The influence of hydrocarbon expulsion on carbon isotopic compositions of individual n-alkanes in pyrolysates of selected terrestrial kerogens

Expulsion of petroleum from source rock is a complex part of the entire migration process. There exist fractional effects on chemical compositions in hydrocarbon expulsion. Does the carbon isotopic fractionation occur during expulsion and to what extent? Here the influence of hydrocarbon expulsion on carbon isotopic compositions of individual n-alkanes from pyrolysates of selected terrestrial kerogens from Tuha basin and Fushun, Liaoning Province of China has been experimentally studied. The pyrogeneration-expulsion experiments were carried out under semi-closed system. The carbon isotopic compositions of individual n-alkanes were measured by GC-IRMS. The main conclusions are as follows. First, there is carbon isotopic fractionation associated with hydrocarbon expulsion from Type III kerogens in Tuha Basin. There exist differences of carbon isotopic compositions between the unexpelled n-alkanes and expelled n-alkanes from Tuha desmocollinite and Tuha mudstone. Second, there is almost no carbon isotopic fractionation associated with hydrocarbon expulsion from Type II kerogens in Fushun and Liaohe Basin. Third, carbon isotopic fractionation in hydrocarbon expulsion should be considered in making oil-source correlation of Type III kerogens at least in the Tuha Basin. Further studies need to be carried out to determine whether this is true in other basins. Fourth, oil and source at different maturity levels cannot be correlated directly for Type III kerogens since the carbon isotopic compositions of expelled hydrocarbons at different temperatures are different. The expelled hydrocarbons are usually lighter (depleted in ¹³C) than the hydrocarbons remaining in the source rock at the same maturity.     

Evaluation of the liquid hydrocarbon potential of coal by artificial maturation techniques

In certain areas, relatively large accumulations of liquid hydrocarbons have been attributed to coals. Evaluating the source rock potential of coal requires definition of both the generative potential (quantity and composition of generated hydrocarbons), and expulsion efficiency. Hydrous pyrolysis experiments were completed using Tertiary lignites (R_o < 0.35%) from North Dakota and the Far East to evaluate the source rock potential of coal. The North Dakota lignite is vitrinite-rich (93%) and liptinite-poor (3%); the Far East lignite is liptinite-rich (32% of total maceral content). These lignites have Hydrogen Index values of 123 and 483 mg HC/g OC, respectively. Differences in oil-pyrolysate yield, composition, and temperature of maximum pyrolysate yield from hydrous pyrolysis experiments for these two lignites are related to the type and amount of liptinite and vitrinite macerals. A maximum of 48 and 158 mg oil-pyrolysate/g OC is generated and expelled from the North Dakota and Far East lignites, respectively. Although these lignites consist predominantly of gas-prone vitrinitic components, their organic-rich nature can compensate for their poor convertibility to liquid hydrocarbons. The composition of these artificially generated oil-pyrolysates are similar to some non-marine oils, suggesting that this type of organic matter can be a significant contributor to many oils. Although the overall composition of the generated products from the two lignites is similar, the distribution of these products is significantly different. Homologous series of methyl ketones and alkyl benzenes have been identified in both oil-pyrolysates. Their presence and characteristic distribution suggest that microbial degradation occurred during the formation of these lignites. Although many coals generate significate amounts of liquid hydrocarbons that are similar to naturally occurring oils, poor explusion efficiency limits their source rock potential. Significant amounts of liquid products are assimilated by the vitrinitic matrix of most coals prior to expulsion, severely limiting the amount of petroleum available for migration and reservoir accumulation. However, adequate expulsion may occur in certain liptinite-rich coals or coals occurring in unique depositional settings.     

Guidelines for assessing the petroleum potential of coaly source rocks using Rock-Eval pyrolysis

Coaly source rocks are sufficiently different from marine and lacustrine source rocks in their organic matter characteristics to warrant separate guidelines for their assessment using Rock-Eval pyrolysis. The rank threshold for oil generation is indicated by the increase in BI (S1/TOC) at Rank(S_r)9–10 (T_max 420–430 °C, R_o 0.55–0.6%), and the threshold for oil expulsion is indicated by the peak in QI ([S1+S2]/TOC) at Rank(S_r)11–12.5 (T_max 430–440 °C, R_o 0.65–0.85%). The pronounced rank-related increase in HI (S2/TOC) prior to oil expulsion renders the use of immature samples inappropriate for source rock characterisation. A more realistic indication of the petroleum generative potential and oil expulsion efficiency of coaly source rocks can be gained from samples near the onset of expulsion. Alternatively, effective HI′ values (i.e. HIs near the onset of expulsion) can be estimated by translating the measured HIs of immature samples along the maturation pathway defined by the New Zealand (or other defined) Coal Band. Coaly source rocks comprise a continuum of coaly lithologies, including coals, shaly coals and coaly mudstones. Determination of the total genetic potential of coaly source rock sequences is best made using lithology-based samples near the onset of expulsion.     

The petroleum generation potential and effective oil window of humic coals related to coal composition and age

A worldwide data set of more than 500 humic coals from the major coal-forming geological periods has been used to analyse the evolution in the remaining (Hydrogen Index, HI) and total (Quality Index, QI) generation potentials with increasing thermal maturity and the ‘effective oil window’ (‘oil expulsion window’). All samples describe HI and QI bands that are broad at low maturities and that gradually narrow with increasing maturity. The oil generation potential is completely exhausted at a vitrinite reflectance of 2.0–2.2%R_o or T_max of 500–510 °C. The initial large variation in the generation potential is related to the original depositional conditions, particularly the degree of marine influence and the formation of hydrogen-enriched vitrinite, as suggested by increased sulphur and hydrogen contents. During initial thermal maturation the HI increases to a maximum value, HI_max. Similarly, QI increases to a maximum value, QI_max. This increase in HI and QI is related to the formation of an additional generation potential in the coal structure. The decline in QI with further maturation is indicating onset of initial oil expulsion, which precedes efficient expulsion. Liquid petroleum generation from humic coals is thus a complex, three-phase process: (i) onset of petroleum generation, (ii) petroleum build-up in the coal, and (iii) initial oil expulsion followed by efficient oil expulsion (corresponding to the effective oil window). Efficient oil expulsion is indicated by a decline in the Bitumen Index (BI) when plotted against vitrinite reflectance or T_max. This means that in humic coals the vitrinite reflectance or T_max values at which onset of petroleum generation occurs cannot be used to establish the start of the effective oil window. The start of the effective oil window occurs within the vitrinite reflectance range 0.85–1.05%R_o or T_max range 440–455 °C and the oil window extends to 1.5–2.0%R_o or 470–510 °C. For general use, an effective oil window is proposed to occur from 0.85 to 1.7%R_o or from 440 to 490 °C. Specific ranges for HI_max and the effective oil window can be defined for Cenozoic, Jurassic, Permian, and Carboniferous coals. Cenozoic coals reach the highest HI_max values (220–370 mg HC/g TOC), and for the most oil-prone Cenozoic coals the effective oil window may possibly range from 0.65 to 2.0%R_o or 430 to 510 °C. In contrast, the most oil-prone Jurassic, Permian and Carboniferous coals reach the expulsion threshold at a vitrinite reflectance of 0.85–0.9%R_o or T_max of 440–445 °C.     

Hydrocarbon migration characteristics of the Lower Cretaceous in the Erlian Basin

The paper systematically analyzes the hydrocarbon migration characteristics of the Lower Cretaceous in the Erlian Basin, based on the geochemical data of mudstone and sandstone in the main hydrocarbon-generating sags. (1) The source rocks in K1ba and K1bt1 are estimated to be the mature ones, their hydrocarbon expulsion ratio can reach 32%-72%. The Type-I sags in oil windows possess good hydrocarbon generation and expulsion conditions, where commercial reservoirs can be formed. (2) According to the curves of the mudstone compaction and evolution of clay minerals, the rapid compaction stage of mudstones is the right time of hydrocarbon expulsion, i.e., primary migration. (3) The timing between hydrocarbon generation and expulsion is mainly related to the accordance of the oil window and the rapid compaction stage of mudstones in the hydrocarbon generation sags of Type-I. That forms the most matching relation between hydrocarbon generation and migration. (4) The faults and unconformities are the important paths for the secondary hydrocarbon migration. Especially, the unconformity between K1ba and K1bt1 has a favorable condition for oil accumulation, where the traps of all types are the main exploration targets. (5) Hydrocarbon migration effect, in the Uliastai sag, is most significant; that in the Saihan Tal and Anan sags comes next, and that in the Bayandanan and Jargalangt sags is worst.     

Compound-specific stable carbon isotope analysis as a tool for correlating coal-sourced oils and interbedded shale-sourced oils in coal measures: an example from Turpan basin, north-western China

Molecular geochemical methods have shown that it is often difficult to differentiate between coal- and interbedded shale-sourced oils, even though coals and interbedded shales may exhibit considerable organic influx variation (e.g. land plant vs algal organic matter) due to the changes of depositional setting. However, compound-specific stable carbon isotopic compositions are sensitive to the source input variations. Typically, specific molecules are more depleted in ¹³C with increasing content of aqueous biota. This hypothesis is examined and exemplified by comparing the stable carbon isotopic ratios of n-alkanes from source rock extracts and related oils of the Turpan basin, north-western China. Stable carbon isotopic values of n-alkanes extracted from coals and interbedded shales show that δ¹³C values of n-alkanes with less than 20 carbon atoms vary only slightly. However, there are dramatic changes in the isotopic compositions of higher molecular weight n-alkanes. Furthermore, n-alkanes from coal extracts are enriched in ¹³C relative to that of interbedded shales with excursions up to 2–3‰. This comparison enables the differentiation of coal- and interbedded shale-sourced oils, and provides information useful in assessing the hydrocarbon system of a basin.     

Oxygen isotopic fractionation during inorganic calcite precipitation ― Effects of temperature, precipitation rate and pH

Stable oxygen isotopic fractionation during inorganic calcite precipitation was experimentally studied by spontaneous precipitation at various pH (8.3 < pH < 10.5), precipitation rates (1.8 < log R < 4.4 μmol m^− 2 h^− 1) and temperatures (5, 25, and 40 °C) using the CO₂ diffusion technique.The results show that the apparent stable oxygen isotopic fractionation factor between calcite and water (α_{calcite–water}) is affected by temperature, the pH of the solution, and the precipitation rate of calcite. Isotopic equilibrium is not maintained during spontaneous precipitation from the solution. Under isotopic non-equilibrium conditions, at a constant temperature and precipitation rate, apparent 1000lnα_{calcite–water} decreases with increasing pH of the solution. If the temperature and pH are held constant, apparent 1000lnα_{calcite–water} values decrease with elevated precipitation rates of calcite. At pH = 8.3, oxygen isotopic fractionation between inorganically precipitated calcite and water as a function of the precipitation rate (R) can be described by the expressions

at 5, 25, and 40 °C, respectively.The impact of precipitation rate on 1000lnα_{calcite–water} value in our experiments clearly indicates a kinetic effect on oxygen isotopic fractionation during calcite precipitation from aqueous solution, even if calcite precipitated slowly from aqueous solution at the given temperature range. Our results support Coplen's work [Coplen T. B. (2007) Calibration of the calcite–water oxygen isotope geothermometer at Devils Hole, Nevada, a natural laboratory. Geochim. Cosmochim. Acta 71, 3948–3957], which indicates that the equilibrium oxygen isotopic fractionation factor might be greater than the commonly accepted value.     

Coal as a source rock for oil: a review

The geological debate about whether, and to what extent, humic coals have sourced oil is likely to continue for some time, despite some important advances in our knowledge of the processes involved. It is clear that not only liptinites, but also perhydrous vitrinites have the potential to generate hydrocarbon liquids in the course of natural coalification. Some liptinites, especially alginite, cutinite, and suberinite, contain a higher proportion of aliphatic moieties in their structure than other liptinites such as sporinite and resinite and are, therefore, more oil-prone. It is of potential value to be able to predict the several environments of deposition in which coals with high liptinite contents or containing perhydrous vitrinites may have been formed. Review of the distribution of oil-prone coals in time and space reveals that most are Jurassic–Tertiary with key examples from Australia, New Zealand, and Indonesia. Methods based both on experimental simulations and the examination of naturally matured samples have been used to determine the order of generation of hydrocarbons from different macerals. Results are not entirely consistent among the different approaches, and there is much overlap in the ranges of degradation, but it seems probable that in the natural environment vitrinites begin to generate early, followed by labile liptinites such as suberinite, then cutinite, sporinite, and, finally, alginite.Petroleum potential may be determined by experimental simulation of natural coalification or inferred through various micro-techniques, especially fluorescence and infrared (IR) spectroscopy, or bulk techniques such as elemental analysis and ¹³C NMR spectroscopy. The latter three techniques enable a measure of the polymethylene component of the coal, which now appears to be one of the best available approaches for determining petroleum potential. No method of experimental simulation of petroleum generation from coals is without criticism, and comparative results are highly variable. However, hydrous pyrolysis, confined pyrolysis, and forms of open-system hydrous pyrolysis approach acceptable simulations.Whether, and to what degree generated liquid hydrocarbons are expelled, has long been the central problem in ‘oil from coal’ studies. The structure of vitrinite was believed until recently to contain an interconnected microporous network in which generated oil would be contained until an expulsion threshold was attained. Recent studies show the pores are not interconnected. Combined with a dynamic model of pore generation, it now seems that expulsion of hydrocarbons is best explained by activated diffusion of molecules to maceral boundaries and ultimately by cleats and fractures to coal seam boundaries. The main reason for poor expulsion is the adsorption of oil on the organic macromolecule, which may be overcome (1) if coals are thin and interbedded with clastic sediments, or (2) if the coals are very hydrogen-rich and generate large quantities of oil.The existence of oil in vitrinite is attested to by solvent extractions, fluorescence properties, and by microscopic observations of oil and bitumen. Experimental simulation of expulsion of oil from coals has only recently been attempted. The relative timing of release of generated CO₂ and CH₄ could have considerable importance in promoting the expulsion of liquid hydrocarbons but the mechanism is unclear. As it is universally agreed that dispersed organic matter (DOM) in some shales readily generates and expels petroleum, it is curious that few consistent geochemical differences have been found between coal macerals and DOM in interbedded shales.Unambiguous evidence of expulsion from coals is limited, and in particular only a few commercial oil discoveries can be confidently correlated to coals. These include Upper Cretaceous Fruitland Formation coals in the USA, from which oil is produced; New Zealand Tertiary coals; and Middle Jurassic coals from the Danish North Sea. It is likely that coals have at least contributed to significant oil discoveries in the Gippsland Basin, Australia; in the Turpan Basin, China; and in the Kutei and Ardjuna basins in Indonesia, but this remains unproven. Early reports that early Jurassic coals in mid-Norway were a major source of the reservoired oils have been shown to be inaccurate.None of the proposed ‘rules of thumb’ for generation or expulsion of petroleum from coals seem particularly robust. Decisions on whether a particular coal is likely to have been an active source for oil should consider all available geological and geochemical information. The assumptions made in computational models should be well understood as it is likely with new understandings of processes involved that some of these assumptions will be difficult to sustain.     

欠压实泥岩顶底板形成机理及其对油气运移的影响

欠压实泥岩顶底板是指比中部欠压实泥岩较致密的泥岩表层,是趋于正常压实的泥岩层,发育于低渗透率的厚层泥岩的上、下部位。以低速渗流定律为理论基础,从微观机理上分析欠压实泥岩顶底板的形成过程,提出穿过欠压实泥岩顶底板流体运移阻力的计算公式。当含顶底板泥岩作为盖层时,分为连续沉积型、抬升型和压裂型3种。压裂型泥岩盖层的封闭能力等于底板排替压力与达到顶板破裂的剩余压力之和,其他两种盖层的封闭能力就等于盖层顶底板的排替压力之和。当含顶底板泥岩作为源岩时,在连续型源岩中,油气排放的方向主要取决于泥岩顶底板渗透性地层的发育程度;在压裂型源岩中,大量油气沿裂缝向上排烃。此外,源岩的排烃方向还受断层的控制。通过欠压实泥岩顶底板形成机理的研究,有助于评价泥岩盖层的封烃能力,了解泥质烃源岩油气初次运移的方向。     

Carbon isotopes of Middle–Lower Jurassic coal-derived alkane gases from the major basins of northwestern China

Coal-derived hydrocarbons from Middle–Lower Jurassic coal-bearing strata in northwestern China are distributed in the Tarim, Junggar, Qaidam, and Turpan-Harmi basins. The former three basins are dominated by coal-derived gas fields, distributed in Cretaceous and Tertiary strata. Turpan-Harmi basin is characterized by coal-derived oil fields which occur in the coal measures. Based on analysis of gas components and carbon isotopic compositions from these basins, three conclusions are drawn in this contribution: 1) Alkane gases with reservoirs of coal measures have no carbon isotopic reversal, whereas alkane gases with reservoirs not of coal measures the extent of carbon isotopic reversal increases with increasing maturity; 2) Coal-derived alkane gases with high δ¹³C values are found in the Tarim and Qaidam basins (δ¹³C₁: − 19.0 to − 29.9‰; δ¹³C₂: − 18.8 to − 27.1‰), and those with lowest δ¹³C values occur in the Turpan-Harmi and Junggar basins (δ¹³C₁: − 40.1 to − 44.0‰; δ¹³C₂: − 24.7 to − 27.9‰); and 3) Individual specific carbon isotopic compositions of light hydrocarbons (C_5–8) in the coal-derived gases are lower than those in the oil-associated gases. The discovered carbon isotopic reversal of coal-derived gases is caused by isotopic fractionation during migration and secondary alteration. The high and low carbon isotopic values of coal-derived gases in China may have some significance on global natural gas research, especially the low carbon isotope value of methane may provide some information for early thermogenic gases. Coal-derived methane typically has much heavier δ¹³C than that of oil-associated methane, and this can be used for gas–source rock correlation. The heavy carbon isotope of coal-derived ethane is a common phenomenon in China and it shed lights on the discrimination of gas origin. Since most giant gas fields are of coal-derived origin, comparative studies on coal-derived and oil-associated gases have great significance on future natural gas exploration in the world.     

Constraining the hydrocarbon expulsion history of the coals in Qinshui Basin, North China, from the analysis of fluid inclusions

From the comprehensive study on the homogenization temperatures and the occurrence of fluid inclusions in the framework minerals of the strata between or above the Carboniferous–Permian coals in the Qinshui basin, Shanxi, three stages are predicted of hydrocarbon expulsion from the coals. Combined with the known history of basin evolution, it is deduced that the expulsion of hydrocarbons happened during the J₁ (210–180 Ma), the early K₁ (150–130 Ma) and K₂E₁ (110–60 Ma). In the early stage, the coals produced and discharged coal-generated oils. The average GOI value of four sandstone samples is relatively high, as they have been exposed to high paleo-oil saturation in the strata between or above the coals. The biomarker compositions of oil-bearing fluid inclusions are similar to those of extracts from the coals, and so it is concluded that those oils were derived from the same family of the coals.     

Organic petrology and geochemistry of the Carboniferous coal seams from the Central Asturian Coal Basin (NW Spain)

This paper presents for the first time a petrological and geochemical study of coals from the Central Asturian Coal Basin (North Spain) of Carboniferous (Pennsylvanian), mainly of Moscovian, age. A paleoenvironmental approach was used, taking into account both petrographic and organic geochemical studies. Vitrinite reflectance (R_r) ranges from 0.5% to 2.5%, which indicates a high volatile bituminous to semianthracite and anthracite coal rank. The coal samples selected for paleoenvironmental reconstruction are located inside the oil–gas-prone phase, corresponding to the interval between the onset of oil generation and first gas generation and efficient expulsion of oil. This phase is represented by coals that have retained their hydrocarbon potential and also preserved biomarker information. Paleodepositional reconstruction based on maceral and petrographic indices points to a swamp environment with vitrinite-rich coal facies and variable mineral matter content. The gelification index (GI) and groundwater influence index (GWI) indicate strong gelification and wet conditions. The biomarkers exhibit a high pristane/phytane ratio, suggesting an increase in this ratio from diagenetic processes, and a high diterpanes ratio. This, in turn, would seem to indicate a high swamp water table and a humid climate. The maximum point of coal accumulation occurred during the regressive part of the Late Moscovian sequence and in the most humid climate described for this period of time in the well-known coal basins of Europe and North America.     

Isotopic and molecular composition of coal-bed gas in the Amasra region (Zonguldak basin—western Black Sea)

Previous studies on the coal-bed methane potential of the Zonguldak basin have indicated that the gases are thermogenic and sourced by the coal-bearing Carboniferous units. In this earlier work, the origin of coal-bed gas was only defined according to the molecular composition of gases and to organic geochemical properties of the respective source rocks, since data on isotopic composition of gases were not available. Furthermore, in the western Black Sea region there also exist other source rocks, which may have contributed to the coal-bed gas accumulations. The aim of this study is to determine the origin of coal-bed gas and to try a gas-source rock correlation. For this purpose, the molecular and isotopic compositions of 13 headspace gases from coals and adjacent sediments of two wells in the Amasra region have been analyzed. Total organic carbon (TOC) measurements and Rock-Eval pyrolysis were performed in order to characterize the respective source rocks. Coals and sediments are bearing humic type organic matter, which have hydrogen indices (HI) of up to 300 mgHC/gTOC, indicating a certain content of liptinitic material. The stable carbon isotope ratios (δ¹³C) of the kerogen vary from −23.1 to −27.7‰. Air-free calculated gases contain hydrocarbons up to C₅, carbon dioxide (<1%) and a considerable amount of nitrogen (up to 38%). The gaseous hydrocarbons are dominated by methane (>98%). The stable carbon isotope ratios of methane, ethane and propane are defined as δ¹³C₁: −51.1 to −48.3‰, δ¹³C₂: −37.9 to −25.3‰, δ¹³C₃: −26.0 to −19.2 ‰, respectively. The δD₁ values of methane range from −190 to −178‰. According to its isotopic composition, methane is a mixture, partly generated bacterially, partly thermogenic. Molecular and isotopic composition of the gases and organic geochemical properties of possible source rocks indicate that the thermogenic gas generation took place in coals and organic rich shales of the Westphalian-A Kozlu formation. The bacterial input can be related to a primary bacterial methane generation during Carboniferous and/or to a recent secondary bacterial methane generation. However, some peculiarities of respective isotope values of headspace gases can also be related to the desorption process, which took place by sampling.     

Chemical and chronologic complexity in the convecting upper mantle: Evidence from the Taitao ophiolite, southern Chile

Exposure of the ca. 6 Ma Taitao ophiolite, Chile, located 50 km south of the Chile Triple Junction, allows detailed chemical and isotopic study of rocks that were recently extracted from the depleted mantle source of mid-ocean ridge basalts (DMM). Ultramafic and mafic rocks are examined for isotopic (Os, Sr, Nd, and O), and major and trace element compositions, including the highly siderophile elements (HSE). Taitao peridotites have compositions indicative of variable extents of partial melting and melt extraction. Low δ¹⁸O values for most whole rock samples suggest some open-system, high-temperature water–rock interaction, most likely during serpentinization, but relict olivine grains have δ¹⁸O values consistent with primary mantle values. Most of the peridotites analyzed for Nd–Sr isotopes have compositions consistent with estimates for the modern DMM, although several samples are characterized by ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd indicative of crustal contamination, most likely via interactions with seawater. The peridotites have initial ¹⁸⁷Os/¹⁸⁸Os ratios that range widely from 0.1168 to 0.1288 (γ_Os = −8.0 to +1.1), averaging 0.1239 (γ_Os = −2.4), which is comparable to the average for modern abyssal peridotites. A negative correlation between the Mg^# of relict olivine grains and Os isotopic compositions of whole rock peridotites suggests that the Os isotopic compositions reflect primary mantle Re/Os fractionation produced by variable extents of partial melting at approximately 1.6 Ga. Recent re-melting at or near the spatially associated Chile Ridge further modified these rocks, and Re, and minor Pt and Pd were subsequently added back into some rocks by late-stage melt–rock or fluid–rock interactions.In contrast to the peridotites, approximately half of the mafic rocks examined have whole rock δ¹⁸O values within the range of mantle compositions, and their Nd and Sr isotopic compositions are all generally within the range of modern DMM. These rocks have initial ¹⁸⁷Os/¹⁸⁸Os ratios, calculated for 6 Ma, that range from 0.126 (γ_Os = −1) to as high as 0.561 (γ_Os = +342). The Os isotopic systematics of each of these rocks may reflect derivation from mixed lithologies that include the peridotites, but may also include pyroxenites with considerably more radiogenic Os than the peridotites. This observation supports the view that suprachondritic Os present in MORB derives from mixed mantle source lithologies, accounting for some of the worldwide dichotomy in ¹⁸⁷Os/¹⁸⁸Os between MORB and abyssal peridotites.The collective results of this study suggest that this >500 km³ block of the mantle underwent at least two stages of melting. The first stage occurred at 1.6 Ga, after which the block remained isolated and unmixed within the DMM. A final stage of melting recently occurred at or near the Chile Ridge, resulting in the production of at least some of the mafic rocks. Convective stirring of this mantle domain during a >1 Ga period was remarkably inefficient, at least with regard to Os isotopes.     

Gaseous hydrocarbons generated during pyrolysis of petroleum source rocks using unconventional grain-size: implications for natural gas composition

Open-system pyrolysis experiments were performed on a suite of immature to marginally mature source rocks to investigate the influence of kerogen type on primary gas composition and the effect of grain size on gas expulsion characteristics. The pyrolysis of rock powders confirmed that hydrogen-rich kerogens yielded wetter gases than did hydrogen-poor kerogens. Gases detected from the pyrolysis of rock chips were drier than those from powders of equivalent samples. This was due to two processes: the retention and secondary cracking of higher molecular weight pyrolysis products and the preferential expulsion of methane from the rock matrix. These two effects, one chemical the other physical, could be distinguished using a novel approach involving multi-step pyrolysis of rock chips followed by on-line crushing of the residues. The enrichment of methane in natural gas attributed, by earlier workers, to be a consequence of fractionation during secondary migration (post-expulsion) has been proven to be real also during expulsion from source rocks at least for pyrolysis conditions.     

Organic geochemical characteristics and depositional environments of the Jurassic coals in the eastern Taurus of Southern Turkey

In this study, organic matter content, type and maturity as well as some petrographic and physical characteristics of the Jurassic coals exposed in the eastern Taurus were investigated and their depositional environments were interpreted.The total organic carbon (TOC) contents of coals in the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc areas are 24.54, 66.78 and 49.15%, respectively. The Feke–Akkaya and Kozan–Kizilinc coals have low Hydrogen Index (HI) values while the Kozan–Gedikli coals show moderate HI values. All coal samples display very low Oxygen Index (OI) values. The Kozan–Gedikli coals contain Type II organic matter (OM), the Feke–Akkaya coals contain a mixture of type II and type III OM; and the Kozan–Kizilinc coals are composed of Type III OM. Sterane distribution was calculated as C₂₇ > C₂₉ > C₂₈ from the m/z 217 mass chromatogram for all coal samples.T_max values for the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc coals are 439, 412 and 427 °C. Vitrinite reflectance values (%R_o) for the Feke–Akkaya and Kozan–Kizilinc coal samples were measured as 0.65 and 0.51 and these values reveal that the Feke–Akkaya and Kozan–Kizilinc coals are at subbituminous A or high volatile C bituminous coal stage. On the basis of biomarker maturity parameters, these coals have a low maturity.The pristane/phytane (Pr/Ph) ratios for the Feke–Akkaya, Kozan–Gedikli and Kozan–Kizilinc coals are 1.53, 1.13 and 1.25, respectively. In addition, all coals show a homohopane distribution which is dominated by low carbon numbers, and C₃₅ homohopane index is very low for all coal samples. All these features may indicate that these coals were deposited in a suboxic environment.The high sterane/hopane ratios with high concentrations of steranes, low Pr/Ph ratios and C₂₅/C₂₆ tricyclic ratios > 1 may indicate that these coals formed in a swamp environment were temporarily influenced by marine conditions.     

Predicted CO2 emissions from maceral concentrates of high volatile bituminous Kentucky and Illinois coals

A large collection of well-characterized coals, documented in the Center for Applied Energy Research's (CAER) database, was used to estimate the CO₂ content of maceral concentrates from Kentucky and Illinois high volatile bituminous coals. The data showed no correlation between CO₂ versus coal ranks and between CO₂ versus maceral content. Subsequently, eight sets of low-ash density-gradient centrifugation (DGC) maceral concentrates from five coal beds were examined, spanning in the high volatile rank range. Heating value was not determined on the concentrates, but instead was calculated using the Mott–Spooner formula. There was a good correlation between predicted CO₂ and maceral content for the individual iso-rank (based on vitrinite reflectance, analyzed on whole (parent) coal) sets. In general, the predicted CO₂ increases from liptinite-rich through vitrinite-rich to inertinite-rich concentrates (note: no “concentrates” are absolutely monomaceral).     

Lithium speciation in aqueous fluids at high P and T studied by ab initio molecular dynamics and consequences for Li-isotope fractionation between minerals and fluids

Ab initio molecular dynamics simulations are performed to study the speciation changes in lithium bearing aqueous fluids at high temperature (T = 1000 K) and high pressures, P, between about 0.3 and 6.0 GPa. The simulations show a linear increase in Li coordination with fluid density, from 3.2 to about five in the considered pressure range. Towards low densities, associated LiF complexes are becoming increasingly stable, which is quantified by evaluating the dynamic behavior of the respective species. In the high-density region, HF complexes are observed. The differences in speciation may be related to structural changes of the solvent under compression. At a fluid density of 1.2 g/cm³, kinks in the pressure dependences of the oxygen–oxygen nearest neighbor distance and the oxygen–oxygen coordination are observed, which indicates a change in compaction mechanism. Assuming that the Li coordination difference between crystal and fluid is a major determinant for the isotopic fractionation between minerals and fluids, we expect only a small pressure dependence of the Li isotopic fractionation between Li bearing fluids and minerals. Our simulation results are consistent with experimental data that show reverse fractionation of ⁷Li between fluid and mineral, when Li is in tetrahedral instead of octahedral coordination in the crystal.     

陆相成熟烃源岩区连通砂体对油气运移的控制作用

基于成熟烃源岩稳态连续排烃机制,分析陆相成熟烃源岩区内连通砂体对油气运移的控制作用,并深入探讨烃源岩内砂体与烃源岩的接触面积、砂泥互层烃源岩层系中砂岩含量、砂体物性、砂体分布及其连续性对排烃效率的影响。结果表明：将连通砂体与烃源岩的接触类型分为垂向沉积相变接触型、侧向沉积相变接触型及交错复合接触型,其中前两者是烃源岩-连通砂体的主要接触类型;烃源岩-连通砂体配置组合以在异常压力驱动下的稳态连续排烃为主;烃源岩内砂体与烃源岩的接触面积越大、砂岩含量越大、砂岩物性越好、砂体分布稳定及连续性好有利于成熟烃源岩排烃,则排烃效率越大,进而控制主要排烃方向和资源量。烃源岩内连通砂体对油气二次运移的作用主要取决于其与烃源岩外连通砂体的分布连续性与物性连通性。如果烃源岩内砂体是孤立的,油气无法运移出烃源岩区,则形成烃源岩内油气藏;如果烃源岩内砂体与烃源岩外砂体分布连续且物性连通,则油气运移距离大,可在更为有利的圈闭分布区成藏。     

A preliminary stable isotope study on Mogok Ruby, Myanmar

The primary occurrence of ruby in the Mogok area, northern Myanmar is exclusively found in marble along with spinel–forsterite-bearing marble and phlogopite–graphite marble. These marble units are enclosed within banded biotite–garnet–sillimanite–oligoclase gneisses. Samples of these marbles collected for C–O stable isotope analysis show two trends of δ¹³C–δ¹⁸O variation resulting most likely from fluid–rock interactions. Ruby-bearing marble and phlogopite–graphite marble follow a trend with coupled C–O depletion, whereas spinel–forsterite-bearing marble follows a δ¹⁸O depletion trend with relatively constant δ¹³C values. Ruby formation might have resulted from CO₂-rich fluid–rock interaction, while spinel–forsterite-bearing marble was genetically related to CO₂-poor fluid–rock interaction. Both fluids may have arisen from external sources. Based on graphite Raman spectral thermometry, the estimated temperature for phlogopite–graphite marble, and probably ruby-bearing marble, was lower than 607 °C, and for spinel–forsterite-bearing marble, lower than 710 °C. Contrasting C/O diffusion between graphite/ruby/spinel/forsterite and calcite, local variations of isotopic compositions of newly formed minerals as a result of non-pervasive fluid infiltration, and open-system isotopic disturbance during cooling may have affected C-/O-isotopic fractionations between minerals. The estimated high formation temperatures for ruby and spinel/forsterite imply that the parental fluids may have been related to nearby igneous intrusions and/or metamorphic processes. Whether these two types of fluid were genetically related is unclear based on the present data.