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10 1016@j Coal 2019 103350
10 1016@j Coal 2019 103350
PII: S0166-5162(19)30372-6
DOI: https://doi.org/10.1016/j.coal.2019.103350
Reference: COGEL 103350
Please cite this article as: X. Kong, Z. Jiang, C. Han, et al., Organic matter enrichment and
hydrocarbon accumulation models of the marlstone in the Shulu Sag, Bohai Bay Basin,
Northern China, International Journal of Coal Geology(2018), https://doi.org/10.1016/
j.coal.2019.103350
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Xiangxin Kong 1,2,3 , Zaixing Jiang 1,3 * , Chao Han2 , Ruifeng Zhang4
1 School of Energy Resources, China University of Geosciences (Beijing), Beijing 100083, China
2 College of Earth Science and Engineering, Shandong University of Science and Technology,
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3 Key Laboratory of Marine Reservoir Evolution and Hydrocarbon Enrichment Mechanism,
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Ministry of Education, China University of Geosciences (Beijing), Beijing 100083, China
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4 PetroChina Huabei Oilfield Company, Renqiu, 062552, China
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* Corresponding author. E-mail address: Jiangzx@cugb.edu.cn
ABSTRACT
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intervals. Organic matter enrichment, hydrocarbon migration, and the spatial relationship of
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source rocks and reservoirs have important influences on differential hydrocarbon accumulation
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within the system. Most studies have ignored the complexity of hydrocarbon accumulation in
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unconventional oil reservoirs. A typical hybrid lithology system with a combination of marlstone
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and rudstone has been discovered in the lower part of the third member of the Shahejie Formation
of the Shulu Sag, Bohai Bay Basin, Northern China. The basin showcases a strong heterogeneity
accumulation within hybrid unconventional systems. However, relevant work in the study area
was scarce. A study of the mechanisms of organic matter enrichment and hydrocarbon
accumulation was required to understand the heterogeneity of the oil reservoirs. Nine units in
ascending order, namely I L, IU , IIL , IIU , IIIL , IIIU, IV, VL , and VU , were proposed in this study. A
detailed geochemical analysis was carried out to distinguish the organic matter sources and
preservation conditions among the different units, and assess the migration patterns of the
hydrocarbons. The results show that Unit II L has the highest total organic carbon (TOC) content.
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Unit II L has a higher quantity of aquatic sourced organic matter, w ith relatively high abundance of
short chain n-alkanes, C27 /C29 sterane, and 4-methyl steranes. Based on the low ratios of pristane
to phytane, the varve-like lamination structure of the lithology and suitable salinity, w e can
speculate that good organic matter preservation conditions existed in Unit II L . Maturity of the
source rocks increases with depth. Biomarkers indicate that hydrocarbons within the marlstones
were retained in situ, whereas hydrocarbons within the rudstones were derived from source rocks
via short- or long-distance migrations. Fractures can act as effective pathways for hydrocarbon
migration. Organic matter sources, preservation conditions, maturity, and hydrocarbon migration
ways jointly controlled the formation of oil reservoirs in the Shulu Sag. The results of this study
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provide a better understanding of organic matter enrichment and hydrocarbon accumulation and
1. Introduction
As the demand for unconventional oil and gas resources gradually increases, shale and tight
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reservoirs have become key exploration target areas in global petroleum geology (Jarvie, 2012a, b;
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Han et al., 2016; Liang et al., 2017). A common understanding is that most unconventional sources,
especially shale oil, are stored in source rocks; however, hydrocarbon migration from source rocks
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(Jarvie et al., 2012b; Kong et al., 2019a). For example, the Bakken shale oil is generated in the
upper and lower mudstone sections and accumulated in the tight carbonate and sandstone
reservoirs within the middle member (Smith and Bustin, 2000). The hydrocarbon migration
process within the unconventional system mainly occurs in a hybrid lithology association, which
and carbonate (Jarvie et al., 2012b). For the hybrid lithology system, the quality of source rocks
controls the potential of unconventional sources (Liang et al., 2017), and organic-lean lithology
reservoirs influence hydrocarbon accumulation and production scale (Lei et al., 2015). Therefore,
organic matter enrichment and hydrocarbon migration within unconventional systems are key
factors to control the formation of hydrocarbon accumulation, such as the Granite Wash tight
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rudstone oil reservoir in the Anadarko Basin (Mitchell, 2011), Eagle Ford shale oil reservoir in the
Texas (Jarvie et al., 2012b), and Yanchang tight mudstone-siltstone reservoir in the Ordos Basin
(Xu et al., 2017). The spatial relationship between source rocks and reservoirs has an important
(Smith and Bustin, 2000; Ko et al., 2017), multiple potential unconventional resources have been
found in lacustrine basins in China, such as Bohai Bay Basin (Zhao et al., 2014; Liang et al.,
2018b), Jianghan Bas in (Li et al., 2018), Jiuquan Basin (Guo et al., 2018), Ordos Basins (Li et al.,
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2016), and Songliao Bas in (Zou et al., 2019). Lacustrine unconventional systems showcase strong
systems, and the prediction of hydrocarbon distribution. The Shulu Sag is a small half-graben
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basin in the Bohai Bay Basin. It has recently become a research hotspot because it is estimated
marlstone-rudstone strata (Zhao et al., 2014). Previous studies suggest that the hydrocarbons in
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marlstones are self-sourced, while those in rudstone reservoirs are from nearby organic matter-rich
marlstones (Li et al., 2017). Vertical hydrocarbon migration is proposed based on the
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heterogeneity of thermal maturity biomarkers (Tang et al., 2018). Moreover, production results
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show that the main oil production is from lower units in the formation (Kong et al., 2017), which
have a relationship with vertical organic and lithological characteristics (Kong et al., 2019a).
Therefore, the Shulu Sag is an appropriate case to study the heterogeneity of continental
organic matter enrichment and hydrocarbon accumulation in the Shulu Sag must be understood;
The major goals of this work are as follows: (1) to study the mechanism of organic matter
enrichment and discuss the relationship between depositional environments and hydrocarbon
generation potential; and (2) to analyse the migration characteristics of hydrocarbons in the Shulu
Sag and build a model of hydrocarbon accumulation to predict exploration potential in the basin.
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2. Geological setting
From the latest Cretaceous through the Paleogene, active mantle convection and the
India-Eurasia collision have caused lithospheric extension and thinning beneath the Bohai Bay
Basin, North China (Ye et al., 1987). This tectonic process created a series of grabens and
half-grabens within the Bohai Bay Basin, such as the Jizhong Depression (Fig. 1). The Shulu Sag,
which lies in the southwestern corner of the Jizhong Depression, is a NE-SW-trending elongated
half-graben basin (Figs. 1, 2A). It formed during the early Paleogene, c ontrolled by the
downthrow of the Xinhe Fault (Jiang et al., 2007). The Shulu Sag is bounded by the Xinhe Fault
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to the southeast and Ningjin Uplift to the west, and contains three tectonic belts from west to east:
gentle slope, subsag, and steep slope (Fig. 2B). The W-E to WNW-ESE trending faults, including
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the Hengshui, Taijiazhuang, and Jingqiu faults, divide the basin into three segments from north to
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south (Fig. 2B).
The Paleogene lacustrine strata in the Shulu Sag directly overlapped the
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updip onto the western slope to the Ningjin Uplift (Jiang et al., 2017). In descending order, the
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overlying strata include the Pingyuan, Minghuazhen, Guantao, Dongying, and Shahejie formations
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(Fig. 2C). The Shahejie Formation consist of three members; these are: No. 1 (Es 1 ), No. 2 (Es 2 ),
and No. 3 (Es 3) (Jiang et al., 2017). The Shahejie 3 (Es 3 ) Member can be further divided into
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upper and lower submembers. Organic matter-rich marlstones containing carbonate rudstones are
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developed in the lower submember of Shahejie 3 (Es 3 ), and these are the exploration target for
A previous study divided Es 3 L submember into five units: I, II, III, IV, and V (Zheng et al.,
2015). The stratigraphic classification of Es 3L in this study is an improved version combined with
the previous scheme and characteristics of organic geochemistry and lithology. Units I, II, III, and
V contain lower and upper units based on changes of lithology and TOC contents. Thick rudstone
intervals are mainly developed in units I L and IIIL. Other units are mainly composed of
marlstones.
Six wells were selected in this study (Fig. 2), including Well J94 (located in the upper gentle
slope zone), Well J97, Well J98X, Well J116X and Well ST1H (located in the lower gentle slope
zone), and Well JG13 (located in the subsag zone adjacent to the steep slope).
analyses were ground to < 200 mesh using an agate pestle and mortar. The TOC content was
measured by a LECO CS-200 carbon/sulphur instrument after carbonate removal using excessive
diluted hydrochloric acid (HCl). Rock-Eval pyrolys is was conducted using an OGE-VI Rock
Pyrolysis instrument based on the procedures described by Espitalié et al. (1977). The kerogen
elements were determined using an Elementar vario MARCO CHNS elemental analyzer. The
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sample powders were pretreated with HCl and a mixed solution of HCl and hydrofluoric acid (HF)
to remove carbonate and silicate minerals. The residue was separated by heavy liquids , and
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chloroform (CHCl3 ) was used to extract the soluble components. Whole-rock mineralogical
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analyses were measured using a D8 DISCOVER X-Ray Diffractometer (XRD) to provide
The vitrinite reflectance (Ro) was analysed using a ×50 oil immersion objective lens and a
Leitz MPV-SP microphotometer, following the procedures described by Schoenherr et al. (2007).
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A total of 17 samples from wells ST1H, J94, J97, J98X, J116X, and JG13 were selected for
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hydrocarbons stored in rudstones, and oil samples from production. The gas chromatographic
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analyses of the saturated hydrocarbon fraction were performed with a HP 6890 chromatograph
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equipped with an HP-5 column (30 m × 0.32 mm i.d.; film thickness 0.25 μm). The oven
temperature was initially set at 35 ℃ for 5 min, increased to 325 ℃ at 3 ℃/min and maintained for
20 min. Helium was utilised as the carrier gas. Gas chromatography-mass spectrometry analyses
of the saturated hydrocarbon fraction were carried out on an Agilent 5975i instrument interfaced to
a HP 6890 chromatograph equipped with the same type of column used during the gas
chromatographic analyses. The oven temperature was initially set at 50 ℃ for 1 min, increased to
120 ℃ at 20 ℃/min, to 310 ℃ at 4℃/min, and maintained for 30 min. Helium was utilised as the
carrier gas again. The abundance ratios of selected biomarkers were calculated from peak areas in
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4. Results
4.1. Lithology characteristics
Five fine-grained rock lithofacies and three rudstone lithofacies have been identified in
carbonate rudstones (Kong et al., 2017, 2019a). These lithofacies can be grouped into two types
according to their origins: normal sediment facies and event sediment facies (Kong et al., 2017).
Therefore, we simplified the eight lithofacies into three groups: (1) varve-like, laminated
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marlstones; (2) graded laminated to massive marlstones and siltstones; and (3) carbonate rudstones.
The varve-like, laminated marlstones are characterised by alternating light, calcite laminae and
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dark, clay laminae. It represents normal, suspended sediment that was controlled by the seasonal
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plankton activity and variable material input, and deposited in a still, anoxic environment (Kong et
al., 2017). The graded laminated to massive marlstones and siltstones are characterised by a very
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faint lamination or a fining upwards lamination and correspond to deposits developed from
turbidity currents (Kong et al., 2017). The carbonate rudstones are derived from the western
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Ningjin Uplift by mechanical transportation (Jiang et al., 2007). Their distribution characteristics
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The richness of organic matter in wells ST1H and J116X shows significant fluctuation among
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different units (Fig. 3). The highest TOC contents occur in Unit II L, with an average of 2.62 wt%
in Well ST1H, and an average of 2.44 wt% in Well J116X (Fig. 4). Of the remaining units, II U and
VL have higher TOC contents (Fig. 4). Units I L and VU display the lowest TOC contents, and their
average TOC contents are all less than 1.0 wt% (Fig. 4).
The Rock-Eval parameter S2 and TOC can be used to evaluate the hydrocarbon generation
potential of source rocks (Peters and Cassa, 1994). The average values of TOC and S 2 indicate that
most of the samples from Unit II L are very good source rocks, whereas samples from units I L and
VU indicate that they are fair to poor source rocks (Fig. 5). The results show that the remaining
units are good source rocks (Fig. 5). The variation in the source rock quality in wells ST1H and
J116X is basically the same as the variation in the richness of organic matter.
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The Tma x values of Well ST1H range from 424 to 452 ℃ with an average of 444 ℃ (Fig. 6A),
which is in the range of mature zone of hydrocarbon generation (Espitalié et al., 1986). The
vitrinite reflection (Ro) values of Well ST1H range from 0.38 to 0.62, indicating them to be
immature to early mature (Fig. 7). The lower Ro values than expected may be influenced by the
composition of kerogen maceral (Hao and Chen, 1992; Zhao et al., 2014).
The plot of HI versus Tmax indicates that types of organic matter vary with various units in
Well ST1H (Fig. 6A). Most of organic matters of Units IIL , IIU, and VL belong to type I. In
contrast, units IL and VU mainly contain type III organic matter. The remaining units contain
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organic matter including type II and transitional type between type II and type III. Organic matter
types can also be identified by atomic H/C versus O/C (Van Krevelen, 1961; Tissot et al., 1974).
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The results show that kerogen of Well ST1H is mainly Type I to Type II (Fig. 6B). Even though
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the results of HI versus Tmax and atomic H/C versus O/C have a difference in the range of organic
matter types, all results show that changes of organic matter types follow a consistent pattern. The
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Normal alkanes and isoprenoids are the dominant compounds in sedimentary rocks. C15-C35
n-alkanes are present as shown in Fig. 7. Samples from different units of Es 3 L show unimodal
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distribution of n-alkanes with the maxima changing from nC17 to nC25 (Fig. 7). The
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terrigenous/aquatic ratio (TAR) can be used to identify changes in the relative amounts of
terrigenous and aquatic organic matters (Bourbonniere and Meyers, 1996). The results show that
samples from units III L, IIIU, IV, and VU have relatively higher TAR values (average value of 2.51)
than the other samples (average value of 0.81) (Table 1). Ratio of nC21-/nC22 + is biomarker
parameter used to analyse oil-source correlation in the study area (Li et al., 2017). Figure 8A
shows that nC21 -/nC22+ ratios have a negative correlation with TAR values such that nC21 -/nC22 +
ratios decrease with the increase in TAR values. This may be because the two parameters are
contrasting in their response to land plant inputs (Peters et al., 2005). Carbon preference index
(CPI) and odd-to-even predominance (OEP) provides information regrading organic matter source,
depositional environment, and thermal maturity (Peters et al., 2005). CPI values indicate that
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majority of the samples from units I L , IU, and IIL have an even-carbon preference, apart from
samples J94-1, and J98-1 (Table 1). Sample ST1H-5 has a distinct odd-carbon preference with CPI
and OEP values at 1.35 and 1.59, respectively (Table 1). Other samples have CPI values of
approximately 1.0 (Table 1). Pristane (Pr) to phytane (Ph) ratios vary with samples, with high
values ranging from 1.14 to 1.71 (samples ST1H-4, ST1H-5, ST1H-6, ST1H-8, J94-2, J98-2, and
JG13-1) and low values ranging from 0.33 to 0.53 (samples ST1H-1, ST1H-2, ST1H-3, ST1H-9,
and J97-1) (Fig. 9A). The ratio of isoprenoids to n-alkanes has been calculated, with 0.26–0.88 for
Pr/nC17 and 0.30–1.48 for Ph/nC18 (Table 1). The plot of Pr/nC17 versus Ph/nC18 can be used to
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4.4.2. Hopanes
from C31 homohopane to C35 homohopane (Fig. 7). Ts/(Tm+Ts) ratios from samples of Well ST1H
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increase with depth except for Sample ST1H-5 (Table 2). Moreover, C30 M/C30 H ratios from the
same samples show a tendency to decrease with increase in depth (Table 2). The values of two
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parameters from other samples are shown in Table 2 and are discussed below. Gammacerane is a
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peculiarity of the m/z 191 chromatogram. Samples from units IL, IU, and VU of Es 3L have high
ratios of samples from Unit II L range from 0.20 to 0.29. Other samples have low
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Gammacerane/C31 homohopane ratios ranging from 0.08 to 0.11; the data are presented in Table 2.
4.4.3. Steranes
C27 , C28 , and C29 steranes are the most common sterane homologues of regular steranes and
diasteranes. The relative abundance of C27 , C28, and C29 steranes shows sensitivity to organic
matter type (Huang and Meinschein, 1979). Their abundance in majority of the samples exhibit a
roughly “V” type distribution (Fig. 7). The ternary diagram of C 27, C28 , and C29 steranes from
samples of Well ST1H suggests that marlstones in this study are characterised by organic matter
derived from a mixture of plankton and land plants (Fig. 10). Figure 8B shows that ratios of
C27 /C29 sterane of most samples have negative correlation with TAR values, while some samples
are exceptions such as samples J98-1, J116X-1, and JG13-1. The ratios of C29 20S/(20S+20R) and
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C29 ββ/(αα+ββ) are in the range of 0.17–0.50 and 0.28–0.47, respectively (Table 2).
5. Discussion
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5.1. Evolution of the thermal maturity of Es 3
Biological markers can be used to assess the maturity of source rocks (Gürgey, 1999).
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Variations in the vertical thermal maturity associated with biomarkers related to Es 3 are present in
the marlstone samples from Well ST1H (Fig. 11). Isomerization in the C29 regular sterane causes
increases in the 20S/(20S+20R) and ββ/(αα+ββ) ratios, as thermal maturity increases at a certain
stage of oil generation (Mackenzie, 1984; Huang et al., 1990; Han et al., 2017). The ratios of the
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two parameters show a similar tendency in which both have low values in upper units of Es 3 (VU ,
VL , and IV) and reach relatively stable high values with increasing burial depth (Fig. 11).
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Differences in thermal stability cause the Ts/(Ts+Tm) values to increase, and the C30 M/C30 H
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values to decrease with increasing thermal maturity (Seifert and Moldowan, 1978; Peters et al.,
2005). The results suggest that the Ts/(Ts+Tm) values of marlstone samples in Well ST1H are
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relatively low in the upper and middle units of Es 3 (from VU to IIU) and high in the lower units of
Es 3 L (IIL, IU , and IL) (Fig. 11). Accordingly, the C30 M/C30 H values are relatively higher in upper
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units of Es 3 L (VU , VL , and IV) and decrease gradually in the middle units of Es 3 L (IIIU , IIIL , and
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IIU ), reaching a low stable value in lower units of Es 3 L (IIL , IU , and IL ) (Fig. 11). Maturity markers
Ro and Tmax also tend to increase as depth increases (Fig. 11). The abnormally low Tmax values of
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samples from units I L and IU are due to low abundance of S2 , which lead to inaccurate Tmax values.
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Combined with various maturity parameters, we propose that Es 3 strata were not influenced by
late tectonic activity because all the parameters have obvious correlations with burial depth. All
the Es 3 L strata may be located in relatively mature zones based on values of Tmax and CPI and OEP
as shown in previous studies (Zhao et al., 2014). Most CPI and OEP values are near 1, suggesting
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that they have been modified by maturity (Peters et al., 2005). The Es 3 strata of Well ST1H area
can be divided into three groups based on the evolution of their maturity. Group I include units VU ,
VL , and IV, and are characterised by relatively low thermal maturity evolution, as shown in Fig. 11.
Group II include units III U, IIIL, and II U, and represent the transition from low maturity to maturity.
Group III include II L , IU , and IL and have obvious characteristics of relatively high maturity. We
adopted this scheme as the basic premise in the following discussion on sources of organic matter
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and Pr/Ph. The ratio of Ga/C31 H is a salinity index used to show the relative change in salinity of a
water body (Peters et al., 2005). Figure 12 indicates that the hydrological properties of Es 3 L strata
in the basin underwent changes in salinity, from relatively high to low, and the increasing to
relatively high. The Pr/Ph ratio can be used to reflect redox conditions (Powell and McKirdy, 1973;
Didyk et al., 1978; Peters et al., 2005); Pr/Ph values less than 0.8 indicate anoxic conditions
during deposition (Chen et al., 1996), whereas values ranging from 1.0 to 2.0 have been reported
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in anoxic-subanoxic and fresh-brackish water environments (Chen et al., 1996). Figure 9A
indicates that the Pr/Ph ratios of marlstone samples have a negative correlation with Ga/C 31 H,
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suggesting reducing conditions that increase with salinity (Peters and Moldowan, 1993). This
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conclusion can be further supported by Fig. 9B, which shows that most of samples with high
salinity are located in the range of the reductive environment. According to the two parameters of
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samples ST1H-2, J97-2, and JG13-1, Unit I U is characterised by relatively high salinity and its
anoxic conditions are gradually noticeable from the basin edge to basin centre (Table 1). The high
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salinity of the unit may be caused by strong evaporation and relatively low precipitation during the
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initial stage (Jiang et al., 2007; Kong et al., 2017). Dramatic changes in the Ga/C31 H ratios
between Es 3L strata and Es 3 U were found in a previous study (Li et al., 2017), which revealed that
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Ga/C31 H ratios of Es 3U samples are in the range of 1.0–4.0. Considering that no obvious tectonic
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change occurred in the basin during the stage between Es 3 and Es 3 (Jiang et al., 2007) and that
there was an intermittent increase in the dry climate from Es 3 to Es 1 according to palynological
and paleontological data from Shulu Sag (Ren, 1986), we propose that the increase in salinity may
be related to the climate. Therefore, the high value of Ga/C31 H of Unit VU in Well ST1H indicates
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that the unit is the transition between Es 3 and Es 3 (Fig. 12). Unit II L has a relatively lower
salinity than Unit I U based on Ga/C31 H ratios (Table 2). However, their Pr/Ph ratios are similar,
indicating similar reducing conditions (Table 1). The lake water level likely increased significantly
in Unit II L , which would have been beneficial to the formation of varve-like, laminated marlstones
(Kong et al., 2017). The stratified water column formed in Unit II L may have been caused by both
temperature and salinity (Sinninghe Damsté et al., 1995). Sample ST1H-3, which has a relatively
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higher salinity, has a lower Pr/Ph ratio than Sample ST1H-8 even though they have the same
lithologic association (Fig. 12). Terrestrial inputs can increase Pr/Ph ratios because event
sediments can carry a certain amount of oxygen to the lake bottom (Limbach, 1975; Liang et al.,
2016). The injection of fresh water can also reduce salinity of the waterbody. Therefore, other
units formed in an oxidising or transitional environment have low Ga/C31 H values and high Pr/Ph
Previous studies suggested that the organic matter in marlstones from Es 3L in Shulu Sag were
derived from both plankton and land plants (Li et al., 2017; Tang et al., 2018). Influences from
organic matter sources on hydrocarbon accumulation were ignored because organic matters in
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Es 3 have similar characteristics (Tang et al., 2018). Even though the relative abundances of C 27,
C28 , and C29 steranes supporting the organic matter in Well ST1H are mixed-source type (Fig. 10),
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differences in organic matter compositions can also be presented by pyrolysis parameters (HI and
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Tma x), kerogen elements, and C27/C29 steranes ratios (Figs. 6, 8B). The n-alkane distribution of
saturated hydrocarbons can be used to deduce the sources of organic matter (Brassell et al., 1978;
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Hakimi et al., 2016). Higher TAR values indicate more input from land materials, compared to
aquatic sources, from the surrounding watershed (Bourbonniere and Meyers, 1996; Lai et al.,
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2018). The plot of TAR versus nC21 -/nC22 + can also be used to evaluate the differences in
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abundances of light and heavy hydrocarbons among various samples (Fig. 8A). However, thermal
cracking may change the relative abundance of molecular homologs to influence TAR and
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nC21 -/nC22 + ratios (Peters et al., 2005). Biomarkers of samples from units IU , IIL , and IIU of Well
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ST1H may have been affected by thermal maturity because their TAR ratios are low, and they
have similar values (Fig. 12). Samples ST1H-3 and ST1H-8 have similar lithological associations;
however, the TAR ratio of the former is lower than the latter, possibly in relation to the thermal
cracking of long chain n-alkane. We chose a low maturity sample (J94-3) from Unit II L for the
comparison, which indicated that values of TAR and nC21 -/nC22 + between J94-3 and ST1H-3 were
similar (Table 2). The results suggest that even though thermal cracking may modify values of
biomarkers (e.g. TAR ratio of ST1H-4), the organic matter from units I U and IIL still show a
predominantly aquatic source. This can be deduced from the low maturity samples from same
units and the ratios of the C27 /C29 steranes. High C27 /C29 ratios can reflect a predominantly
plankton/algal source (Huang and Meinschein, 1979; Hakimi et al., 2016). Therefore, values of
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C27 /C29 and TAR of most samples show the inverse relationship (Fig. 8B). Samples from units IU
and IIL have C30 sterane, possibly in the form of 4-methyl steranes, which suggests a contribution
from algae (e.g., dinoflagellates) to the sediments (Goodwin et al., 1988). This finding further
supports the idea that units I U and IIL had aquatic sourced organic matter. Abnormally low CPI
values for these units may also indicate the presence of organic matter derived from aquatic
organisms under hypersaline environments, given their maturity (Palacas et al., 1984; Peters et al.,
2005). Figure 6 shows that organic matter within Unit I U may have come from mixed sources,
suggesting that the unit had a certain amount of higher plant input. Sample JG13-1 from this unit
may have been affected by terrigenous organic matter inputs and thus had a relatively low C27 /C29
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ratio and a relatively high Pr/Ph ratio (Fig. 9A); this is because Well JG13 is near the eastern steep
slope area where nearshore subaqueous fan systems developed (Jiang et al., 2007). The sample
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may also have been influenced by thermal cracking, which would have caused the low TAR ratio,
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given its maturity (Table 2). We speculated that some hydrocarbons within Unit I U may have
migrated from Unit II L because the low TOC content of Unit I U would have limited its
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hydrocarbon generation potential; this would account for the sample from Unit I U (ST1H-2)
having characteristics similar to those seen in the gas chromatograms and mass chromatograms in
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a sample from Unit II L (ST1H-3) (Fig. 7). Therefore, it is not possible to determine the organic
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matter source of Unit I U based on available data. Thus, considering multiple parameters, we
propose that Unit II L has more aquatic organic matters than other units.
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sources and depositional environments. The deposits that filled Es 3 L in the Shulu Sag were mainly
source-controlled, in that abundant terrigenous clasts were transported into the basin from
catchment given the tectonic activity occurring at the time (Jiang et al., 2007; Zheng et al., 2015).
Previous lithologic analyses have suggested that there were more event sediments present in the
basin at the time compared to the normal background sediments (Jiang et al., 2007; Kong et al.,
2017). Variations in vertical of representation of organic matter sources are seen in the ratios of
C27 /C29 sterane in Fig. 12 and in the other parameters discussed in section 5.2. When the terrestrial
input increased, the TOC contents decreased (e.g. units III U and IV), which may have been related
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to the dilution of inorganic material and adverse preservation conditions (Liang et al., 2016; Wu et
al., 2019). Salinity has a complex relationship with the accumulation of organic matter (Hammer,
1981; Li et al., 2015; Yang and Schulz, 2019). Increases in salinity do not necessarily lead to
decreases in primary productivity, because the number of individuals surviving within a particular
species can increase even though overall species diversity decreases (Clark and Philp, 1989).
Comparative study conducted by Horsfield et al. (1994) indicates that source rocks deposited in an
alkaline lake have better potential than those in a freshwater lake. Studies also suggest that the
salinity stratification of water column is beneficial for preserving organic matter (Kirkland and
Evans, 1981; Clark and Philp, 1989). However, the degradation caused by sulfate-reducing
f
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bacteria in a saline lake can result in a loss of organic matter (Didyk et al., 1978; Kelts, 1988; Katz,
2001). When the waterbody had a high salinity in units I L , IU, and VU , the organic matter content
pr
in the sediments were low (Fig. 4, Fig. 12). However, the highest organic matter content in the
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study area was found in Unit II L under conditions of moderate salinity, rather than in other units
under low salinity conditions (Fig. 12). Therefore, organic matter accumulation is likely the result
Pr
of interaction of productivity and preservation (Tyson, 2005). The details of how organic matter
During the initial rift stage (Unit I L ), the lake basin was narrow and shallow (Kong et al.,
rn
2017). Abundant rudstones that formed after sudden floods or tectonic events occurred in the
bottom of the basin (Liu et al., 2017). Following the rudstone deposits, the basin developed
u
greyish-green shallow water facies marlstone-siltstones (Kong et al., 2017). The primary
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productivity of the unit was at its lowest, based on its TOC content and the type of organic matter
present (Figs. 4, 6). This suggests that a high input of terrigenous materials and oxic environments
did not benefit the accumulation of organic matter in the Shulu Sag.
Unit IU mainly developed grey coloured, non-regular laminated marlstones, suggesting that
lake water level obviously increased there compared to in Unit I L . The number of aquatic
organisms may have increased in a high salinity environment; however, the relatively low TOC
content of the unit may be related to the degradation of organic matter caused by bacteria (Katz,
2001). Therefore, the influence of primary productivity on the accumulation of organic matter is
For Unit II L, the lake water level rose further, and salinity decreased accordingly. The unit
13
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developed varve-like, laminated marlstones with alternating calcite laminae and clay laminae
(Kong et al., 2017). The rhythm feature supported algal blooms such that the formation of calcite
laminae was induced by biochemical processes (Kong et al., 2017). The suitable salinity did not
damage preservation conditions of organic matter and maintained the reductive environment. Such
environments were also beneficial for the preservation of varve textures (Anderson, 1986).
Therefore, a high organic matter content is the result of high productivity and a strong reductive
From Unit II U to IV, the basin was in an active stage of tectonic activity and seismic
development was abundant (Zheng et al., 2015; Kong et al., 2019b). The rudstones interval in Unit
f
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IIIL is considered to be related to paleo-earthquakes (Liu et al., 2017). Therefore, few varve-like,
laminated marlstones occur in these units (Fig. 3). Low Ga/C 31 H values suggest that these units
pr
had a low salinity (Fig. 12). Figure 12 shows that TOC values varied with the values of TAR,
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C27 /C29 sterane, and Pr/Ph. The results suggest that enrichment by organic matter is controlled by
terrigenous material input, primary productivity, and redox conditions. The abundant terrigenous
Pr
materials may have been brought into the basin by bottom flows, which could also have carried a
large amount of oxygen that would have affected reductive conditions (Liang et al., 2016).
al
Terrestrial inorganic material inputs could have diluted the accumulation of organic matter and led
rn
to the low TOC values observed today. Therefore, an increased input of terrestrial materials did
The Unit VL was a stage in which the water level of the lake rose again, and the basin was a
Jo
still environment with weak inputs of terrestrial material. The environment caused the unit to
develop varve-like, laminated marlstones. However, the low salinity caused the unit to have worse
preservation conditions than those in Unit II L . Planktonic organic matter may have been oxidised
in the upper water column because TOC values of this unit were relatively low.
biomarker (Fig. 12). However, rapid salinization may have caused a rapid die-off in aquatic
organisms as they would not have been able to adapt to the changes in their environment. The
sudden change may have been related to climatic conditions, as discussed in section 5.2. The
decrease in aquatic organisms affected the percentage of terrestrial organic matter; therefore, the
TAR value is high and the C27 /C29 sterane ratio is low. Thus, this unit presents low TOC values
14
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due to the low primary productivity level and the unfavourable preservation conditions caused by
Previous studies have suggested that source rocks from Es3 L in the Shulu Sag were all in the
mature zone (Zhao et al., 2014), which is supported by Tmax values of various units (Fig. 6A).
Therefore, all the source rocks from Es3 L have hydrocarbon generation potentials to a certain
extent. Thermal maturity profile of marlstones along the depth (Fig. 11) suggests that
f
oo
to be the primary model of hydrocarbon accumulation in previous studies (Li et al., 2017), because
both marlstones and rudstones in Es 3 L have very low porosity (0.4–2.6 %) and permeability (0.04–
pr
17.1 md) (Li et al., 2017; Kong et al., 2019a). Short distance hydrocarbon migration from source
e-
rocks to rudstones was responsible for formation of oil production sweet pots (Tang et al., 2018).
According to the short distance migration model, hydrocarbons from rudstones should have
Pr
biomarkers between rudstones and their nearby source rocks should be found. Values of
al
Ts/(Ts+Tm), CPI, and OEP from Sample ST1H-5 are obviously higher than those of nearby
rn
marlstones (Fig. 12). The ratio of Ts/(Ts+Tm) depends on maturity, as well as source and
depositional environment (Moldowan et al., 1986). A possible reason for abnormal values of the
u
ratio from Sample ST1H-5 is that hydrocarbons in Unit III L rudstones of Well ST1H were derived
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from more mature organic matter. The influence of the lithology of the source rocks can be
ignored as all the source rocks in Es 3 L are rich in carbonate. Salinity may influence the ratio of
Ts/(Ts+Tm) (Fan et al., 1987) as Sample ST1H-9 has higher value of the biomarker than Sample
ST1H-8 (Table 2). However, thermal maturity was the main factor influenc ing the biomarker with
respect to the values of Ts/(Ts+Tm) of units I U and VU . Abnormal high values of CPI and OEP
from Sample ST1H-5 suggest that organic matter is derived mainly from land plants (Bary and an
Evans, 1961), based on its Ro value, corresponding to its depositional background of strong
Figure 13 shows the relationship of maturity biomarkers between source rocks and rudstones
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and oils from production. As stated above, hydrocarbons from Unit III L (Sample ST1H-5) belong
to mature source rocks (Fig. 13). Hydrocarbons from rudstone sample ST1H-1 (Unit I L ) have
similar maturity biomarkers as mature source rocks (Fig. 13), suggesting they are migrated from
nearby source rocks with abundant organic matter content. However, hydrocarbons from rudstone
samples of Well J94 have greater differences in maturity biomarkers. Hydrocarbons of Sample
J94-1 (Unit I L ) may be migrated from mature source rocks in deeper strata, while hydrocarbons of
Sample J94-2 (Unit I U ) may from low mature source rocks in its overlying unit because Sample
J94-2 has similar maturity biomarkers as Sample J94-3 (Unit II L ) (Fig. 13). Moreover, the
differences in maturity biomarkers between rudstone sample J97-1 (Unit I L ) and marlstone sample
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(Unit I U ) suggest that hydrocarbons from upper low maturity source rocks were also migrated into
lower rudstones reservoirs (Fig. 13). Two oil samples achieved by production show high maturity
pr
and have similar characteristic gas chromatograms and mass chromatograms as compared to
mature source rocks (Fig. 7) suggesting that main hydrocarbons in Es 3 L were migrated from
e-
mature source rocks.
Pr
L
A new hydrocarbon accumulation model of Es 3 submember in the Shulu Sag is proposed
(Fig. 14). Hydrocarbons in the study area can be divided into two types depending on burial depth:
al
mature and low mature. Based on the organic matter sources analyses thus far, varve-like,
rn
laminated marlstones have highest TOC contents; therefore, these marlstones located in the deep
strata have the best hydrocarbon generation quality and potential for the formation of in situ
u
marlstone oil reservoirs. Hydrocarbons can migrate into adjacent rudstones to form rudstone oil
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reservoirs; these reservoirs have similar maturity characteristics as their neighbouring source rocks.
Numerical simulation of the stress field suggests that the lower gentle slope developed abundant
structural fractures (Wang et al., 2007). The slope break linking the gentle slope and subsag is
located in the release zone of the tensile stress, which was conducive to formation of fractures. On
the other hand, the Shulu Sag developed multiple NE-SW trending faults in the gentle slope,
which may have caused secondary faults during tectonically active s tages. These fractures
provided effective channels for long distance migration of hydrocarbons. Solid residual bitumen
unconventional hydrocarbon systems in Es 3L of the Shulu Sag have multiple oil accumulation
ways: (1) retained in situ; (2) migration over short distances; and (3) migration over long distances.
16
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L
Due to the lower maturity and organic matter content, the upper strata of Es 3 have lower
hydrocarbon generation potential than the lower strata. Therefore, previous studies have shown
that the lower strata have better production potential than the upper strata (Tang et al., 2018; Kong
et al., 2019a). Even though some low mature hydrocarbons could migrate into lower rudstone
deposits through fractures, they may play a limited role in effective oil reservoirs, as evidenced by
the oil samples obtained. In contrast, hydrocarbons released from mature source rocks within
lower strata could migrate through continuous rudstone deposits with multiple fractures from
deeper strata to the gentle slope, which could lead to potential hydrocarbon accumulation. Organic
matter sources, preservation conditions, maturity, and hydrocarbon migration ways jointly
f
oo
L
controlled the formation of oil reservoirs in Es 3 of the Shulu Sag. Therefore, deeper strata with
high TOC contents and effective migration channels is considered to be the target area with
L
The Es 3 submember in the Shulu Sag has three primary lithologic assemblages, including: (1)
varve-like, laminated marlstones; (2) graded laminated to massive marlstones and siltstones; and
al
(3) carbonate rudstones. The submember can be subdivided into nine units: I L , IU , IIL , IIU , IIIL , IIIU,
rn
IV, VL , and VU . Varve-like, laminated marlstones are mainly developed in units II L and VL .
Organic matter types vary with the units of Es3 L in the Shulu Sag. Normal alkane
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distributions combined with other biomarkers suggest that compared to other units, Unit II L
possesses organic matter that is primarily aquatic in origin. The depositional filling of Es 3 L in the
Shulu Sag was controlled by basin evolution. During the depositional period of Unit II L , the basin
activity was at a stable stage with suitable salinity, which developed abundant varve-like,
laminated marlstones with low terrestrial clasts input. High primary productivity and good
preservation conditions were beneficial for organic matter accumulation. Therefore, source rocks
Analyses of biomarkers from marlstone samples suggest that the thermal maturity of the
source rocks increases with burial depth. The heterogeneity of thermal maturity of hydrocarbons
within the rudstone samples suggests that different hydrocarbon migration patterns existed within
17
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L
the Es 3 submember. In situ marlstone oil reservoirs were developed in organic matter-rich
marlstone intervals in which hydrocarbons were retained in matrix pores due to low porosity and
with organic matter-rich marlstones. Hydrocarbons can also migrate over a long distance through
fractures. Potential high-quality oil reservoirs are formed in deeper strata having mature, high
Acknowledgements
f
This work was supported by the National Major Research Program for Science and
oo
Technology of China [Grant No. 2017ZX05009-002], and the Natural Science Foundation [Grant
No. 41772090]. We thank editor-in-chief and two anonymous reviewwes for their insightful
pr
comments, which have significantly improved our initial manuscript.
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Pr
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ST1H-1
ST1H-2
IL
IU
R
M
0.41
0.51
0.27
0.38
0.51
0.65
1.11
0.98
o f0.63
0.70
0.77
0.84
0.93
0.96
ST1H-3 IIL M 0.50 0.26 0.31
r o
1.01 0.70 0.88 1.02
ST1H-4
ST1H-5
IIU
IIIL
M
R
1.14
1.71
0.53
0.81
0.33
-0.3
p 1.03
3.16
0.61
0.30
0.94
1.35
1.15
1.59
ST1H-6 IIIU M 1.25
r
0.8
e 0.36 1.96 0.37 1.07 1.30
P
ST1H-7 IV M 0.90 0.6 0.52 2.69 0.34 1.00 1.10
l
ST1H-8 VL M 1.20 0.53 0.45 1.35 0.56 1.04 1.12
ST1H-9
J94-1
VU
IL
M
R
n a
0.53
0.88
0.78
0.88
1.32
0.4
2.21
0.54
0.42
0.40
0.94
1.05
1.02
1.05
J94-2
J94-3
IU
IIL
u rR
M
1.29
0.88
0.53
0.58
0.61
0.65
0.83
0.98
0.96
0.68
0.83
0.98
0.83
0.98
J97-1
J97-2
J98-1
IL
IU
IIL Jo R
M
O
0.33
0.67
0.97
0.53
0.44
0.48
1.48
0.63
0.51
1.24
0.58
0.55
0.51
0.91
1.00
0.67
0.77
1.07
0.95
1.03
1.02
J116X-1 IL O 0.74 0.43 0.60 0.57 1.15 0.85 1.01
JG13-1 IU M 1.17 0.62 0.54 0.83 0.68 0.84 1.03
M- Marlstone, R- rudstone, O- Oil, Pr- Pristane, Ph- Phytane, TAR- Terrigenous/ aquatic ratio: (nC27 + nC29 + nC31 )/ (nC15 + nC17 + nC19 ) (Peters et al., 2005), CPI-
Carbon preference index: [(nC25 + nC27 + nC29 + nC31 + nC33 ) / (nC24 + nC26 + nC28+ nC30 + nC32 ) + (nC25 + nC27 + nC29+ nC31 + nC33 ) / (nC26 + nC28 + nC30 + nC32 +
i+1
nC34 )]/2 (Bray and Evans, 1961), OEP- Odd-to-even predominance: [(Ci + 6×Ci+2 +Ci+4 )/ (4×Ci+1 + 4×Ci+3 )] ×(-1) i=maxima carbon number (Marzi et al., 1993).
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Table 2. Biomarker parameters of hopanes and steranes from the Shulu Sag.
Hopanes Steranes
Sample ID Unit Sample
Ts/(Tm+Ts) C30 M/C30 H Ga/C31 H C27 /C29 C28 /C29 C29 20S/(20S+20R) C29 ββ/(αα+ββ)
ST1H-1
ST1H-2
IL
IU
R
M
0.57
0.55
0.11
0.10
0.94
0.54
1.06
0.86
0.50
0.43
o f 0.45
0.46
0.55
0.55
ST1H-3 IIL M 0.51 0.09 0.29 0.99
r o
0.27 0.5 0.47
ST1H-4
ST1H-5
IIU
IIIL
M
R
0.38
0.54
0.11
0.13
0.08
0.08
0.67
-
0.47
p 0.23
0.25
0.45
0.42
0.42
0.4
ST1H-6 IIIU M 0.39 0.13
r
0.08
e0.50 0.20 0.41 0.41
P
ST1H-7 IV M 0.35 0.19 0.11 0.65 0.43 0.29 0.23
l
ST1H-8 VL M 0.33 0.20 0.11 1.01 0.28 0.32 0.18
ST1H-9
J94-1
VU
IL
M
R
0.39
0.71
n a
0.16
0.12
0.60
0.53
0.66
1.19
0.37
0.54
0.26
0.33
0.26
0.41
J94-2
J94-3
IU
IIL
R
M
0.34
u
0.38 r 0.16
0.17
0.60
0.21
0.92
0.79
0.42
0.32
0.27
0.30
0.27
0.23
J97-1
J97-2
J98-1
IL
IU
IIL
R
M
O J o
0.27
0.35
0.43
0.22
0.13
0.08
0.84
0.41
0.20
0.79
1.20
0.65
0.37
0.33
0.35
0.17
0.30
0.46
0.28
0.46
0.56
J116X-1 IL O 0.47 0.08 0.29 0.59 0.35 0.43 0.53
JG13-1 IU M 0.66 0.12 0.35 0.64 0.39 0.47 0.35
M- Marlstone, R- rudstone, O- Oil, C30 M- C30 Moretane, C30 H- C30 Hopane, Ga- Gammacerane, C31 H- C31 Hopane.
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Fig. 1. Tectonic setting of the Shulu Sag, located in the southwestern corner of the Jizhong
Depression (I) of the Bohai Bay Bas in, which is composed of six depressions, denoted by letters
Fig. 2. (A) Overview of the Shulu Sag. (B) Detailed structural map of the Shulu Sag. (C)
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Fig. 3. Correlation of well data and stratigraphic framework of the samples from the Es 3
submember. The well names with numbers (e.g., ST1H-1) indicate the location of the sample for
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biomarker analyses. Black arrows denote marlstone samples. Red arrows denote rudstone samples.
Fig. 5. Plot of average TOC contents versus average S 2 values of different units showing
hydrocarbon generation potential in the Shulu Sag (modified after Peters and Cassa, 1994).
al
rn
Fig. 6. (A) Plot of hydrogen index (HI) versus the pyrolysis temperature of maximum yield of
pyrolysate (Tma x) for different lithofacies within the Es 3 L submemeber in the Shulu Sag, displaying
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the kerogen types and the thermal maturity stages (boundary lines modified from Mukhopadhyay
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triterpanes (m/z=191; middle column), and steranes (m/z=217; right column) of selected samples
L
of Es 3 submemeber in the Shulu Sag. Locations of samples are shown in Fig. 3. C 30 H = C30
hopane; C30 M = C30 mortane; C27 RS = C27 regular steranes; C28 RS = C28 regular steranes; C29 RS
Fig. 8. (A) Plot of terrigenous/aquatic ratio (TAR) versus nC21 -/nC22 +. (B) Plot of
terrigenous/aquatic ratio (TAR) versus C27 /C29 sterane. R denotes hydrocarbons from rudsrone
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Fig. 9. (A) Plot of Pr/Ph versus Ga/C31 H. (B) Plot of Pr/nC17 versus Ph/nC18 (the boundary lines
hydrocarbons from rudsrone samples and O indicates the oil samples obtained by production.
Fig. 10. Ternary diagram of regular steranes (C27 , C28, and C29 ) from samples of Well ST1H
showing the relationship between sterane composition and organic matter sources (modified after
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Fig. 11. Variations in vertical profile of Ro, Tma x, and maturity biomarkers of various units of Es 3L
L
biomarkers of various units of Es 3 in Well ST1H. Ga/C31 H = Gammacerane/C31 hopane.
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Fig. 13. (A) Plot of C30 M/C30 H versus Ts/(Ts+Tm). (B) Plot of C29 ββ/(αα+ββ) versus C29
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Fig. 14. Hydrocarbon accumulation model of the Es 3 L submember in the Shulu Sag.
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Fig. 15. Fracture characteristics in the Shulu Sag. (A) High-angle fractures with dissolution pores
(Unit I L from Well ST3: 4266.74 m). (B) Ruptured rudstones developed in a fault zone with
residual bitumen (Unit I L from Well ST3: 4273.6 m). (C) Horizontal fractures with residual
bitumen (Unit II L from Well J94: 3335.39 m). (D) Horizontal fractures with residual bitumen and
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Declaration of interests
□√ The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which may be
considered as potential competing interests:
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Highlights
Source rock quality and migration ways influence oil reservoir heterogeneity
Mature, high TOC source rocks can form high-quality oil reservoirs
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Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
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Figure 13
Figure 14
Figure 15