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Marine and Petroleum Geology 24 (2007) 566578 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 Arfaoui, 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 chromatographymass spectrometry (GCMS) 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 GCMS 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; GCMS; 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 specic compounds, known as biomarkers which have
Corresponding author. Fax: +216 74 274 437.

E-mail address: arfmon@yahoo.fr (A. Arfaoui). 0264-8172/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.marpetgeo.2007.05.002

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.

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Fig. 1. Paleogeographic map of Tunisia showing the distribution of Ypresian facies (modied from Za r et al., 1998).

This paper interprets the geochemical pattern of organicrich carbonates of the Ypresian Basin located to the west Kairouan, in central-northern Tunisia (Fig. 2). The principal objective of this study is to attempt to understand the organic matter type, its depositional environment and thermal maturity utilising a combination by confrontation of RE pyrolysis and gas chromatographymass spectrometry (GCMS) analysis.

Theses deposits are found in a progradation sequence which shows a regressive tendency from SW to NE. 2.2. Geographic location and lithostratigraphy The studied Ypresian outcrops are located in the northly part of central Tunisia and manifest in a carbonatic megasequence. From east to west, it is possible to distinguish the Es-Sfe a, Chaker, and Serj Jebels which crop out 40 km to the west of Kairouan (central-northern Tunisia) (Fig. 3). In this area, the Ypresian Chaker and Es-Sfe a deposits exhibit a preferred alignment with the NorthSouth axis which is a sub-meridian orogenic segment of central Tunisia (Fig. 3) (Rigane, 1991; Rigane et al., 1994; Gourmelen et al., 2000). To the west of Kairouan, 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. 4) (Boukadi et al., 2000). Within the Metlaoui Formation, three different facies can be distinguished from bottom to top (Rigane et al., 1994): microcrystalline limestones with small pelagic and benthic foraminifera (Bou Dabbous source rock, I), bioclastic and nummulithoclastic limestones (transition facies, II) and massive crystalline limestones with large nummulites (El Garia reservoir, III). The transition from the upper facies (III) to the overlying Souar Formation is characterized by a ne clay marly sequence rich in oriented

2. Geological setting 2.1. Paleogeography of the Lower Eocene in Tunisia The Ypresian Metlaoui Formation shows a wide facies variation from its northern to southern outcrops (Fig. 1) and is coevals to the main phosphatic facies (Chouabine Formation) that crop out extensively in western Tunisia (Burollet, 1956; Ben Ferjani et al., 1990). The previous sedimentological and paleogeographical study by Ben Jemia-Fakhfakh (1991), 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. 2). This passage takes place in a multi-kilometric transition zone which corresponds to an external platform (nummulitoclastic facies), the extension of which is related to the paleomorphology (Fig. 2) (Ben Jemia-Fakhfakh, 1991).

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Fig. 2. Relationship between Metlaoui Formation deposits at (A) Ousselat-Bou Dabbous, (B) Es-Sfe a-Afa r, and (C) Serj Jebels (Ben Jemia-Fakhfakh, 1991).

Fig. 3. Ypresian facies distribution in West of Kairouan and the location of Es-Sfe a, Chaker, and Serj Jebels (after Boukadi et al., 2000).

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organic carbon (mg HC/g TOC), and is a function of relative H/C in the organic matter. Aliphatic hydrocarbons were analyzed by gas chromatographymass spectrometry HP 6890-HP 5973 MSD combination (Agilent Technologies, Wilmington, DE, USA). The GC was used with a 30 m fused-silica column (0.25 mm i.d.) coated with 5% phenyl methyl siloxane. Helium was used as the carrier gas at a ow rate of 1.4 ml/ min. A temperature programme of 100290 1C was employed with ramping at 4 1C/min. The samples were injected in the splitless mode with an injector temperature of 280 1C. Samples were run in the electron impact mode at 70 eV with a 2.9 s scan time over a 50550 amu range resolution. The GCMS analysis was based on fragmentograms at m/z 99, 191, and 217. The relative contents of particular compounds were calculated from peak areas.

4. Results and discussion 4.1. Organic matter source and depositional environment 4.1.1. 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. This area gives the quantity of free hydrocarbons (oil and gas) contained in the rock, expressed in milligram hydrocarbon per gram of rock (mg HC/g rock). 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). This area (S2), gives the residual petroleum potential of the rock, expressed in mg HC/g rock. S2 corresponds in addition to the thermal degradation products of the involatile but extractable asphaltenes and resins. In this present study, S1 values are extremely low ranging from 0.05 to 0.95 mg HC/g rock (Table 1). These low values may suggest that (i) signicant 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, thus the rocks were from high maturity levels. The S2 values which rise from 0.62 to 19.75 mg HC/g rock and average between 5 and 12, at the three localities (Table 1). Given these data the sediments are immature. It is clear that the petroleum potential of the Ypresian sediments is remaining intact. The ratio of S2 to the TOC of the rock is the HI. HI is a key source rock parameter used in quantitative modeling of the phase and volume of expelled hydrocarbons (e.g. Pepper and Corvi, 1995b) and the classication of kerogen type. In the present work, the HI values (Table 1), averaged 400500 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. 4. Lithostratigraphic cross-section of the Ypresian series in centralnorthern Tunisia (Gourmelen et al., 2000).

nummulites and surrounded by two areas of hard ground (Gourmelen et al., 2000; Fig. 4). 3. Materials and methods 3.1. Materials of study All rocks, which are predominantly limestones, have been sampled at outcrop in the Ypresian Basin. Approximately 5001000 g of sample was collected. Immediately after collection all samples were dried at 40 1C. Then, the samples were ground into a ne powder prior to analysis. The geographic locations of the collected samples are shown in Fig. 3. They concern the Jebels of Serj, Chaker, and Es-Sfe a. 3.2. Techniques of study To obtain total organic carbon (TOC) content, hydrogen index (HI, mg HC/g TOC), and Tmax (1C), Rock-Eval analyses were performed on 20 selected samples. These analyses were undertaken mainly by the Entreprise s Pe trolie ` re (ETAP) using RockTunisienne dActivite et al. (1977) Eval II instrument, according to the Espitalie procedure. The pyrolysis of organic matter was performed over the temperature range of 300600 1C with the rate of temperature rise of 25 1C/min. The HI is determined as the yield of reduced products of pyrolysis (S2) relative to the total

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570 A. Arfaoui et al. / Marine and Petroleum Geology 24 (2007) 566578 Table 1 Result of Rock-Eval analyses of representative samples from Es-Sfe a, Chaker, and Serj Jebels Sampling location Sample TOC (wt%) mg HC/g rock S1 J. Es-Sfe 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 2.97 0.09 2.40 3.71 1.54 2.14 1.04 1.82 1.15 1.23 1.57 1.42 1.48 1.68 1.42 0.40 0.54 0.39 1.35 1.37 3.12 1.68 1.26 0.78 0.07 0.62 0.95 0.44 0.57 0.18 0.42 0.14 0.72 0.31 0.20 0.28 0.27 0.31 0.05 0.09 0.05 0.20 0.16 0.73 0.54 0.26 S2 16.15 00.20 14.56 19.75 09.21 12 04.81 08.77 04.97 05.51 05.47 05.51 05.41 06.28 05.34 00.70 01.41 00.62 05.81 03.58 17.99 14.47 06.37 544 222 607 532 598 500.6 463 482 432 448 348 388 366 385 414 175 261 159 430 261 577 861 389.1 0.05 0.26 0.04 0.05 0.05 0.09 0.04 0.05 0.03 0.12 0.05 0.04 0.05 0.04 0.05 0.07 0.06 0.07 0.03 0.04 0.04 0.04 0.05 431 431 430 430 430.5 433 433 436 434 435 436 438 436 435.1 442 439 439 430 431 427 427 433.6 HI PI Tmax (1C)

J. Chaker

J. Serj

TOC: total organic carbon (%); HI: hydrogen index (S2/TOC 100); PI: production index (S1/(S1+S2); Tmax: maximum pyrolysis temperature.

catagenesis) (Fig. 5), and reects a uniform source of organic matter, which is of Type-II, for all studied samples. Furthermore, it seems that no external contribution of migrated hydrocarbons was added to the Ypresian organicrich facies as indicated by the low S1 values, and the production index (IP S1/S1+S2) (Table 1). The average of TOC content in Serj is 1.26 wt%; Chaker 1.42 wt%; and Es-Sfe a 2.14 wt% (Table 1). It reveals that the sediments in the Ypresian Basin display a clear uctuation of TOC values (Fig. 6(a)(c)). Some samples are lean in organic matter (o1wt%). In contrast several samples containing visible carbonaceous matter and showing high TOC values which reached 3.71 wt% in Es-Sfe a Jebel (Table 1). 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, 1984). In contrast, the less oxic environment promoted better organic preservation in the depositional environment. In this respect, our results, particularly Es-Sfe a area, display a relative high TOC contents. This result due to episodes that are generally more conductive for preservation/accumulation of high amount of organic matter in central-northern Tunisia. 4.1.2. n-Alkanes (m/z 99) distribution In this present study, m/z 99 fragmentograms indicate that the hydrocarbons present in the sediments from the

Fig. 5. Organic matter type discrimination diagram of the studied sedimentary rock samples from the Ypresian Basin based on crossplot of Tmax and hydrogen index.

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Fig. 6. (a) Stratigraphic log of the Ypresian sequence at Jebel Serj with location of the samples of organic matter rich rocks. Lower part I: Interbedded gray marl and limestone. Upper part II: Predominant gray to dark organic matter limestones. (b) Stratigraphic log of the Ypresian sequence at Jebel Chaker with location of the samples of organic matter rich rocks. Lower part I: Predominant gray to dark organic matter rich limestones. Upper part II: Gray limestone package. (c) Stratigraphic log of the Ypresian sequence at Jebel Es-Sfe a with location of the samples of organic matter rich rocks. Lower part I: Predominant organic matter rich gray limestones. Middle part II: Interbedded gray marl and limestone. Upper part III: Gray limestone package.

Ypresian Basin have a carbon numbers ranging from 13 to 28 (Fig. 7(a)(c)). 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., 1999). Generally speaking, the n-C15n-C20 alkane series is related to organic source of microorganisms and/or algae (Peters and Moldowan, 1993). If the signatures of algal-marine Type-II organic matter are clearly present with predominance of short-chain n-alkanes (n-C20n-C26) that of continental higher plants with predominance of longchain odd carbon numbered are undetectable. This is evident from the unimodal hydrocarbon distribution with a major mode centered at n-C18 or n-C21. On the other hand, the n-alkanes distribution with relative high abundance of isoprenoids (pristanes and phytane) relative to n-C17 and n-C18, respectively (Fig. 7(a)(c)), shows an unequivocal evidence of the low thermal maturity of the Ypresian phytoplanctonic product

in west of Kairouan. However, Tissot et al. (1977) and Belayouni (1983) suggest that such geochemical ngerprint was found in carbonatic or phosphatic facies when the organic matter was generated dominantly prior to the peak stage of the conventional oil window. 4.1.3. Steranes (m/z 217) distribution The mass chromatograms obtained for representative samples are shown in Fig. 8. The labeled peaks are summarized in Table 2. In this work, following compounds have been identied: C27-cholestane, C28-ergostane, C29-stigmastane and propylcholestanes with their 20S and 20R epimers (Philp, 1985). Cholestane (C27) was consistently the most abundant pseudohomologue comprising 4363% of the total C27C29 regular steranes), followed by ergostane (C28) comprising 1034%, and stigmastane (C29) comprising 1827% (Table 4).

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Fig. 7. (a) Mass chromatograms (m/z 99) of the aliphatic hydrocarbon fractions for some representative samples from Serj area. Pr: pristane; Ph: phytane. (b) Mass chromatograms (m/z 99) of the aliphatic hydrocarbon fractions for some representative samples from Chaker area. Pr: pristane; Ph: phytane. (c) Mass chromatograms (m/z 99) of the aliphatic hydrocarbon fractions for some representative samples from Es-Sfe a area. Pr: pristane; Ph: phytane.

As known, the sterane distributions can be used as effective source facies discriminators to group oils in a region on the basis of genetic relationships. A predominance of C29 steranes is related to a strong terrestrial contribution, whereas a predominance of C27 and C28 indicate a predominance of marine phytoplankton and lacustrine algae, respectively (Peters and Moldowan, 1993). Homologous distributions of steranes, C27C28C29, are often expressed in ternary plots to show similarity or

dissimilarity in source facies among the oils of interest (Fig. 9). In this present study, the ternary plot shows that the outcrop samples are indistinguishable by sterane distributions, indicating that these sediments extracts were derived from a similar marine source. On the other hand, C27/C29 sterane ratios rise from 1.72 to 2.77 (Table 4). Seeing that C27 steranes and C29 steranes are related, respectively, to marine and terrestrial sources (Tissot and Welte, 1984; Waples, 1985), such data conrms

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Fig. 8. Mass chromatograms showing the distribution of steranes (m/z 217) and pentacyclic triterpanes (m/z 191) of some representative samples from Serj (KZ-16), Chaker (JC-28), and Es-Sfe a (JE-01) Jebels.

the marine origin of Ypresian organic matter. This assumption has been conrmed by RE pyrolysis data. The occurrence of C29 steranes may be, also, related to the microscopic algae which are able to secrete major C27, C29, and C31 hydrocarbons (Gelpi et al., 1968, 1970). Diasterane/sterane ratios are commonly used to distinguish carbonate from clay-rich source rocks. However, low diasterane/sterane ratios are associated with anoxic, claypoor, carbonate source rocks, whilst high ratios are generally found in oils derived from clastic sediments, where clay minerals may act as catalysts in their formation from other steranes (Peters and Moldowan, 1993). However, diasterane/sterane ratios are also generally low in immature/early mature sediment extracts. Table 4 shows that the diasteranes index, of all outcrop sample extracts, rise from 0.49 to 0.88. The occurrence of diasteranes in relative low abundance in Ypresian organic

matter implies generation of these oils from source rocks lean in clay minerals. 4.1.4. 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., 1982). Aquino Neto et al. (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, 1993). In this present study, tricyclic terpanes have been found in all the extracts (Fig. 8 and Table 3). Generally, outcrop samples from Serj, Chaker, and Es-Sfe a areas have relatively high C23-tricyclic terpane.

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574 A. Arfaoui et al. / Marine and Petroleum Geology 24 (2007) 566578 Table 2 Steranes (m/z 217) identication in chromatograms of Fig. 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, 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),14b(H),7b(H)-Pregnane Diahomopregnane 5a(H),14b(H),17b(H)-Methylpregnane 13b(H),17a(H)-Diacholestane (20S) 13b(H),17a(H)-Diacholestane (20R) 13a(H),17b(H)-Diacholestane (20S) 13a(H),17b(H)-Diacholestane (20R) 13b(H),17a(H)-24-Methyldiacholestane (20S) 24R/S isomers (?) 13b(H),17a(H)-24-Methyldiacholestane (20S) 24R/S isomers (?) 13b(H),17a(H)-24-Methyldiacholestane (20S) 24R/S isomers (?) 13b(H),17a(H)-24-Methyldiacholestane (20S) 5a(H),14a(H),17a(H)-Cholestane (20S) 5a(H),14b(H),17b(H)-Cholestane (20R)+ 13b(H),17a(H)-24-Ethyldiacholestane (20S) 5a(H),14b(H),17b(H)-Cholestane (20S) 13a(H),17b(H)-24-Methyldiacholestane (20R) 5a(H),14a(H),17a(H)-Cholestane (20R) 13b(H),17a(H)-24-Ethyldiacholestane (20R) 13a(H),17b(H)-24-Ethyldiacholestane (20S) 5a(H),14a(H),17a(H)-24-Methyldiacholestane (20S) 13a(H),17b(H)-24-Ethyldiacholestane (20R) 5a(H),14b(H),17b(H)-24-Methylcholestane (20R) 5a(H),14b(H),17b(H)-24-Methylcholestane (20S) 5a(H),14a(H),17a(H)-24-Methylcholestane (20R) 5a(H),14a(H),17a(H)-24-Ethylcholestane (20S) 5a(H),14b(H),17b(H)-24-Ethylcholestane (20R) 5a(H),14b(H),17b(H)-24-Ethylcholestane (20S) 5a(H),14a(H),17a(H)-24-Ethylcholestane (20R) 5a(H),14a(H),17a(H)-24-Propylcholestane (20S) 5a(H),14b(H),17b(H)-24-Propylcholestane (20R) 5a(H),14b(H),17b(H)-24-Propylcholestane (20S) 5a(H),14a(H),17a(H)-24-Propylcholestane (20R)

Fig. 9. Ternary plot showing the distribution of regular steranes (C27C28C29) of studied samples.

The C24 tetracyclic terpane is also present in Ypresian organic matter (Fig. 8 and Table 3). It is known that the proportion of C24 tetracyclic terpane relative to triterpanes

may also be facies dependent, with relatively high concentrations in source rocks and oils with terrigenous input, or in sediments with low clastic content (Peters and Moldowan, 1993). In outcrop samples the C23/C24 ratios rise from 2 to 3.20 (Table 5). Such result reects the occurrence of the C23-tricyclic terpane in high concentrations compared to the C24-tetracyclic terpane. Thus, the relatively low abundance of the C24 tetracyclic in Serj, Chaker, and Es-Sfe a outcrop samples suggests a marine ngerprint of the Ypresian organic matter (Aquino Neto et al., 1982; Connan et al., 1986; Peters and Moldowan, 1993). The ratios of 17b(H),21a(H)-moretanes to their corresponding 17a(H),21b(H)-hopane (ba-moretane/ab-hopane) rise from 0.13 to 0.26 (Table 5). Generally, these ratios increase in organic matter deposited in depositional environment with high salinity (Rullkotter and Marzi, 1988). Thus, these relative low ratios reect an open sea with absence of terrestrial contribution of organic matter. Furthermore, Connan (1993) interprets the distribution of terpanes with predominance of hopane series (ab-hopanes and ba-moretane) as a reection of microbial activity.

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A. Arfaoui et al. / Marine and Petroleum Geology 24 (2007) 566578 Table 3 Pentacyclic triterpanes (m/z 191) identication in chromatograms of Fig. 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. 4.2.2. 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. Only the R conguration at C-20 (called 20R) is found in steroid precursors in living organisms, and it gradually converts during burial maturation to a mixture of the R and S sterane congurations. Thus, the ratios [20S/(20S+20R)] for C29 steranes are the only epimer ratios that could be measured with condence (Table 4) (Peters and Moldowan, 1993). Another maturity parameter derived from C29 regular steranes is the proportion of 5a(H),14b(H),17b(H) C29 sterane and 5a(H),14a(H),17a(H) C29 sterane forms (isomerization at C14 and C17) expressed as the ratio abb/ (abb+aaa) sterane. As the maturity increases, the aa form, which is produced biologically, converts gradually into a mixture of aa and bb. This ratio is somewhat slower to reach equilibrium than the 20S/(20S+20R) ratio, thus making it effective at higher levels of maturity (Peters and Moldowan, 1993; Ramon and Dzou, 1999). In this present study, 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), rise from 0.26 to 0.50 and from 0.32 to 0.43, respectively. 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, 1993) as indicated by Tmax values and Tmax/HI diagram (Fig. 5). 4.2.3. Hopane maturity parameters The ratio of 17b(H),21a(H)-moretanes to their corresponding 17a(H),21b(H)-hopane (ba-moretane/ab-hopane) decrease with increasing thermal maturity. Usually, this ratio decreases from about 0.8 in the immature stage to values of less than 0.15 in mature stage and a minimum of 0.05 (Rullkotter and Marzi, 1988; Peters and Moldowan, 1993). The ratios of ba-moretane/ab-hopane of the samples from Serj, Es-Sfe a, and Chaker in the Ypresian Basin are listed in Table 4. Samples show this ratio in the range of 0.130.31, indicating the early mature stage for these biomarkers (equivalent to Ro 0.5%, Peters and Moldowan, 1993). The 17a(H)-22,29,30-trisnorhopane (called Tm) and 18a(H)-22,29,30-trisnorhopane (called Ts), two C27 pentacyclic tristerpanes, are often applied to assess the maturity level of sediments (Rullkotter and Marzi, 1988; Peters and Moldowan, 1993). The abundance of Ts relative to Tm is inuenced by both maturity and source rock mineralogy (catalytic versus inert minerals; Philp and Fan, 1987). 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)-22,29,30Trisnorneohopane (Ts) Pentacyclic terpane 17a(H)-22,29,30Trisnorhopane (Tm) Tricyclic triterpane (22R) Tricyclic triterpane (22S) 17a(H),21b(H)-28,30Bisnorhopane 17a(H),21b(H)-25Norhopane 17a(H),21b(H)-30Norhopane 18a(H)-Norneohopane (29Ts) Diahopane 17b(H),21a(H)-30Normoretane 18a(H)-Oleanane 17a(H),21b(H)-Hopane 17b(H),21a(H)-Moretane 17a(H),21b(H)-Homohopane (22S) 17a(H),21b(H)-Homohopane (22R) Gammacerane

4.2. Thermal evolution of organic matter 4.2.1. 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. This was found to vary with the thermal evolution formerly undergone by the rock sample , 1975; Espitalie et al., under analysis (Tissot and Espitalie 1977). In this work, a general assessment of thermal maturity using Tmax values shows a small difference between the four areas. Samples from the western part of the Ypresian Basin (J. Serj) have the higher Tmax values, which reached 442 1C, whereas samples from the eastern part (particularly J. Es-Sfe a), have much lower Tmax values of 430431 1C (Table 1). Generally, all the Tmax values suggest that the

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576 A. Arfaoui et al. / Marine and Petroleum Geology 24 (2007) 566578 Table 4 Sterane parameters (m/z 217) of studied samples Sample Sterane (%)a C27 J. Serj KZ-06 KZ-11 KZ-16 Average J. Chaker JC-01 JC-16 JC-28 Average J. Es-Sfe 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

1.96 2.09 1.91 2 1.76 1.84 1.72 1.77 2.33 2.77 2.30 2.40

0.65 0.71 0.55 0.63 0.85 0.49 0.59 0.64 0.85 0.88 0.83 0.86

0.50 0.26 0.33 0.37 0.41 0.40 0.38 0.40 0.34 0.42 0.42 0.40

0.40 0.37 0.34 0.37 0.43 0.35 0.37 0.39 0.32 0.35 0.43 0.37

5a(H),14a(H),17a(H)-20R-Steranes. C27/C29 (5a(H),14a(H),17a(H)-20R-Steranes). 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)]. d 20S/(20S+20R) for C29-5a(H),14a(H),17a(H)-Steranes. e 5a(H),14b(H),17b(H)/[5a(H),14b(H),17b(H)+5a(H),14a(H),17a(H)] for C29-Steranes.

Table 5 Pentacyclic triterpanes (m/z 191) parameters of studied samples Sample C23/C24a 22S/ (22S+22R)b ba/abc Ts/Tmd

J. Serj KZ-06 KZ-11 KZ-16 Average J. Chaker JC-01 JC-16 JC-28 Average J. Es-Sfe a JE-01 JE-05 JE-11 Average
a b

2.00 2.72 2.56 2.42 2.94 3.18 2.53 2.88 3.20 2.51 2.48 2.73

0.56 0.55 0.60 0.57 0.55 0.60 0.59 0.58 0.55 0.58 0.50 0.54

0.31 0.23 0.17 0.24 0.18 0.17 0.13 0.16 0.20 0.19 0.26 0.21

0.89 0.67 0.61 0.72 0.49 0.56 0.63 0.56 0.44 0.48 0.52 0.48

C23-Tricyclic terpanes/C24-tetracyclic terpane 22S/(22S+22R) for C31-17a,21b-homohopane. c 17b,21a(H)-Moretane /17a,21b(H)-hopane for C30-triterpanes. d 18a(H)-22,29,30-Trisnorneohopane/17a(H)-22,29,30-trisnorhopane.

(Hostettler et al., 1999). Therefore, 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., 1994; Hostettler et al., 1999).

Tm/Ts 1 was considered as a limit between immature (Ts/Tmo1), and mature (Ts/Tm41) organic matter (Seifert and Moldoman, 1978; Volkman et al., 1983a; Waples, 1985). In Serj, Es-Sfe a, and Chaker samples, values of the ratio 18a(H)-22,29,30-trisnor-neohopane (Ts)/17a(H)-22,29,30trisnorhopane (Tm) vary in the range 0.440.88 (Table 5). Such a range also conrms the presence of relative immature petroleum in sediments in the presence of inert minerals in such area (e.g. carbonates Philp and Fan, 1987). The stereochemistry at the C22 chiral center in the side chain for homohopanes (extended hopanes) forms the basis for a second maturity measurement. The biologically produced precursors for hopanes have the R conguration at the C22 position (called 22R). The 22R compounds are gradually converted to a mixture of 22R and 22S diastereomers. Thus, usually C31- or C32-homohopanes are used for calculations of the 22S/(22S+22R) ratio. The 22S/(22S+22R) ratio rises from 0 to about 0.6 (0.570.62 equilibrium) during maturation. Sediments with the maturity level equivalent to Ro 0.6% shows 22S/(22S+22R) ratios in the range 0.50.54 (Peters and Moldowan, 1993; Kvenvolden et al., 1995). In this present study, the 22S/(22S+22R) ratio of the C31 17a-hopanes in the Ypresian samples extracts range from 0.50 to 0.60 (Table 5). 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.

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In the case of studied samples, such ratio was conrmed by Rock-Eval pyrolysis data (Tmax: 427442 1C; S1o1 mg HC/g rock). Ts/Tm gives a best evidence of the low thermal maturity of Ypresian organic matter. However, 22S/ (22S+22R) ratio may be related to other factors which affect the isomerization speed of 17a(H)-homohopanes. Moldowan et al. (1992) have found that homohopanes were totally isomerized in immature carbonatic source rocks from the Adriatic Basin. 5. Conclusions Utilizing the Rock-Eval pyrolysis and the GCMS techniques made it possible to arrive at a clear characterization and classication of organic matter according to its source. The geochemical comparison between Rock-Eval pyrolysis and biomarkers parameters suggesting a similar geochemical ngerprint of all studied source rocks in central-northern Tunisia. 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, which was generated dominantly prior to the peak stage of the conventional oil window (end of diagenesis-beginning of catagenesis); (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; (3) the Rock-Eval pyrolysis and GCMS methods remain useful for a detailed characterization of the organic matter geochemical patterns such as the depositional environment, origin and diagenetic/maturation history of geological organic matter.

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. We are also grateful to Professors F. Kamoun and A. Rigane for helpful comments and suggestions that improved this paper. We would like to extend our sincere thanks to anonymous reviewers for helpful reviews. References
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