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CO2 – brine – sandstone wettability evaluation at reservoir

conditions via nuclear magnetic resonance measurements
Auby Baban
Edith Cowan University

Ahmed Al-Yaseri
Edith Cowan University

Alireza Keshavarz
Edith Cowan University

R. Amin

Stefan Iglauer
Edith Cowan University

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10.1016/j.ijggc.2021.103435 Baban, A., Al-Yaseri, A., Keshavarz, A., Amin, R., & Iglauer, S. (2021).
CO2–brine–sandstone wettability evaluation at reservoir conditions via nuclear magnetic resonance
measurements. International Journal of Greenhouse Gas Control, 111, article 103435. https://doi.org/10.1016/
j.ijggc.2021.103435
This Journal Article is posted at Research Online.
https://ro.ecu.edu.au/ecuworkspost2013/10986
 International Journal of Greenhouse Gas Control 111 (2021) 103435

Contents lists available at ScienceDirect

International Journal of Greenhouse Gas Control

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

CO2 – brine – sandstone wettability evaluation at reservoir conditions via

Nuclear Magnetic Resonance measurements
A. Baban a, *, A. Al-Yaseri a, *, A. Keshavarz a, R. Amin b, S. Iglauer a
a
Petroleum Engineering, School of Engineering Department, Edith Cowan University, 270 Joondalup Drive, Joondalup WA 6027, Australia
b
Zana Enterprise, 2 ST. Georges Terrace, Perth WA 6000, Australia

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

Index terms: CO2-rock wettability is a key parameter which governs CO2 trapping capacities and containment security in the
5114, Permeability and porosity context of CO2 geo-sequestration schemes. However, significant uncertainties still exist in terms of predicting
3947, Surfaces and interfaces CO2 rock wettability at true reservoir conditions. This study thus reports on wettability measurements via in­
5139,Transport properties
dependent Nuclear Magnetic Resonance (NMR) experiments on sandstone (CO2–brine systems) to quantify
Keywords: Wettability Indices (WI) using the United States Bureau of Mines (USBM) scale. The results show that CO2 (either
Wettability
molecularly dissolved or as a separate supercritical phase) significantly reduced the hydrophilicity of the
Nuclear Magnetic Resonance
Carbone dioxide (CO2)
sandstone from strongly water-wet (WI ≈ 1) to weakly water-wet (WI = 0.26), and associated with that the
geo-sequestration water-wetness of the rock for the two-phase systems. This was caused by additional protonation of surface silanol
Carbon Capture and Storage (CCS) groups on the quartz, induced by carbonic acid. Capillary pressure and relative permeability curves and residual
Sandstone CO2 saturation were also measured; these results were compared with literature data, and general consistency
was found. NMR T2 distribution measurements also demonstrated preferential water displacement in large pores
(r > 1 µm) following scCO2 flooding, while no change was observed for smaller pores (r < 1 µm). These insights
add confidence to the assessments of CO2-rock wettability and therefore reduce project risk. This work thus aids
in the implementation of large-scale CO2 sequestration.

security (e.g. Abramov et al., 2019; Al-Khdheeawi et al., 2018;

1. Introduction
Carbon geo-sequestration (CGS) has been recognized as a strategic
technology to minimize the impact of carbon dioxide (CO2) emissions
arising from anthropogenic activities, thus mitigating global warming
(IPCC, 2005). Injecting CO2, at high pressure and temperature into
geological storage formations, where it can be permanently immobi­
lized, has been identified as the most effective way to capture and
securely store carbon for millions of years into the future (IPCC, 2005;
Bachu and Adams, 2003; Orr, 2009). Once injected, the supercritical
carbon dioxide (scCO2) is more buoyant than local fluids present in the
pore space (CO2 has a lower density than local brine); thus, it percolates
upwards through the porous rock until it reaches an impermeable
caprock layer, where it can be trapped by capillary forces (Iglauer, 2018;
Le Guen et al., 2007). Furthermore, CO2 can be trapped in the pore
network of the storage rock (“residual trapping”), again by capillary
forces, where it dissolves in formation water and sinks deep into the
reservoir (Riaz et al., 2006). For all these storage mechanisms, CO2-rock
wettability is a key parameter that influences storage capacity and
Al-Menhali et al., 2015; Broseta et al., 2012; Garing and Benson, 2019;
Iglauer et al., 2015a; Krevor et al., 2012; Rahman et al., 2016, Ali et al.,
2019). Therefore, it is of vital importance to accurately measure rock
CO2 wettability. However, conventional methods, such as Amott-Harvey
(AH), US Bureau of mines (USBM), contact angle and tomographic im­
aging measurements have serious limitations. amott–harvey (AH) and
US Bureau of mines (USBM) are expensive, time-consuming and prone to
error (so far they have not succeeded for scCO2-brine-rock systems)
(Iglauer et al., 2015b). Similarly, 2D contact angle measurements
overlook 3D pore geometry, surface roughness and chemical heteroge­
neity (at least in a classic contact angle experiment) (Al-Yaseri et al.,
2016a;; Valori and Nicot, 2019; Espinoza and Santamarina, 2010), while
medical CT resolution is too low (only averaged saturations can be
measured), and microCT curvature measurements may be biased due to
their voxelized nature (Iglauer et al., 2019).
NMR is fast, robust and can measure valuable structural insights on
fluid molecules in confined environment. Transverse relaxation time
(T2) can be used to determine petrophysical properties (porosity,
permeability, water saturation, wettability) and measures pore size

* Corresponding author.
E-mail addresses: a.baban@ecu.edu.au (A. Baban), a.yaseri@ecu.edu.au (A. Al-Yaseri).

https://doi.org/10.1016/j.ijggc.2021.103435
Received 22 December 2020; Received in revised form 22 May 2021; Accepted 12 August 2021
Available online 3 September 2021
1750-5836/© 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
A. Baban et al. International Journal of Greenhouse Gas Control 111 (2021) 103435

the core fluid from the confining fluid. This setup was housed in a cor­
Nomenclature list eflood apparatus (see Figure 1) with an integrated NMR (GeoSpec+
2.4MHz) instrument that consisted of four high precision syringe pumps
WI Wettability index (Teledyne Isco pumps, model 260D; pressure accuracy of 0.1 % full
Nc Capillary number scale). The first two pumps provided and maintained a confining pres­
Krnw Relative permeability of non-wetting phase sure of 13 MPa around the sample. Fluorine based oil (Fluorinert™ FC-
Krw Relative permeability of wetting phase 40) was used as the confining fluid (this is a non-hydrogenated fluid that
Sw Water saturation does not interfere with the NMR signal and has superior heat trans­
Pe Capillary entry pressure mission characteristics). The third pump injected fluids into the core,
Pc Capillary pressure while the fourth production pump applied backpressure and received
Sw* Normalised water saturation the produced fluids. A mixing reactor was used to equilibrate CO2 and
λ Pore size distribution index brine, yielding live brine (i.e. fully CO2-saturated brine at high pressure
T1 Longitudinal relaxation time and elevated temperature) as described by El-Maghraby et al. (2012).
T2 Transverse relaxation time The temperature of the pumps was controlled by a Jabala oil bath
r radius of the pores with heating tape wrapped around delivering and confining tubes to
ρ Surface relaxivity control the core temperature throughout the experiment (i.e. to
isothermal conditions of 333 K). Two high-accuracy pressure sensors
(Keller 33X, accuracy of ±1500 Pa) were attached to both ends of the
core to measure absolute pressure and pressure drop across the core
distribution (PSD) (Zhao et al., 2020; Lyu et al., 2018). T2 is very sen­ plug.
sitive to fluid-surface interactions and very responsive to paramagnetic During CO2 sequestration processes, initially a fraction of injected
ions from rock matrix minerals (Mitchell et al., 2013; Connolly et al., CO2 dissolves in the local brine and creates a live brine (brine saturated
2019; Korb, 2009; Washburn, 2017). Here we therefore used an inde­ with CO2) (Iglauer 2011). To simulate reservoir conditions, the core
pendent technique (NMR), which has a molecular resolution, to over­ sample inside the NMR coreflood apparatus was vacuumed for 48 h
come some of the abovementioned limitations, and to add to the before injecting 10 pore volumes (PV) of dead brine at a preset flowrate
fundamental understanding of flow processes of scCO2 through brine value of 1 ml/min, with 8 MPa backpressure. The saturated core was left
saturated porous rock. This work will thus aid in the implementation of for 24 h to ensure full brine saturation was achieved (effective stress was
large scale CO2 geo-sequestration and increase the certainity of constant throughout the experiment at 8 MPa). T1-T2 and T2 measure­
geo-sequestration schemes and carbon capture and storage projects. ments (note that T1 is the longitudinal relaxation time and T2 is the
transverse relaxation time) were performed and then 10 PV of live brine
2. Experimental Methodology were injected into the core at the same conditions as above to displace
all dead brine with live brine. Once the pressure drop stabilized, T1-T2
All experiments were performed on a cylindrical homogenous San and T2 responses for live-brine saturated core were obtained. Prior to
Saba sandstone sample (5 cm in length and 3.5 cm in diameter). The scCO2 injection, the outlet pressure was maintained constant at 8 MPa
sample consisted of 94 wt% α-quartz, 2 wt% Plagioclase and 4 wt% of (using an ISCO pump as a back-pressure regulator). Subsequently,
Alkali Feldspar; measured via a Bruker-AXS D8 Advance Diffractometer. capillary drainage pressures were measured by injecting 20 PV of scCO2
The sample had a porosity of 21 % and a permeability of 35 mD into the core plug at a constant flowrate of 0.1 ml/min, which was
(measured by a CoreLab UltraPoroPerm-910). The core plug was incrementally increased to 0.5, 1, 2, 4, 6 and 8 ml/min (Ramakrishnan
wrapped in polytetrafluoroethylene (PTFE) tape and sealed with double and Cappiello, 1991) with multiple T1-T2 and T2 scans taken for each
PTFE heat-shrink tubes, and a rubber sleeve (ends were open for the flow rate. Note that the capillary number (NC=Qμ/γ) varied between
injection and desaturation of fluids) was applied to adequately separate 6.23 × 10− 7 and 3.74 × 10− 5 consequently capillary forces dominated

Figure 1. Schematic diagram of the experimental apparatus

2
A. Baban et al.
(Dullien et al., 1989; Garing and Benson, 2019).
Once scCO2 injection started, water was displaced from the core until
steady-state was reached, i.e. no more water production was observed at
steady-state and the pressure drop across the core reached a constant
value. Further scCO2 flow maintained the pressure gradient within the
core and at each point in the core the pressure difference between CO2
and water equalled the capillary pressure (ΔP = PCO2 at inlet – Pwater at
outlet) (Ramakrishnan and Cappiello, 1991; Pini et al. 2013; Andersen
et al., 2017). Furthermore, the capillary pressure measurements were
made at the inlet of the core sample by successively increasing the CO2
flow rate, while average fluid saturations were measured via NMR T2. To
account for the capillary end-effect (Gupta and Maloney; Virnovsky
et al., 1998; Andersen et al., 2017), and to accurately determine the Pc
and Krg, the capillary end-effect analytical correction for saturation and
relative permeability were performed as detailed in Supplementary 1
(Virnovsky et al., 1998). The experiment was conducted twice, and
reproducibility of the experiments and results was good.
Finally, 10 PV of live brine were reinjected (forced imbibition) at the
same flow rates with capillary numbers between 4.17 × 10− 6 and 6.6 ×
10− 5 until residual CO2 saturation (SCO2,r) was achieved.
In addition, Darcy’s law can be generalized as a simplified rela­
tionship between flux and pressure gradient with relative permeability
described in terms of local saturation. Hence, the relative permeability
of CO2 (Kr,CO2) as a function of water saturation (Sw) was measured,
using below equation (with CO2 = i) (Dullien, 1992).
ui L μi
kri = (1)
ΔPi K
Where ui is the volumetric CO2 fow rate, K is the absolute core
permeability, µi is the CO2 viscosity, L is the core length and ΔPi is the
pressure drop at the inlet of the core. Water saturations (Sw) were
measured via NMR, and corrected for the capillary end effect (see
Supplementary 1). As outlined above, the viscous pressure drop across
the sample was taken as the capillary pressure (Pc) at the inlet face of the
core, Ramakrishnan and Capiello 1991).
Equation (2) is a general representation of capillary pressure (Pc) as a
function of saturation (Dullien, 1992).
( )− 1 times (τc) at Larmor frequency and T1 and T2 relaxation times should in
Pc = Pe S∗w λ
(2)
Pe is the minimum pressure required for the non-wetting phase to
enter the pores of the sample, i.e. the capillary entry pressure, and λ is a
fitting parameter (known as pore size distribution index) that tunes the
curvature of the Pc – Sw curves. The value of λ corresponds to the degree
of homogeneity of the pores size distribution in the sample; uniform
pore-size reservoir rocks have large values of λ, whereas broad pore size
distribution yield lower values of λ; Laliberte (1969), S∗w is the normal­
ized wetting phase saturation (Dullien, 1992).
Sw − Swr
S∗w = . (3)
1 − Swr
Where Swr is the residual saturation of the wetting phase. The
Brooks-Corey model is usually used to predict relative permeability of
the wetting and non-wetting ina multiphase flow systems (Dullien,
1992). The non-wetting (Krnw) relative permeability was thus predicted
via Eqs. 5, (Corey, 1954).
( )2+3λ
Krw = S∗w λ (4)
( ]
[ ( )2+λ
Krnw = 1 − S∗w )2 1 − S∗w λ
(5)
The transverse relaxation time (T2) of a spin-echo, in a confined
environment, such as pore spaces, fluids exhibit three independent
relaxation mechanisms; diffusion, bulk, and surface. The bulk fluids
(water, brine, light oil) have long transverse relaxation times and are
mainly controlled by spin – spin interactions between fluid molecules
3
International Journal of Greenhouse Gas Control 111 (2021) 103435
(Dunn et al., 2002; Freedman et al., 2003; Connolly et al., 2019), while
diffusion is induced by the presence of magnetic field gradient caused by
variation in magnetic susceptibility between the fluid and grains
composing the rock matrix (Brownstein and Tarr, 1979). However, for
short echo times (TE) and low magnetic field strengths, as used in this
study, the internal gradients are relatively weak, their effects are
negligible (Dunn et al., 2002; Connolly et al., 2019; Korb, 2009).
Furthermore, the bulk fluid (water) is diamagnetic and is mainly
controlled by spin – spin interactions between water molecules (Dunn
et al., 2002; Connolly et al., 2019). Thus, the surface transverse relax­
ation is more dominate and T2 can be written as function of the ratio of
the pore’s specific surface area to the total pore volume.
( )
1 S
= ρ2 (6)
T2 V pore
A simple limitation of using NMR to measure pore size distribution
(PSD) is unavailability of a fixed value of surface relaxivity (Almen­
ningen et al., 2020). Furthermore, the pore network in a porous medium
conceptually consist of pore-throats (cylindrical) and pore-bodies
(spherical) (Dullien, 1992) and no geologic porous medium will be
perfectly symmetric or have spherical pores. This is typically dealt with
a shape factor (c) and c is typically 2 for cylindrical (Mesquita et al.,
2016) and 3 for spherical pores, (Looyestijn, 2008; Djebbar and
Donaldson, 2015).
The measured T2 surface relaxation time is used to determine the
distribution of water in the different pores of the rock (Coates et al.,
1999; Akitt and Mann, 2000; Li et al., 2019).
r = cρ2 T2 (7)
r is the radius of the pores (µm), c is the shape factor and sphereical
pores assumed (c = 3) (Li et al., 2019), and ρ2 is relaxivity ≈ 18.3 µm.s −
1
for homogenous sandstone (Lucas-Oliveira et al., 2020; Washburn
et al., 2017; Li et al., 2019).
The T1/T2 ratio is a quantitative measurement of the strength of the
interaction between the fluid molecules in the pore space and the solid
surface (Katika et al., 2017; Guan et al., 2002). Thus, fast moving mol­
ecules and isotropic, i.e. nonviscous fluid, have a very short correlation
principle be similar or equal (T1/T2 = 1). However, in complex mole­
cules or for slow motion systems such as anisotropic (very viscous fluid
such as asphaltene or solid surfaces) T1 and T2 are affected differently
and hence T1/T2 differs from unity (Valori et al., 2017; Zielinski et al.,
2010; Lessenger et al., 2015). This is primarily due to affinity of the
wetting fluid to the surface of the minerals which significantly shorten
T2 relaxation time (Korb et al., 2009; Katika et al., 2017; Wang et al.,
2018).
The acquired T1/T2 ratios were selected at the point of highest in­
tensity in the T1 - T2 spectra (which correspond to hydrogen intensity
distribution of the pore fluid), are correlated to the USBM scale as an
independent wettability indicator [− 1 strongly oil-wet, 0 intermediate
and +1 strongly water-wet], via Eq. (8) which was deriven from Valorie
et al. 2013 data (Valori et al., 2013);
T1/T2 = − 2.25 WI + 2.25 (8)
The T1/T2 value is obtained from Fig. 2 and wettability index (WI)
can readily be determined, (If 0 < WI < 1, the rock is water-wet (WI ≈ 1
strongly water-wet), conversely if − 1 < WI < 0 the rock oil-wet (WI ≈
− 1 strongly oil-wet) (Looyestijn, 2008; Valori et al., 2017). A practical
limitation of Eq. (8) arises when measuring mixed-wet systems as NMR
uses an inhomogeneous magnetic field which cannot differentiate be­
tween water and oil (resonance frequency); the NMR response is
therefore a combination and an overlap of the responses of all 1H con­
taining fluids (oil and water) in the rock (Looyestijn, 2008; Valori et al.,
2017).
A. Baban et al. International Journal of Greenhouse Gas Control 111 (2021) 103435

3. Results and Discussion

3.1. NMR wettability indices

Initially, the sandstone sample was strongly water-wet a T1/T2 ratio

equal to 1 was measured, (see Table 1 and Figure 2a). However, the T1/
T2 ratio increased significantly to 1.7 following live brine saturation,
and remained so for the rest of the experiment (i.e. after primary
drainage with CO2 and live brine imbibition and secondary drainage).
This increase in T1/T2 ratio indicates a drastic reduction in sandstone
hydrophilicity due to live brine exposure. This reduction in hydrophi­
licity was caused by additional protonation of surface silanol groups
(Stumm and Morgan, 2012) (which are located on the quartz surface;
Chen et al., 2015), induced by the carbonic acid (note: CO2 chemically
reacts with H2O to carbonic acid which partially dissociates into H+,
HCO−3 , and CO2− 3 , Adamczyk et al. (2009); the pH value of live brine
under the experimental conditions was 3.6; Peng et al. (2013)). This led
to a lower surface potential and lower polarity of the quartz surface (the
surface become more electrically neutral), which again reduced the
surface’s affinity to (polar) H2O, and thus reduced hydrophilicity
(Iglauer, 2017; Abramov et al., 2019). Importantly, the system remained
weakly water-wet after CO2 was introduced as a separate supercritical
phase (for both, initial CO2 saturation (SCO2,i) – drainage, and residual
CO2 saturation (SCO2,r) – imbibition), i.e. WI = 0.26 was measured,
Table 1. This is consistent with most data in the literature as measured
via video contact angle, microCT and micromodel imaging, capillary
pressure and relative permeability measurements; see also further dis­
cussion below (and compare (Akbarabadi and Piri, 2013; Al-Yaseri et al.,
2016a; Andrew et al., 2014; Chalbaud et al., 2009; Chiquet et al., 2007;
Krevor et al., 2012). Further, as Figure 2a shows, the vertical dashed line
intersects with T2 at 20 ms as compared to T2 = 10 ms for all other
conditions (Figure 2b, c and d). The reduction of high intensity areas
(red band) in Figure 2c, 2d is due to decrease of hydrogen contents in the
fluid inside the rock which demonstrates displacement of water in the
large pores by CO2. This is a clear indication that scCO2 displaced water
in the large pores, which is again an indication of a water-wet system
(Blunt, 2017), consistent with all above observations.
Table 1 looks very confusing in its current format below. There
should be 3 columns x 5 rows (refer to the original format in the
manuscript). Separating the numbers from the text by wide spaces will
make the table neat and tidy.

3.2. Capillary pressure and relative permeability curves

The capillary drainage pressure (Pc) for San Saba sandstone ranged
from 10 to 124 kPa, as shown in Figure 3. The difference between the
San Saba Pc − Sw data and data in the literature (also shown for com­
parison) can be attributed to variations in petro-physical characteristics
of the samples and differences in applied thermo-physical conditions
that can change fluid properties (Abdoulghafour et al., 2020; Al-Yaseri
et al., 2016a; Iglauer et al., 2015a; Iglauer et al., 2015b; Saraji et al.,
2013). A total of 20 PV of scCO2 was injected to displace brine

Table 1
T1
NMR ratio and NMR wettability indices measured for San Saba sandstone for
T2
Figure 2. NMR T1− T2 maps used to determine the T1/T2 ratio and the each process. Note that a wettability index and a NMR T1/T2 ratio of 1 indicate a
wettability indices (WI) for San Saba sandstone (measured at 8 MPa and 333 K), completely water-wet system, while a wettability index of 0 indicates an
the solid diagonal line indicates T1 = T2, a) fully saturated with dead brine, b) intermediate-wet system and a wettability index of − 1 indicates a strongly oil-
fully saturated with live brine, c) initial CO2 saturation (after drainage). d) wet (Al-Muthana et al., 2012; Valori et al., 2017).
residual CO2 saturation (after r drainage). d) residual CO2 saturation (after
Process T1 Wettability index
imbibition). Note that the T1/T2 ratios were selected at the point of highest NMR ratio
T2
intensity in the map (red bands) for WI calculation.
Dead brine 1 -
Live brine 1.7 -
Drainage (CO2 injection) 1.7 0.26
Imbibition (brine injection) 1.7 0.26

4
A. Baban et al. International Journal of Greenhouse Gas Control 111 (2021) 103435

Table. 2
CO2 saturations during primary and secondary drainage and secondary imbi­
bition (measured via NMR) as a function of flow rate.
Flowrate (ml/min) 0.1 0.5 1 2 4 6 8

Primary drainage 0.08 0.15 0.20 0.242 0.288 0.31 0.31

(SCO2,i)
Secondary drainage 0.09 0.13 0.20 0.246 0.292 0.34 0.34
(SCO2,i)
Imbibition (SCO2,r) 0.23

T2 measurements were used to determine the pore-size distribution

via Eq. (7) and to observe the variation of the brine distribution in the
rock’s pore network. It is clear that the scCO2 displaced the (live) brine
from large pores indicating water-wet behaviour (represented by the
shaded area in Figure 5); thus, the T2 relaxation time peak shifted to the
Figure 3. Primary and secondary drainage (scCO2) capillary pressure versus
left (from pores with radii larger than 20 µm to pores with radii less than
brine saturation measured for the San Saba sandstone sample. □ Blue open
10 µm). The preferiential CO2 occupancy by large pores after CO2
squares: primary drainage for San Saba, o red circles: secondary drainage for
San Saba, Black symbols: literature data, added for comparison. The dotted blue
saturated (live) brine flooding is consistent with work reported by
line is the Brooks-Corey model fit. (Connolly et al., 2017) and is also consistent with the observations of
more surface wetting characteristic for CO2 reported by contact angle
method (Al-Yaseri et al., 2016; Iglauer et al., 2015; Iglauer et al., 2014)
(drainage) until SCO2,i (initial CO2 saturation) was established, SCO2,i was
and with results of pore scale residual trapping by x-ray micro-computed
31% at 110 KPa (irreducible water saturation Sw,irr was 69%) and SCO2,r
tomography (μCT) (Igaluer et al., 2011; Niu et al., 2014; Iglauer et al.,
(residual CO2 saturation) (after imbibition) was 23%, consistent with
2019). In contrast, water content in the small pores, (pore radii r < 1
literature values for water-wet sandstone (Akbarabadi and Pini, 2013;
µm), remained unchanged. The lower water saturation of the imbibition
Al-Menhali and Krevor, 2016; Iglauer et al., 2011; Krevor et al., 2012;
T2 peak (incremental porosity black curve in Figure 5) is attributed to
Pentland et al., 2011). As Figure 3 shows, the secondary drainage
the presence of scCO2 in large pores (CO2 is not detected by the NMR
capillary pressure curve shifted very slightly to the right, indicating a
signal).
slight increase in CO2-rock wettability.
Steady state drainage relative permeability data measured as a
4. Conclusions
function of water saturation at representative reservoir temperature and
pressure are presented in Figure 4 and Table 2. Brooks – Corey model
CO2-wettability of storage and caprock is a vital parameter as it
curves (shown as black solid lines ___, obtained via Equations (4) and 5,
determines storage capacities and containment security (Chiquet et al.,
were fitted to the measured datapoints. The Krw - Krg intersection point
2007; Iglauer 2017; Broseta et al., 2012; Iglauer et al., 2015). However,
(for primary drainage) at Sw = 0.7 (Figure 4) indicates strongly water-
there still exists significant uncertainty regarding this parameter, which
wet characteristics of the sample, and is comparable to values stated
leads to high project risk. Thus, we measured the wettability of a
in the literature (Abdoulghafour et al., 2020; Krevor et al., 2012; Niu
quartz-rich sandstone via NMR measurements to reduce this uncer­
et al., 2014; Perrin and Benson, 2009; Pini and Benson, 2013). The slight
tainty. Interestingly, the initially strongly hydrophilic sample turned
variation of the wettability estimation (relative permeability curves
significantly less hydrophilic when exposed to CO2 (either in the form of
intersection), when compared to some of the curves in the literature, are
molecularly dissolved or free supercritical CO2) − the T1/T2 ratio
due to the impact of rock structure and composition; samples with low
increased from 1 to 1.7. These changes in hydrophilicity of the
porosity have overall lower CO2 saturations, rocks with lower void
spaces permit less fluid to pass through them, and thus lower
non-wetting relative permeabilites (Knw), whereas formations with
larger porosity have higher average CO2 saturations and thus higher Knw
values (Perrin and Benson, 2009; Krevor et al., 2012).

Figure 4. Steady-state drainage relative permeability curves for the San Saba
sandstone (o red open circles). black lines () are best fit Brooks – Corey (BC)
curves. Literature data is also plotted for comparison.
Figure 5. Water saturation in the pore network of the San Saba sandstone after
drainage (CO2 flooding) and imbibition (secondary live brine flooding). The
entire T2 drainage curve (red) shifted left which depicts that CO2 displaced
water from the large pores during drainage. This indicates water-wet behav­
iour. Note that T2 times were converted into pore radii via Eq. 8.

5
A. Baban et al.
sandstone surface we explain by additional protonation of surface sila­
nol groups and consequently reduced affinity of the quartz surface to
polar H2O, which reduces hydrophilicity (Chen et al., 2015). Related to
this a weakly water-wet behaviour for all two phase (CO2 and brine)
systems (primary and secondary drainage and secondary imbibition)
was observed, i.e. WI = 0.26. The capillary pressure, relative perme­
ability and sequential NMR T2 distributions (for each process step) were
comparable with results in the literature acquired via independent X-ray
tomography experiments (Abdoulghafour et al., 2020; Iglauer et al.,
2011; Krevor et al., 2012; Niu et al., 2014; Pentland et al., 2011). As here
an independent technique (NMR) was used, the confidence in the pre­
vious datasets is signficiantly increased. Interestingly, water-wettability
was further slightly reduced during secondary drainage. Finally, we
used the NMR T2 relaxation time distributions to demonstrate water
displacement by CO2 in large pores only (r > 1 µm), while water
remained unchanged in small pores (r < 1 µm).
The overall conclusion is that CO2 significantly reduces sandstone
hydrophilicity and water-wettability. This work therefore provides
fundamental insights into CO2-water displacement processes, and will
aid in the large-scale implementation of CO2 geo-sequestration schemes
and carbon capture and storage projects.
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.
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.ijggc.2021.103435.
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