Phenanthrene biomarkers in the organic matter of Precambrian and Phanerozoic deposits and in the oils of the Siberian Platform

The composition and distribution of phenanthrenes (polyaromatic compounds) have been studied in chloroform extracts from dispersed organic matter (OM) of clayey, siliceous, carbonate, and terrigenous rocks of different ages and facies and from some oils of the Siberian Platform. Phenanthrenes have been analyzed by gas chromatography-mass spectrometry. High contents of 1,7,8-trimethylphenanthrene and 1,1,7,8-tetramethyl-1,2,3,4-tetrahydrophenanthrene are present in the OM of Vendian and Cambrian carbonate-shale deposits and in ancient oils of the Nepa-Botuobiya and Anabar anteclises. The OM of Permian continental deposits and oils of the Vilyui syneclise is dominated by 1-methyl-7-isopropylphenanthrene (retene). A triangular diagram for identification of the types of original OM of rocks and classification of genetically related oils has been constructed based on the assessment of phenanthrene biomarker distribution. Putative pathways of the formation of phenanthrene biomarkers are discussed.     

New monoaromatic steroids in organic matter of the apocatagenesis zone

According to the materials of geochemical study in the core of the ultradeep hole SV-27 of aromatic fractions of bitumoids of the Vilyui syneclise (East Siberia) by the method of chromatography–mass spectrometry, starting from the depth of >5000 m, four diastereomers of previously unknown hydrocarbons, which become predominant in the fraction at a depth of ～6500 m, were distinguished. Similar hydrocarbons were found in organic matter of Upper Paleozoic rocks of the Kharaulakh anticlinorium in the Verkhoyansk folded area. According to the intense molecular ion m/z 366 and the character of the basic fragmental ions (m/z 238, 309, and 323), the major structure of the compounds studied was determined as 17-desmethyl-23-methylmonoaromatic steroid C₂₇. The absence of such steroids in oil of the Vilyui syneclise shows that deep micro-oils did not participate in the formation of oil fringes of gas condensate deposits of the region.     

Natural bitumen fields in the northeast of the Siberian Platform (Russian Arctic sector)

In the northern and northeastern Siberian Platform, within the Anabar and Olenek zones, there are a number of hypergene bitumen accumulations (fields) and natural bitumen seeps, whose total resources are estimated at >5 bln tons. Bitumen fields are confined to a wide stratigraphic range from Precambrian to Mesozoic. A detailed geochemical study was performed for bitumens of the largest Olenek field, whose naphthides are localized mainly in Permian sandstones of deltaic and coast-marine genesis. Chromato-mass spectrometric analysis showed that normal alkanes are drastically reduced in the saturated fraction of the bitumens and most of terpanes are a homologous series of 25-norhopanes, which evidences the intense bacterial degradation of hydrocarbon pools. Identification of bicyclic sesquiterpenes, tetracyclic onocerane, and other biomarkers testifies that the organic matter of source rocks was rich in higher-plants remains. The concentrations of steranes are low, whereas those of earlier unknown 8-14-secosteranes are rather high. The set of geochemical data on the Permian bitumens of the Olenek field, including the isotopic characteristics of carbon (δ¹³C of ?25.8 to ?31.3‰), suggests that the coeval oil source rocks on the passive continental margin (at the place of the present-day Verkhoyansk fold belt) were the main source of hydrocarbons for the field. Assessment of oil and gas resources, including giant bitumen pools, and their exploration in the framework of “The fundamentals of Russian state policy in Arctic up to 2020” have become a top-priority problem. Petroleum refining products might be economically feasible raw materials in the eastern Russian Arctic sector to be supplied via the Northern Sea Route.     

Petroleum potential of Baikal deposits

We analyzed oils, gases, and bitumens of bottom sediments from natural shows on the southeastern shore of Lake Baikal, in the mouth of the Stvolovaya River near Capes Tolstyi and Gorevoi Utes. Based on a set of geological data, we have established that: (1) the lake oils underwent biodegradation to a variable degree: “Fresh” nondegraded paraffin oil floats up near Cape Gorevoi Utes; in the mouth of the Stvolovaya River and near Cape Tolstyi, aromatic-naphthene oil lacks n-alkanes, monomethyl alkanes, and acyclic isoprenoids; (2) Cenozoic oil originated from the organic matter of fresh-water basins with significant amounts of higher land plant remains, including angiosperm plants (oleanane), which suggests the lake or delta genesis of oil source formations of Cretaceous and younger ages. Judging from the carbon isotope composition (average δ¹³C = −43.84‰), methane from the bottom sediments near Cape Gorevoi Utes is catagenetic. The initial in-place resources in the Baikal sedimentary basins are estimated by the volumetric-statistical method at 500 mln tons of equivalent hydrocarbons.     

New homologous series of biomarker molecules from Vendian deposits of the Sayan-adjacent Biryusa area

We studied the organochemical distribution of saturated hydrocarbons in organic matter of mudstones of the Vendian Marna Formation in the Sayan-adjacent Biryusa area. The formation is composed of glacial, glacio-alluvial, and lacustrine deposits.In the fraction of saturated hydrocarbons in chloroform extracts (bitumoids), a homologous series of earlier unknown 2,7-dimethyl alkanes has been identified, with molecules having the even number of carbon atoms prevailing. The possible sources of such abundant biomarkers are considered.     

Distribution of monoalkylbenzenes C12H18–C27H48 in Vendian–Cambrian oils of the Siberian Platform

The peculiarities of the distribution of high-molecular normal alkylbenzenes in Vendian–Cambrian oils of the Siberian Platform were studied according to GC-MS data. A predominance of high-molecular homologues with the odd number of carbon atoms in the molecule has been established. Possible biochemical precursors and the probable mechanism of formation of “odd” monoalkylbenzenes are considered.     

Biomarkers and adamantanes in crude oils from Cenomanian deposits of northern West Siberia

Chromato-mass-spectrometric studies made it possible to identify a wide spectrum of hydrocarbon biomarkers in crude oils from Cenomanian pools of northern West Siberia (Russkoe, Pangodinskoe, Van-Eganskoe, Severo-Komsomol’skoe). The distribution pattern of the main hydrocarbon components (n-alkanes, acyclic isoprenanes, steranes, terpanes) shows that most of the oils underwent intense microbial oxidation. We have established high concentrations of 25-norhopanes typical of high-degree degradation; demethylated hopanes are also revealed in “alkane” crude oils. Among low-molecular chemofossils, bi- and tricyclic mono and sesquiterpanes have been recognized, whose precursors are usually biomolecules synthesized by plants. Unsaturated precursors of mono and sesquiterpanes might have been the starting material for thermocatalytical synthesis of framework adamantanoid structures, whose high concentrations have been found in alkane-free crude oils.