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Sample records for kerogen

  1. Realistic molecular model of kerogen's nanostructure.

    Science.gov (United States)

    Bousige, Colin; Ghimbeu, Camélia Matei; Vix-Guterl, Cathie; Pomerantz, Andrew E; Suleimenova, Assiya; Vaughan, Gavin; Garbarino, Gaston; Feygenson, Mikhail; Wildgruber, Christoph; Ulm, Franz-Josef; Pellenq, Roland J-M; Coasne, Benoit

    2016-05-01

    Despite kerogen's importance as the organic backbone for hydrocarbon production from source rocks such as gas shale, the interplay between kerogen's chemistry, morphology and mechanics remains unexplored. As the environmental impact of shale gas rises, identifying functional relations between its geochemical, transport, elastic and fracture properties from realistic molecular models of kerogens becomes all the more important. Here, by using a hybrid experimental-simulation method, we propose a panel of realistic molecular models of mature and immature kerogens that provide a detailed picture of kerogen's nanostructure without considering the presence of clays and other minerals in shales. We probe the models' strengths and limitations, and show that they predict essential features amenable to experimental validation, including pore distribution, vibrational density of states and stiffness. We also show that kerogen's maturation, which manifests itself as an increase in the sp(2)/sp(3) hybridization ratio, entails a crossover from plastic-to-brittle rupture mechanisms.

  2. Chemo-mechanical coupling in kerogen gas adsorption/desorption.

    Science.gov (United States)

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

    2018-05-09

    Kerogen plays a central role in hydrocarbon generation in an oil/gas reservoir. In a subsurface environment, kerogen is constantly subjected to stress confinement or relaxation. The interplay between mechanical deformation and gas adsorption of the materials could be an important process for shale gas production but unfortunately is poorly understood. Using a hybrid Monte Carlo/molecular dynamics simulation, we show here that a strong chemo-mechanical coupling may exist between gas adsorption and mechanical strain of a kerogen matrix. The results indicate that the kerogen volume can expand by up to 5.4% and 11% upon CH4 and CO2 adsorption at 192 atm, respectively. The kerogen volume increases with gas pressure and eventually approaches a plateau as the kerogen becomes saturated. The volume expansion appears to quadratically increase with the amount of gas adsorbed, indicating a critical role of the surface layer of gas adsorbed in the bulk strain of the material. Furthermore, gas uptake is greatly enhanced by kerogen swelling. Swelling also increases the surface area, porosity, and pore size of kerogen. Our results illustrate the dynamic nature of kerogen, thus questioning the validity of the current assumption of a rigid kerogen molecular structure in the estimation of gas-in-place for a shale gas reservoir or gas storage capacity for subsurface carbon sequestration. The coupling between gas adsorption and kerogen matrix deformation should be taken into consideration.

  3. Kerogen-bound and free hopanoic acids in the messel oil shale kerogen.

    Science.gov (United States)

    Abbott, G D; Bashir, F Z; Sugden, M A

    2001-08-01

    The distribution of the free and bound hopanoic acids in both unheated and heated (350 degrees C for 50 h) kerogens, isolated from the Messel oil shale, were analyzed by GC-MS. The bound acids were released by subjecting the kerogen to three different treatments, namely, thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH), as well as basic and acidic hydrolyses. All of these methods gave a series of hopanoic acids ranging from C(30) to C(34), in which the biological 17beta, 21beta(H) configuration is prominent. Both 22R and 22S epimers are present for the C(30) acid, whereas the others are dominated by the sidechain 22R-configuration. Thermochemolysis in the presence of TMAH was the most efficient in releasing kerogen-bound hopanoids. Following pyrolysis, the acids are generated and released into the free fraction with apparent epimerization occurring at C-17, C-21, and C-22. The bound hopanoic acids may be both chemically bonded as well as possibly being physically encapsulated within the macromolecular fraction of sedimentary organic matter. They are therefore either generated by breaking the bonds which bind them to the kerogen or they are released as a result of the macromolecular cage being broken apart. Copyright 2001 Wiley-Liss, Inc.

  4. Variations in origin and composition of kerogen constituents as revealed by analytical pyrolysis of immature kerogens before and after desulphurization

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Gelin, F.; Harrison, W.; Maxwell, J.R.

    1996-01-01

    Kerogens isolated from nine samples from a single marl bed of the Gessoso-solfifera formation in the Vena del Gesso basin (Upper Miocene, Italy) were treated with CrCl2 and Li/EtNH2 to remove inorganic and organic sulphur, respectively. The untreated and 'desulphurized' (CrCl2 and Li/EtNH2) kerogens

  5. Pyrolysis-gas chromatographic method for kerogen typing

    Energy Technology Data Exchange (ETDEWEB)

    Larter, S.R.; Douglas, A.G.

    1980-01-01

    The classification of kerogens according to their type and rank is important for the definition of any kerogen assemblage. Whereas optical methods of rank determination are well known, vitrinite reflectance and spore coloration being the most widely accepted chemical methods for typing kerogens are less developed. In this work we show that pyrograms, produced by pyrolyzing microgram quantities of solvent-extracted kerogens, enable not only their characterization in terms of a chromatographic fingerprint but also the production of a numerical type index determined as the ratio of m(+p)-xylene/n-octene (oct-1-ene) in the pyrogram. This index appears to be a close function of kerogen type. Type 3 kerogens (Tissot et al., 1974), including vitrinite, provide a high type index and have pyrolysates dominated by aromatic and phenolic compounds whereas type 1 kerogens provide an aliphatic-rich pyrolysate and consequently a low type index. The type index described here correlates well with microscopic and elemental analysis data and the pyrogram fingerprint provides an additional level of characterization not attainable with other current typing techniques.

  6. Rapid quantification of biomarkers during kerogen microscale pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Stott, A.W.; Abbott, G.D. [Fossil Fuels and Environmental Geochemistry NRG, The University, Newcastle-upon-Tyne (United Kingdom)

    1995-02-01

    A rapid, reproducible method incorporating closed system microscale pyrolysis and thermal desorption-gas chromatography/mass spectrometry has been developed and applied to the quantification of sterane biomarkers released during pyrolysis of the Messel oil shale kerogen under confined conditions. This method allows a substantial experimental concentration-time data set to be collected at accurately controlled temperatures, due to the low thermal inertia of the microscale borosilicate glass reaction vessels, which facilitates kinetic studies of biomarker reactions during kerogen microscale pyrolysis

  7. From cellulose to kerogen: molecular simulation of a geological process.

    Science.gov (United States)

    Atmani, Lea; Bichara, Christophe; Pellenq, Roland J-M; Van Damme, Henri; van Duin, Adri C T; Raza, Zamaan; Truflandier, Lionel A; Obliger, Amaël; Kralert, Paul G; Ulm, Franz J; Leyssale, Jean-Marc

    2017-12-01

    The process by which organic matter decomposes deep underground to form petroleum and its underlying kerogen matrix has so far remained a no man's land to theoreticians, largely because of the geological (Myears) timescale associated with the process. Using reactive molecular dynamics and an accelerated simulation framework, the replica exchange molecular dynamics method, we simulate the full transformation of cellulose into kerogen and its associated fluid phase under prevailing geological conditions. We observe in sequence the fragmentation of the cellulose crystal and production of water, the development of an unsaturated aliphatic macromolecular phase and its aromatization. The composition of the solid residue along the maturation pathway strictly follows what is observed for natural type III kerogen and for artificially matured samples under confined conditions. After expulsion of the fluid phase, the obtained microporous kerogen possesses the structure, texture, density, porosity and stiffness observed for mature type III kerogen and a microporous carbon obtained by saccharose pyrolysis at low temperature. As expected for this variety of precursor, the main resulting hydrocarbon is methane. The present work thus demonstrates that molecular simulations can now be used to assess, almost quantitatively, such complex chemical processes as petrogenesis in fossil reservoirs and, more generally, the possible conversion of any natural product into bio-sourced materials and/or fuel.

  8. Experimental simulation of the natural transformation of kerogen

    Energy Technology Data Exchange (ETDEWEB)

    Monin, J C [Institut Francais du Petrole, Rueil-Malmaison, France; Durand, B; Vandenbroucke, M; Huc, A Y

    1980-01-01

    Analytical techniques such as elemental analysis, infrared spectroscopy, ESR, dark-field electron microscopy and reflectance analysis applied to kerogens enables the geochemist to describe how they evolve at depth. Simulation of this evolution is obtained by the temperature-programmed heating of immature samples in a stream of inert gas. Comparison of naturally occurring samples at increasing stages of maturation, and artificially matured samples demonstrates that this simulation generally reproduces the overall characteristics of evolution at depth. However, agreement is better for hydrogen-rich than for oxygen-rich kerogens. In fact, oxygen is eliminated in nature, and in the laboratory, by different mechanisms. In nature, elimination takes place mainly at the beginning of burial. Temperatures used in the laboratory are necessarily much higher and appear to cause secondary reactions which favor water formation. Elimination of hydrogen occurs, during natural maturation, at greater depths and temperatures - i.e., in the oil and gas formation zone. Therefore, laboratory simulation is better for kerogens which have already reached the oil formation stage. Hydrocarbons released by natural and laboratory-simulated maturation are compared. Although quantities and distributions are different, similarities exist which can be used, to a first approximation, to predict the distribution of hydrocarbons obtained from naturally-evolving kerogens.

  9. Detecting Kerogen as a Biosignature Using Colocated UV Time-Gated Raman and Fluorescence Spectroscopy.

    Science.gov (United States)

    Shkolyar, Svetlana; Eshelman, Evan J; Farmer, Jack D; Hamilton, David; Daly, Michael G; Youngbull, Cody

    2018-04-01

    The Mars 2020 mission will analyze samples in situ and identify any that could have preserved biosignatures in ancient habitable environments for later return to Earth. Highest priority targeted samples include aqueously formed sedimentary lithologies. On Earth, such lithologies can contain fossil biosignatures as aromatic carbon (kerogen). In this study, we analyzed nonextracted kerogen in a diverse suite of natural, complex samples using colocated UV excitation (266 nm) time-gated (UV-TG) Raman and laser-induced fluorescence spectroscopies. We interrogated kerogen and its host matrix in samples to (1) explore the capabilities of UV-TG Raman and fluorescence spectroscopies for detecting kerogen in high-priority targets in the search for possible biosignatures on Mars; (2) assess the effectiveness of time gating and UV laser wavelength in reducing fluorescence in Raman spectra; and (3) identify sample-specific issues that could challenge rover-based identifications of kerogen using UV-TG Raman spectroscopy. We found that ungated UV Raman spectroscopy is suited to identify diagnostic kerogen Raman bands without interfering fluorescence and that UV fluorescence spectroscopy is suited to identify kerogen. These results highlight the value of combining colocated Raman and fluorescence spectroscopies, similar to those obtainable by SHERLOC on Mars 2020, to strengthen the confidence of kerogen detection as a potential biosignature in complex natural samples. Key Words: Raman spectroscopy-Laser-induced fluorescence spectroscopy-Mars Sample Return-Mars 2020 mission-Kerogen-Biosignatures. Astrobiology 18, 431-453.

  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. Copyright © 2011 Elsevier B.V. All rights reserved.

  11. Sorption of phenanthrene and benzene on differently structural kerogen: Important role of micropore-filling

    International Nuclear Information System (INIS)

    Zhang, Yulong; Ma, Xiaoxuan; Ran, Yong

    2014-01-01

    Shale was thermally treated to obtain a series of kerogen with varied maturation. Their chemical, structural and porous properties were related to the sorption and/or desorption behaviors of phenanthrene and benzene. As the treatment temperature increases, aliphatic and carbonyl carbon of the kerogen samples decrease, while their aromaticity and maturation increase. Meanwhile, the isothermal nonlinearity of phenanthrene and benzene increases whereas the sorption capacity and micropore adsorption volumes (V o,d ) initially increase and then decrease. The V o,d of benzene is significantly correlated with, but higher than that of phenanthrene, suggesting similar micropore filling mechanism and molecular sieve effect. The benzene desorption exhibits hysteresis, which is related to the pore deformation of the kerogen and the entrapment of solute in the kerogen matrix. The V o,d of phenanthrene and benzene on the kerogen samples accounts for 23–46% and 36–65% of the maximum sorption volumes, respectively, displaying the importance of the micropore filling. -- Highlights: • The microporosity estimated by benzene vapor differs greatly from that by N 2 . • The micropore volume changes with kerogen maturation. • The phenanthrene or benzene sorption is related to the microporosity of kerogen. • Higher adsorption volume for benzene than for phenanthrene suggests molecular sieve effect. • The pore-filling plays an important role in the sorption of phenanthrene and benzene. -- The sorption behaviors of benzene and phenanthrene are related to the microporosity of the differently matured kerogen, indicating the importance of pore-filling

  12. Model representations of kerogen structures: An insight from density functional theory calculations and spectroscopic measurements.

    Science.gov (United States)

    Weck, Philippe F; Kim, Eunja; Wang, Yifeng; Kruichak, Jessica N; Mills, Melissa M; Matteo, Edward N; Pellenq, Roland J-M

    2017-08-01

    Molecular structures of kerogen control hydrocarbon production in unconventional reservoirs. Significant progress has been made in developing model representations of various kerogen structures. These models have been widely used for the prediction of gas adsorption and migration in shale matrix. However, using density functional perturbation theory (DFPT) calculations and vibrational spectroscopic measurements, we here show that a large gap may still remain between the existing model representations and actual kerogen structures, therefore calling for new model development. Using DFPT, we calculated Fourier transform infrared (FTIR) spectra for six most widely used kerogen structure models. The computed spectra were then systematically compared to the FTIR absorption spectra collected for kerogen samples isolated from Mancos, Woodford and Marcellus formations representing a wide range of kerogen origin and maturation conditions. Limited agreement between the model predictions and the measurements highlights that the existing kerogen models may still miss some key features in structural representation. A combination of DFPT calculations with spectroscopic measurements may provide a useful diagnostic tool for assessing the adequacy of a proposed structural model as well as for future model development. This approach may eventually help develop comprehensive infrared (IR)-fingerprints for tracing kerogen evolution.

  13. Molecular characterization of kerogens by mild selective chemical degradation - ruthenium tetroxide oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Boucher, R.J.; Standen, G.; Eglinton, G. (University of Bristol, Bristol (UK). Organic Geochemistry Unit)

    1991-06-01

    Molecular characterization of two kerogen isolates (Messel and Kimmeridge Clay), two kerogen-rich shales (green River and Maoming) and a coal, (Loy Yang) was undertaken using selective chemical degradation with ruthenium tetroxide (RuO{sub 4}). The RuO{sub 4} oxidation gave extracts which were soluble in dichloromethane and contained series of straight chain monocarboxylic acids, {alpha},{omega}-dicarboxylic acids, branched mono- and dicarboxylic acids, isoprenoid and cyclic acids. Straight chain carboxylic acids were predominant (65-87% of quantified chromatogram components for the range of sedimentary organic matter studied), reflecting the major content of polymethylene chains in these kerogens. This mild, oxidative technique serves to differentiate kerogens at a molecular level, thereby supplementing existing conventional chemical, pyrolytic, n.m.r. and other techniques. 39 refs., 3 figs., 5 tabs.

  14. Preservation of peptide moieties in three Spanish sulfur-rich Tertiary kerogens

    Energy Technology Data Exchange (ETDEWEB)

    Rio, J.C. del [Consejo Superior de Investigaciones Cientificas, Seville (Spain). Inst. de Recursos Naturales y Agrobiologia; Olivella, M.A.; Heras, F.X.D. de las [Escola Universitaria Politecnica de Manresa, Catalonia (Spain); Knicker, H. [Technische Universitaet Muenchen (Germany). Lehrstuhl fuer Bodenkunde

    2004-09-01

    Thermochemolysis with tetramethylammonium hydroxide (TMAH) and solid-state {sup 15}N NMR were utilized for the characterization of refractory organic nitrogen in Tertiary Spanish kerogens. The samples included sulfur-rich oil shales from the Ribesalbes (Serravallian), Libros (Tortonian) and Cerdanya (Tortonian) basins. Analysis using solid state {sup 15}N NMR showed that part of the refractory nitrogen in the kerogens corresponds to amide groups. Moreover, the release of amino acid derivatives after pyrolysis in the presence of TMAH indicated that this amide-N arose from peptide moieties. The amino acids released from the kerogens were dominated by high amounts of glycine and alanine. Minor amounts of aspartic acid, serine, {alpha}-aminobutyric acid and other unidentified amino acids were also detected. Because proteinaceous structures, including small peptides, are generally considered as being highly sensitive to diagenetic degradation, encapsulation of labile peptide material into aliphatic structures in S-rich kerogens (probably via lipid sulfurization) has been proposed to explain the survival of these moieties. Substantial amounts of fatty acids (as methyl esters) were also released from all the kerogens after pyrolysis/TMAH, indicating their highly aliphatic character. The production of both fatty acids and amino acids from the kerogens supports the encapsulation process. (author)

  15. Biological marker distribution in coexisting kerogen, bitumen and asphaltenes in Monterey Formation diatomite, California

    Science.gov (United States)

    Tannenbaum, E.; Ruth, E.; Huizinga, B. J.; Kaplan, I. R.

    1986-01-01

    Organic-rich (18.2%) Monterey Formation diatomite from California was studied. The organic matter consist of 94% bitumen and 6% kerogen. Biological markers from the bitumen and from pyrolysates of the coexisting asphaltenes and kerogen were analyzed in order to elucidate the relationship between the various fractions of the organic matter. While 17 alpha(H), 18 alpha(H), 21 alpha(H)-28,30-bisnorhopane was present in the bitumen and in the pryolysate of the asphaltenes, it was not detected in the pyrolysates of the kerogen. A C40-isoprenoid with "head to head" linkage, however, was present in pyrolysates of both kerogen and asphaltenes, but not in the bitumen from the diatomite. The maturation level of the bitumen, based on the extent of isomerization of steranes and hopanes, was that of a mature oil, whereas the pyrolysate from the kerogen showed a considerably lower maturation level. These relationships indicate that the bitumen may not be indigenous to the diatomite and that it is a mature oil that migrated into the rock. We consider the possibility, however, that some of the 28,30-bisnorhopane-rich Monterey Formation oils have not been generated through thermal degradation of kerogen, but have been expelled from the source rock at an early stage of diagenesis.

  16. Characterization of kerogen from Messel shale based on multistage alkaline permanganate degradation

    Energy Technology Data Exchange (ETDEWEB)

    Vitorovic, D.; Ambles, A.; Bajc, S.; Cvetkovic, O.

    1988-07-01

    A 17-step alkaline permanganate degradation of kerogen from Messel shale (F.R.G.) was carried out. A very high total yield of oxidation products was obtained (91.7% based on original kerogen). Detailed g.c.-m.s. analyses of ether-soluble acids, soluble products of further controlled permanganate degradation of precipitated acids and acids from aqueous solutions, served as a basis for the quantitative estimation of the participation of various types of products and for comparison with other kerogens. Taking into account the slight aliphatic nature of the acidic oxidation products (53.4%), the existence of an aliphatic cross-linked nucleus in the Messel shale kerogen is postulated. However, on the basis of high participation of both aromatic (21.2%), and alkane-polycarboxylic (20.2%) and cyloalkanoic (5.2%) acids, a high proportion of alicyclic, heterocyclic and aromatic structural elements in the structure of this kerogen was demonstrated. The most interesting finding was the isolation and identification, in significant amounts, of a series of monocarboxylic mono- and bicyclic cycloalkanoic acids. A small quantity of isoprenoid acids was found in the oxidation products. A homogeneous structure of the Messel shale kerogen is suggested. 17 refs., 9 figs., 4 tabs.

  17. Release of organic nitrogen compounds from Kerogen via catalytic hydropyrolysis

    Directory of Open Access Journals (Sweden)

    Bennett B

    2000-12-01

    Full Text Available High hydrogen pressure pyrolysis (hydropyrolysis was performed on samples of solvent extracted Kimmeridge Clay Formation source rock with a maturity equivalent to ca. 0.35% vitrinite reflectance. We describe the types and distributions of organic nitrogen compounds in the pyrolysis products (hydropyrolysates using GC-MS. Compounds identified included alkyl-substituted indoles, carbazoles, benzocarbazoles, quinolines and benzoquinolines. The distributions of the isomers of methylcarbazoles, C2-alkylcarbazoles and benzocarbazoles in the hydropyrolysates were compared to a typical North Sea oil. The hydropyrolysates compared to the North Sea oil, showed increased contributions from alkylcarbazole isomers where the nitrogen group is "exposed" (no alkyl substituents adjacent to the nitrogen functionality and appreciable levels of benzo[b]carbazole relative to benzo[a]- and benzo[c]carbazoles. Hydropyrolysis is found to be an ideal technique for liberating appreciable quantities of heterocyclic organic nitrogen compounds from geomacromolecules. The products released from the immature Kimmeridge Clay are thought to represent a potential source of nitrogen compounds in the bound phase (kerogen able to contribute to the free bitumen phase during catagenesis.

  18. Structural Evolution of Kerogen and Bitumen during Thermal Maturation examined by Fourier-Transform Infrared Spectroscopy

    Science.gov (United States)

    Craddock, P. R.; Le Doan, T. V.; Pomerantz, A.

    2014-12-01

    Kerogen—the organic matter that is solid and insoluble in organic solvents—is a key component of organic-rich mudstones. The composition of kerogen affects the storage and transport of hydrocarbons in these unconventional resources and is known to change with thermal maturity. We report here using FTIR spectroscopy, the compositional characteristics of kerogen as a function of thermal maturity, together with the compositional characteristics of the organic phase, bitumen—the organic matter that is solid, but soluble in organic solvents. Kerogen is consumed during thermal maturation, whereas bitumen is an intermediary formed at low maturity from kerogen and consumed at higher maturities in formation of oil and gas. Bitumen relative to kerogen has higher aliphatic content, lower aromatic content, and lower abundance of oxygenated functions. At low maturity (vitrinite reflectance equivalent VRe ~ 0.5-0.9 %), the average length of aliphatic chains in bitumen increases during bitumen formation. At higher thermal maturities (VRe > 1.0-1.3 %), average aliphatic chain length decreases as bitumen is consumed. This evolution contrasts to that in kerogen, where aliphatic chain lengths shorten during all stages of maturation. Breakdown of kerogen appears to be driven by cleavage of oxygen functions at low maturity and removal of aliphatic carbons at higher maturities. These aliphatic-rich fragments may comprise the bitumen, and may in part explain the solubility of bitumen in organic solvents. Bitumen shows evidence of oxidation at low thermal maturity, a phenonemom not documented for kerogen. Bitumen maturation and degradation at higher thermal maturity is driven by cleavage and loss of aliphatic carbons, and is coincident with the maximum generation of oil and gas. The aromatic content of bitumen and of kerogen both increase during maturation as a consequence of the loss of aliphatic carbon. The oil and gas generation potential of the residual organic matter thus

  19. Sorption of phenanthrene and benzene on differently structural kerogen: important role of micropore-filling.

    Science.gov (United States)

    Zhang, Yulong; Ma, Xiaoxuan; Ran, Yong

    2014-02-01

    Shale was thermally treated to obtain a series of kerogen with varied maturation. Their chemical, structural and porous properties were related to the sorption and/or desorption behaviors of phenanthrene and benzene. As the treatment temperature increases, aliphatic and carbonyl carbon of the kerogen samples decrease, while their aromaticity and maturation increase. Meanwhile, the isothermal nonlinearity of phenanthrene and benzene increases whereas the sorption capacity and micropore adsorption volumes (Vo,d) initially increase and then decrease. The Vo,d of benzene is significantly correlated with, but higher than that of phenanthrene, suggesting similar micropore filling mechanism and molecular sieve effect. The benzene desorption exhibits hysteresis, which is related to the pore deformation of the kerogen and the entrapment of solute in the kerogen matrix. The Vo,d of phenanthrene and benzene on the kerogen samples accounts for 23-46% and 36-65% of the maximum sorption volumes, respectively, displaying the importance of the micropore filling. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. Kerogen-mineral reactions at raised temperatures in the presence of water

    Energy Technology Data Exchange (ETDEWEB)

    Eglinton, T I; Rowland, S J; Curtis, C D; Douglas, A G

    1986-01-01

    Kerogen has been artificially matured under hydrous pyrolysis conditions in the presence of various minerals in order to investigate the influence of the latter on the organic products. In addition to three clay minerals (montmorillonite, illite, kaolinite), calcium carbonate and limonite were also employed as inorganic substrates. Kerogen (Type II) isolated from the Kimmeridge Blackstone band was heated in the presence of water and a 20-fold excess of mineral phase at two different temperatures (280 and 330/sup 0/C) for 72 hr. Control experiments were also carried out using kerogen and water only and kerogen under anhydrous conditions. This preliminary study describes the bulk composition of the pyrolysates with detailed analyses of the aliphatic hydrocarbon distributions being provided by gas chromatography and combined gas chromatography-mass spectrometry. In the 280/sup 0/C experiments, considerably more organic-soluble pyrolysate (15% by weight of original kerogen) was produced when calcium carbonate was the inorganic phase. At 330/sup 0/C, all samples generated much greater amounts of organic-soluble products with calcium carbonate again producing a large yield (approx. 40% wt/wt). Biomarker epimerization reactions have also proceeded further in the 330/sup 0/C pyrolysate formed in the presence of calcium carbonate than with other inorganic phases. Implications of these and other observations are discussed.

  1. Shale kerogen as a macromolecular substance, and the origin of shales. Khimiya i genezis tverd. goryuch. iskopaemykh, trudy i vsesoyuz

    Energy Technology Data Exchange (ETDEWEB)

    Kogerman, P N

    1950-01-01

    Ideas and general laws concerning the chemistry of high polymers were used to study the organic matter of oil shale (Estonian kukersite). The insolubility of kerogen in water, alkali, acids, or organic solvents is similar to two or three dimensional polymers. In an aqueous solution of chloral hydrate, kerogen swells to a certain extent but does not dissolve. This is similar to high polymers. The softening point of kerogen is between 340 and 380/sup 0/C., at which temperature it acquires plastic properties and resembles high-molecular-weight thermoplastics. Kerogen does not distill without decomposition even at reduced pressures and consequently must have a molecular weight above 1,000. Thermal decomposition products of kerogen are mixtures of low-molecular-weight compounds, the composition of which gives little information concerning the original kerogen. Starch, proteins, lignins, and other natural products give similar materials. The average specific gravity of kukersite kerogen is 1.08 and corresponds approximately to that of polymeric hydrocarbons, cellulose ethers, and natural resins such as copal, sandarac, and others. From these facts, kerogen can be considered to be a high-polymeric substance. Most modern geologists hold that marine deposits of microscopic blue-green algae are the parent substances of kerogen. However, other plankton organisms, especially diatoms, may have contributed to the organic material present in kukersite. Modern blue-green algae contain 60 percent proteins, 3 percent fat, 5 percent pentosan, 1 percent cellulose, and 31 percent other carbohydrates. Chemical studies of kerogen, such as halogenation, nitration, permanganate oxidation, and others indicate that kerogen contains both carbon-chain and hetero-chain compounds. The former may have originated from the nonnitrogenous compounds present in the parent blue-green algae, preserved by adsorption on the inorganic portion of kukersite.

  2. Attachment of di- and tricarboxylic acids to the starting structure of kukersite kerogen

    Energy Technology Data Exchange (ETDEWEB)

    Pobul, L; Mannik, A

    1974-01-01

    Oxidation of the kerogen of kukersite by alkaline permanganate at 50/sup 0/C gave a product containing straight-chain dicarboxylic acids (up to 80%), among which C/sub 4/-C/sub 10/ acids predominated (over 70%). Tricarboxylic acids (15 to 20%) and ..cap alpha..-methyl dicarboxylic acids (4 to 10%) were present. Straight-chain monocarboxylic acids, their isomers, and phenyl derivatives contributed less than 1%. Probably, ..cap alpha..-methyl dicarboxylic and tricarboxylic acids were original structural units of the kerogen. Similar oxidations of Baltic shale indicated that kerogens of different combustible shales differ in chemical composition, but the content of polymers of fatty acids was characteristic. Oxidation of the polymeric acids gave straight-chain mono- and dicarboxylic acids.

  3. Characterisation of Tertiary Catalan lacustrine oil shales: Discovery of extremely organic sulphur-rich type I kerogens

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Las Heras, F.X.C. de; Bergen, P.F. van; Leeuw, J.W. de

    1993-01-01

    The kerogens of three Tertiary Catalan lacustrine oil shales were analyzed by light microscopy, flash pyrolysis-gas chromatography-mass spectrometry, and bulk composition methods (elemental analysis, Rock Eval pyrolysis). Two of the three kerogens (Ribesalbes and Campins) are extremely rich in

  4. Melanoidins-kerogen precursors and geochemical lipid sinks: a study using pyrolysis gas chromatography (PGC)

    Energy Technology Data Exchange (ETDEWEB)

    Larter, S R; Douglas, A G

    1980-12-01

    Melanoidins, acidic polymeric products of amino acid/sugar condensation reactions, are shown to be capable of reacting with and binding functionalized lipid molecules. Pyrolysis gas chromatography is used to monitor the inclusion of lipids (alcohols and acids) into, and to monitor the changes in composition caused by artificial diagenesis of, the melanoidins. Artificial diagenesis of the lipid-containing melanoidins produces a material resembling kerogen. The possible role of melanoidins in the formation of krogen is discussed as are internal transformations within kerogens during diagenesis.

  5. The composition of acids in bitumen and in products from saponification of kerogen: Investigation of their role as connecting kerogen and mineral matrix

    Energy Technology Data Exchange (ETDEWEB)

    Razvigorova, M.; Budinova, T.; Tsyntsarski, B.; Petrova, B. [Bulgarian Academy of Sciences, Institute of Organic Chemistry, 1113 Sofia, Acad. Bonchev Str., bl. 9 (Bulgaria); Ekinci, E. [ISIK University, Kumbaba Mevkii, 34980 Istanbul (Turkey); Atakul, H. [Istanbul Technical University, Department of Chemical Engineering, Maslak, 34469 Istanbul (Turkey)

    2008-11-03

    In order to obtain more information and to understand the nature of relation between organic and mineral matter in oil shales, the compositions of soluble bitumen fractions obtained by extraction from Bulgarian oil shales before and after demineralization with 10% HCl, concentrated HF, and a HF/HCl mixture were investigated. The four extracts were quantitatively examined by IR and {sup 1}H NMR spectroscopy. The investigation of isolated acidic material of the bitumen fractions showed that the fatty acids are present in bitumen fractions as free acids, esters and salts. The amount of free acids in bitumen is very small. The dominant part of bitumen acids is associated with mineral components of the oil shales as well as part of them is included in the mineral matrix, and can be separated only after deep demineralization. The kerogen of the oil shales, obtained after separation of the bitumen fractions and mineral components, was subjected to saponification in order to determine the amount of acids, bound as esters to the kerogen matrix. The major components found were n-carboxylic, {alpha},{omega}-di-carboxylic, and aromatic acids. The connection of kerogen with mineral components is accomplished by the participation of carboxylic and complicated ester bonds. Experimental data for the composition of bitumen acids give evidence that algae and terrestrial materials are initial sources in the formation of soluble organic matter of Bulgarian oil shale. (author)

  6. Petrographic and geochemical composition of kerogen in the Furongian (U. Cambrian) Alum Shale, central Sweden

    DEFF Research Database (Denmark)

    Sanei, H.; Petersen, H. I.; Schovsbo, N. H.

    2014-01-01

    that organic-rich Alum Shale (TOC: 8.9-28.0. wt.%) contains mainly immature, predominantly algal-derived kerogen with unusually reduced hydrocarbon generation potential as suggested by relatively low Hydrogen Index (HI) values (HI: 251-471. mg HC/g TOC) and high degree of aromaticity. In the absence of thermal...

  7. Structural and isotopic analysis of kerogens in sediments rich in free sulfurised Botryococcus braunii biomarkers

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Grice, K.; Schouten, S.; Blokker, P.; Derenne, S.; Largeau, C.; Nissenbaum, A.

    2003-01-01

    Type I kerogens of two relatively immature, unusual hypersaline sediments [with extracts rich in sulfurised Botryococcus braunii (B. braunii) biomarkers] of Miocene/Pliocene age from the Sdom Formation (Dead Sea, Israel), have been investigated using a variety of organic geochemical techniques. Py

  8. Methodological comparison for quantitative analysis of fossil and recently derived carbon in mine soils with high content of aliphatic kerogen

    Czech Academy of Sciences Publication Activity Database

    Vindušková, O.; Sebag, D.; Cailleau, G.; Brus, Jiří; Frouz, J.

    89-90, December (2015), s. 14-22 ISSN 0146-6380 Institutional support: RVO:61389013 Keywords : kerogen * geogenic carbon * soil organic matter Subject RIV: DD - Geochemistry Impact factor: 2.990, year: 2015

  9. Compaction of TOC-rich shales due to kerogen conversion. Implications for fluid flow and overpressure

    International Nuclear Information System (INIS)

    Hanebeck, D.; Krooss, B.M.; Leythaeuser, D.

    1998-01-01

    TOC-rich shales (10% TOC) have been artificially matured at temperatures between 200 and 350 deg C under controlled axial stress (20 - 40 MPa) for up to 350 hours. The volume change of the cylindrical samples was monitored continuously throughout the experiment. The performed experiments showed that the compaction associated with the thermal decomposition of the kerogen is significantly larger under hydrous than under dry pyrolysis conditions. This observation points at an important role of water in the conversion of kerogen. Semi quantitative permeability tests indicated that sample permeability had decreased at least one order of magnitude after the compaction pyrolysis experiments. This permeability reduction in combination with the observed compaction is the most probable mechanism for overpressure formation in TOC-rich source rock sequences. (author)

  10. Characterization of Tertiary Catalan lacustrine oil shales: Discovery of extrmely organic sulphur-rich Type I kerogens

    Energy Technology Data Exchange (ETDEWEB)

    Sinninghe Damste, J.S.; Heras, F.X.C. De Las; Bergen, P.F. Van; Leeuw, J.W. De (Delft Univ. of Technology (Netherlands))

    1993-01-01

    The kerogens of three Tertiary Catalan lacustrine oil shales were analyzed by light microscopy, flash pyrolysis-gas chromatography-mass spectrometry, and bulk composition methods (elemental analysis, Rock Eval pyrolysis). Two of the three kerogens (Ribesalbes and Campins) are extremely rich in organic sulfur (atomic S[sub org]/C ratio > 0.04) and hydrogen (atomic ratio H/C ratio > 1.5) and are, consequently, classified as Type I-S kerogens. Very characteristic distribution patterns of flash pyrolysis products (e.g., alkan-9- and -10-ones, alkadienes) of the Ribesalbes kerogen revealed that it is predominantly composed of fossilized organic matter of the freshwater alga Botryococcus braunii. These two findings demonstrate that sulfurization of organic matter may also occur in lacustrine sediments provided that sulfate is supplied by external sources. Data on the third kerogen sample (Cerdanya) suggest that the freshwater alga Pediastrum may contain a (partly) aromatic biomacromolecule that is selectively preserved upon diagenesis. These findings testify to the large variability in palaeodepositional conditions in lacutrine environments. A comparison of the biomarker composition of the extract of the Ribesalbes oil shale with the kerogen composition indicate that biomarkers often cannot be used to assess the major sources of organic matter in such settings. A similar conclusion can be drawn from a comparison of literature data concerning the Messel Oil Shale. 75 refs., 18 figs., 7 tabs.

  11. Characterization of Tertiary Catalan lacustrine oil shales: Discovery of extremely organic sulphur-rich Type I kerogens

    Science.gov (United States)

    Sinninghe Damsté, Jaap S.; de las Heras, F. Xavier C.; van Bergen, Pim F.; de Leeuw, Jan W.

    1993-01-01

    The kerogens of three Tertiary Catalan lacustrine oil shales were analyzed by light microscopy, flash pyrolysis-gas chromatography-mass spectrometry, and bulk composition methods (elemental analysis, Rock Eval pyrolysis). Two of the three kerogens (Ribesalbes and Campins) are extremely rich in organic sulphur (atomic S org/C ratio > 0.04) and hydrogen (atomic ratio H/C ratio > 1.5) and are, consequently, classified as Type I-S kerogens. Very characteristic distribution patterns of flash pyrolysis products (e.g., alkan-9- and -10-ones, alkadienes) of the Ribesalbes kerogen revealed that it is predominantly composed of fossilized organic matter of the freshwater alga Botryococcus braunii. These two findings demonstrate that sulphurization of organic matter may also occur in lacustrine sediments provided that sulphate is supplied by external sources. Data on the third kerogen sample (Cerdanya) suggest that the freshwater alga Pediastrum may contain a (partly) aromatic biomacromolecule that is selectively preserved upon diagenesis. These findings testify to the large variability in palaeodepositional conditions in lacustrine environments. A comparison of the biomarker composition of the extract of the Ribesalbes oil shale with the kerogen composition indicate that biomarkers often cannot be used to assess the major sources of organic matter in such settings. A similar conclusion can be drawn from a comparison of literature data concerning the Messel Oil Shale.

  12. Molecular Simulation of Shale Gas Adsorption onto Overmature Type II Model Kerogen with Control Microporosity.

    Czech Academy of Sciences Publication Activity Database

    Michalec, Lukáš; Lísal, Martin

    2017-01-01

    Roč. 115, 9-12 (2017), s. 1086-1103 ISSN 0026-8976 R&D Projects: GA ČR(CZ) GA16-12291S EU Projects: European Commission(XE) 640979 - ShaleXenvironmenT Institutional support: RVO:67985858 Keywords : barnett shale * clay * multiscale kerogen model Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.870, year: 2016

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

    Science.gov (United States)

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

    2016-06-01

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

  14. Sorption Hysteresis of Light Hydrocarbons and Carbon Dioxide in Shale and Kerogen

    KAUST Repository

    Zhao, Huangjing

    2017-11-20

    We present adsorption and desorption isotherms of methane, ethane, propane, n-butane and iso-butane as well as carbon dioxide for two shales and isolated kerogens determined by a gravimetric method. The sorption measurements of two shales were performed at three different temperatures, 308.15, 323.15, and 338.15 K. For the isolated kerogens, the measurements were conducted at 338.15 K. Methane and ethane sorption isotherms were measured to 35 bar. Carbon dioxide sorption isotherms were studied to 30 bar. Due to the low vapor pressure at room temperature, the sorption isotherms of propane, n-butane and iso-butane were measured to 8, 2, and 2 bar, respectively. The adsorptions of propane, n-butane, and iso-butane were much higher than methane at the highest pressures where the measurements were conducted. The adsorption of n-butane was 10 times higher than methane by mole at 2 bar, followed by iso-butane and propane. Our data show significant adsorption hysteresis in ethane, propane, n-butane and iso-butane. The most pronounced hysteresis was found in n-butane and iso-butane. Significant hysteresis is attributed to the reversible structural changes of kerogens. Dissolution of adsorbates into organic matter may also affect the hysteresis. This is the first report of propane and butane sorption isotherms in shales.

  15. Sorption Hysteresis of Light Hydrocarbons and Carbon Dioxide in Shale and Kerogen

    KAUST Repository

    Zhao, Huangjing; Lai, Zhiping; Firoozabadi, Abbas

    2017-01-01

    We present adsorption and desorption isotherms of methane, ethane, propane, n-butane and iso-butane as well as carbon dioxide for two shales and isolated kerogens determined by a gravimetric method. The sorption measurements of two shales were performed at three different temperatures, 308.15, 323.15, and 338.15 K. For the isolated kerogens, the measurements were conducted at 338.15 K. Methane and ethane sorption isotherms were measured to 35 bar. Carbon dioxide sorption isotherms were studied to 30 bar. Due to the low vapor pressure at room temperature, the sorption isotherms of propane, n-butane and iso-butane were measured to 8, 2, and 2 bar, respectively. The adsorptions of propane, n-butane, and iso-butane were much higher than methane at the highest pressures where the measurements were conducted. The adsorption of n-butane was 10 times higher than methane by mole at 2 bar, followed by iso-butane and propane. Our data show significant adsorption hysteresis in ethane, propane, n-butane and iso-butane. The most pronounced hysteresis was found in n-butane and iso-butane. Significant hysteresis is attributed to the reversible structural changes of kerogens. Dissolution of adsorbates into organic matter may also affect the hysteresis. This is the first report of propane and butane sorption isotherms in shales.

  16. Evidence for porphyrins bound, via ester bonds, to the Messel oil shale kerogen by selective chemical degradation experiments

    Science.gov (United States)

    Huseby, B.; Ocampo, R.

    1997-09-01

    High amounts of nickel mono- and di-acid porphyrins were released from Messel oil shale kerogen (Eocene, Germany) by selective chemical degradation (acid and base hydrolysis). The released porphyrin fractions were quantified (UV-vis) and their constituents isolated and characterized at the molecular level (UV-vis, MS, NMR). The mono-acid porphyrin fraction released contained four compounds of similar abundance which arise from an obvious chlorophyll or bacteriochlorophyll precursor. The di-acid porphyrin fraction was, however, dominated by far by one compound, mesoporphyrin IX, which must have originated from heme-like precursors (heme, cytochromes, etc.). These results show unambigously that the released mono- and di-acid porphyrins were linked to the macromolecular kerogen network via ester bonds and suggest that precursor heme-like pigments could be selectively and/or more readily incorporated into the macromolecular kerogen network than precursor chlorophylls and bacteriochlorophylls.

  17. Effect of Thermal Maturation on n-alkanes and Kerogen in Preserved Organic Matter: Implications for Paleoenvironment Biomarkers

    Science.gov (United States)

    Craven, O. D.; Longbottom, T. L.; Hockaday, W. C.; Blackaby, E.

    2017-12-01

    Understanding the effects of maturity on biomarkers is vital in assessing biomarker reliability in mature sediments. It is well known for n-alkanes that increased maturity shortens chain lengths and decreases the odd over even preference however, the amount of change in these variables has not been determined for different maturities and types of preserved organic matter. For this reason, it is difficult to judge the trustworthiness of even lightly matured samples for paleoenvironment reconstruction. Another complication is the difficulty of accurately determining maturity as many maturity indicators are error-prone or not appropriate at low maturities. Using hydrous pyrolysis, we artificially matured black shale samples with type I (lacustrine) and type II (marine) kerogen to measure changes in n-alkane length and odd over even preference. Whole rock samples underwent hydrous pyrolysis for 72 hours, at 250 °C, 300 °C, 325 °C, 350 °C, and 375 °C to cover a wide maturity range. From the immature and artificially matured samples, the bitumen was extracted and the saturate fraction was separated using column chromatography. The saturate fraction was analyzed for n-alkanes using gas chromatography-mass spectroscopy. Kerogen structural changes were also measured using solid-state 13C NMR to relate changes in n-alkane biomarkers to changes in kerogen structure. Results show that for type I bitumen the n-alkanes did not change at low maturities considered premature in terms of oil generation (<325 °C). The NMR spectra of the type I kerogen support the lack of change, at low maturities no changes in the aliphatic portion (Fal) were observed, however, after 325 °C Fal decreased with increasing maturity. The loss of Fal indicates kerogen contributing hydrocarbons to bitumen that cause changes in n-alkane measurements. The type II kerogen's Fal also decreased with increasing maturity, but unlike the type I kerogen Fal loss started at low maturities. The differences

  18. THE HISTORY OF EXPLORATION AND EXPLOITATION OF BITUMINOUS AND KEROGENOUS DEPOSITS IN CROATIA

    Directory of Open Access Journals (Sweden)

    Berislav Šebečić

    1995-12-01

    Full Text Available It is assumed thal the first known sedimens of natural bitumen or asphalt in coastal Croatia were exploited as the early moddle ages. Yet authenticated written documents about Vinišće near Trogir derive from no earlier than 1628, about Vrgorac/Paklina from only 1753. By the end of the 18th century, many deposits were discovered in Dalmatia, but it was Škrip on the Island of Brač and Suhi Dolac that were important. The earliest known deposits and occurrences of kerogenous rocks, or bituminous or oil shales, are mentioned as stone or fossil coal in Sovinjak, in the upper course of the River Mirna, and in Rebići in Istria; near Sinj, Slivno not far from the River Neretva, Mirta and near Nerežišće on the Island uf Brač. All if these were well known and described in 1804, while Sovinjak was mentioned in the 16th century. In the article, some of new information derived from mining and geological research into bituminous and kerogenous sediments and deposits are provided (the paper is published in Croatian.

  19. Study of Kerogen Maturity using Transmission Fourier Transform Infrared Spectroscopy (FTIR)

    Science.gov (United States)

    Dang, S. T.

    2014-12-01

    Maturity of kerogen in shale governs the productivity and generation hydrocarbon type. There are generally two accepted methods to measure kerogen maturity; one is the measurement of vitrinite reflectance, %Ro, and another is the measurement of Tmax through pyrolysis. However, each of these techniques has its own limits; vitrinite reflectance measurement cannot be applied to marine shale and pre-Silurian shales, which lack plant materials. Furthermore, %Ro, requires the isolation and identification of vitrinite macerals and statistical measurements of at least 50 macerals. Tmax measurement is questionable for mature and post-mature samples. In addition, there are questions involving the effects of solvents on Tmax determinations. Fourier Transmission Infrared Spectroscopy, FTIR, can be applied for both qualitative and quantitative assessment on organics maturity in shale. The technique does not require separating organic matter or identifying macerals. A CH2/CH3 index, RCH, calculated from FTIR spectra is more objective than other measurements. The index increases with maturity (both natural maturation and synthetic maturation through hydrous and dry pyrolysis). The new maturity index RCH can be calibrated to vitrinite reflectance which allows the definition of the following values for levels of maturity: 1) immature—RCH > 1.6±0.2; 2) oil window-- 1.6±0.2 1.3±0.3; 3) wet gas window--1.3±0.3 1.13±0.05; and 4) dry gas window RCH < 1.13±0.05.

  20. Rapid estimation of the organic sulphur content of kerogens, coals and asphaltenes by pyrolysis-gas chromatography

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Eglinton, T.I.; Kohnen, M.E.L.; Leeuw, J.W. de

    1990-01-01

    A pyrolysis-gas Chromatographic (py-g.c.) method for estimation of the Sorg/C ratio in kerogens and other forms of sedimentary macromolecular organic matter is described. The method is based upon flash pyrolysis at 610 °C for 10s and areal integration of the FID peaks attributed to

  1. Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Putchew, A.; Schaeffer-Reiss, C.; Schaeffer, P.; Koopmans, M.P.; Leeuw, J.W. de; Lewan, M.D.

    1998-01-01

    An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons

  2. Kerogen chemistry 5. Anhydride formation in, solvent swelling of, and loss of organics on demineralization of Kimmeridge shales

    International Nuclear Information System (INIS)

    Larsen, John W.; Flores, Carlos Islas

    2008-01-01

    The results of three short and related, but experimentally independent, studies of 4 Kimmeridge shales and their kerogens are reported. Differential scanning calorimeter (DSC) studies of the kerogens reveal that three of the four show evidence of anhydride formation when heated at 20 C/min between 50 C and 180 C. There is no regular rank dependence of anhydride formation. After solvent swelling in tetrahydrofuran (THF), extracted organics were isolated from the THF and the recovered kerogens were swollen a second time in fresh THF. The second solvent swelling ratios were slightly larger than the first because the presence of the extracts in the original THF lowers solvent activity thus reducing swelling. The shales were demineralized in the usual way except that methylene chloride was added to dissolve any organics that were liberated from the rock as a consequence of mineral dissolution. Small amounts of organics were found in the methylene chloride supporting Price and Clayton's conclusion that organics are expelled from the kerogen and are present in lacunae in the minerals. (author)

  3. Kerogen morphology and geochemistry at the Permian-Triassic transition in the Meishan section, South China: Implication for paleoenvironmental variation

    Science.gov (United States)

    Sawada, Ken; Kaiho, Kunio; Okano, Kazuki

    2012-08-01

    Detailed fluorescent microscopic observations and organic geochemical analyses for insoluble sedimentary organic matter (kerogens) are conducted on the end-Permian to earliest Triassic sediments in the Meishan section A of South China. The main objectives of the present study are to reconstruct variations of marine and terrestrial environments, and to evaluate bulk characteristics of terrestrial input in the palaeo-Tethys ocean for the Permian-Triassic boundary (PTB). Most of kerogens in the Meishan section are mainly composed of marine algae-derived amorphous organic matter, while terrestrial plant-derived amorphous organic matter is remarkably dominant in the mass extinction horizon reported previously. The relative abundances of marine organic matter may vary depending on marine production rather than terrestrial input in the palaeo-Tethys associated with changing terrestrial vegetation. We also identified aromatic furans as major compounds in kerogen pyrolysate of all layers. It is possible that sources of aromatic furans with alkyl group, fungi and lichen, proliferated as disaster biota in terrestrial ecosystem through the PTB. Higher abundances of herbaceous organic matter are observed in the layers above the mass extinction horizon. However, the conifer biomarker retene can be identified in kerogen pyrolysates of all layers. These results imply that the productions of herbaceous plants increased as dominant pioneer biota in early stage of recovery for terrestrial ecosystem after its collapse, but also that woody plant potentially continued to be produced in land area throughout the end-Permian and earliest-Triassic.

  4. Role of NSO compounds during primary cracking of a Type II kerogen and a Type III lignite

    Science.gov (United States)

    Behar, F.; Lorant, F.; Lewan, M.

    2008-01-01

    The aim of this work is to follow the generation of NSO compounds during the artificial maturation of an immature Type II kerogen and a Type III lignite in order to determine the different sources of the petroleum potential during primary cracking. Experiments were carried out in closed system pyrolysis in the temperature range from 225 to 350 ??C. Two types of NSOs were recovered: one is soluble in n-pentane and the second in dichloromethane. A kinetic scheme was optimised including both kerogen and NSO cracking. It was validated by complementary experiments carried out on isolated asphaltenes generated from the Type II kerogen and on the total n-pentane and DCM extracts generated from the Type III lignite. Results show that kerogen and lignite first decompose into DCM NSOs with minor generation of hydrocarbons. Then, the main source of petroleum potential originates from secondary cracking of both DCM and n-pentane NSOs through successive decomposition reactions. These results confirm the model proposed by Tissot [Tissot, B., 1969. Premie??res donne??es sur les me??canismes et la cine??tique de la formation du pe??trole dans les bassins se??dimentaires. Simulation d'un sche??ma re??actionnel sur ordinateur. Oil and Gas Science and Technology 24, 470-501] in which the main source of hydrocarbons is not the insoluble organic matter, but the NSO fraction. As secondary cracking of the NSOs largely overlaps that of the kerogen, it was demonstrated that bulk kinetics in open system is a result of both kerogen and NSO cracking. Thus, another kinetic scheme for primary cracking in open system was built as a combination of kerogen and NSO cracking. This new kinetic scheme accounts for both the rate and amounts of hydrocarbons generated in a closed pyrolysis system. Thus, the concept of successive steps for hydrocarbon generation is valid for the two types of pyrolysis system and, for the first time, a common kinetic scheme is available for extrapolating results to natural

  5. Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

    Science.gov (United States)

    Putschew, A.; Schaeffer-Reiss, C.; Schaeffer, P.; Koopmans, M.P.; De Leeuw, J. W.; Lewan, M.D.; Sinninghe, Damste J.S.; Maxwell, J.R.

    1998-01-01

    An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330??C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH2 and HI/LiAIH4) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis-GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260??C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak Carbon-heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220??C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.

  6. Effects of CO2 injection and Kerogen Maturation on Low-Field Nuclear Magnetic Resonance Response

    Science.gov (United States)

    Prasad, M.; Livo, K.

    2017-12-01

    Low-field Nuclear Magnetic Resonance (NMR) is commonly used in petrophysical analysis of petroleum reservoir rocks. NMR experiments record the relaxation and polarization of in-situ hydrogen protons present in gaseous phases such as free-gas intervals and solution gas fluids, bulk fluid phases such as oil and aquifer intervals, and immovable fractions of kerogen and bitumen. Analysis of NMR relaxation spectra is performed to record how fluid composition, maturity, and viscosity change NMR experimental results. We present T1-T2 maps as thermal maturity of a water-saturated, sub-mature Woodford shale is increased at temperatures from 125 to 400 degrees Celsius. Experiments with applied fluid pressure in paraffinic mineral oil and DI water with varying fluid pH have been performed to mimic reservoir conditions in analysis of the relaxation of bulk fluid phases. We have recorded NMR spectra, T1-T2 maps, and fluid diffusion coefficients using a low-field (2 MHz) MagritekTM NMR. CO2 was injected at a pressure of 900 psi in an in house developed NMR pressure vessel made of torlon plastic. Observable 2D NMR shifts in immature kerogen formations as thermal maturity is increased show generation of lighter oils with increased maturity. CO2 injection leads to a decrease in bulk fluid relaxation time that is attributed to viscosity modification with gas presence. pH variation with increased CO2 presence were shown to not effect NMR spectra. From this, fluid properties have been shown to greatly affect NMR readings and must be taken into account for more accurate NMR reservoir characterization.

  7. Differences in bitumen and kerogen-bound fatty acid fractions during diagenesis and early catagenesis in a maturity series of New Zealand coals

    DEFF Research Database (Denmark)

    Glombitza, Clemens; Mangelsdorf, Kai; Horsfield, Brian

    2016-01-01

    network. Application of the carbon preference index for fatty acids (CPIFA) of bitumen and kerogen-bound acids revealed a linear correlation to the Tmax maturity parameter. This shows that the CPIFA has a clear relation to thermal stability and, thus, reactivity of the buried organic matter....... The difference in slopes of CPIFA vs. Tmax for short and long chain as well as bitumen and kerogen-bound acids may indicate their different degradation susceptibilities. The short chain fatty acids of the bitumen show the highest susceptibility whereas the kerogen-bound long chain fatty acids seem to be most...

  8. Chitin: 'Forgotten' Source of Nitrogen: From Modern Chitin to Thermally Mature Kerogen: Lessons from Nitrogen Isotope Ratios

    Science.gov (United States)

    Schimmelmann, A.; Wintsch, R.P.; Lewan, M.D.; DeNiro, M.J.

    1998-01-01

    Chitinous biomass represents a major pool of organic nitrogen in living biota and is likely to have contributed some of the fossil organic nitrogen in kerogen. We review the nitrogen isotope biogeochemistry of chitin and present preliminary results suggesting interaction between kerogen and ammonium during thermal maturation. Modern arthropod chitin may shift its nitrogen isotope ratio by a few per mil depending on the chemical method of chitin preparation, mostly because N-containing non-amino-sugar components in chemically complex chitin cannot be removed quantitatively. Acid hydrolysis of chemically complex chitin and subsequent ion-chromatographic purification of the "deacetylated chitin-monomer" D-glucosamine (in hydrochloride form) provides a chemically well-defined, pure amino-sugar substrate for reproducible, high-precision determination of ??15N values in chitin. ??15N values of chitin exhibited a variability of about one per mil within an individual's exoskeleton. The nitrogen isotope ratio differed between old and new exoskeletons by up to 4 per mil. A strong dietary influence on the ??15N value of chitin is indicated by the observation of increasing ??15N values of chitin from marine crustaceans with increasing trophic level. Partial biodegradation of exoskeletons does not significantly influence ??15N values of remaining, chemically preserved amino sugar in chitin. Diagenesis and increasing thermal maturity of sedimentary organic matter, including chitin-derived nitrogen-rich moieties, result in humic compounds much different from chitin and may significantly change bulk ??15N values. Hydrous pyrolysis of immature source rocks at 330??C in contact with 15N-enriched NH4Cl, under conditions of artificial oil generation, demonstrates the abiogenic incorporation of inorganic nitrogen into carbon-bound nitrogen in kerogen. Not all organic nitrogen in natural, thermally mature kerogen is therefore necessarily derived from original organic matter, but may

  9. Cretaceous – Paleogene boundary Fish Clay at Højerup (Stevns Klint, Denmark: Zn, Pb and REE in kerogen

    Directory of Open Access Journals (Sweden)

    MILOS G. DJORDJEVIC

    2008-04-01

    Full Text Available Geochemical analyses of Zn, Pb and rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu in the kerogen of the black marl at the Cretaceous – Paleogene boundary Fish Clay at Højerup were performed. Substantial proportions of the Zn, Pb and rare earths were probably contained in terrestrial humic substances (the kerogen precursor arriving at the marine sedimentary site. This is in accord with a previous hypothesis that kerogen is mainly derived from humic acids of an oxic soil in of the adjacent coastal areas of eastern Denmark. It is also suggested that humics enriched in Zn, Pb and rare earth elements were transported mainly through fluvial transport into the deposition site of the Fish Clay. Local weathering/leaching of the impact–eject fallout on the land surface and local terrestrial rocks by impact-induced? acid surface waters perhaps played an important role in providing Zn, Pb and rare earths to these humic substances. Apparently, chondritic and non-chondritic Zn originated from the impact fallout; Pb and rare earth elements were most likely sourced by exposed rocks in the coastal areas of eastern Denmark.

  10. Paleovegetation changes recorded by n-alkyl lipids bound in macromolecules of plant fossils and kerogens from the Cretaceous sediments in Japan

    Science.gov (United States)

    Miyata, Y.; Sawada, K.; Nakamura, H.; Takashima, R.; Takahashi, M.

    2014-12-01

    Resistant macromolecules composing living plant tissues tend to be preserved through degradation and diagenesis, hence constituate major parts of sedimentary plant-derived organic matter (kerogen), and their monomer compositions vary widely among different plant taxa, organs and growth stages. Thus, analysis of such macromolecule may serve as new technique for paleobotanical evaluation distinctive from classical paleobotnical studies depends on morphological preservation of fossils. In the present study, we analyzed plant fossils and kerogens in sediments from the Cretaceous strata in Japan to examine chemotaxonomic characteristics of fossil macromolecules and to reconstruct paleovegetation change by kerogen analysis. The kerogens were separated from the powdered sediments of Cretaceous Yezo Group, Hokkaido, Japan. All kerogens have been confirmed to be mostly originated from land plant tissues by microscopic observation. Mummified angiosperm and gymnosperm fossil leaves were separated from carbonaceous sandstone of the Cretaceous Ashizawa Formation, Futaba Group. The kerogens and plant fossils were extracted with methanol and dichloromethane, and were subsequently refluxed under 110°C to remove free compounds completely. The residues are hydrolyzed by KOH/methanol under 110°C. These released compounds are analyzed by GC-MS. As main hydrolyzed products (ester-bound molecular units) from all kerogens, C10-C28 n-alkanoic acids and C10-C30 n-alkanols were detected. Recent studies on the hydrolysis products of plant tissues suggested the long chain (>C20) n-alkanols were predominantly abundant in deciduous broadleaved angiosperms. Correspondingly, the stratigraphic variation of the ratios of long chain (>C20) n-alkanols to fatty acids was concordant with the variation of angiosperm/gymnosperm ratios recorded by land plant-derived terpenoid biomarkers. In addition, we found that the long chain n-alkanols/fatty acids ratio in the angiosperm fossil leaf was

  11. Unique distributions of hydrocarbons and sulphur compounds released by flash pyrolysis from the fossilised alga Gloeocapsomorpha prisca, a major constituent in one of four Ordovician kerogens

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Douglas, A.G.; Fowler, M.G.; Eglinton, T.I.

    1991-01-01

    Kerogens isolated from four rocks of Ordovician age from North America have been analysed by combined pyrolysis-gas chromatography-mass spectrometry to compare and contrast the type and distribution of sulphur-containing compounds and aromatic and aliphatic hydrocarbons present in the

  12. Extensive Sorption of Organic Compounds to Black Carbon, Coal and Kerogen in Sediments and Soils: Mechanisms and Consequences for Distribution, Bioaccumulation and Biodegradation (Critical Review)

    NARCIS (Netherlands)

    Cornelissen, G.; Gustafsson, O.; Bucheli, T.D.; Jonker, M.T.O.; Koelmans, A.A.; Noort, van P.C.M.

    2005-01-01

    Evidence is accumulating that sorption of organic chemicals to soils and sediments can be described by "dual-mode sorption": absorption in amorphous organic matter (AOM) and adsorption to carbonaceous materials such as black carbon (BC), coal, and kerogen, collectively termed "carbonaceous

  13. Geochemical characterisation of kerogen from the Boom Clay Formation (Mol, Belgium) and evolution under different thermal stress

    International Nuclear Information System (INIS)

    Deniau, I.

    2002-12-01

    The Boom clay formation in Belgium has been chosen as test site for the disposal of high level radioactive wastes. The organic matter present in the clay (kerogen) is sensible to the thermal stress and can generate a huge number of gaseous and liquid compounds leading to local pH changes and to fracturing processes. In particular, some polar compounds can complex radionuclides. The samples analyzed in this work were taken in the underground laboratory of Mol at a 223 m depth. They have been analyzed in detail using geochemical methods (Rock-Eval pyrolysis, element analysis, transmission and scanning electron microscopy), spectroscopic methods (Fourier transformation infrared spectroscopy, solid state 13 C NMR, Raman) and pyrolytic methods (off-line, on-line and in sealed tubes combined with coupled CG/SM analyses). The study of a representative sample of this formation has permitted to characterize the organic matter at the molecular scale, to determine its fossilization mechanisms and the nature of the organic compounds trapped inside the kerogen. The organic matter of the Boom clays comes mainly from phyto-planktonic matter with an important contribution of terrestrial and bacterial matter. The degradation-recondensation played an important role in its preservation but the presence of numerous oxygenated molecules implies that oxidative incorporation also participated to this preservation. Finally, various products (hydrocarbons, oxygenated and nitrogenous polar compounds) trapped in significant amount inside the macro-molecular structure are released under a relatively weak thermal stress. Moreover several small polar organic molecules are released and can play a significant role in the retention or migration of radionuclides inside the geologic barrier. A sample submitted to a in-situ thermal stress of 80 deg. C during 5 years (Cerberus experiment) do not show any significant change in its kerogen structure with respect to the non-heated reference sample

  14. The kinetics of sterane biological marker release and degradation processes during the hydrous pyrolysis of vitrinite kerogen

    Science.gov (United States)

    Abbott, G. D.; Wang, G. Y.; Eglinton, T. I.; Home, A. K.; Petch, G. S.

    1990-09-01

    The hydrous pyrolysis of a mineral-free vitrinite kerogen (Dinantian coal Lower Carboniferous, North East England) has been carried out at four temperatures (270, 300, 330, and 350°C) for heating times ranging from 2 to 648 h. No significant differences in the epimer-based maturation parameters 20S/(20S + 20R)-5α(H),14α(H),17α(H) C 29 non-rearranged steranes and 22S/(22S+22R)-17α(H), 21β(H) homohopanes were found for a comparison between "expelled oil" and "bitumen" fractions in the resulting pyrolysates. A deuterated model compound ((20R)-5α(H),14α(H),17α(H)-[2,2,4,4-d 4] cholestane) was added to a number of preextracted kerogens (vitrinite, Kimmeridge, Messel and Monterey) and the mixtures were heated under typical hydrous pyrolysis conditions. These experiments showed that direct chiral isomerisation at C-20 in the non-rearranged steranes appears to be relatively unimportant during hydrous pyrolysis which has also been suggested by other recent studies on geological samples.A kinetic model comprising consecutive release and degradation processes was derived to measure first-order rate coefficients from the bi-exponential concentration-time functions of both the (20R)-and (20S)-5α(H),14α(H),17α(H) C 29 "free" steranes in the vitrinite kerogen pyrolysates. This data was then used to calculate preliminary Arrhenius parameters for release ((20S): ΔEa = 125 ± 30 kJ mol -1, A ≈ 4.7 × 10 5 s -1;(20R): ΔEa = 151 ± 39 kJ mol -1, A ≈ 2.7 × 10 9 s -1) and degradation ((20S): ΔEa = 104 ± 22 kJ mol -1, A ≈ 5.8 × 10 3 s -1; (20R): Δa = 87 ± 6 kJ mol -1, A ≈ 2.2 × 10 2 s -1) of the above individual isomers and the values were found to be consistent with a free-radical chain mechanism. This work helps in the greater understanding of the important biomarker reactions that prevail in hydrous pyrolysis experiments.

  15. Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

    Science.gov (United States)

    Socki, Richard A.; Pernia, Denet; Evans, Michael; Fu, Qi; Bissada, Kadry K.; Curiale, Joseph A.; Niles, Paul B.

    2014-01-01

    Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas- and liquids-rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make qualitative and semi-quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II-S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = -215.2 per mille (V-SMOW), ranging from - 271.8 per mille for the Marcellus Shale to -51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of -89.7 per mille, ranging from -156.0 per mille for the Barnett Shale to -50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with

  16. Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa

    Science.gov (United States)

    Beukes, N. J.; Klein, C.; Kaufman, A. J.; Hayes, J. M.

    1990-01-01

    The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic

  17. A kinetic study of the depyritization of oil shale HCl-kerogen concentrate by Thiobacillus ferrooxidans at different temperatures

    Directory of Open Access Journals (Sweden)

    OLGA CVETKOVIC

    2003-05-01

    Full Text Available The results of kinetic studies of bacterial depyritization of HCl-kerogen concentrate of Aleksinac (Serbia oil shale by the chemolithoautotrophic thionic bacteria Thiobacillus ferrooxidans under discontinuous laboratory conditions at various temperatures (0, 20, 28 and 37°C at a pH of ca. 1.5 are presented in this paper. Low pH prevents the occurrence of the precipitation of iron(III-ion hydrolysis products on the substrate particles and thereby reduces the process efficiency. Bacterial depyritization is developed as per kinetics of the first order. The activation energy which points to a successive mechanism of pyrite biooxidation, was computed from the Arrhenius plot. The biochemical kinetics indicators point to a high affinity of the bacteria toward pyrite but small values of Vmax, which are probably the result of decelerated metabolic processes due to the low pH value of the environment resp. the large difference of the pH between the external medium and the cell interior.

  18. Composition, peat-forming vegetation and kerogen paraffinicity of Cenozoic coals: Relationship to variations in the petroleum generation potential (Hydrogen Index)

    Energy Technology Data Exchange (ETDEWEB)

    Petersen, H.I.; Lindstroem, S.; Nytoft, H.P.; Rosenberg, P. [Geological Survey of Denmark and Greenland (GEUS), Oester Voldgade 10, DK-1350 Copenhagen (Denmark)

    2009-04-01

    Coals with similar thermal maturity and from the same deposit normally show a considerable range in petroleum generation potential as measured by the Hydrogen Index (HI). This variation may partly be related to variations in plant input to the precursor mires and organic matter preservation. It is widely accepted that some Cenozoic coals and coaly sediments have the potential to generate oil, which is related to the coal's paraffinicity. Coal paraffinicity is not readily reflected in the bulk HI. In this paper, the relationships between measured HI and coal composition, coal kerogen paraffinicity and floral input have been investigated in detail for three sets of coals from Colombia/Venezuela, Indonesia, and Vietnam. The samples in each coal set are largely of iso-rank. The petroleum generation potential was determined by Rock-Eval pyrolysis. Reflected light microscopy was used to analyse the organic matter (maceral) composition and the thermal maturity was determined by vitrinite reflectance (VR) measurements. The botanical affinity of pollen and spores was analysed by palynology. Coal kerogen paraffinicity was determined by ruthenium tetroxide-catalysed oxidation (RTCO) followed by chain length analysis and quantification (mg/g TOC) of the liberated aliphatic chains. The coals are dominated by huminite, in particular detrohuminite. Only the Vietnamese coals are rich in microscopically visible liptinite. The pollen and spores suggest that the coals were derived principally from complex angiosperm mire vegetations, with subordinate proportions of ferns that generally grew in a subtropical to tropical climate. Measured HI values vary considerably, but for the majority of the coals the values lie between approximately 200 mg HC/g TOC and 300 mg HC/g TOC. Aliphatics yielding monocarboxylic acids dominate in the coal kerogen, whereas aliphatics yielding dicarboxylic acids are secondary. However, the dicarboxylic acids show that cross-linking long-chain aliphatics

  19. 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.

  20. Organic richness, kerogen types and maturity in the shales of the Dakhla and Duwi formations in Abu Tartur area, Western Desert, Egypt: Implication of Rock–Eval pyrolysis

    Directory of Open Access Journals (Sweden)

    Mohamed M. El Nady

    2015-12-01

    Full Text Available The objective of this study is to assess the organic material for petroleum potential and characterize the relationships between organic material, thermal maturity, and the depositional environments. This is done using “14” samples from the shales of the Dakhla and Duwi formations in Abu Tartur area. The samples have been analyzed using the geochemical method of Rock–Eval pyrolysis. The analysis shows that the total organic carbon content lies between 0.56 and 1.96 wt%. It also shows that kerogen is a mixture of type II and III that is dominant, and is deposited in the shallow and restricted marine environment under prevailing reducing conditions. This type of kerogen is prone to oil and oil/gas production. The geochemical diagrams show that all the studied samples have good thermal maturation. The Dakhla and Duwi formations which have been divided into all zones are mature (have Tmax over 435 °C, and have organic carbon content located at the oil window (Tmax between 435 and 443 °C.

  1. Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence Vena del Gesso, Italy III. Stratigraphic changes in the molecular structure of kerogen in a single marl bed as revealed by flash pyrolysis

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Gelin, F.; Harrison, W.N.; Maxwell, J.R.

    1995-01-01

    Kerogens of nine samples from a single marl bed of the Gessoso-solfifera Formation in the Vena del Gesso basin (Messinian, Italy) were qualitatively and quantitatively studied by analytical pyrolysis. Relationships between the nature of the pyrolysis products and the source organisms were

  2. Catalytic generation of methane at 60-100 °C and 0.1-300 MPa from source rocks containing kerogen Types I, II, and III

    Science.gov (United States)

    Wei, Lin; Schimmelmann, Arndt; Mastalerz, Maria; Lahann, Richard W.; Sauer, Peter E.; Drobniak, Agnieszka; Strąpoć, Dariusz; Mango, Frank D.

    2018-06-01

    Low temperature (60 and 100 °C) and long-term (6 months to 5 years) heating of pre-evacuated and sterilized shales and coals containing kerogen Types I (Mahogany Shale), II (Mowry Shale and New Albany Shale), and III (Springfield Coal and Wilcox Lignite) with low initial maturities (vitrinite reflectance Ro 0.39-0.62%) demonstrates that catalytically generated hydrocarbons may explain the occurrence of some non-biogenic natural gas accumulations where insufficient thermal maturity contradicts the conventional thermal cracking paradigm. Extrapolation of the observed rate of catalytic methanogenesis in the laboratory suggests that significant amounts of sedimentary organic carbon can be converted to relatively dry natural gas over tens of thousands of years in sedimentary basins at temperatures as low as 60 °C. Our laboratory experiments utilized source rock (shale and coal) chips sealed in gold and Pyrex® glass tubes in the presence of hydrogen-isotopically contrasting waters. Parallel heating experiments applied hydrostatic pressures from 0.1 to 300 MPa. Control experiments constrained the influence of pre-existing and residual methane in closed pores of rock chips that was unrelated to newly generated methane. This study's experimental methane yields at 60 and 100 °C are 5-11 orders of magnitude higher than the theoretically predicted yields from kinetic models of thermogenic methane generation, which strongly suggests a contribution of catalytic methanogenesis. Higher temperature, longer heating time, and lower hydrostatic pressure enhanced catalytic methanogenesis. No clear relationships were observed between kerogen type or total organic carbon content and methane yields via catalysis. Catalytic methanogenesis was strongest in Mowry Shale where methane yields at 60 °C amounted to ∼2.5 μmol per gram of organic carbon after one year of hydrous heating at ambient pressure. In stark contrast to the earlier findings of hydrogen isotopic exchange between

  3. Chemical and nanometer-scale structure of kerogen and its change during thermal maturation investigated by advanced solid-state 13C NMR spectroscopy

    Science.gov (United States)

    Mao, J.; Fang, X.; Lan, Y.; Schimmelmann, A.; Mastalerz, Maria; Xu, L.; Schmidt-Rohr, K.

    2010-01-01

    We have used advanced and quantitative solid-state nuclear magnetic resonance (NMR) techniques to investigate structural changes in a series of type II kerogen samples from the New Albany Shale across a range of maturity (vitrinite reflectance R0 from 0.29% to 1.27%). Specific functional groups such as CH3, CH2, alkyl CH, aromatic CH, aromatic C-O, and other nonprotonated aromatics, as well as "oil prone" and "gas prone" carbons, have been quantified by 13C NMR; atomic H/C and O/C ratios calculated from the NMR data agree with elemental analysis. Relationships between NMR structural parameters and vitrinite reflectance, a proxy for thermal maturity, were evaluated. The aromatic cluster size is probed in terms of the fraction of aromatic carbons that are protonated (???30%) and the average distance of aromatic C from the nearest protons in long-range H-C dephasing, both of which do not increase much with maturation, in spite of a great increase in aromaticity. The aromatic clusters in the most mature sample consist of ???30 carbons, and of ???20 carbons in the least mature samples. Proof of many links between alkyl chains and aromatic rings is provided by short-range and long-range 1H-13C correlation NMR. The alkyl segments provide most H in the samples; even at a carbon aromaticity of 83%, the fraction of aromatic H is only 38%. While aromaticity increases with thermal maturity, most other NMR structural parameters, including the aromatic C-O fractions, decrease. Aromaticity is confirmed as an excellent NMR structural parameter for assessing thermal maturity. In this series of samples, thermal maturation mostly increases aromaticity by reducing the length of the alkyl chains attached to the aromatic cores, not by pronounced growth of the size of the fused aromatic ring clusters. ?? 2010 Elsevier Ltd. All rights reserved.

  4. The palaeoenvironmental implications of carbonate petrography, kerogen distribution and carbon and oxygen isotope variations in the early Proterozoic transition from Campbellrand limestone to Kuruman iron-formation deposition in Griqualand West

    International Nuclear Information System (INIS)

    Beukes, N.J.; Klein, C.; Kaufman, A.J.; Hayes, J.M.

    1990-01-01

    The Griqualand West area of the Transvaal basin in South Africa offers a unique opportunity to study the relationships between the deposition of limestone and iron-formation. The stratigraphic sequence includes the transition from microbialaminated Campbellrand carbonates to the conformably Kuruman iron formation composed mainly of microbanded iron-formation. The relationships between carbonate mineral paragenesis, kerogen abundance, and isotopic compositions of carbon and oxygen for the same drill core samples are reported. The significance of whole rock carbon-isotopic compositions of iron-formations relative to those of limestones and dolomites are explored. 6 refs

  5. Sulphur and oxygen sequestration of n-C37 and n-C38 unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

    Science.gov (United States)

    Koopmans, M.P.; Schaeffer-Reiss, C.; De Leeuw, J. W.; Lewan, M.D.; Maxwell, J.R.; Schaeffer, P.; Sinninghe, Damste J.S.

    1997-01-01

    Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature (Ro = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330??C for 72 h to study the diagenetic fate of n-C37 and n-C38 di-and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260??C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S-and O-bound n-C37 and n-C38 skeletons, saturated n-C37 and n-C38 methyl, ethyl, and mid-chain ketones, C37 and C38 mid-chain 2,5-di-n-alkylthiophenes, C37 and C38 1,2-di-n-alkylbenzenes, and C37 and C38 n-alkanes. With increasing thermal maturation, three forms of the n-C37 and n-C38 skeletons are relatively stable (saturated hydrocarbons, 1,2-di-n-alkylbenzenes and saturated ketones), whereas the S-and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C37 and n-C38 skeleton can be expected as well as the corresponding hydrocarbons. Copyright ?? 1997 Elsevier Science Ltd.

  6. Sulphur and oxygen sequestration of n-C{sub 37} and n-C{sub 38} unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

    Energy Technology Data Exchange (ETDEWEB)

    Koopmans, M.P.; De Leeuw, J.W.; Damste, J.S.S. [Netherlands Institute for Sea Research (NIOZ), Den Burg (Netherlands)] [and others

    1997-06-01

    Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature (R{sub o} = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330{degrees}C for 72 h to study the diagenetic fate of n-C{sub 37} and n-C{sub 38} di- and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260{degrees}C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S- and O-bound n-C{sub 37} and n-C{sub 38} skeletons, saturated n-C{sub 37} and n-C{sub 38} methyl, ethyl, and mid-chain ketones, C{sub 37} and C{sub 38} mid-chain 2,5-di-n-alkylthiophenes, C{sub 37} and C{sub 38} 1,2-di-n-alkylbenzenes, and C{sub 37} and C{sub 38} n-alkanes. With increasing thermal maturation, three forms of the n-C{sub 37} and n-C{sub 38} skeletons are relatively stable (saturated hydrocarbons, 1,2-di-n-alkylbenzenes and saturated ketones), whereas the S- and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C{sub 37} and n-C{sub 38} skeleton can be expected as well as the corresponding hydrocarbons. 58 refs., 8 figs., 2 tabs.

  7. Sulphur and oxygen sequestration of n-C 37 and n-C 38 unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

    Science.gov (United States)

    Koopmans, Martin P.; Schaeffer-Reiss, Christine; de Leeuw, Jan W.; Lewan, Michael D.; Maxwell, James R.; Schaeffer, Philippe; Sinninghe Damsté, Jaap S.

    1997-06-01

    Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature ( Ro = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330°C for 72 h to study the diagenetic fate of n-C 37 and n-C 38 di- and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260°C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S- and O-bound n-C 37 and n-C 38 skeletons, saturated n-C 37 and n-C38 methyl, ethyl, and mid-chain ketones, C 37 and C 38 mid-chain 2,5-di- n-alkylthiophenes, C 37 and C 38 1,2-di- n-alkylbenzenes, and C 37 and C 38n-alkanes. With increasing thermal maturation, three forms of the n-C 37 and n-C 38 skeletons are relatively stable (saturated hydrocarbons, 1,2-di- n-alkylbenzenes and saturated ketones), whereas the S- and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C 37 and n-C 38 skeleton can be expected as well as the corresponding hydrocarbons.

  8. Simulation thermique de l'évolution diagénétique des kérogènes : étude par résonance paramagnétique électronique Thermal Simulation of the Diagenetic Evolution of Kerogens: Electron Paramagnetic Resonance Analysis

    Directory of Open Access Journals (Sweden)

    Villey M.

    2006-11-01

    Full Text Available Dans cet article sont exposés les résultats obtenus en résonance paramagnétique électronique (RPE sur des séries chauffées en laboratoire, d'échantillons de kérogènes, illustrant les trois lignées évolutives. L'évolution de ces kérgènes est caractérisée par la susceptibilité paramagnétique, la largeur et la forme de la raie RPE et le facteur de décomposition spectrale g. Ces résultats sont, d'une part comparés à ceux obtenus (sur les mêmes échantillons en microscopie électronique à haute résolution, en spectroscopie infra-rouge, en analyse thermique et élémentaire, d'autre part confrontés aux données RPE de kérogènes différents précédemment étudiés. Enfin, le modèle d'évolution d'un carbonisat proposé par la microscopie électronique est ici complété. This article describes the results obtained by electron paramagnetic resonance (EPR analysis of heated series of kerogen samples in the laboratory to illustrate three evolutive lines. The evolution of these kerogens is characterized by paramagnet susceptibility, the width and shape of the EPR line and the spectral decomposition factor g. These results are compared with those obtained (with the same samples by high-resolution electron microscopy, infrared spectroscopy and thermal and elemental analysis. They are also compared with EPR data from previous kerogen analyses. The evolution model of a carbonizate proposed by electron microscopy is completed here.

  9. Cementation of kerogen-rich marls by alkaline fluids released during weathering of thermally metamorphosed marly sediments. Part II: Organic matter evolution, magnetic susceptibility and metals (Ti, Cr, Fe) at the Khushaym Matruk natural analogue (Central Jordan)

    International Nuclear Information System (INIS)

    Elie, M.; Techer, I.; Trotignon, L.; Khoury, H.; Salameh, E.; Vandamme, D.; Boulvais, P.; Fourcade, S.

    2007-01-01

    Spontaneous combustion, less than 1 Ma ago, affected a 60-m thick sediment pile of bio-micrite at the Khushaym Matruck site (Jordan). The present study shows that three retrograde alteration stages occurred: weathering, thermal stress and oxidative alkaline perturbation. μ-FT-i.r. spectra of isolated kerogens and oxygen index of whole rocks indicate that oxidation of organic matter occurred down to similar to 10 m beneath the metamorphosed zone at Khushaym Matruck. The occurrence of the oxidative weathering bacterially mediated, as suggested by the mass chromatograms of saturated hydrocarbons, can explain high Rock-Eval T max values and low petroliferous potential measured along the sedimentary pile. On the other hand, the thermal extent of combustion events was limited to the first 2 m from the contact. The mean reflectance of 0.20-0.24% and porosity of ca. 50% of the grey clayey bio-micrites indicate that organic matter was very immature and sediments were unconsolidated at the time of the combustion event. Using mineralogy, microscopic analyses of vegetable debris and magnetic susceptibility, a suite of characteristic points corresponding to the thermal imprint can be assessed: (i) x = 0 m, T similar to 1000 degrees C, (ii) x 1 m, T similar to 350 degrees C, (iii) x = 2 m, T similar to 150 degrees C and (iv) x ≥ ∼ 8 m, T similar to 30 degrees C. Paleo-circulation of meteoric groundwater in the 'cement-marbles' generated high-pH fluids that have circulated via fractures and through the matrix porosity of the underlying bio-micrites but have also induced alkaline hydrolysis and oxidative attack of the organic matter. The polysaccharide/lignin ratio derived from mu-FT-i.r. analyses shows that the delignification of vegetable debris and degradation of polysaccharides progressively decline in the indurated zone, which indicates a decrease in the pH of migrating solutions. The latter, also severely oxidized organic matter at 2. 10 and 3.05 m as revealed by the

  10. Analysis of the kerogen of oil shales

    Energy Technology Data Exchange (ETDEWEB)

    Quass, F W; Down, A L

    1939-01-01

    Comments are given on the method developed by F. W. Quass for reducing the amount of mineral matter present in certain coals and oil shales (torbanites). The method consisted of grinding oil shale with water in a porcelain ball mill in the presence of oil. The oil formed a paste with the carbonaceous material, and a greater portion of the mineral matter remained suspended in the water and was separated. Ultimate analyses of the enriched samples indicated that the percent of carbon was higher, the percent of hydrogen and oxygen was lower, and the ratio of carbon to hydrogen and carbon to oxygen increased in the enriched samples.

  11. Représentation chimique de la structure des kérogènes et des asphaltènes en fonction de leur origine et de leur degré d'évolution Chemical Modeling of the Structure of Kerogens and Asphaltenes As a Function of Their Origin and Evolution Stage

    Directory of Open Access Journals (Sweden)

    Behar F.

    2006-11-01

    Full Text Available Dans cet article nous proposons des modèles de structures chimiques de kérogènes et d'asphaltènes de roche. Nous avons choisi de représenter les kérogènes appartenant aux trois types classiques de matières organiques aux stades d'évolution suivants : - début de la diagenèse sensu-stricto; - début de la catagenèse (formation de l'huile; - fin de la catagenèse (formation du gaz. Les asphaltènes représentés correspondent à la phase de formation de l'huile. Nous avons tenu compte des données d'analyse obtenues sur des échantillons naturels : analyse élémentaire, microscopie électronique, RMN 13C, thermogravimétrie, analyse fonctionnelle, dégradation par pyrolyse. Afin d'obtenir une représentation chimique ayant une valeur statistique suffisante, nous avons choisi une masse moléculaire de 25 000 environ, identique pour les trois kérogènes au début de la diagenèse, et une masse de 8000 environ pour les asphaltènes associés. Nous avons ensuite dessiné à l'échelle moléculaire les structures correspondantes. This paper proposes models for the chemical structures of kerogens and asphaltenes from rocks. The kerogens belonging to the three conventional types of organic matter are represented in the following stages of evolution: (1 beginning of diagenesis sensu stricto,(2 beginning of catagenesis (formation of oil, and (3 end of catagenesis (formation of gas. The asphaltenes represented here correspond to the phase of oil formation. Models are based on analytical data obtained on natural samples, i. e. elemental analysis, electron microscopy, 13C NMR, thermogravimetry, functional analysis and pyrolysis. To get enough statistical value for the chemical modelling, a same molecular mass of about 25 000 was chosen for the three kerogens at the beginning of diagenesis. A molecular mass of about 8000 was chosen for the related asphaltenes. The chemical structures were then constructed at the molecular scale.

  12. Etude par Spectrométrie de masse de la décomposition thermique sous vide de kérogènes appartenant à deux lignées évolutives distinctes Mass Spectrometry Investigation of the Vaccum Thermal Decomposition of Kerogens from Two Distinct Evolutive Lines

    Directory of Open Access Journals (Sweden)

    Souron C.

    2006-11-01

    Full Text Available Le but de cette étude est la connaissance qualitative et quantitative des composés dégagés lors de la décomposition thermique sous vide de quelques échantillons de kérogènes appartenant à deux lignées différentes. La principale technique utilisée est la spectrométrie de masse, appuyée sur des études préliminaires par thermogravi métrie et analyse élémentaire. Une adaptation particulière de l'appareillage et une mise au point de la méthode d'étalonnage permettent de doser les quatre composés minéraux les plus abondants et de donner une représentation des composés organiques. Cette étude montre que les composés formés au cours du chauffage comprennent, pour tous les kérogènes étudiés, des composés oxygénés et soufrés (CO, H2O, SH2, SOJ libérés principalement dans l'intervalle de température 200-400° C, et des composés hydrocarbonés, plus abondants, dans l'intervalle 300-500° C. On commente dans cet article l'origine supposée de ces composés; la formation de S02 au cours de la pyrolyse est particulièrement mal connue. On remarque que le rapport H2O/C02 peut être un critère de distinction des deux lignées de kérogènes étudiés. La distinction observée sur les produits hydrocarbonés nécessitera des recherches complémentaires pour être utilisée avec plus de sûreté. The aim of this investigation is to obtain a qualitative and quantitative understanding of the compounds given off during the vacuum thermal decomposition of several kerogen samples from two different lines. The main technique used is mass spectrometry, based on prior investigations by thermogravimetry and element onalysis. The equipment was specially adapted and a calibration method was developed for titrating the four most abundant minerai compounds and for representing the organic compounds. This investigation shows that the compounds formed during heating include, for oil the kerogens examined, oxygen-and sulfur

  13. Contribution de la géochimie organique à une esquisse paléoécologique des shistes bitumeux du Toarcien de l'Est du bassin de Paris. Etude de la matière organique insoluble (kérogènes Contribution of Organic Geochemistry to a Paleoecological Sketch of Toarcian Oil Shales in the Eastern Paris Basin. Analysis of Insoluble Organic Matter (Kerogens

    Directory of Open Access Journals (Sweden)

    Huc A. Y.

    2006-11-01

    Full Text Available L'étude des kérogènes des schistes cartons du Toarcien inférieur du bassin de Paris au niveau de l'affleurement oriental (du Luxembourg au Morvan confirme l'homogénéité globale de la matière organique dans cette formation. Il s'agit d'une matière organique d'origine marine autochtone. Cependant l'existence de fluctuations (de faible amplitude répondant à une logique géographique conforte la notion de provinces géochimiques dans ce bassin, telle qu'elle avait été définie à l'occasion de l'étude de la fraction soluble (CHCIsJ. La distinction entre une province nord (Lorraine et une province sud (Avallonais,Haute-Saône, Haute-Marne pourrait être imputable à un apport détritique plus sensible dans la partie septentrionale du bassin et/ou aux conditions de milieu ayant régné au moment du dépôt. The present study of kerogens isolated from early Toorcion shales sompled on the eastern out-trop of the Paris Basin (from Luxembourg to Morvan verifies the overall homogeneity of the organic matter in this formation. This organic matter is of autoch thonous marine origin. However, the occurrence of small variations related to different geogrophical locations reinforces the concept of geochemical provinces in this basin as revealed by a previous analysis of the chloroform extracts. Differences between a northern province (Lorraine and a southern province (Avallon area, Haute-Saône, Haute-Marne could be interpreted as the consequence of a more important detrital input in the northern part of the basin and/or of different environmental conditions at the time of deposition.

  14. Geochemical study of the insoluble organic material (kerogen) in the Oklo uranium ore and the associated Francevillian schists

    International Nuclear Information System (INIS)

    Vandenbroucke, M.; Rouzaud, J.N.; Oberlin, A.

    1978-01-01

    The purpose of this study was to describe the organic material associated with uranium ore and ore transformations undergone by it, in terms of the following problems: (1) In the natural reactor zones, evolution of the organic material in the core and as a function of the distance away from it; (2) Comparison of organic materials from a rich and a poor ore; (3) Intercomparison of organic materials in the dispersed and concentrated state; (4) Comparison of organic materials in the uranium ore zones and in the adjacent non-mineralized Francevillian. The organic material from the reactor core could not be isolated by the normal techniques of treatment with acid. It is found in other cases that the organic material is oxidized in the uranium-bearing sediments and that the nearer to the reaction zone, the greater the oxidation, irrespective of the state of dispersion of the organic material in the rock. The uranium content does not affect this phenomenon, which is attributed to the action of the water raised to a high temperature in the vicinity of the reaction zones. On the basis of the present distribution of organic material and uranium the authors suggest a pattern for the formation of the deposit that would take into account localization of the ore in the sandstones and the part played by organic material in the accumulation process. (author)

  15. Molecular analysis of sulphur-rich brown coals by flash pyrolysis-gas chromatography-mass spectrometry: The type III-S kerogen

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Las Heras, F.X.C. de; Leeuw, J.W. de

    1992-01-01

    The molecular composition of five brown coals from three different basins (Maestrazgo, Mequinenza and Rubielos) in Spain was investigated by flash pyrolysis-gas chromatography and flash pyrolysis-gas chromatography-mass spectrometry. In these techniques, the macromolecular material is thermally

  16. Characterization of insoluble organic matter of the Lokpanta oil ...

    African Journals Online (AJOL)

    Conventional infrared (IR) spectroscopy was used to get quantitative information on the structure of the isolated kerogen of the Lokpanta oil shales in the Anambra basin. The kerogen was extracted from six shale samples collected from different geographical locations in the basin. Only about 1 to 14% of the kerogen ...

  17. Cementation of kerogen-rich marls by alkaline fluids released during weathering of thermally metamorphosed marly sediments. Part I: Isotopic (C,O) study of the Khushaym Matruk natural analogue (central Jordan)

    International Nuclear Information System (INIS)

    Fourcade, Serge; Trotignon, Laurent; Boulvais, Philippe; Techer, Isabelle; Elie, Marcel; Vandamme, Didier; Salameh, Elias; Khoury, Hani

    2007-01-01

    The Khushaym Matruk site in central Jordan may represent a natural analogue depicting the interaction of alkaline solutions with a clayey sedimentary formation or with clay-rich confining barriers at the interface with concrete structures in waste disposal sites. In this locality, past spontaneous combustion of organic matter in a clayey biomicritic formation produced a ca. 60 m-thick layer of cement-marble containing some of the high-temperature phases usually found in industrial cements (e.g., spurrite, brucite, and Ca-aluminate). A vertical cross-section of the underlying sediments was used in order to study the interaction between cement-marbles and neighbouring clayey limestones under weathering conditions. A thermodynamic approach of the alteration parageneses (calcite-jennite-afwillite-brucite and CSH phases) in the cement-marbles constrains the interacting solutions to have had pH-values between 10.5 and 12. Over 3 m, the sediments located beneath the metamorphic unit were compacted and underwent carbonation. They display large C and O isotopic variations with respect to 'pristine' sediments from the bottom of the section. Low δ 13 C-values down to -31.4 per mille /PDB show the contribution of CO 2 derived from the oxidization of organic matter and from the atmosphere to the intense carbonation process affecting that particular sedimentary level. The size of the C isotopic anomalies, their geometrical extent and their coincidence with the variations of other markers like the Zn content, the structure of organic matter, the mineralogical composition, all argue that the carbonation process was induced by the percolation of high pH solutions which derived from the alteration of cement-marbles. The temperature of the carbonation process remains conjectural and some post-formation O isotopic reequilibration likely affected the newly-formed carbonate. Carbonation induced a considerable porosity reduction, both in fractures and matrixes. The Khushaym Matruk site may have some bearing to the early life of a repository site, when water saturation of the geological formations hosting the concrete structures is incomplete, enabling simultaneous diffusion of alkaline waters and gaseous CO 2 in the near field

  18. Methane adsorption on the surface of a model of shale: A density functional theory study

    International Nuclear Information System (INIS)

    Zhu, Yuan-qiang; Su, Hong; Jing, Ya; Guo, Jianchun; Tang, Junlei

    2016-01-01

    Highlights: • The adsorption of methane on kerogen was investigated by DFT method with D3 dispersion correction. • Methane prefers to be adsorbed on the sites directly above the carbon atoms of the kerogen. • The interaction energy with BSSE corrections is around 14 kJ mol −1 . • RDG gradient isosurface depicted the van der Waals interactions between methane and kerogen. • The adsorption of methane on kerogen slightly depends upon the adsorption sites on kerogen as well as the orientations of methane. - Abstract: As a model of shale, one part of polycyclic aromatic ring was used to represent the kerogen surface with the structural heterogeneity. The adsorption mechanisms of methane on the surface of the kerogen were investigated by M06-2× functional with D3 dispersion correction. Nine stable adsorption sites and the orientations of methane (CH 4 ) on the surface of the kerogen were systematically considered. Information from different methods lead to the same conclusion that methane prefers to be adsorbed on the sites directly above the carbon atoms of the kerogen rather than above the center of the six-membered rings. The interactions between methane and the surface of the kerogen are the van der Waals interactions. The interaction energies with the basis set superposition error (BSSE) corrections are around 14 kJ mol −1 at the M06-2×-D3/Jun-cc-pVDZ level. The RDG scatter graphs and the RDG gradient isosurface further illustrate that the interactions between methane and the surface of the kerogen belong to the van der Waals interactions. The weak interactions indicate that the adsorption of methane on the surface of the kerogen is physical adsorption and it slightly depends upon the adsorption sites on kerogen as well as the orientations of methane. These results are helpful for the understanding of the microcosmic mechanism of methane–shale interactions and for the exploitation of shale gas.

  19. Petroleum under the microscope

    Energy Technology Data Exchange (ETDEWEB)

    Scott, J

    1920-01-01

    Kerogen may have been formed by a gradual change of vegetable matter into kerogen globules that were intimately mixed with clay and other minerals. As these globules accumulated, the more volatile constituents were eliminated, leaving the remainder as a heavy residue. This process is termed inspissation.

  20. The organic petrology and thermal maturity of Lower Carboniferous and Upper Devonian source rocks in the Liard Basin, at Jackfish Gap-Yohin Ridge and North Beaver River, northern Canada: Implications for hydrocarbon exploration

    Energy Technology Data Exchange (ETDEWEB)

    Potter, J. (Univ. of Newcastle-upon-Tyne (United Kingdom)); Richards, B.C.; Goodarzi, G. (Geological Survey, Calgary, Alberta (Canada))

    Basinal shales of the Besa River Fm. have TOC values ranging from 1 to 4% and contain abundant type II, dominantly amorphous, kerogen of marine origin. Shales in the Yohin, Clausen, Prophet, and Golata Formations are of mixed maring and terrestrial origins and yield TOC values of 1 to 3%. Kerogen in the Golata and Yohin Formations are dominated by terrestrial components, while the Clausen and Flett kerogen comprises marine liptinites and bitumens. Kerogen from the deltaic Mattson shales at Jackfish Gap are types II and III, having mixed marine and terrestrial origins consistent with shallow, nearshore, subtidal environments. The coals are sapropelic and probably lacustrine in origin. Algal laminites associated with coals in the Upper Mattson have >10% TOC values, while non-laminite shales contain between 2 and 5% TOC. Comparable measured and calculated vitrinite reflectance data indicate that kerogen in the Lower Carboniferous at Jackfish Gap is mature. Kerogen in correlative formations in the subsurface at North Beaver River is more marine. Vitrinites are rate and oxidized, but four populations of bitumens are distinguished on the basis of relative reflectivity and morphological or petrophysical associations. Types A and B bitumens are primary and by-products of hydrocarbon generation from type II (algal and amorphous) kerogens. Correlations between depth and reflectance of bitumens A and B are very good. Vitrinite reflectance data calculated from bitumen reflectance measurements for the Besa River, Prophet, and Golata indicate that they are potential sources of catagenic gas. The Mattson kerogen is mature, oil and gas-prone.

  1. Pétrographie du kérogène dans le Paléozoïque inférieur : méthode de préparation et exemple d'application Petrography of Lower-Paleozoic Kerogen: Preparation Method and Applied Example

    Directory of Open Access Journals (Sweden)

    Bertrand R.

    2006-11-01

    Full Text Available Une nouvelle méthode de préparation des matières organiques dispersées, destinées à être étudiées au microscope, est décrite et proposée. Le montage de la matière organique est fait par des lames de verre. Il permet de faire tous les types d'observations microscopiques (lumière transmise, réfléchie ou fluorescente sur une même préparation. Ses avantages sur la méthode classique d'imprégnation sur des briquettes sont illustrés par un exemple dans la séquence ordovicienne et siluro-dévonienne de l'île d'Anticosti et de l'est des Appalaches québécoises au Canada. This paper presents a new method to be used in the preparation of dispersed organic matter for microscopic studies. The organic matter is spread on a glass slide in order to permit all types of microscopic observation (transmitted, reflected or fluorescent light on a single mount. An example of its application, taken from the Ordovician and Siluro-Devonian sequence of Anticosti Island and Eastern Appalachians of Quebec, shows the advantages of this new method over the traditional plugmethod.

  2. Methane adsorption on the surface of a model of shale: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Yuan-qiang, E-mail: zhuline518@163.com [School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500 (China); State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500 (China); Su, Hong; Jing, Ya [School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500 (China); Guo, Jianchun [State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500 (China); Tang, Junlei [School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500 (China)

    2016-11-30

    Highlights: • The adsorption of methane on kerogen was investigated by DFT method with D3 dispersion correction. • Methane prefers to be adsorbed on the sites directly above the carbon atoms of the kerogen. • The interaction energy with BSSE corrections is around 14 kJ mol{sup −1}. • RDG gradient isosurface depicted the van der Waals interactions between methane and kerogen. • The adsorption of methane on kerogen slightly depends upon the adsorption sites on kerogen as well as the orientations of methane. - Abstract: As a model of shale, one part of polycyclic aromatic ring was used to represent the kerogen surface with the structural heterogeneity. The adsorption mechanisms of methane on the surface of the kerogen were investigated by M06-2× functional with D3 dispersion correction. Nine stable adsorption sites and the orientations of methane (CH{sub 4}) on the surface of the kerogen were systematically considered. Information from different methods lead to the same conclusion that methane prefers to be adsorbed on the sites directly above the carbon atoms of the kerogen rather than above the center of the six-membered rings. The interactions between methane and the surface of the kerogen are the van der Waals interactions. The interaction energies with the basis set superposition error (BSSE) corrections are around 14 kJ mol{sup −1} at the M06-2×-D3/Jun-cc-pVDZ level. The RDG scatter graphs and the RDG gradient isosurface further illustrate that the interactions between methane and the surface of the kerogen belong to the van der Waals interactions. The weak interactions indicate that the adsorption of methane on the surface of the kerogen is physical adsorption and it slightly depends upon the adsorption sites on kerogen as well as the orientations of methane. These results are helpful for the understanding of the microcosmic mechanism of methane–shale interactions and for the exploitation of shale gas.

  3. New Extraterrestrial Signature of the Insoluble Organic Matter of the Orgueil, Murchison and Tagish Lake Meteorites as Revealed by Electron Paramagnetic Resonance

    Science.gov (United States)

    Binet, L.; Gourier, D.; Derenne, S.; Robert, F.; Ciofini, I.

    2003-03-01

    EPR of the insoluble organic matter (IOM) of three chondrites revealed heterogeneously spread radicals including diradicaloids. These features not observed in terrestrial kerogens appear as an extraterrestrial signature of the chondritic IOM.

  4. A geochemical and petrographical characterization of organic matter in the Jurassic Mikulov Marls from the Czech Republic

    Czech Academy of Sciences Publication Activity Database

    Geršlová, E.; Opletal, V.; Sýkorová, Ivana; Sedláková, I.; Geršl, M.

    141-142, MAR 1 (2015), s. 42-50 ISSN 0166-5162 Institutional support: RVO:67985891 Keywords : Mikulov Marls * kerogen type * thermal maturity Subject RIV: DB - Geology ; Mineralogy Impact factor: 3.294, year: 2015

  5. Shale oil. I. Genesis of oil shales and its relation to petroleum and other fuels

    Energy Technology Data Exchange (ETDEWEB)

    McKee, R H; Manning, P D.V.

    1927-01-01

    Oil-shale kerogen originated from resinous vegetation residues of past eras, whereas well petroleum was formed from oil shales by pressure and mild heat. Petroleum migrated to its present reservoir from neighboring oil-shale deposits, leaving a residue of black bituminous shales. The high carbon dioxide content of gases present in petroleum wells originated from kerogen, as it gives off carbon dioxide gas before producing soluble oil or bitumen.

  6. Getting Over the Barrel- Achieving Independence from Foreign Oil in 2018

    Science.gov (United States)

    2009-02-03

    material called kerogen. Kerogen can be converted into oil via heating in the chemical process of pyrolysis .44 Depending on the richness of oil shale, it...vegetable oil, animal fat, corn , soybeans, jatropha seed oil, palm oil, switch grass and even algae. Biofuel production techniques and technologies...vary widely based on the input source – sugar-based, starch-based or oil-based. This document only examines corn -based ethanol production. The other

  7. Composition and structure of natural organic matter through advanced nuclear magnetic resonance techniques

    Directory of Open Access Journals (Sweden)

    Dainan Zhang

    2017-02-01

    Full Text Available Abstract Natural organic matter (NOM plays important roles in biological, chemical, and physical processes within the terrestrial and aquatic ecosystem. Despite its importance, a clear and exhaustive knowledge on NOM chemistry still lacks. Aiming to prove that advanced solid-state 13C nuclear magnetic resonance (NMR techniques may contribute to fill such a gap, in this paper we reported relevant examples of its applicability to NOM components, such as biomass, deposition material, sediments, and kerogen samples. It is found that nonhydrolyzable organic carbons (NHC, chars, and polymethylene carbons are important in the investigated samples. The structure of each of the NHC fractions is similar to that of kerogens, highlighting the importance of selective preservation of NOM to the kerogen origin in the investigated aquatic ecosystems. Moreover, during the artificial maturation experiments of kerogen, the chemical and structural characteristics such as protonated aromatic, nonprotonated carbons, and aromatic cluster size play important roles in the origin and variation of nanoporosity during kerogen maturation. Graphical abstract NMR parameters of thermally stimulated kerogens

  8. Hydrocarbons and oxygen compounds in the bitumens of kukersite oil shales

    Energy Technology Data Exchange (ETDEWEB)

    Pais, R; Klesment, I; Pobul, L

    1979-01-01

    This is a continuation of an earlier work which described commercial batches of kukersite in terms of oxidative kerogen destruction. The low concentration of bitumen in the kerogen and its group composition indicate that this bitumen is syngenetic. The authors studied the way in which the bitumen and kerogen are structurally connected. They also analyzed four commercial batches of kukersite and asphaltite, the organic-rich dark-colored layer found in the middle of the kukersite strate. Whereas American studies of Colorado shales containing 10-20% bitumen from organic matter have indicated, based on the identical structures of the bitumen and kerogen that there is a genetic relationship between them, the present study rarely found such structural elements in the bitumen and kerogen. The kukersite contained little bitumen--0.7% of the total organic matter. The authors believed that the different composition of the bitumen and kerogen does not prove that they are epigenetic. Kukersite also fails to follow the rule that the paraffins of ancient shales have KHapprox.1 and carbon chains shorter than C/sub 22/.

  9. Dike intrusions into bituminous coal, Illinois Basin: H, C, N, O isotopic responses to rapid and brief heating

    Science.gov (United States)

    Schimmelmann, A.; Mastalerz, Maria; Gao, L.; Sauer, P.E.; Topalov, K.

    2009-01-01

    Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., 2H/1H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., {single bond}OH, {single bond}COOH, {single bond}NH2). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ???2.5 to ???3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong ??13Ckerogen vs. ??15Nkerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back

  10. Kinetics of the generation of the petroleum: Principles and application in the Colombian basins

    International Nuclear Information System (INIS)

    Goncalves, F T T; Garcia, D F; Penteado, H L B; Giraldo, B N; Bedregal, R P; Gomez

    2001-01-01

    Most of the mathematical models that describe the conversion of kerogen into petroleum are based on the formulations of first-order kinetics. Although the application of such models requires the knowledge of the kinetic parameters (activation energies and frequency factor) of the kerogen, the usual practice in basin modeling studies is to use kinetic data of standard kerogen types (I, II or III) when measured data are not available. In this study, Rock-Eval pyrolysis under different heating rates and numerical optimization techniques were used to determine the kinetic parameters of cretaceous and tertiary source rocks of the upper Magdalena and llanos basins. The obtained kinetic parameters revealed a significant variability, which appears to be unrelated to the kerogen type classification based on hydrogen and oxygen indices. Modeling exercises under a constant heating rate (1.25 degrades C/M.y., 274.5K/M.y.) using the measured kinetic data indicates that kerogen conversion of organic facies with distinct kinetic parameters may be out of phase by 20-30M.y. therefore, petroleum generation and expulsion history might be longer and more complex than if the kinetic behavior of these rocks was considered homogeneous. These differences are critical in defining the timing between petroleum generations a trap formation/destruction, particularly in the case of the Colombian sedimentary basins, characterized by a highly complex tectonic evolution

  11. Chemistry of the pyrolysis of torbanite

    Energy Technology Data Exchange (ETDEWEB)

    Cane, R F

    1948-01-01

    Vacuum heating of torbanite was carried out to establish the lowest temperature at which decomposition could be detected. Slight vapors appeared at 131/sup 0/C., vapor of pH2 from 200 to 275/sup 0/C, and oil and H/sub 2/S from 327 to 336/sup 0/C. A quantity of bitumen was prepared by heating rich torbanite for extended periods at about 300/sup 0/C. The torbanite was then extracted with benzene and a black semisolid residue was obtained. The bitumen was distilled at atmospheric pressure and under vacuum at temperatures of 350 to 400/sup 0/C. As the kerogen was heated, slight oxidation took place followed by initial decomposition, which caused loss of sulfur, hydrogen, and oxygen, and the disappearance of some cross-linkages. Kerogen decomposition may be represented by: kerogen ..-->.. bitumen ..-->.. oil ..-->.. naphtha + gas + coke. The decomposition appeared to be a cracking reaction, and the formation of bitumen was not due entirely to depolymerization, as the carbon-hydrogen ratio of the reactants and products remain unchanged in a true depolymerization. In the original kerogen, the molecules consist of many units, each containing one or more cyclic nuclei possessing long sidechains. The occurrence of paraffin wax in the crude oil leaves no doubt that long-chain paraffin structures are present, as such, in the kerogen molecule.

  12. Biogeochemical and micropaleontological study of black chert, Sete Lagoas Formation, Bambui Group (Late Proterozoic), Sao Gabriel (GO), Brazil

    International Nuclear Information System (INIS)

    Subacius, S.M.R.

    1985-01-01

    The biogeochemical study of amorphous and structured organic matter (OM) in two samples of thinly laminated black cherts (SG-1 and SG-2) from Sete Lagoas Formation, State of Goias, Brazil, is presented. The spectra analysis of infra-red, electron paramagnetic resonance and isotope ratio of C-12 and C-13 shown that: the amorphous OM consists of a soluble fraction (SF) and a insoluble fraction (Kerogen), which only the latter is syngenetic; the allochthonous SF comes from several sources, mainly from Phanerozoic sediments and soil contamination; the SG-1 and SG-2 Kerogens have δ 13 C values (-27.2 per mille and - 29.2 per mille respectively), which suggest OM photosynthetized and submitted to a mild thermal hystory; although the preserved microbiota is dominated by allochthonous elements (colonial fragments) and planktonic forms, both Kerogens were derived for the most part from photo-autotrophic benthonic communities, probably responsible for the lamination in the original carbonate rock, both SG-1 and SG-2 Kerogens exhibits O/C and H/C ratios comparable to Proterozoic humic Kerogens (type IV); the preserved microflora represents a microbial community of the chert-algae facies typical of the Middle and upper Proterozoic; and the occurence of rare acritarchs (Kildinella spp.) in the microflora is biostratigraphically significant in that it suggests a Late Riphean or Vendian age (950-570 m.y.) for the Sete Lagoas Formation. (Author) [pt

  13. A chemical and thermodynamic model of oil generation in hydrocarbon source rocks

    Science.gov (United States)

    Helgeson, Harold C.; Richard, Laurent; McKenzie, William F.; Norton, Denis L.; Schmitt, Alexandra

    2009-02-01

    Thermodynamic calculations and Gibbs free energy minimization computer experiments strongly support the hypothesis that kerogen maturation and oil generation are inevitable consequences of oxidation/reduction disproportionation reactions caused by prograde metamorphism of hydrocarbon source rocks with increasing depth of burial.These experiments indicate that oxygen and hydrogen are conserved in the process.Accordingly, if water is stable and present in the source rock at temperatures ≳25 but ≲100 °C along a typical US Gulf Coast geotherm, immature (reduced) kerogen with a given atomic hydrogen to carbon ratio (H/C) melts incongruently with increasing temperature and depth of burial to produce a metastable equilibrium phase assemblage consisting of naphthenic/biomarker-rich crude oil, a type-II/III kerogen with an atomic hydrogen/carbon ratio (H/C) of ˜1, and water. Hence, this incongruent melting process promotes diagenetic reaction of detritus in the source rock to form authigenic mineral assemblages.However, in the water-absent region of the system CHO (which is extensive), any water initially present or subsequently entering the source rock is consumed by reaction with the most mature kerogen with the lowest H/C it encounters to form CO 2 gas and a new kerogen with higher H/C and O/C, both of which are in metastable equilibrium with one another.This hydrolytic disproportionation process progressively increases both the concentration of the solute in the aqueous phase, and the oil generation potential of the source rock; i.e., the new kerogen can then produce more crude oil.Petroleum is generated with increasing temperature and depth of burial of hydrocarbon source rocks in which water is not stable in the system CHO by a series of irreversible disproportionation reactions in which kerogens with higher (H/C)s melt incongruently to produce metastable equilibrium assemblages consisting of crude oil, CO 2 gas, and a more mature (oxidized) kerogen with a lower

  14. Effect of concentration of dispersed organic matter on optical maturity parameters. Interlaboratory results of the organic matter concentration working group of the ICCP

    Energy Technology Data Exchange (ETDEWEB)

    Mendonca Filho, J.G.; Kern, M.L.; Mendonca, J.O. [Palynofacies and Organic Facies Laboratory (LAFO), DEGL, IGEO, UFRJ, Cidade Universitaria, Rio de Janeiro (Brazil); Araujo, C.V.; Menezes, T.R.; Souza, I.V.A.F. [Petrobras R and D Center, Rio de Janeiro (Brazil); Borrego, A.G.; Suarez-Ruiz, I. [Instituto Nacional del Carbon, CSIC, Oviedo (Spain); Cook, A.; Ranasinghe, P. [Keiraville Konsultants Pty. Ltd, NSW (Australia); Flores, D. [University of Porto, Departamento de Geologia (Portugal); Hackley, P. [U.S. Geological Survey, MS 956 National Center Reston, VA (United States); Hower, J.C. [University of Kentucky, Center for Applied Energy Research, Lexington (United States); Kommeren, K. [Shell International Exploration and Production, Rijswijk (Netherlands); Kus, J. [Germany Federal Institute for Geosciences and Natural Resources in Geozentrum, Hannover (Germany); Mastalerz, M. [Indiana Geological Survey, Indiana University, Bloomington (United States); Newman, J. [Newman Energy Research Ltd, Christchurch (New Zealand); Ujiie, Y. [Graduate School of Science and Technology, Hirosaki University (Japan)

    2010-12-01

    The main objective of this work was to study the effect of the kerogen isolation procedures on maturity parameters of organic matter using optical microscopes. This work represents the results of the Organic Matter Concentration Working Group (OMCWG) of the International Committee for Coal and Organic Petrology (ICCP) during the years 2008 and 2009. Four samples have been analysed covering a range of maturity (low and moderate) and terrestrial and marine geological settings. The analyses comprise random vitrinite reflectance measured on both kerogen concentrate and whole rock mounts and fluorescence spectra taken on alginite. Eighteen participants from twelve laboratories from all over the world performed the analyses. Samples of continental settings contained enough vitrinite for participants to record around 50 measurements whereas fewer readings were taken on samples from marine setting. The scatter of results was also larger in the samples of marine origin. Similar vitrinite reflectance values were in general recorded in the whole rock and in the kerogen concentrate. The small deviations of the trend cannot be attributed to the acid treatment involved in kerogen isolation but to reasons related to components identification or to the difficulty to achieve a good polish of samples with high mineral matter content. In samples difficult to polish, vitrinite reflectance was measured on whole rock tended to be lower. The presence or absence of rock fabric affected the selection of the vitrinite population for measurement and this also had an influence in the average value reported and in the scatter of the results. Slightly lower standard deviations were reported for the analyses run on kerogen concentrates. Considering the spectral fluorescence results, it was observed that the {lambda}max presents a shift to higher wavelengths in the kerogen concentrate sample in comparison to the whole-rock sample, thus revealing an influence of preparation methods (acid treatment

  15. Importance of inorganic geochemical characteristics on assessment of shale gas potential in the Devonian Horn River Formation of western Canada

    Science.gov (United States)

    Hong, Sung Kyung; Shinn, Young Jae; Choi, Jiyoung; Lee, Hyun Suk

    2017-04-01

    The gas generation and storage potentials of shale has mostly been assessed by original TOC (TOCo) and original kerogen type. However, in the Horn River Formation, organic geochemical tools and analysis are barely sufficient for assessing the TOCo and original kerogen type because residual carbon contents represent up to 90% of TOC in shales. Major and trace elements are used as proxies for the bottom water oxygen level, for terrestrial sediment input and for productivity, which is related with variation of kerogen type. By using the inorganic geochemical proxies, we attempt to assess original kerogen type in shale gas formation and suggest its implication for HIo (original Hydrogen Index) estimation. The estimated HIo in this study allows us to calculate a reliable TOCo. These results provide new insights into the accurate estimation of the hydrocarbon potential of shale gas resources. The inorganic geochemical proxies indicate vertical variations of productivity (EX-SiO2 and Baauth), terrestrial sediment input (Al2O3, Zr, Hf, and Nb) and oxygen content in bottom water during deposition (Moauth, Uauth and Th/U), which represent the temporal changes in the mixing ratio between Type II and III kerogens. The Horn River Formation has different HIo values calculated from EX-SiO2 (biogenic origin) and it is ranked by HIo value in descending order: Evie and Muskwa members (500-700 mgHC/gTOC) > middle Otterpark Member (400-500 mgHC/gTOC) > upper Otterpark Member (300-400 mgHC/gTOC) > lower Otterpark Member (200 mgHC/gTOC). Based on the original kerogen type and TOCo, the gas generation and storage potentials of the Evie, middle Otterpark and Muskwa members are higher than those of other members. The source rock potential is excellent for the Evie Member with a remarkable difference between TOCo and measured TOC.

  16. 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.

  17. Evaluation of kinetic uncertainty in numerical models of petroleum generation

    Science.gov (United States)

    Peters, K.E.; Walters, C.C.; Mankiewicz, P.J.

    2006-01-01

    Oil-prone marine petroleum source rocks contain type I or type II kerogen having Rock-Eval pyrolysis hydrogen indices greater than 600 or 300-600 mg hydrocarbon/g total organic carbon (HI, mg HC/g TOC), respectively. Samples from 29 marine source rocks worldwide that contain mainly type II kerogen (HI = 230-786 mg HC/g TOC) were subjected to open-system programmed pyrolysis to determine the activation energy distributions for petroleum generation. Assuming a burial heating rate of 1??C/m.y. for each measured activation energy distribution, the calculated average temperature for 50% fractional conversion of the kerogen in the samples to petroleum is approximately 136 ?? 7??C, but the range spans about 30??C (???121-151??C). Fifty-two outcrop samples of thermally immature Jurassic Oxford Clay Formation were collected from five locations in the United Kingdom to determine the variations of kinetic response for one source rock unit. The samples contain mainly type I or type II kerogens (HI = 230-774 mg HC/g TOC). At a heating rate of 1??C/m.y., the calculated temperatures for 50% fractional conversion of the Oxford Clay kerogens to petroleum differ by as much as 23??C (127-150??C). The data indicate that kerogen type, as defined by hydrogen index, is not systematically linked to kinetic response, and that default kinetics for the thermal decomposition of type I or type II kerogen can introduce unacceptable errors into numerical simulations. Furthermore, custom kinetics based on one or a few samples may be inadequate to account for variations in organofacies within a source rock. We propose three methods to evaluate the uncertainty contributed by kerogen kinetics to numerical simulations: (1) use the average kinetic distribution for multiple samples of source rock and the standard deviation for each activation energy in that distribution; (2) use source rock kinetics determined at several locations to describe different parts of the study area; and (3) use a weighted

  18. Application of organic-geochemistry, coal-petrology and isotope-geochemistry to facies-analysis and hydrocarbon exploration in the NE-Paris Basin (Trias-Lias Luxemburg)

    International Nuclear Information System (INIS)

    Flekken, P.M.

    1978-01-01

    Triassic and Liassic sediments of NE-Paris Basin (Luxemburg) were investigated by organic-geochemical, coal petrographical and isotope-geochemical methods. The objective was to characterize the stratigraphic stages and to investigate the facies relations between them with a view to possible hydrocarbon exploration. The sediments contain an average of 3.1% organic carbon, 413 ug/g extractable organic matter (bitumen) and 0.65% insoluble, isolatable organic particles which constitute part of the kerogen. The non-isolatable kerogen is 2.4% of the whole rock. (orig./BR) [de

  19. Comparison of natural gases accumulated in Oligocene strata with hydrous pyrolysis gases from Menilite Shales of the Polish Outer Carpathians

    Science.gov (United States)

    Kotarba, M.J.; Curtis, John B.; Lewan, M.D.

    2009-01-01

    This study examined the molecular and isotopic compositions of gases generated from different kerogen types (i.e., Types I/II, II, IIS and III) in Menilite Shales by sequential hydrous pyrolysis experiments. The experiments were designed to simulate gas generation from source rocks at pre-oil-cracking thermal maturities. Initially, rock samples were heated in the presence of liquid water at 330 ??C for 72 h to simulate early gas generation dominated by the overall reaction of kerogen decomposition to bitumen. Generated gas and oil were quantitatively collected at the completion of the experiments and the reactor with its rock and water was resealed and heated at 355 ??C for 72 h. This condition simulates late petroleum generation in which the dominant overall reaction is bitumen decomposition to oil. This final heating equates to a cumulative thermal maturity of 1.6% Rr, which represents pre-oil-cracking conditions. In addition to the generated gases from these two experiments being characterized individually, they are also summed to characterize a cumulative gas product. These results are compared with natural gases produced from sandstone reservoirs within or directly overlying the Menilite Shales. The experimentally generated gases show no molecular compositions that are distinct for the different kerogen types, but on a total organic carbon (TOC) basis, oil prone kerogens (i.e., Types I/II, II and IIS) generate more hydrocarbon gas than gas prone Type III kerogen. Although the proportionality of methane to ethane in the experimental gases is lower than that observed in the natural gases, the proportionality of ethane to propane and i-butane to n-butane are similar to those observed for the natural gases. ??13C values of the experimentally generated methane, ethane and propane show distinctions among the kerogen types. This distinction is related to the ??13C of the original kerogen, with 13C enriched kerogen generating more 13C enriched hydrocarbon gases than

  20. Sorption of organic compounds to activated carbons. Evaluation of isotherm models

    NARCIS (Netherlands)

    Pikaar, I.; Koelmans, A.A.; Noort, van P.C.M.

    2006-01-01

    Sorption to 'hard carbon' (black carbon, coal, kerogen) in soils and sediments is of major importance for risk assessment of organic pollutants. We argue that activated carbon (AC) may be considered a model sorbent for hard carbon. Here, we evaluate six sorption models on a literature dataset for

  1. Biosphere in 3.5 Ga submarine hydrothermal system

    Energy Technology Data Exchange (ETDEWEB)

    Ueno, Yuichiro [Tokyo Univ. (Japan). Dept. of Earth Science and Astronomy

    2003-04-01

    Abundant organic matter (kerogen) was identified in {approx}3.5 Ga hydrothermal silica dikes from the North Pole area in the Pilbara craton, Western Australia. The silica dikes developed in the uppermost 1000 m of the ancient oceanic crust. Thus, they would have been deposited in the 3.5 Ga sub-seafloor hydrothermal system. The carbon and nitrogen isotopic compositions of the kerogen were analyzed in this study. Their highly {sup 13}C-depleted isotopic compositions ({delta}{sup 13}C = -38 to -33 per mille) strongly suggest that they are originally derived from biologically produced organic matter. The remarkable similarity of the {delta}{sup 13}C values between the kerogen and modern hydrothermal vent organisms may suggest that the kerogen was derived from chemoautotrophic organisms. This idea is also consistent with their nitrogen isotopic compositions ({delta}{sup 15}N = -4 to +4 per mille). The silica dikes consist mainly of fine-grained silica with minor pyrite and sphalerite. These mineral assemblages indicate that the silica dike was deposited from relatively low-temperature (probably less than 150degC) reducing hydrothermal fluid. Thus, anaerobic thermophilic/hyperthermophilic organisms could have survived in the hydrothermal fluid, which formed the silica dikes. Therefore, it is plausible that a chemoautotrophic-based biosphere (possibly methanogenesis) probably existed in the Early Archean sub-seafloor hydrothermal system. (author)

  2. Origin of oil shales

    Energy Technology Data Exchange (ETDEWEB)

    Weeks, W G

    1923-01-01

    The theory by Jones was questioned. Oil shales do not contain partly decomposed vegetable matter, and, where particles of vegetation are identified, they do not prove that kerogen was formed in its place. Some shales do contain free oil that can be extracted with solvents.

  3. Organic sulphur in macromolecular sedimentary organic matter. II. Analysis of distributions of sulphur-containing pyrolysis products using multivariate techniques

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Eglinton, T.I.; Pool, W.; Leeuw, J.W. de; Eijkel, G.; Boon, J.J.

    1992-01-01

    This study describes the analysis of sulphur-containing products from Curie-point pyrolysis (Py) of eighty-five samples (kerogens, bitumen, and petroleum asphaltenes and coals) using gas chromatography (GC) in combination with sulphur-selective detection. Peak areas of approximately forty individual

  4. Shale oil. II. Gases from oil shale

    Energy Technology Data Exchange (ETDEWEB)

    McKee, R H; Manning, P D.V.

    1927-01-01

    Oil shale (from Colorado) was pyrolyzed, and the gaseous products obtained were studied. The organic material present in oil shale contains carboxyl groups that lose carbon dioxide during pyrolysis before the formation of soluble bitumen. Nitrogen was evolved as ammonia in two stages and was not continuous. The first evolution was from loosely combined nitrogen structures, whereas the second was from more stable forms. No hydrocarbons were present as such in the kerogen. The gaseous products from oil-shale pyrolysis were similar to those obtained by distillation of colophony, amber, coal, and wood. This places the kerogen of the oil shale in the same series of carbonaceous substances as those from which coals are formed. Kerogen appeared to be decomposed in three steps; namely, to insoluble bitumen, to soluble bitumen, and to oil (gas evolution accompanied each step). Its low solubility and the character of its pyrolytic gas indicated that kerogen is largely a resinous residue from vegetation of the past era and may have been formed by the tranportation of coal-forming organic debris to inland salty lakes or carried to the sea by clay-laden waters. The salt water and the natural settling action precipitated the clay and organic matter in an almost homogeneous deposit. Oil shales have existed to the present time because they have not been subjected to high pressures or elevated temperatures that would have changed them to petroleum.

  5. Fossil fuel energy resources of Ethiopia | Ahmed | Bulletin of the ...

    African Journals Online (AJOL)

    The Ethiopian oil shales reach a maximum thickness of 60 m, and contain mixtures of algal, herbaceous and higher plant taxa. Type II and I kerogen dominated the studied oil shales. Pyrolysis data revealed that the Ethiopian oil shales are good to excellent source rocks types up to 34.5 % TOC values and up to 130 HC g/kg ...

  6. Development of Nuclear Renewable Oil Shale Systems for Flexible Electricity and Reduced Fossil Fuel Emissions

    Energy Technology Data Exchange (ETDEWEB)

    Daniel Curtis; Charles Forsberg; Humberto Garcia

    2015-05-01

    We propose the development of Nuclear Renewable Oil Shale Systems (NROSS) in northern Europe, China, and the western United States to provide large supplies of flexible, dispatchable, very-low-carbon electricity and fossil fuel production with reduced CO2 emissions. NROSS are a class of large hybrid energy systems in which base-load nuclear reactors provide the primary energy used to produce shale oil from kerogen deposits and simultaneously provide flexible, dispatchable, very-low-carbon electricity to the grid. Kerogen is solid organic matter trapped in sedimentary shale, and large reserves of this resource, called oil shale, are found in northern Europe, China, and the western United States. NROSS couples electricity generation and transportation fuel production in a single operation, reduces lifecycle carbon emissions from the fuel produced, improves revenue for the nuclear plant, and enables a major shift toward a very-low-carbon electricity grid. NROSS will require a significant development effort in the United States, where kerogen resources have never been developed on a large scale. In Europe, however, nuclear plants have been used for process heat delivery (district heating), and kerogen use is familiar in certain countries. Europe, China, and the United States all have the opportunity to use large scale NROSS development to enable major growth in renewable generation and either substantially reduce or eliminate their dependence on foreign fossil fuel supplies, accelerating their transitions to cleaner, more efficient, and more reliable energy systems.

  7. Molecular and elemental analyses of the carbonaceous matter in the gold and uranium bearing Vaal Reef carbon seams, Witwatersrand sequence

    International Nuclear Information System (INIS)

    Zumberge, J.E.; Sigleo, A.C.; Nagy, B.

    1978-01-01

    The thin Vaal Reef carbon seams consist of a complex, solid, and solvent insoluble, polymer-like substance, containing mainly hydrocarbons and some organic sulphur and oxygen compounds. These carbon seams are not pure carbon, e.g. graphite, and do not contain only hydrocarbons. According to modern terminology the Vaal Reef carbonaceous matter is most appropriately referred to as kerogen rather than carbon or thucholite. This kerogen is not the result of the polymerization of gaseous or liquid hydrocarbons, but rather of the polymerization of biochemicals from decayed, primitive Precambrian micro-organisms. These microbiota formed mats in which uranium minerals and gold became incorporated before burial under younger sediments. Organic geochemistry was first developed as a means to elucidate the nature and composition of petroleum and coal. Later it was successfully used in lunar sample, planetary surface, and meteorite studies as well as in investigations of kerogens in terrestrial sediments of various ages. Considering economic geology, organic geochemistry holds promise for elucidating the origin and helping in the exploration of carbonaceous ore deposits. The purpose of this report is to review some of the major current organic geochemical methods and to illustrate these by the analysis of the Vaal Reef kerogen. The samples were analysed by a directly connected high vacuum pyrolysis system-gas chromatograph-organic mass spectrometer. Additional analyses were performed by a combined scanning electron microscope-electron microprobe, by the techniques of electron paramagnetic resonance spectroscopy, and by neutron activation analysis

  8. Towards an understanding of the role of clay minerals in crude oil formation, migration and accumulation

    Science.gov (United States)

    Wu, Lin Mei; Zhou, Chun Hui; Keeling, John; Tong, Dong Shen; Yu, Wei Hua

    2012-12-01

    This article reviews progress in the understanding of the role of clay minerals in crude oil formation, migration and accumulation. Clay minerals are involved in the formation of kerogen, catalytic cracking of kerogen into petroleum hydrocarbon, the migration of crude oil, and the continued change to hydrocarbon composition in underground petroleum reservoirs. In kerogen formation, clay minerals act as catalysts and sorbents to immobilize organic matter through ligand exchange, hydrophobic interactions and cation bridges by the mechanisms of Maillard reactions, polyphenol theory, selective preservation and sorptive protection. Clay minerals also serve as catalysts in acid-catalyzed cracking of kerogen into petroleum hydrocarbon through Lewis and Brønsted acid sites on the clay surface. The amount and type of clay mineral affect the composition of the petroleum. Brønsted acidity of clay minerals is affected by the presence and state of interlayer water, and displacement of this water is a probable driver in crude oil migration from source rocks. During crude oil migration and accumulation in reservoirs, the composition of petroleum is continually modified by interaction with clay minerals. The clays continue to function as sorbents and catalysts even while they are being transformed by diagenetic processes. The detail of chemical interactions and reaction mechanisms between clay minerals and crude oil formation remains to be fully explained but promises to provide insights with broader application, including catalytic conversion of biomass as a source of sustainable energy into the future.

  9. Acoustic and Petrophysical Evolution of Organic-Rich Chalk Following Maturation Induced by Unconfined Pyrolysis

    Science.gov (United States)

    Shitrit, Omri; Hatzor, Yossef H.; Feinstein, Shimon; Vinegar, Harold J.

    2017-12-01

    Thermal maturation is known to influence the rock physics of organic-rich rocks. While most studies were performed on low-porosity organic-rich shales, here we examine the effect of thermal maturation on a high-porosity organic-rich chalk. We compare the physical properties of native state immature rock with the properties at two pyrolysis-simulated maturity levels: early-mature and over-mature. We further evaluate the applicability of results from unconfined pyrolysis experiments to naturally matured rock properties. Special attention is dedicated to the elastic properties of the organic phase and the influence of bitumen and kerogen contents. Rock physics is studied based on confined petrophysical measurements of porosity, density and permeability, and measurements of bedding-normal acoustic velocities at estimated field stresses. Geochemical parameters like total organic carbon (TOC), bitumen content and thermal maturation indicators are used to monitor variations in density and volume fraction of each phase. We find that porosity increases significantly upon pyrolysis and that P wave velocity decreases in accordance. Solids density versus TOC relationships indicate that the kerogen increases its density from 1.43 to 1.49 g/cc at the immature and early-mature stages to 2.98 g/cc at the over-mature stage. This density value is unusually high, although increase in S wave velocity and backscatter SEM images of the over-mature samples verify that the over-mature kerogen is significantly denser and stiffer. Using the petrophysical and acoustic properties, the elastic moduli of the rock are estimated by two Hashin-Shtrikman (HS)-based models: "HS + BAM" and "HS kerogen." The "HS + BAM" model is calibrated to the post-pyrolysis measurements to describe the mechanical effect of the unconfined pyrolysis on the rock. The absence of compaction in the pyrolysis process causes the post-pyrolysis samples to be extremely porous. The "HS kerogen" model, which simulates a

  10. Thermal-maturity limit for primary thermogenic-gas generation from humic coals as determined by hydrous pyrolysis

    Science.gov (United States)

    Lewan, Michael; Kotarba, M.J.

    2014-01-01

    Hydrous-pyrolysis experiments at 360°C (680°F) for 72 h were conducted on 53 humic coals representing ranks from lignite through anthracite to determine the upper maturity limit for hydrocarbon-gas generation from their kerogen and associated bitumen (i.e., primary gas generation). These experimental conditions are below those needed for oil cracking to ensure that generated gas was not derived from the decomposition of expelled oil generated from some of the coals (i.e., secondary gas generation). Experimental results showed that generation of hydrocarbon gas ends before a vitrinite reflectance of 2.0%. This reflectance is equivalent to Rock-Eval maximum-yield temperature and hydrogen indices (HIs) of 555°C (1031°F) and 35 mg/g total organic carbon (TOC), respectively. At these maturity levels, essentially no soluble bitumen is present in the coals before or after hydrous pyrolysis. The equivalent kerogen atomic H/C ratio is 0.50 at the primary gas-generation limit and indicates that no alkyl moieties are remaining to source hydrocarbon gases. The convergence of atomic H/C ratios of type-II and -I kerogen to this same value at a reflectance of indicates that the primary gas-generation limits for humic coal and type-III kerogen also apply to oil-prone kerogen. Although gas generation from source rocks does not exceed vitrinite reflectance values greater than , trapped hydrocarbon gases can remain stable at higher reflectance values. Distinguishing trapped gas from generated gas in hydrous-pyrolysis experiments is readily determined by of the hydrocarbon gases when a -depleted water is used in the experiments. Water serves as a source of hydrogen in hydrous pyrolysis and, as a result, the use of -depleted water is reflected in the generated gases but not pre-existing trapped gases.

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

    Science.gov (United States)

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

    2014-01-01

    The Utica-Lower Paleozoic Total Petroleum System (TPS) in the Appalachian Basin Province is named for the Upper Ordovician Utica Shale, which is the source rock, and for multiple lower Paleozoic sandstone and carbonate units that are the important reservoirs. The total organic carbon (TOC) values for the Utica Shale are usually greater than 1 weight percent. TOC values ranging from 2 to 3 weight percent outline a broad, northeast-trending area that extends across western and southern Pennsylvania, eastern Ohio, northern West Virginia, and southeastern New York. The Utica Shale is characterized by type II kerogen, which is a variety of kerogen that is typically prone to oil generation. Conondont color-alteration index (CAI) isograds, which are based on samples from the Upper Ordovician Trenton Limestone (or Group), indicate that a pod of mature Utica Shale source rocks occupies most of the TPS.

  12. ) Organic Facies Variations in the Middle Cretaceous Black Shales of the Abakaliki Fold Belt, South-East, Nigeria

    International Nuclear Information System (INIS)

    Ehinola, O. A.; Badejoko, T.A.; Ekweozor, C.M.; Adebowale, K. O.

    2003-01-01

    An assessment, based on organic facies characteristics, have been carried out on the middle Cretaceous black shales, in order to determine their hydrocarbon source potential, thermal maturity, and depositional environments. The methods employed include evaluation of organic carbon content, rockeval pyrolysis, extractable organic matter, maceral composition and biomarker distributions.Organic facies criteria such as TOC, HI, Tmax, liptinite content, SOMIFOC and SHC/AHC indicate that Albian to middle Cenomanian shales are could only generate gas. The late Cenomanian to early Turonian shales are characterized by Type I/II kerogen, mature and could generate both oil and characterized by Type III kerogen, immature and could generate gas with little oil. The biomarker distributions indicate immature to mature source rock, moderately biodegraded and with reduced marine environment prevailing during the deposition of the lack shales. The late Cenomanian to early Turonian black shales show the highest source-rock potential

  13. Ideas and perspectives: hydrothermally driven redistribution and sequestration of early Archaean biomass - the "hydrothermal pump hypothesis"

    Science.gov (United States)

    Duda, Jan-Peter; Thiel, Volker; Bauersachs, Thorsten; Mißbach, Helge; Reinhardt, Manuel; Schäfer, Nadine; Van Kranendonk, Martin J.; Reitner, Joachim

    2018-03-01

    Archaean hydrothermal chert veins commonly contain abundant organic carbon of uncertain origin (abiotic vs. biotic). In this study, we analysed kerogen contained in a hydrothermal chert vein from the ca. 3.5 Ga Dresser Formation (Pilbara Craton, Western Australia). Catalytic hydropyrolysis (HyPy) of this kerogen yielded n-alkanes up to n-C22, with a sharp decrease in abundance beyond n-C18. This distribution ( ≤ n-C18) is very similar to that observed in HyPy products of recent bacterial biomass, which was used as reference material, whereas it differs markedly from the unimodal distribution of abiotic compounds experimentally formed via Fischer-Tropsch-type synthesis. We therefore propose that the organic matter in the Archaean chert veins has a primarily microbial origin. The microbially derived organic matter accumulated in anoxic aquatic (surface and/or subsurface) environments and was then assimilated, redistributed and sequestered by the hydrothermal fluids (hydrothermal pump hypothesis).

  14. Application of binomial-edited CPMG to shale characterization.

    Science.gov (United States)

    Washburn, Kathryn E; Birdwell, Justin E

    2014-09-01

    Unconventional shale resources may contain a significant amount of hydrogen in organic solids such as kerogen, but it is not possible to directly detect these solids with many NMR systems. Binomial-edited pulse sequences capitalize on magnetization transfer between solids, semi-solids, and liquids to provide an indirect method of detecting solid organic materials in shales. When the organic solids can be directly measured, binomial-editing helps distinguish between different phases. We applied a binomial-edited CPMG pulse sequence to a range of natural and experimentally-altered shale samples. The most substantial signal loss is seen in shales rich in organic solids while fluids associated with inorganic pores seem essentially unaffected. This suggests that binomial-editing is a potential method for determining fluid locations, solid organic content, and kerogen-bitumen discrimination. Copyright © 2014 Elsevier Inc. All rights reserved.

  15. Geochemical evaluation of Pabdeh Formation in Nosrat field, southeast Persian Gulf using Rock- Eval VI pyrolysis

    Directory of Open Access Journals (Sweden)

    mohammad sadeghi

    2015-02-01

    Full Text Available The present study was performed on 59 drillhole cuttings from Pabdeh Formation in Nosrat oil field using Rock- Eval VI pryrolysis. Geochemical analysis indicated that Pabdeh Formation possesses poor to good hydrocarbon potential. Plotting S1 against TOC suggests that samples were not affected by polluting substances such as crude oil and lubricants while drilling operation. Jones organic fancies diagram shows B-BC area indicating that Pabdeh Formation was deposited in marine anoxic to oxic environments. HI vesus Tmax shows that most samples initially have had type II kerogen and now reflecting a mixture of type II to III kerogen (capable of generating oil that have already entered oil generation window. In addition, S1+S2 versus TOC plot also suggests that Pabdeh Formation can be considered as a capable hydrocarbon generating source rock in the study area.

  16. Significance of Isotopically Labile Organic Hydrogen in Thermal Maturation of Organic Matter

    Energy Technology Data Exchange (ETDEWEB)

    Arndt Schimmelmann; Maria Mastalerz

    2010-03-30

    Isotopically labile organic hydrogen in fossil fuels occupies chemical positions that participate in isotopic exchange and in chemical reactions during thermal maturation from kerogen to bitumen, oil and gas. Carbon-bound organic hydrogen is isotopically far less exchangeable than hydrogen bound to nitrogen, oxygen, or sulfur. We explore why organic hydrogen isotope ratios express a relationship with organic nitrogen isotope ratios in kerogen at low to moderate maturity. We develop and apply new techniques to utilize organic D/H ratios in organic matter fractions and on a molecular level as tools for exploration for fossil fuels and for paleoenvironmental research. The scope of our samples includes naturally and artificially matured substrates, such as coal, shale, oil and gas.

  17. Oil shale derived pollutant control materials and methods and apparatuses for producing and utilizing the same

    Science.gov (United States)

    Boardman, Richard D.; Carrington, Robert A.

    2010-05-04

    Pollution control substances may be formed from the combustion of oil shale, which may produce a kerogen-based pyrolysis gas and shale sorbent, each of which may be used to reduce, absorb, or adsorb pollutants in pollution producing combustion processes, pyrolysis processes, or other reaction processes. Pyrolysis gases produced during the combustion or gasification of oil shale may also be used as a combustion gas or may be processed or otherwise refined to produce synthetic gases and fuels.

  18. On the changing petroleum generation properties of Alum Shale over geological time caused by uranium irradiation

    Science.gov (United States)

    Yang, Shengyu; Schulz, Hans-Martin; Horsfield, Brian; Schovsbo, Niels H.; Noah, Mareike; Panova, Elena; Rothe, Heike; Hahne, Knut

    2018-05-01

    An interdisciplinary study was carried out to unravel organic-inorganic interactions caused by the radiogenic decay of uranium in the immature organic-rich Alum Shale (Middle Cambrian-Lower Ordovician). Based on pyrolysis experiments, uranium content is positively correlated with the gas-oil ratios and the aromaticities of both the free hydrocarbons residing in the rock and the pyrolysis products from its kerogen, indicating that irradiation has had a strong influence on organic matter composition overall and hence on petroleum potential. The Fourier Transform Ion Cyclotron Resonance mass spectrometry data reveal that macro-molecules in the uranium-rich Alum Shale samples are less alkylated than less irradiated counterparts, providing further evidence for structural alteration by α-particle bombardment. In addition, oxygen containing-compounds are enriched in the uranium-rich samples but are not easily degradable into low-molecular-weight products due to irradiation-induced crosslinking. Irradiation has induced changes in organic matter composition throughout the shale's entire ca. 500 Ma history, irrespective of thermal history. This factor has to be taken into account when reconstructing petroleum generation history. The Alum Shale's kerogen underwent catagenesis in the main petroleum kitchen area 420-340 Ma bp. Our calculations suggest the kerogen was much more aliphatic and oil-prone after deposition than that after extensive exposure to radiation. In addition, the gas sorption capacity of the organic matter in the Alum Shale can be assumed to have been less developed during Palaeozoic times, in contrast to results gained by sorption experiments performed at the present day, for the same reason. The kerogen reconstruction method developed here precludes overestimations of gas generation and gas retention in the Alum Shale by taking irradiation exposure into account and can thus significantly mitigate charge risk when applied in the explorations for both

  19. Petroleum source-rock potentials of the cretaceous transgressive-regressive sedimentary sequences of the Cauvery Basin

    Science.gov (United States)

    Chandra, Kuldeep; Philip, P. C.; Sridharan, P.; Chopra, V. S.; Rao, Brahmaji; Saha, P. K.

    The present work is an attempt to contribute to knowledge on the petroleum source-rock potentials of the marine claystones and shales of basins associated with passive continental margins where the source-rock developments are known to have been associated with the anoxic events in the Mesozoic era. Data on three key exploratory wells from three major depressions Ariyallur-Pondicherry, Thanjavur and Nagapattinam of the Cauvery Basin are described and discussed. The average total organic carbon contents of the transgressive Pre-Albian-Cinomanian and Coniacian/Santonian claystones/shales range from 1.44 and 1.16%, respectively. The transgressive/regressive Campanian/Maastrichtian claystones contain average total organic carbon varying from 0.62 to 1.19%. The kerogens in all the studied stratigraphic sequences are classified as type-III with Rock-Eval hydrogen indices varying from 30 to 275. The nearness of land masses to the depositional basin and the mainly clastic sedimentation resulted in accumulation and preservation of dominantly type-III kerogens. The Pre-Albian to Cinomanian sequences of peak transgressive zone deposited in deep marine environments have kerogens with a relatively greater proportion of type-II components with likely greater contribution of planktonic organic matters. The global anoxic event associated with the Albian-Cinomanian marine transgression, like in many other parts of the world, has pervaded the Cauvery Basin and favoured development of good source-rocks with type-III kerogens. The Coniacian-Campanian-Maastrichtian transgressive/regressive phase is identified to be relatively of lesser significance for development of good quality source-rocks.

  20. Formation evaluation in Devonian shale through application of new core and log analysis methods

    International Nuclear Information System (INIS)

    Luffel, D.L.; Guidry, F.K.

    1990-01-01

    In the Devonian shale of the Appalachian Basin all porosity in excess of about 2.5 percent is generally occupied by free hydrocarbons, which is mostly gas, based on results of new core and log analysis methods. In this study, sponsored by the Gas Research Institute, reservoir porosities averaged about 5 percent and free gas content averaged about 2 percent by bulk volume, based on analyses on 519 feet of conventional core in four wells. In this source-rich Devonian shale, which also provides the reservoir storage, the rock everywhere appears to be at connate, or irreducible, water saturation corresponding to two or three percent of bulk volume. This became evident when applying the new core and log analysis methods, along with a new plotting method relating bulk volume of pore fluids to porosity. This plotting method has proved to be a valuable tool: it provides useful insight on the fluid distribution present in the reservoir, it provides a clear idea of porosity required to store free hydrocarbons, it leads to a method of linking formation factor to porosity, and it provides a good quality control method to monitor core and log analysis results. In the Devonian shale an important part of the formation evaluation is to determine the amount of kerogen, since this appears as hydrocarbon-filled porosity to conventional logs. In this study Total Organic Carbon and pyrolysis analyses were made on 93 core samples from four wells. Based on these data a new method was used to drive volumetric kerogen and free oil content, and kerogen was found to range up to 26 percent by volume. A good correlation was subsequently developed to derive kerogen from the uranium response of the spectral gamma ray log. Another important result of this study is the measurement of formation water salinity directly on core samples. Results on 50 measurements in the four study wells ranged from 19,000 to 220,000 ppm NaCl

  1. Transfer of organic carbon through marine water columns to sediments – insights from stable and radiocarbon isotopes of lipid biomarkers

    OpenAIRE

    S. G. Wakeham; A. P. McNichol

    2014-01-01

    Compound-specific 13C and 14C compositions of diverse lipid biomarkers (fatty acids, alkenones, hydrocarbons, sterols and fatty alcohols) were measured in sinking particulate matter collected in sediment traps and from underlying surface sediments in the Black Sea, the Arabian Sea and the Ross Sea. The goal was to develop a multiparameter approach to constrain relative inputs of organic carbon (OC) from marine biomass, terrigenous vascular-plant and relict-kerogen sources. U...

  2. SIMS analyses of the oldest known assemblage of microfossils document their taxon-correlated carbon isotope compositions

    Science.gov (United States)

    Schopf, J. William; Kitajima, Kouki; Spicuzza, Michael J.; Kudryavtsev, Anatoliy B.; Valley, John W.

    2018-01-01

    Analyses by secondary ion mass spectroscopy (SIMS) of 11 specimens of five taxa of prokaryotic filamentous kerogenous cellular microfossils permineralized in a petrographic thin section of the ˜3,465 Ma Apex chert of northwestern Western Australia, prepared from the same rock sample from which this earliest known assemblage of cellular fossils was described more than two decades ago, show their δ13C compositions to vary systematically taxon to taxon from ‑31‰ to ‑39‰. These morphospecies-correlated carbon isotope compositions confirm the biogenicity of the Apex fossils and validate their morphology-based taxonomic assignments. Perhaps most significantly, the δ13C values of each of the five taxa are lower than those of bulk samples of Apex kerogen (‑27‰), those of SIMS-measured fossil-associated dispersed particulate kerogen (‑27.6‰), and those typical of modern prokaryotic phototrophs (‑25 ± 10‰). The SIMS data for the two highest δ13C Apex taxa are consistent with those of extant phototrophic bacteria; those for a somewhat lower δ13C taxon, with nonbacterial methane-producing Archaea; and those for the two lowest δ13C taxa, with methane-metabolizing γ-proteobacteria. Although the existence of both methanogens and methanotrophs has been inferred from bulk analyses of the carbon isotopic compositions of pre-2,500 Ma kerogens, these in situ SIMS analyses of individual microfossils present data interpretable as evidencing the cellular preservation of such microorganisms and are consistent with the near-basal position of the Archaea in rRNA phylogenies.

  3. SIMS analyses of the oldest known assemblage of microfossils document their taxon-correlated carbon isotope compositions.

    Science.gov (United States)

    Schopf, J William; Kitajima, Kouki; Spicuzza, Michael J; Kudryavtsev, Anatoliy B; Valley, John W

    2018-01-02

    Analyses by secondary ion mass spectroscopy (SIMS) of 11 specimens of five taxa of prokaryotic filamentous kerogenous cellular microfossils permineralized in a petrographic thin section of the ∼3,465 Ma Apex chert of northwestern Western Australia, prepared from the same rock sample from which this earliest known assemblage of cellular fossils was described more than two decades ago, show their δ 13 C compositions to vary systematically taxon to taxon from -31‰ to -39‰. These morphospecies-correlated carbon isotope compositions confirm the biogenicity of the Apex fossils and validate their morphology-based taxonomic assignments. Perhaps most significantly, the δ 13 C values of each of the five taxa are lower than those of bulk samples of Apex kerogen (-27‰), those of SIMS-measured fossil-associated dispersed particulate kerogen (-27.6‰), and those typical of modern prokaryotic phototrophs (-25 ± 10‰). The SIMS data for the two highest δ 13 C Apex taxa are consistent with those of extant phototrophic bacteria; those for a somewhat lower δ 13 C taxon, with nonbacterial methane-producing Archaea; and those for the two lowest δ 13 C taxa, with methane-metabolizing γ-proteobacteria. Although the existence of both methanogens and methanotrophs has been inferred from bulk analyses of the carbon isotopic compositions of pre-2,500 Ma kerogens, these in situ SIMS analyses of individual microfossils present data interpretable as evidencing the cellular preservation of such microorganisms and are consistent with the near-basal position of the Archaea in rRNA phylogenies.

  4. Source rock

    Directory of Open Access Journals (Sweden)

    Abubakr F. Makky

    2014-03-01

    Full Text Available West Beni Suef Concession is located at the western part of Beni Suef Basin which is a relatively under-explored basin and lies about 150 km south of Cairo. The major goal of this study is to evaluate the source rock by using different techniques as Rock-Eval pyrolysis, Vitrinite reflectance (%Ro, and well log data of some Cretaceous sequences including Abu Roash (E, F and G members, Kharita and Betty formations. The BasinMod 1D program is used in this study to construct the burial history and calculate the levels of thermal maturity of the Fayoum-1X well based on calibration of measured %Ro and Tmax against calculated %Ro model. The calculated Total Organic Carbon (TOC content from well log data compared with the measured TOC from the Rock-Eval pyrolysis in Fayoum-1X well is shown to match against the shale source rock but gives high values against the limestone source rock. For that, a new model is derived from well log data to calculate accurately the TOC content against the limestone source rock in the study area. The organic matter existing in Abu Roash (F member is fair to excellent and capable of generating a significant amount of hydrocarbons (oil prone produced from (mixed type I/II kerogen. The generation potential of kerogen in Abu Roash (E and G members and Betty formations is ranging from poor to fair, and generating hydrocarbons of oil and gas prone (mixed type II/III kerogen. Eventually, kerogen (type III of Kharita Formation has poor to very good generation potential and mainly produces gas. Thermal maturation of the measured %Ro, calculated %Ro model, Tmax and Production index (PI indicates that Abu Roash (F member exciting in the onset of oil generation, whereas Abu Roash (E and G members, Kharita and Betty formations entered the peak of oil generation.

  5. Contribution of the geology and geochemistry modelling to the petroleum industry

    International Nuclear Information System (INIS)

    Tissot, B.

    1993-01-01

    Evolution of modelling and model interpretation in the domain of geology, geophysics and geochemistry applied to petroleum industry, is first summarized. Hydrocarbon geological formation modelling is then presented in details with examples of kinetic models such as the discrete distribution and the Gaussian distribution based models, and the kerogene to petroleum process modelling. Petroleum basin modelling is also discussed with methods such as back-stripping, conductive thermal transfers, etc. 14 figs., 26 refs

  6. The role of alkenes produced during hydrous pyrolysis of a shale

    Energy Technology Data Exchange (ETDEWEB)

    Leif, R.N.; Simoneit, B.R.T. [Oregon State Univ., Corvallis, OR (United States). College of Oceanic and Atmospheric Sciences

    2000-07-01

    Hydrous pyrolysis experiments conducted on Messel shale with D{sub 2}O demonstrated that a large amount of deuterium becomes incorporated into the hydrocarbons generated from the shale kerogen. In order to understand the pathway of deuterium (and protium) exchange and the role of water during hydrous pyrolysis, we conducted a series of experiments using aliphatic compounds (1,13-tetradecadiene, 1-hexadecene, eicosane and dotriacontane) as probe molecules. These compounds were pyrolyzed in D{sub 2}O, shale/D{sub 2}O, and shale/H{sub 2}O and the products analyzed by GC-MS. In the absence of powdered shale, the incorporation of deuterium from D{sub 2}O occurred only in olefinic compounds via double bond isomerization. The presence of shale accelerated deuterium incorporation into the olefins and resulted in a minor amount of deuterium incorporation in the saturated n-alkanes. The pattern of deuterium substitution of the diene closely matched the deuterium distribution observed in the n-alkanes generated from the shale kerogen in the D{sub 2}O/shale pyrolyses. The presence of the shale also resulted in reduction (hydrogenation) of olefins to saturated n-alkanes with concomitant oxidation of olefins to ketones. These results show that under hydrous pyrolysis conditions, kerogen breakdown generates n-alkanes and terminal n-alkenes by free radical hydrocarbon cracking of the aliphatic kerogen structure. The terminal n-alkenes rapidly isomerize to internal alkenes via acid-catalyzed isomerization under hydrothermal conditions, a significant pathway of deuterium (and protium) exchange between water and the hydrocarbons. These n-alkenes simultaneously undergo reduction to n-alkanes (major) or oxidation to ketones (minor) via alcohols formed by the hydration of the alkenes. (Author)

  7. Study of the thermal conversions of organic carbon of Huadian oil shale during pyrolysis

    International Nuclear Information System (INIS)

    Chen, Bin; Han, Xiangxin; Li, Qingyou; Jiang, Xiumin

    2016-01-01

    Highlights: • Long-chain alkenes’ formation needs less energy than short ones. • The rupture tends to happen at the middle position of long alkyl chains first. • Cycloparaffins tend to be cracked rather than to be dehydrogenated. - Abstract: The essence of kerogen decomposition in retorting process is organic carbon conversion. FTIR and GC-MS methods were employed in analyzing the conversion process of “kerogen → bitumen” and “bitumen → shale oil” in this paper. To achieve a deeper investigation of thermochemical transformation of organic carbon during the oil shale retorting, a set of physical models of carbon chains were constructed and analyzed using the transition state theory (TST) of quantum chemistry with gauss03 package. According to the results, the main reactions in the transformation of kerogen to bitumen are the re-integration of macromolecular structure and the breakup of oxygen-bridged bonds. Long alkyl chains containing functional groups decompose and transform to shorter alkanes, alkenes and aliphatic free radicals. The rupture of alkanes happens first at the middle position of long carbon chains. Alkyl free radicals further convert to alkanes, alkenes or aromatic rings. The alkanes take the highest content in shale oil.

  8. Selective release of D and 13C from insoluble organic matter of the Murchison meteorite by impact shock

    Science.gov (United States)

    Mimura, Koichi; Okamoto, Michioki; Sugitani, Kenichiro; Hashimoto, Shigemasa

    2007-03-01

    We performed shock-recovery experiments on insoluble organic matter (IOM) purified from the Murchison meteorite, and determined the abundances and isotope ratios of hydrogen and carbon in the shocked IOM sample. We also performed shock experiments on type III kerogen and compared the results of these experiments with the experimental results regarding IOM.The shock selectively released D and 13C from the IOM, while it preferably released H and 12C from the kerogen. The release of these elements from IOM cannot be explained in terms of the isotope effect, whereas their release from kerogen can be explained by this effect. The selective release of heavier isotopes from IOM would be due to its structure, in which D and 13C-enriched parts are present as an inhomogeneity and are weakly attached to the main network. Shock gave rise to a high release of D even at a lower degree of dehydrogenation compared with the stepwise heating of IOM. This effective release of D is probably an inherent result of shock, in which a dynamic high-pressure and high-temperature condition prevails. Thus, shock would effectively control the hydrogen isotope behavior of extraterrestrial organic matter during the evolution of the solar nebula.

  9. Distribution, classification, petrological and related gochemical (SRA) characteristics of a tropical lowland peat dome in the Kota Samarahan-Asajaya area, West Sarawak, Malaysia

    Science.gov (United States)

    Zulkifley, Mohamad Tarmizi Mohamad; Fatt, Ng Tham; Abdullah, Wan Hasiah; Raj, John Kuna; Paramanathan Param, S.; Hashim, Roslan; Ashraf, Muhammad Aqeel

    2013-06-01

    Petrographic studies indicate that lateral variations in the decomposition levels of peat are associated with the predominantly occurring peat macerals. Source Rock Analyzer (SRA) results indicate lateral variation in peat organic matter types from type II to III and back again to type II, occurring laterally within the top 0-m to 0.5-m layer at the basin margin to the midsection and further towards the near-center areas of the peat dome. This variation is most likely caused by a combination of factors: (a) Horizontal zonation and lateral variation of the dominant species of plant assemblages (b) Fibric (marginal) peats and hemic to sapric peats associated with type II organic matter (kerogen). Sample organic matter (coal-equivalent kerogen) typing indicates that the relative abundance of phytoclasts and palynomorphs generally supports the organic matter classification obtained by the SRA method. Lateral variations in the peat organic matter types may support the lateral vegetation variation concept. The classification of peat organic matter types (interpreted from visual analyses of palynological slides) occurring from the basin periphery to the mid-section and further towards the basin center yields organic matter of type II to type III and mixed types II to III (coal kerogen-equivalent), respectively.

  10. Contribution to physico-chemical study of Timahdit bituminous schists (Morocco): Organic matters and metalloporphyrins

    International Nuclear Information System (INIS)

    Saoiabi, A.

    1982-01-01

    The Timahdit bituminous schists have been analysed by different methods. The experimental results obtained using these methods concern the behaviour of the schists and the Kerogen facing the pyrolysis, as well as the separation of the hydrocarbons and the metalloporphyrins. For this purpose the techniques used are: 'Rock Eval' pyrolysis, thermogravimetric analysis and electron paramagnetic resonance (E.P.R.) for the raw rock and the Kerogen; infrared (I.R.), gas chromatography and E.P.R. for the extracted organic matters; E.P.R., I.R., nuclear magnetic resonance (N.M.R.), ultraviolet (U.V.) and mass spectrometry for the metalloporphyrins identification and characterization. The analysis of these schists has shown that: We can extract per solvent only 1% of organic matters, ferric oxide hasn't any effect neither on the pyrolysis nor on the organic matters extraction and that the Kerogen of these schists are relatively rich in hydrocarbonic compounds. The gas chromatography reveal the presence of alkanes with odd number of carbons and isoprenoids. All these criteria indicate an immature, little developped organic matter which having probably a marine origin but possessing a good oil potential. It has also been observed that a part of Iron, Nickel and Vanadium in the schists are incorporated into the organic matters. Nickel and Vanadium are into macrocycles which are porphyrins. A method for extracting and separating these porphyrins has been developped. 43 figs., 21 tabs., 58 refs. (author)

  11. Classes of organic molecules targeted by a methanogenic microbial consortium grown on sedimentary rocks of various maturities

    Directory of Open Access Journals (Sweden)

    Margaux eMesle

    2015-06-01

    Full Text Available Organic-rich shales are populated by methanogenic consortia that are able to degrade the fossilized organic matter into methane gas. To identify the organic fraction effectively degraded, we have sequentially depleted two types of organic-rich rocks, shales and coal, at two different maturities, by successive solvent extractions to remove the most soluble fractions (maltenes and asphaltenes and isolate kerogen. We show the ability of the consortia to produce methane from all rock samples, including those containing the most refractory organic matter, i.e. the kerogen. Shales yielded higher methane production than lignite and coal. Mature rocks yielded more methane than immature rocks. Surprisingly, the efficiency of the consortia was not influenced by the removal of the easily biodegradable fractions contained in the maltenes and asphaltenes. This suggests that one of the limitations of organic matter degradation in situ may be the accessibility of the carbon and energy source. Indeed, bitumen has a colloidal structure that may limit the accessibility to asphaltenes in the bulk rock. Solvent extractions might favor the access to asphaltenes and kerogen by modifying the spatial organization of the molecules in the rock matrix.

  12. Analysis of over-pressure mechanisms in the Uinta Basin, Utah

    Energy Technology Data Exchange (ETDEWEB)

    McPherson, B.; Bredehoeft, J. [Geological Survey, Menlo Park, CA (United States)

    1995-03-01

    Extremely high pore fluid pressures exist in the area of the Altamount/Bluebell oil field in the Uinta basin, Utah. We discuss two possible mechanisms for the cause of these over-pressures in this paper: (1) compaction disequilibrium, and (2) conversion of kerogen to liquid hydrocarbon (oil). Compaction disequilibrium occurs during periods of rapid sedimentation. If the permeability of deeply buried strata is low, then connate water within the rock matrix does not escape rapidly enough as compaction occurs; as sedimentary deposition continues, high pore fluid pressures develop. Conversion of solid kerogen to a liquid generates both a liquid and additional pore space for the liquid to occupy. If the volume of the liquid generated is just sufficient to fill the pore space generated, then there will be no accompanying effect on the pore pressure. If the liquid is less dense than the solid it replaces, then there is more liquid than pore space created; pore pressure will increase, causing flow away from the area of the reaction. Pore pressure is a sensitive measure of the balance between hydrocarbon generation and expulsion from the source into adjacent strata. If high pore pressures exist only where source rocks are thought to be generating oil, then kerogen conversion is a likely over-pressure mechanism. However, if over-pressures are found in low-permeability strata regardless of source rock proximity, then sedimentary compaction is probably a more dominant mechanism.

  13. Potensi Batuan Induk Batu Serpih dan Batu Lempung di Daerah Watukumpul Pemalang Jawa Tengah

    Directory of Open Access Journals (Sweden)

    Sachrul Iswahyudi

    2009-02-01

    Full Text Available Shale and claystone of Watukumpul Area have capability to become the source rock of hydrocarbon because of the ability to conserve the organic material better. Potential of the rock become source rock is depend on its maturity and total organic carbon. This research test eight example of rock to analysis their total organic carbon (TOC and rock eval pyrolisis. Only one sample is claystone, while the seven others are shales. The analyses provide data of total organic carbon, hydrogen index, and vitrinite reflectances which was used to interpret source rock potential of research area. Through this research is known that the organic material content of shale and claystone of research area own the fair level of total organic carbon. Organic material is included Kerogen Type III with the origin of land organism or plant. These kerogens of research area prefer to produce gas or gas prone. Organic material or kerogens have reached the matured phase to generate hydrocarbon (mature level. Special follow the rock sample came from Location 8 which have over mature level. Its high maturity is suspect have relationship with the intrusion of diorite igneous rock in this research area. Further research is needed to investigate the relationship between diorite intrusion and organic material in this research area.

  14. Late production of hydrocarbon gases in sedimentary basins: kinetic and isotopic study; Genese tardive des gaz hydrocarbures dans les bassins sedimentaires: etude cinetique et isotopique

    Energy Technology Data Exchange (ETDEWEB)

    Lorant, F.

    1999-06-23

    The thermal decomposition of sedimentary organic matter, or kerogen, within the metagenesis zone (T > 170 deg. C) leads to the formation of large amounts of late gas, mainly composed by methane. The work reported in this dissertation aims at understanding and quantifying the mechanisms of late methane generation and isotopic fractionation. With this purpose, natural samples of Type II and Type III mature kerogens (Ro > 1.3%, H/C < 0.65), were artificially heated in both open (T = 350 to 900 deg. C at 25 deg. C/min) and closed (T = 375 to 550 deg. C with t = 1 to 216 h) systems. For each experiment, mass and atomic (C, H, O) balances were obtained by recovering, fractionating and quantifying the entire pyrolysis effluents. Moreover, the isotopic compositions ({sup 13}C/{sup 12}C ratios) of methane and insoluble residue produced in closed system were measured. These experimental simulations have shown that the amounts of methane generated in an open-pyrolysis system (9 to 40 mg/gC) are systematically inferior to that observed in a closed-pyrolysis system (44 to 68 mg/gC), even after correction of the possible C{sub 2}-C{sub 5} and C{sub 6+} hydrocarbons secondary cracking. This shift, which is larger for Type II kerogens compared to coals and Type II-S kerogens, seems to be correlated with the pyrite content of the samples. Based on the closed-pyrolysis system data, a kinetic scheme, suitable for both Type II and Type III kerogens, was established. It includes three consecutive reactions, whose apparent kinetic parameters do not allow accounting for the corresponding rate constants observed in open system: E{sub 1} = 64.7 kcal/mol and A{sub 1} = 2.58 x 10{sup 15} s{sup -1}, E{sub 2} = 52.8 kcal/mol and A{sub 2} = 5.50 x 10{sup 10} s{sup -1}, E{sub 3} = 55-58 kcal/mol and A{sub 3} = 7.52 x 10{sup 9} s{sup -1}. By extrapolation to geological setting, it was thus predicted that kerogens might generate about 15 mg/gC of late methane between 170 and 200 deg. C. In order

  15. Change in mechanical properties of Antrim oil shale on retorting

    Energy Technology Data Exchange (ETDEWEB)

    Singh, S. P.; Hockings, W. A.; Kim, K.

    1979-01-01

    The decomposition of kerogen in oil shale and subsequent extraction of the decomposition products during the retorting process are known to alter the pore structure, resulting in changes in permeability, deformation and strength properties. Prediction of these changes is of fundamental importance in the design of in-situ retorting processes. This paper summarizes a comprehensive laboratory investigation on the changes in mechanical properties of Antrim oil shale on retorting at 500/sup 0/C. It was observed that kerogen plays an important role in the change of the properties on retorting. When subjected to heat, the degree of deformation, the extent of fracturing and the structural instability of the specimens appeared to be strongly dependent upon kerogen content. The values of elastic modulus, strength, and density decreased whereas maximum strain at failure increased on retorting. Significant increases in permeability and porosity also resulted from retorting. The most pronounced increase was observed in the permeability in the direction parallel to bedding which exceeded in some cases as much as 3 orders of magnitude. Microscopic observations of pore structures provided a qualitative support to data obtained in measurements of porosity and permeability.

  16. Mining and oil. Oil shale's contribution to future oil supply; Bergbau und Oel. Der Beitrag des Oelschiefers zur Oelversorgung

    Energy Technology Data Exchange (ETDEWEB)

    Linden, Eike von der [Linden Advisory, Dreieich (Germany)

    2012-05-15

    Crude oil contributes in Germany and globally approximately one third to the consumption of primary energies and actually is and in the foreseeable future will be the most important energy source. Recently shale oil as an unconventional oil has gained attention in public discussions. Depending on temperatures oil shale contains either already matured fluid shale oil or immature waxy kerogen. For determination of kerogen containing oil shale and shale oil common definitions for fluid hydrocarbons will be presented. Fluid hydrocarbons (molecular chains > C{sub 5}H{sub 12}) originate from animal substance which had been settled millions of years in sediments on sea- or lakebeds under anaerobic conditions. High pressure and high temperatures effect conversion to hydrocarbons. With sufficient permeability the liquid hydrocarbons migrate from the sediment as the source rock and get assembled in porous rocks under the cover of an impermeable rock strata, in so called entrapment structures. In case there is no impermeable rock strate the hydrocarbons will diffuse into the atmosphere. The hydrocarbons in entrapment structures are called conventional oil and are extracted by drilling wells. The extractable oil as part of the oil in place depends on the viscosity of the oil, the permeability of the host rock and applied exploitation methods which can affect pressure, viscosity and permeability. The exploitation achieves 30 to 50% of the oil in place. When the source rock consisting of strata hundreds of meters thick is not sufficiently permeable the matured hydrocarbons remain at its place of origination. These hydrocarbons are called shale oil and belong to the unconventional oil resources. For exploitation of shale oil by wells the source rock must be treated by intensive energy input, amongst others, by fracking which creates artificial permeability and by pressure which affects migration of the hydrocarbons to the well. The exploitation methods for shale oil do not

  17. Compositional controls on early diagenetic pathways in fine-grained sedimentary rocks: Implications for predicting unconventional reservoir attributes of mudstones

    Science.gov (United States)

    Keller, Margaret A.; Macquaker, Joe H.S.; Taylor, Kevin G.; Polya, David

    2014-01-01

    Diagenesis significantly impacts mudstone lithofacies. Processes operating to control diagenetic pathways in mudstones are poorly known compared to analogous processes occurring in other sedimentary rocks. Selected organic-carbon-rich mudstones, from the Kimmeridge Clay and Monterey Formations, have been investigated to determine how varying starting compositions influence diagenesis.The sampled Kimmeridge Clay Formation mudstones are organized into thin homogenous beds, composed mainly of siliciclastic detritus, with some constituents derived from water-column production (e.g., coccoliths, S-depleted type-II kerogen, as much as 52.6% total organic carbon [TOC]) and others from diagenesis (e.g., pyrite, carbonate, and kaolinite). The sampled Monterey Formation mudstones are organized into thin beds that exhibit pelleted wavy lamination, and are predominantly composed of production-derived components including diatoms, coccoliths, and foraminifera, in addition to type-IIS kerogen (as much as 16.5% TOC), and apatite and silica cements.During early burial of the studied Kimmeridge Clay Formation mudstones, the availability of detrital Fe(III) and reactive clay minerals caused carbonate- and silicate-buffering reactions to operate effectively and the pore waters to be Fe(II) rich. These conditions led to pyrite, iron-poor carbonates, and kaolinite cements precipitating, preserved organic carbon being S-depleted, and sweet hydrocarbons being generated. In contrast, during the diagenesis of the sampled Monterey Formation mudstones, sulfide oxidation, coupled with opal dissolution and the reduced availability of both Fe(III) and reactive siliciclastic detritus, meant that the pore waters were poorly buffered and locally acidic. These conditions resulted in local carbonate dissolution, apatite and silica cements precipitation, natural kerogen sulfurization, and sour hydrocarbons generation.Differences in mud composition at deposition significantly influence subsequent

  18. Burial history, thermal history and hydrocarbon generation modelling of the Jurassic source rocks in the basement of the Polish Carpathian Foredeep and Outer Carpathians (SE Poland)

    Science.gov (United States)

    Kosakowski, Paweł; Wróbel, Magdalena

    2012-08-01

    Burial history, thermal maturity, and timing of hydrocarbon generation were modelled for the Jurassic source rocks in the basement of the Carpathian Foredeep and marginal part of the Outer Carpathians. The area of investigation was bounded to the west by Kraków, to the east by Rzeszów. The modelling was carried out in profiles of wells: Będzienica 2, Dębica 10K, Góra Ropczycka 1K, Goleszów 5, Nawsie 1, Pławowice E1 and Pilzno 40. The organic matter, containing gas-prone Type III kerogen with an admixture of Type II kerogen, is immature or at most, early mature to 0.7 % in the vitrinite reflectance scale. The highest thermal maturity is recorded in the south-eastern part of the study area, where the Jurassic strata are buried deeper. The thermal modelling showed that the obtained organic matter maturity in the initial phase of the "oil window" is connected with the stage of the Carpathian overthrusting. The numerical modelling indicated that the onset of hydrocarbon generation from the Middle Jurassic source rocks was also connected with the Carpathian thrust belt. The peak of hydrocarbon generation took place in the orogenic stage of the overthrusting. The amount of generated hydrocarbons is generally small, which is a consequence of the low maturity and low transformation degree of kerogen. The generated hydrocarbons were not expelled from their source rock. An analysis of maturity distribution and transformation degree of the Jurassic organic matter shows that the best conditions for hydrocarbon generation occurred most probably in areas deeply buried under the Outer Carpathians. It is most probable that the "generation kitchen" should be searched for there.

  19. Process for retorting shale

    Energy Technology Data Exchange (ETDEWEB)

    1952-03-19

    The method of retorting oil shale to recover valuable liquid and gaseous hydrocarbons consists of heating the oil shale in a retorting zone to a temperature sufficient to convert its kerogenic constituents to normally liquid and normally gaseous hydrocarbons by contact with hot gas previously recovered from shale, cooling the gases and vapors effluent from the retorting zone by direct countercurrent contact with fresh shale to condense the normally liquid constituents of the gases and vapors, separating the fixed gas from the liquid product, heating the fixed gas, and returning it to the retorting zone to contact further quantities of shale.

  20. Source rock evaluation and organic geochemistry of Belayim Marine Oil Field, Gulf of Suez, Egypt

    Directory of Open Access Journals (Sweden)

    Mohamed Abu Al-Atta

    2014-09-01

    In general, TOC analyses showed that the Nubia-A and B formation sediments are fairly immature compared to good source rocks with very high Hydrogen Index indicative of kerogen type II. The geochemical investigations of two oil samples indicate that the Upper Rudeis oil of Belayim Marine was derived from a marine carbonate rich source, which is relatively rich in algal organic matter and has moderate sulfur content. The maturity of the analyzed oils (about 0.75% R0 falls short from the stage of peak hydrocarbon generation which is known to be reached at about 0.85% R0.

  1. Investigation of the Geokinetics horizontal in situ oil-shale-retorting process. Fourth annual report, 1980

    Energy Technology Data Exchange (ETDEWEB)

    Hutchinson, D.L. (ed.)

    1981-03-01

    The Geokinetics in situ shale oil project is a cooperative venture between Geokinetics Inc. and the US Department of Energy. The objective is to develop a true in situ process for recovering shale oil using a fire front moving in a horizontal direction. The project is being conducted at a field site, Kamp Kerogen, located 70 miles south of Vernal, Utah. This Fourth Annual Report covers work completed during the calendar year 1980. During 1980 one full-size retort was blasted. Two retorts, blasted the previous year, were burned. A total of 4891 barrels of oil was produced during the year.

  2. Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems

    Science.gov (United States)

    Zhang, Tongwei; Ellis, Geoffrey S.; Ruppel, Stephen C.; Milliken, Kitty; Yang, Rongsheng

    2012-01-01

    A series of methane (CH4) adsorption experiments on bulk organic rich shales and their isolated kerogens were conducted at 35 °C, 50 °C and 65 °C and CH4 pressure of up to 15 MPa under dry conditions. Samples from the Eocene Green River Formation, Devonian–Mississippian Woodford Shale and Upper Cretaceous Cameo coal were studied to examine how differences in organic matter type affect natural gas adsorption. Vitrinite reflectance values of these samples ranged from 0.56–0.58 %Ro. In addition, thermal maturity effects were determined on three Mississippian Barnett Shale samples with measured vitrinite reflectance values of 0.58, 0.81 and 2.01 %Ro. For all bulk and isolated kerogen samples, the total amount of methane adsorbed was directly proportional to the total organic carbon (TOC) content of the sample and the average maximum amount of gas sorption was 1.36 mmol of methane per gram of TOC. These results indicate that sorption on organic matter plays a critical role in shale-gas storage. Under the experimental conditions, differences in thermal maturity showed no significant effect on the total amount of gas sorbed. Experimental sorption isotherms could be fitted with good accuracy by the Langmuir function by adjusting the Langmuir pressure (PL) and maximum sorption capacity (Γmax). The lowest maturity sample (%Ro = 0.56) displayed a Langmuir pressure (PL) of 5.15 MPa, significantly larger than the 2.33 MPa observed for the highest maturity (%Ro > 2.01) sample at 50 °C. The value of the Langmuir pressure (PL) changes with kerogen type in the following sequence: type I > type II > type III. The thermodynamic parameters of CH4 adsorption on organic rich shales were determined based on the experimental CH4 isotherms. For the adsorption of CH4 on organic rich shales and their isolated kerogen, the heat of adsorption (q) and the standard entropy (Δs0) range from 7.3–28.0 kJ/mol and from −36.2 to −92.2 J/mol/K, respectively.

  3. Isoprenoid hydrocarbons produced by thermal alteration of Nostoc muscorum and Rhodopseudomonas spheroides

    Science.gov (United States)

    Philp, R. P.; Brown, S.; Calvin, M.

    1978-01-01

    The potential of algae and photosynthetic bacteria to serve as precursors of kerogen was studied to determine what factors affect the relative rates of formation of precursor hydrocarbons. Cells of Nostoc muscorum and Rhodopseudomonas spheroides were subjected to thermal alteration (by heating samples in glass tubes sealed under nitrogen) for two, four, and twelve weeks. Both unextracted and extracted cells in the absence and presence of montmorillonite were investigated, and the isoprenoid hydrocarbons produced in these experiments were determined. Phytane and five isomeric phytenes were the main hydrocarbons observed; their relative rates of formation in the different experimental conditions are described. No phytadienes, pristane, or pristenes were detected.

  4. Gas pressure from a nuclear explosion in oil shale

    International Nuclear Information System (INIS)

    Taylor, R.W.

    1975-01-01

    The quantity of gas and the gas pressure resulting from a nuclear explosion in oil shale is estimated. These estimates are based on the thermal history of the rock during and after the explosion and the amount of gas that oil shale releases when heated. It is estimated that for oil shale containing less than a few percent of kerogen the gas pressure will be lower than the hydrostatic pressure. A field program to determine the effects of nuclear explosions in rocks that simulate the unique features of oil shale is recommended. (U.S.)

  5. Origin of oil shale

    Energy Technology Data Exchange (ETDEWEB)

    Cunningham-Craig, E H

    1915-01-01

    Kerogen was believed to be formed by the inspissation of petroleum. During this process nitrogen and sulfur compounds were concentrated in the most inspissated or weathered products. At a certain stage, reached gradually, the organic matter became insoluble in carbon-disulfide and ceased to be a bitumen. Oil shale was formed by the power of certain clays or shales to absorb inspissated petroleum, particularly unsaturated hydrocarbons. This adsorption apparently depended on the colloid content of the argillaceous rock. This rock retained these impregnated petroleum residues long after porous sandstones in the vicinity had lost all traces of petroleum by weathering and leaching.

  6. Chemistry of the Estonian oil-shale kukersite

    Energy Technology Data Exchange (ETDEWEB)

    Kogerman, P N

    1931-01-01

    Estonian oil shale is one of the oldest and richest oil shales in the world. The deposits occur in the Middle-Ordovician strata having a total thickness of 2.2 meters. The ultimate composition of the kerogen varied within the following limits: carbon 76.5 to 76.7 percent, hydrogen 9.1 to 9.2 percent, nitrogen 0.2 to 0.4 percent, sulfur 1.6 to 2.2 percent, chlorine 0.5 to 0.7 percent, and oxygen (by difference) 11.2 to 12.2 percent. The composition of kukersite kerogen corresponds nearly to the empirical formula (C/sub 8/H/sub 11/O)n. One of the most significant differences between kukersite, coal, and lignite is the amount of alkali-soluble substances present. Kukersite has almost no humic acids. Samples of kukersite were brominated and chlorinated. The halogenated shales showed a solubility in absolute alcohol of 26 percent compared to only 0.31 percent for untreated shale. Enriched shale (4.5 percent ash) did not react with chlorine as much as did raw shale. Apparently the mineral matter acted catalytically during chlorination. The amount of soluble extract obtained by solvent treatment of kukersite ranged from 0.22 percent with chloroform to 2.20 percent with tetrachloroethane. Heat was the most effective agent for the depolymerization of kukersite kerogen. The percentage loss of weight due to drying in air was much less than in the presence of carbon dioxide. The results indicated that on drying in air, the powdered shale loses water and a volatile substance, probably the oxides of carbon, up to 80/sup 0/C. Carbon dioxide was also found to be present in the gases eliminated at the temperature of initial decomposition. Pulverized shale, heated for 6 hours at 220/sup 0/C, lost 2.6 percent of its weight; its solubility in carbon disulfide was 2.11 percent. Kukersite kerogen was formed from compounds that were resistent to bacteriological decomposition, such as waxes and resins, plus decomposition products of proteins, cellulose, and putrefaction products of

  7. Air oxidation of samples from different clay formations of East Paris basin: quantitative and qualitative consequences on the dissolved organic matter

    International Nuclear Information System (INIS)

    Blanchart, Pascale; Faure, Pierre; Michels, Raymond; Parant, Stephane

    2012-01-01

    Document available in extended abstract form only. During the excavation and the building of an underground research laboratory in clay geological formations, exposure to air is one of the most important parameters affecting the composition of fossil organic matter. Indeed the net effect of air oxidation of the organic matter is enrichment in oxygen and carbon combined with a loss of hydrogen. Effluents formed are CO 2 and water as well as the liberation of hydrocarbons. This process may have an impact on water chemistry of the clay, especially on the quantity and composition of Dissolved Organic Matter (DOM). The clays studied were the following and may be distinguished on the basis of their organic matter content: - The Callovo-Oxfordian argillite, collected in the Bure Underground Research Laboratory (Meuse, France), which contains a mixture of type II and III kerogen; - The Toarcian shales of East Paris Basin collected from drilling EST 204 (Meuse, France) contains type II kerogen; - The Kimmeridgian shales of East Paris Basin collected from drilling HTM 102 (Meuse, France) also contains type II kerogen. The powdered clay samples were oxidized in a ventilated oven at 100 C under air flow during 2, 256, 512 and 1088 hours for Callovo-Oxfordian samples and during 512 and 2048 hours for Toarcian and Kimmeridgian samples. The DOM of each sample was extracted by soxhlet using pure water. Different analyses were carried out: - Quantitative evolution of DOM with the oxidation process; - Evolution of several chemical parameters of DOM with oxidation using molecular analyses (PyGC-MS) molecular weight distribution (GPC-HPLC) as well as spectroscopic measurements (3D-Fluorescence). Increasing oxidation induces an increase of DOC values for all samples. Also, Changes in the chemical composition of the DOM are observed: decrease in the molecular weight range; enrichment in acidic functional groups (alkane-dioic acids, alkanoic acids, aromatics poly acids). Moreover the

  8. Modelling hydrothermal venting in volcanic sedimentary basins: Impact on hydrocarbon maturation and paleoclimate

    Science.gov (United States)

    Iyer, Karthik; Schmid, Daniel W.; Planke, Sverre; Millett, John

    2017-06-01

    Vent structures are intimately associated with sill intrusions in sedimentary basins globally and are thought to have been formed contemporaneously due to overpressure generated by gas generation during thermogenic breakdown of kerogen or boiling of water. Methane and other gases generated during this process may have driven catastrophic climate change in the geological past. In this study, we present a 2D FEM/FVM model that accounts for 'explosive' vent formation by fracturing of the host rock based on a case study in the Harstad Basin, offshore Norway. Overpressure generated by gas release during kerogen breakdown in the sill thermal aureole causes fracture formation. Fluid focusing and overpressure migration towards the sill tips results in vent formation after only few tens of years. The size of the vent depends on the region of overpressure accessed by the sill tip. Overpressure migration occurs in self-propagating waves before dissipating at the surface. The amount of methane generated in the system depends on TOC content and also on the type of kerogen present in the host rock. Generated methane moves with the fluids and vents at the surface through a single, large vent structure at the main sill tip matching first-order observations. Violent degassing takes place within the first couple of hundred years and occurs in bursts corresponding to the timing of overpressure waves. The amount of methane vented through a single vent is only a fraction (between 5 and 16%) of the methane generated at depth. Upscaling to the Vøring and Møre Basins, which are a part of the North Atlantic Igneous Province, and using realistic host rock carbon content and kerogen values results in a smaller amount of methane vented than previously estimated for the PETM. Our study, therefore, suggests that the negative carbon isotope excursion (CIE) observed in the fossil record could not have been caused by intrusions within the Vøring and Møre Basins alone and that a contribution

  9. A 200 year sedimentary record of progressive eutrophication in lake Greifen (Switzerland): Implications for the origin of organic-carbon-rich sediments

    Science.gov (United States)

    Hollander, David J.; McKenzie, Judith A.; Lo Ten Haven, H.

    1992-09-01

    Over the past 200 years Lake Greifen, a small lake in northeastern Switzerland, has undergone dramatic changes in primary productivity and eutrophication due to increased nutrient supply from agricultural activity and industrialization. A 40 year historical record of the water-column chemistry indicates that productivity and eutrophication reached a maximum in 1974, after which stricter regulations on the input of nutrients resulted in a progressive decrease. Collected cores show the sedimentary expression of this anthropogenically induced eutrophication by a well-developed annual sedimentation and by enhanced values of total organic carbon, organic-carbon accumulation rates, and hydrogen indices (HI) of the kerogens. Analyses of the carbon isotopic composition of sedimentary carbonates and organic matter reveal that the fractionation between these two phases varies with the HI of kerogens. This observation is explicable in terms of changing productivity and preservation of the organic matter, and the CO2(aq) budget of the water body. We propose that if high primary productivity were primarily responsible for the preservation and accumulation of organic matter, then a negative correlation will occur between Δδ13Ccalcite-organic matter (Δδ13Ccal-om) and HI values. In an environment with relatively low to moderate productivity but with bottom-water anoxia, a positive correlation will exist between Δδ13Ccal-om and HI values. This study of Lake Greifen has implications for understanding paleoenvironmental controls on ancient organic-carbon-rich sediments.

  10. Brent coal typing by combined optical and geochemical studies

    Energy Technology Data Exchange (ETDEWEB)

    Ducazeaux, J.; Le Tran, K.; Nicolas, G. (Societe Nationale des Petroles d' Aquitaine (SNPA), 64 - Pau (France))

    1991-12-01

    Palynological,petrographical and organic geochemical studies show that various kinds of coal occur throughout the Middle Jurassic Brent Group in the Viking Graben. Two types of coal with strong contrast in terms of source rock potential are thoroughly investigated in this study. It is found that they are relevant to two distinct organic facies. Though having the same organic carbon content, they are very different with respect to the petroleum generating potential, one being a conventional gas-prone coal of type III kerogen and the other one of type II-(III) kerogen which should be considered as an oil-generating coal. Explanations are sought for the difference observed, both geochemically and optically. Palynological study shows the occurrence of two distinct communities of land plants in relation with the depositional environment and climatic changes, whilst coal petrographical study shows that the macerals are unevenly and differently distributed in these two coal types. The original organic material and the depositional environment appear to be the main controlling factors. 13 Refs.; 8 Figs.

  11. Shale gas characterization based on geochemical and geophysical analysis: Case study of Brown shale, Pematang formation, Central Sumatra Basin

    Science.gov (United States)

    Haris, A.; Nastria, N.; Soebandrio, D.; Riyanto, A.

    2017-07-01

    Geochemical and geophysical analyses of shale gas have been carried out in Brown Shale, Middle Pematang Formation, Central Sumatra Basin. The paper is aimed at delineating the sweet spot distribution of potential shale gas reservoir, which is based on Total Organic Carbon (TOC), Maturity level data, and combined with TOC modeling that refers to Passey and Regression Multi Linear method. We used 4 well data, side wall core and 3D pre-stack seismic data. Our analysis of geochemical properties is based on well log and core data and its distribution are constrained by a framework of 3D seismic data, which is transformed into acoustic impedance. Further, the sweet spot of organic-rich shale is delineated by mapping TOC, which is extracted from inverted acoustic impedance. Our experiment analysis shows that organic materials contained in the formation of Middle Pematang Brown Shale members have TOC range from 0.15 to 2.71 wt.%, which is classified in the quality of poor to very good. In addition, the maturity level of organic material is ranging from 373°C to 432°C, which is indicated by vitrinite reflectance (Ro) of 0.58. In term of kerogen type, this Brown shale formation is categorized as kerogen type of II I III, which has the potential to generate a mixture of gasIoil on the environment.

  12. DEPOSITIONAL ENVIRONMENT AND ORGANIC GEOCHEMICAL CHARACTERISTICS OF LOWER EOCENE BITUMINOUS ROCKS, IN THE KÜRNÜÇ/GÖYNÜK-BOLU AREA

    Directory of Open Access Journals (Sweden)

    Ali SARI

    2016-12-01

    Full Text Available In this study, dark gray and dark brown colored, organic-carbon rich bituminous rocks (bituminous marl and bituminous shale exposing around the Kürnüç area (Göynük, Bolu are investigated by means of or- ganic geochemical characteristics. In this respect, rock lithologies, depositional environments, rock source potential, kerogen and organic maturity types and hydrocarbon generation potentials of bituminous rocks were determined. For this reason, pyrolysis (Rock Eval–VI analysis, gas chromatography (GC and gas chromatography-mass spectrometer (GC-MS analyses were carried out. In addition, spore color index (SCI was determined with organic petrographic method and stable carbon analysis (δ13C of the samples were also conducted. Lithology of the studied samples is of clastic source and the depositional environ- ment is a lagoon with a partial connection to the sea. In bituminous rocks with excellent source rock potential TOC values are in the range of 2.52-8.38 wt % (average 6.08 wt %. With the exception of two samples (Type II kerogen type of all samples is Type I. According to pyrolysis, GC and GC-MS organic maturity results, all the samples are in immature stage. Organic geochemical data indicate that bituminous rocks have an excellent oil generation potential and there is no organic contamination.

  13. Heterogeneous carbonaceous matter in sedimentary rock lithocomponents causes significant trichloroethylene (TCE) sorption in a low organic carbon content aquifer/aquitard system.

    Science.gov (United States)

    Choung, Sungwook; Zimmerman, Lisa R; Allen-King, Richelle M; Ligouis, Bertrand; Feenstra, Stanley

    2014-10-15

    This study evaluated the effects of heterogeneous thermally altered carbonaceous matter (CM) on trichloroethylene (TCE) sorption for a low fraction organic carbon content (foc) alluvial sedimentary aquifer and aquitard system (foc=0.046-0.105%). The equilibrium TCE sorption isotherms were highly nonlinear with Freundlich exponents of 0.46-0.58. Kerogen+black carbon was the dominant CM fraction extracted from the sediments and accounted for >60% and 99% of the total in the sands and silt, respectively. Organic petrological examination determined that the kerogen included abundant amorphous organic matter (bituminite), likely of marine origin. The dark calcareous siltstone exhibited the greatest TCE sorption among aquifer lithocomponents and accounted for most sorption in the aquifer. The results suggest that the source of the thermally altered CM, which causes nonlinear sorption, was derived from parent Paleozoic marine carbonate rocks that outcrop throughout much of New York State. A synthetic aquifer-aquitard unit system (10% aquitard) was used to illustrate the effect of the observed nonlinear sorption on mass storage potential at equilibrium. The calculation showed that >80% of TCE mass contained in the aquifer was sorbed on the aquifer sediment at aqueous concentration TCE groundwater plume in the aquifer studied. It is implied that sorption may similarly contribute to TCE persistence in other glacial alluvial aquifers with similar geologic characteristics, i.e., comprised of sedimentary rock lithocomponents that contain thermally altered CM. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Middle to late Jurassic in Poland; Mellem - Oevre jura i Polen

    Energy Technology Data Exchange (ETDEWEB)

    Poulsen, N.E.; Bojesen-Koefoed, J.; Drewniak, A.; Glowniak, E.; Ineson, J.; Matyja, B.A.; Merta, T.; Wierzbowski, A.

    1998-12-01

    Results of this project have contributed to the renewed research in the area of the Middle Jurassic ammonite stratigraphy. Upper Jurassic ammonite stratigraphy is a very actively researched field at the Geological Institute of the Warsaw University. The stratigraphical distribution of dinoflagellate cysts within the Upper Bajocian-Bathonian-Lower Callovian has provided a detailed correlation between the Polish Submediterranean Province (northern Tethyan realm) and the Subboreal Province of the North Sea area (chronostratigraphy and dinoflagellate zonation). One of the most interesting results is the improved correlation of the Oxfordian/Kimmeridgean boundary between these two provinces. The source mineral research contributed new data about the oil/gas potential of megafacies in the central Poland. The planned model development of catagenesis of Middle Jurassic clay sediments in relation to salt deposits could not be established from the found low TOC values and very low hydrogen index values between 6 and 141. The organic material can be characterized as kerogen-type III/IV. Kerogen is considered generally immature with regard to oil/gas formation. The detailed study of sponge bioherms in North-Western Poland has resulted in better understanding of the architecture and evolution of these bioherms. (EG)

  15. Biogenicity and Syngeneity of Organic Matter in Ancient Sedimentary Rocks: Recent Advances in the Search for Evidence of Past Life

    Energy Technology Data Exchange (ETDEWEB)

    Oehler, Dorothy Z.; Cady, Sherry L.

    2014-12-01

    he past decade has seen an explosion of new technologies for assessment of biogenicity and syngeneity of carbonaceous material within sedimentary rocks. Advances have been made in techniques for analysis of in situ organic matter as well as for extracted bulk samples of soluble and insoluble (kerogen) organic fractions. The in situ techniques allow analysis of micrometer-to-sub-micrometer-scale organic residues within their host rocks and include Raman and fluorescence spectroscopy/imagery, confocal laser scanning microscopy, and forms of secondary ion/laser-based mass spectrometry, analytical transmission electron microscopy, and X-ray absorption microscopy/spectroscopy. Analyses can be made for chemical, molecular, and isotopic composition coupled with assessment of spatial relationships to surrounding minerals, veins, and fractures. The bulk analyses include improved methods for minimizing contamination and recognizing syngenetic constituents of soluble organic fractions as well as enhanced spectroscopic and pyrolytic techniques for unlocking syngenetic molecular signatures in kerogen. Together, these technologies provide vital tools for the study of some of the oldest and problematic carbonaceous residues and for advancing our understanding of the earliest stages of biological evolution on Earth and the search for evidence of life beyond Earth. We discuss each of these new technologies, emphasizing their advantages and disadvantages, applications, and likely future directions.

  16. Multiscale properties of unconventional reservoir rocks

    Science.gov (United States)

    Woodruff, W. F.

    A multidisciplinary study of unconventional reservoir rocks is presented, providing the theory, forward modeling and Bayesian inverse modeling approaches, and laboratory protocols to characterize clay-rich, low porosity and permeability shales and mudstones within an anisotropic framework. Several physical models characterizing oil and gas shales are developed across multiple length scales, ranging from microscale phenomena, e.g. the effect of the cation exchange capacity of reactive clay mineral surfaces on water adsorption isotherms, and the effects of infinitesimal porosity compaction on elastic and electrical properties, to meso-scale phenomena, e.g. the role of mineral foliations, tortuosity of conduction pathways and the effects of organic matter (kerogen and hydrocarbon fractions) on complex conductivity and their connections to intrinsic electrical anisotropy, as well as the macro-scale electrical and elastic properties including formulations for the complex conductivity tensor and undrained stiffness tensor within the context of effective stress and poroelasticity. Detailed laboratory protocols are described for sample preparation and measurement of these properties using spectral induced polarization (SIP) and ultrasonics for the anisotropic characterization of shales for both unjacketed samples under benchtop conditions and jacketed samples under differential loading. An ongoing study of the effects of kerogen maturation through hydrous pyrolysis on the complex conductivity is also provided in review. Experimental results are catalogued and presented for various unconventional formations in North America including the Haynesville, Bakken, and Woodford shales.

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

    Science.gov (United States)

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

    2018-05-01

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

  18. Spectrophotometry and organic matter on Iapetus. 1: Composition models

    Science.gov (United States)

    Wilson, Peter D.; Sagan, Carl

    1995-01-01

    Iapetus shows a greater hemispheric albedo asymmetry than any other body in the solar system. Hapke scattering theory and optical constants measured in the laboratory are used to identify possible compositions for the dark material on the leading hemisphere of Iapetus. The materials considered are poly-HCN, kerogen, Murchison organic residue, Titan tholin, ice tholin, and water ice. Three-component mixtures of these materials are modeled in intraparticle mixture of 25% poly-HCN, 10% Murchison residue, and 65% water ice is found to best fit the spectrum, albedo, and phase behavior of the dark material. The Murchison residue and/or water ice can be replaced by kerogen and ice tholin, respectively, and still produce very good fits. Areal and particle mixtures of poly-HCN, Titan tholin, and either ice tholin or Murchison residue are also possible models. Poly-HCN is a necessary component in almost all good models. The presence of poly-HCN can be further tested by high-resolution observations near 4.5 micrometers.

  19. Updated methodology for nuclear magnetic resonance characterization of shales

    Science.gov (United States)

    Washburn, Kathryn E.; Birdwell, Justin E.

    2013-08-01

    Unconventional petroleum resources, particularly in shales, are expected to play an increasingly important role in the world's energy portfolio in the coming years. Nuclear magnetic resonance (NMR), particularly at low-field, provides important information in the evaluation of shale resources. Most of the low-field NMR analyses performed on shale samples rely heavily on standard T1 and T2 measurements. We present a new approach using solid echoes in the measurement of T1 and T1-T2 correlations that addresses some of the challenges encountered when making NMR measurements on shale samples compared to conventional reservoir rocks. Combining these techniques with standard T1 and T2 measurements provides a more complete assessment of the hydrogen-bearing constituents (e.g., bitumen, kerogen, clay-bound water) in shale samples. These methods are applied to immature and pyrolyzed oil shale samples to examine the solid and highly viscous organic phases present during the petroleum generation process. The solid echo measurements produce additional signal in the oil shale samples compared to the standard methodologies, indicating the presence of components undergoing homonuclear dipolar coupling. The results presented here include the first low-field NMR measurements performed on kerogen as well as detailed NMR analysis of highly viscous thermally generated bitumen present in pyrolyzed oil shale.

  20. A Study of Porphyrins in Petroleum Source Rocks

    Energy Technology Data Exchange (ETDEWEB)

    Huseby, Berit

    1997-12-31

    This thesis discusses several aspects of porphyrin geochemistry. Degradation experiments have been performed on the Messel oil shale (Eocene, Germany) to obtain information on porphyrins bound or incorporated into macromolecular structures. Thermal heating of the preextracted kerogen by hydrous pyrolysis was used to study the release of porphyrins and their temperature dependent changes during simulated diagenesis and catagenesis. Selective chemical degradation experiments were performed on the preextracted sediment to get more detailed information about porphyrins that are specifically bound to the macromolecular structures via ester bonds. From the heating experiments, in a separate study, the porphyrin nitrogen content in the generated bitumens was compared to the bulk of organic nitrogen compounds in the fraction. The bulk nitrogen contents in the generated bitumens, the water phase and the residual organic matter was recorded to establish the distribution of nitrogen between the kerogen and product phases. Porphyrins as biomarkers were examined in naturally matured Kimmeridge clay source rocks (Upper Jurassic, Norway), and the use of porphyrins as general indicators of maturity was evaluated. Underlying maturity trends in the biomarker data was investigated by Partial Least Squares analysis. Porphyrin as indicators of depositional conditions was also addressed, where the correlations between the (amounts) abundance of nickel and vanadyl porphyrins were mapped together with other descriptors that are assumed to be indicative of redox depositional conditions. 252 refs., 28 figs., 4 tabs.

  1. Hydrogenation of Estonian oil shale and shale oil

    Energy Technology Data Exchange (ETDEWEB)

    Kogerman, P N; Kopwillem, J

    1932-01-01

    Kukersite was heated in an atmosphere of hydrogen, nitrogen, or water in three series of experiments. Shale samples were heated at 370/sup 0/ to 410/sup 0/C for 2 to 3/sup 1///sub 2/ hours in the presence of 106 to 287 kg/sq cm pressure of water, nitrogen, or hydrogen. In some experiments 5 percent of iron oxide was added to the shale. The amount of kerogen liquefied by hydrogenation was not greater than the amount of liquid products obtained by ordinary distillation. On hydrogenation, kukersite absorbed 1.8 weight-percent of hydrogen. Almost no hydrogenation took place below the decomposition point of kerogen, and the lighter decomposition products were mainly hydrogenated. Hydrogenation of the shale prevented coke formation. Heating kukersite or its crude oil at temperatures of 400/sup 0/ to 410/sup 0/C under 250 kg/sq cm hydrogen pressure produced paraffinic and naphthenic oils of lower boiling points. At higher temperatures and after long-continued heating, the formation of aromatic hydrocarbons was observed.

  2. Carbon-14 measurements and characterization of dissolved organic carbon in ground water

    International Nuclear Information System (INIS)

    Murphy, E.M.

    1987-01-01

    Carbon-14 was measured in the dissolved organic carbon (DOC) in ground water and compared with 14 C analyses of dissolved inorganic carbon (DIC). Two field sites were used for this study; the Stripa mine in central Sweden, and the Milk River Aquifer in southern Alberta, Canada. The Stripa mine consists of a Precambrian granite dominated by fracture flow, while the Milk River Aquifer is a Cretaceous sandstone aquifer characterized by porous flow. At both field sites, 14 C analyses of the DOC provide additional information on the ground-water age. Carbon-14 was measured on both the hydrophobic and hydrophilic organic fractions of the DOC. The organic compounds in the hydrophobic and hydrophilic fractions were also characterized. The DOC may originate from kerogen in the aquifer matrix, from soil organic matter in the recharge zone, of from a combination of these two sources. Carbon-14 analyses, along with characterization of the organics, were used to determine this origin. Carbon-14 analyses of the hydrophobic fraction in the Milk River Aquifer suggest a soil origin, while 14 C analyses of the hydrophilic fraction suggest an origin within the Cretaceous sediments (kerogen) or from the shale in contact with the aquifer

  3. Variations in vitrinite reflectance with organic facies - examples from Pennsylvanian cyclothems of the Midcontinent, USA

    Energy Technology Data Exchange (ETDEWEB)

    Wenger, L M; Baker, D R

    1987-01-01

    Significant variations in vitrinite reflectance (% R/sub o/) with organic facies have been demonstrated from Pennsylvanian -aged cyclothems of the Midcontinent, USA. Thermal alteration index (TAI) and Rock-Eval T/sub m/ax values remain relatively constant through these thin lithologic successions, regardless of facies, and are in reasonable agreement with R/sub o/ measurements on interbedded coal. Organic-rich black and phosphatic black-shales, which contain significant component of liptinitic organic matter of presumed marine algal derivation, display R/sub o/ values which are suppressed relative to the coal benchmark. A distinct correlation between increased hydrogen index (HI) and liptinite content with suppressed reflectivities is apparent. More oxic facies (e.g. calcareous and fossiliferous gray shales and limestones) often display R/sub o/'s that are considerably higher than for coal. Soxhlet extraction prior to maceration yielded no variation in reflectance compared to non-extracted kerogens suggesting bitumen adsorption was not the cause of the apparent suppression in the organic-rich black-shales. Lower total organic carbon (TOC)-normalized bitumen contents and Rock-Eval transformations ratios in liptinite-rich facies suggest differential reaction kinetics for kerogen types, with terrestrial organic matter 'maturing' at an earlier stage than hydrogen-rich marine-derived organic matter. 8 refs., 6 figs., 1 tab.

  4. Palaeoceanographic controls on geochemical characteristics of organic-rich Exshaw mudrocks: role of enhanced primary production

    Energy Technology Data Exchange (ETDEWEB)

    Caplan, M.L.; Bustin, R.M. [University of British Columbia, Vancouver (Canada). Dept. of Earth and Ocean Sciences

    1999-07-01

    Organic-rich source rocks have generally been attributed to enhanced preservation of organic matter under anoxic bottom waters. Here geochemical analysis of kerogen and whole rock samples of organic-rich (lithofacies B{sub 1}) and organic-lean (lithofacies B{sub 2}) laminated mudrocks of the Devonian-Carboniferous Exshaw Formation, Alberta, highlight the importance of primary production in governing the quantity and quality of organic matter. Lower Si/Al, K/Al, Ti/Al and quartz/clay ratios in lithofacies B{sub 2}, similar maceral types and the laminated fabric of the two lithofacies indicate that the quality and quantity of organic matter are not related to grain size, redox or organic matter source changes. High Total Organic Carbon (TOC) and Hydrogen Index (HI), low Oxidation Index (Ox.I. ratio of oxygen functional groups to aliphatic groups derived by FTIR), lighter {delta}{sup 15}N{sub tot} and heavier {delta}{sup 13}C{sub org} isotopes indicate that kerogen of lithofacies B{sub 1} accumulated during periods of high organic-carbon production and delivery of relatively fresh, labile, well-preserved organic matter to the sea floor. In contrast, low TOC, HI, high Ox.I., heavier {delta}{sup 15}N{sub tot} and lighter {delta}{sup 13}C{sub org} isotopes indicate low primary productivity and delivery, high recycling and poor preservation of organic matter during accumulation of lithofacies B{sub 2}. (author)

  5. Biogenicity and Syngeneity of Organic Matter in Ancient Sedimentary Rocks: Recent Advances in the Search for Evidence of Past Life

    Science.gov (United States)

    Oehler, Dorothy Z.; Cady, Sherry L.

    2014-08-01

    The past decade has seen an explosion of new technologies for assessment of biogenicity and syngeneity of carbonaceous material within sedimentary rocks. Advances have been made in techniques for analysis of in situ organic matter as well as for extracted bulk samples of soluble and insoluble (kerogen) organic fractions. The in situ techniques allow analysis of micrometer-to-sub-micrometer-scale organic residues within their host rocks and include Raman and fluorescence spectroscopy/imagery, confocal laser scanning microscopy, and forms of secondary ion/laser-based mass spectrometry, analytical transmission electron microscopy, and X-ray absorption microscopy/spectroscopy. Analyses can be made for chemical, molecular, and isotopic composition coupled with assessment of spatial relationships to surrounding minerals, veins, and fractures. The bulk analyses include improved methods for minimizing contamination and recognizing syngenetic constituents of soluble organic fractions as well as enhanced spectroscopic and pyrolytic techniques for unlocking syngenetic molecular signatures in kerogen. Together, these technologies provide vital tools for the study of some of the oldest and problematic carbonaceous residues and for advancing our understanding of the earliest stages of biological evolution on Earth and the search for evidence of life beyond Earth. We discuss each of these new technologies, emphasizing their advantages and disadvantages, applications, and likely future directions.

  6. Biogenicity and Syngeneity of Organic Matter in Ancient Sedimentary Rocks: Recent Advances in the Search for Evidence of Past Life

    Directory of Open Access Journals (Sweden)

    Dorothy Z. Oehler

    2014-08-01

    Full Text Available The past decade has seen an explosion of new technologies for assessment of biogenicity and syngeneity of carbonaceous material within sedimentary rocks. Advances have been made in techniques for analysis of in situ organic matter as well as for extracted bulk samples of soluble and insoluble (kerogen organic fractions. The in situ techniques allow analysis of micrometer-to-sub-micrometer-scale organic residues within their host rocks and include Raman and fluorescence spectroscopy/imagery, confocal laser scanning microscopy, and forms of secondary ion/laser-based mass spectrometry, analytical transmission electron microscopy, and X-ray absorption microscopy/spectroscopy. Analyses can be made for chemical, molecular, and isotopic composition coupled with assessment of spatial relationships to surrounding minerals, veins, and fractures. The bulk analyses include improved methods for minimizing contamination and recognizing syngenetic constituents of soluble organic fractions as well as enhanced spectroscopic and pyrolytic techniques for unlocking syngenetic molecular signatures in kerogen. Together, these technologies provide vital tools for the study of some of the oldest and problematic carbonaceous residues and for advancing our understanding of the earliest stages of biological evolution on Earth and the search for evidence of life beyond Earth. We discuss each of these new technologies, emphasizing their advantages and disadvantages, applications, and likely future directions.

  7. GKI water quality studies. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Hutchinson, D L

    1980-01-01

    GKI water quality data collected in 1978 and early 1979 was evaluated with the objective of developing preliminary characterizations of native groundwater and retort water at Kamp Kerogen, Uintah County, Utah. Restrictive analytical definitions were developed to describe native groundwater and GKI retort water in an effort to eliminate from the sample population both groundwater samples affected by retorting and retort water samples diluted by groundwater. Native groundwater and retort water sample analyses were subjected to statistical manipulation and testing to summarize the data to determine the statistical validity of characterizations based on the data available, and to identify probable differences between groundwater and retort water based on available data. An evaluation of GKI water quality data related to developing characterizations of native groundwater and retort water at Kamp Kerogen was conducted. GKI retort water and the local native groundwater both appeared to be of very poor quality. Statistical testing indicated that the data available is generally insufficient for conclusive characterizations of native groundwater and retort water. Statistical testing indicated some probable significant differences between native groundwater and retort water that could be determined with available data. Certain parameters should be added to and others deleted from future laboratory analyses suites of water samples.

  8. Permeability changes in coal resulting from gas desorption. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Levine, J.R.; Johnson, P.W.

    1992-11-30

    This report documents studies on the effects of gas sorption on coal, with the intent of eventually evaluating how sorption and strain affect permeability. These studies were, carried out at the University of Alabama during the period from 1989 through 1992. Two major experimental methods were developed and used. In the strain experiments, electronic strain gauges were attached to polished blocks of coal in order to measure linear and volumetric swelling due to gas sorption. The effects of bedding plane orientation, of gas type, and of coal type were investigated. In the gravimetric experiment the weight of small samples of coal was measured during exposure to high pressure gases. Sample measurements were corrected for buoyancy effects and for sample swelling, and the results were plotted in the form of Langmuir isotherms. Experiments were conducted to determine the effect of grain size, coal type, moisture, and of sorbant gas. The advantage of this method is that it can be applied to very small samples, and it enabled comparison liptinite versus vitrinite concentrates, and kerogen rich versus kerogen depleted oil shales. Also included is a detailed discussion of the makeup of coal and its effect on gas sorption behavior.

  9. Permeability changes in coal resulting from gas desorption

    Energy Technology Data Exchange (ETDEWEB)

    Levine, J.R.; Johnson, P.W.

    1992-11-30

    This report documents studies on the effects of gas sorption on coal, with the intent of eventually evaluating how sorption and strain affect permeability. These studies were, carried out at the University of Alabama during the period from 1989 through 1992. Two major experimental methods were developed and used. In the strain experiments, electronic strain gauges were attached to polished blocks of coal in order to measure linear and volumetric swelling due to gas sorption. The effects of bedding plane orientation, of gas type, and of coal type were investigated. In the gravimetric experiment the weight of small samples of coal was measured during exposure to high pressure gases. Sample measurements were corrected for buoyancy effects and for sample swelling, and the results were plotted in the form of Langmuir isotherms. Experiments were conducted to determine the effect of grain size, coal type, moisture, and of sorbant gas. The advantage of this method is that it can be applied to very small samples, and it enabled comparison liptinite versus vitrinite concentrates, and kerogen rich versus kerogen depleted oil shales. Also included is a detailed discussion of the makeup of coal and its effect on gas sorption behavior.

  10. Characteristics of the Triassic Source Rocks of the Aitutu Formation in the (West Timor Basin

    Directory of Open Access Journals (Sweden)

    Asep Kurnia Permana

    2014-12-01

    Full Text Available DOI:10.17014/ijog.v1i3.192The Triassic rocks of the (West Timor Basin have been identified that was mainly deposited in the  marine environment. The fine grained clastics and carbonate  rocks of this Triassic marine  facies are considered to be the most promising source rocks potential in this basin. In this paper we present geochemical and petrographic data from outcrop samples of the Triassic carbonate Aitutu Formation, due to emphasized the organic maturation, kerogen type of the organic matter and the origin of the organic matter.  A representative of selected sample were subjected to the Rock-Eval Pyrolisis, vitrinite reflectance and thermal alteration index, bitumen extraction, were analyzed on the GC-MS. The samples were collected from marine deposit of the Triassic Sequence. The TOC values of the analyzed sample range between rich and rich organic richness (0.51% - 9.16%, wt.%, TOC, which consists mainly of type II and III kerogen and the organic matter consider to be predominantly oil/gas prone and gas prone potential. The thermal maturity assessed from Tmax, TAI, and vitrinite reflectance shows an immature to early peak mature stage of the organic matter. The GC-MS analyses of the biomarkers indicate mainly the organic matter derived from mixed source rocks facies containing alga debris and higher plant terrestrial origin.

  11. Development of new estimation method for CO2 evolved from oil shale

    International Nuclear Information System (INIS)

    Sato, S.; Enomoto, M.

    1997-01-01

    The quality of fossil fuels tends to be evaluated by amounts of CO 2 emissions. For the evaluation of an oil shale from this point, an on-line thermogravimetric-gas chromatographic system was used to measure CO 2 evolution profiles on temperature with a small oil shale sample. This method makes it possible to estimate the amounts of CO 2 evolved from kerogen and carbonates in retorting and those from carbonates in combustion, respectively. These results will be basic data for a novel oil shale retorting process for the control of CO 2 emissions. The profiles for Thai and Colorado oil shales have shown CO 2 mainly evolved by the pyrolysis of kerogen below 550 degree C, and that evolved by the decomposition of carbonates above that temperature. On the other hand, the profile for Condor oil shale showed that most carbonates decomposed below 550 degree C, while only small amounts of carbonates decomposed above this temperature. 14 refs., 2 figs., 3 tabs

  12. Triassic oils and related hydrocarbon kitchens in the Adriatic basin

    Energy Technology Data Exchange (ETDEWEB)

    Novelli, L.; Demaison, G. (AGIP, Milan (Italy))

    1988-08-01

    Without exception, the oils from both the Abruzzi basin and Albanian foredeep are of lower Liassic to Upper Triassic origin. This is demonstrated by biological marker-based correlations between the oils and stratigraphically controlled, carbonate-rich source rocks. The biomarker studies also provided proof to conclude that many of the oils possess low API gravities and high sulfur contents because they are immature rather than biodegraded. Following the geochemical investigations, a computer-aided, basinwise maturation simulation of the hydrocarbon kitchens was carried out, with backstripping in geologic time. The simulations, performed with the Tissot-Espitalie kinetic model, used basin-specific kerogen activation energies obtained by the optimum method. These simulated values were calibrated with observed values in deep wells. Two characteristics diverge from normal petroleum basin situations (e.g., the North Sea basin): sulfur-rich kerogens in the source rocks, featuring relatively low activation energy distributions, and low geothermal gradients in the subsurface. The geographic outlines of simulated Triassic-lower Liassic hydrocarbon kitchens closely coincide with the zones of petroleum occurrence and production in the Adriatic basin. Furthermore, API gravities of the oils are broadly predicted by the mathematical simulations. This methodology has once again shown its ability to rationally high-grade the petroleum-rich sectors of sedimentary basin while identifying those areas where chances of success are extremely low regardless of the presence of structures.

  13. A Study of Porphyrins in Petroleum Source Rocks

    Energy Technology Data Exchange (ETDEWEB)

    Huseby, Berit

    1996-12-31

    This thesis discusses several aspects of porphyrin geochemistry. Degradation experiments have been performed on the Messel oil shale (Eocene, Germany) to obtain information on porphyrins bound or incorporated into macromolecular structures. Thermal heating of the preextracted kerogen by hydrous pyrolysis was used to study the release of porphyrins and their temperature dependent changes during simulated diagenesis and catagenesis. Selective chemical degradation experiments were performed on the preextracted sediment to get more detailed information about porphyrins that are specifically bound to the macromolecular structures via ester bonds. From the heating experiments, in a separate study, the porphyrin nitrogen content in the generated bitumens was compared to the bulk of organic nitrogen compounds in the fraction. The bulk nitrogen contents in the generated bitumens, the water phase and the residual organic matter was recorded to establish the distribution of nitrogen between the kerogen and product phases. Porphyrins as biomarkers were examined in naturally matured Kimmeridge clay source rocks (Upper Jurassic, Norway), and the use of porphyrins as general indicators of maturity was evaluated. Underlying maturity trends in the biomarker data was investigated by Partial Least Squares analysis. Porphyrin as indicators of depositional conditions was also addressed, where the correlations between the (amounts) abundance of nickel and vanadyl porphyrins were mapped together with other descriptors that are assumed to be indicative of redox depositional conditions. 252 refs., 28 figs., 4 tabs.

  14. Ideas and perspectives: hydrothermally driven redistribution and sequestration of early Archaean biomass – the “hydrothermal pump hypothesis”

    Directory of Open Access Journals (Sweden)

    J.-P. Duda

    2018-03-01

    Full Text Available Archaean hydrothermal chert veins commonly contain abundant organic carbon of uncertain origin (abiotic vs. biotic. In this study, we analysed kerogen contained in a hydrothermal chert vein from the ca. 3.5 Ga Dresser Formation (Pilbara Craton, Western Australia. Catalytic hydropyrolysis (HyPy of this kerogen yielded n-alkanes up to n-C22, with a sharp decrease in abundance beyond n-C18. This distribution ( ≤  n-C18 is very similar to that observed in HyPy products of recent bacterial biomass, which was used as reference material, whereas it differs markedly from the unimodal distribution of abiotic compounds experimentally formed via Fischer–Tropsch-type synthesis. We therefore propose that the organic matter in the Archaean chert veins has a primarily microbial origin. The microbially derived organic matter accumulated in anoxic aquatic (surface and/or subsurface environments and was then assimilated, redistributed and sequestered by the hydrothermal fluids (hydrothermal pump hypothesis.

  15. Evaluating Re-Os systematics in organic-rich sedimentary rocks in response to petroleum generation using hydrous pyrolysis experiments

    Science.gov (United States)

    Rooney, A.D.; Selby, D.; Lewan, M.D.; Lillis, P.G.; Houzay, J.-P.

    2012-01-01

    Successful application of the 187Re–187Os geochronometer has enabled the determination of accurate and precise depositional ages for organic-rich sedimentary rocks (ORS) as well as establishing timing constraints of petroleum generation. However, we do not fully understand the systematics and transfer behaviour of Re and Os between ORS and petroleum products (e.g., bitumen and oil). To more fully understand the behaviour of Re–Os systematics in both source rocks and petroleum products we apply hydrous pyrolysis to two immature hydrocarbon source rocks: the Permian Phosphoria Formation (TOC = 17.4%; Type II-S kerogen) and the Jurassic Staffin Formation (TOC = 2.5%; Type III kerogen). The laboratory-based hydrous pyrolysis experiments were carried out for 72 h at 250, 300, 325 and 350 °C. These experiments provided us with whole rock, extracted rock and bitumen and in some cases expelled oil and asphaltene for evaluation of Re–Os isotopic and elemental abundance. The data from these experiments demonstrate that the majority (>95%) of Re and Os are housed within extracted rock and that thermal maturation does not result in significant transfer of Re or Os from the extracted rock into organic phases. Based on existing thermodynamic data our findings suggest that organic chelating sites have a greater affinity for the quadravalent states of Re and Os than sulphides. Across the temperature range of the hydrous pyrolysis experiments both whole rock and extracted rock 187Re/188Os ratios show small variations (3.3% and 4.7%, for Staffin, respectively and 6.3% and 4.9% for Phosphoria, respectively). Similarly, the 187Os/188Os ratios show only minor variations for the Staffin and Phosphoria whole rock and extracted rock samples (0.6% and 1.4% and 1.3% and 2.2%). These isotopic data strongly suggest that crude oil generation through hydrous pyrolysis experiments does not disturb the Re–Os systematics in ORS as supported by various studies on natural systems. The

  16. Integrated petrographic and geochemical study of coal and gas shales from the Sabinas and Chihuahua basins, North of Mexico: estimation of methane gas resources

    International Nuclear Information System (INIS)

    De La O Burrola, Francisco

    2013-01-01

    This comprehensive characterization study was performed using organic petrology and geochemistry conducted in the Sabinas basin and Chihuahua in northern Mexico. This information allowed a numerical modeling of gas formation, considering the thermal subsidence of coal and carbonaceous shales. The objectives of this thesis are: - Establish a characterization methodology for the studied rocks - Estimate potential gas generator and its regional distribution - Estimate the methane gas resources For the development of this project, we conducted an intensive campaign representative sampling of coal, carbonaceous shales and coal gas 'in situ'. For the Sabinas basin were studied 97 samples and 114 samples in the basin of Chihuahua. The analyses carried out that were used on the samples analyzed allowed to characterize the kerogen and gas. The methodology used to cross petrographic and geochemical information to analyze the petroleum system by numerical modeling. Analyses were: Petrographic, reflectance %Ro, elemental analysis and immediate, Rock Eval6 R (Bulk rock), isotopic analysis, δ 13 C, δD, (coal gas), scanning electron microscopy, image analysis and analysis of macerals fluid inclusions. The analyzes that were used on the samples allowed to characterize the sample, the kerogen and gas. The methodology used to cross petrographic and geochemical information for analyze the oil system by numerical modeling. Analyses were: Petrographic, reflectance %Ro, elemental analysis and immediate, Rock Eval6 R (Bulk rock), isotopic analysis, δ 13 C, δD, (coal gas), scanning electron microscopy, image analysis and analysis of macerals fluid inclusions A computer program was constructed to cross the information with the analysis of samples of artificial maturation experiments in the laboratory. This approach allowed estimation of methane gas resources generated by coal and carbonaceous shales. The main results obtained for Sabinas Basin were: - The kerogen of the

  17. Standardization of reflectance measurements in dispersed organic matter: results of an exercise to improve interlaboratory agreement

    Science.gov (United States)

    Hackley, Paul C.; Araujo, Carla Viviane; Borrego, Angeles G.; Bouzinos, Antonis; Cardott, Brian; Cook, Alan C.; Eble, Cortland; Flores, Deolinda; Gentzis, Thomas; Gonçalves, Paula Alexandra; Filho, João Graciano Mendonça; Hámor-Vidó, Mária; Jelonek, Iwona; Kommeren, Kees; Knowles, Wayne; Kus, Jolanta; Mastalerz, Maria; Menezes, Taíssa Rêgo; Newman, Jane; Pawlewicz, Mark; Pickel, Walter; Potter, Judith; Ranasinghe, Paddy; Read, Harold; Reyes, Julito; Rodriguez, Genaro De La Rosa; de Souza, Igor Viegas Alves Fernandes; Suarez-Ruiz, Isabel; Sýkorová, Ivana; Valentine, Brett J.

    2015-01-01

    Vitrinite reflectance generally is considered the most robust thermal maturity parameter available for application to hydrocarbon exploration and petroleum system evaluation. However, until 2011 there was no standardized methodology available to provide guidelines for vitrinite reflectance measurements in shale. Efforts to correct this deficiency resulted in publication of ASTM D7708: Standard test method for microscopical determination of the reflectance of vitrinite dispersed in sedimentary rocks. In 2012-2013, an interlaboratory exercise was conducted to establish precision limits for the D7708 measurement technique. Six samples, representing a wide variety of shale, were tested in duplicate by 28 analysts in 22 laboratories from 14 countries. Samples ranged from immature to overmature (0.31-1.53% Ro), from organic-lean to organic-rich (1-22 wt.% total organic carbon), and contained Type I (lacustrine), Type II (marine), and Type III (terrestrial) kerogens. Repeatability limits (maximum difference between valid repetitive results from same operator, same conditions) ranged from 0.03-0.11% absolute reflectance, whereas reproducibility limits (maximum difference between valid results obtained on same test material by different operators, different laboratories) ranged from 0.12-0.54% absolute reflectance. Repeatability and reproducibility limits degraded consistently with increasing maturity and decreasing organic content. However, samples with terrestrial kerogens (Type III) fell off this trend, showing improved levels of reproducibility due to higher vitrinite content and improved ease of identification. Operators did not consistently meet the reporting requirements of the test method, indicating that a common reporting template is required to improve data quality. The most difficult problem encountered was the petrographic distinction of solid bitumens and low-reflecting inert macerals from vitrinite when vitrinite occurred with reflectance ranges overlapping

  18. Fácies Orgânica da Formação La Luna, Bacia do Valle Superior del Magdalena, Colômbia:Implicações para a Geração de Petróleo e Caracterização Paleoambiental.

    Directory of Open Access Journals (Sweden)

    Juliana Andrade Iemini

    2007-08-01

    Full Text Available Upper Cretaceous pelitic rocks generate most of the oil reserves in Colombia. In Del Magdalena Upper Valley (MUV, the existenceof good quality outcrops and thermal evolution levels that vary from immaturity to the end of the oil generation “window” makes it one of themost appropriate regions for the study of primary migration and generation of oil in Upper Cretaceous. The main objectives of this work wereto study the organic facies of La Luna Formation in an outcrop section called Riacho Bambuca (Bambuca Creek, determine the oil generationpotential and characterize the paleoenvironment. For this research, 24 samples were used in palynofacies analysis (characterization ofthe kerogen components assembly and in organic geochemistry analysis (Total Organic Carbon – TOC analysis and Rock-Eval pyrolysis,provided by Colombia Oil Institute – ECOPETROL. The palynofacies analysis included the use of microscopy techniques (transmitted whitelight and incident blue light. Furthermore, a Spore Coloration Index (SCI analysis was made in order to determine the thermal maturationstage. The studied material was composed mainly of an amorphous organic substance, with its fluorescent coloration varying from yellow tobright orange. The palynomorph group is represented by spore morph and dinoflagellate cysts. The ligneous material are present in very lowpercentages; they are mainly opaque phytoclasts. The results of geochemical analysis showed TOC contents ranging from medium to high,excellent potential for the generation of hydrocarbons (PG > 4 mg HC/g of rock, hydrogen index ranging from 329 to 589 mg HC/g, andlow values of oxygen index, characterizing type II kerogen. The low degree of thermal maturation was determined by Spore Coloration Indexvalues ranging from 2,5 to 3,0, Tmax values below 440°C and Hydrocarbon Production Index inferior to 0,2. According to the organic faciesdata, La Luna Formation deposited in a marine environment with facies from

  19. The influence of shale depositional fabric on the kinetics of hydrocarbon generation through control of mineral surface contact area on clay catalysis

    Science.gov (United States)

    Rahman, Habibur M.; Kennedy, Martin; Löhr, Stefan; Dewhurst, David N.; Sherwood, Neil; Yang, Shengyu; Horsfield, Brian

    2018-01-01

    Accurately assessing the temperature and hence the depth and timing of hydrocarbon generation is a critical step in the characterization of a petroleum system. Clay catalysis is a potentially significant modifier of hydrocarbon generation temperature, but experimental studies of clay catalysis show inconsistent or contradictory results. This study tests the hypothesis that source rock fabric itself is an influence on clay mineral catalysis as it controls the extent to which organic matter and clay minerals are physically associated. Two endmember clay-organic fabrics distinguish the source rocks studied: (1) a particulate fabric where organic matter is present as discrete, >5 μm particles and (2) a nanocomposite fabric in which amorphous organic matter is associated with clay mineral surfaces at sub-micron scale. High-resolution electron imaging and bulk geochemical characterisation confirm that samples of the Miocene Monterey Formation (California) are representative of the nanocomposite source rock endmember, whereas samples from the Permian Stuart Range Formation (South Australia) represent the particulate source rock endmember. Kinetic experiments are performed on paired whole rock and kerogen isolate samples from these two formations using open system, non-isothermal pyrolysis at three different heating rates (0.7, 2 and 5 K/min) to determine the effects of the different shale fabrics on hydrocarbon generation kinetics. Extrapolation to a modelled geological heating rate shows a 20 °C reduction in the onset temperature of hydrocarbon generation in Monterey Formation whole rock samples relative to paired kerogen isolates. This result is consistent with the Monterey Formations's nanocomposite fabric where clay catalysis can proceed because reactive clay minerals are intimately associated with organic matter. By contrast, there is no significant difference in the modelled hydrocarbon generation temperature of paired whole rock and kerogen isolates from the

  20. The Lower Jurassic Posidonia Shale in southern Germany: results of a shale gas analogue study

    Science.gov (United States)

    Biermann, Steffen; Schulz, Hans-Martin; Horsfield, Brian

    2013-04-01

    The shale gas potential of Germany was recently assessed by the Federal Institute for Geosciences and Natural Resources (2012 NiKo-Project) and is - in respect of the general natural gas occurrence in Germany - regarded as a good alternative hydrocarbon source. The Posidonia Shale in northern and southern Germany is one of the evaluated rock formation and easily accessible in outcrops in the Swabian Alps (southern Germany). The area of interest in this work is located in such an outcrop that is actively used for open pit mining next to the town of Dotternhausen, 70 km southwest of Stuttgart. 31 samples from the quarry of Dotternhausen were analyzed in order to characterize the immature Posidonia Shale (Lower Toarcian, Lias ɛ) of southern Germany as a gas shale precursor. Methods included are Rock Eval, Open Pyrolysis GC, SEM, Mercury Intrusion Porosimetry, XRD, and other. The samples of Dotternhausen contain exclusively type II kerogen. The majority of the organic matter is structureless and occurs in the argillaceous-calcareous matrix. Structured organic matter appears predominantly as alginite, in particular the algae "tasmanite" is noticeable. The TOC content ranges up to 16 wt% with a high bitumen content. The mineral content characterizes the Posidonia Shale as a marlstone or mudstone with varying clay-calcite ratios. The quartz and pyrite content reaches up to 20 wt% and 9 wt%, respectively. The rock fabric is characterized by a fine grained and laminated matrix. The mean porosity lies between 4 and 12 %. Fractures other than those introduced by sample preparation were not observed. The Posidonia Shale is predicted to have an excellent source rock potential and will generate intermediate, P-N-A low wax oil when exposed to higher P-T-conditions ("oil kitchen"). Contact surfaces between the kerogen and matrix will be vulnerable to pressure induced fracturing caused by hydrocarbon formation. Additional porosity will be formed during maturation due to the

  1. Morphological and ecological complexity in early eukaryotic ecosystems.

    Science.gov (United States)

    Javaux, E J; Knoll, A H; Walter, M R

    2001-07-05

    Molecular phylogeny and biogeochemistry indicate that eukaryotes differentiated early in Earth history. Sequence comparisons of small-subunit ribosomal RNA genes suggest a deep evolutionary divergence of Eukarya and Archaea; C27-C29 steranes (derived from sterols synthesized by eukaryotes) and strong depletion of 13C (a biogeochemical signature of methanogenic Archaea) in 2,700 Myr old kerogens independently place a minimum age on this split. Steranes, large spheroidal microfossils, and rare macrofossils of possible eukaryotic origin occur in Palaeoproterozoic rocks. Until now, however, evidence for morphological and taxonomic diversification within the domain has generally been restricted to very late Mesoproterozoic and Neoproterozoic successions. Here we show that the cytoskeletal and ecological prerequisites for eukaryotic diversification were already established in eukaryotic microorganisms fossilized nearly 1,500 Myr ago in shales of the early Mesoproterozoic Roper Group in northern Australia.

  2. Process for oil shale retorting

    Science.gov (United States)

    Jones, John B.; Kunchal, S. Kumar

    1981-10-27

    Particulate oil shale is subjected to a pyrolysis with a hot, non-oxygenous gas in a pyrolysis vessel, with the products of the pyrolysis of the shale contained kerogen being withdrawn as an entrained mist of shale oil droplets in a gas for a separation of the liquid from the gas. Hot retorted shale withdrawn from the pyrolysis vessel is treated in a separate container with an oxygenous gas so as to provide combustion of residual carbon retained on the shale, producing a high temperature gas for the production of some steam and for heating the non-oxygenous gas used in the oil shale retorting process in the first vessel. The net energy recovery includes essentially complete recovery of the organic hydrocarbon material in the oil shale as a liquid shale oil, a high BTU gas, and high temperature steam.

  3. Characterization of some sedimentary sequences from Cambay basin, India, by pyrolysis-GC

    Science.gov (United States)

    Philp, R. P.; Garg, A. K.

    Pyrolysis-gas chromatography of sedimentary sequences from a key exploratory well of the southern Cambay Basin, India, has been performed to characterize the nature of the source material and its maturity. In samples from the Eocene-Paleocene section (2960-3407 m), the pyrolysate is dominated by hydrocarbons in the lower molecular weight region indicating a significant input algal source material. The presence of various xylenes and phenols in the pyrograms is indicative of a significant input from higher plant material. The organic material in this section is interpreted to have been derived from marine-terrestrial source inputs deposited under swampy to marine and reducing environments. Good mature source rocks with type III kerogens which are wet gas/gas condensate-prone have been identified in this region. This paper intends to discuss the characterization of source rocks using the pyrolysis-gas chromatography approach and the significance of the distribution of the pyrolysis product.

  4. Condensation Mechanism of Hydrocarbon Field Formation.

    Science.gov (United States)

    Batalin, Oleg; Vafina, Nailya

    2017-08-31

    Petroleum geology explains how hydrocarbon fluids are generated, but there is a lack of understanding regarding how oil is expelled from source rocks and migrates to a reservoir. To clarify the process, the multi-layer Urengoy field in Western Siberia was investigated. Based on this example, we have identified an alternative mechanism of hydrocarbon field formation, in which oil and gas accumulations result from the phase separation of an upward hydrocarbon flow. There is evidence that the flow is generated by the gases released by secondary kerogen destruction. This study demonstrates that oil components are carried by the gas flow and that when the flow reaches a low-pressure zone, it condenses into a liquid with real oil properties. The transportation of oil components in the gas flow provides a natural explanation for the unresolved issues of petroleum geology concerning the migration process. The condensation mechanism can be considered as the main process of oil field formation.

  5. Complex conductivity of organic-rich shales

    Science.gov (United States)

    Woodruff, W. F.; Revil, A.; Torres-Verdin, C.

    2013-12-01

    We can accurately determine the intrinsic anisotropy and material properties in the laboratory, providing empirical evidence of transverse isotropy and the polarization of the organic and metallic fractions in saturated and unsaturated shales. We develop two distinct approaches to obtain the complex conductivity tensor from spectral induced polarization (SIP) measurements. Experimental results indicate clear anisotropy, and characterize the effects of thermal maturation, TOC, and pyrite, aiding in the calibration and interpretation of geophysical data. SIP is a non-intrusive measurement, sensitive to the surface conductance of mineral grains, frequency-dependent polarization of the electrical double layer, and bulk conductivity of the pore water. The in-phase and quadrature components depend upon parameters of principal importance in unconventional shale formation evaluation (e.g., the distribution of pore throat sizes, formation factor, permeability, salinity and cation exchange capacity (CEC), fluid saturation and wettability). In addition to the contribution of the electrical double layer of non-conducting minerals to surface conductivity, we have observed a clear relaxation associated with kerogen pyrolysis, pyrite distribution, and evidence that the CEC of the kerogen fraction may also contribute, depending on thermal maturation history. We utilize a recent model for anisotropic complex conductivity, and rigorous experimental protocols to quantify the role of kerogen and pyrolysis on surface and quadrature conductivity in mudrocks. The complex conductivity tensor σ* describes the directional dependence of electrical conduction in a porous medium, and accounts for both conduction and polarization. The complex-valued tensor components are given as σ*ij , where σ'ij represents in-phase and σ"ij denotes quadrature conductivities. The directional dependence of the complex conductivity tensor is relegated to the textural properties of the material. The

  6. Thermochemolysis: A New Sample Preparation Approach for the Detection of Organic Components of Complex Macromolecules in Mars Rocks via Gas Chromatography Mass Spectrometry in SAM on MSL

    Science.gov (United States)

    Eugenbrode, J.; Glavin, D.; Dworkin, J.; Conrad, P.; Mahaffy, P.

    2011-01-01

    Organic chemicals, when present in extraterrestrial samples, afford precious insight into past and modern conditions elsewhere in the Solar System . No single technology identifies all molecular components because naturally occurring molecules have different chemistries (e.g., polar vs. non-polar, low to high molecular weight) and interface with the ambient sample chemistry in a variety of modes (i.e., organics may be bonded, absorbed or trapped by minerals, liquids, gases, or other organics). More than 90% of organic matter in most natural samples on Earth and in meteorites is composed of complex macromolecules (e.g. biopolymers, complex biomolecules, humic substances, kerogen) because the processes that tend to break down organic molecules also tend towards complexation of the more recalcitrant components. Thus, methodologies that tap the molecular information contained within macromolecules may be critical to detecting extraterrestrial organic matter and assessing the sources and processes influencing its nature.

  7. A model of oil-generation in a waterlogged and closed system

    Science.gov (United States)

    Zhigao, He

    This paper presents a new model on synthetic effects on oil-generation in a waterlogged and closed system. It is suggested based on information about oil in high pressure layers (including gas dissolved in oil), marsh gas and its fermentative solution, fermentation processes and mechanisms, gaseous hydrocarbons of carbonate rocks by acid treatment, oil-field water, recent and ancient sediments, and simulation experiments of artificial marsh gas and biological action. The model differs completely from the theory of oil-generation by thermal degradation of kerogen but stresses the synthetic effects of oil-generation in special waterlogged and closed geological systems, the importance of pressure in oil-forming processes, and direct oil generation by micro-organisms. Oil generated directly by micro-organisms is a particular biochemical reaction. Another feature of this model is that generation, migration and accumulation of petroleum are considered as a whole.

  8. Oil Shale and Its Relation to Petroleum and Other Fuels (Summary Les schistes à l'huile et leurs relation avec le pétrole et les autres combustibles (résumé

    Directory of Open Access Journals (Sweden)

    Billo S. M.

    2006-10-01

    Full Text Available World oil reserves in oil shales (1. 2 to 2 trillion barrels are at least 4 times as large as proven crude oil petroleum reserves (310 billion barrels. Petroleum is produced from oil shale by pyrolysis (destructive distillation by hecit. Coal can also be converted ta synthetic petroleum products by direct hydrogenation and by the modified Fischer-Tropsch process. Rising cost of oil exploration and production and increasing efficiency of synthetizing processes indicate that synthetic fuels may increase the supply of natural liquid fuels in the foreseeable future. The term kerogen is often used to comprise all the organic matter contained in sediments and may be of two kinds: 1 coalylike kerogen, and 2 sapropellic kerogen - oil shale type. It is believed that both kerogen and petroleum were formed from hypothetical ancestor - protopetroleum. They are found together in sedimenfs and their C13C12 ratios are similar. The largest producer of oil shale ore China, the USSR and Sweden. The USA is technologically prepared to begin production of synthetized fuels through varying economic condition. Richness and size of deposits, cost of mining, cost of retorting, character of products, and location of deposit in relation to plant and market, determine the economic value of a given deposit. Les réserves mondiales de schistes à huile (1,2 à 2 x 10. 12 barils sont au moins quatre fois supérieures aux réserves prouvées de pétrole brut (310 x 10. 9 barils. On extrait le pétrole des schistes par pyrolyse (distillation destructive thermique. Le charbon peut aussi être transformé en hydrocarbures par hydrogénation et par le procédé Fischer-Tropsch modifié. L'augmentation des coûts de l'exploration et de la production du pétrole et amélioration de l'efficacité des procédés synthétiques montrent que les produits synthétiques vont jouer un rôle croissant dans l'approvisionnement en combustibles liquides au cours des années à venir. Le terme k

  9. Organic geochemistry and petrology of oil source rocks, Carpathian Overthrust region, southeastern Poland - Implications for petroleum generation

    Science.gov (United States)

    Kruge, M.A.; Mastalerz, Maria; Solecki, A.; Stankiewicz, B.A.

    1996-01-01

    The organic mailer rich Oligocene Menilite black shales and mudstones are widely distributed in the Carpathian Overthrust region of southeastern Poland and have excellent hydrocarbon generation potential, according to TOC, Rock-Eval, and petrographic data. Extractable organic matter was characterized by an equable distribution of steranes by carbon number, by varying amounts of 28,30-dinor-hopane, 18??(H)-oleanane and by a distinctive group of C24 ring-A degraded triterpanes. The Menilite samples ranged in maturity from pre-generative to mid-oil window levels, with the most mature in the southeastern portion of the study area. Carpathian petroleum samples from Campanian Oligocene sandstone reservoirs were similar in biomarker composition to the Menilite rock extracts. Similarities in aliphatic and aromatic hydrocarbon distributions between petroleum asphaltene and source rock pyrolyzates provided further evidence genetically linking Menilite kerogens with Carpathian oils.

  10. Deposition and alteration of carbonaceous series within a Neotethyan rift at the western boundary of the Arabian plate: The late Permian Um Irna Formation, NW Jordan, a petroleum system

    Energy Technology Data Exchange (ETDEWEB)

    Dill, H.G.; Kus, J. [Federal Institute for Geosciences and Natural Resources, P.O. Box 51 01 53 D-30631 Hannover (Germany); Bechtel, A.; Gratzer, R. [Department of Applied Geosciences and Geophysics, University of Leoben, Peter Tunner Strasse 5, A-8700 Leoben (Austria); Abu Hamad, A.M.B. [Geology Department, University of Jordan, Amman 11942 (Jordan)

    2010-01-07

    During the late Permian (Kungurian to Kazanian) a Neotethyan rift basin evolved at the western boundary of the Arabian Plate, in what is called today the Dead Sea Valley of western Jordan. The break-up of Pangaea was accompanied by low-sinuosity sandy braided- to meandering-fluvial drainage systems which were fed by the uplift of the Arabian Shield and by poorly aerated swamps and ponds that concentrated plant debris of the Cathaysian floral province in the Um Irna Formation. These proximal wet fan sediments are overlain by a dry fan characterized by extensive reddish floodplain deposits, anastomosing channel systems and paleosols. The wet fan is underlain by Cambrian sandstones. These units serve as the top and bottom seals of the OM-bearing system of the Um Irna Formation. The sedimentary rocks of the OM-bearing Um Irna Formation underwent supergene, diagenetic and epigenetic hydrothermal alteration under an elevated geothermal gradient. The temperature increased from the time of deposition of the wet to the time of deposition of the dry fan and caused remobilization of manganese already pre-concentrated in the Cambrian footwall rocks of the rift basin. The anomalous heat regime may be accounted for as a predecessor stage of the Dead Sea Rift which is still active today. Oil seeps are found along faults and fractures near this deep-seated lineamentary fault zone. The deposition and alteration of the organic matter in this late Permian rift are of great consequence for oil generation in the region. Organic petrographic investigations revealed that organic-rich terrestrial carbonaceous and coal rich sediments of mainly of type III kerogen are dominant in the Um Irna Formation. In addition, aquatic liptinite rich sedimentary input (fresh water lake and/or lacustrine swamp) of type I kerogen is also noted. Coal derived organic matter occurs in the form of coaly particles with ranks from subbituminous A to high volatile bituminous C. Higher plant-derived macerals as

  11. The investigation for attaining the optimal yield of oil shale by integrating high temperature reactors

    International Nuclear Information System (INIS)

    Bhattacharyya, A.T.

    1984-03-01

    This work presents a systemanalytical investigation and shows how far a high temperature reactor can be integrated for achieving the optimal yield of kerogen from oil shale. About 1/3 of the produced components must be burnt out in order to have the required high temperature process heat. The works of IGT show that the hydrogen gasification of oil shale enables not only to reach oil shale of higher quality but also allows to achieve a higher extraction quantity. For this reason a hydro-gasification process has been calculated in this work in which not only hydrogen is used as the gasification medium but also two high temperature reactors are integrated as the source of high temperature heat. (orig.) [de

  12. A novel procedure to detect low molecular weight compounds released by alkaline ester cleavage from low maturity coals to assess its feedstock for deep microbial life

    DEFF Research Database (Denmark)

    Glombitza, Clemens; Mangelsdorf, Kai; Horsfield, Brian

    2009-01-01

    and South Island of New Zealand (NZ) were examined to assess the amount of bound LMW organic acids. Formate, acetate and oxalate were detected in significant amounts whereas the amounts of these compounds decrease with increasing maturity of the coal sample. This decrease of LMW organic acids mainly...... for the investigation of low molecular weight (LMW) organic acids linked to the kerogen matrix is presented. These LMW organic acids form a potential feedstock for deep microbial populations. Twelve coal samples of different maturity (vitrinite reflectance (R0) of 0.28–0.80%) from several coal mines on the North...... and generation rates of LMW organic acids indicate that the NZ coals investigated exhibit the potential to feed deep terrestrial microbial life with appropriate substrates over geological time spans....

  13. New Zealand Coals - A Potential Feedstock for Deep Microbial Life

    DEFF Research Database (Denmark)

    Glombitza, Clemens

    2010-01-01

    into the surrounding. Previous studies showed that especially oxygen containing compounds are lost from the macromolecular matrix during diagenesis and early catagenesis. Oxygen containing low molecular weight organic acids (LMWOAs) such as formate, acetate and oxalate represent important substrates for microbial...... reactions. Formate, acetate and oxalate were found to decrease continously from early diagenesis to early catagenesis. This suggests a constant release of these compounds during this maturation interval providing a suitable feedstock for microbial ecosystems in geological time spans. Investigation...... of kerogen-bound high molecular weight fatty acids show for the long chain fatty acids (C20-C30), representing a terrestrial plant material signal, a constant decrease during diagenesis and early catagenesis. In contrast the short chain fatty acids (mainly C16 and C18) show an increase again during early...

  14. The improved flotation of gold from the residues of Orange Free State ores

    International Nuclear Information System (INIS)

    Cabassi, P.A.J.; Loveday, B.K.; Wilkinson, M.J.; Radcliffe, P.H.

    1983-01-01

    The recovery of gold, uranium, and pyrite from accumalated residues at mines in the Orange Free State is adversely affected by the presence of pyrophyllite, which is naturally floatable and must be prevented from floating with the desired constituents by the use of a mica depressant, and of thucholite (uraniferous kerogen), which contains significant quantities of uranium and gold but does not float readily in the presence of a mica depressant. In laboratory tests on these residues, the use of a mixture of MIBC (methyl isobutyl carbinol) and paraffin in addition to the suite of reagents normally used was found to increase the gold recovery substantially, but the sulphur grade was lower. The recovery of thucholite also increased considerably, but the proportion of uranium, associated with this mineral was small. Plant trials, which are continuing, have been encouraging, indicating an increase in the gold recovery of 4,6 per cent

  15. Organic petrology and Rock-Eval characteristics in selected surficial samples of the Tertiary Formation, South Sumatra Basin

    Directory of Open Access Journals (Sweden)

    M. H. Hermiyanto

    2014-06-01

    Full Text Available http://dx.doi.org/10.17014/ijog.vol4no3.20096Organic petrologic data of the DOM of Talangakar and Muaraenim Formations show that the organic matter consisting mainly of vitrinite group is essentially composed of telocollinite (1.0 – 70.8 % and desmocollinite (0.8 – 66.6 % with minor telinite (0.6 – 9.4 %, detrovitrinite (0.6 – 6.0 %, and cor- pocollinite (0.6 – 2.0 %. Minor exinite (0.4 – 7.8 % and inertinite (0.4 – 8.0 % are also determined. However, mineral matter varies from 0.6 – 99.44 %. Downwards, the increase in vitrinite reflectance (0.33 – 0.48 % is concomitant with the depth of each formation. Furthermore, based on Rock-eval pyrolysis, TOC value of the Talangakar Formation ranges from 0.09 – 15.38 %, Gumai 0.34 – 0.39 %, Airbenakat 0.32 – 4.82 %, and Muaraenim between 0.08 – 15.22 %. Moreover the PY (Potential Yield value variation of the Talangakar, Gumai, Airbenakat, and Muaraenim Formations are between 0.04 – 36.61 mg HC/g rock, 0.53 – 0.81 mg HC/g rock, 0.1 – 4.37 mg HC/g rock, and 0.07 – 129.8 mg HC/g rock respectively. Therefore, on the basis of those two parameters, the four formations are included into a gas - oil prone source rock potential. However, the Talangakar and Muaraenim Formations are poor to excellent category, whereas the Air Benakat tends to indicate a poor – fair category and Gumai Formation are only within a poor category. Tmax value of the Talangakar ranges from 237 – 4380 C, Gumai 316 – 3590 C, Airbenakat 398 – 4340 C with exceptions of 4970 C and 5180 C, and Muaraenim Forma- tions 264 – 4250 C. The Talangakar Formation contains kerogen Type II dan III, with the HI (Hydrogen Index value varies from 45.16 – 365.43. However two samples show value of 0. The organic content of the Gumai and Air Benakat Formations are included into kerogen type III, with HI value ranges from11.87 – 40.82, and 19 – 114 respectively. Moreover the Muaraenim Formation has two category of

  16. 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.

  17. Palynology of the middle jurassic lower graben sand formation of the U-1 well, Danish Central Trough

    Energy Technology Data Exchange (ETDEWEB)

    Hoelstad, T.

    1986-01-01

    Twenty-one sidewall core samples from the lower 56 metres of the Lower Graben Sand Formation in the U-1 well are described with respect to their kerogen content and microflora in order to gain a better understanding of the depositional environment and the age relations. Based on e.g. the inconsistent dinoflagellate cyst occurrences, marginal marine conditions are concluded. The dinoglagellate cyst Pareodinia prolongata, Acanthaulax senta, Scriniodinium crystallinum, Energlynia acollaris, Wanaea thysanota and Hystrichogonyaulax cladophora and the recovered playnomorph assemblage in general permit an age determination as follows: 21 m Collovian undifferentiated, 7.9 latest Middle Callovian - earliest Late Callovian, 6.1 m latest Late Callovian and 21 m latest Late Callovian. - earliest Early Oxfordian.

  18. The upper limit of maturity of natural gas generation and its implication for the Yacheng formation in the Qiongdongnan Basin, China

    Science.gov (United States)

    Su, Long; Zheng, Jianjing; Chen, Guojun; Zhang, Gongcheng; Guo, Jianming; Xu, Yongchang

    2012-08-01

    Vitrinite reflectance (VR, Ro%) measurements from residual kerogen of pyrolysis experiments were performed on immature Maoming Oil Shale substituted the samples for the gas-prone source rocks of Yacheng formation of the Qiongdongnan Basin in the South China Sea. The work was focused on determination an upper limit of maturity for gas generation (ULMGG) or "the deadline of natural gas generation". Ro values at given temperatures increase with increasing temperature and prolonged heating time, but ΔRo-value, given a definition of the difference of all values for VR related to higher temperature and adjacent lower temperature in open-system non-isothermal experiment at the heating rate of 20 °C/min, is better than VR. And representative examples are presented in this paper. It indicates that the range of natural gas generation for Ro in the main gas generation period is from 0.96% to 2.74%, in which ΔRo is in concordance with the stage for the onset and end of the main gas generation period corresponding to 0.02% up to 0.30% and from 0.30% up to 0.80%, respectively. After the main gas generation period of 0.96-2.74%, the evolution of VR approach to the ULMGG of the whole rock for type II kerogen. It is equal to 4.38% of VR, where the gas generation rates change little with the increase of maturation, ΔRo is the maximum of 0.83% corresponding to VR of 4.38%Ro, and the source rock does not nearly occur in the end process of hydrocarbon gas generation while Ro is over 4.38%. It shows that it is the same the ULMGG from the whole rock for type II kerogen as the method with both comparison and kinetics. By comparing to both the conclusions of pyrolysis experiments and the data of VR from the source rock of Yacheng formation on a series of selected eight wells in the shallow-water continental shelf area, it indicate that the most hydrocarbon source rock is still far from reaching ULMGG from the whole rock for type II kerogen. The source rock of Yacheng formation in the

  19. Synchrotron Radiation X-Ray Fluorescence nanoanalyses of the metallome of a ~3.3 Ga-old microbial biofilm from the Barberton greenstone belt, South Africa.

    Science.gov (United States)

    Hubert, A.; Lemelle, L.; Salome, M.; Cloetens, P.; Westall, F.; Simionovici, A.

    2012-04-01

    Combining in situ nanometer-scale techniques on the fossilized Josefsdal Chert Microbial Biofilm (JCMB) reveals a distinct vertical structural and compositional organisation: the lower part is calcified as aragonite, while the upper non-calcified kerogenous layer is characterised by up to 1% sulphur [1]. The in situ analysis of all the metals as a group represents a useful microbial fingerprint [2] and we will continue to explore it. Synchrotron Radiation X-Ray Fluorescence maps of high spatial resolution (Conference Proceedings, 1221, 131-138. 4. Bleuet P., et al., 2008. App. Phys. Lett., 92, 213111-1-3. 5. Golosio B., et al., 2003. Appl. Phys., 94, 145-157. 6. M. Haschke, 2003. PhD dissertation, T.U. Berlin. 7. Simionovici A. S., et al., 2010. Proceedings of the Meteoritical Society Conference, N.Y., USA. 8. Solé V.A., et al., 2006, Elsevier, 62, 63-68.

  20. NASA Curiosity rover hits organic pay dirt on Mars

    Science.gov (United States)

    Voosen, Paul

    2018-06-01

    Since NASA's Curiosity rover landed on Mars in 2012, it has sifted samples of soil and ground-up rock for signs of organic molecules—the complex carbon chains that on Earth form the building blocks of life. Past detections have been so faint that they could be just contamination. Now, samples taken from two different drill sites on an ancient lakebed have yielded complex organic macromolecules that look strikingly similar to kerogen, the goopy fossilized building blocks of oil and gas on Earth. At a few dozen parts per million, the detected levels are 100 times higher than previous finds, but scientists still cannot say whether they have origins in biology or geology. The discovery positions scientists to begin searching for direct evidence of past life on Mars and bolsters the case for returning rock samples from the planet, an effort that begins with the Mars 2020 rover.

  1. Anticipating flow assurance challenges through geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Flannery, M. [Fluid Evaluation and Sampling Technologies (FEAST) Team, Shell International Exploration and Production (United Kingdom)

    2008-07-01

    The behaviour of reservoir fluids pose a challenge at all stages of petroleum production, from the reservoir to refinery. The challenges sometimes stem from sub-optimal operations or inappropriate system design, with assumptions of similar fluid properties across the field. Hydrocarbon fluid phase behaviour is the product of local PVT conditions and the geochemical identity of the fluids. An appropriate development scenario along with anticipation of production challenges, can benefit from early integration of engineering and geochemical understanding of hydrocarbon fluids. This paper presented field examples of how the kerogen type and maturity, and later post-generation alteration processes such as biodegradation, water washing, TSR can influence likely flow assurance challenges in the production stream. The confounding issues of multiple charges and overlaying signatures were also discussed.

  2. Hydrocarbon potential of the Trinidad area - 1977

    Energy Technology Data Exchange (ETDEWEB)

    Persad, K.M.

    1978-06-01

    It is recognized that deltaic and associated sands, together with porous marine limestones, form the vast majority of the reservoirs in the major accumulations of hydrocarbons throughout the world. The source of the hydrocarbons is now thought to be kerogen which is generated from the organic content of principally marine shales which are formed in or near the continental shelves. The Trinidad area contains several sedimentary subbasins, most of which consist largely of deltaic and associated sediments. These sediments, like most of the ancient deltas of the world, contain major reserves of oil and gas. Other less important reserves should occur in sporadic (time-wise) porous limestones. The total proven and probable reserves of the Trinidad area are around 5 billion bbl of oil, of which 1.6 billion bbl already have been produced, and over 47 TCF of gas.

  3. Organic material of the Messel oil shales

    Energy Technology Data Exchange (ETDEWEB)

    Jankowski, B.; Littke, R.

    1986-05-01

    According to chemism, the Messel oil shales belong to the Kerogen type II, formed by algae with additions of huminite detritus, i.e. residues of higher plants. This has been confirmed by the organo-petrographic studies reported. The oil shale deposits are characterised by their content of organic materials, the occurrence of a cream-coloured inertinite maceral, and of siderite. Hence, two facies can be clearly discriminated, the lower one containing relatively much organic material and the cream-coloured inertinite, but no siderite, and the upper facies exhibiting just the opposite. As the detritus is finely grained and quite uniform in content of huminite and silicate material, and only few spores and pollen have been found, there is reason to assume that the two facies represent sediments formed far from the border of the lake.

  4. Specific acyclic isoprenoids as biological markers of methanogenic bacteria in marine sediments.

    Science.gov (United States)

    Brassell, S C; Wardroper, A M; Thomson, I D; Maxwell, J R; Eglinton, G

    1981-04-23

    The widespread occurrence of extended hopanoids in sediments and petroleums illustrates the importance of bacterial lipid contributions to geological materials. In archaebacteria, however, hopanoids are absent; their role as structural components of biomembranes is fulfilled by acyclic isoprenoids. Recent studies of the lipid constituents of archaebacteria have greatly extended the range of acyclic isoprenoid skeletons known in organisms (Fig. 1). In particularly, isoprenoids with head-to-head linkages have been identified, and such compounds (for example, 3,7,11,15,18,22,26,30-octamethyldotriacontane, I) have been recognized in petroleum and as degradation products of Messel shale kerogen. Here we report the first recognition of 2,6,10,15,19-pentamethyleicosane (II), a known component of methanogens, in marine sediments of Recent to Cretaceous age (Table 1) and suggest that it and certain other acyclic isoprenoids may be used as biological markers for methanogens.

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

    International Nuclear Information System (INIS)

    Galindo, C.; Mougin, L.; Nourreddine, A.; Fakhi, S.

    2006-01-01

    Attention has been recently focused on the use of Moroccan's black shale as the raw material for production of a new type of adsorbents. The purpose of the present work was to characterize a black shale specimen, collected in the region of Timahdit, in terms of the total uranium and thorium contents, measurements of some geochemically important elements (Al, Fe, Si, K, Mn, P, Ca), and XRD/SEM analysis. Selective leaching procedure, followed by radiochemical purification and alpha-counting, was also performed to assess the distribution of 238 U, 234 U, 235 U, 232 Th, 228 Th, 230 Th in the main structures. It was found that calcite, dolomite, quartz, clays constitute the main bulk composition of inorganic matrix. Organic matter counts for at least 15 wt. % of the sample. As in most other organic rich rocks, uranium is highly enriched in the black shale. It was interpreted to have been concentrated over a long period of time under anaerobic environment. This actinide is associated predominantly with humic acids, the precursor of kerogen. An integrated isotopic approach points out its mobilization from these humic acids to carbonates and apatite phases. The radionuclide that is the less mobile in this environment is 232 Th, as was expected from its chemical properties, and in agreement with the most common view in the literature. It is partitioned between silicate minerals (49%), pyrite and kerogen (51%). Speciation, chemical behaviour of uranium and thorium and alpha decay related processes are widely responsible for disequilibria in the uranium decay series. (author)

  6. Iridium, sulfur isotopes and rare earth elements in the Cretaceous-Tertiary boundary clay at Stevns Klint, Denmark

    Science.gov (United States)

    Schmitz, Birger; Andersson, Per; Dahl, Jeremy

    1988-01-01

    Microbial activity and redox-controlled precipitation have been of major importance in the process of metal accumulation in the strongly Ir-enriched Cretaceous-Tertiary (K-T) boundary clay, the Fish Clay, at Stevns Klint in Denmark. Two important findings support this view: 1) Kerogen, recovered by leaching the Fish Clay in HCl and HF, shows an Ir concentration of 1100 ppb; this represents about 50% of the Ir present in the bulk sample Fish Clay. Strong organometallic complexes is the most probable carrier phase for this fraction of Ir. Kerogen separated from the K-T boundary clay at Caravaca, Spain, similarly exhibits enhanced Ir concentrations. 2) Sulfur isotope analyses of metal-rich pyrite spherules, which occur in extreme abundance (about 10% by weight) in the basal Fish Clay, give a δ 34S value of -32%.. This very low value shows that sulfide formation by anaerobic bacteria was intensive in the Fish Clay during early diagenesis. Since the pyrite spherules are major carriers of elements such as Ni, Co, As, Sb and Zn, microbial activity may have played an important role for concentrating these elements. In the Fish Clay large amounts of rare earth elements have precipitated from sea water on fish scales. Analyses reveal that, compared with sea water, the Fish Clay is only about four times less enriched in sea-water derived lanthanides than in Ir. This shows that a sea-water origin is plausible for elements that are strongly enriched in the clay, but whose origin cannot be accounted for by a lithogenic precursor.

  7. Low-field nuclear magnetic resonance characterization of organic content in shales

    Science.gov (United States)

    Washburn, Kathryn E.; Birdwell, Justin E.; Seymour, Joseph D.; Kirkland, Catherine; Vogt, Sarah J.

    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. Longitudinal T1 and transverse T2 relaxation time measurements made using LF-NMR on conventional reservoir systems provides information on rock porosity, pore size distributions, and fluid types and saturations in some cases. Recent improvements in LF-SNMR instrument electronics have made it possible to apply these methods 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 some types of T2 relaxation during correlation measurements allows for improved resolution of solid phase photons. LF-NMR measurements of T1 and T2 relaxation time correlations were carried out on raw oil shale samples from resources around the world. These shales vary widely in mineralogy, total organic carbon (TOC) content and kerogen type. NMR results were correlcated with Leco TOC and geochemical data obtained from Rock-Eval. There is excellent correlation between NMR data and programmed pyrolysis parameters, particularly TOC and S2, and predictive capability is also good. To better understand the NMR response, the 2D NMR spectra were compared to similar NMR measurements made using high-field (HF) NMR equipment.

  8. 2D compositional modeling of petroleum generation, expulsion and migration in the Southern compartment of the Reconcavo Basin, Brazil; Modelisation compositionnelle 2D de la genese, expulsion et migration du petrole dans le compartiment sud du Bassin de Reconcavo, Bresil

    Energy Technology Data Exchange (ETDEWEB)

    Barroz Penteado, H.L. de

    1999-01-07

    The Reconcavo Basin is part of a rift formed between the Late Jurassic and the Early Cretaceous in northeastern Brazil. The objective of this thesis was the compositional modeling of petroleum generation, expulsion and migration along a cross-section in the Southern Compartment of the basin with the Temispack basin simulation software. A geochemical study of the lacustrine shales of the Gomo Member (Candelas Fm.) has been performed to determine their petroleum potential, the evolution of maturation with depth and changes in petroleum composition. Hydrogen indices of immature kerogens (400-850 mg/g TOC) were shown to be higher than those of whole rocks, thus indicating a retention of Rock-Eval pyrolysis products in the mineral matrix of these type I source rocks. Saturates (30-50% of organic extracts in the immature zone) increase both in absolute and in relative (60-80%) terms in the oil window (2000-2600 m) because of a partial secondary cracking of NSOs and aromatics. After having tested several scenarios of geodynamic evolution between the Aptian and the Oligocene, a variable thickness of post-rift sediments (maximum of 1200 m) has been shown to be necessary to calibrate maturity parameters. Petroleum migration has been modeled to understand migration pathways as well as the role of faults as drains. Thus, two petroleum migration systems have been identified for the Dom Joao and Cexis accumulations. Petroleum compositional variations have been modeled by coupling the processes of retention and secondary cracking. A good calibration of compositions was obtained with secondary cracking parameters for NSOs and aromatics which are close to those of the main primary cracking reaction of a type I kerogen, coupled with a retention of 50% of NSOs within the source rocks. (author)

  9. Environmental consequences of shale gas exploitation and the crucial role of rock microfracturing

    Science.gov (United States)

    Renard, Francois

    2015-04-01

    The growing exploitation of unconventional gas and oil resources has dramatically changed the international market of hydrocarbons in the past ten years. However, several environmental concerns have also been identified such as the increased microseismicity, the leakage of gas into freshwater aquifers, and the enhanced water-rock interactions inducing the release of heavy metals and other toxic elements in the produced water. In all these processes, fluids are transported into a network of fracture, ranging from nanoscale microcracks at the interface between minerals and the kerogen of the source rock, to well-developed fractures at the meter scale. Characterizing the fracture network and the mechanisms of its formation remains a crucial goal. A major difficulty when analyzing fractures from core samples drilled at depth is that some of them are produced by the coring process, while some other are produced naturally at depth by the coupling between geochemical and mechanical forces. Here, I present new results of high resolution synchrotron 3D X-ray microtomography imaging of shale samples, at different resolutions, to characterize their microfractures and their mechanisms of formation. The heterogeneities of rock microstructure are also imaged, as they create local stress concentrations where cracks may nucleate or along which they propagate. The main results are that microcracks form preferentially along kerogen-mineral interfaces and propagate along initial heterogeneities according to the local stress direction, connecting to increase the total volume of fractured rock. Their lifetime is also an important parameter because they may seal by fluid circulation, fluid-rock interactions, and precipitation of a cement. Understanding the multi-scale processes of fracture network development in shales and the coupling with fluid circulation represents a key challenge for future research directions.

  10. The HC potential of pre-Westphalian sediments in the North German basin. A synthesis; Das Kohlenwasserstoff-Potential des Praewestfals im norddeutschen Becken. Eine Synthese

    Energy Technology Data Exchange (ETDEWEB)

    Gerling, P.; Kockel, F.; Krull, P. [Bundesanstalt fuer Geowissenschaften und Rohstoffe, Berlin (Germany).]|[Bundesanstalt fuer Geowissenschaften und Rohstoffe, Hannover (Germany)

    1999-07-01

    It was the aim of the interdisciplinary and interinstitutional research program to investigate the possibilities of HC generation from pre-Westphalian sediments in the North German basin in space and time. Potential source rock horizons exist within all pre-Westphalian structural units in Northern Europe, ranging from Cambrian to the Namurian in age and deposited in different environments. The structural framework of the basement of the North German Permian basin was described, the position of the Variscan outer front newly defined and the maturation history during the Late Palaeozoic, Mesozoic and Cainozoic deciphered. Pyrolysis experiments have shown that HC generation, especially from type III kerogen, is possible even beyond a maturity of 4% Rmax. Detailed geochemical and isotope-geochemical investigations of the natural gases from all North German fields indicate gas contributions from pre-Westphalian sources in special regions (Ems Estuary region, Altmark). By integrating all the results of the study an estimation of the possibilities of pre-Westphalian gas occurrences in Northern Germany could be made and the most promising areas for prospecting have been outlined. (orig.) [Deutsch] Aufgabe des interdisziplinaeren und interinstitutionellen Forschungsvorhabens war es, die Moeglichkeiten der Kohlenwasserstoff-Bildung aus praewestfalen Sedimenten im Norddeutschen Becken in Raum und Zeit zu erkunden. In allen praewestfalen strukturellen Grosseinheiten Nordeuropas existieren potentielle Muttergesteinshorizonte kambrischen bis namurischen Alters aus unterschiedlichen Ablagerungsmilieus. Das strukturelle Inventar des Untergrundes des norddeutschen Permbeckens, der Verlauf der Variszidenfront in Norddeutschland und die Reifungsgeschichte der praewestfalen Muttergesteine im Verlauf der jungpalaeozoischen, mesozoischen und tertiaeren Entwicklung wurden entschluesselt. Pyrolyseversuche zeigten, dass eine KW-Genese, vor allem fuer Kerogen des Typs III, auch jenseits

  11. Oil shale : could Shell's experimental oil shale technology be adapted to Alberta's bitumen carbonates?

    Energy Technology Data Exchange (ETDEWEB)

    Roche, P.

    2006-07-01

    Although Shell has been trying to develop technologies to economically extract oil from shale containing kerogen for the last 25 years, the volume of oil Shell produced from its Mahogany Research Project in Colorado has added up to less than 2500 bbls in total, and the company has recently devoted $400 million to purchase leases on carbonate reservoirs in Alberta. This article examined whether or not the technologies developed by Shell for oil shales could be used to profitably extract bitumen from carbonates. Extracting bitumen from carbonates may be easier than producing oil from shale, as the resource in carbonates is already oil, whereas the oil in oil shale is actually kerogen, which needs to be chemically cracked at extremely high temperatures. Although the technical feasibility of an in situ cracking process has been proven, work remains to be done before Shell can invest in a commercial-scale oil shale project. Challenges to oil shale production include preventing groundwater from entering target zones and keeping produced fluids out of the groundwater. However, a freeze wall test has recently been designed where chilled liquid is circulated through a closed-loop pipe system to freeze formation water, sealing off an area about the size of a football field from the surrounding strata. The energy requirements of the process that Shell is testing to produce shale oil in Colorado remain unprofitably high, as higher temperatures are necessary for thermal cracking. Shell has yet to make a decision as to what energy sources it will use to make the production process economically viable. An energy conservation group in Colorado has claimed that production of 100,000 bbls of shale oil would require the largest power plant in Colorado history. 2 figs.

  12. Preliminary organic geochemical investigation of the Kimmeridgian oil shales. [United Kingdom

    Energy Technology Data Exchange (ETDEWEB)

    Williams, P F.V.; Douglas, A G

    1980-01-01

    The Kimmeridge oil shales have assumed renewed significance because of their role as the prime source-rock for North Sea oil, and because of the need to assess their potential as a possible future supply of shale oil. This paper presents the results of a preliminary investigation of selected Kimmeridge oil shales. The immature shales are rich in organic matter with a dominantly marine type II kerogen showing evidence of algal contributions and a general sparsity of land-derived, higher plant detritus. Column chromatographic and capillary column gas chromatographic examinations of bitumens, pyrolysates and pyrolysis gas chromatograms of kerogen isolates show a predominance of aromatics in the hydrocarbon fractions, with bitumen n-alkane gas chromatograms showing evidence of algal-derived organic matter with n-alkane maxima in the n-C/sub 17/ region. Possible contributions from lower land plants are indicated by a second n-alkane maximum at n-C/sub 23/, whilst higher land plant detritus makes only a limited contribution. Reflected light microscopic examination of the shales also shows a general sparsity of recognizable land-derived woody or herbaceous material. Shale oil compositions reflect their pyrolytic origin, with unsaturates forming a large part of the aliphatic hydrocarbon fraction, together with significant amounts of isoprenoid alkanes; organic sulphur compounds are also prominent in the hydrocarbon fractions. Finally, considerable amounts of sterane and pentacyclic triterpane hydrocarbons have been found in the bitumen aliphatic hydrocarbon fractions, their distributions allowing Blackstone samples to be differentiated from those of lower stratigraphic levels.

  13. Correlation of resource plays and biodiversity patterns: accumulation of organic-rich shale tracks taxonomic turnover

    Science.gov (United States)

    Eoff, Jennifer D.

    2012-01-01

    Similar paleogeographic and paleotectonic settings characterize most self-sourced shale hydrocarbon plays. Their deposition occurred within similar orders of magnitude of eustatic events and during geologic periods characterized by “warm” (or transitional) climates and calcitic seas. In addition, the stratigraphic occurrence of shale plays parallels certain historical patterns of marine metazoan biodiversity. Such strong agreement among several correlation tools elucidates why these resources may be limited to discrete intervals of geological time. Correlation of self-sourced shale with biodiversity trends indicates that the factors controlling the deposition of marine organic matter may not be independent of those that induced taxonomic turnover. Paleoecological changes promoted accumulation and preservation of Type II kerogen. Deposition of self-sourced shale appears to correspond to reductions in absolute biodiversity and declining percentages of bioturbating taxa, with concomitant increases in proportions of pelagic taxa relative to infaunal and epifaunal organisms. Whereas upwelling and anoxia may have contributed to the deposition of kerogen in source rocks throughout much of the sedimentary record, diminished consumption of biomass by benthic metazoans likely augmented the preservation of organic carbon during deposition of this shale type. Rapid tectonic-plate reconfiguration induced coeval events, creating basins with sufficiently high rates of accommodation creation necessary to preserve additional organic material accumulating as the heterotrophic benthos suffered in response to rapidly changing environments. Combining sea-level curves, paleogeography, climate, and seawater chemistry provides a first-order approximation of the distribution of potential self-sourced shale in the geologic record. A model that predicts the stratigraphic distribution of self-sourced-shale deposition can aid in exploration of continuous hydrocarbon accumulations in self

  14. Organic compositions of lacustrine source rocks in Jiyang super-depression and its implication to petroleum geology

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The compositions of organic matter in four immature source rocks from Tertiary strata of Jiyang super-depression, the most typical continental rift subsidence basin in East China, have been studied by different extracting methods with CHCl3, MAC and CS2/NMP, respectively. The results suggest that there are great differences among the chemical compositions of organic matter in the source rocks derived from different depositional environments. About 79% of all the organic matter exists by non- covalent bond in the Es4 source rocks which were deposited under the saline lacustrine, indicating that its organic matter is not the real kerogen, but mainly composed of soluble organic matter which is easy to generate hydrocarbon at lower temperature. This is why the immature oils were derived from Es4 source rocks in Dongying depression. In contrast, around 60% of organic matter exists by covalent bond in Es3 source rocks which were deposited under the deep brackish-fresh lacustrine, showing that Es3 source rocks are mainly composed of kerogen producing mature hydrocarbon at higher temperature. The thermal simulation experiments, upon the remaining solid source rocks which were sequentially extracted by the three solvents, have been carried out. The chloroform extracts from the simulation product have been compared with the other three solvent extracts gained at room temperature. It is obvious that remarkable odd/even predominance (OEP) is mainly the characteristic of soluble organic matter; phytane mostly exists in the soluble organic matter by means of non-covalent bonds and characteristics of soluble organic matter are similar to these in immature oils produced in Jiyang super-depression.

  15. The fate of river organic carbon in coastal areas: A study in the Rhône River delta using multiple isotopic (δ13C, Δ14C) and organic tracers

    Science.gov (United States)

    Cathalot, C.; Rabouille, C.; Tisnérat-Laborde, N.; Toussaint, F.; Kerhervé, P.; Buscail, R.; Loftis, K.; Sun, M.-Y.; Tronczynski, J.; Azoury, S.; Lansard, B.; Treignier, C.; Pastor, L.; Tesi, T.

    2013-10-01

    A significant fraction of the global carbon flux to the ocean occurs in River-dominated Ocean Margins (RiOMar) although large uncertainties remain in the cycle of organic matter (OM) in these systems. In particular, the OM sources and residence time have not been well clarified. Surface (0-1 cm) and sub-surface (3-4 cm) sediments and water column particles (bottom and intermediate depth) from the Rhône River delta system were collected in June 2005 and in April 2007 for a multi-proxy study. Lignin phenols, black carbon (BC), proto-kerogen/BC mixture, polycyclic aromatic hydrocarbons (PAHs), carbon stable isotope (δ13COC), and radiocarbon measurements (Δ14COC) were carried out to characterize the source of sedimentary organic material and to address degradation and transport processes. The bulk OM in the prodelta sediment appears to have a predominantly modern terrigenous origin with a significant contribution of modern vascular C3 plant detritus (Δ14COC = 27.9‰, δ13COC = -27.4‰). In contrast, the adjacent continental shelf, below the river plume, seems to be dominated by aged OM (Δ14COC = -400‰, δ13COC = -24.2‰), and shows no evidence of dilution and/or replacement by freshly produced marine carbon. Our data suggest an important contribution of black carbon (50% of OC) in the continental shelf sediments. Selective degradation processes occur along the main dispersal sediment system, promoting the loss of a modern terrestrial OM but also proto-kerogen-like OM. In addition, we hypothesize that during the transport across the shelf, a long term resuspension/deposition loop induces efficient long term degradation processes able to rework such refractory-like material until the OC is protected by the mineral matrix of particles.

  16. Geochemistry and habitat of the oils in Italy

    Energy Technology Data Exchange (ETDEWEB)

    Mattavelli, L.; Novelli, L. (Agip S.p.A., Milano (Italy))

    1990-10-01

    All varieties of liquid petroleum, ranging from condensates (> 50{degree}API) to immature sulfur-rich heavy oils (as low as 5{degree} API), have been found in Italy. However, nonbiodegraded heavy oils account for about 70% of the total original oil in place. Geochemical analyses indicate that 11 oil groups are present in the Italian basins and two main types of source rocks have been identified: Triassic carbonates and Tertiary shales. About 95% of the oils were originated from Middle and Upper Triassic carbonates containing type II kerogen (about 1% total organic carbon (TOC) and 500 mg hydrocarbon/g TOC). Only a relatively minor amount of oil was generated by Tertiary shales containing type III kerogen with TOC generally less than 1%. Timing of generation and migration and bulk properties of oils were controlled by geodynamic histories of the three main Italian geologic settings: (1) Apennine and Southern Alp thrust belts, (2) foredeep (depression bordering the thrust belts), and (3) foreland (nondeformed African continental margin). Within the Apennine thrust belts, deep burial during the Neogene resulted in the generation of substantially lighter oils, not only from deeply buried Triassic but sometimes also from Tertiary source rocks. In the late Neogene, foredeep depocenters located in the central Adriatic and southern Sicily, high subsidence (up to 1,000 m/m.y.), a low geothermal gradient (22C/km) and compressional tectonics caused the generation of immature heavy oils generally at depths below 5,000 m and temperatures greater than 100C. Rapid burial and higher geothermal gradients (32C/km), which occurred since the Jurassic, resulted in the generation of light oils from the Late Cretaceous to the Oligocene in the southern sector of Adriatic foreland.

  17. The origin of oil in the Cretaceous succession from the South Pars Oil Layer of the Persian Gulf

    Science.gov (United States)

    Rahmani, Omeid; Aali, Jafar; Junin, Radzuan; Mohseni, Hassan; Padmanabhan, Eswaran; Azdarpour, Amin; Zarza, Sahar; Moayyed, Mohsen; Ghazanfari, Parviz

    2013-07-01

    The origin of the oil in Barremian-Hauterivian and Albian age source rock samples from two oil wells (SPO-2 and SPO-3) in the South Pars oil field has been investigated by analyzing the quantity of total organic carbon (TOC) and thermal maturity of organic matter (OM). The source rocks were found in the interval 1,000-1,044 m for the Kazhdumi Formation (Albian) and 1,157-1,230 m for the Gadvan Formation (Barremian-Hauterivian). Elemental analysis was carried out on 36 samples from the source rock candidates (Gadvan and Kazhdumi formations) of the Cretaceous succession of the South Pars Oil Layer (SPOL). This analysis indicated that the OM of the Barremian-Hauterivian and Albian samples in the SPOL was composed of kerogen Types II and II-III, respectively. The average TOC of analyzed samples is less than 1 wt%, suggesting that the Cretaceous source rocks are poor hydrocarbon (HC) producers. Thermal maturity and Ro values revealed that more than 90 % of oil samples are immature. The source of the analyzed samples taken from Gadvan and Kazhdumi formations most likely contained a content high in mixed plant and marine algal OM deposited under oxic to suboxic bottom water conditions. The Pristane/nC17 versus Phytane/nC18 diagram showed Type II-III kerogen of mixture environments for source rock samples from the SPOL. Burial history modeling indicates that at the end of the Cretaceous time, pre-Permian sediments remained immature in the Qatar Arch. Therefore, lateral migration of HC from the nearby Cretaceous source rock kitchens toward the north and south of the Qatar Arch is the most probable origin for the significant oils in the SPOL.

  18. Late Cretaceous coal overlying karstic bauxite deposits in the Parnassus-Ghiona Unit, Central Greece: Coal characteristics and depositional environment

    Energy Technology Data Exchange (ETDEWEB)

    Kalaitzidis, Stavros; Siavalas, George; Christanis, Kimon [Dept. of Geology, University of Patras, 26504 Rio-Patras (Greece); Skarpelis, Nikos [Dept. of Geology and Geoenvironment, University of Athens, 15784 Zografou (Greece); Araujo, Carla Viviane [Petrobras-Cenpes GEOQ/PDEXP, Rua Horacio Macedo n 950, Cidade Universitaria - Ilha do Fundao, 21941-915 Rio de Janeiro (Brazil)

    2010-04-01

    The Pera-Lakkos coal located on top of bauxite deposits in the Ghiona mining district (Central Greece), is the only known Mesozoic (Late Cretaceous) coal in the country. It was derived from herbaceous plants and algae growing in mildly brackish mires that formed behind a barrier system during a regression of the sea, on a karstified limestone partly filled in with bauxitic detritus. Petrological, mineralogical and geochemical data point to the predominance of reducing conditions and intense organic matter degradation in the palaeomires. O/C vs. H/C and OI vs. HI plots, based on elemental analysis and Rock-Eval data, characterize kerogen types I/II. This reflects the relatively high liptinite content of the coal. Besides kerogen composition, O/C vs. H/C plot for the Pera-Lakkos coals is in accordance with a catagenesis stage of maturation in contrast with vitrinite reflectance and T{sub max} from Rock-Eval pyrolysis, which indicate the onset of oil window maturation stage. Suppression of vitrinite reflectance should be considered and the high liptinite content corroborates this hypothesis. Despite some favourable aspects for petroleum generation presented by the Pera-Lakkos coal, its maximum thickness (up to 50 cm) points to a restricted potential for petroleum generation. Coal oxidation took place either during the late stage of peat formation, due to wave action accompanying the subsequent marine transgression, or epigenetically after the emergence of the whole sequence due to percolation of drainage waters. Both options are also supported by the REE shale-normalized profiles, which demonstrate an upwards depletion in the coal layer. Oxidation also affected pyrite included in the coal; this led to the formation of acidic (sulfate-rich) solutions, which percolated downwards resulting in bleaching of the upper part of the underlying bauxite. (author)

  19. Molecular Simulation of Adsorption in Microporous Materials

    Directory of Open Access Journals (Sweden)

    Yiannourakou M.

    2013-11-01

    Full Text Available The development of industrial software, the decreasing cost of computing time, and the availability of well-tested forcefields make molecular simulation increasingly attractive for chemical engineers. We present here several applications of Monte-Carlo simulation techniques, applied to the adsorption of fluids in microporous solids such as zeolites and model carbons (pores < 2 nm. Adsorption was computed in the Grand Canonical ensemble with the MedeA®-GIBBS software, using energy grids to decrease computing time. MedeA®-GIBBS has been used for simulations in the NVT or NPT ensembles to obtain the density and fugacities of fluid phases. Simulation results are compared with experimental pure component isotherms in zeolites (hydrocarbon gases, water, alkanes, aromatics, ethanethiol, etc., and mixtures (methane-ethane, n-hexane-benzene, over a large range of temperatures. Hexane/benzene selectivity inversions between silicalite and Na-faujasites are well predicted with published forcefields, providing an insight on the underlying mechanisms. Also, the adsorption isotherms in Na-faujasites for light gases or ethane-thiol are well described. Regarding organic adsorbents, models of mature kerogen or coal were built in agreement with known chemistry of these systems. Obtaining realistic kerogen densities with the simple relaxation approach considered here is encouraging for the investigation of other organic systems. Computing excess sorption curves in qualitative agreement with those recently measured on dry samples of gas shale is also favorable. Although still preliminary, such applications illustrate the strength of molecular modeling in understanding complex systems in conditions where experiments are difficult.

  20. Multi-scale Multi-dimensional Imaging and Characterization of Oil Shale Pyrolysis

    Science.gov (United States)

    Gao, Y.; Saif, T.; Lin, Q.; Al-Khulaifi, Y.; Blunt, M. J.; Bijeljic, B.

    2017-12-01

    The microstructural evaluation of fine grained rocks is challenging which demands the use of several complementary methods. Oil shale, a fine-grained organic-rich sedimentary rock, represents a large and mostly untapped unconventional hydrocarbon resource with global reserves estimated at 4.8 trillion barrels. The largest known deposit is the Eocene Green River Formation in Western Colorado, Eastern Utah, and Southern Wyoming. An improved insight into the mineralogy, organic matter distribution and pore network structure before, during and after oil shale pyrolysis is critical to understanding hydrocarbon flow behaviour and improving recovery. In this study, we image Mahogany zone oil shale samples in two dimensions (2-D) using scanning electron microscopy (SEM), and in three dimensions (3-D) using focused ion beam scanning electron microscopy (FIB-SEM), laboratory-based X-ray micro-tomography (µCT) and synchrotron X-ray µCT to reveal a complex and variable fine grained microstructure dominated by organic-rich parallel laminations which are tightly bound in a highly calcareous and heterogeneous mineral matrix. We report the results of a detailed µCT study of the Mahogany oil shale with increasing pyrolysis temperature. The physical transformation of the internal microstructure and evolution of pore space during the thermal conversion of kerogen in oil shale to produce hydrocarbon products was characterized. The 3-D volumes of pyrolyzed oil shale were reconstructed and image processed to visualize and quantify the volume and connectivity of the pore space. The results show a significant increase in anisotropic porosity associated with pyrolysis between 300-500°C with the formation of micron-scale connected pore channels developing principally along the kerogen-rich lamellar structures.

  1. Land to ocean transfer of erosion-related organic carbon, Waipaoa sedimentary system, East Coast, New Zealand

    International Nuclear Information System (INIS)

    Brackley, H.L.

    2006-01-01

    efficiency of the Waipaoa River in transferring terrestrial OC directly to the marine environment. Flood layers are preserved in the marine sedimentary record. Continental shelf sediments indicate that during Cyclone Bola (March 1988, a rainfall event with a >100 year return period), the extreme river discharge produced a hyperpycnal (negatively buoyant) plume, preserved as a ∼10 cm thick layer on the inner shelf and a ∼ 1 cm thick layer on the mid-shelf. The flood layer contains a significant amount of terrestrially-sourced OC (up to 86% of total OC in >25 mm fraction) which subsequently was rapidly buried by normal marine deposits (in which ∼ 60% of OC in >25 mm fraction is terrestrial), thereby preserving its strong terrestrial source signature. As sediments are physically and biologically processed at various depositional sites across the continental shelf and slope, they lose some of their modern terrestrial OC, and the concurrent addition of marine sourced OC results in the sediments gaining a stronger marine biogeochemical signature (δ 1 3C values increasing from -26.2 permille for floodplain sediments to -21.6 permille for upper continental slope sediments). Carbon loading (OC:SA) and 1 4C data revealed the contributions of kerogen, modern terrestrial OC and modern marine OC to the total OC of continental shelf and slope surface sediments. Sediments retain about 40% of their terrestrial OC following transport to the continental slope, of which a significant amount consists of kerogen. Because of high erosion rates within the catchment, kerogen associated with the particles escapes oxidation, and therefore makes up a large part of the POC flux. Kerogen is preserved across the margin to the mid-slope, where only 8% of the bulk sediment OC consists of modern terrestrial OC, 58% is modern marine OC and 34% is kerogen. Biomarker analyses of surface samples also support findings that terrestrial OC is being transferred across the continental margin, with plant

  2. A Mechanical Modelling of the Primary Migration Modélisation mécanique de l'expulsion

    Directory of Open Access Journals (Sweden)

    Schneider F.

    2006-12-01

    Full Text Available In order to address the question of oil-induced microfracturing, we propose under specific assumptions (plane circular kerogen flake surrounded by an homogeneous microfractured porous medium an analytical method for the determination of the oil pressure increase. It is based on a mechanical modelling of the kerogen-oil-rock interaction at the microscopicscale of a kerogen particle. It is shown that the oil pressure tends towards an asymptotic value when the chemical transformation of kerogen is completed. The effect of the macroscopic stress variation during oil formation process proves to be negligible. However, this effect must be taken into account for describing the evolution of oil pressure at earlier stages of oil formation process. The increase in burial depth induces an increase of oil pressure as well as a variation of the macroscopic stress which both determine the microscopic stress field. The possibility of microfracturing depends on the position of the microscopic stress state with respect to the fracture criterion. If the duration of the oil formation process is short enough, so that the macroscopic stress change associated with the corresponding (small burial depth increase can be neglected, it is found that microfracturing is likely for the usual values of rock tensile strength. However, in the general case, neglecting the macroscopic stress change can significantly overestimate the possibility of fracture initiation due to oil-pressure increase. Considering now the macroscopicscale of the source bed, the evolution equation of the oil pressure are derived within the framework of Biot's poroelasticity theory. The oil pressure rate proves to be the sum of a diffusion term which accounts for oil migration within the source bed, and of two source terms respectively associated with the volume expansion tendency of the kerogen - oil transformation and the overburden pressure increase. Dans le but d'étudier le problème de la

  3. Characterization of coal-derived hydrocarbons and source-rock potential of coal beds, San Juan Basin, New Mexico and Colorado, U.S.A.

    Science.gov (United States)

    Rice, D.D.; Clayton, J.L.; Pawlewicz, M.J.

    1989-01-01

    .5 ppt), are chemically wetter (C1/C1-5 values range from 0.85 to 0.95), and contain less CO2 (< 2%). These gases are interpreted to have been derived from type III kerogen dispersed in marine shales of the underlying Lewis Shale and nonmarine shales of the Fruitland Formation. In the underlying Upper Cretaceous Dakota Sandstone and Tocito Sandstone Lentil of the Mancos Shale, another gas type is produced. This gas is associated with oil at intermediate stages of thermal maturity and is isotopically lighter and chemically wetter at the intermediate stage of thermal maturity as compared with gases derived from dispersed type III kerogen and coal; this gas type is interpreted to have been generated from type II kerogen. Organic matter contained in coal beds and carbonaceous shales of the Fruitland Formation has hydrogen indexes from Rock-Eval pyrolysis between 100 and 350, and atomic H:C ratios between 0.8 and 1.2. Oxygen indexes and atomic O:C values are less than 24 and 0.3, respectively. Extractable hydrocarbon yields are as high as 7,000 ppm. These values indicate that the coal beds and carbonaceous shales have good potential for the generation of liquid hydrocarbons. Voids in the coal filled with a fluorescent material that is probably bitumen is evidence that liquid hydrocarbon generation has taken place. Preliminary oil-source rock correlations based on gas chromatography and stable carbon isotope ratios of C15+ hydrocarbons indicate that the coals and (or) carbonaceous shales in the Fruitland Formation may be the source of minor amounts of condensate produced from the coal beds at relatively low levelsof thermal maturity (Rm=0.7). ?? 1989.

  4. Effect of organic matter properties, clay mineral type and thermal maturity on gas adsorption in organic-rich shale systems

    Science.gov (United States)

    Zhang, Tongwei; Ellis, Geoffrey S.; Ruppel, Stephen C.; Milliken, Kitty; Lewan, Mike; Sun, Xun; Baez, Luis; Beeney, Ken; Sonnenberg, Steve

    2013-01-01

    A series of CH4 adsorption experiments on natural organic-rich shales, isolated kerogen, clay-rich rocks, and artificially matured Woodford Shale samples were conducted under dry conditions. Our results indicate that physisorption is a dominant process for CH4 sorption, both on organic-rich shales and clay minerals. The Brunauer–Emmett–Teller (BET) surface area of the investigated samples is linearly correlated with the CH4 sorption capacity in both organic-rich shales and clay-rich rocks. The presence of organic matter is a primary control on gas adsorption in shale-gas systems, and the gas-sorption capacity is determined by total organic carbon (TOC) content, organic-matter type, and thermal maturity. A large number of nanopores, in the 2–50 nm size range, were created during organic-matter thermal decomposition, and they significantly contributed to the surface area. Consequently, methane-sorption capacity increases with increasing thermal maturity due to the presence of nanopores produced during organic-matter decomposition. Furthermore, CH4 sorption on clay minerals is mainly controlled by the type of clay mineral present. In terms of relative CH4 sorption capacity: montmorillonite ≫ illite – smectite mixed layer > kaolinite > chlorite > illite. The effect of rock properties (organic matter content, type, maturity, and clay minerals) on CH4 adsorption can be quantified with the heat of adsorption and the standard entropy, which are determined from adsorption isotherms at different temperatures. For clay-mineral rich rocks, the heat of adsorption (q) ranges from 9.4 to 16.6 kJ/mol. These values are considerably smaller than those for CH4 adsorption on kerogen (21.9–28 kJ/mol) and organic-rich shales (15.1–18.4 kJ/mol). The standard entropy (Δs°) ranges from -64.8 to -79.5 J/mol/K for clay minerals, -68.1 to -111.3 J/mol/K for kerogen, and -76.0 to -84.6 J/mol/K for organic-rich shales. The affinity of CH4 molecules for sorption on organic matter

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

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yifeng [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Nuclear Waste Disposal Research and Analysis; Xiong, Yongliang [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Repository Performance; Criscenti, Louise J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Geochemistry; Ho, Tuan Ahn [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Geochemistry; Weck, Philippe F. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Storage and Transportation Technology; Ilgen, Anastasia G. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Geochemistry; Matteo, Edward [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Nuclear Waste Disposal Research and Analysis; Kruichak, Jessica N. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Nuclear Waste Disposal Research and Analysis; Mills, Melissa M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Nuclear Waste Disposal Research and Analysis; Dewers, Thomas [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Geomechanics; Gordon, Margaret E. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Dept. of Materials, Devices and Energy Technologies; Akkutlu, Yucel [Texas A & M Univ., College Station, TX (United States). Dept. of Petroleum Engineering

    2016-09-01

    The recent boom in shale gas production through hydrofracturing has reshaped the energy production landscape in the United States. Wellbore production rates vary greatly among the wells within a single field and decline rapidly with time, thus bring up a serious concern with the sustainability of shale gas production. Shale gas production starts with creating a fracture network by injecting a pressurized fluid in a wellbore. The induced fractures are then held open by proppant particles. During production, gas releases from the mudstone matrix, migrates to nearby fractures, and ultimately reaches a production wellbore. Given the relatively high permeability of the induced fractures, gas release and migration in low-permeability shale matrix is likely to be a limiting step for long-term wellbore production. Therefore, a clear understanding of the underlying mechanisms of methane disposition and release in shale matrix is crucial for the development of new technologies to maximize gas production and recovery. Shale is a natural nanocomposite material with distinct characteristics of nanometer-scale pore sizes, extremely low permeability, high clay contents, significant amounts of organic carbon, and large spatial heterogeneities. Our work has shown that nanopore confinement plays an important role in methane disposition and release in shale matrix. Using molecular simulations, we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~ 30 - 47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. The long-term production decline appears controlled by the second stage of gas release. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD

  6. Depositional environment and source rock potential of Cenomanian and Turonian sedimentary rocks of the Tarfaya Basin, Southwest Morocco

    Energy Technology Data Exchange (ETDEWEB)

    Ghassal, B.I.; Littke, R.; Sachse, V.; Sindern, S.; Schwarzbauer, J.

    2016-07-01

    from bituminite-fair to bituminite-rich and to higher percentages of visible organic matter towards the younger interval. These differences in the organic matter type are attributed to i) early diagenetic kerogen sulfurization and ii) the upwelling depositional environment. Moreover, kerogen sulfurization was controlled by the relationship between carbonate, iron and sulfur as well as the organic matter. Thus, the organic carbon-rich deposits can be grouped into: i) low Sorg and moderately organic matter-rich oil prone source rocks, ii) moderate Sorg and organic-carbon-rich oil prone source rocks, iii) high Sorg and organic carbon-rich oil prone source rocks and iv) very high Sorg and organic carbon-rich oil prone source rocks, the latter representing the CTBE interval. Types 2 to 4 will generate sulfur-rich petroleum upon maturation or artificial oil shale retorting. This integrated organic and inorganic approach sheds light on the various processes leading to the development of the world-class oil shales deposited through the Cenomanian to Turonian. In addition, this study shows how the changes in the depositional environment might have controlled kerogen sulfurization and organic matter preservation and structure. This detailed approach provides a better understanding on source rock development during the Cenomanian to Turonian in a global context, as many of the geochemical features were identified worldwide for deposits related to OAE2. (Author)

  7. Deep-Time drilling in the Australian Archean: the Agouron Institute geobiological drilling project. (Invited)

    Science.gov (United States)

    Buick, R.

    2010-12-01

    The Agouron Institute has sponsored deep-time drilling across the South African Archean-Proterozoic boundary, investigating the rise of oxygen over an onshore-offshore environmental transect. It is now supporting a drilling program in the Australian Archean of the Pilbara Craton, addressing a similar theme but with the added goal of resolving controversy over the age and origin of hydrocarbon biomarker molecules in ancient kerogenous shales. As these have been claimed to provide evidence for the evolution of oxygenic photosynthesis long before the rise of atmospheric oxygen to persistently high levels during the ~2.3 Ga “Great Oxidation Event”, their syngenesis with their host shales is thus of critical importance for the interpretation of Earth’s early oxygenation history. During the first drilling season, 3 holes were drilled using techniques and equipment to minimize organic geochemical contamination (new drill-string components cleaned before drilling potentially biomarker-bearing rocks, pre-contamination of drilling fluid with a synthetic organic compound of similar geochemical characteristics to biomarkers, sterile cutting and storage of samples immediately upon retrieval from the core-barrel). The initial hole was a blank control for organic geochemistry, drilled into rocks too metamorphosed to retain biomarker molecules. These rocks, cherts, carbonates and pelites of the 3.52 Ga Coucal Formation, Coonterunah Group, have been metamorphosed to upper greenschist facies at temperatures near 500°C and so should have had any ancient soluble hydrocarbons destroyed. However, because they contain both carbonate and organic carbon, these rocks can instead provide isotopic information about the earliest evolution of biological metabolism as they possess residues of both the reactant and product sides of the carbon-fixation reaction. The second hole sampled an on-shore section of carbonates and kerogenous shales in the ~2.65 Ga Carawine Dolomite and Lewin Shale

  8. Thermal maturity and burial history modelling of shale is enhanced by use of Arrhenius time-temperature index and memetic optimizer

    Directory of Open Access Journals (Sweden)

    David A. Wood

    2018-03-01

    Full Text Available Thermal maturity indices and modelling based on Arrhenius-equation reaction kinetics have played an important role in oil and gas exploration and provided petroleum generation insight for many kerogen-rich source rocks. Debate continues concerning how best to integrate the Arrhenius equation and which activation energies (E and frequency factors (A values to apply. A case is made for the strong theoretical basis and practical advantages of the time-temperature index (∑TTIARR method, first published in 1998, using a single, carefully selected E-A set (E = 218 kJ/mol (52.1 kcal/mol; A = 5.45E+26/my from the well-established A-E trend for published kerogen kinetics. An updated correlation between ∑TTIARR and vitrinite reflectance (Ro is provided in which the ∑TTIARR scale spans some 18 orders of magnitude. The method is readily calculated in spreadsheets and can be further enhanced by visual basic for application code to provide optimization. Optimization is useful for identifying possible geothermal gradients and erosion intervals covering multiple burial intervals that can match calculated thermal maturities with measured Ro data. A memetic optimizer with firefly and dynamic local search memes is described that flexibly conducts exploration and exploitation of the feasible, multi-dimensional, thermal history solution space to find high-performing solutions to complex burial and thermal histories. A complex deep burial history example, with several periods of uplift and erosion and fluctuating heat flow is used to demonstrate what can be achieved with the memetic optimizer. By carefully layering in constraints to the models specific insights to episodes in their thermal history can be exposed, leading to better characterization of the timing of petroleum generation. The objective function found to be most effective for this type of optimization is the mean square error (MSE of multiple burial intervals for the difference between

  9. Position-specific 13C distributions within propane from experiments and natural gas samples

    Science.gov (United States)

    Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael D.; Eiler, John M.

    2018-01-01

    Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, 'bulk' isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in

  10. Artificial maturation of an immature sulfur- and organic matter-rich limestone from the Ghareb Formation, Jordan

    Science.gov (United States)

    Koopmans, M.P.; Rijpstra, W.I.C.; De Leeuw, J. W.; Lewan, M.D.; Damste, J.S.S.

    1998-01-01

    An immature (Ro=0.39%), S-rich (S(org)/C = 0.07), organic matter-rich (19.6 wt. % TOC) limestone from the Ghareb Formation (Upper Cretaceous) in Jordan was artificially matured by hydrous pyrolysis (200, 220 ..., 300??C; 72 h) to study the effect of progressive diagenesis and early catagenesis on the amounts and distributions of hydrocarbons, organic sulfur compounds and S-rich geomacromolecules. The use of internal standards allowed the determination of absolute amounts. With increasing thermal maturation, large amounts of alkanes and alkylthiophenes with predominantly linear carbon skeletons are generated from the kerogen. The alkylthiophene isomer distributions do not change significantly with increasing thermal maturation, indicating the applicability of alkylthiophenes as biomarkers at relatively high levels of thermal maturity. For a given carbon skeleton, the saturated hydrocarbon, alkylthiophenes and alkylbenzo[b]thiophenes are stable forms at relatively high temperatures, whereas the alkylsulfides are not stable. The large amount of alkylthiophenes produced relative to the alkanes may be explained by the large number of monosulfide links per carbon skeleton. These results are in good agreement with those obtained previously for an artificial maturation series of an immature S-rich sample from the Gessoso-solfifera Formation.An immature (Ro = 0.39%), S-rich (Sorg/C = 0.07), organic matter-rich (19.6 wt.% TOC) limestone from the Ghareb Formation (Upper Cretaceous) in Jordan was artificially matured by hydrous pyrolysis (200, 220, ..., 300??C; 72 h) to study the effect of progressive diagenesis and early catagenesis on the amounts and distributions of hydrocarbons, organic sulfur compounds and S-rich geomacromolecules. The use of internal standards allowed the determination of absolute amounts. With increasing thermal maturation, large amounts of alkanes and alkylthiophenes with predominantly linear carbon skeletons are generated from the kerogen. The

  11. Multi-technical approach to characterize the dissolved organic matter from clay-stone

    International Nuclear Information System (INIS)

    Blanchart, Pascale; Michels, Raymond; Faure, Pierre; Parant, Stephane; Bruggeman, Christophe; De Craen, Mieke

    2012-01-01

    Document available in extended abstract form only. Currently, different clay formations (Boom Clay, Callovo-Oxfordian argilites, Opalinus Clay, Toarcian shales...) are studied as reference host rocks for methodological studies on the geological disposal of high-level and long-lived radioactive waste. While a significant effort is being done on the characterization of the mineral composition and the reactivity of the clays as barriers, the occurrence of organic matter, even in low proportion cannot be neglected. The organic matter appears as gas (C 1 -C 4 as identified in the Bure underground facilities), as solid (kerogen), as hydrocarbon liquids (free hydrocarbons within the kerogen or adsorbed on minerals) as well as in the aqueous phase (Dissolved Organic Matter - DOM). DOM raises specific interest, as it may have complexation properties towards metals and rare earth elements and is potentially mobile. Therefore, it is important to characterize the DOM as part of a study of feasibility of geological disposal. In this study, four host rocks were studied: - The Callovo-Oxfordian shales of Bure Underground Research Laboratory (Meuse, France); - The Opalinus Clay of Mont Terri Underground Research Laboratory (Switzerland); - The Toarcian shales of Tournemire (Aveyron, France); - The Boom Clay formation studied in The HADES Underground Research Laboratory (Mol, Belgium). Organic matter characteristics vary upon formation in terms of (i) origin (mainly marine type II; mixtures of marine type II and higher plants type III organic matter often poorly preserved), (ii) TOC contents, (iii) thermal maturity (for instance, Opalinus Clay and Toarcian shales are more mature and have poor oxygen content compare to Callovo-Oxfordian shales and Boom Clay). These differences in organic matter quality may have an influence on the quantity and the quality of DOM. The DOM of the rocks was isolated by Soxhlet extraction using pure water. A quantitative and qualitative multi

  12. Impact of dia- and catagenesis on sulphur and oxygen sequestration of biomarkers as revealed by artificial maturation of an immature sedimentary rock

    Science.gov (United States)

    Koopmans, M.P.; De Leeuw, J. W.; Lewan, M.D.; Sinninghe, Damste J.S.

    1996-01-01

    Hydrous pyrolysis of an immature (R(a)??? 0.25%) sulphur-rich marl from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin was carried out at 160C ??? T ???330 C for 72 h, to study the effect of progressive diagenesis and early catagenesis on the abundance and distribution of sulphur-containing and sulphur- and oxygen-linked carbon skeletons in low-molecular-weight and highmolecular-weight fractions (e.g. kerogen). To this end, compounds in the saturated hydrocarbon fraction, monoaromatic hydrocarbon fraction, polyaromatic hydrocarbon fraction, alkylsulphide fraction and ketone fraction were quantified, as well as compounds released after desulphurisation of the polar fraction and HI/LiAIH4 treatment of the desulphurised polar fraction. Sulphur-bound phytane and (20R)-5??,14??,17??(H) and (20R)-5??,14??,17??(H) C27 C29 steranes in the polar fraction become less abundant with increasing maturation temperature, whereas the amount of their corresponding hydrocarbons increases in the saturated hydrocarbon fraction. Carbon skeletons that are bound in the kerogen by multiple bonds (e.g. C38 n-alkane and isorenieratane) are first released into the polar fraction, and then as free hydrocarbons. These changes occur at relatively low levels of thermal maturity (R(a) <0.6%), as evidenced by the 'immature' values of biomarker maturity parameters such as the ????/(????+ ???? + ????) C35 hopane ratio and the 22S/(22S + 22R)-17??,21??(H) C35 hopane ratio. Sulphur- and oxygen-bound moieties, present in the polar fraction, are not stable with increasing thermal maturation. However, alkylthiophenes, ketones. 1,2-di-n-alkylbenzenes and free n-alkanes seem to be stable thermal degradation products of these sulphur- and oxygen-bound moieties. Thus, apart from free n-alkanes, which are abundantly present in more mature sedimentary rocks and crude oils, alkylthiophenes, 1,2-di-n-alkylbenzenes and ketones can also be expected to occur. The positions of the thiophene

  13. Position-specific 13C distributions within propane from experiments and natural gas samples

    Science.gov (United States)

    Piasecki, Alison; Sessions, Alex L.; Lawson, Michael; Ferreira, A.A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael; Eilers, J.M.

    2018-01-01

    Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, ‘bulk’ isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in

  14. Analyse quantitative des effluents de pyrolyse en milieu ouvert et fermé Quantitative Analysis of Pyrolysis Effluents in an Open and Closed System

    Directory of Open Access Journals (Sweden)

    Behar F.

    2006-11-01

    Full Text Available Dans la première partie de l'article, nous décrivons une technique de pyrolyse en milieu ouvert qui permet de caractériser les matières organiques complexes comme le kérogène, le charbon, les asphaltènes de roche et d'huiles, les substances humiques et fulviques etc. Les effluents de pyrolyse sont récupérés et fractionnés quantitativement puis analysés par des techniques spécifiques comme la chromatographie en phase gazeuse et le couplage chromatographie/spectrométrie de masse. Dans la deuxième partie, est présentée une technique de pyrolyse en milieu fermé pour simuler au laboratoire l'évolution thermique des kérogènes, asphaltènes ou huiles. Nous nous sommes surtout attachés à dresser des bilans massiques et des bilans de l'hydrogène sur l'ensemble des produits de pyrolyse. Pour cela, nous avons distingué cinq classes de poids moléculaire croissant : C1, C2-C5, C6-C13, C14+ et coke. La récupération quantitative et la séparation de chacune des cinq fractions permet une analyse moléculaire détaillée de chacune d'elles. The first part of this article describes an open pyrolysis system in order to characterize complex organic matter such as kerogen, coal, rock and oil asphaltenes and humic substances, etc. Pyrolysis effluents are recovered, fractionated quantitatively by liquid chromatography, and then they are analyzed by specific techniques such as gas chromatography and chromatography/mass-spectrometry coupling. The second part describes a pyrolysis technique in a closed system, used for the laboratory simulation of the thermal evolution of kerogens, asphaltenes or oils. A special effort has been made to give the mass and hydrogen balances for all pyrolysis products. For this, five classes have been distinguised with increasing molecular weight: C1, C2-C5, C6-C13, C14+ and coke. The quantitative recovery and the separation of each of the five fractions is used to make a detailed molecular analysis of each of

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

    Science.gov (United States)

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

    2008-12-01

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

  16. Exploring the relationship between polycyclic aromatic hydrocarbons and sedimentary organic carbon in three Chinese lakes

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Fengchang; Xu, Libin; Liao, Haiqing; Zhao, Xiaoli [Chinese Research Academy of Environmental Sciences, Beijing (China). State Key Lab. of Environmental Criteria and Risk Assessment; Sun, Yongge [Zhejiang Univ., Hangzhou (China). Inst. of Environmental and Biogeochemistry; Guo, Jianyang [Chinese Academy of Sciences, Guiyang (China). State Key Lab. of Environmental Geochemistry

    2012-05-15

    Purpose: Previous studies have shown a positive correlation between concentrations of polycyclic aromatic hydrocarbons (PAHs) and total organic carbon (TOC) in lake sediments. However, with respect to the complex organic matter in recent sediments, it is still unclear which part of TOC plays a key role in controlling PAHs distributions in natural sediments. The aim of this study was to examine the relationships between PAHs and TOC components of different origins in lake sediments. Materials and methods: Sediment cores from three Chinese lakes with different trophic conditions - Lakes Bosten, Dianchi, and Poyang - were collected using a piston core sampler. The cores were sectioned into 1- or 2-cm intervals immediately after collection and transported on ice to the laboratory where they were stored at -20 C. The subsamples were freeze-dried and ground with a mortar and pestle for analyses. PAHs were analyzed by GC-MS and TOC was determined with a PE elemental analyzer after the removal of carbonates. Rock-Eval 6 pyrolysis technique was used to deconvolute the TOC in the sediments into free and volatile hydrocarbons (S1), kerogen-derived hydrocarbons (S2), and residual carbon (RC); S2 was further separated into thermal less stable macromolecular organic matter (S2a) and high molecular weight kerogens (S2b). Results and discussion: Positive correlations between TOC and PAHs were observed in these lakes. Results show that the more labile, minor components of TOC (S1 and S2a) played a more important role in controlling PAH distributions than the major components of TOC (S2b and RC), probably due to the different accessibilities of the organic components. The algae-derived organic carbon had a greater influence on the distribution of low molecular weight PAHs than that of high molecular weight PAHs in sediments. This suggests that PAHs scavenging in the water column by algae is mainly targeted at low molecular weight PAHs, and that preferential scavenging of low

  17. Unconventional Liquids, Peak Oil and Climate Change

    Science.gov (United States)

    Hughes, J. D.

    2015-12-01

    Oil is the largest source of primary energy in the world, at 32% of 2014 consumption. Forecasts by the International Energy Agency suggest oil will continue to provide the largest share of global energy through 2040, even with new policies to mitigate greenhouse gas emissions. The IPCC's Representative Concentration Pathway (RCP) scenarios indicate that between 1.5 and 3.8 trillion barrels of oil will be burnt between 2015 and 2100. Various sources suggest that the world has 5 to 6 trillion barrels of remaining recoverable oil, more than half of which are in low grade deposits. Although oil sands and extra heavy oil are claimed to hold 1.5 trillion barrels, assessments of major deposits in the Canadian oil sands and the Venezuela Orinoco Belt, which hold the bulk of these resources, total less than 500 billion barrels of recoverable oil. Kerogen oil (oil shale), which has never been produced in anything but miniscule volumes, comprises an additional trillion barrels of these estimates. These unconventional deposits are very different from the conventional oil of the past as: - they are rate constrained, as they require massive upfront capital investments and lengthy construction periods, and therefore cannot be scaled up quickly in response to declines in conventional production. - they are expensive, both in terms of cost per barrel and the large energy inputs required for production. The best in situ oil sands deposits may yield an energy return of 3:1 and kerogen oil even less if it ever becomes commercially viable. This compares to 10:1 or more for conventional oil. Shale oil (light tight oil), may yield another 300 billion barrels worldwide, but suffers from high decline rates, expensive wells and limited availability of high quality deposits. The most productive and economically viable portions of these unconventional deposits tend to be exploited first, leaving the less productive, higher cost oil for later. As a result, increasing global oil consumption

  18. A study of light hydrocarbons (C{sub 4}-C{sub 1}3) in source rocks and petroleum fluid

    Energy Technology Data Exchange (ETDEWEB)

    Odden, Wenche

    2000-07-01

    This thesis consists of an introduction and five included papers. Of these, four papers are published in international journals and the fifth was submitted for review in April 2000. Emphasis has been placed on both naturally and artificially generated light hydrocarbons in petroleum fluids and their proposed source rocks as well as direct application of light hydrocarbons to oil/source rock correlations. Collectively, these papers describe a strategy for interpreting the source of the light hydrocarbons in original oils and condensates as well as the source of the asphaltene fractions from the reservoir fluids. The influence of maturity on light hydrocarbon composition has also been evaluated. The papers include (1) compositional data on the light hydrocarbons from thermal extracts and kerogen pyrolysates of sediment samples, (2) light hydrocarbon data of oils and condensates as well as the pyrolysis products of the asphaltenes from these fluids, (3) assessment of compositional alteration effects, such as selective losses of light hydrocarbons due to evaporation, thermal maturity, phase fractionation and biodegradation, (4) comparison of naturally and artificially generated light hydrocarbons, and (5) compound-specific carbon isotope analysis of the whole range of hydrocarbons of all sample types. (author)

  19. The US Geological Survey, digital spectral reflectance library: version 1: 0.2 to 3.0 microns

    Science.gov (United States)

    Clark, Roger N.; Swayze, Gregg A.; King, Trude V. V.; Gallagher, Andrea J.; Calvin, Wendy M.

    1993-01-01

    We have developed a digital reflectance spectral library, with management and spectral analysis software. The library includes 500 spectra of 447 samples (some samples include a series of grain sizes) measured from approximately 0.2 to 3.0 microns. The spectral resolution (Full Width Half Maximum) of the reflectance data is less than or equal to 4 nm in the visible (0.2-0.8 microns) and less than or equal 10 nm in the NIR (0.8-2.35 microns). All spectra were corrected to absolute reflectance using an NBS Halon standard. Library management software lets users search on parameters (e.g. chemical formulae, chemical analyses, purity of samples, mineral groups, etc.) as well as spectral features. Minerals from sulfide, oxide, hydroxide, halide, carbonate, nitrate, borate, phosphate, and silicate groups are represented. X-ray and chemical analyses are tabulated for many of the entries, and all samples have been evaluated for spectral purity. The library also contains end and intermediate members for the olivine, garnet, scapolite, montmorillonite, muscovite, jarosite, and alunite solid-solution series. We have included representative spectra of H2O ice, kerogen, ammonium-bearing minerals, rare-earth oxides, desert varnish coatings, kaolinite crystallinity series, kaolinite-smectite series, zeolite series, and an extensive evaporite series. Because of the importance of vegetation to climate-change studies we have include 17 spectra of tree leaves, bushes, and grasses.

  20. Geology of the oil shales of Messel near Darmstadt

    Energy Technology Data Exchange (ETDEWEB)

    Matthess, G.

    1966-07-25

    The oil shale, with a thickness of nearly 190 m, represents the middle part of the strata of Messel. Freshly mined, it consists of about 40% water and about 25% organic matter. The rest are clay minerals, chiefly montmorillonite. Kaolinite, messelite, vivianite, pyrites, markasite, siderite, and gypsum occur in small quantities. The organic components are kerogens which are extraordinary rich in oxygen. They are tied adsorptively to montmorillonite. The bitumina are supposed to be chiefly derived from algae, in a smaller extent from fungi and pollen. Plants as well as the large ganoid fishes and the crocodiles indicate a tropical to subtropical climate and a larger extent of the former water system. The oil shales of Messel are preserved in a tectonic graben that is 1,000 m long and up to 700 m wide. This graben is divided into 3 depressions. Both depressions are close together in the south and diverge northward. The ground water lifted in the open mining shows high degrees of total hardness and unusual high sulfate and phosphate contents. These matters can be derived from the weathering events in the exposed oil shale. (133 refs.)

  1. Proterozoic microbial reef complexes and associated hydrothermal mineralizations in the Banfora Cliffs, Burkina Faso

    Science.gov (United States)

    Álvaro, J. Javier; Vizcaïno, Daniel

    2012-07-01

    The Proterozoic Guena-Souroukoundinga Formation of the Mopti arm (Gourma Aulacogen, southerm Taoudeni Basin) consists of a shale-dominated succession, up to 200 m thick, with scattered microbial reef complexes. Quarry exposures of the Tiara reef complex allow reconstruction of a transect across back-reef peritidal laminites, reef margin and peri-reef ooidal shoals, and fore-reef slope strata. Microbial carbonate productivity nucleated on isolated palaeohighs during transgression, whereas its end was controlled by two tectonically induced drowning pulses that led to the successive record of onlapping kerogenous limestones and pelagic shales. Reef carbonates are crosscut by fractures and fissures occluded by hydrothermal mineralizations, which are related to the rifting activity of the Gourma Aulacogen. The Tiara reef complex is similar to other Proterozoic reefs in being composed nearly entirely of stromatolites, although calcimicrobial (filamentous) and thromboid textures are locally abundant, which contrast with their scarcity or absence in coeval stable-platform microbial reefs of the northern Taoudeni Basin.

  2. Physical and chemical controls on habitats for life in the deep subsurface beneath continents and ice

    Science.gov (United States)

    Parnell, John; McMahon, Sean

    2016-01-01

    The distribution of life in the continental subsurface is likely controlled by a range of physical and chemical factors. The fundamental requirements are for space to live, carbon for biomass and energy for metabolic activity. These are inter-related, such that adequate permeability is required to maintain a supply of nutrients, and facies interfaces invite colonization by juxtaposing porous habitats with nutrient-rich mudrocks. Viable communities extend to several kilometres depth, diminishing downwards with decreasing porosity. Carbon is contributed by recycling of organic matter originally fixed by photosynthesis, and chemoautotrophy using crustal carbon dioxide and methane. In the shallow crust, the recycled component predominates, as processed kerogen or hydrocarbons, but abiotic carbon sources may be significant in deeper, metamorphosed crust. Hydrogen to fuel chemosynthesis is available from radiolysis, mechanical deformation and mineral alteration. Activity in the subcontinental deep biosphere can be traced through the geological record back to the Precambrian. Before the colonization of the Earth's surface by land plants, a geologically recent event, subsurface life probably dominated the planet's biomass. In regions of thick ice sheets the base of the ice sheet, where liquid water is stable and a sediment layer is created by glacial erosion, can be regarded as a deep biosphere habitat. This environment may be rich in dissolved organic carbon and nutrients accumulated from dissolving ice, and from weathering of the bedrock and the sediment layer. PMID:26667907

  3. Volatile characteristic of trace elements during microwave pyrolysis of oil shale

    Energy Technology Data Exchange (ETDEWEB)

    Bai, Jing-ru; Wang, Qing; Kong, Ling-wen; Bai, Zhang [Northeast Dianli Univ., Jilin (China). Engineering Research Centre

    2013-07-01

    Oil shale is abundant in the world. Today, the industry of oil shale retorting for producing shale oil is developing owing to high price of oil in the world. In order to study migratory behavior of trace elements in oil shale at microwave pyrolysis, tests were performed in laboratory with oil shale of the Huadian deposit of China at different powers from 400 to 700 W. The trace elements As, Cd, Hg, Mo, Pb, Se, Cr, Cu, Ni, V, Zn, Ba, Co, Mn present in oil shale and shale char were determined by the inductively coupled plasma-mass spectrometry (ICP-MS). By comparing the content of trace elements in oil shale and shale char, distribution characteristics of trace elements at retorting were studied. The overall trends of volatile ratio of trace elements are ascending with higher microwave power and higher than the conventional pyrolysis. The differences in the volatile ratio indicate that the trace elements investigated are bound with the oil shale kerogen and its mineral matter in different manner. So Float-sink experiments (FSE) were performed on oil shale. Huadian oil shale has more included mineral. The volatilization of organic matter is not the main reason for the volatilization of trace elements in oil shale. The trace elements combined with the mineral elements may be also certain volatility.

  4. Log-based identification of sweet spots for effective fracs in shale reservoirs

    Energy Technology Data Exchange (ETDEWEB)

    Hashmy, K.; Barnett, C.; Jonkers, J. [Weatherford (United States); Abueita, S. [Anadarko Petroleum (United States)

    2011-07-01

    Shale reservoir exploitation requires horizontal hydro-fracturing, often in a multi-stage configuration. Fracture stages are usually evenly spaced along the horizontal well, regardless of reservoir characteristics, even though wireline logs or logging-while-drilling (LWD) methods could be used to determine sweet spots for more cost-effective fracturing locations. This paper aims to show how failure to take into consideration a reservoir's geological properties can lead to less effective exploitation, and then goes on to describe logging techniques, LWD and wireline logs combined, and their usefulness in effectively placing fracturing stages on a reservoir's sweet spots. By studying logs from different LWD and wireline log techniques, such as gamma ray, resistivity, X-ray fluorescence or shockwave sonic measurements for different existing wells, the study shows how sweet spots, where kerogen concentration is higher, with higher porosity, can be determined. These logging techniques, requiring low investments, offer a variety of methods for identifying sweet spots in shale reservoirs, and fracturing only these spots will avoid unnecessary expenditure on frac stages in zones with poor reservoir characteristics.

  5. 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.

  6. Geological implications of radium and helium in oil-field brines: observations, inferences and speculations

    International Nuclear Information System (INIS)

    Lerche, I.

    1993-01-01

    The 1600 yr half-life of radium restricts the time and thus the distance over which radium can migrate in sediments. The dominant source of unsupported radium in sandstone reservoir brines must then be close by and is likely in shales adjacent to the oil-field reservoirs. The chemical similarity of calcium and radium can be used to argue for a local shale-source contribution to the calcium in reservoir sands -suggesting the probability of calcite cementation early in the sedimentary sequence. Helium production by radium decay increases with time. Concentrations of helium found in reservoir oil field brines are then used to suggest that: (a) such reservoirs are dominantly closed systems over geological times; (b) neither methane nor helium in the reservoirs have migrated any significant distance; and (c) the mechanism responsible for the observed helium in the brine is a continuous on-going process operative today. Diagenetic studies should then deal with both sands and shales interdependently, the two are not separable. Shales control the transport mechanisms of migration so that the primary migration of hydrocarbons, the result of kerogen catagenesis in shales, should occur sufficiently early in the sedimentary sequence in order to avoid exclusion from the reservoir by calcite cementation in association with radium transport. (author)

  7. Geologic models and evaluation of undiscovered conventional and continuous oil and gas resources: Upper Cretaceous Austin Chalk

    Science.gov (United States)

    Pearson, Krystal

    2012-01-01

    The Upper Cretaceous Austin Chalk forms a low-permeability, onshore Gulf of Mexico reservoir that produces oil and gas from major fractures oriented parallel to the underlying Lower Cretaceous shelf edge. Horizontal drilling links these fracture systems to create an interconnected network that drains the reservoir. Field and well locations along the production trend are controlled by fracture networks. Highly fractured chalk is present along both regional and local fault zones. Fractures are also genetically linked to movement of the underlying Jurassic Louann Salt with tensile fractures forming downdip of salt-related structures creating the most effective reservoirs. Undiscovered accumulations should also be associated with structure-controlled fracture systems because much of the Austin that overlies the Lower Cretaceous shelf edge remains unexplored. The Upper Cretaceous Eagle Ford Shale is the primary source rock for Austin Chalk hydrocarbons. This transgressive marine shale varies in thickness and lithology across the study area and contains both oil- and gas-prone kerogen. The Eagle Ford began generating oil and gas in the early Miocene, and vertical migration through fractures was sufficient to charge the Austin reservoirs.

  8. Repeated Carbon-Cycle Disturbances at the Permian-Triassic Boundary Separate two Mass Extinctions

    Science.gov (United States)

    Nicol, J. A.; Watson, L.; Claire, M.; Buick, R.; Catling, D. C.

    2004-12-01

    Non-marine organic matter in Permian-Triassic sediments from the Blue Mountains, eastern Australia shows seven negative δ13C excursions of up to 7%, terminating with a positive excursion of 4%. Fluctuations start at the late Permian Glossopteris floral extinction and continue until just above the palynological Permian-Triassic boundary, correlated with the peak of marine mass extinction. The isotopic fluctuations are not linked to changes in depositional setting, kerogen composition or plant community, so they evidently resulted from global perturbations in atmospheric δ13C and/or CO2. The pattern was not produced by a single catastrophe such as a meteorite impact, and carbon-cycle calculations indicate that gas release during flood-basalt volcanism was insufficient. Methane-hydrate melting can generate a single -7% shift, but cannot produce rapid multiple excursions without repeated reservoir regeneration and release. However, the data are consistent with repeated overturning of a stratified ocean, expelling toxic gases that promoted sequential mass extinctions in the terrestrial and marine realms.

  9. AMMONIA IN THE EARLY SOLAR SYSTEM: AN ACCOUNT FROM CARBONACEOUS METEORITES

    International Nuclear Information System (INIS)

    Pizzarello, S.; Williams, L. B.

    2012-01-01

    This study presents a survey of abundance distribution and isotopic composition of the ammonia found incorporated in the kerogen-like insoluble material of selected carbonaceous chondrite meteorites; the ammonia was released upon hydrothermal treatment at 300°C and 100 MPa. With the exception of Allende, a metamorphosed and highly altered stone, all the insoluble organic materials (IOM) of the meteorites analyzed released significant amounts of ammonia, which varied from over 4 μg mg –1 for the Orgueil IOM to 0.5 μg mg –1 for that of Tagish Lake; the IOM of the pristine Antarctica find GRA95229 remains the most rich in freeable ammonia with 10 μg mg –1 . While the amounts of IOM bound ammonia do not appear to vary between meteorites with a recognizable trend, a possible consequence of long terrestrial exposure of some of the stones, we found that the δ 15 N composition of the ammonia-carrying materials is clearly distinctive of meteorite types and may reflect a preservation of the original 15 N distribution of pre- and proto-solar materials.

  10. Ammonia in the Early Solar System: An Account from Carbonaceous Meteorites

    Science.gov (United States)

    Pizzarello, S.; Williams, L. B.

    2012-04-01

    This study presents a survey of abundance distribution and isotopic composition of the ammonia found incorporated in the kerogen-like insoluble material of selected carbonaceous chondrite meteorites; the ammonia was released upon hydrothermal treatment at 300°C and 100 MPa. With the exception of Allende, a metamorphosed and highly altered stone, all the insoluble organic materials (IOM) of the meteorites analyzed released significant amounts of ammonia, which varied from over 4 μg mg-1 for the Orgueil IOM to 0.5 μg mg-1 for that of Tagish Lake; the IOM of the pristine Antarctica find GRA95229 remains the most rich in freeable ammonia with 10 μg mg-1. While the amounts of IOM bound ammonia do not appear to vary between meteorites with a recognizable trend, a possible consequence of long terrestrial exposure of some of the stones, we found that the δ15N composition of the ammonia-carrying materials is clearly distinctive of meteorite types and may reflect a preservation of the original 15N distribution of pre- and proto-solar materials.

  11. AMMONIA IN THE EARLY SOLAR SYSTEM: AN ACCOUNT FROM CARBONACEOUS METEORITES

    Energy Technology Data Exchange (ETDEWEB)

    Pizzarello, S. [Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287-1604 (United States); Williams, L. B., E-mail: pizzar@asu.edu [School of Earth and Space Exploration, Arizona State University, Tempe, AZ 85287-1404 (United States)

    2012-04-20

    This study presents a survey of abundance distribution and isotopic composition of the ammonia found incorporated in the kerogen-like insoluble material of selected carbonaceous chondrite meteorites; the ammonia was released upon hydrothermal treatment at 300 Degree-Sign C and 100 MPa. With the exception of Allende, a metamorphosed and highly altered stone, all the insoluble organic materials (IOM) of the meteorites analyzed released significant amounts of ammonia, which varied from over 4 {mu}g mg{sup -1} for the Orgueil IOM to 0.5 {mu}g mg{sup -1} for that of Tagish Lake; the IOM of the pristine Antarctica find GRA95229 remains the most rich in freeable ammonia with 10 {mu}g mg{sup -1}. While the amounts of IOM bound ammonia do not appear to vary between meteorites with a recognizable trend, a possible consequence of long terrestrial exposure of some of the stones, we found that the {delta}{sup 15}N composition of the ammonia-carrying materials is clearly distinctive of meteorite types and may reflect a preservation of the original {sup 15}N distribution of pre- and proto-solar materials.

  12. Hydrocarbons thermal maturation: Leopatin method applied to the Parana basin; Maturacao termica de hidrocarbonetos: aplicacao do metodo de Lopatin a Bacia do Parana

    Energy Technology Data Exchange (ETDEWEB)

    Eston, Sergio Medici de; Jardim, Niza S

    1987-12-31

    One of the requirements for the existent of economic deposits of hydrocarbons is that the organic matter has undergone adequate thermal maturation. Several techniques have been proposed in order to quantity the catagenetic state of kerogen, and the Lopatin-Waples methodology permits quantification at any past time and does not require laboratory tests on samples of the material. For this reason it is an useful techniques for predicting mature zones using as basic information the thermal and subsidence histories of each stratum. Lopatin`s technique was applied to the Parana basin, with McKenzie`s crustal stretching model fitted to the data of 18 wells, and the areas predicted as mature for oil and/or gas were in good agreement with the field results. The technique predicted oil phone areas at the east border of the basin for the Ponta Grossa and Irati formation, and also that most of the thermal maturation occurred after the basalt flows of the Cretaceous period. (author) 41 refs., 6 figs., 6 tabs.

  13. Liquid hydrocarbon generation potential from Tertiary Nyalau Formation coals in the onshore Sarawak, Eastern Malaysia

    Science.gov (United States)

    Hakimi, Mohammed Hail; Abdullah, Wan Hasiah

    2013-01-01

    Tertiary coals exposed in the north-central part of onshore Sarawak are evaluated, and their depositional environments are interpreted. Total organic carbon contents (TOC) of the coals range from 58.1 to 80.9 wt. % and yield hydrogen index values ranging from 282 to 510 mg HC/g TOC with low oxygen index values, consistent with Type II and mixed Type II-III kerogens. The coal samples have vitrinite reflectance values in the range of 0.47-0.67 Ro %, indicating immature to early mature (initial oil window). T max values range from 428 to 436 °C, which are good in agreement with vitrinite reflectance data. The Tertiary coals are humic and generally dominated by vitrinite, with significant amounts of liptinite and low amounts of inertinite macerals. Good liquid hydrocarbons generation potential can be expected from the coals with rich liptinitic content (>35 %). This is supported by their high hydrogen index of up to 300 mg HC/g TOC and Py-GC ( S 2) pyrograms with n-alkane/alkene doublets extending beyond C30. The Tertiary coals are characterised by dominant odd carbon numbered n-alkanes ( n-C23 to n-C33), high Pr/Ph ratio (6-8), high T m / T s ratio (8-16), and predominant regular sterane C29. All biomarkers parameters clearly indicate that the organic matter was derived from terrestrial inputs and the deposited under oxic condition.

  14. Carbonaceous Survivability on Impact

    Science.gov (United States)

    Bunch, T. E.; Becker, Luann; Morrison, David (Technical Monitor)

    1994-01-01

    In order to gain knowledge about the potential contributions of comets and cosmic dust to the origin of life on Earth, we need to explore the survivability of their potential organic compounds on impact and the formation of secondary products that may have arisen from the chaotic events sustained by the carriers as they fell to Earth. We have performed a series of hypervelocity impact experiments using carbon-bearing impactors (diamond, graphite, kerogens, PAH crystals, and Murchison and Nogoya meteorites) into Al plate targets at velocities - 6 km/s. Estimated peak shock pressures probably did not exceed 120 GPa and peak shock temperatures were probably less than 4000 K for times of nano- to microsecs. Nominal crater dia. are less than one mm. The most significant results of these experiments are the preservation of the higher mass PAHs (e. g., pyrene relative to napthalene) and the formation of additional alkylated PAHs. We have also examined the residues of polystyrene projectiles impacted by a microparticle accelerator into targets at velocities up to 15 km/s. This talk will discuss the results of these experiments and their implications with respect to the survival of carbonaceous deliverables to early Earth. The prospects of survivability of organic molecules on "intact" capture of cosmic dust in space via soft: and hard cosmic dust collectors will also be discussed.

  15. Geochemical investigation of petroleum source rocks by using Rock- Eval data in the Agha-Jari oilfield

    Directory of Open Access Journals (Sweden)

    Behzad khani

    2015-01-01

    Full Text Available In this study, 40 drilling cutting of the Pabdeh, Gurpi, kazhdumi and Gadvan Formations from the Agha-Jari Oilfield were analyzed by using Rock-Eval pyrolysis. In order to recognizing sedimentary environmental conditions of studied Formations, they are divided to 4 zones which A (Kazhdumi Formation#187 and C (Kazhdumi Formation#140 zones show reduction conditions by presence of sea organic materials and B (Gadvan Formation #140 and D(Gadvan Formation#187 zones show oxidation conditions by presence of continental organic materials to basin. Based on the Rock-Eval pyrolysis data, the Pabeh, Gurpi, Kazhdumi and Gadvan Formations have variable hydrocarbon generative potential. HI vs. OI plot revealed that the kerogen type in this Formations is a mixed of types II & III. The intensity of matrix effect in the Pabdeh, Gurpi, Kazhdumi and Gadvan Formations was compared by using S2 vs. TOC plot and calculating its regression equation. The results show that the significant amount of S2 adsorption by matrix was happened in the Pabdeh (4.98-6.96 mg HC/gr rock in wells 113 and 121 and Gurpi Formations ‌(4.33 mg HC/gr rock in well 113 which is due to their low thermal maturity‌(Tmax

  16. An experimental platform for triaxial high-pressure/high-temperature testing of rocks using computed tomography

    Science.gov (United States)

    Glatz, Guenther; Lapene, Alexandre; Castanier, Louis M.; Kovscek, Anthony R.

    2018-04-01

    A conventional high-pressure/high-temperature experimental apparatus for combined geomechanical and flow-through testing of rocks is not X-ray compatible. Additionally, current X-ray transparent systems for computed tomography (CT) of cm-sized samples are limited to design temperatures below 180 °C. We describe a novel, high-temperature (>400 °C), high-pressure (>2000 psi/>13.8 MPa confining, >10 000 psi/>68.9 MPa vertical load) triaxial core holder suitable for X-ray CT scanning. The new triaxial system permits time-lapse imaging to capture the role of effective stress on fluid distribution and porous medium mechanics. System capabilities are demonstrated using ultimate compressive strength (UCS) tests of Castlegate sandstone. In this case, flooding the porous medium with a radio-opaque gas such as krypton before and after the UCS test improves the discrimination of rock features such as fractures. The results of high-temperature tests are also presented. A Uintah Basin sample of immature oil shale is heated from room temperature to 459 °C under uniaxial compression. The sample contains kerogen that pyrolyzes as temperature rises, releasing hydrocarbons. Imaging reveals the formation of stress bands as well as the evolution and connectivity of the fracture network within the sample as a function of time.

  17. Some aspects of the development of the Vaal Reef uranium-gold carbon seams, Witwatersrand sequence: organic geochemical and microbiological considerations

    International Nuclear Information System (INIS)

    Zumberge, J.E.; Nagy, B.; Nagy, L.A.

    1981-01-01

    The solvent-insoluble organic matter (kerogen) that is the predominant syngenetic component of the Vaal Reef carbon seams was analyzed by combined high-vacuum pyrolysis gas-chromatography mass spectrometry, combined electron microprobe-scanning electron microscopy and electron paramagnetic resonance spectroscopy. The pyrolysis results indicate that the Vaal Reef carbon is a random polymer-type matter consisting mainly of aromatic and short-chain aliphatic hydrocarbons, as well as aromatic and other organic-sulfur constituents. Scanning electron microscopy revealed coccoid and filamentous microstructures in the carbonaceous seams. These structures are conceivably of biological affinity and may be fossil blue-green algae and (or) bacteria. Gold is often concentrated at the interfaces of admixed clay-carbon microenvironments. This implies physical and chemical interactions between clays and organic matter conducive to the entrapment of detrital gold during deposition and the crystallization of colloidal/dissolved gold in the carbon seams. High concentrations of organic free radicals (molecules with unpaired electrons) in the carbonaceous matter, deduced from electron paramagnetic resonance spectroscopy, suggest that radiation emitted from uranium played a unique role in the reconstitution and polymerization of the progenitor biochemicals

  18. First record of Telephina (Trilobita from the Ordovician of northeastern Estonia and its stratigraphical implications

    Directory of Open Access Journals (Sweden)

    Helje Pärnaste

    2011-06-01

    Full Text Available For the first time a telephinid trilobite was recorded from the shallow-water rocks of the North Estonian Confacies Belt in the oil-shale mining area of northeast Estonia. A cranidium of Telephina (Telephops biseriata (Asklund was collected from a loose boulder of the kerogenous limestone of the Viivikonna Formation, Kukruse Stage, together with a rich assemblage of other trilobites, bryozoans, ostracods and rare graptolites. In its type area Jämtland, Sweden, T. biseriata occurs together with Pygodus anserinus and Hustedograptus teretiusculus in the Ståltorp Limestone Member of the Andersö Shale Formation, marking the latest Darriwilian. The occurrence in the North Estonian Confacies Belt of Telephina, known as a pelagic trilobite inhabiting deeper-water areas, probably reflects a transgression event at this time. Together with T. biseriata, other trilobite taxa such as Remopleurides and Lonchodomas, common in the Hustedograptus teretiusculus Biozone in deeper-water areas, arrive in the North Estonian Confacies Belt. Graptolites from the other loose boulders at the same locality have been identified as Hustedograptus cf. uplandicus, which occur together with a few dendroids.

  19. An insight into the mechanism and evolution of shale reservoir characteristics with over-high maturity

    Directory of Open Access Journals (Sweden)

    Xinjing Li

    2016-10-01

    Full Text Available Over-high maturity is one of the most vital characteristics of marine organic-rich shale reservoirs from the Lower Paleozoic in the south part of China. The organic matter (OM in shale gas reservoirs almost went through the entire thermal evolution. During this wide span, a great amount of hydrocarbon was available and numerous pores were observed within the OM including kerogen and solid bitumen/pyrobitumen. These nanopores in solid bitumen/pyrobitumen can be identified using SEM. The imaging can be dissected and understood better based on the sequence of diagenesis and hydrocarbon charge with the shape of OM and pores. In terms of the maturity process showed by the various typical cases, the main effects of the relationship between the reservoir porosity and organic carbon abundance are interpreted as follows: the change and mechanism of reservoirs properties due to thermal evolution are explored, such as gas carbon isotope from partial to complete rollover zone, wettability alteration from water-wet to oil-wet and then water-wet pore surface again, electrical resistivity reversal from the increasing to decreasing stage, and nonlinearity fluctuation of rock elasticity anisotropy. These indicate a possible evolution pathway for shale gas reservoirs from the Lower Paleozoic in the southern China, as well as the general transformation processes between different shale reservoirs in thermal stages.

  20. Stable isotope (δ13Cker, δ13Ccarb, δ18Ocarb distribution along a Cambrian outcrop section in the eastern Tarim Basin, NW China and its geochemical significance

    Directory of Open Access Journals (Sweden)

    Hu Liu

    2017-01-01

    Full Text Available This study investigated the geochemical features of the lower Paleozoic strata of Yaerdang Mountain outcrop along with the core samples from well TD2∈ in the eastern Tarim Basin, NW China. The total organic carbon abundance, hydrocarbon-generating precursor biospecies, and stable isotope ratios of organics and carbonate (δ13Cker, δ13Ccarb and δ18Ocarb were comprehensively studied for their possible correlative constraints during sedimentary evolution. The results revealed that the δ13Cker (VPDB of Cambrian kerogens along the outcrop section varied from −34.6‰ to −28.4‰, indicating an increasing tendency from the lower Cambrian to the upper Cambrian. This was on the whole accompanied by the variation in the δ13Ccarb and δ18Ocarb along the profile, which might be associated with the changes in the sea level and also in the compositional variation of benthic and planktonic biomass. The large variation in the stable carbon isotope ratios up to 6‰ along the outcrop section reflected the heterogeneity of the Cambrian source rocks from the eastern Tarim Basin. Hence, the 13C-enriched crude oils from well TD2∈ might have been derived from a localized stratum of Cambrian source rocks. The results from this study showed the possibility of multiple source kitchens in the Cambrian–lower Ordovician portion of Tarim Basin.

  1. The potentiality of hydrocarbon generation of the Jurassic source rocks in Salam-3x well,

    Directory of Open Access Journals (Sweden)

    Mohamed M. El Nady

    2016-03-01

    Full Text Available The present work deals with the identification of the potential and generating capability of oil generation in the Jurassic source rocks in the Salam-3x well. This depending on the organo-geochemical analyses of cutting samples representative of Masajid, Khatatba and Ras Qattara formations, as well as, representative extract samples of the Khatatba and Ras Qattara formations. The geochemical analysis suggested the potential source intervals within the encountered rock units as follows: Masajid Formation bears mature source rocks and have poor to fair generating capability for generating gas (type III kerogen. Khatatba Formation bears mature source rock, and has poor to good generating capability for both oil and gas. Ras Qattara Formation constituting mature source rock has good to very good generating capability for both oil and gas. The burial history modeling shows that the Masajid Formation lies within oil and gas windows; Khatatba and Ras Qattara formations lie within the gas window. From the biomarker characteristics of source rocks it appears that the extract is genetically related as the majority of them were derived from marine organic matters sources (mainly algae deposited under reducing environment and take the direction of increasing maturity and far away from the direction of biodegradation. Therefore, Masajid Formation is considered as effective source rocks for generating hydrocarbons, while Khatatba and Ras Qattara formations are the main source rocks for hydrocarbon accumulations in the Salam-3x well.

  2. Geochemical markers of soil anthropogenic contaminants in polar scientific stations nearby (Antarctica, King George Island).

    Science.gov (United States)

    Prus, Wojciech; Fabiańska, Monika J; Łabno, Radosław

    2015-06-15

    The organic contamination of Antarctic soils and terrestrial sediments from nearby of five polar scientific stations on King George Island (Antarctica) was investigated. Gas chromatography-mass spectrometry (GC-MS) was applied to find composition of dichloromethane extracts of soil and terrestrial sediments. The presence of geochemical markers, such as n-alkanes, steranes, pentacyclic triterpenoids, and alkyl PAHs, their distribution types, and values of their ratios indicates the predominating source of organic fossil fuels and products of their refining rather than from the natural Antarctic environment. Fossil fuel-originated compounds well survived in conditions of Antarctic climate over long times thus enabling to characterize geochemical features of source fossil fuel identified as petroleum expelled from kerogen II of algal/bacterial origins deposited in sub-oxic conditions and being in the middle of catagenesis. Both microbial activity and water leaching play an important role in degradation of terrestrial oil spills in the Antarctica climate, and petroleum alteration occurs lowly over long periods of time. Synthetic anthropogenic compounds found in terrestrial Antarctica sediments included diisopropylnaphthalenes, products of their sulfonates degradation in paper combustion, and organophosporus compounds used as retardants and plasticizers. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Co-Firing Oil Shale with Coal and Other Fuels for Improved Efficiency and Multi-Pollutant Control

    Energy Technology Data Exchange (ETDEWEB)

    Robert A. Carrington; William C. Hecker; Reed Clayson

    2008-06-01

    Oil shale is an abundant, undeveloped natural resource which has natural sorbent properties, and its ash has natural cementitious properties. Oil shale may be blended with coal, biomass, municipal wastes, waste tires, or other waste feedstock materials to provide the joint benefit of adding energy content while adsorbing and removing sulfur, halides, and volatile metal pollutants, and while also reducing nitrogen oxide pollutants. Oil shale depolymerization-pyrolysis-devolatilization and sorption scoping studies indicate oil shale particle sorption rates and sorption capacity can be comparable to limestone sorbents for capture of SO2 and SO3. Additionally, kerogen released from the shale was shown to have the potential to reduce NOx emissions through the well established “reburning” chemistry similar to natural gas, fuel oil, and micronized coal. Productive mercury adsorption is also possible by the oil shale particles as a result of residual fixed-carbon and other observed mercury capture sorbent properties. Sorption properties were found to be a function particle heating rate, peak particle temperature, residence time, and gas-phase stoichmetry. High surface area sorbents with high calcium reactivity and with some adsorbent fixed/activated carbon can be produced in the corresponding reaction zones that exist in a standard pulverized-coal or in a fluidized-bed combustor.

  4. Petroleum systems of the Upper Magdalena Valley, Colombia

    Energy Technology Data Exchange (ETDEWEB)

    Sarmiento, L.F.; Rangel, A. [Instituto Colombiano del Petroleo, Bucaramanga (Colombia). ECOPETROL

    2004-03-01

    In the Upper Magdalena Valley, Colombia, four petroleum systems were identified. Two petroleum systems are located in the Girardot sub-basin and the other two in the Neiva sub- basin. Limestones laterally changing to shales of the lower part of the Villeta Gp, deposited during Albian and Turonian marine flooding events, constitutes the main source rocks of the oil families. These rocks contain 1-4% TOC and type II kerogen. The littoral quartz arenites of the Caballos (Albian) and Monserrate (Maastrichtian) Fms. are the main reservoir rocks. Seal rocks are Cretaceous and Paleocene shales. Overburden includes the Cretaceous rocks and the Tertiary molasse deposited simultaneously with development of two opposite verging thrust systems during Cenozoic time. These deformation events were responsible for trap creation. Except for the Villarrica area, where the source rock reached maturity during the Paleocene, generation occurred during Miocene. Two oil families are identified, each in both sub-basins: One derived from a clay-rich source and the second from a carbonate-rich source rock lithofacies of the lower part of Villeta Gp. Geochemical source-rock to oil correlations are demonstrated for the three of the petroleum systems. Up-dip lateral migration distances are relatively short and faults served as vertical migration pathways. A huge amount of oil was probably degraded at surface, as a result of Miocene deformation and erosion. (author)

  5. Petroleum generation 3D modeling of Espirito Santo Basin, Brazil; Modelagem 3D da geracao de petroleo na Bacia do Espirito Santo, Brasil

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Daniella A.; Lemgruber, Adriana; Goncalves, Felix T.T. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Coordenacao dos Programas de Pos-graduacao de Engenharia (COPPE). Lab. de Modelagem Multidisciplinar de Bacias Sedimentares (LAB2M); Petersohn, Eliane [Agencia Nacional do Petroleo, Gas Natural e Biocombustiveis (ANP), Rio de Janeiro, RJ (Brazil)

    2008-07-01

    Intervals of potential source rocks were identified and characterized by the analysis and interpretation of total organic carbon (TOC) and Rock-Eval pyrolysis data. The rift section presents the best conditions for hydrocarbon generation, especially in Mariricu formation, that presents high TOC, hydrogen index and type I Kerogen. The drift section possesses low source rock potential, the intervals with best organic matter characteristic (quantity and quality) are represented by thin packages positioned in the superior portion of Regencia and Sao Mateus formation and in the basis of Urucutuca formation. The geochemistry data was integrated, on a regional scale, into the thermal maturation and petroleum generation three-dimensional model. Four potentially source rock intervals were simulated, two in the pre-salt section and two in the post-salt section. The results point out that the pre-salt intervals have reached thermal maturity in the proximal shelf and were overmatured in deep water. The thermal evolution obtained for the post-salt zone was very similar to those obtained for the rift section (pre-salt section). (author)

  6. Search for biochemical fossils on earth and non-biological organic molecules on Jupiter, Saturn and Titan

    Science.gov (United States)

    Nagy, Bartholomew

    1982-07-01

    Recognizable remnants of ancient biochemicals may survive under mild/moderate geological environments. Acyclic isoprenoid hydrocarbons, cyclic hydrocarbons with terpenoid carbon skeletons (e.g. hopanes) and vanadyl and nickel porphyrins have been isolated from organic matter, including petroleum, in Phanerozoic sedimentary rocks. Remnants of lignin have also been found. Usually, carbohydrates do not survive long; they degrade and/or react with other organic substances to form macromolecular matter. Proteins, e.g. apparently those in dinosaur bone collagen, break down relatively rapidly. Life arose during the Precambrian and potential biochemical fossils, e.g. n-alkanes, 2,5-dimethylfuran have been isolated from Precambrian kerogens. Traces of hydrocarbons, NH3, PH3 occur on Jupiter and Saturn. Hydrocarbons, N2 and HCN, the latter a key intermediary in the laboratory abiological syntheses of amino acids and nucleic acid bases, are present on Titan where life could not have evolved. Precursor abiological organic molecules of some complexity may have been synthesized on Titan and the Jovian planets.

  7. Preferred Orientation and Anisotropy of Clay minerals and Pores in Posidonia Shales

    Science.gov (United States)

    Kanitpanyacharoen, W.; Chen, K.; Wenk, H.

    2010-12-01

    Shales compose a large part of sedimentary basins and form the seal and source rocks for hydrocarbon reservoirs. They are also of great interest in context of repositories for nuclear waste and carbon sequestration. A comprehensive study of shale properties is thus crucial for seismic prospecting, particularly due to high elastic anisotropy that is contributed by the alignment of constituent clay minerals during compaction and diagenesis. In this study, we quantitatively analyze composition, crystal preferred orientation (or texture), and the 3D porosity structure in four Posidonia shales from Germany using high energy synchrotron x-rays. We can infer texture information from x-ray diffraction images relying on the Rietveld method, as well as determine the 3D porosity structure from tomography images. We observed that quartz and calcite are dominating phases while illite-smectite, illite-mica and kaolinite are the major clay minerals. The texture strength of clays range from 4.22 to 6.12 m.r.d. A comparison of shallow Posidonia shales with deep shales from the North Sea, Saudi Arabia, and the Gulf of Mexico documents that P-wave anisotropy increases with increasing phyllosilicate content (mainly illite-smectite and kaolinite) and increasing burial. Low absorption features in microtomography images indicate porosity (including kerogen and fractures), which is estimated at 1 vol% and observed to be anisotropic, mainly organized parallel to bedding with little connectivity of flat pores in direction perpendicular to the bedding plane.

  8. Thoughts about uranium-bearing quartz-pebble conglomerates: a summary of ideas presented at the workshop

    International Nuclear Information System (INIS)

    Skinner, B.J.

    1981-01-01

    A summation of papers given at the Workshop on the Genesis of Uranium- and Gold-Bearing Precambrian Quartz-Pebble Conglomerates held at Golden, Colorado, on October 13-15, 1975, is presented. Seven pertinent topics, chosen by the author, are compiled from the several papers and are critically discussed. The time of formation of these deposits is between 3- and 2-billion years ago. The uraniferous conglomerates appear to be of fluvial origin and the known uranium reserves are plotted along an idealized fluviatile system. The source areas for the placers are related to 3 billion year old granites, greenstones and metamorphic rocks of the cratons - these most probably were located paleogeographically in a polar region. The role of diagenesis in the formation of uranium ores is discussed with respect to oxygen content of Precambrian atmospheres and of subsurface waters. The effect of subsequent metamorphism and recrystallization upon indigenous pyrites and kerogen is related. Finally characteristics of known uranium deposits are correlated to suggest a strategy to be employed while prospecting for undiscovered uranium ores. (DT)

  9. Bolide impacts and their significance in fossil fuel geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Saxby, J.D. (CSIRO Division of Coal Technology (Australia))

    1989-01-01

    One of the most dramatic scientific theories of the past ten years has been that a collision between the earth and a large meteor or bolide about 10 km in diameter caused mass extinctions of most of the then-existing species (including dinosaurs) at the end of the Cretaceous, 65 million years ago. Controversy continues but, by and large, organic geochemists researching fossil fuels have not been active participants. Only recently has a relationship between kerogen and the all-important iridium anomaly been investigated (Schmitz et al., 1988). Sediment samples at the Cretaceous-Tertiary boundary contain anomalously high concentrations of iridium, an element whose abundance in the earth's crust is only one ten thousandth of that found in meteorites and presumably in other solar system debris. The purpose of this paper is to briefly raise some questions regarding the bolide impact theory as it affects coal and petroleum deposits. It may well be that organic geochemical evidence will be crucial in either supporting or refuting the impact hypothesis or one of its variations. Even if future research tends to favor widespread explosive volcanism, rather than bolide impacts, the significance of such catastrophic events to the formation and characteristics of fossil fuels needs to be assessed.

  10. Petroleum potential of dysaerobic carbonate source rocks in an intra-shelf basin: the Lower Cretaceous of Provence, France

    Energy Technology Data Exchange (ETDEWEB)

    Machhour, L.; Oudin, J.-L.; Lambert, B.; Lapointe, P. [TOTAL, Centre Scientifique et Technique, Saint-Remy-les-Chevreuse, 78 (France); Masse, J.-P. [Universite de Provence, Centre de Sedimentologie-Paleontologie, Marseille, 13 (France)

    1998-05-01

    Barremian-Aptian Carbonate sediments in southern Provence belong to a drowning sequence within an intra-shelf basin and display organic-carbon-rich horizons corresponding to the demise of a rudists platform system and the onset of dysaerobic conditions. These horizons depart from the classical anoxic model accepted for most marine organic-carbon-rich deposits. They have a rich and diverse fauna documenting nutrient-rich waters with low oxygen content - an environment in which organic matter is preserved from both biological and chemical degradation. Sedimentological, geochemical and palaeoecological investigations suggest that the organic-carbon-rich carbonates reflect dysaerobic conditions favourable for organic matter preservation, the amount of dissolved oxygen being lower than the geochemical threshold for organic matter decay. These organic-carbon-rich sediments are the result of high sea surface productivity and sea bottom conditions favouring preservation. The kerogen is mainly amorphous sapropelic organic matter, essentially algal, with a high hydrogen index and is of marine origin, deposited during high sea-level. (Author)

  11. Hydrocarbon Source Rock Potential of the Sinamar Formation, Muara Bungo, Jambi

    Directory of Open Access Journals (Sweden)

    Moh. Heri Hermiyanto Zajuli

    2014-07-01

    Full Text Available DOI: 10.17014/ijog.v1i1.175The Oligocene Sinamar Formation consists of shale, claystone, mudstone, sandstone, conglomeratic sandstone, and intercalation of coal seams. The objective of study was to identify the hydrocarbon source rock potential of the Sinamar Formation based on geochemichal characteristics. The analyses were focused on fine sediments of the Sinamar Formation comprising shale, claystone, and mudstone. Primary data collected from the Sinamar Formation well and outcrops were analyzed according to TOC, pyrolisis analysis, and gas chromatography - mass spectometry of normal alkanes that include isoprenoids and sterane. The TOC value indicates a very well category. Based on TOC versus Pyrolysis Yields (PY diagram, the shales of Sinamar Formation are included into oil prone source rock potential with good to excellent categories. Fine sediments of the Sinamar Formation tend to produce oil and gas originated from kerogen types I and III. The shales tend to generate oil than claystone and mudstone and therefore they are included into a potential source rock. 

  12. Hydrocarbons thermal maturation: Leopatin method applied to the Parana basin; Maturacao termica de hidrocarbonetos: aplicacao do metodo de Lopatin a Bacia do Parana

    Energy Technology Data Exchange (ETDEWEB)

    Eston, Sergio Medici de; Jardim, Niza S.

    1986-12-31

    One of the requirements for the existent of economic deposits of hydrocarbons is that the organic matter has undergone adequate thermal maturation. Several techniques have been proposed in order to quantity the catagenetic state of kerogen, and the Lopatin-Waples methodology permits quantification at any past time and does not require laboratory tests on samples of the material. For this reason it is an useful techniques for predicting mature zones using as basic information the thermal and subsidence histories of each stratum. Lopatin`s technique was applied to the Parana basin, with McKenzie`s crustal stretching model fitted to the data of 18 wells, and the areas predicted as mature for oil and/or gas were in good agreement with the field results. The technique predicted oil phone areas at the east border of the basin for the Ponta Grossa and Irati formation, and also that most of the thermal maturation occurred after the basalt flows of the Cretaceous period. (author) 41 refs., 6 figs., 6 tabs.

  13. Source rock potential of the organic rich Turonian - Upper Campanian carbonates of northern Lebanon

    Energy Technology Data Exchange (ETDEWEB)

    Daher, S. Bou; Littke, R. [RWTH Aachen Univ. (Germany). Energy and Mineral Resources Group (EMR); Nader, F.H. [IFP Energies nouvelles, Paris (France). Dept. of Sedimentology-Stratigraphy

    2013-08-01

    Upper Cretaceous chalks, marls, and shales are arguably the most prolific petroleum source rocks in the eastern Mediterranean region. 209 core samples from the Turonian - Upper Campanian rock succession in north Lebanon were collected and analyzed for their organic matter (OM) content, quality, and maturity. The total organic carbon (TOC) measurements revealed a very good source rock potential for a 150 m interval within the Upper Santonian - Upper Campanian, with an average of 2% TOC. High HI values (average 707 mg/g TOC) characterize these source rocks as type I kerogen and reflect a very good preservation of the organic matter. T{sub max} values (average 421 C) match the other maturity parameters such as vitrinite reflectance (average 0.35%), and all point towards immature organic matter. The equivalent Upper Cretaceous in the offshore Levant basin has enough overburden to have reached maturity. However, the accurate extrapolation of the organic matter quality and quantity to the offshore is yet a challenge with the data at hand. (orig.)

  14. Disentangling Diagenesis From the Rock Record: An Example From the Permo-Triassic Wordie Creek Formation, East Greenland

    Science.gov (United States)

    Roberts, J.; Turchyn, A. V.; Wignall, P. B.; Newton, R. J.; Vane, C. H.

    2018-01-01

    The measurement of isotope ratios in sedimentary rocks deposited over geological time can provide key insights to past environmental change over important intervals in the past. However, it is important to be aware that secondary alteration can overprint the original isotopic records. We demonstrate this principle using high-resolution carbon, sulfur, and oxygen isotope measurements in organic carbon, pyrite, and carbonate minerals (δ13Corg, δ34Spyr, δ34SCAS, δ13Ccarb, and δ18Ocarb) and kerogen analyses (HI and OI) from the Wordie Creek Formation, East Greenland. These sediments were initially deposited across the Permo-Triassic transition, but as we will show, the carbonate record has been altered by interaction with meteoric water significantly after initial deposition. Comparison of the better preserved organic carbon and pyrite records with a proximal Permo-Triassic sequence reveals significant pyrite-sulfur isotope variability across the Permo-Triassic transition. This regional heterogeneity argues against basin-wide euxinia and instead suggests localized changes in sulfur fractionation in response to variations in organic carbon flux. This hypothesis can be used to explain seemingly inconsistent regional trends in other sulfur isotopes across the Permo-Triassic transition.

  15. The central Myanmar (Burma) oil family - composition and implications for source

    Energy Technology Data Exchange (ETDEWEB)

    Curiale, J A; Kyi, P; Collins, I D; Din, A; Nyein, K; Nyunt, M; Stuart, C J [Unocal Inc., Brea, CA (United States). Energy Resources Division

    1994-11-01

    Geochemical characteristics of 13 Miocene through Eocene oils/seeps, an Eocene coal and an Eocene resin from the central Myanmar (Burma) basin system are examined. Geologic arguments suggest a deep Paleogene source for these oils. Two geochemical arguments that support this inference are (a) the occurrence of saturated and unsaturated C-15 and C-30 cadinane monomers and dimers in pyrolyzates of an Eocene resin and the kerogen from an Eocene coal, and (b) identical compound-specific carbon isotope ratios for selected isoprenoids and n-alkanes in a typical central Myanmar oil and the hydrous pyrolyzate expelled from an Eocene coal. The authors propose an Eocene resinous shale/coal source for these oils, with the oldest (Eocene) reservoirs filling first and the youngst (Miocene) reservoirs filling last, consistent with the observation that the least mature oils are present in the oldest reservoirs. According to this model, surface seepage and near-surface oil could result from subsurface traps that are filled to spillpoint.

  16. Centennial review-forecast--oil sands, shales spar for markets

    Energy Technology Data Exchange (ETDEWEB)

    Pamenter, C B

    1967-09-01

    The relationship between possible developments of tar sands and oil shale deposits to the future of the oil and gas industry is examined. The Athabasca tar sands are estimated to contain 85 billion bbl of synthetic crude oil which can be exploited using currently available mining equipment and proven techniques. Another 240 billion bbl of synthetic crude are potentially available through in-situ extraction methods. Great Canadian Oil Sands Ltd. is using an extraction procedure which involves a surface mining operation, extraction and processing of the bitumen, and product shipments via a 266-mile pipeline. This procedure will be used to produce 45,000 bpd of synthetic crude and 300 ton per day of sulfur. Syncrude Canada Ltd. and Shell Canada Ltd. both have applied to the Alberta government for permission to operate 100,000-bpd operations. Syncrudes is a mining operation and Shell plans to use in-situ extraction. A number of companies have conducted research projects concerning shale oil recovery. The majority of these projects have been aimed at improving mining operations. In-situ retorting of kerogen and extraction of oil has also received consideration.

  17. Regional assessments of the hydrocarbon generation potential of selected North American proterozoic rock sequences. Progress report, September 1989--April 1990

    Energy Technology Data Exchange (ETDEWEB)

    Engel, M.H.; Elmore, R.D.

    1990-04-01

    Our primary research objectives for the first year of this grant are nearing completion. This includes comprehensive sedimentologic/organic geochemical studies of two depositionally distinct, unmetamorphosed units, the Nonesuch Formation ({approximately}1.1 Ga lacustrine rift deposit) and the Dripping Spring Quartzite ({approximately}1.3 Ga marine shelf deposit). As discussed in this progress report, an attempt has been made to (1) identify source rocks by quantification and characterization of constituent organic matter, (2) recognize depositional/diagenetic/catagenetic factors that may have influenced source rock quality and (3) evaluate the possibility of previous or current hydrocarbon generation and migration. Organic petrology and geochemical analyses suggest important differences between kerogens in the Michigan (MI) and Wisconsin (WI) Nonesuch Formation study areas. When considered within a geographic/stratigraphic framework, the Nonesuch Formation in the MI study area exhibits superior source rock potential. It is suggested that sedimentary organic matter in the WI area was subject to more extensive microbial alteration during early diagenesis. It is also possible that thermal maturity levels were slightly to moderately higher in WI than MI. Petrologic evidence for migrated bitumens and the stable isotope composition of late vein carbonates suggest, furthermore, that oil generation and migration may have actually been more extensive in the WI study area.

  18. Causes and timing of future biosphere extinctions

    Directory of Open Access Journals (Sweden)

    S. Franck

    2006-01-01

    Full Text Available We present a minimal model for the global carbon cycle of the Earth containing the reservoirs mantle, ocean floor, continental crust, biosphere, and the kerogen, as well as the combined ocean and atmosphere reservoir. The model is specified by introducing three different types of biosphere: procaryotes, eucaryotes, and complex multicellular life. During the entire existence of the biosphere procaryotes are always present. 2 Gyr ago eucaryotic life first appears. The emergence of complex multicellular life is connected with an explosive increase in biomass and a strong decrease in Cambrian global surface temperature at about 0.54 Gyr ago. In the long-term future the three types of biosphere will die out in reverse sequence of their appearance. We show that there is no evidence for an implosion-like extinction in contrast to the Cambrian explosion. In dependence of their temperature tolerance complex multicellular life and eucaryotes become extinct in about 0.8–1.2 Gyr and 1.3–1.5 Gyr, respectively. The ultimate life span of the biosphere is defined by the extinction of procaryotes in about 1.6 Gyr.

  19. Mud Lake, a modern analog of oil shale deposition in Florida

    Energy Technology Data Exchange (ETDEWEB)

    Burgess, J.D.

    1987-01-01

    Mud Lake in north-central Florida was identified by Bradley as an analog of oil shale-type kerogen deposition. This lake supports an abundant diatom and algal flora which is unique in that the accumulating algal ooze does not decay as long as it stays oxygenated. This same material does not nutritionally support many invertebrates, owing to its flocculent consistency and apparent indigestibility, although fish are abundant and an occasional crocodile is found in the lake. Accumulation of the algal ooze is very slow at roughly 1 foot per 52,000 years based on radiocarbon dates. An understanding of oil shale depositional conditions could be translated into a predictive model for location and recognition of hydrocarbon generating source rocks. When oil shales are mentioned the first association is likely to be that with the Eocene Green River Formation of the Western US. Conditions leading to deposition and preservation of this massive quantity of organic debris is difficult to comprehend, but recognition of modern analogs provide an available area for study and comparison.

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

    Directory of Open Access Journals (Sweden)

    Agnieszka Włodarczyk

    2018-05-01

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

  1. Variation in stable carbon isotopes in organic matter from the Gunflint Iron Formation

    International Nuclear Information System (INIS)

    Barghoorn, E.S.; Knoll, A.H.; Dembicki, H. Jr.; Meinschein, W.G.

    1977-01-01

    In order to examine possible variations in organic carbon isotopic ratios within a single Precambrian formation, the kerogen separated from 15 samples of the approximately 2000 m.y. old Gunflint Iron Formation and the conformably overlying Rove Formation, representing a wide range of lithologies and geographic localities, was isotopically analyzed. From the resulting data, four conclusions can be drawn: (1) delta 13 C values of the shallow water algal chert facies are significantly more negative (-25 to -30 parts per thousand) than those of the deeper water chert-carbonate and taconite facies (-15 to -20 parts per thousand). Comparative data for modern marine algal mats shows a range of delta 13 C values from -8.4 to -19 parts per thousand PDB. Values obtained for fresh water mats were slightly more negative. (2) These differences in isotopic ratios can be correlated with similar differences in preserved microbiotas. (3) Anthraxolite lenses are depleted in 13 C relative to the reduced carbon in surrounding sediments. (4) The effect of Keweenawan diabase intrusions upon the carbon isotopic composition is pronounced, but limited to the immediate vicinity of the contact. (author)

  2. Characteristics of stable carbon isotopic composition of shale gas

    Directory of Open Access Journals (Sweden)

    Zhenya Qu

    2016-04-01

    Full Text Available A type Ⅱ kerogen with low thermal maturity was adopted to perform hydrocarbon generation pyrolysis experiments in a vacuum (Micro-Scale Sealed Vessel system at the heating rates of 2 °C/h and 20 °C/h. The stable carbon isotopic compositions of gas hydrocarbons were measured to investigate their evolving characteristics and the possible reasons for isotope reversal. The δ13C values of methane became more negative with the increasing pyrolysis temperatures until it reached the lightest point, after which they became more positive. Meanwhile, the δ13C values of ethane and propane showed a positive trend with elevating pyrolysis temperatures. The carbon isotopic compositions of shale gasses were mainly determined by the type of parent organic matter, thermal evolutionary extent, and gas migration in shale systems. Our experiments and study proved that the isotope reversal shouldn't occur in a pure thermogenic gas reservoir, it must be involved with some other geochemical process/es; although mechanisms responsible for the reversal are still vague. Carbon isotopic composition of the Fayetteville and Barnett shale gas demonstrated that the isotope reversal was likely involved with water–gas reaction and Fischer-Tropsch synthesis during its generation.

  3. Origin of natural gas; Tennen gas no kigen

    Energy Technology Data Exchange (ETDEWEB)

    Katayama, Y. [The Institute of Applied Energy, Tokyo (Japan)

    1996-03-20

    Natural gas, which is a general term of flammable hydrocarbon gases such as methane, is classified by origin into the following categories : (1) oil field gas (oil gas), (2) aquifers (bacteria-fermented methane), (3) coal gas (coal field gas), and (4) abiogenetic gas. The natural gas which has (1-4) origins and is now used as resource in a large quantity is (1) oil field gas. This gas is a hydrocarbon gas recovered in the production process of petroleum and contains components such as ethane, propane and butane. To the contrary, (2) aquifers and (3) coal gas have methane as main component. As (4) abiogenetic methane, there are gas formed in inorganic reaction in activities of submarine volcanos and deep gas (earth origin gas). Oil field gas has kerogen origin. Aquifers were formed by fermentation of organic matters. Coal gas was formed by coalification of vitrinite. As abiogenetic methane, there are inorganic reaction formation gas and deep gas, the latter of which exists little as resource. 7 refs., 11 figs., 1 tab.

  4. Shale characterization in mass transport complex as a potential source rock: An example from onshore West Java Basin, Indonesia

    Science.gov (United States)

    Nugraha, A. M. S.; Widiarti, R.; Kusumah, E. P.

    2017-12-01

    This study describes a deep-water slump facies shale of the Early Miocene Jatiluhur/Cibulakan Formation to understand its potential as a source rock in an active tectonic region, the onshore West Java. The formation is equivalent with the Gumai Formation, which has been well-known as another prolific source rock besides the Oligocene Talang Akar Formation in North West Java Basin, Indonesia. The equivalent shale formation is expected to have same potential source rock towards the onshore of Central Java. The shale samples were taken onshore, 150 km away from the basin. The shale must be rich of organic matter, have good quality of kerogen, and thermally matured to be categorized as a potential source rock. Investigations from petrography, X-Ray diffractions (XRD), and backscattered electron show heterogeneous mineralogy in the shales. The mineralogy consists of clay minerals, minor quartz, muscovite, calcite, chlorite, clinopyroxene, and other weathered minerals. This composition makes the shale more brittle. Scanning Electron Microscope (SEM) analysis indicate secondary porosities and microstructures. Total Organic Carbon (TOC) shows 0.8-1.1 wt%, compared to the basinal shale 1.5-8 wt%. The shale properties from this outcropped formation indicate a good potential source rock that can be found in the subsurface area with better quality and maturity.

  5. Accumulation conditions and exploration potential of Wufeng-Longmaxi Formations shale gas in Wuxi area, Northeastern Sichuan Basin, China

    Directory of Open Access Journals (Sweden)

    Wei Wu

    2017-12-01

    Full Text Available Wufeng-Longmaxi Formations shale gas is a new exploration field in Wuxi area, Sichuan Basin, China. Some geological parameters related to shale gas evaluation of the new exploration wells in Wuxi area have been studied, including shale reservoir, gas-bearing, geochemical and paleontological characteristics. The study suggests that the original shale gas generation conditions of the area were good, but later this area went through serious and multi-phase tectonic damage. The major evidences include that: the δ13C2 value of shale gas is obviously higher than that in areas with the same maturity, indicating the shale gas is mainly late kerogen cracking gas and high hydrocarbon expulsion efficiency; the porosity of shale in Wuxi area is very low because of strong tectonic movements and lack of retained oil in the shale; some shale cores near faults even show very weak metamorphic characteristics with intense cleavage, and the epidermis of graptolite fossils was pyrolyzed. The comprehensive study shows shale gas in Wuxi area has prospective resources, but the possibility to get scale commercial production in recent time is very low.

  6. Rotationally resolved spectroscopy of Jupiter Trojans (624) Hektor and (911) Agamemnon

    Science.gov (United States)

    Perna, D.; Bott, N.; Hromakina, T.; Mazzotta Epifani, E.; Dotto, E.; Doressoundiram, A.

    2018-03-01

    We present the first-ever rotationally resolved spectroscopic investigation of (624) Hektor and (911) Agamemnon, the two largest Jupiter Trojans. The visible and near-infrared spectra that we have obtained at the TNG telescope (La Palma, Spain) do not show any feature or hints of heterogeneity. In particular, we found no hints of water-related absorptions. No cometary activity was detected down to ˜23.5 R mag arcsec-2 based on the complementary photometric data. We estimated upper limits on the dust production rates of Hektor and Agamemnon to be ≈30 and ≈24 kg s-1, respectively. We modelled complete visible and near-infrared spectra of our targets using the Shkuratov formalism to define the upper limit to the presence of water ice and more in general to constrain their surface composition. For both objects, successful models include amorphous carbon, magnesium-rich pyroxene, and kerogen, with an upper limit to the amount of water ice of a few per cent.

  7. Organic geochemistry investigations of crude oils from Bayoot oilfield in the Masila Basin, east Yemen and their implication for origin of organic matter and source-related type

    Directory of Open Access Journals (Sweden)

    Mohammed Hail Hakimi

    2018-03-01

    Full Text Available Thirteen crude oil samples from fractured basement reservoir rocks in the Bayoot oilfield, Masila Basin were studied to describe oil characteristics and to provide information on the source of organic matter input and the genetic link between oils and their potential source rock in the basin. The bulk geochemical results of whole oil and gasoline hydrocarbons indicate that the Bayoot oils are normal crude oil, with high hydrocarbons of more than 60%. The hydrocarbons are dominated by normal, branched and cyclic alkanes a substantial of the light aromatic compounds, suggesting aliphatic oil-prone kerogen. The high abundant of normal, branched and cyclic alkanes also indicate that the Bayoot oils are not biodegradation oils.The biomarker distributions of isoprenoid, hopane, aromatic and sterane and their cross and triangular plots suggest that the Bayoot oils are grouped into one genetic family and were generated from marine clay-rich source rock that received mixed organic matter and deposited under suboxic conditions. The biomarker distributions of the Bayoot oils are consistent with those of the Late Jurassic Madbi source rock in the basin. Biomarker maturity and oil compositions data also indicate that the Bayoot oils were generated from mature source rock with peak oil-window maturity. Keywords: Crude oil, Basement reservoir rocks, Biomarker, Organic source input, Bayoot oilfield, Masila Basin

  8. Pre-Messinian (Sub-Salt Source-Rock Potential on Back-Stop Basins of the Hellenic Trench System (Messara Basin, Central Crete, Greece

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    Maravelis A.

    2016-01-01

    Full Text Available The Greek part of the Mediterranean Ridge suggests, in terms of its hydrocarbon potential, further frontier exploration. The geological similarities between its prolific portions, within the Cyprus and Egyptian Exclusive Economic Zones, indicate possible recoverable natural gas reserves in its Greek portion. Nevertheless it lacks of systematic frontier exploration although direct petroleum indicators occur. Active mud volcanoes on the Mediterranean Ridge, still emitting concurrently gas and gas hydrates, have not been yet assessed even though are strongly related to hydrocarbon occurrence worldwide (Caspian Sea, Gulf of Mexico, Western African Basin, Trinidad-Tobago, the Nile Cone. For this reason, the source rock potential of the Late Miocene lacustrine deposits on a backstop basin of the Hellenic Trench System (Messara Basin, Crete, Greece, was studied. The obtained pyrolysis data indicate that the containing organic matter is present in sufficient abundance and with good enough quality to be regarded as potential source rocks. The observed type III kerogen suggests gas generation potential. Although indications of higher thermal evolution occur the studied rocks suggest low maturation levels. The biogenic gas seeps in the studied research well further demonstrate the regional gas generation potential.

  9. Generation and migration of Bitumen and oil from the oil shale interval of the Eocene Green River formation, Uinta Basin, Utah

    Science.gov (United States)

    Johnson, Ronald C.; Birdwell, Justin E.; Mercier, Tracey J.

    2016-01-01

    The results from the recent U.S. Geological Survey assessment of in-place oil shale resources of the Eocene Green River Formation, based primarily on the Fischer assay method, are applied herein to define areas where the oil shale interval is depleted of some of its petroleum-generating potential along the deep structural trough of the basin and to make: (1) a general estimates of the amount of this depletion, and (2) estimate the total volume of petroleum generated. Oil yields (gallons of oil per ton of rock, GPT) and in-place oil (barrels of oil per acre, BPA) decrease toward the structural trough of the basin, which represents an offshore lacustrine area that is believed to have originally contained greater petroleum-generating potential than is currently indicated by measured Fischer assay oil yields. Although this interval is considered to be largely immature for oil generation based on vitrinite reflectance measurements, the oil shale interval is a likely source for the gilsonite deposits and much of the tar sands in the basin. Early expulsion of petroleum may have occurred due to the very high organic carbon content and oil-prone nature of the Type I kerogen present in Green River oil shale. In order to examine the possible sources and migration pathways for the tar sands and gilsonite deposits, we have created paleogeographic reconstructions of several oil shale zones in the basin as part of this study.

  10. Relationships between coal-quality and organic-geochemical parameters: A case study of the Hafik coal deposits (Sivas Basin, Turkey)

    Energy Technology Data Exchange (ETDEWEB)

    Erik, N. Yalcin; Sancar, S. [Cumhuriyet University, Department of Geological Engineering, Sivas (Turkey)

    2010-09-01

    This study provides coal-quality, organic-petrographic and organic-geochemical data on Tertiary subbituminous coal of the Hafik area, northwestern part of the Sivas Basin, Turkey. Coal-petrological studies along with proximate and ultimate analyses were undertaken to determine the organic-petrographic characteristics of the Hafik coals. Huminite reflectances were found to be between 0.38 and 0.48% (corresponding to an organic-material-rich and coal layers), values characteristic of low maturity. This parameter shows a good correlation with calorific values (average 21,060 kJ/kg) and average T{sub max} (422 C) mineral-matter diagenesis, indicating immaturity. The studied coals and organic material underwent only low-grade transformation, a consequence of low lithostatic pressure. Therefore, the Hafik coals are actually subbituminous in rank. Rock-Eval analysis results show types II/III and III kerogens. The organic fraction of the coals is mostly comprised of humic-group macerals (gelinites), with small percentages derived from the inertinite and liptinite groups. In this study, organic-petrographic, organic-geochemical and coal quality data were compared. The Hafik deposit is a high-ash, high-sulfur coal. The mineral matter of the coals is comprised mainly of calcite and clay minerals. (author)

  11. Contribution of chronic petroleum inputs to Narragansett Bay and Rhode Island Sound sediments

    Energy Technology Data Exchange (ETDEWEB)

    Van Vleet, E S; Quin, J G

    1978-05-01

    Sediment cores from Narragansett Bay and Rhode Island Sound have been analyzed for petroleum hydrocarbons and compared with a relatively unpolluted sediment core from the Gulf of Maine. The sediments were analyzed for unbound hydrocarbons, hydrocarbons bound or closely associated with humic substances, and residual hydrocarbons bound or closely associated with the clay mineral or kerogen matrix. Results indicated that in general 90-100% of the hydrocarbons were in the unbound form and could be easily extracted with organic solvents. The petroleum hydrocarbons decreased with depth at all stations. Biogenic hydrocarbons (nC/sub 25/, nC/sub 27/, nC/sub 29/, and nC/sub 31/) made up an increasingly greater percentage of the total with increasing depth. The hydrocarbons in the Narragansett Bay sediments and near surface Rhode Island Sound sediments strongly resembled the hydrocarbons previously reported for the Providence River and upper Narragansett Bay. These petroleum-like hydrocarbons were shown to be largely introduced to the river and bay through chronic inputs from a municipal wastewater treatment plant. These hydrocarbons then undergo sedimentation throughout the entire bay and into Rhode Island Sound. Preliminary calculations indicate that over 0.2 million t (tonne) of petroleum hydrocarbons may be transported to the marine environment annually from municipal treatment plants. Most of these hydrocarbons appear to accumulate in estuarine and coastal sediments.

  12. Bolide impacts and their significance in fossil fuel geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Saxby, J D [CSIRO Division of Coal Technology (Australia)

    1989-01-01

    One of the most dramatic scientific theories of the past ten years has been that a collision between the earth and a large meteor or bolide about 10 km in diameter caused mass extinctions of most of the then-existing species (including dinosaurs) at the end of the Cretaceous, 65 million years ago. Controversy continues but, by and large, organic geochemists researching fossil fuels have not been active participants. Only recently has a relationship between kerogen and the all-important iridium anomaly been investigated (Schmitz et al., 1988). Sediment samples at the Cretaceous-Tertiary boundary contain anomalously high concentrations of iridium, an element whose abundance in the earth's crust is only one ten thousandth of that found in meteorites and presumably in other solar system debris. The purpose of this paper is to briefly raise some questions regarding the bolide impact theory as it affects coal and petroleum deposits. It may well be that organic geochemical evidence will be crucial in either supporting or refuting the impact hypothesis or one of its variations. Even if future research tends to favor widespread explosive volcanism, rather than bolide impacts, the significance of such catastrophic events to the formation and characteristics of fossil fuels needs to be assessed.

  13. STUDY OF GAS POTENCY BASED ON GRAVITY ANOMALY MODELING AND SEISMIC PROFILE ANALYSIS AT BANGGAI-SULA BASIN

    Directory of Open Access Journals (Sweden)

    Ediar Usman

    2017-07-01

    Full Text Available Banggai-Sula Basin is one of the basins with character of the micro-continent derived from northern part of Australia. Some traces the migration in the central part of Papua are slate, schist, and gneiss, current movement is facilitated by the Sorong Fault, which runs from the northern part of Papua to eastern part of Sulawesi. Results of gravity anomaly model (2D and 3D, seepage distribution, seismic and fields existing of oil and gas production in the western part of the Banggai-Sula Basin obtained a new prospect area in the northern part of Peleng Island, western part of Banggai Island, southern part of Banggai-Taliabu Islands, western and eastern part of Sulabesi Island. The new prospect area is reflected in the centre with form of the low morphology on gravity model and prospect trap on seismic data in the western part of Tolo Bay. Results of chemical analysis on the source rock of Buya Formation on Tmax vs Hydrogen Index (Tmax vs HI Diagram shows the type III kerogen quality and the Oxygen Index vs Hydrogen Index (OI vs HI Diagram shows the gas prone Type II, so that giving the impression that this area has the potential to containing the gas. The quality of the gas is included in the category of immature to mature type.

  14. Geochemical characteristics of Lower Jurassic source rocks in the Zhongkouzi Basin

    Science.gov (United States)

    Niu, Haiqing; Han, Xiaofeng; Wei, Jianshe; Zhang, Huiyuan; Wang, Baowen

    2018-01-01

    Zhongkouzi basin is formed in Mesozoic and Cenozoic and developed on the Hercynian folded belt, the degree of exploration for oil and gas is relatively low hitherto. In order to find out the geochemical characteristics of the source rocks and the potentials for hydrocarbon generation. The research result shows that by analysis the geochemical characteristics of outcrop samples and new core samples in Longfengshan Group, Longfengshan Group are most developed intervals of favorable source rocks. They are formed in depression period of the basin when the sedimentary environments is salt water lacustrine and the water is keeping stable; The organic matter abundance is middle-higher, the main kerogen type is II1-II2 and few samples act as III type, The organic matter maturity is low maturity to medium maturity. The organic matter maturity of the source rock from eastern part of the basin is higher than in the western region. The source rock of Longfengshan Group are in the hydrocarbon generation threshold. The great mass of source rocks are matured and in the peak stage of oil generation.

  15. Anomalies of natural gas compositions and carbon isotope ratios caused by gas diffusion - A case from the Donghe Sandstone reservoir in the Hadexun Oilfield, Tarim Basin, northwest China

    Science.gov (United States)

    Wang, Yangyang; Chen, Jianfa; Pang, Xiongqi; Zhang, Baoshou; Wang, Yifan; He, Liwen; Chen, Zeya; Zhang, Guoqiang

    2018-05-01

    Natural gases in the Carboniferous Donghe Sandstone reservoir within the Block HD4 of the Hadexun Oilfield, Tarim Basin are characterized by abnormally low total hydrocarbon gas contents ( δ13C ethane (C2) gas has never been reported previously in the Tarim Basin and such large variations in δ13C have rarely been observed in other basins globally. Based on a comprehensive analysis of gas geochemical data and the geological setting of the Carboniferous reservoirs in the Hadexun Oilfield, we reveal that the anomalies of the gas compositions and carbon isotope ratios in the Donghe Sandstone reservoir are caused by gas diffusion through the poorly-sealed caprock rather than by pathways such as gas mixing, microorganism degradation, different kerogen types or thermal maturity degrees of source rocks. The documentation of an in-reservoir gas diffusion during the post entrapment process as a major cause for gas geochemical anomalies may offer important insight into exploring natural gas resources in deeply buried sedimentary basins.

  16. Preservation of uropygial gland lipids in a 48-million-year-old bird.

    Science.gov (United States)

    O'Reilly, Shane; Summons, Roger; Mayr, Gerald; Vinther, Jakob

    2017-10-25

    Although various kinds of organic molecules are known to occur in fossils and rocks, most soft tissue preservation in animals is attributed to melanin or porphyrins. Lipids are particularly stable over time-as diagenetically altered 'geolipids' or as major molecular constituents of kerogen or fossil 'geopolymers'-and may be expected to be preserved in certain vertebrate tissues. Here we analysed lipid residues from the uropygial gland of an early Eocene bird using pyrolysis gas chromatography mass spectroscopy. We found a pattern of aliphatic molecules in the fossil gland that was distinct from the host oil shale sediment matrix and from feathers of the same fossil. The fossil gland contained abundant n -alkenes, n -alkanes and alkylbenzenes with chain lengths greater than 20, as well as functionalized long-chain aldehydes, ketones, alkylnitriles and alkylthiophenes that were not detected in host sediment or fossil feathers. By comparison with modern bird uropygial gland wax esters, we show that these molecular fossils are likely derived from endogenous wax ester fatty alcohols and fatty acids that survived initial decay and underwent early diagenetic geopolymerization. These data demonstrate the high fidelity preservation of the uropygial gland waxes and showcase the resilience of lipids over geologic time and their potential role in the exceptional preservation of lipid-rich tissues of macrofossils. © 2017 The Author(s).

  17. The Messel oil shale - an algae laminate. [A]. Der Messeler Oelschiefer - ein Algenlaminit

    Energy Technology Data Exchange (ETDEWEB)

    Goth, K. (Forschungsinstitut Senckenberg, Frankfurt am Main (Germany). Palaeontologische Sektion)

    1990-12-31

    The lacustrine sediment exposed at the former open cast mine 'Grube Messel', the Messel Oil Shale, consists of allochthonous, autochthonous and autigenous components. A low sedimentation rate (0,1-0,2 mm/a) and an increasing content of coarser clastic material towards the edges of the structure indicate that the Messel lake was small and deep, with a limited drainage basin. The high organic content of the oil shale is made up mainly by cell walls of the coccal green alga Tetraedron minimum. This alga bloomed once a year and caused the lamination of the sediment, which was achieved by sinking of the dead cells. Synsedimentary slumping and sliding of the uppermost sediment layers destroyed the varve pattern in several horizons. These turbidite-like layers often yield a higher amount of coarse grains than the laminations above and below. By counting the seasonal laminae, and taking into account of slumped sediments an age of one million years for the deposition of the Messel Oil Shale is suggested. In extant lakes varved sediments are usually deposited below a chemocline. Therefore a meromictic stratification of the Messel lake water column is suggested. Chemical analyses of Tetraedron minimum cell wall material revealed that it is composed of a highly aliphatic biopolymer. In the Messel Oil Shale this biopolymer forms the kerogen which is, in this case, a result of selective preservation, not of abiological random polymerization of monomers during diagnesis. (orig.) With 29 tabs., 27 figs.

  18. Estimating thermal maturity in the Eagle Ford Shale petroleum system using gas gravity data

    Science.gov (United States)

    Birdwell, Justin E.; Kinney, Scott A.

    2017-01-01

    Basin-wide datasets that provide information on the geochemical properties of petroleum systems, such as source rock quality, product composition, and thermal maturity, are often difficult to come by or assemble from publically available data. When published studies are available and include these kinds of properties, they generally have few sampling locations and limited numbers and types of analyses. Therefore, production-related data and engineering parameters can provide useful proxies for geochemical properties that are often widely available across a play and in some states are reported in publically available or commercial databases. Gas-oil ratios (GOR) can be calculated from instantaneous or cumulative production data and can be related to the source rock geochemical properties like kerogen type (Lewan and Henry, 1999) and thermal maturity (Tian et al., 2013; U.S. Energy Information Administration [EIA], 2014). Oil density or specific gravity (SG), often reported in American Petroleum Institute units (°API = 141.5 /SG – 131.5), can also provide information on source rock thermal maturity, particularly when combined with GOR values in unconventional petroleum systems (Nesheim, 2017).

  19. The fate of oil and gas in a constrained natural system - implications from the Bakken petroleum system

    Energy Technology Data Exchange (ETDEWEB)

    Muscio, G P.A.

    1995-07-01

    When petroleum is produced from its reservoir at present day, it has already been submitted to a complex array of natural processes, which have left their imprint on its chemical and physical properties. These processes involve the generation of petroleum in its source rock as a function of thermal evolution, and its migration to the reservoir. In order to achieve a better understanding of the effects that these processes have on the nature and occurrence of petroleum, it is crucial to investigate a study area that represents an integrated system encompassing all processes from the beginning of crude oil formation to entrapment. The Bakken Shale petroleum system of the Williston Basin (U.S.A./Canada) appears to fulfil these requirements as it covers a broad range of maturity incorporating all stages of catagenesis, and source and reservoir are closely associated, i.e. Bakken petroleum has not been submitted to long secondary migration routes. Combined with a basinwide uniformity in kerogen type, the latter feature constrains the broad scope of potential influences, and therefore the Bakken petroleum system is an ideal candidate to study petroleum generation, its expulsion and migration under natural conditions. By using a selected set of wells/core samples which were considered to be representative for the entire Bakken petroleum system based on comprehensive screening analyses on both kerogen and bitumen, the present study focussed on the following principal aspects: (1) Evolution of petroleum generation as a function of maturation; (2) Primary migration and distribution of crude oil in a constrained natural system; (3) Occurrence of gas in the immature zone; (4) Evaluation of the natural maturity series with simulation experiments. (orig./HS) [Deutsch] Die Prozesse und Phaenomene der natuerlichen Bildung und Migration von Erdoel und Erdgas laufen waehrend der Katagenese sowohl zeitlich als auch raeumlich zu grossen Teilen parallel zueinander ab und praegen die

  20. Microbiology and geochemistry of hydrocarbon-rich sediments erupted from the deep geothermal Lusi site, Indonesia

    Science.gov (United States)

    Krüger, Martin; Straten, Nontje; Mazzini, Adriano; Scheeder, Georg; Blumenberg, Martin

    2016-04-01

    The Lusi eruption represents one of the largest ongoing sedimentary hosted geothermal systems, which started in 2006 following an earthquake on Java Island. Since then it has been producing hot and hydrocarbon rich mud from a central crater with peaks reaching 180.000 m3 per day. Numerous investigations focused on the study of offshore microbial colonies that commonly thrive at offshore methane and oil seeps and mud volcanoes, however very little has been done for onshore seeping structures. Lusi represents a unique opportunity to complete a comprehensive study of onshore microbial communities fed by the seepage of CH4 as well as of heavier liquid hydrocarbons originating from one or more km below the surface. While the source of the methane at Lusi is clear (Mazzini et al., 2012), the origin of the seeping oil, either form the deep mature Eocene Ngimbang (type II kerogen) or from the less mature Pleistocene Upper Kalibeng Fm. (type III kerogen), is still discussed. In the framework of the Lusi Lab project (ERC grant n° 308126) we analysed an oil film and found that carbon preference indices among n-alkanes, sterane and hopane isomers (C29-steranes: 20S/(20S+20R) and α,β-C32 Hopanes (S/(S+R), respectively) are indicative of a low thermal maturity of the oil source rock (~0.5 to 0.6 % vitrinite reflectance equivalents = early oil window maturity). Furthermore, sterane distributions, the pristane to phytane ratio and a relatively high oleanane index, which is an indication of an angiosperm input, demonstrate a strong terrestrial component in the organic matter. Together, hydrocarbons suggest that the source of the oil film is predominantly terrestrial organic matter. Both, source and maturity estimates from biomarkers, are in favor of a type III organic matter source and are therefore suggestive of a mostly Pleistocene Upper Kalibeng Fm. origin. We also conducted a sampling campaign at the Lusi site collecting samples of fresh mud close to the erupting crater

  1. Effects of smectite on the oil-expulsion efficiency of the Kreyenhagen Shale, San Joaquin Basin, California, based on hydrous-pyrolysis experiments

    Science.gov (United States)

    Lewan, Michael D.; Dolan, Michael P.; Curtis, John B.

    2014-01-01

    The amount of oil that maturing source rocks expel is expressed as their expulsion efficiency, which is usually stated in milligrams of expelled oil per gram of original total organic carbon (TOCO). Oil-expulsion efficiency can be determined by heating thermally immature source rocks in the presence of liquid water (i.e., hydrous pyrolysis) at temperatures between 350°C and 365°C for 72 hr. This pyrolysis method generates oil that is compositionally similar to natural crude oil and expels it by processes operative in the subsurface. Consequently, hydrous pyrolysis provides a means to determine oil-expulsion efficiencies and the rock properties that influence them. Smectite in source rocks has previously been considered to promote oil generation and expulsion and is the focus of this hydrous-pyrolysis study involving a representative sample of smectite-rich source rock from the Eocene Kreyenhagen Shale in the San Joaquin Basin of California. Smectite is the major clay mineral (31 wt. %) in this thermally immature sample, which contains 9.4 wt. % total organic carbon (TOC) comprised of type II kerogen. Compared to other immature source rocks that lack smectite as their major clay mineral, the expulsion efficiency of the Kreyenhagen Shale was significantly lower. The expulsion efficiency of the Kreyenhagen whole rock was reduced 88% compared to that of its isolated kerogen. This significant reduction is attributed to bitumen impregnating the smectite interlayers in addition to the rock matrix. Within the interlayers, much of the bitumen is converted to pyrobitumen through crosslinking instead of oil through thermal cracking. As a result, smectite does not promote oil generation but inhibits it. Bitumen impregnation of the rock matrix and smectite interlayers results in the rock pore system changing from water wet to bitumen wet. This change prevents potassium ion (K+) transfer and dissolution and precipitation reactions needed for the conversion of smectite to

  2. Mechanical study of the Chartreuse Fold-and-Thrust Belt: relationships between fluids overpressure and decollement within the Toarcian source-rock

    Science.gov (United States)

    Berthelon, Josselin; Sassi, William; Burov, Evgueni

    2016-04-01

    Many source-rocks are shale and constitute potential detachment levels in Fold-and-Thrust Belts (FTB): the toarcian Schistes-Cartons in the French Chartreuse FTB for example. Their mechanical properties can change during their burial and thermal maturation, as for example when large amount of hydrocarbon fluids are generated. A structural reconstruction of the Chartreuse FTB geo-history places the Toarcian Formation as the major decollement horizon. In this work, a mechanical analysis integrating the fluids overpressuring development is proposed to discuss on the validity of the structural interpretation. At first, an analogue of the Chartreuse Toarcian Fm, the albanian Posidonia Schist, is documented as it can provide insights on its initial properties and composition of its kerogen content. Laboratory characterisation documents the vertical evolution of the mineralogical, geochemical and mechanical parameters of this potential decollement layer. These physical parameters (i.e. Total Organic Carbon (TOC), porosity/permeability relationship, friction coefficient) are used to address overpressure buildup in the frontal part of the Chartreuse FTB with TEMISFlow Arctem Basin modelling approach (Faille et al, 2014) and the structural emplacement of the Chartreuse thrust units using the FLAMAR thermo-mechanical model (Burov et al, 2014). The hydro-mechanical modeling results highlight the calendar, distribution and magnitude of the overpressure that developed within the source-rock in the footwall of a simple fault-bend fold structure localized in the frontal part of the Chartreuse FTB. Several key geological conditions are required to create an overpressure able to fracture the shale-rocks and induce a significant change in the rheological behaviour: high TOC, low permeability, favourable structural evolution. These models highlight the importance of modeling the impact of a diffuse natural hydraulic fracturing to explain fluids propagation toward the foreland within

  3. Air oxidation and biodegradation of the organic matter from the Boom Claycomparison between artificial and natural altered series

    International Nuclear Information System (INIS)

    Blanchart, Pascale; Faure, Pierre; Michels, Raymond; Bruggeman, Christophe; De Craen, Mieke

    2010-01-01

    Document available in extended abstract form only. The Boom Clay formation (Belgium) is studied as the reference host rock for methodological studies on the geological disposal of high-level and long-lived radioactive waste. The drilling of galleries in the Boom Clay at Mol lead to the perturbation of the initial physical and chemical conditions. Since organic matter is present in this argillaceous formation, it is important to know its response to these new conditions. The Boom Clay is of Tertiary age (Rupelian) and has a TOC content up to 5%. Its pore water (20% in mass of rock) contains significant quantities of Dissolved Organic Carbon (DOC) with a mean concentration of 115+/-15 mg/L, determined on the basis of piezometer water as well as squeezing and leaching experiments. Yet, in piezometers, the DOC may show considerable and irregular variations through time, with values ranging between 80 and 425 mg/L. The origin and bio-physico-chemical controls of such variations are yet unknown. Perturbation of the in-situ conditions of the clay is a possible reason for such observation. More likely the introduction of air as well as micro-organisms may have an impact that needs to be estimated. Well-preserved, freshly-drilled Boom Clay samples, as well as samples of different degrees of alteration (air exposed clay from the older galleries) were collected with the aim of determining and quantifying different molecular markers representative for the alteration degree. Additionally, increasing artificial air oxidation experiments were carried out on fresh Praclay samples (sampled during the PRACLAY gallery excavation) in order to obtain an altered reference series. Moreover PRACLAY samples previously extracted with an organic solvent (dichloromethane) were also prepared in order to identify the influence of the kerogen during oxidation. In these experiments, powdered clay was heated at 80 deg. C under air flow during 1, 3, 6, 9, 12, 18 months. Organic matter composition

  4. Organic metamorphism in the California petroleum basins; Chapter B, Insights from extractable bitumen and saturated hydrocarbons

    Science.gov (United States)

    Price, Leigh C.

    2000-01-01

    Seventy-five shales from the Los Angeles, Ventura, and Southern San Joaquin Valley Basins were extracted and analyzed. Samples were chosen on the basis of ROCK-EVAL analyses of a much larger sample base. The samples ranged in burial temperatures from 40 ? to 220 ? C, and contained hydrogen-poor to hydrogen-rich organic matter (OM), based on OM visual typing and a correlation of elemental kerogen hydrogen to carbon ratios with ROCK-EVAL hydrogen indices. By extractable bitumen measurements, rocks with hydrogen- poor OM in the Los Angeles Basin began mainstage hydrocarbon (HC) generation by 90 ? C. The HC concentrations maximized by 165 ? C, and beyond 165 ? C, HC and bitumen concentrations and ROCK-EVAL hydrogen indices all began decreasing to low values reached by 220 ? C, where HC generation was largely complete. Rocks with hydrogen-poor OM in the Southern San Joaquin Valley Basin commenced mainstage HC generation at 135 ? C and HC concentrations maximized by 180 ? C. Above 180 ? C, HC and bitumen concentrations and ROCK-EVAL hydrogen indices all decreased to low values reached by 214 ? C, again the process of HC generation being largely complete. In both cases, bell-shaped HC-generation curves were present versus depth (burial temperature). Mainstage HC generation had not yet begun in Ventura Basin rocks with hydrogen-poor OM by 140 ? C. The apparent lower temperature for initiation of mainstage generation in the Los Angeles Basin is attributed to very recent cooling in that basin from meteoric-water flow. Thus, HC generation there most probably occurred at higher burial temperatures. In contrast, mainstage HC generation, and all aspects of organic metamorphism, were strongly suppressed in rocks with hydrogen-rich OM at temperatures as high as 198 ? C. For example, shales from the Wilmington field (Los Angeles Basin) from 180 ? to 198 ? C retained ROCK-EVAL hydrogen indices of 550- 700 and had saturated-HC coefficients of only 4-15 mg/g organic carbon. The rocks

  5. Géochimie des résines et asphaltènes Geochernistry of Resins and Asphaltenes

    Directory of Open Access Journals (Sweden)

    Tissot B.

    2006-11-01

    Full Text Available Les produits lourds des huiles brutes (résines et asphaltènes jouent un rôle important dans la genèse et l'accumulation du pétrole, ainsi que dans la mise en production par des méthodes conventionnelles ou par récupération assistée. Les asphaltènes et résines sont considérés ici comme des fragments de kérogène, avec une structure d'ensemble comparable : ils peuvent constituer des intermédiaires dans la genèse de l'huile brute par dégradation thermique du kérogène. De plus, la pyrolyse des asphaltènes séparés à partir d'un pétrole biodégradé peut produire de nouveaux hydrocarbures saturés qui reproduisent la fraction saturée primitive, détruite par la dégradation ; on peut ainsi disposer d'un nouvel outil pour corréler ce type d'huiles brutes. Les produits lourds semblent défavorisés par rapport aux hydrocarbures, dans la migration de la roche-mère vers le réservoir, où les résines et asphaltènes sont proportionnellement moins abondants. La structure physique des asphaltènes et résines dans les pétroles, et en particulier l'existence d'une macrostructure du type micelles ou agrégats, est probablement responsable de la viscosité élevée des huiles lourdes. Une meilleure connaissance de cette macrostructure pourrait suggérer de nouvelles méthodes pour diminuer la viscosité et améliorer la récupération des huiles lourdes. The heavy constituents of crude oil (resins and asphaltenes play an important role in generation and accumulation of petroleum, and also in production by conventional and enhanced oil recovery processes. Asphaltenes and resins are considered here as small fragments of kerogen, with a comparable overall structure: they may act as intermediate compounds in oil generation by thermal breakdown of kerogen. Furthermore, pyrolysis of asphaltenes separated from a degraded crude oil is able to generate a new saturated hydrocarbon fraction which duplicates the original one, now degraded

  6. Identifying early Earth microfossils in unsilicified sediments

    Science.gov (United States)

    Javaux, Emmanuelle J.; Asael, Dan; Bekker, Andrey; Debaille, Vinciane; Derenne, Sylvie; Hofmann, Axel; Mattielli, Nadine; Poulton, Simon

    2013-04-01

    Renaut, 2007) or inside gaz bubbles (Brasier et al, 2009; Bengston et al., 2010); or as mobile hydrocarbon microspheres (Wanger et al, 2012). However, these processes cannot explain the formation of large recalcitrant (acid-resistant) hollow vesicles flattened in 2D parallel to bedding, with structurally preserved organic walls, and occurring in shallow-water shales. They do not occur in the right geological conditions, or do not produce the right taphonomy nor structurally preserved morphology; or the right chemistry (acid resistant kerogen, not bitumen); or the right size range and unimodal size distribution. Therefore the carbonaceous microstructures are interpreted as organic-walled microfossils of unknown biological origin (the definition of acritarchs, which may of prokaryotic or eukaryotic origin). In our study, ultrastructural analyzes by transmission electron microscopy provided a crucial test to evidence that large organic-walled vesicles from the 3.2 Ga Moodies Group were true microfossils and not just large kerogen particles (Javaux et al, 2010). This discovery showed that fine-grained siliciclastic window is an interesting target, not only for the proterozoic record, but also for archean paleobiology. Such study also suggests that aqueous fine-grained silicilastic or clay deposits from the Noachian on Mars should be high priority astrobiological targets. To improve the Archean record, siliciclastic sedimentary rocks from new cores recovered through the ICDP Barberton "peering into the cradle of life" will be investigated for discovering and characterizing traces of life (organics, microfossils, microbial mat structures) and their paleohabitat and preservation conditions. Analytical approaches will include in situ study by petrography, organics extraction, optical and electronic microscopy, Raman and FTIR microspectroscopy, pyrolysis, datings, stable isotope analyzes, and a range of redox proxies, in collaboration with partners from the ICDP Barberton project

  7. 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

    and the evolution of organic material to bitumen characterise these sediments as overmature. The HI and OI results reveal that the Collingham and Whitehill sediments are type II kerogen and the Prince Albert is type III kerogen sediment. XRD data shows major rock forming minerals of the black shales to be quartz, illite, muscovite and chlorite with some plagioclase and large amounts of accessory pyrite. Average meso-and macro-porosity of these black shales is 1.5% and SEM images confirm that these sediments are tightly packed. The samples are highly affected by the Cape Fold Belt due to its location so far south and is unlikely to hold gas at this position, however this ongoing investigation will give greater insight to the gas potential of these black shales which are found more north of the region. At the GFZ open system pyrolyses and thermovaporization analyses are still underway.

  8. Relation of peat to oil shale

    Energy Technology Data Exchange (ETDEWEB)

    Linker, S

    1924-01-01

    Samples of oil shale from the Green River formation and from Elko (Nev.), Brazil, Austria, and South Africa were examined, and several varieties of shale were found. Green River oil shale represents three of the more common types plus one less common type. These were: contorted shale with a velvety appearance, thin paper shale resembling the curled-up leaves of a book, massive black shale resembling a piece of rubber, and a less common type, which showed the bedding planes very clearly. The Elko (Nev.) shale was a light buff color; the shale from Brazil resembled a piece of petrified peat. When the shales were cut very thin, their colors ranged from yellow to reddish-brown. The composition, as seen under the microscope, was of well-preserved plant material such as spores, pollen grains, fragments of cell tissues, algae, fungi, bacteria, macerated organic residue, small pieces of resin, animal fossils, and translucent bodies. Oil shale was produced from organic material that accumulated in peat bogs, marshes, or swamps in fresh or salt waters. The organic matter was decomposed by bacterial action. Certain parts of the plants decayed more readily than others. Before lithification occurred, a chemical action took place that changed the softer tissues of the plant debris into a gel. This collodial matter penetrated and surrounded the more resistant fragments and preserved them from further decay. Certain bog waters contain a high percentage of humic acids in solution or collodial suspension and produce insoluble humates when neutralized. These humates are probably the so-called kerogen bodies.

  9. Geochemical constraints on the origin and volume of gas in the New Albany Shale (Devonian-Mississippian), eastern Illinois Basin

    Science.gov (United States)

    Strapoc, D.; Mastalerz, Maria; Schimmelmann, A.; Drobniak, A.; Hasenmueller, N.R.

    2010-01-01

    This study involved analyses of kerogen petrography, gas desorption, geochemistry, microporosity, and mesoporosity of the New Albany Shale (Devonian-Mississippian) in the eastern part of the Illinois Basin. Specifically, detailed core analysis from two locations, one in Owen County, Indiana, and one in Pike County, Indiana, has been conducted. The gas content in the locations studied was primarily dependent on total organic carbon content and the micropore volume of the shales. Gas origin was assessed using stable isotope geochemistry. Measured and modeled vitrinite reflectance values were compared. Depth of burial and formation water salinity dictated different dominant origins of the gas in place in the two locations studied in detail. The shallower Owen County location (415-433 m [1362-1421 ft] deep) contained significant additions of microbial methane, whereas the Pike County location (832-860 m [2730-2822 ft] deep) was characterized exclusively by thermogenic gas. Despite differences in the gas origin, the total gas in both locations was similar, reaching up to 2.1 cm3/g (66 scf/ton). Lower thermogenic gas content in the shallower location (lower maturity and higher loss of gas related to uplift and leakage via relaxed fractures) was compensated for by the additional generation of microbial methane, which was stimulated by an influx of glacial melt water, inducing brine dilution and microbial inoculation. The characteristics of the shale of the Maquoketa Group (Ordovician) in the Pike County location are briefly discussed to provide a comparison to the New Albany Shale. Copyright ??2010. The American Association of Petroleum Geologists. All rights reserved.

  10. Multiscale model reduction for shale gas transport in fractured media

    KAUST Repository

    Akkutlu, I. Y.

    2016-05-18

    In this paper, we develop a multiscale model reduction technique that describes shale gas transport in fractured media. Due to the pore-scale heterogeneities and processes, we use upscaled models to describe the matrix. We follow our previous work (Akkutlu et al. Transp. Porous Media 107(1), 235–260, 2015), where we derived an upscaled model in the form of generalized nonlinear diffusion model to describe the effects of kerogen. To model the interaction between the matrix and the fractures, we use Generalized Multiscale Finite Element Method (Efendiev et al. J. Comput. Phys. 251, 116–135, 2013, 2015). In this approach, the matrix and the fracture interaction is modeled via local multiscale basis functions. In Efendiev et al. (2015), we developed the GMsFEM and applied for linear flows with horizontal or vertical fracture orientations aligned with a Cartesian fine grid. The approach in Efendiev et al. (2015) does not allow handling arbitrary fracture distributions. In this paper, we (1) consider arbitrary fracture distributions on an unstructured grid; (2) develop GMsFEM for nonlinear flows; and (3) develop online basis function strategies to adaptively improve the convergence. The number of multiscale basis functions in each coarse region represents the degrees of freedom needed to achieve a certain error threshold. Our approach is adaptive in a sense that the multiscale basis functions can be added in the regions of interest. Numerical results for two-dimensional problem are presented to demonstrate the efficiency of proposed approach. © 2016 Springer International Publishing Switzerland

  11. From the Earliest Evidence of Life to Complex Single-cell Organisms: The First 3 Gyr on Earth

    Science.gov (United States)

    Buick, Roger

    2006-12-01

    Life has probably been present on Earth since the time of the oldest sedimentary rock record 3.8 Gyr ago, as indicated by graphite with light carbon isotope ratios consistent with derivation from organic matter. But certain evidence for life appears only at 3.52 Gyr, in the form of kerogen (insoluble organic matter) in sedimentary carbonate showing a -25‰ carbon isotope fractionation identical to that imparted by biological carbon fixation. Soon after, at 3.48 Gyr, the first visible evidence for life appears as stromatolites (sediment mounds constructed by microbes), as well as the first evidence for a specific metabolism (large negative sulfur isotope fractionations indicating microbial sulfate reduction). By 2.7 Gyr ago, molecular biomarkers (hydrocarbons derived from biomolecules with distinctive carbon skeletons such as steroids) indicate that all 3 Domains of life: bacteria, eukaryotes (organisms with compartmentalized cells like us) and archaea (bacteria-like organisms with different biochemistry, often inhabiting extreme environments); had evolved. The first multicellular eukaryotes appeared by 1.84 Gyr in the form of fossilized filamentous algae, after the atmosphere changed from anoxic to moderately oxygenated at 2.4 Gyr and following a series of extreme “Snowball Earth” glaciations between 2.4-2.2 Gyr. Planktonic algae diversified thereafter and modern algal groups arose 1.2 Gyr ago, apparently at the end of a prolonged period of ocean anoxia when the deep sea was sulfidic and presumably toxic. Animal evolution was delayed until 0.65 Gyr ago when biomarkers for sponges first appear in the record, evidently after a further rise in atmospheric oxygen to modern levels but surprisingly pre-dating the last of another series of “Snowball Earth” glaciations. These sponges co-existed with an enigmatic extinct group of large flat marine organisms called “Ediacaran fossils” that may have been ancestral to modern animal groups but might also have been

  12. Fluid Behavior and Fluid-Solid Interactions in Nanoporous Media

    Science.gov (United States)

    Xu, H.

    2015-12-01

    Although shale oil/gas production in the US has increased exponentially, the low energy recovery is a daunting problem needed to be solved for its sustainability and continued growth, especially in light of the recent oil/gas price decline. This is apparently related to the small porosity (a few to a few hundred nm) and low permeability (10-16-10-20 m2) of tight shale formations. The fundamental question lies in the anomalous behavior of fluids in nanopores due to confinement effects, which, however, remains poorly understood. In this study, we combined experimental characterization and observations, particularly using small-angle neutron scattering (SANS), with pore-scale modeling using lattice Boltzmann method (LBM), to examine the fluid behavior and fluid-solid interactions in nanopores at reservoir conditions. Experimentally, we characterized the compositions and microstructures of a shale sample from Wolfcamp, Texas, using a variety of analytical techniques. Our analyses reveal that the shale sample is made of organic-matter (OM)-lean and OM-rich layers that exhibit different chemical and mineral compositions, and microstructural characteristics. Using the hydrostatic pressure system and gas-mixing setup we developed, in-situ SANS measurements were conducted at pressures up to 20 kpsi on shale samples imbibed with water or water-methane solutions. The obtained results indicate that capillary effect plays a significant role in fluid-nanopore interactions and the associated changes in nanopore structures vary with pore size and pressure. Computationally, we performed LBM modeling to simulate the flow behavior of methane in kerogen nanoporous structure. The correction factor, which is the ratio of apparent permeability to intrinsic permeability, was calculated. Our results show that the correction factor is always greater than one (non-continuum/non-Darcy effects) and increases with decreasing nanopore size, intrinsic permeability and pressure. Hence, the

  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

    2003-02-10

    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.

  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

    2003-04-28

    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.

  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

    2003-02-11

    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.

  16. Khadum Formation of Pre-Caucasus region as potential source of oil shales: geology and geochemistry

    Directory of Open Access Journals (Sweden)

    N.Sh. Yandarbiev1

    2017-05-01

    Full Text Available One of the main modern aim for oil industry is the development of hydrocarbon extraction technologies from «oil shale». In Russia there are kerogen-saturated carbonate-clayey-siliceous deposits of the Bazhenov Formation, carbonate rocks of the Volga-Ural and Timan-Pechora oil and gas bearing basins and clayey Maikop series of Pre-Caucasus region. The Khadum Formation is lower part of the Maikop series represented by carbonate-clay and clayey deposits. On the basis of long-term field and laboratory investigation conducted by specialists of the Oil and Gas Department from Geological Faculty of the Lomonosov Moscow State University. a comprehensive study of the lithological composition, structure, geochemical, hydrogeological and hydrodynamic characteristics of the Paleogene section and monitoring of the drilled wells, the prospects of the oil and gas potential of the Khadum deposits of the Oligocene in the Eastern Pre-Caucasus oil and gas bearing basin were estimated. 11 gas and 19 oil deposits are discovered within the Khadum deposits, and they are confined to the sand layers and lenses, but most of the Khadum section belongs to «unconventional» sources of hydrocarbons. Based on the integrated approach, a map of oil and gas potential prospects for the Khadum deposits was constructed. Highly prospective territories for drilling for oil, areas with small and medium perspectives, and gas prospecting areas have been singled out. Recommendations are given for drilling and technology for the development of the Pre-Caucasus oil shales, based on the world experience in the development of such formations.

  17. Méthode rapide de caractérisation des roches mètres, de leur potentiel pétrolier et de leur degré d'évolution Rapid Method for Source Rocks Characrerysation and for Determination of Petroleum Potential and Degree of Evolution

    Directory of Open Access Journals (Sweden)

    Espitalié J.

    2006-11-01

    Full Text Available Les études fondamentales réalisées sur les kérogènes à l'aide de diverses méthodes physico-chimiques d'analyse ont permis de mettre au point une méthode et un appareillage adaptés à l'exploration pétrolière. On expose dans cet article la mise au point de cette méthode et on montre, à l'aide des paramètres qu'elle permet d'obtenir, ses applications dans le domaine de l'exploration pétrolière - reconnaissance des différents types de roche mère et de leur potentiel pétrolier; - caractérisation de leur degré d'évolution (zone à huile - zone à gaz. On montre aussi que cette méthode convient particulièrement bien à l'estimation du rendement en huile des roches bitumineuses et à l'étude de la qualité et du rang des charbons. Fundamental research on kerogens by different physico-chemical analysis methods have led to the development of a method and equipment suited for petroleum exploration. This article describes the development of this method and, by means of the parameters it determines, shows how it con be applied in the field of petroleum exploration - exploring different types of source rock and their petroleum potential ; - characterizing their degree of evolution (ail zone/gas zone. This method is also shown ta be particularly suited for estimating the oil yield of cil shales and investigating the quality and classification of cool.

  18. Palynological and bulk geochemical constraints on the paleoceanographic conditions across the Frasnian-Famennian boundary, New Albany Shale, Indiana

    Energy Technology Data Exchange (ETDEWEB)

    Rue, Sarah R. de la [Department of Geology and Geophysics, Louisiana State University, Baton Rouge, Louisiana 70803-4101 (United States); Rowe, Harold D.; Rimmer, Susan M. [Department of Earth and Environmental Sciences, Slone Research Building, University of Kentucky, Lexington KY 40506-0053 (United States)

    2007-06-01

    A down-core record of stable isotope and geochemical results is integrated with palynofacies (kerogen) data from the New Albany Shale (Indiana) to reconstruct environmental changes that occurred across the Frasnian-Famennian boundary. Preliminary interpretations are focused on developing several multiproxy linkages that will potentially lead toward a more robust understanding of the occurrence and significance of phytoplankton assemblage variations during the Late Devonian, a time of widespread black shale formation. Development of such linkages will potentially provide a more comprehensive assessment of the various controls on 1) primary production, and 2) carbon sequestration in a large, low-paleolatitude intracratonic basin. An abrupt change in the geochemical and biotic proxies for particulate organic matter across the Frasnian-Famennian boundary coincides with a distinct lithological change, characterized by laminated, brownish-black Famennian mudstones unconformably overlying alternating bioturbated, greenish-gray and non-bioturbated, dark-gray Frasnian mudstones. Elemental and isotopic profiles reflect different patterns of production, degradation, and removal of organic carbon in the two shale facies. A shift from acritarch- to prasinophyte-dominated waters across the boundary indicates the overall importance of bathymetric fluctuations, chemico-physical conditions, and nutrient availability related to eustatic sea-level change. A positive {delta}{sup 13}C{sub V-PDB} shift of 1.1 permille across the boundary is interpreted to be correlative with the global Upper Kellwasser Event. A preliminary model is proposed to explain the sustainable primary production during times of maximum flooding, thereby enhancing organic preservation during black shale formation. (author)

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

    Science.gov (United States)

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

    1981-01-01

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

  20. The influence of petrography, mineralogy and chemistry on burnability and reactivity of quicklime produced in Twin Shaft Regenerative (TSR) kilns from Neoarchean limestone (Transvaal Supergroup, South Africa)

    Science.gov (United States)

    Vola, Gabriele; Sarandrea, Luca; Della Porta, Giovanna; Cavallo, Alessandro; Jadoul, Flavio; Cruciani, Giuseppe

    2017-12-01

    This study evaluates the influence of chemical, mineralogical and petrographic features of the Neoarchean limestone from the Ouplaas Mine (Griqualand West, South Africa) on its burnability and quicklime reactivity, considering the main use as raw material for high-grade lime production in twin shaft regenerative (TSR) kilns. This limestone consists of laminated clotted peloidal micrite and fenestrate microbial boundstone with herringbone calcite and organic carbon (kerogen) within stylolites. Diagenetic modifications include hypidiotopic dolomite, micrite to microsparite recrystallization, stylolites, poikilotopic calcite, chert and saddle dolomite replacements. Burning and technical tests widely attest that the Neoarchean limestone is sensitive to high temperature, showing an unusual and drastically pronounced sintering or overburning tendency. The slaking reactivity, according to EN 459-2 is high for lime burnt at 1050 °C, but rapidly decreases for lime burnt at 1150 °C. The predominant micritic microbial textures, coupled with the organic carbon, are key-factors influencing the low burnability and the high sintering tendency. The presence of burial cementation, especially poikilotopic calcite, seems to promote higher burnability, either in terms of starting calcination temperature, or in terms of higher carbonate dissociation rate. In fact, the highest calcination velocity determined by thermal analysis is consistent with the highest slaking reactivity of the lower stratum of the quarry, enriched in poikilotopic calcite. Secondly, locally concentered dolomitic marly limestones, and sporadic back shales negatively affects the quicklime reactivity, as well. This study confirms that a multidisciplinary analytical approach is essential for selecting the best raw mix for achieving the highest lime reactivity in TSR kilns.

  1. Origin of a Tertiary oil from El Mahafir wildcat & geochemical correlation to some Muglad source rocks, Muglad basin, Sudan

    Science.gov (United States)

    Fadul Abul Gebbayin, Omer. I. M.; Zhong, Ningning; Ali Ibrahim, Gulfan; Ali Alzain, Mohamed

    2018-01-01

    Source rock screening analysis was performed on four stratigraphic units from the Muglad basin namely; Abu Gabra, Zarqa, Ghazal, and Baraka formations using pyrolysis and Vitrinite Reflectance (Ro). Results, integrated with the chromatographic and isotopic data from these rocks extracts and a Tertiary oil from El Mahafir-1 wild cat, were used to determine the origin of the oil. A good organic source within the Middle Abu Gabra Formation is observed in wells El Toor-6 and Neem Deep-1 (TOC, 1.0-2.0% & S2 5.0-10.0 mg C/g rock), with mixed kerogens I, II, & III, and thermally mature (% Ro = 0.74-0.94). The Campanian-Early Maastrichtian sequence, i.e. Zarqa and Ghazal formations are generally poor (TOC, diversity, both in space and time and is characterized by dominant algal input at some areas and or stratigraphic intervals [Elevated tricyclics, higher C29/C30 hopanes (0.5-1.14), and relatively low Gammacerane indices (4.6-14.4)], while mixed with abundant terrigenous material at others. A direct correlation between El Mahafir oil and the Abu Gabra extracts is thus inferred based on: its mixed organic source nature, oxic to sub-oxic depositional environment (Pr/Ph 1.22), relatively low C29/C30 hopanes (0.54), low C28 steranes (29%), and a high gammacerane index (20.5). This is largely supported by the maturity modeling results which suggest generation is only from the Abu Gabra at this location.

  2. Bioaccumulation of petroleum hydrocarbons in arctic amphipods in the oil development area of the Alaskan Beaufort Sea.

    Science.gov (United States)

    Neff, Jerry M; Durell, Gregory S

    2012-04-01

    An objective of a multiyear monitoring program, sponsored by the US Department of the Interior, Bureau of Ocean Energy Management was to examine temporal and spatial changes in chemical and biological characteristics of the Arctic marine environment resulting from offshore oil exploration and development activities in the development area of the Alaskan Beaufort Sea. To determine if petroleum hydrocarbons from offshore oil operations are entering the Beaufort Sea food web, we measured concentrations of hydrocarbons in tissues of amphipods, Anonyx nugax, sediments, Northstar crude oil, and coastal peat, collected between 1999 and 2006 throughout the development area. Mean concentrations of polycyclic aromatic hydrocarbons (PAH), saturated hydrocarbons (SHC), and sterane and triterpane petroleum biomarkers (StTr) were not significantly different in amphipods near the Northstar oil production facility, before and after it came on line in 2001, and in amphipods from elsewhere in the study area. Forensic analysis of the profiles (relative composition and concentrations) of the 3 hydrocarbon classes revealed that hydrocarbon compositions were different in amphipods, surface sediments where the amphipods were collected, Northstar crude oil, and peat from the deltas of 4 North Slope rivers. Amphipods and sediments contained a mixture of petrogenic, pyrogenic, and biogenic PAH. The SHC in amphipods were dominated by pristane derived from zooplankton, indicating that the SHC were primarily from the amphipod diet of zooplankton detritus. The petroleum biomarker StTr profiles did not resemble those in Northstar crude oil. The forensic analysis revealed that hydrocarbons in amphipod tissues were not from oil production at Northstar. Hydrocarbons in amphipod tissues were primarily from their diet and from river runoff and coastal erosion of natural diagenic and fossil terrestrial materials, including seep oils, kerogens, and peat. Offshore oil and gas exploration and development

  3. Sulfur-binding in recent environments: II. Speciation of sulfur and iron and implications for the occurrence of organo-sulfur compounds

    Science.gov (United States)

    Hartgers, Walter A.; Lòpez, Jordi F.; Sinninghe Damsté, Jaap S.; Reiss, Christine; Maxwell, James R.; Grimalt, Joan O.

    1997-11-01

    Speciation of iron and sulfur species was determined for two recent sediments (La Trinitat and Lake Cisó) which were deposited in environments with a high biological productivity and sulfate-reducing activity. In sediments from calcite ponds of La Trinitat an excess of reactive iron species (iron monosulfides, iron hydroxides) results in a depletion of reactive sulfur which is accompanied by a virtual absence of organo-sulfur compounds, both in low (LMW) and high molecular-weight (HMW) fractions. Small amounts of phytanyl and highly branched isoprenoid (HBI) thiophenes in the extract demonstrate that these molecules exhibit a higher reactivity towards reduced sulfur species as compared to detrital iron. Euxinic sediments from Lake Cisó are characterised by an excess of reduced sulfur species which can rapidly trap reactive iron. High concentrations of H 2S results in the formation of organo-sulfur compounds which were encountered in both LMW and HMW fractions. The major part of the organic sulfur is bound to the carbohydrate portion of woody tissues, whose presence was revealed by a specific alkylthiophene distribution in the flash pyrolysate and by Li/EtNH 2 desulfurisation of the kerogen which resulted in the solubilisation of the sulfur-enriched hemicellulose fraction. Relatively high amounts of sulfurised C 25 HBI compounds in the sediment extract of Lake Cisó reflect the incorporation of sulfur into algal derived organic matter upon early diagenesis. The combined approach of the speciation of iron and sulfur species and the molecular analysis of sedimentary fractions demonstrates that abiotic sulfur binding to organic matter occurs at the earliest stages of diagenesis under specific depositional conditions (anoxic, stratified water column) in which an excess of reduced sulfur species relative to the amount of reactive iron is a controlling factor.

  4. Application of organic petrography in North American shale petroleum systems: A review

    Science.gov (United States)

    Hackley, Paul C.; Cardott, Brian J.

    2016-01-01

    Organic petrography via incident light microscopy has broad application to shale petroleum systems, including delineation of thermal maturity windows and determination of organo-facies. Incident light microscopy allows practitioners the ability to identify various types of organic components and demonstrates that solid bitumen is the dominant organic matter occurring in shale plays of peak oil and gas window thermal maturity, whereas oil-prone Type I/II kerogens have converted to hydrocarbons and are not present. High magnification SEM observation of an interconnected organic porosity occurring in the solid bitumen of thermally mature shale reservoirs has enabled major advances in our understanding of hydrocarbon migration and storage in shale, but suffers from inability to confirm the type of organic matter present. Herein we review organic petrography applications in the North American shale plays through discussion of incident light photographic examples. In the first part of the manuscript we provide basic practical information on the measurement of organic reflectance and outline fluorescence microscopy and other petrographic approaches to the determination of thermal maturity. In the second half of the paper we discuss applications of organic petrography and SEM in all of the major shale petroleum systems in North America including tight oil plays such as the Bakken, Eagle Ford and Niobrara, and shale gas and condensate plays including the Barnett, Duvernay, Haynesville-Bossier, Marcellus, Utica, and Woodford, among others. Our review suggests systematic research employing correlative high resolution imaging techniques and in situ geochemical probing is needed to better document hydrocarbon storage, migration and wettability properties of solid bitumen at the pressure and temperature conditions of shale reservoirs.

  5. Near-Infrared Imaging for Spatial Mapping of Organic Content in Petroleum Source Rocks

    Science.gov (United States)

    Mehmani, Y.; Burnham, A. K.; Vanden Berg, M. D.; Tchelepi, H.

    2017-12-01

    Natural gas from unconventional petroleum source rocks (shales) plays a key role in our transition towards sustainable low-carbon energy production. The potential for carbon storage (in adsorbed state) in these formations further aligns with efforts to mitigate climate change. Optimizing production and development from these resources requires knowledge of the hydro-thermo-mechanical properties of the rock, which are often strong functions of organic content. This work demonstrates the potential of near-infrared (NIR) spectral imaging in mapping the spatial distribution of organic content with O(100µm) resolution on cores that can span several hundred feet in depth (Mehmani et al., 2017). We validate our approach for the immature oil shale of the Green River Formation (GRF), USA, and show its applicability potential in other formations. The method is a generalization of a previously developed optical approach specialized to the GRF (Mehmani et al., 2016a). The implications of this work for spatial mapping of hydro-thermo-mechanical properties of excavated cores, in particular thermal conductivity, are discussed (Mehmani et al., 2016b). References:Mehmani, Y., A.K. Burnham, M.D. Vanden Berg, H. Tchelepi, "Quantification of organic content in shales via near-infrared imaging: Green River Formation." Fuel, (2017). Mehmani, Y., A.K. Burnham, M.D. Vanden Berg, F. Gelin, and H. Tchelepi. "Quantification of kerogen content in organic-rich shales from optical photographs." Fuel, (2016a). Mehmani, Y., A.K. Burnham, H. Tchelepi, "From optics to upscaled thermal conductivity: Green River oil shale." Fuel, (2016b).

  6. Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4-CO2-H2O) Interactions in Shale Nanopores under Reservoir Conditions.

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yifeng [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2018-02-01

    Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO2 and H2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO2 has been suggested as an alternative fluid for subsurface fracturing such that CO2 enhanced gas recovery can also serve as a CO2 sequestration process. Limited data indicate that CO2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH4 in shale matrix. Therefore, fundamental understanding of CH4-CO2-H2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO2 sequestration. This project focuses on the systematic study of CH4-CO2-H2O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.

  7. Paleothermicity in the Central Asturian Coal Basin, North Spain

    Energy Technology Data Exchange (ETDEWEB)

    Piedad-Sanchez, Noe; Izart, Alain; Martinez, Luis; Elie, Marcel; Menetrier, Cedric [UMR G2R/7566-Geologie et Gestion des Ressources Minerales et Energetiques, Equipe Dynamique des Bassins Sedimentaires et des Matieres Organiques, Faculte des Sciences, Universite Henri Poincare, Nancy 1, BP-239, Boulevard des Aiguillettes, 54506 Vandoeuvre-les-Nancy Cedex (France); Suarez-Ruiz, Isabel [Instituto Nacional del Carbon (CSIC), C/ Francisco Pintado Fe, 26, 33011-Oviedo (Spain)

    2004-06-23

    This research shows for the first time maps of vitrinite reflectances and paleotemperatures from the Central Asturian Coal Basin (North Spain) which is a Carboniferous (Pennsylvanian) Basin mainly of Moscovian age. Vitrinite reflectance values decrease from north to south whereas volatile matter distribution increases from south to north. Vitrinite reflectance and volatile matter parameters indicate a coal rank ranging from high volatile bituminous coal in the north, to semianthracite and anthracite in the south. Rock-Eval data show that the organic matter of this basin is Type III kerogen, with a maturation ranging from oil to gas window. Paleotemperatures were calculated by diverse methods using vitrinite reflectance data for different durations of heating and Rock-Eval results. The calculated paleotemperatures and vertical paleotemperature gradients decrease from south to north. The thermal gradient variation in the Central Asturian Coal Basin points to the influence of at least two heating events that affected the organic matter. The first associated with a regular geothermal gradient operating over a long period of time, and the second linked to a southern granitic event of short duration estimated by tectonic data. The short thermal event was located at the end of sedimentation (Late Moscovian and Late Westphalian D) and after folding, but before the overthrusting during the Asturian tectonic phase located before the Early Kasimovian (Cantabrian and Stephanian) deposits. Finally, a simulation of paleotemperatures around the granitic pluton was calculated and compared to maps of paleotemperatures obtained by various methods. These maps refer to an initial depth of one or two km in accordance with the selected methods that are compatible with local erosion. This approach was preferred in order to explain the metamorphism of coal, rather than the hypothesis of hydrothermal fluid flow proposed for other foreland basins. This regional thermal anomaly could be

  8. The organic surface of 5145 Pholus: Constraints set by scattering theory

    Science.gov (United States)

    Wilson, Peter D.; Sagan, Carl; Thompson, W. Reid

    1994-01-01

    No known body in the Solar System has a spectrum redder than that of object 5145 Pholus. We use Hapke scattering theory and optical constants measured in this laboratory to examine the ability of mixtures of a number of organic solids and ices to reproduce the observed spectrum and phase variation. The primary materials considered are poly-HCN, kerogen, Murchison organic extract, Titan tholin, ice tholin, and water ice. In a computer grid search of over 10 million models, we find an intraparticle mixture of 15% Titan tholin, 10% poly-HCN, and 75% water ice with 10-micrometers particles to provide an excellent fit. Replacing water ice with ammonia ice improves the fits significantly while using a pure hydrocarbon tholin, Tholin alpha, instead of Titan tholin makes only modest improvements. All acceptable fits require Titan tholin or some comparable material to provide the steep slope in the visible, and poly-HCN or some comparable material to provide strong absorption in the near-infrared. A pure Titan tholin surface with 16-micrometers particles, as well as all acceptable Pholus models, fit the present spectrophotometric data for the transplutonian object 1992 QB(sub 1). The feasibility of gas-phase chemistry to generate material like Titan tholin on such small objects is examined. An irradiated transient atmosphere arising from sublimating ices may generate at most a few centimeters of tholin over the lifetime of the Solar System, but this is insignificant compared to the expected lag deposit of primordial contaminants left behind by the sublimating ice. Irradiation of subsurface N2/CH4 or NH3/CH4 ice by cosmic rays may generate approximately 20 cm of tholin in the upper 10 m of regolith in the same time scale but the identity of this tholin to its gas-phase equivalent has not been demonstrated.

  9. Heterogeneity of the organic matter in the Guayuta group, Eastern Venezuelan Basin

    Energy Technology Data Exchange (ETDEWEB)

    Alberdi, M.; Gallango, O.; Ruggiero, A.; Jordan, N. (Intevep, S.A., Caracas (Venezuela)); Lefargue, E. (I.F.P., Rueil Malmaison (France))

    1993-02-01

    The purpose of this study is to evaluate the organic matter heterogeneities in the Guayuta Group as a principal hydrocarbon source rock in the Eastern Venezuelan Basin. In order to do this, thirteen wells and five work stations on outcrops of the Interior Mountain Belt were analyzed to study the regional and vertical variations in the geochemical characteristics of the organic matter. It is possible to detect significant differences in quality and quantity of the organic matter which could corroborate the regional development of two organic facies from North to South in the Maturin Subbasin. The northern organic facies show excellent characteristics as source rock. The study of vertical distribution of organic matter was carried out in a well of northern part of the Monagas state, which represents the southern organic facies. It shows an irregular input of continental organic matter, thermally immature. Besides the organic matter content was low (around 1.5%) without depth tendencies. These sediments are clastic and bioclastic in contrast with carbonates and pelagic shales of the Guayuta Group in the Interior Mountain Belt. The outcrop samples studied show a high total organic content (2-6%) despite the high maturity determined on kerogen. The systematic study of this geochemical parameter show pseudocyclic relationships with a general tendency to increase toward the bottom of the section. V, Ni, and S determinations could indicate that anoxic conditions were developing toward the North where the marine organic matter was sedimenting. The results of this study are in agreement with paleogeographic model of sedimentation during middle and late Cretaceous, with sources of sediments from South and a progressive depth of the basin toward the North.

  10. Molecular Evidence for Radical Changes in Ocean Chemistry Across the Permian Triassic Boundary at Meishan in South China

    Science.gov (United States)

    Love, G. D.; Cao, C.; Jin, Y.; Summons, R. E.

    2004-12-01

    Samples from outcrop and from a new core drilled through the Permian Triassic Boundary at the type section at Meishan have been examined for biomarker and isotopic evidence of biotic and associated environmental change. Late Permian sediments from Meishan Beds 22-27 are characterized by indicators of anoxia including low Pr/Ph ratios and abundant aryl isoprenoids and isoreneieratane derived from the precursor carotenoid isorenieratene. The latter compounds are biomarkers for green sulfur bacteria (Chlorobiaceae) and are considered reliable indicators of euxinic water columns where sulfide extends to the photic zone. The peak of Chlorobiaceae biomarker abundance coincides with a rapid and synchronous drop in the ƒO13C and ƒO15N values of kerogen. On passing up into the Early Triassic, the biomarker signal for Chlorobiaceae wanes and is almost absent by Bed 30 where it is replaced by one for cyanobacteria including abundant hopanes and 2-methylhopanes and accompanying methyl and dimethyl alkanes. A very high value for the hopane/sterane ratio from Beds 30-38 indicates continuing dominant cyanobacterial productivity and only minor inputs from an algal plankton. The prevalence of aryl isoprenoids in P-Tr sediments at the Meishan section of South China is also recorded in a recently cored borehole, Hovea-3, of the Perth Basin, Western Australia. This suggests similar paleoenvironmental conditions prevailed across the Tethys Ocean during and immediately after the P-Tr Boundary. In particular, the presence of biomarkers for Chlorobiaceae at two separate locations indicates that water column euxinia was pervasive during the extinction event and suggests that sulfide may have been a key toxic agent.

  11. Laboratory Study of Aliphatic Organic Spectral Signatures and Applications to Ceres and Primitive Asteroids

    Science.gov (United States)

    Kaplan, H. H.; Milliken, R.

    2017-12-01

    Aliphatic organics were recently discovered on the surface of Ceres with Dawn's Visible and InfraRed (VIR) mapping spectrometer, which has implications for prebiotic chemistry of Ceres and other asteroids. An absorption in the spectrum at 3.4 µm was used to identify and provide initial estimates of the amount of organic material. We have studied the 3.4 µm absorption in reflectance spectra of bulk rock and meteorite powders and isolated organic materials in the NASA RELAB facility at Brown University to determine how organic composition and abundance affects absorption strength. Reflectance spectra of insoluble organic matter (IOM) extracted from carbonaceous chondrites were measured from 0.35 - 25 µm. These IOM have known elemental (H, C, N, O) and isotopic compositions that were compared with spectral properties. Bulk meteorites were measured as chips and particulates over the same wavelength range. Despite overall low reflectance values (albedo IOM samples, specifically those with a H/C ratio greater than 0.4. The absorption strength (band depth) increases with increasing H/C ratio, which corroborates similar findings in our previous study of sedimentary rocks and isolated kerogens. The absorption strength in the bulk meteorites reflects both H/C of the IOM and the concentration of IOM in the inorganic (mineral) matrix. Overlapping absorptions from carbonates and phyllosilicates (OH/H2O) can also influence the aliphatic organic bands in bulk rocks and meteorites. This laboratory work provides a foundation that can be used to constrain the composition of Ceres' aliphatic organic matter using band depth as a proxy for H/C. Reflectance spectra collected for this work will also be used to model the Dawn VIR data and obtain abundance and H/C estimates assuming that the organic material on Ceres' surface is similar to carbonaceous chondrite IOM. These spectra and findings can aid interpretation of reflectance data from Ceres and other asteroid missions, such as

  12. Geochemistry of formation waters from the Wolfcamp and “Cline” shales: Insights into brine origin, reservoir connectivity, and fluid flow in the Permian Basin, USA

    Science.gov (United States)

    Engle, Mark A.; Reyes, Francisco R.; Varonka, Matthew S.; Orem, William H.; Lin, Ma; Ianno, Adam J.; Westphal, Tiffani M.; Xu, Pei; Carroll, Kenneth C.

    2016-01-01

    Despite being one of the most important oil producing provinces in the United States, information on basinal hydrogeology and fluid flow in the Permian Basin of Texas and New Mexico is lacking. The source and geochemistry of brines from the basin were investigated (Ordovician- to Guadalupian-age reservoirs) by combining previously published data from conventional reservoirs with geochemical results for 39 new produced water samples, with a focus on those from shales. Salinity of the Ca–Cl-type brines in the basin generally increases with depth reaching a maximum in Devonian (median = 154 g/L) reservoirs, followed by decreases in salinity in the Silurian (median = 77 g/L) and Ordovician (median = 70 g/L) reservoirs. Isotopic data for B, O, H, and Sr and ion chemistry indicate three major types of water. Lower salinity fluids (100 g/L), isotopically heavy (O and H) water in Leonardian [Permian] to Pennsylvanian reservoirs (2–3.2 km depth) is evaporated, Late Permian seawater. Water from the Permian Wolfcamp and Pennsylvanian “Cline” shales, which are isotopically similar but lower in salinity and enriched in alkalis, appear to have developed their composition due to post-illitization diffusion into the shales. Samples from the “Cline” shale are further enriched with NH4, Br, I and isotopically light B, sourced from the breakdown of marine kerogen in the unit. Lower salinity waters (3 km depth), which plot near the modern local meteoric water line, are distinct from the water in overlying reservoirs. We propose that these deep meteoric waters are part of a newly identified hydrogeologic unit: the Deep Basin Meteoric Aquifer System. Chemical, isotopic, and pressure data suggest that despite over-pressuring in the Wolfcamp shale, there is little potential for vertical fluid migration to the surface environment via natural conduits.

  13. Lunar and Planetary Science XXXVI, Part 4

    Science.gov (United States)

    2005-01-01

    Contents include the following: High-Resolution Electron Energy-Loss Spectroscopy (HREELS) Using a Monochromated TEM/STEM. Dynamical Evolution of Planets in Open Clusters. Experimental Petrology of the Basaltic Shergottite Yamato 980459: Implications for the Thermal Structure of the Martian Mantle. Cryogenic Reflectance Spectroscopy of Highly Hydrated Sulfur-bearing Salts. Implications for Core Formation of the Earth from High Pressure-Temperature Au Partitioning Experiments. Uranium-Thorium Cosmochronology. Protracted Core Differentiation in Asteroids from 182Hf-182W Systematics in the Eagle Station Pallasite. Maximizing Mission Science Return Through Use of Spacecraft Autonomy: Active Volcanism and the Autonomous Sciencecraft Experiment. Classification of Volcanic Eruptions on Io and Earth Using Low-Resolution Remote Sensing Data. Isotopic Mass Fractionation Laws and the Initial Solar System (sup26)Al/(sup27)Al Ratio. Catastrophic Disruption of Porous and Solid Ice Bodies (sup187)Re-(sup187)Os Isotope Disturbance in LaPaz Mare Basalt Meteorites. Comparative Petrology and Geochemistry of the LaPaz Mare Basalt Meteorites. A Comparison of the Structure and Bonding of Carbon in Apex Chert Kerogenous Material and Fischer-Tropsch-Type Carbons. Broad Spectrum Characterization of Returned Samples: Orientation Constraints of Small Samples on X-Ray and Other Spectroscopies. Apollo 14 High-Ti Picritic Glass: Oxidation/Reduction by Condensation of Alkali Metals. New Lunar Meteorites from Oman: Dhofar 925, 960 and 961. The First Six Months of Iapetus Observations by the Cassini ISS Camera. First Imaging Results from the Iapetus B/C Flyby of the Cassini Spacecraft. Radiative Transfer Calculations for the Atmosphere of Mars in the 200-900 nm Range. Geomorphologic Map of the Atlantis Basin, Terra Sirenum, Mars. The Meaning of Iron 60: A Nearby Supernova Injected Short-lived Radionuclides into Our Protoplanetary Disk.

  14. Dynamic mechanical properties and anisotropy of synthetic shales with different clay minerals under confining pressure

    Science.gov (United States)

    Gong, Fei; Di, Bangrang; Wei, Jianxin; Ding, Pinbo; Shuai, Da

    2018-03-01

    The presence of clay minerals can alter the elastic behaviour of reservoir rocks significantly as the type of clay minerals, their volume and distribution, and their orientation control the shale's intrinsic anisotropic behaviours. Clay minerals are the most abundant materials in shale, and it has been proven extremely difficult to measure the elastic properties of natural shale by means of a single variable (in this case, the type of clay minerals), due to the influences of multiple factors, including water, TOC content and complex mineral compositions. We used quartz, clay (kaolinite, illite and smectite), carbonate and kerogen extract as the primary materials to construct synthetic shale with different clay minerals. Ultrasonic experiments were conducted to investigate the anisotropy of velocity and mechanical properties in dry synthetic and natural shale as a function of confining pressure. Velocities in synthetic shale are sensitive to the type of clay minerals, possibly due to the different structures of the clay minerals. The velocities increase with confining pressure and show higher rate of velocity increase at low pressures, and P-wave velocity is usually more sensitive than S-wave velocity to confining pressure according to our results. Similarly, the dynamic Young's modulus and Poisson's ratio increase with applied pressure, and the results also reveal that E11 is always larger than E33 and ν31 is smaller than ν12. Velocity and mechanical anisotropy decrease with increasing stress, and are sensitive to stress and the type of clay minerals. However, the changes of mechanical anisotropy with applied stress are larger compared with the velocity anisotropy, indicating that mechanical properties are more sensitive to the change of rock properties.

  15. Depositional environment, organic matter characterization and hydrocarbon potential of Middle Miocene sediments from northeastern Bulgaria (Varna-Balchik Depression

    Directory of Open Access Journals (Sweden)

    Zdravkov Alexander

    2015-10-01

    Full Text Available The depositional environments and hydrocarbon potential of the siliciclastic, clayey and carbonate sediments from the Middle Miocene succession in the Varna-Balchik Depression, located in the south-eastern parts of the Moesian Platform, were studied using core and outcrop samples. Based on the lithology and resistivity log the succession is subdivided from base to top into five units. Siliciclastic sedimentation prevailed in the lower parts of units I and II, whereas their upper parts are dominated by carbonate rocks. Unit III is represented by laminated clays and biodetritic limestone. Units IV and V are represented by aragonitic sediments and biomicritic limestones, correlated with the Upper Miocene Topola and Karvuna Formations, respectively. Biogenic silica in the form of diatom frustules and sponge spicules correlates subunit IIa and unit III to the lower and upper parts of the Middle Miocene Euxinograd Formation. Both (subunits contain organic carbon contents in the order of 1 to 2 wt. % (median: 0.8 for subunit IIa; 1.3 for unit III, locally up to 4 wt. %. Based on Hydrogen Index values (HI and alkane distribution pattern, the kerogen is mainly type II in subunit IIa (average HI= 324 mg HC/g TOC and type III in unit III (average HI ~200 mg HC/g TOC. TOC and Rock Eval data show that subunit IIa holds a fair (to good hydrocarbon generative potential for oil, whereas the upper 5 m of unit III holds a good (to fair potential with the possibility to generate gas and minor oil. The rocks of both units are immature in the study area. Generally low sulphur contents are probably due to deposition in environments with reduced salinity. Normal marine conditions are suggested for unit III. Biomarker composition is typical for mixed marine and terrestrial organic matter and suggests deposition in dysoxic to anoxic environments.

  16. Anoxic environments and oil source bed genesis

    Energy Technology Data Exchange (ETDEWEB)

    Demaison, G J [Chevron Overseas Petroleum Inc., San Francisco, CA; Moore, G T

    1980-01-01

    The anoxic, aquatic, environment is a mass of water so depleted in oxygen that virtually all aerobic biological activity has ceased. Anoxic conditions occur where the demand for oxygen in the water column exceeds the supply. The specific cause for preferential lipid enrichment probably relates to the biochemistry of anaerobic bacterial activity. Recent evidence suggests that ancient organic-rich sediments containing hydrogen-rich kerogens (potential oil source beds) were deposited in similar anoxic environments. We propose the following classification for modern aquatic anoxic settings: (1) Large anoxic lakes - Permanent stratification promotes development of anoxic bottom water, particularly in large, deep lakes, which are not subject to seasonal overturn, e.g., Lake Tanganyika. (2) Anoxic silled basins - Landlocked silled basins with positive water balance tend to become anoxic. Typical are the Baltic and Black Seas. In arid region seas (Red and Mediterranean Seas), evaporation exceeds river inflow, causing negative water balance and well-aerated, nutrient-depleted bottom waters. (3) Anoxic layers caused by upwelling - Develop only when the oxygen supply in deep water cannot match demand by decaying organisms. Examples are the Benguela current and Peru coastal upwelling. (4) Open ocean anoxic layers - Found at intermediate depths in the northeastern Pacific and northern Indian Oceans; due to distance from deep, oxygenated polar water sources. Analogous to world-wide anoxic events at times of global climatic warm-ups and major transgressions, as in late Jurassic and middle Cretaceous time. Petroleum exploration can be greatly assisted by using geochemistry to identify paleo-anoxic events in the stratigraphic record. Recognition of the proposed anoxic models in ancient sedimentary basins should help in regional mapping of oil shales and oil-source beds. 17 figures.

  17. An analysis of natural gas exploration potential in the Qiongdongnan Basin by use of the theory of “joint control of source rocks and geothermal heat”

    Directory of Open Access Journals (Sweden)

    Zhang Gongcheng

    2014-10-01

    Full Text Available The Oligocene Yacheng Fm contains the most important source rocks that have been confirmed by exploratory wells in the Qiongdongnan Basin. The efficiency of these source rocks is the key to the breakthrough in natural gas exploration in the study area. This paper analyzes the hydrocarbon potential of each sag in this basin from the perspective of control of both source rocks and geothermal heat. Two types of source rocks occur in the Yacheng Fm, namely mudstone of transitional facies and mudstone of neritic facies. Both of them are dominated by a kerogen of type-III, followed by type-II. Their organic matter abundances are controlled by the amount of continental clastic input. The mudstone of transitional facies is commonly higher in organic matter abundance, while that of neritic facies is lower. The coal-measure source rocks of transitional facies were mainly formed in such environments as delta plains, coastal plains and barrier tidal flat-marshes. Due to the control of Cenozoic lithosphere extension and influence of neotectonism, the geothermal gradient, terrestrial heat flow value (HFV and level of thermal evolution are generally high in deep water. The hot setting not only determines the predominance of gas generation in the deep-water sags, but can promote the shallow-buried source rocks in shallow water into oil window to generate oil. In addition to promoting the hydrocarbon generation of source rocks, the high geothermal and high heat flow value can also speed up the cracking of residual hydrocarbons, thus enhancing hydrocarbon generation efficiency and capacity. According to the theory of joint control of source quality and geothermal heat on hydrocarbon generation, we comprehensively evaluate and rank the exploration potentials of major sags in the Qiongdongnan Basin. These sags are divided into 3 types, of which type-I sags including Yanan, Lingshui, Baodao, Ledong and Huaguang are the highest in hydrocarbon exploration potential.

  18. Isotope reversals in hydrocarbon gases of natural shale systems and well head production data

    Energy Technology Data Exchange (ETDEWEB)

    Berner, U.; Schloemer, S.; Stiller, E. [Bundesanstalt fuer Geowissenschaften und Rohstoffe (BGR), Hannover (Germany); Marquardt, D. [Rijksuniversiteit Utrecht (Netherlands)

    2013-08-01

    Relationships between gas geochemical signatures and the thermal maturity of source rocks containing aquatic organic matter are based on on pyrolysis experiments and have been successfully used in conventional hydrocarbon exploration since long. We demonstrate how these models can be applied to the evaluation of unconventional shale resources. For this purpose hydrocarbon gases have been extracted from low and high mature source rocks (type II kerogens) using laboratory desorption techniques. We determined the molecular composition of the gases as well as the carbon isotope ratios of methane to propane. In the extracted gases we observe an increase of {sup 13}C content in methane with increasing dry gas ratio (C1/{Sigma}C1-6). The carbon isotope ratios of ethane and propane initially increase with increasing dryness but start to become isotopically lighter above a dry gas ratio of 0.8. We show that oil-to-gas cracking explains the observed gas geochemical data, and that mixing between gases from different processes is a key factor to describe natural hydrocarbon systems of shales. However, data from published case studies using well head gases which show 'isotope roll-over' effects indicate that the isotopic reversal observed in well head samples deviate from those observed in natural shale systems in a fundamental way. We show that isotope reversals related to well head gases are best explained by an additional isotope fractionation effect induced through hydraulic fracturing and gas migration from the shale to the well head. Although, this induced isotope fractionation is an artifact which obscures isotopic information of natural systems to a large extend, we suggest a simple classification scheme which allows distinguishing between hot and cool spot areas using well head or mud line gas data. (orig.)

  19. Chemical aspects of shale and shale oils

    Energy Technology Data Exchange (ETDEWEB)

    Hackford, J E

    1922-01-01

    To prove that the kerogen in oil shale is a form of bitumen, several experiments were made with oil shale and a heavy asphaltic oil mixed with fuller's earth. When distilled, both the oil shale and asphalt-impregnated fuller's earth yielded paraffin oil, wax, and hydrogen sulfide (if sulfur was present). Both yielded ammonia if nitrogen was present. The organic material in each was partly isolated by extraction with pyridine and appeared to be the same. Oil shale is a marl that was saturated with oil or through which oil has passed or filtered. The insolubilities of its organic compounds are due to a slightly elevated temperature for a prolonged period and to the retaining effect exerted by the finely divided marl. The marl exerted a selective action on the oil and absorbed the asphaltum, sulfur, and nitrogen compounds from the oil. The class of oil evolved from a shale depended on the nature of the original compounds absorbed. Asphaltenes obtained from crude oil by precipitation with ethyl ether produced distillation products of water, hydrogen sulfide, ammonia, oil, wax, and a carbonaceous residue. Water was formed by decomposition of oxyasphaltenes and hydrogen sulfide by decomposition of thioasphaltenes. Ammonia was evolved during decomposition if lime was present, but if there was not sufficient free lime present, pyridine and pyrrole derivatives were redistilled as such. The oil and wax that resulted from the dry distillation were true decomposition products and equaled about 60 weight-percent of the asphaltenes. The oil and wax content of the mixture varied between 8 and 10 percent. The carbonaceous residue, which represented approximately 40 percent of the original asphaltene, was a decomposition product of the asphaltenes. Geologic comparisons of oil-shale deposits and oil-well fields were also made.

  20. Allochthonous Addition of Meteoritic Organics to the Lunar Regolith

    Science.gov (United States)

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

    2013-01-01

    Preparation of lunar samples 74220,861 was discussed in detail in [3, 4]. Our analysis sequence was as follows: optical microscopy, UV fluorescence imaging, -Raman, FESEM-EDX imaging and mapping, FETEMEDX imaging and mapping of a Focused Ion Beam (FIB) extracted section, and NanoSIMs analysis. We observed fluffytextured C-rich regions of interest (ROI) on three different volcanic glass beads. Each ROI was several m2 in size and fluoresced when exposed to UV. Using FESEM/EDX, the largest ROI measured 36 m and was located on an edge of a plateau located on the uppermost surface of the bead. The ROI was covered on one edge by a siliceous filament emanating from the plateau surface indicating it was attached to the bead while on the Moon. EDX mapping of the ROI shows it is composed primarily of heterogeneously distributed C. Embedded with the carbonaceous phase are localized concentrations of Si, Fe, Al and Ti indicating the presence of glass and/or minerals grains. -Raman showed strong D- and G-bands and their associated second order bands; intensity and location of these bands indicates the carbonaceous matter is structurally disorganized. A TEM thin section was extracted from the surface of a glass bead using FIB microscopy. High resolution TEM imaging and selected area electron diffraction demonstrate the carbonaceous layer to be amorphous; it lacked any long or short range order characteristic of micro- or nanocrystalline graphite. Additionally TEM imaging also revealed the presence of submicron mineral grains, typically < 50 nm in size, dispersed within the carbonaceous layer. NanoSIMs data will be presented and discussed at the meeting. Given the noted similarities between the carbonaceous matter present on 74220 glass beads and meteoritic kerogen, we suggest the allochthonous addition of meteoritic organics as the most probable source for the C-rich ROIs.

  1. Four dimensional X-ray imaging of deformation modes in organic-rich Green River Shale retorted under uniaxial compression

    Science.gov (United States)

    Kobchenko, M.; Pluymakers, A.; Cordonnier, B.; Tairova, A.; Renard, F.

    2017-12-01

    Time-lapse imaging of fracture network development in organic-rich shales at elevated temperatures while kerogen is retorted allows characterizing the development of microfractures and the onset of primary migration. When the solid organic matter is transformed to hydrocarbons with lower molecular weight, the local pore-pressure increases and drives the propagation of hydro-fractures sub-parallel to the shale lamination. On the scale of samples of several mm size, these fractures can be described as mode I opening, where fracture walls dilate in the direction of minimal compression. However, so far experiments coupled to microtomography in situ imaging have been performed on samples where no load was imposed. Here, an external load was applied perpendicular to the sample laminations and we show that this stress state slows down, but does not stop, the propagation of fracture along bedding. Conversely, microfractures also propagate sub-perpendicular to the shale lamination, creating a percolating network in three dimensions. To monitor this process we have used a uniaxial compaction rig combined with in-situ heating from 50 to 500 deg C, while capturing three-dimensional X-ray microtomography scans at a voxel resolution of 2.2 μm; Data were acquired at beamline ID19 at the European Synchrotron Radiation Facility. In total ten time-resolved experiments were performed at different vertical loading conditions, with and without lateral passive confinement and different heating rates. At high external load the sample fails by symmetric bulging, while at lower external load the reaction-induced fracture network develops with the presence of microfractures both sub-parallel and sub-perpendicular to the bedding direction. In addition, the variation of experimental conditions allows the decoupling of the effects of the hydrocarbon decomposition reaction on the deformation process from the influence of thermal stress heating on the weakening and failure mode of immature

  2. Spatially-resolved isotopic study of carbon trapped in ∼3.43 Ga Strelley Pool Formation stromatolites

    Science.gov (United States)

    Flannery, David T.; Allwood, Abigail C.; Summons, Roger E.; Williford, Kenneth H.; Abbey, William; Matys, Emily D.; Ferralis, Nicola

    2018-02-01

    The large isotopic fractionation of carbon associated with enzymatic carbon assimilation allows evidence for life's antiquity, and potentially the early operation of several extant metabolic pathways, to be derived from the stable carbon isotope record of sedimentary rocks. Earth's organic carbon isotope record extends to the Late Eoarchean-Early Paleoarchean: the age of the oldest known sedimentary rocks. However, complementary inorganic carbon reservoirs are poorly represented in the oldest units, and commonly reported bulk organic carbon isotope measurements do not capture the micro-scale isotopic heterogeneities that are increasingly reported from younger rocks. Here, we investigated the isotopic composition of the oldest paired occurrences of sedimentary carbonate and organic matter, which are preserved as dolomite and kerogen within textural biosignatures of the ∼3.43 Ga Strelley Pool Formation. We targeted least-altered carbonate phases in situ using microsampling techniques guided by non-destructive elemental mapping. Organic carbon isotope values were measured by spatially-resolved bulk analyses, and in situ using secondary ion mass spectrometry to target microscale domains of organic material trapped within inorganic carbon matrixes. Total observed fractionation of 13C ranges from -29 to -45‰. Our data are consistent with studies of younger Archean rocks that host biogenic stromatolites and organic-inorganic carbon pairs showing greater fractionation than expected for Rubisco fixation alone. We conclude that organic matter was fixed and/or remobilized by at least one metabolism in addition to the CBB cycle, possibly by the Wood-Ljungdahl pathway or methanogenesis-methanotrophy, in a shallow-water marine environment during the Paleoarchean.

  3. Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4-CO2-H2O) Interactions in Shale Nanopores under Reservoir Conditions: Quarterly Report.

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yifeng [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2017-11-01

    Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO2 and H2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO2 has been suggested as an alternative fluid for subsurface fracturing such that CO2 enhanced gas recovery can also serve as a CO2 sequestration process. Limited data indicate that CO2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH4 in shale matrix. Therefore, fundamental understanding of CH4-CO2-H2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO2 sequestration. This project focuses on the systematic study of CH4-CO2-H2O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.

  4. Organic Geochemistry and Rock-Eval Pyrolysis of Eocene fine Sediments, East Ketungau Basin, West Kalimantan

    Directory of Open Access Journals (Sweden)

    M.H. Hermiyanto Zajuli

    2014-06-01

    Full Text Available DOI: 10.17014/ijog.v6i2.119Indonesia contains many Paleogene and Neogene basins which some of them have been proven to be a very prolific producer of oil and gas. A study on the result of Rock-Eval pyrolysis and biomarker undertaken on the Eocene Mandai Group was able to assess hydrocarbon potential of the Paleogene fine sediments in the frontier basin, especially West Kalimantan area. East Ketungau Basin is located in the western Kalimantan, bounded with Melawi Basin by the Semitau High in the south and West Ketungau Basin in the west. The Mandai Group was deposited in the East Ketungau Basin during Eocene, consisting of sandstone and mudstone facies. Mudstone facies comprises shale, claystone, and coal. Seven samples of Eocene fine sediments collected from East Ketungau Basin were analyzed by Rock-Eval pyrolisis and three samples for biomarker to evaluate their hydrocarbon potential. The Rock-Eval pyrolisis result of Mandai Group shows that TOC value of this facies ranges from 0.34 % to 5.16 %, Potential Yield (PY between 0.06 and 4.78 mg HC/g rock, and Hydrogen Index (HI from 12 to 89. Based on that result, the fine sediments of Mandai Group are included into a gas prone source rock potential with poor to fair categories. Moreover Tmax values vary from 426o C to 451o C. The Eocene fine sediments of Mandai Group fall under kerogen type III. Based on Tmax and biomarker analyses, the maturity of the sediments is situated within immature to mature level. The fine sediments of Mandai Group were deposited in a terrestrial to marine environment under anoxic to sub-oxic condition.

  5. 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.

  6. 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.

  7. 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.

  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

    2005-01-01

    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.

  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

    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.

  10. Natural gas geochemistry and its origins in Kuqa depression

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    According to gas compositional and carbon isotopic measurement of 114 gas samples from the Kuqa depression,accumulation of the natural gases in the depression is dominated by hydrocarbon gases, with high gas dryness(C1/C1-4)at the middle and northern parts of the depression and low one towards east and west sides and southern part.The carbon isotopes of methane and its homologues are relatively enriched in 13 C,and the distributive range ofδ13C 1 ,δ13C 2 andδ13C 3 is-32‰―-36‰,-22‰―-24‰and-20‰―-22‰,respectively.In general,the carbon isotopes of gaseous alkanes become less negative with the increase of carbon numbers.Theδ13C CO2 value is less than-10‰in the Kuqa depression,indicating its organogenic origin.The distributive range of 3 He/ 4 He ratio is within n×10-8 and a decrease in 3 He/ 4 He ratio from north to south in the depression is observed.Based on the geochemical parameters of natural gas above,natural gas in the Kuqa depression is of characteristics of coal-type gas origin.The possible reasons for the partial reversal of stable carbon isotopes of gaseous alkanes involve the mixing of gases from one common source rock with different thermal maturity or from two separated source rock intervals of similar kerogen type,multistages accumulation of natural gas under high-temperature and over-pressure conditions,and sufficiency and diffusion of natural gas.

  11. AN APPROACH TO PROVENANCE, TECTONIC AND REDOX CONDITIONS OF JURASSIC-CRETACEOUS AKKUYU FORMATION, CENTRAL TAURIDS, TURKEY

    Directory of Open Access Journals (Sweden)

    Ali SARI

    2012-06-01

    Full Text Available - Late Jurassic-Early Cretaceous Akkuyu formation was deposited in a marine carbonate platform in Central Tarurids. The organic material of the unit is composed of Type III kerogen which is woody material transported from the land. Late Jurassic- Early Cretaceous is an important period which great anoxic events in deep sea bottom occurred due to the primary organic productivity in global sea surface. Use of several trace elements values (Ni, V, U, Cr, Co, Th revealed that Late Jurassic-Early Cretaceous Akkuyu formation shows oxic, disoxic and anoxic paleoredox conditions. In this period the primary productivity was considerably high. Examination of specimen derived from Akkuyu formation revealed that there exists a very good positive relationship between the major oxides of Al2O3, SiO2, Fe2O3, TiO2, and K2O. These combinations of major oxides indicate a detrital origin of source rock. Chemical weathering evaluations of Central Taurids in the Jurassic-Cretaceous period indicated moderate and strong weathering of source rock. K2O/Na2O versus SiO2; SiO2/Al2O3 versus K2O/Na2O; Al2O3/ SiO2 versus Fe2O3 + MgO ve TiO2 versus Fe2O3 + MgO diagrams indicated that Akkuyu formation was deposited along active and/or passive continental margin and derived from basalt and basalt+granite mixed rocks.

  12. Features of the first great shale gas field in China

    Directory of Open Access Journals (Sweden)

    Ruobing Liu

    2016-04-01

    Full Text Available On the 28th of November 2012, high shale gas flow was confirmed to be 203 × 103 m3 in Longmaxi Formation; this led to the discovery of the Fuling Shale Gas Field. On the 10th of July in 2014, the verified geological reserves of the first shale gas field in China were submitted to the National Reserves Committee. Practices of exploration and development proved that the reservoirs in the Fuling Shale Gas Field had quality shales deposited in the deep-shelf; the deep-shelf had stable distribution, great thickness with no interlayers. The shale gas field was characterized by high well production, high-pressure reservoirs, good gas elements, and satisfactory effects on testing production; it's from the mid-deep depth of the quality natural gas reservoirs that bore high pressure. Comprehensive studies on the regional sedimentary background, lithology, micropore structures, geophysical properties, gas sources, features of gas reservoirs, logging responding features, and producing features of gas wells showed the following: (1 The Longmaxi Formation in the Fuling Shale Gas Field belongs to deep-shelf environment where wells developed due to organic-rich shales. (2 Thermal evolution of shales in Longmaxi Formation was moderate, nanometer-level pores developed as well. (3 The shale gas sources came from kerogens the Longmaxi Formation itself. (4 The shale gas reservoirs of the Fuling Longmaxi Formation were similar to the typical geological features and producing rules in North America. The findings proved that the shale gas produced in the Longmaxi Formation in Fuling was the conventional in-situ detained, self-generated, and self-stored shale gas.

  13. ) Geochemistry and Hydrocarbon Potential of Cretaceous Shales in the Chad Basin

    International Nuclear Information System (INIS)

    Alalade, B.; Ogunyemi, A. T.; Abimbola, A.F.; Olugbemiro, R. O.

    2003-01-01

    The Chad Basin is the largest intracratonic basin in Africa and is filled with more than 400m of Cretaceous to Recent sediments. Geochemical and petrographic studies of Cretaceous shales form the Bima, Gongola and Fika Formations were carried out to establish their hydrocarbon potential and thermal maturity. Ditch cuttings of the shales were collected from the Wa di and Karen's exploration wells located in the Nigerian sector of the Chad Basin.The geochemical analysis of the shales indicate that, except for Si02 and K20, all other oxides (Mg O, Fe2O3, AL2O3, CaO) are more abundant in the Fika shale than the Gongola shale. This suggests a more marine condition for the Fika shale compared to the Gongola shale. The Fika and Gongola shales were further classified into Iron shale and shale respectively. Organic carbon contents of the Bima, Gongola and exceed the minimum (0.5wt%) usually required for siliciclastic petroleum source rock. However, the soluble organic matter (SOM) and saturated hydrocarbon (SHC) contents of the shales, which ranges from 108pm to 743ppm and 23ppm to 100ppm respectively, are generally low and are therefore, organically lean. The organic matter of the shales is predominantly terrestrially derived, vitrinite rich, Type III kerogen and are therefore, gas prone. Thermal maturity assessed from SOM/TOC, SHC/TOC ratios and spore color index (SCI) indicate that the Fika shale is immature while the Gongola and Bima shales are within the oil window

  14. Hydrocarbons on Saturn's satellites Iapetus and Phoebe

    Science.gov (United States)

    Cruikshank, D.P.; Wegryn, E.; Dalle, Ore C.M.; Brown, R.H.; Bibring, J.-P.; Buratti, B.J.; Clark, R.N.; McCord, T.B.; Nicholson, P.D.; Pendleton, Y.J.; Owen, T.C.; Filacchione, G.; Coradini, A.; Cerroni, P.; Capaccioni, F.; Jaumann, R.; Nelson, R.M.; Baines, K.H.; Sotin, Christophe; Bellucci, G.; Combes, M.; Langevin, Y.; Sicardy, B.; Matson, D.L.; Formisano, V.; Drossart, P.; Mennella, V.

    2008-01-01

    Material of low geometric albedo (pV ??? 0.1) is found on many objects in the outer Solar System, but its distribution in the saturnian satellite system is of special interest because of its juxtaposition with high-albedo ice. In the absence of clear, diagnostic spectral features, the composition of this low-albedo (or "dark") material is generally inferred to be carbon-rich, but the form(s) of the carbon is unknown. Near-infrared spectra of the low-albedo hemisphere of Saturn's satellite Iapetus were obtained with the Visible-Infrared Mapping Spectrometer (VIMS) on the Cassini spacecraft at the fly-by of that satellite of 31 December 2004, yielding a maximum spatial resolution on the satellite's surface of ???65 km. The spectral region 3-3.6 ??m reveals a broad absorption band, centered at 3.29 ??m, and concentrated in a region comprising about 15% of the low-albedo surface area. This is identified as the C{single bond}H stretching mode vibration in polycyclic aromatic hydrocarbon (PAH) molecules. Two weaker bands attributed to {single bond}CH2{single bond} stretching modes in aliphatic hydrocarbons are found in association with the aromatic band. The bands most likely arise from aromatic and aliphatic units in complex macromolecular carbonaceous material with a kerogen- or coal-like structure, similar to that in carbonaceous meteorites. VIMS spectra of Phoebe, encountered by Cassini on 11 June 2004, also show the aromatic hydrocarbon band, although somewhat weaker than on Iapetus. The origin of the PAH molecular material on these two satellites is unknown, but PAHs are found in carbonaceous meteorites, cometary dust particles, circumstellar dust, and interstellar dust. ?? 2007 Elsevier Inc. All rights reserved.

  15. Temperature effects on chemical structure and motion in coal. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Maciel, G.E.

    1996-09-30

    The objective of this project was to apply recently developed, state-of-the-art nuclear magnetic resonance (NMR) techniques to examine in situ changes in the chemical structure and molecular/macromolecular motion in coal as the temperature is increased above room temperature. Although alterations in the chemical structure of coal have been studied previously by {sup 13}C NMR, using quenched samples, the goal of this project was to examine these chemical structural changes, and changes in molecular/macromolecular mobility that may precede or accompany the chemical changes, at elevated temperatures, using modern {sup 13}C and {sup 1}H NMR techniques, especially {sup 1}H dipolar-dephasing techniques and related experiments pioneered in the laboratory for examining pyridine-saturated coals. This project consisted of the following four primary segments and related efforts on matters relevant to the first four tasks. (1) {sup 1}H NMR characterization of coal structure and mobility as a function of temperature variation over a temperature range (30--240 C) for which substantial chemical transformations were not anticipated. (2) {sup 1}H NMR characterization of coal structure, mobility and conversion as a function of temperature variation over a temperature range (240--500 C) for which chemical transformations of coal are known to occur. (3) {sup 13}C NMR investigation of coal structure/mobility as a function of temperature over a temperature range (30--240 C) for which substantial chemical transformations were not anticipated. (4) {sup 13}C NMR investigation of coal structure, dynamics and conversion as a function of temperature variation over a range (240--500 C) for which chemical transformations of coal are known to occur. (5) Related matters relevant to the first four tasks: (a) {sup 1}H CRAMPS NMR characterization of oil shales and their kerogen concentrates; and (b) improved quantitation in {sup 13}C MAS characterization of coals.

  16. Carbonaceous Chondrite Meteorites: the Chronicle of a Potential Evolutionary Path between Stars and Life.

    Science.gov (United States)

    Pizzarello, Sandra; Shock, Everett

    2017-09-01

    The biogenic elements, H, C, N, O, P and S, have a long cosmic history, whose evolution can still be observed in diverse locales of the known universe, from interstellar clouds of gas and dust, to pre-stellar cores, nebulas, protoplanetary discs, planets and planetesimals. The best analytical window into this cosmochemical evolution as it neared Earth has been provided so far by the small bodies of the Solar System, some of which were not significantly altered by the high gravitational pressures and temperatures that accompanied the formation of larger planets and may carry a pristine record of early nebular chemistry. Asteroids have delivered such records, as their fragments reach the Earth frequently and become available for laboratory analyses. The Carbonaceous Chondrite meteorites (CC) are a group of such fragments with the further distinction of containing abundant organic materials with structures as diverse as kerogen-like macromolecules and simpler compounds with identical counterparts in Earth's biosphere. All have revealed a lineage to cosmochemical synthetic regimes. Several CC show that asteroids underwent aqueous alteration of their minerals or rock metamorphism but may yet yield clues to the reactivity of organic compounds during parent-body processes, on asteroids as well as larger ocean worlds and planets. Whether the exogenous delivery by meteorites held an advantage in Earth's molecular evolution remains an open question as many others regarding the origins of life are. Nonetheless, the natural samples of meteorites allow exploring the physical and chemical processes that might have led to a selected chemical pool amenable to the onset of life. Graphical Abstract ᅟ.

  17. 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.

  18. A mathematical model of fluid and gas flow in nanoporous media.

    Science.gov (United States)

    Monteiro, Paulo J M; Rycroft, Chris H; Barenblatt, Grigory Isaakovich

    2012-12-11

    The mathematical modeling of the flow in nanoporous rocks (e.g., shales) becomes an important new branch of subterranean fluid mechanics. The classic approach that was successfully used in the construction of the technology to develop oil and gas deposits in the United States, Canada, and the Union of Soviet Socialist Republics becomes insufficient for deposits in shales. In the present article a mathematical model of the flow in nanoporous rocks is proposed. The model assumes the rock consists of two components: (i) a matrix, which is more or less an ordinary porous or fissurized-porous medium, and (ii) specific organic inclusions composed of kerogen. These inclusions may have substantial porosity but, due to the nanoscale of pores, tubes, and channels, have extremely low permeability on the order of a nanodarcy (~109-²¹ m² ) or less. These inclusions contain the majority of fluid: oil and gas. Our model is based on the hypothesis that the permeability of the inclusions substantially depends on the pressure gradient. At the beginning of the development of the deposit, boundary layers are formed at the boundaries of the low-permeable inclusions, where the permeability is strongly increased and intensive flow from inclusions to the matrix occurs. The resulting formulae for the production rate of the deposit are presented in explicit form. The formulae demonstrate that the production rate of deposits decays with time following a power law whose exponent lies between -1/2 and -1. Processing of experimental data obtained from various oil and gas deposits in shales demonstrated an instructive agreement with the prediction of the model.

  19. Hydrocarbon potential of a new Jurassic play, central Tunisia

    International Nuclear Information System (INIS)

    Beall, A.O.; Law, C.W.

    1996-01-01

    A largely unrecognized Jurassic Sag Basin has been identified in central Tunisia, proximal to the Permo-Carboniferous flexure delineating the northern boundary of the Saharan platform of north Africa. The northwestern margin of the Sag is delineated by an extensive region of salt-cored anticlines and localized salt diapirs extending north and west. Due to lack of deep drilling, delineation of the Sag is largely based on regional gravity data. Subsidence of the Jurassic Sag Basin is characterized by rapid expansion of Jurassic sediments from 400 m. of tidal flat and shelf carbonate at the western outcrop to over 2000 meters of tidal flat and basinal carbonate and shale within the basin center, a five-fold expansion. Rapid loading of the basin continued into Lower Cretaceous time, marked by lateral flowage of Triassic salt into pronounced structural trends. Published source rock data and interpreted subsurface well data provided the basis for GENEX 1-D hydrocarbon generation and expulsion modeling of the Sag. Middle Jurassic black source shales typically contain Type II and Type III kerogens with T.O.C.'s ranging up to 4 percent. Modeling results indicate that middle Jurassic shales are presently mature for liquid generation within portions of the Sag, with maximum generation taking place during the Tertiary. Potential hydrocarbon generation yields, based on 60 meters of mature source shale, are 20,000 BOE/acre for gas and 75,000 BOE/acre for liquids. Prospects within the region could contain an estimated potential reserve of several T.C.F. or over 1 billion barrels of oil

  20. The role of fossil organic matter in the ecosystem development of post-mining sites revealed by isotope analyses

    Science.gov (United States)

    Jandova, Katerina; Hyodo, Fujio; Vindušková, Olga; Moradi, Jabbar; Frouz, Jan

    2017-04-01

    Sediments rich in kerogen ( 19 Ma old, 14C-free) are present in the overburden at post-mining area in Western Bohemia, near Sokolov city, the Czech Republic. There are two successional chronosequences, an alder reclamation and spontaneous succession, consisting of sites that differ in time since heaping. Both chronosequences accumulate recent organic matter over time, although the process is initially faster at reclamation. We hypothesized that (i) radiocarbon age of soil organic matter would be decreasing with time since spoil heaping; (ii) the detrital food web would show the assimilation of fossil carbon by heterotrophic organisms in the initial stages of succession when fossil organic matter is the predominant source of carbon; (iii) the isotopic track of fossil organic matter in the detrital food web would be more prominent at sites with lower vegetation cover and litter production. Nitrogen isotopic ratios of soils were high at the young sites and the decrease in δ15N was correlated with the increase in content of recent organic carbon. Nitrogen isotopic ratios of soil detritivores equalled to that of tree leaves at reclamation but were higher at successional sites. Possibly, other food sources were used apart from tree leaves litter at the latter. Interestingly, soil animals but not primary producers were 14C depleted in the youngest relative to the oldest sites. The depletion in 14C of detritivores relative to primary producers was likely due to the geophagy behaviour of the millipedes at the young sites where fossil organic matter is the largest carbon pool.

  1. The hydrocarbon potential of the West Bengal basin of Eastern India and Western Bangladesh

    International Nuclear Information System (INIS)

    Moore, L.V.; Lenengerger, T.L.

    1994-01-01

    Within the Bengal Basin is an extensively developed Eocene shelf system with fair to good potential for stratigraphic oil accumulations. The best quality data available to evaluate this play are from the Bogra Shelf area of Bangladesh. Within this general area Stanvac participated in the drilling of 13 wells in the late 1950's, including critical wells on the Bogra Shelf. This well data, combined with modern excellent quality seismic data, has allowed definition of a geological and geophysical constrained hydrocarbon system model. Potential source, reservoir and seal units can be identified or postulated from both well and seismic data within the Eocene depositional systems tracts. The most promising potential source rock unit identified on the Bogra Shelf to date are Upper Jalangi (Early Ecocene) shales containing oil-prone kerogens that average 4.7% TOC. Four wells, structurally up-dip of the defined play area, have good oil shows in thermally immature Jalangi sands indicating possible up dip migration. Reservoir strata have not been penetrated on the Bogra Shelf. Based basin modelling and seismic data, however, a foraminiferal grain stone facies within the Middle Eocene Sylthet Limestone carbonate buildups could provide a suitable reservoir. The tight micritic facies within the Sylhet Limestone and the overlying late Eocene Kopilli Shale form the updip, lateral and top seals for these stratigraphic traps. Exploration risks associated with this play include the following: (1) Limited drainage areas for the identified leads; (2) Carbonate build-ups may be perched on impermeable strata, precluding vertical charging; (3) presence, and up-dip limit of reservoir is speculative. (author)

  2. Isotopic Signature of the Ancient Biosphere

    Science.gov (United States)

    DesMarais, D. J.; Chang, Sherwood (Technical Monitor)

    1997-01-01

    The age distribution of 261 field localities, sampled for their well-preserved Archean and Proterozoic sedimentary rocks, revealed a 500-700 Ma episodicity. Assuming that the numbers of sites are a proxy for mass of sediments, the record of well-preserved sediments is more abundant in the intervals 3.5-3.3, 2.8-2.5, 2.1-1.8, 1.5-1.3, and 1.0-0.54 Ga than in the intervening intervals. It is proposed that the crustal inventory of photosynthetic organic carbon was modulated by the volume of sedimentation in sites favorable for the burial and long-term preservation of organic carbon. Tectonic processes controlled this sediment volume. Episodic increases in the organic inventory led to stepwise increases in oxidized reservoirs (e.g., O2, SO4(2-), Fe(3+). The interval 2.9-2.5 Ga recorded a large rise in seawater Sr-87/Sr-86, the oldest-known extensive banded iron formations, and the first evidence (C-13-depleted kerogens) of O2 use by methylotrophic bacteria. The interval 2.2-1.8 Ga has both carbon isotopic evidence for a stepwise increase in the organic reservoir and also paleosol evidence for an O2 increase. The interval 1.1-0.6 Ga shows isotopic evidence for another organic carbon increase. The interval 1.5-1.3 Ga revealed no such increases as yet, perhaps because incomplete rifting of the mid-Proterozoic supercontinent was associated with extensive sedimentation in oxidized continental basins, producing redbeds, coarse clastics, etc. Such sedimentation did not promote the burial of reduced carbon.

  3. THE FIRST DISCOVERY OF PRESOLAR GRAPHITE GRAINS FROM THE HIGHLY REDUCING QINGZHEN (EH3) METEORITE

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yuchen; Lin, Yangting; Zhang, Jianchao; Hao, Jialong, E-mail: linyt@mail.iggcas.ac.cn [Key Laboratory of Earth and Planetary Physics, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029 (China)

    2016-07-10

    Presolar graphite grains have been extensively studied, but are limited in carbonaceous chondrites, particularly in Murchison (CM2) and Orgueil (CI1), which sampled materials from the oxidizing regions in the solar nebula. Here, we report the first discovery of presolar graphite grains from the Qingzhen (EH3) enstatite chondrite which formed under a highly reducing condition. Eighteen presolar graphite grains were identified by C-isotope mapping of the low-density fraction (1.75–1.85 g cm{sup 3}) from Qingzhen acid residue. Another 58 graphite spherules were found in different areas of the same sample mount using a scanning electron microscope and were classified into three morphologies, including cauliflower, onion, and cauliflower–onion. The Raman spectra of these spherules vary from ordered, disordered, and glassy to kerogen-like, suggestive of a wide range of thermal metamorphisms. NanoSIMS analysis of the C- and Si-isotopes of these graphite spherules confirmed 23 presolar grains. The other 35 graphite spherules have no significant isotopic anomalies, but they share similar morphologies and Raman spectra with the presolar ones. Another three grains were identified during NanoSIMS analysis. Of all the 44 presolar graphite grains identified, six grains show {sup 28}Si-excesses, suggestive of supernovae origins, and four grains are {sup 12}C- and {sup 29,30}Si-rich, consistent with low-metallicity asymptotic giant branch star origins. Another two graphite spherules have extremely low {sup 12}C/{sup 13}C ratios with marginal solar Si-isotopes. The morphologies, Raman spectra, and C- and Si-isotopic distributions of the presolar graphite grains from the Qingzhen enstatite chondrite are similar to those of the low-density fractions from Murchison carbonaceous chondrites. This study suggests a homogeneous distribution of presolar graphite grains in the solar nebula.

  4. THE FIRST DISCOVERY OF PRESOLAR GRAPHITE GRAINS FROM THE HIGHLY REDUCING QINGZHEN (EH3) METEORITE

    International Nuclear Information System (INIS)

    Xu, Yuchen; Lin, Yangting; Zhang, Jianchao; Hao, Jialong

    2016-01-01

    Presolar graphite grains have been extensively studied, but are limited in carbonaceous chondrites, particularly in Murchison (CM2) and Orgueil (CI1), which sampled materials from the oxidizing regions in the solar nebula. Here, we report the first discovery of presolar graphite grains from the Qingzhen (EH3) enstatite chondrite which formed under a highly reducing condition. Eighteen presolar graphite grains were identified by C-isotope mapping of the low-density fraction (1.75–1.85 g cm 3 ) from Qingzhen acid residue. Another 58 graphite spherules were found in different areas of the same sample mount using a scanning electron microscope and were classified into three morphologies, including cauliflower, onion, and cauliflower–onion. The Raman spectra of these spherules vary from ordered, disordered, and glassy to kerogen-like, suggestive of a wide range of thermal metamorphisms. NanoSIMS analysis of the C- and Si-isotopes of these graphite spherules confirmed 23 presolar grains. The other 35 graphite spherules have no significant isotopic anomalies, but they share similar morphologies and Raman spectra with the presolar ones. Another three grains were identified during NanoSIMS analysis. Of all the 44 presolar graphite grains identified, six grains show 28 Si-excesses, suggestive of supernovae origins, and four grains are 12 C- and 29,30 Si-rich, consistent with low-metallicity asymptotic giant branch star origins. Another two graphite spherules have extremely low 12 C/ 13 C ratios with marginal solar Si-isotopes. The morphologies, Raman spectra, and C- and Si-isotopic distributions of the presolar graphite grains from the Qingzhen enstatite chondrite are similar to those of the low-density fractions from Murchison carbonaceous chondrites. This study suggests a homogeneous distribution of presolar graphite grains in the solar nebula.

  5. Carbon, nitrogen, and sulfur geochemistry of Archean and Proterozoic shales from the Kaapvaal Craton, South Africa

    Science.gov (United States)

    Watanabe, Yumiko; Naraoka, Hiroshi; Wronkiewicz, David J.; Condie, Kent C.; Ohmoto, Hiroshi

    1997-08-01

    The C, N, and S contents and VC and δ 13Cδ 34S values were analyzed for 100 shale samples from ten formations, 3.0 to 2.1 Ga in age, in the central and eastern regions of the Kaapvaal Craton, South Africa. The Kaapvaal shales are characterized by generally low contents of organic C (range 0.06-2.79 wt%, average 0.47 wt%), N (range facies). From the theoretical relationships between the H/C ratios of kerogen and organic C contents of shales, the original C contents of the Archean and Proterozoic shales from the Kaapvaal Craton are estimated to be on average ˜2 wt%. These values are similar to the average organic C content of modern marine sediments. This suggests that the primary organic productivity and the preservation of organic matter in the ocean during the period of 3.0 to 2.1 Ga were similar to those in the Phanerozoic era, provided the flux of clastic sediments to the ocean was similar. This would also imply that the rate of O 2 accumulation in the atmosphere-ocean system, which has equaled the burial rate of organic matter in sediments, has been the same since ˜3.0 Ga. The δ 34S values of bulk-rock sulfides (mostly pyrite) range from +2.7 to +7.4%‰ for seven sulfide-rich samples of ˜2.9 Ga to ˜2.6 Ga. These values are consistent with a suggestion by Ohmoto (1992) and Ohmoto et al. (1993) that most pyrite crystals in Archean shales were formed by bacterial reduction of seawater sulfate with δ 34S values between +2 and +10‰, and that the Archean seawater was sulfate rich. Changes in the δ 13C org values during maturation of kerogen were evaluated with theoretical calculations from the experimental data of Peters et al. (1981) and Lewan (1983), and from the observations by Simoneit et al. (1981) on natural samples. These evaluations suggest that the magnitudes of δ 13C org increase are much less than those estimated by Hayes et al. (1983) and Des Marais et al. (1992), and only about 2 to 3%‰ for the kerogens that decreased their H/C ratios from

  6. Characterization and quantification by mass spectrometry of mobile organic matter from clay rock: influence of the origin and of the sampling

    International Nuclear Information System (INIS)

    Huclier-Markai, S.; Landesman, C.; Montavon, G.; Grambow, B.; Monteau, F.; Fernandez, A.M.; Vinsot, A.

    2012-01-01

    probable low velocity, that the inventory was focused on the small organic molecules. The influence of the sampling was studied, notably by performing an experiment in which the argillite core sample was squeezed for 28 days at 175 MPa. The initial water content of the sample was 5.3% and the concentration of organic matter XX mol C/L. The structural features observed for the DOM were different from the percolated water samples either obtained in situ from the POX 1601 borehole or in lab from EST 34399 cores than for the squeezed water sample. The influence of the water collection will be discussed. Additionally, a part of organic matter can be extracted and isolated by HCl/HF treatment. This corresponds to the kerogen fraction which is insoluble in the pore water. 150 Myears solid-bound organic matter of the COx has been already investigated in several studies and originates from a mixture of marine and terrestrial sources. In addition to this, the CCl4 soluble organic fraction (bitumen) has been already characterized by liquid and gas chromatography coupled to mass spectrometry. And finally, a small fraction of the kerogen can be mobilized under alkaline conditions from the COx, a scenario which could happen at the COx/cement interface. This fraction (approx. 0,002 mol C/L) could be transported in the pore water and has been characterized to contain small molecules with carboxylic and phenolic groups. Nonetheless, in order to predict the speciation of metals and radionuclides for a given scenario, Dissolved Organic Matter (DOM) either in the pore water or that could be mobilized from the kerogen fraction must be supported by quantitative data. Thus, the present study is focused the quantification of these low molecular weight compounds using mass spectrometry. Several simple, sensitive, and reproducible methods of quantification, such as internal calibration, calibrated addition of external standard or sequential tandem mass spectrometry, have been developed and are

  7. 2D seismic interpretation and characterization of the Hauterivian-Early Barremian source rock in Al Baraka oil field, Komombo Basin, Upper Egypt

    Science.gov (United States)

    Ali, Moamen; Darwish, M.; Essa, Mahmoud A.; Abdelhady, A.

    2018-03-01

    Komombo Basin is located in Upper Egypt about 570 km southeast of Cairo; it is an asymmetrical half graben and the first oil producing basin in Upper Egypt. The Six Hills Formation is of Early Cretaceous age and subdivided into seven members from base to top (A-G); meanwhile the B member is of Hauterivian-Early Barremian and it is the only source rock of Komombo Basin. Therefore, a detailed study of the SR should be carried out, which includes the determination of the main structural elements, thickness, facies distribution and characterization of the B member SR which has not been conducted previously in the study area. Twenty 2D seismic lines were interpreted with three vertical seismic profiles (VSP) to construct the depth structure-tectonic map on the top of the B member and to highlight the major structural elements. The interpretation of depth structure contour map shows two main fault trends directed towards the NW-SE and NE to ENE directions. The NW-SE trend is the dominant one, creating a major half-graben system. Also the depth values range from -8400 ft at the depocenter in the eastern part to -4800 ft at the shoulder of the basin in the northwestern part of the study area. Meanwhile the Isopach contour map of the B member shows a variable thickness ranging between 300 ft to 750 ft. The facies model shows that the B member SR is composed mainly of shale with some sandstone streaks. The B member rock samples were collected from Al Baraka-1 and Al Baraka SE-1 in the eastern part of Komombo Basin. The results indicate that the organic matter content (TOC) has mainly good to very good (1-3.36 wt %), The B member samples have HI values in the range 157-365 (mg HC/g TOC) and dominated by Type II/III kerogen, and is thus considered to be oil-gas prone based on Rock-Eval pyrolysis, Tmax values between 442° and 456° C therefore interpreted to be mature for hydrocarbon generation. Based on the measured vitrinite equivalent reflectance values, the B member SR

  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

    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

  9. 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

  10. Influence of sulfate reduction on the organic matter of Wealden sediments of the Lower Saxony Basin (Germany)

    Energy Technology Data Exchange (ETDEWEB)

    Berner, U. [Bundesanstalt fuer Geowissenschaften und Rohstoffe (BGR), Hannover (Germany)

    2013-08-01

    Sediments of the Wealden (Lower Saxony Basin, Germany) as obtained from the well Isterberg 1001 consist of clay stones, marls and few massive carbonate horizons. Although, the basin is predominantly characterized as lacustrine geochemical data indicate significant influences of marine ingression which have introduced sulfur into the depositional system. Consequently the organic matter of the sediments has been substantially affected by bacterial sulfate reduction, which has led to losses of the initial organic carbon of 5 to 80 wt.- percent, which is a minimum estimate as losses of H{sub 2}S form the sediments were not taken into account for the mass balance consideration. Complete uptake of reactive iron into sulfides has led in a significant number of samples to the presence of excess sulfur not contained in sulfides. In our argumentation we assume that excess sulfur is at least partly incorporated into the organic matter. Pyrolysis investigations show that organic matter in samples containing higher amounts of excess sulfur generates hydrocarbons at lower temperatures than samples with low concentrations of excess sulfur. These observations are compatible with findings usually reported for Type S-II kerogens. The likely organically bound excess sulfur introduces a bias with thermal maturities from RockEval pyrolysis, which implies that T{sub max} data rather reflect quality changes of the organic matter than thermal maturity in the investigated Wealden sediments. The hydrocarbon potential has been reduced significantly in samples which have been affected strongly by the microbial process as indicated by hydrogen indices of the sediments. The observations of variable degrees of sulfate reduction indicate also a variation of organic matter fluxes to the sediment surface of the palaeo-lake likely resulting from changes in biological surface productivity. Low carbon fluxes likely coincide with extensive use of organic substrate by sulfate reducers whereas high

  11. Pore system characteristics of the Permian transitional shale reservoir in the Lower Yangtze Region, China

    Directory of Open Access Journals (Sweden)

    Taotao Cao

    2016-10-01

    Full Text Available The Permian shale, a set of transitional shale reservoir, is considered to be an important shale gas exploration target in the Lower Yangtze region. Due to little research conducted on the pore system characteristic and its controlling factors of the shale gas reservoir, SEM, FE-SEM, low-pressure N2 adsorption, and mercury intrusion tests were carried out on the Permian shales from the outcrop and HC well in the southern Anhui. The results show that the Permian shales mainly consist of organic matter, quartz, illite, calcite, and pyrite, of which pyrite occurs as framboids coexisting with organic matter and the organic matter is distributed in shales in stripped, interstitial, thin film and shell shapes. The basic pore types are inorganic mineral pore (intercrystalline pore, intergranular edge pore, intergranular pore, and interlayer pore in clay minerals and the organic pore and microfracture, of which organic pore and microfracture are the dominating pore types. In shale, organic pores are not developed at all in some organic grains but are well developed in others, which may be related to the types of and maceral compositions of kerogen. Under tectonic stress, shale rocks could develop mylonitization phenomenon exhibiting organic grains well blend with clay minerals, and produce a mass of microfractures and nanopores between organic matter grains and clay minerals. Mercury intrusion tests show that the shale is mainly composed of micropore and transition pore with high porosity, good pore connectivity and high efficiency of mercury withdraw, while the shale that mainly dominated by mesopore and macropore has a low porosity, poor pore connectivity, and low efficiency of the mercury withdraw. The volume percentage of mesopore and marcopore is increasing with the increase of quartz, and that of micropore and transition pore has a decreased tendency along with the increase of soluble organic matter (S1. Organic matter is the main contributor to

  12. Geochemistry of coal-measure source rocks and natural gases in deep formations in Songliao Basin, NE China

    Energy Technology Data Exchange (ETDEWEB)

    Mi, Jingkui; Zhang, Shuichang; Hu, Guoyi; He, Kun [State Key Laboratory for Enhanced Oil Recovery, Beijing (China); Petroleum Geology Research and Laboratory Center, Research Institute of Petroleum Exploration and Development, PetroChina (China); Key Laboratory for Petroleum Geochemistry, China National Petroleum Corp. (China)

    2010-12-01

    The natural gases developed in deep volcanic rock reservoirs of the Songliao Basin, NE China are characterized by enriched {delta}{sup 13}C value for methane and frequently reversal carbon isotopic distribution pattern. Although many researchers consider such gas type as an abiogenic origin, we believe the natural gases have a biogenic origin mainly except little inorganic gases and the reversal carbon isotopic distribution pattern of gases is caused by mixing of different origin gases. Methane carbon isotopic values for majority samples fall in the range from - 24 permille to - 32 permille, which is heavier than typical coal-type gases in other Chinese basins. There are several reasons caused heavy carbon isotope of methane: (1) Carbon isotopic values of source kerogen are 3-5 permille heavier than these from other basins; (2) Source rocks are at extremely high maturity stage with vitrinite reflectance mostly above 3.0%; (3) Portion of gas is derived from basement mudrock or slate with higher maturity. The observation on the organic from deep formation reveals that there is a relatively high content for liptinite, which reaches approximately 8 to 10%. The macerals component of source rock shows that the source rocks have some ability to generate oil. Small portion of oil was generated from high hydrogen content macerals in coals and shales as proof by oil found in microcrack and in micropore of coal and oil-bearing fluid inclusions grown in volcanic reservoir. The occurrence of pyrobitumen in volcanic reservoir indicates preexisted oil had been cracked into wet gas, and this kind of gas had also been found in gas pools. Heavy isotopic methane is derived from coal at extremely high maturity stage. There may be little inorganic alkane gases in deep layers for their geochemistry and special geological setting of Songliao Basin. Artificial mixing experiments of different origins gases confirm that inorganic gas such as gas from well FS1 mixed with other end members

  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

    2003-07-28

    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

  14. Organic Matter in the Early Toarcian Shales, Paris Basin, France: a Response to Environmental Changes La matière organique dans les argiles du Toarcien inférieur du bassin de Paris, France : un enregistrement des changements d'environnement

    Directory of Open Access Journals (Sweden)

    Hollander D. J.

    2006-11-01

    Full Text Available A freshly drilled core from the Paris Basin contains a 16 m section of Early Toarcian Shale deposition. The organic matter and carbonates in these black-shale sediments were investigated using isotopic, petrologic and molecular organic geochemical methods. Throughout the studied section, molecular organic geochemical and organic petrographic characteristics remain remarkably uniform and suggest that the organic matter is overwhelmingly of marine origin (bacterial and algal with only minor contributions of terrigenous organic matter. In contrast, TOC content of the sediments, hydrogen indices of the kerogens, isotopic composition of co-existing kerogens and carbonates, and isotopic fractionation between the organic and inorganic carbon vary greatly and follow systematic trends. In general, higher values of hydrogen indices and TOC content are associated with the significantly depleted 13C values in both kerogens and carbonates and greater values of carbon isotopic fractionation. The integration of carbon isotopic fractionation between carbonates and kerogens (a proxy for surface water [CO2(aq] and hydrogen indices (a reflection of organic matter preservation suggests that the greatest accumulation of hydrocarbon-rich organic matter occurred at a time when surface water [CO2(aq] was extremely high. This implies that intermediate waters enriched in 12C-CO2 and [CO2(aq] were recycled into the photic zone of the surface water masses and provided the waters necessary to produce the observed negative isotopic excursions and maximum carbon isotopic fractionations. The settling of organic matter through a primarily anoxic water column with deposition in a highly reducing and quiescent bottom water mass was ideal for the extraordinary preservation of the organic matter. In turn, these results suggest that the depositional environment prevailing during the early Toarcian in the Paris Basin was a stratified-silled basin type environment. Si le cadre pal

  15. Hydrocarbon potential of Ordovician and Silurian rocks. Siljan Region (Sweden)

    Energy Technology Data Exchange (ETDEWEB)

    Berner, U. [Bundesanstalt fuer Geowissenschaften und Rohstoffe (BGR), Hannover (Germany); Lehnert, O. [Erlangen-Nuernberg Univ., Erlangen (Germany); Meinhold, G. [Goettingen Univ. (Germany)

    2013-08-01

    Hydrocarbon exploration in the vicinity of Europe's largest impact structure (Siljan, Central Sweden) focused for years on abiogenic concepts and largely neglected state of the art knowledge on hydrocarbon generation via thermal decomposition of organic matter. In our study we use sedimentary rocks obtained from three drill sites (Mora001, Stumsnaes 1 and Solberga 1) within the ring structure around the central uplift to investigate the hydrocarbon potential of Ordovician and Silurian strata of the region and also for comparison with the shale oil and gas potential of age equivalent rocks of the Baltic Sea. Elemental analyses provided information on concentrations of carbonate and organic carbon, total sulfur as well as on the composition of major and minor elements of the sediments. The data has been used to evaluate the depositional environment and possible diagenetic alterations of the organic matter. RockEval pyrolysis and solvent hydrocarbon extraction gave insight into the hydrocarbon generation potential and the type and thermal maturity of the sediments. From the geochemistry data of the studied wells it is obvious that changes of depositional environments (lacustrine - marine) have occurred during Ordovician and Silurian times. Although, the quality of the organic matter has been influenced in marine and brackish environments through sulfate reduction, we observe for a number of marine and lacustrine sediments a good to excellent preservation of the biological precursors which qualify the sediments as hydrocarbon source rocks (Type II kerogens). Lacustrine source rocks show a higher remaining hydrocarbon potential (up to {proportional_to}550 mg HC per g C{sub org}) than those of marine or brackish environments. Our investigations indicate that the thermal maturity of organic matter of the drill sites has reached the initial stage of oil generation. However, at Mora001 some of the sediments were stained with oil indicating that hydrocarbons have

  16. Angola: source rock control for Lower Congo Coastal and Kwanza Basin petroleum systems

    Energy Technology Data Exchange (ETDEWEB)

    Burwood, R. [Fina Exploration Ltd, Epsom (United Kingdom)

    1999-07-01

    The purpose of this paper is to provide an overview of petroleum occurrence and provenance for the 1000 km West African Atlantic Margin from Cabinda to mid-Angola. Over this margin the Lower Congo Coastal and Kwanza provinces cumulatively account for reserves of c. 6 gigabarrels oil recoverable (GBOR). These are dominantly reservoired in Pinda carbonate traps of the former basin. However, with production from a range of aggradational wedge, carbonate platform and pre-salt reservoirs, a diversity in oil character presupposes complex hydrocarbon habitats charged by multiple sourcing. Each of these two major Atlantic margin salt basins constitutes a different, source rock driven, hydrocarbon habitat. As classic passive margin pull-apart basins, Early Cretaceous initiated rift events (Pre-rift, Syn-rift I, II, etc.) evolved into the drift phase opening of the southern Atlantic. A striking feature of this progression was widespread evaporite deposition of the Aptian Loeme salt. This separates two distinct sedimentary and tectonic domains of the Pre- and Post-Salt. The core Lower Congo Coastal habitat is dominated by the Pre-Salt Bucomazi Formation sourced 'poly' petroleum system. These lacustrine, often super-rich, sediments reveal considerable organofacies variation between their basin fill (Syn-rift I) and sheet drape (Syn-rift II) development, accounting for the compositional diversity in their progenic petroleums. Of crucial impact is a cognate diversity in their kerogen kinetic behaviour. This controls the conditions and timing of generation and realization of charge potential. With the Lower Congo Coastal habitat extending southwards towards the Ambriz Spur, the Bucomazi facies proper appears restricted to the northern and deeper proto-lake trend. Over the more weakly subsident margins such troughs host inferior sheet drape potential. Elswhere, Upper Cretaceous-Palaeogene marine clastic Iabe Formation sourced petroleum systems are hydrocarbon productive

  17. THE ADVANCED CHEMISTRY BASINS PROJECT

    Energy Technology Data Exchange (ETDEWEB)

    William Goddard; Peter Meulbroek; Yongchun Tang; Lawrence Cathles III

    2004-04-05

    phase equilibrium, and physical flow through porous media. The chemical kinetic scheme includes thermal indicators including vitrinite, sterane ratios, hopane ratios, and diamonoids; and a user-modifiable reaction network for primary and secondary maturation. Also provided is a database of type-specific kerogen maturation schemes. The phase equilibrium scheme includes modules for primary and secondary migration, multi-phase equilibrium (flash) calculations, and viscosity predictions.

  18. New insights on the Frasnian/Famennian mass extinction: a role for soil erosion?

    Science.gov (United States)

    Algeo, T.; Gordon, G.; Anbar, A.; Sauer, P.; Schwark, L.; Bates, S.; Lyons, T.; Turgeon, S.; Creaser, R.; Nabbefeld, B.; Grice, K.

    2008-12-01

    The Frasnian/Famennian (F/F) mass extinction, which killed off a previously thriving tabulate coral- stromatoporoid reef community, was the most severe biotic crisis of the middle Paleozoic. The present study examines the geochemistry of a 28-m stratigraphic interval straddling the F/F boundary in the West Valley drillcore from the northern Appalachian Basin (western New York State), comprising bioturbated shales of the Hanover Formation and mostly laminated shales of the overlying Dunkirk Formation. Paleoredox proxies (DOP, FeT/Al, δ98Mo) indicate an increase in the frequency and intensity of anoxia at the F/F boundary. Proxies for hydrographic conditions (Mo/TOC, Re/TOC, U/TOC) suggest that the depositional basin experienced an interval of deepwater restriction around the boundary, possibly as a consequence of eustatic fall. The boundary is characterized by a large decrease in Zr/Al, indicating lower silt:clay ratios, and by a large decrease in excess Ba (i.e., total Ba-detrital Ba), implying reduced levels of primary productivity. Organic C- and N-isotopic data provide evidence of a major change in organic matter fluxes commencing ~7 meters below the boundary and persisting ~10 m above it. This change is characterized by ca. +5‰ and +15‰ excursions in kerogen δ13C and total organic δ13C, respectively, and by short- term excursions in organic δ15N to as low as -1‰ CDT (from background values of +1 to +2‰) that may provide evidence of cyanobacterial N fixation. Biomarker analysis, still in progress, may provide additional clues concerning changes in organic matter sources. The existing data are consistent with a model of enhanced terrigenous siliciclastic flux to the northern Appalachian Basin at the F/F boundary linked to climatic cooling, eustatic regression, and soil erosion. The rapid development of soils as a consequence of the spread of vascular land plants during the Middle and Late Devonian (Algeo et al., 1995, GSA Today, v. 5(5)) may have

  19. Hydrocarbon Maturation and Os Mixing on Bolide Impact at the Frasnian-Famennian Boundary

    Science.gov (United States)

    Stein, H.; Zimmerman, A.; Yang, G.; Hannah, J.; Egenhoff, S.

    2009-04-01

    An intractable problem in the application of Re-Os geochemistry has been knowledge of the distribution of Re and Os between source rock and generated hydrocarbon. Solutions lie in combined experimental work with controlled and induced maturation, and field studies optimized by known source rock and time of hydrocarbon generation. The Siljan impact site with its variably tilted but largely intact Ordovician-Silurian sections provides an unsurpassed opportunity to examine the Re-Os systematics of source rock and generated crude oil, and the Re-Os imprint of the bolide. This three-component system contains (1) a time pin for maturation (377 ± 2 Ma; laser argon dating of impact melt, Reimold et al. 2005) arguably at the Frasnian-Famennian boundary, (2) known source rocks with kerogens still intact, and (3) crude oils generated on impact. Modeling takes into consideration the possibility of pre-impact maturation as well. At Siljan, numerous quarries expose the Upper Ordovician Boda and Kullsberg limestone mounds, and locally, the underlying and laterally equivalent Tretaspis (Fjäcka) shale. We obtained a sample of crude oil seeping from a drill hole in the quarry floor at Solberga. Preliminary Re-Os analyses on four aliquots of this oil form an excellent linear array in 187Re/188Os versus 187Os/188Os space. The associated age, however, is impossibly old (Neoproterozoic), and the initial 187Os/188Os unreasonably low (0.2). Rather, this linear array fits a mixing line between a meteoritic component and a hydrocarbon generated from the Tretaspis shale. We are presently performing further tests to isolate the two end-members. Filtering suggests that the extraterrestrial component consists of small physical particles which can be largely removed from the petroleum fraction. The extreme contrast in Re-Os composition between meteorite (known) and black shale (in progress) end-members maximizes the sensitivity of the isotopic study. Reimold, W.U., Kelley, S.P., Sherlock, S

  20. Glacial and tectonic influence on terrestrial organic carbon delivery to high latitude deep marine systems: IODP Site U1417, Surveyor Fan, Gulf of Alaska

    Science.gov (United States)

    Childress, L. B.; Ridgway, K. D.

    2014-12-01

    Glacial and tectonic processes on active margins are intrinsically coupled to the transport of sediment and associated organic carbon (OC). Glaciation/deglaciation and the formation of ice sheets can alter the quantity and composition of OC delivered to the marine environment. Over geologic time scales (>1 Ma), exhumation and mass wasting of sedimentary rock from uplifted accretionary wedges inject recycled OC (e.g. kerogen), along with modern OC into the marine environment. The sedimentary record of glacial and tectonic processes along the southern Alaska margin is particularly well preserved at Integrated Ocean Drilling Program (IODP) Site U1417. Lithofacies of Site U1417 can be divided into 3 sedimentary packages that we interpret as linked to the onset of tidewater glaciation along, and tectonic convergence of the Yakutat Terrane with, the continental margin of northwestern Canada and southern Alaska. Based on previous studies linking the development of the Cordilleran Ice Sheet and the movement of the Yakutat Terrane to the development of the Surveyor Fan System, we hypothesize biogeochemical variations in the deposited sediments as a result of changing provenance. Preservation of terrestrial OC that has been documented in sediments of the Alaskan continental shelf margin and sediment routing through the deep-sea Surveyor Channel from the Pleistocene to modern time implies a long-term conduit for this OC to reach the distal portion of the Surveyor Fan system. To correlate marine deposits with terrestrial formations, bulk geochemical and detailed biomarker analyses are used to delineate source material. Preliminary bulk OC content and stable carbon isotope analyses of the Yakataga, Poul Creek, and Kultheith Fms. reveal notable differences. Detailed biomarker analysis by pyrolysis-gas chromatograph-mass spectrometry has revealed further differences between the three primary formations. Using the biogeochemical fingerprints of the Yakataga, Poul Creek, and coal

  1. Geochemical characteristics of crude oil from a tight oil reservoir in the Lucaogou Formation, Jimusar Sag, Junggar Basin

    Science.gov (United States)

    Cao, Z.

    2015-12-01

    Jimusar Sag, which lies in the Junggar Basin,is one of the most typical tight oil study areas in China. However, the properties and origin of the crude oil and the geochemical characteristics of the tight oil from the Lucaogou Formation have not yet been studied. In the present study, 23 crude oilsfrom the Lucaogou Formation were collected for analysis, such as physical properties, bulk composition, saturated hydrocarbon gas chromatography-mass spectrometry (GC-MS), and the calculation of various biomarker parameters. In addition,source rock evaluation and porosity permeability analysis were applied to the mudstones and siltstones. Biomarkers of suitable source rocks (TOC>1, S1+S2>6mg/g, 0.7%kerogen. In addition, a higher proportion of bacteria and algae was shown to contribute to the formation of crude oil in the lower section when compared with the upper section of the Lucaogou Formation. Oil-source correlations demonstrated that not all mudstones within the Lucaogou Formation contributed to oil accumulation.Crude oil from the upper and lower sections originated from thin-bedded mudstones interbedded within sweet spot sand bodies. A good coincidence of filling history and hydrocarbon generation history indicated that the Lucaogou reservoir is a typical in situ reservoir. The mudstones over or beneath the sweet spot bodies consisted of natural caprocks and prevented the vertical movement of oil by capillary forces. Despite being thicker, the thick-bedded mudstone between the upper and lower sweet spots had no obvious contribution to

  2. Hydrocarbon potential, palynology and palynofacies of four sedimentary basins in the Benue Trough, northern Cameroon

    Science.gov (United States)

    Bessong, Moïse; Hell, Joseph Victor; Samankassou, Elias; Feist-Burkhardt, Susanne; Eyong, John Takem; Ngos, Simon, III; Nolla, Junior Désiré; Mbesse, Cecile Olive; Adatte, Thierry; Mfoumbeng, Marie Paule; Dissombo, Edimo André Noel; Ntsama, Atangana Jacqueline; Mouloud, Bennami; Ndjeng, Emmanuel

    2018-03-01

    Organic geochemical, palynological and palynofacies analyses were carried out on 79 selected samples from four sedimentary basins (Mayo-Rey, Mayo-Oulo-Lere, Hamakoussou and Benue) in northern Cameroon. Rock-Eval pyrolysis and Total Organic Carbon results indicate that most of the samples of the studied basins are thermally immature to mature. The organic matter consists of terrestrial components (peat, lignite, bituminous coal, and anthracite) associated with organic matter of marine origin. Based on the appraisal of multiple parameters: Total Organic Carbon (TOC), maximum Temperature (T-max), Hydrogen Index (HI), Oxygen Index (OI) and Production Index (PI), some samples are organically rich both in oil and/or gas-prone kerogen Type-II, II/III and III. The source rock quality ranges from poor to very good. The source material is composed of both algae and higher plants. Samples from these basins yielded palynological residue composed of translucent and opaque phytoclasts, Amorphous Organic Matter (AOM), fungal remains, algal cysts pollen and pteridophyte spores. Abundance and diversity of the palynomorphs overall low and include Monoporopollenites annulatus (= Monoporites annulatus), indeterminate periporate pollen, indeterminate tetracolporate pollen, indeterminate tricolporate pollen, indeterminate triporate pollen, indeterminate trilete spores, Polypodiaceoisporites spp., Biporipsilonites sp., Rhizophagites sp., Striadiporites sp., Botryococcus sp. (colonial, freshwater green algae), and Chomotriletes minor (cyst of zygnematalean freshwater green algae). Age assigned confidently for all these basins the palynological data except for one sample of Hamakoussou that can be dated as Early to Mid-Cretaceous in age. Callialasporites dampieri, Classopollis spp., Eucommiidites spp. and Araucariacites australis indicate, an Aptian to Cenomanian age. The other pollen and spores recovered may indicate a Tertiary or younger age (especially Monoporopollenites annulatus), or

  3. 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

  4. Geochemical analysis of Lower Toarcian black shale from Mecsek Mountain, Hungary

    Science.gov (United States)

    Podobni, András; Rübsam, Wolfgang; Schwark, Lorenz; Kovács, János; Fekete, József

    2016-04-01

    section investigated. Variable, but mainly high HI values (100-700 mgHC/gTOC) allow attributing the OM to a type II kerogen. Results are in agreement with previous studies showing that the OM is mainly composed of liptinites, which point to algal and land plant-derived OM [2]. Moreover, variable contributions from marine and terrigenous sources are also attested by the ratio of isoprenoids (pristane and phytane) and the corresponding n-alkanes. Accumulation of OM occurred under mildly reducing, most likely anoxic, conditions as indicated by Pr/Phy ratios of about 1.5 and mainly low HHI values Guide: Volume 2, Biomarkers and Isotopes in Petroleum Systems and Earth History. Cambridge University Press, 1132 pp.

  5. Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

    Science.gov (United States)

    Shuai, Yanhua; Douglas, Peter M.J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

    2018-01-01

    Multiply isotopically substituted molecules (‘clumped’ isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature–time conditions corresponding to ‘low,’ ‘mature,’ and ‘over-mature’ stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions (‘high’ to ‘over-mature’ stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where ‘secondary’ cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation

  6. Microfacies of mappable Archean biomats, Moodies Group, Barberton Greenstone Belt, South Africa

    Science.gov (United States)

    Gamper, Antonia; Heubeck, Christoph; Ohnemueller, Frank; Walsh, Maud

    2010-05-01

    The ca. 3.22 Ga-old Moodies Group, Barberton Mountain Land, South Africa, arguably includes the world's oldest regionally mappable biofacies. There, abundant smooth, wavy, domal or cuspate, interwoven or parallel-stratified laminae of isotopically light kerogen (Noffke et al. 2006) in shallow-water or coastal environments show a microtopography of several cm, deform cohesively, trap and bind grains, and were surficially rapidly silicified. In order to investigate the microfacies and habitat of these extensive biomats, we measured stratigraphic sections, sampled for petrography and composition, and documented sedimentary structures throughout. Seven stratigraphic sections allow the reconstruction of a coastal depositional system with an thickness of approx. 240 m along an > 11 km long outcrop belt. The system can be subdivided in (from base to top deepening) terrestrial coastal, low-angle shoreline, subtidal and shoreface facies. Biomats are most densely (mm- to cm-) spaced in the shoreface unit whereas they are least common in the basal terrestrial unit in which single-pebble trains and thin gravel conglomerates occur. Biomats (mean 4 mm thick) reach their greatest individual thickness (up to 0,8 cm) and dominate the spectrum of sedimentary structures in the subtidal unit where they form black, internally laminated chert bands. Most chert bands overlie lenses of elongate, well-sorted, coarse-grained sandstone but are in turn sharply overlain by medium- and fine-grained sandstone, suggesting cyclic current activity. Clustered or regularly spaced (sub-)vertical fluid escape structures penetrate and ductily deform densely spaced interwoven biomats. They occur most widely in the shoreface facies, show a mean height of 49 cm, are commonly offset horizontally, and reach up to 230 cm. The margins of several shallow (max. 1 m deep) and up to 8 m wide channels erosively truncate wrinkled biomats of the terrestrial coastal facies. Channel fill includes dominant medium- to

  7. Reservoir petrophysics and hydrocarbon occurrences of the Bahariya Formation, Alamein-Yidma fields, Western Desert of Egypt

    Energy Technology Data Exchange (ETDEWEB)

    Abdel-Aziz Younes, Mohamed [Alexandria Univ. (Egypt). Geology Dept.

    2012-12-15

    < 0.47. The burial history modeling revealed that the potential source rock in the Alamein basin is the marine shale source rock of the Middle Jurassic (Khatatba Formation). The Khatatba shale has mixed kerogen types II-III and entered the mid- mature stage of oil generation window at vitrinite reflectance measurements 0.9 Ro% at approximately 90 million years ago (Early Cenomanian). These similarities in geologic occurrences and biomarker characteristics suggest the possibility that the hydrocarbon expulsion would have been initiated from deeply buried Jurassic source rocks and trapped in the Pre-Laramide structures of Bahariya Formation throughout the extensional faults. (orig.)

  8. Biogeochemical Cycling of Fe, S, C, N, and Mo in the 3.2 Ga ocean: Constraints from DXCL-DP Black Shales from Pilbara, Western Australia

    Science.gov (United States)

    Yamaguchi, K. E.; Naraoka, H.; Ikehara, M.; Ito, T.; Kiyokawa, S.

    2014-12-01

    Records of geochemical cycling of bio-essential, redox-sensitive elements have keys to decipher mysteries of the co-evolution of Earth and life. To obtain insight into biogeochemical cycling of those elements and early evolution of microbial biosphere from high-quality samples, we drilled through Mesoarchean strata in coastal Pilbara (Dixon Island-Cleaverville Drilling Project, see Yamaguchi et al., 2009; Kiyokawa et al., 2012), and obtained 3.2 Ga old drillcores (CL1, CL2, and DX) of sulfide-rich black shales in the Cleaverville Group, Pilbara Supergroup. We conducted a systematic geochemical study involving sequential extractions of Fe, S, C, and N for phase-dependent contents (e.g., pyrite-Fe, reactive-Fe, highly reactive-Fe, unreactive-Fe, pyrite-S, sulfate-S, organic-S, elemental-S, Corg, Ccarb, Norg, and Nclay) and their stable isotope compositions, micro FT-IR and laser Raman spectroscopy for extracted kerogen, in addition to major and trace (redox-sensitive; e.g., Mo) element analysis, for >100 samples. Here we integrate our recent multidisciplinary investigations into the redox state of ocean and nature of microbial biosphere in the ocean 3.2 Ga ago. All of the obtained data are very difficult to explain only by geochemical processes in strictly anoxic environments, where both atmosphere and oceans were completely anoxic, like an environment before the inferred "Great Oxidation Event" when pO2 was lower than 0.00001 PAL (e.g., Holland, 1994). Our extensive data set consistently suggests that oxygenic photosynthesis, bacterial sulfate reduction, and microbially mediated redox-cycling of nitrogen, possibly involving denitrification and N2-fixation, are very likely to have been operating, and may be used as a strong evidence for at least local and temporal existence of oxidized environment as far back as 3.2 Ga ago. Modern-style biogeochemical cycling of Fe, S, C, N, and Mo has been operating since then. The atmosphere-hydrosphere system 3.2 Ga ago would have

  9. Paleoclimate records at high latitude in Arctic during the Paleogene

    Science.gov (United States)

    Salpin, Marie; Schnyder, Johann; Baudin, François; Suan, Guillaume; Labrousse, Loïc; Popescu, Speranta; Suc, Jean-Pierre

    2015-04-01

    fraction, Rock-Eval pyrolysis, palynology, palynofacies, carbon isotopes. The organic matter of the two sections is dominated by Type III kerogens. First results from palynology and clay minerals proportions suggest episodes of warming that could be compared to similar warming intervals recorded on the Siberian margin. In addition, in the northern Yukon the mineralogical results suggests fluctuations of the local detrital sources, either driven by tectonic or eustatism, that could be surimposed on the climatic patterns.

  10. Astrophysics and Weak Form of Panspermia Hypothesis and Exogenous Factors in the Evolution of the Earth

    Science.gov (United States)

    Adushkin, V. V.; Vityazev, A. V.; Glazachev, D. O.; Pechernikova, G. V.

    2014-10-01

    The problems of the origin of Earth and life are fundamental in the modern science. We, relying on the data of resent years, contemplate a new course of research in this old problem. On the base of astrophysical data, obtained during the last 30-50 years, and the resent results of the study of small bodies in the Solar System (comets in particular) it is possible to combine the old idea about panspermia in a comprehensive sense and the search of the basis of life on the early Earth grounded on theoretical and laboratory data on the Earth evolution. Most likely, the Sun and a gas-and-dust disk surrounding it were created in a Giant molecular cloud near young giants - blue O-B-stars which ultraviolet radiation provided a weak chirality (to 15% of EEs) in organics of interstellar dust. Further a part of interstellar dust beyond orbits larger than 3-4 a.u. remained cold and then entered into the first planetesimals. The organics, after melting of interiors of the first planetesimals due to the heating by shortliving 26Al and 60Fe, sank, in the form of kerogens, into the core where formation of the first complex organic compounds began. This occurred in the first 3-4 Myr after the CAI. Apparently, it is necessary to look for anaerobic life in comets. In geosciences obtained various data banks, such as data on the endogenous activity of the Earth, mass extinctions of life and changes in biodiversity, impacts of cosmic bodies, inversions of the magnetic field, climate change, etc. The problem of cyclicity and correlation of all these processes is studied for 50 years. Results of spectral, wavelet and correlation analysis of the data series, representing some of these processes are given. We conclude, that most of them are cyclic, some of the periods are present in all the processes. The mechanisms of the influence of the galaxy on the processes occurring on the Earth are discussed.

  11. Survey for Life-related Species During a Planetary Surface Exploration; System Type I - UV Stimulated Fluorescent Sensor

    Science.gov (United States)

    Wang, Alian; Haskin, L. A.; Gillis, J. J.

    2003-01-01

    The widely accepted minimum requirements for life on Earth include the presence of water and accessible sources of carbon. We assume that the same criteria must hold for putative life on past or present Mars. The evidence for CO2 and H2O at or near the Martian surface, carbon in Martian meteorites, aqueous alteration, and probable hydrothermal activity suggest that conditions conducive to the origin and evolution of life on Mars may have existed for long periods of time and may still obtain at present. Surface exploration on Mars that enables the direct detection of water in minerals and of organic carbon (including not just organic and biogenic materials but their degradation products such as kerogen-like hydrocarbons and graphitized carbon) that might be products or residues of biologic activity, is crucial. The search for evidence of life, past or present, will nevertheless be difficult. The lack of direct evidence for organic carbon and the low amounts of water found in the soils at the Viking sites demonstrated the difficulties. Recent results of GRS experiment of Odyssey mission indicated the existence of abundant water ice beneath the Mars surface. Mineralogical evidence for the presence of carbonate, sulfates, or clay minerals, products of weathering and aqueous deposition, have not been identified unambiguously on Mars. Rocks such as shales and, more particularly, limestones, which we associate with moist and benign environments on Earth, are evidently not abundant. Presumably, then, neither were the photosynthetic organisms that might have produced them. In addition, the harsh present environment on Mars (e.g., dryness, low temperatures, large temperature cycles, high level of UV light on the surface, frequent dust storms, etc.) can both destroy carbon- and water-bearing materials and hide them. Therefore, directly detecting life-related materials on Mars was likened to seeking and examining proverbial needles in haystacks. We argue that survey type

  12. Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

    Science.gov (United States)

    Kenig, F.; Damste, J. S.; Frewin, N. L.; Hayes, J. M.; De Leeuw, J. W.

    1995-01-01

    those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.

  13. Pore formation and occurrence in the organic-rich shales of the Triassic Chang-7 Member, Yanchang Formation, Ordos Basin, China

    Directory of Open Access Journals (Sweden)

    Chuang Er

    2016-12-01

    .75%. Consequently, low organic pores could have been caused by the combination effect of low maturity and compaction. In addition, hydrocarbon is adsorbed on the surface of the organic matter, which could have caused the expansion of kerogen and then the reduction of organic pore.

  14. Chemical characteristics of Upper Cretaceous (Turonian) jet of the Gosau Group of Gams/Hieflau (Styria, Austria)

    Energy Technology Data Exchange (ETDEWEB)

    Bechtel, A.; Gratzer, R.; Sachsenhofer, R.F. [Institut fuer Geowissenschaften, Prospektion und Angewandte Sedimentologie, Montanuniversitaet Leoben, Peter-Tunner-Str. 5, A-8700 Leoben (Austria)

    2001-03-01

    Jet and coaly sediments within the Upper Cretaceous (Gosau) Schoenleiten Formation were collected from two outcrops near Gams/Hieflau (Styria, Austria). For comparison, additional jet and coal samples from different Gosau localities were included in the study. The identification of jet as bituminous driftwood (collotelinite) has been provided by microscopical examination of organic matter [Kollmann, H.A. and Sachsenhofer, R.F., Mitt. Ref. Geol. und Palaeont. Landesmuseum Joanneum SH 2 (1998) 223]. Rock-Eval analyses revealed enhanced HI and lower T{sub max} values of jet compared with the coals and coaly shales. The results reflect the higher contents of bituminous organic matter compared to vitrain-rich coals of similar maturity. In comparison with the coals and coaly shales, high amounts of liberated hydrocarbons (mg HC/g C{sub org}) are in contrast to generally lower yields of soluble organic matter during extraction with dichloromethane, indicating that portions of the hydrocarbons are liberated from lipids loosely bound to kerogen during pyrolysis. Further differences in n-alkane distribution patterns, odd over even predominance, pristane/phytane, and pristane/n-C{sub 17} ratios exist between jet, coals and coaly shales. The microbial origin of short-chain n-alkanes presumably resulted from the degradation of the predominant odd-numbered long-chain n-alkanes within the jet. The occurrence of biological markers (sesqui and diterpenoids) within the sediments (coaly shales), coals and jet samples indicates the origin of terrestrial organic matter from conifers. Biomarker composition of jet samples indicates enhanced aromatisation of sesqui and diterpenoids. These results correspond to enhanced aromatisation of steranes, as reflected by generally higher relative contents of triaromatic steroids in the jet. Because of comparable maturation (0.5-0.6% R{sub r}) of the coals, coaly shales and the jet samples, confirmed by the isomerisation of {alpha}{beta} C{sub 31

  15. Unpacking paleoenvironmental change across OAE2 using paired d34S records of pyrite and organic matter

    Science.gov (United States)

    Raven, M. R.; Gomes, M.; Fike, D. A.

    2017-12-01

    Pyrite sulfur isotopes have proven to be a powerful tool for reconstructing major changes in global redox state and the emergence of microbial metabolisms. Still, pyrite can be a challenging archive, as its formation depends on the availability of reactive iron species and can occur over multiple generations of sedimentary processes. Accordingly, pyrite δ34S records commonly have large point-to-point variability reflecting local processes. By pairing pyrite δ34S records with those of coexisting organic matter (OM), including both kerogens and extractable bitumens, we can begin to parse the various potential causes of this variability and gain greater insights into changes in the sedimentary paleoenvironment. Here, we present the first collection of records of OM δ34S for the Cretaceous, focusing on sections spanning Ocean Anoxic Event 2 (OAE2, 94 Mya), a period of globally widespread marine anoxia and carbon cycle disruption. In carbonates and shales from OAE2 in Pont d'Issole, France, pyrite and OM δ34S values vary in parallel throughout most of the section, consistent with their shared sulfide source. There are also distinct exceptions: In one interval, an excursion in pyrite δ34S is entirely absent from the organic sulfur record but associated with unusual organic sulfur redox speciation (by XAS), potentially reflecting later exposure to oxic porewaters. Across the core interval of shale deposition during OAE2, the offset between pyrite and OM δ34S values declines smoothly from +17.4 to -7.9‰, which we interpret in terms of changes in the speciation of detrital iron minerals that may have regional implications. We then compare these results with data for other well-characterized OAE2 sections, including Cismon (Italy), Tarfaya (Morocco), and the Demerara Rise (offshore Brazil), which represent environments with a variety of apparent redox states. These paired pyrite - OM δ34S profiles yield new information about how the local and global forcings

  16. Signatures of Chemical Evolution in Protostellar Nebulae

    Science.gov (United States)

    Nuth, Joseph A., III; Johnson, Natasha

    2011-01-01

    the Haber-Bosch reactions used in industry, the surface catalyzed reactions seen in our laboratory do not produce a simple product stream of methane or ammonia, respectively. Instead, such reactions produce a wide range of both aliphatic and aromatic hydrocarbons, as well as reduced nitrogen compounds such as ammonia, amines, amides and imides, as gas phase products together with a heavy, macromolecular, kerogen-like surface coating that remains on the grains. While CO and N2 will certainly be depleted by conversion into more complex and less volatile species via reaction on grain surfaces, it may be very difficult to monitor such changes from outside the system.

  17. Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

    Science.gov (United States)

    Shuai, Yanhua; Douglas, Peter M. J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael D.; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

    2018-02-01

    Multiply isotopically substituted molecules ('clumped' isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature-time conditions corresponding to 'low,' 'mature,' and 'over-mature' stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions ('high' to 'over-mature' stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where 'secondary' cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl

  18. 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

  19. 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

  20. Structural effects of C60+ bombardment on various natural mineral samples-Application to analysis of organic phases in geological samples

    International Nuclear Information System (INIS)

    Siljestroem, S.; Lausmaa, J.; Hode, T.; Sundin, M.; Sjoevall, P.

    2011-01-01

    Organic phases trapped inside natural mineral samples are of considerable interest in astrobiology, geochemistry and geobiology. Examples of such organic phases are microfossils, kerogen and oil. Information about these phases is usually retrieved through bulk crushing of the rock which means both a risk of contamination and that the composition and spatial distribution of the organics to its host mineral is lost. An attractive of way to retrieve information about the organics in the rock is depth profiling using a focused ion beam. Recently, it was shown that it is possible to obtain detailed mass spectrometric information from oil-bearing fluid inclusions, i.e. small amounts of oil trapped inside a mineral matrix, using ToF-SIMS. Using a 10 keV C 60 + sputter beam and a 25 keV Bi 3 + analysis beam, oil-bearing inclusions in different minerals were opened and analysed individually. However, sputtering with a C 60 + beam also induced other changes to the mineral surface, such as formation of topographic features and carbon deposition. In this paper, the cause of these changes is explored and the consequences of the sputter-induced features on the analysis of organic phases in natural mineral samples (quartz, calcite and fluorite) in general and fluid inclusions in particular are discussed. The dominating topographical features that were observed when a several micrometers deep crater is sputtered with 10 keV C 60 + ions on a natural mineral surface are conical-shaped and ridge-like structures that may rise several micrometers, pointing in the direction of the incident C 60 + ion beam, on an otherwise flat crater bottom. The sputter-induced structures were found to appear at places with different chemistry than the host mineral, including other minerals phases and fluid inclusions, while structural defects in the host material, such as polishing marks or scratches, did not necessarily result in sputter-induced structures. The ridge-like structures were often covered

  1. North Slope, Alaska: Source rock distribution, richness, thermal maturity, and petroleum charge

    Science.gov (United States)

    Peters, K.E.; Magoon, L.B.; Bird, K.J.; Valin, Z.C.; Keller, M.A.

    2006-01-01

    Four key marine petroleum source rock units were identified, characterized, and mapped in the subsurface to better understand the origin and distribution of petroleum on the North Slope of Alaska. These marine source rocks, from oldest to youngest, include four intervals: (1) Middle-Upper Triassic Shublik Formation, (2) basal condensed section in the Jurassic-Lower Cretaceous Kingak Shale, (3) Cretaceous pebble shale unit, and (4) Cretaceous Hue Shale. Well logs for more than 60 wells and total organic carbon (TOC) and Rock-Eval pyrolysis analyses for 1183 samples in 125 well penetrations of the source rocks were used to map the present-day thickness of each source rock and the quantity (TOC), quality (hydrogen index), and thermal maturity (Tmax) of the organic matter. Based on assumptions related to carbon mass balance and regional distributions of TOC, the present-day source rock quantity and quality maps were used to determine the extent of fractional conversion of the kerogen to petroleum and to map the original TOC (TOCo) and the original hydrogen index (HIo) prior to thermal maturation. The quantity and quality of oil-prone organic matter in Shublik Formation source rock generally exceeded that of the other units prior to thermal maturation (commonly TOCo > 4 wt.% and HIo > 600 mg hydrocarbon/g TOC), although all are likely sources for at least some petroleum on the North Slope. We used Rock-Eval and hydrous pyrolysis methods to calculate expulsion factors and petroleum charge for each of the four source rocks in the study area. Without attempting to identify the correct methods, we conclude that calculations based on Rock-Eval pyrolysis overestimate expulsion factors and petroleum charge because low pressure and rapid removal of thermally cracked products by the carrier gas retards cross-linking and pyrobitumen formation that is otherwise favored by natural burial maturation. Expulsion factors and petroleum charge based on hydrous pyrolysis may also be high

  2. Geochemical characteristics and implications of shale gas from the Longmaxi Formation, Sichuan Basin, China

    Directory of Open Access Journals (Sweden)

    Chunhui Cao

    2016-04-01

    Full Text Available Gas geochemical analysis was conducted on the shale gas from the Longmaxi Formation in the Weiyuan-Changning areas, Sichuan Basin, China. Chemical composition was measured using an integrated method of gas chromatography combined with mass spectrometry. The results show that the Longmaxi shale gas, after hydraulic fracturing, is primarily dominated by methane (94.0%–98.6% with low humidity (0.3%–0.6% and minor non-hydrocarbon gasses which are primarily comprised of CO2, N2, as well as trace He. δ13CCO2 = −2.5‰−6.0‰3He/4He = 0.01–0.03Ra.The shale gas in the Weiyuan and Changning areas display carbon isotopes reversal pattern with a carbon number (δ13C1 > δ13C2 and distinct carbon isotopic composition. The shale gas from the Weiyuan pilot has heavier carbon isotopic compositions for methane (δ13C1: from −34.5‰ to −36.8‰, ethane (δ13C2: −37.6‰ to −41.9‰, and CO2 (δ13CCO2: −4.5‰ to −6.0‰ than those in the Changning pilot (δ13C1: −27.2‰ to −27.3‰, δ13C2: −33.7‰ to −34.1‰, δ13CCO2: −2.5‰ to −4.6‰. The Longmaxi shale was thermally high and the organic matter was in over mature stage with good sealing conditions. The shale gas, after hydraulic fracturing, could possibly originate from the thermal decomposition of kerogen and the secondary cracking of liquid hydrocarbons which caused the reversal pattern of carbon isotopes. Some CO2 could be derived from the decomposition of carbonate. The difference in carbon isotopes between the Weiyuan and Changning areas could be derived from the different mixing proportion of gas from the secondary cracking of liquid hydrocarbons caused by specific geological and geochemical conditions.

  3. Quantitative on-line analysis of sulfur compounds in complex hydrocarbon matrices.

    Science.gov (United States)

    Djokic, Marko R; Ristic, Nenad D; Olahova, Natalia; Marin, Guy B; Van Geem, Kevin M

    2017-08-04

    An improved method for on-line measurement of sulfur containing compounds in complex matrices is presented. The on-line system consists of a specifically designed sampling system connected to a comprehensive two-dimensional gas chromatograph (GC×GC) equipped with two capillary columns (Rtx ® -1 PONA×SGE BPX50), a flame ionization detector (FID) and a sulfur chemiluminescence detector (SCD). The result is an unprecedented sensitivity down to ppm level (1 ppm-w) for various sulfur containing compounds in very complex hydrocarbon matrices. In addition to the GC×GC-SCD, the low molecular weight sulfur containing compounds such as hydrogen sulfide (H 2 S) and carbonyl sulfide (COS) can be analyzed using a thermal conductivity detector of a so-called refinery gas analyzer (RGA). The methodology was extensively tested on a continuous flow pilot plant for steam cracking, in which quantification of sulfur containing compounds in the reactor effluent was carried out using 3-chlorothiophene as internal standard. The GC×GC-FID/-SCD settings were optimized for ppm analysis of sulfur compounds in olefin-rich (ethylene- and propylene-rich) hydrocarbon matrices produced by steam cracking of petroleum feedstocks. Besides that is primarily used for analysis of the hydrocarbon matrix, FID of the GC×GC-FID/-SCD set-up serves to double check the amount of added sulfur internal standard which is crucial for a proper quantification of sulfur compounds. When vacuum gas oil containing 780 ppm-w of elemental sulfur in the form of benzothiophenes and dibenzothiophenes is subjected to steam cracking, the sulfur balance was closed, with 75% of the sulfur contained in the feed is converted to hydrogen sulfide, 13% to alkyl homologues of thiophene while the remaining 12% is present in the form of alkyl homologues of benzothiophenes. The methodology can be applied for many other conversion processes which use sulfur containing feeds such as hydrocracking, catalytic cracking, kerogen

  4. Laboratory simulated hydrothermal alteration of sedimentary organic matter from Guaymas Basin, Gulf of California. Ph.D. Thesis

    Science.gov (United States)

    Leif, Roald N.

    1993-01-01

    hydrocarbons generated from kerogen was observed to go through alkene intermediates, and the rate of alkene isomerization was influenced by the ionic strength and catalytic mineral phases. Confinement of the organic pyrolysate to the bulk sediment accelerated the rates of the biomarker epimerization reactions, suggesting that these reactions are influenced strongly by the association of the inorganic matrix, and that the relative rates of some ionic and radical reactions can be influenced by the water/rock ratio during the pyrolysis experiments.

  5. Clean and Secure Energy from Domestic Oil Shale and Oil Sands Resources

    Energy Technology Data Exchange (ETDEWEB)

    Spinti, Jennifer [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Birgenheier, Lauren [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Deo, Milind [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Facelli, Julio [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Hradisky, Michal [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Kelly, Kerry [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Miller, Jan [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); McLennan, John [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Ring, Terry [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Ruple, John [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Uchitel, Kirsten [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States)

    2015-09-30

    (March, 2012); Conjunctive Surface and Groundwater Management in Utah: Implications for Oil Shale and Oil Sands Development (May, 2012); Development of CFD-Based Simulation Tools for In Situ Thermal Processing of Oil Shale/Sands (February, 2012); Core-Based Integrated Sedimentologic, Stratigraphic, and Geochemical Analysis of the Oil Shale Bearing Green River Formation, Uinta Basin, Utah (April, 2011); Atomistic Modeling of Oil Shale Kerogens and Asphaltenes Along with their Interactions with the Inorganic Mineral Matrix (April, 2011); Pore Scale Analysis of Oil Shale/Sands Pyrolysis (March, 2011); Land and Resource Management Issues Relevant to Deploying In-Situ Thermal Technologies (January, 2011); Policy Analysis of Produced Water Issues Associated with In-Situ Thermal Technologies (January, 2011); and Policy Analysis of Water Availability and Use Issues for Domestic Oil Shale and Oil Sands Development (March, 2010)

  6. Biosignatures observed by Raman mapping in silicified materials

    Science.gov (United States)

    Foucher, F.; Westall, F.; Knoll, A.

    2012-04-01

    converts to quartz but, in this case where the rocks are very poorly metamorphosed, conversion seems to have been inhibited by the kerogen matrix within which the opal precipitated. Both anatase and pyrite may be formed abiogenically but their intimate association with the remnants of microorganisms suggests a link between the diagenesis of the dead organisms and the precipitation of these minerals. Interestingly, the Raman maps of the Draken microfossils also document differences in the D/G peak ratios within a particular microfossil structure. Thus, we demonstrate that mapping using micro-Raman spectrometry is a rapid method of investigation of potential biosignatures and an excellent complement to other methods of biosignature detection. Reference: [1] Knoll, A. H., Swett, K., and Mark, J., 1991, Journal of Paleontology 65, 531-569.

  7. Organic geochemistry and stable isotope composition of New Zealand carbonate concretions and calcite fracture fills

    International Nuclear Information System (INIS)

    Pearson, M.J.; Nelson, C.S.

    2005-01-01

    occur in Northland calcite concretion bodies, but not in their septarian fracture fill. Release from kerogen into migrating pore fluid during an early organic maturation stage is suggested as a plausible origin of the diacids. Their site of entrapment may have been serendipitous, depending on the timing of concretion body and fracture fill carbonate precipitation. (author). 60 refs., 7 figs., 4 tabs

  8. Whole-core analysis by 13C NMR

    International Nuclear Information System (INIS)

    Vinegar, H.J.; Tutunjian, P.N.; Edelstein, W.A.; Roemer, P.B.

    1991-01-01

    This paper reports on a whole-core nuclear magnetic resonance (NMR) system that was used to obtain natural abundance 13 C spectra. The system enables rapid, nondestructive measurements of bulk volume of movable oil, aliphatic/aromatic ratio, oil viscosity, and organic vs. carbonate carbon. 13 C NMR can be used in cores where the 1 H NMR spectrum is too broad to resolve oil and water resonances separately. A 5 1/4-in. 13 C/ 1 H NMR coil was installed on a General Electric (GE) CSI-2T NMR imager/spectrometer. With a 4-in.-OD whole core, good 13 C signal/noise ratio (SNR) is obtained within minutes, while 1 H spectra are obtained in seconds. NMR measurements have been made of the 13 C and 1 H density of crude oils with a wide range of API gravities. For light- and medium-gravity oils, the 13 C and 1 H signal per unit volume is constant within about 3.5%. For heavy crudes, the 13 C and 1 H density measured by NMR is reduced by the shortening of spin-spin relaxation time. 13 C and 1 H NMR spin-lattice relaxation times were measured on a suite of Cannon viscosity standards, crude oils (4 to 60 degrees API), and alkanes (C 5 through C 16 ) with viscosities at 77 degrees F ranging from 0.5 cp to 2.5 x 10 7 cp. The 13 C and 1 H relaxation times show a similar correlation with viscosity from which oil viscosity can be estimated accurately for viscosities up to 100 cp. The 13 C surface relaxation rate for oils on water-wet rocks is very low. Nonproton decoupled 13 C NMR is shown to be insensitive to kerogen; thus, 13 C NMR measures only the movable hydrocarbon content of the cores. In carbonates, the 13 C spectrum also contains a carbonate powder pattern useful in quantifying inorganic carbon and distinguishing organic from carbonate carbon

  9. Trace element characterisation of Cretaceous Orange Basin hydrocarbon source rocks

    International Nuclear Information System (INIS)

    Akinlua, A.; Adekola, S.A.; Swakamisa, O.; Fadipe, O.A.; Akinyemi, S.A.

    2010-01-01

    Research highlights: → Vanadium and nickel contents indicate that the rock samples from the Orange Basin have marine organic matter input. → The organic matter of the Orange Basin source rocks were deposited in reducing conditions. → Despite the similarities in the organic matter source input and depositional environment of the samples from the two well, cross plots of Co/Ni versus V/Ni and Mo/Ni versus Co/Ni were able to reveal their subtle differences. → Cluster analysis classified the samples into three groups based on subtle differences in their .thermal maturity. - Abstract: Trace elements in the kerogen fraction of hydrocarbon source rock samples from two wells obtained from the Cretaceous units of the Orange Basin, South Africa were determined using X-ray fluorescence spectrometry, in order to determine their distribution and geochemical significances. The concentrations of the elements (As, Ce, Co, Cu, Fe, Mo, Ni, Pb and V) determined ranged from 0.64 to 47,300 ppm for the samples analysed. The total organic carbon (TOC) values indicate that the samples are organic rich but did not show any trend with the distribution of the trace metals except Ce, Mo and Pb. Dendrogram cluster analysis discriminated the samples into three groups on the basis of their level of thermal maturity. Thermal maturity has a significant effect on the distribution of the trace metals. Cobalt/Ni and V/Ni ratios and cross plots of the absolute values of V and Ni indicate that the samples had significant marine organic matter input. The V and Ni contents and V/(V + Ni) ratio indicate that the organic matter of the source rocks had been deposited in reducing conditions. Despite the similarities in the organic matter source input and depositional environment of the organic matter of the samples from the two well, cross plots of Co/Ni versus V/Ni and Mo/Ni versus Co/Ni were able to reveal subtle differences. Cluster analysis of the samples was also able to reveal the subtle

  10. Sill intrusion driven fluid flow and vent formation in volcanic basins: Modeling rates of volatile release and paleoclimate effects

    Science.gov (United States)

    Iyer, Karthik; Schmid, Daniel

    2016-04-01

    main sill in the region. We use a 2D, hybrid FEM/FVM model that solves for fully compressible fluid flow to quantify the thermogenic release and transport of methane and to evaluate flow patterns within these systems. Additionally, vent formation in the model is implemented by simple fracture criteria that modify the permeability structure when the fluid pressure exceeds a threshold determined by the lithostatic pressure. The model with fracture formation is able to reproduce a single vent complex at the observed location above the main sill tip. This is very different from hydrothermal plume formation elsewhere in the region and occurs over short time scales (hundreds of years) and results in fluid focusing in that region. The rate of degassing and the resulting negative δ13C excursion from the vent model is then compared to models where only hydrothermal plume formation results in gas transportation. Lastly, variations in the amount of gas liberated in the system are investigated based on kerogen type and other mineral reactions such as limestone decarbonation and halite breakdown in the affected source rock.

  11. Complex resistivity spectra in relation to multiscale pore geometry in carbonates and mixed-siliciclastic rocks

    Science.gov (United States)

    Norbisrath, Jan Henrik

    Carbonate rocks are known to have complex and heterogeneous pore structures, which result from their biogenic origin and strong affinity for diagenetic processes that change their pore structure after burial. The combination of sheer endless variations of precursor biogenic material, depositional environments, and diagenetic effects results in rocks that are interesting to study but intricate to understand. Many schemes to categorize the diversity of carbonate rocks are in use today; most are based on the macropore structure and qualitative thin-section analysis. Many studies, however, acknowledge that micropores have a significant influence on the macroscopic petrophysical rock properties, which are essential to determine reservoir quality. Micropores are, by definition, smaller than the thickness of a thin-section (four major carbonate microporosity types: (1) small intercrystalline, (2) large inter-crystalline, (3) intercement, and (4) micromoldic. Each microporosity type shows a distinct capacity to conduct electrical charge, which largely controls the magnitude and range of cementation factors (m) in rocks with such microporosity type. The BIB-SEM method is also used on a dataset of mixed carbonate-siliciclastic (mudrock) samples with high kerogen and pyrite content. Results show that the nanopore geometry here has little influence on cementation factors, and instead porosity is the main control on m in mudrocks. Cementation factors are crucial for estimates of oil-in-place and water saturation in a wireline application, and a slight change of (assumed) cementation factor can change the interpreter's evaluation from dry hole to discovery. Therefore, accurate determination of cementation factors is a critical task in formation evaluation, similar to accurate estimates of permeability. To achieve this goal, this dissertation utilizes a new approach of using complex resistivity spectra (CRS) to assess the pore geometry and its resulting electrical and fluid flow

  12. 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

    incursions make up a greater deal of the sedimentary record than mangrove swamps. Terra rossa paleosols mark the end of accumulation of organic material (OM) and herald supratidal conditions at the passage of Rusayl Formation into the overlying Seeb Formation. In the subtidal-supratidal cycles of lithofacies unit VIII the terra rossa horizons are thining upwards and become gradually substituted for by deep-water middle ramp sediments of lithofacies unit IX. Framboidal pyrite, (ferroan) dolomite with very little siderite are indicative of an early diagenetic alteration stage I under rather moderate temperatures of formation. During a subsequent stage II, an increase in the temperature of alteration was partly induced by burial and a high heat flow from the underlying Semail Ophiolite. Type-III kerogen originating from higher plants and, in addition, some marine biota gave rise to the generation of small amounts of soluble organic matter during this stage of diagenesis. The average reflectance of humic particles marks the beginning of the oil window and the production index reveals the existence of free hydrocarbons. Further uplift of the Eocene strata and oxidation during stage IIII caused veins of satin spar to form from organic sulfur and pyrite in the carbonaceous material. Lowering of the pH value of the pore fluid led to the precipitation of jarosite and a set of hydrated aluminum sulfates dependant upon the cations present in the wall rocks. AMD minerals (= acid mine drainage) are not very widespread in this carbonaceous series intercalated among calcareous rocks owing to the buffering effect of carbonate minerals. These carbonate-hosted carbonaceous rocks are below an economic level as far as the mining of coal is concerned, but deserves particular attention as source rocks for hydrocarbons in the Middle East, provided a higher stage of maturity is reached. (author)

  13. Organic chemical composition of mud from the LUSI mud volcano, Sidoarjo, East Java, Indonesia

    Science.gov (United States)

    Rosenbauer, R. J.; Campbell, P.; Lam, A.

    2009-12-01

    Sidoarjo, East Java, Indonesia is the site of LUSI, a terrestrial mud volcano that has been erupting since May 29, 2006. In response to a U.S. Department of State request, the U.S. Geological Survey has been assisting the Indonesian Government to describe the geological and geochemical aspects and potential health risk of the mud eruption. We report here on the organic chemical composition of the mud. Organic chemical analyses were carried out by gas chromatography/mass spectroscopy following organic extraction by microwave-assisted solvent extraction and compound fractionation by adsorption chromatography. There is a petroliferous component in the mud that is fresh, immature, and nonbiodegraded. There is a complete suite of n-alkanes with a bell-shaped pattern typical of fresh petroleum with a Cmax around C20. The alkane content ranges from 0.12 to 1.01 mg/kg dry mud. The presence of certain hopanes (i.e. 17 α,21β(H)-30-norhopane and 17α,21β(H)-hopane) is also indicative of the presence of oil. The proportions of other biomarker compounds (pristane/phytane = 2.4) and the dominance of the C27 sterane (5α(H),14α(H),17α(H)-chlolestane) suggest that oil formed under oxic conditions and has a likely coastal marine or terrigenous source. The presence of oleanane indicates a Cretaceous or younger age for the petrogenic material. These geochemical parameters are consistent with Indonesian oil derived from Tertiary marlstone source rocks that contained kerogen deposited under oxic conditions, probably the upper Miocene Klasafet Formation. Polycyclic aromatic hydrocarbons (PAHs) are present and range in content from 0.1 to 2.2 mg/kg dry mud. The low molecular weight (LMW) PAHs, in particular, naphthalene and methyl-naphthalene are dominant except for perylene which is ubiquitous in the environment. The presence of both parent and higher homologue PAHs indicate a petrogenic rather than combustion source. PAHs are known carcinogens but toxicity data in sediments are

  14. The Bakken - An Unconventional Petroleum and Reservoir System

    Energy Technology Data Exchange (ETDEWEB)

    Sarg, J.

    2011-12-31

    effective stress as the Middle Bakken suggesting that the shale will not contain induced fractures, and will contribute hydrocarbons from interconnected micro-fractures. Organic-rich shale impedance increases with a reduction in porosity and an increase in kerogen stiffness during the burial maturation process. Maturation can be directly related to impedance, and should be seismically mappable. Fractures enhance permeability and production. Regional fractures form an orthogonal set with a dominant NE-SW trend, and a less prominent NW-SE trend. Many horizontal 1 direction to intersect these fractures. Local structures formed by basement tectonics or salt dissolution generate both hinge parallel and hinge oblique fractures that may overprint and dominate the regional fracture signature. Horizontal microfractures formed by oil expulsion in the Bakken shales, and connected and opened by hydrofracturing provide permeability pathways for oil flow into wells that have been hydro-fractured in the Middle Bakken lithofacies. Results from the lithofacies, mineral, and fracture analyses of this study were used to construct a dual porosity Petrel geo-model for a portion of the Elm Coulee Field. In this field, dolomitization enhances reservoir porosity and permeability. First year cumulative production helps locate areas of high well productivity and in deriving fracture swarm distribution. A fracture model was developed based on high productivity well distribution, and regional fracture distribution, and was combined with favorable matrix properties to build a dual porosity geo-model.

  15. The origin of the methane in deep aquifers of the Pannonian Basin

    International Nuclear Information System (INIS)

    Futo, I.; Svingor, E.; Szanto, Zs.

    2004-01-01

    Complete text of publication follows. Bacterial methanogenesis and thermally induced generation of gaseous and liquid hydrocarbons have long been considered as processes strictly separated in space and time [1]. As the compositional and isotopic analysis of the hydrocarbon gas (HC) became a routinely used technique in petroleum exploration, the beginning of thermal gas generation in relatively cold and immature strata was recognized [2]. The discovery of living bacteria at temperatures as high as 50-55 deg C implied that bacterial methane may be formed at temperatures considerably higher than previously supposed. The great number of water wells penetrating the deep aquifers of the hot Pannonian Basin, which is at the same time a mature petroleum province, offers a unique possibility for studying the spatial and temporal relationships between bacterial methanogenesis and thermal generation of HC gases. H and O isotope ratios of water and H and C isotope ratios of methane as well as the abundances of some major and minor dissolved components were measured in 26 subsurface waters from SE Hungary, produced from late Neogene aquifers within the upper two kilometers in depth [3]. The HC gas content of the great majority of the waters is dominated by isotopically light bacterial methane. The depth of the onset of thermal gas generation varies from 0.7 to 1.2 km but the amount of thermogenic methane leaving the kerogen was not sufficient to overprint the light isotopic signature of the methane in the waters. About two thirds of the waters are characterised by low sulfate content ( 20) and methane δD values less negative than - 260%. They also show a direct relationship between the H isotope ratio of the methane and that of the water. These waters experienced exhaustive bacterial sulfate reduction followed by a relatively shallow bacterial methanogenesis. The methanogens started to operate immediately after the sulfate content dropped below 0.1 mmol/l due to bacterial

  16. Oil generation potential assessment and paleoenvironmental interpretation based on bio markers and stable carbon isotopes of the Pliensbachian - lower Toarcian (Lower Jurassic) of the Peniche region (Lusitanian Basin, Portugal); Avaliacao do potencial gerador de petroleo e interpretacao paleoambiental com base em biomarcadores e isotopos estaveis de carbono da secao Pliensbaquiano - Toarciano inferior (Jurassico Inferior) da regiao de Peniche (Bacia Lusitanica, Portugal)

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Luiz Carlos Veiga de; Rodrigues, Rene; Duarte, Luis Vitor; Lemos, Valesca Brasil [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas (CENPES). Gerencia de Bioestratigrafia e Paleoecologia]. E-mail: lcveiga@petrobras.com.br

    2006-05-15

    The Lusitanian Basin (Portugal) is located on the western margin of the Iberian Plate with maximum sedimentary thickness around 5 km. In spite of containing promising petroleum systems and more than a hundred wells, its hydrocarbon generation potential has not been fully evaluated yet. These sediments range from upper Triassic to upper Cretaceous, mainly from the Jurassic age. The Lower Jurassic is particularly well represented in the Lusitanian Basin, specifically in the Peniche region, where there are more than 450 m thick outcrops of carbonate rocks aged between Sinemurian and Toarcian. This study presents the evaluation of the hydrocarbon generation potential of the Pliensbachian . lower Toarcian of the Peniche section; which includes the Vale das Fontes Formation, Lemede Formation and Cabo Carvoeiro Formation (CC1 and CC2 members) based on 233 rock samples analyzed for total organic carbon (TOC), Rock-Eval pyrolysis and bio markers. Available data of oxygen and carbon stable isotopes were also used in the paleoenvironmental interpretation. Marls and limestones with the bituminous facies (Mlbf) of the Vale das Fontes Formation, present the highest TOC values, up to 14.95%, corresponding to the ibex (upper part), davoei and margaritatus ammonites zones and part of the NJ4a and NJ4b nanno fossils bio zones (Pliensbachian). In thermal immature sections (T max about 430 deg C), this member also shows high S{sub 2} values (10 to 50 mgHC/g rock) and Hydrogen index (HI: 200 to 555 mgHC/g TOC). The correlation between HI x OI shows that type II kerogen is predominant in the portion of the section where TOC values are higher. The good positive correlation between TOC values and the bio markers ratio P/nC17 and sterane (C{sub 27}/C{sub 29}) throughout the Mlbf Member suggests a gradual increase of anoxia and higher contribution of algae in relation to terrestrial organic matter. Usually {delta}{sup 18}O variations observed in the basins of the Iberian Peninsula have been

  17. Experimental investigation of changes in methane adsorption of bitumen-free Woodford Shale with thermal maturation induced by hydrous pyrolysis

    Science.gov (United States)

    Hu, Haiyan; Zhang, Tongwei; Wiggins-Camacho, Jaclyn D.; Ellis, Geoffrey S.; Lewan, Michael D.; Zhang, Xiayong

    2014-01-01

    This study quantifies the effects of organic-matter (OM) thermal maturity on methane (CH4) sorption, on the basis of five samples that were artificially matured through hydrous pyrolysis achieved by heating samples of immature Woodford Shale under five different time–temperature conditions. CH4-sorption isotherms at 35 °C, 50 °C, and 65 °C, and pressures up to 14 MPa on dry, solvent-extracted samples of the artificially matured Woodford Shale were measured. The results showed that CH4-sorption capacity, normalized to TOC, varied with thermal maturity, following the trend: maximum oil (367 °C) > oil cracking (400 °C) > maximum bitumen/early oil (333 °C) > early bitumen (300 °C) > immature stage (130 °C). The Langmuir constants for the samples at maximum-oil and oil-cracking stages are larger than the values for the bitumen-forming stages. The total pore volume, determined by N2 physisorption at 77 K, increases with increased maturation: mesopores, 2–50 nm in width, were created during the thermal conversion of organic-matter and a dramatic increase in porosity appeared when maximum-bitumen and maximum-oil generation stages were reached. A linear relationship between thermal maturity and Brunauer–Emmett–Teller (BET) surface area suggests that the observed increase in CH4-sorption capacity may be the result of mesopores produced during OM conversion. No obvious difference is observed in pore-size distribution and pore volume for samples with pores 2 physisorption at 273 K. The isosteric heat of adsorption and the standard entropy for artificially matured samples ranged from 17.9 kJ mol−1 to 21.9 kJ mol−1 and from −85.4 J mol−1 K−1 to −101.8 J mol−1 K−1, respectively. These values are similar to the values of immature Woodford kerogen concentrate previously observed, but are larger than naturally matured organic-rich shales. High-temperature hydrous pyrolysis might have induced Lewis acid sites on both organic and mineral surfaces

  18. Organic petrology and geochemistry of mudrocks from the lacustrine Lucaogou Formation, Santanghu Basin, northwest China: Application to lake basin evolution

    Science.gov (United States)

    Hackley, Paul C.; Fishman, Neil; Wu, Tao; Baugher, Gregory

    2016-01-01

    Exploration for tight oil in the frontier Santanghu Basin of northwest China has resulted in recent commercial discoveries sourced from the lacustrine Upper Permian Lucaogou Formation, already considered a “world class source rock” in the Junggar Basin to the west. Here we apply an integrated analytical program to carbonate-dominated mudrocks from the Lucaogou Formation in Santanghu Basin to document the nature of organic matter (OM) in the context of an evolving lake system. The organic-rich samples (TOC 2.8–11.4 wt%; n = 10) were widely spaced from an ~ 200 m cored section, interpreted from textural and mineralogical evidence to document transition from a lower under-filled to an overlying balanced-filled lake. Organic matter is dominated by moderate to strongly fluorescent amorphous material with Type I geochemical signature (HI values 510–755; n = 10) occurring in a continuum from lamellar stringers, 10–20 μm thick, some ≥ 1 mm in length (possible microbial mat; preserved only in lower under-filled section) to finely-disseminated amorphous groundmass intimately intermixed with mineral matrix. Biomarkers for methanotrophs and photosynthetic cyanobacteria indicate a complex microbial consortium. A unicellular prasinophyte green alga(?), similar to Tasmanites in marine rocks, is present as discrete flattened discs 50–100 μm in diameter. Type III OM including vitrinite (some fluorescent) and inertinite also is abundant. Solid bitumen, indicating local kerogen conversion, fills voids and occurs throughout the cored section. Vitrinite reflectance values are 0.47–0.58%, consistent with strong OM fluorescence but may be “suppressed”. Other proxies, e.g., biomarker parameters, indicate the Lucaogou Formation is in the early oil window at this location. On average, slightly more amorphous OM and telalginite are present in the lower section, consistent with a shallow, stratified, saline environment with low sediment dilution. More

  19. Radiolytic alteration of biopolymers in the Mulga Rock (Australia) uranium deposit

    International Nuclear Information System (INIS)

    Jaraula, Caroline M.B.; Schwark, Lorenz; Moreau, Xavier; Pickel, Walter; Bagas, Leon; Grice, Kliti

    2015-01-01

    Highlights: • Bulk kerogen compositions indicate land plant sources for organic matter in the uranium deposit. • Radiolysis led to cleavage of straight long chain forming medium chain length n-alkyl moieties. • Secondary and tertiary reactions with OH − radicals promoted the formation of alkanones. • “Radiolytic molecular markers” imply molecular markers resulting from radiolytic cracking. • A mechanism is proposed for the production of n-alkanes and n-alkanones. - Abstract: We investigated the effect of ionizing radiation on organic matter (OM) in the carbonaceous uranium (U) mineralization at the Mulga Rock deposit, Western Australia. Samples were collected from mineralized layers between 53 and 58.5 m depths in the Ambassador prospect, containing <5300 ppm U. Uranium bears a close spatial relationship with OM, mostly finely interspersed in the attrinite matrix and via enrichments within liptinitic phytoclasts (mainly sporinite and liptodetrinite). Geochemical analyses were conducted to: (i) identify the natural sources of molecular markers, (ii) recognize relationships between molecular markers and U concentrations and (iii) detect radiolysis effects on molecular marker distributions. Carbon to nitrogen ratios between 82 and 153, and Rock–Eval pyrolysis yields of 316–577 mg hydrocarbon/g TOC (HI) and 70–102 mg CO 2 /g TOC (OI) indicate a predominantly lipid-rich terrigenous plant OM source deposited in a complex shallow swampy wetland or lacustrine environment. Saturated hydrocarbon and ketone fractions reveal molecular distributions co-varying with U concentration. In samples with <1700 ppm U concentrations, long-chain n-alkanes and alkanones (C 27 –C 31 ) reveal an odd/even carbon preference indicative of extant lipids. Samples with ⩾1700 ppm concentrations contain intermediate-length n-alkanes and alkanones, bearing a keto-group in position 2–10, with no carbon number preference. Such changes in molecular distributions are

  20. Evaluation quantitative des produits formés lors de l'évolution géochimique de la matière organique Quantitative Evaluation of Products Formed During the Geochemical Evolution of Organic Matter

    Directory of Open Access Journals (Sweden)

    Pelet R.

    2006-11-01

    Full Text Available L'évaluation quantitative des produits mobiles formés lors de l'évolution géochimique de la matière organique est nécessaire parce qu'on ne peut jamais retrouver ces produits en place dans. la roche où ils ont pris naissance. Ils ont, en effet, pu migrer durant l'histoire géologique, et de toute manière une fraction, importante et non connue, se perd lors de la prise des échantillons puis de leur conservation avant analyse. La connaissance de l'analyse d'un état E et d'un état plus évolué E' ne suffit pas pour reconstituer les quantités de produits formés. La pyrolyse type Rock-Eval sur kérogènes, avec détermination du carbone résiduel, permet par contre, à partir d'une hypothèse raisonnable, de calculer les hydrocarbures produits. L'analyse élémentaire permet d'y ajouter CO2, H2O, H2S et N2 (considérés comme seuls produits à côté des hydrocarbures. Une analyse chromatographique sommaire supplémentaire permet d'estimer la composition globale des hydrocarbures. Dans le cas des roches, on propose des techniques de correction de l'effet de matrice pratiquement utilisables et qui permettent de retrouver les résultats précédents, au prix d'une incertitude accrue. The mobile products formed during the geochemical evolution of organic matter must be quantitatively evaluated because these products can never be found in place in the rock where they were formed. Indeed, they may have migrated during geological history, and in any case a large and unknown fraction gets lost when samples are taken and then stored before being analysed. Knowing the elemental analysis of a state E and of a more evolved state E' does not suffice for recreating the amounts of products formed. On the other hand Rock-Eval type pyrolysis of kerogens, including the determination of the residual carbon, can be used to compute the hydrocarbons produced, on the basis of a reasonable hypothesis. Elemental analysis then enables the evaluation of CO2, H2O

  1. Estudio y clasificación de la materia orgánica dispersa (MOD en el Lías de la Playa de Peñarrubia (Asturias

    Directory of Open Access Journals (Sweden)

    González Prado, J. J.

    1990-04-01

    Full Text Available A study of the organic matter of a marine sequence of the west part from Peñarrubia Beach (Asturias has been carried out using pyrolysis tests and petrographic and geochemical techniques. White light and fluorescence microscopic observations have permitted to establish a general classification of the disperse organic matter, its distribution and concentration along the series, and also the variation with the litology. The organic components have been classified into nine groups which are mainly found in the Upper part of the Pliensbachian marlaceous and lutitic beds. These bituminous leveis are composed of a kerogen type 11 or mixed, with a small contribution of terrestrial humic materials. The rank of DOM has been determined by huminite reflectance and Rock-Eval (Tmax, being both results concordant. The DOM is in an inmature stage before the oil generation window. The highest oil yields determined by pyrolysis tests at 500°C correspond to the richest DOM levels. Petrographic and geochemical data show a good correlation. AIgae, fibers, organic-mineral matrix and other submicroscopic associations are the main source for oil generation.En el presente trabajo se estudia por técnicas petrográficas y mediante ensayos de pirólisis o técnicas geoquímicas la serie marina del borde Oeste de la Playa de Peñarrubia (Asturias para conocer la naturaleza de su parte orgánica. Las observaciones microscópicas en luz blanca y por fluorescencia han permitido establecer una clasificación general de la materia orgánica dispersa, su distribución y concentración a lo largo de toda la serie y según las diferentes litologías. Se han clasificado los componentes orgánicos en 9 grupos mayoritarios que se concentran, principalmente en los niveles margosos y lutíticos del Pliensbachiense, habiéndose delimitado niveles bituminosos en la parte superior de la serie. Estos están constituidos por un kerógeno de tipo 11 mixto formado por un material aut

  2. L'evolution thermique de la matière organique des sédiments : applications d'une simulation mathématique. Potentiel pétrolier des bassins sédimentaires de reconstitution de l'histoire thermique des sédiments Thermal Evolution of Organic Matter in Sediments : Application of a Mathematical Simulation. Petrleum Potential of Sedimentary Basins and Reconstructing the Thermal History of Sediments

    Directory of Open Access Journals (Sweden)

    Tissot B.

    2006-11-01

    particular discusses the distribution of activation energies and its significance in relation to the composition of the kerogen. The other data required are the geological reconstruction of burial and the geothermal gradient. The reconstruction of ancient geothermics raises a special problem. By combining the measurement of vitrinite reflectance and the law of burial, a vitrinite évolution model con be used in most cases to reestablish the thermal history of the organic motter. This is of course of great interest for petroleum prospection, but its range of application goes far beyond this field and reaches all the way to problems of general geology such as geothermics, sediment diagenesis, global tectonics, etc.

  3. Thermal alterations of organic matter in coal wastes from Upper Silesia, Poland

    Science.gov (United States)

    Misz-Kennan, Magdalena

    2010-01-01

    lacking suggests that they originated elsewhere and subsequently migrated through the dump piles. During their migration, the compounds fractionated, were adsorbed on minerals and/or interacted. The absence of alkenes, and of other unsaturated organic compounds, may reflect primary diagenetic processes that occurred in coals and coal shales during burial and/or organic matter type. Their absence may also be a consequence of heating that lasted many years, hydropyrolysis, and/or the participation of minerals in the reactions occurring within the dumps. The wastes contain compounds typical of organic matter of unaltered kerogen III type and the products of pyrolytic processes, and mixtures of both. In some wastes, organic compounds are completely absent having been destroyed by severe heating. The distributions of n-alkanes in many samples are typical of pyrolysates. In some wastes, narrow n-alkane distributions reflect their generation over small temperature ranges. In others, wider distributions point to greater temperature ranges. Other wastes contain n-alkane distributions typical of unaltered coal and high pristane content or mixtures of pyrolysates and unaltered waste material. The wastes also contain significant amounts of final αβ hopanes. Polycyclic aromatic hydrocarbons are represented only by two- to five-ring compounds as is typical of the thermal alteration of hard coal. Correlations between the degree of organic matter alteration and the relative contents of individual PAHs and hopanes and geochemical indicators of thermal alteration are generally poor. The properties of the organic matter (its composition and rank), temperature fluctuations within the dumps, migration of organic compounds and mineral involvement are probably responsible for this. The processes taking place in coal waste dumps undergoing self-heating and self-combustion are complicated; they are very difficult to estimate and define. The methods of organic petrology and geochemistry give

  4. On-site investigations of hydrocarbon contaminated soil by the Pollut-Eval methodology

    International Nuclear Information System (INIS)

    Benoit, Y.; Prigent, S.; Haeseler, F.

    2005-01-01

    The Pollut-Eval method is based on the Rock-Eval pyrolysis method, founded on an IFP patent that has been used for decades for oil prospecting in sedimentary basins all over the world. This equipment provides data on the quantity and the quality of organic matter in sedimentary rocks. With the increasing demand for cost effective and rapid contaminated site diagnosis, it became obvious that the field of application of the Rock-Eval technology should be enlarged to environmental problematic. The Pollut-Eval methodology was developed since 1996 and firstly qualified through the design of a laboratory version. Compared to the previous apparatus dedicated to the geochemistry, innovations allow acquisition of data for accurate quantification of complex organic pollutants and mineral carbon distribution. New methods were developed especially for the characterisation of hydrocarbon pollutants in soil. Compared to kerogen analysis, the characterisation of light petroleum cuts entrapped in soil as pollutants was available by the design of an adapted refrigerated auto-sampler. The prevention of the loss of the high vapour tension pollutants couldn't be avoided for the new environmental field of applications. Site after site, the various experiments involving the 'laboratory' version of the Pollut-Eval analyser extended the application field of the methodology. The efficiency of the thermal extraction applied directly on the soil showed useful advantages compared to conventional solvent extraction techniques, especially for pollutants originating from former gas plants. The method was especially suitable for the determination of the complete carbon mass balance in the case of non-extractable organic pollutant such as coal tar or for heavy petroleum cut such as heavy fuel, vacuum distillation residue and bitumen. By the way, the Pollut-Eval method became rapidly complementary to more conventional GC quantification dedicated to complex organic pollution characterisation. By the

  5. The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope and Water Chemistry Characterizations

    Science.gov (United States)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.; Romanek, Christopher; Datta, Saugata; Darnell, Mike; Bissada, Adry K.

    2013-01-01

    estimated by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 C, and higher than the values measured at orifices (77.3 to 90.0 C). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The C-13 fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 C) is suggested as being responsible for the generation of CO2 in SVHS.

  6. The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope aud Water Chemistry Characterizations

    Science.gov (United States)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.; Romanek, Christopher; Datta, Saugata; Darnell, Mike; Bissada, Adry K.

    2013-01-01

    by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 oC, and higher than the values measured at orifices (77.3 to 90.0 oC). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The 13C fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 oC) is suggested as being responsible for the generation of CO2 in SVHS.

  7. Organic geochemical characteristics and paleoclimate conditions of the Miocene coals at the Çan-Durali (Çanakkale)

    Science.gov (United States)

    Hoş-Çebi, Fatma

    2017-05-01

    In this study, n-alkane and isoprenoid, saturated and aromatic biomarker distributions of Miocene coals in the Çan (Çanakkale) region, were studied to investigate organic geochemical characteristics, depositional environment, and hydrocarbon potential of these coals. Çan formation (Middle Miocene) unconformably overlies the basement Çan volcanites (Upper Oligocene-Lower Miocene). This formation is composed of lignite, clayey lignite, and ligniferous clayey levels of various thicknesses interlayering with clay and tuffite. The formation represents sediments of small lacustrine basins that are isolated by faults that are formed contemporaneously with Early-Middle Eocene volcanism. Coaliferous units are overlain by lower agglomerate levels. The Rock Eval analyses show that the average TOC (Total Organic Carbon) content of the coal is 53.71% and the average HI (Hydrogen Index) value is 180.5 mgHC/gTOC. OI (Oxygen Index) values (avg. 22.33 mgCO2/gTOC) show that the depositional environment of peat deposits is suboxic. According to HI-Tmax, S2-TOC classification diagrams and Pr/n-C17vs. Ph/n-C18 diagram, the organic matter is composed of Type II and Type III kerogen mixing and represents a transitional environment. In gas chromatograms, n-alkanes with high, mostly odd-numbered carbons are dominant and they are associated with a slight algal contribution. CPI22-30 (Carbon Preference Index) and TARHC (Terrigenous/Aquatic Ratio) values indicate a dominance of high-carbon numbered n-alkanes, indicating the presence of terrestrial organic matter. Paq (aquatic plant n-alkane proxy) values (0.2; 0.3) indicate a climate with relatively wet conditions or low precipitation, the presence of emergent macrophyteses, and the scarcity of hydrophilic plants. Pwax (vascular plant n-alkane proxy) ratio (0.8; 0.7) shows moderately wet conditions and a relatively low water level. The TOC, ACL (n-alkane average chain length), Qwood/grass, Qwood/plant, and Qgrass/plant values indicate the

  8. The Boron Isotopic Composition of Elephant Dung: Inputs to the Global Boron Budget

    Science.gov (United States)

    Williams, L. B.; Hervig, R. L.

    2011-12-01

    A survey of boron in kerogen showed isotopically light δ11B values (0 to -50%) that are distinctly different from most mineral and natural water B reservoirs. Diagenesis releases this isotopically light B into pore fluids when hydrocarbons are generated, thus enriching oilfield brines in 10B. This observation suggests that borated biomolecules (BM) are primarily tetrahedral favoring 10B, whereas 11B is preferred in trigonal coordination. Plants, with optimal concentrations up to 100ppm, contribute more B than animal remains to sediment. Elephants are one of the largest herbivores on earth, consuming 200 - 250 kg of plant material/day and producing 50 kg of manure/day. They are inefficient at digestion, thus the manure contains >50% undigested plant material. Dung samples are therefore ideal for studying the δ11B of both the food input and digested output of a significant B supply to sedimentary systems. Horse and rabbit manure were studied for comparison to evaluate B isotope variations in the food supply and potential vital effects on the output. B-content and isotopic composition of dung plant material and digested fractions were measured in the solid state by secondary ion mass spectrometry. The digests were rinsed in 1.8% mannitol, a B-complexing agent, to remove surface adsorbed-B, then air dried and Au-coated for charge compensation. Results showed that the elephant diet contains 3-13 ppm B, with an average δ11B of -20 ± 0.8% (1σ), while rabbit food had 88 ppm B with a δ11B of -50 ± 1.3 %. The digested fraction of the elephant dung contains 4-10ppm B with average δ11B values of -12 ± 1.2%. In comparison, horse manure with 11-21 ppm B has a δ11B of -10.7 ± 0.5% and rabbit manure contains 2-3 ppm B with a δ11B of -8.8 ± 1%. Boron isotope compositions of these manures are indistinguishable (within error). Clearly plant material is a major contributor of isotopically light B to sediments. The herbivores studied fractionate their total B intake in

  9. NATURAL GAS RESOURCES IN DEEP SEDIMENTARY BASINS

    Energy Technology Data Exchange (ETDEWEB)

    Thaddeus S. Dyman; Troy Cook; Robert A. Crovelli; Allison A. Henry; Timothy C. Hester; Ronald C. Johnson; Michael D. Lewan; Vito F. Nuccio; James W. Schmoker; Dennis B. Riggin; Christopher J. Schenk

    2002-02-05

    From a geological perspective, deep natural gas resources are generally defined as resources occurring in reservoirs at or below 15,000 feet, whereas ultra-deep gas occurs below 25,000 feet. From an operational point of view, ''deep'' is often thought of in a relative sense based on the geologic and engineering knowledge of gas (and oil) resources in a particular area. Deep gas can be found in either conventionally-trapped or unconventional basin-center accumulations that are essentially large single fields having spatial dimensions often exceeding those of conventional fields. Exploration for deep conventional and unconventional basin-center natural gas resources deserves special attention because these resources are widespread and occur in diverse geologic environments. In 1995, the U.S. Geological Survey estimated that 939 TCF of technically recoverable natural gas remained to be discovered or was part of reserve appreciation from known fields in the onshore areas and State waters of the United. Of this USGS resource, nearly 114 trillion cubic feet (Tcf) of technically-recoverable gas remains to be discovered from deep sedimentary basins. Worldwide estimates of deep gas are also high. The U.S. Geological Survey World Petroleum Assessment 2000 Project recently estimated a world mean undiscovered conventional gas resource outside the U.S. of 844 Tcf below 4.5 km (about 15,000 feet). Less is known about the origins of deep gas than about the origins of gas at shallower depths because fewer wells have been drilled into the deeper portions of many basins. Some of the many factors contributing to the origin of deep gas include the thermal stability of methane, the role of water and non-hydrocarbon gases in natural gas generation, porosity loss with increasing thermal maturity, the kinetics of deep gas generation, thermal cracking of oil to gas, and source rock potential based on thermal maturity and kerogen type. Recent experimental simulations

  10. Distinguishing "new" from "old" carbon in post mining soils

    Science.gov (United States)

    Vindušková, Olga; Frouz, Jan

    2014-05-01

    Introduction Soils developing on heaped overburden after open pit coal mining near Sokolov, Czech Republic, provide an exceptional opportunity to study sites of different ages (0-70 years) developing on similar substrate under relatively well-known conditions. Soil organic carbon (SOC) is an useful indicator of soil quality and represents an important global carbon pool. Post-mining soils would be a perfect model for long-term study of carbon dynamics. Unfortunately, quantifying SOC in Sokolov post-mining soils is quite complicated, since conventional quantification methods cannot distinguish between SOC derived from plant residues and fossil organic carbon derived from coal and kerogen present in the overburden. Moreover, also inorganic carbon may sometimes bias SOC quantification. Up to now, the only way to directly estimate recently derived SOC in these soils is radiocarbon dating (Rumpel et al. 1999; Karu et al. 2009). However, this method is costly and thus cannot be used routinely. The aim of our study is to find an accessible method to quantify recently derived SOC. We would highly appreciate ideas of other soil scientists, organic geochemists and sedimentologists on how to solve this challenge. Methods and hypotheses A set of 14 soil samples were analysed by radiocarbon (14C-AMS) analysis, near-infrared spectroscopy (NIRS), 13C CPMAS NMR spectroscopy, Rock-Eval and XRD. For calibration of NIRS, also 125 artificial mixtures were produced by mixing different amounts of claystone, coal and partially decomposed litter. NIRS (1000-2500 nm) as well as younger mid-infrared spectroscopy has been widely applied to soils (Janik et al. 2007; Vasques et al. 2009; Michel et al. 2009). When combined with multivariate chemometric techniques, it can be used to predict concentration of different compounds. No study has yet focused on NIRS application to soils where fossil carbon is found in two chemically different forms - whereas coal is rather aromatic, kerogen in our

  11. La pyrolyse Rock-Eval et ses applications. Deuxième partie. Rock-Eval Pyrolysis and Its Applications (Part Two

    Directory of Open Access Journals (Sweden)

    Espitalie J.

    2006-11-01

    techniques du raffinage et de la récupération secondaire des bruts. The Rock-Eval pyrolysis method was designed to meet the needs of petroleum prospection and has now gained widespread use. It quickly provides different data on the organic content of rocks, such as the petroleum potential of series encountered, the nature of kerogens and their state of maturity. Two new versions of this equipment have been developed by Institut Français du Pétrole (IFP since the appearance of the first Rock-Eval devices in 1977. One is a Rock-Eval II that is completely automated thanks to its microprocessor and is also equipped with a module for determining the organic-carbon content. The other is a Rock-Eval III (Oil Show Analyzer which is different from the preceding one in that it makes a separate analysis of gas and oil as well as determining the organic-carbon content in place of peak S3. Concerning the interpretation of the method, experience gained both by applications to sedimentary basins and by experimental investigations in the laboratory has provided a better understanding of the parameters used (peaks S1, S2 and S3, pyrolysis temperature Tmax through their variations and, from this, better insight into the application limits of the method. Concerning the application of the method, the vertical representation of results in the form of geochemical logs leads to an interpretation that is both effective and practical. Reference charts and diagrams are used to characterize source rocks (petroleum potentials, types of organic matter, degree of evolution, weathering, etc. as well as migration phenomena. The compiling of geochemical maps on a basin-wide scale then becomes possible. Likewise, the method has left the field of petroleum prospection per se and found applications in the analyzing of coals, bituminous rocks, recent sediments and even techniques of the refining and secondary recovery of crude oils.

  12. La pyrolyse Rock-Eval et ses applications. Troisième partie. Rock-Eval Pyrolysis and Its Applications (Part Three

    Directory of Open Access Journals (Sweden)

    Espitalie J.

    2006-11-01

    techniques du raffinage et de la récupération secondaire des bruts. The Rock-Eval pyrolysis method was designed to meet the needs of petroleum prospection and has now gained widespread use. It quickly provides different data on the organic content of rocks, such as the petroleum potential of series encountered, the nature of kerogens and their state of maturity. Two new versions of this equipment have been developed by Institut Français du Pétrole (IFP since the appearance of the first Rock-Eval devices in 1977. One is a Rock-Eval II that is completely automated thanks to its microprocessor and is also equipped with a module for determining the organic-carbon content. The other is a Rock-Eval III (Oil Show Analyzer which is different from the preceding one in that it makes a separate analysis of gas and oil as well as determining the organic-carbon content in place of peak S3. Concerning the interpretation of the method, experience gained both by applications to sedimentary basins and by experimental investigations in the laboratory has provided a better understanding of the parameters used (peaks S1, S2 and S3, pyrolysis temperature Tmax through their variations and, from this, better insight into the application limits of the method. Concerning the application of the method, the vertical representation of results in the form of geochemical logs leads to an interpretation that is both effective and practical. Reference charts and diagrams are used to characterize source rocks (petroleum potentials, types of organic matter, degree of evolution, weathering, etc. as well as migration phenomena. The compiling of geochemical maps on a basin-wide scale then becomes possible. Likewise, the method has left the field of petroleum prospection per se and found applications in the analyzing of coals, bituminous rocks, recent sediments and even techniques of the refining and secondary recovery of crude oils.

  13. La pyrolyse Rock-Eval et ses applications. Première partie. Rock-Eval Pyrolysis and Its Applications (Part One

    Directory of Open Access Journals (Sweden)

    Espitalie J.

    2006-11-01

    techniques du raffinage et de la récupération secondaire des bruts. The Rock-Eval pyrolysis method was designed to meet the needs of petroleum prospection and has now gained widespread use. It quickly provides different data on the organic content of rocks, such as the petroleum potential of series encountered, the nature of kerogens and their state of maturity. Two new versions of this equipment have been developed by Institut Français du Pétrole (IFP since the appearance of the first Rock-Eval devices in 1977. One is a Rock-Eval II that is completely automated thanks to its microprocessor and is also equipped with a module for determining the organic-carbon content. The other is a Rock-Eval III (Oil Show Analyzer which is different from the preceding one in that it makes a separate analysis of gas and oil as well as determining the organic-carbon content in place of peak S3. Concerning the interpretation of the method, experience gained both by applications to sedimentary basins and by experimental investigations in the laboratory has provided a better understanding of the parameters used (peaks S1, S2 and S3, pyrolysis temperature Tmax through their variations and, from this, better insight into the application limits of the method. Concerning the application of the method, the vertical representation of results in the form of geochemical logs leads to an interpretation that is both effective and practical. Reference charts and diagrams are used to characterize source rocks (petroleum potentials, types of organic matter, degree of evolution, weathering, etc. as well as migration phenomena. The compiling of geochemical maps on a basin-wide scale then becomes possible. Likewise, the method has left the field of petroleum prospection per se and found applications in the analyzing of coals, bituminous rocks, recent sediments and even techniques of the refining and secondary recovery of crude oils.

  14. La migration des hydrocarbures dans les bassins sédimentaires: aspects géologiques et géochimiques Migration of Hydrocarbons in Sedimentary Basins: Geological and Geochemical Aspects

    Directory of Open Access Journals (Sweden)

    Tissot B. P.

    2006-11-01

    expulsion from the source rock where it was formed (primary migration, has long remained one of the least well understood problems in all petroleum geology. The displacement of oil and gas occurs in a separate hydrocarbon phase. Water, which is often considered as the vehicle for oil during migration, effectively plays a negative role. Water saturation must have been sufficiently diminished (by expulsion and hydrocarbon saturation must be sufficiently increased (by generation from kerogen for the flow of a hydrocarbon phase to become possible. The driving force for this expulsion is the pressure gradient. A rise in pressure in the pore volume of source rocks results from three causes (the sedimentary load, the formation of hydrocarbons, and the thermal expansion of water. Microfracturing, which occurs when the internal pressure of fluids exceeds the mechanical strength of the rock, may play an important role. Observations of well documented cases in sedimentary basins are still too rare. In particular, it is difficult to compute the reserves mobilized on the scale of a permit or basin. The numerical modeling of migration combined with that of the formation of oil and gas opens up perspectives in this direction, but it still requires further work. Among the consequences of migration, mention can be made of the possibility of oil/source-rock correlation, the lower content of heavy products in reservoirs than in source rocks, and the role often played by a displacement in which liquid and gaseous hydrocarbons form a single phase that migrates while progressively leaving the heavier fractions behind it, by retrograde condensation.

  15. Non disturbing characterization and quantification of natural organic matter (NOM) contained in clay rock pore water by mass spectrometry using electro-spray and atmospheric pressure chemical ionization modes

    International Nuclear Information System (INIS)

    Huclier-Markai, S.; Landesman, C.; Grambow, B.; Rogniaux, H.; Monteau, F.; Vinsot, A.

    2010-01-01

    Document available in extended abstract form only. The Callovo-Oxfordian formation (COx) rock may contain up to 1% w/w of organic Carbon. Most of the Organic Matter (OM) is attached to the mineral particles whereas a small portion is present as Dissolved Organic Matter (DOM) in the pore water. In environmental studies, Natural Organic Matter (NOM) plays a key role on the bioavailability and the toxicity of metallic compounds. It is necessary to know the structure of any organic substance in order to assess which chemical and biological reactions occur under environmentally relevant conditions. The 150 Myears solid-bound organic matter of the COx (kerogen) has been already investigated in several studies and originates from a mixture of marine and terrestrial sources. In addition to this, the CCl 4 soluble organic fraction (bitumen) has been already characterized by liquid and gas chromatography coupled to mass spectrometry. It allows proportion and distribution of biological markers to be determined as polar compounds with aromatic and saturated hydrocarbons. DOM was extracted from a crushed clay rock of the COx formation with a high rock/water ratio of about 1500 g/L. Part of the OM from the COx is known to be sensitive to air oxidation which can significantly modify the nature of the bitumen by an overall shift towards lower molecular weight compounds. Therefore, the characteristics of the DOM must be determined in in-situ like conditions if one wants to assess the mobility of DOM in the clay pore space and to evaluate the mobility of heavy metals/ radionuclides. Due to their high binding capacity with metal ions and their colloidal sizes in natural waters, these macromolecules, through complexation reactions, might either enhance the mobility of trace elements, or reduce their migration rates by sorption processes in relation with their size and that of the porous medium. Consequently, the characterization of DOM in anoxic pore water samples from the COx

  16. Space-weathering processes and products on volatile-rich asteroids

    Science.gov (United States)

    Britt, D.; Schelling, P.; Consolmagno, G.; Bradley, T.

    2014-07-01

    recombine with available solar-wind-implanted hydrogen to form trace amounts of water and OH. Mineral decomposition can be thought of as the first stage of space weathering. It produces weathered surfaces somewhat depleted in volatile elements, creates a predictable set of minor or trace minerals, and leaves the surfaces with catalytic species, primarily npFe0. However, a second stage of further reactions and weathering depends upon the presence of ''feed-stock'' components that can participate in catalyzed chemical reactions on exposed surfaces. For volatile-rich small bodies, the available materials are not only silicates, but a volatile feedstock that can include water, carbon monoxide, ammonia, to name a few. Thermodynamically-driven decomposition of silicates will produce trace amounts of npFe0 which are ideal sites for Fischer-Tropsch type (FTT) catalytic reactions that can produce organics in situ on the asteroids including alkanes, polyaromatic hydrocarbons, and amino acids (J.E. Elsila, 2012, MAPS 47). The mix and range of products depends on the composition and morphology of the mineral surface, energy inputs produced by the micrometeorite impacts or other processes, and the composition of the input volatile feedstock. FFT reactions generate long-chain carbon compounds and amino acids. Secondary reactions that generate more complex carbon compounds and amino acids are likely to occur as the organic material matures. Weathering maturity can be thought of as a function of the abundance and diversity of the weathering products. Since the npFe0 is not destroyed in the reaction, continued micrometeorite bombardment would result in continuing processing and recombination of the existing organic feedstock. More weathering would result in progressively longer-chain carbon compounds as well as more complex and diverse amino acids, and eventually the kerogen-like insoluble-organic matter that forms a large fraction of carbonaceous meteorites. This insight has several major

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

    Science.gov (United States)

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

    1983-01-01

    The Parachute Creek Member of the lacustrine Green River Formation contains thick sequences of rich oil-shale. The richest sequence and the richest oil-shale bed occurring in the member are called the Mahogany zone and the Mahogany bed, respectively, and were deposited in ancient Lake Uinta. The name "Mahogany" is derived from the red-brown color imparted to the rock by its rich-kerogen content. Geochemical abundance and distribution of eight major and 18 trace elements were determined in the Mahogany zone sampled from two cores, U. S. Geological Survey core hole CR-2 and U. S. Bureau of Mines core hole O1-A (Figure 1). The oil shale from core hole CR-2 was deposited nearer the margin of Lake Uinta than oil shale from core hole O1-A. The major- and trace-element chemistry of the Mahogany zone from each of these two cores is compared using elemental abundances and Q-mode factor modeling. The results of chemical analyses of 44 CR-2 Mahogany samples and 76 O1-A Mahogany samples are summarized in Figure 2. The average geochemical abundances for shale (1) and black shale (2) are also plotted on Figure 2 for comparison. The elemental abundances in the samples from the two cores are similar for the majority of elements. Differences at the 95% probability level are higher concentrations of Ca, Cu, La, Ni, Sc and Zr in the samples from core hole CR-2 compared to samples from core hole O1-A and higher concentrations of As and Sr in samples from core hole O1-A compared to samples from core hole CR-2. These differences presumably reflect slight differences in depositional conditions or source material at the two sites. The Mahogany oil shale from the two cores has lower concentrations of most trace metals and higher concentrations of carbonate-related elements (Ca, Mg, Sr and Na) compared to the average shale and black shale. During deposition of the Mahogany oil shale, large quantities of carbonates were precipitated resulting in the enrichment of carbonate-related elements

  18. Geochemistry and mineralogy

    Energy Technology Data Exchange (ETDEWEB)

    Plecas, I.; Dimovic, S.; Orta, M.M.; Alba, M.D.; Alvero, R.; Becerro, A.I.; Castro, M.A.; Chain, P.; Escudero, A.; Naranjo, M.; Pavon, E.; Trillo, J.M.; Vejsada, J.; Vokal, A.; Zadvernyuk, H.P.; Fedorenko, Y.G.; Zlobenko, B.P.; Koromyslichenko, T.I.; Battaglia, S.; Cervelli, M.; Millot, R.; Girard, J.P.; Missana, T.; Garcia-Gutierrez, M.; Alonso, U.; Muurinen, A.; Carlsson, T.; Chain, P.; Alba, M.D.; Becerro, A.I.; Castro, M.A.; Escudero, A.; Gonzalez-Carrascosa, T.; Hurtado, S.; Pavon, E.; Villa, M.; Bourg, I.C.; Sposito, G.; Bourg, A.C.M.; Marques Fernandes, M.; Rabung, Th.; Dahn, R.; Baeyens, B.; Bradbury, M.H.; Breynaert, E.; Maes, A.; Bruggeman, C.; Maes, I.A.; Vancluysen, J.; Credoz, A.; Bildstein, O.; Jullien, M.; Raynal, J.; Petronin, J.C.; Trotignon, L.; Pokrovsky, O.; Jacquier, P.; Beaucaire, C.; Vuillaume, A.L.; Wittebroodt, Ch.; Ly, J.; Page, J.; Savoye, S.; Pitsch, H.; Jacques, D.; Wang, L.; Galunin, E.; Chain, P.; Alba, M.D.; Vidal, M.; Grandia, F.; Domenech, C.; Arcos, D.; Duro, L.; Bruno, J.; Andre, L.; Pauwels, H.; Azaroual, M.; Albrecht, A.; Romero, M.A.; Aerts, S.; Boven, P.; Van Geet, M.; Boever, P. de; Alonso, U.; Albarran, N.; Missana, T.; Garcia-Gutierrez, M.; Truche, L.; Berger, G.; Guillaume, D.; Jacquot, E.; Tournassat, Ch.; Lerouge, C.; Brendle, J.; Greneche, J.M.; Touzelet, St.; Blanc, Ph.; Gaucher, E.C.; Thoenen, T.; Klinkenberg, M.; Kaufhold, S.; Dohrmann, R.; Siegesmund, S.; Liu, D.J.; Bruggeman, C.; Maes, N.; Weber, T.; Trotignon, L.; Pozo, C.; Bildstein, O.; Combarieu, G. de; Frugier, P.; Menut, D

    2007-07-01

    Na- and Ca- Montmorillonite; the effect of temperature on the proton charge of Montmorillonite; the transformation of organic matter in the presence of smectite: fate of lanthanides during polymerization reactions; a surface complexation modelling using multi-components approach: sorption of selenium on argilite; the in-situ characterization of the Callovo- Oxfordian pore water composition; the natural organic matter fractionation on mineral surfaces: a spectroscopic approach; an examination of clay minerals-organic matter interactions at submicron-scale during confined pyrolysis of a simplified system Volclay bentonite -type II kerogen; the sorption of Np(v), U(vi) and Cs onto bentonite and clayey soils; the PHREEQC / traces coupling tool within the ALLIANCEs platform; is pore water close to the surfaces of a clay rock enriched in heavy water isotopes as compared to free pore water?; the ageing effect on the chemical and isotopic (Sr and Ar) characteristics of cored Mont Terri Opalinus Clays; the effect of concentration of the couples of Cation (Cu{sup 2+}, Pb{sup 2+}) on the natural selectivity phenomena in the case of Na-Montmorillonite: qualitative XRD analysis; and a qualitative study of synthetic Na- Hectorite saturated by heavy metals cations.

  19. Low Energy Electrons as Probing Tool for Astrochemical Reaction Mechanisms

    Science.gov (United States)

    Hendrik Bredehöft, Jan; Swiderek, Petra; Hamann, Thorben

    The complexity of molecules found in space varies widely. On one end of the scale of molecular complexity is the hydrogen molecule H2 . Its formation from H atoms is if not understood than at least thoroughly investigated[1]. On the other side of said spectrum the precursors to biopolymers can be found, such as amino acids[2,3], sugars[4], lipids, cofactors[5], etc, and the kerogen-like organic polymer material in carbonaceous meteorites called "black stuff" [6]. These have also received broad attention in the last decades. Sitting in the middle between these two extremes are simple molecules that are observed by radio astronomy throughout the Universe. These are molecules like methane (CH4 ), methanol (CH3 OH), formaldehyde (CH2 O), hydrogen cyanide (HCN), and many many others. So far more than 40 such species have been identified.[7] They are often used in laboratory experiments to create larger complex molecules on the surface of simulated interstellar dust grains.[2,8] The mechanisms of formation of these observed starting materials for prebiotic chemistry is however not always clear. Also the exact mechanisms of formation of larger molecules in photochemical experiments are largely unclear. This is mostly due to the very complex chemistry going on which involves many different radicals and ions. The creation of radicals and ions can be studied in detail in laboratory simulations. They can be created in a setup mimicking interstellar grain chemistry using slow electrons. There is no free electron radiation in space. What can be found though is a lot of radiation of different sorts. There is electromagnetic radiation (UV light, X-Rays, rays, etc.) and there is particulate radiation as well in the form of high energy ions. This radiation can provide energy that drives chemical reactions in the ice mantles of interstellar dust grains. And while the multitude of different kinds of radiation might be a little confusing, they all have one thing in common: Upon