweden)

    K. E. Yttri

    2009-03-01

    Full Text Available Little is known regarding levels and source strength of carbonaceous aerosols in Scandinavia. In the present study, ambient aerosol (PM10 and PM2.5 concentrations of elemental carbon (EC, organic carbon (OC, water-insoluble organic carbon (WINSOC, and water-soluble organic carbon (WSOC are reported for a curbside site, an urban background site, and a suburban site in Norway in order to investigate their spatial and seasonal variations. Aerosol filter samples were collected using tandem filter sampling to correct for the positive sampling artefact introduced by volatile and semivolatile OC. Analyses were performed using the thermal optical transmission (TOT instrument from Sunset Lab Inc., which corrects for charring during analysis. Finally, we estimated the relative contribution of OC from wood burning based on the samples content of levoglucosan.

    Levels of EC varied by more than one order of magnitude between sites, likely due to the higher impact of vehicular traffic at the curbside and the urban background sites. In winter, the level of particulate organic carbon (OCp at the suburban site was equal to (for PM10 or even higher (for PM2.5 than the levels observed at the curbside and the urban background sites. This finding was attributed to the impact of residential wood burning at the suburban site in winter, which was confirmed by a high mean concentration of levoglucosan (407 ng m−3. This finding indicates that exposure to primary combustion derived OCp could be equally high in residential areas as in a city center. It is demonstrated that OCp from wood burning (OCwood accounted for almost all OCp at the suburban site in winter, allowing a new estimate of the ratio TCp/levoglucosan for both PM10 and PM2.5. Particulate carbonaceous material (PCM

  15. Organic compounds in carbonaceous meteorites.

    Science.gov (United States)

    Sephton, Mark A

    2002-06-01

    The carbonaceous chondrite meteorites are fragments of asteroids that have remained relatively unprocessed since the formation of the solar system 4.6 billion years ago. These carbon-rich objects contain a variety of extraterrestrial organic molecules that constitute a record of chemical evolution prior to the origin of life. Compound classes include aliphatic hydrocarbons, aromatic hydrocarbons, amino acids, carboxylic acids, sulfonic acids, phosphonic acids, alcohols, aldehydes, ketones, sugars, amines, amides, nitrogen heterocycles, sulfur heterocycles and a relatively abundant high molecular weight macromolecular material. Structural and stable isotopic characteristics suggest that a number of environments may have contributed to the organic inventory, including interstellar space, the solar nebula and the asteroidal meteorite parent body. This review covers work published between 1950 and the present day and cites 193 references.

  16. Shale oil potential and thermal maturity of the Lower Toarcian Posidonia Shale in NW Europe

    NARCIS (Netherlands)

    Song, J.; Littke, R.; Weniger, P.; Ostertag-Henning, C.; Nelskamp, S.

    2015-01-01

    A suite of drilling cores and outcrop samples of the Lower Toarcian Posidonia Shale (PS) were collected from multiple locations including the Swabian Alb and Franconian Alb of Southwest-Germany, Runswick Bay of UK and Loon op Zand well (LOZ-1) of the West Netherlands Basin. In order to assess the th

  17. Fracturing and brittleness index analyses of shales

    Science.gov (United States)

    Barnhoorn, Auke; Primarini, Mutia; Houben, Maartje

    2016-04-01

    The formation of a fracture network in rocks has a crucial control on the flow behaviour of fluids. In addition, an existing network of fractures , influences the propagation of new fractures during e.g. hydraulic fracturing or during a seismic event. Understanding of the type and characteristics of the fracture network that will be formed during e.g. hydraulic fracturing is thus crucial to better predict the outcome of a hydraulic fracturing job. For this, knowledge of the rock properties is crucial. The brittleness index is often used as a rock property that can be used to predict the fracturing behaviour of a rock for e.g. hydraulic fracturing of shales. Various terminologies of the brittleness index (BI1, BI2 and BI3) exist based on mineralogy, elastic constants and stress-strain behaviour (Jin et al., 2014, Jarvie et al., 2007 and Holt et al., 2011). A maximum brittleness index of 1 predicts very good and efficient fracturing behaviour while a minimum brittleness index of 0 predicts a much more ductile shale behaviour. Here, we have performed systematic petrophysical, acoustic and geomechanical analyses on a set of shale samples from Whitby (UK) and we have determined the three different brittleness indices on each sample by performing all the analyses on each of the samples. We show that each of the three brittleness indices are very different for the same sample and as such it can be concluded that the brittleness index is not a good predictor of the fracturing behaviour of shales. The brittleness index based on the acoustic data (BI1) all lie around values of 0.5, while the brittleness index based on the stress strain data (BI2) give an average brittleness index around 0.75, whereas the mineralogy brittleness index (BI3) predict values below 0.2. This shows that by using different estimates of the brittleness index different decisions can be made for hydraulic fracturing. If we would rely on the mineralogy (BI3), the Whitby mudstone is not a suitable

  18. Micro mechanical study of shales

    Science.gov (United States)

    Bonnelye, Audrey; Picard, David; Gharbi, Hakim; Dimanov, Alexandre; Bornert, Michel; Conil, Nathalie

    2017-04-01

    In the following years, the French nuclear wastes will be buried in the underground repository in shales, that will be excavated at 490 m in depth, within the Callovo Oxfordian (Cox) argillaceous formation. The hydro-mechanical behavior of the argillaceous rock is complex, like the multiphase and multi-scale structured material itself. The argilaceous matrix is composed of interstratified Illite-Smectite particles, it contains detritic quartz and calcite, accessory pyrite, and the rock porosity ranges from micrometre to nanometre scales. Besides the bedding anisotropy, structural variabilities exist at all scales, from the decametric-metric scales of the geological formation to the respectively millimetric and micrometric scales of the aggregates of particles and clay particles Our study aims at understanding the complex mechanisms which are activated at the micro-scale and are involved in the macroscopic inelastic deformation of such a complex material.An experimental protocol was developed in order to perform uniaxial deformation experiment at controlled displacement rate, inside an environmental scanning electron microscope (ESEM), under controlled relative humidity, in order to preserve as much as possible the natural state of saturation of shales. Three sample orientations (90°, 45° and 0°) were used in order to characterize the mechanical anisotropy and the mechanisms involved in the deformation. The observed smple surfaces were polished by broad ion beam in order to reveal the fine microstructures of the argillaceous matrix. Digital images were acquired at different loading stages during the deformation process and Digital Image Correlation Technique (DIC) was applied in order to retrieve full strain fields at various scales from sample scale to microstructure scale. The analysis allows for identification of the active mechanisms, their relationships to the microstructure and their interactions.

  19. Alteration of Mancos Shale by synthetic hydrofracturing fluid

    Science.gov (United States)

    Kruichak, J. N.; Ilgen, A.; Wang, Y.; Griego, J.; Rodriguez, M.

    2015-12-01

    Shale gas produced through hydrofracturing has changed the energy perspective in the United States. Shale gas extraction is complicated by the fast decline in wellbore production, to mitigate which re-stimulation and drilling new wells are required. Our goal is to conduct laboratory experiments that examine methane transport from low-permeability matrices to fracture networks induced by hydraulic fracturing. In particular, we address whether mineralogical alteration of shale by hydrofracturing fluids has an effect on matrix-to-fracture methane transport. We performed a set of laboratory experiments addressing the alteration of Mancos shale by synthetic hydrofracturing fluid at hydrothermal conditions (90 °C). Both powdered shale and shale chips were investigated. Solid characterization was done using bulk and micro-X-ray diffraction (XRD, μXRD), and micro-X-ray Fluorescence mapping (µXRF). Analysis of the aqueous samples was done using ion chromatography (IC) for major anions and cations and inductively coupled plasma mass spectrometry (ICP-MS) - for trace metals. Our results indicate that calcium, barium, strontium , magnesium, manganese, silica, sodium, chloride and sulfate were released from Mancos shale after reaction with hydrofracturing fluid. Altered zones on shale surface after 2 months of reaction are thin - likely, within a few microns. The XRD patterns normalized to the 100% peak for quartz indicate that the dolomite, calcite, biotite, and kaolinite peaks decrease in intensity relative to the quartz peaks with increased alteration time, indicative of the partial dissolution of these minerals. Understanding mineralogical composition of an altered layer of Mancos shale will provide insight whether methane transport through these zones will be affected compared to the unaltered material. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the

  20. Shale Gas Geomechanics for Development and Performance of Unconventional Reservoirs

    Science.gov (United States)

    Domonik, Andrzej; Łukaszewski, Paweł; Wilczyński, Przemysław; Dziedzic, Artur; Łukasiak, Dominik; Bobrowska, Alicja

    2017-04-01

    Mechanical properties of individual shale formations are predominantly determined by their lithology, which reflects sedimentary facies distribution, and subsequent diagenetic and tectonic alterations. Shale rocks may exhibit complex elasto-viscoplastic deformation mechanisms depending on the rate of deformation and the amount of clay minerals, also bearing implications for subcritical crack growth and heterogeneous fracture network development. Thus, geomechanics for unconventional resources differs from conventional reservoirs due to inelastic matrix behavior, stress sensitivity, rock anisotropy and low matrix permeability. Effective horizontal drilling and hydraulic fracturing technologies are required to obtain and maintain high performance. Success of these techniques strongly depends on the geomechanical investigations of shales. An inelastic behavior of shales draws increasing attention of investigators [1], due to its role in stress relaxation between fracturing phases. A strong mechanical anisotropy in the vertical plane and a lower and more variable one in the horizontal plane are characteristic for shale rocks. The horizontal anisotropy plays an important role in determining the direction and effectiveness of propagation of technological hydraulic fractures. Non-standard rock mechanics laboratory experiments are being applied in order to obtain the mechanical properties of shales that have not been previously studied in Poland. Novel laboratory investigations were carried out to assess the creep parameters and to determine time-dependent viscoplastic deformation of shale samples, which can provide a limiting factor to tectonic stresses and control stress change caused by hydraulic fracturing. The study was supported by grant no.: 13-03-00-501-90-472946 "An integrated geomechanical investigation to enhance gas extraction from the Pomeranian shale formations", funded by the National Centre for Research and Development (NCBiR). References: Ch. Chang M. D

  1. Validation Results for Core-Scale Oil Shale Pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Staten, Josh; Tiwari, Pankaj

    2015-03-01

    This report summarizes a study of oil shale pyrolysis at various scales and the subsequent development a model for in situ production of oil from oil shale. Oil shale from the Mahogany zone of the Green River formation was used in all experiments. Pyrolysis experiments were conducted at four scales, powdered samples (100 mesh) and core samples of 0.75”, 1” and 2.5” diameters. The batch, semibatch and continuous flow pyrolysis experiments were designed to study the effect of temperature (300°C to 500°C), heating rate (1°C/min to 10°C/min), pressure (ambient and 500 psig) and size of the sample on product formation. Comprehensive analyses were performed on reactants and products - liquid, gas and spent shale. These experimental studies were designed to understand the relevant coupled phenomena (reaction kinetics, heat transfer, mass transfer, thermodynamics) at multiple scales. A model for oil shale pyrolysis was developed in the COMSOL multiphysics platform. A general kinetic model was integrated with important physical and chemical phenomena that occur during pyrolysis. The secondary reactions of coking and cracking in the product phase were addressed. The multiscale experimental data generated and the models developed provide an understanding of the simultaneous effects of chemical kinetics, and heat and mass transfer on oil quality and yield. The comprehensive data collected in this study will help advance the move to large-scale in situ oil production from the pyrolysis of oil shale.

  2. Pulsed-Laser Irradiation Space Weathering Of A Carbonaceous Chondrite

    Science.gov (United States)

    Thompson, M. S.; Keller, L. P.; Christoffersen, R.; Loeffler, M. J.; Morris, R. V.; Graff, T. G.; Rahman, Z.

    2017-01-01

    Grains on the surfaces of airless bodies experience irradiation from solar energetic particles and melting, vaporization and recondensation processes associated with micrometeorite impacts. Collectively, these processes are known as space weathering and they affect the spectral properties, composition, and microstructure of material on the surfaces of airless bodies, e.g. Recent efforts have focused on space weathering of carbonaceous materials which will be critical for interpreting results from the OSIRIS-REx and Hayabusa2 missions targeting primitive, organic-rich asteroids. In addition to returned sample analyses, space weathering processes are quantified through laboratory experiments. For example, the short-duration thermal pulse from hypervelocity micrometeorite impacts have been simulated using pulsed-laser irradiation of target material e.g. Recent work however, has shown that pulsed-laser irradiation has variable effects on the spectral properties and microstructure of carbonaceous chondrite samples. Here we investigate the spectral characteristics of pulsed-laser irradiated CM2 carbonaceous chondrite, Murchison, including the vaporized component. We also report the chemical and structural characteristics of specific mineral phases within the meteorite as a result of pulsed-laser irradiation.

  3. Shale gas characteristics of the Lower Toarcian Posidonia Shale in Germany: from basin to nanometre scale

    Science.gov (United States)

    Schulz, Hans-Martin; Bernard, Sylvain; Horsfield, Brian; Krüger, Martin; Littke, Ralf; di primio, Rolando

    2013-04-01

    The Early Toarcian Posidonia Shale is a proven hydrocarbon source rock which was deposited in a shallow epicontinental basin. In southern Germany, Tethyan warm-water influences from the south led to carbonate sedimentation, whereas cold-water influxes from the north controlled siliciclastic sedimentation in the northwestern parts of Germany and the Netherlands. Restricted sea-floor circulation and organic matter preservation are considered to be the consequence of an oceanic anoxic event. In contrast, non-marine conditions led to sedimentation of coarser grained sediments under progressively terrestrial conditions in northeastern Germany The present-day distribution of Posidonia Shale in northern Germany is restricted to the centres of rift basins that formed in the Late Jurassic (e.g., Lower Saxony Basin and Dogger Troughs like the West and East Holstein Troughs) as a result of erosion on the basin margins and bounding highs. The source rock characteristics are in part dependent on grain size as the Posidonia Shale in eastern Germany is referred to as a mixed to non-source rock facies. In the study area, the TOC content and the organic matter quality vary vertically and laterally, likely as a consequence of a rising sea level during the Toarcian. Here we present and compare data of whole Posidonia Shale sections, investigating these variations and highlighting the variability of Posidonia Shale depositional system. During all phases of burial, gas was generated in the Posidonia Shale. Low sedimentation rates led to diffusion of early diagenetically formed biogenic methane. Isochronously formed diagenetic carbonates tightened the matrix and increased brittleness. Thermogenic gas generation occurred in wide areas of Lower Saxony as well as in Schleswig Holstein. Biogenic methane gas can still be formed today in Posidonia Shale at shallow depth in areas which were covered by Pleistocene glaciers. Submicrometric interparticle pores predominate in immature samples. At

  4. What controls the strength and brittleness of shale rocks?

    Science.gov (United States)

    Rybacki, Erik; Reinicke, Andreas; Meier, Tobias; Makasi, Masline; Dresen, Georg

    2014-05-01

    With respect to the productivity of gas shales, in petroleum science the mechanical behavior of shales is often classified into rock types of high and low 'brittleness', sometimes also referred to as 'fraccability'. The term brittleness is not well defined and different definitions exist, associated with elastic properties (Poisson's ratio, Young's modulus), with strength parameters (compressive and tensile strength), frictional properties (cohesion, friction coefficient), hardness (indentation), or with the strain or energy budget (ratio of reversible to the total strain or energy, respectively). Shales containing a high amount of clay and organic matter are usually considered as less brittle. Similarly, the strength of shales is usually assumed to be low if they contain a high fraction of weak phases. We performed mechanical tests on a series of shales with different mineralogical compositions, varying porosity, and low to high maturity. Using cylindrical samples, we determined the uniaxial and triaxial compressive strength, static Young's modulus, the tensile strength, and Mode I fracture toughness. The results show that in general the uniaxial compressive strength (UCS) linearly increases with increasing Young's modulus (E) and both parameters increase with decreasing porosity. However, the strength and elastic modulus is not uniquely correlated with the mineral content. For shales with a relatively low quartz and high carbonate content, UCS and E increase with increasing quartz content, whereas for shales with a relatively low amount for carbonates, but high quartz content, both parameters increase with decreasing fraction of the weak phases (clays, kerogen). In contrast, the average tensile strength of all shale-types appears to increase with increasing quartz fraction. The internal friction coefficient of all investigated shales decreases with increasing pressure and may approach rather high values (up to ≡ 1). Therefore, the mechanical strength and

  5. Preliminary study on collectorless flotation of chalcocite, bornite and copper-bearing shale in the presence of selected frothers

    Directory of Open Access Journals (Sweden)

    Drzymala Jan

    2016-01-01

    Full Text Available Flotation of carbonaceous copper-bearing shale and copper sulfide minerals such as chalcocite and bornite in the presence of only frother was investigated. It was determined that all investigated solids did not float in pure water in the absence of flotation reagents. However, an addition of a frother rendered both shale and bornite floatable, while the recovery of chalcocite was negligible. These findings suggest that removal of carbonaceous matter from the ore by the so-called pre-flotation process can be a suitable procedure to reduce the amount of organic carbon in the concentrates provided that the feed does not contain bornite. Otherwise, simple pre-flotation must be replaced with a more sophisticated process in which flotation of bornite is suppressed.

  6. Petrology of the Devonian gas-bearing shale along Lake Erie helps explain gas shows

    Energy Technology Data Exchange (ETDEWEB)

    Broadhead, R.F.; Potter, P.E.

    1980-11-01

    Comprehensive petrologic study of 136 thin sections of the Ohio Shale along Lake Erie, when combined with detailed stratigraphic study, helps explain the occurrence of its gas shows, most of which occur in the silty, greenish-gray, organic poor Chagrin Shale and Three Lick Bed. Both have thicker siltstone laminae and more siltstone beds than other members of the Ohio Shale and both units also contain more clayshales. The source of the gas in the Chagrin Shale and Three Lick Bed of the Ohio Shale is believed to be the bituminous-rich shales of the middle and lower parts of the underlying Huron Member of the Ohio Shale. Eleven petrographic types were recognized and extended descriptions are provided of the major ones - claystones, clayshales, mudshales, and bituminous shales plus laminated and unlaminated siltstones and very minor marlstones and sandstones. In addition three major types of lamination were identified and studied. Thirty-two shale samples were analyzed for organic carbon, whole rock hydrogen and whole rock nitrogen with a Perkin-Elmer 240 Elemental Analyzer and provided the data base for source rock evaluation of the Ohio Shale.

  7. Combined In Situ Micro X-Ray Diffraction and Raman Study of Carbonaceous Matter in Ureilites and Terrestrial Materials

    Science.gov (United States)

    Izawa, M. R. M.; Wright, A. J.; McCausland, P. J. A.; Flemming, R. L.; Muirhead, D. K.; Parnell, J.

    2008-03-01

    In situ ?XRD and Raman microspectroscopy have been applied to carbonaceous material in two ureilite and four terrestrial samples. This reconnaissance provides context and impetus for other, more invasive analytical techniques.

  8. Fire and explosion hazards of oil shale

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

    The US Bureau of Mines publication presents the results of investigations into the fire and explosion hazards of oil shale rocks and dust. Three areas have been examined: the explosibility and ignitability of oil shale dust clouds, the fire hazards of oil shale dust layers on hot surfaces, and the ignitability and extinguishment of oil shale rubble piles. 10 refs., 54 figs., 29 tabs.

  9. Fire and explosion hazards of oil shale

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

    The US Bureau of Mines publication presents the results of investigations into the fire and explosion hazards of oil shale rocks and dust. Three areas have been examined: the explosibility and ignitability of oil shale dust clouds, the fire hazards of oil shale dust layers on hot surfaces, and the ignitability and extinguishment of oil shale rubble piles. 10 refs., 54 figs., 29 tabs.

  10. Cyclone oil shale retorting concept. [Use it all retorting process

    Energy Technology Data Exchange (ETDEWEB)

    Harak, A.E.; Little, W.E.; Faulders, C.R.

    1984-04-01

    A new concept for above-ground retorting of oil shale was disclosed by A.E. Harak in US Patent No. 4,340,463, dated July 20, 1982, and assigned to the US Department of Energy. This patent titled System for Utilizing Oil Shale Fines, describes a process wherein oil shale fines of one-half inch diameter and less are pyrolyzed in an entrained-flow reactor using hot gas from a cyclone combustor. Spent shale and supplemental fuel are burned at slagging conditions in this combustor. Because of fines utilization, the designation Use It All Retorting Process (UIARP) has been adopted. A preliminary process engineering design of the UIARP, analytical tests on six samples of raw oil shale, and a preliminary technical and economic evaluation of the process were performed. The results of these investigations are summarized in this report. The patent description is included. It was concluded that such changes as deleting air preheating in the slag quench and replacing the condenser with a quench-oil scrubber are recognized as being essential. The addition of an entrained flow raw shale preheater ahead of the cyclone retort is probably required, but final acceptance is felt to be contingent on some verification that adequate reaction time cannot be obtained with only the cyclone, or possibly some other twin-cyclone configuration. Sufficient raw shale preheating could probably be done more simply in another manner, perhaps in a screw conveyor shale transporting system. Results of the technical and economic evaluations of Jacobs Engineering indicate that further investigation of the UIARP is definitely worthwhile. The projected capital and operating costs are competitive with costs of other processes as long as electric power generation and sales are part of the processing facility.

  11. Mechanical Properties of Gas Shale During Drilling Operations

    Science.gov (United States)

    Yan, Chuanliang; Deng, Jingen; Cheng, Yuanfang; Li, Menglai; Feng, Yongcun; Li, Xiaorong

    2017-07-01

    The mechanical properties of gas shale significantly affect the designs of drilling, completion, and hydraulic fracturing treatments. In this paper, the microstructure characteristics of gas shale from southern China containing up to 45.1% clay were analyzed using a scanning electron microscope. The gas shale samples feature strongly anisotropic characteristics and well-developed bedding planes. Their strength is controlled by the strength of both the matrix and the bedding planes. Conventional triaxial tests and direct shear tests are further used to study the chemical effects of drilling fluids on the strength of shale matrix and bedding planes, respectively. The results show that the drilling fluid has a much larger impact on the strength of the bedding plane than that of the shale matrix. The impact of water-based mud (WBM) is much larger compared with oil-based mud. Furthermore, the borehole collapse pressure of shale gas wells considering the effects of drilling fluids are analyzed. The results show that the collapse pressure increases gradually with the increase of drilling time, especially for WBM.

  12. Experimental investigations of the wettability of clays and shales

    Science.gov (United States)

    Borysenko, Artem; Clennell, Ben; Sedev, Rossen; Burgar, Iko; Ralston, John; Raven, Mark; Dewhurst, David; Liu, Keyu

    2009-07-01

    Wettability in argillaceous materials is poorly understood, yet it is critical to hydrocarbon recovery in clay-rich reservoirs and capillary seal capacity in both caprocks and fault gouges. The hydrophobic or hydrophilic nature of clay-bearing soils and sediments also controls to a large degree the movement of spilled nonaqueous phase liquids in the subsurface and the options available for remediation of these pollutants. In this paper the wettability of hydrocarbons contacting shales in their natural state and the tendencies for wettability alteration were examined. Water-wet, oil-wet, and mixed-wet shales from wells in Australia were investigated and were compared with simplified model shales (single and mixed minerals) artificially treated in crude oil. The intact natural shale samples (preserved with their original water content) were characterized petrophysically by dielectric spectroscopy and nuclear magnetic resonance, plus scanning electron, optical and fluorescence microscopy. Wettability alteration was studied using spontaneous imbibition, pigment extraction, and the sessile drop method for contact angle measurement. The mineralogy and chemical compositions of the shales were determined by standard methods. By studying pure minerals and natural shales in parallel, a correlation between the petrophysical properties, and wetting behavior was observed. These correlations may potentially be used to assess wettability in downhole measurements.

  13. CO2 mineral sequestration in oil-shale wastes from Estonian power production.

    Science.gov (United States)

    Uibu, Mai; Uus, Mati; Kuusik, Rein

    2009-02-01

    In the Republic of Estonia, local low-grade carbonaceous fossil fuel--Estonian oil-shale--is used as a primary energy source. Combustion of oil-shale is characterized by a high specific carbon emission factor (CEF). In Estonia, the power sector is the largest CO(2) emitter and is also a source of huge amounts of waste ash. Oil-shale has been burned by pulverized firing (PF) since 1959 and in circulating fluidized-bed combustors (CFBCs) since 2004-2005. Depending on the combustion technology, the ash contains a total of up to 30% free Ca-Mg oxides. In consequence, some amount of emitted CO(2) is bound by alkaline transportation water and by the ash during hydraulic transportation and open-air deposition. The goal of this study was to investigate the possibility of improving the extent of CO(2) capture using additional chemical and technological means, in particular the treatment of aqueous ash suspensions with model flue gases containing 10-15% CO(2). The results indicated that both types of ash (PF and CFBC) could be used as sorbents for CO(2) mineral sequestration. The amount of CO(2) captured averaged 60-65% of the carbonaceous CO(2) and 10-11% of the total CO(2) emissions.

  14. Weathering characteristics of the Lower Paleozoic black shale in northwestern Guizhou Province, south China

    Indian Academy of Sciences (India)

    Yang Liu; Jinchuan Zhang; Xuan Tang; Chao Yang; Shuai Tang

    2016-07-01

    The northwestern Guizhou in the Yangtze Craton of south China has a tremendous potential of shale gas resource. In this paper, we present results from major and trace elements, total organic carbon, mineralogical composition analysis and petrophysical parameters to characterise shale weathering features. Further, the differences of black shale between underground and outcrops have also been presented to examine the changes of black shale after weathering. Our results show that the trace elements of shale have varying degrees of loss in the weathering leaching process, both in Niutitang shale and Longmaxi shale, the loss of B, V, Ni, Cu, Zn and Ba is obvious, but the element migration quantity in the formeris greater than in the latter. Decomposition of minerals such as pyrite, feldspar and calcite result in the leaching of Na, Ca, Mg and Fe. The loss rate of total organic carbon (TOC) in black shales ranges from 18% to 70% with an average of 43%; moreover, the loss of organic carbon in samples with high TOC contentis larger than in those samples with low TOC content. Results following the testing of porosity and permeability show that porosity increases significantly after weathering but permeability changes little. Furthermore, the increment of porosity is greater in the Niutitang shale (with more sulphide minerals) than in the Longmaxi shale, suggesting that the oxidation of sulphide minerals may have led to the formationof an acidic environment, causing the other minerals in the black shale to weather more quickly, thus resulting in increased porosity. The content of clay minerals in the core samples is slightly lesser than the outcrop samples, but the TOC content in the core samples is greater and has a larger specific surface area. This suggest that the TOC content played a decisive role on the specific surface area of shale. In addition, changes in the black shale caused by the weathering process mainly depend on the mineral composition and the TOC content in

  15. Weathering characteristics of the Lower Paleozoic black shale in northwestern Guizhou Province, south China

    Science.gov (United States)

    Liu, Yang; Zhang, Jinchuan; Tang, Xuan; Yang, Chao; Tang, Shuai

    2016-07-01

    The northwestern Guizhou in the Yangtze Craton of south China has a tremendous potential of shale gas resource. In this paper, we present results from major and trace elements, total organic carbon, mineralogical composition analysis and petrophysical parameters to characterise shale weathering features. Further, the differences of black shale between underground and outcrops have also been presented to examine the changes of black shale after weathering. Our results show that the trace elements of shale have varying degrees of loss in the weathering leaching process, both in Niutitang shale and Longmaxi shale, the loss of B, V, Ni, Cu, Zn and Ba is obvious, but the element migration quantity in the former is greater than in the latter. Decomposition of minerals such as pyrite, feldspar and calcite result in the leaching of Na, Ca, Mg and Fe. The loss rate of total organic carbon (TOC) in black shales ranges from 18% to 70% with an average of 43%; moreover, the loss of organic carbon in samples with high TOC content is larger than in those samples with low TOC content. Results following the testing of porosity and permeability show that porosity increases significantly after weathering but permeability changes little. Furthermore, the increment of porosity is greater in the Niutitang shale (with more sulphide minerals) than in the Longmaxi shale, suggesting that the oxidation of sulphide minerals may have led to the formation of an acidic environment, causing the other minerals in the black shale to weather more quickly, thus resulting in increased porosity. The content of clay minerals in the core samples is slightly lesser than the outcrop samples, but the TOC content in the core samples is greater and has a larger specific surface area. This suggest that the TOC content played a decisive role on the specific surface area of shale. In addition, changes in the black shale caused by the weathering process mainly depend on the mineral composition and the TOC content

  16. Pressurized fluidized-bed hydroretorting of Eastern oil shales. Progress report, December 1991--February 1992

    Energy Technology Data Exchange (ETDEWEB)

    Lau, F.S.; Mensinger, M.C.; Roberts, M.J.; Rue, D.M.

    1992-03-01

    The objective is to perform the research necessary to develop the pressurized fluidized-bed hydroretorting (PFH) process for producing oil from Easter oil shales. The program also incorporates research on technologies in areas such as raw shale preparation, beneficiation, product separation, and waste disposal that have the potential of improving the economics and/or environmental acceptability of recovering oil from oil shales using the PFH process. Accomplishments for this period are presented for the following tasks: Testing of Process Improvement Concepts; Beneficiation Research; Operation of PFH on Beneficiated Shale; Environmental Data and Mitigation Analyses; Sample Procurement, Preparation, and Characterization; and Project Management and Reporting. 24 figs., 19 tabs. (AT)

  17. The Importance of Geochemical Parameters and Shale Composition on Rock Mechanical Properties of Gas Shale Reservoirs: a Case Study From the Kockatea Shale and Carynginia Formation From the Perth Basin, Western Australia

    Science.gov (United States)

    Labani, Mohammad Mahdi; Rezaee, Reza

    2015-05-01

    Evaluation of the gas shale mechanical properties is very important screening criteria for determining the potential intervals for hydraulic fracturing and as a result in gas shale sweet spot mapping. Young's modulus and Poisson's ratio are two controlling mechanical properties that dictate the brittleness of the gas shale layers. These parameters can be determined in the laboratory by testing the rock sample under different conditions (static method) or can be calculated using the well-logging data including sonic and density log data (dynamic method). This study investigates the importance of the shale composition and geochemical parameters on the Young's modulus and Poisson's ratio using log data. The data set of this study is coming from five different wells targeting the Kockatea Shale and Carynginia formation, two potential gas shale formations in the Perth Basin, Western Australia. The results show that converse to the common idea the effect of organic matter quantity and maturity on the rock mechanical properties of the gas shale reservoirs is not so much prominent, while the composition of the rock has an important effect on these properties. Considering the weight percentage of shale composition and organic matter quantity it could be concluded that effect of these parameters on rock mechanical properties is dependent on their weight contribution on the shale matrix. As well as effect of thermal maturity on the shale matrix and consequently on the rock mechanical properties of the shales is dependent on the organic matter content itself; therefore, obviously with a low organic matter content thermal maturity has no prominent effect on the brittleness as well.

  18. Nanometer-Scale Pore Characteristics of Lacustrine Shale, Songliao Basin, NE China.

    Directory of Open Access Journals (Sweden)

    Min Wang

    Full Text Available 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.

  19. Microfracturing during primary migration in shales

    Science.gov (United States)

    Teixeira, Marcello Goulart; Donzé, Frédéric; Renard, François; Panahi, Hamed; Papachristos, Efthymios; Scholtès, Luc

    2017-01-01

    In several geological environments, chemical reactions are coupled to rock deformation and the associated stresses induced locally interact with the far field loading. This is the case in immature shales that undergo burial and diagenesis, where the organic matter evolves with temperature into hydrocarbons which induces local volume expansion. At large scale, this mechanism is responsible for the transport of hydrocarbons from source to reservoir rocks, a process referred to as primary migration. However, how the interactions between local fluid production, microfracturing, and transport are coupled remain to be understood. Here, we analyze this coupling phenomenon by developing a discrete element model where the generation of local overpressures occurring in kerogen patches is simulated, while the surrounding rock is subjected to external loading. It is shown that, due to local fluid overpressure; microfracturing occurs and brings the fluids to migrate through the medium. The numerical results are confirmed by laboratory experiments where the network of microfractures induced in an immature Green River shale sample heated under small differential stress was imaged in three dimensions using X-ray microtomography. Moreover, the numerical simulations identify that the state of differential stress and the initial kerogen distribution constitute two key parameters that control the formation of the three-dimensional percolating microfracture network and could thus explain primary migration in shale rocks.

  20. PGE-Re concentrations in carbonaceous siltstones from the Barberton Drilling Project: Sources and processes

    Science.gov (United States)

    Rammensee, Philipp; Aulbach, Sonja

    2014-05-01

    The emergence, diversification and disappearance of Earth's life forms are closely tied to the redox state of the oceans, and the sources and sinks of metabolically cycled metals. It is generally accepted that the early terrestrial atmosphere contained extremely low levels of free oxygen [1]. While a significant change to atmospheric oxygen levels has been constrained to ca. 2.45 Ga ago, the details of the complex prior redox evolution of the oceans and atmosphere, and their influence on continental weathering, are still blurry [1]. Among the trace metals that have been applied to this problem, Re and the platinum-group elements (PGE) have variable redox chemistry that has been successfully exploited to identify detrital vs. hydrogenous sources and the presence of oxic vs. suboxic or euxinic conditions both in young and ancient sediments, including predominantly outcrop samples from the Barberton Greenstone Belt (BGB) [2,3]. As 187Re decays to 187Os, the Re-Os isotope system can additionally be used to date the deposition of carbonaceous shales through construction of isochrons and obtain the initial Os isotope composition, which is a tracer for continental input of radiogenic Os [4]. The sampling approach here was to choose 8+ samples from narrow intervals (≤1 m, to avoid initial Os isotope heterogeneity) from the Barberton Drilling Project (two depths in core BARB5/Fig Tree Group and one interval in core BARB3/Buck Reef Chert. We are currently finalising institution of the sample preparation and analytical techniques, involving (1) high-pressure asher digestion and (2) low-temperature leaching of presumably hydrogenous, acid-soluble components of spiked samples, followed by solvent extraction of Os and cation exchange column chromatography to isolate PGE-Re from the residue, further purification with BPHA and measurement of Ru-Pd-Ir-Pt by ICPMS and of Re-Os by MC-ICPMS. Preliminary tests with the SDO-1 standard have revealed that concentrations of Ir and Pt in

  1. Investigating Rare Earth Element Systematics in the Marcellus Shale

    Science.gov (United States)

    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

  2. Significance of Shale Gas Development

    Institute of Scientific and Technical Information of China (English)

    John Shelton; Mike D. Bumaman; Wenwu Xia; Nathaniel Harding

    2009-01-01

    Natural gas production from shale formations is growing exponentially in the United States. This paper introduces the five major shale formations in the United States and the technologies used to produce them. The Barnett, Haynesville,Fayetteville, Woodford, and Marcellus combined hold an estimated 978 trillion cubic feet of total gas reserves. These findings along with recent technological advances in horizontal drilling and completion methods have transformed the natural gas exploration and production industry in the U.S. and have fundamentally changed the U.S. energy picture. Specifically this paper states that the United States through the utilization of natural gas from shale can reduce its carbon emissions and can become more energy self-sufficient. Finally, the Harding & Shelton Group states in this paper that the opportunity to locate and produce shale gas in China is very similar to that which has taken place in the United States.

  3. Molybdenum isotopic evidence for the origin of chondrules and a distinct genetic heritage of carbonaceous and non-carbonaceous meteorites

    Science.gov (United States)

    Budde, Gerrit; Burkhardt, Christoph; Brennecka, Gregory A.; Fischer-Gödde, Mario; Kruijer, Thomas S.; Kleine, Thorsten

    2016-11-01

    Nucleosynthetic isotope anomalies are powerful tracers to determine the provenance of meteorites and their components, and to identify genetic links between these materials. Here we show that chondrules and matrix separated from the Allende CV3 chondrite have complementary nucleosynthetic Mo isotope anomalies. These anomalies result from the enrichment of a presolar carrier enriched in s-process Mo into the matrix, and the corresponding depletion of this carrier in the chondrules. This carrier most likely is a metal and so the uneven distribution of presolar material probably results from metal-silicate fractionation during chondrule formation. The Mo isotope anomalies correlate with those reported for W isotopes on the same samples in an earlier study, suggesting that the isotope variations for both Mo and W are caused by the heterogeneous distribution of the same carrier. The isotopic complementary of chondrules and matrix indicates that both components are genetically linked and formed together from one common reservoir of solar nebula dust. As such, the isotopic data require that most chondrules formed in the solar nebula and are not a product of protoplanetary impacts. Allende chondrules and matrix together with bulk carbonaceous chondrites and some iron meteorites (groups IID, IIIF, and IVB) show uniform excesses in 92Mo, 95Mo, and 97Mo that result from the addition of supernova material to the solar nebula region in which these carbonaceous meteorites formed. Non-carbonaceous meteorites (enstatite and ordinary chondrites as well as most iron meteorites) do not contain this material, demonstrating that two distinct Mo isotope reservoirs co-existed in the early solar nebula that remained spatially separated for several million years. This separation was most likely achieved through the formation of the gas giants, which cleared the disk between the inner and outer solar system regions parental to the non-carbonaceous and carbonaceous meteorites. The Mo isotope

  4. The micro-distribution of carbonaceous matter in the Murchison meteorite as investigated by Raman imaging

    Science.gov (United States)

    Amri, Chahrazade El; Maurel, Marie-Christine; Sagon, Gérard; Baron, Marie-Hélène

    2005-07-01

    The carbonaceous Murchison chondrite is one of the most studied meteorites. It is considered to be an astrobiology standard for detection of extraterrestrial organic matter. Considerable work has been done to resolve the elemental composition of this meteorite. Raman spectroscopy is a very suitable technique for non-destructive rapid in situ analyses to establish the spatial distribution of carbonaceous matter. This report demonstrates that Raman cartography at a resolution of 1 μm 2 can be performed. Two-dimensional distribution of graphitised carbon, amorphous carbonaceous matter and minerals were obtained on 100 μm 2 maps. Maps of the surface of native stones and of a powdered sample are compared. Graphitic and amorphous carbonaceous domains are found to be highly overlapping in all tested areas at the surface of the meteorite and in its interior as well. Pyroxene, olivine and iron oxide grains are embedded into this mixed carbonaceous material. The results show that every mineral grain with a size of less than a few μm 2 is encased in a thin carbonaceous matrix, which accounts for only 2.5 wt.%. This interstitial matter sticks together isolated mineral crystallites or concretions, including only very few individualized graphitised grains. Grinding separates the mineral particles but most of them retain their carbonaceous coating. This Raman study complements recent findings deduced from other spatial analyses performed by microprobe laser-desorption laser-ionisation mass spectrometry (μL 2MS), transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM).

  5. The Description of Shale Reservoir Pore Structure Based on Method of Moments Estimation

    Science.gov (United States)

    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

  6. New Rock-Eval Method for Characterization of Unconventional Shale Resource Systems

    Directory of Open Access Journals (Sweden)

    Romero-Sarmiento Maria-Fernanda

    2016-05-01

    Full Text Available Unconventional resources such as tight, fractured and hybrid shale gas and oil plays as well as oil or kerogen shale systems, are considered exploitable self-contained source and reservoir rocks. A better understanding of the thermal cracking of sedimentary organic matter, hydrocarbons generation, expulsion, storage and retention mechanisms constitutes a key point, estimating the oil and gas in-place, free or adsorbed, for their exploration and exploitation. Herein, we introduce a new “ready to use” method of analysis and interpretation for the Rock-Eval 6 device for better assessment of free or sorbed hydrocarbons in unconventional shale plays. This method was developed at IFP Energies nouvelles (France and was tested on 15 actual or potential unconventional shale samples from Silurian Shale (Algeria, Mississippian Barnett Shale (USA, Early Jurassic Shale (France, Late Jurassic Bazhenov Shale (Russia and Eocene Green River Shale at different thermal maturity stages. Results indicate a better quantification of free and/or sorbed hydrocarbons (Sh0 and Sh1 peaks as well as a more accurate determination of the Rock-Eval Tmax maturity parameter.

  7. Developments in CO2 mineral carbonation of oil shale ash.

    Science.gov (United States)

    Uibu, M; Velts, O; Kuusik, R

    2010-02-15

    Solid waste and atmospheric emissions originating from power production are serious problems worldwide. In the Republic of Estonia, the energy sector is predominantly based on combustion of a low-grade carbonaceous fossil fuel: Estonian oil shale. Depending on the combustion technology, oil shale ash contains 10-25% free lime. To transport the ash to wet open-air deposits, a hydraulic system is used in which 10(7)-10(8) cubic meters of Ca(2+)-ion-saturated alkaline water (pH level 12-13) is recycled between the plant and sedimentation ponds. The goals of the current work were to design an ash-water suspension carbonation process in a continuous mode laboratory-scale plant and to search for potential means of intensifying the water neutralization process. The carbonation process was optimized by cascading reactor columns in which the pH progressed from alkaline to almost neutral. The amount of CO(2) captured from flue gases can reach 1-1.2 million ton at the 2007 production level of the SC Narva Power Plants. Laboratory-scale neutralization experiments were carried out to compare two reactor designs. Sedimentation of PCC particles of rhombohedral crystalline structure was demonstrated and their main characteristics were determined. A new method providing 50x greater specific intensity is also discussed.

  8. The structural evolution of carbonaceous material during metamorphism : a geothermometer

    Science.gov (United States)

    Beyssac, O.; Goffe, B.; Brunet, F.; Bollinger, L.; Avouac, J.; Rouzaud, J.

    2003-12-01

    With increasing metamorphic temperature, the organic matter present in sedimentary rocks is progressively transformed into graphite (graphitization). The degree of organization of this carbonaceous material (CM) as characterized by Raman spectroscopy (RSCM), can be used as a geothermometer which yields the maximum temperature reached during the metamorphic cycle (Beyssac et al., 2002). We used this RSCM geothermometer to map the maximum metamorphic temperatures through the Lesser Himalaya (LH) in Nepal. This study provides a large dataset (80 samples) to estimate uncertainty of this method and to ascertain its reliability by comparison with conventional petrological investigations. We show that the RSCM geothermometer might be used to detect inter-samples temperature variations as small as 10° C or so, but absolute temperatures are only loosely determined to +/- 50° C due to the uncertainty on the calibration. This successful application of the RSCM geothermometer confirms that, at the timescale of regional metamorphism (several My), the transformation of CM is mainly controlled by temperature. However, laboratory investigations suggest that, in addition to temperature, pressure should also play a role (Beyssac et al. 2003). As a matter of fact, high degree of organizations encountered in natural CM cannot be reproduced in laboratory without pressure, even at temperatures as high as 3000° C. In addition to the data acquired on natural CM, we will discuss laboratory experiments performed up to 8 GPa which show that (1) a few kbar of hydrostatic pressure are required to initiate microtextural and subsequent structural transformations within CM and (2) the overall effect of increasing pressure is to speed up graphitization process. Beyssac, O., Goffe, B., Chopin, C., and Rouzaud, J.N., 2002, Raman spectra of carbonaceous material in metasediments: a new geothermometer. Journal of Metamorphic Geology, 20, 859-871. Beyssac, O., Brunet, F., Petitet, J.P., Goffe, B

  9. Trace metal emissions from the Estonian oil shale fired power

    DEFF Research Database (Denmark)

    Aunela-Tapola, Leena A.; Frandsen, Flemming; Häsänen, Erkki K.

    1998-01-01

    Emission levels of selected trace metals from the Estonian oil shale fired power plant were studied. The plant is the largest single power plant in Estonia with an electricity production capacity of 1170 MWe (1995). Trace metals were sampled from the flue gases by a manual method incorporating...... a two-fraction particle sampling and subsequent absorption of the gaseous fraction. The analyses were principally performed with ICP-MS techniques. The trace metal contents of Estonian oil shale were found to be in the same order of magnitude as of coal on average. The high total particle concentrations...... in the flue gases of the studied oil shale plant contribute, however, to clearly higher total trace metal emission levels compared to modern coal fired power plants. Although the old electrostatic precipitators in the plant have been partly replaced by state-of-the-art electrostatic precipitators...

  10. An in situ FTIR step-scan photoacoustic investigation of kerogen and minerals in oil shale.

    Science.gov (United States)

    Alstadt, Kristin N; Katti, Dinesh R; Katti, Kalpana S

    2012-04-01

    Step-scan photoacoustic infrared spectroscopy experiments were performed on Green River oil shale samples obtained from the Piceance Basin located in Colorado, USA. We have investigated the molecular nature of light and dark colored areas of the oil shale core using FTIR photoacoustic step-scan spectroscopy. This technique provided us with the means to analyze the oil shale in its original in situ form with the kerogen-mineral interactions intact. All vibrational bands characteristic of kerogen were found in the dark and light colored oil shale samples confirming that kerogen is present throughout the depth of the core. Depth profiling experiments indicated that there are changes between layers in the oil shale molecular structure at a length scale of micron. Comparisons of spectra from the light and dark colored oil shale core samples suggest that the light colored regions have high kerogen content, with spectra similar to that from isolated kerogen, whereas, the dark colored areas contain more mineral components which include clay minerals, dolomite, calcite, and pyrite. The mineral components of the oil shale are important in understanding how the kerogen is "trapped" in the oil shale. Comparing in situ kerogen spectra with spectra from isolated kerogen indicate significant band shifts suggesting important nonbonded molecular interactions between the kerogen and minerals.

  11. 40Ar/39Ar Ages of Carbonaceous Xenoliths in 2 HED Meteorites

    Science.gov (United States)

    Turrin, B.; Lindsay, F. N.; Park, J.; Herzog, G. F.; Delaney, J. S.; Swisher, C. C., III; Johnson, J.; Zolensky, M.

    2016-01-01

    The generally young K/Ar and 40Ar/39Ar ages of CM chondrites made us wonder whether carbonaceous xenoliths (CMX) entombed in Howardite–Eucrite–Diogenite (HED) meteorites might retain more radiogenic 40Ar than do ‘free-range’ CM-chondrites. To find out, we selected two HED breccias with carbonaceous inclusions in order to compare the 40Ar/39Ar release patterns and ages of the inclusions with those of nearby HED material. Carbonaceous inclusions (CMXs) in two HED meteorites lost a greater fraction of radiogenic 40Ar than did surrounding host material, but a smaller fraction of it than did free-range CM-chondrites such as Murchison or more heavily altered ones. Importantly, however, the siting of the CMXs in HED matrix did not prevent the 40Ar loss of about 40 percent of the radiogenic 40Ar, even from phases that degas at high laboratory temperatures. We infer that carbonaceous asteroids with perihelia of 1 astronomical unit probably experience losses of at least this size. The usefulness of 40Ar/39Ar dating for samples returned from C-type asteroids may hinge, therefore, on identifying and analyzing separately small quantities of the most retentive phases of carbonaceous chondrites.

  12. Pressurized fluidized-bed hydroretorting of Eastern oil shales

    Energy Technology Data Exchange (ETDEWEB)

    Roberts, M.J.; Mensinger, M.C.; Rue, D.M.; Lau, F.S. (Institute of Gas Technology, Chicago, IL (United States)); Schultz, C.W. (Alabama Univ., University, AL (United States)); Parekh, B.K. (Kentucky Univ., Lexington, KY (United States)); Misra, M. (Nevada Univ., Reno, NV (United States)); Bonner, W.P. (Tennessee Technological Univ., Cookeville, TN (United States))

    1992-11-01

    The Devonian oil shales of the Eastern United States are a significant domestic energy resource. The overall objective of the multi-year program, initiated in October 1987 by the US Department of Energy is to perform the research necessary to develop the Pressurized Fluidized-Bed Hydroretorting (PFH) process for producing oil from Eastern oil shales. The program also incorporates research on technologies in areas such as raw shale preparation, beneficiation, product separation, and waste disposal that have the potential of improving the economics and/or environmental acceptability of recovering oil from oil shales using the PFH process. The results of the original 3-year program, which was concluded in May 1991, have been summarized in a four-volume final report published by IGT. DOE subsequently approved a 1-year extension to the program to further develop the PFH process specifically for application to beneficiated shale as feedstock. Studies have shown that beneficiated shale is the preferred feedstock for pressurized hydroretorting. The program extension is divided into the following active tasks. Task 3. testing of process improvement concepts; Task 4. beneficiation research; Task 5. operation of PFH on beneficiated shale; Task 6. environmental data and mitigation analyses; Task 7. sample procurement, preparation, and characterization; and Task 8. project management and reporting. In order to accomplish all the program objectives, the Institute of Gas Technology (IGT), the prime contractor, worked with four other institutions: the University of Alabama/Mineral Resources Institute (MRI), the University of Kentucky Center for Applied Energy Research (UK-CAER), the University of Nevada (UN) at Reno, and Tennessee Technological University (TTU). This report presents the work performed during the program extension from June 1, 1991 through May 31, 1992.

  13. Lithology and minerageny of black shale of the Taimyr-Severnaya Zemlya region

    Science.gov (United States)

    Mozoleva, Irina

    2014-05-01

    In the Taimyr Peninsula and Severnaya Zemlya Archipelago, black shale deposits are widespread - subaqueous fine-grained, often thin-bedded, dark-coloured rocks of clayey, carbonate, silica or mixed composition, significantly enriched (1-18%) with organic matter (OM). Two large age intervals of accumulation are distinguished: Riphean and Early-Middle Paleozoic (with maxima in the Ordovician and Silurian). Black shale Riphean complexes are spread in the northern part of the Taimyr Peninsula, where they build up a strip 100-150 km wide along the coast from the Gulf of Minin to the Gulf of Thaddeus and on Bolshevik Isl. Two types of black shale deposits are distinguished (Zabiyaka, 1972; Kabankov, 1980). The first type - predominantly siliciclastic deposits. Represented by cyclical alternation of flyschoid and turbidite types of terrigenous deposits with carbonaceous shale members. Deposits are unevenly enriched in OM in the form of filamentous, lenticular, lumpy accumulations and are often accompanied by pyrite. OM content to 2.5%, rarely to 6%. The second type - carbonate-terrigenous-clayey deposits. Represented by intensely displaced metamorphosed sandstone, siltstone, and mudstone interbedded with marble and limestone. Carbonaceous deposits are intensively. OM content 0.66-2.3%. OM is distributed unevenly, often localized along fractures. Black shale complexes of Middle-Lower Paleozoic age include deposits from the Lower Cambrian to Lower Carboniferous (Sobolevskaya et al., 1979; Lazarenko, 1980). On October Revolution Isl., the Lower Cambrian-Lower Ordovician deposits are spread. In Taimyr, black shale complexes build up a relatively narrow, about 75-100 km, strip stretching in sublatitudinal direction, limited by regional faults (Main Taimyr in the north, Pyasina-Faddey in the south). Deposits are represented by a wide range of lithological genetic rock types. Carbonate-argillaceous rocks with terrigenous material admixture and siliceous-terrigenous with a small

  14. Upper Devonian radiolarians separated from chert of the Ford Lake Shale, Alaska

    Science.gov (United States)

    Holdsworth, Brian K.; Jones, D.L.; Allison, C.

    1978-01-01

    Leaching of black bedded chert from the Ford Lake Shale, Kandik Basin, Alaska, with dilute hydrofluoric acid resulted in the complete separation of moderately well preserved radiolarians. Preliminary study of an assemblage obtained from the lower half of the formation revealed six to eight forms apparently identical to specimens previously known from the Tournaisian of southern France and northwestern Turkey, including four genera not previously described from North America. Sparse, poorly preserved conodonts in the same sample are of Late Devonian age. We conclude that certain radiolarian species, hitherto known only from the early Carboniferous, span the Devonian-Carboniferous boundary. The radiolarian assemblage of the Ford Lake Shale sample contrasts markedly with Late Devonian assemblages known from the Canol Shale of northern Canada and the Huron Member of the Ohio Shale; the Ford Lake Shale fauna may reflect greater oceanic influences than these other localities, which lie farther inland from the Devonian continental margin.

  15. Iron isotope biogeochemistry of Neoproterozoic marine shales

    Science.gov (United States)

    Kunzmann, Marcus; Gibson, Timothy M.; Halverson, Galen P.; Hodgskiss, Malcolm S. W.; Bui, Thi Hao; Carozza, David A.; Sperling, Erik A.; Poirier, André; Cox, Grant M.; Wing, Boswell A.

    2017-07-01

    Iron isotopes have been widely applied to investigate the redox evolution of Earth's surface environments. However, it is still unclear whether iron cycling in the water column or during diagenesis represents the major control on the iron isotope composition of sediments and sedimentary rocks. Interpretation of isotopic data in terms of oceanic redox conditions is only possible if water column processes dominate the isotopic composition, whereas redox interpretations are less straightforward if diagenetic iron cycling controls the isotopic composition. In the latter scenario, iron isotope data is more directly related to microbial processes such as dissimilatory iron reduction. Here we present bulk rock iron isotope data from late Proterozoic marine shales from Svalbard, northwestern Canada, and Siberia, to better understand the controls on iron isotope fractionation in late Proterozoic marine environments. Bulk shales span a δ 56Fe range from -0.45 ‰ to +1.04 ‰ . Although δ 56Fe values show significant variation within individual stratigraphic units, their mean value is closer to that of bulk crust and hydrothermal iron in samples post-dating the ca. 717-660 Ma Sturtian glaciation compared to older samples. After correcting for the highly reactive iron content in our samples based on iron speciation data, more than 90% of the calculated δ 56Fe compositions of highly reactive iron falls in the range from ca. -0.8 ‰ to +3 ‰ . An isotope mass-balance model indicates that diagenetic iron cycling can only change the isotopic composition of highly reactive iron by oxygen levels. Alternatively, increasing oxygen levels would have led to a higher proportion of Fe(II) being oxidized, without decreasing the initial size of the ferrous seawater iron pool. We consider the latter explanation as the most likely. According to this hypothesis, the δ 56Fe record reflects the redox evolution of Earth's surface environments. δ 56Fe values in pre-Sturtian samples

  16. Variations in the geochemistry of closely interbedded oil-prone coals and shales

    Energy Technology Data Exchange (ETDEWEB)

    Curry, D.J. (Exxon Production Research, Houston, TX (United States))

    1994-07-01

    Paralic and deltaic environments frequently contain closely interbedded oil-prone coals and carbonaceous shales of similar organic facies. However, differences in depositional and diagenetic conditions can result in significant variations in geochemistry between these coals and shales. These variations are observed in sediments from a range of ages and areas, including Australia, New Zealand, and Indonesia. For example, pristane/phytane and pristane/n-C[sub 17] ratios are frequently higher in coals than in associated shales, although n-alkane distributions are similar. The C[sub 27] Ts/Tm ratios are frequently much lower in coals, although most other biomarker ratios are generally the same for coals and shales. However, absolute biomarker concentrations, particularly of C[sub 27] Tm hopane, can be two to four times higher in coals. Significantly, many coals contain high concentrations of diasteranes (equivalent to those observed in shales). Differences in other parameters such as the C[sub 30] diahopane/C[sub 30] hopane ratios and pyrolysate compositions are also evident. Data indicate that rocks begin to become more coal-like at TOCs of approximately 25%. The variations in these parameters are probably the result of variability in early depositional and diagenetic conditions, such as eH, pH, and microbial action. In addition, these parameters are probably influenced by the effects of an organic vs. an inorganic matrix. The impact of this variability must be considered when conducting oil-source correlation studies and when assessing the relative contributions of coals and shales to the generation of oil in a basin.

  17. Preparation and Characterization of Single-handed Helical Carbonaceous Nanoifbers using 1,4-Phenylene Bridged Polybissilsesquioxanes

    Institute of Scientific and Technical Information of China (English)

    XIAO Zeli; GUO Yongmin; LI Baozong; LI Yi

    2016-01-01

    Single-handed helical carbonaceous materials attracted much attention for varieties of potential applications. Herein, single-handed helical 1, 4-phenylene bridged polybissilsesquioxane nanoifbers were prepared through a supramolecular templating approach using a pair of enantiomers. After carbonization at 700℃ for 2.0 h and removal of silica using HF aqueous solution, single-handed helical carbonaceous nanoifbers were obtained. The obtained samples were characterized using the ifeld-emission scanning electron microscopy, transmission electron microscopy, N2 sorptions, X-ray diffraction, Raman spectroscopy and diffuse relfectance circular dichroism (DRCD). The Raman spectrum indicated that the carbon was amorphous. The DRCD spectra indicated that the carbonaceous nanoifbers exhibited optical activity. The surface area of the left-handed helical carbonaceous nanoifbers was 907 m2/g. Such material has potential applications as chirality sensor and supercapacitor electrode.

  18. Paraho oil shale project. [Coloardo

    Energy Technology Data Exchange (ETDEWEB)

    Pforzheimer, H.

    1976-01-01

    The Paraho Oil Shale Project is a privately financed program to prove the Paraho retorting process and hardware on oil shale at Anvil Points, Colo., near Rifle. The project was launched in late 1973 under the sponsorship of 17 participants many of whom were active in earlier oil shale research. Two new Paraho retorts, a pilot and a semiworks size unit, were installed at Anvil Points. The oil-shale mine on the adjacent Naval Oil Shale Reserve was reactivated. The mine and new retorts were put into operation during 1974. The pilot plant is used to explore operating parameters in order to define conditions for testing in the larger semiworks size retort. The experimental operations in 1974 set the stage for the successful runs in 1975 and early 1976. The results of the Paraho operations to date have been encouraging. They demonstrate that the process works, that the equipment is durable, and that both are environmentally acceptable on a pilot and a semiworks plant scale.

  19. Source apportionment of carbonaceous aerosol in southern Sweden

    Directory of Open Access Journals (Sweden)

    J. Genberg

    2011-05-01

    Full Text Available A one-year study was performed at the Vavihill background station in southern Sweden to estimate the anthropogenic contribution to the carbonaceous aerosol. Weekly samples of the particulate matter PM10 were collected on quartz filters, and the amounts of organic carbon, elemental carbon, radiocarbon (14C and levoglucosan were measured. This approach enabled source apportionment of the total carbon in the PM10 fraction using the concentration ratios of the sources. The sources considered in this study were emissions from the combustion of fossil fuels and biomass, as well as biogenic sources. During the summer, the carbonaceous aerosol mass was dominated by compounds of biogenic origin (82 %, which are associated with biogenic primary and secondary organic aerosols. During the winter months, biomass combustion (38 % and fossil fuel combustion (33 % were the main contributors to the carbonaceous aerosol. Elemental carbon concentrations in winter were about twice as large as during summer, and can be attributed to biomass combustion, probably from domestic wood burning. The contribution of fossil fuels to elemental carbon was stable throughout the year, although the fossil contribution to organic carbon increased during the winter. Thus, the organic aerosol originated mainly from natural sources during the summer and from anthropogenic sources during the winter. The result of this source apportionment was compared with results from the EMEP model. The model and measurements were generally consistent for total atmospheric organic carbon, however, the contribution of the sources varied substantially. E.g. the biomass burning contributions of OC were underestimated by the model by a factor of 8.2 compared to the measurements.

  20. Stress dependence of permeability of intact and fractured shale cores.

    Science.gov (United States)

    van Noort, Reinier; Yarushina, Viktoriya

    2016-04-01

    Whether a shale acts as a caprock, source rock, or reservoir, understanding fluid flow through shale is of major importance for understanding fluid flow in geological systems. Because of the low permeability of shale, flow is thought to be largely confined to fractures and similar features. In fracking operations, fractures are induced specifically to allow for hydrocarbon exploration. We have constructed an experimental setup to measure core permeabilities, using constant flow or a transient pulse. In this setup, we have measured the permeability of intact and fractured shale core samples, using either water or supercritical CO2 as the transporting fluid. Our measurements show decreasing permeability with increasing confining pressure, mainly due to time-dependent creep. Furthermore, our measurements show that for a simple splitting fracture, time-dependent creep will also eliminate any significant effect of this fracture on permeability. This effect of confinement on fracture permeability can have important implications regarding the effects of fracturing on shale permeability, and hence for operations depending on that.

  1. Experimental Study of Shale Rock Self-Heating

    Science.gov (United States)

    Restuccia, Francesco; Ptak, Nicolas; Rein, Guillermo

    2016-04-01

    Self-heating phenomena due to spontaneous exothermic reactions in oxidative environments are common for many porous materials, even at low temperatures. Combustion of shale outcrop formations has been reported in recent years, with self-heating a potential initiating cause. This work studies experimentally and for the first time the self-heating behavior of shale rock, a porous sedimentary rock. Using field samples collected from shale outcrop at Kimmeridge Bay (UK) and the Frank-Kamenetskii theory of criticality, we determine effective kinetic parameters and thermal properties for different shale particle size distributions and upscale the results to field formations of different thicknesses. We show that for fine particle sizes, with diameter below 2mm, spontaneous ignition is possible for rock formations of thickness between 25m and 5.4m at ambient temperatures between 16°C and 44°C. For the same temperature range, the required thickness is between 375km and 15km for coarse particles of diameter below 17mm. This shows that shale rock is reactive, with reactivity highly dependent on particle diameter, and self-ignition is possible for small particles in outcrops or formations accidentally exposed to oxygen.

  2. Electric property evidences of carbonification of organic matters in marine shales and its geologic significance: A case study of the Lower Cambrian Qiongzhusi shale in the southern Sichuan Basin

    Directory of Open Access Journals (Sweden)

    Yuman Wang

    2014-12-01

    Full Text Available Searching for some reliable evidences that can verify the carbonification of organic matters in marine shales is a major scientific issue in selecting shale gas fairways in old strata. To this end, based on core, logging and testing data, the electric property of two organic-rich shale layers in the Lower Cambrian Qiongzhusi Fm. and the Lower Silurian Longmaxi Fm. in the southern Sichuan Basin was compared to examine the carbonification signs of organic matters in the Qiongzhusi shale and its influence on gas occurrence in the shales. The following conclusions were reached: (1 the electric property experiment shows that the Qiongzhusi shale in the study area has had carbonification of organic matters. The low resistivity of dry samples from this highly mature organic-rich shale and ultra-low resistivity on downhole logs can be used to directly judge the degree of organic matter carbonification and the quality of source rocks; (2 in the Changning area, the Qiongzhusi shale shows low resistivity of dry samples and low to ultra-low resistivity on logs, indicating that organic matters are seriously carbonized, while in the Weiyuan area, the Qiongzhusi shale shows a basically normal resistivity on log curves, indicating its degree of graphitization between the Longmaxi Fm. and Qiongzhusi Fm. in the Changning area; (3 shale with medium-to-high resistivity is remarkably better than that with ultra-low resistivity in terms of gas generation potential, matrix porosity and gas adsorption capacity; (4 industrial gas flow has been tested in the organic shales with medium-to-high resistivity in the Jianwei–Weiyuan–Tongnan area in the north, where the Qiongzhusi shale is a favorable shale gas exploration target.

  3. Uranium favorability of tertiary sedimentary rocks of the Pend Oreille River valley, Washington. [Measurement and sampling of surface sections, collection of samples from isolated outcrops, chemical and mineralogical analyses of samples, and examination of available water logs

    Energy Technology Data Exchange (ETDEWEB)

    Marjaniemi, D.K.; Robins, J.W.

    1975-08-01

    Tertiary sedimentary rocks in the Pend Oreille River valley were investigated in a regional study to determine the favorability for potential uranium resources of northeastern Washington. This project involved measurement and sampling of surface sections, collection of samples from isolated outcrops, chemical and mineralogical analyses of samples, and examination of available water well logs. The Box Canyon Dam area north of Ione is judged to have very high favorability. Thick-bedded conglomerates interbedded with sandstones and silty sandstones compose the Tiger Formation in this area, and high radioactivity levels are found near the base of the formation. Uranophane is found along fracture surfaces or in veins. Carbonaceous material is present throughout the Tiger Formation in the area. Part of the broad Pend Oreille valley surrounding Cusick, Washington, is an area of high favorability. Potential host rocks in the Tiger Formation, consisting of arkosic sandstones interbedded with radioactive shales, probably extend throughout the subsurface part of this area. Carbonaceous material is present and some samples contain high concentrations of uranium. In addition, several other possible chemical indicators were found. The Tiger-Lost Creek area is rated as having medium favorability. The Tiger Formation contains very hard, poorly sorted granite conglomerate with some beds of arkosic sandstone and silty sandstone. The granite conglomerate was apparently derived from source rocks having relatively high uranium content. The lower part of the formation is more favorable than the upper part because of the presence of carbonaceous material, anomalously high concentrations of uranium, and other possible chemical indicators. The area west of Ione is judged to have low favorability, because of the very low permeability of the rocks and the very low uranium content. (auth)

  4. Measurement of water activity from shales through thermo hygrometer

    Energy Technology Data Exchange (ETDEWEB)

    Rabe, Claudio [Pontificia Univ. Catolica do Rio de Janeiro, RJ (Brazil). Dept. de Engenharia Civil. Grupo de Tecnologia e Engenharia de Petroleo (GTEP)

    2004-07-01

    This paper presents a campaign of lab tests to obtain the water activity from shales and its pore fluid originated from offshore and onshore basin. The results of water activity from shales indicate that the values rang from 0.754 to 0.923 and for the pore fluid are between 0.987 and 0.940. The results show that the water activity of interstitial water can be obtained in 6 days and the rock in 10 days using the thermo hygrometer used. The degree of saturation, water content, kind and tenor of expansible and hydratable clay mineral, total and interconnected porosity, salinity of interstitial fluid and the capillary pressure of shale samples affected the results of water activity. (author)

  5. Steep Decline and Low Hydrocarbon Recovery in Fractured Shale: What and Why?

    Science.gov (United States)

    Hu, Q.; Barber, T.; Gao, Z.; Gao, X.; Ewing, R. P.

    2014-12-01

    Since 2000, the technological advances of horizontal drilling and hydraulic fracturing in the United States have led to a dramatic increase in hydrocarbon (gas and oil) production from shale formations, changing the energy landscape in the US and worldwide. Since 2005, the surge in tight oil production from shale formations has provided tremendous optimism regarding future United States hydrocarbon production, unexpectedly becoming the fastest-growing frontier of unconventional resources. According to the Energy Information Administration's newly released report in 2014, US oil output from tight oil prospects will almost double from the 2012 level of 2.5 million barrels per day, to 4.8 by 2019. However, total gas recovery from the Barnett play was reported to be only12-30%, and the tight-oil recovery rate from shale formations is even lower at 5-10%. The main barrier to sustainable development of US shale, the pore structure of the nanopores storing and transporting hydrocarbons, has been quietly ignored. We have studied pore structure, edge-accessible porosity, and how wettability is associated with mineral and organic kerogen phases, from four complementary tests: vacuum saturation with vacuum-pulling on dry shale followed with tracer introduction, tracer diffusion into fluid-saturated shale, fluid and tracer imbibition into partially-saturated shale, and Wood's metal intrusion followed with SEM imaging and elemental mapping. The first three tests use tracer-bearing fluids (API brine or n-decane), with tracer distribution on shale mapped with micro-scale laser ablation-ICP-MS analyses. These innovative approaches indicate the limited accessibility (several millimeters from shale sample edge) and connectivity of nanopores in shales under atmospheric condition, which is linked to the steep initial (e.g., 1st year) decline and low overall recovery because of the limited connection of hydrocarbon molecules in the shale matrix to the stimulated fracture network.

  6. Oil-shale plants in Estonia

    Energy Technology Data Exchange (ETDEWEB)

    Suurkuusk, T. (Power Engineering Department, Tallinn Technical University, Tallinn, Estonia (SU))

    1991-08-01

    The specific feature of the Estonian energy system is the oil-shale based energy production. The total capacity of the Estonian energy system is 3311 MW, and from this 3104 MW is oil-shale based. There are four oil-shale based power plants in the North-East region of Estonia. (author).

  7. Deformation and Fracture of Shale at the Nanoscale

    Science.gov (United States)

    Bennett, K. C.; Borja, R. I.

    2013-12-01

    The deformation and fracture properties of shales depend on the mechanical properties of their basic constituents, including the solid clay particles, inclusions such as silt and organics, and the multi-scale porosity comprised of existing micro-fractures and the nano-scale porosity of the porous clay matrix. A great deal of understanding of the overall macroscopic (field scale) mechanical properties of shales can be gained by studying the deformation and fracture properties of these constituents along with their composite behavior, i.e., the mechanisms of deformation and fracture of shale. This project builds upon our recently acquired ability to image with fixed ion beam scanning electron microscopy (FIB-SEM) the 3D geometry of a porous shale sample to nanometer resolution, as well as to test this sample on a nanoindenter at both the particle and composite scales, in order to develop a 3D mechanistic model to interpret the results of nanoindentation tests. The pore-scale study considers the intrinsic deformation and fracture properties of clay particles, and the effect of silt inclusions and particle packing into an anisotropic composite matrix. The analysis accounts for anisotropic and heterogeneous shale elasticity, plasticity, damage, and fissility. A finite element (FE) model is being developed which uses a recently developed finite deformation crystal plasticity algorithm and an enhanced FE method for capturing strong discontinuity. The model aims to capture the effects of the particle elasticity, plastic yielding, and the damage induced by the indenter, including the fracturing and chipping within the mineral grains and around the perimeter of the indent. Anisotropy of fracture properties is examined with respect to delamination of the clay matrix in the bed-parallel direction and to breaking of plate-like clay particles. The ultimate goal of this research is to establish a framework for investigating the poromechanical properties of shale at the nano

  8. Assessing Radium Activity in Shale Gas Produced Brine

    Science.gov (United States)

    Fan, W.; Hayes, K. F.; Ellis, B. R.

    2015-12-01

    The high volumes and salinity associated with shale gas produced water can make finding suitable storage or disposal options a challenge, especially when deep well brine disposal or recycling for additional well completions is not an option. In such cases, recovery of commodity salts from the high total dissolved solids (TDS) of the brine wastewater may be desirable, yet the elevated concentrations of the naturally occurring radionuclides such as Ra-226 and Ra-228 in produced waters (sometimes substantially greater than the EPA limit of 5 pCi/L) may concentrate during these steps and limit salt recovery options. Therefore, assessing the potential presence of these Ra radionuclides in produced water from shale gas reservoir properties is desirable. In this study, we seek to link U and Th content within a given shale reservoir to the expected Ra content of produced brine by accounting for secular equilibrium within the rock and subsequent release to Ra to native brines. Produced brine from a series of Antrim shale wells and flowback from a single Utica-Collingwood shale well in Michigan were sampled and analyzed via ICP-MS to measure Ra content. Gamma spectroscopy was used to verify the robustness of this new Ra analytical method. Ra concentrations were observed to be up to an order of magnitude higher in the Antrim flowback water samples compared to those collected from the Utica-Collingwood well. The higher Ra content in Antrim produced brines correlates well with higher U content in the Antrim (19 ppm) relative to the Utica-Collingwood (3.5 ppm). We also observed an increase in Ra activity with increasing TDS in the Antrim samples. This Ra-TDS relationship demonstrates the influence of competing divalent cations in controlling Ra mobility in these clay-rich reservoirs. In addition, we will present a survey of geochemical data from other shale gas plays in the U.S. correlating shale U, Th content with produced brine Ra content. A goal of this study is to develop a

  9. Texture and anisotropy analysis of Qusaiba shales

    KAUST Repository

    Kanitpanyacharoen, Waruntorn

    2011-02-17

    Scanning and transmission electron microscopy, synchrotron X-ray diffraction, microtomography and ultrasonic velocity measurements were used to characterize microstructures and anisotropy of three deeply buried Qusaiba shales from the Rub\\'al-Khali basin, Saudi Arabia. Kaolinite, illite-smectite, illite-mica and chlorite show strong preferred orientation with (001) pole figure maxima perpendicular to the bedding plane ranging from 2.4-6.8 multiples of a random distribution (m.r.d.). Quartz, feldspars and pyrite crystals have a random orientation distribution. Elastic properties of the polyphase aggregate are calculated by averaging the single crystal elastic properties over the orientation distribution, assuming a nonporous material. The average calculated bulk P-wave velocities are 6.2 km/s (maximum) and 5.5 km/s (minimum), resulting in a P-wave anisotropy of 12%. The calculated velocities are compared with those determined from ultrasonic velocity measurements on a similar sample. In the ultrasonic experiment, which measures the effects of the shale matrix as well as the effects of porosity, velocities are smaller (P-wave maximum 5.3 km/s and minimum 4.1 km/s). The difference between calculated and measured velocities is attributed to the effects of anisotropic pore structure and to microfractures present in the sample, which have not been taken into account in the matrix averaging. © 2011 European Association of Geoscientists & Engineers.

  10. Laboratory Studies Of Circumstellar Carbonaceous Grain Formation

    Science.gov (United States)

    Contreras, Cesar; Sciamma-O'Brien, Ella; Salama, Farid

    2014-06-01

    The study of the formation processes of dust is essential to understand the budget of extraterrestrial organic molecules. Although dust with all its components plays an important role in the evolution of interstellar (IS) chemistry and in the formation of organic molecules, little is known on the formation processes of carbonaceous dust. We report the progress that was recently achieved in this domain using NASA Ames’ COSmIC facility (Contreras & Salama 2013, ApJS, 208, 6). PAHs are important chemical building blocks of IS dust. They are detected in IDPs and in meteoritic samples. Additionally, observational, laboratory, and theoretical studies have shown that PAHs are an important, ubiquitous component of the ISM. The formation of PAHs from smaller molecules has not been extensively studied. Therefore, we have performed laboratory experiments to study the dynamic processes of carbon grain formation, starting from the smallest hydrocarbon molecules into the formation of larger PAH and further into nanograins. Studies of IS dust analogs formed from a variety of PAH and hydrocarbon precursors as well as species that include the atoms O, N, and S, have recently been performed in our laboratory using the COSmIC facility to provide conditions that simulate IS and circumstellar environments. The species formed in the COSmiC chamber through a pulsed discharge nozzle plasma source are detected and characterized with a cavity ringdown spectrometer coupled to a time-of-flight mass spectrometer, thus providing both spectroscopic and ion mass information in-situ. Analysis of solid soot particles was also conducted using scanning electron microscopy at the UCSC/NASA Ames’ MACS facility. The SEM analysis of the deposition of soot from methane and acetylene precursors seeded in argon plasmas provide examples on the types of nanoparticles and micrograins that are produced in these gas mixtures under our experimental conditions. From these measurements, we derive information on

  11. Mineralogy and geochemistry of Mississippian and Lower Pennsylvanian black shales at the northern margin of the Variscan mountain belt (Germany and Belgium)

    Energy Technology Data Exchange (ETDEWEB)

    Rippen, D.; Uffmann, A.K.; Littke, R. [RWTH Aachen Univ. (Germany). Energy and Mineral Resources Group (EMR)

    2013-08-01

    Ongoing exploration on unconventional gas resources in Central Europe led to a focus of interest on Paleozoic black shale formations. The work presented here comprises diverse assessment-critical data of potentially economic black shale formations of the Carboniferous, including mineralogy, geochemical data, petrophysical data and geological parameters such as burial and thermal history. The sampled and investigated Paleozoic black shales are highly mature to overmature in terms of oil generation, although some gas generation potential remains. Especially the shales of the uppermost Mississippian (Upper Alum Shale/Chokier Formation) have high contents of organic carbon, are tens of meters thick and reached the gas window. Adjacent carbonates are often stained black and rich in solid bitumen, indicating a former oil impregnation of these reservoirs. Furthermore, the geochemical and petrophysical properties of the Upper Alum Shale and Chokier Formation black shales are similar to those of already producing shale gas plays like the Barnett shale in the USA. These shale sequences are enriched in silica, needed for enhanced fraccability performance at production stage. Although all hydrocarbon potential for the Mississippian shales is exhausted, a high retention potential of thermally generated gas is favored by thick overlying sequences of greywackes and shales in most of the investigated areas. Based on these observations, the Upper Alum Shale and the Chokier formation can be regarded as potential gas shale targets. Any exploration will have to take place north of the outcrop areas, because present-day Mississippian strata are completely eroded south of the studied outcrops. Most other Mississippian and Pennsylvanian black shales are relatively thin and are therefore not considered as primary targets for shale gas plays. (orig.)

  12. Nuclear magnetic biosignatures in the carbonaceous matter of ancient cherts: comparison with carbonaceous meteorites.

    Science.gov (United States)

    Gourier, Didier; Delpoux, Olivier; Binet, Laurent; Vezin, Hervé

    2013-10-01

    The search for organic biosignatures is motivated by the hope of understanding the conditions of emergence of life on Earth and the perspective of finding traces of extinct life in martian sediments. Paramagnetic radicals, which exist naturally in amorphous carbonaceous matter fossilized in Precambrian cherts, were used as local structural probes and studied by electron paramagnetic resonance (EPR) spectroscopy. The nuclear magnetic resonance transitions of elements inside and around these radicals were detected by monitoring the nuclear modulations of electron spin echo in pulsed EPR. We found that the carbonaceous matter of fossilized microorganisms with age up to 3.5 billion years gives specific nuclear magnetic signatures of hydrogen (¹H), carbon (¹³C), and phosphorus (³¹P) nuclei. We observed that these potential biosignatures of extinct life are found neither in the carbonaceous matter of carbonaceous meteorites (4.56 billion years), the most ancient objects of the Solar System, nor in any carbonaceous matter resulting from carbonization of organic and bioorganic precursors. These results indicate that these nuclear signatures are sensitive to thermal episodes and can be used for Archean cherts with metamorphism not higher than the greenschist facies.

  13. Amino and fatty acids in carbonaceous meteorites

    Science.gov (United States)

    Kvenvolden, K. A.

    1974-01-01

    Analyses of two carbonaceous meteorites have provided much of the latest evidence which seems to support Oparin's theory on the origin of life. The meteorites involved are the Murray meteorite, which fell in 1950, and the Murchison meteorite, which fell in 1969. The amino acids in the two meteorites are similar in composition. Eight of the twenty amino acids found belong to amino acids present in proteins. A number of monocarboxylic and dicarboxylic fatty acids were also found in the meteorites.

  14. Carbonaceous particles reduce marine microgel formation

    OpenAIRE

    Shiu, Ruei-Feng; Chin, Wei-Chun; Lee, Chon-Lin

    2014-01-01

    An increase in ambient carbonaceous particle (CNP) levels has been found, potentially leading to significant environmental/health hazards. These particles will ultimately enter the oceanic environment and interact with dissolved organic carbon. However, a detailed mechanistic understanding of their behavior, transport, and fate in marine systems is still much needed. This study, using carbon black (CB, 14?nm) nanoparticles as a model, aimed to investigate the impact of CNPs on marine microgel...

  15. Geomechanical Characterization of Marcellus Shale

    Science.gov (United States)

    Villamor Lora, Rafael; Ghazanfari, Ehsan; Asanza Izquierdo, Enrique

    2016-09-01

    Understanding the reservoir conditions and material properties that govern the geomechanical behavior of shale formations under in situ conditions is of vital importance for many geomechanical applications. The development of new numerical codes and advanced multi-physical (thermo-hydro-chemo-mechanical) constitutive models has led to an increasing demand for fundamental material property data. Previous studies have shown that deformational rock properties are not single-value, well-defined, linear parameters. This paper reports on an experimental program that explores geomechanical properties of Marcellus Shale through a series of isotropic compression (i.e. σ 1 = σ 2 = σ 3) and triaxial (i.e. σ 1 > σ 2 = σ 3) experiments. Deformational and failure response of these rocks, as well as anisotropy evolution, were studied under different stress and temperature conditions using single- and multi-stage triaxial tests. Laboratory results revealed significant nonlinear and pressure-dependent mechanical response as a consequence of the rock fabric and the occurrence of microcracks in these shales. Moreover, multi-stage triaxial tests proved to be useful tools for obtaining failure envelopes using a single specimen. Furthermore, the anisotropic nature of Marcellus Shale was successfully characterized using a three-parameter coupled model.

  16. Mechanical Characterization of Mancos Shale

    Science.gov (United States)

    Broome, S.; Ingraham, M. D.; Dewers, T. A.

    2015-12-01

    A series of tests on Mancos shale have been undertaken to determine the failure surface and to characterize anisotropy. This work supports additional studies which are being performed on the same block of shale; fracture toughness, permeability, and chemical analysis. Mechanical tests are being conducted after specimens were conditioned for at least two weeks at 70% constant relative humidity conditions. Specimens are tested under drained conditions, with the constant relative humidity condition maintained on the downstream side of the specimen. The upstream is sealed. Anisotropy is determined through testing specimens that have been cored parallel and perpendicular to the bedding plane. Preliminary results show that when loaded parallel to bedding the shale is roughly 50% weaker. Test are run under constant mean stress conditions when possible (excepting indirect tension, unconfined compression, and hydrostatic). Tests are run in hydrostatic compaction to the desired mean stress, then differential stress is applied axially in displacement control to failure. The constant mean stress condition is maintained by decreasing the confining pressure by half of the increase in the axial stress. Results will be compared to typical failure criteria to investigate the effectiveness of capturing the behavior of the shale with traditional failure theory. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. SAND2015-6107 A.

  17. The Influence of Shales on Slope Instability

    Science.gov (United States)

    Stead, Doug

    2016-02-01

    Shales play a major role in the stability of slopes, both natural and engineered. This paper attempts to provide a review of the state-of-the-art in shale slope stability. The complexities of shale terminology and classification are first reviewed followed by a brief discussion of the important physical and mechanical properties of relevance to shale slope stability. The varied mechanisms of shale slope stability are outlined and their importance highlighted by reference to international shale slope failures. Stability analysis and modelling of anisotropic rock slope masses are briefly discussed and the potential role of brittle rock fracture and damage highlighted. A short review of shale slopes in open pits is presented.

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

    Science.gov (United States)

    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

  19. Idealized Shale Sorption Isotherm Measurements to Determine Pore Volume, Pore Size Distribution, and Surface Area

    Science.gov (United States)

    Holmes, R.; Wang, B.; Aljama, H.; Rupp, E.; Wilcox, J.

    2014-12-01

    One method for mitigating the impacts of anthropogenic CO2-related climate change is the sequestration of CO2 in depleted gas and oil reservoirs, including shale. The accurate characterization of the heterogeneous material properties of shale, including pore volume, surface area, pore size distributions (PSDs) and composition is needed to understand the interaction of CO2 with shale. Idealized powdered shale sorption isotherms were created by varying incremental amounts of four essential components by weight. The first two components, organic carbon and clay, have been shown to be the most important components for CO2 uptake in shales. Organic carbon was represented by kerogen isolated from a Silurian shale, and clay groups were represented by illite from the Green River shale formation. The rest of the idealized shale was composed of equal parts by weight of SiO2 to represent quartz and CaCO3 to represent carbonate components. Baltic, Eagle Ford, and Barnett shale sorption measurements were used to validate the idealized samples. The idealized and validation shale sorption isotherms were measured volumetrically using low pressure N2 (77K) and CO2 (273K) adsorbates on a Quantachrome Autosorb IQ2. Gravimetric isotherms were also produced for a subset of these samples using CO2 and CH4adsorbates under subsurface temperature and pressure conditions using a Rubotherm magnetic suspension balance. Preliminary analyses were inconclusive in validating the idealized samples. This could be a result of conflicting reports of total organic carbon (TOC) content in each sample, a problem stemming from the heterogeneity of the samples and different techniques used for measuring TOC content. The TOC content of the validation samples (Eagle Ford and Barnett) was measured by Rock-Eval pyrolysis at Weatherford Laboratories, while the TOC content in the Baltic validation samples was determined by LECO TOC. Development of a uniform process for measuring TOC in the validation samples is

  20. Micro Raman spectroscopy of carbonaceous material in microfossils and meteorites: improving a method for life detection.

    Science.gov (United States)

    Bower, D M; Steele, A; Fries, M D; Kater, L

    2013-01-01

    The identification of biosignatures in Earth's ancient rock record and detection of extraplanetary life is one of the primary goals in astrobiology. Intrinsic to this goal is the improvement of analytical techniques and protocols used to identify an unambiguous signal of life. Micro Raman spectroscopy is a nondestructive method that allows for in situ identification of a wide range of minerals and compounds. The use of D (∼1350 cm(-1)) and G (∼1580 cm(-1)) band parameters to infer the biogenicity of carbonaceous materials in fossils has become a commonly used analytical tool, but carbonaceous compounds from different sources often share the same spectroscopic characteristics. Microfossil studies do not always take into consideration a nonbiological source for the carbon in their samples and therefore still rely on morphology as the primary mode of identification. Comprehensive studies that consider all carbon sources are typically done on metasediments, coals, or meteorites, and the results are not clearly applicable to microfossil identification. In this study, microfossils from a suite of sedimentary rock samples of various ages were analyzed with micro Raman spectroscopy to investigate the nature and provenance of carbonaceous material. To further constrain D- and G-band carbon characteristics, micro Raman analyses were also performed on well-characterized meteorite samples as abiological controls. The results appear to show a correlation of precursor carbonaceous material with D-band parameters and thermal history with G-band parameters. This systematic study lays the groundwork for improving the use of the G- and D-band trends as useful indicators of the origin of carbon in microfossils. Before unambiguous biosignatures can be established, further work characterizing the carbonaceous material in microfossils of different ages, thermal histories, and host rock compositions is needed.

  1. Pore Scale Analysis of Oil Shale/Sands Pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Chen-Luh [Univ. of Utah, Salt Lake City, UT (United States); Miller, Jan [Univ. of Utah, Salt Lake City, UT (United States)

    2011-03-01

    There are important questions concerning the quality and volume of pore space that is created when oil shale is pyrolyzed for the purpose of producing shale oil. In this report, 1.9 cm diameter cores of Mahogany oil shale were pyrolyzed at different temperatures and heating rates. Detailed 3D imaging of core samples was done using multiscale X-ray computed tomography (CT) before and after pyrolysis to establish the pore structure. The pore structure of the unreacted material was not clear. Selected images of a core pyrolyzed at 400oC were obtained at voxel resolutions from 39 microns (Οm) to 60 nanometers (nm). Some of the pore space created during pyrolysis was clearly visible at these resolutions and it was possible to distinguish between the reaction products and the host shale rock. The pore structure deduced from the images was used in Lattice Boltzmann simulations to calculate the permeability in the pore space. The permeabilities of the pyrolyzed samples of the silicate-rich zone were on the order of millidarcies, while the permeabilities of the kerogen-rich zone after pyrolysis were very anisotropic and about four orders of magnitude higher.

  2. Organic Substances from Unconventional Oil and Gas Production in Shale

    Science.gov (United States)

    Orem, W. H.; Varonka, M.; Crosby, L.; Schell, T.; Bates, A.; Engle, M.

    2014-12-01

    Unconventional oil and gas (UOG) production has emerged as an important element in the US and world energy mix. Technological innovations in the oil and gas industry, especially horizontal drilling and hydraulic fracturing, allow for the enhanced release of oil and natural gas from shale compared to conventional oil and gas production. This has made commercial exploitation possible on a large scale. Although UOG is enormously successful, there is surprisingly little known about the effects of this technology on the targeted shale formation and on environmental impacts of oil and gas production at the surface. We examined water samples from both conventional and UOG shale wells to determine the composition, source and fate of organic substances present. Extraction of hydrocarbon from shale plays involves the creation and expansion of fractures through the hydraulic fracturing process. This process involves the injection of large volumes of a water-sand mix treated with organic and inorganic chemicals to assist the process and prop open the fractures created. Formation water from a well in the New Albany Shale that was not hydraulically fractured (no injected chemicals) had total organic carbon (TOC) levels that averaged 8 mg/L, and organic substances that included: long-chain fatty acids, alkanes, polycyclic aromatic hydrocarbons, heterocyclic compounds, alkyl benzenes, and alkyl phenols. In contrast, water from UOG production in the Marcellus Shale had TOC levels as high as 5,500 mg/L, and contained a range of organic chemicals including, solvents, biocides, scale inhibitors, and other organic chemicals at thousands of μg/L for individual compounds. These chemicals and TOC decreased rapidly over the first 20 days of water recovery as injected fluids were recovered, but residual organic compounds (some naturally-occurring) remained up to 250 days after the start of water recovery (TOC 10-30 mg/L). Results show how hydraulic fracturing changes the organic

  3. Using Neutrons to Study Fluid-Rock Interactions in Shales

    Science.gov (United States)

    DiStefano, V. H.; McFarlane, J.; Anovitz, L. M.; Gordon, A.; Hale, R. E.; Hunt, R. D.; Lewis, S. A., Sr.; Littrell, K. C.; Stack, A. G.; Chipera, S.; Perfect, E.; Bilheux, H.; Kolbus, L. M.; Bingham, P. R.

    2015-12-01

    Recovery of hydrocarbons by hydraulic fracturing depends on complex fluid-rock interactions that we are beginning to understand using neutron imaging and scattering techniques. Organic matter is often thought to comprise the majority of porosity in a shale. In this study, correlations between the type of organic matter embedded in a shale and porosity were investigated experimentally. Selected shale cores from the Eagle Ford and Marcellus formations were subjected to pyrolysis-gas chromatography, Differential Thermal Analysis/Thermogravimetric analysis, and organic solvent extraction with the resulting affluent analyzed by gas chromatography-mass spectrometry. The pore size distribution of the microporosity (~1 nm to 2 µm) in the Eagle Ford shales was measured before and after solvent extraction using small angle neutron scattering. Organics representing mass fractions of between 0.1 to 1 wt.% were removed from the shales and porosity generally increased across the examined microporosity range, particularly at larger pore sizes, approximately 50 nm to 2 μm. This range reflects extraction of accessible organic material, including remaining gas molecules, bitumen, and kerogen derivatives, indicating where the larger amount of organic matter in shale is stored. An increase in porosity at smaller pore sizes, ~1-3 nm, was also present and could be indicative of extraction of organic material stored in the inter-particle spaces of clays. Additionally, a decrease in porosity after extraction for a sample was attributed to swelling of pores with solvent uptake. This occurred in a shale with high clay content and low thermal maturity. The extracted hydrocarbons were primarily paraffinic, although some breakdown of larger aromatic compounds was observed in toluene extractions. The amount of hydrocarbon extracted and an overall increase in porosity appeared to be primarily correlated with the clay percentage in the shale. This study complements fluid transport neutron

  4. Simultaneous Measurement of Elastic and Electrical Anisotropy of Shales under Elevated Pressure: A Preliminary Study

    Science.gov (United States)

    Ou, L.; Niu, Q.; Prasad, M.

    2015-12-01

    Low-porosity shales are generally considered as transverse isotropic (TI) material, both elastically and electrically. We explore the correlation of elastic and electrical anisotropy of shales to mineralogy and organic richness. Both, elastic and electrical anisotropies in rocks are known to be functions of clay and kerogen contents. The elastic anisotropy in clay- and organic-rich shales is related to their laminated and lenticular texture that is enhanced with compaction and diagenesis leading. The correlation of complex resistivity and anisotropy in shales with clay content has theoretically modeled using cation exchange capacity of the clay minerals. Although, it is appear likely that elastic and electrical anisotropy might be controlled by similar petrophyiscal properties, very little research exists that explores the relationship between these two anisotropies and how petrophysical properties might influence them. We present an experimental data of elastic and electrical anisotropy in shales acquired with a new system that allows simultaneous measurements of acoustic velocities and complex resistivities under hydrostatic pressure in three directions: parallel, 45° and perpendicular to any orientation, such as bedding planes. Our results of five shale samples show: Elastic and electrical anisotropy are inversely related to pressure Electrical anisotropy is generally higher than elastic anisotropy Electrical anisotropy is more sensitive to pressure change Complex resistivity anisotropy for in-phase resistivity and phase is highly frequency dependent In future, we plan to measure shale samples with varying clay and organic contents and correlate anisotropy to petrophysical properties.

  5. Characterization of oil shale, isolated kerogen, and post-pyrolysis residues using advanced 13 solid-state nuclear magnetic resonance spectroscopy

    Science.gov (United States)

    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.

  6. Shipboard measurements of concentrations and properties of carbonaceous aerosols during ACE-2

    OpenAIRE

    2011-01-01

    Mass concentrations of total, organic and black carbon were derived by analyzing the supermicron and submicron aerosol fractions of shipboard collected samples in the easternAtlantic Ocean as part of the second Aerosol Characterization Experiment (ACE-2). These analyses were complemented by experiments intended to estimate the water-soluble fraction of the submicron carbonaceous material. Our results can be summarized as follows. Depending on the sample, between 35% and 80% of total aerosol c...

  7. Mineralogical, geochemical and hydrocarbon potential of subsurface Cretaceous shales, Northern Western Desert, Egypt

    Directory of Open Access Journals (Sweden)

    D.A. Mousa

    2014-03-01

    Full Text Available Twenty four Cretaceous shale core samples of Gibb Afia-1, Betty-1, Salam-1X and Mersa Matruh-1 wells were mineralogically and geochemically studied using XRD, XRF and Rock Eval Pyrolysis. Kaolinite, smectite and illite are the main clay minerals in addition to rare chlorite, while the non-clay minerals include quartz, calcite, dolomite and rare siderite. The shales were derived through intensive chemical weathering of mafic basement and older sedimentary rocks. These sediments were deposited in a near-shore shallow marine environment with some terrestrial material input. The shales have poor to fair organic content. It is marginally to rarely mature.

  8. The atmospheric inventory of Xenon and noble cases in shales The plastic bag experiment

    Science.gov (United States)

    Bernatowicz, T. J.; Podosek, F. A.; Honda, M.; Kramer, F. E.

    1984-01-01

    A novel trapped gas analysis protocol is applied to five shales in which the samples are sealed in air to eliminate the possibility of gas loss in the preanalysis laboratory vacuum exposure of a conventional protocol. The test is aimed at a determination concerning the hypothesis that atmospheric noble gases occur in the same proportion as planetary gases in meteorites, and that the factor-of-23 deficiency of air Xe relative to planetary Xe is made up by Xe stored in shales or other sedimentary rocks. The results obtained do not support the shale hypothesis.

  9. Carbonaceous Aerosols in Fine Particulate Matter of Santiago Metropolitan Area, Chile

    Science.gov (United States)

    Toro Araya, Richard; Flocchini, Robert; Morales Segura, Rául G. E.; Leiva Guzmán, Manuel A.

    2014-01-01

    Measurements of carbonaceous aerosols in South American cities are limited, and most existing data are of short term and limited to only a few locations. For 6 years (2002–2007), concentrations of fine particulate matter and organic and elemental carbon were measured continuously in the capital of Chile. The contribution of carbonaceous aerosols to the primary and secondary fractions was estimated at three different sampling sites and in the warm and cool seasons. The results demonstrate that there are significant differences in the levels in both the cold (March to August) and warm (September to February) seasons at all sites studied. The percent contribution of total carbonaceous aerosol fine particulate matter was greater in the cool season (53 ± 41%) than in the warm season (44 ± 18%). On average, the secondary organic carbon in the city corresponded to 29% of the total organic carbon. In cold periods, this proportion may reach an average of 38%. A comparison of the results with the air quality standards for fine particulate matter indicates that the total carbonaceous fraction alone exceeds the World Health Organization standard (10 µg/m3) and the United States Environmental Protection Agency standard (15 µg/m3) for fine particulate matter. PMID:24587753

  10. Spectro-Microscopic Measurements of Carbonaceous Aerosol Aging in Central California

    Energy Technology Data Exchange (ETDEWEB)

    Moffet, Ryan C.; Rodel, Tobias; Kelly, Stephen T.; Yu, Xiao-Ying; Carroll, Gregory; Fast, Jerome D.; Zaveri, Rahul A.; Laskin, Alexander; Gilles, Mary K.

    2013-10-29

    Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES) was designed to study carbonaceous aerosols in the natural environment of Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of pollution accumulation event (June 27-29, 2010), when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX) and scanning transmission X-ray microscopy coupled with near edge X-ray absorption spectroscopy (STXM/NEXAFS) were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm diameter) increased with plume age as did the organic mass per particle. Comparison of the CARES spectro-microscopic data set with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that individual particles in Mexico City contained twice as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (30%) was larger than at the CARES urban site (10%) and the most aged samples from CARES contained less carbon-carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed results provided by these spectro-microscopic measurements

  11. Spectro-microscopic measurements of carbonaceous aerosol aging in Central California

    Directory of Open Access Journals (Sweden)

    R. C. Moffet

    2013-04-01

    Full Text Available Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES was designed to study carbonaceous aerosols in the natural environment of Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of pollution accumulation event (27–29 June 2010, when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX and scanning transmission X-ray microscopy coupled with near edge X-ray absorption spectroscopy (STXM/NEXAFS were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm diameter increased with plume age as did the organic mass per particle. Comparison of the CARES spectro-microscopic data set with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that individual particles in Mexico City contained twice as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (30% was larger than at the CARES urban site (10% and the most aged samples from CARES contained less carbon-carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed results provided by these spectro

  12. Spectro-microscopic measurements of carbonaceous aerosol aging in Central California

    Science.gov (United States)

    Moffet, R. C.; Rödel, T. C.; Kelly, S. T.; Yu, X. Y.; Carroll, G. T.; Fast, J.; Zaveri, R. A.; Laskin, A.; Gilles, M. K.

    2013-10-01

    Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES) was designed to study carbonaceous aerosols in the natural environment of the Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of a pollution accumulation event (27-29 June 2010), when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer-controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX) and scanning transmission X-ray microscopy coupled with near-edge X-ray absorption spectroscopy (STXM/NEXAFS) were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm equivalent circular diameter) increased with plume age, as did the organic mass per particle. Comparison of the CARES spectro-microscopic dataset with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that fresh particles in Mexico City contained three times as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (ranging from 16.6 to 47.3%) was larger than at the CARES urban site (13.4-15.7%), and the most aged samples from CARES contained fewer carbon-carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed

  13. Shale Oil Value Enhancement Research

    Energy Technology Data Exchange (ETDEWEB)

    James W. Bunger

    2006-11-30

    Raw kerogen oil is rich in heteroatom-containing compounds. Heteroatoms, N, S & O, are undesirable as components of a refinery feedstock, but are the basis for product value in agrochemicals, pharmaceuticals, surfactants, solvents, polymers, and a host of industrial materials. An economically viable, technologically feasible process scheme was developed in this research that promises to enhance the economics of oil shale development, both in the US and elsewhere in the world, in particular Estonia. Products will compete in existing markets for products now manufactured by costly synthesis routes. A premium petroleum refinery feedstock is also produced. The technology is now ready for pilot plant engineering studies and is likely to play an important role in developing a US oil shale industry.

  14. Chiral Biomarkers and Microfossils in Carbonaceous Meteorites

    Science.gov (United States)

    Hoover, Richard B.

    2010-01-01

    Homochirality of the biomolecules (D-sugars of DNA and RNA and L-amino acids of proteins) is a fundamental property of all life on Earth. Abiotic mechanisms yield racemic mixtures (D/L=1) of chiral molecules and after the death of an organism, the enantiopure chiral biomolecules slowly racemize. Several independent investigators have now established that the amino acids present in CI1 and CM2 carbonaceous meteorites have a moderate to strong excess of the L-enantiomer. Stable isotope data have established that these amino acids are both indigenous and extraterrestrial. Carbonaceous meteorites also contain many other strong chemical biomarkers including purines and pyrimidines (nitrogen heterocycles of nucleic acids); pristine and phytane (components of the chlorophyll pigment) and morphological biomarkers (microfossils of filamentous cyanobacteria). Energy dispersive X-ray Spectroscopy (EDS) analysis reveals that nitrogen is below the detectability level in most of the meteorite filaments as well as in Cambrian Trilobites and filaments of 2.7 Gya Archaean cyanobacteria from Karelia. The deficiency of nitrogen in the filaments and the total absence of sugars, of twelve of the life-critical protein amino acids, and two of the nucleobases of DNA and RNA provide clear and convincing evidence that these filaments are not modern biological contaminants. This paper reviews the chiral, chemical biomarkers morphological biomarkers and microfossils in carbonaceous meteorites. This paper reviews chiral and morphological biomarkers and discusses the missing nitrogen, sugars, protein amino acids, and nucleobases as ?bio-discriminators? that exclude modern biological contaminants as a possible explanation for the permineralized cyanobacterial filaments found in the meteorites.

  15. Chiral biomarkers and microfossils in carbonaceous meteorites

    Science.gov (United States)

    Hoover, Richard B.

    2010-09-01

    Homochirality of the biomolecules (D-sugars of DNA and RNA and L-amino acids of proteins) is a fundamental property of all life on Earth. Abiotic mechanisms yield racemic mixtures (D/L=1) of chiral molecules and after the death of an organism, the enantiopure chiral biomolecules slowly racemize. Several independent investigators have now established that the amino acids present in CI1 and CM2 carbonaceous meteorites have a moderate to strong excess of the L-enantiomer. Stable isotope data have established that these amino acids are both indigenous and extraterrestrial. Carbonaceous meteorites also contain many other strong chemical biomarkers including purines and pyrimidines (nitrogen heterocycles of nucleic acids); pristine and phytane (components of the chlorophyll pigment) and morphological biomarkers (microfossils of filamentous cyanobacteria). Energy dispersive X-ray Spectroscopy (EDS) analysis reveals that nitrogen is below the detectability level in most of the meteorite filaments as well as in Cambrian Trilobites and filaments of 2.7 Gya Archaean cyanobacteria from Karelia. The deficiency of nitrogen in the filaments and the total absence of sugars, of twelve of the life-critical protein amino acids, and two of the nucleobases of DNA and RNA provide clear and convincing evidence that these filaments are not modern biological contaminants. This paper reviews the chiral, chemical biomarkers morphological biomarkers and microfossils in carbonaceous meteorites. This paper reviews chiral and morphological biomarkers and discusses the missing nitrogen, sugars, protein amino acids, and nucleobases as "bio-discriminators" that exclude modern biological contaminants as a possible explanation for the permineralized cyanobacterial filaments found in the meteorites.

  16. Fossil Diatoms in a New Carbonaceous Meteorite

    Science.gov (United States)

    Wickramasinghe, N. C.; Wallis, J.; Wallis, D. H.; Samaranayake, Anil

    2013-01-01

    We report the discovery for the first time of diatom frustules in a carbonaceous meteorite that fell in the North Central Province of Sri Lanka on 29 December 2012. Contamination is excluded by the circumstance that the elemental abundances within the structures match closely with those of the surrounding matrix. There is also evidence of structures morphologically similar to red rain cells that may have contributed to the episode of red rain that followed within days of the meteorite fall. The new data on "fossil" diatoms provide strong evidence to support the theory of cometary panspermia.

  17. Mechanism for Burgess Shale-type preservation

    DEFF Research Database (Denmark)

    Gaines, Robert R.; Hammarlund, Emma U.; Hou, Xianguang;

    2012-01-01

    Exceptionally preserved fossil biotas of the Burgess Shale and a handful of other similar Cambrian deposits provide rare but critical insights into the early diversification of animals. The extraordinary preservation of labile tissues in these geographically widespread but temporally restricted...... soft-bodied fossil assemblages has remained enigmatic since Walcott's initial discovery in 1909. Here, we demonstrate the mechanism of Burgess Shale-type preservation using sedimentologic and geochemical data from the Chengjiang, Burgess Shale, and five other principal Burgess Shale-type deposits......, provided by bed-capping cements that were emplaced at the seafloor, is a feature that is shared among Burgess Shale-type deposits, and resulted from the unusually high alkalinity of Cambrian oceans. Thus, Burgess Shale-type preservation of soft-bodied fossil assemblages worldwide was promoted by unique...

  18. Mechanism for Burgess Shale-type preservation

    DEFF Research Database (Denmark)

    Gaines, Robert R.; Hammarlund, Emma U.; Hou, Xianguang

    2012-01-01

    Exceptionally preserved fossil biotas of the Burgess Shale and a handful of other similar Cambrian deposits provide rare but critical insights into the early diversification of animals. The extraordinary preservation of labile tissues in these geographically widespread but temporally restricted...... soft-bodied fossil assemblages has remained enigmatic since Walcott's initial discovery in 1909. Here, we demonstrate the mechanism of Burgess Shale-type preservation using sedimentologic and geochemical data from the Chengjiang, Burgess Shale, and five other principal Burgess Shale-type deposits......, provided by bed-capping cements that were emplaced at the seafloor, is a feature that is shared among Burgess Shale-type deposits, and resulted from the unusually high alkalinity of Cambrian oceans. Thus, Burgess Shale-type preservation of soft-bodied fossil assemblages worldwide was promoted by unique...

  19. Field and Lab-Based Microbiological Investigations of the Marcellus Shale

    Science.gov (United States)

    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

  20. Appraisal of transport and deformation in shale reservoirs using natural noble gas tracers

    Energy Technology Data Exchange (ETDEWEB)

    Heath, Jason E. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Kuhlman, Kristopher L. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Robinson, David G. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Bauer, Stephen J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Gardner, William Payton [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Univ. of Montana, Missoula, MT (United States)

    2015-09-01

    This report presents efforts to develop the use of in situ naturally-occurring noble gas tracers to evaluate transport mechanisms and deformation in shale hydrocarbon reservoirs. Noble gases are promising as shale reservoir diagnostic tools due to their sensitivity of transport to: shale pore structure; phase partitioning between groundwater, liquid, and gaseous hydrocarbons; and deformation from hydraulic fracturing. Approximately 1.5-year time-series of wellhead fluid samples were collected from two hydraulically-fractured wells. The noble gas compositions and isotopes suggest a strong signature of atmospheric contribution to the noble gases that mix with deep, old reservoir fluids. Complex mixing and transport of fracturing fluid and reservoir fluids occurs during production. Real-time laboratory measurements were performed on triaxially-deforming shale samples to link deformation behavior, transport, and gas tracer signatures. Finally, we present improved methods for production forecasts that borrow statistical strength from production data of nearby wells to reduce uncertainty in the forecasts.

  1. Beyond the Burgess Shale: Cambrian microfossils track the rise and fall of hallucigeniid lobopodians.

    Science.gov (United States)

    Caron, Jean-Bernard; Smith, Martin R; Harvey, Thomas H P

    2013-09-22

    Burgess Shale-type deposits are renowned for their exquisite preservation of soft-bodied organisms, representing a range of animal body plans that evolved during the Cambrian 'explosion'. However, the rarity of these fossil deposits makes it difficult to reconstruct the broader-scale distributions of their constituent organisms. By contrast, microscopic skeletal elements represent an extensive chronicle of early animal evolution--but are difficult to interpret in the absence of corresponding whole-body fossils. Here, we provide new observations on the dorsal spines of the Cambrian lobopodian (panarthropod) worm Hallucigenia sparsa from the Burgess Shale (Cambrian Series 3, Stage 5). These exhibit a distinctive scaly microstructure and layered (cone-in-cone) construction that together identify a hitherto enigmatic suite of carbonaceous and phosphatic Cambrian microfossils--including material attributed to Mongolitubulus, Rushtonites and Rhombocorniculum--as spines of Hallucigenia-type lobopodians. Hallucigeniids are thus revealed as an important and widespread component of disparate Cambrian communities from late in the Terreneuvian (Cambrian Stage 2) through the 'middle' Cambrian (Series 3); their apparent decline in the latest Cambrian may be partly taphonomic. The cone-in-cone construction of hallucigeniid sclerites is shared with the sclerotized cuticular structures (jaws and claws) in modern onychophorans. More generally, our results emphasize the reciprocal importance and complementary roles of Burgess Shale-type fossils and isolated microfossils in documenting early animal evolution.

  2. A new Burgess Shale-type deposit from the Ediacaran of western Mongolia

    Science.gov (United States)

    Dornbos, Stephen Q.; Oji, Tatsuo; Kanayama, Akihiro; Gonchigdorj, Sersmaa

    2016-03-01

    Preservation of soft-bodied organisms is exceedingly rare in the fossil record. One way that such fossils are preserved is as carbonaceous compressions in fined-grained marine sedimentary rocks. These deposits of exceptional preservation are known as Burgess Shale-type (BST) deposits. During the Cambrian Period, BST deposits are more common and provide a crucial view of early animal evolution. The earliest definitive fossil evidence for macroscopic animal-grade organisms is found in the preceding Ediacaran Period. BST deposits from the Ediacaran are rarer and lack conclusive evidence for animals. Here we report the discovery of a new Ediacaran BST deposit with exceptional preservation of non-mineralizing macro-organisms in thinly bedded black shale from Zavkhan Province, western Mongolia. This fossil assemblage, here named the Zuun-Arts biota, currently consists of two new species of probable macroscopic multicellular benthic algae. One species, Chinggiskhaania bifurcata n. gen., n. sp., dominates the biota. The other species, Zuunartsphyton delicatum n. gen., n. sp., is known from three specimens. SEM-EDS analysis shows that the fossils are composed of aluminosilicate clay minerals and some carbon, a composition comparable to fossils from the Cambrian Burgess Shale biota. This discovery opens a new window through which to view late Precambrian life.

  3. Nanoscale simulation of shale transport properties using the lattice Boltzmann method: permeability and diffusivity

    Science.gov (United States)

    Chen, Li; Zhang, Lei; Kang, Qinjun; Viswanathan, Hari S.; Yao, Jun; Tao, Wenquan

    2015-01-01

    Porous structures of shales are reconstructed using the markov chain monte carlo (MCMC) method based on scanning electron microscopy (SEM) images of shale samples from Sichuan Basin, China. Characterization analysis of the reconstructed shales is performed, including porosity, pore size distribution, specific surface area and pore connectivity. The lattice Boltzmann method (LBM) is adopted to simulate fluid flow and Knudsen diffusion within the reconstructed shales. Simulation results reveal that the tortuosity of the shales is much higher than that commonly employed in the Bruggeman equation, and such high tortuosity leads to extremely low intrinsic permeability. Correction of the intrinsic permeability is performed based on the dusty gas model (DGM) by considering the contribution of Knudsen diffusion to the total flow flux, resulting in apparent permeability. The correction factor over a range of Knudsen number and pressure is estimated and compared with empirical correlations in the literature. For the wide pressure range investigated, the correction factor is always greater than 1, indicating Knudsen diffusion always plays a role on shale gas transport mechanisms in the reconstructed shales. Specifically, we found that most of the values of correction factor fall in the slip and transition regime, with no Darcy flow regime observed. PMID:25627247

  4. Observations of the release of non-methane hydrocarbons from fractured shale.

    Science.gov (United States)

    Sommariva, Roberto; Blake, Robert S; Cuss, Robert J; Cordell, Rebecca L; Harrington, Jon F; White, Iain R; Monks, Paul S

    2014-01-01

    The organic content of shale has become of commercial interest as a source of hydrocarbons, owing to the development of hydraulic fracturing ("fracking"). While the main focus is on the extraction of methane, shale also contains significant amounts of non-methane hydrocarbons (NMHCs). We describe the first real-time observations of the release of NMHCs from a fractured shale. Samples from the Bowland-Hodder formation (England) were analyzed under different conditions using mass spectrometry, with the objective of understanding the dynamic process of gas release upon fracturing of the shale. A wide range of NMHCs (alkanes, cycloalkanes, aromatics, and bicyclic hydrocarbons) are released at parts per million or parts per billion level with temperature- and humidity-dependent release rates, which can be rationalized in terms of the physicochemical characteristics of different hydrocarbon classes. Our results indicate that higher energy inputs (i.e., temperatures) significantly increase the amount of NMHCs released from shale, while humidity tends to suppress it; additionally, a large fraction of the gas is released within the first hour after the shale has been fractured. These findings suggest that other hydrocarbons of commercial interest may be extracted from shale and open the possibility to optimize the "fracking" process, improving gas yields and reducing environmental impacts.

  5. Fractured shale gas potential in New York

    Energy Technology Data Exchange (ETDEWEB)

    Hill, D.G.; Lombardi, T.E. [Ticora Geosciences Inc., Arvada, CO (United States); Martin, J.P. [New York State Energy Research and Development Authority, Albany, NY (United States)

    2002-07-01

    The history of gas production in the Devonian and Silurian age shales of New York dates back 180 years with the discovery of hundreds of shallow shale wells along the Lake Erie shoreline. Although the resource potential for shale gas in New York is large, ranging from 163-313 trillion cubic feet, it has not been a major contributor to natural gas production in the state. Ordovician Utica shale may also hold potential as a new commercial shale gas reservoir. More than 20,000 Devonian shale wells are currently producing in the Appalachian Basin. Experience has shown that each shale play is unique and requires solutions to problems associated with commercial production that are unique to each play. The authors note that continued examination of the shale potential in New York is warranted, although more information is needed to address geological and reservoir properties in the shale, including resource distribution, natural fracture patterns, and limitations of the reservoir. Devonian shales have been recognized as a major gas resource that require advanced production methods for recovery. This paper described the depositional environment and thickness of black shale sequences in the Appalachian Basin, which consists of an alluvial plain, a shelf-delta front, the base of the slope, and the deep basin. The extensive natural fractures which are oriented in an east-north direction are considered to be potential conduits for hydrocarbon flow. The amount of organic carbon in the rock also contributes to the natural gas storage through either adsorption or solution within the reservoir system. This paper also outlines strategies for exploration and development of fractured gas shale reservoirs. It was suggested that exploration strategies should focus on finding areas that have significant natural gas resources as well as sufficient permeability for economic production. 94 refs., 21 tabs., 24 figs.

  6. Characteristics of deltaic deposits in the Cretaceous Pierre Shale, Trinidad Sandstone, and Vermejo Formation, Raton Basin, Colorado.

    Science.gov (United States)

    Flores, R.M.; Tur, S.M.

    1982-01-01

    Detailed facies analyses of closely spaced measured surface sections in the Trinidad and adjacent areas of Colorado reflect deposition in the river-influenced delta. That this deltaic system was accompanied by abandonment of subdeltas is indicated by a destructional-deltaic facies of heavily bioturbated, carbonaceous sandstones, siltstones, and shales best recorded in the delta front deposits of the Trinidad Sandstone. Coal accumulation of the Vermejo deposits nevertheless remained primarily controlled by persistent organic sedimentation in interdistributary backswamps. These backswamps, which accumulated thick, lenticular coals, were formed during the normal constructional phase of the delta plain. -from Authors

  7. Detailed description of oil shale organic and mineralogical heterogeneity via fourier transform infrared mircoscopy

    Science.gov (United States)

    Washburn, Kathryn E.; Birdwell, Justin E.; Foster, Michael; Gutierrez, Fernando

    2015-01-01

    Mineralogical and geochemical information on reservoir and source rocks is necessary to assess and produce from petroleum systems. The standard methods in the petroleum industry for obtaining these properties are bulk measurements on homogenized, generally crushed, and pulverized rock samples and can take from hours to days to perform. New methods using Fourier transform infrared (FTIR) spectroscopy have been developed to more rapidly obtain information on mineralogy and geochemistry. However, these methods are also typically performed on bulk, homogenized samples. We present a new approach to rock sample characterization incorporating multivariate analysis and FTIR microscopy to provide non-destructive, spatially resolved mineralogy and geochemistry on whole rock samples. We are able to predict bulk mineralogy and organic carbon content within the same margin of error as standard characterization techniques, including X-ray diffraction (XRD) and total organic carbon (TOC) analysis. Validation of the method was performed using two oil shale samples from the Green River Formation in the Piceance Basin with differing sedimentary structures. One sample represents laminated Green River oil shales, and the other is representative of oil shale breccia. The FTIR microscopy results on the oil shales agree with XRD and LECO TOC data from the homogenized samples but also give additional detail regarding sample heterogeneity by providing information on the distribution of mineral phases and organic content. While measurements for this study were performed on oil shales, the method could also be applied to other geological samples, such as other mudrocks, complex carbonates, and soils.

  8. A perspective on Canadian shale gas

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Mike; Davidson, Jim; Mortensen, Paul

    2010-09-15

    In a relatively new development over just the past few years, shale formations are being targeted for natural gas production. Based on initial results, there may be significant potential for shale gas in various regions of Canada, not only in traditional areas of conventional production but also non-traditional areas. However, there is much uncertainty because most Canadian shale gas production is currently in experimental or early developmental stages. Thus, its full potential will not be known for some time. If exploitation proves to be successful, Canadian shale gas may partially offset projected long-term declines in Canadian conventional natural gas production.

  9. A perspective on Canadian shale gas

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Mike; Davidson, Jim; Mortensen, Paul

    2010-09-15

    In a relatively new development over just the past few years, shale formations are being targeted for natural gas production. Based on initial results, there may be significant potential for shale gas in various regions of Canada, not only in traditional areas of conventional production but also non-traditional areas. However, there is much uncertainty because most Canadian shale gas production is currently in experimental or early developmental stages. Thus, its full potential will not be known for some time. If exploitation proves to be successful, Canadian shale gas may partially offset projected long-term declines in Canadian conventional natural gas production.

  10. Chemical analysis of organic molecules in carbonaceous meteorites

    NARCIS (Netherlands)

    Torrao Pinto Martins, Zita Carla

    2007-01-01

    Meteorites are extraterrestrial objects that survive the passage through the Earth’s atmosphere and impact the Earth's surface. They can be divided into several classes, the carbonaceous chondrites being one of them. Carbonaceous chondrites are the oldest and best preserved meteorites and contain a

  11. Chemical analysis of organic molecules in carbonaceous meteorites

    NARCIS (Netherlands)

    Torrao Pinto Martins, Zita Carla

    2007-01-01

    Meteorites are extraterrestrial objects that survive the passage through the Earth’s atmosphere and impact the Earth's surface. They can be divided into several classes, the carbonaceous chondrites being one of them. Carbonaceous chondrites are the oldest and best preserved meteorites and contain a

  12. Organic geochemical characterization of Aleksinac oil shale deposit (Serbia)

    Science.gov (United States)

    Gajica, Gordana; Kašanin-Grubin, Milica; Šajnović, Aleksandra; Stojanović, Ksenija; Kostić, Aleksandar; Jovančićević, Branimir

    2016-04-01

    Oil shales represent a good source of energy and industrial raw material. The Aleksinac oil shale deposit is the biggest and most important oil shale deposit in Serbia. It covers an area of over 20 km2, and it has three fields: "Dubrava", "Morava" and "Logorište". The potential reserves of oil shale in the Aleksinac deposit are estimated at about 2.1 billion tons. The genesis of oil shales is associated with the lacustrine depositional environments, which existed from Upper to Lower Miocene. In order to determine the generative potential, type of organic matter (OM) and thermal maturity, Rock-Eval pyrolysis was used. In analyzed oil shale samples the content of total organic carbon (TOC), as a general indicator of petroleum generation potential, range from 1.48 to 29.57%. The content of naturally generated hydrocarbons, expressed as S1 peak from the Rock-Eval pyrolysis in most analyzed samples have extremely low values 0.002-0.28, which indicate low maturity level [1]. The pyrolysable hydrocarbons expressed as S2 peak from the Rock-Eval pyrolysis, represent the potential to generate hydrocarbons and with that the potential of oil generation through thermal decomposition of kerogen. S2 ranging 3.93-141.36 mg HC/g rock is higher than 20 mg HC/g rock and indicates excellent source rock potential [1]. In order to accept a formation as a source rock, it should exhibit TOC more than 0.5 % and sufficient maturity, but also OM types should be suitable for the oil and gas generation. The kerogen type is determined by Hydrogen Index (HI) and diagram HI vs. Tmax (temperature, corresponding to S2 peak maximum). HI in range 265-728 mg HC/g TOC, indicates Type I and Type II kerogen or their mixture i.e. oil prone kerogen [1], whereas only one sample appears to be oil/gas prone (Type II/III). Similar results are obtained by plotting the Tmax against HI. Maturation degree depends on the overall thermal history of the evaluated rocks; it is very important parameter for evaluation

  13. ANALYSIS OF DEVONIAN BLACK SHALES IN KENTUCKY FOR POTENTIAL CARBON DIOXIDE SEQUESTRATION AND ENHANCED NATURAL GAS PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall

    2003-02-11

    Proposed carbon management technologies include geologic sequestration of CO{sub 2}. A possible, but untested, strategy is to inject CO{sub 2} into organic-rich shales of Devonian age. Devonian black shales underlie approximately two-thirds of Kentucky and are generally thicker and deeper in the Illinois and Appalachian Basin portions of Kentucky. The Devonian black shales serve as both the source and trap for large quantities of natural gas; total gas in place for the shales in Kentucky is estimated to be between 63 and 112 trillion cubic feet. Most of this natural gas is adsorbed on clay and kerogen surfaces, analogous to the way methane is stored in coal beds. In coals, it has been demonstrated that CO{sub 2} is preferentially adsorbed, displacing methane at a ratio of two to one. Black shales may similarly desorb methane in the presence of CO{sub 2}. If black shales similarly desorb methane in the presence of CO{sub 2}, the shales may be an excellent sink for CO{sub 2} with the added benefit of serving to enhance natural gas production. The concept that black, organic-rich Devonian shales could serve as a significant geologic sink for CO{sub 2} is the subject this research. To accomplish this investigation, drill cuttings and cores will be selected from the Kentucky Geological Survey Well Sample and Core Library. CO{sub 2} adsorption analyses will be performed in order to determine the gas-storage potential of the shale and to identify shale facies with the most sequestration potential. In addition, new drill cuttings and sidewall core samples will be acquired to investigate specific black-shale facies, their uptake of CO{sub 2}, and the resultant displacement of methane. Advanced logging techniques (elemental capture spectroscopy) will be used to investigate possible correlations between adsorption capacity and geophysical log measurements.

  14. ANALYSIS OF DEVONIAN BLACK SHALES IN KENTUCKY FOR POTENTIAL CARBON DIOXIDE SEQUESTRATION AND ENHANCED NATURAL GAS PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall

    2003-02-10

    Proposed carbon management technologies include geologic sequestration of CO{sub 2}. A possible, but untested, strategy is to inject CO{sub 2} into organic-rich shales of Devonian age. Devonian black shales underlie approximately two-thirds of Kentucky and are generally thicker and deeper in the Illinois and Appalachian Basin portions of Kentucky. The Devonian black shales serve as both the source and trap for large quantities of natural gas; total gas in place for the shales in Kentucky is estimated to be between 63 and 112 trillion cubic feet. Most of this natural gas is adsorbed on clay and kerogen surfaces, analogous to the way methane is stored in coal beds. In coals, it has been demonstrated that CO{sub 2} is preferentially adsorbed, displacing methane at a ratio of two to one. Black shales may similarly desorb methane in the presence of CO{sub 2}. If black shales similarly desorb methane in the presence of CO{sub 2}, the shales may be an excellent sink for CO{sub 2} with the added benefit of serving to enhance natural gas production. The concept that black, organic-rich Devonian shales could serve as a significant geologic sink for CO{sub 2} is the subject this research. To accomplish this investigation, drill cuttings and cores will be selected from the Kentucky Geological Survey Well Sample and Core Library. CO{sub 2} adsorption analyses will be performed in order to determine the gas-storage potential of the shale and to identify shale facies with the most sequestration potential. In addition, new drill cuttings and sidewall core samples will be acquired to investigate specific black-shale facies, their uptake of CO{sub 2}, and the resultant displacement of methane. Advanced logging techniques (elemental capture spectroscopy) will be used to investigate possible correlations between adsorption capacity and geophysical log measurements.

  15. ANALYSIS OF DEVONIAN BLACK SHALES IN KENTUCKY FOR POTENTIAL CARBON DIOXIDE SEQUESTRATION AND ENHANCED NATURAL GAS PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall

    2003-04-28

    Proposed carbon management technologies include geologic sequestration of CO{sub 2}. A possible, but untested, strategy is to inject CO{sub 2} into organic-rich shales of Devonian age. Devonian black shales underlie approximately two-thirds of Kentucky and are generally thicker and deeper in the Illinois and Appalachian Basin portions of Kentucky. The Devonian black shales serve as both the source and trap for large quantities of natural gas; total gas in place for the shales in Kentucky is estimated to be between 63 and 112 trillion cubic feet. Most of this natural gas is adsorbed on clay and kerogen surfaces, analogous to the way methane is stored in coal beds. In coals, it has been demonstrated that CO{sub 2} is preferentially adsorbed, displacing methane at a ratio of two to one. Black shales may similarly desorb methane in the presence of CO{sub 2}. If black shales similarly desorb methane in the presence of CO{sub 2}, the shales may be an excellent sink for CO{sub 2} with the added benefit of serving to enhance natural gas production. The concept that black, organic-rich Devonian shales could serve as a significant geologic sink for CO{sub 2} is the subject this research. To accomplish this investigation, drill cuttings and cores will be selected from the Kentucky Geological Survey Well Sample and Core Library. CO{sub 2} adsorption analyses will be performed in order to determine the gas-storage potential of the shale and to identify shale facies with the most sequestration potential. In addition, new drill cuttings and sidewall core samples will be acquired to investigate specific black-shale facies, their uptake of CO{sub 2}, and the resultant displacement of methane. Advanced logging techniques (elemental capture spectroscopy) will be used to investigate possible correlations between adsorption capacity and geophysical log measurements.

  16. Carbonaceous Dye-Sensitized Solar Cell Photoelectrodes.

    Science.gov (United States)

    Batmunkh, Munkhbayar; Biggs, Mark J; Shapter, Joseph G

    2015-03-01

    High photovoltaic efficiency is one of the most important keys to the commercialization of dye sensitized solar cells (DSSCs) in the quickly growing renewable electricity generation market. The heart of the DSSC system is a wide bandgap semiconductor based photoelectrode film that helps to adsorb dye molecules and transport the injected electrons away into the electrical circuit. However, charge recombination, poor light harvesting efficiency and slow electron transport of the nanocrystalline oxide photoelectrode film are major issues in the DSSC's performance. Recently, semiconducting composites based on carbonaceous materials (carbon nanoparticles, carbon nanotubes (CNTs), and graphene) have been shown to be promising materials for the photoelectrode of DSSCs due to their fascinating properties and low cost. After a brief introduction to development of nanocrystalline oxide based films, this Review outlines advancements that have been achieved in the application of carbonaceous-based materials in the photoelectrode of DSSCs and how these advancements have improved performance. In addition, several of the unsolved issues in this research area are discussed and some important future directions are also highlighted.

  17. Keto-acids in Carbonaceous Meteorites

    Science.gov (United States)

    Cooper, G.; Chang, P. M.; Dugas, A.; Byrd, A.; Chang, P. M.; Washington, N.

    2005-01-01

    The Murchison and Murray meteorites are the best-characterized carbonaceous meteorites with respect to organic chemistry and are generally used as references for organic compounds in extraterrestrial material. Among the classes of organic compounds found in these meteorites are amino acids, carboxylic acids, hydroxy acids, purines, and pyrimidines. Such compounds, important in contemporary biochemistry, are thought to have been delivered to the early Earth in asteroids and comets and may have played a role in early life and/or the origin of life. Absent among (today's) critically important biological compounds reported in carbonaceous meteorites are keto acids, i.e., pyruvic acid, acetoacetic acid, and higher homologs. These compounds are key intermediates in such critical processes as glycolysis and the citric acid cycle. In this study several individual meteoritic keto acids were identified by gas chromatography-mass spectrometry (GC-MS) (see figure below). All compounds were identified as their trimethylsilyl (TMS), isopropyl ester (ISP), and tert-butyldimethylsilyl (tBDMS) derivatives. In general, the compounds follow the abiotic synthesis pattern of other known meteorite classes of organic compounds [1,2]: a general decrease in abundance with increasing carbon number within a class of compounds and many, if not all, possible isomers present at a given carbon number. The majority of the shown compounds was positively identified by comparison of their mass spectra to commercially available standards or synthesized standards.

  18. Oil shale, shale oil, shale gas and non-conventional hydrocarbons

    Directory of Open Access Journals (Sweden)

    Clerici A.

    2015-01-01

    Full Text Available In recent years there has been a world “revolution” in the field of unconventional hydrocarbon reserves, which goes by the name of “shale gas”, gas contained inside clay sediments micropores. Shale gas finds particular development in the United States, which are now independent of imports and see a price reduction to less than one third of that in Europe. With the high oil prices, in addition to the non-conventional gas also “oil shales” (fine-grained sedimentary rocks that contain a large amount of organic material to be used both to be directly burned or to extract liquid fuels which go under the name of shale oil, extra heavy oils and bitumen are becoming an industrial reality. Both unconventional gas and oil reserves far exceed in the world the conventional oil and gas reserves, subverting the theory of fossil fuels scarcity. Values and location of these new fossil reserves in different countries and their production by comparison with conventional resources are presented. In view of the clear advantages of unconventional fossil resources, the potential environmental risks associated with their extraction and processing are also highlighted.

  19. Size dependent pore size distribution of shales by gas physisorption

    Science.gov (United States)

    Roshan, Hamid; Andersen, Martin S.; Yu, Lu; Masoumi, Hossein; Arandian, Hamid

    2017-04-01

    Gas physisorption, in particular nitrogen adsorption-desorption, is a traditional technique for characterization of geomaterials including the organic rich shales. The low pressure nitrogen is used together with adsorption-desorption physical models to study the pore size distribution (PSD) and porosity of the porous samples. The samples are usually crushed to a certain fragment size to measure these properties however there is not yet a consistent standard size proposed for sample crushing. Crushing significantly increases the surface area of the fragments e.g. the created surface area is differentiated from that of pores using BET technique. In this study, we show that the smaller fragment sizes lead to higher cumulative pore volume and smaller pore diameters. It is also shown that some of the micro-pores are left unaccounted because of the correction of the external surface area. In order to illustrate this, the nitrogen physisorption is first conducted on the identical organic rich shale samples with different sizes: 20-25, 45-50 and 63-71 µm. We then show that such effects are not only a function of pore structure changes induced by crushing, but is linked to the inability of the physical models in differentiating between the external surface area (BET) and micro-pores for different crushing sizes at relatively low nitrogen pressure. We also discuss models currently used in nano-technology such as t-method to address this issue and their advantages and shortcoming for shale rock characterization.

  20. Ion Irradiation Experiments on the Murchison CM2 Carbonaceous Chondrite: Simulating Space Weathering of Primitive Asteroids

    Science.gov (United States)

    Keller, L. P.; Christoffersen, R.; Dukes, C. A.; Baragiola, R. A.; Rahman, Z.

    2015-01-01

    Remote sensing observations show that space weathering processes affect all airless bodies in the Solar System to some degree. Sample analyses and lab experiments provide insights into the chemical, spectroscopic and mineralogic effects of space weathering and aid in the interpretation of remote- sensing data. For example, analyses of particles returned from the S-type asteroid Itokawa by the Hayabusa mission revealed that space-weathering on that body was dominated by interactions with the solar wind acting on LL ordinary chondrite-like materials [1, 2]. Understanding and predicting how the surface regoliths of primitive carbonaceous asteroids respond to space weathering processes is important for future sample return missions (Hayabusa 2 and OSIRIS-REx) that are targeting objects of this type. Here, we report the results of our preliminary ion irradiation experiments on a hydrated carbonaceous chondrite with emphasis on microstructural and infrared spectral changes.

  1. Global cloud condensation nuclei influenced by carbonaceous combustion aerosol

    Directory of Open Access Journals (Sweden)

    D. V. Spracklen

    2011-09-01

    Full Text Available Black carbon in carbonaceous combustion aerosol warms the climate by absorbing solar radiation, meaning reductions in black carbon emissions are often perceived as an attractive global warming mitigation option. However, carbonaceous combustion aerosol can also act as cloud condensation nuclei (CCN so they also cool the climate by increasing cloud albedo. The net radiative effect of carbonaceous combustion aerosol is uncertain because their contribution to CCN has not been evaluated on the global scale. By combining extensive observations of CCN concentrations with the GLOMAP global aerosol model, we find that the model is biased low (normalised mean bias = −77 % unless carbonaceous combustion aerosol act as CCN. We show that carbonaceous combustion aerosol accounts for more than half (52–64 % of global CCN with the range due to uncertainty in the emitted size distribution of carbonaceous combustion particles. The model predicts that wildfire and pollution (fossil fuel and biofuel carbonaceous combustion aerosol causes a global mean cloud albedo aerosol indirect effect of −0.34 W m−2, with stronger cooling if we assume smaller particle emission size. We calculate that carbonaceous combustion aerosol from pollution sources cause a global mean aerosol indirect effect of −0.23 W m−2. The small size of carbonaceous combustion particles from fossil fuel sources means that whilst pollution sources account for only one-third of the emitted mass they cause two-thirds of the cloud albedo aerosol indirect effect that is due to carbonaceous combustion aerosol. This cooling effect must be accounted for, along with other cloud effects not studied here, to ensure that black carbon emissions controls that reduce the high number concentrations of fossil fuel particles have the desired net effect on climate.

  2. ANALYSIS OF DEVONIAN BLACK SHALES IN KENTUCKY FOR POTENTIAL CARBON DIOXIDE SEQUESTRATION AND ENHANCED NATURAL GAS PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall

    2004-01-01

    CO{sub 2} emissions from the combustion of fossil fuels have been linked to global climate change. Proposed carbon management technologies include geologic sequestration of CO{sub 2}. A possible, but untested, sequestration strategy is to inject CO{sub 2} into organic-rich shales. Devonian black shales underlie approximately two-thirds of Kentucky and are thicker and deeper in the Illinois and Appalachian Basin portions of Kentucky than in central Kentucky. The Devonian black shales serve as both the source and trap for large quantities of natural gas; total gas in place for the shales in Kentucky is estimated to be between 63 and 112 trillion cubic feet. Most of this natural gas is adsorbed on clay and kerogen surfaces, analogous to methane storage in coal beds. In coals, it has been demonstrated that CO{sub 2} is preferentially adsorbed, displacing methane. Black shales may similarly desorb methane in the presence of CO{sub 2}. The concept that black, organic-rich Devonian shales could serve as a significant geologic sink for CO{sub 2} is the subject of current research. To accomplish this investigation, drill cuttings and cores were selected from the Kentucky Geological Survey Well Sample and Core Library. Methane and carbon dioxide adsorption analyses are being performed to determine the gas-storage potential of the shale and to identify shale facies with the most sequestration potential. In addition, sidewall core samples are being acquired to investigate specific black-shale facies, their potential CO{sub 2} uptake, and the resulting displacement of methane. Advanced logging techniques (elemental capture spectroscopy) are being investigated for possible correlations between adsorption capacity and geophysical log measurements. For the Devonian shale, average total organic carbon is 3.71 (as received) and mean random vitrinite reflectance is 1.16. Measured adsorption isotherm data range from 37.5 to 2,077.6 standard cubic feet of CO{sub 2} per ton (scf/ton) of

  3. ANALYSIS OF DEVONIAN BLACK SHALES IN KENTUCKY FOR POTENTIAL CARBON DIOXIDE SEQUESTRATION AND ENHANCED NATURAL GAS PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall

    2003-10-29

    CO{sub 2} emissions from the combustion of fossil fuels have been linked to global climate change. Proposed carbon management technologies include geologic sequestration of CO{sub 2}. A possible, but untested, sequestration strategy is to inject CO{sub 2} into organic-rich shales. Devonian black shales underlie approximately two-thirds of Kentucky and are thicker and deeper in the Illinois and Appalachian Basin portions of Kentucky than in central Kentucky. The Devonian black shales serve as both the source and trap for large quantities of natural gas; total gas in place for the shales in Kentucky is estimated to be between 63 and 112 trillion cubic feet. Most of this natural gas is adsorbed on clay and kerogen surfaces, analogous to methane storage in coal beds. In coals, it has been demonstrated that CO{sub 2} is preferentially adsorbed, displacing methane. Black shales may similarly desorb methane in the presence of CO{sub 2}. The concept that black, organic-rich Devonian shales could serve as a significant geologic sink for CO{sub 2} is the subject of current research. To accomplish this investigation, drill cuttings and cores were selected from the Kentucky Geological Survey Well Sample and Core Library. Methane and carbon dioxide adsorption analyses are being performed to determine the gas-storage potential of the shale and to identify shale facies with the most sequestration potential. In addition, sidewall core samples are being acquired to investigate specific black-shale facies, their potential CO{sub 2} uptake, and the resulting displacement of methane. Advanced logging techniques (elemental capture spectroscopy) are being investigated for possible correlations between adsorption capacity and geophysical log measurements. For the Devonian shale, average total organic carbon is 3.71 (as received) and mean random vitrinite reflectance is 1.16. Measured adsorption isotherm data range from 37.5 to 2,077.6 standard cubic feet of CO{sub 2} per ton (scf/ton) of

  4. ANALYSIS OF DEVONIAN BLACK SHALES IN KENTUCKY FOR POTENTIAL CARBON DIOXIDE SEQUESTRATION AND ENHANCED NATURAL GAS PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall

    2004-04-01

    CO{sub 2} emissions from the combustion of fossil fuels have been linked to global climate change. Proposed carbon management technologies include geologic sequestration of CO{sub 2}. A possible, but untested, sequestration strategy is to inject CO{sub 2} into organic-rich shales. Devonian black shales underlie approximately two-thirds of Kentucky and are thicker and deeper in the Illinois and Appalachian Basin portions of Kentucky than in central Kentucky. The Devonian black shales serve as both the source and trap for large quantities of natural gas; total gas in place for the shales in Kentucky is estimated to be between 63 and 112 trillion cubic feet. Most of this natural gas is adsorbed on clay and kerogen surfaces, analogous to methane storage in coal beds. In coals, it has been demonstrated that CO{sub 2} is preferentially adsorbed, displacing methane. Black shales may similarly desorb methane in the presence of CO{sub 2}. The concept that black, organic-rich Devonian shales could serve as a significant geologic sink for CO{sub 2} is the subject of current research. To accomplish this investigation, drill cuttings and cores were selected from the Kentucky Geological Survey Well Sample and Core Library. Methane and carbon dioxide adsorption analyses are being performed to determine the gas-storage potential of the shale and to identify shale facies with the most sequestration potential. In addition, sidewall core samples are being acquired to investigate specific black-shale facies, their potential CO{sub 2} uptake, and the resulting displacement of methane. Advanced logging techniques (elemental capture spectroscopy) are being investigated for possible correlations between adsorption capacity and geophysical log measurements. For the Devonian shale, average total organic carbon is 3.71 percent (as received) and mean random vitrinite reflectance is 1.16. Measured adsorption isotherm data range from 37.5 to 2,077.6 standard cubic feet of CO{sub 2} per ton (scf

  5. Rates and Mechanisms of Oil Shale Pyrolysis: A Chemical Structure Approach

    Energy Technology Data Exchange (ETDEWEB)

    Fletcher, Thomas; Pugmire, Ronald

    2015-01-01

    Three pristine Utah Green River oil shale samples were obtained and used for analysis by the combined research groups at the University of Utah and Brigham Young University. Oil shale samples were first demineralized and the separated kerogen and extracted bitumen samples were then studied by a host of techniques including high resolution liquid-state carbon-13 NMR, solid-state magic angle sample spinning 13C NMR, GC/MS, FTIR, and pyrolysis. Bitumen was extracted from the shale using methanol/dichloromethane and analyzed using high resolution 13C NMR liquid state spectroscopy, showing carbon aromaticities of 7 to 11%. The three parent shales and the demineralized kerogens were each analyzed with solid-state 13C NMR spectroscopy. Carbon aromaticity of the kerogen was 23-24%, with 10-12 aromatic carbons per cluster. Crushed samples of Green River oil shale and its kerogen extract were pyrolyzed at heating rates from 1 to 10 K/min at pressures of 1 and 40 bar and temperatures up to 1000°C. The transient pyrolysis data were fit with a first-order model and a Distributed Activation Energy Model (DAEM). The demineralized kerogen was pyrolyzed at 10 K/min in nitrogen at atmospheric pressure at temperatures up to 525°C, and the pyrolysis products (light gas, tar, and char) were analyzed using 13C NMR, GC/MS, and FTIR. Details of the kerogen pyrolysis have been modeled by a modified version of the chemical percolation devolatilization (CPD) model that has been widely used to model coal combustion/pyrolysis. This refined CPD model has been successful in predicting the char, tar, and gas yields of the three shale samples during pyrolysis. This set of experiments and associated modeling represents the most sophisticated and complete analysis available for a given set of oil shale samples.

  6. ‘Indicator’ carbonaceous phyllite/graphitic schist in the Archean Kundarkocha gold deposit, Singhbhum orogenic belt, eastern India: Implications for gold mineralization vis-a-vis organic matter

    Indian Academy of Sciences (India)

    P R Sahoo; A S Venkatesh

    2014-10-01

    Carbonaceous rocks in the form of graphitic schist and carbonaceous phyllite are the major host rocks of the gold mineralization in Kundarkocha gold deposit of the Precambrian Singhbhum orogenic belt in eastern India. The detection of organic carbon, essentially in the carbonaceous phyllite and graphitized schist within the Precambrian terrain, is noted from this deposit. A very close relationship exists between gold mineralization and ubiquitous carbonaceous rocks containing organic carbon that seems to play a vital role in the deposition of gold in a Precambrian terrain in India and important metallogenetic implications for such type of deposits elsewhere. However, the role played by organic matter in a Precambrian gold deposit is debatable and the mechanism of precipitation of gold and other metals by organic carbon has been reported elsewhere. Fourier transform infrared spectroscopy (FTIR) results and total organic carbon (TOC) values suggest that at least part of the organic material acted as a possible source for the reduction that played a significant role in the precipitation of gold. Lithological, electron probe analysis (EPMA), fluid inclusions associated with gold mineralization, Total Carbon (TC), TOC and FTIR results suggest that the gold mineralization is spatially and genetically associated with graphitic schist, carbonaceous phyllite/shale that are constituted of immature organic carbon or kerogen. Nano-scale gold inclusions along with free milling gold are associated with sulfide mineral phases present within the carbonaceous host rocks as well as in mineralized quartz-carbonate veins. Deposition of gold could have been facilitated due to the organic redox reactions and the graphitic schist and carbonaceous phyllite zone may be considered as the indicator zone.

  7. Cloud albedo increase from carbonaceous aerosol

    Directory of Open Access Journals (Sweden)

    W. R. Leaitch

    2010-08-01

    Full Text Available Airborne measurements from two consecutive days, analysed with the aid of an aerosol-adiabatic cloud parcel model, are used to study the effect of carbonaceous aerosol particles on the reflectivity of sunlight by water clouds. The measurements, including aerosol chemistry, aerosol microphysics, cloud microphysics, cloud gust velocities and cloud light extinction, were made below, in and above stratocumulus over the northwest Atlantic Ocean. On the first day, the history of the below-cloud fine particle aerosol was marine and the fine particle sulphate and organic carbon mass concentrations measured at cloud base were 2.4 μg m−3 and 0.9 μg m−3 respectively. On the second day, the below-cloud aerosol was continentally influenced and the fine particle sulphate and organic carbon mass concentrations were 2.3 μg m−3 and 2.6 μg m−3 respectively. Over the range 0.06–0.8 μm diameter, the shapes of the below-cloud size distributions were similar on both days and the number concentrations were approximately a factor of two higher on the second day. The cloud droplet number concentrations (CDNC on the second day were approximately three times higher than the CDNC measured on the first day. Using the parcel model to separate the influence of the differences in gust velocities, we estimate from the vertically integrated cloud light scattering measurements a 6% increase in the cloud albedo principally due to the increase in the carbonaceous components on the second day. Assuming no additional absorption by this aerosol, a 6% albedo increase translates to a local daytime radiative cooling of ∼12 W m−2. This result provides observational evidence that the role of anthropogenic carbonaceous components in the cloud albedo effect can be much larger than that of anthropogenic sulphate, as some global simulations have indicated.

  8. Microfossils of Cyanobacteria in Carbonaceous Meteorites

    Science.gov (United States)

    Hoover, Richard B.

    2007-01-01

    During the past decade, Environmental and Field Emission Scanning Electron Microscopes have been used at the NASA/Marshall Space Flight Center to investigate freshly fractured interior surfaces of a large number of different types of meteorites. Large, complex, microfossils with clearly recognizable biological affinities have been found embedded in several carbonaceous meteorites. Similar forms were notably absent in all stony and nickel-iron meteorites investigated. The forms encountered are consistent in size and morphology with morphotypes of known genera of Cyanobacteria and microorganisms that are typically encountered in associated benthic prokaryotic mats. Even though many coccoidal and isodiametric filamentous cyanobacteria have a strong morphological convergence with some other spherical and filamentous bacteria and algae, many genera of heteropolar cyanobacteria have distinctive apical and basal regions and cellular differentiation that makes it possible to unambiguously recognize the forms based entirely upon cellular dimensions, filament size and distinctive morphological characteristics. For almost two centuries, these morphological characteristics have historically provided the basis for the systematics and taxonomy of cyanobacteria. This paper presents ESEM and FESEM images of embedded filaments and thick mats found in-situ in the Murchison CM2 and Orgueil cn carbonaceous meteorites. Comparative images are also provided for known genera and species of cyanobacteria and other microbial extremophiles. Energy Dispersive X-ray Spectroscopy (EDS) studies indicate that the meteorite filaments typically exhibit dramatic chemical differentiation with distinctive difference between the possible microfossil and the meteorite matrix in the immediate proximity. Chemical differentiation is also observed within these microstructures with many of the permineralized filaments enveloped within electron transparent carbonaceous sheaths. Elemental distributions of

  9. Nanoscale simulation of shale transport properties using the lattice Boltzmann method: permeability and diffusivity

    CERN Document Server

    Chen, Li; Kang, Qinjun; Yao, Jun; Tao, Wenquan

    2014-01-01

    Porous structures of shales are reconstructed based on scanning electron microscopy (SEM) images of shale samples from Sichuan Basin, China. Characterization analyzes of the nanoscale reconstructed shales are performed, including porosity, pore size distribution, specific surface area and pore connectivity. The multiple-relaxation-time (MRT) lattice Boltzmann method (LBM) fluid flow model and single-relaxation-time (SRT) LBM diffusion model are adopted to simulate the fluid flow and Knudsen diffusion process within the reconstructed shales, respectively. Tortuosity, intrinsic permeability and effective Knudsen diffusivity are numerically predicted. The tortuosity is much higher than that commonly employed in Bruggeman equation. Correction of the intrinsic permeability by taking into consideration the contribution of Knudsen diffusion, which leads to the apparent permeability, is performed. The correction factor under different Knudsen number and pressure are estimated and compared with existing corrections re...

  10. Dynamic imaging of oil shale pyrolysis using synchrotron X-ray microtomography

    Science.gov (United States)

    Saif, Tarik; Lin, Qingyang; Singh, Kamaljit; Bijeljic, Branko; Blunt, Martin J.

    2016-07-01

    The structure and connectivity of the pore space during the pyrolysis of oil shales determines hydrocarbon flow behavior and ultimate recovery. We image the time evolution of the pore and microfracture networks during oil shale pyrolysis using synchrotron X-ray microtomography. Immature Green River (Mahogany Zone) shale samples were thermally matured under vacuum conditions at temperatures up to 500°C while being periodically imaged with a 2 µm voxel size. The structural transformation of both organic-rich and organic-lean layers within the shale was quantified. The images reveal a dramatic change in porosity accompanying pyrolysis between 390 and 400°C with the formation of micron-scale heterogeneous pores. With a further increase in temperature, the pores steadily expand resulting in connected microfracture networks that predominantly develop along the kerogen-rich laminations.

  11. Thermophysical properties of Conasauga shale

    Energy Technology Data Exchange (ETDEWEB)

    Smith, D.D.

    1978-12-04

    Thermophysical-property characterizations of five Conasauga shale cores were determined at temperatures between 298 and 673 K. Methods of specimen fabrication for different tests were evaluated. Thermal-conductivity and thermal-expansion data were found to be dependent on the structure and orientation of the individual specimens. Thermal conductivities ranged between 2.8 and 1.0 W/m-K with a small negative temperature dependence. Thermal expansions were between 2 and 5 x 10/sup -3/ over the temperature range for the group. Heat capacity varied with the composition. 17 figures, 3 tables.

  12. Scales over Shale: How Pennsylvania Got Fracked

    Science.gov (United States)

    Sica, Carlo E.

    Shale gas has become one of Pennsylvania's major resources in recent years and the gas boom has proceeded in spite of uncertainty over the environmental risks of its production process. This thesis argues that location alone cannot explain why shale gas boomed in Pennsylvania. Using interviews with corporate and state executives, I argue that the scalar dimensions of the neoliberal environmental governance of shale gas were critical to understanding why shale gas boomed in Pennsylvania. These actors supported the preemption of local scales of governance by the state as a scalar fix for capital accumulation from shale gas development. They also legitimated the scalar fix by assembling a neat stack of scale frames that made shale gas seem to benefit everyone. These scale frames made shale gas appear as if it would provide local employment, regional supplies of cheap gas, national energy security, abundant gas for tight global markets, and a mitigating strategy for global climate change. In arguing this point, I present a history of how shale gas became a resource that outlines the critical role of the state in that process.

  13. Different Methods of Predicting Permeability in Shale

    DEFF Research Database (Denmark)

    Mbia, Ernest Ncha; Fabricius, Ida Lykke; Krogsbøll, Anette

    Permeability is often very difficult to measure or predict in shale lithology. In this work we are determining shale permeability from consolidation tests data using Wissa et al., (1971) approach and comparing the results with predicted permeability from Kozeny’s model. Core and cuttings materials...

  14. Shale nanopore reconstruction with compressive sensing

    Science.gov (United States)

    Guo, Long; Xiao, Lizhi

    2017-03-01

    With increasing global demand for energy resources, shale gas has been paid considerable attention in recent years. Nanopore geometry is the basis for all microscopic rock physics and petrophysical numerical experiments for shale. At present, nano digital cores can be acquired via thin section reconstruction, nanometer-scale x-ray computed tomography (nano-CT), and focused ion beam and scanning electron microscopy (FIB-SEM). FIB-SEM detects nanoscale pores in the xy-plane with a resolution of up to 0.8 nm voxel‑1, and it is usually provides higher resolution than nano-CT. The main workload associated with FIB-SEM is the need to recut the sample many times and scan every section, with these then being overlaid to create a three-dimensional (3D) pore model. Each cutting distance can be ascertained, but this cannot be controlled precisely because of the fundamental limits of focused ion beams. Many interpolation methods can be used to fit the anisotropy resolution. However, these methods can also alter the geometry of the pores. Nanopores that are close to the limiting resolution are particularly susceptible to stretching. Linear interpolation is likely to lengthen the pores in the low-resolution direction. The subsequent calculation of sensitive physical attributes will be affected by geometric alterations. Through foundational work in the compressive sensing (CS) method, we present a reconstruction workflow for maintaining the pore shape using prior knowledge and reliable information. The images are reassembled with equal distance, so the nanoscale structures can have a resolution of unity in three dimensions.

  15. Carbonaceous aerosols at urban influenced sites in Norway

    Directory of Open Access Journals (Sweden)

    K. E. Yttri

    2008-11-01

    Full Text Available Little is known regarding levels and source strength of carbonaceous aerosols in Scandinavia. In the present study, ambient aerosol (PM10 and PM2.5 concentrations of elemental carbon (EC, organic carbon (OC, water-insoluble organic carbon (WINSOC, and water-soluble organic carbon (WSOC are reported for a curbside site, an urban background site, and a suburban site in Norway in order to investigate their spatial and seasonal variations. Aerosol filter samples were collected using tandem filter sampling to correct for the positive sampling artefact introduced by semi volatile OC. Analyses were performed using the thermal optical transmission (TOT instrument from Sunset Lab Inc., which corrects for charring during analysis. Finally, we estimated the relative contribution of OC from wood burning based on the samples content of levoglucosan.

    Levels of EC varied by more than one order of magnitude between sites, likely due to the higher impact of vehicular traffic at the curbside and the urban background sites. In winter, the level of particulate organic carbon (OCp at the suburban site was equal to (for PM10 or even higher (for PM2.5 than the levels observed at the curbside and the urban background sites. This finding was attributed to the impact of residential wood burning at the suburban site in winter, which was confirmed by a high mean concentration of levoglucosan (407 ng m−3. This finding indicates that exposure to primary combustion derived OCp could be equally high in residential areas as in a city center. It is demonstrated that OCp from wood burning (OCwood accounted for almost all OCp at the suburban site in winter, allowing a new estimate of the ratio TCp/levoglucosan for both PM10 and PM2.5. Particulate carbonaceous material (PCM = Organic matter + Elemental matter accounted for 46–83

  16. Shale Gas Play Screening and Evaluation Criteria

    Institute of Scientific and Technical Information of China (English)

    Michael D. Burnaman; Wenwu Xia; John Shelton

    2009-01-01

    The uniqueness of shale gas plays is contrasted with conventional oil and gas exploration. Based on our ten year history in shale gas exploration, a practical 17 point list of criteria to use for screening shale gas projects and ranking that encompasses geoscience, geochemistry, reservoir engineering, drilling, completions and production operations is developed and explained. Other considerations that will impact shale gas development are identified and discussed. Some key methodologies to incorporate in the evaluation process are also proposed. The outcome of this proposed screening process, if rigorously applied,should quickly identify the projects that have the most likely chance for success for recommendation to management. Examples from active shale gas plays in the United States are used to support these criteria and references to relevant recent publications and presentations are provided.

  17. Intelligent fracture creation for shale gas development

    KAUST Repository

    Douglas, Craig C.

    2011-05-14

    Shale gas represents a major fraction of the proven reserves of natural gas in the United States and a collection of other countries. Higher gas prices and the need for cleaner fuels provides motivation for commercializing shale gas deposits even though the cost is substantially higher than traditional gas deposits. Recent advances in horizontal drilling and multistage hydraulic fracturing, which dramatically lower costs of developing shale gas fields, are key to renewed interest in shale gas deposits. Hydraulically induced fractures are quite complex in shale gas reservoirs. Massive, multistage, multiple cluster treatments lead to fractures that interact with existing fractures (whether natural or induced earlier). A dynamic approach to the fracturing process so that the resulting network of reservoirs is known during the drilling and fracturing process is economically enticing. The process needs to be automatic and done in faster than real-time in order to be useful to the drilling crews.

  18. Tuneable porous carbonaceous materials from renewable resources.

    Science.gov (United States)

    White, Robin J; Budarin, Vitaly; Luque, Rafael; Clark, James H; Macquarrie, Duncan J

    2009-12-01

    Porous carbon materials are ubiquitous with a wide range of technologically important applications, including separation science, heterogeneous catalyst supports, water purification filters, stationary phase materials, as well as the developing future areas of energy generation and storage applications. Hard template routes to ordered mesoporous carbons are well established, but whilst offering different mesoscopic textural phases, the surface of the material is difficult to chemically post-modify and processing is energy, resource and step intensive. The production of carbon materials from biomass (i.e. sugars or polysaccharides) is a relatively new but rapidly expanding research area. In this tutorial review, we compare and contrast recently reported routes to the preparation of porous carbon materials derived from renewable resources, with examples of our previously reported mesoporous polysaccharide-derived "Starbon" carbonaceous material technology.

  19. Carbonaceous chondrites and the origin of life

    Science.gov (United States)

    Hartman, Hyman; Sweeney, Michael A.; Kropp, Michael A.; Lewis, John S.

    1993-01-01

    Organic matter in carbonaceous chondrites can be separated into three fractions. The first component, the fraction that is insoluble in chloroform and methanol, has a part which is of interstellar origin. The other two fractions (chloroform-soluble hydrocarbons and methanol-soluble polar organics) are hypothesized to have been synthesized on a planetoid body. We propose that the polar organics, i.e., amino acids, were synthesized close to its surface by the radiolysis of hydrocarbons and ammonium carbonate in a liquid water environment. Some hydrocarbons may have been synthesized by a Fischer-Tropsch mechanism in the interior of the body. Ferrous ion acted as a protection against back reactions. The simultaneous synthesis of iron-rich clays with the polar organics may be indicative of events related to the origin of life on Earth.

  20. Characterization Of Carbonaceous Particles Along A North South Transect Of The Atlantic Ocean

    Science.gov (United States)

    Herckes, P.; Cox, J.; Lohmann, R.; Nizzetto, L.

    2006-12-01

    In recent years an increasing number of studies have investigated carbonaceous aerosols in urban and remote locations. However, little data on carbonaceous particles in remote marine environments exists, particularly on individual organic species concentrations including so-called molecular marker species. These markers can provide valuable insights into the sources of carbonaceous material, when stable during atmospheric transport. We will present results on organic aerosol characterization performed on samples collected along a North/South Transect from Bremerhaven (Germany) to Capetown (South Africa) aboard the Polarstern research vessel. Total Suspended Particulate matter (TSP) filter samples were analyzed for total carbon as well as carbon isotope ratios. Individual organic species (including n-alkanes, n-alkanoic acids, polyaromatic hydrocarbons, hopanes, steranes, dicarboxylic acids, and levoglucosan) were quantified in discrete (12h) and pooled (24-72h) samples, following solvent extraction and analysis by gas chromatography coupled to mass spectrometry (GC/MS). Preliminary results indicate relatively low concentrations of organic matter during most of the research cruise ( <1ug/m3) with higher concentrations in less pristine areas, mostly along Europe. Carbon isotope ratios were variable (-20 < delta13C < -27) and consistent with a change from C3 to C4 vegetation, suggesting an important biomass contribution to the observed particulate matter concentrations. These observations will be discussed with a focus on our observations of molecular marker concentrations. Although marker species were generally close to the detection limit, some markers were clearly detectable during high carbon events and are indicative of the sources of the carbonaceous particles.

  1. Sampling

    CERN Document Server

    Thompson, Steven K

    2012-01-01

    Praise for the Second Edition "This book has never had a competitor. It is the only book that takes a broad approach to sampling . . . any good personal statistics library should include a copy of this book." —Technometrics "Well-written . . . an excellent book on an important subject. Highly recommended." —Choice "An ideal reference for scientific researchers and other professionals who use sampling." —Zentralblatt Math Features new developments in the field combined with all aspects of obtaining, interpreting, and using sample data Sampling provides an up-to-date treat

  2. Study of Reaction Between Slag and Carbonaceous Materials

    Science.gov (United States)

    Maroufi, Samane; Mayyas, Mohannad; Mansuri, Irshad; O'Kane, Paul; Skidmore, Catherine; Jin, Zheshi; Fontana, Andrea; Sahajwalla, Veena

    2017-10-01

    The chemical interaction of a typical slag of EAF with three different carbon sources, coke, rubber-derived carbon (RDC), coke-RDC blend, was studied in atmospheric pressure at 1823 K (1550 °C). Using an IR-gas analyzer, off-gases evolved from the sample were monitored. While the coke-RDC blend exhibited the best reducing performance in reaction with molten slag, the RDC sample showed poor interaction with the molten slag. The gasification of the coke, RDC, and coke-RDC blend was also carried out under oxidizing conditions using a gas mixture of CO2 (4 wt pct) and Ar (96 wt pct) and it was shown that the RDC sample had the highest rate of gasification step C0 \\mathop{\\longrightarrow}\\limits{{k3 }}{CO} + nCf (11.6 site/g s (×6.023 × 1023/2.24 × 104)). This may be attributed to its disordered structure confirmed by Raman spectra and its nano-particle morphology observed by FE-SEM. The high reactivity of RDC with CO2 provided evidence that the Boudouard reaction was fast during the interaction with molten slag. However, low reduction rate of iron oxide from slag with RDC can be attributed to the initial weak contact between RDC and molten slag implying that the contact between carbonaceous matter and slag plays significant roles in the reduction of iron oxide from slag.

  3. Using Archean and Paleoproterozoic Shales and Tillites as a Window into Crustal Evolution and Surface Conditions

    Science.gov (United States)

    Bindeman, I. N.; Bekker, A.; Zakharov, D. O.

    2014-12-01

    Precambrian shales and tillites have been insufficiently studied so far. We present oxygen and hydrogen isotope data for 103 bulk shale and tillites that were collected from drillholes on all continents from 3.2 to 1.4Ga. These samples have also been analyzed for total organic and inorganic carbon, total sulfur, δ13Corg values and by XRF for major and trace elements to calculate chemical index of alteration (CIA). Having uncompromised fresh samples from drillcores is a must for this kind of investigation. We have a particularly good coverage for the ca. 2.7-2.2 Ga time interval when Earth experienced 3-4 Snowball Earth glaciations associated with the rapid rise in atmospheric O2 and fluctuations in CO2, thus affecting weathering cycle and attainment of isotopic fractionation. All units have similar to Phanerozoic ranges in δ13Corg values (-23 to -33‰ PDB) and Corg content (0.1 to 10 wt. %). Compared to Phanerozoic shales, Precambrian shales have comparable ranges in δ18O values (+7 to +20‰), with slightly decreasing means with increasing age, and identical δ17O-δ18O slope (0.528). Shales in some drill holes display wide δ18O ranges over short stratigraphic intervals suggesting significant variability in the provenance. We however observe a significant, several permil downward shift and decrease in the range of δ18O values (7-9‰) in 2.2-2.5 Ga shales from several continents that are associated with the Paleoproterozoic glaciations. Scattered negative correlation of CIA with δ18O, for some of these shales broadly associated with the Paleoproterozoic glaciations suggest contact with glacial meltwater having ultra-low-δ18O values during deposition or diagenesis of these shales. The δD values of shales range from -50 to -75‰, and are comparable to Phanerozoic values, with the exception of the ~2.5-2.2 Ga shales that reach to -100‰. We also compare O isotope values of ultra-low-δ18O, +8 to -27‰ SMOW subglacial hydrothermal rocks recently discovered

  4. Investigation of organo-carbonate associations in carbonaceous chondrites by Raman spectroscopy

    Science.gov (United States)

    Chan, Queenie H. S.; Zolensky, Michael E.; Bodnar, Robert J.; Farley, Charles; Cheung, Jacob C. H.

    2017-03-01

    Carbonates record information regarding the timing, nature and conditions of the fluids circulating through asteroid parent bodies during aqueous alteration events. Determining carbonate abundances and their relationships with organic matter improves our understanding of the genesis of major carbonaceous components in chondritic materials. In this study, five CM2 carbonaceous chondrites (CM2.2 Nogoya, CM2.3 Jbilet Winselwan, CM2.5 Murchison, CM2 Santa Cruz, and CM2TII Wisconsin Range 91600) were studied with Raman spectroscopy. Carbonates were identified in these meteorite samples by the distinctive Raman band in the ∼1100 cm-1 region, representing the symmetric stretching vibration mode (ν1) of the (CO3)2- anion. Carbonates identified in the meteorite samples are all calcite, with the exception of a single dolomite grain in Nogoya. The v1 positions of the CM calcites are 2-3 cm-1 higher than in pure calcite, which suggests that they contain significant impurity cations. Typical graphitic first-order D and G bands were identified in the meteorite matrix as well as in ∼25% of the analyzed carbonate grains. From the Raman results, we postulate that the carbonates might not have formed under equilibrium conditions from a single fluid. The first generation of carbonate is interpreted to have formed from highly oxidized fluids that led to the oxidation of organic matter (OM) and produced carbonates that are OM-barren. The second generation of carbonate was formed from a more evolved aqueous fluid with the presence of OM. The Raman parameters of the organics in carbonates clearly deviate from the matrix OM which suggests that the carbonate organics contain very different carbonaceous components that are distinct from the typical amorphous OM of the CM matrix. The occurrence of different generations of carbonate in close proximity may be partly responsible for the wide range in estimated ages of carbonates in carbonaceous chondrites reported in previous studies.

  5. Origin of fine carbonaceous particulate matter in the Western Mediterranean Basin: fossil versus modern sources

    Science.gov (United States)

    Cruz Minguillón, María.; Perron, Nolwenn; Querol, Xavier; Szidat, Sönke; Fahrni, Simon; Wacker, Lukas; Reche, Cristina; Cusack, Michael; Baltensperger, Urs; Prévôt, André S. H.

    2010-05-01

    The present work was carried out in the frame of the international field campaign DAURE (Determination of the sources of atmospheric Aerosols in Urban and Rural Environments in the western Mediterranean). The objective of this campaign is to study the aerosol pollution episodes occurring at regional scale during winter and summer in the Western Mediterranean Basin. As part of this campaign, this work focuses on identifying the origin of fine carbonaceous aerosols. To this end, fine particulate matter (PM1) samples were collected during two different seasons (February-March and July 2009) at two sites: an urban site (Barcelona, NE Spain) and a rural European Supersite for Atmospheric Aerosol Research (Montseny, NE Spain). Subsequently, 14C analyses were carried out on these samples, both in the elemental carbon (EC) fraction and the organic carbon (OC) fraction, in order to distinguish between modern carbonaceous sources (biogenic emissions and biomass burning emissions) and fossil carbonaceous sources (mainly road traffic). Preliminary results from the winter period show that 40% of the OC at Barcelona has a fossil origin whereas at Montseny this percentage is 30%. These values can be considered as unexpected given the nature of the sites. Nevertheless, the absolute concentrations of fossil OC at Barcelona and Montseny differ by a factor of 2 (the first being higher), since the total OC at Montseny is lower than at Barcelona. Further evaluation of results and comparison with other measurements carried out during the campaign are required to better evaluate the origin of the fine carbonaceous matter in the Western Mediterranean Basin. Acknowledgements: Spanish Ministry of Education and Science, for a Postdoctoral Grant awarded to M.C. Minguillón in the frame of Programa Nacional de Movilidad de Recursos Humanos del Plan nacional de I-D+I 2008-2011. Spanish Ministry of Education and Science, for the Acción Complementaria DAURE CGL2007-30502-E/CLI.

  6. Phanerozoic black shales and the Wilson Cycle

    Science.gov (United States)

    Trabucho-Alexandre, J.; Hay, W. W.; de Boer, P. L.

    2011-09-01

    The spatial and temporal distribution of black shales is related to the development of the environments in which they accumulate and to a propitious combination of environmental variables. Whereas much has been done in recent years to improve our understanding of the mechanisms behind the temporal distribution of black shales in the Phanerozoic, the interpretation of the palaeogeographical distribution of black shales is still dominated by an oversimplistic set of three uniformitarian depositional models that do not capture the complexity and dynamics of environments of black shale accumulation. These three models, the restricted circulation, the (open) ocean oxygen minimum and the continental shelf models, are in fact a uniformitarian simplification of the variety of depositional environments that arise and coexist throughout the course of a basin's Wilson Cycle, i.e. the dynamic sequence of events and stages that characterise the evolution of an ocean basin, from the opening continental rift to the closing orogeny. We examine the spatial distribution of black shales in the context of the Wilson Cycle using examples from the Phanerozoic. It is shown that the geographical distribution of black shales, their position in the basin infill sequence and their nature (e.g. type of organic matter, lithology) depend on basin evolution because the latter controls the development of sedimentary environments where black shales may be deposited.

  7. Mineral composition and preferred orientation of minerals in shales from Palaeozoic Baltic Basin

    Science.gov (United States)

    Gąsiński, Arkadiusz

    2017-04-01

    Ordovician and Silurian rocks from the Palaeozoic Baltic Basin in northern Poland, often described simply as "shale", embrace a wide range of siliceos and argillaceous rocks. The little knowledge that is available about their detailed mineralogical is mainly limited to qualitative data, so the main aim of this work was to obtain their quantitative mineral composition, based on analysis of thin sections with SEM, FIB and EDS techniques supported by XRD data. The mineral composition of shales dictates their chemical properties and is also a major factor determining their physical properties, especially relating to their stability during drilling, hydraulic fracturing, and hydrocarbon production. Knowledge of the mineral composition of different shales plays a very important role in identifying optimal proppants, fracture fluids and pumping schedules. The mineralogy of the shale is an important influence on total gas capacity. Carbonate-rich shales indicate adjacent carbonate platform and embayment succession origins, and commonly have a lower organic carbon content and porosity, and a corresponding lower gas capacity, than shales with lower carbonate content. All samples show a rather complex mineralogical composition with illite, micas, quartz, calcite, dolomite and chlorites as major minerals. It was possible to point out the microzones that contain higher amount of brittle minerals and therefore should be especially prone to cracking. Anisotropy in clay-rich sedimentary rocks is receiving increasing attention. This feature is very important for the prospecting for hydrocarbon deposits and for hydraulic fracturing. Anisotropy of diffusion has become relevant for environmental contaminants, including nuclear waste. In both cases, the orientation of component minerals is a critical ingredient. In this study I also show the orientation of different mineral components in shales with image analysis methods that allow me to characterize the shape of grains and its

  8. Composition, diagenetic transformation and alkalinity potential of oil shale ash sediments

    Energy Technology Data Exchange (ETDEWEB)

    Motlep, Riho, E-mail: riho.motlep@ut.ee [Department of Geology, University of Tartu, Ravila 14A, 50411 Tartu (Estonia); Sild, Terje, E-mail: terje.sild@maaamet.ee [Estonian Land Board, Mustamaee tee 51, 10621 Tallinn (Estonia); Puura, Erik, E-mail: erik.puura@ut.ee [Institute of Technology, University of Tartu, Nooruse 1, 50411 Tartu (Estonia); Kirsimaee, Kalle, E-mail: kalle.kirsimae@ut.ee [Department of Geology, University of Tartu, Ravila 14A, 50411 Tartu (Estonia)

    2010-12-15

    Oil shale is a primary fuel in the Estonian energy sector. After combustion 45-48% of the oil shale is left over as ash, producing about 5-7 Mt of ash, which is deposited on ash plateaus annually almost without any reuse. This study focuses on oil shale ash plateau sediment mineralogy, its hydration and diagenetic transformations, a study that has not been addressed. Oil shale ash wastes are considered as the biggest pollution sources in Estonia and thus determining the composition and properties of oil shale ash sediment are important to assess its environmental implications and also its possible reusability. A study of fresh ash and drillcore samples from ash plateau sediment was conducted by X-ray diffractometry and scanning electron microscopy. The oil shale is highly calcareous, and the ash that remains after combustion is derived from the decomposition of carbonate minerals. It is rich in lime and anhydrite that are unstable phases under hydrous conditions. These processes and the diagenetic alteration of other phases determine the composition of the plateau sediment. Dominant phases in the ash are hydration and associated transformation products: calcite, ettringite, portlandite and hydrocalumite. The prevailing mineral phases (portlandite, ettringite) cause highly alkaline leachates, pH 12-13. Neutralization of these leachates under natural conditions, by rainwater leaching/neutralization and slow transformation (e.g. carbonation) of the aforementioned unstable phases into more stable forms, takes, at best, hundreds or even hundreds of thousands of years.

  9. A new laboratory approach to shale analysis using NMR relaxometry

    Science.gov (United States)

    Washburn, Kathryn E.; Birdwell, Justin E.; Baez, Luis; Beeney, Ken; Sonnenberg, Steve

    2013-01-01

    Low-field nuclear magnetic resonance (LF-NMR) relaxometry is a non-invasive technique commonly used to assess hydrogen-bearing fluids in petroleum reservoir rocks. Measurements made using LF-NMR provide information on rock porosity, pore-size distributions, and in some cases, fluid types and saturations (Timur, 1967; Kenyon et al., 1986; Straley et al., 1994; Brown, 2001; Jackson, 2001; Kleinberg, 2001; Hurlimann et al., 2002). Recent improvements in LF-NMR instrument electronics have made it possible to apply methods used to measure pore fluids to assess highly viscous and even solid organic phases within reservoir rocks. T1 and T2 relaxation responses behave very differently in solids and liquids; therefore the relationship between these two modes of relaxation can be used to differentiate organic phases in rock samples or to characterize extracted organic materials. Using T1-T2 correlation data, organic components present in shales, such as kerogen and bitumen, can be examined in laboratory relaxometry measurements. In addition, implementation of a solid-echo pulse sequence to refocus T2 relaxation caused by homonuclear dipolar coupling during correlation measurements allows for improved resolution of solid-phase protons. LF-NMR measurements of T1 and T2 relaxation time distributions were carried out on raw oil shale samples from the Eocene Green River Formation and pyrolyzed samples of these shales processed by hydrous pyrolysis and techniques meant to mimic surface and in-situ retorting. Samples processed using the In Situ Simulator approach ranged from bitumen and early oil generation through to depletion of petroleum generating potential. The standard T1-T2 correlation plots revealed distinct peaks representative of solid- and liquid-like organic phases; results on the pyrolyzed shales reflect changes that occurred during thermal processing. The solid-echo T1 and T2 measurements were used to improve assessment of the solid organic phases, specifically

  10. A new CH carbonaceous chondrite from Acfer, Algeria

    OpenAIRE

    Moggi-Cecchi, V.; Salvadori, A; Pratesi, G.; Franchi, Ian; Greenwood, Richard

    2006-01-01

    A single stone weighing 1456 g was found in November 2002 in the Acfer area, Algeria. Oxygen isotope, chondrules-matrix ratio as well as other petrographic features point to a classification as CH carbonaceous chondrite.

  11. Bacterial morphologies in carbonaceous meteorites and comet dust

    Science.gov (United States)

    Wickramasinghe, Chandra; Wallis, Max K.; Gibson, Carl H.; Wallis, Jamie; Al-Mufti, Shirwan; Miyake, Nori

    2010-09-01

    Three decades ago the first convincing evidence of microbial fossils in carbonaceous chondrites was discovered and reported by Hans Dieter Pflug and his collaborators. In addition to morphology, other data, notably laser mass spectroscopy, confirmed the identification of such structures as putative bacterial fossils. Balloon-borne cryosampling of the stratosphere enables recovery of fragile cometary dust aggregates with their structure and carbonaceous matter largely intact. SEM studies of texture and morphology of particles in the Cardiff collection, together with EDX identifications, show two main types of putative bio-fossils - firstly organic-walled hollow spheres around 10μm across, secondly siliceous diatom skeletons similar to those found in carbonaceous chondrites and terrestrial sedimentary rocks and termed 'acritarchs'. Since carbonaceous chondrites (particularly Type 1 chondrites) are thought to be extinct comets the data reviewed in this article provide strong support for theories of cometary panspermia.

  12. Fungal-Transformation of Surrogate Sulphides and Carbonaceous ...

    African Journals Online (AJOL)

    user

    Refractory gold ores contain metal sulphides that encapsulate gold and prevent its dissolution by cyanide, and carbonaceous ... Several bacteria are known to oxidize sulphides but ..... Baako, A. B. (1972), Mining geology of Prestea gold.

  13. Bacterial morphologies in carbonaceous meteorites and comet dust

    CERN Document Server

    Wickramasinghe, N Chandra; Gibson, Carl H; Wallis, Jamie; Al-Mufti, Shirwan; Miyake, Nori

    2010-01-01

    Three decades ago the first convincing evidence of microbial fossils in carbonaceous chondrites was discovered and reported by Hans Dieter Pflug and his collaborators. In addition to morphology, other data, notably laser mass spectroscopy, confirmed the identification of such structures as putative bacterial fossils. Balloon-borne cryosampling of the stratosphere enables recovery of fragile cometary dust aggregates with their structure and carbonaceous matter largely intact. Scanning electron microscope studies of texture and morphology of particles in the Cardiff collection, together with Energy Dispersive X-ray identifications, show two main types of putative bio-fossils - firstly organic-walled hollow spheres around 10 microns across, secondly siliceous diatom skeletons similar to those found in carbonaceous chondrites and terrestrial sedimentary rocks and termed "acritarchs". Since carbonaceous chondrites (particularly Type 1 chondrites) are thought to be extinct comets the data reviewed in this article p...

  14. TESTING OF CARBONACEOUS ADSORBENTS FOR REMOVAL OF POLLUTANTS FROM WATER

    Directory of Open Access Journals (Sweden)

    RAISA NASTAS

    2012-03-01

    Full Text Available Testing of carbonaceous adsorbents for removal of pollutants from water. Relevant direction for improving of quality of potable water is application of active carbons at various stages of water treatments. This work includes complex research dealing with testing of a broad spectrum of carbonaceous adsorbents for removal of hydrogen sulfide and nitrite ions from water. The role of the surface functional groups of carbonaceous adsorbents, their acid-basic properties, and the influence of the type of impregnated heteroatom (N, O, or metals (Fe, Cu, Ni, on removal of hydrogen sulfide species and nitrite ions have been researched. The efficiency of the catalyst obtained from peach stones by impregnation with Cu2+ ions of oxidized active carbon was established, being recommended for practical purposes to remove the hydrogen sulfide species from the sulfurous ground waters. Comparative analysis of carbonaceous adsorbents reveals the importance of surface chemistry for oxidation of nitrite ions.

  15. Mixing state of aerosols and direct observation of carbonaceous and marine coatings on African dust by individual particle analysis

    Science.gov (United States)

    Deboudt, Karine; Flament, Pascal; ChoëL, Marie; Gloter, Alexandre; Sobanska, Sophie; Colliex, Christian

    2010-12-01

    The mixing state of aerosols collected at M'Bour, Senegal, during the Special Observing Period conducted in January-February 2006 (SOP-0) of the African Monsoon Multidisciplinary Analysis project (AMMA), was studied by individual particle analysis. The sampling location on the Atlantic coast is particularly adapted for studying the mixing state of tropospheric aerosols since it is (1) located on the path of Saharan dust plumes transported westward over the northern tropical Atlantic, (2) influenced by biomass burning events particularly frequent from December to March, and (3) strongly influenced by anthropogenic emissions from polluted African cities. Particle size, morphology, and chemical composition were determined for 12,672 particles using scanning electron microscopy (automated SEM-EDX). Complementary analyses were performed using transmission electron microscopy combined with electron energy loss spectrometry (TEM-EELS) and Raman microspectrometry. Mineral dust and carbonaceous and marine compounds were predominantly found externally mixed, i.e., not present together in the same particles. Binary internally mixed particles, i.e., dust/carbonaceous, carbonaceous/marine, and dust/marine mixtures, accounted for a significant fraction of analyzed particles (from 10.5% to 46.5%). Western Sahara was identified as the main source of mineral dust. Two major types of carbonaceous particles were identified: "tar balls" probably coming from biomass burning emissions and soot from anthropogenic emissions. Regarding binary internally mixed particles, marine and carbonaceous compounds generally formed a coating on mineral dust particles. The carbonaceous coating observed at the particle scale on African dust was evidenced by the combined use of elemental and molecular microanalysis techniques, with the identification of an amorphous rather than crystallized carbon structure.

  16. Geomechanical and anisotropic acoustic properties of Lower Jurassic Posidonia shales from Whitby (UK)

    Science.gov (United States)

    Zhubayev, Alimzhan; Houben, Maartje; Smeulders, David; Barnhoorn, Auke

    2014-05-01

    The Posidonia Shale Formation (PSF) is one of the possible resource shales for unconventional gas in Northern Europe and currently is of great interest to hydrocarbon exploration and production. Due to low permeability of shales, economically viable production requires hydraulic fracturing of the reservoir. The design of hydrofractures requires an estimate of stress state within the reservoir and geomechanical properties such as Young's modulus and Poisson's ratio. Shales are often highly anisotropic and the models which neglect shale anisotropy may fail to predict the behaviour of hydrofractures. Seismic attenuation anisotropy, on the other hand, can play a key role in quantitative rock characterization. Where the attenuation anisotropy can potentially be linked to anisotropic permeability of shales, its fluid/gas saturation and preferred development of anisotropic fracture orientations. In this research, by utilizing the so-called Thomsen's notations, the elastic anisotropy of our (fractured and unfractured) shales has been investigated using a pulse transmission technique in the ultrasonic frequency range (0.3-1 MHz). Assuming transverse isotropy of the shales, and taking the axis x3 as the axis of rotational symmetry, directional Young's moduli and Poisson's ratios were obtained. The Young's modulus measured parallel to bedding (E1) is found to be larger than the Young's modulus measured orthogonal to bedding (E3). In case of the Poisson's ratios, we found that ν31 is larger than ν12, where νijrelates elastic strain in xj direction to stress applied in xi direction. Finally, attenuation anisotropy in dry and layer-parallel fractured Posidonia shale samples has been studied in the same frequency range. The attenuation of compressional (QP-1) and shear (QS-1) waves increases substantially with a macro (or wavelength) fracture introduction, especially for P and S waves propagating orthogonal to the bedding. In non-fractured and fractured dry shales, QP-1 is

  17. Bacterial morphologies in carbonaceous meteorites and comet dust

    OpenAIRE

    2010-01-01

    Three decades ago the first convincing evidence of microbial fossils in carbonaceous chondrites was discovered and reported by Hans Dieter Pflug and his collaborators. In addition to morphology, other data, notably laser mass spectroscopy, confirmed the identification of such structures as putative bacterial fossils. Balloon-borne cryosampling of the stratosphere enables recovery of fragile cometary dust aggregates with their structure and carbonaceous matter largely intact. Scanning electron...

  18. Mechanism for electrochemical hydrogen insertion in carbonaceous materials

    Science.gov (United States)

    Qu, Deyang

    The mechanism for safe and reversible storage of hydrogen in porous carbonaceous materials by electrochemical decomposition of water in alkaline electrolyte is proposed. Atomic H was found to be inserted into the microdomains of defective graphene layers. Hydrogen storage capacity increases with increasing interlayer distance between carbon sheets. Hydrogen insertion in carbonaceous materials occurs at ambient conditions. Static potential acts as an electrochemical valve which can retain the hydrogen in the carbon structure, thus preventing leakage during storage.

  19. CARES: Carbonaceous Aerosol and Radiative Effects Study Science Plan

    Energy Technology Data Exchange (ETDEWEB)

    Zaveri, RA; Shaw, WJ; Cziczo, DJ

    2010-05-27

    Carbonaceous aerosol components, which include black carbon (BC), urban primary organic aerosols (POA), biomass burning aerosols, and secondary organic aerosols (SOA) from both urban and biogenic precursors, have been previously shown to play a major role in the direct and indirect radiative forcing of climate. The primary objective of the CARES 2010 intensive field study is to investigate the evolution of carbonaceous aerosols of different types and their effects on optical and cloud formation properties.

  20. Distinct Purine Distribution in Carbonaceous Chondrites

    Science.gov (United States)

    Callahan, Michael P.; Smith, Karen E.; Cleaves, Henderson J.; Ruzicka, Josef; Stern, Jennifer C.; Glavin, Daniel P.; House, Christopher H.; Dworkin, Jason P.

    2011-01-01

    Carbonaceous chondrite meteorites are known to contain a diverse suite of organic compounds, many of which are essential components of biochemistry. Amino acids, which are the monomers of proteins, have been extensively studied in such meteorites (e.g. Botta and Bada 2002; Pizzarello et aI., 2006). The origin of amino acids in meteorites has been firmly established as extraterrestrial based on their detection typically as racemic mixtures of amino acids, the presence of many non-protein amino acids, and non-terrestrial values for compound-specific deuterium, carbon, and nitrogen isotopic measurements. In contrast to amino acids, nucleobases in meteorites have been far less studied. Nucleobases are substituted one-ring (pyrimidine) or two-ring (purine) nitrogen heterocyclic compounds and serve as the information carriers of nucleic acids and in numerous coenzymes. All of the purines (adenine, guanine, hypoxanthine, and xanthine) and pyrimidines (uracil) previously reported in meteorites are biologically common and could be interpreted as the result of terrestrial contamination (e.g. van del' Velden and Schwartz, 1974.) Unlike other meteoritic organics, there have been no observations of stochastic molecular diversity of purines and pyrimidines in meteorites, which has been a criterion for establishing extraterrestrial origin. Maltins et al. (2008) performed compound-specific stable carbon isotope measurements for uracil and xanthine in the Murchison meteorite. They assigned a non-terrestrial origin for these nucleobases; however, the possibility that interfering indigenous molecules (e.g. carboxylic acids) contributed to the 13C-enriched isotope values for these nucleobases cannot be completely ruled out. Thus, the origin of these meteoritic nucleobases has never been established unequivocally. Here we report on our investigation of extracts of II different carbonaceous chondrites covering various petrographic types (Cl, CM, and CR) and degrees of aqueous alteration

  1. Hydrogen Absorbing Material in Carbonaceous-Metal Hydride

    Directory of Open Access Journals (Sweden)

    Farid Mulana

    2006-06-01

    Full Text Available One of the most promising materials for storing hydrogen in solid state would be included in metal-carbon composites. In order to obtain nanocrystalline metal particles encapsulated by crystalline or amorphous carbon, mechanosynthesis of zirconium-carbonaceous composites and alkali metal-carbonaceous composites was performed. For zirconium-carbonaceous composites, only zirconium-carbon black composite absorbed more hydrogen than expected for a mere mixture with the same composition. The higher hydrogen capacity on the zirconium-carbon black composite would be due to some specific sites on the carbonaceous material created during the milling. Another effect of the composite formation was stabilization of zirconium, that is, the composites did not ignite in air. On alkali metal-carbonaceous composites, carbon black has superior effect in composite formation compared with graphite in which some cooperative effect was only detected on alkali metal-carbon black composite. The effect of the carbonaceous composite formation was resistance to air and anti-sticking characteristics to balls and the wall of the vial during the ball milling.

  2. 4D synchrotron X-ray imaging to understand porosity development in shales during exposure to hydraulic fracturing fluid

    Science.gov (United States)

    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

  3. Safe Management of Waste Generated during Shale Gas Operations

    Science.gov (United States)

    Kukulska-Zając, Ewa; Król, Anna; Holewa-Rataj, Jadwiga

    2017-04-01

    Exploration and exploitation of hydrocarbon deposits, regardless of their type, are connected with the generation of waste, which may have various environmental effects. Such wastes may pose a serious risk to the surrounding environment and public health because they usually contain numerous potentially toxic chemicals. Waste associated with exploration and exploitation of unconventional hydrocarbon deposits is composed of a mixture of organic and inorganic materials, the qualitative and quantitative composition of which changes widely over time, depending on numerous factors. As a result the proper characteristic of this type of waste is very important. Information gained from detailed chemical analyses of drilling chemicals, drilling wastes, and flowback water can be used to manage shale gas-related wastes more appropriately, to develop treatment methods, to store the waste, and assess the potential environmental and health risk. The following paper will focus mainly on the results of research carried out on waste samples coming from the unconventional hydrogen exploration sites. Additionally, regulatory frameworks applicable to the management of wastes produced during this type of works will be discussed. The scope of research concerning physicochemical parameters for this type of wastes will also be presented. The presented results were obtained during M4ShaleGas project realization. The M4ShaleGas project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement no. 640715.

  4. Depositional Environment of the Sangkarewang Oil Shale, Ombilin Basin, Indonesia

    Directory of Open Access Journals (Sweden)

    Komang Anggayana

    2014-12-01

    Full Text Available Five samples from 56 m long drill core of lacustrine Sangkarewang oil shale have been studied by means of petrography and organic geochemistry to investigate the organic matter composition and depositional environments of the shale. The organic matter consists of abundant lamalginite (30%, v/v and very limited amount of vitrinite, suggesting aquatic depositional environments with minor terrestrial influence. Organic geochemical analysis exhibits the dominance of pristane, phytane, and generally n-alkanes compounds. These compounds might originate mostly from aquatic photosynthetic organisms. The oil shale was likely deposited in anoxic lake environments, suggested by the presence of framboidal pyrite (6%, v/v and preserved organic matter with total organic carbon (TOC about 4.9%. The pristane/phytane ratio is relatively high about 3.9 and thought as source sensitive rather than redox sensitive. Hopanoid and aryl isoprenoid compounds are present in minor amounts. The latter compounds are interpreted to be derived from green sulfur bacteria dwelling in anoxic and the presence of H2S in bottom water.

  5. Sulfide Generation by Dominant Halanaerobium Microorganisms in Hydraulically Fractured Shales

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-07-05

    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 microor- ganisms to catalyze thiosulfate-dependent sulfidogenesis. From these field data, we investigated biogenic sulfide production catalyzed by a Halanaerobium strain iso- lated from the produced fluids using proteogenomics and laboratory growth experi- ments. 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 sul- fide. 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 produc- tion by the same isolate. Increased production of sulfide and organic acids during the stationary growth phase suggests that fermentative Halanaerobium uses thiosul- fate 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 diagnos- tics.

  6. Low extraction recovery of fullerene from carbonaceous geological materials spiked with C{sub 60}

    Energy Technology Data Exchange (ETDEWEB)

    Jehlicka, J.; Frank, O.; Hamplova, V.; Pokorna, Z.; Juha, L.; Bohacek, Z.; Weishauptova, Z. [Charles University, Prague (Czech Republic). Inst. for Geochemical Mineral & Mineral Resources

    2005-08-01

    Soxhlet extraction, sonication, and ultracritical extraction were tested with respect to their capacity to extract fullerenes from natural carbonaceous materials. Toluene solutions with various contents of synthetic C{sub 60} were added to powdered graphite, shungite, bituminous coal, and quartz, with final C{sub 60} concentration 0.1-100 ppm. The C{sub 60}-doped materials were leached in three kinds of extraction apparatus. High-performance liquid chromatography (HPLC) was used to analyse the fullerene content in the obtained toluene extracts. Surprisingly low yields of the C{sub 60} extraction (most of them well below 5%) were determined for all the carbonaceous matrices and all the extraction techniques employed in the fullerene isolation. This finding has serious consequences for better understanding of the reported fullerene occurrence in the geological environment, because a greatly limited extraction yield can be responsible for some negative results of fullerene analyses in various geological samples. Both fullerene stability in solvents and fullerene interaction with the surfaces of geological carbonaceous matrices are discussed to explain the obtained results.

  7. Carbonaceous matter deposition in the high glacial regions of the Tibetan Plateau

    Science.gov (United States)

    Li, Chaoliu; Chen, Pengfei; Kang, Shichang; Yan, Fangping; Li, Xiaofei; Qu, Bin; Sillanpää, Mika

    2016-09-01

    Carbonaceous matter at glacial region plays important role in river ecosystems fed by glacier and albedo reduction of glacier surface. However, currently, limited knowledge are available on the carbonaceous matter within the glacial region of the Tibetan Plateau (TP). In this study, the data from six snowpits in the glacial region across the TP were reported. The results showed that dissolved organic carbon (DOC) concentrations of snowpit samples of the TP were comparable to those of European Alps and the Arctic. The ratio of DOC to carbonaceous matter (40.25 ± 8.98%) was lower than that of Alpine glaciers, thus indicating greater particulate carbon content in the TP glacial region. In addition, the DOC was significantly correlated with insoluble particulate carbon (IPC), indicating that IPC and DOC likely came from the same sources. Spatially, the DOC concentration decreased from the north (0.42 ± 0.29 mg-C L-1) to the south TP (0.15 ± 0.06 mg-C L-1), which was consistent with variations in the distribution of dust storm on the TP. Principal component analysis of major ions and DOC showed that mineral dust contributed the major part of DOC, followed by biogenic sources such as agriculture and livestock. Finally, based on DOC concentrations and precipitation amounts at different periods, the mean annul flux of DOC in the glacial region of the TP was calculated to be 0.11 ± 0.05 g-C m-2 yr-1.

  8. Analyzing the Chemical and Spectral Effects of Pulsed Laser Irradiation to Simulate Space Weathering of a Carbonaceous Chondrite

    Science.gov (United States)

    Thompson, M. S.; Keller, L. P.; Christoffersen, R.; Loeffler, M. J.; Morris, R. V.; Graff, T. G.; Rahman, Z.

    2017-01-01

    Space weathering processes alter the chemical composition, microstructure, and spectral characteristics of material on the surfaces of airless bodies. The mechanisms driving space weathering include solar wind irradiation and the melting, vaporization and recondensation effects associated with micrometeorite impacts e.g., [1]. While much work has been done to understand space weathering of lunar and ordinary chondritic materials, the effects of these processes on hydrated carbonaceous chondrites is poorly understood. Analysis of space weathering of carbonaceous materials will be critical for understanding the nature of samples returned by upcoming missions targeting primitive, organic-rich bodies (e.g., OSIRIS-REx and Hayabusa 2). Recent experiments have shown the spectral properties of carbonaceous materials and associated minerals are altered by simulated weathering events e.g., [2-5]. However, the resulting type of alteration i.e., reddening vs. bluing of the reflectance spectrum, is not consistent across all experiments [2-5]. In addition, the microstructural and crystal chemical effects of many of these experiments have not been well characterized, making it difficult to attribute spectral changes to specific mineralogical or chemical changes in the samples. Here we report results of a pulsed laser irradiation experiment on a chip of the Murchison CM2 carbonaceous chondrite to simulate micrometeorite impact processing.

  9. Magnetic anisotropy of Silurian organic-rich shale rocks and calcareous concretions from Northern Poland

    Science.gov (United States)

    Niezabitowska, Dominika; Szaniawski, Rafał

    2017-04-01

    The research has been performed on Wenlockian shales of Pelplin formation from the Pomerania region located in Northern Poland. These organic-rich marine shales were deposited on the western shelf of the Baltica paleo-continent and currently they constitute the cover of East European Platform. The studied shales lie almost completely flat without signs of tectonic deformations. Rock magnetic studies were carried out with the aim of recognizing ferro- and paramagnetic minerals in shales and thus fully understanding the origin of the magnetic anisotropy. The typical dark shales and spherical calcareous concretions from two boreholes were sampled. Based on deflection of shales beds bordered with a concretions, we deduce that such concretions were formed in the early stage of diagenesis, before the final compaction and lithification of surrounding shales. We obtained similar rockmagnetic results for both of rock types. The results of thermal variation of magnetic susceptibility and hysteresis loops show that the magnetic susceptibility is mainly controlled by paramagnetic minerals, due to domination of phyllosilicate minerals, with a smaller impact of ferromagnetic phase. The results of the hysteresis studies documented the domination of low coercivity ferromagnetic minerals, that is magnetite and pyrrhotite. The deposition alignment of flocculated phyllosilicates and further compaction determine distinct bedding parallel foliation of the AMS (Anisotropy of Magnetic Susceptibility) in the both drill cores. In one of the drill core the maximal AMS axes are almost randomly distributed in the bedding plane and show only a weak tendency for grouping. In the second drill core the magnetic lineation is better defined. In the case of concretions the bedding parallel magnetic foliation is also evident but it is much weaker than in shales. In turn, the magnetic lineation in the both drill cores is well developed and the maximal AMS axes are well grouped. In both of the cores

  10. Fourier Transform Infrared Spectroscopic Determination of Shale ...

    African Journals Online (AJOL)

    acer

    Square analysis; Mineralogy; Reservoir rocks; Shales. INTRODUCTION ... oxidation reactions of Turkish Goynuk and US. Green River .... handled which is essential in FTIR analysis because of ..... Conference Paper Number 9308. pp. Basalm ...

  11. Oil shale mining and processing in Estonia

    Energy Technology Data Exchange (ETDEWEB)

    Viilup, V. (Eesti Polevkivi Co., Johvi (Estonia))

    1994-01-01

    The overview begins with some background information containing historical data about the shale oil deposite in Estonia, which are well known since the 17th century. One major issue is the importance of the deposits in Estonia regarding the energy supply. Shale oil mining has been taking place there since 1919. More detailed information is supplied about the geology of those deposits that are close to the surface. They, today, are being exploited in six underground mines as well as three surface mines. Recent, most modern, technology is applied for working these mines. The mining methods, as well as the machines used for exploiting the shale oil, will be described in some more detail, followed by a closer look on the numerous possibilities of application of the shale oil products. In order to complete the overview some data and production numbers will be supplied. (orig.)

  12. Military jet fuel from shale oil

    Science.gov (United States)

    Coppola, E. N.

    1980-01-01

    Investigations leading to a specification for aviation turbine fuel produced from whole crude shale oil are described. Refining methods involving hydrocracking, hydrotreating, and extraction processes are briefly examined and their production capabilities are assessed.

  13. Ordovician faunas of Burgess Shale type.

    Science.gov (United States)

    Van Roy, Peter; Orr, Patrick J; Botting, Joseph P; Muir, Lucy A; Vinther, Jakob; Lefebvre, Bertrand; el Hariri, Khadija; Briggs, Derek E G

    2010-05-13

    The renowned soft-bodied faunas of the Cambrian period, which include the Burgess Shale, disappear from the fossil record in the late Middle Cambrian, after which the Palaeozoic fauna dominates. The disappearance of faunas of Burgess Shale type curtails the stratigraphic record of a number of iconic Cambrian taxa. One possible explanation for this loss is a major extinction, but more probably it reflects the absence of preservation of similar soft-bodied faunas in later periods. Here we report the discovery of numerous diverse soft-bodied assemblages in the Lower and Upper Fezouata Formations (Lower Ordovician) of Morocco, which include a range of remarkable stem-group morphologies normally considered characteristic of the Cambrian. It is clear that biotas of Burgess Shale type persisted after the Cambrian and are preserved where suitable facies occur. The Fezouata biota provides a link between the Burgess Shale communities and the early stages of the Great Ordovician Biodiversification Event.

  14. Paleontology: a new Burgess Shale fauna.

    Science.gov (United States)

    Briggs, Derek E G

    2014-05-19

    A spectacular Cambrian soft bodied fauna some 40 km from Walcott's original Burgess Shale locality includes over 50 taxa, some 20% new to science. New anatomical evidence from this site will illuminate the evolution of early marine animals.

  15. Aqueous processing of organic compounds in carbonaceous asteroids

    Science.gov (United States)

    Trigo-Rodríguez, Josep Maria; Rimola, Albert; Martins, Zita

    2015-04-01

    A (2002) Clay mineral-organic matter relationships in the early solar system. Meteorit Planet Sci 37:1829-1833. Rimola A, Costa D, Sodupe M, Lambert JF, Ugliengo P (2013) Silica surface features and their role in the adsorption of biomolecules: computational modeling and experiments. Chem Rev 113:4216-4313. Rimola A, Sodupe M, Ugliengo P (2007) Aluminosilicate as promoters for peptide bond formation: an assessment of Bernal's hypothesis by ab initio methods. J Am Chem soc 129:8333-8344 Trigo-Rodríguez JM, Moyano-Cambero CE, Llorca J, Formasier S, Barucci MA, Belskaya I, Martins Z, Rivkin AS, Dotto E, Madiedo JM, Alonso-Azcárate J (2014) UV to far-IR reflectance spectra of carbonaceous chondrites - I. Implications for remote characterization of dark primitive asteroids targeted by sample-return missions. Mon Not R Astron Soc 437:227-240. Trigo-Rodríguez JM, Alonso-Azcárate J, Abad MM, Lee MR (2015) Ultra high resolution Transmission Electron Microscopy of matrix mineral grains in CM chondrites: preaccretionary or parent body aqueous processing? LPI constribution, 46th LPSC, abstract #1198.

  16. Mineralized remains of morphotypes of filamentous cyanobacteria in carbonaceous meteorites

    Science.gov (United States)

    Hoover, Richard B.

    2005-09-01

    rocks, living, cryopreserved and fossilized extremophiles and cyanobacteria. These studies have resulted in the detection of mineralized remains of morphotypes of filamentous cyanobacteria, mats and consortia in many carbonaceous meteorites. These well-preserved and embedded microfossils are consistent with the size, morphology and ultra-microstructure of filamentous trichomic prokaryotes and degraded remains of microfibrils of cyanobacterial sheaths. EDAX elemental studies reveal that the forms in the meteorites often have highly carbonized sheaths in close association with permineralized filaments, trichomes, and microbial cells. The eextensive protocols and methodologies that have been developed to protect the samples from contamination and to distinguish recent contaminants from indigenous microfossils are described recent bio-contaminants. Ratios of critical bioelements (C:O, C:N, C:P, and C:S) reveal dramatic differences between microfossils in Earth rocks and meteorites and in the cells, filaments, trichomes, and hormogonia of recently living cyanobacteria. The results of comparative optical, ESEM and FESEM studies and EDAX elemental analyses of recent cyanobacteria (e.g. Calothrix, Oscillatoria, and Lyngbya) of similar size, morphology and microstructure to microfossils found embedded in the Murchison CM2 and the Orgueil CI1 carbonaceous meteorites are presented

  17. Important geological properties of unconventional resource shales

    Science.gov (United States)

    Slatt, Roger

    2011-12-01

    The revelation of vast global quantities of potentially productive gas and oil-prone shales has led to advancements in understanding important geological properties which impact reservoir performance. Based upon research on a variety of shales, several geological properties have been recognized as being common and important to hydrocarbon production. (1) transport/depositional processes include hemipelagic `rain', hyperpycnal flows, turbidity current flows, tempestites, wave-reworking, and contour currents in both shallow and deep water settings. (2) Common shale minerals include clays, quartz, calcite, dolomite, apatite, and pyrite; organic constituents include spores (Tasmanites), plant remains, biogenic quartz and calcite, and arenaceous foraminifera. (3) Porosity and permeability are characteristically low with pore sizes ranging down to the nanoscale. Main pore types include intergranular (including pores within clay floccules), porous organic matter, porous fecal pellets, and microfractures. (4) Important geochemical characteristics include organic richness (>3%), maturity (>1.1%Ro for shale gas and 0.6-0.9% for shale oil) and type (I-IV), in addition to certain biomarkers which are indicators of bottom water oxicity during deposition. Remaining hydrocarbon potential [RHP = (S1 + S2)/TOC] also reflects temporal environmental changes. `Isotopic reversals' can be used to detect best producing areas in shale-gas plays. (5) Lithofacies stacking patterns and sequence stratigraphy are the result of eustatic depositional history. A general sequence stratigraphic model is presented here that highlights this commonality. (6) Geomechanical properties are key to drilling, fracturing and production of hydrocarbons. Brittle-ductile couplets at several scales occur in shale sequences. (7) Geophysical properties, when calibrated to rock properties, provide a means of regionally to locally mapping the aforementioned properties. (8) Economic and societal considerations in the

  18. Analyses and characterization of fossil carbonaceous materials for silicon production

    Energy Technology Data Exchange (ETDEWEB)

    Myrvaagnes, Viktor

    2008-01-15

    Production of high silicon alloys is carried out in submerged arc furnaces by reduction of silicon bearing oxides (typically quartz) with carbon materials. Carbonaceous materials like coal, coke, charcoal and woodchips are commonly used as reduction materials in the process. Primarily based on historical prices of charcoal compared to fossil reduction materials, the Norwegian Ferroalloy Industry has mostly been using coal and coke (char) as the source of carbon. From a process point of view, the most important role of the carbonaceous material is to react with SiO gas to produce SiC. The ability of the reduction materials to react with SiO gas can be measured and the value is recognized as the reactivity of the carbon source. Reactivity is one of the most important parameters in the smelting process and is commonly acknowledged to strongly affect both productivity and specific energy consumption. The main objectives of this work has been to establish methods to characterize the material properties of fossil carbonaceous reduction materials used in the silicon process and to evaluated how these properties affect the reactivity towards SiO gas. In order to accomplish these objectives, three run of mine (ROM) single seam coals which are particularly well suited for ferroalloy production were selected. Two Carboniferous coals from USA (Blue Gem) and Poland (Staszic) with similar rank, but significantly different composition as well as a Permian coal from Australia (Peak Downs) have been characterized by chemical- and petrographical methods. Blue Gem is a homogeneous coal, low in mineral inclusions and macerals of the inertinite group and determined to have a random vitrinite reflectance of 0.71 %. Staszic has a similar reflectance of vitrinite (0.72 %), but is determined to be a very inhomogeneous coal with both inertinite macerals and minerals embedded in the vitrinite matrix. Peak Downs has a random reflectance of vitrinite of 1.32 % and is hence the coal sample of

  19. [Chemical hazards arising from shale gas extraction].

    OpenAIRE

    Daria Pakulska

    2015-01-01

    The development of the shale industry is gaining momentum and hence the analysis of chemical hazards to the environment and health of the local population is extremely timely and important. Chemical hazards are created during the exploitation of all minerals, but in the case of shale gas production, there is much more uncertainty as regards to the effects of new technologies application. American experience suggests the increasing risk of environmental contamination, mainly groundwater. The g...

  20. Highlights of the Messel Oil Shale

    Institute of Scientific and Technical Information of China (English)

    Stephan Schaal

    2008-01-01

    The Messel oil shale, Germany, was deposited in a maar crater that formed 47 million years ago. Since 1975 the Senckenberg Research Institute in Frankfurt am Main, has conducted systematic scientific excavations of this oil shale with much success. Besides plants and insects, more than 130 species of well-preserved fossil vertebrates like reptiles, fishes, birds and mammals have been found and have made Messel world-famous. Some examples of these vertebrates are presented.

  1. Mechanism for Burgess Shale-type preservation

    OpenAIRE

    Robert R. Gaines; Hammarlund, Emma U.; Hou, Xianguang; Qi, Changshi; Gabbott, Sarah E.; Zhao, Yuanlong; Peng, Jin; Canfield, Donald E.

    2012-01-01

    Exceptionally preserved fossil biotas of the Burgess Shale and a handful of other similar Cambrian deposits provide rare but critical insights into the early diversification of animals. The extraordinary preservation of labile tissues in these geographically widespread but temporally restricted soft-bodied fossil assemblages has remained enigmatic since Walcott’s initial discovery in 1909. Here, we demonstrate the mechanism of Burgess Shale-type preservation using sedimentologic and geochemic...

  2. The influence of shale gas on steamcracking

    Energy Technology Data Exchange (ETDEWEB)

    Rupieper, A. [Linde Engineering Dresden GmbH, Dresden (Germany)

    2013-11-01

    US shale gas reserves with more than 860 TCF (Source: U.S. Energy Information Administration study World Shale Gas Resources) account for 2 of the global largest reserves after China. In 7 areas of the US, these reserves are systematically explored, providing a significant amount of cheap natural gas source for decades. The ethane share, carried by such shale gas, can reach up to 16%. Ethane has been already in the past 2 most important feedstock for Steamcrackers, being the backbone of the Petrochemical Industry. Due to availability of vast shale gas, the US steamcracker industry is facing a shift from naphtha to shale gas ethane, as the margin of Ethylene produced from shale gas ethane is significantly larger than that of naphtha based Ethylene (app. + 630 USD/t Ethylene). As a consequence shale gas is ''the magic bullet'' incinerating investments into Steamcrackers and downstream plants for U.S petrochemical industry. Steamcracker Projects with an additional ethylene production capacity of more than 17 million tons/a by 2020 are announced or already under construction. Investments into downstream plants refining the C2 derivatives will follow or are already in planning/engineering phase. But the US market cannot absorb all related products, causing a significant export exposure, which will influence global trade flows for C2 derivatives and affect prices. This article presents the impact of shale gas ethane cracking on: - Trade flow of C2 derivatives; - By-product deficits; - Alternate C3+ derivative production routes; - Challenges related to engineering requirements and project execution for Steamcracker projects. (orig.)

  3. Long-Term Acid-Generating and Metal Leaching Potential of a Sub-Arctic Oil Shale

    Directory of Open Access Journals (Sweden)

    Kathryn A. Mumford

    2014-04-01

    Full Text Available Shales are increasingly being exploited for oil and unconventional gas. Exploitation of sub-arctic oil shales requires the creation of gravel pads to elevate workings above the heaving effects of ground ice. These gravel pads can potentially generate acidic leachate, which can enhance the mobility of metals from the shale. To examine this potential, pyrite-bearing shale originating from sub-Arctic gravel pad sites were subjected to leaching tests for 600 days at initial pH values ranging from 2 to 5, to simulate potential real world conditions. At set times over the 600 day experiment, pH, oxidation reduction potential (ORP, dissolved oxygen and temperature were recorded and small liquid samples withdrawn and analysed for elemental concentrations using total reflection X-ray fluorescence spectrometry (TRXRF. Six of eight shale samples were found to be acid generating, with pH declining and ORP becoming increasingly positive after 100 days. Two of the eight shale samples produced increasingly alkaline leachate conditions with relatively low ORP after 100 days, indicating an inbuilt buffering capacity. By 600 days the buffering capacity of all samples had been consumed and all leachate samples were acidic. TRXRF analyses demonstrated significant potential for the leaching of S, Fe, Ni, Cu, Zn and Mn with greatest concentrations found in reaction vessels with most acidic pH and highest ORP.

  4. Geochemical characterisation and of black shales from the Tarfaya-Layoune Basin (SW Morocco) : Implications for palaeoenvironmental controls on sulfurisation process of the organic matter

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Kolonic, S.; Wagner, T.; Kuypers, M.M.M.; Botcher, M.; Kuhn, W.; Whener, H.

    2002-01-01

    Organic geochemical and petrological investigations were carried out on Cenomanian/Turonian black shales from three sample sites in the Tarfaya Basin (SW Morocco) to characterize the sedimentary organic matter. These black shales have a variable bulk and molecular geochemical composition reflecting

  5. High efficiency shale oil recovery. Fifth quarterly report, January 1, 1993--March 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Adams, D.C.

    1993-04-22

    The overall project objective is to demonstrate the high efficiency of the Adams Counter-Current shale oil recovery process. The efficiency will first be demonstrated on a small scale, in the current phase, after which the demonstration will be extended to the operation of a small pilot plant. Thus the immediate project objective is to obtain data on oil shale retorting operations in a small batch rotary kiln that will be representative of operations in the proposed continuous process pilot plant. Although an oil shale batch sample is sealed in the batch kiln from the start until the end of the run, the process conditions for the batch are the same as the conditions that an element of oil shale would encounter in a continuous process kiln. Similar chemical and physical conditions (heating, mixing, pyrolysis, oxidation) exist in both systems.The two most important data objectives in this phase of the project are to demonstrate (1) that the heat recovery projected for this project is reasonable and (2) that an oil shale kiln will run well and not plug up due to sticking and agglomeration. The following was completed this quarter. (1) Twelve pyrolysis runs were made on five different oil shales. All of the runs exhibited a complete absence of any plugging, tendency. Heat transfer for Green River oil shale in the rotary kiln was 84.6 Btu/hr/ft{sup 2}/{degrees}F, and this will provide for ample heat exchange in the Adams kiln. (2) One retorted residue sample was oxidized at 1000{degrees}F. Preliminary indications are that the ash of this run appears to have been completely oxidized. (3) Further minor equipment repairs and improvements were required during the course of the several runs.

  6. Indigenous Carbonaceous Phases Embedded Within Surface Deposits on Apollo 17 Volcanic Glass Beads

    Science.gov (United States)

    Thomas-Keprta, K. L.; Clemett, S. J.; Ross, D. K.; Le, L.; McKay, D. S.; Gibson, E. K.; Gonzalez, C.

    2012-01-01

    The assessment of indigenous organic matter in returned lunar samples was one of the primary scientific goals of the Apollo program. Prior studies of Apollo samples have shown the total amount of organic matter to be in the range of approx 50 to 250 ppm. Low concentrations of lunar organics may be a consequence not only of its paucity but also its heterogeneous distribution. Several processes should have contributed to the lunar organic inventory including exogenous carbonaceous accretion from meteoroids and interplanetary dust particles, and endogenous synthesis driven by early planetary volcanism and cosmic and solar radiation.

  7. Relationship between indoor and outdoor carbonaceous particulates in roadside households

    Energy Technology Data Exchange (ETDEWEB)

    Funasaka, K.; Miyazaki, T.; Tsuruho, K. [Osaka City Institute of Public Health and Environmental Sciences (Japan); Tamura, K. [The National Institute for Minamata Disease, Kumamoto (Japan); Mizuno, T. [Mie University (Japan). Dept. of Chemistry for Materials; Kuroda, K. [Osaka City University Medical School (Japan). Dept. of Preventive Medicine and Environmental Health

    2000-07-01

    Concentrations of particulate matter (PM) and carbonaceous particulates in indoor and outdoor air at roadside private households were measured in Osaka, Japan. The particulate samples were collected on filters using a portable AND sampler capable of separating particles into three different size ranges: over 10 {mu}m, 2-10 {mu}m (coarse) and below 2 {mu}m (fine) in aerodynamic diameter. The filters were weighed and then analyzed for elemental carbon (EC) and organic carbon (OC) by thermal oxidation using a CHN CORDER. The results showed that indoor fine PM concentration is considerably affected by fine EC and the fine EC in indoor air is significantly correlated to that in outdoor air, r = 0.86 (n = 30, p < 0.001). A simple estimation from EC content ratio in diesel exhaust particles indicated that about 30% of indoor particulates of less than 10 {mu}m (PM10) were contributed from diesel exhaust. Additionally, the size characteristics of outdoor PM at roadside and background sites were examined using Andersen Cascade Impactors. (author)

  8. Evidence for Extended Aqueous Alteration in CR Carbonaceous Chondrites

    Science.gov (United States)

    Trigo-Rodriquez, J. M.; Moyano-Cambero, C. E.; Mestres, N.; Fraxedas, J.; Zolensky, M.; Nakamura, T.; Martins, Z.

    2013-01-01

    We are currently studying the chemical interrelationships between the main rockforming components of carbonaceous chondrites (hereafter CC), e.g. silicate chondrules, refractory inclusions and metal grains, and the surrounding meteorite matrices. It is thought that the fine-grained materials that form CC matrices are representing samples of relatively unprocessed protoplanetary disk materials [1-3]. In fact, modern non-destructive analytical techniques have shown that CC matrices host a large diversity of stellar grains from many distinguishable stellar sources [4]. Aqueous alteration has played a role in homogeneizing the isotopic content that allows the identification of presolar grains [5]. On the other hand, detailed analytical techniques have found that the aqueously-altered CR, CM and CI chondrite groups contain matrices in which the organic matter has experienced significant processing concomitant to the formation of clays and other minerals. In this sense, clays have been found to be directly associated with complex organics [6, 7]. CR chondrites are particularly relevant in this context as this chondrite group contains abundant metal grains in the interstitial matrix, and inside glassy silicate chondrules. It is important because CR are known for exhibiting a large complexity of organic compounds [8-10], and only metallic Fe is considered essential in Fischer-Tropsch catalysis of organics [11-13]. Therefore, CR chondrites can be considered primitive materials capable to provide clues on the role played by aqueous alteration in the chemical evolution of their parent asteroids.

  9. Legal Regime of Shale Gas Extraction

    Directory of Open Access Journals (Sweden)

    Ovidiu – Horia Maican

    2013-12-01

    Full Text Available Some countries with large reserves intend to promote shale gas production, in order to reduce their dependency on imported gas. Shale gas will be an important new aspect in the world energy scene, with many effects.European Union wants secure and affordable sources of energy. Natural gas is the cleanest fossil fuel and a vital component of European Union's energy strategy. One of the most important aspects is that gas produces significantly cleaner energy than other fossil fuels.From a legal point of view, extraction of oil and natural gas is one of the most highly-regulated activities.In European Union, the regulation of shale gas activities is different if we compare with United States. United States has a complete framework of federal and state regulation of shale gas extraction. More than that, these regulations have evolved in order to respond to the United States shale gas boom.Legal regime of shale gas extraction in every member state of European Union must put together national and European Union regulations in this field of activity.

  10. Environmental control costs for oil shale processes

    Energy Technology Data Exchange (ETDEWEB)

    None

    1979-10-01

    The studies reported herein are intended to provide more certainty regarding estimates of the costs of controlling environmental residuals from oil shale technologies being readied for commercial application. The need for this study was evident from earlier work conducted by the Office of Environment for the Department of Energy Oil Shale Commercialization Planning, Environmental Readiness Assessment in mid-1978. At that time there was little reliable information on the costs for controlling residuals and for safe handling of wastes from oil shale processes. The uncertainties in estimating costs of complying with yet-to-be-defined environmental standards and regulations for oil shale facilities are a critical element that will affect the decision on proceeding with shale oil production. Until the regulatory requirements are fully clarified and processes and controls are investigated and tested in units of larger size, it will not be possible to provide definitive answers to the cost question. Thus, the objective of this work was to establish ranges of possible control costs per barrel of shale oil produced, reflecting various regulatory, technical, and financing assumptions. Two separate reports make up the bulk of this document. One report, prepared by the Denver Research Institute, is a relatively rigorous engineering treatment of the subject, based on regulatory assumptions and technical judgements as to best available control technologies and practices. The other report examines the incremental cost effect of more conservative technical and financing alternatives. An overview section is included that synthesizes the products of the separate studies and addresses two variations to the assumptions.

  11. Spectro-microscopic measurements of carbonaceous aerosol aging in Central California

    Directory of Open Access Journals (Sweden)

    R. C. Moffet

    2013-10-01

    Full Text Available Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES was designed to study carbonaceous aerosols in the natural environment of the Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of a pollution accumulation event (27–29 June 2010, when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer-controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX and scanning transmission X-ray microscopy coupled with near-edge X-ray absorption spectroscopy (STXM/NEXAFS were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm equivalent circular diameter increased with plume age, as did the organic mass per particle. Comparison of the CARES spectro-microscopic dataset with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that fresh particles in Mexico City contained three times as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (ranging from 16.6 to 47.3% was larger than at the CARES urban site (13.4–15.7%, and the most aged samples from CARES contained fewer carbon–carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol

  12. Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

    Science.gov (United States)

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

    2009-01-01

    Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop-Zones A-C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite-smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C

  13. Developments in CO{sub 2} mineral carbonation of oil shale ash

    Energy Technology Data Exchange (ETDEWEB)

    Uibu, M., E-mail: maiuibu@staff.ttu.ee [Laboratory of Inorganic Materials, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn (Estonia); Velts, O.; Kuusik, R. [Laboratory of Inorganic Materials, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn (Estonia)

    2010-02-15

    Solid waste and atmospheric emissions originating from power production are serious problems worldwide. In the Republic of Estonia, the energy sector is predominantly based on combustion of a low-grade carbonaceous fossil fuel: Estonian oil shale. Depending on the combustion technology, oil shale ash contains 10-25% free lime. To transport the ash to wet open-air deposits, a hydraulic system is used in which 10{sup 7}-10{sup 8} cubic meters of Ca{sup 2+}-ion-saturated alkaline water (pH level 12-13) is recycled between the plant and sedimentation ponds. The goals of the current work were to design an ash-water suspension carbonation process in a continuous mode laboratory-scale plant and to search for potential means of intensifying the water neutralization process. The carbonation process was optimized by cascading reactor columns in which the pH progressed from alkaline to almost neutral. The amount of CO{sub 2} captured from flue gases can reach 1-1.2 million ton at the 2007 production level of the SC Narva Power Plants. Laboratory-scale neutralization experiments were carried out to compare two reactor designs. Sedimentation of PCC particles of rhombohedral crystalline structure was demonstrated and their main characteristics were determined. A new method providing 50x greater specific intensity is also discussed.

  14. CO2 Rebinding by Oil Shale CFBC Ashes: Effect of Pre-Treatment

    Science.gov (United States)

    Trikkel, Andres; Keelmann, Merli; Aranson, Aljona; Kuusik, Rein

    Power production in Estonia is predominantly based on combustion of a local low-grade fossil fuel Estonian oil shale. Due to the high content of carbonaceous mineral matter in oil shale, its combustion is related to formation of lime-containing ashes (content of free CaO 10-30%) which could be utilized as sorbents for CO2. In the present research CO2 uptake by circulating fluidized bed and pulverized firing ashes from different technological devices (furnace, cyclones etc) of an operating power plant was studied and the effect of pre-treatment (grinding, calcination at different temperatures) of these ashes on their capture capacity was estimated using thermogravimetric, SEM, X-Ray and EDX analysis methods. It was found that capture capacities were determined mainly by free CaO content in the ashes, thereby, fluidized bed ashes showed higher CaO conversion levels (19.2-74.2%) as compared to pulverized firing ones (8.7-51.8%). Pre-treatment conditions influenced noticeably CO2 uptake. Grinding decreased CO2 capture capacity of fluidized bed ashes, calcination at higher temperatures decreased capture capacity of both types of ashes. Clarification of this phenomenon was given. Kinetic analysis of the process has been carried out, mechanism of the reactions and respective kinetic constants have been estimated.

  15. Assessment of undiscovered shale gas and shale oil resources in the Mississippian Barnett Shale, Bend Arch–Fort Worth Basin Province, North-Central Texas

    Science.gov (United States)

    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.

  16. Assessment of undiscovered shale gas and shale oil resources in the Mississippian Barnett Shale, Bend Arch–Fort Worth Basin Province, North-Central Texas

    Science.gov (United States)

    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.

  17. Analyses and characterization of fossil carbonaceous materials for silicon production

    Energy Technology Data Exchange (ETDEWEB)

    Myrvaagnes, Viktor

    2008-01-15

    Production of high silicon alloys is carried out in submerged arc furnaces by reduction of silicon bearing oxides (typically quartz) with carbon materials. Carbonaceous materials like coal, coke, charcoal and woodchips are commonly used as reduction materials in the process. Primarily based on historical prices of charcoal compared to fossil reduction materials, the Norwegian Ferroalloy Industry has mostly been using coal and coke (char) as the source of carbon. From a process point of view, the most important role of the carbonaceous material is to react with SiO gas to produce SiC. The ability of the reduction materials to react with SiO gas can be measured and the value is recognized as the reactivity of the carbon source. Reactivity is one of the most important parameters in the smelting process and is commonly acknowledged to strongly affect both productivity and specific energy consumption. The main objectives of this work has been to establish methods to characterize the material properties of fossil carbonaceous reduction materials used in the silicon process and to evaluated how these properties affect the reactivity towards SiO gas. In order to accomplish these objectives, three run of mine (ROM) single seam coals which are particularly well suited for ferroalloy production were selected. Two Carboniferous coals from USA (Blue Gem) and Poland (Staszic) with similar rank, but significantly different composition as well as a Permian coal from Australia (Peak Downs) have been characterized by chemical- and petrographical methods. Blue Gem is a homogeneous coal, low in mineral inclusions and macerals of the inertinite group and determined to have a random vitrinite reflectance of 0.71 %. Staszic has a similar reflectance of vitrinite (0.72 %), but is determined to be a very inhomogeneous coal with both inertinite macerals and minerals embedded in the vitrinite matrix. Peak Downs has a random reflectance of vitrinite of 1.32 % and is hence the coal sample of

  18. Eo-Oligocene Oil Shales of the Talawi, Lubuktaruk, and Kiliranjao Areas, West Sumatra: Are they potential source rocks?

    Directory of Open Access Journals (Sweden)

    M. Iqbal

    2014-12-01

    Full Text Available DOI:10.17014/ijog.v1i3.198To anticipate the increasing energy demand, additional data and information covering unconventional fossil fuels such as oil shale must be acquired to promote the usage of alternative energy sources to crude oil. The Talawi and Lubuktaruk regions situated within intra-montane Ombilin Basin, and the Kiliranjao assumed to be a small intra montane basin are occupied by Eo-Oligocene sediments of Sangkarewang and Kiliran Formations, respectively. Field activity, geochemical screening techniques, and organic petrographic analysis, supported by SEM mode, are methods used. Most of the oil shale sequence is typically of an organically rich-succession comprising predominantly well-bedded, laminated and fissile, brownish to dark grey organic-rich shale and mudstone rocks. The exinite macerals within oil shale comprise mainly Pediastrum-lamalginite with minor cutinite, resinite, liptodetrinite, sporinite, bituminite, and rare Botryococcus-telalginite. Therefore; the oil shale deposits can be described as “lamosites”. Minor vitrinite maceral is also recognized. TOC analysis on selected shale samples corresponds to a fair up to excellent category of source rock characterization. The hydrogen index (HI for all samples shows a range of values from 207 - 864, and pyrolysis yield (PY ranges from 2.67 to 79.72 mg HC/g rock. The kerogen is suggested to be of mixed Type II and Type I autochthonous materials such as alginite, with minor allochthonous substances. Oil samples collected appear to be positioned within more oil prone rather than gas prone. Thermal maturity of the oil shales gained from Tmax value and production index (PI tends to show immature to marginally/early mature stage. A consistency in the thermal maturity level results by using both Tmax and vitrinite reflectance value is recognized. On the basis of  SEM analysis, the oil shale has undergone a late eodiagenetic process. Thereby, overall, vitrinite reflectance

  19. Eo-Oligocene Oil Shales of the Talawi, Lubuktaruk, and Kiliranjao Areas, West Sumatra: Are they potential source rocks?

    Directory of Open Access Journals (Sweden)

    M. Iqbal

    2014-12-01

    Full Text Available DOI:10.17014/ijog.v1i3.198To anticipate the increasing energy demand, additional data and information covering unconventional fossil fuels such as oil shale must be acquired to promote the usage of alternative energy sources to crude oil. The Talawi and Lubuktaruk regions situated within intra-montane Ombilin Basin, and the Kiliranjao assumed to be a small intra montane basin are occupied by Eo-Oligocene sediments of Sangkarewang and Kiliran Formations, respectively. Field activity, geochemical screening techniques, and organic petrographic analysis, supported by SEM mode, are methods used. Most of the oil shale sequence is typically of an organically rich-succession comprising predominantly well-bedded, laminated and fissile, brownish to dark grey organic-rich shale and mudstone rocks. The exinite macerals within oil shale comprise mainly Pediastrum-lamalginite with minor cutinite, resinite, liptodetrinite, sporinite, bituminite, and rare Botryococcus-telalginite. Therefore; the oil shale deposits can be described as “lamosites”. Minor vitrinite maceral is also recognized. TOC analysis on selected shale samples corresponds to a fair up to excellent category of source rock characterization. The hydrogen index (HI for all samples shows a range of values from 207 - 864, and pyrolysis yield (PY ranges from 2.67 to 79.72 mg HC/g rock. The kerogen is suggested to be of mixed Type II and Type I autochthonous materials such as alginite, with minor allochthonous substances. Oil samples collected appear to be positioned within more oil prone rather than gas prone. Thermal maturity of the oil shales gained from Tmax value and production index (PI tends to show immature to marginally/early mature stage. A consistency in the thermal maturity level results by using both Tmax and vitrinite reflectance value is recognized. On the basis of  SEM analysis, the oil shale has undergone a late eodiagenetic process. Thereby, overall, vitrinite reflectance

  20. Reconstruction of paleoenvironment recorded in the Ediacaran Lantain black shales

    Science.gov (United States)

    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.

  1. Experimental study on the physical and chemical properties of the deep hard brittle shale

    Directory of Open Access Journals (Sweden)

    Jian Xiong

    2016-03-01

    Full Text Available In the hard brittle shale formation, rock composition, physical and chemical properties, mechanics property before and after interacting with fluid have direct relation with borehole problems, such as borehole wall collapse, mud loss, hole shrinkage. To achieve hard brittle shale micro-structure, physical–chemical properties and mechanics property, energy-dispersive X-ray diffraction (XRD, cation exchange capacity experiment and hardness test are conducted. The result of laboratory experiments indicates that, clay mineral and quartz is dominated in mineral composition. In clay mineral, illite and illite/semectite mixed layers are abundant and there is no sign of montmorillonite. Value of cation exchange capacity (CEC ranges from 102.5–330 mmol/kg and average value is 199.56 mmol/kg. High value of CEC and content of clay mineral means hard brittle shale has strong ability of hydration. The image of XRD shows well developed micro-cracks and pores, which make rock failure easily, especially when fluid invades rock inside. Shale sample soaked with anti-high temperature KCL drilling fluid on shorter immersing time has stronger strength, whereas shale sample soaked with plugging and film forming KCL drilling fluid on longer immersing time has stronger strength.

  2. Many-body dissipative particle dynamics modeling of fluid flow in fine-grained nanoporous shales

    Science.gov (United States)

    Xia, Yidong; Goral, Jan; Huang, Hai; Miskovic, Ilija; Meakin, Paul; Deo, Milind

    2017-05-01

    A many-body dissipative particle dynamics model, namely, MDPD, is applied for simulation of pore-scale, multi-component, multi-phase fluid flows in fine-grained, nanoporous shales. Since this model is able to simultaneously capture the discrete features of fluid molecules in nanometer size pores and continuum fluid dynamics in larger pores, and is relatively easy to parameterize, it has been recognized as being particularly suitable for simulating complex fluid flow in multi-length-scale nanopore networks of shales. A remarkable feature of this work is the integration of a high-resolution FIB-SEM (focused ion beam scanning electron microscopy) digital imaging technique to the MDPD model for providing 3D voxel data that contain the invaluable geometrical and compositional information of shale samples. This is the first time that FIB-SEM is seamlessly linked to a Lagrangian model like MDPD for fluid flow simulation, which offers a robust approach to bridging gaps between the molecular- and continuum-scales, since the relevant spatial and temporal scales are too big for molecular dynamics, and too small for computational fluid dynamics with known constitutive models. Simulations ranging from a number of benchmark problems to a forced two-fluid flow in a Woodford shale sample are presented. Results indicate that this model can be used to deliver reasonable simulations for multi-component, multi-phase fluid flows in arbitrarily complex pore networks in shales.

  3. Permeability, compressibility and porosity of Jurassic shale from the Norwegian-Danish Basin

    DEFF Research Database (Denmark)

    Mbia, Ernest Ncha; Fabricius, Ida Lykke; Krogsbøll, Anette

    2014-01-01

    . Porosity measurements obtained using helium porosimetry-mercury immersion (HPMI), mercury injection capillary pressure (MICP) and nuclear magnetic resonance (NMR) techniques on the shale samples show that MICP porosity is 6-10% lower than HPMI or NMR porosity. Compressibility, from uniaxial loading......, and elastic wave velocities were measured simultaneously on saturated samples under drained conditions at room temperature. Uniaxial loading tests indicate that shale is significantly stiffer in situ than is normally assumed in geotechnical modelling. Permeability can be predicted from elastic moduli......, and from combined MICP and NMR data. The permeability predicted from Brunauer-Emmett-Teller (BET)-specific surface-area measurements using Kozeny's formulation for these shales, being rich in silt and kaolinite, falls in the same order of magnitude as permeability measured from constant rate of strain (CRS...

  4. Quantitative multi-scale analysis of mineral distributions and fractal pore structures for a heterogeneous Junger Basin shale

    Science.gov (United States)

    Wang, Y. D.; Liu, K. Y.; Yang, Y. S.; Ren, Y. Q.; Hu, T.; Deng, B.; Xiao, T. Q.

    2016-04-01

    Three dimensional (3D) characterization of shales has recently attracted wide attentions in relation to the growing importance of shale oil and gas. Obtaining a complete 3D compositional distribution of shale has proven to be challenging due to its multi-scale characteristics. A combined multi-energy X-ray micro-CT technique and data-constrained modelling (DCM) approach has been used to quantitatively investigate the multi-scale mineral and porosity distributions of a heterogeneous shale from the Junger Basin, northwestern China by sub-sampling. The 3D sub-resolution structures of minerals and pores in the samples are quantitatively obtained as the partial volume fraction distributions, with colours representing compositions. The shale sub-samples from two areas have different physical structures for minerals and pores, with the dominant minerals being feldspar and dolomite, respectively. Significant heterogeneities have been observed in the analysis. The sub-voxel sized pores form large interconnected clusters with fractal structures. The fractal dimensions of the largest clusters for both sub-samples were quantitatively calculated and found to be 2.34 and 2.86, respectively. The results are relevant in quantitative modelling of gas transport in shale reservoirs.

  5. Assessment of potential shale gas and shale oil resources of the Norte Basin, Uruguay, 2011

    Science.gov (United States)

    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.

  6. Shale Hydrocarbon Potential of Brown Shale, Central Sumatera Basin Based on Seismic and Well Data Analysis

    Science.gov (United States)

    Haris, Abdul; Agil Almunawwar, Husein; Riyanto, Agus; Bachtiar, Andang

    2017-04-01

    The development of unconventional shale hydrocarbon is really depending on integrating approach of wide range disciplines. The integrated approach for analysing organic-rich shale reservoirs involves calibration of core and well-log data, building petrophysical and rock-physics models, and finally characterizing the key reservoir parameters (TOC, porosity, and natural fractures) and mechanical properties evaluation from seismic data. In this research, integrated approach of geochemical, geomechanical, mineralogy, petrophysical, and geophysical analysis are carried out in Brown Shale, Central Sumatera Basin. Total Organic Carbon (TOC), maturity, and brittleness index are the main parameters used in this study to analyse the shale hydrocarbon potential. The result of geochemical analysis shows that the maturity level of shale in the interest zone in oil window, which means it can generate shale oil in early mature phase at depth of 6400 ft. Quantity of shale hydrocarbon potential is indicated by the TOC value of 0.5-1.2 wt. % (fair to good), with average of shale thickness for over 50 ft. The result of geomechanical analysis shows that brittleness index of interest zone for over 0.48 and rock strength below 10000 Psi.

  7. The carbonaceous concrete based on sawdust

    Directory of Open Access Journals (Sweden)

    BELOUSOVA Elena Sergeevna

    2015-06-01

    Full Text Available Today there are many requirements for strength, ecology and economy of produced concretes. The authors of the paper study attenuation of electromagnetic radiation of carbonaceous powders in the concrete composition. Carbon black was selected as a carbon powder for addition in concrete composition. Carbon black is a nanomaterial with disoriented structure of particles (average size is about 50 nm. The composition of the carbon black contains at least 90 wt.% amorphous carbon, more than 5 wt. % chemisorbed oxygen and about 4 wt.% of impurities. Materials with the addition of carbon black have electrical conductivity due to the high content of carbon. These materials are able to absorb electromagnetic radiation. For cement composition with addition of carbon black (more than 30 wt. % and water transmission coefficient of electromagnetic radiation is about –10 dB, for cement composition with 20 wt. % of carbon black the reflection coefficient is –8 dB in the frequency range 8–12 GHz. The concretes with a saturated aqueous solution of calcium chloride and 10% of carbon black possess minimal reflection coefficient (–14... –8 dB. Electromagnetic radiation shielding of concrete with the addition of sawdust was investigated. The concrete with sawdust (40 wt. % impregnated with an aqueous solution with carbon black has the reflection coefficient less than –8 dB and transmission coefficient –40 dB in the frequency range 8–12 GHz. These concretes can be used for creation of a shielded room with the technical equipment for information processing to prevent data leakage through the compromising emanations and crosstalk.

  8. Carbonaceous Components in the Comet Halley Dust

    Science.gov (United States)

    Fomenkova, M. N.; Chang, S.; Mukhin, L. M.

    1994-01-01

    Cometary grains containing large amounts of carbon and/or organic matter (CHON) were discovered by in situ measurements of comet Halley dust composition during VEGA and GIOTTO flyby missions. In this paper, we report the classification of these cometary, grains by means of cluster analysis, discuss the resulting compositional groups, and compare them with substances observed or hypothesized in meteorites, interplanetary dust particles, and the interstellar medium. Grains dominated by carbon and/or organic matter (CHON grains) represent approx. 22% of the total population of measured cometary dust particles. They, usually contain a minor abundance of rock-forming elements as well. Grains having organic material are relatively more abundant in the vicinity of the nucleus than in the outer regions of the coma, which suggests decomposition of the organics in the coma environment. The majority of comet Halley organic particles are multicomponent mixtures of carbon phases and organic compounds. Possibly, the cometary CHON grains may be related to kerogen material of an interstellar origin in carbonaceous meteorites. Pure carbon grains, hydrocarbons and polymers of cyanopolyynes, and multi-carbon monoxides are present in cometary dust as compositionally simple and distinctive components among a variety of others. There is no clear evidence of significant presence of pure formaldehyde or HCN polymers in Halley dust particles. The diversity of types of cometary organic compounds is consistent with the inter-stellar dust model of comets and probably reflects differences in composition of precursor dust. Preservation of this heterogeneity among submicron particles suggest the gentle formation of cometary, nucleus by aggregation of interstellar dust in the protosolar nebula without complete mixing or chemical homogenization at the submicron level.

  9. EVALUATION AND STANDARDIZATION OF ESTONIAN OIL SHALE QUALITY CHARACTERISTICS

    OpenAIRE

    Aruküla, Heino

    1997-01-01

    The most important mineral wealth of Estonia is oil shale, which is used as fuel for generating electricity, thermal energy, for producing the shale oil, impregnation oil, cement, concrete and other products.Estonian oil shale (Kukersite) deposit occupies an extensive territory (about of 1830 square km). Proved reserves in this deposit were estimated' about 4 billions tons of bil shale. (Fig. 1). The industrial oil shale seam (thickness 2,5 - 3,2 m) contains 6 "oil shale' layers (A - F2) whic...

  10. Uranium, yttrium, and rare earth elements accumulation during the Cretaceous anoxic events in carbonaceous rocks in the Pacific Ocean

    Science.gov (United States)

    Savelyeva, Olga; Philosofova, Tatyana; Bergal-Kuvikas, Olga; Savelyeva, Svetlana

    2017-04-01

    We have studied the carbonate-siliceous section of paleooceanic Albian-Cenomanian deposits on the Kamchatsky Mys peninsula (Eastern Kamchatka, Russia) [1].The section is represented by a rhythmic alternation of planktonic limestones and jaspers, accumulated in the open ocean environment. The rhythmicity can be attributed to climate variations that reflect a fluctuation of astronomical parameters (Milankovitch cycles) [2, 3].The section contains two beds enriched in organic carbon, corresponding to the two oceanic anoxic events - MCE and OAE2 [3]. The maximum content of organic matter in those beds reaches 68%. Our geochemical studies revealed an enrichment of the carbonaceous rocks in some major and trace elements including PGE, in comparison with the surrounding limestone and jasper [4].The accumulation of the ore elements in carbonaceous beds is caused by euxinic conditions during sedimentation.The content of uranium, yttrium, and rare earth elements in carbonaceous rocks is up to 60, 142 and 312 ppm respectively. Phosphate grains (bone detritus) with microinclusions of yttrium and uranium minerals were revealed in the carbonaceous rocks using the scanning electron microscope. These data prove the hypothesis of the sorbtion of U and Y by phosphate detritus from seawater. Microprobe analysis also showed an increased content of Cu, Zn, V in some pyrite framboids, which indicates that these elements are fixed in rocks by Fe-sulphide phase or organic matter under euxinic conditions. Our research may bring us closer to understanding the mechanism of syngenetic accumulation of metals in the black shales. This work was supported by the RFBR (No. 16-05-00546). [1] Palechek, T.N., Savelyev, D.P., Savelyeva, O.L. (2010) Stratigraphy and Geological Correlation 18, (1) 63-82. [2] Savelyeva, O.L. (2010). Vestnik Kraunts. Nauki o zemle 1 (15), 45-55 (in Russian). [3] Savelyev, D.P., Savelyeva, O.L., Palechek, T.N., Pokrovsky, B.G. (2012) Geophysical Research Abstracts, 14, EGU

  11. Synthesis of ordered carbonaceous frameworks from organic crystals.

    Science.gov (United States)

    Nishihara, Hirotomo; Hirota, Tetsuya; Matsuura, Kenta; Ohwada, Mao; Hoshino, Norihisa; Akutagawa, Tomoyuki; Higuchi, Takeshi; Jinnai, Hiroshi; Koseki, Yoshitaka; Kasai, Hitoshi; Matsuo, Yoshiaki; Maruyama, Jun; Hayasaka, Yuichiro; Konaka, Hisashi; Yamada, Yasuhiro; Yamaguchi, Shingi; Kamiya, Kazuhide; Kamimura, Takuya; Nobukuni, Hirofumi; Tani, Fumito

    2017-07-24

    Despite recent advances in the carbonization of organic crystalline solids like metal-organic frameworks or supramolecular frameworks, it has been challenging to convert crystalline organic solids into ordered carbonaceous frameworks. Herein, we report a route to attaining such ordered frameworks via the carbonization of an organic crystal of a Ni-containing cyclic porphyrin dimer (Ni2-CPDPy). This dimer comprises two Ni-porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni2-CPDPy crystal is thermally converted into a crystalline covalent-organic framework at 581 K and is further converted into ordered carbonaceous frameworks equipped with electrical conductivity by subsequent carbonization at 873-1073 K. In addition, the porphyrin's Ni-N4 unit is also well retained and embedded in the final framework. The resulting ordered carbonaceous frameworks exhibit an intermediate structure, between organic-based frameworks and carbon materials, with advantageous electrocatalysis. This principle enables the chemical molecular-level structural design of three-dimensional carbonaceous frameworks.Carbon-based materials are promising alternatives to noble metal catalysts, but their structures are typically disordered and difficult to control. Here, the authors obtain ordered carbonaceous frameworks with advantageous electrocatalytic properties via the carbonization of nickel-containing porphyrin dimer networks.

  12. Formation of nanoporous pyrobitumen residues during maturation processes within the Barnett Shale (Fort Worth Basin)

    Science.gov (United States)

    Bernard, S.; Wirth, R.; Schreiber, A.; Schulz, H.-M.; Horsfield, B.

    2012-04-01

    Hydrocarbon generation processes occur within organic-rich shales as a response to increases in thermal maturation. Shale gas reservoir quality is thought to be largely dependent on the extent to which solid organic material has been converted to pore space during catagenesis. Although pores may drastically vary in variety and abundance within differing shales, the occurrence of nanopores within organic particles has recently been documented for an important number of gas shale systems (i.e., Barnett, Haynesville, Utica, Eagle Ford, Woodford, Horn River, Marcellus, Posidonia …). However, despite their ubiquitous nature, the formation and the geochemical nature of these nanoporous organic compounds remain unclear. Here, we present the characterization of samples from the organic-rich Mississippian Barnett shale gas system (Fort Worth Basin, Texas, USA) at varying stages of thermal maturation. Using a combination of compositional organic geochemistry and spectromicroscopy techniques, including synchrotron-based scanning transmission X-ray microscopy (STXM - data collected using the CLS 10ID-1 STXM beamline) and transmission electron microscopy (TEM), we document a net increase in sample geochemical heterogeneity with increasing maturity. In addition to the presence of bitumen in samples of oil window maturity, very likely genetically derived from thermally degraded kerogen, the formation of nanoporous pyrobitumen has been inferred for samples of gas window maturity, likely resulting from the formation of gaseous hydrocarbons by secondary cracking of bitumen compounds. By providing in-situ insights into the fate of bitumen and pyrobitumen as a response to the thermal evolution of the macromolecular structure of kerogen, the present contribution constitutes an important step towards better constraining hydrocarbon generation processes occurring within unconventional gas shale systems.

  13. Pressurized fluidized-bed hydroretorting of Eastern oil shales. Annual report, June 1991--May 1992

    Energy Technology Data Exchange (ETDEWEB)

    Roberts, M.J.; Mensinger, M.C.; Rue, D.M.; Lau, F.S. [Institute of Gas Technology, Chicago, IL (United States); Schultz, C.W. [Alabama Univ., University, AL (United States); Parekh, B.K. [Kentucky Univ., Lexington, KY (United States); Misra, M. [Nevada Univ., Reno, NV (United States); Bonner, W.P. [Tennessee Technological Univ., Cookeville, TN (United States)

    1992-11-01

    The Devonian oil shales of the Eastern United States are a significant domestic energy resource. The overall objective of the multi-year program, initiated in October 1987 by the US Department of Energy is to perform the research necessary to develop the Pressurized Fluidized-Bed Hydroretorting (PFH) process for producing oil from Eastern oil shales. The program also incorporates research on technologies in areas such as raw shale preparation, beneficiation, product separation, and waste disposal that have the potential of improving the economics and/or environmental acceptability of recovering oil from oil shales using the PFH process. The results of the original 3-year program, which was concluded in May 1991, have been summarized in a four-volume final report published by IGT. DOE subsequently approved a 1-year extension to the program to further develop the PFH process specifically for application to beneficiated shale as feedstock. Studies have shown that beneficiated shale is the preferred feedstock for pressurized hydroretorting. The program extension is divided into the following active tasks. Task 3. testing of process improvement concepts; Task 4. beneficiation research; Task 5. operation of PFH on beneficiated shale; Task 6. environmental data and mitigation analyses; Task 7. sample procurement, preparation, and characterization; and Task 8. project management and reporting. In order to accomplish all the program objectives, the Institute of Gas Technology (IGT), the prime contractor, worked with four other institutions: the University of Alabama/Mineral Resources Institute (MRI), the University of Kentucky Center for Applied Energy Research (UK-CAER), the University of Nevada (UN) at Reno, and Tennessee Technological University (TTU). This report presents the work performed during the program extension from June 1, 1991 through May 31, 1992.

  14. Biomarker geochemistry of bituminous shale sequence and crude oil in the Ereǧli-Bor Basin (Konya-Niǧde), Central Anatolia, Turkey

    Science.gov (United States)

    Kara-Gulbay, Reyhan; Erdogan, Mert; Korkmaz, Sadettin; Kadinkiz, Gökhan

    2016-04-01

    In the Ereǧli-Bor Basin (Konya-Niǧde), Central Anatolia, bituminous shale sequence with thickness ranging between 72 and 160 m occurs in lacustrine deposits of Upper Miocene-Pliocene age. The live oil has also been observed in this bituminous shale sequence. Rock-Eval/TOC, GC and GC-MS analyses were conducted on selected bituminous shale samples from four borehole (key-12/1, key-12/2, key-12/3 key-12/4) and one crude oil sample from a borehole (key-12/2) in the basin. In this study, organic matter type, maturity and depositional environment of bituminous shale are evaluated and the origin of crude oil is determined by the bituminous shale-crude oil correlation. The total organic carbon (TOC) values of the bituminous shale samples range from 1.21-13.98 wt% with an average TOC value of 4.75wt%. The bituminous shale sequence is characterized by high HI (127-662 mg HC/g TOC) and low OI (7-50 mgCO2/TOC). Tmax varies from 332-419ᵒC. Very low Pr/Ph ratios of bituminous shale (0.09-0.22) are indicative of anoxic depositional conditions. C27 is dominate sterane for bituminous shale and crude oil samples with C27>C29>C28. Normal steranes are more dominant compare to iso- and diasteranes. Ouite high sterane/hopane ratios (1.14-2.70) indicate dominant algal organic matter input for bituminous shale and source rock of crude oil. C31R/hopane ratio for bituminous shale and crude oil samples are very low (0.09-0.13) and these ratio show a lacustrine depositional envirronment for bituminous shale and source rock of crude oil. Sterane and terpane distributions of bituminous shale and crude oil are very similar. A very good correlation in terms of biomarker between bituminous shale and crude oil samples indicate that source rock of crude oil is bituminous shale. The 22S/(22R + 22S) C32 homohopane ratios of bituminous shale and crude oil samples are found to be 0.56 and 0.61, indicating that homohopane isomerization has attained equilibrium and bituminous shale and crude oil are

  15. Characterization and separation of pyrite from Abu Tartur black shale

    Institute of Scientific and Technical Information of China (English)

    Ibrahim S.S.; El Kammar A.M.; Guda A.M.

    2015-01-01

    This work aimed for pyrite separation from Abu Tartur black shale as a source of sulfur to be an added economic value of Abu Tartur area. The considered samples in the present work were collected from a core drilled in Abu Tartur plateau representing the pyrite-rich black shale of the U. Cretaceous age. Sample characterization was carried out using petrographic microscope, XRD, DTA/DTG, C/S and XRF techniques. Clay minerals, silt-sized quartz, calcite, and hematite were the main minerals associating pyr-ite (5.34%). Liberation behavior of the sample was about 80%below 5 lm. Sample processing was achieved through one-day soaking followed by classification using 1 inch Mozley hydro-cyclone where about 35.5% by weight went to underflow and 64.5% went to overflow. The underflow product was subjected to an advanced gravity separation process using SB-40 Falcon Concentrator through a CCD statistical design prepared by Design-Expert 6.0 software proposed to opti-mize the separation process through a study for the effects of frequency (Hz) and water pressure (Psi) on both assay and recovery of the sulfur-rich heavy fraction. A heavy concentrate weighed 10.90%with inorganic sulfur content reached 11.37%(21.24%pyrite) with overall recovery (50.01%) was obtained after two cleaning at the optimum conditions.

  16. ANALYSIS OF DEVONIAN BLACK SHALES IN KENTUCKY FOR POTENTIAL CARBON DIOXIDE SEQUESTRATION AND ENHANCED NATURAL GAS PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall

    2003-07-28

    CO{sub 2} emissions from the combustion of fossil fuels have been linked to global climate change. Proposed carbon management technologies include geologic sequestration of CO{sub 2}. A possible, but untested, sequestration strategy is to inject CO{sub 2} into organic-rich shales. Devonian black shales underlie approximately two-thirds of Kentucky and are thicker and deeper in the Illinois and Appalachian Basin portions of Kentucky than in central Kentucky. The Devonian black shales serve as both the source and trap for large quantities of natural gas; total gas in place for the shales in Kentucky is estimated to be between 63 and 112 trillion cubic feet. Most of this natural gas is adsorbed on clay and kerogen surfaces, analogous to methane storage in coal beds. In coals, it has been demonstrated that CO{sub 2} is preferentially adsorbed, displacing methane. Black shales may similarly desorb methane in the presence of CO{sub 2}. The concept that black, organic-rich Devonian shales could serve as a significant geologic sink for CO{sub 2} is the subject of current research. To accomplish this investigation, drill cuttings and cores were selected from the Kentucky Geological Survey Well Sample and Core Library. Methane and carbon dioxide adsorption analyses are being performed to determine the gas-storage potential of the shale and to identify shale facies with the most sequestration potential. In addition, sidewall core samples are being acquired to investigate specific black-shale facies, their potential CO{sub 2} uptake, and the resulting displacement of methane. Advanced logging techniques (elemental capture spectroscopy) are being investigated for possible correlations between adsorption capacity and geophysical log measurements. Initial estimates indicate a sequestration capacity of 5.3 billion tons CO{sub 2} in the Lower Huron Member of the Ohio shale in parts of eastern Kentucky and as much as 28 billion tons total in the deeper and thicker portions of the

  17. Carbonaceous particles in the atmosphere: A historical perspective to the Fifth International Conference on Carbonaceous Particles in the Atmosphere

    Science.gov (United States)

    Penner, Joyce E.; Novakov, T.

    1996-08-01

    Carbonaceous aerosol species together with sulfates, other water-soluble inorganic compounds, and mineral particles play an important role in a variety of environmental effects. Carbonaceous particles contribute to the extinction of visible light by both scattering and absorption, thus influencing visibility degradation and radiative transfer through the atmosphere. These particles may serve as sites for condensation of water vapor and organic compounds. Components of carbonaceous material may contribute to atmospheric chemical processes because of their chemical and catalytic properties. Many of the original results in this field of research were first presented at the International Conferences on Carbonaceous Particles in the Atmosphere held in Berkeley (1978 and 1987) and in Linz and Vienna, Austria (1983 and 1991, respectively). At the fifth conference, August 23-26, 1994, at Lawrence Berkeley Laboratory, 85 papers were presented. This volume contains papers accepted for publication after peer review. In this introduction we attempt to provide an overview of research on carbonaceous particles from the 1950s to mid-1970s, which provided the backdrop for the first conference. We follow this by outlining research accomplishments and evolution of emphasis (as evidenced by the material presented at these conferences) and by summarizing the present state of this field of research.

  18. Provenance and weathering depth of carbonaceous gotland sandstone by use of carbon and oxygen isotopes

    Science.gov (United States)

    Åberg, G.; Löfvendahl, R.; Stijfhoorn, D.; Råheim, A.

    Carbon and oxygen isotope ratios of carbonates (calcite) from different sites and stratigraphic levels of the Gotland sandstone show that it might be possible to fingerprint the different quarries. Preliminary tests of nine samples of Gotland sandstone from different buildings show that the laser microprobe is an excellent tool for estimating depth of weathering on this carbonaceous sandstone. Analyses perpendicular to the stone surface gave a similar trend for the carbon and oxygen isotope ratios, although changes go deeper with δ13C than δ18O. Depth of weathering is controlled by exposure, location, biologic overgrowth and salt efflorescence. The effect of earlier conservation treatment with linseed oil can also be traced.

  19. Investigation into co-pyrolysis characteristics of oil shale and coal

    Institute of Scientific and Technical Information of China (English)

    Miao Zhenyong; Wu Guoguang; Li Ping; Meng Xianliang; Zheng Zhilei

    2012-01-01

    Samples of five types of coal and oil shale from the Daqing region have been subjected to co-pyrolysis in different blending ratios with thermo-gravimetry (TG).given a heating rate of 30 ℃/min to a final temperature of 900 ℃.Investigations on pyrolysis of mixing coal and oil shale in different proportions were carried out,indicating that the main scope of weight loss corresponding to hydrocarbon oil and gas release was between 350 and 550 ℃.At higher temperatures,significant weight loss was attributed to coke decomposition.Characteristic pyrolysis parameters of blends from oil shale and the high ranked XZ coal varied with the blending ratio,but oil shale dominated the process.At the same blending proportions,highly volatile medium and low ranked coal of low moisture and ash content reacted well during pyrolysis and could easily create synergies with oil shale.Medium and high ranked coal with high moisture content played a negative role in co-pyrolysis.

  20. Piceance Basin Oil Shale Data: Assays, Boreholes and Formation Tops

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This database contains Oil Shale Assays, Borehole Locations and Formation Tops that were used in support of the 2009 Oil Shale Assessment (Survey Fact Sheet...

  1. Control of Oxygen Concentration by Using a Carbonaceous Substance

    Directory of Open Access Journals (Sweden)

    Mohanad Jadan

    2005-01-01

    Full Text Available The control of oxygen concentration in gas flow may be used in chemical industry, heat power engineering, ecology, automobile construction and other industrial branches. This control is realized over a broad range of oxygen concentrations. The control of the oxygen concentration is based on passing of gas flow through a measuring cavity of radio spectrometer and measurement of a magnetic resonance signal. A change in the magnetic resonance signal of a dispersed carbonaceous substance, placed into the cavity, indicates to the changes in oxygen concentrations. The dispersed anthracite and thermal treatment cellulose substance in the oxygen-free medium are proposed to use as a carbonaceous substance.

  2. Short and long-term strength of shale rocks

    Science.gov (United States)

    Rybacki, Erik; Dresen, Georg

    2016-04-01

    Stimulation of oil and gas bearing shales commonly utilizes advanced hydraulic fracturing techniques to enhance the production rate. Successful hydrofrac campaigns depend on the geomechanical properties of the reservoir. For example, the short term strength and brittleness may control the hydraulic breakdown pressure and borehole stability. The long term creep properties may determine the closure rate of hydraulically induced fractures, for example by proppant embedment. We performed a series of mechanical tests on shales with different mineral content, porosity and maturity. Cylindrical samples of 1-5 cm in diameter and 2-10 cm in length were deformed at confining pressures of 0.1 - 400 MPa and temperatures of 25°-400°C in constant strain rate and constant stress mode in order to evaluate the influence of loading conditions and composition on their strength and ductility. Short-term constant strain rate tests show that, at fixed loading direction with respect to bedding orientation, the peak strength and Young's modulus vary with mineral content, humidity and porosity, but depend also on applied pressure, temperature and strain rate. The (porosity-corrected) variation of peak strength and Young's modulus with composition can be roughly estimated from the mechanical behavior of all components at given pressure-temperature conditions and their volumetric proportion. Samples deforming in the brittle-semibrittle regime may be characterized by empirical brittleness indices based on their deformation behavior, Young's modulus, or bulk composition. These indices are correlated at low pressure-temperature conditions (corresponding to long-term deformation experiments at constant load show transient viscoplastic creep behavior. The associated strain rates increase with increasing differential stress, increasing temperature and decreasing pressure, accompanied by slight porosity reduction. Therefore, estimates of fracture healing rates by proppant embedment require to

  3. New method for prediction of shale gas content in continental shale formation using well logs

    Science.gov (United States)

    Li, Sheng-Jie; Cui, Zhe; Jiang, Zhen-Xue; Shao, Yu; Liao, Wei; Li, Li

    2016-06-01

    Shale needs to contain a sufficient amount of gas to make it viable for exploitation. The continental heterogeneous shale formation in the Yan-chang (YC) area is investigated by firstly measuring the shale gas content in a laboratory and then investigating use of a theoretical prediction model. Key factors controlling the shale gas content are determined, and a prediction model for free gas content is established according to the equation of gas state and a new petrophysical volume model. Application of the Langmuir volume constant and pressure constant obtained from results of adsorption isotherms is found to be limited because these constants are greatly affected by experimental temperature and pressures. Therefore, using measurements of adsorption isotherms and thermodynamic theory, the influence of temperature, total organic carbon (TOC), and mineralogy on Langmuir volume constants and pressure constants are investigated in detail. A prediction model for the Langmuir pressure constant with a correction of temperatures is then established, and a prediction model for the Langmuir volume constant with correction of temperature, TOC, and quartz contents is also proposed. Using these corrected Langmuir constants, application of the Langmuir model determined using experimental adsorption isotherms is extrapolated to reservoir temperature, pressure, and lithological conditions, and a method for the prediction of shale gas content using well logs is established. Finally, this method is successfully applied to predict the shale gas content of the continental shale formation in the YC area, and practical application is shown to deliver good results with high precision.

  4. Elemental composition of airborne dust in the shale shaker house during an offshore drilling operation

    DEFF Research Database (Denmark)

    Hansen, A.B.; Larsen, E.; Hansen, L.V.

    1991-01-01

    During 2 days of an offshore drilling operation in the North Sea, 16 airborne dust samples from the atmosphere of the Shale Shaker House were collected onto filters. During this operation, drilling mud composed of a water slurry of barite (BaSO4) together with minor amounts of additives, among them...... coupled plasma-mass spectrometry). The total amount of dust collected varied from 0.04 to 1.41 mg m-3 with barium (Ba) as the single most abundant element. The open shale shakers turned out to be the major cause of generation of dust from the solid components of the drilling mud....

  5. Molecular characterization and comparison of shale oils generated by different pyrolysis methods using FT-ICR mass spectrometry

    Science.gov (United States)

    Jin, J.M.; Kim, S.; Birdwell, J.E.

    2011-01-01

    Fourier transform ion cyclotron resonance mass spectrometry (FT ICR-MS) was applied in the analysis of shale oils generated using two different pyrolysis systems under laboratory conditions meant to simulate surface and in situ oil shale retorting. Significant variations were observed in the shale oils, particularly the degree of conjugation of the constituent molecules. Comparison of FT ICR-MS results to standard oil characterization methods (API gravity, SARA fractionation, gas chromatography-flame ionization detection) indicated correspondence between the average Double Bond Equivalence (DBE) and asphaltene content. The results show that, based on the average DBE values and DBE distributions of the shale oils examined, highly conjugated species are enriched in samples produced under low pressure, high temperature conditions and in the presence of water.

  6. Multiphysical Testing of Soils and Shales

    CERN Document Server

    Ferrari, Alessio

    2013-01-01

    Significant advancements in the experimental analysis of soils and shales have been achieved during the last few decades. Outstanding progress in the field has led to the theoretical development of geomechanical theories and important engineering applications. This book provides the reader with an overview of recent advances in a variety of advanced experimental techniques and results for the analysis of the behaviour of geomaterials under multiphysical testing conditions. Modern trends in experimental geomechanics for soils and shales are discussed, including testing materials in variably saturated conditions, non-isothermal experiments, micro-scale investigations and image analysis techniques. Six theme papers from leading researchers in experimental geomechanics are also included. This book is intended for postgraduate students, researchers and practitioners in fields where multiphysical testing of soils and shales plays a fundamental role, such as unsaturated soil and rock mechanics, petroleum engineering...

  7. Shale gas development: a smart regulation framework.

    Science.gov (United States)

    Konschnik, Katherine E; Boling, Mark K

    2014-01-01

    Advances in directional drilling and hydraulic fracturing have sparked a natural gas boom from shale formations in the United States. Regulators face a rapidly changing industry comprised of hundreds of players, operating tens of thousands of wells across 30 states. They are often challenged to respond by budget cuts, a brain drain to industry, regulations designed for conventional gas developments, insufficient information, and deeply polarized debates about hydraulic fracturing and its regulation. As a result, shale gas governance remains a halting patchwork of rules, undermining opportunities to effectively characterize and mitigate development risk. The situation is dynamic, with research and incremental regulatory advances underway. Into this mix, we offer the CO/RE framework--characterization of risk, optimization of mitigation strategies, regulation, and enforcement--to design tailored governance strategies. We then apply CO/RE to three types of shale gas risks, to illustrate its potential utility to regulators.

  8. Thermocatalytical processing of coal and shales

    Directory of Open Access Journals (Sweden)

    Zhaksyntay Kairbekov

    2012-12-01

    Full Text Available The article investigates the questions of thermocatalytical conversion of organic mass of coal (OMC, it is shown that in the absence of a catalyst process is carried out by a radical process. Accumulated data on the properties for radicals of different structure and therefore different reaction capacity enables us to understand and interpret the conversion of OMC. Thermal conversion of OMC regarded as a kind of depolymerization, accompanied by decomposition of the functional groups with the formation of radicals, competing for hydrogen atom. Catalyst can change the direction and conditions of the process. Modern catalysts can reduce the process pressure up to 50 atm., with a high degree of coal conversion. We consider examples of simultaneous conversion of coal and shale, shale and masut, shale and tar.

  9. The Eocene Rusayl Formation, Oman, carbonaceous rocks in calcareous shelf sediments: Environment of deposition, alteration and hydrocarbon potential

    Energy Technology Data Exchange (ETDEWEB)

    Dill, H.G.; Wehner, H.; Kus, J. [Federal Institute for Geosciences and Natural Resources, P.O. Box 510163, D-30631 Hannover (Germany); Botz, R. [University Kiel, Geological-Paleontological Department, Olshausenstrasse 40-60, D-24118 Kiel (Germany); Berner, Z.; Stueben, D. [Technical University Karlsruhe, Institute for Mineralogy and Geochemistry, Fritz-Haber-Weg 2, D-76131 Karlsruhe (Germany); Al-Sayigh, A. [Sultan Qaboos University, Geological Dept. PO Box 36, Al-Khod (Oman)

    2007-10-01

    Paralic carbonaceous series intercalated among calcareous shelf sediments have seldom been investigated. During the early Eocene, calcareous and siliciclastic sediments were deposited on a wide shelf in front of low-reliefed hinterland in the Al Khawd region in NE Oman. The siliciclastic-calcareous sediments originated from strongly reworked debris of the Arabic Shield. The underlying Semail Ophiolite did not act as a direct source of debris but provided some heat to increase the maturity of carbonaceous rocks and modify the isotope signal of the calcareous minerals in the Rusayl Formation. A multidisciplinary approach involving sedimentology, mineralogy, chemistry, coal petrography and paleontology resulted in the establishment of nine stratigraphic lithofacies units and provides the reader with a full picture from deposition of the mixed carbonaceous-calcareous-siliciclastic rocks to the most recent stages of post-depositional alteration of the Paleogene formations. The calcareous Jafnayn Formation (lithofacies unit I) developed in a subtidal to intertidal regime, influenced episodically by storms. Deepening of the calcareous shelf towards younger series was ground to a halt by paleosols developing on a disconformity (lithofacies unit II) and heralding the onset of the Rusayl Formation. The stratigraphic lithofacies units III and IV reflect mangrove swamps which from time to time were flooded through washover fans from the open sea. The presence of Spinozonocolpites and the taxon Avicennia, which today belong to a coastal marsh vegetational community, furnish palynological evidence to the idea of extensive mangrove swamps in the Rusayl Formation [El Beialy, S.Y., 1998. Stratigraphic and palaeonenvironmental significance of Eocene palynomorphs from the Rusayl Shale Formation, Al Khawd, northern Oman. Review of Palaeobotany and Palynology 102, 249-258]. During the upper Rusayl Formation (lithofacies units V through VII) algal mats episodically flooded by marine

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

    Science.gov (United States)

    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

  11. Fluid flow from matrix to fractures in Early Jurassic shales

    NARCIS (Netherlands)

    Houben, M.E.; Hardebol, N.J.; Barnhoorn, A.; Boersma, Quinten; Carone, A.; Liu, Y.; de Winter, D.A.M.; Peach, C.J.; Drury, M.R.

    2017-01-01

    The potential of shale reservoirs for gas extraction is largely determined by the permeability of the rock. Typical pore diameters in shales range from the μm down to the nm scale. The permeability of shale reservoirs is a function of the interconnectivity between the pore space and the natural

  12. Joint DoD/DoE Shale Oil Project. Volume 3. Testing of Refined Shale Oil Fuels.

    Science.gov (United States)

    1983-12-01

    10-9. GROWTH RATINGS OF CLADOSPORIUM RESINAE AT VARIOUS INCUBATION STAGES ......................... 10-25 S 0 xv - LIST OF TABLES (Continued) TABLE 10...both shale DFM and shale JP-5 support heavy growth of Cladosporium resinae . Short-term engine performance tests were conducted on two gas turbine...microbiological growth of shale DFM and shale JP-5 was investigated by inoculating a mixture of fuel and 0 nutrient medium with Cladosporium resinae

  13. CO2 Utilization and Storage in Shale Gas Reservoirs

    Science.gov (United States)

    Schaef, T.; Glezakou, V.; Owen, T.; Miller, Q.; Loring, J.; Davidson, C.; McGrail, P.

    2013-12-01

    Surging natural gas production from fractured shale reservoirs and the emerging concept of utilizing anthropogenic CO2 for secondary recovery and permanent storage is driving the need for understanding fundamental mechanisms controlling gas adsorption and desorption processes, mineral volume changes, and impacts to transmissivity properties. Early estimates indicate that between 10 and 30 gigatons of CO2 storage capacity may exist in the 24 shale gas plays included in current USGS assessments. However, the adsorption of gases (CO2, CH4, and SO2) is not well understood and appears unique for individual clay minerals. Using specialized experimental techniques developed at PNNL, pure clay minerals were examined at relevant pressures and temperatures during exposure to CH4, CO2, and mixtures of CO2-SO2. Adsorbed concentrations of methane displayed a linear behavior as a function of pressure as determined by a precision quartz crystal microbalance. Acid gases produced differently shaped adsorption isotherms, depending on temperature and pressure. In the instance of kaolinite, gaseous CO2 adsorbed linearly, but in the presence of supercritical CO2, surface condensation increased significantly to a peak value before desorbing with further increases in pressure. Similarly shaped CO2 adsorption isotherms derived from natural shale samples and coal samples have been reported in the literature. Adsorption steps, determined by density functional theory calculations, showed they were energetically favorable until the first CO2 layer formed, corresponding to a density of ~0.35 g/cm3. Interlayer cation content (Ca, Mg, or Na) of montmorillonites influenced adsorbed gas concentrations. Measurements by in situ x-ray diffraction demonstrate limited CO2 diffusion into the Na-montmorillonite interlayer spacing, with structural changes related to increased hydration. Volume changes were observed when Ca or Mg saturated montmorillonites in the 1W hydration state were exposed to

  14. CO2 Sequestration within Spent Oil Shale

    Science.gov (United States)

    Foster, H.; Worrall, F.; Gluyas, J.; Morgan, C.; Fraser, J.

    2013-12-01

    Worldwide deposits of oil shales are thought to represent ~3 trillion barrels of oil. Jordanian oil shale deposits are extensive and of high quality, and could represent 100 billion barrels of oil, leading to much interest and activity in the development of these deposits. The exploitation of oil shales has raised a number of environmental concerns including: land use, waste disposal, water consumption, and greenhouse gas emissions. The dry retorting of oil shales can overcome a number of the environmental impacts, but this leaves concerns over management of spent oil shale and CO2 production. In this study we propose that the spent oil shale can be used to sequester CO2 from the retorting process. Here we show that by conducting experiments using high pressure reaction facilities, we can achieve successful carbonation of spent oil shale. High pressure reactor facilities in the Department of Earth Sciences, Durham University, are capable of reacting solids with a range of fluids up to 15 MPa and 350°C, being specially designed for research with supercritical fluids. Jordanian spent oil shale was reacted with high pressure CO2 in order to assess whether there is potential for sequestration. Fresh and reacted materials were then examined by: Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Thermogravimetric Analysis (TGA), X-Ray Fluorescence (XRF) and X-Ray Diffraction (XRD) methods. Jordanian spent oil shale was found to sequester up to 5.8 wt % CO2, on reacting under supercritical conditions, which is 90% of the theoretical carbonation. Jordanian spent oil shale is composed of a large proportion of CaCO3, which on retorting decomposes, forming CaSO4 and Ca-oxides which are the focus of carbonation reactions. A factorially designed experiment was used to test different factors on the extent of carbonation, including: pressure; temperature; duration; and the water content. Analysis of Variance (ANOVA) techniques were then used to determine the significance of

  15. A new CO carbonaceous chondrite from Acfer, Algeria

    OpenAIRE

    Salvadori, A; Moggi-Cecchi, V.; Pratesi, G.; I. Franchi; Greenwood, R.

    2006-01-01

    Many small fragments, totally weighing 118 g were found in the Acfer area by an Italian dealer. Chondrules size and types (predominance of granular olivine type), occurrence of twinned clinoenstatite and absence of plagioclase suggested a classification as CO carbonaceous chondrite.

  16. A new CK carbonaceous chondrite from Hammada Al Hamra, Libya

    OpenAIRE

    Pratesi, G.; Salvadori, A; Moggi-Cecchi, V.; I. Franchi; Greenwood, R.

    2006-01-01

    A single stone weighing 198 g was found in 2001 in the Hammada al Hamra region of Libya. Petrographic features (mean chondrules dimensions, coarse grained matrix and presence of AOIs and CAIs) point to a classification as CK carbonaceous chondrite. \\ud

  17. Surfactant-assisted liquefaction of particulate carbonaceous substances

    Science.gov (United States)

    Hsu, G. C. (Inventor)

    1978-01-01

    A slurry of carbonaceous particles such as coal containing an oil soluble polar substituted oleophilic surfactant, suitably an amine substituted long chain hydrocarbon, is liquefied at high temperature and high hydrogen presence. The pressure of surfactant results in an increase in yield and the conversion product contains a higher proportion of light and heavy oils and less asphaltene than products from other liquefaction processes.

  18. Modeling orbital gamma-ray spectroscopy experiments at carbonaceous asteroids

    Science.gov (United States)

    Lim, Lucy F.; Starr, Richard D.; Evans, Larry G.; Parsons, Ann M.; Zolensky, Michael E.; Boynton, William V.

    2017-01-01

    To evaluate the feasibility of measuring differences in bulk composition among carbonaceous meteorite parent bodies from an asteroid or comet orbiter, we present the results of a performance simulation of an orbital gamma-ray spectroscopy (GRS) experiment in a Dawn-like orbit around spherical model asteroids with a range of carbonaceous compositions. The orbital altitude was held equal to the asteroid radius for 4.5 months. Both the asteroid gamma-ray spectrum and the spacecraft background flux were calculated using the MCNPX Monte-Carlo code. GRS is sensitive to depths below the optical surface (to ≈20-50 cm depth depending on material density). This technique can therefore measure underlying compositions beneath a sulfur-depleted (e.g., Nittler et al.) or desiccated surface layer. We find that 3σ uncertainties of under 1 wt% are achievable for H, C, O, Si, S, Fe, and Cl for five carbonaceous meteorite compositions using the heritage Mars Odyssey GRS design in a spacecraft-deck-mounted configuration at the Odyssey end-of-mission energy resolution, FWHM = 5.7 keV at 1332 keV. The calculated compositional uncertainties are smaller than the compositional differences between carbonaceous chondrite subclasses.

  19. [Investigation of Carbonaceous Airborne Particles by Scanning Proton Microprobe].

    Science.gov (United States)

    Bao, Liang-man; Liu, Jiang-feng; Lei, Qian-tao; Li, Xiao-lin; Zhang, Gui-lin; Li, Yan

    2016-01-15

    Carbonaceous particles are an important component of the atmospheric aerosol particles and important for global climate change, air quality and human health. The PM₁₀ single particles from two environmental monitor locations and seven pollution emission sources were analyzed using scanning proton microprobe (SPM) techniques. The concentration of carbon in individual particles was quantitatively determined by proton non-Rutherford elastic backscattering spectrometry (EBS). The results of this investigation showed that carbonaceous particles were dominant in the pollution sources of coal and oil combustions, diesel busexhaust and automobile exhaust, while inorganic particles were dominant in the sources of steel industry, cement dust and soil dust. Carbonaceous matter was enriched in particles from the city center, while mineral matter was the main component of airborne particles in the industrial area. Elemental mapping of single aerosol particles yielded important information on the chemical reactions of aerosol particles. The micro-PIXE (particle induced X-ray emission) maps of S, Ca and Fe of individual carbonaceous particles showed that sulfuration reaction occurred between SO₂and mineral particles, which increased the sulfur content of particles.

  20. In situ remediation of contaminated sediments using carbonaceous materials

    NARCIS (Netherlands)

    Rakowska, M.I.; Kupryianchyk, D.; Harmsen, J.; Grotenhuis, J.T.C.; Koelmans, A.A.

    2012-01-01

    Carbonaceous materials (CM), such as activated carbons or biochars, have been shown to significantly reduce porewater concentrations and risks by binding hydrophobic organic compounds (HOCs) present in aquatic sediments. In the present study, the authors review the current state-of-the-art use of CM

  1. Comparison of static and dynamic properties in a shale rock

    Science.gov (United States)

    Bonnelye, Audrey; Pimienta, Lucas; Schubnel, Alexandre; David, Christian

    2017-04-01

    When trying to understand the elastic properties of rocks in order to ultimately compare laboratory and field data, two opposite measuring techniques can be used: the "static" and "dynamic" measurement techniques. The "static" measurement technique consists in characterising the medium by its strain response to an applied stress. The strain rate is generally low enough that the measurement can be addressed as static. Using ultrasonic wave velocity, the "dynamic" measurements are obtained. Those allow obtaining accurately the full set of elastic constants characterising the medium. However, such measuring procedure is at high frequency, implying the risk for dispersion and attenuation effects to occur. When comparing the "static" and "dynamic" measurements, and investigating their differences, the effect of the measuring frequency is often the parameter considered. However, it is not the only parameter that may play a role. Indeed, often, "static" measurements rely on strain amplitudes above 10-4. On the other hand, "dynamic" measurements rely on strain amplitudes below 10-6. Such difference may play an important role in comparing measurements in weak materials such as shales. For this particular rock, the effect of strain amplitude on the "static" measurements is investigated by decreasing the amplitude of stress variations. Moreover, due to both multiscale and sedimentary nature, shale materials can exhibit strong anisotropic properties, usually described as transversly isotropic. In this study we propose to compare the different ways of measuring elastic moduli of Tournemire shale (IRSN underground laboratory, Aveyron, Southern France). In a first part, static moduli were calculated on three sets of samples with different bedding orientations (90°, 0°, 45°) deformed under deviatoric pressure at different confining pressures (2.5, 5, 10, 20, 40, 80MPa). During these deformation experiments, elastic wave velocities were continuously measured along different

  2. Characteristics of atmospheric depositions of ionic and carbonaceous components at remote sites in Japan

    Science.gov (United States)

    Sato, K.; Inomata, Y.; Kajino, M.; Tang, N.; Hayakawa, K.; Hakamata, M.; Morisaki, H.

    2015-12-01

    Atmospheric deposition process is important to evaluate lifetimes and budget of atmospheric components. Deposition amounts of sulfur and nitrogen compounds have been evaluated not only in East Asian region but also worldwide. On the other hand, atmospheric deposition of carbonaceous components including organic carbon (OC), elementary carbon (EC) and Polycyclic Aromatic Hydrocarbons (PAHs) were monitored only at a few sites in Europe, North America and Africa, which will obscure removal process and atmospheric concentration distribution of those components. In this study, ionic and carbonaceous components in precipitation and aerosol are monitored at remote sites in Japan, and the characteristics of atmospheric deposition amounts were evaluated.Field observations have been implemented at the Noto station since November 2013 and the Sado station since May 2011. Wet deposition samples were collected by rain samplers, and dry deposition samples were collected by high volume or low volume aerosol samplers. Concentrations of Cl-, NO3-, SO42-, NH4+, Na+, K+, Mg2+, Ca2+ were measured by ion chromatography, EC and OC by the IMPROVE protocol, and PAHs by HPLC with a fluorescence detector. Wet deposition amounts were calculated as the products of aqueous concentration and precipitation amounts, and dry deposition amounts were as the products of aerosol concentrations and deposition velocity estimated by the Inferential Method.Total (wet and dry) annual deposition amounts of carbonaceous components of NO3-, SO42-, EC, water insoluble OC, Fluoranthene at Noto (Nov. 2013 to Oct. 2014) were 4353.81 mg/m2, 7020.50 mg/m2, 149.84 mg/m2, 1191.09 mg/m2, 28.6 μg/m2, respectively. These amounts are comparable total annual deposition amounts of OC and EC at Sado (May 2011 to Feb. 2012), which were 166.04 mg/m2 and 834.0 mg/m2. Higher deposition amounts of ionic and carbonaceous components were observed, which would be attributable to long range transportation of the East Asian

  3. Estimating emissions of toxic hydrocarbons from natural gas production sites in the Barnett Shale region

    Science.gov (United States)

    Marrero, J. E.; Townsend-Small, A.; Lyon, D. R.; Tsai, T.; Meinardi, S.; Blake, D. R.

    2015-12-01

    Throughout the past decade, shale gas operations have moved closer to urban centers and densely populated areas, contributing to growing public concerns regarding exposure to hazardous air pollutants (HAPs). These HAPs include gases like hexane, 1,3-butadiene and BTEX compounds, which can cause minor health effects from short-term exposure or possibly cancer due to prolonged exposure. During the Barnett Shale Coordinated Campaign in October, 2013, ground-based whole air samples revealed enhancements in several of these toxic volatile organic compounds (VOCs) downwind of natural gas well pads and compressor stations. Two methods were used to estimate the emission rate of several HAPs in the Barnett Shale. The first method utilized CH4 flux measurements derived from the Picarro Mobile Flux Plane (MFP) and taken concurrently with whole air samples, while the second used a CH4 emissions inventory developed for the Barnett Shale region. From these two approaches, the regional emission estimate for benzene (C6H6) ranged from 48 ± 16 to 84 ± 26 kg C6H6 hr-1. A significant regional source of atmospheric benzene is evident, despite measurement uncertainty and limited number of samples. The extent to which these emission rates equate to a larger public health risk is unclear, but is of particular interest as natural gas productions continues to expand.

  4. Geochemical Characteristics and its Geological Significance of Oil Shale from the Youganwo Formation, Maoming Basin, China

    Science.gov (United States)

    Zhou, Yuanyuan; Qiu, Nansheng

    2016-04-01

    Geochemical elements of oil shale in the Maoming Basin were analyzed to discuss provenance attribute and depositional environment of the Youganwo formation. Experimental date of the major elements, trace elements and rare earth elements of 24 samples from the Maoye 1 well were examined.The analyzed oil shale samples were characterized by enrichment of Th, U, Pb and LREE, depleted of Zr, Cr and Hf,negative Eu and Ce anomalies, indicating that these samples were originated from continental crust. The chemical index of alteration (CIA) values and the Zr/Sc-Th/Sc diagrams indicate that source rocks had undergone intense chemical weathering and deposition recirculation. Based on the La/Th-Hf and La/Yb-∑REE diagrams and the negative anomaly of Eu element, the oil shale in the Maoming Basin has diverse sources, which mainly came from felsic source region of the upper crust or the mixture of felsic volcanic rocks, granite and sedimentary rocks. Ratios of the Sr/Cu, MgO/CaO suggest that oil shale was formed in fresh water under warm and humid climate, shallow water column became deeper during the middle and late sedimentary period. The depositional environment is interpreted to be limnetic with weak reduction at the early stage and gradually turned into semi-deep to deep lacustrine.

  5. Thermal maturity of northern Appalachian Basin Devonian shales: Insights from sterane and terpane biomarkers

    Science.gov (United States)

    Hackley, Paul C.; Ryder, Robert T.; Trippi, Michael H.; Alimi, Hossein

    2013-01-01

    To better estimate thermal maturity of Devonian shales in the northern Appalachian Basin, eleven samples of Marcellus and Huron Shale were characterized via multiple analytical techniques. Vitrinite reflectance, Rock–Eval pyrolysis, gas chromatography (GC) of whole rock extracts, and GC–mass spectrometry (GCMS) of extract saturate fractions were evaluated on three transects that lie across previously documented regional thermal maturity isolines. Results from vitrinite reflectance suggest that most samples are immature with respect to hydrocarbon generation. However, bulk geochemical data and sterane and terpane biomarker ratios from GCMS suggest that almost all samples are in the oil window. This observation is consistent with the presence of thermogenic gas in the study area and higher vitrinite reflectance values recorded from overlying Pennsylvanian coals. These results suggest that vitrinite reflectance is a poor predictor of thermal maturity in early mature areas of Devonian shale, perhaps because reported measurements often include determinations of solid bitumen reflectance. Vitrinite reflectance interpretations in areas of early mature Devonian shale should be supplanted by evaluation of thermal maturity information from biomarker ratios and bulk geochemical data.

  6. Geochemical Proxies as an Effective Tool for Determining Depositional Environments for Burgess Shale-Type Fossil Localities

    Science.gov (United States)

    Powell, W.; Handle, K.

    2012-04-01

    A variety of models have been presented to account for the arrest of decay processes in Burgess Shale-type (BST) fossil beds. These models include sustained anoxia, fluctuating oxyclines, and hypersaline brines. Despite being questioned in the published literature, patterns in redox-sensitive metals may differentiate between these chemical environments of deposition. Accordingly, the redox indices V versus Al, V/Sc, Ni/Al, Ni/Co, and Mo were applied to two well-documented North American BST localities: 1) the Wheeler Formation (Utah, USA) with palaeontological characteristics indicating deposition within a fluctuating oxycline; and 2) the Burgess Shale (British Columbia, Canada) with field evidence indicating an association of fossil deposits with hypersaline brine pools. In addition, the chemical characteristics of the Kinzers Formation (Pennsylvania, USA), a BST fossil locality in which details of depositional environment are unclear due to limited outcrop exposure, were compared to those of the Wheeler and Burgess Shale formations. A set of eighty-four Wheeler Shale samples yielded a range of Ni/Co values from 0.6 to 10.5, and V/Sc values up to 27.9. Barren shales cluster along the line that defines the lithogenic maximum for V, whereas fossiliferous samples yielded a scattered distribution of V versus Al values above the lithogenic maximum. Molybdenum content was Shale samples. These data are consistent with deposition under a range of redox conditions, with fossils (both BST and trilobites) correlating with low-oxygen environments. In contrast, a set of 53 samples from the Burgess Shale and associated units yielded a restricted range of both Ni/Co (Burgess Shale strata beneath an oxygenated water column. Geochemical palaeo-redox proxies are consistent with field relationships and palaeontological data. This demonstrates that geochemical proxies can be applied effectively to BST fossil-bearing strata. Two units within the Kinzers Formation were studied: 1) the

  7. The Climate Effects Of Seasonally Varying Tropical Carbonaceous Aerosols

    Science.gov (United States)

    Jeong, G.; Wang, C.

    2008-12-01

    Biomass-burning emitted carbonaceous aerosols (BBCA) in the tropical region play an important role in the earth's radiation budget and hydrological cycle by absorbing and scattering sunlight and by acting as condensation nuclei for clouds. Due to the characteristics of their sources, the appearance of BBCA and thus their radiative forcing has a very strong seasonality. The climate effects of this type of seasonal aerosol forcing are not fully understood. In this study, the climate impact of strong periodic emissions of BBCA has been examined by using a three-dimensional interactive aerosol-climate system model developed based on the Community Atmospheric Model (CAM3) of NCAR. The aerosol module of this model describes size and mixing-state dependent physiochemical and radiative processes of seven aerosol modes using a two-moment scheme, including major anthropogenic aerosol constituents of sulfate, BC, and OC as well as their mixtures. The biomass burning emissions of carbonaceous aerosols were prepared based on the Global Emissions Inventory Activity (GEIA) monthly biomass burning black carbon data (http://www.geiacenter.org). The climate effect of seasonality of tropical carbonaceous aerosol forcing is derived by comparing modeled results of two 60-year integrations (driven by a slab ocean model) respectively using the constant and seasonal emissions of carbonaceous aerosols. We will discuss the difference in the BBCA-climate interaction caused by the seasonality of biomass-burning carbonaceous emissions, and the changes in the source and sink of aerosols as well as the transformation of their radiative and hygroscopic properties due to the seasonal emissions.

  8. ANALYSIS OF DEVONIAN BLACK SHALES IN KENTUCKY FOR POTENTIAL CARBON DIOXIDE SEQUESTRATION AND ENHANCED NATURAL GAS PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall

    2005-07-29

    Devonian gas shales underlie approximately two-thirds of Kentucky. In the shale, natural gas is adsorbed on clay and kerogen surfaces. This is analogous to methane storage in coal beds, where CO{sub 2} is preferentially adsorbed, displacing methane. Black shales may similarly desorb methane in the presence of CO{sub 2}. Drill cuttings from the Kentucky Geological Survey Well Sample and Core Library were sampled to determine CO{sub 2} and CH{sub 4} adsorption isotherms. Sidewall core samples were acquired to investigate CO{sub 2} displacement of methane. An elemental capture spectroscopy log was acquired to investigate possible correlations between adsorption capacity and mineralogy. Average random vitrinite reflectance data range from 0.78 to 1.59 (upper oil to wet gas and condensate hydrocarbon maturity range). Total organic content determined from acid-washed samples ranges from 0.69 to 14 percent. CO{sub 2} adsorption capacities at 400 psi range from a low of 14 scf/ton in less organic-rich zones to more than 136 scf/ton. There is a direct correlation between measured total organic carbon content and the adsorptive capacity of the shale; CO{sub 2} adsorption capacity increases with increasing organic carbon content. Initial estimates based on these data indicate a sequestration capacity of 5.3 billion tons of CO{sub 2} in the Lower Huron Member of the Ohio Shale of eastern Kentucky and as much as 28 billion tons total in the deeper and thicker parts of the Devonian shales in Kentucky. Should the black shales of Kentucky prove to be a viable geologic sink for CO{sub 2}, their extensive occurrence in Paleozoic basins across North America would make them an attractive regional target for economic CO{sub 2} storage and enhanced natural gas production.

  9. ANALYSIS OF DEVONIAN BLACK SHALES IN KENTUCKY FOR POTENTIAL CARBON DIOXIDE SEQUESTRATION AND ENHANCED NATURAL GAS PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall

    2004-08-01

    Devonian gas shales underlie approximately two-thirds of Kentucky. In the shale, natural gas is adsorbed on clay and kerogen surfaces. This is analogous to methane storage in coal beds, where CO{sub 2} is preferentially adsorbed, displacing methane. Black shales may similarly desorb methane in the presence of CO{sub 2}. Drill cuttings from the Kentucky Geological Survey Well Sample and Core Library are being sampled to collect CO{sub 2} adsorption isotherms. Sidewall core samples have been acquired to investigate CO{sub 2} displacement of methane. An elemental capture spectroscopy log has been acquired to investigate possible correlations between adsorption capacity and mineralogy. Average random vitrinite reflectance data range from 0.78 to 1.59 (upper oil to wet gas and condensate hydrocarbon maturity range). Total organic content determined from acid-washed samples ranges from 0.69 to 4.62 percent. CO{sub 2} adsorption capacities at 400 psi range from a low of 19 scf/ton in less organic-rich zones to more than 86 scf/ton in the Lower Huron Member of the shale. Initial estimates based on these data indicate a sequestration capacity of 5.3 billion tons of CO{sub 2} in the Lower Huron Member of the Ohio Shale of eastern Kentucky and as much as 28 billion tons total in the deeper and thicker parts of the Devonian shales in Kentucky. Should the black shales of Kentucky prove to be a viable geologic sink for CO{sub 2}, their extensive occurrence in Paleozoic basins across North America would make them an attractive regional target for economic CO{sub 2} storage and enhanced natural gas production.

  10. ANALYSIS OF DEVONIAN BLACK SHALES IN KENTUCKY FOR POTENTIAL CARBON DIOXIDE SEQUESTRATION AND ENHANCED NATURAL GAS PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall

    2005-01-28

    Devonian gas shales underlie approximately two-thirds of Kentucky. In the shale, natural gas is adsorbed on clay and kerogen surfaces. This is analogous to methane storage in coal beds, where CO{sub 2} is preferentially adsorbed, displacing methane. Black shales may similarly desorb methane in the presence of CO{sub 2}. Drill cuttings from the Kentucky Geological Survey Well Sample and Core Library were sampled to determine CO{sub 2} and CH{sub 4} adsorption isotherms. Sidewall core samples were acquired to investigate CO{sub 2} displacement of methane. An elemental capture spectroscopy log was acquired to investigate possible correlations between adsorption capacity and mineralogy. Average random vitrinite reflectance data range from 0.78 to 1.59 (upper oil to wet gas and condensate hydrocarbon maturity range). Total organic content determined from acid-washed samples ranges from 0.69 to 14 percent. CO{sub 2} adsorption capacities at 400 psi range from a low of 14 scf/ton in less organic-rich zones to more than 136 scf/ton. There is a direct correlation between measured total organic carbon content and the adsorptive capacity of the shale; CO{sub 2} adsorption capacity increases with increasing organic carbon content. Initial estimates based on these data indicate a sequestration capacity of 5.3 billion tons of CO{sub 2} in the Lower Huron Member of the Ohio Shale of eastern Kentucky and as much as 28 billion tons total in the deeper and thicker parts of the Devonian shales in Kentucky. Should the black shales of Kentucky prove to be a viable geologic sink for CO{sub 2}, their extensive occurrence in Paleozoic basins across North America would make them an attractive regional target for economic CO{sub 2} storage and enhanced natural gas production.

  11. ANALYSIS OF DEVONIAN BLACK SHALES IN KENTUCKY FOR POTENTIAL CARBON DIOXIDE SEQUESTRATION AND ENHANCED NATURAL GAS PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall

    2005-04-26

    Devonian gas shales underlie approximately two-thirds of Kentucky. In the shale, natural gas is adsorbed on clay and kerogen surfaces. This is analogous to methane storage in coal beds, where CO{sub 2} is preferentially adsorbed, displacing methane. Black shales may similarly desorb methane in the presence of CO{sub 2}. Drill cuttings from the Kentucky Geological Survey Well Sample and Core Library were sampled to determine CO{sub 2} and CH{sub 4} adsorption isotherms. Sidewall core samples were acquired to investigate CO{sub 2} displacement of methane. An elemental capture spectroscopy log was acquired to investigate possible correlations between adsorption capacity and mineralogy. Average random vitrinite reflectance data range from 0.78 to 1.59 (upper oil to wet gas and condensate hydrocarbon maturity range). Total organic content determined from acid-washed samples ranges from 0.69 to 14 percent. CO{sub 2} adsorption capacities at 400 psi range from a low of 14 scf/ton in less organic-rich zones to more than 136 scf/ton. There is a direct correlation between measured total organic carbon content and the adsorptive capacity of the shale; CO{sub 2} adsorption capacity increases with increasing organic carbon content. Initial estimates based on these data indicate a sequestration capacity of 5.3 billion tons of CO{sub 2} in the Lower Huron Member of the Ohio Shale of eastern Kentucky and as much as 28 billion tons total in the deeper and thicker parts of the Devonian shales in Kentucky. Should the black shales of Kentucky prove to be a viable geologic sink for CO{sub 2}, their extensive occurrence in Paleozoic basins across North America would make them an attractive regional target for economic CO{sub 2} storage and enhanced natural gas production.

  12. Organic Matter from Comet 81p/Wild 2, IDPS and Carbonaceous Meteorites; Similarities and Differences

    Energy Technology Data Exchange (ETDEWEB)

    Wirick, S.; Flynn, G; Keller, L; Nakamura Messenger, K; Peltzer, C; Jacobsen, C; Sandford, S; Zolensky, M

    2009-01-01

    During preliminary examination of 81P/Wild 2 particles collected by the NASA Stardust spacecraft, we analyzed seven, sulfur embedded and ultramicrotomed particles extracted from five different tracks. Sections were analyzed using a scanning transmission X-ray microscope (SXTM) and carbon X-ray absorption near edge structure (XANES) spectra were collected. We compared the carbon XANES spectra of these Wild 2 samples with a database of spectra on thirty-four interplanetary dust particles (IDPs) and with several meteorites. Two of the particles analyzed are iron sulfides and there is evidence that an aliphatic compound associated with these particles can survive high temperatures. An iron sulfide from an IDP demonstrates the same phenomenon. Another, mostly carbon free containing particle radiation damaged, something we have not observed in any IDPs we have analyzed or any indigenous organic matter from the carbonaceous meteorites, Tagish Lake, Orgueil, Bells and Murchison. The carbonaceous material associated with this particle showed no mass loss during the initial analysis but chemically changed over a period of two months. The carbon XANES spectra of the other four particles varied more than spectra from IDPs and indigenous organic matter from meteorites. Comparison of the carbon XANES spectra from these particles with 1. the carbon XANES spectra from thirty-four IDPs (<15 micron in size) and 2. the carbon XANES spectra from carbonaceous material from the Tagish Lake, Orgueil, Bells, and Murchison meteorites show that 81P/Wild 2 carbon XANES spectra are more similar to IDP carbon XANES spectra then to the carbon XANES spectra of meteorites.

  13. [Chemical hazards arising from shale gas extraction].

    Science.gov (United States)

    Pakulska, Daria

    2015-01-01

    The development of the shale industry is gaining momentum and hence the analysis of chemical hazards to the environment and health of the local population is extreiely timely and important. Chemical hazards are created during the exploitation of all minerals, but in the case of shale gas production, there is much more uncertainty as regards to the effects of new technologies application. American experience suggests the increasing risk of environmental contamination, mainly groundwater. The greatest, concern is the incomplete knowledge of the composition of fluids used for fracturing shale rock and unpredictability of long-term effects of hydraulic fracturing for the environment and health of residents. High population density in the old continent causes the problem of chemical hazards which is much larger than in the USA. Despite the growing public discontent data on this subject are limited. First of all, there is no epidemiological studies to assess the relationship between risk factors, such as air and water pollution, and health effects in populations living in close proximity to gas wells. The aim of this article is to identify and discuss existing concepts on the sources of environmental contamination, an indication of the environment elements under pressure and potential health risks arising from shale gas extraction.

  14. Chemical hazards arising from shale gas extraction

    Directory of Open Access Journals (Sweden)

    Daria Pakulska

    2015-02-01

    Full Text Available The development of the shale industry is gaining momentum and hence the analysis of chemical hazards to the environment and health of the local population is extremely timely and important. Chemical hazards are created during the exploitation of all minerals, but in the case of shale gas production, there is much more uncertainty as regards to the effects of new technologies application. American experience suggests the increasing risk of environmental contamination, mainly groundwater. The greatest concern is the incomplete knowledge of the composition of fluids used for fracturing shale rock and unpredictability of long-term effects of hydraulic fracturing for the environment and health of residents. High population density in the old continent causes the problem of chemical hazards which is much larger than in the USA. Despite the growing public discontent data on this subject are limited. First of all, there is no epidemiological studies to assess the relationship between risk factors, such as air and water pollution, and health effects in populations living in close proximity to gas wells. The aim of this article is to identify and discuss existing concepts on the sources of environmental contamination, an indication of the environment elements under pressure and potential health risks arising from shale gas extraction. Med Pr 2015;66(1:99–117

  15. Electromagnetic De-Shaling of Coal

    NARCIS (Netherlands)

    De Jong, T.P.R.; Mesina, M.B.; Kuilman, W.

    2003-01-01

    The efficiency with which an electromagnetic sensor array is able to distinguish density and ash content of coal and shale mixtures was determined experimentally. The investigated sensor was originally designed for automatic metal detection and sorting in industrial glass recycle processing, where i

  16. China organic-rich shale geologic features and special shale gas production issues

    Directory of Open Access Journals (Sweden)

    Yiwen Ju

    2014-06-01

    Full Text Available The depositional environment of organic-rich shale and the related tectonic evolution in China are rather different from those in North America. In China, organic-rich shale is not only deposited in marine environment, but also in non-marine environment: marine-continental transitional environment and lacustrine environment. Through analyzing large amount of outcrops and well cores, the geologic features of organic-rich shale, including mineral composition, organic matter richness and type, and lithology stratigraphy, were analyzed, indicating very special characteristics. Meanwhile, the more complex and active tectonic movements in China lead to strong deformation and erosion of organic-rich shale, well-development of fractures and faults, and higher thermal maturity and serious heterogeneity. Co-existence of shale gas, tight sand gas, and coal bed methane (CBM proposes a new topic: whether it is possible to co-produce these gases to reduce cost. Based on the geologic features, the primary production issues of shale gas in China were discussed with suggestions.

  17. The application of thermal methods for determining chemical composition of carbonaceous aerosols: a review.

    Science.gov (United States)

    Chow, Judith C; Yu, Jian Zhen; Watson, John G; Ho, Steven Sai Hang; Bohannan, Theresa L; Hays, Michael D; Fung, Kochy K

    2007-09-01

    Thermal methods of various forms have been used to quantify carbonaceous materials. Thermal/optical carbon analysis provides measurements of organic and elemental carbon concentrations as well as fractions evolving at specific temperatures in ambient and source aerosols. Detection of thermally desorbed organic compounds with thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) identifies and quantifies over 100 individual organic compounds in particulate matter (PM) samples. The resulting mass spectra contain information that is consistent among, but different between, source emissions even in the absence of association with specific organic compounds. TD-GC/MS is a demonstrated alternative to solvent extraction for many organic compounds and can be applied to samples from existing networks. It is amenable to field-deployable instruments capable of measuring organic aerosol composition in near real-time. In this review, thermal stability of organic compounds is related to chemical structures, providing a basis for understanding thermochemical properties of carbonaceous aerosols. Recent advances in thermal methods applied to determine aerosol chemical compositions are summarized and their potential for uncovering aerosol chemistry are evaluated. Current limitations and future research needs of the thermal methods are included.

  18. Testing for fullerenes in geologic materials: Oklo carbonaceous substances, Karelian shungites, Sudbury Black Tuff

    Science.gov (United States)

    Mossman, David; Eigendorf, Guenter; Tokaryk, Dennis; Gauthier-Lafaye, François; Guckert, Kristal D.; Melezhik, Victor; Farrow, Catharine E. G.

    2003-03-01

    Fullerenes have been reported from diverse geologic environments since their discovery in shungite from Karelian Russia. Our investigation is prompted by the presence of onionskin-like structures in some carbonaceous substances associated with the fossil nuclear fission reactors of Oklo, Gabon. The same series of extractions and the same instrumental techniques, laser desorption ionization and high-resolution mass spectroscopy (electron-impact mass spectroscopy), were employed to test for fullerenes in samples from three different localities: two sites containing putative fullerenes (Sudbury Basin and Russian Karelia) and one new location (Oklo, Gabon). We confirm the presence of fullerenes (C60 and C70) in the Black Tuff of the Onaping Formation impact breccia in the Sudbury Basin, but we find no evidence of fullerenes in shungite samples from various locations in Russian Karelia. Analysis of carbonaceous substances associated with the natural nuclear fission reactors of Oklo yields no definitive signals for fullerenes. If fullerenes were produced during sustained nuclear fission at Oklo, then they are present below the detection limit (˜100 fmol), or they have destabilized since formation. Contrary to some expectations, geologic occurrences of fullerenes are not commonplace.

  19. Blackening of fault gouge by comminution and pyrolysis of carbonaceous materials during earthquake slip

    Science.gov (United States)

    Kaneki, S.; Hirono, T.

    2015-12-01

    Fault gouges often exhibit various colors (white-pink-green-brown-gray-black), and particularly those developed in sedimentary rocks show gray to black. However, the physicochemical process for the color transition accompanied with seismic slip has not yet been fully understood. On the other hand, determination of the peak temperature during slip is crucial to identify the faulting mechanism during an earthquake, so that various temperature proxies have been proposed. For example, 1) magnetite formation at high temperature of ≥400 °C, 2) anomalies in the concentrations of fluid-mobile trace elements (Sr, Cs, Rb, and Li) and in the Sr isotope ratios, indicating presence of high-temperature fluid of ≥350 °C, 3) dehydroxylation of clay minerals, 4) thermal decomposition of carbonate minerals, and 5) thermal maturation of carbonaceous material examined by vitrinite reflectance measurement and by infrared and Raman spectroscopies. However, these proxies required high-level analyses in laboratory, so easy method to detect the record of high temperature preliminarily on field would be expected. In this study, we reproduced the blackening of synthetic fault sample by using high-velocity friction apparatus, thermogravimetric, and milling machine, and evaluated the color transition and organic chemical property of the samples by using UV-visible/NIR spectrophotometer and pyrolysis-gas chromatography-mass spectrometry. We discuss the process of the blackening taking comminution and pyrolysis of carbonaceous materials into consideration.

  20. Nanoscale Experimental Characterization and 3D Mechanistic Modeling of Shale with Quantified Heterogeneity

    Science.gov (United States)

    Bennett, K. C.; Borja, R. I.

    2014-12-01

    Shale is a fine-grained sedimentary rock consisting primarily of clay and silt, and is of particular interest with respect to hydrocarbon production as both a source and seal rock. The deformation and fracture properties of shale depend on the mechanical properties of its basic constituents, including solid clay particles, inclusions such as silt and organics, and multiscale porosity. This paper presents the results of a combined experimental/numerical investigation into the mechanical behavior of shale at the nanoscale. Large grids of nanoindentation tests, spanning various length scales ranging from 200-20000 nanometers deep, were performed on a sample of Woodford shale in both the bedding plane normal (BPN) and bedding plane parallel (BPP) directions. The nanoindentions were performed in order to determine the mechanical properties of the constituent materials in situ as well as those of the highly heterogeneous composite material at this scale. Focused ion beam (FIB) milling and scanning electron microscopy (SEM) were used in conjunction (FIB-SEM) to obtain 2D and 3D images characterizing the heterogeneity of the shale at this scale. The constituent materials were found to be best described as consisting of near micrometer size clay and silt particles embedded in a mixed organic/clay matrix, with some larger (near 10 micrometers in diameter) pockets of organic material evident. Indented regions were identified through SEM, allowing the 200-1000 nanometer deep indentations to be classified according to the constituent materials which they engaged. We use nonlinear finite element modeling to capture results of low-load (on the order of milliNewtons) and high-load (on the order of a few Newtons) nanoindentation tests. Experimental results are used to develop a 3D mechanistic model that interprets the results of nanoindentation tests on specimens of Woodford shale with quantified heterogeneity.

  1. Oxidative weathering recorded by U-Th-Pb behavior in shales

    Science.gov (United States)

    Krogstad, E. J.; Bekker, A.

    2009-12-01

    Pb-isotope data from eleven suites of sedimentary (shales) and metasedimentary rocks (metapelites), new data or from the literature, are studied for indications of their Th/U histories. Variations in 208Pb/204Pb versus 206Pb/204Pb can be interpreted as indicating syn-depositional and/or post-depositional variations in Th/U. REE data can be used to test if apparent Th/U variations resulted from placer concentration of REE-, U-, and Th-rich heavy minerals. Such placer Th- or U-enrichment has not been identified in any of the shale Pb-Pb v. REE data. The early and middle Archean metasedimentary suites described (Isua, Barberton, Buhwa) show no evidence for separation of Th/U, suggesting that surficial conditions were too poor in free oxygen for uranium to be substantially transformed into U6+. A 2.7 Ga graphitic metapelite suite, the Vermilion Lake Formation from NE Minnesota, shows some decrease in Th/U consistent with addition of U upon reduction of U6+to U4+ by the sediments. Younger suites from the Early Proterozoic (Black Hills, 1.8 Ga shelf sediments of the S.W. U.S.A., Belt Supergroup), to samples from the late Paleozoic of the Appalachians, show profound separation of Th from U, consistent with oxic weathering in the modern style. Studies that showed U-enrichment in organic-rich shales as the effect of the rise of atmospheric oxygen neglect the effect of oxidative U-loss in sediments; in this study U-loss in contemporary organic-poor shales is shown to be the necessary, complementary reservoir to account for oxidative U mobility. Both high Th/U in organic-poor shales, or low Th/U in organic-rich shales, therefore, show the effect of oxidation on U.

  2. Composition, diagenetic transformation and alkalinity potential of oil shale ash sediments.

    Science.gov (United States)

    Mõtlep, Riho; Sild, Terje; Puura, Erik; Kirsimäe, Kalle

    2010-12-15

    Oil shale is a primary fuel in the Estonian energy sector. After combustion 45-48% of the oil shale is left over as ash, producing about 5-7 Mt of ash, which is deposited on ash plateaus annually almost without any reuse. This study focuses on oil shale ash plateau sediment mineralogy, its hydration and diagenetic transformations, a study that has not been addressed. Oil shale ash wastes are considered as the biggest pollution sources in Estonia and thus determining the composition and properties of oil shale ash sediment are important to assess its environmental implications and also its possible reusability. A study of fresh ash and drillcore samples from ash plateau sediment was conducted by X-ray diffractometry and scanning electron microscopy. The oil shale is highly calcareous, and the ash that remains after combustion is derived from the decomposition of carbonate minerals. It is rich in lime and anhydrite that are unstable phases under hydrous conditions. These processes and the diagenetic alteration of other phases determine the composition of the plateau sediment. Dominant phases in the ash are hydration and associated transformation products: calcite, ettringite, portlandite and hydrocalumite. The prevailing mineral phases (portlandite, ettringite) cause highly alkaline leachates, pH 12-13. Neutralization of these leachates under natural conditions, by rainwater leaching/neutralization and slow transformation (e.g. carbonation) of the aforementioned unstable phases into more stable forms, takes, at best, hundreds or even hundreds of thousands of years. Copyright © 2010 Elsevier B.V. All rights reserved.

  3. The enrichment behavior of natural radionuclides in pulverized oil shale-fired power plants.

    Science.gov (United States)

    Vaasma, Taavi; Kiisk, Madis; Meriste, Tõnis; Tkaczyk, Alan Henry

    2014-12-01

    The oil shale industry is the largest producer of NORM (Naturally Occurring Radioactive Material) waste in Estonia. Approximately 11-12 million tons of oil shale containing various amounts of natural radionuclides is burned annually in the Narva oil shale-fired power plants, which accounts for approximately 90% of Estonian electricity production. The radionuclide behavior characteristics change during the fuel combustion process, which redistributes the radionuclides between different ash fractions. Out of 24 operational boilers in the power plants, four use circulating fluidized bed (CFB) technology and twenty use pulverized fuel (PF) technology. Over the past decade, the PF boilers have been renovated, with the main objective to increase the efficiency of the filter systems. Between 2009 and 2012, electrostatic precipitators (ESP) in four PF energy blocks were replaced with novel integrated desulphurization technology (NID) for the efficient removal of fly ash and SO2 from flue gases. Using gamma spectrometry, activity concentrations and enrichment factors for the (238)U ((238)U, (226)Ra, (210)Pb) and (232)Th ((232)Th, (228)Ra) family radionuclides as well as (40)K were measured and analyzed in different PF boiler ash fractions. The radionuclide activity concentrations in the ash samples increased from the furnace toward the back end of the flue gas duct. The highest values in different PF boiler ash fractions were in the last field of the ESP and in the NID ash, where radionuclide enrichment factors were up to 4.2 and 3.3, respectively. The acquired and analyzed data on radionuclide activity concentrations in different PF boiler ashes (operating with an ESP and a NID system) compared to CFB boiler ashes provides an indication that changes in the fuel (oil shale) composition and boiler working parameters, as well as technological enhancements in Estonian oil shale fired power plants, have had a combined effect on the distribution patterns of natural radionuclides

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

    Science.gov (United States)

    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.

  5. Brittle Creep of Tournemire Shale: Orientation, Temperature and Pressure Dependences

    Science.gov (United States)

    Geng, Zhi; Bonnelye, Audrey; Dick, Pierre; David, Christian; Chen, Mian; Schubnel, Alexandre

    2017-04-01

    Time and temperature dependent rock deformation has both scientific and socio-economic implications for natural hazards, the oil and gas industry and nuclear waste disposal. During the past decades, most studies on brittle creep have focused on igneous rocks and porous sedimentary rocks. To our knowledge, only few studies have been carried out on the brittle creep behavior of shale. Here, we conducted a series of creep experiments on shale specimens coming from the French Institute for Nuclear Safety (IRSN) underground research laboratory located in Tournemire, France. Conventional tri-axial experiments were carried under two different temperatures (26˚ C, 75˚ C) and confining pressures (10 MPa, 80 MPa), for three orientations (σ1 along, perpendicular and 45˚ to bedding). Following the methodology developed by Heap et al. [2008], differential stress was first increased to ˜ 60% of the short term peak strength (10-7/s, Bonnelye et al. 2016), and then in steps of 5 to 10 MPa every 24 hours until brittle failure was achieved. In these long-term experiments (approximately 10 days), stress and strains were recorded continuously, while ultrasonic acoustic velocities were recorded every 1˜15 minutes, enabling us to monitor the evolution of elastic wave speed anisotropy. Temporal evolution of anisotropy was illustrated by inverting acoustic velocities to Thomsen parameters. Finally, samples were investigated post-mortem using scanning electron microscopy. Our results seem to contradict our traditional understanding of loading rate dependent brittle failure. Indeed, the brittle creep failure stress of our Tournemire shale samples was systematically observed ˜50% higher than its short-term peak strength, with larger final axial strain accumulated. At higher temperatures, the creep failure strength of our samples was slightly reduced and deformation was characterized with faster 'steady-state' creep axial strain rates at each steps, and larger final axial strain

  6. Atmospheric outgassing and native-iron formation during carbonaceous sediment-basalt melt interactions

    Science.gov (United States)

    Pernet-Fisher, John F.; Day, James M. D.; Howarth, Geoffrey H.; Ryabov, Victor V.; Taylor, Lawrence A.

    2017-02-01

    . These anomalous ages probably reflect concurrent assimilation of high Re/Os, radiogenic 187Os crust during crystallization of native-Fe, consistent with the character of local West Greenland sediments. In all three locations, calculations of combined assimilation of crustal sediments and fractional crystallization indicate between 1-7% assimilation can account for the Os-isotope systematics. In the case of Siberian samples, incompatible trace-element abundances indicate that lower crustal assimilation may have also occurred, consistent with the suggestion that crustal assimilation took place prior to native-Fe precipitation. The extent of local crustal contamination at Siberia, West Greenland, and Bühl necessitates that significant quantities of CH4, CO, CO2, SO2 and H2 O were released during assimilation of carbonaceous sediments. Consequently, carbonaceous sediment-basalt melt interactions have collateral effects on total gas output from flood basalt volcanism into the atmosphere. However, the amount of carbonaceous sediment contamination experienced by melts forming the Khungtukun and Dzhaltul intrusions alone, cannot explain the major C-isotope excursions at the Permo-Triassic mass-extinction event. Instead, further unsampled intrusions that also experienced significant carbonaceous sediment-melt interactions would be required. Enhanced greenhouse gas-emission during the Permo-Triassic mass extinction may have been facilitated by a combination of mantle melting and carbonaceous sediment-melt interactions, together with other proposed mechanisms, including wildfires, or by microbial metabolic exhalation.

  7. Characterization of Chiral Carbonaceous Nanotubes Prepared from Four Coiled Tubular 4,4'-biphenylene-silica Nanoribbons

    Directory of Open Access Journals (Sweden)

    Shuwei Lin

    2014-04-01

    Full Text Available Four dipeptides derived from phenylalanine were synthesized, which can self-assemble into twisted nanoribbon in deionized water. The handedness of the organic self-assemblies was controlled by the chirality of the phenylalanine at the terminals. Coiled 4,4'-biphenylene bridged polybissilsesquioxane tubular nanoribbons were prepared using the organic self-assemblies as the templates. The circular dichroism spectra indicated that the biphenylene rings preferred to twist in one-handedness within the walls of the samples. After carbonization and removal of silica, single-handed coiled carbonaceous tubular nanoribbons were obtained. The Raman spectra indicated that the carbon was amorphous. The diffuse reflectance circular dichroism spectra indicated the tubular carbonaceous nanoribbons exhibited optical activity.

  8. Triaxial coreflood study of the hydraulic fracturing of Utica Shale

    Science.gov (United States)

    Carey, J. W.; Frash, L.; Viswanathan, H. S.

    2015-12-01

    One of the central questions in unconventional oil and gas production research is the cause of limited recovery of hydrocarbon. There are many hypotheses including: 1) inadequate penetration of fractures within the stimulated volume; 2) limited proppant delivery; 3) multiphase flow phenomena that blocks hydrocarbon migration; etc. Underlying any solution to this problem must be an understanding of the hydrologic properties of hydraulically fractured shale. In this study, we conduct triaxial coreflood experiments using a gasket sealing mechanism to characterize hydraulic fracture development and permeability of Utica Shale samples. Our approach also includes fracture propagation with proppants. The triaxial coreflood experiments were conducted with an integrated x-ray tomography system that allows direct observation of fracture development using x-ray video radiography and x-ray computed tomography at elevated pressure. A semi-circular, fracture initiation notch was cut into an end-face of the cylindrical samples (1"-diameter with lengths from 0.375 to 1"). The notch was aligned parallel with the x-ray beam to allow video radiography of fracture growth as a function of injection pressure. The proppants included tungsten powder that provided good x-ray contrast for tracing proppant delivery and distribution within the fracture system. Fractures were propagated at injection pressures in excess of the confining pressure and permeability measurements were made in samples where the fractures propagated through the length of the sample, ideally without penetrating the sample sides. Following fracture development, permeability was characterized as a function of hydrostatic pressure and injection pressure. X-ray video radioadiography was used to study changes in fracture aperture in relation to permeability and proppant embedment. X-ray tomography was collected at steady-state conditions to fully characterize fracture geometry and proppant distribution.

  9. Molecular characterization and comparison of shale oils generated by different pyrolysis methods

    Science.gov (United States)

    Birdwell, Justin E.; Jin, Jang Mi; Kim, Sunghwan

    2012-01-01

    Shale oils generated using different laboratory pyrolysis methods have been studied using standard oil characterization methods as well as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI) and atmospheric photoionization (APPI) to assess differences in molecular composition. The pyrolysis oils were generated from samples of the Mahogany zone oil shale of the Eocene Green River Formation collected from outcrops in the Piceance Basin, Colorado, using three pyrolysis systems under conditions relevant to surface and in situ retorting approaches. Significant variations were observed in the shale oils, particularly the degree of conjugation of the constituent molecules and the distribution of nitrogen-containing compound classes. Comparison of FT-ICR MS results to other oil characteristics, such as specific gravity; saturate, aromatic, resin, asphaltene (SARA) distribution; and carbon number distribution determined by gas chromatography, indicated correspondence between higher average double bond equivalence (DBE) values and increasing asphaltene content. The results show that, based on the shale oil DBE distributions, highly conjugated species are enriched in samples produced under low pressure, high temperature conditions, and under high pressure, moderate temperature conditions in the presence of water. We also report, for the first time in any petroleum-like substance, the presence of N4 class compounds based on FT-ICR MS data. Using double bond equivalence and carbon number distributions, structures for the N4 class and other nitrogen-containing compounds are proposed.

  10. Spatial and spectral resolution of carbonaceous material from hematite (α-Fe2O3) using multivariate curve resolution-alternating least squares (MCR-ALS) with Raman microspectroscopic mapping: implications for the search for life on Mars.

    Science.gov (United States)

    Smith, Joseph P; Smith, Frank C; Booksh, Karl S

    2017-08-21

    The search for evidence of extant or past life on Mars is a primary objective of both the upcoming Mars 2020 rover (NASA) and ExoMars 2020 rover (ESA/Roscosmos) missions. This search will involve the detection and identification of organic molecules and/or carbonaceous material within the Martian surface environment. For the first time on a mission to Mars, the scientific payload for each rover will include a Raman spectrometer, an instrument well-suited for this search. Hematite (α-Fe2O3) is a widespread mineral on the Martian surface. The 2LO Raman band of hematite and the Raman D-band of carbonaceous material show spectral overlap, leading to the potential misidentification of hematite as carbonaceous material. Here we report the ability to spatially and spectrally differentiate carbonaceous material from hematite using multivariate curve resolution-alternating least squares (MCR-ALS) applied to Raman microspectroscopic mapping under both 532 nm and 785 nm excitation. For this study, a sample comprised of hematite, carbonaceous material, and substrate-adhesive epoxy in spatially distinct domains was constructed. Principal component analysis (PCA) reveals that both 532 nm and 785 nm excitation produce representative three-phase systems of hematite, carbonaceous material, and substrate-adhesive epoxy in the analyzed sample. MCR-ALS with Raman microspectroscopic mapping using both 532 nm and 785 nm excitation was able to resolve hematite, carbonaceous material, and substrate-adhesive epoxy by generating spatially-resolved chemical maps and corresponding Raman spectra of these spatially distinct chemical species. Moreover, MCR-ALS applied to the combinatorial data sets of 532 nm and 785 nm excitation, which contain hematite and carbonaceous material within the same locations, was able to resolve hematite, carbonaceous material, and substrate-adhesive epoxy. Using multivariate analysis with Raman microspectroscopic mapping, 785 nm excitation more effectively

  11. Environmental hazard of oil shale combustion fly ash.

    Science.gov (United States)

    Blinova, Irina; Bityukova, Liidia; Kasemets, Kaja; Ivask, Angela; Käkinen, Aleksandr; Kurvet, Imbi; Bondarenko, Olesja; Kanarbik, Liina; Sihtmäe, Mariliis; Aruoja, Villem; Schvede, Hedi; Kahru, Anne

    2012-08-30

    The combined chemical and ecotoxicological characterization of oil shale combustion fly ash was performed. Ash was sampled from the most distant point of the ash-separation systems of the Balti and Eesti Thermal Power Plants in North-Eastern Estonia. The fly ash proved potentially hazardous for tested aquatic organisms and high alkalinity of the leachates (pH>10) is apparently the key factor determining its toxicity. The leachates were not genotoxic in the Ames assay. Also, the analysis showed that despite long-term intensive oil-shale combustion accompanied by considerable fly ash emissions has not led to significant soil contamination by hazardous trace elements in North-Eastern Estonia. Comparative study of the fly ash originating from the 'new' circulating fluidized bed (CFB) combustion technology and the 'old' pulverized-fired (PF) one showed that CFB fly ash was less toxic than PF fly ash. Thus, complete transfer to the 'new' technology will reduce (i) atmospheric emission of hazardous trace elements and (ii) fly ash toxicity to aquatic organisms as compared with the 'old' technology. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    Qiao Lyu

    2016-08-01

    Full Text Available 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.

  13. Characterization and analysis of Devonian shales as related to release of gaseous hydrocarbons. Well K-4 Johnson County, Kentucky

    Energy Technology Data Exchange (ETDEWEB)

    Kalyoncu, R.S.; Snyder, M.J.

    1979-08-15

    Various characterization tasks were performed on 54 cored shale samples from Johnson County, Kentucky. Core samples were obtained from depths of 967 to 1510 feet. A total of 126 samples were canned for several DOE contractors, including Battelle Columbus. Free gas analyses indicate the presence of significant quantities of higher chain hydrocarbon gases in the K-4 shales. Hydrocarbon gas release rates and kinetic studies indicate that diffusion coefficients are inversely proportional to the square root of the molecular weight of diffusing species. Although wide scatter is observed in the chemical and physical characterization data, good correlations exist between the hydrocarbon gas contents and various laboratory characterization values (physical and chemical). A number of one-to-one relationships are pointed out and discussed. Lithologically, inorganic portions of K-4 shales are composed predominantly of quartz and illite with small quantities of pyrite and various carbonate minerals.

  14. Organic compounds in produced waters from shale gas wells.

    Science.gov (United States)

    Maguire-Boyle, Samuel J; Barron, Andrew R

    2014-01-01

    A detailed analysis is reported of the organic composition of produced water samples from typical shale gas wells in the Marcellus (PA), Eagle Ford (TX), and Barnett (NM) formations. The quality of shale gas produced (and frac flowback) waters is a current environmental concern and disposal problem for producers. Re-use of produced water for hydraulic fracturing is being encouraged; however, knowledge of the organic impurities is important in determining the method of treatment. The metal content was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Mineral elements are expected depending on the reservoir geology and salts used in hydraulic fracturing; however, significant levels of other transition metals and heavier main group elements are observed. The presence of scaling elements (Ca and Ba) is related to the pH of the water rather than total dissolved solids (TDS). Using gas chromatography mass spectrometry (GC/MS) analysis of the chloroform extracts of the produced water samples, a plethora of organic compounds were identified. In each water sample, the majority of organics are saturated (aliphatic), and only a small fraction comes under aromatic, resin, and asphaltene categories. Unlike coalbed methane produced water it appears that shale oil/gas produced water does not contain significant quantities of polyaromatic hydrocarbons reducing the potential health hazard. Marcellus and Barnett produced waters contain predominantly C6-C16 hydrocarbons, while the Eagle Ford produced water shows the highest concentration in the C17-C30 range. The structures of the saturated hydrocarbons identified generally follows the trend of linear > branched > cyclic. Heterocyclic compounds are identified with the largest fraction being fatty alcohols, esters, and ethers. However, the presence of various fatty acid phthalate esters in the Barnett and Marcellus produced waters can be related to their use in drilling fluids and breaker additives

  15. Preliminary Study on PAHs Distribution in High-grade Oil Shale and Its Spontaneous Combustion Product in Fushun, Liaoning Province

    Institute of Scientific and Technical Information of China (English)

    ZHANG Liping; ZENG Rongshu; XU Wendong

    2007-01-01

    Spontaneous combustion of oil shale is very common as a result of long-time exposure to the air in the Fushun West Open-Pit Mine and West Dump. The PAHs in the high-grade oil shale and its spontaneous combustion product were analyzed semiquantitatively by GC-MS in order to investigate their distribution in different states and their potential negative effects on the environment. Totally 57and 60 PAHs and their alkyl homologues were identified in the two analyzed samples, among which the alkyl derivatives were predominant, taking up to about 65 % in the total PAHs. Those low-molecular mass PAHs (3- or 4-ring) were the main compounds in the two samples. Ten of sixteen USEPA priority pollutant PAHs were detected in two samples, of which phenanthrene was the richest whose contents were 6.93% and 15.03%. Based on comparison of analysis results, the amount and contents of PAHs,except for triaromatic steroid group, were higher in the burning oil shale. So it can be determined that the effects caused by spontaneous combustion of oil shale would be more serious and that the effects of the Fushun oil shale and its spontaneous combustion on the environment should not be ignored in the future work.

  16. Fracture development in shale and its relationship to gas accumulation

    Directory of Open Access Journals (Sweden)

    Wenlong Ding

    2012-01-01

    Full Text Available Shale with high quartz, feldspar and carbonate, will have low Poisson’s ratio, high Young’s modulus and high brittleness. As a result, the shale is conducive to produce natural and induced fractures under external forces. In general, there is a good correlation between fracture development in shale and the volume of brittle minerals present. Shale with high TOC or abnormally high pressure has well-developed fractures. Shale fracture development also shows a positive correlation with total gas accumulation and free gas volume, i.e., the better shale fractures are developed, the greater the gas accumulation and therefore the higher the gas production. Fractures provide migration conduits and accumulation spaces for natural gas and formation water, which are favorable for the volumetric increase of free natural gas. Wider fractures in shale result in gas loss. In North America, there is a high success ratio of shale gas exploration and high gas production from high-angle fracture zones in shale. Good natural gas shows or low yield producers in the Lower Paleozoic marine organic matter-rich rocks in the Sichuan Basin are closely related to the degree of fracture development in brittle shales.

  17. Carbonaceous matter and putative microfossils of the mid-Archean Kromberg type-section re-visited, Barberton Greenstone Belt, South Africa

    Science.gov (United States)

    McLoughlin, Nicola; Grosch, Eugene

    2014-05-01

    Silicified seafloor sediments of the Kromberg Formation from the Onverwacht Group of the Barberton greenstone belt (BGB), South Africa, have been argued to contain some of the world's oldest preserved carbonaceous microfossils. Previous studies of these cherts have reported filamentous, spheroidal and ellipsoidal microfossils in thin-section (Walsh 1992); and bacteriomorph like structures in HF-etched samples (Westall et al. 2001). These microtextural studies however, lack supporting in-situ geochemical data, and are hampered to some degree by re-mobilisation of the carbonaceous matter (Van Zuilen et al. 2007). In light of these concerns, and ongoing debates surrounding carbonaceous remains in other Archean cherts (e.g., W Australia), further in-situ data from the Kromberg is required to positively identify carbonaceous matter of biogenic origin. New data will also help to address outstanding questions regarding the relative contribution of benthic versus planktonic microorganisms, and the putative microbial metabolisms involved. This study focuses on surface samples and drill core from the Barberton Scientific Drilling Programme, (BSDP, Grosch et al. 2009) from the southeastern limb of the Onverwacht anticline of the BGB. We sampled the Footbridge chert and a second chert horizon in drill core KD1 of the BSDP in the upper Kromberg Fm; and surface outcrops of two black cherts from the lower Kromberg Fm. Sedimentological logging reveals horizons rich in volcaniclastics with interbedded finely laminated grey-black chert, also intrusive black cherts, and sulphide rich horizons. The TOC of the sampled cherts is 1.24 to 5.40 wt%. Preliminary bulk carbon isotope values range from δ13C -21.1 to -35.3o values that are consistent with organic matter produced by anoxygenic photosynthesis. Microfabrics preserved in the Kromberg cherts include, primary wispy-laminated carbonaceous films suggesting compaction of early carbonaceous laminae. Also large composite carbonaceous

  18. Atmospheric pressure MALDI for the noninvasive characterization of carbonaceous ink from Renaissance documents.

    Science.gov (United States)

    Grasso, Giuseppe; Calcagno, Marzia; Rapisarda, Alessandro; D'Agata, Roberta; Spoto, Giuseppe

    2017-06-01

    The analytical methods that are usually applied to determine the compositions of inks from ancient manuscripts usually focus on inorganic components, as in the case of iron gall ink. In this work, we describe the use of atmospheric pressure/matrix-assisted laser desorption ionization-mass spectrometry (AP/MALDI-MS) as a spatially resolved analytical technique for the study of the organic carbonaceous components of inks used in handwritten parts of ancient books for the first time. Large polycyclic aromatic hydrocarbons (L-PAH) were identified in situ in the ink of XVII century handwritten documents. We prove that it is possible to apply MALDI-MS as a suitable microdestructive diagnostic tool for analyzing samples in air at atmospheric pressure, thus simplifying investigations of the organic components of artistic and archaeological objects. The interpretation of the experimental MS results was supported by independent Raman spectroscopic investigations. Graphical abstract Atmospheric pressure/MALDI mass spectrometry detects in situ polycyclic aromatic hydrocarbons in the carbonaceous ink of XVII century manuscripts.

  19. Preliminary Results of the Investigation of the Carbonaceous Chondrites Nagoya, Allende, and Murray

    Science.gov (United States)

    Rozanov, Alexei Yu.; Hoover, Richard B.; Rose, M. Franklin (Technical Monitor)

    2000-01-01

    As part of a long-term study of morphological biomarkers in Astromaterials, we are documenting a variety of features considered to be indigenous to ancient terrestrial rocks and carbonaceous meteorites. In preparation for the study of samples returned from Mars and other bodies of our Solar System, it is imperative that we establish a database of the nature and morphology of known bacterial fossils in Earth rocks and biomorphic microstructures which may represent microfossils in meteorites. The process of fossilization or mineralization can cause major changes in morphologies and textures of the original organisms and the study of fossilized terrestrial organisms can help provide insight into the interpretation of mineral biomarkers and abiotic microstructures which may mimic certain aspects of microfossils. One class of biomarkers consists of biominerals which have either been precipitated directly by microorganisms, or whose precipitation has been influenced by the organisms. Such microbe-mediated mineral formation may include important clues to the size, shape, and environment of the microorganisms. This paper describes the detection of possible microbe-mediated minerals, biomorphic microstructures and possible microfossils in the Nagoya, Allende, and Murray Carbonaceous Chondrites.

  20. Preliminary Results of the Investigation of the Carbonaceous Chondrites Nagoya, Allende, and Murray

    Science.gov (United States)

    Rozanov, Alexei Yu.; Hoover, Richard B.; Rose, M. Franklin (Technical Monitor)

    2000-01-01

    As part of a long-term study of morphological biomarkers in Astromaterials, we are documenting a variety of features considered to be indigenous to ancient terrestrial rocks and carbonaceous meteorites. In preparation for the study of samples returned from Mars and other bodies of our Solar System, it is imperative that we establish a database of the nature and morphology of known bacterial fossils in Earth rocks and biomorphic microstructures which may represent microfossils in meteorites. The process of fossilization or mineralization can cause major changes in morphologies and textures of the original organisms and the study of fossilized terrestrial organisms can help provide insight into the interpretation of mineral biomarkers and abiotic microstructures which may mimic certain aspects of microfossils. One class of biomarkers consists of biominerals which have either been precipitated directly by microorganisms, or whose precipitation has been influenced by the organisms. Such microbe-mediated mineral formation may include important clues to the size, shape, and environment of the microorganisms. This paper describes the detection of possible microbe-mediated minerals, biomorphic microstructures and possible microfossils in the Nagoya, Allende, and Murray Carbonaceous Chondrites.

  1. A Carbonaceous Chondrite Based Simulant of Phobos

    Science.gov (United States)

    Rickman, Douglas L.; Patel, Manish; Pearson, V.; Wilson, S.; Edmunson, J.

    2016-01-01

    In support of an ESA-funded concept study considering a sample return mission, a simulant of the Martian moon Phobos was needed. There are no samples of the Phobos regolith, therefore none of the four characteristics normally used to design a simulant are explicitly known for Phobos. Because of this, specifications for a Phobos simulant were based on spectroscopy, other remote measurements, and judgment. A composition based on the Tagish Lake meteorite was assumed. The requirement that sterility be achieved, especially given the required organic content, was unusual and problematic. The final design mixed JSC-1A, antigorite, pseudo-agglutinates and gilsonite. Sterility was achieved by radiation in a commercial facility.

  2. Coal and oil shale of Early Carboniferous age in northern Canada - significance for paleoenvironmental and paleoclimatic interpretations. [Canada - Northwest Territories and Yukon Territory

    Energy Technology Data Exchange (ETDEWEB)

    Cameron, A.R.; Goodarzi, F.; Potter, J. (Geological Survey of Canada, Calgary, AB (Canada))

    1994-01-01

    Lower Carboniferous (Mississippian) coal beds and oil shale occur at several locations in northern Canada. In the northern Yukon Territory coal of semi-anthracite/anthracite rank occurs in the Kayak Formation in the British Mountains and at Hoidahl Dome near the headwaters of Blow River. Farther south in the Liard Basin, Northwest Territories, coals of high volatile bituminous rank occur in the Mattson Formation. In the Arctic Islands thicker beds of the Emma Fiord Formation, the oldest unit in the Sverdrup Basin, contain thin coal seams and oil shale on Devon Island, near the southern edge of the basin and on Axel Heiberg and Ellesmere islands on the north side of the basin. Organic matter in the Devon Island section is at a low maturity level (R[sub o, max] % 0.26-0.50), whereas that from Ellesmere and Axel Heiberg has reached the level of meta-anthracite. Depositional environments for these carbonaceous sediments were different. The coal-bearing Kayak strata accumulated in a coastal plain setting overlain transgressively by younger marine beds. The Mattson coal beds appear to have formed in a prograding delta, but coal and oil shale in the Emma Ford were deposited in lacustrine environments in a rift basin. These Canadian occurrences resemble penecontemporaneous deposits in Svalbard and elsewhere, adjacent to the present-day Arctic Ocean. They formed at low latitudes where conditions were favourable for the preservation of carbonaceous matter. Prior to the opening of the Arctic Ocean basin in Mesozoic times, sites on the mainland were undoubtedly closer to sites in the Arctic Islands than they are today.

  3. Structure and properties of carbonaceous adsorbents obtained from furanformolites

    Energy Technology Data Exchange (ETDEWEB)

    Pokonova, Y.B.; Oleinik, M.S.; Proskuryakov, V.A.

    1982-12-10

    We have shown previously (1) that a new copolycondensate based on petroleum residues -- fuaranformolite -- is a valuable carbon-containing raw material by the use of which carbonaceous adsorbents have been obtained. The latter can be used as catalysts and catalyst supports and also for the fine purification and separation of gases. The present paper is devoted to the study of the porous structure and sorption characteristics of the adsorbents obtained. High-strength carbonaceous adsorbents obtained from new copolymers of asphaltite -- fuaranformolites may, depending on the degree of burn-off, be used for the adsorption of poorly sorbed gases, of vapors of organic solvents, and of substances from solution. By varying the composition of the copolymer it is possible to direct the formation of the porous structure of the adsorbents in a desired manner.

  4. The kinetic parameters of carbonaceous materials activated with potassium hydroxide

    Energy Technology Data Exchange (ETDEWEB)

    Yong, Z.; Han, B.X.

    2000-07-01

    On the basis of microspore formation in carbonaceous materials, the activation energy for the potassium hydroxide activation of Chinese petroleum coke and coal has been deduced theoretically as dB(O)/dt = A exp(-E(a)) is an element of/RT), where is an element of is the formation energy for the metastable solid formed at the activation temperature. The kinetic parameters (frequency factor, A, and apparent activation energy, E(a) were calculated from this equation as being 5.319 mg/(g min), 36.51 kJ/mol and 6.64 mg/(g min), 49.46 kJ/mol, respectively, for the two carbonaceous materials studied.

  5. Yamato-82042: An unusual carbonaceous chondrite with CM affinities

    OpenAIRE

    Grady,Monica M./Graham,A.L./Barber,D.J./Aylmer,D./Kurat,G./Ntaflos,T./Ott,U./Palme,H./Spettel,B.

    1987-01-01

    The Yamato-82042 carbonaceous chondrite has been the subject of a consortium study, designed to determine its properties and hence attempt a more precise classification of the meteorite. Major and minor elemental abundance and oxygen isotope data indicate that the specimen is a CM chondrite, but on textural and petrologic grounds the meteorite is more akin to CI stones. It is possible that Y-82042 is the first CM1 chondrite recognized.

  6. Organic matter in carbonaceous meteorites: past, present and future research.

    Science.gov (United States)

    Sephton, Mark A

    2005-12-15

    Carbonaceous meteorites are fragments of ancient asteroids that have remained relatively unprocessed since the formation of the Solar System. These carbon-rich objects provide a record of prebiotic chemical evolution and a window on the early Solar System. Many compound classes are present reflecting a rich organic chemical environment during the formation of the planets. Recent theories suggest that similar extraterrestrial organic mixtures may have acted as the starting materials for life on Earth.

  7. Temperatures of aqueous alteration on carbonaceous chondrite parent bodies

    OpenAIRE

    Guo, W; Perronnet, M.; Zolensky, M.E.; Eiler, J. M.

    2007-01-01

    Aqueous alteration of primitive meteorites is among the earliest and the most widespread geological processes in the solar system. A better understanding of these processes would help us constrain the early evolution condition of the solar system and test models of thermal and chemical evolution of planetesimals. In this study, we extended our previous work on CM chondrites by further applying carbonate clumped isotope thermometry to other types of carbonaceous chondrites (G...

  8. Comets, carbonaceous meteorites, and the origin of the biosphere

    OpenAIRE

    2006-01-01

    International audience; The Biosphere is considered to represent the Earth's crust, atmosphere, oceans, and ice caps and the living organisms that survive within this habitat. This paper considers the significance of comets and carbonaceous meteorites to the origin and evolution of the Biosphere and presents new Field Emission Scanning Electron Microscope (FESEM) images of indigenous microfossils in the Orgueil and Murchison meteorites. The discovery of microbial extremophiles in deep crustal...

  9. Processes for liquefying carbonaceous feedstocks and related compositions

    Energy Technology Data Exchange (ETDEWEB)

    MacDonnell, Frederick M.; Dennis, Brian H.; Billo, Richard E.; Priest, John W.

    2017-02-28

    Methods for the conversion of lignites, subbituminous coals and other carbonaceous feedstocks into synthetic oils, including oils with properties similar to light weight sweet crude oil using a solvent derived from hydrogenating oil produced by pyrolyzing lignite are set forth herein. Such methods may be conducted, for example, under mild operating conditions with a low cost stoichiometric co-reagent and/or a disposable conversion agent.

  10. Environmental contamination due to shale gas development.

    Science.gov (United States)

    Annevelink, M P J A; Meesters, J A J; Hendriks, A J

    2016-04-15

    Shale gas development potentially contaminates both air and water compartments. To assist in governmental decision-making on future explorations, we reviewed scattered information on activities, emissions and concentrations related to shale gas development. We compared concentrations from monitoring programmes to quality standards as a first indication of environmental risks. Emissions could not be estimated accurately because of incomparable and insufficient data. Air and water concentrations range widely. Poor wastewater treatment posed the highest risk with concentrations exceeding both Natural Background Values (NBVs) by a factor 1000-10,000 and Lowest Quality Standards (LQSs) by a factor 10-100. Concentrations of salts, metals, volatile organic compounds (VOCs) and hydrocarbons exceeded aquatic ecotoxicological water standards. Future research must focus on measuring aerial and aquatic emissions of toxic chemicals, generalisation of experimental setups and measurement technics and further human and ecological risk assessment.

  11. Organic and inorganic composition and microbiology of produced waters from Pennsylvania shale gas wells

    Science.gov (United States)

    Akob, Denise M.; Cozzarelli, Isabelle M.; Dunlap, Darren S.; Rowan, Elisabeth L.; Lorah, Michelle M.

    2015-01-01

    Hydraulically fractured shales are becoming an increasingly important source of natural gas production in the United States. This process has been known to create up to 420 gallons of produced water (PW) per day, but the volume varies depending on the formation, and the characteristics of individual hydraulic fracture. PW from hydraulic fracturing of shales are comprised of injected fracturing fluids and natural formation waters in proportions that change over time. Across the state of Pennsylvania, shale gas production is booming; therefore, it is important to assess the variability in PW chemistry and microbiology across this geographical span. We quantified the inorganic and organic chemical composition and microbial communities in PW samples from 13 shale gas wells in north central Pennsylvania. Microbial abundance was generally low (66–9400 cells/mL). Non-volatile dissolved organic carbon (NVDOC) was high (7–31 mg/L) relative to typical shallow groundwater, and the presence of organic acid anions (e.g., acetate, formate, and pyruvate) indicated microbial activity. Volatile organic compounds (VOCs) were detected in four samples (∼1 to 11.7 μg/L): benzene and toluene in the Burket sample, toluene in two Marcellus samples, and tetrachloroethylene (PCE) in one Marcellus sample. VOCs can be either naturally occurring or from industrial activity, making the source of VOCs unclear. Despite the addition of biocides during hydraulic fracturing, H2S-producing, fermenting, and methanogenic bacteria were cultured from PW samples. The presence of culturable bacteria was not associated with salinity or location; although organic compound concentrations and time in production were correlated with microbial activity. Interestingly, we found that unlike the inorganic chemistry, PW organic chemistry and microbial viability were highly variable across the 13 wells sampled, which can have important implications for the reuse and handling of these fluids

  12. Indigenous Carbonaceous Matter in the Nakhla Mars Meteorite

    Science.gov (United States)

    Clemett, S. J.; Thomas-Keprta, K. L.; Rahman, Z.; Le, L.; Wentworth, S. J.; Gibson, E. K.; McKay, D. S.

    2016-01-01

    Detailed microanalysis of the Martian meteorite Nakhla has shown there are morphologically distinct carbonaceous features spatially associated with low-T aqueous alteration phases including salts and id-dingsite. A comprehensive suite of analytical instrumentation including optical microscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) spectroscopy, focused ion beam (FIB) microscopy, transmission electron microscopy (TEM), two-step laser mass spectrometry (mu-L(sup 2)MS), laser mu-Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and nanoscale secondary ion mass spectrometry (NanoSIMS) are being used to characterize the carbonaceous matter and host mineralogy. The search for carbonaceous matter on Mars has proved challenging. Viking Landers failed to unambiguously detect simple organics at either of the two landing sites although the Martian surface is estimated to have acquired at least 10(exp15) kg of C as a consequence of meteoritic accretion over the last several Ga. The dearth of organics at the Martian surface has been attributed to various oxidative processes including UV photolysis and peroxide activity. Consequently, investigations of Martian organics need to be focused on the sub-surface regolith where such surface processes are either severely attenuated or absent. Fortuitously since Martian meteorites are derived from buried regolith materials they provide a unique opportunity to study Martian organic geochemistry.

  13. Kirishites—high-carbonaceous hairlike fibers associated with volkhovites

    Science.gov (United States)

    Skublov, G. T.; Marin, Yu. B.; Skublov, S. G.; Vasil'Ev, E. V.; Gembitskaya, I. M.; Nechaeva, E. S.; Tarasenko, Yu. N.

    2009-12-01

    Kirishites are highly carbonaceous hairlike fibers 30-100 μm in thickness and 3-30 mm long, which jut out as bunches on the surface of cinder and shungite fragments associated with volkhovites (Holocene tectitelike glasses corresponding to the rocks of kimberlite-lamproite-carbonatite series in composition). Kirishite fibers are zonal. Their inner (axial) zone is composed of high-nitrogen proteinlike compounds, whereas the outer zone is essentially carbonaceous, with a high content of organoelemental complexes (Si, Fe) and numerous micrometer-sized anomalies of major, volatile, trace, and ore elements. Longitudinal zoning is established in aposhungite kirishites: the consecutive change of maximum concentrations—K, Na, Cl, C, Mn → C, S, V, Ni, Cu, Zn → S, N, Ba, Te, Pb, Bi, Nd—is traced from the roots of fibers to their ends. It is suggested that as volkhovites were forming, fragments of cinder and shungite underwent partial melting. The highly carbonaceous compounds released due decompression and explosion were squeezed out from fragments and solidified as fibers during fall of fragments on the Earth’s surface.

  14. Design of new carbonaceous catalysts and photocatalysts for organic synthesis

    Science.gov (United States)

    Rajpara, Vikul B.

    Pristine and modified carbonaceous materials are introduced as convenient catalysts for oxidation, photooxidation and alkylation of aromatic hydrocarbons. Oxidation reactions have been carried out by air and effect of cyclohexene and light has also been investigated. Availability of the reagents, light source (ambient light), minimum chemical waste, low toxicity and reusability of the catalysts make developed processes green alternatives of traditional methods for the synthesis of industrially important organic compounds. Catalytic performance and selectivity of carbonaceous materials have been linked to their morphology (graphite, carbon black, multi-walled, single-walled carbon nanotubes, fullerene C60) and modification oxidation, conjugation with nanoparticles). The reported study is the first step toward targeted design of new carbonaceous catalysts for organic synthesis. Graphite is known for its electric conductivity and quantum dots are known for transfer of energy to attached molecules and their conjugation may provide a unique hybrid material for photocatalysis of organic reactions. Quantum dots with known number of functional group hold an especially great promise in the field of catalysis. However, controlling the number of functionalities on the surface of quantum dots is very challenging. We demonstrated monofuncationalization of gold nanoparticles using trityl (solid) support. Similar approach was used for the monofunctionalization of quantum dots and our preliminary data showed that quantum dots can be attached and detached from the solid support under mild conditions.

  15. Modeling Orbital Gamma-Ray Spectroscopy Experiments at Carbonaceous Asteroids

    CERN Document Server

    Lim, Lucy F; Evans, Larry G; Parsons, Ann M; Zolensky, Michael E; Boynton, William V

    2016-01-01

    To evaluate the feasibility of measuring differences in bulk composition among carbonaceous meteorite parent bodies from an asteroid or comet orbiter, we present the results of a performance simulation of an orbital gamma-ray spectroscopy ("GRS") experiment in a Dawn-like orbit around spherical model asteroids with a range of carbonaceous compositions. The orbital altitude was held equal to the asteroid radius for 4.5 months. Both the asteroid gamma-ray spectrum and the spacecraft background flux were calculated using the MCNPX Monte-Carlo code. GRS is sensitive to depths below the optical surface (to ~20--50 cm depth depending on material density). This technique can therefore measure underlying compositions beneath a sulfur-depleted (e.g., Nittler et al. 2001) or desiccated surface layer. We find that 3\\sigma\\ uncertainties of under 1 wt% are achievable for H, C, O, Si, S, Fe, and Cl for five carbonaceous meteorite compositions using the heritage Mars Odyssey GRS design in a spacecraft- deck-mounted configu...

  16. Biomass-derived carbonaceous materials as components in wood briquettes

    Energy Technology Data Exchange (ETDEWEB)

    Stengl, S.; Koch, C.; Stadlbauer, E.A.; Scheer, J. [Univ. of Applied Sciences, THM Campus Giessen, Giessen (Germany); Weber, B. [Instituto de Ingenieria de la Universidad Nacional Autonoma de Mexico (UNAM), Coyoacan (Mexico); Strohal, U.; Fey, J. [Strohal Anlagenbau, Staufenberg (Germany)

    2012-11-01

    The present paper describes a briquette composed of a substantial amount of wooden biomass and up to 35% of carbonaceous materials derived from biogenic residues. The cellulosic component may be a mixture of any wooden residue. Suitable substrates for the carbonaceous fraction are vegetation wastes from land management or agriculture. Depending on physical and chemical nature of the substrate, Hydrothermal Carbonisation (HTC) or Low Temperature Conversion (LTC) may be used to produce the carbonaceous part of the briquette. HTC turns wet biomass at temperatures around 200 deg C in an autoclave into lignite whereas LTC treatment at 400 deg C and atmospheric pressure produces black coal. This is manifested by a molar ratio of 0.1 {<=} H/C (LTC) {<=} 0.7; 0.05{<=} O/C (LTC) {<=} 0.4 and 0.7 < H/C (HTC) <1.5 ; 0.2< O/C (HTC) < 0.5. Solid state {sup 13}C-NMR confirms these findings showing a strong absorption band for sp{sup 2}-hybridized carbon atoms at chemical shifts of 100 ppm und 165 ppm for LTC biochar. Depending on the substrate, HTC gives rise to an increase in the specific calorific value (MJ/kg) by a factor of {Psi} {approx} 1.2 - 1.4; LTC by 1.5 - 1.8. In addition ash melting points are significantly increased; in case of wheat straw by about 200 deg C. Compacted products may have a cylindrical or rectangular profile.

  17. Distinct Distribution of Purines in CM and CR Carbonaceous Chondrites

    Science.gov (United States)

    Callahan, Michael P.; Stern, Jennifer C.; Glavin, Daniel P.; Smith, Karen E.; Martin, Mildred G.; Dworkin, Jason P.

    2010-01-01

    Carbonaceous meteorites contain a diverse suite of organic molecules and delivered pre biotic organic compounds, including purines and pyrimidines, to the early Earth (and other planetary bodies), seeding it with the ingredients likely required for the first genetic material. We have investigated the distribution of nucleobases in six different CM and CR type carbonaceous chondrites, including fivc Antarctic meteorites never before analyzed for nucleobases. We employed a traditional formic acid extraction protocol and a recently developed solid phase extraction method to isolate nucleobases. We analyzed these extracts by high performance liquid chromatography with UV absorbance detection and tandem mass spectrometry (HPLC-UV -MS/MS) targeting the five canonical RNAIDNA bases and hypoxanthine and xanthine. We detected parts-per-billion levels of nucleobases in both CM and CR meteorites. The relative abundances of the purines found in Antarctic CM and CR meteorites were clearly distinct from each other suggesting that these compounds are not terrestrial contaminants. One likely source of these purines is formation by HCN oligomerization (with other small molecules) during aqueous alteration inside the meteorite parent body. The detection of the purines adenine (A), guanine (0), hypoxanthine (HX), and xanthine (X) in carbonaceous meteorites indicates that these compounds should have been available on the early Earth prior to the origin of the first genetic material.

  18. 重庆东北城口地区黑色岩系地球化学异常模式%A Geochemical Anomaly Model for Black Shales in Chengkou Region of Northeast Chongqing

    Institute of Scientific and Technical Information of China (English)

    雷恩; 王丹; 杨洪永; 秦林

    2012-01-01

    Good prospecting effect is gained by stream sediment survey in black shales area in Chengkou region of Northeast Chongqing, which consists of Upper Sinian to Lower Cambrian rocks such as black carbonaceous aleurolite, carbonaceous silty slate, and carbonaceous siliceous rocks. Focusing on the study of black shales and based on comprehensive analysis, this paper has pointed out that manganese, vanadium, silver, and barium are the main ore-forming elements, while manganese mainly enriches in Dengying and Doushantuo formations, vanadium and silver in Lujiaping Formation, and barium in Bashan Formation. The paper has also established a geochemical anomaly model for black shales and shown a clear direction for prospecting.%重庆东北城口地区黑色岩系广泛发育,主要岩性有上震旦统到下武寒统的黑色碳质粉砂岩、含碳粉砂质板岩、含碳硅质岩等,在区内进行水系沉积物测量工作取得了良好的找矿效果.以区内的黑色岩系为重点研究对象,通过对样品分析数据的综合研究,指出了区内的主要成矿元素有Mn、V、Ag、Ba等,其中Mn主要富集在灯影组和陡山沱组中,V、Ag主要富集在鲁家坪组中,Ba则富集在巴山组中,初步确定了黑色岩系的地球化学异常模式,指明了区内黑色岩系的找矿方向.

  19. Extraction of hydrocarbons from high-maturity Marcellus Shale using supercritical carbon dioxide

    Science.gov (United States)

    Jarboe, Palma B.; Philip A. Candela,; Wenlu Zhu,; Alan J. Kaufman,

    2015-01-01

    Shale is now commonly exploited as a hydrocarbon resource. Due to the high degree of geochemical and petrophysical heterogeneity both between shale reservoirs and within a single reservoir, there is a growing need to find more efficient methods of extracting petroleum compounds (crude oil, natural gas, bitumen) from potential source rocks. In this study, supercritical carbon dioxide (CO2) was used to extract n-aliphatic hydrocarbons from ground samples of Marcellus shale. Samples were collected from vertically drilled wells in central and western Pennsylvania, USA, with total organic carbon (TOC) content ranging from 1.5 to 6.2 wt %. Extraction temperature and pressure conditions (80 °C and 21.7 MPa, respectively) were chosen to represent approximate in situ reservoir conditions at sample depth (1920−2280 m). Hydrocarbon yield was evaluated as a function of sample matrix particle size (sieve size) over the following size ranges: 1000−500 μm, 250−125 μm, and 63−25 μm. Several methods of shale characterization including Rock-Eval II pyrolysis, organic petrography, Brunauer−Emmett−Teller surface area, and X-ray diffraction analyses were also performed to better understand potential controls on extraction yields. Despite high sample thermal maturity, results show that supercritical CO2 can liberate diesel-range (n-C11 through n-C21) n-aliphatic hydrocarbons. The total quantity of extracted, resolvable n-aliphatic hydrocarbons ranges from approximately 0.3 to 12 mg of hydrocarbon per gram of TOC. Sieve size does have an effect on extraction yield, with highest recovery from the 250−125 μm size fraction. However, the significance of this effect is limited, likely due to the low size ranges of the extracted shale particles. Additional trends in hydrocarbon yield are observed among all samples, regardless of sieve size: 1) yield increases as a function of specific surface area (r2 = 0.78); and 2) both yield and surface area increase with increasing

  20. Carbon isotope-constrained seasonality of carbonaceous aerosol sources from an urban location (Kanpur) in the Indo-Gangetic Plain

    Science.gov (United States)

    Bikkina, Srinivas; Andersson, August; Ram, Kirpa; Sarin, M. M.; Sheesley, Rebecca J.; Kirillova, Elena N.; Rengarajan, R.; Sudheer, A. K.; Gustafsson, Örjan

    2017-05-01

    The Indo-Gangetic Plain (IGP) in northern India, Pakistan, and Bangladesh is a major source of carbonaceous aerosols in South Asia. However, poorly constrained seasonality of their sources over the IGP leads to large uncertainty in climate and health effects. Here we present a first data set for year-round radiocarbon (Δ14C) and stable carbon (δ13C)-based source apportionment of total carbon (TC) in ambient PM10 (n = 17) collected from an urban site (Kanpur: 26.5°N, 80.3°E) in the IGP during January 2007 to January 2008. The year-round 14C-based fraction biomass (fbio-TC) estimate at Kanpur averages 77 ± 7% and emphasizes an impact of biomass burning emissions (BBEs). The highest fbio-TC (%) is observed in fall season (October-November, 85 ± 6%) followed by winter (December-February, 80 ± 4%) and spring (March-May, 75 ± 8%), while lowest values are found in summer (June-September, 69 ± 2%). Since biomass/coal combustion and vehicular emissions mostly contribute to carbonaceous aerosols over the IGP, we predict δ13CTC (δ13Cpred) over Kanpur using known δ13C source signatures and the measured Δ14C value of each sample. The seasonal variability of δ13Cobs - δ13Cpred versus Δ14CTC together with air mass back trajectories and Moderate Resolution Imaging Spectroradiometer fire count data reveal that carbonaceous aerosols in winter/fall are significantly influenced by atmospheric aging (downwind transport of crop residue burning/wood combustion emissions in the northern IGP), while local sources (wheat residue combustion/vehicular emissions) dominate in spring/summer. Given the large temporal and seasonal variability in sources and emission strength of TC over the IGP, 14C-based constraints are, thus, crucial for reducing their uncertainties in carbonaceous aerosol budgets in climate models.

  1. Effects of day-of-week trends and vehicle types on PM{sub 2.5}-bounded carbonaceous compositions

    Energy Technology Data Exchange (ETDEWEB)

    Pongpiachan, Siwatt, E-mail: pongpiajun@gmail.com [NIDA Center for Research & Development of Disaster Prevention & Management, School of Social and Environmental Development, National Institute of Development Administration (NIDA), 118 Moo 3, Sereethai Road, Klong-Chan, Bangkapi, Bangkok 10240 (Thailand); SKLLQG, Institute of Earth Environment, Chinese Academy of Sciences (IEECAS), Xi' an 710075 (China); Kositanont, Charnwit [Department of Microbiology, Faculty of Sciences, Chulalongkorn University, Bangkok 10330 (Thailand); Palakun, Jittree [Faculty of Education, Valaya Alongkorn Rajabhat University under the Royal Patronage (VRU), No.1 Moo 20, Phaholyothin Road, Klong luang, Pathumthani 13180 (Thailand); Liu, Suixin; Ho, Kin Fai; Cao, Junji [SKLLQG, Institute of Earth Environment, Chinese Academy of Sciences (IEECAS), Xi' an 710075 (China)

    2015-11-01

    Carbonaceous compositions of PM{sub 2.5} were measured in the heart of Bangkok from 17th November 2010 to 19th January 2012, and a data set of 94 samples was constructed. Effects of day-of-week trends and vehicle types on PM{sub 2.5}-bound TC, OC, and EC were carefully investigated. In this study, OC was the most important contributor to the total PM{sub 2.5} mass concentration. The average PM{sub 2.5}-bound OC content measured at CHAOS (18.8 ± 9.18 μg m{sup −3}) was approximately 11 times higher than at Chaumont, Switzerland (1.7 μg m{sup −3}), but approximately five times lower than at Xi'an, China (93.0 μg m{sup −3}). The application of diagnostic binary ratios of OC/EC and estimations of secondary organic carbon (SOC) coupled with autocorrelation plots (Box and Jenkins) highlight the enhanced impacts of traffic emissions, especially from diesel vehicles, on PM{sub 2.5}-bound carbonaceous compositions on weekdays relative to weekends. Hierarchical cluster analysis (HCA) coupled with principal component analysis (PCA) underline the importance of diesel emissions as the primary contributors of carbonaceous aerosols, particularly during weekdays. - Highlights: • Traffic emissions play an important role in governing OC and EC during weekdays. • Time series analysis shows the existence of day-of-week trends of OC and EC. • Diesel vehicles are the main contributors of carbonaceous compositions.

  2. Gamma 60Co-irradiation of organic matter in the Phosphoria Retort Shale

    Science.gov (United States)

    Lewan, M. D.; Ulmishek, G. F.; Harrison, W.; Schreiner, F.

    1991-04-01

    Irradiation experiments were conducted on a thermally immature rock sample of the Phosphoria Retort Shale and its isolated kerogen. A 60Co-source for gamma radiation was employed at dosages ranging from 81 to 885 Mrads, which are attainable by Paleozoic and Precambrian black shales with syngenetic uranium enrichments. Kerogen elemental, isotopic, and pyrolysate compositions are not affected at these dosages, but the bitumens extracted from the irradiated rock are affected. The major effects are reductions in the amounts of bitumen, acyclic isoprenoids, and high-molecular weight acyclic carboxylic acids. Natural differences in the amounts of bitumen and acyclic isoprenoid due to regional and stratigraphie variations in organic source input and depositional conditions make the radiation-induced reductions in these parameters difficult to use as indicators of natural radiation damage in black shales. However, the preferential reduction in the high-molecular weight acyclic carboxylic acids, which are ubiquitous in the living precursory organic matter, is diagnostic of experimental γ-irradiation but may not be diagnostic of natural irradiation. The overall process associated with radiation damage is polymerization by cross-linking through a free radical mechanism. As a result, irradiation of organic matter in black shales is more likely to retard rather than enhance petroleum generation.

  3. Geochemistry of phosphatic-shales and associated authigenic minerals of the Miocene Monterey Formation: Implications for paragenetic evolution

    Science.gov (United States)

    Sandoval, A.; Loyd, S. J.

    2016-12-01

    The Monterey Formation is a petroleum source and reservoir rock in California that was deposited in several basins during the tectonically-active Middle Miocene. The middle carbonaceous marl member of the Monterey Formation contains intervals of phosphatic-shales that are rhythmically cemented by dolomite as layers and concretions. Diagenetic minerals can form as the result of organic matter remineralization facilitated by microbes utilizing oxygen, nitrate, iron (III), sulfate and fermentation products as electron acceptors. Precipitation of phosphate and carbonate minerals tends to occur in suboxic-anoxic sediments, generally experiencing sulfate reduction, where degradation of organic matter yields alkalinity, sulfide and phosphate ions. Here, we present sulfur and carbon geochemical data in order to better characterize the conditions that led to the precipitation of phosphorous-rich minerals (e.g., carbonate-fluorapatite (CFA)) and dolomite that occur in close stratigraphic proximity. These data include concentration of CFA-associated sulfate, carbonate associated sulfate (CAS) and the respective δ°S values. The concentration of inorganic/organic carbon and associated δC values have been determined for CFA, dolomite and the host-shale, in order to further characterize the diagenetic environment of precipitation. These data indicate that authigenesis occurred in pore waters influenced by multiple microbial reactions, including respiration and methanogenesis reactions, and ultimately highlight the complexity of the Monterey diagenetic environment.

  4. Shale gas. Opportunities and challenges for European energy markets

    Energy Technology Data Exchange (ETDEWEB)

    De Joode, J.; Plomp, A.J.; Ozdemir, O. [ECN Policy Studies, Petten (Netherlands)

    2013-02-15

    The outline of the presentation shows the following elements: Introduction (Shale gas revolution in US and the situation in the EU); What could be the impact of potential shale gas developments on the European gas market?; How may shale gas developments affect the role of gas in the transition of the power sector?; and Key messages. The key messages are (1) Prospects for European shale gas widely differ from US case (different reserve potential, different competition, different market dynamics); (2) Shale gas is unlikely to be a game changer in Europe; and (3) Impact of shale gas on energy transition in the medium and long term crucially depends on gas vs. coal prices and the 'penalty' on CO2 emissions.

  5. Plan for addressing issues relating to oil shale plant siting

    Energy Technology Data Exchange (ETDEWEB)

    Noridin, J. S.; Donovan, R.; Trudell, L.; Dean, J.; Blevins, A.; Harrington, L. W.; James, R.; Berdan, G.

    1987-09-01

    The Western Research Institute plan for addressing oil shale plant siting methodology calls for identifying the available resources such as oil shale, water, topography and transportation, and human resources. Restrictions on development are addressed: land ownership, land use, water rights, environment, socioeconomics, culture, health and safety, and other institutional restrictions. Descriptions of the technologies for development of oil shale resources are included. The impacts of oil shale development on the environment, socioeconomic structure, water availability, and other conditions are discussed. Finally, the Western Research Institute plan proposes to integrate these topics to develop a flow chart for oil shale plant siting. Western Research Institute has (1) identified relative topics for shale oil plant siting, (2) surveyed both published and unpublished information, and (3) identified data gaps and research needs. 910 refs., 3 figs., 30 tabs.

  6. Comparative study on direct burning of oil shale and coal

    Science.gov (United States)

    Hammad, Ahmad; Al Asfar, Jamil

    2017-07-01

    A comparative study of the direct burning processes of oil shale and coal in a circulating fluidized bed (CFB) was done in this study using ANSYS Fluent software to solve numerically the governing equations of continuity, momentum, energy and mass diffusion using finite volume method. The model was built based on an existing experimental combustion burner unit. The model was validated by comparing the theoretical results of oil shale with proved experimental results from the combustion unit. It was found that the temperature contours of the combustion process showed that the adiabatic flame temperature was 1080 K for oil shale compared with 2260 K for coal, while the obtained experimental results of temperatures at various locations of burner during the direct burning of oil shale showed that the maximum temperature reached 962 K for oil shale. These results were used in economic and environmental analysis which show that oil shale may be used as alternative fuel for coal in cement industry in Jordan.

  7. Non-isothermal pyrolysis kinetics of three Turkish oil shales

    Energy Technology Data Exchange (ETDEWEB)

    Dogon, O.M.; Uysal, B.Z. [Gazi University, Ankara (Turkey). Dept. of Chemical Engineering

    1996-10-01

    A non-isothermal experimental study using thermogravimetric analysis (t.g.a.) was conducted to determine the overall kinetics of pyrolysis of three Turkish oil shales: Beypazari, Seyitomer and Himmetoglu. The integral method was used in the analysis of the t.g.a. data to determine first-order pyrolysis kinetics. Particle sizes of 0.7, 1.3. and 2.6 mm and final temperatures of 400, 550 and 700{degree}C were used. Himmeltoglue oil shale was found to give better yields than the other two shales. The extent of pyrolysis was found to be practically independent of particle size for all the shales. The rates of decomposition of Seyitomer and Himmetoglu oil shales were found to change at critical temperatures of {approximately} 300 and {approximately} 350{degree}C respectively. Porosities and surface areas of raw and spent shales were also determined. 35 refs., 3 figs., 5 tabs.

  8. Shale engineering application: the MAL-145 project in West Virginia

    Energy Technology Data Exchange (ETDEWEB)

    Vassilellis, George D.; Li, Charles; Bust, Vivian K. [Gaffney, Cline and Associates (United States); Moos, Daniel; Cade, Randal [Baker Hughes Inc (United States)

    2011-07-01

    With the depletion of conventional fossil fuels and the rising energy demand, oil shale and shale gas are becoming an important component of the oil and gas markets in North America. The aim of this paper is to present a novel methodology for predicting production in shale and tight formations. This method, known as the shale engineering approach and modeling, provides reservoir simulations based on modeling the propagation of the simulated rock volume. This technique was applied to an Upper Devonian shale formation in West Virginia, United States, and was compared to available data such as production logs and downhole microseismic data. Results showed a good match between the shale engineering approach data and early well performance. This paper presented a new reservoir simulation methodology which is successful in forecasting production and which can also be used for field development design and optimization.

  9. Geomechanical Properties of Unconventional Shale Reservoirs

    Directory of Open Access Journals (Sweden)

    Mohammad O. Eshkalak

    2014-01-01

    Full Text Available Production from unconventional reservoirs has gained an increased attention among operators in North America during past years and is believed to secure the energy demand for next decades. Economic production from unconventional reservoirs is mainly attributed to realizing the complexities and key fundamentals of reservoir formation properties. Geomechanical well logs (including well logs such as total minimum horizontal stress, Poisson’s ratio, and Young, shear, and bulk modulus are secured source to obtain these substantial shale rock properties. However, running these geomechanical well logs for the entire asset is not a common practice that is associated with the cost of obtaining these well logs. In this study, synthetic geomechanical well logs for a Marcellus shale asset located in southern Pennsylvania are generated using data-driven modeling. Full-field geomechanical distributions (map and volumes of this asset for five geomechanical properties are also created using general geostatistical methods coupled with data-driven modeling. The results showed that synthetic geomechanical well logs and real field logs fall into each other when the input dataset has not seen the real field well logs. Geomechanical distributions of the Marcellus shale improved significantly when full-field data is incorporated in the geostatistical calculations.

  10. Fugitive emissions from the Bakken shale illustrate role of shale production in global ethane shift

    Science.gov (United States)

    Kort, E. A.; Smith, M. L.; Murray, L. T.; Gvakharia, A.; Brandt, A. R.; Peischl, J.; Ryerson, T. B.; Sweeney, C.; Travis, K.

    2016-05-01

    Ethane is the second most abundant atmospheric hydrocarbon, exerts a strong influence on tropospheric ozone, and reduces the atmosphere's oxidative capacity. Global observations showed declining ethane abundances from 1984 to 2010, while a regional measurement indicated increasing levels since 2009, with the reason for this subject to speculation. The Bakken shale is an oil and gas-producing formation centered in North Dakota that experienced a rapid increase in production beginning in 2010. We use airborne data collected over the North Dakota portion of the Bakken shale in 2014 to calculate ethane emissions of 0.23 ± 0.07 (2σ) Tg/yr, equivalent to 1-3% of total global sources. Emissions of this magnitude impact air quality via concurrent increases in tropospheric ozone. This recently developed large ethane source from one location illustrates the key role of shale oil and gas production in rising global ethane levels.

  11. The Role of Global Emission Inventory of Carbonaceous Emissions

    Science.gov (United States)

    Fatima, H.; Sharma, O. P.; Updhyaya, H.

    2010-12-01

    Aerosols - liquid or solid particles suspended in the air - are important constituents of the global atmosphere. They have a direct effect on climate by scattering and/or absorbing solar radiation modifying the radiative balance of the atmosphere and indirect effect by acting as condensation nuclei, their increase in number concentration may give rise to increased number of cloud condensation nuclei, which might increase the droplet concentration with relatively smaller size droplets for fixed liquid water content, making clouds more reflective (Twomey, 1977). Recent measurements show that atmospheric black carbon (BC) and organic carbon (OC) aerosol particles frequently contribute significantly to the total aerosol mass (Novakov et al. 1997). BC is emitted as primary particles from incomplete combustion process, such as fossil fuel and biomass burning, and therefore much atmospheric BC is of anthropogenic origin. OC is emitted as both primary particles and by secondary production from gaseous compounds via condensation or gas phase oxidation of hydrocarbons. Primary organic aerosols come from both anthropogenic sources (fossil fuel and biomass burning) and from natural sources (such as debris, pollen, spores, and algae). Carbonaceous aerosols make up a large but highly variable fraction of the atmospheric aerosol. Black carbon aerosols absorb the solar radiation and induce positive forcing whereas organic matter aerosols reflect solar radiation and produce negative forcing. Various emission inventories have been developed for carbonaceous aerosols. Detailed emission inventories for both BC and OC have been developed (e.g., Penner et al., 1993; Cooke and Wilson, 1996; Liousse et al., 1996; Cooke et al., 1999, Bond et al. 2004) that consider both fossil fuel and biomass components. The inventories of biomass- burning BC and OC particles are more difficult to constrain than fossil fuel emissions, owing to the paucity of data. In the present study we have compared the

  12. Military Fuels Refined from Paraho-II Shale Oil.

    Science.gov (United States)

    1981-03-01

    Laboratories showed that growth of Cladosporium resinae was supported by the shale-derived JP-5 and DFM. 1t The performances of shale fuels in a turbine...27 11 Corrosion Tendencies of Shale Fuels ............................. 28 12 Growth Rating of Cladosporium Resinae in Tubes After Days of...screw cap test tubes and overlayed with 3 ml of the test fuel. Each tube was inoculated with one drop of a spore suspension of Cladosporium resinae , QM

  13. Map of assessed shale gas in the United States, 2012

    Science.gov (United States)

    ,; 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.

  14. Environmental Impact of Estonian Oil Shale CFB Firing

    Science.gov (United States)

    Loosaar, J.; Parve, T.; Konist, A.

    Oil shale based power production has been the basement of Estonia's energetical independency and economy for over 60 years. At the same time oil shale power plants emissions still give the biggest share of Estonian stationary source pollution, having significant impact to the environment. Thanks to the introduction of oil shale large scale CFB firing, reduction of the total environmental impact was achieved in last years.

  15. Fe and O EELS Studies of Ion Irradiated Murchison CM2 Carbonaceous Chondrite Matrix

    Science.gov (United States)

    Keller, L. P.; Christofferson, R.; Dukes, C. A.; Baragiola, R. A.; Rahman, Z.

    2015-01-01

    Introduction: The physical and chemical response of hydrated carbonaceous chondrite materials to space weathering processes is poorly understood. Improving this understanding is a key part of establishing how regoliths on primitive carbonaceous asteroids respond to space weathering processes, knowledge that supports future sample return missions (Hayabusa 2 and OSIRISREx) that are targeting objects of this type. We previously reported on He+ irradiation of Murchison matrix and showed that the irradiation resulted in amorphization of the matrix phyllosilicates, loss of OH, and surface vesiculation. Here, we report electron energy-loss spectroscopy (EELS) measurements of the irradiated material with emphasis on the Fe and O speciation. Sample and Methods: A polished thin section of the Murchison CM2 carbonaceous chondrite was irradiated with 4 kilovolts He(+) (normal incidence) to a total dose of 1 x 10(exp 18) He(+) per square centimeter. We extracted thin sections from both irradiated and unirradiated regions in matrix using focused ion beam (FIB) techniques with electron beam deposition for the protective carbon strap to minimize surface damage artifacts from the FIB milling. The FIB sections were analyzed using a JEOL 2500SE scanning and transmission electron microscope (STEM) equipped with a Gatan Tridiem imaging filter. EELS spectra were collected from 50 nanometer diameter regions with an energy resolution of 0.7 electronvolts FWHM at the zero loss. EELS spectra were collected at low electron doses to minimize possible artifacts from electron-beam irradiation damage. Results and Discussion: Fe L (sub 2,3) EELS spectra from matrix phyllosilicates in CM chondrites show mixed Fe(2+)/Fe(3+) oxidation states with Fe(3+)/Sigma Fe approximately 0.5. Fe L(sub 2,3) spectra from the irradiated/ amorphized matrix phyllosilicates show higher Fe(2+)/Fe(3+) ratios compared to spectra obtained from pristine material at depths beyond the implantation/amorphization layer. We

  16. Role of smectite-rich shales in frequent foundation failures in southeast Nigeria

    Indian Academy of Sciences (India)

    Raphael Iweanya Maduka; Nnadozie Onyekachi Ayogu; Chinero Nneka Ayogu; Gabriel Auodugu Gbakurun

    2016-08-01

    This paper investigated the geotechnical properties of smectite-rich shale, and its implications as foundationmaterial. Ten expansive shale samples were collected from foundation materials at Akpugo in Nkanu West L.G.A. of Enugu State, southeast Nigeria. Samples were subjected to grading, Atterberg limitscum-compaction tests, slake durability, specific gravity, permeability, undrained triaxial tests and x-raydiffraction scan. Fines and sand contents of the soil samples range from 51–97% and 3–49% respectively. Liquid limit, plastic limit and plasticity index have average values of 60.7, 19.1 and 43.3% respectively. Linear shrinkage and free swell showed average of 16.3% and 76%. These results are indicative of predominantclay soil with high plasticity, compressibility and water holding capacity. XRD scan established presence of smectite and illite clay minerals, confirming soil high plasticity, capable of causing instability in foundation soil. The shale achieved maximum dry density range between 1.79 and 1.94 kg/m$^3$ atoptimum moisture content range of 6.9–12.8%, indicating poor to fair foundation materials. The shale cohesion ranges from 15 to 30 kPa while the angle of friction ranges between 10◦ and 18◦, signifying an average strength soil material. Samples slake durability index and specific gravity fall within 24–55%and 2.50–2.58 respectively, suggesting non-durable and weak soil. Permeability of the samples ranges between 7.36×10$^{−6}$ and 4.77×10$^{−8}$ cm/s which suggested low drainage capable of causing water-log at sites. Therefore, the shale could be generally classified as poor to fair foundation material, which on moistureinflux experience reduction in strength due to deterioration of its constituent minerals, especiallyclay and cement materials during the lifespan of engineering structures. Authors therefore recommendmodification of foundation soil, appropriate foundation design and good drainage control as ways ofimproving

  17. Role of smectite-rich shales in frequent foundation failures in southeast Nigeria

    Science.gov (United States)

    Maduka, Raphael Iweanya; Ayogu, Nnadozie Onyekachi; Nneka Ayogu, Chinero; Gbakurun, Gabriel Auodugu

    2016-08-01

    This paper investigated the geotechnical properties of smectite-rich shale, and its implications as foundation material. Ten expansive shale samples were collected from foundation materials at Akpugo in Nkanu West L.G.A. of Enugu State, southeast Nigeria. Samples were subjected to grading, Atterberg limits-cum-compaction tests, slake durability, specific gravity, permeability, undrained triaxial tests and x-ray diffraction scan. Fines and sand contents of the soil samples range from 51-97% and 3-49% respectively. Liquid limit, plastic limit and plasticity index have average values of 60.7, 19.1 and 43.3% respectively. Linear shrinkage and free swell showed average of 16.3% and 76%. These results are indicative of predominant clay soil with high plasticity, compressibility and water holding capacity. XRD scan established presence of smectite and illite clay minerals, confirming soil high plasticity, capable of causing instability in foundation soil. The shale achieved maximum dry density range between 1.79 and 1.94 kg/m3 at optimum moisture content range of 6.9-12.8%, indicating poor to fair foundation materials. The shale cohesion ranges from 15 to 30 kPa while the angle of friction ranges between 10° and 18°, signifying an average strength soil material. Samples slake durability index and specific gravity fall within 24-55% and 2.50-2.58 respectively, suggesting non-durable and weak soil. Permeability of the samples ranges between 7.36 ×10-6 and 4.77 ×10-8 cm/s which suggested low drainage capable of causing water-log at sites. Therefore, the shale could be generally classified as poor to fair foundation material, which on moisture influx experience reduction in strength due to deterioration of its constituent minerals, especially clay and cement materials during the lifespan of engineering structures. Authors therefore recommend modification of foundation soil, appropriate foundation design and good drainage control as ways of improving stability of

  18. Acidization of shales with calcite cemented fractures

    Science.gov (United States)

    Kwiatkowski, Kamil; Szymczak, Piotr; Jarosiński, Marek

    2017-04-01

    Investigation of cores drilled from shale formations reveals a relatively large number of calcite-cemented fractures. Usually such fractures are reactivated during fracking and can contribute considerably to the permeability of the resulting fracture network. However, calcite coating on their surfaces effectively excludes them from production. Dissolution of the calcite cement by acidic fluids is investigated numerically with focus on the evolution of fracture morphology. Available surface area, breakthrough time, and reactant penetration length are calculated. Natural fractures in cores from Pomeranian shale formation (northern Poland) were analyzed and classified. Representative fractures are relatively thin (0.1 mm), flat and completely sealed with calcite. Next, the morphology evolution of reactivated natural fractures treated with low-pH fluids has been simulated numerically under various operating conditions. Depth-averaged equations for fracture flow and reactant transport has been solved by finite-difference method coupled with sparse-matrix solver. Transport-limited dissolution has been considered, which corresponds to the treatment with strong acids, such as HCl. Calcite coating in reactivated natural fractures dissolves in a highly non-homogeneous manner - a positive feedback between fluid transport and calcite dissolution leads to the spontaneous formation of wormhole-like patterns, in which most of the flow is focused. The wormholes carry reactive fluids deeper inside the system, which dramatically increases the range of the treatment. Non-uniformity of the dissolution patterns provides a way of retaining the fracture permeability even in the absence of the proppant, since the less dissolved regions will act as supports to keep more dissolved regions open. Evolution of fracture morphology is shown to depend strongly on the thickness of calcite layer - the thicker the coating the more pronounced wormholes are observed. However the interaction between

  19. Water Resources Management for Shale Energy Development

    Science.gov (United States)

    Yoxtheimer, D.

    2015-12-01

    The increase in the exploration and extraction of hydrocarbons, especially natural gas, from shale formations has been facilitated by advents in horizontal drilling and hydraulic fracturing technologies. Shale energy resources are very promising as an abundant energy source, though environmental challenges exist with their development, including potential adverse impacts to water quality. The well drilling and construction process itself has the potential to impact groundwater quality, however if proper protocols are followed and well integrity is established then impacts such as methane migration or drilling fluids releases can be minimized. Once a shale well has been drilled and hydraulically fractured, approximately 10-50% of the volume of injected fluids (flowback fluids) may flow out of the well initially with continued generation of fluids (produced fluids) throughout the well's productive life. Produced fluid TDS concentrations often exceed 200,000 mg/L, with elevated levels of strontium (Sr), bromide (Br), sodium (Na), calcium (Ca), barium (Ba), chloride (Cl), radionuclides originating from the shale formation as well as fracturing additives. Storing, managing and properly disposisng of these fluids is critical to ensure water resources are not impacted by unintended releases. The most recent data in Pennsylvania suggests an estimated 85% of the produced fluids were being recycled for hydraulic fracturing operations, while many other states reuse less than 50% of these fluids and rely moreso on underground injection wells for disposal. Over the last few years there has been a shift to reuse more produced fluids during well fracturing operations in shale plays around the U.S., which has a combination of economic, regulatory, environmental, and technological drivers. The reuse of water is cost-competitive with sourcing of fresh water and disposal of flowback, especially when considering the costs of advanced treatment to or disposal well injection and lessens

  20. Geothermal alteration of clay minerals and shales: diagenesis

    Energy Technology Data Exchange (ETDEWEB)

    Weaver, C.E.

    1979-07-01

    The objective of this report is to perform a critical review of the data on the mineral and chemical alterations that occur during diagenesis and low-grade metamorphism of shale and other clay-rich rocks - conditions similar to those expected from emplacement of heat-producing radioactive waste in a geologic repository. The conclusions drawn in this document are that the following type of alterations could occur: smectite alteration, ion mobilization, illitic shales, kaolinite reactions, chlorite reactions, organic reactions, paleotemperatures, low temperature shales, high temperature shales, and phase equilibrium changes.

  1. Developments in production of synthetic fuels out of Estonian shale

    Energy Technology Data Exchange (ETDEWEB)

    Aarna, Indrek

    2010-09-15

    Estonia is still the world leader in utilization of oil shale. Enefit has cooperated with Outotec to develop a new generation of solid heat carrier technology - Enefit280, which is more efficient, environmentally friendlier and has higher unit capacity. Breakeven price of oil produced in Enefit280 process is competitive with conventional oils. The new technology has advantages that allow easy adaptation to other oil shales around the world. Hydrotreated shale oil liquids have similar properties to crude oil cuts. Design for a shale oil hydrotreater unit can use process concepts, hardware components, and catalysts commercially proven in petroleum refining services.

  2. Pyrolysis and co-pyrolysis of coal and oil shale

    Energy Technology Data Exchange (ETDEWEB)

    Qiumin Zhang; Demin He; Jun Guan [Dalian University of Technology, Dalian (China). Institute of Coal Chemical Engineering

    2007-07-01

    Pyrolysis and co-pyrolysis of coal and oil shale was investigated by using Yilan oil shale, Longkou oil shale, Huolinhe lignite, Taiji gas coal and Ruqigou anthracite as raw materia1s. A fixed-bed pyrolysis and co-pyrolysis of these coal and oil shale were investigated. The results indicated that synergetic effect existed with the oil yield increased, water yield decreased, and the synergetic effect varied with the mass percentage of coal differed. The co-pyrolysis oil yield of Yilan oil shale and Ruqigou anthracite is a little higher than the linear sum of their oil yield in the pyrolysis process. But for the co-pyrolysis of Taiji gas coal and Yilan oil shale, no significant change of the oil yield was found. Huolinhe lignite and Longkou oil shale were chosen as the material for the solid heat carrier experiment. Synergetic effect analyses of both the fixed-bed pyrolysis and the retorting process with solid heat carrier were given. Huolinhe lignite is an ideal material for oil recovery by pyrolysis, with high volatile and low ash, its oil content is 8.55%. Longkou oil shale is an ideal material for oil recovery by pyrolysis, with high oil content of 14.38%. The optimum co-pyrolysis temperature for Huolinhe lignite and Longkou oil shale is 510{sup o}C. Synergetic effect was found with the oil increased 9% and water decreased 36%. 5 refs., 2 figs., 10 tabs.

  3. Thermal evolution and shale gas potential estimation of the Wealden and Posidonia Shale in NW-Germany and the Netherlands : a 3D basin modelling study

    NARCIS (Netherlands)

    Bruns, B.; Littke, R.; Gasparik, M.; van Wees, J.-D.; Nelskamp, S.

    2016-01-01

    Sedimentary basins in NW-Germany and the Netherlands represent potential targets for shale gas exploration in Europe due to the presence of Cretaceous (Wealden) and Jurassic (Posidonia) marlstones/shales as well as various Carboniferous black shales. In order to assess the regional shale gas prospec

  4. ANALYSIS OF DEVONIAN BLACK SHALES IN KENTUCKY FOR POTENTIAL CARBON DIOXIDE SEQUESTRATION AND ENHANCED NATURAL GAS PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Brandon C. Nuttall

    2005-01-01

    Devonian gas shales underlie approximately two-thirds of Kentucky. In the shale, natural gas is adsorbed on clay and kerogen surfaces. This is analogous to methane storage in coal beds, where CO{sub 2} is preferentially adsorbed, displacing methane. Black shales may similarly desorb methane in the presence of CO{sub 2}. Drill cuttings from the Kentucky Geological Survey Well Sample and Core Library were sampled to determine CO{sub 2} and CH{sub 4} adsorption isotherms. Sidewall core samples were acquired to investigate CO{sub 2} displacement of methane. An elemental capture spectroscopy log was acquired to investigate possible correlations between adsorption capacity and mineralogy. Average random vitrinite reflectance data range from 0.78 to 1.59 (upper oil to wet gas and condensate hydrocarbon maturity range). Total organic content determined from acid-washed samples ranges from 0.69 to 14 percent. CO{sub 2} adsorption capacities at 400 psi range from a low of 14 scf/ton in less organic-rich zones to more than 136 scf/ton. Initial estimates based on these data indicate a sequestration capacity of 5.3 billion tons of CO{sub 2} in the Lower Huron Member of the Ohio Shale of eastern Kentucky and as much as 28 billion tons total in the deeper and thicker parts of the Devonian shales in Kentucky. Should the black shales of Kentucky prove to be a viable geologic sink for CO{sub 2}, their extensive occurrence in Paleozoic basins across North America would make them an attractive regional target for economic CO{sub 2} storage and enhanced natural gas production.

  5. Ion irradiation of carbonaceous chondrites: A new view of space weathering on primitive asteroids

    Science.gov (United States)

    Lantz, C.; Brunetto, R.; Barucci, M. A.; Fornasier, S.; Baklouti, D.; Bourçois, J.; Godard, M.

    2017-03-01

    We present an experimental study on ion irradiation of carbonaceous chondrites, simulating solar wind irradiation on primitive asteroids, to better constrain the space weathering processes of low albedo objects. The irradiations were performed on pressed pellets of the CV Allende, CO Frontier Mountain 95002 and Lancé, CM Mighei, CI Alais, and ungrouped Tagish Lake meteorites, as well as on some silicate samples (olivine and diopside). We used 40keV He+ with fluences up to 6 × 1016 ions/cm2 corresponding to timescales of 103-104 years for an object in the Main Belt. Reflectance spectra were acquired ex situ before and after irradiations in the visible to mid-infrared range (0.4-16 μm). Several spectral modifications are observed. In the MIR range, we observe a shift of the phyllosilicates (near 3 and 10 μm) and silicates (near 10 μm) bands toward longer wavelength. In the visible-NIR range, spectral darkening and reddening are observed for some samples, while others show spectral brightening and blueing. Results are also compared with previous irradiation on ordinary and carbonaceous chondrites. We find that the spectral modifications in the visible range are correlated with the initial albedo/composition. We propose a model for space weathering effects on low albedo objects, showing that those with initial albedo between 5 and 9% shall not suffer SpWe effects in the visible range. These experiments provide new clues on spectroscopic features modifications within the visible-infrared ranges that could be detected in situ by future sample return missions (Hayabusa-2/JAXA and OSIRIS-REx/NASA).

  6. Characteristics of carbonaceous aerosols emitted from peatland fire in Riau, Sumatra, Indonesia

    Science.gov (United States)

    Fujii, Yusuke; Iriana, Windy; Oda, Masafumi; Puriwigati, Astiti; Tohno, Susumu; Lestari, Puji; Mizohata, Akira; Huboyo, Haryono Setiyo

    2014-04-01

    Biomass burning is a significant source of fine particulate matter (PM2.5). Forest, bush, and peat fires in Kalimantan and Sumatra, Indonesia are major sources of transboundary haze pollution in Southeast Asia. However, limited data exist regarding the chemical characteristics of aerosols at sources. We conducted intensive field studies in Riau Province, Sumatra, Indonesia, during the peatland fire and non-burning seasons in 2012. We characterized PM2.5 carbonaceous aerosols emitted from peatland fire based on ground-based source-dominated sampling. PM2.5 aerosols were collected with two mini-volume samplers using Teflon and quartz fiber filters. Background aerosols were also sampled during the transition period between the non-burning and fire seasons. We analyzed the carbonaceous content (organic carbon (OC) and elemental carbon (EC)) by a thermal optical reflectance utilizing the IMPROVE_A protocol and the major organic components of the aerosols by a gas chromatography/mass spectrometry. PM2.5 aerosols emitted from peatland fire were observed in high concentrations of 7120 ± 3620 μg m-3 and were primarily composed of OC (71.0 ± 5.11% of PM2.5 mass). Levoglucosan exhibited the highest total ion current and was present at concentrations of 464 ± 183 μg m-3. The OC/EC ratios (36.4 ± 9.08), abundances of eight thermally-derived carbon fractions, OC/Levoglucosan ratios (10.6 ± 1.96), and Levoglucosan/Mannosan ratios (10.6 ± 2.03) represent a signature profile that is inherent in peatland fire. These data will be useful in identifying contributions from single or multiple species in atmospheric aerosol samples collected from peatland fires.

  7. Blackening of fault gouge by comminution and pyrolysis of carbonaceous materials during earthquake slip

    Science.gov (United States)

    Kaneki, Shunya; Hirono, Tetsuro

    2016-05-01

    Black fault gouges sometimes develop, mainly in sedimentary rocks, but the cause of the color transformation is not well understood. Here we demonstrated the blackening of synthetic mixtures of montmorillonite and bituminous coal and of montmorillonite and magnetite in milling, heating, and friction experiments. Mixed samples with a higher volume fraction of coal or magnetite before the experiments showed lower L* values (lightness index; lower values indicate darker blacks), because coal and magnetite are intrinsically black. The milling and heating experiments showed that the L* values of mixed samples of montmorillonite and coal drastically decreased with longer milling times and higher temperatures. The L* values of mixed samples of montmorillonite and magnetite also decreased with longer milling times, but no notable change was observed in the samples after the heating experiments. Because comminution by milling induces granulation of the constituent materials, blackening of the experimental samples was primarily caused by dispersal through the sample of fine black particles such as coal and magnetite, but it could be strengthened by adsorption onto host particles of organic gases produced by pyrolysis of carbonaceous material at high temperature. The friction experiment with mixed samples of montmorillonite and coal produced the remarkably low L* values. Friction induces both comminution and heating of samples, so the blackening could be greater than after either milling or heating alone. Therefore, relatively black fault gouges, compared with the surrounding host rocks, might have experienced comminution and heating, probably related to earthquake slip. Thus, black coloration could be one of the important information on fieldwork.

  8. Petroleum source rock evaluation of the Alum and Dictyonema Shales (Upper Cambrian-Lower Ordovician) in the Baltic Basin and Podlasie Depression (eastern Poland)

    Science.gov (United States)

    Kosakowski, Paweł; Kotarba, Maciej J.; Piestrzyński, Adam; Shogenova, Alla; Więcław, Dariusz

    2017-03-01

    We present geochemical characteristics of the Lower Palaeozoic shales deposited in the Baltic Basin and Podlasie Depression. In the study area, this strata are represented by the Upper Cambrian-Lower Ordovician Alum Shale recognized in southern Scandinavia and Polish offshore and a equivalent the Lower Tremadocian Dictyonema Shale from the northern Estonia and the Podlasie Depression in Poland. Geochemical analyses reveal that the Alum Shale and Dictyonema Shale present high contents of organic carbon. These deposits have the best source quality among the Lower Palaeozoic strata, and they are the best source rocks in the Baltic region. The bituminous shales complex has TOC contents up to ca. 22 wt%. The analysed rocks contain low-sulphur, oil-prone Type-II kerogen deposited in anoxic or sub-oxic conditions. The maturity of the Alum and Dictyonema Shales changes gradually, from the east and north-east to the west and south-west, i.e. in the direction of the Tornquist-Teisseyre Zone. Samples, located in the seashore of Estonia and in the Podlasie region, are immature and in the initial phase of "oil window". The mature shales were found in the central offshore part of the Polish Baltic Basin, and the late mature and overmature are located in the western part of the Baltic Basin. The Alum and Dictyonema Shales are characterized by a high grade of radioactive elements, especially uranium. The enrichment has a syngenetic or early diagenetic origin. The measured content of uranium reached up to 750 ppm and thorium up to 37 ppm.

  9. Petroleum source rock evaluation of the Alum and Dictyonema Shales (Upper Cambrian-Lower Ordovician) in the Baltic Basin and Podlasie Depression (eastern Poland)

    Science.gov (United States)

    Kosakowski, Paweł; Kotarba, Maciej J.; Piestrzyński, Adam; Shogenova, Alla; Więcław, Dariusz

    2016-05-01

    We present geochemical characteristics of the Lower Palaeozoic shales deposited in the Baltic Basin and Podlasie Depression. In the study area, this strata are represented by the Upper Cambrian-Lower Ordovician Alum Shale recognized in southern Scandinavia and Polish offshore and a equivalent the Lower Tremadocian Dictyonema Shale from the northern Estonia and the Podlasie Depression in Poland. Geochemical analyses reveal that the Alum Shale and Dictyonema Shale present high contents of organic carbon. These deposits have the best source quality among the Lower Palaeozoic strata, and they are the best source rocks in the Baltic region. The bituminous shales complex has TOC contents up to ca. 22 wt%. The analysed rocks contain low-sulphur, oil-prone Type-II kerogen deposited in anoxic or sub-oxic conditions. The maturity of the Alum and Dictyonema Shales changes gradually, from the east and north-east to the west and south-west, i.e. in the direction of the Tornquist-Teisseyre Zone. Samples, located in the seashore of Estonia and in the Podlasie region, are immature and in the initial phase of "oil window". The mature shales were found in the central offshore part of the Polish Baltic Basin, and the late mature and overmature are located in the western part of the Baltic Basin. The Alum and Dictyonema Shales are characterized by a high grade of radioactive elements, especially uranium. The enrichment has a syngenetic or early diagenetic origin. The measured content of uranium reached up to 750 ppm and thorium up to 37 ppm.

  10. Why stratigraphy and sedimentology in shales are important : an example from the Woodford Shale, Permian Basin, west Texas

    Energy Technology Data Exchange (ETDEWEB)

    Harris, N.B. [Alberta Univ., Edmonton, AB (Canada); Colorado School of Mines, Boulder, CO (United States); Hemmesch, N.T.; Mnich, C.A. [Colorado School of Mines, Boulder, CO (United States). Geology and Geological Engineering; Aoudia, K.; Miskimins, J. [Colorado School of Mines, Boulder, CO (United States). Dept. of Petroleum Engineering

    2010-07-01

    This presentation explained why stratigraphy and sedimentology in shales are important. The presentation provided an example from the Woodford Shale, Permian Basin, located in western Texas. Several illustrations were presented to demonstrate a stratigraphic sequence in black shale. Other topics that were discussed included geologic settings; paleogeography; silled basins; motivation for rock properties research; and factor analysis results. It was concluded that sequence stratigraphic analyses in black shales requires an integrated, multidisciplinary approach. The presentation showed that third and fourth order stratigraphic cycles are indicated by the repetition of exotic beds whose composition vary regionally. tabs., figs.

  11. Baseline groundwater chemistry characterization in an area of future Marcellus shale gas development

    Science.gov (United States)

    Eisenhauer, P.; Zegre, N.; Edwards, P. J.; Strager, M.

    2012-12-01

    The recent increase in development of the Marcellus shale formation for natural gas in the mid-Atlantic can be attributed to advances in unconventional extraction methods, namely hydraulic fracturing, a process that uses water to pressurize and fracture relatively impermeable shale layers to release natural gas. In West Virginia, the Department of Energy estimates 95 to 105 trillion cubic feet (TCF) of expected ultimately recovery (EUR) of natural gas for this formation. With increased development of the Marcellus shale formation comes concerns for the potential of contamination to groundwater resources that serve as primary potable water sources for many rural communities. However, the impacts of this practice on water resources are poorly understood because of the lack of controlled pre versus post-drilling experiments attributed to the rapid development of this resource. To address the knowledge gaps of the potential impacts of Marcellus shale development on groundwater resources, a pre versus post-drilling study has been initiated by the USFS Fernow Experimental Forest in the Monongahela National Forest. Drilling is expected to start at three locations within the next year. Pre-drilling water samples were collected and analyzed from two groundwater wells, a shallow spring, a nearby lake, and river to characterize background water chemistry and identify potential end-members. Geochemical analysis includes major ions, methane, δ13C-CH4, δ2H-CH4, 226Radium, and δ13C-DIC. In addition, a GIS-based conceptual ground water flow model was developed to identify possible interactions between shallow groundwater and natural gas wells given gas well construction failure. This model is used to guide management decisions regarding groundwater resources in an area of increasing shale gas development.

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

    Science.gov (United States)

    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.

  13. Source apportionment of the summer time carbonaceous aerosol at Nordic rural background sites

    Directory of Open Access Journals (Sweden)

    K. E. Yttri

    2011-06-01

    Full Text Available In the present study, natural and anthropogenic sources of particulate organic carbon (OCp and elemental carbon (EC have been quantified based on weekly filter samples of PM10 collected at four Nordic rural background sites (Birkenes (Norway, Hyytiälä (Finland Vavihill (Sweden, Lille Valby (Denmark during late summer (5 August–2 September 2009. Levels of source specific tracers, i.e. cellulose, levoglucosan, mannitol and the 14C/12C ratio of total carbon (TC, have been used as input for source apportionment of the carbonaceous aerosol, whereas Latin Hypercube Sampling (LHS was used to statistically treat the multitude of possible combinations resulting from this approach.

    The carbonaceous aerosol (here: TCp; i.e. particulate TC was totally dominated by natural sources (69–86 %, with biogenic secondary organic aerosol (BSOA being the single most important source (48–57 %. Interestingly, primary biological aerosol particles (PBAP were the second most important source (20–32 %. The anthropogenic contribution was mainly attributed to fossil fuel sources (OCff and ECff (10–24 %, whereas no more than 3–7 % was explained by combustion of biomass (OCbb and ECbb in this late summer campaign i.e. emissions from residential wood burning and/or wild/agricultural fires. Fossil fuel sources totally dominated the ambient EC loading, accounting for 4–12 % of TCp, whereas <1.5 % was attributed to combustion of biomass. The carbonaceous aerosol source apportionment showed only minor variation between the four selected sites. However, Hyytiälä and Birkenes showed greater resemblance to each other, as did Lille Valby and Vavihill, the two latter being somewhat more influenced by anthropogenic sources.

    Ambient levels of organosulphates and nitrooxy-organosulphates in the Nordic rural background environment are reported for

  14. Source apportionment of the summer time carbonaceous aerosol at Nordic rural background sites

    Directory of Open Access Journals (Sweden)

    K. E. Yttri

    2011-12-01

    Full Text Available In the present study, natural and anthropogenic sources of particulate organic carbon (OCp and elemental carbon (EC have been quantified based on weekly filter samples of PM10 (particles with aerodynamic diameter <10 μm collected at four Nordic rural background sites [Birkenes (Norway, Hyytiälä (Finland, Vavihill (Sweden, Lille Valby, (Denmark] during late summer (5 August–2 September 2009. Levels of source specific tracers, i.e. cellulose, levoglucosan, mannitol and the 14C/12C ratio of total carbon (TC, have been used as input for source apportionment of the carbonaceous aerosol, whereas Latin Hypercube Sampling (LHS was used to statistically treat the multitude of possible combinations resulting from this approach. The carbonaceous aerosol (here: TCp; i.e. particulate TC was totally dominated by natural sources (69–86%, with biogenic secondary organic aerosol (BSOA being the single most important source (48–57%. Interestingly, primary biological aerosol particles (PBAP were the second most important source (20–32%. The anthropogenic contribution was mainly attributed to fossil fuel sources (OCff and ECff (10–24%, whereas no more than 3–7% was explained by combustion of biomass (OCbb and ECbb in this late summer campaign i.e. emissions from residential wood burning and/or wild/agricultural fires. Fossil fuel sources totally dominated the ambient EC loading, which accounted for 4–12% of TCp, whereas <1.5% of EC was attributed to combustion of biomass. The carbonaceous aerosol source apportionment showed only minor variation between the four selected sites. However, Hyytiälä and Birkenes showed greater resemblance to each other, as did Lille Valby and Vavihill, the two latter being somewhat more influenced by anthropogenic sources. Ambient levels of organosulphates and nitrooxy-organosulphates in the Nordic rural

  15. Carbonaceous species in PM2.5 and PM10 in urban area of Zhengzhou in China: Seasonal variations and source apportionment

    Science.gov (United States)

    Wang, Qun; Jiang, Nan; Yin, Shasha; Li, Xiao; Yu, Fei; Guo, Yue; Zhang, Ruiqin

    2017-07-01

    PM2.5 and PM10 samples were simultaneously collected in an urban site in Zhengzhou, China from October 2014 to July 2015 representing the four seasons. Organic carbon (OC), elemental carbon (EC), and non-polar organic compounds including n-alkanes (C8-C40) and polycyclic aromatic hydrocarbons (PAHs) were quantified. The characteristics of their concentrations, seasonal variations, and sources of n-alkanes and PAHs were investigated. Diagnostic ratios and positive matrix factorization (PMF) were used to characterize carbonaceous species, identify their possible sources, and apportion the contributions from each possible source. The concentrations of the components exhibited distinct seasonal variation, that is, the concentrations are high in winter and low in summer. This finding could be associated with increase in air pollutant emissions during heating season and stable weather condition. The estimated total carbonaceous aerosol accounts for 32% of PM2.5 and 30% of PM10. Hence, carbonaceous compounds were the major components of particulate matter in the study area. Moreover, OC, EC, PAHs, and n-alkanes preferentially accumulated into fine particles. The carbonaceous components exhibited high correlation in PM2.5 and PM10, thereby indicating that their sources were similar. The PMF results revealed that the main sources of PAHs were coal combustion (40%) and motor vehicles (29%); n-alkanes were mainly from burning of fossil fuel (48%). These sources were consistent with the diagnostic ratios obtained. This study provides guidance for improving air quality and reducing human exposure to toxic air pollutants.

  16. Application of Scanning-Imaging X-Ray Microscopy to Fluid Inclusion Candidates in Carbonates of Carbonaceous Chondrites

    Science.gov (United States)

    Tsuchiyama, Akira; Nakano, Tsukasa; Miyake, Akira; Akihisa, Takeuchi; Uesugi, Kentaro; Suzuki, Yoshio; Kitayama, Akira; Matsuno, Junya; Zolensky, Michael E.

    2016-01-01

    In order to search for such fluid inclusions in carbonaceous chondrites, a nondestructive technique using x-ray micro-absorption tomography combined with FIB sampling was developed and applied to a carbonaceous chondrite. They found fluid inclusion candidates in calcite grains, which were formed by aqueous alteration. However, they could not determine whether they are really aqueous fluids or merely voids. Phase and absorption contrast images can be simultaneously obtained in 3D by using scanning-imaging x-ray microscopy (SIXM). In refractive index, n=1-sigma+i(beta), in the real part, 1-sigma is the refractive index with decrement, sigma, which is nearly proportional to the density, and the imaginary part, beta, is the extinction coefficient, which is related to the liner attenuation coefficient, mu. Many phases, including water and organic materials as well as minerals, can be identified by SIXM, and this technique has potential availability for Hayabusa-2 sample analysis too. In this study, we examined quantitative performance of d and m values and the spatial resolution in SIXM by using standard materials, and applied this technique to carbonaceous chondrite samples. We used POM ([CH2O]n), silicon, quartz, forsterite, corundum, magnetite and nickel as standard materials for examining the sigma and mu values. A fluid inclusion in terrestrial quartz and bi-valve shell (Atrina vexillum), which are composed of calcite and organic layers with different thickness, were also used for examining the spatial resolution. The Ivuna (CI) and Sutter's Mill (CM) meteorites were used as carbonaceous chondrite samples. Rod- or cube-shaped samples 20-30 micron in size were extracted by using FIB from cross-sectional surfaces of the standard materials or polished thin sections of the chondrites, which was previously observed with SEM. Then, the sample was attached to a thin W-needle and imaged by SIXM system at beamline BL47XU, SPring-8, Japan. The slice thickness was 109.3 nm

  17. Radar-enabled recovery of the Sutter's Mill meteorite, a carbonaceous chondrite regolith breccia.

    Science.gov (United States)

    Jenniskens, Peter; Fries, Marc D; Yin, Qing-Zhu; Zolensky, Michael; Krot, Alexander N; Sandford, Scott A; Sears, Derek; Beauford, Robert; Ebel, Denton S; Friedrich, Jon M; Nagashima, Kazuhide; Wimpenny, Josh; Yamakawa, Akane; Nishiizumi, Kunihiko; Hamajima, Yasunori; Caffee, Marc W; Welten, Kees C; Laubenstein, Matthias; Davis, Andrew M; Simon, Steven B; Heck, Philipp R; Young, Edward D; Kohl, Issaku E; Thiemens, Mark H; Nunn, Morgan H; Mikouchi, Takashi; Hagiya, Kenji; Ohsumi, Kazumasa; Cahill, Thomas A; Lawton, Jonathan A; Barnes, David; Steele, Andrew; Rochette, Pierre; Verosub, Kenneth L; Gattacceca, Jérôme; Cooper, George; Glavin, Daniel P; Burton, Aaron S; Dworkin, Jason P; Elsila, Jamie E; Pizzarello, Sandra; Ogliore, Ryan; Schmitt-Kopplin, Phillipe; Harir, Mourad; Hertkorn, Norbert; Verchovsky, Alexander; Grady, Monica; Nagao, Keisuke; Okazaki, Ryuji; Takechi, Hiroyuki; Hiroi, Takahiro; Smith, Ken; Silber, Elizabeth A; Brown, Peter G; Albers, Jim; Klotz, Doug; Hankey, Mike; Matson, Robert; Fries, Jeffrey A; Walker, Richard J; Puchtel, Igor; Lee, Cin-Ty A; Erdman, Monica E; Eppich, Gary R; Roeske, Sarah; Gabelica, Zelimir; Lerche, Michael; Nuevo, Michel; Girten, Beverly; Worden, Simon P

    2012-12-21

    Doppler weather radar imaging enabled the rapid recovery of the Sutter's Mill meteorite after a rare 4-kiloton of TNT-equivalent asteroid impact over the foothills of the Sierra Nevada in northern California. The recovered meteorites survived a record high-speed entry of 28.6 kilometers per second from an orbit close to that of Jupiter-family comets (Tisserand's parameter = 2.8 ± 0.3). Sutter's Mill is a regolith breccia composed of CM (Mighei)-type carbonaceous chondrite and highly reduced xenolithic materials. It exhibits considerable diversity of mineralogy, petrography, and isotope and organic chemistry, resulting from a complex formation history of the parent body surface. That diversity is quickly masked by alteration once in the terrestrial environment but will need to be considered when samples returned by missions to C-class asteroids are interpreted.

  18. Removal of fluoride ions from water by adsorption onto carbonaceous materials produced from coffee grounds.

    Science.gov (United States)

    Ogata, Fumihiko; Tominaga, Hisato; Yabutani, Hitoshi; Kawasaki, Naohito

    2011-01-01

    Carbonaceous material for the removal of fluoride ions from water was prepared from coffee grounds (CGs) by calcination and subsequent HCl treatment. The characteristics of the CGs, including the surface area, mean pore diameter, pore volume, and surface functional groups were determined, and the morphological characteristics were evaluated using scanning electron microscopy. The adsorption isotherms, saturated amount of fluoride ions adsorbed, and the effect of contact time and temperature on the adsorption of fluoride ions were investigated for a sample of tap water. The specific surface area of CG calcined at 600° (CG600) was larger than that of CGs calcined at 400, 800, and 1000°. Phenolic, lactonic, and carboxyl groups were detected on the CG600 surface. The adsorption capacity of the carbonized CGs for fluoride was ranked in the order CG400 water.

  19. Predicting heating values of lignocellulosics and carbonaceous materials from proximate analysis

    Energy Technology Data Exchange (ETDEWEB)

    Cordero, T.; Marquez, F.; Rodriguez-Morasol, J.; Rodriguez, J.J. [University of Malaga, Malaga (Spain). Dept. of Chemical Engineering

    2001-09-21

    A simple equation based on proximate analysis (volatile matter and fixed carbon contents) is presented which allows calculation of the higher heating value of lignocellulosics as well as the charcoals resulting form their carbonization. The equation has been tested with different lignocellulosic wastes and chars obtained from carbonization at different temperatures. Deviations from the experimental heating values fall in most cases below 2%. A comparison is presented with some other equations from the literature based on proximate, ultimate and chemical analysis data. As a general conclusion the equation proposed in this paper leads to comparable and in many cases more accurate predictions of heating values and has the advantage of being applicable to a wide range of carbonaceous materials, requiring only a simple rapid and cheap proximate analysis of the samples. 14 refs., 5 tabs.

  20. Carbonaceous particles and aerosol mass closure in PM2.5 collected in a port city

    Science.gov (United States)

    Genga, A.; Ielpo, P.; Siciliano, T.; Siciliano, M.

    2017-01-01

    Mass concentrations of PM2.5, mineral dust, organic carbon (OC) and elemental carbon (EC), water-soluble organic carbon (WSOC), sea salts and anthropogenic metals have been studied in a city-port of south Italy (Brindisi). This city is characterized by different emission sources (ship, vehicular traffic, biomass burning and industrial emissions) and it is an important port and industrial site of the Adriatic sea. Based on diagnostic ratios of carbonaceous species we assess the presence of biomass burning emissions (BBE), fossil fuel emissions (FFE) and ship emission (SE). Our proposed conversion factors from OC to OM are higher than those reported in the literature for urban site: the reason of this could be due to the existence of aged combustion aerosols during the sampling campaign (WSOC/OC = 0.6 ± 0.3).

  1. Determination of ultimate carbonaceous BOD and the specific rate constant (K1)

    Science.gov (United States)

    Stamer, J.K.; Bennett, J.P.; McKenzie, Stuart W.

    1982-01-01

    Ultimate carbonaceous biochemical oxygen demand (BODu) and the specific rate constant (K1) at which the demand is exerted are important parameters in designing biological wastewater treatment plants and in assessing the impact of wastewater on receiving streams. An analytical method is presented which uses time-series concentrations of BOD, defined as the calculated sum of dissolved oxygen (DO) losses at each time of measurement, for determining BODu and K1. Time-series DO measurements are obtained from a water sample that is incubated in darkness at 20 degrees Celsius in the presence of nitrapyrin, a chemical nitrification inhibitor. Time-series concentrations of BOD that approximate first order kinetics can be analyzed graphically or mathematically to compute BODu and K1.

  2. Radar-Enabled Recovery of the Sutters Mill Meteorite, a Carbonaceous Chondrite Regolith Breccia

    Science.gov (United States)

    Jenniskens, Petrus M.; Fries, Marc D.; Yin, Qing-Zhu; Zolensky, Michael E.; Krot, Alexander N.; Sandford, Scott A.; Sears, Derek; Beauford, Robert; Ebel, Denton S.; Friedrich, Jon M.; Nagashima, Kazuhide; Wimpenny, Josh; Yamakawa, Akane; Nishiizumi, Kunihiko; Hamajima, Yasunori; Caffee, Marc W.; Welten, Kees C.; Laubenstein, Matthias; Davis, Andrew M.; Simon, Steven B.; Heck, Phillipp R.; Young, Edward D.; Kohl, Issaku E.; Thiemens, Mark H.; Nunn, Morgan H.; Mikouchi, Takashi; Hagiya, Kenji; Ohsumi, Kazumasa; Cahill, Thomas A.; Lawton, Jonathan A.; Barnes, David; Steele, Andrew; Rochette, Pierre; Verosub, Kenneth L.; Gattacceca, Jerome

    2012-01-01

    Doppler weather radar imaging enabled the rapid recovery of the Sutter's Mill meteorite after a rare 4-kiloton of TNT-equivalent asteroid impact over the foothills of the Sierra Nevada in northern California. The recovered meteorites survived a record high-speed entry of 28.6 kilometers per second from an orbit close to that of Jupiter-family comets (Tisserand's parameter = 2.8 +/- 0.3). Sutter's Mill is a regolith breccia composed of CM (Mighei)-type carbonaceous chondrite and highly reduced xenolithic materials. It exhibits considerable diversity of mineralogy, petrography, and isotope and organic chemistry, resulting from a complex formation history of the parent body surface. That diversity is quickly masked by alteration once in the terrestrial environment but will need to be considered when samples returned by missions to C-class asteroids are interpreted.

  3. Comparison of quartz sand, anthracite, shale and biological ceramsite for adsorptive removal of phosphorus from aqueous solution.

    Science.gov (United States)

    Jiang, Cheng; Jia, Liyue; Zhang, Bo; He, Yiliang; Kirumba, George

    2014-02-01

    The choice of substrates with high phosphorus adsorption capacity is vital for sustainable phosphorus removal from waste water in constructed wetlands. In this study, four substrates were used: quartz sand, anthracite, shale and biological ceramsite. These substrate samples were characterized by Xray diffractometry and scanning electron microscopy studies for their mineral components (chemical components) and surface characteristics. The dynamic experimental results revealed the following ranking order for total phosphorus (TP) removal efficiency: anthracite > biological ceramsite > shale > quartz sand. The adsorptive removal capacities for TP using anthracite, biological ceramsite, shale and quartz sand were 85.87, 81.44, 59.65, and 55.98 mg/kg, respectively. Phosphorus desorption was also studied to analyze the substrates' adsorption efficiency in wastewater treatment as well as the substrates' ability to be reused for treatment. It was noted that the removal performance for the different forms of phosphorus was dependent on the nature of the substrate and the adsorption mechanism. A comparative analysis showed that the removal of particulate phosphorus was much easier using shale. Whereas anthracite had the highest soluble reactive phosphorus (SRP) adsorptive capacity, biological ceramsite had the highest dissolved organic phosphorus (DOP) removal capacity. Phosphorus removal by shale and biological ceramsite was mainly through chemical adsorption, precipitation or biological adsorption. On the other hand, phosphorus removal through physical adsorption (electrostatic attraction or ion exchange) was dominant in anthracite and quartz sand.

  4. More gaps than shale: stratigraphic incompleteness of marine shale successions using a Toarcian example

    Science.gov (United States)

    Trabucho-Alexandre, J. P.

    2014-12-01

    Marine shale successions are probably the best archives of earth history. The degree of completeness of a marine shale succession is a critical factor in the interpretation of the geologic record of climatic, oceanic, and biogeochemical processes, in the prediction of timescales of those processes, in the determination of the duration of events, and in the establishment of correlations between successions. The sedimentation rates of marine shale successions are often calculated by dividing the thickness of a succession by the duration of the stratigraphic interval it occupies. Sedimentation rates calculated this way are always much lower than rates measured directly in equivalent modern environments. When we apply modern rates to the deposits left behind by their ancient equivalents, and correct for compaction due to overburden and time, we find that the entire succession can be deposited in a relatively short time. Since we know that the stratigraphic interval occupied by such ancient deposits is much longer, we must conclude that the succession is very incomplete. In this presentation, I will use a few different methods to show that 65 to >80% of the duration of the Toarcian oceanic anoxic event in Yorkshire, U.K., is represented by gaps rather than shale. This means that the Toarcian oceanic anoxic event is not as short as proposed by authors who studied the cyclostratigraphy of the Yorkshire succession, and that it probably represents a much longer-term history of environmental change driven by processes acting on longer time scales.

  5. [Characteristics of carbonaceous aerosol concentration in snow and ice of glaciers in Tianshan Mountains].

    Science.gov (United States)

    Wang, Sheng-Jie; Zhang, Ming-Jun; Wang, Fei-Teng; Li, Zhong-Qin

    2012-03-01

    The snow and ice samples, collected at Glacier No. 1 at the headwaters of Urumqi River (UG1) and Glacier No. 51 at Haxilegen of Kuytun River (HG51) in 2002 and 2004, were analyzed for organic carbon (OC) and element carbon (EC) by thermal/ optical reflectance (TOR). The spatio-temporal characteristics and environmental significance of OC and EC concentration were discussed in details. The concentration order of total carbon (TC) was: snowpack of west branch on UG1 (1 943 ng x g(-1)) > snowpack of east branch on UG1 (989 ng x g(-1)) > snowpack of HG51 (150 ng x g(-1)) > glacier ice of east branch on UG1 (77 ng x g(-1)), and the concentration order of OC and EC lay similar as TC. The concentration of OC and EC in snowpack of Tianshan Mountains were 557 ng x g(-1) and 188 ng x g(-1), respectively. Concentration peak of carbonaceous aerosol usually appeared near the dust layer at the bottom section of snowpack, but the some sudden events could increase the concentration in the surface snow. Because of the seasonality of carbon emission (e. g. heating and agricultural activities) and transportation (e. g. atmospheric circulation), the concentration of carbonaceous aerosol increased from July to November with fluctuations. Difference on the order of magnitude might exist between the concentration in snow (firn) and glacier ice, which was influenced by the glacier surroundings, sampling situation and other factors. EC on the surface snow affected the albedo significantly, and an average albedo reduction of 0.22 in the wavelength of 300-700 nm was simulated by SNICAR (snow, ice, and aerosol radiative) model.

  6. Carbonaceous aerosols in megacity Xi'an, China: Implications of thermal/optical protocols comparison

    Science.gov (United States)

    Han, Y. M.; Chen, L.-W. A.; Huang, R.-J.; Chow, J. C.; Watson, J. G.; Ni, H. Y.; Liu, S. X.; Fung, K. K.; Shen, Z. X.; Wei, C.; Wang, Q. Y.; Tian, J.; Zhao, Z. Z.; Prévôt, André S. H.; Cao, J. J.

    2016-05-01

    Carbonaceous aerosol is an important component that influences the environment, climate, and human health. Organic and elemental carbon (OC and EC) are the two main constituents of carbonaceous aerosols that have opposite, i.e., cooling versus warming, effects on the Earth's radiation balance. Knowledge on the variability of OC/EC splits measured by different thermal/optical protocols is useful for understanding the uncertainty in the climate models. This study shows good correlations within OC or EC (r2 > 0.83, P burning samples. However, EC concentrations differ by more than two folds, and OC/EC ratios differ up to a factor of 2.7. The discrepancies were attributed to the selection between the reflectance and transmittance corrections and the different peak inert-atmosphere temperature. The IMPROVE and IMPROVE_A protocols also quantified different char and soot concentrations, two subtypes of EC with distinct chemical and optical properties. Char, but not soot, was found to correlate with the humic-like substances (HULIS) content in the samples, suggesting that both char and HULIS originate mainly from biomass burning. A one-year (2012-2013) ambient aerosol monitoring in Xi'an, China, shows that OC, EC, and char displayed winter highs and summer lows, while soot had no seasonal trend. The char/soot ratios showed a "single peak" in winter, while OC/EC ratios exhibited "dual peak" feature due to the influence of secondary organic aerosol formation. In addition to commonly measured OC and EC, we recommend both char and soot from a common reference method to be considered in the chemical transport and climate models.

  7. Microporous carbonaceous adsorbents for CO2 separation via selective adsorption

    KAUST Repository

    Zhao, Yunfeng

    2015-01-01

    Selective adsorption of CO2 has important implications for many energy and environment-related processes, which require the separation of CO2 from other gases (e.g. N2 and CH4) with high uptakes and selectivity. The development of high-performance adsorbents is one of the most promising solutions to the success of these processes. The present review is focused on the state-of-the-art of carbon-based (carbonaceous) adsorbents, covering microporous inorganic carbons and microporous organic polymers, with emphasis on the correlation between their textural and compositional properties and their CO2 adsorption/separation performance. Special attention is given to the most recently developed materials that were not covered in previous reviews. We summarize various effective strategies (N-doping, surface functionalization, extra-framework ions, molecular design, and pore size engineering) for enhancing the CO2 adsorption capacity and selectivity of carbonaceous adsorbents. Our discussion focuses on CO2/N2 separation and CO2/CH4 separation, while including an introduction to the methods and criteria used for evaluating the performance of the adsorbents. Critical issues and challenges regarding the development of high-performance adsorbents as well as some overlooked facts and misconceptions are also discussed, with the aim of providing important insights into the design of novel carbonaceous porous materials for various selective adsorption based applications. This journal is © The Royal Society of Chemistry.

  8. Characterization of airborne particles during production of carbonaceous nanomaterials.

    Science.gov (United States)

    Yeganeh, Behnoush; Kull, Christy M; Hull, Matthew S; Marr, Linsey C

    2008-06-15

    Despite the rapid growth in nanotechnology, very little is known about the unintended health or environmental effects of manufactured nanomaterials. The development of nanotechnology risk assessments and regulations requires quantitative information on the potential for exposure to nanomaterials. The objective of this research isto characterize airborne particle concentrations during the production of carbonaceous nanomaterials, such as fullerenes and carbon nanotubes, in a commercial nanotechnology facility. We measured fine particle mass concentrations (PM2.5), submicrometer size distributions, and photoionization potential, an indicator of the particles' carbonaceous content, at three locations inside the facility: inside the fume hood where nanomaterials were produced, just outside the fume hood, and in the background. The measurements were not selective for engineered nanomaterials and may have included both engineered nanomaterials and naturally occurring or incidental particles. Average PM2.5 and particle number concentrations were not significantly different inside the facility versus outdoors. However, large, short-term increases in PM2.5 and particle number concentrations were associated with physical handling of nanomaterials and other production activities. In many cases, an increase in the number of sub-100 nm particles accounted for the majority of the increase in total number concentrations. Photoionization results indicate that the particles suspended during nanomaterial handling inside the fume hood were carbonaceous and therefore likely to include engineered nanoparticles, whereas those suspended by other production activities taking place outside the fume hood were not. Based on the measurements in this study, the engineering controls at the facility appear to be effective at limiting exposure to nanomaterials.

  9. Characteristics and sources of carbonaceous aerosols from Shanghai, China

    Directory of Open Access Journals (Sweden)

    J.-J. Cao

    2012-07-01

    Full Text Available An intensive investigation of carbonaceous PM2.5 and TSP from Pudong (China was conducted as part of the MIRAGE-Shanghai Experiment in 2009. Data for organic and elemental carbon (OC and EC, organic species, including C17 to C40 n-alkanes and 17 polycyclic aromatic hydrocarbons (PAHs, and stable C isotopes OC (δ13COC and EC (δ13CEC were used to evaluate the aerosols' temporal variations and identify presumptive sources. High OC/EC ratios indicated a large fraction of secondary organic aerosol (SOA; high char/soot ratios indicated stronger contributions to EC from motor vehicles and coal combustion than biomass burning. Diagnostic ratios of PAHs indicated that much of the SOA was produced via coal combustion. Isotope abundances (δ13COC = −24.5 ± 0.8‰ and δ13CEC = −25.1 ± 0.6‰ indicated that fossil fuels were the most important source for carbonaceous PM2.5, with lesser impacts from biomass burning and natural sources. An EC tracer system and isotope mass balance calculations showed that the relative contributions to total carbon from coal combustion, motor vehicle exhaust, and SOA were 41%, 21%, and 31%: other primary sources such as marine, soil and biogenic emissions contributed 7%. Combined analyses of OC and EC, n-alkanes and PAHs, and stable carbon isotopes provide a new way to apportion the sources of carbonaceous particles.

  10. Characteristics and sources of carbonaceous aerosols from Shanghai, China

    Directory of Open Access Journals (Sweden)

    J.-J. Cao

    2013-01-01

    Full Text Available An intensive investigation of carbonaceous PM2.5 and TSP (total suspended particles from Pudong (China was conducted as part of the MIRAGE-Shanghai (Megacities Impact on Regional and Global Environment experiment in 2009. Data for organic and elemental carbon (OC and EC, organic species, including C17 to C40 n-alkanes and 17 polycyclic aromatic hydrocarbons (PAHs, and stable carbon isotopes OC (δ13COC and EC (δ13CEC were used to evaluate the aerosols' temporal variations and identify presumptive sources. High OC/EC ratios indicated a large fraction of secondary organic aerosol (SOA; high char/soot ratios indicated stronger contributions to EC from motor vehicles and coal combustion than biomass burning. Diagnostic ratios of PAHs indicated that much of the SOA was produced via coal combustion. Isotope abundances (δ13COC = −24.5 ± 0.8‰ and δ13CEC = −25.1 ± 0.6‰ indicated that fossil fuels were the most important source for carbonaceous PM2.5 (particulate matter less than 2.5 micrometers in diameter, with lesser impacts from biomass burning and natural sources. An EC tracer system and isotope mass balance calculations showed that the relative contributions to total carbon from coal combustion, motor vehicle exhaust, and SOA were 41%, 21%, and 31%; other primary sources such as marine, soil and biogenic emissions contributed 7%. Combined analyses of OC and EC, n-alkanes and PAHs, and stable carbon isotopes provide a new way to apportion the sources of carbonaceous particles.

  11. Shale gas wastewater management under uncertainty.

    Science.gov (United States)

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

    2016-01-01

    This work presents an optimization framework for evaluating different wastewater treatment/disposal options for water management during hydraulic fracturing (HF) operations. This framework takes into account both cost-effectiveness and system uncertainty. HF has enabled rapid development of shale gas resources. However, wastewater management has been one of the most contentious and widely publicized issues in shale gas production. The flowback and produced water (known as FP water) generated by HF may pose a serious risk to the surrounding environment and public health because this wastewater usually contains many toxic chemicals and high levels of total dissolved solids (TDS). Various treatment/disposal options are available for FP water management, such as underground injection, hazardous wastewater treatment plants, and/or reuse. In order to cost-effectively plan FP water management practices, including allocating FP water to different options and planning treatment facility capacity expansion, an optimization model named UO-FPW is developed in this study. The UO-FPW model can handle the uncertain information expressed in the form of fuzzy membership functions and probability density functions in the modeling parameters. The UO-FPW model is applied to a representative hypothetical case study to demonstrate its applicability in practice. The modeling results reflect the tradeoffs between economic objective (i.e., minimizing total-system cost) and system reliability (i.e., risk of violating fuzzy and/or random constraints, and meeting FP water treatment/disposal requirements). Using the developed optimization model, decision makers can make and adjust appropriate FP water management strategies through refining the values of feasibility degrees for fuzzy constraints and the probability levels for random constraints if the solutions are not satisfactory. The optimization model can be easily integrated into decision support systems for shale oil/gas lifecycle

  12. Comets, carbonaceous meteorites, and the origin of the biosphere

    Directory of Open Access Journals (Sweden)

    r. b. Hoover

    2006-01-01

    Full Text Available The Biosphere is considered to represent the Earth's crust, atmosphere, oceans, and ice caps and the living organisms that survive within this habitat. This paper considers the significance of comets and carbonaceous meteorites to the origin and evolution of the Biosphere and presents new Field Emission Scanning Electron Microscope (FESEM images of indigenous microfossils in the Orgueil and Murchison meteorites. The discovery of microbial extremophiles in deep crustal rocks, hydrothermal vents and ancient ice has established that the biosphere is far more extensive than previously recognized. Chemical and molecular biomarkers and microfossils in Archaean rocks indicate that life appeared very early on the primitive Earth and the origin of the biosphere is closely linked with the emergence of life. The role of comets, carbonaceous meteorites, interstellar dust and asteroids in the delivery of water, organics and prebiotic chemicals to Earth during the Hadean (4.5–3.8 Ga period of heavy bombardment has become more widely recognized. Spacecraft observations of the chemical compositions and characteristics of the nuclei of several comets (Halley, Borrelly, Wild 2, and Tempel 1 have established that comets contain complex organic chemicals; that water is the predominant volatile; and that high temperatures (~400 K can be reached on the black (albedo~0.03 nuclei when near perihelion. The microscopic dust particles in the Tempel 1 ejecta are similar in size to the particulates of the Orgueil meteorite and evidence is mounting that comets may represent the parent bodies of the CI meteorites. Impact craters and pinnacles on comet Wild 2 suggest a thick crust. Episodic outbursts and jets of Halley, Borrelly, Wild 2 and Tempel 1 near perihelion indicate that localized regimes of liquid water may periodically exist beneath the thick crust of many comets. This increases the possibility that microbial life might survive in comets and therefore the

  13. Lithium storage into carbonaceous materials obtained from sugarcane bagasse

    Energy Technology Data Exchange (ETDEWEB)

    Matsubara, Elaine Y.; Lala, Stella M.; Rosolen, Jose Mauricio, E-mail: rosolen@ffclrp.usp.b [University of Sao Paulo (FFCLRP/USP), Ribeirao Preto, SP (Brazil). Dept. of Chemistry

    2010-07-01

    Carbonaceous materials with different structures are prepared by carbonization of sugarcane bagasse. Depending on carbonization conditions, it is possible to obtain soot rich in flakes or in honeycomb-shaped micrometric particles, whose concentration has large influence on lithium storage into electrodes. The soot rich in honeycomb-shaped particles provides the best electrochemical performance, with a reversible specific capacity of 310 mAh g{sup -1}. The results suggest that the sugarcane bagasse can be potentially used in the design of anodic materials for lithium ion batteries. (author)

  14. Sugar-Related Organic Compounds in Carbonaceous Meteorites

    Science.gov (United States)

    Cooper, G.; Kimmich, N.; Belisle, W.; Sarinana, J.; Brabham, K.; Garrel, L.; DeVincenzi, Donald L. (Technical Monitor)

    2001-01-01

    Sugars and related polyols are critical components of all organisms and may have been necessary for the origin of life. To date, this class of organic compounds had not been definitively identified in meteorites. This study was undertaken to determine if polyols were present in the early Solar System as constituents of carbonaceous meteorites. Results of analyses of the Murchison and Murray meteorites indicate that formaldehyde and sugar chemistry may be responsible for the presence of a variety of polyols. We conclude that polyols were present on the early Earth through delivery by asteroids and possibly comets.

  15. Oil Shale: History, Incentives, and Policy

    Science.gov (United States)

    2006-04-13

    of Crude Oil (for July 2005 to Jan. 2006), at [http://tonto.eia.doe.gov/dnav/pet/pet_pri_rac2_dcu_nus_m.htm]. Crude oil production costs vary widely by... oil production declined through the 1970s, many marginally profitable and often smaller refineries were closed or idled.48 Of the 324 refineries...whereas Shell’s estimate is based on oil field-based technology for resource extraction. The Ideal Size for an Oil Shale Facility As domestic crude

  16. Catalytic gasification of oil-shales

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.; Avakyan, T. [I.M. Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation); Strizhakova, Yu. [Samara State Univ. (Russian Federation)

    2012-07-01

    Nowadays, the problem of complex usage of solid fossil fuels as raw materials for obtaining of motor fuels and chemical products is becoming increasingly important. A one of possible solutions of the problem is their gasification with further processing of gaseous and liquid products. In this work we have investigated the process of thermal and catalytic gasification of Baltic and Kashpir oil-shales. We have shown that, as compared with non-catalytic process, using of nickel catalyst in the reaction increases the yield of gas, as well as hydrogen content in it, and decreases the amount of liquid products. (orig.)

  17. A fly ash and shale fired brick production line

    Institute of Scientific and Technical Information of China (English)

    ZhuYali

    2005-01-01

    The article describes the fly ash and shale fired brick production line with annual output of 1250 million bricks, designed by Xi'an Research and Design Institute of Wall and Roof Material, commissioned by QinDian Building Material Subcompany, and set an example for using fly ash and shale in China.

  18. Shale Gas in Europe: pragmatic perspectives and actions

    Directory of Open Access Journals (Sweden)

    Horsfield B.

    2012-10-01

    Full Text Available 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.

  19. Shale Gas in Europe: pragmatic perspectives and actions

    Science.gov (United States)

    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.

  20. The Geopolitical Impact of Shale Gas: The Modelling Approach

    NARCIS (Netherlands)

    Auping, W.L.; De Jong, S.; Pruyt, E.; Kwakkel, J.H.

    2014-01-01

    The US’ shale gas revolution, a spectacular increase in natural gas extraction from previously unconventional sources, has led to considerable lower gas prices in North America. This study focusses on consequences of the shale gas revolution on state stability of traditional oil and gas exporting co

  1. Implementation of an anisotropic mechanical model for shale in Geodyn

    Energy Technology Data Exchange (ETDEWEB)

    Attia, A; Vorobiev, O; Walsh, S

    2015-05-15

    The purpose of this report is to present the implementation of a shale model in the Geodyn code, based on published rock material models and properties that can help a petroleum engineer in his design of various strategies for oil/gas recovery from shale rock formation.

  2. Market analysis of shale oil co-products. Appendices

    Energy Technology Data Exchange (ETDEWEB)

    1980-12-01

    Data are presented in these appendices on the marketing and economic potential for soda ash, aluminia, and nahcolite as by-products of shale oil production. Appendices 1 and 2 contain data on the estimated capital and operating cost of an oil shales/mineral co-products recovery facility. Appendix 3 contains the marketing research data.

  3. Nuclear Waste Disposal: A Cautionary Tale for Shale Gas Development

    Science.gov (United States)

    Alley, William M.; Cherry, John A.; Parker, Beth L.; Ryan, M. Cathryn

    2014-07-01

    Nuclear energy and shale gas development each began with the promise of cheap, abundant energy and prospects for national energy independence. Nuclear energy was touted as "too cheap to meter," and shale gas promised jobs and other economic benefits during a recession.

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

    Science.gov (United States)

    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 circulating fluidized bed technology with fractional combustion.

  5. Elemental and carbonaceous characterization of TSP and PM10 during Middle Eastern dust (MED) storms in Ahvaz, Southwestern Iran.

    Science.gov (United States)

    Shahsavani, Abbas; Yarahmadi, Maryam; Hadei, Mostafa; Sowlat, Mohammad Hossein; Naddafi, Kazem

    2017-08-21

    Middle Eastern dust (MED) storms carry large amounts of dust particles to the Southern and Western cities of Iran. This study aimed to characterize the elemental and carbonaceous composition of total suspended particles (TSP) and PM10 in Ahvaz, Iran. TSP and PM10 samples were collected using two separate high-volume air samplers. The sampling program was performed according to EPA guidelines and resulted in 72 samples. Twenty-eight elements and two carbonaceous components in TSP and PM10 were measured. Over the entire study period, the mean concentration (SD) of TSP and PM10 was 1548.72 μg/m(3) (1965.11 μg/m(3)) and 1152.35 μg/m(3) (1510.34 μg/m(3)), respectively. The order of concentrations of major species were Si > Al > Ca > OC > Na > B > Zn > Mn > K > Mg and Si > Ca > Al > Na > OC > B > K > Mn > Cu > Mg for TSP and PM10, respectively. Almost all elements (except for Cd, Cr, and Cu) and carbonaceous components (except for organic carbon) had dust days/non-dust days (DD/NDD) ratios higher than 1, implying that all components are somehow affected by dust storms. Crustal elements constituted the major portion of particles for both TSP and PM10 in both DDs and NDDs. The enrichment factor of elements such as Ca, Fe, K, Mg, Na, and Ti was near unity. Species such as Al, Ca, Fe, K, Na, Si, and EC had high correlation coefficients in both TSP and PM10 (except for EC). In conclusion, Ahvaz is exposed to high concentrations of TSP and PM10 during the MED period. Immediate actions must be planned to decrease the high concentrations of particulate matter in Ahvaz's ambient air.

  6. Shale gas characterization of the Dinder and Blue Nile Formations in the Blue Nile Basin, East Sudan

    Science.gov (United States)

    Shoieb, Monera Adam; Sum, Chow Weng; Bhattachary, Swapan Kumar; Abidin, Nor Syazwani Zainal; Abdelrahim, Omer Babiker

    2016-11-01

    The development of gas and oil in unconventional plays in United State and Northern Europe has affected the finances and the energy security. Geochanical properties of shale rocks can have a major impact on the efficiency of shale gas exploration. The goal of this study is to evaluate shale gas potentiality in the Blue Nile Basin, using samples from existing drilled wells. All the samples were analyzed in detail with the following organic geochemical techniques: total organic carbon (TOC), Rock-eval pyrolysis, to determine the quality and quantity of the organic matter. The total organic carbon (TOC) values for the shale intervals vary from 0.6 to 4.5weight% in FARASHA-1 Well, while in TAWAKUL-1 Well range from 0.4 to 2.4weight%, suggesting that fair to good source generative potential, as revealed by the S2 v's TOC plot. Hydrogen index (HI) values range from 12 to 182 mg HC/g TOC in the two wells, indicating type III and IV derived-input in the samples and their potential to generate gas. However, the Blue Nile and Dinder Formation have Tmax values in the range of 437 to 456°C, indicating early maturity in the oil window. Thus, higher maturity levels have affected the hydrocarbon generation potential and HI of the samples.

  7. An evaluation of water quality in private drinking water wells near natural gas extraction sites in the Barnett Shale formation.

    Science.gov (United States)

    Fontenot, Brian E; Hunt, Laura R; Hildenbrand, Zacariah L; Carlton, Doug D; Oka, Hyppolite; Walton, Jayme L; Hopkins, Dan; Osorio, Alexandra; Bjorndal, Bryan; Hu, Qinhong H; Schug, Kevin A

    2013-09-03

    Natural gas has become a leading source of alternative energy with the advent of techniques to economically extract gas reserves from deep shale formations. Here, we present an assessment of private well water quality in aquifers overlying the Barnett Shale formation of North Texas. We evaluated samples from 100 private drinking water wells using analytical chemistry techniques. Analyses revealed that arsenic, selenium, strontium and total dissolved solids (TDS) exceeded the Environmental Protection Agency's Drinking Water Maximum Contaminant Limit (MCL) in some samples from private water wells located within 3 km of active natural gas wells. Lower levels of arsenic, selenium, strontium, and barium were detected at reference sites outside the Barnett Shale region as well as sites within the Barnett Shale region located more than 3 km from active natural gas wells. Methanol and ethanol were also detected in 29% of samples. Samples exceeding MCL levels were randomly distributed within areas of active natural gas extraction, and the spatial patterns in our data suggest that elevated constituent levels could be due to a variety of factors including mobilization of natural constituents, hydrogeochemical changes from lowering of the water table, or industrial accidents such as faulty gas well casings.

  8. Study of Carbonaceous Material in cherts from Barberton Greenstone Belt and the Astrobiological Implications.

    Science.gov (United States)

    Rull, F.; Venegas, G.; Montero, O.; Medina, J.

    2012-04-01

    Carbonaceous matter is present in chert deposits of Barberton Greenstone Belt (BGB), South Africa. This is a famous place in the world for its Archean geology, wich represents around 3.5 billion years of earth's history. Therefore this area provides us the opportunity to study and understand an important part history of our planet, and also allow to compare with the geological history of other planets in our solar system [1]. Raman micro-spectroscopy has proved to be a very important and non-destructive powerful tool for distinguish micro-sized particles of C-polymorphs, as it is very sensitive to the nature of carbon bonding [2]. The connection between the Raman characterization of these carbonaceous phases with ancient biogenic activity it's of special interest. Cherts of BGB have been interpreted as precipitates or diagenetic replacements of preexisting sedimentary and pyroclastic deposits in a silica saturated Archean ocean [3]. Several layered Samples of cherts from BGB utility for the present study were collected during the expedition carried out in August 2010 sponsored by CNES and ESA. A detailed Raman spectral analysis of carbon C-C vibrations has been performed in the first (1200-1800 cm-1) and second (2500-3200 cm-1) order regions [4]. The results show important changes in the G-D bands in the layered structure of chert. Additionally a UPLC-ESI-QTOF-MS was carried out trying to introduce new insight in the Raman interpretation of the bands and in the possible assignments to particular molecular groups which could be related with biotic or abiotic origin of the carbonaceous material. Among the tentative compounds obtained from UPLC-ESI-QTOF-MS study it is worth to mention hydroxy-lycopene and the hydroxyl derivative of β-carotene (i.e. β-cryptoxanthin), which are carotenoids produced by cyanobacteria. These results are consistent with the presence of 22-Hopanol and Tetrahymanol, which are characteristic hopanoids of photosynthetic cyanobacteria and have

  9. Oil shale and nahcolite resources of the Piceance Basin, Colorado

    Science.gov (United States)

    ,

    2010-01-01

    This report presents an in-place assessment of the oil shale and nahcolite resources of the Green River Formation in the Piceance Basin of western Colorado. The Piceance Basin is one of three large structural and sedimentary basins that contain vast amounts of oil shale resources in the Green River Formation of Eocene age. The other two basins, the Uinta Basin of eastern Utah and westernmost Colorado, and the Greater Green River Basin of southwest Wyoming, northwestern Colorado, and northeastern Utah also contain large resources of oil shale in the Green River Formation, and these two basins will be assessed separately. Estimated in-place oil is about 1.5 trillion barrels, based on Fischer a ssay results from boreholes drilled to evaluate oil shale, making it the largest oil shale deposit in the world. The estimated in-place nahcolite resource is about 43.3 billion short tons.

  10. Assessment of industry needs for oil shale research and development

    Energy Technology Data Exchange (ETDEWEB)

    Hackworth, J.H.

    1987-05-01

    Thirty-one industry people were contacted to provide input on oil shale in three subject areas. The first area of discussion dealt with industry's view of the shape of the future oil shale industry; the technology, the costs, the participants, the resources used, etc. It assessed the types and scale of the technologies that will form the industry, and how the US resource will be used. The second subject examined oil shale R D needs and priorities and potential new areas of research. The third area of discussion sought industry comments on what they felt should be the role of the DOE (and in a larger sense the US government) in fostering activities that will lead to a future commercial US oil shale shale industry.

  11. Market enhancement of shale oil: The native products extraction technology

    Energy Technology Data Exchange (ETDEWEB)

    Bunger, J.W. (Bunger (James W.) and Associates, Inc., Salt Lake City, UT (United States)); DuBow, J.B. (Utah Univ., Salt Lake City, UT (United States))

    1991-10-01

    The overall objective of this work was to assess the feasibility of enhancing shale oil commercialization through SO/NPX technology. Specific objectives were: (1) To determine the properties and characteristics of fractions isolable from shale oil utilizing separation sequences which are based on thermodynamic considerations; (2) To identify product streams of market value for promising technology development; (3)To conduct technology development studies leading to a shale oil extraction and processing sequence which promises economic enhancement of shale oil commercialization; (4) To develop an analytical methodology and model for obtaining engineering design data required for process development; (5) To estimate the economics of SO/NPX including the potential for enhancing the profitability of a commercial-scale shale oil MIS retort.

  12. Development of Shale Gas Supply Chain Network under Market Uncertainties

    Directory of Open Access Journals (Sweden)

    Jorge Chebeir

    2017-02-01

    Full Text Available The increasing demand of energy has turned the shale gas and shale oil into one of the most promising sources of energy in the United States. In this article, a model is proposed to address the long-term planning problem of the shale gas supply chain under uncertain conditions. A two-stage stochastic programming model is proposed to describe and optimize the shale gas supply chain network. Inherent uncertainty in final products’ prices, such as natural gas and natural gas liquids (NGL, is treated through the utilization of a scenario-based method. A binomial option pricing model is utilized to approximate the stochastic process through the generation of scenario trees. The aim of the proposed model is to generate an appropriate and realistic supply chain network configuration as well as scheduling of different operations throughout the planning horizon of a shale gas development project.

  13. Developing Fayetteville shale gas plays : focus on geology and engineering

    Energy Technology Data Exchange (ETDEWEB)

    Marble, B. [Hallwood Petroleum, Dallas, TX (United States)

    2007-07-01

    This presentation provided details of the underlying geology of the Fayetteville shale gas plays and discussed engineering strategies used to improve productivity. Like the Barnett shale gas play, the Fayetteville play is comprised of Mississippian shale, and contains both free and adsorbed gas. Operators in Fayetteville use seismic data in order to avoid faults in the play, which has large variations in structure and depth over short distances. A typical well is drilled in 40 days. Microseismic aids will be used to plan future horizontal development and for 3-dimensional fracture analysis. Multiple short wings are used to create more concentrated frac patterns. However, once broken, the laminated shales will not re-align when frac pressure is released. The high clay content of the shale reduces frac efficiency. It was concluded that modified slick water fracs are now being used at the play along with air drilling to reduce costs, and straighten holes. tabs., figs.

  14. Migration and Enrichment of Arsenic in the Rock-Soil-Crop Plant System in Areas Covered with Black Shale, Korea

    Directory of Open Access Journals (Sweden)

    Ji-Min Yi

    2003-01-01

    Full Text Available The Okchon black shale, which is part of the Guryongsan Formation or the Changri Formation of Cambro-Ordovician age in Korea provides a typical example of natural geological materials enriched with potentially toxic elements such as U, V, Mo, As, Se, Cd, and Zn. In this study, the Dukpyung and the Chubu areas were selected to investigate the migration and enrichment of As and other toxic elements in soils and crop plants in areas covered with black shale. Rock and soil samples digested in 4-acid solution (HCl+HNO3+HF+HClO4 were analyzed for As and other heavy metals by ICP-AES and ICP-MS, and plant samples by INAA. Mean concentration of As in Okchon black shale is higher than those of both world average values of shale and black shale. Especially high concentration of 23.2 mg As kg-1 is found in black shale from the Dukpyung area. Mean concentration of As is highly elevated in agricultural soils from the Dukpyung (28.2 mg kg-1 and the Chubu areas (32.6 mg kg-1. As is highly elevated in rice leaves from the Dukpyung (1.14 mg kg-1 and the Chubu areas (1.35 mg kg-1. The biological absorption coefficient (BAC of As in plant species decreases in the order of rice leaves > corn leaves > red pepper = soybean leaves = sesame leaves > corn stalks > corn grains. This indicates that leafy plants tend to accumulate As from soil to a greater degree than cereal products such as grains.

  15. Potential small-scale development of western oil shale

    Energy Technology Data Exchange (ETDEWEB)

    Smith, V.; Renk, R.; Nordin, J.; Chatwin, T.; Harnsberger, M.; Fahy, L.J.; Cha, C.Y.; Smith, E.; Robertson, R.

    1989-10-01

    Several studies have been undertaken in an effort to determine ways to enhance development of western oil shale under current market conditions for energy resources. This study includes a review of the commercial potential of western oil shale products and byproducts, a review of retorting processes, an economic evaluation of a small-scale commercial operation, and a description of the environmental requirements of such an operation. Shale oil used as a blend in conventional asphalt appears to have the most potential for entering today's market. Based on present prices for conventional petroleum, other products from oil shale do not appear competitive at this time or will require considerable marketing to establish a position in the marketplace. Other uses for oil shale and spent shale, such as for sulfur sorbtion, power generation, cement, aggregate, and soil stabilization, are limited economically by transportation costs. The three-state area area consisting of Colorado, Utah, and Wyoming seems reasonable for the entry of shale oil-blended asphalt into the commercial market. From a review of retorting technologies and the product characteristics from various retorting processes it was determined that the direct heating Paraho and inclined fluidized-bed processes produce a high proportion of heavy material with a high nitrogen content. The two processes are complementary in that they are each best suited to processing different size ranges of materials. An economic evaluation of a 2000-b/d shale oil facility shows that the operation is potentially viable, if the price obtained for the shale oil residue is in the top range of prices projected for this product. Environmental requirements for building and operating an oil shale processing facility are concerned with permitting, control of emissions and discharges, and monitoring. 62 refs., 6 figs., 10 tabs.

  16. Source apportionment of the carbonaceous aerosol in Norway – quantitative estimates based on 14C, thermal-optical and organic tracer analysis

    Directory of Open Access Journals (Sweden)

    K. Stenström

    2011-09-01

    Full Text Available In the present study, source apportionment of the ambient summer and winter time particulate carbonaceous matter (PCM in aerosol particles (PM1 and PM10 has been conducted for the Norwegian urban and rural background environment. Statistical treatment of data from thermal-optical, 14C and organic tracer analysis using Latin Hypercube Sampling has allowed for quantitative estimates of seven different sources contributing to the ambient carbonaceous aerosol. These are: elemental carbon from combustion of biomass (ECbb and fossil fuel (ECff, primary and secondary organic carbon arising from combustion of biomass (OCbb and fossil fuel (OCff, primary biological aerosol particles (OCPBAP, which includes plant debris, OCpbc, and fungal spores, OCpbs, and secondary organic aerosol from biogenic precursors (OCBSOA. Our results show that emissions from natural sources were particularly abundant in summer, and with a more pronounced influence at the rural compared to the urban background site. 80% of total carbon (TCp, corrected for the positive artefact in PM10 and ca. 70% of TCpin PM1 could be attributed to natural sources at the rural background site in summer. Natural sources account for about 50% of TCp in PM10 at the urban background site as well. The natural source contribution was always dominated by OCBSOA, regardless of season, site and size fraction. During winter anthropogenic sources totally dominated the carbonaceous aerosol (80–90%. Combustion of biomass contributed slightly more than fossil-fuel sources in winter, whereas emissions from fossil-fuel sources were more abundant in summer. Mass closure calculations show that PCM made significant contributions to the mass concentration of the ambient PM regardless of size fraction, season, and site. A larger fraction of PM1 (ca. 40–60% was accounted for by carbonaceous matter compared to PM10 (ca. 40–50%, but only by a small margin. In general, there were no pronounced differences in the

  17. Source apportionment of the carbonaceous aerosol in Norway – quantitative estimates based on 14C, thermal-optical and organic tracer analysis

    Directory of Open Access Journals (Sweden)

    K. Stenström

    2011-03-01

    Full Text Available In the present study, source apportionment of the ambient summer and winter time particulate carbonaceous matter (PCM in aerosol particles (PM1 and PM10 has been conducted for the Norwegian urban and rural background environment. Statistical treatment of data from thermal-optical, 14C and organic tracer analysis using Latin Hypercube Sampling has allowed for quantitative estimates of seven different sources contributing to the ambient carbonaceous aerosol. These are: elemental carbon from combustion of biomass (ECbb and fossil fuel (ECff, organic carbon from combustion of biomass (OCbb, fossil fuel (OCff, primary biological aerosol particles (OCPBAP, which includes plant debris, OCpbc, and fungal spores, OCpbs, and secondary organic aerosol from biogenic precursors (OCBSOA. Our results show that emissions from natural sources were particularly abundant in summer, and with a more pronounced influence at the rural compared to the urban background site. 80% of total carbon (TCp, corrected for the positive artefact in PM10 and 70% of TCp in PM1 could be attributed to natural sources at the rural background site in summer. Natural sources account for about 50% of TCp in PM10 at the urban background site as well. The natural source contribution was always dominated by OCBSOA, regardless of season, site and size fraction. During winter anthropogenic sources totally dominated the carbonaceous aerosol (83–90%. Combustion of biomass contributed slightly more than fossil-fuel sources in winter, whereas emissions from fossil-fuel sources were more abundant in summer. Mass closure calculations show that PCM likely dominated the mass concentration of the ambient PM regardless of size fraction, season, and site. A larger fraction of PM1 (64–69% was accounted for by carbonaceous matter compared to PM10 (51–67%, but only by a small margin. In general, there were no pronounced differences in the relative contribution of carbonaceous matter to PM with

  18. Risk assessment methodology in oil shale mining

    Energy Technology Data Exchange (ETDEWEB)

    Sabanov, S. [Tallinn Univ. of Technology, Tallinn (Estonia)

    2009-07-01

    The safety challenges posed by different mining processes were discussed in terms of geotechnical risk factors. Various mining processes can result in work hazards, a production shut-down, economic damage to the enterprise, and environmental impacts. In Estonia, risk assessment methods are utilized in different branches of industry. However, the literature on solving mining problems is limited. Various methods are applicable for solving complicated mining problems. This paper elaborated on a modified risk assessment methodology for oil shale mining in Estonia. The paper specifically discussed problems associated with oil shale mining as well as risk assessment methods such as risk analysis and risk evaluation. Topics that were introduced included risk analysis; risk identification; risk estimation; risk evaluation; risk mitigation; and risk acceptance. The modified risk assessment methodology was successfully applied to the extraction of mineral resources, stability of a mining block, and their influence on the environment. It was concluded that the methodology provides opportunity to find improved methods for new mine planning in accordance with environmental performances and the economical profit for companies. 8 refs., 2 figs.

  19. Ion chromatographic analysis of oil shale leachates

    Energy Technology Data Exchange (ETDEWEB)

    Butler, N.L.

    1990-10-01

    In the present work an investigation of the use of ion chromatography to determine environmentally significant anions present in oil shale leachates was undertaken. Nadkarni et al. have used ion chromatography to separate and quantify halogen, sulfur and nitrogen species in oil shales after combustion in a Parr bomb. Potts and Potas used ion chromatography to monitor inorganic ions in cooling tower wastewater from coal gasification. Wallace and coworkers have used ion chromatography to determine anions encountered in retort wastewaters. The ions of interest in this work were the ions of sulfur oxides including sulfite (SO{sub 3}{sup 2{minus}}), sulfate (SO{sub 4}{sup 2{minus}}), thiosulfate (S{sub 2}O{sub 3}{sup 2{minus}}), dithionite (S{sub 2}O{sub 4}{sup 2{minus}}), dithionate (S{sub 2}O{sub 6}{sup 2{minus}}), peroxyodisulfate (S{sub 2}O{sub 8}{sup 2{minus}}), and tetrathionate (S{sub 4}O{sub 6}{sup 2{minus}}), and thiocyanate (SCN{sup {minus}}), sulfide (S{sup 2{minus}}) hydrosulfide (HS{sup {minus}}), cyanide (CN{sup {minus}}), thiocyanate (SCN{sup {minus}}), and cyanate (OCN{sup {minus}}). A literature search was completed and a leaching procedure developed. 15 refs., 6 figs., 1 tab.

  20. Uncertainties in Carbonaceous Aerosol Emissions, Scavenging Parameterizations, and Optical Properties

    Science.gov (United States)

    Koch, D.; Bond, T.; Kinne, S.; Klimont, Z.; Sun, H.; van Aardenne, J.; van der Werf, G.

    2006-12-01

    Estimates of human influence on climate are especially hindered by poor constraint on the amount of anthropogenic carbonaceous aerosol absorption in the atmosphere. Coordination of observation and model analyses attempt to constrain particle absorption amount, however these are limited by uncertainties in aerosol emission estimates, model scavenging parameterization, aerosol size assumption, contributions from organic aerosol absorption, air concentration observational techniques and by sparsity of data coverage. We perform multiple simulations using GISS modelE and six present-day emission estimates for black carbon (BC) and organic carbon (OC) (Bond et al 2004 middle and upper estimates, IIASA, EDGAR, GFED v1 and v2); for one of these emissions we apply 4 different BC/OC scavenging parameterizations. The resulting concentrations will be compared with a new compilation of observed BC/OC concentrations. We then use these model concentrations, together with effective radius assumptions and estimates of OC absorption to calculate a range of carbonaceous aerosol absorption. We constrain the wavelength-dependent model τ- absorption with AERONET sun-photometer observations. We will discuss regions, seasons and emission sectors with greatest uncertainty, including those where observational constraint is lacking. We calculate the range of model radiative forcing from our simulations and discuss the degree to which it is constrained by observations.