The geochemical characteristics of Tazhong crude oils from the Tarim Basin, northwestern

China
Author(s): Yungan Liang, Jianbing Xu, Wenwen Li, Bin Cheng, Qian Deng, Haizu Zhang and
Zewen Liao
Source: Energy Exploration & Exploitation , July 2018, Vol. 36, No. 4, Special Issue:
Advances of Petroleum Exploration and Geology Research in West China’s petroliferous
basins (July 2018), pp. 764-786
Published by: Sage Publications, Inc.

Stable URL: https://www.jstor.org/stable/10.2307/90023367

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Special Issue: Advances of Petroleum Exploration and Geology Research in West China’s petroliferous basins

Energy Exploration & Exploitation

The geochemical 2018, Vol. 36(4) 764–786
! The Author(s) 2017

characteristics of Tazhong DOI: 10.1177/0144598717742969

journals.sagepub.com/home/eea

crude oils from the Tarim

Basin, northwestern China
Yungan Liang,1,2 Jianbing Xu,1,2 Wenwen Li,3 Bin Cheng,1
Qian Deng,1,2 Haizu Zhang4 and Zewen Liao1

Abstract
Recent exploration work in the Tazhong district has gradually transferred to the exploitation of
high and over mature oils in deep and ultra-deep layers. This has proved problematic, however, as
the distribution of crude oils in the Tazhong is complex. This means that the geochemical char-
acterization of high and over mature oils, especially for light crude oils, have become increasingly
important. The stability of concerted ring structure of aromatics makes them having stronger
thermal stability and resistance to biodegradation. This means that there are abundant aromatic
compounds in high and over mature oils. This study presents a series of geochemical analyses of
the maturity parameters of 89 crude oils from the Tazhong area, including stable carbon and
hydrogen isotope analyses of compounds from 43 light crude oils. These analyses are then
compared with other data from the Tazhong Number I fault zone, as well as the Tazhong
Number 10 and Tazhong Uplift structural zones. Results show that the geochemical parameters
of oils from Tazhong Number I fault zone generally encompass a wider range than those from the
Tazhong Number 10 structural zone, which indicates that the Tazhong Number I slope belt is
more active than its counterpart structural belt and generates oils with more complex geochem-
ical characteristics. The positive correlation between the toluene/methyl cyclohexane ratio and
the dibenzothiophene/phenanthrene ratio, as well as with the naphthalene/phenanthrene ratio
indicates that aromatization parameters can be used to evaluate the maturity of light crude oils,
and there may be inherited relationships between toluene and methyl cyclohexane in crude oils.

Keywords
Aromatic compounds, light crude oils, high maturity, stable carbon/hydrogen isotope, Tarim Basin

1
State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Guangzhou, China
2
University of Chinese Academy of Sciences, Beijing, China
3
Faculty of Resource, China University of Geosciences, Wuhan, China
4
Research Institute of Petroleum Exploration & Development, Korla, China
Corresponding author:
Zewen Liao, Kehua Street 511, Tianhe District, Guangzhou 510640, China.
Email: [email protected]
Creative Commons CC-BY: This article is distributed under the terms of the Creative Commons
Attribution 4.0 License (http://www.creativecommons.org/licenses/by/4.0/) which permits any use,
reproduction and distribution of the work without further permission provided the original work is attributed as
specified on the SAGE and Open Access pages (https://us.sagepub.com/en-us/nam/open-access-at-sage).
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Liang et al. 765

Introduction
The Tarim Basin has experienced a number of structural movements, which has led to
a series of complex and diverse structural styles, and consequently large differences in
oil characteristics between different zones. The fact that large volumes of light crude oil
have been extracted from the Tazhong (TZ) area within the Tarim Basin highlights the
great potential for massive petroleum exploration from deep layers in this region (He
et al., 2016; Wang et al., 2014). Zhu et al. (2015) reported the newly discovered
Rewapu oilfield in Tarim Basin, which was well preserved due to low geothermal
stress and quick deep burial. Wang et al. (2015) analyzed sulfur-containing compounds
in Ha9 and ZS1C crude oils, identifying DBT (dibenzothiophene) series compounds in
Ha9 crude oil and thiadiamondoids with 1–3 cages in ZS1C crude oil. Zhang et al.
(2015a) conducted a series of geochemical analysis on oil reservoir fluids, suggesting
that thermal cracking and TSR have contributed a lot to the deep formation oil.
However, because of the high maturity of light crude oils, a number of normal geo-
chemical evaluation parameters cannot be applied. In addition, several structural move-
ments have changed, or even destroyed, crude oils within the Tarim Basin to different
degrees; the geothermal changes induced by these movements have affected the thermal
evolution of hydrocarbon source rocks and caused large differences in the maturity of
crude oils at different phases.
Two sets of source rocks from the CambrianLower Ordovician and Middleto-Upper
Ordovician mainly contributed to the oils from Tarim Basin (Zhang and Huang, 2005;
Hu et al., 2016; Huang et al., 2017), but the problem which one is the main source have
been debated for a few of years (Huang et al., 2016). While some workers believe the main
source of hydrocarbons is Middle-to-Upper Ordovician rocks (Hanson et al., 2000; Zhang
et al., 2000; Zhao et al., 2005), others have argued that the Cambrian-Lower Ordovician is
the main source (Liang et al., 2000; Sun et al., 2003). As this debate remains unresolved, the
main aim of this work is to provide a geochemical characterization and discussion of the
usage of aromatic compounds in the TZ area rather than to discuss the main source of
hydrocarbons within the Tarim Basin.
Compared with other molecules, aromatic hydrocarbons with higher thermal stability are
an important research object as their highly delocalized electronic conjugated system makes
their energy system low (Xing et al., 2005). This is important because deep layer source rocks
in the Tarim Basin are in high mature; source rocks from Cambrian and lower Ordovician
strata are considered over mature, and most of these rocks from the middle-to-upper
Ordovician fall within the peak oil generation and later oil windows. One good example is
the TC 1 well; the equivalent vitrinite reflectance of this well between 5713m and 7124m
depth within Ordovician layers is between 1.29% and 2.25% (Zhang et al., 2004), which
means that most normal geochemical parameters are invalid because of high maturity (Liang
and Chen, 2005). Therefore, this work also discusses the rules governing changes in aromatic
hydrocarbons within TZ crude oils.
Light hydrocarbon is another series of compounds for petroleum research. Liu et al.
(2015) reported the light composition, hydrogen and carbon isotope of the upper
Paleozoic gases in the Ordos Basin and suggested that they were all sourced from
Carboniferous–Permian coal-bed source rocks, distinguishing two type of natural gas.
Han et al. (2017) used MCH (methyl cyclohexane) index to identify Upper Paleozoic

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766 Energy Exploration & Exploitation 36(4)

gas source rocks in Shenmu gas field and think they are mainly of humic genesis of
swamp facies.

Samples and methods

Samples
A total of 89 oils samples were selected for analysis in this work from the TZ Number I fault
zone, the TZ Number 10 structural zone, and the central uplift zone. These samples comprise
49 black oils and 40 light crude oils, collected from different districts of TZ area. The black
oils are mainly from depths between 3000 m and 5000 m, while light crude oils mainly from
depths between 5000 m and 6500 m. The distribution of oil samples is shown in Figure 1.

Methods
The samples were treated by following steps.
(1) About 3 mg of the TZ black oils were taken and separated into saturates and aromatics
by successively using hexane and a mixture solvents (hexane: dichloromethane ¼ 1:3) in a
9 cm column filled with 3:1 silica gel and aluminum oxide.
(2) All separated components were analyzed with a Thermo TRACE GC Ultra combined to
a DSQ II mass instrument which was fitted with a HP-5 mass spectrometry (MS) capil-
lary column (30 m  0.32 mm  0.25 mm). Helium was used as the carrier gas at a current
speed of 1.2 mL/min, and the injection temperature was set at 295 C. The heating pro-
cedure for saturates is set as 80 C for 4 min, followed by heating of 4 C/min up to

Figure 1. Tectonic units that comprise the Tazhong Uplift and locations of the oil samples discussed in
this work.

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Liang et al. 767

295 C, and then held for 20 min. The heating procedure for aromatics as 80 C for 4 min,
followed by heating of 3 C/min up to 295 C, then held for 20 min.
(3) The light crude oils were directly used for the analyses without separation, and then the
heating procedure is set as 35 C held steady for 4 min, followed by heating at a rate of
4 C/min up to 295 C, and then held for 30 min.
(4) TZ light crude oils were analyzed using a GV isoprime GC–MS to determine the specific
stable carbon (C) and hydrogen (H) isotope values of their toluene and methyl cyclo-
hexane compounds. Thus, compounds specific C isotope values were analyzed using a
GV isoprime GC–MS fitted with a capillary column HP-1MS (30 m  0.25 mm 
0.25 mm). Finally, compound specific C isotope values were analyzed using a
ThermoFisher gas chromatography GC-IRMS fitted with a HP-1MS capillary column
(30 m  0.25 mm  0.25 mm). The heating procedure and carrier gas are the same as
previously described for GC–MS.

Results and discussion

The geochemical analysis results of the black oils and light crude oils are presented in
Tables 1 and 2, respectively.

Distribution characteristics of saturates and aromatics in TZ black oils

A total ion chromatogram (TIC) and the compounds identified in selected TZ black oil
samples are presented in Figure 2; within these samples, TZ26, TZ44 and TZ241 are located
within the TZ Number I fault zone, while TZ4, TZ104 and TZ404 are located within TZ
Number 10 structural zone, and TZ12, TZ35 and TZ162 are located within the central
uplift zone.
The distribution of n-alkanes showed that TZ black oils mainly ranges between C13 and
C30, with the main peak between C15 and C16. The pristane (Pr)/phytane (Ph) ratio falls
between 0.83 and 1.32; this ratio for samples from TZ Number 10 structural zone mainly
ranges between 0.80 and 1.00, while mainly ranges between 1.00 and 1.20 for samples from
TZ Number I fault zone. The UCM (Unidentified Complex Mixture) peaks in some samples
suggested their suffering from biodegrading, which means that these TZ oil reservoirs may
have experienced more than once charges. And it seems that the early charged oils were
biodegraded before being mixed with the later charged oils.
Table 1 lists the biomarker parameters of tricyclic terpanes, hopanes, steranes, and gam-
maceranes. These data show that the gammacerane/C30 ab hopane ratio for oils from the TZ
Number 10 structural zone as well as the central uplift zone mostly range between 0.05 and
0.31, while samples from the TZ Number I fault zone mainly range between 0.08 and 0.21.
Data also reveal a low abundance of tricyclic terpanes as well as a relatively high abundance
of pentacyclic terpanes; the C23/C21 tricyclic terpane ratio ranges between 1.05 and 2.42,
while that of C29/C30 hopanes ranges between 0.42 and 1.39. The distribution of steranes in
these samples is C27 regular steranes between 19.00% and 50.14%, while C28 steranes occur
between 16.66% and 37.63% abundance, and C29 steranes occur between 33.13% and
55.58%, which is generally characterized by an overall ratio relationship C27 > C28 < C29.
At the same time, however, a few sterane parameters of these samples display the ratio
C27 < C28 < C29. These results indicate hydrocarbon precursors derived from bacteria

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 Table 1. Geochemical parameters of Tazhong black oils.
768

Depth G/ C23/ C29/ C27 C28 C29 4-/1- 4-MDBT/ Ro Ro

Zone Well (m) Strata pr/ph C30 H C21 TT C30 H (%) (%) (%) MDBT DBT (MDR) DBT/P MPI1 MPI2 (MPI)

tz241 4618.47–4725.74 O 1.20 0.05 1.21 0.74 50.14 16.66 33.19 6.42 1.47 1.40 0.26 0.68 0.74 0.81
tz242 4065.15 S 0.92 / 1.42 0.64 35.07 13.46 51.47 4.91 0.62 1.33 1.71 0.68 0.78 0.81
tz26 4300–4315 O 1.08 0.08 1.51 0.72 23.28 25.86 50.86 4.93 1.37 1.33 0.62 0.65 0.74 0.79
tz26 4335–4360 O1 1.04 0.17 1.43 0.65 10.43 26.25 63.32 4.46 1.18 1.30 0.45 0.60 0.67 0.76
tz30 4997–5026 O 1.10 0.31 1.58 0.42 19.00 32.13 48.87 6.22 1.44 1.39 0.49 0.55 0.62 0.73
tz30 4244.5–4260 S 1.23 0.19 1.47 0.56 27.96 26.28 45.76 2.22 1.49 1.12 0.43 0.73 0.90 0.84
tz44 4854–4888.31 C2+3 0.97 0.07 1.94 1.01 21.76 34.84 43.40 6.04 1.34 1.38 0.75 0.57 0.60 0.74
tz44 4822.00 O1+2 1.12 0.15 1.50 0.74 19.79 34.50 45.70 5.19 1.36 1.34 1.06 0.66 0.76 0.80
tz45 6020–6150 O1 0.97 / 1.77 1.39 41.33 23.58 35.09 6.14 1.62 1.39 1.24 0.63 0.75 0.78

Tazhong No. I fault zone

tz451 6050–6297.62 O1+2 0.97 / 1.92 0.98 41.85 25.01 33.15 6.92 1.80 1.42 1.52 0.67 0.77 0.80
tz452 6376.76–6550 O1+2 1.04 0.25 1.62 0.54 21.09 36.70 42.22 4.64 1.64 1.31 0.23 0.42 0.47 0.65
tz54 5832–5858 O 0.94 0.13 1.66 0.52 30.22 31.30 38.48 13.12 3.58 1.59 0.30 0.66 0.72 0.80
tz62 4700.5–4758 O 1.03 0.04 1.59 0.66 12.76 29.99 57.25 9.12 1.38 1.49 0.89 0.81 0.91 0.89
tz622 4913.52–4925 O 0.94 0.08 1.93 0.67 32.61 15.46 51.94 5.19 1.51 1.34 2.07 0.66 0.73 0.80
tz72 4964–4978 O 1.11 0.10 1.53 0.53 33.55 24.70 41.75 8.64 1.66 1.48 0.60 0.64 0.73 0.78
tz72 5125–5130 O 1.04 / 1.81 0.65 48.30 18.56 33.13 1.93 1.31 1.08 2.08 0.46 0.51 0.68
tz83 5433–5441 O 1.06 0.02 1.62 0.62 44.54 21.00 34.47 8.89 1.65 1.49 0.67 0.75 0.85 0.85
tz824 5744.59–5750 O 0.87 0.06 1.40 0.54 19.78 30.36 49.87 24.66 2.82 1.76 0.37 0.75 0.84 0.85
tz828 5595–5603 O 1.04 0.13 1.57 0.45 33.25 29.03 37.72 7.43 2.84 1.44 0.26 0.66 0.71 0.80

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tz117 4422.57–4436.12 S 0.89 0.06 1.97 0.88 20.56 18.64 60.80 3.61 1.08 1.25 1.62 0.66 0.84 0.80
tz117 4450–4453 S 0.94 0.06 1.90 0.85 21.67 17.33 60.99 4.81 1.10 1.32 1.15 0.66 0.81 0.79

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tz12 4631.88–4733.92 O 0.83 0.03 2.01 0.75 34.55 21.77 43.68 5.87 1.84 1.37 0.42 0.71 0.83 0.83
tz12 4695.5–4777.5 O 0.91 0.07 1.79 0.70 26.95 21.36 51.69 4.68 1.67 1.31 0.43 0.78 0.92 0.87
tz12 4374.5–4413.5 S 0.94 0.09 1.91 0.71 26.79 22.18 51.03 3.01 1.29 1.20 0.78 0.84 1.05 0.90
tz122 4707.88–4733.92 O 0.96 0.03 2.42 0.78 36.14 21.83 42.03 5.98 1.71 1.38 0.44 0.66 0.78 0.80
tz122 4333.8–4344.4 S 1.02 0.08 2.20 0.76 27.56 21.62 50.83 3.28 1.48 1.22 0.63 0.82 0.98 0.89
tz122 4349–4352.7 S 0.98 0.08 1.88 0.72 32.30 22.94 44.76 5.79 1.97 1.37 0.80 0.78 0.89 0.87
tz15 4300–4306.5 S 0.89 0.11 1.74 0.76 35.24 26.41 38.36 2.12 1.48 1.10 0.42 1.12 1.60 1.07
tz161 4178–4181 S 0.99 0.08 1.73 0.72 29.34 18.76 51.90 4.44 0.98 1.30 1.34 0.66 0.75 0.80
tz162 3840–3842.5 C 0.98 0.28 1.22 0.54 33.69 26.21 40.10 3.39 1.28 1.23 1.18 0.86 1.03 0.91
tz169 4241.09–4283.52 O 0.94 0.06 2.02 0.79 33.94 20.94 45.12 5.12 2.22 1.34 0.63 0.73 0.82 0.84
tz169 4119.56–4149.16 S 1.32 0.10 1.72 0.59 42.45 22.85 34.70 2.10 1.35 1.10 0.40 0.83 0.99 0.90

Tazhong No.10 structural zone

(continued)
Energy Exploration & Exploitation 36(4)
 Liang et al.

Table 1. Continued

Depth G/ C23/ C29/ C27 C28 C29 4-/1- 4-MDBT/ Ro Ro

Zone Well (m) Strata pr/ph C30 H C21 TT C30 H (%) (%) (%) MDBT DBT (MDR) DBT/P MPI1 MPI2 (MPI)

tz35 4269.68–4333.92 C3 0.99 0.07 1.84 0.64 30.97 28.85 40.18 3.90 3.66 1.27 0.28 1.22 1.36 1.13
tz35 4946–4951 S 0.97 0.03 1.73 0.76 25.59 24.33 50.09 3.21 1.47 1.21 0.50 0.72 0.83 0.83
tz40 4334–4340 C3 0.89 0.13 2.06 0.86 21.72 22.68 55.60 4.89 1.29 1.33 1.97 0.76 0.91 0.86
tz47 4978.5–4986 S 1.03 0.10 1.79 0.83 24.13 17.85 58.02 6.22 1.66 1.39 1.25 0.85 0.98 0.91
tz50 4378.5–4385 S 0.88 0.08 1.60 0.75 33.15 18.99 47.86 5.22 2.05 1.34 0.32 0.68 0.80 0.81
tz69 4368.5–4377 S 1.02 / 1.05 0.99 37.91 23.96 38.13 3.50 1.68 1.24 0.37 0.74 0.88 0.84
tz104 3647–3669 C2 1.22 0.05 2.01 0.86 26.85 20.97 52.18 7.22 1.69 1.43 1.17 0.74 0.81 0.84
tz4 3532–3548 C3 0.99 0.06 2.10 0.98 21.20 37.63 41.18 6.91 1.94 1.42 1.73 0.78 0.83 0.87
tz404 3619.47–3681.81 C 1.01 0.11 2.16 0.82 31.46 20.94 47.60 6.49 1.84 1.40 2.20 0.83 0.90 0.90
tz406 3646.92–3692.26 C 0.90 0.21 0.81 0.79 25.94 18.82 55.23 4.37 1.62 1.30 0.71 0.55 0.69 0.73
tz406 3646.92–3692.27 C 0.88 0.22 2.12 0.91 36.00 18.47 45.53 5.87 1.96 1.37 0.84 0.68 0.76 0.81

the central uplift zone

tz406 3952.5–4128.63 C3 0.99 0.10 2.09 0.82 24.64 14.78 60.58 5.89 1.59 1.38 1.79 0.73 0.82 0.84
tz411 3263–3450 C 0.96 0.08 2.12 1.01 28.83 20.82 50.36 5.38 2.49 1.35 1.66 0.81 0.91 0.89

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tz422 3537–3554 C1 0.99 0.06 2.03 1.34 26.47 17.94 55.58 5.67 1.89 1.37 1.11 0.74 0.79 0.84
tz43 3652–3554 O 1.01 0.15 1.30 0.65 42.01 8.47 49.52 13.22 1.75 1.59 0.91 0.78 0.88 0.87

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tz4-7-38-1 3936.43–3985.5 O 0.92 0.10 1.69 1.10 30.54 18.74 50.73 2.74 1.28 1.17 0.75 0.78 0.91 0.87
tz52 3808.46–3831.5 O 1.20 0.04 1.22 0.79 20.44 18.40 61.16 10.53 1.94 1.53 1.21 0.86 0.98 0.91

G/C30 H: gammacerane/C30 hopane; C23/C21 TT: C23 tricyclic terpane/C21 tricyclic terpane; C29/C30 H: C29 hopane/C30 hopane; C27 (%), C28 (%), and C29 (%) refer to C27, C28,
and C29 steranes; MDBT: methyldibenzothiophene; DBT: dibenzothiophene; MDR ¼ 4-/1-MDBT; MPI1: methylphenanthrene indicator 1; MPI2: methylphenanthrene indicator 2.
769
 770

Table 2. Geochemical parameters of Tazhong light crude oils.

Depth Tol/ 2-/ MN/ DMN/ 4-MDBT/ 4-/1- Ro Ro

Zone Well (m) Strata MCH 1-MN DMN TMN N/P DBT/P DBT MDBT (MDR) MPI1 MPI2 (MPI)

ZG10 6198–6309 O 1.61 1.68 1.13 2.24 8.86 2.55 1.10 4.59 1.31 0.80 0.93 0.88
ZG101 6998–6309 1.16 2.24 0.77 1.18 4.84 2.04 1.29 2.06 1.10 1.06 1.21 1.03
ZG102 6022.5–6410 1.77 2.73 0.80 3.26 9.04 5.84 0.80 5.88 1.38 0.74 0.76 0.84
ZG103 6105–6223 1.19 1.51 0.59 1.33 7.44 0.64 1.24 6.23 1.39 0.72 0.84 0.83
ZG105 5936–6829.28 O1y 1.37 1.98 0.51 0.90 5.04 4.47 0.97 2.81 1.18 0.72 0.79 0.83
ZG106 6110–6115 1.40 2.48 0.69 1.66 15.21 3.54 4.20 6.73 1.41 0.86 0.92 0.92
ZG11-7H 6263–6302.7 O 1.16 2.81 0.88 1.61 30.14 3.37 3.42 3.02 1.20 0.79 0.88 0.87
ZG12 6059.58–6279 O 1.60 1.67 0.84 1.73 6.90 1.71 1.40 10.84 1.54 0.54 0.64 0.72
ZG13 6458–6550.36 O3L 1.35 1.43 0.54 1.25 4.63 2.81 1.52 5.84 1.37 0.57 0.75 0.74
ZG13-1H 5886–7135 0.93 1.93 0.65 1.03 3.18 1.09 1.62 5.88 1.38 0.80 0.89 0.88
ZG14-1 6133–6298 O 2.01 2.08 0.77 1.54 10.56 3.52 1.16 5.16 1.34 0.78 0.82 0.87
ZG151 6083.75–6223.81 O2 1.84 1.64 0.69 1.44 15.98 2.20 1.08 4.91 1.33 0.50 0.59 0.70
ZG162-H2 6104.05–7495 O 1.36 1.43 1.04 2.36 30.25 1.90 1.55 3.69 1.25 0.67 0.60 0.80

Tazhong No. I fault zone

ZG163 6140–6224 0.98 1.48 0.64 0.91 6.63 2.09 1.62 6.14 1.39 0.58 0.71 0.75
ZG164 6122.13–6213.58 O 1.34 1.91 0.58 1.14 5.53 2.39 1.44 5.45 1.36 0.51 0.56 0.70
ZG17 6206–6446 O1y 1.16 1.81 0.82 1.51 10.08 4.33 0.60 3.72 1.25 0.67 0.77 0.80
ZG17-H1 6088–6887 1.01 1.21 1.14 2.32 6.36 1.01 1.42 4.59 1.31 0.54 0.64 0.73

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ZG19 6381–6438.5 O 0.63 1.23 0.63 1.22 3.63 0.64 1.80 6.54 1.40 0.73 0.79 0.84

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ZG21-H 5995–6060 O 1.46 1.81 0.79 1.00 9.06 2.36 0.82 3.10 1.20 0.66 0.66 0.80

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ZG22 5605–5736.66 O 1.55 1.79 0.59 1.13 5.06 1.82 1.49 6.62 1.41 0.71 0.79 0.83
ZG501 6515.5–6790.4 1.17 1.87 0.52 1.21 3.68 4.19 1.48 9.55 1.50 0.54 0.62 0.72
ZG503 5919–6100 1.67 1.50 0.51 1.14 6.00 3.37 1.49 4.61 1.31 0.79 0.91 0.87
ZG6 5934.5–6172.73 O1y 2.37 1.49 0.63 1.30 13.52 6.23 0.91 3.65 1.25 0.67 0.81 0.80
ZG6-2 5898.25–6143.17 O1y 2.12 1.63 0.59 1.53 10.16 5.50 1.21 4.31 1.29 0.72 0.84 0.83
ZG7 5865–5885 1.73 2.53 0.79 1.78 3.88 4.40 1.40 3.86 1.26 0.64 0.85 0.78
ZG70 5714–5728 1.32 1.31 0.68 0.95 9.22 4.54 0.97 2.86 1.18 0.68 0.85 0.81
ZG702 5628–5890 O 2.21 2.02 0.85 1.69 12.59 9.64 0.91 5.49 1.36 0.61 0.74 0.76
(continued)
Energy Exploration & Exploitation 36(4)
 Liang et al.

Table 2. Continued

Depth Tol/ 2-/ MN/ DMN/ 4-MDBT/ 4-/1- Ro Ro

Zone Well (m) Strata MCH 1-MN DMN TMN N/P DBT/P DBT MDBT (MDR) MPI1 MPI2 (MPI)

ZG43-1 5200–5348 O1H 1.30 1.78 0.71 1.44 5.98 2.67 1.21 9.65 1.51 0.60 0.70 0.76
ZG43-1 5200–5798 O1y 1.17 1.37 0.70 0.87 6.48 2.05 1.18 4.06 1.28 0.66 0.77 0.79
ZG441 5414.38–5522 1.21 1.57 0.68 1.10 4.08 1.38 0.92 5.23 1.34 0.59 0.69 0.75
ZG44C 5432–5861.50 1.27 2.03 0.62 1.21 7.77 3.06 1.13 4.87 1.33 0.74 0.78 0.84
ZG45 5637.2–5650.17 O3 1.19 1.36 0.65 1.08 2.92 1.85 1.12 4.24 1.29 0.65 0.77 0.79
ZG46 5039.40–5367.34 O3 3.03 1.52 0.70 1.44 14.71 3.91 1.37 4.43 1.30 0.83 0.95 0.90
ZG461 5479.64–5745 1.04 1.42 0.75 1.23 4.63 1.49 1.26 4.83 1.32 0.63 0.65 0.78
ZG461 5479.64–5740 1.07 1.71 0.67 1.41 4.94 1.58 1.24 5.77 1.37 0.60 0.71 0.76

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ZG462 5431–5981 1.16 1.63 0.49 0.85 2.48 3.25 1.08 2.86 1.18 0.82 0.86 0.89
ZG47 5811–6095 0.79 1.51 0.66 0.83 8.13 0.86 2.14 6.20 1.39 0.65 0.74 0.79

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ZG47CH 6489–6606 0.80 1.92 0.59 1.19 4.71 0.87 2.03 6.22 1.39 0.74 0.81 0.84
ZG48 5498.1–5531.54 0.86 1.26 1.15 2.18 3.51 0.80 0.80 3.65 1.25 0.54 0.62 0.73

Tazhong No.10 structural zone

ZS1 6426–6497 2 1.10 2.18 1.30 2.35 2.89 0.24 2.26 5.67 1.37 1.18 1.35 1.11

Abbreviations (in addition to those already listed in the text and below Table 1): Tol: toluene; MCH: methyl cyclohexane; MN: methylnaphthalene; DMN: dimethylnaphthalene;
TMN: trimethylnaphthalene; N: naphthalene; P: phenanthrene.
771
772 Energy Exploration & Exploitation 36(4)

Figure 2. Selected TICs of some Tazhong black oil samples. Wells TZ26, TZ44 and TZ241 are located
within the Tazhong Number I fault zone, while TZ4, TZ104 and TZ404 are located within the Tazhong
Number 10 structural zone, and TZ12, TZ35 and TZ162 are located within the central uplift zone. The
numbers above peaks denote n-alkane carbon numbers.
TIC: total ion chromatogram.

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Liang et al. 773

and seaweed, while differences in sterane distribution might be the result of several
charging phases.
Results (Table 1) show little difference between the oil samples from different structural
zones concerning the distribution of regular biomarker parameters because these parameters
have been homogenized by the facts that the oil generating rocks within the Tarim Basin
comprise several sources (Jin, 2005; Yun et al., 2014), which have experienced several char-
ging phases (Chang et al., 2013; Zhao et al., 2012) and characterized by the adjustment and
destruction of generated hydrocarbons (Zhuo and Wang, 1999). Thus, three tectonic
phases can be identified corresponding with the end of the Early Paleozoic, the Late
Paleozoic-to-Early Mesozoic, and the Late Cenozoic; these match with the oil charging
phases of the Tarim Basin, specifically named as the late Caledonian-to-Hercynian, the
late Hercynian and Himalayan periods (Zhang et al., 2011). Oils from the Cambrian
source rocks (late Caledonian-to-Hercynian) have generally been destroyed, which is accord-
ant to that the Late Hercynian is the main oil reserved period of the two source rocks. The
Himalayan period was the main time for gas generation, as gas invading condensate gas
reservoirs formed during this period (Zhang et al., 2012). In contrast, samples containing
crude oils from these three generating phases also have particular characteristics as they
formed in distinct structural zones, all of which were highly saline marine facies derived from
bacterial and seaweed precursors.
The aromatic hydrocarbon components of samples mainly comprise naphthalene and
alkylnaphthalene, as well as phenanthrene and alkylphenanthrene, fluorene and alkylfluor-
ene, and dibenzothiophenes, particularly among which the naphthalene and phenanthrene
homologues occur at higher abundances. Earlier work concerning methylphenanthrene par-
ameters have been related to maturity (Radke et al., 1982). Indeed, both the methylphenan-
threne indicator 1 (MPI1) and methylphenanthrene indicator 2 (MPI2) values of source
rocks initially increase and then decrease as depth increases; calculated MPI1 values [MPI ¼
1.5  (2-methylphenanthrene + 3-methylphenanthrene)/(phenanthrene + 1-methylphenanthrene +
9-methylphenanthrene)] for TZ black oils range between 0.42 (TZ452) and 1.22 (TZ35)
(although mainly concentrated between 0.55 and 0.85), while MPI2 values [MPI2 ¼ 3  (2-
methylphenanthrene)/(phenanthrene + 1-methylphenanthrene + 9-methylphenanthrene)] of
these samples range between 0.47 (TZ452) and 1.36 (TZ35) (mainly between 0.69 and 0.91).
Equivalent vitrinite reflectances (Ro%) calculated based on MPI (Ro% ¼ 0.60 
MPI1 + 0.40) (i.e. 0.65  Ro% < 1.35) range between 0.73 and 1.13.TZ oils derived from
marine source rock while MPI mainly works for type III kerogen, thus calculated Ro cannot
well correlate to source rock and then less reliable.
In terms of sulfur-containing aromatic compounds, it is informative of different loca-
tions of methyl groups within methyldibenzothiophenes as they are indicative of thermal
stability (4-MDBT > 1-MDBT). Research in this area was performed by Dzou et al. (1995)
who reported that the relationship between MDR (4-MDBT/1-MDBT) and equivalent
vitrinite reflectance is Ro% ¼ 0.2663  Ln (MDR) + 0.9034. Compounds of this type
have been studied in details (Chakhmakhchev et al., 1997; Luo et al., 2001; Santamarı́a-
Orozco et al., 1998). Zhou et al. (2008), for example, calculated the maturity of source
rocks at different depths within the TC1 well using this formula. The MDR of oil samples
ranged between 1.93 and 24.66, while MDR4 (4-MDBT/DBT) ranged between 0.62 and
3.66, and Ro% ranged between 1.08 and 1.76, which is more reliable than the Ro calcu-
lated by MPI. At the same time, it is also noteworthy that, in addition to maturity,

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774 Energy Exploration & Exploitation 36(4)

aromatic sulfur-containing compound parameters may also be influenced by other factors

including biodegradation.

Geochemical characterization of Tazhong light crude oils

Overall geochemical properties of the light crude oils. Some TIC results of TZ light crude oils are
illustrated in Figure 3, among which ZG10, ZG70 and ZG12 are located within the TZ

Figure 3. Partial TICs of selected light crude oil samples. Numbers above peaks represent n-alkane
carbon numbers.
TIC: total ion chromatogram; C2B: C2 substituted benzene; C3B: C3 substituted benzene; C4B: C4 substi-
tuted benzene.

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Liang et al. 775

Number I fault zone, while ZG46, ZG47 and ZG48 are located within the TZ Number 10
structural zone, and the ZS1 reservoir is located in the central uplift zone deposited in
Cambrian strata. As these samples mainly belong to light crude oils, the n-alkanes in samples
are light hydrocarbons with low carbon number. As an example, the sample from well ZG12
has a peak n-alkane at C8 which demonstrates high maturity; this also means that most
normally detected biomarkers are not present and so the regular geochemical parameters
usually applied to sample characterization are also invalid. Rich aromatic hydrocarbons are
detectable in all these samples including alkylbenzene, alkylnaphthalene and alkylphenan-
threne as well as biphenyl, alkyldibenzothiophene.

Figure 4. Partial mass chromatograms of light crude oils from ZG17.

MCH: methylcyclohexane; N: naphthalene; MN: methylnaphthalene; DMN: C2 substituted naphthalene;
TMN: C3 substituted naphthalene; Phen: phenanthrene; MP: methylphenanthrene; DBT: dibenzothiophene;
MDBT: methyldibenzothiophene.

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776 Energy Exploration & Exploitation 36(4)

For ZG17 light crude oil, the mass chromatograms exemplified by ions of m/z 91, 98, 128,
142, 156, 170, 178, 184, 192 and 198 are presented in Figure 4. Toluene and methylcyclohex-
ane in the samples may share some common geochemical origin as they may have been
derived from the same precursor molecules and even the toluene may be derived from
methylcyclohexane in the oil reservoirs, and then the ratio of toluene to methyl cyclohexane
will be further discussed concerning their geochemical characteristics including maturity.

Geochemical characteristics of the aromatics of the light crude oils. Some geochemical parameters of
aromatic compounds in TZ light crude oils are shown in Figure 5. In terms of the first group,
the ratio between toluene and methyl cyclohexane ranges between 0.63 and 3.03 (mainly
between 0.98 and 2.01). The ratio between these compounds in samples from the TZ Number
I fault zone ranges more widely than those for the TZ Number 10 structural zone, with ratios
for the latter concentrated between 0.79 and 1.30, however with the exception for ZG46
sample (also see the following discussion).
Some previous research has suggested that a high abundance of naphthalene series com-
pounds is indicative of highly mature source rocks (Price, 1993). In TZ45 condensate oils and
light crude oils, the abundance of naphthalene series is relatively high (Zhou et al., 2008).
Similarly, in terms of methylnaphthalene (MN) molecular characteristics, methyl in location
b tend to be more stable than those in location a, which means that 2-MN tend to exhibit
higher thermal stability than their 1-MN counterparts. Thus, the ratio between 2-MN and 1-
MN compounds can be applied for maturity comparisons of light crude oils.

Figure 5. Cross-plots for Tazhong light crude oils: (A) 4-MDBT/1-MDBT ratios versus 4-MDBT/DBT
ratios; (B) toluene/MCH ratios versus DBT/phenanthrene ratios; (C) naphthalene/phenanthrene ratios
versus toluene/MCH ratios; and (D) DMN/TMN ratios versus MN/DMN ratios.
MDBT: methyldibenzothiophene; DBT: dibenzothiophene; MCH: methylcyclohexane; DMN: C2 substi-
tuted naphthalene; TMN: C3 substituted naphthalene; MN: methylnaphthalene.

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Liang et al. 777

Our results show that the MN indicators (2-MN/1-MN) in TZ light crude oils range
between 1.21 and 2.81. Comparing these results with research on MN compounds from
Li and Wang (2005) suggests that the Ro% of samples should be more than 1.0%; however,
this previous result was based on low maturity samples and so a difference should be
expected when compared to the high maturity oils discussed in this work. Indeed, in the
case of multiple-substituted naphthalene parameters, MN/C2 substituted naphthalenes
(DMN) ratios of our samples range between 0.49 and 1.30; specifically, this ratio for samples
from the TZ Number I fault mainly between 0.51 and 0.88 while those from the TZ Number
10 structural zone between 0.59 and 0.75. At the same time, DMN/C3 substituted naphtha-
lenes (TMN) ratios range between 0.83 and 3.25; this ratio in samples from the TZ Number I
fault zone mainly between 0.90 and 1.78, while for samples from the TZ Number 10 struc-
tural zone range between 0.83 and 1.44.
Values of MPI were chosen to illustrate the parameters of phenanthrene series com-
pounds. Results show that MPI1 values for light crude oils range between 0.61 and 1.18
while MPI2 values range between 0.56 and 1.35. Thus, equivalent Ro% values calculated
using MPI (i.e. Ro%a ¼ 0.60  MPI1 + 0.40; 0.65  Ro% < 1.35; Ro%b ¼ 0.60  MPI1 +
2.30; 1.35  Ro% < 2.00) range between 0.72% and 1.11% and between 1.59% and 2.00%,
respectively. At the same time, the ratios between naphthalene and phenanthrene range
between 2.48 and 30.25; results show that N/phenanthrene ratios for samples from the TZ
Number I fault zone range between 3.18 and 30.25, a much wider variation than those from
the TZ Number 10 structural zone between 2.48 and 8.13 (with the exception for ZG46).
The MDR of oil samples ranged between 2.06 and 10.84, while MDR4 (4-MDBT/DBT)
ranged between 0.60 and 4.20, and Ro% ranged between 1.10 and 1.51.
Our results show that the DBT/phenanthrene ratios of TZ oil samples range between 0.24
and 9.6; these ratios in samples from the TZ Number I fault zone are between 0.64 and 9.64,
a wider range than samples from the TZ Number 10 structural zone of 0.80 and 3.91 (with
the exception for ZG46). Reported by Zhang et al. (2015b), the extremely high DBT/phen-
anthrene ratios may be influenced by TSR (Thermal Sulfate Reduction). The results of MN/
DMN, DMN/TMN, toluene/MCH, DBT/phenanthrene, and naphthalene/phenanthrene
ratios of light crude oils from the TZ Number I fault zone range widely, while those from
the TZ Number 10 fault zone encompass a relatively narrow range (Figure 5). This result
indicates that oil samples from the TZ Number I fault zone have undergone more oil
charging than their counterparts; indeed, even oils generated from the same hydrocarbon
source rock with the same original material exhibit differences in maturity because they were
generated in different hydrocarbon expulsion phases. In other words, the oil samples from
the TZ Number I fault zone are more complicated in composition than their counterparts
from the TZ Number 10 structural zone, as illustrated by the geochemical parameters dis-
cussed in this study.
Qiu et al. (1997, 2010, 2012) and Liu et al. (2017) performed a lot of work in investigating
hydrocarbon charge. In earlier work, Qiu et al. (1997, 2010, 2012) analyzed a series of
integrated thermal indicators of apatite and zircon (U–Th)/He ages, as well as apatite fission
tracks, and equivalent vitrinite reflectance data from TZ source rocks. Their results were
used to hypothesize that Indosinian and Yanshan movements lifted strata in this region and
made multistage accumulation possible as source beds moved into a detained stage and
stopped generating oil and gas following rapid source rock maturation. In a similar study,
Yang et al. (2011) performed research on fluid inclusions within a TZ Ordovician carbonate
reservoir and suggested three distinct phases of oil charging, namely Caledonian-to-early

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778 Energy Exploration & Exploitation 36(4)

Hercynian, late Hercynian, and Himalayan stages. The last phase of the Himalayan, was
mainly charged with gas. Thus, as the characteristics of TZ light crude oils were influenced
by oil charging during Himalayan gas invading stage, they share similar features with con-
dense oils as the late Hercynian. In contrast, as oil charging during the Caledonian was
destroyed this leads to degradation characteristics if original crude oils are considered. In
earlier work, Zhang et al. (2009) also considered different structural zones during a variety of
evolutionary phases can influence oil accumulation. These researchers showed that the TZ
Number 10 structural zone shared the same accumulation phase as the TZ Number I fault
zone, but that the tectonic activity within the structural zone was less than that within the
fault zone. This resulted in an intact clastic rock layer which hindered oil migration above
the limestone. The advantage of this migration within the TZ Number I fault zone is that oils
generated there tend to be more complex in their composition than their counterparts
formed within the TZ Number 10 structural zone. These differences also mean that the
geochemical characteristics of oils formed within the TZ Number I fault zone tend to
vary more widely.
A large number of strike slip faults formed within the TZ area caused marked improve-
ments in the growth of reservoir carbonate voids and stems linking different reservoirs (Wu
et al., 2012; Yang et al., 2007; Zhou et al., 2013). At the same time, these strike slip faults
controlled the migration and accumulation of oil into reservoirs. Most notably, the end of
Silurian-to-early Devonian and late Permian periods were two most active phases of strike
slip faults within the Tarim Basin (Jia, 2004). Zhang et al. (2008) reported that middle-to-
upper Ordovician gas reservoirs formed by the pyrolysis of paleo-oil accumulations under-
neath Cambrian salt deposits as the growth of main and strike slip faults provided a number
of possibilities for hydrocarbons to migrate upwards. As shown on a geological map of this
area (Figure 1), light crude oils within the TZ Number 10 structural zone are mostly located
within the boundaries of the main fault while there are more strike slip faults within the TZ
Number I fault zone. These smaller faults provided a large number of effective channels
connecting different reservoirs and resulted in several phases of oil charging (Li et al., 2006);
this range of crude oils with markedly different geochemical characteristics is the cause of the
parameter variation seen within this region. Notably, although well ZG46 is located within
the TZ Number 10 structural zone, a number of strike slip faults connect it to the TZ
Number I fault zone nearby; this might be the cause of several distinct episodes of oil
charging. In addition, structures within the Tarim Basin tend to become less active from
east-to-west and the ZG46 well is located within the western TZ Number 10 fault, a possible
advantage that prevented the degradation of high maturity oils. Indeed, a highly mature oil
reservoir in the eastern TZ Number 10 structural zone was destroyed as it lacked good cover
even though strike slip faults were present in the vicinity. These structural observations
explain why the toluene/MCH ratio of ZG46 oils sample is 3.03, the naphthalene/phenan-
threne ratio is 14.71, and the DBT/phenanthrene ratio is 3.91, markedly higher than the
values recorded for other oil samples within the TZ Number 10 structural zone.

Geochemical features of toluene and methylcyclohexane in the light crude oils. Regarding the geo-
chemical characterization of toluene and methyl cyclohexane in TZ light crude oils, data
demonstrate that saturated ring hydrocarbons can transform into aromatic hydrocarbons by
dehydrogenating as maturity gets higher. This is at least one important way in which aro-
matic hydrocarbons are generated. Several recent studies have shown that alkyl cyclohexane
can transform into alkyl benzene series compounds by dehydrogenating (Darwin et al.,

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Liang et al. 779

2016a, 2016b). Based on these results, it is supposed that a close evolutionary origin may
exist between toluene and methyl cyclohexane in light crude oils, maybe some toluene can be
directly derived from methylcyclohexane, and basically in crude oils toluene and methylcy-
clohexane should have been derived from the same or some likewise structural units of
precursor molecules. Thus, during geological evolution process, changes in relative concen-
tration and stable isotope values of toluene and methylcyclohexane can be used to reveal the
geochemical characteristics of high mature oils. Therefore, some more discussion has been
made to the TZ light crude oils concerning their toluene and methylcyclohexane.
There are more methylcyclohexane than n-heptanes in samples from the TZ Number 10
fault zone (Figure 6), which is accordant to the characterization of marine crude oil. But this
relationship is different in samples from the TZ Number I fault zone, among which some
samples have more methylcyclohexanes while others have more n-heptane (Figure 6). These
results are accordant to the fact that some light crude oils from the TZ Number I fault zone
had contributed to some oil-cracking gas, and then depleted in methylcyclohexane (Hu et al.,
2005; Yu et al., 2013), and therefore enriched in toluene showing a higher maturity as shown
in Figure 6. Thus, these results reveal that the TZ Number I fault zone had undergone more
complicated geological evolution. As discussed above, ZG46 was obviously enriched in
toluene because it is at a very special tectonic location, so the ratio between toluene and
methylcyclohexane can be used to distinguish depositional environments and differentiate
the maturity of light crude oils.
Stable carbon and hydrogen isotope values for toluene and methylcyclohexane in TZ light
crude oils are listed in Table 3. Results show that toluene C isotope values in TZ light crude
oils range between 32.69% and 22.88%, while H isotope values range between

Figure 6. Plot of concentration relationship between n-heptane, methylcyclohexane and toluene in

Tazhong light crude oil.

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 780

Table 3. Stable carbon/hydrogen isotope values of toluene and methylcyclohexane of the light crude oils.

Toluene Methyl cyclohexane Toluene Methyl cyclohexane

13 13 13
Well Depth (m) Strata  C D  C D Well Depth (m) Strata  C D 13C D

ZG10 6198–6309 O 29.08 98.72 29.50 91.35 ZG432 5131–5520 O 27.21 147.10 26.27 157.53
ZG101 6998–6309 29.57 91.90 30.12 84.17 ZG441 5414.38–5522 29.03 109.98 29.94 124.49
ZG103 6105–6223 28.33 96.20 29.14 96.29 ZG441-2H 5259.81–5485 O 28.80 109.36 28.98 108.32
ZG103 6148.44–6233.46 O3 27.77 101.54 29.62 96.90 ZG44C 5432–5861.50 29.34 104.70 29.00 109.47
ZG105 5936–6829.28 O1y 29.87 94.70 29.51 92.92 ZG45 5637.2–5650.17 O3 29.06 113.57 29.96 120.86
ZG106 6110–6130 O1 28.86 101.94 29.87 96.75 ZG46 5039.40–5367.34 O3 32.69 115.24 31.31 125.28
ZG111 6008–6250 O 28.76 75.30 27.50 74.00 ZG461 5479.64–5745 28.37 101.30 29.05 114.29
ZG12 6059.58–6279 O 28.23 95.95 28.03 112.21 ZG461 5475–5745 28.25 111.60 28.06 119.50
ZG13-1H 5886–7135 29.44 70.42 30.59 83.49 ZG461 5479.64–5740 27.39 110.39 28.14 117.46
ZG14-1 6133–6298 O 29.95 102.66 30.12 111.59 ZG462 5431–5981 30.04 114.83 29.73 119.57
ZG15 6125–6138 O 30.22 78.92 30.88 81.36 ZG47 5811–6185 29.06 93.69 29.11 94.52
ZG151 6083.75–6223.81 O2 29.68 110.30 30.70 124.80 ZG47CH 6489–6606 28.91 102.51 29.16 110.56
30.59 77.50 29.46 86.38 29.33 104.92 29.76 98.80

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ZG162 6123–6198 O 29.90 114.92 30.41 120.19 ZG5 6351.64–6460 29.38 98.67 30.00 93.28
ZG17 6206–6446 O1y 29.14 102.39 30.00 88.27 ZG501 6515.5–6790.4 30.90 109.41 30.14 115.70

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ZG17 6438–6448 27.66 101.73 27.28 96.14 ZG503 5949–6100 O1y 30.67 75.08 31.04 77.87
ZG17-H1 6088–6887 29.94 117.26 29.66 120.76 ZG6-2 5937.81–6118 O1y 28.61 110.28 29.13 127.37
ZG19 6381–6438.5 O 28.76 73.08 30.06 89.72 ZG6-2 5898.25–6143.17 O1y 28.52 116.00 29.20 92.18
ZG2 5866–5893 O 28.44 72.88 28.81 84.77 ZG70 5714–5728 27.86 97.48 29.78 117.17
ZG22 5605–5736.66 O 29.87 111.87 29.56 112.68 ZG702 5628–5890 O 29.52 101.46 28.27 118.80
ZG42 4980.08–5334.09 O1y 28.72 106.17 30.28 105.20 ZS1 6426–6497 2 32.10 121.49 32.54 114.17
ZG43-1 5200–5798 O1y 29.62 121.34 29.84 124.41
Energy Exploration & Exploitation 36(4)
Liang et al. 781

Figure 7. Graphs to show: (A) d13C of toluene versus methylcyclohexane; (B) dD of toluene versus
methylcyclohexane; (C) d13C versus dD of toluene; and (D) d13C versus dD of methylcyclohexane in
Tazhong light crude oils.

147.10% and 70.42%. At the same time, methylcyclohexane C isotope values in TZ light
crude oils range between 32.54% and 26.27%, while H isotope values range between
157.53% and 74.00%. A positive correlation is also seen between toluene and methyl
cyclohexane d13C values (Figure 7A). Measured differences in d13C between toluene and
methyl cyclohexane are mostly within 1% of one another, while differences in dD between
toluene and methyl cyclohexane are mostly within 10%. This result, that the isotope values
of toluene and methylcyclohexane are close, indicates that these two molecules might share
the same precursors or the presence of an inheritance relationship from methylcyclohexane
to toluene as discussed above.
The data distribution of d13C and dD in toluene and methyl cyclohexane (Figure 7A,B)
fall around a line with a slope of 1, while the dD of toluene and methyl cyclohexane in
Figure 7(B) fall below this line, especially the samples from TZ Number 10 structural zone.
This result suggested that the dD of toluene is generally heavier than those of methyl

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782 Energy Exploration & Exploitation 36(4)

Figure 8. Plots of toluene/methylcyclohexane ratios versus: (A) d13C values of toluene; (B) dD values of
toluene; (C) d13C values of methylcyclohexane; and (D) dD values of methyl cyclohexane in Tazhong light
crude oils.

cyclohexane. As discussed above, one important way that aromatic hydrocarbons are gen-
erated via the transmutation of saturated ring hydrocarbons in crude oils via dehydrogen-
ation as maturity increases. This will cause the breakage of C–H bonds in the molecule and
then enriched in deuterium for toluene.
No distinct correlation between d13C and dD in either toluene or methylcyclohexane is
evident from the TZ light crude oils, as the former is sensitive to both precursors and
depositional environments but less so to thermal evolution, whereas the latter is more sen-
sitive to thermal stress. After oil charging, crude oils containing different kinds of com-
pounds from different charging phases will exhibit different stable isotope features, which
will be commingled into the geochemical outcomes of the light crude oils. So in Figure 8
these characteristics are reflected on plots of toluene and methylcyclohexane ratios versus
d13C and dD in TZ light crude oils. No matter how these ratios vary, no obvious regular
pattern is found in our data between toluene and methylcyclohexane and their d13C or dD,
so long as crude oils contain compounds charged during different geological phases when
they were derived from different precursors and depositional environments. However, in the
geochemical study on light crude oils, toluene and methylcyclohexane should be investigated
in details as they are abundant in the light crude oils and may be with genetic relationships,
so further work will be helpful to the study on light crude oils from the composition, stable
carbon/hydrogen isotope analyses of toluene and methylcyclohexane.

Conclusions
A total of 89 crude oils were analyzed in this study with emphasis on TZ light crude oil
aromatic hydrocarbons from different structural zones. The aim of this study was to evaluate

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Liang et al. 783

the geochemical parameters of these crude oils and to investigate their stable carbon/hydro-
gen isotope ratios.
Results reveal that the crude oils from TZ area are highly mature, especially true for the
light crude oils. At high mature stage the normal biomarker parameters are invalid and then
the aromatic hydrocarbon compounds are the main study targets in this work.
The distribution of aromatic hydrocarbons is different between crude oils from different
structural zone. Thus, the MN/DMN, DMN/TMN, MCH/Tol, DBT/phenanthrene, and
naphthalene/phenanthrene ratios of crude oils from the TZ Number I fault zone range
widely while those from the TZ Number 10 structural zone encompass a relatively narrow
range of variation. This difference highlights the fact that the TZ Number I fault zone
experienced more intense structural movements than the TZ Number 10 structural zone.
The former also formed a more effective migration pathway as a result; thus, the crude oils
that formed within the TZ Number I fault zone have undergone several charging phases and
are more complicated in composition.
The distribution of stable carbon/hydrogen isotope values revealed by this study indicates
a relationship between the origin of toluene and methylcyclohexane. Toluene can be derived
from the dehydrogenation of methylcyclohexane in crude oils. Nevertheless, the ratios of
toluene and methylcyclohexane are complicated within the TZ area and no regular pattern is
evident due to multiple charging events and the complex geological evolution of the TZ area.
The results of this study nevertheless reveal that the geochemical characteristics and signifi-
cance of toluene and methylcyclohexane in light crude oils are worthy of further study.

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or
publication of this article.

Funding
The author(s) disclosed receipt of the following financial support for the research, authorship and/or
publication of this article: This work was financially supported by the National Natural Science
Foundation of China (Grant No. 41472109), the Strategic Priority Research Program of the
Chinese Academy of Sciences (XDA14010103) and the National Oil and Gas Project of China
(2017ZX05008002).

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