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M. D. Lewan

Publications and source records attributed to M. D. Lewan.

At least 37 records · Page 2Linked to original sources
USGS2004

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

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 generation from the cracking of oil, which occurred in the early to late Eocene (52 to 41 Ma). For the Mesaverde Group, which also contains a mix of type-II and type-III kerogen, peak oil generation occurred only in the deepest parts of the province during middle Eocene (50 to 41 Ma). Only at Adobe Town did cracking of oil occur and gas generation reach peak in the earliest Oligocene (33 Ma). Gas-prone source rocks (type-III kerogen) of the Mowry and Baxter (and equivalents) Shales reached peak gas generation in the latest Cretaceous (66 Ma) in the deepest parts of the province. At the shallower Bear 1 location, the Mancos Shale (Baxter equivalent) source rocks reached peak gas generation at about this same time. Gas generation from the gas-prone Mesaverde source rocks started at all of the modeled locations, but reached peak generation at only the deepest locations in the early Eocene (54 to 49 Ma). The Lewis Shale, Lance Formation, and Fort Union Formation all contain gas-prone source rocks with type-III kerogen. Peak generation of gas from the Lewis Shale occurred only at Eagles Nest and Adobe Town in the early Eocene (52 Ma). Source rocks of the Lance reached peak gas generation only at the deepest locations during the middle Eocene (48 to 45 Ma) and the Fort Union reached peak gas generation only at Adobe Town also in the middle Eocene (44 Ma).

Mountain Geologist↗
USGS2003

Comparison of artificial maturation of lignite in hydrous and nonhydrous conditions

The objectives of the study are to compare product compositions and yields generated from lignite artificially matured by open nonhydrous pyrolysis, closed nonhydrous pyrolysis, and hydrous pyrolysis. The pyrolysis products were fractionated into CO2, H2O, CH4, C2-C5, C8-C14, C14+ saturates, C14+ aromatics and NSOs (resins+asphaltenes). All three methods generated high and similar quantities of water during pyrolysis that ranged between 14.6 and 15.2 wt.% of the original lignite. As a result of this high water content generated by the lignite, the experiments with no added water are referred to as nonhydrous rather than anhydrous. Rock-Eval pyrolysis and elemental analyses were conducted on the recovered lignite after solvent extraction to determine their residual hydrocarbon generation potential and to plot their position in a van Krevelen diagram, respectively. Residual lignite from the closed nonhydrous and hydrous experiments showed relationships between vitrinite reflectance (%Ro) values and atomic H/C ratios that occurred within the fields observed for natural maturation of coal. Although no significant differences in the atomic H/C ratios were observed between closed nonhydrous and hydrous pyrolysis, the vitrinite reflectance values were on the average 0.2% Ro lower in the residual lignite from the nonhydrous experiments. The remaining hydrocarbon generation potential as determined by Rock-Eval pyrolysis of the residual lignite showed that the nonhydrous residuals had on the average 16 mg more hydrocarbon potential per gram of original lignite than the hydrous residuals. This suggests there is a better release of the pyrolysis products from the lignite network in the hydrous experiments once generation occurs. For gas generation, at maximum yields, open nonhydrous pyrolysis generates the most hydrocarbon gas (21.0 mg/g original lignite), which is 20% more than closed nonhydrous pyrolysis and 29% more than hydrous pyrolysis. Closed nonhydrous pyrolysis generates on the average 14% more gas than hydrous pyrolysis, but the proportionality of the generated hydrocarbon gases is essentially the same for both pyrolysis methods. At maximum yields, CO2 generation is greatest in hydrous pyrolysis (99.5 mg/g original lignite), with yields being 37 percent higher than closed nonhydrous pyrolysis and 26% higher than open nonhydrous pyrolysis. The maximum yields of C14+ products are highest and similar for open nonhydrous pyrolysis and hydrous pyrolysis (125.6 and 125.9 mg/g lignite, respectively), and are more than 70% higher than closed nonhydrous pyrolysis. This difference in the maximum yields of C14+ products can be explained by differences in the proportionality between either cracking reactions that result in liquid product and char formation or trapping of generated products within the coal network (cross-linking reactions). Maximum yields of C14+ aliphatics from hydrous experiments may not have been attained, but the maximums that were observed and their GC traces are similar for the three pyrolysis systems.

Organic Geochemistry↗
USGS2003

The New Albany Shale petroleum system, Illinois basin - Data and map image archive from the material-balance assessment

The data files and explanations presented in this report were used to generate published material-balance approach estimates of amounts of petroleum 1) expelled from a source rock, and the sum of 2) petroleum discovered in-place plus that lost due to 3) secondary migration within, or leakage or erosion from a petroleum system. This study includes assessment of cumulative production, known petroleum volume, and original oil in place for hydrocarbons that were generated from the New Albany Shale source rocks. More than 4.00 billion barrels of oil (BBO) have been produced from Pennsylvanian-, Mississippian-, Devonian-, and Silurian-age reservoirs in the New Albany Shale petroleum system. Known petroleum volume is 4.16 BBO; the average recovery factor is 103.9% of the current cumulative production. Known petroleum volume of oil is 36.22% of the total original oil in place of 11.45 BBO. More than 140.4 BBO have been generated from the Upper Devonian and Lower Mississippian New Albany Shale in the Illinois Basin. Approximately 86.29 billion barrels of oil that was trapped south of the Cottage Grove fault system were lost by erosion of reservoir intervals. The remaining 54.15 BBO are 21% of the hydrocarbons that were generated in the basin and are accounted for using production data. Included in this publication are 2D maps that show the distribution of production for different formations versus the Rock-Eval pyrolysis hydrogen-indices (HI) contours, and 3D images that show the close association between burial depth and HI values.The primary vertical migration pathway of oil and gas was through faults and fractures into overlying reservoir strata. About 66% of the produced oil is located within the generative basin, which is outlined by an HI contour of 400. The remaining production is concentrated within 30 miles (50 km) outside the 400 HI contour. The generative basin is subdivided by contours of progressively lower hydrogen indices that represent increased levels of thermal maturity and generative capacity of New Albany Shale source rocks. The generative basin was also divided into seven oil-migration catchments. The catchments were determined using a surface-flow hydrologic model with contoured HI values as input to the model.

Illinois, Indiana↗
USGS2002

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

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 Geochemistry↗
USGS2002

Material-balance assessment of the New Albany-Chesterian petroleum system of the Illinois basin

The New Albany-Chesterian petroleum system of the Illinois basin is a well-constrained system from which petroleum charges and losses were quantified through a material-balance assessment. This petroleum system has nearly 90,000 wells penetrating the Chesterian section, a single New Albany Shale source rock accounting for more than 99% of the produced oil, well-established stratigraphic and structural frameworks, and accessible source rock samples at various maturity levels. A hydrogen index (HI) map based on Rock-Eval analyses of source rock samples of New Albany Shale defines the pod of active source rock and extent of oil generation. Based on a buoyancy-drive model, the system was divided into seven secondary-migration catchments. Each catchment contains a part of the active pod of source rock from which it derives a petroleum charge, and this charge is confined to carrier beds and reservoirs within these catchments as accountable petroleum, petroleum losses, or undiscovered petroleum. A well-constrained catchment with no apparent erosional or leakage losses is used to determine an actual petroleum charge from accountable petroleum and residual migration losses. This actual petroleum charge is used to calibrate the other catchments in which erosional petroleum losses have occurred. Petroleum charges determined by laboratory pyrolysis are exaggerated relative to the actual petroleum charge. Rock-Eval charges are exaggerated by a factor of 4-14, and hydrouspyrolysis charges are exaggerated by a factor of 1.7. The actual petroleum charge provides a more meaningful material balance and more realistic estimates of petroleum losses and remaining undiscovered petroleum. The total petroleum charge determined for the New Albany-Chesterian system is 78 billion bbl, of which 11.4 billion bbl occur as a accountable in place petroleum, 9 billion bbl occur as residual migration losses, and 57.6 billion bbl occur as erosional losses. Of the erosional losses, 40 billion bbl were lost from two catchments that have highly faulted and extensively eroded sections. Anomalies in the relationship between erosional losses and degree of erosion suggest there is potential for undiscovered petroleum in one of the catchments. These results demonstrate that a material-balance assessment of migration catchments provides a useful means to evaluate and rank areas within a petroleum system. The article provides methodologies for obtaining more realistic petroleum charges and losses that can be applied to less data-rich petroleum systems.

Illinois, Indiana, Kentucky↗
USGS2001

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

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 Geochemistry↗
USGS1999

D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III

Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310–381°C), time (12–144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil–hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330°C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ≈ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381°C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350°C for 72 h, or 330°C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115°C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected by exchange with water hydrogen at typical reservoir conditions over geologic time. It will be difficult to utilize D/H ratios of thermally mature bulk or fractions of organic matter to quantitatively reconstruct isotopic aspects of paleoclimate and paleoenvironment. Hope resides in compound-specific D/H ratios of thermally stable, extractable biomarkers (“molecular fossils”) that are less susceptible to hydrogen exchange with water-derived hydrogen.

Geochimica et Cosmochimica Acta↗
USGS1999

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

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 higher amount of precursors of Pr compared to Ph, and not to the different timing of generation of Pr and Ph.

Organic Geochemistry↗
USGS1999

Fluid inclusion and vitrinite-reflectance geothermometry compared to heat-flow models of maximum paleotemperature next to dikes, western onshore Gippsland Basin, Australia

Nine basalt dikes, ranging from 6 cm to 40 m thick, intruding the Upper Jurassic–Lower Cretaceous Strzelecki Group, western onshore Gippsland Basin, were used to study maximum temperatures ( T max ) reached next to dikes. T max was estimated from fluid inclusion and vitrinite-reflectance geothermometry and compared to temperatures calculated using heat-flow models of contact metamorphism . Thermal history reconstruction suggests that at the time of dike intrusion the host rock was at a temperature of 100–135°C. Fracture-bound fluid inclusions in the host rocks next to thin dikes (<3.4 m thick) suggest T max systematically increases towards the dike margin to at least 500°C. The estimated T max next to the thickest dike (thickness ( D )=40 m) suggests an extended zone of elevated R v-r to at least a distance from the dike contact ( X ) of 60 m or at X / D >1.5, using a normalized distance ratio used for comparing measurements between dikes regardless of their thickness. In contrast, the pattern seen next to the thin dikes is a relatively narrow zone of elevated R v-r . Heat-flow modeling, along with whole rock elemental and isotopic data, suggests that the extended zone of elevated R v-r is caused by a convection cell with local recharge of the hydrothermal fluids . The narrow zone of elevated R v-r found next to thin dikes is attributed to the rise of the less dense, heated fluids at the dike contact causing a flow of cooler groundwater towards the dike and thereby limiting its heating effects. The lack of extended heating effects suggests that next to thin dikes an incipient convection system may form in which the heated fluid starts to travel upward along the dike but cooling occurs before a complete convection cell can form. Close to the dike contact at X / D <0.3, R v-r often decreases even though fluid inclusion evidence indicates that T max is still increasing. Further, fluid inclusion evidence indicates that the evolution of water vapor or supercritical fluids in the rock pores corresponds to the zone where R v-r begins to decrease. The generation of the water vapor or supercritical fluids near the dike contact seems to change vitrinite evolution reactions. These metamorphic conditions, closer to the dike than X / D =0.3 make vitrinite-reflectance unreliable as a geothermometer. The form of the R v-r profile, as it indicates T max , can be interpreted using temperature profiles estimated from various heat-flow models to infer whether the dike cooled by conduction, incipient convection, or a convection cell. A contact aureole that consists of decreasing R v-r or T max extending out to X / D ≥2 and that has a T contact ≫( T magma + T host )/2 appears to be a signature of simple conductive cooling. Incipient convection is indicated by a R v-r profile that decreases to background levels at X / D <1. A convection cell is indicated by a wave-like form of the R v-r profile and consistently high R v-r that may not decrease to background levels until beyond distances of X / D >1.5.

International Journal of Coal Geology↗
USGS1998

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

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 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, alkylthiophene 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.

Organic Geochemistry↗
USGS1998

Biomarker generation from Type II-S kerogens in claystone and limestone during hydrous and anhydrous pyrolysis

A claystone and a limestone containing immature Type II-S kerogen were thermally matured in the presence and absence of water, to study the influence of water and clay minerals on the generation of biomarkers. In contrast to hydrous pyrolysis, anhydrous pyrolysis of the claystone did not generate biomarkers, which resulted in the loss of important information. Desulfurization of the polar fraction of the claystone showed that anhydrous pyrolysis is not capable of converting S-bound biomarkers to free biomarkers. For the limestone, the differences between hydrous and anhydrous pyrolysis are less dramatic. Adsorption of the polar fraction of the claystone to smectite interlayers probably leads to cross-linking reactions, preventing the generation of free biomarkers. During hydrous pyrolysis, the smectite interlayers are occupied by water so that generation of biomarkers can take place. In addition, cross-linking reactions during anhydrous pyrolysis of the claystone may be enhanced because of the presence of S-S bonds in the organic matter of the claystone. These results show that water is important in closed system laboratory experiments designed to simulate natural maturation of sedimentary organic matter.A claystone and a limestone containing immature Type II-S kerogen were thermally matured in the presence and absence of water, to study the influence of water and clay minerals on the generation of biomarkers. In contrast to hydrous pyrolysis, anhydrous pyrolysis of the claystone did not generate biomarkers, which resulted in the loss of important information. Desulfurization of the polar fraction of the claystone showed that anhydrous pyrolysis is not capable of converting S-bound biomarkers to free biomarkers. For the limestone, the differences between hydrous and anhydrous pyrolysis are less dramatic. Adsorption of the polar fraction of the claystone to smectite interlayers probably leads to cross-linking reactions, preventing the generation of free biomarkers. During hydrous pyrolysis, the smectite interlayers are occupied by water so that generation of biomarkers can take place. In addition, crosslinking reactions during anhydrous pyrolysis of the claystone may be enhanced because of the presence of S-S bonds in the organic matter of the claystone. These results show that water is important in closed system laboratory experiments designed to simulate natural maturation of sedimentary organic matter.

Conference Paper↗
USGS1998

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

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.

Organic Geochemistry↗
USGS1998

Sulphur-radical control on petroleum formation rates

Most petroleum is formed through the partial decomposition of kerogen (an insoluble sedimentary organic material) in response to thermal stress during subsurface burial in a sedimentary basin. Knowing the mechanisms and kinetics of this process allows the determination of the extent and timing of petroleum formation, which, in turn, are critical for evaluating the potential for petroleum occurrences within a sedimentary basin. Kinetic models of petroleum generation are derived mainly from pyrolysis experiments, in which it is usually assumed that formation rates are controlled by the strength of the bonds within the precursor compounds: this agrees with the observation that petroleum formation rates increase with increasing sulphur content of thermally immature kerogen, C-S bonds being weaker than C-C bonds. However, this explanation fails to account for the overall composition of petroleum. Here I argue, on the basis of pyrolysis experiments, that it is the presence of sulphur radicals, rather than the relative weakness of C-S bonds, that controls petroleum formation rates. My findings suggest that the rate of petroleum formation depends critically on the concentration of sulphur radicals generated during the initial stages of thermal maturation. The proposed mechanism appears to provide a realistic explanation for both the overall composition of petroleum and the observed variation in formation rates.

Nature↗
USGS1997

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

Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature ( R o = 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 38 n -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.

Vena del Gesso Basin↗
USGS1997

Experiments on the role of water in petroleum formation

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 2 O 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 generation of exogenous hydrogen and excess oxygen as CO 2 . One reaction series involves water oxidizing existing carbonyl groups to form hydrogen and carbonyl groups, with the latter forming CO 2 by decarbonylation with increasing thermal stress. Another reaction series involves either hydrogen or oxygen in dissolved water molecules directly interacting with unpaired electrons to form a hydrogen-terminated free-radical site or an oxygenated functional group, respectively. The latter is expected to be susceptible to oxidation by other dissolved water molecules to generate additional hydrogen and CO 2 . In addition to water acting as an exogenous source of hydrogen, it is also essential to the generation of an expelled saturate-enriched oil that is similar to natural crude oil. This role of water is demonstrated by the lack of an expelled oil in an experiment where a liquid Ga In alloy is substituted for liquid water. Experiments conducted with high salinity water and high water/rock ratios indicate that selective aqueous solubility of hydrocarbons is not responsible for the expelled oil generated in hydrous pyrolysis experiments. Similarly, a hydrous pyrolysis experiment conducted with isolated kerogen indicates that expelled oil in hydrous pyrolysis is not the result of preferential sorption of polar organic components by the mineral matrix of a source rock. It is envisaged that dissolved water in the bitumen network of a source rock causes an immiscible saturate-enriched oil to become immiscible with the thermally decomposing polar-enriched bitumen. The overall geochemical implication of these results is that it is essential to consider the role of water in experimental studies designed to understand natural rates of petroleum generation, expulsion mechanisms of primary migration, thermal stability of crude oil, reaction kinetics of biomarker transformations, and thermal maturity indicators in sedimentary basins.

Geochimica et Cosmochimica Acta↗