Journal of African Earth Sciences 161 (2020) 103676

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Journal of African Earth Sciences

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Assessment of sedimentary environment from PAHs and aliphatic T

biomarkers: The case study of Fahdene black shales in northern Tunisia
Tahani Halleka,∗, Dhaou Akrouta, Riadh Ahmadib, Mabrouk Montacera
a
Research Unity of Geo-systems, Geo-resources and Geo-environments (UR3G), Faculty of Science of Gabes, University of Gabes, City Campus Erriadh-Zrig, 6072, Gabes,
Tunisia
b
Research Laboratory of Water, Energy and Environment (LR3E), University of Sfax, Road of Aeroport Km 0.5BP 1169, 3029, Sfax, Tunisia

ARTICLE INFO ABSTRACT

Keywords: Polyaromatic and aliphatic biomarkers extracted from the Albian-Early Cenomanian source rock (Fahdene
Albian-cenomanian Formation) were evaluated by Gas Chromatography – Mass Spectrometry (GC-MS) and are compared to classic
Fahdene geochemical and mineralogical data. In addition to terpanes, hopanes, diasteranes and steranes, thirty-seven
Source rock aromatic hydrocarbon elements were identified.
Biomarkers
The absence of the angiosperm-derived biomarker (18α(H)-Oleanane) and the low abundance of tri-
Fracture
Tunisia
methylnaphthalenes isomers (1,2,5-TMN and 1,2,7-TMN) suggest that no land-plant traces were founded in the
studied organic matter. In this fact, the Kerogene III identified by Rock Eval is not detected, and we can attribute
these indices to the algae effect. The check of maturity by Tmax and the biomarker parameters (C27 18α-
22,29,30-trinorneohopane (Ts), sterane isomerization ratio ββ/(αα+ββ), C32 22S/(22S + 22R) HH and the
methylphenanthrene index (MPI-1)) indicates that these organic rich sediments are reached the early stage of oil
window. In the other hand, aliphatic and polyaromatic biomarkers confirm classic data of X-ray diffraction and
calcimetry and suggest a carbonate facies with some clayey intercalations in the middle part. The fracturing
analysis of these carbonates prove the presence of high density of fractures with various sizes and directions.
About filling, the fibrous calcite is the major element of mineralized veins, with the presence of bitumen traces.
These fractures have two main orgin; the fluid pressure and the regional tectonic stress regime.
Therefore, the Albian-Early Cenomanian fractured carbonates in the Mahjouba area were deposited, under
suboxic conditions, in a marine environment affected by the eutrophication phenomenon, and have just reached
the equilibrium stage of maturity.

1. Introduction
Biomarkers or biological markers (Eglinton et al., 1964; Eglinton
and Hamilton, 1967) are a molecular fossils used because of their
complex composition in order to identify several geochemical para-
meters (origin, stage of maturity, lithology; Peters and Moldowan,
1993; Waples and Curiale, 1999) for crude oils, petroleum seeps and
source rocks. Biodegradation can affect these biomarkers according to
their structure, and both aliphatic and aromatic biomarkers provide
good results about the characterization of organic contents. However,
using aromatic compounds is more credible for the identification of the
organic matter origin, and because of their complex structures, micro-
organisms and bacteria do not biosynthesize complex cycles of hydro-
carbons in appreciable quantities (Hase and Hites, 1976). For this
reason, we choose to apply the concept of polyaromatic biomarkers and
relate their presence with the environment of deposit during the Albian-
Early Cenomanian. Burollet (1956) attributed the Fahdene Formation
to this interval characterized in Northern Tunisia by the abundance of
organic rich sediments and the expansion of the oxygen minimum zones
(OMZ) in the sedimentary basins (i.g. Talbi, 1991; Saidi and Belayouni,
1994; Amédro et al., 2005; Robaszynski et al., 2007; Robaszynski et al.,
2010; Ben Fadhel et al., 2011).
Previous works (e.g. Ben Fadhel et al., 2011; Soua, 2015; Zina et al.,
2018; Touati and Haji, 2019) using classic geochemical data and ali-
phatic biomarkers, show that the Fahdene organic matter have a mix-
ture origin (marine and continental), and have been deposited in a
platform environment with land-plant input. The purpose of this paper
is to extract the aromatic compounds from the Fahdene Formation and
to use these biomarkers for the first time to control the organic matter
input, to determinate the environment of deposit and to highlight

∗
Corresponding author.
E-mail address: tahanihallek@gmail.com (T. Hallek).

https://doi.org/10.1016/j.jafrearsci.2019.103676
Received 25 April 2019; Received in revised form 26 September 2019; Accepted 22 October 2019
Available online 25 October 2019
1464-343X/ © 2019 Elsevier Ltd. All rights reserved.
T. Hallek, et al.
Fig. 1. Location map of Jebal Mahjouba (from the geological map of Kalaat Senan 1/50000).
biological and geological process controlling the deposit palaeoenvir-
onment of Fahdene black shales.
2. Geological setting
The study area (Mahjouba structure) is located in Northwestern
Tunisia, in the South of Tedjerouine city (Fig. 1). The paleogeography
of this structure, during the Albian-Early Cenomanian, corresponds to a
transition platform limited in the South by the stable continental shelf
and the deep basin towards the North (Fournie and Pacaud, 1973; Zghal
and Arnaud, 2005; Chihaoui et al., 2010). Jebal Mahjouba is a mono-
cline truncated by the Kalaa Khasba trough (Fig. 1; Zaier, 1999;
Ouertani, 2004).
During the Aptian-Albian transition, Northwestern Tunisia was an
external platform marked by several sea level fluctuations and con-
tinental inputs causing episodic emersion and submersion anomalies
(Zghal and Arnaud, 2005; Chihaoui et al., 2010). The Aptian subsidence
variations cause an evident hiatus in Tunisia during this transition (Ben
Ferjani et al., 1990; Zghal et al., 1997; Ouahchi et al., 1998; Marco
et al., 2014). This sedimentary gap was explained by tectonic activities
and eustatic events (e.g. Rabhi and Ben Ayed, 1990; Bouaziz et al.,
2
Journal of African Earth Sciences 161 (2020) 103676
2002; Zghal and Arnaud, 2005).
The Albian transgression in Central and Northern Tunisia was
controlled by a deep sediments onlapping the pre-existent Aptian
platform (Zghal and Arnaud, 2005). Then, during the Early and Middle
Albian, syn-sedimentary deformations affected the deposition of the
Fahdene organic matter and these tectonic anomalies were sealed by
the Upper Albian (Rigane et al., 2010; Jaillard et al., 2013).
During the Cenomanian, the study area was characterized by a
transitional environment of deposit from the carbonate shelf towards
the deep terrigenous facies (Robaszynski, 2005). These successions of
marly basinal sediments include the Upper Fahdene and the lower part
of Bahloul black shale (Robaszynski, 2005). This variability of facies
was controlled by halokinetic activities (Bechtel et al., 1998; Lüning
et al., 2004; Soua and Tribovillard, 2007; Soua et al., 2009; Soua,
2015).
3. Lithostratigraphy
The basement of the studied section is characterized by black
sandstone argilites with ferrous minerals traces, interbedded with car-
bonates, forming the top of Hameima Formation (Burollet, 1956;
T. Hallek, et al. Journal of African Earth Sciences 161 (2020) 103676

Fig. 2. Simplified stratigraphic column of Albian-Cenomanian Fahdene Formation outcrop in the study area.

Table 1
Bulk geochemical and mineralogical results for Fahdene Formation samples.
Samples TOC Tmax S1 S2 S3 PP IH IO CaCO3 EOM SAT AROM NSO SAT/AROM

Fah-11 0.87 444 0.09 0.45 0.12 0.54 51.72 13.79 75.18 9.25 14.62 31.21 54.17 0.47
Fah-10 1.06 446 0.1 1.33 0.51 1.43 125.47 48.11 75.67 8.00 11.21 33.14 55.65 0.34
Fah-9 0.98 447 0.03 2.01 0.45 2.04 205.10 45.92 63.45 13.50 2.11 10.25 87.64 0.21
Fah-8 0.46 446 0.04 0.98 0.18 1.02 213.04 39.13 17.72 4.00 9.14 23.11 67.75 0.40
Fah-7 1.97 445 0.09 4.05 0.94 4.14 205.58 47.72 47.83 3.65 6.72 15.06 78.22 0.45
Fah-6 1.22 447 0.12 1.3 0.88 1.42 106.56 72.13 17.91 2.25 9.02 15.74 75.24 0.57
Fah-5 0.93 444 0.09 0.41 0.29 0.5 44.09 31.18 5.81 2.25 14.17 29.15 56.68 0.49
Fah-4 0.48 446 0.11 0.54 0.41 0.65 112.50 85.42 44.41 2.40 22.98 30.45 46.57 0.75
Fah-3 0.53 445 0.14 1.02 0.44 1.16 192.45 83.02 64.94 2.25 10.65 21.84 67.51 0.49
Fah-2 0.28 445 0.01 0.12 0.18 0.13 42.86 64.29 45.24 2.50 3.22 24.61 72.17 0.13
Fah-1 0.62 447 0.02 0.11 0.22 0.13 17.74 35.48 52.52 2.20 4.04 30.87 65.09 0.13

TOC: total organic carbon (%), Tmax: S2 maximum peak temperature (°C), S1 (mg HC.g-1 rock), S2 (mg HC.g-1 rock), S3 CO2 (mg CO2.g-1 rock), PP: Petroleum
potential (mg HC.g-1 rock), IH: Hydrogen Index (mg HC.g-1 TOC), IO: Oxygen Index (mg CO2.g-1 TOC), CaCO3: Rate of calcium carbonate (%), EOM: extractable
organic matter, SAT: Saturate hydrocarbon fraction, AROM: Aromatic hydrocarbon fraction.

Dubourdieu, 1956). The Fahdene Formation is mainly composed of
marls, calcareous claystone and argillaceous limestone beds. These li-
thostratigraphic changes are in accordance with eustatic variations
(Albian transgression, Burollet, 1956; ERBA, 1996; Hart et al., 1996;
Kennedy et al., 2000; Hancock, 2001; Owen, 2002; Chihaoui et al.,
2010), and tectonic upheavals (Cotillon, 1989; Guiraud and Maurin,
1992; Chaabani and Razgallah, 2006; Bouaziz et al., 2002; Bulot and
Ferry, 2007) (the Austrian and Albian unconformities) accompanied the
Aptian-Albian rifting (Rigane et al., 2010). Depending on the synthetic
lithostratigraphic column (Fig. 2), The Fahdene Formation is divided in
three main parts; 1). The basement is a limestone dominated interval
with dark marls levels, 2). The middle part includes grey marls

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T. Hallek, et al.
Fig. 3. Rock Eval parameters of the Fahdene studied samples.
interbedded with argillaceous limestone beds, 3). The top of Fahdene is
controlled by carbonate sediments and argillaceous laminated lime-
stone intercalations.
4. Material and methods
This study is based on 11 samples of the Fahdene black shales col-
lected from Mahjouba outcrops. These samples were carefully chosen
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Journal of African Earth Sciences 161 (2020) 103676
by referring to the organic richness, and they were finely powdered, by
an automatic pounder, prior to analysis.
Bulk organic geochemical parameters were determined using
RockEval pyrolysis under standard conditions with a Rock-Eval 6 ap-
paratus (Espitalié et al., 1985; Lafargue et al., 1998; Behar et al., 2001).
The Rock-Eval pyrolysis method is based on heating a small amount of
rock (100 mg) using a programmed temperature under inert atmo-
sphere (helium). Free hydrocarbons pre-existing in the rock are
T. Hallek, et al.
Fig. 4. Vertical variation of geochemical and mineralogical parameters. TOC: total organic carbon, CaCO3: carbonate rates from calcimetry analysis, EOM: ex-
tractable organic matter, SHC: saturated hydrocarbons, AHC: aromatic hydrocarbons, NSO: polar compounds.
expelled at 300 °C without cracking (S1; mg HC/g Rock). S2 peak
presents the potential hydrocarbons (mg HC.g-1 rock) expelled after the
thermal cracking of kerogen (300–550 °C). The third peak S3 is the
quantity of evolved CO2 (mg HC/g rock) after pyrolysis (300–390 °C).
Tmax (°C) is the Rock-Eval pyrolysis oven temperature at the maximum
of hydrocarbons peak (S2) used to measure thermal maturity (Hunt,
1996).
Soluble factions (bitumen) were extracted from powdered samples
using organic solvent (Dichloromethane, CH2Cl2, 150 ml/20 g sample).
Then, we obtained the bitumen or the extractable organic matter (EOM)
(Durand, 1993; Hunt, 1995). The EOM was fractionated using liquid
chromatography with a single column packed with activated silica gel
and alumina (65:35, v/v). The column was eluted with pentane to
obtain the saturate hydrocarbons and with pentane/CH2Cl2 (65:35, v/
v) to obtain the aromatic fraction. The NSO fraction was retained at the
top of the column because of its polarity.
The Gas Chromatography Mass Spectrometry (GC-MS) of saturated
and aromatic hydrocarbon fractions were analyzed on Agilent 7890
Series coupled to Agilent 5973 Series Mass Selective Detector (Peters
et al., 2005). The separation was carried out using a DB-1MS of
30 m × 0.32 mm x 0.25 μm capillary column operated at constant flow
(3.2 ml/min). Column program started at 50 °C (2 min) to 170 °C at
5 °C/min and to 300 °C at 1.5 °C/min, for saturated fractions. For aro-
matic hydrocarbons, column program started at 80 °C (2min) to 300 °C
at 3 °C/min. The ion source was operated in electronic impact (EI) mode
at 70 eV at 280 °C. The MS was operated in selective ion monitoring
(SIM) for the following ions: alkanes (m/z 57), steranes (m/z 217),
terpanes (m/z 191) and PAHs (m/z 142, 156, 170, 178, 184, 192, 198).
The mineralogical analyses were effectuated by X-ray diffraction
(XRD) with a Philips X'Pert diffractmeter via Cu Kα radiation
(1.5418 Å). The content of total calcium (CaCO3) was estimated by the
Bernard calcimeter method (Müller and Gastner, 1971; Vatan, 1967;
Nelson, 1982). Thin sections are observed by optical microscopy.
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Journal of African Earth Sciences 161 (2020) 103676
5. Results
5.1. Bulk chemical compositions
The TOC content of samples from the Fahdene Formation are dis-
played in Table 1. TOC and pyrolysis S2 yield range from 0.3 to 2% and
from 1.3 to 4.05 mg HC/g rock, respectively. Hydrogen Index (HI) and
Tmax vary between 18 and 206 mg HC/g TOC and 444–447 °C, re-
spectively. Tmax reflects thermal maturity (Espitalié et al., 1977), but
may also be influenced by kerogen type (Hunt, 1996; Vecoli et al.,
2009). Thus, the typical HI-Tmax (Fig. 3) correlation indicates that
Fahdene samples are plotted in the mature Type II-III organic matter
region.
5.2. Bitumen richness and composition
The extractable organic matter (EOM) ranges from 2.2 to 13.5%
(Table 1), and the polar components were the major fractions with
percentage of 47–88% (Table 1, Fig. 4). The low saturate/aromatic
ratios (< 0.6) are related to the remaining phase of hydrocarbons
(Curiale and Bromley, 1996; Dzou and Hughes, 1993; Matyasik et al.,
2000; Thompson, 1987, 1988; Van Graas et al., 2000; Zhang, 2000).
5.3. Normal -alkanes characteristics
The total ion chromatograms (TICs) of saturated fractions show that
the n-alkanes are the main compounds with a significant dominance of
C16–C20 short-chain, and a maximum at C17 (Fig. 5). Long-chain n-al-
kanes (> C27) present less than 20% of the saturated fraction. Ad-
ditionally, the studied samples have high ratios of ∑C21−/∑C22+ and
(C21+C22)/(C28+C29) in the range of 1.06–1.33 and 4.41–8.14, re-
spectively.
The degree of waxiness expressed by the Σ(C21–C31)/Σ(C15–C20)
ratio, ranging from 0.4 to 0.55 (Table 2), indicates low land-plant input.
The carbon preference index (CPI) and the odd-to-even predominance
(OEP), obtained from the n-alkanes distribution, range from 1.07 to
T. Hallek, et al. Journal of African Earth Sciences 161 (2020) 103676

Fig. 5. (a) Partial m/z 85 GC-MS of aliphatic hydrocarbon fractions from lower (Fah-1), middle (Fah-3; Fah-7) and upper (Fah-10) Fahdene showing n-alkanes and
isoprenoids distributions. (b) Normalized n-alkanes profiles for the studied samples.

1.28 (average 1.24) and 0.97–1.04 (average 1.02), respectively in the range of 2.08–2.87 and the isoprenoid/n-alkanes ratios vary from
(Table 2). 0.76 to 1.23 and 0.39 to 0.52 for the Pr/n-C17 and Ph/n-C18 respectively
The 2,6,10,14-tetramethyl pentadecane (pristane) is more abundant (Table 2).
than 2,6,10,14-tetramethyl hexadecane (phytane). The Pr/Ph ratios are

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T. Hallek, et al. Journal of African Earth Sciences 161 (2020) 103676

Table 2 dominated by C31HH. The homohpane index HHI = [C35/∑(C31–C35)

Biomarkers parameters based on GC-MS results from the Fahdene source rock (22S + 22R)] have high values (Table 2) varied from 0.08 to 0.18, and
aliphatic fractions. the C35/C34HH ratios range in the 0.69–1.02 interval.
Parameters Fah-1 Fah-3 Fah-7 Fah-10 The 18α(H)-22,29,30-norneohopane (Ts) has a little abundance
comparing to 17α(H)22,29,30-norhopane (Tm), and Ts/(Ts + Tm)
N-alkanes Pr/Ph 2.08 2.12 2.87 2.77 ratio is around 0.5 for all of studied samples. The 17α(h)-diahopane
Pr/n-C17 0.76 0.82 1.23 1.17
(C30D)/18α(H)-22,29,30-norneohopane (C29 Ts) ratio range from 0.5 to
Ph/n-C18 0.39 0.49 0.52 0.49
OEP*1 0.47 0.42 0.39 0.44 0.66. Gammacerane index (gammacerane/C30 αβ hopane) ranges from
CPI*2 1.28 1.19 1.07 1.25 0.12 to 0.2.
Waxiness*3 0.55 0.51 0.42 0.46
(C21+C22)/(C28+C29) 8.40 4.18 5.07 4.67
5.6. Steranes
∑C21−/∑C22+ 2.73 2.91 3.40 3.25

Terpanes C19 TT/C23 TT 0.50 0.37 0.32 0.39 Regular steranes distribution (C27, C28, C29) is dominated by
C19 TT/(C19 TT + C23 TT) 0.34 0.27 0.24 0.28 5α(H),14α(H),17α(H)-20R-steranes, with the abundance of C27
C23 TT/C24 TeT 1.48 2.08 2.07 1.70 (41%–44%), C29 is intermediate (25%–39%), and C28 is minor
C24 TeT/(C24 TeT + C23 TT) 0.40 0.33 0.32 0.36
(18%–32%; Table 2, Fig. 12). C29/C27ααα-20R steranes ratios range
C24 TT/C26 TT 1.78 1.50 1.50 1.47
C25 TT/C26 TT 1.28 1.03 1.16 1.04 from 0.71 to 0.85 (Table 2). C27βα/(αββ+ααα) and C29βα/(αβ-
β+ααα) ratios range from 0.95 to 1.01 and from 0.96 to 1.17, re-
Hopanes C35/C34 HH 1.02 0.74 0.80 0.69 spectively (Table 2).
C35 HHI*4 0.18 0.12 0.11 0.08
C29H/C30H 0.54 0.50 0.61 0.62
C30D/C29 Ts 0.60 0.66 0.52 0.50
5.7. Aromatic biomarkers
Gammacerane Index 0.20 0.16 0.12 0.19
Oleanane/Hopane 0.00 0.00 0.00 0.00 Thirty-seven aromatic hydrocarbon elements were detected using GC-
Ts/(Ts + Tm) 0.50 0.50 0.51 0.51 MS fragmentograms (m/z 142 + 156 + 170 + 178 + 184 + 192 + 198)
C29 20S/(20S + 20R) 0.47 0.47 0.45 0.32
of analyzed samples (Figs. 7–10). Methylphenanthrene indices (MPI-1, MPI-
C32 HH 22S/(22S + 22R) 0.54 0.56 0.55 0.54
ETR*5 0.72 0.50 0.78 0.72 2, MPI-3, MPR, and MPDF) based on methlphenanthrene parameters (3-MP,
Moretane/Hopane 0.20 0.16 0.086 0.078 2-MP, 9-MP, and 1-MP) are given in Table 3. These ratios are less than unit
for all of samples (MPI-1: 0.58–0.84, MPI-2: 0.59–0.86, MPI-3: 0.6–0.7,
Steranes % C27 Steranes 41 44 43 43
MPR: 0.64–0.78, MPDF: 0.37–0.41). The calculated vitrinite reflectance
% C28 Steranes 22 21 32 18
% C29 Steranes 37 35 25 39
form MPI-1 (RC, %) range from 0.72 to 0.87%, and have the same rates for
C29/C27 Steranes 0.85 0.81 0.86 0.93 RMPR (0.74–0.83%) and RMPDF (0.66–0.75%).
C27βα/(αββ+ααα) 0.96 1.01 0.95 1.01 The distribution of dimethlnaphtalene (DMN) and tri-
C29βα/(αββ+ααα) 1.08 1.17 0.96 1.07 methylnaphtalene (TMN) homologues leads to defining DNR-1, TNR-1,
C29 αββ/(αββ + ααα) 0.42 0.41 0.42 0.54
TNR-2, and TMNr indices ranging from 0.36 to 0.52, 0.97 to 1.04, 0.79
*1 OEP = 1/4 × (n-C25 + n-C27 + n-C29)/(n-C26 + n-C28). to 0.85, and from 0.35 to 0.68, respectively (Table 3). The calculated
*2 CPI = 1/2 [(C25+C27 + C29 + C31 + C33)/(C24 + C26 + C28 + C30 + C32) reflectance from DNR-1 (Rca, %) and from TNR-2 (Rcb, %) are less than
+ (C25 + C27 + C29 + C31 + C33)/(C26 + C28 + C30 + C32 + C34)]. unit (0.52–0.54% and 0.87–0.91%, respectively). The isomer ratio of
*3 Waxiness = ∑C21n-C31/∑C15n-C20. trimethylnaphtalene TDE-1 (1,2,5-TMN/1,2,4-TMN), used to identify
*4 HHI]C35/(C31–C35); *5 ETR= (C28+C29)/(C28+C29+Ts). the source rock origin and high plants input, ranges from 0.26 to 0.5
(Table 3). Methylnaphtalene ratio MNR has very nearly rates (around
1.3), and it is used as a maturity parameter. Tetramethylnaphthalene
ratios TeMNR-1 and TeMNr range from 0.26 to 0.62 and 0.23 to 0.44,
5.4. Terpanes respectively (Table 3).
The dimethyldibenzothiophene ratio (MDBTR) was proposed by
Tricyclic and tetracyclic terpanes (C19–C26) have low concentrations Radke et al. (1986) as an indicator of maturity, ranges between 1.68
compared to pentacyclic hopanes (Fig. 6). All of studied samples have a and 1.75 (Table 3) with an average of 1.72. The dibenzothiophene/
significant amount of C23 tricyclic terpane. The C19TT/C23TT and phenanthrene ratios (DBT/P) have low rates (0.088–0.138), and it's an
C19TT/(C19TT + C23TT) ratios are less than unit (Table 2). The C23 indicator of sediment lithology and depositional environment (Cortes
tricyclic terpane is more abundant than the T24 tetracyclic terpane et al., 2018).
(C23TT/C24Tet > 1; C24Tet/(C24Tet + C23TT) < 1; Table 2). C26 tri-
cyclic terpane is less abundant than C24 tetracyclic terpane and C25 6. Discussion
tricyclic terpane (C24Tet/C26TT > 1; C25TT/C26TT > 1; Table 2).
6.1. Organic matter input
5.5. Hopanes
The abundance of short-chain n-alkanes (< C20) indicates an algal
Pentacyclic hopanes are the principal elements of m/z 191 ionic derived organic matter (Eglinton and Hamilton, 1967; Meyers, 1997;
chromatograms (Fig. 5). All of samples are dominated by 17α,21β(H)- Tissot and Welte, 1984; Peters et al., 2005). The total ionic chromato-
hopane (C30) and 17α,21β(H)-norhopane (C29) and the C29/C30 ratios grams of the saturated hydrocarbon fraction (Fig. 5) show unimodal
range from 0.5 to 0.62. distribution centered on n-alkanes with low molecular weight (C17) and
Homohopanes (S and R) decrease towards C35HH and are a regular decrease beyond n-C17. This distribution indicates a marine

7
T. Hallek, et al.
Fig. 6. Partial mass chromatograms of aliphatic hydrocarbon fraction showing the distribution of terpanes/hopanes (m/z 191) and steranes (m/z 217) of selected
samples from the Fahdene Formation.
origin of the studied samples and the Pr/n-C17 and Ph/n-C18 ratios
plotted in Fig. 11 confirm this result.
Steranes are sterol-derived biomarkers and are founded in eu-
karyote walls but rare or absent in prokaryotic organisms. These bio-
markers are used to identify the organic matter origins (Huang and
Meinschein, 1979). C27 sterols are derived from algae, while C29 sterols
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Journal of African Earth Sciences 161 (2020) 103676
are synthesized from land plants (Volkman, 1986). According to the
diagram in Fig. 12, the studied samples show the predominance of C27
steranes compared to other homologues (C28 and C29) confirming ba-
sically the marine origin. The cross plot of C24TT/C26T vs. %C29 ster-
anes (Fig. 13) shows that the Fahdene organic matter was deposited in a
marine environment controlled by algal input.
T. Hallek, et al.
Fig. 7. Partial mass chromatograms (m/z 142, 156, 170, 178, 184, 192,198) of aromatic hydrocarbon fraction of the Fah-1 sample (lower Fahdene Formation).
18α(H)-Oleanane biomarkers are used to indicate the woody an-
giosperms contributions from Late Cretaceous flowering plants
(Ekweozor and Telnaes, 1990; Moldowan et al., 1994; Murray et al.,
1994; Peters et al., 2005). This compound is completely absent in
Fahdene samples, accordingly, we note the absence of any land trace in
the studied organic matter.
The aromatic fraction is the major component of organic matter,
and can be useful to determinate its origin. The isomer ratio of tri-
methylnaphthalenes (TMN) allows to evaluate the contribution of land
plants in organic rich strata (Peters et al., 2005). 1,2,5- and 1,2,7-tri-
methylnaphthalenes are used as an indicator of angiosperms contribu-
tion (Strachan et al., 1988), however 1,2,4- and 1,2,6-tri-
methylnaphthalenes indicate microbial marks in the organic matter
(Alexander et al., 1992). Low values of TDE-1 and TDE-2 (Table 3)
suggest the absence of any land plants contribution. According to DBT/
P vs. Pr/Ph ratios plot (Fig. 13), Fahdene black shales are deposited in a
marine-lacustrine environment.
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Journal of African Earth Sciences 161 (2020) 103676
6.2. Salinity
Gammacerane comes from the reduction of tetrahymena
(Venkatesan, 1989). The main source of tetrahymena is the bacterial
ciliates in the oxygen minimum zone (OMZ) with stratified water col-
umns (Jiamo et al., 1986; Sinninghe Damsté et al., 1995). Therefore,
the presence of Gammaceranes indicates, besides the stratified water
column, hypersaline environment. Gammacerane index GI values are
relatively low (Table 2), and suggest an unstratified water column and
the absence of hypersaline conditions during deposition. Low rates of
ETR (Table 2) confirm the absence of salinity marks in the depositional
environment (Niu et al., 2018).
6.3. Redox condition
Pristane (C19) and Phytane (C20) are used to control the oxygenation
degree in the depositional environment and lead to detect three classes
T. Hallek, et al.
Fig. 8. Partial mass chromatograms (m/z 142, 156, 170, 178, 184, 192,198) of aromatic hydrocarbon fraction of the Fah-3 sample (middle Fahdene Formation).
of redox conditions (Peters and Moldowan, 1993; Jiang and George,
2018). Anoxic conditions are characterized by Pr/Ph ratios low than
unit, while high Pr/Ph ratios (> 3) indicate oxidizing conditions with
land plants traces (Peters and Moldowan, 1993). For the analyzed
samples, Pr/Ph ratios range between 1 and 3 (Table 2) suggesting
suboxic conditions. The cross-plot of the C27/C29 ααα20R steranes
ratios vs. the pristane/phytane ratios (Fig. 13) confirms this result.
C31–C35 extended hopanes (homohopanes) are dominated by C31
HH and are decreased towards C35 HH (Fig. 6). The C35/C34 ratio is
commonly used to indicate redox conditions during the source rock's
deposition. high C35/C34 hopane ratios suggest anoxic conditions, while
low values are associated with suboxic to oxic environment (Peters and
Moldowan, 1991). The studied samples have high C35/C34 ratios
(0.69–1.02; Table 2) suggesting their marine anoxic environment. C35
homohopane index (HHI) indicate that the Fahdene organic matter is
deposited in a marine environment under anoxic conditions. The rela-
tively high C29/C30 hopane ratios (Table 2) indicate the same result of
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Journal of African Earth Sciences 161 (2020) 103676
redox conditions.
Furthermore, C3017a-diahopane (C30D) and C2918a (H)-30-norneo-
hopane (C29Ts) are sensitive to redox conditions, and we can apply
C30D/C29Ts to detect oxygen concentrations (Peters et al., 2005). The
studied samples from Fahdene black shales have C30D/C29Ts ratios low
than unit, indicating fairly low oxygen concentrations.
6.4. Maturity assessment
During catagenesis, C27 18α-22,29,30-trisnorneohopane (Ts) is
more stable than C27 17α-22,29,30-trisnorhopane (Tm) (Seifert et al.,
1978). Thus, high Ts/(Ts + Tm) ratios (Table 2) for the analyzed se-
diments suggest their maturity. In other hand, C30 diahopane/C30 ho-
pane ratio increases with maturity because of the unstability of regular
hopanes comparing to diahopanes. For this study, C30D/C30H ratios
(Table 2) indicate that the maturity decreases from the basement of
Fahdene column toward the top.
T. Hallek, et al.
Fig. 9. Partial mass chromatograms (m/z 142, 156, 170, 178, 184, 192,198) of aromatic hydrocarbon fraction of the Fah-7 sample (middle Fahdene Formation).
Isomerization at C-22 position in homohopanes has mainly been
used to assess thermal maturation of organic matter (Brooks et al.,
1992). The biologically produced precursors for hopanes (22R) are
gradually converted to 22R and 22S diastereomers mixture (Peters
et al., 2005). The 22S/(22S + 22R) ratio for C32 homohopanes in-
creases during maturity from 0 to about 0.6 (Equilibrium = 0.54–0.56;
Mackenzie et al., 1980). For the analyzed organic matter from Fahdene
Formation this ratio is in the range of 0.55 indicating that these sedi-
ments are thermally mature and reach the equilibrium stage.
Isomerization at C-20 in the C29 5α,14α,17α(H)- steranes causes the
rise of 20S/(20S + 20R) ratio from 0 to 0.5 (0.52–0.55 = equilibrium)
with the increase of thermal maturity (Seifert and Moldowan, 1986).
The analyzed samples show that this ratio is low and close to the
equilibrium value (0.32 and 0.47, Table 2) indicating that the organic
matter derived from these sediments is at low-mature stage.
Isomerization at C-14 and C-17 in the C29 20S and 20R regular
steranes causes the rise of ββ/(αα+ββ) from near-zero values to 0.7
11
Journal of African Earth Sciences 161 (2020) 103676
(0.67–0.71 = equilibrium) with the increase of maturity (Seifert and
Moldowan, 1986). For this study, ββ/(αα+ββ) ratios have low values
(0.41–0.54, Table 2) indicating that these organic rich strata have not
yet reached the mature stage.
For the aromatic fractions, the methylphenanthrene index (MPI-1)
and their calculated vitrinite reflectance (Rc) listed in Table 3, are used
to control the source rock maturity (Radke et al., 1982a, 1982b). The
MPI-1 and Rc values calculated for this study range from 0.58 to 0.84
and 0.72%–0.87%, respectively (Table 3), and the MPI-1 vs. methyl-
phenanthrene ratio (MNR) plot indicates that this organic matter is
mature (Fig. 13). Therefore, the basement of Fahdene Formation ex-
tended to peak oil, while the top have just reached the oil window.
The relatively low maturity of the Fahdene Formation can be ex-
plained also by high CPI values (> 1, Table 2, Bray and Evans, 1961),
the distribution patterns of TeMN isomers, with 1,2,5,6- and 1,2,3,5-
TeMN dominance (Figs. 7–10; Van Aarssen et al., 1999), and the alkyl
phenanthrenes display the predominance of 9-MP over 1-MP
T. Hallek, et al.
Fig. 10. Partial mass chromatograms (m/z 142, 156, 170, 178, 184, 192,198) of aromatic hydrocarbon fraction of the Fah-10 sample (upper Fahdene Formation).
(Figs. 7–10; Radke et al., 1982a,b).
The presence of bitumen traces in the thin sections (Fig. 14) con-
firms that these sediments are mature and have been reached the oil
generation window.
6.5. Selective biodegradation
High concentrations of NSO compounds, over saturates and aro-
matics hydrocarbons, are generally related to microbiological de-
gradation (Escobar et al., 2011). In the other hand, biomarker biode-
gradation rate is based on the vulnerability of the hydrocarbon
compound to the biodegradation (Peters et al., 2005). N-alkanes from
C8 to C12 are preferentially removed and signifying the first indication
of biodegradation (Peters et al., 2005). For this study, the absence of
short-chain normal alkanes (< C13, Fig. 5) indicates a selective
12
Journal of African Earth Sciences 161 (2020) 103676
biodegradation of organic matter, and the pristane/phytane (Pr/Ph)
ratios confirm the effect of biodegradation.
The susceptibility to biodegradation of alkylated PAH isomers de-
creases with increasing number of alkyl substituents (e.g. Volkman
et al., 1984; Williams et al., 1986). Three alkylnaphthalene biode-
gradation ratios are identified (Fisher et al., 1998): (i) Di-
methylnaphthalene ratio (DBR) = 1,6-DMN/1,5-DMN; (ii) Tri-
methylnaphthalene ratio (TBR) = 1,3,6-TMN/1,2,4-DMN; and (iii)
Tetramethylnaphthalene (TeBR) = 1,3,6,7-TeMN/1,3,5,7-TeMN. These
ratios indicate that the organic matter of Fahdene Formation is affected
by low biodegradation rates.
6.6. Lithology
Abundance of regular steranes over diasteranes (m/z 217; Fig. 6,
T. Hallek, et al. Journal of African Earth Sciences 161 (2020) 103676

Table 3
Aromatic biomarkers parameters based on GC-MS results from Fahdene source
rock.
Parameters Fah-1 Fah-3 Fah-7 Fah-10

MPI-1 0.84 0.58 0.60 0.70

MPI-2 0.86 0.59 0.66 0.75
MPI-3 0.69 0.70 0.60 0.66
Rc (MPI-1) 0.87 0.72 0.73 0.79
MPR 0.64 0.65 0.76 0.78
RMPR 0.74 0.75 0.82 0.83
MPDF 0.40 0.41 0.37 0.39
RMPDF 0.73 0.75 0.66 0.71
MNR 1.31 1.34 1.30 1.32
DNR 0.36 0.36 0.50 0.52
MDR 1.72 1.68 1.73 1.75
TNR-1 0.97 1.04 1.01 1.03
TNR-2 0.84 0.79 0.85 0.82
Rca (DNR) 0.52 0.52 0.53 0.54
Rcb (TNR-2) 0.90 0.87 0.91 0.89
MBpR 14.50 15.00 14.00 15.00
TDE-1 0.35 0.50 0.26 0.46
TDE-2 1.50 1.20 1.54 1.35
TMNr 0.66 0.35 0.68 0.52
TeMNR-1 0.26 0.29 0.62 0.47
TeMNr 0.23 0.23 0.44 0.35
DBT/P 0.097 0.098 0.138 0.088 Fig. 12. Ternary diagram showing the relative abundances of C27, C28, and C29
regular steranes in the saturate fractions of studied samples from Fahdene
MPI-1 = 1,5 x (2-MP+3-MP)/(P+1-MP+9-MP); MPI-2 = 3(2-MP)/(P+1-MP Formation.
+9-MP); MPI-3=(2-MP+3-MP)/(1-+9-MP); Rc (MPI-1) = 0.6 x MPI
1 + 0.37; MPR = 2-MP/1-MP; RMPR=(0.99 x log10 MPR) + 0.94;
MPDF = [3-MP+2-MP]/∑MPs; RMPDF=(2.2424 x MPDF) – 0.166; MNR = 2-
MN/1-MN; DNR = [2,6 + 2,7-DMN]/1,5-DMN; MDR = 4-MDBT/1-MDBT;
TNR-1 = 2,3,6-TMN/[1,4,6-+1,3,5-TMN]; TNR-2 = 2,3,6-+1,3,7-TMN/ Table 2) suggests a carbonate lithology approved by the important
[1,4,6-+1,3,5-+1,3,6-TMN]; Rca (DNR)= (0.09 x DNR-1) + 0.49; Rcb (TNR- concentrations of tetracyclic terpane T24 (Palacas et al., 1984; Connan
2)= (0.6 x TNR-2) + 0.4; MBpR = 3-MBp/2-MBp; TDE-1 = 1,2,5-TMN/1,2,4- and Dessort, 1987, Fig. 6). Moreover, Ts/(Ts + Tm) appears to be
TMN; TDE-2 = 1,2,7-TMN/1,2,6-TMN; TMNr = 1,3,7-TMN/[1,3,7-+1,2,5- sensitive to clay-catalyzed reactions (Peters et al., 2005). In fact, low
TMN]; TeMNR-1 = 2,3,6,7-TeMN/1,2,3,6-TeMN; TeMNr = 1,3,6,7-TeMN/ Ts/(Ts + Tm) ratios (Table 2) indicate that the Fahdene sediments have
[1,3,6,7 + 1,2,5,6-TeMN]; From George and Ahmed, 2002. a carbonate lithology (McKirdy et al., 1983, 1984;Rullkötter et al.,
1985; Price et al., 1987). However, the dibenzothiophene/phenan-
threne ratio (DBT/P) is used as an indicator of source rock lithology,

Fig. 11. Cross-plot of Pr/n-C17 Vs. Ph/n-C18 of Fahdene Formation's samples, Pr: pristane; Ph: phytane.

13
T. Hallek, et al.
Fig. 13. (a) C24TT/C26 T V %C29 regular steranes plot. (b) Plot of DBT/Phenathrene vs. Pr/Ph ratios. (c) Plot of C27/C29 ααα20R steranes ratios vs. the pristane/
phytane ratios. (d) Maturity parameters from methylphenanthrene index (MPI-1) and methylphenanthrene ratio (MPR).
and the carbonate sediments are proven by DBT/P ratios higher than
unit (Radke et al., 1986; Hughes et al., 1995), while the analyzed
samples have low ratios (Table 3) suggesting a clay facies.
X-ray diffraction can be also used to attest the lithology of these
organic deposits (Fig. 15), outlining the presence of carbonate minerals
(Calcite and Ankerite) for the Fahdene Formation extremities, and a
siliciclastic trend (Illite, Chlorite and Kaolinite) in the middle part. In
the other hand, the clacimetry check (Fig. 4) confirms these results
showing high CaCO3 values in the lower and upper parts of Fahdene
(52% (Fah-1)-75% (Fah-11); Table 1, Fig. 4) with low rates in the
middle part (≈5%).
6.7. Fracturing analysis
The Albian-Early Cenomanian interval outcrops in Northern Tunisia
are characterized by fluid overpressure marks with various sizes and
directions of fractures. Many authors (Fertl, 1976; Hunt, 1990; Lee and
Bethke, 1994; Bigelow, 1994; Bjørlykke, 1994; Swarbrick and Osborne,
1998; Akrout et al., 2011) have indicated that the fluid overpressure is
frequently observed in sedimentary basins. This phenomenon have a
great importance in petroleum fields (Fertl et al., 1994; Xie et al., 2001;
Song et al., 2002).
14
Journal of African Earth Sciences 161 (2020) 103676
The microscopic observations of the collected samples from
Fahdene Formation (Fig. 14) prove the presence of high density of
fractures with various sizes and directions (parallel or oblique to the
stratification). About filling, the fibrous calcite is the major element of
mineralized veins, noting the existence of bitumen traces. The fractures
composition results from the chemical elements disposal in the source
rock. These fractures have two main origins; the fluid pressure pro-
cesses and the regional tectonic stress regime.
The observed sample in the basement (Fah-1, Fig. 14) shows many
calcite filled sets of veins and shear joints. These microfracture haven't
the same direction indicating that they are not contemporaneous and/
or not belonging to the same tectonic phase. Some of the veins show
possible late folding deformation (sinuous shape wide vein to the top).
It shows as well conjugate system of simple shear joints indicating the
contraction stress direction in the acute angle between joint sets.
Thin section view on MH3 sample (basement of Fahdene Formation,
Fig. 14) shows micro-fossiliferous packstone (forams rich). Most of
fossils are dissolved and their mold is actually filled with calcite.
For the Fah-7 sample, thin section show argillaceous packstone
highly fossiliferous containing forams (benthic and planktonic) and
macrofissile debries (shell fragments), with no microfracture observed.
Cross bed section view on the Fah-11 sample (Fig. 14) shows clearly
T. Hallek, et al.
Fig. 14. Microscopic observations of thin section of selected samples from Albian-Cenomanian Fahdene source rock, (A), (B) and (C) from Fah-1; (D) from Fah-3; (E)
and (F) from Fah-7; (G), (H) and (I) from Fah-11.
very thin laminations between clay and limestone. This sample is
composed of high concentrations of benthic forams and present some
inclusions of bitumen.
The fracture arrangement allows to identify three main zones: (i)
the lower part characterized mainly by dense networks of a micro-
fractures complex, noting the appearance of macro fractures within the
Aptian-Albian transition (Fig. 16); (ii) the middle part includes multi-
directional macro-fracture networks, with the absence of small scale
homologues, and appearance of a large number of Foraminifera dis-
solved and filled by calcite (Fig. 17); (iii) the top of Fahdene source rock
displays small visible cracks showing a paradox in thin sections. It is a
beach of foraminifera having deposited and preserved in the Vraconian
sediments parallel to strata (Fig. 14).
15
Journal of African Earth Sciences 161 (2020) 103676
We can retrace the history of these organic rich strata, focusing on
the presence of both foraminifera and algae (Fig. 14). The nitrogen
present in the diagenesis stage results from the denitrification phe-
nomenon which consists of reducing the nitrate ion to produce mole-
cules absorbable by plants (nitrite NO2-, nitrogen monoxide NO, ni-
trous oxide N2O, dinitrogen N2). These high nitrogen inputs provide
both the eutrophication reaction and the proliferation of algae. How-
ever, the abundance of microorganisms, especially planktonic for-
aminifers prevents the incident radiations, causing then the reduction
of algae. In addition, anoxic events during the Albian-Cenomanian in-
terval causes the foraminifer's death, decantation and accumulation in
the sediment with the already present algae. Consequently, the studied
organic matter have been deposited in a transition environment
T. Hallek, et al. Journal of African Earth Sciences 161 (2020) 103676

Fig. 15. X-ray diffraction patterns obtained from Fahdene Formation's selected samples.

between the external and internal platforms, where the plant traces organic matter, and that the Albian-Cenomanian interval was the seat
resulting from Rock Eval data come from algae overgrowth in situ. of ecological disturbance ensured mainly by the phenomenon of eu-
Therefore, we can affirm that no land plant input in the Fahdene trophication.

16
T. Hallek, et al. Journal of African Earth Sciences 161 (2020) 103676

Fig. 16. Macro fractures in the Aptian-albian transition and their small scale homologous in microscopic observations (micro fractures).

Fig. 17. Macro fractures in the Middle Fahdene and absence of homologous in thin sections showing dissolved foraminifera filled by calcite.

17
T. Hallek, et al.
7. Conclusions
Based on our integrated organic geochemical and mineralogical
investigation of samples collected from Fahdene source rock, the fol-
lowing conclusions can be drawn.
1. The Fahdene Formation have fair to good petroleum potential.
2. Organic matter of Fahdene source rock have a marine origin and has
been deposited under suboxic conditions and slightly affected by
biodegradation.
3. The Albian-Cenomanian was the seat of ecological disturbance en-
sured mainly by the phenomenon of eutrophication.
4. Aromatic and aliphatic biomarkers attest that the Fahdene source
rock is low-mature, and having just reached the oil window.
5. Fahdene Formation's lithology is dominated by carbonates with
presence of terrigenous facies in the middle part.
6. The fracturing analysis of Fahdene Formation leads to differentiate
three main parts, according the presence, size and type of fractures.
Declaration of competing interest
There is no conflict of interest.
Acknowledgements
This work was supported by the research unit “Geosystems,
Georesources and Geoenvironments” (UR3G), Tunisia. We are deeply
grateful to Professor Nouri HATIRA for his help and assistance with
XRD analysis, and to the University of Gabes staff for assistance with
geochemical analysis.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.jafrearsci.2019.103676.
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