Carbon isotopic composition of individual n-alkanes in asphaltene pyrolysates of biodegraded crude oils from the Liaohe Basin, China

Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C₁₆–C₂₉ range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.     

Hydrous pyrolysis of sediments: Composition and proportions of aromatic hydrocarbons in pyrolysates

Hydrous pyrolysis (closed vessel autoclaving in the presence of excess water) of organic-rich rocks is said to generate oils which closely resemble natural crude oils in their broad characteristics and composition. However there are only a few accounts of the proportions and compositions of hydrocarbons in hydrous pyrolysates and none of these discuss the aromatic hydrocarbon composition in detail. The present paper presents some data on the latter.Hydrous pyrolysis (3 days) of a dolomitic siltstone (Permian, Marl Slate) at 280, 300,320, 340 and 360°C produced significant amounts of oils in which the aromatic hydrocarbons were one and a half to two times as abundant as the saturated hydrocarbons.The overall composition of the aromatic hydrocarbons was similar to most crude oils; the major components isolated by our methods from natural oils and from pyrolysates were C_1–4 alkylnaphthalenes. At the lowest pyrolysis temperature (280°C) the distributions of the more minor components of the pyrolysates (e.g. alkylphenanthrenes, aromatic steroids) were also generally similar to those found in natural crudes. However, a number of components (e.g. methylanthracenes, Diels' hydrocarbon) which are not usually reported in crudes, were also detected and the relative proportions of these increased at the higher temperatures. Hydrous pyrolysis (340°C) of an organic-rich oil shale (Jurassic, Kimmeridge) and an asphaltic-material containing no minerals produced pyrolysates in which many of these unusual compounds were also present. In addition the pyrolysate of the oil-shale contained higher proportions of organic sulphur compounds. It appears that the formation of the unusual compounds is not simply a function of the type of organic matter or mineralogy but rather of the high temperatures or fast heating rates employed.     

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

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

Effects of chemical environment on the solubility and incorporation mechanism for hydrogen in olivine

To investigate the solubility and the sites of incorporation of hydrogen in olivine as a function of point defect concentration, two-stage high-temperature annealing experiments have been carried out. The first annealing stage (the dry preannealing stage) was conducted at a total pressure of 0.1 MPa, a temperature of 1300° C and various oxygen fugacities in the range 10^?11–10^?4 MPa for times > 12 h. In these heat treatments, the samples were buffered against either orthopyroxene or magnesiowustite, or they remained unbuffered. The second annealing stage (the hydrothermal annealing stage) was performed at 300 MPa and 900–1050 ° C under a hydrogen fugacity of ～ 158 MPa for 1–5 h. Infrared spectra from the annealed samples revealed two distinct groups of bands. Group I bands occurred at wavenumbers in the range 3450–3650 cm^?1, while Group II bands occurred in the range 3200–3450 cm^?1. The hydrogen solubility associated with Group I bands is proportional to f _{O 2} to the 1/6 power for samples preannealed in contact with orthopyroxene, to the 1/3 power for samples preannealed in contact with magnesiowustite, and to the 1/13 power for samples preannealed in the absence of a solid-state buffer. The hydrogen concentration for Group II bands varies with f _{o 2} to the 1/3 power for opxbuffered samples, to the 1/2 power for mw-buffered samples, and to the 1/3 power for unbuffered samples. The dependence of hydrogen solubility on oxygen fugacity and orthopyroxene activity suggests that hydrogen is incorporated into the olivine structure via association with point defects. The presence of two distinct groups of absorption bands indicates that hydrogen is associated with two distinct lattice defects. The following point defect model for the mechanism of incorporation of hydrogen in olivine is consistent with these results: Hydrogen ions responsible for the Group I bands are associated with doubly charged oxygen interstitials, while hydrogen ions responsible for the Group II bands are associated with singly charged oxygen interstitials. Furthermore, the infrared bands observed in naturally derived olivines are present in spectra from our hydrothermally annealed crystals. Thus, the mechanisms of incorporation of hydrogen in olivine under geological conditions are the same as those operative under laboratory conditions. The maximum solubility reached in these experiments was ～ 360H/10⁶Si, which corresponds to ～ 0.002 wt% of H₂O. This value is a lower bound for the solubility of hydrogen in olivine under upper mantle conditions.     

Release of organic nitrogen compounds from Kerogen via catalytic hydropyrolysis

High hydrogen pressure pyrolysis (hydropyrolysis) was performed on samples of solvent extracted Kimmeridge Clay Formation source rock with a maturity equivalent to ca. 0.35% vitrinite reflectance. We describe the types and distributions of organic nitrogen compounds in the pyrolysis products (hydropyrolysates) using GC-MS. Compounds identified included alkyl-substituted indoles, carbazoles, benzocarbazoles, quinolines and benzoquinolines. The distributions of the isomers of methylcarbazoles, C₂-alkylcarbazoles and benzocarbazoles in the hydropyrolysates were compared to a typical North Sea oil. The hydropyrolysates compared to the North Sea oil, showed increased contributions from alkylcarbazole isomers where the nitrogen group is "exposed" (no alkyl substituents adjacent to the nitrogen functionality) and appreciable levels of benzo[b]carbazole relative to benzo[a]- and benzo[c]carbazoles. Hydropyrolysis is found to be an ideal technique for liberating appreciable quantities of heterocyclic organic nitrogen compounds from geomacromolecules. The products released from the immature Kimmeridge Clay are thought to represent a potential source of nitrogen compounds in the bound phase (kerogen) able to contribute to the free bitumen phase during catagenesis.     

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.     

Thermal cracking history by laboratory kinetic simulation of Paleozoic oil in eastern Tarim Basin, NW China, implications for the occurrence of residual oil reservoirs

The thermal stability of Paleozoic oil in eastern Tarim Basin, NW China was investigated through laboratory kinetic simulation experiments. Laboratory cracking of a selected marine oil sample from Ordovician strata in well LG-1 of Tarim Basin was performed by confined, dry pyrolysis system at T = 300–650 °C, P = 50 MPa. Results indicated the oil required higher temperature for cracking. At laboratory heating rates, oil cracking started at 390–400 °C and the laboratory cracking was completed at around 650 °C. At geological heating rates, the onset temperature is about 148–162 °C for cracking start and was completed at 245–276 °C. The oil-cracking history was recovered using the acquired kinetic parameters and the geothermal history of TD-2, and the threshold temperature for oil cracking under geological conditions was calculated. The oil cracking started at 165 °C (R_o = 1.45%) and stopped in early Devonian (390 Ma), and the oil-cracking rates in the strata of -O₁ reached 60–70% at the end of Silurian. The calculated oil generation and oil cracking windows overlapped to some extent and were completed rapidly. The possible geological controls for the occurrence of residual oil reservoirs in Eastern Tarim basin have been discussed, including the high stability of the Paleozoic oil in Tarim Basin, the fast heating rate and longer duration time for oil cracking, the slight biodegradation in later uplift, the good preservation of the paleo-reservoirs and the moderate structural adjustment, which were critical for the exploration of residual oil and gases in this area.     

中国西北侏罗纪煤系显微组分热解油生物标志物特征及其意义

从西北地区侏罗纪煤中分离出来的不同显微组分热解油生物标志物总体上比较相似,但在一些特殊生物标志物的分布上存在明显差异。藻类体、孢子体、角质体热解油Pr/Ph比值一般在1.5～2.0之间,镜质体和基质镜质体热解油Pr/Ph比值在3～4之间,但均只有相应原煤抽提物Pr/Ph比值的一半。在常规生物标志物甾烷和萜烷组成中,藻类体和孢子体含有相对丰富的C27甾烷,角质体其次,镜质体和基质镜质体C27甾烷含量很低或者基本不含C27甾烷;藻类体和角质体含有较高的伽马蜡烷,而与藻类体来自相同原煤的孢子体伽马蜡烷含量很低;镜质体和基质镜质体基本上不含伽马蜡烷;分离显微组分的原煤伽马蜡烷含量均很低。由此可见,伽马蜡烷的含量不仅与有机质沉积水体的盐度有关,与母源的成分也有关系。显微组分热解油与煤系原油生物标志物组成特征对比表明,煤系原油是藻类体、孢子体、角质体等富氢组分和相对贫氢的镜质组生成产物的混合物。不同油气藏中的原油,每一类显微组分的贡献可能不尽相同,有些原油可能主要来源于藻类体和孢子体等富氢显微组分,而有些原油除了富氢显微组分有贡献外,镜质组对其也有一定的贡献,但富氢显微组分应该是煤系含油气盆地中主要的生油显微组分。     

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.     

Petroleum geochemistry of the Potwar Basin, Pakistan: 1. Oil-oil correlation using biomarkers, δC and δD

Geochemical characterisation of 18 crude oils from the Potwar Basin (Upper Indus), Pakistan is carried out in this study. Their relative thermal maturities, environment of deposition, source of organic matter (OM) and the extent of biodegradation based on the hydrocarbon (HC) distributions are investigated. A detailed oil-oil correlation of the area is established. Gas chromatography-mass spectrometry (GC-MS) analyses and bulk stable carbon and hydrogen isotopic compositions of saturated and aromatic HC fractions reveals three compositional groups of oils. Most of the oils from the basin are typically generated from shallow marine source rocks. However, group A contains terrigenous OM deposited under highly oxic/fluvio-deltaic conditions reflected by high pristane/phytane (Pr/Ph), C₃₀ diahopane/C₂₉Ts, diahopane/hopane and diasterane/sterane ratios and low dibenzothiophene (DBT)/phenanthrene (P) ratios. The abundance of C₁₉-tricyclic and C₂₄-tetracyclic terpanes are consistent with a predominant terrigenous OM source for group A. Saturated HC biomarker parameters from the rest of the oils show a predominant marine origin, however groups B and C are clearly separated by bulk δ¹³C and δD and the distributions of the saturated HC fractions supporting variations in source and environment of deposition of their respective source rocks. Moreover, various saturated HC biomarker ratios such as steranes/hopanes, diasteranes/steranes, C₂₃-tricyclic/C₃₀ hopane, C₂₈-tricyclic/C₃₀ hopane, total tricyclic terpanes/hopanes and C₃₁(R + S)/C₃₀ hopane show that two different groups are present. These biomarker ratios show that group B oils are generated from clastic-rich source rocks deposited under more suboxic depositional environments compared to group C oils. Group C oils show a relatively higher input of algal mixed with terrigenous OM, supported by the abundance of extended tricyclic terpanes (up to C₄₁₊) and steranes.Biomarker thermal maturity parameters mostly reached to their equilibrium values indicating that the source rocks for Potwar Basin oils must have reached the early to peak oil generation window, while aromatic HC parameters suggest up to late oil window thermal maturity. The extent of biodegradation of the Potwar Basin oils is determined using various saturated HC parameters and variations in bulk properties such as API gravity. Groups A and C oils are not biodegraded and show mature HC profiles, while some of the oils from group B show minor levels of biodegradation consistent with high Pr/n-C₁₇, Ph/n-C₁₈ and low API gravities.     

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.     

Modification of thermal and oxidative properties of biodiesel produced from vegetable oils

Trans esterification of three vegetable oils, sunflower oil, linseed oil and mixed oils as; sunflower-soyabean and olein were carried out using methanol, and potasium hydroxide as catalyst. The methyl esters of the corresponding oils were separated from the crude glycerol and characterized by physical-chemical methods to evaluate their thermal properties. This methods are determination of densities, cloud points, pour points, flash points, kinematic viscosities, hydrogen/carbon ratios, sulfur contents, ash contents and triglycerides. The physico-chemical characteristic of biodiesel treated with ozone showed improvement of pour point and flash point indicating higher degree of safety for fuel. Methyl esters mixed with their corresponding ozonated oil were subjected to comparison and evaluation for their thermal properties by the thermo gravimetric analysis differential thermal analysis from which the calculated heat of enthalpy and comparison with the heat of conventional diesel. The results showed that the oxygen content of biodiesel samples treated with ozone increased weight % and resulted in more extensive chemical reaction, promoted combustion characteristics and less carbon residue was produced. Gas chromatography appeared more suitable to address the problem of determining/verifying biodiesel methyl ester and showed that methyl ester content was impurity free. Ultra violet-detection was used for rapid quantization of triglycerols. From the analyses performed biodiesel treated with ozone modified the thermal and oxidative stability shown by the high combustion efficiency indicated by the high heat of enthalpy and reducing the emission of particulate matter.     

Use of biomarker distributions and compound specific isotopes of carbon and hydrogen to delineate hydrocarbon characteristics in the East Sirte Basin (Libya)

Biomarker ratios, together with stable carbon (δ¹³C) and hydrogen (δD) isotopic compositions of individual hydrocarbons have been determined in a suite of crude oils (n = 24) from the East Sirte Basin to delineate their sources and respective thermal maturity. The crude oil samples are divided into two main families (A and B) based on differences in source inputs and thermal maturity. Using source specific parameters including pristane/phytane (Pr/Ph), hopane/sterane, dibenzothiophene/phenanthrene (DBT/P), Pr/n-C₁₇ and Ph/n-C_l8 ratios and the distributions of tricyclic and tetracyclic terpanes, family B oils are ascribed a marine source rock deposited under sub-oxic conditions, while family A oils have a more terrigenous source affinity. This genetic classification is supported by the stable carbon isotopic compositions (δ¹³C) of the n-alkanes. Using biomarker maturity parameters such as the abundance of Pr and Ph relative to n-alkanes and the distribution of sterane and hopane isomers, family A oils are shown to be more thermally mature than family B oils. The contrasting maturity of the two families is supported by differences between the stable hydrogen isotopic compositions (δD) of Pr and Ph and the n-alkanes, as well as the δ¹³C values of n-alkanes in their respective oils.     

Biodiesel synthesis from non-edible oils by transesterification using the activated carbon as heterogeneous catalyst

The need for renewable environmentally friendly energy resources is growing every day. Biodiesel is one of the most promising alternatives to the conventional non-renewable energy resources. Heterogeneous catalysts proved a high efficiency in the transesterification of oils to produce biodiesel. In this research, activated carbon was tested as a heterogeneous catalyst in the transesterification of two non-edible oils (waste cooking oil and Jatropha oil) with methanol to produce biodiesel. Activated carbon was characterized using X-ray diffraction, scanning electron microscope and Fourier transformed infrared. The effect of different operating parameters, namely operation time (30, 60, 120 and 180 min), alcohol-to-oil molar ratio (4:1, 6:1, 8:1 and 10:1), catalyst loading [0.5, 1, 2, 3 and 5% (w/w)] and rotational speed (100, 200, 300 and 400 rpm), was investigated. Results showed that increasing the operational time, the alcohol-to-oil molar ratio and the catalyst loading increases the conversion to biodiesel but only to some extent; increasing the stirring rate was found to be beneficial to the process. The optimum conditions were found to be 2 h of heating, 6:1 alcohol-to-oil ratio, 1 wt% catalyst loading and 400 rpm stirring. Under optimum conditions, the conversion to biodiesel reached 93.95 and 93.27% for the waste cooking oil and the Jatropha oil, respectively. The properties of the obtained biodiesel (density, viscosity, flash point, pour point and cloud point) were measured giving promising results.     

Solubility of crude oil in methane as a function of pressure and temperature

The solubility of a 44° API (0.806 sp. gr.) whole crude oil has been measured in methane with water present at temperatures of 50 to 250°C and pressures of 740 to 14,852 psi, as have the solubilities of two high molecular weight petroleum distillation fractions at temperatures of 50 to 250°C and pressures of 4482 to 25,266 psi. Both increases in pressure and temperature increase the solubility of crude oil and petroleum distillation fractions in methane, the effect of pressure being greater than that of temperature. Unexpectedly high solubility levels (0.5–1.5 grams of oil per liter of methane—at laboratory temperature and pressure) were measured at moderate conditions (50–200°C and 5076–14504 psi). Similar results were found for the petroleum distillation fractions, one of which was the highest molecular weight material of petroleum (material boiling above 266°C at 6 microns pressure). Unexpectedly mild conditions (100°C and 15,200 psi; 200°C and 7513 psi) resulted in cosolubility of crude oil and methane. Under these conditions, samples of the gas-rich phase gave solubility values of 4 to 5 g/l, or greater.Qualitative analyses of the crude-oil solute samples showed that at low pressure and temperature equilibration conditions, the solute condensate would be enriched in C₅–C₁₅ range hydrocarbons and in saturated hydrocarbons in the C₁₅₊ fraction. With increases in temperature and especially pressure, these tendencies were reversed, and the solute condensate became identical to the starting crude oil.The data of this study, compared to that of previous studies, shows that methane, with water present, has a much greater carrying capacity for crude oil than in dry systems. The presence of water also drastically lowers the temperature and pressure conditions required for cosolubility.The data of this and/or previous studies demonstrate that the addition of carbon dioxide, ethane, propane, or butane to methane also has a strong positive effect on crude oil solubility, as does the presence of fine grained rocks.The n-paraffin distributions (as well as the overall composition) of the solute condensates are controlled by the temperature and pressure of solution and exsolution, as well as by the composition of the original starting material. It appears quite possible that primary migration by gaseous solution could ‘strip’ a source rock of crude-oil like components leaving behind a bitumen totally unlike the migrated crude oil. The data of this study demonstrate previous criticisms of primary petroleum migration by gas solution are invalid; that primary migration by gaseous solution cannot occur because methane cannot dissolve sufficient volumes of crude oil or cannot dissolve the highest molecular weight components of petroleum (tars and asphaltenes).     

Petrology, rank and evidence for petroleum generation, Upper Triassic to Middle Jurassic coals, Central Alborz Region, Northern Iran

Upper Triassic to Middle Jurassic coals from the Alborz region of northern Iran were analyzed by reflected light-fluorescence microscopy and Rock Eval 6® pyrolysis to evaluate their regional rank variation, degree of hydrothermal alteration, and petroleum generative potential. The coal ranks in the region range from a low of 0.69%Ro_R in the Glanddeh-Rud area to a high of 1.02%Ro_R in the Gajereh area. T_max (°C) values (Rock Eval 6 pyrolysis) also increase progressively with increasing vitrinite %Ro values, however T_max is suppressed lower than would be expected for each rank ranging from 428 °C for the Glandeeh coal to 438 °C for the Gajereh coal. T_max suppression may be caused by maceral composition and soluble organics within the coal. Moderately high hydrogen indices, persistent and oily exudations from the coals during UV exposure, and traces of hydrocarbon fluid inclusions suggest that liquid petroleum was likely generated within some of the coals.     

Geochemical Characteristics of Different Kinds of Crude Oils in the Tarim Basin,Northwest China

Based on the compositions and distributions of biomarkers in thirty-five representative oil samples, oils from the Tarim Basin of northwestern China are mainly divided into two oil families. One oil family contains relatively low amounts of C₁₅-C₂₀ isoprenoid hydrocarbons and shows pristane predominance with Pr/Ph ratios ranging from 1.50 to 3.00. The GC/MS analytical data of these oils show the occurrence of abundant hopanes, and low concentrations of steranes and tricyclic terpanes with hopanes/steranes ratios from 6.25 to 12.24 and tricyclic terpanes/hopanes ratios from 0.03 to 0.24. These oils contain low drimane relative to homodrimane (C₁₅/C₁₆ < 1.0) and abundant rearranged bicyclanes in bicyclic sesquiterpanes. They are dominated by low carbon number (C₁₉-C₂₁) compounds in the tricyclic terpanes, and are rich in rearranged hopanes, C₂₉Ts and an unknown C₃₀ compound in pentacyclic triterpanes. These geochemical characteristics suggest that the oils were generated mainly from terrigenous organic matter. The other oil family shows remarkably different biomarker compositions and distributions. The oils revealed Pr/Ph ratios of about 1.0, high drimane/homodrimane ratios (>1.0), low hopanes/steranes ratios (0.65–2.50), high tricyclic terpanes/hopanes ratios (0.30–2.00) and a dominant peak at C₂₃ in tricyclic tepanes, suggesting a marine organic origin. Oil-source rock correlation indicates that these two oil families seem to have been derived from Mesozoic Jurassic-Triassic terrestrial source rocks (shales and coal seams) and Lower Paleozoic Ordovician-Cambrian marine source rocks, respectively.     

Limitations of ‘Rock-Eval’ pyrolysis for typing organic matter

Laboratory experimentation on whole-rock ‘Rock-Eval’ pyrolysis has shown that the characterization of organic matter through the use of a modified van Krevelen diagram, in which the hydrogen and oxygen indices are substituted for the atomic H/C and O/C ratios, produces questionable results. The hydrogen and oxygen indices have been found to be strongly affected by both matrix mineralogy and level of organic enrichment. It appears, therefore, that although the modified van Krevelen diagram maybe useful for tracing evolutionary pathways as organic matter matures, it can be very misleading when used to assess kerogen type.     

Graphite oxidation in the Apollo 17 orange glass magma: Implications for the generation of a lunar volcanic gas phase

An Apollo 17 picritic orange glass composition has been used to experimentally investigate the conditions at which graphite would oxidize to form a CO-rich gas, and ultimately produce lunar fire-fountain eruptions. Isothermal decompression experiments run above the A17 orange glass liquidus temperature (>1350 °C) suggest that the initial CO-rich gas phase produced by graphite oxidation would be generated during magma ascent at a pressure of 40 MPa, 8.5 km beneath the lunar surface. Additional experiments with 2000 ppm S and 1000 ppm Cl showed that the presence of these dissolved gas species would not affect the depth of graphite oxidation, verifying that the first volcanic gas phase would be generated by the oxidation of graphite.A simple ideal chemical mixing model for calculating melt FeO activity in a Fe-metal/silicate melt system was tested with a series of 0.1 MPa controlled oxygen fugacity experiments. Agreement between the model and experiments allows the model to be used to calculate oxygen fugacity in picritic lunar glass compositions such as the A17 orange glass. Using this model in a reanalysis of chemical equilibria between the natural A17 orange glass melt and the metal spherules (Fe₈₅Ni₁₄Co₁) trapped within the glass beads indicates a log oxygen fugacity of −11.2, 0.7 log units, more oxidized than previous estimates. At the A17 orange glass liquidus temperature (1350 ± 5 °C), this f_O2 corresponds to a minimum pressure of 41 MPa on the graphite–C–O surface. The fact that the same critical graphite oxidation pressure was determined in decompression experiments and from the Fe–FeO activity model for the natural A17 orange glass–metal assemblage strongly supports this pressure (8.5 km depth) for volcanic gas formation in lunar basalts. Generation of a gas by oxidation of C in ascending magma is likely to have been important in getting dense lunar magmas to the surface as well as in generating fire-fountain eruptions. The vesicles common in many lunar basalts and the ubiquitous Fe-metal in these rocks are also likely generated by the oxidation of carbon. The presence of carbon in the lunar basalts and the recent discovery of ppm levels of water in lunar basalts indicate that at least parts of the lunar interior still contained volatiles at 3.9 bybp.     

Assessment of generation temperatures of crude oils

Biological marker maturity parameters were used to estimate the minimum HC generation temperatures of crude oils from Eastern Hungary. More than 50 oils and oil shows were analysed. Molecular- and homologous-ratios of biological marker compounds (triterpanes, steranes, mono- and triaromatic steroid hydrocarbons) were used as maturation parameters. The oils have at least five maturity stages, i.e. they have been generated under different thermal conditions. The highest reservoir temperature in each group was chosen as the best estimate of the groups' temperature just below the generation temperature, i.e. reservoirs of the group might be expected to be at shallower depths (lower temperatures) than those of the generation zone due to vertical migration into pools. For each maturation level, a threshold temperature range for genesis was inferred from reservoir temperatures; they are from 130–135°C for the least mature oils to 210–215°C for the most mature oils. In the least mature oils cracking was not observed, hence carbon–carbon cracking reactions had not taken place during their genesis. The most mature oils are intensively cracked oils; they are almost condensates. Two major genetic groups (families) of oils were found in the area. Both are present in each maturation level. The effects of migration were checked, and no influence on maturation was found. A number of the oils are in overpressured reservoirs within, or just above, the zone of the present-day active oil generation, hence the present-day temperatures of the pools must have been maximum temperatures. Contrary to the traditionally accepted temperature range for petroleum generation–maturation reactions (50–150°C), there is strong evidence from this study that the onset of oil generation requires temperatures higher than 130°C and is still proceeding above 215°C.