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.     

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.     

New aromatic biomarkers and possible maturity indicators found in New Albany Shale extracts

Aromatic hydrocarbons from benzene extracts of New Albany Shale were characterized. A biomarker that has a molecular weight of 546 and a structural configuration consistent with that of an alkyl-aromatic hydrocarbon (C₄₀H₆₆) was tentatively identified. It was found that the relative concentrations of the biomarker are indicative of differing levels of thermal maturity of the shale organic matter. A 40-carbon bicyclic carotenoid (C₄₀H₄₈) is proposed as the geochemical precursor of this biomarker. Thermal maturity of the shale organic matter can also be differentiated by observing differences in “fingerprints” as obtained by field-ionization mass spectrometry on the aromatic hydrocarbon fraction. Using this technique, we found that the more mature shale samples from southeastern Illinois contain more low molecular weight extractable aromatic hydrocarbons and the less mature shale samples from northwestern Illinois contain more high molecular weight extractable aromatic hydrocarbons. It was demonstrated that field-ionization and tandem mass spectrometric techniques through fingerprint and individual compound identification, are useful for shale aromatic hydrocarbon fraction characterization and for thermal maturation interpretation.     

Laboratory sulfurisation of the marine microalga Nannochloropsis salina

To understand more fully the mode of preservation of organic matter in marine sediments, laboratory sulfurisation of intact cells of the cultured microalga Nannochloropsis salina was performed using inorganic polysulfides in seawater at 50°C. Solvent extractable and non-extractable materials were analysed by GC–MS and Py–GC–MS, respectively, to study the incorporation of sulfur into the microalgal organic matter. No GC-amenable sulfur-containing compounds were found in the extracts apart from some minor thiophenes with a phytanyl carbon skeleton. The residue after extraction and hydrolysis contained abundant macromolecular sulfur-containing moieties as revealed by the presence of dominant C₂₈–C₃₂ thiols, thiophenes, thianes and thiolanes in the flash pyrolysates. These products are thought to be formed from moieties derived from sulfurisation of C₂₈–C₃₂ diols and alkenols, characteristic lipids of N. salina. C₁–C₂ alkylated thiophenes were also found in the pyrolysates and probably result from moieties formed upon sulfurisation of carbohydrates. The highly resistant biomacromolecule (algaenan) synthesised by N. salina remains unaffected by sulfurisation. The non-hydrolysable residue isolated from the sulfurised N. salina thus comprises algaenan and (poly)sulfide-bound long alkyl chains. The sulfurisation experiments show that both selective preservation of algaenans and lipid and carbohydrate “vulcanisation” can be involved in the preservation of algal organic matter in marine environments.     

A new approach to interpreting Rock-Eval S2 and TOC data for kerogen quality assessment

A simple method for application in source potential mapping is used to assess the original oil and gas potentials in source rock horizons based upon Rock-Eval potential (S₂) and total organic carbon (TOC) values. The method assumes that kerogens consist of mixtures of end-members with assigned hydrogen index values. Based on suggested algorithms, the average amounts of oil-prone, gas-prone and inert organic material over source rock intervals are determined in TOC units. The method uses regression lines from plots of remaining hydrocarbon potentials (S₂) versus total organic carbon (TOC), and “quick-look” transparent overlays are used to read the appropriate kerogen mixture.Mineral matrix effects during pyrolysis, when strong, can cause erroneous results. This effect which occurs for oil-prone kerogens and adsorptive minerals can cause problems particularly for lean samples (S₂ = 0–3 mg HC/g rock) whilst the errors for richer samples are less.The method is applied on three sections of Upper Jurassic organic-rich rocks from the Danish North Sea sector, which are at different maturity stages. One of these sections is dominated by gas-prone material, one is dominated by oil-prone material and the third section contains a mixture of oil- and gas-prone material.The method has been compared with other methods that split kerogens in oil and gas generating potential and has given reasonable results.Experience using the method and a presented example suggest that sedimentological, system tract information may be derived from S₂ to TOC cross-plots. A constructed modelling example suggests that the end-member concept used in this approach may be used in forward type source rock prediction models when combined with sedimentological models. The resulting S₂–TOC plots can be used in order to check the forward modelling results against observed values.     

TG/plus—a pyrolysis method for following maturation of oil and gas generation zones using Tmax of methane

Thermogravimetric Fourier transform infrared spectroscopy (TG-FTIR) analyses were carried out on two sets of isolated kerogens covering a wide maturity range from low mature (0.46% R_o) through the end of oil and gas generation (maximum R_{o = 5.32%}). Data onweight percent and T_max for evolution of methane, volatile tars, ethylene, SO₂, NH₃, CO₂, and CO are reported. The T_max of methane shows the most consistent response to increasing maturation in both sets of samples. Results are comparable to those of whole rocks from an Alaskan North Slope well analyzed previously. The collective data for both whole rocks and isolated kerogens shows a generally linear correlation between %R_o and T_max of methane, with the exception of R_o of about 2.0% where a dip in the curve occurs. The slope of the correlation line was steeper for the predominantly terrigenous Wilcox kerogen than for more marine Colorado kerogen or for the Alaskan North Slope whole rock samples, probably reflecting differences in the chemical nature of various kerogen sets, which is also reflected by differences in the shapes of the pyrolysis curves of SO₂, CO₂, CO, H₂O, and ethylene. These preliminary data indicate that T_max of methane is a good maturation indicator for whole rocks and isolated kerogens up to an R_o of about 4%, which includes all of the wet gas and a considerable portion of the dry gas generation zones. This correlation was also observed for samples containing migrated bitumen, where it was not possible to obtain a reliable T_max for the volatile tar (S2) peak. The more terrigenous Wilcox kerogens also showed a good correlation of the T_max of ethylene with %R_o. T_max of ammonia evolution did not correlate with maturity and occurred 100–200°C lower than previously found for whole rocks, consistent with a whole-rock source of pyrolytic ammonia for Alaskan whole rock samples. HI and OI indices were calculated in several ways and plotted to reflect kerogen type as well as both the residual oil and gas generation potential. The ratio of pyrolyzable to combustible sulfur (evolved as SO₂) was independent of maturity and showed a clear difference between the more terrigenous Wilcox kerogens and the more marine Colorado kerogens.     

Stable isotope geochemistry of coals, humic kerogens and related natural gases

Isotope systematics are well defined for conventional sapropelic, Type I/II kerogens and their associated bacterial and thermogenic natural-gas products. These geochemical tools are used to estimate source type, maturity and depositional environment, and as a correlation technique. In many cases the natural gas signatures in near-surface samples and drill cuttings can be used to classify or predict a deeper lying source rock or reservoir.Corresponding interpretative schemes for coals, Type III kerogens and their associated hydrocarbons are progressing quickly. The shift in attention to humic sources is driven primarily by depletion of conventional oil and gas resources and the economic and societal requirements of coal and coal-bed methane.Carbon, hydrogen and nitrogen stable isotope variations can be large between different coals and humic kerogens. These differences can often be recognized in their bulk δ¹³C_org, δD_org and δ¹⁵N_org values. Isotope signatures of coals can be diagnostic of several factors, including deposit age, type, geographic location, maturity and generation history. However, these characteristic isotopic variations are substantially better defined by the C-, H- and N-isotope ratios of the separate maceral groups, such as vitrinite, exinite and inertinite. This new application of stable isotopes, at the maceral and compound levels, have great potential to improve the interpretative precision over conventional whole coal or bulk techniques.Hydrocarbon gases, including coal gases, derived from coals and humic kerogens can be distinguished from Type I/II sources, based on their molecular rations, i.e., C₁/(C₂ + C₃) and by comparing their stable isotope compositions, especially δ¹³C_CH4 and δD_CH4. The δ¹³C_C2H6 can also be valuable, but ethane is generally present in small amount (<1 vol. %) and requires     

Similar morphological and chemical variations of Gloeocapsomorpha prisca in Ordovician sediments and cultured Botryococcus braunii as a response to changes in salinity

Most Ordovician source rocks consist of accumulation of a colonial marine microorganism, Gloeocapsomorpha prisca (G. prisca) whose nature, ecology and affinity with extant organisms have been in dispute for years. Furthermore, recent studies have shown major differences in phenol moieties between two G. prisca-rich samples. Examination of five G. prisca-rich kerogens by electron microscopy and pyrolysis studies revealed (i) the occurrence of two markedly distinct “morpho/chemical” types: a “closed/phenol-rich” type (Baltic samples) and an “open/phenol-poor” one (North American samples) and (ii) the selective preservation of the resistant micromolecular material building up the thick cell walls in the original organism. Comparison with extant Botryococcus braunii (a widespread green microalga) grown on media of increasing salinity suggests that G. prisca is likely to be a planktonic green microalga related to B. braunii, which can adapt to large salinity variations which, in turn, control its polymorphism. The large differences in colony morphology and in the content of phenol moieties observed in fossil G. prisca and the resulting occurrence of two “morpho/chemical” types, should therefore reflect depositional environments with different salinities. The presence of thick, highly aliphatic, resistant walls in G. prisca selectively preserved during fossilization, accounts for the major contribution of this organism to Ordovician organic-rich sediments and for the resulting typical signature of Ordovician oils.     

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.     

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.     

Simulation of the fluorescence evolution of “live” oils from kerogens in a diamond anvil cell: Application to inclusion oils in terms of maturity and source

The evolution of fluorescence has been measured for “live” oils generated from 14 oil-prone kerogens or coals from varying depositional environments during closed system pyrolysis in a diamond anvil cell at three heating rates (3, 8, and 25 °C/min), and temperatures up to 600 °C. The measured fluorescence intensities of the samples, employing using violet excitation at 405 nm, increases significantly during maturation intervals within the oil window, while the fluorescence spectra of oils generated from all studied kerogens exhibit progressive blue-shift of peak wavelengths (λ_max) and red/green quotients (I₆₅₀/I₅₀₀) upon increasing maturity. The observed trend is consistent with a maturity dependence of the spectral shift, which is widely recognized in natural hydrocarbon inclusions and crude oils using ultraviolet (UV) excitation (365 nm). The data presented herein suggest that the λ_max of spectra for inclusion oils shift in similar direction despite differences in composition or source kerogen. This implies that the reverse or anomalous trends reported for inclusion oils in nature may be attributed to other processes, which significantly alters the fluorescence properties of oils subsequent to their generation. Oils with the similar color (λ_max or I₆₅₀/I₅₀₀) can be derived from diverse kerogens with maturities that vary by ±0.3% Ro, suggesting that the fluorescent colors of crude and inclusion oils are both maturity- and source-dependent, and therefore cannot be used as universal maturity indicators. In addition, the blue-shifts observed for cumulative oils generated from all kerogens approaches similar minima λ_max values around the green-yellow wavelength (564 nm) and at I₆₅₀/I₅₀₀ values around 0.6, at maturities close to the middle or late stage of oil generation. This suggests that most late-stage cumulative oils will exhibit similar colors. Oils generated during late-stage maturity intervals, however, can exhibit colors with shorter wavelengths.     

Organic geochemistry of Deep Sea Drilling Project sediments from the Gulf of Calofornia—hydrothermal effects on unconsolidated diatom ooze

The effects of intrusive thermal stress have been studied on a number of Pleistocene sediment samples obtained from Leg 64 of the DSDP-IPOD program in the Gulf of California. Samples were selected from Sites 477, 478 and 481 where the organic matter was subjected to thermal stress from sill intrusions. For comparison purposes, samples from Sites 474 and 479 were selected as representative of unaltered material.The GC and GC-MS data show that lipids of the thermally unaltered samples were derived from microbial and terrestrial higher-plant detritus. Samples from sill proximities were found to contain thermally-derived distillates and those adjacent to sills contained essentially no lipids. Curie point pyrolysis combined with GC and GC-MS was used to show that kerogens from the unaltered samples reflected their predominantly autochthonous microbial origin. Pyrograms of the altered kerogens were much less complex than the unaltered samples, reflecting the thermal effects. The kerogens adjacent to the sills produce little or no pyrolysis products since these intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter.Examination of the kerogens by ESR showed that spin density and line width pass through a maximum during the course of alteration but ESR g-values show no correlation with maturity. Stable carbon isotope (δ¹³C) values of kerogens decrease by 1–1.5‰ near the sills at Sites 477 and 481 and the atomic N/C decreases slightly with proximity to a smaller sill at Site 478. Differences in maturation behavior between Site 477 and 481 and Site 478 are attributed to dissimilarities in thermal stress and to chemical and isotopic heterogeneity of Guaymas Basin protokerogen.     

Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.     

Effect of artificial maturation on carbazole distributions, as revealed by the hydrous pyrolysis of an organic-sulphur-rich source rock (Ghareb Formation, Jordan)

Hydrous pyrolysis experiments were performed on the Ghareb Formation (Upper Cretaceous, Jordan), a carbonate- and organic-rich (TOC 19.6%) source rock, using a temperature range of 200 to 360°C (72 h). The original sediment contains only low amounts of carbazoles, (maximum 2.2 μg/g bitumen for 1-methylcarbazole). With increasing thermal maturation, intense generation begins at temperatures only in excess of 300°C, reaching a maximum at 360°C. Likewise, during natural maturation, generation occurs at later stages of maturity (e.g. for Tithonian source rocks at >0.81% R_r and for Posidonia Shale at >0.88% R_r). Some isomeric changes during hydrous pyrolysis do not resemble those in nature whereas others do. The relative abundances of selected C₁- and C₂-alkylcarbazoles on ternary diagrams reveal differences, whereas the benzo[a]carbazole/benzo[a]carbazole+benzo[c]carbazole ratio is closely similar. The latter result supports the contention that maturation plays a key role in controlling carbazole distributions in source rocks. However, the results for alkylcarbazoles, especially the C₂-carbazoles, are not easy to interpret.     

The use of bisnorhopane as a stratigraphic marker in the Oseberg Back Basin, North Viking Graben, Norwegian North Sea

This paper discusses the occurrence of 28,30-dinor-17α,18α,21β-hopane (bisnorhopane) in stratigraphically, fairly well preserved Viking Group sections from wells in local depressions in the North Viking Graben Area. The results show the presence of high relative amounts of bisnorhopane in the “Syn-rift sections”, whilst the “Post-rift sections” contain little or no bisnorhopane. Since most exploration wells are drilled on structural highs, primarily penetrating the “Post-rift Draupne”, this may explain why many analyzed source rock sections in this area contain little bisnorhopane.As a correlation of Draupne sections using the vertical, relative bisnorhopane distributions, it is suggested to be a potential stratigraphic marker for the area, indicating the presence of “Syn-rift Draupne” sediments.The relative bisnorhopane amounts follow a logarithmic reduction with depth and thermal maturity. The bisnorhopane signal is nearly extinguished at 3700 m depth at a maturity of R_o = 0.9–1.0%.     

Determination of thermal maturity and organic matter type by principal components analysis of the distributions of polycyclic aromatic compounds

The thermal maturity and organofacies sensitivity of polycyclic aromatic compound (PAC) distributions was explored by examination of the aromatic fractions of solvent extracts from a diverse set of 53 shales, coals and kerogen macerals which have undergone either natural or artificial maturation and which represent all three principal sedimentary organic matter (OM) types. Systematic changes with maturation were observed in the following groups of isomers: tri- and tetramethylnaphthalenes, methyl- and dimethylphenanthrenes, methyl- and dimethyldibenzothiophenes, methylpyrenes, and methylchrysenes. The maturity differences were quantified by mathematical ratios of the relative concentrations of the more thermally stable isomers to the less stable, on the basis of theoretical considerations and empirical observations. The PAC maturity parameters, unlike those derived from saturated biomarker stereoisomers, are typically effective across the entire oil generation window. To compensate for the effects of OM type on the maturity parameters, they were combined using principal components analysis. The resulting first principal component was in good agreement with independent indicators of maturity. The relative distributions of C₀–C₃ alkylphenanthrenes, dibenzothiophene, methyldibenzothiophenes and methyldibenzofurans were evaluated by a separate principal components analysis. The results permitted an independent grouping of the samples by OM type and suggested additional, simple molecular ratios that allow graphical recognition of OM type, including the ratio of dibenzothiophenes to dibenzofurans and a ratio using C₂-alkylphenanthrene isomers.     

Characteristics of amorphous kerogens fractionated from terrigenous sedimentary rocks

A preliminary attempt to fractionate amorphous kerogens from terrigenous bulk kerogen by a benzene-water two phase partition method under acidic condition was made. Microscopic observation revealed that amorphous kerogens and structured kerogens were fractionated effectively by this method. Characteristics of the amorphous and structured kerogens fractionated by this method were examined by some chemical analyses and compared with those of the bulk kerogen and humic acid isolated from the same rock sample (Haizume Formation, Pleistocene, Japan). The elemental and infrared (IR) analyses showed that the amorphous kerogen fraction had the highest atomic$\text{H}\text{C}$ ratio and the lowest atomic $\text{N}\text{C}$ ratio and was the richest in aliphatic structures and carbonyl and carboxyl functional groups. Quantities of fatty acids from the saponification products of each geopolymer were in agreement with the results of elemental and IR analyses. Distribution of the fatty acids was suggestive that more animal lipids participate in the formation of amorphous kerogens because of the abundance of relatively lower molecular weight fatty acids (such as C₁₆ and C₁₈ acids) in saponification products of amorphous kerogens. On the other hand, although the amorphous kerogen fraction tends to be rich in aliphatic structures compared with bulk kerogen of the same rock samples, van Krevelen plots of elemental compositions of kerogens from the core samples (Nishiyama Oil Field, Tertiary, Japan) reveal that the amorphous kerogen fraction is not necessarily characterized by markedly high atomic $\text{H}\text{C}$ ratio. This was attributed to the oxic environment of deposition and the abundance of biodegraded terrestrial amorphous organic matter in the amorphous kerogen fraction used in this work.     

Biomarker transformations as constraints for the depositional environment and for maximum temperatures during burial of Opalinus Clay and Posidonia Shale in northern Switzerland

Samples from two argillaceous formations (Opalinus Clay and Posidonia Shale) of near-identical maturity from northern Switzerland were subjected to a geochemical characterisation of organic matter and to confined-system pyrolysis experiments. Throughout the study area, the characteristics of organic matter are similar, indicating a spatially homogeneous sedimentary facies. Posidonia Shale contains marine organic matter deposited in a reducing environment, while a predominantly terrigenous source and a more oxidising environment of deposition was identified for Opalinus Clay. In the western and central parts of the study area, organic maturity is close to the onset of oil generation. In the easternmost part, a higher maturity has been reached due to a deeper burial below thick Tertiary Molasse deposits.Isothermal pyrolysis experiments were conducted at temperatures between 250 and 390 °C over 24 h. Bitumen yields increase along similar pathways for both Opalinus Clay and Posidonia Shale, but the maximum values are displaced by 10–20 °C. Data pertaining to maturity were determined from GC–MS analyses of saturated hydrocarbons, and specific attention was given to C₂₉-sterane and C₃₂-hopane isomerisation ratios. The evolution of these parameters with rising temperature is slightly different in the two formations, which is attributed to the contrasting organic facies. The pyrolysis data, together with literature data from natural basins, were used to calculate kinetic parameters for C₂₉-sterane and C₃₂-hopane, assuming a single-step isomerisation scheme according to the Arrhenius law. The resulting values based on pyrolysis data alone are very similar to those based on the combination of pyrolysis and natural data. Activation energies are similar in both formations, while the frequency factors are up to one order of magnitude higher for Posidonia Shale when compared to Opalinus Clay. For the Benken site, maximum temperature during Cretaceous burial was calculated on the basis of the kinetic data, using the TTI approach. The resulting temperatures of 75–80 °C are 5–10 °C below those derived in the literature from apatite fission-track analysis, vitrinite reflectance and basin modelling.     

贵州中三叠统烂泥沟金矿有机质的初步研究

烂泥沟金矿是以浊积岩为容矿岩石的微细浸染型金矿。有机岩石学分析表明,矿石与围岩中干酪根类型无明显差别,同属腐泥-腐植型。与围岩相比,矿石中干酪根成熟度(R₀=2.74%-3.06%)和含金性(6.15-24.8μg/g)均较高;干酪根总含金量在全岩中所占的比例是围岩高于矿石。氯仿沥青“A”的检测说明,矿石样品中可溶性有机质形成于强还原和高盐度环境,沥青质和含硫有机化合物发育。研究认为,干酪根含金性与碳的活化有关;不饱和的有机基因对金的动一定转换可能具有重要意义。     

Geological and laboratory evidence for early generation of large amounts of liquid hydrocarbons from suberinite and subereous components

Suberinite, and subereous components of amorphous nature, comprise largely unrecognized, proficient sources of liquid hydrocarbons. Due to difficulties in recognizing the presence of subereous components and suberinite in organic sediments, the contributions of these liptinitic components to the organic input of source rocks are easily underestimated. Severe chemical alterations of suberinite in the vitrinite reflectance range of R_o = 0.35–0.60% are demonstrated. Organic geochemical data, obtained from samples subjected to natural maturation, reveal that subereous components/suberinite undergoes early thermal degradation to generate large amounts of hydrocarbons below R_o = 0.60%. Data obtained from laboratory maturation of immature, suberinite-rich coals indicate that about 50% of the potential of suberinite for generating C₁₂₊ hydrocarbons has already been exhausted during natural maturation of the samples, prior to the onset of the traditionally defined “oil window”. The present data (a) contradict the assumption that suberinite is mainly sourced by selective preservation/enrichment of a stable, highly aliphatic biopolymer, i.e. “suberan” and (b) suggest that suberinite contains appreciable amounts of aliphatic and aromatic moieties which are released at low thermal stress.