Energy and Climate Change 2 (2021) 100029

Contents lists available at ScienceDirect

Energy and Climate Change

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

Experimental investigation of the geochemical and mineralogical

interaction between CO2 and carbonate: Evaluation of CO2 sequestration in
dolomite-calcite formations
F. Famoori a, R. Azin a,∗, Sh. Osfouri b, N. Arya c,d
a
Department of Petroleum Engineering, Faculty of Petroleum, Gas & Petrochemical Engineering, Persian Gulf University, Bushehr, Iran
b
Department of Chemical Engineering, Faculty of Petroleum Gas & Petrochemical Engineering, Persian Gulf University, Bushehr, Iran
c
Bushehr University of Medical Sciences, Bushehr, Iran
d
Arya Medical Imaging Center, Bushehr, Iran

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

Keywords: Sequestration of CO2 in saline aquifers has become a renowned procedure owing to the availability of this type
CO2 sequestration of reservoir. This study aims to identify the induced rock and fluid interactions during CO2 injection and their
Saline aquifer influence on the reservoir rock properties like porosity and permeability. A systematic study is required for
Mineralogical reaction
further evaluation of these interaction effects. The experiments were collected from Iranian Asmari formations
Imaging technology (X-ray CT)
in Fars province with significant quantities of dolomite revealed by XRD analysis. The carbonate rock sample is
considered for this study since most of the oil reservoirs in Iran are produced from carbonate Asmari formation.
A series of core-flood experiments were carried out to assess the potential of dolomites to buffer brine and
further promote mineral precipitation over time. Carbonate samples were exposed to CO2 for 2 weeks and 4
weeks. The dissolution and precipitation of minerals were investigated using CBCT to determine the impact of
these processes on rock properties. The result of 4-weeks experiments showed that the reaction with CO2 causes
salt precipitation which is observed in FE-SEM and EDS. The ICP and IC analysis tests showed that long-term
CO2 reaction also creates a significant CO2 drying-out effect and salt (NaCl) crystallization in the aquifer’s rock
pore space by altering the pore structure. Such mineralogical alterations considerably affect the saline aquifer
properties, producing noteworthy outcomes in the sequestration process. For example, the core permeability (C2 )
at 1 ml/s CO2 injection rate and confining pressure of 22 MPa decreased considerably from 51.8 to 15.06 mD
with decrease in porosity from 22.90 to 15.56 using imaging technology (dental X-ray CT). Furthermore, CO2
storage capacity of both core samples was measured for a brine system with a salt concentration of 150,000 ppm.

Introduction Even though, the sequestration process in such reservoirs can be

Global warming has become a major concern amongst scientists. In
order to achieve sustainable use of energy, it is of utmost importance
to control and reduce CO2 which is known as the main constituent of
greenhouse gas. Amongst many possible options for CO2 sequestration,
geological and oceanic reservoirs have found reasonable attention of
researchers [1–4]. Saline aquifers have proven to be the best choice
as the CO2 storage capacity of nearly 10ˆ4 Gt [1,5–7]. According to
some findings, the most preferred aquifers for CO2 sequestration due to
its high storage capacity are located from 1000 to –3000 m below the
earth’s surface [8,9]. Therefore, deep saline aquifers are more adequate
for CO2 storage.
somewhat unpredictable over the long term due to uncertain interac-
tions of CO2 , rock, and brine affecting hydro-mechanical properties of
the rock [10]. Nonetheless, properties such as porosity and permeability
are vital for the sequestration process to be efficient and intact. Accord-
ingly, any unanticipated change in these properties may cause sudden
leakage of CO2 and harm the environment. As a result, owing to the im-
portance of these properties, they have become a major research interest
[11].
Experimental works in the literature have mostly focused on geo-
chemistry and mineralogy in short time periods [12, 13]. An experi-
ment conducted by Muller et al. on sandstone showed a reduction in
permeability causing by precipitation of salt while injecting CO2 into

Abbreviations: CBCT, Cone Beam Computed Tomography; EDS, Energy-dispersive X-ray spectroscopy; EOS, equation of State; FE-SEM, Field Emission Scanning
Electron Microscopes; IC, Ion Chromatography; ICP, Inductively coupled plasma; XRD, X-ray Powder Diffraction.
∗
Corresponding author.
E-mail address: reza.azin@pgu.ac.ir (R. Azin).

https://doi.org/10.1016/j.egycc.2021.100029
Received 6 May 2020; Received in revised form 2 February 2021; Accepted 21 February 2021
Available online 27 February 2021
2666-2787/© 2021 Published by Elsevier Ltd.
F. Famoori, R. Azin, Sh. Osfouri et al.
Nomenclature
Lists of Symbol
𝑝1 cell pressure
𝑝2 standard pressure
𝑉1 the volume of gas injected in the core sample
𝑉2 standard injected volume
𝑇1 the temperature at the cell equal to 30 °C
𝑇2 standard temperature
𝑞 injected rate
𝑞∗ volumetric injected rate
𝑄 cumulative volumetric injected rate
𝜌 gas density
M gas Molecular weight
m cum cumulative CO2 mass injected
NaCl saturated core sample [14]. Ross et al. conducted hydro-chemical
laboratory experiments on sandstone rock and observed porosity and
permeability increase due to the dissolution of carbonate minerals [15].
Theoretically, the relation between porosity and permeability in car-
bonate rock types are not associated. Therefore, changes in porosity
is not dependent on permeability variations. Elkhoury et al. reported
that porosity and permeability were not clearly associated. Experiments
were undertaken on a fractured carbonate and a rise in permeability
was witnessed which was deduced to be due to a mineral dissolution
effect [16]. However, all the mentioned research works have been con-
ducted in short time spans (1 to 3 days) and there is lack of knowledge
about influences of CO2 and mineral reactions in weeks or months. Over
longer periods of time such as weeks or months, rock minerals such as
calcite, dolomite, and clay mineral undergo a reaction with carbonic
acid, derived from CO2 , leading to a rock dissolution, hence affecting
flow patterns [11,14,17].
Credoz et al. conducted a long term batch experiment on crushed
clayey samples [18]. Several crushed rock samples were tested, one type
of sample consisted of 13% calcite, 40% quartz and 7% other minerals
and the other type consisted 45% calcite, 15% mixed illite and smectite,
and other minerals [18]. Some feature has been conducted for the test
series; 1. Providing high temperatures up to 150 °C in order to accel-
erate the chemical reaction. 2. Providing the lower temperature at 80
°C and 3. Providing two injection pressures 1 MPa and 15 MPa of CO2
to check the reactivity of rock-brine near wellbore and far away from
the wellbore. Results of the first test series with 150 °C depicted that a
small calcite dissolution was observed near the CO2 injection and not
any mineralogical reaction was detected in 1 year. Thus it is concluded
that carbonate rock dissolution and the rock-brine reaction occur in a
shorter time span (less than 1 year) with a lower temperature of 150 °C.
Besides, reaction time and precipitation time is different for every rock
samples with different properties and crushed rock samples accelerate
the reaction.
The experiments from Credoz et al. conducted at partial pressures
of 1 MPa and 15 MPa with second rock type represented that the new
form of porosity structure was observed in the rock sample. However,
this research has not established the relationship between chemical and
mineralogical reactions. Moreover, comparing different rock types from
a different location is not very interconnected. In this study, two Ira-
nian Asmari core samples are collected in order to compare the storage
capacity of actual field in different CO2 injection scenarios.
Smith et al. [19] conducted the same experiment with coreflood ap-
paratus to discover the effect of mineralogy on carbonate-dolomite rock
samples. Dissolved CO2 in brine was injected into the rock sample at
the pressure of 22 MPa. Mineral dissolution was observed after 10 days
and let to porosity and permeability enhancement and not any precipi-
tation was observed in the rock sample. The presence of dolomite min-
eral in the rock sample indicated that precipitation could be increased
2
Energy and Climate Change 2 (2021) 100029
and could retain the rock sample integrity. Moreover, the work stated
that dolomite increased the rock-brine equilibrium in a short period and
could limit the enhancement of permeability and porosity structure. On
the other hand, due to better confirmation of dissolution and precipita-
tion in the rock samples, the experiments should be conducted over a
long period of time (more than a week or a month).
A more thorough survey is required to achieve a proper understand-
ing of any change in the stored CO2 . However, research works focus-
ing on both geochemistry and mineralogy are limited. This study is a
comprehensive, combined experimental investigation of geochemical,
mineralogical, and rock properties alteration in saline aquifers for long
term CO2 sequestration over 1 month; considering two reaction period;
one sample for 2 weeks and another for 4 weeks; to identify the
probable changes of rock minerals interacting with CO2 , based on the
time required to complete the reaction of dolomite-calcite minerals. It
is recognized that different rock minerals require dissimilar timescale
and degree of dis-equilibrium to complete their reaction with CO2 and
brine [20]. Depending upon existing rock minerals, adequate time is
needed to create the equilibrium under reservoir conditions. For exam-
ple, the sandstone reservoir showed 1 to 2 years in order to achieve
this equilibrium [21-23]. Hence, in order to understand any reaction
impact in sandstone formations, short term experimentation is inappro-
priate. However, unlike sandstone, carbonate entities have proven to
react much faster with CO2 and brine. Interactions of CO2 and brine
with entities such as magnesite, calcite, and siderite have shown to hap-
pen within 2 to 4 weeks [12,14,24]. Subsequently, considering time as
the main constraint of the experiment, a duration of 2 and 4 weeks have
been chosen as adequate time spans to draw suitable conclusions in this
work. It aims to provide the parameters required for reservoir modeling
of CO2 sequestration by allowing sufficient time for interaction since re-
actions related to minerals only occur in long term exposures. Moreover,
the synthetic brine in this work consists of 100 g/l water NaCl, 50 g/l
MgCl2 , and 50 g/l of KCl which is the composition in the actual for-
mation. However, previous studies mostly conducted the experiments
considering NaCl as the synthetic brine which is not analogous to the
actual aquifer [21,27]. The main purpose of this paper is to introduce
Asmari Carbonate reservoir rock as one of the best applicable forma-
tion in order to provide the safe and secure CO2 sequestration due to
decrease in permeability. This research, therefore, would be widely ap-
plicable to understand the actual behavior of rock properties and rock
structure under reservoir conditions.
Materials and methods
Sample preparation
Asmari carbonate blocks were collected and cored. The sample di-
ameter was selected to be 37.75 mm and the cored samples were sized
as 87 mm and 75 mm long cylinders. The samples were left for a day to
dry completely in an oven before starting the experimental procedure;
the low temperature of 50 °C is selected to prevent cracking.
Sample description
The carbonate samples were collected from an Asmari site in Fars
province which is chosen for carbon storage in this study. This forma-
tion belongs to Oligocene to Miocene era. The main constituents of the
rock specimens are dolomite and calcite whose composition is confirmed
with X-ray diffraction XRD analysis; approximately 71 wt% dolomite
and 17 wt% calcite.
Deep saline aquifers with appropriate rock properties of porosity and
permeability have been considered in many CO2 sequestration proce-
dures. Among the possible carbonate formations, dolomite-carbonate
formations are more preferred for CO2 sequestration due to a poten-
tial to trap great amounts of CO2 through carbonate reaction and less
F. Famoori, R. Azin, Sh. Osfouri et al.
Fig. 1. schematic of coreflood apparatus.
Table 1
Geochemical and Mineralogical characteristics of carbonate reservoir
rock.
Lithology Dolomite-Carbonate Sample
Macroscopic description Color: white-gray yellowish
Formation Oligocene to Miocene ‘dolomite-carbonate’
Structure un-layered, nonhomogeneous
Mineralogy(XRD) 71%Dolomite, 17% Calcite,
(EDS,wt%) 27.44% Ca, 12.24 Mg, 16.63 C, 43.68% O
Porosity Sample C1 : 21.44% Sample C2 : 20.61%
Permeability Sample C1 : 71.83mD Sample C2 : 58.72mD
unexpected dissolution of pore structure that can create an undesir-
able increase in permeability; which is the main reason for choosing
dolomite-carbonate in the current study. Table 1 provides thorough in-
formation regarding mineralogical and geochemical aspects of dolomite
carbonate. Two dolomite-carbonate samples, with almost the same char-
acteristics, were considered for this study named as C1 and C2 . The As-
mari formation consists of un-layered, white-gray colored, and medium
to fine-grained rock mass that shows mostly heterogeneous structure.
Therefore, homogeneous and seamless samples were collected.
Test design
The coreflood tests were designed to simulate the continuous injec-
tion of CO2 in a saline aquifer. A slug of pure CO2 (with the purity
of 99.89%) was injected into the core samples. Synthetic brine with
150,000 ppm was used to represent the saline aquifer. The synthetic
brine used in this study is chemically similar to an aquifer salinity. Tests
were run at the temperature of 31 °C (the temperature where CO2 is at
the supercritical condition). Backpressure or the outlet of the system
was kept closed for all experiments. CO2 is injected to brine saturated
dolomite-carbonate samples every day for 30 min at a constant rate
(1 ml/min and 2 ml/min). This procedure is constantly repeated for
two dolomite samples one for 2 weeks and the other one for 4 weeks.
Core flood setup
The coreflood apparatus was considered for this study is depicted in
Fig. 1. A Syringe pump was used to displace the fluid from the piston
of transfer vessels. Two stainless steel accumulators were used to store
the synthetic brine and CO2 . Swagelok valves were installed at the ac-
cumulator’s inlet and outlet to control the fluid alteration during CO2
3
Energy and Climate Change 2 (2021) 100029
injection. To maintain the pressure at the core inlet and outlet, a pres-
sure gauge was fixed at the core holder ends. A Hassler core holder was
used to hold the core samples during the coreflood test. Viton shore 90
rubber sleeves were used to resist CO2 diffusion into overburden flu-
ids. A hand pump was used to apply overburden pressure around the
core; the overburden pressure was kept 7 MPa higher than the core in-
let pressure. A pressure drop across the core was measured by a pressure
transducer and the data acquisition system to a computer that records
the data through Net Dp software. A summary of coreflood experiments
is listed in Table 2.
Experimental procedure
The core samples were located inside the core holder and synthetic
brine with 150,000 ppm salinity was injected at ambient condition un-
der vacuum, the pressure difference across the core was monitored. CO2
was injected at a constant rate for 30 min each day. The permeabil-
ity and porosity of the cores are measured before and after CO2 injec-
tion. In order to comprehend the influence of precipitation and dissolu-
tion, quantifying porosity and permeability is performed right after the
washout procedure of the core samples, and the porosity and permeabil-
ity difference was compared at these three conditions.
The pore volume of the core sample for brine density of 1.020 g/cm
was calculated after saturation. With the help of CBCT (Dental X-ray
CT scanner) the samples were scanned before CO2 injection, after injec-
tion and after the washing out of the core. Just before the porosity and
permeability tests, the core samples were removed from the core holder
and oven-dried for 1 day. Then, freshwater and Ethanol are alternatively
injected at high pressure to wash out all the probable salt precipitation,
then samples are oven-dried for 1day to be prepared for porosity and
permeability tests.
The brine inside the core samples was removed by opening the back-
pressure valve under 10 MPa confining pressure, this procedure was
carried out until the removal of brine stopped. There should not be any
mobile brine inside the core sample because there could be brine held in
place by capillary force, therefore CO2 is injected at 1 MPa to make sure
all brine is removed. The main reason for continuing the reactions for
different time span was to provide sufficient time for CO2 /brine/rock
reactions and for the samples’ pore structure to change consequently
over time. The porosity and permeability tests on these altered cores
gave a chance to realize how samples’ flow characteristics had changed.
For instance, for C1 sample, CO2 was injected at 2 ml/min injection
rate, the pressure difference at the two core holder ends was recorded
constantly. The pressure was increased during CO2 injection and it be-
F. Famoori, R. Azin, Sh. Osfouri et al.
Table 2
Summary of coreflood experiments scenarios.
Core Name Pore Volume (brine saturation) No of CO2 injection Cycles
C1 5 13
C2 5 22
came constant after 20 to 24 h, and the experiment proceeded and CO2
injection cycle was repeated until brine was fully saturated by CO2 in-
jection (at the pressure of 18 MPa). At this stage, CO2 injection cycle
was stopped. At this step, the valves were closed and let the pressure
reached a constant level for 4 to 5 days. This experiment was taken for
21 days. Similarly, the equivalent experiment was taken for C2 sample
apart from the injection rate (1 ml/min). For a better understanding of
the precipitation effect and dissolution of CO2 , two different injection
rates were evaluated and compared for this study.
Surface morphology analysis
The surface morphology of both C1 and C2 samples was primarily
studied using EDS and FE-SEM. FE-SEM method is capable to produce
high-resolution images of the carbonate surface morphology. Both fresh
and treated CO2 samples were investigated using FE-SEM and EDS and
the results from such analyses were compared and evaluated.
ICP and IC analysis
ICP- MS, and IC were used to investigate the ion and elemental prop-
erties of the brine inside the core samples. Both conditions before and
after CO2 treated brine were investigated using ICP and IC analyses.
Image analysis technique
X-ray CT scanners are generally used for medical applications, i.e.
scanning parts of the human body without damaging the tissue. Over
the past few decades, this technique has been applied in petroleum engi-
neering. Almost all previous studies used a medical X-ray CT scanner for
conducting experiments. However, Dental CBCT is used for this study for
the first time. CBCT is an imaging method that uses X-ray beams rotat-
ing around an object. The importance of choosing dental X-ray imaging
is to provide fast, non-invasive way rather than conventional medical
X-ray CT scanners.
The Dental X-ray CT is the Cranex 3D scanner that provides image by
rotating the object in 360°. It has 2 axes, a detector, a flat X-ray screen
and a processor that could get the clearest images. The resolution of the
images obtained from CBCT is 200 micrometers. Also, Dental CBCT pro-
vides 3D information including hard tissue and soft tissue of the object.
Besides, the accessibility of dental CBCT devices with high-quality imag-
ing makes it even more practical for engineers and researchers. Fig. 2
depicts the dental CBCT device below.
Digital core samples were obtained using CBCT, and after a series of
image segmentation using On Demand 3D, they were converted to the
JPG file. The JPG files were imported to MATLAB software for a series
of image processing to measure local porosity, porosity distribution, and
average mean porosity of the core samples.
Firstly, after image reconstruction, each scanned image has a number
that can be used to express the properties of the objects which is called
voxel number; the available information includes a series of different
numbers based on their densities. Therefore, it is essential to convert
them into grayscale images. For example, +1000 scale numbers are con-
sidered as a white color and −1000 ones are considered as black color.
Hence, there are 2000 grayscale levels between black and white scale
colors.
Human eyes can differentiate 256 grayscales colors. Therefore, de-
pending on the ability of human eyes, grayscale is divided into 256
grayscales colors.
4
Energy and Climate Change 2 (2021) 100029
Injection flow rate(ml/min) Temperature °C Case
2 31 Effect of dissolution
1 31 Effect of precipitation
These subtracted grayscale levels are scaled from 0 to 256 and from 0
to 1 with an integer interval respectively. Hence, it is possible to express
these images in the form of a Cartesian coordinate system as shown in
Eq. (1):
⎡ 𝑓 (1, 1) ⋅⋅ ⋅⋅ 𝑓 (1 , 𝑌 ) ⎤
⎢ ⎥
⋅⋅ ⋅⋅ ⋅⋅ ⋅⋅ ⎥
𝑓 (𝑖, 𝑗 )⎢ (1)
⎢ ⋅⋅ ⋅⋅ ⋅⋅ ⋅⋅ ⎥
⎢𝑓 (𝑋, 1) ⋅⋅ ⋅⋅ 𝑓 (𝑋, 𝑌 )⎥⎦
⎣
Where
i = 1 to X
j = 1 to Y
After converting the images to a function, it is essential to pre-
treating the images before starting the image analysis. Firstly, all im-
ported images are cropped into square size in MATLAB software and
then converted to a black and white scale (Fig. 3).
The next step is image contrast improvement. It can help to achieve
microstructure material and it develops the contrast between different
inner materials which is called histogram equalization transformation.
The last step is the noise elimination technique. Digital images are dis-
posed to a range of noises and it could be generated in many ways.
Therefore, to obtain a precise result, the noise removal method should
be applied. Usage of median filter has been found as an appropriate
noise elimination method that would not blur the edges of the images.
It is a non- linear type filter which is able to change the pixel value of
the images.
Experimental results and discussion
The main purpose of this study was to identify the effect of sample
porosity and permeability on the interaction between brine, rock, and
minerals. Therefore, coreflood tests were run for two carbonate samples
(C1 and C2 ), and the pressure difference across the inlet and outlet of
the core holder was recorded.
Fig. 4 illustrates the pressure increase in C1 sample from 2 MPa to
almost 18 MPa after 2 weeks. According to the Figure, the pressure was
increasing after each CO2 injection cycle. After almost 2 weeks of repeat-
ing the same injection scenario, a sudden pressure rise from 3.5 MPa
to almost 18 MPa was observed. We concluded that the sudden rise
in pressure for a moment while injection, could represent a fully satu-
rated brine with CO2 on day 14 and no more CO2 gas could dissolve
in the brine. At this moment gas injection flow was stopped and let the
injected CO2 to reach equilibrium. On day 20 to 21, the pressure be-
havior remained steady at 7 MPa. An equivalent experiment was taken
for C2 sample with a different injection rate (1 ml/min). This test was
performed for almost 1 month and after 21 days the pressure reached
almost 22 MPa which proposed that brine was fully saturated with CO2
and no more CO2 could be dissolved in brine after the sudden increase
in pressure (Fig. 5). The sudden pressure rise while injecting CO2 with
an injection rate of 1 ml/min occurred on day 21 (1 week more than
C1 sample with 2 ml/min injection rate). The injected CO2 rate for C1
sample was 2 ml/min for the duration 30 min each day and CO2 was in-
jected for 12 days continuously. Therefore, total CO2 injected in C1 core
sample was 720 ml. The injected CO2 rate for C2 sample was 1 ml/min
each day that lasted for 22 days and total amount of CO2 injected in C2
was 660 ml.
In both experiments, same condition has been conducted except
CO2 injection rate. For instance, CO2 was injected at constant rate of
F. Famoori, R. Azin, Sh. Osfouri et al. Energy and Climate Change 2 (2021) 100029

Fig. 2. Dental X-ray CT scanner device.

Fig. 3. cropped sample of a scanned segment.

Fig. 4. pressure profile for C1 sample during CO2 in-

1st Day
20 C1 2nd Day
jection.

3rd Day
4th Day
5th Day
6th Day
Pressure(MPa)

7th Day
9th Day
10 10th Day
11th Day
12th Day
13th Day
14&15 th Day
20th Day
0
0 100 200 300 400 500
Time(hr)

5
F. Famoori, R. Azin, Sh. Osfouri et al. Energy and Climate Change 2 (2021) 100029

Fig. 5. pressure profile for C2 sample during CO2 in-

25 jection.
1st Day 2nd Day
3rd Day 4th Day C2
5th Day 6th Day
20 7th Day 8th Day
9th Day 10th Day
11th Day 12th Day
13th Day 14th Day
Pressure (MPa)

15 15th Day 16th Day

17th Day 18th Day
19th Day 20th Day
21th Day 22nd Day
10 23rd Day 24th Day
25th Day 26th Day
27th Day

0
0 100 200 300 400 500 600 700
Time (hr)

2 cc/min each day for 30 min. After 12 days of constant CO2 injection,
the pressure increased to 18 MPa suddenly. Sudden increase in pressure
represented that the core sample is fully saturated with CO2 (produced
2 phase of CO2 and brine). However, in the slower CO2 injection rate
(C2 ) the pressure increased to 18 MPa after 22 days of constant injection
rate. Also, from mathematical estimation of CO2 solubility (mathemat-
ical modeling section), we observed that CO2 storage in C2 was more
than C1 . Results indicated that the slower injection rate could provide
the more secure CO2 storage in rock sample.
The pressure behavior of both core samples were similar except for
the injection rate. However, injected CO2 with a 1 ml/min rate could dis-
solve more CO2 before a sudden increase in pressure. Interaction of CO2 -
rock-brine is a slow process and the moderate injection rate (1 ml/min)
could let more dissolution of CO2 with the existing brine. Therefore, this
work illustrates that the second experiment could be a better scenario
to inject more CO2 gas in the core sample.
Figures above show a gradual increase in pressure during the CO2
flow while injection. The next CO2 injection cycle caused a more remark-
able rise in pressure. This mechanism of this phenomenon explains that
the increase in pressure was due to damage introduced by the migration
of fine elements, that originally involved the dissolution of carbonate
minerals, which later caused precipitation of the chemically reaction in
the pore-throat of core samples. Generally, CO2 flows in the larger pore
throats and brine traps in smaller pores. However, fine products cause
more resistance to CO2 flow; due to the reaction between CO2 and the
formation rock precipitation at the pore throat. After sometimes, when
precipitation continues, CO2 is diverted into the smaller pore throats and
tries to displace the brine and start to flow in the smaller pores. At this
moment, an increase in pressure drop occurs. But, brine cannot displace
further because the backpressure is kept closed. The closed back pres-
sure in Core flood set up characterizes a closed actual reservoir. Hence,
CO2 has enough time to dissolve with brine after injection ended and
sudden pressure drop happens after stopping the CO2 injection. After al-
most 20 h the pressure drop decreases gradually until it stops to a point
where when no pressure drop is evidenced. At that time, the next CO2
cycle is injected.
Visualization and quantification of porosity using X-ray CT scan
The images constructed from the CBCT scan are in greyscale and can
be converted to JPG using On Demand 3D software. The image is then
improved and processed with the image tool in MATLAB. Figs. 6 and 7
represent the 3D view and a different segment (slice) along the length
of the core samples respectively.
It is important to keep the samples at the same location during CT
scanning. CT scans are made for fresh samples as well as treated CO2
saturated brine and also after washing out the core samples. The core
samples are scanned for 30 s. About 300 images were taken per scan,
with a distance of 0.027 mm between every image. For these 300 images
porosity is averaged and estimated for each core sample. However, to
reduce processing time 50 segments are collected to evaluate porosity
and pores structures.
Porosity and permeability alteration before and after CO2
injection
One of the many major challenges for CO2 sequestration in saline
aquifers, both pre and post-injection, is the possibility and prediction of
any change in rock characteristics of the formation. Especially, changes
in porosity and permeability in the reservoir are caused by CO2 , rock,
and brine interaction. To date, the majority of experimental works have
represented samples taken from near-wellbore areas over a short time
span [9,25,26]. Rock characteristics alteration during CO2 injection is a
very crucial issue in order to understand the geophysical behavior and
reaction mechanism during a real field time frame, and it was a failure
to capture long-term reaction mechanisms. Therefore, porosity and per-
meability alteration before, after CO2 injection, and after washing out
the core sample is evaluated in this study. Injection of CO2 in aquifer
causes porosity and permeability increase in rock formation which leads
to leakage and return of CO2 to the surface of the earth over time.
Appropriate gas injection scenarios investigated in this study increase
the performance of secondary trapping mechanisms by giving sufficient
time for the CO2 to dissolve in the brine, which ensures a better storage
safety.
Table 3 depicts the porosity and permeability of C1 and C2 core sam-
ples before and after injection. Porosity and permeability are measured
using an X-ray CT scanner and Helium porosimeter to compare and val-
idate the Dental CT-scanner measurements.
Reduction of porosity and permeability for both core samples could
be the result of sedimentation of salt and rock minerals which leads to
reducing the rock properties of the samples and guarantied CO2 seques-
tration. However, C1 sample porosity using X-ray CT is decreased after
CO2 injection and increased after washing out the procedure. Hence,
permeability is reduced (from 71.83 to 56.60) with an increment of

6
F. Famoori, R. Azin, Sh. Osfouri et al. Energy and Climate Change 2 (2021) 100029

Fig. 6. 3D view of C1 (left side) and C2 (right side) samples using CBCT.

Fig. 7. segments of C1 and C2 samples using CBCT.

Table 3
Calculated porosity and permeability using Helium porosimeter and X-ray CT scanner.

C1 Before Injection After Injection After washing out the core

Porosity(%) CT X-ray 22.08 17.45 24.24

Porosity(%) (Porosimeter) 21.44 20.08 21.22
Permeability (mD) 71.83 54.23 56.60
C2 Before Injection After Injection After washing out the core
Porosity(%) CT X-ray 22.90 9.15 15.56
Porosity(%) (Porosimeter) 20.61 14.57 20.24
Permeability (mD) 58.72 6.09 15.06

Fig. 8. Variation of local porosity of C1 sample us-

Before Injection After Injection After washing ing X-ray CT scan.
30 C1
Porosity (%)

25

20

15
0 10 20 30 40 50
Segments

porosity from 22.08 to 24.24. Luhman et al. conducted the experiment
to evaluate porosity-permeability relationship over different flow rates
for dolomite carbonate core samples. Results highlighted that porosity
and permeability were not associated with one another [27]. This study
was also proven by Smith et al. [28]. Fig. 8 shows the variation in local
porosity of C1 sample before injection, after injection and after washing
out condition. As expected, sample porosity increased after washing out
the core, but surprisingly sample permeability decreased with increasing
porosity.
However, after exposure to CO2 for 4 weeks, C2 sample porosity and
permeability were both reduced. It is assumed that in this case porosity
and permeability are clearly associated. Fig. 9 depicts that the porosity

7
F. Famoori, R. Azin, Sh. Osfouri et al. Energy and Climate Change 2 (2021) 100029

Fig. 9. C2 Porosity & permeability ratio.

1
0.9 Enhancement Damage
Kfinal/Kinitial Phi final/Phi initial

0.8
0.697574893
0.7
0.6 K ratio
0.5
phi ratio
0.4
0.3 0.258662093

0.2
0.1
0

Fig. 10. Variation of local porosity of C2 sample us-

before injection After Injection After washing ing X-ray CT scan.

21 C2
Local porosity

16

11

6
0 10 20 30 40 50
Segments

ratio and permeability ratio are reduced due to salt deposits and min- difference in both C1 and C2 samples which indicates the heterogeneity
eral precipitations. However, the reduction ratio of permeability was of such rock samples.
significantly greater than the porosity ratio. 𝜙𝑓 𝑖𝑛𝑎𝑙 − 𝜙𝑖𝑛𝑖𝑡𝑖𝑎𝑙
Generally, when CO2 injection pressure reaches 8.26 MPa (the pres- 𝜙= × 100 (2)
𝜙𝑖𝑛𝑖𝑡𝑖𝑎𝑙
sure which CO2 is in supercritical condition), the solubility increases,
and eventually the precipitation of salt and rock mineral increases which
leads to a decrease in porosity and permeability of rock [29]. Fig. 10 de- Chemical analysis
picts the variation of C2 sample local porosity in three conditions; before
CO2 injection, after CO2 injection and after washing out the core. Chemical analysis was aimed to identify any change in the pore struc-
The local porosity along the C2 sample showed a decreasing trend in ture which may have been caused by interactions of CO2 brine and rock
porosity. Even after washing out condition, the initial porosity (before minerals. ICP (inductively-coupled plasma mass spectroscopy) and IC
CO2 injection) is considerably greater than the treated CO2 condition. were utilized for elemental determinations of fluid (brine) in this study.
It should be noted that both C1 and C2 samples were collected from A plain unreacted brine sample and CO2 reacted brine sample were
one piece of rock and have almost the same properties. However, the tested. Dissolved Na+ , K+ , Mg2+ , Ca+ , Fe2+ , were determined using ICP,
behavior of C1 and C2 samples are quite different. When CO2 is exposed and Cl− and Br− obtained using the IC method. The results are reported
in a longer time span, the rock properties’ behavior changes relatively. in Table 4.
Therefore, longer the CO2 exposed to the rock the greater the solubility With the help of ICP and IC tools, the leach-ability of various min-
reaction and precipitation of rock mineral. erals was determined amongst which calcite showed a considerable dis-
According to the variation of local porosity results from (CBCT), the solution; a rise in Ca2 + ion in the solution is a manifestation of this
pores of the sample were completely non-homogeneous. In heteroge- dissolution effect. Ca2 + ion rose from 1360 mg/l to 2000 mg/l. This ob-
neous reservoirs, CO2 cannot directly move upward due to gravity force servation is therefore believed to be due to the contact of carbonic acid
in heterogeneous formations. The displacement of water would not be that was formed by the supercritical CO2 in the solution. These reactions
the piston like process in aquifer. Generally, Water occupies in smaller are shown in Eqn 6–(7).
pores and CO2 remains in large pores. Therefore, CO2 cannot move di- ( )
H2 O + CO2 + CaCO3 ≪ Ca HCO3 2 (3)
rectly due to various size of the pores in reservoir rock [30]. Hence, the
contribution of residual gas increases, and a large amount of CO2 gas
is stored in such types of reservoirs. Fig. 11 depicts the local porosity CO2 (gas) ≪ CO2 (aq) (4)

8
F. Famoori, R. Azin, Sh. Osfouri et al.
Fig. 11. local porosity ratio for C1 and C2 core samples.
Table 4
ICP/IC analysis of pure brine and reacted brine (Concentration in mg/l).
Condition Na Ca K Mg
Initial Brine 7300 1360 16,700 1013
Reacted Brine 9000 1980 21,800 1060
CO2 (aq) + H2 O ≪ H2 CO3 (aq)
H2 CO3 (aq) ≪ HCO3 − + H+
HCO3 − ≪ CO3 −2 + H+
Previous researches pointed out the link between CO2 dissolution in
brine and solubility trapping in CO2 sequestration [24,31]. Nonetheless,
the mentioned dissolution is a prominent factor in both solubility and
mineral trapping mechanisms; The Hydrogen ion (H+ ) is predicted to
react with the minerals of the reservoir, changing the pore structure.
Gledhill and Morse emphasized that the dissolution of calcite in car-
bonate rock reservoirs significantly changes the pore structures [32].
Additionally, this dissolution phenomenon could create induced pores,
which are made by alteration of flow properties of the formation. More-
over, incremental of Fe2+ (in Table 4) shows siderite dissolution in the
core sample and the rise in the amount of Mn2+ is from the dissolution of
probable clay minerals. Except for dissolution effects, CO2 dry out phe-
nomenon and salt precipitation in the core sample are reported from
ICP analyses. These two effects have been reported to occur near the
wellbore, by previous research works, to cause a reduction in porosity
and permeability on CO2 injection into aquifer [33, 34]. Precipitation
of salt occurs due to the evaporation of water in the aquifer as soon as
CO2 is injected into the formation. For this to happen, the concentra-
tion of salt must be greater than of dissolution effect. Hence precipita-
tion of salt is undoubtedly associated with a rise in salinity (Na+ and
K+ concentration). Results from ICP depicted that Na+ and K+ increase
from 7300 to 9000 mg/l and 16,700 to 21,800 mg/l respectively. This
result is also confirmed with FE-SEM analysis. The CO2 treated sam-
ple displays the deposition of salt precipitation inside the rock structure
(Fig. 12).
Dissolution of calcite is proposed as the following reactions:
CaCO3 +H2 CO03 ≪ Ca2 +2HCO−
3 SRK as suitable ones to identify supercritical characteristics such as that
CaCO3 +H+ ≪ CO2+ +HCO−
3 (9)
Energy and Climate Change 2 (2021) 100029
Cl Li Cr Fe Br Mn Ni
2364 0.024 — — 0.18 0.07 0.07
2889 0.059 0.021 0.51 0.22 2 7.2
(5) CaCO3 +H2 O ≪ Ca2+ +HCO− −
3 +OH (10)
These reactions are mainly dependent on the reservoir temperature,
(6)
CO2 pressure, and pH. The calcite dissolution rate is dependent on CO2
pressure. It increases with increasing CO2 pressure and a reduction in
(7) the pH of the solution [35]. Wigand et al. reported a rise in the disso-
lution of calcite, in more than five days after CO2 injection, and sub-
sequent fall in pH value. the calcite reaction rate is reduced after 2
months of CO2 interaction associated with an increment of pH over-
time (two months) [21]. While in this work it was not feasible to mea-
sure the dissolution rate of calcite, the concentration rate of Ca+ from
1380 mg/l to 1980 mg/l show significant dissolution of minerals, which
is due to longer interaction of CO2 with brine. In accordance with this
study, there is a higher possibility of enrichment of calcite dissolution
rate with CO2 , brine, and rock interactions; since geological storage is
directed over a long time span in the field.
Mathematical modeling of CO2 sequestration
CO2 solubility in brine (pore fluid)
One of the important concerns in the geological storage of CO2 in
saline aquifers is to fully comprehend the phase behavior of the stored
gas and the solution. Moreover, regarding transfer modeling, density
and viscosity are the main physical characteristics that matter. And as
for the disposal capacity calculation, CO2 solubility factor in water and
in saline becomes of great interest. There are various models applica-
ble for calculation of CO2 solubility in pure water or brine [36,37]. The
EOSs have been modifying since 1873, hence there is a countless num-
ber of EOS equations by now. Among these, the PR, RK, and SRK are
the best equations that have received most modifications and obtained
from empirical original form. Accordingly, many research works have
focused on the capability of these equations, and they have found PR and
(8)
of vapor pressure [38–40], liquid molar volume [38,41,42] vapor mo-
lar volume [40] and enthalpies of vaporization [43]. Though the latest
9
F. Famoori, R. Azin, Sh. Osfouri et al. Energy and Climate Change 2 (2021) 100029

Fig. 12. FE-SEM results, a-b) fresh sample c) C1 sample at the inlet d) C1 sample at the outlet e) C2 sample at the inlet f) C2 sample at the outlet.

Fig. 13. comparison of EOSs models of CO2 solubility

C O 2 S ol ub i l i t y in brine at the temperature of 30 with Zirrahi et al.
[43].
0.1

0.01
XCO2

SRK
PR
Zirrahi et al

0.001
0 5 10 15 20
Pressure(MPa)

studies of Nasrifar and Bolland [44] and Le Guennec et al. [45] discov- Equation of state
ered that PR EOS had no clear advantage over the SRK EOS in predicting
vapor pressure. In this study, both SRK and PR EOSs are modeled and Fugacity of gaseous and aqueous phases become equal at the condi-
compared to calculate the solubility of CO2 in brine. Results depicted tion of thermodynamic equilibrium.
that from experimental pressure and temperature, there is no difference
between these two models.
𝑓𝑖𝑣 = 𝑓𝑖𝑎𝑞 (11)

10
 F. Famoori, R. Azin, Sh. Osfouri et al. Energy and Climate Change 2 (2021) 100029

Where 𝑓𝑖𝑣 is the fugacity of species in the gas phase and 𝑓𝑖𝑎𝑞 denotes CO2 storage capacity accurately. CO2 storage in the deep saline aquifer
fugacity in the aqueous phase. Fugacity of species in the gas phase is is considered an outstanding means of storing due to large storage ca-
defined as: pacities and it is dependent on a variety of conditions such as pressure,
temperature, and brine compositions. Both experimental and solubility
𝑓𝑖𝑣 = 𝑦𝑖 𝜙𝑖 𝑃 (12)
modeling indicated that an increase in pressure would significantly in-
Where 𝑃 , 𝑦𝑖 and 𝜙𝑖 represent the total pressure, the mole fraction of the crease the solubility. On the other hand, temperature changes are less
i component, and the fugacity coefficient respectively. effective than pressure changes. For instance, at lower temperatures (be-
The ionization of CO2 in aqueous solution could be neglected due to low 100 °C), solubility increases, and higher temperatures, the solubility
the low solubility of CO2 in aqueous solution. Therefore, the fugacity of is less effective to temperature changes (above 200 °C). Brine salinity is
the aqueous phase can be obtained by using Henry’s law as given by: the other parameter that affects the CO2 solubility and the higher salin-
ity leads to a decrease in CO2 solubility. However, if the CO2 pressure
𝑓𝑖𝑎𝑞 = 𝑥𝑖 𝜙𝑖 𝑃 (13)
increase more CO2 would dissolve with H2 O of the brine and would
In this work, Kij binary interaction parameter is determined using favor the solubility reaction. Hence, the CO2 storage capacity would in-
Henry’s law constant (𝜙𝜙approach). crease considerably.
𝑓𝑖𝑎𝑞 ( )
𝐻 = lim = lim 𝑃 𝜙𝑎𝑞
𝑖 (14) Storage capacity
𝑥→0 𝑥𝑖 𝑥→0

Where 𝜙𝑎𝑞𝑖 is the fugacity coefficient of solute in the aqueous phase and The storage capacity of CO2 stored in aquifer depends on many pa-
can be calculated by combining EOS and classical mixing rule. However rameters that have a significant effect on many processes of sequestra-
modeling solubility of the gas in water is often reported by 𝜙𝛾 approach tion such as porosity, permeability, pressure, salinity, reservoir type,
[46,47]. In 𝜙𝛾method EOS identifies the state of the gas, while Henry’s and reservoir boundary condition. A method for measuring the storage
law determines the behavior of the solution. These models are best to capacity of closed storage formation is suggested in this study. The ba-
characterize low-pressure conditions of the gas in the solution. However, sic principle is that CO2 injection into a closed system leads to a rise in
three major drawbacks have been introduced for this method: pressure. This rise in pressure is accompanied by a replacement of brine
with the injected CO2 , displacing the brine to the expanded pore space
(i) Although it is feasible to closely determine Henry’s law constant, it is
or causing it to store in the seals or even leak through the seals into over-
difficult to accurately calculate and estimate infinite dilution partial
lying layers. In this study, the storage capacity mainly depends on pores
molar volume of the solute in a solvent.
and brine compressibility that provides expanded pore space available
(ii) This method is unable to describe the state of the system in critical
for storing the injected CO2 and on maximum pressure buildup that the
point conditions by showing unusual behavior.
formation could withstand. In order to store the injected CO2 in a closed
(iii) This approach fails to fully identify the vapor-liquid equilibria
system, a rise in the density of the brine and enlargement of the pore
[48,49].
structures are determining factors. This paper represents measurements
The 𝜙𝜙 method does not include such drawbacks. The only required of experimental Z-factor and standard volume of CO2 injected in these
parameter in this approach is the binary interaction factor. The equation experiments for pressure ranging from 1 to 23 MPa.
of state can be considered for a high-pressure condition with no need to
partially dilute the solute in the solvent. Furthermore, using this method, Procedure for CO2 mass determination
the equation of state approach does not show unusual behavior near
the critical point. Hence, in the current work, we have opted for the The CO2 mass storage is determined by manipulating the real gas
𝜙𝜙approach to describe the solubility of CO2 in brine. law and assuming that gas will behave ideally at ambient pressure and
Both Peng Robinson and SRK EOSs are modeled in order to compare temperature.
these two models. Results depicted that both EOSs with experimental The real gas law is defined as follows:
conditions in this study have the same behavior. Fig. 12 shows the CO2
𝑝𝑣 = 𝑍𝑛𝑅𝑇 (15)
solubility in brine for both EOSs. In order to validate our data, we com-
pare our model to Zirrahi et al. model [47]. Zirrahi et al. have described For standard composition system, the product of pressure and tem-
the 𝜙𝛾 approach using Peng Robinson EOS coupled with a nonrandom perature is constant, thus:
mixing rule to model sour and acid gas phase in various ranges of pres- 𝑃1 𝑉1 𝑍 𝑛𝑅𝑇1 𝑃 𝑞 𝑍 𝑛𝑅𝑇1
sure and temperature (pressure range to 60 MPa and temperature range = 1 𝑜𝑟 1 1 = 1 (16)
𝑃2 𝑉2 𝑍2 𝑛𝑅𝑇2 𝑃2 𝑞2 𝑍2 𝑛𝑅𝑇2
between 23 and 103° °C) for the salinity of 200,000 ppm. To calculate
the water content of acid gas with brine, a correlation factor was de- Where the subscripts are
fined by Katz et al. [50]. This proposed correlation factor is very accu- 1 Experimental condition in the cell
rate than other salt effect correlations and is applicable for salinity up to 2 Ambient or standard condition
200,000 ppm. The conversion factor for the salinity of 150,000 ppm is
0.92. Therefore, using this correlation factor helps to compare the CO2 At standard condition pressure and temperature are assumed to be-
solubility of this study with Zirrahi et al. have like an ideal gas, so the compressibility factor is unity. Z1 is mea-
The importance of solubility modeling can be used to accurately sured using the Peng Robinson Flash calculation for pressure ranging
calculate the CO2 solubility with the number of conditions that are from 1 to 23 MPa. Hence the standard volumetric rate can be calculated
provided using correct EOS. Besides, laboratory experiments consist of as follows:
many uncertainties that geochemical modeling and thermodynamics as- 𝑞1 ∗ 𝑍 𝑝
sist to accurately measure the CO2 solubility. Generally, laboratory ex- = 1 2 (17)
𝑞2 ∗ 𝑝1
periments could be conducted in a shorter time. However, thermody-
Where 𝑞 ∗ is defined as:
namic modeling could predict the geochemical reaction and storage ca-
pacity for a long time (100 to 1000 years). On the other hand, variables 𝑞𝑀 = 𝑞∗ (18)
like pressure, temperature, and brine salinity would increase the com-
The standard cumulative volumetric rate can be written as follows:
plexity of the formation behavior. Therefore, in this study, a comparison
between PR and SRK was conducted under the experimental conditions 𝑞1 ∗ 𝑝1
and the models were validated with Zirrahi et al. model to estimate the 𝑄2 = (19)
∫ 𝑍1 𝑝2

11
F. Famoori, R. Azin, Sh. Osfouri et al.
10
1
Mass CO2 (Kg)
0.1
0.01
0.001
0 100 200 300 400 500
Injected Time (min)
CO2 mass injected is defined as:
𝑚2 = 𝑄2 𝜌 (20)
( )
𝑞1 ∗ 𝑝1
𝑚=𝜌 (21)
𝑍1 𝑝2
Cumulative CO2 mass injected is defined as follows:
𝑀 𝑞1 ∗ 𝑝1
𝑚𝑐𝑢𝑚 = (22)
∫ 𝑍1 𝑅𝑇2
Fig. 14 shows the storage capacity of C1 and C2 core samples. It
indicated that CO2 storage capacity is highly dependent on the injection
time and the duration of injection. For instance, the C1 injection rate is
2 times greater than C2 core sample, and results in C1 storage capacity
are approximately half of C2 core sample. Therefore, the injection rate,
injection time, and duration of CO2 injection have significant effects on
CO2 storage capacity.
Despite being a non-polar molecule, CO2 demonstrates a strong sol-
vent capacity at low pressure and high temperature. In a supercritical
state, the amount of CO2 that could dissolve in H2 O is determined by
its salinity, pressure, and temperature. Generally, more CO2 is dissolved
into H2 O in high pressure and temperature. Therefore, at higher pres-
sure and temperature, salt content increases eventually. The high sol-
ubility of water in the ScCO2 (Supercritical CO2 ) may alter the equi-
librium in the aqueous phase and even lead to phase separation which
could be a threat to the CO2 injectivity. But if salt content increases dur-
ing the injection process, it lowers the water solubility. Mineral trapping
may also occur over a very long period of time and we could not ensure
that the precipitation observed in the core sample, would be mineral
precipitation. However, mineral dissolution and solubility of mineral in
these type of reservoir rock was observed in 2 weeks to 1 months. This
indicated that Dolomite-Calcite reservoir rock reacted with CO2 very
faster than we expected.
This Study presented a gas injection scenario that is given sufficient
time to dissolve the CO2 in brine, caused soaring the solubility of the
CO2 in brine and safety of full CO2 storage overall.
Consequently, each experiment includes 30 min of CO2 injection ev-
ery day and 20 h is given for CO2 to dissolve with brine with a high
salinity of 150,000 ppm. The effect of the injection rate on rock struc-
ture has been studied and analyzed with the help of XRD, EDS, and
FE-SEM. Chemical analysis is conducted to determine the rock-brine in-
teraction evidence ion (H+ ) is expected to react with the minerals of
the reservoir, changing the pore structure and caused an increase in
pH value. Consequently, pH reduced considerably after continuing the
CO2 injection. Therefore, precipitation is more significant in the core
samples compared to mineral dissolution strength. Results from CBCT
12
Energy and Climate Change 2 (2021) 100029
Fig. 14. C1 & C2 core samples storage capacity
(discontinuous CO2 injection).
C1
C2
600 700
analysis depicted that the permeability of both C1 and C2 core samples
decreased drastically after almost 1 month of CO2 injection. As men-
tioned in previous sections, carbonate-dolomite rock-CO2 -brine inter-
action could happen in the duration of 2 weeks to 1 month. Therefore,
indicating an injection scenario helps to decrease the risk of CO2 leakage
in the actual field. Several analyses such as FE-SEM and CBCT of local
porosity depicted that precipitation in the outlet of both core sample was
detected. Therefore, it may be possible to have mineral precipitation in
the actual reservoir in longer period of time.
A key to the successful development of CO2 sequestration primar-
ily focuses on the effective and safe storage of CO2 . Therefore, in this
research, we propose an injection scenario to rise the security of CO2 se-
questration. Besides, the estimation of CO2 storage capacity under the
experimental condition complements this study to propose a better un-
derstanding the reservoir behavior.
Conclusion
CO2 sequestration into saline aquifer causes its geochemical proper-
ties to be significantly changed, and the purpose of this study is to find
how CO2 storage impact the mineralogical structure. According to the
results of porosity tests and permeability tests obtained from the Asmari
reservoir, the following conclusion can be drawn:
• The changes in pore structure due to CO2 reaction caused a de-
crease in porosity and permeability and it was observed that As-
mari dolomite carbonate reservoir rock is a preferable reservoir for
sequestration purposes. The fact that highly fractured geological for-
mations could safely store CO2 has large implications in terms of CO2
storage capacity around the world and could increase the number of
locations where CO2 storage could take place.
• Results from Coreflood experiments and mathematical estimation of
CO2 storage declared that; the slower injection rate could provide
the more secure CO2 storage.
• Results from XRD, FE-SEM, and EDS analyses indicated that salt and
mineral precipitation is evident in the samples.
• In the long term, CO2 reaction creates a noteworthy dry-out phe-
nomenon and NaCl precipitation in the aquifer’s pore space by
changing the pore structure. The test depicted that Na+ concentra-
tion increases from 7300 to 9000 mg/l and also considerable en-
hancement of K+ and Mg+ in the pore fluid after CO2 reaction.
• Results from CBCT depicted that the pore structure of the core sam-
ple after CO2 reaction was completely non-homogeneous. Due to the
non-homogeneous size of the pore structure, CO2 can be stored safely
for 100 s of years in these types of reservoir, provided that no major
geological structures allow for the rapid surfacing of CO2 .
F. Famoori, R. Azin, Sh. Osfouri et al.
• In the long term CO2 sequestration, the secondary trapping mecha-
nisms increases the overall storage security over time.
• CBCT is suggested as a new method that could scan core samples
with high resolution. Results showed the porosity measured by CBCT
is more precise than laboratory methods (mercury porosimeter).
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.
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