Journal of Petroleum Geology, Vol.

29(2), April 2006, pp 175 - 188 175

BIOMARKER GEOCHEMISTRY OF CRUDE OILS

FROM THE QAIDAM BASIN, NW CHINA

Yi Duan*+, Chaoyang Zheng*, Zhiping Wang**, Baoxiang Wu*,

Chuanyuan Wang*, Hui Zhang*, Yaorong Qian*** and Guodong Zheng#

A suite of 16 crude oil samples from 13 oilfields in the Qaidam Basin were analyzed using
techniques including gas chromatography and gas chromatography - mass spectrometry. Biomarker
compositions and parameters were used to investigate the palaeoenvironmental and depositional
conditions and to correlate the oils with eachother. Oils from the western Qaidam Basin have
pristane/phytane (Pr/Ph) ratios of less than 0.7, and contain abundant gammacerane, C27 steranes,
4-methyl steranes and long-chain tricyclic terpanes. C29 sterane 20S/(20S+20R) and ββ/(ββ+αα)
ratios show that the western Qaidam oils have variable maturities ranging from immature to
mature. Oils from the northern Qaidam Basin, by contrast, have Pr/Ph ratios greater than 3, low
gammacerane contents, and relatively abundant C 29 steranes, bicyclic terpanes and
alkylcyclohexanes. C29 sterane 20S/(20S+20R) and ββ/(ββ+αα) ratios indicate that the northern
Qaidam oils are mature.
δ13C values, which range from –25.4‰ to –28.3‰ with the exception of one oil from the
north (–31.6‰), are similar for oils from both the northern and western parts of the Qaidam
Basin. The oils’ carbon isotope compositions are similar to those of the organic matter in potential
source rocks.
The western Qaidam oils are inferred to have originated from Tertiary source rocks deposited
under anoxic and saline-hypersaline lacustrine conditions with dominant algal organic matter. The
northern Qaidam oils are interpreted to be derived from Jurassic source rocks which were deposited
in a freshwater lacustrine environment and which are dominated by terrigenous organic matter.

INTRODUCTION oil was first discovered in the late-1950s. The majority

Eighteen oilfields have been discovered in the
Mesozoic-Cenozoic Qaidam Basin, NW China, since
* Lanzhou Institute of Geology, Chinese Academy of
Sciences, Lanzhou, Gansu Province 730000, People’s
Republic of China.
+ author for correspondence, email: duany@ns.lzb.ac.cn
** Laboratory of Quantitative Vegetation Ecology,
Institute of Botany, Chinese Academy of Sciences, Beijing
100093, People’s Republic of China.
*** Analytical Chemistry Branch BEAD/Office of Pesticide
Programs, US EPA 701 Mapes Rd, Fort Meade, MD 20755-
5350, USA.
of these oilfields are located in the western part of
the basin but several are located in the north.
Production from many wells in the north is declining
and some wells have been abandoned due to
increasing water cuts. In spite of intensive exploration
in recent years, the petroleum geology of the Qaidam
Basin is still not well understood. Some recent studies
have focussed on the geology and geochemical
characteristics of selected source rocks (e.g. Huang
et al., 1991; Ritts et al., 1999; Hanson et al., 2001;
Jin et al., 2002; Pang et al., 2004), while others have
reported on crude oils (e.g. Philp et al., 1989, 1991;
Huang et al., 1991, 1994; Ritts et al., 1999; Hanson
et al., 2001). However, the lack of a comprehensive
data-set on oils from throughout the basin continues

# W.M. Keck Geoenvironmental Laboratory Center for

Environmental Systems, Stevens Institute of Technology, Key words: Qaidam Basin, crude oils, source rocks,
Castle Point on Hudson, Hoboken, NJ 07030, USA. biomarkers, carbon isotopes, maturation, origin.
176 Biomarker geochemistry, Qaidam Basin, NW China

s
N
nt ain Qi 30km
n Mou lia
nM
Altu 3
ou
4
Huatugou nt
5N ai
Mangaizhen ort ns
hF
au
Hongliuquan lt B
loc
Mangai k

Yilipin
We
st D
500km epr
ess
Qaidam Basin ion
Gansen
Eas
t De
pre
Beijing ssio
Ku n
Tibet
China nl
un
Moun Dazaohuo
tains
Fault Tectonic boundary Town
Oil sample site and number Geermu
QH01,02 QH03 QH04 QH05,06
QH07 QH08 QH09 QH10
QH11,12 3QH13 5QH14 4QH15
QH16

Fig. 1. Outline map of the Qaidam Basin, NW China, showing sample locations.
to hamper our understanding of the geology and
geochemistry of the hydrocarbons present there. The
basin contains oils from both saline-hypersaline
carbonate-rich source rocks, and freshwater lacustrine
source-rocks poor in carbonate, with wide ranging
maturities. It therefore provides a suitable setting for
the application of biomarker parameters to oilfield
studies.
In this paper, crude oils collected from 13 oilfields
and inferred source rocks, located in both the western
and northern Qaidam Basin, were geochemically
analyzed. The aim of the study was to identify different
genetic types of crude oils in the basin using
established geochemical parameters, and to determine
source-rock ages and depositional environments by
correlating geochemical data between the oils and
source rock extractss. In addition, we discuss
differences in biomarker composition and distribution
between saline-hypersaline lacustrine and freshwater
lacustrine depositional environments.
GEOLOGICAL BACKGROUND
The Qaidam Basin consists of three tectonic elements,
a northern fault block together with western and
eastern depressions (Fig. 1). Mesozoic and Cenozoic
sedimentary rocks are generally approximately 11km
thick reaching a maximum of 17km (Lee, 1984).
Effective source rocks include Oligocene-Lower
Pliocene lacustrine deposits (Fig. 2) in the west of the
basin, and Lower-Middle Jurassic lacustrine strata
(Fig. 2) which are confined to the north (Ritts et al.,
1999; Hanson et al., 2001).
Tertiary source rocks in western Qaidam
Oligocene - lower Pliocene source rocks in the west
of the basin mainly consist of mudstones, marls and
calcareous mudstones deposited in a deep-water
lacustrine environment. During the Oligocene - early
Pliocene, the climate in the Qaidam Basin area was
arid and the water supply was limited. Oligocene-
lower Pliocene source rocks were therefore deposited
under saline-hypersaline conditions (Huang et al.,
1991) over much of the western Qaidam Basin. They
are characterized by high carbonate contents (15% -
40%: Huang et al., 1993), and have average TOC
contents of about 0.59%. Organic matter is mainly
Type II kerogen of low maturity (Fig. 2).
Lateral variations in source rock characteristics in
the western Qaidam Basin reflect changes in
sedimentary facies during basin evolution.
Unpublished data from Qinghai oilfield suggest that
alluvial–fluvial and fluvial-deltaic conditions were
dominant during the Paleocene-Early Oligocene, with
lacustrine deposition restricted to the central and
southern parts of the western depression. From Late
Oligocene to Miocene times, lacustrine conditions
occurred more widely throughout the depression with
 Yi Duan et al. 177

Mean
Epoch Formation Thickness Sedimentary Source Reservoir TOC Maturity
(m) Facies (%) Parameter

Ro Sterane
Shizigou 300-1300 (%) Ratio
Pliocene Shallow
(N 2 ) lacustrine
0.39
Youshashan 800-4000 0.22
0.45

Miocene Upper
(N 1 ) Ganchaigou 500-900 0.47 0.26
Shallow-deep
lacustrine
Oligocene Lower 0.35
(E 3 ) Ganchaigou 500-3100 0.65 0.29
0.53

Eocene
(E 2 )
300-1000 Aliuvial
Lulehe
Paleocene
(E 1 )

Cretaceous Quyagou 200-1300 Fluvial

Upper
Jurassic 100-1300 Fluvial
(J 3 ) Hongshigou

Middle Chaishiling
Jurassic 300-2500 Shallow-deep 1.1-2.7 0.88
(J 2 ) lacustrine
Dameigou

Lower
Jurassic Shallow
Xiaomeigou 100-200 lacustrine 2.2
(J 1 )

Fig. 2. Jurassic-Tertiary stratigraphy, depositional environments, reservoirs, possible source rocks and source-
rock parameters in the Qaidam Basin. Ro: Vitrinite reflectance in source rocks (Tertiary at well Lucan 1;
Jurassic in the Lenghu region). Sterane ratio: C29 sterane 20S/(20R+20S).

Saturated Aromatic Polar Asphaltic Saturated+ Aromatic

Sample Reservoir Depth
Oilfield fraction fraction fraction fraction Polar+ Asphaltic
No.+ age (m)
(%) (%) (%) (%)
QH01 N1 Shizigou 1134 26.9 14.1 55.8 3.2 0.69
QH02 E3 1 Shizigou 4110 38.7 2.1 39.1 20.1 0.69
QH03 N22 Huatugou 489 32.3 9.8 55.0 2.9 0.73
QH04 N1 Qigequan 635 37.3 11.0 50.0 1.7 0.93
QH05 N21 Gasi 1499 44.4 7.9 34.9 12.8 1.10
QH06 E3 1 Gasi 3401 50.1 8.1 36.9 5.0 1.39
QH07 N1 Youshashan 889 49.9 15.1 30.3 4.7 1.86
QH08 E3 1 Shaxi 4141 13.2 7.0 66.2 13.6 0.25
QH09 N22 Xianshuiquan 731 34.6 8.4 55.0 2.0 0.75
QH10 N22 Nanyishan 1192 45.2 6.9 46.9 1.0 1.09
QH11 N22 Youquanzi 36.3 7.4 52.1 4.2 0.78
QH12 N21 Youquanzi 1250 78.7 10.2 9.7 1.4 8.01
QH13 J2 Lenghu3 628 54.9 8.9 34.7 1.5 1.76
QH14 N1 Lenghu5 700 80.0 4.4 14.8 0.8 5.41
QH15 N1 Lenghu4 615 51.1 8.8 37.2 2.9 1.49
QH16 N1 Nanbaxian 1811 92.2 2.4 5.1 0.4 17.20

Table 1. Bulk geochemical parameters for crude oils from the Qaidam Basin.
178 Biomarker geochemistry, Qaidam Basin, NW China
high rates of deposition. Effective source rocks of this
age are on average 1,000m thick. Meanwhile, turbidites
were deposited in the foredeep in front of the Altun
Mountains. During the Early-Middle Pliocene, due to
uplift of the Altun and Kunlun Mountains, the
lacustrine area became smaller and the depocentre
migrated to the NE, resulting in rapid lacustrine
deposition in the northern part of the depression.
Alluvial, fluvial and deltaic facies developed along
margin of the basin.
Thus, from south to north in the western Qaidam
depression, source rock characteristics change
progressively as follows:
(1) the TOC content decreases; thus the TOC of
Upper Oligocene source rock changes from 0.69%
to 0.40%;
(2) the organic type changes from mixed to humic;
(3) the maturity of the organic matter increases.
(ii) Jurassic source rocks in northern Qaidam
Lower-Middle Jurassic strata in the northern fault block
and along the southern margin of the Altun Mountains
consist mainly of fluvial and lacustrine siliciclastcs
deposited under humid climatic conditions (Ritts et al.,
1999). Lower and Middle Jurassic source rocks are
probably not contiguous across the entire Qaidam
Basin as the NE and western parts of the basin are
geodynamically distinct (Ritts et al., 1999). Upper
Jurassic - Cretaceous deposits consist of fluvial and
alluvial fan strata, lacking well-developed lacustrine
intervals and probably deposited under semi-arid to
arid climatic conditions. Their source-rock potential
is therefore likely to be low.
Lower and Middle Jurassic source rocks in the
northern fault block include mudstones, carbonaceous
mudstones and coals. The mudstones and carbonaceous
mudstones have mean organic carbon contents of 1.1-
2.7%, and variable kerogen types with dominant Type
III kerogen (Huang et al., 1993). Although the Lower-
Middle Jurassic source rocks have variable maturities,
they are mainly mature to highly mature based on
vitrinite reflectance measurements (Fig. 2; Huang et
al., 1993; Ritts et al., 1999).
SAMPLES AND METHODS
Sixteen crude oil samples were collected from 13
oilfields in the western and northern Qaidam Basin in
2001. The existence in all the studied samples of
abundant n-alkanes (Fig.3a) and the absence of C10
demethylated hopanes (Seifert and Moldowan, 1979;
Trendel et al., 1990) show that they are not biodegraded
crude oils. Reservoir rocks are Middle Jurassic to
Pliocene sandstones (Fig. 2).
Asphaltenes were removed from the oils (42.3-
103.4mg) by precipitation with n-hexane followed by
filtration. The deasphalted crude oils were further
fractionated by column chromatography using a
50cm×1cm i.d. column filled with 6g alumina (70-
230 mesh, activated for 12h at 450oC; bottom) and
9g silica (80-120 mesh, activated for 12h at 150 oC;
top). Neutral silica gel and alumina as well as filters
and cottons used were extracted with a mixture of
dichloromethane and methanol (2:1, v/v) in a Soxhlet
apparatus for 36h. Aliphatic hydrocarbon, aromatic
hydrocarbon and non-hydrocarbon fractions were
separated by elution with 180-2,00ml of n-hexane,
160-200ml of benzene and 30-50ml of methanol,
respectively, and then evaporated.
The aliphatic hydrocarbon fractions were
analyzed with a Shimadzu GC-9A gas
chromatography (GC) using a fused silica capillary
column (SE-54, 50m × 0.30mm i.d.; 0.25μm film
thickness). GC oven temperature was programmed
to rise from 60 to 300oC at 4oC min-1 then held at 300
o
C for 30min.
Biomarkers in the aliphatic fraction were
determined with a Hewlett-Packard 5890 II GC/
5989A mass spectrometer (GC-MS) equipped with
an HP-5 capillary column (50m × 0.25mm i.d.;
0.11μm film thickness). The GC oven temperature
was programmed to rise from 80 to 300oC at 4 oC
min-1, then maintained at this temperature for 30min.
The GC-MS system was operated in the full scan
mode and m/z 20 to 800.
The gasoline range (C 5 -C 8 ) hydrocarbon
compounds in crude oils were analyzed with an
Argilent Technologies 6890N GC using a Pona
19091S-001 capillary column (50m×0.2mm i.d.;
0.5μm film thickness). The GC oven was initially set
at 30oC for 4 min, subsequently programmed to 100oC
at 1.5 oCmin -1 and 290 oC at 12 oCmin -1 and then
maintained at this temperature for 20min.
Stable carbon isotope compositions of the crude
oils and rocks (from which inorganic carbon had been
removed) were determined after combustion of the
samples in quartz tubes. The tubes were opened in a
vacuum line (2×10-3 torr) and the water was removed
by trapping at –70 o C. The produced CO 2 was
collected in a sampling ampoule at –196 oC and
transferred directly to the inlet system of a Finnigan
MAT 252 mass spectrometer for carbon isotope ratio
determination. Carbon isotope values are expressed
relative to PDB carbonate (0‰).
RESULTS AND DISCUSSION
Bulk properties of crude oils
Physical properties and bulk chemical parameters of
the western Qaidam oils are different from those of
the northern Qaidam oils (Table 1). Thus specific
gravities range from 0.8180 to 0.8642 for the western
 Yi Duan et al. 179

A Ph C 20 Sample QH01 C 30
West Qaidam D Hopane
GC Sample QH03 m/z 191
Tricyclic terpane Gammacerane
Pr C 23
TmC 31
C 35
C 14 Ts
C 30

C 30
C 16
North Qaidam Sample QH15
Sample QH15
Gammacerane
C 29 C 31

Pr Ts C 33
C 14 Tm C 35
Ph C 30 C 23

Sample QH01 Sample QH01

B E
m/z 217 C 27 C 29 m/z 123 C 16
C 28 C 15

Diasterane

C 21 C 22 C 23
Relative Abundance

Sample QH15 C 27 C 29 C 15
Sample QH16
C 16

C 28

C 14

C F C 18 Sample QH01
C 29 Sample QH01
m/z 231 m/z 83
C 30
C 28
β-Carotane

C 36

Sample QH15 C 20
Sample QH15

Time

Fig. 3. Representative chromatograms of (a) n-alkanes, (b) steranes, (c) 4-methyl steranes, (d) tricyclic and
pentacyclic terpanes, (e) bicyclic terpanes and (f) long-chain alkylcyclohexanes and β-carotanes for the oils
analysed from western Qaidam (above) and northern Qaidam (below).
180 Biomarker geochemistry, Qaidam Basin, NW China
Fig. 4. Cross-plot of Pr/n-C17 vs. Ph/n-C18 for crude oil samples from the Qaidam Basin.
Qaidam oils and from 0.8040 to 0.8146 g/cm3 for the
northern Qaidam oils; viscosities are 7.9-25.2 and 1.5-
6.6 mPa·s, respectively; and pour points 17.0-36.0 and
–2.0 to –9oC, respectively. The western Qaidam oils
are dominated by polar components, while the northern
Qaidam oils consist largely of saturated hydrocarbons
(Table 1). The ratio of hydrocarbons to polar and
asphaltic components is 0.25 to 1.86 for the western
Qaidam oils (with the exception of sample QH12),
and 1.49-17.20 for the northern Qaidam oils. These
characteristics of the crude oils are closely related to
their maturity.
Categorization of oils
On the basis of the biomarker and carbon isotope data,
the oil samples from the Qaidam Basin were divided
into two groups: Group 1 (samples QH01-12) from
western Qaidam; and Group 2 (samples QH013-16)
from northern Qaidam.
Group 1 oils
This group of oils has CPI (carbon preference index)
values of <1 and Pr/Ph (pristane/phytane) ratios of <0.7
(Fig. 3a and Table 2). A low Pr/Ph ratio has been taken
to indicate anoxic hypersaline depositional conditions
(ten Haven et al., 1987, 1988). A cross-plot of Pr/n-
C 17 versus Ph/n-C 18 can be used to indicate oil
maturatity as well as the redox state of the depositional
environment and the organic matter type of the source-
rock (Connan and Cassou, 1980; Peters et al., 1999;
Hanson et al., 2000). From this plot (Fig. 4), the
western Qaidam oils appear to have originated from a
source rock deposited in a reducing environment. Note
that oils in the western Qaidam Basin, which are
believed to have originated from hypersaline lacustrine
source rocks, have Pr/n-C17 and Ph/n-C18 ratios typical
of a marine environment (Fig. 4; Peters et al., 1999).
A high relative abundance of β-carotane was found
in the western Qaidam oils (Fig. 3f). β-carotane is
commonly associated with anoxic and algal-rich
lacustrine environments (Fu et al., 1986; Hanson et
al., 2001).
The western Qaidam oils have low contents of
diasterane, with diasterane/regular sterane ratios
ranging from 0.05 to 0.1 (Table 2). The ratio of
diasteranes/regular steranes has been used as a
maturation index. However, it was also observed that
the concentrations of diasteranes in samples QH02
and QH10 are low although C 29 -sterane 20S/
(20S+20R) ratios are high for these two samples (0.5
and 0.4, respectively).
Previous studies have shown that carbonate-
derived oils contain relatively low amounts of
diasteranes due to the absence of clay minerals which
can catalyze sterane rearrangment reactions (Mello
et al., 1988; Peters and Moldowan, 1993). Philp et
al. (1991) suggested that the amount of diasteranes
in an oil may decrease in highly reducing non-
carbonate environments with increasing salinities.
The low diasterane/regular sterane ratios for the
western Qaidam oils therefore indicates generally
saline-hypersaline depositional conditions.
A high content of gammacerane in a source rock
or an oil is generally associated with a hypersaline
depositional environment (Moldowan et al., 1985; Fu
et al., 1986; Philp et al., 1991). The relative
abundance of gammacerane is high in all the western
Qaidam oils (Fig. 3d), which have gammacerane/C30
αβ-hopane ratios of 0.3-1 (Fig. 5).
The western Qaidam oils also contain high amount
of >C30 hopanes (Fig. 5). In addition, the positive
correlation of >C 30 hopane contents with
gammacerane/C30 hopane ratios indicates that the
occurrence of >C 30 hopanes, in common with
gammacerane (Fig. 5), may be controlled by the
salinity of the environment, although it has been noted
2001).
4-meth. ster. dia. C2920S Ts bicyc.
Sample Reservoir Oil Depth
Crange Cmax CPI C21–/C21+ Pr/Ph reg. ster. reg. ster. 20S+20R Tm terp.
No. age field (m)
hop.
QH01 N1 Shizigou 1134 14-32 16 0.88 1.03 0.49 0.38 0.095 0.41 0.23 0.093
QH02 E31 Shizigou 4110 14-34 18 0.99 1.20 0.53 0.21 0.073 0.46 0.43 0.152
QH03 N22 Huatugou 489 14-30 20 0.93 1.17 0.51 0.14 0.109 0.40 0.56 0.191
QH04 N1 Qigequan 635 13-34 16 0.88 1.00 0.40 0.26 0.079 0.30 0.28 0.088
QH05 N21 Gasi 1499 14-34 17 0.94 1.18 0.41 0.19 0.057 0.25 0.30 0.033
QH06 E31 Gasi 3401 14-35 16 0.98 1.20 0.55 0.13 0.057 0.30 0.39 0.144
QH07 N1 Youshashan 889 14-34 18 0.91 1.06 0.49 0.18 0.061 0.28 0.25 0.088
QH08 E31 Shaxi 4141 14-35 17 0.95 1.17 0.48 0.15 0.092 0.37 0.67 0.142
QH09 N22 Xianshuiquan 731 14-30 16 0.87 1.10 0.44 0.13 0.066 0.28 0.39 0.161
QH10 N22 Nanyishan 1192 13-34 16 0.98 1.07 0.66 0.25 0.141 0.43 0.53 0.219
QH11 N22 Youquanzi 13-31 18 0.97 0.85 0.55 0.32 0.083 0.30 0.44 0.156
QH12 N21 Youquanzi 1250 14-34 22 0.94 0.72 0.64 0.25 0.053 0.27 0.33 0.123

al., 1985; Philp et al., 1991; Hanson et al., 2000). Figs.

of source rocks and organic matter type (Moldowan et
organic matter (Moldowan et al., 1989; Hanson et al.,

3b and 6 show that the oils from the western Qaidam

has been used to determine the depositional environment
The relative abundance of C27-C29 steranes in oils
of a reducing environment or of bacterial sourced-

Basin contain relatively large amounts of algal-derived

C27 steranes. This observation is consistent with Pr/n-
that the C34 and C35 homohopanes are a possible indicator
QH13 J2 Lenghu3 628 13-30 16 1.10 2.47 3.86 0 0.280 0.54 1.55 0.623
QH14 N1 Lenghu5 700 13-31 16 1.08 2.39 3.08 0 0.399 0.46 1.76 1.495
QH15 N1 Lenghu4 615 14-30 16 1.06 1.98 3.23 0 0.250 0.48 1.75 0.471
Yi Duan et al.

QH16 N1 Nanbaxian 1811 11-31 15 1.12 4.67 3.75 0 0.350 0.51 2.47 4.460
Reg. ster. ü Regular sterane; 4-Meth. ster. — 4-Methyl sterane; Dia. — Diasterane; Gam.— gammacerane; hop.— hopane; Bicyc.terp. — Bicyclic terpane.
The individual parameters used here were calculated with peak heights of the compounds on the chromatograms

Table 2. Molecular parameters (n-alkanes, isoprenoids, steranes and terpanes) in crude oils from the Qaidam Basin.

organic matter for this group of oils.

probably derived from algal material.

steranes suggests that the western Qaidam oils are
181

(Philp et al., 1991). The presence of 4-methyl

western Qaidam oils (Fig. 3c and Table 2). These

Volkman et al., 1993; Huang et al., 1994), although

from dinoflagellates (Robinson et al., 1984;
compounds have been used to infer a contribution
C17 and Ph/n-C18 ratios from algal and bacterial

they have also been reported to be present in bacteria

In addition, 4-methyl steranes are present in the
182 Biomarker geochemistry, Qaidam Basin, NW China

1.2

Gammacerane/C 30 hopane
Northern Qaidam
Western Qaidam
Hypersaline
0.8

ity
lin
Sa
0.4 Saline

Freshwater
0
0 20 40 60
> C 30 hopane
Fig. 5. Cross-plot of gammacerane/C30 αβ hopane ratio versus relative contents of >C30 hopanes for the
Qaidam oils.

C 27
0 0
10

50
50

Western Qaidam oils

Northern Qaidam oils

10
0 0
C 28 C 29
0 50 100

Fig. 6. Ternary diagram of sterane C27, C28 and C29 compositions for the crude oil samples analysed.

The western Qaidam oils contain abundant long-
chain tricyclic terpanes (Fig. 3d). The tricyclic terpane/
hopane ratios of the oils range from 0.4 to 0.7 (Fig.
7). Long-chain terpanes are thought to be derived from
algae and bacteria (Aquino Neto et al., 1983),
although it has been reported that tricyclic terpanes
vary with depositional environment (Philp et al.,
1989). Because C27 steranes are mainly derived from
C27 sterols in algae, the positive correlation between
the tricyclic terpane/hopane ratio and C27 sterane
abundance in the oils indicates that the tricyclic
terpanes are likely to be derived from algal sources in
these samples (Fig. 7).
Bicyclic sesquiterpanes are present in small
amounts in this group of oils (Fig. 3e) and bicyclic
terpane/hopane ratios range from 0.03 to 0.2 (Table
2). Long-chain alkylcyclohexanes are also found in
these oils (Fig. 3f) with carbon numbers ranging from
C14 to C37 with one or two maxima between C16 and
C22 (Table 3). Alkylcyclohexane/hopane ratios for this
group oils are low, ranging from 7.1 to 16.2.
Carbon isotope ratios for oils and organic matter
have been used widely in oil to source-rock
correlations (Sofer, 1984; Chung et al., 1992; Duan
et al., 1997a, 1997b). Carbon isotope ratios for oils
from western Qaidam range from –25.4‰ to –27.5‰
with an average value of –26.6‰ (Table 2). These
values are within the range of lacustrine organic matter
in source-rocks deposited in a saline-hypersaline
environment (Peters et al., 1996).
 Yi Duan et al. 183

Fig. 7. Cross-plot of tricyclic terpane/hopane ratios versus relative contents of C27 steranes for the crude oils
analysed.
0.6
C 29 sterane 20S/(20S+20R)

n Mature
0.5 a tio
ur
at
0.4 M
Low-mature
0.3

0.2 Immature
Northern Qaidam
0.1 Western Qaidam
0
0 0.1 0.2 0.3 0.4 0.5 0.6
C 29 sterane ββ/(ββ+αα)
Fig. 8. Cross-plot of C29 sterane 20S/(20R+20S) ratio versus ββ/(ββ+αα) ratios for the crude oil samples
analysed.

Group 2 oils 6), and 4-methyl steranes are not found (Table 2). The
This group of oils have high CPI values (>1) and high oils have relatively small amounts of long-chain
Pr/Ph ratios (3 to 3.9; Fig. 3a and Table 2), suggesting tricyclic terpanes compared to Group 1 oils (Fig. 3d)
that they were derived from terrestrial organic matter and tricyclic terpane/hopane ratios range from 0.09
(Powell and McKirdy, 1973; Moldowan et al., 1985; to 0.2 (Fig. 7). However, Group 2 oils have relatively
Hughes et al., 1995; Duan, 2001). Although the higher amounts of bicyclic sesquiterpanes and long-
validity of using Pr/Ph ratio above 1 as an index of chain alkylcyclohexanes compared to Group 1 oils
the depositional environment has been questioned, a (Fig. 3e and 3f). Bicyclic terpane/hopane ratios range
high Pr/Ph ratio (greater than 3) is indicative of from 0.4 to 4.5 (Table 2). The high relative abundance
precursor higher plant material and is typical of coal- of bicyclic terpanes is probably associated with higher
sourced oils (Hughes et al., 1995). On the other hand, plant organic matter. Long-chain alkylcyclohexanes
Fig. 4 shows that the northern Qaidam oils were have a carbon number range of C12-C34 with maxima
generated in an oxidizing environment, and this is at C16-C19 (Table 3). Alkylcyclohexane/hopane ratios
consistent with the absence of β-carotane (Fig. 3f and range between 7.12 and 16.15; the abundance of long-
Table 3). chain alkylcyclohexanes probably also reflects
Group 2 oils contain larger amounts of diasterane derivation from higher plants (Dong et al, 1993). Thus
than Group 1 oils (Table 2) indicating shale-rich in summary, the results strongly indicate a significant
source rocks (Mello et al., 1988). However, the oils contribution by terrestrial organic matter to the oils
contain small amounts of gammacerane (Fig. 3d), with in this group.
gammacerane/C30 αβ-hopane ratios of 0.03-0.08 (Fig. The northern Qaidam oils have carbon isotopic
5). Concentrations of >C30 hopanes are also low in compositions ranging from –26.7‰ to –28.3‰ with
this group of oils. These observations indicate the exception of one sample (–31.6‰). Organic matter
freshwater depositional conditions (Fig. 5). in coal and freshwater lacustrine source rocks in
In contrast to the Group 1 oils, relative northern Qaidam have isotope ratios ranging from
concentrations of C29 steranes in Group 2 oils are -26‰ to -29‰ (unpublished data). This is consistent
higher than concentrations of C27 or C28 steranes (Fig. with observed isotope data from oils in this area.
184 Biomarker geochemistry, Qaidam Basin, NW China

Sample Cyclohex. Carotane 2,4-/ Temp. į13C values

Crange Cmax CPI C21–/C21+
No. hop. hop. 2,3-DMP (ć) (ă,PDB)
QH01 15-35 18 1.01 0.86 7.34 0.186 –25.4
QH02 15-36 19 1.08 0.65 16.15 0.328 –26.3
QH03 15-33 18,21 0.96 0.67 15.80 0.201 –26.7
QH04 14-34 18,19 0.95 0.74 7.98 0.188 –26.3
QH05 15-36 18,20 0.93 0.69 7.27 0.144 0.13 109.4 –26.2
QH06 15-37 18 0.92 0.60 14.35 0.165 –27.5
QH07 15-35 22 0.98 0.53 10.35 0.197 0.18 114.3 –27.1
QH08 15-36 19 1.09 0.55 13.62 0.131 0.16 112.5 –27.0
QH09 15-36 16 0.91 0.64 6.42 0.204 –26.4
QH10 14-34 17 1.11 0.82 15.70 0.157 –26.5
QH11 15-35 19 0.99 0.52 13.38 0.091 –26.8
QH12 14-36 16 0.86 0.60 7.12 0.073 0.18 114.3 –26.7
QH13 13-34 16 0.94 0.78 26.08 0 0.51 129.9 –31.6
QH14 14-32 19 1.06 0.99 35.96 0 0.47 128.7 –26.7
QH15 15-34 18,19 0.88 0.82 20.71 0 0.40 126.3 –28.3
QH16 12-34 18 0.96 1.44 63.55 0 0.50 129.6 –28.1
Cyclohex.—alkylcyclohexane; hop.—hopane; 2,4-/2,3-DMP—2,4-/2,3-dimethylpentane ratio;
Temperature (ć)—hydrocarbon generation temperature determined from 2,4-/2,3-DMP ratio.
The individual parameters used here were calculated with peak height of the compounds on the chromatograms

Table 3. Molecular parameters (alkylcyclohexanes, β-carotane and light hydrocarbons) together with carbon
isotope compositions for crude oils from the Qaidam Basin.

Thermal maturities Philippi, 1975; Hunt, 1984; Mango, 1987, 1990).

Oil maturity can be indicated by a variaety of
biomarker parameters such as extended hopane ratios
22S/(22S+22R) and hopane αβ/βα; sterane 20S/
(20S+20R) and ββ/(ββ+αα); and the methyl-
phenanthrene indices (MPI-1 and MPI-2) of aromatic
hydrocarbons.
Our results from the Qaidam Basin suggest that
the hopane ratios 22S/(22S+22R) and αβ/βα and the
methylphenanthrene indices do not reflect the maturity
of oils. For example, although the maturities of
samples QH05 and QH15 are significantly different
(with C29-sterane 20S/(20S+20R) ratios of 0.25 and
0.48, respectively), they have similar MPI-1 values
(0.7 and 0.8). The C 29-sterane parameters 20S/
(20S+20R) and ββ/(ββ+αα) were found to indicate
the maturity of the Qaidam oils more consistently
(Seifert and Moldowan, 1978; Mackenzie, 1984;
Mackenzie and Mackenzie, 1983; Peters et al., 1999).
Differences in the maturity of Group 1 and Group
2 oils can clearly be illustrated using the ratios 20S/
(20S+20R) and ββ/(ββ+αα) of C29 steranes (Fig. 8).
Group 1 oils include immature, early mature and
mature oils with a predominance of early mature oils,
while the Group 2 oils are mature.
In addition to the sterane maturity index, the
terpane Ts/Tm ratio is commonly used as a maturity
parameter. The northern Qaidam oils have higher Ts/
Tm ratios (>1.55) than the western Qaidam oils
(<0.67, Table 2). This also indicates that the northern
Qaidam oils are more mature than the western Qaidam
oils.
The analysis of gasoline-range hydrocarbons can
also indicate maturity differences between oils (e.g.
Mango (1987, 1990) proposed the 2,4-/2,3-
dimethylpentane ratio to be a function of maturity,
independent of source input and depositional
environment. BeMent et al. (1995) established the
relationship between this ratio and the generation
temperature of the oil. Using BeMent’s calibration,
we calculated the generation temperatures of some of
the studied oils, and values obtained vary between
109.4oC and 114.3oC for western Qaidam oils, and
between 126.3oC and 129.9oC for northern Qaidam
oils (Table 3). These data also indicate that western
Qaidam oils have higher maturities than northern
Qaidam oils.
Oil source
To investigate the genetic link between the oils studied
and potential source rocks, we analyzed extracts from
one Tertiary mudstone and one Jurassic mudstone by
GC-MS using the experimental conditions described
above. Analytical results are presented in Fig. 9.
The carbonate-rich Tertiary mudstone had a low
Pr/Ph ratio, abundant β-carotane (Ritts et al., 1999),
and abundant gammacerane and C27 steranes (Fig. 9),
as well as 13C-rich carbon isotope ratios (–21‰
to –26‰). Biomarkers in the samples are very similar
to those found in Tertiary rock samples by Huang et
al. (1993), Jin et al. (2002) and Zhu et al. (2003; Table
4). These rocks also have C29 sterane 20S/(20S+20R)
and ββ/(ββ+αα) ratios of 0.01-0.55 and 0.10-0.56,
respectively (Huang et al., 1991). These data for
Tertiary rocks in western Qaidam are consistent with
observations on the Group 1 oils described above.
Consequently, the Tertiary rocks are considered to be
 C30 C 30
Western Qaidam Western Qaidam
m/z 217 Tertiary m/z 217 m/z 191 Tertiary m/z 191 oils
oils
source rock source rock
Gammacerane
C27 C29 C29
C27
C28 C28 Gammacerane
Oleanane Oleanane

C30 C30
Northern Qaidam
m/z 217 Jurassic m/z 217 C27 oils m/z 191 Jurassic m/z 191 Northern Qaidam
source rock C29 source rock oils
Yi Duan et al.

C28
C29

Relative abundance
C27
C28 Gammacerane Gammacerane

Time

Fig. 9. Biomarker compounds in Tertiary and Jurassic postulated source rocks, showing the correlation between oils and source rocks.
185
 Sample Reservoir/ CPI Pr/Ph C27 (%) C2 8 (%) C29 (%) į13C values
186

Gam. Gam. Dia.

source rock (PDB)
C30 Įȕ hop. C31 hop. reg. ster.
age
Western
0.88-0.98 39.0-52.7 18.1-24.9 28.8-39.8 0.053-0.141 –25.4̚–27.5
Qaidam E3-N2 0.40-0.64 (12) 0.27-1.00 (12) n.c.
(12) (12) (12) (12) (12) (12)
oils

Northern
1.06-1.12 0.03-0.08 34.6-38.3 14.8-21.5 40.7-50.6 0.250-0.350 –26.7̚–31.6
Qaidam J2- N1 3.08-3.86 (4) n.c.
(4) (4) (4) (4) (4) (4) (4)
oils

E3 0.95 0.55 0.55 n.c. 45.8 21.7 32.5 n.c.

Western –21.0̚–26.0
Qaidam 28.2-64.2 (40) 18.6-35.5 23.1-37.2 (9)
E-N 0.16-0.93 (40)*
source 0.74-2.17 0.31-1.13 1.33-2.42 * (40) * (40) * 0.032-0.110

gammacerane and higher maturities.

rocks (40)* + (40)* (20)+ 19.0-38.0 21.0-48.0 (9)* –21.0 ̚–26.0
E3 0.27-0.89 (20) 24.0-56.0 (20)+
(20)+ (20)+ (20)+
J1 1.08 3.11 0.06 n.c 19.6 17.9 62.5 n.c.
Northern –26.0̚–29.0
Qaidam 1.17-4.64 41.8-75.0 (8)
J 8.0-37.1 (11) * 15.1-22.1(11)*
source 1.21-2.22 (11)* 0.02-0.19 0.02-0.14 (11)* 0.120-0.36
rocks (11)* + (11)* (20)+ + + 41.0-67.0 (7) * –27.1̚–30.4
J1 1.72-4.27 (20) 16.0-35.0 (20) 12.0-30.0 (20)

(Qinghai Petroleum Administration, unpublished

rocks, they would have low concentrations of

contributions to oils in western Qaidam, because pre-

data). If the oils originated from pre-Tertiary source

Tertiary lacustrine source rocks were deposited under
the most probable source rocks for this group of oils.

freshwater conditions and have higher maturities

We rule out the possibility of pre-Tertiary source
(20)+ (20)+
Reg. ster.üRegular sterane; Dia.—Diasterane; Gam.—gammacerane; hop.—hopane
*Data from Zhu et al. (2003)
#
Data from Huang et al. (1993)
+
Data from Jin et al. (2002)
Numbers in bracket represent the analytical sample numbers
Biomarker geochemistry, Qaidam Basin, NW China

Table 4 A summary of typical geochemical parameter distributions for the crude oils and potential source rock extracts analysed.

Lower-Middle Jurassic rocks are assumed to be

have high Pr/Ph ratios (Ritts et al., 1999), low contents

9), and lack β-carotane (Ritts et al., 1999); also, they

of gammacerane, a dominance of C29 steranes (Fig.
lacustrine environment with a significant input of
Basin, and were deposited in clay-rich, freshwater

have light carbon isotope compositions (–26‰ to –

higher plant organic matter as described above. They
the main effective source rocks in the northern Qaidam
 Yi Duan et al.
29‰).The organic matter in the Lower-Middle
Jurassic source rocks is primarily mature (Fig. 2;
Huang et al., 1993; Ritts et al., 1999). These features
are similar to those of the Group 2 oils as described
above, and strongly suggest that these oils are derived
from the Jurassic source rocks.
Huang et al. (1993), Jin et al. (2002) and Zhu et
al. (2003) investigated biomarker compositions in
Jurassic rock samples (Table 4). The data show that
biomarker parameters and carbon isotope
compositions in Jurassic rocks are different from those
in Tertiary rocks in the western Qaidam and Group 1
oils, but are a close match for the Group 2 oils. Further
evidence is that minor oleanane is present in the Group
1 oils and Tertiary rocks, but is absent in the Group 2
oils and Jurassic rocks (Fig. 9). This compound is
thought to be derived from angiosperm higher plants
which were not prtesent before the Late Cretaceous
(Ekweozor and Udo, 1988); oleanane is therefore an
age-diagnostic biomarker. Its existence in Group 1 oils
and Tertiary rocks, and its absence from Group 2 oils
and Jurassic rocks, indicates that Group 1 oils originate
from Tertiary source rocks, while Group 2 oils are
derived from pre-Tertiary (Jurassic) source rocks.
CONCLUSIONS
Hydrocarbon biomarkers and carbon isotope
compositions of oils from both the western and
northern Qaidam Basin were analysed in order to
establish the origins of these oils. For western Qaidam
oils, the distinct even-odd preference of n-alkanes, the
low Pr/Ph ratios, the presence of β-carotane, and
abundant gammacerane and >C30 hopanes, together
with carbon isotope compositions averaging –26‰
suggest an anoxic and saline-hypersaline depositional
environment for the respective source rocks. Relatively
high contents of C27 steranes, regular steranes, 4-
methyl steranes and long-chain tricyclic terpanes, and
relatively low contents of bicyclic terpanes and
alkylcyclohexanes indicate that the source of organic
matter was dominantly algal. The C29 sterane 20S/
(20S+20R) and ββ/(ββ+αα) ratios of oils from
western Qaidam show variable maturities, but
immature to low maturity oils are dominant. These
results are consistent with those from extracts of
Tertiary hypersaline lacustrine deposits, which are
therefore inferred to be the source of oils in western
Qaidam.
In contrast, the northern Qaidam oils are
characertized by an apparent odd-even preference of
n-alkanes, high Pr/Ph ratios, the absence of β-carotane,
and a low content of gammacerane and >C30 hopanes,
which indicate a suboxic and freshwater depositional
environment. The abundance of C29 steranes, bicyclic
terpanes and alkylcyclohexanes, together with the low
187
content of regular steranes and long chain tricyclic
terpanes and the absence of 4-methyl steranes, suggest
that the source of the precursor organic matter was
dominated by terrigenous higher plant material. The
high C29 steranes 20S/(20S+20R) and ββ/(ββ+αα)
ratios indicate that the north Qaidam oils are mature.
The molecular parameters of these oils are consistent
with those of extracts from Jurassic freshwater
lacustrine deposits, which are consequently inferred
to be the source of the oils.
ACKNOWLEDGEMENTS
This study was supported by Knowledge Innovation
Project in Resource and Environment Field, Chinese
Academy of Sciences, Grant No. KZCX3-SW-128;
Important Project of the Bureau of International Co-
operation, Chinese Academy of Sciences, Grant No.
GJHZ0530; and the “973” Program of China Grant
No. 2005CB422105. We are grateful to Kliti Grace
for constructive criticisms; and also Maowen Li, Mike
Pearson and anonymous referee for reviews which
significantly improved the manuscript.
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