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

PubMed

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.

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

NASA Technical Reports Server (NTRS)

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.

D/H ratios and hydrogen exchangeability of type-II kerogens with increasing thermal maturity

USGS Publications Warehouse

Lis, G.P.; Schimmelmann, A.; Mastalerz, Maria

2006-01-01

Stable isotope ratios of non-exchangeable hydrogen (??Dn) and of carbon were measured in type-II kerogens from two suites of Late Devonian to Early Mississippian black shale, one from the New Albany Shale (Illinois Basin) and the other from the Exshaw Formation (Alberta Basin). The largely marine-derived organic matter had similar original stable isotope ratios, but today the suites of kerogens express gradients in thermal maturity that have altered their chemical and isotopic compositions. In both suites, ??D n values increase with maturation up to a vitrinite reflectance of Ro 1.5%, then level out. Increasing ??Dn values suggest isotopic exchange of organic hydrogen with water-derived deuterium and/or preferential loss of 1H-enriched chemical moieties from kerogen during maturation. The resulting changes in ??Dn values are altering the original hydrogen isotopic paleoenvironmental signal in kerogen, albeit in a systematic fashion. The specific D/H response of each kerogen suite through maturation correlates with H/C elemental ratio and can therefore be corrected to yield paleoenvironmentally relevant information for a calibrated system. With increasing thermal maturity, the abundance of hydrogen in the kerogen that is isotopically exchangeable with water hydrogen (expressed as Hex, in % of total hydrogen) first decreases to reach a minimum at Ro ??? 0.8-1.1%, followed by a substantial increase at higher thermal maturity. ?? 2005 Elsevier Ltd. All rights reserved.

Geochemistry of the alginite and amorphous organic matter from type II-S kerogens

USGS Publications Warehouse

Stankiewicz, B.A.; Kruge, M.A.; Mastalerz, Maria; Salmon, G.L.

1996-01-01

Maceral fractions of the Type II-S kerogens from the Monterey Formation (Miocene. California. U.S.A.) and Duwi Formation (Campanian/Maastrichtian, Egypt) were separated by density gradient centrifugation. The Monterey Fm. kerogen sample was comprised chiefly of light red-fluorescing amorphous organic matter (AOM), the flash pyrolyzate of which was characterized by a predominance of alkylbenzenes, alkylthiophenes and alkylpyrroles. In contrast, the pyrolyzates of its alginite concentrate showed a highly aliphatic character, typical of this maceral, with the series of n-alkenes and n-alkanes (C6- C26) predominating. The pyrolyzate of the dominant light brown-fluorescing AOM of the Duwi Fm. kerogen had a relatively high concentration of alkylbenzenes and alkylthiophenes, while its elginite concentrate showed a more aliphatic character upon pyrolysis. There was a marked enrichment of thiophenic sulfur in the light-colored AOM of both samples (and also pyrrolic nitrogen in the case of the Monterey) relative to the alginite. The results support a bacterially-mediated, degradative origin for Type II-S amorphous organic matter, with algal remains as the primary source of the kerogen.

Estimation of porphyrin concentration in the kerogen fraction of shales using high-resolution reflectance spectroscopy

NASA Technical Reports Server (NTRS)

Holden, Peter N.; Gaffey, Michael J.; Sundararaman, P.

1991-01-01

An interpretive model for estimating porphyrin concentration in bitumen and kerogen from spectral reaflectance data in the visible and near-ultraviolet region of the spectrum is derived and calibrated. Preliminary results obtained using the model are consistent with concentrations determined from the bitumen extract and suggest that 40 to 60 percent of the total porphyrin concentration remains in the kerogen after extraction of bitumen from thermally immature samples. The reflectance technique will contribute to porphyrin and kerogen studies and can be applied at its present level of development to several areas of geologic and paleo-oceanographic research.

Impact of kerogen heterogeneity on sorption of organic pollutants. 2. Sorption equilibria

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

Yang, C.; Yu, Z.Q.; Xiao, B.H.

2009-08-15

Phenanthrene and naphthalene sorption isotherms were measured for three different series of kerogen materials using completely mixed batch reactors. Sorption isotherms were nonlinear for each sorbate-sorbent system, and the Freundlich isotherm equation fit the sorption data well. The Freundlich isotherm linearity parameter n ranged from 0.192 to 0.729 for phenanthrene and from 0.389 to 0.731 for naphthalene. The n values correlated linearly with rigidity and aromaticity of the kerogen matrix, but the single-point, organic carbon-normalized distribution coefficients varied dramatically among the tested sorbents. A dual-mode sorption equation consisting of a linear partitioning domain and a Langmuir adsorption domain adequately quantifiedmore » the overall sorption equilibrium for each sorbent-sorbate system. Both models fit the data well, with r{sup 2} values of 0.965 to 0.996 for the Freundlich model and 0.963 to 0.997 for the dual-mode model for the phenanthrene sorption isotherms. The dual-mode model fitting results showed that as the rigidity and aromaticity of the kerogen matrix increased, the contribution of the linear partitioning domain to the overall sorption equilibrium decreased, whereas the contribution of the Langmuir adsorption domain increased. The present study suggested that kerogen materials found in soils and sediments should not be treated as a single, unified, carbonaceous sorbent phase.« less

Increasing maturity of kerogen type II reflected by alkylbenzene distribution from pyrolysis-gas chromatography-mass spectrometry

USGS Publications Warehouse

Lis, G.P.; Mastalerz, Maria; Schimmelmann, A.

2008-01-01

A series of Late Devonian to Early Mississippian type II kerogens with vitrinite reflectance values Ro 0.29-2.41% were analyzed using py-GC-MS. In addition, a low maturity kerogen with Ro 0.44% was separated into fractions via density gradient centrifugation, followed by py-GC-MS of the alginite and amorphinite maceral concentrates. Alkylbenzenes and n-alk-1-ene/n-alkane doublets represented the main compound classes identified in all pyrolysates. The pyrolysate from alginite featured 1,2,4-trimethylbenzene and toluene as the two most prominent alkylbenzenes. In contrast, alkylbenzenes in pyrolysates from amorphinite and low maturity bulk kerogens with Ro 0.29-0.63% were dominated by 1,2,3,4-tetramethylbenzene. With increasing thermal maturity, pyrolysates were increasingly dominated by (i) alkylbenzenes with fewer methyl groups, namely by tri- and dimethylbenzenes at medium maturity (Ro 0.69-1.19%), and (ii) by toluene at higher maturity (Ro 1.30-2.41%). With increasing maturity of kerogen type II, the decreasing abundance of highly methyl-substituted alkylbenzenes and the parallel increase in less methyl-substituted alkylbenzenes in flash pyrolysates suggest that demethylation is an important chemical process in the thermal maturation of kerogen type II. ?? 2008 Elsevier Ltd. All rights reserved.

Steranes and triterpanes generated from kerogen pyrolysis in the absence and presence of minerals

NASA Technical Reports Server (NTRS)

Tannenbaum, E.; Ruth, E.; Kaplan, I. R.

1986-01-01

Changes in the degree of isomerization of steranes and triterpanes during kerogen pyrolysis in the absence or presence of minerals are described. Kerogen from a Monterey Formation diatomite core sample was pyrolyzed under reduced pressure at 300 C for 2-1000 hrs in the presence or absence of calcite, illite, and montmorillonite. It is observed that the extent of isomerization of biomakers in C-20 in 14 alpha(H), 17 alpha(H)-steranes, at C-22 in 17 alpha(H), 21 beta(H)-hopanes and of 17 beta(H), 21 beta(H)-hopanes correlates to early diagenetic stages in rock extracts from sedimentary basins, and faster isomerization for steranes and triterpanes in the bitumen then for those in the kerogen structure are detected. The effects of the minerals on the isomerization reactions are examined; calcite inhibits, and illite and montmorillonite catalyze the reactions.

Factors controlling the abundance of organic sulfur in flash pyrolyzates of Upper Cretaceous kerogens from Sergipe Basin, Brazil

USGS Publications Warehouse

Carmo, A.M.; Stankiewicz, B.A.; Mastalerz, Maria; Pratt, L.M.

1997-01-01

The molecular and elemental composition of immature kerogens isolated from Upper Cretaceous marine carbonates from Sergipe Basin, Brazil were investigated using combined pyrolysis-gas chromatography/mass spectrometry and organic petrographic techniques. The kerogens are predominantly composed of reddish-fluorescing amorphous organic matter (AOM) and variable amounts of yellow-fluorescing alginite and liptodetrinite. The abundance of organic sulfur in the kerogens inferred from the ratio 2-ethyl-5-methylthiophene/(1,2-dimethylbenzene + dec-1-ene) in the pyrolyzates is variable and may be related to changes in the type of primary organic input and/or to variations in rates of bacterial sulfate reduction. A concomitant increase in S/C and O/C ratios determined in situ using the electron microprobe is observed in AOM and alginites and may be related to a progressive oxidation of the organic matter during sulfurization. The S/C ratio of the AOM is systematically higher than the S C ratio of the alginites. Combined with a thiophene distribution characteristic of pyrolyzates of Type II organic matter, the higher S/C of AOM in Sergipe kerogens suggests that sulfurization and incorporation of low-molecular weight lipids derived from normal marine organic matter into the kerogen structure predominated over direct sulfurization of highly aliphatic algal biomacromolecules.The molecular and elemental composition of immature kerogens isolated from Upper Cretaceous marine carbonates from Sergipe Basin, Brazil were investigated using combined pyrolysis-gas chromatography/mass spectrometry and organic petrographic techniques. The kerogens are predominantly composed of reddish-fluorescing amorphous organic matter (AOM) and variable amounts of yellow-fluorescing alginite and liptodetrinite. The abundance of organic sulfur in the kerogens inferred from the ratio 2-ethyl-5-methylthiophene/(1,2-dimethylbenzene+dec-1-ene) in the pyrolyzates is variable and may be related to changes in

Differential retention and release of CO 2 and CH 4 in kerogen nanopores: Implications for gas extraction and carbon sequestration

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

Ho, Tuan Anh; Wang, Yifeng; Xiong, Yongliang

Methane (CH 4) and carbon dioxide (CO 2), the two major components generated from kerogen maturation, are stored dominantly in nanometer-sized pores in shale matrix as (1) a compressed gas, (2) an adsorbed surface species and/or (3) a species dissolved in pore water (H 2O). In addition, supercritical CO 2 has been proposed as a fracturing fluid for simultaneous enhanced oil/gas recovery (EOR) and carbon sequestration. A mechanistic understanding of CH 4-CO 2-H 2O interactions in shale nanopores is critical for designing effective operational processes. Using molecular simulations, we show that kerogen preferentially retains CO 2 over CH 4 andmore » that the majority of CO 2 either generated during kerogen maturation or injected in EOR will remain trapped in the kerogen matrix. The trapped CO 2 may be released only if the reservoir pressure drops below the supercritical CO 2 pressure. When water is present in the kerogen matrix, it may block CH 4 release. Furthermore, the addition of CO 2 may enhance CH 4 release because CO 2 can diffuse through water and exchange for adsorbed methane in the kerogen nanopores.« less

Differential retention and release of CO 2 and CH 4 in kerogen nanopores: Implications for gas extraction and carbon sequestration

DOE PAGES

Ho, Tuan Anh; Wang, Yifeng; Xiong, Yongliang; ...

2018-02-06

Methane (CH 4) and carbon dioxide (CO 2), the two major components generated from kerogen maturation, are stored dominantly in nanometer-sized pores in shale matrix as (1) a compressed gas, (2) an adsorbed surface species and/or (3) a species dissolved in pore water (H 2O). In addition, supercritical CO 2 has been proposed as a fracturing fluid for simultaneous enhanced oil/gas recovery (EOR) and carbon sequestration. A mechanistic understanding of CH 4-CO 2-H 2O interactions in shale nanopores is critical for designing effective operational processes. Using molecular simulations, we show that kerogen preferentially retains CO 2 over CH 4 andmore » that the majority of CO 2 either generated during kerogen maturation or injected in EOR will remain trapped in the kerogen matrix. The trapped CO 2 may be released only if the reservoir pressure drops below the supercritical CO 2 pressure. When water is present in the kerogen matrix, it may block CH 4 release. Furthermore, the addition of CO 2 may enhance CH 4 release because CO 2 can diffuse through water and exchange for adsorbed methane in the kerogen nanopores.« less

The use of kerogen data in understanding the properties and evolution of interstellar carbonaceous dust

NASA Astrophysics Data System (ADS)

Papoular, R.

2001-11-01

A number of authors have, in the past decade, pointed to the similarity of the 3.4-mu m band of kerogen with that of the Galactic Centre (GC). Kerogen is a family of solid terrestrial sedimentary materials essentially made of C, H and O interlocked in a disordered, more or less aliphatic, structure. Here, the most recent results of the astronomical literature and the rich quantitative geochemical literature are tapped with two purposes in mind: extend the analogy to the mid-IR bands and, based on these new constraints, quantitatively assess the properties of the carrier dust. It is shown that the great diversity of IR astronomical IS (interstellar) dust is paralleled by the changes in kerogen spectra as the material spontaneously and continuously evolves (aromatizes) in the earth. Since the composition and structure of kerogen are known all along its evolution, it is possible, by spectral analogy, to estimate these properties for the corresponding astronomical carriers. The Galactic Centre 3.4 mu m feature is thus found to correspond to an early stage of evolution, for which the composition in C, H and O and the structure of the corresponding kerogen are known and reported here. The role of oxygen in the subsequent evolution and its contribution to different bands are stressed. The above provides new arguments in favour of the 3.4-mu m band, as well as the observed accompanying mid-IR bands, being carried by kerogen-like dust born in CS (circumstellar) envelopes, mostly of AGB (asymptotic giant branch) objects. Subsequent dust evolution in composition and structure (aromatization) is fast enough that the unidentified infrared bands can already show up in well-developed planetary nebulae (PNe), as observed. A fraction of incompletely evolved dust can escape into the diffuse IS medium and molecular clouds. As a consequence, aliphatic and aromatic features can both be detected in the sky, in emission (Proto-PNe, PNe and PDRs (photo-dissociation regions)) as well as in

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

USGS Publications Warehouse

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

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

NASA Astrophysics Data System (ADS)

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

Prediction of brittleness based on anisotropic rock physics model for kerogen-rich shale

NASA Astrophysics Data System (ADS)

Qian, Ke-Ran; He, Zhi-Liang; Chen, Ye-Quan; Liu, Xi-Wu; Li, Xiang-Yang

2017-12-01

The construction of a shale rock physics model and the selection of an appropriate brittleness index ( BI) are two significant steps that can influence the accuracy of brittleness prediction. On one hand, the existing models of kerogen-rich shale are controversial, so a reasonable rock physics model needs to be built. On the other hand, several types of equations already exist for predicting the BI whose feasibility needs to be carefully considered. This study constructed a kerogen-rich rock physics model by performing the selfconsistent approximation and the differential effective medium theory to model intercoupled clay and kerogen mixtures. The feasibility of our model was confirmed by comparison with classical models, showing better accuracy. Templates were constructed based on our model to link physical properties and the BI. Different equations for the BI had different sensitivities, making them suitable for different types of formations. Equations based on Young's Modulus were sensitive to variations in lithology, while those using Lame's Coefficients were sensitive to porosity and pore fluids. Physical information must be considered to improve brittleness prediction.

Selective preservation and origin of petroleum-forming aquatic kerogen

USGS Publications Warehouse

Hatcher, P.G.; Spiker, E. C.; Szeverenyi, N.M.; Maciel, G.E.

1983-01-01

Studies of a marine algal sapropel from Mangrove Lake, Bermuda, by 13C NMR and stable carbon isotopic methods show that precursors of aquatic kerogen (insoluble, macromolecular, paraffinic humic substances) are primary components of algae and possibly associated bacteria and that these substances survive microbial decomposition and are selectively preserved during early diagenesis. ?? 1983 Nature Publishing Group.

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

NASA Astrophysics Data System (ADS)

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

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

USGS Publications Warehouse

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.

Influences of kerogen-rich bedrock on the molecular and isotopic composition of modern soils; implications for global C cycling

NASA Astrophysics Data System (ADS)

Longbottom, T. L.; Hockaday, W. C.

2016-12-01

Kerogen represents the largest terrestrial organic carbon (OC) reservoir on earth and is vulnerable to remineralization upon exposure to earth's atmosphere. Oxidative weathering of ancient sedimentary organic matter is an immensely transformative process with poorly-constrained mechanisms and flux values in contemporary carbon cycle models. The weathered residuum of organic-rich mudrocks serves as parent material for many modern soils, and it is likely that the structure and dynamics of the resulting soil organic matter pool is inherited directly from kerogen-rich bedrock. We used a combination of solid-state 13-C nuclear magnetic resonance (NMR) spectroscopy, and carbon isotope techniques to describe molecular and isotopic changes that occur throughout oxidative weathering of marine kerogens, and the subsequent formation of modern soils, in two outcropping Cretaceous mudstones of the Eagle Ford and Pepper Formations in central, TX. Gradational production of O-containing functionalities was observed, coupled with reductions in characteristically abundant polymethylenic components of type II kerogens. Organic matter structural parameters, derived from C-H dephasing NMR experiments, also provide the basis for a novel weathering index that accounts for the degree of post-sedimentary diagenetic alteration of samples along the kerogen-soil continuum. Molecular and isotopic mixing models were employed in estimating the proportions of modern and ancient C in soils, as increased incorporation and vulnerability of ancient OC under climatic shifts in temperature and/or precipitation is likely.

Role of water in hydrocarbon generation from Type-I kerogen in Mahogany oil shale of the Green River Formation

USGS Publications Warehouse

Lewan, M.D.; Roy, S.

2011-01-01

Hydrous and anhydrous closed-system pyrolysis experiments were conducted on a sample of Mahogany oil shale (Eocene Green River Formation) containing Type-I kerogen to determine whether the role of water had the same effect on petroleum generation as reported for Type-II kerogen in the Woodford Shale. The experiments were conducted at 330 and 350??C for 72h to determine the effects of water during kerogen decomposition to polar-rich bitumen and subsequent bitumen decomposition to hydrocarbon-rich oil. The results showed that the role of water was more significant in bitumen decomposition to oil at 350??C than in kerogen decomposition to bitumen at 330??C. At 350??C, the hydrous experiment generated 29% more total hydrocarbon product and 33% more C15+ hydrocarbons than the anhydrous experiment. This is attributed to water dissolved in the bitumen serving as a source of hydrogen to enhance thermal cracking and facilitate the expulsion of immiscible oil. In the absence of water, cross linking is enhanced in the confines of the rock, resulting in formation of pyrobitumen and molecular hydrogen. These differences are also reflected in the color and texture of the recovered rock. Despite confining liquid-water pressure being 7-9 times greater in the hydrous experiments than the confining vapor pressure in the anhydrous experiments, recovered rock from the former had a lighter color and expansion fractures parallel to the bedding fabric of the rock. The absence of these open tensile fractures in the recovered rock from the anhydrous experiments indicates that water promotes net-volume increase reactions like thermal cracking over net-volume decrease reactions like cross linking, which results in pyrobitumen. The results indicate the role of water in hydrocarbon and petroleum formation from Type-I kerogen is significant, as reported for Type-II kerogen. ?? 2010.

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

NASA Astrophysics Data System (ADS)

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

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 pyrolysates. When pyrolysed, all of the kerogens released several series of heterocyclic sulphur compounds including alkylthiophenes, alkylthiolanes, alkylthianes and alkylbenzothiophenes together with n-alkanes, n-alklenes and alkylcyclohexanes as well as alkyl-substituted benzenes and naphthalenes. One of the kerogens, isolated from the Guttenberg oil rock, consisted predominantly of the alga Gloeocapsomorpha prisca, which produced sulphur compounds and hydrocarbons with fingerprint pyrograms that were different from those of the other three kerogens. The data provide prima facie evidence that these distributions may act as pseudo "biological markers" for this species of alga, namely that unsaturated kerogen moieties available for the uptake of sulphur, or which can cyclise to form hydrocarbons, distinguish Gloeocapsomorpha prisca from the contributing organisms of the other kerogens analysed.

Thermal alteration of young kerogen in relation to petroleum genesis

NASA Technical Reports Server (NTRS)

Ishiwatari, R.; Ishiwatari, M.; Kaplan, I. R.; Rohrback, B. G.

1976-01-01

Kerogen, humic acid, and lipid material were separated from a young marine sediment and heated in sealed tubes in a nitrogen atmosphere at 150 and 410 C. Gaseous and liquid products generated during heating, and also the residual organic material, were characterized by gas-liquid chromatography, elemental analysis, infrared and electron spin resonance spectroscopy, and X-ray diffraction.

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

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

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

PubMed Central

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

2016-01-01

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

Rapid and direct screening of H:C ratio in Archean kerogen via microRaman Spectroscopy

NASA Astrophysics Data System (ADS)

Ferralis, N.; Matys, E. D.; Allwood, A.; Knoll, A. H.; Summons, R. E.

2015-12-01

Rapid evaluation of the preservation of biosignatures in ancient kerogens is essential for the evaluation of the usability of Earth analogues as proxies of Martian geological materials. No single, non-destructive and non-invasive technique currently exists to rapidly determine such state of preservation of the organic matter in relation to its geological and mineral environment. Due to its non-invasive nature, microRaman spectroscopy is emerging as a candidate technique for the qualitative determination maturity of organic matter, by correlating Raman spectral features and aromatic carbon cluster size. Here we will present a novel quantitative method in which before-neglected Raman spectral features are correlated directly and with excellent accuracy with the H:C ratio. In addition to providing a chemical justification of the found direct correlation, we will show its applicability and predictive capabilities in evaluating H:C in Archean kerogens. This novel method opens new opportunities for the use of Raman spectroscopy and mapping. This includes the non-invasively determination of kerogen preservation and microscale chemical diversity within a particular Earth analogue, to be potentially extended to evaluate Raman spectra acquired directly on Mars.

Oil-generation kinetics for organic facies with Type-II and -IIS kerogen in the Menilite Shales of the Polish Carpathians

USGS Publications Warehouse

Lewan, M.D.; Kotarba, M.J.; Curtis, John B.; Wieclaw, D.; Kosakowski, P.

2006-01-01

The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S2 generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S2 generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S2 generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as

Isotopic characteristics of simulated meteoritic organic matter. I - Kerogen-like material

NASA Technical Reports Server (NTRS)

Kerridge, John F.; Mariner, Ruth; Flores, Jose; Chang, Sherwood

1989-01-01

Carbonaceous residues from a variety of laboratory syntheses yield release patterns for C and H isotopes during stepwise combustion that fail to mimic the striking patterns characteristic of meteoritic kerogen-like residues that otherwise superficially resemble them. It seems likely that the meteoritic material comprises a complex mixture of substances having different origins and/or synthesis conditions.

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

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

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

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

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

DOE PAGES

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

2016-06-16

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

Source indicators of humic substances and proto-kerogen - Stable isotope ratios, elemental compositions and electron spin resonance spectra

NASA Technical Reports Server (NTRS)

Stuermer, D. H.; Peters, K. E.; Kaplan, I. R.

1978-01-01

Stable isotope ratios of C, N and H, elemental compositions, and electron spin resonance (ESR) data of humic acids and proto-kerogens from twelve widely varying sampling locations are presented. Humic acids and proto-kerogens from algal sources are more aliphatic and higher in N than those from higher plant sources. Oxygen content appears to represent a measure of maturation, even in Recent sediments, and S content may reflect redox conditions in the environment of deposition. The ESR data indicate that the transformation of humic substances to proto-kerogens in Recent sediments is accompanied by an increase in aromatic character. A combination of stable carbon isotope ratio and H/C ratio may be a simple but reliable source indicator which allows differentiation of marine-derived from terrestrially-derived organic matter. The stable nitrogen isotope ratios are useful indicators of nitrogen nutrient source. Deuterium/hydrogen isotope ratios appear to reflect variations in meteoric waters and are not reliable source indicators.

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

NASA Technical Reports Server (NTRS)

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

Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

NASA Technical Reports Server (NTRS)

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

2013-01-01

The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in 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, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes

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

NASA Astrophysics Data System (ADS)

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.

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

USGS Publications Warehouse

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

2005-01-01

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

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

USGS Publications Warehouse

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

Thermal maturity of type II kerogen from the New Albany Shale assessed by13C CP/MAS NMR

USGS Publications Warehouse

Werner-Zwanziger, U.; Lis, G.; Mastalerz, Maria; Schimmelmann, A.

2005-01-01

Thermal maturity of oil and gas source rocks is typically quantified in terms of vitrinite reflectance, which is based on optical properties of terrestrial woody remains. This study evaluates 13C CP/MAS NMR parameters in kerogen (i.e., the insoluble fraction of organic matter in sediments and sedimentary rocks) as proxies for thermal maturity in marine-derived source rocks where terrestrially derived vitrinite is often absent or sparse. In a suite of samples from the New Albany Shale (Middle Devonian to the Early Mississippian, Illinois Basin) the abundance of aromatic carbon in kerogen determined by 13C CP/MAS NMR correlates linearly well with vitrinite reflectance. ?? 2004 Elsevier Inc. All rights reserved.

Investigating Oil-Prone Kerogen Conversion to Hydrocarbons Using AFM-based Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Eoghan, D.; Cook, D.; Hackley, P. C.; Kjoller, K.; Dawson, D.; Shetty, R.

2016-12-01

Understanding in situ chemical changes occurring during thermal conversion of oil-prone kerogen to hydrocarbons can provide fundamental information regarding the origin of the earth's fossil fuel endowment and reduce uncertainty in hydrocarbon prospecting and resource assessment. Tasmanites algal bodies were studied using an Atomic Force Microscope-based IR spectroscopy technique (AFM-IR) that offers chemical characterization of organic materials with spatial resolution below the diffraction limit. The AFM allows precise positioning within the algal bodies. A tunable IR laser irradiates the sample under the AFM probe. At absorbing wavenumbers, the sample heats up and expands. The AFM detects the expansion of the material under the probe tip to generate local IR spectra. The Tasmanites algal bodies from the Devonian-Mississippian Woodford Shale were contained in two polished rock fragment pellets. To simulate maturation, one was subjected to isothermal hydrous pyrolysis at 320 °C for 72 hours. AFM-IR spectra were collected at multiple sites on algal bodies in both samples (Figure 1). The aromatic C=C ring stretching at 1600 cm-1 (unheated) shifted to 1606 cm-1 with increased absorption in the heated algal bodies, indicating development of increased aromaticity with thermal maturation. The ratio of the 1606 cm-1 peak to peaks at 1708 cm-1 (C=O stretching) and 1460 cm-1 (CH2 wag) was higher in the heated sample, indicating loss of oxygenated functional groups and aliphatic components with thermal advance. A shift of the 1372 cm-1 peak to 1376 cm-1 with lower absorption in the heated samples suggests reduction in the abundance of methyl substituents and development of preferred localization. These results are consistent with extant information from FTIR analysis and demonstrate the ability of AFM-IR to provide in situ characterization of organic matter with respect to thermal maturity advance, and its application to understanding conversion of oil-prone kerogen to

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

NASA Technical Reports Server (NTRS)

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

Kerogen maturation data in the Uinta Basin, Utah, USA, constrain predictions of natural hydrocarbon seepage into the atmosphere

NASA Astrophysics Data System (ADS)

Mansfield, Marc L.

2014-03-01

Natural seepage of methane from the lithosphere to the atmosphere occurs in regions with large natural gas deposits. According to some authors, it accounts for roughly 5% of the global methane budget. I explore a new approach to estimate methane fluxes based on the maturation of kerogen, which is the hydrocarbon polymer present in petroleum source rocks and whose decomposition leads to the formation of oil and natural gas. The temporal change in the atomic H/C ratio of kerogen lets us estimate the total carbon mass released by it in the form of oil and natural gas. Then the time interval of active kerogen decomposition lets us estimate the average annual formation rate of oil and natural gas in any given petroleum system, which I demonstrate here using the Uinta Basin of eastern Utah as an example. Obviously, this is an upper bound to the average annual rate at which natural gas seeps into the atmosphere. After adjusting for biooxidation of natural gas, I conclude that the average annual seepage rate in the Uinta Basin is not greater than (3100 ± 900) tonne yr-1. This is (0.5 ± 0.15)% of the total flux of methane into the atmosphere over the Basin, as measured during aircraft flights. I speculate about the difference between the regional 0.5% and the global 5% estimates.

Isotopic composition of carbonaceous-chondrite kerogen Evidence for an interstellar origin of organic matter in meteorites

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1983-01-01

Stepwise combustion has revealed systematic patterns of isotopic heterogeneity for C, H and N in the insoluble organic fraction (m-kerogen) from the Orgueil and Murray carbonaceous chondrites. Those patterns are essentially identical for both meteorites, indicating a common source of m-kerogen. The data cannot be reconciled with a single mass-fractionation process acting upon a single precursor composition. This indicates either a multi-path history of mass-dependent processing or a significant nucleogenetic contribution, or both. If mass-fractionation were the dominant process, the magnitude of the observed isotopic variability strongly suggests that ion-molecule reactions at very low temperatures, probably in interstellar clouds, were responsible. In any case, an interstellar, rather than solar nebular, origin for at least some of the meteoritic organic matter is indicated. This has interesting implications for the origin of prebiotic molecules, temperatures in the early solar system, and the isotopic compositions of volatiles accreted by the terrestrial planets.

Applications of palynology and kerogen analysis to California Paleogene stratigraphy and paleoenvironment

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

Lucas-Clark, J.

1988-03-01

Paleogene strata of California commonly yield usable preserved organic material. Fossil pollen, spores, and dinoflagellates of chronostratigraphic significance are recovered from Paleogene rocks that contain no other usable fossil material. Palynofacies analysis, which combines data from fossil species with data from kerogen analysis, is used to interpret paleo-environmental aspects such as paleobathymetry, probable upwelling, turbulence, and rates of sedimentation. Examples of applications come from Paleogene submarine canyon deposits, the northern California Franciscan coastal belt, and southern California Transverse Ranges.

Molecular Imaging of Kerogen and Minerals in Shale Rocks across Micro- and Nano- Scales

NASA Astrophysics Data System (ADS)

Hao, Z.; Bechtel, H.; Sannibale, F.; Kneafsey, T. J.; Gilbert, B.; Nico, P. S.

2016-12-01

Fourier transform infrared (FTIR) spectroscopy is a reliable and non-destructive quantitative method to evaluate mineralogy and kerogen content / maturity of shale rocks, although it is traditionally difficult to assess the organic and mineralogical heterogeneity at micrometer and nanometer scales due to the diffraction limit of the infrared light. However, it is truly at these scales that the kerogen and mineral content and their formation in share rocks determines the quality of shale gas reserve, the gas flow mechanisms and the gas production. Therefore, it's necessary to develop new approaches which can image across both micro- and nano- scales. In this presentation, we will describe two new molecular imaging approaches to obtain kerogen and mineral information in shale rocks at the unprecedented high spatial resolution, and a cross-scale quantitative multivariate analysis method to provide rapid geochemical characterization of large size samples. The two imaging approaches are enhanced at nearfield respectively by a Ge-hemisphere (GE) and by a metallic scanning probe (SINS). The GE method is a modified microscopic attenuated total reflectance (ATR) method which rapidly captures a chemical image of the shale rock surface at 1 to 5 micrometer resolution with a large field of view of 600 X 600 micrometer, while the SINS probes the surface at 20 nm resolution which provides a chemically "deconvoluted" map at the nano-pore level. The detailed geochemical distribution at nanoscale is then used to build a machine learning model to generate self-calibrated chemical distribution map at micrometer scale with the input of the GE images. A number of geochemical contents across these two important scales are observed and analyzed, including the minerals (oxides, carbonates, sulphides), the organics (carbohydrates, aromatics), and the absorbed gases. These approaches are self-calibrated, optics friendly and non-destructive, so they hold the potential to monitor shale gas

Dicarboxylic acids generated by thermal alteration of kerogen and humic acids

NASA Technical Reports Server (NTRS)

Kawamura, Kimitaka; Kaplan, I. R.

1987-01-01

Significant amounts (up to 2 percent of organic geopolymers) of low-molecular-weight (LMW) dicarboxylic acids (C2-C10) have been detected during thermal alteration (270 C, 2 h) of kerogens and humic acids isolated from young or ancient lithified sediments. Their distribution is characterized by the predominance of oxalic acid followed by succinic, fumaric, and methylsuccinic acids. These acids are probably released by the breakdown of macromolecular structures, which have incorporated biogenic organic compounds, including diacids, during early digenesis in sediments. Because of their reactivity, LMW diacids may play geochemically important roles under natural conditions.

Changes in kerogen composition across an oxidation front in map turbidites as revealed by pyrolysis GC-MS

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

Hoefs, M.J.L.; Sinninghe Damste, J.S.; Lange, G.L. de

1996-12-31

We have studied four Madeira Abyssal Plain (MAP) TOC rich turbidites for the influence of post depositional oxidation on organic matter composition. Kerogens were isolated and studied by pyrolysis-GC-MS analysis. This showed that the kerogen of the oxidized part of the turbidite is chemically significantly different from the unoxidized part. The relative amount of saturated and unsaturated n-alkanes has increased substantially (e.g. increase from 39 to 62%), at the cost of the isoprenoid alkanes and alkylated thiophenes (e.g. decrease from 16 to 6%, 8 to 3% respectively). In addition, large differences in the internal distributions of the various compound groupsmore » of the pyrolysates were observed. For example, prist-1-ene and 1,2,3,4-tetramethylbenzene were markedly decreased in the pyrolysates of the oxidized part of the turbidites. These results strongly support the selective preservation of high molecular weight aliphatic biopolymeric substances under oxidative conditions.« less

Comparison of the bulk geochemical features and thermal reactivity of kerogens from Mol (Boom Clay), Bure (Callovo-Oxfordian argillite) and Tournemire (Toarcian shales) underground research laboratories.

PubMed

Deniau, I; Devol-Brown, I; Derenne, S; Behar, F; Largeau, C

2008-01-25

Deep argillaceous formations are potential repositories for the long-term disposal of nuclear waste because of their low permeability and high sorption capacity with respect to radioelements and heavy metals. Such sedimentary rocks contain organic matter, mostly macromolecular and insoluble (kerogen). Upon temperature elevation related to high-level long-lived radioactive waste disposal, the kerogen may release significant quantities of gaseous and liquid effluents, especially oxygen-containing ones, which may influence the ability of the clay to retain radionuclides. The aim of the present study is to assess the global geochemical features and the thermal reactivity of the kerogens isolated from samples collected in the Bure and Tournemire sites, France (Callovo-Oxfordian Clay and Toarcian Shales, respectively) and to draw comparisons with data previously obtained for the Mol site, Belgium (Boom Clay). The study is based on a combination of elemental, spectroscopic (FTIR, solid state (13)C NMR) and pyrolytic (Rock-Eval pyrolysis, Curie point pyrolysis-gas chromatography/mass spectrometry) analyses. Different levels of maturity and resulting differences in the relative abundance of oxygen-containing groups were thus observed for the three kerogens. This is linked with differences in their ability to generate CO(2) and various oxygen-containing, low molecular weight, water-soluble compounds under thermal stress, decreasing from Mol to Bure and to Tournemire.

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

USGS Publications Warehouse

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

1982-01-01

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

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

USGS Publications Warehouse

Cao, Xiaoyan; Birdwell, Justin E.; Chappell, Mark A.; Li, Yuan; Pignatello, Joseph J.; Mao, Jingdong

2013-01-01

Characterization of oil shale kerogen and organic residues remaining in postpyrolysis spent shale is critical to the understanding of the oil generation process and approaches to dealing with issues related to spent shale. The chemical structure of organic matter in raw oil shale and spent shale samples was examined in this study using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Oil shale was collected from Mahogany zone outcrops in the Piceance Basin. Five samples were analyzed: (1) raw oil shale, (2) isolated kerogen, (3) oil shale extracted with chloroform, (4) oil shale retorted in an open system at 500°C to mimic surface retorting, and (5) oil shale retorted in a closed system at 360°C to simulate in-situ retorting. The NMR methods applied included quantitative direct polarization with magic-angle spinning at 13 kHz, cross polarization with total sideband suppression, dipolar dephasing, CHn selection, 13C chemical shift anisotropy filtering, and 1H-13C long-range recoupled dipolar dephasing. The NMR results showed that, relative to the raw oil shale, (1) bitumen extraction and kerogen isolation by demineralization removed some oxygen-containing and alkyl moieties; (2) unpyrolyzed samples had low aromatic condensation; (3) oil shale pyrolysis removed aliphatic moieties, leaving behind residues enriched in aromatic carbon; and (4) oil shale retorted in an open system at 500°C contained larger aromatic clusters and more protonated aromatic moieties than oil shale retorted in a closed system at 360°C, which contained more total aromatic carbon with a wide range of cluster sizes.

Electron-probe microanalysis of light elements in coal and other kerogen

USGS Publications Warehouse

Bustin, R.M.; Mastalerz, Maria; Raudsepp, M.

1996-01-01

Recent advances in electron microprobe technology including development of layered synthetic microstructures, more stable electronics and better matrix-correction programs facilitated routine microanalysis of the light elements in coal. Utilizing an appropriately equipped electron microprobe with suitable standards, it is now possible to analyze directly the light elements (C, O and N, if abundant) in coal macerals and other kerogen. The analytical results are both accurate compared to ASTM methods and highly precise, and provide an opportunity to access the variation in coal chemistry at the micrometre scale. Our experiments show that analyses using a 10 kV accelerating voltage and 10 nA beam current yield the most reliable data and result in minimum sample damage and contamination. High sample counts were obtained for C, O and N using a bi-elemental nickel-carbon pseudo-crystal (2d = 9.5 nm) as an analyzing crystal. Vitrinite isolated from anthracite rank coal proves the best carbon standard and is more desirable than graphite which has higher porosity, whereas lower rank vitrinite is too heterogeneous to use routinely as a standard. Other standards utilized were magnesite for oxygen and BN for nitrogen. No significant carbon, oxygen or nitrogen X-ray peak shifts or peak-shape changes occur between standards and the kerogen analyzed. Counting rates for carbon and oxygen were found to be constant over a range of beam sizes and currents for counting times up to 160 s. Probe-determined carbon and oxygen contents agree closely with those reported from ASTM analyses. Nitrogen analyses compare poorly to ASTM values which probably is in response to overlap between the nitrogen Ka peak with the carbon K-adsorption edge and the overall low nitrogen content of most of our samples. Our results show that the electron microprobe technique provides accurate compositional data for both minor and major elements in coal without the necessity and inherent problems associated with

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

NASA Astrophysics Data System (ADS)

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.

Biological markers from Green River kerogen decomposition

NASA Astrophysics Data System (ADS)

Burnham, A. K.; Clarkson, J. E.; Singleton, M. F.; Wong, C. M.; Crawford, R. W.

1982-07-01

Isoprenoid and other carbon skeletons that are formed in living organisms and preserved essentially intact in ancient sediments are often called biological markers. The purpose of this paper is to develop improved methods of using isoprenoid hydrocarbons to relate petroleum or shale oil to its source rock. It is demonstrated that most, but not all, of the isoprenoid hydrocarbon structures are chemically bonded in kerogen (or to minerals) in Green River oil shale. The rate constant for thermally producing isoprenoid, cyclic, and aromatic hydrocarbons is substantially greater than for the bulk of shale oil. This may be related to the substantial quantity of CO 2 which is evolved coincident with the isoprenoid hydrocarbons but prior to substantial oil evolution. Although formation of isoprenoid alkenes is enhanced by rapid heating and high pyrolysis temperatures, the ratio of isoprenoid alkenes plus alkanes to normal alkenes plus alkanes is independent of heating rate. High-temperature laboratory pyrolysis experiments can thus be used to predict the distribution of aliphatic hydrocarbons in low temperature processes such as in situ shale oil production and perhaps petroleum formation. Finally, we demonstrate that significant variation in biological marker ratios occurs as a function of stratigraphy in the Green River formation. This information, combined with methods for measuring process yield from oil composition, enables one to relate time-dependent processing conditions to the corresponding time-dependent oil yield in a vertical modified- in situ retort even if there is a substantial and previously undetermined delay in drainage of shale oil from the retort.

Organic geochemical studies on kerogen precursors in recently deposited algal mats and oozes

NASA Technical Reports Server (NTRS)

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

1978-01-01

The same kerogen-like residue from the algal mats and oozes at Laguna Mormona, Baja California, is examined following degradation by saponification, alkaline KMnO4 oxidation, and HBr treatment. For comparison, pyrolytic degradation is performed for the residue and five others, two of which are obtained from algal mats at Baffin Bay, Texas. Major conclusions are that (1) Saponification of a residue specimen from the algal-ooze residue results in minor amounts of components bonded to it as esters; (2) Alkaline KMnO4 oxidation reveals that the same residue consists of a cross-linked aliphatic nucleus with additional components attached to it as esters; (3) the major products from pyrolysis of the residue include phytenes, pristenes, sterenes, and triterpenes; and (4) the HBr treatment yielded only one product, indicating the absence of a large number of ether-linkages readily cleaved by HBr.

The organic geochemical characterization: An indication of type of kerogen and maturity of early - Mid Jurassic shale in the Blue Nile formation

NASA Astrophysics Data System (ADS)

Shoieba, Monera Adam; Sum, Chow Weng; Abidin, Nor Syazwani Zainal; Bhattachary, Swapan Kumar

2018-06-01

The heterogeneity and complexity of shale gas has become clear as the development of unconventional resources have improved. The Blue Nile Basin, is one of the many Mesozoic rift basins in Sudan associated with the Central African Rift System (CARS). It is located in the eastern part of the Republic of Sudan and has been the major focus for shale gas exploration due to the hydrocarbon found in the basin. But so far no success of discovery has been achieved because the shale gas potentiality of the study area is still unknown. The objective of this study is to assess the type of kerogen and maturity of the shale samples from the Blue Nile Formation within the Blue Nile Basin. This was done by employing organic geochemical methods such as pyrolysis gas chromatography (Py-GC) and petrographic analysis such as vitrinite reflectance (Ro%). Ten representative shale samples from TW-1 well in the Blue Nile Formation have been used to assess the quality of the source rock. Pyrolysis GC analysis indicate that all the selected shale samples contain Type II kerogen that produces oil and gas. The Blue Nile Formation possesses vitrinite reflectance (Ro%) of 0.60-0.65%, indicating that the shale samples are mature in the oil window.

Methane and CO2 Adsorption Capacities of Kerogen in the Eagle Ford Shale from Molecular Simulation.

PubMed

Psarras, Peter; Holmes, Randall; Vishal, Vikram; Wilcox, Jennifer

2017-08-15

Over the past decade, the United States has become a world leader in natural gas production, thanks in part to a large-fold increase in recovery from unconventional resources, i.e., shale rock and tight oil reservoirs. In an attempt to help mitigate climate change, these depleted formations are being considered for their long-term CO 2 storage potential. Because of the variability in mineral and structural composition from one formation to the next (even within the same region), it is imperative to understand the adsorption behavior of CH 4 and CO 2 in the context of specific conditions and pore surface chemistry, i.e., relative total organic content (TOC), clay, and surface functionality. This study examines two Eagle Ford shale samples, both recovered from shale that was extracted at depths of approximately 3800 m and having low clay content (i.e., less than 5%) and similar mineral compositions but distinct TOCs (i.e., 2% and 5%, respectively). Experimentally validated models of kerogen were used to the estimate CH 4 and CO 2 adsorption capacities. The pore size distributions modeled were derived from low-pressure adsorption isotherm data using CO 2 and N 2 as probe gases for micropores and mesopores, respectively. Given the presence of water in these natural systems, the role of surface chemistry on modeled kerogen pore surfaces was investigated. Several functional groups associated with surface-dissociated water were considered. Pressure conditions from 10 to 50 bar were investigated using grand canonical Monte Carlo simulations along with typical outgassing temperatures used in many shale characterization and adsorption studies (i.e., 60 and 250 °C). Both CO 2 and N 2 were used as probe gases to determine the total pore volume available for gas adsorption spanning pore diameters ranging from 0.3 to 30 nm. The impacts of surface chemistry, outgassing temperature, and the inclusion of nanopores with diameters of less than 1.5 nm were determined for applications

A new boundary scheme for simulation of gas flow in kerogen pores with considering surface diffusion effect

NASA Astrophysics Data System (ADS)

Wang, Lingquan; Zeng, Zhong; Zhang, Liangqi; Qiao, Long; Zhang, Yi; Lu, Yiyu

2018-04-01

Navier-Stokes (NS) equations with no-slip boundary conditions fail to realistically describe micro-flows with considering nanoscale phenomena. Particularly, in kerogen pores, slip-flow and surface diffusion are important. In this study, we propose a new slip boundary scheme for the lattice Boltzmann (LB) method through the non-equilibrium extrapolation scheme to simulate the slip-flow considering surface diffusion effect. Meanwhile, the second-order slip velocity can be taken into account. The predicted characteristics in a two-dimensional micro-flow, including slip-velocity, velocity distribution along the flow direction with/without surface diffusion are present. The results in this study are compared with available analytical and reference results, and good agreements are achieved.

Experimental controls on D/H and 13C/12C ratios of kerogen, bitumen and oil during hydrous pyrolysis

USGS Publications Warehouse

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

2001-01-01

Large isotopic transfers between water-derived hydrogen and organic hydrogen occurred during hydrous pyrolysis experiments of immature source rocks, in spite of only small changes in organic 13C/12C. Experiments at 330 ??C over 72 h using chips or powder containing kerogen types I and III identify the rock/water ratio as a main factor affecting ????D for water and organic hydrogen. Our data suggest that larger rock permeability and smaller rock grain size increase the H-isotopic transfer between water-derived hydrogen and thermally maturing organic matter. Increasing hydrostatic pressure may have a similar effect, but the evidence remains inconclusive. ?? 2001 Elsevier Science Ltd. All rights reserved.

Organic sulphur in macromolecular sedimentary organic matter: I. Structure and origin of sulphur-containing moieties in kerogen, asphaltenes and coal as revealed by flash pyrolysis

NASA Astrophysics Data System (ADS)

Sinninghe Damsté, Jaap S.; Eglinton, Timothy I.; De Leeuw, Jan W.; Schenck, P. A.

1989-04-01

The distributions of sulphur-containing compounds generated by flash pyrolysis of macromolecular sedimentary organic matter (kerogen, coal, asphaltenes) were studied by gas chromatography in combination with Sselective flame photometric detection or mass spectrometry. The abundance of S-containing pyrolysis products in the pyrolysates relative to other products was highly variable depending on the sample but the types of products were generally similar, being mainly composed of "gaseous" compounds ( e.g., hydrogen sulphide) and low molecular weight alkylthiophenes and alkylbenzothiophenes. The distribution patterns of the alkylated thiophenes were dominated by a limited number of all theoretically possible isomers. The alkyl substitution patterns of the dominant isomers bear a strong similarity to those of the organic S compounds present in the GC-amenable fractions of bitumens and immature oils. Therefore, it is suggested that these S-containing pyrolysis products are formed by pyrolysis of related thiophenic and benzothiophenic moieties present in the macromolecular sedimentary substances. Specific examples include those with linear alkyl, iso and anteiso alkyl, isoprenoid alkyl and steroidal carbon skeletons. The presence of higher molecular weight alkylthiophenes and alkylbenzothiophenes with these same carbon skeletons in pyrolysates of S-rich kerogens provided further evidence for the presence of these S-containing moieties. It is likely that these moieties have been formed by abiogenic S incorporation into sedimentary organic matter during early diagenesis.

Kerogen maturation and incipient graphitization of hydrocarbon source rocks in the Arkoma Basin, Oklahoma and Arkansas: A combined petrographic and Raman spectrometric study

USGS Publications Warehouse

Spotl, C.; Houseknecht, D.W.; Jaques, R.C.

1998-01-01

Dispersed kerogen of the Woodford-Chattanooga and Atoka Formations from the subsurface of the Arkoma Basin show a wide range of thermal maturities (0.38 to 6.1% R(o)) indicating thermal conditions ranging from diagenesis to incipient rock metamorphism. Raman spectral analysis reveals systematic changes of both the first- and second-order spectrum with increasing thermal maturity. These changes include a pronounced increase in the D/O peak height ratio accompanied by a narrowing of the D peak, a gradual decrease in the D/O peak width ratio, and a shift of both peaks toward higher wave numbers. Second-order Raman peaks, though less intensive, also show systematic peak shifting as a function of R(o). These empirical results underscore the high potential of Raman spectrometry as a fast and reliable geothermometer of mature to supermature hydrocarbon source rocks, and as an indicator of thermal maturity levels within the anchizone.Dispersed kerogen of the Woodford-Chattanooga and Atoka Formations from the subsurface of the Arkoma Basin show a wide range of thermal maturities (0.38 to 6.1% Ro) indicating thermal conditions ranging from diagenesis to incipient rock metamorphism. Raman spectral analysis reveals systematic changes of both the first- and second-order spectrum with increasing thermal maturity. These changes include a pronounced increase in the D/O peak height ratio accompanied by a narrowing of the D peak, a gradual decrease in the D/O peak width ratio, and a shift of both peaks toward higher wave numbers. Second-order Raman peaks, though less intensive, also show systematic peak shifting as a function of Ro. These empirical results underscore the high potential of Raman spectrometry as a fast and reliable geothermometer of mature to supermature hydrocarbon source rocks, and as an indicator of thermal maturity levels within the anchizone.

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

USGS Publications Warehouse

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.

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

NASA Astrophysics Data System (ADS)

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.

Re-Os geochronology and Os isotope fingerprinting of petroleum sourced from a Type I lacustrine kerogen: Insights from the natural Green River petroleum system in the Uinta Basin and hydrous pyrolysis experiments

NASA Astrophysics Data System (ADS)

Cumming, Vivien M.; Selby, David; Lillis, Paul G.; Lewan, Michael D.

2014-08-01

Rhenium-osmium (Re-Os) geochronology of marine petroleum systems has allowed the determination of the depositional age of source rocks as well as the timing of petroleum generation. In addition, Os isotopes have been applied as a fingerprinting tool to correlate oil to its source unit. To date, only classic marine petroleum systems have been studied. Here we present Re-Os geochronology and Os isotope fingerprinting of different petroleum phases (oils, tar sands and gilsonite) derived from the lacustrine Green River petroleum system in the Uinta Basin, USA. In addition we use an experimental approach, hydrous pyrolysis experiments, to compare to the Re-Os data of naturally generated petroleum in order to further understand the mechanisms of Re and Os transfer to petroleum. The Re-Os geochronology of petroleum from the lacustrine Green River petroleum system (19 ± 14 Ma - all petroleum phases) broadly agrees with previous petroleum generation basin models (∼25 Ma) suggesting that Re-Os geochronology of variable petroleum phases derived from lacustrine Type I kerogen has similar systematics to Type II kerogen (e.g., Selby and Creaser, 2005a,b; Finlay et al., 2010). However, the large uncertainties (over 100% in some cases) produced for the petroleum Re-Os geochronology are a result of multiple generation events occurring through a ∼3000-m thick source unit that creates a mixture of initial Os isotope compositions in the produced petroleum phases. The 187Os/188Os values for the petroleum and source rocks at the time of oil generation vary from 1.4 to 1.9, with the mode at ∼1.6. Oil-to-source correlation using Os isotopes is consistent with previous correlation studies in the Green River petroleum system, and illustrates the potential utility of Os isotopes to characterize the spatial variations within a petroleum system. Hydrous pyrolysis experiments on the Green River Formation source rocks show that Re and Os transfer are mimicking the natural system. This

Re-Os geochronology and Os isotope fingerprinting of petroleum sourced from a Type I lacustrine kerogen: insights from the natural Green River petroleum system in the Uinta Basin and hydrous pyrolysis experiments

USGS Publications Warehouse

Cumming, Vivien M.; Selby, David; Lillis, Paul G.; Lewan, Michael D.

2014-01-01

Rhenium–osmium (Re–Os) geochronology of marine petroleum systems has allowed the determination of the depositional age of source rocks as well as the timing of petroleum generation. In addition, Os isotopes have been applied as a fingerprinting tool to correlate oil to its source unit. To date, only classic marine petroleum systems have been studied. Here we present Re–Os geochronology and Os isotope fingerprinting of different petroleum phases (oils, tar sands and gilsonite) derived from the lacustrine Green River petroleum system in the Uinta Basin, USA. In addition we use an experimental approach, hydrous pyrolysis experiments, to compare to the Re–Os data of naturally generated petroleum in order to further understand the mechanisms of Re and Os transfer to petroleum. The Re–Os geochronology of petroleum from the lacustrine Green River petroleum system (19 ± 14 Ma – all petroleum phases) broadly agrees with previous petroleum generation basin models (∼25 Ma) suggesting that Re–Os geochronology of variable petroleum phases derived from lacustrine Type I kerogen has similar systematics to Type II kerogen (e.g., Selby and Creaser, 2005a, Selby and Creaser, 2005b and Finlay et al., 2010). However, the large uncertainties (over 100% in some cases) produced for the petroleum Re–Os geochronology are a result of multiple generation events occurring through a ∼3000-m thick source unit that creates a mixture of initial Os isotope compositions in the produced petroleum phases. The 187Os/188Os values for the petroleum and source rocks at the time of oil generation vary from 1.4 to 1.9, with the mode at ∼1.6. Oil-to-source correlation using Os isotopes is consistent with previous correlation studies in the Green River petroleum system, and illustrates the potential utility of Os isotopes to characterize the spatial variations within a petroleum system. Hydrous pyrolysis experiments on the Green River Formation source rocks show that Re and Os transfer

Geochemistry and organic facies of La Luna-Tres Esquinas cycle: Maturity, biomarkers and kerogen issues

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

Olivares, C.; Lorente, M.A.; Cassani, F.

1996-08-01

Four surface sections from the Venzuelan Andes were chosen for this study. The results show interesting trends for exploration of the Andean Belt. In the Eastern Andes (Trujillo), sections San Lazaro and Chejende yield thick, post-mature, highly tectonically disturbed La Luna Formation. San Lazaro section has a fault contact showing La Luna post-mature, inertinitic shales in contact with gray shales, ftanites and carbonates bearing marginally mature, highly fluorescent organic gels. Biomarkers show a high level of hopanes, predominance of C27/C29, and S/R ratio=64% characteristic of marine, moderate mature organic matter. Chejende section has almost the same pattern of marine organicmore » matter (COT=9%) but post-mature. In the Central Andes (Merida), El Valle and San Javier sections yield extremely rich source rocks with very different organic matter. El Valle section (Tres Esquinas Member) has very rich structured algal matter (COT=8%), marginally mature, which is correlated with a short term carbon isotope ({delta}{sup 13}C) fluctuation found in the Campanian-Santonian (anoxic?) cycle. The abundance of C27/C29, and high levels of hopanes are related to marine anoxic conditions. The San Javier section shows evidence of a very rich type I/II kerogen, bearing algal-bacterial amorphous masses, marginally mature and rich (COT=3%); this pattern matches with the abundance of C27/C29 as well as with the ratio S/R=64%, which means moderate maturity. From these results, two provinces can be separated today: a highly tectonized, post-mature, Eastern Andes Province and a very rich, marginally mature, Central Andes Province.« less

Metals in Devonian kerogenous marine strata at Gibellini and Bisoni properties in southern Fish Creek Range, Eureka County, Nevada

USGS Publications Warehouse

Desborough, George A.; Poole, F.G.; Hose, R.K.; Radtke, A.S.

1979-01-01

A kerogen-rich sequence of siliceous mudstone, siltstone, and chert as much as 60 m thick on ridge 7129 in the southern Fish Creek Range, referred to as Gibellini facies of the Woodruff Formation, has been evaluated on the surface and in drill holes principally for its potential resources of vanadium, zinc, selenium, molybdenum, and syncrude oil content. The strata are part of a strongly deformed allochthonous mass of eugeosynclinal Devonian marine rocks that overlie deformed allochthonous Mississippian siliceous rocks and relatively undeformed autochthonous Mississippian Antler flysch at this locality. The vanadium in fresh black rocks obtained from drill holes and fresh exposures in trenches and roadcuts occurs chiefly in organic matter. Concentrations of vanadium oxide (V2O5) in unoxidized samples range from 3,000 to 7,000 ppm. In oxidized and bleached rock that is prevalent at the surface, concentrations of vanadium oxide range from 6,000 to 8,000 ppm, suggesting a tendency toward enrichment due to surficial weathering and ground-water movement. Zinc occurs in sphalerite, and selenium occurs in organic matter; molybdenum appears to occur both in molybdenite and in organic matter. Concentrations of zinc in unoxidized rock range from 4,000 to 18,000 ppm, whereas in oxidized rock they range from 30 to 100 ppm, showing strong depletion due to weathering. Concentrations of selenium in unoxidized rock range from 30 to 200 ppm, whereas in oxidized rock they range from 200 to 400 ppm, indicating some enrichment upon weathering. Concentrations of molybdenum in unoxidized rock range from 70 to 960 ppm, whereas in oxidized rock they range from 30 to 80 ppm, indicating strong depletion upon weathering. Most fresh black rock is low-grade oil shale, and yields as much as 12 gallons/short ton of syncrude oil. Metahewettite is the principal vanadium mineral in the oxidized zone, but it also occurs sparsely as small nodules and fillings of microfractures in unweathered strata

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

NASA Astrophysics Data System (ADS)

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

Modeling oil generation with time-temperature index graphs based on the Arrhenius equation

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

Hunt, J.M.; Lewan, M.D.; Hennet, R.J.C.

1991-04-01

The time and depth of oil generation from petroleum source rocks containing type II kerogens can be determined using time-temperature index (TTI) graphs based on the Arrhenius equation. Activation energies (E) and frequency factors (A) used in the Arrhenius equation were obtained from hydrous pyrolysis experiments on rock samples in which the kerogens represent the range of type II kerogen compositions encountered in most petroleum basins. The E and A values obtained were used to construct graphs that define the beginning and end of oil generation for most type II kerogens having chemical compositions in the range of these standards.more » Activation energies of these standard kerogens vary inversely with their sulfur content. The kerogen with the highest sulfur content had the lowest E value and was the fastest in generating oil, whereas the kerogen with the lowest sulfur content had the highest E value and was the slowest in generating oil. These standard kerogens were designated as types IIA, B, C, and D on the basis of decreasing sulfur content and corresponding increasing time-temperature requirements for generating oil. The {Sigma}TTI{sub ARR} values determined graphically with these type II kerogen standards in two basin models were compared with a computer calculation using 2,000 increments. The graphical method came within {plus minus} 3% of the computer calculation. As type II kerogens are the major oil generators in the world, these graphs should have wide application in making preliminary evaluations of the depth of the oil window in exploration areas.« less

Publications - GMC 24 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 24 Publication Details Title: Total organic carbon, rock-eval pyrolysis, visual kerogen Unknown, [n.d.], Total organic carbon, rock-eval pyrolysis, visual kerogen/vitrinite reflectance of the Information gmc024.pdf (79.0 K) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon

Publications - GMC 23 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 23 Publication Details Title: Total organic carbon, rock-eval pyrolysis, visual kerogen Unknown, [n.d.], Total organic carbon, rock-eval pyrolysis, visual kerogen/vitrinite reflectance for Information gmc023.pdf (199.0 K) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon

Publications - GMC 22 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 22 Publication Details Title: Total organic carbon, rock-eval pyrolysis, visual kerogen Unknown, 1984, Total organic carbon, rock-eval pyrolysis, visual kerogen/vitrinite reflectance for the gmc022.pdf (247.0 K) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite

Publications - GMC 12 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

- 11,850 feet; total organic carbon, rock-eval pyrolysis and visual kerogen/vitrinite reflectance Authors River #1 well 10,255 - 11,850 feet; total organic carbon, rock-eval pyrolysis and visual kerogen gmc012.pdf (384.0 K) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite

Micro-fracture Behavior of Organic Matters in Kerogen-Rich Shale (KRS) Composites from Micro- to Milli-meter Scales

NASA Astrophysics Data System (ADS)

Haque, M. H.; Han, Y.; Hull, K. L.; Abousleiman, Y. N.

2017-12-01

Understanding the failure behavior of kerogen-rich shale (KRS) at multiscale is critical to efficient hydraulic fracture stimulations in unconventional source shale reservoirs. As a composite material consisting of compacted clay particles, silt-sized grains, and organic matter (OM), KRS is highly complex both structurally and mechanically. The OM, which is intertwined within the shale matrix, presents a particular challenge as it can be much more compliant than its surrounding minerals while at the same time have a significantly higher tensile strength. The mode-I fracture toughness and tensile failure behavior of KRS has been studied at the core scale by traditional rock mechanics methods i.e., Brazilian tests and more recently with non-traditional approaches at the micro-scale using nanoindentation techniques. However, core scale testing fails in precisely capturing the effects of OM due to its coarse resolution, while nanoindention may capture the behavior of isolated component but in some cases miss the collective properties of the composite system. To bridge this gap, while still complying with ASTM/ISRM standards in principle, we investigate fracture initiation and propagation in KRS using the single-edge notched beam (SENB) miniature samples with span length in the millimeter scale. The size scale attempts to isolate the contributions from individual components, especially the OM, to the emergent and systematic fracturing behavior of KRS. Crack propagation along and across the bedding planes have left noticeable signatures on fractured OM while travelling through and around an OM body depending upon its size and spatial position along the crack path illustrating what looks like crack arrest and/or crack bridging in a composite porous matrix. The fractured surface of OM, even being polymeric in nature, exhibits smooth and even surface profile when ripped apart but not in all observed surfaces. Unique microscale features such as- ridges, twists, and

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

USGS Publications Warehouse

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

Comparison of petroleum generation kinetics by isothermal hydrous and nonisothermal open-system pyrolysis

USGS Publications Warehouse

Lewan, M.D.; Ruble, T.E.

2002-01-01

This study compares kinetic parameters determined by open-system pyrolysis and hydrous pyrolysis using aliquots of source rocks containing different kerogen types. Kinetic parameters derived from these two pyrolysis methods not only differ in the conditions employed and products generated, but also in the derivation of the kinetic parameters (i.e., isothermal linear regression and non-isothermal nonlinear regression). Results of this comparative study show that there is no correlation between kinetic parameters derived from hydrous pyrolysis and open-system pyrolysis. Hydrous-pyrolysis kinetic parameters determine narrow oil windows that occur over a wide range of temperatures and depths depending in part on the organic-sulfur content of the original kerogen. Conversely, open-system kinetic parameters determine broad oil windows that show no significant differences with kerogen types or their organic-sulfur contents. Comparisons of the kinetic parameters in a hypothetical thermal-burial history (2.5 ??C/my) show open-system kinetic parameters significantly underestimate the extent and timing of oil generation for Type-US kerogen and significantly overestimate the extent and timing of petroleum formation for Type-I kerogen compared to hydrous pyrolysis kinetic parameters. These hypothetical differences determined by the kinetic parameters are supported by natural thermal-burial histories for the Naokelekan source rock (Type-IIS kerogen) in the Zagros basin of Iraq and for the Green River Formation (Type-I kerogen) in the Uinta basin of Utah. Differences in extent and timing of oil generation determined by open-system pyrolysis and hydrous pyrolysis can be attributed to the former not adequately simulating natural oil generation conditions, products, and mechanisms.

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

NASA Astrophysics Data System (ADS)

Eglinton, Timothy I.; Sinninghe Damsté, Jaap S.; Pool, Wim; de Leeuw, Jan W.; Eijk, Gert; Boon, Jaap J.

1992-04-01

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 organic sulphur pyrolysis products (OSPP) were measured, and the results analysed with the aid of multivariate data reduction techniques (principal components analysis, (PCA)). The structural relationships proposed in an earlier publication ( SINNINGHE DAMSTé et al., 1989a) in which OSPP can be grouped according to common "carbon skeletons" are supported by PCA. The distribution of OSPP varies both as a function of kerogen type (as defined by elemental composition) and maturity, reflecting differences in the relative abundance of the various carbon skeleton types. Sulphur-containing products from Type I, Type II, and, to some extent, Type II-S kerogens are dominated by OSPP derived from "moieties" (i.e., discrete structural components within the macromolecule) possessing linear carbon skeletons, while coals and Type III kerogens give rise to higher relative abundances of OSPP with branched carbon skeletons. Type I kerogens are distinguished from Type II kerogens due to the type of linear carbon skeleton, the former yielding higher relative amounts of 2- n-alkylthiophenes and thiolanes and the latter 2,5-di-substituted sulphur-containing products. Products from sulphur-rich (Type II-S) kerogens differ by higher relative abundances of OSPP derived from precursors with isoprenoid and/or steroidal side-chain carbon skeletons, and by higher absolute abundances of all OSPP. Petroleum and, to a lesser extent, bitumen asphaltenes give rise to OSPP with longer carbon skeletons than do kerogens or coals. This observation supports the models proposed by SINNINGHE DAMSTé et al. (1990a) in which sulphur-containing moieties in asphaltenes are bound by fewer intermolecular bridges

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

USGS Publications Warehouse

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.

Use of laboratory simulated pyrolysis in tracing the history of sedimentary organic matter

NASA Technical Reports Server (NTRS)

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

1986-01-01

Results from laboratory simulated pyrolyses experiments show that in addition to depth of burial, preservation of kerogen, and hence any morphologic structure in it, is also dependent on the mineral matrix with which it is associated. In the presence of clay minerals, and especially under dry conditions, extractable lipids released during kerogen decomposition are more rapidly destroyed than in the presence of calcite or chert matrices. The result is production of gas, polar bitumen and pyrobitumen and destruction of biomarkers. During such an early reorganization of the kerogen, the biomarker constituents can be destroyed, or unrecognizably altered. The above process of organic residues maturation appears to be inhibited in the presence of water and is significantly reduced where kerogen is hosted in limestones, dolomites or cherts. These minerals have been characteristically found to be the most reliable in yielding morphological fossils and small quantities of extractable bitumen in Archean and Proterozoic rocks. To understand the validity of chemical and morphological fossils, in the early geologic record, it will be necessary to understand the process of kerogen in sedimentary rocks. To test the role of various minerals on the preservation process, kerogen extracted from a variety of rocks has been heated together with montmorillonite, illite and calcite. The kinetics of the process has been monitored and the products quantitatively identified.

Publications - GMC 15 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 15 Publication Details Title: Visual kerogen and thermal maturation (vitrinite) data for the Reference Unknown, 1981, Visual kerogen and thermal maturation (vitrinite) data for the SOCAL Cape Espenberg

Publications - GMC 121 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 121 Publication Details Title: Vitrinite reflectance and visual kerogen data of cuttings from -Strat, Inc., 1989, Vitrinite reflectance and visual kerogen data of cuttings from the Texaco Inc

Publications - GMC 32 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 32 Publication Details Title: Visual kerogen and vitrinite reflectance data, and a thermal . Bibliographic Reference Maynard, J., and Hemler, Tom, 1983, Visual kerogen and vitrinite reflectance data, and a

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

NASA Astrophysics Data System (ADS)

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

Publications - GMC 249 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 249 Publication Details Title: Source rock geochemical and visual kerogen data from cuttings Reference Unknown, 1995, Source rock geochemical and visual kerogen data from cuttings (2,520-8,837') of the

Role of minerals in the thermal alteration of organic matter. I - Generation of gases and condensates under dry condition

NASA Technical Reports Server (NTRS)

Tannenbaum, E.; Kaplan, I. R.

1985-01-01

Pyrolysis experiments conducted at 200 and 300 C on kerogen and bitumen from the Monterey formation and on the Green River Formation kerogen with montmorillonite, illite, and calcite added are described. The pyrolysis products are identified and gas and condensate analyses are performed. A catalytic effect is detected in the pyrolysis of kerogen with montmorillonite; however, illite and calcite display no catalytic activity. The increased production of C1-C6 hydrocarbons and the dominance of branched hydrocarbons in the C4-C6 range reveals a catalytic influence. It is observed that the catalysis of montmorillonite is greater during bitumen pyrolysis than for kerogen, and catalysis with minerals affects the production of CO2. It is concluded that a mineral matrix is important in determining the type and amount of gases and condensates forming from organic matter under thermal stress.

Role of minerals in thermal alteration of organic matter. II - A material balance

NASA Technical Reports Server (NTRS)

Tannenbaum, Eli; Huizinga, Bradley J.; Kaplan, I. R.

1986-01-01

The paper presents the results of pyrolysis experiments which were carried out on Green River and Monterey Formation kerogens with and without calcite, illite, or montmorillonite at 300 C for 2 to 1,000 hours under dry and hydrous conditions. The data reveal significant differences in the products generated by pyrolysis of kerogens with and without minerals. Both illite and montmorillonite adsorb a considerable portion of the generated bitumen. In the case of calcite, the pyrolysis products are similar to those from kerogen heated alone, and bitumen adsorption is negligible.

Publications - GMC 147 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 147 Publication Details Title: Visual kerogen and TAI data of select cuttings and core (1260 , F.F., 1989, Visual kerogen and TAI data of select cuttings and core (1260 - 8130 feet) from the Union

Publications - GMC 129 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 129 Publication Details Title: Visual kerogen and TAI data of select cuttings and core from , Visual kerogen and TAI data of select cuttings and core from the Chevron USA Inc. Akulik #1 well: Alaska

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

USGS Publications Warehouse

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

Evaluation of kinetic uncertainty in numerical models of petroleum generation

USGS Publications Warehouse

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

Identifying Fossil Biosignatures and Minerals in Mars Analog Materials Using Time-Resolved Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Shkolyar, S.; Farmer, J.; Alerstam, E.; Maruyama, Y.; Blacksberg, J.

2013-12-01

Mars sample return has been identified as a top priority in the planetary science decadal survey. A Mars sample selection and caching mission would be the likely first step in this endeavor. Such a mission would aim to select and prioritize for return to Earth aqueously formed geological samples present at a selected site on Mars, based upon their potential for biosignature capture and preservation. If evidence of past life exists and is found, it is likely to come via the identification of fossilized carbonaceous matter of biological origin (kerogen) found in the selected samples analyzed in laboratories after return to Earth. Raman spectroscopy is considered one of the primary techniques for analyzing materials in situ and selecting the most promising samples for Earth return. We have previously performed a pilot study to better understand the complexities of identifying kerogen using Raman spectroscopy. For the study, we examined a variety of Mars analog materials representing a broad range of mineral compositions and kerogen maturities. The study revealed that kerogen identification in many of the most promising lithologies is often impeded by background fluorescence that originates from long (>10 ns to ms) and short (<1 ns) lifetime fluorophores in both the mineral matrixes and preserved organic matter in the samples. This work explores the potential for time-gated Raman spectroscopy to enable clear kerogen and mineral identifications in such samples. The JPL time-resolved Raman system uses time gating to reduce background fluorescence. It uses a custom-built SPAD (single photon avalanche diode) detector, featuring a 1-ns time-gate, and electronically variable gate delay. Results for a range of fluorescent samples show that the JPL system reduces fluorescence, allowing the identification of both kerogen and mineral components more successfully than with conventional Raman systems. In some of the most challenging samples, the detection of organic matter is

Publications - GMC 20 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

, rock-eval/pyrolysis, total organic carbon) and core logs for the David River USA #1-A, Hoodoo Lake Unit , 1969, Geochemical analysis (vitrinite reflectance, visual kerogen, rock-eval/pyrolysis, total organic gmc020.pdf (3.2 M) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite

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

NASA Astrophysics Data System (ADS)

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.

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

USGS Publications Warehouse

Mendonca, Filho J.G.; Araujo, C.V.; Borrego, A.G.; Cook, A.; Flores, D.; Hackley, P.; Hower, J.C.; Kern, M.L.; Kommeren, K.; Kus, J.; Mastalerz, Maria; Mendonca, J.O.; Menezes, T.R.; Newman, J.; Ranasinghe, P.; Souza, I.V.A.F.; Suarez-Ruiz, I.; Ujiie, Y.

2010-01-01

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 ??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) on

Absence of preserved glucosamine and amino acids in fossil crustacean exoskeletons

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

Schimmelmann, A.; Krause, R.G.F.; DeNiro, M.J.

1988-01-01

No glucosamine and only traces of amino acids were detected in kerogen prepared from fossil crustacean exoskeletons. The elemental C/N ratios of the kerogen samples were above 20, indicating that most of the organic nitrogen was eliminated from the chitin biopolymer during diagenesis. The results contradict earlier reports of the stability of chitin during fossilization.

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

NASA Astrophysics Data System (ADS)

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

Biofacies expression of Upper Cretaceous sequences in the Rock Springs uplift

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

Chen, Y.Y.; Pflum, C.E.; Wright, R.C.

1991-03-01

The sequence-stratigraphic framework and vertical succession of depositional environments in the Upper Cretaceous section of the Rock Springs uplift is expressed in the biofacies patterns as well as in the stratal stacking patterns. Vertical trends in six biofacies parameters track affinities to marine and nonmarine environments as well as proximity to the paleoshoreline. These six parameters and their environmental significance include the relative proportion of herbaceous kerogen (land-derived), amorphous kerogen (marine), dinoflagellates (marine), bisaccate pollen (land-derived but buoyant and easily transported offshore), and the abundance and diversity of benthic foraminifera (both increase offshore). Shoaling marine environments are characterized by anmore » increasing proportion of herbaceous kerogen and decreasing proportions of amorphous kerogen, dinoflagellated, bisaccates, and the abundance and diversity of benthic foraminifera. Conversely, a deepening-upward marine sedimentary succession is characterized by an opposite trend in these parameters. A synthesis of the six biofacies parameters emphasizes the third-order cyclicity of the stratal succession as reflected in the well-developed third-order downlap surfaces and condensed sections. The biofacies trends indicate the transgressive nature of the lower Rock Springs and lower Lewis formations, and the progradational nature of the upper arts of the Baxter, Blair, and Rock Springs formations. An overall progradational (i.e., shoaling) character is exhibited in the three lower sequences (Baxter through Rock Springs) by the progressively decreasing abundance of amorphous kerogen, dinoflagellates, and foraminifera.« less

Generation and migration of petroleum in the Mahakam delta, Indonesia

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

Durand, B.; Bessereau, G.; Doligez, B.

1988-08-01

The Mahakam delta, located east of Kalimantan, Indonesia, contains sediments of Miocene-Pliocene age. Their thickness may reach more than 8,000 m in places, and sections which have been drilled are generally overpressured below 3,000 to 4,000 m. Petroleum was formed essentially from a kerogen originating in terrestrial land plants grown in an equatorial climate. The kerogen may occur either dispersed in clays or concentrated in humic coal beds. Petroleum potential (oil and gas) of this kerogen at the beginning of catagenesis is 200-250 mg HC/g organic carbon on the average (as measured by Rock-Eval pyrolysis) but is highly variable aroundmore » this mean value (100-400 mg HC/g organic carbon approximately). Although the kerogen is of terrestrial origin, the kerogen-containing sediments have the capacity to produce and expel oil at depth, as shown by large quantities of oil pooled in sandy reservoirs together with gas in a relatively small area. Depth of top oil kitchen varies from 2,500 to 4,000 m and is greater in synclines than on top of structures. Present isotherms follow more or less the same pattern. Migration is very recent and is till at work. Light hydrocarbons have migrated farther from their source than heavy ones did. Thus condensate in pooled gas and the density of pooled oil tend to increase with depth. These variations of oil and gas compositions along secondary and tertiary migration routes are likely to be provoked by evaporative fractionation processes.« less

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Thermal alteration experiments on organic matter from recent marine sediments in relation to petroleum genesis

NASA Technical Reports Server (NTRS)

Ishiwatari, R.; Ishiwatari, M.; Rohrback, B. G.; Kaplan, I. R.

1977-01-01

Three fractions of organic matter: lipid (benzene:methanol-extractable), humic acid (alkali-extractable) and kerogen (residue) were extracted from a young marine sediment (Tanner Basin, offshore southern California) and heated for different times (5-116 hr) and temperatures (150-410 C). The volatile (gases) and liquid products, as well as residual material, were then analyzed. On a weight basis, the lipid fraction produced 58% of the total identified n-alkanes, the kerogen fraction 41%, and the humic acid less than 1%. The volatiles produced by heating the lipid and humic acid fractions were largely CO2 and water, whereas those produced from heated kerogen also included methane, hydrogen gas and small amounts of C2-C4 hydrocarbons. A mechanism for hydrocarbon production due to the thermal alteration of organic constituents of marine sediment is discussed.

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

DTIC Science & Technology

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

Stable sulfur isotope partitioning during simulated petroleum formation as determined by hydrous pyrolysis of Ghareb Limestone, Israel

USGS Publications Warehouse

Amrani, A.; Lewan, M.D.; Aizenshtat, Zeev

2005-01-01

Hydrous pyrolysis experiments at 200 to 365??C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2 S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2??? in 34S during thermal maturation compared with the initial ??34S values. The ??34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1??? of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21??? lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the ??34S-enriched secondary pyrite decomposes above 300??C resulting in a corresponding decrease in the ??34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen ??34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The

Oil Shale

USGS Publications Warehouse

Birdwell, Justin E.

2017-01-01

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

The role of minerals in the thermal alteration of organic matter. IV - Generation of n-alkanes, acyclic isoprenoids, and alkenes in laboratory experiments

NASA Technical Reports Server (NTRS)

Huizinga, Bradley J.; Tannenbaum, Eli; Kaplan, Isaac R.

1987-01-01

The effect of common sedimentary minerals (illite, Na-montmorillonite, or calcite) under different water concentrations on the generation and release of n-alkanes, acyclic isoprenoids, and select alkenes from oil-prone kerogens was investigated. Matrices containing Green River Formation kerogen or Monterey Formation kerogen, alone or in the presence of minerals, were heated at 200 or 300 C for periods of up to 1000 hours, and the pyrolysis products were analyzed. The influence of the first two clay minerals was found to be critically dependent on the water content. Under the dry pyrolysis conditions, both minerals significantly reduced alkene formation; the C12+ n-alkanes and acyclic isoprenoids were mostly destroyed by montmorillonite, but underwent only minor alteration with illite. Under hydrous conditions (mineral/water of 2/1), the effects of both minerals were substantially reduced. Calcite had no significant effect on the thermal evolution of the hydrocarbons.

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

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

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 kerogensmore » 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.« less

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

USGS Publications Warehouse

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.

Generation of aliphatic acid anions and carbon dioxide by hydrous pyrolysis of crude oils

USGS Publications Warehouse

Kharaka, Y.K.; Lundegard, P.D.; Ambats, G.; Evans, William C.; Bischoff, J.L.

1993-01-01

Two crude oils with relatively high (0.60 wt%) and low (0.18 wt%) oxygen contents were heated in the presence of water in gold-plated reactors at 300??C for 2348 h. The high-oxygen oil was also heated at 200??C for 5711 h. The compositions of aqueous organic acid anions of the oils and of the headspace gases were monitored inn order to investigate the distribution of organic acids that can be generated from liquid petroleum. The oil with higher oxygen content generated about five times as much organic anions as the other oil. The dominant organic anions produced were acetate, propionate and butyrate. Small amounts of formate, succinate, methyl succinate and oxalate were also produced. The dominant oxygen-containing product was CO2, as has been observed in similar studies on the hydrous pyrolysis of kerogen. These results indicate that a significant portion (10-30%) of organic acid anions reported i be generated by thermal alteration of oils in reservoir rocks. The bulk of organic acid anions present in formation waters, however, is most likely generated by thermal alteration of kerogen in source rocks. Kerogen is more abundant than oil in sedimentary basins and the relative yields of organic acid anions reported from the hydrous pyrolysis of kerogen are much higher than the yields obtained for the two oils. ?? 1993.

The interfacial energetics of the oil molecules interactions with shale media using molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Zhang, Z.; Wang, J.

2017-12-01

Characterizing the behavior of oil molecules in nanopore is vital to the understanding of geochemistry of hydrocarbon-bearing fluid in ultra-tight source rocks, such as shale. The heterogeneous nature of hydrocarbon system of nanoscale complicates experimental studies of oil / shale interfacial interaction. Therefore, to gain mechanistic understanding of the interplay of oil molecules in rock nanopore, molecular dynamics simulations have been applied to study the interactions of polar and non-polar oil on both calcite and kerogen surfaces. The effect of surface wetting, oil polarity, and temperature on the Gibbs free energy of adsorption have been investigated. The free energy, entropy, and enthalpy profiles have been calculated using advanced molecular dynamics method: umbrella sampling. In agreement with experiment, 1) surface with adsorbed water layer significantly reduces the oil adsorption energy on kerogen and turns the calcite surface to highly oil-repellent; 2) polar oil has overall stronger adsorption free energy than that of non-polar oil on both non-wetted calcite and kerogen surface; 3) organic interface (e.g. kerogen) exhibits stronger adsorption of oil molecules compared to inorganic one (e.g. calcite). The finding of this study indicates that oil displacement in nanopores can be enhanced by promoting the water adsorption on surface and reducing the polarity of oil on both inorganic and organic interfaces.

Mineralogy and source rock evaluation of the marine Oligo-Miocene sediments in some wells in the Nile Delta and North Sinai, Egypt

NASA Astrophysics Data System (ADS)

El sheikh, Hassan; Faris, Mahmoud; Shaker, Fatma; Kumral, Mustafa

2016-06-01

This paper aims to study the mineralogical composition and determine the petroleum potential of source rocks of the Oligocene-Miocene sequence in the Nile Delta and North Sinai districts. The studied interval in the five wells can be divided into five rock units arranged from the top to base; Qawasim, Sidi Salem, Kareem, Rudeis, and Qantara formations. The bulk rock mineralogy of the samples was investigated using X-Ray Diffraction technique (XRD). The results showed that the sediments of the Nile Delta area are characterized by the abundance of quartz and kaolinite with subordinate amounts of feldspars, calcite, gypsum, dolomite, and muscovite. On the other hand, the data of the bulk rock analysis at the North Sinai wells showed that kaolinite, quartz, feldspar and calcite are the main constituents associated with minor amounts of dolomite, gypsum, mica, zeolite, and ankerite. Based on the organic geochemical investigations (TOC and Rock-Eval pyrolysis analyses), all studied formations in both areas are thermally immature but in the Nile delta area, Qawasim, Sidi Salem and Qantara formations (El-Temsah-2 Well) are organically-rich and have a good petroleum potential (kerogen Type II-oil-prone), while Rudeis Formation is a poor petroleum potential source rock (kerogen Type III-gas-prone). In the North Sinai area, Qantara Formation has a poor petroleum potential (kerogen Type III-gas-prone) and Sidi Salem Formation (Bardawil-1 Well) is a good petroleum potential source rock (kerogen Type II-oil-prone).

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

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

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 westernmore » 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.« less

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed Central

Meslé, Margaux; Dromart, Gilles; Haeseler, Frank; Oger, Philippe M.

2015-01-01

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 sedimentary rocks, shale, 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 to the carbon and energy source. Indeed, bitumen has a colloidal structure that may prevent the microbial consortia from reaching the 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. PMID:26136731

Biomarkers Indigenous to Late Archean Rocks

NASA Astrophysics Data System (ADS)

Eigenbrode, J. L.; Freeman, K. H.; Summons, R. E.; Love, G. D.; Snape, C. E.

2003-12-01

Two new lines of evidence support the authenticity of molecular fossils in late Archean rocks of the Hamersley Province, Western Australia. Specifically, they support 1) a syngenetic relationship between the kerogen and extractable biomarkers, and 2) a indigenous relationship between extractable compounds and the host rocks. Carbon skeletons released from kerogen via high-pressure hydropyrolysis match those found in associated extracted bitumen. Biomarker ratios indicate less mature steranes and terpanes (i.e. hopanes and tricyclic terpanes) are embedded in the kerogen matrix as compared to the highly mature steranes and terpanes in the extracts, which is similar to findings in other hydropyrolysis experiments. Lithology-associated variations in biomarker distributions are noteworthy and suggest environmental settings are associated with differing biotic ecosystems. The evidence reported here confirms the 2.7 Ga antiquity of diverse biosynthetic pathways. Molecular data, together with isotopic data, indicate aerobic and anaerobic respiration pathways were fundamental to the complex microbial biogeochemistry of the late Archean. The biomarkers in these rocks support an early radiation of the three domains of life and radiation within the bacteria, such that clades of cyanobacteria, green sulfur bacteria, and proteobacteria had been established.

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

NASA Astrophysics Data System (ADS)

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

Analysis of the effectiveness of steam retorting of oil shale

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

Jacobs, H.R.; Pensel, R.W.; Udell, K.S.

A numerical model is developed to describe the retorting of oil shale using superheated steam. The model describes not only the temperature history of the shale but predicts the evolution of shale oil from kerogen decomposition and the breakdown of the carbonates existing in the shale matrix. The heat transfer coefficients between the water and the shale are determined from experiments utilizing the model to reduce the data. Similarly the model is used with thermogravimetric analysis experiments to develop an improved kinetics expression for kerogen decomposition in a steam environment. Numerical results are presented which indicate the effect of oilmore » shale particle size and steam temperature on oil production.« less

A Thermoplasticity Model for Oil Shale

DOE PAGES

White, Joshua A.; Burnham, Alan K.; Camp, David W.

2016-03-31

Several regions of the world have abundant oil shale resources, but accessing this energy supply poses a number of challenges. One particular difficulty is the thermomechanical behavior of the material. When heated to sufficient temperatures, thermal conversion of kerogen to oil, gas, and other products takes place. This alteration of microstructure leads to a complex geomechanical response. In this work, we develop a thermoplasticity model for oil shale. The model is based on critical state plasticity, a framework often used for modeling clays and soft rocks. The model described here allows for both hardening due to mechanical deformation and softeningmore » due to thermal processes. In particular, the preconsolidation pressure—defining the onset of plastic volumetric compaction—is controlled by a state variable representing the kerogen content of the material. As kerogen is converted to other phases, the material weakens and plastic compaction begins. We calibrate and compare the proposed model to a suite of high-temperature uniaxial and triaxial experiments on core samples from a pilot in situ processing operation in the Green River Formation. In conclusion, we also describe avenues for future work to improve understanding and prediction of the geomechanical behavior of oil shale operations.« less

Petroleum Source Rock Maturation Data Constrain Predictions of Natural Hydrocarbon Seepage into the Atmosphere

NASA Astrophysics Data System (ADS)

Mansfield, M. L.

2013-12-01

Natural seepage of methane from the lithosphere to the atmosphere occurs in regions with large natural gas deposits. According to some authors, it accounts for roughly 5% of the global methane budget. I explore a new approach to estimate methane fluxes based on the maturation of kerogen, which is the hydrocarbon polymer present in petroleum source rocks, and whose pyrolysis leads to the formation of oil and natural gas. The temporal change in the atomic H/C ratio of kerogen lets us estimate the total carbon mass released by it in the form of oil and natural gas. Then the time interval of active kerogen pyrolysis lets us estimate the average annual formation rate of oil and natural gas in any given petroleum system. Obviously, this is an upper bound to the average annual rate at which natural gas seeps into the atmosphere. After adjusting for bio-oxidation of natural gas, I conclude that the average annual seepage rate in the Uinta Basin of eastern Utah is not greater than (3100 × 900) tonne/y. This is (0.5 × 0.15)% of the total flux of methane into the atmosphere over the Basin, as measured during aircraft flights. I speculate about the difference between the regional 0.5% and the global 5% estimates.

Piceance Creek Basin, Colorado, Oil Shale Geodatabase

USGS Publications Warehouse

,

2006-01-01

This geodatabase is a digital reproduction of three legacy USGS oil shale publications--MF-958 (Pitman and Johnson, 1978), MF-1069 (Pitman, 1979), and OC-132 (Pitman and others, 1990). The database consists of 106 feature classes in three feature datasets organized by publication. Each dataset contains isopach contours, isoresource contours, isoresource polygons, and corehole and drillhole locations with resource values for 12 kerogen-rich (R) and kerogen-lean (L) oil shale zones in the Piceance Creek Basin, Colorado. The uppermost zones, Mahogany and R-6, also contain detailed structure files. The zones in descending order are: Mahogany, R-6, L-5, R-5, L-4, R-4, L-3, R-3, L-2, R-2, L-1, and R-1.

Antiquity of the biological sulphur cycle: evidence from sulphur and carbon isotopes in 2700 million-year-old rocks of the Belingwe Belt, Zimbabwe.

PubMed Central

Grassineau, N V; Nisbet, E G; Bickle, M J; Fowler, C M; Lowry, D; Mattey, D P; Abell, P; Martin, A

2001-01-01

Sulphur and carbon isotopic analyses on small samples of kerogens and sulphide minerals from biogenic and non-biogenic sediments of the 2.7 x 10(9) years(Ga)-old Belingwe Greenstone Belt (Zimbabwe) imply that a complex biological sulphur cycle was in operation. Sulphur isotopic compositions display a wider range of biological fractionation than hitherto reported from the Archaean. Carbon isotopic values in kerogen record fractionations characteristic of rubisco activity methanogenesis and methylotrophy and possibly anoxygenic photosynthesis. Carbon and sulphur isotopic fractionations have been interpreted in terms of metabolic processes in 2.7 Ga prokaryote mat communities, and indicate the operation of a diverse array of metabolic processes. The results are consistent with models of early molecular evolution derived from ribosomal RNA. PMID:11209879

Publications - GMC 71 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 71 Publication Details Title: Visual kerogens and rock evaluation pyrolysis determinations for evaluation pyrolysis determinations for 16 North Slope wells: Alaska Division of Geological & Geophysical

Publications - GMC 21 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

#1 well Authors: Unknown Publication Date: Unknown Publisher: Alaska Division of Geological & for more information. Bibliographic Reference Unknown, [n.d.], Visual kerogen analysis - transmitted

The geochemistry of oils and gases from the Cumberland overthrust sheet in Virginia and Tennessee: Chapter G.12 in Coal and petroleum resources in the Appalachian basin: distribution, geologic framework, and geochemical character

USGS Publications Warehouse

Dennen, Kristen O.; Deering, Mark; Burruss, Robert A.; Ruppert, Leslie F.; Ryder, Robert T.

2014-01-01

This study presents high-resolution gas chromatograms of oils and molecular and isotopic analyses of oil-associated gases from 17 wells producing in the Upper Cambrian to Lower Ordovician Knox Group, the Middle and Upper Ordovician Stones River Group, and the Upper Ordovician Trenton Limestone in the Cumberland overthrust sheet. The wells are located in the Ben Hur and Rose Hill fields in Lee County, Va., and in the Swan Creek field in Hancock and Claiborne Counties, Tenn. They produce oils typical of those from source rocks that are rich in Gloeocapsomorpha prisca (G. prisca) (Assemblage A-type kerogen). The Rose Hill oils appear to come from a source that contains a higher proportion of Assemblage A-type kerogen than the Ben Hur and Swan Creek oils. Extrapolation of the δ13C compositions of oil-associated gases to possible kerogen compositions gives estimates of -23 to -24 per mil within the range of isotopic compositions of known G. prisca source material. Gases produced from the Knox Group wells in the Swan Creek field are different from those in the Middle and Upper Ordovician reservoirs and come from a source with a broader range of isotopic values. Trends in isotopic and gasoline-range compositional parameters of the oils and associated gas isotopic and molecular compositions are most likely influenced by changes in local source depositional facies.

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

USGS Publications Warehouse

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.

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

NASA Astrophysics Data System (ADS)

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

A thermal and chemical degradation approach to decipher pristane and phytane precursors in sedimentary organic matter

USGS Publications Warehouse

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

1999-01-01

A thermal and chemical degradation approach was followed to determine the precursors of pristane (Pr) and phytane (Ph) in samples from the Gessoso-solfifera, Ghareb and Green River Formations. Hydrous pyrolysis of these samples yields large amounts of Pr and Ph carbon skeletons, indicating that their precursors are predominantly sequestered in high-molecular-weight fractions. However, chemical degradation of the polar fraction and the kerogen of the unheated samples generally does not release large amounts of Pr and Ph. Additional information on the precursors of Pr and Ph is obtained from flash pyrolysis analyses of kerogens and residues after hydrous pyrolysis and after chemical degradation. Multiple precursors for Pr and Ph are recognised in these three samples. The main increase of the Pr/Ph ratio with increasing maturation temperature, which is associated with strongly increasing amounts of Pr and Ph, is probably due to the higher amount of precursors of Pr compared to Ph, and not to the different timing of generation of Pr and Ph.A thermal and chemical degradation approach was followed to determine the precursors of pristane (Pr) and phytane (Ph) in samples from the Gessoso-solfifera, Ghareb and Green River Formations. Hydrous pyrolysis of these samples yields large amounts of Pr and Ph carbon skeletons, indicating that their precursors are predominantly sequestered in high-molecular-weight fractions. However, chemical degradation of the polar fraction and the kerogen of the unheated samples generally does not release large amounts of Pr and Ph. Additional information on the precursors of Pr and Ph is obtained from flash pyrolysis analyses of kerogens and residues after hydrous pyrolysis and after chemical degradation. Multiple precursors for Pr and Ph are recognised in these three samples. The main increase of the Pr/Ph ratio with increasing maturation temperature, which is associated with strongly increasing amounts of Pr and Ph, is probably due to the

Determining the Biogenicity of Microfossils in the Apex Chert, Western Australia, Using Transmission Electron Microscopy

NASA Technical Reports Server (NTRS)

DeGregorio, B. T.; Sharp, T. G.

2003-01-01

For over a decade, the oldest evidence for life on this planet has been microfossils in the 3.5 Ga Apex Chert in Western Australia. Recently, the biogenicity of these carbon-rich structures has been called into question through reanalysis of the local geology and reinterpretation of the original thin sections. Although initially described as a stratiform, bedded chert of siliceous clasts, the unit is now thought to be a brecciated hydrothermal vein chert. The high temperatures of a hydrothermal environment would probably have detrimental effects to early non-hyperthermophilic life, compared to that of a shallow sea. Conversely, a hydrothermal origin would suggest that if the microfossils were valid, they might have been hyperthermophilic. Apex Chert controversy. The Apex Chert microfossils were originally described as septate filaments composed of kerogen similar in morphology to Proterozoic and modern cyanobacteria. However new thin section analysis shows that these carbonaceous structures are not simple filaments. Many of the original microfossils are branched and have variable thickness when the plane of focus is changed. Hydrothermal alteration of organic remains has also been suggested for the creation of these strange morphologies. Another point of contention lies with the nature of the carbon material in these proposed microfossils. Kerogen is structurally amorphous, but transforms into well-ordered graphite under high pressures and temperatures. Raman spectrometry of the carbonaceous material in the proposed microfossils has been interpreted both as partially graphitized kerogen and amorphous graphite. However, these results are inconclusive, since Raman spectrometry cannot adequately discriminate between kerogen and disordered graphite. There are also opposing views for the origin of the carbon in the Apex Chert. The carbon would be biogenic if the proposed microfossils are indeed the remains of former living organisms. However, an inorganic Fischer

Review of oil families and their petroleum systems of the Williston Basin

USGS Publications Warehouse

Lillis, Paul G.

2013-01-01

Oil bulk properties such as API gravity, sulfur content, and pour point are much underutilized in the recent geochemical literature and are found to be useful here in differentiating oil families. The Red River petroleum system has two oil families that can be differentiated based on pour point. The oils in the Madison petroleum system can be divided into two families based on API gravity-sulfur content relationships, with one family derived from Type II-S kerogen and the other family derived from Type II kerogen with medium sulfur content. The Tyler petroleum system of the Williston Basin may be distinguished from the Heath-Tyler petroleum system in central Montana based on differences in geology and petroleum geochemistry, with Tyler petroleum system oils having a higher pour point and lower sulfur content.

Transition metal catalysis in the generation of petroleum and natural gas. Progress report, [1992--1993

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

Mango, F.

1993-08-01

A new hypothesis is introduced for the generation of petroleum and natural gas. The transition metals, activated under the reducing conditions of diagenesis, are proposed as catalysts in the generation of light hydrocarbons. The objective of this proposal is to test that hypothesis. Transition metals (Ni, V, Ti, Co, Fe), in kerogen, porphyrins, and as pure compounds, will be tested under catagenic conditions for catalytic activity in the conversion of normal paraffins and hydrogen into light hydrocarbons. If the hypothesis is correct, kerogenous transition metals should become catalytically active under the reducing conditions of diagenesis and catalyze the conversion ofmore » paraffins into the light hydrocarbons seen in petroleum. Moreover, the C{sub 1}-C{sub 4} hydrocarbons generated catalytically should be similar in molecular and isotopic compositions to natural gas.« less

Hydrocarbon source potential of the Tanezzuft Formation, Murzuq Basin, south-west Libya: An organic geochemical approach

NASA Astrophysics Data System (ADS)

El Diasty, W. Sh.; El Beialy, S. Y.; Anwari, T. A.; Batten, D. J.

2017-06-01

A detailed organic geochemical study of 20 core and cuttings samples collected from the Silurian Tanezzuft Formation, Murzuq Basin, in the south-western part of Libya has demonstrated the advantages of pyrolysis geochemical methods for evaluating the source-rock potential of this geological unit. Rock-Eval pyrolysis results indicate a wide variation in source richness and quality. The basal Hot Shale samples proved to contain abundant immature to early mature kerogen type II/III (oil-gas prone) that had been deposited in a marine environment under terrigenous influence, implying good to excellent source rocks. Strata above the Hot Shale yielded a mixture of terrigenous and marine type III/II kerogen (gas-oil prone) at the same maturity level as the Hot Shale, indicating the presence of only poor to fair source rocks.

Publications - GMC 253 | Alaska Division of Geological & Geophysical

Science.gov Websites

of the following Copper River basin oil and gas exploratory wells: Amoco Production Company Ahtna Inc Reference Unknown, 1995, Source rock geochemical and visual kerogen data from cuttings of the following

Organic geochemical characterisation of shallow marine Cretaceous formations from Yola Sub-basin, Northern Benue Trough, NE Nigeria

NASA Astrophysics Data System (ADS)

Sarki Yandoka, Babangida M.; Abdullah, Wan Hasiah; Abubakar, M. B.; Hakimi, Mohammed Hail; Jauro, Aliyu; Adegoke, Adebanji Kayode

2016-05-01

The shallow marine shales of the Cretaceous formations namely Yolde, Dukul, Jessu, Sekuliye and Numanha ranging in age from Cenomanian to Coniacian within the Yola Sub-basin in the Northern Benue Trough, northeastern Nigeria were analysed to provide an overview on their hydrocarbon generation potential. This study is based on pyrolysis analysis, total organic carbon content (TOC), extractable organic matter (EOM), biomarker distributions and measured vitrinite reflectance. The present-day TOC contents range between 0.24 and 0.71 wt. % and Hydrogen Index (HI) values between 8.7 and 113 mg HC/g TOC with Type III/IV kerogens. Based on the present-day kerogen typing, the shale sediments are expected to generate mainly gas. Biomarker compositions indicates deposition in a marine environment under suboxic conditions with prevalent contribution of aquatic organic matter and a significant amount of terrigenous organic matter input. Organic matter that is dominated by marine components contains kerogens of Type II and Type II-III. This study shows that the organic matter has been affected by volcanic intrusion and consequently, have reached post-mature stage of oil generation. These higher thermal maturities levels are consistent with the vitrinite reflectance ranging from 0.85 to 2.35 Ro % and high Tmax (440-508 °C) values as supported by biomarker maturity ratios. Based on this study, a high prospect for major gas and minor oil generation potential is anticipated from the shallow marine Cretaceous formations from Yola Sub-basin.

Distribution, origin and prediction of carbon dioxide in petroleum reservoirs

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

Thrasher, J.; Fleet, A.J.

1995-08-01

High concentrations of carbon dioxide (CO{sub 2}) in petroleum reservoirs can significantly reduce the value of the discovery, by diluting any hydrocarbons, and by increasing production costs because of the increased likelihood of corrosion and scale formation. Huge volumes of CO{sub 2} have been found, for example in the Indonesian Natuna d-Alpha structure (estimated 240 tcf gas, of which around 70% is CO{sub 2}). This study reviews the possible sources of CO{sub 2} in the petroleum system, and the geological and geochemical data from some CO{sub 2} {open_quotes}polluted{close_quotes} reservoirs, to improve future predictions of the exploration risk of finding significantmore » CO{sub 2}. A number of case studies show that the most common geological circumstances for the occurrence of high concentrations of CO{sub 2} include: carbonates associated with post-trap igneous activity (e.g. Ibleo Platform, Sicily); reservoir close to hot basement (e.g. Cooper-Eromanga Basin, Australia) and deep faults close to traps (e.g. Gulf of Thailand). Less common circumstances for high proportions of CO{sub 2} in gas include: post-trap igneous activity and coals (e.g. Taranaki, New Zealand) and reservoirs associated with pre-oil window coaly kerogen (e.g. Malay Trough), although the volumes of CO{sub 2} generated from kerogen are usually low relative to volumes of hydrocarbons generated from kerogen.« less

Organic geochemistry of the 9.6 km Bertha Rogers No. 1. well, Oklahoma

USGS Publications Warehouse

Price, L.C.; Clayton, J.L.; Rumen, L.L.

1981-01-01

Organic geochemical analyses of fine-grained rocks from the 9.590 km Bertha Rogers No. 1 well have been carried out: total organic carbon, Soxhlet extraction and silica gel chromatography, C15+ saturated and aromatic hydrocarbon gas chromatography and mass spectrometry, pyrolysis, kerogen analysis, X-ray diffraction and visual kerogen analysis. Rocks ranged in age from Permian to Ordovician; the well has an estimated bottom hole temperature of 225??C. Some data from this study are inconsistent with conventional theories concerning the generation and thermal destruction of hydrocarbons. For example, appreciable amounts of C15+ gas-condensate-like hydrocarbons are present in very old rocks currently at temperatures where current theory predicts that only methane and graphite should remain. Also, substantial amounts of pyrolyzable C15+ hydrocarbons remain on the kerogen in these deeply buried Paleozoic rocks. This suggests, at least in somes cases, that temperatures much higher than those predicted by current theory are required for generation and thermal destruction of hydrocarbons. The data from this well also suggest that original composition of organic matter and environment of deposition may have a much stronger influence on the organic geochemical characteristics of fine-grained sediments than has previously been ascribed to them. The results from this well, from other deep hot wells in which temperatures exceed 200??C, and from laboratory experiments, suggest that some of the basic concepts of the generation and maturation of petroleum hydrocarbons may be in error and perhaps should be reexamined. ?? 1981.

Publications - GMC 148 | Alaska Division of Geological & Geophysical

Science.gov Websites

feet) from the Chevron USA Eagle Creek #1 well Authors: Weber, F.F. Publication Date: 1989 Publisher ., 1989, Visual kerogen and TAI data of select cuttings (1530 - 12000 feet) from the Chevron USA Eagle

Precambrian organic geochemistry - Preservation of the record

NASA Technical Reports Server (NTRS)

Hayes, J. M.; Wedeking, K. W.; Kaplan, I. R.

1983-01-01

A review of earlier studies is presented, and new results in Precambrian organic geochemistry are discussed. It is pointed out that two lines of evidence can be developed. One is based on structural organic chemistry, while the other is based on isotopic analyses. In the present investigation, the results of both structural and isotopic investigations of Precambrian organic matter are discussed. Processes and products related to organic geochemistry are examined, taking into account the carbon cycle, an approximate view of the principal pathways of carbon cycling associated with organic matter in the present global ecosystem, processes affecting sedimentary organic matter, and distribution and types of organic matter. Attention is given to chemical fossils in Precambrian sediments, kerogen analyses, the determination of the structural characteristics of kerogen, and data concerning the preservation of the Precambrian organic geochemical record.

Controls on the molecular and carbon isotopic composition of organic matter deposited in a Kimmeridgian euxinic shelf sea: evidence for preservation of carbohydrates through sulfurisation

NASA Astrophysics Data System (ADS)

Van Kaam-Peters, Heidy M. E.; Schouten, Stefan; Köster, Jörgen; Sinninghe Damstè, Jaap S.

1998-10-01

Thirteen samples from the Kimmeridge Clay Formation (KCF) in Dorset, covering all different lithologies, were studied using bulk and molecular geochemical and microscopical techniques. Our data show that the positive correlation between TOC and δ 13C TOC reported for shales (Huc et al., 1992) also holds for other lithologies (e.g., limestones) if we correct for dilution by carbonate (TOC∗). Despite the wide range of δ 13C TOC values (-26.7 to -20.7‰), the δ 13C values of individual biomarkers of algal and green sulfur bacterial origin and of kerogen pyrolysis products (i.e., n-alkanes) show in general only small changes (<2‰). This indicates that changes in the concentration of dissolved inorganic carbon (DIC) or δ 13C of DIC (δ 13C DIC) in the palaeowater column cannot account for the 6‰ difference in δ 13C TOC. Kerogen pyrolysates indicated that with increasing TOC∗, and thus increasing δ 13C TOC, carbon isotopically heavy C 1-C 3 alkylated thiophenes with a linear carbon skeleton become increasingly abundant; in the case of the Blackstone Band kerogen (TOC∗ = 63%) they dominate the pyrolysate. These thiophenes are probably derived from sulfur-bound carbohydrates in the kerogen. Algal carbohydrates are typically 5-10‰ heavier than algal lipids and differences in preservation of labile carbohydrate carbon through sulfurisation may thus explain the range in δ 13C TOC values without the need to invoke any change in water column conditions. The increasing dominance of thiophenes in the kerogen pyrolysate with increasing TOC∗ is consistent with the increasing Sulfur Index (mg S org/g TOC), the decreasing S PYRITE/S TOT ratio, and the increasing dominance of orange amorphous organic matter produced by natural sulfurisation. The organic matter of all sediments was deposited under euxinic conditions as revealed by the occurrence of isorenieratene derivatives indicating (periodic) photic zone euxinia. At times of reduced run-off from the hinterland

A new laboratory approach to shale analysis using NMR relaxometry

USGS Publications Warehouse

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

2013-01-01

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

Oxygen isotope analysis of fossil organic matter by secondary ion mass spectrometry

NASA Astrophysics Data System (ADS)

Tartèse, Romain; Chaussidon, Marc; Gurenko, Andrey; Delarue, Frédéric; Robert, François

2016-06-01

We have developed an analytical procedure for the measurement of oxygen isotope composition of fossil organic matter by secondary ion mass spectrometry (SIMS) at the sub-per mill level, with a spatial resolution of 20-30 μm. The oxygen isotope composition of coal and kerogen samples determined by SIMS are on average consistent with the bulk oxygen isotope compositions determined by temperature conversion elemental analysis - isotope ratio mass spectrometry (TC/EA-IRMS), but display large spreads of δ18O of ∼5-10‰, attributed to mixing of remnants of organic compounds with distinct δ18O signatures. Most of the δ18O values obtained on two kerogen residues extracted from the Eocene Clarno and Early Devonian Rhynie continental chert samples and on two immature coal samples range between ∼10‰ and ∼25‰. Based on the average δ18O values of these samples, and on the O isotope composition of water processed by plants that now constitute the Eocene Clarno kerogen, we estimated δ18Owater values ranging between around -11‰ and -1‰, which overall correspond well within the range of O isotope compositions for present-day continental waters. SIMS analyses of cyanobacteria-derived organic matter from the Silurian Zdanow chert sample yielded δ18O values in the range 12-20‰. Based on the O isotope composition measured on recent cyanobacteria from the hypersaline Lake Natron (Tanzania), and on the O isotope composition of the lake waters in which they lived, we propose that δ18O values of cyanobacteria remnants are enriched by about ∼18 ± 2‰ to 22 ± 2‰ relative to coeval waters. This relationship suggests that deep ocean waters in which the Zdanow cyanobacteria lived during Early Silurian times were characterised by δ18O values of around -5 ± 4‰. This study, establishing the feasibility of micro-analysis of Phanerozoic fossil organic matter samples by SIMS, opens the way for future investigations of kerogens preserved in Archean cherts and of the

Indirect heating pyrolysis of oil shale

DOEpatents

Jones, Jr., John B.; Reeves, Adam A.

1978-09-26

Hot, non-oxygenous gas at carefully controlled quantities and at predetermined depths in a bed of lump oil shale provides pyrolysis of the contained kerogen of the oil shale, and cool non-oxygenous gas is passed up through the bed to conserve the heat

Underground Organic-Rich Fluids on Mars: Biotic vs Abiotic Processes

NASA Astrophysics Data System (ADS)

Lin, Y.; El Goresy, A.; Hu, S.; Zhang, J.; Gillet, P.; Xu, Y.; Hao, J.; Miyahara, M.; Ouyang, Z.; Ohtani, E.; Xu, L.; Yang, W.; Feng, L.; Zhao, X.; Yang, J.; Ozawa, S.

2013-09-01

We report kerogen-like organic carbon in fractures of silicates and a few in shock melt veins in the Tissint Martian meteorite. The D-enrichment evidences for a Martian origin, and the δ^13C down to -33 permil is consistent with a biogenic origin.

Publications - GMC 25 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 25 Publication Details Title: Geochemical analysis (total organic carbon, rock-eval pyrolysis Reference Unknown, 1984, Geochemical analysis (total organic carbon, rock-eval pyrolysis, kerogen type ; Total Organic Carbon; Vitrinite Reflectance Top of Page Department of Natural Resources, Division of

Thermal alteration experiments on organic matter in recent marine sediments as a model for petroleum genesis

NASA Technical Reports Server (NTRS)

Baedecker, M. J.; Ikan, R.; Ishiwatari, R.; Kaplan, I. R.

1977-01-01

The fate of naturally occurring lipids and pigments in a marine sediment exposed to elevated temperatures was studied. Samples of a young marine sediment from Tanner Basin, California, were heated to a series of temperatures (65-200 C) for varying periods of time (7-64 days). The sediment was analyzed prior to and after heating for pigments, isoprenoid compounds, alcohols, fatty acids, and hydrocarbons. Structural changes caused by heating unextractable organic material (kerogen) were also studied, and the significance of the results for understanding petroleum genesis is considered. Among other results, fatty acids and hydrocarbons increased in abundance although there appeared to be no obvious precursor-to-product relationship via simple decarboxylation reactions. Chlorins were partially converted into porphyrins. The phytyl side chain of pheophytin was initially preserved intact by reduction of the phytyl double bond, but later converted to a variety of isoprenoid compounds including alkanes. Thermal grafting of components onto kerogen occurred as well as structural changes caused by heat.

Geochemical study of the organic matter from Querecual formation, Anzoategui State, Venezuela

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

Garban, G.; Lopez, L.; Lo Monaco, S.

1996-08-01

Kerogen and bitumen fractions extracted from twenty-one limestone samples from kind section of Querecual formation (Querecual River, Anzoategui State, Venezuela) were analyzed for their content of Co, Cr, Fe, Mn, Mo, Ni, S, Sr, V and Zn. S and trace-metals content from the kerogen fraction were used to obtain information about paleoenvironmental sedimentation conditions of the Querecual formation. Based on these data, and especially on the V and S content variations plus V/Ni, VIV+Ni and Mo/Mo+Cr ratios, we confirm an ancient-reducer condition on this region according with a sulfur-reducer environment. Trace-metals content variations from the bitumen fraction along the studymore » section were used as possible primary migration indicators. V and Ni were the only elements showing a clear tendency to be used as primary migration indicators. The observed tendency allows us to postulate a vertical migration of the bitumen, from center to the extremes of the section.« less

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

NASA Astrophysics Data System (ADS)

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).

Spectrophotometry and organic matter on Iapetus. 1: Composition models

NASA Technical Reports Server (NTRS)

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.

Subcontinuum mass transport of condensed hydrocarbons in nanoporous media

PubMed Central

Falk, Kerstin; Coasne, Benoit; Pellenq, Roland; Ulm, Franz-Josef; Bocquet, Lydéric

2015-01-01

Although hydrocarbon production from unconventional reservoirs, the so-called shale gas, has exploded recently, reliable predictions of resource availability and extraction are missing because conventional tools fail to account for their ultra-low permeability and complexity. Here, we use molecular simulation and statistical mechanics to show that continuum description—Darcy's law—fails to predict transport in shales nanoporous matrix (kerogen). The non-Darcy behaviour arises from strong adsorption in kerogen and the breakdown of hydrodynamics at the nanoscale, which contradict the assumption of viscous flow. Despite this complexity, all permeances collapse on a master curve with an unexpected dependence on alkane length. We rationalize this non-hydrodynamic behaviour using a molecular description capturing the scaling of permeance with alkane length and density. These results, which stress the need for a change of paradigm from classical descriptions to nanofluidic transport, have implications for shale gas but more generally for transport in nanoporous media. PMID:25901931

The composition of the Trojan asteroids

NASA Technical Reports Server (NTRS)

Gradie, J.; Veverka, J.

1980-01-01

Consideration is given to the composition of those Trojan asteroids, Hilda asteroids and 944 Hidalgo with very low albedos and spectral reddening between 0.4 and 1.1 microns with respect to the C asteroids, termed RD objects. It is proposed that the albedo and reddening of these objects can be explained by the presence of very opaque, very red, polymer-type organic compounds structurally similar to kerogen, presumably resulting from Fischer-Tropsch-type reactions in the early solar nebula. The spectra and various mixtures of powdered montmorillonite, magnetite, coal-tar residue containing kerogen substances and carbon black are shown to provide a good match to the RD asteroid spectral properties. It is suggested that the nonsoluble carbonaceous residue may have required lower temperatures for its formation and preservation than carbonaceous materials in the carbonaceous chondrites and C asteroids, and thus explain the absence of RD objects closer than 4 AU from the sun.

Publications - GMC 122 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 122 Publication Details Title: Total organic carbon, rock-eval pyrolysis, vitrinite for more information. Bibliographic Reference Exxon, and Geo-Strat, Inc., 1989, Total organic carbon Information gmc122.pdf (1.4 M) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon

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)

NASA Astrophysics Data System (ADS)

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.

Examining Archean methanotrophy

NASA Astrophysics Data System (ADS)

Slotznick, Sarah P.; Fischer, Woodward W.

2016-05-01

The carbon isotope ratios preserved in sedimentary rocks can be used to fingerprint ancient metabolisms. Organic carbon in Late Archean samples stands out from that of other intervals with unusually low δ13C values (∼-45 to -60‰). It was hypothesized that these light compositions record ecosystem-wide methane cycling and methanotrophy, either of the aerobic or anaerobic variety. To test this idea, we studied the petrography and carbon and oxygen isotope systematics of well-known and spectacular occurrences of shallow water stromatolites from the 2.72 Ga Tumbiana Formation of Western Australia. We examined the carbonate cements and kerogen produced within the stromatolites, because methanotrophy is expected to leave an isotopic fingerprint in these carbon reservoirs. Mathematical modeling of Archean carbonate chemistry further reveals that methanotrophy should still have a discernible signature preserved in the isotopic record, somewhat diminished from those observed in Phanerozoic sedimentary basins due to higher dissolved inorganic carbon concentrations. These stromatolites contain kerogen with δ13Corg values of ∼ - 50 ‰. By microsampling different regions and textures within the stromatolites, we determined that the isotopic compositions of the authigenic calcite cements show a low degree of variation and are nearly identical to values estimated for seawater at this time; the lack of low and variable δ13Ccarb values implies that methanotrophy does not explain the low δ13Corg seen in the coeval kerogen. These observations do not support a methanotrophy hypothesis, but instead hint that the Late Archean may constitute an interval wherein autotrophs employed markedly different biochemical processes of energy conservation and carbon fixation.

Evaluation of current techniques for isolation of chars as natural adsorbents

USGS Publications Warehouse

Chun, Y.; Sheng, G.; Chiou, C.T.

2004-01-01

Chars in soils or sediments may potentially influence the soil/sediment sorption behavior. Current techniques for the isolation of black carbon including chars rely often on acid demineralization, base extraction, and chemical oxidation to remove salts and minerals, humic acid, and refractory kerogen, respectively. Little is known about the potential effects of these chemical processes on the char surface and adsorptive properties. This study examined the effects of acid demineralization, base extraction, and acidic Cr2O72- oxidation on the surface areas, surface acidity, and benzene adsorption characteristics of laboratory-produced pinewood and wheat-residue chars, pure or mixed with soils, and a commercial activated carbon. Demineralization resulted in a small reduction in the char surface area, whereas base extraction showed no obvious effect. Neither demineralization nor base extraction caused an appreciable variation in benzene adsorption and presumably the char surface properties. By contrast, the Cr2O 72- oxidation caused a >31% reduction in char surface area. The Boehm titration, supplemented by FTIR spectra, indicated that the surface acidity of oxidized chars increased by a factor between 2.3 and 12 compared to nonoxidized chars. Benzene adsorption with the oxidized chars was lower than that with the non-oxidized chars by a factor of >8.9; both the decrease in char surface area and the increase in char surface acidity contributed to the reduction in char adsorptive power. Although the Cr 2O72- oxidation effectively removes resistant kerogen, it is not well suited for the isolation of chars as contaminant adsorbents because of its destructive nature. Alternative nondestructive techniques that preserve the char surface properties and effectively remove kerogen must be sought.

Impact of Diagenesis on Biosignature Preservation Potential in Playa Lake Evaporites in Verde Formation, Arizona: Implications for Mars Exploration

NASA Astrophysics Data System (ADS)

Shkolyar, S.; Farmer, J. D.

2015-12-01

Major priorities for Mars science include assessing the preservation potential and impact of diagenesis on biosignature preservation in aqueous sedimentary environments. We address these priorities with field and lab studies of playa evaporites of the Verde Formation (upper Pliocene) in Arizona. Evaporites studied include bottom-nucleated halite and displacive growth gypsum in magnesite-rich mudstone. These lithotypes are potential analogs for ancient lacustrine habitable environments on Mars. This study aimed to understand organic matter preservation potential under different diagenetic histories. Methods combined outcrop-scale field observations and lab analyses, including: (1) thin-section petrography to understand diagenetic processes and paragenesis; (2) X-ray powder diffraction to obtain bulk mineralogy; (3) Raman spectroscopy to identify and place phases (and kerogenous fossil remains) within a microtextural context; (4) Total Organic Carbon (TOC) analyses to estimate weight percentages of preserved organic carbon for each subfacies endmember; and (5) electron microprobe to create 2D kerogen maps semi-quantifying kerogen preservation in each subfacies. Results revealed complex diagenetic histories for each evaporite subfacies and pathways for organic matter preservation. Secondary gypsum grew displacively within primary playa lake mudstones during early diagenesis. Mudstones then experienced cementation by Mg-carbonates. Displacive-growth gypsum was sometimes dissolved, forming crystal molds. These molds were later either infilled by secondary sulfates or recrystallized to gypsum pseudomorphs with minor phases present (i.e., glauberite). These observations helped define taphonomic models for organic matter preservation in each subfacies. This work has the potential to inform in situ target identification, sampling strategies, and data interpretations for future Mars Sample Return missions (e.g., sample caching strategies for NASA's Mars 2020 mission).

Publications - GMC 72 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 72 Publication Details Title: Organic carbon, rock-eval pyrolysis, kerogen type, maturation , and vitrinite reflectance geochemical data, and a source rock evaluation for the Exxon OCS-Y-0280-1 publication sales page for more information. Bibliographic Reference Texaco, Inc., 1987, Organic carbon, rock

Enhanced late gas generation potential of petroleum source rocks via recombination reactions: Evidence from the Norwegian North Sea

NASA Astrophysics Data System (ADS)

Erdmann, Michael; Horsfield, Brian

2006-08-01

Gas generation in the deep reaches of sedimentary basins is usually considered to take place via the primary cracking of short alkyl groups from overmature kerogen or the secondary cracking of petroleum. Here, we show that recombination reactions ultimately play the dominant role in controlling the timing of late gas generation in source rocks which contain mixtures of terrigeneous and marine organic matter. These reactions, taking place at low levels of maturation, result in the formation of a thermally stable bitumen, which is the major source of methane at very high maturities. The inferences come from pyrolysis experiments performed on samples of the Draupne Formation (liptinitic Type II kerogen) and Heather Formation (mixed marine-terrigeneous Type III kerogen), both Upper Jurassic source rocks stemming from the Norwegian northern North Sea Viking Graben system. Non-isothermal closed system micro scale sealed vessel (MSSV) pyrolysis, non-isothermal open system pyrolysis and Rock Eval type pyrolysis were performed on the solvent extracted, concentrated kerogens of the two immature samples. The decrease of C 6+ products in the closed system MSSV pyrolysis provided the basis for the calculation of secondary gas (C 1-5) formation. Subtraction of the calculated secondary gas from the total observed gas yields a "remaining" gas. In the case of the Draupne Formation this is equivalent to primary gas cracked directly from the kerogen, as detected by a comparison with multistep open pyrolysis data. For the Heather Formation the calculated remaining gas formation profile is initially attributable to primary gas but there is a second major gas pulse at very high temperature (>550 °C at 5.0 K min -1) that is not primary. This has been explained by a recondensation process where first formed high molecular weight compounds in the closed system yield a macromolecular material that undergoes secondary cracking at elevated temperatures. The experiments provided the input for

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

USGS Publications Warehouse

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

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

NASA Astrophysics Data System (ADS)

Rooney, Alan D.; Selby, David; Lewan, Michael D.; Lillis, Paul G.; Houzay, Jean-Pierre

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 elemental

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

USGS Publications Warehouse

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

Hydrocarbon generation and expulsion in shale Vs. carbonate source rocks

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

Leythaeuser, D.; Krooss, B.; Hillebrand, T.

1993-09-01

For a number of commercially important source rocks of shale and of carbonate lithologies, which were studied by geochemical, microscopical, and petrophysical techniques, a systematic comparison was made of the processes on how hydrocarbon generation and migration proceed with maturity progress. In this way, several fundamental differences between both types of source rocks were recognized, which are related to differences of sedimentary facies and, more importantly, of diagenetic processes responsible for lithification. Whereas siliciclastic sediments lithify mainly by mechanical compaction, carbonate muds get converted into lithified rocks predominantly by chemical diagenesis. With respect to their role as hydrocarbon source rocks,more » pressure solution processes appear to be key elements. During modest burial stages and prior to the onset of hydrocarbon generation reactions by thermal decomposition of kerogen, pressure solution seams and stylolites. These offer favorable conditions for hydrocarbon generation and expulsion-a three-dimensional kerogen network and high organic-matter concentrations that lead to effective saturation of the internal pore fluid system once hydrocarbon generation has started. As a consequence, within such zones pore fluids get overpressured, leading ultimately to fracturing. Petroleum expulsion can then occur at high efficiencies and in an explosive fashion, whereby clay minerals and residual kerogen particles are squeezed in a toothpaste-like fashion into newly created fractures. In order to elucidate several of the above outlined steps of hydrocarbon generation and migration processes, open-system hydrous pyrolysis experiments were performed. This approach permits one to monitor changes in yield and composition of hydrocarbon products generated and expelled at 10[degrees]C temperature increments over temperature range, which mimics in the laboratory the conditions prevailing in nature over the entire liquid window interval.« less

Inorganic carbon and fossil organic carbon are source of bias for quantification of sequestered carbon in mine spoil

NASA Astrophysics Data System (ADS)

Vindušková, Olga; Frouz, Jan

2016-04-01

Carbon sequestration in mine soils has been studied as a possibility to mitigate the rising atmospheric CO2 levels and to improve mine soil quality (Vindu\\vsková and Frouz, 2013). Moreover, these soils offer an unique opportunity to study soil carbon dynamics using the chronosequence approach (using a set of sites of different age on similar parent material). However, quantification of sequestered carbon in mine soils is often complicated by fossil organic carbon (e.g., from coal or kerogen) or inorganic carbon present in the spoil. We present a methodology for quantification of both of these common constituents of mine soils. Our recommendations are based on experiments done on post-mining soils in Sokolov basin, Czech Republic. Here, fossil organic carbon is present mainly as kerogen Type I and II and represents 2-6 wt.% C in these soils. Inorganic carbon in these soils is present mainly as siderite (FeCO3), calcite (CaCO3), and dolomite (CaMg(CO3)2). All of these carbonates are often found in the overburden of coal seams thus being a common constituent of post-mining soils in the world. Vindu\\vsková O, Frouz J, 2013. Soil carbon accumulation after open-cast coal and oil shale mining in Northern Hemisphere: a quantitative review. ENVIRONMENTAL EARTH SCIENCES, 69: 1685-1698. Vindu\\vsková O, Dvořáček V, Prohasková A, Frouz J. 2014. Distinguishing recent and fossil organic matter - A critical step in evaluation of post-mining soil development - using near infrared spectroscopy. ECOLOGICAL ENGINEERING. 73: 643-648. Vindu\\vsková O, Sebag D, Cailleau G, Brus J, Frouz J. 2015. Methodological comparison for quantitative analysis of fossil and recently derived carbon in mine soils with high content of aliphatic kerogen. ORGANIC GEOCHEMISTRY, 89-90:14-22.

Experiments on δ34S mixing between organic and inorganic sulfur species during thermal maturation

USGS Publications Warehouse

Amrani, Alon; Said-Ahamed, Ward; Lewan, Michael D.; Aizenshtat, Zeev

2006-01-01

Reduced sulfur species were studied to constrain isotopic exchange-mixing with synthetic polysulfide cross-linked macromolecules (PCLM), model sulfur containing molecules and natural sulfur-rich kerogen, asphalt and oil of the Dead Sea area. PCLM represents protokerogens that are rich in sulfur and thermally unstable. Mixing rates of PCLM with HS-(aq) (added as (NH4)2S(aq)) at low to moderate temperatures (50–200 °C) are rapid. Elemental sulfur and H2S(gas) fully mix isotopes with PCLM during pyrolysis conditions at 200 °C. During these reactions significant structural changes of the PCLM occur to form polysulfide dimers, thiolanes and thiophenes. As pyrolysis temperatures or reaction times increase, the PCLM thermal products are transformed to more aromatic sulfur compounds. Isotopic mixing rates increase with increasing pyrolysis temperature and time. Polysulfide bonds (S–S) in the PCLM are responsible for most of these structural and isotopic changes because of their low stability. Conversely, sulfur isotope mixing does not occur between dibenzothiophene (aromatic S) or hexadecanthiol (C–SH) and HS-(aq) at 200 °C after 48 h. This shows that rates of sulfur isotope mixing are strongly dependent on the functionality of the sulfur in the organic matter. The order of isotopic mixing rates for organic matter is kerogen > asphalt > oil, which is inverse to their sulfur thermal stability. Asphalt and oil with more refractory sulfur show significantly lower isotopes mixing rates than the kerogen with more labile sulfur. Based on the findings of the present study we suggest that sulfur isotopes mixing can occur from early diagenesis into catagenesis and result in isotopic homogenization of the inorganic and organic reduced sulfur pools.

Relationships between carbon isotope evolution and variation of microbes during the Permian-Triassic transition at Meishan Section, South China

NASA Astrophysics Data System (ADS)

Luo, Genming; Huang, Junhuang; Xie, Shucheng; Wignall, Paul B.; Tang, Xinyan; Huang, Xianyu; Yin, Hongfu

2010-06-01

This paper investigates kerogen carbon isotopes, the difference between carbonate and kerogen carbon isotopes (Δ13Ccarb-kero = δ 13Ccarb - δ 13Ckero) and the difference between carbonate and n-C19 alkane compound-specific carbon isotopes (Δ13Ccarb- n-C19 = δ 13Ccarb - δ 13C n-C19) during the Permian-Triassic transition at Meishan, South China. The results show that kerogen carbon isotopes underwent both gradual and sharp shifts in beds 23-25 and 26-29, respectively. The differences between carbonate and organic carbon isotopes, both the Δ13Ccarb-kero and Δ13Ccarb- n-C19, which are mainly affected by CO2-fixing enzyme and pCO2, oscillated frequently during the Permian-Triassic transition. Both the variations of Δ13Ccarb- n-C19 and Δ13Ccarb-kero coupled with the alternation between cyanobacteria and green sulfur bacteria indicated by biomarkers. The episodic low values of Δ13Ccarb- n-C19 corresponded to episodic blooms of green sulfur bacteria, while the episodic high values of Δ13Ccarb- n-C19 corresponded to episodic blooms of cyanobacteria. The relationships between the variation of carbon isotopes and biota show that the microbes which flourished after the extinction of macroorganism affected the carbon isotope fractionation greatly. Combining the carbon isotope compositions and the pattern of size variation of the conodont Neogondolella, this paper supposes that anoxia of the photic zone at bed 24 was episodic and it would be caused by the degradation of terrigenous organic matters by sulfate reducing bacteria in the upper water column. Considered together with results from previous research, the high resolution variation of the biogeochemistry presents the sequence of the important geo-events during the Permian-Triassic crisis.

Long-term controls on the composition of particulate organic carbon buried offshore from the Waipaoa River, North Island, New Zealand

NASA Astrophysics Data System (ADS)

Leithold, E. L.; Blair, N. E.; Childress, L. B.; Brulet, B.

2009-12-01

In the Waipaoa watershed on the North Island of New Zealand, as in many small mountainous watersheds around the world, high sediment yields are accommodated by the weathering and mass wasting of bedrock as well as of its mantle of soil and vegetation. Investigation of both the contemporary Waipaoa system and the sedimentary record preserved in adjacent marine depocenters reveals that these three sources of sediment have also been the primary sources of riverine POC throughout the watershed’s Holocene history, but that their relative roles have varied as a function of environmental perturbations. Mass balance calculations using stable and radiogenic carbon isotopic ratios of organic matter associated with both bulk sediments and clay-sized isolates point to a large and persistent contribution of kerogen to POC in the Waipaoa system. This material has accumulated on the continental margin along with terrestrial plant-derived OC, much of which apparently had a short residence time in the watershed. The accelerated contribution of OC-poor volcanic tephra to the Waipaoa sediment load beginning about 4000 years ago led to dilution of both the kerogen and plant fraction, and ultimately to enhanced marine OC burial on the shelf via production of new mineral surface area and sorption from porewaters. Beginning around 700 years BP, anthropogenic influences have left their mark on the watershed and offshore record, including the introduction of a pulse of fine-grained charcoal from biomass burning. Deforestation of the headwaters has led to more widespread shallow landsliding and to the development of large gully complexes incised into tectonically crushed mudstones. The increased kerogen flux due to chronic gully erosion is apparent in the offshore record, but its impact on the composition and age of OC buried on the continental shelf is muted compared to the increase in riverine sediment discharge and sediment accumulation observed on the margin.

Diphytanyl glycerol ether distributions in sediments of the Orca Basin

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

Pease, T.K.; VanVleet, E.S.; Barre, J.S.

1992-09-01

Archaebacterially produced diphytanyl glycerol ether (DPGE) was examined in core sediments from the Orca Basin, an anoxic hypersaline basin in the northwestern Gulf of Mexico, to observe its spatial variability and potential origin. A differential extraction protocol was employed to quantify the isopranyl glycerol ethers associated with unbound, intermediate-bound, and kerogen-bound lipid fractions. Archaebacterial lipids were evident at all depths for the unbound and intermediate-bound fractions. Concentrations of DPGE ranged from 0.51 to 2.91 [mu]g/g dry sediment at the surface and showed secondary maxima deeper in basin sediments. Intermediate-bound DPGE concentrations exhibited an inverse relationship to unbound DPGE concentrations. Kerogen-boundmore » DPGE concentrations were normally below detection limits. Earlier studies describing the general homogeneity of lipid components within the overlying brine and at the brine/seawater interface suggest that the large-scale sedimentary DPGE variations observed in this study result from spatial and temporal variations in in-situ production by methanogenic or extremely halophilic archaebacteria.« less

Decrease of aliphatic CHs from diatoms by in situ heating infrared microspectroscopy

NASA Astrophysics Data System (ADS)

Alipour, Leila; Nakashima, Satoru

2016-04-01

In situ heating IR microspectroscopy at 260-300°C under air and N2 conditions has been conducted on diatom frustules to examine aliphatic CH losses during heating, simulating their changes with burial-diagenesis. Assuming a reaction model made up of two first-order kinetic relations, reaction rate constants k1 and k2 and activation energies (Ea) were evaluated for aliphatic CHs. The rate constants for loss of aliphatic CHs of diatom frustules under air and N2 flow are much larger, with much smaller activation energies (57-109 kJ/mol: air; 14-44 kJ/mol: N2), than those for conventional hydrocarbon generation reactions from kerogens (170-370 kJ/mol) studied at higher temperatures (350-450°C). The CH decrease rates are somewhat different from the amide I decrease (protein degradation) rates. The obtained results suggest that organic transformation reactions including degradation of aliphatic CHs inside the diatom silica frustules might be quite different from those of kerogens separated from the biological structures.

Timing of oil and gas generation of petroleum systems in the Southwestern Wyoming Province

USGS Publications Warehouse

Roberts, L.N.R.; Lewan, M.D.; Finn, T.M.

2004-01-01

Burial history, thermal maturity, and timing of petroleum generation were modeled for eight key source-rock horizons at seven locations throughout the Southwestern Wyoming Province. The horizons are the bases of the Lower Permian Phosphoria Formation, the Upper Cretaceous Mowry Shale, Niobrara Formation, Baxter Shale (and equivalents), upper part of the Mesaverde Group, Lewis Shale, Lance Formation, and the Tertiary (Paleocene) Fort Union Formation. Burial history locations include three in the deepest parts of the province (Adobe Town in the Washakie Basin, Eagles Nest in the Great Divide Basin, and Wagon Wheel in the northern Green River Basin); two at intermediate basin depths (Federal 31-1 and Currant, Creek in the central and southern parts of the Green River Basin, respectively); and two relatively shallow locations (Bear 1 on the southeastern margin of the Sand Wash Basin and Bruff 2 on the Moxa arch). An overall ranking of the burial history locations in order of decreasing thermal maturity is Adobe Town > Eagles Nest > Wagon Wheel > Currant Creek > Federal 31-1 > Bear-1 > Bruff 2. The results of the models indicate that peak petroleum generation from Cretaceous oil- and gas-prone source rocks in the deepest parts of the province occurred from Late Cretaceous through middle Eocene. At the modeled locations, peak oil generation from source rocks of the Phosphoria Formation, which contain type-IIS kerogen, occurred in the Late Cretaceous (80 to 73 million years ago (Ma)). Gas generation from the cracking of Phosphoria oil reached a peak in the late Paleocene (57 Ma) only in the deepest parts of the province. The Mowry Shale, Niobrara Formation, and Baxter Shale (and equivalents) contain type-IIS or a mix of type-II and type-III kerogens. Oil generation from these units, in the deepest parts of the province, reached peak rates during the latest Cretaceous to early Paleocene (66 to 61 Ma). Only at these deepest locations did these units reach peak gas

Carbon Dioxide Corrosion and Acetate: A Hypothesis on the Influence of Microorganisms

DTIC Science & Technology

2008-11-01

thermocatalytic degradation of kero- gen,5 oxidation of suitable acid precursors," "and the pyrolytic destruction of kerogen or oil components.*IS... oil industry. Both chemical compounds can be produced and consumed by microorganisms during the anaerobic biodegradation of organic matter- including...hydrocarbons. We contend that the principles governing anaerobic biodegration activity can be extrapolated to above ground oil production facilities

Oil/source rock correlations in the Polish Flysch Carpathians and Mesozoic basement and organic facies of the Oligocene Menilite Shales: Insights from hydrous pyrolysis experiments

USGS Publications Warehouse

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

2004-01-01

The Oligocene Menilite Shales in the study area in the Polish Flysch Carpathians are organic-rich and contain varying mixtures of Type-II, Type-IIS and Type-III kerogen. The kerogens are thermally immature to marginally mature based on atomic H/C ratios and Rock-Eval data. This study defined three organic facies, i.e., sedimentary strata with differing hydrocarbon-generation potentials due to varying types and concentrations of organic matter. These facies correspond to the Silesian Unit and the eastern and western portions of the Skole Unit. Analysis of oils generated by hydrous pyrolysis of outcrop samples of Menilite Shales demonstrates that natural crude oils reservoired in the flysch sediments appear to have been generated from the Menilite Shales. Natural oils reservoired in the Mesozoic basement of the Carpathian Foredeep appear to be predominantly derived and migrated from Menilite Shales, with a minor contribution from at least one other source rock most probably within Middle Jurassic strata. Definition of organic facies may have been influenced by the heterogeneous distribution of suitable Menilite Shales outcrops and producing wells, and subsequent sample selection during the analytical phases of the study. ?? 2004 Elsevier Ltd. All rights reserved.

Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale

NASA Technical Reports Server (NTRS)

Chicarelli, M. I.; Hayes, J. M.; Popp, B. N.; Eckardt, C. B.; Maxwell, J. R.

1993-01-01

The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.

Indigenous Precambrian petroleum revisited

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

Murray, G.E.; Kaczor, M.J.; McArthur, R.E.

1980-10-01

Irrefutable evidence of fossil remains from Precambrian sediments and proved petroleum reserves in upper Proterozoic (Riphean-Vendian) strata of the Irkutsk basin, USSR, suggest that unmetamorphosed Precambrian sedimentary rocks should be a focus for hydrocarbon exploration. Since 1965, a dramatic increase in publications which document worldwide occurrences of Precambrian life forms discloses that, by the end of the Proterozoic, organic evolution had produced diversified assemblages of relatively highly developed macroorganisms and microorganisms. Some of these organisms have generated crude oil in the Nonesuch Shale of northern Michigan and kerogen in stromatolitic carbonate rocks in Africa Kerogen has been extracted from approx.more » 2300-m.y. old Transvaal (Africa) stromatolitic limestone containing coccoid and complex filamentous cyanophytes. Also, aromatic and aliphatic hydrocarbons have been obtained from the approx. 2800-m.y. old Bulawayan stromatolitic limestone of Rhodesia. Additional evidence indicates that commercial reserves of petroleum from Precambrian strata are possible. An oil discovery in Lower Cambrian rocks in 1962, at Markovo in the Irkutsk basin of the Siberian platform area, led to four noncommercial and eight commercial fields producing from Lower Cambrian and Upper Proterozoic strata.« less

Shale-oil-recovery systems incorporating ore beneficiation. Final report.

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

Weiss, M.A.; Klumpar, I.V.; Peterson, C.R.

This study analyzed the recovery of oil from oil shale by use of proposed systems which incorporate beneficiation of the shale ore (that is concentration of the kerogen before the oil-recovery step). The objective was to identify systems which could be more attractive than conventional surface retorting of ore. No experimental work was carried out. The systems analyzed consisted of beneficiation methods which could increase kerogen concentrations by at least four-fold. Potentially attractive low-enrichment methods such as density separation were not examined. The technical alternatives considered were bounded by the secondary crusher as input and raw shale oil as output.more » A sequence of ball milling, froth flotation, and retorting concentrate is not attractive for Western shales compared to conventional ore retorting; transporting the concentrate to another location for retorting reduces air emissions in the ore region but cost reduction is questionable. The high capital and energy cost s results largely from the ball milling step which is very inefficient. Major improvements in comminution seem achievable through research and such improvements, plus confirmation of other assumptions, could make high-enrichment beneficiation competitive with conventional processing. 27 figures, 23 tables.« less

Nonprevalence of biochemical fossils in kerogen from pre-Phanerozoic sediments

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

Leventhal, J.; Suess, S. E.; Cloud, P.

Evidence of biochemical and geochemical evolution was sought in insoluble carbonaceous matter from 30 selected pre-Phanerozoic sediments ranging in age from about 3.8 to about 0.7 x 10 9 years. The carbon isotope ratios observed were in the range of -20 to -32 per mil with reference to the Peedee belemnite standard, similar to those previously reported. No systematic trends are obvious to us. Stepwise pyrolysis-gas-chromatography showed only molecules with fewer than 8 carbon atoms at the level of sensitivity of 10 -9 g of organics in a 10 mg rock sample. Carbon, hydrogen, and nitrogen analyses showed noncarbonate carbonmore » from less than 0.1 percent to more than 3 percent, with very small amounts of N. The H/C (atomic) ratios on HCl-leached and HF-treated samples were generally less than 0.3. Evidence of low pyrolysis yields (micro-analysis) and low H/C atomic ratios (macro-analysis) implies that the carbonaceous solids in even the least metamorphosed of these ancient sediments have evolved far toward amorphous carbon or graphite and do not yield useful ''biochemical fossils.''« less

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

USGS Publications Warehouse

Ribeiro da Luz, Beatriz; Crowley, James K.

2012-01-01

We describe evidence of biogenicity in the morphology and carbon content of well-preserved, Neoarchean samples of banded iron formation (BIF) from Carajás, Brazil. Silica-rich BIF layers contain translucent ellipsoidal or trapezoidal structures (∼5–10 μm diameter) composed of silica, hematite, and kerogen, which are arranged in larger ring-like forms (rosettes). Stable carbon isotope analysis yields a δ13C value of −24.5‰ indicating that the contained carbon is likely biogenic. Raman and SEM analyses, as well as wavelength-dispersive X-ray elemental maps, show kerogen inside the rosette forms. Within the iron-rich BIF layers, tubular structures (0.5–5 μm) were observed between hematite granules and blades. Kerogen and kaolinite are present in these structures. Both the rosettes and the tubular structures resemble morphologies that are characteristic of some bacterial species.We hypothesize that the Carajás BIFs originated as biomats formed by one or more species that over time produced large stromatolitic structures. The rosettes and the tubular structures, associated with chert-rich and iron-rich BIF layers, respectively, may represent two different species, or perhaps, two phases of a bacterium life cycle. For example, some modern myxobacteria exhibit similar morphologies in their resting and vegetative stages.Fe(III) precipitation may have occurred by contact of Fe(II) with bacterial slime, leading to oxidation by chemical reactions with exposed polysaccharide hydroxyl and carboxyl groups. The Fe(III) would then have been available for use as a source of energy in a dissimilatory iron reduction type of metabolism. Organic carbon input presumably came from primary producers (not necessarily aerobic) within the local water column, perhaps in shallow-water communities. Alternatively, the carbon may have originated by Fischer–Tropsch synthesis at ocean hydrothermal vents. The observed lateral continuity of BIF layers may perhaps be explained by

Investigation of Coupled model of Pore network and Continuum in shale gas

NASA Astrophysics Data System (ADS)

Cao, G.; Lin, M.

2016-12-01

Flow in shale spanning over many scales, makes the majority of conventional treatment methods disabled. For effectively simulating, a coupled model of pore-scale and continuum-scale was proposed in this paper. Based on the SEM image, we decompose organic-rich-shale into two subdomains: kerogen and inorganic matrix. In kerogen, the nanoscale pore-network is the main storage space and migration pathway so that the molecular phenomena (slip and diffusive transport) is significant. Whereas, inorganic matrix, with relatively large pores and micro fractures, the flow is approximate to Darcy. We use pore-scale network models (PNM) to represent kerogen and continuum-scale models (FVM or FEM) to represent matrix. Finite element mortars are employed to couple pore- and continuum-scale models by enforcing continuity of pressures and fluxes at shared boundary interfaces. In our method, the process in the coupled model is described by pressure square equation, and uses Dirichlet boundary conditions. We discuss several problems: the optimal element number of mortar faces, two categories boundary faces of pore network, the difference between 2D and 3D models, and the difference between continuum models FVM and FEM in mortars. We conclude that: (1) too coarse mesh in mortars will decrease the accuracy, while too fine mesh will lead to an ill-condition even singular system, the optimal element number is depended on boundary pores and nodes number. (2) pore network models are adjacent to two different mortar faces (PNM to PNM, PNM to continuum model), incidental repeated mortar nodes must be deleted. (3) 3D models can be replaced by 2D models under certain condition. (4) FVM is more convenient than FEM, for its simplicity in assigning interface nodes pressure and calculating interface fluxes. This work is supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB10020302), the 973 Program (2014CB239004), the Key Instrument Developing Project of the

Density gradient centrifugation: Application to the separation of macerals of type I, II, and III sedimentary organic matter

USGS Publications Warehouse

Stankiewicz, B.A.; Kruge, M.A.; Crelling, J.C.; Salmon, G.L.

1994-01-01

Samples of organic matter from nine well-known geological units (Green River Fm., Tasmanian Tasmanite, Lower Toarcian Sh. of the Paris Basin, Duwi Fm., New Albany Sh., Monterey Fm., Herrin No. 6 coal, Eocene coal, and Miocene lignite from Kalimantan) were processed by density gradient centrifugation (DGC) to isolate the constituent macerals. Optimal separation, as well as the liberation of microcrystalline pyrite from the organic matter, was obtained by particle size minimization prior to DGC by treatment with liquid N2 and micronization in a fluid energy mill. The resulting small particle size limits the use of optical microscopy, thus microfluorimetry and analytical pyrolysis were also employed to assess the quality and purity of the fractions. Each of the samples exhibits one dominant DGC peak (corresponding to alginite in the Green River Fm., amorphinite in the Lower Toarcian Sh., vitrinite in the Herrin No. 6, etc.) which shifts from 1.05 g mL-1 for the Type I kerogens to between 1.18 and 1.23 g mL-1 for Type II and II-S. The characteristic densities for Type III organic matter are greater still, being 1.27 g mL-1 for the hydrogen-rich Eocene coal, 1.29 g mL-1 for the Carboniferous coal and 1.43 g mL-1 for the oxygen-rich Miocene lignite. Among Type II kerogens, the DGC profile represents a compositional continuum from undegraded alginite through (bacterial) degraded amorphinite; therefore chemical and optical properties change gradually with increasing density. The separation of useful quantities of macerals that occur in only minor amounts is difficult. Such separations require large amounts of starting material and require multiple processing steps. Complete maceral separation for some samples using present methods seems remote. Samples containing macerals with significant density differences due to heteroatom diversity (e.g., preferential sulfur or oxygen concentration in the one maceral), on the other hand, may be successfully separated (e.g., coals and

Bitumen II from the Paleoproterozoic Here’s Your Chance Pb/Zn/Ag deposit: Implications for the analysis of depositional environment and thermal maturity of hydrothermally-altered sediments

NASA Astrophysics Data System (ADS)

Holman, Alex I.; Grice, Kliti; Jaraula, Caroline M. B.; Schimmelmann, Arndt

2014-08-01

The formation of sedimentary exhalative (SEDEX) Pb/Zn deposits is linked to ocean euxinia, but recent evidence suggests that ferruginous conditions may have dominated the deep ocean during the Middle Proterozoic, a maximum period for SEDEX distribution. Biomarkers of sulfate-reducing and sulfide-oxidising bacteria are valuable indicators of euxinic conditions in such settings. Organic matter (OM) from SEDEX deposits is often affected by alteration and/or migration, but OM entrapped within the kerogen/mineral matrix (Bitumen II) may be less affected than the freely-extractable OM (Bitumen I). We analysed Bitumen II from the Paleoproterozoic Here’s Your Chance (HYC) Pb/Zn/Ag deposit to find evidence of euxinic conditions in the depositional environment. n-Alkane distributions in Bitumen II are markedly distinct from previously-reported Bitumen I. Bitumen II contains long-chain n-alkanes (up to C36 or C38) and a strong even-over-odd distribution in a number of samples, which are 4‰ to 7‰ depleted in 13C compared to n-alkanes in Bitumen I and verified as indigenous by comparison with δ13C of isolated kerogen. These features are interpreted as evidence of sulfate-reducing and sulfide-oxidising bacteria, confirming that HYC was deposited under euxinic conditions. Bitumen II has the potential to reveal information from OM that is degraded and/or overprinted in Bitumen I. Commonly-used methylphenanthrene maturity ratios give conflicting information as to the relative maturity of Bitumens I and II. Bitumen I contains a far higher proportion of methylated phenanthrenes than Bitumen II. As Bitumen II is sequestered within the kerogen/mineral matrix it may have restricted access to the ‘methyl pool’ of organic compounds that can donate methyl groups to aromatic hydrocarbons. Parameters that include both phenanthrene and methylphenanthrenes do not appear suitable to compare the maturity of Bitumens I and II; hence there is no clear evidence that Bitumen II is of

The Decomposition of Carbonates and Organics on Mars

NASA Technical Reports Server (NTRS)

Quinn, Richard C.; Zent, Aaron; McKay, Chris; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

The return and analysis of pristine material that is relict of a putative period of chemical evolution is a fumdamental goal of the exobiological exploration of Mars. In order to accomplish this objective, it is desirable to find oxidant-free regions where pristine material can be accessed at the shallowest possible depth (ideally directly from the surface). The objective of our ongoing research is to understand the spatial and temporal distribution of oxidants in the martian regolith and the redox chemistry of the soil; in effect to understand the chemical mechanisms and kinetics relating to the in-situ destruction of organics and the formation of the reactive species responsible for the Viking biology results. In this work, we report on experimental studies of oxidizing processes that may contribute to carbonate and organic degradation on Mars. Organic molecules directly exposed to solar UV may decomposed either directly into CO2, or into more volatile organic fragments. Organic macromolecules not directly exposed to high UV flux are most likely to be affected by atmospheric oxidants which can diffuse to their surfaces. The oxidizing processes examined include: gas-phase oxidants, UV photolysis, and UV-assisted heterogeneous catalysis. For example, assuming a meteroritic infall rate of 4 x 10(exp -4) g/m^2yr (Flynn and McKay 1990) and a flux of organic carbon of 2 x 10(exp -5) g/m^2yr, laboratory measurements of the UV-assisted decomposition of benzenehexacarboxylic acid (mellitic acid, a likely intermediate of kerogen oxidation), indicate its decomposition rate on Mars would exceed the total flux of organic carbon to the planet by over four orders of magnitude. Our measurements indicate that although the decomposition temperature of kerogens in some cases exceeds the temperature limit of the Viking GCMS, it is unlikely kerogens or their decomposition intermediates were present at the Viking landings sites at levels above the GCMS detection limits.

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

NASA Astrophysics Data System (ADS)

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

Geological and geochemical characterization of the Lower Cretaceous Pearsall Formation, Maverick Basin, south Texas: A future shale gas resource?

USGS Publications Warehouse

Hackley, Paul C.

2012-01-01

As part of an assessment of undiscovered hydrocarbon resources in the northern Gulf of Mexico onshore Mesozoic section, the U.S. Geological Survey (USGS) evaluated the Lower Cretaceous Pearsall Formation of the Maverick Basin, south Texas, as a potential shale gas resource. Wireline logs were used to determine the stratigraphic distribution of the Pearsall Formation and to select available core and cuttings samples for analytical investigation. Samples used for this study spanned updip to downdip environments in the Maverick Basin, including several from the current shale gas-producing area of the Pearsall Formation.The term shale does not adequately describe any of the Pearsall samples evaluated for this study, which included argillaceous lime wackestones from more proximal marine depositional environments in Maverick County and argillaceous lime mudstones from the distal Lower Cretaceous shelf edge in western Bee County. Most facies in the Pearsall Formation were deposited in oxygenated environments as evidenced by the presence of biota preserved as shell fragments and the near absence of sediment laminae, which is probably caused by bioturbation. Organic material is poorly preserved and primarily consists of type III kerogen (terrestrial) and type IV kerogen (inert solid bitumen), with a minor contribution from type II kerogen (marine) based on petrographic analysis and pyrolysis. Carbonate dominates the mineralogy followed by clays and quartz. The low abundance and broad size distribution of pyrite are consistent with the presence of oxic conditions during sediment deposition. The Pearsall Formation is in the dry gas window of hydrocarbon generation (mean random vitrinite reflectance values, Ro = 1.2–2.2%) and contains moderate levels of total organic carbon (average 0.86 wt. %), which primarily resides in the inert solid bitumen. Solid bitumen is interpreted to result from in-situ thermal cracking of liquid hydrocarbon generated from original type II kerogen

Advanced Tomographic Imaging Methods for the Analysis of Materials

DTIC Science & Technology

1991-08-01

used in composite manufacture: aluminum, silicon carbide, and titanium aluminide . Also depicted in Fig. 2 are the energy intervals which can...SiC-fiber (SCS6) in a titanium - aluminide matrix. The contrast between SiC and AtIis only 10% over a broad eiaergy range. Therefore, distinguishing the...borehole logging, orrodent detection on turbine blades , kerogen analysis of shale, and contents of coals (sulfur, minerals, and btu). APSTNG

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

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

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 withmore » 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.« less

Eastern Devonian shales: Organic geochemical studies, past and present

USGS Publications Warehouse

Breger, I.A.; Hatcher, P.G.; Romankiw, L.A.; Miknis, F.P.

1983-01-01

The Eastern Devonian shales are represented by a sequence of sediments extending from New York state, south to the northern regions of Georgia and Alabama, and west into Ohio and to the Michigan and Ilinois Basins. Correlatives are known in Texas. The shale is regionally known by a number of names: Chattanooga, Dunkirk, Rhinestreet, Huron, Antrim, Ohio, Woodford, etc. These shales, other than those in Texas, have elicited much interest because they have been a source of unassociated natural gas. It is of particular interest, however, that most of these shales have no associated crude oil, in spite of the fact that they have some of the characteristics normally attributed to source beds. This paper addresses some of the organic geochemical aspects of the kerogen in these shales, in relation to their oil generating potential. Past organic geochemical studies on Eastern Devonian shales will be reviewed. Recent solid state 13C NMR studies on the nature of the organic matter in Eastern Devonian shales show that Eastern Devonian shales contain a larger fraction of aromatic carbon in their chemical composition. Thus, despite their high organic matter contents, their potential as a petroleum source rock is low, because the kerogen in these shales is of a "coaly" nature and hence more prone to producing natural gas.

Updated methodology for nuclear magnetic resonance characterization of shales

NASA Astrophysics Data System (ADS)

Washburn, Kathryn E.; Birdwell, Justin E.

2013-08-01

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

Terminal proterozoic mid-shelf Benthic microbial mats in the Centralian Superbasin and their environmental significance

NASA Astrophysics Data System (ADS)

Logan, Graham A.; Calver, Clive R.; Gorjan, Paul; Summons, Roger E.; Hayes, John M.; Walter, Malcolm R.

1999-05-01

A combined sedimentological and biogeochemical study has been conducted on several Terminal Proterozoic mid-shelf microbial mat facies from the Centralian Super-basin. Isotopic and organic geochemical analysis of the bitumen and kerogen indicated that two sources of organic matter from 'planktonic' and 'benthic microbial-mat' populations contributed to the sediment. The 'planktonic' source provided a suite of n-alkanes with C 20, whereas, the 'benthic' source contributed an overlay of n-alkanes >C 20 with a strong even preference, together with mid-chain methyl alkanes. Kerogen and biomarkers derived from the microbial mat were found to be depleted in 13C relative to planktonic material. Pyrite in the micorbial mats was also found to be depleted in 34S compared to surrounding facies. The combination of these observations suggested that the mats may have been at least partly composed of sulfide oxidising bacteria. These organisms have specific environmental tolerances that set limits on palaeo-environment. Their requirement for oxygen indicates that the water column above the mid-shelf could not have been anoxic. Accordingly, from the results and age determinations reported here, it would appear that mid-shelf environments of the Centralian Superbasin of Australia were seeing significant levels of oxygen through the Ediacarian.

Converting oil shale to liquid fuels: energy inputs and greenhouse gas emissions of the Shell in situ conversion process.

PubMed

Brandt, Adam R

2008-10-01

Oil shale is a sedimentary rock that contains kerogen, a fossil organic material. Kerogen can be heated to produce oil and gas (retorted). This has traditionally been a CO2-intensive process. In this paper, the Shell in situ conversion process (ICP), which is a novel method of retorting oil shale in place, is analyzed. The ICP utilizes electricity to heat the underground shale over a period of 2 years. Hydrocarbons are produced using conventional oil production techniques, leaving shale oil coke within the formation. The energy inputs and outputs from the ICP, as applied to oil shales of the Green River formation, are modeled. Using these energy inputs, the greenhouse gas (GHG) emissions from the ICP are calculated and are compared to emissions from conventional petroleum. Energy outputs (as refined liquid fuel) are 1.2-1.6 times greater than the total primary energy inputs to the process. In the absence of capturing CO2 generated from electricity produced to fuel the process, well-to-pump GHG emissions are in the range of 30.6-37.1 grams of carbon equivalent per megajoule of liquid fuel produced. These full-fuel-cycle emissions are 21%-47% larger than those from conventionally produced petroleum-based fuels.

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

NASA Astrophysics Data System (ADS)

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.

Photocatalytic decomposition of carboxylated molecules on light-exposed martian regolith and its relation to methane production on Mars.

PubMed

Shkrob, Ilya A; Chemerisov, Sergey D; Marin, Timothy W

2010-05-01

We propose that the paucity of organic compounds in martian soil can be accounted for by efficient photocatalytic decomposition of carboxylated molecules due to the occurrence of the photo-Kolbe reaction at the surface of particulate iron(III) oxides that are abundant in the martian regolith. This photoreaction is initiated by the absorption of UVA light, and it readily occurs even at low temperature. The decarboxylation is observed for miscellaneous organic carboxylates, including the nonvolatile products of kerogen oxidation (that are currently thought to accumulate in the soil) as well as alpha-amino acids and peptides. Our study indicates that there may be no "safe haven" for these organic compounds on Mars; oxidation by reactive radicals, such as hydroxyl, is concerted with photocatalytic reactions on the oxide particles. Acting together, these two mechanisms result in mineralization of the organic component. The photooxidation of acetate (the terminal product of radical oxidation of the aliphatic component of kerogen) on the iron(III) oxides results in the formation of methane; this reaction may account for seasonably variable production of methane on Mars. The concomitant reduction of Fe(III) in the regolith leads to the formation of highly soluble ferrous ions that contribute to weathering of the soil particles.

Geosynthesis of organic compounds: I. Alkylphenols

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

Ioppolo-Armanios, M.; Alexander, R.; Kagi, R.I.

1995-07-01

Methylation, isopropylation, and sec-butylation are proposed as geosynthetic processes to account for the alkylphenol compositions of crude oils with phenol distributions dominated by ortho and para substituted compounds. Phenol distributions in eleven crude oils and four kerogen pyrolysates were analysed using GC-MS (gas chromatography-mass spectrometry). Ten of the crude oils show high relative abundances of ortho and para substituted phenol isomers and some were also enriched in C{sub 3}-C{sub 5} alkylphenols compared to the kerogen pyrolysates. Because the distributions of products obtained from the laboratory alkylation of cresols closely resemble those of phenols in these crude oils, we propose thatmore » similar alkylation processes occur in source rocks. Alkylation ratios reflecting the degree of methylation, isopropylation, and sec-butylation, which were based on the relative abundance of the dominant alkylation products compared to their likely precursor ortho-cresol, indicate that high levels of methylation occurred in crude oils over a wide range of maturities, whereas high levels of isopropylation and sec-butylation were observed only in mature samples. Dissolution of the phenols in crude oils by water contact was discounted as an explanation for the observed phenol distributions based on the relative distribution coefficients of phenols between a hydrocarbon phase and water.« less

Alkyl substituted cyclic ethers in 2,300 M yr old Transvaal algal stromatolite

NASA Technical Reports Server (NTRS)

Zumberge, J. E.; Nagy, B.

1975-01-01

Two cyclic ethers have been identified for the first time from insoluble polymer-like kerogen in a Precambrian rock by ozonolysis, gas chromatography, and mass spectrometry. The ethers are 2-n-propyl-3-methyltetrahydrofuran and 2-n-propyltetrahydropyran. These compounds could prove to be the oldest indigenous biochemical fossils. The sample was obtained 750 m stratigraphically above the base of the Transvaal Sequence from an outcrop approximately 315 km north-east of Johannesburg, South Africa.

In Situ Stabilization of Persistent Organic Contaminants in Marine Sediments

DTIC Science & Technology

2004-04-01

dyes (25, 26), amino acids (27), and polymer additives (28, 29). In this study we extend the capabilities of µL2MS to detect PCBs. Using 212 nm...organic carbon followed by treatment with acid to remove inorganic carbon and analysis of the remaining carbon. The soot carbon material isolated by...aliphatic natural organic matter types (algae, cellulose, collagen, cuticle, lignin, kerogen, and humic acid ) and concluded that aliphatic organic matter

Complex conductivity of organic-rich shales

NASA Astrophysics Data System (ADS)

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

Standardization of vitrinite reflectance measurements in shale petroleum systems: How accurate are my Ro data?

USGS Publications Warehouse

Hackley, Paul C.

2014-01-01

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 D7708-11: 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 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 (Ro 0.31-1.53%), from organic-rich to organic-lean (1-22 wt.% total organic carbon), and contained Type I (lacustrine), Type II (marine), and Type III (terrestrial) kerogens. Repeatability values (difference between repetitive results from same operator, same conditions) ranged from 0.03-0.11% absolute reflectance, whereas reproducibility values (difference between results obtained on same test material by different operators, different laboratories) ranged from 0.12-0.54% absolute reflectance. Repeatability and reproducibility 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 the other components. Discussion among

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

DOEpatents

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.

Proceedings of the twentieth annual meeting of the society for organic petrology

USGS Publications Warehouse

Bragg, Linda J.; Lentz, Erika E.; Warwick, Peter D.; Finkelman, Robert B.; Trippi, Michael H.; Karlsen, Alex W.

2004-01-01

The Society for Organic Petrology (TSOP; pronounced "Tee'-sop") was established in 1984 to consolidate and foster the organizational activities of scientists and engineers involved with coal petrology, kerogen petrology, organic geochemistry, and related disciplines. The following report, "Proceedings of the Twentieth Annual Meeting of The Society for Organic Petrology" (ISSN 1060-7250), features technical talks, poster presentations, business meetings, short courses, and field trips from the Fall 2003 annual meeting held in Washington, D.C.

Upper Cretaceous Shannon Sandstone Reservoirs, Powder River Basin, Wyoming: Evidence for organic acid diagenesis

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

Hansley, P.L.; Nuccio, V.F.

Comparison of the petrology of shallow and deep oil reservoirs in the Upper Cretaceous Shannon Sandstone Beds of the Steele Member of the Cody Shale strongly suggests that organic acids have had a more significant impact on the diagenetic alteration of aluminosilicate grains and carbonate cements in the deep reservoirs than in the shallow reservoirs. In shallow reservoirs, detrital grains exhibit minor dissolution, sparse and small overgrowths, and secondary porosity created by dissolution of early calcite cement. However, deeper sandstones are characterized by extensive dissolution of detrital K-feldspar and detrital glauconite grains, and precipitation of abundant, large quartz and feldsparmore » overgrowths. Throughout the Shannon and Steele, dissolution of glauconite and degradation of kerogen were probably aided by clay mineral/organic catalysis, which caused simultaneous reduction of iron and oxidation of kerogen. This process resulted in release of ferrous iron and organic acids and was promoted in the deep reservoirs by higher formation temperatures accounting for more extensive dissolution of aluminosilicate grains. Carbonic acid produced from the dissolution of early calcite cement, decarboxylation of organic matter, and influx of meteoric water after Laramide uplift produced additional dissolution of cements and grains. Dissolution by organic acids and complexing by organic acid anions, however, best explain the intensity of diagenesis and absence of dissolution products in secondary pores and on etched surfaces of framework grains in deep reservoirs.« less

Eastern Devonian shales: Organic geochemical studies

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

Berger, I.A.; Hatchner, P.G.; Miknis, F.P.

The Eastern Devonian shales are represented by a sequence of sediments extending from New York state, south to the northern regions of Georgia and Alabama, and west into Ohio and to the Michigan and Illinois Basins. Correlatives are known in Texas. The shale is regionally known by a number of names: Chattanooga, Dunkirk, Rhinestreet, Huron, Antrim, Ohio, Woodford, etc. These shales, other than those in Texas, have elicited much interest because they have been a source of unassociated natural gas. It is of particular interest, however, that most of these shales have no associated crude oil, in spite of themore » fact that they have some of the characteristics normally attributed to source beds. This paper addresses some of the organic geochemical aspects of the kerogen in these shales, in relation to their oil generating potential. Past organic geochemical studies on Eastern Devonian shales are reviewed. Recent solid state /sup 13/C NMR studies on the nature of the organic matter in Eastern Devonian shales show that Eastern Devonian shales contain a larger fraction of aromatic carbon in their chemical composition. Thus, despite their high organic matter contents, their potential as a petroleum source rock is low, because the kerogen in these shales is of a ''coaly'' nature and hence more prone to producing natural gas.« less

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

NASA Astrophysics Data System (ADS)

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.

Organic geochemistry of sediments of the Deep Gulf of Mexico Basin

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

Sassen, R.; Fang Jiasong

1990-05-01

Analysis of 716 core samples cored at DSDP (Deep Sea Drilling Project) Leg 96 in the Mississippi submarine fan and the Orca and Pigmy basins in the Louisiana continental slope using a Rock-Eval pyrolysis unit with a TOC (total organic carbon) module allows computations of hydrogen index (HI), total organic carbon, kerogen type, and oil generative capacity assessment. No samples are obviously oil prone. TOC content ranges from 0.12 to 2.29%, with an overall average of 9.82%. HI values are generally less than 150 mg HC/g TOC. T{sub max} (maximum temperature of S{sub 2}) values (average = 425{degree}C) show themore » sediments are thermally immature through-out the study area. Hydrocarbon generative potential of the sediments ranges from 492 to 1,107 ppm, with an average of 854 ppm. Higher PI (Production index) values, ranging from 0.12 to 0.32 and averaging 0.15, suggest the presence of hydrocarbon seepage. Because of organically lean, thermally immature, and gas-prone terrestrial kerogen, there is little reason to assume that the sediments of the Mississippi fan can provide oil source rock for the Gulf of Mexico Basin, or that sediments of anoxic basins in the Louisiana continental slope are analogs to past environments where source rocks for crude oil have been deposited.« less

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

NASA Astrophysics Data System (ADS)

Lewan, M. D.; Buchardt, B.

1989-06-01

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

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

NASA Technical Reports Server (NTRS)

Hollander, D. J.; Sinninghe Damste, J. S.; Hayes, J. M.; de Leeuw, J. W.; Huc, A. Y.

1993-01-01

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.

Geochemical evaluation of upper cretaceous fruitland formation coals, San Juan Basin, New Mexico and Colorado

USGS Publications Warehouse

Michael, G.E.; Anders, D.E.; Law, B.E.

1993-01-01

Geochemical analyses of coal samples from the Upper Cretaceous Fruitland Formation in the San Juan Basin of New Mexico and Colorado were used to determine thermal maturity, type of kerogen, and hydrocarbon generation potential. Mean random vitrinite reflectance (%Rm) of the Fruitland coal ranges from 0.42 to 1.54%. Rock-Eval pyrolysis data and saturated to aromatic hydrocarbon ratio indicate that the onset of thermal hydrocarbon generation begins at about 0.60% Rm and peak generation occurs at about 0.85% Rm. Several samples have hydrogen index values between 200 and 400, indicating some potential for liquid hydrocarbon generation and a mixed Type III and II kerogen. Pentacyclic and tricyclic terpanes, steranes, aromatic steroids and methylphenanthrene maturity parameters were observed through the complete range of thermal maturity in the Fruitland coals. Aromatic pentacyclic terpanes, similar to those found in brown coals of Australia, were observed in low maturity samples, but not found above 0.80% Rm. N-alkane depleted coal samples, which occur at a thermal maturity of approx. 0.90% Rm, paralleling peak hydrocarbon generation, are fairly widespread throughout the basin. Depletion of n-alkanes in these samples may be due to gas solution stripping and migration fromthe coal seams coincident with the development of pressure induced fracturing due to hydrocarbon generation; however, biodegradation may also effect these samples. ?? 1993.

Numerous nanopores developed in organo-clay complexes during the shale formations

NASA Astrophysics Data System (ADS)

Wang, Q.; Wang, T.; Lu, H.; Liao, J.

2017-12-01

Shale gas as new energy resource is either stored in nano pores and microfractures or absorbed on the surface of kerogen and clay aggregate (Chalmers et al., 2012). Nano pores developed in organic matters is very important, because these organic pores have better connectivity than inorganic pores (Loucks et al., 2012) and can form an effective pore system where shale gas flows dominantly (Curtis et al., 2010). In order to figure out how the organic pores is affected by shale compositions, we conduct in-situ FE-SEM and EDS analysis on organic-rich Longmaxi shales. The data indicate that 1) organic matter, mixed with clay minerals, can form an organo-clay complex containing many nanopores; 2)furthermore, larger organic pores are developed in organo-clay complexes with higher clay content than in those with lower clay content(Wang et al., 2017). It seems that the presence of organo-clay complex raises the heterogeneous than pure organic matters. Organo-clay complex may bring in lots of intergranular nanopores between organic matter and clay minerals. Another potential interpretation is that clay minerals may influence kerogen thermal decomposition, generation of hydrocarbons and thus the development of organic pores. The presence of numerous nanopores in organo-clay complexes may promote the connectivity of the pore network and enhance the hydrocarbon production efficiency for shale gas field.

Multiscale properties of unconventional reservoir rocks

NASA Astrophysics Data System (ADS)

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.

Updated methodology for nuclear magnetic resonance characterization of shales

USGS Publications Warehouse

Washburn, Kathryn E.; Birdwell, Justin E.

2013-01-01

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

Biogeochemistry and biogeology research projects

NASA Technical Reports Server (NTRS)

Cloud, P.

1973-01-01

Summaries of work initiated or completed during the year in the areas of biochemistry and biology are reported. Topics include: studying humic substances through geologic time; analyzing the benzene and hexane soluble portions of the benzene-methanol extracts from the same standard suite for hydrocarbons; finding a pyrolytic technique and applying it to single taxa of fossil microorganisms and individual microorganisms; and discovering to what extent humic substances become converted to kerogen and retained in sediments. A list of publications is included.

Parameters Affecting the Characteristics of Oil Shale-Derived Fuels.

DTIC Science & Technology

1981-03-01

rock with essentially no organic matter. The oil shale of the Uinta Basin in Utah and extreme western Colorado is richer than the Wyoming shales, but...could be used in several areas of the Uinta Basin . Once the oil shale is mined, it must be heated to about 900’F to hreak down the kerogen. A variety... Uinta Basin of eastern Utah. The sections presented above d.l not exhaust the supply of retorting tech- niques that are in various stages of

Organic Matter Polymerization by Disulfide Bonding Near the Chemocline in Cariaco Basin

NASA Astrophysics Data System (ADS)

Raven, M. R.; Adkins, J. F.; Sessions, A. L.

2013-12-01

The preservation of organic carbon in sediments as kerogen is an essential pathway in the global carbon cycle, but the chemical reactions involved in kerogen formation remain poorly understood. Previous researchers have found that many sediments deposited under euxinic conditions contain sulfur-bearing non-polar lipids as well as disulfide bonds among lipid and carbohydrate monomers. It remains unclear, however, when during organic matter decomposition and diagenesis these different sulfur-bearing structures form, and how different environmental conditions affect the extent of organic matter sulfurization. We investigate organic sulfurization processes armed with a technique for measuring the sulfur-isotopic compositions of individual organosulfur compounds by coupled gas chromatography - inductively coupled plasma mass spectrometry. Organic compounds were extracted from sediments and water column sediment traps from Cariaco Basin, a euxinic basin in the Caribbean Sea. We measured the sulfur-isotopic compositions of both non-polar lipids and of derivatized disulfide-bound compounds from eight sediment trap profiles and a six-meter-long sediment core. In Cariaco Basin, lipid sulfurization processes appear to begin near the chemocline and continue in sediments on timescales of thousands of years. Slow diagenetic sulfurization in sediments produces lipid monomers with sulfur atoms in ring structures that are 34S-depleted relative to coexisting dissolved sulfide. Lipid monomers become progressively enriched in 34S over time, indicating ongoing formation coinciding with an increase in the amount of total sulfur in bulk kerogen. One of the most abundant monomers observed in Cariaco sediments, a phytol-related thiophene, is also produced intermittently near the chemocline. Phytol thiophene δ34S values in sediment traps are similar to those observed in shallow Cariaco sediments except during occasional ';enrichment events,' when phytol thiophene δ34S values increase to

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

NASA Astrophysics Data System (ADS)

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

Development of Simultaneous in situ Analysis of Carbon and Nitrogen Isotope Ratios in the Organic Matter by Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Ishida, A.; Kitajima, K.; Williford, K. H.; Kakegawa, T.; Valley, J. W.

2017-12-01

An in-situ analytical method for simultaneous analysis of carbon and nitrogen isotope ratios in organic matter was developed for 12 μm spots by secondary ion mass spectrometry (IMS 1280 at WiscSIMS). Secondary ions of 12C12C-, 12C13C-, 12C14N-, and 12C15N- are simultaneously measured by three Faraday cups and one electron multiplier. Ions of 12C12CH- are measured to monitor hydride interferences. The spot-by-spot reproducibility of δ13C and δ15N values of UWLA-1 anthracite standard (95.7 wt%C and 1.2 wt%N), which was selected as a running reference material, are 0.16‰ and 0.56‰ (2SD), respectively. A negative correlation is observed between the instrumental mass fractionation (mass bias) of carbon and 12C12CH-/12C12C- ratios of examined reference materials. In contrast, there is no correlation of mass bias and hydride cps for nitrogen isotope measurements, suggesting the mass bias of nitrogen can be determined independently of the hydrogen. Values of 22 individual globules of organic matter in a carbonate rock from the 1.9 Ga Gunflint Formation, determined by the new procedure, average δ13C = -33.5 ± 0.25‰ (VPDB) and δ15N = +5.2 ± 0.81‰ (Air). Values of δ13C of both SIMS and bulk kerogen analyses are consistent within analytical error. In contrast, a difference of 1.7‰, which is larger than the 2SD error of each analysis, is observed in δ15N values for in situ vs. bulk kerogen analyses (δ15Nbulk = +6.9 ± 0.6‰). This difference in δ15N might be caused by the preferential removal of low-δ15N components in the organic matter by HCl/HF acid treatment during the bulk kerogen isolation. Simultaneous analyses of carbon and nitrogen in the same micro-volume of organic matter in Precambrian sedimentary rocks will allow correlations with textures and mineralogical occurrences, which will provide more detailed constraints on environments and life of the early Earth. Furthermore, this method is applicable to a wide variety of other research fields

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

USGS Publications Warehouse

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

Coupled Thermo-Hydro-Mechanical Numerical Framework for Simulating Unconventional Formations

NASA Astrophysics Data System (ADS)

Garipov, T. T.; White, J. A.; Lapene, A.; Tchelepi, H.

2016-12-01

Unconventional deposits are found in all world oil provinces. Modeling these systems is challenging, however, due to complex thermo-hydro-mechanical processes that govern their behavior. As a motivating example, we consider in situ thermal processing of oil shale deposits. When oil shale is heated to sufficient temperatures, kerogen can be converted to oil and gas products over a relatively short timespan. This phase change dramatically impact both the mechanical and hydrologic properties of the rock, leading to strongly coupled THMC interactions. Here, we present a numerical framework for simulating tightly-coupled chemistry, geomechanics, and multiphase flow within a reservoir simulator (the AD-GPRS General Purpose Research Simulator). We model changes in constitutive behavior of the rock using a thermoplasticity model that accounts for microstructural evolution. The multi-component, multiphase flow and transport processes of both mass and heat are modeled at the macroscopic (e.g., Darcy) scale. The phase compositions and properties are described by a cubic equation of state; Arrhenius-type chemical reactions are used to represent kerogen conversion. The system of partial differential equations is discretized using a combination of finite-volumes and finite-elements, respectively, for the flow and mechanics problems. Fully implicit and sequentially implicit method are used to solve resulting nonlinear problem. The proposed framework is verified against available analytical and numerical benchmark cases. We demonstrate the efficiency, performance, and capabilities of the proposed simulation framework by analyzing near well deformation in an oil shale formation.

New insights on timing of oil and gas generation in the central Gulf Coast interior zone based on hydrous-pyrolysis kinetic parameters

USGS Publications Warehouse

Lewan, Michael D.; Dutton, Shirley P.; Ruppel, Stephen C.; Hentz, Tucker F.

2002-01-01

Timing of oil and gas generation from Turonian and Smackover source rocks in the central Gulf CoastInterior Zone was determined in one-dimensional burial-history curves (BHCs) using hydrous-pyrolysis kinetic parameters. The results predict that basal Smackover source-rock intervals with Type-IIS kerogen completed oil generation between 121 and 99 Ma, and Turonian source-rocks with Type-II kerogen remain immature over most of the same area. The only exception to the latter occurs in the northwestern part of the Mississippi salt basin, where initial stages of oil generation have started as a result of higher thermal gradients. This maturity difference between Turonian and Smackover source rocks is predicted with present-day thermal gradients. Predicted oil generation prior to the Sabine and Monroe uplifts suggests that a significant amount of the oil emplaced in Cretaceous reservoirs of these uplifts would have been lost during periods of erosion. Hydrous-pyrolysis kineticparameters predict that cracking of Smackover oil to gas started 52 Ma, which postdates major uplift and erosional events of the Sabine and Monroe uplifts. This generated gas would accumulate and persist in these uplift areas as currently observed. The predicted timing of oil and gas generation with hydrous-pyrolysis kinetic parameters is in accordance with the observed scarcity of oil from Turonian source rocks, predominance of gas accumulations on the Sabine and Monroe uplifts, and predominance of oil accumulations along the northern rim of the Interior Zone.

Multivariate analysis relating oil shale geochemical properties to NMR relaxometry

USGS Publications Warehouse

Birdwell, Justin E.; Washburn, Kathryn E.

2015-01-01

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

Uranium in the Upper Cambrian black shale of Sweden

USGS Publications Warehouse

McKelvey, Vincent Ellis

1955-01-01

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

Burial history, thermal maturity, and oil and gas generation history of petroleum systems in the Wind River Basin Province, central Wyoming: Chapter 6 in Petroleum systems and geologic assessment of oil and gas resources in the Wind River Basin Province, Wyoming

USGS Publications Warehouse

Roberts, Laura N.R.; Finn, Thomas M.; Lewan, Michael D.; Kirschbaum, Mark A.

2007-01-01

Burial history, thermal maturity, and timing of oil and gas generation were modeled for eight key source rock units at nine well locations throughout the Wind River Basin Province. Petroleum source rocks include the Permian Phosphoria Formation, the Cretaceous Mowry Shale, Cody Shale, and Mesaverde, Meeteetse, and Lance Formations, and the Tertiary (Paleocene) Fort Union Formation, including the Waltman Shale Member. Within the province boundary, the Phosphoria is thin and only locally rich in organic carbon. Phosphoria oil produced from reservoirs in the province is thought to have migrated from the Wyoming and Idaho thrust belt. Locations (wells) selected for burial history reconstructions include three in the deepest parts of the province (Adams OAB-17, Bighorn 1-5, and Coastal Owl Creek); three at intermediate depths (Hells Half Acre, Shell 33X-10, and West Poison Spider); and three at relatively shallow locations (Young Ranch, Amoco Unit 100, and Conoco-Coal Bank). The thermal maturity of source rocks is greatest in the deep northern and central parts of the province and decreases to the south and east toward the basin margins. The results of the modeling indicate that, in the deepest areas, (1) peak petroleum generation from Cretaceous rocks occurred from Late Cretaceous through middle Eocene time, and (2) onset of oil generation from the Waltman Shale Member occurred from late Eocene to early Miocene time. Based on modeling results, gas generation from the cracking of Phosphoria oil reservoired in the Park City Formation reached a peak in the late Paleocene/early Eocene (58 to 55 Ma) only in the deepest parts of the province. The Mowry Shale and Cody Shale (in the eastern half of the basin) contain a mix of Type-II and Type-III kerogens. Oil generation from predominantly Type-II source rocks of these units in the deepest parts of the province reached peak rates during the latest Cretaceous to early Eocene (65 to 55 Ma). Only in these areas of the basin did

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

NASA Astrophysics Data System (ADS)

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.

Source potential of the Zairian onshore pre-salt subbasins of the West African Aptian salt basin

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

Swirydczuk, K.; Tshiband, D.; Nyimi, M.

1996-08-01

Three pre-salt subbasins are located onshore in Zaire in the Congo-Cabinda Basin. Production exists to the west, and extensive outcrops of Mavuma tar sands are located immediately to the east of these subbasins. Five pre-salt wells confirmed that thick Barremian lacustrine claystones of the Bucomazi Formation form the main source horizon in all the subbasins. Upper Bucomazi claystones average 4% and reach 12% TOC. Lower Bucomazi claystones average 2% (high of 6%). A mixed Type I/Type II algal oil-prone kerogen predominates. Up to 1% TOC is present in claystones in the underlying Lucula section. Dry pyrolysis shows significant differences inmore » kerogen kinetics from subbasin to subbasin. R{sub o} and T{sub max} were used to model heat flow through time. Ages were from biostratigraphic analyses and radiometric dating of thin volcanics within the Lucula and Bucomazi formations. Apatite fission track analyses provided control on uplift history. Pseudowells were used in maturation modelling to predict source rock maturity in the subbasins. The upper Bucomazi is immature except in the deeper parts of two of the subbasins. The Lower - Bucomazi and Upper Lucula are mature in all subbasins and in the deepest subbasins are overmature. Oil generation occurred shortly after deposition of the Loeme Salt. Analyses of Lindu oil support this early migration. Estimates of oil that may have been generated in the eastern-most subbasin suggest that extensive Mavuma tar sands, which have been typed to lacustrine source, could have been sourced from this subbasin.« less

Petroleum source potential of the Lower Cretaceous mudstone succession of the NPRA and Colville Delta area, North Slope Alaska, based on sonic and resistivity logs

USGS Publications Warehouse

Keller, Margaret A.; Bird, Kenneth J.

2003-01-01

Resource assessment of the North Slope of Alaska by the U. S. Geological Survey includes evaluation of the petroleum source potential of Mesozoic and Cenozoic rocks using the delta log R technique (Passey and others, 1990). Porosity and resistivity logs are used in combination with thermal maturity data to produce a continuous profile of total organic carbon content in weight % (TOC). From the pattern and amount of TOC in the profile produced, the depositional setting and thus the petroleum source-rock potential (kerogen type) of the organic matter can be inferred and compared to interpretations from other data such as Rock-Eval pyrolysis. TOC profiles determined by this technique for the contiguous interval of pebble shale unit, Hue Shale (including the Gamma Ray Zone or GRZ), and lower part of the Torok Formation indicate important potential for petroleum generation in the Tunalik 1, Inigok 1, N. Inigok 1, Kuyanak 1, Texaco Colville Delta 1, Nechelik 1, and Bergschrund 1 wells of the western North Slope region. TOC profiles suggest that this interval contains both type II and III kerogens – consistent with proposed depositional models -- and is predominantly greater than 2 wt. % TOC (cut-off used for effective source potential). Average TOC for the total effective section of the pebble shale unit + Hue Shale ranges from 2.6 to 4.1 wt % TOC (values predominantly 2-8% TOC) over 192-352 ft. Source potential for the lower Torok Formation, which also has interbedded sandstone and lean mudstone, is good to negligible in these 7 wells.

Preliminary source rock evaluation and hydrocarbon generation potential of the early Cretaceous subsurface shales from Shabwah sub-basin in the Sabatayn Basin, Western Yemen

NASA Astrophysics Data System (ADS)

Al-Matary, Adel M.; Hakimi, Mohammed Hail; Al Sofi, Sadam; Al-Nehmi, Yousif A.; Al-haj, Mohammed Ail; Al-Hmdani, Yousif A.; Al-Sarhi, Ahmed A.

2018-06-01

A conventional organic geochemical study has been performed on the shale samples collected from the early Cretaceous Saar Formation from the Shabwah oilfields in the Sabatayn Basin, Western Yemen. The results of this study were used to preliminary evaluate the potential source-rock of the shales in the Saar Formation. Organic matter richness, type, and petroleum generation potential of the analysed shales were assessed. Total organic carbon content and Rock- Eval pyrolysis results indicate that the shale intervals within the early Cretaceous Saar Formation have a wide variation in source rock generative potential and quality. The analysed shale samples have TOC content in the range of 0.50 and 5.12 wt% and generally can be considered as fair to good source rocks. The geochemical results of this study also indicate that the analysed shales in the Saar Formation are both oil- and gas-prone source rocks, containing Type II kerogen and mixed Types II-III gradient to Type III kerogen. This is consistent with Hydrogen Index (HI) values between 66 and 552 mg HC/g TOC. The temperature-sensitive parameters such as vitrinite reflectance (%VRo), Rock-Eval pyrolysis Tmax and PI reveal that the analysed shale samples are generally immature to early-mature for oil-window. Therefore, the organic matter has not been altered by thermal maturity thus petroleum has not yet generated. Therefore, exploration strategies should focus on the known deeper location of the Saar Formation in the Shabwah-sub-basin for predicting the kitchen area.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

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

PubMed

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 <1000 μgL(-1). These results show that sorption is likely a significant contributor to the persistence of a 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.

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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 < 1000 μg L- 1. These results show that sorption is likely a significant contributor to the persistence of a 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.

Hydrocarbon source rock potential of the Karoo in Zimbabwe

NASA Astrophysics Data System (ADS)

Hiller, K.; Shoko, U.

1996-07-01

The hydrocarbon potential of Zimbabwe is tied to the Karoo rifts which fringe the Zimbabwe Craton, i.e. the Mid-Zambezi basin/rift and the Mana Pools basin in the northwest, the Cabora Bassa basin in the north and the Tuli-Bubye and Sabi-Runde basins in the south. Based on the geochemical investigation of almost one thousand samples of fine clastic Karoo sediments, a concise source rock inventory has been established showing the following features. No marine source rocks have been identified. In the Mid-Zambezi area and Cabora Bassa basin, the source rocks are gas-prone, carbonaceous to coaly mudstones and coal of Lower Karoo age. In the Cabora Bassa basin, similar gas-prone source rocks occur in the Upper Karoo (Angwa Alternations Member). These kerogen type III source rocks are widespread and predominantly immature to moderately mature. In the southern basins, the Lower Karoo source rocks are gas-prone; in addition some have a small condensate potential. Most of the samples are, however, overmature due to numerous dolerite intrusions. Samples with a mixed gas, condensate and oil potential (mainly kerogen types II and III) were identified in the Lower Karoo (Coal Measure and Lower Madumabisa Mudstone Formations) of the Mid-Zambezi basin, and in the Louver Karoo (Mkanga Formation) and Upper Karoo (Upper Angwa Alternations Member Formation) of the Cabora Bassa basin. The source rocks, with a liquid potential, are also immature to moderately mature and were deposited in swamp, paludal and lacustrine environments of limited extent.

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

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

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

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

Thermal history of sedimentary basins, maturation indices, and kinetics of oil and gas generation

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

Tissot, B.P.; Pelet, R.; Ungerer, P.

1987-12-01

Temperature is the most sensitive parameter in hydrocarbon generation. Thus, reconstruction of temperature history is essential when evaluating petroleum prospects. No measurable parameter can be directly converted to paleotemperature. Maturation indices such as vitrinite reflectance, T/sub max/ from Rock-Eval pyrolysis, spore coloration, Thermal Alteration Index (TAI), or concentration of biological markers offer an indirect approach. All these indices are a function of the thermal history through rather complex kinetics, frequently influenced by the type of organic matter. Their significance and validity are reviewed. Besides the problems of identification (e.g. vitrinite) and interlaboratory calibration, it is important to simultaneously interpret kerogenmore » type and maturation and to avoid difficult conversions from one index to another. Geodynamic models, where structural and thermal histories are connected, are another approach to temperature reconstruction which could be calibrated against the present distribution of temperature and the present value of maturation indices. Kinetics of kerogen decomposition controls the amount and composition of hydrocarbons generated. An empirical time-temperature index (TTI), originally introduced by Lopatin, does not allow such a quantitative evaluation. Due to several limitations (no provision for different types of kerogen and different rates of reactions, poor calibration on vitrinite reflectance), it is of limited interest unless one has no access to a desk-top computer. Kinetic models, based on a specific calibration made on actual source rock samples, can simulate the evolution of all types of organic matter and can provide a quantitative evaluation of oil and gas generated. 29 figures.« less

Organic molecules as chemical fossils - The molecular fossil record

NASA Technical Reports Server (NTRS)

Eglinton, G.

1983-01-01

The study of biochemical clues to the early earth and the origin of life is discussed. The methods used in such investigation are described, including the extraction, fractionation, and analysis of geolipids and the analysis of kerogen. The occurrence of molecular fossils in the geological record is examined, discussing proposed precursor-product relationships and the molecular assessment of deep sea sediments, ancient sediments, and crude petroleums. Alterations in the molecular record due to diagenesis and catagenesis are considered, and the use of microbial lipids as molecular fossils is discussed. The results of searches for molecular fossils in Precambrian sediments are assessed.

Sea Level and Paleoenvironment Control on Late Ordovician Source Rocks, Hudson Bay Basin, Canada

NASA Astrophysics Data System (ADS)

Zhang, S.; Hefter, J.

2009-05-01

Head Rapids Formation. 2) Type I kerogen is normally formed in quiet, oxygen-deficient, shallow water environment. Rock-Eval6 data from 40 samples of the three oil shale intervals, collected from outcrops on Southampton Island, demonstrate that the proportion of Type I kerogen gradually increases in the mixed Type I-Type II kerogen from the lower to upper oil shale intervals. 3) Pristane/phytane ratio can be used as a paleoenvironment indicator. The low ratios in the three oil shale intervals range from 0.5 to 0.9 and indicate anoxic and hypersaline conditions. In addition, the presence of isorenieratene derivatives from green phototrophic sulfur bacteria (Chlorobiaceae), with highest relative concentrations in the lower oil shale intervals, points to anoxia reaching into the photic zone of the water column.

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

USGS Publications Warehouse

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

Hydrocarbon potential evaluation of the source rocks from the Abu Gabra Formation in the Sufyan Sag, Muglad Basin, Sudan

NASA Astrophysics Data System (ADS)

Qiao, Jinqi; Liu, Luofu; An, Fuli; Xiao, Fei; Wang, Ying; Wu, Kangjun; Zhao, Yuanyuan

2016-06-01

The Sufyan Sag is one of the low-exploration areas in the Muglad Basin (Sudan), and hydrocarbon potential evaluation of source rocks is the basis for its further exploration. The Abu Gabra Formation consisting of three members (AG3, AG2 and AG1 from bottom to top) was thought to be the main source rock formation, but detailed studies on its petroleum geology and geochemical characteristics are still insufficient. Through systematic analysis on distribution, organic matter abundance, organic matter type, organic matter maturity and characteristics of hydrocarbon generation and expulsion of the source rocks from the Abu Gabra Formation, the main source rock members were determined and the petroleum resource extent was estimated in the study area. The results show that dark mudstones are the thickest in the AG2 member while the thinnest in the AG1 member, and the thickness of the AG3 dark mudstone is not small either. The AG3 member have developed good-excellent source rock mainly with Type I kerogen. In the Southern Sub-sag, the AG3 source rock began to generate hydrocarbons in the middle period of Bentiu. In the early period of Darfur, it reached the hydrocarbon generation and expulsion peak. It is in late mature stage currently. The AG2 member developed good-excellent source rock mainly with Types II1 and I kerogen, and has lower organic matter abundance than the AG3 member. In the Southern Sub-sag, the AG2 source rock began to generate hydrocarbons in the late period of Bentiu. In the late period of Darfur, it reached the peak of hydrocarbon generation and its expulsion. It is in middle mature stage currently. The AG1 member developed fair-good source rock mainly with Types II and III kerogen. Throughout the geological evolution history, the AG1 source rock has no effective hydrocarbon generation or expulsion processes. Combined with basin modeling results, we have concluded that the AG3 and AG2 members are the main source rock layers and the Southern Sub-sag is

Synchrotron X-ray Applications Toward an Understanding of Elastic Anisotropy

NASA Astrophysics Data System (ADS)

Kanitpanyacharoen, Waruntorn

technique was applied to characterize LPO and phase proportions of Posidonia Shale collected in the Hils Syncline from Germany, in order to examine the influence of clay content, burial depth, and thermal history. The samples used in this study had experienced different local temperatures during burial and uplifting, as established by the maturity of kerogen (0.68-1.45% vitrinite reflectance, Ro), but their constituent clay minerals, including kaolinite, illite-mica, and illite-smectite, show similar degrees of LPO in all samples, ranging between 3.7 and 6.3 multiple of random distribution (m.r.d.). These observations imply that the difference in local thermal history, which significantly affects the maturity of kerogen, at most marginally influences LPO of clays, as the alignment of clays was established early in the history. In Chapter 4, the SPO of constituents phases in Kimmeridge Shale (North Sea, UK) and Barnett Shale (Gulf of Mexico, USA) was quantified to a resolution of ˜1 mum by using synchrotron X-ray microtomography (SXMT) technique. Measurements were done at different facilities (ALS, APS, and SLS) to characterize 3D microstructures, explore resolution limitations, and develop satisfactory procedures for data quantification. Segmentation images show that the SPO of low density features, including pores, fractures, and kerogen, is mostly anisotropic and oriented parallel to the bedding plane. Small pores are generally dispersed, whereas some large fractures and kerogen have irregular shapes and remain aligned horizontally. In contrast, pyrite exhibits no SPO. The volume fractions and aspect ratios of low density features extracted from three synchrotron sources show excellent agreement with 6.3(6)% for Kimmeridge Shale and 4.5(4)% for Barnett Shale. A small variation is mainly due to differences of optical instruments and technical setups. The SXMT is proven to be a crucial technique to investigate 3D internal structures of fine-grained materials at high

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

USGS Publications Warehouse

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.

Modeling of gas generation from the Barnett Shale, Fort Worth Basin, Texas

USGS Publications Warehouse

Hill, R.J.; Zhang, E.; Katz, B.J.; Tang, Y.

2007-01-01

The generative gas potential of the Mississippian Barnett Shale in the Fort Worth Basin, Texas, was quantitatively evaluated by sealed gold-tube pyrolysis. Kinetic parameters for gas generation and vitrinite reflectance (Ro) changes were calculated from pyrolysis data and the results used to estimate the amount of gas generated from the Barnett Shale at geologic heating rates. Using derived kinetics for Ro evolution and gas generation, quantities of hydrocarbon gas generated at Ro ??? 1.1% are about 230 L/t (7.4 scf/t) and increase to more that 5800 L/t (186 scf/t) at Ro ??? 2.0% for a sample with an initial total organic carbon content of 5.5% and Ro = 0.44%. The volume of shale gas generated will depend on the organic richness, thickness, and thermal maturity of the shale and also the amount of petroleum that is retained in the shale during migration. Gas that is reservoired in shales appears to be generated from the cracking of kerogen and petroleum that is retained in shales, and that cracking of the retained petroleum starts by Ro ??? 1.1%. This result suggests that the cracking of petroleum retained in source rocks occurs at rates that are faster than what is predicted for conventional siliciclastic and carbonate reservoirs, and that contact of retained petroleum with kerogen and shale mineralogy may be a critical factor in shale-gas generation. Shale-gas systems, together with overburden, can be considered complete petroleum systems, although the processes of petroleum migration, accumulation, and trap formation are different from what is defined for conventional petroleum systems. Copyright ?? 2007. The American Association of Petroleum Geologists. All rights reserved.

Sensitivity of the North Atlantic Basin to cyclic climatic forcing during the early Cretaceous

USGS Publications Warehouse

Dean, W.E.; Arthur, M.A.

1999-01-01

Striking cyclic interbeds of laminated dark-olive to black marlstone and bioturbated white to light-gray limestone of Neocomian (Early Cretaceous) age have been recovered at Deep Sea Drilling Project (DSDP) and Ocean Drilling Project (ODP) sites in the North Atlantic. These Neocomian sequences are equivalent to the Maiolica Formation that outcrops in the Tethyan regions of the Mediterranean and to thick limestone sequences of the Vocontian Trough of France. This lithologic unit marks the widespread deposition of biogenic carbonate over much of the North Atlantic and Tethyan seafloor during a time of overall low sealevel and a deep carbonate compensation depth. The dark clay-rich interbeds typically are rich in organic carbon (OC) with up to 5.5% OC in sequences in the eastern North Atlantic. These eastern North Atlantic sequences off northwest Africa, contain more abundant and better preserved hydrogen-rich, algal organic matter (type II kerogen) relative to the western North Atlantic, probably in response to coastal upwelling induced by an eastern boundary current in the young North Atlantic Ocean. The more abundant algal organic matter in sequences in the eastern North Atlantic is also expressed in the isotopic composition of the carbon in that organic matter. In contrast, organic matter in Neocomian sequences in the western North Atlantic along the continental margin of North America has geochemical and optical characteristics of herbaceous, woody, hydrogen-poor, humic, type III kerogen. The inorganic geochemical characteristics of the dark clay-rich (80% CaCO3) interbeds in both the eastern and western basins of the North Atlantic suggest that they contain minor amounts of relatively unweathered eolian dust derived from northwest Africa during dry intervals.

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

USGS Publications Warehouse

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

The art of maturity modeling. Part 2. Alternative models and sensitivity analysis

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

Waples, D.W.; Suizu, Masahiro; Kamata, Hiromi

1992-01-01

The sensitivity of exploration decisions to variations in several input parameters for maturity modeling was examined for the MITI Rumoi well, Hokkaido, Japan. Decisions were almost completely insensitive to uncertainties about formation age and erosional removal across some unconformities, but were more sensitive to changes in removal during unconformities which occurred near maximum paleotemperatures. Exploration decisions were not very sensitive to the choice of a particular kinetic model for hydrocarbon generation. Uncertainties in kerogen type and the kinetics of different kerogen types are more serious than differences among the various kinetic models. Results of modeling using the TTI method weremore » unsatisfactory. Thermal history and timing and amount of hydrocarbon generation estimated or calculated using the TTI method were greatly different from those obtained using a purely kinetic model. The authors strongly recommend use of the kinetic R{sub o} method instead of the TTI method. If they had lacked measured R{sub o} data, subsurface temperature data, or both, their confidence in the modeling results would have been sharply reduced. Conceptual models for predicting heat flow and thermal conductivity are simply too weak at present to allow one to carry out highly meaningful modeling unless the input is constrained by measured data. Maturity modeling therefore requires the use of more, not fewer, measured temperature and maturity data. The use of sensitivity analysis in maturity modeling is very important for understanding the geologic system, for knowing what level of confidence to place on the results, and for determining what new types of data would be most necessary to improve confidence. Sensitivity analysis can be carried out easily using a rapid, interactive maturity-modeling program.« less

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

Burwood, R.; Fortems, G.; Mycke, B.

Deposited under lacustrine conditions during the rift-phase opening of the southern Atlantic, the lower Congo Bucomazi Formation is a highly productive source rock sequence. Reaching considerable thickness (1.8 km), a heterogeneous organofacies reflects both rapid accumulation and changing conditions during Early Cretaceous Barremian sedimentation. As a component of organofacies, low resolution studies showed kerogen kinetic parameters (Ea/A) varied widely according to the gross paleoenvironmental conditions prevailing during deposition. As a a general trend, refractory (type I, higher Ea) kerogens of the [open quotes]basin fill[close quotes] Organic Rich Zone (ORZ) give way to more labile (type II, lower Ea) assemblages inmore » the up-section [open quotes]sheet drape[close quotes] sediments. At higher resolution, a considerable fine structure in Ea fluctuation, presumably reflecting micropaleoenvironment control, becomes evident. Using Ea values assembled for the Bucomazi type section, subsidence modeling for a Ponta Vermelha depocenter section showed a wide disparity in behavior. Being more representative of the sheet-drape episode, type II assemblages matured earlier, at lesser overburdens, and provided the initial hydrocarbon charge. For the ORZ assemblages, the dominant type I component was of retarded maturation, only becoming productive at commensurately greater overburdens. Cumulatively, these events merge to provide an extended period of hydrocarbon generation with implications for production of aggregate oils of varied emplacement histories. Significantly, the net effect of the observed Ea contrast results in the less prolific (but more labile) uppermost Bucomazi assuming a more important charging role than the ORZ of superior source richness. The latter can only realize its full potential under the greatest overburdens attainable in the most subsident depocenters.« less

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Technical Reports Server (NTRS)

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.

Organic matter in meteorites and comets - Possible origins

NASA Technical Reports Server (NTRS)

Anders, Edward

1991-01-01

At least six extraterrestrial environments may have contributed organic compounds to meteorites and comets: solar nebula, giant-planet subnebulae, asteroid interiors containing liquid water, carbon star atmospheres, and diffuse or dark interstellar clouds. The record in meteorites is partly obscured by pervasive reheating that transformed much of the organic matter to kerogen; nonetheless, it seems that all six formation sites contributed. For comets, the large abundance of HCHO, HCN, and unsaturated hydrocarbons suggests an interstellar component of 50 percent or more, but the contributions of various interstellar processes, and of a solar-nebula component, are hard to quantify. A research program is outlined that may help reduce these uncertainties.

Isotopically exchangeable organic hydrogen in coal relates to thermal maturity and maceral composition

USGS Publications Warehouse

Mastalerz, Maria; Schimmelmann, A.

2002-01-01

Hydrogen isotopic exchangeability (Hex) and ??Dn values of non-exchangeable organic hydrogen were investigated in coal kerogens ranging in rank from lignite to graphite. The relative abundance of Hex is highest in lignite with about 18% of total hydrogen being exchangeable, and decreases to around 2.5% in coals with Ro of 1.7 to ca. 5.7%. At Still higher rank (Ro > 6%), Hex increases slightly, although the abundance of total hydrogen decreases. ??Dn is influenced by original biochemical D/H ratios and by thermal maturation in contact with water. Therefore, ??Dn does not show an overall consistent trend with maturity. ?? 2002 Elsevier Science Ltd. All rights reserved.

The effect of coal bed dewatering and partial oxidation on biogenic methane potential

USGS Publications Warehouse

Jones, Elizabeth J.P.; Harris, Steve H.; Barnhart, Elliott P.; Orem, William H.; Clark, Arthur C.; Corum, Margo D.; Kirshtein, Julie D.; Varonka, Matthew S.; Voytek, Mary A.

2013-01-01

Coal formation dewatering at a site in the Powder River Basin was associated with enhanced potential for secondary biogenic methane determined by using a bioassay. We hypothesized that dewatering can stimulate microbial activity and increase the bioavailability of coal. We analyzed one dewatered and two water-saturated coals to examine possible ways in which dewatering influences coal bed natural gas biogenesis by looking at differences with respect to the native coal microbial community, coal-methane organic intermediates, and residual coal oxidation potential. Microbial biomass did not increase in response to dewatering. Small Subunit rRNA sequences retrieved from all coals sampled represented members from genera known to be aerobic, anaerobic and facultatively anaerobic. A Bray Curtis similarity analysis indicated that the microbial communities in water-saturated coals were more similar to each other than to the dewatered coal, suggesting an effect of dewatering. There was a higher incidence of long chain and volatile fatty acid intermediates in incubations of the dewatered coal compared to the water-saturated coals, and this could either be due to differences in microbial enzymatic activities or to chemical oxidation of the coal associated with O2 exposure. Dilute H2O2 treatment of two fractions of structural coal (kerogen and bitumen + kerogen) was used as a proxy for chemical oxidation by O2. The dewatered coal had a low residual oxidation potential compared to the water-saturated coals. Oxidation with 5% H2O2 did increase the bioavailability of structural coal, and the increase in residual oxidation potential in the water saturated coals was approximately equivalent to the higher methanogenic potential measured in the dewatered coal. Evidence from this study supports the idea that coal bed dewatering could stimulate biogenic methanogenesis through partial oxidation of the structural organics in coal once anaerobic conditions are restored.

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

NASA Astrophysics Data System (ADS)

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.

Thermal maturation history of the Wilcox group (Paleocene-Eocene), Texas: Results of regional-scale multi-1D modeling

USGS Publications Warehouse

Rowan, E.L.; Warwick, Peter D.; Pitman, Janet K.; Kennan, Lorcan; Pindell, James; Rosen, Norman C.

2007-01-01

The thermal maturation history of the Paleocene-Eocene Wilcox Group has been reconstructed based on burial history models of 53 wells in the Texas coastal plain. This modeling study has been conducted in conjunction with a geologically based assessment of the oil and gas resources in Cenozoic strata of the Gulf of Mexico coastal plain and state waters. In the onshore Texas coastal plain, coals and organic-rich shales, predominantly of terrestrial origin, within the Wilcox Group are the primary source of oil (Wenger et al., 1994) as well as a source of gas. The Wilcox, however, is modeled as a single unit, without subdivision into source rock and non-source rock intervals.Generation of oil from Type III kerogen within the Wilcox Group is modeled using hydrous pyrolysis reaction kinetic parameters (Lewan, M.D., written communication, 2006). Gas generation from Type III kerogen is represented using calculated Ro values. The models are calibrated with bottom hole temperature (BHT), and vitrinite reflectance (Ro %) data for the Wilcox Group. Ro data from near-coastal sites have been selected to minimize the possible effects of uplift and erosion and then composited to give a regional Rodepth trend.Model calculations for the study area, the onshore Texas coastal plain, indicate that downdip portions of the basal Wilcox had reached sufficient thermal maturity to generate hydrocarbons by early Eocene (~50 Ma). This relatively early maturation is explained by rapid sediment accumulation in the early Tertiary combined with the reaction kinetic parameters used in the models. Thermal maturation increases through time with increasing burial depth and temperature, gradually moving the maturation front updip. At present day, hydrocarbon generation is complete in the downdip Wilcox within the study area but is currently ongoing in the updip portions of the formation.

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

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.

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

USGS Publications Warehouse

Finn, Thomas M.

2014-01-01

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

Noble gas trapping and fractionation during synthesis of carbonaceous matter. [in meteorites

NASA Technical Reports Server (NTRS)

Frick, U.; Mack, R.; Chang, S.

1979-01-01

An investigation of noble gas entrapment during synthesis of carbonaceous, macromolecular, and kerogen-like substances is presented. High molecular weight organic matter synthesized in aqueous condensation reactions contained little gas, and the composition was consistent with fractionation due to noble gas solubility in water; however, propane soot produced during a modified Miller-Urey experiment in an aritificial gas mixture contained high concentrations of trapped noble gases that displayed strong elemental fractionation from their reservoirs. It is concluded that theses experiemnts show that processes exist for synthesis of carbonaceous carriers that result in high noble gas concentrations and strong elemental fractionation at temperatures well above those required by absorption to achieve similar effects.

Altering wettability to recover more oil from tight formations

DOE PAGES

Brady, Patrick V.; Bryan, Charles R.; Thyne, Geoffrey; ...

2016-06-03

We describe here a method for chemically modifying fracturing fluids and overflushes to chemically increase oil recovery from tight formations. Oil wetting of tight formations is usually controlled by adhesion to illite, kerogen, or both; adhesion to carbonate minerals may also play a role. Oil-illite adhesion is sensitive to salinity, dissolved divalent cation content, and pH. We measure oil-rock adhesion with middle Bakken formation oil and core to verify a surface complexation model of reservoir wettability. The agreement between the model and experiments suggests that wettability trends in tight formations can be quantitatively predicted and that fracturing fluid and overflushmore » compositions can be individually tailored to increase oil recovery.« less

Thermal maturity map of the lower part of the Upper Cretaceous Mesaverde Group, Uintah Basin, Utah

USGS Publications Warehouse

Nuccio, Vito F.; Johnson, Ronald C.

1986-01-01

The ability of rock to generate oil and gas is directly related to the type and quantity of kerogen and to its thermal maturity; therefore, thermal maturity is a commonly used tool for oil and gas exploration.  The purpose of this study ws to provide a thermal-maturity map for the lower part of the Upper Cretaceous Mesaverde Group in the eastern part of the Uinta Basin.  Prior to this study, thermal-maturity data were not available for the Uinta Basin.  This study uses coal rank to show the thermal maturity of the associated rocks.  The map was prepared in cooperation with the U.S. Department of Energy under its western gas sands project.

Altering wettability to recover more oil from tight formations

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

Brady, Patrick V.; Bryan, Charles R.; Thyne, Geoffrey

We describe here a method for chemically modifying fracturing fluids and overflushes to chemically increase oil recovery from tight formations. Oil wetting of tight formations is usually controlled by adhesion to illite, kerogen, or both; adhesion to carbonate minerals may also play a role. Oil-illite adhesion is sensitive to salinity, dissolved divalent cation content, and pH. We measure oil-rock adhesion with middle Bakken formation oil and core to verify a surface complexation model of reservoir wettability. The agreement between the model and experiments suggests that wettability trends in tight formations can be quantitatively predicted and that fracturing fluid and overflushmore » compositions can be individually tailored to increase oil recovery.« less

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

NASA Astrophysics Data System (ADS)

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

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

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

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

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

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

NASA Astrophysics Data System (ADS)

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, <0.5% & S2 <2.5 mg C/g rock), dominated by type III kerogens, and immature at the studied locations. The Baraka shale nevertheless, is good at El Mahafir-1 well (avg. TOC 1.8% & S2 5.0-10.0 mg C/g rock) and fair at Timsah-1 well (Avg. TOC 0.69% & S2 2.5-5.0 mg C/g rock) with a Kerogen that is predominantly Sapropellic at the former, and an exclusively Humic at the later. The formation is mature at Timsah (% Ro = 0.77-1.16) and early mature at El Mahafir-1 (% Ro = 0.64-0.81). Consistent with the pyrolysis, chromatographic data of the rock extracts confirms the mixed source nature of the Abu Gabra Formation which consists of both algal [prominent LMW n-alkanes & elevated C27 steranes (36-47%)], as well as terrigenous material [higher diasterane/regular sterane ratios (0.50-0.56), abundant rearranged hopanes, & relatively high CPIs (1.22-1.9)], accumulated in an oxic to sub-oxic environment (Pr/Ph, 1.3-3.0). Abu Gabra further shows low C29/C30 hopanes (0.45-0.54), low C28 steranes (21-26%) with high Gammacerane index (20.3). In contrast, the environment during the Late Cretaceous was strongly reducing (Pr/Ph, 0.37-1.0), associated with a wide organic diversity, both in space and time and is characterized by dominant algal input at some areas and or stratigraphic intervals

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

USGS Publications Warehouse

Leventhal, J.S.

1981-01-01

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

Partial resolution of sources of n-alkanes in the saline portion of the Parachute Creek Member, Green River Formation (Piceance Creek Basin, Colorado)

NASA Technical Reports Server (NTRS)

Collister, J. W.; Lichtfouse, E.; Hieshima, G.; Hayes, J. M.

1994-01-01

Systematic variations in the 13C contents of individual extractable n-alkanes (C16-C29) can be modelled quantitatively and interpreted as indicating contributions from at least five distinct sources. These appear to be cyanobacterial (C16-C18, delta 13C = -37% vs PDB), phytoplanktonic (C16-C23, delta = -32%), chemoautotrophic bacterial (C20-C29, delta = -38%), phytoplanktonic or heterotrophic bacterial (C20-C29, delta = -30%), and vascular plants (C23-C29, delta = -29%). Hydrous pyrolysis of related kerogens yields large quantities of additional n-alkanes with different and much more uniform delta values. The latter materials are apparently derived from the thermolysis of aliphatic biopolymers whose presence in the Green River Oil Shale has been recognized visually.

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

Not Available

An Apple IIe microcomputer is being used to collect data and to control a pyrolysis system. Pyrolysis data for bitumen and kerogen are widely used to estimate source rock maturity. For a detailed analysis of kinetic parameters, however, data must be obtained more precisely than for routine pyrolysis. The authors discuss the program which controls the temperature ramp of the furnace that heats the sample, and collects data from a thermocouple in the furnace and from the flame ionization detector measuring evolved hydrocarbons. These data are stored on disk for later use by programs that display the results of themore » experiment or calculate kinetic parameters. The program is written in Applesoft BASIC with subroutines in Apple assembler for speed and efficiency.« less

Shale Oil Value Enhancement Research

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

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 nowmore » ready for pilot plant engineering studies and is likely to play an important role in developing a US oil shale industry.« less

Search for Organic Matter on Mars: Complementarity of In Situ Analyses and Laboratory Analyses of Martian Samples

NASA Astrophysics Data System (ADS)

Brack, A.; Commeyras, A.; Derenne, S.; Despois, D.; Dhamelincourt, P.; Dobrijevic, M.; Engrand, C.; Geffard, M.; Grenier-Loustalot, M. F.; Largeau, C.

2000-07-01

On Earth, the molecules which participated in the emergence of life about 4 Ga ago have been erased by plate tectonics, the permanent presence of running water, unshielded solar ultraviolet radiation and by oxygen produced by life. Since the environment of the early Mars about 3.5-4 Ga ago was probably very close to that of the early Earth, life might have emerged on Mars as well and might give us some insight into the prebiotic chemistry that took place on Earth about 4 Ga ago. Furthermore, there is a possibility that life still exists on Mars, protected from the harsh environment in some specific locales. In order to search for life on Mars, one should look for potential biogenic markers such as organic matter and inorganic signatures (microfossils, biominerals, biogenic etching, isotopic fingerprints...) which have different degrees of resistance to the Martian environment. As biomarkers could be organic or inorganic in nature, complete organic and mineral analyses should therefore be conducted in parallel on the same sets of samples, going from the least destructive to the most destructive technique of micro-analysis. Furthermore, in situ analyses should be complemented by high precision and high sensitivity laboratory measurements of returned Martian samples. Due to the very oxidized Martian environment, organic molecules should be searched for in protected sites, either surface boulders or near sub-surface, in layers deep enough for avoiding the oxidizing effect of the atmosphere. Molecules that should be looked for include low and high molecular weight organics (like alkanoic acids, peroxiacids, PAHs and amino acids, respectively), and macromolecular com-pounds like kerogens or kerogen-like materials. Previous in situ analyses were performed using pyrolysis systems which allow to detect organic compounds but do not always permit the identification of individual molecules. New possible analytical solutions could include gas chromatography-based techniques

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

NASA Astrophysics Data System (ADS)

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

Hydrocarbon potential of Early Cretaceous lacustrine sediments from Bima Formation, Yola Sub-basin, Northern Benue Trough, NE Nigeria: Insight from organic geochemistry and petrology

NASA Astrophysics Data System (ADS)

Sarki Yandoka, Babangida M.; Abdullah, Wan Hasiah; Abubakar, M. B.; Adegoke, Adebanji Kayode; Maigari, A. S.; Haruna, A. I.; Yaro, Usman Y.

2017-05-01

The Early Cretaceous lacustrine sediments from Bima Formation in the Yola Sub-basin, Northern Benue Trough, northeastern Nigeria were studied based on organic geochemistry and petrology. This is in other to provide information on hydrocarbon generation potential; organic matter type (quality), richness (quantity), origin/source inputs, redox conditions (preservation) and thermal maturation in relation to thermal effect of Tertiary volcanics. The total organic carbon (TOC) contents ranges from 0.38 to 0.86 wt % with extractable organic matter (EOM) below 1000 ppm and pyrolysis S2 yield values from 0.16 to 0.68 mg/g, suggesting poor to fair source rock richness. Based on kerogen pyrolysis and microscopy coupled with biomarker parameters, the organic matters contain Type I (lacustrine algae), Type III (terrestrially derived land-plants) and Type IV kerogens deposited in a mixed lacustrine-terrestrial environment under suboxic to relatively anoxic conditions. This suggest potential occurrence of Early Cretaceous lacustrine sediments (perhaps Lower Cretaceous petroleum system) in Yola Sub-basin of the Northern Benue Trough as present in the neighbouring basins of Chad, Niger and Sudan Republics that have both oil and gas generation potential within the same rift trend (WCARS). Vitrinite reflectance (%Ro) and Tmax values of the lacustrine shales ranges from 1.12 to 2.32 VRo% and 448-501 °C, respectively, indicating peak-late to post-maturity stage. This is supported by the presence of dark brown palynomorphs, amorphous organic matter and phytoclasts as well as inertinite macerals. Consequently, the organic matters in the lacustrine shales of Bima Formation in the Yola Sub-basin appeared as a source of oil (most likely even waxy) and gas prone at a relatively deeper part of the basin. However, the high thermal maturity enhanced the organic matters and most of the hydrocarbons that formed in the course of thermal maturation were likely expelled to the reservoir rock units

Examination of factors dominating the sediment-water diffusion flux of DDT-related compounds measured by passive sampling in an urbanized estuarine bay.

PubMed

Feng, Yan; Wu, Chen-Chou; Bao, Lian-Jun; Shi, Lei; Song, Lin; Zeng, Eddy Y

2016-12-01

The fate of hydrophobic organic compounds in aquatic environment are largely determined by their exchange at sediment-water interface, which is highly dynamic and subject to rapidly evolving environmental conditions. In turn, environmental conditions may be governed by both physicochemical parameters and anthropogenic events. To examine the importance of various impact factors, passive sampling devices were deployed at the seafloor of Hailing Bay, an urbanized estuarine bay in Guangdong Province of South China to measure the sediment-water diffusion fluxes of several metabolites of dichlorodiphenyltrichloroethane (DDT), p,p'-DDE, p,p'-DDD and o,p'-DDD. The physicochemical properties of water (temperature, pH, salinity and dissolved oxygen) and surface sediment (sediment organic matter, physical composition, pH, water content, colony forming unit and catalase activity) were also measured. The results showed that the diffusion fluxes of o,p'-DDD, p,p'-DDD and p,p'-DDE at sites A1 and A2 near a fishing boat maintenance facility ranged from 0.42 to 4.73 ng m -2 d -1 (from sediment to overlying water), whereas those at offshore sites varied between -0.03 and -3.02 ng m -2 d -1 (from overlying water to sediment), implicating A1 and A2 as the sources of the target compounds. The distribution patterns of the diffusion fluxes of the target compounds were different from those of water and sediment parameters (water temperature, salinity, sediment texture, pH, colony forming unit and catalase activity) at six sampling sites. This finding suggested that none of these parameters were critical in dictating the sediment-water diffusion fluxes. Besides, decreases in the contents of kerogen and black carbon by 6.7% and 11% would enhance the diffusion fluxes of the target compounds by 11-14% and 12-23%, respectively, at site A1, indicating that kerogen and black carbon were the key factors in mediating the sediment-water diffusion fluxes of DDT-related compounds in field

Chemical composition, structural properties, and source apportionment of organic macromolecules in atmospheric PM10 in a coastal city of Southeast China.

PubMed

Chen, Yanting; Du, Wenjiao; Chen, Jinsheng; Hong, Youwei; Zhao, Jinping; Xu, Lingling; Xiao, Hang

2017-02-01

Particulate matter (PM 10 ) associated with the fractions of organic macromolecules, including humic acid (HA), kerogen + black carbon (KB), and black carbon (BC), was determined during summer and winter at urban and suburban sites in a coastal city of southeast China. The organic macromolecules were characterized by elemental analysis (EA), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR), and their sources were identified by using stable carbon/nitrogen isotope (δ 13 C/δ 15 N) and the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) Model. The results showed that HA, kerogen (K), and BC accounted for the range of 3.89 to 4.55 % in PM 10 , while they were the dominant fractions of total organic carbon (TOC), ranging from 64.70 to 84.99 %. SEM analysis indicated that BC particles were porous/nonporous and consisted of spherical and non-spherical (i.e., cylindrical and elongate) structures. The FTIR spectra of HA, KB, and BC exhibited similar functional groups, but the difference of various sites and seasons was observed. HA in PM 10 contained a higher fraction of aliphatic structures, such as long-chain fatty and carbohydrates with a carboxylic extremity. The C/N ratio, SEM, and δ 13 C/δ 15 N values provided reliable indicators of the sources of HA, K, and BC in PM 10 . The results suggested that HA and K majorly originated from terrestrial plants, and BC came from the mixture of combustion of terrestrial plants, fossil fuel, and charcoal. The air masses in winter originated from Mongolia (4 %), the northern area of China (48 %), and northern adjacent cities (48 %), suggesting the influence of anthropogenic sources through long-range transport, while the air masses for the summer period came from South China Sea (34 %) and Western Pacific Sea (66 %), representing clean marine air masses with low concentrations of organic macromolecules.

Isotope excursions and shifting oxidation states recorded in the Paleoproterozoic Franceville Basin

NASA Astrophysics Data System (ADS)

Wang, V.; Junium, C. K.; Lu, Z.; Préat, A.

2014-12-01

Geochemical studies of Paleoproterozoic rocks have revealed that the initial rise of oxygen was protracted and that Earth's surface environments fluctuated between oxic and anoxic states over hundreds of millions of years. Marine sediments of the 2.1 Gyr-old Franceville Basin of west central Africa are only lightly metamorphosed, and their geochemistry may thus reveal unique insights into the environmental and metabolic conditions during the history of rising oxygen levels. In the Franceville Basin stratigraphic variation totaling 10‰ in δ13Ccarb was previously documented. This contribution builds on this work and characterizes changes in C, N, and S cycles using stable isotope values. The results from systematic analysis of several biologically mediated redox proxies preserved in carbonates from the Franceville Basin will be presented, including δ34S values of pyrite and δ13C and δ15N values of bulk organic carbon and kerogens. Consistent with independent reports of an excursion in δ13Corg in the Franceville Basin and elsewhere, we find ~20‰ stratigraphic variation in δ13C of bulk organic carbon. Initial results for δ15N of bulk organic matter range from -6 to 6 ‰, a wider distribution of values than previously reported for the Franceville Basin and more negative than values reported for the similarly aged Onega Basin in Fennoscandia. I/Ca ratios range from near zero to near Phanerozoic levels and are consistent with the presence of iodate. Chromium reducible sulfide has been extracted from all but one sample, confirming the presence of pyrite. δ34S of pyrite as well as δ13C and δ15N of kerogen will also be presented. The biochemically diverse array of proxy analyses presented here have varying thresholds of sensitivity to oxygen levels and hence will allow detailed reconstruction of the redox history of basin waters. As minimum O2 thresholds are often needed for certain biochemical processes, the resulting data will also have implications for key

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

Molina, J.

The Chipaque-Lower Carbonera({circ}) Petroleum System of the northernmost Llanos Basin of Colombia, covers 11,100 km{sup 2} and includes two major oil fields: Caho Limon in Colombia, and Guafita in Venezuela, jointly with three more relatively small fields in Colombia: Redondo, Cano Rondon, and Jiba. Ultimate recoverable reserves are in the order of 1.4 BBO. The sedimentary section penetrated in the Northern Llanos has been informally subdivided into four Cretaceous formations: K3, K2B, K2A, and Lower K1 deposited during the Albian-Senonian, and into four Tertiary formations: Lower Carbonera, Upper Carbonera, Leon, and Guayabo deposited during the Late Eocene to Pliocene time.more » The main reservoir is the Lower Carbonera Formation, which contains 81% of the total reserves. The Cretaceous K2A and Lower K1 reservoirs contain 6% and 8%, respectively of the reserves. Minor reserves are accumulated in the discontinuous sandstones of the Oligocene Upper Carbonera Formation Geochemical analyses of the Cano Limon/Guafita oils indicate that these are aromatic intermediate to paraffinic-naphthenic, non degradated, genetically related to a common marine-derived type of kerogen. These oils were generated by a mature, marine clastic source rock with a small contribution of continental organic matter. The geochemistry of the hydrocarbon suggest a genetic relationship with the shales of the Chipaque formation, basin-ward equivalent of the K2 Formation, which presents kerogen type II organic matter and has been recognized as a good source rock. The petroleum system is hypothetical because a definite oil-source rock correlation is lacking. The development of the petroleum system is directly related to the history of movement of the Santa Maria, La Yuca, Caho Limon, and Matanegra wrench faults. It has been determined that these faults of pre-Cretaceous rifting origin, created the Santa Maria Graben of which the Espino Graben is the continuation in Venezuela.« less

Detecting Nonvolatile Life- and Nonlife-Derived Organics in a Carbonaceous Chondrite Analogue with a New Multiplex Immunoassay and Its Relevance for Planetary Exploration.

PubMed

Moreno-Paz, Mercedes; Gómez-Cifuentes, Ana; Ruiz-Bermejo, Marta; Hofstetter, Oliver; Maquieira, Ángel; Manchado, Juan M; Morais, Sergi; Sephton, Mark A; Niessner, Reinhard; Knopp, Dietmar; Parro, Victor

2018-04-11

Potential martian molecular targets include those supplied by meteoritic carbonaceous chondrites such as amino acids and polycyclic aromatic hydrocarbons and true biomarkers stemming from any hypothetical martian biota (organic architectures that can be directly related to once living organisms). Heat extraction and pyrolysis-based methods currently used in planetary exploration are highly aggressive and very often modify the target molecules making their identification a cumbersome task. We have developed and validated a mild, nondestructive, multiplex inhibitory microarray immunoassay and demonstrated its implementation in the SOLID (Signs of Life Detector) instrument for simultaneous detection of several nonvolatile life- and nonlife-derived organic molecules relevant in planetary exploration and environmental monitoring. By utilizing a set of highly specific antibodies that recognize D- or L- aromatic amino acids (Phe, Tyr, Trp), benzo[a]pyrene (B[a]P), pentachlorophenol, and sulfone-containing aromatic compounds, respectively, the assay was validated in the SOLID instrument for the analysis of carbon-rich samples used as analogues of the organic material in carbonaceous chondrites or even Mars samples. Most of the antibodies enabled sensitivities at the 1-10 ppb level and some even at the ppt level. The multiplex immunoassay allowed the detection of B[a]P as well as aromatic sulfones in a water/methanol extract of an Early Cretaceous lignite sample (c.a., 140 Ma) representing type IV kerogen. No L- or D-aromatic amino acids were detected, reflecting the advanced diagenetic stage and the fossil nature of the sample. The results demonstrate the ability of the liquid extraction by ultrasonication and the versatility of the multiplex inhibitory immunoassays in the SOLID instrument to discriminate between organic matter derived from life and nonlife processes, an essential step toward life detection outside Earth. Key Words: Planetary exploration

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

USGS Publications Warehouse

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

Biogeochemistry of Neoproterozoic Snowball Earth and its Aftermath in South China

NASA Astrophysics Data System (ADS)

Li, C.; Love, G.; Sessions, A.; Lyons, T.; Chu, X.; Peng, P.

2007-12-01

Using a combination of lipid biomarkers, inorganic geochemical proxies (Fe speciation and trace element analyses) and stable isotopic abundances (13C, 34S, 98Mo), we are reconstructing ocean chemistry and aquatic microbial community structure around the Neoproterozoic Sturtian and Marinoan glacial events and later into the Ediacaran in South China. We have sampled outcrop sediment extensively at four locations (Yichang, Shimen, Minle and Zhaoxin), obtaining sedimentary facies ranging from shallow shelf to the deep basin. Our stratigraphic coverage spans from unweathered sediments of the pre-Sturtian Gongdong Formation up to the post-Marinoan Doushantuo Formation. This approach allows us to compile, for the first time, a highly detailed, spatial and temporal record of Neoproterozoic marine biogeochemistry in South China. To assess and augment conventional extractable biomarker hydrocarbon data, we are using the technique of catalytic hydropyrolysis (HyPy) on kerogen residues to release well-preserved kerogen-bound biomarkers that are much less susceptible to contamination since they are covalently bound within an immobile solid matrix deposited synchronously with the host sediment. Interglacial Datangpo and Ediacaran Doushantuo formations that sandwich the Marinoan diamictites are most interesting for detailed organic and inorganic examination and comparison in this study due to their distinct stratigraphic context and unique spatial preservation. A diverse range of normal, branched (2-methyl, 3-methyl and mid-chain monomethylalkanes) and polycyclic alkanes (steranes and hopanes) have been successfully isolated from Doushantuo sediments in Shimen, and a distinct correlation between host-rock lithology and molecular and isotopic characteristics of detected alkane biomarkers was observed, suggesting that the hydrocarbon signals are indigenous and syngenetic with the host rocks. Sediments with appreciable inorganic carbonate content appear to hold most promise for

Organic pi-stacking Semiconducting Material: Design, Synthesis and the Analysis of Structure and Properties

NASA Astrophysics Data System (ADS)

Wilkinson, Taylor Marie

Oil shales are naturally occurring heterogeneous composites with micro-scale, micro-structural variations. They may be found throughout the world, with large deposits located in the United States; shales are composed of organic matter known as kerogen, clays, calcite, quartz, and other minerals. Typically their microstructure consists of a composite network where the organic matter is housed in open and closed pores between different mineral phases that range in size from sub-micron to several microns. Currently, it is unknown how the micro-scale heterogeneity of the shale will impact hydraulic fracture, which is the key extraction technique used for these materials. In this thesis, high-resolution topographic and modulus maps were collected from oil shales with the use of new nanoindentation techniques in order to characterize the micro-scale, micro-structural variations that are typical for these materials. Dynamic modulus mapping allows for substantially higher spatial resolution of properties across grains and intragranular regions of kerogen than has previously been produced with standard quasistatic indentation methods. For accurate scanning, surface variations were minimized to maintain uniform contact of the tip and appropriate quasi-static and dynamic forces were used to maintain displacement amplitudes that avoid plastic deformation of the sample. Sample preparation to minimize surface roughness was completed with the use of focused ion beam milling, however, some variation was still noted. Due to the large changes in modulus values between the constituents of the shale, there were variations in the recorded displacement amplitude values as well. In order to distinguish biased data due to surface topography or a lack of displacement amplitude, filtering techniques were developed, optimization and implemented. Variations in surface topography, which resulted in the indenter tip not being able to accurately resolve surface features, and inadequate

Thermal Desorption/GCMS Analysis of Astrobiologically Relevant Organic Materials

NASA Technical Reports Server (NTRS)

McDonald, Gene D.

2001-01-01

Several macromolecular organic materials, both biologically-derived (type II kerogen and humic acid) and abiotic in origin (Murchison insoluble organic material, cyanide polymer, and Titan tholin) were subjected to thermal desorption using a Chromatoprobe attachment on a Varian Saturn 2000 GCMS system. Each sample was heated sequentially at 100, 200, and 300 C to release volatile components. The evolved compounds were then separated on a Supelco EC-1 dimethylsilica GC column and detected by the Saturn 2000 ion trap mass spectrometer. The various types of macromolecular organic material subjected to thermal desorption produced distinctly different GCMS chromatograms at each temperature, containing fractions of both low and high chromatographic mobility. The relative amounts of detectable volatiles released at each temperature also differed, with type II kerogen and cyanide polymer containing the highest percentage of low-temperature components. In all the samples, the highest yield of released compounds occurred at 300 C. Only cyanide polymer evolved a homologous hydrocarbon series, suggesting that it is the only material among those examined that contains a truly polymeric structure. Pyrolysis/gas chromatography/mass spectrometry has been used extensively for analysis of terrestrial organic macromolecular materials, and was also part of the instrument package on the Viking landers. Thorough analysis by pyrolysis usually employs temperatures of 500 C or higher, which for in situ analyses can be problematic given spacecraft power and materials constraints. This study demonstrates that heating of organic materials of astrobiological relevance to temperatures as low as 200-300 C for short periods releases volatile components that can be analyzed by gas chromatography and mass spectrometry. Even in the absence of full pyrolysis, useful chemical information on samples can be obtained, and materials from different biological and abiological sources can be distinguished

Application of binomial-edited CPMG to shale characterization

USGS Publications Warehouse

Washburn, Kathryn E.; Birdwell, Justin E.

2014-01-01

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.

Metal speciation in Julia Creek oil shale

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

Hirner, A.V.

1989-03-01

The concentrations of 19 elements were determined in organic and inorganic phases of the Julia Creek Oil Shale (Queensland/Australia). The phases were obtained by solvent and alkaline extractions as well as by stepwise demineralization with strong acids. Together with the results of other groups, a consistent model concerning the partition of trace elements in the various sedimentary components could be achieved. Whereas V, Ni and Ag show distributions comparable to the abundances of the correspondent phases in the sample, Ca, Mn and Co are concentrated in the mineral components, and B, As and Pb are enriched in kerogen. Al, Cr,more » Fe, Cu, Zn, Mo, Cd and Sb range between these extremes, while Au and Hg are contained in the humic substances only.« less

Optical properties of poly-HCN and their astronomical applications

NASA Technical Reports Server (NTRS)

Khare, B. N.; Sagan, C.; Thompson, W. R.; Arakawa, E. T.; Meisse, C.; Tuminello, P. S.

1994-01-01

Matthews (1992) has proposed that HCN "polymer" is ubiquitous in the solar system. We apply vacuum deposition and spectroscopic techniques previously used on synthetic organic heteropolymers (tholins), kerogens, and meteoritic organic residues to the measurement of the optical constants of poly-HCN in the wavelength range 0.05-40 micrometers. These measurements allow quantitative comparison with spectrophotometry of organic-rich bodies in the outer solar system. In a specific test of Matthews' hypothesis, poly-HCN fails to match the optical constants of the haze of the Saturnian moon, Titan, in the visible and near-infrared derived from astronomical observations and standard models of the Titan atmosphere. In contrast, a tholin produced from a simulated Titan atmosphere matches within the probable errors. Poly-HCN is much more N-rich than Titan tholin.

Organic Analysis in Miller Range 090657 and Buckley Island 10933 CR2 Chondrites: Part 1 In-Situ Observation of Carbonaceous Material

NASA Technical Reports Server (NTRS)

Cao, T.; Nakamura-Messenger, K.; Berger, E. L.; Burton, A. S.; Messenger, S.; Clemett, S. J.

2016-01-01

Primitive carbonaceous chondrites contain a wide variety of organic material, ranging from soluble discrete molecules to insoluble unstructured kerogen-like component as well as structured nano-globules of macromolecular carbon. The relationship between the soluble organic molecules, macromolecular organic material, and host minerals are poorly understood. Due to the differences in extractability of soluble and insoluble organic materials, the analysis methods for each differ and are often performed independently. The combination of soluble and insoluble analyses, when performed concurrently, can provide a wider understanding on spatial distribution, and elemental, structural and isotopic composition of organic material in primitive meteorites. Furthermore, they can provide broader perspective on how extraterrestrial organic ma-terials potentially contributed to the synthesis of life's essential compounds such as amino acids, sugar acids, activated phosphates and nucleobases.

The influence of extractable organic matter on vitrinite reflectance suppression: A survey of kerogen and coal types

USGS Publications Warehouse

Barker, C.E.; Lewan, M.D.; Pawlewicz, M.J.

2007-01-01

The vitrinite reflectance suppression literature shows that while bitumen impregnation of the vitrinite group is often invoked as a significant contributor to suppression, its existence is not often supported by petrological evidence. This study examines bitumen impregnation as a factor in vitrinite suppression by comparing the vitrinite reflectance of source rock and coal samples before and after solvent-extraction. Bitumen, often defined as organic matter soluble or extractable in certain organic solvents, should be removed by Soxhlet method solvent extraction using chloroform. Removing the extractable bitumen should restore the suppressed reflectance to its true higher value. However, the solvent extracted samples averaged 0.014% Rv less than that of the unextracted samples. We conclude from these results and from other published data that reflectance suppression by bitumen impregnation in the vitrinite maceral group, above the huminite stage of gelification, is seemingly a rare phenomenon and whose effect on suppressing vitrinite reflectance is typically negligible. ?? 2006.

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

USGS Publications Warehouse

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.

Oil source bed distribution in upper Tertiary of Gulf Coast

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

Dow, W.G.

1985-02-01

Effective oil source beds have not been reported in Miocene and younger Gulf Coast sediments and the organic matter present is invariably immature and oxidized. Crude oil composition, however, indicates origin from mature source beds containing reduced kerogen. Oil distribution suggests extensive vertical migration through fracture systems from localized sources in deeply buried, geopressured shales. A model is proposed in which oil source beds were deposited in intraslope basins that formed behind salt ridges. The combination of silled basin topography, rapid sedimentation, and enhanced oxygen-minimum zones during global warmups resulted in periodic anoxic environments and preservation of oil-generating organic matter.more » Anoxia was most widespread during the middle Miocene and Pliocene transgressions and rare during regressive cycles when anoxia occurred primarily in hypersaline conditions such as exist today in the Orca basin.« less

Morphological and ecological complexity in early eukaryotic ecosystems.

PubMed

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.

Process for oil shale retorting

DOEpatents

Jones, John B.; Kunchal, S. Kumar

1981-10-27

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

Nitrogen cycling following The Great Oxidation Event, evidence from the Paleoproterozoic of Fennoscandia.

NASA Astrophysics Data System (ADS)

Junium, C. K.; Kump, L.; Arthur, M. A.; Melezhik, V.; Lepland, A.; Members of the FAR-DEEP Drilling Team

2011-12-01

The Fennoscandia Arctic Russia - Drilling Early Earth Project (FAR-DEEP) recovered core materials spanning the early Paleoproterozoic of Arctic Russia under the auspices of the International Continental Scientific Drilling Program. Here we present N and C isotopic data documenting N and C cycle dynamics during this critical interval of Earth history. Additionally, we will discuss the challenges of nitrogen isotope studies in such ancient sediments and the methods that we have utilized to test the fidelity of our nitrogen isotope data. Nitrogen isotope studies in very ancient sedimentary rocks, like those recovered by the FAR-DEEP are plagued by the concerns of diagenetic and metamorphic overprinting. Nitrogen is often present in very low concentrations and in a variety of inorganic phases that may or may not be derived from the ambient organic matter. For these reasons, bulk sediment δ15N data can be at best, ambiguous. To overcome these issues we have utilized kerogens for δ15N and δ13C analyses. The large difference between bulk and kerogen δ15N data demonstrates that inorganic N is anomalously 15N-enriched, by up to 7% and bulk δ15N values substantially overestimate the magnitude of the 15N variability in the Onega Basin (OB) sediments. Metasomatic processes during basinal magamatic activity resulted in the addition of 15N-enriched inorganic-N. Authigenic K-bearing micas are common in intervals where bulk δ15N values are 15N-enriched, suggesting that secondary mineral phases have retained 15N-enriched ammonia generated during metsomatism. The FAR-DEEP drilling team has documented an anomalously large, and rapid δ13C shift of -17% in carbonates and organic matter of the Zhaoneskaya Formation (ZF) of the OB following the extended period of 13Ccarb-enrichment know as the Lomagundi-Jatuli event. The isotopic shift in reduced carbon has also been recognized in the Franceville Formation of Gabon, termed here as "Shunga-Francevillian" anomaly, and may reflect

In Situ Carbon and Sulfur Isotope Analysis of Archean Organic Matter and Pyrite

NASA Technical Reports Server (NTRS)

Williford, K. H.; Ushikubo, T.; LePot, K.; Kitajima, K.; Spicuzza, M. J.; Valley, J. W.; Hallman, C.; Summons, R.; Eigenbrode, J. L.

2012-01-01

Stable isotopic compositions of biologically important elements (e.g., C and S) in sedimentary rocks are valuable biosignatures to the extent that they indicate the presence and variable expression of microbial metabolisms in space and time. Strong interactions between the carbon and sulfur cycles (e.g., via organic matter remineralization during microbial sulfate reduction) make coordinated, in situ C and S isotope analysis by secondary ion mass spectrometry (SIMS) a particularly powerful tool. In rocks ranging in age from 2.7-2.5 Ga, expansions in the ranges of delta C-13 of organic matter and delta S-34 of pyrite likely reflect the increasing influence of oxygenic photosynthesis in the surface ocean (as well as methane and sulfur metabolisms in deeper waters), whereas the large range of mass independent sulfur isotope fractionation (Delta S-33) suggests that the atmosphere remained anoxic until approx 2.4 Gyr ago. We report in situ delta C-13 measurements of organic matter in the approx 2.7-2.6 Ga Carawine Dolomite, Marra Mamba Iron Formation, and Jeerinah, Wittenoom, and Tumbiana Formations, as well as the approx 2.5 Ga Mount McRae Shale. We also report in situ delta S-24 and Delta S-33 measurements of pyrite associated with organic matter in a subset of these samples. In a single square cm sample of the Tumbiana Formation with bulk delta C-13(sub org) of -49.7% (VPDB), two distinct kerogen types have delta C-13 values, measured in situ, consistent with oxygenic photosynthesis (-33%) and methane metabolism (-52%). In a sample from the ABDP-9 core, radiobitumen associated with a uraniferous mineral grain is C-13-enriched by 8% (-26.8%0) relative to average in situ kerogen (-34.9%0) and similar in delta C-13 to solvent extractable hydrocarbons from the Mount McRae Shale (avg delta C-13 = -27.1 %). Average reproducibility for delta C-13 was 0.4% (2 SD) using a 6 micron spot and 0.8% using a 3 micron spot. In situ sulfur isotope analyses of 33 authigenic pyrite

Carbon and Sulfur Isotopic Signatures of Ancient Life and Environment at the Microbial Scale: Neoarchean Shales and Carbonates

NASA Technical Reports Server (NTRS)

Williford, K. H.; Ushikubo, T.; Lepot, K.; Kitajima, K.; Hallmann, C.; Spicuzza, M. J.; Kozdon, R.; Eigenbrode, J. L.; Summons, R. E.; Valley, J. W.

2015-01-01

An approach to coordinated, spatially resolved, in situ carbon isotope analysis of organic matter and carbonate minerals, and sulfur three- and four-isotope analysis of pyrite with an unprecedented combination of spatial resolution, precision, and accuracy is described. Organic matter and pyrite from eleven rock samples of Neoarchean drill core express nearly the entire range of delta(sup 13)C, delta(sup 34)S, Delta(sup 33)S, and Delta(sup 36)S known from the geologic record, commonly in correlation with morphology, mineralogy, and elemental composition. A new analytical approach (including a set of organic calibration standards) to account for a strong correlation between H/C and instrumental bias in SIMS delta(sup 13)C measurement of organic matter is identified. Small (2-3 microns) organic domains in carbonate matrices are analyzed with sub-permil accuracy and precision. Separate 20- to 50-micron domains of kerogen in a single approx. 0.5 cu cm sample of the approx. 2.7 Ga Tumbiana Formation have delta(sup 13)C = -52.3 +/- 0.1per mille and -34.4 +/- 0.1per mille, likely preserving distinct signatures of methanotrophy and photoautotrophy. Pyrobitumen in the approx. 2.6 Ga Jeerinah Formation and the approx. 2.5 Ga Mount McRae Shale is systematically 13C-enriched relative to co-occurring kerogen, and associations with uraniferous mineral grains suggest radiolytic alteration. A large range in sulfur isotopic compositions (including higher Delta(sup 33)S and more extreme spatial gradients in Delta(sup 33)S and Delta(sup 36)S than any previously reported) are observed in correlation with morphology and associated mineralogy. Changing systematics of delta(sup 34)S, Delta(sup 33)S, and Delta(sup 36)S, previously investigated at the millimeter to centimeter scale using bulk analysis, are shown to occur at the micrometer scale of individual pyrite grains. These results support the emerging view that the dampened signature of mass-independent sulfur isotope fractionation

Burial History, Thermal Maturity, and Oil and Gas Generation History of Source Rocks in the Bighorn Basin, Wyoming and Montana

USGS Publications Warehouse

Roberts, Laura N.R.; Finn, Thomas M.; Lewan, Michael D.; Kirschbaum, Mark A.

2008-01-01

Burial history, thermal maturity, and timing of oil and gas generation were modeled for seven key source-rock units at eight well locations throughout the Bighorn Basin in Wyoming and Montana. Also modeled was the timing of cracking to gas of Phosphoria Formation-sourced oil in the Permian Park City Formation reservoirs at two well locations. Within the basin boundary, the Phosphoria is thin and only locally rich in organic carbon; it is thought that the Phosphoria oil produced from Park City and other reservoirs migrated from the Idaho-Wyoming thrust belt. Other petroleum source rocks include the Cretaceous Thermopolis Shale, Mowry Shale, Frontier Formation, Cody Shale, Mesaverde and Meeteetse Formations, and the Tertiary (Paleocene) Fort Union Formation. Locations (wells) selected for burial history reconstructions include three in the deepest parts of the Bighorn Basin (Emblem Bench, Red Point/Husky, and Sellers Draw), three at intermediate depths (Amoco BN 1, Santa Fe Tatman, and McCulloch Peak), and two at relatively shallow locations (Dobie Creek and Doctor Ditch). The thermal maturity of source rocks is greatest in the deep central part of the basin and decreases to the south, east, and north toward the basin margins. The Thermopolis and Mowry Shales are predominantly gas-prone source rocks, containing a mix of Type-III and Type-II kerogens. The Frontier, Cody, Mesaverde, Meeteetse, and Fort Union Formations are gas-prone source rocks containing Type-III kerogen. Modeling results indicate that in the deepest areas, (1) the onset of petroleum generation from Cretaceous rocks occurred from early Paleocene through early Eocene time, (2) peak petroleum generation from Cretaceous rocks occurred during Eocene time, and (3) onset of gas generation from the Fort Union Formation occurred during early Eocene time and peak generation occurred from late Eocene to early Miocene time. Only in the deepest part of the basin did the oil generated from the Thermopolis and

A nuclear wind/solar oil-shale system for variable electricity and liquid fuels production

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

Forsberg, C.

2012-07-01

The recoverable reserves of oil shale in the United States exceed the total quantity of oil produced to date worldwide. Oil shale contains no oil, rather it contains kerogen which when heated decomposes into oil, gases, and a carbon char. The energy required to heat the kerogen-containing rock to produce the oil is about a quarter of the energy value of the recovered products. If fossil fuels are burned to supply this energy, the greenhouse gas releases are large relative to producing gasoline and diesel from crude oil. The oil shale can be heated underground with steam from nuclear reactorsmore » leaving the carbon char underground - a form of carbon sequestration. Because the thermal conductivity of the oil shale is low, the heating process takes months to years. This process characteristic in a system where the reactor dominates the capital costs creates the option to operate the nuclear reactor at base load while providing variable electricity to meet peak electricity demand and heat for the shale oil at times of low electricity demand. This, in turn, may enable the large scale use of renewables such as wind and solar for electricity production because the base-load nuclear plants can provide lower-cost variable backup electricity. Nuclear shale oil may reduce the greenhouse gas releases from using gasoline and diesel in half relative to gasoline and diesel produced from conventional oil. The variable electricity replaces electricity that would have been produced by fossil plants. The carbon credits from replacing fossil fuels for variable electricity production, if assigned to shale oil production, results in a carbon footprint from burning gasoline or diesel from shale oil that may half that of conventional crude oil. The U.S. imports about 10 million barrels of oil per day at a cost of a billion dollars per day. It would require about 200 GW of high-temperature nuclear heat to recover this quantity of shale oil - about two-thirds the thermal output of

Prediction of Reservoir Properties for Geomechanical Analysis Using 3-D Seismic Data and Rock Physics Modeling in the Vaca Muerta Formation, Neuquen Basin, Argentina

NASA Astrophysics Data System (ADS)

Convers-Gomez, Carlos E.

The Vaca Muerta Formation in the Neuquen Basin has recently received a lot of attention from oil companies interested in developing its shale resources. Early identification of potential zones with possible good production is extremely important to optimize the return on capital investment. Developing a work flow in shale plays that associates an effective hydraulic fracture response with the presence of hydrocarbons is crucial for economic success. The vertical and lateral heterogeneity of rock properties are critical factors that impact production. The integration of 3D seismic and well data is necessary for prediction of rock properties and identifies their distribution in the rock, which can also be integrated with geomechanical properties to model the rock response favorable to hydraulic stimulation. This study includes a 3D seismic survey and six vertical wells with full log suites in each well. The well logs allowed for the computation of a pre-stack model-based inversion which uses seismic data to estimate rock property volumes. An inverse relationship between P-impedance and Total Organic Content (TOC) was observed and quantified. Likewise, a direct relationship between P-impedance and volume of carbonate was observed. The volume of kerogen, type of clay, type of carbonate and fluid pressure all control the geomechanical properties of the formation when subject to hydraulic fracturing. Probabilistic Neural Networks were then used to predict the lateral and vertical heterogeneity of rock properties. TOC and volume of kerogen behaved as adequate indicators of possible zones with high presence of hydrocarbons. Meanwhile, the volume of carbonate was a valid indicator of brittle-ductile rock. The predicted density volume was used to estimate geomechanical properties (Young's Modulus and Poisson's Ratio) and to identify the zones that have a better response to hydraulic stimulation. During the analysis of geomechanical properties, Young's Modulus was observed to

Aquifers survey in the context of source rocks exploitation: from baseline acquisition to long term monitoring

NASA Astrophysics Data System (ADS)

Garcia, Bruno; Rouchon, Virgile; Deflandre, Jean-Pierre

2017-04-01

Producing hydrocarbons from source rocks (like shales: a mix of clays, silts, carbonate and sandstone minerals containing matured organic matter, i.e. kerogen oil and gas, but also non-hydrocarbon various species of chemical elements including sometimes radioactive elements) requires to create permeability within the rock matrix by at least hydraulically fracturing the source rock. It corresponds to the production of hydrocarbon fuels that have not been naturally expelled from the pressurized matured source rock and that remain trapped in the porosity or/and kerogen porosity of the impermeable matrix. Azimuth and extent of developed fractures can be respectively determined and mapped by monitoring the associated induced microseismicity. This allows to have an idea of where and how far injected fluids penetrated the rock formation. In a geological context, aquifers are always present in the vicinity -or on fluid migration paths- of such shale formations: deep aquifers (near the shale formation) up to sub-surface and potable (surface) aquifers. Our purpose will be to track any unsuitable invasion or migration of chemicals specifies coming from matured shales of production fluids including both drilling and fracturing ones into aquifers. Our objective is to early detect and alarm of any anomaly to avoid any important environmental issue. The approach consists in deploying a specific sampling tool within a well to recover formation fluids and to run a panoply of appropriate laboratory tests to state on fluid characteristics. Of course for deep aquifers, such a characterization process may consider aquifer properties prior producing shale oil and gas, as they may contain naturally some chemical species present in the source rocks. One can also consider that a baseline acquisition could be justified in case of possible previous invasion of non-natural fluids in the formation under survey (due to any anthropogenic action at surface or in the underground). The paper aims

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

USGS Publications Warehouse

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

Timing and petroleum sources for the Lower Cretaceous Mannville Group oil sands of northern Alberta based on 4-D modeling

USGS Publications Warehouse

Higley, D.K.; Lewan, M.D.; Roberts, L.N.R.; Henry, M.

2009-01-01

The Lower Cretaceous Mannville Group oil sands of northern Alberta have an estimated 270.3 billion m3 (BCM) (1700 billion bbl) of in-place heavy oil and tar. Our study area includes oil sand accumulations and downdip areas that partially extend into the deformation zone in western Alberta. The oil sands are composed of highly biodegraded oil and tar, collectively referred to as bitumen, whose source remains controversial. This is addressed in our study with a four-dimensional (4-D) petroleum system model. The modeled primary trap for generated and migrated oil is subtle structures. A probable seal for the oil sands was a gradual updip removal of the lighter hydrocarbon fractions as migrated oil was progressively biodegraded. This is hypothetical because the modeling software did not include seals resulting from the biodegradation of oil. Although the 4-D model shows that source rocks ranging from the Devonian-Mississippian Exshaw Formation to the Lower Cretaceous Mannville Group coals and Ostracode-zone-contributed oil to Mannville Group reservoirs, source rocks in the Jurassic Fernie Group (Gordondale Member and Poker Chip A shale) were the initial and major contributors. Kinetics associated with the type IIS kerogen in Fernie Group source rocks resulted in the early generation and expulsion of oil, as early as 85 Ma and prior to the generation from the type II kerogen of deeper and older source rocks. The modeled 50% peak transformation to oil was reached about 75 Ma for the Gordondale Member and Poker Chip A shale near the west margin of the study area, and prior to onset about 65 Ma from other source rocks. This early petroleum generation from the Fernie Group source rocks resulted in large volumes of generated oil, and prior to the Laramide uplift and onset of erosion (???58 Ma), which curtailed oil generation from all source rocks. Oil generation from all source rocks ended by 40 Ma. Although the modeled study area did not include possible western

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

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

Fungal colonization of an Ordovician impact-induced hydrothermal system

PubMed Central

Ivarsson, Magnus; Broman, Curt; Sturkell, Erik; Ormö, Jens; Siljeström, Sandra; van Zuilen, Mark; Bengtson, Stefan

2013-01-01

Impacts are common geologic features on the terrestrial planets throughout the solar system, and on at least Earth and Mars impacts have induced hydrothermal convection. Impact-generated hydrothermal systems have been suggested to possess the same life supporting capability as hydrothermal systems associated with volcanic activity. However, evidence of fossil microbial colonization in impact-generated hydrothermal systems is scarce in the literature. Here we report of fossilized microorganisms in association with cavity-grown hydrothermal minerals from the 458 Ma Lockne impact structure, Sweden. Based on morphological characteristics the fossilized microorganisms are interpreted as fungi. We further infer the kerogenization of the microfossils, and thus the life span of the fungi, to be contemporaneous with the hydrothermal activity and migration of hydrocarbons in the system. Our results from the Lockne impact structure show that hydrothermal systems associated with impact structures can support colonization by microbial life. PMID:24336641

Fungal colonization of an Ordovician impact-induced hydrothermal system

NASA Astrophysics Data System (ADS)

Ivarsson, Magnus; Broman, Curt; Sturkell, Erik; Ormö, Jens; Siljeström, Sandra; van Zuilen, Mark; Bengtson, Stefan

2013-12-01

Impacts are common geologic features on the terrestrial planets throughout the solar system, and on at least Earth and Mars impacts have induced hydrothermal convection. Impact-generated hydrothermal systems have been suggested to possess the same life supporting capability as hydrothermal systems associated with volcanic activity. However, evidence of fossil microbial colonization in impact-generated hydrothermal systems is scarce in the literature. Here we report of fossilized microorganisms in association with cavity-grown hydrothermal minerals from the 458 Ma Lockne impact structure, Sweden. Based on morphological characteristics the fossilized microorganisms are interpreted as fungi. We further infer the kerogenization of the microfossils, and thus the life span of the fungi, to be contemporaneous with the hydrothermal activity and migration of hydrocarbons in the system. Our results from the Lockne impact structure show that hydrothermal systems associated with impact structures can support colonization by microbial life.

Fungal colonization of an Ordovician impact-induced hydrothermal system.

PubMed

Ivarsson, Magnus; Broman, Curt; Sturkell, Erik; Ormö, Jens; Siljeström, Sandra; van Zuilen, Mark; Bengtson, Stefan

2013-12-16

Impacts are common geologic features on the terrestrial planets throughout the solar system, and on at least Earth and Mars impacts have induced hydrothermal convection. Impact-generated hydrothermal systems have been suggested to possess the same life supporting capability as hydrothermal systems associated with volcanic activity. However, evidence of fossil microbial colonization in impact-generated hydrothermal systems is scarce in the literature. Here we report of fossilized microorganisms in association with cavity-grown hydrothermal minerals from the 458 Ma Lockne impact structure, Sweden. Based on morphological characteristics the fossilized microorganisms are interpreted as fungi. We further infer the kerogenization of the microfossils, and thus the life span of the fungi, to be contemporaneous with the hydrothermal activity and migration of hydrocarbons in the system. Our results from the Lockne impact structure show that hydrothermal systems associated with impact structures can support colonization by microbial life.

Spectroscopic studies of wood fossils from the Crato Formation, Cretaceous Period.

PubMed

da Silva, J H; Freire, P T C; Abagaro, B T O; Silva, J A F; Saraiva, G D; de Lima, F J; Barros, O A; Bantim, R A; Saraiva, A A F; Viana, B C

2013-11-01

In this work we study two types of wood fossils (Gymnosperms, Araucariaceae) from the Crato Formation of Araripe Basin in Brazil, from the Cretaceous Period. The samples were characterized by Raman and infrared spectroscopies, X-ray diffraction and scanning electron microscopy. The results obtained by different techniques showed that although the rocks surrounding the fossils have predominantly the same constitution - calcite - however, the formation processes of these types of wood fossils are quite different. One of the fossils, denominated as light wood, is predominantly composed of gypsum, while the other fossil, the dark wood, is rich in amorphous carbon, possibly the kerogen type. Implications relative to the environment where the plants lived millions years ago are also given. Finally, the results highlight the constitution of one of the most important paleontological sites of the Cretaceous Period in the South America. Copyright © 2013 Elsevier B.V. All rights reserved.

Diagenesis of metabolites and a discussion of the origin of petroleum hydrocarbons

USGS Publications Warehouse

Breger, I.A.

1960-01-01

Proteins and carbohydrates are rapidly degraded to compounds of no direct interest in the problem of the origin of petroleum. Lignin, if carried into marine basins in the form of humic substances, is probably the major progenitor of kerogen rather than the precursor of petroleum. Pigments are but minor contributors to petroleum. The fate of fatty acids in a marine environment is not completely understood. Although they may not be directly decarboxylated biochemically, it is shown how they can be converted into oxygenated or dehydrogenated acids more reactive than the parent compounds. Illustrations are also given for Diels-Alder reactions that could account for the formation from these compounds of the alicyclic and aromatic hydrocarbons in petroleum. It is most likely that crude oil is generated in sediments containing concentrations of lipids, the character of which governs the nature of the oil that is formed. ?? 1960.

NASA Curiosity rover hits organic pay dirt on Mars

NASA Astrophysics Data System (ADS)

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.

Activated desorption at heterogeneous interfaces and long-time kinetics of hydrocarbon recovery from nanoporous media.

PubMed

Lee, Thomas; Bocquet, Lydéric; Coasne, Benoit

2016-06-21

Hydrocarbon recovery from unconventional reservoirs (shale gas) is debated due to its environmental impact and uncertainties on its predictability. But a lack of scientific knowledge impedes the proposal of reliable alternatives. The requirement of hydrofracking, fast recovery decay and ultra-low permeability-inherent to their nanoporosity-are specificities of these reservoirs, which challenge existing frameworks. Here we use molecular simulation and statistical models to show that recovery is hampered by interfacial effects at the wet kerogen surface. Recovery is shown to be thermally activated with an energy barrier modelled from the interface wetting properties. We build a statistical model of the recovery kinetics with a two-regime decline that is consistent with published data: a short time decay, consistent with Darcy description, followed by a fast algebraic decay resulting from increasingly unreachable energy barriers. Replacing water by CO2 or propane eliminates the barriers, therefore raising hopes for clean/efficient recovery.

Resource and energy management of synfuels production with hydrogen and oxygen requirements from electrolysis

NASA Astrophysics Data System (ADS)

Shannon, R. H.; Richardson, R. D.

The Resource and Energy Management System (REM), which uses electrolytic H2 and O2 to produce synthetic crude and light oils from heavy hydrocarbons is described. The heavy hydrocarbon feedstocks include heavy oils, tar sand bitumens, heavy residual oils, oil shale kerogens, liquefied coal, and pyrolytically-extracted coal liquids. The system includes mini-upgraders, which can be implemented in modular form, to pump electrolytically-derived H2 into heavy oils to upgrade their energy content. Projected costs for the production of synthetic light oils using U.S. coal reserves with the REM process after liquefaction are $30-35/bbl, with the H2 costs being a controlling factor. The modular systems could be built in a much shorter time frame than much larger projects, and would be instrumental in establishing the electrolytic H2 production infrastructure needed for eventual full conversion to an H2-based economy.

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Technical Reports Server (NTRS)

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.

Relationships between thermal maturity indices calculated using Arrhenius equation and Lopatin method: implications for petroleum exploration

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

Wood, D.A.

1988-02-01

Thermal maturity can be calculated with time-temperature indices (TTI) based on the Arrhenius equation using kinetics applicable to a range of Types II and III kerogens. These TTIs are compared with TTI calculations based on the Lopatin method and are related theoretically (and empirically via vitrinite reflectance) to the petroleum-generation window. The TTIs for both methods are expressed mathematically as integrals of temperature combined with variable linear heating rates for selected temperature intervals. Heating rates control the thermal-maturation trends of buried sediments. Relative to Arrhenius TTIs, Lopatin TTIs tend to underestimate thermal maturity at high heating rates and overestimate itmore » as low heating rates. Complex burial histories applicable to a range of tectonic environments illustrate the different exploration decisions that might be made on the basis of independent results of these two thermal-maturation models. 15 figures, 8 tables.« less

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

NASA Astrophysics Data System (ADS)

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.

Natural Product Molecular Fossils.

PubMed

Falk, Heinz; Wolkenstein, Klaus

The natural products synthesized by organisms that were living a long time ago gave rise to their molecular fossils. These can consist of either the original unchanged compounds or they may undergo peripheral transformations in which their skeletons remain intact. In cases when molecular fossils can be traced to their organismic source, they are termed "geological biomarkers".This contribution describes apolar and polar molecular fossils and, in particular biomarkers, along the lines usually followed in organic chemistry textbooks, and points to their bioprecursors when available. Thus, the apolar compounds are divided in linear and branched alkanes followed by alicyclic compounds and aromatic and heterocyclic molecules, and, in particular, the geoporphyrins. The polar molecular fossils contain as functional groups or constituent units ethers, alcohols, phenols, carbonyl groups, flavonoids, quinones, and acids, or are polymers like kerogen, amber, melanin, proteins, or nucleic acids. The final sections discuss the methodology used and the fundamental processes encountered by the biomolecules described, including diagenesis, catagenesis, and metagenesis.

Distribution, richness, quality, and thermal maturity of source rock units on the North Slope of Alaska

USGS Publications Warehouse

Peters, K.E.; Bird, K.J.; Keller, M.A.; Lillis, P.G.; Magoon, L.B.

2003-01-01

Four source rock units on the North Slope were identified, characterized, and mapped to better understand the origin of petroleum in the area: Hue-gamma ray zone (Hue-GRZ), pebble shale unit, Kingak Shale, and Shublik Formation. Rock-Eval pyrolysis, total organic carbon analysis, and well logs were used to map the present-day thickness, organic quantity (TOC), quality (hydrogen index, HI), and thermal maturity (Tmax) of each unit. To map these units, we screened all available geochemical data for wells in the study area and assumed that the top and bottom of the oil window occur at Tmax of ~440° and 470°C, respectively. Based on several 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 organic richness prior to thermal maturation.

The Organic Composition of Carbonaceous Meteorites: The Evolutionary Story Ahead of Biochemistry

PubMed Central

Pizzarello, Sandra; Shock, Everett

2010-01-01

Carbon-containing meteorites provide a natural sample of the extraterrestrial organic chemistry that occurred in the solar system ahead of life's origin on the Earth. Analyses of 40 years have shown the organic content of these meteorites to be materials as diverse as kerogen-like macromolecules and simpler soluble compounds such as amino acids and polyols. Many meteoritic molecules have identical counterpart in the biosphere and, in a primitive group of meteorites, represent the majority of their carbon. Most of the compounds in meteorites have isotopic compositions that date their formation to presolar environments and reveal a long and active cosmochemical evolution of the biogenic elements. Whether this evolution resumed on the Earth to foster biogenesis after exogenous delivery of meteoritic and cometary materials is not known, yet, the selective abundance of biomolecule precursors evident in some cosmic environments and the unique L-asymmetry of some meteoritic amino acids are suggestive of their possible contribution to terrestrial molecular evolution. PMID:20300213

Early photosynthetic microorganisms and environmental evolution

NASA Technical Reports Server (NTRS)

Golubic, S.

1980-01-01

Microfossils which are preserved as shrivelled kerogenous residues provide little information about cellular organization and almost none about the metabolic properties of the organisms. The distinction between prokaryotic vs eukaryotic, and phototrophic vs chemo- and organotrophic fossil microorganisms rests entirely on morphological comparisons with recent counterparts. The residual nature of the microbial fossil record promotes the conclusion that it must be biased toward (a) most abundant organisms, (b) those most resistant to degradation, and (c) those inhabiting environments with high preservation potential e.g., stromatolites. These criteria support the cyanophyte identity of most Precambrian microbial fossils on the following grounds: (1) as primary producers they dominate prokaryotic communities in modern extreme environments, e.g., intertidal zone; (2) several morphological counterparts of modern cyanophytes and microbial fossils have been established based on structure, cell division patterns and degradation sequences. The impact of anaerobic and oxygenic microbial photosynthesis on the evolution of Precambrian environments is discussed.

Constraints on the Organic Composition of Meteoroids

NASA Technical Reports Server (NTRS)

McKay, Chris P.; Steel, D. I.; Cuzzi, Jeffrey (Technical Monitor)

1996-01-01

One of the major results obtained from the spacecraft experiments at Comet Halley, and subsequent telescopic observations of comets, is the identification of a substantial organic fraction of cometary dust. There are also various meteor observations which indicate that there may also be a significant heavy organic component of small (mm-cm) meteoroids entering the terrestrial atmosphere. Here we describe the results of thermodynamic modelling of idealized meteoroids which was directed towards discovering which volatile species could survive for the (typically) millennia between release from a comet and entry into the atmosphere. We find that the most likely species to survive from plausible volatile constituents axe organic species with carbon numbers greater than -20 (i.e., tarry or kerogen-type chemicals). This result is in accord with recent observations of the heights of ablation of meteors observed using radar techniques, and provides supportive evidence for the idea that organic molecules are continually raining down upon our planet.

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

NASA Astrophysics Data System (ADS)

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.

Activated desorption at heterogeneous interfaces and long-time kinetics of hydrocarbon recovery from nanoporous media

PubMed Central

Lee, Thomas; Bocquet, Lydéric; Coasne, Benoit

2016-01-01

Hydrocarbon recovery from unconventional reservoirs (shale gas) is debated due to its environmental impact and uncertainties on its predictability. But a lack of scientific knowledge impedes the proposal of reliable alternatives. The requirement of hydrofracking, fast recovery decay and ultra-low permeability—inherent to their nanoporosity—are specificities of these reservoirs, which challenge existing frameworks. Here we use molecular simulation and statistical models to show that recovery is hampered by interfacial effects at the wet kerogen surface. Recovery is shown to be thermally activated with an energy barrier modelled from the interface wetting properties. We build a statistical model of the recovery kinetics with a two-regime decline that is consistent with published data: a short time decay, consistent with Darcy description, followed by a fast algebraic decay resulting from increasingly unreachable energy barriers. Replacing water by CO2 or propane eliminates the barriers, therefore raising hopes for clean/efficient recovery. PMID:27327254

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

NASA Astrophysics Data System (ADS)

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.

Investigation of the Reactions and Distribution of Polycyclic Aromatic Hydrocarbons and Fullerenes in Extraterrestrial Material

NASA Technical Reports Server (NTRS)

Zare, Richard N.

2005-01-01

The work funded by this research grant includes four specific projects: (1) Mapping the spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. (2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe laser-desorption laser-ionization mass spectrometry ( pL2MS) and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. (3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. (4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames.

Carbon, nitrogen, and sulfur geochemistry of Archean and Proterozoic shales from the Kaapvaal Craton, South Africa

NASA Astrophysics Data System (ADS)

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 <0.01-0.09 wt%, average 0.1 wt%), and S (range <0.01-1.63 wt%, average 0.1 wt%). The low N/C (<0.005) and H/C (mostly ˜0.2) atomic ratios in kerogens from the shales indicated that the Kaapvaal shales lost considerable amounts of N, C, S, and H during diagenesis and regional metamorphism (up to the greenschist 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

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

USGS Publications Warehouse

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

Compound-specific carbon isotope analysis of instantaneous gas generated from shaly coal during hydrous pyrolysis

NASA Astrophysics Data System (ADS)

Tsai, Wen-Yu; Sun, Chih-Hsien; Huang, Wuu-Liang

2010-05-01

Isotopes of natural gases have provided important information for indicating their maturation, origins and influencing factors during the generation processes. In order to distinguish compositions of gas generated at different intervals of maturities, the present study investigates the variation of compound-specific carbon isotope (CSI) ratios of hydrocarbon gases from a shaly coal by instantaneous hydrous pyrolysis, during which the earlier generated gas was evacuated before the start of next maturation stage. The experiments were conducted at ten different maturity stages (0.65 to 2.02 % Ro) from a terrestrial shaly coal with 0.48 % Ro. The gas products were analyzed by GC-IR-MS. The results show that, in general, the δ13C values of methane (C1), ethane (C2), propane (C3) slightly increase, then decrease and finally increase with increasing maturities. This reverse phenomenon indicates the heterogeneous and complex compositions of the kerogen. The isotope compositions of gases exhibit three distinct clusters in natural gas plot of δ13C values versus 1/n (where n is carbon number of the gaseous molecule), corresponding to three different groups of maturity stages. By linking the same maturity stage of δ13C values, all lines show nearly parallel in each group with consistently reverse trend of δ13C3 < δ13C2 > δ13C1. These three distinct clusters were also observed in the cross plotting of iC4/nC4 versus iC5/nC5 isomer ratios. This may imply that the kerogen is composed of three discrete structural domains which were progressively cracked at three major groups of maturity stages. The reverse trend was inconsistent with data for gas collected cumulatively in most prior pyrolysis experiments and the linear relationship predicted from kinetic isotope effect (KIE) model. Although the non-linear relationship or reverse trend, δ13C3 < δ13C2, was also reported for some natural gases, it was interpreted as a result of mixing from different source rocks or other

Formation and processing of organics in the early solar system.

PubMed

Kerridge, J F

1999-01-01

Until pristine samples can be returned from cometary nuclei, primitive meteorites represent our best source of information about organic chemistry in the early solar system. However, this material has been affected by secondary processing on asteroidal parent bodies which probably did not affect the material now present in cometary nuclei. Production of meteoritic organic matter apparently involved the following sequence of events: Molecule formation by a variety of reaction pathways in dense interstellar clouds; Condensation of those molecules onto refractory interstellar grains; Irradiation of organic-rich interstellar-grain mantles producing a range of molecular fragments and free radicals; Inclusion of those interstellar grains into the protosolar nebula with probable heating of at least some grain mantles during passage through the shock wave bounding the solar accretion disc; Agglomeration of residual interstellar grains and locally produced nebular condensates into asteroid-sized planetesimals; Heating of planetesimals by decay of extinct radionuclides; Melting of ice to produce liquid water within asteroidal bodies; Reaction of interstellar molecules, fragments and radicals with each other and with the aqueous environment, possibly catalysed by mineral grains; Loss of water and other volatiles to space yielding a partially hydrated lithology containing a complex suite of organic molecules; Heating of some of this organic matter to generate a kerogen-like complex; Mixing of heated and unheated material to yield the meteoritic material now observed. Properties of meteoritic organic matter believed to be consistent with this scenario include: Systematic decrease of abundance with increasing C number in homologous series of characterisable molecules; Complete structural diversity within homologous series; Predominance of branched-chain isomers; Considerable isotopic variability among characterisable molecules and within kerogen-like material; Substantial

Unconventional Liquids, Peak Oil and Climate Change

NASA Astrophysics Data System (ADS)

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

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

USGS Publications Warehouse

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.

Increased likelihood of induced seismicity in highly overpressured shale formations

NASA Astrophysics Data System (ADS)

Eaton, David W.; Schultz, Ryan

2018-05-01

Fluid-injection processes such as disposal of saltwater or hydraulic fracturing can induce earthquakes by increasing pore pressure and/or shear stress on faults. Natural processes, including transformation of organic material (kerogen) into hydrocarbon and cracking to produce gas, can similarly cause fluid overpressure. Here we document two examples from the Western Canada Sedimentary Basin where earthquakes induced by hydraulic fracturing are strongly clustered within areas characterized by pore-pressure gradient in excess of 15 kPa/m. Despite extensive hydraulic-fracturing activity associated with resource development, induced earthquakes are virtually absent in the Montney and Duvernay Formations elsewhere. Statistical analysis suggests a negligible probability that this spatial correlation developed by chance. This implies that, in addition to known factors such as anthropogenic pore-pressure increase and proximity to critically stressed faults, high in-situ overpressure of shale formations may also represent a controlling factor for inducing earthquakes by hydraulic fracturing. On a geological timescale, natural pore-pressure generation may lead to fault-slip episodes that regulate magnitude of formation-overpressure.

Effects of rock mineralogy and pore structure on stress-dependent permeability of shale samples

PubMed Central

Al Ismail, Maytham I.; Zoback, Mark D.

2016-01-01

We conducted pulse-decay permeability experiments on Utica and Permian shale samples to investigate the effect of rock mineralogy and pore structure on the transport mechanisms using a non-adsorbing gas (argon). The mineralogy of the shale samples varied from clay rich to calcite rich (i.e. clay poor). Our permeability measurements and scanning electron microscopy images revealed that the permeability of the shale samples whose pores resided in the kerogen positively correlated with organic content. Our results showed that the absolute value of permeability was not affected by the mineral composition of the shale samples. Additionally, our results indicated that clay content played a significant role in the stress-dependent permeability. For clay-rich samples, we observed higher pore throat compressibility, which led to higher permeability reduction at increasing effective stress than with calcite-rich samples. Our findings highlight the importance of considering permeability to be stress dependent to achieve more accurate reservoir simulations especially for clay-rich shale reservoirs. This article is part of the themed issue ‘Energy and the subsurface’. PMID:27597792

Structure and Bonding of Carbon in Clays from CI Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Garview, Laurence a. J.; Buseck, Peter R.

2005-01-01

Carbonaceous chondrites (CC) contain a diverse suite of C-rich materials. Acid dissolution of these meteorites leaves a C-rich residue with chemical and structural affinities to kerogen. This material has primarily been analyzed in bulk, and much information has been provided regarding functional groups and elemental and isotopic compositions. However, comparatively little work has been done on C in unprocessed meteorites. Studies of CCs suggest a spatial relationship of some C-rich materials with products of aqueous alteration. Recent studies revealed discrete submicronsized, C-rich particles in Tagish Lake and a range of CM2 meteorites. A challenge is to correlate the findings from the bulk acid-residue studies with those of high-spatial resolution-mineralogical and spectroscopic observations of unprocessed meteorites. Hence, the relationship between the C-rich materials in the acid residues and its form and locations in the unprocessed meteorite remains unclear. Here we provide information on the structure and bonding of C associated with clays in CI carbonaceous chondrites. Additional information is included in the original extended abstract.

Fires at the K/T boundary - Carbon at the Sumbar, Turkmenia, site

NASA Technical Reports Server (NTRS)

Wolbach, Wendy S.; Anders, Edward; Nazarov, Michael A.

1990-01-01

Results are reported on carbon analysis and on C and Ir correlations in samples from the marine K-T boundary site SM-4 at the Sumbar River in Turkmenia (USSR), which has the largest known Ir anomaly (580 ng/cq cm). In addition, the boundary clay is thick, and is undisturbed by bioturbation. Kerogen and delta-C-13 elemental carbon in the boundary clay were resolved using a Cr2O7(2-) oxidation method of Wolbach and Anders (1989). It was found that Ir and shocked quartz, both representing impact ejecta, rise sharply at the boundary, peak in the basal layer, and then decline. On the other hand, soot and total elemental C show a similar spike in the basal layer but then rise rather than fall, peking at 7 cm. Results indicate that fires at the SM-4 K-T boundary site started before the basal layer had settled, implying that ignition and spreading of major fires became possible at the time of or very soon after the meteorite impact.

Sembar Goru/Ghazij Composite Total Petroleum System, Indus and Sulaiman-Kirthar Geologic Provinces, Pakistan and India

USGS Publications Warehouse

Wandrey, C.J.; Law, B.E.; Shah, Haider Ali

2004-01-01

Geochemical analyses of rock samples and produced oil and gas in the Indus Basin have shown that the bulk of the hydrocarbons produced in the Indus Basin are derived from the Lower Cretaceous Sembar Formation and equivalent rocks. The source rocks of the Sembar are composed of shales that were deposited in shallow marine environments, are of mixed type-II and type-III kerogen, with total organic carbon (TOC) content ranging from less than 0.5 percent to more than 3.5 percent; the average TOC of the Sembar is about 1.4 percent. Vitrinite reflectance (Ro) values range from immature (1.35 percent Ro). Thermal generation of hydrocarbons in the Sembar Formation began 65 to 40 million years ago, (Mya) during Paleocene to Oligocene time. Hydrocarbon expulsion, migration, and entrapment are interpreted to have occurred mainly 50 to 15 Mya, during Eocene to Miocene time, prior to and contemporaneously with the development of structural traps in Upper Cretaceous and Tertiary reservoirs. The principal reservoirs in the Sembar-Goru/Ghazij Composite Total Petroleum System are Upper Cretaceous through Eocene sandstones and limestones.

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

USGS Publications Warehouse

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.

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

USGS Publications Warehouse

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).

The role of minerals in the thermal alteration of organic matter. III - Generation of bitumen in laboratory experiments

NASA Technical Reports Server (NTRS)

Huizinga, Bradley J.; Tannenbaum, Eli; Kaplan, I. R.

1987-01-01

A series of pyrolysis experiments, utilizing two different immature kerogens (from the Monterey and Green River Formations) mixed with common sedimentary minerals (calcite, illite, or Na-montmorillonite), was conducted to study the impact of the mineral matrix on the bitumen that was generated. Calcite has no significant influence on the thermal evolution of bitumen and also shows virtually no adsorption capacity for any of the pyrolysate. In contrast, montmorillonite (M) and illite, to a lesser extent, alter bitumen during dry pyrolysis. M and illite also display strong adsorption capacities for the polar constituents of bitumen. By this process, hydrocarbons are substantially concentrated within the pyrolysate that is not strongly adsorbed on the clay matrices. The effects of the clay minerals are significantly reduced during hydrous pyrolysis. The strong adsorption capacities of M and illite, as well as their thermocatalytic properties, may in part explain why light oils and gases are generated from certain argillaceous source-rock assemblages, whereas heavy immature oils are often derived from carbonate source rocks.

Depletion of 13C in Cretaceous marine organic matter: Source, diagenetic, or environmental sigal?

USGS Publications Warehouse

Dean, W.E.; Arthur, M.A.; Claypool, G.E.

1986-01-01

Geochemical studies of Cretaceous strata rich in organic carbon (OC) from Deep Sea Drilling Project (DSDP) sites and several land sections reveal several consistent relationships among amount of OC, hydrocarbon generating potential of kerogen (measured by pyrolysis as the hydrogen index, HI), and the isotopic composition of the OC. First, there is a positive correlation between HI and OC in strata that contain more than about 1% OC. Second, percent OC and HI often are negatively correlated with carbon isotopic composition (?? 13C) of kerogen. The relationship between HI and OC indicates that as the amount of organic matter increases, this organic matter tends to be more lipid rich reflecting the marine source of the organic matter. Cretaceous samples that contain predominantly marine organic matter tend to be isotopically lighter than those that contain predominantly terrestrial organic matter. Average ?? 13C values for organic matter from most Cretaceous sites are between -26 and -28???, and values heavier than about -25??? occur at very few sites. Most of the ?? 13C values of Miocene to Holocene OC-rich strata and modern marine plankton are between -16 to -23???. Values of ??13C of modern terrestrial organic matter are mostly between -23 and -33???. The depletion of terrestial OC in 13C relative to marine planktonic OC is the basis for numerous statements in the literature that isotopically light Cretaceous organic matter is of terrestrial origin, even though other organic geochemical and(or) optical indicators show that the organic matter is mainly of marine origin. A difference of about 5??? in ?? 13C between modern and Cretaceous OC-rich marine strata suggests either that Cretaceous marine planktonic organic matter had the same isotopic signature as modern marine plankton and that signature has been changed by diagenesis, or that OC derived from Cretaceous marine plankton was isotopically lighter by about 5??? relative to modern plankton OC. Diagenesis does

Stabilization of kerogen thermal maturation: Evidence from geothermometry and burial history reconstruction, Niobrara Limestone, Berthoud oil field, western Denver Basin, Colorado

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

Barker, C.E.; Crysdale, B.L.

1990-05-01

The burial history of this fractured Niobrara Limestone reservoir and source rock offers a setting for studying the stabilization of thermal maturity because soon after peak temperature of approximately 100{degree}C was reached, exhumation lowered temperature to about 60-70{degree}C. Vitrinite reflectance (Rm = 0.6-0.7%) and published clay mineralogy data from the Niobrara Limestone indicate that peak paleotemperature was approximately 100{degree}C. Fluid inclusion data also indicate oil migration occurred at 100{degree}C. Burial history reconstruction indicates 100{degree}C was reached in the Niobrara Limestone only during minimum burial, which occurred at 70 Ma and 8000 ft depth. However, erosion beginning at 70 Ma andmore » continuing until 50 Ma removed over 3,000 ft of rock. This depth of erosion agrees with an Rm of 0.4% measured in surface samples of the Pierre Shale. The exhumation of the reservoir decreased temperature by about 30{degree}C to near the corrected bottom-hole temperature of 50-70{degree}C. Lopatin time-temperature index (TTI) analysis suggests the Niobrara Limestone as a source rock matured to the oil generation stage (TTI = 10) about 25 Ma, significantly later than maximum burial, and after exhumation caused cooling. The Lopatin TTI method in this case seems to overestimate the influence of heating time. If time is an important factor, thermal maturity should continue to increase after peak burial and temperature so that vitrinite reflectance will not be comparable to peak paleotemperatures estimated from geothermometers set at near-peak temperature and those estimated from burial history reconstruction. The agreement between geothermometry and the burial history reconstruction in Berthoud State 4 suggests that the influence of heating time must be small. The elapsed time available at near peak temperatures was sufficient to allow stabilization of thermal maturation in this case.« less

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

Low temperature hydrothermal maturation of organic matter in sediments from the Atlantis II Deep, Red Sea.

PubMed

Simoneit, B R; Grimalt, J O; Hayes, J M; Hartman, H

1987-01-01

Hydrocarbons and bulk organic matter of two sediment cores (No. 84 and 126, CHAIN 61 cruise) located within the Atlantis II Deep have been analyzed. Although the brines overlying the coring areas were reported to be sterile, microbial inputs and minor terrestrial sources the major sedimentary organic material. This input is derived from the upper water column above the brines. Both steroid and triterpenoid hydrocarbons show that extensive acid-catalyzed reactions are occurring in the sediments. In comparison with other hydrothermal (Guaymas Basin) or intrusive systems (Cape Verde Rise), the Atlantis II Deep exhibits a lower degree of thermal maturation. This is easily deduced from the elemental composition of the kerogens and the absence of polynuclear aromatic hydrocarbons of a pyrolytic origin in the bitumen. The lack of carbon number preference among the n-alkanes suggests, especially in the case of the long chain homologs, that the organic matter of Atlantis II Deep sediments has undergone some degree of catagenesis. However, the yields of hydrocarbons are much lower than those observed in other hydrothermal areas. The effect of lower temperature and poor source-rock characteristics appear to be responsible for the differences.

Modelling of the petroleum formation in the Mahakam sediments (Indonesia): Organic geochemical controls of the results

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

Brosse, E.; Burris, J.; Ouidin, J.L.

1990-06-01

Since the Miocene, the delta of the Mahakam River has accumulated thousands of meters of sediments in the eastern part of the Kutei Basin (Kalimantan, Indonesia). Source-rock candidates are the coals of the deltaic plain and several types of shales, mainly the delta front/prodelta area. Organic matter basically derives from higher plants, but each source facies presents important intrinsic variations of petroleum potential. These variations are overprinted by subsequent maturation trends. Geochemical and petrographical data are integrated on the general framework provided by a new synthetic interpretation of the sedimentary sequences, relying upon the concepts of seismic stratigraphy. From coremore » samples at a given level of maturation, the variations of several organic parameters are discussed in relation to the depositional paleoenvironment and to the possible precursors. 1D and 2D numerical routines are used to reconstruct the maturation history of source rocks. These tools are based upon a kinetic modeling of kerogen cracking. Model outputs are compared with observed maturation trends. The understanding of the initial organic facies distribution provides precise constraints in the selection of a homogenous samples set for this comparison purpose.« less

The origin of organic matter in the Martian meteorite ALH84001.

PubMed

Becker, L; Popp, B; Rust, T; Bada, J L

1999-01-01

Stable carbon isotope measurements of the organic matter associated with the carbonate globules and the bulk matrix material in the ALH84001 Martian meteorite indicate that two distinct sources are present in the sample. The delta 13C values for the organic matter associated with the carbonate globules averaged -26% and is attributed to terrestrial contamination. In contrast, the delta 13C values for the organic matter associated with the bulk matrix material yielded a value of -15%. The only common carbon sources on the Earth that yield similar delta 13C values, other then some diagenetically altered marine carbonates, are C4 plants. A delta 13C value of -15%, on the other hand, is consistent with a kerogen-like component, the most ubiquitous form of organic matter found in carbonaceous chondrites such as the Murchison meteorite. Examination of the carbonate globules and bulk matrix material using laser desorption mass spectrometry (LDMS) indicates the presence of a high molecular weight organic component which appears to be extraterrestrial in origin, possibly derived from the exogenous delivery of meteoritic or cometary debris to the surface of Mars.

The origin of organic matter in the Martian meteorite ALH84001.

PubMed

Becker, L; Popp, B; Rust, T; Bada, J L

1999-03-30

Stable carbon isotope measurements of the organic matter associated with the carbonate globules and the bulk matrix material in the ALH84001 Martian meteorite indicate that two distinct sources are present in the sample. The delta 13C values for the organic matter associated with the carbonate globules averaged -26% and is attributed to terrestrial contamination. In contrast, the delta 13C values for the organic matter associated with the bulk matrix material yielded a value of -15%. The only common sources of carbon on the Earth that yield similar delta 13C values, other then some diagenetically altered marine carbonates, are C4 plants. A delta 13C value of -15%, on the other hand, is consistent with a kerogen-like component, the most ubiquitous form of organic matter found in carbonaceous chondrites such as the Murchison meteorite. Examination of the carbonate globules and bulk matrix material using laser desorption mass spectrometry (LDMS) indicates the presence of a high molecular weight organic component which appears to be extraterrestrial in origin, possibly derived from the exogenous delivery, of meteoritic or cometary debris to the surface of Mars.

NanoSIMS analysis of organic carbon from the Tissint Martian meteorite: Evidence for the past existence of subsurface organic-bearing fluids on Mars

NASA Astrophysics Data System (ADS)

Lin, Yangting; El Goresy, Ahmed; Hu, Sen; Zhang, Jianchao; Gillet, Philippe; Xu, Yuchen; Hao, Jialong; Miyahara, Masaaki; Ouyang, Ziyuan; Ohtani, Eiji; Xu, Lin; Yang, Wei; Feng, Lu; Zhao, Xuchao; Yang, Jing; Ozawa, Shin

2014-12-01

Two petrographic settings of carbonaceous components, mainly filling open fractures and occasionally enclosed in shock-melt veins, were found in the recently fallen Tissint Martian meteorite. The presence in shock-melt veins and the deuterium enrichments (δD up to +1183‰) of these components clearly indicate a pristine Martian origin. The carbonaceous components are kerogen-like, based on micro-Raman spectra and multielemental ratios, and were probably deposited from fluids in shock-induced fractures in the parent rock of Tissint. After precipitation of the organic matter, the rock experienced another severe shock event, producing the melt veins that encapsulated a part of the organic matter. The C isotopic compositions of the organic matter (δ13C = -12.8 to -33.1‰) are significantly lighter than Martian atmospheric CO2 and carbonate, providing a tantalizing hint for a possible biotic process. Alternatively, the organic matter could be derived from carbonaceous chondrites, as insoluble organic matter from the latter has similar chemical and isotopic compositions. The presence of organic-rich fluids that infiltrated rocks near the surface of Mars has significant implications for the study of Martian paleoenvironment and perhaps to search for possible ancient biological activities on Mars.

Sulfur isotopes of organic matter preserved in 3.45-billion-year-old stromatolites reveal microbial metabolism

PubMed Central

Bontognali, Tomaso R. R.; Sessions, Alex L.; Allwood, Abigail C.; Fischer, Woodward W.; Grotzinger, John P.; Summons, Roger E.; Eiler, John M.

2012-01-01

The 3.45-billion-year-old Strelley Pool Formation of Western Australia preserves stromatolites that are considered among the oldest evidence for life on Earth. In places of exceptional preservation, these stromatolites contain laminae rich in organic carbon, interpreted as the fossil remains of ancient microbial mats. To better understand the biogeochemistry of these rocks, we performed microscale in situ sulfur isotope measurements of the preserved organic sulfur, including both Δ33S and . This approach allows us to tie physiological inference from isotope ratios directly to fossil biomass, providing a means to understand sulfur metabolism that is complimentary to, and independent from, inorganic proxies (e.g., pyrite). Δ33S values of the kerogen reveal mass-anomalous fractionations expected of the Archean sulfur cycle, whereas values show large fractionations at very small spatial scales, including values below -15‰. We interpret these isotopic patterns as recording the process of sulfurization of organic matter by H2S in heterogeneous mat pore-waters influenced by respiratory S metabolism. Positive Δ33S anomalies suggest that disproportionation of elemental sulfur would have been a prominent microbial process in these communities. PMID:22949693

Geochemistry of Israeli oil shales - A review

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

Shirav, M.; Ginzbury, D.

1983-02-01

The oil shales in Israel are widely distributed throughout the country. Outcrops are rare and the information is based on boreholes data. The oil shale sequence is of UpperCampanian - Maastrichtian age and belongs to the Chareb Formation. In places, part of the phosphorite layer below the oil shales is also rich in kerogen. The host rocks are biomicritic limestones and marls, in which the organic matter is generally homogeneously and finely dispersed. The occurrence of authigenic feldspar and the preservation of the organic matter (up to 26% of the total rock) indicate euxinic hypersaline conditions which prevailed in themore » relative closed basins of deposition during the Maastrichtian. Current reserves of oil shales in Israel are about 3,500 million tons, located in the following deposits: Zin, Oron, Ef'e, Hartuv and Nabi-Musa. The 'En Bokek deposit, although thoroughly investigated, is of limited reserves and is not considered for future exploitation. Other potential areas, in the Northern Negev and along the Coastal Plain are under investigation. Future successful utilization of the Israeli oil shales, either by fluidizid-bed combustion or by retorting will contribute to the state's energy balance.« less

Mineralogical, chemical and K-Ar isotopic changes in Kreyenhagen Shale whole rocks and <2 µm clay fractions during natural burial and hydrous-pyrolysis experimental maturation

USGS Publications Warehouse

Clauer, Norbert; Lewan, Michael D.; Dolan, Michael P.; Chaudhuri, Sambhudas; Curtis, John B.

2014-01-01

Large amounts of smectite layers in the illite–smectite mixed layers of the pyrolyzed outcrop <2 μm fraction remain during thermal experiments, especially above 310 °C. With no illitization detected above 310 °C, smectite appears to have inhibited rather than promoted generation of expelled oil from decomposition of bitumen. This hindrance is interpreted to result from bitumen impregnating the smectite interlayer sites and rock matrix. Bitumen remains in the <2 μm fraction despite leaching with H2O2. Its presence in the smectite interlayers is apparent by the inability of the clay fraction to fully expand or collapse once bitumen generation from the thermal decomposition of the kerogen is completed, and by almost invariable K–Ar ages confirming for the lack of any K supply and/or radiogenic 40Ar removal. This suggests that once bitumen impregnates the porosity of a progressively maturing source rock, the pore system is no longer wetted by water and smectite to illite conversion ceases. Experimental attempts to evaluate the smectite conversion to illite should preferentially use low-TOC rocks to avoid inhibition of the reaction by bitumen impregnation.

The Athena Raman Spectrometer

NASA Technical Reports Server (NTRS)

Wang, Alian; Haskin, Larry A.; Jolliff, Bradley; Wdowiak, Tom; Agresti, David; Lane, Arthur L.

2000-01-01

Raman spectroscopy provides a powerful tool for in situ mineralogy, petrology, and detection of water and carbon. The Athena Raman spectrometer is a microbeam instrument intended for close-up analyses of targets (rock or soils) selected by the Athena Pancam and Mini-TES. It will take 100 Raman spectra along a linear traverse of approximately one centimeter (point-counting procedure) in one to four hours during the Mars' night. From these spectra, the following information about the target will extracted: (1) the identities of major, minor, and trace mineral phases, organic species (e.g., PAH or kerogen-like polymers), reduced inorganic carbon, and water-bearing phases; (2) chemical features (e.g. Mg/Fe ratio) of major minerals; and (3) rock textural features (e.g., mineral clusters, amygdular filling and veins). Part of the Athena payload, the miniaturized Raman spectrometer has been under development in a highly interactive collaboration of a science team at Washington University and the University of Alabama at Birmingham, and an engineering team at the Jet Propulsion Laboratory. The development has completed the brassboard stage and has produced the design for the engineering model.

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

USGS Publications Warehouse

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

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

NASA Astrophysics Data System (ADS)

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

Isotopic fractionation of nitrogen and carbon in Paleoarchean cherts from Pilbara craton, Western Australia: Origin of 15N-depleted nitrogen

NASA Astrophysics Data System (ADS)

Pinti, Daniele L.; Hashizume, Ko; Sugihara, Akiyo; Massault, Marc; Philippot, Pascal

2009-07-01

Nitrogen and carbon isotopic compositions, together with mineralogy and trace element geochemistry, were studied in a few kerogen-rich Paleoarchean cherts, a barite and a dolomitic stromatolite belonging to the eastern (Dixon Island Formation) and western (Dresser and Strelley Pool Chert Formations; North Pole Dome and Marble Bar) terranes of Pilbara Craton, Western Australia. The aim of the study was to search for 15N-depleted isotopic signatures, often found in kerogens of this period, and explain the origin of these anomalies. Trace elements suggest silica precipitation by hydrothermal fluids as the main process of chert formation with a contamination from volcanoclastic detritus. This is supported by the occurrence of hydrothermal-derived minerals in the studied samples indicating precipitation temperatures up to 350 °C. Only a dolomitic stromatolite from Strelley Pool shows a superchondritic Y/Ho ratio of 72 and a positive Eu/Eu * anomaly of 1.8, characteristic of chemical precipitates from the Archean seawater. The bulk δ 13C vs. δ 15N values measured in the cherts show a roughly positive co-variation, except for one sample from the North Pole (PI-85-00). The progressive enrichment in 15N and 13C from a pristine source having δ 13C ⩽ -36‰ and δ 15N ⩽ -4‰ is correlated with a progressive depletion in N content and to variations in Ba/La and Co/As ratios. These trends have been interpreted as a progressive hydrothermal alteration of the cherts by metamorphic fluids. Isotopic exchange at 350 °C between NH 4+(rock) and N 2(fluid) may explain the isotopic and elemental composition of N in the studied cherts. However, we need to assume isotopic exchange at 350 °C between carbonate C and graphite to explain the large 13C enrichment recorded. Only sample PI-85-00 shows a large N loss (90%) with a positive δ 15N value (+11‰), while C (up to 120 ppm and δ 13C -38‰) seems to be unaffected. This pattern has been interpreted as the result of

Rhenium uptake and distribution in phaeophyceae macroalgae, Fucus vesiculosus

PubMed Central

Racionero-Gómez, B.; Sproson, A. D.; Selby, D.; Gröcke, D. R.; Redden, H.; Greenwell, H. C.

2016-01-01

Owing to Rhenium (Re) having no known biological role, it is not fully understood how Re is concentrated in oil kerogens. A commonly held assumption is that Re is incorporated into decomposing biomass under reducing conditions. However, living macroalgae also concentrate Re to several orders of magnitude greater than that of seawater. This study uses Fucus vesiculosus to assess Re uptake and its subsequent localization in the biomass. It is demonstrated that the Re abundance varies within the macroalgae and that Re is not located in one specific structure. In F. vesiculosus, the uptake and tolerance of Re was evaluated via tip cultures grown in seawater of different Re(VII) compound concentrations (0–7450 ng g−1). A positive correlation is shown between the concentration of Re-doped seawater and the abundance of Re accumulated in the tips. However, significant differences between Re(VII) compounds are observed. Although the specific cell structures where the Re is localized is not known, our findings suggest that Re is not held within chloroplasts or cytoplasmic proteins. In addition, metabolically inactivated F. vesiculosus does not accumulate Re, which indicates that Re uptake is via syn-life bioadsorption/bioaccumulation and that macroalgae may provide a source for Re phytomining and/or bioremediation. PMID:27293798

A molecular and isotopic study of the organic matter from the Paris Basin, France

NASA Technical Reports Server (NTRS)

Lichtfouse, E.; Albrecht, P.; Behar, F.; Hayes, J. M.

1994-01-01

Thirteen Liassic sedimentary rocks of increasing depth and three petroleums from the Paris Basin were studied for 13C/12C isotopic compositions and biological markers, including steranes, sterenes, methylphenanthrenes, methylanthracenes, and triaromatic steroids. The isotopic compositions of n-alkanes from mature sedimentary rocks and petroleums fall in a narrow range (2%), except for the deepest Hettangian rock and the Trias petroleum, for which the short-chain n-alkanes are enriched and depleted in 13C, respectively. Most of the molecular parameters increase over the 2000-2500 m depth range, reflecting the transformation of the organic matter at the onset of petroleum generation. In this zone, carbonate content and carbon isotopic composition of carbonates, as well as molecular parameters, are distinct for the Toarcian and Hettangian source rocks and suggest a migration of organic matter from these two formations. Two novel molecular parameters were defined for this task: one using methyltriaromatic steroids from organic extracts; the other using 1-methylphenanthrene and 2-methylanthracene from kerogen pyrolysates. The anomalous high maturity of the Dogger petroleum relative to the maturity-depth trend of the source rocks is used to estimate the minimal vertical distance of migration of the organic matter from the source rock to the reservoir.

Cross-Scale Molecular Analysis of Chemical Heterogeneity in Shale Rocks

DOE PAGES

Hao, Zhao; Bechtel, Hans A.; Kneafsey, Timothy; ...

2018-02-07

The organic and mineralogical heterogeneity in shale at micrometer and nanometer spatial scales contributes to the quality of gas reserves, gas flow mechanisms and gas production. Here, we demonstrate two molecular imaging approaches based on infrared spectroscopy to obtain mineral and kerogen information at these mesoscale spatial resolutions in large-sized shale rock samples. The first method is a modified microscopic attenuated total reflectance measurement that utilizes a large germanium hemisphere combined with a focal plane array detector to rapidly capture chemical images of shale rock surfaces spanning hundreds of micrometers with micrometer spatial resolution. The second method, synchrotron infrared nano-spectroscopy,more » utilizes a metallic atomic force microscope tip to obtain chemical images of micrometer dimensions but with nanometer spatial resolution. This chemically "deconvoluted" imaging at the nano-pore scale is then used to build a machine learning model to generate a molecular distribution map across scales with a spatial span of 1000 times, which enables high-throughput geochemical characterization in greater details across the nano-pore and micro-grain scales and allows us to identify co-localization of mineral phases with chemically distinct organics and even with gas phase sorbents. Finally, this characterization is fundamental to understand mineral and organic compositions affecting the behavior of shales.« less

Chemical Mapping of Proterozoic Organic Matter at Sub-Micron Spatial Resolution

NASA Technical Reports Server (NTRS)

Oehler, Dorothy Z.; Robert, Francois; Mostefaoui, Smail; Meibom, Anders; Selo, Madeleine; McKay, David S.

2006-01-01

We have used a NanoSIMS ion microprobe to map sub-micron-scale distributions of carbon, nitrogen, sulfur, silicon, and oxygen in organic microfossils and laminae from the approximately 0.85 Ga Bitter Springs Formation of Australia. The data provide clues about the original chemistry of the microfossils, the silicification process, and biosignatures of specific microorganisms and microbial communities. Chemical maps of fossil unicells and filaments reveal distinct wall-and sheath-like structures enriched in C, N and S, consistent with their accepted biological origin. Surprisingly, organic laminae, previously considered to be amorphous, also exhibit filamentous and apparently compressed spheroidal structures defined by strong enrichments in C, N and S. By analogy to data from the well-preserved microfossils, these structures are interpreted as being of biological origin, most likely representing densely packed remnants of microbial mats. Because the preponderance of organic matter in Precambrian sediments is similarly "amorphous," our findings open a large body of generally neglected material to in situ structural, chemical, and isotopic study. Our results also offer new criteria for assessing biogenicity of problematic kerogenous materials and thus can be applied to assessments of poorly preserved or fragmentary organic residues in early Archean sediments and any that might occur in meteorites or other extraterrestrial samples.

Possible Microfossils (Warrawoona Group, Towers Formation, Australia, approximately 3.3 - 3.5 Ga)

NASA Technical Reports Server (NTRS)

Morris, P. A.; Wentworth, S. J.; Allen, C. C.; McKay, D. S.

1998-01-01

Early in the twentieth century there were reports of Archean stromatolite-like structures that were similar to organic rich stromatolites from the base of the Cambrian (600 m.y.). It was not until the latter half of this century that fossilized Archean-age (3.9-2.5 Ga) life forms were found in the Fig Tree Formation of South Africa and the Towers Formation of Australia. Some of the ancient stromatolites contained streaks and clots of kerogen, pyrite grains, remnants of microbial cells, and filaments that represented various stages of preservation, while others appeared to lack fossils. A set of physical criteria was established for evaluating the biogenicity of these Archean discoveries: (1) rocks of unquestionable Archean age; (2) microfossils indigenous to Archean sediments; and (3) microfossils occurring in clasts that are syngenetic with deposition of the sedimentary unit. In the case of bedded cherts, the fossils should predate the cherts; (4) the microfossils are biogenic; and (5) replicate sampling of the fossil-iferous outcrop firmly demonstrates the provenance of these microfossils. Sample 002 from the Precambrian Paleobiology Research Group (PPRG) was examined. This stromatolitic carbonaceous chert contains microbial remains that meet the established criteria [10]. Using a scanning electron microscope (SEM), we have analyzed the morphologies and chemistry of these possible microbial remains.

Sulfur species in source rock bitumen before and after hydrous pyrolysis determined by X-ray absorption near-edge structure

USGS Publications Warehouse

Bolin, Trudy B.; Birdwell, Justin E.; Lewan, Michael; Hill, Ronald J.; Grayson, Michael B.; Mitra-Kirtley, Sudipa; Bake, Kyle D.; Craddock, Paul R.; Abdallah, Wael; Pomerantz, Andrew E.

2016-01-01

The sulfur speciation of source rock bitumen (chloroform-extractable organic matter in sedimentary rocks) was examined using sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy for a suite of 11 source rocks from around the world. Sulfur speciation was determined for both the native bitumen in thermally immature rocks and the bitumen produced by thermal maturation of kerogen via hydrous pyrolysis (360 °C for 72 h) and retained within the rock matrix. In this study, the immature bitumens had higher sulfur concentrations than those extracted from samples after hydrous pyrolysis. In addition, dramatic and systematic evolution of the bitumen sulfur moiety distributions following artificial thermal maturation was observed consistently for all samples. Specifically, sulfoxide sulfur (sulfur double bonded to oxygen) is abundant in all immature bitumen samples but decreases substantially following hydrous pyrolysis. The loss in sulfoxide sulfur is associated with a relative increase in the fraction of thiophene sulfur (sulfur bonded to aromatic carbon) to the extent that thiophene is the dominant sulfur form in all post-pyrolysis bitumen samples. This suggests that sulfur moiety distributions might be used for estimating thermal maturity in source rocks based on the character of the extractable organic matter.

Molecular evidence of Late Archean archaea and the presence of a subsurface hydrothermal biosphere

PubMed Central

Ventura, Gregory T.; Kenig, Fabien; Reddy, Christopher M.; Schieber, Juergen; Frysinger, Glenn S.; Nelson, Robert K.; Dinel, Etienne; Gaines, Richard B.; Schaeffer, Philippe

2007-01-01

Highly cracked and isomerized archaeal lipids and bacterial lipids, structurally changed by thermal stress, are present in solvent extracts of 2,707- to 2,685-million-year-old (Ma) metasedimentary rocks from Timmins, ON, Canada. These lipids appear in conventional gas chromatograms as unresolved complex mixtures and include cyclic and acyclic biphytanes, C36–C39 derivatives of the biphytanes, and C31–C35 extended hopanes. Biphytane and extended hopanes are also found in high-pressure catalytic hydrogenation products released from solvent-extracted sediments, indicating that archaea and bacteria were present in Late Archean sedimentary environments. Postdepositional, hydrothermal gold mineralization and graphite precipitation occurred before metamorphism (≈2,665 Ma). Late Archean metamorphism significantly reduced the kerogen's adsorptive capacity and severely restricted sediment porosity, limiting the potential for post-Archean additions of organic matter to the samples. Argillites exposed to hydrothermal gold mineralization have disproportionately high concentrations of extractable archaeal and bacterial lipids relative to what is releasable from their respective high-pressure catalytic hydrogenation product and what is observed for argillites deposited away from these hydrothermal settings. The addition of these lipids to the sediments likely results from a Late Archean subsurface hydrothermal biosphere of archaea and bacteria. PMID:17726114

Shale characterization on Barito field, Southeast Kalimantan for shale hydrocarbon exploration

NASA Astrophysics Data System (ADS)

Sumotarto, T. A.; Haris, A.; Riyanto, A.; Usman, A.

2017-07-01

Exploration and exploitation in Indonesia now are still focused on conventional hydrocarbon energy than unconventional hydrocarbon energy such as shale gas. Tanjung Formation is a source rock of Barito Basin located in South Kalimantan that potentially as shale hydrocarbon. In this research, integrated methods using geochemical analysis, mineralogy, petrophysical analysis and seismic interpretation has been applied to explore the shale hydrocarbon potential in Barito Field for Tanjung formation. The first step is conducting geochemical and mineralogy analysis to the shale rock sample. Our analysis shows that the organic richness is ranging from 1.26-5.98 wt.% (good to excellent) with the depth of early mature window of 2170 m. The brittleness index is in an average of 0.44-0.56 (less Brittle) and Kerogen type is classified into II/III type that potentially produces oil and gas. The second step is continued by performing petrophysical analysis, which includes Total Organic Carbon (TOC) calculation and brittleness index continuously. The result has been validated with a laboratory measurement that obtained a good correlation. In addition, seismic interpretation based on inverted acoustic impedance is applied to map the distributions of shale hydrocarbon potential. Our interpretation shows that shale hydrocarbon potential is localized in the eastern and southeastern part of the study area.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

Marine petroleum source rocks and reservoir rocks of the Miocene Monterey Formation, California, U.S.A

USGS Publications Warehouse

Isaacs, C.M.

1988-01-01

The Miocene Monterey Formation of California, a biogenous deposit derived mainly from diatom debris, is important both as a petroleum source and petroleum reservoir. As a source, the formation is thought to have generated much of the petroleum in California coastal basins, which are among the most prolific oil provinces in the United States. Oil generated from the Monterey tends to be sulfur-rich and heavy (<20° API), and has chemical characteristics that more closely resemble immature source extracts than "normal" oil. Thermal-maturity indicators in Monterey kerogens appear to behave anomalously, and several lines of evidence indicate that the oil is generated at lower than expected levels of organic metamorphism. As a reservoir, the Monterey is important due both to conventional production from permeable sandstone beds and to fracture production from fine-grained rocks with low matrix permeability. Fractured reservoirs are difficult to identify, and conventional well-log analysis has not proven to be very useful in exploring for and evaluating these reservoirs. Lithologically similar rocks are broadly distributed throughout the Circum-Pacific region, but their petroleum potential is unlikely to be realized without recognition of the distinctive source and reservoir characteristics of diatomaceous strata and their diagenetic equivalents.

Cross-Scale Molecular Analysis of Chemical Heterogeneity in Shale Rocks

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

Hao, Zhao; Bechtel, Hans A.; Kneafsey, Timothy

The organic and mineralogical heterogeneity in shale at micrometer and nanometer spatial scales contributes to the quality of gas reserves, gas flow mechanisms and gas production. Here, we demonstrate two molecular imaging approaches based on infrared spectroscopy to obtain mineral and kerogen information at these mesoscale spatial resolutions in large-sized shale rock samples. The first method is a modified microscopic attenuated total reflectance measurement that utilizes a large germanium hemisphere combined with a focal plane array detector to rapidly capture chemical images of shale rock surfaces spanning hundreds of micrometers with micrometer spatial resolution. The second method, synchrotron infrared nano-spectroscopy,more » utilizes a metallic atomic force microscope tip to obtain chemical images of micrometer dimensions but with nanometer spatial resolution. This chemically "deconvoluted" imaging at the nano-pore scale is then used to build a machine learning model to generate a molecular distribution map across scales with a spatial span of 1000 times, which enables high-throughput geochemical characterization in greater details across the nano-pore and micro-grain scales and allows us to identify co-localization of mineral phases with chemically distinct organics and even with gas phase sorbents. Finally, this characterization is fundamental to understand mineral and organic compositions affecting the behavior of shales.« less

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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.

Carbonaceous Survivability on Impact

NASA Technical Reports Server (NTRS)

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.

Petroleum geology of the mid-Atlantic continental margin, offshore Virginia

USGS Publications Warehouse

Bayer, K.C.; Milici, R.C.

1989-01-01

The Baltimore Canyon Trough, a major sedimentary basin on the Atlantic continental shelf, contains up to 18 km of Mesozoic and Cenozoic strata. The basin has been studied extensively by multichannel common depth point (CDP) seismic reflection profiles and has been tested by drilling for hydrocarbon resources in several places. The Mesozoic and Cenozoic strata contained in the basin were deposited in littoral to bathyal depositional settings and contain immature to marginally mature oil-prone and gas-prone kerogen. The more deeply buried strata of Early Mesozoic age are more likely to be thermally mature than are the younger strata with respect to hydrocarbon generation, but contain terrestrially derived coaly organic matter that would be prone to yield gas, rather than oil. An analysis of available CDP seismic reflection data has indicated that there are several potential hydrocarbon plays in the area offshore of Virginia. These include: (1) Lower Mesozoic synrift basins that appear similar to those exposed in the Appalachian Piedmont, (2) a stratigraphic updip pinchout of strata of Early Mesozoic age in the offshore region near the coast, (3) a deeply buried paleoshelf edge, where seismic reflectors dip sharply seaward; and (4) a Cretaceous/Jurassic shelf edge beneath the present continental rise. Of these, the synrift basins and Cretaceous/Jurassic shelf edge are considered to be the best targets for exploration. ?? 1989.

Paralavas in the Cretaceous Paraná volcanic province, Brazil - A genetic interpretation of the volcanic rocks containing phenocrysts and glass.

PubMed

Baggio, Sérgio B; Hartmann, Léo A; Bello, Rosa M S

2016-01-01

The occurrences of glassy rocks containing long and curved phenocrysts in the Paraná volcanic province, South America, are here interpreted as paralavas. The large number of thin (0.1-0.5 m) dikes and sills of glassy volcanic rocks with hopper, hollow or curved, large crystals of clinopyroxene (up to 10 cm), plagioclase (up to 1 cm), magnetite and apatite are contained in the core of thick (>70 m) pahoehoe flows. They are strongly concentrated in the state of Paraná, coincident with the presence of the large number of dikes in the Ponta Grossa arch. These rocks were previously defined as pegmatites, although other names have also been used. A paralava is here interpreted as the product of melting of basaltic rocks following varied, successive processes of sill emplacement in high-kerogen bituminous shale and ascent of the resultant methane. As the gas reached the lower portion of the most recent lava flow of the volcanic pile, the methane reacted with the silicate and oxide minerals of the host volcanic rock (1,000 ºC) and thus elevated the local temperature to 1,600 ºC. The affected area of host rock remelted (possibly 75 wt.%) and injected buoyantly the central and upper portion of the core. This methane-related mechanism explains the evidence found in the paralavas from this volcanic province, one of the largest in the continents.

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

PubMed

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

2018-01-01

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

Organic geochemistry of sediments of deep Gulf of Mexico basin

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

Fang, J.; Sassen, R.; Nunn, J.

1989-09-01

An analysis of 716 core samples from DSDP (Deep Sea Drilling Project) Leg 96 in the Mississippi submarine fan and the Orca and Pigmy basins in the Louisiana continental slope was done using a Rock-Eval pyrolysis unit with TOC (total organic carbon) module. The analysis allows computation of the hydrogen index (HI), TOC, and kerogen type, and assessment of the oil-generative capacity of the sediments in the Louisiana continental slope. No samples are obviously oil prone. TOC content ranges from 0.12 to 2.29%, with an overall average of 0.82%. HI values are generally less than 150 mg HC/g TOC. T{submore » max} (temperature of the maximum of the S{sub 2} peak) values (425{degree}C average) show the sediments are immature throughout the study area. Hydrocarbon-generative potential of the sediments ranges from 492 to 1,107 ppm, with an average of 854 ppm. Because of organic lean, thermally immature, and gas-prone terrestrial organic matter, there is little reason to assume that the sediments from the Mississippi fan can provide oil source rock for the Gulf Coast basin, and that sediments of anoxic basins in the Louisiana continental slope are analogs to the past environments where source rocks for crude oil have been deposited.« less

Study on the Adsorption Phenomenon in Shale with the Combination of Molecular Dynamic Simulation and Fractal Analysis

NASA Astrophysics Data System (ADS)

Zhang, Liehui; Li, Jianchao; Jia, Du; Zhao, Yulong; Xie, Chunyu; Tao, Zhengwu

As one of the key status of gas in shale reservoir, adsorption gas accounts for considerable percentage of total gas amount. Due to the complexity and nanostructure of shale gas reservoir, it is very challenging to represent adsorption gas through traditional methods. However, the integration of the fractal theory and molecular dynamics (MD) simulation may provide a new perspective of understanding such nanostructure and the micro-phenomenon happening in it. The key purpose of this paper is to investigate the adsorption phenomenon in shale kerogen. By using MD simulation and grand canonical Monte Carlo (GCMC) algorithm, the adsorption of methane in 2, 5 and 10nm slit-like pores is simulated for different temperature and pressure status. According to the results, the average gas density in smaller pores is higher than that in bigger pores, and multilayer adsorption presents on some areas of pore surfaces. Then, the simulation results are analyzed using the multilayer fractal adsorption model. The analysis indicates that the number of adsorption layer increases with pressure increase: four-layer adsorption presents in 10nm pores while three-layer adsorption shows up in 2nm and 5nm pores due to pore volume limit. Fractal dimension of pore wall surface generated in this study is in the range of 2.31-2.63. Moreover, high temperature could decrease the adsorption behavior in reservoir condition.

Pore-Scale X-ray Micro-CT Imaging and Analysis of Oil Shales

NASA Astrophysics Data System (ADS)

Saif, T.

2015-12-01

The pore structure and the connectivity of the pore space during the pyrolysis of oil shales are important characteristics which determine hydrocarbon flow behaviour and ultimate recovery. We study the effect of temperature on the evolution of pore space and subsequent permeability on five oil shale samples: (1) Vernal Utah United States, (2) El Lajjun Al Karak Jordan, (3) Gladstone Queensland Australia (4) Fushun China and (5) Kimmerdige United Kingdom. Oil Shale cores of 5mm in diameter were pyrolized at 300, 400 and 500 °C. 3D imaging of 5mm diameter core samples was performed at 1μm voxel resolution using X-ray micro computed tomography (CT) and the evolution of the pore structures were characterized. The experimental results indicate that the thermal decomposition of kerogen at high temperatures is a major factor causing micro-scale changes in the internal structure of oil shales. At the early stage of pyrolysis, micron-scale heterogeneous pores were formed and with a further increase in temperature, the pores expanded and became interconnected by fractures. Permeability for each oil shale sample at each temperature was computed by simulation directly on the image voxels and by pore network extraction and simulation. Future work will investigate different samples and pursue insitu micro-CT imaging of oil shale pyrolysis to characterize the time evolution of the pore space.

Geology of the Devonian Marcellus Shale--Valley and Ridge province, Virginia and West Virginia--a field trip guidebook for the American Association of Petroleum Geologists Eastern Section Meeting, September 28-29, 2011

USGS Publications Warehouse

Enomoto, Catherine B.; Coleman, James L.; Haynes, John T.; Whitmeyer, Steven J.; McDowell, Ronald R.; Lewis, J. Eric; Spear, Tyler P.; Swezey, Christopher S.

2012-01-01

Detailed and reconnaissance field mapping and the results of geochemical and mineralogical analyses of outcrop samples indicate that the Devonian shales of the Broadtop Synclinorium from central Virginia to southern Pennsylvania have an organic content sufficiently high and a thermal maturity sufficiently moderate to be considered for a shale gas play. The organically rich Middle Devonian Marcellus Shale is present throughout most of the synclinorium, being absent only where it has been eroded from the crests of anticlines. Geochemical analyses of outcrop and well samples indicate that hydrocarbons have been generated and expelled from the kerogen originally in place in the shale. The mineralogical characteristics of the Marcellus Shale samples from the Broadtop Synclinorium are slightly different from the averages of samples from New York, Pennsylvania, northeast Ohio, and northern West Virginia. The Middle Devonian shale interval is moderately to heavily fractured in all areas, but in some areas substantial fault shearing has removed a regular "cleat" system of fractures. Conventional anticlinal gas fields in the study area that are productive from the Lower Devonian Oriskany Sandstone suggest that a continuous shale gas system may be in place within the Marcellus Shale interval at least in a portion of the synclinorium. Third-order intraformational deformation is evident within the Marcellus shale exposures. Correlations between outcrops and geophysical logs from exploration wells nearby will be examined by field trip attendees.

Paleoenvironmental reconstruction based on palynofacies analyses of the Cansona Formation (Late Cretaceous), Sinú-San Jacinto Basin, northwest Colombia

NASA Astrophysics Data System (ADS)

Juliao-Lemus, Tatiana; Carvalho, Marcelo de Araujo; Torres, Diego; Plata, Angelo; Parra, Carlos

2016-08-01

To reconstruct the paleoenvironments of the Cansona Formation, a Cretaceous succession in Colombia that has controversial paleoenvironmental interpretation, occasionally deep marine and occasionally shallow marine, palynofacies analyses were conducted on 93 samples from four sections of the Sinú San Jacinto Basin in the north, midwest, and southwest sectors. For the palynofacies analyses, the kerogen categories were counted and subjected to cluster analyses. Four palynofacies associations were revealed for the four sections: Palynofacies Association I (PA I), which consisted of microforaminiferal linings, scolecodonts, dinoflagellate cysts, pollen grains, and fungi hyphae; PA II, which consisted of phytoclast translucent non-biostructured and biostructured, opaque phytoclasts (equidimensional and lath shaped); PA III, which consisted of pseudoamorphous particles, cuticles, resin, and fungal spores; and PA IV, which consisted of fluorescent and non-fluorescent amorphous organic matter and the fresh-water algae Botryococcus. In contrast to early studies that suggested a generalization of the depositional environment for the Cansona Formation (deep or shallow conditions), this study suggests that the formation reflects conspicuous stratigraphic and lateral changes and hence different depositional environments. The Cerro Cansona (CC4 section) and Chalán (AP section) areas are a more marine proximal settings (Early Campanian-Maastrichtian), and there is an intermediate setting for the Lorica area (SC section) and deeper conditions for the Montería area (CP2 section).

Pressurized fluidized-bed hydroretorting of Eastern oil shales -- Sulfur control

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

Roberts, M.J.; Abbasian, J.; Akin, C.

1992-05-01

This topical report on Sulfur Control'' presents the results of work conducted by the Institute of Gas Technology (IGT), the Illinois Institute of Technology (IIT), and the Ohio State University (OSU) to develop three novel approaches for desulfurization that have shown good potential with coal and could be cost-effective for oil shales. These are (1) In-Bed Sulfur Capture using different sorbents (IGT), (2) Electrostatic Desulfurization (IIT), and (3) Microbial Desulfurization and Denitrification (OSU and IGT). The objective of the task on In-Bed Sulfur Capture was to determine the effectiveness of different sorbents (that is, limestone, calcined limestone, dolomite, and siderite)more » for capturing sulfur (as H{sub 2}S) in the reactor during hydroretorting. The objective of the task on Electrostatic Desulfurization was to determine the operating conditions necessary to achieve a high degree of sulfur removal and kerogen recovery in IIT's electrostatic separator. The objectives of the task on Microbial Desulfurization and Denitrification were to (1) isolate microbial cultures and evaluate their ability to desulfurize and denitrify shale, (2) conduct laboratory-scale batch and continuous tests to improve and enhance microbial removal of these components, and (3) determine the effects of processing parameters, such as shale slurry concentration, solids settling characteristics, agitation rate, and pH on the process.« less

Pressurized fluidized-bed hydroretorting of Eastern oil shales -- Sulfur control. Topical report for Subtask 3.1, In-bed sulfur capture tests; Subtask 3.2, Electrostatic desulfurization; Subtask 3.3, Microbial desulfurization and denitrification

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

Roberts, M.J.; Abbasian, J.; Akin, C.

1992-05-01

This topical report on ``Sulfur Control`` presents the results of work conducted by the Institute of Gas Technology (IGT), the Illinois Institute of Technology (IIT), and the Ohio State University (OSU) to develop three novel approaches for desulfurization that have shown good potential with coal and could be cost-effective for oil shales. These are (1) In-Bed Sulfur Capture using different sorbents (IGT), (2) Electrostatic Desulfurization (IIT), and (3) Microbial Desulfurization and Denitrification (OSU and IGT). The objective of the task on In-Bed Sulfur Capture was to determine the effectiveness of different sorbents (that is, limestone, calcined limestone, dolomite, and siderite)more » for capturing sulfur (as H{sub 2}S) in the reactor during hydroretorting. The objective of the task on Electrostatic Desulfurization was to determine the operating conditions necessary to achieve a high degree of sulfur removal and kerogen recovery in IIT`s electrostatic separator. The objectives of the task on Microbial Desulfurization and Denitrification were to (1) isolate microbial cultures and evaluate their ability to desulfurize and denitrify shale, (2) conduct laboratory-scale batch and continuous tests to improve and enhance microbial removal of these components, and (3) determine the effects of processing parameters, such as shale slurry concentration, solids settling characteristics, agitation rate, and pH on the process.« less

Interactions of soil-derived dissolved organic matter with phenol in peroxidase-catalyzed oxidative coupling reactions.

PubMed

Huang, Qingguo; Weber, Walter J

2004-01-01

The influence of dissolved soil organic matter (DSOM) derived from three geosorbents of different chemical composition and diagenetic history on the horseradish peroxidase (HRP) catalyzed oxidative coupling reactions of phenol was investigated. Phenol conversion and precipitate-product formation were measured, respectively, by HPLC and radiolabeled species analysis. Fourier transform infrared (FTIR) spectroscopy and capillary electrophoresis (CE) were used to characterize the products of enzymatic coupling, and the acute toxicities of the soluble products were determined by Microtox assay. Phenol conversion and precipitate formation were both significantly influenced by cross-coupling of phenol with dissolved organic matter, particularly in the cases of the more reactive and soluble DSOMs derived from two diagenetically "young" humic-type geosorbents. FTIR and CE characterizations indicate that enzymatic cross-coupling in these two cases leads to incorporation of phenol in DSOM macromolecules, yielding nontoxic soluble products. Conversely, cross-coupling appears to proceed in parallel with self-coupling in the presence of the relatively inert and more hydrophobic DSOM derived from a diagenetically "old" kerogen-type shale material. The products formed in this system have lower solubility and precipitate more readily, although their soluble forms tend to be more toxic than those formed by dominant cross-coupling reactions in the humic-type DSOM solutions. Several of the findings reported may be critically important with respect to feasibility evaluations and the engineering design of associated remediation schemes.

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

NASA Technical Reports Server (NTRS)

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.

Hydrocarbons related to early Cretaceous source rocks, reservoirs and seals, trapped in northeastern Neuqun basin, Argentina

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

Gulisano, C.; Minniti, S.; Rossi, G.

1996-08-01

The Jurassic-Cretaceous backarc Neuqun Basin, located in the west central part of Argentina, is currently the most prolific oil basin of the country. The primary objective of this study is to evaluate an Early Cretaceous to Tertiary petroleum system in the northeastern portion of the basin, where oil and gas occurrences (e.g., Puesto Hernandez, Chihuido de la Sierra Negra, El Trapial and Filo Morado oil fields, among others) provide 82 MMBO/yr comprising 67% of the basin oil production and 31% of Argentina. The source rocks are represented by two thick sections of basinal kerogen type I and II organic-rich shales,more » deposited during transgressive peaks (Agrio Formation), with TOC content up to 5.1%. Lowstand sandstones bodies, 10 to 100 m thick, are composed of eolian and fluvial facies with good reservoir conditions (Avil and Troncoso Sandstones). The seals are provided by the organic-rich shales resting sharply upon the Avil Sandstone and a widespread Aptian-Albian evaporitic event (Huitrin Formation) on top of the Troncoso reservoir. Tertiary structural traps (duplex anticlines) are developed in the outer foothills, whereas structural, combined and stratigraphic traps are present in the adjacent stable structural platform. Oil-to-source rock and oil-to-oil correlation by chromatographic and biomarker fingerprints, carbon isotopic composition and the geological evidences support the proposed oil system.« less

Sensitivity analysis of 1-D dynamical model for basin analysis

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

Cao, S.

1987-01-01

Geological processes related to petroleum generation, migration and accumulation are very complicated in terms of time and variables involved, and it is very difficult to simulate these processes by laboratory experiments. For this reasons, many mathematic/computer models have been developed to simulate these geological processes based on geological, geophysical and geochemical principles. The sensitivity analysis in this study is a comprehensive examination on how geological, geophysical and geochemical parameters influence the reconstructions of geohistory, thermal history and hydrocarbon generation history using the 1-D fluid flow/compaction model developed in the Basin Modeling Group at the University of South Carolina. This studymore » shows the effects of some commonly used parameter such as depth, age, lithology, porosity, permeability, unconformity (eroded thickness and erosion time), temperature at sediment surface, bottom hole temperature, present day heat flow, thermal gradient, thermal conductivity and kerogen type and content on the evolutions of formation thickness, porosity, permeability, pressure with time and depth, heat flow with time, temperature with time and depth, vitrinite reflectance (Ro) and TTI with time and depth, and oil window in terms of time and depth, amount of hydrocarbons generated with time and depth. Lithology, present day heat flow and thermal conductivity are the most sensitive parameters in the reconstruction of temperature history.« less

Time and temperature in petroleum formation: application of Lopatin's method to petroleum exploration

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

Waples, D.W.

1980-06-01

N.V. Lopatin in the Soviet Union has developed a method for taking both time and temperature into account as factors in thermal maturation of kerogen. Lopatin's time-temperature index of maturity (TTI) values correlate with the thermal regimes corresponding to generation and preservation of hydrocarbons. Because such information is potentially of great interest for oil exploration, a calibration and evaluation have been made of Lopatin's method. Within the limitations of the date presently available the following statements can be made: 1. The rate of the chemical reactions involved in thermal maturation of organic material appears to double with every 10/sup 0/Cmore » (18/sup 0/F) rise in temperature. 2. Threshold values of Lopatin's time-temperature index of maturity (TTI) are: 15 onset of oil generation; 75 peak oil generation; 160 end oil generation; approx. 500 40/sup 0/ oil preservation deadline; approx. 1000 50/sup 0/ oil preservation deadline; approx. 1500 wet gas preservation deadline; and > 65,000 dry gas preservation deadline. 3. TTI values calculated from Lopatin reconstructions consistently agree with other maturation parameters commonly used by petroleum geochemists. Potential applications of Lopatin's method for oil exploration include timing of oil generation, calculation of volume of hydrocarbons generated within a basin, and determination of economic deadlines. 13 figures, 5 tables.« less

Parameters on reconstructions of geohistory, thermal history, and hydrocarbon generation history in a sedimentary basin

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

Cao, S.; Lerche, I.

1988-01-01

Geological processes related to petroleum generation, migration, and accumulation are very complicated in terms of time and variables involved, and are very difficult to simulate by laboratory experiments. For this reason, many mathematic/computer models have been developed to simulate these geological processes based on geological, geophysical, and geochemical principles. Unfortunately, none of these models can exactly simulate these processes because of the assumptions and simplifications made in these models and the errors in the input for the models. The sensitivity analysis is a comprehensive examination on how geological, geophysical, and geochemical parameters affect the reconstructions of geohistory, thermal history, andmore » hydrocarbon generation history. In this study, a one-dimensional fluid flow/compaction model has been used to run the sensitivity analysis. The authors will show the effects of some commonly used parameters such as depth, age, lithology, porosity, permeability, unconformity (time and eroded thickness), temperature at sediment surface, bottom hole temperature, present day heat flow, thermal gradient, thermal conductivity and kerogen type, and content on the evolutions of formation thickness, porosity, permeability, pressure with time and depth, heat flow with time, temperature with time and depth, vitrinite reflectance (R/sub 0/) and TTI with time and depth, oil window in terms of time and depth, and amount of hydrocarbon generated with time and depth.« less

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

Sari, A.; Geze, Y.

The studied area is a lake basin located in Bolu basin in Turkey. In the basin, from Upper Cretaceous to Upper Miocene 3,000-m thickness sediments were deposited. Upper Miocene Himmetoglu formation consisted of sandstone, claystone, and marl. To the middle level of the formation are located coal, bituminous limestone, and bituminous shales. In the basin, there are two coal beds whose thicknesses range from 1 to 13 m. The coals are easily breakable and black in color. In the coal beds exists some bituminous limestone and bituminous shales, and their thicknesses are between 5 and 45 cm. The amount ofmore » organic matter of the bituminous rocks from the Upper Miocene Himmetoglu formation are between 6.83 and 56.34 wt%, and the amount of organic matter of the bituminous limestone from the formation are between 13.58 and 57.16 wt%. These values indicate that these rocks have very good source potential. According to hydrogen index (HI), S2/S3, HI-T{sub max}, and HI-OI (oxygen index) parameters, kerogen types of the bituminous rocks and coals belonging to Upper Miocene Himmetoglu formation are Type I, Type II, and Type III. In accordance with HI, S2/S3, HI-T{sub max}, and HI-OI parameters, the bituminous rocks and coals from the Upper Miocene Himmetoglu formation are mostly immature.« less

Hydrocarbon potential of the Early Oligocene Menilite shales in the Eastern Outer Carpathians (Tarcău and Vrancea Nappes, Romania)

NASA Astrophysics Data System (ADS)

Wendorff, Małgorzata; Rospondek, Mariusz; Kluska, Bartosz; Marynowski, Leszek

2017-04-01

During Oligocene to early Miocene time an extensive accumulation of organic-rich sedimentary rocks occurred in entire Paratethyan Basin, including its central part, i.e. the Carpathian Foredeep basin. Rocks of so-called Menilite facies formed there, burying significant amounts of organic matter (OM). These Menilite shales are now widely considered as a source of hydrocarbons throughout the Carpathian region. For the purpose of presented study, rock samples of the Menilite facies (mainly of the Lower Menilite and Bituminous Marl Members) were collected from two sections located in the different tectonic units (the Tarcău and Vrancea Nappes, Romania) of the Outer Carpathians. The main goal of the study was to assess and compare their hydrocarbon potential by examination of bulk geochemistry (total organic carbon content, pyrolysis Rock-Eval), vitrinite reflectance (Ro) and application of lipid biomarker parameters. The data show high variability in OM quantity and quality. Total organic carbon (TOC) content reaches peak values in the siliceous facies of the Lower Menilite Member (up to 8.6 wt% TOC), which contains type II kerogen represented by mainly marine OM type. Such results are confirmed by the presence of short-chain n-alkanes and hopanes. Mixed type II/III kerogen gains importance together with increasing contribution of turbiditic sedimentation. Terrigenous input is marked by occurrence of conifer aromatic biomarkers (such as simonellite, retene and 1,2,3,4-tetrahydroretene) and odd over even long chain n-alkanes predominance, characteristic for epicuticular leaf waxes. The analysed source rocks can be classified as oil-prone and subordinately mixed oil/gas-prone. OM in the inner tectonic unit (Tarcău Nappe; Tmax 430° C, Ro 0.5%) reaches onset of hydrocarbon generation, while in the outer unit (Vrancea Nappe) OM is immature (Tmax 425° C, Ro 0.4%). This maturity trend may be an effect of different burial histories of these units, as well as variation in

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

NASA Astrophysics Data System (ADS)

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

The thermal maturation degree of organic matter from source rocks revealed by wells logs including examples from Murzuk Basin, Libya

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

Negoita, V.; Gheorghe, A.

1995-08-01

The customary technique used to know the organic matter quantity per rock volume it as well as the organic matter maturation stage is based on geochemical analyses accomplished on a preselected number of samples and cuttings drawn from boreholes during the drilling period. But the same objectives can be approached without any extra cost using the continuous measurements of well logs recorded in each well from the ground surface to the total depth. During the diagenetic stage, the identification of potential source rocks out of which no hydrocarbon have been generated may be carried out using a well logging suitemore » including Gamma Ray Spectrometry, the Compensated Neutron/Litho Density combination and a Dual Induction/Sonic Log. During the catagenetic stage the onset of oil generation brings some important changes in the organic matter structure as well as in the fluid distribution throughout the pore space of source rocks. The replacement of electric conductive water by electric non-conductive hydrocarbons, together with water and oil being expelled from source rocks represent a process of different intensities dependent of time/temperature geohistory and kerogen type. The different generation and expulsion scenarios of hydrocarbons taking place during the catagenetic and metagenetic stages of source rocks are very well revealed by Induction and Laterolog investigations. Several crossplots relating vitrinite reflectance, total organic carbon and log-derived physical parameters are illustrated and discussed. The field applications are coming from Murzuk Basin, where Rompetrol of Libya is operating.« less

Accumulation of organic matter in the in the Rome trough of the Appalachian basin and its subsequent thermal history

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

Curtis, J.B.; Faure, G.

1997-03-01

We used geochemical data to examine the origin and preservation of organic matter contained in the lower part of the Huron Member of the Ohio Shale formation and the Rhinestreet Shale Member of the West Falls Formation (Devonian) in Kentucky, Ohio, West Virginia, and Virginia. The thermal history of the organic matter was determined by relating relative temperatures experienced by the organic matter to the geologic setting. The organic matter in these formations is predominantly marine in origin and was most probably derived largely from algal organisms. Although the rate of production of marine organic matter may have been uniformmore » within the basin, its preservation apparently was controlled by the existence of a set of fault-bounded anoxic subbasins associated with the Rome trough, a Cambrian structural complex. These subbasins apparently were anoxic because they limited oxygen recharge by circulating waters. Preservation of organic matter was also enhanced by periodic blooms of the alga Tasmanites and similar organisms in the waters above the subbasins during both early Huron and Rhinestreet deposition. A significant negative correlation was identified between the vitrinite reflectance peak temperature, and integrated measure of the thermal history of a rock, and the hydrogen index, a measure of the remaining hydrocarbon-generation potential of kerogen. Although peak temperatures were controlled by burial depth, excess heating occurred locally, perhaps by hot brines rising from depth through fractures associated with major structures in the study area.« less

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

USGS Publications Warehouse

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.

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

NASA Astrophysics Data System (ADS)

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 (<65%), low methane contents (<10%) and low dryness coefficients (<0.5), and a reversal of the normal trend of carbon isotope ratios, showing δ13C methane (C1) > δ13C ethane (C2) < δ13C propane (C3) < δ13C butane (C4). Specifically, methane is enriched in 13C with the variations in δ13C1 values between gases from Block HD4 and gases from its neighboring blocks reaching 10‰. This type of abnormal 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.

Laboratory experiments simulating poroelastic stress changes associated with depletion and injection in low-porosity sedimentary rocks

NASA Astrophysics Data System (ADS)

Ma, Xiaodong; Zoback, Mark D.

2017-04-01

We characterized the poroelastic deformation of six cores from three formations associated with the Bakken play in the Williston Basin (the Lodgepole, Middle Bakken, and Three Forks formations). All are low-porosity, low-permeability formations, but vary considerably in clay, kerogen, and carbonate content. The experimental program simulated reservoir stress changes associated with depletion and injection via cycling both the confining pressure (Pc) and pore pressure (Pp). We measured volumetric strain, derived the corresponding bulk modulus, and calculated the Biot coefficient (α). We found α, which generally ranges between 0.3 and 0.9, to vary systematically with Pc and Pp for each of the specimens tested. The effect of pore pressure on α is much larger at low simple effective stress (σ = Pc-Pp) during depletion than injection. The α decreases with σ for all pore pressures. For the same Pc and Pp, the Biot coefficient is consistently higher during injection than during depletion. Given the observed variations of α with Pc and Pp, the modeling of reservoir stress changes using a constant α could be problematic as poroelastic stress changes during depletion and injection are not likely to follow the same path. Scanning electron microscope examination of microstructures suggests that the variations of the bulk modulus and the Biot coefficient can be attributed to the abundance of compliant components (pores, microcracks, clays, and organic matter) and how they are distributed throughout the rock matrix.

Preliminary thermal-maturity map of the Cameo and Fairfield or equivalent coal zone in the Piceance Creek Basin, Colorado

USGS Publications Warehouse

Nuccio, Vito F.; Johnson, Ronald C.

1983-01-01

This map was prepared in cooperation with the U.S. Department of Energy's Western Gas Sands Project and was constructed to show the thermal maturity of the Upper Cretaceous Mesaverde Formation (or Group) in the Piceance Creek Basin. The ability of a source rock to generate oil and gas is directly related to its kerogen content and thermal maturity; hence, thermal maturity is commonly used as an exploration tool. This publication consists of two parts: a coal rank map for the basinwide Cameo and Fairfield or equivalent coal zone and three cross sections showing the variation in a coal rank for the entire Mesaverde. Structure contours on the map show the top of the Rollins Sandstone Member of the Mesaverde Formation and its equivalent the Trout Creek Sandstone Member of the Iles Formation of the Mesaverde Group, which immediately underlie the Cameo and Fairfield zone. The structure contours show the fairly strong correlation between structure and coal rank in the basin, suggesting that maximum overburden was the key factor in determining the coal ranks. Even in the southern part of the basin where extensive plutonism occurred during the Oligocene, coal ranks still generally follow structure; indicating that the plutons had little affect on the coals. On the cross sections both the top of the Rollins and Trout Creek, and the top of the Mesaverde Formation/Group are shown. A complete analysis of the entire Mesaverde in the basin would require more information than is presently available.

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

PubMed Central

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

Darkness after the K-T impact: Effects of soot

NASA Technical Reports Server (NTRS)

Wolbach, Wendy S.; Anders, Edward; Orth, Charles J.

1988-01-01

Dust from the K-T impact apparently settled from the atmosphere in less than 6 months, restoring sunlight to minimum photosynthesis levels in about 4 months. However, the discovery of a global soot component in the boundary clay makes it necessary to reconsider the problem, as soot particles not only are smaller (0.1 vs. about 0.5 micrometer) and thus settle more slowly, but also are better light absorbers (optical depth of 13 mg soot cm(-2) about 1800; and are more resistant to rainout. Still, the darkness cannot have lasted very much longer than 6 months, else no larger animals would have survived. Perhaps the soot coagulated with the rock dust and fell out with it. Evidence on this point may be sought at a relatively undisturbed K-T boundary site, such as Woodside Creek, N.Z. There the boundary clay and lowermost Tertiary strata are finely laminated and show large chemical and isotopic differences on a millimeter scale, apparently representing a detailed time sequence. Researchers studied a 3 m section across the boundary at this site, analyzing the principal forms of carbon (soot, elemental C, kerogen, and carbonate) as well as 33 elements. Correlations among the elements were sought. Apparently soot came early and coagulated with the ejecta, staying with them for the primary fallout and in the next 5 cm, but then parting company, perhaps due to size sorting.

Microbial mat structures in the basal Ediacaran Doushantuo cap dolostone from the Yangtze Gorges area of South China and their environmental implications

NASA Astrophysics Data System (ADS)

Wang, Z.; Wang, J.; Xiao, S.; Hu, J.

2014-12-01

Environmental changes after the terminal Cryogenian snowball Earth event have been debated extensively in the literature. But there have been relatively few studies on the biotic response in the aftermath of this snowball Earth event. In fact, a variety of potential microbial facies are preserved in basal Ediacaran cap dolostones as peloids, clotted fabrics, and morphologically diverse microbialites (e. g., tube-like stromatolites and stratiform biolaminites). In South China, centimeter-sized domal and conical stromatolites consisting of wavy or wrinkled microbial mats occur at the top of the Doushantuo cap dolostone. Sedimentological investigation of these stromatolites on outcrop and in core samples from the Yangtze Gorges area suggests that they are likely biological in origin. These stromatolites are characterized by vertical accumulation of dark and light laminae. The dark laminae are sub-millimetric in thickness and are composed of probably biogenic kerogen as determined by Raman spectroscopy. The dark laminae is also rich in pyrite, likely derived from organic degradation by sulfate reduction bacteria. Microsparry calcite occur as cements between the dark laminae. Within the Doushantuo stromatolites, there are patches of randomly oriented calcite needles. The precipitation of these calcite needles may have also been facilitated by microbial processes such bacterial sulfate reduction. Our study shows that shallow marine environment became habitable soon after the snowball Earth glaciation ended and benthic microbes were among some of the first organisms to colonize these environments.

Complete suite of geochemical values computed using wireline logs

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

Lancaster, J.R.; Atkinson, A.

1996-12-31

Geochemical values of {open_quotes}black shale{close_quotes} source rocks can be computed from a complete suite of wireline log data. The computed values are: Total Organic Carbon (Wt%). S1, S2, S3, Hydrogen Index, Oxygen Index, Atomic H/C and O/C ratios, Genetic Potential (S1+S2), S2/S3, and Transfomation Ratio (S1/(S1+S2)). The results are most reliable when calibrated to laboratory analyses of samples in the study area. However, in the absence of samples, reasonable estimates can be made using calibration data from analogous depositional and thermal environments and/or professional judgement and experience. The evaluations provide answers to critical geochemical questions relative to: (1) Organic Mattermore » Quantity; T.O.C. (Wt%), S1, and S2. (2) Kerogen Types; I, II, and III, based on T.O.C. vs S2 cross plot and the van Krevelen diagram of Atomic O/C vs Atomic H/C ratios. (3) Thermal Maturation levels; Transfomation Ratio can be converted to Level of Organic Metamorphism (LOM), pyrolysis Tmax (degC), Vitrinite Reflectance (Ro), Time Temperature Index (TTI) and others. Various analog plots and cross plots can be prepared for interpretation. Case history examples are shown and discussed. Lowstand fan deposits on Barbados were studied in outcrop to construct a conceptual reservoir model for prediction of facies assemblages.« less

Complete suite of geochemical values computed using wireline logs

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

Lancaster, J.R.; Atkinson, A.

1996-01-01

Geochemical values of [open quotes]black shale[close quotes] source rocks can be computed from a complete suite of wireline log data. The computed values are: Total Organic Carbon (Wt%). S1, S2, S3, Hydrogen Index, Oxygen Index, Atomic H/C and O/C ratios, Genetic Potential (S1+S2), S2/S3, and Transfomation Ratio (S1/(S1+S2)). The results are most reliable when calibrated to laboratory analyses of samples in the study area. However, in the absence of samples, reasonable estimates can be made using calibration data from analogous depositional and thermal environments and/or professional judgement and experience. The evaluations provide answers to critical geochemical questions relative to: (1)more » Organic Matter Quantity; T.O.C. (Wt%), S1, and S2. (2) Kerogen Types; I, II, and III, based on T.O.C. vs S2 cross plot and the van Krevelen diagram of Atomic O/C vs Atomic H/C ratios. (3) Thermal Maturation levels; Transfomation Ratio can be converted to Level of Organic Metamorphism (LOM), pyrolysis Tmax (degC), Vitrinite Reflectance (Ro), Time Temperature Index (TTI) and others. Various analog plots and cross plots can be prepared for interpretation. Case history examples are shown and discussed. Lowstand fan deposits on Barbados were studied in outcrop to construct a conceptual reservoir model for prediction of facies assemblages.« less

Origin and migration of hydrocarbon gases and carbon dioxide, Bekes Basin, southeastern Hungary

USGS Publications Warehouse

Clayton, J.L.; Spencer, C.W.; Koncz, I.; Szalay, A.

1990-01-01

The Bekes Basin is a sub-basin within the Pannonian Basin, containing about 7000 m of post-Cretaceous sedimentary rocks. Natural gases are produced from reservoirs (Precambrian to Tertiary in age) located on structural highs around the margins of the basin. Gas composition and stable carbon isotopic data indicate that most of the flammable gases were derived from humic kerogen contained in source rocks located in the deep basin. The depth of gas generation and vertical migration distances were estimated using quantitative source rock maturity-carbon isotope relationships for methane compared to known Neogene source rock maturity-depth relationships in the basin. These calculations indicate that as much as 3500 m of vertical migration has occured in some cases. Isotopically heavy (> - 7 > 0) CO2 is the predominant species present in some shallow reservoirs located on basin-margin structural highs and has probably been derived via long-distance vertical and lateral migration from thermal decompositon of carbonate minerals in Mesozoic and older rocks in the deepest parts of the basin. A few shallow reservoirs (< 2000m) contain isotopically light (-50 to -60%0) methane with only minor amounts of C2+ homologs (< 3% v/v). This methane is probably mostly microbial in origin. Above-normal pressures, occuring at depths greater than 1800 m, are believed to be the principal driving force for lateral and vertical gas migration. These pressures are caused in part by active hydrocarbon generation, undercompaction, and thermal decomposition of carbonates. 

Oxygenation of Earth's atmosphere and its impact on the evolution of nitrogen-based metabolisms

NASA Astrophysics Data System (ADS)

Papineau, D.; Mojzsis, S. J.

2002-12-01

The evolution of metabolic pathways is closely linked to the evolution of the redox state of the terrestrial atmosphere. Nitrogen has been an essential biological element since the emergence of life when reduced nitrogen compounds (e.g. ammonia) were utilized in the prebiotic synthesis of proteins and nucleic acids. The nitrogen isotopic composition of sediments has been used to trace the origin of sedimentary organic matter in the rock record. Nitrogen is therefore suitable as a biosignature to trace the emergence of life on Earth or other planetary bodies as well as to follow the subsequent evolution of the biosphere in response to global redox changes. Evidence is strong that biological nitrogen fixation evolved very early in the history of life. The Last Common Ancestor (LCA) on Earth was most likely capable of nitrogen fixation as seen from the phylogenetic distribution of nitrogen-fixing organisms in both the domains of Bacteria and Archaea. Phylogenetic trees plotted with nitrogen-fixing gene (Nif) sequences from lineages of Bacteria and Archaea suggest that the Nif genes originated in a common ancestor of the two domains. Other phylogenetic analyses have also demonstrated that the paralogous duplication of the nifDK and nifEN operons, central to nitrogen fixation, predated the divergence of Archaea from Bacteria and therefore occurred prior to the emergence of the LCA. Although the same may be true for denitrification, this metabolic pathway probably did not become dominant until atmospheric pO2 increased between ~2.4 to 1.9 Ga during the Great Oxygenation Event (GOE). Recent work has shown a general depletion in 15N content of Archean (pre-2.5 Ga) relative to Phanerozoic (<540 Ma) kerogens. Studies have shown that the distribution of the δ15N values in kerogens shift from negative values in the Early Archean (from -6 to +6‰ with an average near 0‰ ) to approximately contemporary positive values (from +2 to +10‰ with an average at +6‰ ) by the

Identifying early Earth microfossils in unsilicified sediments

NASA Astrophysics Data System (ADS)

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

The optimized log interpretation method and sweet-spot prediction of gas-bearing shale reservoirs

NASA Astrophysics Data System (ADS)

Tan, Maojin; Bai, Ze; Xu, Jingjing

2017-04-01

Shale gas is one of the most important unconventional oil and gas resources, and its lithology and reservoir type are both different from conventional reservoirs [1,2]. "Where are shale reservoirs" "How to determine the hydrocarbon potential" "How to evaluate the reservoir quality", these are some key problems in front of geophysicists. These are sweet spots prediction and quantitative evaluation. As we known, sweet spots of organic shale include geological sweet spot and engineering sweet spot. Geophysical well logging can provide a lot of in-site formation information along the borehole, and all parameters describing the sweet spots of organic shale are attained by geophysical log interpretation[2]. Based on geological and petrophysical characteristics of gas shale, the log response characteristics of gas shales are summarized. Geological sweet spot includes hydrocarbon potential, porosity, fracture, water saturation and total gas content, which can be calculated by using wireline logs[3]. Firstly, the based-logging hydrocarbon potential evaluation is carried out, and the RBF neural network method is developed to estimate the total organic carbon content (TOC), which was proved more effective and suitable than empirical formula and ΔlogR methods [4]. Next, the optimized log interpretation is achieved by using model-searching, and the mineral concentrations of kerogen, clay, feldspar and pyrite and porosity are calculated. On the other hand, engineering sweet spot of shale refers to the rock physical properties and rock mechanism parameters. Some elastic properties including volume module, shear modulus and Poisson's ratio are correspondingly determined from log interpretation, and the brittleness index (BI), effective stress and pore pressure are also estimated. BI is one of the most important engineering sweet spot parameters. A large number of instances show that the summarized log responses can accurately identify the gas-bearing shale, and the proposed RBF

Mars mission relevant investigations on a ~ 3.5 Ga Mars analogue rock from the Pilbara and Barberton

NASA Astrophysics Data System (ADS)

Westall, F.; Pullan, D.; Schröder, C.; Klingelhöfer, G.; Fernández-Sánchez, J.; Jorge, S.; Edwards, H.; Cressey, G.

2007-08-01

and the Raman spectrometers. The silicified volcanics also contain feldspar, identified by the Raman, whereas the XRF analyses showed that they are K-feldspars. The traces of Ba and Cu in this sample are probably related to the mostly hydothermal origin of the silica that cemented the volcanic sediments. Raman spectroscopy also identified a greater abundance of carbon (matured kerogen) in the black layers of this sample (finer grained volcaniclastics). The stromatolite sample, on the other hand, consists largely of quartz although Raman showed some dolomite and carbon (mature kerogen) in the grey layers (silicified stromatolitic layers). The layering in the laminated volcaniclastic sediment was too fine for the Mössbauer spectrometer to pick up any details. The Mössbauer was able to detect a very thin layer of Fe oxide <<0.2 mm on the surface of the stromatolite. Compositional layering in the BIF was clearly visible using multispectral imaging with the Nuance camera and the Mössbauer could identify highly crystalline and chemically pure goethite in the Fe-rich layers with minor goethite and hematite occurring in the quartz-rich layers. The combination of the instrumentation used for imaging and chemical analysis was quite sufficient to identify the sedimentary origin of the finely laminated volcaniclastic and stromatolite rocks and to demonstrate their pervasive silicification. The presence of carbon in these rocks would, in a Mars scenario, make them ideal subjects for organo-geochemical analysis. The same suite of instruments was also able to demonstrate the origin of the BIF, again, a suitable candidate for further analysis. * Planetary Analogue Field Study network (main coordinator D. Pullan)

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

USGS Publications Warehouse

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

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

NASA Astrophysics Data System (ADS)

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).

The role of fossil organic matter in the ecosystem development of post-mining sites revealed by isotope analyses

NASA Astrophysics Data System (ADS)

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.

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

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

Wang, Yifeng

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). CO 2 and H 2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested asmore » an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH 4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH 4 in shale matrix. Therefore, fundamental understanding of CH 4-CO 2-H 2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4-CO 2-H 2O 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.« less

Volcanogenic Pseudo-Fossils from the ∼3.48 Ga Dresser Formation, Pilbara, Western Australia

PubMed Central

Noffke, Nora; Saunders, Martin; Guagliardo, Paul; Pyle, David M.

2018-01-01

Abstract The ∼3.48 billion-year-old Dresser Formation, Pilbara Craton, Western Australia, is a key geological unit for the study of Earth's earliest life and the habitats it occupied. Here, we describe a new suite of spheroidal to lenticular microstructures that morphologically resemble some previously reported Archean microfossils. Correlative microscopy shows that these objects have a size distribution, wall ultrastructure, and chemistry that are incompatible with a microfossil origin and instead are interpreted as pyritized and silicified fragments of vesicular volcanic glass. Organic kerogenous material is associated with much of the altered volcanic glass; variable quantities of organic carbon line or fill the insides of some individual vesicles, while relatively large, tufted organic-rich laminae envelop multiple vesicles. The microstructures reported herein constitute a new type of abiogenic artifact (pseudo-fossil) that must be considered when evaluating potential signs of early life on Earth or elsewhere. In the sample studied here, where hundreds of these microstructures are present, the combined evidence permits a relatively straightforward interpretation as vesicular volcanic glass. However, reworked, isolated, and silicified microstructures of this type may prove particularly problematic in early or extraterrestrial life studies since they adsorb carbon onto their surfaces and are readily pyritized, mimicking a common preservation mechanism for bona fide microfossils. In those cases, nanoscale analysis of wall ultrastructure would be required to firmly exclude a biological origin. Key Words: Microfossils—Pseudo-fossils—Volcanic vesicles—Archean life—Pilbara Craton—Dresser Formation. Astrobiology 18, 539–555. PMID:29461869

Fundamental Understanding of Methane-Carbon Dioxide-Water (CH 4-CO 2-H 2O) Interactions in Shale Nanopores under Reservoir Conditions

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

Wang, Yifeng

2016-04-29

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). CO 2 and H 2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested asmore » an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH 4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH 4 in shale matrix. Therefore, fundamental understanding of CH 4-CO 2-H 2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4-CO 2-H 2O 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.« less

Carbonaceous Chondrite Meteorites: the Chronicle of a Potential Evolutionary Path between Stars and Life

NASA Astrophysics Data System (ADS)

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. [Figure not available: see fulltext.

Rotational reflectance properties of Arkoma Basin dispersed vitrinite: insights for understanding reflectance populations in high thermal maturity regions

USGS Publications Warehouse

Houseknecht, D.W.; Bensley, D.F.; Hathon, L.A.; Kastens, P.H.

1993-01-01

Analysis and interpretation of dispersed vitrinite reflectance data in regions of high thermal maturity (> 2% vitrinite reflectance) have been equivocal partly because of an increase in width and complexity of reflectance histograms with increasing mean reflectance. Such complexity is illustrated by random reflectance (Rran) data from the Arkoma Basin that display a linear increase in standard deviation of Rran with an increase in mean Rran from 1 to 5%. Evaluating how much of the dispersion in these data is the result of vitrinite anisotropy and how much is the result of mixing of kerogen populations by sedimentary processes and/or sampling procedures has been problematic. Automated collection of reflectance data during polarizer rotation provides preliminary data for solution of this problem. Rotational reflectance data collected from a subset of Arkoma Basin samples reveal positive, linear relationships among maximum (R???max), random (Rran), rotational (Rrot), and minimum (R???min) reflectance, as well as a systematic increase in bireflectance (R???max-R???min) with increasing reflectance. R???max and Rrot display lower standard deviations and narrower, more nearly unimodal histograms than Rran and R???min, suggesting that R???max and Rrot are superior (less ambiguous) indices of thermal maturity. These data patterns are inferred to be mostly an indication of increasing vitrinite anisotropy with increasing thermal maturity, suggesting that the linear covariance observed between mean Rran and standard deviation in dispersed organic data sets from regions of high thermal maturity may be explained mostly as the result of increasing vitrinite anisotropy with increasing thermal maturity. ?? 1993.

Electron spin resonance. Part two: a diagnostic method in the environmental sciences.

PubMed

Rhodes, Christopher J

2011-01-01

A review is presented of some of the ways in which electron spin resonance (ESR) spectroscopy may be useful to investigate systems of relevance to the environmental sciences. Specifically considered are: quantititave ESR, photocatalysis for pollution control; sorption and mobility of molecules in zeolites; free radicals produced by mechanical action and by shock waves from explosives; measurement of peroxyl radicals and nitrate radicals in air; determination of particulate matter polyaromatic hydrocarbons (PAH), soot and black carbon in air; estimation of nitrate and nitrite in vegetables and fruit; lipid-peroxidation by solid particles (silica, asbestos, coal dust); ESR of soils and other biogenic substances: formation of soil organic matter carbon capture and sequestration (CCS) and no-till farming; detection of reactive oxygen species in the photosynthetic apparatus of higher plants under light stress; molecular mobility and intracellular glasses in seeds and pollen; molecular mobility in dry cotton; characterisation of the surface of carbon black used for chromatography; ESR dating for archaeology and determining seawater levels; measurement of the quality of tea-leaves by ESR; green-catalysts and catalytic media; studies of petroleum (crude oil); fuels; methane hydrate; fuel cells; photovoltaics; source rocks; kerogen; carbonaceous chondrites to find an ESR-based marker for extraterrestrial origin; samples from the Moon taken on the Apollo 11 and Apollo 12 missions to understand space-weathering; ESR studies of organic matter in regard to oil and gas formation in the North Sea; solvation by ionic liquids as green solvents, ESR in food and nutraceutical research.

Selected pioneering works on humus in soils and sediments during the 20th century: A retrospective look from the International Humic Substances Society view

NASA Astrophysics Data System (ADS)

Feller, Christian; Brossard, Michel; Chen, Yona; Landa, Edward R.; Trichet, Jean

Organic matter in general, and humic substances (HS) in particular, are involved in many processes in soils, sediments, rocks and natural waters. These include rock weathering, plant nutrition, pH buffering, trace metal mobility and toxicity, bioavailability, degradation and transport of hydrophobic organic chemicals, formation of disinfection by-products during water treatment, heterotrophic production in blackwater ecosystems and, more generally, the global carbon cycle. Before the 1970s, natural organic matter of different ecosystem pools ( i.e., soils, sediments, and natural waters) was often studied in isolation, although many similarities exist between them. This is particularly so for HS. In this historical context, a need appeared at the international level for bringing together environmental chemists, soil scientists, hydrologists, and geologists who were interested in HS to provide a forum for the exchange of ideas, to standardize analytical procedures and agree on definitions of HS. The International Humic Substances Society (IHSS) was founded in Denver, Colorado (USA) in 1981 with several objectives among them “to bring together scientists in the coal, soil, and water sciences with interests in humic substances” (home page of the IHSS web site: http://ihss.gatech.edu/ihss2/index.html). This paper presents selected pioneering works on humus in soils and sediments during the 20th century with a special focus on the links between the studies of soil HS and the formation, during early diagenesis, of the precursors of kerogens. Temporal coverage includes key contributions preceding the founding of the IHSS, and a brief history of the organization is presented.

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

USGS Publications Warehouse

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.

Petroleum source rock evaluation of the Alum and Dictyonema Shales (Upper Cambrian-Lower Ordovician) in the Baltic Basin and Podlasie Depression (eastern Poland)

NASA Astrophysics Data System (ADS)

Kosakowski, Paweł; Kotarba, Maciej J.; Piestrzyński, Adam; Shogenova, Alla; Więcław, Dariusz

2017-03-01

We present geochemical characteristics of the Lower Palaeozoic shales deposited in the Baltic Basin and Podlasie Depression. In the study area, this strata are represented by the Upper Cambrian-Lower Ordovician Alum Shale recognized in southern Scandinavia and Polish offshore and a equivalent the Lower Tremadocian Dictyonema Shale from the northern Estonia and the Podlasie Depression in Poland. Geochemical analyses reveal that the Alum Shale and Dictyonema Shale present high contents of organic carbon. These deposits have the best source quality among the Lower Palaeozoic strata, and they are the best source rocks in the Baltic region. The bituminous shales complex has TOC contents up to ca. 22 wt%. The analysed rocks contain low-sulphur, oil-prone Type-II kerogen deposited in anoxic or sub-oxic conditions. The maturity of the Alum and Dictyonema Shales changes gradually, from the east and north-east to the west and south-west, i.e. in the direction of the Tornquist-Teisseyre Zone. Samples, located in the seashore of Estonia and in the Podlasie region, are immature and in the initial phase of "oil window". The mature shales were found in the central offshore part of the Polish Baltic Basin, and the late mature and overmature are located in the western part of the Baltic Basin. The Alum and Dictyonema Shales are characterized by a high grade of radioactive elements, especially uranium. The enrichment has a syngenetic or early diagenetic origin. The measured content of uranium reached up to 750 ppm and thorium up to 37 ppm.

Functional group and individual maceral chemistry of high volatile bituminous coals from southern Indiana: Controls on coking

USGS Publications Warehouse

Walker, R.; Mastalerz, Maria

2004-01-01

The individual maceral chemistries of two Pennsylvanian, high volatile bituminous coals, the Danville Coal Member (Dugger Formation, R o=0.55%) and the Lower Block Coal Member (Brazil Formation, R o=0.56%) of Indiana, were investigated using electron microprobe and Fourier Transform Infrared Spectrometry (FTIR) techniques, with the purpose of understanding differences in their coking behavior. Microprobe results reveal that carbon contents are highest in inertinite and sporinite, followed by desmocollinite and telocollinite. Oxygen and organic nitrogen are most abundant in telocollinite and desmocollinite; sporinite and inertinite contain lesser amounts of these two elements. Organic sulfur contents are highest in sporinite, lowest in inertinite, and intermediate in desmocollinite and telocollinite. Vitrinites within the Danville and Lower Block coals are very similar in elemental composition, while Lower Block inertinites and sporinites have higher carbon, lower oxygen, and sulfur contents which, when combined with the inertinite-and sporinite-rich composition of the Lower Block seam, strongly influences its whole coal chemistry. Fourier transform infrared spectrometry revealed greater aromatic hydrogen in the Lower Block coal, along with higher CH2/CH3 ratios, which suggest that liptinites contribute considerable amounts of long-chain, unbranched aliphatics to the overall kerogen composition of the Lower Block coal. Long-chain, unbranched aliphatics crack at higher temperatures, producing tar and oily byproducts during coking; these may help increase Lower Block plasticity. Electron microprobe and FTIR results indicate that individual maceral chemistries, combined with the maceral composition of the seam, are the primary control of better coking properties of the Lower Block coal. ?? 2003 Elsevier B.V. All rights reserved.

Isotopic Signature of the Ancient Biosphere

NASA Technical Reports Server (NTRS)

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.

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

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

Wang, Yifeng

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). CO 2 and H 2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested asmore » an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 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 CH 4 in shale matrix. Therefore, fundamental understanding of CH 4-CO 2-H 2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4-CO 2-H 2O 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.« less

Sediment facies, depositional environments, and distribution of phytoclasts in the recent Mahakam River delta, Kalimantan, Indonesia

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

Gastaldo, R.A.; Huc, A.Y.

1992-12-01

The Mahakam River delta is a tide- and wave-dominated delta located on the edge of the Kutei basin, eastern Kalimantan, Borneo. It is a coastal deltaic sequence, Neogene to Holocene in age, from which all recoverable hydrocarbons (crude oil and natural gas) are considered to be derived from kerogen III predecessors. However, a complete understanding of the types of sediments sourcing the hydrocarbons has not yet been achieved. A vibracoring program sampled the principal fine-grained depositional environments in two transects; one within the fluvially-dominated regime, one within the tidally-dominated regime. Ten sedimentary facies are distinguished and phytoclasts have been recoveredmore » from all environments of deposition. Canopy parts from the mixed tropical forest community are preserved throughout the delta, whereas dicotyledonous angiosperm mangroves are restricted to the subtidal zone and delta front. Nypa parts are preserved in most depositional environments. In sites where there appears to be an absence of macrodetritus, dispersed cuticle is recoverable. Identifiable plant parts include wood and fibrous tissues, Nypa petioles and leaf laminae, dicotyledonous angiosperm leaves and isolated cuticles, fruits and seeds, roots and rootlets, and moss. Dammar is found either as dispersed resin ducts or amorphous clasts. Additional biotic components found in bedded plant litters include insects, gastropods, bivalves, sand dollars, ostracods, and crabs. Fluvial channels and depositional sites associated with these systems in the delta front can be differentiated from Nypa swamps and mixed tropical hardwood-palm swamps based on their phytological components and accessory biotic elements. 39 refs., 10 figs., 3 tabs.« less

Chemical and Isotopic Analysis of Trace Organic Matter on Meteorites and Interstellar Dust Using a Laser Microprobe Instrument

NASA Technical Reports Server (NTRS)

Zare, Richard N.; Boyce, Joseph M. (Technical Monitor)

2001-01-01

Polycyclic Aromatic Hydrocarbons (PAHs) are of considerable interest today because they are ubiquitous on Earth and in the interstellar medium (ISM). In fact, about 20% of cosmic carbon in the galaxy is estimated to be in the form of PAHs. Investigation of these species has obvious uses for determining the cosmochemistry of the solar system. Work in this laboratory has focused on four main areas: 1) Mapping the spatial distribution of PAHs in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. 2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe Laser Desorption Ionization Mass Spectroscopy and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. 3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. 4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames. All areas involve elucidation of the solar system formation and chemistry using microprobe Laser Desorption Laser Ionization Mass Spectrometry. A brief description of microprobe Laser Desorption Ionization Mass Spectroscopy, which allows selective investigation of subattomole levels of organic species on the surface of a sample at 10-40 micrometer spatial resolution, is given.

Spatially-resolved isotopic study of carbon trapped in ∼3.43 Ga Strelley Pool Formation stromatolites

NASA Astrophysics Data System (ADS)

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.

Carbonaceous Chondrite Meteorites: the Chronicle of a Potential Evolutionary Path between Stars and Life.

PubMed

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.

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)

NASA Astrophysics Data System (ADS)

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.

Chronostratigraphy and hydrocarbon habitat associated with the Jurassic carbonates of Abu Dhabi, United Arab Emirates

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

Alsharahan, A.S.; Whittle, G.L.

1995-08-01

Deposition of Jurassic epeiric shelf carbonates and evaporates were controlled by epeirogenic movement and sea level fluctuations which formed an excellent combination of source rocks, reservoirs and seats in Abu Dhabi. At the end of the Triassic, a relative drop in sea level, caused by eustatic sea level lowering in conjunction with minor tectonic uplift, resulted in non-deposition or erosion. In the Toarcian, deposition of carbonates and terrigenous, clastics produced the Marrat Formation. In the mid-Aalenian, a drop in sea level eroded much of the Marrat and some of the Triassic in offshore U.A.E. The deposition of the Hamlah Formationmore » followed, under neritic, well-oxygenated conditions. The Middle Jurassic was characterized by widespread, normal marine shelf carbonates which formed the cyclic Izhara and Araej formations (reservoirs). In the Upper Jurassic, the carbonate shelf became differentiated into a broad shelf with a kerogen-rich intrashelf basin, formed in response to a eustatic rise coupled with epeirogenic downwarping and marine flooding. The intrashelf basin fill of muddy carbonate sediments constitutes the Diyab Formation and its onshore equivalent, the Dukhan Formation (source rocks). In the late Upper Jurassic, the climate became more arid and cyclic deposition of carbonates and evaporates prevailed, forming alternating peritidal anhydrite, dolomite and limestone in the Arab Formation (reservoir). Arid conditions continued into the Tithonian, fostering the extensive anhydrite of the Hith Formation (seal) in a sabkha/lagoonal setting on the shallow peritidal platform, the final regressive supratidal stage of this major depositional cycle.« less

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

USGS Publications Warehouse

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.

Unconventional shale-gas systems: The Mississippian Barnett Shale of north-central Texas as one model for thermogenic shale-gas assessment

USGS Publications Warehouse

Jarvie, D.M.; Hill, R.J.; Ruble, T.E.; Pollastro, R.M.

2007-01-01

Shale-gas resource plays can be distinguished by gas type and system characteristics. The Newark East gas field, located in the Fort Worth Basin, Texas, is defined by thermogenic gas production from low-porosity and low-permeability Barnett Shale. The Barnett Shale gas system, a self-contained source-reservoir system, has generated large amounts of gas in the key productive areas because of various characteristics and processes, including (1) excellent original organic richness and generation potential; (2) primary and secondary cracking of kerogen and retained oil, respectively; (3) retention of oil for cracking to gas by adsorption; (4) porosity resulting from organic matter decomposition; and (5) brittle mineralogical composition. The calculated total gas in place (GIP) based on estimated ultimate recovery that is based on production profiles and operator estimates is about 204 bcf/section (5.78 ?? 109 m3/1.73 ?? 104 m3). We estimate that the Barnett Shale has a total generation potential of about 609 bbl of oil equivalent/ac-ft or the equivalent of 3657 mcf/ac-ft (84.0 m3/m3). Assuming a thickness of 350 ft (107 m) and only sufficient hydrogen for partial cracking of retained oil to gas, a total generation potential of 820 bcf/section is estimated. Of this potential, approximately 60% was expelled, and the balance was retained for secondary cracking of oil to gas, if sufficient thermal maturity was reached. Gas storage capacity of the Barnett Shale at typical reservoir pressure, volume, and temperature conditions and 6% porosity shows a maximum storage capacity of 540 mcf/ac-ft or 159 scf/ton. Copyright ?? 2007. The American Association of Petroleum Geologists. All rights reserved.

Hydrocarbons on Saturn's satellites Iapetus and Phoebe

USGS Publications Warehouse

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.

Gas play opportunities in deeper Jurassic sequences of the Neuquen basin embayment, Argentina

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

Fernandez-Seveso, F.; Figueroa, D.E.; Rodriguez, H.

1996-08-01

We have defined new gas plays at around 4000 m depth near the giant Loma La Lata gas field. The plays, in lower Jurassic sandstones, were developed using a different approach in stratigraphic signatures as well as deformation styles. Two initial rifting stages led to the Triassic-Early Liassic volcanoclastic deposition (Precuyo s.l.) into a suite of discrete half-grabens. The late rifting stage amalgamated the Precuyo depocenters into notably extended subsiding half-grabens where the Pliensbachian-Toarcian deposits were accommodated. This lower Cuyo sequence-set (LC) consists of basinal marine shales (Molles Formation) and a progradational stacking of slope and shelf sandstones (Lajas Formation),more » bearing a kerogen type III-II within the gas window with TOC values range 2-6%. The LC top matches with a conspicuous regional unconformity related to the thermo-mechanic subsidence. The overlying Bajocian-early Callovian upper Cuyo sequence set exhibits outer shelf argillaceous sediments at the base. The identified plays are related to two deformation mechanisms: mud diapirism and tectonic inversion. The thick, rapidly deposited LC sandstones triggered the ductile flow of the underlying, overpressured shales. Soon after, the tectonic inversion of the Precuyo half-grabens produced a series of aligned anticlines parallel to Huincul Arch. Scattered incipient diapirism toward the embayment resulted in dome-like structures. Sandstones with gas shows could act as {open_quotes}tight gas reservoirs.{close_quotes} However, increased permeability through natural fracturing in the structures would increase their viability. The estimated resources of several TCF in untested closures and the industry infrastructure make these plays particularly attractive for gas exploration.« less

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

NASA Astrophysics Data System (ADS)

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.

Methylhopane Biomarker and Carbon Isotopic Evidence for Late Archean Aerobic Ecosystems

NASA Technical Reports Server (NTRS)

Eigenbrode, Jennifer L.; Freeman, Katherine H.; Summons, Roger E.

2007-01-01

Molecular fossils are particularly valuable in early Earth studies because they provide information about microbial sources and ecology. Here we report on the distribution of 2- methyl and 3-methylhopanes preserved in a 2.72-2.56 billion-year-old section of shallow and deepwater sediments of the Hamersley Province [Eigenbrode et aI., submitted]. These biomarkers are mostly from cyanobacteria and oxygen-respiring methanotrophs, respectively. The relative abundance of 2-methylhopanes increases with carbonate abundance in shallow-water facies indicating cyanobacteria were key microbes in shallow ecosystems and suggesting they supplied both molecular oxygen and fixed carbon. The relative abundance of 3-methylhopane strongly correlates with kerogen-carbon isotopic values, and is more abundant in the samples with 13C-enriched signatures. Thus, molecular data provides evidence for cycling of methane in shallow settings, even though the anoxic deeper environments bear stronger 13C-depletion, which together suggests a more complex methane cycle than previously envisioned. Detailed facies analysis of the Hamersley carbon-isotope record reveals temporal changes suggesting continued oxidation of shallow settings favoring the expansion of aerobic ecosystems and respiring organisms [Eigenbrode et aI., 2006, PNAS, 103: 15759]. Similar analysis of published carbon-isotopic records suggests similar, but diachronous, expansion of oxygenated habitats in shallow then deep waters as anaerobic microbial communities gave way to respiring communities fueled by oxygenic photosynthesis before the post 2.45-Ga atmospheric oxygenation event [Eigenbrode et aI., 2006]. The robust relationships observed provide geochemical support for methanogenesis, aerobic methanotrophy, and oxygenic photosynthesis in the late Archean, as well as major ecological shifts linked to biogeochemical reorganization.

Hydrous pyrolysis of crude oil in gold-plated reactors

USGS Publications Warehouse

Curiale, J.A.; Lundegard, P.D.; Kharaka, Y.K.

1992-01-01

Crude oils from Iraq and California have been pyrolyzed under hydrous conditions at 200 and 300??C for time periods up to 210 days, in gold-plated reactors. Elemental (vanadium, nickel), stable isotopic (carbon), and molecular (n-alkanes, acyclic isoprenoids, steranes, terpanes and aromatic steroid hydrocarbons) analyses were made on the original and pyrolyzed oils. Various conventional crude oil maturity parameters, including 20S/(20S + 20R)-24-ethylcholestane ratios and the side-chain-length distribution of aliphatic and aromatic steroidal hydrocarbons, were measured in an effort to assess the modification of molecular maturity parameters in clay-free settings, similar to those encountered in "clean" reservoirs. Concentrations of vanadium and nickel in the Iraq oil decrease significantly and the V/(V + Ni) ratio decreases slightly, with increasing pyrolysis time/temperature. Whole oil carbon isotope ratios remain fairly constant during pyrolysis, as do hopane/sterane ratios and carbon number distribution of 5??(H),14??(H),17??(H),20R steranes. These latter three parameters are considered maturity-invariant. The ratios of short side-chain components to long side-chain components of the regular steranes [C21/(C21 + C29R)] and the triaromatic steroid hydrocarbons [C21/(C21 + C28)] vary systematically with increasing pyrolysis time, indicating that these parameters may be useful as molecular maturity parameters for crude oils in clay-free reservoir rocks. In addition, decreases in bisnorhopane/hopane ratio with increasing pyrolysis time, in a clay-free and kerogen-free environment, suggest that the distribution of these compounds is controlled by either differential thermal stabilities or preferential release from a higher-molecular weight portion of the oil. ?? 1992.

A mathematical model of fluid and gas flow in nanoporous media.

PubMed

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.

The Hollow Spheres of the Orgueil Meteorite: A Re-Examination

NASA Technical Reports Server (NTRS)

Hoover, Richard B.; Jerman, Gregory; Rossignold-Strick, Maritine

2005-01-01

In 1971, Rossignol-Strick and Barghoorn provided images and a description of a number of spherical hollow microstructures showing well-defined walls in acid macerated extract of the Orgueil CI carbonaceous meteorite. Other forms such as membranes and spiral shaped structures were also reported. The carbon-rich (kerogen) hollow spheres were found to be in a narrowly constrained distribution of sizes (mainly 7 to 10 microns in diameter). Electron microprobe analysis revealed that these spheres contained Carbon, possibly P, N, and K. It was established that these forms could not be attributed to pollen or other recent terrestrial contaminants. It was concluded that they most probably represented organic coatings on globules of glass, olivine or magnetite in the meteorite. However, recent studies of the Orgueil meteorite have been carried out at the NASA/Marshall Space Flight Center with the S-4000 Hitachi Field Emission Scanning Electron Microscope (FESEM). These investigations have revealed the presence of numerous carbon encrusted spherical magnetite platelets and spherical and ovoidal bodies of elemental iron in-situ in freshly fractured interior surfaces of the meteorite. Their size range is also very narrowly constrained (typically approximately 6 to 12 microns) in diameter. High resolution images reveal that these bodies are also encrusted with a thin carbonaceous sheath and are surrounded by short nanofibrils that are shown to be composed of high purity iron by EDAX elemental analysis. We present Secondary and Backscatter Electron FESEM images and associated EDAX elemental analyses and 2D X-ray maps of these forms as we re-examine the hollow spheres of Orgueil and attempt to determine if they are representatives of the same population of indigenous microstructures.

Carbonaceous Components in the Comet Halley Dust

NASA Technical Reports Server (NTRS)

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.

Nitrogen isotope record of a perturbed paleoecosystem in the aftermath of the end-Triassic crisis, Doniford section, SW England

NASA Astrophysics Data System (ADS)

Paris, Guillaume; Beaumont, ValéRie; Bartolini, Annachiara; CléMence, Marie-Emilie; Gardin, Silvia; Page, Kevin

2010-08-01

The Triassic-Jurassic transition (TJ) is characterized by successive perturbations of the carbon cycle during a time of biotic disruption as recorded by the carbon isotopic composition of organic matter (δ13Corg). The nitrogen isotopic composition of sedimentary organic matter (δ15Norg) constitutes a key parameter to explore the functioning of the ecosystem during carbon cycle perturbations and biological crises, because it provide information on seawater redox conditions and/or nutrient cycling. Here we report the first continuous δ15Norg record across the TJ transition at the Doniford Bay section (Bristol Channel Basin, UK), combined with δ13Corg, kerogen typology and carbon (δ13Cmin) and oxygen (δ18Omin) isotopic composition of bulk carbonates. The end Triassic is characterized by a major negative excursion both in δ13Corg and δ13Cmin, very low TOC (Total Organic Carbon, wt%) and high δ15Norg values, associated with a sea level lowstand. A second δ13Corg negative excursion occurs during the lower Hettangian. This interval is characterized by phases of carbonate production increase alternated with phases of exceptional accumulations of type I organic matter (up to 12%) associated with lower δ15Norg and δ13Corg. This alternation likely reflects a succession of nutrient input increase to the basin leading to enhanced productivity and eutrophication, which promoted a primary production driven by organic-walled prokaryotic organisms. The following OM export increase generates anaerobic conditions within the basin. These events occur between periods of relatively good seawater column ventilation and nutrient recycling boosting the carbonate producer recovery. Ecosystems remain perturbed in the Bristol Channel Basin during the aftermath of the end-Triassic crisis.

Petroleum generation and migration in the Mesopotamian Basin and Zagros fold belt of Iraq: Results from a basin-modeling study

USGS Publications Warehouse

Pitman, Janet K.; Steinshouer, D.; Lewan, M.D.

2004-01-01

A regional 3-D total petroleum-system model was developed to evaluate petroleum generation and migration histories in the Mesopotamian Basin and Zagros fold belt in Iraq. The modeling was undertaken in conjunction with Middle East petroleum assessment studies conducted by the USGS. Regional structure maps, isopach and facies maps, and thermal maturity data were used as input to the model. The oil-generation potential of Jurassic source-rocks, the principal known source of the petroleum in Jurassic, Cretaceous, and Tertiary reservoirs in these regions, was modeled using hydrous pyrolysis (Type II-S) kerogen kinetics. Results showed that oil generation in source rocks commenced in the Late Cretaceous in intrashelf basins, peak expulsion took place in the late Miocene and Pliocene when these depocenters had expanded along the Zagros foredeep trend, and generation ended in the Holocene when deposition in the foredeep ceased. The model indicates that, at present, the majority of Jurassic source rocks in Iraq have reached or exceeded peak oil generation and most rocks have completed oil generation and expulsion. Flow-path simulations demonstrate that virtually all oil and gas fields in the Mesopotamian Basin and Zagros fold belt overlie mature Jurassic source rocks (vertical migration dominated) and are situated on, or close to, modeled migration pathways. Fields closest to modeled pathways associated with source rocks in local intrashelf basins were charged earliest from Late Cretaceous through the middle Miocene, and other fields filled later when compression-related traps were being formed. Model results confirm petroleum migration along major, northwest-trending folds and faults, and oil migration loss at the surface.

The effect of oil-water-rock partitioning on the occurrence of alkylphenols in petroleum systems

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

Taylor, P.; Larter, S.; Jones, M.

1997-05-01

Low molecular weight (C{sub 0}-C{sub 3}) alkylphenols are ubiquitous constituents of crude oils and formation waters of petroleum systems, and they represent legislatively monitored pollutants in produced oils and waters from offshore petroleum facilities. Their origin and the controls on their abundance are uncertain. Analysis of forty-four oils from various petroleum provinces, together with laboratory partitioning experiments, has provided further information on these controls. Although phenols are clearly partitioned between oil and water in petroleum systems, the consistency of most nondegraded petroleum phenol distributions (despite the apparent decrease of phenol concentrations in petroleums with increasing secondary migration distance) requires phenolmore » partitioning between petroleum, water, and solid phases-chiefly kerogen in the carrier bed. The retention of significant phenol concentrations in petroleums that have migrated tens of kilometres does indicate that petroleum typically only equilibrates with minor volumes of rock and associated waters. Laboratory experiments indicate that oils which have migrated approximately 25 km in the North Sea Tampen Spur through Jurassic sandstones may have equilibrated with less than 20 vol of rock and water, and possibly much less than 1 vol, depending on the sorbing phases within the rock (i.e., mineral or organic matter) and the wetting phase (oil or water). We conclude, supporting the hypothesis of Ioppolo-Armanios et al. (1995), that although ortho-substituted isomers dominate the phenol distributions of many petroleums, this reflects catalytic alkylation/isomerisation of unknown alkylphenol precursors in source rocks, rather than selective removal of meta- and para-substituted alkylphenol isomers from petroleum by water washing. 35 refs., 7 figs., 2 tabs.« less

Basin analysis of South Mozambique graben

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

Iliffe, J.; Lerche, I.; De Buyl, M.

1987-05-01

Basin analysis of the South Mozambique graben between latitudes 25/sup 0/ and 26/sup 0/ and longitudes 34/sup 0/ and 35/sup 0/ demonstrates how modeling techniques may help to assess the oil potential of a speculative basin with only minimal seismic data. Two-dimensional restoration of the seismic profiles, using a backstripping and decompaction program on pseudowells linked with structural reconstruction, assesses the rift's two-phase extensional history. Since no well or thermal indicator data exist within the basin, the thermal history had to be derived from extensional models. The best fit of observed subsidence curves and those predicted by the models resultsmore » in values of lithospheric extension (gamma). The disagreement in observed and theoretical basement subsidence curves was minimized by taking a range of gamma for each model for each well. These extension factors were then used in each model's equations for paleoheat flux to derive the heat-flow histories. (It is noted that a systematic basinwide variance of gamma occurs.) The heat-flux histories were then used with a one-dimensional fluid flow/compaction model to calculate TTI values and oil windows. A Tissot generation model was applied to each formation in every well for kerogen Types I, II, and III. The results were contoured across the basin to assess possible oil- and gas-prone formations. The extensional, burial, and thermal histories are integrated into an overall basin development picture and provide an oil and gas provenance model. Thus they estimate the basinwide hydrocarbon potential and also gain insight into the additional data necessary to significantly decrease the uncertainty.« less

Burial thermal histories, vitrinite reflectance, and laumontite isograd

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

McCulloh, T.H.; Fan, J.J.

1985-02-01

The optical reflectance of vitrinite has become the standard basis for quantitative judgments of integrated temperature-time (burial) histories. Inferences about the crystallization temperature of the calcium zeolite laumontite also have been used repeatedly for such purposes. In a few cases, these 2 approaches have been combined or their results compared. As generally employed, neither approach has quantitative validity. Factors other than temperature and time play roles in the way that burial history affects vitrinite reflectance (R/sub o/). In particular, the organic geochemical environment exerts a strong and variable local-to-regional influence on the rate of increase of R/sub o/ versus temperature.more » Hydrocarbon-rich environments retard the rate of R/sub o/ increase; hydrocarbon-deficient environments accelerate it. Local (interbed) R/sub o/ divergencies up to 0.5% result, and regional (interbasin) divergencies are equal or possibly greater. Much of the scatter in compilation plots of R/sub o/ versus TTI may result from such divergencies. Laumontite, where it can crystallize at all, precipitates according to specific stringent requirements of fluid pressure and temperature. The crystallization temperature at the laumontite isograd ranges from 32/sup 0/C (1 atm) to 193/sup 0/C (P/sub f/ = 1325 atm). The crystallization rate is geologically instantaneous, completely unlike the time-dependent organic reactions responsible for the progressive aromatization of coal macerals during kerogen maturation, providing an instantaneous pressure-sensitive maximum-recording thermometer. Paleotemperatures to constrain interpretations of R/sub o/ data may be one of the greatest values to be gained from studies of diagenetic laumontite.« less

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

Burwood, R.; Mycke, B.

The Lower Congo Coastal and Kwanza provinces cumulatively account for reserves of ca 6 GBOR. These are dominantly reservoired in Pinda carbonate traps of the former basin. However, with production from a range of accretionary 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, Synrift I, II, etc.) evolved into the Drift phase opening of the southern Atlantic. A striking featuremore » of this progression was widespread evaporate deposition of the Aptian Loeme Salt. This separates two distinct sedimentary and tectonic domains of the Pre- and Post-Salt. The core Lower Congo habitat is dominated by the Pre-Salt Bucomazi (!) petroleum system. These lacustrine, often super-rich, sediments reveal considerable organofacies variations between their basin fill (Synrift I) and sheet drape (Synrift 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 habitat extending southwards to 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. Elsewhere, the Upper Cretaceous-Paleogene marine clastic labe (!) petroleum system is hydrocarbon productive, yielding petroleums of unique, and/or mixed Pre-Salt, source provenance.« less

Geological setting of oil shales in the Permian phosphoria formation and some of the geochemistry of these rocks

USGS Publications Warehouse

Maughan, E.K.

1983-01-01

Recent studies of the Meade Peak and the Retort Phosphatic Shale Members of the Phosphoria Formation have investigated the organic carbon content and some aspects of hydrocarbon generation from these rocks. Phosphorite has been mined from the Retort and Meade Peak members in southeastern Idaho, northern Utah, western Wyoming and southwestern Montana. Organic carbon-rich mudstone beds associated with the phosphorite in these two members also were natural sources of petroleum. These mudstone beds were differentially buried throughout the region so that heating of these rocks has been different from place to place. Most of the Phosphoria source beds have been deeply buried and naturally heated to catagenetically form hydrocarbons. Deepest burial was in eastern Idaho and throughout most of the northeastern Great Basin where high ambient temperatures have driven the catagenesis to its limit and beyond to degrade or to destroy the hydrocarbons. In southwest Montana, however, burial in some areas has been less than 2 km, ambient temperatures remained low and the kerogen has not produced hydrocarbons (2). In these areas in Montana, the kerogen in the carbonaceous mudstone has retained the potential for hydrocarbon generation and the carbon-rich Retort Member is an oil shale from which hydrocarbons can be synthetically extracted. The Phosphoria Formation was deposited in a foreland basin between the Cordilleran geosyncline and the North American craton. This foreland basin, which coincides with the area of deposition of the two organic carbon-rich mudstone members of the Phosphoria, has been named the Sublett basin (Maughan, 1979). The basin has a northwest-southeast trending axis and seems to have been deepest in central Idaho where deep-water sedimentary rocks equivalent to the Phosphoria Formation are exceptionally thick. The depth of the basin was increasingly shallower away from central Idaho toward the Milk River uplift - a land area in Montana, the ancestral Rocky

Experiments on the role of water in petroleum formation

NASA Astrophysics Data System (ADS)

Lewan, M. D.

1997-09-01

Pyrolysis experiments were conducted on immature petroleum source rocks under various conditions to evaluate the role of water in petroleum formation. At temperatures less than 330°C for 72 h, the thermal decomposition of kerogen to bitumen was not significantly affected by the presence or absence of liquid water in contact with heated gravel-sized source rock. However, at 330 and 350°C for 72 h, the thermal decomposition of generated bitumen was significantly affected by the presence or absence of liquid water. Carbon-carbon bond cross linking resulting in the formation of an insoluble bitumen (i.e., pyrobitumen) is the dominant reaction pathway in the absence of liquid water. Conversely, thermal cracking of carbon-carbon bonds resulting in the generation of saturate-enriched oil, which is similar to natural crude oils, is the dominant reaction pathway in the presence of liquid water. This difference in reaction pathways is explained by the availability of an exogenous source of hydrogen, which reduces the rate of thermal decomposition, promotes thermal cracking, and inhibits carbon-carbon bond cross linking. The distribution of generated n-alkanes is characteristic of a free radical mechanism, with a broad carbon-number distribution (i.e., C 5 to C 35) and only minor branched alkanes from known biological precursors (i.e., pristane and phytane). The generation of excess oxygen in the form of CO 2 in hydrous experiments and the high degree of hydrocarbon deuteration in a D 2O experiment indicate that water dissolved in the bitumen is an exogenous source of hydrogen. The lack of an effect on product composition and yield with an increase in H + activity by five orders of magnitude in a hydrous experiment indicates that an ionic mechanism for water interactions with thermally decomposing bitumen is not likely. Several mechanistically simple and thermodynamically favorable reactions that are consistent with the available experimental data are envisaged for the

Experiments on the role of water in petroleum formation

USGS Publications Warehouse

Lewan, M.D.

1997-01-01

Pyrolysis experiments were conducted on immature petroleum source rocks under various conditions to evaluate the role of water in petroleum formation. At temperatures less than 330??C for 72 h, the thermal decomposition of kerogen to bitumen was not significantly affected by the presence or absence of liquid water in contact with heated gravel-sized source rock. However, at 330 and 350??C for 72 h, the thermal decomposition of generated bitumen was significantly affected by the presence or absence of liquid water. Carbon-carbon bond cross linking resulting in the formation of an insoluble bitumen (i.e., pyrobitumen) is the dominant reaction pathway in the absence of liquid water. Conversely, thermal cracking of carbon-carbon bonds resulting in the generation of saturate-enriched oil, which is similar to natural crude oils, is the dominant reaction pathway in the presence of liquid water. This difference in reaction pathways is explained by the availability of an exogenous source of hydrogen, which reduces the rate of thermal decomposition, promotes thermal cracking, and inhibits carbon-carbon bond cross linking. The distribution of generated n-alkanes is characteristic of a free radical mechanism, with a broad carbon-number distribution (i.e., C5 to C35) and only minor branched alkanes from known biological precursors (i.e., pristane and phytane). The generation of excess oxygen in the form of CO2 in hydrous experiments and the high degree of hydrocarbon deuteration in a D2O experiment indicate that water dissolved in the bitumen is an exogenous source of hydrogen. The lack of an effect on product composition and yield with an increase in H+ activity by five orders of magnitude in a hydrous experiment indicates that an ionic mechanism for water interactions with thermally decomposing bitumen is not likely. Several mechanistically simple and thermodynamically favorable reactions that are consistent with the available experimental data are envisaged for the

Geological studies of the COST nos. G-1 and G-2 wells, United States North Atlantic outer continental shelf

USGS Publications Warehouse

Scholle, Peter A.; Wenkam, Chiye R.

1982-01-01

limestones overlain by Upper Cretaceous unconsolidated sands, sandstones, and calcareous shales. Pliocene, Miocene, Eocene, and Paleocene strata are disconformable over Santonian rocks; uppermost Cretaceous rocks are missing at this site, as at G-1. The sedimentary rocks in the COST No. G-2 well were deposited in somewhat deeper water, farther away from sources of terrigenous material than those at G-l, but still in marginal marine to shallow marine environments. Data from geophysical logs and examination of conventional cores, wellcuttings, and sidewall cores show that below 10,000 ft {3,048 m), the strata in both wells have moderate porosities {< 20 percent) and low to moderate permeabilities {< 100 mD) and are thus considered adequate to poor reservoir rocks. Above 10,000 ft (3,000 m) the porosities range from 16 to 39 percent, and the permeabilities are highly variable, ranging from 0.01 to 7,100 mD. Measurements of vitrinite reflectance, color alteration of visible organic matter, and various organic geochemical properties suggest that the Tertiary and Cretaceous strata of the COST Nos. G-1 and G-2 are not prospective for oil and gas. These sediments have not been buried deeply enough for hydrocarbon generation, and the kerogen and extractable organic matter in them are thermally immature. However, the Jurassic rocks at the G-1 site do contain small amounts of thermally mature gas-prone kerogens. The Jurassic rocks at COST No. G-2 are also gas-prone and are slightly richer in organic carbon and total extractable hydrocarbons than the G-1 rocks, but both sites have only poor to fair oil and gas source-rock potential.

Sedimentary organic matter characterization of the Triassic-Jurassic boundary GSSP at Kuhjoch (Austria)

NASA Astrophysics Data System (ADS)

Ruhl, M.; Veld, H.; Kürschner, W. M.

2010-03-01

The Triassic-Jurassic (T-J) boundary interval coincides with enhanced extinction rates in the marine realm and pronounced changes in terrestrial ecosystems on the continents. It is further marked by distinct negative excursions in the δ13C org and δ13C carb signature that may represent strong perturbations of the global carbon cycle. We present integrated geochemical, stable-isotope and palynological data from the Kuhjoch section, the Global boundary Stratotype Section and Point (GSSP) for the base of the Jurassic (Northern Calcareous Alps, Austria). We show that the initial carbon isotope excursion (CIE), coinciding with the marine extinction interval and the formation of black shales in the western Tethys Eiberg Basin, is marked by only minor changes in kerogen type, which is mainly of terrestrial origin. Increased Total Organic Carbon (TOC) concentrations of 9% at the first half of the initial CIE coincide with Hydrogen Index (HI) values of over 600 mg HC/g TOC. The high correlation (with R2 = 0.93) between HI values and terrestrial Cheirolepidiaceaen conifer pollen suggests a terrestrial source for the hydrogen enriched organic compounds. The lack of major changes in source of the sedimentary organic matter suggests that changes in the δ13C org composition are genuine and represent true disturbances of the global C-cycle. The sudden decrease in total inorganic carbon (TIC) concentrations likely represents the onset of a biocalcification crisis. It coincides with a 4.5‰ negative shift in δ13C org values and possibly corresponds to the onset of CAMP related volcanic activity. The second half of the initial CIE is marked by the dramatic increase of green algae remains in the sediment. The simultaneous increase of the C org/N tot ratio suggests increased marine primary production at the final stage of black shale formation.

The First Discovery of Presolar Graphite Grains from the Highly Reducing Qingzhen (EH3) Meteorite

NASA Astrophysics Data System (ADS)

Xu, Yuchen; Lin, Yangting; Zhang, Jianchao; Hao, Jialong

2016-07-01

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 28Si-excesses, suggestive of supernovae origins, and four grains are 12C- and 29,30Si-rich, consistent with low-metallicity asymptotic giant branch star origins. Another two graphite spherules have extremely low 12C/13C 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.

Application of Fractal Geometry in Evaluation of Effective Stimulated Reservoir Volume in Shale Gas Reservoirs

NASA Astrophysics Data System (ADS)

Sheng, Guanglong; Su, Yuliang; Wang, Wendong; Javadpour, Farzam; Tang, Meirong

According to hydraulic-fracturing practices conducted in shale reservoirs, effective stimulated reservoir volume (ESRV) significantly affects the production of hydraulic fractured well. Therefore, estimating ESRV is an important prerequisite for confirming the success of hydraulic fracturing and predicting the production of hydraulic fracturing wells in shale reservoirs. However, ESRV calculation remains a longstanding challenge in hydraulic-fracturing operation. In considering fractal characteristics of the fracture network in stimulated reservoir volume (SRV), this paper introduces a fractal random-fracture-network algorithm for converting the microseismic data into fractal geometry. Five key parameters, including bifurcation direction, generating length (d), deviation angle (α), iteration times (N) and generating rules, are proposed to quantitatively characterize fracture geometry. Furthermore, we introduce an orthogonal-fractures coupled dual-porosity-media representation elementary volume (REV) flow model to predict the volumetric flux of gas in shale reservoirs. On the basis of the migration of adsorbed gas in porous kerogen of REV with different fracture spaces, an ESRV criterion for shale reservoirs with SRV is proposed. Eventually, combining the ESRV criterion and fractal characteristic of a fracture network, we propose a new approach for evaluating ESRV in shale reservoirs. The approach has been used in the Eagle Ford shale gas reservoir, and results show that the fracture space has a measurable influence on migration of adsorbed gas. The fracture network can contribute to enhancement of the absorbed gas recovery ratio when the fracture space is less than 0.2 m. ESRV is evaluated in this paper, and results indicate that the ESRV accounts for 27.87% of the total SRV in shale gas reservoirs. This work is important and timely for evaluating fracturing effect and predicting production of hydraulic fracturing wells in shale reservoirs.

Lunar and Planetary Science XXXVI, Part 4

NASA Technical Reports Server (NTRS)

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.

The source rock potential of the Karroo coals of the south western Rift Basin of Tanzania

NASA Astrophysics Data System (ADS)

Mpanju, F.; Ntomola, S.; Kagya, M.

For many years geoscientists believed that coals (Type III Kerogen) generate gas only. The geochemical study of Durand and Parrante ( Petrolum Geochemistry and Exploration of Europe, pp. 255-265, 1983) revealed that coals have reasonable potential for oil generation. On this basis forty outcrop samples of Lower and Upper Permian age, i.e. coals and carbonaceous shales, were collected from the south western Rift Basin of Tanzania. The aim of the study was to determine the richness, type, maturity and hydrocarbon potential of the above samples. These samples were subjected to both geochemical and petrological analyses. Geochemical analyses included solvent extraction, TOC, GC, GC-MS and pyrolysis. The petrological analysis included vitrinite reflectance, spore fluorescence and maceral content. The geochemical analyses showed all samples to be rich in organic matter of Types II and III and samples from Songwe Kiwira, Namwele, Mbamba Bay, Njuga and Mhukuru coalfields were in an early mature-mature stage of hydrocarbon generation. Whereas samples from Ketewaka and Ngaka coalfields showed a GC-trace of early generated waxy oil. All samples contained organic matter derived from terrestrial material which was deposited under oxic environment. The Hydrogen Index of most coals and carbonaceous shales was greater than 200 indicating that they can generate oil or light oil. Petrological observations showed all samples to be in the range of 0.47-0.67% Ro and some of them were rich in both liptinite and vitrinite macerals. From both geochemical and petrological observations it was concluded that the Lower and Upper Permian coals and carbonaceous shales under study are probably capable of generating oil. The oil generated has the same characteristics as that generated by Cretaceous and Tertiary coals discovered from other parts of the world, i.e. Adjuna and Kutei Basins in Indonesia and the Gippsland Basin in Australia (Kirkland et al., AAPG Bull.71, 577, 1987).

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

NASA Technical Reports Server (NTRS)

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.

Evaluation of shale gas potential based on organic matter characteristics and gas concentration in the Devonian Horn River Formation, Canada

NASA Astrophysics Data System (ADS)

Choi, Jiyoung; Hong, Sung Kyung; Lee, Hyun Suk

2017-04-01

In this study, we investigate organic matter characteristics from the analysis of Rock-Eval6 and biomarker, and estimate methane concentration from headspace method in the Devonian Horn River Formation, which is one of the largest shale reservoir in western Canada. The Horn River Formation consists of the Evie, Otterpark and Muskwa members in ascending stratigraphic order. Total Organic Carbon (TOC) ranges from 0.34 to 7.57 wt%, with an average of 2.78 wt%. The Evie, middle Otterpark and Muskwa members have an average TOC of more than 3%, whereas those of the lower and upper Otterpark Member are less than 2%. Based on Pristane/n-C17 (0.2 0.6) and Phytane/n-C18 (0.3 0.9) ratios, the organic matter in the Evie, middle Otterpark and Muskwa members mainly consists of type II kerogen which are formed in reducing marine environment. Thermal maturity were examined through the use of the distributions of Phenanthrene (P) and Methylphenantrenes (MP) based on m/z 178 and 192 mass chromatograms, respectively (Radke et al., 1982). The methylphenanthrene index (MPI-1) are calculated as follows : MPI-1 = 1.5 × (2MP+3MP)/(P+1MP+9MP), and Ro are calculated as follows : Ro = -0.6 × MPI-1 + 2.3. Estimated Ro ranges between 1.88 and 1.93%, which indicates the last stage of wet gas generation. The methane concentrations in headspace range from 15 to 914 ppmv, with an average of 73.5 ppmv. The methane concentrations in the Evie, middle Otterpark and Muskwa members (up to 914 ppmv) are higher than those of the lower and upper Otterpark Member (up to 75 ppmv). Considering the organic geochemical characteristics and gas concentrations, the shale gas potentials of the Evie, middle Otterpark and Muskwa members are higher than those of other members.

Behavior of water in supercritical CO2: adsorption and capillary condensation in porous media

NASA Astrophysics Data System (ADS)

Heath, J. E.; Bryan, C. R.; Dewers, T. A.; Wang, Y.

2011-12-01

The chemical potential of water in supercritical CO2 (scCO2) may play an important role in water adsorption, capillary condensation, and evaporation under partially saturated conditions at geologic CO2 storage sites, especially if initially anhydrous CO2 is injected. Such processes may affect residual water saturations, relative permeability, shrink/swell of clays, and colloidal transport. We have developed a thermodynamic model of water or brine film thickness as a function of water relative humidity in scCO2. The model is based on investigations of liquid water configuration in the vadose zone and uses the augmented Young-Laplace equation, which incorporates both adsorptive and capillary components. The adsorptive component is based on the concept of disjoining pressure, which reflects force per area normal to the solid and water/brine-scCO2 interfaces. The disjoining pressure includes van der Waals, electrostatic, and structural interactions. The van der Waals term includes the effects of mutual dissolution of CO2 and water in the two fluid phases on partial molar volumes, dielectric coefficients, and refractive indices. Our approach treats the two interfaces as asymmetric surfaces in terms of charge densities and electrostatic potentials. We use the disjoining pressure isotherm to evaluate the type of wetting (e.g., total or partial wetting) for common reservoir and caprock minerals and kerogen. The capillary component incorporates water activity and is applied to simple pore geometries with slits and corners. Finally, we compare results of the model to a companion study by the coauthors on measurement of water adsorption to mineral phases using a quartz-crystal microbalance. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

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

PubMed

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

Four dimensional X-ray imaging of deformation modes in organic-rich Green River Shale retorted under uniaxial compression

NASA Astrophysics Data System (ADS)

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

Organic Analysis in the Miller Range 090657 CR2 Chondrite: Part 2 Amino Acid Analyses

NASA Technical Reports Server (NTRS)

Burton, A. S.; Cao, T.; Nakamura-Messenger, K.; Berger, E. L.; Messenger, S.; Clemett, S. J.; Aponte, J. C.; Elsila, J. E.

2016-01-01

Primitive carbonaceous chondrites contain a wide variety of organic material, ranging from soluble discrete molecules to insoluble, unstructured kerogen-like components, as well as structured nano-globules of macromolecular carbon. The relationship between the soluble organic molecules, macromolecular organic material, and host minerals are poorly understood. Due to the differences in extractability of soluble and insoluble organic materials, the analysis methods for each differ and are often performed independently. The combination of soluble and insoluble analyses, when performed concurrently, can provide a wider understanding of spatial distribution, and elemental, structural and isotopic composition of organic material in primitive meteorites. Using macroscale extraction and analysis techniques in combination with in situ microscale observation, we have been studying both insoluble and soluble organic material in the primitive CR2 chondrite Miller Range (MIL) 090657. In accompanying abstracts (Cao et al. and Messenger et al.) we discuss insoluble organic material in the samples. By performing the consortium studies, we aim to improve our understanding of the relationship between the meteorite minerals and the soluble and insoluble organic phases and to delineate which species formed within the meteorite and those that formed in nebular or presolar environments. In this abstract, we present the results of amino acid analyses of MIL 090657 by ultra performance liquid chromatography with fluorescence detection and quadrupole-time of flight mass spectrometry. Amino acids are of interest because they are essential to life on Earth, and because they are present in sufficient structural, enantiomeric and isotopic diversity to allow insights into early solar system chemical processes. Furthermore, these are among the most isotopically anomalous species, yet at least some fraction are thought to have formed by aqueously-mediated processes during parent body alteration.

Diversity of Microfossils and Preservation of Thermally Altered Stromatolites from Anomalous Precambrian Paleoenvironments

NASA Astrophysics Data System (ADS)

Osterhout, Jeffrey Thomas

Studies of Precambrian life on Earth have been dominated by those of shallow marine deposits, and in order to gain a more complete picture of life's early evolution it is important to consider a wider range of inhabited environments, including deep marine and terrestrial ecosystems. Evidence for early microbial life comes primarily from fossil microorganisms (microfossils), microbial sedimentary structures (e.g., stromatolites), and sedimentary organic matter (e.g., kerogen). The diversity and preservation of these different forms of fossil evidence introduces several challenges to their interpretation, requiring thorough analysis for accurately determining their biological origins. Investigating the paleobiology, organic geochemistry, and thermal maturity of such deposits provides a holistic approach to exploring the Precambrian biosphere in unfamiliar paleoenvironments. This thesis presents two studies of unique Precambrian ecosystems: a diverse microfossil assemblage from a 2.52-billion-year-old (Ga) deep marine deposit, and thermally altered stromatolites from a 1.4-billion-year-old evaporitic lacustrine deposit. Black cherts from the upper Gamohaan Formation (2.52 Ga) contain a consortium of organic-walled large and small coccoids, tubular filaments, and mat-like biofilm structures. Geochemical analyses of stromatolitic chert-carbonate from the Middlebrun Bay Member (1.4 Ga) in contact with a mafic sill show a trend in organic carbon isotopes relative to thermal maturity that is contrary to theoretical predictions. Findings from these studies reveal, for the first time, microfossil evidence of a diverse microbial community in the open Archean ocean prior to the Great Oxidation Event (GOE) 2.4 billion years ago, and provide insight on the relationship between thermal maturity and organic carbon isotopes within a set of terrestrial stromatolites. Together, these studies help capture the enigmatic nature of the Precambrian fossil record and expand our full

Reaction rate kinetics for in situ combustion retorting of Michigan Antrim oil shale

USGS Publications Warehouse

Rostam-Abadi, M.; Mickelson, R.W.

1984-01-01

The intrinsic reaction rate kinetics for the pyrolysis of Michigan Antrim oil shale and the oxidation of the carbonaceous residue of this shale have been determined using a thermogravimetric analysis method. The kinetics of the pyrolysis reaction were evaluated from both isothermal and nonisothermal rate data. The reaction was found to be second-order with an activation energy of 252.2 kJ/mole, and with a frequency factor of 9.25 ?? 1015 sec-1. Pyrolysis kinetics were not affected by heating rates between 0.01 to 0.67??K/s. No evidence of any reactions among the oil shale mineral constituents was observed at temperatures below 1173??K. However, it was found that the presence of pyrite in oil shale reduces the primary devolatilization rate of kerogen and increases the amount of residual char in the spent shale. Carbonaceous residues which were prepared by heating the oil shale at a rate of 0.166??K/s to temperatures between 923??K and 1073??K, had the highest reactivities when oxidized at 0.166??K/s in a gas having 21 volume percent oxygen. Oxygen chemisorption was found to be the initial precursor to the oxidation process. The kinetics governing oxygen chemisorption is (Equation Presented) where X is the fractional coverage. The oxidation of the carbonaceous residue was found also to be second-order. The activation energy and the frequency factor determined from isothermal experiments were 147 kJ/mole and 9.18??107 sec-1 respectively, while the values of these parameters obtained from a nonisothermal experiment were 212 kJ/mole and 1.5??1013 sec-1. The variation in the rate constants is attributed to the fact that isothermal and nonisothermal analyses represent two different aspects of the combustion process.

Micro-Scale Sulfur and Carbon Isotope Analysis of a Neoarchean Stromatolite: Evidence for a Profound Redox Transition in Shelf Margins prior to the Great Oxidation Event

NASA Astrophysics Data System (ADS)

Ilhardt, P.; House, C. H.; Altermann, W.

2016-12-01

Neoarchean shelf margin environments such as the Campbellrand-Malmani platform are believed to have been sites of substantial O2 accumulation and nutrient cycling prior to the Great Oxidation Event (GOE). Stromatolites in particular serve as biogeochemical "hotspots" where evidence of various metabolic pathways and bacterial lineages can be traced through geochemical fingerprints. We identified morphologically-unique, organic-rimmed pyrite grains embedded in the dolomitic lamina of a Campbellrand Subgroup stromatolite (2.6 Ga). Carbon and sulfur isotopes measured in situ revealed a multi-layered microbial community employing photoautotrophic carbon fixation, organic matter respiration, sulfate reduction, and potentially assimilation of methane. In particular, unusually high kerogen δ13Corg and pyrite δ34S compositions are consistent with a semi-aerobic ecosystem recycling photosynthetic biomass and sulfate reduction in sulfate-limited porewaters, respectively. In addition, an array of positive Δ33S values suggests incorporation of atmospherically-derived sulfur formed from volcanic SO2 photochemistry and isolated in particulate form. We argue the Δ33S-δ34S trend is best explained by mixing between a δ34S-enriched coastal marine sulfate reservoir and stratospheric Δ33S-positive sulfate or elemental sulfur aerosols. The hypothesized buildup of sulfur gases at higher altitudes agrees with prior arguments for increased subaerial felsic volcanism and intense plume activity coinciding with oxidation of the upper mantle. We suggest explosive subaerial eruptions sustained a stratospheric SO2 reservoir that underwent photochemistry via long-wavelength (250-330 nm) UV radiation to produce positive MIF-carrying aerosol particles (sulfate or sulfur) in the Neoarchean. This contrasts with Paleoarchean sulfur chemistry dominated by SO2 photolysis in the 190-220 nm excitation band and points to an evolving Archean atmosphere, culminating in a coupled biogeochemical

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

NASA Astrophysics Data System (ADS)

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.

Petroleum systems of Zhu III depression in Pearl River Mouth Basin, South China Sea

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

Weilin, Zhu; Li Mingbi; Wu Peikang

Zhu III depression is located in the west part of Pearl River Mouth Basin, and covers an area of 11,000 sq km. Until now more than twenty wells have been drilled in the depression and its surrounding area, and all oil-gas fields and oil-gas discoveries are concentrated inside the depression. Integrated study indicates that there are two petroleum systems in Zhu III depression. One is Wenchang - Zhuhai, Zhujiang oil system which is mainly distributed in Wenchang B sag in the southwest part of the depression. Its source rock, the Wenchang formation is mainly composed of dark mudstone of lacustrinemore » facies, with thicknesses up to more than 1000 m. Its reservoir includes tidal sandstone of transitional facies of Zhuhai formation and neritic sandstone of the lower part of Zhujiang formation. Through bounding faults and margin coarse sediment zone, oil generated from the Wenchang formation migrated into overlying sandstone of Zhuhai formation, which was overlaid by mudstone beds of bay facies of Zhuhai formation or neritic facies of Zhujiang formation, and formed oil accumulations. The other system is Enping - Zhuhai gas system, distributed in Wenchang A sag in the northeast part of the depression, whose source rock in the Enping formation deposited in the contracting stage of the lake, dominated by swamp coal measure in lithology and terrestrial plant clastics in kerogen components. The gas generated from Enping formation directly migrated into overlying tidal sandstone of Zhuhai formation and formed gas accumulations. Therefore, exploration in Wenchang A sag in the northeast part of the depression is for gas accumulations, and oil accumulations in Wenchang B sag in the southwest part of the depression, while oil-gas mixed accumulations are likely to be found in the transitional area of two systems.« less

A Modern Analogue for Proterozoic Inverse Carbon Isotope Signatures

NASA Astrophysics Data System (ADS)

Close, H. G.; Diefendorf, A. F.; Freeman, K. H.; Pearson, A.

2008-12-01

The carbon isotope distribution preserved in sedimentary lipids changes near the Neoproterozoic-Cambrian boundary. In older samples, n-alkyl lipids contain more 13C than both isoprenoid lipids and kerogen [1]. In younger samples, the opposite prevails. Although extreme heterotrophy has been invoked as a mechanism to explain the enrichment in 13C [2], here we suggest another explanation. The switch may reflect a fundamental transition from an oligotrophic ocean dominated by prokaryotic biomass, to an ocean in which carbon fixation is more intensive and burial is dominated by eukaryotic biomass. An analogue for Proterozoic ordering is found in the modern, oligotrophic Pacific Ocean, where n-alkyl lipids of picoplankton (0.2-0.5 μm particulate matter) contain excess 13C relative to the same lipids found in larger size classes (> 0.5 μm). Picoplanktonic lipids are heavier isotopically (-18 ‰) than both the sterols of eukaryotes (-23 ‰ to -26 ‰) and the total organic matter (-20 ‰; TOM). The 0.2-0.5 μm size class also has a distinct chain-length abundance profile. Although large particles must be the vehicle for total carbon export, paradoxically the lipid component of export production appears to be dominated by the 0.2-0.5 μm source. The picoplanktonic chain lengths and isotopic composition dominate lipids of TOM at 670 meters. When the ratio of prokaryotic to eukaryotic production is high, as in the modern central Pacific Ocean, it appears that exported material has an inverse carbon isotope signature similar to that preserved in Precambrian samples. [1] Logan, G. A. et al., Nature 376:53-56 (1995). [2] Rothman, D. H. et al., PNAS 100:8124-8129 (2003).

THE FIRST DISCOVERY OF PRESOLAR GRAPHITE GRAINS FROM THE HIGHLY REDUCING QINGZHEN (EH3) METEORITE

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

Xu, Yuchen; Lin, Yangting; Zhang, Jianchao

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,more » 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.« less

Organic and clay mineral diagenesis in Neogene sediments of western Taiwan

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

Hsueh, C.M.

1985-01-01

Three deep wells (two in the northern region and one in the southern region) with completion depths of over 5000m have been selected and the rock samples thoroughly examined. The TOC data of most samples studied are less than 1%, which is the TOC of an average shale. The low TOC is unfavorable for the Neogene sediments in western Taiwan as good source rocks. The data of C,H elemental analysis and Rock-Eval pyrolysis imply that the quality of kerogen in the northern region inclines to type II wet-gas prone, and in the southern region inclines to type III dry-gas prone.more » The maturity parameters of bitumen ratio, vitrinite reflectance, Tmax of Rock-Eval pyrolysis, and TTI of Lopatin's method show that the threshold of the oil-generative zone (about 0.6% Ro) in the northern region is in middle Miocene (about 3000m) and in the southern region is in lower Pliocene (about 4500m). The result of clay mineral analysis reveals that the transformation of smectitic clays to ordered mixed-layered smectite-illite can be identified and correlated with 0.6% Ro vitrinite reflectance. The illite crystallinity values are in the range of incipient to weak metamorphism and decrease with burial depth implying that the source area of low-grade metamorphic rocks has been uplifted rapidly so that the erosion from the exposed source area where the metamorphic grade became higher and higher was sufficiently fast to prevent weathering of illite. The Neogene sediments studied would not be expected to generate substantial amounts of oil. However, it can be expected that the pre-Miocene sediments in the northern region and the pre-Pliocene sediments in the southern region should have generated substantial amounts of gas at deeper depths.« less

Evolution of oil-generative window and oil and gas occurrence in Tertiary Niger delta basin/sup 1/

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

Ejedawe, J.E.; Adoh, F.O.; Alofe, K.B.

1984-11-01

Assuming a simple model of delta development involving progradation and uniform burial at 500 m/m.y. (1,640 ft/m.y.) to present depths, oil-genesis nomographs derived from the time-temperature index (TTI) method were constructed for geothermal gradients ranging from 2.2/sup 0/ to 5.1/sup 0/ C/100 m (1.2/sup 0/-2.8/sup 0/ F/100 ft) of the Niger delta and used in mapping the positions (depth, temperature) of the top of the oil-generative window (OGW) at various times between 40 m.y.B.P. and the present. During the active subsidence phase, oil generation within any megasedimentary unit was initiated at a temperature of 140/sup 0/-146/sup 0/C (284/sup 0/-294.8/sup 0/F)more » and depth of 3,000-5,200 m (9,843-17,060 ft) within 7-11 m.y. after deposition of the potential source rocks. After cessation of subsidence, vertical upward movement of the OGW by 800-1,600 m (2,625-5,249 ft) was accompanied by a temperature lowering of 23/sup 0/-54/sup 0/C (41/sup 0/-97/sup 0/F), producing correspondingly heavier crudes. In a central belt of the delta, hydrocarbon generation and expulsion from the lower part of the Agbada Formation predate the cessation of subsidence and structural deformation, whereas, in other areas, it postdates the cessation of subsidence and structural deformation. In this central belt, the Agbada is the major oil source, with the Akata serving as a gas source. In the other areas, both the Agbada and Akata constitute oil sources, which implies that the thermal conditions rather than the kerogen type influence the oil/gas mix in the Niger delta basin.« less

Mesozoic black shales, source mixing and carbon isotopes

NASA Astrophysics Data System (ADS)

Suan, Guillaume

2016-04-01

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

Allochthonous Addition of Meteoritic Organics to the Lunar Regolith

NASA Technical Reports Server (NTRS)

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.

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

Schiefelbein, C.; Ho, T.

Changes in the physical properties (measured in terms of vitrinite reflectance, elemental analysis, and C-13 nuclear magnetic resonance) of an immature coal (0.46% R{sub o}) from Craig County, Colorado, that was thermally altered using hydrous pyrolysis were used to establish a correspondence between hydrous pyrolysis time/temperature reaction conditions and relative maturity (expressed in terms of vitrinite reflectance). This correspondence was used to determine the oil generation maturity limits for an immature hydrogen-rich (Type I fluorescing amorphous oil-prone kerogen) source rock from an offshore Congo well that was thermally altered using the same reaction conditions as applied to the immature coal.more » The resulting changes in the physical properties of the altered source rock, measured in terms of decreasing reactive carbon content (from Rock-Eval pyrolysis), were used to construct a hydrocarbon yield curve from which the relative maturity associated with the onset, main phase, and peak of oil generation was determined. Results, substantiated by anhydrous pyrolysis techniques, indicate that the source rock from Congo has a late onset of appreciable ({gt}10% transformation) oil generation (0.9% R{sub o} {plus minus} 0.1%), generates maximum quantities of oil from about 1.1 to 1.3% R{sub o}, and reaches the end (or peak) of the primary oil generating window at approximately 1.4% R{sub o} ({plus minus}0.1%) when secondary cracking reactions become important. However, the bottom of the oil window can be extended to about 1.6% R{sub o} because the heavy molecular weight degradation by-products (asphaltenes) that are not efficiently expelled from source rocks continue to degrade into progressively lower molecular weight hydrocarbons.« less

Fatty acids in sparry calcite fracture fills and microsparite cement of septarian diagenetic concretions

NASA Astrophysics Data System (ADS)

Pearson, M. J.; Hendry, J. P.; Taylor, C. W.; Russell, M. A.

2005-04-01

Sparry calcite fracture fills and concretion body cements in concretions from the Flodigarry Shale Member of the Staffin Shale Formation, Isle of Skye, Scotland, entrap and preserve mineral and organic materials of sedimentary and diagenetic origin. Fatty acids are a major component of the lipids recovered by decarbonation and comprise mainly n-alkanoic and α-ω dicarboxylic acids. Two generations of fracture-fill calcite (early brown and later yellow) and the concretion body microspar yield significantly different fatty acid profiles. Early brown calcites yield mainly medium-chain n-alkanoic acids with strong even predominance; later yellow calcites are dominated by α-ω dicarboxylic acids with no even predominance. Both fracture fills lack the long-chain n-alkanoic and α-ω dicarboxylic acids additionally recovered from the concretion bodies. The absence of longer chain acids in the calcite spar fracture fills is inferred to result from the transport of fatty acids by septarian mineralising fluids whereby low-aqueous solubility of longer chain acids or their salts accounts for their relative immobility. Comparative experiments have been carried out using conventional solvent extraction on the concretion body and associated shales, both decarbonated and untreated. Extracted lipid yields are higher, but the fatty acids probably derive from mixed locations in the rock including both kerogen- and carbonate-associated lipid pools. Only experiments involving decarbonation yielded α-ω dicarboxylic acids in molecular distributions probably controlled mainly by fluid transport. Alkane biomarker ratios indicate very low thermal maturity has been experienced by the concretions and their host sediments. Septarian cracks lined by brown calcite formed during early burial. Microbial CO 2 from sulphate-reducing bacteria was probably the main source of mineralising carbonate. Emplacement of the later septarian fills probably involved at least one episode of fluid invasion.

Understanding the application of Raman spectroscopy to the detection of traces of life.

PubMed

Marshall, Craig P; Edwards, Howell G M; Jehlicka, Jan

2010-03-01

Investigating carbonaceous microstructures and material in Earth's oldest sedimentary rocks is an essential part of tracing the origins of life on our planet; furthermore, it is important for developing techniques to search for traces of life on other planets, for example, Mars. NASA and ESA are considering the adoption of miniaturized Raman spectrometers for inclusion in suites of analytical instrumentation to be placed on robotic landers on Mars in the near future to search for fossil or extant biomolecules. Recently, Raman spectroscopy has been used to infer a biological origin of putative carbonaceous microfossils in Early Archean rocks. However, it has been demonstrated that the spectral signature obtained from kerogen (of known biological origin) is similar to spectra obtained from many poorly ordered carbonaceous materials that arise through abiotic processes. Yet there is still confusion in the literature as to whether the Raman spectroscopy of carbonaceous materials can indeed delineate a signature of ancient life. Despite the similar nature in spectra, rigorous structural interrogation between the thermal alteration products of biological and nonbiological organic materials has not been undertaken. Therefore, we propose a new way forward by investigating the second derivative, deconvolution, and chemometrics of the carbon first-order spectra to build a database of structural parameters that may yield distinguishable characteristics between biogenic and abiogenic carbonaceous material. To place Raman spectroscopy as a technique to delineate a biological origin for samples in context, we will discuss what is currently accepted as a spectral signature for life; review Raman spectroscopy of carbonaceous material; and provide a historical overview of Raman spectroscopy applied to Archean carbonaceous materials, interpretations of the origin of the ancient carbonaceous material, and a future way forward for Raman spectroscopy.

The Future of Fossil Fuels: A Century of Abundance or a Century of Decline?

NASA Astrophysics Data System (ADS)

Nelder, C.

2012-12-01

Horizontal drilling, hydraulic fracturing, and other advanced technologies have spawned a host of new euphoric forecasts of hydrocarbon abundance. Yet although the world's remaining oil and gas resources are enormous, most of them are destined to stay in the ground due to real-world constraints on price, flow rates, investor appetite, supply chain security, resource quality, and global economic conditions. While laboring under the mistaken belief that it sits atop a 100-year supply of natural gas, the U.S. is contemplating exporting nearly all of its shale gas production even as that production is already flattening due to poor economics. Instead of bringing "energy independence" to the U.S. and making it the top oil exporter, unrestricted drilling for tight oil and in the federal outer continental shelf would cut the lifespan of U.S. oil production in half and make it the world's most desperate oil importer by mid-century. And current forecasts for Canadian tar sands production are as unrealistic as their failed predecessors. Over the past century, world energy production has moved progressively from high quality resources with high production rates and low costs to lower quality resources with lower production rates and higher costs, and that progression is accelerating. Soon we will discover the limits of practical extraction, as production costs exceed consumer price tolerance. Oil and gas from tight formations, shale, bitumen, kerogen, coalbeds, deepwater, and the Arctic are not the stuff of new abundance, but the oil junkie's last dirty fix. This session will highlight the gap between the story the industry tells about our energy future, and the story the data tells about resource size, production rates, costs, and consumer price tolerance. It will show why it's time to put aside unrealistic visions of continued dependence on fossil fuels, face up to a century of decline, and commit ourselves to energy and transportation transition.

New insights on the Frasnian/Famennian mass extinction: a role for soil erosion?

NASA Astrophysics Data System (ADS)

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

In situ trace metal analysis of Neoarchaean--Ordovician shallow-marine microbial-carbonate-hosted pyrites.

PubMed

Gallagher, M; Turner, E C; Kamber, B S

2015-07-01

Pre-Cambrian atmospheric and oceanic redox evolutions are expressed in the inventory of redox-sensitive trace metals in marine sedimentary rocks. Most of the currently available information was derived from deep-water sedimentary rocks (black shale/banded iron formation). Many of the studied trace metals (e.g. Mo, U, Ni and Co) are sensitive to the composition of the exposed land surface and prevailing weathering style, and their oceanic inventory ultimately depends on the terrestrial flux. The validity of claims for increased/decreased terrestrial fluxes has remained untested as far as the shallow-marine environment is concerned. Here, the first systematic study of trace metal inventories of the shallow-marine environment by analysis of microbial carbonate-hosted pyrite, from ca. 2.65-0.52 Ga, is presented. A petrographic survey revealed a first-order difference in preservation of early diagenetic pyrite. Microbial carbonates formed before the 2.4 Ga great oxygenation event (GOE) are much richer in pyrite and contain pyrite grains of greater morphological variability but lesser chemical substitution than samples deposited after the GOE. This disparity in pyrite abundance and morphology is mirrored by the qualitative degree of preservation of organic matter (largely as kerogen). Thus, it seems that in microbial carbonates, pyrite formation and preservation were related to presence and preservation of organic C. Several redox-sensitive trace metals show interpretable temporal trends supporting earlier proposals derived from deep-water sedimentary rocks. Most notably, the shallow-water pyrite confirms a rise in the oceanic Mo inventory across the pre-Cambrian-Cambrian boundary, implying the establishment of efficient deep-ocean ventilation. The carbonate-hosted pyrite also confirms the Neoarchaean and early Palaeoproterozoic ocean had higher Ni concentration, which can now more firmly be attributed to a greater proportion of magnesian volcanic rock on land rather

North Slope, Alaska: Source rock distribution, richness, thermal maturity, and petroleum charge

USGS Publications Warehouse

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

Using Neutrons to Study Fluid-Rock Interactions in Shales

NASA Astrophysics Data System (ADS)

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

Compaction bands in high temperature/pressure diagenetically altered unconventional shale gas reservoirs

NASA Astrophysics Data System (ADS)

Regenauer-Lieb, K.; Veveakis, M.; Poulet, T.

2014-12-01

Unconventional energy and mineral resources are typically trapped in a low porosity/permeability environment and are difficult to produce. An extreme end-member is the shale gas reservoir in the Cooper Basin (Australia) that is located at 3500-4000 m depth and ambient temperature conditions around 200oC. Shales of lacustrine origin (with high clay content) are diagenetically altered. Diagenesis involves fluid release mineral reactions of the general type Asolid ↔ Bsolid +Cfluid and switches on suddenly in the diagenetic window between 100-200oC. Diagenetic reactions can involve concentrations of smectite, aqueous silica compound, illite, potassium ions, aqueous silica, quartz, feldspar, kerogen, water and gas . In classical petroleum engineering such interlayer water/gas release reactions are considered to cause cementation and significantly reduce porosity and permeability. Yet in contradiction to the expected permeability reduction gas is successfully being produced. We propose that the success is based on the ductile equivalent of classical compaction bands in solid mechanics. The difference being that that the rate of the volumetric compaction is controlled by the diagenetic reactions. Ductile compaction bands are forming high porosity fluid channels rather than low porosity crushed grains in the solid mechanical equivalent. We show that this new type of volumetric instability appears in rate-dependent heterogenous materials as Cnoidal waves. These are nonlinear and exact periodic stationary waves, well known in the shallow water theory of fluid mechanics. Their distance is a direct function of the hydromechanical diffusivities. These instabilities only emerge in low permeability environment where the fluid diffusivity is about an order of magnitude lower than the mechanical loading. The instabilities are expected to be of the type as shown in the image below. The image shows a CT-scan of a laboratory experiment kindly provided by Papamichos (pers

Mongolian Oil Shale, hosted in Mesozoic Sedimentary Basins

NASA Astrophysics Data System (ADS)

Bat-Orshikh, E.; Lee, I.; Norov, B.; Batsaikhan, M.

2016-12-01

Mongolia contains several Mesozoic sedimentary basins, which filled >2000 m thick non-marine successions. Late Triassic-Middle Jurassic foreland basins were formed under compression tectonic conditions, whereas Late Jurassic-Early Cretaceous rift valleys were formed through extension tectonics. Also, large areas of China were affected by these tectonic events. The sedimentary basins in China host prolific petroleum and oil shale resources. Similarly, Mongolian basins contain hundreds meter thick oil shale as well as oil fields. However, petroleum system and oil shale geology of Mongolia remain not well known due to lack of survey. Mongolian oil shale deposits and occurrences, hosted in Middle Jurassic and Lower Cretaceous units, are classified into thirteen oil shale-bearing basins, of which oil shale resources were estimated to be 787 Bt. Jurassic oil shale has been identified in central Mongolia, while Lower Cretaceous oil shale is distributed in eastern Mongolia. Lithologically, Jurassic and Cretaceous oil shale-bearing units (up to 700 m thick) are similar, composed mainly of alternating beds of oil shale, dolomotic marl, siltstone and sandstone, representing lacustrine facies. Both Jurassic and Cretaceous oil shales are characterized by Type I kerogen with high TOC contents, up to 35.6% and low sulfur contents ranging from 0.1% to 1.5%. Moreover, S2 values of oil shales are up to 146 kg/t. The numbers indicate that the oil shales are high quality, oil prone source rocks. The Tmax values of samples range from 410 to 447, suggesting immature to early oil window maturity levels. PI values are consistent with this interpretation, ranging from 0.01 to 0.03. According to bulk geochemistry data, Jurassic and Cretaceous oil shales are identical, high quality petroleum source rocks. However, previous studies indicate that known oil fields in Eastern Mongolia were originated from Lower Cretaceous oil shales. Thus, further detailed studies on Jurassic oil shale and its

Evaluating transition-metal catalysis in gas generation from the Permian Kupferschiefer by hydrous pyrolysis

USGS Publications Warehouse

Lewan, M.D.; Kotarba, M.J.; Wieclaw, D.; Piestrzynski, A.

2008-01-01

Transition metals in source rocks have been advocated as catalysts in determining extent, composition, and timing of natural gas generation (Mango, F. D. (1996) Transition metal catalysis in the generation of natural gas. Org. Geochem.24, 977–984). This controversial hypothesis may have important implications concerning gas generation in unconventional shale-gas accumulations. Although experiments have been conducted to test the metal-catalysis hypothesis, their approach and results remain equivocal in evaluating natural assemblages of transition metals and organic matter in shale. The Permian Kupferschiefer of Poland offers an excellent opportunity to test the hypothesis with immature to marginally mature shale rich in both transition metals and organic matter. Twelve subsurface samples containing similar Type-II kerogen with different amounts and types of transition metals were subjected to hydrous pyrolysis at 330° and 355 °C for 72 h. The gases generated in these experiments were quantitatively collected and analyzed for molecular composition and stable isotopes. Expelled immiscible oils, reacted waters, and spent rock were also quantitatively collected. The results show that transition metals have no effect on methane yields or enrichment. δ13C values of generated methane, ethane, propane and butanes show no systematic changes with increasing transition metals. The potential for transition metals to enhance gas generation and oil cracking was examined by looking at the ratio of the generated hydrocarbon gases to generated expelled immiscible oil (i.e., GOR), which showed no systematic change with increasing transition metals. Assuming maximum yields at 355 °C for 72 h and first-order reaction rates, pseudo-rate constants for methane generation at 330 °C were calculated. These rate constants showed no increase with increasing transition metals. The lack of a significant catalytic effect of transition metals on the extent, composition, and timing of

Simulations of the origin of fluid pressure, fracture gen­ eration, and the movement of fluids in the Uinta Basin, Utah

USGS Publications Warehouse

Bredehoeft, J.D.; Wesley, J.B.; Fouch, T.D.

1994-01-01

The Altamont oil field in the deep Uinta basin is known to have reservoir fluid pressures that approach lithostatic. One explanation for this high pore-fluid pressure is the generation of oil from kerogen in the Green River oil shale at depth. A three-dimensional simulation of flow in the basin was done to test this hypothesis.In the flow simulation, oil generation is included as a fluid source. The kinetics of oil generation from oil shale is a function of temperature. The temperature is controlled by (1) the depth of sediment burial and (2) the geothermal gradient.Using this conceptual model, the pressure buildup results from the trade-off between the rate of oil generation and the flow away from the source volume. The pressure increase depends primarily on (1) the rate of the oil-generation reaction and (2) the permeability of the reservoir rocks. A sensitivity analysis was performed in which both of these parameters were systematically varied. The reservoir permeability must be lower than most of the observed data for the pressure to build up to near lithostatic.The results of the simulations indicated that once oil generation was initiated, the pore pressure built up rapidly to near lithostatic. We simulated hydrofractures in that part of the system in which the pressures approach lithostatic by increasing both the horizontal and the vertical permeability by an order of magnitude. Because the simulated hydrofractures were produced by the high pore pressure, they were restricted to the Altamont field. A new flow system was established in the vicinity of the reservoir; the maximum pore pressure was limited by the least principal stress. Fluids moved vertically up and down and laterally outward away from the source of oil generation. The analysis indicated that, assuming that one is willing to accept the low values of permeability, oil generati n can account for the observed high pressures at Altamont field.

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

NASA Astrophysics Data System (ADS)

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

Determination of elemental carbon in lake sediments using a thermal-optical transmittance (TOT) method

NASA Astrophysics Data System (ADS)

Khan, A. J.; Swami, Kamal; Ahmed, Tanveer; Bari, A.; Shareef, Akhtar; Husain, Liaquat

2009-12-01

An improved chemical oxidation pretreatment method has been developed for the determination of elemental carbon (EC) [also known as black carbon (BC) or soot] in lake sediments, using a thermal-optical transmittance (TOT) carbon analyzer. The method employs six steps: (1) removal of carbonates by treatment with HCl; (2) removal of silicates by treatment with HF + HCl; (3) removal of any remaining carbonates by treatment with HCl; (4) removal of humic acids by treatment with NaOH; and (5) oxidation of kerogens by K 2Cr 2O 7 + H 2SO 4. A critical step of zinc chloride treatment was added; this apparently changes EC's morphology and enhances retention on quartz fiber filter, resulting in several-fold increased chemical yield. EC was determined using the TOT method with modified combustion timings. Carbon black (acetylene) and four NIST standard reference materials (SRMs) were used for quality control, and to assess the precision of the analysis. The EC recoveries from 18 carbon black samples varied from 90 to 111%, with a mean value of 99 ± 6%. The high EC recoveries confirmed the validity of the method. Char reference materials (i.e. chestnut wood and grass char) were used to determine potential contribution to EC in our measurements. The char references containing about 700 mg total organic carbon (OC) contributed ˜1.5% EC. The measured EC values from four NIST standards were 17.0 ± 0.6, 24.2 ± 3.2, 5.6, and 1.9 ± 0.1 mg g dw-1 for SRM-1648, SRM-1649a, SRM-1941b and SRM-8704, respectively. These values in SRMs were in agreement (<±4%) with the previously reported values. The method was applied to determine the EC in sediment cores from an urban lake and a remote mountain lake in the Northeastern United States. The EC concentrations in two lakes mimic the model EC emissions from the industrial revolution in United States.

A surface vitrinite reflectance anomaly related to Bell Creek oil field, Montana, U.S.A.

USGS Publications Warehouse

Barker, C.E.; Dalziel, M.C.; Pawlewicz, M.J.

1983-01-01

Vitrinite reflectance measurements from surface samples of mudrock and coal show anomalously high values over the Bell Creek oil field. The average vitrinite reflectance (Rm) increases to a maximum of 0.9 percent over the field against background values of about 0.3 percent. The Rm anomaly coincides with a geochemical anomaly indicated by diagenetic magnetite in surface rocks and a geobiologic anomaly indicated by ethane-consuming bacteria. These samples were taken from the Upper Cretaceous Hell Creek and Paleocene Fort Union Formations which form an essentially conformable sequence. The depositional environment is similar in both formations, and we expect little variation in the source and composition of the organic matter. The surface R m should be approximately constant because of a uniform thermal history across the field. Temperature studies over local oil fields with similar geology suggest the expected thermal anomaly would be less than 10?C (50?F), which is too small to account for the significantly higher rank over the field. Coal clinkers are rare in the vicinity of Bell Creek and an Rm anomaly caused by burning of the thin, discontinuous coal seams is unlikely. The limited topographic relief, less than 305 m (1,000 ft), over the shallow-dipping homoclinal structure and the poor correlation between Rm and sample locality elevation (r = -0.2) indicate that the Rm anomaly is not due to burial, deformation and subsequent erosion. We conjecture that activity by petroleum-metabolizing bacteria is a possible explanation of the Rm anomaly. Microseepage from oil reservoirs supports large colonies of these organisms, some of which can produce enzymes that can cleave hydrocarbon side-chains on the kerogen molecule. The loss of these side chains causes condensation of the ring structures (Stach and others, 1982) and consequently increases its reflectance. These data indicate that vitrinite reflectance may be a useful tool to explore for stratigraphic traps in the

Astrophysics and Weak Form of Panspermia Hypothesis and Exogenous Factors in the Evolution of the Earth

NASA Astrophysics Data System (ADS)

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.

Subcritical water extraction of organic matter from sedimentary rocks.

PubMed

Luong, Duy; Sephton, Mark A; Watson, Jonathan S

2015-06-16

Subcritical water extraction of organic matter containing sedimentary rocks at 300°C and 1500 psi produces extracts comparable to conventional solvent extraction. Subcritical water extraction of previously solvent extracted samples confirms that high molecular weight organic matter (kerogen) degradation is not occurring and that only low molecular weight organic matter (free compounds) are being accessed in analogy to solvent extraction procedures. The sedimentary rocks chosen for extraction span the classic geochemical organic matter types. A type I organic matter-containing sedimentary rock produces n-alkanes and isoprenoidal hydrocarbons at 300°C and 1500 psi that indicate an algal source for the organic matter. Extraction of a rock containing type II organic matter at the same temperature and pressure produces aliphatic hydrocarbons but also aromatic compounds reflecting the increased contributions from terrestrial organic matter in this sample. A type III organic matter-containing sample produces a range of non-polar and polar compounds including polycyclic aromatic hydrocarbons and oxygenated aromatic compounds at 300°C and 1500 psi reflecting a dominantly terrestrial origin for the organic materials. Although extraction at 300°C and 1500 psi produces extracts that are comparable to solvent extraction, lower temperature steps display differences related to organic solubility. The type I organic matter produces no products below 300°C and 1500 psi, reflecting its dominantly aliphatic character, while type II and type III organic matter contribute some polar components to the lower temperature steps, reflecting the chemical heterogeneity of their organic inventory. The separation of polar and non-polar organic compounds by using different temperatures provides the potential for selective extraction that may obviate the need for subsequent preparative chromatography steps. Our results indicate that subcritical water extraction can act as a suitable

Stable isotopic compositions of carbonates from the Mesoproterozoic Bangemall Group, northwestern Australia

NASA Technical Reports Server (NTRS)

Buick, R.; Des Marais, D. J.; Knoll, A. H.

1995-01-01

Marine carbonate rocks from the Mesoproterozoic Bangemall Group of northwestern Australia show little deviation (+/-1.3%) in whole-rock delta 13C(carb)-values about a mean of -0.5%. This narrow range persists despite close sampling (every 10-20 m) through long sections (up to 2500 m) that are geographically widespread (up to 250 km apart), over many depositional environments (supralittoral to outer shelf), sediment sources (stromatolitic bioherms to detrital calcilutites) and rock types (pure limestones to dolomitic shales). The only major excursions from the norm seem related to unusual environmental or post-depositional processes, as they are correlated with large enrichments (to -3%) or depletions (to -16%) in 18O. Relatively heavy delta 13C-values, up to +2.5%, occur in a single bed of brecciated ferruginous dolostone at a single locality; these abnormal values may result from local evaporitic conditions. Limey and shaley nodular dolostones have delta 13C-values as low as -4.3%, probably caused by remineralization of organic matter during late and patchy dolomitization. Most notably, sharp negative excursions in delta 13C, up to -8.4%, occur in bleached kerogen-free rocks with mineral assemblages of dolomite + quartz + calcite +/- tremolite + talc, reflecting isotopic re-equilibration in thick metamorphic aureoles around dolerite intrusions. General environmental variations are minor, with delta 13C-values of peritidal facies tending to be slightly positive whereas those of subtidal facies are slightly negative. There are no strong secular trends, but subtle fluctuations within the range -2 to +l% can be correlated along the northwestern margin of the basin. This resembles the pattern seen in other Mesoproterozoic successions, but is markedly unlike the heavy background (> +5%) and extreme variations (up to l0%) in delta 13C evident in Neoproterozoic successions of similar thickness and environmental setting. Hence, in contrast to the Neoproterozoic, the global

Late Cretaceous marine arthropods relied on terrestrial organic matter as a food source: Geochemical evidence from the Coon Creek Lagerstätte in the Mississippi Embayment.

PubMed

Vrazo, M B; Diefendorf, A F; Crowley, B E; Czaja, A D

2018-03-01

The Upper Cretaceous Coon Creek Lagerstätte of Tennessee, USA, is known for its extremely well-preserved mollusks and decapod crustaceans. However, the depositional environment of this unit, particularly its distance to the shoreline, has long been equivocal. To better constrain the coastal proximity of the Coon Creek Formation, we carried out a multiproxy geochemical analysis of fossil decapod (crab, mud shrimp) cuticle and associated sediment from the type section. Elemental analysis and Raman spectroscopy confirmed the presence of kerogenized carbon in the crabs and mud shrimp; carbon isotope (δ 13 C) analysis of bulk decapod cuticle yielded similar mean δ 13 C values for both taxa (-25.1‰ and -26‰, respectively). Sedimentary biomarkers were composed of n-alkanes from C 16 to C 36 , with the short-chain n-alkanes dominating, as well as other biomarkers (pristane, phytane, hopanes). Raman spectra and biomarker thermal maturity indices suggest that the Coon Creek Formation sediments are immature, which supports retention of unaltered, biogenic isotopic signals in the fossil organic carbon remains. Using our isotopic results and published calcium carbonate δ 13 C values, we modeled carbon isotope values of carbon sources in the Coon Creek Formation, including potential marine (phytoplankton) and terrestrial (plant) dietary sources. Coon Creek Formation decapod δ 13 C values fall closer to those estimated for terrigenous plants than marine phytoplankton, indicating that these organisms were feeding primarily on terrigenous organic matter. From this model, we infer that the Coon Creek Formation experienced significant terrigenous organic matter input via a freshwater source and thus was deposited in a shallow, nearshore marine environment proximal to the shoreline. This study helps refine the paleoecology of nearshore settings in the Mississippi Embayment during the global climatic shift in the late Campanian-early Maastrichtian and demonstrates for the

Gas storage in the Upper Devonian-Lower Mississippian Woodford Shale, Arbuckle Mountains, Oklahoma: how much of a role do the cherts play?

USGS Publications Warehouse

Fishman, Neil S.; Ellis, Geoffrey S.; Paxton, Stanley T.; Abbott, Marvin M.; Boehlke, Adam

2010-01-01

Microfractures also contribute to Woodford Shale porosity but they appear to be lithologically controlled. Fractures are relatively well-developed and are typically perpendicular to bedding in cherts, but these fractures typically end abruptly or become much more diffuse in adjacent mudstones. The brittle nature of the cherts, due to their high quartz content, is most likely the reason for their excellent fracture development, particularly relative to the mudstones, which are composed of much more ductile clay and Tasmanites constituents. Interestingly, the overlap of some petrophysical properties of cherts and mudstones (e.g., porosity, pore apertures) in the Woodford Shale for samples from the Arbuckle Mountains indicates that for shallowly-buried (i.e. minimally compacted) parts of the formation, both lithologies may have exhibited similar behavior relative to fluid movement. Where the Woodford has been more deeply buried and subjected to more intense compaction (i.e. in the Anadarko Basin), the petrophysical characteristics of cherts are likely to have changed only minimally due to their rigid fabric, whereas the petrophysical characteristics of the mudstones are likely to have changed significantly due to compaction and the resultant compression and collapse of ductile constituents such as clays and Tasmanites microfossils (those without quartz infilling). Moldic porosity, which could be expected to develop in kerogen as a consequence of maturation (Loucks and others, 2009), is more likely in the high TOC mudstones, but would also occur in Woodford cherts, which contain lower TOC contents. Owing to the potential for Woodford cherts to better retain porosity, coupled with their contained TOC, cherts may indeed provide important overlooked intervals of gas generation and overall gas storage in the formation. Thus, Woodford cherts may contribute a significant portion of the gas that is produced from the formation. As such, chert beds may play a very significant

Comets, Carbonaceous Meteorites, and the Origin of the Biosphere

NASA Technical Reports Server (NTRS)

Hoover, Richard B.

2005-01-01

The biosphere comprises the Earth s crust, atmosphere, oceans, and ice caps and the living organisms that survive within this habitat. The discoveries of barophilic chemolithoautotrophic thermophiles living deep within the crust and in deep-sea hydrothermal vents, and psychrophiles in permafrost and deep within the Antarctic Ice Sheet indicate the Earth s biosphere is far more extensive than previously recognized. Molecular biomarkers and Bacterial Paleontology provide evidence that life appeared very early on the primitive Earth and the origin of the biosphere is closely linked with the emergence of life. The role of comets, meteorites, and interstellar dust in the delivery of water, organics and prebiotic chemicals has long been recognized. Deuterium enrichment of seawater and comets indicates that comets delivered oceans to the early Earth. Furthermore, the similarity of the D/H ratios and the chemical compositions of CI carbonaceous meteorites and comets indicate that the CI meteorites may be remnants of cometary nuclei with most volatiles removed. Comets, meteorites, and interstellar dust also contain complex organic chemicals, amino acids, macromolecules, and kerogen-like biopolymers and may have played a crucial role in the delivery of complex organics and prebiotic chemicals during the Hadean (4.5-3.8 Gyr) period of heavy bombardment. The existence of indigenous microfossils of morphotypes of cyanobacteria in the CI and CM carbonaceous meteorites suggests that the paradigm that life originated endogenously in the primitive oceans of early Earth may require re-consideration. Recent data on the hot (300-400 K) black crust on comet P/Halley and Stardust images of P/Wild 2 showing depressions, tall cliffs, and pinnacles, indicate the presence of thick, durable, dark crusts on comets. If cavities within the ice and crust sustain vapor pressures in excess of 10 millibar, then localized pools of liquid water and brines could exist within the comet. Since life

Noble gas partitioning behavior in the Sleipner Vest hydrocarbon field

NASA Astrophysics Data System (ADS)

Barry, P. H.; Lawson, M.; Warr, O.; Mabry, J.; Byrne, D. J.; Meurer, W. P.; Ballentine, C. J.

2015-12-01

Noble gases are chemically inert and variably soluble in crustal fluids. They are primarily introduced into hydrocarbon reservoirs through exchange with formation waters, and can be used to assess migration pathways, mechanisms and reservoir storage. Of particular interest is the role groundwater plays in hydrocarbon transport, which is reflected in hydrocarbon-water volume ratios. We present compositional, stable isotope and noble gas isotope and abundance data from the Sleipner Vest field, in the Norwegian North Sea. Sleipner gases are generated from primary cracking of kerogen and the thermal cracking of oil, sourced from type II marine source, with relatively homogeneous maturities and a range in vitrinite reflectance (1.2-1.7%). Gases are hosted in the lower shoreface sandstones of the Jurassic Hugin formation, which is sealed by the Jurassic Upper Draupne and Heather formations. Gases are composed of N2 (0.6-0.9%), CO2 (5.4-15.3%) and hydrocarbons (69-80%). Helium isotopes (3He/4He) are radiogenic and range from 0.065 to 0.116 RA, showing a small mantle contribution, consistent with Ne isotopes (20Ne/22Ne from 9.70-9.91; 21Ne/22Ne from 0.0290-0.0344) and Ar isotopes (40Ar/36Ar from 315-489). 20Ne/36Ar, 84Kr/36Ar and 132Xe/36Ar values are systematically higher relative to air saturated water ratios. These data are discussed within the framework of several conceptual models: i) Total gas-stripping model, which defines the minimum volume of water to have interacted with the hydrocarbon phase; ii) Equilibrium model, assuming simple equilibration between groundwater and hydrocarbon phase at reservoir P,T and salinity; and iii) Open and closed system gas-stripping models. Using Ne-Ar, we estimate gas-water ratios for the Sleipner system of 0.02-0.09, which compare with geologic gas-water estimates of ~0.24, and suggest more groundwater interaction than a static system estimate. Kr and Xe show evidence for an additional source or process involving oil or sediments.

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

USGS Publications Warehouse

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

1981-01-01

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

Quantitative on-line analysis of sulfur compounds in complex hydrocarbon matrices.

PubMed

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

Similarity of nannobacterial lifeforms in cultures, in the human body, in minerals

NASA Astrophysics Data System (ADS)

Folk, R.

Nearly a dozen labs world-wide have succeeded in culturing minute organisms in the 50-200 nm size range, so the characterization of nannobacteria as some form of "life" is no longer arguable. Within the human body, they are found in blood, kidney stones, dental plaque, arterial disease and cataracts as shown by the Kajander group in Finland, and by our work with Mayo Clinic (e.g. Folk et al., 2001 GSA abs.). Nannobacteria can be concentrated in waters from hot springs, lakes, rivers and the sea. Their charged cell walls attract ions thus triggering precipitation of such varied authigenic minerals as aragonite, calcite, dolomite and siderite; sulfur, pyrite, chalcocite, chalcopyrite; phosphates; chalcedony quartz; and smectite, illite, kaolinite, chlorite and palygorskite clay. So it should be no surprise that on Mars, with reactive FeMg minerals, subsurface (and once surface) water, and internal heat, nannobacteria would be able to thrive both in vein-fill carbonates (McKay et al, 1996) and on the altered surfaces of unstable pyroxenes (Folk and Taylor, in press Met. &Plan. S i., 2002). Striking identities of sizes, shapes, and colonial affinitiesc are found between Martian nannobacteria and those in clays from Sicily and elsewhere (Folk and Lynch, 1997 SPIE). Extraterrestrial forms range from spheroids and ovoids of 30-80 nm, to worm- and caterpillar-shaped objects (40 X 150 nm) and chains of 40 nm beads. Even in the Allende carbonaceous chondrite, groups of 40- 150 nm bodies resembly earthly Streptococcus and Staphylococcus are found (Folk and Lynch 1998 SPIE). The highly-matured nature of the kerogen-like carbon in Allende demonstrates that it is not the result of earthly contamination; furthermore Allende contains clay minerals which demand the former presence of some water, a requirement for biology.The only objection to the claimed discovery of extraterrestrial life in the form of nannobacteria is the Old Testament view that God created life only on Earth and

Survey for Life-related Species During a Planetary Surface Exploration; System Type I - UV Stimulated Fluorescent Sensor

NASA Technical Reports Server (NTRS)

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

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

NASA Astrophysics Data System (ADS)

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 <0.01), the 3.4 µm absorption is observed for some 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

Carbonaceous Material in Extraterrestrial Matter

NASA Astrophysics Data System (ADS)

Martins, Zita

2015-08-01

Comets, asteroids and their fragments (i.e. meteorite, micrometeorites and interplanetary dust particles (IDPs)) are known to contain carbonaceous material. IDPs have ~10% of carbon by mass [1-3], while both micrometeorites and IDPs contain organic molecules. However, it is not certain whether these molecules are indigenous or terrestrial contamination [4-7]. On the other hand, ultra-carbonaceous Antarctic micrometeorites (UCAMMs) contain 50-80% of carbonaceous material, which is one of the highest organic matter contents detected in an extraterrestrial body [8]. Comets also have several extraterrestrial organic molecules [9, 10], including the simplest amino acid glycine [11]. In addition, the impact-shock of a typical comet ice mixture produces several amino acids from simple precursors [12]. Carbonaceous meteorites contain up to 5wt% of organic carbon [13], which is either locked in an insoluble kerogen-like polymer, or in a rich organic inventory of soluble organic compounds [14-16]. Bulk analysis of the meteoritic soluble organic fraction has revealed a high molecular diversity of tens of thousands of different molecular compositions [17]. The analysis of the carbonaceous content of comets, asteroids and their fragments provides a window into the resources delivered to the early Earth.[1] Brownlee (1985) Ann. Rev. Earth and Plan. Sci. 13, 147. [2] Schramm et al. (1989) Meteoritics 24, 99. [3] Messenger (2002) MAPS 37, 1491. [4] Clemett et al. (1993) Science 262, 721. [5] Brinton et al. (1998) OLEB 28, 413. [6] Flynn (2003) GCA 67, 4791. [7] Matrajt et al. (2004) MAPS 39, 1849. [8] Duprat et al. (2010) Science 328, 742-745. [9] Bockelée-Morvan et al. (2004) in: Comets II. pp. 391-423. [10] Mumma and Charnley (2011) ARAA 49, 471. [11] Elsila et al. (2009) MAPS 44, 1323. [12] Martins et al. (2013) Nature Geoscience 6, 1045. [13] Alexander et al. (2013) GCA 123, 244. [14] Cronin and Chang (1993) in: The Chemistry of Life’s Origin. pp. 209-258. [15] Cody and

Laboratory simulated hydrothermal alteration of sedimentary organic matter from Guaymas Basin, Gulf of California. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

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.

Molecular Ecological and Stable Isotopic Studies of Nitrogen Fixation in Modern Microbial Mats

NASA Technical Reports Server (NTRS)

Bebout, B. M.; Crumbliss, L. L.; DesMarais, D. J.; Hogan, M. E.; Omoregie, E.; Turk, K. A.; Zehr, J. P.

2003-01-01

Nitrogen is usually the element limiting biological productivity in the marine environment. Microbial mats, laminated microbial communities analogous to some of the oldest forms of life on Earth, are often the sites of high rates of N fixation (the energetically expensive conversion of atmospheric dinitrogen into a biologically useful form). The N fixing enzyme nitrogenase is generally considered to be of ancient origin, and is widely distributed throughout the Bacterial and Archaeal domains of life, indicating an important role for this process over evolutionary time. The stable isotopic signature of N fixation is purportedly recognizable in organic matter (ancient kerogens as well as present-day microbial mats) as a delta (15)N(sub organic) near zero. We studied two microbial mats exhibiting different rates of N fixation in order to better understand the impact of N fixation on the delta (15)N (sub organic) of the mats, as well as what organisms are important in this process. Mats dominated by the cyanobacterium Microcoleus chthonoplastes grow in permanently submerged hypersaline salterns, and exhibit low rates of N fixation, whereas mats dominated by the cyanobacterium Lyngbya spp grow in an intertidal area, and exhibit rates of N fixation an order of magnitude higher. To examine successional stages in mat growth, both developing and established mats at each location were sampled. PCR and RT-PCR based approaches were used to identify, respectively, the organisms containing nifH (one of the genes that encode nitrogenase) as well as those expressing nifH in these mats. Both mats exhibited a distinct diel cycle of N fixation, with highest rates occurring at night. The delta (15)N(sub organic) of the subtidal Microcoleus mats is near zero whereas the delta (15)N(sub organic) is slightly more positive (+ 2-3%), in the intertidal Lyngbya mats, an interesting difference in view of the fact that overall rates of activity in the intertidal mats are much higher that those