Journal of Petroleum Science and Engineering 191 (2020) 107308

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Journal of Petroleum Science and Engineering

journal homepage: http://www.elsevier.com/locate/petrol

Fractionation of alkylated carbazoles in petroleum during subsurface

migration: Evidence from molecular simulation and application in
sandstone reservoirs☆
Qiuya Han a, Meijun Li a, b, *, Xiaoqiang Liu a, c, Weidong Jiang c, **, Shengbao Shi a, Youjun Tang b,
Daxiang He b
a
State Key Laboratory of Petroleum Resources and Prospecting, College of Geosciences, China University of Petroleum, Beijing, 102249, China
b
Key Laboratory of Exploration Technologies for Oil and Gas Resources, Ministry of Education, College of Resources and Environment, Yangtze University, Wuhan,
430100, China
c
College of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, Zigong, 643000, China

A R T I C L E I N F O A B S T R A C T

Keywords: Carbazole (CA) and alkylated carbazoles are common nitrogen-containing heterocyclic aromatic compounds
Geo-chromatographic fractionation widely found in crude oils and sedimentary rocks extracts. Their geochemical significances in petroleum
Alkylcarbazole exploration have been widely investigated in previous studies. Using density functional theory (DFT) and mo­
Petroleum migration orientation
lecular dynamics (MD) simulation, we calculated the polarity of alkylated carbazole isomers/homologues and
Molecular dynamics simulation
Sandstone reservoir
their adsorption energy with water and α-quartz, respectively. The calculated results show that there are sig­
nificant differences in migration fractionation effects for alkylated carbazole isomers/homologues. This study
confirmed the validity of previously proposed carbazole migration indicators, i.e. 4-/1-MCA (the relative
abundance of 4-methylcarbazole to 1-methylcarbazole), 2,5-/1,8-DMCA (2,5-dimethylcarbazole to 1,8-dimethyl­
carbazole) and 2,4-/1,8-DMCA (2,4-dimethylcarbazole to 1,8-dimethylcarbazole) on the basis of quantum
chemistry and molecular simulation. All these three parameters have been successfully applied in a lacustrine
sandstone reservoir in the Fushan Depression, Beibuwan Basin (South China Sea). The calculations of Gibbs free
energy show that the differences in thermal stability between the isomers of alkylcarbazoles can be negligible.
The source input and depositional environment have no significant effect on these indicators for oils from a same
oil family. Hence, the values of these parameters are mainly controlled by subsurface petroleum migration
processes. Therefore, the molecular parameters relative to alkylated carbazoles can be used as practically
effective geochemical markers to trace the oil filling orientation and pathways for subsurface oil migration.

1. Introduction
Organic nitrogen compounds with heterocyclic aromatic structures
are representative nonhydrocarbon constituents of crude oils. (Tissot
and Welte, 1980). Heterocyclic aromatic nitrogen compounds in pe­
troleum can be classified into two main categories: neutral pyrrolic and
basic pyridinic compounds. As important neutral pyrrolic compounds,
carbazole (CA) and its derivatives have been widely applied in petro­
leum geochemistry during past two decades because they are effective
molecular markers tracing oil migration distances and filling pathways.
(Li et al., 1995, 1998b; Larter et al., 1996; Silliman et al., 2002; Wang
et al., 2004).
The biological origin of carbazole and its homologues/isomers in
crude oils still remains controversial. According to the compositions of
nitrogen compounds in Californian oils, Snyder (1965) proposed that
most alkylcarbazoles and alkylbenzocarbazoles in crude oils may be
derived from alkaloids with an indole nucleus in higher plants and
blue-green algae (cyanobacteria). However, Li et al. (1995) found that

The abstract was originally presented at the 35th Annual Meeting of The Society for Organic Petrology (TSOP) in Beijing, China.
☆

* Corresponding author. State Key Laboratory of Petroleum Resources and Prospecting, College of Geosciences, China University of Petroleum, Beijing, 102249,
China.
** Corresponding author.
E-mail address: meijunli@cup.edu.cn (M. Li).

https://doi.org/10.1016/j.petrol.2020.107308
Received 26 December 2019; Received in revised form 12 February 2020; Accepted 14 April 2020
Available online 18 April 2020
0920-4105/© 2020 Elsevier B.V. All rights reserved.
Q. Han et al. Journal of Petroleum Science and Engineering 191 (2020) 107308

the distribution and compositions of nitrogen compounds in crude oils
from marine and lacustrine sources are significantly different from those
of higher wax oils derived from higher plants. It believes that alkaloids
are not the main source of carbazoles in crude oils (Li et al., 1995).
Besides, a contribution from proteins and plant pigments within sedi­
mentary organic matter during diagenesis cannot be ruled out.
Carbazole and its C1 and C2 alkylated homologues are usually
detected and identified from crude oils and rock extracts by gas chro­
matography–mass spectrometry (GC–MS). In addition, gas chromatog­
raphy (GC)–nitrogen specific detection and direct insertion probe mass
spectrometry (PMS) are also common techniques (Li et al., 1992; Bowler
et al., 1997). Isolation of the nitrogen fraction was mainly performed
using two-step liquid column (LC) chromatographic separation method
reported by Later et al. (1981) and with slight modifications of adding a
deasphalting step prior to the LC steps (Li et al., 1995).
CAs, important molecular markers in reservoir geochemistry, are
ubiquitous in petroleum and sedimentary organic matter although pre­
sent in such low abundance (Li et al., 1995). Previous studies indicated
that the occurrence and distributions of CAs are predominantly influ­
enced by migration fractionation effect (Yamamoto, 1992; Li et al.,
1995, 1998a; Larter et al., 1996; Wilhelms et al., 1997). In addition, the
effect of depositional facies and environment (Clegg et al., 1997; Bakr
and Wilkes, 2002; Zhang et al., 2008), thermal maturity (Harrison et al.,
1997; Li et al., 1997; Clegg et al., 1998a, 1998b; Horsfield et al., 1998;
Zhang et al., 2011), and biodegradation (Zhang et al., 1999; Huang
et al., 2003) cannot be neglected. Therefore, these factors should be
indicators for the secondary petroleum migration.
Here we demonstrated some oil migration tracers relative to CAs
proposed in previous studies on the basis of dipole moment (μ) and
interaction energy (EIn) of alkylcarbazoles with α-quartz by MD simu­
lation and practical application in a typical sandstone reservoir.
2. Experiments and methods
2.1. The identification and quantitation of alkylated carbazoles
The nitrogen fractions were isolated from crude oils samples using
the method reported by Li et al. (1995). First, add 40 ml n-hexane to oil
samples and filter for deasphalting. Then, the n-hexane solutions were
further separated into saturated hydrocarbons, aromatic hydrocarbons
and nonhydrocarbons using neutral alumina chromatography columns
eluting with 50 ml n-hexane, 50 ml methylbenzene and 70 ml chlor­
oform/methanol (98:2, v:v), respectively. Finally, the pyrrolic nitrogen
fraction were eluted with 50 ml n-hexane/toluene (1:1, v:v) from non­
hydrocarbons using silicic acid chromatography columns.
GC–MS (gas chromatography–mass spectrometry) analysis of the
nitrogen fractions of oil samples was performed on an Agilent 5975i
mass spectrometer coupled with an HP 6890 GC with 60 � 0.32 mm HP-
5MS fused silica capillary column (0.25μ film thickness coating). Helium
was used as a carrier gas at a constant flow of 1.0 ml/min. The GC oven
temperature was initially set to 80 � C for 1 min and then ramped to 150
C at 15 C/min, then rose to 290 � C at 5 C/min. The injection tem­
� �
�

taken into account when utilizing CAs as migration markers. perature was set at 300 C. The MS was running in full-scan mode with a
�

CAs react with formation water and mineral surfaces via forming scanning range of 50–600 Da and electron ionization (EI) mode at 70 eV.
hydrogen bond between an H atom of its N–H functional group on the CA, MCA (methylcarbazole) and C2-CA (dimethylcarbazole and
pyrrolic ring and high electronegative atoms (like oxygen atom) in ethylcarbazole) can be identified in oils (Fig. 1) by comparison of rela­
carrier beds (Dorbon et al., 1984; Krooss et al., 1991). Thus, the absolute tive retention time and retention indices on m/z 167, 181, 195 mass
concentrations of CAs and the relative abundance for some alkylcarba­ chromatograms with those in published work (Li et al., 1992; Bowler
zole isomers will change during secondary migration processes. And a et al., 1997). The carbazoles were quantified using known amount of
series of geochemical parameters relative to carbazoles have been pro­ 9-phenylcarbazole as an internal standard which was added prior to
posed to trace the oil migration orientation. Previous studies indicated GC–MS analysis of the pyrrolic nitrogen fraction. The concentration of
that the formation of hydrogen bond could be influenced by alkylation individual carbazole compounds were obtained on basis of integrated
positions in terms of steric hindrance which leads to differences in peak areas compared with that of the internal standard.
fractionation effect during oil migration for alkylcarbazoles. The relative
enrichments of N–H-shielded to N–H-exposed isomers and the higher
homologues to the lower homologous species with increasing migration
distances have been observed in the laboratory experiments (Li and
Larter, 1993; Li et al., 1994; Larter et al., 2000) and successively applied
in case studies of a variety of fields (Li et al., 1995, 1998b).
In recent years, molecular simulations have been preliminarily
applied in petroleum geochemistry (Liu et al., 2016; Yan and Yuan,
2016; Li et al., 2018) based on quantum chemistry and statistical me­
chanics via computers. Duin and Larter (1998) used this technique to
simulate the affinity of benzacarbazole isomers for oil and water phases.
The simulation results indicate that benzo[a]carbazole is more easily
removed from the oil phase due to its higher affinity for the water phase
than benzo[c]carbazole, which explain partly why benzo[a]carbazo­
le/benzo[c]carbazole decreases with increasing migration distances.
However, less such MD simulations have been performed on alkylcar­
bazoles to reveal their microscopic mechanism of migration fraction­
ation during subsurface oil migration.
To a large extent, the interaction energy (EIn) of CAs adsorption on
silica can indirectly determinate the oil migration orientation in carrier
beds through molecular modeling. Li et al. (2018) have been proved
experimentally and theoretically that the relative abundances of 1-meth­
yldibenzofuran (1-MDBF) to 4-methyldibenzofuran (4-MDBF) could
serve as potential molecular indicators to trace oil filling pathways and
migration orientation. Ideally, as increasing migration distances, the
alkylcarbazole of a small interaction energy with silica is relatively
enriched comparing with their counterparts of a large interaction energy
with silica. Therefore, we may choose the alkylcarbazole isomer­
s/homologues with significant differences of interaction energy as Fig. 1. Identification of CA, C1-CA and C2-CA isomers in oils.

2
Q. Han et al.
2.2. Density functional theory calculations
Geometry optimizations were carried out at the B3LYP/6–311þþG
(d,p) level of theory by using the Gaussian 09 program (Fig. 2). Fre­
quency outcomes were examined at the same level of theory to confirm
stationary points as zero imaginary frequencies. The thermodynamic
properties of CA isomers were obtained including entropy, enthalpy,
electron energy, internal energy and Gibbs free energy.
2.3. MD simulations
All MD calculations were carried out with the consistent-valence
force fields (cvff) (Dauber-Osguthorpe et al., 1988) by using Forcite
code. Temperature was kept at 298 K for all simulations. The model of
H2O cell adopts the previous work by our research group (Li et al.,
2018). In addition, α-quartz-(001) surface is investigated to probe the
effect of small molecule adsorption. To achieve stable structures of
adsorption systems were performed with a geometry optimization, fol­
lowed by MD simulations including (1) the simulation was run in an
NVT ensemble to ensure that the systems are at the correct temperature;
(2) after equilibration, the systems were run in the NVE ensemble. In all
MD simulations, 2 ns simulations were conducted to relax the systems
fully with 1 fs stepsize. In order to avoid interactions between adjacent
structures for both H2O cell and α-quartz-(001) surface, vacuum thick­
ness set as 80 Å. The interaction energies between H2O/α-quartz-(001)
surface and CA homologues (CAH) were calculated by using the
following equation,
EIn ¼ (ETotal – ESurface – ECAH) (1)
Where ETotal is the energy of H2O/α-quartz-(001) surface and the CAH,
ESurface is the energy of H2O/α-quartz-(001) surface without the CAH,
and ECAH is the energy of the CAH without the H2O/α-quartz-(001)
surface.
3. Geological background
The Fushan Depression, located in the northern of the Hainan Island
and southern of the Qiongzhou Strait, is a typical Mesozoic-Cenozoic
“half-graben” rift in the southeastern of the Beibuwan Basin (Li et al.,
2008). The Fushan Depression was developed on the basement of the
Paleozoic strata and the Mesozoic intermediate acidic igneous rocks
(Chen et al., 1991). It is a NE-E trending depression bounded by the
Changliu Fault to the east, the Anding Fault to the south and the Lingao
Fault to the northwest, respectively, which is filled with over 9000 m of
Cenozoic sediments with an area of 2920 km2 (Fig. 3) (Luo and Pang,
Fig. 2. The optimized geometries of (a) 1-MCA, (b) 2-MCA, (c) 3-MCA, (d) 4-MCA, (e) 1,8-DMCA, (f) 1,4-DMCA, (g) 1,7-DMCA and (h) 2,5-DMCA at the B3LYP/
6–311þþG(d,p) level.
3
Journal of Petroleum Science and Engineering 191 (2020) 107308
2008; Ma et al., 2012).
The Fushan Depression can be divided into four tectonic units from
south to north: the southern slope zone, the central structural zone, the
central fault trough zone and the northern step-fault zone. Moreover, a
series of sub-structural can be further identified mainly including
Huangtong sag, Bailian sag, Yong’an anticline, etc.
Four tectonic events occurring during the late Mesozoic to Neogene
controlled the consequent tectonic evolution and sedimentary filling of
the Beibuwan Basin (Gong, 1997; Qiu and Gong, 1999; Liu et al., 2014).
The Shenhu orogeny in the Late Cretaceous leaded to the formation of a
number of grabens and half-grabens. The Zhuqiong orogeny during the
Paleocene and Eocene have great effects on the formation of rifting,
governing the formation of the current configuration of the Beibuwan
Basin. Fluvial and alluvial red pebbled sandstones and mudstones of the
Changliu Formation (E1c) were deposited during the early rifting period.
Subsequently, organic-rich mudstones of the Liushagang Formation
(E2l) were deposited in a suite of well-developed lakes in the late rifting
stage, which formed the most significant source rock in the Beibuwan
Basin. During the early Nanhai orogeny, the area was mainly filled with
lacustrine sediments and swamps, resulting in that the Weizhou For­
mation (E3w) was dominated by organic-rich mudstones with thin coal
interbeds. During Dongsha orogeny, block faulting controlled the basin
evolution accompanied by extrusive volcanism (Liu et al., 2015).
The major discoveries in the Fusan Depression include condensate
and light oils from the Huachang uplift, the Bailian fault blocks and
Jinfeng faulted nose structure, and normal gravity oils in the Meitai fault
blocks in the first (E2l1) and third (E2l3) members of the Liushagang
Formation. Besides, heavy oils from the Yong’an and Bohou-Chaoyang
oil pools in the Weizhou Formation (E3w) were also discovered (Li
et al., 2008, 2009). Although the oils from different regions have a wide
variety of physical property, the oils in this study sampled from the
Huachang Oilfield are dominated by light oils and condensate with an
average gravity of 45 (oAPI). The density of these samples is commonly
around 0.8200 g/cm3 (Li et al., 2008).
In the Fushan Depression, the major source of oil and gas are the
black mudstone and shale of the Liushagang Formation occurring in
Huangtong and Bailian sags (Li et al., 2008; Liu et al., 2012). These
lacustrine fine-grained rocks contain on average 1.5% total organic
carbon mainly consisting of type II and III kerogens (Ding et al., 2003),
and the burial depth of which exceeds 3000 m, mainly within the hy­
drocarbon generative window.
Q. Han et al.
Fig. 3. The schematic map showing the location and regional geological background (after Yang et al., 2016).
4. Results and discussion
4.1. Chemical structures and migration fractionation effects of alkylated
CAs in petroleum
Adsorption, partition, ionic exchange and size exclusion are possible
mechanisms resulting in geo-chromatography during subsurface
migration of oils, of which adsorption is considered to be the prevailing
process (Carlson and Chamberlain, 1986; Krooss et al., 1991).
Liquid-liquid (resembling oil-pore water) and liquid-solid (resembling
oil-water free mineral) geo-chromatographic fractionation occurring in
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Journal of Petroleum Science and Engineering 191 (2020) 107308
petroleum secondary migration are two primary potential
geo-chromatographic effects. The former is regarded to be of minor
importance with respect to primary migration owing to the low
permeability of source rocks and less water involved relatively in prin­
cipal phase of petroleum generation (Krooss et al., 1991). Previous
studies suggested that molecular fractionation mainly occurred in aro­
matic compounds, especially nitrogen-containing compounds, whereas
that of saturated hydrocarbons is slight (Chakhmakhchev et al., 1983;
Brother et al., 1991).
Migration fractionation effects occur for carbazole and their de­
rivatives during the oil migration process. Because the nitrogen atom is
Q. Han et al. Journal of Petroleum Science and Engineering 191 (2020) 107308

more electronegative than the carbon atom resulting in the electron Table 1
density on the CA molecule is shared unevenly between the N and C Connolly surface (Occupied Volume and Surface Area), interaction energies,
atoms. The N atom creates an active site on these molecules to enhance dipole moment and Gibbs free energies of carbazole, C1-CA and C2-CA isomers.
their polarity. Due to the polarity of CAs molecules, CAs tend to interact Carbazole Connolly Surface μ(Debye) Eln(kcal/mol) △G(kcal/
with other polar molecules in surrounding media via hydrogen bond Vo(Å3) Sa(Å2) H2O SiO2
mol)
during primary oil migration out of the source rocks and secondary
CA 163.01 181.71 1.6692 19.23 8.93
migration in the carrier beds (Dorbon et al., 1984; Li et al., 1995; Silli­
1-MCA 182.23 198.93 1.9995 19.78 6.08 0.0004
man et al., 2002). And the hydrogen bond mentioned above is formed by 3-MCA 182.04 200.50 1.5116 13.86 10.37 0.0010
the interaction between an H atom of the N–H functional group on 2-MCA 181.96 200.51 1.7942 17.59 8.77 0.0000
pyrrolic ring and atoms with higher electronegativity in organic matter 4-MCA 181.35 195.95 1.3244 14.91 10.50 0.0001
or on the surface of silica. Consequently, the amount of CAs theoretically 1,8- 200.69 215.93 2.2870 20.63 10.07 0.0006
DMCA
decreases along with oil migration. 1,3- 200.76 217.60 1.8846 17.62 10.82 0.0014
Alkylated carbazoles can be categorized into three groups, G1 (pyr­ DMCA
rolic N–H shielded), G2 (pyrrolic N–H partially shielded) and G3 (pyr­ 1,6- 200.90 217.59 1.7942 15.33 11.06 0.0012
rolic N–H exposed), respectively, based on the present or absence of DMCA
1,7- 200.66 217.58 2.0470 20.85 10.08 0.0006
alkyl substituent(s) at C-1 and C-8 positions which have different
DMCA
chemical properties due to the steric hindrance of the alkyl substituents 1,4- 198.30 213.76 1.6586 20.00 10.62 0.0020
(Li et al., 1995). The study by Yamamoto (1992) for migration frac­ DMCA
tionation of alkylbenzoquinolines suggested the preferential migration 1,5- 200.20 213.01 1.6534 17.79 10.34 0.0020
of nitrogen-masked isomers (NMIs) with the increasing of migration DMCA
2,6- 200.57 219.26 1.5207 18.79 11.23 0.0011
distances is attributed to NMIs’ weak adsorption on clay minerals. 1, DMCA
8-Dimethylcarbazole (1,8-DMCA) is an NMI and should have a weaker 2,7- 200.31 219.25 1.7613 16.91 10.67 0.0000
interaction with polar molecules in the carrier beds relative to NEIs, such DMCA
as 2,5-dimenthylcarbazole (2,5-DMCA). Therefore, the relative abun­ 1,2- 200.09 214.70 2.1554 16.69 10.89 0.0031
DMCA
dance of 2,5-DMCA to 1,8-DMCA could theoretically decrease with
2,4- 200.21 214.79 1.4841 19.96 11.17 0.0013
increasing migration distance. DMCA
2,5- 199.84 214.73 1.4732 18.36 11.64 0.0017
4.2. Molecular simulation of geo-chromatographic fractionation of DMCA
2,3- 199.56 216.07 1.7347 17.79 10.47 0.0042
alkylated CAs
DMCA
3,4- 199.22 211.70 1.1471 15.16 10.69 0.0065
The surface characteristics of molecules play significant roles in the DMCA
interaction between the molecules and the surrounding medium. Con­
nolly Surface (Connolly, 1983) were calculated with the optimization of
the equilibrium structure and by Atom Volumes & Surface (AVS) func­ (Yamamoto, 1992) and pyrrolic nitrogen compounds (Li et al., 1995)
tion in Materials Studio. The computed configuration followed: the grid with increasing migration distance. The authors contributed the mo­
spacing is set to 0.15 Å, van der Waals scale factor is set to1.00 Å, the lecular fractionation mainly to their stronger adsorption with clay
isosurface value is set to 0.05 Å, and the water probe radius is set to 1.5 mineral. To gain more insight into the interaction between CAs and
Å. (Liu et al., 2016). The calculated results and charge distributions are formation water/clay minerals (water molecules, α-quartz-(001) surface
shown in Table 1 and Fig. 4 (the negative partial charges are marked in as simulation models, respectively), molecular dynamics simulation
blue, while the positive partial charges are marked in yellow). As seen were performed in this study. Although there are also feldspar, clay
from the computed results, carbazole has the minimum area and volume minerals and rock fragments as well as the other matter in sandstone,
of Connolly Surface comparing to methlycarbazoles and dime­ quartz is the main component that causes the migration fractionation
thylcarbazoles, and it observed that slight increase in the value of the effect. Therefore, only the quartz is placed in the model considering the
area and volume of Connolly Surface with the increasing of substituents complexity of the simulation calculation and the occupied computing
numbers. However, there is no significant differences among carbazole resources. As shown in Table 1 and Fig. 5, for MCA isomers, the inter­
isomers with the same number of substituents. action energy (EIn) with α-quartz-(001) surface of 1-MCA is the mini­
The dipole moment can characterize the polarity of a molecule mum ( 6.08 kcal/mol), while that of 4-MCA is the maximum ( 10.50
linking the microcosmic and macroscopic performance properties. The kcal/mol). Therefore, the 1-MCA isomer, which has a relatively larger
calculated dipole moment of carbazole here is 1.67 Debye which is close dipole moment hasn’t gained a larger interaction energy on the
to an experimental value (1.7 Debye) (Shimamori and Sato, 1994). α-quartz-polarity surface comparing with the 4-MCA of a relatively
Therefore, the chosen calculation method in this study is quite reason­ smaller dipole moment. The methyl on 1-MCA can shield the hydrogen
able. The position of the substituents has significant effect on the dipole bond formation of N–H⋯O (O is the atom on α-quartz-surface), which
moment. Table 1 shows that 1-methylcarbazole (1-MCA) has the may lead to such results. This is why 4-MCA would be preferentially
maximum dipole moment value (2.00 Debye), whereas 4-methylcarba­ adsorbed on α-quartz-(001) surface during oil migration process than
zole (4-MCA) is the minimum one (1.32 Debye) among all methyl­ 1-MCA. Similarly, for DMCA isomers, the interaction energy (EIn) with
carbazole isomers. Judging from the dipole moment of α-quartz-(001) surface of 1,8-DMCA is the minimum ( 10.07 kcal/mol),
dimethylcarbazoles, 1,8-dimethylcarbazole (1,8-DMCA) yields the while that of 2,5-DMCA is the maximum ( 11.64 kcal/mol). Because
largest value (μ ¼ 2.29 Debye), whereas the smallest value (μ ¼ 1.47 two methyl groups at C-1 and C-8 positions of 1,8-DMCA totally shield
Debye) was presented in 2,5-dimethylcarbazole (2,5-DMCA). The large the N–H⋯O (O is the atom on α-quartz-surface) hydrogen bond forma­
differences in molecular polarity of alkylcarbazoles indicates there is tion, it suggests that 2,5-DMCA would be preferentially adsorbed on
significant differences in alkylcarbazoles’ ability to interact with the α-quartz-(001) surface during oil migration process than 1,8-DMCA
media of the carrier beds. Therefore, we can legitimately deduce that the though the dipole moment of 2,5-DMCA is smaller than that of 1,
relative abundance of alkylcarbazoles with different molecular polarity 8-DMCA.
in oils can be used to estimate oil migration distance. In addition, H2O cell (001) present adsorption as shown in Table 1
Previous studies elucidated a regular decline of nitrogen-exposed and Fig. 6. The EIn value of 1-MCA is 19.1824 kcal/mol while 4-MCA
relative to nitrogen-masked isomers in alkylbenzoquinolines presents a low interaction energy ( 14.9139 kcal/mol). 1,8-DMCA is

5
Q. Han et al. Journal of Petroleum Science and Engineering 191 (2020) 107308

Fig. 4. Connolly surface of CA and selective C1-and C2-CA isomers: (a) CA, (b) 1-MCA, (c) 1,8-DMCA, (d) 2,5-DMCA. The blue areas show the negative partial
charges, while yellow areas show the positive partial charges. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web
version of this article.)

Fig. 5. The adsorption of CA homologues on α-quartz-(001) surface (a) CA, (b) 4-MCA, (c) 1-MCA, (d) 1,8-DMCA, (e) 1,6-DMCA, (f) 2,5-DMCA.

adsorbed on the H2O cell (001) surface along with EIn of 20.6258 kcal/
mol, whereas 2,5-DMCA presents a lower EIn ( 18.3632 kcal/mol). It
can be possibly inferred that the larger interaction of 1-MCA and 1, 8-
DMCA with water could make them easier to migrate along with for­
mation water.
Here we think that the two molecular geochemical parameters pro­
posed by previous studies, i.e. the ratio of 4-/1-MCA (4-methyl­
carbazole/1-methylcarbazole: the relative abundance of compound
peak area of 4-MCA to 1-MCA in m/z 181 mass chromatograms) and the
ratio of 2,5-/1,8-DMCA (2,5-dimethylcarbazole/1,8-dimethylcarbazole:
the relative abundance of compound peak area of 2,5-DMCA to 1,8-
DMCA in m/z 195 mass chromatograms) to trace oil migration and
filling pathways are theoretically supported.
Furthermore, the dipole moment of 2,4-DMCA is the second lowest
value after 2,5-DMCA, and the interaction energy (EIn) with α-quartz-
(001) surface of 2,4-DMCA is also close to that of 2,5-DMCA. Therefore,
it can be further proposed a potential molecular parameter, 2,4-/1,8-
DMCA to trace the oil migration orientation. And the parameter shows
positive correlations with the most theoretical parameters i.e. 4-/1-MCA
and 2, 5-/1, 8-DMCA proposed above (Fig. 7). It will also be helpful for
tracing the oil migration orientation in the future.

6
Q. Han et al. Journal of Petroleum Science and Engineering 191 (2020) 107308

Fig. 6. The adsorption of CA homologues on H2O cell (001) (a) CA, (b) 4-MCA, (c) 1-MCA, (d) 1,8-DMCA, (e) 1,6-DMCA, (f) 2,5-DMCA.

Fig. 7. Cross plots between (a) 2,4-/1,8-DMCA and 2,5-/1,8-DMCA, (b) 2,4-/1,8-DMCA and 4-/1-MCA in the Tertiary sandstone reservoir in the Fushan Depression,
Beibuwan Basin.

4.3. Application to sandstone reservoir in the Fushan oilfield of the
Beibuwan Basin
4.3.1. Oil-to-oil correlation and oil families
Previous studies on the oil-to-oil correlation of the Fushan oilfield
have shown that the crude oils from this region are characterized by
high oleanane/C30hopane and C30diasteranes/C30hopane ratios and low
gammacerane/C30hopane ratios, indicating an oxic depositional envi­
ronment with dominant terrigenous organic matter input (Li et al.,
2008). And these crude oils have a “V” shape distribution pattern of C27,
C28 and C29 regular steranes, which further elucidate these samples
clearly belong to the same oil family (Yang et al., 2016).

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Q. Han et al. Journal of Petroleum Science and Engineering 191 (2020) 107308

In present study, we also selected a total of 36 oils sampled from the

Eocene sandstone reservoir of the Liushagang Formation in the Fushan
Depression (Table 2). Based on the GC–MS analysis of these 36 oil
samples, various molecular markers such as normal alkanes, acyclic
isoprenoids and C27–C29 regular sterane could be obtained and applied
for oil-to-oil correlation and oil family classification. However, the crude
oils from the Fushan Depression are dominated by light oils and con­
densates with quite low concentrations of steroids and terpenoids. In
conventional GC–MS analysis, it is a little difficult to accurately identify
the compounds and quantify the relative abundance of individual bio­
markers due to the low signal-to-noise of the mass chromatograms.
Therefore, normal alkanes and acyclic isoprenoids were regarded as
useful geochemical parameters to classify oil family.
The cross plot of Ph/nC18 vs. Pr/nC17, can reflect a variety of
geochemical information, such as depositional environments, organic
matter type, thermal maturity and biodegradation, and can also be used
to oil-to-oil correlation analysis (Shanmugam, 1985; Yandoka et al.,
2015). In the cross plot of Ph/nC18 vs. Pr/nC17 ratios, all the oil samples
were clustered in one zone suggesting that the relative source rocks were Fig. 8. Cross plots of pristane to nC17 alkane (Pr/nC17) vs. phytane to nC18
deposited under an oxic environment with dominant terrigenous alkane (Ph/nC18) of crude oils from the Tertiary sandstone reservoir in the
organic matter input except for two samples, wells Jf6 (2734.0–2738.0 Fushan Depression Beibuwan Basin (after Shanmugam, 1985).
m) and Jfn1(2213.5–2216.0 m) with relatively higher values of Pr/nC17
and Ph/nC18, indicating they may be at lower maturity (Fig. 8). northeast to southwest in the Huachang oil/gas field and towards north
to south in the Bailian oilfield in general. Therefore, the overall migra­
4.3.2. Oil charging orientation and filling pathway tion orientation is generally identical and the major source kitchen is
We preliminarily applied the three proposed molecular parameters predicted to be located in the Bailian Sag. In addition, the Huangtong
relative to methylcarbazoles and dimethylcarbazoles to trace the di­ Sag may have minor contributions to oil wells in the west of the Hua­
rection of oil migration. The values of 4-/1-MCA, 2,5-/1,8-DMCA and chang oilfield. There are three main oil filling points around well H3 in
2,4-/1,8-DMCA ratios for wells in Fushan Depression are listed in Huachang oil/gas field, well L3 in the Bailian oilfield and well Hd1 in
Table 2. Fig. 9 shows the isopleth map of 4-/1-MCA ratios. The Huadong region, respectively.
decreasing direction of 4-/1-MCA values shows a tendency towards The isopleth map of 2,5-/1,8-DMCA ratios from the data of 36 oils

Table 2
Selected molecular geochemical parameters for oils from the Fushan Depression, Beibuwan Basin.
3
Well Depth (m) Formation Density (g cm ) 4-/1-MCA 2,5-/1,8-DMCA 2,4-/1,8-DMCA Pr/nC17 Ph/nC18 MPI-1

H1-1 3347.2–3401.1 E2l3 0.83 0.51 0.47 0.48 0.39 0.11 0.88
H2 2970.6–3014.0 E2l3 0.79 0.43 0.39 0.40 0.39 0.12 1.18
H2-1 2909.8–2954.6 E2l3 0.78 0.42 0.41 0.39 0.50 0.13 0.83
H2-2 2973.0–3021.0 E2l3 0.80 0.50 0.50 0.48 0.46 0.12 0.77
H2-3 2994.6–3084.0 E2l3 0.78 0.44 0.41 0.41 0.41 0.11 0.82
H3 3015.0–318206 E2l3 0.78 0.67 0.57 0.54 0.31 0.10 0.76
H3-1 3949.6–3286.2 E2l3 0.80 0.53 0.54 0.53 0.39 0.12 0.79
H3-2 3087.0–3144.6 E2l3 0.79 0.54 0.54 0.51 0.40 0.13 0.78
H3-3 3158.6–3221.0 E2l3 0.79 0.48 0.49 0.48 0.38 0.12 0.77
Hx4 3253.0–3259.6 E2l3 0.82 0.46 0.50 0.47 0.51 0.13 0.75
H5 2715.8–2731.0 E2l3 0.77 0.40 0.34 0.30 0.61 0.15 0.64
H7 3516.6–3521.0 E2l3 0.81 0.84 0.52 0.59 0.28 0.08 0.64
H4-3 3015.4–3060.6 E2l3 0.81 0.40 0.42 0.45 0.46 0.12 0.77
H10 2961.6–2981.8 E2l3 0.76 1.04 1.03 1.01 0.41 0.15 0.97
H2-18a 3151.6–3160.0 E2l3 n.d. 0.82 0.74 0.75 0.45 0.12 0.82
H3-12x 3194.4–3238.8 E2l3 0.79 0.68 0.47 0.48 0.35 0.11 0.78
H3-5 3109.1–3128.2 E2l3 0.76 0.83 1.23 1.06 0.46 0.16 0.84
H3-6 3114.4–3148.2 E2l3 0.77 0.94 1.10 1.03 0.45 0.14 0.84
H8-1 3585.2–3669.2 E2l3 0.79 0.61 0.57 0.65 0.38 0.12 1.16
H7-3 3141.4–3539.6 E2l3 0.80 0.57 0.49 0.57 0.37 0.13 1.16
Hd4-2 3818.7–3826.7 E2l3 n.d. 0.51 0.47 0.50 0.33 0.11 1.17
Hd5 3467.0–3473.4 E2l3 0.82 0.58 0.52 0.56 0.38 0.11 1.34
Hd2 2542.0–2563.0 E2l3 0.83 0.37 0.35 0.40 0.66 0.18 0.78
Hd1 3329.4–3372.8 E2l3 0.79 1.02 0.96 0.97 0.49 0.16 1.09
Hd1-1 3347.0–3384.0 E2l3 0.80 1.06 1.18 1.17 0.41 0.14 1.05
L1 2921.6–2934.8 E2l3 0.79 0.42 0.39 0.44 0.51 0.14 0.92
L11 2842.4–2846.0 E2l3 0.82 0.40 0.32 0.44 0.56 0.15 0.71
L1-2x 2795.0–2823.4 E2l3 0.79 0.47 0.32 0.36 0.50 0.15 1.26
L4 2678.4–2698.2 E2l3 0.75 0.39 0.40 0.41 0.40 0.09 1.35
L8x 2459.4–2474.4 E2l3 0.83 0.52 0.48 0.49 0.57 0.16 0.99
L9x 2140.0–2146.8 E2l3 0.82 0.51 0.39 0.48 0.63 0.18 0.93
L3 3390.6–3410.0 E2l3 n.d. 0.53 0.60 0.46 0.44 0.13 1.00
L12 2794.8–2801.0 E2l3 0.86 0.37 0.32 0.32 0.60 0.15 0.70
Jf4 1969.4–1986.8 E2l3 0.81 0.37 0.30 0.34 0.68 0.11 0.73
Jf6 2734.0–2738.0 E2l3 0.82 0.43 0.44 0.41 1.12 0.34 0.56
Jfn1 2213.5–2216.0 E2l3 0.84 0.36 0.31 0.35 0.85 0.22 0.79

8
Q. Han et al. Journal of Petroleum Science and Engineering 191 (2020) 107308

Fig. 9. The isopleth map of 4-/1-methylcarbazole ratios showing oil migration orientation and filling pathways of the Tertiary sandstone reservoir in the Fushan
Depression, Beibuwan Basin.

samples is illustrated in Fig. 10. The decreasing direction and the pro­
jecting locus of 2,5-/1,8-DMCA ratios indicates the oil migration direc­
tion and preferential filling pathways. The overall migration orientation
in the study area is from north to south: one filling pathway is charged to
Huachang oil/gas field along wells Hd1-1, Hd1 and H2-18a; and the
other is charged to Balian oilfield along wells L3, L8x and L9x. Besides,
in the west area of Huachang oil/gas field, some oil wells may be
charged partly from the Huangtong Sag from northwest to southeast
along well H3. Thus, it can be seen that three main oil filling points are
also located around wells Hd1, L3 and H3, respectively.
From the results of molecule simulation, the properties of 2,4-DMCA
is close to 2,5-DMCA, and 2,4-/1,8-DMCA shows positive correlations
with the parameters i.e. 4-/1-MCA and 2,5-/1,8-DMCA. Therefore, we
proposed 2,4-/1,8-DMCA as a potential oil migration tracer and drawn
the isopleth map of 2,4-/1,8-DMCA ratios in the oils (Fig. 11). The
isopleth trend and distribution of three molecular parameters relative to

Fig. 10. The isopleth map of 2,5-/1,8-dimethylcarbazole ratios showing oil migration orientation and filling pathways of the Tertiary sandstone reservoir in the
Fushan Depression, Beibuwan Basin.

9
Q. Han et al.
Fig. 11. The isopleth map of 2,4-/1,8-dimethylcarbazole ratios showing oil migration orientation and filling pathways of the Tertiary sandstone reservoir in the
Fushan Depression, Beibuwan Basin.
CAs are generally consistent, so the overall migration orientation and
filling pathways based on the 2,4-/1,8-DMCA ratios are similar to that of
the 4-/1-MCA and 2,5-/1,8-DMCA ratios. And the tracing results of the
CAs are also in consistence with those of other molecular markers (Li
et al., 2008, 2018; Yang et al., 2016).
4.4. Effects of source input, depositional environment, biodegradation and
maturity
The source input and depositional environment have considerable
impact on the occurrence and distributions of CAs in oils and sedimen­
tary organic matter (Clegg et al., 1997; Bakr and Wilkes, 2002). The
precondition of using molecular geochemical parameters to trace oil
migration orientation is that all oils should belong to the same oil family.
In this study, all oils samples are derived from the same source kitch­
en/bed belonging to a single oil family as mentioned above in section
4.3.1. Therefore, the effects of source input and depositional environ­
ment for composition of CAs were negligible in this study.
Previous studies indicated that a slight biodegradation in reservoir
affects little to the carbazole and alkylcarbazoles in the crude oils. With
the increasing of the biodegradation, the concentrations of carbazole
and alkylcarbazoles decrease for mid-degree biodegraded oils and
sharply decrease in the heavily biodegraded oils (Zhang et al., 1999;
Huang et al., 2003). However, the oils samples from Tertiary sandstone
reservoirs in the Fushan Depression were not subjected to apparent
biodegradation (Yang et al., 2016). In consequence, the influence of
biodegradation on the distribution of CAs can be neglected.
In addition, the distribution of carbazoles are also related to maturity
differences. (Li et al., 1997; Clegg et al., 1998b; Zhang et al., 2011). The
study by Li et al. (1997) suggested that concentrations of various pyr­
rolic nitrogen compounds increase with increasing thermal maturity,
which can provide background information for calibrate such data in
migrated petroleum. The study by Zhang et al. (2011) showed the
relative distributions of C1-, C2-carbazoles and benzocarbazoles dis­
played “two-stage” variation in a wide maturity range indicating the
different geochemical controls between the immature and mature
stages. The methylphenanthrene index (MPI-1) is the common aromatic
10
Journal of Petroleum Science and Engineering 191 (2020) 107308
hydrocarbon maturity parameters, appearing to be as useful as vitrinite
reflectance for maturity assessment (Radke et al., 1982; Radke, 1988).
Cross-plots showing the relationship between 4-/1-MCA, 2,5-/1,
8-DMCA, 2,4-/1,8-DMCA and MPI-1 are illustrated in Fig. 12a, b and c,
respectively. As shown in Fig. 12, there is no certain relationship be­
tween these three parameters and MPI-1, respectively, suggesting that
thermal maturity have no significant effect on these molecular
geochemical indicators.
Moreover, we further calculated Gibbs free energies of alkylated
carbazole isomers/homologues in order to illustrate the relationship
between the migration indicators and thermal maturity. Gibbs free en­
ergy (G ¼ H – TS) is a thermodynamic potential including the enthalpy
effect and the entropy effect, which can be applied to describe the sta­
bility of a molecule. Generally speaking, the lower potential energy of a
system, the more stable it is. As can be seen from Table 1, the relative
values of G (△G) could indicate a stable molecule. △G is defined as,
△G ¼ Gi – Glowest (2)
Where Gi is a G of any of several isomers, Glowest is a G of the lowest
molecule among isomers. For example, 2-MCA has a lowest (△G2-MCA ¼
G2-MCA – G2-MCA) ¼ 0.00 kcal/mol, whereas the △G for MCA isomers is
relative to 2-MCA. The same situation is occurring in other isomers.
Gibbs free energies of MCA isomers and DMCA isomers here indicate no
significant differences respectively (Table 1) which indirectly means
they have little effect on thermal maturity.
Therefore, the proposed migration orientation molecular parameters
in this study are principally controlled by migration fractionation effect.
5. Conclusions
By using density functional theory (DFT) and molecular dynamics
(MD) simulations, this study investigated the potential mechanisms for
fractionation effect of alkylated carbazoles during oil migration process.
Molecular dynamics simulations show that the differences of interaction
energies between alkylated carbazoles and α-quartz/water of carrier
beds lead to their migration fractionation effect. For methylcarbazole
(MCA) isomers, 4-methylcarbazole (4-MCA) has a much higher
Q. Han et al.
Fig. 12. Cross-plots showing the relationship between 4-/1-MCA, 2,5-/1,8-
DMCA, 2,4-/1,8-DMCA and MPI-1 of crude oils from the Tertiary sandstone
reservoir in the Fushan Depression, Beibuwan Basin.
adsorption energy with α-quartz-(001) surface than 1-methylcarbazole
(1-MCA). And for dimethylcarbazole (DMCA) isomers, the interaction
energy (EIn) with α-quartz-(001) surface of 2,5-dimethylcarbazole (2,5-
DMCA) is the maximum, while that of 1,8-dimethylcarbazole (1,8-
DMCA) is the minimum. The interaction energy (EIn) with α-quartz-
(001) surface of 2,4-dimethylcarbazole (2,4-DMCA) is close to that of
2,5-dimethylcarbazole (2,5-DMCA).
Three theoretically proven migration parameters, i.e. 4-/1-MCA,
11
Journal of Petroleum Science and Engineering 191 (2020) 107308
2,5-/1,8-DMCA and 2,4-/1,8-DMCA are considered as effective migra­
tion indicators to trace oil migration orientation and filling pathways.
And three migration parameters were also successfully applied in
lacustrine sandstone reservoir in the Fushan Depression, Beibuwan
Basin.
The calculations of Gibbs free energy show that there are no signif­
icant differences of thermal dynamical stabilities among MCAs and
DMCAs, respectively, which means the proposed parameters are less
affected by thermal maturity. In this study, all oils samples are derived
from the same source kitchen/bed belonging to the same oil family. And
previous studies indicated that these oils samples were not subjected to
apparent biodegradation. Therefore, the variations of 4-/1-MCA, 2,5-/
1,8-DMCA and 2,4-/1,8-DMCA in petroleum during subsurface migra­
tion are mainly controlled by migration fractionation in this region.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
CRediT authorship contribution statement
Qiuya Han: Data curation, Writing - original draft. Meijun Li:
Conceptualization, Writing - review & editing, Project administration.
Xiaoqiang Liu: Software, Methodology. Weidong Jiang: Visualization,
Resources, Investigation. Shengbao Shi: Methodology. Youjun Tang:
Funding acquisition. Daxiang He: Investigation.
Acknowledgements
This work was funded by the National Natural Science Foundation of
China [Grant No.41972148], the National Key R & D Program of China
(Grant No. 2017YFC0603102) and the Foundation of the State Key
Laboratory of Petroleum Resources and Prospecting, China University of
Petroleum-Beijing (No. PRP/open-1503). The authors are grateful for
the assistance of Lei Zhu and Jianfeng Zhang for the GC–MS analysis. All
calculated results were supported by Sichuan University of Science &
Engineering High Performance Computing Center for providing
computational.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.petrol.2020.107308.
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