Russian Geology and Geophysics 52 (2011) 773780 www.elsevier.

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Hydrocarbons of the lanostane homologous series in the Phanerozoic organic matter and their probable biologic sources
T.M. Parfenova*
A.A. Trofimuk Institute of Petroleum Geology and Geophysics, Siberian Branch of the Russian Academy of Sciences, pr. Akademika Koptyuga 3, Novosibirsk, 630090, Russia Received 14 March 2011

Abstract The paper deals with the geochemistry of lanostane homologue molecules, the age and localization of organic matter (OM) enriched in lanostane biomarkers, and organisms synthesizing lanosterol and other lanostane compounds. Steranes of the OM bitumens of the Lower Cambrian Sinyaya Formation on the northern slope of the Aldan syneclise were studied by chromato-mass spectrometry. Lanostanes C30 have been found for the first time in the organic fossil of the Cambrian sedimentary basins, and the presence of norlanostanes C29 is assumed. The sedimentation and diagenesis conditions and the degree of maturity of OM containing lanostane and its derivates are considered. Lanostanes are proposed to use as biomarkers of the petroleum-generating rocks of the Sinyaya Formation for elucidating the source of naphthides in the eastern Siberian Platform. 2011, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.
Keywords: lanostanes; steranes; geochemistry; carbonate black shales; Sinyaya Formation; Cambrian; Siberian Platform

Introduction Lanosteroids are tetracyclic triterpenoids, whose molecule, in contrast to steroids, has additional methyl substituents at the fourth and fourteenth carbon atoms (Fig. 1, I, III). Compounds of lanostane structure (Fig. 1, I) are produced in live organisms. In 1953, Abe et al. (1993) were the first to put forward the hypothesis of the synthesis of oxidosqualene from squalene with the participation of oxygen in cell membranes. The cyclization of oxidosqualene results in lanosterol. The first experimental proof of lanosterol biosynthesis was reported in the 1960s (Abe et al., 1993). According to modern concepts, oxidosqualene successively produces protosteryl cation and protosterols (lanosterol and/or cycloartenol). The further oxidation leads to the loss of methyl substituents at C4 and C14 in the steroid core and the formation of molecules of sterane structure (Fig. 1, II) (Abe et al., 1993; Chen et al., 1989; Semenov and Kartsev, 2009; Summons et al., 2006). In the 1980s, the progress in biogeochemistry made it possible to synthesize lanostane for its subsequent identification in organic fossil (Petrov et al., 1986; Philp, 1985). * Corresponding author.
E-mail address: ParfenovaTM@ipgg.nsc.ru (T.M. Parfenova)

Saturated lanostane hydrocarbons (HCs) were first discovered in dispersed OM and oil of Eocene deposits in Central China (Chen et al., 1989). Lanostane homologue series C30C32 was identified in the OM of Oligocene deposits in North China (Bao and Li, 2001). Norlanostane (Fig. 1, III), lanostane, and methyl lanostane were found in the OM of Miocene deposits in Italy (Birgel and Peckmann, 2008; Peckmann et al., 2004). Oxygen-containing 19,28-bisnorlanostanes were revealed in the extract from the fossil plant trunk in deposits dated at 2 Ma in Japan (Murae et al., 1990; Naora et al., 1986). Lanostane sulfides were found in the oil from the Hubei province in China. These oils were generated from the OM of Paleocene sedimentary rocks (Peng et al., 1998). Thus, the available data were concerned only with lanosteroids in the OM of Cenozoic deposits in Eurasia (Table 1). In this paper we discuss the first findings of lanostanes in the Cambrian Sinyaya Formation in the Siberian Platform, the geochemistry of lanostane compounds in the ancient deposits, and their possible biologic sources. The geologo-geographic position of the study object The Lower Cambrian Sinyaya Formation was recognized by I.P. Atlasov in 1935. It is composed of alternating dark

1068-7971/$ - see front matter D 201 1, V . S. S o bolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved. doi:10.1016/j.rgg.2011.07+.003

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Fig. 1. Structural formulas: I, lanostanes; II, regular steranes; III, norlanostanes; IV, diasteranes; R, substituent in lanostane and sterane homologues.

gray and brown massive and fine-layered limestones. The formation is observed in the sections of the exposures along the Sinyaya, Batoma, and Lyutinga Rivers (tributaries of the Lena River). Its type section is localized on the Sinyaya River (left tributary of the Lena). The thickness of the Sinyaya deposits increases from 30 to 7580 m in passing from east to west. The formation is recognized in the Sinyaya-Botom area of the AnabarSinyaya facies region on the northern slope of the Aldan syneclise and is a facies analog of the Lower and Middle Cambrian Kuonamka, Inikan, Shumnaya, and Sekteken Formations. The rocks of the Sinyaya Formation are enriched in OM and are suggested to be petroleum-generating (Kashirtsev, 2003; Kontorovich, 1976; Savitskii et al., 1972; Zelenov, 1957).

Material and methods For study, we used a collection of OM-enriched limestones from the Lower Cambrian Sinyaya Formation, which were sampled from the Sinyaya River section in the southeastern Siberian Platform (Fig. 2). The rocks (31 samples) were treated with 10% HCl, and the obtained insoluble residue (IR) was used for analysis. The content of organic carbon (Corg) was determined by the rock combustion in oxygen on an AN-7529 express analyzer. The bitumen was extracted with chloroform from 50 g rock samples in a centrifuge at room temperature. After the extract cleaning with mercury from elemental sulfur, the bitumen was separated with petroleum ether into maltenes and asphaltenes.

Table 1. Lanostane compounds in Cenozoic organic matter Erathem Cenozoic System Quaternary Neogene Paleogene Sample Compounds Sampling localities Southern Nakatsugo and Ninio-Tog deposits, Tottori Prefecture, Japan Outcrop in the Pietralunga region, Italy Bohai Bay Basin, North China Biyang Basin, Central China References (Murae et al., 1990) (Peckmann et al., 2004) (Birgel et al., 2008) (Bao and Li, 2001) (Chen and Summons, 2001) (Chen et al., 1989) Lanostane sulfides Jianghan Basin, Hubei Province, China (Peng et al., 1998)

Fossil plant trunk Oxygen-cntaining 19,28-bisnorlanostanes DOM DOM DOM DOM, O O Norlanostane, lanostane, methyl lanostane Lanostane, methyl lanostane, ethyl lanostane Lanostane, methyl lanostane, ethyl lanostane

Note. DOM, dispersed organic matter; O, oil.

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Fig. 2. Sampling scheme. 1, boundaries of the Siberian Platform; 2, sampling localities.

Maltenes were separated into the fractions of saturated hydrocarbons, aromatic compounds, and benzene and alcoholbenzene resins. Saturated HCs were studied on an Agilent 5973N chromato-mass-spectrometric setup (gas chromatograph 6890 with a high-efficiency mass-selective detector and a computer registration system) in the TIC (total ionic current) scanning regime at 100320 C (23 samples). The chromatograph was equipped with a quartz capillary column (length 30 m, diameter 0.25 mm) filled with impregnated HP-5MS phase. The rate of the carrier gas (helium) was 1 ml/min. The HCs were identified by their retention time and its comparison with that for known compounds and with the published data.

Lanostanes in the organic matter of the Sinyaya Formation The studied rocks contain 1.123.2% IR (the average is 7.5%), 0.137.03% Corg, and 0.010.60% bitumens (the average is 0.14%). Saturated HCs amount to 1.111.7% (the average is 4.0%) in the bitumens. On the m/z 217 mass chromatograms we identified regular steranes ( and )) and diasteranes () C27C30 (Fig. 1, II, IV and Fig. 2, a). Analysis showed the following variations in the sterane contents: cholestanes C272537% (the average is 33%), methyl cholestanes C28813% (the average is 10%), and ethyl cholestanes C294962% (the

average is 56%) and C3014% (the average is 2%). Ethyl cholestanes are predominant independently of the Corg content in the rocks. The contents of steranes decrease in the series: C29, C27, C28, C30. This distribution of steranes is typical of the OM of the carbonaceous rocks of the LowerMiddle Cambrian Kuonamka Formation in the eastern Siberian Platform (Kashirtsev, 2003; Parfenova et al., 2004). In all samples, the ratios of cholestane and ethyl cholestane isomers (20S/(20S + 20R)) in the OM of the Sinyaya Formation are 0.6 and 0.5, respectively. The /( + ) values are 0.10.4 (the average is 0.2%). The m/z 259 mass chromatograms of diasteranes (22 samples) show two peaks (Fig. 3, b). Their spectra (Fig. 4) are identical and are the same as the spectrum of lanostane C30. This compound is recognized from the molecular mass (M) equal to 414, fragmentary ion [MCH3]+ = 399, and high intensity of ions259, 190, 231, and 274 (Chen et al., 1989; Peckmann et al., 2004; Peng et al., 1998; Petrov et al., 1986; Philp, 1985). Methyl and ethyl lanostanes are absent from the fractions of saturated HCs in the Sinyaya Formation bitumens. The m/z 245 mass chromatograms have four HC peaks (Fig. 5); M = 400, [MCH3]+ = 385, and the intensities of other fragmentary ions are 245, 176, 217, and 260 (Fig. 5). The molecular masses and masses of the main ions of the unknown HCs and lanostane C30 differ by 14 units. This indicates the absence of one methyl substituent from the ring A of the cyclic sterane structure. The spectra of peaks 1 and 3 (Fig. 5) totally coincide with the spectrum of one HC in the

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C27C29. For several samples, the heights of the peaks of lanostanes, norlanostanes, and steranes are nearly the same (Fig. 6). The study of steranes of the Sinyaya Formation showed the presence of lanostanes in the OM of much older Cambrian deposits (Fig. 7). The probable biologic sources of lanostane homologues Saturated lanostanes, lanostane sulfides, and oxygen-containing lanostanes are, most likely, produced from lanosterole and other lanostane biomolecules during diagenesis (Chen et al., 1989; Peckmann et al., 2004; Peng et al., 1998). Triterpenoids of the lanostane type are synthesized in the cell membranes of eukaryotes. Compounds of lanostane structure were extracted from fungi and yeast (Abe et al., 1993; Chen and Summons, 2001; Connolly and Hill, 2000; Feng et al., 2010; Handa et al., 2010; Kamalov et al., 2000; Rsecke and Knig, 1999, 2000; Semenov and Kartsev, 2009; Summons et al., 2006; Tkhaper et al., 1991; Zamuner et al., 2005; Zheng and Yang, 2008). Lanostane derivates were extracted from holothurias (Goad et al., 1985) and liver of sucking-pigs and rats (Abe et al., 1993). Biosynthesis of lanostane triterpenoids was detected in many animals (Chen and Summons, 2001; Semenov and Kartsev, 2009; Summons et al., 2006). According to some opinions (Abe et al., 1993; Summons et al., 2006), the intermediate product of sterane synthesis in plants is cycloartenol rather than lanostanol. At the same time, the research performed in 19602000 showed that lanostane compounds can be extracted from leaves, stems, bulbs, and pericarps of higher terrestrial plants (Alam et al., 2000; Camacho et al., 2001; Chen and Summons, 2001; Chen et al., 2001; Hui et al., 1971; Isaev et al., 2007; Kuroda et al., 2002; Kuroyanagi et al., 2000; Majumder et al., 2003; Mamedova

Fig. 3. The m/z 217 and 259 mass chromatograms of HCs of the Sinyaya Formation. a, Diasteranes (1) and regular steranes (C27, C28, C29), b, diasteranes (1) and lanostanes (2).

Miocene OM (Birgel and Peckmann, 2008). This HC has probably the norlanostane C29 structure. We recognized two lanostane and four norlanostane isomers in the studied bitumens. Analysis of the m/z 259 and 245 mass chromatograms showed that the intensity of the peaks of lanostanes C30 and C29 is usually lower than the intensity of the peaks of steranes

Fig. 4. The mass spectrum and structural formula of lanostane C30.

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Fig. 5. The m/z 245 mass chromatogram and mass spectra of HCs of the Sinyaya Formation.

et al., 2003a,b; Ori et al., 2003; Rukachaisirikul et al., 2000; Semenov and Kartsev, 2009; Uyeo et al., 1968; Vieira et al., 2004). The possibility of steroid biosynthesis in prokaryotes is discussed in scientific literature. Sallal et al. (1987) extracted

lanosterol from lipids of cyanobacterium cells. Bode et al. (2003) identified mixobacterial steroids. According to another hypothesis, methanotrophic bacteria might also be the biologic source of lanostanes (Birgel and Peckmann, 2008; Bouvier et al., 1976; Peckmann et al., 2004).

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OM? One of the probable reasons is that lanostane molecules in many organisms are the intermediate product of sterol biosynthesis, with a short life time. Therefore, they are scarce in live organisms in contrast to other biologic compounds.

The geochemistry of lanostanes Lithological, paleontological, and geochemical studies showed that the autochthonous organic matter of the carbonate rocks of the Sinyaya Formation accumulated and transformed in the sea basin with excess H2S in the sediments and, probably, bottom waters (Ivantsov et al., 2005; Kashirtsev, 2003; Kontorovich, 1976; Parfenova et al., 2010; Savitskii et al., 1972; Zelenov, 1957). In China, the lanostanes of the Biyang sedimentary basin were studied. Chen et al. (1989) established that the lanostanecontaining dolomite clays formed in a saline lake. Lanostanes C30C32 were identified in the calcareous-mudstone bitumen (CaCO3 = 44%) of the evaporate sediments in the Bohai Bay Basin. Sedimentation and diagenesis of the lacustrine sediments took place in reducing conditions (Bao and Li, 2001). Study of the oils from the Jianghan Basin in the Hubei Province revealed lanostane sulfides. The authors assume that these oils were generated by the evaporate deposits, which accumulated in the reducing conditions of saline lakes (Peng et al., 1998). The Pietralunga lanostanes were extracted from the lipids of marine limestones. Norlanostane, lanostane, and methyl lanostane have an abnormally light carbon isotope composition (13C varies from 70.0 to 92.2) (Birgel and Peckmann, 2008; Peckmann et al., 2004). The reason is that the OM of the carbonate sediments formed in unique environments where microbial mat might have been developed. The authors suppose that the microorganisms were fed by the sediment methane enriched in light carbon isotope. The OM has been preserved owing to the change of oxidizing conditions by reducing ones (Birgel and Peckmann, 2008; Peckmann et al., 2004). Oxygen-containing bisnorlanostanes formed in reducing conditions. Murae et al. (1990) assume a possible microbi-

Fig. 6. The m/z 217 mass chromatograms of steranes (1, 5, 14, 17-ethyl cholestane 20S; 2, 5, 14, 17-ethyl cholestane 20R; 3, 5, 14, 17-ethyl cholestane 20S; 4, 5, 14, 17-ethyl cholestane 20R), m/z 259 mass chromatograms of lanostanes (1), and m/z 245 mass chromatograms of norlanostanes (2) of the OM of the Sinyaya Formation.

Compounds of norlanostane structure were extracted from flowers (Dutta et al., 1983), lily bulbs (Kuroda et al., 2002), holothurias (Connolly and Hill, 2000), and sponges (Campagnuolo et al., 2001). The results of biochemical experiments suggest that in the modern biosphere, the synthesis of molecules with a lanostane framework occurs in eukaryotes and prokaryotes dwelling in water basins and land. The same organisms lived on the Earth millions years ago. So, why are lanostanes known to chemists and geologists since the 1980s seldom identified in the fossil

Fig. 7. Distribution of lanostanes in the Phanerozoic OM. Q, Quaternary system. Samples: 1, fossils; 2, rocks with dispersed OM; 3, oils; 4, rocks with dispersed OM of the Sinyaya Formation.

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ologic degradation of lanostanes at the early stage of the sediment diagenesis. Cenozoic lanosteroids were found in immature oils (Chen et al., 1989; Peng et al., 1998) and immature dispersed OM of rocks (Birgel and Peckmann, 2008; Chen et al., 1989; Murae et al., 1990; Peckmann et al., 2004; Peng et al., 1998). The low content of saturated HCs in the bitumens, the presence of unsaturated homohopene C31 and 28-bisnorhopene C31, and Ts/Tm = 0.10.4 evidence that the OM of the Cambrian Sinyaya Formation was also weakly transformed. The temperature of its transformation corresponds to the protoand mesocatagenesis boundary (Parfenova et al., 2010). All this suggests that lanostanes are better preserved in immature OM. However, the results of analysis of one sample from a depth of 3167 m from the Bohai Bay Basin (Bao and Li, 2001) showed the presence of lanostanes in mature OM (Corg = 1.05%). The HC content in the bitumen is 57%, and the vitrinite reflectance Rr is 0.70%. According to the Rock-Eval vt pyrolysis data, Tmax = 439 C, PI (productivity index) > 40%, and HI (hydrogen index) < 50 mg HC/g Corg. The oils and dispersed OM in the Proterozoic and Phanerozoic deposits in East Siberia contain saturated steranes and alkyl steranes and aromatic and alkyl-aromatic steroids (Kashirtsev, 2003; Kashirtsev and Kontorovich, 2006; Kontorovich, 2004; Kontorovich et al., 2005a,b; Parfenova et al., 2004; Timoshina, 2004). In addition to steranes C27C28, the earlier unknown structures of 8-14-secosteranes C27C28 have been recently identified in the bitumens from the Olenekskoe field in the northeastern Siberian Platform (Kashirtsev et al., 2010). Lanostanes have not been found in the fossil OM in Siberia yet. Additional studies of the HCs of the Kuonamka Formation showed the absence of lanostanes. Therefore, to determine the source of naphthides in the eastern Siberian Platform, we recommend using lanostanes as biomarkers of the oil-generating rocks of the Sinyaya Formation.

Presidium of the Russian Academy of Sciences, and Interdisciplinary Integration Project 36 from the Siberian Branch of the Russian Academy of Sciences.

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Conclusions The new results of the study of Cambrian steranes and the review of the literature on lanostane biosynthesis in the Earths modern organisms show that lanostanes can be identified not only in Cenozoic but also in Mesozoic, Paleozoic, and, probably, Proterozoic OM. The analysis of the geochemical features of the Sinyaya Formation lanostanes and the published data on lanostane derivates permit these chemofossils to be considered lithologic and paleogeographic indicators. It has been established that lanostanes accumulate in the carbonate or carbonate-containing sediments of lake and sea basins in reducing conditions during diagenesis. Discovery of these biologic markers in the naphthides on the northern slope of the Aldan anteclise will prove the petroleum potential of the Sinyaya Formation rocks. This work was supported by grants 10-05-00705 and NSh-6244.2010.5 from the Russian Foundation for Basic Research, basic-research programs 15 and ONZ-1 from the

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