ISSN 0016-7029, Geochemistry International, 2008, Vol. 46, No. 10, pp. 10231037. Pleiades Publishing, Ltd., 2008.

Original Russian Text A. Arfaoui, M. Montacer, 2008, published in Geokhimiya, 2008, No. 10, pp. 10921105.

Organic Geochemical Study of Ypresian Sediments

at Jebel Ousselat, Tunisia1
A. Arfaoui and M. Montacer
GEOGLOB code 03/UR/10602 University of Sfax, Faculty of Sciences, Department of Earth Sciences,
P.O. Box 802, 3038 Sfax, Tunisia
e-mail: arfmon@yahoo.fr; Mabrouk.Montacer@univgb.rnu.tn
Received January 24, 2006

AbstractThis new study was carried out in order to accurately characterize the geochemical pattern of Ousselat organic-rich facies from the Ypresian basin in central-northern Tunisia. It has been found that the organic
matter is located towards the end of diagenesis/beginning of catagenesis. This assumption is supported by the
relative low Tmax values (429439C) and by steranes maturity parameters such as C29 20S/(20S + 20R), and
C29 /( + ). High HI values and the abundance of saturates (183%) compared to aromatics (227%) are
unequivocal evidence of type-II organic matter as indicated by a high abundance of cholestane and the predominance of short-chain n-alkanes centred at n-18 and at n-20. Total organic carbon (TOC) content and petroleum potential values suggest that the Ypresian period corresponds to an anoxic event which led to the accumulation and preservation of large quantities of organic matter with high primary production. Due to their
geochemical characteristics, the Lower Eocene facies represent a new potential source rocks in central-northern
Tunisia.
DOI: 10.1134/S0016702908100078
1

INTRODUCTION

GEOLOGICAL SETTING

On the southern Tethys margin, an Early Eocene

nummulite platform covered the area between Central
and Eastern Tunisia [1, 2]. This series, know as the Metlaoui Formation [3], shows a wide range of facies (Fig. 1).
It represents the main phosphatic facies (Chouabine
formation) in western Tunisia and the major oil exploration objective in the Gulf of Gabes (offshore Tunisia).

The early Eocene outcrops are located west of Kairouan in central-northern Tunisia. They correspond to a
portion of the Tunisian Atlas dominated by Atlasic folding referred to the orogenic phases and the so-called
NorthSouth Axis (NOSA), which has been an active
area since the beginning of the Mesozoic [3].
In the west of Kairouan, the Ousselat outcrops are
delimited to the east by Chaker and Es-Sfea Jebels. To
the west and north they are bordered by Serj and BouDabbous Jebels. To the south they are delimited by
Trozza and Cherichira Jebels (Fig. 2). These outcrops
are unique in that they expose the basin to mid-ramp
transition along continuous, three-dimensional outcrops in an area 10 km by 20 km [5]. Jebel Ousselat,
whose core is occupied by Ypresian carbonates (Fig. 3),
is a boxed anticline several kilometers wide in many
places, injected style, because the anticline is stacked
by a fault at its edge, the fault has locally evolved
through reverse fold-fault into a backthrust [6].
The field observation show that this block is abnormally thick from the Campanian to the Ypresian age
(Fig. 3), the same sequence is rapidly reduced across
the fault, and there is a lateral facies change as well.
Until the Ypresian age, Ousselat was a graben, before
subsidence inversion occurred [6].

In this study, special attention was paid to organicrich carbontes which outcrop in the central part of the
Ypresian basin in the West of Kairouan, (Fig. 2). These
facies correspond to the Ypresian Metlaoui Carbonate
Group located about 40 km east of Kairouan city in the
region of the intermediate Atlas, which is characterised
by NESW trending anticlinals and faults [4].
To further assess the petroleum potential of organicrich facies in central-northern Tunisia, the aim of the
present paper is to characterize the organic matter (origin, thermal maturity composition, etc.) in the Ousselat
area from the Ypresian basin through geochemical
analysis.
1 The

text was submitted by the authors in English.

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ARFAOUI, MONTACER

Algeria

Tunis
Karirouan

Metlaoui
1

100
km

100
km

Globigerina limestone

Bioclastic limestone

Dolomite and anhydrite

Nummuliticlaste limestone

Sandy limestone with alga

Anhydrite

Nummulite limestone

Gasteropod limestone

Terrogenous silty clay

Fig. 1. Lithofacies distribution of the Ypresian in Tunisia [1]. (after Bishop, 1988 modified).

METHODOLOGY
Sampling
Organic-rich facies, predominantly limestone, were
collected from Ousselat outcrops, on average 5001000 g
per sample. Immediately after collection, all samples
were dried at 40C. Then the samples were finely
ground prior to analyses.
Analytical Procedures
Bitumen extraction. Bitumen was extracted from a
powdered sample (3040 g) with dichloromethane as
the solvent (300400 cm3) for 1 hour at 40C. After filtration, the solvent was evaporated (a rotary evaporator
with a water aspirator, evaporation temperature of
40C). Then, the extracts (freeoils or bitumen) were
concentrated by allowing the oil-solvent solution to
stand at room temperature until the CH2 CI2 was
removed.
Liquid-column chromatography. The free oils
were fractionated by column chromatography on alumina over silica gel. A variety of lipid fractions, including non-aromatics or aliphatics (F1), aromatics (F2)

and polar compounds (F3), were obtained. Hexane and

hexane:dichloromethane (65 : 35 Vol/Vol) were used as
eluants for F1 and F2, respectively.
Rock-Eval II analyses. To obtain Total Organic
Carbon (TOC) content, Hydrogen Index (HI, mg HC/g
TOC), Oxygen Index (OI, mg CO2/g TOC), and max
(), Rock-Eval analyses were performed on some
selected samples. These analyses were undertaken
mainly by the Entreprise Tunisienne dActivits
Ptrolire (E.T.A.P.) using Rock-Eval 11 plus instrument, according to [7].
The pyrolysis of organic matter was performed at
the temperature range 300 600C, with the temperature rising at 25C/min. HI is determined as the yield of
reduced products of pyrolysis (S2) relative to the total
organic carbon (mg HC/g TOC) and OI is the yield of
the oxygen and bound organic carbon (S3) relative to
TOC (mg CO2/g TOC). The hydrogen index HI is a
function of relative H/C in organic matter. The oxygen
index OI reflects the relative content of the oxygen containing functional group.

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ORGANIC GEOCHEMICAL STUDY OF YPRESIAN SEDIMENTS AT JEBEL OUSSELAT

J O
U S
E L
A I

J.SERJ

Kgt. Zelga

J. BJU-DABBOUS

11

36

1025

J. CHAKER
J. Rouissat
J. ES-SFEIA
Kairouan

KAIROUAN
SFAX
34

GABES

J. Trozza
0

10 km

J.F. Houarcb

Facies of globigerinids

Facies of nummulites

Fault

Fig. 2. Structural map of Jebel Ousselat [4] (modified from Boukadri et al., 2000). Cross section EW of this study area is shown
in Fig. 3.

GC/MS analysis. Aliphatic (fraction F1) were analyzed by gas chromatography/mass 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 flow rate of 1.4 ml min1. The following
temperature programme was employed: 100290C
with ramping at 4C min1. The samples were injected
in the splitless mode with an injector temperature of
280C. Samples were run in the electron impact mode
at 70 eV with a 2.9 s scan time over a 50550 a.m.u.
range resolution. n-Alkanes and steranes distribution
analysis were based on fragmentograms at m/z 99 and
m/z 217, respectively. The relative contents of particular compounds were calculated from peak areas.
RESULTS AND DISCUSSION
Bitumen Extraction and Liquid Chromatogrmaphy
The results of the hydrocarbon extractions and their
chromatographic separations are listed in Tables 1 and 2.
The concentrations of the chloroform extracts are
exceedingly low, ranging from 0.10 to 3.29 mg/g dry
weight for the analyzed samples. The low concentrations probably result from the low thermal maturity of
organic matter [8, 9], and can be related to differences
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in the mineral composition of the investigated rocks

[10]. However, it can be assumed that a considerable
amount of bitumen is bound to argillaceous minerals
[10]. In this study, the lowest extractability can be
explained by the predominance of limestone facies in
studied areas.
A general feature of studied samples that they are
enriched in asphaltic (NSO) compounds (295%)
(Table 1). On the other hand, compared to the aromatic
fractions (227%), the aliphatic hydrocarbons are
present in relatively higher concentrations (183%),
suggesting probable type-II organic matter, as indicated
by the saturated/aromatic ratios (F1/F2) greater than
one in most of studied samples (Table 1). The normalized percentage compositions of these three fractions of
each sample are plotted in a ternary diagram (Fig. 4).
The hachured area in the figure represents typical conventional petroleum compositions [8]. The samples in
this study are scattered in the ternary plot. Lower abundances of aliphatic and aromatic hydrocarbons in the
Ypresian sediments are attributed to the low thermal
maturity of organic matter [8, 10] and the possible
removal of these compounds by a combination of postgeneration processes such as weathering and biodegradation [11].
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250
50 m
0

Ypresian limestone
100

Faleocene el haria Shale

Jebel ousselat

1000 m
500

500

1000 m

Fig. 3. EW section of the Jebel Ousselat [6] (after Rigane, 1994 modified).

Aromatic H.C.
100 %

50

100%
Aliphatic H.C.

50

50

100%
Asphaltic H.C.

Fig. 4. Ternary diagram of saturated hydrocarbons, aromatic hydrocarbons, and NSO plus asphaltic compounds. Typical crude oils
fall within the hachured area (Tissot and Welte, 1984) [8].
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Table 1. Extract yields and relative percentages of saturated hydrocarbons, aromatic hydrocarbons and asphaltic (NSO) compounds of Ousselat samples
Total bitumen extract Aliphatic hydrocarbons Aromatic hydrocarbons Asphaltic (NSO) compounds
Sample

Total yield
(mg/g dry weight)

F1
(% of three fractions)

F2
(% of three fractions)

F3
(% of three fractions)

F1/F2

AS-0
AS-01
AS-02
AS-03
AS-04
AS-05
AS-06
AS-07
AS-08
AS-09
AS-10
AS-11
AS-12
AS-13
AS-14
AS-15
AS-16
AS-17
AS-18
AS-19
AS-20
AS-21
AS-22
AS-23
AS-24
AS-25
AS-26
AS-27
AS-28
AS-29
AS-30
AS-31
AS-32
AS-33
AS-34
AS-35
AS-36
AS-37
AS-38
AS-39
AS-40
AS-41
AS-42
AS-43
AS-44
AS-45
AS-46
AS-47
AS-48
AS-49
AS-50
AS-51

00.35
00.38
01.63
00.28
00.10
00.47
00.29
01.47
00.27
00.32
00.23
00.25
00.30
00.31
00.23
00.19
00.24
00.34
00.29
00.48
03.29
00.11
00.19
02.06
00.33
00.13
01.92
00.52
02.17
00.46
00.42
00.60
02.90
00.50
01.22
00.71
00.38
00.21
00.12
00.67
00.89
01.23
00.20
00.45
02.80
00.36
02.24
00.78
00.79
00.59
02.10
00.46

10.00
17.00
82.00
30.00
33.00
01.00
18.00
83.00
25.00
22.00
16.00
26.00
23.00
07.00
08.00
17.00
06.00
04.00
38.00
28.00
76.00
08.00
11.00
92.00
22.00
39.00
19.00
14.00
13.00
33.00
32.00
14.00
47.00
32.00
12.00
19.00
26.00
30.00
27.00
09.00
15.00
22.00
24.00
32.00
25.00
14.00
37.00
19.00
18.00
16.00
63.00
09.00

12.00
07.00
09.00
17.00
17.00
04.00
09.00
04.00
18.00
05.00
27.00
14.00
21.00
20.00
08.00
17.00
06.00
14.00
09.00
13.00
03.00
17.00
11.00
06.00
10.00
17.00
04.00
09.00
04.00
17.00
02.00
11.00
05.00
11.00
06.00
16.00
11.00
07.00
09.00
08.00
08.00
14.00
19.00
17.00
12.00
14.00
11.00
09.00
17.00
09.00
05.00
02.00

78.00
76.00
09.00
53.00
50.00
95.00
73.00
13.00
57.00
73.00
58.00
60.00
56.00
73.00
84.00
66.00
88.00
82.00
53.00
59.00
21.00
75.00
78.00
02.00
68.00
44.00
77.00
77.00
83.00
50.00
66.00
75.00
48.00
57.00
82.00
65.00
63.00
63.00
64.00
83.00
77.00
64.00
57.00
51.00
63.00
72.00
52.00
72.00
65.00
75.00
32.00
89.00

00.80
02.40
09.10
01.70
01.90
00.20
02.00
21.00
01.40
04.40
00.60
01.90
01.10
00.30
01.00
01.00
01.00
00.30
04.20
02.1.0
25.00
00.50
01.00
15.00
02.20
02.30
04.80
01.60
03.20
01.90
16.00
01.30
09.40
02.90
02.00
01.10
02.30
04.20
03.00
01.10
01.80
01.50
01.20
01.90
02.00
01.00
03.30
02.10
01.00
01.80
12.00
04.50

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Table 2. Result of Rock-Eval analyses of representative sample from Ousselat Jebel

mg hydrocrbons per g. rock
Sample

TOC (wt %)a

S1

S2

PIb

PPc

HId

OIe

Tmax

AS-01

00.86

00.11

03.03

00.04

03.14

352.0

00.34

434.0

AS-04

00.35

00.08

00.62

00.11

00.70

177.0

01.34

439.0

AS-08

00.64

00.13

01.38

00.09

01.51

216.0

00.91

436.0

AS-12

00.64

00.12

01.69

00.07

01.81

264.0

00.67

433.0

AS-15

00.50

00.12

00.69

00.15

00.81

138.0

01.28

432.0

AS-18

00.83

00.11

02.51

00.04

02.62

302.0

00.46

433.0

AS-22

00.62

00.09

01.25

00.07

01.34

202.0

01.27

435.0

AS-25

00.61

00.08

01.33

00.06

01.41

218.0

01.03

436.0

AS-29

01.32

00.16

05.35

00.03

05.51

405.0

00.38

432.0

AS-33

01.17

00.20

04.66

00.04

04.86

398.0

00.62

431.0

AS-37

00.79

00.16

02.08

00.07

02.24

263.0

01.05

433.0

AS-40

01.76

00.30

07.16

00.04

07.46

407.0

00.52

430.0

AS-43

01.26

00.29

05.11

00.05

05.40

406.0

00.48

432.0

AS-45

01.19

00.22

05.11

00.04

05.33

429.0

00.61

432.0

AS-48

01.66

00.27

07.05

00.04

07.32

425.0

00.44

430.0

AS-51

01.38

00.32

05.86

00.05

06.18

425.0

00.58

429.0

Average

00.97

00.17

03.43

00.06

03.60

292.4

74.90

433.0

a TOC:

Carbone Organique total (weight percent)

PI: Production index (S1/S1 + S2)
c PP: Petroleum Potential (S1 + S2)
d HI: Hydrogen Index (S2/COT 100)
e OI: Oxygen Index (mg CO /TOC 100).
2
b

Rock-Eval Parameters
The bulk of the sedimentary organic matter is
termed kerogen, which is a mixture of large geopolymers formed by either diagenetic repolymerization,
condensation of molecules produced by breakdown of
biopolymers, or by the selective preservation of
biopolymeric debris, which is resistant to alterations [8,
12]. Most of the biopolymers are extensively decomposed during early diagenesis and the organic matter is
composed mainly of kerogen when late diagenesis is
reached. The classification of kerogens by the RE
method is based on the amount of hydrocarbonaceous
compounds yielded by heating experiments carried out
under inert atmosphere.

The RE data for the studied sedimentary rock samples measured by standard RE methods using RE II are
presented in Table 2. This table gives RE parameters of
some outcrop samples judiciously selected from Ousselat Jebel, in western of Kairouan. Because of their
organic matter richness, these facies are selected as a
potential hydrocarbons source rock.
Type and maturity of the organic matter are shown
in the HI versus Tmax diagram (Fig. 5).
Free (SI), and potential (S2) hydrocarbons. SI
is the area of peak PI, which corresponds to thermovaporized free hydrocarbonaceous compounds
present in the rock, volatilizing at temperatures below
300C. Such an area gives the quantity of free hydrocar-

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Hydrogen Index [mg HC/g TOC]

Type-I
750

600

Type-II

450

300

150
Type-III
0
400

420
Immature

440

460

Gas zone

480

500
520
T max (C)
Oil zone

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

bons (oil and gas) contained in the rock, expressed in

mg hydrocarbon per gram of rock. S2 is the area of
peak P2, which corresponds to the hydrocarbonaceous
compounds originating from kerogen cracking (pyrolysis of the kerogen up to 530C). This area (S2) gives the
residual petroleum potential of the rock, expressed in
mg hydrocarbon per gram of rock. S2 additionally corresponds to the thermal degradation products of the
involatile but extractable asphaltenes and resins. In this
study, SI and S2 values show no major differences
between all studied samples. However, the free hydrocarbons (SI) are extremely low ranging: from 0.08 to
0.32 mg hydrocarbon per gram of rock (Table 2). These
low values may reflect the low thermal maturity of
organic matter in Ousselat area. Compared to bitumen
extraction data, these values are relatively low as a
result of peak PI depreciation. S2 ranges from 0.62 to
7.16 mg hydrocarbon per gram of rock, as demonstrated in
Table 2. Generally, all these data show that the petroleum
potantial (S1 + S2) of Ypresian organic-rich facie in the
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studied area is not neglected, reaching 7.46 mg hydrocarbures par g. rock; as demonstrated in Table 2.
Maximum pyrolysis temperature (Tmax). The temperature for which the S2 peak is maximum (Tm) 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 under
analysis [7].
However, in sedimentary series, hydrocarbonaceous
compounds are mainly generated during catagenesis as
a result of thermal degradation of kerogen. Thus, the
more condensed the mature organic matter is, the more
difficult it is to pyrolyze because of higher activation
energies, i.e., a higher temperature is required to crack
the condensed structure. In addition, heating experiments proved that organic fragments inherited directly
from organisms with no or minor change (linked to kerogen by chemical bonds or entrapped in the kerogen
matrix) are also mostly released upon catagenesis. In
this study, Tm values range from 429C to 439C
(Table 2). Generally, all the Tm values suggest that the
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As-49

Pr

As-04

Time

n-C23
n-C24

n-C21
n-C20

n-C19

n-C18

n-C16
n-C17

n-C22

Response

n-C21

n-C19

n-C20

n-C16

n-C18

n-C15

Ph

n-C25
n-C26
n-C27
n-C28

n-C24
n-C25
n-C26
n-C27

n-C14

n-C15

n-C17

Response

Ph

n-C22
n-C23

Pr

Time

(n-C14) Tetradecane; (n-C15) Pentadecane; (n-C16) Hexadecane; (n-C17) Heptadecane; (n-C18) Octadecane;
(n-C19) Nonadecane; (n-C20) Eicosane; (n-C21) Heneicosane; (n-C22) Docosane; (n-C23) Tricosane; (n-C24) Tricosane;
(n-C25) Pentacosane; (n-C26) Hexacosane; (n-C27) Heptacosane; (n-C28) Octacosane; (c) 2,6,10-trimethyldodecane;
(d) 2,6,10-trimethyltridecane; (e) 2,6,10-trimethyltetradecane; (f) nor-pristane; (Pr) pistane; (Ph) Phitane;
(g) 2,6,10,14,18-pentamethyleicosane.
Fig. 6. Mass ghromatograms (m/z 99) of the aliphatic hydrocarbon fractions for representative samples from Ousselat Jebel.

organic matter has reached a relative low thermal maturity in Ousselat area, corresponding to the end of
diagenesis and the beginnig of catagenesis.
On the other hand, types-I (and II) kerogens are
known to have relatively simpler molecular compositions and structures than type-III. For type II, the
beginning of the oil genesis occurs at lower maturities
(around 0.6% Ro equivalent and Tm = 430435C)
[13, 14].
Thus, in this study the relative low Tm values of the
studied samples may reflect the fingerprint of dominantly type-II organic matter as demonstrated by the predominance of saturated hydrocarbons over aromatics.
Hydrogen and oxygen index. The ratio of S2 to the
total organic carbon (TOC) of the rock is the hydrocarbon index (HI). This latter is a key source rock parameter used in the quantitative modelling of the phase and
volume of expelled hydrocarbons [14] and the classification of the kerogen type. Peters [15] proposed the following three-fold classification of kerogen, assuming a
level of thermal maturation equivalent to Ro 0.6%.
(1) oil-prone: HI > 300 (mg HC/g TOC)
(2) gas- and oil-prone: HI 200300
(3) gas-prone: HI 50200.
In our study, the marine source of Ypresian organic
matter is supported by the dominance of algal-derived
organic matter with HI-values ranging from 138 to
429 mg HC/g TOC (Table 2). On the other hand, the

peak P3 corresponds to the CO2 released during the

pyrolysis; the ratio of the peak area S3 and the TOC
gives the oxygen index (OI). Rock Eval analysis of bulk
samples provided low OI values of 34 to 134 (mg CO2/g
TOC) (Table 2). Classifying the OM and specifying its
main biological precursors is obtained on the basis of a
diagram of HI versus Tm. Figure 5 shows the relationship between hydrogen index, Tm, and kerogen types.
According to this figure, the predominance of marine
source is clearly indicated for the Ypresian organic. The
comparison of Tm-temperatures with Hi-indices
allows us to define three organic matter evolution pathways [16]. Therefore, the localization of samples
within HI-vs. Tm-diagram suggests that the Ypresian
organic matter is at the end of diageneisis/beginning of
catagenesis
Total Organic Carbon (TOC)
The measurements of TOC were performed using
Rock-Eval II module. Table 2 shows TOC distribution
of the studied outcrop samples.
It is revealed that the sediments in Ousselat Jebel
display a clear fluctuation of TOC values. Some samples are lean in organic matter (<1 wt %). In contrast, several samples contain visible carbonaceous matter and
show high TOC values (reached 1.76 wt %) (Table 2). The
organic content of sediments can be attributed to three
factors: the primary biological productivity, the preservation rate of organic matter and the rate of organic

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Table 3. Analytical results of n-alkanes for the representative samples from Ousselat Jebel
n-Alkanes

Isoprenoids

Sample
Range

Cmax

Pristane/Phytane

Pr/n-C17

Ph/n-C18

AS-04

C14C27

C18 (monomodal)

1.88

2.42

1.17

AS-08

C15C27

C18 (monomodal)

1.48

1.96

1.27

AS-12

C15C26

C18 (monomodal)

2.03

2.46

1.11

AS-18

C15C27

C21 (monomodal)

2.23

4.61

1.67

AS-25

C15C27

C21 (monomodal)

1.84

2.70

1.35

AS-29

C15C26

C21 (monomodal)

0.99

4.37

2.12

AS-33

C15C27

C21 (monomodal)

1.80

3.68

1.80

AS-37

C15C28

C21 (monomodal)

1.28

1.40

0.84

AS-43

C15C27

C21 (monomodal)

1.74

4.45

2.18

AS-48

C15C26

C21 (monomodal)

0.97

3.13

1.86

AS-49

C15C27

C21 (monomodal)

1.97

3.00

1.34

1.65

3.10

1.52

Average

A = Pristane/n-C17

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The n-alkane distributions have been used to indicate the organic sources, depositional environments
and secondary process [15]. It is known that the molecularly light n-alkanes (< C21) are derived from algae
and bacteria (Wakeham, 1990), while the molecularly
heavy homologues (> C22) mainly originate from the
wax of higher plants [17].
In this present study, m/z 99 fragmentogram (Fig. 6)
indicate that hydrocarbons present in the sediments at
Ousselat Jebel have carbon numbers ranging from 13
through 28. As shown in Fig. 6, three n-alkane series,
i.e., n-13 ~ n-C20, n-20 ~ n-C25, and n-25 ~ n-C28 alkane

10

n-Alkanes Distribution

series are present in the sediments. Generally speaking,

the n-C13 ~ n-C21 alkane series is related to the organic
source of microorganisms and/or algae [15]. If the signatures of algal-marine type-II organic matter are
clearly present with a predominance of short-chain
n-alkanes (n-C13 ~ n-21), those of continental higher

deposition versus mineral deposition [8]. The relatively

low TOC content measured on some outcrop samples
(Table 2) is probably due to the dilution effect caused
by a high sedimentation rate and poor preservation of
the fresh organic matter. However, it is known that the
low abundance of TOC suggest that a relative oxicity of
the depositional environment affects the amount and elemental composition of the stored organic matter. In contrast, the less oxic environment promoted better organic
preservation in the depositional environment [8].
On other hand, the majority of the samples display a
relative high TOC contents. This result is due to Ypresian episode, which is generally more conductive for
preserving/accumulating relative high amounts of
organic matter.

A/B = 2
A/B = 1

F/B = 0.5
ON

I
AT

0.1

RE

CI

UR

AT

0.1

1
B = Phytane/n-C18

Fig. 7. Location of representative samples of Ousselat Jebel

in the diagram Pristane/n-C17 vs. Phytane/n-C18.
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18

As-29

15

25
29

5
19

10
22
9 13 16
27
21
78
17
26 28
20

RESPONSE

24 23

11,12
14

30

31
32 33

18
5

As-48

15

25

21
22

10

29

13 16 19

17

20

26

28

27
24 23

79
8

11,12
14

30
31 33
32

TIME
Fig. 8. Mass chromatograms (m/z 217) showing the distribution of steranes in some representative samples from Ousselat area.

plants with a predominance of long-chain odd-carbon

numbers are undetectable. This is evident from the unimodal hydrocarbon distribution with a major mode
centred at n-C18 or n-21.

as originally proposed by Lijmbach (1975), infers that the

Ypresian organic matter from the Ousselat area was
deposited under oxic to suboxic conditions.

Pristane and phytane also occur in very high concentrations in sample extracts (Fig. 6 and Table 3). The
two isoprenoids, pristane (Pr) and phytane (Ph), were
proposed to be primarily derived from the phytyl side
chain of chlorophyll in phototrophic organisms. During
early diagenesis, under anoxic conditions the phytyl
side chain is cleaved to yield phytol, which is reduced
to dihydrophytol and then phytane (20). In contrast,
under anoxic conditions, phytol is oxidized to phytenic
acid, decarboxylated to pristene and then reduced to
pristine (C19) [8, 15]. In the present study, the (Pr/Ph)
ratios of the most outcrop samples rise from 0.97 to
2.23 (Table 3). Thus, the relatively high Pr/Ph ratios
imply that the Ypresian organic matter was, probably,
deposited in suboxic depositional environments in the
Ousselat area [18, 19].

Steranes Distribution
Mass chromatograms (m/z 217) show that the distributions of steranes were remarkably similar for representative outcrop samples. They comprise most of the
known C26 to C30-pseudohomologues and diasteranes
(Fig. 8 and Table 4). The molecularly lighter C21 and
C22 steranes (pregnanes) also occur in the bitumen.
Regular steranes are generally biomarkers indicating organic matter sources that contributed to the
organic portion of the sediment. The following compounds have been identified: C27-cholestane, C28-ergostane, C29-stigmastane and propylcholestanes with their
20S and 20R epimers (Philp, 1985). In this work,
Cholestane (C27) was consistently the most abundant
pseudohomologue [comprising 42 to 48% of the total
C27 to C29-regular-steranes (Table 5)], followed by
ergostane (C28) [comprising (2834%)] and stigmastane (C29) [comprising (2426%)]. The predominance
of C27 and C28 indicate a predominance of marine phytoplankton and lacustrine algae, respectively [20, 21].

On the other hand, Pr to normal C17-alkane (r/n-17)

and Ph to normal C18-alkane (Ph/n-C18) ratios are quite
varied, ranging from 1.40 to 4.45 and 0.84 to 2.18, respectively (Table 3). The Pr/n-C17 vs. Ph/n-C18 diagram (Fig. 7),

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Table 4. Identification of peaks in the m/z 217 fragmentograms
Peak
number

Formula

Molecular weight

C2lH36

288

diapregnane

C21H36

288

5(H), 14(H), 17(H)-pregnane

C22H38

302

Diahomopregnane

C22H38

302

5(H), 14(H), 17(H)-methy lpregnane

C27H48

372

13(H), 17(H)-diacholestane (20S)

C27H48

372

13(H), 17(H)-diacholestane (20R)

C27H48

372

13(H), 17(H)-diacholestane (20S)

C27H48

372

13(H), 17(H)-diacholestane (20R)

C28H50

386

13(H), 17(H)-24-methyldiacholestane (20S) 24R/S isomers (?)

10

C28H50

386

13(H), 17(H)-24-methyldiacholestane (20S) 24R/S isomers (?)

11,12

C28H50

386

13(H), 17(H)-24-methyldiacholestane (20S) 24R/S isomers (?)

13

C28H50

386

13(H), 17(H)-24-methyldiacholestane (20S)

14

C27H48

372

5(H), 14(H), 17(H)-cholestane (20S)

15

C27H48

372

5(H), 14(H), 17(H)-cholestane (20R) +

C29H52

400

13(H), 17(H)-24-ethyldiacholestane (20S)

16

C27H48

372

5(H), 14(H), 17(H)-cholestane(20S)

17

C28H50

386

13(H), 17(H)-24-methyldiacholestane (20R)

18

C27H48

372

5(H), 14(H), 17(H)-cholestane (20R)

19

C29H52

400

13(H), 17(H)-24-ethyldiacholestane (20R)

20

C29H52

400

13(H), 17(H)-24-ethyldiacholestane (20S)

21

C28H50

386

5(H), 14(H), 17(H)-24-methyldiacholestane (20S)

22

C29H52

400

13(H), 17(H)-24-ethyldiacholestane (20R)

23

C28H50

386

5(H), 14(H), 17(H)-24-methy lcholestane (20R)

24

C28H50

386

5(H), 14(H), 17(H)-24-methylcholestane (20S)

25

C28H50

386

5(H), 14(H), 17(H)-24-methylcholestane (20R)

26

C29H52

400

5(H), 14(H), 17(H)-24-ethylcholestane (20S)

27

C29H52

400

5(H), 14(H), 17(H)-24-ethylcholestane (20R)

28

C29H52

400

5(H), 14(H), 17(H)-24-ethylcholestane (20S)

29

C29H52

400

5(H), 14(H), 17(H)-24-ethylcholestane (20R)

30

C30H54

414

5(H), 14(H), 17(H)-24-propylcholestane (20S)

31

C30H54

414

5(H), 14(H), 17(H)-24-propylcholestane (20R)

32

C30H54

414

5(H), 14(H), 17(H)-24-propylcholestane (20S)

33

C30H54

414

5(H), 14(H), 17(H)-24-propylcholestane(20R)

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Table 5. Sterane biomarker parameters in some representative samples from Ousselat r

Sterane (%)a
Isosteranes
(%)b

Sample
C27

C28

Diasteranes
indexc

20S/ (20S + 20R)d

/ ( + )e

PIf

C29

AS-01

42

32

26

22

0.82

0.34

0.43

15.00

AS-29

48

28

24

21

0.86

0.22

0.39

17.00

AS-48

42

34

24

20

1.03

0.26

0.58

15.00

Average

44.00

31.33

24.66

21.00

0.90

0.28

0.47

15.70

5(H), 14(H), 17(H)-20R-steranes.

Ratio of concentrations of the isosterane series to concentrations of total sterane 100.
c 24-ethyl-13(H)-17(H)-diacholestanes (20R + 20S)/[24-ethyl-14(H)-17(H)-cholestanes (20R + 20S) + 24-ethyl-14(H)-17(H)-cholestanes
(20R + 20S)].
d 20S/(20S + 20R) for C -5(H), 14(H), 17(H)-steranes.
29
e 5(H), 14(H), 17(H)/[5(H), 14(H), 17(H) + 5(H), 14(H), 17(H)] for C -steranes.
29
f Pregnane index, sum of concentrations of C and C steranes (pregnanes) over total
concentration of steranes 100.
21
22
b

The homologous distributions of steranes C27C28

C29 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
show that the outcrop samples are indistinguishable by
sterane distributions, indicating these oils were derived
from marine source.
It is generally considered that diasternaes formation
is mainly controlled by three factors: clay mineral

catalysis, thermal maturation and oxic/anoxic depositional conditions [20]. Diasterane/sterane ratios are
commonly used to distinguish carbonate from clay-rich
source rocks. However, low diasterane/sterane ratios
are associated with anoxic, clay-poor, 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 [15].

C27(%)
0 100

25

75

As-29

50
As-48

50

As-01

75

100
C28(%) 0

25

25

50

75

0
100 C29(%)

Fig. 9. Ternary plot showing the relative distribution of C27C28C29 steranes in the studied samples.
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ORGANIC GEOCHEMICAL STUDY OF YPRESIAN SEDIMENTS AT JEBEL OUSSELAT

Table 5 shows that the diasteranes index of the represented samples rises from 0.82 to 1.03. The relative
abundance of diasteranes in organic matter implies the
generation of these oils from source rocks relatively
rich in clay minerals.
Molecularly light steranes, i.e., pregnane (C2-sterane) and methylpregnane (C22-sterane), typically
appear in highly mature condensates [15]. In our Ypresian outcrop samples, the C21 and C22 steranes are significantly abundant compared to C27-steranes (Fig. 8;
Tables 4 and 5). The occurrence of pregnanes is a good
indicator of the relative maturity and/or alteration of
organic matter in the Ypresian basin.
Maturity Parameters of Steranes
20S/(20S + 20R) and bb/(aa + bb)-C29 steranes
ratios. One major application of steranes in organic
geochemistry is determining maturity based on thermal
effects of their basic skeletons on the stereochemical
complexity. Only the R configuration 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 configurations. The
extent of side-chain epimerisation at C-20 (20R = 20R +
20S), measured as 20S/(20S + 20R) for the 5(H)14(H),
17(H) C29-steranes, rises from 0 to about 0.5 (0.52 to
0.55 = equilibrium, equivalent to Ro = 0.8%) with increasing maturity [15]. Thus the ratios [20S/(20S + 20R)] for
C29 steranes are the only epimer ratios that could be measured with confidence (Table 5).
Another maturity parameter derived from C29 regular steranes is the proportion of 5(H), 14 (H), 17 (H)
C29 sterane and 5(H), 14(H), 17(H) C29 sterane
forms (isomerization at 14 and C17) expressed as the
ratio /( + ) sterane. As maturity increases,
the form, which is produced biologically, converts
gradually into a mixture of and . The equilibrium
value is about 0.670.71 [22]. This ratio is somewhat
slower to reach equilibrium than the 20S/(20S + 20R)
ratio, thus making it effective at higher levels of maturity.
In this present study, samples are dominated by 5,
14, 17(H)-20R and 5, 14, 17(H)-20R steranes
(biological configuration) (Fig. 8, Table 4). This steroid
hydrocarbon fingerprint is typical of thermally immature sediments [15]. The ratios of 20S/(20S + 20R) for
C29 steranes and /( + ) for 5-29 steranes
in the Ypresian outcrop samples (Table 5) are 0.22 to
0.34 and to 0.39 to 0.58, respectively. These relatively
low values suggest that these oils were dominantly generated prior to the peak stage of the conventional oil
window.
Diasteranes/regular steranes ratios. Ypresian
organic matter contains diasteranes in predominantly
20S configuration relative to C27, C28, and C29-diasteranes (Fig. 8). This steroid hydrocarbon fingerprint indicates thermally mature organic matter. The high conGEOCHEMISTRY INTERNATIONAL

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centration of diasteranes may be attributed to the higher

maturity of the organic matter [15]. Furthermore, the
concentration of diasteranes might also increase, compared to regular steranes, with thermal maturity [23]
and might be influenced by chromatographic processes
during subsurface fluid flow [24]. In the Ypresian bitumens, the diasteranes index is subject to large variations (Table 5). The observed values are probably consistent with the relatively high thermal maturities (end
of diagenesis/beginning of catagenesis).
Biodegradation-Weathering Effects
Many authors have observed that n-alkanes are utilized first by bacteria, then by acylic isoprenoid alkanes
and alkyl cycloalkanes, while the molecularly lighter
compounds are preferably consumed [25, 26]. In this
respect, Pristane/n-17 (Pr/n-17) and phytane/n-C18
(Ph/n-C18) indices have been widely used as indicators
of oil biodegradation [27, 28]. As the easily degraded
normal hydrocarbons (n-C17 and n-C18) are lost, the
more degradation resistant isoprenoids (pristane and
phytane) are conserved, resulting in a relative increase
of the ratios of Pr/n-C17 and Ph/n-C18 in outcrop samples
(Fig. 7).
The epimer ratios of 20S/(20S + 20R) for the C29
steranes are commonly used as maturity parameters
[29] and as source tracers of weathered oil residues
[30]. It was also possible that sterane isomers might be
selectively degraded or lost during severe weathering
processes [30]. The lower C29 20S/(20S + 20R) might
be caused by the selective loss of sterane isomers during severe weathering processes.
The value of the pregnane index (PI in Table 4),
defined as the percentage of the concentrations of C21
and C22 steranes (compounds 14 in Table 4) to the total
concentration of steranes (compounds 133 in Table 4),
range from 15 to 17% for the representative samples,
indicated a slight difference which may be the result of
the degree of conservation of the organic matters.
The relative abundances of isosteranes in Ousselat
samples were 2022% (Table 5). This may be the result
of the severe weathering, which could have resulted in
the loss of more isosteranes than other steranes.
CONCLUSIONS
The main conclusions of this work are summarized
below:
According to Rock-Eval pyrolysis, the organic matter was easily recognizable in most of the studied samples with high contents of total organic carbon (TOC).
The organic matter of the richest samples is typically
marine plankton (type II). This assumption is supported
by the high Hi-values and the low OI-values. Tmax values support the low level of Ypresian organic matter
maturity as indicated by the predominance of the hetero
(NSO) compounds.
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Utilizing the GC/MS technique made it possible to

arrive at a clear characterization and classification of
organic matter according to its source. This has been
achieved from n-alkanes and steranes biomarkers. The
presence of steranes with a predominance of C27 over
C28 and C29R configurations suggests favorable
conditions for deposition of algae or bacterial source
organic matter in suboxic environments. The thermal
maturity level, assessed by values of several biomarker
parameters, has been estimated to be at the end of
diagenesis/beginning of catagenesis and corresponds to
the theoretical vitrinite values (R0) in the range 0.53
0.63%.
The Ypresian period was prone to the preservation
of organic matter in suboxic environments. Due to these
geochemical features, Ousselat could be a promising
area for hydrocarbon exploration in Central-northern
Tunisia.
ACKNOWLEDGMENTS
Financial support for this study was provided by
GEOGLOB (code : 03/UR/10-02). We are grateful to the
crew of LARSEN (Sfax) for providing GC/MS facilities and we are especially deeply indebted to Dr. M. Kallel
for providing logistical support. The authors are also
deeply indebted to Drs. N. Chine and M. Saidii from
E.T.A.P. (Tunis) for their assistance with Rock-Eval pyrolysis. Our special thanks go to anonymous reviewers for
their help.
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