Biomarker signatures from Neoproterozoic–Early Cambrian oil,western India

The Neoproterozoic–Early Cambrian time is the cradle of multicellular, eukaryotic life and thereafter metazoan life started populating the planet. Biomarkers, which record the chronicles of biotic events on Earth, have been investigated using gas chromatography–mass spectrometry from a suite of nine oil samples extracted from oil stained sediments and a crude oil of Neoproterozoic–Early Cambrian age from Bikaner-Nagaur Basin, western India. The biomarker distribution is characterized by high concentration of both tricyclic terpanes and pentacyclic hopanes. The predominance of C₂₉ regular sterane over C₂₇ and C₂₈ steranes indicates green algal contribution and may imply the prominence and diversification of the same algal group. The low pristane/phytane ratio and occurrence of substantial quantity of gammacerane, monomethyl 2-methyl-2-(2,4,8-trimethyltridecyl) chroman and 1,1,7,8-tetramethyl-1,2,3,4 tetrahydrophenanthrene are indicative of stratified water column as well as anoxic and enhanced salinity condition of the environment of deposition. This paper reports for the first time the presence of methyltrimethyltridecyl chromans (MTTCs) from Neoproterozoic–Early Cambrian time. Putative C₁₉ norsteranes, probably indicative of sponge input, are recorded in the studied samples and also reported from other infracambrian oils and sediments. Normal alkanes (n-C₁₇ and n-C₁₈) and isoprenoids (pristane and phytane) are highly depleted in δ¹³C. The overall biomarker distribution and carbon isotope data of oils from Bikaner-Nagaur Basin show similarities with those of other infracambrian oils like Huqf oils from Oman and Baykit High oils from eastern Siberia.     

Carbon and sulfur isotopic compositions of Early Cambrian black shales,NW Hunan,China: Implications for the Paleoceanographic sedimentary environment

In order to better understand the paleoceanographic sedimentary environment of the Lower Cambrian black shales extensively distributed in South China, outcropped along the present southern margin of the Yangtze Platform with a width of ca. 200-400 km and a length of more than 1500 km, we present new paired δ13C data on carbonates (δ13Ccarb) and associated organic carbon (δ13Corg) and δ34Spy data on sedimentary pyrite in black shales from three sections (Ganziping, Shancha and Xiaohekou) located in NW Hunan, China. In these sections, a total of 82 Lower Cambrian black shale samples have δ13Ccarb values ranging from -4.0‰ to 1.7‰ with an average value of -2.1‰, and δ13Corg values between -34.9‰ and -28.8‰, averaging -31.9‰. The ?34Spy values of 16 separated sedi-mentary pyrite samples from the black shales vary between +10.2‰ and +28.7‰ with an average value of +19.5‰, presenting a small isotope fractionation between seawater sulfate and sedimentary sulfide. The model calculation based on credible data from the paired analyses for δ13Ccarb and δ13Corg of 11 black shale samples shows a high CO2 concentration in the Early Cambrian atmosphere, about 20 times higher than pre-industrial revolution values, consis-tent with previous global predictions. The small sulfur isotope fractionation between seawater sulfate and sedimen-tary sulfide in black shales, only 15.5‰ on average, implies a low sulfate level in the Early Cambrian seawater around 1 mmol. In combination with a high degree of pyritization (DOP) in the black shales, it is suggested that sul-fidic deep-ocean water could have lingered up to the earliest Cambrian in this area. The black shale deposition is envisaged in a stratified marine basin, with a surface euphotic and oxygenated water layer and sulfidic deeper water, controlled by a continental margin rift.     

Predominance of archaea-derived hydrocarbons in an Early Triassic microbialite

We investigated the distribution of lipids in Lower Triassic sedimentary rocks (252–247 myr) from South China, including a shallow water microbialite in the uppermost section of the outcrop. Archaeal derived hydrocarbons were the major constituents of the microbialite from the latest Early Triassic. Among these, we detected (i) abundant C₄₀ acyclic and monocyclic biphytanes (possibly derived from glycerol dialkyl glycerol tetraether lipids) and their degradation products, C_30–39 pseudohomologues and (ii) a C₂₅ head-to-tail linked (regular) isoprenoid hydrocarbon [possibly derived from dialkyl glycerol diether lipids (DGDs)] and its degradation products, C_21–24 pseudohomologues and abundant pristane and phytane. Through combination of compound-specific stable carbon isotope analysis of isoprenoid hydrocarbons, which had average δ¹³C values of −35‰ to −30‰, and their molecular distribution, it was not possible to unambiguously define the archaeal source for the biphytanes in the microbialite. The δ¹³C values for pristane and phytane were similar to those for head-to-tail linked C_21–25 isoprenoids; potential source organisms for these compounds were halophilic archaea. Except for methane seep microbialites, no other ancient or recent phototrophic microbialites have been reported to contain predominantly archaeal isoprenoid hydrocarbons. Our findings suggest the presence of a new type of microbialite.     

Paleoceanographic Indicators for Early Cambrian Black Shales from the Yangtze Platform,South China: Evidence from Biomarkers and Carbon Isotopes

The lower Cambrian Niutitang Formation, a widespread black shale deposition, is of geological interest because of its polymetallic beds, Cambrian explosion, depositional ages, dramatic environmental changes and so on. Previous study focused mainly on inorganic geochemistry and few studies have investigated the organic fractions of upper Neoproterozoic-lower Cambrian strata in South China. Here we report a study of biomarkers plus organic carbon isotopes for black shales from Ganziping, Hunan Province (China). All the saturated hydrocarbon fractions have a unimodal distribution of n-alkanes, a high content of short-chain alkanes and maximize at C 19 or C 20 (C 23 for sample Gzh00-1). The C 27 /C 29 sterane ratio ranges from 0.77 to 1.20 and 4-methylsteranes are in low abundance. These parameters indicate that algae and bacteria are the important primary producers. Furthermore, biomarker maturity proxies show the samples to be higher maturity. The low Pr/Ph values (<0.7) suggest that the samples were deposited under anoxic conditions and, likely, under stratified water columns. In addition, 25-norhopanes and gammacerane are present as diagnostic indicators of normal marine salinity and dysoxic to anoxic conditions. During the Early Tommotian, known to coincide with a transgression event, small shelly fossils increased in abundance and diversity. Moreover, positive δ 13 C org excursions close to 1.4‰ occur at the base of the Tommotian stage. In summary, the Early Cambrian black shales were deposited under dramatic paleoenvironmental changes, including oceanic anoxia, higher primary productivity and sea-level rise.     

Early cambrian carbon isotope stratigraphy in the tarim basin and a correlation with the yangtze platform

Carbon isotope chemostratigraphy has been used worldwide for stratigraphic correlation.In this study,δ13Ccarb values are estimated for the Early Cambrian Sugaitebulake section in the Tarim Basin,Xinjiang Autonomous Region,China.As a result,one positive and two negative carbon isotope excursions in the studied section were iden-tified.The δ13Ccarb values reached the maximum negative excursion(N1:-12.39‰) at the basal of the Yuertusi For-mation,and then increased to P1.After P1,δ13Ccarb values sharply decreased to about-7.06‰(N2) in the studied section.The pattern of δ13Ccarb in the Early Cambrian is comparable to the synchronous records of other sections,such as the Laolin section,the Xiaotan section and the Anjiahe section of the Yangtze Platform.It is concluded that the Early Cambrian Yuertusi Formation from the Tarim Basin is within the Nemakit-Daldynian stage,and the lower strata of the Yuertusi Formation may belong to the Zhujiaqing Formation(Meishucun Formation) of the Yangtze Platform.The Ediacaran/Cambrian boundary of the Tarim Block should be located in cherts and phosphorites suc-cessions at the basal of the Yuertusi Formation.The δ13Ccarb negative excursion N1 is just across the PC/C boundary,and may be related to certain biomass extinction due to anoxic sedimentary environment,transgression and/or the oceanic overturn.The second δ13Ccarb negative excursion N2 may account for the sea-level falling in the Early Cam-brian.     

Nitrogen isotope chemostratigraphy of the Ediacaran and Early Cambrian platform sequence at Three Gorges,South China

The appearance of multicellular animals and subsequent radiation during the Ediacaran/Cambrian transition may have significantly changed the oceanic ecosystem. Nitrogen cycling is essential for primary productivity and thus its connection to animal evolution is important for understanding the co-evolution of the Earth's environment and life. Here, we first report on coupled organic carbon and nitrogen isotope chemostratigraphy from the entire Ediacaran to Early Cambrian period by using drill core samples from the Yangtze Platform, South China. The results show that δ¹⁵N_TN values were high (~ + 6‰) until middle Ediacaran, gradually dropping down to − 1‰ at the earliest Cambrian, then rising back to + 4‰ in the end of the Early Cambrian. Organic carbon and nitrogen contents widely varied with a relatively constant C/N ratio in each stratigraphic unit, and do not apparently control the carbon and nitrogen isotopic trends. These observations suggest that the δ¹⁵N_TN and C/N trends mainly reflect secular changes in nitrogen cycling in the Yangtze Platform. Onset of the observed negative N isotope excursion coincided with a global carbon isotope excursion event (Shuram excursion). Before the Shuram event, the high δ¹⁵N probably reflects denitrification in a nitrate-limited oceanic condition. Also, degradation of dissolved and particulate organic matter could be an additional mechanism for the ¹⁵N-enrichment, and may have been significant when the ocean was rich in organic matter. At the time of the Shuram event, both δ¹³C_carb and δ¹⁵N_TN values were dropped probably due to massive re-mineralization of organic matter. This scenario is supported by an anomalously low C/N ratio, implying that enhanced respiration resulted in selective loss of carbon as CO₂ with recycled organic nitrogen. After the Shuram event, the δ¹⁵N value continued to decrease despite that δ¹³C_carb rose back to + 4‰. The continued δ¹⁵N drop appears to have coincided with a decreasing phosphorus content in carbonate. This suggests that ocean oxygenation may have generated a more nitrate-rich condition with respect to phosphorus as a limiting nutrient. Similar to the Shuram event, another negative δ¹³C_carb event in the Canglanpuan stage of the Early Cambrian is also characterized by carbon isotopic decoupling as well as the low C/N ratio. The results strongly support that the two stages of the decoupled negative δ¹³C_carb excursions reflect a disappearance of a large organic carbon pool in the ocean. The two events appear to relate with the appearance of new metazoan taxa with novel feeding strategies, suggesting a link between ocean oxygenation, nutrient cycling and the appearance and adaptation of metazoans. The nitrogen isotope geochemistry is very useful to understand the link between the environmental, ecological and biological evolutions.     

Distinguishing Cambrian from Upper Ordovician source rocks: Evidence from sulfur isotopes and biomarkers in the Tarim Basin

The reported source rocks for the abundant petroleum in the Tarim Basin, China range from Cambrian to Lower Ordovician and/or Upper Ordovician in age. However, the difference between the two groups of source rocks is not well characterized. In this study, pyrite was removed from eleven mature to over mature kerogen samples from source rocks using the method of CrCl₂ reduction and grinding. The kerogen and coexisting pyrite samples were then analyzed for δ³⁴S values. Results show that the kerogen samples from the Cambrian have δ³⁴S values between +10.4‰ and +19.4‰. The values are significantly higher than those from the Lower Ordovician kerogen (δ³⁴S of between +6.7‰ and +8.7‰), which in turn are generally higher than from the Upper Ordovician kerogen samples (δ³⁴S of between ?15.3 and +6.8‰). The associated pyrite shows a similar trend but with much lower δ³⁴S values. This stratigraphically controlled sulfur isotope variation parallels the evolving contemporary marine sulfate and dated oil δ³⁴S values from other basins, suggesting that seawater sulfate and source rock age have an important influence on kerogen and pyrite δ³⁴S values. The relatively high δ³⁴S values in the Cambrian to Lower Ordovician source rocks are associated with abundant aryl isoprenoids, gammacerane and C₃₅ homohopanes in the extractable organic matter, indicating that these source rocks were deposited in a bottom water euxinic environment with water stratification. Compared with the Upper Ordovician, the Cambrian to Lower Ordovician source rocks show abundance in C₂₈ 20R sterane, C₂₃ tricyclic terpanes, 4,23,24-trimethyl triaromatic dinosteroids and depletion in C₂₄ tetracyclic terpane, C₂₉ hopane. Thus, δ³⁴S values and biomarkers of source rock organic matter can be used for distinguishing the Cambrian and Upper Ordovician source rocks in the Tarim Basin.     

Hydrocarbons in 60 northeast Gulf of Mexico shelf sediments: a preliminary survey

Hydrocarbon results from gas chromatography of 60 recent sediment and 10 benthic algae samples delineate two distinct shelf environments in the northeastern Gulf of Mexico.Sediments off Florida (shell hashes and sands) have moderate amounts of lipids/total sediment (average 113ppm ± 80%) but low hydrocarbon levels (average 3.06 ppm ± 41%). Aliphatic hydrocarbons are dominated by a series of branched or cyclic, unsaturated C₂₅ isomers. The major n-alkane is n-C₁₇. The n-alkane and isoprenoid patterns are consistent with a marine hydrocarbon source.Sediments closer to the Mississippi River (silts and clays) contain large amounts of lipids (average 232 ppm ± 53%) and hydrocarbons (average 11.7 ppm ± 55%) to total sediment. Aliphatic hydrocarbons are mainly odd carbon number high molecular weight n-alkanes, indicating a terrigenous hydrocarbon source. Isoprenoids are present in greater abundance than in sediments off Florida (n-C₁₇/ pristane and n-C₁₈/phytane ratios ~2to 3). Relatively large amounts of n-C₁₆, together with an even distribution of n-alkanes in the range C₁₄–C₂₀ and a substantial unresolved envelope all point to a fossil fuel input to the Mississippi samples.Samples off the Alabama coast show intermediate characteristics.     

Hopanes and hopenes of the Lower Cambrian Sinyaya Formation (northern slope of the Aldan Anteclise)

Hopane hydrocarbons contained in organic matter from the Lower Cambrian Sinyaya Formation, southeast of the Siberian platform, were analyzed by gas chromatography/mass spectrometry. This study first identified C₂₈ 28, 30-bisnorhopane and its homologues present in high concentrations in autochthonous organic matter from East Siberian sedimentary basins. These biomarkers can be used in distinguishing between the sources of naphthides on the northern slope of the Aldan anteclise. Two saturated naphthenic hydrocarbons, C₃₁ homohopene and C₃₁ 28-norhomohopene, were also detected. This study provides some details on hopane distribution, organic matter accumulation conditions, and the degree of OM catagenesis.     

Impact of anaerobic biodegradation on alkylphenanthrenes in crude oil

The biodegradation of crude oil by microorganisms from well Luo-801, China, was examined in cultures grown under conditions that promoted either methanogenesis or sulfate reduction, at 35 °C and 55 °C. Headspace gas and oil compositions were characterized at 180 d and 540 d. Alkylphenanthrenes are relatively recalcitrant to bacterial attack and the biodegradation of these compounds appeared to be insignificant after 180 d under both conditions, but is evident after 540 d. The depletion of alkylphenanthrenes was monitored through evaluation of the ratio of alkylphenanthrenes to the most bioresistant, analyzed component (C₂₈ 20R triaromatic steroid hydrocarbon) and isomer susceptibility also was evaluated by relative abundance comparison within the compound class. The influence of growth temperature varied. Only slight differences in alkylphenanthrene concentrations were observed after 180 d whereas the greater degrees of biodegradation were observed at 35 °C in the methanogenic culture and at 55 °C in the sulfate reducing culture. Overall, higher biodegradation rates occur under sulfate reducing condition, which is consistent with the conclusion that methanogens are generally less able to compete for substrates than sulfate reducers. The biodegradation susceptibility of alkylphenanthrenes decreases with increasing degree of alkylation, i.e., phenanthrene (P) and methylphenanthrenes (MPs) were more easily biodegradable than C₂-alkylphenanthrenes (C₂-Ps) and C₃-alkylphenanthrenes (C₃-Ps). Biodegradation selectivity for specific homologues is not striking for the limited time duration of the experiments. However, 3-MP seems slightly more vulnerable than other methylphenanthrene isomers and 1,7-DMP has slightly higher ability to resist biodegradation than the other C₂-P isomers. The commonly used thermal maturity parameters derived from methylphenanthrene isomer ratios are altered insignificantly by biodegradation and remain valid for geochemical assessment. This information should be useful for assessing the limits of in situ crude oil biodegradation.     

Strike-slip faults in the Vostochnyy range of Shmidt peninsula on Sakhalin

A genetic link between oils and source rocks of lower Paleozoic deposits of the Baltic syneclise is revealed from the identity of change in individual composition of hydrocarbons (HC) and their ratios along the section. It is marked most clearly from the pristane/phytane ratio and from the identical trend of n-alkane and isoprenoid distribution curves for oils and dispersed organic matter (OM). The patterns observed are complemented by the coincidence of maximums of carbon atoms in the higher molecular part (C₂₅ - C₃₅) of n-alkanes and by the odd/even (O/E) molecular ratio. The sterane/triterpane and mononaphthenonaphthalene/ phenanthrene ratios are found to be close. —Authors.     

Stable isotope and organo-geochemical studies on phanerozoic sediments of the Williston Basin,North America

Carbon isotope studies have been carried out on marine Phanerozoic sediments of the Williston Basin, North America. Special attention was given to the recognition of systematic variations with age.δ ¹³C measurements on the carbonate fraction show a 3%₀ depletion from the Cambrian to the Mississippian and a 1–2%₀ enrichment to the Jurassic. Both the sign of these displacements and a good correlation with the organic carbon content suggest that real variations in the rate of photosynthesis may have been the driving force for these changes with age.Because of the large isotopic heterogeneities in the organic biomass, systematic fluctuations with age in the δ ¹³C-values of the total organic carbon record are hard to prove. Nevertheless, a significant 3%₀ depletion was observed from the Devonian to the end of the Carboniferous. This depletion seems to occur on a worldwide scale. It is therefore proposed that a rise in the rate of photosynthesis as a consequence of the colonization of the continents by higher plants is the global cause of this displacement in the isotope record of the total organic carbon.The bitumen fraction does not show any systematic isotope variations with age.Comparison of coexisting δ ¹³C_org?δ ¹³C_bit pairs demonstrates that during the Ordovician-Mississippian time period no significant (> 1%₀) differences in the isotope values of these two organic carbon sources can be observed. In contrast the bitumen fraction is depleted in ¹³C as compared to the total organic carbon in the Cambrian as well as in the Pennsylvanian-Cretaceous time interval. Several parameters, i.e. the depth of burial of these sediments, the $\text{1}\text{2}$(pristane/n-C₁₇ + phytane/n-C₁₈) ratio and the n-alkane distribution pattern support the theory that the rank of the organic matter may be responsible for the observed isotopic pattern.     

Carbon geochemistry of serpentinites in the Lost City Hydrothermal System (30°N, MAR)

The carbon geochemistry of serpentinized peridotites and gabbroic rocks recovered at the Lost City Hydrothermal Field (LCHF) and drilled at IODP Hole 1309D at the central dome of the Atlantis Massif (Mid-Atlantic Ridge, 30°N) was examined to characterize carbon sources and speciation in oceanic basement rocks affected by long-lived hydrothermal alteration. Our study presents new data on the geochemistry of organic carbon in the oceanic lithosphere and provides constraints on the fate of dissolved organic carbon in seawater during serpentinization. The basement rocks of the Atlantis Massif are characterized by total carbon (TC) contents of 59 ppm to 1.6 wt% and δ¹³C_TC values ranging from −28.7‰ to +2.3‰. In contrast, total organic carbon (TOC) concentrations and isotopic compositions are relatively constant (δ¹³C_TOC: −28.9‰ to −21.5‰) and variations in δ¹³C_TC reflect mixing of organic carbon with carbonates of marine origin. Saturated hydrocarbons extracted from serpentinites beneath the LCHF consist of n-alkanes ranging from C₁₅ to C₃₀. Longer-chain hydrocarbons (up to C₄₀) are observed in olivine-rich samples from the central dome (IODP Hole 1309D). Occurrences of isoprenoids (pristane, phytane and squalane), polycyclic compounds (hopanes and steranes) and higher relative abundances of n-C₁₆ to n-C₂₀ alkanes in the serpentinites of the southern wall suggest a marine organic input. The vent fluids are characterized by high concentrations of methane and hydrogen, with a putative abiotic origin of hydrocarbons; however, evidence for an inorganic source of n-alkanes in the basement rocks remains equivocal. We propose that high seawater fluxes in the southern part of the Atlantis Massif likely favor the transport and incorporation of marine dissolved organic carbon and overprints possible abiotic geochemical signatures. The presence of pristane, phytane and squalane biomarkers in olivine-rich samples associated with local faults at the central dome implies fracture-controlled seawater circulation deep into the gabbroic core of the massif. Thus, our study indicates that hydrocarbons account for an important proportion of the total carbon stored in the Atlantis Massif basement and suggests that serpentinites may represent an important—as yet unidentified—reservoir for dissolved organic carbon (DOC) from seawater.     

Molecular fossils and sources of Cambrian heavy oil of Well Tadong-2 in the Tarim Basin,Xinjiang, China

Research on the molecular fossil characteristics of heavy oil from Well Tadong-2 is of great importance to constrain the source of marine crude oils in the Tarim Basin, Xinjiang, China. The authors synthetically applied the isotope mass spectrograph, chromatography and chromatography-mass spectrography to the studies of molecular fossil characteristics of heavy oil from Well Tadong-2 in the Tarim Basin, and the results obtained revealed that heavy oil from Well Tadong-2 is characterized by high gammacerane, high C₂₈ sterane, low rearranged sterane and high C₂₇-triaromatic steroid, these characteristics are similar to those of Cambrian-Lower Ordovician source rocks, demonstrating that Cambrian crude oils came from Cambrian-Lower Ordovician source rocks; condensed compounds (fluoranthene, pyrene, benzo[a]anthracene, bow, benzo fluoranthene, benzopyrene) of high abundance were detected in heavy oil from Well Tadong-2, and the carbon isotopic values of whole oil are evidently heavy, all the above characteristics revealed that hydrocarbons in the crude oils became densified in response to thermal alteration.     

Geochemical Evidence for Coal and Carbonaceous Mudstone as the Possible Major Oil Source Rock in the Jurassic Turpan Basin,Northwest China

Petroleum geologists have debated whether the hydrocarbons from Jurassic coal measures are derived from the coals, carbonaceous mudstones or coal-measure mudstones in the Turpan Basin. Based on the geochemistry analysis of the 20 crude oils and 40 source rocks from the Turpan Basin, some data have been obtained as follows: carbon preference index and methylphenanthrene index of the Jurassic oils are 1.16–1.45 and 0.28–0.80, and the ααα C29 sterane 20S/(20S+20R) and C29 sterane ββ/(ββ+αα) are 0.44–0.51 and 0.4–0.54 respectively, which show the normal maturity of oils; the vitrinite reflectance of the source rocks from the Xishanyao to Badaowan Formations range from 0.47% to 0.97%, which indicate immature to mature thermal evolutionary stage and sufficient conditions for generating mass mature oil. The effect of hydrocarbon expulsion should be considered when studying the source of coal-derived oil by using Biomarkers. Biomarkers in the Jurassic oils from the basin are similar to those in the coals and carbonaceous mudstones, with a strong predominant content of pristane, relatively high ratio of C15/C16 sesquiterpenoids (>1), a relatively high content of low carbon number tricyclic terpanes and C24 tetracyclic terpane, little gammacerane and C29 Ts detected, an absolute predominant content of C29 sterane and a relatively high content of diasterane. However, the opposite characteristics are shown in mudstones, with an approximately equal content of pristane and phytane, relatively low ratio of C15/C16 sesquiterpenoids (<1), a relatively high content of high carbon number tricyclic terpanes and a low content of C24 tetracyclic terpane, peaks of gammacerane and C29 Ts detected obviously and an increasing C27 sterane content. All of these characteristics identify the coals and carbonaceous mudstones as the possible major oil source rocks in this area, and they were formed in the stronger oxidizing environment with shallower water than mudstones.     

Hydrocarbon biomarkers from Ordovician sediments and the fossil alga Gloeocapsomorpha prisca Zalessky 1917

Numerous Ordovician oils worldwide are known to show unusual and distinctive distributions of hydrocarbons which, it has been suggested, are derived from a “unique benthonic mat-forming non-photosynthetic prokaryotic organism”, Gloeocapsomorpha prisca Zalessky 1917, which is the major contributor of organic matter. Organic matter-rich sediments from the Canning and Amadeus Basins of Australia, known to contain G. prisca fossils and to have the characteristic predominance of odd carbon number (C₁₃–C₁₉) n-alkanes, were investigated to determine other hydrocarbon distributions. Sediments from both basins contained abundant n-alkylcyclohexanes with odd carbon number predominance (C₁₃–C₁₉) and methyl-n-alkylcyclohexanes (C₁₄–C₂₀) which, in immature sediments, showed an even carbon number predominance. The isomer distribution of these latter compounds was determined by direct comparison with synthetic standards. The sediments from both basins also contained very similar distributions of steranes and pentacyclic triterpanes and the derived kerogens had a characteristically light carbon isotope signature.Pyrolysis of a G. prisca-rich kerogen yielded a hydrocarbon mixture with a similar composition to the sediment extract, except that there was a marked increase in the relative abundance of pristane, phytane, alkylcyclohexanes, steranes and hopanes relative to n-alkanes. We argue on the basis of the geological, geochemical and palynological data that G. prisca was probably planktonic, photosynthetic and very possibly eukaryotic and that the striking character of Ordovician oils and sediments derive from bacterial and other diagenetic imprints superimposed on the primary signature of this organism.     

Hydrocarbons of the hypersaline basins of Shark Bay,Western Australia

Shark Bay is an 8000 sq. km shallow marine embayment on the western coast of Western Australia. The waters exhibit a well established salinity gradient from oceanic to hypersaline. The chemical assemblage of sediment hydrocarbons along the salinity gradient may be classified into two distinct chemogeographic types. Firstly, oceanic sediments contain n-alkanes and a suite of highly branched and branched/cyclic C₂₅ alkenes. Hypersaline sediments are characterised by a high relative abundance of a C₂₅H₅₀ alkene together with an analogous C₂₀H₄₀ alkene and its parent C₂₀H₄₂ alkene (2,6,10-trimethyl-7-(3-methylbutyl)-dodecane). A pair of alkanes C₂₁H₄₂ and C₂₂H₄₄ increase in concentration and relative abundance with depth. The hydrocarbons of the hypersaline basins are found in only trace amounts in oceanic sediments. These chemical signals are overlain by further input indicative of the immediate biotic community.     

Stable isotope(δ~(13)C_(ker),δ~(13)C_(carb),δ~(18)O_(carb)) distribution along a Cambrian outcrop section in the eastern Tarim Basin,NW China and its geochemical significance

This study investigated the geochemical features of the lower Paleozoic strata of Yaerdang Mountain outcrop along with the core samples from well TD2∈ in the eastern Tarim Basin,NW China.The total organic carbon abundance,hydrocarbon-generating precursor biospecies,and stable isotope ratios of organics and carbonate(δ~(13)C_(ker),δ~(13)C_(carb) and δ~(18)O_(carb)) were comprehensively studied for their possible correlative constraints during sedimentary evolution.The results revealed that the δ~(13)C_(ker)(VPDB) of Cambrian kerogens along the outcrop section varied from-34.6‰ to-28.4‰,indicating an increasing tendency from the lower Cambrian to the upper Cambrian.This was on the whole accompanied by the variation in the δ~(13)C_(carb) and δ~(18)O_(carb) along the profile,which might be associated with the changes in the sea level and also in the compositional variation of benthic and planktonic biomass.The large variation in the stable carbon isotope ratios up to 6‰ along the outcrop section reflected the heterogeneity of the Cambrian source rocks from the eastern Tarim Basin.Hence,the ~(13)C-enriched crude oils from well TD2∈might have been derived from a localized stratum of Cambrian source rocks.The results from this study showed the possibility of multiple source kitchens in the Cambrian-lower Ordovician portion of Tarim Basin.     

The significance of 24-norcholestanes,triaromatic steroids and dinosteroids in oils and Cambrian–Ordovician source rocks from the cratonic region of the Tarim Basin,NW China

Two oil families in Ordovician reservoirs from the cratonic region of the Tarim Basin are distinguished by the distribution of regular steranes, triaromatic steroids, norcholestanes and dinosteroids. Oils with relatively lower contents of C₂₈ regular steranes, C₂₆ 20S, C₂₆ 20R + C₂₇ 20S and C₂₇ 20R regular triaromatic steroids, dinosteranes, 24-norcholestanes and triaromatic dinosteroids originated from Middle–Upper Ordovician source rocks. In contrast, oils with abnormally high abundances of the above compounds are derived from Cambrian and Lower Ordovician source rocks. Only a few oils have previously been reported to be of Cambrian and Lower Ordovician origin, especially in the east region of the Tarim Basin. This study further reports the discovery of oil accumulations of Cambrian and Lower Ordovician origin in the Tabei and Tazhong Uplifts, which indicates a potential for further discoveries involving Cambrian and Lower Ordovician sourced oils in the Tarim Basin. Dinosteroids in petroleum and ancient sediments are generally thought to be biomarkers for dinoflagellates and 24-norcholestanes for dinoflagellates and diatoms. Therefore, the abnormally high abundance of these compounds in extracts from the organic-rich sediments in the Cambrian and Lower Ordovician and related oils in the cratonic region of the Tarim Basin suggests that phytoplankton algae related to dinoflagellates have appeared and might have flourished in the Tarim Basin during the Cambrian Period. Steroids with less common structural configurations are underutilized and can expand understanding of the early development history of organisms, as well as define petroleum systems.     

Lipid geochemistry in a sediment core from Ruoergai Marsh deposit (Eastern Qinghai-Tibet plateau, China)

Peats in a sediment core from Ruoergai bog, which has a cold and moist plateau climate with major source input from herbaceous plants, have been studied by GC–MS in order to understand the composition and diagenetic processes of lipids in this depositional environment. Long chain components (C₂₁–C₃₅) predominate in the n-alkanes, n-alk-1-enes, n-fatty acids, n-alkan-2-ones and n-alkanols with a maximum of C₃₁, C_27, C₂₂ or C_24, C₂₃ or C₂₅ and C₂₂, respectively. A herbaceous origin for these long chain compounds is suggested, and this is supported by their stable carbon isotopic compositions. Diterpenoid hydrocarbons with abietane, pimarane and kaurane skeletons, some of which have not been reported often in modern sediments, are prominent and are derived from higher plants. Several triterpenoid ketones and alcohols with oleanane or lupane skeletons, and a series of des-A-triterpenoid hydrocarbons which have not been reported often in modern sediments are also present, and are assigned to a higher plant source. Hopanoids, including their alkanes, alkenes, ketones, alcohols and esters, are abundant and of bacterial origin. Steroid ketones and alkanols are dominated by C₂₉ homologues. C₂₈ and C₂₉ steroids are derived mainly from higher plants, whereas the C₂₇ component is assigned to a microbial source. The presence of short-chain n-alkanes with no odd-even carbon predominance, bacterially derived fatty acids (C₁₄, C₁₅, iso- and unsaturated acids), n-alkan-2-ones, des-A-triterpenoid hydrocarbons, hopanoids and some steroid ketones indicate that intense microbial reworking of the organic matter has taken place in this depositional environment. The chemical and biochemical conversions of some cyclic alkenes to alkanes, such as tricyclic diterpenoids, tetracyclic terpenoids and steroid ketones, are also evident with depth. The dominance of C₂₀ components in the diterpenoid hydrocarbons may reflect an oxidizing or reducing depositional condition.