Insights into oil cracking based on laboratory experiments

The objectives of this pyrolysis investigation were to determine changes in (1) oil composition, (2) gas composition and (3) gas carbon isotope ratios and to compare these results with hydrocarbons in reservoirs. Laboratory cracking of a saturate-rich Devonian oil by confined, dry pyrolysis was performed at T=350–450 °C, P=650 bars and times ranging from 24 h to 33 days. Increasing thermal stress results in the C₁₅₊ hydrocarbon fraction cracking to form C_6–14 and C_1–5 hydrocarbons and pyrobitumen. The C_6–14 fraction continues to crack to C_1–5 gases plus pyrobitumen at higher temperatures and prolonged heating time and the δ ¹³C_ethane–δ¹³C_propane difference becomes greater as oil cracking progresses. There is considerable overlap in product generation and product cracking. Oil cracking products accumulate either because the rate of generation of any product is greater than the rate of removal by cracking of that product or because the product is a stable end member under the experimental conditions. Oil cracking products decrease when the amount of product generated from a reactant is less than the amount of product cracked. If pyrolysis gas compositions are representative of gases generated from oil cracking in nature, then understanding the processes that alter natural gas composition is critical.     

Gas maturity and alteration systematics across the Western Canada Sedimentary Basin from four mud gas isotope depth profiles

Carbon isotope and molecular compositions of Mississippian to Upper Cretaceous mud gases have been examined from four depth profiles across the Western Canada Sedimentary Basin (WCSB). The profiles range from the shallow oil sands in the east (R₀ = 0.25) to the very mature sediments in the overthrust zone to the west (R₀ = 2.5). In the undisturbed WCSB, δ¹³C₁–δ¹³C₂ and δ¹³C₂–δ¹³C₃ cross-plots show three maturity and alteration trends: (1) pre-Cretaceous gas sourced from type II kerogen; (2) Cretaceous Colorado Group gas; and (3) Lower Cretaceous Mannville Group biodegraded gas. A fourth set of distinctly different maturity trends is recognized for Lower Cretaceous gas sourced from type III kerogen in the disturbed belt of the WCSB. Displacement of these latter maturity trends to high δ¹³C₂ values suggests that the sampled gas was trapped after earlier formed gas escaped, probably as a result of overthrusting. Unusually ¹³C-enriched gas (δ¹³C₁ = −34‰, δ¹³C₂ = −13‰, and δ¹³C₃ = 0‰), from the Gething Formation in the disturbed belt, is the result of late stage gas cracking in a closed system. In general, gas maturity is consistent with the maturity of the host sediments in the WCSB, suggesting that migration and mixing of gases was not pervasive on a broad regional and stratigraphic scale. The ‘Deep Basin’ portion of the WCSB is an exception. Here extensive cross-formational homogenization of gases has occurred, in addition to updip migration along the most permeable stratigraphic units.     

The effect of oil expulsion or retention on further thermal degradation of kerogen at the high maturity stage: A pyrolysis study of type II kerogen from Pingliang shale,China

High maturity oil and gas are usually generated after primary oil expulsion from source rocks, especially from oil prone type I/II kerogen. However, the detailed impacts of oil expulsion, or retention in source rock on further thermal degradation of kerogen at the high maturity stage remain unknown. In the present study, we collected an Ordovician Pingliang shale sample containing type II kerogen. The kerogens, which had previously generated and expelled oil and those which had not, were prepared and pyrolyzed in a closed system, to observe oil expulsion or oil retention effects on later oil and gas generation from kerogen. The results show that oil expulsion and retention strongly impacts on further oil and gas generation in terms of both the amount and composition in the high maturity stage. Gas production will be reduced by 50% when the expulsion coefficient reaches 58%, and gas from oil-expelled kerogen (less oil retained) is much drier than that from fresh kerogen. The oil expulsion also causes n-alkanes and gas compounds to have heavier carbon isotopic compositions at high maturity stages. The enrichment of ¹³C in n-alkanes and gas hydrocarbons are 1‰ and 4–6‰ respectively, compared to fresh kerogen. Oil expulsion may act as open system opposite to the oil retention that influences the data pattern in crossplots of δ¹³C₂–δ¹³C₃ versus C₂/C₃, δ¹³C₂–δ¹³C₃ versus δ¹³C₁ and δ¹³C₁–δ¹³C₂ versus ln(C₁/C₂), which are widely used for identification of gas from kerogen cracking or oil cracking. These results suggest that the reserve estimation and gas/source correlation in deep burial basins should consider the proportion of oil retention to oil expulsion the source rocks have experienced.     

Recognising biodegradation in gas/oil accumulations through the δC compositions of gas components

A large suite of natural gases (93) from the North West Shelf and Gippsland and Otway Basins in Australia have been characterised chemically and isotopically resulting in the elucidation of two types of gases. About 26% of these gases have anomalous stable carbon isotope compositions in the C₁–C₄ hydrocarbons and CO₂ components, and are interpreted to have a secondary biogenic history. The characteristics include unusually large isotopic separations between successive n-alkane homologues (up to +29‰ PDB) and isotopically heavy CO₂ (up to +19.5‰ PDB). Irrespective of geographic location, these anomalous gases are from the shallower accumulations (600–1700 m) where temperatures are lower than 75°C. The secondary biogenic gases are readily distinguishable from thermogenic gases (74% of this sample suite), which should assist in the appraisal of hydrocarbons during exploration where hydrocarbon accumulations are under 2000 m. While dissolution effects may have contributed to the high ¹³C enrichment of the CO₂ component in the secondary biogenic gases, the primary signature of this CO₂ is attributed to biochemical fractionation associated with anaerobic degradation and methanogenesis. Correlation between biodegraded oils and biodegraded “dry” gas supports the concept that gas is formed from the bacterial destruction of oil, resulting in “secondary biogenic gas”. Furthermore, the prominence of methanogenic CO₂ in these types of accumulations along with some isotopically-depleted methane provides evidence that the processes of methanogenesis and oil biodegradation are linked. It is further proposed that biodegradation of oil proceeds via a complex anaerobic coupling that is integral to and supports methanogenesis.     

Gas accumulation from oil cracking in the eastern Tarim Basin: A case study of the YN2 gas field

Oil and gas exploration in eastern Tarim Basin, NW China has been successful in recent years, with several commercial gas accumulations being discovered in a thermally mature to over-mature region. The Yingnan2 (YN2) gas field, situated in the Yingnan structure of the Yingjisu Depression, produces gases that are relatively enriched in nitrogen and C₂₊ alkanes. The δ¹³C₁ (−38.6‰ to −36.2‰) and δ¹³C₂ values (−30.9‰ to −34.7‰) of these gases are characteristic of marine sourced gases with relatively high maturity levels. The distributions of biomarkers in the associated condensates suggest close affinities with the Cambrian–Lower Ordovician source rocks which, in the Yingjisu Sag, are currently over-mature (with 3–4%Ro). Burial and thermal maturity modeling results indicate that paleo-temperatures of the Cambrian–Lower Ordovician source rocks had increased from 90 to 210 °C during the late Caledonian orogeny (458–438 Ma), due to rapid subsidence and sediment loading. By the end of Ordovician, hydrocarbon potential in these source rocks had been largely exhausted. The homogenization temperatures of hydrocarbon fluid inclusions identified from the Jurassic reservoirs of the YN2 gas field suggest a hydrocarbon emplacement time as recent as about 10 Ma, when the maturity levels of Middle–Lower Jurassic source rocks in the study area were too low (<0.7%Ro) to form a large quantity of oil and gas. The presence of abundant diamondoid hydrocarbons in the associated condensates and the relatively heavy isotopic values of the oils indicate that the gases were derived from thermal cracking of early-formed oils. Estimation from the stable carbon isotope ratios of gaseous alkanes suggests that the gases may have been formed at temperatures well above 190 °C. Thus, the oil and gas accumulation history in the study area can be reconstructed as follows: (1) during the late Caledonian orogeny, the Cambrian–Lower Ordovician marine source rocks had gone through the peak oil, wet gas and dry gas generation stages, with the generated oil and gas migrating upwards along faults and fractures to form early oil and gas accumulations in the Middle–Upper Ordovician and Silurian sandstone reservoirs; (2) since the late Yanshanian orogeny, the early oil accumulations have been buried deeper and oil has undergone thermal cracking to form gas; (3) during the late Himalayan orogeny, the seals for the deep reservoirs were breached; and the gas and condensates migrated upward and eventually accumulating in the relatively shallow Jurassic reservoirs.     

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.     

The optical features and hydrocarbon-generating model of “barkinite” from Late Permian coals in South China

Leping coal is known for its high content of “barkinite”, which is a unique liptinite maceral apparently found only in the Late Permian coals of South China. “Barkinite” has previously identified as suberinite, but on the basis of further investigations, most coal petrologists conclude that “barkinite” is not suberinite, but a distinct maceral. The term “barkinite” was introduced by (State Bureau of Technical Supervision of the People's Republic of China, 1991, GB 12937-91 (in Chinese)), but it has not been recognized by ICCP and has not been accepted internationally.In this paper, elemental analyses (EA), pyrolysis-gas chromatography, Rock-Eval pyrolysis and optical techniques were used to study the optical features and the hydrocarbon-generating model of “barkinite”. The results show that “barkinite” with imbricate structure usually occurs in single or multiple layers or in a circular form, and no definite border exists between the cell walls and fillings, but there exist clear aperture among the cells.“Barkinite” is characterized by fluorescing in relatively high rank coals. At low maturity of 0.60–0.80%R_o, “barkinite” shows strong bright orange–yellow fluorescence, and the fluorescent colors of different cells are inhomogeneous in one sample. As vitrinite reflectance increases up to 0.90%R_o, “barkinite” also displays strong yellow or yellow–brown fluorescence; and most of “barkinite” lose fluorescence at the maturity of 1.20–1.30%R_o. However, most of suberinite types lose fluorescence at a vitrinite reflectance of 0.50% Ro, or at the stage of high volatile C bituminous coal. In particular, the cell walls of “barkinite” usually show red color, whereas the cell fillings show yellow color under transmitted light. This character is contrary to suberinite.“Barkinite” is also characterized by late generation of large amounts of liquid oil, which is different from the early generation of large amounts of liquid hydrocarbon. In addition, “barkinite” with high hydrocarbon generation potential, high elemental hydrogen, and low carbon content. The pyrolysis products of “barkinite” are dominated by aliphatic compounds, followed by low molecular-weight aromatic compounds (benzene, toluene, xylene and naphthalene), and a few isoprenoids. The pyrolysis hydrocarbons of “barkinite” are mostly composed of light oil (C₆–C₁₄) and wet gas (C₂–C₅), and that heavy oil (C₁₅⁺) and methane (C₁) are the minor hydrocarbon.In addition, suberinite is defined only as suberinized cell walls—it does not include the cell fillings, and the cell lumens were empty or filled by corpocollinites, which do not show any fluorescence. Whereas, “barkinite” not only includes the cell walls, but also includes the cell fillings, and the cell fillings show bright yellow fluorescence.Since the optical features and the hydrocarbon-generating model of “barkinite” are quite different from suberinite. We suggest that “barkinite” is a new type of maceral.     

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     

Environmental control of carbon isotope variations in Pennsylvania black-shale sequences, Midcontinent, U.S.A.

A reversal of the conventional carbon isotope relationship, “terrestrial-lighter-than-marine” organic matter, has been documented for two Pennsylvanian (Desmoinesian) cyclothemic sequence cores from the Midcontinent craton of the central United States. “Deep” water organic-rich phosphatic black shales contain a significant proportion of algal-derived marine organic matter (as indicated by organic petrography, Rock-Eval hydrogen index and ratios) and display the lightest δ¹³C-values (max −27.80‰ for kerogen) while shallower water, more oxic facies (e.g. fossiliferous shales and limestones) contain dominantly terrestrial organic matter and have heavier δ¹³C_kerogen-values (to −22.87‰ for a stratigraphically adjacent coal). δ¹³C-values for extract fractions were relatively homogeneous for the organic-rich black shales with the lightest fraction (often the aromatics) being only 1‰, or less, more negative than the kerogen. Differences between extract fractions and kerogens were much greater for oxic facies and coals (e.g. saturates nearly 5‰ lighter than the kerogen).A proposed depositional model for the black shales calls upon a large influx of nutrients and humic detritus to the marine environment from the laterally adjacent, extremely widespread Pennsylvanian (peat) swamps which were rapidly submerged by transgression of the epicontinental seas. In this setting marine organisms drew upon a CO₂-reservoir which was in a state of disequilibrium with the atmosphere, being affected by isotopically light “recycled-CO₂” derived from the decomposition of peaty material in the water column and possibly from the anoxic diagenesis of organic matter in the sediments.     

An experimental comparison of gas generation from three oil fractions: Implications for the chemical and stable carbon isotopic signatures of oil cracking gas

Although oil cracking has been documented as one of the important sources of gas in many overmature marine sedimentary basins, the chemical and carbon isotopic signatures of gases of this origin are still open to question. In this study a Cambrian crude oil from the central Tarim basin, along with its main separated fractions (saturates, aromatics and asphaltenes), were pyrolyzed in sealed gold tubes to investigate how generated gases vary in chemical and carbon isotopic composition and how this variation would influence the genetic interpretation of oil cracking gas. The results indicate that the gases from cracking of aromatics and asphaltenes are much drier and more enriched in ¹³C than the gases from the cracking of saturates and crude oil at the same level of thermal maturity. In the experimental run of 20 °C/h, the dryness index of the gases (defined as the volume percentage of C₁ in C_1–5) from the cracking of saturates ranges from 26.2–90.6% with the methane carbon isotope change ranging from −54.8‰ to −35.5‰, whereas the dryness index is never lower than 60.6% for the gases from the cracking of aromatics with methane carbon isotope ranging from −39.9‰ to −32.2‰. Correspondingly, experimental data for the four samples plot in different areas in diagrams designed to distinguish oil cracking gas from kerogen cracking gas, such as ln(C₂/C₃) vs. δ¹³C₂–δ¹³C₃ and δ¹³C₁ vs. δ¹³C₂–δ¹³C₃, indicating compositional variability of crude oil could assert an important influence in these diagrams. Therefore it is prudent to bring other geological constraints into consideration to avoid misinterpretation.The kinetic parameters for the bulk generation of C_1–5 gas and the methane carbon isotope fractionation extrapolated to geological conditions of 2 °C/Ma and an initial temperature of 50 °C show that the temperatures of C_1–5 gas generation from the aromatics and asphaltenes are lower than those from the saturates and crude oil due to their lower activation energies and frequency factors. Generation of C_1–5 gases from the aromatics is modeled to be initiated about 122 °C whereas the initiation temperature for the saturates sample is 176 °C. Below 189 °C (EasyRo = 1.8%), the yields of C_1–5 gases follow the order: aromatics > asphaltenes > crude oil > saturates. At similar thermal maturity levels, the methane carbon isotopic compositions are significantly different for the four samples, with an order of ¹³C enrichment: aromatics > asphaltenes > crude oil > saturates, however the difference in methane carbon isotopes becomes smaller with increasing temperature. This indicates that methane carbon isotopic values can be significantly different for gases cracked from oils that are compositionally diverse, especially in the early stage of methane generation.     

Chemical and isotopic characterization of hydrocarbon gas traces in porewater of very low permeability rocks: The example of the Callovo-Oxfordian argillites of the eastern part of the Paris Basin

A methodology has been developed to determine chemical and carbon isotopic compositions of trace amounts of hydrocarbon gas compounds (methane, ethane, propane, iso- and normal-butane) present as dissolved compounds in the porewater of the low permeability Callovo-Oxfordian argillites in eastern Paris Basin, France. Results indicate that the studied hydrocarbons contain significant amounts of ethane, butane and propane, in addition to methane. Carbon isotopic compositions reflect primarily thermogenic origin (thermal cracking of organic matter), and lack of any significant biodegradation. Because temperature did not exceed 50 °C in the studied argillites, investigated hydrocarbons must have originated in hotter/deeper organic-bearing formations, possibly Stephanian coals. Data supports the predominance of high maturity thermogenic gas in the upper part of the Callovo-Oxfordian, and low maturity thermogenic gas mixed with minor bacterially produced methane in the lower part of the formation. A mixing between three end-member gases models quite well the data: one thermogenic gas with a low maturity (42% methane, with a δ¹³C of − 53‰), a gas with higher maturity (55% methane, with a δ¹³C of − 47‰) and a bacterial gas (99.45% methane, with a δ¹³C of − 80‰). This study illustrates that migration of hydrocarbon gases can take place in rocks with very low permeability and porosity, such as compacted mudrocks, given enough time. It further suggests that the studied fluid migration and transfer in aquitards would help characterization and understanding of fluid movements in sedimentary basins, as a complement to studies focused on water aquifers and hydrocarbon reservoirs. Chemical and isotopic composition of dissolved hydrocarbons in porewater can be used as natural tracers of fluid circulation in sedimentary basins, in addition to more conventional tracers.     

Use of comprehensive two-dimensional gas chromatography for the characterization of ultra-deep condensate from the Bohai Bay Basin,China

A gas condensate from well ND1 in the Jizhong Depression of the Bohai Bay Basin, China is characterized by two-dimensional gas chromatography with flame ionization detector (GC × GC–FID) and time-of-flight mass spectrometry (GC × GC–TOFMS). This condensate is sourced from the fourth member of the Shahejie Formation (Es4) but reservoired in the Mesoproterozoic Wumishan Formation carbonate at a depth of 5641–6027 m and the reservoir temperature is 190–201 °C. It is the deepest and the highest temperature discovery in the basin to date. The API gravity of the condensate is 51° and the sulfur content is < 0.04%. A total of 4955 compounds were detected and quantified. Saturated hydrocarbons, aromatic hydrocarbons and non-hydrocarbon account for 94.8%, 5.1% and 0.02% of the condensate mass, respectively. Some long chain alkylated cyclic alkanes, decahydronaphthalenes and diamondoids are tentatively identified in this condensate. The C₆–C₉ light hydrocarbon parameters show that the gas condensate was generated at relatively high maturity but its generation temperature derived from the dimethylpentane isomer ratio seems far lower than the current reservoir temperature. Some light hydrocarbon parameters indicate evaporative fractionation may also be involved due to multiple-charging and mixing. The diamondoid concentrations and gas oil ratio (GOR) suggest that the ND1 condensate results from 53.3–55% cracking. Since significant liquids remain, the exploration potential of ultra-deep buried hill fields in the Bohai Bay Basin remains high.     

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.     

Stable carbon isotope compositions and source rock geochemistry of the giant gas accumulations in the Ordos Basin, China

Ordos Basin, the second largest sedimentary basin in China, contains enormous natural gas resources. Each of the four giant gas fields discovered so far in this basin (i.e., Sulige, Yulin, Wushenqi and Jingbian) has over 100 billion cubic meters (bcm) or 3.53 trillion cubic feet (tcf) of proven gas reserves. This study examines the stable carbon isotope data of 125 gas samples collected from the four giant gas fields in the Ordos Basin. Source rocks in the Upper Paleozoic coal measures are suggested by the generally high δ¹³C values of C₁–C₄ gaseous hydrocarbons in the gases from the Sulige, Yulin and Wushenqi gas fields. While the δ¹³C_iC4 value is higher than that of the δ¹³C_nC4, the dominant ranges for the δ¹³C₁, δ¹³C₂, and δ¹³C₃ values in these Upper Paleozoic reservoired gases are −34 to −32‰, −27 to −23‰, and −25 to −24‰, respectively. The δ¹³C values of methane, benzene and toluene in gases from the Lower Paleozoic reservoirs of the Jingbian field indicate a significant contribution from humic source rocks, as they are similar to those in the Upper Paleozoic reservoirs of the Sulige, Yulin and Wushenqi gas fields. However, the wide variation and reversal in the δ¹³C₁, δ¹³C₂ and δ¹³C₃ values in the Jinbian gases cannot be explained using a single source scenario, thus the gases were likely derived dominantly from the Carboniferous-Permian coal measures with some contribution from the carbonates in the Lower Permian Taiyuan Formation. The gas isotope data and extremely low total organic carbon contents (<0.2% TOC) suggest that the Ordovician Majiagou Formation carbonates are unlikely to be a significant gas source rock, thus almost all of the economic gas accumulations in the Ordos Basin were derived from Upper Paleozoic source rocks.     

Geochemistry and occurrence of inorganic gas accumulations in Chinese sedimentary basins

Inorganic gases are commonly seen in eastern China and occasionally in southern China from the shallow water columns above hot and cold springs. The gases contain 68% to nearly 100% CO₂, with δ¹³C_CO2 and δ¹³C₁ values in the range of −1.18‰ to −6.00‰ and −19.48‰ to −24.94‰, respectively. All of the 34 large inorganic CO₂ and one inorganic methane accumulations discovered in China are distributed in eastern parts of the country, from both onshore and continental shelf basins. No commercial inorganic gas accumulation has been found in central and western China. This is a review of the occurrence and geochemical characteristics of inorganic gas accumulations in Chinese sedimentary basins. A detailed study of gas samples collected from four representative inorganic CO₂ pools and one possible inorganic methane pool indicates that inorganic alkane gases typically show δ¹³C₁ values greater than −10‰ versus PDB (mostly −30‰), with a positive stable carbon isotope sequence of δ¹³C₁ < δ ¹³C₂ < δ¹³C₃ < δ ¹³C₄. In contrast, the δ¹³C₁ values of biogenic alkane gases are lighter than −30‰, with a negative isotope sequence (i.e. δ¹³C₁ > δ¹³C₂ > δ ¹³C₃ > δ¹³C₄). Inorganic gases also tend to show less negative δ¹³C_CO2 values (−10‰) than biogenic gases (<−10‰).     

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

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

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.     

Middle Pleistocene climate and habitat change at Zhoukoudian, China, from the carbon and oxygen isotopic record from herbivore tooth enamel

The Pleistocene deposits at Zhoukoudian, often referred to as the “Peking Man” site, contain dental remains from a diverse group of herbivores, including Equus sanmeniensis, Cervus elaphus, Cervus nippon, Megaloceros pachyosteus, Sus lydekkeri, and Dicerorhinus choukoutienensis. The carbon and oxygen isotopic compositions of structural carbonate within the enamel of these teeth are used to reconstruct the paleodiet and paleoenvironment of the mammals. The δ¹³C values of enamel from Zhoukoudian range from −2.3‰ to −13.0‰, indicating that these mammals consumed between 25% and 100% C₃ plants. The presence of significant amounts of C₄ plants in the diets of some herbivore species indicates that at the onset of the Middle Pleistocene local habitats included mixed C₃/C₄ vegetation. By approximately 470,000 yr ago, C₃ plants dominated the diets of herbivores studied, suggesting that the abundance of C₄ flora had decreased in the area. For all deer analyzed in this study, the values of δ¹³C and δ¹⁸O decrease substantially from about 720,000 to 470,000 yr ago. This trend may be due to a strengthening of the winter monsoon during the Middle Pleistocene.     

Using GC-MS/Combustion/IRMS to determine the C/C ratios of individual hydrocarbons produced from the combustion of biomass materials--application to biomass burning

Simultaneous mass spectral detection and stable carbon isotope analysis was performed on individual indigenous n-alkanes isolated from single C₄ and C³ plant species and on a series of aliphatic and polycyclic aromatic hydrocarbons (PAH) produced from the combustion of these same biomass materials. The analysis technique used a combined gas chromatograph-mass spectrometer/combustion/isotope ratio mass spectrometer (GC-MS/C/IRMS). Precision (2σ) for replicate measurements of individual compounds in standard solutions using this novel configuration ranged between 0.2 and 0.5‰ for n-alkanes and 0.3 and 0.8‰ for PAH. Accuracy of the n-alkane measurements ranged between 0.1 and 0.4‰ and that of the PAH measurements ranged between 0.2 and 0.9‰. Replicate GC-MS/C/IRMS measurements on the combustion-derived n-alkene/alkane pairs were performed to within a precision of between 0.1 and 1.1‰ and the precision for the combustion PAH was similar to the standard PAH solution. No notable isotopic effects were observed when altering the temperature of the combustion process from 900 to 700°C, or as a result of the individual n-alkenes/alkanes partitioning between the gaseous and condensate fractions. Combustion-derived n-alkenes/alkanes ranged from C₁₁ to C₃₁, and the C₄-derived n-alkenes/alkanes were approx. 8‰ more enriched in ¹³C than the C₃-derived compounds. Both the C₄ and C₃-derived n-alkenes/alkanes (C₂₀-C₃₀) were isotopically similar to the indigenous n-alkanes and were 2-3‰ more depleted in ¹³C than the lower mol. wt (C₁₁₁₁-C₁₉) n-alkenes/alkanes, suggesting an independent origin for the lower mol. wt compounds. Combustion-generated C₄ and C₃-derived 2-, 3-, and 4-ring PAH were also isotopically distinct (Δδ = 10‰). Unlike the n-alkenes/alkanes, no compound-to-compound variations were observed between the low and high mol. wt PAH. This study demonstrates that the isotopic composition of original plant biomass material is mainly preserved in the aliphatic hydrocarbons and PAH generated by its combustion. Consequently, analyses of these compounds in sediments impacted by fire occurrences may provide useful information about paleo-fire activity that may help elucidate the impact biomass burning may have had and could have on climate-biosphere interactions.     

Stable isotopes of carbon dioxide in soil gas over massive sulfide mineralization at Crandon, Wisconsin

Stable isotope ratios of oxygen and carbon were determined for CO₂ in soil gas in the vicinity of the massive sulfide deposit at Crandon, Wisconsin with the objective of determining the source of anomalously high CO₂ concentrations detected previously by McCarthy et al. (1986). Values of δ¹³C in soil gas CO₂ from depths between 0.5 and 1.0 m were found to range from −12.68‰ to −20.03‰ (PDB). Organic carbon from the uppermost meter of soil has δ¹³C between −24.1 and −25.8‰ (PDB), indicating derivation from plant species with the C₃ (Calvin) type of photosynthetic pathway. Microbial decomposition of the organic carbon and root respiration from C₃ and C₄ (Hatch-Slack) plants, together with atmospheric CO₂ are the likely sources of carbon in soil gas CO₂. Values of δ¹⁸O in soil-gas CO₂ range from 32 to 38‰ (SMOW). These δ¹⁸O values are intermediate between that calculated for CO₂ gas in isotopic equilibrium with local groundwaters and that for atmospheric CO₂. The δ¹⁸O data indicate that atmospheric CO₂ has been incorporated by mixing or diffusion. Any CO₂ generated by microbial oxidation of organic matter has equilibrated its oxygen isotopes with the local groundwaters.The isotopic composition of soil-gas CO₂ taken from directly above the massive sulfide deposit was not distinguishable from that of background samples taken 1 to 2 km away. No enrichment of the δ¹³C value of soil-gas CO₂ was observed, contrary to what would be expected if the anomalous CO₂ were derived from the dissolution of Proterozoic marine limestone country rock or of Paleozoic limestone clasts in glacial till. Therefore, it is inferred that root respiration and decay of C₃ plant material were responsible for most CO₂ generation both in the vicinity of the massive sulfide and in the “background” area, on the occasion of our sampling. Interpretation of our data is complicated by the effects of rainfall, which significantly reduced the magnitude of the CO₂ anomaly. Therefore, we cannot rule out the possible mechanism of carbonate dissolution driven by pyrite oxidation, as proposed by Lovell et al. (1983) and McCarthy et al. (1986). Further work is needed on seasonal and daily variations of CO₂ concentrations and stable isotope ratios in various hydrogeologic and ecologic settings so that more effective sampling strategies can be developed for mineral exploration using soil gases.