Ore Geology Reviews 113 (2019) 103070

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Ore Geology Reviews

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Organic matter and metal contents within the Cretaceous rocks of the Slata- T
Guern Halfaya area, North-Central Tunisia: Implication for ore genesis
⁎
Larbi Rddada, , Nejib Jemmalib, Emmanuel John M. Carranzac, Markus Wälled
a
Earth and Planetary Division, Physical Sciences Department, Kingsborough Community College, City University of New York, 2001 Oriental Boulevard, Brooklyn, NY
11235, USA
b
Faculté des Sciences de Gafsa, Sidi Ahmed Zarrouk, 2112 Gafsa, Tunisia
c
Discipline of Geological Sciences, School of Agricultural, Earth and Environmental Sciences, University of KwaZulu-Natal, Westville Campus, Durban, South Africa
d
CREAIT, Memorial University of Newfoundland, St. John’s, NL, Canada

A R T I C LE I N FO A B S T R A C T

Keywords: The proximity of ore deposits, in the Slata-Guern Halfaya area (north-central Tunisia), to the Cretaceous Fahdene
Fahdene Formation and Bahloul Formations raises the question of the role that these formations played in the emplacement of the
Bahloul Formation ore. These formations are rich in organic matter (OM) with total organic carbon (TOC) values in the range of
MVT ore deposits 0.2–1.4% and 0.62–5.46%, respectively, for the Albian–Vraconian facies of the Fahdene Formation at Slata and
Organic matter maturity
the Cenomano–Turonian facies of the Bahloul Formation at Guern Halfaya. Rock-Eval pyrolysis data indicates
Halokinesis
that the OM in the Fahdene Formation at Slata is relatively mature (oil window, 431 °C < Tmax < 447 °C) and
Tunisian diapiric zone
with variable Production Index (PI, %)). Conversely, the OM preserved in the Bahloul Formation at Guern-
Halfaya is immature (423 °C < Tmax < 433 °C). The analysis of whole rocks and the LA-ICP-MS analysis of
inorganic fraction reveal high concentrations of trace elements (e.g., Pb, Zn) in both formations. We infer that
seawaters were enriched in trace elements during the deposition of both formations. These trace elements were
then sequestered by both organic and inorganic matter. Given the similar OM-rich lithologies (carbonates and
marls) of these formations, the difference in trace element concentrations can be due to their contrasting thermal
maturities. Concentrations of trace elements (Pb, Zn, Cd, and Ni) moderately correlate with OM content (TOC,
pyrolyzable hydrocarbons and residual OM) positively in the organically-immature Guern-Halfaya ore district
and negatively in the organically-mature Slata mining district. Subsidence of the OM-rich Cretaceous Formations
(Fahdene and Bahloul), located in the deep part of the basin, resulted in thermal cracking of kerogen in these
formations. This catagenesis allowed the dissociation of organo-metal ligands and subsequent expulsion of
metals in low viscosity hydrocarbons during the Alpine orogeny. Metals and hydrocarbons migrated together
from the subsiding areas of the basin and ultimately encountered salt diapirs. The mixing between metal-rich
hydrocarbons and ore-bearing associated fluids, on the one hand, and the Triassic-derived sulfate-rich fluids, on
the other hand, led to the precipitation of sulfides and sulfates at different times. A potentially effective trilogy to
be targeted for base metal exploration is the juxtaposition of (i) mature OM-rich formations – potential sources of
metals and hydrocarbons – with (ii) diapiric evaporites that served as a source of sulfur and sulfate, and (iii) a
permeable reservoir that acted as a suitable site for ore precipitation.

1. Introduction
Sedimentary formations rich in organic matter (OM) have been
targeted for ore exploration throughout the world (USA: Parnell, 1988;
Spirakis and Heyl, 1993; Canada: Anderson and MacQueen, 1982; Po-
land: Kucha, 1982; Ireland: Carter and Cazalet, 1984; Tunisia: Montacer
et al., 1988; Chile: Cisternas and Hermosilla, 2006). Such formations
usually have anomalous concentrations of metals (e.g., Pb, Zn, Cu, Fe)
compared to average crustal rocks (Taylor, 1964). These anomalies are
mainly due to bio-concentration of metals by marine organisms
(Bowen, 1966; Saxby, 1976; Trundinger and Swaine, 1979; Eisler,
1981; Noriki et al., 1985; Arthur et al., 1988; Gavshin, 1991) and to the
removal of metals from solution during early diagenesis (Disnar and
Trichet, 1983; Gauthier and Disnar, 1984; Trichet et al., 1987; Gize
et al., 1991; Disnar, 1982, 1996). It is well known that hydrocarbons
(e.g., crude oils) contain certain amounts of dissolved metals (Parnell,

⁎
Corresponding author.
E-mail address: Lrddad@gmail.com (L. Rddad).

https://doi.org/10.1016/j.oregeorev.2019.103070
Received 19 September 2018; Received in revised form 30 July 2019; Accepted 8 August 2019
Available online 10 August 2019
0169-1368/ Published by Elsevier B.V.
L. Rddad, et al.
1988; Seward et al., 2014; Migdisov et al., 2017; Saintilan et al., 2019).
The association of OM with Zn-Pb Mississippi Valley-type (MVT) de-
posits is common worldwide (Powell and Macqueen, 1984; Giordano,
1985; Leventhal, 1990; Kesler et al., 1994; Disnar and Sureau, 1990;
Disnar, 1996; Charef and Sheppard, 1987; Montacer et al., 1988;
Parnell, 1994; Gize and Barnes, 1994; Spangenberg and Macko, 1998;
Gize, 1999; Coveney, 2000; Huston et al., 2006; Perona et al., 2018).
The proximity of these OM-rich formations to the Pb-Zn ore deposits
raises the question of the possible contribution of these formations as
source of metals and hydrocarbons for the genesis of the diapir-related
ore deposits. The salt diapiric structures associated with these OM-rich
formations are a fundamental factor in the emplacement of ore
worldwide (Price et al., 1983; Kyle and Price, 1986; Orgeval et al.,
1986; Rouvier et al., 1985; Ravenhurst and Zentilli, 1987; Posey et al.,
1987).
In Tunisia, and precisely in the diapiric zone, the juxtaposition of
the Cretaceous formations that are rich in OM (Fahdene and Bahloul
Formations) to the Triassic diapir evaporites and the ore deposits is
common. In the Tunisian diapiric zone, the frequent juxtaposition of (i)
the Triassic salt diapirs, (ii) the ore host rocks, and (iii) OM-rich facies
(e.g., Bou Grine, Bou Jaber, Fej Lahdoum, Slata, Guern Halfaya) incites
consideration of the genesis of the mineralization by taking into ac-
count all these three elements (i to iii). Indeed, the Triassic evaporites
have been considered as a source of sulfur for sulfides and sulfate for
barite and celestite for the diapir-related ore deposits (Smati, 1986;
Jemmali et al., 2013a; Bouhlel et al., 2016). The Paleozoic basement
was proposed to be the source of metals for the ores in the diapir-re-
lated ore deposits (Bouhlel et al., 2013; Bouhlel et al., 2016). With
regards to the ore-forming processes, previous studies proposed fluid
mixing between metalliferous fluids derived from the basement and
local Triassic sulfate rich-fluids as the main mechanism for ore pre-
cipitation. Some authors, however, considered the organic-matter- rich
Cretaceous formations as another source of metals for the Bou Grine ore
deposits for example (Montacer, 1989; Orgeval, 1994; Charef, 1986;
Bechtel et al., 1998). On the basis of Pb isotopic data, Fariss (2000) also
considered Cretaceous formations as a contributing source for base
metals for the Bou Grine and Bou Jaber ore deposits. In the studied
area, the importance of the Triassic salt diapir and tectonic in the
emplacement of the ores is highlighted in Slata (Smati, 1986) and
Guern Halfaya (Kassaâ, 1998; Jemmali et al., 2013a). These authors
also proposed the Paleozoic rocks as the source of metals for the ore in
the Slata-Guern Halfaya districts. Besides the Paleozoic basement as a
source of metals, this project seeks to verify if the Cretaceous OM-rich
formations are another possible ore reservoir in the Slata-Guern Halfaya
districts. These districts, where the OM-rich formations are proximal to
both the salt diapirs and mineralized host rocks, are ideal for this
purpose. To the best of our knowledge, there is no systematic geo-
chemical study about the distribution, concentration of trace elements,
and their relation to OM content within these formations has not been
investigated. The role these formations played as another source of
metals in these ore districts has not been examined. Hence, the objec-
tive of this paper is to examine the possible contribution of the OM-rich
Cretaceous formations (Fahdene and Bahloul) as another source of
metals in the genesis of the ore in the Slata-Guern Halfaya districts. To
that end, OM geochemistry of both formations was investigated and
bulk rocks and inorganic fractions were analyzed for trace elements.
2. Geological setting
2.1. Regional geology of the diapiric zone and ore distribution
The Slata-Guern Halfaya region is situated in the diapiric zone,
which extends over 300 km in length and 100 km in width (Fig. 1)
(Jemmali et al., 2013a). The diapiric zone is marked by numerous
NE–SW-trending Triassic evaporite diapirs that pierced the Jurassic and
the Early Cretaceous sedimentary formations (Sainfeld, 1956;
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Ore Geology Reviews 113 (2019) 103070
Perthuisot, 1978, 1981; Perthuisot and Rouvier, 1996). The Pre-
cambrian basement is composed of igneous and metamorphic rocks
whereas the Paleozoic basement consists of siliciclastic rocks (Ben
Ferjani and Burrolet, 1990). The Triassic series unconformably overlies
the Precambrian-Paleozoic basement (Ben Ferjani and Burrolet, 1990)
and consists of ~1000 m-thick evaporitic sequence (halite and gypsum)
intercalated with siliciclastic rocks (Perthuisot, 1978, 1981).
During Middle Jurassic to Early Cretaceous, the rifting in the Tethys
Ocean was pronounced and led to the development of the Tunisian
Trough in the north and the Central Tunisian carbonate platform in the
south (Bolze et al., 1952; M’Rabet, 1987; Vially et al., 1994; Bouaziz
et al., 2002). The sequence in the carbonate platform is composed of
siliciclastic and limestone rocks (Marie et al., 1984; M’Rabet, 1987),
whereas the Tunisian Trough consists of a 5000-m thick sequence of
mainly pelagic sediments (Perthuisot, 1978, 1981).
During Late Aptian-Albian, the reactivation of the NE–SW-trending
basinal faults led to two episodes of halokinesis (salt flow and dome
formation). The first piercing diapirism occurred during the Late Aptian
(Snoke et al., 1988) whereas the second took place during the Middle
Albian (Perthuisot, 1981). The first halokinetic activity created paleo-
highs on which Aptian reef and carbonate platforms of the Serdj For-
mation were developed (e.g. Slata, Bou Jaber, Jerissa, and Ouenza;
Dubourdieu, 1956; Smati, 1986; Perthuisot and Rouvier, 1992; Bouhlel,
1993; Perthuisot et al., 1998). A regional marine transgression occurred
during the Late Albian and continued until the end of Paleocene. During
this time, a thick sequence of pelagic and hemipelagic sediments was
deposited (e.g., Burollet, 1956). The lower section of the sequence is
represented by the Albian-Vraconian alternating layers of marl and
limestone of the Fahdene Formation (Burollet, 1956) and the Late
Cenomanian-Early Turonian platy limestone and black shale and marls
of the Bahloul Formation (Burollet, 1956). The Fahdene Formation
sealed the Aptian carbonate platforms. The Late Albian Mouehla
member of the Fahdene Formation and the Bahloul Formation are both
known to be rich in OM (~2% and ~13% TOC, respectively) (Saïdi,
1986; Talbi 1986; Layeb, 1990; Montacer et al., 1988; Saïdi and
Belayouni, 1994; Soua, 2009). These OM-rich Cretaceous formations
were deposited mainly in anoxic environments with high organic pro-
ductivity (Soua, 2010; Affouri et al., 2013; Touati and Haji, 2019).
These formations were followed by the deposition of a 2000-m thick
sequence of marls and limestone of Turonian-Paleocene age.
The collision between the African and European plates resulted in
the inversion of the North Tunisian Tethyan margin (Cohen et al., 1980;
Dewey et al., 1989; Guirand and Maurin, 1991). This Alpine tectonic
phase consists of alternating compressional and extensional tectonic
events that affected the region. The first major tectonic Alpine phase
occurred during the Middle Eocene compressional tectonic event
(Burollet, 1956; Erraoui, 1994; Tlig et al., 1991, 2010; Souquet et al.,
1997; Frizon de Lamotte et al., 2000; Bouaziz et al., 2002; Frizon de
Lamotte et al., 2009). Succeeding this compressional event is the first
period of relaxation that occurred in relation to an Oligocene-Early
Miocene extensional event (Bouaziz et al., 2002; Frizon de Lamotte
et al., 2009). The second shortening Atlasic event took place during the
Middle Miocene (Bouaziz et al., 2002; Frizon de Lamotte et al., 2009).
This tectonic phase affected the post-Neogene facies, leading to the
present NE–SW-, N–S-, and E–W- trending folds and mountains of the
region (Turki et al., 1988; Chikhaoui and Turki, 1995). It is during the
first and second compressional tectonic phases that the third phase of
halokinetic and diapirism took place, leading to the emplacement of the
present diapir structures (Perthuisot, 1981; Bouhlel, 1993). A second
relaxation period took place in the Late Miocene (Tortonian–Messinian)
during which molasse and lacustrine limestone were deposited
(Rouvier, 1977).
The Pb-Zn ± (Ba, Sr, F) mineralization in the diapiric zone is part of
the Zn-Pb province of the Circum-Mediterranean Sea and Alpine Europe
(e.g., Rouvier et al., 1985). The Tunisian diapir-related mineralization
occurs at the contact between the Triassic diapirs and the Cretaceous
L. Rddad, et al.
Fig. 1. Map (after Jemmali et al., 2013a) showing locations of diapir-related ore deposits in the diapiric zone as well as the locations of the Slata and Guern Halfaya
areas. Red line next to Slata is location of cross section shown in Fig. 15. (For interpretation of the references to color in this figure legend, the reader is referred to the
web version of this article.)
organic-rich formations (e.g. Fahdene and Bahloul Formations). The ore
is hosted mainly at the Triassic-Cretaceous contact zone and in the Late
Cretaceous strata above the Triassic salt diapirs (Sainfeld, 1952;
Rouvier et al., 1985; Orgeval, 1994; Jemmali et al., 2013b). In the Slata
Ba-Pb-( ± Zn) district, the ore is hosted in the Aptian carbonates and
occurs mainly as vein-filling mainly along NE–SW-, NW–SE-, and N–S-
trending faults (Smati, 1986). The Aptian carbonate host rock is sealed
by the semi-permeable marly limestone rocks of the Fahdene Forma-
tion. In the Guern Halfaya Pb-Zn ore district, the ore is hosted in the
Triassic – Upper Cretaceous contact and in the Cenomanian-Turonian
marl-limestone alternations. The ore is hosted along the NE–SW- and
N–S- trending faults and is sealed by the Coniacian-Santonian marls.
2.2. Geology and tectonics of the studied areas
The Slata-Guern Halfaya mining districts (Figs. 2 and 3), located
230 km SW of Tunis and 10 km from the town of Tajeroiune, belongs to
the SW part of the diapiric zone, locally named “Zone des Domes”.
These mining districts are affected by three main tectonic phases
(Smati, 1986; Kassaâ, 1998): (i) extensional Aptian phase; (ii) intra-
Albian phase; and (iii) the Alpine orogeny. The major faults that were
reactivated during these tectonic phases are the E–W-, NW–SE-, and
NE–SW- trending faults. During the major Miocene Alpine event, the
inversion of the NE–SW- trending faults and the compression of various
structures formed the present-day NE–SW- trending structures in the
Slata-Guern Halfaya mining districts. The combined effect of tectonism
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Ore Geology Reviews 113 (2019) 103070
and halokinetic activities controlled the sedimentation during the Early
Cretaceous. One of the most important geological events that took place
as a result of these activities is the development of anoxic events that
led to the accumulation and preservation of OM-rich formations (Fah-
dene and Bahloul Formations) (Soua et al., 2009; Touati and Haji, 2019;
Affouri et al., 2013).
In the Slata mining district, the lithostratigraphy of Jebel Slata is
mainly composed of the following rocks (Smati, 1986; Perthuisot et al.,
1988; Chihaoui et al., 2010; Jaillard et al., 2013) (Fig. 2):
• Aptian rocks (~700 m thick) composed of carbonates intercalated
with siliciclastic rocks (Serdj and Hammeima Formations) (Burollet,
1956; M’Rabet et al., 1995). The Serdj carbonate Formation hosts
the Pb-Ba-(Zn) ore.
• Albian-Vraconian rocks comprised of three members described
below:
• The lower member consists mainly of marl and shale beds which
contain pyritized ammonites alternating with few limestone beds
rich in bioclasts, belemnites and pyritized ammonites with a thick-
ness reaching up to 130 m.
• The Middle Albian “Allam limestone member”, defined by Burollet
(1956), is ~140 m thick (Smati, 1986). It is composed of OM-rich
black massive laminated limestones with bioclastic fauna. These
limestone layers alternate with dark grey marls rich in pyrite and
bioclastic marls with small-scale oil seeps (Chihaoui et al., 2010).
• The Late Albian (Vraconian) (~200 m thick) was extensively studied
L. Rddad, et al.
Fig. 2. Geologic map of Slata area (modified after Smati, 1986).
and described by Smati (1986), Perthuisot et al. (1988), and
Chihaoui et al. (2010). The Vraconian series is transgressive with a
base locally marked by a 1-m thick conglomerate and by an angular
unconformity (Perthuisot et al., 1998). The lower part of the Vra-
conian is characterized by the Mouelha member which is rich in OM
and consists of alternating dark black laminated limestones and
marls.
The Bahloul Formation of Cenomanian–Turonian age, outcropping
in the Koudiat Ben Jaou area, is unconformably overlying the Triassic
series. It is composed of ~110 m thick alternating black shales with
some marly intercalations of limestone and is regionally known to be
rich in OM (Fig. 4).
The geology of Guern Halfaya has been described by many authors
(Sainfeld, 1952; Miadi and Mongi, 1988; Hammami and Smati, 1993;
Hatira and Zouari, 1997; Kassaâ, 1998; Jemmali, 2011; Jemmali et al.,
2013a,b), and its lithostratigraphy consists of (Fig. 3):
• Triassic chaotic gypsiferous clays and black dolomitic-limestones,
which are overlain in the subsurface by large amounts of anhydrite
with halite core;
• Lower Cretaceous rocks comprised of Aptian micritic limestones and
sandy clays overlain by thick limestone beds and Albian limestones
and marls with Radiolarians (Ticinella and Hedbergella);
• Upper Cretaceous rocks comprised of Cenomanian marl-limestone
alternations overlain by yellowish limestones, Cenomanian – Lower
Turonian laminated gray to black organic-rich limestones of the
Bahloul Formation with Globigerina, Turonian marls and banded
limestones, Coniacian-Santonian marls (Aleg Formation) and Upper
Campanian – Lower Maastrichtian marl-limestones and limestones
(Abiod Formation);
• Paleocene – Lower Eocene rocks (El Haria Formation) composed of
clays with marl, gypsum and rare limestone intercalations;
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Ore Geology Reviews 113 (2019) 103070
• Ypresian Nummulite-bearing limestone (Metlaoui Formation);
• Miocene series starting with coarse conglomerates and carbonates
and continues with micro-conglomerates, which are well re-
presented at the northern foot of Koudiat el Hamra, and ends with
sandstones and sandy clays; and
• Quaternary alluvium and clayey sand aureoles on Miocene con-
glomerates.
During the major Miocene Alpine event, the inversion of the
NE–SW- trending faults and the compression of various structures
formed the present-day NE–SW- trending structures of Slata-Guern
Halfaya.
3. Ore geology
The Slata Ba-Pb-( ± Zn) ore deposit is hosted in the Aptian carbo-
nates and sealed by the impermeable OM-rich Albian Fahdene
Formation. The mineralization, which is tectonically and unconformity
controlled, is hosted in faults/fractures, dissolution cavities/karsts, and
unconformities (Fig. 5A-F). The paragenetic sequence is diagenetic
pyrite → siderite-ankerite → barite 1 → galena-sphalerite/calcite 1 →
late barite → late calcite (Fig. 5A-4F). Pyrite is disseminated in the
matrix as isolated small euhedral pyrite and/or framboidal pyrite
(Fig. 6B). Pyrite is often oxidized into Fe(oxy) hydroxides (Fig. 6C).
Ankerite crystals (Fig. 5A) predates tabular, lamellar, translucent Barite
(Ba-1) (Fig. 5A, B). Galena occurs as disseminations (Fig. 5B) and in
veins (Fig. 5C). Barite 2 (Ba-2) occurs as white fibrous and fibro-radial
crystal and postdates galena (Fig. 5E). Two generations of calcite are
associated with the mineralized fractures: calcite 1 and calcite 2. Calcite
1 is co-genetic with galena and sphalerite (Smati, 1986) and is sub-
stituted by barite 2 (Fig. 5D). Calcite 2 occurs in small fractures as
euhedral crystals (sparry white calcite and dark brown calcite) hosted
in (Fig. 5F).
L. Rddad, et al. Ore Geology Reviews 113 (2019) 103070

Fig. 3. Geologic map of Slata and Guern Halfaya area (modified after Hammami and Smati, 1993).

The Guern Halfaya comprises two longitudinal Triassic outcrops
defining the Koudiat el Hamra – Jebel Oum Edeboua zone in the
northwestern part. The northern–northwestern parts are cut by NE–SW-
and N–S- trending normal faults, which are locally intruded by the
Triassic evaporites (Fig. 3).
The Pb-Zn mineralization at the Oum Edeboua deposit occurs as
lenticular, stratiform, vein, dissemination, and stockwork (Fig. 7A-F).
The ore is hosted within the contact between the Triassic dolostones
and the Upper Cretaceous series (contact zone) and in the Cenomano-
Turonian marl-limestone alternations. The orebodies are distributed
around the NE–SW- trending evaporite-bearing Triassic rocks and are
closely associated with the NE–SW- and N–S- trending normal faults
(Fig. 3). The early sulfate stage of ore consists of celestite and barite,
which are considered the main gangue minerals. Massive celestite
(Fig. 7A) and massive barite (Fig. 7C) from the contact zone predates
sulfides. This mineralizing event is followed by the sulfide stage which
is represented by galena, sphalerite, pyrite, and chalcopyrite. These
sulfides occur as disseminations in celestite and as stockwork in

Fig. 4. Locations of Fahdene Formation near Sidi Amor Ben Salem in Slata district (A) and Bahloul Formation near Jebel Harigua in Guern Halfaya district (B).

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L. Rddad, et al. Ore Geology Reviews 113 (2019) 103070

Fig. 5. Photographs and microphotographs of hand samples of ore from the Slata ore district. (A) Tabular barite (Ba-1) and ankerite (An) replacement of the Serdj
Limestone (SL). (B) Tabular, translucent barite (Ba-1) and disseminated galena (Gn) in the Serdj Limestone (SL). (C) Euhedral cm-sized galena (Gn) hosted in
Vraconian contact breccia (VCB). (D) Barite-2 (Ba-2) replaces calcite-1(Ca-1) in veins hosted in the Serdj Limestone. (E) Fibro-radial barite 2 (Ba-2) hosted in
dissolution cavities in the Serdj Formation. (F) Fractures filled with sparry white calcite and dark calcite (Ca-2) in the Serdj Limestone.

Turonian carbonate matrix (Fig. 7A, B, D, E, F). The post-ore stage
consists of late calcite followed by the oxidation stage (Jemmali et al.,
2013a,b).
4. Methods and materials
In this study, laminated black marly limestone, black marly lime-
stone, black marls, gray-black limestones constitute a suite of re-
presentative samples collected from different sections of the Fahdene
Formation (n = 36) and the Bahloul Formation (n = 19) (Fig. 8). These
samples were analyzed for their organic and trace element contents.
The trace elements (Pb, Zn, Cu, Ni, Co, Cr, Cd, and Sr) were determined
from 16 and 13 samples from Fahdene and Bahloul Formations, re-
spectively using atomic absorption spectroscopy (AAS) at the Geology
Department of the University of Tunis. For this analysis, 500 mg of each
sample were powdered to 100 μm and then digested with 10 ml of
hydrofluoric acid and 10 ml of perchloric acid for 16 h at 20 °C (cold
digestion) and at 60 °C (hot digestion). The reaction was completed
with 5 ml of perchloric acid and the solution was taken up in 25 ml of
water and 5 ml of nitric acid. After boiling, the solution was cooled off
and poured into a 100-ml vial. Gauging at 100 ml was achieved by the
addition of distilled water. The analytical precision was better than
7‰.
The concentration of TOC was determined by combustion of 50 to
100 mg sample at 1100 °C under oxidant environment in a Carmograph-
8 Wosthoff at the organic geochemistry laboratory, Geology
Department of the University of Tunis. For this analysis, each sample
was powdered and was de-carbonated by the addition of an HCl solu-
tion (2 N) at 60 °C overnight. The obtained dry residue was then placed
in a Carmograph oven at 1100 °C.
Rock samples were pyrolyzed using Rock-Eval at the organic geo-
chemistry laboratory, Geology Department of the University of Tunis.
This technique was used to identify the type of OM, assess the source
rock potential, and the thermal maturity of OM (Tissot and Welte,
1984). 100 mg of a sample was powdered and placed in an inert at-
mosphere (helium) and combusted at a programmable temperature

6
L. Rddad, et al.
from 250 °C to 550 °C, and a speed of 25 °C/min. Pyrolysis analysis
provides important parameters such as S1 and S2. The S1 represents free
hydrocarbons in the kerogen. S2 represents pyrolyzable hydrocarbons
generated by pyrolysis related to the petroleum-generating potential of
the sediment. It is normalized to TOC to calculate the hydrogen index.
Tmax is the temperature at which the S2 peak reaches its maximum
evolution.
The following geochemical parameters were calculated from the
Rock-Eval analysis. The hydrogen index [HI = (S2/TOC) × 100)] is
proportional to the kerogen elemental H/C ratio; it provides an idea
about the hydrocarbon potential of the rock (Tissot and Welte, 1984).
The genetic potential (GP = S1 + S2) is defined as the amount of pet-
roleum that kerogen is able to generate (Tissot and Welte, 1984). The
production index [PI = S1/(S1 + S2)] is a ratio of the hydrocarbons that
already generated (S1) from kerogen to the quantity of whole hydro-
carbons that can be obtained from kerogen (Tissot and Welte, 1984).
The PI is a good indicator of organic maturity (Espitalié et al., 1985).
The pyrolyzable carbon [(PC = ((S1 + S2) × 0.083), Espitalié et al.,
1985] represents the maximum amount of hydrocarbon that a sample is
able to generate. The residual carbon [(RC = TOC-PC)] is the portion of
the TOC, which represents the non-pyrolyzable organic carbon
(Johannes et al., 2006).
Scanning electron microscope (SEM) analyses of representative
samples from both Fahdene (n = 5) and Bahloul (n = 3) Formations
were performed at the Physical Science Department of Kingsborough
Community College using a JEOL JSM 5910LV scanning electron mi-
croscope with an EDAX energy dispersive spectroscope. Energy dis-
persive spectroscopy (EDS) was performed on these samples to in-
vestigate the make-up of the rock matrix and the distribution of OM and
inorganic matter (e.g., sulfides, carbonates). Sample preparation for the
analyses included carbon coating to 150 Å thickness, and processing in
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Ore Geology Reviews 113 (2019) 103070
Fig. 6. BSE (A-B) and SEI (C-D) images of organic
matter-rich limestone of the Fahdene and Bahloul
Formations. (A) Laminated limestone (GH9) with
mainly organic matter (OM) and diagentic pyrite (Py)
disseminated in the matrix. (B) Black laminated
limestone (SA15) with organic matter and pyrite/
framboidal pyrite disseminated in the matrix. (C)
Black laminated limestone with clusters of iron (oxy)
hydroxides (Fe-oxhd) that replaced frambroidal pyr-
ites (SA15). (D) Black laminated marly limestone
with disseminated pyrite (Py), organic matter (OM),
and veinlet of bitumen (Bit) (SA38).
Compo mode under backscattered electron (BSE) imaging detection.
Areas of the targeted rocks for investigation were first determined and
inspected in secondary electron imaging (SEI), and later switched to
backscatter (BSE) mode for qualitative elemental analysis.
SEM analysis allowed the identification of different organic and
inorganic (sulfides and Fe (oxy) hydroxides) fractions. These fractions
were analyzed for trace and major elements by laser ablation-in-
ductively coupled plasma-mass spectrometry (LA-ICP-MS). This ana-
lysis was carried out on samples from both Fahdene (n = 5) and
Bahloul (n = 3) Formations at the facility of Memorial University,
Newfoundland, Canada. Images of grains of interest were used to guide
LA-ICP-MS analyses. A GeoLas Arf Excimer LA system (193 nm) was
coupled to an Element XR ICP-MS. Spot analyses were used for in-
dividual analyses of known location. Single spot analyses were ablated
using 5 pulses/sec (5 Hz) and crater size of 20 µm. Ablated material was
transported via a He carrier gas (1 L/min) was mixed coaxially with Ar
prior to the ICP torch. Concentration and detection limit calculations
were conducted using the protocol of Longerich et al. (1996). Signals
were calibrated using USGS MASS-1 reference material (Wilson et al.
2002) for pyrite and NIST SRM 610 for iron oxide and carbonate. The
reference material (MASS-1 and NIST SRM 610) were analyzed two
times at the beginning and the end of each analytical session and after
20 measurements on samples. Stoichiometric iron (57Fe) content was
used as the internal standard for pyrite whereas a 100%wt oxide nor-
malization was done for Fe (oxy) hydroxide. Carbonates were normal-
ized to a 100 wt% total of CaCO3 while contributions of SiO2 and iron
oxides where taken into account if they were higher than 1%. Sulfur
was monitored to distinguish between Fe (oxy) hydroxide and pyrite.
Signals were de-convoluted from host contribution by using calcium as
a matrix monitor. This de-convolution was necessary since most of the
grains had a similar or smaller size than the LA-crater.
L. Rddad, et al.
Fig. 7. Main ore facies in the Oum Edeboua mine situated in the Vraconian limestones. (A) Celestite (Cel) associated with calcite (Ca) and disseminated galena (Gn).
(B) Stockwork of galena (Gn). (C) Massive centimeter-sized euhedral barite. (D) Crystals of galena (Gn) and sphalerite (Sph) associated with celestite (Cel). (E)
Crystals of galena (Gn) and chalcopyrite in the carbonate matrix (Ca). (F) Framboidal pyrite (Py) with galena crystals (Gn) disseminated in the carbonated matrix
(Ca).
5. Results of geochemical analysis and interpretation
5.1. Bulk mineral geochemistry
The results of trace element analysis of whole rock samples from the
Fahdene Formation of Jebel Slata and the Bahloul Formation of Guern-
Halfaya are reported in Tables 1 and 2, respectively. Geochemical
anomalies with respect to crustal abundance of individual metals in
shales and carbonates (Taylor, 1964) are recognized particularly for Pb,
Zn, and Ni in the Fahdene Formation of Slata with concentrations
reaching up to 114, 2615, and 146 ppm, respectively and also in the
Bahloul Formation of Guern-Halfaya with respective concentrations
reaching up to 4353, 8976, and 236 ppm.
5.2. SEM petrography and LA-ICP-MS of trace elements of organic and
inorganic fractions
SEM petrographic analysis of representative black laminated lime-
stones and marls from both formations reveal the presence of inorganic
and organic fractions. EDS analysis shows that the matrix consists
mainly of carbonate (calcite), pyrite and OM disseminated in the sili-
ciclastic material. SEM and SEI reveals the presence of framboidal
pyrite, Fe (oxy) hydroxides (oxidized framboidal pyrite), and sub-
ordinate barite, which form clusters of fine grains embedded in the
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Ore Geology Reviews 113 (2019) 103070
carbonate-siliciclastic matrix (Fig. 6A-D, Tables 3 and 4). In the mature
Fahdene Formation, bitumen fills veinlets cross-cut the matrix
(Fig. 6D). Given the complexity of the mineralogy of the matrix, we
focused on framboidal pyrite and Fe (oxy) hydroxide (oxidized fram-
boidal pyrite). Due to the high carbon background and the tininess of
the OM, it was not possible to get even a carbon signal from the OM.
Therefore, it was unfortunately not possible to analyze the OM by LA-
ICP-MS. Hence, we reported the trace elements data on pyrite, Fe (oxy)
hydroxides, and carbonates. The LA-ICP-MS analysis of the inorganic
fractions (Fe (oxy) hydroxide and pyrite) of selected samples from both
formations indicate anomalies (trace elements enrichments) (e.g., Pb,
Zn, Cu, Ba, Sr, Ni, Co) (Tables 3 and 4). Of particular interest are the
abnormally high concentrations of Pb (up to 5449 ppm) and Zn (up to
33076 ppm) in Fe (oxy) hydroxides in the Fahdene Formation. These
high concentrations of Pb (up to 2061 ppm) and Zn (up to 15530 ppm)
are also reported in Fe (oxy) hydroxides in the Bahloul Formation. Si-
milarly, anomalies of Pb and Zn are also registered in pyrites with re-
spective concentrations reaching up 706 ppm and 4084 ppm in the
Fahdene Formation and up to 980 and 1159 ppm in the Bahloul For-
mation.
L. Rddad, et al.
Fig. 8. Lithostratigraphic columns of the Fahdene Formation in Sidi Amor Ben Salem, Slata (A) and the Bahloul Formation in Jbel Hariga, Guern Halfaya (B).
5.3. Organic geochemistry
5.3.1. Source facies and total organic carbon
The geochemical analysis indicates that the Albian–Vraconian facies
of Slata and the Cenomanian–Turonian facies of Guern-Halfaya are rich
in OM. The TOC values vary between 0.2% and 1.4% (mean = 1.2%) in
Slata (Table 1) with the highest values registered in laminated black
marly and marly limestone rocks. In Guern-Halfaya, the TOC values
range from 0.62% to 5.46% (mean = 3.04%) (Table 2) with the highest
values recorded in laminated black limestone. These laminated black
limestones generally have the highest concentrations of trace metals.
The relationship OM and metals was investigated through (i) the cor-
relations between OM contents and trace elements concentrations and
(ii) LA-ICP-MS analysis of trace elements in inorganic and organic
fractions.
5.3.2. Type and maturity of organic matter
The diagrams representing the Rock-Eval parameter S2 versus TOC
and HI versus Tmax reveal that the organic matter of the majority of the
samples from the Fahdene and Bahloul Formations is primarily of Type
II with a contribution of Type III (Fig. 9A, B). Additionally, the positions
of the samples in the (S1 + S2) versus TOC and S2 versus TOC diagrams
reveal that the genetic hydrocarbon potential is fair to good quality for
both Fahdene and Bahloul Formations (Fig. 10A, B).
The pyrolysis analysis also reveals that the OM preserved in the
Bahloul Formation is immature (transition to the diagenesis-oil
window) as indicated by the HI versus Tmax diagram (Fig. 11) with Tmax
varying between 423°C and 433°C. Furthermore, the PI varies between
0.04 and 0.07 in this formation, indicating also that the OM is im-
mature. However, the OM of Bahloul Formation, located in the sub-
siding areas, reached maturity (Affouri et al., 2013). The OM within the
Albian–Vraconian facies of Slata is relatively mature as supported by
many lines of evidence. First, the plot of HI versus Tmax places the OM
preserved in this formation within the oil window (Fig. 11) with Tmax
values ranging from 431°C to 447°C. Moreover, the majority of the PI
values falls below 0.10. Furthermore, the TOC versus S1 diagram
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Ore Geology Reviews 113 (2019) 103070
reveals the presence of indigenous hydrocarbons within this formation
(Fig. 12). These results further confirm the maturity of OM preserved in
the Fahdene Formation.
5.4. Correlation between trace elements and organic matter contents
To determine the relationship between the analyzed elements and
OM contents (TOC, PC, RC), correlations between these variables in
both formations were plotted and presented in Figs. 13 and 14. Con-
trasting correlations between the elements and OM contents are noticed
in the Fahdene and Bahloul Formations.
The correlations between metals and OM are overall weak to absent
and moderately positive in the Fahdene and Bahloul Formations, re-
spectively. In the Bahloul Formation, four elements (Pb, Zn, Ni, Sr)
show overall moderate positive correlation with OM contents (Fig. 13).
These moderate positive correlations between OM contents (TOC, PC,
RC) and trace elements suggest a priori the presence of a geochemical
affinity between these elements and the OM preserved in this forma-
tion.
In contrast, the analyzed elements show poor to negative correlation
with OM contents in the Fahdene Formation (Fig. 14). This poor cor-
relation seems to indicate the absence of geochemical affinity between
these elements and OM preserved in this formation.
6. Discussion
The lack or negative correlation between trace elements and OM
contents in the Fahdene Formation is likely due to one or the combi-
nation of the following factors: (i) the partitioning of trace elements
between a mineral fraction and the organic fraction and (ii) the ma-
turity of OM. This kind of partitioning is less pronounced in the Bahloul
Formation where many trace elements moderately correlate positively
with the OM contents. The inability to analyze the OM fraction in both
formations does not necessary mean the metals were not sequestered by
OM. Given the development of anoxic environment (Affouri et al.,
2013; Khalifa et al., 2018; this study) and the high concentrations of
L. Rddad, et al. Ore Geology Reviews 113 (2019) 103070

Table 1
Rock-Eval parameters and concentrations of trace elements (ppm) in the Fahdene Formation. Notes: TOC = total organic carbon, wt %. S1 = volatile/free hydro-
carbon (HC). S2 = remaining HC generative potential, mg HC/ g rock. Tmax = temperature of peak S maximum, °C. HI = hydrogen index = (S2 × 100)/TOC, mg HC/
g TOC. PI = production index = S1/(S1 + S2). PC = pyrolyzable organic carbon = ((S1 + S2)/10) × 0.83, wt %. RC = residual organic carbon = TOC – PC, wt%.
GP = genetic potential = S1 + S2.
Sample Lithology Depth TOC PC RC S1 S2 GP PI HI Tmax Cd Cr Co Cu Ni Pb Sr Zn
(m) wt% wt% wt% mg/g mg/g wt% °C

S68 Black marly limestone 12 1.04 0.11 0.93 0.18 1.19 1.37 0.13 115 438 7 85.3 18 45 104.8 47.7 840 200
S67 Black laminated limestone 30 0.95 0.13 0.82 0.22 1.2 1.42 0.15 144
S66 Black limestone 31.5 1.23 0.16 1.07 0.53 1.37 1.9 0.28 208 440 4.7 68.4 29.7 53.3 81 56.8 809 63.8
S65 Gray marls 37.5 0 0.01 2.55 2.56 0
S64 Black laminated marl-limestone 45 1.4 0.44 0.97 1.4 0 1.4 1 276 447
S63 Black marly limestone 46.5 0.67 0.32 0.35 0.02 3.88 3.9 0.01 22 447 5.6 50.7 22.1 36.5 104.8 63.6 901 124.1
S62 Gray marls 49.5 0.01 0.01 0.15 0.16 0.06
S61 Gray marls 51 0 0.01 0.11 0.12 0.08
S60 Gray marls 56.25 0 0.02 0.01 0.03 0.67
S59 Black laminated limestone 63 1.4 0.42 0.98 1.41 0 1.41 1 260 435
S58 Gray marls 64.5 0.05 0.09 3.65 3.74 0.02 438
S57 Black to gray limestone 66 0.62 0.04 0.58 0.05 0.46 0.51 0.1 109 442 5.6 29.3 36.1 20 146.4 70.5 932 103.5
S56 Gray marly limestone 76.5 0.02 0.01 0.68 0.69 0.01 438
S55 Black laminated marl-limestone 76.95 1.21 0.13 1.08 0.21 0.25 0.46 0.46 115 442
S54 Black limestone 78 1.32 0.14 1.18 0.3 1.4 1.7 0.18 220 438 7 40 16.4 25.5 63.1 47.7 3926 69
S53 Black laminated limestone 79.5 0.91 0.12 0.79 0.1 2.9 3 0.03 146 439
S52 Gray marly limestone 81 0.37 0.21 0.16 0.17 1.33 1.5 0.11 633 438
S51 Black laminated marl limestone 82.5 1.03 0.21 0.82 0.24 2.33 2.57 0.09 296 435 9.7 25.3 23 34 81 68.2 840 148.3
S50 Black marls 84 0.95 0.29 0.66 0.48 3.03 3.51 0.14 142 438 5.6 41.3 27.1 12.8 104.8 70.5 994 103.5
S49 Gray marls 91.5 0.01 0 1.35 1.35 0 444
S48 Gray marly limestone 93 0.19 0.07 0.12 0.26 0.16 0.42 0.62 311 440
S47 Black limestone 103.5 0.56 0.08 0.48 0.33 0.6 0.93 0.35 212 440 2.8 24 28.7 20 81 93.2 1210 241.4
S46 Black laminated marly limestone 105 0.51 0.1 0.41 0.02 1.19 1.21 0.02 67 440 8.4 60 23 34 45.2 81.8 994 612.9
S45 Gray black limestone 115.5 0.04 0.15 0.14 0.29 0.52 445
S44 Gray limestone 117 0.04 0.15 0.14 0.29 0.52 445
S43 Black marls 120 0.56 0.03 0.54 0.33 0.33 0 55 444
S42 Gray marls 121.5 0.26 0.07 0.19 0.26 0.31 0.57 0.46 227 438
S41 Gray limestone 124.5 0.42 0.08 0.34 0.32 0.59 0.91 0.35 255 440 5.8 30.7 17.2 23.5 103.9 86.4 1235 89.7
S40 Gray marls 129.75 0.5 0.15 0.34 0.61 1.07 1.68 0.36 248 437
S39 Gray marls 135 0.21 0.06 0.15 0.34 1.23 1.57 0.22 204 447
S38 Black laminated marly limestone 139.5 0.88 0.06 0.82 0.33 0.43 0.76 0.43 181 441 8.4 21.3 12.3 13 81 63.6 1395 241.4
S37 Gray limestone 145.5 0.28 0.11 0.17 0.55 1.59 2.14 0.26 279 442
S36 Black to gray limestone 148.5 0.79 0.19 0.6 1.46 0.78 2.24 0.65 251 439 8.2 53.1 18.8 31.4 117.6 113.6 933 55.2
S35 Gray marly limestone 153.75 0.26 0.05 0.22 0.17 1.98 2.15 0.08 152 440
S34 Gray marly limestone 156 0.02 0.12 0.4 0.52 0.23
S33 Gray limestone 161.25 0.58 0.12 0.47 0.26 0.09 0.35 0.74 197 440
S32 Gray marly limestone 177 0 0.05 1.15 1.2 0.04
S31 Gray marls 177.75 0.01 0.03 0 0.03 1
S30 Black laminated marly limestone 181.5 0.87 0.18 0.69 0.3 0.04 0.34 0.88 211.49 438
S29 Gray limestone 183.75 0.01 0.01 1.84 1.85 0.01
S28 Black laminated limestone 187.5 0.67 0.02 0.64 0.01 0.1 0.11 0.09 42 442
S27 Gray marly limestone 188.7 0.39 0.03 0.36 0.09 0.28 0.37 0.24 62 439 5.6 58.7 26.2 28 81 63.6 901.2 103.5
S26 Gray marls 189 0.01 0.03 0.24 0.27 0.11
S25 Gray limestone 191.1 0.01 0.02 0.06 0.08 0.25
S24 Gray limestone 191.4 0.01 0.05 0.05 0.1 0.5 0
S23 Gray marls 192 0 0.04 0.06 0.1 0.4
S22 Black to gray limestone 193.05 0.42 0.03 0.39 0.08 0 0.08 1 57 441
S21 Black marly limestone 193.5 0.74 0.06 0.68 0.08 0.24 0.32 0.25 87 439
S20 Black limestone 195 1.23 0.07 1.16 0.2 0.64 0.84 0.24 436 7 56 20.5 29 57.1 45.5 932.1 179.3
S19 Gray marls 196.5 0.88 0.29 0.59 0.24 2.58 2.82 0.09 436
S18 Black limestone 198 1.23 0.1 1.13 0.07 3.23 3.3 0.02 94 435
S17 Black limestone 201.3 0.88 0.07 0.81 0.09 1.16 1.25 0.07 88 439
S16 Gray marls 201.6 0 0 0.78 0.78 0
S15 Black laminated marly limestone 202.05 0.49 0.02 0.47 0.03 0 0.03 1 45 440
S14 Gray marls 202.5 0.01 0.22 0.23 0.04
S13 Gray marls 207.75 0.01 0.03 0.02 0.05 0.6
S12 Gray limestone 208.5 0.7 0.04 0.66 0.07 0.06 0.13 0.54 67 435
S11 Gray marly limestone 213.75 0.74 0.07 0.66 0.13 0.47 0.6 0.22 437
S10 Black laminated marly limestone 217.5 0.9 0.08 0.82 0.26 0.75 1.01 0.26 437 3.5 83.8 15.6 40.8 81 75 1117.3 155.2
S9 Black laminated marly limestone 222 1.05 0.08 0.97 0.07 1.46 1.53 0.05 88 435
S8 Gray marls 223.5 0.71 0 0.71 0.07 0.93 1 0.07
S7 Gray marls 232.5 0 0.05 0.05 0
S6 Black gray marls 242.25 0.97 0.03 0.94 0.07 0.31 0.38 0.18 32 447 4.1 83.8 15.6 45.5 81 97.7 1364.2 124.1
S5 Gray marls 244.5 0.74 0.02 0.71 0.07 0.23 0.3 0.23 31

trace elements in the diagenetic pyrite, it can be inferred that the Al- The incorporation of trace elements in both the inorganic and or-
bian-Vraconian and the Cenomanian-Turonian seawaters were enriched ganic fractions in the Fahdene Formation (Tables 3 and 4; Fig. 15A)
in trace elements during the sedimentation (Fig. 15A). Hence, the OM leads us to consider factor (i) as one explanation for the lack of corre-
must have sequestered a fraction of these trace elements. lation between OM and trace elements. Apart from this partitioning

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Table 2
Rock-Eval parameters and concentrations of trace elements (ppm) in the Bahloul Formation. Notes: TOC = total organic carbon, wt %. S1 = volatile/free hydro-
carbon (HC). S2 = remaining HC generative potential, mg HC/ g rock. Tmax = temperature of peak S maximum, °C. HI = hydrogen index = (S2 × 100)/TOC, mg HC/
g TOC. PI = production index = S1/(S1 + S2). PC = pyrolyzable organic carbon = ((S1 + S2)/10) × 0.83, wt %. RC = residual organic carbon = TOC – PC, wt%.
GP = genetic potential = S1 + S2.
Sample Lithology Depth TOC CP C.R S1 S2 GP IP HI Tmax Cd Cr Co Cu Ni Pb Sr Zn
(m) wt% wt% wt% mg/g mg/g °C

GH19 Gray massive limestone 0.3 0.03 0.03 0.33 0.36 0.08 433
GH18 Black laminated 0.4 1.82 0.17 1.65 0.11 1.97 2.08 0.05 108 433 4.67 22.35 18.75 25.5 57.14 140.91 716.05 1000
limestone
GH17 Gray laminated 1.3 0.83 0.28 0.55 0.09 3.29 3.38 0.03 395 426 5.57 32 21.31 12.75 75.9 163.64 1209.88 1051.72
limestone
GH16 Black laminated 2.15 1.22 0.29 0.93 0.04 3.44 3.48 0.01 282 430
limestone
GH15 Black laminated 3.8 5.46 1.23 4.23 0.8 13.96 14.76 0.05 256 423 22.26 58.67 21.31 505 235.71 1238.64 1271.6 8975.81
limestone
GH14 Gray marly limestone 5.8 0.62 0.5 0.12 0.13 5.95 6.08 0.02 954 430 5.29 51.68 29.69 42.35 103.9 245.55 987.93 1655.17
GH13 Black limestone 7.7 1.56 0.58 0.98 0.35 6.58 6.93 0.05 422 426 6.96 34.67 27.05 25.5 92.86 318.18 1302.47 725.81
GH12 Black marly limestone 9.4 1.3 0.45 0.85 0.13 5.33 5.46 0.02 410 431
GH11 Black limestone 9.9 1.49 0.41 1.07 0.09 4.85 4.94 0.02 327 430
GH10 Black limestone 10.8 1.66 0.59 1.07 0.3 6.86 7.16 0.04 413 423 11.13 32 11.48 28 51.19 247.73 1024.69 1594.48
GH9 Black laminated marly 11.4 1.14 0.45 0.69 0.11 5.3 5.41 0.02 465 423 23.36 34.92 32.81 36.08 100.58 200.27 878.16 1431.03
limestone
GH8 Gray limestone 12.6 0.78 0.36 0.43 0.26 4.04 4.3 0.06 516 423 9.93 16.76 28.13 7.84 51.19 40.91 654.32 793.1
GH7 Black limestone 12.9 1.66 0.46 1.2 0.05 5.54 5.59 0.01 333 427 3.5 47.49 18.75 50.2 93.64 285.45 1344.68 2655.17
GH6 Black laminated 13.9 2.34 0.75 1.59 0.55 8.51 9.06 0.06 364 427 12.52 30.67 40.98 28 128.57 372.73 1611.11 4000.35
limestone
GH5 Black marly limestone 14.4 0.83 0.18 0.65 0.05 2.11 2.16 0.02 253 432 8.18 44.69 18.75 31.37 97.06 370.45 768.39 1672.41
GH4 Black laminated 14.65 1.82 0.6 1.22 0.51 6.67 7.18 0.07 366 426 7.01 61.45 17.19 42.35 131.24 500.91 933.04 2396.55
limestone
GH3 Gray marls 14.9 0.02 0.02 0.17 0.19 0.11
GH2 Black limestone 15.8 1.04 0.25 0.79 0.05 2.94 2.99 0.02 283 427 11.13 41.33 29.51 22 61.9 227.27 1024.69 1161.29
GH1 Gray marls 16.6 0.01 0.01 0.11 0.12 0.08

Table 3
LA-ICP-MS trace elements (ppm) and major elements compositions (wt%) of organic matter-rich facies of the Fahdene Formation (Fe, Py and Cal next to sample
reference indicates hydro(oxy)ide of iron, pyrite, and carbonate, respectively).
Sample SA9-Fe SA9-Cal SA15-Fe SA38-Fe SA38-Cal SA67-Fe SA67-Cal SA8-Py
(n = 11) (n = 11) (n = 5) (n = 10) (n = 6) (n = 10) (n = 8) (n = 3)

Major elements (wt%)

SiO2 4.06 1.8 10.2 5.23 1.9 2.57 4.2 4400
TiO2 0.02 0.02 0.06 0.004 0.03 0.17 0.02 91
Al2O3 0.52 0.60 2.46 0.26 0.52 0.02 0.74 166
Fe2O3 96 0.74 92 94 1.0 99 0.47 466,000
MgO 0.76 0.41 1.23 0.64 0.39 0.43 0.44 113
Na2O 0.05 0.04 0.08 0.02 0.03 0.09 0.04 68
K2O 0.03 0.13 0.23 0.02 0.09 < 0.04 0.17 < 19
P2O5 0.13 0.08 0.20 0.04 0.10 0.20 0.07 < 41
CaCO3 – 98 – – 97 – 95 –

Trace elements (ppm)

As 224 <6 1040 175 5 237 <4 209
Ba 145 19 138 167 11 381 24 457
Cd <7 <5 < 14 <2 <4 < 36 <6 <2
Co 119 <2 95 54 <4 62 <4 147
Cu 552 < 20 2449 246 < 15 495 < 25 293
Mn 1332 121 1144 157 135 240 48 416
Mo 57 <1 385 50 <2 38 < 1.5 9
Ni 811 < 15 2852 768 < 20 471 < 15 287
Pb 353 2 744 320 3 3386 13 394
Se 156 < 15 142 26 < 15 80 < 20 53
Sr 853 668 1356 213 776 87 620 194
Th 2.1 0.4 1.05 0.2 0.5 0.8 0.4 2
U 7 0.5 11 7.1 0.4 6 0.7 0.9
V 124 9 408 246 8 127 9 98
Zn 6299 82 3260 825 50 20,855 119 3207
Zr 3 4 23 9 6 3 3 2

factor (i), the maturity of OM (ii) is, yet, another explanation for the
poor correlation between OM and trace elements in the Fahdene For-
mation. In fact, the thermal cracking of OM in the Fahdene Formation
had caused a decrease of the original TOC content. Consequently, a
fraction of the endowment, initially concentrated within the OM
fraction, mostly likely in the Nitrogen-, Sulfur-, Oxygen-rich compounds
(NSO), underwent dissociation and migrated along with the hydro-
carbons. This is in agreement with the experimental studies carried out
by Disnar (1982) who showed that metals are associated with NSO
compounds. These compounds are abundant in the Fahdene and

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Table 4 maturity of OM in the diapiric zone (Soua, 2009; Affouri et al., 2013;
LA-ICP-MS trace elements (ppm) and major elements compositions (wt%) of Khalifa et al., 2018) implies basinal temperature below 200 °C. Under
organic matter-rich facies of the Bahloul Formation (Fe, Py and Cal next to 200 °C, dissolved organic ligands form stable aqueous metal-organic
sample reference indicates hydro(oxy)ide of iron, pyrite, and carbonate, re- complexes, which promote their solution and transport (Kharaka et al.,
spectively).
1985; Giordano and Kharaka, 1994). The metal-rich hydrocarbons
Sample GH5-Fe GH5-Cal GH11-Fe GH11-Cal GH9-Py migrated from deep subsiding areas to the diapiric paleohighs at Slata
(n = 4) (n = 5) (n = 5) (n = 3) (n = 2) and Guern Halfaya. At the loci of ore deposition, the metal-carrying
hydrocarbons mixed with sulfate- or sulfur-rich fluids which were most
Major elements (wt%)
SiO2 < 0.43 0.06 3.56 3.4 1.50 likely sourced from the Triassic evaporites (Smati, 1986; Jemmali et al.,
TiO2 < 0.003 < 0.001 < 0.002 0.05 0.013 2013a). This fluid mixing led to the precipitation of sulfates and sulfides
Al2O3 < 0.004 0.02 0.13 0.83 0.04 in the Slata and Guern Halfaya mining districts.
Fe2O3/FeS2 99 0.61 97 1.2 100
In the Bahloul Formation of Guern Halfaya area, there is, however, a
MgO 0.46 0.04 0.37 0.50 0.02
Na2O 0.03 0.01 0.015 0.05 0.03
totally different situation. In this area, the moderate positive correla-
K2O < 0.02 < 0.002 0.72 0.12 0.02 tions between trace elements and OM contents indicate that a fraction
P2O5 0.03 0.05 0.04 0.05 < 0.01 of the trace elements were linked to the OM. The trace elements and
CaCO3 – 100 – 95 – TOC contents were preserved due to the immaturity of OM. As a result,
Trace elements (ppm) the dissociation of OM-metals did not or barely occur. The OM content
As 691 < 0.7 585 <2 225 and the metal endowment were likely the same as the ones inherited
Ba 83 <1 50 12 26
during the accumulation of metals within OM via early diagenesis. In
Cd < 22 <2 11 <5 <2
Co 248 < 1.5 339 <4 205 other words, the initial organo-metallic complexes preserved within the
Cu 1072 <6 1525 < 15 342 remaining immature kerogen macromolecules were barely modified
Mn 1095 1127 1490 481 646 because of the low degree of OM maturity (diagenetic zone or immature
Mo 108 < 0.3 48 <1 17 zone). This preservation of metal-OM is reflected by the moderate po-
Ni 1542 <4 809 < 10 579
sitive correlations between trace metals and OM contents. Such im-
Pb 1711 <1 1533 13 942
Se 89 <5 43 < 20 72 mature OM-rich black facies (e.g., Bahloul Formation) would be po-
Sr 331 1086 16 622 31 tential sources of metals if in other areas they underwent possible
Th 0.8 0.03 0.7 1.2 3 catagenetic and/or hydrothermal transformations. The Bahloul
U 7 0.06 6 0.3 0.6
Formation, located in the deep subsiding basin, have reached maturity
V 446 23 112 34 168
Zn 14,090 5 801 31 1044 (Affouri et al., 2013) and, thus, would have acted as a potential con-
Zr <1 27 2 14 3 tributor of metals for the ore deposits of the Slata and Guern Halfaya
mining districts.
The maturity of OM in the Fahdene and Bahloul Formations, located
Bahloul Formations in the diapiric zone (Affouri et al., 2013; Khalifa in the more subsiding basin, required burial of these formations to
et al., 2018). Indeed, the extraction of different hydrocarbon fractions depths of at least 3 km. These depths could have been reached during
from these formations reveals the overall abundance of polar com- the Late Cretaceous to the Early Eocene period (Belayouni, 1992). It is
pounds (NSO) compared to the saturated hydrocarbons (SHC) and during this time that the expulsion of hydrocarbons and the metals
aromatic hydrocarbons (AHC) (Affouri et al., 2013; Khalifa et al., started as a result of thermal cracking of the kerogen. Generation and
2018). These authors reported NSO concentration values that are migration of the hydrocarbons reached their peak during the Eocene
greater than 45% and 65%, in Fahdene and Bahloul Formations, re- period (Belayouni, 1992). This period of maximum hydrocarbon gen-
spectively. This is in line with the findings of Belayouni (1992) who eration is concomitant to the Alpine orogeny, during which large
investigated the oils seeps in the diapiric zone and concluded that the amounts of hydrocarbons, along with the associated metals, migrated
NSO compounds are overall abundant. Given the predominance of these from the deep parts of the basin towards the peridiapiric paleohighs of
compounds, it is likely that the metals were incorporated within the the Slata and Guern Halfaya ore districts. The Alpine orogeny and the
mobile hydrocarbons and specifically the polar fractions and the asso- development of the topographic gradient between the basins and the
ciated waters. The importance of hydrocarbons as a source and carrier paleohighs were effective driving mechanisms for the flow of the ore-
of metals is highlighted by several authors (Saxby, 1976; Giordano, forming fluids (i.e. metal-rich hydrocarbons) (Garven, 1995; Leach
1985; Trichet et al., 1987; Kharaka et al., 1985; Giordano and Kharaka, et al., 2010). At the loci of deposition, metal-rich hydrocarbons mixed
1994; Migdisov et al., 2017; Saintilan et al., 2019). The thermal with dissolved Triassic evaporites or H2S-derived TSR, which led to the

HI 700 HI 400 A HI 700 B

5 20
Type I Type II/III Type I
4.5 Oil Prone Type II 18 Oil Prone
Oil/Gas HI 200 HI 400
Oil Prone
S 2 (mg HC/g rock)

4 Prone 16 Type II
S 2 (mg HC/g rock)

3.5 14 Oil Prone

12 Type II/III HI 200
3
Oil/Gas Prone
2.5 Type III 10
2 Gas Prone 8 Type III
1.5 6 Gas Prone
HI 50
1 4 HI 50
Type IV
0.5 2 Type IV Dry Gas Prone
Dry Gas Prone
0 0
0 0.5 1 1.5 2 0 1.5 3 4.5 6
TOC (%) TOC (%)

Fig. 9. TOC vs S2 diagrams showing type of organic matter in the Fahdene Formation (A) and Bahloul Formation (B).

12
L. Rddad, et al. Ore Geology Reviews 113 (2019) 103070

A B

Poor Fair Good Excellent Poor Fair Good Excellent

Excellent
Exellent

S 2 (mg HC/g rock)

10 10

S2 (mg HC/g rock)

Good Good

Fair
Fair

1 1

Poor
Poor

0.1 0.1
0. 1 1 10 0 .1 1 10
TOC (%) TOC (%)

Fig. 10. TOC vs (S1 + S2) diagram showing the quality of organic matter in the Fahdene Formation (A) and the Bahloul Formation (B). TOC: total organic carbon (%).
S2: potential hydrocarbons (mg HC/g Rock).

precipitation of sulfates and sulfides at different times. 10

7. Ore genesis model

Considering the spatial-temporal relationship between the OM-rich

S1 (mg HC/g rock)

Cretaceous formations, on the one hand, and the Triassic salt-bearing
1
diapir and a favorable reservoir (e.g., Aptian carbonate,
Cenomanian–Turonian facies), on the other hand, it is proposed that
these metal- and OM-rich formations played a role in the genesis of the
ore in the Slata-Guern Halfaya districts. The ore genesis model, sum-
marized in Fig. 15, can be also applied for the diapiric-related ore de-
posits in the diapiric zone. 0.1
Basement rocks were proposed as potential sources of base metals
(Mesozoic basement: Sheppard et al., 1996; Bouhlel, 2005; Jemmali
et al., 2016; Paleozoic series: Jemmali et al., 2013a; Bouhlel et al.,
2016). In that respect, part of the ore-forming fluids stemmed from the
basement and migrated to the peridiapiric paleohighs. At the loci of
deposition, these metalliferous fluids mixed with dissolved Triassic 0.01
sulfate-rich fluids (Souissi et al., 2007; Bouhlel et al., 2016). However, 0.1 1 10
to account for the size of the orebodies in the diapiric zone ore pro- TOC (%)
vince, Cretaceous formations rich in OM should have also contributed
to the metallic stock/budget of the ore deposits. The OM-rich rocks Fig. 12. TOC vs S1 diagram in the Fahdene Formation. (TOC: total organic
have long been proposed as source beds of Pb, Zn, and other metals of carbon (%). S1: free hydrocarbons (mg HC/g Rock)).
MVT ores (Coveney, 1979; Long and Angino, 1982; Coveney and
Glascock, 1989; Saintilan et al., 2019) and a source for Pb, Zn, and where the OM-rich Cretaceous formations contributed as sources of
other metals in oilfield brines (Billings et al., 1969; Carpenter et al., metals. During the Late Aptian, the ascent of the Triassic evaporites
1974). It is also the case for the Slata-Guern Halfaya mining districts along major faults is of immense importance in the genesis of the ore.

Type A 1000 Type I B

1000
I
R0 R0 0.5
Hydrogen Index (mg HC/g TOC)
Hydrogen Index (mg HC/g TOC)

900 900
0.5
800 800
Type Type II
700 700
II
600 600
500 500
400 400
300 R0 300 R0 1.35
200 1.35 200
Type Type III
100 100
III
0 0
400 420 440 460 480 500 400 420 440 460 480 500
Tmax ( o C ) Tmax ( o C )
Fig. 11. Plot HI vs Tmax diagram in the Fahdene Formation (A) and the Bahloul Formation (B). (Tmax: S2 peak maximum pyrolysis temperature (°C). HI: hydrogen
index (mg HC/g TOC)).

13
L. Rddad, et al. Ore Geology Reviews 113 (2019) 103070

600 600 600

500 500 500
400

Pb (ppm)
400 400

Pb (ppm)
Pb (ppm)

300 300 300

200 200 200
100 100 100
0 0 0
0 0.5 1 1.5 2 2.5 0 2 4 6 8 0 0.5 1 1.5 2

5000 5000 5000

4000 4000 4000
Zn (ppm)

Zn (ppm)

Zn (ppm)
3000 3000 3000
2000 2000 2000
1000 1000 1000
0 0 0
0 1 2 3 0 2 4 6 8 0 1 2

140 150
140
120 120
100 100
Ni (ppm)

100

Ni (ppm)
Ni (ppm)

80 80
60 60
50
40 40
20 20
0 0
0 0 0.5 1 1.5 2
0 1 2 3 0 5 10
1800
2000 1600
2000
1400
1500
Sr (ppm)

1500 1200
Sr(ppm)
Sr (ppm)

1000
1000 1000 800
600
500 500 400
200
0 0 0
0 1 2 3 0 5 10 0 1 2
Total organic carbon (%) Residual carbon (%)
Pyrolyzable carbon index (%)

Fig. 13. Correlation between organic matter contents (TOC, PC, RC) and selected trace elements (ppm) in the Bahloul Formation. (TOC: total organic carbon (%). PC:
pyrolyzable carbon (%). RC: residual carbon (%)).

First, this halokinetic event created paleohighs on which carbonate
platforms developed (e.g., Aptian carbonate of Slata). Such carbonate
platforms are suitable reservoirs for the ore deposition. Together with
tectonic activity, this diapirism have also created restricted basins,
adjacent to diapiric paleohighs, in which anoxic conditions were de-
veloped during the deposition of both the Fahdene and Bahloul For-
mations. This led to the accumulation and preservation of OM in these
formations. These anoxic conditions promoted the incorporation of
trace elements, particularly Pb and Zn, in organic and inorganic frac-
tions (Fig. 15A). This metal-enriched OM was accumulated and pre-
served in an anoxic environment.
During the Late Cretaceous to Eocene time, these metal- and OM-
rich formations, located in the deep subsiding basin, underwent cata-
genetic transformations due to substantial subsidence. As a result of this
catagenesis, the organo-metallic ligands were destabilized causing the
liberation and the expulsion of the metals and hydrocarbons from these
formations. These formations are not exclusively made of shale, but
rather of limestone and marly limestone. Hence, the expulsion of metals
could have been achieved with relative ease owing to the good per-
meability/porosity of limestone. Furthermore, the overpressure caused
by the accumulation and saturation of hydrocarbons within the pores
may have cracked the rocks (hydraulic fracturing) allowing the lib-
eration of metals and hydrocarbons.
The Alpine compression and the development of topographic
gradient during the Eocene-Miocene orogenic thrust triggered extensive
migration of the metals-rich hydrocarbons and associated waters from
the subsiding basin (SE) towards the diapir paleohighs (NW) (Fig. 15B).
The proposed migration path (SE to NW) explains the occurrence of
both oil seeps and ore deposits primarily along the southeastern border
of the Triassic outcrops (Chaari et al., 2003). The occurrence of the ore
mainly in the SE flank of the salt diapir is significant in ore exploration.
In that respect, the SE flanks of the diapirs can be used as a geological
guide for base metal exploration.
The trapping of the fluids involved in the genesis of mineralization
occurred when these fluids encountered appropriate stratigraphic, li-
thologic, structural, and geochemical traps. At Slata, metal-bearing
hydrocarbons and associated metal-rich fluids were trapped in the
Aptian carbonate reservoir located between the Triassic evaporite dia-
pirs and the carbonaceous Fahdene Formation. At Guern Halfaya, ore-
bearing fluids were trapped within the Cenomanian and
Cenomanian–Turonian facies (Bahloul Formation) that are overlain by
the impermeable Coniacian–Santonian marls. The Triassic evaporite
diapirs that outcrop in both ore districts played not only a role as
barriers, but also as the primary source of sulfur and sulfate for the ores
in the Slata ore district (Smati, 1986) and the Guern Halfaya ore district
(Jemmali et al., 2013a). Besides the role of OM-rich Cretaceous for-
mations as a source of metals, the generated hydrocarbons from these
formations (i) promoted the reduction of the Triassic sulfates mainly

14
L. Rddad, et al. Ore Geology Reviews 113 (2019) 103070

120 120 120

100 100 100
80 80
Pb (ppm)
80

Pb (ppm)

Pb (ppm)
60 60 60
40 40 40
20 20 20
0 0 0
0 0.5 1 1.5 0 0.1 0.2 0.3 0.4 0 0.5 1 1.5
TOC PCI RC
300 300 300
250 250 250
200 200 200

Zn (ppm)
Zn (ppm)

Zn (ppm)
r = -0.04 r = 0.1
150 150 150
100 100 100
50 50 50
0 0 0
0 0.5 1 1.5 0 0.1 0.2 0.3 0.4 0 0.5 1 1.5
TOC PCI RC
160 160 160
140 140 140
120 120 120

Ni (ppm)
100
Ni (ppm)

Ni (ppm)

100 100
80 80 80
60 60 60
40 40 40
20 20 20
0 0 0
0 0.5 1 1.5 0 0.1 0.2 0.3 0.4 0 0.5 1 1.5

1600 1600 1600

1400 1400 1400
1200 1200 1200 r = -0.1
Sr (ppm)

Sr (ppm)

Sr (ppm)
1000 1000 1000
800 800 800
600 600 600
400 400 400
200 200 200
0 0 0
0 0.5 1 1.5 0 0.1 0.2 0.3 0.4 0 0.5 1 1.5
Total organic carbon (%) Pyrolyzable carbon index (%) Residula carbon (%)

Fig. 14. Correlation between organic matter content (TOC, PC, RC) and selected trace elements (ppm) in the Fahdene Formation. (TOC: total organic carbon (%). PC:
pyrolyzable carbon (%). RC: residual carbon (%)).

through thermochemical sulfate reduction (TSR) and (ii) triggered the
precipitation of sulfides. It is noteworthy to indicate that the Triassic
sulfates can be reduced when they are dissolved. In that respect, me-
teoric waters that descended along major faults are likely the cause of
the dissolution of the Triassic sulfates. The dual source rock role (hy-
drocarbons and metals) of the OM-rich formations was also proposed by
Orgeval et al. (1986) and Montacer et al. (1988) for Bou Grine ore
deposit where the Bahloul Formation simultaneously acted as the
source of metals and hydrocarbons. When the influx of hydrocarbons
decreased, TSR was inhibited, which led to the sluggishness of H2S
production. Subsequently, the unreduced Triassic dissolved sulfates
combined with Sr and Ba, leading to the precipitation of sulfates.
The proposed model reveals the importance of the basinal evolution
and the OM maturity in the genesis of the ore in the Slata-Guern
Halfaya districts and likely also in other diapir-related ore deposits.
This role was also highlighted in North Africa (e.g., Jebel Tirremi
Jurassic carbonate-hosted MVT ore deposit in Northeastern Morocco,
Bouabdellah et al., 2013; Bou-Jaber peridiapiric ore deposit in the
Tunisian diapiric zone, Bouhlel et al., 2016) and Europe (e.g., Murguía
and Orduña-diapir related deposits in the Basque-Cantabrian basin,
Perona et al., 2018).
8. Concluding remarks
analyses of the Albian–Vraconian facies (Fahdene Formation) of the
Slata ore district and the Cenomanian–Turonian facies (Bahloul
Formation) of Guern Halfaya support the following conclusions:
• Organic matter was accumulated and preserved in anoxic environ-
ments during the deposition of Albian-Vraconian and Cenomanian-
Turonian sediments. These sediments acquired their metallic stock
during early diagenetic reactions.
• During Late Cretaceous-Early Eocene time, the organic matter of
these formations reached maturity in the subsiding basin.
• Due to the organic matter thermal cracking, the organo-metallic
ligands were destabilized and dissociated, and the metals were then
incorporated into mobile hydrocarbons and associated waters.
• The post-Cretaceous Alpine orogeny and the development of a to-
pographic gradient caused the transport of metals and hydrocarbons
from the subsiding basin (SE) to the diapir paleohighs (NE).
• The metal-rich hydrocarbons and associated ore-bearing waters in-
vaded the Triassic dissolved sulfate fluids, which led to the pre-
cipitation of sulfates and sulfides at different times.
This study clearly shows the role of the Cretaceous organic-rich
formations and halokinesis in the genesis of the ore in the Slata-Guern
Halfaya districts and likely also in the diapiric-related ore deposits in
the diapiric zone.

The geological data and the mineral and organic geochemical

15
L. Rddad, et al. Ore Geology Reviews 113 (2019) 103070

Fig. 15. Chronological stages leading to the emplacement of ore in the Slata-Guern Halfaya ore districts. (A) Sequestration of metals by organic and inorganic matters
in an anoxic environment. (B) Genetic model of the diapiric-related ore deposits in the studied ore districts as well as in other ore deposits in the Diapir zone. This
model shows the stages of organic matter maturation, migration of hydrocarbons and metals, and the emplacement of ore mainly in the SE flank of the diapirs
(modified after the hydrocarbon migration model of Chaari et al., 2003).

Acknowledgements References

The first author would like to thank the Professional Staff Congress
of the City University of New York (PSC/CUNY) for the partial funding
of this project. We thank Mr. Robert Schenk, Scanning Electron
Microscope operator at the Department of Physical Sciences in
Kingsborough Community College, for assisting the first author to ex-
amine the rocks for trace element analysis. The authors would also like
to thank Dr. David Lentz, Dr. Raymond Coveney, and two anonymous
reviewers for their insightful comments and suggestions that improve
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