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.     

Structural investigations of sulphur-rich macromolecular oil fractions and a kerogen by sequential chemical degradation

Structural studies of a sulphur-rich kerogen and macromolecular oil fractions from the Monterey Formation were performed by selective sequential chemical degradation. The method provides low-molecular weight compounds as former building blocks of the network which allow detailed analyses on a molecular level. The degradation sequence is based on three subsequently performed reactions—a selective cleavage of sulphur bonds in the first step carried out with Ni(0)cene/LiAlD₄, an ether and ester bond cleavage (BCl₃), and an oxidation of aromatic entities by ruthenium tetroxide as a final step. Each step of this sequence afforded a considerable amount of low-molecular weight material which was separated chromatographically and studied by GC and GC/MS, while the high-molecular weight or insoluble fractions were subjected to the next reaction step.The chemical degradation products—hydrocarbons and carboxylic acids—are discussed in terms of incorporation into the macromolecular structure, distribution of heteroatomic bridges and the genetic relationships between the different macromolecular crude oil fractions and kerogen.Labelling experiments with deuterium provided evidence for a simultaneous linkage by oxygen and sulphur functionalities or by aromatic units and sulphur bonds of cross-linking macromolecular network constituents.The determination of sulphur positions in the macromolecule suggests early diagenetic sulphur incorporation into the biological precursor compounds and subsequent formation of a cross-linked network.     

Molecular Structure of Kerogen in the Longmaxi Shale: Insights from Solid State NMR,FT‐IR,XRD and HRTEM

Kerogen plays an important role in shale gas adsorption, desorption and diffusion. Therefore, it is necessary to characterize the molecular structure of kerogen. In this study, four kerogen samples were isolated from the organic-rich shale of the Longmaxi Formation. Raman spectroscopy was used to determine the maturity of these kerogen samples. High-resolution transmission electron microscopy (HRTEM), 13C nuclear magnetic resonance (13C NMR) , X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy were conducted to characterize the molecular structure of the shale samples. The results demonstrate that VReqv of these kerogen samples vary from 2.3% to 2.8%, suggesting that all the kerogen samples are in the dry gas window. The macromolecular carbon skeleton of the Longmaxi Formation kerogen is mainly aromatic (fa’=0.56). In addition, the aromatic structural units are mainly composed of naphthalene (23%), anthracene (23%) and phenanthrene (29%). However, the aliphatic structure of the kerogen macromolecules is relatively low (fal*+falH=0.08), which is presumed to be distributed in the form of methyl and short aliphatic chains at the edge of the aromatic units. The oxygen-containing functional groups in the macromolecules are mainly present in the form of carbonyl groups (fac=0.23) and hydroxyl groups or ether groups (falO=0.13). The crystallite structural parameters of kerogen, including the stacking height (Lc=22.84 ?), average lateral size (La=29.29 ?) and interlayer spacing (d002=3.43 ?), are close to the aromatic structural parameters of anthracite or overmature kerogen. High-resolution transmission electron microscopy reveals that the aromatic structure is well oriented, and more than 65% of the diffractive aromatic layers are concentrated in the main direction. Due to the continuous deep burial, the longer aliphatic chains and oxygen-containing functional groups in the kerogen are substantially depleted. However, the ductility and stacking degree of the aromatic structure increases during thermal evolution. This study provides quantitative information on the molecular structure of kerogen samples based on multiple research methods, which may contribute to an improved understanding of the organic pores in black shale.     

Molecular fossils from chemical degradation of macromolecular organic matter

Hydrogenolysis with rhodium-on-charcoal was found to be an effective method for degrading different types of macromolecular material of geological origin. Between 6 and 70% of coals, kerogens and humic substances were transferred into low-molecular-weight soluble materials. The reaction products contained a series of monomeric and dimeric lignin-derived compounds which strongly suggest intact fossil lignin as their source. The substitutional patterns of the released phenols reflect the type and amount of terrestrial organic matter input and diagenetic alterations.In addition to the lignin constituents, a complete suite of hydrocarbons differing from those of the low-molecular-weight fraction was obtained after hydrogenolysis of the sample material. Hydrocarbons released by the hydrogenolytic degradation technique were attached to the polymeric matrix as monoor polyethers. Deuterium was used in the degradation experiment to evaluate the sites of chemical bonds by which 4-methylsteranes and hopanes are attached to the kerogen matrix. These experiments suggested a linkage of the released molecules with ring A and the side-chain, respectively.     

Molecular characterization of organic matter in sediments from the Keg River formation (Elk Point group), western Canada sedimentary basin

Distributions of free and sulfur-bound biomarkers in organic-rich sediments from the lower and upper Keg River formation (Elk Point group, western Canada) reveal deposition of these sediments under reducing conditions, in agreement with the geological data. The predominance of aryl isoprenoids of Chlorobiaceae origin indicates that photic zone anoxia occurred during time of deposition. A series of novel aryl isoprenoids with a carboxylic acid function was identified by GC–MS and the structure of the predominant 3-methyl-5-(2′,3′,6′-trimethylphenyl)pentanoate was proven by synthesis of an authentic standard. The occurrence of these acids gives evidence that oxidative breakdown at least partially accounts for the diagenetic fate of aromatic carotenoids. Li/EtNH₂ desulfurization of two kerogen concentrates yielded only low amounts of sulfur-bound hydrocarbons, and suggests that either sulfur sequestration was not a predominant process or, more probably, that a major part of the hydrocarbons, initially sulfurized, were released upon maturation, giving further evidence that (poly)sulfide bonds are cleaved at relatively low levels of thermal stress.     

Evidence for the rapid incorporation of hopanoids into kerogen

Hopanoids bound into the insoluble organic matter (kerogen) of Recent sediments from a freshwater lake (Priest Pot) and an anoxic sulphidic fjord (Framvaren) were released by hydropyrolysis and examined by gas chromatography-mass spectrometry. Bound hopanoids are present in high concentration (190-1400 μg/g TOC) and represent 22 to 86% of the total analysable hopanoids (i.e., bound and solvent-soluble), this proportion increasing with depth in Framvaren Fjord. The hopanes generated by hydropyrolysis contain higher amounts of the C₃₅, C₃₂, and C₃₀ homologues, reflecting the carbon number distribution of the bound hopanoids and indicating that both biohopanoids (C₃₀ and C₃₅) and their diagenetic products (dominated by C₃₂) are incorporated into the kerogen on a timescale of only 0 to 350 years. Sequential (multiple temperature) hydropyrolysis experiments gave an indication of the relative strengths of bonds being cleaved in association with hopane generation: The hopanoids of a sediment from Priest Pot are almost entirely bound by strong covalent bonds, interpreted to be mainly ether linkages, whilst a Framvaren sediment contains hopanoids that are bound by a mixture of weak di-/polysulphide linkages and stronger ether bonds. Labelling with deuterium indicated that the strong covalent linkages dominate, even for the Framvaren sediment.     

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.     

Organic pollutants associated with macromolecular soil organic matter: Mode of binding

A study of ether-linked moieties in macromolecular bound residues of polycyclic aromatic hydrocarbons (PAH) generated in bioremediation experiments was performed using high temperature hydrolysis degradation with subsequent analysis of the products by GC-MS. This hydrolysis reaction was specifically designed to cleave ether bonds including relatively stable diarylether structures. Among the reaction products, aromatic alcohols representing typical microbiologically derived metabolites of PAH were found in addition to natural compounds. Thus, parts of the bound residues appeared to be linked within the macromolecular material by ether bonds. Model experiments with an oxidoreductase enzyme and aromatic alcohols indicate the formation of these ether bonds to be an enzyme-catalysed process.     

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.     

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.     

Contact-metamorphic effect on parameters for kerogen maturation

This study examines the effect of contact metamorphism by an igneous dyke on parameters for kerogen maturation, such as elemental composition (H/C, O/C, N/C), ¹H-NMR T₁, vitrinite reflectance and infrared spectra. Although elemental composition and ¹H-NMR T₁ of the kerogen changed only within 1.5 and 5.0 m from the dyke respectively, vitrinite reflectance of the kerogen was thermally affected beyond 10.0 m from the intrusion. It is concluded that vitrinite reflectance is the most sensitive of the parameters evaluated to assess thermal stress of kerogens.     

Biomarker distributions in asphaltenes and kerogens analysed by flash pyrolysis-gas chromatography-mass spectrometry

Biomarker distributions in a suite of asphaltenes and kerogens have been analysed by flash pyrolysis directly coupled to a GCMS system. Attention has been focussed on biomarkers of the sterane and triterpane types. The sample suite under investigation consists of sediments with different kerogen types and some crude oils. Biomarker distributions in the pyrolysates have been compared with the “free” biomarkers in the corresponding saturated hydrocarbon fractions.The analyses show significant differences between the distributions of the free biomarkers and those in the pyrolysates. The latter have lower amounts of steranes while diasteranes are absent or present at low concentrations only. In the triterpane traces a shift of maximum intensity from C₃₀ (free compounds) to C₂₇/C₂₉ is observed. Furthermore, the pyrolysates contain a set of triterpenes (not present among the free compounds), and there is a selective loss of “non-regular” triterpanes that are present in the saturated hydrocarbon fractions. The observed differences between pyrolysates and free hydrocarbons can be explained partly by the processes occurring during pyrolysis such as bond rupture and subsequent stabilisation of primary pyrolysis products. To a certain extent these differences also show that maturation processes occurring in sediments have effects on free biomarker molecules different from those on molecules that are enclosed in a macromolecular matrix (kerogen or asphaltenes).Differences between biomarker distributions of asphaltene and kerogen pyrolysates are relatively small. A comparison with the pyrolysates from extracted whole sediments suggests that these differences are mainly caused by interactions between the organic material and the mineral matrix during pyrolysis.Oil asphaltenes behave differently from sediment asphaltenes as their pyrolysates are more similar to the corresponding saturated hydrocarbon fractions, i.e. the differences described above are observed to a much smaller extent. This different behaviour appears to be the result of coprecipitation of a part of the maltene fraction with the oil asphaltenes.     

Gas-generation potential of shales in small and medium-sized basins: a case study from the Xuanhua Basin,north China

Abstract

Small- and medium-sized basins are widely distributed, and some contain commercial gas reservoirs demonstrating their gas-generation potential. The Xuanhua Basin, which is a small-sized coal-bearing basin in north China, includes a promising target for shale-gas exploration in the Xiahuayuan Formation. In this study, we used this basin as a case study to assess the critical geochemical features for small or medium-sized basins to form commercial gas reservoirs. Total organic carbon (TOC) analysis, Rock-Eval pyrolysis, microscopic observation of macerals, vitrinite reflectance measurement and kerogen stable carbon isotope analysis were performed to characterise the organic geochemistry of the Xiahuayuan shales. The original total organic carbon (TOC_o) content and hydrocarbon-generative potential (S_2o) were reconstructed to further evaluate the gas-generation potential of these shales. In addition, geochemical data of shales from other similar-sized basins with gas discoveries were compared. The results showed that the kerogen from the Xiahuayuan Formation is Type III (gas-prone), and macerals are dominated by vitrinite. TOC values showed a strong heterogeneity in the vertical profiles, with most higher than 1.5?wt%. The measured R_o values ranged from 1.4 to 2.0%. However, thermal maturity was not correlated with the present-day burial depth with higher maturity in the wells closest to the diabase intrusion centre. The remaining generation potential (S₂) averaged 0.91?mg HC/g rock, equal to 1.4?cm³ CH₄/g rock, and the average amount of hydrocarbon generated was 4.33?cm³ CH₄/g rock. In small and medium-sized basins, the TOC content of commercially developed gas shales ranged from 0.5 to 2.5?wt%, organic matter was mainly humic (gas-prone), and the burial depth was generally shallow. Biogenic gas reservoirs for commercial exploitation tend to have larger shale thicknesses (120–800?m) than thermogenic gas reservoirs (60–90?m).

1. The Xiahuayuan Formation is a good gas-source rock with gas-prone kerogen type, relatively high TOC values and moderate thermal maturity.

2. The average amount of hydrocarbon generated from the Xiahuayuan shales is about 4.33?cm³ CH₄/g rock, indicating a potential to form a shale gas reservoir.

3. Owing to the influence of diabase intrusions, the Xiahuayuan shales have entered the dry gas window at relatively shallow-buried depths.

4. Small- and medium-sized basins have the potential to generate commercial gas reservoirs with the generated volume mainly a product of the thickness and maturity of black shales.

     

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.     

Polar and neutral isopranyl glycerol ether lipids as biomarkers of archaea in near-surface sediments from the Nankai Trough

The molecular and carbon isotopic compositions of polar isopranyl glycerol ether lipids, which are direct indicators of viable archaea, and neutral isopranyl glycerol ether lipids, which are derived from polar lipids via hydrolysis, in near-surface sediments from a methane seep in the Nankai Trough (off central Japan) were investigated. Procedures for extracting, separating and derivatizing polar and neutral ether lipids for detection using gas chromatography were first examined with one sediment sample and a cultivated methanogen. For all sediment samples, archaeol and hydroxyarchaeol were detected in both the polar and neutral ether lipid fractions. Acyclic and cyclic biphytanes were also detected in both types of lipid fractions after treatment with HI/LiAlH₄ for ether cleavage and alkylation. The δ¹³C values of archaeol, sn-2-hydroxyarchaeol, and sn-3-hydroxyarchaeol in the sample from 0.82 m below the seafloor were lower than −100‰ relative to PDB, indicating that diverse living methanotrophic archaea are present in the seep sediments. Biphytanes released from polar ether lipids in the same sample were less depleted in δ¹³C (−71‰ to −36‰). The wide range of δ¹³C values suggests that the biphytanes were derived not only from methanotrophic but also from non-methanotrophic archaea, and that the relative contributions of the methanotrophic and non-methanotrophic archaea differed, depending on the biphytane compound. The vertical profiles and δ¹³C values of the neutral ether lipids were similar to those of the intact polar ether lipids, suggesting that neutral ether lipids derived from fossil archaea in the samples had mainly been lost by the time of sampling.     

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.     

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.     

Chemical characterization of the kerogen from Moroccan Timahdit oil shale by analysis of oxidation products

A 33 step alkaline permanganate degradation of the kerogen from Moroccan Timahdit oil shale (M-Zone) was carried out. A very high total yield of oxidation products was obtained (95.4% based on original kerogen). Detailed GC-MS analyses of ether-soluble acids, acids isolated from aqueous solutions and soluble products of further controlled permanganate dedradation of precipitated, ether-insoluble acids, served as a basis for the quantitative estimation of the participation of various types of products and for comparison with other kerogens. The most interesting finding was the observed uniquely high yield of aromatic oxidation products from an intermediate type I–II kerogen. Taking into account the almost equally dominant aliphatic (50.2%) and aromatic (43.2%) nature of the acidic oxidation products, the existence of an aliphatic cross-linked nucleus mixed with cross-linked aromatic units in the Timahdit shale kerogen is postulated. Uniform distribution of oxidation products throughout the degradation suggested a similar reactivity of the various kerogen constituents towards alkaline permanganate.     

Structural relationships between a brown coal and its kerogen and humic acid fractions

A South Australian Tertiary brown coal is fractionated into humic acid and kerogen fractions. These related samples are then subjected to a number of different analytical techniques including infrared and¹³C-Nuclear Magnetic Resonance spectroscopies and pertrifluoroacetic acid oxidation. Structural conclusions are drawn from an integrated consideration of the data. Brown coal aliphatic structure is concentrated in the kerogen and the solvent soluble polar acid fractions. The humic acids are the most aromatic and contain a high degree of hydrogen bonding. Only very minor amounts of long polymethylene chain structures are observed in the humic acids, in complete contrast to the kerogen fraction. Different organic detrital origins are proposed for the coal fractions.     

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.