Organic Geochemistry 80 (2015) 18–34

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Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem

Geochemistry and correlation of crude oils from reservoirs and source

rocks in southern Biyang Sag, Nanxiang Basin, China
Tian Dong a,c,⇑, Sheng He a, Guoquan Liu a,b, Yuguang Hou a, Nicholas B. Harris c
a
Key Laboratory of Tectonics and Petroleum Resources, China University of Geosciences (Wuhan), Ministry of Education, Wuhan 430074, China
b
The Fifth Oil Production Plant in Daqing Oilfield Company, PetroChina, Daqing, Heilongjiang 163000, China
c
Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, AB T6G 2E3, Canada

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

Article history: The Paleogene Hetaoyuan Formation, a sequence of gray to dark calcareous mudstone and dolomitic
Received 14 August 2014 mudstones, is the main source rock and reservoir in the Biyang Sag, Nanxiang Basin, eastern China.
Received in revised form 9 December 2014 Organic geochemical analysis study performed on 57 source rock samples from the Hetaoyuan Formation
Accepted 15 December 2014
demonstrates poor to abundant organic matter content, ranging from 0.24–5.4 wt% (TOC content), char-
Available online 20 December 2014
acterized by oil prone Type II kerogen. Eleven crude oil samples from the Hetaoyuan Formation in south-
ern Biyang Sag were analyzed using bulk properties and molecular methods to determine their maturity
Keywords:
and origin. The results suggest that the crude oils exhibit different maturity and source organic matter.
Oil family
Oil to source correlation
Three groups of oils were identified by integrated analysis of gas chromatography, gas chromatogra-
Hetaoyuan Formation phy–mass spectrometry, stable carbon isotope, physical properties and gross composition of crude oil.
Biyang Sag Group A oils, defined as low mature oil, are characterized by high density, viscosity, sulfur content and
Nanxiang Basin low saturated hydrocarbon content. This group of oils has relatively high values of Ph/n-C18, C24/C26
and gammacerane index, indicating that the original organic matter had more contribution from terrig-
enous plants and was deposited in saline and stratified water columns, under anoxic conditions. Group B
oils, defined as normal maturity oil, are characterized by moderate density, viscosity, sulfur content and
moderate saturated hydrocarbon content. This group of oils has relatively low values of Ph/n-C18, C24/C26
and gammacerane index and displays a slight predominance of C29 steranes, indicating that the original
organic matter had more contribution from marine algae and was deposited under sub-oxic to anoxic
conditions with low salinity. Group C oils, defined as light oil, are characterized by low density, viscosity
and abundant saturated hydrocarbons. Representative source rock samples were selected for further
correlation. The results of oil-source rock correlation suggest that crude oils from the Eh2 member of
Hetaoyuan Formation are mixture derived from source rocks in the Eh2 member and upper layer of
the Eh3 member, while oils from the upper and lower layer of the Eh3 member correlate with source rocks
in the upper and lower layers of the Eh3 member, respectively.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction
The Biyang Sag is an interior tectonic unit in the Nanxiang
Basin, eastern China (Fig. 1). A number of oil fields and numerous
oil and gas shows have been discovered in the sag (Qin and Zhou,
2007). It is a hydrocarbon rich depression in eastern China, with
petroleum resources of 3.61  108 tons (1 ton = 7.33 barrels) in
an area of about 1000 km2 (Cheng, 2007). Petroleum exploration
in the Biyang Sag has entered the mature phase and finding
new oil reserves has become more difficult (Dong et al., 2013).
The discovered oil fields are primarily in Paleogene Hetaoyuan
⇑ Corresponding author at: Department of Earth and Atmospheric Sciences,
University of Alberta, Edmonton, AB T6G 2E3, Canada.
reservoir units (Fig. 2). Previous studies demonstrated that the
Hetaoyuan Formation contains both the main source and reservoir
rocks within Cenozoic strata (Wang and Suzuki, 1992; Zheng and
Yang, 1996; Cheng et al., 2011). Exploration results reveal that
low mature, normal and heavy oils were discovered in Hetaoyuan
reservoir (Hu et al., 2003; Zhou and Wu, 2004). However, the dis-
tribution patterns of different oils remain unresolved. Some stud-
ies identified three distinctly different oil intervals in the upper,
middle and lower members within the Hetaoyuan Formation
(Cheng et al., 2005). Comprehensive studies demonstrate that
the entire Hetaoyuan Formation is rich in organic matter. How-
ever, little is known about the quantity, quality and maturity of
the upper, middle and lower members. Numerous oil-source cor-
relation studies have been performed in the Biyang Sag, yet the

http://dx.doi.org/10.1016/j.orggeochem.2014.12.006
0146-6380/Ó 2014 Elsevier Ltd. All rights reserved.
 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34 19

source of the discovered oils in the southern region of this basin
remains unresolved (Jiang and Jia, 1986; Luo et al., 2008; Li
et al., 2010). These studies suggest that the lower member is
the main source for crude oils and the origin of oils discovered
in the middle member is still unclear.
In this study, we investigated the geochemical characteristics of
source rocks and oils from the Hetaoyuan Formation in the south-
ern Biyang Sag in order to determine the origin of the oils. The first
objective of this study was to characterize the biomarker composi-
tion and determine the true maturity levels of the crude oils. The
second objective was to identify effective source rocks, classify
the oils into families, and determine the respective source rocks.
By addressing these two objectives, this research will facilitate fur-
ther hydrocarbon exploration in this region. In addition, applying
geochemical methods for oil-source correlation to such a small
and hydrocarbon-rich sag would enrich general geochemical
knowledge and can be applied to similar petroliferous sedimentary
basins.
Routine oil-source correlation studies are mainly based on bio-
marker and stable carbon isotopic compositions of crude oil in res-
ervoirs and residual oil in source rocks (Peters et al., 2005; Yu et al.,
2011). Oils from the same family are compositionally related and
originate from a single source rock of relatively uniform deposi-
tional facies and lithology (Peters et al., 1994; Abrams et al.,
1999; George et al., 2004, 2008; Zhang and Huang, 2005), interpre-
tation needs to take into account that oil compositions can be
significantly modified during migration and within reservoirs
(e.g., Thompson, 1987; Peters and Moldowan, 1993).

Fig. 1. (A) Location map of study area in China mainland. (B) Tectonic map of Biyang Sag, the structural subdivision including Northern Slope Region; Central Depression and
Southern Steep Region. (C) Cross section across Biyang Sag showing the structural framework and the key stratigraphic intervals. Abbreviations: Eh23 = lower layer of the lower
member of Hetaoyuan Formation; Eh13 = upper layer of the lower member of Hetaoyuan Formation; Eh2 = the middle member of Hetaoyuan Formation; El = Liaozhuang
Formation; N + Q = Neogene and Quaternary.
20 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34

Fig. 2. Generalized stratigraphy of the Biyang Sag, showing tectonic evolution stages and the major petroleum system elements.

2. Geological setting
The Biyang Sag is located in Nanxiang Basin, Henan Province,
China, and covers an area of approximately 1000 km2, as shown
in Fig. 1 (Fu and Zhan, 2009). This basin can be subdivided into
three structurally distinct tectonic units, Northern Slope Region,
Central Depression and Southern Steep Region (Fig. 1B) (Ma
et al., 2014). This rift basin developed on Cretaceous basement
and the tectonic evolution of the basin can be divided into three
major stages: a syn-rift stage (Late Cretaceous), a post-rift stage
(Paleogene) and a tectonic inversion stage (Neogene).
The sag is filled with a thick Cenozoic sediment sequence,
which comprises the Paleogene Yuhuangding Formation (Ey), Dac-
angfang Formation (Ed), Hetaoyuan Formation (Eh), Liaozhuang
Formation (El) and overlying strata deposited during Neogene
and Quaternary time (Fig. 2). The Hetaoyuan Formation (Eh) is
the main source and reservoir rocks in the sag and can be subdi-
vided into three members, from top to bottom, the upper member
(Eh1), the middle member (Eh2) and the lower member (Eh3). The
Eh3 member is further divided into an upper (Eh13) and a lower
layer (Eh23) (Fu and Zhan, 2009; Dong et al., 2013). The Eh3 member
consists of gray and dark gray mudstone, intercalated with brown–
gray dolomitic mudstone, dolomite, as well as siltstone, sandstone.
The Eh2 member consists of gray mudstone and argillaceous dolo-
mite, interbed with dolomite and oil shales. Previous studies
reported that clastic rocks and carbonates are the two main reser-
voir rocks in Biyang Sag. In these reservoir rocks, porosity ranges
from 0.19%–48%, averaging 18.5%, and permeability ranges from
1  103 lm2 to 17.6 lm2, averaging 355  103 lm2 (Cheng,
2007).
 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34 21

3. Samples and methods 3.2. Rock-Eval pyrolysis and bitumen extraction of source rocks

3.1. Samples
The present study focuses on the southern Biyang Sag, primarily
in the Central Depression and Southern Steep Region (Fig. 1B). A
total of 57 source rock samples and 11 crude oil samples were col-
lected and analyzed. These oil and source rock samples were from
different members of Hetaoyuan Formation, including Eh2, Eh13 and
Eh23 (see Tables 1 and 4 for detailed sampling information). Density,
viscosity, sulfur and wax contents were provided by the Henan
Oilfield Company.
All of the source rock samples were analyzed for Rock-Eval
parameters and TOC (total organic carbon). To investigate possible
oil-to-source rock correlation, 14 source rock samples from the
Eh1, Eh2 and Eh3 members were selected, cleaned and then ground
to powder. All powders were sieved and then Soxhlet extracted for
48 h using dichloromethane to obtain the source rock extracts.
After solvent removal, the extracts were fractionated by column
chromatography over activated silica gel into saturate, aromatic
and resin fractions. Eleven crude oil samples from the three mem-
bers were separated into saturates, aromatics and polars.

Table 1
Rock-Eval data for the source rock samples.

Well Depth (m) Member Lithology S1 S2 S1 + S2 Tmax (°C) TOC (%) HI OI

B197 1453.0 Eh2 Mudstone 0.03 4.55 4.58 438 1.58 288 45
B267 1653.3 Eh2 Dolomitic mudstone 0.43 19.88 20.31 436 3.31 601 11
B257 2102.5 Eh2 Dolomitic mudstone 0.08 1.06 1.14 425 0.86 123 50
YQ20 1938.7 Eh2 Mudstone 0.19 4.33 4.52 432 1.20 361 24
B304 1132.0 Eh2 Shale 0.19 10.11 10.30 433 2.61 387 21
B96 2064.0 Eh2 Mudstone 0.06 0.92 0.98 425 0.91 101 75
B96 1922.6 Eh2 Mudstone 0.50 17.10 17.60 433 2.95 580 19
B197 2188.9 Eh2 Mudstone 1.05 17.24 18.29 435 2.76 625 14
W24 2111.9 Eh2 Muddy dolomite 0.05 0.64 0.69 434 0.50 128 106
B168 1409.9 Eh13 Mudstone 0.02 2.83 2.85 433 0.92 308 32
B214 1412.6 Eh13 Mudstone 0.00 0.11 0.11 434 0.33 33 267
B78 1585.0 Eh13 Mudstone 0.17 10.02 10.19 444 1.70 589 19
B78 970.0 Eh31 Mudstone 0.01 1.58 1.59 441 0.83 190 42
B179 2188.0 Eh13 Mudstone 0.21 10.43 10.64 441 1.60 652 26
B179 2190.6 Eh13 Muddy dolomite 0.02 0.26 0.28 425 0.28 93 225
B176 2196.9 Eh13 Muddy dolomite 0.14 5.61 5.75 431 1.00 561 40
B96 2108.5 Eh13 Dolomitic mudstone 0.03 2.14 2.17 430 0.94 228 103
B214 1079.5 Eh13 Shale 0.18 26.65 26.83 439 4.16 641 15
W24 2417.5 Eh13 Mudstone 0.30 3.90 4.20 444 0.94 415 12
B218 2117.3 Eh13 Mudstone 0.11 4.78 4.89 441 1.32 362 30
B257 2670.0 Eh13 Mudstone 0.02 0.28 0.30 438 0.40 70 128
B176 1710.4 Eh13 Mudstone 0.34 10.89 11.23 432 1.72 633 26
YQ20 2488.2 Eh13 Mudstone 0.19 26.60 26.79 447 4.06 655 5
B96 2197.0 Eh13 Dolomitic mudstone 0.99 32.19 33.18 442 4.50 715 7
B331 1091.0 Eh13 Shale 0.00 0.14 0.14 416 0.24 58 162
B64 2536.5 Eh13 Mudstone 0.00 0.18 0.18 431 0.28 64 100
B96 968.5 Eh13 Mudstone 0.09 3.02 3.11 423 3.29 92 38
B212 1385. 7 Eh13 Mudstone 0.02 3.34 3.36 442 1.07 312 30
B206 653.0 Eh13 Mudstone 0.38 26.91 27.29 444 4.21 639 29
B218 2256.4 Eh13 silty mudstone 0.89 16.21 17.10 428 5.40 300 5
B218 2191.5 Eh13 Shale 1.22 16.21 17.43 445 2.77 585 24
B180 1752.6 Eh13 Mudstone 0.10 3.69 3.79 439 1.18 313 14
B96 2831.5 Eh13 Shale 0.75 5.98 6.73 439 1.75 342 16
B130 1556.5 Eh13 Shale 0.12 21.43 21.55 439 3.27 655 12
B126 790.0 Eh13 Mudstone 0.10 14.78 14.88 436 2.61 566 34
B259 2024.8 Eh13 Dolomitic mudstone 0.39 18.27 18.66 444 2.71 674 8
B259 1561.4 Eh13 Shale 0.21 6.90 7.11 438 1.43 483 28
YQ20 2595.5 Eh13 Shale 0.30 9.44 9.74 445 1.85 510 13
B163 2895.0 Eh13 Muddy dolomite 0.26 0.63 0.89 433 0.37 170 54
B182 2752.5 Eh13 Mudstone 0.32 12.25 12.57 444 2.44 502 11
B191 1531.4 Eh23 Mudstone 0.49 7.80 8.29 433 1.36 574 32
Y2 2747.0 Eh23 Mudstone 0.13 3.08 3.21 436 1.39 222 9
B104 1391.8 Eh23 Mudstone 0.52 15.39 15.91 440 2.48 621 8
B214 1569.5 Eh23 Mudstone 0.11 3.23 3.34 427 0.98 330 33
B170 840.0 Eh23 Mudstone 0.00 0.36 0.36 431 0.44 82 84
YQ3 2871.0 Eh23 Mudstone 0.15 0.99 1.14 436 0.31 319 45
B111 3397.0 Eh23 Dolomitic mudstone 0.33 0.93 1.26 447 1.69 55 8
Y9 2919.0 Eh23 Mudstone 0.09 0.91 1.00 442 0.57 160 42
B168 2135. 7 Eh23 Mudstone 0.20 13.10 13.30 442 2.51 522 37
B342 843.0 Eh23 Mudstone 0.03 1.34 1.37 433 0.67 200 75
B308 1842.9 Eh23 Shale 0.33 12.39 12.72 441 2.33 532 11
Y9 2139.4 Eh23 Mudstone 0.77 23.49 24.26 437 4.43 530 8
Y2 3210.5 Eh23 Mudstone 0.07 0.63 0.70 443 0.54 117 28
Y9 1080.0 Eh23 Shale 0.06 5.03 5.09 431 1.14 441 35
B210 3503.0 Eh23 Mudstone 0.27 0.61 0.88 442 1.47 41 14
B197 746.5 Eh23 Shale 0.26 15.51 15.77 429 2.75 564 36
Y6 3291.2 Eh23 Mudstone 0.36 1.52 1.88 442 0.83 183 22
22 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34

3.3. Gas-chromatography and GC–mass spectrometry
Saturated hydrocarbons from the rock extracts and crude oils
were analyzed by gas chromatography (GC), gas chromatogra-
phy–mass spectrometry (GC–MS) for molecular compositions.
GC analysis of the saturated hydrocarbon from the crude oils
and source rock extracts was performed using an Agilent 7890
chromatograph (fused silica column, 30 m  0.25 mm  0.25 lm)
equipped with a flame ionization detector. The oven temperature
was initially held at 70 °C for 1 min, programmed to 300 °C at
3 °C/min and held at 300 °C for 30 min. GC–MS of saturated hydro-
carbons was carried out on an Agilent 7890 gas chromatograph
coupled to an Agilent 5975C mass spectrometer. A HP-5MS fused
silica column (30 m  0.25 mm  0.25 lm) was used and the car-
rier gas was helium. For analyzing the saturated hydrocarbon frac-
tion, the GC oven was initially set at 60 °C for 2 min, programmed
to 300 °C at 2 °C/min and held at 300 °C for 30 min.
4. Results
4.1. Source rock geochemistry
4.1.1. Organic matter enrichment and kerogen type
The Hetaoyuan Formation is the most important source rock in
Biyang Sag. The second member of the Hetaoyuan Formation (Eh2)
has total organic carbon (TOC) content up to 3.1 wt%, averaging
1.85 wt% (Table 1 and Fig. 3A). The TOC contents of the upper layer
of the third member (Eh13) range from 0.24–5.4 wt%, averaging
1.92 wt%, and the TOC contents of the lower layer of the third
member (Eh23) range from 0.31–4.43 wt%, averaging 1.52 wt%
(Table 1 and Fig. 3A). A plot of Rock-Eval hydrogen index (HI) ver-
sus Tmax (Fig. 3B) for Eh2 and Eh3 samples demonstrates that the
source rocks are primarily Type II kerogen, with some samples that
plot in the type I and type III regions. Based on the organic matter
concentration and kerogen type, all three intervals have the poten-
tial to generate petroleum.
4.1.2. Thermal maturity
Thermal maturity was evaluated on the basis of Rock-Eval Tmax
and vitrinite reflectance. Tmax values were only reported for sam-
ples with S2 values > 0.2 mg HC/g. As shown in Fig. 3B, Tmax values
for samples from Eh2, Eh13 and Eh23 range from 425–438 °C, 416–
447 °C, 427–447 °C, respectively. Thermal maturity at the top of
the Eh13 member ranges from less than 0.5 %Ro to more than 0.6
%Ro, which is in the immature and low mature stage (Fig. 4A).
Source rock at the bottom of Eh13 has a relatively high thermal
maturity ranging from 0.4 %Ro to more than 1.0 %Ro, which is
the early mature and the oil window (Fig. 4B). Source rock at the
bottom of Eh23 has the highest thermal maturity ranging from 0.5
%Ro to more than 1.3 %Ro, which reaches the high mature or gas
generation stage (Fig. 4C).
4.1.3. n-Alkanes and isoprenoids
The distribution of n-alkanes and isoprenoids in the Hetaoyuan
Formation may reflect the organic matter source. The pristane/
phytane ratio is commonly used as an indicator of depositional
environment and organic matter source (Didyk et al., 1978). The
pristane/phytane ratio is believed to be indicative of redox condi-
tions (Powell and McKirdy, 1973; Hunt, 1996; Harris et al., 2004;
Hao et al., 2009). Generally, high Pr/Ph ratios (> 3) indicate terrig-
enous organic matter deposited under oxic conditions (Powell and
Mckirdy, 1973) and Pr/Ph ratios between 1 and 3 are believed to
indicate oxic and suboxic conditions (Hunt, 1996; Peters et al.,
2005). Low Pr/Ph ratios (< 1) indicate anoxic conditions (Hunt,
1996. Harris et al., 2004) and Pr/Ph ratios < 0.8 have been docu-
mented to be related to highly saline and reducing environments
(Peters et al., 2005; Cheng et al., 2013). The ratios of pristane
(Pr)/n-C17, phytane (Ph)/n-C18 and Pr/Ph of source rocks are shown
in Table 2. These three parameters for the 14 samples range from
0.15–1.91, 0.26–3.51 and 0.24–0.93, respectively. Samples from
Eh2 have the highest Ph/n-C18 ratios.
4.1.4. Steranes and terpanes
The relative abundance of C27, C28 and C29 steranes are useful
indicators for the type of organic matter (Hunt, 1996; Samuel
et al., 2009). C27 and C28 steranes are believed to be derived from
marine organic and lacustrine algae, respectively, while C29 ster-
anes generally indicate a contribution from land plant organic mat-
ter (Peters et al., 2005; Albaghdady, 2013). C27–C29 sterane
distributions are often expressed in ternary plots to give informa-
tion on organic facies and source organic matter. The relative dis-
tribution of C27, C28 and C29 aaa (20R) steranes were plotted on
a sterane ternary diagram (Fig. 5A). In comparison to samples from
Eh2 and Eh13, samples from Eh23 shift toward C29 sterane. Sterane
(m/z 217) mass chromatograms of representative source rock sam-
ples are shown in Fig. 6. The C27, C28 and C29 aaa 20R steranes have
relatively equal distribution with a slight predominance of C29
steranes.
Tetracyclic terpanes occur in most source rock extracts and oils
(Peters et al., 2005; Hao et al., 2009). Many studies demonstrate

Table 2
Selected molecular parameters for source rock extracts.

Well Depth Member Lithology Pr/n- Ph/n- Pr/ C29 aaa C29 bb/ C27/ C28/ C29/ C24/ gammacerane/ Ts/ C29 Ts/C29
(m) C17 C18 Ph S/(S + R) (aa + bb) RC27–29 RC27–29 RC27–29 C26 hopane (Ts + Tm) hopane
B78 1922.6 Eh2 Mudstone 1.60 3.51 0.45 0.14 0.25 0.26 0.35 0.38 1.61 0.04 0.16 0.10
B331 1938.7 Eh2 Mudstone 1.91 2.24 0.73 0.14 0.26 0.32 0.33 0.34 2.27 0.09 0.17 0.12
Y9 2064.0 Eh2 Mudstone 0.76 2.02 0.27 0.19 0.21 0.23 0.29 0.47 1.88 0.24 0.20 0.15
Y2 2108.5 Eh13 Dolomitic 0.50 0.44 0.93 0.51 0.53 0.35 0.00 0.65 0.10 0.76 0.74 0.94
mudstone
Y6 2197.0 Eh13 Dolomitic 0.25 2.67 0.24 0.28 0.21 0.32 0.31 0.37 0.94 n.d. 0.04 n.d.
mudstone
B130 2488.2 Eh13 Mudstone 1.04 2.87 0.32 0.14 0.26 0.45 0.25 0.29 0.42 0.33 0.17 0.24
B191 2595.5 Eh13 Shale 0.70 1.45 0.42 0.51 0.41 0.30 0.26 0.45 0.22 0.72 0.36 0.16
B96 2752.5 Eh13 Mudstone 0.27 0.66 0.37 0.58 0.42 0.28 0.28 0.44 0.85 0.18 0.18 0.07
B78 2831.5 Eh13 Shale 0.15 0.53 0.25 0.52 0.54 0.26 0.27 0.48 0.36 0.54 0.60 0.34
B78 2895.0 Eh13 Muddy 0.41 0.99 0.27 0.55 0.55 0.28 0.26 0.46 0.44 0.43 0.42 0.22
dolomite
B197 2871.0 Eh23 Mudstone 1.25 2.59 0.35 0.11 0.16 0.22 0.26 0.51 1.00 0.63 0.20 0.00
B197 3210.5 Eh23 Mudstone 0.59 1.98 0.33 0.24 0.20 0.29 0.33 0.39 0.91 n.d. 0.07 n.d.
B96 3397.0 Eh23 Dolomitic 0.20 0.28 0.65 0.46 0.34 0.32 0.29 0.40 0.48 0.25 0.24 0.12
mudstone
B212 3503.0 Eh23 Mudstone 0.19 0.26 0.40 0.40 0.34 0.32 0.28 0.41 38.00 0.24 0.34 0.14
 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34 23

Table 3 shows a distinct variation (Table 2). Source rock samples from
Statistics on physical properties of crude oils from Biyang Sag. the Eh3 member have high gammacerane indices ranging from
Formation Density (g/cm3) Viscosity (mPa s) Wax (%) Sulfur (%) 0.18–0.76, indicating hypersaline and stratified water column
Eh2 0:84490:9421 3:42687:4 1:433:4 0:050:70 conditions, which is favorable for organic matter preservation.
0:8984ð17Þ 518:9ð17Þ 20:7ð17Þ 0:30ð7Þ
Eh13 0:82800:9144 2:0141:3 14:448:6 0:020:34 Samples from the Eh2 member have relatively low ratios ranging
0:8657ð96Þ 17:4ð96Þ 35:4ð96Þ 0:11ð96Þ
from 0.04–0.24, indicating decreased salinity in the water column.
Eh23 0:74800:9041
0:8240ð64Þ
0:4100:9
6:5ð64Þ
2:044:1
22:7ð64Þ
0:010:30
0:07ð64Þ

minimummaximum
Note: average ðsample numberÞ
. 4.2. Crude oil geochemistry

4.2.1. Physical properties

that abundant C24 tetracyclic terpane in petroleum can be indica-
tive of terrigenous organic matter input (Philp and Gilbert, 1986;
Duan et al., 2008). With the exception of one sample, the Eh23
member has C24/C26 ranging from 0.48–1, and Eh13 member has
C24/C26 ranging from 0.1–0.94, while the Eh2 member displays
C24/C26 between 1.61 and 2.27 (Table 2). The variation of C24/C26
ratios indicates that Eh2 source rocks have more contribution from
terrigenous organic matter.
Gammacerane is commonly used to investigate the salinity of a
depositional environment (Venkatesan, 1989). High concentrations
are usually related to highly reducing and hypersaline conditions
during the deposition of organic matter (Peters et al., 2005; Zhu
et al., 2005; Summons et al., 2008; Albaghdady, 2013). Gammace-
rane index, defined as the ratio of gammacerane/abC30 hopane,
The density, viscosity, sulfur and wax content of crude oils from
Biyang Sag are given in Table 3. Great variations in physical prop-
erties of crude oils can be observed in the different rock units.
Crude oils from Eh2 are characterized by high density, averaging
0.8984 g/cm3, high viscosity, averaging 518.9 mPa s, low wax con-
tent, averaging 20.7%, and high sulfur content, averaging 0.3%.
Crude oils from Eh13 have moderate density (averaging 0.8657 g/
cm3), moderate viscosity (averaging 17.41 mPa s), high wax con-
tent (averaging 35.4%), and low sulfur content (averaging 0.11%).
Compared with oils from the overlying member, crude oils from
Eh23 have the lowest density with average value of 0.824 and the
lowest viscosity with average value of 6.46. Different physical
properties of crude oils in the Biyang Sag indicate a wide range
of maturity.

Table 4
Gross composition of the crude oils from Biyang Sag.

Well Depth (m) Member Saturates (%) Aromatics (%) Resins (%) Asphaltenes (%)
B293 1083.4 Eh2 47.57 25.66 22.05 4.72
B330 1758.3 Eh2 56.44 18.25 18.25 7.05
B344 1776.5 Eh2 55.69 8.67 24.77 10.87
B188 1779.5 Eh2 54.48 16.07 21.15 8.30
B103 1965.8 Eh2 22.65 9.29 34.23 33.83
B331 2381.3 Eh13 77.70 12.18 7.18 2.93
B346 2564.4 Eh13 67.61 19.99 7.65 4.75
B160 2569.0 Eh13 79.10 9.90 4.54 6.46
B343 2728.4 Eh13 71.97 11.87 8.64 7.52
B252 3324.8 Eh23 92.86 5.82 0.79 0.53
B213 3559.5 Eh23 94.25 3.59 0.37 1.79

Note: Sat/Aro, saturate/aromatic hydrocarbon ratios.

Fig. 3. Variation of Rock-Eval S1 + S2 with total organic carbon (TOC) content (A) and hydrogen index with Tmax (B) for samples from the Biyang Sag, Nanxiang Basin, showing
the hydrocarbon-generating potential and organic matter type, respectively. The criteria distinguish poor, fair from good to excellent source rock are from Hao et al., 2007.
24 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34

4.2.2. Gross compositions 4.2.3. n-Alkanes and isoprenoids

The gross compositions (SARA) of the oils from the Biyang Sag
are given in Table 4. Crude oils from Eh2 contain high fractions of
resins and asphaltenes with saturated hydrocarbon fraction abun-
dance less than 60% (Table 4), indicating that those oils are affected
by biodegradation or low maturity. Saturated hydrocarbon frac-
tions for crude oils from Eh13 range from 67.61–77.7%, with a rela-
tively low content of resins and asphaltenes (Table 4). Crude oils
from Eh23 are characterized by a dominant saturated hydrocarbon
fraction with high saturate/aromatic hydrocarbon ratios and high
saturated fraction abundance (> 90%; Table 4).
As shown in Table 5, the Pr/Ph ratios of oils are extremely
low, < 0.6, indicating a hypersaline and reducing environment.
Oils from Eh2 have relatively high Ph/n-C18 ratios (Table 5 and
Fig. 7), ranging from 1.35–5.59. The n-alkane in representative
oil sample from well B103 shows a bimodal distribution,
while oils from Eh13 and Eh23 show unimodal distribution of
n-alkanes and have relatively low Pr/n-C17 and Ph/n-C18 ratios.
The whole oil chromatograms for oil from well B252 shows a
front end biased distribution, indicative of high maturity
(Fig. 7).

Fig. 4. Isoreflectance map of Hetaoyuan source rocks, Biyang Sag, Nanxiang Basin (from Dong et al., 2013). (A) Ro isoline of source rock at the top of upper Eh3 layer; (B) Ro
isoline of source rock at the bottom of upper Eh3 layer; (C) Ro isoline of source rock at the top of lower Eh3 layer.
 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34 25

Fig. 5. Ternary diagram showing the relative abundance of C27, C28 and C29 regular steranes in saturate hydrocarbon fraction of source rock extracts (A) and crude oils (B).

Fig. 6. Sterane (m/z 217) mass chromatograms of the selected source rocks from Biyang Sag.

4.2.4. Steranes and terpanes
Fig. 5B shows the relative distribution of steranes for all crude
oil samples. All of the studied samples plot in the center of the ter-
nary diagram. Representative m/z 217 chromatograms for the ana-
lyzed oil samples from different rock intervals are shown in Fig. 8.
Crude oils from different member source rocks show variation in
the relative distribution of C27, C28 and C29 steranes.
Gammacerane index is relatively high in all of the crude oil
samples, ranging from 0.23–0.48, indicating that the original
source rocks were deposited in saline water.
Biomarker distributions are widely used in oil maturity assess-
ment (Mackenzie, 1984; Seifert and Moldowan, 1986). The ratios of
aaa C29 20S/(20S + 20R) and C29 bb/(aa + bb) are commonly used
indicators for estimation of maturity (Waples and Machihara,
1990; Peters and Moldowan, 1993; Peters et al., 2005). Oils from
Eh2 have C29 20S/(20S + 20R) sterane ratios ranging from
0.14–0.36 and have C29 bb/(aa + bb) sterane ratios between 0.19
and 0.3 (Table 5 and Fig. 9). Oils from Eh13 show relatively high
20S/(20S + 20R) ratios ranging from 0.49 to 0.55 and relatively high
bb/(aa + bb) ratios ranging from 0.37 to 0.44. Oil samples from Eh23
have the highest 20S/(20S + 20R) and bb/(aa + bb) ratios. Unex-
pectedly, oil from well B213 exhibits moderate 20S/(20S + 20R)
ratio and bb/(aa + bb) ratio. These C29 20S/(20S + 20R) and C29
bb/(aa + bb) ratios indicate that oils from Hetaoyuan Formation
have a wide range of thermal maturity spanning the immature to
mature stage (Fig. 9).
More detailed information about the maturity of oils can be
provided by hopane parameters, which are sensitive to changes
in thermal maturity. Specifically, the Ts/(Ts + Tm) and C29 Ts/C29
hopane ratios are reliable maturity indicators that increase with
maturity (Fowler and Brooks, 1990; Farrimond et al., 1996;
Peters et al., 2005; Cheng et al., 2013). As shown in Table 5, crude
oils from Eh2 have low Ts/(Ts + Tm) and C29 Ts/C29 hopane ratios,
ranging from 0.05–0.23, 0.03–0.11, respectively. Oils from Eh13
show higher maturity than oils from Eh2, which can be observed
from the relatively high Ts/(Ts + Tm) and C29 Ts/C29 hopane ratios,
26 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34

ranging from 0.3–0.47 and 0.12–0.29, respectively. However, oil

C29 Ts/C29
samples from Eh23 show low Ts/(Ts + Tm) and C29 Ts/C29 hopane

hopane
ratios or lack terpanes, probably because of over maturity resulting

0.11

0.22
0.29
0.12
0.21
0.03
0.04
0.06
0.05

0.08
n.d.
in cracking of high molecular terpanes to low molecular weight
compounds. In summary, both steranes and hopanes parameters

Ts/(Ts + Tm)
suggest that the oils from the study area have a wide range of
maturity from early mature to highly mature and there is system-
atic variation in the maturity of oils produced from the different

0.23

0.41
0.47

0.41
0.10
0.08
0.10
0.05

0.30

0.20
n.d.
rock units.

gammacerane/
4.3. Carbon isotopic composition

hopane
The carbon isotopic composition of oil is largely dependent

0.42
0.33
0.39
0.37
0.25
0.36
0.24
0.43
0.23

0.48
n.d.
upon the d13C value of the kerogen in the source rock from which
it was derived (Schoell, 1984; Zhang and Huang, 2005). As a result,

C24/C26
the carbon isotopic composition of oil and gross composition are

1.29
0.92
1.03
0.93

0.38
0.39
0.41
0.38
0.80

n.d.
n.d.
useful to determine oil-source rock correlations and the deposi-
tional environment of source rocks (Hayes et al., 1990; Freeman

C29/RC27–29
et al., 1990; Chung et al., 1992).
Carbon isotopic compositions of whole oil and specific fractions
for 11 crude oils from Hetaoyuan Formation are shown in Fig. 10A

0.41
0.38
0.38
0.38
0.35
0.48
0.51
0.41
0.54
0.42
0.38
and Table 6. The d13C values of these oils range from 26.96‰ to
29.37‰, averaging 28.38‰. Saturates, aromatics, resins and

C28/RC27–29
asphaltenes have d13C values ranging from 27.54‰ to 30.63‰,
25.21‰ to 28.12‰, 26.49‰ to 28.00‰ and 26.13‰ to

0.31

0.33
0.25
0.24
0.28
0.25
0.24
0.25
0.30

0.30
0.30
27.89‰, respectively (Table 6).
As shown in Fig. 10A, the d13C values of the fractions in oil sam-
ples from Eh23 are substantially higher than crude oils from Eh2 and
C27/RC27–29

Eh13. The d13C values of oil fractions in oil samples from Eh2 are sim-
ilar to those from Eh13 (Fig. 10A), suggesting that these oils from Eh2
0.31
0.32
0.32
0.32
0.27
0.26
0.31
0.21
0.34
0.37
0.30

may have the same source rock as Eh13 crude oils or at least have
partial contributions from that source rock. Oil from Well B103
(aa + bb)

has obviously low carbon isotopic composition compared to the

C29 bb/

other oils, especially the d13C values of saturates, probably due to

0.26
0.23
0.24
0.19
0.42
0.41
0.44
0.37
0.56
0.33
0.30

low maturity.
C29 aaa 20S/
(20R + 20S)

5. Discussion
0.35
0.36
0.32
0.33
0.14
0.52
0.55
0.49
0.51
0.56
0.40

5.1. Oil family classification

Pr/Ph

The term ‘‘oil families’’ or ‘‘genetic groups’’ have been widely

0.38
0.37

0.31
0.21
0.41

0.48
0.52
0.52
0.46
0.3

0.4

used in the studies of petroleum origins (Peters et al., 1994;

Snowdon et al., 1998; Greene et al., 2004; Hao et al., 2010). An
Ph/n-C18

oil family is defined as a group of oils that originated from the same
0.94

0.71

0.56
1.35
1.37
1.87
1.75
5.59

1.25

1.35

or very similar source rock (Hao et al., 2010). Oil family classifica-
0.7

tion is commonly based on physical properties (Abeed et al., 2012),

bulk composition (Thompson, 1994), molecular compound charac-
Pr/n-C17

teristics (Karavas et al., 1998) and isotopic composition (Murray

0.52
0.41
0.42
0.42
0.97
0.42
0.55
0.39

0.38
0.28
0.80

et al., 1994; Zhang and Huang, 2005). Hierarchical cluster analysis

(HCA) is a commonly used statistical technique to distinguish
1.11

0.82

0.93
0.97
1.03

1.01
1.08
1.04
1.09
1.00
1.00

crude oils from different source rocks using multiple parameters.

OEP

Fig. 11 shows the dendogram using parameters listed in Tables 2

and 5, like Pr/n-C17, Ph/n-C18, Pr/Ph, C29 aaa 20S/(20R + 20S), C29
Group

bb/(aa + bb), C27 sterane, C28 sterane, C29 sterane, C24/C26, gam-
A
A
A
A
A
B
B
C
B
C
C

macerane/hopane and C29 Ts/C29 hopane and stable carbon isotope

Molecular parameters of crude oils.

data. The HCA separates the analyzed oil samples into three
Member

groups, as shown in Fig. 11 and Table 5.

Eh2
Eh2
Eh2
Eh2
Eh2
Eh13
Eh13
Eh13
Eh31
Eh23
Eh23

Group A oils, defined as low mature oil, mainly consist of oils

from the Eh2 member. The term ‘‘immature oils’’ generally refers
to oils derived from source rocks with 0.2–0.7 %Ro (Snowdon and
1758.3
1776.5
1779.5
1965.8
2381.3
2564.4

2728.4
3324.8
3559.5
1083.4

2569.0
Depth

Powell, 1982; Shanmugam, 1985; Snowdon, 1991; Koncz and

(m)

Etler, 1994; Wang, 2000; Pang et al., 2003). As there is no consen-

sus on the definition and diagnostic criteria for immature oil (Pang
B293

B344
B188

B331
B346

B343
B252
B213
B330

B103

B160
Well
Table 5

et al., 2003), here, we define the group A oils as low mature oil. The
Pr/Ph ratios are low and the abundance of phytane are higher than
 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34 27

Fig. 7. Gas chromatograms of representative crude oils from Biyang Sag. The peak labels denote the carbon number of n-alkanes: Pr, pristane; Ph, phytane. Oil sample from
well B103 shows a bimodal distribution of n-alkanes; the two samples from Eh3 member show unimodal distribution of n-alkanes.

Fig. 8. Sterane (m/z 217) mass chromatograms of representative crude oils from Hetaoyuan strata.

the concentration of n-alkane (n-C18) with Ph/n-C18 ranging from
1.35 to 5.59 (Table 5). C27, C28 and C29 aaa (20R) steranes have a
symmetric distribution in a ‘‘V’’ shape. These oils have relatively
high C24 tetracyclic/C26 tricyclic terpanes (> 0.8) and high gam-
macerane index (0.25–0.42) (Table 5 and Fig. 13), which suggests
that source rocks deposited in saline water, under anoxic condi-
tions with significant contributions from terrigenous organic mat-
ter. Their whole oil stable carbon isotope values are relatively low,
in the range of 28.02‰ to 29.08‰ (Fig. 10A). Maturity parame-
ters aaa C29 20S/(20R + 20S) and C29 bb/(aa + bb) have relatively
28 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34
low values. The oils also have low Ts/(Ts + Tm) and C29 Ts/C29
hopane ratios, indicative of low maturity. The relatively high val-
ues of Ph/n-C18, C24/C26 terpane ratios and gammacerane index
could also suggest that the group A oils have undergone biodegra-
dation. This is confirmed by the relatively high density and viscos-
ity of group A oils. These oils are characterized by high density,
high viscosity, high sulfur and low wax content (Table 3). The gross
compositions of these oils are dominated by resins and asphaltenes
with low concentrations of saturates and aromatics (Table 4).
Group B oils, defined as normal oil, primarily occur in the Eh13
reservoirs. This group of oils have relatively low C24 tetracyclic/
C26 tricyclic terpanes (< 0.41) and gammacerane indices similar
to as group A oils (0.23–0.43) (Table 5 and Fig. 13), indicating
source rocks with more contributions of marine organic matter.
The ratios of aaa C29 20S/(20R + 20S) and C29 bb/(aa + bb) range
from 0.40 to 0.55, indicating that those oils are in the mature stage.
Ts/(Ts + Tm) and C29 Ts/C29 hopane ratios exhibit moderate values,
suggesting that those oils have higher maturity that Group A oils.
Their n-alkane distributions are smooth with no odd/even predom-
inance. C27, C28 and C29 aaa (20R) steranes have an asymmetrical
distribution of ‘‘V’’ shape with a predominance of C29 steranes
(Fig. 13). Their whole oil stable carbon isotope values range from
27.67‰ to 29.37‰ (Fig. 10A and Table 6). Compared with group
A oils, these oils generally have lower density, lower viscosity,
higher wax and lower sulfur content. This group of oils is domi-
nated by saturates, with moderate content of aromatics, resins
and asphaltenes.
Group C oils, defined as light oil, originated primarily from the
Eh23 reservoirs. The carbon isotopic compositions of whole oil and
its fractions are obviously heavy, especially the carbon isotopic
composition of aromatics. The n-alkane distributions are also
smooth and with no odd/even predominance. The concentrations
of pristane and phytane are much less than the concentrations of
n-C17 and n-C18, which suggests that these oils are highly mature.
Compared with oil from the overlying reservoirs, they are charac-
terized by the lowest density, viscosity and sulfur content (Table 3).
The gross composition is dominated by saturates (> 90%), with
extremely low concentration of aromatics, resins and asphaltenes
(Table 4). The physical properties and gross composition suggest
that group C oils are highly mature.
5.2. Possible source rocks
An effective petroleum source rock must satisfy requirements
regarding the quantity, quality and thermal maturity of the organic
matter. Shales and mudstones from Eh2, Eh13 and Eh23 reveal a wide
range of source rock quality, from poor source to excellent source
rock. The plot of hydrogen index (HI) versus Tmax reveals that most
source rock samples from Eh2, Eh13 and Eh23 are Type II, which is
prone to generate oil rather than gas. In terms of quantity and
quality of the organic matter, Eh2, Eh13 and Eh23 source rocks are via-
ble source rocks for hydrocarbon generation. However, most of the
Eh2 source rocks are currently immature to marginally mature
with respect to oil generation (Fig. 4A). All of the Eh13 and Eh23
source rocks in the southern Biyang Sag are currently mature,
and the lowest Eh23 source rocks are currently in the gas window
(Fig. 4B and C).
5.3. Oil–oil and oil-source rock correlation
A successful oil-source rock correlation aims to find the genetic
relationship between source rocks and oils and relies on biomarker
composition (Peters and Moldowan, 1993; Peters et al., 2005;
Curiale, 2008). As discussed earlier, based on the physical proper-
ties, chemical compositions, biomarker fingerprints and carbon
isotopic composition, the investigated oils from the Hetaoyuan
Formation belong to group A, B and C. All of the Eh2, Eh13 and Eh23
source rocks are considered be viable sources for the oils. Never-
theless, the Eh2 source rocks seem to have less petroleum generat-
ing potential. In the following section, we will discuss the oil to
source rock correlation using HCA result, gas chromatograms of
saturated hydrocarbon, m/z 191 and m/z 217 mass chromatograms
and carbon isotopic composition, in order to determine genetic
relationships.
5.3.1. Hierarchical cluster analysis
HCA (hierarchical cluster analysis) was applied to relate ana-
lyzed oil to specific source rock intervals. Fig. 11 shows the affini-
ties of analyzed oil and rock samples. Oils from the Eh2 member
could be linked to the Eh2, Eh13 and Eh23 source rocks. This indicates
that group A oils are a mixture of oils generated from different
source rock intervals. Source rock samples from the Eh2 member
(wells B78 and B331) have no link to any oil samples, suggesting
that some Eh2 source rocks samples have no potential for petro-
leum generation, which is consistent with maturity result analyzed
for Eh2 source rock. Group B oils have link limited to rock samples
from the Eh13 member, indicating that they can be attributed to Eh13
source rock. Group C oils have one sample from the Eh13 member
and two samples from the Eh23 member. As shown in Fig. 11, group
C oil could be linked to the Eh13 and Eh23 source rocks.
5.3.2. Biomarker characteristics
5.3.2.1. Group A oils. Group A oils are rich in b-carotane and corre-
late with Eh2 and Eh13 source rock extracts. The group A oils differ
from the Eh23 source rocks, which are poor in b-carotane (Fig. 12).
Ph/n-C18 ratios are relatively high in group A oils and source rocks
from Eh2 and Eh13 with the predominance of phytane (Fig. 12), sug-
gesting that the oils and source rocks have consistent correlations.
The relatively high abundance in steranes and terpanes between n-
C27 and n-C31 suggests a great degree of similarity among group A
oils and Eh2, and Eh13 source rocks (Fig. 12).
Group A oils and the Eh2, and Eh13 source rocks are dominated by
C27 steranes (Figs. 6, 8 and 13), suggesting that they are genetically
related. C29 bb/(aa + bb) ratios in both group A oils and Eh2 source
rocks are relatively low, ranging from 0.19–0.30, 0.21–0.26, respec-
tively. aaa C29 20S/(20S + 20R) ratios in group A oils range from
0.14–0.36, averaging 0.3. However, the ratios in Eh2 source rock
Fig. 9. C29 20S/(20S + 20R) versus C29 bb/(aa + bb) sterane ratios for oils from
Biyang Sag, Nanxiang Basin. Criteria for immature, low mature and mature stage are
from Peters et al. (2005).
 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34
Fig. 10. Stable carbon isotope profiles of crude oils (A) and source rock extracts (B) from Biyang Sag, Nanxiang Basin.
extracts are much lower, ranging from 0.14–0.19, averaging 0.16.
The aaa C29 20S/(20S + 20R) ratios in Eh13 source rock extracts
are relatively high, ranging from 0.14–0.58, averaging 0.44 (Tables
2 and 5). In terms of the sterane parameters, thermal maturity of
group A oils is between that of the Eh2 and Eh13 source rock
extracts.
Terpane parameters that can be used to perform oil-source rock
correlation and include C24/C26, gammacerane index, Ts/(Ts + Tm)
and C29Ts/C29 hopane ratios. The C24/C26 ratios for group A oils
are lower than the Eh2 source rock extracts, but higher than the
Eh13 source rock extracts (Tables 2 and 5, and Fig. 13). The group
A oils and Eh13 source rock extracts have similar gammacerane indi-
ces, ranging from 0.25–0.42, 0.18–0.76, respectively. However, the
Eh2 source rock extracts have relatively lower values in gammace-
rane index, ranging from 0.04–0.24. Eh2 crude oils have relatively
low values of Ts/(Ts + Tm) and C29 Ts/C29 hopane ratios, and corre-
late with the Eh2 source rocks and source rocks within Eh13
Formation.
Overall, group A oils from the Eh2 Formation have moderate to
high values of Ph/n-C18, moderate to high values of C24/C26 ratios
and high gammacerane indices, which are between the values for
the Eh2 and Eh13 source rock extracts. The sterane and terpane
29
parameters, aaa C29 20S/(20S + 20R), C29 bb/(aa + bb), Ts/
(Ts + Tm) and C29 Ts/C29 hopane ratios indicate that the maturities
of Eh2 oils are low, and between those of Eh2 and Eh13 source rocks.
As discussed earlier, in terms of thermal maturity indicated by vitr-
inite reflectance, source rocks in Eh2 Formation are not able to gen-
erate huge amounts of hydrocarbons. Such a biomarker
assemblage indicates that group A oils cannot be attributed only
to one of the two possible source rocks, Eh2 and Eh13, but can be
best explained by mixing of Eh2 oils and Eh13 oils.
5.3.2.2. Group B oils. Oils from Eh13, defined as group B, and extracts
of source rocks from Eh13 generally exhibit similar n-alkane and
biomarker fingerprints. All of the Eh13 oils have moderate Ph/n-
C18 values and low Pr/Ph and correlate with the source rocks
within the Eh13 member (Fig. 12). Eh13 oils have lower b-carotane
than Eh2 oils and correlate with Eh13 source rock extracts (Fig. 12).
Group B oils are dominated by C29 steranes and correlate with
source rock extracts from Eh13 member where most of the source
rock samples are dominated by C29 steranes (Fig. 5A and B). Group
B oils have moderate values in C29 bb/(aa + bb), ranging from 0.37–
0.42, demonstrating that these oils are mainly at the peak oil gen-
eration stage (Fig. 9). Eh13 source rock extracts have similar ranges
30 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34

Table 6
Stable carbon isotope values of the whole oil and specific fractions in crude oils and source rocks from Biyang Sag, Nanxiang Basin.

Well Depth (m) Member Sample Stable carbon isotopes (‰, VPDB)
Whole oil Saturates Aromatics Resins Asphaltenes
B293 1083.35 Eh2 Crude oil 28.02 29.12 27.52 27.58 27.42
B330 1758.3 Eh2 Crude oil 28.62 28.92 27.3 27.09 27.17
B344 1776.5 Eh2 Crude oil 28.52 29.31 27.06 27.3 27.18
B188 1779.5 Eh2 Crude oil 28.33 29.1 27.43 27.15 27.3
B103 1965.8 Eh2 Crude oil 29.08 30.63 27.91 27.78 27.89
B331 2381.25 Eh13 Crude oil 28.61 29.13 27.4 27.76 27.44
B346 2564.35 Eh13 Crude oil 28.72 29.22 28.12 27.24 27.88
B160 2569 Eh13 Crude oil 27.76 28.28 26.48 27.2 27.25
B343 2728.4 Eh13 Crude oil 29.37 29.4 27.87 28 27.77
B252 3324.75 Eh23 Crude oil 26.96 27.54 25.21 26.49 26.13
B213 3559.5 Eh23 Crude oil 28.18 28.35 25.38 27.82 27.48
B78 1922.6 Eh2 Mudstone 32.19 35.28 29.8 30.66 29.83
B331 1938.7 Eh2 Mudstone 30.33 32.62 29.06 29.83 28.43
Y9 2064 Eh2 Mudstone 27.88 28.83 26.96 26.57 26.45
Y6 2197 Eh13 Dolomitic mudstone 26.19 29.11 26.42 26.01 25.69
B130 2488.2 Eh13 Mudstone 27.93 29.22 27.26 27.84 27.58
B191 2595.5 Eh13 Shale 29.28 27.23 25.16 25.36 28.55
B96 2752.5 Eh13 Mudstone 28.97 31.35 28.51 27.41 27.47
B78 2831.5 Eh13 Shale 28.85 29.89 28.16 28.14 28.18
B78 2895 Eh13 Muddy dolomite 27.43 28.08 27.27 26.15 26.82
B96 3397 Eh23 Dolomitic mudstone 24.82 26.31 24.37 24.84 25.6
B212 3503 Eh23 Mudstone 26.05 26.74 25.24 25.88 25.99

Fig. 11. Result of hierarchical cluster analysis (HCA) using biomarker and carbon isotope data, showing crude oil classes and correlation to source rocks. Each colored vertical
line that reaches the base represents one sample. HCA separated the oil samples into three groups. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)

in C29 bb/(aa + bb), between 0.21 and 0.55, indicating similar
maturity of the oils and source rocks.
Group B oils appears to be genetically related to Eh13 source
rocks, because they have similar organic matter source and depo-
sitional environment indicated by C24/C26 ratios and gammacerane
index (Fig. 13). Group B oils have moderate values of C24/C26 ratios
and gammacerane index, ranging from 0.38–0.41, 0.23–0.43,
respectively, and Eh13 source rock extracts have similar values,
ranging from 0.1–0.94 and 0.18–0.76, respectively. Eh2 source rock
extracts have relatively high values of C24/C26 and low values of
gammacerane index. Eh13 crude oils have Ts/(Ts + Tm) and C29 Ts/
C29 hopane ratios similar to Eh13 source rocks, indicating that they
have similar maturities. All of these results demonstrate that oils
in the Eh13 member were mainly derived from source rocks within
Eh13 member.
5.3.2.3. Group C oils. The saturated hydrocarbon gas chromato-
grams of group C oils and Eh23 source rocks are similar (Fig. 12),
characterized by front end biased and unimodal distribution of
n-alkanes with no odd/even predominance. Group C oils have
low phytane concentration and correlate with Eh23 source rocks,
differing from Eh13 source rocks (Fig. 12). Both group C oils and
Eh23 source rock extracts lack b-carotane, which is different from
Eh13 source rocks that have b-carotane (Fig. 12).
As shown in Fig. 12, group C oils and Eh23 source rock extracts
have relatively high concentrations of low carbon number mole-
cules, indicating that they have high maturities. Due to the effect
of maturity, a large proportion of steranes and terpanes have been
cracked, so biomarker parameters become invalid to evaluate the
maturity of crude oils and source rocks, and in some samples,
the steranes and terpanes are not detectable (Figs. 12 and 13).
 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34 31

Fig. 12. Gas chromatogram of saturated hydrocarbons of crude oils and source rocks from Hetaoyuan Formation in southern Biyang Sag.
32 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34

Fig. 13. Mass chromatogram (m/z 217 and m/z 191) of saturated hydrocarbons of crude oils and source rocks from Hetaoyuan Formation in southern Biyang Sag.

5.3.3. Correlation from carbon isotopic composition and lower than the oils from Eh23 (Fig. 10A). This result suggests
Stable carbon isotope values are widely used in oil-source cor- that oils from Eh2 and Eh13 member probably have the same source
relations (Freeman et al., 1990; Schoell et al., 1994). The carbon in organic materials, which differ from Eh23 oils. The d13C values of
isotopic compositions of oil fractions from Eh2 and Eh13 are similar Eh2 crude oils are substantially lower than the two extracts from
 T. Dong et al. / Organic Geochemistry 80 (2015) 18–34
Eh2 source rocks from the B78 and B311 wells (Fig. 10B), suggest-
ing that these oils are not mainly derived from Eh2, but from the
other source rocks. However, the extract from Eh2 source rock in
Y9 well has the same d13C values as Eh2 oils, suggesting that Eh2
source rocks may have partial contribution to the Eh2 oils. The
d13C values of Eh2 crude oils are similar to extracts from Eh13 source
rocks (Fig. 10A and B). Eh13 crude oils have d13C values similar to
Eh13 source rock extracts, which was interpreted to be derived from
the Eh13 source rocks. Both Eh23 crude oils and Eh23 source rock
extracts are characterized by relatively higher d13C values, which
are distinct from other crude oils and source rocks, demonstrating
that oils were generated, and expelled from Eh23 source rocks and
then stored in Eh23 reservoirs.
5.3.4. Further maturation of source rocks and oils
It is a possible that the older Eh23 member provided the source
for oils in the Eh13 member and then underwent high levels of mat-
uration. As discussed earlier, crude oils in the Eh13 member are
characterized by relatively high Pr/n-C17, Ph/n-C18, low gammace-
rane index and light carbon isotope, but crude oils from Eh23 Forma-
tion display relatively low values in Pr/n-C17, Ph/n-C18, high values
in gammacerane index and heavy carbon isotope ratios. Both bio-
marker (Table 5 and Fig. 13) and carbon isotope data (Fig. 10) led
to the suggestion that oils in the reservoir rocks of Eh13 have a
genetic relationship with the Eh13 source rocks, rather than Eh23
source rocks.
Xia et al. (2010) demonstrated that Eh23 source rock reached the
peak generation stage of the oil window at the end of Eh2 deposi-
tion (35.4 Ma), and significant amount of hydrocarbons were
expelled and migrated at the end of Eh1 deposition (29.3 Ma).
Eh13 source rock began to generate hydrocarbons at the end of
Eh2 deposition (35.4 Ma) and reached the peak generation stage
of oil window during the late period of El deposition (26 Ma).
Results of burial history and thermal evolution history reconstruc-
tion (Xia et al., 2010; Dong et al., 2013) indicate that significant
uplift caused by tectonic inversion occurred at the end of Paleo-
gene (23 Ma) and terminated further maturation of source rocks
and oils after accumulation. Studies of hydrocarbon migration
and accumulation confirmed that sandstones acted as the primary
conduit for hydrocarbon migration (Xie and Sheng, 2003; Xia et al.,
2010). Therefore, it was suggested that petroleum expelled from
the source rocks migrated and accumulated in adjacent sandstone
reservoirs as Eh3 Formation is composed of alternating mudstone,
siltstone and sandstone.
6. Conclusions
The three possible source rock intervals, Eh2, Eh13 and Eh23, have
abundant organic carbon content, and are dominated by Type II
kerogen. However, Eh2 source rocks are immature to early mature,
while Eh13 source rocks are in the oil generation stage and Eh23
source rocks are highly mature, and are able to generate conden-
sate and gas.
Based on physical properties, molecular compositions and sta-
ble carbon isotopic composition, crude oils discovered in the
Hetaoyuan Formation generally fall into three families. Group A
oils, defined as low mature oil, primarily exist in the Eh2 member,
while group B oils, defined as normal oil, mainly originate from the
Eh13 member and group C oils, defined as light oil, primarily exist in
the Eh23 member.
Group A oils from the Eh2 member correlate with Eh2 and Eh13
source rocks, while group B oils from the Eh13 member primarily
correlate with Eh13 source rocks, and group C oils from the Eh23
member mainly correlate with Eh23 source rocks.
33
Acknowledgements
This study was supported by SINOPEC Henan Oilfield Company
Research Funds (P07057-2), the National Natural Science Funds
(41072093), the National Science Foundation of China (No.
41302111) and Introducing Talents of Discipline to Universities
of Geoscience (Wuhan) (No. B14031). We thank SINOPEC Henan
Oilfield Company for financial assistance to this research and
arranging access to data files. We appreciate the enthusiastic sup-
port of Sheqing Lin and Jiaqun Luo at Exploration and Development
Research Institute of SINOPEC Henan Oilfield Company. We thank
Dr. Hua Wang, Huajun Gan, State Key Laboratory of Geological Pro-
cesses and Mineral Resources, China University of Geoscience
(Wuhan) for research assistance. We are grateful for the comments
and suggestions by the editor and reviewers, Drs. Ken Peters, Wil-
liam Meredith and Noriyuki Suzuki.
Associate Editor—Ken Peters
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