Unusual biomarker maturation ratio changes through the oil window, a consequence of varied thermal history

Saturated and aromatic biomarker ratios continue to change systematically through the oil window and into the gas-condensate window to high vitrinite reflectances (R_o = 1.16%) in mature marine and lacustrine Mesozoic clastic samples from a South African basin. Two of the ratios reverse above R_o = 0.9%. These unusual maturation effects result from isolated periods of high rates of maturation increase. The basin cooled regionally after the break-up of Gondwana but high heating rates prevailed during the late Cretaceous-early Tertiary, as Africa moved across a hotspot, and again in the late Tertiary as a result of a possible hotspot and hydrothermal event.     

Comparison of source rock geochemistry of selected rocks from the Schei Point group and Ringnes formation, Sverdrup basin, arctic Canada

Organic-rich from the Schei Point group (middle to late Triassic in age) and the Ringnes formation (late Jurassic) from the Sverdrup basin of the Canadian arctic archipelago have been geochemically evaluated for source rock characterization. Most samples from the Schei Point group are organic-rich (> 2% TOC and are considered as immature to mature oil-prone source rocks [kerogen types I, I–II (IIA) and II (IIA)]. These kerogen types contain abundant AOM1, AOM2 and alginite (Tasmanales, Nostocopsis, Leiosphaeridia, acritarch and dinoflagellate) with variable amounts of vitrinite, inertinite and exinite. Samples from the Ringnes formation contain dominant vitrinite and inertinite with partially oxidized AOM2, alginite and exinite forming mostly immature to mature condensate- and gas-prone source rocks [kerogen type II–III (IIB), III and a few II (IIA)]. Schei Point samples contain higher bitumen extract, saturate hydrocarbons and saturate/ aromatic ratio than the Ringnes samples. Triterpane and sterane (dominant C₃₀) distribution patterns and stable carbon isotope of bitumen and kerogen suggest that the analyzed samples from the Schei Point group are at the onset of oil generation and contain a mixture of sapropelic (algal) and minor terrestrial humic organic matter. Sterane carbon number distributions in the Ringnes formation also suggest a mixed algal and terrestrial organic matter type. There are some variations in hopane carbon number distributions, but these are apparently a function of thermal maturity rather than significant genetic differences among samples. Pyrolysis-gas chromatography/mass spectrometry of the two samples with similar maturity shows that the Schei Point sample generates three times more pyrolyzate than the Ringnes sample. Both samples have a dominant aliphatic character, although the Ringnes sample contains phenol and an aromaticity that is higher than that of the Schei Point sample.     

Characterization of high molecular weight biomarkers in crude oils

High-temperature gas chromatography (HTGC) has enhanced our ability to characterize hydrocarbons extending to C₁₂₀ in crude oils. As a result, hydrocarbons in waxes (> C₂₀) have been observed to vary significantly between crude oils, even those presumed to originate from the same source. Prior to this development, microcrystalline waxes containing hydrocarbons above C₄₀ were not characterized on a molecular level due to the analytical limitations of conventional gas chromatography. Routine screenings of high pour-point crude oils by high-temperature gas chromatography has revealed that high molecular weight hydrocarbons (> C₄₀) are very common in most oils and may represent 2% of the crude oil. Precise structures, origins, and significance of these high molecular weight compounds remain elusive. As a preliminary step to expand our knowledge of these compounds their general molecular structures and formulas have been investigated in this study. Initial results suggest that the major high molecular weight compounds include a homologous series of n-alkanes, methylbranched alkanes, alkylcyclopentanes, alkylcyclohexanes, alkylbenzenes and alkylcycloalkanes.     

Root‐related rhodochrosite and concretionary siderite formation in oxygen‐deficient conditions induced by a ground‐water table rise

Sedimentological, mineralogical, stable carbon and oxygen isotope determinations and biomarker analyses were performed on siderite concretions occurring in terrestrial silts to understand their formation and to characterize the sedimentary and diagenetic conditions favouring their growth. High δ¹³C values (6·4‰ on average) indicate that siderite precipitated in an anoxic environment where bacterial methanogenesis operated. The development of anoxic conditions during shallow burial was induced by a change in sedimentary environment from flood plain to swamp, related to a rise of the ground‐water table. Large amounts of decaying plant debris led to efficient oxygen consumption within the pore‐water in the peat. Oxygen depletion, in combination with a decrease in sedimentation rate, promoted anoxic diagenetic conditions under the swamp and favoured abundant siderite precipitation. This shows how a change in sedimentary conditions can have a profound impact on the early‐diagenetic environment and carbonate authigenesis. The concretions contain numerous rhizoliths; they are cemented with calcium‐rhodochrosite, a feature which has not been reported before. The rhodochrosite cement has negative δ¹³C values (?16·5‰ on average) and precipitated in suboxic conditions due to microbial degradation of roots coupled to manganese reduction. The exceptional preservation of the epidermis/exodermis and xylem vessels of former root tissues indicates that the rhodochrosite formed shortly after the death of a root in water‐logged sediments. Rhodochrosite precipitated during the initial stages of concretionary growth in suboxic microenvironments within roots, while siderite cementation occurred simultaneously around them in anoxic conditions. These suboxic microenvironments developed because oxygen was transported from the overlying oxygenated soil into sediments saturated with anoxic water via roots acting as permeable conduits. This model explains how separate generations of carbonate cements having different mineralogy and isotopic compositions, which would conventionally be regarded as cements precipitated sequentially in different diagenetic zones during gradual burial, can form simultaneously in shallow burial settings where strong redox gradients exist around vertically oriented permeable root structures.     

Distribution of the organic matter in the channel-levees systems of the Congo mud-rich deep-sea fan (West Africa). Implication for deep offshore petroleum source rocks and global carbon cycle

The quantity and the source of organic matter preserved in the Recent turbiditic channel-levees systems around 4000 m-depth off the Congo River were determined using bulk geochemical approaches (Rock-Eval, elemental and isotopic analyses) as well as molecular and optical analyses on selected samples. These mud-rich sediments contain high amount of organic matter (3% Corg on average), the origin of which is a mixture of terrestrial higher-plant debris and deeply oxidized phytoplanktonic material. Although the relative contribution of continental source versus marine source of the organic matter cannot be precisely quantified, the continental fraction appears significant (at least 70–80%) especially for such depths and distances from the coast. The organic matter distribution appears very homogeneous at different scales, from the single turbiditic event to the entire levee, and changes in accumulation rates have a little impact on the quantity and quality of preserved organic matter.     

Biomarker-based paleo-record of environmental change for an eutrophic,tropical freshwater lake,Lake Valencia,Venezuela

The lipids in a sediment core from Lake Valencia, a hypereutrophic freshwater lake in Venezuela, are examined to understand environmental changes over the last ∼13,000 years. From the latest Pleistocene to the earliest Holocene, total organic carbon (TOC) substantially increased from 2.2 to 10%, while total organic carbon over total nitrogen (TOC/TN) decreased from as high as 34 to as low as 10. Correspondingly, the concentration of terrestrially derived triterpenoids markedly decreased, and the dominant n-alkane shifted from C₃₁ to C₂₃ or C₂₅. During the same period, algal biomarkers such as botryococcenes, dinosterol, isoarborinol, C₂₀ HBIs and 1,15C₃₂ keto-ol markedly increased in abundance. These changes suggested a greater contribution of algal organic matter at the onset of the Holocene, which was concurrent with increasing rainfall and the formation of a permanent lake (Lake Valencia) in the Aragua Valley, Venezuela. The age profile of Paq, a n-alkane based proxy, showed large oscillations (0.20–0.81), reflecting historical variations in source strength of submerged/floating vs. terrestrial/emergent OM inputs. An abrupt increase in tetrahymanol abundance at ∼7,260 cal years BP suggests the establishment of an oxic–anoxic boundary in the lake’s water column. After reaching its maximum abundance at ∼2,100 cal year BP, botryococcenes, a biomarker of Botryococcus braunii, gradually decreased to below the detection limit in the uppermost sediments, while different algal/microbial biomarkers such as diploptene, dinosterol and isoarborinol substantially increased. These different historical profiles of algal/microbial biomarkers reflect different responses of source organisms to environmental changes throughout this period. The δ¹³C determinations presented exceptionally enriched values for botryococcene isomers (−7.7 to −15.1‰), indicating the utilization of bicarbonate as carbon sources in an extremely productive ecosystem.     

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

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

New geochemical data from the Nigerian sector of the Chad basin: implications on hydrocarbon prospectivity

Organic geochemical studies have been carried out to assess the qualities of source rocks penetrated by four wells (Kemar-1, Murshe-1, Tuma-1 and Ziye-1) in the Nigerian sector of the Chad basin. The Chad basin is a large intracratonic basin in Central West Africa. Commercial hydrocarbon accumulations have been discovered in some sectors of the basin outside the Nigerian border in a structurally related contiguous basin. Fair to poor quality source rocks are inherent in the sequences penetrated by the studied wells. About 80% of all samples have their total organic carbon (TOC) contents more than 0.5 wt.%, the minimum limit for hydrocarbon generation. Juxtaposition of the hydrogen indices against the TOC and T_max indicates that the source rocks are entirely gas-prone. However, biomarker chromatograms and extract vs. TOC plots indicate the presence of oil shows in Ziye-1 well at a depth of 1210 m. Although generated hydrocarbons (wherever they have accumulated) would be overwhelmingly gaseous, gas is the energy of the future. The gas resources of this part of Nigeria's inland basins can be economically exploited through policies that will increase the tempo of gas-utilization projects and the construction of a national grid of gas pipelines with nodal points of input and output.     

Multivariate discriminant analysis distinguishes metal- from non metal-related biomarker responses in the clam Chamaelea gallina

Molecular biomarkers are among the most sensitive and earliest responses to pollutants. However, lack of detailed knowledge on variability of responses and their possible seasonal variation limit their use. In addition, the seasonality of biological processes modulates the response of organisms to pollutant stressors. Using multivariate statistics, we have studied the influence of environmental and biological factors on the response of a battery of molecular biomarkers in the clam Chamaelea gallina collected along the South-Spanish littoral. Multivariate discriminant analysis clearly distinguished biomarker response between clean and polluted areas, using heavy metals as indicator of pollution. Such differences disappeared when the dataset was normalised for metal content, thus indicating that pollution was the main significant cause of the changes observed between clean and polluted sites. In conclusion, this work shows that, when applying a complete biomarker panel, multivariate statistical tools can be used to discern pollutant- from non pollutant-related responses.     

Toxic contaminants and their biological effects in coastal waters of Xiamen,China. II. Biomarkers and embryo malformation rates as indicators of pollution stress in fish

Baseline information is presented on embryo malformation rate and biomarkers in fish as indicators of sub-lethal stress caused by pollution in coastal waters of Xiamen, PR China. Fish and eggs were sampled from several areas in Xiamen coastal waters (Xiamen Harbour, Maluan and Tongan Bays and East Channel), where varying levels of pollutant input have been documented. Comparative sampling was done at a "cleaner" reference site at Dongshan Island. Embryonic malformation rates, which indicate general water quality, varied with location and species of fish, and exceeded background levels for unpolluted waters (assumed approximately 5%) by up to eightfold at some sites. Generally, sites around Xiamen Harbour show signs of poor water quality having highest mean levels of embryo deformity (20-30%) and these decreased towards open waters (Tongan Bay, Eastern Channel) where abnormalities approached background levels. An indication that toxic contaminants may be having a localised effect in the region, particularly in the harbour was reinforced by the biomarker assays. However, activities of the biomarkers ethoxyresorufin O-deethylase (EROD) and glutathione S-transferase in fish livers indicate no clear pattern, and there is no evidence that fish from the four sampling areas have been more or less exposed to PAHs and other compounds that induce these biomarkers. Antioxidant biomarkers (glutathione peroxidase, catalase, superoxide dismutase, and reduced glutathione) suggest that exposure to xenobiotics appears to be lowest in Dongshan and Maluan and highest in the harbour and Tongan. Inhibition of acetylcholinesterase in fish muscle indicated possible effects by organophosphate and carbamate pesticides in Xiamen waters and these effects may be greatest in the area of the harbour.