Geochimica et Cosmochimica Acta, Vol. 65, No. 15, pp.

2555–2570, 2001
Copyright © 2001 Elsevier Science Ltd
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PII S0016-7037(00)00608-1

Pb, Sr, and Nd isotopic features in organic matter from China and their implications for
petroleum generation and migration
ZHU BING-QUAN,1,* ZHANG JING-LIAN,2 TU XIANG-LIN,1 CHANG XIANG-YANG,1 FAN CAI-YUAN,1 LIU YING,1 and LIU JU-YING1
1
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan, Guangzhou 510640, China
2
Northwest Institute of Geology, China National Petroleum Cooperation, Lanzhou 730020, China

(Received October 13, 2000; accepted in revised form March 12, 2001)

Abstract—To better understand processes and sources of crude oil and bitumen generation from kerogen
rocks, a comprehensive study of Pb, Sr, and Nd isotopic systematics was undertaken for bitumen, crude oil,
and kerogen from two large oil fields (Karamay and Liaohe) and two paleo-oil deposits (Tarim and Guizhou)
in China. The bitumen samples from the Karamay oil field have present-day 143Nd/144Nd ratios pointing to
a depleted mantle origin (0.5126 – 0.5130). They define a Rb-Sr isochron age of 286 ⫾ 12 Ma. Pb isotopic
compositions for bitumen and crude oil from Karamay, Liaohe, and Tarim all show features of crust–mantle
mixing. They are evidently different from Pb isotopic compositions of kerogen that occurred in the same strata
of the various oil fields, which mostly show crustal signatures. Sr isotopic compositions in crude oil from
Liaohe are consistent with those of carbonate sediments and volcanic rocks in island arc environments
(0.7065– 0.7100). Radiometric isotope systems can be preserved in the bitumen with low vitrinite reflectance
R0 (⬍0.5%) and therefore allow us to date petroleum generation. Both isotopic data and the geologic setting
of the oil fields indicate that petroleum generation was associated with fluid action from deep sources,
including the mantle, lower crust, and buried strata in rift basins and buried foreland basins at craton margins
or subduction zones. Copyright © 2001 Elsevier Science Ltd

1. INTRODUCTION environments of oil formation and preservation as well as the

influence of crust–mantle interaction on oil generation.
The strontium isotopic ratios of oil field waters, brines, and
formation waters have been widely used for elucidating envi-
2. SAMPLE LOCATION AND OCCURRENCE
ronments of genesis and migration of petroleum (Stueber et al.,
1984, 1993; Chaudhuri et al., 1987; Stueber and Walter, 1991; The samples were collected from four areas: Liaohe and Karamay,
Bullen et al., 1996). However, water is an open system for which are the large oil fields, and Tarim and Guizhou, which are
radiogenic isotopes, and there is unceasing isotope exchange paleo-oil fields with huge bitumen deposits (Fig. 1).
with host rocks. Migration paths and rates of oil field water are
also somewhat different from those of petroleum. Thus, isoto- 2.1. Karamay Bitumen
pic signatures of oil field water cannot trace the environment of The Karamay oil field lies on the western edge of the Junggar Basin
petroleum generation and migration well. Many studies have in northern Xinjiang. The Talabude fault associated with an ophiolite
revealed that metals bound to organic ligands and porphyrin as zone delineates the suture line between the Hasakestan and Junggar
organic complexes are stable at relatively high temperature and plates (Fig. 1a). As shown in the map (Fig. 1a), the oil field is near and
parallel to the suture zone—a distance of ⬃25 to 30 km (Zhang and
pressure (Shock and Koretsky, 1995; Huseby and Ocampo, Zhai, 1993). The Junggar basin is filled with Paleozoic-Mesozoic strata.
1997). Thus, the radiogenic isotopic systematics may be pre- The geologic setting of major oil pools appears to have been controlled
served in bitumen, crude oil, peat, and kerogen as closed by the Karamay-Wuerhe fault. The massive bitumen samples were
systems in environments of petroleum formation and migration. collected from the Wuerhe bitumen veins in the northeastern part of the
Karamay oil field. There are seven bitumen veins at the eastern side of
The study of Pb, Sr, and Nd isotopes shows good potential the Karamay-Wuerhe fault, which intruded into the gentle strata of
for understanding petroleum genesis, comparing oil sources, Cretaceous sandstones and stretched along the fault direction with
dating organic matter formation and migration, and constrain- length of 1 to 4 km and width of 1 to 2 m. Thus, the migration age of
ing tectonic environments in oil field settings (Parnell and bitumen is Cretaceous or younger. The underlying strata are predom-
Swainbank, 1990; Manning et al., 1991; Mossman et al., 1993; inantly Carboniferous argillites, argillaceous limestones, and volcanic
rocks, inferred via island arc derivation. The bitumen is of high purity
Stille et al., 1993; Rowe et al., 1997; Pushekarev et al., 1998; and is brittle, with a glassy luster and shell-like fractures. The vitrinite
Zhang et al., 1999). However, the available results are limited, reflectance R0 is in the range of 0.40 to 0.42%, which indicates that the
and the implications of radiogenic isotopic systematics for bitumen was not metamorphosed at a temperature higher than 200°C
generation and migration of petroleum need to be refined. A (Fu et al., 1989).
comprehensive study on Pb, Sr, and Nd isotopic systematics for
bitumen, crude oil, and kerogen from two large oil fields and 2.2. Tarim Bitumen
two paleo-oil deposits in China is presented in this article. On The Tarim Basin in northwest China was formed during the Late
the basis of isotopic evidence, we discuss the age and tectonic Proterozoic and Early Paleozoic (Fig. 1). The basement of the basin
was formed during the early Archaean to middle Proterozoic (Kang,
1992). The strata are mainly composed of carbonates and detrital rocks
*Author to whom correspondence should be addressed. (Email: with a thickness of 4000 to 17,000 m. The Cambrian black shales and
[email protected]). Ordovician shales and argillaceous limestones are interpreted as con-
2555
2556 Z. Bing-Quan et al.

Fig. 1. (A) Tectonic map of continental China showing distribution of oil fields and sample locations. K ⫽ Kangdian
paleocontinent; N ⫽ Jiangnan paleocontinent; CM ⫽ Central Mongolian block; X ⫽ Xingan block; J ⫽ Jiamusi block; L ⫽
Liaojiao block; S ⫽ Sunan block. (B) Karamay oil field. (C) Tarim paleo-oil field. (D) Guizhou paleo-oil field. (E) Liaohe
oil field and Sr isotopic contours (map scale: 0.1 degree ⫽ 10 km).
 Pb, Sr, and Nd isotopes in organic matter from China 2557

tinental slope deposits and are regarded as the source rocks of petro- water to remove adsorbed metal elements, then further pulverized into
leum generation in the Tarim Basin. The Silurian sandstones are the a powder of 80 to 100 mesh in an agate crusher. The powder of 3 to 5 g
major reservoirs of bitumen. Carbonate sedimentation during the Car- for each sample was ashed in quartz beakers by slowly heating them to
boniferous represented the transgression of seas. Early Permian rifting 750°C in a furnace for ⬃6 h.
was associated with large-scale basalt eruption and diabase emplace- For the crude oil samples, water and solid impurities were first
ment. A great quantity of bitumen was found in cracks and pores in separated by gravity fallout, filtering, and centrifugation separation, and
sandstones and limestones of Silurian and Ordovician strata, with 10 to 15 g each were ashed in a manner similar to the bitumen. The
reserves of ⬃90 billion tons and a thickness of 20 to 67 m in the Keping mass ratios of ash to starting sample were usually lower than 0.35%,
area, at the northwestern edge of the Tarim Basin (Fig. 1b). It is the which indicates that the content of inorganic minerals in bitumen and
largest paleo-oil field in China. crude oil was very low. Kerogen samples were extracted by dissolving
The vitrinite reflectance R0 of bitumen varies from 0.67% to 0.96%, kerogen rocks with high-purity hydrofluorite (HF). Metal minerals,
indicating the metamorphic temperature is within the range of 250 to such as pyrites, were separated from kerogen by heavy liquid separa-
300°C. Samples containing small bitumen veins with a width of 1 to 10 tion. Bitumen-A (soluble organic matter, which represents potential of
mm were collected from these strata via surface and drill cores. The petroleum generation) was extracted by dipping kerogen in double-
samples of TD1-8 are from Silurian sandstones at the TD site, TA-2 distilled chloroform. Kerogen samples of ⬃5 g were ashed in a furnace
and TA-5 are from Lower Ordovician limestones at the TA site, and by heating to 950°C. Two to 3 g of bitumen-A were used; ashing
CP-1 and CP-2 are from Permian limestones at the CP site (Fig. 1b). temperature was 750°C. Two or three batches of ash and one batch of
The samples H-4-8 and LN-59-1 are from Silurian sandstones and clean bitumen powder for each sample were prepared for chemical and
Triassic limestones in the drill cores from 6100 m and 5200 m, isotopic analyses.
respectively, to the east of Akesu. Triassic strata do not crop out in this
area. The kerogen samples were separated from kerogen rocks (black
3.2. Extraction of Sr, Nd, and Pb
shales) of the Ordovician and Cambrian strata in the same areas at TDO
and TDXE sites in Figure 1b, respectively. One batch of ash was spiked with Rb, Sr, Sm, and Nd, then dissolved
with 1:1 HNO3. Residual inorganic minerals (silicates and carbonates)
2.3. Guizhou Bitumen were removed through centrifugation. Rb, Sr, and REE were separated
with a Dowex 50 cation exchange column and 2 N and 4 N HCl for
A second large paleo-oil field in China occurs in a Paleozoic basin in elution. Nd and Sm were extracted from the REE fraction with a
the southeastern Guizhou province (Fig. 1c). It is situated on the eastern HEDHP ion exchange column and 0.2 N and 0.5 N HCl. The second
margin of the Jiangnan paleocontinent. The reservoirs of bitumen are batch of the ash was directly dissolved with 1:1 HNO3, from which Pb
sandstones and shales of Middle Cambrian age and limestones of was extracted in a microexchange column of anion resin of Dowex-I
Ordovician age in the Majiang-Wenan areas (Liu et al., 1988). Bitumen (200 – 400 mesh) in HBr solution. The procedural blanks were lower
veins also widely occur with the Hg, Sb, As, and Sn deposits of the than 5, 10, 50, 20, and 100 pg for Sm, Nd, Rb, Sr, and Pb, respectively,
Devonian and Cambrian strata in this area. The estimated reserves of and can be neglected. The third batch of the ash was dissolved with 1:1
bitumen are ⬃1.8 billion tons. The massive bitumen samples were HNO3 for inductively coupled plasma mass spectrometer (ICP-MS)
collected from the Hg deposits occurring in the Cambrian strata. The elemental analyses.
vitrinite reflectance R0 of the bitumen samples is 2.1 to 3.2%, suggest- To check the influence of Pb loss during sample ashing on Pb
ing the bitumen has suffered thermal metamorphism with temperatures isotopic analyses, some batches of clean bitumen powder were directly
of ⬎350°C (Fu et al., 1989). Kerogen samples were collected from the dissolved with HNO3 for Pb isotopic analyses, according to the pro-
black shales of Middle Cambrian in the area near the sampling site of cedure used by Parnell and Swainbank (1990). These results were
bitumen. comparable to those of the ashing procedure (Tu et al., 1997).

2.4. Liaohe Crude Oil 3.3. Mass Spectrometer Analyses

The Liaohe oil field lies in the Tertiary basin in the northern offshore The isotopic measurements were performed with a VG-354 mass
area of Bohai Sea (Fig. 1d). Early Proterozoic and Archaean basement spectrometer. The precision (2␴) for isotope determination was
floors in this basin. The buried foreland basin trends east–west and ⬍0.08% for Pb and ⬍0.004% for Sr. It was difficult to obtain high-
developed during the Paleozoic-Sinian. The Anshan-Tengao fault precision isotopic ratios for Nd because of its low concentrations. We
marks the suture zone between the North China and Liaojiao blocks. only obtained a precision of ⬍0.005% for most of the bitumen samples
The Paleozoic strata are predominantly Cambrian and Ordovician and for small parts of the crude oil and kerogen samples. 143Nd/144Nd
limestones, and fine sandstones and are interpreted as marine facies. ratios were double normalized to 146Nd/144Nd ⫽ 0.721906 and 145Nd/
The Liaohe Basin is a north–northeast trending continental rift basin of
144
Nd ⫽ 0.348440. The measured mean value of 143Nd/144Nd for La
Tertiary age and is mainly filled with argillites, fine sandstones, and Jolla Standard is 0.511861 ⫾ 10 (n ⫽ 16). 87Sr/86Sr ratios were
minor amounts of basalts (Chen, 1985). The oil field is situated at the normalized to 86Sr/88Sr ⫽ 0.11940. The measured mean value of
overlapped area between the buried foreland basin and the rift basin.
87
Sr/86Sr for the standard SRM-987 is 0.710263 ⫾ 10 (n ⫽ 16). The
Eighty samples of crude oil were collected from oil wells in the average Pb isotopic composition values of the standard SRM-981 are
Liaohe oil field and the neighboring area. The oil wells used for sample
206
Pb/204Pb ⫽ 16.934 ⫾ 0.007, 207Pb/204Pb ⫽ 15.486 ⫾ 0.012, and
collection are parts of reservoirs including the Sha-2, Sha-3, and Sha-4
208
Pb/204Pb ⫽ 36.673 ⫾ 0.033 (n ⫽ 20), respectively. They are in good
benches of the Shahe Formation of Lower Tertiary age and the Dongy- agreement with the recalibrated values from a double spike determi-
ing Formation of Upper Tertiary age, as well as Paleozoic and Pre- nation: 16.9322, 15.4855, and 36.6856, respectively (Todt et al., 1993).
cambrian strata. Kerogen samples were separated from kerogen rocks The Rb, Sr, Sm, and Nd concentrations were determined by the isotope
of the drill cores in the Liaohe Basin of the Tertiary. dilution method (listed in the Tables) with errors better than 0.5%;
some concentrations were analyzed by an ICP-MS (ELAN 6000) with
errors better than 10%. All concentrations of elements are calculated
3. SAMPLE TREATMENT AND ANALYTICAL METHODS relative to the weights of the original sample materials.
3.1. Sample Treatment
4. RESULTS
The samples of massive bitumen or rocks containing bitumen veins
were broken into centimeter- to millimeter-size pieces. The fresh pieces 4.1. Bitumen in Karamay Oil Field
of bitumen were selected by hand picking without contamination of
host rock, then crushed into grains of millimeter size in an agate
The isotopic ratios and concentrations are given in Table 1.
crusher. Impurities were picked out under a binocular microscope. The The concentrations of Sm, Nd, Rb, and Sr in bitumen from
pure grains were washed with alcohol, 2 N HN4Cl, and double-distilled Karamay oil field show large variations, which are 0.004 to 1.4
 2558

Table 1. Pb, Sr, and Nd isotopic compositions in bitumen from the Karamay oil field.
206 207 208 147 143 87 87
No. Pb/204Pb Pb/204Pb Pb/204Pb Sm (ppm) Nd (ppm) Sm/144Nd Nd/144Nd Rb (ppm) Sr (ppm) Rb/86Sr Sr/86Sr

KW-1 18.166 ⫾ 0.009 15.578 ⫾ 0.009 38.359 ⫾ 0.031 0.0263 0.122 0.1303 0.513360 ⫾ 30 0.1787 0.993 0.5193 0.707786 ⫾ 13
KW-2 18.130 ⫾ 0.008 15.418 ⫾ 0.010 38.529 ⫾ 0.028 0.0576 0.274 0.1271 0.512982 ⫾ 20 0.2863 9.587 0.0861 0.706845 ⫾ 10
KW-3 18.409 ⫾ 0.009 15.473 ⫾ 0.010 37.751 ⫾ 0.029 1.412 6.676 0.1279 0.512637 ⫾ 13
KW-4 18.141 ⫾ 0.011 15.652 ⫾ 0.012 38.081 ⫾ 0.032 0.0282 0.120 0.1424 0.513096 ⫾ 20 0.1874 1.587 0.3370 0.707049 ⫾ 9
KW-5 18.422 ⫾ 0.012 15.654 ⫾ 0.012 38.659 ⫾ 0.033 0.0520 0.245 0.1287 0.512726 ⫾ 18 0.1280 0.879 0.4233 0.707655 ⫾ 11
KW-6 18.410 ⫾ 0.013 15.768 ⫾ 0.013 38.835 ⫾ 0.035 0.1060 0.5050 0.1273 0.512772 ⫾ 14 0.0861 0.757 0.3271 0.707054 ⫾ 10
KW-7 18.349 ⫾ 0.010 15.639 ⫾ 0.009 38.464 ⫾ 0.027 0.9088 4.407 0.1274 0.512663 ⫾ 21 5.603 7.399 2.185 0.714761 ⫾ 17
KW-8 18.110 ⫾ 0.008 15.419 ⫾ 0.008 37.703 ⫾ 0.031 1.200 5.585 0.1298 0.512587 ⫾ 14 7.185 15.84 1.309 0.711571 ⫾ 14
KW-9 18.200 ⫾ 0.010 15.548 ⫾ 0.012 37.783 ⫾ 0.032 0.0571 0.2825 0.1222 0.513015 ⫾ 6 0.4532 1.423 0.9184 0.709468 ⫾ 14
KW-10 18.454 ⫾ 0.012 15.649 ⫾ 0.013 38.121 ⫾ 0.033 0.1248 0.6319 0.1194 0.512787 ⫾ 28 0.8666 68.386 0.0366 0.708159 ⫾ 16
Z. Bing-Quan et al.

KW-11 18.274 ⫾ 0.008 15.545 ⫾ 0.009 38.393 ⫾ 0.031 0.0865 0.4048 0.1276 0.512765 ⫾ 15 2.714 13.524 0.5788 0.708632 ⫾ 14
KW-12 18.241 ⫾ 0.010 15.635 ⫾ 0.011 38.696 ⫾ 0.035 0.1641 0.944 0.5000 0.707893 ⫾ 7
KW-13 18.564 ⫾ 0.011 15.606 ⫾ 0.012 38.962 ⫾ 0.030 0.5606 2.829 0.1199 0.512674 ⫾ 13 2.357 7.897 0.8606 0.709736 ⫾ 13
KW-14 18.675 ⫾ 0.08 15.585 ⫾ 0.008 38.456 ⫾ 0.027 0.2153 1.255 0.4948 0.707865 ⫾ 11
KW-15 18.347 ⫾ 0.012 15.661 ⫾ 0.011 38.676 ⫾ 0.032 0.7105 3.509 0.1224 0.512743 ⫾ 22 0.0411 14.462 0.0082 0.709368 ⫾ 15
KW-16 18.310 ⫾ 0.013 15.391 ⫾ 0.013 37.880 ⫾ 0.033 0.7219 3.160 0.1382 0.512602 ⫾ 10 3.313 5.949 1.607 0.712159 ⫾ 17
KW-17 18.125 ⫾ 0.09 15.516 ⫾ 0.010 38.403 ⫾ 0.034 0.0629 0.3137 0.1214 0.512928 ⫾ 24 0.2980 2.259 0.3809 0.707430 ⫾ 12
KW-18 18.325 ⫾ 0.013 15.667 ⫾ 0.012 38.437 ⫾ 0.036 0.0037 0.0181 0.1235 0.513389 ⫾ 30 0.0331 0.481 0.1922 0.706426 ⫾ 9
 Pb, Sr, and Nd isotopes in organic matter from China 2559

143
Fig. 3. Nd/86Sr-1/Nd diagram for bitumen from the Karamay oil
field.

ceous or Tertiary time did not disturb the Rb-Sr isotopic sys-
tematics in the samples with low Sr concentration (⬍7.4 ppm).
The initial ratio of (87Sr/86Sr)I is evidently lower than those of
carbonate strata and seawater strontium in all Earth’s history
(0.7093– 0.7067), suggesting an influence of strontium from
mantle sources. Sample KW-15 shows high Sr concentration
(14.46 ppm), a low 87Rb/86Sr (0.0082), and a 87Sr/86Sr
(0.70936) close to that of present-day or Paleozoic seawater. It
may represent an end member of Sr components derived from
meteoric water influx or buried carbonate strata through migra-
tion of oil field water and organic fluid. The samples with
higher Sr concentrations (⬎7.9 ppm) could result from disturb-
Fig. 2. 87Sr/86Sr-87Rb/86Sr isochron diagram (A) and 87Sr/86Sr-1/Sr ing of this end member to different degree, thus causing the
diagram (B) for the bitumen from the Karamay oil field. Isochron line
1 is for all samples except KW-15 and KW-10. Isochron line 2 is for
deviation from the isochron line.
the samples with Sr concentration ⬍7.4 ppm. The 143Nd/144Nd ratios of Karamay bitumen are mostly
higher than bulk earth (0.512636). 143Nd/144Nd ratios in-
crease from 0.5126 to 0.5130 with decreasing Nd concen-
ppm, 0.02 to 6.7 ppm, 0.03 to 7 ppm, and 0.5 to 68 ppm, tration. Because the Nd concentrations for the samples with
respectively. The 87Sr/86Sr-87Rb/86Sr ratios were well corre- 143
Nd/144Nd ratios higher than 0.5130 are extremely low
lated. The slope of the correlation line corresponds to an age of (0.1– 0.01 ppm), the uncertainty of data may be higher than
284 ⫾ 20 Ma (2␴, mean standard weighted deviation the statistical deviation of analyses. Thus, we do not discuss
(MSWD) ⫽ 60) if samples KW-10 and KW-15 are not in- their geological meaning in particular. The 147Sm/144Nd
cluded (they evidently deviate from the bulk linear trend of the ratios (0.119 – 0.142) are lower than that of the bulk earth
data; Fig. 2a). The resulting initial (87Sr/86Sr)I is 0.70593 ⫾ 25. (0.1967), but higher than the argillaceous sediments (0.116 –
The samples with Sr concentrations below 7.4 ppm are much 0.119) as a representative of mean upper crust reported in
better correlated in the isochron diagram (Fig. 2a; R ⫽ 0.999) China (Zhu, 1998a) and North America (DePaolo, 1988).
than in the mixing diagram (Fig. 2b; R ⫽ 0.710). The slope of There is no isochron relationship for the Sm-Nd isotopic
this linear relationship yields an isochron age of 286 ⫾ 12 Ma systematics, but the 143Nd/144Nd-1/Nd plot shows a positive
(2␴, MSWD ⫽ 0.43) with (87Sr/86Sr)I ⫽ 0.70577 ⫾ 8 (Fig. 2a). correlation (Fig. 3). Thus, the variation of Nd isotopic ratios
Thus, it is possible that the alignment samples with low Sr may have resulted from inhomogeneous mixture of two or
concentrations is not a mixing line but an isochron. Thin- more end components during the bitumen formation. On the
section observations allowed the identification of epigenetic basis of the Rb-Sr isochron age, the ␧Nd(286 Ma) values are
microcrystalline carbonates in the samples with higher Sr con- from 1.5 to 17.4, which are higher than ␧Nd(0) by 2.0 to 2.9.
centration, especially in KW-15 and KW-10. Thus, the Nd isotopic compositions strongly show an influ-
Thus, it is reasonable to reject the samples with higher Sr ence from depleted mantle (␧Nd(286 Ma)⬃⫹8 –⫹11).
concentration in the calculation of the isochron to avoid the The Nd-Sr isotopic data (t ⫽ 286 Ma) on a ␧Nd(t)-␧Sr(t)
influence from carbonate Sr. On the basis of the isochron age diagram all lie in quadrant 1 and show a vertical trend (Fig. 4);
calculation of the two modes (285 ⫾ 20 Ma), the Karamay the data are also located between the ␧Nd(t)-␧Sr(t) fields of
bitumen could be formed during the Late Carboniferous–Early mid-ocean ridge basalt (MORB) and crustal rocks of North
Permian. The bitumen migration in plastic state in Late Creta- Xinjiang (Yu and Gui, 1998).
2560 Z. Bing-Quan et al.

Fig. 6. 143Nd/144Nd-147Sm/144Nd plot for bitumen and kerogen from

Fig. 4. ␧Nd(t)-␧Sr(t) plot for bitumen samples from Karamay (legends different strata in the Tarim Basin. The dashed line is a linear trend for
as in Fig. 2) and Tarim (diamonds). ␧Nd(t) and ␧Sr(t) values of bitumen the surface bitumen samples (TD-2, TD-3, TD-4, TD-6, CP-1, and
are calculated on the basis of t ⫽ 286 Ma for Karamay and t ⫽ 530 Ma CP-2).
for Trim. Ophiolite and MORB fields are from Jacobsen and Wasser-
burg (1979) and Shaw and Wasserburg (1985), the field of upper crust
in North Xinjiang is from Yu and Gui (1998), and the field of lower 4.2. Bitumen and Kerogen from Tarim Basin
crust in China is from Zhu (1998a).
The Sm-Nd isotopic history of bitumen from the Tarim
Basin (Table 2) is evidently different from those of the Kara-
The 206Pb/204Pb ratios of the Karamay bitumen lie in a may oil field. 143Nd/144Nd and 147Sm/144Nd ratios vary within
relatively narrow range of 18.11 to 18.675 (Table 1 and Fig. 5). 0.51157 to 0.51197 and 0.0778 to 0.153, respectively, and yield
However, their 207Pb/204Pb ratios, from 15.39 to 15.67, cover old, depleted mantle Nd model ages of 1.5 to 3.2 Ga. The
the whole range—from mantle to upper crust— of the Plum- samples from surface (TD and CP numbers) and drill core (H
botectonic model proposed by Zartman and Doe (1981). The numbers) show different fields on a 143Nd/144Nd-147Sm/144Nd
206
Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios for mantle- diagram, which indicates that their Sm-Nd isotopic systematics
derived rocks in the areas of Xinjiang show ranges of 17.9 to were involved in different sources (Fig. 6). However, a linear
18.3, 15.40 to 15.60, and 37.7 to 38.2, respectively, and those array for the surface bitumen samples of TD-2, TD-3, TD-4,
for sedimentary rocks are 18.18 to 18.47, 15.55 to 15.67, and TD-6, and CP-1 and CP-2 from Keping can be recognized,
38.0 to 38.5, respectively (Zhu, 1995, 1998a). Thus, the vari- which may represent a mixing line or an isochron line of ⬃530
ations of Pb isotopic compositions of bitumen also cover the Pb Ma. The bitumen deposits mainly distribute along the shear
isotopic range from the local mantle to upper crust. faults developed in the post-Cambrian strata. Thus, this corre-
lation may imply that there was mixing of two sources (Cam-

Fig. 5. 207Pb/204Pb-206Pb/204Pb plot, with the curves from the Plum-

botectonic model (Zartman and Doe, 1981), for bitumen from Kara- Fig. 7. 207Pb/204Pb-206Pb/204Pb plot for bitumen and kerogen from
may. UC ⫽ upper crust; OR ⫽ orogen belt; M ⫽ mantle; LC ⫽ lower Tarim. The dashed lines are linear trends of upper and lower limits for
crust; PM with star ⫽ primitive mantle in North China block (Zhu and kerogen (TDXE-1, TDXE-3, TDXE-4, FeS, TDO-1, and TDO-2) and
Chen, 1984). XM and XC are the fields for mantle-derived rocks and bitumen (TD-1, TD-2, TD-3, TD-4, TD-8, TA-2, TA-5, and LN-59-1),
sediments in North Xinjiang (Zhu, 1998a). respectively.
 Table 2. Pb, Sr, and Nd isotopic data in bitumen and kerogen from the Tarim Basin.

Sm Nd Rb Sr
206 207 208 147 143 87 87
No. Pb/204Pb Pb/204Pb Pb/204Pb (ppm) (ppm) Sm/144Nd Nd/144Nd TDMa (ppm) (ppm) Rb/86Sr Sr/86Sr

Bitumen
TD-1 17.530 ⫾ 0.011 15.517 ⫾ 0.010 38.210 ⫾ 0.021 4.96 30.19 0.0993 0.511743 ⫾ 8 1.79 22.36 27.55 2.345 0.726822 ⫾ 19
TD-2 17.476 ⫾ 0.009 15.476 ⫾ 0.009 38.161 ⫾ 0.019 4.97 32.06 0.0938 0.511644 ⫾ 12 1.84 18.28 23.27 2.226 0.728085 ⫾ 14
TD-3 17.434 ⫾ 0.007 15.488 ⫾ 0.009 38.093 ⫾ 0.018 3.20 16.27 0.1191 0.511717 ⫾ 12 2.22 20.00 27.93 2.069 0.725950 ⫾ 14
TD-4 17.349 ⫾ 0.012 15.466 ⫾ 0.011 37.899 ⫾ 0.025 2.61 16.07 0.0982 0.511632 ⫾ 8 1.92 18.89 31.62 1.722 0.723182 ⫾ 13
TD-5 17.997 ⫾ 0.012 15.623 ⫾ 0.012 38.989 ⫾ 0.027 2.50 14.03 0.1077 0.511805 ⫾ 9 1.84 16.18 19.61 2.385 0.725125 ⫾ 12
TD-6 18.235 ⫾ 0.010 15.652 ⫾ 0.011 39.089 ⫾ 0.027 2.25 17.47 0.0778 0.511573 ⫾ 14 1.69 17.22 27.17 1.831 0.723253 ⫾ 13
TD7 2.35 12.75 0.1112 0.511839 ⫾ 12 1.85 17.61 31.19 1.630 0.720568 ⫾ 13
TD8 17.083 ⫾ 0.013 15.467 ⫾ 0.012 38.551 ⫾ 0.029 2.54 19.08 0.0804 0.511736 ⫾ 10 1.54 17.28 26.27 1.900 0.722467 ⫾ 5
H-4 18.292 ⫾ 0.008 15.633 ⫾ 0.009 38.740 ⫾ 0.025 3.14 22.19 0.0856 0.512038 ⫾ 14 1.23
H-5 18.202 ⫾ 0.011 15.629 ⫾ 0.013 38.523 ⫾ 0.028 14.14 68.62 0.1246 0.511877 ⫾ 15 2.08
H-7 18.218 ⫾ 0.012 15.636 ⫾ 0.012 38.761 ⫾ 0.027 1.88 11.05 0.1030 0.511974 ⫾ 8 1.52
H-8 2.19 12.18 0.1089 0.511814 ⫾ 16 1.85
C-P-1 18.376 ⫾ 0.013 15.632 ⫾ 0.012 38.714 ⫾ 0.028 2.87 11.36 0.1526 0.511820 ⫾ 28 3.23
C-P-2 17.953 ⫾ 0.012 15.636 ⫾ 0.011 38.156 ⫾ 0.026 2.31 9.259 0.1510 0.511831 ⫾ 14 3.11
TA-2 18.587 ⫾ 0.014 15.551 ⫾ 0.012 38.115 ⫾ 0.030
TA-5 18.446 ⫾ 0.013 15.547 ⫾ 0.011 38.302 ⫾ 0.031
LN-59-1 17.658 ⫾ 0.010 15.498 ⫾ 0.009 38.410 ⫾ 0.029
Kerogen
TDOS-2 18.115 ⫾ 0.008 15.608 ⫾ 0.009 38.570 ⫾ 0.021 2.75 16.71 0.0993 0.512262 ⫾ 24 1.08
TDOS-1 18.055 ⫾ 0.011 15.592 ⫾ 0.009 38.462 ⫾ 0.022 2.08 17.80 0.0705 0.512225 ⫾ 9 0.90
206 207 208 206 207 208
No. Pb/204Pb Pb/204Pb Pb/204Pb No. Pb/204Pb Pb/204Pb Pb/204Pb
Pb, Sr, and Nd isotopes in organic matter from China

TDO-1 19.309 ⫾ 0.011 15.788 ⫾ 0.012 39.262 ⫾ 0.033 TDXE-1 20.949 ⫾ 0.013 15.886 ⫾ 0.014 39.309 ⫾ 0.028
TDO-2 19.492 ⫾ 0.012 15.809 ⫾ 0.012 39.592 ⫾ 0.026 TDXE-2 19.848 ⫾ 0.012 15.754 ⫾ 0.012 39.982 ⫾ 0.035
TDO-3 20.110 ⫾ 0.015 15.776 ⫾ 0.013 39.255 ⫾ 0.029 TDXE-3 19.649 ⫾ 0.011 15.803 ⫾ 0.012 39.982 ⫾ 0.029
TDO-5 20.264 ⫾ 0.017 15.791 ⫾ 0.013 39.102 ⫾ 0.033 TDXE-4 20.030 ⫾ 0.009 15.833 ⫾ 0.008 39.999 ⫾ 0.030
TDXE-FeS 18.371 ⫾ 0.009 15.733 ⫾ 0.009 38.550 ⫾ 0.025 TDXE-5 19.218 ⫾ 0.012 15.728 ⫾ 0.013 40.055 ⫾ 0.027
a 143 147
TDM values are calculated on the basis of the present Nd/144Nd ⫽ 0.51305 and Sm/144Nd ⫽ 0.2102.
2561
2562 Z. Bing-Quan et al.

brian and Permian strata) for the surface bitumen generation, or Table 3. Pb isotopic compositions in bitumen and kerogen from
it may imply that the bitumen was formed in Late Cambrian Guizhou.
time and migrated into younger strata during a later stage. The 206
143 No. Pb/204Pb 207
Pb/204Pb 208
Pb/204Pb
Nd/144Nd ratios for the kerogen samples of TDOS
(0.512225– 0.512262) are distinctly higher than those of bitu- Bitumen
men samples. The bitumen samples from drill cores (H-4, H-5, 204-1 19.699 ⫾ 0.008 15.750 ⫾ 0.009 38.468 ⫾ 0.019
H-7, and H-8) also show higher 143Nd/144Nd ratios and a trend 204-3 19.014 ⫾ 0.011 15.769 ⫾ 0.011 38.513 ⫾ 0.023
Hg-2 19.137 ⫾ 0.010 15.779 ⫾ 0.011 38.473 ⫾ 0.024
toward the kerogen samples of TDOS (Fig. 6). This relation- Hg-217 18.966 ⫾ 0.011 15.765 ⫾ 0.009 38.420 ⫾ 0.021
ship may indicate that there was influence from fluids with high Hg-208 19.186 ⫾ 0.008 15.786 ⫾ 0.010 38.555 ⫾ 0.019
143
Nd/144Nd ratios for the drill core samples, or it may indicate Hg-651 18.289 ⫾ 0.010 15.662 ⫾ 0.012 38.601 ⫾ 0.022
that mixing between the bitumen derived from the kerogen Kerogen
G1 34.622 ⫾ 0.029 16.517 ⫾ 0.012 39.084 ⫾ 0.023
rocks of TDOS and the surface bitumen derived from deep G2 285.226 ⫾ 0.094 30.977 ⫾ 0.013 38.458 ⫾ 0.024
sources. G4 42.951 ⫾ 0.023 16.997 ⫾ 0.014 38.803 ⫾ 0.028
The 87Sr/86Sr ratios of bitumen are high and range 0.72056 G5 38.097 ⫾ 0.021 16.870 ⫾ 0.011 39.069 ⫾ 0.031
to 0.72682, which mainly represent Sr isotopic compositions of G6 44.687 ⫾ 0.023 17.284 ⫾ 0.010 39.087 ⫾ 0.029
detrital sedimentary rocks of the upper crust. Because the G7 50.498 ⫾ 0.022 17.422 ⫾ 0.011 39.001 ⫾ 0.029
G8 23.485 ⫾ 0.011 15.996 ⫾ 0.010 38.879 ⫾ 0.031
metamorphic temperature for the Tarim bitumen is higher than G9 139.066 ⫾ 0.032 22.879 ⫾ 0.013 38.302 ⫾ 0.021
that of the Karamay bitumen, the Rb-Sr isotopic systematics are G10 53.989 ⫾ 0.023 17.851 ⫾ 0.012 39.069 ⫾ 0.033
disturbed. Thus, there are no clear 87Sr/86Sr-87Rb/86Sr linear G11 76.932 ⫾ 0.042 19.178 ⫾ 0.013 38.208 ⫾ 0.028
trends. G12 27.062 ⫾ 0.013 16.463 ⫾ 0.012 39.689 ⫾ 0.032
G13 19.985 ⫾ 0.008 16.068 ⫾ 0.009 39.858 ⫾ 0.031
The Pb isotopic compositions of bitumen show large varia-
tions: 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb are 17.349 to
18.587, 15.466 to 15.652, and 37.899 to 39.089, respectively
(Table 2). On the basis of the 207Pb/204Pb-206Pb/204Pb plot of ⬃570 Ma. The Pb isotopic evidence also shows that there are
(Fig. 7), the data can be clearly divided into two groups. One is no direct genetic relationships between surface bitumen and
close to the upper crustal curve of the Plumbotectonic model kerogen. As with Sm-Nd isotope systematics, the Pb isotopic
and includes the samples from the drill core and Permian strata compositions of TDOS kerogen samples are also close to those
(H and CP). The other group, for the surface samples, is located of bitumen samples of H number from the drill core. Thus, the
in between the mantle and orogen belt curves and shows a bitumen lead of H and CP samples could represent mixing
Pb-Pb isochron trend with an age of ⬃490 Ma, which is between the kerogen and the bitumen with the 490-Ma isochron
approximately consistent with the Sm-Nd isochron age. The trend.
evidence of Pb isotopic compositions also indicates that there On the basis of the Sm-Nd isochron age of ⬃530 Ma, the
exists addition of lead derived from mantle or lower crustal calculated ␧Nd(t)-␧Sr(t) data (t ⫽ 530 Ma) for the Tarim bitu-
sources during bitumen formation. men lies in quadrant 4 of Figure 3 and in between the fields of
The kerogen samples of TDO, TDXE, and TDOS from the the upper crust in North Xinjiang and the lower crust in
surface have higher 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb continental China. Even if t changes from 0 to 550 Ma, the
ratios (19.218 –20.949, 15.728 –15.890, and 39.102– 40.044, calculated ␧Nd(t)-␧Sr(t) data field still lies in between those of
respectively) than those of bitumen (Table 2). The upper limit the upper and lower crusts.
to the data in Figure 7, which are mainly composed of Cam-
brian TDXE samples, yields a Pb-Pb isochron trend with an age
4.3. Bitumen and Kerogen from Guizhou
The bitumen from mercury deposits in Guizhou yielded
relatively large variations of 206Pb/204Pb and 207Pb/204Pb—
18.289 to 19.699 and 15.662 to 15.786, respectively— but the
208
Pb/204Pb ratios are in a narrow range of 38.429 to 38.601
(Table 3 and Fig. 8). These isotopic compositions clearly show
features of upper crustal sources and reflect an environment of
chemical sedimentation as their homogenous 208Pb/204Pb ratios
(Zhu, 1998a).
The kerogen samples show extremely radiogenic U-Pb sys-
tematics. Their 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ra-
tios are 19.985 to 285.226, 16.068 to 22.879, and 38.458 to
39.858, respectively. There is a good Pb-Pb isochron correla-
tion (Fig. 8). The isochron age of 514 ⫾ 44 Ma (2␴, MSWD ⫽
7) is in agreement with the age of Middle Cambrian strata in the
area of sample collection and represents the formation age of
kerogen. The Pb isotopic ratios of bitumen basically lie on this
Fig. 8. 207Pb/204Pb-206Pb/204Pb isochron diagram for kerogen from
Pb-Pb isochron line of kerogen, which may imply that the
Cambrian strata in Guizhou and bitumen from the Guizhou paleo-oil bitumen was also formed during Middle Cambrian. If the
field. The means for UC and OR are same as Figure 5. bitumen was directly derived from the kerogen rocks of Middle
 Pb, Sr, and Nd isotopes in organic matter from China 2563

Table 4. Pb and Sr isotopic compositions of bitumen-A in the Liaohe oil field.

206
No. Pb/204Pb 207
Pb/204Pb 208
Pb/204Pb 143
Nd/144Nd 87
Sr/86Sr

Ka25 17.459 ⫾ 0.007 15.418 ⫾ 0.005 37.735 ⫾ 0.017 0.709467 ⫾ 28

Q23-20 17.601 ⫾ 0.009 15.446 ⫾ 0.007 37.801 ⫾ 0.019 0.714118 ⫾ 27
C55 17.424 ⫾ 0.015 15.376 ⫾ 0.013 37.618 ⫾ 0.038
J6 17.448 ⫾ 0.018 15.384 ⫾ 0.010 37.700 ⫾ 0.038
W8 17.514 ⫾ 0.011 15.438 ⫾ 0.010 37.788 ⫾ 0.025 0.716106 ⫾ 19
C612 17.488 ⫾ 0.021 15.426 ⫾ 0.020 37.718 ⫾ 0.040 0.716484 ⫾ 31
N22 17.449 ⫾ 0.014 15.388 ⫾ 0.013 37.667 ⫾ 0.036 0.720201 ⫾ 38
Ha45 17.456 ⫾ 0.007 15.421 ⫾ 0.009 37.804 ⫾ 0.036 0.709829 ⫾ 21
G3-4-3 17.448 ⫾ 0.012 15.399 ⫾ 0.010 37.685 ⫾ 0.026 0.710323 ⫾ 31
R43 17.475 ⫾ 0.010 15.407 ⫾ 0.009 37.708 ⫾ 0.023 0.714501 ⫾ 26
N23-18 17.431 ⫾ 0.011 15.378 ⫾ 0.009 37.620 ⫾ 0.021 0.716708 ⫾ 21
S-1 17.449 ⫾ 0.012 15.390 ⫾ 0.009 37.668 ⫾ 0.020 0.709677 ⫾ 19
D-20 17.489 ⫾ 0.005 15.448 ⫾ 0.007 37.870 ⫾ 0.020 0.712436 ⫾ 49
Ro-25 17.467 ⫾ 0.013 15.405 ⫾ 0.007 37.736 ⫾ 0.038

Cambrian, there should exist extremely large U/Pb fraction- and 208Pb/204Pb, respectively; Chen et al., 1982; Zhu and Chen,
ation. The distinct difference of Pb isotopic ratios between 1984) on either 207Pb/204Pb-206Pb/204Pb or 208Pb/204Pb-207Pb/
204
kerogen and bitumen also can be regarded as material addition Pb diagrams (Figs. 9 and 10). This may imply that the lead
from another source with isotopic compositions of common in the bitumen-A is recently derived from mantle. The range of
lead during the bitumen derivation. Pb isotopic compositions for Quaternary basalts from the North
China block, indicative of the present mantle, is similar to that
4.4. Bitumen-A and Kerogen from the Liaohe Oil Field of bitumen-A (Fig. 9; Peng et al., 1986; Basu et al., 1991; Zhu,
1995, 1998a).
We have previously reported that the bitumen-A samples The Pb isotopic compositions in kerogen are distinct from
from the Liaohe oil field have very homogeneous Pb isotopic those of bitumen-A. The data show large variations of 206Pb/
compositions (Zhang et al., 1999). The 206Pb/204Pb, 207Pb/ 204
Pb, 207Pb/204Pb, and 208Pb/204Pb of 7.748 to 18.735, 15.388
204
Pb, and 208Pb/204Pb ratios are 17.424 to 17.601, 15.378 to to 15.695, and 37.656 to 38.748, respectively (Table 5, Fig. 9),
15.448, and 37.618 to 37.870, respectively (Table 4). The data and mainly lie in between the curves of upper crust and mantle
on the 207Pb/204Pb-206Pb/204Pb diagram lie in between the of the Plumbotectonic model. Thus, the lead in kerogen is
mantle and lower crust curves of the Plumbotectonic model mostly derived from the crust. Although bitumen-A is inter-
(Fig. 9; Zartman and Doe, 1981). It is worth noting that the grown with kerogen, the Pb isotopic features show that bitu-
dispersed trend of data is along the zero-age geochron that men-A is not directly derived from kerogen, and there existed
extrapolates to the primitive mantle (PM) of the North China the addition of mantlelike materials.
block (17.35, 15.33, and 37.47 for 206Pb/204Pb, 207Pb/204Pb, However, the 87Sr/86Sr ratios (0.709677– 0.722772) in bitu-
men-A are higher than those of seawater and similar to sedi-
ments (Fig. 11), which is in contrast with the inference made by
tracing Pb isotopes. The Sr isotopic compositions in kerogen

Fig. 9. 207Pb/204Pb-206Pb/204Pb plot comparing bitumen-A and kero-

gen from the same strata in the Liaohe oil field. The means for UC, OR, Fig. 10. 208Pb/204Pb-207Pb/204Pb plot for crude oil and bitumen-A
M, LC, and PM with star are same as Figure 5. The field of Quaternary from the Liaohe oil field. PM with star ⫽ primitive mantle in North
basalts in North China is from Peng et al. (1986), Basu et al. (1991), China. The shaded area indicates the data field of major and large oil
and Zhu (1995, 1998a). pools.
2564 Z. Bing-Quan et al.

Table 5. Pb, Sr, and Nd isotopic compositions in kerogen from the Liaohe oil field.
206
No. Pb/204Pb 207
Pb/204Pb 208
Pb/204Pb 143
Nd/144Nd 87
Sr/86Sr

H-33 18.050 ⫾ 0.015 15.573 ⫾ 0.014 38.139 ⫾ 0.038 0.511792 ⫾ 6 0.715405 ⫾ 18

Se-82 18.201 ⫾ 0.023 15.654 ⫾ 0.025 38.486 ⫾ 0.067 0.710446 ⫾ 14
Se-111 17.977 ⫾ 0.012 15.529 ⫾ 0.013 38.093 ⫾ 0.028 0.710516 ⫾ 19
R16-4 18.656 ⫾ 0.007 15.661 ⫾ 0.007 38.662 ⫾ 0.012
H2-11-2 17.935 ⫾ 0.020 15.557 ⫾ 0.026 38.087 ⫾ 0.052 0.712229 ⫾ 19
C5 18.735 ⫾ 0.013 15.692 ⫾ 0.011 38.748 ⫾ 0.029 0.712976 ⫾ 18
M16 17.974 ⫾ 0.014 15.469 ⫾ 0.014 38.071 ⫾ 0.030 0.712829 ⫾ 16
X268 18.253 ⫾ 0.029 15.672 ⫾ 0.028 38.619 ⫾ 0.081 0.712875 ⫾ 14
G3-6-18 17.796 ⫾ 0.005 15.506 ⫾ 0.005 38.079 ⫾ 0.011 0.713287 ⫾ 21
S90 17.903 ⫾ 0.010 15.547 ⫾ 0.013 38.164 ⫾ 0.019 0.710451 ⫾ 22
Se101 18.167 ⫾ 0.008 15.569 ⫾ 0.009 38.219 ⫾ 0.026 0.511953 ⫾ 6 0.710747 ⫾ 13
KG25 17.591 ⫾ 0.008 15.486 ⫾ 0.009 37.948 ⫾ 0.018 0.726245 ⫾ 36
Do-13 17.901 ⫾ 0.017 15.593 ⫾ 0.015 38.273 ⫾ 0.037 0.511963 ⫾ 19 0.716087 ⫾ 20
QG23 17.488 ⫾ 0.010 15.388 ⫾ 0.006 37.656 ⫾ 0.014 0.709624 ⫾ 19
H G 45 17.497 ⫾ 0.007 15.407 ⫾ 0.010 37.742 ⫾ 0.020 0.511923 ⫾ 6 0.709950 ⫾ 30
J-3 17.911 ⫾ 0.010 15.511 ⫾ 0.009 38.030 ⫾ 0.020 0.511891 ⫾ 7 0.710597 ⫾ 14
O5 18.403 ⫾ 0.018 15.596 ⫾ 0.006 38.702 ⫾ 0.029 0.511878 ⫾ 5 0.716794 ⫾ 13
N15 18.626 ⫾ 0.012 15.695 ⫾ 0.012 38.737 ⫾ 0.033 0.511915 ⫾ 5 0.718257 ⫾ 15
L10 18.310 ⫾ 0.009 15.616 ⫾ 0.009 38.404 ⫾ 0.027 0.511862 ⫾ 5 0.726240 ⫾ 26
T-2 18.525 ⫾ 0.024 15.678 ⫾ 0.019 38.624 ⫾ 0.069 0.511905 ⫾ 8 0.712834 ⫾ 28
S4-5-7 17.972 ⫾ 0.017 15.488 ⫾ 0.025 38.073 ⫾ 0.052 0.511925 ⫾ 9
Q2-19-2 18.001 ⫾ 0.012 15.550 ⫾ 0.015 38.268 ⫾ 0.053 0.511847 ⫾ 8 0.710953 ⫾ 19
Se-80 18.083 ⫾ 0.007 15.531 ⫾ 0.007 38.079 ⫾ 0.015 0.512004 ⫾ 7 0.710677 ⫾ 18
M123 17.622 ⫾ 0.028 15.605 ⫾ 0.029 37.845 ⫾ 0.068 0.511969 ⫾ 8 0.706346 ⫾ 16

are similar to those of bitumen-A. It is suggested that the 6 to 8000 ppb, and 1 to 50 ppb, respectively, and have low
genetic environment of bitumen-A is related to mantle– crust Rb/Sr (⬃0.1), U/Pb (⬍0.01), and Sm/Nd (0.15– 0.3) ratios.
interaction between fluid derived from mantle or lower crust This suggests that the measured isotopic compositions of these
sources and kerogen in sediments, during which the lead in Tertiary samples are close to the initial ratios.
fluid was mainly from mantle sources but the strontium was The Pb isotopic compositions of crude oil are listed in Table
from sediments. 6. The 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios are
17.25 to 18.78, 15.37 to 15.62, and 37.3 to 38.3, respectively.
4.5. Crude Oil from the Liaohe Oil Field Most of the data on the 206Pb/204Pb-207Pb/204Pb diagram (Fig.
12) are dispersed from the evolution curve of the mantle to that
On the basis of the ICP-MS concentration determination, the
of upper crust and on the right side of the zero age geochron
crude oil samples from the Liaohe Basin of the Tertiary are
according to the Plumbotectonic model (Zartman and Doe,
characterized by Pb, Sr, and Nd concentrations of 4 to 500 ppb,
1981). The data field is triangular in shape and points to the
primitive mantle of North China (Zhu and Chen, 1984). Thus,
the Pb isotopic compositions of crude oil also show a mixing
relationship between crust and mantle, which is similar to that
of the bitumen from Karamay. The 206Pb/204Pb, 207Pb/204Pb,
and 208Pb/204Pb ratios for major and large oil pools lie in a
more narrow range of 17.42 to 18.15, 15.37 to 15.57, and 37.33
to 38.15, respectively. It can be seen in Figure 12 that the data
field of major and large oil pools lie on both sides of mantle
evolution curve and is comparable with that of the Cenozoic
basalts in the North China block (Peng et al., 1986; Basu et al.,
1991; Zhu, 1995, 1998a). The Pb isotopic field of the upper
crustal rocks in the Anshan area, near the oil field (Zhu, 1998a),
is quite different from that of crude oil (Fig. 12). Lower crustal
granulites from northeast China yielded a field of Pb isotopic
compositions with 206Pb/204Pb 14.05⬃16.12, 207Pb/204Pb
14.75⬃15.09, and 208Pb/204Pb 33.9⬃37.13 (Zhu, 1998a),
which greatly deviate from the data field of crude oil. Thus, the
Pb isotopic features of crude oil cannot be explained by mixing
Fig. 11. 87Sr/86Sr-206Pb/204Pb diagram for crude oil, bitumen, and
kerogen from the Liaohe oil field. The dashed lines divide the fields of
between the upper and lower crusts in this area. It can be seen
upper crust, sediments of marine facies, and mantle in subduction on the diagram of 208Pb/204Pb-207Pb/204Pb (Fig. 10) that most
zones. of the crude oil data, especially for those from large and major
 Pb, Sr, and Nd isotopes in organic matter from China 2565

Table 6. Pb, Sr, and Nd isotopic data of crude oil in the Liaohe oil field.
206
Sample No. Pb/204Pb 207
Pb/204Pb 208
Pb/204Pb 87
Sr/86Sr Sra 143
Nd/144Nd

Eastern
Depression
South part, Leng27-11 17.551 ⫾ 0.018 15.437 ⫾ 0.014 37.771 ⫾ 0.036 0.710203 ⫾ 14
large oil pool Leng27-7 17.649 ⫾ 0.025 15.477 ⫾ 0.020 37.801 ⫾ 0.055 0.711984 ⫾ 19
Oil indication Liao1 18.010 ⫾ 0.022 15.640 ⫾ 0.020 38.332 ⫾ 0.051 0.709792 ⫾ 17
Middle part, Long15-122 17.603 ⫾ 0.010 15.456 ⫾ 0.010 37.792 ⫾ 0.024 0.714144 ⫾ 14
medium oil Long16-122 17.848 ⫾ 0.022 15.577 ⫾ 0.019 38.045 ⫾ 0.034 0.709635 ⫾ 78
pool Long22-27 17.837 ⫾ 0.014 15.546 ⫾ 0.012 38.047 ⫾ 0.034 0.709169 ⫾ 24
North part, Niu18 18.184 ⫾ 0.008 15.611 ⫾ 0.007 38.394 ⫾ 0.015 0.709775 ⫾ 19
medium oil Niu27-023 17.465 ⫾ 0.017 15.405 ⫾ 0.014 37.643 ⫾ 0.039 0.708530 ⫾ 62
pool Niu25-320 17.478 ⫾ 0.009 15.417 ⫾ 0.009 37.745 ⫾ 0.024 0.708862 ⫾ 19
Niu53 17.797 ⫾ 0.058 15.518 ⫾ 0.064 38.081 ⫾ 0.193 0.712414 ⫾ 19 1920
Oil indication LC2 0.709572 ⫾ 22
South part, Xiao13 18.769 ⫾ 0.013 15.652 ⫾ 0.017 38.562 ⫾ 0.038 0.709016 ⫾ 35
small oil pool Xiao9 17.780 ⫾ 0.017 15.491 ⫾ 0.014 37.944 ⫾ 0.047
Middle part, Re10 18.214 ⫾ 0.012 15.593 ⫾ 0.013 38.223 ⫾ 0.022 0.709554 ⫾ 29
medium oil Re44 18.098 ⫾ 0.010 15.642 ⫾ 0.009 38.195 ⫾ 0.024 0.708754 ⫾ 22
pool Re10-6 18.173 ⫾ 0.015 15.629 ⫾ 0.015 38.323 ⫾ 0.032 0.709972 ⫾ 23
Re7-07 17.860 ⫾ 0.013 15.532 ⫾ 0.011 38.042 ⫾ 0.039
Re7-6 18.160 ⫾ 0.008 15.626 ⫾ 0.007 37.214 ⫾ 0.021 0.708450 ⫾ 21
Re9-03 17.906 ⫾ 0.012 15.626 ⫾ 0.012 37.878 ⫾ 0.037
Gas pool Rong59-3 17.504 ⫾ 0.009 15.408 ⫾ 0.010 37.709 ⫾ 0.015
TaoQ5 17.837 ⫾ 0.009 15.552 ⫾ 0.008 38.015 ⫾ 0.015 0.709590 ⫾ 17
Oil indication Tie2 18.050 ⫾ 0.014 15.482 ⫾ 0.012 37.849 ⫾ 0.033 0.706532 ⫾ 18
Middle part, Wa12-25 18.417 ⫾ 0.012 15.672 ⫾ 0.011 38.671 ⫾ 0.029 0.708643 ⫾ 22
medium oil Wa10-34 17.968 ⫾ 0.018 15.609 ⫾ 0.022 38.250 ⫾ 0.048
pool Wa15-22 17.489 ⫾ 0.015 15.496 ⫾ 0.015 37.575 ⫾ 0.026 0.709198 ⫾ 32
Wa34-34- 17.975 ⫾ 0.008 15.532 ⫾ 0.007 38.098 ⫾ 0.020 0.710812 ⫾ 30
430
Gas pool Hong8-12 17.878 ⫾ 0.014 15.524 ⫾ 0.015 38.027 ⫾ 0.032 0.710008 ⫾ 16 0.511651 ⫾ 17
South part, Yu578 17.868 ⫾ 0.023 15.564 ⫾ 0.026 38.073 ⫾ 0.033
major oil pool Yu5-8 17.544 ⫾ 0.011 15.430 ⫾ 0.010 37.766 ⫾ 0.021 0.709116 ⫾ 19
Yu6-8 17.870 ⫾ 0.011 15.545 ⫾ 0.010 37.931 ⫾ 0.017 0.709692 ⫾ 18
Hail-1 17.727 ⫾ 0.010 15.520 ⫾ 0.007 37.623 ⫾ 0.009 0.708779 ⫾ 54 8022
Hai13-39 17.446 ⫾ 0.005 15.377 ⫾ 0.005 37.625 ⫾ 0.013 0.709426 ⫾ 28 26.3 0.511816 ⫾ 65
Kai33-18 17.846 ⫾ 0.010 15.432 ⫾ 0.013 37.763 ⫾ 0.040 0.712693 ⫾ 19 5.2 0.512160 ⫾ 36
Kai42-11 17.448 ⫾ 0.008 15.375 ⫾ 0.009 37.615 ⫾ 0.026 0.708874 ⫾ 19
Kuihua9 17.659 ⫾ 0.014 15.422 ⫾ 0.011 37.630 ⫾ 0.035 0.709546 ⫾ 63 0.511840 ⫾ 36
Oil indication Jie13 18.186 ⫾ 0.020 15.617 ⫾ 0.021 38.322 ⫾ 0.062 0.706025 ⫾ 44
Middle part, Huang25-12 18.061 ⫾ 0.014 15.606 ⫾ 0.015 38.241 ⫾ 0.037
medium oil Huang31 18.446 ⫾ 0.004 15.600 ⫾ 0.004 38.271 ⫾ 0.010 0.710915 ⫾ 19 0.512038 ⫾ 32
pool Huang86 17.582 ⫾ 0.010 15.444 ⫾ 0.011 37.781 ⫾ 0.032 0.710102 ⫾ 23 0.511836 ⫾ 55
Ci33-215 18.085 ⫾ 0.017 15.544 ⫾ 0.019 38.056 ⫾ 0.053 0.712360 ⫾ 65 10.3
North part, Ci36-200 17.633 ⫾ 0.005 15.456 ⫾ 0.006 37.821 ⫾ 0.016 0.723305 ⫾ 17
medium oil Ci45-70 17.898 ⫾ 0.017 15.534 ⫾ 0.015 38.034 ⫾ 0.035 0.512064 ⫾ 20
pool Ci46-78 17.251 ⫾ 0.007 15.486 ⫾ 0.008 37.179 ⫾ 0.017 0.709968 ⫾ 20
Ci49-92 17.537 ⫾ 0.012 15.441 ⫾ 0.010 37.752 ⫾ 0.025 0.709997 ⫾ 14 264.0
Ci50-80 18.053 ⫾ 0.009 15.669 ⫾ 0.008 38.441 ⫾ 0.027 0.712195 ⫾ 18
Ci53-84 17.522 ⫾ 0.014 15.425 ⫾ 0.012 37.629 ⫾ 0.034 0.714587 ⫾ 25
Ci54-82 17.729 ⫾ 0.016 15.525 ⫾ 0.016 38.013 ⫾ 0.040 0.709751 ⫾ 29
Ci9-15-09 17.615 ⫾ 0.013 15.498 ⫾ 0.010 37.962 ⫾ 0.021 0.709823 ⫾ 46 23.4
South part, Da11-06 17.502 ⫾ 0.009 15.416 ⫾ 0.008 37.748 ⫾ 0.021
large oil pool Da12-17 17.508 ⫾ 0.007 15.442 ⫾ 0.010 37.835 ⫾ 0.020 0.709257 ⫾ 87
Da12-19 17.512 ⫾ 0.021 15.399 ⫾ 0.026 37.736 ⫾ 0.072 0.707131 ⫾ 15
Da13 17.928 ⫾ 0.011 15.592 ⫾ 0.012 37.864 ⫾ 0.024 0.716957 ⫾ 32
Ou14 17.481 ⫾ 0.010 15.379 ⫾ 0.009 37.601 ⫾ 0.023 0.710198 ⫾ 35
Oil indication FL4 17.894 ⫾ 0.007 15.586 ⫾ 0.008 38.035 ⫾ 0.023 0.710472 ⫾ 19 0.511670 ⫾ 40
Damintun
Small oil pools Xinan19-31 17.638 ⫾ 0.020 15.539 ⫾ 0.018 38.114 ⫾ 0.034 0.720751 ⫾ 61 136.0
Shen95 18.785 ⫾ 0.012 15.633 ⫾ 0.012 38.322 ⫾ 0.025 0.712143 ⫾ 19
Sheng24-10 17.725 ⫾ 0.013 15.474 ⫾ 0.012 37.913 ⫾ 0.024
Sheng24-11 18.402 ⫾ 0.013 15.607 ⫾ 0.012 38.151 ⫾ 0.031 0.711193 ⫾ 35
J61-321 17.838 ⫾ 0.005 15.561 ⫾ 0.007 38.113 ⫾ 0.011 0.709746 ⫾ 46 0.511875 ⫾ 57
J71-263 17.723 ⫾ 0.023 15.516 ⫾ 0.020 38.117 ⫾ 0.057 0.710960 ⫾ 25 31.4
Gang3 17.886 ⫾ 0.010 15.524 ⫾ 0.009 38.004 ⫾ 0.032 0.711903 ⫾ 15 0.511735 ⫾ 56
An22-29 17.844 ⫾ 0.018 15.499 ⫾ 0.015 37.850 ⫾ 0.032 0.721136 ⫾ 32
Qian8 17.780 ⫾ 0.016 15.562 ⫾ 0.013 38.056 ⫾ 0.035 0.722346 ⫾ 23
(continued on next page)
2566 Z. Bing-Quan et al.

Table 6. (Continued)
206
Sample No. Pb/204Pb 207
Pb/204Pb 208
Pb/204Pb 87
Sr/86Sr Sra 143
Nd/144Nd

Western
Depression
Middle part, Ma17 17.521 ⫾ 0.024 15.382 ⫾ 0.018 37.344 ⫾ 0.051 0.709930 ⫾ 14
major oil pool Ma145 17.576 ⫾ 0.008 15.428 ⫾ 0.008 37.751 ⫾ 0.017 0.711433 ⫾ 58 22.4
Qi8 18.149 ⫾ 0.025 15.569 ⫾ 0.020 38.158 ⫾ 0.049 0.709796 ⫾ 30
Shu1-6-011 17.567 ⫾ 0.006 15.451 ⫾ 0.005 37.825 ⫾ 0.014 0.709652 ⫾ 34
Shu1-7-310 17.818 ⫾ 0.021 15.548 ⫾ 0.019 38.123 ⫾ 0.048 0.710652 ⫾ 22 0.512036 ⫾ 33
ShuG11 17.626 ⫾ 0.013 15.445 ⫾ 0.010 37.725 ⫾ 0.026 0.710673 ⫾ 27
Shu4-8-16 17.570 ⫾ 0.032 15.414 ⫾ 0.033 37.739 ⫾ 0.087 0.710993 ⫾ 30 272.9 0.512085 ⫾ 58
Lei46-56-58 17.750 ⫾ 0.032 15.531 ⫾ 0.031 37.805 ⫾ 0.052 0.711818 ⫾ 17
TuG-56 17.658 ⫾ 0.020 15.467 ⫾ 0.013 37.836 ⫾ 0.036
South part, Jin2-4-04 17.468 ⫾ 0.010 15.495 ⫾ 0.009 37.648 ⫾ 0.021 0.709114 ⫾ 14
medium oil Jin45 17.337 ⫾ 0.014 15.518 ⫾ 0.012 37.526 ⫾ 0.032 0.708435 ⫾ 18 0.511866 ⫾ 63
pool
South part, Huan26 18.354 ⫾ 0.007 15.619 ⫾ 0.007 38.360 ⫾ 0.023 0.711638 ⫾ 13
small oil pool Huan30 18.236 ⫾ 0.011 15.626 ⫾ 0.009 38.304 ⫾ 0.023 0.712401 ⫾ 26
North part, Gao2-3-6 17.625 ⫾ 0.011 15.511 ⫾ 0.008 37.947 ⫾ 0.024 0.710611 ⫾ 28
medium oil Gao2-4-052 17.687 ⫾ 0.018 15.478 ⫾ 0.015 37.896 ⫾ 0.039
pool Gao3-5-072 17.500 ⫾ 0.011 15.392 ⫾ 0.010 37.645 ⫾ 0.027 0.719683 ⫾ 63
a
Sr concentration (ppb).

oil pools, constitutes a linear array close to the zero-age geo- 1/Sr plot (Fig. 13) for the data with measured Sr concentrations
chron. This linear array also passes through the primitive man- by isotopic dilution (Table 6) roughly shows two mixing trends
tle point of North China. These Pb isotopic relationships were and 87Sr/86Sr ⫽ 0.70878 as a common end member. It is
not observed in crust-derived rocks. suggested, on the basis of a Sr-Pb isotopic correlation diagram
The 87Sr/86Sr ratios of crude oil from Liaohe range from (Fig. 11), that the bulk of samples with 87Sr/86Sr ⬍0.7110 lie
0.7065 to 0.7240, and most of the samples show Sr isotopic in a range from the upper mantle of subduction zones to the
compositions close to those of Tertiary seawater (0.7077 juvenile crust on the basis of the model proposed by Zhu
⬃0.7092) (Veizer et al., 1999). A Sr isotopic mapping and (1998a). The two ranges also correspond to island arc volcanics
contour line treating for the crude oil samples in the Liaohe oil and oceanic sediments, respectively.
field is shown in Figure 1d. There clearly exists a steep gradient
The crude oil and kerogen from Liaohe show similar varia-
of Sr isotopic ratios, which crosses the Tertiary basin in a
tions of Nd isotopic compositions. The ␧Nd(t)-␧Sr(t) data field
northeasterly direction. High 87Sr/86Sr values occur in the
overlaps with that of the lower crust of continental China and
northwest, and low values occur in the southeast. A 87Sr/86Sr-
shows horizontal dispersion (Fig. 14), a typical feature of
crust-derived rocks (Zhu 1998a). Thus, the sources of neody-
mium in crude oil and kerogen could be involved in mixing
between upper and lower crust.

Fig. 12. 207Pb/204Pb-206Pb/204Pb plot for crude oil from the Liaohe
oil field. The means of UC, OR, M, LC, and PM (with star) are the
same as Figure 5. The field of Tertiary basalts in North China is from
Peng et al. (1986), Basu et al. (1991), and Zhu (1995, 1998a). The field
of upper crust in the Anshan area is from Zhu (1998a). The shaded area Fig. 13. 87Sr/86Sr-1/Sr plot for crude oil samples in the Liaohe oil
indicates the data field of major and large oil pools. field. Dashed lines are possible mixing trends.
 Pb, Sr, and Nd isotopes in organic matter from China 2567

components and vitrinite reflectance R0, (i.e., the higher meta-

morphic temperature, the more addition of crustal compo-
nents).
However, some isotopic features may be explained as mixing
between upper and lower crust, such as the Nd-Sr isotopic
correlation in Tarim and Liaohe (Figs. 4 and 14). We suggest
that there are two possibilities to yield these isotopic features.
First, because there is an Archaean basement with low 143Nd/
144
Nd ratios in Tarim and Liaohe, associated sediments came
from denudation of neighboring Archaean crust. The Nd model
ages of Tarim bitumen lie in the Proterozoic-Archaean range
(Table 2). The Nd isotopic compositions in crude oil are similar
to those of kerogen from sediments in Liaohe. Thus, Nd iso-
Fig. 14. ␧Nd(0)-␧Sr(0) plot for crude oil and kerogen from the Liaohe topic ratios reflect the source area of the sediments. Second,
oil field. The ␧Nd(0)-␧Sr(0) fields of bitumen from Karamay and Tarim fluids came from a deep source, which carried the isotopic
are also shown. signature of the lower crust.
On the basis of the Plumbotectonic model, the Pb isotopic
compositions (206Pb/204Pb-207Pb/204Pb) of crude oil and bitu-
5. DISCUSSION men-A from Liaohe lie in between upper and lower crustal
On the basis of the Pb, Sr, and Nd isotopic features of curves but differ from the range of Pb isotopic compositions of
bitumen, crude oil, and kerogen from large oil fields and local lower crust (Fig. 12). Therefore, petroleum generation and
paleo-oil fields where only bitumen occurs, we can obtain the migration are involved in a complicated interaction between the
following general information for petroleum generation and lower and upper crusts and the mantle.
migration. The evidence for hydrocarbon from mantle-derived rocks
and fluids has been reported in many articles (Giardini et al.,
1982; ODP Leg 110 Scientific Party, 1987; Welhan and Lup-
5.1. Petroleum Generation Is Associated with
ton, 1987; Sugisaki and Mimura, 1994; Chen et al., 1997). The
Crust–Mantle Interaction
natural gas from the Liaohe oil field yielded ␦13C3 and ␦13C2
The Pb and Nd isotopic compositions of crude oil and values from ⫺6.1‰ to ⫺0.37‰ and 3He/4He ⫽ 5.5 ⫻ 10⫺6,
bitumen from large oil fields show features of mantle– crust which indicates that there are considerable mantle components
mixing. The positive ␧Nd(t) in the bitumen from the Karamay in the gas pools (Xu et al., 1990; Chen et al., 1997). Therefore,
oil field provides the best evidence for a source related to hydrocarbon generation, including biogenic or abiogenic, could
depleted mantle, such as mantle-derived rocks (Table 1). Their be related to various interactions of mantle-derived fluid– hy-
correlation of ␧Nd(t)-␧Sr(t), either t ⫽ 0 or t ⫽ 290 Ma, is drocarbon source rock or organic fluid–mantle– derived rock.
similar to that of typical ophiolites and volcanic rocks in island Petroleum exploration has confirmed that most of the large
arcs involved in subduction of oceanic plates (Figs. 4 and 14) oil fields occur in foreland and rift basins along craton margins
where there existed material mixing from depleted mantle, or continental slopes, or close to paleo subduction zones (Szat-
crust, and seawater (Jacobsen and Wasserburg, 1979; Shaw and mari, 1989), which provides conditions for crust–mantle inter-
Wasserburg, 1985). Because Nd/Sr ratios of mantle-derived action. The geologic setting of the Karamay oil field is closely
rocks (⬃0.1) are much greater than those of seawater (⬃10⫺6) associated with the Paleozoic suture zone. The oil fields in the
and land-derived water (⬍10⫺4), mixing results in vertical or eastern China mainly occur on craton margins (Fig. 1) and are
horizontal correlation trends (Fig. 4). The Pb isotopic signa- related to cross areas between Paleozoic foreland basins of the
tures from the Karamay and Liaohe oil fields also provide craton margin and Tertiary rift basins (Zhu, 1998b; Zhu et al.,
evidence of mantle– crust interaction similar to igneous rocks 1998). Roberts and Carney (1997) reported that episodic vent-
occurring in subduction zones (Figs. 5 and 12). ing of brines, formation waters, gas, crude oil, and fine-grained
Although the isotopic compositions of bitumen from the sediments occur on the continental slope in the northern Gulf of
paleo-oil fields Guizhou and Tarim appear in trends of mantle– Mexico. These tectonic environments and material migration
crust mixing, the sources are predominantly from the crust. The processes provided advantageous conditions for interactions of
Pb isotopic data of Guizhou bitumen lie on the upper side of the crust–mantle and fluid–rock.
upper crust curve (Fig. 8). Although the data field of Pb A great deal of isotopic evidence has demonstrated that
isotopes of Tarim bitumen is situated in between the mantle and metal mineralization in the tectonic environments discussed
upper crust curves (Fig. 7), the Nd isotopic ratios (⬍0.5120) above was closely related to crust–mantle interaction (Hou and
evidently show crustal features (Fig. 6). Thus, the isotopic Zhang, 1998; Zhu et al., 1999). Present or paleo-oil fields often
compositions of bitumen indicate that there are predominant coexisted with Hg, Sb, U, Pb-Zn, and Au mineralization. For
mantle components in Karamay, crust–mantle mixing of about example, the paleo-oil field in Guizhou is also a giant Hg, Sb,
equal quantity in Tarim, and predominant upper crustal com- and U mineralization zone in China. Gold mineralization
ponents in Guizhou. The vitrinite reflectance R0 of bitumen widely occurs in Carboniferous strata in the Karamay area. In
shows Guizhou (2.1–3.2%) ⬎ Tarim (0.67 to 0.96%) ⬎ Kara- the Japan Island arc, the black ore zone (Pb, Zn, Cu, and Fe) is
may (0.40 – 0.42). Therefore, there is roughly a positive corre- closely associated with the oil-gas zone. There is paragenesis of
lation between mixing proportion of isotopes from crustal hydrothermal deposits and oil-gas fields in the Okinawa Trough
2568 Z. Bing-Quan et al.

(Simoneit, 1988; Paull et al., 1997; Hou and Zhang, 1998). no difference of stratigraphic units at the both sides of the steep
Oliver (1992) has suggested that the oil fields and Pb-Zn gradient of Sr isotopes in the Tertiary basin, but the steep
deposits of Mississippi valley type in the United States were gradient is consistent with the northwestern boundary of the
formed in the same tectonic environment, associated with sub- buried Paleozoic basin, revealed by drilling exploration. Thus,
duction zones and orogen belts. Therefore, petroleum genera- the gradient contours of Sr isotope in the Liaohe oil field reflect
tion is similar to that of metal epithermal deposits (Zhu et al., the arclike strike of the buried Paleozoic foreland basin on the
1999). craton boundary between the North China and Laojiao blocks.
It is suggested that there was strontium adding from carbonate
5.2. Implications of Sr Isotopic Compositions for Sources strata of the buried Paleozoic basin for the crude oil with low
87
and Migration of Crude Oil and Bitumen Sr/86Sr (⬍0.7100). The high value area of Sr isotopic ratios
may reflect an environment of continental facies, and there was
Because strontium possesses high solubility in water, its
no influence of carbonate Sr from deep sources. The 87Sr/86Sr-
resident time in fluid systems is distinctly longer that those of
1/Sr correlation of crude oil can support such a mixing model
Nd and Pb. Sr isotopic studies of river waters, brines, and
(Fig. 13). The common end component of 87Sr/86Sr ⫽ 0.70878
ground waters have shown that their isotopic ratios reflect
with high Sr concentration is carbonates, and the other end
migration processes of fluids involved with preferential weath-
ering of different minerals, cation exchange during water– host members are those of detrital rocks.
rock interaction, and influx from meteoric water (Stueber et al., (3) There was a contribution of Sr from mantle-derived
1984; Chaudhuri et al., 1987; Brand, 1991; Miller et al., 1993; fluids. The initial 87Sr/86Sr of bitumen in the Karamay oil field
Negrel et al., 1993; Stueber et al., 1993; Bullen et al., 1996; is 0.70570. There are also few data in crude oils with 87Sr/86Sr
Martin and McCulloch, 1999). Because organic matter has the ratios lower than 0.7071, the lower limit of seawater Sr during
attributes of fluids, their Sr isotopic compositions show the the Late Carboniferous–Early Permian. The liquid inclusions of
features similar to river waters, brines, and ground waters. quartz along the Talabude zone in the Karamay area yield
However, some organic matter show closed system for Rb-Sr initial 87Sr/86Sr ratios of 0.7048 to 0.7050 (Li et al., 1998).
decay, and there is increase of radiogenic Sr as time goes on. These data cannot be explained by the addition of carbonate Sr.
Therefore, the implication of Sr isotopic compositions are more In consideration of the evidence from Pb and Nd isotopes, the
complicated than that of Pb and Nd isotopic systematics. The Sr contribution from mantle-derived fluids also cannot be ne-
variations of 87Sr/86Sr ratios in crude oils from Liaohe overlap glected.
those of kerogen rocks, including kerogen and bitumen-A.
However, 52% of the data in crude oil are lower than 0.710 and
85% of the data in kerogen are higher than 0.710 (Fig. 11 and
5.3. Kerogen Degradation Associated with the Action of
Tables 5 and 6). Three possible models can account for this Sr
isotopic variation: Fluid from Deep Sources
(1) The strontium with lower 87Sr/86Sr ratios came from
preferential weathering of minerals with low 87Sr/86Sr ratios, There are distinct differences in Pb isotopic compositions
such as plagioclase. The leached components of detrital sedi- between bitumen-A of chloroform and kerogen from the same
ments usually have 87Sr/86Sr ⬎0.710(Blum et al., 1993; Stu- area and strata in the Liaohe Basin (Fig. 9). The kerogen
eber et al., 1993; Bullen et al., 1996). Bitumen-A can be possesses higher radiogenic Pb with crustal features, whereas
regarded as a product of fluid– black shale interaction. Thus, bitumen-A shows homogeneous Pb isotopic compositions with
their 87Sr/86Sr ratios in Liaohe are comparable to those of mantlelike features. The differences in Pb and Nd isotopes
leached components of detrital sediments. However, more than between bitumen and kerogen are also identified in the paleo-
half of Sr isotopic data of crude oils is clearly lower than 0.710 oil fields of Tarim and Guizhou (Figs. 5, 7, and 8). Thus,
(Fig. 11). Thus, it is not a reasonable explanation for the Sr bitumen was not directly degraded from kerogen. Kerogen
isotopic compositions of crude oil. degradation is not only the result of heating to high tempera-
(2) Mixing of two end components caused the variation of Sr
tures, but also the result of hydrothermal action, which pro-
isotopic compositions. The strontium with high 87Sr/86Sr ratios
vided energy and catalyzed kerogen degradation, and light
was derived from detrital rocks in the Tertiary basin. The end
components of hydrocarbon. Hydrothermal alteration, espe-
member with low 87Sr/86Sr ratios was related to carbonate
cially pyritization, is well developed in the hydrocarbon source
sediments, which have a range of 87Sr/86Sr ratios similar to that
of seawater (0.7067– 0.7092) during the Phanerozoic (Veizer et rocks of the Liaohe Basin. The existence of hydrothermal
al., 1999). Sr concentrations in carbonates are higher than those hydrocarbon has been identified in the ultradeep wells in
of detrital rocks, and carbonates are easily dissolved in fluids. Dongpu Depression of the Bohaiwan Basin, Guaymas Basin,
Thus, carbonates can contribute the major part of strontium in King Geoge Basin, and Okinawa-jima Trough (Schoell et al.,
fluids. The Sr isotopic tracing has identified that the formation 1990; Wakita et al., 1990; Whiticar and Suess, 1990; Hou and
water in the Illinois Basin predominantly carried carbonate Sr Zhang, 1998; Zhang et al., 1999). Organic matter in sediments
(Stueber et al., 1993). Carbonate strata widely occur beneath can be rapidly evolved during reaction with hydrothermal hy-
the Liaohe Tertiary basin, which represent a sedimentary en- drogen (Xiong and Lu, 1996; Demitrivsky, 1998). Therefore,
vironment of marline facies during Sinian and Paleozoic. The hydrocarbon generation in kerogen rocks associated with fluid
Sr isotopic mapping has identified that there exists a steep action from deep sources may have widely occurred in the
gradient of Sr isotopes in the Liao oil field (Fig. 1d). There is continental margins and rift basins in eastern China.
 Pb, Sr, and Nd isotopes in organic matter from China 2569

5.4. Possibility of Dating for Petroleum Generation and isochron correlation for the kerogen from the Guizhou paleo-oil
Migration field, which indicates that the formation age of kerogen is
514 ⫾ 44 Ma. Thus, there is great potential for dating of
Parnell and Swainbank (1990) have reported a good Pb-Pb
petroleum generation and migration by use of Pb-Sr-Nd radio-
isochron age of bitumen, which indicated the migration age of
genic isotopic systematics.
bitumen. Our study in the Karamay oil field provides a Rb-Sr
isochron age (284 –286 Ma) (Fig. 2), which likely represents
the age of petroleum generation because of the low vitrinite Acknowledgments—This project was supported by the National 973
reflectance R0 of bitumen. The isochron age is older than the Project of China (G1999-043213), the National Natural Science Foun-
dation of China (NSFC grant 49773187), and the China National
stratigraphic age of the bitumen reservoir and close to that of Petroleum Cooperation. Thanks to Drs. Cheng Yixian, Piao Mingzhi,
the underlying Carboniferous strata in the Junggar basin. There and Liu Dehan for their help during sample collection and pretreatment.
are more than 10 gold deposits occurring in Carboniferous We particularly thank Dr. Scott McLennan and other reviewers for
strata in this area. Li et al. (1998) have reported two Rb-Sr improving the article’s English and its scientific discussion.
isochron ages of liquid inclusion of quartz for two large gold
deposit in Hatu (Fig. 1a). The ages and initial (87Sr/86Sr)I ratios Associate editor: S. M. McLennan
are 290 ⫾ 2 Ma, 0.7048 ⫾ 1 and 288 ⫾ 12 Ma, and 0.70500 ⫾
2 Ma, respectively. They are in good agreement with the REFERENCES
bitumen Rb-Sr isochron age in Karamay. Therefore, there
existed strong fluid activation, which carried mantle isotopic Basu A. R., Wang J., Huang W., Xie G., and Tasumoto, M. (1991)
Major element, REE, and Pb, Nd and Sr isotopic geochemistry of
signature during the Late Carboniferous–Early Permian. Data Cenozoic volcanic rocks of eastern China: Implications for their
indicate that the bitumen originated in Carboniferous strata and origin from suboceanic-type mantle reservoirs. Earth Planet. Sci.
migrated into the Cretaceous strata during a later stage. U-Pb Lett. 105, 149 –169.
and Pb-Pb age determinations for kerogen usually give good Blum J. D., Erel Y., and Brown K. (1993) 87Sr/86Sr ratios of Sierra
results, as reported by Mossman et al. (1993) and herein. Nevada stream waters: Implications for relative mineral weathering
rates. Geochim. Cosmochim. Acta 57, 5019 –5025.
Therefore, radiogenic isotopic systematics can be preserved as Brand U. (1991) Strontium isotope diagenesis of biogenic aragonite
closed systems in bitumen and kerogen at the temperature of and low-Mg calcite. Geochim. Cosmochim. Acta 55, 505–513.
petroleum generation and migration, thus providing a means for Bullen T. D., Krabbenhoft D. P., and Kendall C. (1996) Kinetic and
petroleum dating. However, to select suitable samples for dat- mineralogic controls on the evolution of groundwater chemistry and
87
Sr/86Sr in a sandy silicate aquifer, northern Wisconsin, USA.
ing, more detailed studies are required. It is suggested, on the Geochim. Cosmochim. Acta 60, 1807–1821.
basis of our study, that the bitumen with low R0 (⬍0.5%), Chaudhuri S., Broedel V., and Chauer N. (1987) Strontium isotopic
where the temperature of thermal metamorphism is lower than evolution of oil-field-waters from carbonate reservoir rocks in Bind-
200°C, should be ideal samples for the dating of petroleum ley Field, central Kansas, USA. Geochim. Cosmochim. Acta 51,
generation. 45–53.
Chen Y. X. (1985) Fracture evolution order of the Liaohe Rift Basin
and formation model of oil pools (in Chinese). Petr. Acta 6, 1–11.
6. CONCLUSION Chen Y. W., Mao C. X., and Zhu B.-Q. (1982) Lead isotopic compo-
sition and genesis of Phanerozoic metal deposits in China. Geochem-
The Pb and Nd isotopic compositions in crude oil and istry 1, 137–158.
bitumen from large oil fields, Karamay and Liaohe, show Chen Z. Y., Yu B. J., and Zheng Z. Y. (1997) Compound genesis of
evidence for mantle– crust mixing. There is a positive correla- nature gas with multi-sources in the Liaohe Basin (in Chinese). Sed.
tion between mixing proportions of isotopes from crustal com- Acta 2, 58 – 62.
Demitrivsky A. H. (1998) Hydrothermal-degassing in hydrocarbon
ponents and vitrinite reflectance R0 for bitumen samples from generation. Petr. Geol. Information 18, 222–230.
the various oil fields. Notable differences in Pb isotopes be- DePaolo D. J. (1988) Nedymium Isotope Geochemistry. Springer-Ver-
tween bitumen and kerogen from same strata are identified in lag.
Liaohe, Tarim, and Guizhou. The isotopic evidence supports Fu J. M., Jia R. F., Liu D. H., and Shi J. X. (1989) Organic Geochem-
the suggestion that petroleum generation in kerogen rocks was istry of Carbonate Sediment(in Chinese). Science Press.
Giardini A. A., Melton C. E., and Mitchell R. S. (1982) The nature of
closely associated with fluid activity from deep sources. The upper 400 km of the earth and its potential as the source for
foreland basins and rift basins in craton margins provide pre- nonbiogenic petroleum. J. Petrol. Geol. 5, 175–190.
ferred environments for crust–mantle interaction during petro- Hou Z. Q. and Zhang Q. L. (1998) CO2-hydrocarbon fluids of the
leum generation and migration. modern active thermal water in Okinawa-Jima trough: Evidence of
fluid inclusion. Sci. Chin. D 28, 142–148.
The Sr isotopic mapping and Sr-Pb isotopic correlation in the Huseby B. and Ocampo R. (1997) Evidence for porpyrin bound, via
Liaohe oil field indicates that the variation of Sr isotopic ester bonds, to the Messel oil shale kerogen by selective chemical
compositions in crude oil and bitumen samples mainly reflects degradation experiments. Geochim. Cosmochim. Acta 61, 3951–
mixing of strontium from various strata. The end members with 3956.
high 87Sr/86Sr ratios were derived from detrital rocks in the Jacobsen S. B. and Wasserburg, G. J. (1979) Nd and Sr isotopic study
of the islands ophiolite complex and the evolution of the source of
Tertiary basin, and the end member with low 87Sr/86Sr ratios midocean ridge basalts. J. Geophy. Res. 84, 7429 –7445.
was related to carbonate sediments in the buried Paleozoic Kang Y. Z. (1992) Oil and Gas Field in the Tarim Paleozoic Basin(in
basins. Chinese). China University of Geoscience Press, Wuhan.
The bitumen samples from the Karamay oil field show low Li H., Xie C., Chang H., Cai H., Zhu J., and Zhou S. (1998) Study on
Metallogenetic Chronology of Nonferrous and Precious Metallic
vitrinite reflectance R0 (⬍0.5%) and yield a Rb-Sr isochron age Ore Deposits in North Xinjiang, China (in Chinese). Geological
of 284 to 286 Ma, which may represent the age of petroleum Publishing House.
generation or fluid activation in this area. There is a good Pb-Pb Liu S. H., Wu W. W., and Yu K. F. (1988) The diagenesis, reservoir
2570 Z. Bing-Quan et al.

types and oil pool types of Wenan paleo-oil pool, Guizhou (in Formation waters from Mississippian-Pennsyvanian reservoirs, Illi-
Chinese). Oil Gas Geol. Mar. Dep. Reg. 2(2), 46 –55. nois Basin, USA: Chemical and isotopic constrains on evolution and
Manning, L. K., Frost C. D., and Brantharer, J. F. (1991) A neodymium migration. Geochim. Cosmochim. Acta 57, 763–784.
isotopic study of the crude oils and source rocks: Potential applica- Sugisaki R. and Mimura K. (1994) Mantle hydrocarbons—Abiotic or
tions for petroleum exploration. Chem. Geol. 91, 125–138. biotic? Geochim. Cosmochim. Acta 58, 2527–2542.
Martin C. E. and McCulloch M. T. (1999) Nd-Sr isotopic trace element Szatmari P. (1989) Petroleum formation by Fischer-Tropsch synthesis
geochemistry of river sediments and soils in a fertilized catchment, in plate tectonics. AAPG Bull. 73, 989 –998.
New South Wales, Australia. Geochim. Cosmochim. Acta 63, 287– Todt W., Cliff R. A., Hanser A., Hofmann A. W. (1993) Re-calibration
305. of NBS lead standards using a 202Pb⫹205Pb double spike (abstract).
Miller E. K., Blum J. D., and Friedland A. J. (1993) Determination of Terra Nova (Suppl.) 5, 396.
soil exchangeable-cation losses and weathering rates using Sr iso- Tu X.-L., Zhu B.-Q., Zhang J.-L., Liu Y., Liu J.-Y., and Shi Z.-A.
topes. Nature 362, 438 – 441. (1997) Pb, Sr, and Nd isotope application in geochronology and the
Mossman D. J., Nagy B., and Davis D. W. (1993) Comparative origin of petroleum (in Chinese). Geochimica 26(2), 7–33.
molecular element and U-Pb isotopic composition of stratiform and Veizer J., Ala D., Azmy K., Bruckschen P., Buhl D., Bruhn F., Carden
dispersed globular organic matter in the lower Proterozoic uranifer- G. A. F., Diener A., Ebneth S., Godderis Y., Jasper T., Korte C.,
ous metasediment, Elliot Lake, Canada. Energy Source 15, 375–386. Pawellek F., Podlaha O. G., and Strauss H. (1999) 87Sr/86Sr, ␦13C
Negrel P., Allegre C. J., Dupre B., and Lewin E. (1993) Erosion and ␦18O evolution of Phanerozoic seawater. Chem. Geol. 161, 59 –
sources determined by inversion of major and trace element ratios 88.
and strontium isotopic ratios in river water: The Congo Basin case. Wakita H., Sano Y., Urabe A., et al. (1990) Origin of methane-rich
Earth Planet. Sci. Lett. 120, 59 –76. natural gas in Japan: Formation of gas field due to large-scale
ODP Leg 110 Scientific Party. (1987) Expulsion of fluids from depth submarine volcanism. Appl. Geochem. 5, 263–278.
along subduction zone decollement horizon. Nature 326, 785–788. Welhan J. A. and Lupton J. E. (1987) Light hydrocarbon gases in
Oliver J. (1992) The spots and stains of plate tectonics. Int. Geol. Guaymas Basin hydrothermal fluids: Thermogenic versus abiogenic
Rev. 32, 77–106. origin. AAPG Bull. 71, 215–223.
Parnell J. and Swainbank I. (1990) Pb-Pb dating of hydrocarbon Whiticar M. J. and Suess E. (1990) Hydrothermal hydrocarbon gases in
migration into a bitumen-bearing ore deposit, North Wales. Geolo- the sediments of the King Geoge Basin, Bronsfield, Antarctica. Appl.
gy 18, 1028 –1030. Geochem. 5, 135–147.
Paull C., Dickens G. R., and Borowski W. (1997) ODP drills gas Xiong S. S. and Lu P. D. (1996) Volcanic eruption– effusion and its
hydrates, the world’s largest source of fossil fuel. ODP’s Greatest
relationship with the formation and type of semi-inorganic gas (in
Hits, pp. 22–23.
Chinese). Exp. Petrol. Geol. 18, 13–35.
Peng Z. C., Zartman R. E., Fuda E., and Chen D. G. (1986) Pb-, Sr- and
Xu Y. C., Shen P., and Tao M. X. (1990) Industrial reservoirs of helium
Nd-isotopic systematics and chemical characteristics of Cenozoic
from mantle sources and the Tanlu fault zone. Chin. Sci. Bull. 12,
basalts, eastern China. Chem. Geol. 59,3–33.
932–935.
Pushkarev Y. D., Gottikh R. P., Pisotsky B. I., and Zhuravlew D. Z.
Yu J. and Gui X. (1998) Isotope geochemistry of granitoids. In Isotope
(1998) Super large oil deposits as a results the crust–mantle inter-
action? Chin. Sci. Bull. (Suppl.) 43, 105. Geochemistry Research in China (eds. G. Tu and T. J. Chow), pp.
Roberts H. H. and Carney R. S. (1997) Evidence of episodic fluids, gas 137–161. Science Press.
and sediment venting on the northern Gulf of Mexico continental Zartman R. E. and Doe B. R. (1981) Plumbotectonics—The model.
slope. Econ. Geol. 92, 863– 879. Tectonophysics 75, 135–162.
Rowe P. J., Richards D. A., and Atkinson T. C. (1997) Geochemistry Zhang C. and Zhai M. G. (1993) Ophiolitic belts and their genetic
and radiometric dating of a middle Pleistone peat. Geochim. Cos- environment in Western Junggar. In New Improvement of Solid
mochim. Acta 61, 4201– 4212. Geoscience in Northern Xinjiang(ed. G. Z. Tu), pp. 53–78. Science
Schoell M., Hwang R. J., and Simoneit B. R. T. (1990) Carbon isotopic Press.
composition of hydrothermal petroleum from Guaymas Basin, Gulf Zhang J. L., Zhu B.-Q., Chen Y. X., Tu X.-L., Chao Z. L., Zhang C. J.,
of California. Appl. Geochem. 5, 65– 69. Xiao Q. H., Li J. Y., and Piao M. Z. (1999) Pb, Sr isotopes in organic
Shaw H. F. and Wasserburg G. J. (1985) Sm-Nd in marine carbonates matter of Lower Tertiary hydrocarbon source rocks in Liaohe Fault
and phosphates: Implications for Nd isotopes in seawater and crustal Depression. Chin. Sci. Bull. 44, 2192–2195.
ages. Geochim. Cosmochim. Acta 49, 503–518. Zhu B.-Q. (1995) The mapping of geochemical provinces in China
Shock E. L. and Koretsky C. M. (1995) Metal-organic complexes in based on Pb isotopes. J. Geochem. Explor. 55, 171–181.
geochemical processes: Estimation of standard partial molal thermo- Zhu B.-Q. (1998a) Theory and Application of Isotopic Systematics in
dynamic properties of aqueous complexes between metal cations and Earth Sciences (in Chinese). Science Press.
monovalent acid ligands at high pressures and temperatures. Zhu B.-Q. (1998b) Study on chemical heterogeneity of crust–mantle
Geochim. Cosmochim. Acta 59, 1497–1532. and geochemical boundaries of blocks (in Chinese). Earth Sci.
Simoneit B. R. T. (1998) Petroleum generation in submarine hydro- Front. 5, 72– 82.
thermal systems: An update. Can. Mineral. 26, 827– 840. Zhu B.-Q. and Chen Y. W. (1984) Features of Pb isotopic composition
Stille P., Gauthier-Lafage F., and Bros R. (1993) The neodymium of ores and evolution of continental crust of China. Sci. Sinica B 6,
isotopic system as a tool for petroleum exploration. Geochim. Cos- 635– 646.
mochim. Acta 57, 4521– 4525. Zhu B.-Q., Chang X. Y. Qiu H. N., and Sun D. Z. (1998) Character-
Stueber A. M., Pushkar P., and Hetherington E. A. (1984) A strontium istics of Proterozoic basement on the geochemical steep zones in the
isotopic study of Smackover brines and associated solids, southern continent of China and their implications for setting of super large
Arkansas. Geochim. Cosmochim. Acta 48, 1637–1650. deposits. Sci. Chin. D (Suppl.) 41, 54 – 64.
Stueber A. M. and Walter L. M. (1991) Origin and chemical evolution Zhu B.-Q., Dong Y.-P., Chang X.-Y., and Zhang Z.-W. (1999) Low-
of formation waters from the Illinois Basin, USA. Geochim. Cos- temperature mineralization domain associated with the parallel po-
mochim. Acta 55, 309 –325. sitions between geochemical steep zones and geophysical gradient
Stueber A. M., Walter L. M., Huston T. J., and Pushkar P. (1993) zones. Chin. Sci. Bull. (Suppl. 2) 44, 166 –168.