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Nano- to Macro-Scale Structural, Mineralogical, and Mechanical Alterations

in a Shale Reservoir Induced by Exposure to Supercritical CO2

Article  in  Applied Energy · November 2022

DOI: 10.1016/j.apenergy.2022.120051

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 Applied Energy 326 (2022) 120051

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Nano- to macro-scale structural, mineralogical, and mechanical alterations

in a shale reservoir induced by exposure to supercritical CO2
Ogochukwu Ozotta c, Oladoyin Kolawole d, Mohamed Lamine Malki c, Tobi Ore e,
Thomas Gentzis f, Hallie Fowler f, 1, Kouqi Liu g, Mehdi Ostadhassan a, b, *
a
Key Laboratory of Continental Shale Hydrocarbon Accumulation and Efficient Development, Ministry of Education, Northeast Petroleum University, Daqing 163318,
China
b
Institute of Geosciences, Marine and Land Geomechanics and Geotectonics, Christian-Albrechts-Universität, Kiel 24118, Germany
c
Department of Petroleum Engineering, University of North Dakota, Grand Forks, ND 58202, USA
d
John A. Reif, Jr. Department of Civil and Environmental Engineering, New Jersey Institute of Technology, Newark, NJ 07102, USA
e
Department of Geology and Geography, West Virginia University, Morgantown, WV 26506, USA
f
Core Laboratories, Reservoir Geology Group, 6316 Windfern Road, Houston, TX 77040, USA
g
Institute of Energy, Peking University, Beijing 100871, China

H I G H L I G H T S

• We showed microstructural and mineralogical alteration of the Middle Bakken after two months of exposure to ScCO2 exposure.
• Nanoindentation was employed to confrim the long-term micromechanical impact of the sample after exposure to ScCO2.
• Lack of understanding of these variations in project planning could lead to potential CO2 leakages and environmental hazards in storing CO2.

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

Keywords: Considering the importance of carbon neutrality, UCCUS which is underground carbon capture, utilization, and
CO2 Storage storage has been widely adopted to mitigate climate change. Studies are being conducted to improve this process,
Carbon sequestration however, there is still a lack of knowledge on the multiscale physicochanical alterations that the storage res­
Shale
ervoirs may endure due to the long-term exposure to supercritical CO2 (ScCO2). These changes happen from
Microstructure evolution
Nanomechanical properties
nano- to macro-scale in mineralogy and pore structures which will impact mechanical and petrophysical attri­
Bakken Formation butes of the host rock. Since unconventional shale reservoirs have become the target of CO2-EOR and CO2
storage, it is imperative to understand the long-term impact of these alterations due to ScCO2 exposure. This
study coupled experimental and theoretical modeling to investigate continuous nano- to macro-scale changes in
mechanical, mineralogical, and structural alterations in the Middle Bakken by exposing samples to ScCO2 for 3,
8, 16, 30 and 60 days. Qualitative analysis of electron micrographs pre and post exposure confirmed certain
minerals have evolved while image processing showed a quantitative change in pore structures. Moreover,
nanomechanical changes pre and post exposure were inspected via nanoindentation method. Furthermore, we
assessed how mineral content was impacted during the exposure using X-ray diffraction analysis. Next, we
adopted two rock physics models based on mechanical and mineralogical observations to upscale mechanical
properties to the macro scale. Analyses of the results indicate that long-term ScCO2 exposure induces mineral
dissolution, precipitation and the development of fractures in the host reservoir. Further, CO2 induced alterations
can lead to long-term macro-scale weakening causing a loss in mechanical integrity of the Middle Bakken by
decreasing its elastic modulus (DS model = –33 %, MT model = -30 %) and increasing its Poisson’s ratio (DS
model = +38 %, MT model = +32 %). Overall, this study can provide new insights for a better design and
implementation of UCCUS projects in shale reservoirs, most especially in the Middle Bakken and other similar
formations, where a lack of understanding of these variations and project planning could lead to potential CO2
leakages and environmental hazards.

* Corresponding author.
E-mail addresses: oladoyin.kolawole@njit.edu (O. Kolawole), mehdi.ostadhassan@nepu.edu.cn, mehdi.ostadhassan@ifg.uni-kiel.de (M. Ostadhassan).
1
Formerly with Core Laboratories.

https://doi.org/10.1016/j.apenergy.2022.120051
Received 28 January 2022; Received in revised form 18 August 2022; Accepted 25 September 2022
0306-2619/© 2022 Elsevier Ltd. All rights reserved.
O. Ozotta et al.
1. Introduction
With the global demand for carbon capture and underground storage
(CCUS), further research is being done to enhance subsurface charac­
terization to safeguard long-term storage operations. Supercritical CO2
(ScCO2) injection and storage into deep geologic reservoirs will help
reduce greenhouse gas emissions [1–7]. In this regard, unconventional
organic-rich shale plays have attracted growing interest as possible host
rocks for CO2 storage because of their relative abundance, lateral extent,
and other factors such as the high organic content that makes them
suitable for trapping the injected gas [8,9]. The CO2 storage operations
involve the injection and pressurization of reservoirs that usually result
in changes (macro − scale) in the in − situ stresses that may perturb the
pre-existing fractures or faults present in the formation [10]. This in-situ
instability may lead to slippage along with the pre-existing fracture
systems and create new shear fractures. Fractures are conduits for fluid
seepage, and their nucleation may prompt an increase in reservoir
pressures [11]. However, the pre-existing natural fractures and artifi­
cially induced fractures from hydraulic fracturing in shale reservoirs can
provide adequate volume for efficient CO2 storage and at the same time
support recovery of the oil [12–14].
CO2 is known to have the potential to affect the properties of the host
rock such as its porosity, permeability, tortuosity, pore structure, min­
eral composition, and specific surface area [1,3,4,7,8,15–17]. One
important property of a shale reservoir that could change because of
long-term exposure to CO2 is its mechanical response. This originates
from alteration on microstructures as well as grain scale (microscale)
changes in mechanical attributes i.e., Young’s modulus (YM) or grain
boundaries stiffness. It’s well understood that mechanical characteristics
are deciding factors for safe operations in both UCCS and EOR
[8,15,16,18–21].
A change in mechanical properties such as Young’s modulus and
hardness may occur as a result of the ScCO2 injection and storage pro­
cedure [22]. Many studies have been conducted to date on the effect of
ScCO2 on shale. A study on shale from Gippsland Basin, Australia to
define the shale sealing efficiency as the caprock [23] revealed that the
rock-forming minerals and the brine-Sc-CO2 system had several chemi­
cal interactions leading to questionable caprock integrity. Lyu et al. [19]
conducted extensive lab measurements to explore how mechanical
properties from a low-clay content shale from Sichuan Basin, China can
be affected by exposure to CO2. They demonstrated that both subcritical
and supercritical CO2 soaking can reduce rock strength while increasing
shale ductility [19]. Ao et al. [15] conducted four types of analyses after
shale samples were exposed to ScCO2 to investigate structural and
chemical alterations. After the Sc-CO2 treatment, samples strength was
reduced, and their mineral makeup changed significantly [15]. Espinoza
et al. [24] studied the impact of CO2-charged brine on the shear strength
and stiffness of various rock samples from an outcrop near a naturally
occurring CO2 seepage through triaxial testing. They observed carbon­
ate precipitation in fractured Mancos Shale will lead to matrix stiffening
and fracture mineralization resulting in overall stiffer and likely tighter
shale over geological time [24].
Overall, majority of the studies are focused on the effects of CO2
exposure on the mechanical properties in the macrometer (plug) scale.
However, considering the presence of various mineral phases such as
quartz, K-feldspar, calcite, dolomite, and clay minerals, confirms shale
reservoirs have very complex mechanical properties as a sedimentary
rock with strong heterogeneity. The mechanical properties of the sam­
ples will invariably be influenced by these individual various mineral
phases while each would react to CO2 exposure differently [25]. This
being said, little is known about how different mineral phases affect the
mechanical properties of shale reservoirs post-CO2 saturation. As a
result, it is important to investigate the mechanical properties of the
various mineral phases in the samples post-CO2 saturation via methods
that can isolate a single mineral response. This can be done through the
nanoindentation method which has been proven to be reliable and
2
Applied Energy 326 (2022) 120051
highly applicable to petroleum geosciences, and which can complement
conventional methods, especially when retrieving plug-sized samples is
time-consuming or costly. Moreover, this method allows observing the
influence of pore structure and mineralogical composition on the me­
chanical properties, grain-grain impact, and the mechanical response of
single grains [22,26].
Nanoindentation is based on the measurement of applied load vs the
depth of penetration of an indenter on the surface and has been used
extensively to quantify mechanical properties in different types of me­
dium [27]. In geosciences and civil engineering, there exist a wealth of
studies, especially on shale formation that has successfully employed
this method for different objectives [7,26,28–33]. Although nano/
micro-indentation has been performed on sandstone, marble, granite,
and shale in the past, majority of these studies have been on dry samples
[26,34]. In a single and limited study, Wang et al. [7] analyzed rock
mechanical changes of the samples from the Bakken Formation by
exposing them to ScCO2 and discovered that Young’s modulus of the
samples decreased as a result. Although the importance of their study,
the samples were only exposed for 40 days and the experiments were
limited to mechanical variations at 10 days intervals. This procedure
made it difficult to capture changes in the first 10 days of the exposure
and explain possible reasons for them which could have been due to
microstructural and mineralogical alterations. Both of these properties
decide if the EOR or the storage operation would be successful in the
field. Thus, there is a lack of comprehensive knowledge and study to
detect physicochemical alterations of shale reservoirs when exposed to
CO2 at supercritical state greater than 40 days with shorter analysis
intervals.
Bakken shale, a prominent unconventional shale play in North
Dakota, North America, and is an important candidate for CO2 seques­
tration and CO2 enhanced oil recovery (CO2-EOR) [35]. Hence, this
study comprehensively investigates continuous, long term nano-scale
changes in mechanical, mineralogical, and structural alterations in
samples from the Middle Bakken after exposure to long-term supercrit­
ical CO2, and further adopts rock physics models to upscale the CO2-
induced changes to macroscale. Shale samples from the Middle Bakken
were analyzed pre- (0 days) and post-CO2 treatment periods (3, 8, 16,
30, and 60 days). The nanoindentation method was used to delineate
nanoscale mechanical variations at each stage of exposure and then two
major rock physics models (dilute scheme (DS) and Mori-Tanaka (MT))
were employed to upscale the resulting modulus to the reservoir/
macroscale. Furthermore, microstructural assessments was done via
visual inspection of the surface using field emission scanning electron
microscopy (FESEM) at the end of the incubation process. Additionally,
to understand how porosity changed after 60 days of exposure, we used
image processing to calculate porosity from electron micrographs. Ul­
timately, we analyzed mineral composition evolution during the ScCO2
exposure using X − Ray diffraction (XRD) and related those changes to
mechanical variations through statistical deconvolution of the results.
2. Sample Preparation, and experimental setup
For this study, subsurface samples from the Middle Bakken (MB)
were retrieved from a well that was drilled in the Williston Basin, ND,
USA, for experimental tests and analysis. The Bakken Formation, located
in the Williston Basin, is one of the most prolific unconventional shale
plays in North America [36–39]. This formation was deposited from the
Late Devonian to Early Mississippian in the Williston Basin and overlies
portions of North Dakota and Montana in the United States, plus spreads
in Manitoba and Saskatchewan in Canadian Provinces. The upper and
lower Bakken shales are the source rocks while the middle member
(mixed clastic/carbonate unit) serves as a reservoir for the oil that is
generated from the upper and lower Bakken [36–38]. The Middle
Bakken is recommended as the best candidate for CO2 injection and
sequestration due to higher pore space for CO2 storage, the presence of
carbonate minerals to improve CO2 mineral trapping, and the upper and
O. Ozotta et al.
lower Bakken shale formations providing a seal to prevent CO2 leakage
from in the middle member [35].
To perform nanoindentation tests an aliquot was selected and pre­
pared parallel to the bedding plane while the remainder was separated
into pieces, and all were ground for the mineralogical analysis during
the incubation process. Since the roughness of the sample surface will
affect the nanoindentation test results [40], the following sample
preparation procedure was followed: the sample chip was left bare, and
polished with different grit sizes of sandpaper from 600 to 1200. Next, a
diamond polisher with various grain sizes (5, 3, and 0.5 μm) was used to
smoothen the sample surface to the proper roughness. The mineralogical
composition of the ground portions was determined on crushed pieces,
sieved with less than 250 μm for homogenization. A portion of the
crushed sample was used to examine pre-ScCO2 saturation and the
remainder was put in a Vinci hydrostatic core holder for series of post-
ScCO2 exposures.
The core holder was connected to a high-pressure CO2 cylinder,
while the pressure was monitored with a regulator attached to the
chamber to ensure supercritical (ScCO2) conditions were maintained
throughout the saturation period. The core holder was closed tightly,
leaving the valve open to bleed out air from the connection pipes before
shutoff. The CO2 saturation chamber was set at supercritical conditions
of a pressure of about 7.4 MPa and a temperature of 31 ◦ C. The samples
prepared for nanoindentation were tested pre-CO2 (MB_0) exposure and
then placed in the core holder for several stages of incubation and
nanoindentation tests. The procedure was as follows: after 3 days, the
sample was taken out of the core holder for nanoindentation testing
(MB_3) while a similar process was repeated after 8 days (MB_8), 16 days
(MB_16), 30 days (MB_30) and 60 days (MB_60) of CO2 exposure under
the same pressure and temperature conditions. The same was followed
on the powders for XRD examination at each stage and prior to the in­
cubation process.
3. Methods
3.1. Mineralogical analysis
For the mineralogical composition analysis, a D8 advanced X-ray
Diffractometer (XRD) with the detection limit of ± 0.5 wt% was used
with a scanning rate of 3◦ /min in the range of 3◦ − 90◦ and 0.7 to 2 gr of
powder from the samples at each stage was analyzed. A curve fitting
method was used to delineate major minerals (major peaks) that exist in
the spectrum with correction for Lorentz Polarization [41]. XRD was
carried out to measure the changes in mineral compositions pre-and and
after each step of post-CO2 saturation. Identification of multiphase
minerals based on the modulus data that was collected from nano­
indentation testing allowed further classification of them into 3 me­
chanical phases: soft (clay, halite, K-feldspar), complex or intermediary
(muscovite), and brittle minerals (quartz, calcite, dolomite, and pyrite)
based on the suggestion by Long et al. [42].
3.2. Structural investigation and image analysis
To investigate the microstructure, sample surface, and quantify pore
structure information, the FEI Quanta 200F field emission scanning
electron microscope (FESEM) was utilized. This enabled us to examine
the sample at pre- and post-CO2 exposure (after the entire 60 days of
incubation) conditions with different magnifications at 10kev. FESEM
characterized and described the morphology, pore structure and pore
size distribution of the sample pre-CO2 and post-CO2 saturation. Image
J, a commercial software extensively used in image analysis in other
fields, was utilized to analyze the pore structures from the grayscale SEM
images [32,43].
The backscattering electron images (BSE) or secondary images (SE)
of the sample have low gray scale values, while the solid components
have a high gray scale value, making it possible to examine the pore
3
Applied Energy 326 (2022) 120051
structure from grayscale FESEM images [44]. All of the images were
segmented into a binary image after choosing an acceptable threshold
value, with the black pixels (larger than the threshold value) repre­
senting the solid matrix of the sample and the white pixels (smaller than
the threshold value) representing the pores [45]. Fig. 1 depicts the
image processing workflow for extracting the sample’s pore structure
and pore size. The critical point technique, which is like the inflection of
the cumulative brightness histogram, was used in this analysis. This was
done to determine the most reliable upper threshold value for image
segmentation [44]. Following this workflow, pore size was quantified
for pre-CO2 and post-CO2 saturation.
3.3. Nanomechanical testing
The nanoindentation test is a non-destructive force spectroscopy
technique and can be done on a small piece of a specimen. Nano­
indentation can be used to evaluate the three basic mechanical attri­
butes of rocks or materials, the elastic modulus, hardness, and fracture
toughness [46]. Nanoindentation was done with a Hysitron Inc. nano­
indenter using a Berkovich tip. The load–displacement curve (Fig. 2)
acquired from nanoindentation testing provides the peak load (Pmax)
and maximum displacement depth (hmax). Here, grid indentation
approach was used to further assess the nanomechanical properties of
shale specimens [47,48]. On the sample surface, several indents were
made, each of which was treated as a separate event while we made sure
the surveyed surface is overall the same at each step of testing. The
Oliver and Pharr approach, also known as energy-based method [27],
was used for calculating the strength and modulus from each curve
[27,49]. The mechanical properties (hardness and Young’s modulus) are
obtained from three measured parameters: peak load (Pmax), maximum
displacement depth (hmax), and contact stiffness as follows [50,51]:
√̅̅̅̅̅
dP 2 Ac
S= = √̅̅̅ = Er (1)
dh π
where, Ac is the contact area, Er is the reduced Young’s modulus, given
by:
1 1 − ν2 1 − ν2i
= + (2)
Er E Ei
where: v is the Poisson’s ratio of the rock; Ei and vi are Young’s modulus
and the Poisson’s ratio of the indenter; E is Young’s modulus of the
material. Young’s modulus of the material can then be determined by
the combination of Eq. (1) and Eq. (2) and the indentation hardness can
be derived by its classical definition, using the following expression:
Pmax
H= (3)
Ac
A grid of 20 × 10 was applied to cover the surface area of (240 μm ×
120 μm). The distance between the two neighboring grids is 10 μm.
Sufficient indents (200 indents) must be taken on a sample to accurately
describe the mechanical properties of the samples in order to expose
their heterogeneous mechanical characteristics [48,52]. As a result, grid
nanoindentation was used in this research to attain this goal. In this
method, a few requirements should be met: the number of indents made
on the surface should be greater than the representative elementary area
(REA). Thus, if each indent is defined by a length scale D and a depth h,
then the value of h should be smaller than D. The space between the
grids should be greater than the indentation characteristics impression
size. This is required to prevent interference between surrounding in­
dents and mechanical phases. Under these conditions, the indentation
spot has no statistical bias in terms of the spatial distribution of these
phases. Furthermore, this will confirm that the likelihood of encoun­
tering different phases is equal to the surface fraction occupied by
several phases on the indentation surface [48,53]. Ultimately, when the
probing size is much larger than the characteristic size (D), each indent
O. Ozotta et al. Applied Energy 326 (2022) 120051

Fig. 1. Microstructural image process workflow.

∑ (kr − k0 )(3k0 + 4μ )
kDS = k0 + fr 0
(4)
r=1
3kr + 4μo

∑ 5μ0 (μr − μ0 )(3k0 + 4μ0 )

μDS = μ0 + fr (5)
r=1
μ0 (9k0 + 8μo ) + 6μ0 (k0 + 2μ0 )

Here, kDS and μDS are the macroscopic bulk and shear modulus of the
homogenized composite obtained by the DS model, respectively; μr and
kr (r = 0, 1, 2) are the shear and bulk moduli of the constituent phases
with μ0 and k0 being that of the carbonate matrix; f r (r = 0, 1, 2) rep­
resents the volume fraction of the phases. The elastic modulus, EDS and
Poisson’s ratio vDS can be estimated from kDS = EDS /3(1 − 2vDS ) and
μDS = EDS /2(1 +vDS ).

3.4.2. Mori − Tanaka (MT) model

The Mori-Tanaka (MT) model considers that each inclusion is
embedded in an infinite medium. MT accounts for the effect of other
inclusions employing uniform screening fields and the interaction be­
tween phases unlike the DM which makes it suitable for composites with
Fig. 2. Schematic of indentation load–displacement curve (modified matrix inclusions [55]. The effective bulk (Equation (6)) and shear
from [49]). moduli (Equation (7)) based on the MT model is given by:
( )( )− 1
∑ ∑
will represent the average property of the composite material. MT
k = fr
kr fs
(6)
r=0
3kr + 4μo s=0
3kr + 4μo

3.4. Macromechanical properties and rock physics modeling ∑ μr

r=0 f r μ0 (9k0 +8μ0 )+6μr (k0 +2μ0 )
μ MT
= ∑ fs
(7)
Succeeding the experimental nanoindentation tests, rock physics s=0 μ0 (9k0 +8μ0 )+6μr (k0 +2μ0 )

models were used to upscale the nanomechanical properties to

macroscopic/reservoir-scale and the results were compared. In the rock
physics models, the volume fractions were specified for the various
phases, and the elastic moduli of the various phases and the geometric
details of how the phases are arranged relative to each other were
determined from XRD and nanoindentation data. Two basic models
adopted are the dilute scheme (DS) and Mori-Tanaka (MT) models.
3.4.1. Dilute model (DM)
The DM model is based on the classical Eshelby solution with an
inhomogeneous ellipsoidal inclusions that are well separated and their
interactions can be ignored [54]. The equivalent bulk (Equation (4)) and
shear moduli (Equation (5)) based on the DM model are calculated as:
4. Results and analysis
4.1. Mineralogical alterations
The pre-and post-CO2 treated samples were each subjected to XRD
analysis to determine their variability in mineral compositions. Because
the chips were sliced from the same core plug and then crushed into
powder, the assumption was made that the samples contained similar
mineral components (homogenization concept). Regarding the sample
mineralogy, quartz, K − feldspar, carbonates, clay, muscovite, pyrite,
and halite are predominant (Table 1) among which quartz, carbonates,

4
O. Ozotta et al.
clay, and muscovite are the most abundant of all minerals present in the
samples. Dolomite and calcite are the carbonate minerals that exist in
the sample while illite and chlorite are the dominant clay minerals. We
detected the variations in major minerals from the initial values that
were found in the pre-exposed samples as follows: pre-CO2, quartz was
38.0 wt%, after 3 days of saturation, quartz decreased to 33.6 wt% (-12
%), after 8 days, to 12.3 wt% (-68 %), after 16 days it changed to 35.0 wt
% (-8%), at 30 days it was quantified as 30.4 wt% (-20 %) and after 60
days it was at 32.1 wt% (-16 %), meaning quartz had a decreasing trend
post-CO2 saturation.
The carbonate minerals were at 30.2 wt% pre-CO2 saturation, after 3
days, their amount was increased to 32.4 wt% (+7%), after 8 days, to
11.1 wt% (-63 %), after 16 days to 24.0 wt% (-21 %), at 30 days, their
amount was measured 30.2 wt% (no change) and finally, after 60 days of
saturation, their quantity was recorded to be 22.7 wt% (-25 %), meaning
carbonate had more decreasing trend post-CO2 saturation, which was
also reported by others [7]. The clay minerals were at 10.9 wt% pre-CO2
saturation, after 3 days their content increased to 18.8 wt% (+73 %),
after 8 days their amount was increased to 51.8 wt% (+375 %), after 16
days to 19.0 wt% (+74 %), at 30 days their amount was 23.4 wt%
(+115 %), and, finally, after 60 days of saturation, the content was
detected to be 10.2 wt% (-7%). This shows that clay minerals exhibited a
more increasing trend post-CO2 saturation. Other minerals showed a
fluctuating trend while halite became more abundant overall. Details of
mineralogical changes are summarized in Table 1 and visually presented
in the corresponding 100 % stacked bar chart in Fig. 3.
4.2. Nanomechanical alterations
Few of the nanoindentation data points and their corresponding
force–displacement curves obtained from the sample are presented in
Fig. 4, pre-CO2 (Fig. 4a) and post-CO2 after 3 days (Fig. 4b), 8 days
(Fig. 4c), 16 days (Fig. 4d), 30 days (Fig. 4e) and 60 days (Fig. 4f)
saturation, for soft, complex/intermediary, and brittle minerals. As the
indenter contacts the sample surface, the behavior of the surface at that
specific spot is initially elastic, but as the indentation pressure increases,
the contact becomes plastic. This phenomenon can be classified as a
mixture of elastic and plastic transformations. This behavior is not size
dependent, and it is the same for a larger rock volume as well on
macroscale. Hence, the displacement curves vary because of the
different mineral grains the indenter contacts on the sample surface on
landing [27]. The behavior of the rock can be assumed to be elastic
during the unloading stage, allowing the deformation response of the
loading to be recovered. The elastic properties can then be determined
using Eq. (1) and Eq. (2) [27]. Fig. 4 illustrates that at the loading stage,
two of the load–displacement curves of the brittle and complex minerals
were smooth without any abnormal phenomena pre-CO2 (Fig. 4a)
saturation and post-CO2 (Fig. 4c-f) saturation, while another
load–displacement curve of the brittle and complex minerals exhibited a
“pop-in” behavior during the loading for post-CO2 saturation of 3 days
(Fig. 4b). This “pop-in” behavior (the sudden jump in the
load–displacement curve) might be caused by the tip interacting with
Table 1
Mineralogical composition of the samples (in wt.%)* pre-CO2 and post-CO2 saturation.
Saturation Time Sample ID Quartz K-Feldspar
0 day MB_0 38 8.1
3 days MB_3 33.6 8.4
8 days MB_8 12.3 5 11.1
16 days MB_16 35 11
30 days MB_30 30.4 7.8
60 days MB_60 32.1 7.4
± Clay minerals consists of illite and Chlorite.
*The detection limit of the equipment is ± 0.5 wt%.
5
Applied Energy 326 (2022) 120051
intra-particle pores in the quartz and carbonates or sudden creation of
fractures [22,42,56].
The recovered elastic deformations of all brittle minerals were large,
and the residual deformations were small in the unloading stages of all
load–displacement curves. Therefore, it was inferred that the brittle
minerals had a dense structure, a high stiffness, and strong mechanical
properties pre-CO2 and post-CO2 saturation. Additionally, the curves
representing the soft material recorded some “pop-in” during the
loading stage. This “pop-in” incident might be caused by the cracks that
formed during the penetrating process of the tip when the load reached
the yield strength of that particular grain [9]. We hypothesize that this
“pop-in” behavior could be the tip encountering microfractures, inter-
particle pores, and soft minerals (e.g., clay, halite, or K-feldspar) dur­
ing loading, and that the displacement experienced an abrupt increase
[57]. It’s important to note that exact determination for the cause of this
phenomenon requires visual observation of the tip-surface interaction
while the indentation is in progress. The recovered elastic deformations
of the soft and complex minerals were small pre-CO2 saturation and
increased post-CO2 saturation during unloading. Moreover, the residual
deformations were large pre-CO2 saturation and reduced post-CO2
saturation. This revealed that the soft minerals have a loose and soft
structure, low stiffness, and weak mechanical properties.
Pre-CO2 saturation, the soft minerals had the highest residual de­
formations, brittle minerals had the smallest, and complex minerals had
residual deformations that were in between these two phases. Post-CO2
saturation, the residual deformation difference between each mineral
phase was reduced. When the maximum load is maintained for 2 s, the
displacement continues to increase, indicating a creep deformation in
the material. Creep deformation is observed more in the post-CO2
saturation (after 3 and 8 days) in the soft minerals than in the complex
and brittle mineral phases. There is a large displacement difference
between different mineral phases pre-CO2 saturation under the same
load. The displacement of the soft mineral is much greater than the
complex mineral, which is again greater than the brittle mineral.
Collectively, the displacement difference between the mineral phases
reduced post-CO2 saturation, although the highest displacement in the
soft mineral was observed 3 days post-CO2 saturation. Finally, the
deformation of clay is much more important than the complex and
brittle minerals during the CO2 exposure which is well documented
[54].
The observed trend in mineral alterations (increasing and decreasing
mineral content) due to exposure to ScCO2 (after 8 days and 30 days)
can be related to the observed trend in variation of the nano-/micro-
scale hardness and Young’s modulus. These fine-scale changes that
occurred after 8 days might be the peak change of the ScCO2-induced
alteration before stability in shales is achieved. Since the nano­
indentation tests focus on individual mineral component that is indented
instead of the bulk mechanical properties, as fluctuation in modulus and
hardness is observed, this occurrence indicates that macroscale me­
chanical behavior may not always correlate to micro or nanoscale me­
chanical properties. This has been reported by other researchers in
materials science with a restricted number of constituent components
Carbonates Clay ± Muscovite Pyrite Halite
30.2 10.9 5.6 7 0.4
32.4 18.8 4.8 1.2 1
51.8 19 0.6 0.9
24 19 3.7 3.5 4
30.2 23.4 7.4 1.13 0.1
22.7 10.2 21.7 2.9 2.9
O. Ozotta et al.
Fig. 3. Mineralogy alterations during ScCO2 exposure times showing quartz (blue), K-feldspar (red), carbonates (green), clay (grey), muscovite (black), pyrite
(yellow), and halite (orange) variations [Clay minerals consist of illite and chlorite]. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
[22,31,42,54]. The frequency count of Young’s modulus (Fig. 5) and
hardness (Fig. 6) displays more than one peak, which infers the com­
posite behavior of the specimen pre-CO2 and post-CO2 stages. In other
words, the existence of several phases in the sample that should be
separated from each other is confirmed. Exhibiting such behavior means
that simply averaging elastic modulus values to obtain bulk mechanical
properties of the sample is not accurate. While this is a common practice,
a rigorous upscaling scheme is required and the results would be pre­
sented and discussed in the following sections of this study.
Fig. 5 shows the distribution of Young’s modulus of the sample pre-
CO2 (Fig. 5a) and post-CO2 saturation for each stage of incubation
(Fig. 5b − f). The presence of various mineral compositions causes
variations in Young’s modulus values in each test at different points, as
the sample is made up of a variety of minerals, each with its own set of
mechanical properties. The minerals with Young’s modulus between 10
and 50 GPa are more prevalent in pre-CO2 saturation, whereas following
the exposure process, the frequency count of these minerals decreased
significantly. Overall, the material phase with the higher Young’s
modulus represents the stiffer minerals and these are dominant in the
rock pre-CO2. Moreover, the phase with lower Young’s modulus values
represents softer materials and their become dominant in post-CO2
saturation, and values in between can be considered as an intermediary
phase [58]. Fig. 6 shows the distribution of the hardness of the sample
pre-CO2 (Fig. 6a) and post − CO2 saturation for different stages of in­
cubation (Fig. 6b-f) which more or less follows a similar pattern as the
Young’s modulus.
4.3. Deconvolution
Nanoindentation curves from the analysis can be deconvolved into
three different mechanical phases (soft, complex, and brittle minerals)
based on the results that was found from the XRD analysis of samples
mineralogical assemblages at each stage. The brittle minerals had elastic
moduli mean ranging from 78.7 to 190.4 GPa while the complex min­
erals had elastic moduli mean varying from 36.8 to 64.6 GPa. Finally,
the soft minerals showed an elastic modulus that is in the 27.0 to 32.9
GPa range (Table 2).
Fig. 7 represents the deconvolution results of the sample pre-CO2
(Fig. 8a) and post-CO2 saturation (Fig. 8b-f). Considering pre-CO2
saturation (Fig. 7a), the first phase indentation response has a mean
value of 28.4 GPa, the second phase 38.4 GPa, and the third phase was
found with a mean value of 190.4 GPa. The first phase likely represents
the soft minerals i.e., clay whereas the second phase with the mean value
of 38.4 GPa represents the complex minerals, which could be due to the
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Applied Energy 326 (2022) 120051
presence of muscovite, other intermediary minerals, or the boundaries
between soft and more brittle minerals. The third phase with the mean
value of 190.4 GPa represents the hard and stiff minerals, which could
be mainly quartz, calcite, dolomite, and pyrite that are abundant in the
sample. The intermediate minerals like muscovite can be described as
the second phase, which has a mean Young’s modulus of approximately
38.4 GPa (between 28.4 GPa and 190.4 GPa). In addition to this value
corresponding to such material in the medium range modulus values,
they can also attribute as some indents have been placed on the
boundary of soft and hard minerals as well [22,59].
Regarding the post − CO2 saturation on day 3 (Fig. 8b), the first
phase indentation response has a mean value of 28.3 GPa, the second
phase was measured with a mean value of 36.8 GPa, and the third phase
showed a mean modulus of 83.8 GPa. Considering the post-CO2 satu­
ration at day 8 (Fig. 8c), the first phase indentation response has a mean
value of 32.6 GPa, the second phase has a mean value of 57.9 GPa, and
the third phase showing 80.4 GPa. Following the post-CO2 saturation at
day 16 (Fig. 8d), the first phase indentation response has a mean value of
27.0 GPa, the second phase 46.9 GPa, and the third phase was found to
have an average mean modulus of 78.7 GPa. Next is the post-CO2
saturation at day 30 (Fig. 8e), where the first phase indentation response
has a mean value of 28.4 GPa, and the second phase has a mean value of
44.3 GPa, while the peak for the third phase disappeared.
Ultimately, the post-CO2 saturation after 60 days (Fig. 8f) displayed
that the first phase indentation response has a mean value of 32.9 GPa,
followed by the second to be 64.6 GPa, and akin to the previous stage we
were not able to delineate any peak representing the third phase. From
these two latest stages of exposure to CO2, it seems that the process has
weakened some of the mechanical properties of the harder minerals
significantly, which could have important implications during opera­
tional processes that rely heavily on the mechanical response of the
formation. Generally speaking, the trends seen in the mechanical
properties of pre-CO2 saturation are consistent with those reported in
other studies where overall the effects of exposure to CO2 will most
likely cause the stiffer minerals to morph into softer ones via interactions
with the gas [60,61].
The surface fraction of each mineral phase can be calculated by
dividing the area under each histogram by the area under the combined
curve. The volume fractions of each mineral phase can thus be estimated
via the deconvolution workflow, which is reported in Fig. 8. This dem­
onstrates the volume fraction of the mineral phases pre-CO2 and post-
CO2 saturation at various stages. Pre-CO2 saturation, the volume percent
of the soft mineral is 29 %, after 3 days of CO2 saturation it decreased to
24 % (-14 %) while after 8 days of CO2 saturation it increased to 41 %
O. Ozotta et al.
Fig. 4. Force curves of samples for (a) pre-CO2 treatment, and post-CO2 treatment after (b) 3 days, (c) 8 days, (d) 16 days, (e) 30 days, (f) 60 days.
(+43 %). After 16 days, the volume fraction increased to 53 % (+43 %),
and after 30 days of CO2 saturation it grew to 42 % (+47 %), and finally,
when the entire incubation period was completed (60 days of CO2
saturation), the volume fraction of soft minerals increased to 54 % (+89
%).
Considering the complex minerals volume fractions, for pre-CO2
saturation, the volume percent was 63 %, after 3 days of CO2 saturation
it increased to 69 % (+9%), and after 8 days of CO2 saturation, it
decreased to 31 % (-52 %). After 16 days, the volume fraction decreased
to 27 % (-57 %), while after 30 days the value decreased to 58 % (-8%),
and ultimately 64 % (-27 %) decline was recorded after 60 days. Finally,
for pre-CO2 saturation, the volume percent of the brittle minerals was 8
%, which decreased to 6 % (–22 %) after 3 days of CO2 saturation, fol­
lowed by an increase to 29 % (+250 %) after 8 days.
When the sample was exposed to CO2 for more than two weeks, the
volume fraction of stiffer minerals increased 20 % (+146 %) but no
brittle minerals were reported after 30 and 60 days of CO2 saturation.
Considering the general outcome from changes in the volume fraction of
various minerals, it was found that the soft minerals exhibited an
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Applied Energy 326 (2022) 120051
increasing trend post-CO2 saturation compared to complex and brittle
minerals while the latter two fluctuated. Based on the above observa­
tions, it appears that stiffer minerals get altered significantly and
become softer after a month of exposure to ScCO2, thus imposing a
notable weakening in the overall strength of the sample.
4.4. Upscaling
Two common rock physics models were utilized for upscaling the
mechanical and elastic properties of the samples from the nanoscale to
macro/reservoir scale. The macroscale geomechanical properties were
estimated with MT and dilute models at pre-CO2 and post-CO2 exposure
conditions. The ranges of elastic modulus of the soft minerals, complex
minerals, and brittle minerals were incorporated from the nano­
indentation test data of pre-CO2 and post-CO2 saturation samples.
However, due to the multiple peaks observed in the histogram obtained
from nanoindentation tests as shown in Figs. 5 and 6, it is difficult to
select the values of modulus for each constituent component precisely.
To resolve this, the elastic modulus and mineral composition fractions
O. Ozotta et al.
Fig. 5. Young’s modulus of distribution of samples (a) pre-CO2 treatment, and post-CO2 treatment after (b) 3 days, (c) 8 days, (d) 16 days, (e) 30 days, (f) 60 days.
derived from the deconvolution step will be incorporated and integrated
to the homogenization step using the rock physics models
[22,31,54,55]. For instance, the elastic modulus of the soft (phase 1),
complex (phase 2), and brittle (phase 3) minerals pre-CO2 and post-CO2
saturation is listed in Table 2, while the Poisson’s ratio (ν) associated
with the phase 1, phase 2, and phase 3 is estimated from bulk and shear
modulus of the minerals according to the literature as 0.36, 0.30 and
0.09 respectively [60]. The final elastic modulus of the samples at each
sate of incubation from dilute and MT models are listed in Tables 3 and 4
for pre-CO2 and post-CO2 saturation stages.
Pre-CO2 exposure, the elastic modulus from dilute and MT models
are 56.48 GPa and 50.56 GPa, while the Poisson’s ratio was calculated
0.24 and 0.25, respectively. At the end of the post-CO2 saturation (60
days), the elastic modulus from dilute and MT models significantly
reduced to 37.76 GPa and 35.29 GPa, whereas the Poisson’s ratio
increased to 0.33.
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Applied Energy 326 (2022) 120051
The macroscale modeling method used in this study has been vali­
dated in previous studies to upscale nano-/micro-scale rock properties to
macroscale [22,31,54,55]. However, some parameters might have
contributed to the extent of the CO2-induced changes observed from
nano-/micro-scale to macroscale alterations in this current study. For
instance, the results from nanoindentation tests (using small sample
sizes) to obtain the fine-scale Young’s modulus, hardness, and Poisson’s
ratio accounted for individual minerals in the sample tested, whereas, at
macroscale, the numerical modeling results will constitute all mineral
grains and the cement in a bulk rock.
5. Discussion
5.1. Fracture development and pore structure alteration
From the comparison of available electron micrographs pre- and
O. Ozotta et al. Applied Energy 326 (2022) 120051

Fig. 6. Hardness of the samples (a) pre-CO2 treatment, and post-CO2 treatment after (b) 3 days, (c) 8 days, (d) 16 days, (e) 30 days, (f) 60 days.

Table 2
The deconvolution results of Young’s modulus for all samples; phase 1 refers to the soft minerals, phase 2 refers to the complex minerals while phase 3 refers to the
brittle/stiff minerals. (SD is the standard deviation; V is the volume fraction).
Sample Phase 1 Phase 2 Phase 3

Mean, GPa SD, GPa V, % Mean, GPa SD, GPa V, % Mean, GPa SD, GPa V, %

MB_0 28.4 0.5 0.3 38.4 1.4 0.6 190.4 24.7 0.1
MB_3 28.3 4.0 0.2 36.8 8.9 0.7 83.8 26.4 0.1
MB_8 32.6 1.8 0.4 57.9 3.8 0.3 80.4 8.0 0.3
MB_16 27.0 0.9 0.5 46.9 1.8 0.3 78.7 2.1 0.2
MB_30 28.4 1.6 0.4 44.3 15.1 0.6 − − −
MB_60 32.9 6.9 0.5 64.6 31.2 0.5 − − −

9
O. Ozotta et al.
Fig. 7. The Young’s Modulus deconvolution results of the samples (a) pre-CO2 treatment, and post-CO2 treatment after (b) 3 days, (c) 8 days, (d) 16 days, (e) 30
days, (f) 60 days.
post-CO2 exposure (only available when the entire 60 days of incubation
was completed), it is evident that fractures are highly developed in the
post-CO2 images. This demonstrate that CO2 exposure should be
responsible for the fracture initiation, propagation, and growth in the
sample resulting in the overall weakening of the sample. This phe­
nomenon has also been observed by others where cracks are formed in
carbonates [62–65]. Moreover, the development of fractures could
happen in quartz-rich specimens too [33], where a fracture prefers to
propagate along the quartz grain easily during the post-CO2 saturation.
This is expected to enhance the permeability of the sample and its
porosity as well. Based on the FESEM analysis of pre-CO2 saturation,
interparticle (interP) and intraparticle (intraP) pores were found in the
sample (Fig. 10a-b). (SEE Fig. 11.).
In the FESEM analysis post-CO2 saturation, interP, intraP pores, and
the creation of new fractures will account for the overall pore space of
the sample (Fig. 9c-d). The interP pores in the sample are triangular and
polygonal in shape and were mainly distributed between the quartz, K-
feldspar, clay minerals, or calcite. The intraP are elliptical or round and
are mainly developed within dolomite, calcite, and quartz grains which
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Applied Energy 326 (2022) 120051
infers interaction has occurred between such minerals and the CO2.
Moreover, various existing minerals are recognized in the electron mi­
crographs including calcite, quartz, dolomite, K-feldspar, and pyrite as
was detected by the XRD analysis. A general pore structure investigation
from the sample pre- and post-CO2 exposure based on the SEM micro­
graphs displays that the majority of the pore sizes pre-CO2 saturation is
below 350 nm while the pore size range post-CO2 saturation is below
200 nm (Fig. 10).
These results demonstrate that the pore sizes were reduced after CO2
saturation, which may indicate that overall, the sample became tighter
[24]. It is important to note that further analysis is required to under­
stand pore space modifications in more detail and address the alteration
of sample permeability, which is beyond the scope of this study. The
overall pore size distribution analysis showed a skewness toward smaller
pore sizes post-CO2 saturation, which can be attributed to scaling from
mineral precipitation as shown in Fig. 12, which is also reported by
other researchers [66]. It is important to note that the major phenom­
enon observed based on these SEM images is mineral dissolution and
precipitation, which has also been reported in previous studies
O. Ozotta et al. Applied Energy 326 (2022) 120051

Fig. 8. The volume fraction of the mineral phases throughout the process of exposure. [The phase refers to soft minerals (black), phase 2 refers to complex minerals
(green,) and phase 3 refers to brittle minerals (yellow)]. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of
this article.)

Fig. 9. FESEM images of the sample for (a, b) pre-CO2, and (c, d) after 60 days of ScCO2 exposure. [Q is quartz, ca is calcite, k-spar is potassium-feldspar, dolo is
dolomite, py is pyrite, interP is interparticle and intraP is intraparticle].

[3–5,67,68]. This means that as the dissolving mineral composition volume fraction of the brittle minerals is reduced post-CO2 saturation,
fraction is reduced in volume, the precipitating mineral composition will the strength and the stiffness of the sample are also reduced which was
increase in volume. As a result, the brittle minerals post-CO2 saturation confirmed via upscaling models as well as the mineralogy of the samples
dissolved, which leads to the precipitation of soft minerals. As the after each stage of incubation.

11
O. Ozotta et al. Applied Energy 326 (2022) 120051

Table 3 introduce fluids to the system and existing components, which presents
Macroscale Elastic modulus from DS and MT models at Pre-CO2 and post-CO2 as a steeper slope value from the initial (Fig. 13). The increase in the
saturation conditions. slope here also verifies the increase in soft minerals as was found by the
Sample CO2-Exposure Elastic Modulus (GPa) deconvolution results (Table 2) and also the increase in the amount of
Period
Dilute Scheme (DS) Mori Tanaka (MT)
that particular mineral phase over the exposure time (Fig. 13). More­
Model Model over, comparing the mineral composition based on the percentage of the
volume phases derived from the XRD analysis with Young’s modulus, a
0 Days 56.48 50.56
3 Days 48.79 47.50 relationship is observed. This means that elastic modulus increased with
8 Days 47.48 44.71 an increase in the soft (phase 1), complex (phase 2), and brittle mineral
16 Days 44.45 42.96 (phase 3) phase volumes. In this regard, Young’s modulus and phase 1
30 Days 38.11 36.79 minerals have a weak positive correlation (Fig. 14a) with a correlation
60 Days 37.76 35.29
coefficient of about 0.10, while Young’s modulus and phase 2 minerals
exhibited a strong positive correlation with a correlation coefficient of
0.83 (Fig. 14b). We also observed that the Young’s modulus and phase 3
Table 4 minerals exhibited a weak positive correlation (Fig. 14c), with a coef­
Macroscale Poisson’s ratio from DS and MT models at Pre-CO2 and post-CO2 ficient of 0.07. We infer those complex minerals (or the boundary and
saturation conditions.
interaction of two distinct mineral phases) would have a more signifi­
Sample CO2-Exposure Poisson’s ratio (-) cant impact on the elastic modulus of the formation for CO2 storage
Period
Dilute Scheme (DS) Mori Tanaka (MT) compared to other minerals.
Model Model

0 Days 0.24 0.25
3 Days 0.24 0.26
8 Days 0.25 0.28
16 Days 0.26 0.29
30 Days 0.32 0.33
60 Days 0.33 0.33
5.2. Mechanical alterations in shales
The statistical analysis of Young’s modulus data of the sample pre-
CO2 and post-CO2 saturation is presented in Fig. 12. The mean Young’s
modulus observed pre-CO2 saturation is 35.4 GPa, and the mean value
after 3 days of saturation is 34.5 GPa (-2%), after 8 days of saturation the
mean value is recorded as 53 GPa (+50 %), followed by a mean value of
38 GPa (+8%) after 16 days of saturation. Finally, after more than two
weeks of incubation, the mean value was measured to be 36 GPa (+2%),
and then 45.3 GPa (+28 %) after one and two months, correspondingly,
when the incubation was completed (Fig. 13a). Based on the results, the
minimum and maximum values had the same non-monotonic trend as
the mean values of Young’s modulus. Considering the measured hard­
ness of the sample pre-CO2 saturation, which was obtained to be 1 GPa,
the mean value after 3 days of saturation was found to be 1.3 GPa (+31
%), 2.5 GPa (+149 %) after 8 days of saturation, followed by a mean
value of 1.8 GPa (+75 %) after 16 days of saturation. Finally, at one
month and two months of incubation, the mean values were measured
1.3 GPa (+29 %) and 2.4 GPa (+136 %), respectively (Fig. 13b). Results
of the hardness show that the minimum and maximum values also had a
fluctuating trend, similar to the average estimated values. It is important
to note that, although we simply averaged elastic properties of this
composite material as a common practice more rigorous upscaling
scheme, such as Mori-Tanaka [22], dilute [69], or effective medium
theory [31,60] can be implemented to represent the macroscale me­
chanical properties of the sample as was performed. The results of the
micromechanical upscaling method and its implication will be discussed
in the following section of this study.
The relationship between the elastic modulus and hardness values of
the samples pre-CO2 and post-CO2 saturation are shown in Fig. 13. The
plot demonstrates that elastic modulus has a positive relationship with
hardness pre-CO2 and post-CO2 saturation with a relatively acceptable
correlation of coefficients. The higher Young’s modulus corresponds to
the higher hardness of the sample for pre-CO2 and post-CO2 saturation.
CO2 interactions with the sample will change the microstructures,
making the sample more ductile [19,70,71] which manifests itself in the
slope of the regressed line between the elastic modulus versus hardness
as shown in Fig. 13.
A longer saturation time increases the extent of interactions between
5.3. Implications for Long-Term CO2 storage in shales
The nano- to micro-scale CO2 induced alterations that was observed
on the Middle Bakken sample properties due to long-term CO2 seques­
tration confirms chemical interactions that’d inevitably takes place be­
tween various components of the rock, mostly minerals and the carbon
dioxide. For instance, some minerals showing a relative decrease in
Young’s modulus and hardness, while other minerals exhibit contrasting
behavior at the end of the CO2 exposure period. The general trend
observed from the results suggests a relative decrease in nano­
mechanical properties of MB due to CO2-induced alterations after 60
days of exposure. This observation is critical and should be considered in
the design and development of CO2 sequestration models in the Middle
Bakken.
In comparing this current study with previously published papers
that investigated changes in properties of the Bakken shale due to ScCO2
treatment [7], this current study provides an in-depth analysis and
presented a comprehensive knowledge of the nano- to macro-scale al­
terations in Bakken due to interactions with ScCO2. For instance, in
terms of ScCO2 treatment and number of samples, the results presented
by Wang et al. [7] were based on 40 days of ScCO2 exposure of only 2
shale samples, whereas this study used multiple shale samples and these
samples were exposed for 60 days of ScCO2 treatment (much longer
exposure time). This enables us to characterize these changes better than
what was carried out in any published literature so far, to the best of our
knowledge. Another important aspect of our study is that we investi­
gated changes in a shorter time intervals while the other study published
on the Bakken [7] simply neglected the changes that could occur in less
than 10 days of exposure to carbon dioxide. Furthermore, our study
provides more robust, longitudinal, continuous, and a better represen­
tative long-term ScCO2-shale observations which can overall provide us
a better understanding of these changes. Furthermore, based on a
significantly greater number of samples tested in this study, we were
able to present macroscale alterations using rock physics modeling.
Another significance of this study is that we provided pore size varia­
tions before and after ScCO2 exposure in shales using image processing,
and this can also support the reliability of the results and analysis.
During time-lapse ScCO2 exposure in shale, there is an alternating
decrease and increase in mineral content which is not an exponential
behavior that was previously reported in [16,72–74]. This current study
is the first to report this significant observation which can be critical for
future CO2 sequestration projects and long-term CO2 storage in shale
formations.
During in-situ CO2 reaction with rock at supercritical conditions,
there is a geochemical reaction between ScCO2 and pore fluid (brine) to
form carbonic acid which further reacts with the host reservoir rock.

12
O. Ozotta et al.
Fig. 10. Pore size analysis of shale samples for (a, b) pre-CO2, and (c, d) after 60 days of ScCO2 exposure.
This ScCO2-saturated brine is slightly denser than the in-situ formation
water and thus vertically migrates into the reservoir [75,76]. Since our
shale cores used in this study are subsurface samples with inherent pore
fluid, thus, this observed carbonic acid-induced mineral dissolution in
shales is suspected as the reason for the observed reduction in strength
and stiffness of shales in this study, with known chemical reactions well
reported [14,16,76,77].
In characterizing the macroscale mechanical properties of the MB
samples, the reservoir-scale CO2-induced alterations were assessed by
upscaling the nanoscale data to a macroscale using rock physics models
(dilute and MT models) (Tables 3 and 4). The macroscale CO2-induced
alterations from dilute and DT models were compared and presented in
Fig. 15. The analyses of the macromechanical results (Fig. 15a) for pre-
CO2 saturation (0 days) indicate that the elastic modulus from the dilute
model varies from the MT model by 10.5 % (i.e., 89.5 % correlation),
and after long-term CO2 exposure (60 days) (Fig. 15a), the correlation
between the macroscale elastic modulus of dilute and MT models was
93.5 %. Similarly, the pre-CO2 saturation (0 days) and post-CO2
macroscale analyses (Fig. 15b) reveal that Poisson’s ratio from dilute
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Applied Energy 326 (2022) 120051
model varies from that of the MT model by 4.2 % (i.e., 95.8 % corre­
lation) and 0 % (100 % correlation), respectively. This further shows
that rock physics upscaling models can be reliable for macroscale me­
chanical assessment of CO2-induced alterations geomaterials.
The analyses of long-term macroscale CO2-induced alterations sug­
gest a relative decrease in elastic modulus (Fig. 15a), with a relative
increase in Poisson’s ratio (Fig. 15b). This observation further validates
the nano- to micro-scale observed changes in mechanical properties due
to long-term CO2 exposure (i.e., after 60 days). The post-60 days CO2
exposure-induced alterations confirm a macroscale weakening in the
mechanical integrity of the host reservoir rock by decreasing of its
elastic modulus (DS model = –33.1 %, MT model = -30.2 %) and
increasing of its Poisson’s ratio (DS model = +37.5 %, MT model = +32
%) after exposure to CO2. These results suggest that shale reservoirs may
be weaker after a long period of CO2 storage, and if the host reservoir is
not protected on top by an overlying formation with high mechanical
integrity (i.e., caprock or seal), it may result in leakage of CO2 from the
storage reservoir through vertical CO2 migration due to failed integrity
of the formation when fractures become abundant. It is necessary to
O. Ozotta et al. Applied Energy 326 (2022) 120051

Fig. 11. Minerals observed on the sample 60-day post-CO2 saturation dolo is dolomite, k-spar is potassium feldspar, py is pyrite and Q is quartz: precipitation
observed (a), cracks observed (b), and more cracks and pores observed (c).

Fig. 12. Statistical analyses for pre-CO2 and post-CO2 saturation conditions: (a) Young’s modulus, and (b) hardness.

emphasize that macroscale mechanical variations that is reported here
should be verified with triaxial measurements which itself is a separate
research topic with its own limitations and has been investigated to
some extent but not with chemical alterations considered through time.
The idea of upscaling results that are the outcome of small (nano/micro)
scale studies is to make us independent from plug (macro) scale mea­
surements which is more time consuming to perform and rely on larger
pieces of samples that’d need extensive sample preparation and exper­
imental setup. Furthermore, as we observed in SEM images and nano­
indentation data, what occurs in large scale studies can only be
explained if finer and more focused scale analysis is conducted from
various angles. For example, based on the results from the electron
microscopy, we can illustrate how fracture initiation, along with salt
precipitation can generally alter the samples pore space and weaken it

14
O. Ozotta et al.
Fig. 13. Relationships between the Young’s Modulus and hardness for (a) pre-CO2 treatment, and post-CO2 treatment after (b) 3 days, (c) 8 days, (d) 16 days, (e) 30
days, (f) 60 days.
mechanically. In this regard, when such nanoscale fractures coincide or
grain contact stiffness is altered from the presence of fluids [75], larger
cracks is expected to be developed within the sample that can highly
impact the core plugs integrity. This will manifest in the field as fault
reactivation and lost caprock integrity that will ultimately endanger the
entire storage process. Therefore, neglecting the nano- to-micro-scale
CO2-induced alterations physicochemically in the design of field oper­
ations can lead to the failure in the integrity of the storage site in the
long-term; therefore, mitigative measures should be put in place to avoid
turning nano-scale changes to become large-scale catastrophic event
either at near-term or long-term. The development of models for CO2
sequestration projects in the Bakken Formation is dependent on geo­
mechanical parameters for accurate and realistic predictions of in-situ
conditions of the host reservoir during pre- and post-CO2 injection
pressures which should be investigated as well separately. Thus, the
nano- and macro-scale alterations observed and presented in this study
due to ScCO2 interaction are important to improve the efficiency of CO2
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Applied Energy 326 (2022) 120051
storage operations and further reduce the long-term leakage risks
associated with CO2 sequestration projects.
6. Conclusions
UCCUS has become widely adopted as a viable option to mitigate
climate change and achieve carbon neutrality. This study coupled
experimental tests and rock physics models to investigate continuous
multiscale multifaceted (mechanical, mineralogical, and structural)
changes in Middle Bakken samples that are exposed to long-term ScCO2.
We used rock physics models to upscale and characterize the CO2-
induced changes at macro/reservoir scale. Based on the results the
following conclusions were made from this study:
i. Shales have higher pore sizes in pre-CO2 than post-CO2 saturation
conditions from the microstructural analyses of electron micro­
graphs via image processing. In this regard, the pore size
O. Ozotta et al.
Fig. 14. Cross-plots of the Young’s Modulus and mineral phase composition for pre-CO2 and post-CO2 saturation conditions: (a) Young’s modulus vs phase 1, (b)
Young’s modulus vs phase 2, (c) Young’s modulus vs phase 3.
distribution of shales showed abundant nanopores (up to 300 nm)
that initially were non-existing in the sample pre-CO2 saturation
but were detected post-CO2 saturation.
ii. The FESEM images revealed mineral alteration, precipitation,
and development of fractures after long-term exposure to CO2. In
addition, During time-lapse ScCO2 exposure in shales, there is an
alternating decrease and increase in mineral content which is not
an exponential behavior based on XRD results.
iii. Based on the nanoindentation test results, the micromechanical
behavior of shale samples showed significant alterations in
Young’s modulus and hardness. Both Young’s modulus and
hardness decreased, and the overall sample weakened with a
higher degree of correlation between these two parameters.
Although there was an overall reduction in microscale Young’s
modulus and hardness, a specific anomaly was established in the
trend of micromechanical properties versus ScCO2 exposure
which can be linked to similarly observed alternating mineral
alterations (increasing and decreasing mineral content). Changes
in mechanical properties are a consequence of variations in
mineralogy and the development of fractures within the tested
samples. In addition, as exposure time surpassed 30 days, stiffer
minerals lost a significant value in Young’s modulus and
hardness.
iv. The interaction between soft and hard minerals or changes that
occur on the intermediate minerals have the highest impact on
the samples’ micromechanical weakening. Overall, CO2 induced
alterations can lead to long-term macroscale weakening in the
mechanical integrity of Middle Bakken shale by decreasing its
elastic modulus (DS model = –33 %, MT model = -30 %) and
increasing its Poisson’s ratio (DS model = +38 %, MT model =
+32 %).
16
Applied Energy 326 (2022) 120051
Integration of the results indicates that due to long-term ScCO2
exposure, minerals in shales evolve, which is followed by precipitation
and the development of microfractures within the tested samples. When
a shale reservoir is exposed to ScCO2 for UCCUS, as in the case of Middle
Bakken shale, alterations in its mechanical, chemical, and microstruc­
tural attributes should be expected. We suggest that the observations
reported in this study are incorporated in future UCCUS projects in shale
formations, and most especially in the Middle Bakken, where a lack of
understanding of these variations and project planning may impact the
project long-term and lead to potential CO2 leakages or environmental
hazards. Therefore, to mitigate possible risks, necessary operational
decisions should be made to ensure the goals of CCUS projects are met
and risks to the environment are minimized.
CRediT authorship contribution statement
Ogochukwu Ozotta: Writing – original draft, Data curation, Formal
analysis. Oladoyin Kolawole: Formal analysis, Writing – review &
editing. Mohamed Lamine Malki: Data curation, Formal analysis.
Thomas Gentzis: Data curation, Writing – review & editing. Hallie
Fowler: Data curation, Investigation. Kouqi Liu: Writing – review &
editing, Validation. Mehdi Ostadhassan: Conceptualization, Funding
acquisition, Methodology, Project administration, Resources, Supervi­
sion, Validation, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
O. Ozotta et al.
Fig. 15. Rock physics models to characterize macroscale ScCO2 induced alteration of Middle Bakken shale mechanical and elastic properties at varying CO2
exposure periods: (a) Young’s modulus, (b) Poisson’s ratio.
Data availability
Data will be made available on request.
Acknowledgment
The financial support of the North Dakota Industrial Commission
(NDIC), Geological Society of America (GSA), Society of Petrophysicists
and Well Log Analysts (SPWLA), and Society of Exploration Geophysics
David Lammlein Scholarship is highly appreciated. The authors would
also like to thank the Advanced Analytical Characterization Laboratory
at the University of North Dakota (UND), for the permission to use their
17
Applied Energy 326 (2022) 120051
equipment and especially the assistance from Dr. Jin Zhang. We would
like to also express our gratitude to the director of the North Dakota core
library, Jeff Baider, and the technical staff, Kent Holland, for providing
the shale samples to us for this study. Last but not list, we’d like to ex­
press our sincere gratitude towards the reviewers of the paper who
meticulously studied it and provided us with valuable comments and
feedbacks in several rounds that for sure improved the quality and the
structure of this work. We’d like to extend our appreciation to the editor,
Professor Yang, for giving us the opportunity to revise the manuscript
and submit improved versions.
O. Ozotta et al. Applied Energy 326 (2022) 120051

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