Accepted Manuscript

Geochemical characterization of source rocks and crude oils in the Upper Cretaceous
Qingshankou Formation, Changling Sag, southern Songliao Basin

Tian Dong, Sheng He, Shiyan Yin, Dexi Wang, Yuguang Hou, Jigang Guo

PII: S0264-8172(15)00080-X
DOI: 10.1016/j.marpetgeo.2015.03.001
Reference: JMPG 2180

To appear in: Marine and Petroleum Geology

Received Date: 23 December 2014

Revised Date: 28 February 2015
Accepted Date: 2 March 2015

Please cite this article as: Dong, T., He, S., Yin, S., Wang, D., Hou, Y., Guo, J., Geochemical
characterization of source rocks and crude oils in the Upper Cretaceous Qingshankou Formation,
Changling Sag, southern Songliao Basin, Marine and Petroleum Geology (2015), doi: 10.1016/
j.marpetgeo.2015.03.001.

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 ACCEPTED MANUSCRIPT

Geochemical characterization of source rocks and crude oils in the

Upper Cretaceous Qingshankou Formation, Changling Sag, southern

Songliao Basin

Tian Dong ab, Sheng He a, Shiyan Yin ad, Dexi Wang ac, Yuguang Hou a, Jigang Guoe

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a
Key Laboratory of Tectonics and Petroleum Resources, China University of Geosciences (Wuhan), Ministry of

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Education, Wuhan 430074, China

b
Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, AB, Canada, T6G 2E3

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c
SINOPEC Northeast Oil and Gas Branch Company, Changchun, Jilin 130062, China

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d
College of Mining Engineering, Hebei United University, Tangshan, Hebei 063009, China
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e
Strategic Research Center of Oil and Gas Resources, Ministry of Land and Resources, Beijing 100034, China

Corresponding author: Tian Dong, Email: td2@ualberta.ca, +1 7807090810

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Abstract: The Upper Cretaceous Qingshankou Formation is one of the main exploration target in
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the Changling Sag, southern Songliao Basin. However, the origin of source rock deposition and
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crude oils remains undiscovered. A comprehensive geochemical study, including Rock-Eval

pyrolysis, gas chromatography-mass spectrometry and carbon isotope analysis on fifteen crude
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oils and twenty-two source rock samples from the Qingshankou Formation were performed in
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order to provide new insights into source organic matter, depositional environment and correlation
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between crude oils and source rocks.

Bulk geochemical analysis on source rock samples indicates that the lower member of the

Qingshankou Formation has more hydrocarbon generating potential than the middle member.

These two potential source rock members were interpreted to be deposited in slightly different

environments and have different sources of organic matter determined by biomarker assemblages.
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The lower member is organically rich (average TOC=1.27 wt.%), oil-prone, mature and deposited

under anoxic conditions with more contribution from sapropelic organic matter. The middle

member is organically poor (average TOC=0.78 wt.%), gas-prone, less mature and deposited

under less anoxic conditions with more terrigenous organic matter input. Biomarker fingerprints

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and carbon isotope compositions suggest that all the crude oils were genetically related and could

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be classified into one oil family, which has significant contribution from the lower member source

rocks and minor contribution from the middle member source rocks.

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Key words: biomarker; oil origins; oil source correlation; Qingshankou Formation; changling Sag;

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Songliao Basin
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1. Introduction

The Songliao Basin, northeastern China, is the largest continental petroliferous basin in China
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and contains over 10 km thick of Cretaceous sediments (Jia et al., 2013; Song et al., 2013). The
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Changling Sag in the southern part of the Songliao Basin is also a prolific hydrocarbon-bearing
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sag (Fig. 1, Dong et al., 2014). In the Changling Sag, two different petroleum systems have been

identified, primarily within the Qingshankou and Nenjiang Formations situated in the Upper
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Cretaceous strata. Recently, numerous small- and mid-sized oil fields have been discovered from
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the Qingshankou Formation which has a cumulative thickness of up to 560 m (Li et al., 2002;
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Wang et al., 2007; Li et al., 2009). Previous studies suggest that both organic-rich source rocks

and reservoirs are developed in the Qingshankou Formation as it contains both source and

reservoir rocks (Song et al., 2013). Recently, it has attracted attention because of its high quality

source rocks and its huge potential of shale oil resource (Bechtel et al., 2012; Huang et al., 2014;

Liu et al., 2014). The sedimentological and geochemical characteristics of the Qingshankou
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Formation have been well documented (Sun et al., 2006; Chen et al., 2010; Bechtel et al., 2012;

Huang et al., 2013; Dong et al., 2014). Most of the previous geochemical studies are focused on

the lower Qingshankou Formation (K2qn1) and the Nenjiang Formation (K2n) (Bechtel et al., 2012;

Song et al., 2013). There has been a lack of study on the middle Qingshankou Formation (K2qn2)

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and comparison between these two intervals (K2qn1 and K2qn2).

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Petroleum exploration in the Changling Sag is in a mature stage, and finding new oil reserves

is a big challenge (Zhang, 2006). Most of the oil and gas fields that have been found are primarily

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located in the Daqingzi uplift and eastern slope region, which are relatively highland areas (Fig.

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1B) (Dong et al., 2014). Since most of structural reservoirs have been drilled, current exploration
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targets have been transferred to subtle reservoirs which are mainly trapped by lithology variation

(Li, 2002; Yang, 2004; Zhang, 2006). It is necessary to investigate the origin of the discovered oils
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and determine where they come from. Characterizing the geochemical signatures of discovered
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oils (Keym et al., 2006; Hao et al., 2009), classifying oil families (Pang et al., 2003) and
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determining the respective source rocks could provide useful information for further hydrocarbon

exploration in subtle reservoirs.

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Previous studies demonstrated that biomarker fingerprints and carbon isotope data have been
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widely used to provide insights into palaeoenvironmental reconstruction, the type and origin of
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organic matter (Hayes et al., 1987; Peters et al., 2005), and investigate the origin of oils and

perform oil to source correlation (Peters et al., 2005; Yu et al., 2011). In this study, one of our aims

is to determine the origin of organic-rich mudstones deposition from K2qn1 to K2qn2 based on core

samples. In addition, the origins and geochemical characteristics of crude oils were determined.

Finally, both biomarker data and carbon isotope data were used for oil-source rock correlation
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study.

2. Geological setting

The Songliao Basin, covering an area of 260,000 km2, is the largest oil- and gas-prone

continental lacustrine basin in northeastern China (Fig. 1A, Feng et al., 2007; Bechtel et al., 2012;

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Jia et al., 2013; Song et al., 2013; Dong et al., 2014). The Songliao Basin overlies Paleozoic

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metamorphic, volcanic and magmatic rocks and includes Jurassic, Cretaceous and Cenozoic

sedimentary deposits (Jia et al., 2013; Wang et al., 2013). This basin had a complex evolution

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history which were devided into four different stages: (1) Late Jurassic thermal rifting, (2) Early

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Cretaceous extensional fracturing, (3) Middle-Early Cretaceous thermal subsidence, and (4) Late
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Cretaceous tectonic inversion (Liu, 1996; Wang et al., 2013). The focus of our study, Changling

Sag, has an area of approximately 7000 km2 and is located in the south of the central sub-sag area
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(Fig. 1B) (Dong et al., 2014). On the basis of regional tectonics and structural position, this sag
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can be subdivided into six tectonic units: the western slope zone, southern uplift zone, eastern
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slope zone, Qianan depression zone, Daqingzi uplift zone and Heidimiao depression zone (Fig.

1B).
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In ascending order, the formations of this sag are as follows: Lower Cretaceous Quantou
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Formation (K1q), Upper Cretaceous Qingshankou (K2qn), Yaojia (K2y), Nenjiang (K2n), Sifangtai
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(K2s) and Mingshui (K2m) formations; Tertiary Daan and Taikang formations (Liu et al., 1992;

Wang et al., 2013; Dong et al., 2014) (Fig. 1C and Fig. 2). The Qingshankou Formation (K2qn) is

widely distributed in the sag, and can be subdivided into three members. The lower member of the

Qingshankou Formation (K2qn1) is one of the major source rocks in the Changling Sag, and is

composed of dark-grey mudstone interbedded with fine- to coarse-grained siltstone and sandstone
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(Sun et al., 2006). It has a thickness of 300 - 500m and has been interpreted as a deep-lacustrine

deposit (Wang et al., 2013). The middle member (K2qn2) consists of grey to green mudstone,

white to grey fine-grained sandstone and siltstone. The upper member (K2qn3) is characterized by

white-gray fine- to coarse-grained sandstone intercalated with red silt-mudstone and green

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mudstone (Dong et al., 2014).

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3. Materials and methods

3.1 Samples

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This study focuses on the Changling Sag, primarily in the Daqingzi uplift and eastern slope

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region (Fig. 1B), as most discovered oil and gas reservoirs are situated in Daqingzi uplift and
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eastern slope region (Dong et al., 2014). A total of twenty-two mudstone samples and fifteen crude

oil samples were collected and analyzed. These samples were from different drilling wells (see
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well location in Fig. 1B) and different members of the Qingshankou Formation, including the
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upper (K2qn3), middle (K2qn2) and lower member (K2qn1) (Table 1 and 2). Eleven of the source
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rock samples were selected for extraction and biomarker studies. These samples were first cleaned

and then ground into powder. Samples were then sieved and Soxhlet extracted for 48 h using
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dichloromethane solution to obtain the source rock extracts. After solvent removal, the rock
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extractions were fractionated by column chromatography over activated silica gel into saturate,
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aromatic and resin fractions.

3.2 Rock-Eval pyrolysis

Total organic carbon (TOC) content for the twenty-two mudstone samples were determined

using Leco CS-200. All the mudstone samples were analyzed using Rock-Eval instrument for

Rock-Eval parameters. S1, S2, S3 and Tmax values were determined, and then hydrogen index (HI)
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and oxygen index (OI) were calculated.

3.3 Gas-chromatography (GC)

In order to determine molecular composition, saturated hydrocarbons of both rock extracts

and crude oils were analyzed by gas chromatography (GC), and gas chromatography-mass

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spectrometry (GC-MS) to determine molecular compositions of the samples.

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Gas chromatographic (GC) analysis of the saturated hydrocarbon from the crude oils and

source rock extracts was performed using an Agilent 7890 chromatograph (fused silica column, 60

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m0.25mm0.25 m) equipped with a flame ionization detector (FID). The oven temperature was

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initially held at 70 for 5 minutes, programmed to 300 at 3 /min and held at 300 for
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30minutes.

3.4 GC- mass spectrometry (GC-MS)

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Gas chromatography-mass spectrometry analyzes for saturated hydrocarbon and aromatic

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hydrocarbon were carried out on an Agilent 7890A gas chromatograph coupled with Agilent
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5975C mass spectrometer. A HP-5MS fused silica column (30 m0.25mm0.25 m) was used.

The carrier gas was helium with a flow rate of 1.2 mL/min. Injections were performed in a
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splitless mode at 300 , and the injection volume was 1.0 L. For analyzing saturated
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hydrocarbon fraction, the GC oven was initially set at 60 for 5 minutes, programmed to 300
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at 3 /min, with a final holding time of 30 min.

3.5 Stable carbon isotope analysis

Stable carbon isotope composition of the crude oils and source rock extracts were analyzed

using DELTA plus XL mass spectrometer and helium was the carrier gas. Isotopic composition is

reported in the notation relative to the Vienna Peedee Belemnite (VPDB).

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4. Results

4.1 Geochemistry of source rocks

4.1.1 Organic matter abundance, type and thermal maturity

The results of Rock-Eval pyrolysis on mudstone samples collected from K2qn2 and K2qn1

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members are displayed in Fig. 3A and Table 1. The TOC values of the mudstone samples from the

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Qingshankou Formation are in the range of 0.05 2.85 wt.%, with an average of 1.09 wt.% (Fig.

3A, Table 1). The K2qn2 displays widely variable organic-matter richness and hydrocarbon

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generating potential, with TOC content ranging from 0.05 to 2.26 wt.%(averaging 0.78 wt.%), and

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S1+S2 from less than 0.1 to 7.69 mg HC/g rock (Table 1). Samples from the lower member of the
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Qingshankou Formation (K2qn1) have relatively high TOC and S1+S2. TOC content ranges from

0.07 to 2.85 wt.%, averaging 1.27 wt.%, and S1+S2 ranges from less than 0.1 to 15.89 mg HC/g
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rock (Table 1). In the plot of S1+S2 versus TOC, most of the K2qn2 mudstone samples plot in the
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poor to fair source rock region, however, samples from K2qn1 plot in the fair to good source rock
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region (Fig. 3A).

In the hydrogen index (HI)-Tmax kerogen type classification diagrams, K2qn1 represents Type
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and Type field, and K2qn2 represents Type and Type kerogen (Fig. 3B). The TOC
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contents and hydrogen indices for the middle member of the Qingshankou Formation (K2qn2) are
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usually lower than those of K2qn1 member.

Tmax data from Rock-Eval analysis and vitrinite reflectance (Ro) are regarded as the most

effective parameters in the assessment of thermal maturity (Hunt, 1996). Samples from the lower

member have a wide range of Tmax data between 433 and 459 , with an average of 445 .

Samples from the middle member, however, have relatively low Tmax data, ranging from 329 to
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454 , average of 428 (Table 1). Dong et al. (2014) reported that the present maturity of the

Qingshankou Formation ranges from less than 0.7% Ro to less than 1% Ro.

4.1.2 n-Alkanes and isoprenoids

Among eleven saturated source rock extracts of K2qn2 and K2qn1 membe, there are minor

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differences in the molecular compositions of the extracts. The n-alkane distribution shows

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maximum intensities between nC16-nC18 alkanes in all samples (Fig. 4A and B). All the n-alkane

distributions of samples from K2qn2 and K2qn1 show front end biased distributions and no obvious

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odd-over-even predominance was observed. Sample from K2qn1 has higher amounts of

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low-molecular weight normal alkanes than that of sample from K2qn2 indicated by more skewed
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shape of gas chromatograms (Fig. 4A and B) and the C21-/C22+ ratio (Table 2).

The Pr/n-C17 and Ph/n-C18 alkane ratios for source rock extracts from the middle and lower
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member are tabulated in Table 2. The Pr/n-C17 and Ph/n-C18 ratios of samples from the lower
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member range from 0.24 - 0.38, 0.18 0.32, respectively. Samples from the middle member have
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relatively high Pr/n-C17 and Ph/n-C18, ranging from 0.19 0.88, 0.14 0.42, respectively. As

discussed earlier, Pr/Ph ratio is commonly used as an effective parameter in the assessment of
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redox conditions; low Pr/Ph reflects anoxic environments. Pr/Ph ratios of source rock samples
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from the lower member range from 1.29 to 2.20, with an average value of 1.71. In comparison,
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samples from the middle member display relatively higher Pr/Ph ratios, ranging from 0.87 to 3.3,

with an average of 1.9.

4.1.3 Steroids

Sterane mass chromatograms (m/z 217) for oils are characterized by a predominance of C29

relative to C28 and C27 steranes, however, there are some variations in the distribution of C27, C28,
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C29 steranes between samples from the middle and the lower member (Fig. 4C and D). The source

rock extracts from the lower member have the relative content of regular C27, C28 and C29 steranes

in the range of 0.18 0.35, 0.23 0.29 and 0.4 0.56, respectively (Fig. 8B and Table 2). The

middle member of the Qingshankou Formation has the relative content of C27, C28 and C29

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steranes ranging from 0.14 0.38, 0.19 0.25, 0.37 0.66, respectively (Fig. 8B and Table 2).

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The two different sterane thermal maturity parameters, C29 20S/(20S+20R) and the C29

/(+), are tabulated in Table 2 and plotted in Fig. 10B. The values of C29 20S/(20S+20R)

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and C29 /(+) for samples from the lower member range from 0.47 0.78, 0.36 0.42,

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averaging 0.67 and 0.39, respectively. Samples from the middle member have relatively low
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values of C29 20S/(20S+20R) and C29 /(+), averaging 0.56 and 0.36, respectively.

4.1.4 Terpenoids
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The mass chromatograms for terpanes (m/z 191) from both the lower and middle member
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samples show high intensities of C30 hopane, and decreasing relative proportions of extended
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hopanes from C31 to C35 (Fig. 4 E and F). Tm and Ts are regarded as effective parameters to assess

the maturity, with high concentration of Ts indicating high maturity (Peters et al., 2005; Cheng et
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al., 2013). As shown in Fig. 4 E and F, samples from the middle and lower member (K2qn1) have
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relatively higher concentration of Ts than that of Tm.

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The three parameter, C19/C23 tricyclic terpane, C24 tetracyclic/C26 tricyclic terpane and

gammacerane/C30 hopane are calculated and listed in Table 2. Samples from the lower member

display C19/C23 tricyclic terpane between 0.25 and 1.09, averaging 0.58, and samples from the

middle have values ranging from 0.41 to 0.96, averaging 0.63. The lower member has C24

tetracyclic/C26 tricyclic terpane between 0.24 and 1.93, with an average of 0.75. The middle
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member has C24 tetracyclic/C26 tricyclic terpane ranging from 0.54 to 2.47, with an average of

1.22.

The gammacerane, which is also resistant to biodegradation, is indicative of stratified water

columns in marine and nonmarne source rock depositional environments (Sinninghe Damst et al.,

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1995; Hao et al., 2009; Chang et al., 2013). Samples from the lower member contain high amounts

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of gammacerane with the values of gammacerane index ranging from 0.13 to 0.61, averaging 0.29.

The investigated source rocks from the middle member has a wide range of gammacerane indices

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and ranging from 0.05 to 0.85, averaging 0.28 (Table 2).

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4.1.5 Stable carbon isotope composition
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Previous studies demonstrated that the carbon isotopic compositions of saturated and

aromatic hydrocarbon are very useful to distinguish various source rocks (Hayers et al., 1987;
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Odden et al., 2002; Yu et al., 2012). The plot of the carbon isotope values of the saturated and
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aromatic hydrocarbons of source rock extracts from the Qingshankou Formation are shown in Fig.
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12A and Table 4. The 13C values of saturated and aromatic hydrocarbon fractions of source rock

extracts from the lower member range from -32.01 to -29.11, and from -30.43 to -27.27,
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respectively. The source rocks from the middle member are characterized by relatively high 13C
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values of saturated and aromatic hydrocarbon fractions, in the range from -29.92 to -27.11,
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and from -27.89 to -25.82, respectively.

4.1.6 Fluorene, dibenzofuran and dibenzothiophene

Fluorene, dibenzofuran and dibenzothiophene have been widely used to study the depositional

environment (Fan et al., 1990; Huang and Pearson, 1999; Asif et al., 2009). Dibenzothiophene can

be concentrated in strongly reducing environment, while dibenzofuran accumulated in freshwater

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environment (Fan et al., 1990). The relative abundance of dibenzofurans in the source rock

samples from K2qn1 and K2qn2 varies from 1.5% to 8.7%, 2.7% to 9.3%, respectively, much lower

than the relative abundance of fluorene and dibenzothiophene (Fig. 5).

4.2 Geochemistry of crude oils

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4.2.1 Crude oil composition

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The gross compositions of all the crude oils are tabulated in Table 3. Amounts of saturates,

aromatics, resins and asphaltenes range from 64.5-72.4, 19.1-24.3, 5.3-13.5, and 0.3-2.9,

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respectively. All the crude oils have similar saturate/aromatic hydrocarbon ratios, ranging from 2.8

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to 3.8, exhibiting the typical characterization of gross compositions in normal maturity oils.
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4.2.2 Normal alkanes and isoprenoid distribution

From the 15 crude oils examination, the patterns of n-alkane distribution are similar and only
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minor differences in the molecular compositions are observed. As shown in Fig. 6, the gas
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chromatograms of selected oils, one from the K2qn3 member, one from the K2qn2 member and
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another one from the K2qn1 member, show front end biased distributions. These oils are

predominantly characterized by short chained n-alkanes, with C21-/C22+ ratios ranging from 1.45
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to 3.25 (Table 2). No even/odd predominance was observed and the OEP for all samples are close
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to 1, indicating mid-oil window thermal maturity of the source at the time of the expulsion. The
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amounts of n-alkanes decrease with increase in the number of carbons.

The Pr/n-C17 and Ph/n-C18 alkane ratios are shown in Table 2. Obviously, all the oil samples

have similar ranges of Pr/n-C17 and Ph/n-C18 ratios. Crude oils from Qingshankou reservoirs have

narrow variations of Pr/n-C17 and Ph/n-C18 ratios, ranging from 0.2 0.31 and 0.15 0.23,

respectively (Table 2).

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It has been long recognized that the relative amounts of pristine and phytane in rock extracts or

crude oils, expressed as Pr/Ph ratios, can be used as indicators of source depositional

environments (Didyk et al., 1987; Zhang and Huang, 2005). High values (Pr/Ph > 3) indicate

terrigenous organic matter input under oxic conditions (Powell and Mckirdy, 1973), whereas low

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values (Pr/Ph < 1) suggest anoxic conditions (Hunt, 1996. Harris et al., 2004). Moreover,

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extremely low Pr/Ph ratios (< 0.8) indicate stratified water column or hypersaline environments

(Peters et al., 2005; Zhang and Huang, 2005; Cheng et al., 2013). All the examined crude oils in

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this study have similar Pr/Ph ratios; ranging from 1.43 to 1.75, averaging 1.58 (Table 2). This

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indicates that oils derived from the source rocks deposited under weak to intense anoxic
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conditions.

4.2.3 Steroids
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In order to extract useful information from biomarker assemblages, gas

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chromatography-mass spectrometry (GC-MS) analysis was conducted on the fifteen oil samples
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and representative mass fragmentograms for steranes and hopanes are shown in Fig. 6. Although

diasteranes are observed in significant amounts, their concentrations are lower than those of the
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regular steranes. The concentrations of regular steranes and diasteranes in crude oils range from
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58.5-73.4, 19.4-29.2, respectively (Table 2). Sterane mass chromatograms (m/z 217) for crude oils
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are characterized by a predominance of C29 relative to the C28 and C27 steranes (Fig. 7). The

relative abundance of C27, C28 and C29 steranes are useful indicators for the source organic matter

input and often used to differentiate oil origins (Hunt, 1996; Samuel et al., 2009). The normalized

relative abundance of C27 steranes varies from 21.5-30.9%, C28 steranes between 19.9-26.9% and

C29 steranes between 44.5-58.4% (Table 2). The ternary diagram of the relative distribution of
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C27-29 steranes (Fig. 8A) shows that all the oils are grouped together and shifted slightly towards

C29.

4.2.4 Terpenoids

The mass chromatograms for terpanes (m/z 191) are characterized by high intensities of C30

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hopane (Fig. 7). Tricyclic terpanes are widely used in classifying crude oil origins (Peters, 2000;

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Peters et al., 2005; Bennett and Olsen, 2007; Hao et al., 2009), and C19/C23 tricyclic terpane is

usually considered to be useful indicator of terrigenous organic matter input (Volk et al., 2005).

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Samples from the lower member display C19/C23 tricyclic terpane between 0.43 and 1.19 (Fig. 9A

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and Table 2). The C19/C23 tricyclic terpane of the middle member ranges from 0.57 to 0.87. The
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only sample from the upper member has a C19/C23 tricyclic terpane of 0.55.

Tetracyclic terpanes are commonly used to classify oil origins and characterize source rocks,
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as they are thermally stable and resistant to biodegradation (Peters et al., 2005). Previous studies
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suggest that abundant tetracyclic terpane in saturated hydrocarbon is indicative of carbonate and
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evaporate source rock setting (Connan et al., 1986; Clark and Philip, 1989; Hao et al., 2009).

However, some studies demonstrate that abundant tetracyclic terpane may indicate high terrestrial
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organic matter input (Zhang and Huang, 2005; Duan et al., 2008). The lower member of the
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Qingshankou Formation displays C24 tetracyclic/C26 tricyclic terpane between 0.4 and 0.67,
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averaging 0.49 (Fig.9B and Table 2). The investigated oils from the middle member have a similar

range of C24 tetracyclic/C26 tricyclic terpane values, ranging from 0.45 to 0.74. The only sample

from the upper member has a value of 0.71. In the Qingshankou Formation, gammacerane was

detected in all crude oil samples (Fig. 7). The gammacerane index, defined as the ratio of

gammacerane to C30 hopane concentration, ranges from 0.17 to 0.64 (Fig. 9C and Table 2).
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Previous studies demonstrated that the ratio of C29 20S/(20S+20R) and C29 /(+)

steranes are the most commonly used indicators to estimate the maturity of oils (Peters and

Moldowan, 1993; Peters et al., 2005). The 20S/(20S+20R) and /(+) C29 sterane ratios of

the oils have similar ranges; 0.64 to 0.77, and from 0.41 to 0.5, respectively (Fig. 10A and Table 2).

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This indicates that all the crude oils from different intervals of the Qingshankou Formation are of

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equivalent maturity. These two parameters suggest that the oils are expelled from source rocks that

were exposed to a thermal maturity level equivalent to the peak oil window stage of petroleum

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generation.

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4.2.5 Bulk stable carbon isotopic compositions
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The carbon isotopic compositions of oils are widely used to determine oil-oil and oil-source

rock correlations (Schoell, 1984; Chung et al., 1992; Zhang and Huang, 2005). The plot of the
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carbon isotope values of the saturated and aromatic hydrocarbons in the oils from the
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Qingshankou Formation are shown in Fig. 12B. The 13C values of saturates and aromatics for the
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15 crude oils range from -31.46 to -30.62 and from -30.21 to -29.14, respectively (Table

4).
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5. Discussion
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5.1 Geochemical characterization and hydrocarbon generation potential of K2qn1 and K2qn2
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members

The plot of TOC content versus S1+S2 reveals that most source rock samples from the lower

member are of fair to good source rock quality, while, the middle member show poor to fair source

rock quality with only a few samples show of good source rock quality (Fig. 3A). Most source

rock samples from the lower member are hydrogen-rich, oil prone and have high hydrocarbon
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generating potential. Samples from the middle member are relatively hydrogen-poor, gas-prone

and have low hydrocarbon generating potential (Fig.3B). Some of the mudstone samples from the

lower member (K2qn1) contain type organic matter. Samples from the lower member are more

mature than samples from the middle member indicated by Tmax data. This is consistent with the

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observation on biomarker fingerprints. Normal alkane distributions of sample from K2qn1 are

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characterized by relatively higher amounts of low-molecular weight normal alkanes and relatively

lower concentration of pristine and phytane than that of sample from the middle member, which is

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indicative of more mature character. The sterane maturation parameters, C29 20S/(20S+20R) and

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C29 /(+) ratios of source rock extracts from the lower member are relatively higher than to
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those of the middle member (Fig. 10B), indicating that the lower member was more mature. It can

be easily concluded that source rocks in the lower member have more hydrocarbon generating
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potentials than the middle member.

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5.2 Origin of organic matter-rich mudstone deposition in the Qingshankou Formation

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The relative abundances of C27-C29 regular steranes, C19/C23 tricyclic terpane, and C24

tetracyclic/C26 tricyclic terpane ratios are good indicators for source organic matter input (Peters
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and Moldowan, 1993; Peters et al., 2005). C27 and C28 steranes are believed to related to marine
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algal influence, while C29 steranes generally indicate a contribution from land plant organic matter
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(Peters et al., 2005; Hakimi and Abdullah, 2013; Dong et al., 2015). The relative distribution of

C27-C29 steranes (Fig. 8B and Table 2) suggest that source rocks in both the lower member and

the middle member have a dominant contribution from terrigenous organic matter, because the

abundance of C29 sterane is higher than C27 and C28 steranes. However, there are still differences in

the relative proportion of terrigenous organic matter and marine organic matter input indicated by
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the C19/C23 tricyclic terpane and C24 tetracyclic/C26 tricyclic terpane ratios. High C19/C23 tricyclic

terpane and C24 tetracyclic/C26 tricyclic terpane ratios are usually indicative of terrigenous organic

matter input (Volk et al., 2005; Zhang and Huang, 2005). Mudstone samples from the lower

member are characterized by relatively low C19/C23 tricyclic terpane (average 0.58) and low C24

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tetracyclic/C26 tricyclic terpane (average 0.75) (Table 2). In contrast, mudstone samples from the

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middle member are characterized by relatively high C19/C23 tricyclic terpane (average 0.63) and

high C24 tetracyclic/C26 tricyclic terpane (average 1.22). This may indicate that the middle member

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source rock has more contribution from terrigenous organic matter compared to the lower member.

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Depositional environment is thought to be another factor that controls organic matter
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enrichment and type in mudstones. The lower member has lower Pr/Ph ratios (average 1.71) than

that of the middle member (average 1.9), indicating that the lower member was deposited in more
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reducing conditions. Gammacerane/C30 hopane ratios range from 0.06 to 0.85 in the mudstone
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samples (Fig. 4E, F and Table 2), indicating a stratified and reducing water column and saline,
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anoxic conditions for the K2qn1 and K2qn2 deposition. This is also confirmed by the relative

abundance of fluorene, dibenzofuran and dibenzothiophene (Fig. 5). In this study, the higher
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abundance of dibenzothiophene than fluorene suggest strongly reducing environment for the
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Qingshankou Formation deposition. As shown in Table 2, gammacerane index in the lower

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member is higher than in the middle member, suggesting a less stratified water column for K2qn2

deposition.

Biomarkers including normal alkanes, isoprenoids, terpenoids and steroids suggest within the

lower member (K2qn1) are different from those within the middle member (K2qn2), reflecting the

differences in source organic matter input, depositional environment and thermal maturity. The
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lower member of the Qingshankou Formation was deposited in anoxic water conditions with more

contribution from sapropelic organic matter, and is more thermally mature. The middle member

was deposited under reduced anoxic conditions with more contribution from terrigenous organic

matter, and is less thermally mature.

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Previous studies demonstrate that the Songliao paleo-lake was a freshwater lake and marine

incursion events occurred during the deposition of the K2qn1 member (Huang et al., 2013). Bechtel

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et al. (2012) suggest a stratified water column and saline, anoxic conditions for the K2qn1

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deposition. Their interpretations on the palaeoenvironmental conditions for K2qn1 deposition are

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consistent with our results. The significant presence of gammacerane and C30 steranes (Fig. 4D, E
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and F) in this study also indicate anoxic conditions with marine influence. In this study, combined

with previous studies, we proposed a new model for the mudstone deposition from K2qn1 to K2qn2.
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During the deposition of the lower member (K2qn1), this basin experienced a post-rift thermal
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subsidence period (Bechtel et al., 2012; Wang et al., 2013), resulting in a marine transgressional
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event. Influx of saline seawater into the basin lead to a stratified water column, creating anoxic

conditions in the water bottom which was beneficial for organic matter deposition. During the
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deposition of K2qn2 member, sea level drop resulted in decreasing water column and less
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connection to the ocean. Less salinity and short water depth would make dissolved oxygen easily
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to reach the water bottom, lead to less anoxic conditions, as demonstrated by the relatively high

Pr/Ph ratios. Meantime, more terrigenous organic matter would be transported into the basin as the

shoreline was dropping, which was suggested by higher C19/C23 tricyclic terpane and C24

tetracyclic/C26 tricyclic terpane ratios (Table 2).

5.3 Origins of crude oils

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Biodegradation is a process that alters fluid properties of hydrocarbon such as gross

composition and molecular composition, and may occur in oil reservoirs (Asif et al., 2011). It is

important to check whether or not the crude oils have been biodegraded. Biodegradation is

characterized by the loss of n-alkanes at an early stage, and is followed by the loss of acyclic

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isoprenoids (Hakimi and Abdullah, 2013). In biodegraded oils, normal alkanes have relatively low

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concentration compared to branched and cyclic saturated hydrocarbons which are more resistant to

biodegradation (Hakimi and Abdullah, 2013). Oils from Qingshankou reservoir contain a complete

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suite of normal alkanes (Fig. 6), indicating that the samples are non-biodegraded. This is also

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indicated by the fact that all the crude oils contain more saturated hydrocarbons than aromatic
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hydrocarbons with saturate/aromatic hydrocarbon ratios > 2.8 (Table 3). The very low values of

Pr/n-C17 (< 0.35) and Ph/n-C18 (<0.25) for all samples, also indicate that there is no sign of
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biodegradation among oil samples (Volkman et al., 1983).

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The gross composition of all the crude oils is characterized by a high amount of saturates with
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saturates/aromatics ratios more than 2.8 show of mature oil character (Table 3). The gas

chromatograms shown in Fig. 6 display front end biased distributions, which is consistent with the
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idea of mature character for all these crude oils. As tabulated in Table 2, all the crude oils have
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narrow range of Pr/n-C17 and Ph/n-C18, indicating compositional similarity and likely origination
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from a single source rock. Similar biomarker fingerprints in m/z 191 and 217 mass chromatograms

are further indications for good oil-oil correlation (Fig. 7).

As discussed earlier, C19/C23 tricyclic terpane and C24 tetracyclic terpane/ C26 tricyclic terpane

are regarded as effective parameters for terrigenous organic matter input, however, no positive

relationship between them was observed (Fig. 9D). It shows us that C19/C23 tricyclic terpane has
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negative correlation to Pr/Ph ratios (Fig. 9A), suggesting that C19/C23 tricyclic terpane is not

related to depositional environment. The positive correlation between C19/C23 tricyclic terpane and

C29 /(+) sterane ratios (Fig. 11) indicate that the variation in C19/C23 tricyclic terpane is

controlled by thermal maturity. Obviously, C24 tetracyclic terpane/ C26 tricyclic terpane increases

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as Pr/Ph increase (Fig. 9B), indicating that C24 tetracyclic terpane/ C26 tricyclic terpane has a close

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relationship to depositional environment and/or organic matter input (Hao et al., 2009). In this

case, C24 tetracyclic terpane/ C26 tricyclic terpane is a more reliable proxy for terrigenous organic

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matter input. The positive correlation between C24 tetracyclic terpane/ C26 tricyclic terpane ratios

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and Pr/Ph (Fig. 9B) demonstrate that as the redox conditions become more reducing, the relative
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proportion of marine-derived organic matter increases. A negative relationship between the

gammacerane index and Pr/Ph ratios was observed for all the crude oils samples (Fig. 9C),
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suggesting that water stratification is probably the main reason for anoxic environment
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development
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All the oil samples from the Qingshankou Formation are classified into one group, as they

have similar ranges of carbon isotope values (Fig. 10A). Both biomarker assemblage and carbon
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isotopic composition of saturated and aromatic hydrocarbon suggest that all the crude oils from
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the Qingshankou reservoir probably originated from a common source rock.

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. The two maturation parameters C29 20S/(20S+20R) and C29 /(+) sterane ratios are

high for all the oil samples (average 0.73 and 0.44, respectively) (Fig. 10A and Table 2), and

equilibrium has been attained, particularly for the C29 20S/(20S+20R) ratios, indicating the all the

crude oils are mature. This is also supported by the fact that the concentration of Ts is much higher

than that of Tm hopane (Fig. 7). There is clearly co-elution of another compound with the C29 20S
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steranes, as the C29 20S/(20S+20R) ratios is very high (Table 2), which makes the evaluation

on maturity using C29 20S/(20S+20R) questionable.

5.4 Oil-source rock correlation and oil migration

9 of the 22 selected mudstone samples are not source rocks at all as they have TOC content of

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less than 0.4 wt.% (Table 1). Only the remaining 13 mudstones could be potential source rocks. 7

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samples out of the 13 potential source rocks were performed on GC-MS and carbon isotope

analysis. We conducted oil to source rock correlation on the 7 mudstone samples and the 15 crude

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oil samples.

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Hierarchical cluster analysis (HCA) is a commonly used statistical technique to distinguish
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crude oils from different source rocks using multiple parameters. Fig. 13 shows the dendrogram

using parameters listed in Table 2 and Table 4, like Pr/n-C17, Ph/n-C18, Pr/Ph, C29 /(+), C27
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sterane, C28 sterane, C29 sterane, C24/C26, gammacerane/hopane and stable carbon isotope data.
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The HCA separates the analyzed oil samples into one group and separates the analyzed source
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rock samples into two groups, as shown in Fig. 13. There are three source rock samples from the

K2qn1 and one source rock sample from K2qn2 falling into the group A. The investigated oils
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belong to one single family, based on their bulk chemical composition, biomarker fingerprints and
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stable carbon isotope. Biomarker parameters (Table 2) and carbon isotopic data (Table 4) for
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source rock samples from the lower member (K2qn1) have a closer match to all the 15 oils from

the lower, middle and upper member of the Qingshankou Formation in this study. Carbon isotopes

of saturates and aromatics from the middle member source rocks are much higher than carbon

isotopes in crude oils (Fig. 12). These data suggests that the lower member was the major source

rock for oil generation.

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Source rocks from the lower and middle members show some similarity and overlap in the

variation of Pr/n-C17, Ph/n-C18, C28/C29 regular steranes, C29 /(+), Ts/Ts+Tm, and

gammacerane/C30 hopane (Table 2). Comparison of the biomarker signatures in the analyzed oils

and organic extracts from K2qn2 shows they exhibit some similarities in n-alkane, steranes and

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terpanesdistribution (Figs. 4, 6 and 7). Here, we propose the possibility of oils are mixture derived

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from both the lower and middle member source rocks, with minor contribution from the middle

member. All the crude oils have an obvious genetic relationship with the lower member source

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rocks, however, the middle member source rocks may secondarily contribute to the discovered

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oils.
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Petroleum potential analysis suggests that the lower member of the Qingshankou Formation is

the primarily effective source rocks in the Changling Sag. Previous studies suggest that strong
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faulting systems striking NE and NW were developed due to the tectonic inversion (Fig. 1C), and
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have acted as effective conduit networks for hydrocarbon migration (Li et al., 2002; Li et al., 2009;
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Dong et al., 2014). Connective sandstone body developed in the Qingshankou Formation is

another carrier beds for hydrocarbon migration (Gong and Shen, 2012). These two main pathways
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connected the lower, middle and upper member of Qingshankou Formation and enable the oil
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produced from the lower member to migrate into the middle and upper members.
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6. Conclusion

Bulk geochemical data, biomarker assemblage coupled with carbon isotopic data were used

to investigate the origins of source rock deposition, oils in the Qingshankou Formation, Changling

Sag and determine the relative source rocks.

The lower member of the Qingshankou Formation (K2qn1) has more hydrocarbon generation
 ACCEPTED MANUSCRIPT

potential than the middle member (K2qn2), because source rocks in the lower member have higher

TOC content and are oil-prone and more mature. K2qn1 source rocks are characterized by

relatively lower Pr/Ph ratios, lower C19/C23 tricyclic terpane, lower C24 tetracyclic/C26 tricyclic

terpane, moderate gammacerane index, and were deposited in saline water column, anoxic

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environments with more contribution from sapropelic organic matter. In comparison to the first

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member, source rocks from the middle member have relatively higher Pr/Ph ratios, higher C19/C23

tricyclic terpane, higher C24 tetracyclic/C26 tricyclic terpane, and were interpreted to deposit in less

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anoxic environments with more contribution from terrigenous organic matter.

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All crude oils discovered in the Qingshankou Formation, Changling Sag generally fall into
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one family, as they display similarity in gross composition and biomarker fingerprints. Biomarker

parameters suggest that all the oils are mature and have significant contribution from the K2qn1
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source rocks and minor contribution from the K2qn2 source rocks.
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Acknowledgements:
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We sincerely thank Dr. Harish Veeramani and two anonymous reviewers for their detailed and

constructive reviews. This study was supported by SINOPEC Northeast Oil and Gas Branch
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Company, the National Major Petroleum Project of China, the Foundation of Key Laboratory of
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Tectonics and Petroleum Resources of Ministry of Education, China University of Geosciences,

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and Introducing Talents of Discipline to Universities of Geoscience (Wuhan) (No.B14031). We

thank SINOPEC Northeast Oil and Gas Branch Company for financial assistance to this research

and arranging access to data files. Also special thanks are extended to the State Key Laboratory of

Geological Processes and Mineral Resources, China University of Geosciences.

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Table 1. Rock-Eval pyrolysis and TOC data for source rock samples from Qingshankou Formation, Changling Sag

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Well Depth(m) Member Lithology TOC (%) S1 (mg/g) S2 (mg/g) S1+S2 (mg/g) Tmax () HI (mg/g TOC) OI (mg/g TOC)
2
ZH1 1401.9 K2qn mudstone 2.26 0.27 1.81 2.08 434 80 10

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YD101 1852.24 K2qn mudstone 0.41 0.05 0.29 0.34 441 71 32
2
Y308 1893.82 K2qn mudstone 0.13 0.01 0.04 0.05 329 31 138

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DB6 2143.3 K2qn2 mudstone 0.07 0.01 0.01 0.02 438 14 129
2
SN307 2160.5 K2qn mudstone 0.05 0 0 0 454 0 140
2

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YX102 2232.9 K2qn mudstone 0.15 0 0.01 0.01 438 7 100
2
SN309 2263.04 K2qn mudstone 0.99 0.1 2.7 2.8 443 273 6

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YN2 2501.8 K2qn2 mudstone 2.16 0.51 7.18 7.69 445 332 2
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ZH1 1567.8 K2qn mudstone 0.15 0 0.03 0.03 433 20 107

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YD101 1941.3 K2qn mudstone 2.13 1.43 11.07 12.5 445 520 5
1
YZ301 1946.72 K2qn mudstone 1.81 0.54 8.62 9.16 442 476 8

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Y308 1963.5 K2qn1 mudstone 0.96 0.16 3.29 3.45 447 343 14

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YZ3 2147.9 K2qn mudstone 0.84 0.61 2.86 3.47 441 340 23
1
SN307 2261.6 K2qn mudstone 1.02 0.17 3.6 3.77 446 353 8
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SN309 2276.3 K2qn mudstone 0.07 0 0.02 0.02 453 29 186
SN309 2291.98 K2qn1 mudstone 0.09 0 0.01 0.01 433 11 56
1
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YX102 2292.75 K2qn mudstone 2.45 0.28 12.18 12.46 446 497 1
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DB6 2365.5 K2qn mudstone 2.59 0.98 14.91 15.89 444 576 3
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YZ2 2425 K2qn mudstone 2.29 2.41 9.56 11.97 446 417 5
YN3 2554.08 K2qn1 mudstone 0.14 0 0.01 0.01 459 7 79
1
YN2 2598.6 K2qn mudstone 2.85 0.58 8.57 9.15 448 301 7
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YN2 2628.1 K2qn1 mudstone 0.36 0.03 0.17 0.2 450 47 3

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Table 2. Molecular composition for source rock samples and crude oils from Qingshankou Formation, Changling Sag
C24

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Regular C27/ C28/ C29/ C19/C23
C29 sterane C29 sterane tetracyclic/ Gammacerane/
Sample Well Depth(m) Member OEP Pr/C17 Ph/C18 Pr/Ph C21-/C22+ Diasterane(%) sterane tricyclic

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20S/20S+20R /+ C26 tricyclic C30 hopane
(%) C27-C29 C27-C29 C27-C29 terpane
terpane
2

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Mudstone YD101 1852.24 K2qn 1.16 0.49 0.30 2.33 1.69 n.m. n.m. 0.14 0.20 0.66 0.50 0.37 0.92 2.47 0.05
2
Mudstone Y308 1893.82 K2qn 0.74 0.42 0.38 1.25 9.64 n.m. n.m. 0.32 0.23 0.45 0.35 0.35 0.41 0.69 0.16
2
Mudstone YX102 2232.9 K2qn 1.11 0.35 0.42 0.87 2.64 n.m. n.m. 0.38 0.25 0.37 0.52 0.38 0.41 0.74 0.19

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Mudstone SN309 2263.04 K2qn 1.03 0.88 0.28 3.30 2.21 n.m. n.m. 0.34 0.19 0.47 0.67 0.30 0.46 1.65 0.14

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Mudstone YN2 2501.8 K2qn 1.04 0.19 0.14 1.77 4.35 n.m. n.m. 0.27 0.24 0.48 0.79 0.41 0.96 0.54 0.85
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Mudstone ZH1 1567.8 K2qn 0.88 0.35 0.32 1.54 7.89 n.m. n.m. 0.35 0.25 0.40 0.47 0.37 0.64 0.69 0.13
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Mudstone YD101 1941.3 K2qn 1.05 0.37 0.31 1.29 1.34 n.m. n.m. 0.19 0.25 0.56 0.77 0.41 0.25 0.32 0.26
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Mudstone SN307 2261.6 K2qn 1.03 0.38 0.18 2.20 1.45 n.m. n.m. 0.23 0.23 0.54 0.74 0.36 0.63 1.93 0.20
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Mudstone YX102 2292.75 K2qn 0.96 0.24 0.21 1.61 4.42 n.m. n.m. 0.28 0.25 0.47 0.75 0.42 1.09 0.96 0.61
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Mudstone YZ2 2425 K2qn 1.03 0.33 0.20 1.69 1.22 n.m. n.m. 0.18 0.29 0.53 0.78 0.39 0.45 0.24 0.26
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Mudstone YN2 2628.1 K2qn 1.07 0.37 0.25 1.93 3.27 n.m. n.m. 0.35 0.24 0.41 0.49 0.40 0.40 0.34 0.30
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Crude oil SK3-2 2176-2179 K2qn 1.01 0.29 0.20 1.75 2.48 19.4 73.4 0.24 0.24 0.52 0.74 0.42 0.55 0.71 0.20
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Crude oil DB25 1956.1-1956.2 K2qn 1.03 0.23 0.18 1.54 2.42 24.5 65.7 0.27 0.25 0.48 0.73 0.46 0.73 0.46 0.44
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Crude oil DB13 2006.6-2008.5 K2qn 1.02 0.22 0.16 1.52 2.54 26.3 64.0 0.25 0.23 0.52 0.71 0.44 0.88 0.45 0.42
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Crude oil SN311 2228.8-2234 K2qn2 1.03 0.30 0.20 1.65 1.45 19.8 71.9 0.25 0.20 0.55 0.73 0.41 0.57 0.74 0.17
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Crude oil SNK301 2241-2243.2 K2qn 1.04 0.27 0.19 1.56 1.55 20.2 72.5 0.31 0.25 0.45 0.77 0.43 0.67 0.67 0.23

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Crude oil DB37 2256.2-2263.8 K2qn 1.03 0.25 0.19 1.43 1.39 22.3 68.3 0.26 0.22 0.52 0.73 0.44 0.69 0.53 0.43
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Crude oil DB33 2265.5-2273 K2qn 0.97 0.21 0.15 1.72 3.22 25.6 65.5 0.26 0.25 0.50 0.74 0.44 0.69 0.65 0.38

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Crude oil Y401 1951.4-1970.1 K2qn 1.07 0.30 0.23 1.63 2.04 23.4 68.9 0.25 0.23 0.52 0.72 0.43 0.43 0.43 0.28
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Crude oil DB16 2024.1-2041.4 K2qn 1.03 0.31 0.20 1.65 1.35 26.9 64.5 0.28 0.24 0.49 0.77 0.41 0.86 0.65 0.21

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Crude oil DB22 2076.6-2181.8 K2qn 1.05 0.22 0.17 1.48 1.75 25.0 63.6 0.27 0.21 0.52 0.73 0.44 0.86 0.43 0.40
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Crude oil DB25 2147.4-2149.9 K2qn 1.04 0.23 0.17 1.54 2.7 26.3 62.2 0.23 0.24 0.53 0.70 0.44 0.74 0.46 0.51
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Crude oil YB1 2247.5-2282.4 K2qn 1.03 0.21 0.15 1.51 1.84 29.2 58.5 0.21 0.20 0.58 0.64 0.50 1.19 0.44 0.53

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Crude oil YB1 2274.7-2282.3 K2qn 1.03 0.20 0.15 1.46 1.85 28.3 60.0 0.24 0.27 0.49 0.72 0.47 1.17 0.40 0.64

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Crude oil DB34 2303.2-2315.5 K2qn 0.97 0.22 0.16 1.54 1.83 23.8 64.1 0.31 0.21 0.49 0.75 0.46 1.05 0.46 0.45
1
Crude oil DB33 2340.1-2351.7 K2qn 1.01 0.21 0.15 1.69 3.25 24.7 66.5 0.28 0.22 0.50 0.75 0.45 0.82 0.67 0.38

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Table 3. Gross composition for crude oils from Qingshankou Formation, Changling Sag
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Well Depth(m) Member Saturates(%) Aromatics(%) Resins(%) Asphaltenes(%) Sat/Aro
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SK3-2 2176-2179 K2qn 72.4 19.8 6.0 1.7 3.7
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DB25 1956.1-1956.2 K2qn 69.5 22.7 6.2 1.6 3.1

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DB13 2006.6-2008.5 K2qn 64.5 20.6 13.5 1.4 3.1
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SN311 2228.8-2234 K2qn 71.5 19.8 7.2 1.6 3.6
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SNK301 2241-2243.2 K2qn 71.6 19.3 6.7 2.3 3.7
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DB37 2256.2-2263.8 K2qn 68.6 21.5 7.1 2.9 3.2
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DB33 2265.5-2273 K2qn2 71.5 19.8 6.4 2.3 3.6

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Y401 1951.4-1970.1 K2qn 72.3 19.1 7.1 1.5 3.8

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DB16 2024.1-2041.4 K2qn 71.9 21.0 6.4 0.7 3.4
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DB22 2076.6-2181.8 K2qn 71.8 21.9 5.3 1.0 3.3

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DB25 2147.4-2149.9 K2qn 69.1 22.3 7.8 0.7 3.1
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YB1 2247.5-2282.4 K2qn 69.1 24.3 6.3 0.3 2.8

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YB1 2274.7-2282.3 K2qn 70.5 22.9 5.7 0.9 3.1
DB34 2303.2-2315.5 K2qn1 71.6 20.3 6.1 2.0 3.5

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DB33 2340.1-2351.7 K2qn 69.7 22.2 6.1 1.9 3.1

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Table 4. Carbon isotope composition source rock samples and crude oils from Qingshankou Formation, Changling Sag

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Stable carbon isotopes(, VPDB)
Well Depth(m) Member Sample
Whole oil Saturates Aomatics Resins Asphaltenes

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2
YD101 1852.24 K2qn Mudstone -26.32 -27.11 -25.82 -25.94 -24.15

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Y308 1893.82 K2qn Mudstone -28.04 -28.74 -27.57 -28.27 -26.9
2
YX102 2232.9 K2qn Mudstone -26.89 -29.48 -27.89 -26.72 -25.58
2
SN309 2263.04 K2qn Mudstone -26.92 -28.15 -26.29 -26.08 -25.13
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YN2 2566.3 K2qn Mudstone -29.22 -29.92 -27.23 -28.03 -27.52
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ZH1 1567.8 K2qn Mudstone -28.46 -29.69 -27.27 -27.3 -26.15
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YD101 1941.3 K2qn Mudstone -31.12 -32.01 -30.43 -30.38 -30.3
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SN307 2261.6 K2qn Mudstone -29.07 -29.78 -27.72 -27.8 -26.21
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YX102 2292.75 K2qn Mudstone -29.66 -30.4 -29.04 -28.97 -28.53
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YZ2 2425 K2qn Mudstone -30.13 -30.75 -28.62 -28.47 -28.13
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YN2 2628.1 K2qn Mudstone -28.26 -29.11 -27.3 -27.55 -26.59
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SK3-2 2176-2179 K2qn3 Crude Oil -30.23 -31.13 -29.54 -28.51 -28.95
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DB25 1956.1-1956.2 K2qn Crude Oil -30.72 -30.86 -30.18 -29.27 -29.48

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DB13 2006.6-2008.5 K2qn Crude Oil -30.88 -31.28 -30.02 -29.57 -29.5
SN311 2228.8-2234 K2qn2 Crude Oil -30.93 -31.18 -29.59 -28.76 -29.15

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SNK301 2241-2243.2 K2qn Crude Oil -30.79 -31.09 -29.14 -28.88 -29.21
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DB37 2256.2-2263.8 K2qn Crude Oil -30.95 -31.11 -29.59 -29.14 -29.22

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DB33 2265.5-2273 K2qn Crude Oil -30.45 -30.62 -29.45 -28.92 -29.02
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Y401 1951.4-1970.1 K2qn Crude Oil -31.29 -31.42 -29.68 -29.48 -29.31

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DB16 2024.1-2041.4 K2qn Crude Oil -30.89 -31.36 -29.61 -28.96 -29
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DB22 2076.6-2181.8 K2qn Crude Oil -31.22 -31.36 -30.21 -29.42 -29.47
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DB25 2147.4-2149.9 K2qn Crude Oil -31.06 -31.46 -29.99 -29.49 -29.36
YB1 2247.5-2282.4 K2qn1 Crude Oil -30.43 -31.44 -29.86 -29.15 -28.77

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YB1 2274.7-2282.3 K2qn Crude Oil -30.92 -31.37 -30.01 -29.47 -29.19
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DB34 2303.2-2315.5 K2qn Crude Oil -31.1 -31.04 -30.08 -29.56 -29.78

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DB33 2340.1-2351.7 K2qn Crude Oil -30.39 -30.68 -29.43 -28.82 -28.92

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Fig. 1. (A) Location map of the study area in China mainland. (B) The sub-tectonic units of the
Changling Sag, southern Songliao Basin. The structural subdivisions include western slope,
southern uplift, eastern slope, Qianan depression, Daqingzi uplift, and Heidimiao depression. (C)
AA cross section across Changling Sag showing the structural pattern and stratigraphic
intervals. K1q: Lower Cretaceous Quantou Formation, K2qn: Upper Cretaceous Qingshankou
Formation, K2y: Yaojia Formation, K2n: Nenjiang Formation, K2s: Sifangtai Formation, K2m:
Mingshui Formation. (modified after Dong et al., 2014).

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Fig. 2. Simplified stratigraphic column of the Changling Sag in the southern of Songliao Basin
(modified from Dong et al., 2014).

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Fig. 3. Variation of Rock-Eval S1+S2 with total organic carbon (TOC) content (A) and hydrogen
index with Tmax (B) for samples from K2qn2 and K2qn1 member in Changling Sag.

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Fig. 4. GC and GC-MS diagrams for two selected source rock samples from K2qn2 (A,C,E) and
K2qn1 (B,D,F) member, respectively.

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Fig. 5. Triangular plot of relative abundance of fluorenes (F), dibenzothiophenes (DBT) and
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dibenzofuranes (DBF) of the nine source rock extracts.

Fig. 6. Whole gas chromatograms of the selected crude oils from the Qingshankou Formation in
Changling Sag. Pr: pristine; Ph: phytane.
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Fig. 7. Terpane (m/z 191) and sterane (m/z 217) mass chromatograms of the selected crude oils
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from the Qingshankou Formation in the Changling Sag.

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Fig. 8. Ternary diagram showing the relative abundances of C27-C29 regular steranes in the crude
oils from the Qiangshankou Formation in the Changling Sag.
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Fig. 9. Correlation between various geochemical parameters for crude oils from the Qingshankou
reservoir in Changling Sag.
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Fig. 10. Two maturity parameters based on steranes for source rock (A) and crude oil samples (B).
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Fig. 11. Plot of C19/C23 tricyclic terpane and C29 /(+) sterane ratios.

Fig. 12. 13C values of saturated and aromatic hydrocarbon fractions of source rock extracts (A)
and crude oils (B) from the Qingshankou Formation in Changling Sag.

Fig. 13. Result of hierarchical cluster analysis (HCA) using biomarker and carbon isotope data,
showing the affinities of analyzed oil and rock samples. Each colored vertical line that reaches the
base represents one sample.
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Fig. 1. (A) Location map of the study area in China mainland. (B) The sub-tectonic units of the
Changling Sag, southern Songliao Basin. The structural subdivisions include western slope,
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southern uplift, eastern slope, Qianan depression, Daqingzi uplift, and Heidimiao depression. (C)
AA cross section across Changling Sag showing the structural pattern and stratigraphic
intervals. K1q: Lower Cretaceous Quantou Formation, K2qn: Upper Cretaceous Qingshankou
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Formation, K2y: Yaojia Formation, K2n: Nenjiang Formation, K2s: Sifangtai Formation, K2m:
Mingshui Formation. (modified after Dong et al., 2014).
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Fig. 2. Simplified stratigraphic column of the Changling Sag in the southern of Songliao Basin
(modified from Dong et al., 2014).
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Fig. 3. Variation of Rock-Eval S1+S2 with total organic carbon (TOC) content (A) and hydrogen
index with Tmax (B) for samples from K2qn2 and K2qn1 member in Changling Sag.

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Fig. 4. GC and GC-MS diagrams for two selected source rock samples from K2qn2 (A,C,E) and
K2qn1 (B,D,F) member, respectively.
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Fig. 5. Triangular plot of relative abundance of fluorenes (F), dibenzothiophenes (DBT) and

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dibenzofuranes (DBF) of the nine source rock extracts.

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Fig. 6. Whole gas chromatograms of the selected crude oils from the Qingshankou Formation in
Changling Sag. Pr: pristine; Ph: phytane.
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Fig. 7. Terpane (m/z 191) and sterane (m/z 217) mass chromatograms of the selected crude oils
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from the Qingshankou Formation in the Changling Sag.

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Fig. 8. Ternary diagram showing the relative abundances of C27-C29 regular steranes in the crude
oils (A) and source rock samples (B) from the Qiangshankou Formation in the Changling Sag.

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Fig. 9. Correlation between various geochemical parameters for crude oils from the Qingshankou
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reservoir in Changling Sag.

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Fig. 10. Two maturity parameters based on steranes for source rock (A) and crude oil samples (B).

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Fig. 11. Plot of C19/C23 tricyclic terpane and C29 /(+) sterane ratios.

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Fig. 12. 13C values of saturated and aromatic hydrocarbon fractions of source rock extracts (A)

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and crude oils (B) from the Qingshankou Formation in Changling Sag.

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Fig. 13. Result of hierarchical cluster analysis (HCA) using biomarker and carbon isotope data,

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showing the affinities of analyzed oil and rock samples. Each colored vertical line that reaches the
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base represents one sample.
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Highlights

Characterization of source rocks and oils were investigated

Lower member source rock has relatively higher hydrocarbon generation potential

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Middle member deposited in less anoxic conditions with more terrigenous organisms

All the crude oils within Qingshankou Formation belong to one oil family

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Oils are primarily from the lower member source rock

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