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Nano-modified CO2 for enhanced deep saline CO2 sequestration:

A review and perspective study

T.D. Rathnaweera, P.G. Ranjith

PII: S0012-8252(19)30579-3
DOI: https://doi.org/10.1016/j.earscirev.2019.103035
Reference: EARTH 103035

To appear in: Earth-Science Reviews

Received date: 27 August 2019

Revised date: 29 October 2019
Accepted date: 14 November 2019

Please cite this article as: T.D. Rathnaweera and P.G. Ranjith, Nano-modified CO2 for
enhanced deep saline CO2 sequestration: A review and perspective study, Earth-Science
Reviews(2019), https://doi.org/10.1016/j.earscirev.2019.103035

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Cover Page

Manuscript Title:

Nano-modified CO 2 for enhanced deep saline CO 2 sequestration: A review and perspective study.

Authors’ names:

T. D. Rathnaweera*1 and P.G. Ranjith1

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1
Department of Civil Engineering, Monash University, Building 60, Melbourne, Victoria, 3800,
Australia.
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*Corresponding author:
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Dr. Rathnaweera TD
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Deep Earth Energy Laboratory, Monash University, Building 60,

Melbourne, Victoria, 3800, Australia.

Phone/Fax: 61-3-9905 5549

E-mail: tharaka.rathnaweera@monash.edu

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Abstract

CO2 sequestration in deep saline aquifers has been well-established as a mode of reducing the anthropogenic
emissions of CO2 and mitigating the risks associated with human-induced global warming. The long-term success
of a deep saline sequestration project depends in particular on the volume of CO 2 sequestrated and the prevention
of risk of leakage. However, current practice still suffers from the slow solubility of injected CO 2 in brine, making
conventional versions of the process inefficient, uneconomical, and unsafe. Therefore, the aim of this study is to
review current techniques and propose a new high-performance technique for CO 2 sequestration in deep saline
aquifers, by introducing nanoparticles into injected CO2 . Nanoparticles are considered promising tools for
improved seepage efficacy in the petroleum industry, and studies of CO2 sequestration have led to exciting
developments in the last few years. Unfortunately, our knowledge of the complex interaction between
nanoparticles, CO2 and reservoir pore fluid and its feedback on other operational and reservoir parameters are
poorly understood. The first part of this article gives an overview of conventional mixing of CO 2 and how nano-

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injection improves convective mixing, based on critical wavelengths and critical onset times calculated using
thirty-two saline aquifers around the world. In addition, several different nano-injection methods and possible

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nanomaterials for deep saline sequestration are discussed. The second part of this article considers the influence of
nano-injection on gravity, viscous and capillary forces and how these non-linear alterations change the
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conventional mechanism of CO2 plume development, and the propagation and transport characteristics of CO 2 in
porous media based on the wettability, interfacial tension and solubility modifications which occur with the
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introduction of nanoparticles into the CO2 stream. The proposed technique promises to enhance CO 2 storage
capacity, reduce operational and monitoring costs, and minimize the risk of leakage to nearby freshwater aquifers.
This study generates valuable new science, applied in technology that can be used for real-world CO2 storage
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enhancement in pilot and field-scale projects. However, further research in related areas is required.
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Keywords: deep saline aquifers, climate change, conventional injection, nano-injection, nanoparticles
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1. Introduction
Climate change is proceeding at an alarming rate, mainly due to elevated levels of anthropogenic CO 2 in the
atmosphere (see Fig. 1 and Table 1). The scientific consensus is clear, and the question is no longer whether but
how much is occurring, how fast, and above all what can be done to halt it? Countries have tried many approaches
to control their CO2 emissions (White et al., 2003; Leung et al., 2014), with mixed success, including 1) improved
energy efficiency and promotion of energy conservation, 2) promotion of the use of low carbon fuels, such as
hydrogen and nuclear power, 3) increased use of renewable energies, such as solar, wind, hydropower, geothermal
and bioenergy, 4) introduction of geo-engineering approaches, such as afforestation and reforestation, and 5) CO2
sequestration or CO2 capture and storage (CCS) (Ampomah et al., 2017; Mac Dowell et al., 2017; Dai et al., 2018;
Newell and Ilgen, 2019).

After much research on these approaches to the mitigation of global climate change (Li et al., 2006; IEA, 2015),

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CO2 sequestration has been identified as the only technology which can reduce CO 2 emissions at a significant scale.

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Three main geological formations, depleted oil and gas reservoirs, un-mineable coal beds, and deep saline aquifers,
have been widely considered for the storage and isolation of anthropogenic CO2 captured from the surface

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environment (Soltanian and Dai, 2017; Sun and Tong, 2017; Li et al., 2018). CO2 sequestration in depleted oil and
gas reservoirs has been in use in the oil and gas extraction industry for decades to enhance the recovery of residual
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oil and gases, and not only offers a solution to mitigate climate change, but also has economic value which can be
effectively used to overcome economic barriers associated with CCS (Dai et al., 2014; Dai et al., 2016; Hoteit et al.,
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2019; Tcvetkov et al., 2019). Although this method is considered to be the most mature technology for the
injection of CO2 for enhanced oil recovery (EOR), disadvantages, mainly the limited available capacity and
potential leakage risks, limit its feasibility for CO2 storage (Jia et al., 2019; Ma and Ranjith, 2019). The ability to
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permanently store injected CO 2 due to the adsorption capability of CO 2 to the coal matrix is a unique advantage
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associated with CO2 sequestration in un-mineable coal beds (Perera et al., 2011; Baena-Moreno et al., 2019). This
method is widely used in the industry to recover the valuable energy product methane (CO2 -enhanced coal bed
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methane recovery) which helps to partly offset the costs of sequestration. However, several key issues associated
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with this process, including limited global storage capacity, storage integrity, physical and chemical processes, loss
of gas injectivity due to swelling, permeability reduction around wellbores and environmental health and safety,
may reduce its likely use as a CO2 storage candidate (White et al., 2003). CO2 sequestration in deep saline aquifers
offers an innovative and ingenious way to combat increased emissions (IPCC, 2016). Such aquifers are the most
abundant geological reservoirs in the sub-surface, both on- and off-shore (Singh, 2008). According to a
comprehensive survey of projects by White et al. (2003), this kind of sequestration is the most technically feasible,
with little or no negative environmental impact. Deep saline aquifers have the largest storage capacity of all
geological media (Bruant et al., 2002); worldwide, it is estimated that they could store up to 10,000 Gt of CO 2
(IPCC, 2016). A comparison of the available storage capacity of the three major geological storage options is
shown in Table 2.

However, there is one fundamental drawback: the slow solubility of injected CO2 in brine, which makes
conventional versions of the process inefficient and uneconomical (Rathnaweera et al., 2016a). Studies of possible

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enhancement techniques show that sequestration can be improved by co-injecting CO2 and brine and CO2 and
water. However, Eke et al. (2011) have found that this demands excessive volumes of water, which in turn means
significant costs in energy and money. In any case, the world cannot afford to lose vast amounts of precious water
to the deep earth. With the Paris Climate Change Agreement in 2016, 138 countries including Australia agreed to
cut CO2 emissions to a rate that would cap global warming at 2 °C above pre-industrial levels (Rogelj et al., 2016).
But as IEA’s study (IEA, 2015) shows, to achieve this target global CO 2 storage and sequestration capacity must
expand to around 4,000 million tonnes by 2040, and 6,000 million tonnes by 2050 (Stephenson et al., 2019).
Capping at 2°C cannot be achieved by renewable or other non-emitting energy technologies; but as IEA (IEA,
2015) modelling also makes clear, 45% of total emissions from the industrial sector can be successfully mitigated
by implementing CO2 geosequestration. However, this is simply not possible with current methods. In the absence
of CO2 sequestration, additional global investment in the electricity sector would cost $2 trillion over 40 years
(Rogelj et al., 2016).

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It is therefore imperative that we invest research effort in radically enhanced storage and sequestration techniques,
to store and isolate captured anthropogenic CO 2 from the surface environment effectively, efficiently, affordably,
safely, and sustainably. The aim of this perspective study is to add to our understanding of cutting-edge
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developments in enhanced CO 2 sequestration in deep saline aquifers through cost-effective and environmentally
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responsible nano-CO2 injection. This study yields quantitative and qualitative recommendations, based on reliable
findings concerning the chemico-mineralogical and hydro-mechanical responses of aquifers to the sequestration
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process. Our findings generate valuable new science, which can be applied in technology that can be used for real-
world CO2 storage enhancement in pilot and field-scale projects.

1.1. Convective mixing of CO 2 in conventional deep saline sequestration

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Over the past few decades, extensive research has been conducted on interactions between CO 2 , brine, and
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reservoir rock when supercritical CO 2 (typically at 7.4 MPa and 31.5 °C) is injected into deep saline aquifers
(Rosenbauer et al., 2005; Kharaka et al., 2006; Rutqvist et al., 2010; Gershenzon et al., 2017). Researchers have
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found that the injected CO 2 first moves sideways next to the well bore. Due to buoyancy differences between the
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supercritical CO2 and in situ interstitial brine, it then migrates upward until it reaches the sealing caprock; it then
spreads radially (Andrew et al., 2015) and dissolves, starting to react with reservoir rock minerals, as shown in Fig.
2. A dense layer of brine with dissolved CO 2 (CO2 –brine) forms at the general interface between the overlying CO2
plume and the residual brine. The positive density contrast between this CO 2 +brine and in situ brine triggers
instability and convective mixing. According to Javadpour and Nicot (2011), the critical times and wavelengths of
the mixing fingers are highly dependent on the characteristics of the reservoir rock and aquifer fluid.

Fig. 3 summarizes some of the short- and long-term mixing mechanisms involved in deep saline aquifers. Short-
term mixing involves gravity override of CO 2 and viscous immiscible displacement, which normally occur in
timeframes of years to decades, and long-term processes like diffusion and convection occur over century-long
timeframes (Hassanzadeh et al., 2007). During the long-term interaction of injected CO2 and aquifer brine,
convection is triggered due to the diffusion of CO2 into the underlying formation (Babaei and Islam, 2018). Based
on the time and space variables, a fraction of ultimate CO 2 dissolution can be characterized in terms of diffusive
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mixing, early convective mixing and late convective mixing (Roques et al., 2018). The mixing takes many years,
and until it is completed, there is increased risk of CO2 back-migration into the atmosphere through the sealing
caprock and also through pathways such as fractures, faults, and abandoned wells. Therefore, a rapid technique is
required for mixing injected CO2 with the underlying brine, to overcome the risk of leakage. Correct estimation of
scaling relationships for the onset of convection, the initial wavelength of convective instabilities, the mixing
duration and the Sherwood number, and a thorough understanding of how the non-linear feedback of the separation
point between diffusion and convective mixing varies in time and space are crucial for the development of an
exciting new CO2 storage- and sequestration-enhancing technique in deep saline aquifers.

2. Nano technology for deep saline aquifers

Injection using supercritical CO 2 with nanoparticles (NPs) in suspension (nano-CO2 ) is a sophisticated new way to
enhance storage and sequestration in deep saline aquifers (Mackay and Gschwend, 2001). Preliminary analysis by

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Javadpour and Nicot (2011) shows that it can improve convective mixing, speeding sequestration and reducing the

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risk of leakage. Such improved convective mixing condition reduces the amount of solar CO 2 in the gas phase ,
which can escape under high pressure conditions. In the present paper, estimations used linear stability analysis for
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the NPs of different materials, including barite, steel, lead, triuranium octaoxide and uranium dioxide; then thirty-
two real-case scenarios were used to test the theoretical analysis. It is assumed that injected CO2 behaves like a
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non-polar liquid, neglecting the adsorbtion process onto mineral grains and its influence on formation permeability.
Table 3 provides the reservoir properties used for the analysis. For the theoretical analysis, two enhancement
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factors were defined, and , to relate (critical time) and (wavelength of the mixing fingers) of CO 2 to
nano-CO2 (Javadpour and Nicot, 2011):
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and ,
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where,
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,
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and is the volume fraction of NPs, is the mass density of each phase, and is the density difference between
brine saturated with CO2 and brine without CO2 .

Fig. 4 shows critical wavelength and critical onset times calculated for the Alberta Basin, Canada and the Gorgon
Basin, Australia with CO2 alone and nano-CO2 of various types, and Table 4 provides more evidence based on
another thirty saline aquifers in the USA, Japan, Germany, Norway, Algeria, and the North Sea. The use of nano-
CO2 decreases the wavelength of the mixing fingers and reduces critical onset time for mixing; a 0.001 volume
fraction of NPs reduces onset time by almost 80% and increases convective mixing by around 50% (Javadpour and
Nicot, 2011). Translated to the field, this would cut the onset time from 5 years to 1 year, and once convective
mixing begins, it could be enhanced by nearly 50%. However, these results are preliminary and rely on the
theoretical analysis of linear stability. Comprehensive field and laboratory experiments are now needed to prove
the technique’s applicability. In particular, there is a need to evaluate the effects of nano-CO2 injection on the

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hydro-mechanical and chemico-mineralogical properties of aquifers, for an accurate appreciation of the
effectiveness and efficiency of the proposed method.

2.1. Possible nano-materials for deep saline sequestration

The proposed method involves the injection of high-mass density NPs into the CO 2 /brine system to improve
convective mixing and decrease the onset time of instability by increasing the density contrast between the CO 2
and brine. Particle size ranges from 1Ƞm to 100Ƞm are normally considered as NPs (Krishnamoorti, 2006). Among
the advantages of NPs, an ultra-small size-induced very high surface-to-volume ratio increases the interactions of
nano-atoms on the CO2 /brine interface. Most importantly, CO2 -wet NPs increase the macroscopic sweep efficiency
by penetrating pores and contacting more sweep zones which conventional CO2 is unable to reach. This is because
NPs are considerably smaller than reservoir pore and throat sizes (Alomair et al., 2014). Due to the ultra-small size

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of NPs, the risk of pore plugging is unlikely to occur, which consequently eliminates the likelihood of reservoir
permeability reduction and increased injection cost. Based on current knowledge of the enhanced oil recovery
(EOR) mechanics of NPs, this novel nano-injection can be carried out in the form of nanofluids, nanoemulsions,
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nanocatalysts, nanocrystals and micro-gel nanospheres (Sun et al., 2017). Fig. 5 summarizes the mechanisms of
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these approaches.

The conventional injection system can be modified by adding NPs which have an average size of less than 100Ƞm
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into the captured CO2 stream and such a system with CO2 and NPs in colloidal suspension can be defined as a
nanofluid system. In nanofluid systems, captured CO2 can be in its liquid or supercritical state, depending on the
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operational pressures and temperatures. Various possible NPs show useful characteristics for enhancing CO2
sequestration. Based on their chemical and physical properties, potential NPs can be categorized as semi-metal
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oxides, metal oxides and natural organic compounds, and most of these NPs are environmentally friendly and
cheaper than other chemicals which can be used to enhance CO2 retention efficiency. Two alternative nanofluid
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injection methods are proposed as possible nanofluid flooding mechanisms : cellulose nanocrystals (CNCs) and
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micro-gel nano-spheres (Molnes et al., 2016). The idea of adding nanocrystals to the CO2 /brine system is supported
by their ability to interact with CO2 and water molecules and alter the intermolecular forces of viscosity by acting
as additives for the CO2 /brine system (Kavitha et al., 2012). This yields an enhanced viscosity contrast reduction
(between nano-CO2 and brine), and consequently improves the sweep efficiency of the reservoir. Some possible
CO2 sequestration enhancing semi-metal oxides, metal oxides and natural organic NPs are presented in Fig. 5.

The application of nano-emulsion in CO2 sequestration is a novel idea which has not previously been used in deep
saline sequestration. Our study proposes a new hybrid concept for CO2 sequestration in deep saline aquifers by
combining nano-emulsion as a CO2 absorbent. Nano-emulsions show better CO2 absorbtion characteristics than
nanofluids (Rodrigues et al., 2019), because, in nanofluid injection, the ageing processes involving ostwald
ripening, precipitation, dissolution, flocculation and aggregation of the injected NPs may restrict mass transfer
performance by weakening their dispersion characteristics under deep reservoir conditions (Kim et al., 2018). It has
even been reported that semi-metal oxide ( ) and metal oxide ( ) nanofluids enhance the

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absorption characteristics of CO 2 , and these processes involving flow impediment may jeopardize the relevant
mechanisms of dispersion of CO 2 (Kouloulias et al., 2016). The main idea of this method is to absorb CO 2 into
nano-emulsion before injection into the reservoir using physical methods which can sustain high operational
pressures and high concentration of CO 2 . This adds an additional benefit to the project, providing a simple
absorption interface that can be used to store additional CO 2 before real CO2 sequestration begins. Nano-emulsions
are on the same particle size-scale as nanofluids at less than 100Ƞm, but their molecular structures are kinetically
controlled such that they can survive in extreme reservoir conditions such as high temperatures, pressures, salinity
and shear (Walia et al., 2019). In addition, the high viscosity characteristic of nano-emulsions appear to have a
greater impact on CO2 plume development, as it effectively controls the mobility of CO2 flooding (Adkins et al.,
2007). The unstable behavior of conventional CO 2 +brine systems due to lack of sufficient permeant dipole
moments and the weak van der Waals forces of captured CO 2 can be eliminated by adding nano-emulsion, which
enhances the stabilization of the CO2 plume and improves CO 2 flooding (Rognmo et al., 2018). However, the

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particle size distribution and electrostatic surface charge alterations of the particles due to complex interactions

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between CO2 and brine significantly modify the stability and formability of the CO 2 plume, which in turn affects
the storage efficiency of the system (Guo et al., 2019). Possible NPs for this application are listed in Fig. 5.
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The use of nano-catalysts has proven to be an effective and efficient method for improving oil recovery in oil
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reservoirs (Borah et al., 2019). Nano-catalysts consist of nano-sized metal particles, and can be successfully used
for CO2 sequestration in deep saline aquifers by applying the already-established knowledge of the
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“aquathermolysis” reaction. This reaction facilitates a fundamental and economical way to reduce the viscosity of
heavy oil deposits by increasing the concentration of saturates and lighter aromatic hydrocarbons (Muraza and
Galadima, 2015). The addition of nano-catalysts actively break the carbon-carbon, carbon-sulfate and carbon-
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oxygen bonds in resins and asphalts, which enhances the proportion of heavier compounds and light linear alkanes
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and finally, the concentration of saturated hydrocarbons (Iskandar et al., 2019). The most recent data suggests the
large viscosity contrast between CO 2 and brine limits the success of deep saline sequestration by lowering sweep
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efficiency (Jiang et al., 2019). Sweep efficiency is important for capacity estimations in deep saline aquifers, and is
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highly dependent on the reservoir thickness, vertical permeability distribution and mobility ratio of the injected
CO2 and formation brine (Myshakin et al., 2019). The injection of nano-catalysts such as , ,
and has the potential to improve the mobility of the system by enhancing
the ratio of the effective permeability to the viscosity of the system. This may occur upon injection of nano-
catalysts due to the reduced viscosity contrast between CO2 and brine. The viscosity of brine is much higher than
that of injected CO2 and the addition of nano-catalysts enhances the viscosity of the nano-CO2 phase, which results
in a viscosity contrast between the CO2 and the brine reduction. In addition, the displacement and saturated
characteristics of the CO2 and brine phases are significantly altered by the viscosity contrast reduction-induced
relative permeability changes of the CO2 and brine. This altered permeability then affects the gravity segregation
and viscous fingering phenomena and finally, the sweep efficiency. However, if the deep saline aquifer is
contaminated with hydrocarbons, the response of viscosity contrast may be significantly different and much more
complicated, as the aquathermolysis reaction comes to play a critical role in the viscosity of the brine phase.

2.2. Possible nano-injection methods

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Two different methods, 1) solid and 2) foam-based are proposed in our study. The proposed nano-CO2 mixture has
a base fluid which is supercritical CO 2 /liquid CO2 and suspended nano-scale solid particles made of surface-active
agents from surface charge methods. The solid-based nano-CO2 method can be achieved through a series of
continuous mixing which involves finding the optimal ratio of CO 2 to NPs for sequestration in deep saline aquifers.
This method requires an additional measure to determine the optimum nano-CO2 -injection regime for sequestration
and includes the efficiency and cost estimations of surface mixing versus separate injection (CO 2 first, followed by
NPs and brine). The aim of the foam-based approach is to produce a mixture with the desired quality and texture
by injecting a single continuous phase or co-injecting CO2 and NPs and creating a foam in the porous reservoir.
The most likely mechanism to occur in this method is snap-off, triggered during the interaction between the non-
wetting nano-foam and wetting brine at the pore throat, forming a curved interface until it reaches critical capillary
entry pressure. Once it reaches that pressure, the foam snaps-off and invades the pore body, acting as a
discontinuous phase. This occurrence hinders the effect of lamella in wetting brine as it tends to separate from the

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upstream pore matrix.

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For nano-CO2 injection, a uniform and stable dispersion of NPs in CO 2 or CO2 +brine is important, which requires

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the manipulation of the chemical and physical properties of NPs in order to achieve an effective and efficient
mixture with the desired properties. One way to manipulate the basic properties is to incorporate surface-active
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agents, which include surfactants and block copolymers. The addition of a surfactant with both polar and apolar
groups enhances the adsorbtion capacity at the interface between CO2 and brine, reducing the surface tension.
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Potential surfactants to promote dispersion of NPs in supercritical CO 2 or CO2 +brine can be classified as cationic,
anionic and nonionic/zwitterionic , based on their electrostatic potential. The interaction between NPs, surfactants
and CO2 occurs due to electrostatic surface charge difference-induced Coulombic attractions. Fig. 6 provides
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possible adsorption and shielding mechanisms of nano-CO2 +polymers/surfactants under aqueous conditions.
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In addition, ageing processes including adsorption, degradation, precipitation, aggregation and sedimentation of
NPs in CO2 +brine govern the stability of the nano-modified CO2 +brine mixture. The stability of NPs can be
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improved by utilizing different NP partitioning scenarios and adding engineered ligands (Mukherjee et al., 2018;
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Sanz-Robinson and Williams-Jones, 2019). Possible NP partitioning scenarios are 1) mix NPs and CO 2 through
the shear dissolution process, 2) NPs remain ahead of CO 2 molecules, and 3) NPs remain behind the CO 2
molecules. During nano-partitioning, NPs and surfactants may disperse, flocculate and stabilize in CO 2 , CO2 +brine
and brine. Fig. 7 shows possible scenarios for the dispersion, flocculation and stabilization of NPs and surfactants
in a CO2 sequestration system.

3. Effect of nano-CO2 injection on gravity, viscous and capillary forces

It is important to understand possible ways of immobilizing injected nano-modified CO2 in a deep saline aquifer.
Based on knowledge gained from conventional trapping mechanisms, CO 2 trapping upon nano-modification may
occur by a variety of mechanisms, including the following: 1) a small amount of nano-CO2 can be trapped as a
separate phase under the caprock, 2) a major amount of nano-CO2 can be trapped by enhanced solubility trapping
due to the dissolution of nano-CO2 in the brine and accelerated chemical reactions of nano-CO2 with constituents of
the brine and rock minerals, and by altered capillary snap-off of a residual nano-CO2 phase. The influence of
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conventional CO2 dissolution on solubility trapping has been studied by many researchers (Rathnaweera et al.,
2015b; Rathnaweera et al., 2016a; Rathnaweera et al., 2018; Hovorka et al., 2019; Ouyang et al., 2019). The
dissolution of CO2 in brine increases the density of the CO 2 +brine phase and significantly affects the mechanisms
of gravity, viscous and capillary forces by altering the flow path of CO 2 . In conventional injection, immediately
after injection, the interface between the CO2 and brine is stable, since CO2 is less dense than the brine phase.
However, nano-modification by high-mass density NPs may interfere with the initial stability of the CO2 +brine
phase, because adding NPs changes the effective physical properties of the conventional CO2 +brine phase.

Fig. 8 reveals that the density of the supercritical CO2 +brine phase increases with the addition of high-mass density
NPs. Here, the density calculation was carried out using experimental densities of reservoir pore fluid obtained
from the Tianjin reservoir, China under sequestration conditions (Zhang et al., 2011) and the influence of adding
five possible NPs to the CO2 +brine phase was analyzed. The density ( ) relationships between nano-CO2 +brine,
CO2 +brine, brine, nano-CO2 and CO2 can be expressed as

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(Javadpour and Nicot, 2011). Altered density contrasts between the nano-CO2 and
brine and the nano-CO2 +brine and brine phases trigger instability and consequently improves the overall mixing

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performance (solubility trapping) of injected CO 2 by inducing convective mixing, resulting in reduced density
stratification. The thickness of the capillary transition zone (single-phase CO2 ) reduces with nano-modification and
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the diffusive boundary layer evolves due to the improved convective mixing. The reduced density contrast (the
density difference between brine and nano-CO2 ) then alters the gravitational forces acting on the system. Since
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nano-CO2 -enriched brine has a greater density than the original brine, nano-injection tends to reduce the upward
migration of CO2 and this leads to gravitational flow instability in the reservoir. With respect to conventional
injection, CO2 -rich brine sinks much faster in the reservoir and forms thicker gravity fingers because of this nano-
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injection-induced gravitational flow instability.

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However, the influence of viscosity is also critical in determining the behavior of the transition from flow
dominated by viscous forces to flow dominated by gravity segregation of injected CO 2 . For viscosity analysis in
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nano-injection, the Einstein (Masoumi et al., 2009) and Brinkman (Sedaghat and Yousefi, 2019) models can be
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incorporated and estimated based on the volume fraction of the NPs and the viscosity of a conventional CO 2 +brine
mixture. Both models reveal that the addition of NPs slightly increases the viscosity of the conventional CO2 +brine
mixture (Javadpour and Nicot, 2011). The induced viscosity increment causes the effective permeability of the
reservoir to be reduced, which eventually hinders the rapid migration of CO2 plume through the rock matrix. On
the other hand, by adding nano-catalysts and ligands to the injected CO2 , this trend can be manipulated using
additional steric repulsion forces to achieve optimum sequestration conditions in the reservoir, which substantially
enhances mixing and storage capacity compared with other nano-injection methods. The variation of the diffusion
coefficient of a CO2 +brine system upon injection of NPs can be simply appraised using the diffusion model
proposed by Joensson et al. (1986) and further comprehensive evaluation incorporating the CO2 and brine layering
effect around the particles can be performed using a model suggested by Von Meerwall et al. (1990). According to
both these models, NPs tend to reduce the diffusion coefficient of a conventional CO 2 +brine mixture.

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One possible way to enhance CO2 sequestration in deep saline aquifers is to decrease the gravity-to-viscous force
ratio ( ) of the system which leads to increased sweep efficiency, resulting in more CO2 trapping as residual gas.
Residual/capillary trapping is enhanced and occurs relatively quickly when the gravitational forces are weaker than
to the viscous forces (low ) (Ide et al., 2007; Gershenzon et al., 2015). In low conditions, the injected CO2
migrates laterally due to the strong viscous forces and near the injection point (the lower region of the aquifer)
where the viscous forces are strong, almost all of the injected CO 2 tends to be immobilized via residual trapping
before it reaches the uppermost region of the aquifer. With time, CO 2 saturation declines and free CO 2 moves
upward due to gravity relaxation after which, there is a possibility that some layers near the caprock may not
contain trapped CO2 (Singh et al., 2019). Therefore, the CO2 which occupies those layers remains mobile. However,
compared to the high conditions, the amount of mobile CO 2 occupying upper layers is very small under low
conditions, which reveals the favorable nature of the low condition for residual trapping. The of a
deep saline sequestration system can be defined as:

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[1]

where, is the vertical effective permeability,

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is the aquifer length, is the density contrast, is the
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acceleration of gravity, is the aquifer height, is the total average Darcy velocity and is the viscosity of
the brine phase.
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Generally, defines the dominant force between gravity and viscous which controls the fluid movement in a
deep sequestration system, and if is large, gravity forces overrule the flow , inducing a thin gravity tongue at
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the top of the capillary zone (Singh et al., 2019). Based on the response of , it is reasonable to assume that
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viscous forces dominate nano-modified flow, since nano-modification diminishes the density contrast between the
nano-CO2 and brine phases. Therefore, in nano-CO2 injection, the evolved viscous forces appear to govern the
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upward flow of injected CO2 . The altered viscous and buoyant forces also modify the conformance control
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mechanics of the buoyancy-driven CO2 flow. In nano-injection, a more dense and viscous nano-CO2 than that in
conventional injection displaces reservoir brine , which is very stable and leads to less gravitationally-driven
viscous fingering, which is an additional benefit of being a multiphase instead of a single phase. A dimensionless
bond number, which defines the interaction between buoyant and capillary forces, can also be used to better
characterize the NP injection-induced gravity forces, capillary forces and buoyancy-driven flow occurring inside
the reservoir pore structure. Eq. (2) provides the general form of the bond number. Since the addition of NPs
reduces the density contrast between brine and nano-CO2 , it is expected that the reservoir will yield a capillary
force-dominant sequestration system, resulting in bond number reduction at the pore scale. Most importantly,
nano-injection has the potential to increase the interfacial tension between CO2 and brine and capillary entry
pressure for large pores. This will change the origin of capillary barriers in tight saline aquifers, enhancing the
long-term capillary trapping of injected CO 2 .

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⁄

[2]

where, is the density difference between brine and nano-CO2 , is the interfacial tension between the two fluids,
is the pore/grain diameter, and is the characteristic length scale.

4. Mechanisms of nano-CO2 plume development

The nano-CO2 plume development mechanisms can be better comprehended by the mechanisms of nanofluid flows,
which involve inertial effects, Brownian diffusion, thermophoresis, diffusiophoresis, the Magnus effect, fluid
drainage, and gravity effects. With respect to conventional injection, the mobility of nano-CO2 is much lower
because nano-CO2 exists as two phases or a foam. The influence of reservoir pore water lamellae on CO 2 migration
through pore constrictions is significant when CO 2 exists as a nano-CO2 (two-phase effect), which produces a

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channeling effect in the pore matrix by blocking off effective flow channels. The induced capillary forces dominant

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in the system over buoyancy forces result in mobility loss and the reduced mobility enables nano-CO2 to penetrate
more pore spaces already bypassed by the bulk fluid. This may reduce the horizontal movement of CO 2 by
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distributing CO2 in the vicinity of the injection point. Fig. 9 shows how nano-injection influences the CO2
saturation and pressure development of the reservoir and its impacts on mobility loss based on laboratory
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experimental data (Senthilnathan, 2017).
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The effects of nano-injection on CO2 migration in deep saline reservoirs can be appreciated by analytical and
numerical studies incorporating the fundamentals of classical nanofluid models and nanofluid convection-diffusion
mechanisms in porous media. Coupling these mechanics with multiphase flow equations will further yield the
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influence of nano-injection on CO2 plume development in deep saline aquifers. Fig. 9 shows the numerical results
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of the CO2 migration characteristics of a pilot-scale CO2 sequestration project in the Jilin oilfield with and without
nano-injection (Yang et al., 2014). As in Fig. 10, whatever the injection method, the initial distribution of CO 2
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portrays homogeneous migration patterns in the vicinity of the injection point. With time, the conventional CO 2
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migration front tends to move forward along a preferential flow path and reaches nearly 9km from the injection
well after 20 years. However, after 1 year, the spatial CO 2 distribution starts to drastically change with the
introduction of NPs, and the conventional belt-shaped distribution begins to change into a quasi-elliptical shape
with an average diameter of 4 km in the nano-injection scenario. This transition from belt-shape to quasi-elliptical
shape indicates that formation heterogeneity effects may not adversely affect CO2 plume development in the nano-
injection case, but strongly influence CO2 migration in conventional injection. Therefore, it is reasonable to suggest
that nano-injection reduces the influence of formation heterogeneity on CO 2 migration.

The other important concern is that NPs may change the velocity field of CO 2 movement in a deep saline
sequestration system. If this occurs, the momentum equilibrium of the whole system changes, since it changes the
gravitational term in the momentum equation. On the other hand, mass and energy transfer mechanisms will
change due to nano-injection-altered local temperature gradients and volume fractions. Moreover, with respect to
the conventional case, nano-injection-induced convection-diffusion undergoes severe modifications due to
Brownian motion and thermophoresis of injected NPs. The changes in the velocity field finally affect the
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interfacial tension gradient, which in turn influences both CO 2 and brine displacement characteristics. Generally,
the interfacial interaction between CO 2 and brine produces shear stresses at the interface between CO2 and brine
and the induced shear stresses have the ability to change the velocity field, because the velocity field is coupled
with the tangential flows at the interface through the relative velocity between the CO2 and brine phases. In nano-
injection, when NPs interact with the interface between CO2 and brine, there is a likelihood of increasing the
relative velocity between the CO 2 and brine phases, since shear stresses in the fluid boundary layer tend to decrease
with the injection of NPs. Even if boundary shear stresses decrease, there is a tendency to increase the interior
shear stresses in fluids with the introduction of NPs, which causes CO2 to migrate homogeneously, eliminating the
antagonistic effects of stratigraphic heterogeneity on the migration and accumulation of the CO2 plume.

5. Propagation and transport of nano-CO2 in porous media

5.1. Wettability alterations

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Complex non-linear responses in the propagation and transportation of injected NPs occur when the colloids
interact with the reservoir formation. The particle number density, the surface characteristics of NPs and mineral
grains, the pH and ionic strength of aquifer brine, injection rates, temperatures, miscibility and viscosity of injected
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CO2 and reservoir pore fluid, and the topology and pore network morphology of the porous media influence the
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behavior of NPs in porous media (Kang et al., 2019). In deep saline sequestration, the propagation and transport
properties of NPs are important because NP injection-induced pore-scale modifications significantly alter the
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fundamental controls of structural and stratigraphic and residual trapping potentials. Generally, residual trapping
contributes 10-90% permanent storage of the total injected volume of CO 2 (Krevor et al., 2012). Formation
wettability and pore-scale heterogeneity are likely to change upon the injection of NPs, consequently contributing
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to differences in residual CO 2 trapping. The residual trapping potential is limited if CO 2 -wet or CO2 -mixed-wet
condition results from NP injection, because the trapping potential is constrained by the formation’s wettability
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(Ali et al., 2019). Wettability plays an important role in deep saline sequestration because the fluid flow and
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distribution mechanism within porous media is governed by this phenomenon (Valle et al., 2018). Here, the
question is how reservoir wettability changes with the injection of NP-modified CO2 .
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To the best of our knowledge, such a study has not been reported to date for the nano-CO2 -brine system. However,
knowledge gained from petroleum industry-related research on NP injection-induced wettability alterations
provides a fundamental understanding to explore and develop this promising technique for enhanced CO2 storage
and sequestration in deep saline aquifers (Yu et al., 2010; Roustaei et al., 2015). One favorable property of NPs is
their ability to change reservoir rock wettability. The contact angle between brine, CO 2 and CO2 dissolved brine
droplets defines the wettability of nano-modified surfaces. Studies using silica NPs have found that the contact
angle of mineral surfaces tends to reduce upon nano-treatment (Bayat et al., 2014; Moghaddam et al., 2015). Table
5 provide evidence for the reported reduction in the contact angle of minerals after treatment with NPs.

Fig. 11 conceptualizes major mechanisms of NP-induced wettability alteration under brine-wet conditions. Two
possible mechanisms are highlighted: bridging and salting-out effects, which may occur due to the interaction of
divalent cations (Buckley et al., 1998). The first three interactions of injected NPs with brine and the rock matrix

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interfere with the wettability modification of the system and the later interactions enhance wettability alteration.
Positively-charged NPs are attracted to the negatively-charged water and CO2 molecules and negatively-charged
NPs are attracted to the positively-charged rock interface (Ali et al., 2019). Bridging between oppositely-charged
interfaces increases the tendency of NPs to bind to the rock interface, affecting the wettability of the system (Li et
al., 2019). The salting-out effect, which releases more ions into the system, changes the electrostatic
interactions between nano-CO2 and brine, keeping the injected NPs in the brine phase, and changing the wettability
to more water-wet conditions (Garing and Benson, 2019). In these two mechanisms, anionic molecules (the net
electrostatic charge of the ion is negative) have the least influence on wettability alteration, because of the
repulsive forces induced between the anionic part and CO 2 , and brine. In the case of cationic interaction,
wettability tends to water-wet due to the resulting electrostatic attraction and ion-pair formation between NPs and
the CO2 /brine/rock system. A digital image analysis algorithm can be adopted to obtain the contact angle, contact
radii, and center heights of the droplets on nano-modified surfaces (De Schryver et al., 2018). The use of nano-

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modified CO2 changes the CO2 -wet rocks strongly to the water-wet condition and water-wet reservoirs are believed
to be favorable for CO2 sequestration (Iglauer et al., 2015). Carbonate reservoirs, which are weakly water-wet
under high CO2 pressure conditions, become strongly water-wet with the introduction of NPs (Soames et al., 2019).
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This transition from strongly CO2 -wet to strongly water-wet improves the structural and residual trapping
capacities of deep saline sequestration systems.
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NP concentration and brine salinity play important roles in influencing the wettability behavior of nano-modified
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CO2 +brine systems. The contact angle reduces with increasing NP concentration (typically >2wt%), and both
water advancing and receding contact angles for CO2 /brine/rock clearly decrease with increasing NP concentration
(Al-Anssari et al., 2016). A higher NP concentration may reduce the reservoir’s effective permeability and the
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stability of nanosuspension (Metin et al., 2011). The salinity of a reservoir varies significantly with depth, even
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reaching levels as high as 30 wt% brine (Krevor et al., 2016). Such high salinity conditions affect the stability of
nano-modified CO2 . Studies of the effect of salinity on wettability for both brine and CO2 /brine systems have
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revealed that both advancing and receding contact angles decrease with increasing salinity for brine systems and
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increase with salinity for CO2 /brine systems (Ahualli et al., 2011). However, at constant temperature and pressure,
a more significant effect of salinity can be expected in CO 2-brine systems than pure brine systems. This is related
to the injected CO2 dissolution-induced acidic condition and its influence on mineral reactivation under reservoir
conditions (Saaltink et al., 2013). The other important finding is that despite the saturation condition of the
reservoir, nano-treatment-induced advancing and receding contact angles both tend to increase with increasing CO2
injection pressure (Arif et al., 2016). The zeta potential of reservoir rock changes with increasing CO 2 pressure (Ali
et al., 2019) and subsequently, under constant temperature, salinity and NP concentration, complex electrostatic
interactions between injected CO 2 , reservoir rock matrix and NPs occur altering the stability, adsorption and aging
processes of NPs which ultimately increase the contact angle and decrease the rock wettability. However, the
quantitative dependence of deep saline reservoir pressure on nano-CO2 behavior has not been well investigated. It
has also been found that the addition of surfactant (such as sodium dodecylsulfate (SDS), Sigma Aldrich) to nano-
CO2 increases the wettability characteristics of the system, due to the interaction of nano-CO2 -brine and the rock
surface with hydrophilic side chains in the added surfactant (Kundu et al., 2013). Fig. 12 shows the impact of NP
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concentration, salinity and injection pressure on advancing and receding contact angles of CO2 /brine systems.
Overall, the addition of NPs to the CO 2 demonstrates the significant potential of wettability modification under
reservoir conditions, which leads to enhanced storage and retention.

5.2. Nano-modified CO2 /brine interfacial tension (IFT)

Despite enhancing the wettability characteristics of nano-CO2 injection, it shows positive responses in modifying
IFT, which is one of the prime parameters in estimating CO 2 storage capacity and its containment security (Jha et
al., 2018). Structural and residual trapping of CO2 are greatly dependent on capillary pressure, which is a function
of IFT. NPs increase the ion composition of the aqueous, occurring complex rock+brine, rock+CO2 and
CO2 +brine+rock interactions due to altered solubility and interfacial activities. It is expected that NPs become
electrically charged due to the forces (shear) which normally exist in CO 2 /brine systems and consequently, result in
the agglomeration of particles (Al-Anssari et al., 2018). This agglomeration of particles alters the IFT

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characteristics of a CO2 /brine/rock system, significantly changing the capillary forces acting in the pores and

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throats.

The estimation of IFT in nano-CO2 -brine systems is a complex process, as it involves multicomponent phases and
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relies on a wide range of variables, including temperature, pressure, salinity, concentration, type of heteroatoms
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present, acid number, base number, pH of the aqueous phase, viscosity, amount of dissolved gases, and the
presence of fine solids (Sztukowski and Yarranton, 2004). The addition of NPs to the CO2 injection stream
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significantly reduces IFT under low salinity conditions (Hassanpour et al., 2018). Upon the injection of NPs,
general IFT values in a high salinity CO2 /brine system tend to reduce from 30-50 mN/m to 22mN/m under high
pressure and temperature conditions (Bachu and Bennion, 2009; Al-Anssari et al., 2018). However, in high saline
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reservoirs, ion segregation at CO 2 -brine interfaces possibly occurs due to NP injection (Levin et al., 2009) and this
occurrence may increase the CO2 /brine IFT by eliminating the influence of NPs and giving reasonable IFT values
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for CO2 sequestration even in the presence of hydrophilic NPs (Chalbaud et al., 2009). Some research findings
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reveal that the hydrophilicity of NPs is the most critical factor which governs IFT under high reservoir temperature
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and pressure conditions (Hendraningrat and Torsaeter, 2014). Considering the behavior of a conventional
CO2 /brine system, it is reasonable to assume that nano-modified system IFT increases with increasing reservoir
temperature and decreases with increasing reservoir pressure (Al-Anssari et al., 2018). Increased reservoir
temperature weakens the anisotropic time-averaged van der Waals attraction between the water molecules and the
CO2 interface, and this leads to increased IFT. On the other hand, increased pressure empowers this attraction,
which also results in IFT reduction (Espinoza et al., 2011). Furthermore, CO2 /brine IFT tends to decrease with
increasing NP concentration, and increasing the NP concentration from 0 to 0.05 wt% results in a 10% IFT
reduction at ambient temperature and 12% at 20MPa pressure and 70°C temperature (Al-Anssari et al., 2018). This
decreasing behavior of IFT at constant pressure and temperature resembles the adsorption capacity of NPs at the
CO2 /brine interface, because once the system reaches its interfacial adsorption capacity, there is no further
reduction in IFT with increasing NP concentration, and that concentration is believed to be the threshold
concentration above which IFT is a constant (Metin et al., 2012).

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During nano-CO2 injection, the ion concentration and chemistry of the aquifer vary widely, influencing the IFT of
the system (Sivasankar and Kumar, 2018). In the case of ion leaching from the nano-modified CO2 phase, the
released free nano-ions interfere with the affinity of the interface by tightly interacting with the brine phase of the
reservoir. The interaction of nano-ions with the brine phase leads to the attraction of more water molecules into the
bulk of the brine phase, making a significant gradient in ionic strength around the interface of CO2 /brine (Bachu
and Bennion et al., 2009). This ion interaction in the interface invades IFT and dominates the influence of salinity
on IFT. The complex mechanisms of the bridging and salting-out processes also enhance this attack of water
molecules on the CO2 and brine interfaces, which leads to increased energy being required for expanding the
interfacial area (Al-Anssari et al., 2018). As a result, IFT increases and this increasing trend is expected to be more
significant at both higher ion concentrations and ion charges. IFT tends to increase with increasing free divalent
ions in the system, and free monovalent ions have an insignificant influence on nano/CO 2 /brine IFT (Johansson
and Eriksson, 1974). However, these processes can be dictated by the polarization properties of nano-ions under

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deep saline reservoir conditions (Koleini et al., 2019).

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6. Solubility of NPs in aqueous environment

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The solubility characteristics of potential nano-materials under aqueous conditions are crucial in the context of
assessing the possible consequences of permanent sequestration of nano+CO2 in underground deep saline aquifers.
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In addition, the rate of solubility of NPs under aqueous conditions governs the density contrast, which in turn
controls the onset times of instability and convective mixing (Hassanzadeh et al., 2007). The injected NPs can
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contaminate the neighboring freshwater aquifers and rock formations via solute transport, in which dissolved NPs
may spread with the aquifer pore fluid due to groundwater flow, diffusion and dispersion. Fig. 13 shows the
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development of a nano+CO2 plume in conventional injection, highlighting possible ageing processes of NPs in
deep saline aquifer environments. The main question here is how these processes alter the chemical composition of
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the aqueous phase and the equilibrium reactions of the CO2 +brine-saturated region. Given the complexity of deep
saline aquifers, it is realistic to consider two types of pore fluid regimes based on the total ionic composition of an
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aquifer, neglecting the pure CO2 -saturated region next to the injection point (Rathnaweera et al., 2015a). One, the
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pure brine pore fluid condition, contains a significantly higher total electrolyte concentration, being especially rich
in sodium, calcium and chlorite ions (Region 1 in Fig. 13). The other, the CO2 +brine pore fluid condition, has
lower pH and total carbonates (Region 2 in Fig. 13). In these two regimes, the solubility of NPs in pore fluid can
either increase or decrease, depending on the geochemistry involved in the interaction of injected NPs, CO2 ,
aquifer brine and reservoir rock. Interfacial interactions (interfacial tension, wettability, capillarity and interfacial
mass transfer), aquifer pH, redox potential, salinity, temperature, and injection pressure significantly overrule
nano+CO2 +brine solubility, distribution and behavior in porous sedimentary media (Rathnaweera et al., 2018).

For instance, even barite, one of the potential NPs for sequestration, shows extremely low solubility characteristics
in water (0.0002448g/100ml at 20°C and 0.000285g/100ml at 30°C) and aqueous alkaline (Tokunaga et al., 2018),
and one of the potential critical concerns with nano-barite disposal in deep saline aquifers is that the injected nano-
particles may dissolve and re-crystalize/precipitate in the reservoir environment. This is important, because
injected nano-barite can increase the likelihood of scaling, and therefore, a thorough understanding of the

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dissolution and precipitation kinetics of barite is required for the prediction of where and how fast scaling is likely
to occur (Popov et al., 2019). The dissolution of nano-barite is possible in deep saline environments due to the
enhanced effective reactive surface area (dissolution kinetics are more active at nano-scale than meso-scale), which
is an advantage for the permeant sequestration of injected CO2 during solubility trapping. According to Fig. 14, the
prevailing pH, saturation state, ionic strength, competitive ions, temperature and pressure considerably influence
the solubility kinetics of barite (Christy and Putnis, 1993; Zhen-Wu et al., 2016; Ouyang et al., 2019). The barite
dissolution rate increases as a linear function of ionic strength, suggesting that when the injected NPs interact with
the brine-saturated region, there may be significant alterations in the chemical equilibrium of the system. However,
pH-dependent behavior appears to be more complex, and the initial increase of solubility tends to occur up to a
neutral point (pH=7), readily achieving equilibrium in the alkaline range. The dissolution rate shows temperature-
dependent behavior, as with increasing temperature, the dissolution rate increases from 25 to 60ºC and decreases
from 60 to 90ºC (Zhen-Wu et al., 2016). Re-crystallization occurs when the system is already saturated (saturation

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index > 0) with dissolved and ions, and super-saturation is triggered when the injected CO2 starts to

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dissolve existing naturally-occurring barite minerals in the reservoir rock (Rathnaweera et al. 2015b). This barite
precipitation in the reservoir can cause both wellbore and pore clogging (scaling effects), which prevent fluid and
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CO2 flow, and hinder other trapping mechanisms such as structural and stratigraphic and residual trapping
(Hajirezaie et al., 2019). Table 6 summarizes the solubility behaviors of other potential NPs for deep saline
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sequestration.
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The interaction between NPs, CO2 and reservoir rock causes the reservoir’s natural properties to change, altering
the hydro-mechanical and geochemical equilibria between the reservoir rock and the formation pore fluid. This
interaction can occur through ageing processes, such as chemical transformation, dissolution, chemical speciation,
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adsorption, degradation, precipitation, aggregation and sedimentation (Bundschuh et al., 2018). The chemic al
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composition and chemical equilibrium of the aqueous phase can be significantly changed upon the injection of NPs
and such changes interfere with the development and migration characteristics of the CO2 plume under reservoir
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conditions. There is a possibility that injected NPs migrate into the caprock, reacting with caprock minerals and
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propping existing micro-fractures in the caprock mass. This would be a serious risk factor for leakage of injected
CO2 into the atmosphere. However, practical limitations, mainly the lack of knowledge of how NPs dissolve in the
aqueous environment and their interaction with both CO 2 and reservoir rock including thermodynamics and
kinetics, hamper the dissemination and transformation of this novel knowledge into practical application.

7. Conclusions
In attempting to reduce the climate-change threat posed by anthropogenic global warming, this perspective study
addresses one of humanity’s most complex and pressing challenges. The aim of this study is to generate new
knowledge in the area of CO 2 sequestration and to improve one of the best options, already adopted by many
countries: deep saline CO 2 sequestration, by exploring a promising technique for enhancing CO 2 storage and
sequestration in deep saline aquifers, by adding NPs to the injected CO 2 . The expected outcomes of this new
method are enhanced and safe CO2 storage. From the economic point of view, the extensive time required for
mixing CO2 in brine is a persistent issue for sequestration in saline aquifers. The adoption of nano-CO2 injection in

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deep saline aquifers will enhance CO 2 storage and sequestration by reducing the onset time of mixing and
enhancing convective mixing. It will also prevent the back-migration of injected CO 2 into the atmosphere and
minimize the associated risk of leakage to nearby freshwater aquifers.

With respect to conventional injection, viscous forces tend to dominate nano-modified flow by eliminating the
influence of gravity forces, which leads to less gravitational-driven viscous fingering. Nano-injection increases the
interfacial tension between CO2 and brine and capillary entry pressure for large pores, enhancing the long-term
capillary trapping of injected CO 2 . The transition from belt-shape (conventional injection) to quasi-elliptical shape
reveals that nano-injection reduces the effect of formation heterogeneity on CO 2 migration. The volatile behavior
of conventional CO2 +brine systems due to lack of sufficient permeant dipole moments and weak van der Waals
forces of captured CO2 can be effectively eliminated by the addition of NPs, which enhances the stabilization of the
CO2 plume and improves CO2 flooding. The other important finding is that nano-injection appears to alter the
velocity field of CO2 movement due to the Brownian motion and thermophoresis of injected NPs. Moreover, the

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contact angle reduces with the addition of NPs into the CO2 +brine+rock system, changing the wettability to more
brine-wet, which is believed to be more favorable for CO2 sequestration. However, to date no available study has

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systematically and quantitatively combined reservoir salinity, temperature, pressure and NP concentration for
nano-CO2 sequestration in deep saline aquifers and it is therefore not possible to reliably demonstrate these effects
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on rock contact angle and wettability.

Importantly, the proposed method provides significant benefits to different stakeholders with shared interests in
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deep saline aquifers, including reductions in current operational and monitoring costs compared with conventional
injection. Therefore, industrial-scale geosequestration projects will benefit in direct economic and environmental
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terms, and have enhanced stature in the global research community for their leadership in a critically important
domain. In addition, many materials currently enter the waste stream because of inefficient recycling. This new
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method offers one of the best solutions, because waste materials can be utilized as nano-modifiers. In conclusion,
the proposed technique promises to make a substantial contribution to limiting our greenhouse gas emissions, and
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to the world’s standing in this critically important field of research.

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Figure Captions
Figure. 1. (a) The Great Barrier Reef, under threat from rising sea temperatures; (b) bushfires have tripled in
Australia; (c) Queensland endured devastating floods in 2010 and 2016; (d) Victoria’s depleted Hume Dam (Baker
et al., 2008).

Figure. 2. (a) NaCl deposits due to drying-out effects of injected CO 2 ; (b) clay mineral dissolution textures; (c)
dissolution of quartz and barite minerals; (d) corrosion of calcite and quartz minerals (Rathnaweera et al., 2015a;
Rathnaweera et al., 2016b).

Figure 3. Short- and long-term mixing mechanisms involved in deep saline aquifers.

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Figure. 4. Effect of different NP materials on (a) wavelength of fingers ( ) induced by Rayleigh instability
analysis and (b) onset time of convective mixing ( ) of Alberta Basin, Canada, and Gorgon Basin, Australia.

Figure 5. Potential nano-materials and their ageing and dispersion mechanisms under deep saline sequestration
conditions.

Figure 6. Possible major adsorption and shielding mechanisms of nano-CO2 +brine with addition of
polymers/surfactants.

Figure 7. Possible scenarios for dispersion, flocculation and stabilization of NPs and surfactants in CO 2
sequestration system.

Figure 8. Calculated density values for conventional and nano-injection scenarios using reservoir pore fluid
obtained from Tianjin reservoir, China at reservoir temperature of 50°C, (a) 0.01 volume fraction of NPs and (b)
0.04 volume fraction of NPs.

Figure 9. Comparison of nano-injection-induced CO2 saturation, pressure drop, and mobility loss compared to
conventional injection. CO 2 saturation profiles evidence that with respect to conventiona l injection, nano-injection

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has the potential to sequestrate more CO 2 , which in turn enhances the residual trapping ratio. The pressure

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development results reveal that mobility reduction occurs upon injection of NPs (modified after Senthilnathan,
2017).

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Figure 10. Results of CO2 migration characteristics of pilot-scale CO2 sequestration project at Jilin oilfield with
and without nano-injection (modified after Yang et al., 2014).
e-
Figure 11. Possible major mechanisms of NP-induced wettability alteration to brine-wet conditions.

Figure 12. Variation of water advancing and receding contact angle as a function of (a) NP concentration in base
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fluid of CO2 +5% NaCl brine, and (b) salinity in base fluid of CO 2 +brine under reaction pressure and temperature
of 15MPa and 70°C (modified after Al-Anssari et al., 2018).

Figure 13. Development of nano+CO2 plume in proposed nano-injection and its interfacial stability and instability
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involving possible ageing processes.

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Figure 14. Dissolution characteristics of nano-barite and their variation with respect to aquifer (a) pH (He et al.,
1994; Zhen-Wu et al., 2016), (b) salinity (Ouyang et al., 2019), and (c) temperature (Zhen-Wu et al., 2016).
u

Table captions
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Table 1. Amount of CO2 emitted from main anthropogenic sources in 2011 (IEA, 2016; Rathnaweera et al., 2017).

Table 2. Storage capacity of three major geological storage options (IPCC, 2016).

Table 3. Reservoir properties incorporated in theoretical estimations of critical time of mixing and wavelength of
mixing fingers (Michael et al., 2010; Javadpour and Nicot, 2011).

Table 4. Estimated critical wavelength and critical onset times for thirty saline aquifers in USA, Japan, Germany,
Norway, Algeria, and North Sea.

Table 5. Contact angle reduction of rocks/minerals after introduction of NPs (Bayat et al., 2014; Moghaddam et al.,
2015; Al-Anssari et al., 2016).

Table 6. Solubility characteristics of other potential NPs for deep saline sequestration (Foster et al., 2019; Thieme
et al., 2019; Ito et al., 2019; Rostami et al., 2019).

Table 1. Amount of CO2 emitted from main anthropogenic sources in 2011 (IEA, 2016; Rathnaweera et al., 2017).

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Anthropogenic sources of CO2 % of CO2 Remarks
emission
1) Fossil fuel use 87% Coal is responsible for 43% of carbon dioxide emissions from fuel
combustion, 36% is produced by oil and 20% from natural gas.
Electricity and heat generation sector 41%
Industrial sector 20%
Transportation sector 22%
Road transport 72%
Marine shipping 14%
Global aviation 11% International flights create about 62% of these emissions with
domestic flights representing the remaining 38%.
2) Land use changes 9% Contributed 3.3 billion tonnes of carbon dioxide emissions in 2011
3) Industrial processes 4%
Cement production Making 1000 kg of cement produces nearly 900 kg of carbon
dioxide
Steel production 1.9 tonnes of CO2 are emitted for every tonne of steel produced

Table 2. Storage capacity of three major geological storage options (IPCC, 2016).

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Storage capacity (GtCO2 )
Reservoir type
Lower estimation Upper estimation
Depleted oil and gas 675 900
Un-mineable coal beds
Deep saline aquifers
3-15
1000
pr 200
10,000
e-
Pr
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Table 3. Reservoir properties incorporated in theoretical estimations of critical time of mixing and wavelength of
mixing fingers (Michael et al., 2010; Javadpour and Nicot, 2011).
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Effective CO2 +brine Brine

Thickness Temperature Pressure Depth
Project permeability Porosity density* viscosity
(m) (°C) (MPa) (m)
(mD) (kg/m3 ) (mPa.s)
u

Alberta Basin, Canada 200 0.15 179 65 16.5 1882 1054.15 0.65
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Appalalachian Basin, 0.045 0.03 90 71 26.5 2170 1075.21 0.77

USA
Arbuckle Group, USA 220 0.2 817 123 34.8 3658 1091.72 0.36
Cedar Keys, USA 220 0.2 373 45 10.6 1073 1066.38 0.85
Cincinnati Arch, USA 105 0.12 100 47 9.72 1000 1072.46 0.61
Decatur, USA 225 0.15 300 64 26.5 1980 1080.37 0.71
Dupuy Fm, USA 25 0.2 100 100 22 2300 1094.11 0.44
Early, USA 560 0.2 150 110 12.1 3140 1081.27 0.57
Fox Hills, USA 220 0.2 255 35.6 7.8 779 1092.30 0.97
Frio, USA 1500 0.3 1058 43 10.1 1021 1083.21 0.87
Gorgon, Australia 25 0.2 250 100 15 2300 1093.21 0.75
Granite Wash, USA 220 0.2 849 69.6 18.3 1900 1087.26 0.62
Haizume Fm, Japan 6 0.2 60 46 11.9 1100 1091.72 0.83
In Salah, Algeria 5 0.17 29 90 17.9 1850 1085.46 0.88
Ketzin, Germany 750 0.23 80 34 7.3 650 1077.41 0.58
Madison Group, USA 6.45 0.2 267 59 14.9 1539 1079.91 0.7
Martin Fm, USA 220 0.15 200 45 10.6 1081 1084.77 0.85
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Michigan Basin, USA 22 0.13 92 47 10.17 1061 1080.73 0.68
Mississippi, USA 1180 0.21 214 110 15.3 2595 1073.27 0.63
Morrison Fm, USA 220 0.2 242 77 20.5 2139 1090.17 0.57
Mt. Simon Fm, USA 225 0.15 160 66 17.5 1841 1090.84 0.65
Nagaoka, Japan 6 0.17 60 46 11.9 1100 1092.4 0.72
Oriskany Fm, USA 220 0.2 11 51 13 1314 1093.65 0.78
Paluxy Group, USA 220 0.2 90 41 10.4 1051 1072.56 0.83
Potomac Group, USA 594 0.2 305 34.9 7.7 753 1092.29 0.98
Repetto Fm, USA 220 0.2 831 92.1 25.3 2642 1090.73 0.48
Sleipner, Norway 5000 0.37 250 48 10.3 1000 1085.46 0.74
Snohvit, Norway 450 0.13 60 60 28.5 2550 1088.34 0.82
Stuttgart Fm., Germany 750 0.23 80 34 1.3 650 1091.81 1
Tuscaloosa Group, USA 220 0.23 45 43.8 10.9 1048 1094.40 0.86
Utsira Fm, North Sea 5000 0.31 250 31 10.3 1000 1094.58 0.95
Woodbine Fm, USA 220 0.22 105 41 10.1 1023 1084.93 0.83

f
(* CO2 +brine density can be calculated using where,

oo
is the mass fraction of dissolved CO 2 in brine)

pr
e-
Pr

Table 4. Estimated critical wavelength and critical onset times for thirty saline aquifers in USA, Japan, Germany,
Norway, Algeria, and North Sea.
al

(m) (Years)
Project
rn

CO2 CO2 - CO2 - CO2 - CO2 - CO2 - CO2 CO2 - CO2 - CO2 - CO2 - CO2 -
barite U3 O 8 steel UO2 lead barite U3 O8 steel UO2 lead
Appalalachian Basin, 7.1 6.52 4.92 4.32 3.87 3.43 41.3 23.3 17.4 15.2 9.4 9.0
USA
u

Arbuckle Group, USA 2.08 1.5 1.16 1.14 0.95 0.92 2.2 1.2 0.7 0.6 0.4 0.4
Jo

Cedar Keys, USA 1.87 1.4 1.09 1.05 0.85 0.86 4.6 2.5 1.5 1.4 1.0 0.9
Cincinnati arch, USA 1.1 0.73 0.54 0.35 0.31 0.28 3.9 3.1 2.8 2.3 1.8 1.8
Decatur, USA 1.42 1.06 0.74 0.62 0.53 0.46 4.0 2.1 1.6 1.6 1.2 1.0
Dupuy Fm, USA 5.31 3.71 2.91 2.73 1.85 1.74 24.4 14.4 10.4 1.0 0.7 0.6
Early, USA 1.82 1.07 0.82 0.75 0.68 0.64 5.3 2.6 2.1 2.1 2.0 2.0
Fox Hills, USA 1.82 1.3 1.05 1.03 0.83 0.83 5.0 2.7 1.7 1.6 1.1 1.1
Frio, USA 0.42 0.3 0.21 0.23 0.18 0.18 0.1 0.1 0.0 0.1 0.0 0.1
Granite Wash, USA 2.03 1.5 1.18 1.15 0.94 0.93 3.7 2.0 1.2 1.1 0.8 0.8
Haizume Fm, Japan 4.98 3.52 2.86 2.04 1.86 1.81 38.6 18.6 13.3 11.7 10.4 9.5
In Salah, Algeria 7.72 4.35 4.02 3.96 3.76 3.27 46.4 25.4 16.4 14.2 13.8 13.2
Ketzin, Germany 0.94 0.42 0.36 0.31 0.28 0.26 3.3 1.6 1.2 1.1 1.0 0.9
M adison Group, USA 6.73 5 3.94 3.8 3.17 3.1 46.0 25.1 15.7 14.8 10.2 9.6
M artin Fm, USA 0.4 0.3 0.27 0.27 0.21 0.22 1.0 0.6 0.4 0.4 0.3 0.3
M ichigan Basin, USA 3.25 2.04 1.85 1.74 1.71 1.68 18.5 9.4 6.4 4.9 4.3 4.2
M ississippi, USA 1.4 0.62 0.57 0.51 0.47 0.44 1.5 0.6 0.5 0.3 0.2 0.2
M orrison Fm, USA 2.1 1.5 1.16 1.17 0.97 0.95 3.4 1.8 1.1 1.1 0.8 0.7

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M t. Simon Fm, USA 1.51 1.1 0.84 0.82 0.7 0.68 2.7 1.5 0.9 0.8 0.6 0.6
Nagaoka, Japan 6.43 4.01 3.95 3.82 3.77 3.62 40.2 21.5 17.4 16.4 13.3 12.9
Oriskany Fm, USA 1.9 1.4 1.17 1.12 0.93 0.9 4.4 2.4 1.5 1.4 1.0 0.9
Paluxy Group, USA 1.88 1.4 1.12 1.1 0.9 0.88 4.5 2.5 1.6 1.5 1.0 1.0
Potomac Group, USA 0.7 0.5 0.4 0.4 0.32 0.33 0.7 0.5 0.3 0.3 0.2 0.2
Repetto Fm, USA 2.1 1.6 1.22 1.18 0.98 0.98 3.0 1.6 1.0 0.9 0.6 0.6
Sleipner, Norway 0.52 0.31 0.3 0.28 0.26 0.26 0.5 0.2 0.1 0.1 0.1 0.1
Snohvit, Norway 1.32 0.63 0.56 0.51 0.43 0.42 2.2 1.2 0.9 0.8 0.8 0.7
Stuttgart Fm., Germany 0.6 0.4 0.37 0.39 0.32 0.32 0.6 0.3 0.2 0.2 0.2 0.2
Tuscaloosa Group, USA 2.2 1.6 1.28 1.23 1.04 1.01 5.4 3.0 1.8 1.7 1.2 1.2
Utsira Fm, North Sea 0.1 0.07 0.13 0.1 0.13 0.1 0.2 0.2 0.2 0.2 0.1 0.1
Woodbine Fm, USA 2.1 0.3 1.26 1.21 1.01 1.01 5.1 2.8 1.8 1.6 1.2 1.1

Table 5. Contact angle reduction of rocks/minerals after introduction of NPs (Bayat et al., 2014; Moghaddam et al.,
2015; Al-Anssari et al., 2016).

f
oo
Volume fraction of NP Base fluid Rock/mineral Condition Measurement Contact angle
(SiO2 ) wt% system reduction
0.01-0.2 0-0.2 wt% brine Calcite 70°C, 20MPa CO2 93°
0-0.5
0.01-0.1
0.1-0.6
0-0.2 wt% brine+ surfactant
3 wt% brine
5 wt% brine
Calcite
Sandstone
Carbonate
pr 70°C, 20MPa
Ambient
Ambient
CO2 +brine
Crude oil
Crude oil
80°
32°
115°
e-
0.005 DI water Limestone 60°C, 0.1MPa Crude oil 72°
0.01-4 0-0.2 wt% brine Calcite Ambient Decane 110°
Pr

Table 6. Solubility characteristics of other potential NPs for deep saline sequestration (Foster et al., 2019; Thieme
et al., 2019; Ito et al., 2019; Rostami et al., 2019).
al

NPs Solubility Solubility in CO2 +brine Toxicity

in water
Uranium di- Insoluble Solubility increases upon interaction with a CO 2+brine system. For instance, Non-toxic,
rn

oxide (UO 2) solubility of 3.5±1.5×10-5 mkg-1 occurs in a system of pH=6.7 at 20°C. Solubility radioactive
can increase up to a maximum of about 2×10-4 mkg-1 with increase of temperature
from 25 to 270°C.
u

Triuranium Insoluble Insoluble, but can slowly dissolve in concentrated mineral acids to form a mixture Non-toxic,
octaoxide of uranium salts. radioactive
(U 3O8)
Jo

Uranium Very Highly reactive, vigorously attacks organic compounds in the reservoir. The Highly
hexafluoride hygroscopic reaction between UF6 and reservoir silica forms silicon tetrafluoride and uranium chemically toxic,
(UF 6) and soluble oxyfluoride. The reaction between UF 6 and carbonic acid can produce corrosive unstable
hydrogen fluoride (HF) and a uranium-fluoride compound, called uranyl fluoride
(UO 2F2).
Uranium Strongly Highly reactive under deep saline reservoir conditions. Highly
tetrachloride hydrolyse UCl4 + aH 2O → [U(H 2O)a ] + 4Cl
4+ − chemically toxic,
(UCl4) unstable
The resulting uranium aqua ions [U(H 2O)a ]4+ easily react with reservoir free
anions which alters chemical equilibrium of the system.
Uranium Very Hardly reacts with CO 2+brine system, but reaction between reservoir minerals is Toxic,
tetrafluoride slightly activated at temperatures above 50°C. moderately
(UF 4) soluble radioactive,
unstable
Lead oxide Very Amphoteric nature of PbO initiates the basic reaction between PbO and Non-toxic
(PbO) slightly CO 2+brine (carbonic acid) resulting in free Pb2+ via the intermediacy of oxo
soluble clusters such as [Pb6O(OH)6]4+ . Once carbonate minerals start to dissolve, PbO
reacts with free OH - in the system and forms plumbite salts [Pb(OH) 3]-.
Iron oxide Insoluble Chemical weathering occurs when Iron oxide interacts with CO 2+brine system Non-toxic
(Fe2O3) which results in free Fe3+ and Fe2+ ions. The altered chemical equilibrium of free
Fe2+ ions tends to change kinetics of siderite and illite precipitation and
dissolution mechanisms in reservoir rock.
Silica (SiO 2) Strongly Highly reactive under deep saline reservoir conditions. Non-toxic

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depends on SiO 2+2H → Si +2OH -
+ 4+
its
The precipitation and dissolution kinetics of kaolinite and feldspar change due to
crystalline
activation of Silica reaction.
form and
temperature.
Copper oxide Insoluble Dissolves slowly under deep saline reservoir conditions. Non-toxic
(CuO)

f
oo
pr
e-
Pr
al

Figure. 1. (a) The Great Barrier Reef, under threat from rising sea temperatures; (b) bushfires have tripled in
Australia; (c) Queensland endured devastating floods in 2010 and 2016; (d) Victoria’s depleted Hume Dam (Baker
rn

et al., 2008).
u
Jo

Figure. 2. (a) NaCl deposits due to drying-out effects of injected CO 2 ; (b) clay mineral dissolution textures; (c)
dissolution of quartz and barite minerals; (d) corrosion of calcite and quartz minerals (Rathnaweera et al., 2015a;
Rathnaweera et al., 2016b).

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f
oo
Figure 3. Short- and long-term mixing mechanisms involved in deep saline aquifers.

(a)

8
pr 10
(b)
e-
6
tc (Years)
𝛌c (m)

4 5
Pr

2
0 0
al
rn

Alberta basin, Canada Alberta basin, Canada

Gorgon basin, Australia Gorgon basin, Australia
u
Jo

Figure. 4. Effect of different NP materials on (a) wavelength of fingers ( ) induced by Rayleigh instability
analysis and (b) onset time of convective mixing ( ) of Alberta Basin, Canada, and Gorgon Basin, Australia.

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(3) Ostwald ripening (4) Flocculation
(1) Reduction in size of CO2
bubbles Weak bonding
Micro-gel nano-spheres
(2) Aggregation

Diffusion at two CO2 molecules

(5) Segregation (6) Coalescence

Absorbed layer
Nanocrystals

Nickel Oxide
Copper Oxide
Fly ash
Aluminium Oxide
SiO2 Silica NPs
MgO Nanoclays
CaO Nanocatalysts NPs Nanoemulsions Fly ash
BaO Iron Oxide
Ni/Al2O3-MgO
Ni-Co/Al2O3-MgO

f
oo
(7) Hydrodynamic effect
Nanofluids
(8) Bubble covering effect
Reduced boundary layer

Semi-metal Oxides pr
Metal Oxides Non-metal
e-
Lead Oxide
Iron Oxide
Silica NPs Barite Walnut shell
Al2O3 Coconut shell
Pr

UO2
CO2 Brine NPs U3O8

Figure 5. Potential nano-materials and their ageing and dispersion mechanisms under deep saline sequestration
al

conditions.
u rn
Jo

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= Brine phase
= CO2 phase
+ = Nano particles

= Polymer matrix

Nano-CO2+brine Polymer matrix

+ - = Electrostatic charges
Aqueous ionic
strength-enhanced
catalytic activation

f
oo
++
+
- +
-
+
+
+
-
-
- -
- +
-
+
+ pr
e-
+ +
+ +
Pr
al

Adsorption of
Shielding by cations
rn

polymer
u

Figure 6. Possible major adsorption and shielding mechanisms of nano-CO2 +brine with addition of
Jo

polymers/surfactants.

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Sulfanole-alkyl aryl sodium Anionic

sulfonate DMF, dimethyl acetamide,
[amidoamine oxide surfactant in dimethyl pyrrolidone
CaCl2, CaBr2 in brine solution]

Cationic Possible surfactants Organic

Diethylenetriamine-penta
[Methylene phosphonic acid]
Sodium dodecyl sulfonate [SDS] Nonionic/ As-40, C14-16, alpha-olefin
zwitterionic sulfonate

f
oo
Dispersion NPs Stabilization

pr CO2+NP
e-
CO2+NP Flocculation
Pr

CO2+brine+NP
al
rn

CO2+brine+NP CO2+NP
u
Jo

Figure 7. Possible scenarios for dispersion, flocculation and stabilization of NPs and surfactants in CO 2
sequestration system.

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CO2+brine
(a)
Nano-barite modified CO2+brine
Nano-U3O8 modified CO2+brine
Nano-steel modified CO2+brine
Nano-UO2 modified CO2+brine
1.12 Nano-lead modified CO2+brine
1.1
Density (g.cm-3)
(b) CO2+brine
Nano-barite modified CO2+brine
Nano-U3O8 modified CO2+brine
Nano-steel modified CO2+brine
Nano-UO2 modified CO2+brine
1.46 Nano-lead modified CO2+brine
1.38

Density (g.cm-3)
1.08 1.3
1.06
1.22
1.04
1.02 1.14
1 1.06
0.98 0.98
10 12 14 16 18 10 12 14 16 18
Reservoir pressure (M Pa) Reservoir pressure (M Pa)

Figure 8. Calculated density values for conventional and nano-injection scenarios using reservoir pore fluid
obtained from Tianjin reservoir, China at reservoir temperature of 50°C, (a) 0.01 volume fraction of NPs and (b)
0.04 volume fraction of NPs.

f
oo
pr
e-
Pr
al
u rn
Jo

Figure 9. Comparison of nano-injection-induced CO2 saturation, pressure drop, and mobility loss compared to
conventional injection. CO 2 saturation profiles evidence that with respect to conventional injection, nano-injection
has the potential to sequestrate more CO 2 , which in turn enhances the residual trapping ratio. The pressure
development results reveal that mobility reduction occurs upon injection of NPs (modified after Senthilnathan,
2017).

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(a) Conventional injection

W
9km

A clear predominant flow

path from West to East

(b) Nano-injection

f
oo
4km

pr
e-
Unclear flow path-primarily
around the injection point
Pr

Figure 10. Results of CO2 migration characteristics of pilot-scale CO2 sequestration project at Jilin oilfield with
and without nano-injection (modified after Yang et al., 2014).
al
u rn
Jo

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Under CO2 surface condition
Carbonate reservoirs (+) - - - - -

Reservoir formation
Silicate reservoirs (-)

- -
Na+ Na+

- Brine -
CO2 Rock
- Na+ Na+
-

Salting out effect Bridging effect

- CO2+hydrophilic NPs Surface charges

f
Attractive force

oo
Wettability alteration

(a) Conventional injection pr (b) Nano- injection

e-
Pr

CO2 wet system

Wedge-film Brine wet system

Reservoir formation Reservoir formation

al
u rn
Jo

CO2+brine system NP (SiO2)+CO2+brine system

Figure 11. Possible major mechanisms of NP-induced wettability alteration to brine-wet conditions.

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120
(a) (b)
Water advancing contact angle (0.05 wt% NP)
100 Water recending contact angle (0.05 wt% NP)
Water advancing contact angle (0.2 wt% NP)
Contact angle (°)

80 Water receding contact angle (0.2 wt% NP)

200 Water advancing contact angle (0.5 wt% NP)
Water receding contact angle (0.5 wt% NP)

Contact angle (°)

60 160
40 120
80
20 40
Water advancing contact…
Water receding contact angle 0
0
0 5 10 15 20 25 30
0 0.1 0.2 0.3 0.4 0.5
NP wt% Salinity (wt% NaCl)

Figure 12. Variation of water advancing and receding contact angle as a function of (a) NP concentration in base
fluid of CO2 +5% NaCl brine, and (b) salinity in base fluid of CO 2 +brine under reaction pressure and temperature
of 15MPa and 70°C (modified after Al-Anssari et al., 2018).

f
oo
pr
e-
Pr
al
u rn
Jo

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Electrostatic modifications

Steric field alterations

Region 2: NPs+CO2+brine phase

Interface between regions 1 and 2

Reservoir depth

Stabilization of the interface

f
oo
Interface between regions 2 and 3
Instability of the interface
Region 1: Brine phase Sedimentation Agglomeration
Region 3: CO2 phase

Injection point
pr
e-
Horizontal distance
Pr

Chemical reaction Crystal growth

al
u rn
Jo

Figure 13. Development of nano+CO2 plume in proposed nano-injection and its interfacial stability and instability
involving possible ageing processes.

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Zhen-Wu et al., (2016)
5 (a)
He et al., (1994)
Dissolution rate (mol.m-2.s-1)

0
0 5 10 15
pH

pH 6.5 (b)
0.09
Dissolution rate (mol.m-2.s-1)

0.08 pH 10
0.07

f
0.06

oo
0.05
0.04
0.03
0.02
0.01
0
0 0.5 1 1.5 2 2.5
pr
e-
NaCl concentration (M )
Pr

(c) 1M NaCl/7pH
9 1.5M NaCl/7pH
Dissolution rate (mol.m-2.s-1)

8
7
al

6
5
rn

4
3
2
u

1
Jo

0
0 20 40 60 80 100
Temperature (°C)

Figure 14. Dissolution characteristics of nano-barite and their variation with respect to aquifer (a) pH (He et al.,
1994; Zhen-Wu et al., 2016), (b) salinity (Ouyang et al., 2019), and (c) temperature (Zhen-Wu et al., 2016).

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Declaration of interests

☒ 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.

☐The authors declare the following financial interests/personal relationships which may be considered as
potential competing interests:

f
oo
pr
e-
Pr
al
u rn
Jo

38