Petroleum Science and Technology
ISSN: 1091-6466 (Print) 1532-2459 (Online) Journal homepage: https://www.tandfonline.com/loi/lpet20
Evaluation of the source rock potential of the
Unyazah Formation (late Carboniferous-Early
Permian) in Dukhan Field, Qatar
Hamad Al-Saad, Amer Jassim Al-Khafaji & Fadhil N. Sadooni
To cite this article: Hamad Al-Saad, Amer Jassim Al-Khafaji & Fadhil N. Sadooni (2019):
Evaluation of the source rock potential of the Unyazah Formation (late Carboniferous-Early
Permian) in Dukhan Field, Qatar, Petroleum Science and Technology
To link to this article: https://doi.org/10.1080/10916466.2019.1602636
Published online: 22 Apr 2019.
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PETROLEUM SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/10916466.2019.1602636
Evaluation of the source rock potential of the Unyazah
Formation (late Carboniferous-Early Permian) in Dukhan
Field, Qatar
Hamad Al-Saada, Amer Jassim Al-Khafajib , and Fadhil N. Sadoonia
a
Environmental Science Center, Qatar University, Doha, Qatar; bChemistry Department College of Science for
Women, University of Babylon, Al Hillah, Iraq
ABSTRACT KEYWORDS
Twenty samples were collected from the Unayzah Formation in three wells Unayzah Formation; Dukhan
from Dukhan Field, Qatar. Many samples were of poor quality due to the Field; Paleozoic; Arabian
low TOC content containing gas prone-kerogen type III and IV. The Rock- Basin; source rocks; Qatar
Eval maturity parameters indicate that many samples were immature, while
the mature samples generated dry gas. The C15þ extracts GC suggests a
marine input, while they have kerogen type III and IV which are usually
derived from terrestrial input. This may be due to the abundance of G.
Prisca which was probably recycled from older sediments. The organic mat-
ter may also have been subjected to oxidation, leaching, biodegradation
or recycling due to the changing nature of the depositional environment
that ranged from braided river system to marine settings.
1. Introduction
The Unayzah Formation was firstly described by (Al-Laboun 1987) to cater for the so-called Pre-
Khuff clastics from the Qusayba area in the Qasim region of the Greater Arabian Basin, Saudi
Arabia. In its type locality, the Formation consists of sandstone, shale and thin beds of argilla-
ceous limestone. The Unayzah includes all the clastics that were deposited from the Late
Carboniferous to the Early Permian. The Formation has been reported from Kuwait (Tanoli et al.
2008) and it is equivalent to the Ga’ara Formation in western Iraq (Al-Hadidy 2007). (Ferguson
and Chambers 1991) described the first subsurface section of the Formation from the well
Hawtah-1 in Saudi Arabia to be formed of two sandstone units separated by upward coarsening
siltstone units.
In Qatar, only few wells penetrated the Paleozoic strata in Dukhan and Ras Matbakh fields
(Al-Saad and Sadooni 2016). Earlier workers named this Formation as the Haushi Formation
(Focke et al. 1986) based on tentative correlation with Oman. A revised stratigraphic nomencla-
ture of the Qatari Paleozoic system was published by (van Buchem et al. 2014) and (Al-Saad and
Sadooni 2016). Accordingly, the name Haushi was replaced with the Unayzah and a correlation
with the Saudi stratigraphic system was established. The Unayzah is overlain by the Khuff
Formation, the main gas reservoir in Qatar and rests on the Tawil Formation.
In in the studied Dukhan three wells, the formation consists mainly of alternations of sand-
stone and shale with a unit of siltstone (Figure 1). The sandstone is pebbly showing cross or
graded bedding. There are also horizons of shale, anhydrite and dolomite. It contains also some
CONTACT Fadhil Sadooni [email protected] Environmental Science Center, Qatar University, P. O. Box 2713,
Doha, Qatar.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpet.
ß 2019 Taylor & Francis Group, LLC
2 H. AL-SAAD ET AL.
Figure 1. Location map and composite lithologic section of the Unayzah Formation in Dukhan Field, Qatar.
PETROLEUM SCIENCE AND TECHNOLOGY 3
Figure 2. Plant remains and wood pieces in cores from Dukhan Field and to the right plant remains from the Unayzah-equiva-
lent Ga’ara Formation, Western Iraq.
horizons of lignite and silty coal beds. The formation has high amount of plant remains and
wood pieces (Figure 2). The formation was deposited in a braided river system that shifted grad-
ually into marine environment (Al-Saad and Sadooni 2016).
The aim of this paper is to understand the sources of the organic matter in the formation and
its potential for hydrocarbon generation. This is the first published work on the formation
in Qatar.
2. Materials and methods
Twenty core samples were collected from the shaly horizons of the Unayzah Formation from
three wells from Dukhan Field (A, B and C) that are deposited at the cores store of Qatar
Petroleum. Depths are ranging between 3409 and 3916 m. Detailed geochemical extracts analyses
were conducted on the samples at the laboratories of Geomark Research Ltd, Houston, USA.
3. Source rock potential by TOC and Rock-Eval pyrolysis analysis
3.1. Quality and quantity of organic matter
The minimum TOC for carbonate and shale to be effective source rocks is 0.3 and 0.5 wt.%,
respectively. Although samples with higher TOC generate higher (S2) values, this is not a rule
because of the variation in the organic matter types, suggesting sometimes a recycled organic
matter. TOC (wt %) is usually greater than the sum of the SI, S2, and S3, (Tissot and Welte
1984), because if a rock contains abundant non-organic matters, it will show high TOC values
but essentially no pyrolysis response. For example, a sample from the well A numbered (C#-6
8H) have a 1.7 wt% TOC but the sum of S1, S2, and S3 is 0.79. This is because the organic mat-
ters were recycled.
The Unayzah Formation in well A shows a variation in the TOC (wt %) values where it ranges
from poor (0.18 to 0.99) to fair (1.03 to 1.7). Well B samples were poor (TOC< 0.5) where all
samples range from (0.1 to 0.41 wt %), and in Well C samples, it ranges from 0.05 to 0.36 except
one sample which has a TOC of 1.43 wt% indicating a fair source rock. This suggests that the
Formation has poor to fair quantity of source rocks of indigenous type, (Peters 1986; Figure 3).
The studied samples have S1 < 0.05, range from (0.02 to 0.12), indicating poor quantity source
rocks. The migration index (S1/TOC) is high, and the Tmax is usually low for migrated hydro-
carbons. Normalized Oil Content, S1/TOC ratio for all samples is shown in (Figure 3a). S1/TOC
¼ 0.1 to 0.2 for oil expulsion for most samples, and many samples from well A and B suggest
4 H. AL-SAAD ET AL.
Figure 3. (a) S1/TOC vs. TOC (wt %) diagram shows that most of Unayzah samples are in the zone of indigenous hydrocarbon
(Hunt 1996). (b) Diagram of TOC (wt %) vs remaining hydrocarbon potential (S2) for Unayzah Formation. Most of the samples
are falling in type IV zone. (c) Petroleum source quality diagram for organic matter diagram of TOC versus Rock-Eval S2/S3 values
of the samples. (d) Modified Van Krevelen diagram (HI vs. OI), indicating the kerogen type for the Unayzah Formation.
indications of contamination. The oil potential (S2) represents hydrocarbons generated by degrad-
ation of the kerogen by pyrolysis, (Peters and Cassa 1994). The oil potential (S2) for all samples
was (S2 < 2.5) ranging from 0.01 to 0.9 suggesting poor quality source rocks especially in well B.
The S2 vs. TOC plotted in (Figure 3b) shows that most samples are falling within the kerogen
type IV (dry gas) and the others in kerogen type III (gas prone) zone. The S2/S3 ratio is a param-
eter describing the type of the generated hydrocarbons. The samples have ratios that range
between 0.04 and 2.73 indicating that most samples are gas prone kerogen type IV, (Figure 3c).
3.2. Types of organic matter
Pyrolysis is used for predicting the quantity of organic matters compounds that could be gener-
ated from a source rock upon further maturation. The hydrogen index (HI ¼ S2/TOC) x 100) for
the studied samples ranges from 10 to 111, whereas, the oxygen index (01 ¼ (S3/TOC) x 100) is
from 12 to 496, indicating a kerogen Type IV which is considered as “dead” carbon. Type IV
kerogen was originated from reworked and oxidized organic matter and may be sourced from
other types of kerogen that were reworked and oxidized. This type of kerogen is common in
Devonian rocks and originated from terrigenous plants. Other samples have kerogen type III,
which is gas prone.
HI decreases as the sample matures and may be lowered by weathering or mineral matrix
interactions, which eventually lead to reduction in the S2 value. Oxidized, highly mature, or Type
IV kerogen usually shows high Tmax values, low HI but lacks S2 peak. These types of kerogen
are common in siltstones and sandstones accessible to oxygenated groundwater, as the clastic
sediments of the Unayzah Formation. The (Espitalie et al. 1977) plot of the hydrogen index vs.
oxygen index is used to describe the type of organic matters in the Unayzah Formation samples.
(Figure 3c), shows that the dominant kerogen in most of the samples is type IV (dry gas) and the
PETROLEUM SCIENCE AND TECHNOLOGY 5
Figure 4. (a) Hydrogen index (HI) vs. Tmax plot, shows the kerogen type and maturity range of Unayzah Formation samples
(after Espitalie et al. 1986). (b) Plot of Tmax versus production index (PI) values reflecting the degree of maturation and hydrocar-
bon-generation zone.
3.3. Thermal maturity of organic matter
The level of thermal maturation can be estimated from the hydrogen index vs. Tmax plot,
(Figure 4a), and the production index (PI) vs. Tmax to estimate the level of maturity, (Figure
6 H. AL-SAAD ET AL.
Figure 5. (a) Saturate fraction gas chromatograms of Unayzah Formation extracts from Dukhan Field, Qatar. (b) Carbon prefer-
ence index (CPI) via pr/ph plot showed that all samples were marine carbonate input and most of them were hypersaline car-
bonate or evaporated. (c) Relationship between Pr/n-C 17 vs Ph/n-C 18, indicating marine origin source rocks deposited in
reducing environment, thermal maturity, and non- biodegradation status (Waples 1983).
4b). Samples with PI > 0.1 and Tmax values less than 435 C, respectively, indicate immature
organic matters. Most sample (about 11 samples) are of immature kerogen with Tmax ranging
from 313 C to 368 C. When Tmax value > 470 C, it suggests a postmature phase and the kero-
gen yield is wet-gas.
Most of the other samples of well A and C have Tmax value ranging from 472 to 535 indicat-
ing wet gas pron. Three samples from wells B, A and C are located within gas prone kerogen
type III and one sample from well A is within oil prone kerogen zone. These data indicate that
most of the mature sample generated dry gas.
4. Gas chromatography interpretation
Gas chromatography fingerprints used in this study to indicate the types of source organic matter
input, depositional environment and maturity. A suite of many ratios was applied to assess the
redox potential including; Pristane/Phytane (Pr/Ph), Isoprenoids/n-alkanes (Pristane/nC17 and
Phytane/nC18) (Figure 5a). These compounds are affected by secondary processes e.g. biodegrad-
ation, maturation, and migration. The studied samples have pr/nC17 and ph/nC18 rations ranging
from 0.15 to 1.08 and 0.12 to 0.63 respectively. The acyclic isoprenoid (Pr/Ph) ratio is considered
as the most common indicator of the redox conditions of the source depositional environment
(Didyk et al. 1978). Pr/Ph ratios in the range of 0.20–0.82, and usually increases with thermal
maturation. Pr/ph >1 indicates oxic depositional conditions. The pristane/nC17 and phytane/nC18
ratios decrease with thermal maturity and increase with biodegradation because aerobic bacteria
PETROLEUM SCIENCE AND TECHNOLOGY 7
Figure 6. Example Geochemical Summary Sheet of a XUNK0109 GC sample, showing bulk properties, gas chromatogram as well
as terpane and sterane biomarker mass chromatograms.
usually attack the n-alkanes before the isoprenoids. The samples have a ratios range of 0.14 to
0.63 and from 0.15 to 1.08 respectively.
Carbon preference index (CPI) is a specific maturity indicator. It is a ratio of peak heights or
areas for odd- to even-numbered n-alkanes in the range of n-C24–n-C34, (Bray and Evans 1961).
Higher CPI values indicate low maturity and terrigenous input. Values of 1.0 suggest that the
rock extract is thermally mature and may indicate the prevalence of marine conditions. Values of
less than 1.0 are typical of a low-maturity bitumen from a carbonate source or a hypersaline
environment. The CPI value for all samples range from 0.57 to 1.3. (Figure 5b).
Most of the Unayzah Formation extracts have Pr/Ph ratios of <0.8, low pr/n C17, and ph/nC18
which may result from increasing thermal maturity, and the carbon preference index (CPI <1),
8 H. AL-SAAD ET AL.
Figure 7. Marine carbonate to shally depositional environment suggested from; (a) Average C35S/C34S and C29/C30 hopane of
samples of Unayzah Formation. (b) Average C31 R/Hopane and C29/C30 hopane ratios of samples of Unayzah Formation. (c)
Heavy-end biomarker maturity indicators (C27 Ts/Tm and TAS3) showing thermal-maturity trends in Unayah Formation. (d)
Diagram of sterane ratio: C 29 20S /R vs. C 29 bbS/aaR for organic matter from Unayzah samples. (Peters and Moldowan 1993).
indicating algal/bacterial organic detritus in the kerogen, which is typical of marine source rocks
that were deposited under open water conditions, hypersaline or carbonate environments (Tissot
and Welte 1984). Plotting pristane/n-C17 against phytane/n-C18 ratios (Figure 5c), may reflect the
nature of the depositional conditions. The plot indicates that the organic precursors in the
Unayzah samples were originated from algal/bacterial organic detritus in the kerogen (Figure 5c).
This is supported also by the predominance of nC15, nC17, and nC19 in the gas chromatograms
and a front-end biased n alkane distribution.
Source rocks that were derived from marine or lacustrine algae have usually abundant short-
chain n-alkanes with almost no odd/even carbon predominance. While the source rocks that
were originated from terrigenous higher-plant waxes input often have abundant long chain n-
alkanes and odd/even carbon predominance. The n-C27, n-C29, and n-C31 n-alkanes are origi-
nated mainly from higher-plants, (Didyk et al. 1978; Peters et al. 2005). For the studied samples,
(Figure 5a) shows maximum peaks of normal alkane distribution occurring in the range n-C17 to
n-C21, which is characteristic of source rocks containing marine organic matter input with little
contribution from land plants.
These conclusions are supported by other geochemical and geologic data. During the
Ordovician Gloeocapsomorpha Prisca was widespread throughout the epicontinental seas, and in
some environments, it was the only organism contributing to the primary biomass. (Blokker et al.
2001). The G. Prisca which appear on (Figure 5a) as indicated by the predominance of nC15,
nC17, nC19 may be recycled from the underlying older clastics sediments. It represents an import-
ant contributor to the organic matter content of the Unayzah Formation.
These conclusions derived from gas chromatograms of the saturated fraction of the samples
appear to be inconsistent with the kerogen types III and IV. These types were common in the
studied rocks and they are assumed to be originated from terrigenous plants. It is important,
however, to notice that the components of type III and IV kerogen of the studied samples do not
necessarily have to contain continental organic matters. Sediments, whose constituents are com-
posed of amorphous organic matters (partially fractured without oxygen) often gives the same
PETROLEUM SCIENCE AND TECHNOLOGY 9
signature of kerogen type III. The kerogen type IV may contain organic substances that are oxi-
dized, synthetically unstable, and derived from soft granules and plankton.
5. Sterane and terpanes interpretations
Gas chromatography-mass spectrometry analysis of seven extracts for steranes (m/z 217) and
hopanes (m/z 191) are shown in (Figure 6). The gammacerane/C31R average is 0.32, the average
C22/C21 tricyclic terpane is 0.94 and the C24/C23 average is 0.62. The C19/C23 tricyclic terpane
ratio average is 0.04, the average ratio C31R/H tricyclic terpane is 0.29, and the average C26/C25,
tricyclic terpane is 0.86, All these data suggest a marine organic matter input with higher salinity,
(Zumberge 1987; Peters et al. 2005). The average value of C35/C34 homohopane is 1.1, and the
Ga/C31R ratio indicates anoxic marine environment with stratified water column as confirmed
also by the pristane/phytane (Pr/Ph) ratio, (Figure 7a and b; Peters et al. 2005).
Many biomarkers ratios are used to assess the thermal maturity levels of the bitumen samples.
The C27 Ts/Tm, (Moldowan et al. 1986), (Figure 7c), C29 20S/R, C29 bbS/aaR, (Figure 7d), and
TAS3 (CR), (Peters et al. 2005). The variation in the C27 Ts/Tm ratio ranges from 0.17 to 0.56.
This may indicate a higher thermal maturity, (Moldowan et al. 1986). The C29 20S/R average of
0.39, the C29 bbS/aaR average of 0.440, and the TAS3 (CR) ratio average of 0.72, all confirm that
the samples were at higher maturity level. This also suggests that maturation of the source rock
also depended on source facies.
5. Conclusions
1. The Unayzah Formation samples were poor quality source rocks due to the lack of TOC con-
tent and the presence gas prone kerogen type III and IV.
2. The Pck-Eval maturity parameters indicate that many samples were immature and most of
the mature sample were generated dry gas.
3. The C15þ extract GC for samples indicate marine input, while the kerogen types III and IV
are usually derived from terrestrial input. This may be due to the predominance of G. Prisca
content which was probably recycled from older deposits or the organic matter was subjected
to oxidation, leaching, biodegradation or recycling.
Acknowledgments
The authors are indebted to Qatar Petroleum for providing the samples and some related data. The analyses were
carried out at the labs of Geomark Research, Houston, USA.
ORCID
Amer Jassim Al-Khafaji http://orcid.org/0000-0001-8489-394X
Fadhil N. Sadooni http://orcid.org/0000-0001-5027-0648
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