Marine and Petroleum Geology 78 (2016) 76e87

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Marine and Petroleum Geology

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Research paper

Geochemical characteristics and isotopic reversal of natural gases in

eastern Kopeh-Dagh, NE Iran
Hossein Saadati a, *, Hayder J. Al-Iessa a, Bahram Alizadeh a, b, Elham Tarhandeh c,
Mohammad Hasan Jazayeri c, Hossein Bahrami c, Mehrab Rashidi c
a
Department of Geology, Faculty of Earth Sciences, Shahid Chamran University of Ahvaz, Iran
b
Petroleum Geology and Geochemistry Research Centre (PGGRC), Shahid Chamran University of Ahvaz, Iran
c
National Iranian Oil Company, Exploration Directorate, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Natural gas samples from two gas fields located in Eastern Kopeh-Dagh area were analyzed for mo-
Received 19 May 2016 lecular and stable isotope compositions. The gaseous hydrocarbons in both Lower Cretaceous clastic
Received in revised form reservoir and Upper Jurassic carbonate reservoir are coal-type gases mainly derived from type III
17 August 2016
kerogen, however enriched dD values of methane implies presence of type II kerogen related material
Accepted 5 September 2016
Available online 7 September 2016
in the source rock. In comparison Upper Jurassic carbonate reservoir gases show higher dryness co-
efficient resulted through TSR, while presence of C1eC5 gases in Lower Cretaceous clastic reservoir
exhibit no TSR phenomenon. Carbon isotopic values indicate gas to gas cracking and TSR occurrence in
Keywords:
Carbon isotope
the Upper Jurassic carbonate reservoir, as the result of elevated temperature experienced, prior to the
Eastern Kopeh-Dagh following uplifts in last 33e37 million years. The d13C of carbon dioxide and d34S of hydrogen sulfide in
TSR Upper Jurassic carbonate reservoir do not primarily reflect TSR, as uplift related carbonate rock
Mixing dissolution by acidic gases and reaction/precipitation of light H2S have changed these values severely.
Gaseous hydrocarbons in both reservoirs exhibit enrichment in C2 gas member, with the carbonate
reservoir having higher values resulted through mixing with highly-mature-completely-reversed shale
gases. It is likely that the uplifts have lifted off the pressure on shale gases, therefore facilitated the
migration of the gases into overlying horizons. However it appears that the released gases during the
first major uplift (33e37 million years ago) have migrated to both reservoirs, while the second
migrated gases have only mixed with Upper Jurassic carbonate reservoir gases. The studied data
suggesting that economic accumulations of natural gas/shale gases deeper than Upper Jurassic car-
bonate reservoir would be unlikely.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Southwest part of the Amu-Darya Basin is locate in NE Iran
which is called as Eastern Kopeh-Dagh (Fig. 1). This basin is
bounded by the Kopeh-Dagh foldbelt along with the frontal fault of
the Kopeh-Dagh (Ulmishek, 2004). The Amu-Darya Basin is ranked
15th among 102 provinces for its original reserves (USGS, 2000).
The largest gas reserves are located in the Murgab depression and
northwest slope of the Badkhyz-Maimana uplift (Fig. 1) (Ulmishek,
2004). The Iranian discovered reserves are found mostly in the
* Corresponding author. þ989144565399.
E-mail address: hsaadati29@gmail.com (H. Saadati).
Kopeh-Dagh foredeep, and near the boundary with the Badkhyz-
Maimana uplift.
Lower to Middle Jurassic coaly clastics and coals, with vitrinite
reflectance ranging 1.15Ro percent at the top (3000 m) to
2.30e2.40Ro percent at depths of 4600e5500 m (Kuleshov and
Ignatova, 1990; Ulmishek, 2004), along Upper Jurassic (primarily
Oxfordian) basinal black shales have known as source rocks in the
Amu-Darya Basin (Brookfield and Hashmat, 2001; Ulmishek,
2004), however the coal beds of the Upper Triassic sequence in
the Agh-Darband could also be considered as the source rock
(Zanchetta et al., 2013). Due to early diagenesis, the Kashafrud
Formation is do not qualified as reservoir but is considered as one
of the main source rocks of the Amu Darya Basin (Poursoltani and
Gibling, 2011). Whole thickness of this Formation have not been

http://dx.doi.org/10.1016/j.marpetgeo.2016.09.004
0264-8172/© 2016 Elsevier Ltd. All rights reserved.
 H. Saadati et al. / Marine and Petroleum Geology 78 (2016) 76e87 77

Fig. 1. General geological map of the studied area, NE Iran and it situation to Amo Darya basin after (Ulmishek, 2004).

drilled but some intervals are considered as a potential shale
(unpublished data). Nevertheless, the organic-rich calcareous
shales (marlstone) and micritic limestone of the Middle Jurassic
Chaman-Bid Formation with total organic carbon (TOC) contents
of about 1.1e2.6% is introduced as the source of the gas in the
eastern part of the Kopeh-Dagh basin (Afshar-Harb, 1979) (Fig. 2).
Most Importantly, the Chaman-Bid Formation have not reached
proper thermal maturity until early Tertiary (late Paleocene:
Moussavi-Harami and Brenner, 1992).
Biomarkers data from condensates show high level of thermal
maturity (gas-window zone) and terrestrial organic matter for
source rocks (Sokolova et al., 1993). There are more similarity
between oils from fields in different stratigraphic intervals than
those same stratigraphic interval with different areas (Ulmishek,
2004). Thermogenic gases in Cretaceous rocks are drier and
contain lower contents of heavier homologues with little or no
sulfur (Semenovich et al., 1983) in comparison to that of Upper
Jurassic carbonates, which have variable amount of condensate and
commonly more sulfur (Ulmishek, 2004). The lithofacies of the
reservoir and seal rocks along reservoir temperature control the
distribution of the hydrogen sulfide (H2S; Isaksen and Khalylov,
2007).
The gas components and their isotope compositions provide a
comprehensive reflection of the sources/paleoenvironments,
78 H. Saadati et al. / Marine and Petroleum Geology 78 (2016) 76e87

Fig. 2. New stratigraphic chart of the Kopeh Dagh belt and of two main adjacent Amu Darya and South Caspian Sea basins (Robert et al., 2014).

organic matter type, evolution degree and processes such as their origin and some secondary processes such as mixing and
migration and the isotopic fractionation effects made happened by thermochemical sulfate reduction (TSR).
the biological, physical and chemical processes through the
geological time. Obtaining comprehensive information about
2. Geological setting
presence or absence of hydrocarbon in an area through geochem-
ical studies would reduce the economic risks majorly. This study
The Kopeh-Dagh is an intracontinental basin which formed after
investigates gaseous hydrocarbon from two structures (A and B) in
Paleo-Tethys closure during Triassic-Jurassic boundary (Golonka,
the Eastern Kopeh-Dagh (Kopeh-Dagh foredeep; Fig. 1) to clarify
2004; Fürsich et al., 2009). Sedimentation started with deposition
 H. Saadati et al. / Marine and Petroleum Geology 78 (2016) 76e87 79

of the Middle Jurassic Kashafrud Formation in the rifting basin.
From Middle Jurassic to Miocene beside five major transgressive-
regressive sequences (Moussavi-Harami and Brenner, 1992) over
6 km of sedimentary rocks were deposited in the basin (Afshar
Harb, 1979). Absence of the Kashafrud Formation from preexist-
ing basement highs and thousands meters thick on hanging walls
are due to a rifting system (Robert et al., 2014). Presence of
erosional surface on top of the Middle Jurassic Kashafrud Formation
indicates brief intra Jurassic hiatus which is followed by the
deposition of the main reservoirs e.g. Upper Jurassic carbonate
reservoir and Lower Cretaceous clastic reservoir formations (Fig. 2)
(Robert et al., 2014). Continuous sedimentation was established
until upper Cretaceous where Turonian and Maastrichtian is
distinguished by general hiatus in the whole Kopeh-Dagh region.
The main inversion phase recorder in the Kopeh-Dagh occurred
during the Late Eocene (Frizon de Lamotte et al., 2011) and resulted
in folding of marine sediments up to the Late Eocene during the
Alpine phase (Robert et al., 2014). Finally, the tectonic rearrange-
ment in North Iran started during the Pliocene age led to privilege
of the strike-slip component in the present-day deformation active
of Kopeh-Dagh.
Upper Jurassic carbonate succession is considered as the main
reservoir in the Eastern Kopeh-Dagh. It is composed mainly of
limestones and dolomites. However, marl/shales, sandstones and
evaporates occur to a lesser extent (Afshar Harb, 1979). It is proved
that the main hydrocarbon pay zones had an aragonite to high-Mg
calcite mineralogy deposited during the Kimmeridgian (Kavoosi,
2014). Hence, reservoir quality is controlled by depositional facies
and diagenetic processes such as dolomitization and dissolution.
Increase in the dolomitization and intercrystalline porosity would
appear to be occurred at the late of highstand systems tract (HST)
particularly where anhydrites cap the parasequences (Kavoosi
et al., 2009; Kavoosi, 2014). It seems that this dolomite type
formed at high temperatures, ranging from 94 to ~ 110  C (Adabi,
2009). Secondary gas reservoir in the Kopeh-Dagh Basin is Lower
Cretaceous clastic sequences with siliciclastic lithology and sub-
litharenitic redbeds in composition (Moussavi-Harami and
Brenner, 1993; Mortazavi et al., 2014). Some process such as early
clay infiltration, and extending silica, calcite and anhydrite
cementation have occurred in the Lower Cretaceous clastic reser-
voir, resulting in poor reservoir quality. Furthermore clay-sized
hematite particles coat most of the grains (Moussavi-Harami and
Brenner, 1993). Diagenetic events led to partial dissolution of
early and late-stage calcite cements that created secondary
porosity in the sandstone units.
3. Samples and methods
All samples collected from production wells using steel bottles
and after flushing the lines for 15e20 min to remove air. The
chemical and isotopic compositions of gaseous hydrocarbon were
determined on a Finnigan Mat Delta S mass spectrometer inter-
faced with an HP 5890II gas chromatograph. Gas components were
separated on the gas chromatograph in a stream of helium, con-
verted into CO2, and then injected into the mass spectrometer. The
stable carbon isotope data are expressed in the delta notation in
permil (‰) relative to VPDB (Vienna Pee Dee Belemnite,
d13CVPDB ¼ 0‰). Measurement precision is ±0.5‰ for d13C. The
stable hydrogen isotope data are reported in delta notation with
respect to VSMOW (Vienna Standard Mean Ocean Water,
dDVSMOW ¼ 0‰). Analytical precision is estimated to be ±3‰.
4. Results
4.1. Gas geochemistry
Geochemical parameters of gas samples from two gas fields are
listed in Table 1. The gases from Lower Cretaceous clastic reservoir
are mainly composed of hydrocarbon gaseous, with non-
hydrocarbons content <5% (H2S, N2 and CO2). The CH4 and wet
gases range from 93.78 to 94.6% and 2.2e2.6%, respectively. The
gases are dry with dryness coefficients (C1/C1eC5) of 0.971e0.976
(Table 1). The H2S content in Lower Cretaceous clastic reservoir is
negligible (0.05) while N2 and CO2 contents are 2.34e2.74% and
<1%, respectively. The natural gases of Upper Jurassic carbonate
reservoir display higher dryness coefficient (C1/C1eC5) of >0.99,
contributed by extremely lower content of wet gases (Table 1).
These contents as well as non-hydrocarbons content are generally
higher than those of gases from clastic reservoir with CO2 and H2S
contents in the range of 5.3e5.9% and 2.1e2.6%, respectively, the N2
contents are lower within the range of 1.2e1.5% (Table 1).
4.2. Carbon and hydrogen isotopes of gaseous alkanes
Isotopic compositions of natural gases from clastic reservoir are
different from that of carbonate reservoir. Collected gases from
clastic reservoir contained sufficient quantity of C1-5 gases for iso-
topic analyses; while the isotopic values were measured only on C1-
3 n-alkanes in Upper Jurassic carbonate reservoir (Table 2). The
d13C1, d13C2, d13C3, d13C4 and d13C5 values of natural gases in the
Lower Cretaceous clastic reservoir range from 34.4 to 31.8‰,
from 21.2 to 18.8‰, from 22.9 to 20‰, from 22 to 19.1‰
and from 22.1 to 17.2‰, respectively (Table 2), whereas these
values for C1, C2 and C3 of natural gases in Upper Jurassic carbonate
reservoir are from 35.7 to 32.1‰, from 15.4 to 13.6‰ and
from 21.8 to 21.3‰, respectively (Table 2). A partial reversal of
carbon isotope values of gaseous alkanes is recognizable in both gas
reservoirs, with Upper Jurassic reservoir gases exhibiting greater

Table 1
Chemical composition of gases.

Field and reservoir CH4 C2H6 C3H8 iC4H10 nC4H10 nC5H12 C2H6/C3H8 Wet Gas C1/C2þC3 N2 H2S CO2 DI% CHC Wetness

B-Clastic-B 93.82 1.41 0.42 0.17 0.25 0.27 3.34 2.34 51.13 2.74 0.05 0.71 97.37 51.13 2.34
B-Clastic-B 94.33 1.42 0.43 0.18 0.26 0.26 3.26 2.39 50.82 2.33 0.05 0.61 97.35 50.82 2.39
B-Clastic-D 93.99 1.71 0.40 0.11 0.18 0.20 4.25 2.71 44.29 2.63 0.05 0.61 97.29 44.29 2.71
B-Clastic-D 93.78 1.69 0.45 0.13 0.22 0.24 3.70 2.62 43.54 2.69 0.05 0.6 97.14 43.54 2.62
A-Clastic-D 94.66 1.59 0.33 0.08 0.12 0.12 4.72 2.22 49.00 2.39 0.05 0.6 97.66 49.00 2.22
A-Clastic-D 93.93 1.69 0.42 0.12 0.20 0.23 3.96 2.56 44.16 2.4 0.05 0.8 97.21 44.16 2.56
B-Carbonate 89.78 0.56 0.06 0.01 0.03 0.03 8.69 0.75 142.52 1.51 2.62 5.35 99.29 142.52 0.75
B-Carbonate 90.15 0.56 0.06 0.01 0.03 0.03 8.72 0.75 142.64 1.22 2.13 5.77 99.22 142.64 0.75
B-Carbonate 89.96 0.56 0.06 0.01 0.03 0.03 8.71 0.75 142.58 1.21 2.43 5.66 99.22 142.58 0.75
B-Carbonate 89.98 0.55 0.06 0.01 0.031 0.03 8.55 0.74 144.91 1.42 2.11 5.56 99.23 144.91 0.74
B-Carbonate 89.67 0.57 0.06 0.01 0.031 0.03 8.64 0.76 141.00 1.32 2.45 5.91 99.21 141.00 0.76

Dryness Indies¼(C1/(C1eC5)*100; CHC ¼CH4/(C2H6þC3H8).

80 H. Saadati et al. / Marine and Petroleum Geology 78 (2016) 76e87

Table 2
Stable isotopic compositions of natural gas from Eastern Kopeh-Dagh.

Field and reservoir d13 d13 a 13

d d13 d13 d13 dD d13 d34S
CH4 C2H6 C2H6 C3H8 nC4H10 nC5H12 CH4 CO2 H2S

B- Clastic -B 31.8 19.6 24.6 22.4 20.9 17.2 163 6.5 e

B- Clastic -B 34.4 20.6 25.6 22.9 20.2 19.3 158 6.6 e
B- Clastic -D 34.2 20 25 21.2 20.1 17.7 163 7.2 e
B- Clastic -D 33 19 24 20.4 19.5 18.7 168 7.8 e
A- Clastic -D 32.9 18.8 23.8 20 19.1 19.4 165 7 e
A- Clastic -D 33.8 21.2 26.2 22.6 22 22.1 161 7.3 e
B- Carbonate 32.7 14.1 e 21.3 e e 158 0 16.5
B- Carbonate 35.7 15.4 e 21.7 e e 163 0.4 16.7
B- Carbonate 33.9 14.1 e 21.5 e e 163 1 16.2
B- Carbonate 32.1 13.6 e 21.8 e e 163 1.1 17
B- Carbonate 32.5 14.1 e 21.5 e e 163 2.1 16.8
a
Initial d13C value of C2H6 plus lower end (5‰) of ethane heavier values than methane ¼ (d13C2þ5).

reversal. The dD1 value of Lower Cretaceous clastic reservoir gases
ranges from 168 to 158‰ (average 163‰), while they are
from 163 to 158‰ (average 162‰) in gases analyzed from
Upper Jurassic carbonate reservoir (Table 2).
The d13CCO2 and d34SH2S values for Upper Jurassic carbonate
reservoir vary from 0.0 to 2.1‰ (average 0.6) and from 16.2 to 17‰
respectively (average 16.6‰; Table 2). The d13CCO2 values for Lower
Cretaceous clastic reservoir range from 6.5 to 7.8‰
(average 7.06‰), however the d34SH2S values were not detectable
due to low amounts of H2S gases.
5. Discussion
5.1. Genetic types of gaseous alkanes
Based on the chemical compositions and isotopic values of
methane and its homologues the type (oil-type or coal-type) of
natural gas could be recognized (Stahl and Carey, 1975; Galimov,
1988; Yongchang and Ping, 1996; Dai et al., 2005; Liu et al.,
2008). Generally thermogenic gases generated from sapropelic
source rocks are characterized by d13C2 and d13C3 values lighter
than 28‰ and 25‰, respectively (depleted in d13C), whereas
ethane and propane gases derived from humic source rocks
display isotopic values heavier than 28‰ and 25‰ respectively
(enriched in d13C; Stahl and Carey, 1975; Dai et al., 1992, 2005).
Isotopic values of ethane in all analyzed samples as well as the
location of the plotted data on Fig. 3, characterize the natural
gases from both reservoirs as thermogenic gases from humic
source (higher values for ethane in Figs. 3 and 5 are due to
migration of gases with reversal properties into both of the res-
ervoirs, which will be discussed later) and confirmed by higher
values of d13C3 (Table 2). Generally ethane in relation to methane
is heavier by 5‰e10‰ PDB (Silverman, 1971; Deines, 1980).
Considering the lower end (d13Ce5, and maintaining the ther-
mogenic gases trend d13C1 < d13C2 < d13C3) isotopic values of
ethane should have been around d13C 26 or 27‰ prior to
migration/mixing. These calculated ethane values put the gases in
the area of coal type gas (Table 2), the difference between present
and calculated/original values of ethane implies mixing with
highly mature gases and/or result of thermochemical sulfate
reduction (TSR). Furthermore during humic kerogen maturation
history, higher amounts of thermogenic methane are generated in
comparison to C2þ components, whereas sapropelic kerogens
generate significant amounts of C2þ hydrocarbons (Hunt, 1996),
which strengthens the idea that the gases in both reservoirs are
humic in nature (Table 1).

Fig. 3. d13C1 versus d13C2 of the natural gases. Data plot introduce the gases as coal-type gas, enriched ethane gas values of Upper Jurassic reservoir gases are due to mixing with
gases contained highly enriched-ethane.
 H. Saadati et al. / Marine and Petroleum Geology 78 (2016) 76e87
Gas dryness index is commonly used by researchers to express
the volume of methane gases versus other n-alkane homologues.
Over the years researchers have used different methods of calcu-
lating gas dryness; C1/SC1-C5 (Tissot and Welte, 2012), C1/SC2-C5
(Cody and Hutcheon, 1994; Draper and Boreham, 2006) and C1/
(C2 þ C3) (Bernard et al., 1976, 1978; Hunt, 1996; Smith and
Pallasser, 1996; Whiticar, 1996, 1999; Faiz and Hendry, 2006;
Flores et al., 2008; Osborn and McIntosh, 2010; Stra˛ po c et al.,
2008, 2011). Calculated dryness coefficients are presented in
Table 1. It is clearly evident that the chemical and carbon isotope
compositions of the natural gases in the Lower Cretaceous clastic
reservoir are different from those of Upper Jurassic carbonate
reservoir. Higher dryness and heavier carbon isotope values of
gaseous n-alkanes (butane and pentane content were below the
detection limit) address Upper Jurassic carbonate reservoir gases as
highly mature dry-gas (Hao et al., 2008; Ma et al., 2008; Liu et al.,
2013).
The ratio of methane to the sum of ethane and propane (C1/
(C2 þ C3)) versus d13CeCH4 of natural gas is widely used in dis-
tinguishing the origin (microbial, thermogenic or a mixture of the
two ends) and the type (Kerogen type II or III) of the natural gas
(Bernard et al., 1978; Osborn and McIntosh, 2010; Stra˛ poc et al.,
2008, 2011). A modified Bernard diagram characterizing natural
gases from both gas reservoirs is shown in Fig. 4. Samples collected
from clastic reservoir were plotted in the area for gases from
kerogen type III, in contrast gases from Upper Jurassic carbonate
reservoir were plotted close to the area of kerogen type II. Even
though Figs. 3 and 5 show these gases to be derived from kerogen
type III with higher maturity. The data does not follow the
increasing thermal maturity trend, the reasons for this observation
could be related to the effects of alteration by TSR (Hao et al., 2008)
and also mixing of gases with different maturity.
With increasing temperature, primary kerogen and other hy-
drocarbons (including oil, condensate or even wet gases) will start
cracking into secondarily products. In order to identify whether the
gases are primary or secondary in origin, a modified Prinzhofer
model (Prinzhofer and Huc, 1995) of C2/C3 and d13C2ed13C3 is used
Fig. 4. Modified Bernard diagram of natural gases from Lower Cretaceous clastic and
Upper Jurassic carbonate reservoir fields. Natural gases are generated from type III
kerogen, however the location of Upper Jurassic carbonate reservoir gases are due to
effects of TSR.
81
(Fig. 5). All gases from Lower Cretaceous clastic reservoir fall in the
area of primary cracking gas (excluding the effects of mixed gases
with higher ethane isotopic values, which will be discussed later)
indicating these gases as primary that have not experienced
enough temperature to start cracking into secondary gases. On the
other hand due to higher maturation, mixing and/or TSR, the
d13C2e d13C3 values of Upper Jurassic carbonate reservoir natural
gases are un-plot-able on the diagram. (The reasons for this
observation will be discussed later), however C2H6/C3H8 values of
Upper Jurassic carbonate reservoir gases are comparable with the
C-III area, implying that Upper Jurassic carbonate reservoir gases
are secondary thermal cracking products of previous gases (Fig 5).
It is believed that the hydrogen isotopic value of the methane is
related to the 1) depositional environment of the source rock and 2)
maturity (Dai et al., 1992; Guoyi et al., 2010). This value like carbon
isotope generally increases (becoming less negative) with
increasing carbon number of the gases. The hydrogen isotopic value
of thermogenic methane generated from marine source rocks is
higher than 180‰, on the other hand gases generated from
terrigenous, freshwater environment source rocks have values
lower than 190‰, while gases from paralic, brackish water
environment values rank in between (Schoell, 1980). Hydrogen
isotope values of gases from Lower Cretaceous clastic reservoir
range from 168 to 158‰ (average 163‰), while Upper Jurassic
carbonate reservoir gases have values from 163 to e 158‰
(average 162‰ Table 2). These values from both reservoirs are
comparable to marine source rocks, despite previous results indi-
cating terrigenous coal-derived gases and the fact that the majority
of the source rocks in the studied area were considered to be
kerogen type III source rocks (Ulmishek, 2004). Therefore possible
explanations could be that the gases have generated from a source
rock consisted mainly from terrigenous organic matter along with
marine organic matter, or terrigenous source rock co-existing with
transitional facies/source rocks deposited through previous trans-
gression/regression sequences (Chen, 1994; Dai et al., 2005; Liu
et al., 2015). While the isotopic values of the gases from two res-
ervoirs show great differences in the carbon isotope values, the
hydrogen isotopic values are almost similar (Table 2). As it was
mentioned earlier the hydrogen values are controlled by deposi-
tional environment and thermal maturity. This observation implies
that the mechanism responsible for the observed differences in
Upper Jurassic carbonate reservoir is secondary processes such as
TSR and mixing rather than thermal cracking.
5.2. In-reservoir mixing of gaseous hydrocarbons
Chung et al. (1988) suggested that gas components generated
from a single source exhibit a semi-linear isotope trends when
stable carbon isotopic compositions of methane and wet gas
(C2eC5) components are plotted against their reciprocal carbon
number (known as Chung plot and/or natural gas plot). As shown in
Fig. 6, the carbon isotopic series of alkanes for both reservoirs
exhibit partial reversals. The natural gases from Lower Cretaceous
clastic reservoir contain complete set of n-alkanes (C1eC5), while
propane is the heaviest n-alkane in Upper Jurassic carbonate
reservoir to be plotted. Both reservoirs show partial reversal in
ethane isotopic values (isotopic reversal is greater in Upper Jurassic
carbonate reservoir; Fig. 6), while isotopic values of methane and
propane in two reservoirs are similar, implying that the source of
gases in both reservoirs is likely to be the same. Geologically clastic
reservoir is located above carbonate reservoir which strengthen the
idea that the gases have generated from the same source rock.
Generally reversed carbon isotope ratios are attributed to be the
result of gas mixing from different sources and/or gases with
different maturity (James, 1983; Jenden et al., 1993, 1988; Hao et al.,
82 H. Saadati et al. / Marine and Petroleum Geology 78 (2016) 76e87
Fig. 5. Comparison of compositional and isotopic data of natural data. Considering the shale gas mixture, clastic reservoir gases are primary derived gases, while due to mixture
with shale gases, carbonate reservoir gases are un-plot-able. (P: primary cracking gas, CeI: secondary cracking of oil, C-II: secondary cracking of oil and gas, C-III: secondary cracking
of gas to gas, C þ P: the mixing gas of primary cracking gas and secondary oil cracking gas).
Fig. 6. “Natural gas plot” of the studied samples Natural gas plot using the Chung et al.
(1988) method. Upper Jurassic carbonate reservoir gases contain C2 gases with higher
isotopic values than Lower Cretaceous clastic, due to mixing with shale gases with
complete reversal.
1998, 2000; Laughrey et al., 2004). Dai et al. (2004) demonstrated
that partial reversal of alkane carbon isotopes could be by following
reasons: 1) mixing of abiogenic and biogenic gases 2) mixing of
coal-derived and oil derived gases 3) bacterial oxidation of alkane
components and 4) mixing of gases with varying thermal maturity
from the same source or gases from different sources. The gases in
the area are proven to be thermogenic in origin and there is no
report of abiogenic gases in the area (as discussed above). Therefore
mixing with abiogenic gases is unlikely. As mentioned above
ethane isotope values generated from sapropelic source rocks
possess values lighter than 28‰ (Stahl and Carey, 1975; Dai et al.,
1992). The data suggest (Figs. 3 and 5, Table 2) that the d13C2 values
of introduced gases were heavier (enriched) than the gases.
Therefore the mixed gas should have been coal-derived gas in na-
ture. The data show no sign of bacterial activity, as the bacterial
activity is recognized by methane isotopic value ranging negative
than 50 or 60‰ (Schoell et al., 1981; Hunt, 1996; Whiticar, 1999).
Therefore the introduced gas responsible for partial reversal of
alkane carbon isotopes in both reservoirs is coal derived gas in
nature.
Mixed gases appear to have only affected the ethane in both
reservoirs, and the rest of the gas homologues do not show
noticeable change, implying that the heaviest n-alkane in the
migrated gas was ethane. With increasing in maturity, methane
and wet gas generation will increase and decrease, respectively,
implying mixing with more mature gases from the same source is
unlikely as methane isotopic values were not shifted to higher
(enriched) values (Table 2). As mentioned previously in the
geological setting section, layers of undrilled/unexplored shales
(shale gas) exist below the studied reservoirs, and unlike relative
openness in coal environment, shale gases are considered to be
closed systems. Isotopic reversals are known to be features of
closed shale systems, which low expulsion efficiency have pre-
vented the oils and gases to be expelled at their respective peak
generation. These propeties seem to be the result of in-situ mixing
and accumulation of gases generated from cracking of different
precursors (kerogen, retained oil and wet gas) at different thermal
maturities (Tilley et al., 2011; Zumberge et al., 2012; Tilley and
Muehlenbachs, 2013).
Hao and Zou (2013) have proposed a conceptual model to
explain the procedure and the reasons for observed anomalies in
isotopic composition of shale gases with high thermal maturities.
At thermal maturities lower than 1.3e1.5% Ro, gases are mainly
generated from kerogen cracking in a closed system, leading to the
normal trend of increasing enrichment of d13C with increasing
carbon number (Lorant et al., 1998) and increases in iC4/nC4 and iC5/
nC5 ratios which exhibit maturity traits similar to gases generated
in an open-system environment.
Partial isotope reversal (d13C2 < d13C1 < d13C3) begins to occur as
thermal maturities increases to about Ro ~1.9 (R2 represented in
Fig 7). Cracking of retained oil causes an increase in ethane and
propane concentrations. The generated gases from oils are gener-
ally enriched in d12C causing depletion in the overall d13C2 and
d13C3. However C3 gases (light isotopes) generates at higher rate,
which results in higher values of (d13C2 - d13C3) with maturity (Fig
7). As thermal maturity further increases (Ro > 2.0%) apart from
 H. Saadati et al. / Marine and Petroleum Geology 78 (2016) 76e87
Fig. 7. Schematic diagram depicting the transition of carbon isotope distribution patterns from normal into complete reversal through increasing thermal maturity and d13C
distribution pattern of C2 and C3 from negative divergence into positive divergence (R1: 1.3e1.5%Ro, R2: 1.9%Ro, R3 &R4: >2.0%Ro; S1: d13C1 < d13C2 < d13C3, S2: d13C2 < d13C1 < d13C3,
S3: d13C2 < d13C3 < d13C1, R4: d13C3 < d13C2 < d13C1) (Hao and Zou, 2013).
previous precursors, wet gases also start to crack and the partial
isotopic reversal (d13C2 < d13C3 < d13C1) changes into complete
isotopic reversal (d13C3 < d13C2 < d13C1) (Fig 7, Hao and Zou, 2013
and references therein).
Considering the present depths of Upper Jurassic carbonate
reservoir, the isotopic values of the gases from these reservoirs as
well as their gas concentrations, the level of TSR occurring in these
reservoirs and also the thermal maturities of shale gas layers, the
authors believe that the gases in lower shale gases are completely
reversed with thermal maturities above 2.0%Ro (Hao and Zou,
2013).
The Closed-system of a shale gas may become more open-
system due to faulting, fracturing and/or intensive erosion of
overburden rocks, which can result in complete loss of free gas or
even undersaturation. Loss of gases under the influence of intensive
tectonic movements after the end of gas generation is probably the
major risk of gas exploration in organic-rich shales (Hao and Zou,
2013).
Burial and thermal history reconstruction revealed that the area
have experienced two noticeable uplifts (Fig. 8), the first uplift
being the major uplift happened at Late Eocene times (37e33)
followed by the last one at 4e7 years ago (Frizon de Lamotte et al.,
2011; Robert et al., 2014; Shabanian et al., 2009). It is likely that
during the first uplift, the deep shale gases have become less
pressurized/confined and have lost some yet adequate volume of
the free gases which then migrated to both Upper Jurassic car-
bonate reservoir and then to Lower Cretaceous clastic reservoir.
During the following uplift and further removal of pressure on
shale gases, gases with higher maturity have been released, which
apparently only migrated to Upper Jurassic carbonate reservoir,
however it is not clear if these gases have experienced TSR in Upper
Jurassic carbonate reservoir.
As previously explained gases taken from Lower Cretaceous
clastic reservoir display no trace of secondary processes. Consid-
ering the in-reservoir mixing with shale gases, the overall con-
centrations of C2 and C3 gases are generally lower than 2% and 0.5%,
respectively (Table 1), while overall C2 concentrations of TSR-
affected Upper Jurassic carbonate reservoir and migrated shale
gases are <0.6%. This implies that the migrated shale gases con-
sisted of low concentrations (only C1 and C2) yet high isotopic
values (higher in case of gases migrated during second uplift). This
explains why only ethane in both reservoirs show gas enrichment,
83
however due to high concentration in both reservoirs, methane
were not affected by the migrated gases.
The carbon isotopic composition of the shale gases in the
studied area below Upper Jurassic carbonate reservoir gas is highly
enriched with complete reversal, indicating progressive loss of all
hydrocarbon gases due to gas loss and/or fluid rock reactions
(Burruss and Laughrey, 2010) suggesting that deeper, economic
accumulations of natural gas/shale gases deeper than Upper
Jurassic carbonate reservoir gas reservoir are unlikely.
5.3. TSR occurrence in Upper Jurassic carbonate reservoir
Thermochemical sulfate reduction is known to occur at tem-
peratures higher than 100e140  C (Orr, 1977; Goldstein and
Aizenshtat, 1994; Goldhaber and Orr, 1995; Machel et al., 1995;
Worden et al., 1995; Machel, 2001; Mougin et al., 2007), involving
sulfate and organic matter/hydrocarbons. During TSR and oxidation
of hydrocarbons, large amounts of H2S, CO2, CH4 and H2O are
produced at different rates (Worden et al., 1995; Worden and
Smalley, 1996; Cai et al., 2004; Pan et al., 2006). This increase in
the gas population leads to an increase in gas dryness coefficient
(Zhang et al., 2008) (Table 1).
The concentration of the H2S gases in Lower Cretaceous clastic
reservoir is below detection and both population and isotopic
values of CO2 gases implying no TSR occurrence in these reservoirs
(Table 1) which is likely due to the clastic nature of the reservoir
(Dai et al., 2014). On the other hand both concentrations and iso-
topic values of H2S and CO2 of Upper Jurassic carbonate reservoir
gases, the presences of saddle and matrix dolomite, bitumens along
with stylolite surface (Kavoosi, 2009) in the reservoir are evidences
for TSR. As mentioned above existence of anhydrites alternative
with dolomite intervals in the carbonate reservoir were reported
(Afshar Harb, 1979; Kavoosi, 2014; Kavoosi et al., 2009). One
dimensional maturity modelling in the B anticline shows that this
reservoir experienced up to 160  C temperature which highlights
the occurrence of TSR (Fig. 8).
Generally in reservoirs with sufficient amounts of sulfate, three
stage sequence described by Hao et al. (2008) occurs. Occurrence of
all three stages of TSR will lead to elevated amounts of H2S and CO2
gases, accompanied by high quantities of sulfur rich pyrobitumens
in the reservoir. However in case of limited amounts of sulfate
concentration, TSR is restricted to condensate or at most to
84 H. Saadati et al. / Marine and Petroleum Geology 78 (2016) 76e87

Fig. 8. Result of one dimensional thermal maturity modelling with calibration data from the B anticline.

condensate and wet gas stage. In these reservoirs TSR mostly
consumes C2þ hydrocarbon gases while leaves the methane d13C1
values unaffected (Hao et al., 2008). This causes relatively constant
d13C1 values but varying C1/(C2þC3) values (Table 1). TSR process at
Upper Jurassic carbonate reservoir is almost at the middle-end of
advanced stage (wet gas stage), and the reason for similar d13C
methane values in TSR affected Upper Jurassic carbonate reservoir
and Lower Cretaceous clastic reservoir with no secondary process is
due to limited concentrations of sulfates. This suggestion is
supported by local existence of anhydrite in Upper Jurassic car-
bonate sequences (Afshar Harb, 1979).
Theoretically, isotopically heavy CH4 and light CO2 are products
of an increase in the level of TSR through hydrocarbon oxidative
alteration. At this stage the light CO2 is mainly derived from hy-
drocarbons. On the other hand with increasing in TSR level, along
with increasing in H2S volume the isotopic values as well as become
enriched (Aali et al., 2006). Upper Jurassic carbonate reservoir gases
possess low quantities of H2S and CO2 (Table 1), but are heavily
 H. Saadati et al. / Marine and Petroleum Geology 78 (2016) 76e87
enriched in d34S and d13C values of H2S and CO2 gases (Table 2),
respectively; implying thermochemical sulfate reduction is not the
only process responsible for these values. Generally due to high
reactivity of H2S gases with transition metals resulting in formation
of pyrite and other metal sulfides, the amount of H2S is majorly
decreases (Orr, 1977; Suleimenov and Krupp, 1994; Kotarba and
Lewan, 2013). Whereas isotopically heavy CO2 occurrence in nat-
ural gases are normally due to reaction/precipitation of lighter
member of the gase with Mg2þ, Fe2þ and Ca2þ of sulfates, through
below equation:
CO2 þ Mg2þ (Ca2þ, Fe2þ) / MgCO3 (CaCO3, FeCO3) Y þ H2O
Through this equation the light CO2 precipitate, while the re-
sidual gases become enriched in d13C values.
Liu et al. (2014) have proposed that CO2 gases in natural gases
with content >5% and isotopic values lower than 3‰, are pri-
marily produced through TSR, while CO2 gases in natural gases with
content >5% but isotopic values higher (enriched) than 3‰, are
the mixture of hydrocarbon-derived CO2 via TSR and carbonate-
dissolution CO2 by acidic fluids.
As TSR proceeds through consuming heavier hydrocarbons, the
acidic gas content (H2S and CO2) increases in the reservoir. As
mentioned previously H2S gas is highly reactive with transition
metals and Mg2þ is considered as an active metal for reacting with
H2S gas (Ma et al., 2008; Machel, 2001; Worden and Smalley, 1996).
Ferroan is generally presents as cement in limestones and dolo-
stones (Liu et al., 2013; Machel, 2001). Therefore Pyrite is prefer-
entially precipitates during TSR in case Fe2þ exists in the
environment; During TSR any FeCO3-component will preferentially
grow into pyrite through following reaction:
FeCO3þ2H2O /FeS2þCO2þH2O þ H2
Since the body part of Upper Jurassic carbonate reservoir is
made of high-Mg calcite and dolomitelayers (Afshar Harb, 1979;
Kavoosi, 2014; Kavoosi et al., 2009), it appears that the heavily
enriched isotopic values of H2S gases are due to preferential reac-
tion/precipitation of Mg2þ (since Mg2þ is considered a highly
reactive transition metal with H2S; Worden and Smalley, 1996;
Machel, 2001; Ma et al., 2008), and Fe2þ with H2S gases. These
reaction/precipitation of lighter isotopes (d12C, d32S) will make the
residual gases to become enriched in heavier isotopes (d13C, d34S).
As mentioned before by burial and thermal model reconstruc-
tion of both gas reservoirs (Fig. 8), the area have experience two
uplifts. Prior to these uplifts Upper Jurassic carbonate reservoir
have experienced temperatures far greater (up to 160  C temper-
ature) than the proposed threshold for TSR process (100e140  C).
During this period TSR at Upper Jurassic carbonate reservoir have
proceeded and reached the end of second stage (wet gas stage), as
described by Hao et al. (2008). During the wet gas level, depleted C2
and C3 gases generated during thermal cracking of retained oils
(Hao and Zou, 2013; Prinzhofer and Huc, 1995) were consumed,
which could be the reason for similar values of C3 gases in both
reservoirs (consumption of light-methane gases generated previ-
ously during thermal cracking and previous levels of TSR at the end
of wet gas level, could be the reason for lower methane concen-
tration in Upper Jurassic carbonate reservoir).
However it appears that the start of uplift have decreased the
temperature, therefore slowed if not stopped the process of n-
alkane cracking and H2S production, as higher temperatures are
needed to cleave the bonds between carbons with decreasing in
carbon number (Curt Wentrup, 1984). As mentioned before TSR
elevates the H2S and CO2 content in the reservoir, after saturating
the reservoir fluids, the lighter isotopes of carbon and sulfur are
85
preferentially precipitated (reacting with Mg2þ and Fe2þ). Start of
uplift and the decrease in temperature and pressure of the reservoir
have driven the reservoir fluids from saturate into sub-saturate
state (Huang et al., 2010). The acidic fluids have dissolved the car-
bonates and the former precipitated crystal, which in turn releases
CO2 gases containing heavy isotopes, mixing of these gases with
previously TSR-generated CO2 have enriched the isotopic values, as
described by Liu et al. (2014).
6. Conclusion
(1) Results of molecular and isotopic composition of natural gases
from Lower Cretaceous clastic reservoir and Upper Jurassic car-
bonate reservoir in the Eastern Kopeh-Dagh area indicate that:
1. Gaseous hydrocarbons accumulated in both reservoirs are
genetically thermogenic in nature, derived mainly from source
rock with kerogen type III, however enriched dD values of
methane implies kerogen type II (marine organic matter) ma-
terial existence in the source.
2. The Upper Jurassic carbonate reservoir natural gas samples have
higher dryness coefficient derived from TSR and gas-gas thermal
cracking, however similar dD values of methane implies that the
mechanism responsible for the observed differences in Upper
Jurassic carbonate reservoir is mainly caused by TSR rather than
thermal cracking.
3. Carbon isotopic profile of both reservoirs exhibit partial reversal
in ethane isotopic values, with Upper Jurassic carbonate reser-
voir gases possess greater reversal resulted from mixture with
highly mature completely reversed shale gases with thermal
maturities above 2.0%Ro.
4. Molecular and isotopic values of natural gases indicate no sec-
(2) ondary processes in Lower Cretaceous clastic reservoir, while
both concentration and isotopic values of H2S and CO2 of Upper
Jurassic carbonate reservoir gases and other petrographic evi-
dence in the reservoir signify TSR occurrence.
5. d13C of carbon dioxide and heavily enriched d34S values of
hydrogen sulfide in Upper Jurassic carbonate reservoir, do not
solely reflect TSR. The enriched isotopic value of CO2 is resulted
from mixing of previously TSR produced CO2 and CO2 produced
through carbonate rock dissolution by acidic gases. While
enriched d34S values are due to reaction/precipitation of light
H2S gases with Mg2þ and Fe2þ in the reservoir.
6. Burial reconstruction model shows that the area has experi-
enced two noticeable uplifts. Prior to these uplifts, Upper
Jurassic carbonate reservoir have experienced temperatures
optimum for thermochemical sulfate reduction, however the
following uplifts have slowed if not stopped the rate of TSR.
7. It is likely that during the first major uplift occurrence (33e37
million years ago), released gases from shale gases have
migrated to both reservoirs resulting in the observed reversal
enrichment, however during subsequent uplift released gases
from shale gases only migrated to Upper Jurassic carbonate
reservoir.
8. Progressive loss of hydrocarbon gases due to gas loss and fluid
rock reactions in shale gases have led to high enrichment and
complete reversal of carbon isotopic composition of the shale
gases in the studied area, suggesting that economic accumula-
tions of natural gas/shale gases deeper than Upper Jurassic
carbonate reservoir are unlikely.
Acknowledgments
The authors would like to extend their thanks to the Exploration
Directorate of the National Iranian Oil Company (NIOC) for
86 H. Saadati et al. / Marine and Petroleum Geology 78 (2016) 76e87
providing the samples and the financial support of the project. The
invaluable help of the anonymous reviewers of this manuscript,
whose ideas and comments improved the manuscript, are also
acknowledged. We wish to thank M. Soltani and as well as Asso-
ciated Editor of JMPG Dr Daniel S Alessi, for his invaluable help and
reviewing thoroughly the whole manuscript.
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