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Marine and Petroleum Geology 24 (2007) 566–578 www.elsevier.com/locate/marpetgeo
Comparative study between Rock-Eval pyrolysis and biomarkers parameters: A case study of Ypresian source rocks in central-northern Tunisia
Adel ArfaouiÃ, Mabrouk Montacer, Fekri Kamoun, Adel Rigane
Laboratory of Organic Geochemistry, Department of Earth Sciences, Sciences Faculty, University of Sfax, GEOGLOB: 03/UR/10-02, P.O. Box 802, 3038 Sfax, Tunisia Received 9 December 2006; received in revised form 3 May 2007; accepted 6 May 2007
Abstract Sedimentary rock samples from the Ypresian Basin, in central-northern Tunisia, were analyzed by two well-proven organic geochemical methods: Rock-Eval (RE) pyrolysis and gas chromatography–mass spectrometry (GC–MS) analysis. These techniques were uses to obtain independent parameters on organic matter composition, its thermal maturity, and environment of deposition. This study reveals a close concordance between Rock-Eval pyrolysis data and polycyclic biomarkers parameters such as hopanes and steranes. RE pyrolysis in conjunction with GC–MS analysis show that the Ypresian Basin sediments contain a variable but notable organic-rich facies during the Ypresian and prove an unequivocal evidence for Type-II organic matter, which lies dominantly prior to the peak stage of the conventional oil window (end of diagenesis-beginning of catagenesis). The case study from the Ypresian Basin shows that these methods remain undoubtedly suitable for a good assessment of the petroleum potential of source rocks and rapid geochemical characterization of sedimentary organic matter. r 2007 Elsevier Ltd. All rights reserved.
Keywords: Organic matter; Rock-Eval pyrolysis; Liquid chromatography; GC–MS; Tunisia
1. Introduction Potential source rocks are described in terms of quantity, quality and level of thermal maturity of organic matter (Bordenave et al., 1993a). Recognizing the need to describe the thermal maturity of sedimentary organic matter accurately, organic geochemists developed various thermal maturity parameters. In this respect, as conventional geochemical method for assessing source rock maturity, ´ et al., 1977, 1985) is an Rock-Eval (RE) pyrolysis (Espitalie appropriate method for a good assessment of petroleum potential of source rocks and rapid geochemical characterization of sedimentary organic matter. On the other hand, organic matter contain source speciﬁc compounds, known as ‘‘biomarkers’’ which have
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quite distinctive chemical structures that are closely related to the biological precursors produced by plants, bacteria, and algae. Complex polycyclic biomarkers such as hopanes and steranes have received much attention in past few decades, mainly because of their usefulness as organic matter type and quality, depositional conditions (e.g. salinity, oxicity, anoxicity, etc.), assessment of maturity level, biodegradation extent and lithology. Such features have made biomarkers potentially applicable to oil-to-oil correlations (Waples and Machihara, 1991; Isaksen, 1993; Peters and Moldowan, 1993; Moldowan, 1994; Willsch and Radke, 1995; Kruge, 2000). In this respect, a special attention was turned to the Ypresian deposits of Tunisia, within the Metlaoui Group (Fig. 1), which shows a wide range of facies from North to South (Burollet, 1956). These sediments have been intensively studied because of the commercial interest in phosphates and hydrocarbons.
it is possible to distinguish the Es-Sfeı¨ a. Geographic location and lithostratigraphy The studied Ypresian outcrops are located in the northly part of central Tunisia and manifest in a carbonatic megasequence. Within the Metlaoui Formation. To the west of Kairouan. the extension of which is related to the paleomorphology (Fig. 1994. From east to west. Geological setting 2. the Ypresian Chaker and Es-Sfeı¨ a deposits exhibit a preferred alignment with the ‘‘North–South axis’’ which is a sub-meridian orogenic segment of central Tunisia (Fig.. 3) (Rigane. 1994): microcrystalline limestones with small pelagic and benthic foraminifera (Bou Dabbous source rock. 1990). of the Lower Eocene in central-northern Tunisia (west Kairouan) suggests a passage between open sea sedimentation (planktonic foraminiferous facies) and the barrier-type sedimentation (large benthic foraminiferous facies) (Fig. 2000). in central-northern Tunisia (Fig. its depositional environment and thermal maturity utilising a combination by confrontation of RE pyrolysis and gas chromatography–mass spectrometry (GC–MS) analysis. Paleogeographic map of Tunisia showing the distribution of Ypresian facies (modiﬁed from Zaı¨ r et al. 2.ARTICLE IN PRESS A.1. This passage takes place in a multi-kilometric transition zone which corresponds to an external platform (nummulitoclastic facies). 3). 2). bioclastic and nummulithoclastic limestones (transition facies. three different facies can be distinguished from bottom to top (Rigane et al. II) and massive crystalline limestones with large nummulites (El Garia reservoir. Chaker. 1) and is coevals to the main phosphatic facies (Chouabine Formation) that crop out extensively in western Tunisia (Burollet. The previous sedimentological and paleogeographical study by Ben Jemia-Fakhfakh (1991). In this area... Arfaoui et al. 1998). Paleogeography of the Lower Eocene in Tunisia The Ypresian Metlaoui Formation shows a wide facies variation from its northern to southern outcrops (Fig. 1991. I). III). the carbonatic megasequence is usually surrounded by Palaeocene clays (El Haria Formation) at the base and Lutetian-Priabonian marls (Souar Formation) at the top (Fig.. Rigane et al. / Marine and Petroleum Geology 24 (2007) 566–578 567 Fig. 2). 2) (Ben Jemia-Fakhfakh.. This paper interprets the geochemical pattern of organicrich carbonates of the Ypresian Basin located to the west Kairouan. The transition from the upper facies (III) to the overlying Souar Formation is characterized by a ﬁne clay marly sequence rich in oriented 2. and Serj Jebels which crop out 40 km to the west of Kairouan (central-northern Tunisia) (Fig. Gourmelen et al. 1956. 4) (Boukadi et al. 1991). The principal objective of this study is to attempt to understand the organic matter type.. Theses deposits are found in a progradation sequence which shows a regressive tendency from SW to NE. . 1. 2000).2. Ben Ferjani et al.
and Serj Jebels (after Boukadi et al. and (C) Serj Jebels (Ben Jemia-Fakhfakh. 2000). Relationship between Metlaoui Formation deposits at (A) Ousselat-Bou Dabbous.ARTICLE IN PRESS 568 A. 1991). Arfaoui et al. . Ypresian facies distribution in West of Kairouan and the location of Es-Sfeı¨ a. 2.. Chaker. Fig. (B) Es-Sfeı¨ a-Afaı¨ r. 3. / Marine and Petroleum Geology 24 (2007) 566–578 Fig.
at the three localities (Table 1). DE. expressed in mg HC/g rock. and Es-Sfeı¨ a. The pyrolysis of organic matter was performed over the temperature range of 300–600 1C with the rate of temperature rise of 25 1C/min. These analyses were undertaken mainly by the ‘‘Entreprise ´ s Pe ´ trolie ` re’’ (ETAP) using RockTunisienne d’Activite ´ et al. Arfaoui et al. The relative contents of particular compounds were calculated from peak areas. In the present work. Approximately 500–1000 g of sample was collected. the samples were ground into a ﬁne powder prior to analysis. The ratio of S2 to the TOC of the rock is the HI. have been sampled at outcrop in the Ypresian Basin. averaged 400–500 mg HC/g TOC at three localities indicating the low thermal maturity of Ypresian organic matter as indicated by the Tmax values (end of diagenesis-beginning of Fig. and Tmax (1C). The HI is determined as the yield of reduced products of pyrolysis (S2) relative to the total . (1977) Eval II instrument.4 ml/ min. Immediately after collection all samples were dried at 40 1C. USA). Pepper and Corvi.75 mg HC/g rock and average between 5 and 12. It is clear that the petroleum potential of the Ypresian sediments is remaining intact. Chaker. / Marine and Petroleum Geology 24 (2007) 566–578 569 organic carbon (mg HC/g TOC). Aliphatic hydrocarbons were analyzed by gas chromatography–mass spectrometry HP 6890-HP 5973 MSD combination (Agilent Technologies.62 to 19. 2000.) coated with 5% phenyl methyl siloxane.d.05 to 0. 191. 3. 4. The samples were injected in the splitless mode with an injector temperature of 280 1C. Materials of study All rocks. Given these data the sediments are immature. The GC–MS analysis was based on fragmentograms at m/z 99. The GC was used with a 30 m fused-silica column (0. thus the rocks were from high maturity levels. nummulites and surrounded by two areas of hard ground (Gourmelen et al.25 mm i. HI is a key source rock parameter used in quantitative modeling of the phase and volume of expelled hydrocarbons (e.1. This area gives the quantity of free hydrocarbons (oil and gas) contained in the rock. Rock-Eval analyses were performed on 20 selected samples. A temperature programme of 100–290 1C was employed with ramping at 4 1C/min.2. Fig.95 mg HC/g rock (Table 1). Techniques of study To obtain total organic carbon (TOC) content.1. according to the Espitalie procedure. the HI values (Table 1). and is a function of relative H/C in the organic matter. Lithostratigraphic cross-section of the Ypresian series in centralnorthern Tunisia (Gourmelen et al. The S2 values which rise from 0.g.ARTICLE IN PRESS A. expressed in milligram hydrocarbon per gram of rock (mg HC/g rock). Organic matter source and depositional environment 4. These low values may suggest that (i) signiﬁcant amounts of the hydrocarbons are not yet produced from source rocks due to the low thermal maturity of the organic matter in all studied areas or (ii) the produced hydrocarbons had already migrated away from source rocks. Then. hydrogen index (HI. mg HC/g TOC).. Materials and methods 3. They concern the Jebels of Serj. Rock-Eval pyrolysis data S1 is the area of peak P1 which corresponds to thermovaporized-free hydrocarbon compounds present in the rock which volatilize at temperatures below 300 1C. 2000).1. The geographic locations of the collected samples are shown in Fig. S2 is the area of peak P2 which corresponds to the hydrocarbon compounds originating from kerogen cracking (pyrolysis of the kerogen up to 530 1C). In this present study. and 217.1. 1995b) and the classiﬁcation of kerogen type. Samples were run in the electron impact mode at 70 eV with a 2. 4. Results and discussion 4. S1 values are extremely low ranging from 0.9 s scan time over a 50–550 amu range resolution. 4). This area (S2).. which are predominantly limestones. gives the residual petroleum potential of the rock. Wilmington. S2 corresponds in addition to the thermal degradation products of the involatile but extractable asphaltenes and resins. Helium was used as the carrier gas at a ﬂow rate of 1. 3. 3.
which is of Type-II. Chaker.05 0.40 3.20 0. and Serj Jebels Sampling location Sample TOC (wt%) mg HC/g rock S1 J. 1984). Organic matter type discrimination diagram of the studied sedimentary rock samples from the Ypresian Basin based on crossplot of Tmax and hydrogen index.41 00.62 05.54 0. The average of TOC content in Serj is 1. and the production index (IP ¼ S1/S1+S2) (Table 1). In contrast.77 04.09 0.04 1. It reveals that the sediments in the Ypresian Basin display a clear ﬂuctuation of TOC values (Fig.28 0. It is known that the low abundance of TOC suggests that a relative oxicity of the depositional environment affects the amount and elemental composition of the stored organic matter (Tissot and Welte.06 0.26 wt%.23 1.97 0. particularly Es-Sfeı¨ a area.54 0.26 0. In contrast several samples containing visible carbonaceous matter and showing high TOC values which reached 3.14 1. Arfaoui et al.35 1.04 0. 5).14 0. and Es-Sfeı¨ a 2. In this respect.27 0. Chaker 1.42 0.6 HI PI Tmax (1C) J.97 05. n-Alkanes (m/z 99) distribution In this present study.28 05.47 06.68 1.51 05.03 0.31 0.04 0.6 463 482 432 448 348 388 366 385 414 175 261 159 430 261 577 861 389.42 0.04 0.72 0. Serj TOC: total organic carbon (%).48 1. it seems that no external contribution of migrated hydrocarbons was added to the Ypresian organicrich facies as indicated by the low S1 values.1.57 0.05 0. 6(a)–(c)). PI: production index (S1/(S1+S2).81 03. m/z 99 fragmentograms indicate that the hydrocarbons present in the sediments from the Fig. 4.56 19.07 0. catagenesis) (Fig.42 1.04 0.75 09.71 1. Some samples are lean in organic matter (o1wt%).58 17. our results.1 442 439 439 430 431 427 427 433.73 0.40 0.37 3.05 0.37 544 222 607 532 598 500.5 433 433 436 434 435 436 438 436 435.05 0.07 0.04 0.12 1.31 0.81 08.14 wt% (Table 1).04 0. .99 14.18 0.62 0.51 05.78 0. 5.05 0. Furthermore.1 0. Es-Sfeı¨ a JE-01 JE-03 JE-05 JE-08 JE-11 Average JC-01 JC-04 JC-08 JC-12 JC-16 JC-21 JC-24 JC-28 Average KZ-01 KZ-03 KZ-06 KZ-09 KZ-11 KZ-14 KZ-16 Average 2.95 0.09 0.70 01.20 0.05 431 – 431 430 430 430.21 12 04.41 06. and reﬂects a uniform source of organic matter.05 0.42 wt%.15 1.26 S2 16.07 0. HI: hydrogen index (S2/TOC Â 100). display a relative high TOC contents.2.ARTICLE IN PRESS 570 A. Chaker J.04 0.34 00. Tmax: maximum pyrolysis temperature.26 0.20 14.05 0.15 00. / Marine and Petroleum Geology 24 (2007) 566–578 Table 1 Result of Rock-Eval analyses of representative samples from Es-Sfeı¨ a. the less oxic environment promoted better organic preservation in the depositional environment.68 1.12 0.39 1.47 05.05 0.54 2.05 0.09 2.16 0. for all studied samples.44 0.82 1.71 wt% in Es-Sfeı¨ a Jebel (Table 1).57 1.03 0. This result due to episodes that are generally more conductive for preservation/accumulation of high amount of organic matter in central-northern Tunisia.
This is evident from the unimodal hydrocarbon distribution with a major mode centered at n-C18 or n-C21. Lower part I: Predominant organic matter rich gray limestones. Generally speaking. following compounds have been identiﬁed: C27-cholestane. Upper part II: Gray limestone package. In this work. respectively (Fig. (c) Stratigraphic log of the Ypresian sequence at Jebel Es-Sfeı¨ a with location of the samples of organic matter rich rocks. If the signatures of algal-marine Type-II organic matter are clearly present with predominance of short-chain n-alkanes (n-C20–n-C26) that of continental higher plants with predominance of longchain odd carbon numbered are undetectable. On the other hand. 8. Ypresian Basin have a carbon numbers ranging from 13 to 28 (Fig. The labeled peaks are summarized in Table 2. followed by ergostane (C28) comprising 10–34%. .ARTICLE IN PRESS A. (a) Stratigraphic log of the Ypresian sequence at Jebel Serj with location of the samples of organic matter rich rocks. (b) Stratigraphic log of the Ypresian sequence at Jebel Chaker with location of the samples of organic matter rich rocks. Middle part II: Interbedded gray marl and limestone. 6. However. Cholestane (C27) was consistently the most abundant pseudohomologue comprising 43–63% of the total C27–C29 regular steranes). Upper part III: Gray limestone package. Upper part II: Predominant gray to dark organic matter limestones. 7(a)–(c)). Arfaoui et al. Tissot et al. 4. C28-ergostane. Lower part I: Predominant gray to dark organic matter rich limestones. shows an unequivocal evidence of the low thermal maturity of the Ypresian phytoplanctonic product in west of Kairouan. 1999). Lower part I: Interbedded gray marl and limestone. (1977) and Belayouni (1983) suggest that such geochemical ﬁngerprint was found in carbonatic or phosphatic facies when the organic matter was generated dominantly prior to the peak stage of the conventional oil window.1. the n-C15–n-C20 alkane series is related to organic source of microorganisms and/or algae (Peters and Moldowan. It is known that the lower molecular weight n-alkanes (oC21) are derived from algae and bacteria (Wakeham. 1990) whilst the high molecular weight homologues (4C22) mainly originate from higher plants wax (Huang et al. and stigmastane (C29) comprising 18–27% (Table 4). 1985). 7(a)–(c)). Steranes (m/z 217) distribution The mass chromatograms obtained for representative samples are shown in Fig. C29-stigmastane and propylcholestanes with their 20S and 20R epimers (Philp.3. 1993). / Marine and Petroleum Geology 24 (2007) 566–578 571 Fig.. the n-alkanes distribution with relative high abundance of isoprenoids (pristanes and phytane) relative to n-C17 and n-C18.
C27–C28–C29. A predominance of C29 steranes is related to a strong terrestrial contribution. Seeing that C27 steranes and C29 steranes are related. Pr: pristane. the sterane distributions can be used as effective source facies discriminators to group oils in a region on the basis of genetic relationships. (b) Mass chromatograms (m/z 99) of the aliphatic hydrocarbon fractions for some representative samples from Chaker area. Pr: pristane.72 to 2. On the other hand. Pr: pristane. respectively (Peters and Moldowan. C27/C29 sterane ratios rise from 1. As known. whereas a predominance of C27 and C28 indicate a predominance of marine phytoplankton and lacustrine algae. / Marine and Petroleum Geology 24 (2007) 566–578 Fig. Ph: phytane. such data conﬁrms . 1993). 1984.77 (Table 4).ARTICLE IN PRESS 572 A. indicating that these sediments extracts were derived from a similar marine source. 7. 1985). Homologous distributions of steranes. (c) Mass chromatograms (m/z 99) of the aliphatic hydrocarbon fractions for some representative samples from Es-Sfeı¨ a area. to marine and terrestrial sources (Tissot and Welte. (a) Mass chromatograms (m/z 99) of the aliphatic hydrocarbon fractions for some representative samples from Serj area. are often expressed in ternary plots to show similarity or dissimilarity in source facies among the oils of interest (Fig. Ph: phytane. Arfaoui et al. Waples. In this present study. the ternary plot shows that the outcrop samples are indistinguishable by sterane distributions. 9). respectively. Ph: phytane.
However. also. carbonate source rocks. Chaker. Chaker (JC-28)..ARTICLE IN PRESS A. However. related to the microscopic algae which are able to secrete major C27. whilst high ratios are generally found in oils derived from clastic sediments. Generally. of all outcrop sample extracts.1. and Es-Sfeı¨ a (JE-01) Jebels. 1993). claypoor. This assumption has been conﬁrmed by RE pyrolysis data. 1982). and C31 hydrocarbons (Gelpi et al. Mass chromatograms showing the distribution of steranes (m/z 217) and pentacyclic triterpanes (m/z 191) of some representative samples from Serj (KZ-16). 8. 1968.88. tricyclic terpanes have been found in all the extracts (Fig. Table 4 shows that the diasteranes index. In this present study. 4. . 1970). rise from 0. and Es-Sfeı¨ a areas have relatively high C23-tricyclic terpane. 8 and Table 3). Arfaoui et al. outcrop samples from Serj. Aquino Neto et al. Hopanes (m/z 191) distribution Tricyclic terpanes widely found in petroleums and source rock extracts have a possible origin in prokaryotic cell membranes (Ourisson et al.4. / Marine and Petroleum Geology 24 (2007) 566–578 573 Fig. where clay minerals may act as catalysts in their formation from other steranes (Peters and Moldowan. 1993). Diasterane/sterane ratios are commonly used to distinguish carbonate from clay-rich source rocks.49 to 0. The occurrence of C29 steranes may be. low diasterane/sterane ratios are associated with anoxic. (1983) systematically investigated the distributions of tricyclic terpanes in oils and source rocks formed in a variety of depositional environments and showed that the C23 member is often the dominant homologue in crude oils of a marine source while the C19 and C20 members are more abundant in terrestrial oils (Peters and Moldowan. diasterane/sterane ratios are also generally low in immature/early mature sediment extracts. The occurrence of diasteranes in relative low abundance in Ypresian organic matter implies generation of these oils from source rocks lean in clay minerals. C29.. the marine origin of Ypresian organic matter.
26 (Table 5). It is known that the proportion of C24 tetracyclic terpane relative to triterpanes may also be facies dependent. Peters and Moldowan.14b(H).14b(H). In outcrop samples the C23/C24 ratios rise from 2 to 3.21a(H)-moretanes to their corresponding 17a(H).14a(H).17a(H)-24-Ethyldiacholestane (20S) 5a(H).17b(H)-24-Methyldiacholestane (20R) 5a(H).17a(H)-Cholestane (20S) 5a(H).14a(H).17a(H)-24-Methylcholestane (20R) 5a(H). 1982.14a(H).17b(H)-Cholestane (20R)+ 13b(H)..14b(H).17b(H)-24-Methylcholestane (20S) 5a(H). Ternary plot showing the distribution of regular steranes (C27–C28–C29) of studied samples.17b(H)-24-Ethylcholestane (20R) 5a(H)..17b(H)-24-Ethyldiacholestane (20S) 5a(H).17b(H)-24-Propylcholestane (20R) 5a(H).17b(H)-24-Ethylcholestane (20S) 5a(H). Generally. Chaker.17a(H)-24-Methyldiacholestane (20S) 24R/S isomers (?) 13b(H). or in sediments with low clastic content (Peters and Moldowan. 1988). 1993).17a(H)-24-Ethylcholestane (20S) 5a(H).14b(H). 8 and Table 3).17a(H)-Diacholestane (20S) 13b(H).17a(H)-24-Ethylcholestane (20R) 5a(H).17b(H)-Diacholestane (20S) 13a(H).14a(H).17a(H)-24-Methyldiacholestane (20S) 24R/S isomers (?) 13b(H).20 (Table 5).14b(H).17b(H)-Diacholestane (20R) 13b(H). Connan et al.17a(H)-Cholestane (20R) 13b(H).17b(H)-24-Ethyldiacholestane (20R) 5a(H).14a(H).17b(H)-24-Propylcholestane (20S) 5a(H). The ratios of 17b(H). 9.17b(H)-Methylpregnane 13b(H). Arfaoui et al. Furthermore. The C24 tetracyclic terpane is also present in Ypresian organic matter (Fig.14a(H).7b(H)-Pregnane Diahomopregnane 5a(H).14a(H). with relatively high concentrations in source rocks and oils with terrigenous input.ARTICLE IN PRESS 574 A. . 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 288 288 302 302 372 372 372 372 386 386 386 386 372 372 400 372 386 372 400 400 386 400 386 386 386 400 400 400 400 414 414 414 414 Diapregnane 5a(H). Thus.14b(H).14b(H). 1993).21b(H)-hopane (ba-moretane/ab-hopane) rise from 0.17a(H)-24-Propylcholestane (20S) 5a(H).17a(H)-24-Propylcholestane (20R) Fig.17a(H)-24-Methyldiacholestane (20S) 5a(H).14b(H). / Marine and Petroleum Geology 24 (2007) 566–578 Table 2 Steranes (m/z 217) identiﬁcation in chromatograms of Fig. these relative low ratios reﬂect an open sea with absence of terrestrial contribution of organic matter.17a(H)-24-Ethyldiacholestane (20R) 13a(H). 8 Peak number Molecular formula C21H36 C21H36 C22H38 C22H38 C27H48 C27H48 C27H48 C27H48 C28H50 C28H50 C28H50 C28H50 C27H48 C27H48 C29H52 C27H48 C28H50 C27H48 C29H52 C29H52 C28H50 C29H52 C28H50 C28H50 C28H50 C29H52 C29H52 C29H52 C29H52 C30H54 C30H54 C30H54 C30H54 Weight Compound 1 2 3 4 5 6 7 8 9 10 11. the relatively low abundance of the C24 tetracyclic in Serj. 1986.14a(H).17a(H)-24-Methyldiacholestane (20S) 24R/S isomers (?) 13b(H).14b(H).17b(H)-24-Methylcholestane (20R) 5a(H). and Es-Sfeı¨ a outcrop samples suggests a marine ﬁngerprint of the Ypresian organic matter (Aquino Neto et al. Such result reﬂects the occurrence of the C23-tricyclic terpane in high concentrations compared to the C24-tetracyclic terpane. Connan (1993) interprets the distribution of terpanes with predominance of hopane series (ab-hopanes and ba-moretane) as a reﬂection of microbial activity.17b(H)-Cholestane (20S) 13a(H).17a(H)-24-Methyldiacholestane (20S) 13a(H).17a(H)-Diacholestane (20R) 13a(H).13 to 0. Thus. these ratios increase in organic matter deposited in depositional environment with high salinity (Rullkotter and Marzi.14b(H).
4.8 in the immature stage to values of less than 0.21a(H)-Moretane 17a(H). all the Tmax values suggest that the . As the maturity increases..21b(H)-28. have much lower Tmax values of 430–431 1C (Table 1). the aa form. 4. this ratio decreases from about 0. Espitalie ´ et al.5%. 1993. 1988. Only the R conﬁguration at C-20 (called 20R) is found in steroid precursors in living organisms. Sterane maturity parameters One major application of steranes in organic geochemistry is the maturity determination based on the thermal effects on the stereochemical complexity of their basic skeletons.30Trisnorhopane (Tm) Tricyclic triterpane (22R) Tricyclic triterpane (22S) 17a(H). respectively. and Chaker in the Ypresian Basin are listed in Table 4. Ramon and Dzou.26 to 0. whereas samples from the eastern part (particularly J. 1987).1. Samples from the western part of the Ypresian Basin (J.29.14a(H).2.43. Arfaoui et al. the ratios [20S/(20S+20R)] for C29 steranes are the only epimer ratios that could be measured with conﬁdence (Table 4) (Peters and Moldowan. 1993).32 to 0. Es-Sfeı¨ a).21b(H)-hopane (ba-moretane/ab-hopane) decrease with increasing thermal maturity.2. This was found to vary with the thermal evolution formerly undergone by the rock sample ´ .30Bisnorhopane 17a(H). This ratio is somewhat slower to reach equilibrium than the 20S/(20S+20R) ratio.31. Thermal evolution of organic matter 4.ARTICLE IN PRESS A. 1975.29. 8 Peak number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 Molecular formula C19H34 C20H36 C21H38 C22H40 C23H42 C24H44 C25H46 C24H42 C26H48 C26H48 C28H52 C28H52 C29H52 C29H52 C27H46 C27H46 C27H46 C30H56 C30H56 C28H48 C29H50 C29H50 C29H50 C30H52 C29H50 C30H52 C30H52 C30H52 C31H54 C31H54 C30H52 Weight Compound 575 organic matter has reached a relative low thermal maturity in the Ypresian Basin corresponds to the end of diagenesis and beginning of catagenesis. Usually.30-trisnorhopane (called Tm) and 18a(H)-22.30-trisnorhopane (called Ts).2. Tm shows lower relative stability than Ts during maturation 262 276 290 304 318 332 346 330 360 360 388 388 402 402 370 370 370 416 416 384 398 398 398 412 398 400 400 412 426 426 412 Tricyclic diterpane Tricyclic diterpane Tricyclic terpane Tricyclic diterpane Tricyclic diterpane Tricyclic diterpane Tricyclic diterpane Tetracyclic terpane Tricyclic triterpane (22R) Tricyclic triterpane (22S) Tricyclic triterpane (22R) Tricyclic triterpane (22S) Tricyclic triterpane (22R) Tricyclic triterpane (22S) 18a(H)-22. 1999).29. rise from 0.13–0.21a(H)-30Normoretane 18a(H)-Oleanane 17a(H). Samples show this ratio in the range of 0.05 (Rullkotter and Marzi. 1993). which reached 442 1C. In this present study.30Trisnorneohopane (Ts) Pentacyclic terpane 17a(H)-22.17b(H) C29 sterane and 5a(H). converts gradually into a mixture of aa and bb. Peters and Moldowan. are often applied to assess the maturity level of sediments (Rullkotter and Marzi.21b(H)-Hopane 17b(H). The abundance of Ts relative to Tm is inﬂuenced by both maturity and source rock mineralogy (catalytic versus inert minerals. Peters and Moldowan.14b(H). Maximum pyrolysis temperature: Tmax The temperature for which the S2 peak is maximum (Tmax) is a useful indicator of the thermal evolution/ maturity of a source rock. indicating the early mature stage for these biomarkers (equivalent to Ro ¼ 0. Philp and Fan.2. two C27 pentacyclic tristerpanes. / Marine and Petroleum Geology 24 (2007) 566–578 Table 3 Pentacyclic triterpanes (m/z 191) identiﬁcation in chromatograms of Fig. The 17a(H)-22. 1988. These relative low values suggesting that these sediments extracts were generated dominantly prior to the peak stage of the conventional oil window (Peters and Moldowan. a general assessment of thermal maturity using Tmax values shows a small difference between the four areas.21b(H)-25Norhopane 17a(H).2. which is produced biologically. 1993).21b(H)-Homohopane (22R) Gammacerane 4.21b(H)-30Norhopane 18a(H)-Norneohopane (29Ts) Diahopane 17b(H). 1993). In this work. Thus.50 and from 0. Es-Sfeı¨ a. Generally. Peters and Moldowan. Serj) have the higher Tmax values. the ratios of 20S/(20S+20R) for aaa C29 steranes and bb/(aa+bb) for 5a-C29 steranes in the Ypresian outcrop samples (Table 5). 5). Another maturity parameter derived from C29 regular steranes is the proportion of 5a(H).15 in mature stage and a minimum of 0. under analysis (Tissot and Espitalie 1977). and it gradually converts during burial maturation to a mixture of the R and S sterane conﬁgurations.3. 1993) as indicated by Tmax values and Tmax/HI diagram (Fig.17a(H) C29 sterane forms (isomerization at C14 and C17) expressed as the ratio abb/ (abb+aaa) sterane. thus making it effective at higher levels of maturity (Peters and Moldowan. The ratios of ba-moretane/ab-hopane of the samples from Serj.21b(H)-Homohopane (22S) 17a(H).21a(H)-moretanes to their corresponding 17a(H). Hopane maturity parameters The ratio of 17b(H).29.
34 0.55 0.40 0.6 (0. Es-Sfeı¨ a JE-01 JE-05 JE-11 Average a b 2.40 0.5–0.19 0. c 24-Ethyl-13b(H)-17a(H)-Diacholestanes (20R+20S)/[24-ethyl-14a(H)-17a(H)-Cholestanes (20R+20S) +24-ethyl-14b(H)-17b(H)-cholestanes (20R+20S)].72 0.29. Tm/Ts ¼ 1 was considered as a limit between immature (Ts/Tmo1).49 0.16 0.30-trisnor-neohopane (Ts)/17a(H)-22.40 0.91 2 1.58 0. Hostettler et al.23 0. the 22S/(22S+22R) ratio of the C31 17a-hopanes in the Ypresian samples extracts range from 0.76 1.54 0.41 0.6% shows 22S/(22S+22R) ratios in the range 0. The stereochemistry at the C22 chiral center in the side chain for homohopanes (extended hopanes) forms the basis for a second maturity measurement.88 0.17b(H)+5a(H).55 0.17 0. (Hostettler et al.49 0.39 0.96 2.50 0.37 0. 1993. 1999)..61 0.29.58 0. / Marine and Petroleum Geology 24 (2007) 566–578 Table 4 Sterane parameters (m/z 217) of studied samples Sample Sterane (%)a C27 J.13 0.14a(H).43 0.g. carbonates Philp and Fan.50 0.42 0.43 0.72 2.55 0.29.60 0. 1983a.56 0.35 0.50 to 0.89 0.30trisnorhopane (Tm) vary in the range 0.. The similarity of these values for all the outcrop samples also suggested that the organic matter in Ypresian Basin has reached a good stage of thermal maturity.14b(H).00 2.17a(H)-20R-Steranes).14b(H).30-Trisnorneohopane/17a(H)-22. Kvenvolden et al.21a(H)-Moretane /17a.18 2.14a(H).37 0. 1985).63 0.54 (Peters and Moldowan.20 2.62 ¼ equilibrium) during maturation. d 18a(H)-22.77 2.09 1.35 0.88 (Table 5).64 0.48 0.17 0.40 0.14a(H).18 0.32 0. In this present study. and mature (Ts/Tm41) organic matter (Seifert and Moldoman. Thus.86 0.42 2.or C32-homohopanes are used for calculations of the 22S/(22S+22R) ratio.37 0.60 0.40 0. e 5a(H).21 0. 1978.30-trisnorhopane.20 0.73 0.84 1.65 0.56 0. Arfaoui et al. 1994.55 0..85 0.30 2.17b(H)/[5a(H).34 0.33 2. The 22S/(22S+22R) ratio rises from 0 to about 0.38 0. Therefore. values of the ratio 18a(H)-22.21b(H)-hopane for C30-triterpanes. The biologically produced precursors for hopanes have the R conﬁguration at the C22 position (called 22R).57–0.57 0. C27/C29 (5a(H).24 0. 1995).. Serj KZ-06 KZ-11 KZ-16 Average J. In Serj.26 0. Es-Sfeı¨ a. .37 0.42 0.21b-homohopane.17a(H)] for C29-Steranes.48 2.31 0. d 20S/(20S+20R) for C29-5a(H). Table 5 Pentacyclic triterpanes (m/z 191) parameters of studied samples Sample C23/C24a 22S/ (22S+22R)b ba/abc Ts/Tmd J.53 2.44–0. usually C31.33 0.17a(H)-Steranes.83 0.77 2.71 0. Chaker JC-01 JC-16 JC-28 Average J.94 3.51 2. The 22R compounds are gradually converted to a mixture of 22R and 22S diastereomers. and Chaker samples. the ratio of Ts over Tm (Ts/Tm) has been documented for characterizing the origin and the degree of maturation of crude oils and for determining their correlation indexes (Wang et al.48 C23-Tricyclic terpanes/C24-tetracyclic terpane 22S/(22S+22R) for C31-17a.72 1..59 0.37 5a(H).17a(H)-20R-Steranes. Volkman et al. Waples. Serj KZ-06 KZ-11 KZ-16 Average J. Chaker JC-01 JC-16 JC-28 Average J.ARTICLE IN PRESS 576 A. c 17b.26 0.56 2.14a(H).88 3.59 0. Such a range also conﬁrms the presence of relative immature petroleum in sediments in the presence of inert minerals in such area (e.60 (Table 5). Es-Sfeı¨ a JE-01 JE-05 JE-11 Average a b C27/C29b C28 C29 Diasteranes indexc 20S/(20S+20R)d bb/(bb+aa)e 49 48 46 48 44 46 43 44 63 50 46 53 26 29 30 28 29 29 32 30 10 32 34 25 25 23 24 24 25 25 25 25 27 18 20 22 1.44 0.63 0. 1999).85 0. 1987).67 0. Sediments with the maturity level equivalent to Ro ¼ 0.29.56 0.52 0.
Bennet. Corvi. Bull. 23–42. Applied Petroleum Geochemistry. Organic geochemistry of paleodepositional environments with predominance of terrigenous higher-plant organic matter. Tunisie centro-septentrionale: Se ` se.A. pp. Laporte. .. J. P.A. B. Conclusions Utilizing the Rock-Eval pyrolysis and the GC–MS techniques made it possible to arrive at a clear characterization and classiﬁcation of organic matter according to its source. J. 1956. Oro. J.... 40.. Warden. Les calcaires de l’Eoce ´ dimentologie et Pale ´ oge ´ ographie.. 40.J. Connan. Schneider. Kamoun and A. In: B.. 1995b. Gjukic.. 2000. G. Vandenbroucke.. (Ed. Tunis. H.. Prentice-Hall. The ` se Doct. Marquis. 559–568. R. 5. C.N.. Institut Franc . O. However. M. 350pp. 2000. Paulet.. Madec. Philp. Hostettler.. Paris. Burollet. 1982. plate-forme tunisienne a 5. 81–104.. Part II. 1977. P. Ge ´ ol..N. Leplat. Moldowan. Occurrence and formation of tricyclicand tetracyclic terpanes in sediments and petroleums.). D. Rigane for helpful comments and suggestions that improved this paper. M. Advances in Organic Geochemistry. 169pp. J. 1991. A. 1990. Coal Geology 43. Rapp. J. (Ed. M.. 1983. J. P. T.. Mines Ge Connan.. J. Pereira.G. In: Huc. Aquino Neto. Albrecht. Moldowan et al.M.D. Revue Institut Franc . Bull.. H. M. Acknowledgements We would like to express our appreciation to the management of GEOGLOB: 03/UR/10-02 for their continuous support and encouragement and for providing all the necessary requirement to achieve this work. P. K. A. C. (3) the Rock-Eval pyrolysis and GC–MS methods remain useful for a detailed characterization of the organic matter geochemical patterns such as the depositional environment. A.. pp. Broquet. 1993. vol. S1o1 mg HC/g rock). Albrecht.Y.. Editions Technip. 563–578. Restle.). A. P. Engelwood Cliffs.M. F. The microbial input in carbonate-anhydrite facies of a Sabkha paleoenvironment from Guatemala: a molecular approach. vol. Univ. Oro. 204pp.H. Salvatori. 236–239... We are also grateful to Professors F. (Eds. of Tunisia..). Trends in Biochemical Science 7. Alageg.. G. 1993.F.. A. S..M. origin and diagenetic/maturation history of geological organic matter. References Aquino Neto. Schneider. France... J.. In: Bordenave. Editions Technip.. J.A.ais du Pe ´ .M. applications. Alaska Environmental Science and Technology 29. Mejri. The geochemical comparison between Rock-Eval pyrolysis and biomarkers parameters suggesting a similar geochemical ﬁngerprint of all studied source rocks in central-northern Tunisia.. Restle.J. E. 194pp.-Y. G. and Source Rocks.M.S. Oleﬁns of high molecular weight in two microscopic algae.... Threlkeld. Part I: Oil and gas generation from kerogen. Applied Petroleum Geochemistry.. vol.J. 115–127. Predictive microbial biochemistry from molecular fossils to procaryotic membranes. Paleography. P. A..ARTICLE IN PRESS A. Science 161. de leur potentiel pe ´ trolier et de leur degre ´ d’e ´ volution. Analyse quantitative de la ´ siens en Tunisie: l’exemple de Jebel fracturation des calcaires ypre ´ ol. Tunisie centrale.R. R. P. 1970. Oudin. Aite. F.. Leplat. 29–50. M. Simple kinetic models of petroleum formation. Isaksen.. 1994. 18.. A. F. J.). Soc. A. H..A. S. Gelpi. (2) the studied organic-rich facies represent new potential source rocks in a promising area such as the Ypresian Basin in central-northern Tunisia as indicated by the relative high TOC.. P.. Arfaoui et al. Oro.. F.L. Bouroullec. The ´ . vol. pp. P. 1995. ´ . / Marine and Petroleum Geology 24 (2007) 566–578 577 In the case of studied samples. 1983.. Tunis. Kruge. Pepper. 2684–2694.). 370–401. R. 1986. Hydrocarbons of geochemical signiﬁcance in microscopic algae... Me ` res. Novel tricyclic terpane (C19. H. ne Ben Ferjani.. E... Albrecht. Espitalie M. ` res structuraux et dynamiques d’un bassin en transtension: la Caracte ` l’Ypre ´ sien terminal. Dessort.. NJ. Deroo. F. (Ed.. Etude de la matie ´ e du bassin de Gafsa-Metlaoui (Tunisie).. K.. Luoma. France 3.D.. J. (Eds... Determination of thermal maturity and organic matter type by principal components analysis of the distributions of polycyclic aromatic compounds. 22S/ (22S+22R) ratio may be related to other factors which affect the isomerization speed of 17a(H)-homohopanes.. 603–612. 2027–2030. (1992) have found that homohopanes were totally isomerized in immature carbonatic source rocks from the Adriatic Basin. 27–51. Hostettler.. Marine and Petroleum Geology 12. Gelpi. 1992. phosphate ´ moire. Ourisson. Kharbachi. 1982. Franche Comte ´ . S.. Petroleum Geology ´ s Pe ´ trolie ` res. 219–224. J. Ts/Tm gives a best evidence of the low thermal maturity of Ypresian organic matter. 77. Phytochemistry 9.. The molecular fossil record of oleanane and its relation to angiosperms. A. R. Ousselat. AAPG. F. Source correlation and maturity assessment of select oils and rocks from the Central Adriatic Basin (Italy and Yugoslavia).. Application a ` la compre ´ hension de la phosphatoge ´(Ed.. (Ed. C. vol..L. Ann. C20) in sediments and petroleums. C. Ourisson. Albrecht. 659–667. La pyrolyse Rock-Eval et ses Espitalie ´ trole. 1999. Demaison. Paris... 40. Organic Geochemistry 10. Anima.L.. ` re organique dans la se ´ rie Belayouni.. J. Revue me ´ trole 32.F. Carlson.. 603–612. R. G. The similarity of these parameters suggested that (1) the organic matter may be autochthonous to the environment where it is deposited with predominance of marine source. 175–204. Connan. M.. Tetrahedran Letters 23.. We would like to extend our sincere thanks to anonymous reviewers for helpful reviews. Lee. J. J.ais du Pe pp.. Mann.. Fuller.L.B.).R. J. Marine Chemistry 64. 309–315. F. 768–771. P. Truillet. Sundararaman. Rohmer. Rigane. G. (Ed. Part I. Screening techniques for source rock evaluation. J.. Entreprise Tunisienne d’Activite ` ne infe ´ rieur en Ben Jemia-Fakhfakh. Boukadi. van Geen. Me ` se. such ratio was conﬁrmed by Rock-Eval pyrolysis data (Tmax: 427–442 1C. Ge ` l’e ´ tude stratigraphique de la Burollet.. pp. 1985. F.C. Soc. Kvenvolden. Albrecht.E. Bordenave. W. Contribution a ´ ol. Univ.. 2000...).R. Paleoclimate. N. Etat. Trendel.P. pp. Espitalie ´ thode rapide de caracte ´ risation des roches Boutefeu.R. pp. A record of hydrocarbon input to San Fransisco Bay as traced by biomarker proﬁles in surface sediment and sediment cores. Biological Markers in Sediments and Petroleum. 1993a. 291–319.. J. In: Bjorøy. Moldowan. Orle ´ ans (France). M. In: Moldowan. Connan. El Ayeb. 1968. Marquis. J. P. J. Ubiquitous tar balls with a California-source signature on the shorelines of Prince William Sound. In: Bordenave. Molecular geochemistry in oil exploration.L. Science 265. which was generated dominantly prior to the peak stage of the conventional oil window (end of diagenesis-beginning of catagenesis).. P. 755–784.. Kvenolden. Gourmelen.).
(Ed. Fingas.. 1977. S. Interpreting Molecular Fossils in Petroleum and Ancient Sediments... 1995. Originalite ´ nome ` nes tectoniques syn-se ´ dimentaires ﬁni-ypre ´ siens en Tunisie phe ´ gion de Kairouan). 743–777.P. 1991.. Soc. Combaz. London. J. R. J. G.A.. Colombia. Organic Geochemistry 30.. a terrigenous saline basin. R. B. 1978. R. Bull.W. 55. R. Alexander.. 1987.I. 231–251. Gourmelen.M. 363pp. Zaı¨ r. Pretice-Hall. D.P. New York.A. Geological Society. 1988.. New York. centro-septentrionale (re 27–35. Special Publication 132. Kagi. China. 2091–2106. Elsevier. 1984. Espitalie ´ diments: application d’une simulation mathe ´ matique. R..P. Seifert. J. Rullkotter. The Biomarker Guide. 699pp.. Z... Polycyclic Aromatic Compounds 7..H. 1991..).. ´ . Sassi. The ´ des Rigane. Moody. C. Volkman. A...). Applications of steranes. AAPG 9. 249–266. 1994. Noble..ARTICLE IN PRESS 578 A. B. Englewood Cliffs.. Geochimica et Cosmochimica Acta 47.K. A.. Waples. Philp. Revue Institut Franc .. Peters.). Fossil Fuel Biomarkers..M. vol. 214pp. Geochemistry in Petroleum Exploration.. 375–393..P. T.P.. Bull. 2177–2193.C. Organic Geochemistry 13. W. Rouache.. 77–95. 1999.E.K. Moldoman. Sergy. 1975. Wang. 1985. J. A geochemical reconstruction of oil generation in the Barrow sub-basin of Western Australia. I. 1998. 549–562. K. France 1. / Marine and Petroleum Geology 24 (2007) 566–578 Tissot. M. septentrionale cartographie. J. 1985. S. Boston. Woodhouse. R.J. Fan. B. Ge ´ ol.G. 1733–1746..L. Z. Geochimica et Cosmochimica Acta 42. organique des se ´ trole 30. A. J. (Eds.. A. Organic Geochemistry 11. Petroleum geochemistry of Middle Magdalena Valley. Distribution of polycyclic aromatic compounds in coals of high rank. migration and source of crude oils. 232pp.. Geochemical investigation of oils and source rocks from Qianjing Depression of Jianhan Basin. 91. M. (Ed.T. Pelet.W. Machihara. R. Basin evolution and deposition during the early Paleogene in Tunisia. terpanes. Petroleum Formation and Occurrence.W. Beji-Sassi. Springer. Wakeham.). ge Tissot. 1994. 1990.. Environmental Science and Technology 28. P. 294pp.. Marzi. Welte.. 639–645. cine ` se Universite ´ de Franche Comte ´ .. Philp. Arfaoui et al. H. 23. Dzou. 1983a. Waples.. and monoaromatics to the maturation. Biomarkers for geologists—a practical guide to the application of steranes and triterpanes in petroleum geology. Natural and artiﬁcial maturation of biological markers in a Toarcian shale from northern Germany. R. Geochimica et Cosmochimica Acta 54. NJ. ´ sien en Tunisie centroRigane. Truillet. A. Les calcaires de l’Ypre ´ matique et dynamique des structures. Moldowan. (Eds.G. 1325–1336. Methods in Geochemistry and Geophysics. G. Willsch. L’e ´ volution thermique de la matie ` re Tissot. Reidel Publushing Company.. R.. Algal and bacterial hydrocarbons in particulate matter and interfacial sediment of the Cariaco Trench. D. D.. Study of 22-year-old arrow oil samples using biomarker compounds by GC/MS. Broquet.ais du Pe . 1993.. Ramon. J. A. Radke. Utilisation des ´ ochimiques indicateurs des environnements alcanes comme fossiles ge ´ ologique.
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