Marine and Petroleum Geology 64 (2015) 294e303

Contents lists available at ScienceDirect

Marine and Petroleum Geology

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

Research paper

Depositional environment of the Lower Silurian Akkas hot shales

in the Western Desert of Iraq: Results from an organic
geochemical study
Mohamed W. Alkhafaji a, *, Zeki A. Aljubouri b, Imad A. Aldobouni c
a
b
c

Department of Applied Geology, College of Science, University of Tikrit, Iraq

Department of Geology, College of Science, University of Mosul, Iraq
Department of Chemistry, College of Science, University of Mosul, Iraq

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 5 February 2014
Received in revised form
27 December 2014
Accepted 11 February 2015
Available online 28 February 2015

The lower Silurian hot shales in the lower part of Akkas Formation in Akkas eld, western Iraq were
studied to determine their depositional environments. For this purpose, organic and inorganic proxies
were used. These include total organic carbon content (TOC), sulfur, pyrite, and carbonate content
measurements, as well as the saturated and aromatic biomarkers. Organic carbon content (TOC), pyrite,
and carbonate contents were high and pristane/phytane ratio (Pr/Ph) was low in these hot shales,
indicating deposition under anoxic marine conditions. The presence of gammacerane suggests water
column stratication; the presence of aryl isoprenoids (originating from aromatic carotenoids of green
photosynthetic sulfur bacteria), indicates deposition under euxinic conditions, extending from the photic
zone to the sedimentewater interface. The conditions became more oxygenated upward, which led to
the deposition of organic-poor gray-green shales in the upper part of Akkas Formation, with low pyrite
and carbonate contents and high Pr/Ph ratios.
2015 Published by Elsevier Ltd.

Keywords:
Hot shales
Akkas Formation
Euxinic conditions

1. Introduction
Transgressive, organic-rich hot shales (the term hot shales
refer to their high gamma-ray response in the lithological proles)
were deposited in North Africa and Arabia during the latest
Ordovician to early Silurian as a result of sea level rise due to global
warming (Luning et al., 2000). These hot shales are considered to be
the main hydrocarbon source rocks in Paleozoic successions in
North Africa and Arabia (Luning et al., 2000, 2005).
The Lower Silurian black shales have been studied intensively in
North Africa and Arabia to determine their hydrocarbon potential
and depositional environment (e.g. Luning et al., 2000, 2005; Le
Heron et al., 2008, 2009; Armstrong et al., 2005, 2009; Vecoli
et al., 2009; Cole et al., 1994; McGillivary and Al-Husseini, 1992;
Mahmoud et al., 1992). However, their origin remains contentious
(Armstrong et al., 2009).

* Corresponding author.
E-mail
addresses:
(M.W. Alkhafaji).

mohamed_wagga@yahoo.com,

http://dx.doi.org/10.1016/j.marpetgeo.2015.02.012
0264-8172/ 2015 Published by Elsevier Ltd.

m.ageel@tu.edu.iq

In Iraq, the hot shales at the base of the Akkas Formation are
probably the main source rocks for the large quantities of sweet gas
and small quantities of condensate and light oils discovered in
Akkas eld (Fig. 1) within the Ordovician and Silurian successions
of Khabour and Akkas Formations, respectively (Al-Habba et al.,
1994).
There exist only a few studies of the hot shales in Iraq, most of
which use palynology to determine their depositional environment
(e.g. Al-Ameri, 2009). Al-Ameri (2009) concluded that these beds
were deposited in an anoxicedysoxic marine shelf environment,
extending from outer to inner neritic, with effects of local
upwelling currents. The aim of this study is to investigate the
depositional environment of the hot shales using an organic and
inorganic geochemical approach.
2. Geological setting
The Silurian Akkas Formation is not exposed in outcrops in Iraq,
however, the formation has been penetrated in many exploration
wells in the Western Desert of Iraq (Fig. 1). The formation consists
of interbedded shales and sandstones and it is subdivided into two
members, the lower member, Hoseiba, and the upper member

M.W. Alkhafaji et al. / Marine and Petroleum Geology 64 (2015) 294e303

295

Figure 1. Geological Map of Iraq showing the major tectonic zones and the location of the study area (After Jassim and Buday, 2006). The Stable Shelf, comprised of Rutba Jezira, Salman
and Mesopotamian Zones, is a tectonically stable monocline little affected by Late Cretaceous and Tertiary deformation and is characterized by the absence of surface anticlines.
Geologically, the Rutba Jezira Zone is dominated by the Rutba uplift. The Salman Zone is a syn-Hercynian high, and subsided strongly in latest Palaeozoic/Triassic time. The
Mesopotamian Zone comprises a complete Mesozoic and Cenozoic section covered with Quaternary sediments. The Unstable Shelf, comprised of the Foothill, High Folded, BalamboTanjero and Northern Thrust (Ora) Zones, is more affected by Late Cretaceous and Tertiary deformation and is characterized by surface folds. The Foothill Zone is characterized by long
anticlines with Neogene cores and broad synclines containing a thick Miocene-Quaternary molasse sequence. The High Folded Zone is characterized by anticlines of high amplitude
with Palaeogene or Mesozoic carbonates exposed in their cores. The Balambo-Tanjero Zone contains thick uvial and marine clastics sequences and is characterized by imbricated
structures. The Northern Thrust (Ora) Zone is characterized by thrusted anticlinal structures. The Zagros Suture is comprised of radiolarian cherts associated with volcanic rocks in the
Qulqula-Khwakurk Zone and metamorphosed volcanic and sedimentary rocks in the Penjween-Walash and Shalair Zones (Jassim and Buday, 2006).

Qaim (Fig. 2) The Qaim member consists of ne grained sandstone

and gray-green shales. The lower Hoseiba member consists of
ssile gray and black pyritic shales. In the lowermost part of this
member, there are two beds of black shales with high TOC and high
level of gamma-ray radiation (hot shales) close to the lower contact
with the Ordovician Khabour formation (Fig. 2).
The total thickness of the formation in Akkas-1 well is 864 m. In
this well, the lower contact between the Akkas and Ordovician
Khabour formations is sharp; the upper contact is unconformable
with the Late Devonian Perispiki Red Beds (Al-Hadidy, 2007).
The lower Silurian hot shales include two beds of black, ssile,
calcareous, bituminous organic-rich shales (Fig. 2). In Akkas-1well,
the upper and lower hot shales have a thickness of 25 and 41 m,
respectively. These two beds of hot shales have high gamma ray
radiation. Between these two beds there are 25 m of gray shales
with normal gamma radiation (Aqrawi, 1998; Al-Hadidy, 2007).
These organic-lean shales represent hemipelagic and prodeltaic,
well-oxygenated shale facies. They are rich in quality kaolin, which
is commercially exploited in the southern desert of Jordan (Luning
et al., 2005).

shale. Most of the analyzed samples were from Akkas-1 well, since
it is the deepest and the samples from it were more easily available
than from the other wells.

3. Materials and methods

3.2. Organic petrology

A total number of fty seven cutting and core shale samples

from the Silurian Akkas Formation, from ve wells (Akkas-1, 2, 3, 4,
and 5) in Akkas eld, western desert of Iraq (Fig. 1), were collected
and analyzed to determine the depositional environment of the hot

Organic petrology analysis followed procedures described by

Taylor et al. (1998). Polished sections were prepared from 20
samples. Firstly, they were embedded in a 10:3 mixture of epoxy
resin and hardener and hardened in an oven at 37
C for about 12 h.

3.1. TOC and sulfur content measurements

Total Organic Carbon (TOC) measurements used Solids Module
1000
C instrument. The carrier gas for combustion is synthetic air
(carbon hydrogen <0.1 ppm; CO2 < 0.1 ppm), pre-pressure 1.5 bar
and ow rate approximately 200 ml/min. The analysis duration was
about 15 min for each sample.
For the determination of Total Carbon (TC), the samples were
rst homogenized and then weighed (100 mg) in a quartz boat. The
samples were combusted and the combustion gases were oxidized
to CO2 on a post-combustion catalyst (platinum on ceramic carrier).
The obtained CO2 was quantied using Infra-Red (IR) spectroscopy,
allowing independent quantication of both TOC and Total
Inorganic Carbon (TIC).
Sulfur content was measured for all samples using LECO S200
sulfur analyzer at temperature 1000
C.

296

M.W. Alkhafaji et al. / Marine and Petroleum Geology 64 (2015) 294e303

Figure 2. Akkas Formation lithology and Gamma-ray prole in Akkas-1 well (After Al-Hadidy, 2007). Note the high values recorded to the lower and upper Hot shale intervals.

M.W. Alkhafaji et al. / Marine and Petroleum Geology 64 (2015) 294e303

The samples were polished using an automatic StruersTegra Pol 21

polishing machine, and examined using a Zeiss Axio Imager M2m
microscope. For data processing, Diskus Fossil software was used.
3.3. Solvent extraction, liquid chromatography, compound class
fractionation, gas chromatography (GC) and GC-mass spectrometry
(GCeMS)

297

supported by the Tmax values of pyrolysis (422e445
C), indicating

that these organic matter is immatureeearly mature stage
(Alkhafaji et al., 2015). From the Rock-Eval pyrolysis data (plot of
TOC vs. S2), the organic matter type is classied as type II marine
planktonic, mainly algae-derived; and deposited under anoxic
conditions (Alkhafaji et al., 2015).
4.2. Pyrite

After the samples were ground, bitumen was extracted from the
resulting powder (ca. 5 g) for 24 h using 50 ml of DCM (dichloromethane; CH2Cl2). After extraction, the solvent was removed with a
rotary evaporator. The extracts were separated by column
chromatography over activated silica gel and eluted sequentially
into three fractions using n-pentane (fraction 1), n-pentane/CH2Cl2
(40/60 v/v, fraction 2), and methanol (fraction 3). GC was carried
out with a Carlo Erba 8000 gas chromatograph equipped with a
30 m  0.25 mm ID  0.25 mm lmZebroneZB 5 fused silica column. The oven temperature was programmed from 60 to 300
C at
a rate of 3
C/min, with a 20 min isothermal period at 300
C. Injection was performed in the split/splitless mode with a splitless
time of 60 s. Hydrogen was used as a carrier gas (injection temperature: 270
C). GC/MS analysis was carried out using a Finnegan
MAT 8222 mass spectrometer linked to an HP 5890 gas
chromatograph. A 30 m  0.25 ID  0.25 mm lm Varina CP Sil-8CB
fused silica column was used. Helium was used as carrier gas. The
temperature was programmed from 80 to 310
C at a rate of
3
C/min, with a 5 min isothermal period at 310
C.
4. Results and discussion
4.1. Organic petrology
The Organic petrology study of selected samples of hot shales
reveals that they consists predominantly of amorphous organic
matter (AOM) with minor amounts of alginate; solid bitumen is
present as well in some samples. In polished sections, AOM appears
as a matrix material with no dened shape, mixed with mineral
grains, but easily recognizable in kerogen concentrate under the
microscope with transmitted light. In transmitted light, AOM
appeared as brown-black ne grain particles with irregular shape.
In the upper part of the Akkas Formation, the organic matter is also
dominated by the AOM, but it is very rare. The organic matter
abundance is reected by the TOC values, where it is high in the hot
shales of the lower part of the formation and very low in the upper
part.
Amorphous organic matter probably originates as bacterial
decomposition products of algae and faunal plankton (Taylor et al.,
1998). In the hot shales, the AOM is believed to have originated
from alginate because both (alginate and AOM) are associated. High
abundance of algal material in the primary organic matter is
supported by the presence of amorphous organic matter associated
with alginite in some samples, especially those of the hot shale,
which indicates a high contribution of planktonic algal organic
matter deposited in anoxic conditions. The amorphous nature of
the organic matter reects signicant microbial interaction within
the sediments under reducing conditions. On the other hand; the
high relative abundance of C30 hopane is interpreted to reect a
primary microbial input and extensive reworking of the organic
matter.
The organic matter of Akkas formation show strong uorescence under blue light excitation and most of them appear as
amorphous uorescence and displays no morphology which can be
assigned to any known maceral type. This indicates that the organic
matter of this part of Akkas Formtion has low level of thermal
maturity. The low thermal maturity level of these organic matter is

In modern anoxic sediments, the pyrite forms as authigenic

mineral, and in ancient rocks it occurs as euhedral crystals and
framboids (Zhou and Jiang, 2009). Pyrite originates from the sulde
sulfur produced by the anaerobic reduction of sulfate (Berner,
1970). Several environmental factors control the formation of
pyrite framboids, beginning with free iron availability in the environment (Nzoussi-Mbassani et al., 2003). The concentration of the
organic matter during early diagenesis probably represents the
most important factor in the formation of pyrite as direct cause of
reducing conditions (Pfendt et al., 1988). Therefore, size distribution of pyrite framboids in modern and ancient sediments was used
as a redox indicator (Zhou and Jiang, 2009; Wignall et al., 2005).
Pyrite has been found in the examined shale samples of Akkas
Formation with different size and abundance. The crystal size
ranges from very ne to several centimeters, and pyrite occurs as
dispersed euhedral particles or as densely packed, spherical
aggregates of euhedral, equigranular crystals (Plate 1A and B). The
density of pyrite crystals varies throughout the section and it is well
correlated with TOC (as evident from the TOCeS relationship).
Pyrite is more abundant in the black shales in the lower part of the
Formation, which has the highest TOC values. In these black shales,
most pyrite crystals occur as small euhedral crystals (about
0.3e3 mm), but some are large enough to be seen with the naked
eye in the rock samples and on the surface of polished sections
(Plate 1A). The gray shales of the upper part (with low TOC values)
have very low abundance of pyrite crystals, which appear as
dispersed euhedral particles and as densely packed euhedral, very
small crystals (less than 0.2 mm) (Plate 1B). In modern sediments,
the size distribution of pyrite framboids is related to the redox
conditions of bottom waters. In euxinic basins, they are smaller
than those contained in sediments of oxic and dysoxic basins
(Wilkin et al., 1996). Tribovillard et al. (2006) observed that if the
chemocline was above sedimentewater interface, the pyrite will
form syngenetically as ne grained, euhedral crystals. On the other
hand, if the chemocline was at or below the sedimentewater
interface, pyrite would form diagenetically as large spherical
framboids. Some of the examined samples from the black shales
have a narrow crystal size range, which may indicate that suldic
water column conditions were persistently developed; and the
high sulfur content (see table below) may indicate that the H2S
layer was thick in the water column, which led to pyrite enrichment
in these sediments. However, the presence of large pyrite crystals
may rather be due to their diagenetic origin.
The abundance of pyrite in the black shales of the lower part of
Akkas Formation indicates that sufcient iron was available to x
most sulfur in the form of iron sulde. This availability of iron is also
supported by the very low abundance of dibenzothiophene in the
aromatic fraction of the sediment extracts, which suggests that
there was no free sulfur to react with organic matter. The abundance of pyrite in the examined samples, associated with the large
quantities of sedimentary organic matter, largely of marine origin,
and the common occurrence of well-developed sedimentary
lamination in these shale beds, indicate that the accumulation of
these shales were under oxygen-depleted conditions. These
conditions led to enrichment of authogenic uranium in these
shales, with concentrations between 10 and 25 ppm (Majidee,

298

M.W. Alkhafaji et al. / Marine and Petroleum Geology 64 (2015) 294e303

personal communication, 1999). The elevated uranium content

produced the high gamma-ray radiation observed for these
samples.
4.3. TOCesulfurecarbonate relationship
The average TOC of the ve wells of Akkas Formation is 2.73%
ranging 0.16e7.3% (Table 1). Other studies recorded even higher
values, up to 16% (Al-Habba et al., 1994). TOC values of the upper

Table 1
Well identication and depths from which the Silurian shales from the Akkas
Formation were collected. Shown are also results from TOC, TIC, CaCO3 and sulfur
analyses as well as the ratio of total sulfur over TOC (TS/TOC).
Well

Age

Depth
(m)

TOC
(wt%)

TIC
(wt%)

CaCO3

TS
(wt%)

TS/TOC

Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-1
Akkas-2
Akkas-2
Akkas-2
Akkas-2
Akkas-2
Akkas-2
Akkas-2
Akkas-3
Akkas-3
Akkas-3
Akkas-3
Akkas-3
Akkas-3
Akkas-3
Akkas-3
Akkas-3
Akkas-3
Akkas-3
Akkas-3
Akkas-3
Akkas-4
Akkas-4
Akkas-4
Akkas-4
Akkas-4
Akkas-4
Akkas-5
Akkas-5

Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian

1450
1579
1590
1606
1650
1680
1710
1715
1785
1825
1855
1896
1960
1990
2015
2025
2065
2210
2214
2218
2222
2225
2280
2290
2300
2310
2315
2320
2325
2180
2220
2227
2231
2273
2306
2323
2180
2190
2195
2200
2235
2280
2285
2290
2295
2300
2305
2310
2315
1456
1697
2243
2259
2325
2372
1687
2036

0.19
0.17
0.19
0.23
0.23
0.18
0.22
0.32
0.22
0.22
0.22
0.16
0.18
0.26
4.76
0.64
0.26
3.22
6.38
6.97
4.73
4.24
2.60
4.26
3.93
4.06
2.76
4.33
4.83
1.92
3.04
7.30
5.08
1.73
4.89
6.48
1.92
3.41
4.84
4.57
0.99
4.73
5.25
5.18
4.94
4.08
3.58
4.76
5.05
0.60
0.58
0.90
1.68
5.03
2.24
0.95
1.54

0.28
0.21
0.20
0.20
0.15
0.25
0.24
0.30
0.21
0.24
0.25
0.06
0.12
0.22
2.15
0.70
0.43
2.19
1.46
2.21
2.31
2.08
1.28
2.19
1.89
1.51
1.50
1.85
1.67
0.69
1.16
1.83
1.91
0.95
1.92
1.47
0.81
1.45
1.32
1.18
0.71
2.10
2.04
1.14
1.34
1.12
0.99
1.62
1.39
0.18
0.12
0.29
0.69
1.62
0.88
0.23
0.36

2.36
1.76
1.68
1.68
1.25
2.06
1.97
2.53
1.75
2.04
2.12
0.49
1.00
1.82
17.91
5.81
3.62
18.23
12.15
18.41
19.24
17.33
10.65
18.24
15.74
12.56
12.50
15.45
13.91
5.71
9.68
15.24
15.91
7.90
15.99
12.26
6.74
12.08
11.00
9.83
5.93
17.49
16.99
9.50
11.16
9.34
8.29
13.49
11.58
1.52
1.03
2.44
5.72
13.49
7.35
1.95
3.02

0.53
0.57
0.4
0.59
0.75
1.03
0.73
0.85
0.61
0.6
0.44
1.49
0.85
0.63
3.41
0.94
1.41
8.4
4.79
4.34
3.61
5.7
2.39
4.74
3.67
4.47
2.74
4.34
4.99
2.97
3.33
5.53
5.06
2.39
4.98
4.41
2.76
6
4.34
3.74
1.78
4.54
3.87
4.08
2.64
3.6
3.71
4.38
4.94
0.58
1.53
1.26
2.06
5
2.06
0.71
0.92

2.79
3.35
2.11
2.57
3.26
5.72
3.32
2.66
2.77
2.73
2.00
9.31
4.72
2.42
0.72
1.47
5.42
2.61
0.75
0.62
0.76
1.34
0.92
1.11
0.93
1.10
0.99
1.00
1.03
1.55
1.10
0.76
1.00
1.38
1.02
0.68
1.44
1.76
0.90
0.82
1.80
0.96
0.74
0.79
0.53
0.88
1.04
0.92
0.98
0.97
2.64
1.40
1.23
0.99
0.92
0.75
0.60

TOC Total Organic Carbon; TIC Total Inorganic Carbon; TS Total Sulfur.

Figure 3. Positive TOCeTS relationship of black shales of Akkas Formation.

r2 Correlation Coefcient (not considering the very high (>8 wt%) point).

part of the formation are very low, whereas those of the hot shale of
the lower part are high.
The total sulfur content (TS), which represents mainly pyritic
sulfur, is generally medium to high. TS values of the shale beds of
Akkas Formation from different wells have an average of 2.86%, and
most values are in the range 0.4e6.0 %, with one exceptional value
(8.4%) which was found at a depth of 2210 m in Akkas-1 well
(Table 1), corresponding to the upper horizon of the hot shale. The
high values were recorded in the lower part of the Formation (hot
shale horizons), where TOC and carbonate content are also high
(Table 1). The low values were recorded in the upper part, in the
organic lean shales which have also low TOC and carbonate
content.
The total sulfur:organic carbon (TS/TOC) ratio reects the
intensity of microbial sulfate reduction in organic matter decomposition, giving an indication of the redox status in the depositional
environment (Sachse et al., 2012). In marine sediments deposited
under aerobic bottom water, there is an empirical relationship
between organic carbon content and sulfur content (Berner, 1984).
The average TS/TOC ratio of Akkas Formation is high with a
value of 1.77, and covers the range 0.53e9.5 (Table 1). Generally, the
TS/TOC values decrease with depth, with the lower values in the
lower part corresponding to the black shales. Very high TS/TOC
ratios in the organic-poor shales of the upper part (average 3.08),
suggest that more organic matter is consumed by sulfate reduction
than under normal marine conditions (Berner, 1984), but TOC
values are low. This indicates only poor primary organic matter

Figure 4. Relationship of Carbonate content with TOC in black shales of Akkas Formation. R2 Correlation Coefcient.

M.W. Alkhafaji et al. / Marine and Petroleum Geology 64 (2015) 294e303

Table 2
Pristane/Phytane (Pr/Ph) and Dibenzothiophene/Phenanthrene (DBT/P) ratios of the
gray-green and the black shales of Akkas Formation from Akkas-1well.
Age

Lithology

Depth (m)

Pr/Ph

DBT/P

Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian
Silurian

Gray shale
Gray shale
Gray shale
Gray shale
Gray shale
Gray shale
Black shale
Black shale
Black shale

1450
1579
1645
1680
1710
1896
2015
2218
2222

1.66
2.08
1.35
1.17
1.12
0.78
0.93
1.15
0.91

0.004
0.018
0.023
0.002
0.012
0.116
0.015
0.011
0.005

preservation, that is, no anoxic bottom water (Sachse et al., 2012).

TS/TOC values of the black shales are generally moderate to high
(average 1.06), with high TOC and relatively high TS. This may
indicate that these shales were deposited under high productivity
conditions (Sachse et al., 2012).
Obviously, there is a positive relationship between TS and TOC of
the black shale samples of the lower part of Akkas Formation
(R2 0.65; Fig. 3). The line of the TOCeTS relationship intercepts
the sulfur axis (at a value of about 1.2%). This is a good indication
that there is an excess of sulde and these black shales were
deposited under euxinic conditions, in which pyrite partially
formed in the water column (Leventhal, 1983).
The calcium carbonate contents (CaCO3) of the measured
samples of Akkas Formation are in the range 0.5e23.8%, with an
average of 7.75%. The high carbonate content was in the black
shales of the lower part of the Formation, where TOC values are also
high. The positive relation between TOC and carbonate content in
the black shales is obvious (R2 0.54; Fig. 4). In the black shales, the
high carbonate content suggests a strong marine effect and an
anoxic depositional environment. Sachse et al. (2012) pointed out
that the margin samples contain less carbonate than the open
marine sediments, reecting continental contributions of clastic
sediment components.
4.4. Pristane/phytane
The pristane/phytane ratio (Pr/Ph) has been used as an indicator
of redox conditions in ancient sediments (Didyk et al., 1978).
Generally, Pr/Ph values above 1.0 indicate oxic conditions, while
values below 1 indicate anoxic conditions.
The (Pr/Ph) ratio of the shale samples from Akkas-1well has a
range of (0.78e2.08) (Table 2). These values show systematic

299

decrease with depth. The high values were recorded in the gray
shales of the upper part of the formation, in the organic-poor
shales, and the low values in the black shales of the lower part, in
the organic-rich shales. These values indicate that these black
shales were deposited under anoxic conditions, whereas the gray
shales were deposited in dysoxiceoxic conditions. The highly
anoxic conditions are also indicated by extended hopane prole
with prominent C31eC35 homohopanes (Peters and Moldowan,
1991) (Fig. 5).
4.5. Dibenzothiophene/phenanthrene
All the samples of Akkas Formation show very low concentrations of dibenzothiophene. This indicates siliciclastic depositional
environment, and suggests that the iron abundance in a depositional environment was sufcient to react with all the sulde
present, leaving no free sulde available to react with the organic
matter (Jiang et al., 2001). This result is supported by the ratio of
dibenzothiophene to phenanthrene of the studied samples, which
is generally less than 1 (Table 2). This indicates that there was no
availability of reduced sulfur to incorporate into the organic matter
(Hughes et al., 1995). The ratio (DBT/Phenanthrene) is also an indicator of source lithology, with carbonate having a ratio greater
than one and shales with a ratio less than one. Figure 6 shows that
most of the studied samples plot in the marine shale eld, but some
samples are located in lacustrine eld. It is believed that these
samples were deposited under highly reducing conditions that led
to the very low Pr/Ph ratios.
4.6. Perylene
Perylene can originate from more than one precursor: from both
aquatic and continental organic matter and through different
microbial processes (Peters et al., 2005 and references therein). Still
other sources include diagenetic formation from non-specic
precursor material (Bechtel et al., 2007). Romero-Sarmiento et al.
(2011) detected this compound in sediments dating from Late
Silurian to early Devonian in southern Tunisia. Grice et al. (2009)
proposed that perylene could be associated with fungi and/or
anoxic conditions. Silliman et al. (1998) indicated that perylene is a
better indicator of depositional environment than of organic matter
source; it forms under anoxic environments. Routh et al. (1999)
detected the highest concentration of this compound in transgressive mudstone which is considered to be representative of
anoxic environments.

Figure 5. m/z 191 mass chromatogram showing gammacerane and homohopanes in black shale sample (Akkas-1 well, depth 2015 m).

300

M.W. Alkhafaji et al. / Marine and Petroleum Geology 64 (2015) 294e303

organic matter of the two parts is composed predominantly of

amorphous organic matter). Therefore, the sedimentary environment may be the major reason for the differences in perylene
abundance between the two parts. The anoxic conditions which
prevailed during deposition of the black shales led to good
preservation of this compound. The distribution of perylene is also
consisted with the highly reducing environment of these shales,
which have low (Pr/Ph) ratios, within the range of 0.73e1.15.
4.7. Aryl isoprenoids and gammacerane

Figure 6. Cross plot of Dibenzothiophene/Phenanthrene (DBT/P) versus Pr/Ph ratios

for the studied samples of the gray and the black shales (Hughes et al., 1995).

This compound has been recorded in the aromatic fraction of

the studied samples from black shales at depths of 2015, 2218, and
2222 m in Akkas-1well (Fig. 7). It has not been detected in the gray
shale samples of the upper part. Regarding the organic matter type,
no signicant differences were observed in the organic matter
source between the upper and lower part of the Formation (the

The presence of aryl isoprenoids in the aromatic fraction of

the examined black shale samples of Akkas Formations
(m/z 133 134) (Fig. 8), originated from aromatic carotenoids of
green photosynthetic sulfur bacteria (Summons and Powell, 1987);
provide an insight to the source facies. Aryl isoprenoids were
recorded from CenomanianeTuronian sediments in the North
Atlantic Ocean (Sinninghe Damste and Koster, 1998), in the Tarfaya
Basin (Kolonic et al., 2002) and from the Betra Formation basin in
Jordan (Armstrong et al., 2009).
It is well accepted that these oxygenic organisms often proliferate at the oxiceanoxic boundary of stratied, sulde rich water
bodies, such as alkaline lakes and silled basins (Sun et al., 2003).
The presence of aryl isoprenoids in the black shales of Akkas Formation reveals that penetration of the photic zone by suldic waters during deposition enabled a prolic growth of photosynthetic
green sulfur bacteria. This suggests that the euxinic water column

Figure 7. Mass chromatograms of m/z 252 showing the distribution of perylene in sediment extracts of the black shales from Akkas-1well (2218 m). The lower view is the mass
spectrum of peak A.

M.W. Alkhafaji et al. / Marine and Petroleum Geology 64 (2015) 294e303

301

Figure 8. Mass chromatograms of (m/z 133 134) showing the distribution of aryl isoprinoids in sediment extracts of the black shales from Akkas-1well (2222 m). The lower view
is the mass spectrum of peak A.

was extended into the photic zone at the time of deposition. The
high abundance of pyrite crystals in these strata reveals that suldic
water columns were developed at those times, supporting
populations of anoxygenic photosynthetic green sulfur bacteria
(Sun et al., 2003).
Sinninghe Damste et al. (1995) suggested that gammacerane is
derived from tetrahymanol, which is present in photosynthetic
sulfur bacteria, and it is an indicator of water column stratication.
Therefore, the presence of photosynthetic sulfur bacteria and water
stratication at the time of deposition of these hot shales of the
Akkas Formation is indicated also by the presence of gammacerane
with a relatively high gammacerane index value of 0.23 (Fig. 5).
Armstrong et al. (2009) recovered isorenieratene, originating from
green sulfur bacteria, in the hot shale horizon of Betra basin in
Jordan, which indicates photic zone anoxia during deposition. They
also conrmed that the lower hot shale was deposited in a salinity
stratied water column during the Hirnantian to early Silurian
deglaciation, in which anoxic conditions were initiated beneath the
halocline, and a fresher surface layer resulted from ice melting
during the early deglaciation (Fig. 9). They point out that Betra
basin record a few hundred thousand years of water column
stratication and basin euxinia during deglacial highstand. The hot
shales of Akkas formation are equivalent to the lowermost part of
Batra formation in northeast Jordan (Jassim, 2006). The lower part
of Batra formation consists of laminated, organic-rich, graptolitic,
pyritic, nonbiotubated black shales, and contains type II kerogen
(Armstrong et al., 2005, 2009). These black shales were deposited
during marine transgression following ice melting. These

sedimentological characteristics are identical to those of the hot

shales of Akkas formation. Therefore, it is believed that similar
conditions prevailed during the deposition of the hot shale beds of
the lower part of the Akkas Formation in Iraq.
Luning et al. (2000) suggested that the poorly oxygenated
conditions prevailed during the initial transgression, which led to
deposition of these black shales, and when sea level continued to
rise, the fully marine oxygenated conditions became established
over the northern Gondwana shelf due to the enhanced circulation,
leading to the deposition of organic poor shales. The anoxic conditions enhanced the preservation of organic matter and led to

Figure 9. Conceptual model of the stratied water column during the deposition of
the hot shales (After Armstrong et al., 2009).

302

M.W. Alkhafaji et al. / Marine and Petroleum Geology 64 (2015) 294e303

depositional environment during progradation of sediments.

This is supported by the low TOC, carbonate, sulfur and pyrite
contents, and high (Pr/Ph) ratio.
 The deposition of the hot shales in the lower part of the Akkas
Formation took place in euxinic marine conditions. The euxinic
conditions led to high TOC, carbonate and pyrite contents, and
low (Pr/Ph) ratios. These conditions extended to the photic zone,
as evidenced from the presence of aryl isoprenoids in these
shales originating from green sulfur bacteria.
 The model suggested by Armstrong et al. (2009) for the deposition of the Upper OrdovicianeSilurian black shale in Jordan is
valid for the interpretation of the deposition of black shales in
the Akkas Formation.
Acknowledgments
The authors thank Iraqi Ministry of Higher Education and
Scientic Research for nancial support of this work. We also would
like to thank North Oil Company (Kirkuk-Iraq) for providing the
samples used in this work. The authors are grateful to associated
editor W. Kalkreuth and two anonymous reviewers for constructive
comments on an earlier draft of this manuscript.
References

Plate 1. Large euhedral pyrite crystals (P) in black shales (sample A), and (B) showing
aggregate of small euhedral crystals of pyrite in gray shales. Sample incident light.

deposition of well laminated, calcareous, pyritic, organic-rich black

shale. The presence of millimeter-scale lamination, which could
reect seasonal to decadal changes in sea ice cover (Armstrong
et al., 2009), associated with the absence of bioturbation in the
black shale of the lower part of Akkas Formation implies that
oxygen levels were low.
A progressive return to lower productivity and less anoxic
conditions, or suboxicedysoxic conditions, after the end of hot
shale deposition, led to deposition of organic lean gray shales in the
upper part of Akkas Formation. Gray shales are associated with
increasing thickness of the sandstone beds, which could indicate
that the marine effect was reduced due to progradation of sediments. This is also indicated by the decreasing TOC, carbonate and
pyrite, and elevated values of (Pr/Ph) in the 1450e1710 m interval
in the Akkas-1well. This decrease in surface productivity could
parallel the documented 3rd or 2nd order sea level fall occurring in
the upper Wenlock (Luning et al., 2000).

5. Conclusions
The results of the organic and inorganic geochemical study of
the Akkas Formation shales can be summarized as follows:
 The deposition of gray and green shales in the upper part of the
Silurian Akkas Formation occurred in an oxicesuboxic

Al-Ameri, T.K., 2009. Palynostratigraphy and the assessment of gas and oil generation and accumulation in the Lower Paleozoic, Western Iraq. Arabian J. Geosci.
3 (2), 155e179.
Al-Habba, Y.K., Al-Samarrai, A., Al-Juboury, F., Georgis, N.N., Ahmed, I.M., 1994.
Exploration for the Paleozoic prospects in western Iraq, Part 1: exploration of
the Paleozoic system in western Iraq. In: Proceedings of the Second Seminar on
Hydrocarbon Potential of Deep Formations in the Arab Countries (OAPEC),
Cairo, p. 21 (in Arabic).
Al-Hadidy, A.H., 2007. Paleozoic stratigraphic lexicon and hydrocarbon habitat of
Iraq. GeoArabia 12 (1), 63e130.
Alkhafaji, M.W., Aljubouri, Z.A., Aldobouni, I.A., Littke, R., 2015. Hydrocarbon potential of Ordovician-Silurian successions in Akkas Field, Western Desert of Iraq.
Am. Assoc. Pet. Geol. Bull. 99 (4), http://dx.doi.org/10.1306/10221413197.
Aqrawi, A.A.M., 1998. Paleozoic stratigraphy and petroleum systems of the Western
and Southwestern Desert of Iraq. GeoArabia 3, 2229e2248.
Armstrong, H.A., Abbott, G.D., Turner, B.R., Makhlouf, I.M., Muhammed, A.B.,
Pedentchouk, N., Peters, H., 2009. Black shale deposition in an upper Ordovician- Silurian permanently stratied, peri-glacial basin, southern Jordan.
Palaeogeogr. Palaeoclimatol. Palaeoecol. 273, 368e377.
Armstrong, H.A., Turner, B.R., Makhlouf, I.M., Weedon, G.P., Williams, M., Al
Smadi, A., Abou Salah, A., 2005. Origin, sequence stratigraphy and depositional
environment of an upper Ordovician (Hirnantian) deglacial black shale, Jordan.
Palaeogeogr. Palaeoclimatol. Palaeoecol. 220, 273e289.
Bechtel, A., Widera, M., Sachsenhofer, R.F., Gratzer, R., Lucke, A., Woszczyk, M., 2007.
Biomarker and stable carbon isotope systematic of fossil wood from the second
Lusatian lignite seam of the Lubstow deposit (Poland). Org. Geochem. 38,
1850e1864.
Berner, R.A., 1970. Sedimentary pyrite formation. Am. J. Sci. 268, 1e23.
Berner, R.A., 1984. Sedimentary pyrite formation: an update. Geochim. Cosmochim.
Acta 48, 605e615.
Cole, G.A., Abu- Ali, M.A., Aoudeh, S.M., Carrigan, W.J., Chen, H.H., Colling, E.L.,
Gwathney, W.J., Al-Hajji, A.A., Halpern, H.I., Jones, P.J., Al- Sharidi, S.H.,
Tobey, M.H., 1994. Organic geochemistry of the Paleozoic petroleum systems of
Saudi Arabia. Energy Fuels 8, 1425e1442.
Didyk, B.M., Simoneit, B.R.T., Brassell, S.C., Eglinton, G., 1978. Organic geochemical
indicators of palaeoenvironmental conditions of sedimentation. Nature 272,
216e222.
Grice, K., Lu, H., Atahan, P., Asif, M., Hallmann, C., Greenwood, P., Maslen, E.,
Tulipani, S., Williford, K., Dodson, J., 2009. New insights into the origin of
perylene in geological samples. Geochem. Cosmochim. Acta 73, 6531e6543.
Hughes, W.B., Holba, A.G., Dzou, L.I.P., 1995. The ratios of dibenzothiophene to
phenanthrene and pristane to phytane as indicators of depositional environment and lithology of petroleum source rocks. Geochem. Cosmochem. Acta 59,
3581e3598.
Jassim, S.Z., 2006. Paleozoic Megasequences (AP-1 to AP-5). In: Jassim, S.Z., Goff, J.C.
(Eds.), Geology of Iraq. Prague and Moravian Museum, Brno, p. 345.
Jassim, S.Z., Buday, T., 2006. Tectonic framework. In: Jassim, S.Z., Goff, J.C. (Eds.),
Geology of Iraq. Prague and Moravian Museum, Brno, p. 345.
Jiang, C., Li, M., Osadetz, K.G., Snowdon, L.R., Obermajer, M., Fowler, M.G., 2001.
Bakken/Madison petroleum systems in the Canadian Willston Basin. Part 2:
molecular markers diagnostic of Bakken and Lodgepole source rocks. Org.
Geochem. 32, 1037e1054.

M.W. Alkhafaji et al. / Marine and Petroleum Geology 64 (2015) 294e303

Kolonic, S., Sinninghe Damste, J.S., Bottcher, M.E., Kuypers, M.M.M., Kuhnt, W.,
Beckmann, B., Scheeder, G., Wagner, T., 2002. Geochemical characterization of
Cenomano/Turonian Black shales from the Tarfaya Basin (SW Morocco). Relationships between palaeoenvironmental conditions and early sulphurization
of sedimentary organic matter. J. Pet. Geol. 25, 325e350.
Le Heron, D.P.L., Criag, J., Etienne, J.L., 2009. Ancient glaciations and hydrocarbon
accumulations in North Africa and the Middle east. Earth-Sci. Rev. 93, 47e76.
Le Heron, D.P.L., Khoukhi, Y., Paris, F., Ghienne, J.F., Herisse, A.L., 2008. Black shale, gray
shale, fossils and glaciers: anatomy of the Upper Ordovician-Silurian succession
in the Tazzeka Massif of the eastern Morocco. Gondwana Res. 14, 483e496.
Leventhal, J.S., 1983. An interpretation of carbon and sulfur relationships in Black
sea sediments as indicators of environments of deposition. Geochem. Cosmochem. Acta 47, 133e137.
Luning, S., Craig, J., Loydell, D.K., Storch, P., Fitches, B., 2000. Lower Silurian hot shale
in North Arabia: regional distribution and depositional model. Earth-Sci. Rev.
49, 121e200.
Luning, S., Shahin, Y.M., Loydell, D., Al-Rabi, H.T., Masri, A., Tarawneh, B., Kolonic, S.,
2005. Anatomy of a world-class source rock: distribution and depositional
model of Silurian organic-rich shales in Jordan and implications for hydrocarbon potential. AAPG Bull. 89 (10), 1397e1427.
Mahmoud, M.D., Vaslet, D., Husseini, M.I., 1992. The lower Silurian Qalibah Formation of Saudi Arabia: an important hydrocarbon source rock. Am. Assoc. Pet.
Geol. Bull. 76 (10), 1491e1506.
McGillivray, J.G., Husseini, M.I., 1992. The paleozoic petroleum Geology of Central
Arabia. AAPG Bull. 76 (10), 1473e1490.
Nzoussi-Mbassani, P., Dinsar, J.R., Laggoun- Defarge, F., 2003. Organic matter characteristics of CenomanianeTuronian source rocks: implications for petroleum
and gas exploration onshore Senegal. Mar. Pet. Geol. 20, 411e427.
Peters, K.E., Moldowan, J.M., 1991. Effects of source, thermal maturity, and
biodegradation on the distribution and isomerization of homohopanes in petroleum. Org. Geochem. 17, 47e51.
Peters, K.E., Walters, C.W., Moldowan, J.M., 2005. The Biomarker Guide. Cambridge
University Press, Cambridge, p. 706.
Pfendt, P.A., Krasmanovic, V.D., Vitorovic, D., 1988. Indication of reducing conditions
in early diagenesis: the Aleksinac oil shale as example. Org. Geochem. 13 (4e6),
791e799.
Romero-Sarmiento, M.-F., Riboulleau, A., Vecoli, M., Versteegh, G.J.-M., 2011.
Aliphatic and aromatic biomarkers from Gondwanan sediments of Late Ordovician to Early Devonian age: an early terrestrialization approach. Org. Geochem. 42, 605e617.

303

Routh, J., McDonald, T.J., Grossman, E.L., 1999. Sedimentary organic matter sources
and depositional environment in the Yegua Formation (Brazos County, Texas).
Org. Geochem. 30, 1437e1453.
Sachse, V.F., Delvaux, D., Littke, R., 2012. Petrological and geochemical investigations of potential source rocks of the central Congo Basin, Democratic
republic of Congo. AAPG Bull. 96 (2), 245e275.
Silliman, J.E., Meyers, P.A., Eadie, B.J., 1998. Perylene: an indicator of alteration
processes or precursor materials? Org. Geochem. 29, 1737e1744.
Sinninghe Damste, J.S., Kenig, F., Koopmans, F.P., Koster, J., Schouten, S., Hayes, J.M.,
de Leeuw, J.W., 1995. Evidence for gammacerane as an indicator of water column stratication. Geochem. Cosmochim. Acta 59, 1895e1900.
Sinninghe Damste, J.S., Koster, J., 1998. A euxinic southern North Atlantic during the
Cenomanian/Turonian oceanic anoxic event. Earth Planet. Sci. Lett. 158,
165e173.
Summons, R.E., Powell, T.G., 1987. Identication of aryl isoprenoids in a source rocks
and crude oils: biological markers for the green sulfur bacteria. Geochem.
Cosmochim. Acta 51, 557e566.
Sun, Y., Xu, S., Lu, H., Cuai, P., 2003. Source facies of the Paleozoic petroleum systems
in the Tabei uplift, Tarim Basin, NW China: implications from aryl isoprenoids in
crude oils. Note. Org. Geochem. 34, 629e634.
Taylor, G.H., Teichmuller, M., Davis, A., Diessel, C.F.K., Littke, R., Robert, P., 1998.
Organic Petrology. GebruderBorntraeger, Berlin. Stuttgart, p. 704.
Tribovillard, N., Algeo, T.J., Lyons, T., Riboulleau, A., 2006. Trace metals as
palaeoredox and paleoproductivity proxies: an update. Chem. Geol. 232,
12e32.
Vecoli, M., Riboulleau, A., Versteegh, G.J.-M., 2009. Palynology, organic geochemistry and carbon isotope analysis of a latest Ordovician through Silurian clastic
succession from borehole Tt1, Ghadams Basin, southern Tunisia, North Africa:
palaenoenvironmental interpretation. Palaeogeogr. Palaeoclimatol. Palaeoecol.
273, 378e394.
Wignall, P.B., Newton, R., Brookeld, M.E., 2005. Pyrite framboid evidence for
oxygenpoor deposition during the PermianeTriassic crisis in Kashmir. Palaeogeogr. Palaeoclimatol. Palaeoecol. 216, 183e188.
Wilkin, R.T., Barnes, H.L., Brantley, S.L., 1996. The size distribution of framboidal
pyrite in modern sediments: an indicator of redox conditions. Geochim. Cosmochim. Acta 60, 3897e3912.
Zhou, C., Jiang, S.Y., 2009. Palaeocenographic redox environments for the lower
Cambrian Hetang Formation in South China: evidence from pyrite framboids,
redox sensitive trace elements, and sponge biota occurrence. Palaeoeogr.
Palaeoclimatol. Palaeoecol. 271, 279e286.