energies

Article
An Investigation into CO2–Brine–Cement–Reservoir Rock
Interactions for Wellbore Integrity in CO2 Geological Storage
Amir Jahanbakhsh 1, * , Qi Liu 1 , Mojgan Hadi Mosleh 2 , Harshit Agrawal 2 , Nazia Mubeen Farooqui 1 ,
Jim Buckman 3 , Montserrat Recasens 1 , Mercedes Maroto-Valer 1 , Anna Korre 2 and Sevket Durucan 2, *

1 Research Centre for Carbon Solutions (RCCS), School of Engineering and Physical Sciences,
Heriot-Watt University, Edinburgh EH14 4AS, UK; [email protected] (Q.L.);
[email protected] (N.M.F.); [email protected] (M.R.); [email protected] (M.M.-V.)
2 Department of Earth Science and Engineering, Royal School of Mines, Imperial College London,
London SW7 2BP, UK; [email protected] (M.H.M.); [email protected] (H.A.);
[email protected] (A.K.)
3 Institute of Geo-Energy Engineering, School of Energy, Geoscience, Infrastructure and Society,
Heriot-Watt University, Edinburgh EH14 4AS, UK; [email protected]
* Correspondence: [email protected] (A.J.); [email protected] (S.D.)

Abstract: Geological storage of CO2 in saline aquifers and depleted oil and gas reservoirs can help
mitigate CO2 emissions. However, CO2 leakage over a long storage period represents a potential



concern. Therefore, it is critical to establish a good understanding of the interactions between CO2 –

 brine and cement–caprock/reservoir rock to ascertain the potential for CO2 leakage. Accordingly,
Citation: Jahanbakhsh, A.; Liu, Q.; in this work, we prepared a unique set of composite samples to resemble the cement–reservoir
Hadi Mosleh, M.; Agrawal, H.; rock interface. A series of experiments simulating deep wellbore environments were performed to
Farooqui, N.M.; Buckman, J.; investigate changes in chemical, physical, mechanical, and petrophysical properties of the composite
Recasens, M.; Maroto-Valer, M.; Korre, samples. Here, we present the characterisation of composite core samples, including porosity,
A.; Durucan, S. An Investigation into permeability, and mechanical properties, determined before and after long-term exposure to CO2 -rich
CO2 –Brine–Cement–Reservoir Rock
brine. Some of the composite samples were further analysed by X-ray microcomputed tomography
Interactions for Wellbore Integrity in
(X-ray µ-CT), X-ray diffraction (XRD), and scanning electron microscopy–energy-dispersive X-ray
CO2 Geological Storage. Energies
(SEM–EDX). Moreover, the variation of ions concentration in brine at different timescales was studied
2021, 14, 5033. https://doi.org/
10.3390/en14165033
by performing inductively coupled plasma (ICP) analysis. Although no significant changes were
observed in the porosity, permeability of the treated composite samples increased by an order
Academic Editor: João of magnitude, due mainly to an increase in the permeability of the sandstone component of the
Fernando Pereira Gomes composite samples, rather than the cement or the cement/sandstone interface. Mechanical properties,
including Young’s modulus and Poisson’s ratio, were also reduced.
Received: 18 May 2021
Accepted: 12 August 2021 Keywords: CO2 geological storage; wellbore integrity; CO2 –brine-cement–reservoir rock interaction;
Published: 16 August 2021 permeability; chemical and petrophysical characterisation

Publisher’s Note: MDPI stays neutral

with regard to jurisdictional claims in
published maps and institutional affil- 1. Introduction
iations.
Carbon dioxide capture, utilisation, and storage (CCUS) is one of the key technologies
proposed to mitigate against climate change caused by carbon dioxide (CO2 ) emissions.
Saline aquifers and depleted oil and gas reservoirs are potential subsurface storage sites.
Although storage capacity and injectivity are important factors in assessing the suitability
Copyright: © 2021 by the authors.
of a candidate reservoir for CO2 storage, confinement conditions required for CO2 storage
Licensee MDPI, Basel, Switzerland.
can be considered as the most important parameter with regards to leakage [1]. The
This article is an open access article
long-term integrity of geologically stored CO2 would depend on an impermeable caprock
distributed under the terms and
and absence of leakage pathways that could potentially result in leakages to groundwater
conditions of the Creative Commons
resources and the atmosphere [2–4].
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
Leakage pathways can be natural (e.g., faults and open fractures) or manmade
4.0/).
(e.g., wells), with the latter being especially important in abandoned wells [5]. Experience

Energies 2021, 14, 5033. https://doi.org/10.3390/en14165033 https://www.mdpi.com/journal/energies

Energies 2021, 14, 5033 2 of 20

from the oil and gas industry has shown that wells represent the highest risk of leakage in
a CO2 storage project [6]. Leakage may be caused by failure of one or more well barrier
elements, such as casing failure, poorly cemented casing, and improper abandonment [6–8].
Possible leakage pathways due to cementing problems include: (i) microannuli caused
by casing contraction and/or expansion, (ii) channels caused by improper mud removal
prior to and during cementing, (iii) lost circulation of cement into fractured formations
during cementing, (iv) flow after cementing by failure to maintain an overbalance pressure,
(v) mud cake leaks, and (vi) tensile fractures in cement caused by temperature and pressure
cycles [9].
Cement–caprock, cement–reservoir rock and cement–casing interfaces are potential
pathways for CO2 leakage. The injected CO2 dissolves in brine, resulting in the formation
of carbonic acid with a pH lower than 6 [10]. The CO2 -rich brine may react with minerals in
the reservoir rock, caprock, or borehole cement, and may cause either mineral dissolution
or mineral precipitation [11]. CO2 -rich brine diffuses through the well cement, resulting in
a gradual carbonation of the cement [12–14]. Cement degradation adjacent to the reservoir
rock and caprock may affect well integrity [15,16]. It is therefore important to understand
the interactions between the fluids and rock in a CO2 storage system to quantify and
possibly predict the long-term evolution of the physical and mechanical properties of the
cement and reservoir/caprock [17]. Previous experimental studies have shown that several
factors, from cement preparation to exposure to CO2 , can cause cement alteration. These
factors include water/cement ratio, cement additives, cement curing conditions, pressure,
temperature, CO2 concentration, pH, flow conditions, surrounding environment (e.g., brine
composition), and exposure time [14,18–22].
Potential effects of casing corrosion on well cement have been studied both in the
laboratory [23] and by using field data [24,25]. Although laboratory experiments suggested
significant erosion of cement by CO2 –brine mixtures, casing corrosion was absent in
samples extracted from CO2 production wells after 30 years of exposure. It was suggested
that the flux of CO2 used in the laboratory experiments was significantly higher than fluxes
at the field sites, thus explaining the discrepancy in results.
Portland cement is the most widely used cement in the industry. The problem,
however, is that Portland cement is not resistant to CO2 . It is not thermodynamically
stable upon contact with CO2 , and is expected to deteriorate over time [26]. Table 1
summarises the main reactions possible in Portland cement, and shows that the main
product is calcium carbonate [1,22,27–29].

Table 1. Dissolution of major cement phases in CO2 -rich brine.

Cement Phase
Reaction
Dissolution
Portlandite Ca(OH)2 + 2H+ ↔ Ca2+ + 2H2 O (Ca(OH)2 (s) + 2H+ + CO3 −2 CaCO3 (s) + 2H2 O)
Calcium silicate
Ca1.2 SiO3.2 ·2.06H2 O + 2.4H+ ↔ 1.2Ca2+ + SiO2 +3.26H2 O
hydrate
Monosulfate Ca4 Al2 O6 (SO4 )·12H2 O + 12H+ ↔ 4Ca2+ + 2Al3+ + SO4 2− + 18H2 O
Trisulfate Ca6 Al2 (SO4 )3 (OH)12 ·26H2 O + 12H+ ↔ 6Ca2+ + 2Al3+ + 3SO4 2− + 38H2 O
Calcium aluminate
Ca3 Al2 (OH)12 + 12H+ ↔ 3Ca2+ + 2Al3+ + 12H2 O
hydrate

Both laboratory and field studies have concluded that migration of CO2 through a
cement matrix was essentially driven by diffusion, and hence is slow [14,20,24,25]. Experi-
mental research has shown that four discrete zones usually can be detected in the cement
after exposure to CO2 , namely unreacted cement (the most inner zone), the portlandite
depleted zone, and the calcium carbonate and amorphous silicate zones [14,20,30,31]. An
experimental study of wellbore integrity and CO2 –brine flow along the casing–cement
interface [32] reported that Portland cement was carbonated to a depth of 50–250 m by a
diffusion-dominated process, which formed a barrier that prevented further diffusion of
CO2 into the cement matrix.
Energies 2021, 14, 5033 3 of 20

Traditionally, wellbore cement has been used to provide zonal isolation in oil and
natural gas wells for many decades. The mechanical strength of the cement contributes to
the geomechanical stability of the wellbore throughout its operational life. The hydration
reactions during setting and hardening of Portland cement is known to result in shrinkage,
and can lead to fracturing of the cement sheath, circumferential crack propagation, and
debonding at the casing–cement and cement–reservoir rock interfaces [33,34]. Further-
more, the cement matrix and reservoir rocks have different thermal expansion and elastic
coefficients, which may result in the formation of a microannulus at the same interface
during production and/or injection operations [35]. CO2 injection wells are expected to
be subjected to significantly higher injection pressures, resulting in early pressure build-
up behind the cement–reservoir rock interface, and a reduction of the effective stress in
the near-well environment. These changes in the state of stresses would increase shear
stresses at the wellbore–reservoir rock interface, which could lead to fracturing or cement
debonding [34,36], providing leakage paths for the stored CO2 .
Interactions between cement and CO2 –brine mixtures have been extensively investi-
gated [14,15,20,26,37–40]. Two competing phenomena were identified: carbonation and
dissolution of cement. CO2 dissolution in brine forms an acidic solution (carbonic acid),
which dissolves many cement phases. This process leads to a lower porosity due to the
precipitation of calcium carbonate, which takes up a larger volume than that of Ca(OH)2 .
On the other hand, in the presence of excess CO2 with a low pH, the CaCO3 would dis-
solve, and the net result may increase porosity and permeability [26,41]. Early research has
suggested that carbonation and dissolution have opposite geomechanical effects on the
cement; the former increases mechanical strength and decreases permeability, while the
latter decreases mechanical strength and increases permeability [42,43].
Mechanical behaviour of the reservoir rock–cement–casing interface has been inves-
tigated under simulated downhole confining stress and temperature conditions using
laboratory wellbore models. These experiments have demonstrated that the changes in
stress conditions during production or injection of fluids can indeed lead to the forma-
tion of a microannulus and radial fissures in the wellbore cement [44,45]. Under con-
ditions representative of relatively shallower depths (7–10 MPa reservoir pressure and
34–40 ◦ C temperature), long-term flow through experiments of CO2 through a brine-
saturated cement–casing/rock interface have displayed self-healing behaviour of the ce-
ment and permeability of the microannulus decreased significantly. This was attributed
to carbonation of cement and precipitation of calcite within the microannuli, as well as
the salt precipitation observed. At much higher reservoir pressures and temperatures
representative of greater depths (35 MPa and 92 ◦ C, respectively), however, the observed
reduction in permeability was insignificant [45]. More recent reactive flow experiments
in large-scale wellbore models at 5.5 MPa have also confirmed similar self-healing and
permeability-decline behaviour of the microannuli in the laboratory [46,47].
Early laboratory experiments carried out with wellbore cement cubes and cores have
suggested that the change in compressive strength of cement was a function of temperature
and pressure conditions during carbonation reactions and curing time, while the change in
permeability was a function of carbonation time [37,42,43]. More recently, it was reported
that triaxial testing of core samples treated with supercritical CO2 at 10 MPa pore pres-
sure resulted in an apparent weakening of the cement at low confining pressures, while
strain-hardening behaviour was observed at higher confining pressures [36]. Simulating
subsurface stress and temperature conditions, a number of researchers have also investi-
gated the effect of CO2 -saturated brine on the mechanical strength of artificially fractured
wellbore cement cores under dynamic conditions. These studies reported an increase in
the mechanical strength of the cores due to calcium carbonate precipitation [33].
A limited number of laboratory experiments on composite cement–caprock cores have
also been reported in the literature [16,22,31,48,49]. A series of core-flood experiments
carried out at 12 MPa effective stress investigated the nature of reaction front development
around artificially created fractures simulating a cement–caprock interface [16,22,48]. Early
Energies 2021, 14, 5033 4 of 20

work reported a 100-fold decrease in total permeability of the fracture in 8 days, while
an increase in overall porosity within the fracture region was also observed [16,22]. In a
more recent publication, the same authors reported mixed results: either an increase or
reduction in fracture permeabilities at various effective stresses, which were attributed to
the variations in the flowpaths observed in different post-reaction samples [48]. In another
study, composite cement–low-permeability basalt caprock cores were used to investigate
the geochemical and geomechanical effects of CO2 -saturated groundwater on the integrity
of wellbores with fractures [49]. Once again, the fractures in the cement and at the interface
between the cement and caprock were initiated artificially by compressive loading at
2.7 MPa, before treatment with CO2 -saturated water at 50 ◦ C and 10 MPa for 3 months.
The results of these experiments, carried out under static conditions, have suggested that,
due to dissolution, the permeability of pre-existing fractures increased in the early stages,
but it eventually decreased as a result of calcium carbonate precipitation [49].
Previous research has shown that dissolution and precipitation of minerals are very
critical at the interface of cement and caprock or reservoir rock for assessing the potential
CO2 leakage. On the other hand, all previous permeability and mechanical properties
measurements on CO2 –brine-treated cement–caprock composites were made on samples
with artificial fractures, created to simulate a cement–rock interface, before treatment
with CO2 -saturated brine or water. These studies investigated fracture response to the
reactive transport processes and reaction products around the fractures, and calculated
permeabilities and mechanical properties of a very small volume at the interface. Research
reported in the current study, on the other hand, used composite cores with a firmly bonded
cement–reservoir rock (sandstone) interface as the starting point for the full cycle of the
experiments carried out, including the measurement of pre- and post-treatment porosities,
permeabilities, and mechanical properties. Except for the reference samples, which were
characterised for their baseline mechanical properties by destructive testing at the start of
the experimental programme, all remaining composite samples were first characterised
for their porosities and permeabilities before being subjected to CO2 -rich brine at high-
pressure and high-temperature (HPHT) conditions. The same characterisation studies
were repeated after the long-term HPHT reactor experiments, followed by destructive
testing of the composite cores. This helped compare pre- and postreaction mechanical and
petrophysical properties of the samples, as well as the chemical reactions and alteration
products at the interface of cement and rock.
Therefore, the focus of this study was understanding the interactions between CO2 –
brine–cement–reservoir rock and to investigate the integrity of the reservoir–cement in-
terface in CO2 storage. Accordingly, a number of well-bonded cement–reservoir rock
composite core samples were prepared to replicate the cement–reservoir rock interface.
A series of HPHT hydrothermal experiments were conducted using these samples for
two timescales (3 and 11 months). Various techniques were used to characterise the brine
and composite samples before and after CO2 exposure, including petrophysical and ge-
omechanical characterisation, inductively coupled plasma optical emission spectrometry
(ICP-OES), X-ray diffraction (XRD), scanning electron microscopy–energy-dispersive X-ray
(SEM–EDX), and X-ray microcomputed tomography (X-ray µ-CT) measurements.

2. Methodology
2.1. Cement–Reservoir Rock Composite Samples and Fluid Preparation
Sandstone samples collected from Cayton Bay, North Yorkshire, were used to represent
the reservoir rock. This is a yellowish sandstone of the Osgodby Formation from the
Callovian age of the Jurassic period. The formation was found to be fine- to medium-
grained calcareous sandstone and clean at most levels, but iron-stained at others, the latter
layers containing small ooliths of iron carbonate (beds of berthierine (chamosite) ooids),
calcareous siltstone, and thin limestone. The sample blocks used in this study were of
the clean sandstone layers and those less bioturbated with horizontal crustacean burrows
(Thalassinoides), which are otherwise abundant.
Energies 2021, 14, 5033 5 of 20

A number of 38 mm diameter cement–sandstone composite core samples were pre-

pared with a diameter-to-length ratio of 1/2 (Figure 1). API Class G Portland cement
with 100 parts cement and 44 parts water was used to prepare the composite core sam-
ples [50]. The composite samples were prepared with the bedding planes of sandstone
either parallel (samples labelled as CBxP) or perpendicular (samples labelled as Cx) to the
cement–sandstone contact in order to investigate directional permeability and chemical-
reaction-related effects near the wellbore. The samples had an average grain density of
2.35 g/cm3 and an average weight of approximately 180 g. The porosity, permeability,
and mechanical and elastic properties of the cement–reservoir composite samples were
measured before and after exposure to CO2 -rich brine at 25 MPa and 90 ◦ C to assess the
effect of HPHT reactions on flow properties and mechanical behaviour. The porosity was
measured using a helium pycnometer. Permeability to nitrogen (N2 ) was measured in a
modified Hassler cell under 2.4 MPa confinement to prevent nitrogen bypass. Multistage
triaxial compression tests at different confinement levels (1.5, 5.0, 8.0, and 14.0 MPa, before
finally being brought to failure at 18.0 MPa confinement) were carried out for the stress–
strain–permeability characterisation of the samples in a four-column, 2000 kN capacity
servo-controlled rock-testing machine (Figure 2) following the ISRM’s suggested meth-
ods [51,52]. Destructive testing of the composite core samples could only be performed
either before or after the HPHT reactor experiments. Those samples, which were tested for
mechanical and elastic properties before the HPHT reactor experiments, were therefore
used as reference samples to compare their properties with those of the samples tested
after long-term HPHT treatment. The mean petrophysical and geomechanical properties of
all the core samples tested before HPHT treatment are presented in Table 2.

Figure 1. Examples of well-bonded cement–sandstone composite samples before the testing programme (samples rotated
by 180◦ for full view): (a) samples with sandstone bedding planes parallel to the cement contact (labelled as CBxP), and
(b) samples with sandstone bedding planes perpendicular to the cement contact (labelled as Cx).
Energies 2021, 14, 5033 6 of 20

Figure 2. Experimental setup for stress–strain–permeability measurements for the 38 mm diameter

composite core samples.

Table 2. Mean baseline petrophysical and geomechanical properties of the samples used.

Young’s
He Porosity N2 Permeability
Sample Type Modulus Poisson’s Ratio
(−) (×10−15 m2 )
(GPa)
Cement–
sandstone 0.12 4.12/0.92 * 20.47 0.31
composites
Sandstone 0.08 10.32 18.96 0.24
Portland cement 0.03 0.15 12.13 0.36
* Permeability of cement–sandstone composite samples when measured with the flow direction paral-
lel/perpendicular to bedding planes, respectively.

The selection of the brine’s composition was based on the typical brine composition
(including brines found in the North Sea), which includes Na+ , K+ , Mg2+ , Ca2+ , Sr2+ , Ba2+ ,
Fe3+ , Cl− , and SO4 2− [53]. A low-salinity brine (10,285 ppm) with major ions including Na+ ,
K+ , Mg2+ , Ca2+ , Sr2+ , and Ba2+ was synthesised by dissolving NaCl, KCl, MgCl2 ·6H2 O,
CaCl2 ·6H2 O, and SrCl2 ·6H2 O in 1 L of Millipore water. Table 3 shows the concentration of
the prepared synthetic brine (unreacted brine) used in the reactor experiments described
here [54].

Table 3. Initial brine composition before HPHT experiments.

Species Ca K Na Mg Ba Sr
Concentration (ppm) 612 303 5433 63 281 54

2.2. Hydrothermal Testing Experiments

The long-term CO2 –brine and cement–reservoir rock interaction experiments were
performed using a set of high-pressure and high-temperature reactors constructed by the
authors. Each reactor, as illustrated in Figure 3, consisted of a vessel, inlet and outlet valves,
a pressure relief valve (PRV), a pressure gauge, and a thermocouple. The inside of the
hydrothermal reactors was fitted with corrosion-resistant polytetrafluoroethylene (PTFE)
liners to avoid any possible corrosion during the course of experiments. A leak test with
duration of one to two months was carried out prior to each experiment. After the leak test,
a composite sample and the synthetic brine were introduced into the vessel, and the reactor
Energies 2021, 14, 5033 7 of 20

was sealed and heated gradually until it reached the target temperature. Supercritical CO2
was then injected and maintained at the target value of 25 MPa. During the experiment, the
pressure and temperature were monitored and controlled to avoid any abrupt pressure loss
or temperature variation. Once the experiment was finished, the reactor was first cooled
down gradually to ambient conditions (20–25 ◦ C). Subsequently, the reactor pressure was
slowly reduced to the atmospheric pressure, and the reacted sample and brine were taken
for a series of different analyses.

Figure 3. Schematic (vertical cross-section) of a typical hydrothermal HPHT vessel used to perform
the experiments. The drawing is not to scale.

3. Results and Discussion

A reference (baseline) characterisation was performed on some of the unreacted
composite core samples by measuring their porosity, permeability, and mechanical and
elastic properties, as well as using SEM–EDX, XRD, and X-ray µ-CT. The composites,
which had not been through destructive testing, were then exposed to CO2 -rich brine
for two periods of 3 and 11 months using the HPHT reactors to mimic typical downhole
environments (25 MPa and 90 ◦ C). Various analytical methods were used to investigate the
chemical and physical effects of CO2 -rich brine on the cement and the cement–sandstone
interfaces. ICP analysis showed a similar trend in the variation of ion concentration for
the majority of the composite samples. The results of the chemical and mineralogical
analyses of the HPHT-treated samples were consistent for all the composite samples tested;
therefore, we used the composite sample CB1P to illustrate those observations made.
However, depending on the bedding plane directionality of the samples tested, the changes
in the flow and mechanical properties of different samples revealed important information
relevant to long-term behaviour at the wellbore. These will be discussed using data from
samples prepared in both orientations. Figure 4 presents examples for each of the two sets
of samples tested.
Energies 2021, 14, 5033 8 of 20

Figure 4. Cement–sandstone composite samples CB1P (a,b) and C1 (c,d) before and after CO2 -rich brine exposure in the
HPHT reactor for 11 months, respectively.

3.1. Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES)

ICP-OES analysis of the synthesised unreacted brine sample was performed to obtain
a baseline for the ion concentration in the solution before running the hydrothermal
experiment. ICP-OES analyses were also conducted for all the solution samples after 3 and
11 months to determine any possible changes in the ion concentration.
Table 4 presents the changes in ion concentration of the reacted brine. Figure S1 in
the Supplementary Materials compares the variations in ion concentrations over 3 and
11 months for two groups of samples, CB1P&CB3P and C1&C3, respectively. Generally,
similar trends were observed in the variation of ion concentrations for all composite
samples tested. Ba, Ca, Mg, and Sr were consumed in the early stages (within 3 months);
however, they redissolved in the solution later, with the exception of Mg, which continued
to decrease with time. The concentrations of Fe, S, and Si (not present in the prepared
brine) increased with time, especially at the later stage of the experiment (11 months).

3.2. XRD Analysis

Sections from the top of composite samples were used for XRD analysis after exposure
to CO2 -rich brine for 11 months.

3.2.1. Cement
The original composition of the cement before exposure to CO2 -rich brine was port-
landite (Ca(OH)2 ), ettringite (Ca6 Al2 (SO4 )3 (OH)12 26H2 O), and calcium silicate hydrate
(Ca(OH)2 SiO2 ). The XRD analysis of the cement portion of a composite sample after expo-
sure to CO2 -rich brine revealed that the phases were portlandite (Ca(OH)2 ), hydrotalcite
(Mg6 Al2 CO3 (OH)16 4(H2 O)), hydroandradite (Ca3 Fe2 (SiO4 )3−x (OH)4X ), and potassium phos-
phate (K3 PO4 ), as well as carbonates in the forms of calcite and aragonite (CaCO3 ). Clearly,
dissolution of most of the cement phases presented in Table 1 occurred during the experiments.
Energies 2021, 14, 5033 9 of 20

Table 4. Brine compositions before and after the HPHT experiments.

Composite Sample Ba Ca K Mg Na S Si Sr Fe
(ppm)
Not Not Not
Unreacted brine 281 612 303 63 5433 54.0
detected detected detected
CB3P (3 months) 1 80 2362 24 2994 0 0 1 0
CB4P (3 months) 2 57 2605 28 3110 0 0 2 0
CB1P (11 months) 4 365 1689 19 6178 305 0 12 47
CB2P (11 months) 7 330 1700 18 6494 256 0 9 66
C3 (3 months) 3 68 1848 45 4416 0 0 1 0
C1 (11 months) 6 274 1332 11 6699 97 0 10 26
C2 (11 months) 1 80 1288 21 8214 141 0 12 29

3.2.2. Sandstone
The unreacted sandstone sample was mainly composed of quartz (SiO2 ), with small
amounts of K-feldspar (KAlSi3 O8 ) and kaolinite (Al2 Si2 O5 (OH)4 ). The XRD analysis of
the sandstone portion of the composite sample after the hydrothermal experiment did not
show any significant changes in composition, with the exception of a weak peak assigned
to calcite (CaCO3 ).

3.3. SEM–EDX Analysis

A series of SEM–EDX analyses was performed on thin sections taken from the top of
composite samples after exposure to CO2 -saturated brine for 11 months to investigate the
composition changes in different parts of the sample, including the cement, sandstone, and
cement–sandstone interface. No significant change was observed in the sandstone portion
of the sample, and therefore, the focus of the following subsections is on cement and the
interface of cement and sandstone. The SEM–EDX results of only one composite sample
will be presented here, as similar observations were made for the other analysed samples.

3.3.1. Cement
The outer cement surface of the CB1P composite sample after exposure to CO2 -
saturated brine for 11 months displayed a crust of variable thickness presenting a different
composition from the original cement. Elemental maps (Figure 5) showed enrichment
in K, Fe, and Na (Figure 5c–e) within the crust, and depletion in S, Ca, Mg, and Cl
(Figure 5b,f–h). This observation confirmed the findings of previous research [1,22,27].
Moreover, enrichment of Cl at the boundary between the crust and unaltered cement was
also observed (Figure 5b).
Void (pore) spaces and hairline fractures within the cement exhibited darker halos
(Figure S2a,e in the Supplementary Materials), and analysis of the elemental maps showed
depletion in Ca and oxygen, with an increase in C (Figure S2). The differences could be due
to higher porosity around bubbles and fractures. Other elements displayed little variation
between cement and darker halos, unlike that seen at the alteration crusts.
A recent study by Mito et al. [55] simulated a wellbore section using a concentric
arrangement of a carbon steel bar (centre), Portland cement (Class A), and a sandstone ring
(outer layer), and performed batch experiments at 50 ◦ C and 10 MPa of CO2 pressure. The
composite samples were exposed to supercritical CO2 , CO2 -saturated brine, or both CO2
and CO2 -saturated brine. Cement carbonation to a depth of few millimetres was observed.
However, due to fast precipitation of CaCO3 around the cement–rock interface, no further
alteration in the interior of the cement was observed after 56 days. As the composition of
brine used in this study was different from that used by Mito et al., a different behaviour in
the change of sampled water composition was observed in the early stages. However, there
were similarities in the general trend of ion-concentration changes. The Ca concentration in
brine increased over time in 56 days in their experiments, and a similar trend was observed
in the current experiments from 3 to 11 months of exposure to CO2 -rich brine.
Energies 2021, 14, 5033 10 of 20

Figure 5. Backscatteredelectron (BSE) image and EDX elemental maps from the same area on the top left corner of CB1P
after exposure to CO2 -rich brine for 11 months: (a) BSE image of the area; (b–h) elemental maps for chlorine, potassium,
iron, sodium, sulphur, calcium, and magnesium, respectively.

Carroll et al. [56] performed batch experiments to investigate the interaction of CO2
with cement–sandstone (or shale)–brine at reservoir conditions. They observed rapid
carbonation in the cement as supercritical CO2 was injected into the brine. The concen-
tration of Ca decreased while dissolved Mg and Si increased, and a low concentration of
Al was observed. Although the cement carbonation was the dominant reaction in their
experiment, chemical activities also were observed in the sandstone, as concentration of Fe
increased when the sandstone began reacting with the CO2 -rich brine. The assemblage of
cement–sandstone in the current work was not the same as the one used in Carroll et al.’s
work, and therefore, we did not expect to observe similar behaviour.

3.3.2. Cement–Sandstone Interface

The boundary between cement and sandstone also exhibited a relative depletion in
S, Cl, and Ca, as well as an apparent slight enrichment in K (Figure 6). However, no clear
depletion in Mg was observed, nor enrichment in Fe or Na. The zone of depletion was
approximately 0.3 mm thick. Figure 6b,c show the relative depletion of S and Cl within
the altered cement zone. Figure 6d shows the relative depletion of Ca within the altered
cement zone, and the position of Ca-rich pods and pore linings. A relative enrichment in
K from the altered cement zone, and the position of K-feldspar (bright area) within the
sandstone, is shown in Figure 6e. The phase map (Figure 6f) clearly shows distinct zones
of cement (CEM) and sandstone (SST) and between the two altered cement zones (ALT), as
well as the occurrence of quartz (Qtz), feldspar (Feld), kaolinite (Kaol), and Ca-rich areas
(Ca), which formed pods and thin layers within the altered cement zone, and occasionally
lined pores within the sandstone.
Energies 2021, 14, 5033 11 of 20

Figure 6. BSE image, EDX elemental maps, and phase map for the interface of cement and sandstone
from the same area on CB1P after exposure to CO2 -rich brine for 11 months: (a) BSE image of the area;
(b–e) elemental maps for sulphur, chlorine, calcium, and potassium, respectively; (f) phase map.

This zone of alteration at the interface of the cement and rock differed from that
observed on the cement surface by the lack of enrichment in Fe and Na, and did not
exhibit an enrichment in Cl at the border between the cement and altered cement. Ca-rich
pods occurred within the alteration zone, and lined pore spaces within the sandstone
(Figure 6d,f).
The ICP analysis of the brine samples after 11 months indicated an increase in Ca, K,
Na, S, Sr, and Fe. This correlated well with the SEM–EDX analysis, which showed a loss of
Ca and S from the crust and alteration zone, but not with an observed enrichment in K, Na,
and Fe.

3.4. X-Ray µ-CT Image Analysis

An X-ray µ-CT image analysis was used to determine the effects of physical and
chemical processes such as dissolution and precipitation on the composite samples. This
was possible through scanning the composite samples using a µ-CT scanner both before
and after exposure to the CO2 -rich brine. Similar to Section 3.3, the image analysis of
one sample is presented here. Figure 7 shows the reconstructed 3D volume and 2D cross-
sections of the cement–sandstone composite sample CB1P before being exposed to CO2 -rich
brine. Different-sized void spaces, as well as hairline fractures (cracks), can be seen in
the cement.
Energies 2021, 14, 5033 12 of 20

Figure 7. Reconstructed 3D volume and 2D cross-sections of the unreacted CB1P composite cement–sandstone sample:
(a) horizontal cross-section; (b) vertical cross-section perpendicular to the interface plane; (c) vertical cross-section, parallel
to the interface plane; (d) reconstructed 3D volume.

Figure 8 shows the reconstructed 3D volume and 2D cross-sections of the same

composite sample (CB1P) after being exposed to CO2 -rich brine for 11 months at 25 MPa
and 90 ◦ C. The 2D images in Figures 7 and 8 represent different positions in the sample, and
therefore are not comparable in terms of exact features; however, the invasion of CO2 -rich
brine into the cement part of the sample is clearly demonstrated in Figure 8 (red arrows).
The changes in grey-scale within the cement showed how far the solution diffused, which
paths were preferred, and possible dissolution and precipitation of minerals during the
experiment. Hairline fractures, due to their high permeability, controlled the invasion path
of the solution into the sample, particularly in the cement section. As fractures provided
CO2 -rich brine with easier access to some areas in the cement, dissolution mainly occurred
where fractures were mostly populated. The X-ray µ-CT images showed that the interface
between cement and sandstone was still intact after the HPHT experiments.
Figures S3 and S4 (in the Supplementary Materials) compare two large void spaces in
the cement section (from different cross-sections), where the former shows a void space
connected with a fracture, and the latter shows an isolated void space with no connection
to any fracture. Precipitation of new minerals can be seen in the void space (red circles)
connected to the fractures as CO2 -saturation solution could pass through; however, no
evidence of any precipitation reaction could be detected in the isolated void space.
It can be seen in Figures S3 and S4 that the hairline fractures also provided a flow path
to the solution to reach the cement–sandstone interface. Both dissolution and precipitation
of species at the interface of the cement–sandstone could be detected; these were also found
in the SEM–EDX analysis.
Energies 2021, 14, 5033 13 of 20

Figure 8. Reconstructed 3D volume and 2D cross-sections of the CB1P composite cement–sandstone

sample after exposure to CO2 -rich brine for 11 months: (a) horizontal cross-section; (b) vertical
cross-section perpendicular to the interface plane; (c) vertical cross-section, parallel to the interface
plane; (d) reconstructed 3D volume.

3.5. Changes in Petrophysical and Geomechanical Properties of the Cement–Sandstone

Composite Samples
The composite core samples were tested for their petrophysical and mechanical prop-
erties before and after being exposed to CO2 -rich brine in the HPHT reactors, and possible
changes in these properties were evaluated. Figure 9 presents and compares the baseline
(before HPHT experiment) stress–strain–permeability behaviour of two different cement–
sandstone composite samples, CB11P and CB12P, with that of two other composite samples,
CB1P and CB2P, after 11 months of treatment with CO2 -rich brine. Figure 10 shows HPHT-
treated composite samples CB1P (also shown in Figure 4b after HPHT treatment, but before
mechanical testing) and CB2P after multistage stress–strain–permeability testing. Both
samples displayed a typical shear failure pattern after being axially loaded to failure at
18.0 MPa confinement stress as illustrated in Figure 9b.
Table 5 presents the baseline Hassler cell porosities and permeabilities of the cement–
sandstone composite samples, and compares these with their porosities, permeabilities,
and mechanical properties after 11 months of exposure to CO2 -rich brine. As Table 5
illustrates, although there was no significant change in the porosities of the treated com-
posites, their permeabilities increased by up to an order of magnitude after 11 months.
As expected, the samples, which were prepared using sandstone with bedding planes
aligned perpendicular to N2 flow during the permeability measurements, began with much
lower baseline permeabilities, and the increases in their permeabilities were relatively less
pronounced (Table 5). The stress-dependent changes in the permeability of the composite
samples shown in Figure 9 were measured during the multistage triaxial tests at each
confinement level to represent permeabilities at different reservoir depths. These values
have also shown an order of magnitude difference between the pre- and post-treatment
permeabilities in general, showing reduction by up to two orders of magnitude for the post-
treatment samples.
Energies 2021, 14, 5033 14 of 20

Figure 9. Multistage triaxial compression test results comparing the stress–strain–permeability behaviour for (a) two
representative composite cement–sandstone samples, CB11P and CB12P (tested to define the baseline properties of
the samples), with that of (b) two composite cement–sandstone samples, CB1P and CB2P, after HPHT treatment with
CO2 -rich brine.

Figure 10. Cement–sandstone composite samples (a) CB1P and (b) CB2P displaying a typical shear failure pattern after being
axially loaded to failure at 18.0 MPa confinement stress as illustrated in Figure 9b above. Note that the cement–sandstone
interface in both samples remained intact after the samples were brought to failure under triaxial loading.

Table 5. Comparison of Hassler cell porosities, permeabilities, and mechanical properties of the
cement–sandstone composite samples before and after the HPHT experiments.

Young’s
N2 Permeability Poisson’s
He Porosity (%) Modulus
(×10−15 m2 ) Ratio
(GPa)
Sample No.
Before After Before After After After
HPHT HPHT HPHT HPHT HPHT HPHT
Experiment Experiment Experiment Experiment Experiment Experiment
CB1P 0.10 0.12 6.67 92.08 15.18 0.29
CB2P 0.09 0.10 5.17 44.23 14.62 0.20
C1 0.12 0.11 0.68 3.33 14.47 0.33
C2 0.14 0.11 0.93 7.30 16.82 0.27
Mean baseline mechanical properties before treatment with CO2 -rich brine in HPHT reactors (from Table 2)
20.47 0.31

The Young’s modulus of the composite samples was reduced significantly (from
a mean E value of 20.47 GPa to 15.25 GPa) after long-term exposure to CO2 -rich brine,
displaying lower stiffness overall. The Poisson’s ratio for the treated samples also was
Energies 2021, 14, 5033 15 of 20

reduced from a mean υ value of 0.31 to 0.27. Note that mechanical-properties testing is
destructive; therefore, the results obtained from triaxial testing of the pretreatment samples
served as the baseline values. The baseline Young’s modulus and Poisson’s ratio values
shown in Table 5 are therefore the mean values taken from Table 2 for comparison.
Contrary to initial expectations, the geochemical reactions that took place during
11 months of HPHT exposure to CO2 -rich brine did not affect the mechanical strength or
permeability of the cement–sandstone interface itself. As illustrated in Figure 4b,d and
Figure 10, it was interesting to note that the well-bonded cement–sandstone interfaces in
all the composite samples were not weakened or debonded during 11 months of HPHT
treatment, and remained intact even after the samples were brought to failure under
triaxial loading. This suggests that well-bonded and plugged cement–reservoir rock contact
zones in CO2 -storage wellbores may not, in the long term, create a permeable leakage
pathway unless these are already mechanically failed/debonded under variable stress and
pressure conditions experienced during hydrocarbon production and/or CO2 injection
periods earlier.
Further analysis of the experimental data showed that the changes in overall perme-
ability of the composite samples could be attributed to the increase in the permeability of
the sandstone component in the main, rather than the cement or the cement–sandstone
interface. As shown in Figures 4 and 10, the permeability contrast between the cement
and the sandstone created the conditions for deposition of materials that were mobilised
through the reactions between the brine and the samples. It was perceived that the brine
solution, which encountered minerals unstable in its presence, dissolved and almost si-
multaneously exchanged them for new minerals that were preferentially deposited along
surfaces where there was a significant permeability contrast, as was the case along the
cement and sandstone interface. As indicated in Table 4, more active chemical reactions
occurred during the early stages of the experiment.
Considering the mineralogy of the samples, within the sandstone portion, the feldspars
were the less-stable minerals (Figure 11), where the grain boundaries became less sharp,
and newly formed flow paths were created along the feldspar mineral grain cleat. The
sandstone permeability increased as a result. In the samples in which the cement was in
contact with sandstone aligned perpendicular to the bedding, the reactions and pathways
were more limited. Therefore, the increase in the initially low permeability of the composite
samples was less pronounced.
Within the cement, which was far less permeable (Table 2), reactions occurred more
readily on the surface of the core and along the contact with the sandstone, enabled by
the substantially higher permeability of the rock. Therefore, the alteration zone was wider
for the samples in which the bedding was parallel to the cement–sandstone interface, and
substantially narrower for the samples with a perpendicular bedding (Figure 4b,d). The
SEM images indicated the depletion in Ca within the cement (from reaction of the carbonate
minerals with the fluid) and its mobilisation. Due to the permeability contrast between
the cement and the sandstone, the fluid flow became stagnant, and replacement reactions
took place within the cement. The new less-dense and smaller-grain-size mineral phases
(kaolinite) were deposited and filled the space between the sandstone and the cement,
further reducing the permeability of the contact between the cement and sandstone.
Energies 2021, 14, 5033 16 of 20

Figure 11. SEM image of the cement–sandstone interface: (a) a pore filled by secondary carbonate
deposition; (b–d) feldspar grains within the sandstone portion illustrating varying degrees of alteration.

4. Conclusions
The aim of this study was to understand the interactions between CO2 -rich brine and
cement–reservoir rock, and to evaluate the integrity of wellbore cement and the interface
between cement and the reservoir rock. In order to achieve this, it was critical to understand
the relationship between the carbonation and dissolution mechanisms and the parameters
that influenced the mechanical integrity of the cement–reservoir rock system. A wide
range of laboratory techniques was used for assessing the chemical, petrophysical, and
mechanical impacts of CO2 –brine on the cement–reservoir rock system.
ICP-OES, XRD, SEM–EDX, and X-ray µ-CT showed degradation of the cement due
to chemical reactions as a result of being exposed to CO2 -saturated brine. SEM–EDX and
X-ray µ-CT suggested that the alteration depth in the cement, which was controlled by
a diffusion process, could be affected by the presence of hairline fractures. Cracks and
fractures provided high permeability pathways to CO2 -rich brine, which increased the
penetration depth and influenced the dissolution and precipitation in the cement.
Precipitation or carbonation increased mechanical strength and decreased perme-
ability in the cement, while dissolution decreased mechanical strength and increased
permeability primarily within the sandstone. Our observations confirmed the findings of
previous research [31,42,43] that the dissolution process in fact increased the permeability
of the samples, while at the same time, lowered their mechanical and elastic properties. The
relationship between the geomechanical changes and their impact on wellbore integrity
is complicated and depends on several parameters, including the acidity, the brine com-
position, the confining pressure, the pore pressure, and the residence time [4]. Although
cement degradation may have a negative impact on the wellbore integrity, the increasing
compressibility due to calcium leaching may result in compression of the affected area and
close any escape pathway in the cement [4,57].
Although no considerable changes in porosity were observed, permeability of com-
posite samples increased by an order of magnitude after exposure to CO2 -rich brine. Small
new pores (void spaces), which may not have been connected, were generated as a result
of dissolution in the cement half of the composite samples. However, most of the hairline
Energies 2021, 14, 5033 17 of 20

fractures in the cement were filled due to precipitation. Therefore, the overall effect of the
dissolution and precipitation processes was more pronounced on the permeability and
less on the porosity of the cement. Geomechanical analysis showed significant reduction
in both the Young’s modulus and the Poisson’s ratio of the composite samples, while the
overall mechanical strength of the samples increased slightly.
After long-term HPHT treatment of the composite samples, an order of magnitude
increase in the mean permeabilities of the samples prepared with the sandstone bedding
planes either parallel and perpendicular to the cement/rock contact was observed. The
analysis of the data obtained from all the experiments confirmed that this was mainly
due to an increase in the permeability of the sandstone component of the composite
samples, rather than the cement or the cement–sandstone interface. Furthermore, both
the initial and post-HPHT treatment permeabilities of the perpendicular samples, which
were representative of the primary fluid flow direction in the reservoir rock at the wellbore,
were relatively small, and an order of magnitude smaller than those of the parallel samples.
These observations suggested that long-term chemical reactions that take place at the
wellbore are not likely to affect upward mobility of CO2 significantly along well-bonded
cement–reservoir rock interfaces.
The experiments we carried out suggested that well-bonded and plugged cement–
reservoir rock interfaces in CO2 -storage reservoirs may not create a permeable leakage
pathway unless the interfaces are already mechanically failed/debonded under variable
stress and pressure conditions experienced during earlier production/injection periods.

Supplementary Materials: The following are available online at https://www.mdpi.com/article/

10.3390/en14165033/s1, Figure S1. Concentration of ions present in the brine at initial conditions,
after CO2 injection for 3 months (for samples CB1P and C3) and 11 months (for samples CB3P and
C1), Figure S2. Top left corner of CB1P after exposure to CO2 –rich brine for 11 months (a) and (e) BSE
images, and (b) to (d) and (f) to (h) EDX elemental maps of areas in (a) and (e). (b) and (f) oxygen, (c)
and (g) carbon, (d) and (h) calcium, Figure S3. CB1P composite sample after 11 months exposure
to CO2 -rich brine; precipitation in the void spaces in the red circle where the access of solution was
possible through several fractures, Figure S4. CB1P composite sample after 11 months exposure to
CO2 -rich brine, no significant precipitation in the voids, which are not connected to the fractures.
Author Contributions: Conceptualization, M.M.-V., A.K. and S.D.; formal analysis, A.J., M.H.M.,
H.A., N.M.F., J.B., M.R., M.M.-V., A.K. and S.D.; funding acquisition, M.M.-V., A.K. and S.D.; in-
vestigation, A.J., Q.L., M.H.M., H.A., N.M.F. and J.B.; methodology, Q.L., M.M.-V., A.K. and S.D.;
project administration, M.M.-V., A.K. and S.D.; supervision, M.M.-V., A.K. and S.D.; visualization,
A.J., M.H.M., H.A. and J.B.; writing—original draft, A.J.; writing—review and editing, A.J., J.B., M.R.,
M.M.-V., A.K. and S.D. All authors have read and agreed to the published version of the manuscript.
Funding: This research was carried out as part of the UK Research Councils’ Energy Programme-
funded consortium project “CO2 injection and storage—short- and long-term behaviour at different
spatial scales” (Grant Reference: EP/K035967/1).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data acquired during this study can be made available upon
request from the corresponding authors.
Acknowledgments: The authors would like to thank the Engineering and Physical Sciences Research
Council for the funding provided. Financial support received from the Robert M. Buchan Chair in
Sustainable Energy Engineering at Heriot-Watt University is gratefully acknowledged. The authors
also thank Dubravka Pokrajac of the University of Aberdeen for the micro-CT imaging.
Conflicts of Interest: The authors declare no conflict of interest.
Energies 2021, 14, 5033 18 of 20

Abbreviations

2D Two-Dimensional
3D Three-Dimensional
CCUS Carbon dioxide Capture, Utilisation, and Storage
X-ray µ-CT X-ray Microcomputed Tomography
XRD X-ray Diffraction
SEM–EDX Scanning Electron Microscopy–Energy-Dispersive X-ray
ICP Inductively Coupled Plasma
ICP-OES Inductively Coupled Plasma-Optical Emission Spectrometry
HPHT High-Pressure and High-Temperature
PRV Pressure-Relief Valve
PTFE Polytetrafluoroethylene
BSE Backscattered Electron
CEM Cement
SST Sandstone
ALT Altered cement zones
Qtz Quartz
Feld Feldspar
Kaol Kaolinite

References
1. Zhang, M.; Bachu, S. Review of integrity of existing wells in relation to CO2 geological storage: What do we know? Int. J. Greenh.
Gas Control 2011, 5, 826–840. [CrossRef]
2. Iyer, J.; Walsh, S.D.C.; Hao, Y.; Carroll, S.A. Assessment of two-phase flow on the chemical alteration and sealing of leakage
pathways in cemented wellbores. Int. J. Greenh. Gas Control 2018, 69, 72–80. [CrossRef]
3. Onishi, T.; Nguyen, M.C.; Carey, J.W.; Will, B.; Zaluski, W.; Bowen, D.W.; Devault, B.C.; Duguid, A.; Zhou, Q.;
Fairweather, S.H.; et al. Potential CO2 and brine leakage through wellbore pathways for geologic CO2 sequestration using the
National Risk Assessment Partnership tools: Application to the Big Sky Regional Partnership. Int. J. Greenh. Gas Control 2019, 81,
44–65. [CrossRef]
4. Bagheri, M.; Shariatipour, S.M.; Ganjian, E. A Review of oil well cement alteration in CO2 -rich environments. Constr. Build. Mater.
2018, 186, 946–968. [CrossRef]
5. Watson, T.L.; Bachu, S. Evaluation of the potential for gas and CO2 leakage along wellbores. SPE Drill. Complet. 2009, 24,
115–126. [CrossRef]
6. Gasda, S.E.; Bachu, S.; Celia, M.A. Spatial characterization of the location of potentially leaky wells penetrating a deep saline
aquifer in a mature sedimentary basin. Environ. Geol. 2004, 46, 707–720. [CrossRef]
7. Celia, M.A.; Bachu, S.; Nordbotten, J.M.; Gasda, S.E.; Dahle, H.K. Quantitative estimation of CO2 leakage from geological storage:
Analytical models, numerical models, and data needs. In Proceedings of the 7th International Conference Greenhouse Gas
Control Technologies, Vancouver, BC, Canada, 5–9 September 2004; pp. 663–671.
8. Dalla Vecchia, F.; dos Santos, V.H.J.M.; Schütz, M.K.; Ponzi, G.G.D.; de Guimarães e Stepanha, A.S.; de Fraga Malfatti, C.; da
Costa, E.M. Wellbore integrity in a saline aquifer: Experimental steel-cement interface degradation under supercritical CO2
conditions representative of Brazil’s Parana basin. Int. J. Greenh. Gas Control 2020, 98, 103077. [CrossRef]
9. Sweatman, R.E.; Marsic, S.D.; McColpin, G.R. Advancements in technology and process approach reduce cost and increase
performance of CO2 -flow monitoring and remediation. In Proceedings of the SPE International Conference CO2 Capture, Storage
and Utilization, Society of Petroleum Engineers, New Orleans, LA, USA, 10–12 November 2010; Volume 20. [CrossRef]
10. Druckenmiller, M.L.; Maroto-Valer, M.M. Carbon sequestration using brine of adjusted pH to form mineral carbonates. Fuel
Process. Technol. 2005, 86, 1599–1614. [CrossRef]
11. Brunet, J.-P.L.; Li, L.; Karpyn, Z.T.; Kutchko, B.G.; Strazisar, B.; Bromhal, G. Dynamic evolution of cement composition and
transport properties under conditions relevant to geological carbon sequestration. Energy Fuels 2013, 27, 4208–4220. [CrossRef]
12. Carey, J.W. Geochemistry of wellbore integrity in CO2 sequestration: Portland cement-steel-brine-CO2 interactions. Rev. Mineral.
Geochem. 2013, 77, 505–539. [CrossRef]
13. Mainguy, M.; Ulm, F.-J. Coupled diffusion-dissolution around a fracture channel: The solute congestion phenomenon. Transp.
Porous Media 2001, 45, 479–495. [CrossRef]
14. Kutchko, B.G.; Strazisar, B.R.; Dzombak, D.A.; Lowry, G.V.; Thauiow, N. Degradation of well cement by CO2 under geologic
sequestration conditions. Environ. Sci. Technol. 2007, 41, 4787–4792. [CrossRef] [PubMed]
15. Duguid, A.; Scherer, G.W. Degradation of oilwell cement due to exposure to carbonated brine. Int. J. Greenh. Gas Control 2010, 4,
546–560. [CrossRef]
16. Walsh, S.D.C.; Du Frane, W.L.; Mason, H.E.; Carroll, S.A. Permeability of wellbore-cement fractures following degradation, by
carbonated brine. Rock Mech. Rock Eng. 2013, 46, 455–464. [CrossRef]
Energies 2021, 14, 5033 19 of 20

17. Richardson, M.G. Carbonation of Reinforced Concrete: Its Causes and Management; Citis: New York, NY, USA, 1988; 205p.
18. Thomas, M.D.A.; Matthews, J.D. Carbonation of flyash concrete. Mag. Concr. Res. 1992, 44, 217–228. [CrossRef]
19. Loo, Y.H.; Chin, M.S.; Tam, C.T.; Ong, K.C. A carbonation prediction model for acclerated carbonation testing of concrete. Mag.
Concr. Res. 1994, 46, 191–200. [CrossRef]
20. Kutchko, B.G.; Strazisar, B.R.; Lowry, G.V.; Dzombak, D.; Thaulow, N. Rate of CO2 attack on hydrated class H well cement under
geologic sequestration conditions. Environ. Sci. Technol. 2008, 42, 6237–6242. [CrossRef]
21. Strazisar, B.; Kutchko, B.; Huerta, N. Chemical reactions of wellbore cement under CO2 storage conditions: Effects of cement
additives. Energy Procedia 2009, 1, 3603–3607. [CrossRef]
22. Walsh, S.D.C.; Mason, H.E.; Du Frane, W.L.; Carroll, S.A. Experimental calibration of a numerical model describing the alteration
of cement/caprock interfaces by carbonated brine. Int. J. Greenh. Gas Control 2014, 22, 176–188. [CrossRef]
23. Carey, J.W.; Svec, R.; Grigg, R.; Lichtner, P.C.; Zhang, J.; Crow, W. Wellbore integrity and CO2 -brine flow along the casing-cement
microannulus. Energy Procedia 2009, 1, 3609–3615. [CrossRef]
24. Carey, J.W.; Wigand, M.; Chipera, S.J.; WoldeGabriel, G.; Pawar, R.; Lichtner, P.C.; Wehner, S.C.; Raines, M.A.; Guthrie, G.D., Jr.
Analysis and performance of oil well cement with 30 years of CO2 exposure from the SACROC Unit, West Texas, USA. Int. J.
Greenh. Gas Control 2007, 1, 75–85. [CrossRef]
25. Crow, W.; Carey, J.W.; Gasda, S.; Williams, B.D.; Celia, M. Wellbore integrity analysis of a natural CO2 producer. Int. J. Greenh. Gas
Control 2010, 4, 186–197. [CrossRef]
26. Krilov, Z.; Loncaric, B.; Miksa, Z. Investigation of a long-term cement deterioration under a high-temperature, sour gas downhole
environment. In Proceedings of the SPE International Symposium on Formation Damage Control, Society of Petroleum Engineers,
Lafayette, LA, USA, 24–26 February 2000; Volume 9.
27. Rochelle, C.A.; Milodowski, A.E. Carbonation of borehole seals: Comparing evidence from short-term laboratory experiments
and long-term natural analogues. Appl. Geochem. 2013, 30, 161–177. [CrossRef]
28. Taylor, H.F.W. Cement Chemistry, 2nd ed.; Thomas Teldford: London, UK, 1997.
29. Carroll, S.; Carey, J.W.; Dzombak, D.; Huerta, N.J.; Li, L.; Richard, T.; Um, W.; Walsh, S.D.C.; Zhang, L. Review: Role of chemistry,
mechanics, and transport on well integrity in CO2 storage environments. Int. J. Greenh. Gas Control 2016, 49, 149–160. [CrossRef]
30. Carey, W.J.; Lichtner, P. Calcium Silicate Hydrate (C-S-H) Solid Solution Model Applied to Cement Degradation Using the
Continuum Reactive Transport Model FLOTRAN. In Transport Properties and Concrete Quality: Materials Science of Concrete;
Mobasher, B., Skalny, J., Eds.; American Ceramic Society: Columbus, OH, USA; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2007;
Special Volume, pp. 73–106.
31. Mason, H.E.; Du Frane, W.L.; Walsh, S.D.C.; Dai, Z.; Charnvanichborikarn, S.; Carroll, S.A. Chemical and mechanical properties of
wellbore cement altered by CO2 -rich brine using a multianalytical approach. Environ. Sci. Technol. 2013, 47, 1745–1752. [CrossRef]
32. Carey, W.J.; Svec, R.; Grigg, R.; Zhang, J.; Crow, W. Experimental investigation of wellbore integrity and CO2 –brine flow along
the casing–cement microannulus. Int. J. Greenh. Gas Control 2010, 4, 272–282. [CrossRef]
33. Wolterbeek, T.K.T.; Hangx, S.J.T.; Spiers, C.J. Effect of CO2 -induced reactions on the mechanical behaviour of fractured wellbore
cement. Geomech. Energy Environ. 2016, 7, 26–46. [CrossRef]
34. Dusseault, M.B.; Gray, M.N.; Nawrocki, P.A. Why oilwells leak: Cement behaviour and long-term consequences. In Proceedings
of the International Oil and Gas Conference and Exhibition in China, Society of Petroleum Engineers, Beijing, China, 7–10
November 2000.
35. Ozyurtkan, M.H.; Radonjic, M. An experimental study of the effect of CO2 rich brine on artificially fractured well-cement. Cem.
Concr. Compos. 2014, 45, 201–208. [CrossRef]
36. Liteanu, E.; Spiers, C.J.; Peach, C.J. Failure behaviour wellbore cement in the presence of water and supercritical CO2 . Energy
Procedia 2009, 1, 3553–3560. [CrossRef]
37. Onan, D.D. Effects of supercritical carbon dioxide on well cements. In Proceedings of the Permian Basin Oil and Gas Recovery
Conference, Society of Petroleum Engineers, Midland, TX, USA, 8–9 March 1984; Volume 14.
38. Šauman, Z. Effect of CO2 on porous concrete. Cem. Concr. Res. 1972, 2, 541–549. [CrossRef]
39. Gervais, C.; Garrabrants, A.C.; Sanchez, F.; Barna, R.; Moszkowicz, P.; Kosson, D.S. The effects of carbonation and drying
during intermittent leaching on the release of inorganic constituents from a cement-based matrix. Cem. Concr. Res. 2005, 34,
119–131. [CrossRef]
40. Lea, F.M. The Chemistry of Cement and Concrete; Edward Arnold: London, UK, 1970.
41. Robins, N.S.; Milodowski, A.E. Borehole cements and the downhole environment: A review. Q. J. Eng. Geol. Hydrogeol. 1986, 19,
175–181. [CrossRef]
42. Claisse, P.A.; El-Sayad, H.I.; Shaaban, I.G. Permeability and pore volume of carbonated concrete. ACI Mater. J. 1999, 96, 378–381.
43. Chi, J.M.; Huang, R.; Yang, C.C. Effects of carbonation on mechanical properties and durability of concrete using accelerated
testing method. J. Mar. Sci. Technol. 2002, 10, 14–20.
44. Boukhelifa, L.; Moroni, N.; James, S.G.; Le Roy-Delage, S.; Thiercelin, M.J.; Lemaire, G. Evaluation of cement systems for oil- and
gas-well zonal isolation in a full-scale annular geometry. SPE Drill. Complet. 2005, 20, Paper SPE-87195-PA. [CrossRef]
45. Syed, A.; Shi, J.-Q.; Durucan, S.; Korre, A.; Nash, G. Experimental and numerical investigations into CO2 interactions with well
infrastructure and its impact on long term well integrity. Energy Procedia 2014, 63, 5707–5714. [CrossRef]
Energies 2021, 14, 5033 20 of 20

46. van Eijden, J.; Cornelissen, E.; Ruckert, F.; Wolterbeek, T. Development of experimental equipment and procedures to evaluate
zonal isolation and well abandonment materials. In Proceedings of the SPE/IADC Drilling Conference and Exhibition, Society of
Petroleum Engineers, The Hague, The Netherlands, 14–16 March 2017. SME/IADC-184640-MS. [CrossRef]
47. Wolterbeek, T.K.T.; Ruckert, F.; van Moorsel, S.G.; Cornelissen, E.K. Reactive transport and permeability evolution in wellbore
defects exposed to periodic pulses of CO2 -rich water. Int. J. Greenh. Gas Control 2019, 91, 102835. [CrossRef]
48. Rhino, K.; Iyer, J.; Walsh, S.D.C.; Carroll, S.A.; Smith, M.M. Influence of effective stress and transport on mechanical and chemical
alteration processes at the Cement-Caprock interface. Int. J. Greenh. Gas Control 2021, 109, 103340. [CrossRef]
49. Jung, H.B.; Kabilan, S.; Carson, J.P.; Kuprat, A.P.; Um, W.; Martin, P.; Michael, D.; Kafentzis, T.; Varga, T.; Stephens, S.; et al.
Wellbore cement fracture evolution at the cement–basalt caprock interface during geologic carbon sequestration. Appl. Geochem.
2014, 47, 1–16. [CrossRef]
50. American Petroleum Institute. Specification for Cements and Materials for Well Cementing, 25th ed.; API Spec 10A; American
Petroleum Institute (API): Washington, DC, USA, 2019.
51. Kovari, K.; Tisa, A.; Einstein, H.H.; Franklin, J.A. Suggested methods for determining the strength of rock materials in triaxial
compression: Revised version. Int. J. Rock Mech. Min. Sci. Geomech. Abstr. 1983, 20, 285–290.
52. Brown, E.T. Rock Characterization, Testing & Monitoring: ISRM Suggested Methods; Pergamon Press: Oxford, UK, 1981.
53. Steal, L. An Investigation of CO2 -Brine Interactions Using North Sea Oil Well Data with Respect to Geological Storage of Carbon
Dioxide and Enhanced Oil Recovery. Ph.D. Thesis, Heriot-Watt University, Edinburgh, UK, 2017.
54. Farooqui, N.M.; Liu, Q.; Maroto-Valer, M.M.; Hadi Mosleh, M.; Korre, A.; Durucan, S. Understanding CO2 -brine-wellbore
cement-rock interactions for CO2 storage. Energy Procedia 2017, 114, 5206–5211. [CrossRef]
55. Mito, S.; Xue, Z.; Sato, H. Experimental assessment of well integrity for CO2 geological storage: Batch experimental results on
geochemical interactions between a CO2 –brine mixture and a sandstone–cement–steel sample. Int. J. Greenh. Gas Control 2015, 39,
420–431. [CrossRef]
56. Carroll, S.A.; McNab, W.W.; Torres, S.C. Experimental study of cement-sandstone/shale-brine-CO2 interactions. Geochem. Trans.
2011, 12, 1–19. [CrossRef] [PubMed]
57. Berkowitz, B. Characterizing flow and transport in fractured geological media: A review. Adv. Water Resour. 2002, 25,
861–884. [CrossRef]