C27 C29 Steranes Research Articles

Pristine biomarker compositions recovered from biodegraded oil samples using MSSV-Hy

Oil-source and oil-oil correlations are challenging when the primary chemical composition of petroleum was altered or destroyed by biodegradation. Biomarkers that are bound to macromolecular matrices rather than being in a free form are largely protected from alteration and may therefore offer a solution to the challenges. Using Microscale Sealed Vessel Catalytic Hydrogenation (MSSV-Hy), the bound biomarkers of two North Sea and two Barents Sea oil samples, with varying levels of biodegradation, were released from their respective asphaltenes. Despite biodegradation having changed the relative concentrations of steranes (C27–C30 steranes) and hopanes (C29–C30 hopanes) in the free biomarker fraction to varying degrees, the asphaltene-bound biomarkers were protected and show pristine ratios unaffected by biodegradation, e.g., the relative content of C27–C29 steranes, the C30/C29 sterane ratio, and the C29/C30 hopane ratio. Empirical calibration then allows these bound biomarkers to be converted into regular biomarker ratios. The MSSV-Hy technique has been shown to be an efficient and effective tool for releasing asphaltene-bound biomarkers from biodegraded oil and revealing genetic information when free biomarkers are altered by biodegradation.

Study on the Applicability of Saturated Hydrocarbon Parameters in the Evaluation of Lacustrine Source Rocks and Oils Based on Thermal Simulation Experiments

Saturated hydrocarbons are widely used in the valuation of source rocks and oils, but the applicability of related parameters has received less attention. Based on the thermal simulation experiments on Mesozoic source rocks in the Yingen-Ejinaqi Basin, and the GC-MS analysis of the saturated hydrocarbon fractions of the expelled oils and extracts from solid residues, the applicability of the parameters related to lacustrine source rocks and oil were discussed. The results indicated that: Controlled by thermal degradation, both the relative abundance of the tricyclic terpenoids in terpenoids and the pregnane (including L pregnane) in steroids increased with the increase in maturity. Maturity had little effect on some environmental parameters of lacustrine source rocks and oils, such as Pr/Ph and gammacerane index, they were still effective even at the high-over maturity stage. But maturity had a significant influence on the method of using saturated hydrocarbons to identify the source of organic matter, because only at the thermal stage of Ro < 1.45%, might it effectively identify the source of organic matter by using the dominant peak of n-alkanes method and the relative abundance of C27–C29 steranes method. Most saturated hydrocarbon maturity parameters had their valid scope of application, such as C29 20S/(20S + 20R) steranes, C29αββ/(ααα + αββ) steranes and C31αβ22S/(22S + 22R) homohopanes were only effective when the Ro value was below 2.06%, for the parameter’s value would be “inverted” in the stage of over-maturity (Ro > 2.06%). However, the parameter Ts/(Ts + Tm) was effective in the whole thermal evolution process, reflecting good applicability. This study clarifies the validity of the application of commonly used saturated hydrocarbon parameters, and it can provide some reference for relevant studies.

Geochemistry of hydrocarbons-biomarkers and carbon isotopes of organic matter in the Domanik Deposits of the Timan-Pechora Basin

It has been established that the average values of some hydrocarbons biomarker coefficients of bitumens from the Domanik deposits and oils from the Domanik–Tournaisian complex coincide. These are the proportions of C27–C29 steranes, tri-/pentacyclanes ratio, and coefficients 2 × С17/С16 + С18 and 2 × С27/С26 + С28 calculated from n-alkane composition. Such indicators as the Pr/Ph, (Pr + Ph)/(n‑C17 + n‑C18), dia-/reg-steranes, and the sterane/hopane ratios in oils are slightly lower than in the bitumen. The average values of δ13C in asphaltene, resin, aromatic hydrocarbons, and aliphatic hydrocarbons fractions from oils of the Domanik genotype and in the studied bitumens are similar. The carbon isotope composition of asphaltenes in oils is depleted in 13С compared to those of resins and aromatic hydrocarbons, and vice versa in bitumens. A heterogeneous composition of the bacterial flora in the sediments of the Domanik Sea is suggested. In some places, species with high concentrations of diplopterol or hexafunctional bacteriohopanes likely dominated over bacteriohopantetrol.

Origin of organic matter and depositional characteristics of early Cambrian Niutitang Formation from South China: New insights using molecular fossils

The early Cambrian Niutitang Formation is broadly developed in South China, especially in the Yangtze region. This research explains the nature of hydrocarbons through bitumen fractions of the early Cambrian sediments of the Niutitang Formation. For this purpose, source rock samples from two diverse outcrop sections are utilized for total organic carbon content (TOC), solvent extraction, and gas chromatography–mass spectrometry (GC–MS). Results show a lower quantity of extractable organic matter in these older sediments because of higher maturation history. The presence of monomethyl alkanes suggests the contribution of prokaryotic organisms, whereas the presence of hopanoids and C27–C29 steranes shows the occurrence of eukaryotic algal sources in organic matter. Likewise, C30‐4‐methyl sterane, dinosteranes, and ß‐carotene also suggested incorporating prokaryotic and eukaryotic sources during the early Cambrian period. Various hopanoid parameters, alkylated aromatic isomers, triaromatic steroids, and vitrinite reflectance via methyl‐phenanthrene index reveal mature to higher thermal evolution levels of these lower Palaeozoic sediments. Similarly, a higher abundance of polyaromatic pyrene and fluoranthene indicates mature organic matter, and their presence could be due to hydrothermal action. The higher gammacerane index, lower pristine/phytane, and the presence of C30 dimethyl steranes indicate the anoxic saline sedimentary condition throughout the deposition of these lower Palaeozoic Niutitang Formation. The early Cambrian Niutitang Formation is deposited in an oxygen‐deficient environment and contains an adequate amount of mature‐high mature organic matter that could have the potential to produce gaseous hydrocarbons.

Hydrocarbon Potential and Biomarker Studies of EE-1 Well, Offshore Eastern Dahomey Basin, SW Nigeria

Abstract The hydrocarbon potential, organic source input, and paleodepositional environment of subsurface sediments from EE-1 well, offshore Eastern Dahomey Basin, were assessed using Rock-Eval pyrolysis and biomarker geochemistry. The total organic carbon (TOC) and soluble organic matter (SOM) in the sediments ranged from 0.96wt% to 8.92wt% and 676.12 ppm to 2883.85 ppm, respectively, indicating adequate to excellent organic richness. The pseudo-Van Krevelen plot classified the sediments as types II and III kerogen, which have the potential to generate both oil and gas. The Tmax and production index (PI) ranged from 422°C to 431°C (average, 426°C) and 0.03 to 0.24, respectively, suggesting low thermal maturity. The presence of C27–C29 steranes, oleanane, and hopane/sterane ratio (1.53/16.11), indicated organic matter from mixed sources with more terrigenous input. Cross plots of Pr/nC17 against Ph/nC18, C35/C31 – C35 homohopane index (0.05 – 0.17) and other related biomarker ratios such as C21/C23 trycyclic terpane ratio (0.33 – 0.82) signified that the sediments were deposited in mixed marine/terrigenous environment under oxic – suboxic conditions. This study has demonstrated that sediments had adequate organic matter with the potential to generate both oil and gas at appropriate thermal maturity.

Oil-charging history constrained by biomarkers of petroleum inclusions in the Dongying Depression, China

Free oils and inclusion oils were extracted from the third member of the Eocene Shahejie Formation (Es3) reservoir sandstones of the wells Chun 51 and Liang 28 in the Dongying Depression, China, and then analyzed by gas chromatography–mass spectrometry (GC–MS). Results show that biomarker distribution characteristics of the free oils and their associated inclusion oils are similar in each Es3 reservoir sandstones of the two wells, but the distributions of Pr/Ph ratio, gammacerane, hopane series and C27–C29 steranes in well Chun 51 oils are strikingly different from those of well Liang 28 oils. However, the C29 sterane ββ/(ββ + αα), Ts/(Ts + Tm) and C31 hopane 22S/(22S + 22R) ratios of inclusion oils are higher than those of related free oils in all the samples, this may indicate that maturity indicators decreased after reaching the maximum and relatively high mature oils were trapped in petroleum inclusions. Comparison with biomarkers of source-rock extracts shows that oils in the Es3 reservoir of well Chun 51 were generated from the upper Es4 source rocks, whereas oils in the Es3 reservoir of well Liang 28 were derived from the lower Es3 source rocks. Moreover, the microthermometric data and burial history indicate one oil-charging episode in the Es3 reservoirs of the two wells, during the late Neogene. It's concluded that different charging histories of these two reservoirs were attributed mainly to the sealing effect of the fault.

Biomarker evidence of algal-microbial community changes linked to redox and salinity variation, Upper Devonian Chattanooga Shale (Tennessee, USA)

AbstractLate Devonian marine systems were characterized by major environmental perturbations and associated biotic community changes linked to climate change and widespread oceanic anoxia. Here, we provide high-resolution lipid biomarker chemostratigraphic records from the Upper Devonian Chattanooga Shale (Tennessee, USA) to investigate algal-microbial community changes in the southern Illinois Basin that were related to contemporaneous shifts in marine redox (as proxied by trace metals, Fe-species, and Corg/P) and salinity conditions (as proxied by B/Ga, Sr/Ba, and S/total organic carbon). The Frasnian was characterized by dominantly bacterial lipids (high hopane/sterane), near-marine salinity, and a shift from oxic to increasingly reducing conditions in response to increasing organic carbon sinking fluxes. Aryl isoprenoids and aryl isoprenoid ratios reveal that the O2-H2S chemocline was unstable and intermittently shallow (i.e., within the photic zone). The Frasnian-Famennian boundary was marked by a shift in microalgal community composition toward green algal (e.g., prasinophyte) dominance (lower C27 and higher C28 and C29 steranes), a sharp reduction in watermass salinity, and a stable O2-H2S chemocline below the photic zone, conditions that persisted until nearly the end of the Famennian. We infer that changing watermass conditions, especially a sharp reduction in salinity to possibly low-brackish conditions (<10 psu), were the primary cause of concurrent changes in the microalgal community, reflecting tolerance of low-salinity conditions by green algae. Transient spikes in moretane/hopane (M/H) ratios may record enhanced terrestrial weathering at the Frasnian-Famennian and Devonian–Carboniferous boundaries, triggered by coeval glacio-eustatic falls and increased inputs of soil organic matter. High M/H and pristane/phytane, in combination with low chemical index of alteration and K/Al, record a decrease in chemical weathering intensity during the Famennian that may have been due to contemporaneous climatic cooling, and a concurrent reduction in silt content may reflect stabilization of land surfaces by vascular plants and resulting reduced sediment yields. This study demonstrates the effectiveness of combining organic and inorganic geochemical proxies (including novel paleosalinity indices) for determination of environmental controls on the composition and productivity of plankton communities in paleomarine systems.

Stable carbon isotope evidence for the origin of C28 steranes in lacustrine source rocks from the Qikou Sag, Bohai Bay Basin, Eastern China

C27–C29 steranes are common constituents of crude oils and hydrocarbon source rocks and are usually dominated by either C27 or C29 compounds. In the current study, however, steranes dominated by C28 components were detected in eight lacustrine source rock samples in the first member of the Shahejie Formation in the Qikou Sag, Bohai Bay Basin of Eastern China. Ratios of C28/(C27 + C28 + C29) ααα 20R steranes in four samples can exceeded 50%. Furthermore, C27 triaromatic steroids, presumably originating from C28 steranes, were also observed at high levels, relative to C26 and C28 homologues. Stable carbon isotope compositions of a C28 ααα 20R sterane and C27 20R triaromatic steroid were found to be similar, with δ13C at −37‰ and −36‰ respectively, much lower than values for pristane (by ∼7‰) and total organic carbon (by ∼10‰). The abnormally low δ13C values of the steroids suggest that C28 ααα 20R sterane was biosynthesized by algae blooming in the water column during phases of overturn and mixing, such as in autumn, during which recycled CO2 and nutrients welling up from hypolimnion to the epilimnion are assimilated, contributing to a high algal productivity and low δ13C in algal organic matter.

Biomarker characteristics of hydrocarbon source rocks in saline lacustrine basin: a case study of Paleogene–Neogene strata in the Western Qaidam Basin, western China

During the Paleogene–Neogene, the Qaidam Basin was a saline lacustrine basin so the biomarkers of hydrocarbon source rocks exhibited unique characteristics under the salinization conditions. Saturated hydrocarbons extracted from a large number of source-rock samples were analyzed using gas chromatography and mass spectrometry. The results showed that n-alkanes in the source rocks were evenly distributed between even and odd carbon numbers, isoprenoid alkenes were predominantly phytanes, and ratios of pristane to phytane (Pr/Ph) were low, mostly in the range from 0.2 to 0.8. Terpanes typically showed high contents of C35 homohopane and gammacerane. Overall, the ratios of gammacerane to C30 hopane (gammacerane/C30 hopane) and C35–C34 homohopane (C35/C34 homohopane) exhibited a positive correlation. Differing concentrations of oleanane were detected. The relative content of C27 and C29 steranes in the hydrocarbon source rocks varied from 25 to 75%, and the relative content of C28 sterane in a considerable number of samples was higher than 30%. C27–C29 steranes generally showed an asymmetric V-shaped distribution, and the distribution of sterane/hopane and Pr/Ph ratios showed negative correlations. The salinity and reducibility indexes of the southern area of the Western Qaidam Basin were significantly higher than those of the northern area of the basin during the Oligocene–Miocene. Source rocks in the northern area were formed in a low-salinity and weakly reductive environment with type II2–III kerogen, whereas the hydrocarbon source rocks in the southern area formed in a high salinity and strongly reductive environment. The sedimentary water salinity and reducibility of the different areas were reduced in the following order: Hongliuquan, Yuejin, Shizigou, and Wunan–Lvcaotan. The best source rocks in this basin were developed in the Hongliuquan, Yuejin, and Shizigou areas with type II1–II2 kerogen. This study lays a foundation for further understanding the geochemical distribution of the hydrocarbon source rocks and crude oil in addition to the characteristics of the oil source in Paleogene and Neogene.

Tricyclic terpane geochemistry of source rocks from Northwestern and Central Niger Delta

ABSTRACTThis distribution of tricyclic terpanes in source rocks from the northwestern and central Niger Delta was used to evaluate their origin, depositional environment and thermal maturity. The rock samples were extracted using Soxhlet extraction method and the saturated hydrocarbon fraction was analysed for biomarkers using gas chromatography-mass spectrometry (GC-MS). The values of soluble organic matter (SOM) and total hydrocarbons for wells AW and OP source rock samples exceeded the minimum 500 ppm and 300 ppm, respectively with values indicating very good to excellent potential source rocks. The tricyclic terpane source parameters and the complementary distribution of hopanes, regular C27-C29 steranes, n-alkanes and acyclic isoprenoid hydrocarbons showed that samples from well AW consist of mixed marine/terrestrial organic matter while those from well OP consist of organic matter largely from terrestrial origin. The values of Pr/Ph ratio for source rock samples from wells AW and OP indicate deposition of the organic matter under suboxic conditions. Sterane and hopane biomarker maturity parameters indicated that the source rock samples from wells AW and OP are at onset of oil generation and main oil window, Most of the source rock samples from well AW are more thermally mature than those from well OP. The results of tricyclic terpane maturity parameters indicated low thermal maturity for the rock samples from both wells with samples from well AW more thermally mature than those from well OP.

Remediation of Petroleum-contaminated Soil Using Bulrush Straw Powder, Biochar and Nutrients.

The aim of this study was to determine the remediation efficiency of petroleum-contaminated soil from an oilfield using different types of remediation treatments under laboratory conditions. Compared with unamended soil as the control treatment (T1), soil samples were amended with bulrush straw powder (T2), with biochar alone (T3) and in combination with nutrients (nitrogen and phosphorus) (T4). The remediation experiment was carried out for 8 weeks. The extent of hydrocarbon degradation was monitored gravimetrically, and the residual oil fractions were analyzed by gas chromatography. The characteristics of the polluted soil (water-holding capacity and nutrients) were improved significantly by biochar addition (p < 0.05). The total microbial count increased significantly in the treatment containing biochar and added nutrients (t = 23.429, p = 0.002). The degradation of total petroleum hydrocarbons (TPH) and the main hydrocarbon fractions was higher in T3 and T4, especially in T4, than in T1 and T2. The intensities of the n-alkane fraction, C27-C29 steranes and C33-C35 homohopanes were efficiently decreased in T4 compared to the other treatments. According to the results, petroleum-contaminated soil can be remediated efficiently by adding biochar and nutrients simultaneously, and this combination of remediation was superior to that observed with added bulrush straw powder.

Changes in Concentration and Distribution of Biomarkers in Biodegraded Oils from Dongying Depression, China.

The alkane fraction of 11 biodegraded oils and five non-biodegraded oils from the Dongying Depression, Bohai Bay Basin, eastern China, were analyzed by gas chromatography-mass spectrometry to investigate the biomarker alteration caused by biodegradation. Results indicated that the concentration of 25-norhopanes was correlated with increased biodegradation. The oil samples showed an increase in the C31 and C32 hopane 22S/(22S + 22R), C29 sterane C2920S/(20S + 20R), and C29ββ/(ββ + αα) thermal maturity parameters in the heavily biodegraded oils. Oleanane was preferentially biodegraded compared with C3017α-hopane, which was preferentially biodegraded compared with C2917α, 21β-norhopane, C30 moretane, and C29 25-norhopane. The selective depletion of C27-C29 steranes followed the order ααα 20R > ααα 20S + αββ 20R > αββ 20S and C27 > C29 > C28, and the diasteranes and C20-C21 steranes were much more resistant to biodegradation than regular C27-C29 steranes. The steranes were generally preferentially biodegraded compared with the hopanes in this study.

Application of sulfur and carbon isotopes to oil–source rock correlation: A case study from the Tazhong area, Tarim Basin, China

Up until now, it has been assumed that oil in the Palaeozoic reservoirs of the Tazhong Uplift was derived from Upper Ordovician source rocks. Oils recently produced from the Middle and Lower Cambrian in wells ZS1 and ZS5 provide clues concerning the source rocks of the oils in the Tazhong Uplift, Tarim Basin, China. For this study, molecular composition, bulk and individual n-alkane δ13C and individual alkyl-dibenzothiophene δ34S values were determined for the potential source rocks and for oils from Cambrian and Ordovician reservoirs to determine the sources of the oils and to address whether δ13C and δ34S values can be used effectively for oil–source rock correlation purposes. The ZS1 and ZS5 Cambrian oils, and six other oils from Ordovician reservoirs, were not significantly altered by TSR. The ZS1 oils and most of the other oils, have a “V” shape in the distribution of C27–C29 steranes, bulk and individual n-alkane δ13C values predominantly between −31‰ to −35‰ VPDB, and bulk and individual alkyldibenzothiophene δ34S values between 15‰ to 23‰ VCDT. These characteristics are similar to those for some Cambrian source rocks with kerogen δ13C values between −34.1‰ and −35.3‰ and δ34S values between 10.4‰ and 21.6‰. The oil produced from the Lower Ordovician in well YM2 has similar features to the ZS1 Cambrian oils. These new lines of evidence indicate that most of the oils in the Tazhong Uplift, contrary to previous interpretations, were probably derived from the Cambrian source rocks, and not from the Upper Ordovician. Conversely, the δ13C and δ34S values of ZS1C Cambrian oils have been shown to shift to more positive values due to thermochemical sulfate reduction (TSR). Thus, δ13C and δ34S values can be used as effective tools to demonstrate oil–source rock correlation, but only because there has been little or no TSR in this part of the section.

Source, depositional environment and maturity levels of some crude oils in southwest Niger Delta, Nigeria

A suite of crude oil samples, that had not been previously characterized geochemically, was collected from two oil fields in the southwest Niger Delta Nigeria. The saturate biomarkers were used to evaluate geochemical characteristics such as depositional environments, sources of organic matter and extent of biodegradation using gas chromatography–flame ionization detector and gas chromatography–mass spectrometry. Distribution of n-alkanes (Pr/Ph, and isoprenoide/n-alkanes ratios), the abundance of hopanes, oleanane skeleton and C27–C29 steranes in the oils indicate that they were formed from mixed sources (marine and terrestrial kerogen) deposited in an oxic paleoenvironment with no particular maturity trend. These parameters also permit the source grouping of the oils into two families.

Geochemical studies of the Silurian oil reservoir in the Well Shun-9 prospect area, Tarim Basin, NW China

Commercial oil flow has been obtained from the sandstone reservoir of the Lower Silurian Kelpintag Formation in the Well Shun-9 prospect area. In the present studies, 10 Silurian oil and oil sand samples from six wells in the area were analyzed for their molecular and carbon isotopic compositions, oil alteration (biodegradation), oil-source rock correlation and oil reservoir filling direction. All the Silurian oils and oil sands are characterized by low Pr/Ph and C21/C23 tricyclic terpane (<1.0) ratios, “V”-pattern C27-C29 steranes distribution, low C28-sterane and triaromatic dinosterane abundances and light δ13C values, which can be correlated well with the carbonate source rock of the O3l Lianglitage Formation. Different oil biodegradation levels have also been confirmed for the different oils/oil sands intervals. With the S1k2 seal, oils and oil sands from the S1k1 interval of the Kelpintag Formation have only suffered light biodegradation as confirmed by the presence of “UCM” and absence of 25-norhopanes, whereas the S1k3-1 oil sands were heavily biodegraded (proved by the presence of 25-norhopanes) due to the lack of the S1k2 seal, which suggests a significant role of the S1k2 seal in the protection of the Silurian oil reservoir. Based on the Ts/(Ts+Tm) and 4-/1-MDBT ratios as reservoir filling tracers, a general oil filling direction from NW to SE has been also estimated for the Silurian oil reservoir in the Well Shun-9 prospect area.

Selective enrichment of steroid and triterpenoid hydrocarbons from crude oil using gel permeation chromatography for stable carbon isotope analysis

Gel permeation chromatography (GPC) using a high performance liquid chromatography (HPLC) system was studied for the separation and enrichment of steroid and hopanoid hydrocarbons from crude oil for stable carbon isotope analysis. A crude oil sample was pretreated using silica gel chromatography and 5A molecular sieve to remove polycyclic aromatic hydrocarbons and n-alkanes. The GPC behavior of both the pretreated saturated hydrocarbon fraction of the oil and standard steroid [5α(H), 14α(H), 17α(H) C27–C29 steranes], hopanoid [17α(H) C27 trisnorhopane, 17α(H), 21β(H) C29–C32 hopanes] and triterpenoid [18α(H)-oleanane, gammacerane] mixtures were examined. The results indicate that 17α(H), 21β(H) hopanes as well as steranes could be enriched efficiently using GPC and that they could be obtained without removing n-alkanes from the oil saturated hydrocarbon fraction. The GPC behavior of steroid and triterpenoid hydrocarbons was controlled by molecular size and shape.

04/02233 Development of kerosene fuel processing systemfor PEFC: Fukunaga, T. et al. Catalysis Today, 2003, 84, (3–4), 197–200

Organic compounds, extracted from snow and ice from the Dasuopu glacier, on the Qinghai-Tibetan Plateau in Southwest China at an altitude of 7000 m above sea level (asl), were identified through pre-enrichment, solvent extraction and subsequent GC–MS analysis. The average concentration of the extractable organic matter reached 45.4 μg/l. C15–C33 n-alkanes, C6–C18 n-alkanoic acids, C24–C31 n-alkan-2-ones and esters were derived from subtropical higher plants, as well as marine algae and bacteria. Organic compounds, indicative of petroleum residues such as automobile and diesel exhaust were also unexpectedly identified in the glacial snow. These included n-alkanes, alkylcyclohexanes, pristane, phytane, extended C19–C29 tricyclic terpanes, a C24 tetracyclic terpane, C27–C35 αβ hopanes, and C27–C29 steranes. Their presence indicates that the remote mountainous region and, to some extent, the middle-upper troposphere are polluted by human activities. Concentrations of some organic compounds, and total extractable organic matter, display a weak seasonal variation, postulated to be related to the location of middle-upper troposphere. The C17 n-alkane abundance and some molecular ratios exhibit a stronger seasonal variation, which may signify strong climatic change.

Morphological and ecological complexity in early eukaryotic ecosystems

Molecular phylogeny and biogeochemistry indicate that eukaryotes differentiated early in Earth history. Sequence comparisons of small-subunit ribosomal RNA genes suggest a deep evolutionary divergence of Eukarya and Archaea; C27-C29 steranes (derived from sterols synthesized by eukaryotes) and strong depletion of 13C (a biogeochemical signature of methanogenic Archaea) in 2,700 Myr old kerogens independently place a minimum age on this split. Steranes, large spheroidal microfossils, and rare macrofossils of possible eukaryotic origin occur in Palaeoproterozoic rocks. Until now, however, evidence for morphological and taxonomic diversification within the domain has generally been restricted to very late Mesoproterozoic and Neoproterozoic successions. Here we show that the cytoskeletal and ecological prerequisites for eukaryotic diversification were already established in eukaryotic microorganisms fossilized nearly 1,500 Myr ago in shales of the early Mesoproterozoic Roper Group in northern Australia.

Distribution of naphthalenes in crude oils from the Java Sea: Source and maturation effects

Amounts and distributions of C1-C3 naphthalenes and cadalene were determined by capillary gas chromatography in sixty crude oil samples from the Java Sea, southeast Asia and in a sample of Talang Akar (Oligocene) resinite supposed to be a major contributor of hydrocarbons to oils in that area. Maturity of the oils was assessed by the Methylphenanthrene Index (MPI-1). Source effects discovered by scatterplots were scrutinized by Principal Component Analysis (PCA).Based on empirical relationships with C27-C29 steranes (measured by gas chromatography-mass spectrometry), dimethylnaphthalenes in oils from the Ardjuna and Jatibarang (sub-)basins are mainly derived from terrestrial sources. Transition to a marine depositional environment in the Sunda basin, as indicated by a decrease in C29 sterane relative abundance from 70 to 30%, results in a decrease of total dimethylnaphthalene (DMN) concentrations from 20 to less than 3 mg/g oil. This is due, mainly, to a decrease in the concentration of the dominant 1,6-DMN. Thus, terrestrial Ardjuna or Jatibarang oils rich in 1,6-DMN (2–15 mg/g oil) are readily discriminated from marine Sunda oils (0.2–2 mg 1,6-DMN/g oil). Resinite of the Talang Akar type (1.4 mg 1,6-DMN/g total organic matter [TOM]) appears to be a significant contributor of 1,6-DMN to oils in the Ardjuna basin.Terrestrial affinities are inferred also for cadalene from concentration levels that are higher in terrestrial oils (1–3 mg/g oil) and Talang Akar resinite (6 mg/g TOM) than in the marine oils (0.1–1 mg/g oil). Ardjuna basin oils have the highest concentrations of cadalene, hence supporting resinite of the Talang Akar type as a possible source. However, 1,6-DMN and cadalene are likely to be derived from different terrestrial organic matter sources, because they load on different factors in PCA.Maturity levels of the oils in the range of 0.6–0.9% calculated vitrinite reflectance (Rcb), as inferred from the Trimethylnaphthalene Ratio (TNR-2), are in reasonably good agreement with MPI-1 measurements and geological constraints, e.g., highest maturities detected near the depocentre of the Ardjuna basin. The TNR-2 parameter hence proved useful for maturity assessment of Java Sea oils.