Journal of Natural Gas Science and Engineering 45 (2017) 670e692

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Journal of Natural Gas Science and Engineering

journal homepage: www.elsevier.com/locate/jngse

Continental shale pore structure characteristics and their controlling

factors: A case study from the lower third member of the Shahejie
Formation, Zhanhua Sag, Eastern China
Tingwei Li a, b, Zhenxue Jiang a, b, *, Zhuo Li a, b, Pengfei Wang a, b, Chenlu Xu c,
Guoheng Liu a, d, Siyuan Su a, b, Chuanxiang Ning a, b
a
State Key Laboratory of Petroleum Resources and Prospecting, China University of Petroleum, Beijing 102249, China
b
Unconventional Natural Gas Research Institute, China University of Petroleum, Beijing 102249, China
c
Key Laboratory of Petroleum Resource Research, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
d
College of Geosciences, China University of Petroleum, Beijing 102249, China

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

Article history: Since shale oil and gas primarily occur in micro-nano pores and fractures, research on pore structure
Received 5 September 2016 characteristics is important to understand shale oil and gas accumulation mechanisms. Studies on the
Received in revised form pore structure of the lower third member of the Shahejie (Esl3) Formation in Zhanhua Sag, Jiyang
27 March 2017
Depression, Bohai Bay Basin, Eastern China, are quite limited, thereby, restricting further investment on
Accepted 10 June 2017
shale oil and gas exploration. We studied continental shale pore structure characteristics and their
Available online 23 June 2017
controlling factors by using a series of laboratory experiments on core samples taken from the Luo-69
Well. The results demonstrate that the Esl3 continental shale has a high proportion of calcareous min-
Keywords:
Zhanhua Sag
erals, low siliceous minerals, and low clay minerals. It is characterized by low total organic carbon (TOC)
Esl3 Formation content, low thermal maturity, and Type I and II organic matter. Five different kinds of pore spaces are
Continental shale developed in the shale samples: organic matter-hosted pores, intergranular pores, intercrystalline pores,
Pore structure dissolution pores, and micro-fractures, with the majority of slit-shaped and ink-bottle-shaped pores.
Controlling factors Macropores make the greatest contribution to the total pore volume, whereas micropores provide the
major surface area. As the organic-rich laminated calcareous shale (ORLCS) presents a larger pore vol-
ume, surface area, and mercury withdrawal efficiency, it is a favourable shale lithofacies for shale oil and
gas storage and flow. Compared with the Longmaxi marine shale, macropores well-developed in the Esl3
shale make great contribution for free hydrocarbon accumulation. Samples with different TOC contents,
mineral compositions, thermal maturities, and lamellar layers exhibit distinct differences in pore
structure. Mineral composition and thermal maturity primarily affect micropores and mesopores.
Macropores are influenced by mineral composition, TOC content, thermal maturity, and lamellar layers.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Shale oil and gas have become important energy sources in
North America (Montgomery et al., 2005; Jarvie et al., 2007; Ross
and Bustin, 2008; Chalmers and Bustin, 2008). The great success
of shale oil and gas exploration and development in North America
has aroused widespread interest across the world. In recent years,
petroleum scientists in China have initiated research on shale oil
* Corresponding author. State Key Laboratory of Petroleum Resources and Pro-
specting, China University of Petroleum, Beijing 102249, China.
E-mail address: zhenxuejiang@163.com (Z. Jiang).
and gas, gradually making them important targets for oil and gas
exploration (Jiang et al., 2012; Guo, 2014; Wang, 2015).
Shale oil and gas refer to the petroleum and natural gas that are
produced from organic-rich black shale and mainly occur in micro-
nano pores (Jarvie et al., 2007; Curtis, 2002; Ji et al., 2015). The
practical exploration and development of shale oil and gas have
demonstrated that micro-nano pore structure plays an extremely
important role in the storage and flow of shale oil and gas (Ji et al.,
2014; Javadpour et al., 2007). Micro-nano pore structure is gener-
ally characterized by size, volume, surface area, shape, connectivity,
and spatial distribution (Haroonabadi and Haghifam, 2013). In
recent years, many qualitative and quantitative techniques have

http://dx.doi.org/10.1016/j.jngse.2017.06.005
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 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692
been used to study the micro-nano pore structure of shale reser-
voirs. The qualitative techniques, such as polarized light micro-
scopy (PLM), field emission scanning electron microscopy (FE-
SEM), and nano-CT, are used to directly observe the shape, size, and
distribution of pores. PLM is a common method that can provide a
variety of pore structure parameters, but it is largely applicable to
the pores with the magnitude of micrometres. FE-SEM is a widely
used method to identify minerals and observe micro-nano pores
using secondary and backscattered electron imagery. However, it
also has some deficiencies, for example, the complicated pretreat-
ment of samples and only two-dimensional imaging (Ambrose
et al., 2010; Loucks et al., 2009; Chalmers et al., 2012; Jiao et al.,
2014). Nano-CT is an advanced three-dimensional imaging
method for obtaining the distribution and connectivity of nano-
scale pores, but its application is limited by the high expense (Wang
et al., 2016a; Tang et al., 2016a). In addition, quantitative tech-
niques, such as low-pressure adsorption (LPA), high-pressure
mercury injection (MIP), and small-angle neutron scattering
(SANS), are used to indirectly characterize the size, shape, volume,
surface area, and connectivity of pores. LPA is able to measure the
pore volume, surface area, and pore size distribution in the samples
using N2 and CO2 as adsorbates, although extremely high vacuum is
needed in N2 adsorption and the theory model of CO2 adsorption is
not yet mature (Mastalerz et al., 2013; Clarkson et al., 2013; Chen
et al., 2011, 2016). MIP can obtain the pore structure parameters
based on the amount of mercury injection as well. Nevertheless, it
is a destructive experiment as the higher pressure of mercury in-
jection may cause induced fractures, sample deformation, and
compression of shale pores (Mastalerz et al., 2013; Ross and Bustin,
2007; Katsube, 1992). SANS allows for a wide pore size distribution
to be investigated. Moreover, the analysis may be performed at
elevated temperature and pressure, unlike LPA, and is nonde-
structive, unlike MIP. However, it is not suitable for the mixed
powder composed of particles with different electron densities or
the powder with micropores (Clarkson et al., 2013; Melnichenko
et al., 2009; Mares et al., 2009).
Being different from sandstone due to the presence of organic
matter, pores that occur in shale reservoirs can be divided into two
types: mineral-hosted pores and organic matter-hosted pores
(Loucks and Ruppel, 2007; Loucks et al., 2009, 2012; Clarkson et al.,
2012; Scherdel et al., 2010; Slatt and O'Brien, 2011). Simultaneously,
according to the definition provided by the International Union of
Pure and Applied Chemistry (IUPAC), pores can be divided into
three types on the basis of pore size: micropores (diameter less
than 2 nm), mesopores (diameter between 2 nm and 50 nm), and
macropores (diameter greater than 50 nm). Various kinds of pores
have great differences in reservoir property and seepage ability.
Since micropores and mesopores have a large surface area, they
mainly host adsorbed hydrocarbons and diffusion processes.
However, since macropores have a large volume, they tend to be
free of hydrocarbons and are dominated by permeation processes
(Slatt and O'Brien, 2011). Additionally, previous studies have
revealed that both TOC content and thermal maturity have a sig-
nificant effect on organic matter-hosted pores and mineral-hosted
pores. During hydrocarbon generation, the consumption and syn-
eresis of organic matter result in considerable organic matter-
hosted pores. Organic acids that are released during the hydro-
carbon generation dissolve eutectic minerals to develop dissolution
pores. Owing to great differences in mechanical properties, brittle
minerals are favourable for developing micro-fractures under slight
force compared to clay minerals (Jarvie et al., 2007; Rickman et al.,
2008; Sondergeld et al., 2010). The development of lamellar layers
has a great influence on micro-nano pore structure, greatly
increasing reservoir space and seepage paths (Wang et al., 2013a,
2015; Liu et al., 2015). As a result, various kinds of shale
671
lithofacies that are ordinarily characterized by mineral composi-
tion, TOC content, and the development of lamellar layers can have
great differences in pore structure. Since pore structure is one of the
important criteria in identifying the sweet spots of resource plays,
shale lithofacies that is favorable to the reservoir and flow of oil and
gas could be selected on the basis of pore structure. Therefore, to
seek the distribution zones of favorable shale lithofacies should be
the key step in the exploration and development of shale oil and
gas.
In recent years, many pore structure studies of shale reservoirs
have been carried out, mainly concentrating on marine shale
(Montgomery et al., 2005; Jarvie et al., 2007; Ross and Bustin, 2008;
Chalmers and Bustin, 2008). Chalmers et al. (2012) utilized drilling
cores to study the mineral composition, pore structure, and organic
geochemical characteristics of the Barnett shale, Woodford shale,
Haynesville shale, Marcellus shale, and Doigunits shale in North
America. In China, research on the pore structure of shale reservoirs
has been conducted as well, primarily focusing on the Silurian
Longmaxi marine shale in the southeast Sichuan Basin (Tang et al.,
2015; Wang et al., 2016b). However, there is little comprehensive
and systematic research on the pore structure of continental shale
reservoirs. Compared with marine shale, the sedimentary envi-
ronments of continental shale change rapidly, and sedimentary
strata of continental shale are relatively young, making continental
shale reservoirs unique (Yuan et al., 2016; Liu et al., 2015). In
Zhanhua Sag the sedimentary environment of the Esl3 Formation
was a warm-wet climate with limited provenance, moderateedeep
lacustrine facies, salt water, strong reduction, and strong alkalinity.
Although many studies on the mineral composition, porosity, and
permeability of shale reservoirs have been done (Li et al., 2015; Liu
et al., 2012; Song et al., 2011), research on pore structure is rela-
tively limited in the study area. The current research on the pore
structure of the Esl3 shale is simple qualitative analysis, especially
lacking quantitative analysis. For example, Wang et al. (2013a)
studied the pore structure of the Esl3 shale and only divided the
pores into the following types: intercrystalline pores, dissolution
pores, and intergranular pores. Li et al. (2015) just identified the
pore types in the Esl3 shale samples via SEM and clarified the ex-
istence of organic matter-hosted pores.
In this study, the Esl3 shale in Zhanhua Sag, Jiyang Depression,
Bohai Bay Basin, Eastern China is taken as the object. Using X-ray
diffraction (XRD), Rock-Eval pyrolysis, TOC analysis, vitrinite
reflectance analysis, thin section observation, soxhlet extraction,
FE-SEM, low-pressure N2 and CO2 adsorption, and MIP analysis, the
micro-nano pore structure and its controlling factors for conti-
nental shale reservoirs were systematically studied in order to
provide a scientific basis for continental shale oil and gas explora-
tion and development (Fig. 1).
2. Geological setting and samples
2.1. Geological setting
Zhanhua Sag lies in the northeast of the Jiyang Depression, Bohai
Bay Basin, Eastern China (Fig. 2). It covers an area of 2800 km2 and
is located south of the Chenjiazhuang High and east of the Kendong
High. The west and north sides are bounded by the Yidong and
Chengdong Faults, respectively. The tectonic units developed in
Zhanhua Sag include the Gubei Sag, Bonan Sag, Gunan Sag, Fulin
Sag, Sikou Sag, Kenxi Sag, Zhuangxi Sag, and Gudao High. The faults
are well-developed in Zhanhua Sag, including three NW-trending
major faults (Luoxi Fault, Guxi Fault, and Wuhaozhuang Fault)
and a series of NE- and EW-trending faults (Li et al., 2015; Wang
and Hu, 2014; Zhang et al., 2005).
Zhanhua Sag has developed very thick Cenozoic strata (Fig. 3).
672 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692
Fig. 1. Workflow chart for the sequence of the current experimental studies.
Cenozoic Paleogene shale is distributed in the Shahejie Formation
(Song et al., 2015). The Esl3 Formation is not only the major horizon
for the development of shale but also the most favourable horizon
for oil and gas exploration and development. According to statistics,
there are more than 80 wells that have drilled the Esl3 Formation in
Zhanhua Sag, 11 wells of which produce high-yielding commercial
oil and gas flows (the highest well production rate up to 140 t/d and
12549 m3/d). In addition, 3 horizontal wells are deployed in
Zhanhua Sag and performed by staged fracturing, the highest well
production rate up to 7.8 t/d (Wang et al., 2013b; Liu et al., 2012;
Zhao et al., 2012).
Owing to the fact that the strong major fault activity resulted in
crustal extension, basin subsidence, and an increase in water depth,
the sedimentary period of the Esl3 Formation in Zhanhua Sag is
known as the main period for the development of source rocks. The
lithology is mainly grey and dark-grey shale, with a small amount of
siltstone. The sedimentary environment of the Esl3 Formation had a
warm-wet climate, limited provenance, moderateedeep lacustrine
facies, salt water, strong reduction, and strong alkalinity (Wang
et al., 2015). The Esl3 shale in Zhanhua Sag is widely distributed,
with the thickness ranging from 200 m to 450 m and increasing
from south to north.
2.2. Samples
Total of 36 core samples of the Esl3 Formation were taken from
the Luo-69 Well (Fig. 2). These core samples were stored at room
temperature in an airtight container. The Luo-69 Well, the only
systematic coring well in the study area, is a vertical exploratory
well that has successively drilled through the Neocene Min-
ghuazhen and Guantao Formations, and the Paleogene Dongying,
Shahejie, and Kongdian Formations (from top to bottom) (Fig. 3).
The Esl3 Formation in the Luo-69 Well, the interval of interest in our
study, is mostly composed of grey and dark-grey tight shale, and its
depth is from 2910 m to 3130 m, with the thickness of 220 m.
3. Experimental methods
The sample number for each experiment analysed is shown in
detail in Table 1. The preparation process for each experimental
method is provided below. All of the experiments were conducted
at the State Key Laboratory of Petroleum Resources and Pro-
specting, China University of Petroleum, Beijing.
3.1. XRD, Rock-Eval, TOC, vitrinite reflectance analysis, thin section
observation, and soxhlet extraction
XRD analysis is a common scientific method for evaluating the
mineral composition of shale reservoirs. Thirty-six samples were
analysed for whole-rock and clay fraction mineralogy using a ZJ207
Bruker D8 advance X-ray diffractometer. Each sample (approxi-
mately 5 g) for XRD analysis was crushed and sieved to a 300 mesh
size fraction. The detailed process of the experiment is similar to
that presented by Kamp and Peter (2008) and Metwally and
Chesnokov (2012).
Rock-Eval pyrolysis is a conventional method for characterizing
the type and thermal maturity of organic matter (Espitalie et al.,
1977). TOC analysis is an available method for determining the
content of total organic carbon (Stasiuk et al., 2006). Thirty-six
samples were used for Rock-Eval pyrolysis and TOC analysis, us-
ing the ROCK-EVAL.II methodology and a CS230HC carbon and
sulphur analyser. Each sample (approximately 60 mg) for Rock-Eval
pyrolysis was crushed and sieved to a 200 mesh size fraction. TOC
measurement samples were immersed in a 5% HCl solution for two
days to eliminate all carbonate minerals. The samples were then
dried in a stoving oven at 65
C for 1.5 days. The vitrinite reflectance
 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692
Fig. 2. Location map of the study area for Zhanhua Sag, Jiyang Depression, Bohai Bay Basin, Eastern China.
values (Ro), a common index for characterizing the thermal
maturity of organic matter, were acquired using a Zeiss microscope
and an MPV-I microphotometer in reflected mode (Taylor et al.,
1998).
Thin section observation is an established method for deter-
mining the mineral composition and optical properties of rock thin
sections using a petrographic microscope (Su et al., 1991). It is
necessary for preparing the thin section to repeatedly grind the
core sample until its thickness reaches 0.02e0.06 mm. Thirty-six
samples were observed using a Leica Leitz Dmrxp apparatus un-
der 2.5  10, 10  10, and 10  20 magnifications.
Soxhlet extraction is a common method for extracting dissol-
uble organic matter (chloroform bitumen “A”) from shale based on
the theory of similarity and intermiscibility (Pan et al., 2015). Each
sample was ground to a <75 mm (<200 mesh) powder. Each sample
was extracted for 24 h using a mixed solution (250 ml CH2Cl2 and
5 ml CH3OH; boiling temperature of 75
C). Eight samples were
used for Soxhlet extraction.
673
3.2. FE-SEM analysis
FE-SEM is an advanced method for directly observing the size,
shape, and distribution of micro-nano pores (Jiao et al., 2012; Wang
et al., 2016b; Loucks et al., 2012). Ar-ion polishing is necessary to
reduce the surface roughness of shale samples. The polished sam-
ple was then coated with Au to prevent electrostatic charging. FE-
SEM analysis was conducted using both secondary and back-
scattered electron imagery at an operating current of 15 kV. The
dimensions of each sample were approximately
10 mm  10 mm  3 mm. Eight samples were observed using an
FE-SEM (FEI HELIOS NANOLAB 650 SEM) in combination with an
argon-ion cross-section polisher and energy dispersive X-ray
spectrometer.
3.3. Gas adsorption and MIP analysis
Low-temperature low-pressure (77.35 K at 101.3 kPa) N2
674 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692

Fig. 3. I: Generalized stratigraphic columns of the Jiyang Depression. II: Logging data of the Luo-69 Well for the Esl3 Formation.
 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692
Table 1
Sample numbers corresponding to experimental methods.
Experimental methods Samples analysed
XRD analysis 36
Rock-Eval analysis 36
TOC analysis 36
Vitrinite reflectance analysis 36
Thin section observation 36
Soxhlet extraction 8
FE-SEM 8 becomes greater with increasing depth.
N2 adsorption analysis 8
CO2 adsorption analysis 8
MIP analysis 8 4.3. Sedimentary structure characteristics
adsorption analysis is a common method for characterizing mes-
oporous structure (Rouquerol et al., 1994). Surface area was ob-
tained using the Brunauere-Emmette-Teller (BET) method
(Brunauer et al., 1938). The pore size distribution and pore volume
were calculated using the Barrette-Joyner-Halenda (BJH) theory
(Brunauer et al., 1938; Barrett et al., 2014). Eight samples were
measured using a four-type automatic surface area and porosity
physical adsorption instrument (USA, Quantachrome Ins,
Quadrasorb-SI). Each sample (approximately 1e2 g) was crushed
into grains of 60e80 mesh size and automatically degassed at
approximately 110
C under vacuum for approximately 14 h to
remove adsorbed moisture and volatile matter before analysing
with N2.
CO2 adsorption analysis is more suitable for micropores
(Chalmers et al., 2012; Cui et al., 2010; Tian et al., 2012). The shale
samples were then used for CO2 adsorption after the N2 adsorption.
Before the test, the samples were put into a vacuum drying oven for
2 h to vacuumize. The surface area was obtained using the CO2
isothermal adsorption method at 273.15 K, whereas the pore size
distribution and pore volume were calculated using the Density
Functional Theory (DFT) model. Eight samples were measured us-
ing a NOVA4200e specific surface area and pore-size distribution
analyser.
MIP analysis is an applicable method for obtaining information
on macroporous structure (Washburn, 1921; Katsube et al., 1998;
Eseme et al., 2006; Ross and Bustin, 2009). As the test pressure is
increased, mercury molecules gradually enter into small pores. The
pore size distribution and pore volume were obtained from the
number of mercury molecular intrusion. The surface area was
calculated according to the YoungeDupre  equation. Eight samples
were measured using an automatic mercury porosimeter (Micro-
meritic Instruments Ltd., Auto Pore IV9500 porosimeter). The di-
ameters of the columnar samples used in the MIP were
approximately 2.5 cm. When getting the samples from the core,
one must be very careful to avoid the generation of micro-fractures.
Before the test, the samples were dried for 24 h at 110
C to remove
any adsorbed and free water.
4. Results
4.1. Mineral composition
The Esl3 shale mainly consists of calcite, clay, and quartz (Fig. 4).
In addition, it contains a small amount of K-feldspar, anorthose,
dolomite, siderite, pyrite, and other particles. With increasing
depth, the calcite content gradually becomes greater, whereas the
clay and quartz contents both become less. Clay minerals mainly
consist of illiteesmectite mixed layer and illite, with only a small
amount of kaolinite and chlorite.
675
4.2. Organic matter characteristics
The TOC content of the Esl3 shale ranges from 0.52 wt% to 9.32 wt
% and has a gradually decreasing trend with increasing depth. The
kerogen in the Esl3 shale contains organic matter of Type I and II,
presenting an incline to Type I and II1 (Fig. 5). The Esl3 shale is
mainly in the oil window at the present time, with Ro ranging from
0.70% to 0.91% (Fig. 4). In addition, the thermal maturity gradually
Using high-resolution core imaging and thin section observa-
tion, it can be observed that the upper part of the Esl3 shale develops
a massive structure with very thick horizontal beddings or no
beddings and all kinds of minerals distributed as a mixture (Fig. 4a).
In contrast, the middle and lower parts universally develop thin
horizontal beddings, consisting of bedded and laminated structures
(Fig. 4bee). The horizontal bedding appears as the interactive dis-
tribution of light and dark lamellar layers. The dark lamellar layers
mainly consist of clay minerals, siliceous minerals, and organic
matter, whereas the light lamellar layers are mostly composed of
calcareous minerals. The lamellar layer thickness of the laminated
structure is much smaller than that of the bedded structure.
Moreover, the boundaries between the light and dark lamellar
layers of the laminated structure are much clearer than those of the
bedded structure.
4.4. Pore structure characteristics through FE-SEM observation
A great deal of complicated pores and fractures at the micro-
and nanoscale in the Esl3 shale samples were observed by FE-SEM.
These micro-nano pores can be divided into two types: organic
matter-hosted pores and mineral-hosted pores, with mineral-
hosted pores including intergranular pores and intraparticle
pores (Loucks et al., 2012).
4.4.1. Organic matter-hosted pores
Two typical types of organic matter-hosted pores were observed
in the shale samples, which is not considered and mentioned in
Zhang et al. (2016). One is that organic matter and inorganic min-
erals tend to form complexes in the form of adsorption, package,
and filling (Fig. 6aee). A large number of organic matter-hosted
pores with irregular polygonal shapes, covering a wide range of
sizes from 108 nm to 2.96 mm, are developed in the complexes. The
other is banded and polygonal organic matter that occurs in
isolation. At the boundaries between organic matter and inorganic
minerals, slit-shaped pores measuring 29e406 nm in diameter are
commonly developed, with a great length-width ratio, similar to
micro-fractures (Fig. 6feg). It is well known that organic matter-
hosted pores are closely related to the hydrocarbon generation of
organic matter. It may be due to the consumptions of organic
components and moisture during the hydrocarbon generation of
solid kerogen. It is also because that the accumulation of newly
generated liquids and gases results in the formation of bubbles.
Owing to the low thermal maturity of organic matter in the Esl3
shale, organic matter-hosted pores primarily exist in the above two
special forms, instead of honeycomb-like pores formed by the
sufficient hydrocarbon generation of organic matter with high
thermal maturity. Organic matter-hosted pores are connected with
mineral-hosted pores and provide reservoir space and permeable
channels for shale oil and gas (Jarvie et al., 2007; Loucks et al., 2009,
2012; Guo et al., 2014; Romero-Sarmiento et al., 2014).
676 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692

Fig. 4. Essential characteristics of the Esl3 shale in Zhanhua Sag. Calcareous minerals: calcite, dolomite, and siderite; Siliceous minerals: quartz and feldspar. a: 2932 m, massive
structure; b: 2942 m, bedded structure; c: 3040 m, laminated structure; d: 3110 m, laminated structure.

4.4.2. Intergranular pores reformed by sedimentation and metharmosis. It may be generated

Intergranular pores are predominantly developed around inor-
ganic mineral grains, which have large sizes of hundreds of nano-
metres and are mostly triangular, polygonal, and slit-shaped, being
the same as Zhang et al. (2016) observed by SEM (Fig. 7aeb). This
kind of pores is the residual space of mineral grains, which are
by the differences in compressive strength between plastic and
brittle minerals, such as clay and calcite (Fig. 7a). It may be also
caused by the mutual support of brittle mineral grains in the pro-
cess of mechanical compaction, such as calcite grains (Fig. 7aeb).
Owing to highly abundant brittle minerals, intergranular pores are
 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692
Fig. 5. Plot of the hydrogen index (HI) versus Tmax for the Esl3 shale in Zhanhua Sag.
well developed in the Esl3 shale. Intergranular pores present great
size and high connectivity, which make great contribution to the
storage and seepage of shale oil and gas (Yang et al., 2014; Jiao et al.,
2014; Cao et al., 2015).
4.4.3. Intraparticle pores
It can be observed by means of FE-SEM that intraparticle pores
are primarily developed within mineral grains. There are two types
of intraparticle pores in the shale samples. One is intercrystalline
pores that are developed among mineral crystals (such as clay and
pyrite) and formed by the loose accumulation of crystals in the
growing process. The other is dissolution pores that are generated
by organic acids dissolving unstable minerals (such as quartz,
feldspar, and calcite) in the process of hydrocarbon generation.
Organic acids generated during the thermal evolution of organic
matter could provide hydrogen ion and complex metallic elements
to improve the solubility of minerals and then result in the disso-
lution of minerals (Liu et al., 2006; Surdam et al., 1989). Intercrys-
talline pores in clay minerals mostly occur as triangular and
irregular polygonal shapes (Fig. 7c). Compared with intergranular
pores, they have small pore sizes with the minimum of 17 nm.
Intercrystalline pores in cluster-shaped pyrite are mainly irregular
polygonal, with nanoscale pore sizes (Fig. 7d). Due to generally
being associated with organic matter, most intercrystalline pores in
cluster-shaped pyrite are filled with organic matter. Dissolution
pores, dot-like and elliptical, have small pore sizes ranging from
84 nm to 232 nm with poor connectivity (Fig. 7eef). Since the Esl3
shale is rich in unstable minerals and organic matter is in the
maturity stage, dissolution pores are observed in the shale samples.
As Zhang et al. (2016) concluded, intraparticle pores with small
pore size make relatively limited contribution to the storage and
677
seepage properties of shale reservoirs.
4.4.4. Micro-fractures
Micro-fractures are closely related to internal stress produced
by dehydration, uniform shrinkage, and recrystallization of shale
reservoirs under overburden pressure during diagenesis (Ji et al.,
2016). A considerable number of micro-fractures are developed in
the inorganic minerals matrix, such as at the boundaries between
calcareous laminas and argillaceous laminas or inside calcareous
laminas (Fig. 7geh). These micro-fractures are relatively bent and
have a good extensibility, covering a wide range of widths from
192 nm to 1.04 mm. In addition, as Li et al. (2015) mentioned, owing
to the consumptions of organic components and moisture during
the hydrocarbon generation of solid kerogen, long and narrow
micro-fractures are commonly developed at the boundaries be-
tween organic matter and inorganic minerals, with the width of
hundreds of nanometres (Fig. 6h). Due to the characteristics of
highly abundant carbonate minerals, organic matter, and lamellar
layers, a great deal of micro-fractures are well developed in the Esl3
shale, which is an important feature of this study area. Like Zhang
et al. (2016) mentioned, micro-fractures interlinked to form
complicated fracture meshes could not only improve the perme-
ability of shale reservoirs, but also provide the favorable space for
hydrocarbon accumulation (Fig. 7h).
4.5. Pore structure characteristics through gas adsorption and MIP
analysis
It was shown that N2 adsorption and desorption isotherms
reflect pore shapes (De Boer and Lippens, 1964). The shapes of
adsorption/desorption isotherms in the samples are slightly
678 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692

Fig. 6. The morphology and distribution of organic matter-hosted pores and micro-fractures in the shale samples. a: a complex of organic matter and clay minerals, 3020 m; b: a
complex of organic matter and K-feldspar, 3025 m; c: a complex of organic matter and quartz, 3020 m; d: banded organic matter associated with pyrite, 3025 m; e: organic matter
filled in cluster-shaped pyrite, 3025 m; f: quadrangular organic matter distributed in calcite grains, 3110 m; g: slit-shaped organic matter-hosted pores developed at the boundaries
between banded organic matter and inorganic minerals, 2947 m; h: organic matter-hosted micro-fractures developed at the boundaries between banded organic matter and
inorganic minerals, 3020 m. OM: organic matter.
 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692 679

Fig. 7. The morphology and distribution of mineral-hosted pores and micro-fractures in the shale samples. a: wedge-shaped and polygonal intergranular pores around clay and
calcite grains, 3055 m; b: silt-shaped and irregular polygonal intergranular pores in calcite, 3055 m; c: intercrystalline pores in clay minerals, 3060 m; d: intercrystalline pores in
cluster-shaped pyrite, 2947 m; e: dissolution pores in calcite grains, 2947 m; f: dissolution pores in K-feldspar grains, 2947 m; g: micro-fractures developed in calcareous laminas or
at the boundaries between calcareous laminas and argillaceous laminas, 3020 m; h: complicated micro-fracture meshes, 3105 m.
680 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692
different, but generally have a characteristic of inverse-S shape
(Fig. 8). The adsorption branches change very slowly and show a
slightly upward convexity at low relative pressure (0 < P/P0 < 0.4).
However, the adsorption branches become steep and present an
obviously downward concave at high relative pressure (0.8 < P/
P0 < 1.0). There is no saturated adsorption at the saturated vapour
pressure, indicating the occurrence of capillary condensation
(Kondou and Ishikawa, 2006). As the phenomenon of capillary
condensation could only occur in the samples with macropores
(Kondou and IshikawaAbe, 2006), we infer that macropores are
developed in the shale samples. When the relative pressure is
greater than 0.4, hysteresis loops are generated by the noncoin-
cidence of the adsorption and desorption branches, reflecting the
development of mesopores in the shale samples. In addition, the
desorption branches generally become steep at medium relative
pressure, but the scarps of the desorption branches are not all
obvious. According to the classification of the IUPAC, the hysteresis
loops are close to type H3 and also have the characteristics of type
H2, respectively, corresponding to slit-shaped and ink-bottle-
shaped pores (Sing et al., 1985). It is concluded that the shale
samples are dominated by slit-shaped and ink-bottle-shaped
pores.
As the Esl3 shale has a very complicated pore structure, micro-
nano pore size distribution is obtained by the combination of CO2
adsorption, N2 adsorption, and MIP analysis. Because CO2 is able
to enter the 0.35 nm pores, CO2 adsorption analysis is primarily
used to obtain the distribution characteristics of micropores,
whose diameter range is less than 2 nm. It is generally known
that N2 adsorption makes use of capillary condensation to
calculate the pore size distribution. Only when the relative
pressure (P/P0) is greater than 0.35 can capillary condensation
occur. In addition, according to the Kelvin Equation, the larger the
pore is, the higher the relative pressure required for capillary
condensation is. When capillary condensation occurs in the large
pores, the relative pressure is close to the saturated vapour
pressure, which is difficult to measure in the experiment.
Therefore, there are upper and lower limits of the N2 adsorption
method, respectively 50 nm and 2 nm (Mastalerz et al., 2013;
Clarkson et al., 2013; Chen et al., 2011, 2016). MIP analysis is
used to acquire the distribution of pore size based on the number
of mercury molecular intrusion under high pressure. However,
the high pressure may cause induced fractures, sample defor-
mation, and compression of shale pores, affecting the results.
Thus, MIP is primarily used to analyse macropores, whose
diameter range is greater than 50 nm (Mastalerz et al., 2013; Ross
and Bustin, 2007; Katsube, 1992). According to the application
scope of the three methods, the pore size distribution of micro-
pores is obtained by CO2 adsorption, mesopores by N2 adsorp-
tion, and macropores by MIP analysis (Figs. 9 and 10).
Micropores, mesopores, and macropores are all well developed
in the shale samples. The total pore volume presents a very small
variation range (Table 2), showing two relatively stable peaks
(respectively, 0.5e0.9 nm and 10e15000 nm) (Fig. 9). As the pore
volume of macropores accounts for most of the total pore volume,
macropores make the greatest contribution to the total pore vol-
ume, followed by mesopores and micropores. In contrast, the total
surface area varies over a wide range and has a relatively stable
peak at the pore size of 0.5e0.9 nm (Fig. 10, Table 2). The total
surface area is mainly provided by micropores, especially the pores
with diameters of 0.5e0.9 nm. The surface area of macropores is
about three orders of magnitude smaller than that of micropores,
showing that macropores make the least contribution to the total
surface area.
5. Discussion
5.1. Characteristics of continental shale with typical lithofacies
According to the present situation in the study area, compre-
hensively taking TOC content, sedimentary structure, and mineral
composition into consideration, the Esl3 shale has developed into
five types of lithofacies: the organic-rich massive mixed shale
(ORMMS, TOC>2 wt%, massive structure, clay, siliceous, and
calcareous minerals contents all less than 50%), the organic-rich
bedded mixed shale (ORBMS, TOC>2 wt%, bedded structure, clay,
siliceous, and calcareous minerals contents all less than 50%), the
organic-rich bedded calcareous shale (ORBCS, TOC>2 wt%, bedded
structure, calcareous minerals content more than 50%), the organic-
rich laminated calcareous shale (ORLCS, TOC>2 wt%, laminated
structure, calcareous minerals content more than 50%), and the
organic-fair laminated calcareous shale (ORLCS, 1 wt%<TOC<2 wt%,
laminated structure, calcareous minerals content more than 50%).
ORMMS is distributed in the topmost part of the Esl3 Formation
(Fig. 4). ORBMS and ORBCS are distributed in the upper and middle
parts of the Esl3 Formation, with ORBMS distributed in the form of
thin interbeds between large sets of ORBCS. ORLCS and OFLCS are
distributed in the lower and lowermost parts of the Esl3 Formation,
respectively. Among these five types, ORBCS, ORLCS, and OFLCS are
the main lithofacies of the Esl3 Formation, accounting for 41%, 18%,
and 21%, respectively. Therefore, we focused on the eight samples
of typical shale lithofacies (ORBCS, ORLCS, and OFLCS) to analyse
the characteristics of pore structure.
ORBCS contains the highest proportions of clay and siliceous
minerals and the lowest calcareous minerals (Table 3). The organic
matter, with type I, possesses a medium content and the lowest
thermal maturity. The chloroform bitumen “A” presents the lowest
content, meaning that ORBCS possesses the least free hydrocarbon
content. ORBCS has a character of bedded structure, with relatively
poorly developed lamellar layers (Fig. 4b). Micro-nano pores are
dominated by slit-shaped and ink-bottle-shaped pores (Fig. 8aec).
The pore volume is the lowest of the three kinds of shale lithofacies
and possesses three relatively stable peaks, respectively,
0.5e0.9 nm, 10e40 nm, and 2000e15000 nm (Table 2 and
Fig. 9aec). The contributions of micropores, mesopores, and mac-
ropores to the total pore volume are approximately equivalent.
However, the surface area, which is mainly provided by micropores,
especially with diameters of 0.5e0.9 nm, is the largest of the three
kinds of typical lithofacies, (Table 2 and Fig. 10aec). Thus, ORBCS
develops mostly micropores, a medium amount of mesopores, and
the fewest macropores.
ORLCS possesses medium contents of clay, siliceous, and calcar-
eous minerals (Table 3). The organic matter has the highest content
and a medium thermal maturity, with Type I and II1. The chloroform
bitumen “A” shows the highest content, indicating that ORLCS bears
the most free hydrocarbon content. ORLCS is characterized by
laminated structure, with lamellar layers extremely well-developed
(Fig. 4c). Micro-nano pores are the result of a combination of slit-
shaped and ink-bottle-shaped pores (Fig. 8def). The pore volume
is the greatest of the three kinds of shale lithofacies and shows a
great peak at a diameter of 50e15000 nm (Table 2 and Fig. 9def).
Macropores show a large contribution to the total pore volume,
followed by mesopores and micropores. The medium surface area is
primarily contributed by micropores and presents a stable peak at
the diameters of 0.5e0.9 nm, but the contributions of mesopores and
macropores are slightly increased compared with ORBCS (Table 2
and Fig. 10def). Therefore, ORLCS develops mostly macropores, a
medium amount of micropores, and the fewest mesopores.
 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692 681

2.0 L1 1.0 L2
adsorption adsorption
1.8
Adsorption/desorption volume (ml/g)

Adsorption/desorption volume (ml/g)

desorption desorption
1.6 0.8

1.4

1.2 0.6

1.0

0.8 0.4

0.6

0.4 0.2

0.2

a 0.0 b 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
1.6 L3 1.6 L4
adsorption Relative pressure (P/P0 ) adsorptionRelative pressure (P/P0 )
Adsorption/desorption volume (ml/g)

Adsorption/desorption volume (ml/g)

desorption desorption

1.2 1.2

0.8 0.8

0.4 0.4

c 0.0 d 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
2.5 L5 3.0 L6
adsorption Relative pressure (P/P0 ) adsorptionRelative pressure (P/P0 )
Adsorption/desorption volume (ml/g)

Adsorption/desorption volume (ml/g)

desorption desorption
2.5
2.0

2.0
1.5

1.5

1.0
1.0

0.5
0.5

e 0.0 f 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
2.5 L7 5.0 L8
adsorption Relative pressure (P/P0 ) adsorptionRelative pressure (P/P0 )
4.5
Adsorption/desorption volume (ml/g)

Adsorption/desorption volume (ml/g)

desorption desorption
2.0 4.0

3.5

1.5 3.0

2.5

1.0 2.0

1.5

0.5 1.0

0.5

0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Relative pressure (P/P0 ) Relative pressure (P/P0 )
g h

Fig. 8. N2 adsorption/desorption isotherms at low temperature for the Esl3 shale samples. Blue: ORBCS; Red: ORLCS; Green: OFLCS. (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)
682 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692

0.0014 L1 0.0014 L2
micropores mesopores macropores micropores mesopores ma cropores
0.0012 0.0012

0.0010 0.0010
Pore volume (ml/g)

Pore volume (ml/g)

0.0008 0.0008

0.0006 0.0006

0.0004 0.0004

0.0002 0.0002

a 0.0000 b 0.0000

500-1000

500-1000
10000-15000

10000-15000
0.3-0.4
0.4-0.5
0.5-.06
0.6-0.7
0.7-0.8
0.8-0.9

1000-1500
0.9-1.0
1.0-1.1
1.1-1.2
1.2-1.3
1.3-1.4
1.4-1.5

50-100

1500-2000
2000-5000

0.3-0.4
0.4-0.5
0.5-.06
0.6-0.7
0.7-0.8
0.8-0.9
0.9-1.0
1.0-1.1
1.1-1.2
1.2-1.3
1.3-1.4
1.4-1.5

50-100

1000-1500
1500-2000
2000-5000
10-11
20-30
30-40
40-50

10-11
20-30
30-40
40-50
9-10

100-150
150-200
200-500

5000-10000

9-10

100-150
150-200
200-500

5000-10000
3-4
4-5
5-6
6-7
7-8
8-9

3-4
4-5
5-6
6-7
7-8
8-9
0.0014 L3 0.0014 L4
micropores mesopores macropores micropores mesopores ma cropores
0.0012 0.0012

0.0010 Pore size (nm) 0.0010 Pore size (nm)

Pore volume (ml/g)

Pore volume (ml/g)

0.0008 0.0008

0.0006 0.0006

0.0004 0.0004

0.0002 0.0002

c 0.0000 d 0.0000
500-1000

10000-15000

500-1000

10000-15000
0.3-0.4
0.4-0.5
0.5-.06
0.6-0.7
0.7-0.8
0.8-0.9
0.9-1.0
1.0-1.1
1.1-1.2
1.2-1.3
1.3-1.4
1.4-1.5

50-100

1000-1500
1500-2000
2000-5000

0.3-0.4
0.4-0.5
0.5-.06
0.6-0.7
0.7-0.8
0.8-0.9
0.9-1.0
1.0-1.1
1.1-1.2
1.2-1.3
1.3-1.4
1.4-1.5

50-100

1000-1500
1500-2000
2000-5000
10-11
20-30
30-40
40-50

10-11
20-30
30-40
40-50
9-10

100-150
150-200
200-500

5000-10000

9-10

100-150
150-200
200-500

5000-10000
3-4
4-5
5-6
6-7
7-8
8-9

3-4
4-5
5-6
6-7
7-8
8-9
0.0014 L5 0.0014 L6
micropores mesopores macropores micropores mesopores ma cropores
0.0012 0.0012

0.0010 Pore size (nm) 0.0010 Pore size (nm)

Pore volume (ml/g)

Pore volume (ml/g)

0.0008 0.0008

0.0006 0.0006

0.0004 0.0004

0.0002 0.0002

e 0.0000 f 0.0000
500-1000

10000-15000

500-1000

10000-15000
0.3-0.4
0.4-0.5
0.5-.06
0.6-0.7
0.7-0.8
0.8-0.9
0.9-1.0
1.0-1.1
1.1-1.2
1.2-1.3
1.3-1.4
1.4-1.5

50-100

1000-1500
1500-2000
2000-5000

0.3-0.4
0.4-0.5
0.5-.06
0.6-0.7
0.7-0.8
0.8-0.9
0.9-1.0
1.0-1.1
1.1-1.2
1.2-1.3
1.3-1.4
1.4-1.5

50-100

1000-1500
1500-2000
2000-5000
10-11
20-30
30-40
40-50

10-11
20-30
30-40
40-50
9-10

5000-10000
100-150
150-200
200-500

9-10

100-150
150-200
200-500

5000-10000
3-4
4-5
5-6
6-7
7-8
8-9

3-4
4-5
5-6
6-7
7-8
8-9

0.0014 L7 0.0014 L8
micropores mesopores macropores micropores mesopores ma cropores
0.0012 0.0012

0.0010 Pore size (nm) 0.0010 Pore size (nm)

Pore volume (ml/g)

Pore volume (ml/g)

0.0008 0.0008

0.0006 0.0006

0.0004 0.0004

0.0002 0.0002

0.0000 0.0000
500-1000

10000-15000

500-1000

10000-15000
0.3-0.4
0.4-0.5
0.5-.06
0.6-0.7
0.7-0.8
0.8-0.9
0.9-1.0
1.0-1.1
1.1-1.2
1.2-1.3
1.3-1.4
1.4-1.5

50-100

1000-1500
1500-2000
2000-5000

0.3-0.4
0.4-0.5
0.5-.06
0.6-0.7
0.7-0.8
0.8-0.9
0.9-1.0
1.0-1.1
1.1-1.2
1.2-1.3
1.3-1.4
1.4-1.5

50-100

1000-1500
1500-2000
2000-5000
10-11
20-30
30-40
40-50

10-11
20-30
30-40
40-50
9-10

100-150
150-200
200-500

5000-10000

9-10

100-150
150-200
200-500

5000-10000
3-4
4-5
5-6
6-7
7-8
8-9

3-4
4-5
5-6
6-7
7-8
8-9

Pore size (nm) Pore size (nm)

g h

Fig. 9. Pore volume distribution of the Esl3 shale samples. The micropores are determined from CO2 adsorption data, the mesopores from N2 adsorption data, and the macropores
from MIP data. Blue: ORBCS; Red: ORLCS; Green: OFLCS. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

OFLCS has the least contents of clay and siliceous minerals and
the highest content of calcareous minerals (Table 3). The organic
matter shows the lowest content and the highest thermal maturity,
with Type II1 and II2. The chloroform bitumen “A” shows a medium
content, signifying that OFLCS contains a medium free hydrocarbon
content. Like ORLCS, OFLCS is distinguished by laminated structure,
but the thickness of lamellar layers is greater than that of ORLCS
(Fig. 4d). Micro-nano pores are predominant by ink-bottle-shaped
pores, with a small amount of slit-shaped pores (Fig. 8geh). The
pore volume, a medium average, possesses a double-peak feature at
10e40 nm and 200e15000 nm, respectively (Table 2 and
Fig. 9geh). Macropores and mesopores provide the main pore
 e
c
a

g
Pore surface area (m2 /g) Pore surface area (m2 /g) Pore surface area (m2 /g) Pore surface area (m2 /g)

0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.3-0.4 0.3-0.4 0.3-0.4 0.3-0.4
0.4-0.5 0.4-0.5 0.4-0.5 0.4-0.5
0.5-.06 0.5-.06 0.5-.06 0.5-.06
0.6-0.7 0.6-0.7 0.6-0.7 0.6-0.7
0.7-0.8 0.7-0.8 0.7-0.8 0.7-0.8
0.8-0.9 0.8-0.9 0.8-0.9 0.8-0.9
0.9-1.0 0.9-1.0 0.9-1.0 0.9-1.0
1.0-1.1 1.0-1.1 1.0-1.1 1.0-1.1

micropores
micropores
micropores
micropores

1.1-1.2 1.1-1.2 1.1-1.2 1.1-1.2

1.2-1.3 1.2-1.3 1.2-1.3 1.2-1.3
1.3-1.4 1.3-1.4 1.3-1.4 1.3-1.4
1.4-1.5 1.4-1.5 1.4-1.5 1.4-1.5
3-4 3-4 3-4 3-4
4-5 4-5 4-5 4-5
5-6 5-6 5-6 5-6
6-7 6-7 6-7 6-7
7-8 7-8 7-8 7-8
8-9 8-9 8-9 8-9
9-10 9-10 9-10 9-10

Pore size (nm)

Pore size (nm)
Pore size (nm)
Pore size (nm)
10-11 10-11 10-11 10-11

mesopores
mesopores
mesopores
mesopores

20-30 20-30 20-30 20-30

30-40 30-40 30-40 30-40
40-50 40-50 40-50 40-50
50-100 50-100 50-100 50-100
100-150 100-150 100-150 100-150
150-200 150-200 150-200 150-200
200-500 200-500 200-500 200-500

dium amount of macropores, and the fewest micropores.

500-1000 500-1000 500-1000 500-1000
1000-1500 1000-1500 1000-1500 1000-1500
1500-2000 1500-2000 1500-2000 1500-2000
2000-5000 2000-5000 2000-5000 2000-5000

macropores
macropores
macropores
macropores

5000-10000 5000-10000 5000-10000 5000-10000

volume and micropores contribute the least. However, the surface

Fig. 10geh). As a result, OFLCS develops mostly mesopores, a me-

pores with diameters of 0.5e0.9 nm and 10e40 nm (Table 2 and
mainly contributed by micropores and mesopores, especially the
area, which is the least in the three types of shale lithofacies, is
L7
L5
L3
L1

10000-15000 10000-15000 10000-15000 10000-15000

h
d
b

Pore surface area (m2 /g) Pore surface area (m2 /g) Pore surface area (m2 /g) Pore surface area (m2 /g)

0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2

0.3-0.4 0.3-0.4 0.3-0.4 0.3-0.4

0.4-0.5 0.4-0.5 0.4-0.5 0.4-0.5
0.5-.06 0.5-.06 0.5-.06 0.5-.06
0.6-0.7 0.6-0.7 0.6-0.7 0.6-0.7
0.7-0.8 0.7-0.8 0.7-0.8 0.7-0.8
0.8-0.9 0.8-0.9 0.8-0.9 0.8-0.9
0.9-1.0 0.9-1.0 0.9-1.0 0.9-1.0
1.0-1.1 1.0-1.1 1.0-1.1 1.0-1.1

micropores
micropores
micropores
micropores

1.1-1.2 1.1-1.2 1.1-1.2 1.1-1.2

1.2-1.3 1.2-1.3 1.2-1.3 1.2-1.3
1.3-1.4 1.3-1.4 1.3-1.4 1.3-1.4
1.4-1.5 1.4-1.5 1.4-1.5 1.4-1.5
T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692

3-4 3-4 3-4 3-4

4-5 4-5 4-5 4-5
5-6 5-6 5-6 5-6
6-7 6-7 6-7 6-7
7-8 7-8 7-8 7-8
8-9 8-9 8-9 8-9
9-10 9-10 9-10 9-10

Pore size (nm)

Pore size (nm)
Pore size (nm)
Pore size (nm)

10-11 10-11 10-11 10-11

mesopores
mesopores
mesopores
mesopores

20-30 20-30 20-30 20-30

30-40 30-40 30-40 30-40
40-50 40-50 40-50 40-50
50-100 50-100 50-100 50-100
100-150 100-150 100-150 100-150
150-200 150-200 150-200 150-200
200-500 200-500 200-500 200-500
500-1000 500-1000 500-1000 500-1000
1000-1500 1000-1500 1000-1500 1000-1500
1500-2000 1500-2000 1500-2000 1500-2000
2000-5000 2000-5000 2000-5000 2000-5000
ma cropores
ma cropores
ma cropores
ma cropores

5000-10000 5000-10000 5000-10000 5000-10000

L8
L6
L4
L2

10000-15000 10000-15000 10000-15000 10000-15000

injection/withdrawal curves present different characteristics

from MIP data. Blue: ORBCS; Red: ORLCS; Green: OFLCS. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 10. Surface area distribution of the Esl3 shale samples. The micropores are determined from CO2 adsorption data, the mesopores from N2 adsorption data, and the macropores

drawal curves of ORLCS decrease quickly, indicating high mercury

In addition, when comparing ORLCS with OFLCS their mercury

under high pressure (Fig. 11a). Additionally, the mercury with-

683

approximately 100 MPa, with a great volume of mercury injection

(Fig. 11). The mercury injection curves of ORLCS increase rapidly
684 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692

withdrawal efficiency. The high mercury withdrawal efficiency

Note: The pore volume of micropores is obtained by CO2 adsorption, mesopores by N2 adsorption, and macropores by MIP. The total pore volume is the sum of the pore volumes of micropores, mesopores, and macropores. The
Macropore
reflects that ORLCS presents good pore connectivity and flow ca-
Proportion of pore surface area (%) pacity. In contrast, the cumulative mercury injection volume of

0.17
0.23
0.31
0.22

2.78
0.63
1.03
1.48

1.02
0.20
0.61

0.82

pore volume proportions of micropores, mesopores, and macropores are equal to the total pore volume divided by the pore volumes of micropores, mesopores, and macropores, respectively. So is the surface area.
OFLCS is considerably smaller than that of ORLCS, though the
mercury injection curves become steep at approximately 100 MPa
as well (Fig. 11b). The mercury withdrawal curves decrease slowly
Mesopore

10.68 with the decreasing pressure and even have no change at the initial

13.63
12.24
11.09

18.18
28.32
23.25

11.30
8.08
4.70

7.46

7.39
stage, which represents small mercury withdrawal efficiency. It
may be because substantial ink-bottle-shaped pores and the lack of
micro-fractures lead to bad connectivity and permeability.
Micropore

91.75
95.07
89.01
92.32

89.83
85.74
86.73
87.43

80.80
71.48
76.14

87.87
5.2. Differences between continental and marine shales in pore
structure
Total

4.01
2.68
1.53
2.74

3.10
2.76
1.61
2.49

1.26
2.29
1.78

2.45
Shale reservoirs formed in different sedimentary environments
show significant differences in pore structure. Considering that the
Longmaxi marine shale in Sichuan Basin, south China is a typical
Macropore

example of marine shale in China, the pore structure features of the

Esl3 shale are compared with those of the Longmaxi shale to discuss
0.007
0.006
0.005
0.006

0.086
0.017
0.017
0.040

0.013
0.005
0.009

0.020

differences between continental and marine shales in pore

structure.
Mesopore

The total pore volume of the Longmaxi shale presents three

Pore surface area (m2/g)

relatively stable peaks, 0.3e0.6 nm, 1.5e4.0 nm, and

0.32
0.13
0.16
0.20

0.23
0.38
0.20
0.27

0.23
0.65
0.44

0.28

10000e15000 nm, which is primarily provided by micropores and

mesopores (accounting for 34.70% and 40.83% respectively)
(Table 4). Macropores make the least contribution to the total pore
Micropore

volume, only accounting for 24.46%. The total surface area of the
3.68
2.55
1.36
2.53

2.78
2.37
1.40
2.18

1.02
1.64
1.33

2.15

Longmaxi shale shows a relatively stable peak (0.3e0.6 nm). Mi-

cropores make the greatest contribution to the total surface area,
up to 76.87%. Compared with the Esl3 shale, the contribution of
Macropore

mesopores to the total surface area presents an increase, account-

23.62
39.58
53.25
37.57

80.58
53.37
76.80
70.25

65.36
44.67
55.02

60.61

ing for 23.05% (Jiang et al., 2016; Wang et al., 2016a, b; Tang et al.,
2015, 2016b).
Proportion of pore volume (%)

Comparing the data of the two formations, it can concluded that

Mesopore

micropores are well developed in the Longmaxi shale while mac-

ropores are well developed in the Esl3 shale. Owing to high thermal
32.32
18.35
26.60
26.46

26.71
13.95
16.10

24.32
43.80
34.06

21.26
7.63

maturity, organic matter in the Longmaxi shale generates a large

amount of gas during the sufficient hydrocarbon generation. As a
result, there are abundant interconnected honeycomb-like pores
Micropore

within organic matter. This kind of organic matter-hosted pores

44.06
42.07
20.15
35.96

11.78
19.93

13.65

10.32
11.53
10.92

18.13
9.25

possesses small pore size and mostly belongs to micropores, which

could greatly increase the pore surface area of shale reservoirs. In
contrast, for the Esl3 shale, the interconnected honeycomb-like
0.00315
0.00232
0.00251
0.00266

0.00851
0.00424
0.00565
0.00613

0.00361
0.00499
0.00430

0.00438

pores are not observed inside organic matter, since organic mat-
Total

ter possesses low thermal maturity and tends to generate oil.

Organic matter-hosted pores in the Esl3 shale show large pore size
and primarily belong to macropores (Fig. 6), which make great
Macropore
Pore volume and surface area parameters of the shale samples.

0.00074
0.00092
0.00134
0.00100

0.00686
0.00226
0.00434
0.00449

0.00236
0.00223
0.00230

0.00265

contribution to the pore volume of shale reservoirs. In addition,

highly abundant micro-fractures lead to the development of mac-
ropores in the Esl3 shale samples.
It is generally known that adsorbed hydrocarbon is primarily
Mesopore

attached to the surfaces of organic matter and inorganic mineral,

0.00102
0.00043
0.00067
0.00070

0.00065
0.00113
0.00079
0.00086

0.00088
0.00219
0.00153

0.00093

whereas free hydrocarbon mainly occurs in the pores and micro-

Pore volume (ml/g)

fractures of shale reservoirs. Therefore, the content of adsorbed

hydrocarbon is closely related to surface area, whereas the content
Micropore

of free hydrocarbon is primarily controlled by pore volume.

0.00139
0.00098
0.00051
0.00096

0.00100
0.00084
0.00052
0.00079

0.00037
0.00058
0.00047

0.00079

For the Longmaxi shale, the methane adsorption content grad-

ually grows with the surface area of micropores increasing
(Fig. 12a). The surface area of mesopores and macropores shows
poor correlation with the methane adsorption content, meaning
Samples Number

that mesopores and macropores are inconclusive for the methane

Total Mean

adsorption content due to the limited surface area of mesopores

and macropores. Therefore, micropores with large surface area
Mean

Mean

Mean
Table 2

have a crucial effect on the adsorbed gas content.

L1
L2
L3

L4
L5
L6

L7
L8

In contrast, for the Esl3 shale, the chloroform bitumen “A”

 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692 685

Table 3
Essential characteristic parameters of the eight shale samples.

Samples Number Lithofacies Depth (m) Organic matter Mineral composition (%)

TOC content (wt%) Ro (%) Chloroform bitumen “A” (%) Type Siliceous minerals Calcareou minerals Clay minerals Pyrite

L1 ORBCS 2947 2.44 0.79 0.29 I 22 56 18 4

L2 2962 2.58 0.72 0.27 I 19 54 25 2
L3 3025 3.70 0.79 0.62 I 21 51 23 5
Mean e 2.91 0.77 0.39 e 20.67 53.67 22.00 3.67

L4 ORLCS 3055 5.63 0.80 1.13 I 18 64 15 3

L5 3060 4.55 0.83 0.77 II1 18 69 10 3
L6 3105 3.21 0.85 0.92 II1 19 63 14 4
Mean e 4.46 0.82 0.94 e 18.33 65.00 13.00 3.67

L7 OFLCS 3110 1.40 0.87 0.42 II1 12 76 9 3

L8 3120 1.42 0.91 0.62 II2 5 89 5 1
Mean e 1.41 0.89 0.52 e 8.50 82.50 7.00 2.00

Total Mean e e 3.23 0.81 0.63 e 17.30 63.97 15.40 3.33

0.020 0.020
mercury injection mercury injection
Cumulative intrusion/extrusion volume (ml/g)

Cumulative intrusion/extrusion volume (ml/g)

mercury withdrawal L4:MWE mercury withdrawal
30%
0.015 0.015

L6:MWE
16%
0.010 0.010
L5:MWE
33% L7:MWE
7%
0.005 0.005
L8:MWE
11%

0.000 0.000
0.01 0.1 1 10 100 1000 0.01 0.1 1 10 100 1000
Pressure (MPa) Pressure (MPa)
a b

Fig. 11. MIP of the Esl3 shale samples. MWE: mercury withdrawal efficiency.

Table 4
Differences between the Longmaxi marine shale and the Esl3 continental shale in pore structure.

Formations Longmaxi marine shale Esl3 continental shale

Parameters

Ro (%) 1.93e3.59 0.70e0.91

Hydrocarbon Gas Oil
Honeycomb-like organic matter-hosted pores Well developed Undeveloped
Pore size range of pore volume peak 3.0e0.6 nm, 1.5e4.0 nm, 10000e15000 nm 0.5e0.9 nm, 10e15000 nm
Pore size range of surface area peak 0.3e0.6 nm 0.5e0.9 nm
Proportion of pore volume (%) Micropores 34.70 18.13
Mesopores 40.83 21.26
Macropores 24.46 60.61
Proportion of surface area (%) Micropores 76.87 87.87
Mesopores 23.05 11.30
Macropores 0.07 0.82

content shows a linearly increasing trend with the pore volume of decisive role in free hydrocarbon accumulation.
macropores while chloroform bitumen “A” content has poor cor- Consequently, micropores well-developed in the Longmaxi
relation with the pore volume of micropores and mesopores shale are favorable for shale gas adsorption, since they could pro-
(Fig. 12b). It means that micropores and mesopores have no vide enough surface area. In contrast, macropores well-developed
determinate role for free hydrocarbon accumulation, since micro- in the Esl3 shale are propitious to free hydrocarbon accumulation,
pores and mesopores make limited contribution to the pore vol- since they could offer enough pore volume. Based on the compar-
ume. Consequently, macropores with large pore volume play a ative analysis, continental shale is completely different from
686 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692
Fig. 12. a: Relationship between CH4 adsorption content and surface area of the Longmaxi shale (according to Jiang et al., 2016); b: Relationship between chloroform bitumen “A”
content and pore volume of the Esl3 shale (The data of chloroform bitumen “A” content is obtained from Soxhlet extraction. The pore volume of micropores is determined from CO2
adsorption, the mesopores from N2 adsorption, and the macropores from MIP.).
marine shale in pore structure. The Esl3 continental shale can
represent a kind of continental shale which has the characteristic of
low thermal maturity, hoping that our study could provide certain
reference for shale reservoirs with similar characteristics.
5.3. Controlling factors of pore structure
Due to the comprehensive effects of mineral composition, TOC
content, thermal maturity, and sedimentary structure, the Esl3 shale
possesses extremely complicated micro-nano pore structure.
Analysing the relationship between pore structure parameters
and controlling factors, it is found that the pore structure param-
eters of micropores show a linearly increasing trend with the in-
crease of clay and siliceous minerals contents, whereas they show a
linearly decreasing trend with the increase of calcareous minerals
content (Fig. 13aef). Conversely, the pore structure parameters of
mesopores present a linearly decreasing trend with the increase of
clay and siliceous minerals contents, but a linearly increasing trend
with the increase of calcareous minerals content (Fig. 14aef). In
other words, clay and siliceous minerals are both favourable for
micropores, whereas calcareous minerals are conducive to meso-
pores. Since calcareous minerals tend to form a relatively rigid
framework that improves the compression strength of shale res-
ervoirs, they are advantageous to the preservation of large pores
(Jarvie et al., 2007; Rickman et al., 2008; Sondergeld et al., 2010; Ji
et al., 2016). As a result, mesopores are primarily contributed by
calcareous minerals, such as intergranular pores and dissolution
pores in calcite (Fig. 7 aeb and e), whereas micropores are mainly
provided by clay and siliceous minerals, such as intercrystalline
pores in clay minerals and dissolution pores in siliceous minerals
(Fig. 7c and f).
Compared with micropores and mesopores, the correlations
between the pore volume of macropores and controlling factors are
relatively complicated, indicating that the development of macro-
pores is controlled by various factors. However, the correlation
between the pore volume of macropores and mineral composition
shows an obvious regularity. The pore volume of macropores be-
comes greater first and then smaller with the increasing clay, sili-
ceous, and calcareous minerals contents (Fig. 15a, c and e). On the
whole, the pore volume of macropores presents a decreasing trend
with the increase of clay and siliceous minerals but an increasing
trend with the increase of calcareous minerals. In other words, clay
and siliceous minerals are both unfavourable to macropores,
whereas calcareous minerals are favourable to macropores.
However, only when the carbonate minerals content is much
higher and simultaneously the contents of clay and siliceous min-
erals reach certain amounts will the pore volume be a relatively
high value. As Li et al. (2015) concluded, calcareous minerals tend to
develop large intergranular pores and generate micro-fractures
under very slight stress, which makes for the development of
macropores (Fig. 7a, b and g). Due to the differences in mechanical
properties between argillaceous and calcareous laminas, there are
considerable micro-fractures at the contact between the two kinds,
leading to significant increases in the pore volume and connectivity
(Fig. 7g) (Jarvie et al., 2007; Rickman et al., 2008; Sondergeld et al.,
2010; Ji et al., 2016; Slatt and O'Brien, 2011; Jiang et al., 2015). Only
when the contents of clay and silicate minerals reach certain values
can frequent interactive distribution of argillaceous and calcareous
laminas be guaranteed. Additionally, the surface area of macro-
pores shows no significant correlation with mineral composition,
proving that macropores make little contribution to the surface
area (Fig. 15b, d and f).
Moreover, the pore structure parameters of micropores and
mesopores have no typical correlation with the TOC content,
whereas the pore structure parameters of macropores possess a
linearly increasing trend with the increase of TOC content
(Fig. 13geh, 14geh, 15geh). It is demonstrated that organic matter
is in favour of macropores, owing to large pores in the complexes of
organic matter and inorganic minerals or micro-fractures at the
boundaries between strip-shaped organic matter and inorganic
minerals (Fig. 6). The lack of correlation between the pore structure
parameters of micropores/mesopores and TOC content may be
because that interconnected honeycomb-like organic matter-
hosted pores with small pore size are not developed in the shale
samples. Moreover, the residual hydrocarbon blocked off the mi-
cropores and mesopores in the shale samples (Pan et al., 2015; Luo
and He, 2014; Furmann et al., 2013; Ross and Bustin, 2009).
In addition, the pore structure parameters of micropores show a
linearly decreasing trend with the increase of thermal maturity,
whereas the pore structure parameters of mesopores possess a
linearly increasing trend with the increase of thermal maturity
(Fig. 13iej, 14iej). This finding may be because as thermal maturity
increases, organic acids released by hydrocarbon generation further
dissolve inorganic mineral particles, leading to the increase of pore
size (Schieber, 2010; Loucks et al., 2012; Yuan et al., 2013). Being the
same as the correlation between the pore structure parameters of
macropores and mineral composition, the pore volume of macro-
pores increases first and then decreases with an increase in thermal
 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692 687

0.0016 4.0

0.0014 3.5

0.0012 3.0

Pore surface area (m /g)

Pore volume (ml/g)
0.0010 2.5

0.0008 2.0

0.0006 1.5

0.0004 1.0

0.0002 0.5

0.0000 0.0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Clay minerals content (%) Clay minerals content (%)
a b

0.0016 4.0

0.0014 3.5

0.0012 3.0

Pore surface area (m /g)

Pore volume (ml/g)

0.0010 2.5

0.0008 2.0

0.0006 1.5

0.0004 1.0

0.0002 0.5

0.0000 0.0
0 5 10 15 20 25 0 5 10 15 20 25
Siliceous minerals content (%) Siliceous minerals content (%)
c d
0.0016 4.0

0.0014 3.5

0.0012 3.0
Pore surface area (m /g)
Pore volume (ml/g)

0.0010 2.5

0.0008 2.0

0.0006 1.5

0.0004 1.0

0.0002 0.5

0.0000 0.0
40 50 60 70 80 90 100 40 50 60 70 80 90 100
Calcareous minerals content (%) Calcareous minerals content (%)
e f

0.0016 4.0

0.0014 3.5

0.0012 3.0
Pore surface area (m /g)
Pore volume (ml/g)

0.0010 2.5

0.0008 2.0

0.0006 1.5

0.0004 1.0

0.0002 0.5

0.0000 0.0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
TOC (%) TOC (%)
g h
0.0016 4.0

0.0014 3.5

0.0012 3.0
Pore surface area (m /g)
Pore volume (ml/g)

0.0010 2.5

0.0008 2.0

0.0006 1.5

0.0004 1.0

0.0002 0.5

0.0000 0.0
0.5 0.6 0.7 0.8 0.9 1.0 0.5 0.6 0.7 0.8 0.9 1.0
Ro (%) Ro (%)
i j

Fig. 13. Correlations between the pore structure parameters of micropores and mineral composition, TOC content, thermal maturity in the shale samples.
688 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692

0.0025 0.7

0.6
0.0020

Pore surface area (m /g)

0.5

Pore volume (ml/g)

0.0015
0.4

0.3
0.0010

0.2
0.0005
0.1

0.0000 0.0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Clay minerals content (%) Clay minerals content (%)
a b

0.0025 0.7

0.6
0.0020

Pore surface area (m /g)

0.5
Pore volume (ml/g)

0.0015
0.4

0.3
0.0010

0.2
0.0005
0.1

0.0000 0.0
0 5 10 15 20 25 0 5 10 15 20 25
Siliceous minerals content (%) Siliceous minerals content (%)
c d

0.0025 0.7

0.6
0.0020
Pore surface area (m /g)

0.5
Pore volume (ml/g)

0.0015
0.4

0.3
0.0010

0.2
0.0005
0.1

0.0000 0.0
40 50 60 70 80 90 100 40 50 60 70 80 90 100
Calcareous minerals content (%) Calcareous minerals content (%)
e f

0.0025 0.7

0.6
0.0020
Pore surface area (m /g)

0.5
Pore volume (ml/g)

0.0015
0.4

0.3
0.0010

0.2
0.0005
0.1

0.0000 0.0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
TOC (%) TOC (%)
g h

0.0025 0.7

0.6
0.0020
Pore surface area (m /g)

0.5
Pore volume (ml/g)

0.0015
0.4

0.3
0.0010

0.2
0.0005
0.1

0.0000 0.0
0.5 0.6 0.7 0.8 0.9 1.0 0.5 0.6 0.7 0.8 0.9 1.0
Ro (%) Ro (%)
i j

Fig. 14. Correlations between the pore structure parameters of mesopores and mineral composition, TOC content, thermal maturity in the shale samples.
 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692 689

Fig. 15. Correlations between the pore structure parameters of macropores and mineral composition, TOC content, thermal maturity in the shale samples.
690 T. Li et al. / Journal of Natural Gas Science and Engineering 45 (2017) 670e692
maturity (Fig. 15i). It is also demonstrated that the development of
lamellar layers has a significant effect on macropores. Moreover,
the pore volume of macropores has an increasing trend with the
increase of thermal maturity as a whole. It means that with the
thermal evolution of organic matter, a large number of organic
matter-hosted pores and micro-fractures are developed by hydro-
carbon generation (Jarvie et al., 2007; Xue et al., 2015; Yang et al.,
2014; Huang and Shen, 2015; Ji et al., 2016). The surface area of
macropores has no correlation with thermal maturity (Fig. 15j),
indicating that macropores make little contribution to the surface
area as well.
The pore structure parameters of micropores, mesopores, and
macropores are all irrelevant to pyrite content. Although pyrite is
developed in the shale samples, it is a small amount with an
average of 3.33% and the cluster-shaped pyrite is almost filled with
organic matter and inorganic minerals (Figs. 4, 6dee, Table 3).
Therefore, due to the poor development of effective pores, pyrite
has hardly any contribution to the pore volume and surface area.
From the above analysis, it can be concluded that micropores
and mesopores are primarily controlled by mineral composition
and thermal maturity, whereas macropores are dominated by
mineral composition, TOC content, thermal maturity, and espe-
cially lamellar layers. Based on the comprehensive influence of
mineral composition, TOC content, thermal maturity, and lamellar
layers, for the three typical lithofacies, micropores are developed
most in ORBCS, whereas mesopores in OFLCS, macropores in
ORLCS. As ORLCS has a large pore volume and mercury withdrawal
efficiency, it is a favourable lithofacies for the storage and flow of
shale oil and gas. Therefore, the key work of shale oil and gas
exploration and development in the study area should be focused
on seeking the distribution zones of ORLCS.
6. Conclusions
A series of laboratory experiments were performed to investi-
gate the pore structure and its controlling factors in the lower third
member of the Shahejie Formation, Zhanhua Sag, Jiyang Depres-
sion, Bohai Bay Basin, Eastern China. The following key conclusions
are reached:
(1) The Esl3 continental shale in the study area is characterized
by high calcareous minerals, low siliceous minerals, low clay
minerals, low TOC content, low thermal maturity, organic
matter of Type I and II, and the general development of
horizontal bedding.
(2) Various types of reservoir space, such as organic matter-
hosted pores, intergranular pores, intraparticle pores, and
micro-fractures, are developed in the shale samples. The
shale samples are dominated by slit-shaped and ink-bottle-
shaped pores. The total pore volume presents two rela-
tively stable peaks at 0.5e0.9 nm and 10e15000 nm,
respectively, which is mainly contributed by macropores.
Conversely, the total surface area is mostly provided by mi-
cropores, especially the pores with diameters of 0.5e0.9 nm.
(3) In the three kinds of typical lithofacies, ORLCS with a greater
pore volume, surface area, and connectivity is the favourable
lithofacies for the storage and flow of shale oil and gas, and it
should be the key research object of shale oil and gas
exploration and development in the study area.
(4) Micropores well-developed in the Longmaxi shale are
favorable for shale gas adsorption. In contrast, macropores
well-developed in the Esl3 shale are propitious to free hy-
drocarbon accumulation.
(5) Mineral composition and thermal maturity have a significant
effect on micropores and mesopores. However, mineral
composition, TOC content, thermal maturity, and lamellar
layers all play important roles in the development of
macropores.
Acknowledgments
The authors are grateful to all the editors and anonymous re-
viewers for their constructive suggestions and comments that have
significantly improved the manuscript. This study was supported
by the National Basic Research Programme of China (973 Project)
(NO.2014CB239105). The authors are indebted to the Geoscience
Institute of Shengli Oilfield Company, Sinopec who supplied us
with the drill cores and basis data used in this study. The authors
are grateful to Dr. Yuan Yuan from the Chinese Academy of Sciences
and M.S. Weitao Chen and M.S. Zhi Wang from China University of
Petroleum for their help in this study. The authors would also like
to thank Elsevier (webshop.elsevier.com) for the English language
review.
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