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3D characterisation of potential CO2 reservoir and seal rocks

a b c a c
A. Golab , R. Romeyn , H. Averdunk , M. Knackstedt & T. J. Senden
a
Digitalcore Pty Ltd , 73 Northbourne Ave, Canberra , ACT , 2600 , Australia
b
Geoscience Australia , GPO Box 378, Canberra , ACT , 2601 , Australia
c
Department of Applied Mathematics , Research School of Physics and Engineering, Australian
National University , Canberra , ACT , 0200 , Australia
Published online: 01 Aug 2012.

To cite this article: A. Golab , R. Romeyn , H. Averdunk , M. Knackstedt & T. J. Senden (2013) 3D characterisation of potential CO2
reservoir and seal rocks, Australian Journal of Earth Sciences: An International Geoscience Journal of the Geological Society of
Australia, 60:1, 111-123, DOI: 10.1080/08120099.2012.675889

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Australian Journal of Earth Sciences (2013)

60, 111–123, http://dx.doi.org/10.1080/08120099.2012.675889

3D characterisation of potential CO2 reservoir

and seal rocks
A. GOLAB1*, R. ROMEYN2, H. AVERDUNK3, M. KNACKSTEDT1 AND T. J. SENDEN3
1
Digitalcore Pty Ltd, 73 Northbourne Ave, Canberra, ACT 2600 Australia.
2
Geoscience Australia, GPO Box 378, Canberra, ACT 2601 Australia.
3
Department of Applied Mathematics, Research School of Physics and Engineering, Australian National
University, Canberra, ACT 0200 Australia.

Digital core analysis at multiple scales incorporating X-ray micro-computed tomography (mCT) imaging
in different states in 3D, and registration of 2D SEM and SEM–energy-dispersive X-ray spectra (EDS)
images into the 3D tomograms, offers an extensive and unique toolbox for characterising potential CO2
reservoir and seal candidates. mCT imaging allows the calculation of connected porosity, and
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subsequently properties such as permeability, formation factor, Archie’s cementation component,

drainage capillary pressure, and Swi can be determined digitally and pore-throat network models can
be generated. Sub-micron scale features in the 3D image can be directly correlated with high-
resolution scanning electron microscope (SEM) images using 2D-to-3D image registration. Additionally,
the in situ mineralogy can be quantified by using an automated mineral and petrological analysis
(SEM–EDS) system. The mineralogy determined in 2D by SEM–EDS can then be interpolated into the 3D
image block for the direct identification of minerals with contrasting X-ray attenuation. The 3D data can
be readily displayed using 3D visualisations that show the pore connectivity, 3D mineralogy, geological
structures, and incorporating the pore-throat network model, SEM, and 2D in situ mineral map.
Additionally the porosity and flow pathways of a potential seal rock can be characterised at the
nanoscale (pores 10–30 nm) using focussed ion beam SEM (FIBSEM) imaging. The behaviour of the
potential reservoir and seal rocks during interaction with supercritical CO2 and water can be directly
investigated by coupling digital core analysis with a high-pressure cell. Multiple images can be
collected of the same plug before, during and after interaction with CO2 and water to directly
characterise in 3D the CO2 trapping, and changes to the pore/throat geometries and mineralogy
owing to interactions with the CO2.

KEY WORDS: CO2 sequestration, reservoir characterisation, seal characterisation, 3D micro-CT,

geochemical reaction, mineral trapping.

INTRODUCTION ability to understand petrophysical response, multi-

X-ray micro-computed tomography (mCT) consists of 3D
X-ray imaging, similar to medical CT scans, but on a
smaller scale, with greatly increased resolution. mCT
yields 3D images of solid opaque objects quickly and
non-destructively (Carlson et al. 2003). mCT is an
established and rapidly evolving technology of great
value for a wide variety of materials at micron scales
including petroleum geology, e.g. clastic (Golab et al.
2010) and carbonate rocks (Arns et al. 2005b), coal
(Mazumder et al. 2006), paper (Roberts et al. 2003),
biomaterials (Knackstedt et al. 2006), bones (Zezabe
et al. 2005), volcanic ash (Ersoy et al. 2010), paleontology
(Long et al. 2006), soil science, meteoritics, and geotech-
nics (Ketcham & Carlson 2001; Mees et al. 2003; Sleutel
et al. 2008; Narsilio et al. 2009). Considerable research is
under way in the digital imaging of core material at the
pore scale in 3D using mCT, which greatly enhances the
phase flow properties and geological heterogeneity
(Arns et al. 2005a).
mCT is a non-destructive imaging method that
provides three-dimensional data. mCT systems typically
achieve resolutions in the range of 50 mm down to 0.5 mm
(Varslot et al. 2011). Pixels (2D) and voxels (3D) represent
the relative radio density, or relative attenuation, of X-
rays through the imaged material (Novelline 1997). For a
given thickness the X-ray attenuation of any material is
a function of both the physical density and effective
atomic number of the species (Van Geet et al. 2001).
Within the tomogram, the X-ray opacity of a material
determines its brightness, i.e. voids are black owing to
low X-ray opacity, while Fe-bearing minerals are
usually light grey owing to high X-ray opacity and Al-
bearing minerals are usually mid-grey owing to inter-
mediate X-ray opacity. While the apparent opacity is a
guide to effective atomic number it must be remembered

*Corresponding author: alexandra.golab@digitalcore.com.au

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112 A. Golab et al.
that physical density is also a factor in determining
overall X-ray attenuation.
The high-resolution and large-field X-ray mCT facility
of ANU/Digitalcore Pty Ltd, Canberra was used for all
images shown in this paper. This is the only facility in
the world performing helical mCT imaging with theore-
tically exact reconstruction methods at very high cone
angles (Varslot et al. 2011). This mCT system routinely
images at 2 mm resolution. X-rays from a micro-focus X-
ray source were used to probe the sample, and an X-ray
camera was used to record a series of X-ray transmis-
sion radiographs at different viewing angles by moving
the position of the rotation stage relative to the X-ray
camera, as described by Sakellariou et al. (2004). The
cores were imaged using mCT analysis yielding 420003
voxels, by the methodology described in Varslot et al.
(2010, 2011).
The CO2 emissions reduction potential of carbon
capture and storage schemes is attractive. However, to
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be fully realised, the long-term behaviour and security of
the sequestered CO2 need to be well understood. This is a
significant challenge because CO2 has different fluid
characteristics to the fluids it would replace such as
water, brine, oil and gas. For example, in its supercritical
state, which would exist in many common geological
settings, CO2 has a density slightly less than water, a
significantly lower surface tension and a viscosity around
ten times less that would allow it to penetrate through
confining layers more easily than water. A further
challenge is that CO2, particularly dissolved as carbonic
acid in the aqueous phase, is reactive and has the
potential to change the nature of the host rock. Through
these chemical reactions the permeability, storage capa-
city, and sealing effectiveness of the reservoir could be
changed, and this has important implications for the
viability of CO2 geosequestration. In light of these
challenges, detailed knowledge of the behaviour of CO2
at the pore scale is vital and mCT has the capacity to
advance our knowledge of this behaviour greatly.
Mineral identification
The direct identification of minerals from tomographic
images relies on contrasts in X-ray attenuation of
different minerals. For example, attenuation contrasts
have been used to estimate the degree of Mg–Fe
substitution in iron–magnesium rich silicates with
sufficiently differing iron contents and CaAl–NaSi
substitution in plagioclase solid solution (Tsuchiyama
et al. 2000). However, it is not uncommon for the X-ray
attenuation of minerals from the same assemblage to
overlap e.g. olivine and Ca pyroxene or quartz and alkali
feldspar (Tsuchiyama et al. 2000), making identification
more difficult. In these cases crystal habit, cleavage or
characteristic alteration textures can still be used to
assist mineral identification but it becomes more
difficult to separate the mineral phases computation-
ally. The most powerful solution is to combine detailed
2D mineralogical images (SEM-energy-dispersive X-ray
spectra (EDS) and/or SEM) to extend the mineral
identification capacity of mCT (e.g. Figure 1).
A range of minerals has been identified as being
reactive in the presence of CO2 and water at elevated
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temperature and pressure. Table 1 details the minerals
and their products after reaction with CO2 and water.
Mineral trapping is likely to play a relatively minor role
in sequestering CO2 in siliclastic aquifer rocks owing to
the inertness of silica-rich rocks under CO2 storage
conditions (Wolff-Boenisch et al. 2006). However, even
minor reactivity may lead to significant porosity and
permeability changes that can have implications for
injectivity into host rocks or the sealing effectiveness of
impermeable cap rocks.
An important consequence of the reaction of injected
CO2 with the host rock is that the physical hydrogeolo-
gical properties of the rock change, particularly poros-
ity and permeability (Izgec et al. 2008). Porosity will tend
to increase where the host rock is being dissolved and
decrease where precipitation occurs (Luquot & Gouze
2009). Injection of CO2 into subsurface host rocks leads
to the formation of a buoyant, immiscible plume
(Johnson et al. 2004) because the density of supercritical
CO2 is generally lower than that of water. In the absence
of a stratigraphic trap, to prevent the injected CO2 from
escaping there should be a low permeability overlying
rock unit that creates an effective hydrodynamic seal
(Johnson et al. 2004). Reactive minerals within the seal
can also be important as they may enhance or decrease
sealing effectiveness over time as reactions progress, for
example, clays rich in Fe–Mg may enhance carbonate
cementation in the cap rock leading to improved seal
integrity over time (Johnson et al. 2004).
Structural changes
mCT is particularly suited to the study of structural
changes that occur in rocks when exposed to CO2-rich
fluids as these changes tend to occur at small scales but
can have significant effects on the hydraulic properties
of the rock. For example, the permeability of carbonate
rocks has been shown, using mCT, to increase owing to
acidic dissolution by CO2-rich fluids, caused by a
combination of particle dissolution and displacement,
solid-fluid interface smoothing (decreasing surface
roughness) and increasing pore connectivity (Noiriel
et al. 2005).
However, the alteration of permeability by CO2
induced dissolution is not always straightforward. For
example, in heterogeneous carbonates containing sig-
nificant amounts of clays, i.e. argillaceous limestone,
the preferential dissolution of calcite can lead to the
formation of a microporous coating of clays at the fluid–
rock interface leading to a decrease in dissolution rate
with time (Noiriel et al. 2007; Ellis et al. 2011). In some
cases, the microporous clay structure can become
unstable, resulting in reorganisation of clays that can
lead to a reduction in fracture permeability even under
chemical conditions that favour carbonate dissolution.
An increase in surface roughness may be another
mechanism for the observed decrease in permeability
(Noiriel et al. 2007).
The grain morphology of the calcite grains has also
been shown to have an impact on the process of
dissolution by CO2-rich fluids. For example, micritic
calcite exhibits a greater reactive surface area than
sparite initially but the reactive surface area of sparite
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Figure 1 Registered images of a horizontal plane through a core of potential reservoir rock; (a) slice of 3D tomogram, (b)
segmentation into pore (black), clay (dark grey), and grain (light grey and white), (c) matching SEM, and (d) matching SEM–
EDS mineralogy map. Horizontal FOV ¼ 8 mm.
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114 A. Golab et al.
Table 1 Reactive minerals occurring in sedimentary reservoir rocks.
Mineral Experimental conditions
Chlorite Simulated kinetic rate parameters
Ferrihydrite 1008C, 82 bar, 24 h
Calcite 258C, 150 bar (simulated)
Feldspars þ clays (illite,
chlorite, smectite)
Dolomite, K-feldspar and albite 608C, 300 bar, 1 M NaCl
increases greatly as dissolution progresses, grain
boundaries are opened up and fluid can access more of
the previously disconnected porous network (Noiriel
et al. 2009). This level of complexity is not captured by
simple spherical grain dissolution models while mCT
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has the advantage of directly imaging the structural
changes at the pore scale facilitating a more detailed
level of analysis.
Seals
Porosity alone is not an accurate predictor of seal rock
quality, especially in rock units with significant diagen-
esis (Rushing et al. 2008). Differentiation and quantifica-
tion of the various porosity types, their connectivity in
3D and their contribution to overall porosity and flow, is
an essential step in understanding and predicting the
integrity of a potential seal. A multi-scale 3D approach
to the characterisation of the porosity, pore and throat
size distribution, pore connectivity, permeability and
petrophysical response is required to better character-
ise seal candidates. This will include characterising the
heterogeneity and connectivity of the key constituents
(e.g., porosity, cements, clays, minerals) at the micron to
millimetre scale and imaging and analysing the poros-
ity, pore throats and connectivity at the nanoscale of
these different constituent phases.
RESULTS AND DISCUSSION
Characterisation of potential reservoir
For characterisation of potential reservoir rocks by
digital core analysis, plugs of usually 25–38 mm dia-
meter (up to 65 mm diameter) are used. Plugs that are
likely to be heterogeneous in terms of petrophysical
properties are imaged using 3D mCT analysis at plug
scale by the methodology described in Varslot et al.
(2010, 2011). The 3D images of the plug are then used to
select a region to extract a sub-plug (2–10 mm diameter)
for the calculation of petrophysical properties. The sub-
plug is then imaged by mCT analysis yielding 420003
voxels at 52 mm resolution. For example, Figure 1a
shows a slice in the Z-plane from the tomogram of an
8 mm-diameter sub-plug of a quartz sandstone potential
reservoir. The 3D image is digitally segmented into key
phases based on the X-ray attenuation, e.g. Figure 1b
with pore (black), clay (grey), and grain (white), yielding
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Products of reaction with Reference
CO2 and water
Ankerite, siderite Xu et al. (2005)
Siderite Murphy et al. (2010)
Calcium ion adsorption on Gunter et al. (1993)
clay particles
Kaolinite, calcite, dolomite,
quartz
Montmorillonite Wigand et al. (2008)
the volume percentages of each phase, in this case 22.1%
porosity. The connectivity of the porosity is determined
in 3D, e.g. Figure 2b, which shows the connected
porosity in red and disconnected porosity in black
(99% connected). Subsequently the properties such as
permeability, formation factor, Archie’s cementation
component, drainage capillary pressure, and Swi can be
determined digitally and pore-throat network models
can be generated, as described in Arns et al. (2005a).
Sub-micron scale features in the 3D image can be
directly correlated with high-resolution microscopy
data using 2D-to-3D image registration. To do so, the
sub-plug is cut and a face within the 3D field of view is
polished for the acquisition of a scanning electron
microscope (SEM) image (e.g. Figure 1c). The SEM
image in 2D is registered to the corresponding slice of
the tomogram using the 2D-to-3D registration technique
summarised in Latham et al. (2008) whereby the soft-
ware searches throughout the entire 420003 voxel block
for the exact slice that matches the SEM. The SEM
provides a higher-resolution image of the rock (down to
nm scales can be probed) and allows the evaluation of
pore-filling material and identification of microporous
regions. Crucially, the SEM image acts as in internal
calibration for the spatial resolution in 3D.
The polished face of the core can also be scanned
using an automated mineral and petrological analysis
(SEM–EDS) system that quantifies the in situ mineral-
ogy (Gottlieb et al. 2000). The SEM–EDS system com-
prises an SEM integrated with multiple light-element X-
ray detectors and pulse processor technology. Back-
scattered electrons (BSE) and energy dispersive X-ray
spectra (EDS) are used to identify minerals based on
their chemical compositions and create digital mineral
and textural maps. The samples are divided into a series
of fields; each field is measured as an individual particle
and then adjacent fields are stitched together to provide
a mineralogical composition map of the scanned area.
To analyse a field, the electron beam is rastered over the
surface, at user-defined pixel spacing down to 2 mm. The
quantified in situ mineralogy map of the registered
polished section (e.g. Figure 1d) allows one to directly
calibrate the mineralogy to the tomogram and SEM. The
mineralogy determined in 2D by SEM–EDS can then be
interpolated into the 3D image block for the direct
identification of minerals with contrasting X-ray at-
tenuation, as discussed by Tsuchiyama et al. (2000).
The 3D data can be readily displayed using 3D
visualisations that show the pore connectivity, 3D
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3D characterisation of reservoirs and seals
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Figure 2 Images of a vertical plane through a core of potential reservoir rock: (a) slice of 3D tomogram, (b) segmentation into
connected pore (red/dark grey in greyscale version), disconnected pore (black), clay (grey), and grain (white). Horizontal
FOV ¼ 8 mm.
mineralogy (e.g. Figure 3), geological structures, and
incorporating the pore-throat network model, SEM, and
2D in situ mineral map.
Characterisation of potential seal
To characterise the integrity of a potential seal and flow
pathways, the geometry and nature of porosity, the
connectivity of the porosity and fractures, and the
distribution and nature of organics and mineral compo-
nents need to be understood in 3D. Digital core analysis
allows this to be done at multiple scales. A sub-plug of
the seal rock can be imaged at the micron scale to
understand the connectivity of pores and imaging can
also be performed at the plug scale in 3D, to establish the
universality of any observations at the micron scale.
As for a reservoir rock, the seal can be imaged
by mCT (e.g. Figure 4a) and the porosity can be
investigated in 3D, e.g. Figure 5 shows slices in the
vertical plane of potential seal rock 1 with minor
porosity that does not connect in 3D. Subsequently an
SEM image can be acquired for a polished section
within the 3D image block and the images can be
registered to one another (e.g. Figure 4b). The registered
SEM provides a higher-resolution image of the seal
candidate (down to nm scales) and allows the evaluation
of the pore-filling material and identification of micro-
porous regions. Also, automated SEM–EDS can be used
to quantify the in situ mineralogy and by registering the
mineral map, it is possible to determine which minerals
are porous (e.g. Figure 4c). The mineralogy can also be
interpolated into the 3D mCT image block to check on the
connectivity of microporous minerals. Additionally the
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115
porosity and flow pathways of the seal rock can be
characterised at the nanoscale (pores 10–30 nm) using
FIBSEM imaging.
A method has also been developed that allows the
determination of connectivity of pores that are smaller
than the resolution of the mCT imaging technique and this
is described in Golab et al. (2010). Briefly the plug is
imaged in 3D in its native state by mCT and then saturated
with an X-ray dense fluid and imaged again by mCT. The
two 3D images are then registered to one another using
the method described in Latham et al. (2008). Image
registration brings into geometric alignment two or more
images, taken at different times, from different orienta-
tions and/or by different instruments. In the case of 3D-to-
3D registration, the entire overlapping blocks of 420003
voxels are aligned to one another in all three dimensions,
so that all voxels within an image coincide in each
tomogram. By comparing the two images with one
another it is possible to characterise the connectivity of
pores and fractures in 3D because only those features that
are connected will have become saturated with the
attenuating fluid. For example, Figure 6 shows matching
images of a bituminous coal sample: (a) imaged in its
native state, (b) imaged saturated with attenuating fluid
and (c) a map of connected porosity and fractures. Such a
technique is very useful for determining the connectivity
and extent of fractures in a potential seal rock, which has
implications for seal integrity.
Interaction with supercritical CO2
The behaviour of the potential reservoir and seal rocks
during interaction with supercritical CO2 and water can
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116 A. Golab et al.
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Figure 3 Example of 3D visualisation of a potential reservoir rock: (a) distribution of porosity (blue/ grey in greyscale
version), (b) distribution of clay (green/medium grey in greyscale version) and heavy mineral sand (red/black in greyscale
version); note the laminations. Sub-plug diameter ¼ 12 mm.
be directly investigated by coupling digital core analysis
with a high pressure cell. Such a cell has been
constructed and it allows multiple imaging by mCT of
the sub-plug during flooding by fluids. The cell is
currently undergoing testing at reservoir pressure with
the aim to use SC-CO2. The multiple imaging process
yields multiple 3D tomograms of the same sub-plug and
these can be registered to one another. This allows the
direct characterisation in 3D of CO2 trapping, and
changes to the pore/throat geometries and mineralogy
owing to interactions with the CO2.
Changes in mineralogy can be directly studied by
acquiring SEM and SEM–EDS images for a polished
section within the 3D image block and the images can be
registered to one another. For example, registered SEM
of potential seal 1 in Figure 4b shows the intergranular
porosity that is present, the fractures present in the clay
and cements, and the porous nature of some mineral
components, e.g. the porous calcite grain near the centre
of the image. The registered mineral map (Figure 4c)
clearly shows the locations of carbonates such as calcite,
ankerite, and minor siderite. These carbonates are
susceptible to reaction with CO2 and water (Gunter
et al. 1993). Porous calcite grains, such as the grain
shown near the centre of the image (Figure 4) would be
particularly susceptible to reaction owing to its in-
creased surface area.
Figure 7 shows an example of potential reservoir
rock 2 with four different images: (a) imaged in 3D in its
native state, (b) imaged in 3D saturated with attenuating
fluid, (c) imaged in 2D by SEM, and (d) analysed in 2D by
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SEM–EDS. With the combination of these images we are
able to determine which minerals are associated with
connected porosity. In addition to the small open pores
(0.8%) visible in Figure 7, the majority of the micro-
porosity in this arkose sandstone is associated with the
clays, illite/muscovite, and chlorite as well as minor
contributions from weathered lithic grains. The sand-
stone contains 3% dolomite and these grains are slightly
porous, indicating a high surface-area-to-volume ratio
and making them susceptible to reaction with CO2 and
water. The sample also contains *2% calcite and minor
ankerite and siderite.
Carbonic acid reactivity study
Some of the CO2 that is injected into the subsurface
dissolves in the aqueous phase of pore fluids forming
carbonic acid, which may react with certain minerals
causing the mechanical or hydraulic properties of the
rock to change. The importance of the aqueous phase
to the reactivity observed in CO2 sequestration
scenarios was demonstrated by Muller (2010) who
recorded dissolution rates two orders of magnitude
lower in a high pressure vessel at 60–2008C, 15–70 MPa
pCO2 with 1–1.5 g water compared with an acid bath
containing 150 g water at pH 3, 50–808C, and open to
the atmosphere. Since the supercritical CO2 phase
appears to be relatively inert, a simple single phase
carbonic acid experiment was designed to give an
indication of CO2 reactivity relevant to sequestration
scenarios.
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Figure 4 Registered images of a selected region of the horizontal plane through a core of potential seal rock 1: (a) slice of 3D
tomogram, (b) matching SEM, and (c) matching SEM–EDS mineralogy map. Horizontal FOV ¼ 3 mm.

Figure 5 Images of a vertical plane through a core of potential seal rock 1: (a) slice of 3D tomogram in the X-plane, (b) slice of
3D tomogram in the Y-plane. FOV ¼ 3 mm.
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118 A. Golab et al.

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Figure 6 Registered images of a selected region of the vertical plane through a bituminous coal sample: (a) slice of 3D
tomogram in native state (black ¼ pore/fracture, dark grey ¼ coal, white ¼ siderite), (b) slice of 3D tomogram saturated with
X-ray dense fluid (light grey ¼ fluid), (c) map of connected porosity (black ¼ open pore; white ¼ non-porous, microporous ¼
shades of grey). FOV ¼ 19 mm.

Mardie Greensand was selected to investigate
changes induced by exposure to carbonic acid because
X-ray powder diffraction (XRD) analysis revealed that it
contains an array of reactive minerals including
ankerite, siderite, and iron-rich glauconitic clays. A
4 mm subplug of the sample was treated to make it
water wet and then imaged (Figure 8a). The sample was
subsequently partially immersed (to a depth of about 1/3
of the height of the core) in a 10 g/L NaCl brine solution
so that it was saturated via capillary rise. The solid–
solution volume ratio was in the order of 1:4. The vessel
containing the solution and sample was placed in a
pressure vessel and subjected to 1000 kPa pCO2 at room
temperature (15–208C) for 329 h (the solution was
stagnant during the experiment). Finally, the subplug
was re-imaged (Figure 8b) after being placed in a beaker
containing 1500 ml of deionised water for 3 days,
changing the water each day, to prevent NaCl from the
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Figure 7 Registered images of a selected region of the horizontal plane through a subplug of potential seal rock 2: (a) slice of 3D
tomogram imaged in its native state, (b) slice of 3D tomogram saturated with X-ray dense fluid (white ¼ fluid), (c) map of
connected porosity (black ¼ open pore; white ¼ non-porous, microporous ¼ shades of grey), (d) matching SEM, and (e)
matching SEM–EDS mineralogy map. FOV ¼ 1.5 mm.

brine from precipitating during imaging. The pH of the
solution was not measured in the pressure cell but was
expected to be in the range of pH 3–3.5 based on the work
of Meyssami et al. (1992).
Although the experimental conditions were milder
than those typical of geological CO2 storage scenarios
i.e., lower temperatures and pressures, some reactivity
was observed following the two weeks of exposure. This
is clearly demonstrated by comparing the tomographic
images (Figure 8a, b) and the difference tomogram
created after 3D to 3D registration (Figure 8c). The
difference tomogram illustrates that the changes
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120 A. Golab et al.

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Figure 8 Registered mCT images of a selected region of the horizontal plane through a 4 mm sub-plug of Mardie Greensand: (a)
slice of 3D tomogram imaged in its initial state, (b) matching slice of 3D tomogram imaged following treatment with carbonic
acid for 329 h under 1 MPa pCO2 and room temperature (15–208C), and (c) the difference between the two 3D tomograms; dark
regions represent a loss of material (e.g. dissolution or particle removal), and light regions indicate material has been gained
(e.g. precipitation or particle dislocation). FOV ¼ 0.8 6 0.7 mm.

induced by carbonic acid exposure occurred in rela-
tively localised regions of the core and were dominated
by a loss of material. From the localised nature of these
changes it was inferred that the permeability of the
sample would not have been altered dramatically as
the significant changes tended to be disconnected from
one another. In addition to being spatially disjointed,
the observed reactivity was also heterogeneous miner-
alogically, i.e. not all grains of a particular mineral
exhibited similar reactivity.
The loss of material, highlighted in Figure 8c and
visualised in 3D in Figure 9, is interpreted as a combi-
nation of dissolution and particle dislocation. Large
changes associated with glauconite pellets seems likely
to involve at least some particle dislocation since these
pellets tend to consist of smaller aggregated particles.
Regions of ankerite–glauconite intergrowth, as shown
in Figure 8, seem to be particularly susceptible to
dissolution by carbonic acid. The reactive glauconite
pellets tend to exhibit significant internal porosity that
may present a large reactive surface area and subse-
quently promote attack by carbonic acid. Some disag-
gregation of glauconite particles from the larger pellets
may occur as the contact surfaces between the particles
are dissolved, enhancing the visible degradation of
the pellet.
The calcite grain displays clear rhombohedral
cleavage and appears to contain microfractures that
also adhere to rhombohedral cleavage angles (Figure
9). These microfractures most likely allowed ingress of
the carbonic acid, increasing the reactive surface area
of the grain and enhanced dissolution relative to un-
fractured ankerite within the sample. This microfrac-
tured morphology may have been a product of the
crystallisation of the ankerite and glauconite in an
intergrowth.
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3D characterisation of reservoirs and seals 121

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Figure 9 3D visualisations of the Mardie Greensand tomograms in the initial state (Figure 8a) and the difference tomogram
(Figure 8c). Green ¼ negative anomalies in the difference tomogram i.e. loss of material through dissolution or particle
dislocation; yellow ¼ X-ray dense phase interpreted as ankerite; pink ¼ low X-ray density phase interpreted as glauconite/
clay (and some overlap with void space); blue ¼ moderate X-ray density phases interpreted as quartz/feldspar. (a) Displays all
phases, (b) phases other than calcite have reduced opacity, (c) ankerite only, (d) ankerite and zones of material loss, and (e)
all phases but ankerite. FOV ¼ 0.7 6 0.5 6 0.4 mm.
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122 A. Golab et al.
The heterogeneous extent of the observed reactivity
of the glauconite phase with carbonic acid may be
explained diagenetically. It is proposed that the reactive
fraction of the glauconite may be autochthonous with a
high Fe content and rough exterior surfaces consisting
of clay plates (Hamilton & Dowen 2001) whereas the
inert fraction may be composed of reworked pellets with
a lower Fe content and smooth exterior surfaces
presenting lower surface areas to pore fluids (Hamilton
& Dowen 2001). The fact that the reactive fraction of the
glauconite tends to be intergrown with ankerite sup-
ports the interpretation that it is autochthonous rather
than reworked, as the contact between the grains would
likely be broken on transport.
CONCLUSIONS
Digital core analysis at multiple scales incorporating X-
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ray micro-computed tomography (mCT) imaging in
different states in 3D, and registration of 2D SEM and
SEM–EDS images into the 3D tomograms, offers an
extensive and unique toolbox for characterising potential
CO2 reservoir and seal candidates. Sub-micron scale
features in the 3D image can be directly correlated with
high-resolution Scanning Electron Microscope (SEM)
images using 2D-to-3D image registration. Additionally,
the in situ mineralogy can be quantified by using an
automated mineral and petrological analysis (SEM–EDS)
system. The mineralogy determined in 2D by SEM–EDS
can then be interpolated into the 3D image block for the
direct identification of minerals with contrasting X-ray
attenuation. The behaviour of the potential reservoir and
seal rocks during interaction with supercritical CO2 and
water can be directly investigated by coupling digital
core analysis with a high-pressure cell. Multiple images
can be collected of the same plug before, during and after
interaction with CO2 and water to directly characterise
in 3D the CO2 trapping, and changes to the pore/throat
geometries and mineralogy owing to interactions with
the CO2. Reservoir porosity and permeability can be
calculated in its native state and compared with values
calculated after reaction with CO2 and water. Seal
integrity in terms of connected porosity and fractures
can be determined in 3D and seal reactivity with CO2 and
water can be imaged and quantified.
REFERENCES
ARNS C. H., BAUGET F., GHOUS A., SAKELLARIOU A., SENDEN T. J.,
SHEPPARD A. P., SOK R. M., PINCZEWSKI W. V., KELLY J. &
KNACKSTEDT M. A. 2005a. Digital core laboratory: Petrophysical
analysis from 3D imaging of reservoir core fragments. Petro-
physics 46, 260–277.
ARNS C. H., BAUGET F., LIMAYE A., SAKELLARIOU A., SENDEN T. J.,
SAKELLARIOU A., SHEPPARD A. P., SOK R. M., PINCZEWSKI W. V.,
BAKKE S., BERGE L. I., OREN P. E. & KNACKSTEDT M. A. 2005b.
Pore scale characterization of carbonates using micro X-ray CT.
Society of Petroleum Engineers Journal, December, 475–484.
CARLSON W. D., ROWE T., KETCHAM R. A. & COLBERT M. W. 2003.
Applications of high-resolution X-ray computed tomography in
petrology, meteoritics and paleontology. In: Mees F., Swennen
R., Van Geet M., Jacobs P. eds. Applications of X-ray computed
tomography in the geosciences, 7–22. Geological Society, London,
Special Publication 215.
~/Desktop/11.03.2013/TAJE_60-01
ELLIS B. R., BROMHAL G. S., MCINTYRE D. L. & PETERS C. A. 2011.
Changes in caprock integrity due to vertical migration of CO2-
enriched brine. Energy Procedia 4, 5327–5334.
ERSOY O., ŞEN E., AYDAR E., TATAR I_ & ÇELIK H. H. 2010. Surface area
and volume measurements of volcanic ash particles using micro-
computed tomography (micro-CT): A comparison with scanning
electron microscope (SEM) stereoscopic imaging and geometric
considerations. Journal of Volcanology and Geothermal Research
196, 281–286.
GOLAB A., KNACKSTEDT M. A., AVERDUNK H., SENDEN T., BUTCHER
A. R. & JAIME P. 2010. 3D porosity and mineralogy character-
ization in tight gas sandstones. The Leading Edge, December,
936–942.
GOTTLIEB P., WILKIE G., SUTHERLAND D., HO-TUN E., SUTHERS S.,
PERERA K., JENKINS B., SPENCER S., BUTCHER A. R. & RAYNER J.
2000. Using quantitative electron microscopy for process miner-
alogy applications. Journal of the Minerals, Metals and Materials
Society, April, 24–25.
GUNTER W. D., PERKINS E. H. & MCCANN T. J. 1993. Aquifer disposal
of CO2-rich gases: Reaction design for added capacity. Energy
Converservation Management 34 (9–11), 941–948.
HAMILTON J. & DOWEN M. 2001. Diagenesis in the Mardie Greensand
of the NW shelf of Australia and its effects on NMR measure-
ments. American Association of Petroleum Geologists Annual
Convention. Denver, Colorado.
IZGEC O., DEMIRAL B., BERTIN H. & AKIN S. 2008. CO2 injection into
saline carbonate aquifer formations I: laboratory investigation.
Transport in Porous Media 72, 1–24.
JOHNSON J. W., NITAO J. J. & KNAUSS K. G. 2004. Reactive transport
modelling of CO2 storage in saline aquifers to elucidate funda-
mental processes, trapping mechanisms and sequestration
partitioning. In: Baines S. J. & Worden R. H. eds. Geological
storage of carbon dioxide, 107–128. Geological Society, London,
Special Publications 233.
KETCHAM R. A. & CARLSON W. D. 2001. Acquisition, optimization
and interpretation of X-ray computed tomographic imagery:
applications to the geosciences. Computers & Geoscience 27,
381–400.
KNACKSTEDT M., ARNS C., SENDEN T. J. & GROSS K. 2006. Structure
and properties of clinical coralline implants measured via 3D
imaging and analysis. Biomaterials 27 (13), 2776–2786.
LATHAM S., VARSLOT T. & SHEPPARD A. 2008. Image registration:
Enhancing and calibrating X-ray micro-CT imaging. In: Proceed-
ings of the International Symposium of the Society of Core
Analysts. SCA2008-35. Abu Dhabi, United Arab Emirates.
LONG J., YOUNG G., HOLLAND T., SENDEN T. & FITZGERALD E. 2006. An
exceptional Devonian fish from Australia sheds light on tetrapod
origins. Nature 444, 199–202.
LUQUOT L. & GOUZE P. 2009. Experimental determination of porosity
and permeability changes induced by injection of CO2 into
carbonate rocks. Chemical Geology 265, 148–159.
MAZUMDER S., WOLF K-H. A. A., ELEWAUT K. & EPHRAIN R. 2006.
Application of X-ray computed tomography for analyzing cleat
spacing and cleat aperture in coal samples. International
Journal of Coal Geology 68, 205–222.
MEES F., SWENNEN R., VAN GEET M. & JACOBS P. 2003. Applications of
X-ray computed tomography in the geosciences. Geological
Society, Special Publication 215, London, 243 p.
MEYSSAMI B., BALABAN M. O. & TEIXEIRA A. A. 1992. Prediction of pH
in model systems pressurized with carbon dioxide. Biotechnology
Progress 8, 149–154.
MULLER N. 2010. Supercritical CO2-brine relative permeability
experiments in reservoir rocks—Literature review and recom-
mendations. Transport in Porous Media, doi:10.1007/s11242-010-
9689-2.
MURPHY R., LAMMERS K., SMIRNOV A., SCHOONEN M. A. A. &
STRONGIN D. R. 2010. Ferrihydrite phase transformation in the
presence of aqueous sulphide and supercritical CO2. Chemical
Geology 271, 26–30.
NARSILIO G. A., BUZZI O., FITYUS S., YUN T. S. & SMITH D. W. 2009.
Upscaling of Navier–Stokes equations in porous media: Theore-
tical, numerical and experimental approach. Computers and
Geotechnics 36 (7), 1200–1206.
NOIRIEL C., BERNARD D., GOUZE P. & THIBAULT X. 2005. Hydraulic
properties and microgeometry evolution accompanying lime-
stone dissolution by acidic water. Oil & Gas Science and
Technology 60 (1), 177–192.
 TAJE_60-01_O.indd Page 123 11/03/13 9:03 PM user-f-401
3D characterisation of reservoirs and seals
NOIRIEL C., LUQUOT L., MADE B., RAIMBAULT L., GOUZE P. & VAN DER
LEE J. 2009. Changes in reactive surface area during limestone
dissolution: An experimental and modelling study. Chemical
Geology 265, 160–170.
NOIRIEL C., MADE B. & GOUZE P. 2007. Impact of coating development
on the hydraulic and transport properties in argillaceous lime-
stone fracture. Water Resources Research 43, W09406
NOVELLINE R. 1997. Squire’s fundamentals of radiology. Harvard
University Press, Harvard.
ROBERTS R., SENDEN T. J., KNACKSTEDT M. A. & LYNE M. B. 2003.
Spreading of aqueous liquids in unsized papers is by film flow.
Journal of Pulp and Paper Science 29, 123–130.
RUSHING J. A., NEWSHAM K. E. & BLASINGAME T. A. 2008. Rock
typing—Keys to understanding productivity in tight gas sands.
Society of Petroleum Engineers Paper 114164.
SAKELLARIOU A., SAWKINS T. J., SENDEN T. J. & LIMAYE A. 2004. X-ray
tomography for mesoscale physics applications. Physica A:
Statistical Mechanics and its Applications 339 (1–2), 152–158.
SLEUTEL S., CNUDDE V., MASSCHAELE B., VLASSENBROEK J., DIERICK
M., VAN HOOREBEKE L., JACOBS P. & DE NEVE S. 2008.
Comparison of different nano- and micro-focus X-ray computed
tomography set-ups for the visualization of the soil microstruc-
ture and soil organic matter. Computers & Geosciences 34, 931–
Downloaded by [University of Sydney] at 20:36 29 January 2014
938.
TSUCHIYAMA A., HANAMOTO T., NAKASHIMA Y. & NAKANO T. 2000.
Quantitative evaluation of attenuation contrast of minerals by
using a medical X-ray CT scanner. Journal of Mineralogical and
Petrological Sciences 95, 125–137.
~/Desktop/11.03.2013/TAJE_60-01
123
VAN GEET M., SWENNEN R. & WEVERS M. 2001. Towards 3D
petrography: application of microfocus computer tomography
in geological science. Computer & Geosciences 27, 1091–1099.
VARSLOT T., KINGSTON A., MYERS G. & SHEPPARD A. 2011. High-
resolution helical cone-beam micro-CT with theoretically-exact
reconstruction from experimental data. Medical Physics 38 (10),
doi:10.1118/1.3633900.
VARSLOT T., KINGSTON A., SHEPPARD A. & SAKALLARIOU A. 2010. Fast
high-resolution micro-CT with exact reconstruction methods. In:
Proceedings SPIE Developments in X-ray Tomography VII, Vol.
7804, 780413, San Diego, CA.
WIGAND M., CAREY J. W., SCHÜTT H., SPANGENBERG E. & ERZINGER J.
2008. Geochemical effects of CO2 sequestration in sandstones
under simulated in situ conditions of deep saline aquifers.
Applied Geochemistry 23, 2735–2745.
WOLFF-BOENISCH D., GISLASON S. R. & OELKERS E. H. 2006. The effect of
crystallinity on dissolution rates and CO2 consumption capacity of
silicates. Geochemica et Cosmochimica Acta 70, 858–870.
XU T., APPS J. A. & PRUESS K. 2005. Mineral sequestration of carbon
dioxide in a sandstone–shale system. Chemical Geology 217, 295–
318.
ZEZABE R., JONES A., KNACKSTEDT M. & SEEMAN E. 2005. Femoral
neck shape and the spatial distribution of its mineral mass
varies with its size: Clinical and biomechanical implications.
Bone 37 (2), 243–252.
Received 20 September 2011; accepted 11 January 2012