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At least 181 records · Page 10Linked to original sources
USGS1994

Geochemical changes in crude oil spilled from the Exxon Valdez supertanker into Prince William Sound, Alaska

North Slope crude oil spilled from the T/V Exxon Valdez in March 1989 and contaminated about 500 km of Prince William Sound shoreline. Aliphatic and aromatic hydrocarbons in oil samples collected in August 1990 and June 1992 from beaches on six islands impacted by the spill have been compared with the hydrocarbons from North Slope crude oil taken from the stricken tanker. Degradation processes have changed the physical appearance of this residual spilled oil; the beached oil as collected ranged from a light brown color, to a heavy black viscous oil, to a black, powder-like residue. In these physically different samples, terpane, sterane, and aromatic sterane distributions, as well as carbon isotope values, are similar and correlate with the original Exxon Valdez oil. On the other hand, n -alkanes, isoprenoids, and many of the polycyclic aromatic hydrocarbons which are present in the original crude oil are dramatically altered in the oil samples collected from the beaches.

Alaska↗
USGS1994

Relationships between data from Rock-Eval pyrolysis and proximate, ultimate, petrographic, and physical analyses of 142 diverse U.S. coal samples

Basic research on coal and oil shale led to automated pyrolysis analysis of petroleum source rocks; most widely used is the Rock-Eval equipment. In order to interpret Rock-Eval analyses in relation to traditional coal data, we analyzed 142 commercial coals with diverse rank, age, maceral and sulfur contents, for most regions of the United States. We compared the Rock-Eval data with traditional industrial coal data, including volatile matter, calorific value, hydrogen and oxygen content, free swelling index, and vitrinite reflectance. We found: (1) there is a close relationship between T max and vitrinite reflectance in the ranges 420–590°C T max and 0.4–3% R o max of most coals. (2) A close relationship between T max and volatile matter (%VM) extends through the entire sample range, including low-rank samples with 35–70% VM, a range where %VM is not considered to be a useful rank parameter. (3) TOC of medium- and high-rank coals is seriously under-measured by Rock-Eval; TOC of low-rank coals (less than 0.8% R o max ) is close to “dry basis” carbon from ultimate analysis. (4) The direct relationships between oxygen index (OI) and %O and between hydrogen index (HI) and %H are clear, though only broadly defined. However, there is virtually no band of concentrated data points on the HI versus OI pseudo-Van Krevelen diagram comparable to the “development line” on the H/C versus O/C diagram. (5) There are systematic relationships between Rock-Eval and industrial coal parameters such as calorific value and FSI, but much standardization would be needed before Rock-Eval could find a place in the coal industry. Tests with blends of coal and quartz sand and with various loads of coal alone showed that the amount of organic matter in the Rock-Eval load greatly influences results. Total load in the crucible, if largely inert, plays a small role, however. Increasing absolute or relative coal content causes under-evaluation of Rock-Eval TOC and over-rating of hydrogen. Blends of several coals yielded hydrogen and oxygen indexes related proportionally to the properties of the individual coals, but T max is not raised by addition of high-rank coal until over 40% is added.

Organic Geochemistry↗
USGS1994

Comparison of 14C ages of hydrothermal petroleums

In order to set limits on the time frame of formation of hydrothermal petroleum, we have obtained 14 C ages on samples from three diverse regions; Gulf of California (Guaymas Basin), Northeast Pacific Ocean (Escanaba Trough and Middle Valley), and the East African Rift (Tanganyika Trough). The results date the source of carbon and therefore provide maximum ages for the formation and emplacement of the hydrothermal petroleums. The youngest petroleum occurs iin the Souther Trough of Guaymas Basin (3200–6600 yr, mean 4692 yr); in the Northern Trough the petroleum is slightly older (7400 yr). Significantly older hydrothermal petroleum occurs in Escanaba Trough (17,000 yr) and Middle Valley (29,000 yr). A continental example from the East African Rift has an age of 25,000 yr, comparable to the ages observed in the oceanic samples from the Northeast Pacific Ocean. These ages affirm that hydrothermal petroleum formation is a very rapid process and took place some time between the latest Pleistocene and the present in these active hydrothermal systems.

Organic Geochemistry↗
USGS1995

Comparison of the petrography, palynology, and paleobotany of the Little Fire Creek coal bed, southwestern Virginia, U.S.A.

Two continuous cores that penetrated the Lower Pennsylvanian Little Fire Creek coal bed in the Southwestern coal field in southwestern Virginia were sampled and X-ray radiographed to determine subunit distinctions. Comparison of petrographic, palynologic, and paleobotanic data from the same sample sets from the two cores allowed for comparison of compositional data within the Little Fire Creek coal bed. The proximate, petrographic, palynologic, and plant tissue data from two sets of samples indicate a high ash, gelocollinite- and liptinite-rich coal consisting of a relatively diverse paleoflora, including lycopsid trees, small lycopsids, tree ferns, small ferns, pteridosperms (seed ferns), and rare calamites and cordaites. The relatively very high ash yields (3–80 wt%), the relatively thin subunits (1–28 cm), and the large scale vertical variations in palynomorph floras suggest that the study area was at the edge of the paleopea-forming environment. As a result, most of the compositional correspondences are among those components indicative of degradation or decomposition.

Virginia↗
USGS1995

The minimal response to contact metamorphism by the Devonian Buchan Caves Limestone, Buchan Rift, Victoria, Australia

A 2.2 m thick, Late Eocene (?) dike that intruded the Devonian Buchan Caves Limestone, near Murrindal, Victoria, has produced a narrow contact aureole only centimeters wide in the adjacent host rock. Mean solid bitumen reflectance ranges from about 2.4 to 2.7% and shows little change up to 6 m away from the dike contact. Carbon and oxygen isotope values also show little change except at the dike contact. The most detectable response of the rock to contact metamorphism is the proportion of solid bitumen grains with finely granular mosaic structure increase towards the dike. Also under cathodoluminescence (CL) excitation, the host rock is initially observed to be recrystallized to a uniform bright orange color. By 1 cm away from the contact, however, CL shows preservation of sharp boundaries in finely zoned burial cements. A regional study of thermal maturation and a geothermometer based on solid bitumen reflectance indicate paleotemperatures near 200°C were widespread in the Buchan Rift during peak burial near the time of the Devonian Tabberabberan Deformation. The lack of response of the Buchan Caves Limestone to contact metamorphism is attributed to: (1) prior heating to near 200°C; and (2) the fact that the dike intruded into cool, near surface, low-porosity rocks which may have been in the vadose zone.

eastern Victoria↗
USGS1996

Elemental composition and molecular structure of Botryococcus alginite in Westphalian cannel coals from Kentucky

Botryococcus-derived alginites from the Westphalian Skyline, No. 5 Block, Leatherwood (eastern Kentucky) and Breckinridge (western Kentucky) coal beds have been analyzed for elemental composition and functional group distribution using an electron microprobe and micro-FTIR, respectively. The alginites from Kentucky show a carbon range of 81.6 to 92% and oxygen content of 3.5 to 9.5%. Sulphur content ranges from 0.66 to 0.84% and Fe, Si, Al and Ca occur in minor quantities. FTIR analysis demonstrates dominant CH2, CH3 bands and subordinate aromatic carbon in all alginites. The major differences between alginites are in the ratios of CH2 and CH3 groups and ratios between aromatic bands in the out-of-plane region. These differences suggest that, although the ancient Botryococcus derives from a selective preservation of a resistant polymer, it undergoes molecular and some elemental changes through the rank equivalent to vitrinite reflectance of 0.5-0.85%. Other differences, such as intensities of ether bridges and those of carboxyl/carbonyl groups, are attributed to differences in depositional environments.

Organic Geochemistry↗
USGS1996

A geochemical study of macerals from a Miocene lignite and an Eocene bituminous coal, Indonesia

Optical and chemical studies of maceral concentrates from a Miocene lignite and an Eocene high-volatile bituminous C coal from southeastern Kalimantan, Indonesia were undertaken using pyro-Lysis, optical, electron microprobe and FTIR techniques Pyrolysis products of vitrinite from bituminous coal were dominated by straight-chain aliphatics and phenols. The huminite of the Miocene lignite produced mostly phenolic compounds upon pyrolysis. Differences in the pyrolysis products between the huminite and vitrinite samples reflect both maturation related and paleobotanical differences. An undefined aliphatic source and/or bacterial biomass were the likely contributors of n-alkyl moieties to the vitrinite. The resinite fraction in the lignite yielded dammar-derived pyrolysis products, as well as aliphatics and phenols as the products of admixed huminite and other liptinites. The optically defined resinite-rich fraction of the bituminous coal from Kalimantan produced abundant n-aliphatic moieties upon pyrolysis, but only two major resin markers (cadalene and 1,6-dimethylnaphthalene). This phenomenon is likely due to the fact that Eocene resins were not dammar-related. Data from the electron microprobe and Fourier transform infrared spectrometry strongly support the results obtained by Py GC MS and microscopy.

Organic Geochemistry↗
USGS2004

Characterizing thermogenic coalbed gas from Polish coals of different ranks by hydrous pyrolysis

To provide a better characterization of origin and volume of thermogenic gas generation from coals, hydrous pyrolysis experiments were conducted at 360??C for 72 h on Polish coals ranging in rank from lignite (0.3% R r) to semi-anthracite (2.0% Rr). Under these conditions, the lignites attained a medium-volatile bituminous rank (1.5% Rr), high-volatile bituminous coals attained a low-volatile bituminous rank (1.7% Rr), and the semi-anthracite obtained an anthracite rank (4.0% R r). Hydrous pyrolysis of a coal, irrespective of rank, provides a diagnostic ??13C value for its thermogenic hydrocarbon gases. This value can be used quantitatively to interpret mixing of indigenous thermogenic gas with microbial methane or exogenous thermogenic gas from other sources. Thermogenic methane quantities range from 20 dm3/kg of lignite (0.3% Rr) to 0.35 dm3/kg of semi-anthracite (2.0% Rr). At a vitrinite reflectance of 1.7% Rr, approximately 75% of the maximum potential for a coal to generate thermogenic methane has been expended. At a vitrinite reflectance of 1.7% Rr, more than 90% of the maximum potential for a coal to generate CO2 has been expended. Assuming that these quantities of generated CO2 remain associated with a sourcing coal bed as uplift or erosion provide conditions conducive for microbial methanogenesis, the resulting quantities of microbial methane generated by complete CO2 reduction can exceed the quantities of thermogenic methane generated from the same coal bed by a factor of 2-5. ?? 2004 Elsevier Ltd. All rights reserved.

Organic Geochemistry↗
USGS2004

Geochemical characterization of tarballs on beaches along the California coast. Part I - Shallow seepage impacting the Santa Barbara Channel Islands, Santa Cruz, Santa Rosa and San Miguel

Tarballs are common along the southern California coastline. This study investigates tarballs from beaches along this coastline, with a focus on Santa Cruz, Santa Rosa, and San Miquel Islands in the Santa Barbara Channel. The tarballs were fingerprinted using biomarker and stable carbon isotope parameters, and then grouped according to genetic similarities. The data show that the tarballs are of natural and not anthropogenic origin and that all originate from source rock within the Miocene Monterey Formation via shallow seeps offshore. Sterane biomarker parameters were found to vary widely in the sample set. Biodegradation, especially of the regular steranes, is the primary process impacting the biomarker distributions in a large group of samples. The most common tarball occurrences appear to come from offshore seepage near the west end of Santa Cruz Island. Another major group most likely was transported north from near Santa Monica Bay. Several individual occurrences of some of these tarball groups also were found on beaches as far north as Pt. Reyes and as far south as San Diego, indicating significant long-distance dispersal by ocean currents. This study begins a library of tarball fingerprints to be used as a database to help distinguish between natural and anthropogenic tar occurrences all along the California coast, and to compare shallow seepage with future samples of deeper production oils from the same area.

Organic Geochemistry↗
USGS2005

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

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.

Organic Geochemistry↗
USGS2006

Carbon isotopic fractionation of CH4 and CO2 during canister desorption of coal

Canister desorption of coal gas from freshly sampled coal is commonly used for exploratory assessment of the coalbed methane (CBM) potential of a basin or prospect, as well as for the sampling of gas for isotopic determination of the gas origin. Compositional and ??13C isotopic time-series of desorbing CBM and carbon dioxide (CO2) over 3-4 months demonstrate considerable compositional and isotopic shifts over time. Non-stationary chemical and isotopic characteristics are due to differences in diffusivity and adsorbance behavior of gas molecules and must be taken into account when attempting to reproducibly sample coal gases. Off-line gas processing on a vacuum line and on-line GC/MS analyses were performed on coal gas samples from the Springfield and Seelyville Coal Members of the Pennsylvanian age that were cored in the SE Illinois Basin in SW Indiana, USA. The coals cover a narrow range of maturity from 0.54% to 0.64% vitrinite reflectance. Methane initially desorbed faster than CO2, resulting in a 50% increase of the CO 2 content in bulk desorbing gas on the 50th day relative to the first day of desorption. After 50 days of desorption, about 90% of all coal gas was desorbed. Over the same time period, ??13C values of incrementally sampled coal gas increased by 2??? and 9???, for CH 4 and CO2, respectively, testifying to the greater retention of 13CH4 and 13CO2 relative to 12CH4 and 12CO2. An isotopic mass balance of the individual, sequentially desorbed and sampled gas amounts yielded weighted mean ??13CCH4 and ??13CCO2 values for characterizing the cumulatively desorbed gas. The overall mean ??13C values were equivalent to ??13C values of gases that desorbed at a time when half of the potentially available gas had been desorbed from coal, corresponding in this study to a time between day 5 and day 12 of canister desorption at 15-18??C. The total expected gas volume and the ???50% midpoint can thus be approximated for a desorbing coal gas sample, based on a dynamic prediction after the first five days of canister desorption. ?? 2005 Elsevier Ltd. All rights reserved.

Organic Geochemistry↗
USGS2006

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

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.

Organic Geochemistry↗
USGS2006

Bacterial biomarkers thermally released from dissolved organic matter

Hopane biomarker products were detected using microscale sealed vessel (MSSV) pyrolysis gas chromatography-mass spectrometry (GC-MS) analysis of dissolved organic matter from natural aquatic systems colonised by bacterial populations. MSSV pyrolysis can reduce the polyhydroxylated alkyl side chain of bacteriohopanepolyols, yielding saturated hopane products which are more amenable to GC-MS detection than their functionalised precursors. This example demonstrates how the thermal conditions of MSSV pyrolysis can reduce the biologically-inherited structural functionality of naturally occurring organic matter such that additional structural fragments can be detected using GC methods. This approach complements traditional analytical pyrolysis methods by providing additional speciation information useful for establishing the structures and source inputs of recent or extant organic material. ?? 2006.

Organic Geochemistry↗
USGS2007

Characterization of the origin of coalbed gases in southeastern Illinois Basin by compound-specific carbon and hydrogen stable isotope ratios

Coalbed gases and waters from exploratory and production gas wells in the southeastern Illinois Basin were sampled to assess geochemically the origin of coalbed gases, with an emphasis on the Springfield and Seelyville Coal Members that are commercially targeted for coalbed methane production in Indiana. On-line analyses of hydrocarbon gases methane to butanes (C1, C2, C3, n-C4, i-C4) and CO2 yielded gas concentrations, plus ??D and ??13C values. The low thermal maturity of Indiana coals with vitrinite reflectance R0 ??? 0.6% is in agreement with an overwhelmingly biogenic isotopic signature of coalbed gases containing ???96% methane generated via bacterial CO2-reduction. In contrast, thermogenic gas was generated in the stratigraphically equivalent coal beds in western Kentucky's Rough Creek Graben zone where higher maturities of up to R0 ??? 0.8% were reached owing to tectonic and hydrothermal activity. No secondary biogenic methane was observed in more mature western Kentucky coal beds where greater burial depth limits the recharge of meteoric water. Biogenic and thermogenic coalbed gases represent two end-members that are compositionally and isotopically distinct. Microbial biodegradation of thermogenic C2+ hydrocarbon gases in Indiana coal beds preferentially targets C3 and introduces isotope fractionation whereby remaining C3 is enriched in deuterium and 13C.

Organic Geochemistry↗
USGS2007

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

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.

Organic Geochemistry↗
USGS2007

An evaluation of petrogenic hydrocarbons in northern Gulf of Alaska continental shelf sediments - The role of coastal oil seep inputs

We compared hydrocarbons in water, suspended particulate matter (SPM), and riparian sediment collected from coastal watersheds along the Yakataga foreland with corresponding hydrocarbons in Gulf of Alaska benthic sediments. This comparison allows an evaluation of hydrocarbon contributions to marine sediments from natural oil seeps, coal and organic matter (e.g., kerogen) associated with eroding siliciclastic rocks. The samples from oil seeps show extensive loss of low-molecular weight n-alkanes (<n-C14) and the presence of large, bimodal unresolved complex mixtures (UCMs), in contrast to the hydrocarbon fingerprints on the SPM and riparian sediment samples collected upstream from the oil seeps. After entering the fluvial systems, hydrocarbons from seep oils are rapidly diluted, and associate with the SPM phase as oil-mineral-aggregates (OMA). Johnston Creek, the watershed containing the most prolific seep, conveys detectable seep-derived hydrocarbons to the Gulf of Alaska, but overall seep inputs are largely attenuated by the (non-seep) petrogenic hydrocarbon content of the high SPM loads. In contrast to the geochemical signature of seep oil, Gulf of Alaska benthic sediments are characterized by abundant alkylated naphthalene homologues, relatively smooth n-alkane envelopes (n-C9 through n-C34, but with elevated levels of n-C27, n-C29, and n-C31), and small UCMs. Further, hydrocarbons in benthic sediments are highly intercorrelated. Taken together, these characteristics indicate that seep oil is a negligible petrogenic hydrocarbon source to the Gulf of Alaska continental shelf. Coaly material separated from the benthic sediment samples using a dense liquid (???2.00 g cm-3) also accounted for a minor portion of the total PAH (1-6%) and total n-alkanes (0.4-2%) in the benthic samples. Most of the hydrocarbon burden in the sediments is found in the denser sediment fraction and likely derives from organic matter contributed by denudation of siliciclastic formations in the Yakutat terrane. We therefore conclude that previous investigations relying on source allocation models have considerably overestimated oil seeps as a hydrocarbon source to the Gulf of Alaska. ?? 2006 Elsevier Ltd. All rights reserved.

Organic Geochemistry↗
USGS2007

The abundance and distribution of diamondoids in biodegraded oils from the San Joaquin Valley: Implications for biodegradation of diamondoids in petroleum reservoirs

The biodegradability of diamondoids was investigated using a collection of crude oil samples from the San Joaquin Valley, California, that had been biodegraded to varying extent in the reservoir. Our results show that diamondoids are subjected to biodegradation, which is selective as well as stepwise. Adamantanes are generally more susceptible to biodegradation than other diamondoids, such as diamantanes and triamantanes. We report a possible pathway for the microbial degradation of adamantane. This cage hydrocarbon possibly breaks down to a metabolic intermediate through the action of microbes at higher levels of biodegradation in petroleum reservoirs. Microbial alteration has only a minor effect on diamondoid abundance in oil at low levels of biodegradation. Our results suggest that most diamondoids (with the exception of adamantane) are resistant to biodegradation, like the polycyclic terpanes (e.g. C19-C24 tricyclic terpanes, hopanes, gammacerane, oleananes, Ts, Tm, C29 Ts), steranes and diasteranes. Microbial alteration of diamondoids has a negligible impact on the quantification of oil cracking achieved using the diamondoid-biomarker method. ?? 2007 Elsevier Ltd. All rights reserved.

Organic Geochemistry↗
USGS2008

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

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 case studies. ?? 2007 Elsevier Ltd. All rights reserved.

Organic Geochemistry↗