Marine and Petroleum Geology 164 (2024) 106830

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Marine and Petroleum Geology

journal homepage: www.elsevier.com/locate/marpetgeo

Silurian to early Devonian overmature hot shales in Eastern Taurus: Source

rock characteristics and links to North African petroleum systems
Turhan Ayyildiz a, *, Eren Aykan Acar b
a
Ankara University Faculty of Engineering, Department of Geological Engineering, TR-06830, Gölbaşı Campus, Ankara, Turkey
b
Cougar Drilling Solutions, Malıköy Başkent Organize Sanayi Bölgesi 1, Başkent Bulvarı, No: 74, Malıköy, Temelli, Ankara, Turkey

A R T I C L E I N F O A B S T R A C T

Keywords: The study area is located in the Eastern Taurus region and is characterized by the Paleozoic autochthonous Geyik
Eastern Taurus Dağı Unit (GDU) in the northern Paleo-Tethys back-arc basin. The Eastern Taurus encompasses Silurian-Early
Lydite Devonian units, which may have the characteristics to be called hot shales. In the study area, the Silurian
Pusçu Tepe Formation
black and organic lean shales and Orthoceras-bearing limestone and shale alternation have directly deposited on
Pridoli-Lochkovian hot shale
the Late Ordovician (Hirnantian) peri-glacial clastics. However, while Hot shale-I unit was deposited over the ice
cover rebound-related paleo-depression areas in the southern Paleo-Tethys (North Africa) during the early
Silurian (Rhuddanian- Early Telychian), turbiditic black lydite successions were deposited due to the radiolarian
bloom in the northern Paleo-Tethys (Taurus Belt). Therefore, the studied black shales overlying the lydite suc­
cessions correspond to the late Telychian hot shale II (Sheinwoodian and Pridoli- Lochkovian), which has only
been defined in the Moroccan basins. On the other hand, both lydite occurrence and late Telychian-
Sheinwoodian, and Pridoli-Lochkovian black shales (equivalents of Akakus and/or Tadrart formations) indi­
cate that the Taurus basin under distinct paleoclimate conditions witnessed different bathymetry and nutrients
source (e.g., silica). In addition, pyrolysis results indicate that the studied black shales belonging to GDU have
lost 85–98% of their HC potential due to the overburden resulted from the allochthonous units. However, iso­
topic composition of the oils from the Adana basin and from the surface seepage samples show that these oils
were expelled from Devonian shales. According to the pyrolysis and isotope data, we suggest that there may be a
Pridoli-Lochkovian source rock unit in the Eastern Taurus, unlike the North Africa basins (except for Tadla
basin). These data indicate that the basins developed over the Silurian-Early Devonian succession, which are
believed not to have been affected by the nappe events, could have yielded an economic petroleum system over
the onshore and/or offshore of eastern Mediterranean basins.

1. Introduction
The interplay between Late Ordovician glaciation events and the
ensuing formation of early Silurian hot shales has been a subject of
intrigue and extensive study due to its significant impact on global pe­
troleum reserves. Notably, organic-rich shales from the Silurian period
are estimated to contribute to approximately 9% of the world’s petro­
leum reserves. This estimation is supported by seminal works such as
those by Klemme and Ulmishek (1991) and Lüning et al. (2000a, b,
2003, 2005), highlighting the global economic and geological signifi­
cance of these deposits. Geographically, during the Late Ordovician
period, the Taurus Belt of Turkey was positioned proximal to Egypt, as
described by Keeley (1989), with a continuous ice front extending from
northern Libya to the southeastern area of Turkey. This positioning was
crucial for the development of the Paleo-Tethys Ocean, which served as
the primary depository for Silurian sequences following the Hirnantian
glaciation. The deposition of these sequences across the North
Africa-Arabian plate and the Anatolid-Taurid area underscores the
extensive reach and influence of these geological processes.
The Silurian period witnessed the deposition of two primary hot
shale units, the Rhuddanian and Telychian, alongside two subordinate
units, the Sheinwoodian and the Piridoli-Lower Devonian (Lochkovian)
black shales (Grabowski Jr, 2005). These units are noted for their lateral
discontinuity yet significant contribution to hydrocarbon source rocks
across vast regions, including North Africa and the Arabian plate.
Notable formations such as the Tanezzuft Formation in Algeria and

* Corresponding author.
E-mail address: ayyildiz@eng.ankara.edu.tr (T. Ayyildiz).

https://doi.org/10.1016/j.marpetgeo.2024.106830
Received 16 November 2023; Received in revised form 17 March 2024; Accepted 25 March 2024
Available online 2 April 2024
0264-8172/© 2024 Elsevier Ltd. All rights reserved.
T. Ayyildiz and E.A. Acar Marine and Petroleum Geology 164 (2024) 106830

Morocco (e.g., Klitzsch, 1968; Destombes et al., 1985; Boote et al., 1998; have received comparatively less attention. This study focuses on the
Lüning et al., 2000a;b; Lüning et al., 2003), Libya and Tunisia, as well as Silurian Pusçu Tepe Formation, which spans from Pınarbaşı (Kayseri) to
the Hoselba Member of Akkaş Formation in Iraq (e.g., Soua, 2014; Ortaköy (Adana), and is notable for its outcrops in certain locations
Al-Khafaji, 2015), among others, serve as key examples of these de­ (Fig. 1). This formation is central to our paleogeographic and
posits’ widespread distribution and importance. Despite the acknowl­ geochemical investigation, aimed at filling the gap in the understanding
edged petroleum potential and detailed depositional analyses of early of this region’s geologic history and potential.
Silurian shales, particularly in the southern part of Previous research has predominantly focused on detailed sedimen­
Gondwana-Paleo-Tethys, the lower Paleozoic deposits in the Taurus Belt tological and paleontological studies of the Late Ordovician Şort Tepe

Fig. 1. Geological sketch-map of the Sarız–Tufanbeyli area, showing the lower Palaeozoic succession and the location of sections 1 to 3 (modified from Metin
et al., 1986).

2
T. Ayyildiz and E.A. Acar
and Silurian Pusçu Tepe formations (Dean and Monod, 1990; Monod
et al., 2003; Göncüoğlu et al., 2004; Ghienne et al., 2010; Kozlu and
Ghienne, 2012; Sachanski et al., 2015). However, organic geochemical
analyses, especially concerning Silurian and Lower Devonian (Lochko­
vian) black shales in the Central and Eastern Taurids, have been limited
(Korkmaz et al., 2008; İlleez et al., 2012; Şen, 2012; Döner et al., 2019;
Acar and Ayyıldız, 2022). These studies, while invaluable, have often
been constrained to single locations, and there is a pressing need for
broader geochemical and stratigraphic studies to enhance our under­
standing of the petroleum systems and deposition models of these
formations.
The present study aims to bridge these gaps by offering a compre­
hensive examination of the Paleozoic (Silurian and Lower Devonian)
stratigraphy and depositional environments of the black shales between
Kayseri-Pınarbaşı and Adana-Ortaköy. By obtaining original Total
Organic Carbon (TOC), Hydrogen Index (HI), and Production Index (PI)
data for the first time, this research endeavors to evaluate the source
rock potential of the Silurian and Lower Devonian shales. Additionally,
it seeks to illuminate the organic geochemical characteristics of these
Paleozoic shales, their shale gas, and oil potential within the studied
area and the broader context of the Adana and İskenderun basins.
Through this effort, we aspire to contribute significantly to the existing
body of knowledge, paving the way for future investigations and the
development of more effective exploration strategies in the region.
2. Materials and methods
Our investigation into the sedimentological and geochemical attri­
butes of Silurian-Devonian units encompassed extensive field studies
complemented by rigorous laboratory analyses, divided into two pri­
mary categories. Fieldwork was strategically planned to cover three
regions along a NE-SW axis, chosen for their prominent exposure of
Silurian-Devonian sequences. The regions selected were Küçükka­
baktepe village (KMS), Halevikdere - Değirmentaş village (HMS), and
Ayvat village (AMS), enabling a comprehensive spatial representation of
the geological formations in question. In each location, Measured
Stratigraphic Sections (MSS) were conducted, focusing on the collection
of samples from the intercalated shale and limestone layers of the Pusçu
Tepe Formation. This approach allowed for the gathering of a diverse
dataset, with fourteen samples meticulously chosen from each MSS for
further detailed analysis. The rationale behind this methodical selection
was to ensure a representative cross-section of the geological variability
across the study area, facilitating a nuanced understanding of the sedi­
mentological and geochemical dynamics at play.
Organic Geochemistry: The heart of our laboratory analyses lay in
the application of Rock-Eval pyrolysis, conducted at the AR-GE
geochemistry department of the Turkish Petroleum Corporation
(TPAO). This technique, a cornerstone in petroleum geochemistry,
served to quantify critical parameters such as Total Organic Carbon
(TOC %), kerogen type, and thermal maturity of the samples. By
analyzing the gases released and the thermal breakdown products of
100 mg of rock samples, we could ascertain the TOC, S1 (free hydro­
carbons), S2 (hydrocarbons from kerogen), S3 (CO2 from combustion at
600 ◦ C), and Tmax (temperature at maximum S2 peak) values. These
data points, integral for evaluating the hydrocarbon generation poten­
tial, were further analyzed to calculate the Hydrogen Index (HI), Oxygen
Index (OI), and Production Index (PI), following established protocols
(Espitalié, 1986; Peters, 1986; Tissot and Welte, 1984). The TOC
threshold for deeming a rock a viable source rock was set at 0.5% for
shales, in line with the literature (Table 1). The maturity of the source
rocks was assessed using Tmax and vitrinite reflectance equivalent (%
Requ), with adjustments for overmature samples leveraging the Jarvie
et al. (2001) formula.
Inorganic Geochemistry: Complementing our organic analyses,
major and minor oxide compositions were determined at the Mineral
Research and Exploration General Directorate (MTA) MAT Department.
3
Marine and Petroleum Geology 164 (2024) 106830
Table 1
% TOC limit values and source rock classification determined by Tissot and
Welte (1984) and Peters and Cassa (1994).
Tissot and Welte (1984) Peters and Cassa (1994)
Total Organic Source rock Total Organic Source rock
Carbon (TOC %) potential Carbon (TOC %) potential
1.1–0.5 Poor <0.5 Poor
0.5 -1.0 Moderate 0.5–1.0 Moderate
1.0–2.0 Good 1.0–2.0 Good
2.0–10 Excellent 2.0–4.0 Very good
>4.0 Excellent
The preparation of the samples involved drying, crushing, grinding, and
quartering, followed by analyses using WD-XRF in a semi-quantitative or
quantitative framework. This step was crucial for understanding the
mineralogical context of the organic geochemical results and providing
a comprehensive geochemical characterization of the formations stud­
ied. By employing these detailed field and laboratory methodologies,
our study aims to bridge the existing knowledge gap regarding the
organic geochemistry and petroleum system potential of the Silurian-
Devonian formations within the Taurus Belt. The integration of sedi­
mentological data with advanced geochemical analyses enables a
multifaceted exploration of the source rock potential, contributing
significantly to the broader understanding of the region’s paleogeog­
raphy and hydrocarbon prospects.
3. Geologic setting and stratigraphy
The geological setting of Southern Turkey, home to our study area,
encompasses diverse tectonic and stratigraphic units including the
Arabian plate, various components of the Taurus Belt (e.g., Beydağları,
Akseki, Sarız platforms), and remnants of the southern Neotethys Ocean
(e.g., Elmalı or Lycian, Antalya, Hadim, Aladağlar, and Bitlis nappes).
These units were positioned along the northern Gondwana margin in the
Early Paleozoic, establishing a passive continental margin (Konert et al.
1999; Ghienne et al., 2010). Our focus, the GDU within the Eastern
Taurus, east of the Ecemiş Fault, features Cambrian-Paleogene rock as­
semblages that have undergone significant structural modifications due
to multiple orogenic events, notably the Huronian, Caledonian, Hercy­
nian, and Alpine phases (Özgül, 1976) (Fig. 1). Turkey’s geological
evolution was notably influenced by the Alpine orogeny, which
restructured the remnants of earlier orogenic activities. The late Creta­
ceous period was critical when the collision of Neotethys oceanic crust
with the Anatolian continental crust led to complex thrusts and overlaps,
further sculpted by Late Cretaceous-Eocene thrust movements, which
also formed the allochthonous Aladağ and Bozkır Units alongside the
para-autochthonous GDU (Özgül, 1976). The study’s focal point, the
Silurian-Early Devonian successions, lies along the northern Gondwana
edge. During the Cambrian, this area featured a cratonic platform and
evolved into a "sag" basin with glacial-fluvial/marine deposits in the
Ordovician, hinting at similar paleo-latitudes with other Gondwana re­
gions under the South Pole ice sheet’s influence (eg., Lüning et al.,
2000a; Torsvik and Cocks, 2011; Sachanski et al., 2015). The Ordovician
icehouse phase’s end led to sea-level rises and anoxic conditions, fa­
voring the deposition of organic-rich shales in the Paleo-Tethys Ocean,
impacting areas now known as North Africa and the Arabian Peninsula
(e.g., Lüning et al., 2000a, b; 2005; Monod et al., 2003; Ghienne et al.,
2010).
Stratigraphically, the GDU commences with the Precambrian Emir­
gazi Formation, succeeded by the Middle-Upper Cambrian Değirmentaş
and Late Middle Ordovician Seydişehir Formations, indicative of varied
depositional environments from quartz sandstones to nodular lime­
stones (Demirtaşlı, 1967). The sequence continues with the Late Ordo­
vician preglacial Şort Tepe and glaciogenic Halevikdere Formations,
followed by the Llandovery-stage indicative Pusçu Tepe Formation
T. Ayyildiz and E.A. Acar
(Özgül et al., 1973; Ghienne et al., 2010; Monod et al., 2003; det.
Sachanski in Kozlu et al., 2012; Sachanski et al., 2015, Figs. 2 and 3).
The sequence culminates with the Silurian-Early Devonian Yukarı Yayla
Formation, transitioning into the Early Devonian Ayıtepesi Formation
characterized by a diverse lithology of limestones, shale, and quartz
arenites, delineating a comprehensive stratigraphic and tectonic narra­
tive crucial for understanding the region’s geological evolution (Demi­
rtaşlı, 1967; Özgül et al., 1973; Özgül, 1976; Metin, 1984; Metin et al.,
1986; Özgül and Kozlu, 2002).
4. Results
4.1. Depositional environment and correlation of hot shale the
stratigraphy
The stratigraphy of the region encompasses Late Ordovician (Hir­
nantian), Silurian, and Devonian aged formations, notably the Hale­
vikdere, Pusçu Tepe, and Halit Yaylası, which are prominently exposed
in the area (e.g., Metin et al., 1986; Monod et al., 2003; Göncüoğlu et al.,
2004; Kozlu et al., 2012). These formations have been extensively
studied for their detailed sedimentological and paleontological charac­
teristics through works such as those by Metin et al. (1986), Monod et al.
(2003), Göncüoğlu et al. (2004), and Kozlu et al. (2012). This study
utilizes three Measured Stratigraphic Sections (MSS) along the NE-SW
direction: Küçükkabaktepe (KMS), Halevikdere (HMS), and Ayvat
(AMS), to delve into the depositional environments and potential cor­
relations within these geological units (Fig. 1). The Halevikdere suc­
cession, being the focal point of this study, has yielded significant
insights into facies variations on a global scale through both facies-based
and graptolite-based studies (Kozlu et al., 2012; Sachanski et al., 2015).
The identification of lydite-shale intercalations deposited during the
Rhuddanian-Aeronian-early Telychian period suggests a depositional
environment akin to the Taurus margin, comparable to similar MSSs in
tropical zones like the Alps, Spain, and southern France (Stampfli,
1996). This comparison underlines the broader paleogeographic impli­
cations of the findings, providing a link between the studied region and
global depositional trends. Focusing on the Halevikdere MS, the pale­
ontological data, particularly from graptolite zones, facilitate the cor­
relation of local stratigraphy with broader geological events. The study
reveals significant fluctuations in sea level during the early Silurian,
attributed to the waxing and waning of ice sheets in NW Gondwana, as
supported by various researchers (e.g., Aldridge et al., 1993; Brenchley
et al., 1994; Loydell, 1998). These sea-level changes, coupled with
rifting events and glaciation periods, have profoundly influenced the
depositional patterns and facies distributions within the region. The
presence of lydite-shale facies, particularly those containing specific
graptolite zones, marks critical episodes in the region’s geological his­
tory. For instance, the Spirodden Secundo episode, characterized by a
sea-level rise and relatively cool climate, contrasts with other periods
marked by significant sea-level drops and glacial advances (Fig. 4).
These facies variations provide insights into the dynamic climatic
and sea-level changes during the Silurian period, highlighting the
complex interplay between glaciation events, sea-level fluctuations, and
sediment deposition. The transition from the Late Telychian to the Early
Wenlock periods is marked by notable changes in depositional envi­
ronments, from predominantly lydite deposits to black graptolitic shales
and finally to fossiliferous limestone and marl-limestone alternations.
This stratigraphic succession reflects significant climatic shifts, as indi­
cated by the Ireviken Event and subsequent anoxic events, which have
had profound implications for biodiversity and the geochemical land­
scape of the region. These events, coupled with the deposition of
organic-rich black shales and the potential for petroleum source rocks,
underscore the geological and geochemical significance of the study
area (Figs. 4 and 5).
The detailed examination of the Halevikdere, Pusçu Tepe, and Halit
Yaylası formations, through the lens of measured stratigraphic sections
4
Marine and Petroleum Geology 164 (2024) 106830
and paleontological data, provides a nuanced understanding of the
depositional environments, stratigraphic correlations, and the geolog­
ical history of the region. The identification of hot shale facies, partic­
ularly those associated with significant anoxic events and potential
source rock intervals holds substantial implications for petroleum
geochemistry. The insights gained from this study not only enrich our
understanding of the geological past but also inform potential explora­
tion and exploitation strategies within the realm of petroleum geology.
4.2. Source rock evaluation
The study evaluates the Total Organic Carbon (TOC) percentage of
shale samples from Küçükkabaktepe (KMS), Halevikdere (HMS), and
Ayvat (AMS), which range between 0.09 and 0.71% wt., 0.29–0.88%
wt., and 0.05–0.23% wt., respectively (Table 2). These TOC values
suggest that the studied samples are categorized within the poor source
rock range, indicating limited potential for hydrocarbon generation.
Through the use of Hydrogen Index (HI)-Oxygen Index (OI) and HI-
Tmax graphs, insights were gained regarding the type and maturity of
organic matter within these rock samples (Fig. 6a and b). HI and OI
values span 7–140 mgHC/TOC and 52–660, respectively, with 15 sam­
ples identified as kerogen type IV (HI below 50 mgHC/TOC) and 3
samples indicating Type III kerogen (HI between 50 and 200 mgHC/
TOC) (Fig. 6a). Tmax values, corrected for a 10% increase observed in
most samples, suggest a range from early mature to overmature zones,
with a notable shift of overmature samples into the oil generation zone
after correction (Fig. 6b).
The TOC-S2 diagram reveals a predominance of type IV kerogen
among the analyzed samples, generally associated with no petroleum
potential or limited gas production capabilities (Fig. 7) (Glennie, 2009;
Jones, 1987).
However, original data plotting suggests that Silurian shales, con­
sisting of type II kerogen, might have generated hydrocarbons to a
limited extent throughout the basin’s geological history. Tmax values,
ranging from 436 to 444 ◦ C for most samples to 493–546 ◦ C for those
from KMS, AMS, and HMS, indicate varying degrees of thermal maturity
across the basin, from early mature to extremely mature zones (Table 2).
The PI values of the samples belonging to the Silurian shales were
measured as 0.15–0.21, 0.17–0.21 and 0.18–0.20, respectively
(Table 2). These data are not available due to low S1 and S2 values. For
this reason, it was determined on the PI vs. Tmax graph that the samples
were in the dry gas zone (Fig. 8). Production Index (PI) values and ge­
netic potential (GP) data further support the conclusion that these shales
are primarily within the dry gas zone, with GP values significantly lower
than the threshold for fair source rock potential. The geochemical
analysis of shale samples from the KMS, HMS, and AMS locations reveals
a general trend of poor source rock potential with limited hydrocarbon
generation capabilities. Despite the low TOC percentages and predom­
inance of type IV kerogen, some potential for gas generation exists,
particularly in Silurian and Lower Devonian (Lochkovian) shales.
However, the thermal maturity range and corrected Tmax data indicate
a nuanced understanding of the basin’s hydrocarbon generation history
and potential.
The re-calculation of original Total Organic Carbon (TOCo) is a
pivotal step in evaluating the generative potential of source rocks,
especially in mature or over-matures formations. Studies have shown
that the %TOC value decreases significantly, by approximately 36%,
from its original value during the processes of petroleum generation and
expulsion, highlighting a substantial transformation of organic matter
into hydrocarbons (Table 3). This decrease is coupled with a dramatic
reduction in the residual potential and hydrogen index, indicating a high
degree of conversion. The analyzed samples from the KMS, HMS, and
AMS formations exhibit varying TOCo contents, which, when evaluated
against established benchmarks, suggest differing source rock potentials
across the basin. This variability underscores the importance of
considering geological and geochemical nuances in assessing
T. Ayyildiz and E.A. Acar Marine and Petroleum Geology 164 (2024) 106830

Fig. 2. Generalized columnar section of the Paleozoic unit in the Eastern Taurus (modified from Metin et al., 1986).

5
T. Ayyildiz and E.A. Acar Marine and Petroleum Geology 164 (2024) 106830

Fig. 3. General view of the Şort Tepe, Halevikdere and Pusçu Tepe formations through the Halevikdere entry.

Fig. 4. Chronostratigraphic chart of the Silurian, showing interpreted ages of sequence boundaries and hot shales in the N. Africa and studied area (modified from
Grabowski Jr, 2005, graptolite data adapted from Sachanski et al., 2015 for Halevikdere).

unconventional petroleum systems. According to the original TOCo (%
wt) values, in terms of unconventional petroleum systems, the northern
part of the basin can be defined as moderate-good whereas the SW of the
basin is of poor source rock potential (e.g., Curtis, 2002; Hackley, 2012;
Jarvie et al., 2007; Kinley et al., 2008; Rodriguez and Philp, 2010).
The original Hydrogen Index (HIo) offers a window into the primary
hydrocarbon products a source rock could potentially generate. By
recalculating HIo values, we can infer the original kerogen type present
in the environment where the source rock was deposited. This recali­
bration is essential for mature or over-mature source rocks, whose un­
corrected HI values might not accurately reflect the original organic
matter’s nature. Therefore, the original HIo value should be calculated
with a formula such as calculating the original HIo = [(S2(o)/TOCo) ×
100]. HIo gives the original value of the shale source rock before it
started to derive hydrocarbons and is an indicator of the primary hy­
drocarbon products that can be produced. As seen in the above formula,
the original S2 value (S2o) must be known to calculate the HIo value.
This value is calculated by the formula: S2 (o) = [(TOCo –TOCpd)/
0.083] + S2 (Jarvie et al., 2004). The HIo values of the samples from the
KMS, HMS and AMS’s are 191–471 and 433–442, 432–466 mg HC/g
TOC, respectively (Table 4). The TRHI ratios of KMS, HMS and AMS’s
shales vary between 85 and 98%, 94–98% and 68–93%, respectively.
These values show that the shales cropping out between Küçükka­
baktepe and Halevikdere are a good risk for gas and consistent with
over-mature kerogen values. The analysis reveals that the shale samples
predominantly consisted of type II kerogen, suggesting a good risk for
gas and compatibility with over-mature kerogen values (Jones, 1987;
Weitkunat, 2015).

6
T. Ayyildiz and E.A. Acar Marine and Petroleum Geology 164 (2024) 106830

Fig. 5. Detailed lithological view of the Değirmentaş-Halevikdere section. A) The slumped and bedded black lydites and siliceous shale levels. B) Dark gray to black
shale interbedded with gray limestone, the Orthoceras limestone is on the right of the photo. C) Creamy-brown colored, platy to massive, argillaceous limestone rich
in Orthoceras. D) General view of interbedded limestone and shale. E) General view of black shale and siltstone succession over the carbonate-shale units. F) Black
shale and siltstone succession in the upper part of the succession.

The potential yield (PYo) of hydrocarbon source rocks, expressed in
barrels of oil per acre, is another critical parameter in assessing a for­
mation’s economic viability. Using the original S1 and S2 values, the
potential yield provides an estimate of the volume of hydrocarbons that
could be generated per unit area. In potential yield calculations, the
original S1 (S1o) value is multiplied by the 20,082 constant suggested by
Fujine (2014) to approximately obtain the barrels of oil per acre-foot;
(mg HC/g) × (20,082 barrels•g/acre•ft mg HC) = in barrels/acre ft.
Similarly, to convert the original S2 (S2o) to approximately one barrel of
oil per acre, it should be multiplied by 20,082; (mg HC/g) × (20,082
barrels•g/acre•ft mg HC) = barrels/acre ft (Table 4). The calculations
indicate that before any transformation, the Silurian shales possessed
good to very good source rock potential, underscoring the significant
hydrocarbon generative potential of the formations.
Distinguishing between generative organic carbon (GOC) and non-
generative organic carbon (NGOC) further refines our understanding
of a source rock’s potential. GOC values, calculated from the original HI
values, reveal the proportion of organic carbon capable of generating
hydrocarbons. GOC values are calculated using the formula suggested by
Jarvie (2010): GOC% of TOCo = (HIo/1177) × 100. GOC potentials of
the shales belonging to KMS, HMS and AMS’s vary between 16.2%–40.0,
36.7–37.5, and 36.7–39.5, respectively. These values are similar to
Silurian shales around the central Taurus (Ovacık region) (Döner et al.,
2019). It was concluded that Silurian aged shales outcropping around
Değirmentaş in the Eastern Taurus are extremely mature and have
completed 85–98% of TRHI. Therefore, it is necessary to calculate what
volume of the shales has generated HCs. Since the original pyrolysis
values were calculated in the above sections, the total produced HC can
now be calculated (Jarvie et al., 2004): Amount of hydrocarbon gener­
ated: HCG (kg HC)– –R × M × 10-6 kg/mg, where R is the amount of
generated hydrocarbon per gram of TOC (R= HIo - HIpd; mg HC/g TOC),
M is the mass of organic carbon (M = V × d × TOCo; g TOC), 10− 6 kg/mg
is a conversion from mg to kg (Table 5). The findings suggest that
Silurian shales in the study area, similar to those around the central
Taurus region (Döner et al., 2019), exhibit substantial GOC potentials.
This distinction is crucial for evaluating the overall generative potential

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T. Ayyildiz and E.A. Acar Marine and Petroleum Geology 164 (2024) 106830

Table 2
TOCpd, Rock-Evalpd data from outcrop samples of the Pusçu Tepe Formation, Pınarbaşı-Kayseri of central Taurus.
Location Sample TOC wt. % S1 mgHC/ S2 mg S3 mgCO2/ S1+S2 Tmax HI (mg OI PI RC PC MINC
0
number g rock HC/g g rock C HC/g % % %
rock TOC)

Ayvat AYV-01 0,13 0.12 0,02 0,06 0,58 0.08 500 46 446 0,20 0.11 0.02 0.07
AYV-03 0,23 0,02 0,07 0,36 0.09 499 30 157 0,19 0.21 0.02 0.09
AYV-05 0,16 0,01 0,06 0,32 0.07 436 38 200 0,19 0.14 0.02 0.06
AYV-08 0,06 0,01 0,06 0,21 0.81 444 100 350 0,18 0.05 0.01 0.08
AYV-09 0,05 0,02 0,07 0,33 1.03 499 140 660 0,19 0.03 0.02 0.06
Halevikdere Devonian 16 ME 15 0,74 0.43 0,02 0,08 1,14 0.10 493 11 154 0,21 0,69 0,05 0,11
HLV-14 0,29 0,02 0,07 0,51 0.58 515 24 176 0,19 0.26 0.03 0.09
16 ME 13 0,71 0,01 0,08 1,03 0.09 440 11 145 0,16 0,67 0,04 0,11
Silurian HLV-11 0,33 0,01 0,05 0,68 0.73 N/A 15 206 0,21 0.31 0.02 0.07
16 ME 10 0,19 0,01 0,01 2,04 0.02 N/A 5 1074 0,18 0,13 0,06 0,07
16 ME 06 0,19 0,01 0,03 0,37 0.04 499 10 123 0,27 0,28 0,02 0,07
HLV-5a 1,24 0,02 0,09 1,44 1.53 546 7 116 0,17 1.18 0.06 0.16
16 ME 02 0,17 0,01 0,03 0,69 0.04 499 18 406 0,24 0,14 0,03 0,10
16 ME 01 0,02 0,01 0,03 0,05 0.04 500 150 250 0,18 0,01 0,01 0,08
K. Kabaktepe KBK-19A 0,09 0.37 0,01 0,06 0,28 0.88 493 67 311 0,20 0.86 0.02 0.08
KBK-21 0,30 0,02 0,07 0,30 1.00 500 23 100 0,19 0.08 0.01 0.08
KBK-22 0,71 0,02 0,06 0,60 0.08 N/A 8 85 0,21 0.28 0.02 3.64
KBK-23¢ 0,28 0,01 0,06 0,67 0.73 440 21 239 0,20 0.69 0.02 0.09
KBK-21A 0,47 0,02 0,09 0,73 0.82 499 19 155 0,15 0.25 0.03 0.24

Fig. 6. A) HI vs. OI diagram, B) HI versus Tmax cross plot after Espitalié (1986) gives an overview of the thermal maturity and variation of organic matter quality for
studied shale samples from Eastern Taurus. The circled part is the organic matter type area obtained with the original calculated values. Kerogen types: Type I - oil
prone, Type II - oil and gas prone, Type III - gas prone.

of the formations and estimating the volume of hydrocarbons that have
been generated.
5. Discussion
5.1. Depositional model of Silurian Pusçu Tepe Shales and correlation to
Northern Africa and Arabian Plate
The Late Proterozoic to Late Paleozoic era was a pivotal period for
the regions that now encompass North Africa, the Arabian Peninsula,
parts of Turkey, and Iran, as these were integral to Gondwana’s northern
passive margin (Beydoun, 1991). This geological setting facilitated
unique depositional environments, particularly during the Late Ordo­
vician and Early Silurian periods, marked by the short-lived (0.5–1.0 m.
y.) Hirnantian glaciation (e.g., Brenchley et al., 1994; Monod et al.,
2003; Ghienne et al., 2007, 2010; Kozlu and Ghienne, 2012; Melchin
et al., 2013). The aftermath of this glaciation, notably the rapid melting
of glaciers, led to significant eustatic sea-level rises, inundating the
North African and Arabian landscapes with organically rich shales
directly atop glacial remnants (Husseini, 1991). The Early Silurian
transgression, while initially flooding only low-lying shelf areas, resul­
ted in the deposition of black shales during the Rhuddanian Stage
(Fig. 9a and b) (Jaeger, 1976; Combaz, 1986), suggesting a decrease in
water circulation within these newly formed basins (Central Arabia,
Murzuk- and Ghadames basins, etc., Semtner and Klitzsch, 1994). This
period contrasts with the deposition environments of the middle-eastern
Taurus region, which, due to its back-arc basin characteristics, was not
conducive to the deposition of clay-rich organic matter (e.g., Kozlu et al.,

8
T. Ayyildiz and E.A. Acar Marine and Petroleum Geology 164 (2024) 106830

Fig. 7. S2 vs. TOC plot (after Langford and Blanc-Valleron, 1990): Circle and
triangle refer to present and original values, respectively.
2012; Varol et al., 2006; Acar and Ayyıldız, 2022). Instead, this area saw
the deposition of lydite-thin shale, indicative of a different sedimentary
regime driven by quartz-rich source transfer and nutrient circulation.
The Pusçu Tepe Formation’s lower hot shales, primarily deltaic
organic-rich marine shales deposited under disoxic-anoxic conditions,
starkly contrast the upper hot shales deposited under more oxic-dioxic
marine conditions (Lüning et al., 2000a). This distinction underlines
the variation in organic matter preservation and depositional environ­
ments over time. The comparison of these shales with those in the
Northern African and Arabian regions, such as the Ghadames and
Murzuk basins, reveals differences in depositional times and environ­
ments, suggesting a broader regional variability in Silurian sedimenta­
tion patterns. In contrast to the Lower hot shales, the Upper hot shales
(Ludlow-Pridoli) have a moderate organic richness (TOC ≥0.5%) and
contain an assemblage of organic matter mostly deposited under
oxic-dioxic marine conditions. Therefore, the Dadaş-I black shales are
represented by Llandovery (late Rhuddanian (?)-early
Aeronian-Telychian) hot shales in the SEA region, while black shales
belonging to the Pusçu Tepe Formation in the Middle-Eastern Taurus are
the equivalent of the upper hot shale level (late Telychian) (Fig. 6).
Compared to the Rhuddanian and Rhuddanian-early Telychian hot

Fig. 8. PI vs. Tmax graph (after Bacon et al., 2000; Peters, 1986; Peters and Cassa, 1994): Circle and triangle refer to present and corrected values, respectively.

Table 3
Calculated results of TOCo, S1o, S2o, HIo, PIo, TRHI.
Sample TOC0 (wt. Slo (mg HC/g S2o (mg HC/ HIo (mg HC/g PIo TRm Slo (bbl/ S2o (bbl/ PYo (mg HC/ GOC GOC NGOC
no %) TOC) g TOC) TOC) (%) ac-ft) ac-ft) g TOC)
Potential
%

KBK 19A 0.14 0.61 0.66 471 0.48 85 12.25 13.45 1.27 40.0. 0.40 –
KBK 21 0.46 2.05 0.67 191 0.48 87 12.45 42.00 1.29 16.2 0.16 0.19
KBK 21a 0.73 3.20 3.22 441 0.49 96 65.77 64.66 6.37 37.4 0.37 0.57
KBK 22 1.10 4.83 4.75 426 0.50 98 97.83 97.83 9.44 36.1 0.36 0.74
KBK 23c 0.43 1.90. 1.86 432 0.49 95 38.30 39.31 3.67 36.7 0.36 0.07
16ME0.1 0.03 0.13 0.15 501.6 0.46 70. 2.60 3.00 2.6 42.6 0.43 –
16ME0.2 0.26 1.09 1.08 417.1 0.50 96 22.0 21.8 22.0. 35.4 0.35 –
HLV 5a 1.93 8.42 8.49 435 0.50 98 169.16 170.56 16.73 36.9 0.37 –
16ME0.6 0.29 1.21 1.23 425.8 0.50 98 24.4 24.80 24.4 36.2 0.36
16ME10. 0.29 1.21 1.21 418.9 0.50 99 24.4 24.40 24.4 35.6 0.36 –
HLV 11 0.51 2.24 2.28 433 0.49 96 45.11 45.91 4.38 36.7 0.37 0.14
16ME13 1.10 4.71 4.78 434.4 0.50 97 94.6 96.00 94.6 36.9 0.37 –
HLV 14 0.45 1.98 2.10 442 0.49 94 39.87 40.87 3.93 37.5 0.38 0.07
16ME15 1.10 4.35 4.42 401.6 0.50 97 87.3 88.70 87.3 34.1 0.34
AYV Ol 0.20 0.90 0.94 450 0.48 89 18.09 18.07 1.76 38.2 0.38 –
AYV 0.3 0.35 1.57 1.51 432 0.49 93 31.07 32.70 2.97 36.7 0.37 –
AYV 0.5 0.25 1.09 1.14 456 0.49 91 21.97 22.89 2.23 38.7 0.39 –
AYV 0.8 0.09 0.41 0.46 466 0.46 78 8.36 8.43 0.79 39.5 0.39 –
AYV 0.9 0.07 0.35 0.40 442 0.45 68 7.20 6.22 0.57 37.5 0.37 –

9
 T. Ayyildiz and E.A. Acar Marine and Petroleum Geology 164 (2024) 106830

Table 4
Values of HCG calculated units by taking the area between Küçükkabaktepe and Mirzaağa (3.93 × 1010 cm2 width), density 2.6 g/cm3 and their original pyrolysis
value.
Sample No TOC S1 mg HC/g rock S2 mg mg HC/g rock S3 mg CO2/g rock HI TOCO Hlo S2o
% %

AYV-01 0,13 0,02 0,06 0,58 46 0,203125 463,2734 0,941,024,096

AYV-03 0,23 0,02 0,07 0,36 30,00 0,359375 453,2132 1,628,734,94
AYV-05 0,16 0,01 0,06 0,32 38,00 0,25 457,7349 1,144,337,349
AYV-08 0,06 0,01 0,06 0,21 100,00 0,09375 497,7349 0,466,626,506
AYV-09 0,05 0,02 0,07 0,33 140,00 0,078125 523,3349 0,408,855,422
HLV-5a 1,24 0,02 0,09 1,44 7,00 1,9375 438,3801 8,493,614,458
HLV-11 0,33 0,01 0,05 0,68 15,00 0,51 443,4319 2,286,445,783
HLV-14 0,29 0,02 0,07 0,51 24,00 0,45 449,1832 2,035,361,446
KBK-19A 0,09 0,01 0,06 0,28 67,00 0,14 476,4016 0,669,939,759
KBK-21 0,30 0,02 0,07 0,30 23,00 0,46 448,6683 2,10,313,253
KBK-22 0,71 0,02 0,06 0,60 8,00 1,109375 439,1434 4,871,746,988
KBK-23¢ 0,28 0,01 0,06 0,67 21,00 0,4375 447,4492 1,957,590,361
KBK-21A 0,47 0,02 0,09 0,73 19,00 0,734375 445,9903 3,275,240,964

during Telychian as hot shale, when the sea inundated the paleohighs
Table 5
(Lüning et al., 2000a; Emiroğlu, 2020) (Fig. 9b). To explain the sporadic
HCG values calculated for Ayvat region.
distribution of Silurian shales, Lüning et al. (2000a) proposed a model of
Sample no M R TOCO glacial affected topography. It is a reliable model for the North Africa
AYV-01 417 2,90469E+12 0,203125 and Middle East region, where hot shales were deposited on a
AYV-03 423 5,13906E+12 0,359375 post-glacial topography of the Paleo-Tethys Ocean (Le Heron et al.,
AYV-05 420 3,575E+12 0,25
2009). However, the Taurus region, where the study area is located,
AYV-08 398 1,34063E+12 0,09375
AYV-09 383 1,11719E+12 0,078125
differs from the SEA (except Korudağ) and Arabian plate in terms of both
HLV-5a 431 2,77063E+13 1,9375 lithological association and depositional time. For example, in the
HLV-11 428 7,37344E+12 0,51 eastern Taurus (Değirmentaş-Kayseri), middle Taurus (Bozyazı-Tekmen,
HLV-14 425 6,47969E+12 0,45 Ovacık) sections, lydite-black shale intercalation was deposited during
KBK-19A 409 2,01094E+12 0,14
the Early Llanddovery (Rhuddanian)-upper Aeronian (det. Sachanski in
KBK-21 426 6,70313E+12 0,46
KBK-22 431 1,58641E+13 1,109375 Kozlu et al., 2012; Sachanski et al., 2015). Black lydite–shale successions
KBK-23¢ 426 6,25625E+12 0,4375 are also recorded in Portugal, Spain, south central Pyrenees, Italy,
KBK-21A 427 1,05016E+13 0,734375 Thuringia Forest, Germany, Poland, Chios-Greece and western Bulgaria
(referred to in article Sachanski et al., 2015) except North African
Paleozoic basins. Therefore, the lydite-black shale intercalation implies
shales in Tunisian (the Ghadames (=Berkine)-the Argiles Principales
that distinct geochemical conditions prevailed during the Rhuddanian in
Formation) and Libyan (Murzuk basin-Tanezzuft Formation) basins (e.
the paleo-valleys in Halevikdere-Ovacık and Tekmen, from those in the
g., Soua, 2014; Shalbak, 2015), the hot shales in SEA and eastern Taurids
North Africa. Following lydite facies, thick fossiliferous limestone (cal­
differ in the depositional time and the environment (Lüning et al.,
carenite, nodular limestone and mudstone, and massive gray limestone
2000a; Cohen et al., 2013; Emiroglu, 2020; Hoşgör and Yılmaz, 2022)
with Orthoceras in an ascending order) is observed to have deposited in
(Fig. 4).
the Late Telychian - Early Wenlock (Sheinwoodian) transition in the
Loydell et al. (2009) suggested that there were two “hot shale” in­
Küçükkabaktepe MSS and Halevikdere MSS (Fig. 9c and d) (Metin et al.,
tervals in Jordan: one in the lower Rhuddanian which consists of
1986; Monod et al., 2003; det. Sachanski, in Kozlu et al., 2012;
ascensus-acuminatus graptolites and the other one in the middle Rhud­
Sachanski et al., 2015). It is thought that the process of carbonate
danian, the Batra Formation (also known as the Mudawwara Shale
deposition develops as follows: atmospheric CO2 dissolves in sea
Formation, Loydell et al., 2009). In addition, they claimed that Middle
water/meteoric water and forms H2CO3, which, in turn, reacts with Ca2+
Rhuddanian “hot shale” probably results from rapid burial of organic
coming into solution following the weathering of plagioclase (CaAl2
carbon associated with a minor regression during which anoxic bottom
Si2O8) minerals in ultramafic rocks. Finally, Ca+2 and CO−3 2 combine to
conditions prevailed for most, but not all of the deposition time. Based
form limestones on a global scale during the Late Telychian - Early
on the graptolites and palynomorph assemblages of the samples taken
Wenlock (Sheinwoodian) (Aldridge et al., 1993; Jeppsson et al., 1995,
from the outcrops (Çat-Hazro MS) and well samples (Bismil I, II and
1997; Brunton et al., 1998; Cramer and Saltzman, 2007). With the
Diyarbakır-1 wells) in the SEA region, the hot shale units in the Dadaş
consumption of high CO2 in the atmosphere as a result of limestone
Formation show a diverse time of deposition, ranging from
formation (diminishing atmospheric CO2 concentration), the third mini
Aeronian-Telychian in Çat-Hazro, Late Rhuddanian-early Telychian in
ice age might have been triggered in the early Sheinwoodian (Ireviken
Bismil I, and Late Telychian-Early Sheinwoodian in Diyarbakir (Lüning
Event) (Lehnert et al., 2010).
et al., 2000a, 2005; Cohen et al., 2013; Emiroğlu, 2020). When evalu­
Upper Silurian (Late Pridoli)-Lower Devonian (Lochkovian) section
ated together with the minor regression in the middle Rhuddanian in
of the studied succession is composed of black shales similar to its lower
south of Jordan, it can be deciphered that the transgression resulting in
Silurian counterparts. Konyukhov (2015) stated that a significant cool­
the deposition of the Silurian sequences didn’t reach the SEA region as
ing period which began in the Late Silurian and continued throughout
this region formed a paleo-high during early Aeronian. Likewise, Lüning
the Early Devonian was consequently followed by a significant decrease
et al. (2000a) and Eschard et al. (2010) suggested that the palaeohigh
in the sea level and the establishment of anoxic conditions in many
was very significant, for it controlled not only the timing of the depo­
marine basins. The resulted anoxic conditions were favorable for the
sition but also the likelihood of its presence and its thickness in the North
accumulation of graptolite shales. For example, the Silurian–Devonian
African Paleozoic petroleum systems. Lüning et al. (2000a) put forward
boundary successions are represented by the upper part of
that due to palaeohighs, Qusaiba area was only flooded in
Xistos-com-Nodulos Formation (Portugal) and are present in Well
post-Rhuddanian times in Saudi Arabia. We suggest that hot shale level
BJ-101 of the Tadla Basin in Morocco (Jabour and Nakayama, 1988).
belonging to upper Dadaş-I member (Lüning et al., 2000a) was deposited

10
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T. Ayyildiz and E.A. Acar Marine and Petroleum Geology 164 (2024) 106830

Fig. 9. A) The Late Ordovician glaciation culmination was covered over the North Africa during the early-mid Hirnantian. B) As a result of the opening of the Paleo-
Tethys at the end of the Ordovician and the melting of the glaciers as a result of this event, independent basins were formed in North Africa as a result of rebound,
while the Taurus micro-continent was almost completely covered by the rising sea level in the back-arc area of the Paleo-Tethys ocean, which opened by rifting. Due
to different geochemical conditions in these areas with antecedent topography, black shales containing graptolite and black lydite were deposited in the south (N.
Africa) and north (Taurus) of the back-arc basin, respectively. During the Telychian, the Taurus and N. African basins reached suitable geochemical conditions to
deposited black shale. C) Greenhouse gases (e.g., CO2) increased as a result of the Paleo-Tethys ocean opening and volcanic range is withdrawn from the atmosphere
by being used for limestone formation as a result of the chemical cycle. After that black shales were deposited in both areas, which gained a regressive character as a
result of carbonate deposition during the late Shenwoodian. D) While the North African basins, which turned into a regressive character as a result of shale
deposition, were filled with deltaic clastics, carbonate deposition started in the Taurus basin, which had a higher sea level. E) While the North African Basins turned
into a fluvial deposition environment after filling up, the Taurus basin continued its black shale-carbonate deposition cycle.

Abrams et al. (1999) concluded that one of the oil families in the
Timan–Pechora basin is generated by Silurian to Lower Devonian
mudstones. In the North Africa-Arabian region (except the Tadla basin),
Lower Devonian is generally represented by clastics with reservoir po­
tential, whereas Upper Silurian-Lower Devonian is characterized with
black shales of high source rock quality in the north of Gondwana,
indicating that the deposition mechanism was partially different (Fig. 9
d, e). In addition, these levels, which contain dark colored black shale,
are proved to be the source rock of the petroleum in the Adana basin
(Baum and Schmitt, 1992).
5.2. Lydite facies deposition
Radiolarian-dominated ribbon chert successions signal deeper paleo-
environments, extending from the deeper distal shelf to the ocean floor,
yet are notably absent in mid to outer shelf zones (Einsele, 1992). Ideal
lydite deposition depths are considered to not exceed 300m, as
suggested by Randon and Caridroit (2008). Bedded radiolarite deposits,
common during glacial periods, indicate cooler temperatures favor silica
preservation over limestone (Hein and Parrish, 1987). This temperature
dynamic aligns with observations in our study area, where chert and
siliceous shale precede the first limestone layers at the
Telychian-Wenlock transition, hinting at CO2 level fluctuations during
mini-glacial and interglacial periods. The absence of carbonate deposi­
tion from the Silurian (Llandovery) to Wenlock (Sheinwoodian) period
suggests a direct correlation with these climatic events. Moreover, gla­
ciation’s role in siliceous sedimentation, while evident, presents esti­
mation challenges due to the continuous availability of silica and
nutrient-rich currents (Hein and Parrish, 1987). Post-glacial continen­
tal rebound likely intensified silicate mineral weathering, providing
nutrients for radiolarian populations in the Paleo-Tethys Ocean and its
margins, as evidenced by chert-rich layers from Iberian to Taurus re­
gions (Tetard et al., 2014). The retreat of glaciers and the post-glacial
rebound of continental crust create massive pieces of land for

11
T. Ayyildiz and E.A. Acar
intensive chemical weathering of silicate minerals in glacial deposits
and in the exposed crystalline basement (Einsele, 1992). The quartzites
of the Infra-Cambrian (?)-Early Cambrian Emirgazi Formation in the
Central and Eastern Taurus or Egypt-Sinia paleohigh might have
chemically decomposed; they must have been used as nutrients by the
radiolarian living in the moderately deep areas. Hydrothermal activity’s
impact on shale deposition is further elucidated through Al–Fe–Mn
ternary diagrams, indicating specific environmental conditions condu­
cive to such accumulation (Adachi et al., 1986; Yamamoto, 1987). The
presence of A-type igneous rocks in the Tauride-Anatolide block and
volcanic deposits in a late Ordovician-Silurian rift basin underscore the
region’s significant hydrothermal contributions to siliceous nutrient
availability, fostering radiolarian growth (Topuz et al., 2021; Bagheri
and Stampfli, 2008; Stampfli et al., 2013). According to Adachi et al.
(1986), the Al – Fe – Mn ternary diagram showed that the samples are in
the region affected by a particular hydrothermal activity (Fig. 10).
It can be said that redox conformations and the presence of hydro­
thermal effect are directly proportional to the accumulation on the sea
floor. A collect of A-type igneous rocks representing the rifting event of
the Paleo-Tethys Ocean in the easternmost part of the Tauride-Anatolide
block might have served as a hydrothermal source (Topuz et al., 2021).
Additionally, a late Ordovician-Silurian rift basin developed in southern
margin the Paleo-Tethys Ocean and filled with very thick volcanic de­
posits. Its development was aborted in Early Devonian time in the Ira­
nian segment of southern margin of the Paleo-Tethys (Bagheri and
Stampfli, 2008; Stampfli et al., 2013). We suggest that anorogenic
magmatism (A-type syenite to granite) and volcanism of Late Ordovician
to Silurian was widespread and resulted in rich siliceous nutrients,
which must have triggered the increase in radiolarian population.
Contrastingly, the “low-silicate, high-nitrate, low-chlorophyll” model
posits that upwelling-supported Si supply drives primary production in
shelf-edge zones, promoting phytoplankton and zooplankton prolifera­
tion (Dugdale and Wilkerson, 1998; Dunne et al., 1999). This dynamic
explains the distinct depositional patterns observed in southern Gond­
wana basins, where antecedent topography and upwelling conditions
restricted lydite formation to specific areas.
Lydite facies is also observed at the base of some Silurian sequences
(in the central and southern parts of the Central Iberian region, in the
Central Taurus - Bozyazı-Tekmen, Ovacık, SEA-Korudağ section)
(Gutiérrez-Marco et al., 1998; Varol et al., 2006, Kozlu et al., 2012).
However, lydite facies form the lower part of the succession in the
Halevikdere section, showing also slump structures in the middle part
(Fig. 4a). Sachanski et al. (2015) interpreted this slump structure as
Fig. 10. Al–Fe–Mn diagram showing compositional difference between hy­
drothermal and non-hydrothermal chert (Modified from Adachi et al., 1986).
12
Marine and Petroleum Geology 164 (2024) 106830
mega-slump events and considered it to have formed during rapid
deglaciation while powerful earthquakes took places. On the other hand,
few researchers suggest that slump structures are probably formed by ice
pushing and shear events (e.g., Caputo et al., 2008). In the Lower Silu­
rian, three mini-glacier formations have been recorded in some regions
of the world: Aronian, latest Aronian-early Telychian and Telychian -
earliest Wenlock-Sheinwoodian (Grahn and Caputo, 1992; Grahn, 1996)
(Fig. 5). Therefore, it seems that a thick ice cover during the climax of
the Hirnantian glaciation might not have totally melted and have caused
in the formation of Alpine-type glaciation in high areas of the basement
rocks with Albedo effect in both North Africa and the Taurus Belt (i.e.,
study area). The ice masses, waning at the end of this mini-glaciation
period, may have pushed lydite layers with plastic character, causing
them to gain a slump structure. We also suggest that these short-term
glacial and interglacial periods probably controlled the deposition of
shale and carbonate alternation. While the units deposited during
short-term glacial are poor in organic matter, those which were depos­
ited during interglacial periods contain higher amount of organic mat­
ter. In addition, the limestone-black shale alternation in KMS and HMSs
must have been deposited during Late Telychian - Early Sheinwoodian
mini-period glaciation and melting. Furthermore, geological and envi­
ronmental factors, including sedimentation rates, burial depths, and
dissolved silica availability, intricately influence black chert formation.
Lydite facies, noted at the base of certain Silurian sequences across
various regions, often exhibit slump structures indicative of rapid
deglaciation and seismic activities, underscoring the complex interplay
of glacial dynamics, sedimentation processes, and structural geology in
their formation (Gutiérrez-Marco et al., 1998; Varol et al., 2006; Kozlu
et al., 2012; Sachanski et al., 2015).
In summary, the deposition of lydite facies is a multifaceted process
influenced by paleo-environmental conditions, hydrothermal activity,
nutrient availability, and glacial-interglacial cycles. These factors
collectively contribute to the unique sedimentary records observed in
the study area, offering insights into the complex geological history of
the Paleo-Tethys Ocean and its adjacent regions.
5.3. Stratigraphic configuration of Pusçu Tepe and Yukarı Yayla
Formations according to SEA and North African hot shales
In the Eastern Taurus, the Pusçu Tepe Formation, identified by
Demirtaşlı (1967) as Lower Silurian black shales, and the overlying
Orthoceras-rich Silurian (Wenlock) – Early Devonian (Lochkovian)
limestone-shale Yukarı Yayla Formation, highlight the region’s complex
lithostratigraphic history (e.g., Demirtaşlı, 1967; Özgül and Kozlu,
2002). Unlike the consistent hot shale units of North Africa’s Llandovery
(Rhuddanian and Telychian) and Ludlow-Pridoli epochs, the Taurus
Belt’s unique tectonic evolution has led to varied lithostratigraphic
patterns and thermal evolutions.
Hot shale units have been investigated by studying the samples taken
from the intervals deposited during the two main epochs in North Africa:
Llandovery (Rhuddanian and Telychian) and Ludlow-Pridoli (e.g.,
Lüning et al., 2003; Soua, 2014). Comparing the hot shales deposited in
North Africa with those from the SEA and Taurus Mountains reveals that
Dadaş-I member of the Dadaş Formation (considered as hot shale) was
deposited in Silurian – Lower Devonian (Bozdoğan et al., 1987; Kozlu
et al., 2012). However, the unique tectonic position and evolution of the
Taurus Belt caused the black shales in this region to have different
lithostratigraphic pattern and thermal evolution from the basins in N.
Africa and SEA. For example, Silurian-Lower Devonian black shale
successions in the eastern Taurus have hitherto been studied under two
different names, the Pusçu Tepe, and Yukarı Yayla (Demirtaşlı, 1967;
Özgül et al., 1973; Özgül and Kozlu, 2002). Furthermore, samples from
HMS can be considered hot shale if their original pyrolysis values
instead of present-day pyrolysis values are taken into account. However,
the fact that the petroleum discovered in Cenozoic reservoir rocks in
Adana Basin has been expelled from the Devonian shales (Baum and
T. Ayyildiz and E.A. Acar
Schmitt, 1992) along with the original pyrolysis values indicate that the
black shales that are the subject of the study can be considered as hot
shale. Therefore, the deposition time of the SEA Silurian shales as well as
the stratigraphy of the Eastern Taurus black shales should be revised in
order to be consistent with that of the N. Africa basins. While Rhudda­
nian hot shale levels are common in North Africa terrain, it was not
penetrated in the wells drilled in the SEA region (Diyarbakır basin)
(Lüning et al., 2000a, b; Emiroğlu, 2020; Hoşgör and Yılmaz, 2022).
Kozlu et al. (2012) stated that Gökiçi-I well around Korudağ cut 32 m of
the black shale-lydite succession, including graptolites (from Rhudda­
nian up to the Upper Wenlock); however, Emiroğlu (2020) re-evaluated
the samples taken from this well using the graptolite fossils and stated
that the Dadaş Formation was deposited in the Llandovery (Aero­
nian-Telychian), which is supported by palynological techniques (Boz­
doğan et al., 1987; Oktay and Wellman, 2019) in Diyarbakır basin
(Molla-Bismil area wells). The age (Aeronian-Telychian) of the samples
from the drilled wells (Hoşgör and Yılmaz, 2022) indicate that the
Llandovery (Rhuddanian) hot shale level in the SEA region is not
deposited due possibly to a paleoridge in some northern Africa areas
(Lüning et al., 2000a). We suggest that Dadaş-I member is the equivalent
of the second hot shale level (Telychian), reported by Lüning et al.
(2000a) (Figs. 4 and 11).
This comparative analysis between SEA, North Africa, and the
Eastern Taurus regions underpins a proposed Silurian (Aeronian-Tely­
chian)-Lower Devonian deposition timeline. The Pusçu Tepe and Yukarı
Yayla formations, reflecting this period, merit reclassification into a
single formation with four distinct members to better encapsulate the
geological narratives of black shales, limestone-shale associations, and
fossiliferous units shaped by the interglacial periods of the Silurian -
Fig. 11. Correlation of the Pusçu Tepe Formation with conjugate formations in the Southeastern Anatolia Region with the Late Ordovician - Silurian sea level
changes and their glaciation periods (modified from Johnson and McKerrow (1991), Grahn and Caputo 1992; modified and updated from Craig et al., 2008 in Soua
2014; Lüning et al., 1999; Emiroğlu 2020).
13
Marine and Petroleum Geology 164 (2024) 106830
Lower Devonian era (Özgül and Kozlu, 2002; Kozlu and Ghienne, 2012;
Sachanski et al., 2015). These members are: I: Lydite-shale facies
(Llandovery-Rhuddanian-Early Telychian), II: Lower black shale facies
(Late Telychian - Early Ludlow), III: Fossiliferous limestone-shale facies
(Late Ludlow-Early Pridoli), and IV: Upper black shale facies (Late Pri­
doli – Lochkovian), each correlating to the stratigraphic insights gained
from comparative studies with North African hot shales.
5.4. Source rock properties of the Pusçu Tepe Formation (late Telychian
and late Pridoli – Lochkovian hot shales equivalent)
Lüning et al. (2000a) underscore the pivotal role of early Silurian
organic-rich shales in the petroleum systems of North Africa, noting an
expulsion of 80–90% of total generated petroleum from these forma­
tions. Extensive studies across the North African margin and Arabian
plate (MacGregor, 1998; Lüning et al., 2005; Grabowski Jr, 2005; Craig
et al., 2008) have documented the widespread distribution of these
graptolitic black shale facies, with TOC values in Iraq’s Akkas Formation
ranging from 0.16% to 7.3% (Al-Khafaji, 2015). In Jordan, the lower
part of the Silurian shales is called Mudawwara, which is 9–18 m thick,
contains 7% TOC and is considered mature (VRo = 1.2%) (Lüning et al.,
2005). In contrast, Turkey’s Silurian shales, particularly those in the
Diyarbakır basin, demonstrate a mean TOC value of 3.86%, with a
maximum of 7.88% in the Dadaş-I member, suggesting a notable organic
richness (Kara, 2021). However, the potential of the studied shales as
source rocks is contested due to signs of overmaturity, such as high Tmax
and low HI values, indicating a poor source rock potential for generating
hydrocarbons.
The Silurian (late Telychian) shales will be generally interpreted
T. Ayyildiz and E.A. Acar
according to the samples of the measured sections, since the Early
Llandovery (Rhuddanian) aged units in the HMS are composed of the
dominant lydite facies, represented by a single sample (16 ME-02). The
late Telychian samples were evaluated from organically rich and
organically lean sections. The present TOC (TOCpd) content for the
shales of the AMS, HMS and KMS ranging from 0.05% to 0.23% (average
0.12%), 0.02 to 0.74 (average 0.43%) and 0.09 to 0.71 (average 0.37%)
in the Eastern Taurus, respectively (Table 3). Average TOC % values
indicate that the all studied samples have poor source rock potential.
Tmax values and HI values show that the studied shale samples are
predominantly in the overmature zone (Table 2). Korkmaz et al. (2008)
studied Cambrian-Silurian shales through Eastern Taurus belt using
three samples from Halevikdere MSS. The studied samples’ TOC, HI and
S2 values range from 0.09 to 2.25 %, 1 to 22, and 0.02–0.03, respec­
tively. Besides, Şen (2012) interpreted the Silurian samples from the
Western Black Sea, Eastern Taurus (Halevikdere) and SEA regions ac­
cording to their pyrolysis values. He stated TOC content of this section
ranged between 0.18 and 1.95 % in the Halevikdere, and indicated that
most samples were poor except four samples. In addition, he suggested
that the Tmax values (between 298 and 440 ◦ C) were not reliable due to
extremely low S2 and HI values. When both studies are examined in
detail, there is a discrepancy between TOC, HI and Tmax data. However,
he unanimously concluded that there is no potential/limited gas po­
tential. He reached this conclusion by using the burial history graph of
the regions (e.g., Demirel and Kozlu, 1997; Göncüoğlu et al., 2004). For
example, Göncüoğlu et al. (2004) showed that the Pusçu Tepe Forma­
tion was buried at 2.0 km and 4.0 km in the Devonian-Early Carbonif­
erous boundary and at the end of the Permian in the burial history
graph, respectively. In this case, it can be said that the shales reached the
over mature zone at the end of the Paleozoic. The Paleozoic successions
in the Central and Eastern Taurus are in the over maturation zone,
because the GDU is tectonically overburden by allochthonous units
(Özgül, 1984). In the Late Cretaceous (Senonian), the Bozkır Unit was
pushed over the Aladağ Unit, in the Paleogene (Early-Middle Eocene)
the Aladağ Unit, carrying the Bozkır Unit on its back, was napped over
the GDU (Özgül and Kozlu, 2002). With the burial, the Early Paleozoic
aged successions reached the over-mature zone and transformed into
residual organic matter by the overlapping of three different allochth­
onous units. This may also explain the high NGOC values (Table 3). The
original TOCo, HIo etc., values of the samples were calculated using the
formulas by Jarvie et al. (2004). It is observed that the original TOC%
values of the shale samples have decreased by approximately 64–70%.
Similarly, the calculated primary HIo and GOCo values were determined
to be of type II marine kerogen rather than type IV, which is inferred
based on the present-day pyrolysis values (Jones, 1987). Hart and Steen
(2015) emphasizes that neither the Van Krevelen diagram nor the
kerogen type and maturity plot is useful for over-mature samples. When
using the original TOCo and S2o values, it was observed that the samples
fell onto the Type II kerogen zone. Döner et al. (2019) also obtained
similar data in Ovacık (Mersin) black shale in the Central Taurus region,
indicating that the Paleozoic succession in both regions may have a
similar tectonic history.
The African shelf and Arabian Plate (including SEA) deposition
model of hot shales and therefore Paleozoic petroleum systems can be
explained by almost a single model (Lüning et al., 2000a). The differ­
ences in hydrocarbon potential of the North African with that of Arabian
plate seems to be due to the geological evolution of the basins after the
Silurian (Kara, 2021). Although the Hercynian orogeny ceased the
depositional phase during the Middle Carboniferous and Early Permian
in the SEA, the Carboniferous unit is represented by 400 m thick in the
Eastern Taurus. While the Early Permian was eroded, the Late Permian
unit is over 410 m thick (Göncüoğlu et al., 2004) owing to the additional
overburden rocks as well as the allochthonous nappe over the GDU,
resulting in almost a depleted HC potential in Silurian shales. The low HI
and high Tmax values of the Pusçu Tepe shales indicate that they are
overmatured. Since there are no vitrinite macerals in Silurian aged
14
Marine and Petroleum Geology 164 (2024) 106830
rocks, %VRo values calculated from Tmax data were used in this study
(Table 2). Most of the calculated %VRo values are higher than 1.2%
(Table 2). In addition, the graptolite - chitinozoa reflection and illite
crystallinity index values of the Silurian units in the Central and Eastern
Taurids showed that shales are in the over mature zone (Varol et al.,
2006; Döner et al., 2019; Bozkaya et al., 2002). The Eastern Taurus
Silurian shales also show that they have lost 85% and 98% of their
original hydrocarbon potentials according to TRHI ratios, except for one
sample. Although the Taurus Belt has a rather complex tectonic history,
Neogene aged Adana and İskenderun basins, which developed over the
Paleozoic basement, do not have the same tectonic history (Fig. 12).
The complex tectonic history of the eastern Taurus region and these
Neogene basins was simply outlined by Yılmaz (2020): the northward
advance of the Arabian Plate resulted in a compression regime, which, in
turn, gave rise to an orthogonal shortening and the Southeast Anatolian
Orogenic Belt (SAOB). Consequently, a wide foreland fold and thrust
belt was developed in the northern part (eastern Taurus) of the Arabian
plate. After the compressional deformation reached an excessive stage
that could no longer be accommodated, N–S compressional deformation
was replaced by the escape tectonic regime. Away from the closure of
the folds, strike-slip faults become dominant, that have sheared the
entire width of the Taurus, down to the Mediterranean (Yılmaz and
Çemen, 2017). In addition, the E–W compressional deformation has
deformed the whole sequence, including the Neogene sediments in the
intermountain basins (Koçyiğit et al., 2000; Koç et al., 2017). The
transtensional regime has also conduced significantly to the enlarge­
ment of the Adana basin (Yılmaz and Çemen, 2017). In the Adana basin,
petroleum with 37API from Bulgurdağı field was discovered in the
Middle Miocene reefal limestone by the Mobil Company in 1960. After
this discovery, 60 onshore (3 oil producing, 4 oil show, 2 oil + gas show,
10 gas show) and 2 offshore wells were drilled by several companies;
however, there has no discovered economic HCs. Few studies indicate
that the oil is derived from a Paleozoic - Miocene mixed source rock
(Baum and Schmitt, 1992).
The δ13Corg of Bulgurdağı oil (− 28.5 ‰ and − 29.0 ‰), Emelcik-1
well’s oil sample (− 29.2 ‰), and the δ13Corg of the oil extracted from
Feke outcrop (− 30.1 ‰) can be correlated (Baum and Schmitt, 1992),
indicating that immature/less mature Paleozoic shales may be present in
the basin. In addition, Loydell et al. (2009) and Loydell and Fryda
(2007) determined δ13Corg values of the late Rhuddanian levels (base of
hot shale) and late Telychian shales to, respectively range between
− 29.01‰ and − 28.82‰, and − 30.24 ‰ and − 29.58 ‰, with the lowest
value appearing in the lower lapworthi Biozone. In addition, Degens
(1969) suggested that Devonian oil δ13Corg values range from − 25 to
− 30. These δ13Corg evidence suggest that well and outcrop oils from the
basin might have been generated from late Telychian and/or early
Devonian shales. We suggest that there could be the Paleozoic (probably
mixed Silurian-Lower Devonian)-Middle Miocene Karaisalı (!) petro­
leum system in the Adana basin in the Eastern Taurus (Fig. 12), based on
the limited subsurface knowledge.
6. Conclusions
- Owing to different paleogeographic positions (southern and northern
paleo-Tethys, respectively) and consequently diverging paleocli­
matic patterns, hot shale deposition dynamics and the time intervals
during which these units were deposited are obviously different from
each other in North Africa and Taurus. The depositional model of
Silurian Pusçu Tepe Shales reveals a complex interplay of glacial,
eustatic, and geochemical factors. This complexity not only shaped
the sedimentation patterns observed in these regions but also high­
lights the diverse environmental and climatic conditions that pre­
vailed during the Silurian period. The comparison of these
depositional models provides valuable insights into the regional
paleogeography and the dynamic processes that have influenced the
geological evolution of Gondwana’s northern margin.
T. Ayyildiz and E.A. Acar
Fig. 12. NW-SE directional geological cross-section between the Central Taurus Belt-Adana-Iskenderun basins (Modified from Kozlu, 1997).
- Through detailed original source rock analyses and recalculations,
this study sheds light on the varying potential of these formations as
unconventional petroleum systems, highlighting the intricate inter­
play between geological processes and petroleum generation dy­
namics. Such insights are invaluable for advancing our
understanding of petroleum geochemistry and improving explora­
tion strategies in similar geological settings.
- Due to the Taurus being located further north and possessing a cooler
climate, nitrate-rich upwelling currents and Si-rich materials were
transferred from different sources into the depressions, triggering a
bloom in the population of radiolaria across the Paleo-Tethys Ocean,
which, in turn, resulted in the formation of mainly lydite (black
chert) or lydite-siliceous rich shale deposition throughout southern
Europe from Iberian to eastern Taurus during 8.3 Ma. Once the
deposition of hot shale I was through, the upper organic-rich hot
shale II was deposited as the highest sea level in both North Africa-
SEA and Taurus depression had been achieved in the Late Llandov­
ery (Telychian).
- We suggest a different scenario for the limestones rich in Orthoceras
formation: slightly more acidic seawater (higher H2CO3) was formed
as a result of the increase in partial pressure of CO2 (due to the
opening of Paleo-Tethys Ocean and the accompanied volcanism
along its southern margin; Bagheri and Stampfli, 2008) in the at­
mosphere, which resulted in the breakdown of Ca-rich plagioclase
minerals. The released Ca2+ ions were taken up by CO2− 3 ions in the
seawater, triggering the formation of limestone units. The subse­
quent decrease in the concentration of CO2 in the atmosphere
resulted in the cooling of the continent, which facilitated the depo­
sition of clastics (i.e., shale). This regressive character may have
helped the deposition of the Wenlock (late Sheinwoodian) and late
Pridoli-Lochkovian black shale sequences observed, for example, in
the Tadla Basin and Taurus depressions.
15
Marine and Petroleum Geology 164 (2024) 106830
- The early-middle Rhuddanian, late Telychian and late Sheinwoodian
hot shales are characterized as effective petroleum source rocks in
the North Africa depressions, while these source units in Taurus were
late Telychian, late Sheinwoodian and late Pridoli-Lochkovian in
terms of age. While original pyrolysis values of black shales have
merely dry gas potential, the original values of the black shales (late
Telychian, late Sheinwoodian and late Pridoli, Lochkovian) are
supposed to have possessed good to very good source rock potential
with Type II kerogen being the dominant kerogen.
- Since it has been determined that the Early Devonian (Lockhovian)
aged black shales in the study area have potential in areas where they
are not affected by overburial, promising results may be obtained
provided that the exploration effort in the Eastern Mediterranean
onshore or offshore area (Adana Basin and/or Iskenderun Bay)
continues.
CRediT authorship contribution statement
Turhan Ayyildiz: Writing – review & editing, Writing – original
draft, Visualization, Supervision, Methodology. Eren Aykan Acar:
Methodology, Investigation, Funding acquisition, Formal analysis, Data
curation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
T. Ayyildiz and E.A. Acar
Acknowledgment
The authors thank to Dr. Arash Vosoughi and Adem Özdemir (Bülent
Ecevit University) for contributing to the grammatical improvement of
the writing language of the draft article and for drawing some figures,
respectively.
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