Petrology and diagenetic history of the upper shale member of the Late Devonian-Early Mississippian Bakken Formation, Williston Basin, North Dakota

USGS Publications Warehouse

Neil S. Fishman,; Sven O. Egenhoff,; Boehlke, Adam; Lowers, Heather A.

2015-01-01

The organic-rich upper shale member of the upper Devonian–lower Mississippian Bakken Formation (Williston Basin, North Dakota, USA) has undergone significant diagenetic alteration, irrespective of catagenesis related to hydrocarbon generation. Alteration includes precipitation of numerous cements, replacement of both detrital and authigenic minerals, multiple episodes of fracturing, and compaction. Quartz authigenesis occurred throughout much of the member, and is represented by multiple generations of microcrystalline quartz. Chalcedonic quartz fills radiolarian microfossils and is present in the matrix. Sulfide minerals include pyrite and sphalerite. Carbonate diagenesis is volumetrically minor and includes thin dolomite overgrowths and calcite cement. At least two generations of fractures are observed. Based on the authigenic minerals and their relative timing of formation, the evolution of pore waters can be postulated. Dolomite and calcite resulted from early postdepositional aerobic oxidation of some of the abundant organic material in the formation. Following aerobic oxidation, conditions became anoxic and sulfide minerals precipitated. Transformation of the originally opaline tests of radiolaria resulted in precipitation of quartz, and quartz authigenesis is most common in more distal parts of the depositional basin where radiolaria were abundant. Because quartz authigenesis is related to the distribution of radiolaria, there is a link between diagenesis and depositional environment. Furthermore, much of the diagenesis in the upper shale member preceded hydrocarbon generation, so early postdepositional processes were responsible for occlusion of significant original porosity in the member. Thus, diagenetic mineral precipitation was at least partly responsible for the limited ability of these mudstones to provide porosity for storage of hydrocarbons.

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

New constraints on Neogene uplift of the northern Colorado Plateau

NASA Astrophysics Data System (ADS)

Van Wijk, J. W.; Raschilla, R.

2013-12-01

The Late Cretaceous Uinta Basin is located in northeastern Utah within the northern most portion of the Colorado Plateau. The basin's uplift and subsidence history and thermal evolution have impacted the maturity of source beds in the Parachute Creek Member of the Green River Formation. Using measured data of the petroleum system of the Uinta Basin, we were able to constrain timing and amplitude of uplift of the northern Colorado Plateau. We used sixty wells in a basin modeling study of the Uinta Basin's thermal structure, tectonic history and petroleum system. The wells reached into basement, and four wells provided vitrinite reflectance measurements. Vitrinite reflectance is a measurement of the percentage of reflected light from a polished vitrinite sample. The percentage of reflected light is related to the temperature conditions the sample experienced during burial, and vitrinite reflectance is a maturity indicator that covers a broad temperature range from diagenesis through the latest stages of catagenesis and records the maximum temperature a rock experiences during its burial history All models were calibrated to measured data, including vitrinite reflectance and transformation ratios from Rock-Eval pyrolysis. The models predict that the heat flow ranges from 65 mW/m2 to 45 mW/m2 from south to north in the study area. Additionally, model calibration provides a means for estimating the amount of uplift and erosion in the Uinta Basin. Uplift predicted for the Uinta Basin ranges from ~2050 m to ~2200 m and started in the Late Miocene. Our models also predicted the maturity of the rich oil shales of the Parachute Creek Member.

Source rock potential of an Eocene carbonate slope: The Armancies Formation of the south-Pyrenean basin, northeast Spain

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

Permanyer, A.; Valles, D.; Dorronsorro, C.

1988-08-01

The Armancies Formation is an Eocene carbonate slope succession in the Catalonian South Pyrenean basin. It ranges from 500 to 700 m in thickness. The first 200 m are made of a thin-bedded facies of wackestones alternating with dark pelagic fauna of miliolid, ostracods, bryozoans, and planktonic foraminifers and show significant bioturbation. They also show a low organic content (< 0.5% TOC). The lime-mudstone beds show a massive structure or planar millimeter laminations. They may contain sparse pelagic fossils of planktonic foraminifers, ostracods, and dinoflagellates; they do not show any bioturbation, and have high TOC values, which can reach individualmore » scores of about 14%. They qualify, therefore, as a typical oil shale. Rock-Eval Pyrolysis analysis affords a mean S{sub 2} value of 25 mg HC/g. Mean S{sub 1} value is around 1.0 mg HC/g. As is typical of an initial oil window, T{sub max} maturity parameter ranges from 432 to 440{degree}C (mean = 434{degree}C). This degree of evolution is in accordance with the very low value of carbonyl and carboxyl groups, as determined by IR spectrometry and NMR on Fischer assay extract. The proton NMR shows an aromatic/aliphatic hydrocarbon ratio of 1:4, as expected in earlier stages of catagenesis. N-alkane gas chromatography profiles show n-C{sub 15} to n-C{sub 19} prevalence and that neither even nor odd carbon numbers prevail. This distribution perfectly matches that of typical sediments of marine origin and also agrees with obtained hydrogen index values (mean HI = 500 mg HC/g TOC). Sedimentological and geochemical results indicate an autochthonous marine organic matter and the potential of these slope shales is good oil-prone source beds.« less

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.

Apparent overconsolidation of mudstones in the Kumano Basin of southwest Japan: Implications for fluid pressure and fluid flow within a forearc setting

NASA Astrophysics Data System (ADS)

Guo, Junhua; Underwood, Michael B.; Likos, William J.; Saffer, Demian M.

2013-04-01

The Kumano Basin is located in the Nankai Trough subduction zone of southwest Japan. During the past 1.6 million years, approximately 800 meters of sandy turbidites and hemipelagic mud were deposited near the distal edge of the forearc basin, at Site C0002 of the Integrated Ocean Drilling Program. Constant-rate-of-strain consolidation tests yield estimates of in situ permeability that range from 2.6 × 10-17 m2 to 2.5 × 10-18 m2; overconsolidation ratios range from 1.7 to 2.6, and values of the compression index range from 0.39 to 0.78. Several processes contributed to the apparent overconsolidation. Strata dip toward land, and pore fluids probably migrate up-dip and vent along a bathymetric notch near the seaward edge of the basin. Efficient lateral drainage through sandy turbidites has kept pore pressures within interbeds of mudstone at (or close to) hydrostatic. In addition, alteration of dispersed volcanic glass, precipitation of authigenic clay minerals, and collapse of random grain fabric has probably strengthened the bonding among grains. Cementation is particularly likely within the lower basin (unit III), where values of porosity remain anomalously high. If fluid overpressures (and underconsolidation) exist anywhere within the basin, the most likely loci are where sandy turbidites terminate against impermeable mudstones along landward-dipping on-lap surfaces. Those types of on-lap geometries, in addition to structural closures, might provide promising targets for oil/gas accumulation in other forearc basins, particularly where petroleum source rocks have been buried to the optimal depths of catagenesis.

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

Guliyev, I.A.; Aliyev, A.A.; Rahmanov, R.R.

Azerbaijan is a classic region for the study of mud volcanism. Of the 700 mud volcanoes known in the world, 220 are in Azerbaijan. These are of great interest, not least in relation to oil and gas exploration since they give information on subsurface sediments beyond the reach of drilling. Mud volcanoes are clearly visible on satellite images. They are confined to structural lineaments and associated fractures. Changes in the morphology of some mud volcanoes post-eruption can be detected from a series of images pre-dating and post-dating eruptions. Mud volcanoes are notable for gradients of temperature that are by anmore » order of magnitude or a factor of 102 greater than the temperature gradients established elsewhere. The gases of mud volcanoes consist mainly of methane (95-100%). There are small amounts of C{sub 2-6}, CO{sub 2}, N{sub 2}, He and Ar. The isotopic composition of carbon (ICC) within the methane varies from -61.29. to -35.W{close_quotes} which is isotopically heavier than the methane from producing fields. The ICC of the CO{sub 2} has a very wide range (from -49.6% to +23.1%), indicating several sources of its formation. The isotopically superheavy CO{sub 2} (+5%) is especially interesting. Oils from mud volcanoes are typically severely biodegraded. Their ICC ranges from -24.76% to -28.2%. A relationship between {partial_derivative}{sup l3}C of oils and ages of accumulations has been established. Waters of mud volcanoes are lightly mineralised, containing chiefly bicarbonates and sodium. The hydrogen composition of the water is abnormally heavy. Ejected rocks from mud volcanoes range in age from Cretaceous - Pliocene. Their study suggests that deeply buried reservoirs maintain good poroperm characteristics because of relatively little catagenesis.« less

Diamondoid hydrocarbons as a molecular proxy for thermal maturity and oil cracking: Geochemical models from hydrous pyrolysis

USGS Publications Warehouse

Wei, Z.; Moldowan, J.M.; Zhang, S.; Hill, R.; Jarvie, D.M.; Wang, Hongfang; Song, F.; Fago, F.

2007-01-01

A series of isothermal hydrous pyrolysis experiments was performed on immature sedimentary rocks and peats of different lithology and organic source input to explore the generation of diamondoids during the thermal maturation of sediments. Oil generation curves indicate that peak oil yields occur between 340 and 360 ??C, followed by intense oil cracking in different samples. The biomarker maturity parameters appear to be insensitive to thermal maturation as most of the isomerization ratios of molecular biomarkers in the pyrolysates have reached their equilibrium values. Diamondoids are absent from immature peat extracts, but exist in immature sedimentary rocks in various amounts. This implies that they are not products of biosynthesis and that they may be generated during diagenesis, not just catagenesis and cracking. Most importantly, the concentrations of diamondoids are observed to increase with thermal stress, suggesting that they can be used as a molecular proxy for thermal maturity of source rocks and crude oils. Their abundance is most sensitive to thermal exposure above temperatures of 360-370 ??C (R0 = 1.3-1.5%) for the studied samples, which corresponds to the onset of intense cracking of other less stable components. Below these temperatures, diamondoids increase gradually due to competing processes of generation and dilution. Calibrations were developed between their concentrations and measured vitrinite reflectance through hydrous pyrolysis maturation of different types of rocks and peats. The geochemical models obtained from these methods may provide an alterative approach for determining thermal maturity of source rocks and crude oils, particularly in mature to highly mature Paleozoic carbonates. In addition, the extent of oil cracking was quantified using the concentrations of diamondoids in hydrous pyrolysates of rocks and peats, verifying that these hydrocarbons are valuable indicators of oil cracking in nature. ?? 2006 Elsevier Ltd. All rights reserved.

Geochemical and multi-isotopic (87Sr/86Sr, 143Nd/144Nd, 238U/235U) perspectives of sediment sources, depositional conditions, and diagenesis of the Marcellus Shale, Appalachian Basin, USA

NASA Astrophysics Data System (ADS)

Phan, Thai T.; Gardiner, James B.; Capo, Rosemary C.; Stewart, Brian W.

2018-02-01

We investigate sediment sources, depositional conditions and diagenetic processes affecting the Middle Devonian Marcellus Shale in the Appalachian Basin, eastern USA, a major target of natural gas exploration. Multiple proxies, including trace metal contents, rare earth elements (REE), the Sm-Nd and Rb-Sr isotope systems, and U isotopes were applied to whole rock digestions and sequentially extracted fractions of the Marcellus shale and adjacent units from two locations in the Appalachian Basin. The narrow range of εNd values (from -7.8 to -6.4 at 390 Ma) is consistent with derivation of the clastic sedimentary component of the Marcellus Shale from a well-mixed source of fluvial and eolian material of the Grenville orogenic belt, and indicate minimal post-depositional alteration of the Sm-Nd system. While silicate minerals host >80% of the REE in the shale, data from sequentially extracted fractions reflect post-depositional modifications at the mineralogical scale, which is not observed in whole rock REE patterns. Limestone units thought to have formed under open ocean (oxic) conditions have δ238U values and REE patterns consistent with modern seawater. The δ238U values in whole rock shale and authigenic phases are greater than those of modern seawater and the upper crust. The δ238U values of reduced phases (the oxidizable fraction consisting of organics and sulfide minerals) are ∼0.6‰ greater than that of modern seawater. Bulk shale and carbonate cement extracted from the shale have similar δ238U values, and are greater than δ238U values of adjacent limestone units. We suggest these trends are due to the accumulation of chemically and, more likely, biologically reduced U from anoxic to euxinic bottom water as well as the influence of diagenetic reactions between pore fluids and surrounding sediment and organic matter during diagenesis and catagenesis.

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 conventional and unconventional hydrocarbons.

Comparison of GC-MS, GC-MRM-MS, and GC × GC to characterise higher plant biomarkers in Tertiary oils and rock extracts

NASA Astrophysics Data System (ADS)

Eiserbeck, Christiane; Nelson, Robert K.; Grice, Kliti; Curiale, Joseph; Reddy, Christopher M.

2012-06-01

Higher plant biomarkers occur in various compound classes with an array of isomers that are challenging to separate and identify. Traditional one-dimensional (1D) gas chromatographic (GC) techniques achieved impressive results in the past, but have reached limitations in many cases. Comprehensive two-dimensional gas chromatography (GC × GC) either coupled to a flame ionization detector (GC × GC-FID) or time-of-flight mass spectrometer (GC × GC-TOFMS) is a powerful tool to overcome the challenges of 1D GC, such as the resolution of unresolved complex mixture (UCM). We studied a number of Tertiary, terrigenous oils, and source rocks from the Arctic and Southeast Asia, with special focus on angiosperm biomarkers, such as oleanoids and lupanoids. Different chromatographic separation and detection techniques such as traditional 1D GC-MS, metastable reaction monitoring (GC-MRM-MS), GC × GC-FID, and GC × GC-TOFMS are compared and applied to evaluate the differences and advantages in their performance for biomarker identification. The measured 22S/(22S + 22R) homohopane ratios for all applied techniques were determined and compare exceptionally well (generally between 2% and 10%). Furthermore, we resolved a variety of angiosperm-derived compounds that co-eluted using 1D GC techniques, demonstrating the superior separation power of GC × GC for these biomarkers, which indicate terrigenous source input and Cretaceous or younger ages. Samples of varying thermal maturity and biodegradation contain higher plant biomarkers from various stages of diagenesis and catagenesis, which can be directly assessed in a GC × GC chromatogram. The analysis of whole crude oils and rock extracts without loss in resolution enables the separation of unstable compounds that are prone to rearrangement (e.g. unsaturated triterpenoids such as taraxer-14-ene) when exposed to fractionation techniques like molecular sieving. GC × GC-TOFMS is particularly valuable for the successful separation of co-eluting components having identical molecular masses and similar fragmentation patterns. Such components co-elute when analysed by 1D GC and cannot be resolved by single-ion-monitoring, which prevents accurate mass spectral assessment for identification or quantification.

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 precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.

Methane clumped isotopes in the Songliao Basin (China): New insights into abiotic vs. biotic hydrocarbon formation

NASA Astrophysics Data System (ADS)

Shuai, Yanhua; Etiope, Giuseppe; Zhang, Shuichang; Douglas, Peter M. J.; Huang, Ling; Eiler, John M.

2018-01-01

Abiotic hydrocarbon gas, typically generated in serpentinized ultramafic rocks and crystalline shields, has important implications for the deep biosphere, petroleum systems, the carbon cycle and astrobiology. Distinguishing abiotic gas (produced by chemical reactions like Sabatier synthesis) from biotic gas (produced from degradation of organic matter or microbial activity) is sometimes challenging because their isotopic and molecular composition may overlap. Abiotic gas has been recognized in numerous locations on the Earth, although there are no confirmed instances where it is the dominant source of commercially valuable quantities in reservoir rocks. The deep hydrocarbon reservoirs of the Xujiaweizi Depression in the Songliao Basin (China) have been considered to host significant amounts of abiotic methane. Here we report methane clumped-isotope values (Δ18) and the isotopic composition of C1-C3 alkanes, CO2 and helium of five gas samples collected from those Xujiaweizi deep reservoirs. Some geochemical features of these samples resemble previously suggested identifiers of abiotic gas (13C-enriched CH4; decrease in 13C/12C ratio with increasing carbon number for the C1-C4 alkanes; abundant, apparently non-biogenic CO2; and mantle-derived helium). However, combining these constraints with new measurements of the clumped-isotope composition of methane and careful consideration of the geological context, suggests that the Xujiaweizi depression gas is dominantly, if not exclusively, thermogenic and derived from over-mature source rocks, i.e., from catagenesis of buried organic matter at high temperatures. Methane formation temperatures suggested by clumped-isotopes (167-213 °C) are lower than magmatic gas generation processes and consistent with the maturity of local source rocks. Also, there are no geological conditions (e.g., serpentinized ultramafic rocks) that may lead to high production of H2 and thus abiotic production of CH4 via CO2 reduction. We propose that the Songliao gas is representative of an atypical type of thermogenic gas that can be mistaken for abiotic gas. Such gases may be encountered more frequently in future exploration of deep or over-mature petroleum systems.

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

USGS Publications Warehouse

Shuai, Yanhua; Douglas, Peter M.J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

2018-01-01

Multiply isotopically substituted molecules (‘clumped’ isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature–time conditions corresponding to ‘low,’ ‘mature,’ and ‘over-mature’ stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions (‘high’ to ‘over-mature’ stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where ‘secondary’ cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.

Geophysical aspects of underground fluid dynamics and mineral transformation process

NASA Astrophysics Data System (ADS)

Khramchenkov, Maxim; Khramchenkov, Eduard

2014-05-01

The description of processes of mass exchange between fluid and poly-minerals material in porous media from various kinds of rocks (primarily, sedimentary rocks) have been examined. It was shown that in some important cases there is a storage equation of non-linear diffusion equation type. In addition, process of filtration in un-swelling soils, swelling porous rocks and coupled process of consolidation and chemical interaction between fluid and particles material were considered. In the latter case equations of physical-chemical mechanics of conservation of mass for fluid and particles material were used. As it is well known, the mechanics of porous media is theoretical basis of such branches of science as rock mechanics, soil physics and so on. But at the same moment some complex processes in the geosystems lacks full theoretical description. The example of such processes is metamorphosis of rocks and correspondent variations of stress-strain state. In such processes chemical transformation of solid and fluid components, heat release and absorption, phase transitions, rock destruction occurs. Extensive usage of computational resources in limits of traditional models of the mechanics of porous media cannot guarantee full correctness of obtained models and results. The process of rocks consolidation which happens due to filtration of underground fluids is described from the position of rock mechanics. As an additional impact, let us consider the porous media consolidating under the weight of overlying rock with coupled complex geological processes, as a continuous porous medium of variable mass. Problems of obtaining of correct storage equations for coupled processes of consolidation and mass exchange between underground fluid and skeleton material are often met in catagenesi processes description. The example of such processes is metamorphosis of rocks and correspondent variations of stress-strain state. In such processes chemical transformation of solid and fluid components, heat release and absorption, phase transitions, rock destruction occurs. Extensive usage of computational resources in limits of traditional models of the mechanics of porous media cannot guarantee full correctness of obtained models and results. The present work is dedicated to the retrieval of new ways to formulate and construct such models. It was shown that in some important cases there is a governing equation of non-linear diffusion equation type (well-known Fisher equation). In addition, some geophysical aspects of filtration process in usual non-swelling soils, swelling porous rocks and coupled process of consolidation and chemical interaction between fluid and skeleton material, including earth quakes, are considered.

In search of early life: Carbonate veins in Archean metamorphic rocks as potential hosts of biomarkers

NASA Astrophysics Data System (ADS)

Peters, Carl A.; Piazolo, Sandra; Webb, Gregory E.; Dutkiewicz, Adriana; George, Simon C.

2016-11-01

The detection of early life signatures using hydrocarbon biomarkers in Precambrian rocks struggles with contamination issues, unspecific biomarkers and the lack of suitable sedimentary rocks due to extensive thermal overprints. Importantly, host rocks must not have been exposed to temperatures above 250 °C as at these temperatures biomarkers are destroyed. Here we show that Archean sedimentary rocks from the Jeerinah Formation (2.63 billion yrs) and Carawine Dolomite (2.55 billion yrs) of the Pilbara Craton (Western Australia) drilled by the Agouron Institute in 2012, which previously were suggested to be suitable for biomarker studies, were metamorphosed to the greenschist facies. This is higher than previously reported. Both the mineral assemblages (carbonate, quartz, Fe-chlorite, muscovite, microcline, rutile, and pyrite with absence of illite) and chlorite geothermometry suggest that the rocks were exposed to temperatures higher than 300 °C and probably ∼400 °C, consistent with greenschist-facies metamorphism. This facies leads to the destruction of any biomarkers and explains why the extraction of hydrocarbon biomarkers from pristine drill cores has not been successful. However, we show that the rocks are cut by younger formation-specific carbonate veins containing primary oil-bearing fluid inclusions and solid bitumens. Type 1 veins in the Carawine Dolomite consist of dolomite, quartz and solid bitumen, whereas type 2 veins in the Jeerinah Formation consist of calcite. Within the veins fluid inclusion homogenisation temperatures and calcite twinning geothermometry indicate maximum temperatures of ∼200 °C for type 1 veins and ∼180 °C for type 2 veins. Type 1 veins have typical isotopic values for reprecipitated Archean sea-water carbonates, with δ13CVPDB ranging from - 3 ‰ to 0‰ and δ18OVPDB ranging from - 13 ‰ to - 7 ‰, while type 2 veins have isotopic values that are similar to hydrothermal carbonates, with δ13CVPDB ranging from - 18 ‰ to - 4 ‰ and δ18OVPDB ranging from - 18 ‰ to - 12 ‰. Evidently, the migration and entrapment of hydrocarbons occurred after peak metamorphism under temperatures congruous with late catagenesis and from fluids of different compositions. The relatively high temperatures of vein formation and the known geotectonic history of the rocks analysed suggest a probable minimum age of 1.8 billion yrs (Paleoproterozoic). Our results demonstrate that post peak-metamorphic veins provide an exciting opportunity in the search for evidence of early life. The integration of petrological and organic geochemical techniques is crucial for any future studies that use biomarkers to reconstruct the early biosphere.

Studying of shale organic matter structure and pore space transformations during hydrocarbon generation

NASA Astrophysics Data System (ADS)

Giliazetdinova, Dina; Korost, Dmitry; Gerke, Kirill

2016-04-01

Due to the increased interest in the study of the structure, composition, and oil and gas potential of unconventional hydrocarbon resources, investigations of the transformation of the pore space of rocks and organic matter alterations during the generation of hydrocarbon fluids are getting attention again. Due to the conventional hydrocarbon resources decreasing, there will be a necessity to develop new unconventional hydrocarbon resources. Study of the conditions and processes of hydrocarbon generation, formation and transformation of the pore space in these rocks is pivotal to understand the mechanisms of oil formation and determine the optimal and cost effective ways for their industrial exploration. In this study, we focus on organic matter structure and its interaction with the pore space of shales during hydrocarbon generation and report some new results. Collected rock samples from Domanic horizon of South-Tatar arch were heated in the pyrolyzer to temperatures closely corresponding to different catagenesis stages. X-ray microtomography method and SEM were used to monitor changes in the morphology of the pore space and organic matter structure within studied shale rocks. By routine measurements we made sure that all samples (10 in total) had similar composition of organic and mineral phases. All samples in the collection were grouped according to initial structure and amount of organics and processed separately to: 1) study the influence of organic matter content on the changing morphology of the rock under thermal effects; 2) study the effect of initial structure on the primary migration processes for samples with similar organic matter content. An additional experiment was conducted to study the dynamics of changes in the structure of the pore space and prove the validity of our approach. At each stage of heating the morphology of altered rocks was characterized by formation of new pores and channels connecting primary voids. However, it was noted that the samples with a relatively low content of the organic matter had less changes in pore space morphology, in contrast to rocks with a high organic content. Second part of the study also revealed significant differences in resulting pore structures depending on initial structure of the unaltered rocks and connectivity of original organics. Significant changes in the structure of the pore space were observed during the sequential heating in the range from 260 C to 430 C, which corresponds to the most intense stage of the hydrocarbons formation. This work was partially supported by RSF grant 14-17-00658.

Living microbial ecosystems within the active zone of catagenesis: Implications for feeding the deep biosphere

NASA Astrophysics Data System (ADS)

Horsfield, B.; Schenk, H. J.; Zink, K.; Ondrak, R.; Dieckmann, V.; Kallmeyer, J.; Mangelsdorf, K.; di Primio, R.; Wilkes, H.; Parkes, R. J.; Fry, J.; Cragg, B.

2006-06-01

Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m 2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

Organic geochemical study of domanik deposits, Tatarstan Republic.

NASA Astrophysics Data System (ADS)

Nosova, F. F.; Pronin, N. V.

2010-05-01

High-bituminous argillo-siliceous carbonate deposits of domanik formation (DF) occurring within pale depressions and down warps in the east of the Russian platform are treated by many investigators as a main source of oil and gas in the Volga-Ural province. In this study a special attention was turned to organic-rich rocks DF witch outcrop in the central part (Uratminskaya area 792, 806 boreholes) and in the west part (Sviyagskaya, 423) of the Tatarstan Republic. The aim of the present paper is to characterize the organic matter: origin, depositional environments, thermal maturity and biodegradation-weathering effects. Nowadays the most informative geochemical parameters are some biomarkers which qualitatively and are quantitatively defined from distributions of n-alkanes and branched alkanes. Biomarkers - it's original fingerprints of biomass of organic matter, that reflect molecular hydrocarbonic structure. The bulk, molecular composition of oil is initially a function of the type and maturity of the source rock from which it has been expelled, while the source rock type reflects both the nature of precursor organisms and the conditions of its deposition. Methodology used in this study included sampling, bitumen extraction, liquid-column chromatography and gas chromatography/mass spectrometry analyses. The bitumen was fractionated by column chromatography on silica gel. Non-aromatic or alifatics, aromatics and polar compounds were obtained. Alifatic were analysed by gas chromatography/mass spectrometry Percin Elmer. The hydrocarbons present in the sediments of DF and have a carbon numbers ranging from 12 through 38. The samples contain variably inputs from both terrigenous and non-terrigenous (probably marine algal) organic matter as evident in bimodal GC fingerprints of some samples. Pristane and phytane, also, occur in very high concentration in sample extracts. The relatively low Pr/Ph ratios, CPI and OEP<1 imply that the domanik organic matter was deposited in reducing environments. Mass chromatograms show the distribution of regular steranes, iso-steranes, lower molecular weight C21 and C22 steranes (pregnanes) (m/z 217) and triterpanes (m/z 191). The biomarkers distribution of the domanic samples generally suggests a major marine phytoplankton contribution relative to terrigenous land plant source input. The marine affinity is evident from the relatively abundant C27 steranes, which are biomarkers for marine algal contribution to organic matter and low C29 sterane contens. In this present study, samples are dominated by 5α, 14α, 17α (H)-20R and 5β, 14α, 17α (H)-20R steranes (biological configuration). The ratios of 20S/(20S+20R) for αααC29 steranes and ββ/(αα + ββ) for 5α-C29 steranes in the samples, are 0.21 to 0.55 and to 0.12 to 0.50, respectively. The thermal maturity level, assessed by values of several biomarker parameters has been estimated to be within end of diagenesis/eginning of catagenesis and correspond to theoretical vitrinite values (R0) in the range 0.57-0.65%.

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 Mountains. The basin is composed of land areas in Colorado, the Humboldt highland in northeastern Nevada and intervening carbonate shelves in Utah and Wyoming. The phosphorites and the carbonaceous mudstones were deposited on the foreslope between the carbonate and littoral sand deposits on the shelf and the dominantly cherty mudstone sediments in the axial part of the basin. Paleomagnetic evidence indicates that in the Permian the region would have been within the northern hemispheric trade wind belt; and wind-direction studies determined from studies of sand dunes, indicate that the prevailing winds from the Milk River uplift would have blown offshore across the Phosphoria sea. Offshore winds would have carried surface water away from the shore and generated upwelling in the sea in eastern Idaho and adjacent areas in Montana, Wyoming and Utah. Prior to deposition of the Phosphoria, the region was the site of extensive deposition of shallow-water carbonate sediments. Equivalent rocks in the northern part of the basin are dominantly sandstone derived from the adjacent Milk River uplift and similar sandstone strata in the southeastern sector were derived from the ancestral Rocky Mountains uplift. Tectonic subsidence of the Sublett basin in part of the region seems to have provided a sea-floor profile favorable for upwelling circulation and the shift in deposition from regional carbonates and local sandstone into a more complex depositional pattern that included the accumulation of the mudstone-chert-phosphorite facies that comprises the Phosphoria Formation. High biological productivity and the accumulation of sapropel on the sea floor is associated with contemporary coastal upwelling (1) and similar environmental and depositional conditions are attributed to the rich accumulations of organic matter in the Phosphoria Formation. Sapropelic mudstone and phosphorite composing the Meade Peak Member are approximately 60 m thick near the center of the Sublett basin. The Meade