Hydrothermal pyrolysis of organic matter in Riphean mudstone

The catagenesis of organic matter (OM) was modeled by the hydrothermal pyrolysis of a source rock (Riphean mudstone from eastern Siberia). Isothermal experiments 72-h long were carried out in an aqueous environment in autoclaves at temperatures of 300, 310, 320,..., 370°. The pyrolysis products were analyzed for yield of extract, organic carbon, and parameters of Rock-Eval pyrolysis. The amount of the generated liquid hydrocarbon (HC) compounds increased to a temperature of 340°C and then decreased. The experimental trend of the hydrogen index (HI) dependence on the T _Max temperature generally coincided with that for natural OM maturation. The carbon isotopic composition of the insoluble (in organic solvents) OM remained practically unchanged in the course of the experiments. The carbon structure of the solid remnants of the experimental samples was ordered (after the experiments) with the origin of turbostratic graphite with a spacing of d ₀₀₂≈3.5 A°. We also conducted pyrolysis in a diamond anvil cell equipped with a digital camera in order to obtain additional qualitative and quantitative information on oil generation and emigration in the source rock and isolated kerogen. Chemical kinetic parameters of kerogen cracking were calculated for pyrolysis in an open system. The extrapolation of the high-temperature experimental results is discussed with reference to natural OM maturation.     

Biological markers in bitumens and pyrolyzates of Upper Cretaceous bituminous chalks from the Ghareb Formation (Israel)

The sterane and triterpane distributions of three bituminous chalks from the Upper Cretaceous Ghareb Formation (Israel) were investigated both in the original extractable bitumens and in extracts obtained after pyrolysis of whole rock and isolated kerogen samples at 450°C. Pyrolysis was performed in a closed system under hydrous (whole rock) and anhydrous conditions (isolated kerogens). The carbon number distributions of steranes and triterpanes differ significantly between original bitumen and pyrolyzates. Unlike the bitumens in which diasteranes were not detected, the anhydrous pyrolyzates contain small amounts of diasteranes. The presence of water during pyrolysis leads to an increase of sterane isomerization, the abundant formation of diasteranes and an increase of the $\text{18α(}\text{H}\text{)-}\text{trisnorneohopane}\text{17α(}\text{H}\text{)-}\text{trisnorhopane}$ ratio. Sterane isomerization maturation parameters show a closer match between original bitumen and pyrolyzates after pyrolysis in a closed system when compared with an open system.     

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

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

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

Pyrolysis experiments were carried out on Monterey formation kerogen and bitumen and Green River formation kerogen (Type II and I, respectively), in the presence and absence of montmorillonite, illite and calcite at 200 and 300°C for 2–2000 hours. The pyrolysis products were identified and quantified and the results of the measurements on the gas and condensate range are reported here.A significant catalytic effect was observed for the pyrolysis of kerogen with montmorillonite, whereas small or no effects were observed with illite and calcite, respectively. Catalytic activity was evident by the production of up to five times higher C₁–C₆ hydrocarbons for kerogen with montmorillonite than for kerogen alone, and by the dominance of branched hydrocarbons in the C₄–C₆ range (up to 90% of the total amount at any single carbon number). This latter effect in the presence of montmorillonite is attributed to cracking via a carbonium-ion [carbocation] intermediate which forms on the acidic sites of the clay. No catalytic effect, however, was observed for generation of methane and C₂ hydrocarbons which form by thermal cracking. The catalysis of montmorillonite was significantly greater during pyrolysis of bitumen than for kerogen, which may point to the importance of the early formed bitumen as an intermediate in the production of low molecular weight hydrocarbons. Catalysis by minerals was also observed for the production of carbon dioxide.These results stress the importance of the mineral matrix in determining the type and amount of gases and condensates forming from the associated organic matter under thermal stress. The literature contains examples of gas distributions in the geologic column which can be accounted for by selective mineral catalysis, mainly during early stages of organic matter maturation.     

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

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

Low-temperature gas from marine shales

Thermal cracking of kerogens and bitumens is widely accepted as the major source of natural gas (thermal gas). Decomposition is believed to occur at high temperatures, between 100 and 200°C in the subsurface and generally above 300°C in the laboratory. Although there are examples of gas deposits possibly generated at lower temperatures, and reports of gas generation over long periods of time at 100°C, robust gas generation below 100°C under ordinary laboratory conditions is unprecedented. Here we report gas generation under anoxic helium flow at temperatures 300° below thermal cracking temperatures. Gas is generated discontinuously, in distinct aperiodic episodes of near equal intensity. In one three-hour episode at 50°C, six percent of the hydrocarbons (kerogen & bitumen) in a Mississippian marine shale decomposed to gas (C₁–C₅). The same shale generated 72% less gas with helium flow containing 10 ppm O₂ and the two gases were compositionally distinct. In sequential isothermal heating cycles (~1 hour), nearly five times more gas was generated at 50°C (57.4 μg C₁–C₅/g rock) than at 350°C by thermal cracking (12 μg C₁–C₅/g rock). The position that natural gas forms only at high temperatures over geologic time is based largely on pyrolysis experiments under oxic conditions and temperatures where low-temperature gas generation could be suppressed. Our results indicate two paths to gas, a high-temperature thermal path, and a low-temperature catalytic path proceeding 300° below the thermal path. It redefines the time-temperature dimensions of gas habitats and opens the possibility of gas generation at subsurface temperatures previously thought impossible.     

Pyrolysis of Transvaal kerogens. II. An evaluation of vacuum pyrolysis with polyethylene,polystyrene and their mixtures with minerals

A series of experiments have been conducted with polyethylene and polystyrene standards in an attempt to define the advantages and limitations of a vacuum pyrolysis—gas chromatography—mass spectrometry procedure for the characterization of kerogen and other macromolecular substances. Effects of variations in pyrolysis temperatures and times, sample sizes (weights) and thickness were evaluated together with the reproducibility of the nature and abundances of pyrolyzates. The effects of minerals (illite and quartz) admixed in the polymers were also considered with reference to the nature of the breakdown products. Optimal pyrolysis conditions, where primary pyrolyzates were sufficiently abundant and secondary products did not hinder characterization, were attained at 450°C and 60–90 min. The reproducibility of the nature and quantities of pyrolyzates was rather satisfactory at this temperature and pyrolysis time. However, relatively large samples of macromolecular matter, which is considerably volatile at this temperature, led to the synthesis of an abundant yield of secondary products, but sample thickness does not affect the nature of pyrolyzates. Admixed mineral matter affected the nature and relative abundances of the pyrolyzates but did not impede characterization of samples, as primary breakdown products were discernible. Macromolecular substances of limited volatility, heterogeneous chemical composition and containing intractable mineral matter, such as many kerogens, need to be pyrolyzed as relatively large samples. The vacuum procedure used in these studies may be to advantage, as compared with some other methods, to pyrolyze such samples. This method seems to be also suitable for the pyrolysis of volatile macromolecular matter, provided that small samples are employed.     

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/LiAlH₄) 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.     

The polymer-like organic material in the Orgueil meteorite

The insoluble organic material in the Orgueil (Cl) chondrite was analyzed by combined high vacuum pyrolysis-gas chromatography-mass spectrometry. Stepwise pyrolyses at 150, 300, 450 and 600°C of Orgueil meteorite powder which had been exhaustively extracted with solvents yielded a series of alkenes and alkanes to C₈, an extensive series of alkylbenzene isomers, thiophene, alkylthiophenes, and benzothiophene, together with the nitrogen- and oxygen-containing breakdown products, acetonitrile, acrylonitrile, benzonitrile, acetone and phenol. The Orgueil polymer fragmentation products are very similar both qualitatively and quantitatively to pyrolysis products of solvent-extracted Pueblito de Allende (C3) chondrite described in the literature.Changes in the relative abundances of polymer degradation products between 150 and 600°C imply the preferential loss of aliphatic and certain heteroatomic portions of the polymer at lower temperatures to leave highly condensed aromatic and heteroaromatic portions of the polymer which begin to fragment only at 450–600°C. The Orgueil polymer-like matter thus appears to be a complex mixture of polymerized materials having different thermal stabilities. Similarities between vacuum pyrolyzates of the Orgueil polymer and terrestrial kerogen suggest the possibility that meteorite organic matter may have been subjected on the meteorite parent bodies to diagenetic processes similar to those by which terrestrial kerogen is formed.     

Coalification stages from confined pyrolysis of an immature humic coal

An immature humic coal (subbituminous rank) from the Mahakam delta (Kutei basin, Kalimantan, Indonesia) was isothermally pyrolyzed in confined conditions at temperatures ranging from 250 to 400°C (10°C steps) at 700 bar pressure for 72 h. Solid, liquid and thermodesorbable phases originating from the pyrolyzates have been analyzed by different analytical techniques. Results indicate that a 10°C pyrolysis step is necessary to determine the timing and the sequence of the different transformations affecting the kerogen as well as the effluents. Four maturation/coalification stages are distinguished. Stage 1 (75–80 wt.% C) occurs when modifications mainly concern the oxygen-bearing functions of the kerogen. Stage 2 (82–85 wt.%o C) is characterized by the decrease of the aliphaticity and the primary cracking of the coal. Stage 3 (86–89 wt.% C) corresponds to the production of methane and the condensation of aromatic rings in the solid residue.     

Effects of thermal maturation on stable organic carbon isotopes as determined by hydrous pyrolysis of Woodford Shale

Acquiring crude oils that have been expelled from the same rock unit at different levels of thermal maturation is currently not feasible in the natural system. This prevents direct correlation of compositional changes between the organic matter retained in a source rock and its expelled crude oil at different levels of thermal maturation. Alleviation of this deficiency in studying the natural system requires the use of laboratory experiments. Natural generation of petroleum from amorphous type-II kerogen in the Woodford Shale may be simulated by hydrous pyrolysis, which involves heating crushed rock in contact with water at subcritical temperatures (<374°C). Four distinct stages of petroleum generation are observed from this type of pyrolysis; (1) pre-oil generation, (2) incipient-oil generation, (3) primary-oil generation, and (4) post-oil generation.The effects of thermal maturation on the δ¹³C values of kerogen, bitumen, and expelled oil-like pyrolysate from the Woodford Shale have been studied through these four stages of petroleum generation. Similar to the natural system, the kerogens isolated from the pyrolyzed rock showed no significant change in δ¹³C. This suggests that the δ¹³C value of kerogens may be useful in kerogen typing and oil-to-source rock correlations. δ¹³C values of bitumens extracted from the pyrolyzed rock showed an initial decrease during the incipient-oil generation stage, followed by depletion during the primary- and post-oil generation stages. This reversal is not favorable for geochemical correlation or maturity evaluation. Saturated and polar components of the bitumen show the greatest δ¹³C variations with increasing thermal maturation. The difference between the δ¹³C of these two components gives a unidirectional trend that serves as a general indicator of thermal maturation and is referred to as the bitumen isotope index (BII).δ¹³C values of the expelled pyrolysates show a unidirectional increase with increasing thermal maturation. The constancy and similarity of δ¹³C values of the aromatic components in the expelled pyrolysates and bitumens, with increasing thermal maturation, encourages their use in oil-to-oil and oil-to-source rock correlations. Isotopic type-curves for expelled pyrolysates indicate that they may be useful in oil-to- oil correlations, but have a limited use in oil-to-source rock correlations.     

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-IIS 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.     

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

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

Evaluation of the petroleum composition and quality with increasing thermal maturity as simulated by hydrous pyrolysis: A case study using a Brazilian source rock with Type I kerogen

Hydrous pyrolysis (HP) experiments were used to investigate the petroleum composition and quality of petroleum generated from a Brazilian lacustrine source rock containing Type I kerogen with increasing thermal maturity. The tested sample was of Aptian age from the Araripe Basin (NE-Brazil). The temperatures (280–360 °C) and times (12–132 h) employed in the experiments simulated petroleum generation and expulsion (i.e., oil window) prior to secondary gas generation from the cracking of oil. Results show that similar to other oil prone source rocks, kerogen initially decomposes in part to a polar rich bitumen, which decomposes in part to hydrocarbon rich oil. These two overall reactions overlap with one another and have been recognized in oil shale retorting and natural petroleum generation. During bitumen decomposition to oil, some of the bitumen is converted to pyrobitumen, which results in an increase in the apparent kerogen (i.e., insoluble carbon) content with increasing maturation.The petroleum composition and its quality (i.e., API gravity, gas/oil ratio, C₁₅₊ fractions, alkane distribution, and sulfur content) are affected by thermal maturation within the oil window. API gravity, C₁₅₊ fractions and gas/oil ratios generated by HP are similar to those of natural petroleum considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. API gravity of the HP expelled oils shows a complex relationship with increasing thermal maturation that is most influenced by the expulsion of asphaltenes. C₁₅₊ fractions (i.e., saturates, aromatics, resins and asphaltenes) show that expelled oils and bitumen are compositionally separate organic phases with no overlap in composition. Gas/oil ratios (GOR) initially decrease from 508–131 m³/m³ during bitumen generation and remain essentially constant (81–84 m³/m³) to the end of oil generation. This constancy in GOR is different from the continuous increase through the oil window observed in anhydrous pyrolysis experiments. Alkane distributions of the HP expelled oils are similar to those of natural crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. Isoprenoid and n-alkane ratios (i.e., pristane/n-C₁₇ and phytane/n-C₁₈) decrease with increasing thermal maturity as observed in natural crude oils. Pristane/phytane ratios remain constant with increasing thermal maturity through the oil window, with ratios being slightly higher in the expelled oils relative to those in the bitumen. Generated hydrocarbon gases are similar to natural gases associated with crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous, with the exception of elevated ethane contents. The general overall agreement in composition of natural and hydrous pyrolysis petroleum of lacustrine source rocks observed in this study supports the utility of HP to better characterize petroleum systems and the effects of maturation and expulsion on petroleum composition and quality.     

Effect of hydrocarbon volatility and adsorption on source-rock pyrolysis

Petroleum source-rock evaluations by pyrolysis are based on the concept that free hydrocarbons in rock samples are volatilized below 300°C while hydrocarbons cracked from kerogen come off at higher temperatures. The pyrolysis of pure hydrocarbons with different mineral matrices shows that free hydrocarbons containing 16 or more carbon atoms may not be evolved eblow 300°C, but at varying higher temperatures. The extent to which this occurs depends on the hydrocarbon volatility, the mineral matrix and the pyrolysis instrument design. Source-rock parameters which use the P₁ (S₁) peak may be not be reproducible between instruments if the rock contains appreciable amounts of high molecular weight hydrocarbons.     

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

This study examined the molecular and isotopic compositions of gases generated from different kerogen types (i.e., Types I/II, II, IIS and III) in Menilite Shales by sequential hydrous pyrolysis experiments. The experiments were designed to simulate gas generation from source rocks at pre-oil-cracking thermal maturities. Initially, rock samples were heated in the presence of liquid water at 330 °C for 72 h to simulate early gas generation dominated by the overall reaction of kerogen decomposition to bitumen. Generated gas and oil were quantitatively collected at the completion of the experiments and the reactor with its rock and water was resealed and heated at 355 °C for 72 h. This condition simulates late petroleum generation in which the dominant overall reaction is bitumen decomposition to oil. This final heating equates to a cumulative thermal maturity of 1.6% R_r, which represents pre-oil-cracking conditions. In addition to the generated gases from these two experiments being characterized individually, they are also summed to characterize a cumulative gas product. These results are compared with natural gases produced from sandstone reservoirs within or directly overlying the Menilite Shales. The experimentally generated gases show no molecular compositions that are distinct for the different kerogen types, but on a total organic carbon (TOC) basis, oil prone kerogens (i.e., Types I/II, II and IIS) generate more hydrocarbon gas than gas prone Type III kerogen. Although the proportionality of methane to ethane in the experimental gases is lower than that observed in the natural gases, the proportionality of ethane to propane and i-butane to n-butane are similar to those observed for the natural gases. δ¹³C values of the experimentally generated methane, ethane and propane show distinctions among the kerogen types. This distinction is related to the δ¹³C of the original kerogen, with ¹³C enriched kerogen generating more ¹³C enriched hydrocarbon gases than kerogen less enriched in ¹³C. The typically assumed linear trend for δ¹³C of methane, ethane and propane versus their reciprocal carbon number for a single sourced natural gas is not observed in the experimental gases. Instead, the so-called “dogleg” trend, exemplified by relatively ¹³C depleted methane and enriched propane as compared to ethane, is observed for all the kerogen types and at both experimental conditions. Three of the natural gases from the same thrust unit had similar “dogleg” trends indicative of Menilite source rocks with Type III kerogen. These natural gases also contained varying amounts of a microbial gas component that was approximated using the Δδ¹³C for methane and propane determined from the experiments. These approximations gave microbial methane components that ranged from 13–84%. The high input of microbial gas was reflected in the higher gas:oil ratios for Outer Carpathian production (115–1568 Nm³/t) compared with those determined from the experiments (65–302 Nm³/t). Two natural gas samples in the far western part of the study area had more linear trends that suggest a different organic facies of the Menilite Shales or a completely different source. This situation emphasizes the importance of conducting hydrous pyrolysis on samples representing the complete stratigraphic and lateral extent of potential source rocks in determining specific genetic gas correlations.     

Light hydrocarbons in subsurface sediments

The major features and numerous compositional details of the indigenous C₂–C₇ hydrocarbon suites of argillaceous sediments are systematically temperature dependent. The relative concentrations of alicyclic compounds exhibit a consistent maximum at subsurface temperatures close to 170°F (77°C) without regard to the chemical nature of the bulk of the kerogen, whether rich or poor in hydrogen, though this strongly affects the specific yield. A continuous increase in relative alkane content follows at higher temperatures. Indices of paraffinicity may be devised. One such, termed the ‘heptane value’ (essentially the percentage of n-heptane in the b.p. range 80.7–100.9°C), possesses a linear association with temperature, provides an index of catagenesis, and frequently provides a means of appraising paleotemperatures. Regressions of heptane value on temperature are compared in two composite stratigraphic sections dominated by kerogens representing two extremes of composition. The regression coefficients differ by 7%. Yields of light hydrocarbons increase exponentially in these sections by more than three orders of magnitude along sub-parallel, temperature-dependent curves. These similarities infer universally similar generating reactions and compositionally similar suites of light hydrocarbons at given subsurface temperatures, regardless of kerogen type, particularly for sections which underwent burial and heating during the Tertiary period.     

Pyrolysis of transvaal kerogens I. Diagenesis of kerogen in a stromatolite near Zeerust,South Africa: One possible chemical evolution process

This study represents an attempt to understand some of the many post-lithification chemical processes which affect the evolution of kerogen. Kerogens separated from four carbonate stromatolites, collected over a horizontal distance of ～ 350 km from the Malmani Dolomite of the Olifants River Group in the Transvaal Supergroup, were characterized by combined vacuum pyrolysis—gas chromatography-mass spectrometry. The relative profiles of the gas chromatographic peak distributions and intensities (·finger print patterns’) of three of the kerogen pyrolyzates were closely similar. The Zeerust stromatolite kerogen yielded a different pattern, showing a greater abundance of higher molecular weight aliphatic and alkyl aromatic hydrocarbon moieties than the other three samples. Many of the stromatolites near the Zeerust area contain epigenetic fluorite introduced by aqueous solutions. Fluid inclusion homogenization analysis showed that the emplacement temperature of fluorite in the sample studied was 100–200°C. Fluoride ion initiated base catalyzed condensations may have been a feasible cause for the production of higher molecular weight aliphatic and (indirectly) some alkyl aromatic moieties in this stromatolite, as compared to those in the other three samples. Acid-catalyzed condensations may also achieve similar results in aqueous diagenetic environments.     

An application of least-squares inverse analysis in kinetic interpretations of hydrous pyrolysis experiments

A least-squares inverse method is applied to the estimation of optimum kinetic parameters with statistical error bounds from concentration data obtained in isothermal hydrous pyrolysis experiments. The inverse method requires the specification of a data-parameter relationship (e.g., classical kinetic theory), the prior covariance matrices of data and parameter errors, as well as the prior central estimates of data and parameters. The reaction scheme considered is the common case of kerogen breakdown by Gaussian-weighted independent parallel first-order reactions and bitumen cracking by a single first-order reaction. The nonlinearity of the problem is reduced by a logarithmic transformation, which suggests a parameterization in terms of logarithmic concentrations, activation energies, and logarithmic Arrhenius factors. The linearized variance analysis is valid for the case studied, and the posterior covariance matrix reveals which parameters are constrained by the data. We find that the statistical errors in the average activation energy and the associated Arrhenius factor are strongly correlated. Hence, the parameters which determine the temperature dependence of the reaction rate have not been resolved independently. Furthermore, the kinetic results are very sensitive to the presence of a distribution of activation energies in kerogen breakdown. This distribution is not constrained by the data. As a consequence, neglecting the consideration of distributions of activation energies results in activation parameter values which are much too low. This is the major reason for the commonly encountered discrepancy between kinetic parameter values obtained from hydrous pyrolysis and micropyrolysis experiments, respectively.     

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

Steranes and triterpanes generated from pyrolysis of immature Monterey Formation kerogen in the presence and absence of calcite, illite and montmorillonite reveal results that are both consistent and divergent with published data that reflect the use of these biological markers as maturation indicators. The extent of isomerization of biomarkers generated from pyrolysis of kerogen at 300°C for 2 hours, at C-20 in 14α(H),17α(H)-steranes, at C-22 in 17α(H),21β(H)-hopanes and of 17β(H),21β(H)-hopanes correspond to early diagenetic stages in rock extracts from sedimentary basins. Isomerization increases with heating time and, after 1000 hours, attains values which correspond to the catagenetic stage in sedimentary basins, or equivalent to that of mature oil. Stepwise pyrolysis of the kerogen indicates faster isomerization rates for steranes and triterpanes in the bitumen than for those retained in the kerogen structure, confirming earlier studies.Presence of a mineral matrix can influence the isomerization of steranes and triterpanes considerably. Comparisons with results from kerogen heated alone, for a given maturation stage, show that calcite inhibits, illite catalyzes slightly and montmorillonite has a pronounced catalytic effect on these reactions. This effect results in early isomerization of steranes and hopanes corresponding to the catagenetic stage in the presence of montmorillonite, while kerogen or kerogen with calcite held at the same temperature (300°C) and time (10 hours) only yield isomerized products which correspond to a diagenetic stage. Further, illite and montmorillonite affect various isomerization reactions differently. The fastest reaction is the isomerization at C-20 in 14α(H),17α(H)-steranes followed by that at C-22 in 17α(H),21β(H)-hopanes and the slowest is the formation of 14β(H),17β(H) steranes.These results show that maturation measurements of rock or oil samples from sedimentary basins which use biological markers have to take into account the mineral matrix effects, which have been largely ignored until present.