Marine and Petroleum Geology 107 (2019) 407–422

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Marine and Petroleum Geology

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

Research paper

Pore connectivity and water accessibility in Upper Permian transitional T

shales, southern China
Mengdi Suna,b, Linhao Zhanga, Qinhong Huc, Zhejun Pana,b,∗, Bingsong Yud, Liangwei Sune,
Liangfei Baie, Luke D. Connellb, Yifan Zhangd, Gang Chengf,∗∗
a
Key Laboratory of Tectonics and Petroleum Resources, Ministry of Education, China University of Geosciences, Wuhan 430074, China
b
CSIRO Energy, Private Bag 10, Clayton South, VIC 3169, Australia
c
Department of Earth and Environment Sciences, University of Texas at Arlington, Arlington, TX 76019, USA
d
School of Earth Sciences and Resources, China University of Geosciences, Beijing 100083, China
e
Key Laboratory of Neutron Physics and Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics (CAEP), Mianyang 621999, China
f
College of Life Science and Technology, Beijing University of Chemical Technology, Beijing 100029, China

A R T I C LE I N FO A B S T R A C T

Keywords: Pore connectivity of shale controls shale gas migration and production behavior. The pore connectivity and
Transitional shale water accessibility in clay-rich Upper Permian transitional shales remain unclear. Contrast matching small-angle
Pore connectivity neutron scattering (CM-SANS) tests were used to determine the accessibility of water to pores in the transitional
Water accessibility shales. Complementary analyses with SANS, gas (CO2 and N2) physisorption isotherm, mercury intrusion ca-
Small angle neutron scattering
pillary pressure (MICP), helium ion microscopy (HIM), as well as field emission-scanning electron microscopy
Contrast matching
(FE-SEM) were conducted to study the pore connectivity and distribution characteristics of closed pores. The
results show that closed pores (inaccessible to nitrogen molecules and mercury) are mainly distributed in pore
diameters ＜10 nm and associated with organic pores and interlayer spaces of illite-smectite mixed-layer mi-
neral. The pore volume values obtained from MICP and N2 adsorption underestimate the large pores (pore
diameters ＞100 nm) in shales. Based on deuterated water CM-SANS tests, 87–98% of the pores (2–200 nm
diameters) are water-connected in transitional samples. The low accessibility to water is at pore-sizes of 5–10 nm
and 20–30 nm. Results from in-situ gas contents show that closed pores have a certain gas bearing capacity, but
micropores (pore diameters ＜2 nm) control the gas occurrence in transitional samples. The connectivity of the
organic pore network and between organic pores and surrounding interparticle pores is directly supported by FE-
SEM and HIM imaging. Overall, improving pore-fracture connectivity through effective fracturing techniques is a
means of mitigating the rapid decline in shale gas production.

1. Introduction Carboniferous-Permian shales developed in northern and northwestern

Shale gas industry in China has entered the stage of commercial
exploitation since 2014 (Guo, 2015). Up until the end of 2018, the
Fuling gas field in southern China has produced more than 20 billion
cubic meters of shale gas from overmature marine shales. Given the
successful research and development of marine shale in United States,
Chinese industry and academics are more focused on marine shales in
the Sichuan Basin and its neighboring areas (Hao et al., 2013; Zhang
et al., 2016, 2018). China has three types of organic-rich shales (by
area: marine shale 26%, lacustrine shale 18%, and marine-terrestrial
transitional shale 56%). Marine-terrestrial transitional shales mainly
include Permian Longtan Formation shales of southern China and
China (Zhang and Fu, 2018). Upper Permian transitional shales were
mainly deposited in coastal swamp environment. It resulted in rapid
changes in lithofacies with interlayers of coal beds or fine sandstone
(Mani et al., 2015; Pan et al., 2015). The vast geological distribution
area and multiple gas sources (shale, coalbed, and tight-sand gas) of
transitional shales provide many opportunities for shale gas exploration
and development in China.
Some comparative studies have carried out between transitional
shale and marine shale (Mao and Guo, 2018; Yang et al., 2017). The
transitional shales exampled by Upper Permian shales have more clay
content (usually＞50%) than that of marine shales, and high to over
maturity (Jiang et al., 2017). With the pore structures characterized by

∗
Corresponding author. Key Laboratory of Tectonics and Petroleum Resources, Ministry of Education, China University of Geosciences, Wuhan 430074, China..
∗∗
Corresponding author..
E-mail addresses: Zhejun.Pan@csiro.au (Z. Pan), chenggang@mail.buct.edu.cn (G. Cheng).

https://doi.org/10.1016/j.marpetgeo.2019.05.035
Received 7 March 2019; Received in revised form 25 April 2019; Accepted 27 May 2019
Available online 30 May 2019
0264-8172/ © 2019 Elsevier Ltd. All rights reserved.
M. Sun, et al.
Fig. 1. Location map of sampling wells in southern China (modified after Sun et al., 2017a,b).
field emission-scanning electron microscopy (FE-SEM), mercury intru-
sion, and low-pressure nitrogen physisorption (LPNP), transitional
shales have a larger average pore size and a higher heterogeneity of OM
pore development, compared with marine shales (Ju et al., 2018; Zhang
et al., 2017). The studies on the pore structures of the transitional shales
have mainly focused on geometrical attributes and size distribution of
pores. However, closed pore (inaccessible to fluids) characteristics and
pore connectivity in the shale matrix is still poorly understood.
The characteristics of closed pores in various coals have been ex-
tensively studied (Radlinski and Mastalerz, 2018; Radlinski et al., 2004;
Zhang et al., 2015b). In most coals, the closed porosity, for a given pore
size of 12 nm, decreases linearly with the total number of pores
(Sakurovs et al., 2018b). The existence of closed pores in shale has been
reported in some literature (Chen et al., 2018; Niu et al., 2017).
Nevertheless, the controlling factors and gas-bearing properties of
closed pores in shales are poorly studied. Through FIB-SEM (focused ion
beam-scanning electron microscopy) and nano-CT (nano-computed to-
mography) characterization, closed pores not only refer to the isolated
pores but also include the pore network systems that enclosed by the
surrounding minerals (Gu et al., 2015; Tang et al., 2016; Zhou et al.,
2016). Therefore, if the closed pores in organic-rich shale have a certain
gas-bearing capacity, it is essential to evaluate the geological and re-
coverable reserves of shale gas.
With the application of SANS/USANS (small-angle neutron scat-
tering/ultra small-angle neutron scattering) techniques, two methods
can be used to characterize the closed pores. One method is based on
the differences between different characterization techniques. SANS/
USANS can provide information on the total porosity (open and closed
pores) and pore size distribution within a sample (Sun et al., 2017b,
2018; Zhao et al., 2017). Mercury injection capillary pressure (MICP)
and low-pressure gas physisorption isotherm techniques allow for the
characterization of accessible, or open, pores (Clarkson et al., 2013;
Davudov et al., 2018; Mastalerz et al., 2012). Therefore, the parameters
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Marine and Petroleum Geology 107 (2019) 407–422
of closed pores can be obtained by comparing intrusion techniques and
that from the scattering techniques. The second one takes advantage of
a unique property of neutrons; the contrast-matching small-angle neu-
tron scattering (CM-SANS) technique can distinguish the accessible and
inaccessible pores for a specific fluid in a certain pore size range. The
contrast variation was implemented by mixing deuterated solvents such
as D2O with regular solvents such as H2O. CM-SANS technology was
initially used in the closed pore and connectivity studies of other ma-
terials such as coal char, coke, and silica (Liu et al., 2017; Melnichenko
et al., 2012; Sakurovs et al., 2018a). More recently, deuterated water
and methane were used in CM-SANS experiments on shale for the de-
termination of closed porosity (Bahadur et al., 2018; Gu et al., 2016;
Ruppert et al., 2013). Meanwhile, CM-SANS method can avoid the er-
rors that may be introduced by applying different models to calculate
pore size distribution measured by various techniques. Additional
background information of CM-SANS method can be found in Chapter 8
and references in Melnichenko (2015).
A quantitative characterization of pore connectivity in shale is still a
challenge in reservoir evaluation. For conventional reservoirs, the
hysteresis of MICP is often used to calculate the mercury withdrawal
efficiency and pore body/throat ratio to indicate pore connectivity
(Bary, 2006; Katz and Thompson, 1986; Li et al., 2015). On the mi-
crometer scale, the slopes of spontaneous imbibition curves and nano-
sized tracer diffusion coefficient and distance were used to assess the
connectivity of shale by some researchers (Gao and Hu, 2018; Hu et al.,
2015b; Sun et al., 2017a). On the nanometer scale, the FIB-SEM and
nano-CT were utilized to rebuild 3D visual models of limited areas by
numerical simulation (Starnoni et al., 2017; Zhao et al., 2018). On the
other hand, CM-SANS obtains the averaged data on the macroscopic
scale (＞mm3) and quantitatively characterizes pore connectivity at the
nanometer scale.
Although waterless fracturing is being tried, hydraulic fracturing is
still a key technology for shale gas development (Westwood et al.,
M. Sun, et al. Marine and Petroleum Geology 107 (2019) 407–422

Fig. 2. Schematic of experimental setup for in-situ gas content measurement and desorption curve.

Table 1
Mineralogical composition and organic petrographic characteristics of shale samplesa.
Sample Well Depth (m) Quantitative analysis of whole-rock minerals (wt.%) Relative content of clay TOC Ro (%) OM elemental analyses (wt.%)
minerals (wt.%) (wt.%)

Quartz Plagioclase Calcite Dolomite Pyrite Clays C I I/S %Sm N C H O

(X)Y1-16 (X)Y1 467.7 23 0 7 0 29 41 0 30 70 25 4.21 2.77 0.67 39.21 1.87 5.34

(X)Y1-2 (X)Y1 542.1 23 4 7 0 25 41 0 22 78 15 15.4 2.82 0.64 42.60 2.01 3.90
(X)Y1-1 (X)Y1 549 12 3 0 16 11 58 0 24 76 15 8.53 2.82 0.75 61.78 2.59 10.25
FY1-6 FY1 937 31 3 0 0 6 60 1 10 89 15 34.1 2.52 0.78 61.43 2.62 17.86
FY1-8 FY1 940 58 0 0 0 4 38 18 0 82 40 3.20 2.57 0.68 60.01 2.59 15.99
FY1-13 FY1 962 32 4 0 7 10 47 24 0 76 35 2.01 2.56 0.48 44.63 1.82 15.35

a
C = chlorite; I = illite; I/S = illite-smectite mixed-layer mineral; %Sm = percentage of smectite in mixed-layer mineral; TOC = total organic carbon;
Ro = vitrinite reflectance; OM = organic matter; A part of data for (X)Y1-1 were previous published by Sun et al. (2017a,b).

2017). A large volume of water (2–6 million gallons) was pumped into
shale formations to create hydraulic fractures for economic production
(Singh, 2016). Across all shale plays in US, only 6–10% of the pumped
water is recovered (Singh, 2016). The abundant retention of injected
water in shale matrix keeps the hydrocarbons from migrating into
hydraulic fractures by reducing the relative permeability of gas (Gupta
et al., 2018). Therefore, it is significant to study the water accessibility
in shale which is conveniently investigated here by CM-SANS that uses
H2O/D2O as the solvents.
In this work, six core samples of two wells from Upper Permian

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Table 2 to 70° for quantitative mineralogy analyses. Total organic carbon (TOC)
Parameters used in calculating Scattering Length Density (SLD)a. and vitrinite reflectance (Ro) of samples were determined by a Leco
Mineral Density, (g/ Elemental composition SLD ( × 1010 cm−2) carbon analyzer and an MPV-3 microphotometer 806 apparatus, re-
cm3) spectively. The organic matter extraction and elemental (CHON) ana-
lyses of samples were conducted following the standard methods of GB/
Quartz 2.65 SiO2 4.18
T19143-2003 and GB/T19144-2010.
Calcite 2.71 CaCO3 4.69
Dolomite 2.86 CaMg(CO3)2 5.44
Plagioclase 2.61 NaAlSi3O8 3.97
2.2. SANS experiments
Pyrite 5.01 FeS2 3.81
Illite 2.70 K(Al3Mg)(Si7Al)O20(OH)4 3.80
Smectite 2.35 Na0.7(Al3.3,Mg0.7) 3.26 SANS measurements were carried out on the General Purpose SANS
Si8O20(OH)4H2O (GP-SANS) instrument at Oak Ridge National Laboratory (ORNL), USA.
Chlorite 3.00 (Mg9Al3)(Al3Si5)O20(OH)16 3.75
A wide Q range (0.001 Å−1 ≤Q ≤ ∼0.5 Å−1) was obtained by collecting
Kerogen 1.50 C90H47O15N 3.39
SANS data at three sample-to-detector distances of 19.2 m, 10.7 m, and
a
Online calculators are available at https://www.ncnr.nist.gov/resources/ 1.7 m using neutron wavelengths of λ = 4.57 Å (10.7 m, 1.7 m) and
activation/. λ = 12 Å (19.2 m), where Q = 4πλ−1 sin (θ) and 2θ is the scattering
angle. Core samples were pulverized and sieved into specific size ranges
Longtan formation transitional shales were selected. Although these (35–80 mesh), such that more than 99.6% neutron transmission is
limited samples cannot adequately represent the transitional shales, the achieved (Sun et al., 2018). Samples were then oven-dried at 60 °C for
methodology is applicable for other organic-rich transitional shales in 48 h before loaded into 1 mm path length quartz glass cells for mea-
evaluating their pore connectivity and water accessibility. With a surement, yielding an effective thickness of ∼0.5 mm (Bahadur et al.,
combination of SANS, CM-SANS, MICP, low-pressure gas physisorption, 2015).
FE-SEM, HIM, the main objectives of this work are as follows: (1) CM-SANS experiments were performed on the Suanni SANS spec-
characterize the closed pore (e.g., pore volume, pore size distribution, trometer at 20 MW China Mianyang Research Reactor (CMRR). The Q
and relationship with gas content); (2) assess the pore connectivity; (3) range of this study covered from 0.003 Å−1 to 0.3 Å−1 with neutron
determine the water accessibility in clay-rich transitional shales. This wavelengths of λ = 5.3 Å (4 m, 1 m) and λ = 8 Å (10 m). The mixtures
work is beneficial to understand the pore connectivity and water ac- of H2O/D2O (water/d-water) with different SLDs were added into the
cessibility of transitional shales, and provides guidelines for future ac- 1 mm path length Hellma cells (Hellma Analytics, 404-1-46). The shale
tive development. samples were slowly poured into the cells approximately 8 h before
SANS analyses to ensure that samples were fully in contact with H2O/
D2O mixtures.
2. Shale samples and experiments The raw 2D scattering patterns were corrected by subtraction of
scattering data of empty-cell and acid-washed quartz sand with the
2.1. Sampling and analyses same particle size (35–80 mesh). Corrected scattering from acid-washed
quartz sand is to eliminate the influence of pore space between sample
A total of six fresh core samples were selected from the Upper particles. The original SANS data was reduced to 1D absolute scale via
Permian marine-terrestrial transitional Longtan Formation in Well (X) IGOR Pro software. The data were analyzed using IRENA macros
Y1 and Well FY1 (Fig. 1). The powdered whole-rock samples (less than (https://usaxs.xray.aps.anl.gov/software/irena) and PRINSAS software
200 mesh) and clay minerals separated using gravity method were (http://smallangle.org/content/software). Prior to the analysis, the
carried out on a Bruker X-ray diffractometer with a step of 0.02° from 2° background scattering intensity, as calculated from the slope of a plot of

Fig. 3. SANS profiles of (a) samples and (b) corrected for background.

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Table 3
Values of porosity and other parameters obtained from SANS analysesa.
Sample ID SANS SLD H2O/D2O PI porosity PDSP porosity PDSM porosity PDSM PDSM NDP PDSM porosity PDSM Pore volume
( × 1010 cm−2) volume (2–400 nm) (%) (2–400 nm) (%) (2–400 nm) (%) SSA (m2/ ( × 1017cm−3) (3–400 nm) (%) (2–100 nm)
ratio g) (10−2 cm3/g)

(X)Y1-16 3.86 1:1.75 10.8 13.6 13.46 24.81 27.5 12.00 2.37
(X)Y1-2 3.71 – 3.5 4.12 3.65 6.13 6.3 3.34 0.70
(X)Y1-1 3.93 1:1.83 2.9 3.78 3.38 11.20 9.5 2.88 0.93
FY1-6 3.63 1:1.52 3.9 4.79 4.73 5.98 3.8 4.54 0.97
FY1-8 3.90 – 6.3 7.83 7.33 13.11 7.4 7.00 2.68
FY1-13 3.92 1:1.81 4.4 5.82 5.42 5.95 2.8 5.28 0.97

a
PI= Porod invariant; PDSP= Polydisperse Spheres; PDSM= Polydisperse sphere model; SSA= Specific surface area; NDP= Number density of pores.

2.4. FE-SEM and HIM imaging

Before the imaging with FE-SEM (Zeiss Merlin) equipped with an

energy-dispersive spectrometer observation, samples were prepared by
cutting as 5 mm × 5 mm × 2 mm slices which parallel to bedding and
ion milled perpendicular to the bedding plane by Ilion + II (Model 697,
Gatan) for a smooth surface. Before imaging, the samples were coated
with carbon at a thickness of 5 nm on the surface to enhance the
electrical conductivity. Then, FE-SEM images were collected at a
2–4 mm working distance with an acceleration voltage of 1 kV. HIM
(Zeiss Orion NanoFab) has a higher resolution than FE-SEM and can
produce ultra-high resolution images of nonconductive surfaces, espe-
cially useful for observing sub-10 nm pores in shale. The instrument
was operated at a working distance of 7 mm, a beam current set at
0.9–1 pA, and a scan dwell time of 0.5 μs.

2.5. Gas content test

Fig. 4. SANS-generated pore size distribution (from PDSM analysis) for tested
samples.
Q4I(Q) vs. Q4, was subtracted.
2.3. Mercury injection capillary pressure (MICP) and low-pressure gas
physisorption isotherm analyses
MICP tests were performed using a Micromeritics AutoPore V 9620
with an initial filling pressure of 5 psi (0.034 MPa) to a maximum
pressure of 60000 psi (413 MPa). This pressure range corresponds to a
pore-throat range of 36 μm to 3 nm based on Washburn equation using
physical constants: surface tension = 485 mN/m, and contact
angle = 130° (Katz and Thompson, 1986). Prior to the test, 1 cm-sized
cuboid samples were oven-dried at 60 °C for 48 h to remove moisture
and then cooled down to room temperature (∼23 °C) in a desiccator.
Three bulb penetrometer with 0.096 mL stem volume is most suitable
for shale samples with low-porosity (less than 8%). The mercury com-
pressibility and blank penetrometer errors in high pressure have been
corrected.
N2 and CO2 adsorption measurements were conducted at 77 K and
273 K by a Micromeritics ASPS 2020 apparatus. The samples were
crushed into 35–80 mesh as same in the SANS test and degassed at
110 °C under vacuum for about 5 h prior to the adsorption experiments.
The pore volume and pore size distribution of pores with diameters
between 0.35 nm and hundreds of nanometers were characterized
based on density functional theory (DFT) (Sang et al., 2018; Sun et al.,
2016).
The in-situ gas content in this study can be divided into lost gas
content, desorbed gas content, and residual gas content (Ma et al.,
2015; Tang et al., 2017). The AD-LJ-150-3 in-situ gas desorption ap-
paratus manufactured by China University of Geosciences was used to
carry out the desorbed gas and residual gas content (Fig. 2a and b). The
rate of minimum response flow is 0.1 ml/h, while the precision of
pressure and temperature measurements are 0.01 MPa and 0.1 °C, re-
spectively. During the first 3 h, the instrument recorded one datum
every 10 s. The initial gas desorption rate was measured at reservoir
temperatures by placing at least 1 kg core sample into the desorption
canister. The lost gas content was estimated by the initial gas deso-
rption rate and the time of samples coring from underground to can-
ister. Reservoir temperature setting was based on sample depth and
geothermal gradient in this area. Then, the samples were heated to
90 °C until the released gas cannot be detected. Thus, the desorbed gas
content includes the amount of gas desorbed at reservoir temperature
and 90 °C. Finally, the core samples were crushed into powder in the
canister to obtain the residual gas content. A schematic diagram of an
in-situ gas content curve is shown in Fig. 2c. The measured in-situ gas
content was converted into the gas content under standard temperature
and pressure conditions (STP, 0 °C, and 101.325 kPa).
3. Results
3.1. Geochemical characteristics
The results of mineral composition, TOC content, vitrinite re-
flectance index and organic matter elemental value for samples are
listed in Table 1. All shale samples in this study with a vitrinite re-
flectance greater than 2% are over-mature and within the dry gas
window. TOC contents of marine-terrestrial transitional shale vary
greatly (2.01%∼34.1%) due to the change of microfacies. Clay and
quartz are the dominant minerals, and the illite-smectite mixed-layer
mineral accounts for 70% or more of the clays in these shale samples. In

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M. Sun, et al.
Fig. 5. Combined SANS raw data and water contrast matching data for samples showing pores in all samples being penetrated by deuterated water.
general, clay content is higher than quartz content in transitional shale
samples, which is consistent with the results in literature studies (Jiang
et al., 2017; Mao and Guo, 2018). Brittle minerals such as pyrite and
carbonate mineral are ubiquitous in these shale samples. Though CHON
analysis, the average elemental composition of kerogen was calculated.
The scattering length density (SLD) of each components, calculated
based on above analyses, are listed in Table 2.
3.2. Pore characterization
3.2.1. SANS and CM-SANS analyses
Fig. 3 shows the raw SANS profiles and the profiles corrected for
background scattering. An approximate relation between the pore ra-
dius (r) and scattering vectors (Q), (r ≈ 2.5/Q) has been used in poly-
disperse spherical pores in shale samples (Radlinski et al., 2000). A
comparative analysis of data was carried out for Q range between
0.25 Å−1 and 0.00125 Å−1 (equivalent to pore diameter between 2 nm
and 400 nm). The formula that used for the SLD calculation of shale
samples was the same as in previous studies (Bahadur et al., 2015; Sun
et al., 2018).
A total non-negative least-squares (TNNLS) method was used in the
Irena macros to obtain porosity, specific surface area (SSA), number
density of pores (NDP; the number of pores per unit volume (in units of
cm−3)), and generate pore size distribution (PSD) within a certain size
range. An optional ‘Q-weighting’ of intensity is implemented to improve
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Marine and Petroleum Geology 107 (2019) 407–422
convergence when data span large Q ranges and intensity (Ilavsky and
Jemian, 2009). The polydisperse size-distribution model (PDSM) was
used to analyze to data in the Irena macros software with the SLDs
shown in Table 3. The assumption of the PDSM was that pore network
conforms to polydisperse spherical pore network in shale and ignores
the contribution from the structure factor term. In this case, the scat-
tering intensity in this PDSM is defined as (King et al., 2015; Zhang
et al., 2019b):
I (Q) = (ρ1 − ρ2 )2 ∑ P (Q, r )2F (r ) V (r )2NΔr (1)
where ρ1 and ρ2 are the SLDs of shale matrix and pores, r is the radius of
sphere, P (Q, r ) is the form factor of spheres with radius r, F (r ) is the
pore size distribution function, V (r ) is the volume for spheres with
radius r, N is the number of sphere. The calculated porosity, specific
surface area (SSA), and number density of pores (NDP) for samples are
listed in Table 3. A plot of pore size distribution (PSD) of samples for
comparison is given in Fig. 4.
In addition, the Porod invariant (PI) method has been utilized to
calculate the porosity when shale samples are treated as a two-phase
system. The porosity can be calculated by Eq. (2) using a scattering
contrast ( Δρ ) (Porod et al., 1982):
∞
∫ Q2I (Q) dQ = 2π 2 (Δρ)2∅ (1 − ∅)
0 (2)
M. Sun, et al. Marine and Petroleum Geology 107 (2019) 407–422

Fig. 6. Pore size distributions derived from neutron scattering data for dry and water-contrast-matching samples to show water-inaccessible pores.

Table 4
Pore parameters of samples from MICP and gas adsorptiona.
Sample ID MICP Bulk MICP MICP porosity Mercury Body-throat N2 Pore volume N2 SSA N2 APD CO2 Pore volume CO2 SSA
density (g/ porosity (%) (3–400 nm) (%) Withdrawal ratio (2–100 nm) (m2/g) (nm) (10−2 cm3/g) (m2/g)
cm3) Efficiency (%) (10−2 cm3/g)

(X)Y1-16 2.94 2.59 2.46 28.9 32.5–8.2 1.00 5.72 8.35 0.26 8.66
(X)Y1-2 2.89 3.21 2.00 41.4 3.5–1.4 0.28 0.51 30.00 1.41 40.38
(X)Y1-1 2.07 3.70 2.80 86.1 1.3–1.1 0.76 7.58 4.71 2.12 62.21
FY1-6 1.94 5.79 3.60 47.8 1.6–1.1 0.25 0.44 28.10 2.29 62.33
FY1-8 2.55 6.31 5.80 35.6 13.3–1.8 2.18 7.58 13.02 0.46 15.24
FY1-13 2.56 3.27 3.10 33.9 11.4–4.5 0.47 1.74 11.95 0.072 2.32

a
APD = Average pore size distribution.

The PI porosities of samples generated from the PRINSAS software model (Radlinski, 1999; Sun et al., 2017b), the two algorithms are
are listed in Table 3. In the Porod invariant method, the SANS intensity consistent with each other.
is considered to follow the power law scattering and independent of the rmax
∅
shape of the scattering object (Porod et al., 1982). Nevertheless, the I (Q) = Δρ2
V¯
∫ V 2F (r ) P (Q) dr
SANS intensity shows a deviation in the higher-Q region due to non- rmin (3)
fractal scattering of small pores (Bahadur et al., 2018). The porosity ∞
calculated from PDSM model is not restricted to fractal pore structure where V̄ = ∫ V 2f(r)dr is the average pore volume and
and general higher than the PI porosity. 0
2
sin(Qr) − (Qr)cos(Qr)
The porosity and PSD of shale also can be calculated from the P(Q) = 9 ⎡ ⎤ is a form factor for spheres. The PDSP
⎣ (Qr)3 ⎦
polydisperse spheres (PDSP) model in the PRINSAS software. The PDSP porosities of specimens are very close to PDSM porosities. The slight
and the PDSM models both assume that the pores are in spherical shape discrepancies may be due to the differences in data fitting.
and have a random size distribution. According to Eq. (3) of PDSP In order to investigate the water accessibility of shale, four samples

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M. Sun, et al.
Fig. 7. Intrusion/extrusion curves (a) and pore volume distribution (b) from MICP and gas physisorption isotherms (low-pressure N2 ad/de-sorption isotherms (c)
and low-pressure CO2 adsorption isotherms (d)) for all samples.
were tested on CMRR for CM-SANS following their SANS measurements
at ORNL. Based on the SLD difference between water (SLD:
−0.56 × 1010 cm−2) and heavy water (SLD: 6.39 × 1010 cm−2), the
contrast matched liquid mixture of H2O/D2O corresponding to the
average SLD of shale was mixed with the samples about 8 h before the
CM-SANS test. The ratio of H2O/D2O at the contrast match point for
each shale samples is given in Table 3. Given the different conditions of
the two SANS instruments, the absolute intensity of neutron scattering
was calibrated by the same standard sample of the Al-4. Fig. 5 shows
the decrease of scattering intensity of contrast-matched shale samples
due to accessible pores filled with water. The residual scattering in-
tensity can be used to reveal information about inaccessible pores to
water (Bahadur et al., 2018). The PSDs and porosities of original
samples and contrast-matched samples estimated using Eq. (1), are
shown in Fig. 6. It is evident from Fig. 6 that water accessibility in shale
samples varies with pore sizes. SANS data within the same Q range were
used for the analysis.
3.2.2. MICP and gas physisorption
MICP tests give information about pore volume of mercury acces-
sible pores and pore-throat size distribution. Pore volume and porosity
of samples obtained from the mercury intrusion curves were listed in
Table 4. Fig. 7a is used to calculate the connective pore volume related
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Marine and Petroleum Geology 107 (2019) 407–422
to pore throat size during MICP tests and the results are shown in
Fig. 7b. Fig. 7b shows most pore volumes are connected by pore-throat
with diameters smaller than 50 nm. Meanwhile, the efficiency of mer-
cury withdrawal and pore-body-to-throat aspect ratio (mercury sa-
turation more than 80%) can be obtained from the hysteresis loop be-
tween intrusion and extrusion curves (Fig. 8 and Table 4).
Nitrogen adsorption/desorption and carbon dioxide adsorption
isotherms of shale samples are shown in Fig. 7c and d, respectively. The
pore volume, surface area and average pore diameter of the samples
within a specific pore diameter (based on Kelvin Equation) can be
calculated by nitrogen adsorption and the results are shown in Table 4.
BET specific surface area of N2 adsorption does not include the con-
tribution of micropores; therefore the BET values cannot represent the
real surface areas of shales. Nevertheless, the reproducible BET values
under carefully controlled conditions have been used to evaluate the
“apparent” surface area of shale for decades (Gregg and Sing, 1982;
Mastalerz et al., 2012; Sun et al., 2018). Based on the CO2 adsorption
data, the micropore surface area and DFT micropore volume are de-
rived and also shown in Table 4. The difference between SSA derived
from N2 and CO2 adsorption reflects the contribution of different sizes
and types of pores to surface area.
M. Sun, et al.
Fig. 8. Plots of pore-throat diameter and pore body-to-throat aspect ratio vs. mercury saturation for all samples.
3.2.3. Observation of FE-SEM and HIM
According to the classification proposed by some researchers, pores
in shale are divided into interparticle pores (Inter-pores), intraparticle
pores (Intra-pores) and organic matter (OM) pores (Loucks et al., 2012;
Milliken et al., 2013). The type and connectivity of pores affect the
permeability and wettability of shale reservoirs (Gao and Hu, 2016).
FE-SEM images (Figs. 9–10) show that various types of pores are de-
veloped in the Upper Permian marine-terrestrial transitional shales.
Meanwhile, the OM pores and Inter-pores are mainly developed in
Longtan Formation shales (Fig. 9a). Abundant OM pores within nano-
and micron-meter scales are observed in FE-SEM and HIM images
(Fig. 9b and c), and these pores with bubble-like, rounded or elliptical
shapes are unevenly distributed within OM. Considering that the ma-
turity of Longtan shale range from 2.52% to 2.82% within the dry gas
generation window, the OM pores may mostly come from the genera-
tion and expulsion of hydrocarbons (Bernard and Horsfield, 2014).
Fig. 9c shows a HIM image of a higher magnification of the OM pore
network. Numerous pores less than 10 nm in diameter can be seen in
the image. The internal structure observed in the HIM image reveals
that the OM pore network is internally connected. Meanwhile, a few
large OM pores made up of several small interconnected OM pores
(Fig. 9c). The OM pores in Fig. 9d illustrate the heterogeneity of OM
pore development in organic matter. The two closed organic particles
shown in Fig. 9d with likely the same maturity have very different
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Marine and Petroleum Geology 107 (2019) 407–422
development of OM pores. Fig. 9d clearly shows that the dissolution
leads to further expansion of Inter-pores and facilitates the connection
of OM pore network. In such a well-connected pore network, hydro-
carbon will migrate out from the OM pore system along the conductive
pathway. In addition, some organic particles are mixed with clay mi-
nerals to form organo-clay complexes (Fig. 9e), which developed nu-
merous pores at the edge of contact between minerals and OM (Fig. 9f).
Pyrite mainly exists in the form of framboidal grains and associates
with OM in Longtan shale samples (Fig. 10a). Dissolution causes the
deformation of crystals in pyrite framboids (Fig. 10b), while the crystals
are generally of euhedral shape in marine shales. A complete dissolu-
tion of some crystals forms crystal-mold pores in pyrite framboids
(Fig. 10a). Also, the interparticle space between crystals in some pyrite
framboids are filled with OM (Fig. 10c). The HIM image shows that the
OM within pyrite framboids contains OM pores with a similar pore size
less than 20 nm (Fig. 10d). Sheet-like pores are usually occurred in clay
particles in samples (Fig. 10e). From the observation of FE-SEM
(Fig. 9a, d, 10f), the dissolution mostly occurs along the interparticle
pores between brittle and plastic minerals. Fig. 10f demonstrates that
the quartz cement produced by dissolution contains some tiny pores.
3.3. In-situ gas content
Bases on the volume of gas released over time, the measured
M. Sun, et al. Marine and Petroleum Geology 107 (2019) 407–422

Fig. 9. FE-SEM and HIM photomicrographs for Longtan transitional shale samples. (a) Pore types overview of sample (X)Y1-16; (b) OM pores in a single OM grain of
sample (X)Y1-1; (c) An enlargement of organic pores by HIM in the rectangle area marked in Fig. 9 (a); (d) Heterogeneously distributed OM pores within OM grains
and dissolution of inorganic minerals of sample (X)Y1-16; (e) Organo-clay complex of sample FY1-6; (f) An enlargement of abundant pores in organo-clay complex in
the rectangle area marked in Fig. 9 (e).

desorbed and residual gas contents and the estimated lost gas content
were listed in Table 5. All the samples have some residual gas, ap-
proximately average 29% of the total in-situ gas content, which cannot
be desorbed. Moreover, methane accounted for 89.1% of the total
content by analyzing the composition of the desorbed gas.
4. Discussion
4.1. Closed (inaccessible) pores analyses
Pore parameters determined from SANS, MICP, and nitrogen ad-
sorption offer important insight into the structure of closed pores in
shale samples (Tables 3–4). The parameters of MICP and nitrogen ad-
sorption in the pore-throat range of 3–400 nm and in the pore size range
of 2–100 nm were used to calculate the fraction of closed pores by
comparing with SANS results in the same size range, respectively
(Table 5). The SANS porosity and pore volume, especially obtained
from PDSM model, are much higher than that from MICP and nitrogen
adsorption in each sample (Tables 3–4). The total fractions of
inaccessible pores for mercury and nitrogen molecules range from 2.8%
to 79.5% and from 18.3% to 74.2%, respectively (Table 5). The fraction
of closed-pores of nitrogen is generally higher than that of mercury,
except for sample (X)Y1-16. In order to characterize the closed-pore
distribution, the pore volume distributions derived from SANS, gas
adsorption (N2 and CO2), and MICP results were plotted in Fig. 11.
The pore volume distribution curves of each sample derived from
MICP and SANS cross each other within the pore-size range between 30
and 70 nm (Fig. 11). The pore volume distribution from SANS is higher
in magnitude than that from MICP after these cross points; similar re-
sults were found in U.S. shale oil samples (Zhao et al., 2017) and other
gas-bearing shale samples (King et al., 2015). One reason is that SANS
measured total porosity of the pores while MICP measures pores in-
truded by mercury. That is to say, there are closed pores in this size
range where MICP cannot access. Another reason is related to MICP
itself. As shown in Figs. 9b and 10b, some OM or inorganic pore net-
works containing macropores (＞50 nm) connected with surrounding
space through smaller pore throats. Other studies also have reported
that MICP would underestimate the volume of some macropores in fine-

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M. Sun, et al. Marine and Petroleum Geology 107 (2019) 407–422

Fig. 10. FE-SEM and HIM photomicrographs for Longtan transitional shale samples. (a) Pyrite framboids distributed in organic matter of sample FY1-8; (b)
Dissolution causing the deformation of crystals in pyrite framboid of sample FY1-8; (c) Organic matter within the space between pyrite crystals of sample (X)Y1-2; (d)
An enlargement of organic pores within a pyrite framboid by HIM in the rectangle area marked in Fig. 10 (c); (e) Sheet-like pores in clay particles of sample FY1-13;
(f) Quartz cement produced by dissolution containing some tiny pores of sample FY1-13.

Table 5
In-situ gas content and multiple-scale fraction of closed-pores of studied samplesa.
Sample ID In-situ gas content (cm3/g,STP) Fraction of closed-pores Fraction of closed-pores from LPNP and SANS (%) Fraction of water
from MICP and SANS (%) inaccessible Pores (%)
Lost gas Desorbed gas Residual gas 2–5 nm 5–10 nm 10–50 nm 50–100 nm Total
content content content

(X)Y1-16 0.88 1.69 2.29 79.5 85.7 72.2 3.2 75.4 57.8 4.31
(X)Y1-2 0.57 2.12 0.94 40.1 81.8 57.7 9.5 73.7 60.0 –
(X)Y1-1 0.51 5.71 0.47 2.8 42.9 0.1 16.4 73.0 18.3 5.28
FY1-6 0.89 4.15 1.22 20.7 99.9 79.0 44.7 85.2 74.2 2.04
FY1-8 0.52 1.23 0.92 17.1 59.5 41.3 0.1 28.5 18.7 –
FY1-13 0.67 1.39 1.43 41.3 67.6 65.5 20.6 76.3 51.5 12.63

Fraction of closed-pores from LPNP and SANS =(V PDSM Pore volume (2–100 nm)-V N2 Pore volume (2–100 nm))/V PDSM Pore volume (2–100 nm).
Fraction of water inaccessible Pores = ∅contrast matched sample/∅ original sample (data in Fig. 6).
a
Fraction of closed-pores from MICP and SANS =(∅PDSM porosity (3–400 nm)- ∅MICP porosity (3–400 nm))/∅PDSM porosity (3–400 nm).

417
M. Sun, et al. Marine and Petroleum Geology 107 (2019) 407–422

Fig. 11. Comparison of pore volume distribution obtained from SANS, MICP, and gas (CO2 and N2) adsorption for the studied samples.

grained rocks due to complicated pore shapes (Hildenbrand and Urai, Since the 3 nm pore-throat is the limit of MICP, the data in this area
2003; Wang et al., 2016). Meanwhile, the underestimation is usually show some fluctuations (Fig. 11). In some shale samples ((X)Y1-2, FY1-
related to the pore body-to-throat aspect ratio (Abell et al., 1999; 6, FY1-8, FY1-13), the pore volumes of MICP were higher than the
Dewhurst et al., 1998). results of SANS in the mesopore range (2–50 nm) (Fig. 11). Since MICP

418
M. Sun, et al.
Fig. 12. Fraction of accessible pores to water in four Longtan transitional shale
samples by H2O/D2O contrast matching.
represents the distribution of pore throats, the pore throats connect the
pores with large pore sizes, resulting in an overestimate of pore volume
in this range. Therefore, MICP would overestimate the pore volume of
mesopores due to the complex pore morphology. However, as in sample
(X)Y1-1, if the body-throat ratio is small and mercury withdrawal ef-
ficiency is high with good pore connectivity, the overestimation will be
significantly reduced. Meanwhile, as in sample (X)Y1-16, if the fraction
of closed-pores is high in this pore-size range, it may conceal this
phenomenon.
The fraction of nitrogen-inaccessible pores with different pore dia-
meters were obtained by comparing SANS pore volume with that de-
rived from the nitrogen adsorption experiments (Table 5). In order to
study the relation between fractions of closed-pores and pore size, the
fraction of nitrogen-inaccessible pores were divided into four pore-
diameter intervals, as SANS and N2 adsorption both measure pore
bodies. For pores with diameters larger than 50 nm, the fractions of
nitrogen-inaccessible pores may be overestimated. Based on the Kelvin
equation, the pressure P/P0 of nitrogen adsorption is higher than 0.981
when determining the pore diameter larger than 50 nm (Gregg and
Sing, 1982). When the shale pore size distribution is extensive, the
Ⅳ-type isotherm can become the Ⅱ-type isotherm, and it is difficult to
measure the accurate saturation adsorption (Kuila and Prasad, 2013;
Tian et al., 2015). Therefore, both nitrogen adsorption and MICP un-
derestimated the pore volume of macropores. The partial OM pores and
inorganic pores with pore-size diameters larger than 50 nm are not
reflected in FE-SEM images (Figs. 9b, 10b and e). Within the pore
diameter range of 10–50 nm, the proportion of closed pores is relatively
low. This is consistent with the overlaped curves of the pore volume
distribution of the SANS and nitrogen adsorption analysis shown in
Fig. 11. The closed pores ratio increased within the pore diameter range
of 5–10 nm, except for sample (X)Y1-1.
According to Table 5, the percentage of nitrogen-inaccessible pores
with diameters less than 5 nm is the highest, consistent with the results
of U.S. shale oil research and Longmaxi Shale (Sun et al., 2017b; Zhao
et al., 2017). The organic pores in U.S. shale oil samples with maturity
ranging from 0.67% to 1.05% are inchoately developed by FE-SEM
observation (Grathoff et al., 2016). Zhao et al. (2017) indicated that
clay-associated pores with pore diameters less than 10 nm are in-
accessible to nitrogen in oil shale samples. The internal space of mon-
tmorillonite is inaccessible to nitrogen molecules in shale which cannot
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Marine and Petroleum Geology 107 (2019) 407–422
be detected by gas adsorption (Sang et al., 2018). In the study of marine
Niutitang gas shale, the closed pores are mainly related to organic pores
(Sun et al., 2018). Therefore, closed pores, inaccessible to nitrogen and
mercury, are mainly distributed in the pore-size range of less than
10 nm and associated with OM, clay minerals and organo-clay com-
plexes in transitional shales.
4.2. Shale connectivity and water accessibility
The connectivity of pores in the shale matrix is a significant con-
trolling factor for hydrocarbons migration, enrichment, and production
behavior (Hu et al., 2015a; Zhang et al., 2015a). Over the past decades,
experimental permeability measurements are often used to evaluate
pore connectivity in rock (Cui et al., 2018; Davudov and Moghanloo,
2018). However, for shale with extremely low matrix permeability, the
determination of absolute permeability is challenging, and the aniso-
tropy is extreme. Therefore, the pore connectivity can be reflected by
the fractions of water, mercury, and nitrogen molecule inaccessible
pores in shale (King et al., 2015; Zhao et al., 2017; Bahadur et al.,
2018).
In this work, CM-SANS tests were used to evaluate the pore con-
nectivity of Longtan transitional shales. Shown in Fig. 12, under am-
bient pressure, accessibility of pores to water varies with pore size and
show similar trends in four samples. The lowest accessibility to water is
associated with pore sizes of 5–10 nm, which also exhibited a peak at
the CM-SANS volume distribution in Fig. 6. Approximately 87–98% of
the pores (2–200 nm diameters) in these four shale samples are water-
connected (Table 5). In the CM-SANS tests, the water accessibility of the
shale samples in the pore-size range of 2–5 nm are considerably dif-
ferent from each other (Fig. 6). Though the qualitative observation by
FE-SEM and HIM (Figs. 9 and 10), OM pores and clay-associated pores
are generally developed in shale samples. In general, OM pores are oil-
wet, and clay-associated pores are water-wet (Gao and Hu, 2016). Some
nitrogen-inaccessible pores with diameters of 2–5 nm are penetrable by
water and this may due to the wettability. Water also appears to access
more of the pores with pore size diameters less than 30 nm than me-
thane in Barnett Shale in a previous study (Ruppert et al., 2013). An-
other reason is that the strong capillary pressure of small pores makes it
more accessible for water by spontaneous imbibition (Gao and Hu,
2018; Sun et al., 2017a). The results of water accessibility in transi-
tional shales are higher than previous studies on Marcellus Shale and
Barnett Shale (Bahadur et al., 2018; Gu et al., 2016; Ruppert et al.,
2013), which may be indicative of different pore connectivity. The
Permian transitional shale samples in this work are very clay-rich (clay
content 38–60%) with a high concentration of illite-smectite mixed-
layer mineral. In contrast, the clay mineral contents in marine shales
are usually less than 30% which are mainly composed of illite. Some
internal pores contained in illite-smectite mixed-layer mineral (in par-
ticular of smectite in the I/S group) are inaccessible to nitrogen mole-
cules but accessible to water due to different wettability (Sang et al.,
2018).
The water-inaccessible pores are mainly distributed in the pore size
range of 5–10 nm and 20–30 nm in all samples (Fig. 12). Interestingly,
Table 5 shows that the sample (X)Y1-1 has the lowest fraction of ni-
trogen-inaccessible pores (0.1%) in pore-size range of 5–10 nm. Its
fraction of mercury-inaccessible pores is also very low, 2.8%. One ex-
planation is that water film confined inside hydrophobic organic na-
nopores prevent the pores from being filled by water in ambient con-
dition (Li et al., 2017; Zhang et al., 2019a). Bahadur et al. (2018)
suggested that the water-inaccessible pores in 5–50 nm pore size range
are associated with OM and not with a specific mineral in Marcellus
Shale.
Fig. 13a exhibits a positive relationship between residual gas con-
tent and total closed pore volume. The latter was obtained from com-
paring SANS with N2 adsorption results (V PDSM Pore volume (2–100 nm)-V
nitrogen pore volume (2–100 nm)) (Tables 3 and 4). Here the closed pores
M. Sun, et al. Marine and Petroleum Geology 107 (2019) 407–422

Fig. 13. Relationships between (a) Closed pore (inaccessible to N2) volume vs. residual gas content; (b) Closed pore (inaccessible to water) porosity vs. residual gas
content; (c) CO2 pore volume vs. lost and desorbed gas content; (d) Total organic carbon vs. CO2 pore volume (Black: Longtan Shale in this work; Green: Longmaxi
Shale from Sun et al., 2017a,b; Red: Niutitang Shale from Sun et al., 2016). (For interpretation of the references to colour in this figure legend, the reader is referred
to the Web version of this article.)

correspond to those which are not penetrated by nitrogen. This corre-
lation indicates that the closed-pore system of transitional shale sam-
ples has certain gas-bearing properties. The porosity of water-in-
accessible pores shows no apparent positive correlation with residual
gas content (Fig. 13b). This means that part of gas-bearing space can be
occupied by water. This process will affect the shale gas diffusion and
lead to abundant retention of fracturing fluid (Phan et al., 2018; Singh,
2016). A better understanding of the behavior of water in shale pores
will improve fracturing fluid management and ultimately enhance re-
covery.
In addition, the lost and desorbed gas content increase as CO2-
measured pore volume increases in transitional shale samples
(Fig. 13c), suggesting that the shale gas in transitional shale samples
mainly occurs in micropores, similar to the occurrence of coalbed me-
thane (Cai et al., 2013; Mastalerz et al., 2018). Moreover, the pore
volume determined by MICP and N2 adsorption does not exhibit a linear
relationship with lost and desorbed gas content. The average pore size
of transitional shale samples determined by N2 adsorption (Table 4) is
larger than that of marine shale samples (Mao and Guo, 2018; Yang
et al., 2017). Therefore, mesopores in transitional shale samples con-
tribute less specific surface area than marine shale samples. The dis-
crepancy of pore structure in shales is the fundamental factor that leads
to the difference of shale gas occurrence state.
Although micropores (pore size＜2 nm) are difficult to be observed

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M. Sun, et al.
by FE-SEM and HIM, the positive correlation of micropores volume
with TOC (Fig. 13d) indicates that OM provides the main development
space for micropores. For this, the connection between the organic pore
network system and its surroundings determines the expulsion of shale
gas. The inter-particle pores formed by dissolution play an essential role
in the connectivity of some samples (Fig. 9d). If the organic pore net-
work system is disconnected with surrounding pore networks, over-
pressure will be formed when the shale gas content exceeds the max-
imum methane adsorption capacity of the organic pores (Hao et al.,
2013). Therefore, the pressure coefficient of shale formation will also
reflect characteristics of pore connectivity.
Moreover, unlike sandstone reservoirs, shale sample usually does
not have a single geometric pore body-to-throat aspect ratio (Fig. 8). To
compare the data in Table 4, the lower pore body-to-throat aspect ratio
of MICP is usually associated with a higher mercury withdrawal effi-
ciency. For sample (X)Y1-1 with highest mercury withdrawal efficiency
and lowest pore body/throat ratio, MICP curve overlaps best with SANS
data (Fig. 11). MICP curves have been used in some literature to reflect
pore connectivity in shale (Davudov et al., 2018; Zuo et al., 2018).
However, the compressibility or destructiveness in the high-pressure
segment to the shale samples needs to be clarified in further work.
5. Conclusions
Six Upper Permian Longtan Formation transitional shale samples
were examined using neutron scattering tests, MICP, gas adsorption
experiments, and FE-SEM/HIM techniques to characterize the pore
connectivity and water accessibility within the shale matrix. Based on
results and discussion, the following conclusions can be drawn:
(1) Closed pores, inaccessible to nitrogen and mercury, are mainly
distributed in the pore-size range of less than 10 nm and associated
with organic pores and interlayer spaces of illite-smectite mixed-
layer mineral.
(2) CM-SANS test using water shows that 87–98% of the pores
(2–200 nm diameters) are water-connected in transitional samples,
which are higher than that of the marine shales from the U.S.A. The
inaccessible pores to water are mainly distributed in the pore size
range of 5–10 nm and 20–30 nm in all samples, which may be due
to the influence of water film confined inside hydrophobic organic
nanopores.
(3) In-situ gas behaviors indicate that closed pores have a certain gas
bearing capacity. Meanwhile, the occurrence of shale gas in tran-
sitional samples is more related to micropores.
Acknowledgements
The authors sincerely thank the National Natural Science
Foundation of China (Grant Nos. 41802146; 41830431; 41572134),
Fundamental Research Funds for the Central Universities (No.
CUG180608), Key Laboratory of Tectonics and Petroleum Resources
(TPR-2017-09), and Key Laboratory of Unconventional Oil & Gas
Geology of China Geological Survey (DD20160181-YQ17W06JJ01), for
their financial support. We acknowledge support by Oak Ridge National
Laboratory for instrument time on the High Flux Isotope Reactor which
was sponsored by the Laboratory Directed Research and Development
Program and the Scientific User Facilities Division, Office of Basic
Energy Sciences, U.S. Department of Energy. We thank Dr. Lilin He of
ORNL for his discretionary neutron beam time and his help with SANS
experiments at GP-SANS and Core Lab of Institute of Geology and
Geophysics at Chinese Academy of Sciences for the help with FE-SEM
and HIM analyses.
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