Pyrolysis-GC characterization of whole rock and kerogen-concentrate samples of immature Jurassic source rocks from NW-Germany

Nine rock samples from three Jurassic stratigraphic units of a shallow core from NW Germany were analyzed by pyrolysis-gas chromatography. The units contain a mixed Type-II/III kerogen (Dogger-α), a hydrogen-rich Type-II kerogen (Lias-), and a hydrogen-poor Type-III kerogen (Lias-δ). All of the kerogen was immature (R_o = 0.5%). Two sets of kerogen concentrates (“AD”: HCl/HF followed by a density separation, and “A”: only acid treatment) prepared from the rock samples were also analyzed to make a detailed comparison of the pyrolysates of rock and corresponding kerogen-concentrates.Hydrogen-index (HI) values of the kerogen concentrates prepared from organic-carbon poor rock were nearly 200% higher than HI values of the rock samples. Changes in HI were minimal for the samples containing Type-II kerogen. The A and AD samples from the C_org-poor rock yielded pyrolysates with n-alkane series of very different molecular lengths. Pyrograms of the rock samples had n-alkane series extending to n-C₁₄; the chromatograms of the A samples reached the n-C₁₄-nC₂₀ range. The AD samples from C_org-poor rock and all three sample types from the C_org-rich rock had n-alkane series up to n-C₂₉. The benzene/hexane and toluene/heptane ratios for the C_org-poor rock and A samples were far higher than for the AD samples, which had ratios similar to those of all three sample types from the C_org-rich rocks. These results indicate that choice of kerogen preparation method is critical when C_org-poor samples are analyzed.     

The effects of radioactive decay of uranium on elemental and isotopic ratios of Alum shale kerogen

The organic matter in the Alum Shale of Sweden is believed to have been affected post-depositionally by irradiation from the natural decay of U. Alum Shale kerogen H/C ratios are inversely proportional to the natural log of the U concentration, presumably as a result of the liberation of H by irradiation of the organic matter. Stable isotopic ratios of¹³C/¹²C in Alum Shale kerogen are directly proportional to the natural log of the U concentration. Experimental irradiation of Green River shale generated hydrocarbon gases 18% lighter than the parent organic matter, which demonstrates the possibility that irradiation induced generation of isotopically light gases could lower¹³C/¹²C ratios in parent organic matter. Irradiation may be a factor governing the relation between¹³C/¹²C ratios in the Alum Shales. Alum Shale O/C ratios generally increase with increasing U concentration and it is suggested that irradiation of organic matter may facilitate oxidation. The “Rock-Eval” maturity parameters “P.I.” and “Tmax” decrease with increasing U concentration. “P.I.” is presumed to decrease as a result of bitumen destruction or polymerization by irradiation.     

Molecular characterization of Type I kerogen from the Green River Formation using advanced NMR techniques in combination with electrospray ionization/ultrahigh resolution mass spectrometry

This study describes a new approach for characterizing high molecular weight compounds in Type I kerogen, involving both nuclear magnetic resonance (NMR) spectroscopy and Fourier transform ion cyclotron mass spectrometry (FTICR-MS). Kerogen isolated from the Mahogany zone of the Green River Formation was examined directly using high resolution magic angle spinning (HRMAS) NMR to obtain liquid-like multidimensional spectra. It was then successively extracted with n-pentane, dichloromethane and pyridine. Pyridine extraction was also performed for comparison with the successive extractions. Using solid-state NMR, we show that the sum of the successive extracts and the single pyridine extract are quantitatively representative of the unextracted kerogen. This suggests that a non-invasive characterization of Green River kerogen can be obtained by examining the soluble extracts, all of which were subjected to ESI-FTICR-MS to identify a wide series of compounds. Series of polar CHO, CHOS and CHON compounds between C₁₂ and C₅₀₊ were found. In all the extracts the two homologous series of acids (C_nH_2nO₂ and C_nH_2n−2O₄) dominated. Collision-induced dissociation was also employed to identify the different functional groups comprising the different series. The CHO series contained carboxylic acid and alkoxyl groups, whereas the CHOS and CHON series contained sulfoxide groups and nitrile-type compounds. The results also show that pyridine extraction can be used either for screening a large series of samples or for the specific study of CHO compounds. However for a detailed and complete study of the different homologous series we recommend using the successive extraction protocol.     

Molecular mechanics and quantum mechanical modeling of hexane soot structure and interactions with pyrene

Molecular simulations (energy minimizations and molecular dynamics) of an n-hexane soot model developed by Smith and co-workers (M. S. Akhter, A. R. Chughtai and D. M. Smith, Appl. Spectrosc., 1985, 39, 143; ref. 1) were performed. The MM+ (N. L. Allinger, J. Am. Chem. Soc., 1977, 395, 157; ref. 2) and COMPASS (H. Sun, J. Phys. Chem., 1998, 102, 7338; ref. 3) force fields were tested for their ability to produce realistic soot nanoparticle structure. The interaction of pyrene with the model soot was simulated. Quantum mechanical calculations on smaller soot fragments were carried out. Starting from an initial 2D structure, energy minimizations are not able to produce the observed layering within soot with either force field. Results of molecular dynamics simulations indicate that the COMPASS force field does a reasonably accurate job of reproducing observations of soot structure. Increasing the system size from a 683 to a 2732 atom soot model does not have a significant effect on predicted structures. Neither does the addition of water molecules surrounding the soot model. Pyrene fits within the soot structure without disrupting the interlayer spacing. Polycyclic aromatic hydrocarbons (PAH), such as pyrene, may strongly partition into soot and have slow desorption kinetics because the PAH-soot bonding is similar to soot–soot interactions. Diffusion of PAH into soot micropores may allow the PAH to be irreversibly adsorbed and sequestered so that they partition slowly back into an aqueous phase causing dis-equilibrium between soil organic matter and porewater.     

Characterization of Estonian Kukersite by spectroscopy and pyrolysis: Evidence for abundant alkyl phenolic moieties in an Ordovician, marine, type II/I kerogen

The kerogen of a sample of Estonian Kukersite (Ordovician) was examined by spectroscopic (solid state ¹³C NMR, FTIR) and pyrolytic (“off-line”, flash) methods. This revealed an important contribution of long, linear alkyl chains in Kukersite kerogen. The hydrocarbons formed upon pyrolysis are dominated by n-alkanes and n-alk-1-enes and probably reflect a major contribution of selectivity preserved, highly aliphatic, resistant biomacromolecules from the outer cell walls of Gloeocapsomorpha prisca. This is consistent with the abundant presence of this fossilized organism in Kukersite kerogen. In addition high amounts of phenolic compounds were identified in the pyrolysates. Series of non-methylated, mono-, di- and trimethylated 3-n-alkylphenols, 5-n-alkyl-1,3-benzenediols and n-alkylhydroxybenzofurans were identified. All series of phenolic compounds contain long (up to C₁₉), linear alkyl side-chains. Kukersite kerogen is, therefore, an aliphatic type II/I kerogen, despite the abundance of free phenolic moieties. This study shows that phenol-derived moieties are not necessarily associated with higher plant-derived organic matter.The flash pyrolysate of Kukersite kerogen was also compared with that of the kerogen of the Guttenberg Oil Rock (Ordovician) which is also composed of accumulations of fossilized G. prisca. Similarities in the distributions of hydrocarbons and sulphur compounds were noted, especially for the C₁–C₆ alkylbenzene and alkylthiophene distributions. However, no phenolic compounds were detected in the flash pyrolysate of the Guttenberg kerogen. Possible explanations for the observed similarities and differences are discussed.     

Chemical structural studies of natural lignin by dipolar dephasing solid-state 13C nuclear magnetic resonance

Two natural lignins, one from a gymnosperm wood the other from angiosperm wood, were examined by conventional solid-state and dipolar dephasing ¹³C nuclear magnetic resonance (NMR) techniques. The results obtained from both techniques show that the structure of natural lignins is consistent with models of softwood and hardwood lignin. The dipolar dephasing NMR data provide a measure of the degree of substitution on aromatic rings which is consistent with the models.     

Elucidation of the Alum Shale kerogen structure using a multi-disciplinary approach

The significance and validity of integrating data obtained from a variety of analytical techniques to understand, elucidate and model kerogen's complex chemical structure is reported here using degradative (open and closed system pyrolysis, chemical oxidation), non-degradative (¹³C CP/MAS NMR) and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging in maturity from immature to post-mature with respect to petroleum generation, were studied and were chosen for their simple geological history, uniform organic matter type and high organic carbon content. The Alum Shale kerogens, which primarily consist of algal organic matter, liberate low molecular weight gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic acids on chemical oxidation. ¹³C NMR spectroscopy shows that the Alum Shale kerogens are anomalously rich in oxygen-bearing functional groups (such as C = O, ArCO, CHO, CH_xO), most of which apparently remain intact within the kerogen macro-molecule (KMM) through the diagenetic and catagenetic stages. Fragments released by different degradative techniques are quantified and the aromaticity (f_a), O/C and relative proportions of various carbon types estimated by ¹³C NMR. A synthesis of these data has allowed us to better understand the chemistry of the Alum Shale kerogen.     

The effect of organic matter type and organic carbon content on Rock-Eval hydrogen index in oil shales and source rocks

The amount of “gas-prone” kerogen (woody, fungal and “inert”) and the organic carbon content (TOC) are the two predominant factors affecting the hydrogen index (HI) in the 226 samples of lacustrine and marine oil shales and source rocks studied. HI decreases as a function of the amount of “gas-prone” kerogen and increases as a function of TOC. In addition, the type of amorphous kerogen influences the hydrogen index, and this can be roughly estimated from the fluorescence intensity of the amorphous kerogen. Nearly eighty percent of the variation in HI in these samples can be accounted for by the percentage of “gas-prone” kerogen, the TOC content, and the fluorescence of the amorphous kerogen in a multiple regression analysis.Hydrogen index increases as a function of TOC up to about 10% TOC (the relationship can be approximated by a quadratic equation) and then levels off. A possible explanation for this is that the capability of a rock to generate and expel hydrocarbons during pyrolysis increases with TOC. When the retention capacity of the rock matrix is saturated (at about 10% TOC) further increases in TOC have no effect on HI. It is also possible that the quality (i.e. oil-proneness) of the amorphous kerogen is poorer in low TOC samples than in high TOC samples.The samples came from the following oil shales and source rocks: Rundle (Queensland Eocene-Miocene), Mae Sot (northwestern Thailand, Eocene-Pliocene), River River (northwestern Colorado, Eocene), Toolebuc (western Queensland, Late Albian), the “Posidonienschiefer” (southwestern Germany, Toarcian), an Argentinian lacustrine deposit (Eocene-Miocene), the Kimmeridgian sections from four North Sea wells (blocks 21, 30, and 210), Monterey Shale (California, Miocene), and sections from six wells from the Alaskan Tertiary (North Slope, North Aleutian Shelf, Navarin Basin, Norton Sound). Most samples appear to be thermally immature (T.A.I. less than 1.8; R_o less than 0.6%) so they should be considered only potential source rocks.The lacustrine oil shales have a higher conversion ratio (yeild/TOC or S₁ + S₂/TOC) than do the marine oil shales in samples with only amorphous and algal kerogen. These, in turn, have a higher conversion ratio than the marine source rocks. These differences are roughly reflected in the fluorescence intensity of the amorphous kerogen. Free hydrocarbons are higher in the marine source rocks than in the marine oil shales, and are lowest in the lacustrine oil shales.     

Differences in the mode of incorporation and biogenicity of the principal aliphatic constituents of a Type I oil shale

Compound-specific stable carbon isotope (δ ) measurements on the aliphatic hydrocarbons released from an immature Tertiary oil shale (Göynük, Turkey) via hydropyrolysis, following solvent extraction and a milder hydrogenation treatment, have further highlighted that significant compositional differences may exist between the principal aliphatic constituents of the solvent extractable (bitumen) phase and the insoluble macromolecular network (kerogen) comprising the bulk of sedimentary organic matter. Whilst inputs from diverse sources; including algae, bacteria and terrestrial higher plants, were implied from analysis of solvent-extractable alkanes, the much larger quantities of kerogen-bound n-alkyl constituents released by hydropyrolysis had a uniform isotopic signature which could be assigned to (freshwater) algae. Remarkably, the aliphatics bound to the kerogen by relatively weak covalent bonds, liberated via catalytic hydrogenation, appeared to comprise mainly allochthonous higher plant-derived n-alkanes. These results provide further compelling evidence that the molecular constituents of bitumen and, indeed, of low-yield kerogen degradation products, are not necessarily reliable indicators of kerogen biogenicity, particularly for immature Type I source rocks. The isotopic uniformity of aliphatic n-hydrocarbons released by the high-conversion hydropyrolysis step for the ultralaminae-rich Göynük oil shale, lends further support to the theory that selective preservation of highly resistant aliphatic biomacromolecules is an important mechanism in kerogen formation, at least for alginite.     

Application of the pyrolysis-carbon isotope method for determining the maturity of kerogen in the Bakken shale

A maturity indexing procedure based on the isotopic difference between the total accumulated methane produced by exhaustive pyrolysis and the kerogen (Δ¹³C) and the mole ratio of methane to kerogen carbon (CMR), has been tested by applying a standardized technique, i.e. exhaustive pyrolysis (600°C for 120 hr) of extracted-powdered samples and measurement of the amounts and isotopic composition of the methane and kerogen carbon, on a suite of 15 Bakken shale samples.A linear relation was found between the carbon mole ratio of pyrolysis-derived methane and total organic carbon and the δ¹³C difference between the pyrolysis-derived methane and total organic carbon (r = −0.79); and between the amount of CH₄ generated from exhaustive pyrolysis and H/C atomic ratios (r = +0.91).     

An organic geochemical investigation on organic rich sediments from two Neogene formations in the Klias Peninsula area,West Sabah,Malaysia

Twenty organic rich outcrop samples from the Belait and Setap Shale formations in the Klias Peninsula area, West Sabah, were analysed by means of organic petrology and geochemical techniques. The aims of this study are to assess the type of organic matter, thermal maturity and established source rock characterization based primarily on Rock-Eval pyrolysis data. The shales of the Setap Shale Formation have TOC values varying from 0.6 wt%–1.54 wt% with a mean hydrogen index (HI) of 60.1 mg/g, whereas the shal...     

Lignin pyrolysis products: Their structures and their significance as biomarkers

Pyrolysis in combination with gas chromatography and mass spectormetry was used to characterize softwood, hardwood and grass lignins as well as the corresponding synthetic dehydro-polymers. The method permitted differentiation of the three types of lignins. Softwood lignins yielded exclusively guaiacyl derivatives, coniferaldehyde and coniferyl alcohol being major compounds. Hardwood lignins gave rise to guaiacyl and syringyl derivatives, among which syringaldehyde, coniferyl alcohol and sinapyl alcohol were the most prominent. Grass lignins, represented by bamboo lignin, yielded p-vinylphenol as major compound. In addition, other guaiacyl and syringyl pyrolysis products were identified. The results indicate that guaiacyl and syringyl compounds are unique pyrolysis products of lignins and woods. Because of the relatively high resistance of lignins these pyrolysis products can be considered as characteristic biomarkers for terrestrial plant input.     

Study of petroleum generation by pyrolysis—I. Pyrolysis experiments by Rock-Eval and assumption of molecular structural change of kerogen using13C-NMR

Green River shale (Type I kerogen), Yaamba shale (Type II kerogen) and Sarufutsu coal (Type III kerogen) were heated to various temperatures using Rock-Eval. The amount of hydrocarbons generated and weight loss by pyrolysis were measured to obtain a better understanding of petroleum generation. After the pyrolysis experiments, elemental analysis (C, H), vitrinite reflectance (%R_o) measurement, maceral observation, infrared spectroscopy (IR) and¹³C-NMR spectroscopy were carried out on the coal samples. Changes in H/C atomic ratio, IR and NMR spectra indicate that experiments by Rock-Eval resemble those of the natural evolution of kerogen. However, the petrographic changes of the coal show more similarity to coal liquefaction and coking than to natural coalification. Changes in the amount of generated hydrocarbons with increasing maturation show that Type II kerogen produces more hydrocarbons than does Type I when R_o does not exceed 1.1%. Petroleum generation curves for the three samples were concordant with trends in natural systems, and a conceptual model of petroleum generation curve classified into three types is proposed, namely (1) curve of total amount enerated, (2) curve of generation rate, and (3) curve of fluid composition. Changes of IR and NMR spectra after pyrolysis imply that generated hydrocarbons are derived from aliphatic C structures of kerogen macromolecules. Moreover, the difference in genetic potential between Type I and Type III reflects different amounts of aliphatic structures. Type I is assumed to have a simple assemblage (mainly polymethylene carbons), and Type III is assumed to have a more complex variety of structures that are responsible for the difference in generation rates between the two kerogen Types. A quantitative analysis of C species of various bond structure by¹³C-NMR confirms that petroleum generation is the process of bond cleavage of kerogen macromolecules; lower-energy bonds decrease at an earlier stage of reaction, while aromatic carbons with higher bond energies survive to form graphitic structure at postmature stages. Emphasis is placed on the idea that the most important and direct factor in petroleum generation is a change in the molecular structure of kerogen with increasing maturation. NMR and other methods providing information about molecular structures of kerogen will become strong tools for evaluating source rocks and sedimentary basins in the future.     

Primary alteration—oxidation of marine algal organic matter from oil source rocks of the North Sea and Norwegian Arctic: new findings

The presence of partially oxidized algal organic matter in oil-prone marine source rocks, is the rule rather than the exception. Partially oxidized, algal kerogen can still act as a significant source of liquid hydrocarbons. However, the corresponding peak of C₁₂ + hydrocarbon generation is shifted to a considerably lower maturity level compared with that of the classical Type II kerogen. The extent of primary alteration-oxidation of marine algal kerogen is monitored by means of solid state microfluorescence spectroscopy. A new parameter, the Primary Alteration Factor (PAF) is established, and the relationships between PAF and H/C, O/C, HI, TOC and between PAF and %₀δ¹³C are determined. The present data show large variations in the bulk chemistry of immature marine algal kerogens, and reveal evidence for gradational dehydrogenation/oxidation of the source organic matter. This contrasts with the recently proposed mechanism for kerogen formation. SEM analysis reveals a relationship between the physical breakdown of algal organic matter and the formation of liptodetrinite. FTIR analysis shows that the incorporation of primary oxygen in the kerogen macromolecules is not in the form of carbonyl or carboxyl functionalities. The presence of highly unreactive, stable oxygen, associated with aromatic structures in partially oxidized algal kerogen, is suggested by resistance of the kerogen to graphitization. The FTIR data also suggest the presence of aryl ether oxygen. The present findings raise fundamental questions regarding the mechanisms of kerogen cracking and kerogen formation, and have important implications for petroleum exploration.     

Models of natural organic matter and interactions with organic contaminants

Adsorption of organic contaminants onto soils, sediments and other particulates has the potential to be a major controlling factor in their bioavailability, fate and behavior in the environment. Models for estimating the amount and stability of sorbed organic contaminants based on the fraction of organic carbon in a soil or sediment can oversimplify the process of sorption in the environment. In order to help understand sorption of organic contaminants in soils and sediments, we modeled various components of natural organic matter (NOM) that are possible substrates for sorption. These substrates include soot particles, lignin, humic and fulvic acids. The molecular scale interactions of selected aromatic hydrocarbons with different substrates were also simulated. Results of the simulations include the 3-D structures of the NOM components, changes in structure with protonation state and solvation and the sorption energy between PAH and substrate. This last parameter is an indicator of the amount of contaminant that will sorb and the energy required to free the contaminant from the substrate. Although the simulation results presented in this paper represent a first-order examination of NOM and contaminant interactions, the findings highlight a number of essential features that should be included in future molecular models of NOM and contaminant sorption.     

Long-chain carboxylic acids in pyrolysates of Green River kerogen

Long-chain fatty acids (C₁₀-C₃₂), as well as C₁₄-C21 isoprenoid acids (except for C₁₈), have been identified in anhydrous and hydrous pyrolyses products of Green River kerogen (200–400°C, 2–1000 hr). These kerogen-released fatty acids are characterized by a strong even/odd predominance (CPI: 4.8-10.2) with a maximum at C₁₆ followed by lesser amounts of C₁₈ and C₂₂ acids. This distribution is different from that of unbound and bound geolipids extracted from Green River shale. The unbound fatty acids show a weak even/odd predominance (CPI: 1.64) with a maximum at C₁₄, and bound fatty acids display an even/odd predominance (CPI: 2.8) with maxima at C₁₈ and C₃₀. These results suggest that fatty acids were incorporated into kerogen during sedimentation and early diagenesis and were protected from microbial and chemical changes over geological periods of time. Total quantities of fatty acids produced during heating of the kerogen ranged from 0.71 to 3.2 mg/g kerogen. Highest concentrations were obtained when kerogen was heated with water for 100 hr at 300°C. Generally, their amounts did not decrease under hydrous conditions with increase in temperature or heating time, suggesting that significant decarboxylation did not occur under the pyrolysis conditions used, although hydrocarbons were extensively generated.     

Hydrocarbons and fatty acids in the Evergreen Shale,Surat Basin,Queensland, Australia

Alkane hydrocarbon and n-fatty acid distributions have been examined in cores taken over a 550 ft thickness through the lower Jurassic, largely non-marine Evergreen Shale, Surat Basin, Queensland, Australia. No depth trends in compound abundances or carbon preference indices are discernible. There is no evidence for significant generation of n-alkanes from kerogen nor for cracking of long-chain n-alkanes. The present distribution patterns of the biochemicals probably reflect closely the nature of the original organic matter. The general strong dominance of long-chain (C₂₀₊) n-alkanes; the lack of evidence for diagenetic change; and the absence of correlation between abundances of n-alkanes and n-fatty acids (among both the longer- and shorter-chain compounds), lead to the conclusion that at least the long-chain n-alkanes were largely deposited as such in the sediment, having originated in land-plant material, remains of which are abundant in the samples. In the upper 170 ft. (possibly marine), n-alkanes with chain lengths below C₂₀ become important, suggesting greater significance of aquatic life as a source of organic matter at the time of deposition, a conclusion which is in general accord with the geological history of the basin, although this history is not well known.     

A molecular and carbon isotope biogeochemical study of biomarkers and kerogen pyrolysates of the Kimmeridge Clay Facies: palaeoenvironmental implications

Structures and carbon isotopic compositions of biomarkers and kerogen pyrolysis products of a dolomite, a bituminous shale and an oil shale of the Kimmeridge Clay Formation (KCF) in Dorset were studied in order to gain insight into (i) the type and extent of water column anoxia and (ii) changes in the concentration and isotopic composition of dissolved inorganic carbon (DIC) in the palaeowater column. The samples studied fit into the curve of increasing δ¹³C of the kerogen (δ¹³C_TOC) with increasing TOC, reported by Huc et al. (1992). Their hypothesis, that the positive correlation between TOC and δ¹³C_TOC is the result of differing degrees of organic matter (OM) mineralisation in the water column, was tested by measuring the δ¹³C values of primary production markers. These δ¹³C values were found to differ on average by only 1‰ among the samples, implying that differences in the extent of OM mineralisation cannot fully account for the 3‰ difference in δ¹³C_TOC. The extractable OM in the oil shale differs from that in the other sediments due to both differences in maturity, and differences in the planktonic community. These differences, however, are not likely to have significantly influenced δ¹³C_TOC either. All three sediments contain abundant derivatives of isorenieratene, indicating that periodically euxinia was extending into the photic zone. The sediments are rich in organic sulfur, as revealed by the abundant sulfur compounds in the pyrolysates. The prominence of C₁-C₃ alkylated thiophenes over n-alkanes and n-alkenes is most pronounced in the pyrolysate of the sediment richest in TOC. This suggests that sulfurisation of OM may have played an important role in determining the TOC-δ¹³C_TOC relationship reported by Huc et al. (1992).     

Origin of low-molecular-weight alkylthiophenes in pyrolysates of sulphur-rich kerogens as revealed by micro-scale sealed vessel pyrolysis

Micro-scale sealed vessel (MSSV) pyrolysis experiments have been conducted at temperatures of 150, 200, 250, 300, 330 and 350°C for various times on a thermally immature Type II-S kerogen from the Maastrichtian Jurf ed Darawish Oil Shale (Jordan) in order to study the origin of low-molecular-weight (LMW) alkylthiophenes. These experiments indicated that the LMW alkylthiophenes usually encountered in the flash pyrolysates of sulphur-rich kerogens are also produced at much lower pyrolysis temperatures (i.e. as low as 150°C) as the major (apart from hydrogen sulfide) sulphur-containing pyrolysis products. MSSV pyrolysis of a long-chain alkylthiophene and an alkylbenzene indicated that at 300°C for 72 h no β-cleavage leading to generation of LMW alkylated thiophenes and benzene occurs. In combination with the substantial production of LMW alkylthiophenes with a linear carbon skeleton at these conditions, this indicated that these thiophenes are predominantly formed by thermal degradation of multiple (poly)sulfide-bound linear C₅–C₇ skeletons, which probably mainly originate from sulphurisation of carbohydrates during early diagenesis. LMW alkylthiophenes with linear carbon skeletons seem to be unstable at MSSV pyrolysis temperatures of ≥330°C either due to thermal degradation or to methyl transfer reactions. LMW alkylthiophenes with a branched carbon skeleton most likely derive from both multiple (poly)sulfide-bound branched C₅–C₇ skeletons and alkylthiophene units present in the kerogen.     

Comparative studies of the kinetic parameters of various algaenans and kerogens via open-system pyrolyses

Kinetic parameters were determined for the first time, via open-system pyrolyses, on algaenans (highly resistant biomacromolecules that are selectively preserved during kerogen formation) isolated from extant microalgae. Parallel studies were also carried out on 10 kerogens exhibiting, with one exception, a low level of maturity. These kerogens included samples chiefly derived from the selective preservation of the above algaenans and samples mainly, or almost exclusively, derived from the “natural vulcanization” pathway. Important differences in activation energy (E_a) distributions were observed between the four algaenans investigated and correlated with their chemical structures. The kerogens predominantly derived from algaenan-selective preservation (Pula alginite, NE 70 and BJ 248 Torbanites, Rundle Oil Shale) also exhibited pronounced differences in E_a distributions. These distributions provided: (i) information on the diversity of the source materials; and (ii) reflected the occurrence of important differences in chemical structures and thermal behaviour between three of the tested kerogens, even though they are all classified as low maturity type I. The Kimmeridge Clay samples and the Lorca Oil Shale showed broad E_a distributions shifted to low energies when compared with the above algaenans and kerogens. Such shifts reflect an important (or even almost exclusive for some of these kerogens) contribution of materials originating from sulphur incorporation into various lipids during early diagenesis. Finally, the kinetic data derived for the nine low maturity fossil samples were extrapolated to a very low, geological heating rate of 3°C Ma⁻¹ and the generation rate curves and cumulative yield curves thus obtained were compared.