International Journal of Coal Geology 108 (2013) 2–9

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International Journal of Coal Geology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i j c o a l g e o

Influence of CO2 on New Albany Shale composition and pore structure

Richard Lahann, Maria Mastalerz ⁎, John A. Rupp, Agnieszka Drobniak
Indiana Geological Survey, Indiana University, 611 North Walnut Grove Ave., Bloomington, IN 47405-2208, United States

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

Article history: To determine the possible influence of CO2 on the pore structure and mineralogy of the New Albany Shale
Received 16 December 2010 (Devonian–Mississippian), experiments were conducted utilizing Indiana shale samples of varying total
Received in revised form 2 May 2011 organic carbon content under various conditions. After the shale samples were heated to as high as 150 °C in
Accepted 16 May 2011
Teflon-lined high-pressure reaction cells with either distilled water or NaCl brine and CO2, the reaction
Available online 19 May 2011
products were characterized by mesopore and micropore analysis, X-ray diffraction and scanning electron
Keywords:
microscope analysis of the shale residue, and fluid chemistry analysis of the reactant brine. Results from
Shales CO2-saturated shale and distilled water showed no changes in shale pore structure relative to shale samples
CO2 sorption without CO2 surface saturation.
Brine composition A second series of experiments was run at 80 °C, using 50,000 ppm NaCl brine, 60-mesh ground shale (2:1 by
mass), and varying amounts of solid CO2 (dry ice). The pressure in the reaction cells was controlled by the partial
pressure of CO2 and ranged from 100 to 3500 psi (0.69 to 24.13 MPa). Post-reaction brine samples showed up to
thousands of ppm of K, Mg, and Ca in solution. The concentration of Ca and Mg in the brine tended to increase in
proportion to the increasing partial pressure of CO2. The same experiments using chips of shale from the New
Albany Shale showed lower concentrations of the cations in solution, but displayed a similar pattern of
increasing Ca and Mg with increasing CO2 pressure. Scanning electron microscope examination of the shale chips
confirmed the dissolution of carbonate-mineralized biogenic structures in the shale.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction dissolution of silicates and precipitation of carbonates might

influence porosity, permeability, and diffusion properties, possibly
Geological sequestration of carbon dioxide (CO2) is one of the enhancing CO2 transport upon sequestration.
favored options to prevent CO2 increase in the atmosphere. Several The purpose of this study is to investigate the possible changes to the
rock types including saline aquifers, depleted oil and gas reservoirs, pore structure and mineralogy that could be caused by CO2 injection into
coals, and organic-rich shales show potential to store large quantities an organic-rich shale. The shale being evaluated is the New Albany Shale
of CO2. Saline aquifers and depleted oil and gas reservoirs employ (Upper Devonian–Lower Mississippian) of the Illinois Basin. The
displacement phenomena, hydrodynamic solubility, and mineral production of natural gas from the New Albany Shale horizon
trapping mechanisms to sequester the CO2 in conventional reservoirs commenced in 1885 and, with some breaks, has taken place until the
(Bruant et al., 2002; Gunter et al., 2000; White et al., 2003). In contrast, present (Partin, 2004). Controls on shale gas potential of the New
coals and organic-rich shales dominantly utilize adsorption onto organic Albany Shale were discussed in the recent paper by Strąpoć et al. (2010).
matter present in the rock as the storage mechanism (e.g., Arri et al., In addition to its gas potential, this horizon is also of interest for CO2
1992; Fulton et al., 1980; Reznik et al., 1984; White et al., 2005). sequestration (Nuttall et al., 2009). The depth of the New Albany Shale
Organic matter-rich shales are capable of storing significant volumes ranges from 0 to 5200 ft (1585 m) (Strąpoć et al., 2010), and its
of CO2 by fixing the CO2 as a solid precipitate via mineral reactions temperature (13–66 °C, 56–150 °F) and pressure (up to 2236 psi)
and sorption onto organic matter as well as mineral matter surfaces ranges indicate that there is a significant depth zone (approximately
(Krooss et al., 2003). Several studies have demonstrated that gas below 2500 ft) where stored CO2 would be a supercritical fluid. This
sorption in shales is influenced by both the organic and clay contents zone is of special interest for CO2 sequestration.
of the rock (e.g., Chalmers and Bustin, 2007; Manger et al., 1991; Ross
and Bustin, 2007). Recent experimental study on a shale sample from 2. Materials and methods
Australia (the Muderong Shale, Cretaceous) attributed CO2 fixation
to a combination of aqueous solubility, chemical reactions, and 2.1. Sample material
physical sorption (Busch et al., 2008). That study also suggested that
In order to evaluate the reactivity of organic-matter bearing shales
⁎ Corresponding author. Fax: +1 812 855 2862. in the presence of CO2 under simulated reservoir conditions, four
E-mail address: mmastale@indiana.edu (M. Mastalerz). samples of New Albany Shale were collected from two archived but

0166-5162/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.coal.2011.05.004
 R. Lahann et al. / International Journal of Coal Geology 108 (2013) 2–9 3

well preserved cores and ground to 250 μm. The samples were chosen vessel for a time period from 3 to 42 days (Table 4). The purpose of
to represent a range of CO2 adsorption capacities (Fig. 1, data from this process was to create a CO2-saturated environment that could
Nuttall et al., 2009) and a range of total organic carbon (TOC) contents interact with the surface of the pores. At the end of the heating
from 5.3 to 15.8% (Table 1, Fig. 2A, B). The samples were initially period, the shale was analyzed by XRD and porosimetry methods.
characterized by X-ray diffraction (XRD), whole rock geochemistry, 3) Experiments to test the influence of CO2 on shale mineralogy and
organic petrology, and mesopore and micropore distribution. Bulk pore structure at high pressure (up to 24.13 MPa, 3500 psi). In
geochemical data were generated by X-ray fluorescence analysis, these experiments, 2-gram (250 μm size particles) samples MM1,
along with organic and inorganic carbon. Bulk mineralogy (Table 2) MM3, and MM4 were added to 2 ml of 50,000 ppm NaCl brine, to
was determined by a normative composition procedure employing mimic the salinity of the formation fluids of the New Albany Shale
the XRD and elemental composition data. (50,000 ppm total dissolved solids, primarily NaCl, is approxi-
mately the lower limit of observed salinities in the New Albany
2.2. Experimental design and analyses Shale). Variable amounts (including none) of solid CO2 (to simulate
various pressures) were added to the Teflon reaction chamber and
Previous studies (Nuttall et al., 2009) have shown that CO2 the chamber was heated to 80 °C for 21 days. The chamber was
adsorption of New Albany Shale samples correlates strongly with sealed immediately after the CO2 addition, but some minor loss of
TOC, but no data are available on the response of minerals to the CO2 may have occurred during this process which would reduce
CO2 injected under high pressure in these shales. Our experimental slightly the calculated internal pressure. Since pressure transducers
objectives were to determine whether adsorbed CO2 would interact were not available, the final internal pressure of CO2 in the chamber
with minerals so as to increase the total CO2 fixation potential, or was calculated using the known volumes of shale and water
whether any interactions would occur that would decrease the shale reactants and equation of state data for CO2. Estimated internal CO2
permeability (e.g., by swelling, or precipitation of carbon-bearing pressures ranged from 100 psi (0.69 MPa) up to about 3500 psi
minerals, Kűhn et al., 2009) and prevent CO2–organic interaction. To (24.1 MPa). In addition, a few experiments in this third category
address both objectives, the experiments were conducted on shales were conducted using rock chips instead of ground powders. After
having both high and relatively low TOC contents. In all experiments, the period of heating, the reaction cell was allowed to cool and the
shale samples were placed in a Teflon reaction chamber (Fig. 2C) and CO2 pressure vented. The shale products of the reaction were then
loaded into a high-pressure vessel (Fig. 2D). separated from the fluid by filtration and the filtrate captured for
Experiments run on the samples can be grouped as follows: plasma spectroscopic analysis of Na, K, Mg, Ca and Fe contents. The
shale was washed with distilled water, in order to prevent halite
1) Experiments to test the influence of temperature alone on possible precipitation, and then analyzed by XRD and porosimetry and the
changes in the fabric (pore system) of the shale at low pressure results compared with analyses of unreacted materials.
(up to 719 mm Hg, 95.86 kPa, 13.9 psi). In these experiments,
samples MM1 and MM3 with no CO2 added were heated at 150 °C BET (Brunauer–Emmett–Teller) specific surface area, BJH
for 4 and 21 days (Table 3). This temperature is higher than the (Barrett–Joyner–Halenda) mesopore volumes, micropore surface
regional reservoir temperature for the New Albany Shale but it was area, monolayer capacity, and micropore volumes of shale samples
chosen to promote reactions and to compensate for a short before and after experiments were determined using an ASAP 2020
duration of experiments. porosimeter. Pore classification (mesopores 2–50 nm and micro-
2) Experiments to test the influence of adsorbed CO2 on shale pores less than 2 nm) of the International Union of Pure and Applied
mineralogy and pore structure at low pressure. In these experi- Chemistry (Orr, 1977) was used. BET specific surface area and BJH
ments, 2 g samples MM1 (TOC 15.8%) and MM3 (TOC 5.8%) were mesopore volume analyses were carried out using nitrogen gas as
enriched in CO2 by equilibrating with CO2 at 550 psi (3.8 MPa) at the adsorptive medium at the boiling point temperature of liquid
about 15 °C in a volumetric high-pressure adsorption apparatus. It nitrogen (77.35 K) in a pressure range of 0–to 800 mm Hg. For
is possible that some loss of CO2 occurred after this equilibration. mesopore volume determination, the adsorption branch of the
The samples with CO2 added were combined with 2 ml of distilled isotherm was used. Micropore volume, micropore specific surface
water and the resulting paste heated at 150 °C in a Teflon reaction area, and monolayer capacity were determined using CO2 as the

10 320

9 MM1 (TOC 15.8%)

288
Quantity adsorbed (scf/ton)

MM2 (TOC 5.3%) 256

8
Quantity adsorbed (m3/t)

MM3 (TOC 5.8%)

7 MM4 (TOC 13.0%) 224

6 192

5 160

4 128

3 96

2 64

1 32

0 0
0 2 4 6 8 10
Pressure (MPa)

Fig. 1. High pressure methane adsorption isotherms of the samples MM1–MM4 (data from Nuttall et al., 2009).
4 R. Lahann et al. / International Journal of Coal Geology 108 (2013) 2–9

adsorptive at a temperature of 273 K. Before analysis with either N2

D–A micropore volume

or CO2, the samples were automatically degassed by heating at

BJH mesopore vol

~ 110 °C in vacuum for about 20 h to remove adsorbed moisture and
General information (depth, stratigraphic member, TOC, vitrinite reflectance — Ro) of the samples and their mesopore (based on nitrogen adsorption) and micropore (based on CO2 adsorption) characteristics. Sa — surface area. atmospheric gases.

0.021628
0.036089
0.018564
0.014749

0.015577
0.012363
0.009260
0.015003
cm3/g

cm3/g
3. Results and discussion

3.1. Characteristics of the original shale samples

Shale samples from two Illinois Basin wells located in Indiana

(IGSID-107310, Lawrence County and IGSID-119139, Sullivan County)
were used in these experiments. They come from three members
D–R monolayer capacity
of the New Albany Shale: the Clegg Creek, Camp Run and Blocher
Members (Table 1). Total organic carbon content in these samples
BJH mesopore sa

ranges from 5.34 to 15.8%, and the vitrinite reflectance values are
around 0.55% for the shallower well and 0.61% for the deeper one.
Mineralogically the shales are composed dominantly of illite and quartz
m2/g

m3/g
15.0
7.8

5.2
4.3

4.9
3.5
1.5
2.9 (Table 2). Their mesopore (determined by nitrogen adsorption) and
micropore (determined by CO2 adsorption) characteristics are listed
in Table 1. As Table 1 demonstrates, the micropore volume of these
shales depends to a large extent on the content of organic matter
(r 2 = 0.76). High pressure CO2 adsorption isotherms of these four
moisture-equilibrated samples are presented in Fig. 1, also doc-
D–R micropore sa

umenting higher adsorption capacity for samples with higher TOC.

Langmuir sa

Based on TOC values and mineralogical composition, initially two

samples, MM1 (Clegg Creek Member) and MM3 (Camp Run Member),
m2/g

m2/g

were selected for experiments. The rationale for this selection was to
8.3
7.2

6.9
12.1
26.0

22.4
15.9

13.2

have one sample having high organic matter content (MM1) and one
Nitrogen adsorption

sample with low organic matter content but higher carbonate content
(MM3, Table 2, Fig. 2). Later, sample MM4 (Clegg Creek Member, high
CO2 adsorption

TOC of 13%, Table 1) was also added to supplement the data.

BET sa

BET sa

3.2. Influence of temperature and adsorbed CO2 on shale at low pressure

m2/g

m2/g
7.3

5.0
4.3

5.3
9.9
15.6

15.5
11.1

X-ray examination of the heating experiment products of

organic-matter-rich sample MM1 showed no detectable changes in
shale matrix mineralogy. Occasionally an orange sheen was observed
on the water surface after heating or on top of the dried shale samples
0.55
0.57
0.62
0.61

0.55
0.57
0.62
0.61

after reaction or both. In contrast, sample MM3, which contained

Ro

Ro
%

considerably less TOC and slightly more carbonate minerals, consis-

tently displayed orange–red discoloration at the base of the clay
sediments on the filter paper. X-ray diffraction indicated possibly
smaller amounts of carbonate minerals in the post-heating sediment
of this sample, but no consistent pattern of decreased carbonate with
15.8

13.0

15.8

13.0
5.3
5.8

5.3
5.8
TOC

TOC

time. The color development was present in both original and

%

CO2-enriched samples. The development of the red color in the

MM3 sample is strong evidence for a reactive matrix. We infer that
some minor oxidation of pyrite occurred during the heating phase,
followed by oxidation and formation of iron oxyhydroxide phases
during subsequent atmospheric exposure and drying.
Clegg Creek

Clegg Creek

Clegg Creek

Clegg Creek
Camp Run

Camp Run

Surface area measurements and mesopore and micropore charac-

Member

Member
Blocher

Blocher

teristics of the samples without CO2 and those after CO2 adsorption
are listed in Tables 3 and 4. Table 3 compares data for MM1 and MM3
without CO2 added, after experiments run at 150 °C, whereas Table 4
compares data for the same samples with CO2 added and kept at
150 °C for different times. We acknowledge that the temperature of
150 °C is higher than would be encountered under shale reservoir
Depth

Depth
(feet)

(feet)

conditions where CO2 sequestration is considered. Such a high temper-

1020
2552
2506

1020
2552
2506
940

940

ature was selected to compensate for short experimental time,

assuming that higher temperature would accelerate by some unknown
factor reactions related to the introduction of CO2. These porosimetry
data show that:
Sample

Sample

1) For both samples, there is a small increase in BET surface area

Table 1

MM1
MM2
MM3
MM4

MM1
MM2
MM3
MM4

(measured by nitrogen adsorption) as a result of temperature alone.

A similar trend is also noticed for BJH mesopore volume (Table 3,
 R. Lahann et al. / International Journal of Coal Geology 108 (2013) 2–9 5

MM1

al am

MM3

C D

Fig. 2. A and B — Lithology of shale samples MM1 and MM3. Note the darker color of MM1 as a result of higher organic matter content. Photomicrographs (reflected light, oil
immersion) of these samples are included on the right. Note much more abundant organic matter in sample MM1 than in MM3. al — alginite, am — amorphinite, and p — pyrite. Scale
bar is 20 μm. C — Teflon reaction chamber and a shale sample. D — External containment and Teflon reaction chamber used in the experiments.

Fig. 3A). This change, as small as it is, indicates that this low maturity 2) There is a similar increase in BET surface area and BJH mesopore
shale is sensitive to temperature changes. Such a change in surface volume as a result of the combined effect of temperature and CO2
area and mesopore volume may reflect transformation of some (Table 4, Fig. 3A).
macropores (pores larger than 50 nm) to mesopores (pores of 50 to 3) For the micropore characteristics (measured by CO2 adsorption),
2 nm range) in response to high temperature. no regular changes occur as a result of temperature alone or
temperature coupled with adsorbed CO2 (Tables 3 and 4, Fig. 3B).

Table 2 These observations demonstrate that CO2 did not add to the effect
Petrographic characteristics of the samples studied. Identification of minerals was done of the temperature alone or, in other words, that the presence of
by XRD and XRF was used to obtain elemental composition and modal analysis to adsorbed CO2 did not have a measurable influence either on mesopore
distribute elements across observed mineral phases. Organic matter (total organic
or micropore characteristics.
carbon, TOC) was determined on a Leco TOC analyzer.
The similarity in micro- and mesoporosity of the original (no CO2
Sample Organic matter Pyrite Apatite Dolomite Illite Chlorite Quartz added) and CO2-enriched reaction products may be interpreted as an
MM1 16.4 10 0.3 0.3 37 3 33 indication that the total CO2 present in these experiments does not
MM2 6 2 0.1 1.9 53 8 29 involve the mesopore and micropore system. An alternative inter-
MM3 5.6 4 0.1 3.3 54 7 26 pretation is that all/most of the adsorbed CO2 is lost from the sample
MM4 13.8 3 0.2 1.0 39 4 39
in the 30-second +/− exposure of the CO2-enriched sample to the
6 R. Lahann et al. / International Journal of Coal Geology 108 (2013) 2–9

Table 3
Mesopore (based on nitrogen adsorption) and micropore (based on CO2 adsorption) characteristics on M1 and M3 samples kept at 150 °C without CO2. Sa — surface area.

Nitrogen adsorption CO2 adsorption

Sample BET sa BJH volume Ave mesop. size BET sa D–R msa D–R mon cap D–A mic vol
and time m2/g cm3/g nm m2/g m2/g cm3/g cm3/g

MM1 — at 150 °C, no CO2

Original 7.3 0.021628 12.2 15.5 22.4 4.9 0.015577
4 days 7.3 0.026802 14.9 19.78 26.6 5.8 0.019936
21 days 10.4 0.029441 11.6 16.7 24.4 5.3 0.015597

MM3 — at 150 °C, no CO2

Original 5.0 0.018564 15.5 5.3 6.9 1.5 0.00926
21 days 5.5 0.023079 17.0 7.0 9.5 2.0 0.013587

Table 4
Mesopore (based on nitrogen adsorption) and micropore (based on CO2 adsorption) characteristics on M1 and M3 samples kept at 150 °C with CO2 adsorbed. Sa — surface area.

Nitrogen adsorption CO2 adsorption

Sample BET sa BJH volume Ave mesop. size BET sa D–R msa D–R mon cap D–A mic vol
and time m2/g cm3/g nm m2/g m2/g cm3/g cm3/g

MM1 — at 150 °C, CO2 adsorbed

Original 7.38 0.021628 12.2 15.5 22.4 4.9 0.015577
3 days 9.1 0.024400 11.0 16.8 24.1 5.3 0.017850
7 days 8.5 0.024943 11.9 17.0 24.4 5.4 0.016870
14 days 10.2 0.025508 10.3 16.8 24.0 5.3 0.016860
28 days 10.9 0.028889 10.2 17.3 24.8 5.4 0.018579
42 days 11.0 0.027137 10.2 24.6 27.2 5.9 0.012249

MM3 — at 150 °C, CO2 adsorbed

Original 5.00 0.018564 15.5 5.3 6.9 1.5 0.009260
21 days 6.7 0.022018 13.4 9.1 9.4 2.1 0.006433

atmosphere prior to the heating experiment. This interpretation is

A considered unlikely, however, because our previous experiments on
BJH mesopore volume (cm3/g)

coal indicated that if any porosity changes occurred as a result of CO2

0.035 adsorption, they remained unchanged after a period of one month
R² = 0.67 (Mastalerz et al., 2008).
0.030

0.025
3.3. Influence of CO2 on shale mineralogy and pore structure at high
0.002 pressure
0.015
The strongest indicators of matrix response to the CO2 in the high
0.010 pressure experiments were the observed changes in the brine chemistry
0 10 20 30 40 50
after the experiments. The measured concentrations of Mg, Ca, and K in
Time (in days)
the filtrate were used to calculate the concentrations of these elements
Carbon dioxide adsorbed No carbon dioxide in the brine after 21 days of heating of MM3 are they are shown in Figure
4A. The concentration of Mg and Ca tended to increase with an increase
B in pressure, while the K concentration was relatively constant. The
D-A micropore volume (cm3/g)

0.035
concentration of ferrous iron (not graphed) was occasionally elevated.
In general, the data show tremendous variability (scatter) that cannot
0.030 be explained without more observational data. The CO2 quantities
were sufficient to ensure, at least for the highest quantities, that a
0.025 separate CO2 liquid phase was present during the 21 days at elevated
temperatures. Some of the CO2 would dissolve in the aqueous
0.002
phase (up to about 0.08 g at the highest pressure), resulting in
0.015 lowered pH and possible dissolution of carbonate/pyrite and
dissolution/ion exchange with clay minerals. At the end of the
0.010 reaction period (see Materials and methods), the sample was
0 10 20 30 40 50
cooled and the CO2 pressure released to the atmosphere. This
Time (in days)
process creates the possibility of degassing of the aqueous phase,
Carbon dioxide adsorbed No carbon dioxide
as well as release of CO2 gas/liquid. The combination of cooling
and degassing creates opportunities for re-precipitation of dis-
Fig. 3. A — BJH mesopore volume of MM1 sample kept at 150 °C without CO2 and with solved components. The cooling and degassing steps are probably
CO2 adsorbed into the sample. Increase in mesopore volume with time is similar for the
sample with and without CO2 added. B — Dubinin–Astakhov (D–A) micropore volume
responsible for much of the scatter in element concentrations
with time for sample MM1 kept at temperature of 150 °C without CO2 and with shown in Fig. 4A; sampling at the experimental pressure was not
adsorbed CO2. possible with the available reaction vessels.
 R. Lahann et al. / International Journal of Coal Geology 108 (2013) 2–9 7

A Mg Ca K
A
10000
Filtrate (ppm)

Etch pits
1000

100
0.0 500 1000 1500 2000 2500 3000 3500

CO2 pressure (psi - calculated)

B
10000
Filtrate (ppm)

1000

B
Backscatter mineralization 200 µm
100
0 500 1000 1500 2000 2500 3000 3500
CO2 pressure (psi - calculated)

Ca-MM1 Mg-MM1 K-MM1 Ca-MM3 Mg-MM3 K-MM3 Ca-MM4 Mg-MM4 K-MM4

C
10000
Filtrate (ppm)

1000

100
0 500 1000 1500 2000 2500 3000 3500 4000
CO2 pressure (psi - calculated)
Ca-powder Mg-powder K-poder Ca-chip Mg-chip K-chip
Fig. 5. A — SEM image of carbonate mineralized biogenic structure. Note the
well-developed etch pits especially at the lower right. B — SEM image of carbonate
Fig. 4. A — Plot of log cation concentration in brine after heating with CO2 versus CO2
mineralized biogenic structures. The inset image at the upper right was taken in
pressure for MM3 powder samples. 1 psi = 0.006895 MPa; B — plot of log cation
back-scatter mode. The light colored areas in the inset image indicate carbonate
concentration in brine after heating with CO2 against CO2 pressure for MM3, MM1, and
mineralization.
MM4 powder samples. 1 psi = 0.006895 MPa; C — plot of log cation concentration in
brine after heating with CO2 against CO2 pressure for MM3 powder and chip samples.
1 psi = 0.006895 MPa. The data in Fig. 4C contrast the MM3 powder data with filtrate data
from experiments that employed a single chip of MM3, rather than a
Fig. 4B shows a comparison of the filtrate analyses for the MM1 powder. As noted previously for the MM3 powder, the Ca concentra-
and MM4 shales with the MM3 shale. The Mg and K concentrations tion was greater than the Mg concentration, which was greater than
are similar for the three shales while the Ca values for MM3 and MM4 the K concentration. As noted for the MM3 powder, the Ca/Mg ratio
are similar and slightly higher than for MM1. The Ca/Mg ratio for the for the chip was greater than can be accounted for by dolomite
MM1 filtrates averaged 1.9, roughly the expected ratio for dolomite dissolution. The Mg and Ca concentrations observed for the chip
dissolution; the Ca/Mg ratio for the MM3 samples averaged 3.4 and experiments were lower than for the powder experiments. We
the MM4 samples averaged 4.1. The latter two values are considerably interpret the lower concentration to be due to increased reaction rate
richer in Ca than appropriate for dolomite. The MM3 and MM4 in the powder experiments due to increased surface area, relative to
samples may have contained some calcite that contributed to the Ca the low permeability rock chip.
concentration in the filtrate. Relative reaction rates for calcite and The X-ray diffraction patterns show some changes in mineral
dolomite under the experimental conditions are not known; the content with the addition of CO2. However, the results of this analysis
difference in dolomite/calcite abundance in the solid was too small to indicate no clear pattern of removal or addition of specific mineral
be detected by XRD. phases with the addition of CO2. This result is most likely due to the
8 R. Lahann et al. / International Journal of Coal Geology 108 (2013) 2–9

limited solubility of components in the brine relative to the abundance buffered by reactions with silicate phases/oxide/carbonate phases.
of those phases in the shale sample. Based on the volume of brine The buffering reactions could include feldspar weathering, hydro-
present in the experiment, an assumption of 2000 ppm Ca in the brine nium ion exchange with clay minerals, and clay mineral dissolution/
and 1200 ppm Mg (appropriate for dolomite dissolution and consistent alteration, all of which release cations from mineral phases into the
with experimental results) indicates that dissolution of only 1 mg of solution and thus buffer the hydronium content of the solution.
dolomite would produce the dissolved components. Removal of 1 mg of These reactions are discussed in more detail in Busch et al. (2008).
material from a 2000 mg sample (2 g of shale) would not be The rise in pH (with time) may be associated with precipitation of
recognizable using X-ray diffraction methodologies. carbonate or other phases in the porosity system (Xu et al., 2010).
SEM studies provide a set of observations that confirm reaction Even though some experiments on the changes in permeability
occurring in the shale during CO2 exposure. Examination of numerous in response to injected CO2 were conducted (Wollenweber et al.,
dolomitic structures visible with the SEM on the sample surface of an 2010), the net effect of phase dissolution/reprecipitation on per-
MM3 chip from the 3500 psi experiment showed clear evidence of meability is, however, not known.
etching by the CO2-rich solution in high-pressure environment Etching of the carbonates demonstrated in this study raises the
(Fig. 5A). Similar circular ferroan dolomite structures were noted in question as to what extent this phenomenon can increase the storage
untreated chips (Fig. 5B) but without any evidence of etching. The capacity of organic-matter bearing shales. Although, samples with
inset in Fig. 5B shows the same field of view as the larger view in B, but high carbonate content were not available in this study, comparing
with the image captured in back-scatter SEM mode. The light-colored the effects of the carbonate dissolution between the organic-rich and
areas indicate elements of higher atomic weight, relative to the darker organic-lean shales with high carbonate contents could help to
shale matrix. Elemental ratios captured in the back-scatter mode address this issue.
indicate that the light-colored material is a ferroan dolomite/ankerite. The New Albany Shale is somewhat unique compared to many
While there were changes in brine chemistry and in the texture silicate reservoirs because of the abundance of relatively unreactive
of dolomitic structures in response to the presence of CO2 at high illite (when contrasted with other clay minerals such as kaolinite or
pressure, no distinct changes have been observed in mesopore and montmorillonite; see Busch et al., 2008 and Xu et al., 2010).
micropore characteristics (Table 5). Similar to the low pressure Additionally, the abundance of organic matter in the New Albany
experiments, the BJH mesopore volume does not change with pres- Shale will make adsorption a more important mechanism than for
sure, and the differences between samples reflect the mesopore many siliciclastic reservoirs (Strąpoć et al., 2010). CO2 adsorption onto
volume differences of the original samples (Fig. 6A). No differences organic matter would likely act as a pH buffer similar to silicate
are observed in micropore surface area with increase in pressure dissolution. However, the long-term CO2 balance and reservoir
(Fig. 6B). performance implications of acid-soluble dolomite and high CO2
adsorption onto organic matter are not known.

3.4. Implications for storage of CO2

4. Conclusions
The brine chemistry and SEM images documented in this study
indicate that one of the first responses to injection of CO2 into a New 1. Low CO2-pressure studies indicate that heating CO2-saturated
Albany Shale reservoir will be carbonate dissolution, of either ankerite/ shales does not change the porosity structure relative to heating
ferroan dolomite, calcite, or a mixture of both. Similarly, Kaszuba et al. shales in distilled water or brine only (native state) environment,
(2005) reported magnesite dissolution to be an early reaction in hydro- probably due to the small amount of CO2 present in these
thermal experiments using shales and Kharaka et al. (2006) reported experiments.
dissolution of carbonate and iron oxide following CO2 injection. With 2. High CO2-pressure studies indicate that carbonate minerals enter
time, the initially low pH of the environment that forms as a result solution when contacted by CO2-enriched fluids. Ca and Mg
of the CO2 interacting with the formation brine is expected to be concentrations in filtrate fluids generally increase with the

Table 5
Mesopore (based on nitrogen adsorption) and micropore (based on CO2 adsorption) characteristics on M1, M3 and M4 samples with CO2 added. Pressure was calculated based on
the amount of dry ice used in the experiment. Sa — surface area.

Pressure Nitrogen adsorption CO2 adsorption

MPa
BET sa BJH volume Ave mesop. size BET sa D–R msa D–R mon cap D–A mic vol
m2/g cm3/g nm m2/g m2/g cm3/g cm3/g

MM1
0 7.3 0.021628 12.2 15.5 22.4 4.9 0.015577
6.9 11.3 0.024770 9.1 16.5 23.8 5.2 0.018098
17.2 9.5 0.024590 10.7 16.0 23.0 5.0 0.016847
24.1 9.6 0.022947 9.9 15.5 22.4 4.9 0.016447

MM3
0 5.0 0.018564 15.5 5.3 6.9 1.5 0.009260
4.1 5.5 0.017396 13.0 6.1 7.9 1.7 0.011818
6.9 7.0 0.022296 13.0 8.5 10.1 2.2 0.015628
6.9 5.3 0.018487 14.1 5.7 7.6 1.7 0.009181
17.2 5.0 0.017500 13.0 10.5 10.5 2.3 0.025179
24.1 5.9 0.019300 13.4 6.3 8.4 1.9 0.009853
24.1 5.7 0.018300 13.5 9.8 13.4 2.9 0.016319

MM4
0 4.3 0.014749 14.4 9.9 13.2 2.9 0.015003
6.9 4.6 0.014364 12.9 10.2 13.7 3.0 0.017617
24.1 4.6 0.014364 12.89 9.8 13.4 2.9 0.015998
 R. Lahann et al. / International Journal of Coal Geology 108 (2013) 2–9 9

BJH mesopore volume (cm3/g) A Smith in the Geochemistry Section of the IGS. We thank the Indiana
M1 M3 M4 Geological Survey Review Committee and Nancy Hasenmueller for
0.030 help with stratigraphic position of the samples.
0.025

0.020
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