International Journal of Coal Geology 277 (2023) 104340

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International Journal of Coal Geology

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

Subcritical CO2 adsorption on geomaterials of coal-bearing strata in the

context of geological carbon sequestration
Maram Almolliyeh a, *, Snehasis Tripathy a, Sivachidambaram Sadasivam a, Shakil Masum a,
Sara Edwards Rassner b, Andy Mitchell c, Hywel Rhys Thomas a
a
Geoenvironmental Research Centre (GRC), School of Engineering, Cardiff University, The Queen's Buildings, The Parade, Cardiff CF24 3AA, United Kingdom
b
Department of Life Sciences, IBERS Building, Aberystwyth University, Aberystwyth SY23 3FG, United Kingdom
c
Department of Geography and Earth Sciences, Llandinam Building, Aberystwyth University, Aberystwyth SY23 3DB, United Kingdom

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

Keywords: This paper explores the adsorption behaviour of geomaterials in the framework of CO2 sequestration in shallow
CO2 Adsorption level coal seams. Manometric adsorption experiments were carried out on two anthracite coal samples, two rock
Coal seam samples from East Irish Sea, MX80-bentonite, Speswhite kaolinite, dry, wet and biofilm-laden (Bascillus moja­
Caprock
vensis-laden) sand at subcritical pressure range (up to 6.4 MPa) of isothermal condition at 298.15 K. The ex­
Biofilm
periments were aimed to investigate the influence of the biogeological conditions of coal and caprock
Water
CO2 sequestration in geological formations constitutions on CO2 adsorption. At lower pressures, the moisture had an influence on the CO2 adsorption on coal
CCS resulted in reduced adsorption capacity. At elevated pressures, the volume expulsion behaviour and coal-water
CCUS interaction had an influence on the adsorption capacities of moist coal sample and resulted in comparable
adsorption capacities to dry sample. The disparity in the adsorption capacities between the wet powdered and
wet intact core samples showed that the results obtained with powder samples may not reflect the field con­
ditions. Wet conditions and Bascillus mojavensis bacteria influenced the adsorption capacity of sand and showed
CO2 chemisorption capacity. The desorption isotherm pattern of wet and biofilm sand showed that the CO2 was
continuously adsorbed independent of the gas phase pressure. Among the clay minerals, bentonite had greater
affinity towards CO2. Despite the fact that the adsorption capacity of the cap rock is smaller than that of the coal
samples, the experimental investigation with constituents of the cap rock provides insights into the effect of
biogeological conditions of coal and rock sample constituents on CO2 storage in coal seams.

1. Introduction higher the amount of polar functional groups such as OH− , carboxyl
(COOH), methoxy (-OCH3), and carboxyl (C=O) groups present in coal,
CO2 adsorption capacity and kinetics are associated with coal rank, the more hydrophilic it is (Mahajan and Walker, 1971; Allardice and
moisture content, swelling characteristics, porosity, temperature, and Evans, 1971; Nishino, 2001; Qi and LeVan, 2005; Miura et al., 2001;
operating pressures (White et al., 2005). The biogeological conditions of Kadioǧlu and Varamaz, 2003). The carbon-containing groups
coal and adjacent caprock have also had an impact on the coal seams' mentioned above decompose and increase the fixed carbon content of
CO2 sequestration potential. The adsorption capacity was suppressed in high-rank anthracite coal while decreasing its hydrophilicity (Stach
the presence of moisture for low-rank coals, and the experimental results et al., 1982; Allardice and Evans, 1971; Murata et al., 2000; Allardice
showed that CO2 prefers the H2O sites (competing with water) (Day et al., 2003; Charrière and Behra, 2010), which would reflect on the CO2
et al., 2008; Ozdemir and Schroeder, 2009; Pone et al., 2009). There is a adsorption capacity. The CO2 can interact with adsorbed water on coal
scarcity of data on the adsorption of CO2 on wet intact coal samples and raise the carbonic acid content, dissolve alkaline (Ca, Na, K, and
apart from the studies conducted on constructed coal samples or mois­ Mg-containing) minerals from the coal, and induce CO2 mineralisation
ture equilibrated powdered samples (Zhang et al., 2019; Wang et al., as CaCO3 (Massarotto et al., 2010).
2017), which may not represent the field conditions. Water molecules The rock strata above the coal seam serve as a caprock system for the
form hydrogen bonds with the functional groups on the coal surface. The CO2 reservoir in the coal seam. Testing the integrity of the caprock and

* Corresponding author.
E-mail address: [email protected] (M. Almolliyeh).

https://doi.org/10.1016/j.coal.2023.104340
Received 9 March 2023; Received in revised form 20 August 2023; Accepted 20 August 2023
Available online 22 August 2023
0166-5162/© 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
M. Almolliyeh et al. International Journal of Coal Geology 277 (2023) 104340

associated minerals will be necessary for mitigating the level of risk in Table 1
CO2 injection in coal seams. The CO2 gas can permeate, trapped in the Proximate and ultimate analysis of the coal samples from 9 ft. and 18 ft.
porous structure of the rock, chemically interact with water, and adsorb Aberpergwm.
on the rock minerals. CO2 can be captured in the caprock system through Analytical 18 ft. Aberpergwm 9 ft. Aberpergwm
a variety of mechanisms, including structural trapping, residual trap­ Coal Coal
ping, solubility trapping, mineral trapping, and adsorption (Depaolo and Proximate analysis
Cole, 2013). Sandstone and mudstone formations dominate the rock Water Content % 0.78 0.91
strata above the coal seams. Sandstone is primarily composed of quartz, Ash Content mass 1.38 4.62
Volatiles content % 5.08 5.73
with trace amounts of clays (e.g., kaolinite and bentonite). In conse­
mass
quence, studying the CO2 adsorption capacity of sand (quartz) and clays %
would advance our understanding of CO2 sequestration in un-minable mass
coal seams (Wang et al., 2003; Yang and Yang, 2011; Botan et al., Calorimetry
2010; McGrail et al., 2009; Kwak et al., 2011; Loring et al., 2011; Shao High calorific value Mj/kg 35.04 35.60
Low calorific value Mj/kg 34.30 32.89
et al., 2011; Tokunaga and Wan, 2013; Chen and Lu, 2015; Jeon et al., Ultimate analysis
2014; Wensink et al., 2000; Rahaman et al., 2008; Malani and Ayappa, Total Carbon % 92.05 89.5
2009; Kerisit et al., 2012). Total sulphur mass 0.73 0.87
Microbial activities have also been reported in rock strata and in­ Sulphur combustion % 0.01 0.25
Sulphur after full mass
fluence the fate and transport mechanism of CO2 at potential geological
combustion % 0.72 0.62
carbon sequestration (GCS) sites (Morozova et al., 2010; Lavalleur and Combustible sulphur mass 92.05 89.5
Colwell, 2013; Peet et al., 2015). Supercritical CO2 is used as a disin­ Total hydrogen % 3.31 3.16
fectant against microorganisms (Dai et al., 2016). Yet, biofilms formed Nitrogen mass 1.27 1.31
by Bacillus mojavensis bacteria are able to withstand supercritical CO2. Oxygen 0.5 0.33
%
Bacillus mojavensis is a commonly found microorganism in the sandstone
mass
cores from coal field and can withstand high-pressure conditions %
(Kamihira et al., 1987; Enomoto et al., 1997; Zhang et al., 2006; Mitchell mass
et al., 2009). Previous studies indicate that Bacillus mojavensis are %
mass
capable of resisting CO2 exposure than many other bacteria (Mitchell
%
et al., 2008). This finding highlights the importance of conducting mass
additional experiments on Bacillus mojavensis biofilm-loaded sand sam­ Petrography
ples at various pressure ranges to examine the impact of the biogeo­ Vitrinite reflectance % Vol 2.72 2.84
chemical nature of the rock strata on CO2 adsorption capacity. Vitrinite content % Vol 86 86
Liptynite (egsynite) % Vol 0 0
In this work, two high-rank anthracite coals, two rock samples from
Inertynite % Vol 14 14
East Irish Sea, dry, wet and biofilm loaded sand, kaolinite and bentonite Mineral matter content % Vol 0 0
samples were investigated for their CO2 adsorption capacity to improve As received
our understanding of CO2 adsorption in coal seams under field Transient moisture % 0.84 0.65
content mass 1.61 1.56
conditions.
Total moisture % 1.37 4.59
Ash content mass 5.04 5.69
2. Materials and methods Volatile matter content % 0.72 0.86
Total sulphur content mass 33.99 32.66
2.1. Materials Low calorific value %
mass
%
The adsorption experiments were carried out on two coal samples mass
and caprock constituents. The two anthracite coal samples were ob­ Mj/kg
tained from the Aberpergwm coal mine (51◦ 44′28.8”N 3◦ 38′36.0”W), Dry state
Ash % 1.39 4.66
Wales, UK and referred as to 9 ft. AB and 18 ft. AB with natural water
Total sulphur mass 0.74 0.88
content of 0.91% and 0.78%, respectively. Commercially available %
MX80 bentonite, Speswhite kaolinite and sand samples were used in the mass
CO2 adsorption experiments. The supplementary section contains x-ray Daf state
diffraction (XRD) mineralogical identifications of clay minerals. The Volatile matter content % 5.19 6.07
High calorific value mass 33.82 35.57
British Geological Survey (BGS) provided the two rock core samples
%
from the East Irish Sea that measured 2.54 cm in diameter referred as to mass
R1 and R2. The Proximate and ultimate analysis of the coal samples and
the properties of geomaterials have been provided in Table 1. Fig. 1
shows the representative examples of the materials used in the study. diffraction patterns clearly show that The rock samples are primarily
composed of quartz (SiO2, primary peaks 2Ɵ = 26.64◦ , 20.86◦ and
2.2. Geological settings and properties of the coal and rock samples 50.13◦ ), ankerite (dolomite with iron substitution, Ca (Mg0.67Fe0.3)
(CO3)2, primary peak 2Ɵ = 30.81◦ ) and showed peaks attributes for
The 9 ft. coal samples were procured from the depth of 550 and the halite (primary peaks at 2Ɵ = 31.69◦ , 45.45◦ ), kaolinite (major peak at
18 ft. coal seam is located at 500 m. The strata consist of sandstone, 2Ɵ = 12.28◦ ) and orthoclase (major peak at 2Ɵ = 25.65◦ ).
siltstone, mudstone, and coal seams from the Carboniferous period and The chemical composition of the rock samples obtained from an x-
dip between 25 and 45◦ to the south and southwest. The detailed ray fluorescence spectrometer is shown in Table 2. The compositions of
geological settings and baseline geochemistry of the coal seams provided major oxides (SiO2, Al2O3, CaO, FeO, K2O, and TiO2) confirm the
by Sadasivam et al. (2019). The properties of coal seams are found in mineralogical identification of the rock samples by XRD. Quartz (SiO2 =
Table 1. 50%–89% SiO2) is the predominant constituent of the rock samples,
The X-ray diffraction (XRD) patterns of East Irish Sea rock samples followed by iron (1.3% to 6.6%) and calcium (3.4%–25%) containing
collected from different depths are displayed in Fig. 2. The X-ray minerals (Table 2).

2
M. Almolliyeh et al. International Journal of Coal Geology 277 (2023) 104340

Fig. 1. (a) Intact coal core, (b) powdered coal, (c) dry sand, MX-80 m bentonite and kaolinite and (d) East Irish Sea rock samples (R1 and R2) and wet sand and
biofilm loaded sand.

Clearly, the overburden would contain a range of minerals, partic­ left in the cells for minimum of 21 days to attain saturation equilibrium
ularly carbonate minerals (Fig. 2; Table 2), which are ubiquitous in under 1 MPa pressure. The saturation pressure was chosen to maintain
sedimentary rocks and react more rapidly than silicates. Ankerite (which the water pressure above 0.1 MPa to saturate the microfractures (Zhang
contains Fe) is the most common carbonate mineral after calcite, dolo­ et al., 2022). Moist powder coal samples were prepared as described in
mite, and siderite. CO2-laden groundwater can dissolve iron and previous literatures (ASTM D1412–072007; Krooss et al., 2002; Wang
calcium-containing minerals such as ankerite (Doner and Lynn, 1989). et al., 2017, Mukherjee and Misra, 2018). The resulted water content of
intact 9 ft. AB sample was about 2.34%, intact 18 ft. AB was about 4.07%
2.3. Methods and powder samples of 18 ft. AB was about 1.2%. Adsorption experi­
ments were conducted on samples of water equilibrated and samples
2.3.1. Preparation of wet intact and powdered coal samples with natural water content to compare the effect of water on CO2
Intact samples were drilled from the large coal blocks using a core adsorption.
drill with a 5 cm internal diameter diamond core bit for the adsorption
experiments. The core samples were saturated with water using an
oedometer to prepare moist coal samples (Fig. 3). The core samples were

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M. Almolliyeh et al. International Journal of Coal Geology 277 (2023) 104340

Counts

Quartz, syn
1600

Ankerite
900

Quartz, syn
Quartz, syn

Quartz, syn
Halite, syn

Quartz, syn
Quartz, syn
Halite, syn

Ankerite
Quartz, syn

Quartz, syn
Quartz, syn
Quartz, syn

Quartz, syn
400

Quartz, syn

Quartz, syn
Ankerite
Ankerite

Ankerite
100

0
10 20 30 40 50 60 70
Position [°2Theta]

Counts
Quartz, low

Quartz, low; Ankerite; Orthoclase

Quartz, low; Orthoclase
Quartz, low

1600
Ankerite; Orthoclase

Quartz, low; Orthoclase

Quartz, low; Orthoclase

Ankerite
Quartz, low; Ankerite
Halite, syn; Orthoclase

Quartz, low

Quartz, low; Ankerite

Quartz, low

lowlow
Quartz, low

low;
Quartz,
Quartz, low

Quartz,
Quartz,
400

0
10 20 30 40 50 60 70
Position [°2Theta]

Fig. 2. X-ray diffraction patterns of X-ray diffraction (XRD) patterns of powdered East Irish Sea rock samples (depth of the samples indicated): (a) R1; 4064 m to
4065 m, (b) R2; 8379 m to 8379.57 m.

Bacillus mojavensis grown in Nutrient Broth E was added to the sand

Table 2
samples. The biofilm loading was developed in syringe sand columns
Chemical composition of the rock samples (values are within ±5% error).
(Fig. 4). Each sand column was filled with 50 mL of fine sand. Prior to
Rock sample SiO2% Al2O3% CaO FeO K2O TiO2% % biofilm loading, the sand was heated to 150 ◦ C for 1 h in order to kill any
core number % % % mass
bacteria present in the sand. The assembly is designed for single-pass
(depth in m)/
% composition flow of medium, nutrient solution, and deionised water (Milli-Q
Water). The fluids were introduced into the system using a Watson-
R1 (4064 to 63.26 1.17 20.25 4.92 9.05 1.33 99.98
4065 m)
Marlow pump 205S multichannel pump (8 channels). To flush the sys­
R2 (6499 to 80.73 0.42 9.54 1.18 1.67 0.34 93.87 tem, autoclaved deionised water was run through the sand columns
6500 m) overnight.
Bacillus mojavensis starter culture was prepared and left to grow
overnight at 30 ◦ C (optimum temperature to grow the culture). To grow
2.3.2. Dry, Wet sand and biofilm-laden (Bacillus mojavensis) sand sample
the biofilm, six syringe columns were prepared, one of which served as a
preparation
control. Four millilitres of the prepared Bacillus mojavensis culture was
The sand samples were dried at 105 ◦ C for 24 h and referred as to dry
injected and pushed into the sand column at a rate of 4.17 mL/min. The
sand. To avoid microbial growth, a dried portion of sand was equili­
pump flow rate was then reduced to 0.056 mL/min to pump 60 mL of
brated with water and stored in a freezer. One day prior to the adsorp­
fluid media to allow the bacteria to attach and form a biofilm on the
tion tests, the samples were transferred to a refrigerator. These samples
sand.
were designated as wet sand samples.
Following biofilm loading, the liquid was drained and sand portions

Fig. 3. Schematic for intact coal saturation procedure using oedometer.

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M. Almolliyeh et al. International Journal of Coal Geology 277 (2023) 104340

Fig. 4. (a) Schematic and (b) Photographs of the syringe sand columns with single-pass flow system for loading biofilm (Bacillus mojavensis grown in Nutrient
Broth E).

were transferred to sterile 50 mL Falcon tubes and stored in a freezer 2.3.3. Adsorption experiment
prior to adsorption experiments. The samples were taken out of the Fig. 5 illustrates a simplified schematic of the volumetric/mano­
freezer 24 h prior to the adsorption experiments. metric adsorption experimental setup. The apparatus is made up of a gas
supply, an adsorption apparatus with a reference cell (RC), a sample cell

Fig. 5. (a) Schematic illustration of the volumetric/manometric experimental setup, (b) known amount of CO2 prepared in Reference Cell (RC) and (c) CO2 expanded
into Sample cell (SC) and allowed to reach equilibrium.

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M. Almolliyeh et al. International Journal of Coal Geology 277 (2023) 104340

(SC), and pressure transducers for measuring the gas phase pressure in
pCO 2

the adsorption cell. The entire setup is contained within a thermostat (2)
eq
nCO
e
2
= vd
RTZ(p,v)
(water bath) to maintain a constant temperature of 298.15 K (Fig. 5). A
known mass (ms) of adsorbent is placed in the sample cell that has been
nCO2 − nCO2 nCO 2 − nCO2
vacuum degassed to remove any trapped gas in the sample. A known nCO 2
ad =
t e
adsorption; nCO 2
de =
e e
desorption (3)
ms ms
quantity (nt) of gas (CO2) is injected into the RC, expanded into the SC,
and adsorbed on the adsorbent. Not all gas molecules are adsorbed and a
where nCOt
2
is the known amount present in the gas phase at the begin­
small amount of gas remains in the gas phase at equilibrium. The
ning of the adsorption experiment (mol), nCO 2
is number of moles of CO2
amount adsorbed is the difference between the amount of gas in the gas e

phase (ne) and the known amount (nt) of gas (CO2) injected into the RC at equilibrium stage (mol), nCO
ad/de is amount of CO2 adsorbed over known
2

(Keller and Staudt, 2005; Myers and Monson, 2014). The experiments mass of adsorbent (mol/kg) during adsorption/desorption, vd is void
were carried out at pressure step-up stages ranges from 0.5 MPa to 6.5 volume available for gas, (vd is sample cell volume with sample loaded +
MPa at isothermal conditions (298.15 K). The adsorbed amount is reference cell volume), pCO2 is pressure of CO2 at the beginning of each
arithmatically added to calculate the cumulative amount of CO2 experimental stage, pCO
eq is equilibrium pressure of CO2 (Pa) measured in
2

adsorbed at each pressure step up stages. The desorption pressure step- RC + SC, R is gas constant 8.314 (J/mol.K), T is temperature (298.15 K)
down experiments were carrried out to claculate the amount of CO2 and Z-is compressibility factor of CO2. The compressibility factor (Z) was
released from the adsorbed phase. The amount adsorbed during the determined using the Peng-Robinson equation of state (Elliott and Lira,
adsorption and desorption experiments were calculated for each gas 2012). The experimental results were fit into isotherm models (Lang­
equilibrium stages as follow. muir and Brunauer-Emmer-Teller [BET]) and psudeo-first-order (PFO)
pCO2 and psudeo second-order (PSO) kinetic models (Langmuir, 1915, 1916,
nCO
t
2
= vd (1) 1917, 1918; Brunauer et al., 1938; Guo et al., 2017; Hu et al., 2020).
RTZ(p,v)
To substantiate the influence of the physical and chemical nature of

Fig. 6. Adsorption isotherms of (a) 9 ft. AB (0.9%, 2.35% water content), (b) 18 ft. AB (0.78% and 4.07% water content), (c) powdered 18 ft. AB (0.78% and 1.2%)
and (d) adsorption-desorption isotherms of 18 ft. AB powder (0.78% and 1.2%).

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M. Almolliyeh et al. International Journal of Coal Geology 277 (2023) 104340

water on adsorption of coal samples, water retention characteristic

curves, pH buffering of coal and evidence of the presence of bioflim on
coal were also obtained. Procedure of these experiments are detailed in
the supplimentary section.

3. Results and discussions

3.1. CO2 adsorption on moist coal samples

The CO2 adsorption isotherms of intact samples of 9 ft. AB coal with

water content of 0.91% and 2.35%, respectively, are depicted in Fig. 6a.
When the adsorption isotherms were compared, a marginal increase in
CO2 adsorption was observed for the sample with greater moisture
content at the higher-pressure range. At an equilibrium pressure of 3.6
MPa, adsorption capacity of the sample with 2.35% water content was
about 79 g/kg (1.8 mol CO2/kg), whereas the sample with lower
moisture content (0.91%) showed about 70.42 (1.6 mol CO2/kg). In
contrast, the wet sample (2.35% water content) had a lower adsorption
capacity than dry samples (0.91% water content) at equilibrium pres­
sures below 2 MPa. This is likely due to the water content affecting bulk
pore diffusion, the primary mode of adsorption mechanism at low
pressures. The adsorption isotherm patterns of 18 ft. AB intact samples
are presented in Fig. 6b. The sample showed an increased adsorption
capacity than the sample with a much lower water content of 0.78% at
elevated pressures of 3.6 MPa. The 18 ft. AB sample with 4.07% water
content showed an adsorption capacity of 70.42 g/kg (1.6 mol of CO2/
kg) of coal and 0.78% water content exhibited an adsorption capacity of
48.41 g/kg (1.1 mol of CO2/kg) of coal (Fig. 6b). Fig. 7. Signs of residual water after CO2 adsorption test on intact 18 ft. coal - a)
At increased pressures, the increased adsorption capacity of wet at the bottom on the adsorption cell, b) at the bottom of the sample core (insert
samples can be attributed to complex mechanisms such as CO2 adsorp­ show the SEM images of nanosized fractures).
tion at water activated sites by expelling the adsorbed water (Day et al.,
2008; Sun et al., 2016a) and mineralisation of CO2. The observations capacity grew. Powdered samples of 18 ft. AB with 0.78% water content
made during the adsorption experiments with wet samples are repre­ adsorbed 66.02 g/kg (1.5 mol of CO2/kg) of coal, while samples with
sented in Fig. 7. After completing the adsorption-desorption tests on wet 1.2% water content had an adsorption capacity of 44.41 (1.1 mol of
intact 18 ft. AB with water content 4.07%, the sample cell's bottom was CO2/kg) of coal at 3.5 MPa, showing a 33% reduction in adsorption
found to be wet (Fig. 7a). The possible reason of water expulsion from capacity (Fig. 6c). This pattern reflects the findings of Wang et al.
the coal structure is that CO2 can diffuse/dissolve into capillary water to (2011), who found that the amount of adsorbed CO2 on wet coal samples
access the coal matrix interior, causing the water molecules to desorb was reduced by 69% when compared to dry powdered samples. The
from the surfaces of nano, micro and mesopores (Fig. 7b - insert shows trends observed for the powdered samples (Fig. 6c) is expected as the
the image of nanosized pores and micro cleats found in the anthracite adsorbed water forms hydrogen bonds with the polar functional group
coal). This volume expulsion behaviour was previously reported in a and carbon-containing groups of coal structure (Mahajan and Walker,
study of CO2 gas-water exchange experiments performed at pressures up 1971; Allardice and Evans, 1971; Nishino, 2001; Kadioǧlu and Varamaz,
to 4.5 MPa and temperatures up to 298.15 K (Sun et al., 2016a), which 2003; Qi and LeVan, 2005; Miura et al., 2001). By pulverising the coal
are similar to the parameters set up in the current investigation. With samples, these polarisation sites are exposed for water to absorb. Since
increasing CO2 pressure, water molecules shift their contact angle and H2O molecules have a high heat of adsorption, it is difficult for CO2 to
distribution, which in turn affects their adsorption capacity. Coal sur­ replace the water molecules adsorbed on the polarised sites on the coal
faces become hydrophobic, and the arrangements of water molecules surface of the powdered samples (Day et al., 2008). This shows the effect
are altered due to the increased H+ ion by CO2's solubility. H2O's of the pulverising the sample on adsorption capacity which may not
interaction with coal weakens as the energy of van der Waals dispersive represent the field conditions (Almolliyeh et al., 2023).
forces grows (Sun et al., 2018, 2022; Wiebe and Gaddy, 1940; Ibrahim Fig. 6d depicts the CO2 adsorption-desorption isotherms of powdered
and Nasr-El-Din, 2016). The present study's finding of enhanced samples of 18 ft. AB coal with 0.78% and 1.2% water content. The
adsorption is consistent with these prior findings. isotherm patterns displayed the type II adsorption isotherm and H3
The intact wet samples of both 9 ft. AB and 18 ft. AB anthracite coals hysteresis pattern described by International Union of Pure and Applied
had comparable isotherm patterns (Fig. 6a and b). However, the Chemistry (IUPAC) (Sing et al., 1985; Thommes et al., 2015). The
marginally enhanced adsorption capacity seen above 1 MPa equilibrium adsorption-desorption isotherm of sample with 0.78% water content
pressures with 9 ft. AB samples is correlated with the sample's low showed clear hysteresis by exhibiting a positive deviation. The sample
carbon content (89.5%) in comparison to 18 ft. AB (92.05%). The low with 1.2% water content did not exhibit the substantial positive devia­
carbon content coals contain higher polarised sites with functional and tion at higher pressure (> 2 MPa). The reason for this could be that in
carbon containing groups where CO2 and water molecules generally wet samples, CO2 must compete with water molecules at activated sites
prefer to adsorb (Mahajan and Walker, 1971; Allardice and Evans, 1971; and be easily released from weakly adsorbed external sites at higher
Nishino, 2001; Kadioǧlu and Varamaz, 2003; Qi and LeVan, 2005; Miura pressures (> 2 MPa). The CO2 molecules adsorbing inside the narrow
et al., 2001; Day et al., 2008). pores were not ready for desorption at lower pressure range (< 2 MPa)
Fig. 6c compares the isotherm patterns of powdered 18 ft. AB coal and reflected as hysteresis in the isotherm (Fig. 6d).
samples with 0.78% and 1.2% water content. The adsorption capacity of The calculated amount of CO2 remain adsorbed at zero equilibrium
the dry powdered sample was significantly greater than that of the wet pressure set up during desorption is referred to as residual CO2. When
samples. When the pressure was increased, the disparity in adsorption

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M. Almolliyeh et al. International Journal of Coal Geology 277 (2023) 104340

the residual amount of CO2 on the powdered dry sample (0.78% water long-term sequestration of CO2 within coal deposits.
content) of 18 ft. AB coal was compared to the wet sample (1.2% water The chemical conditions of the retained water at high pressures can
content) of 18 ft. AB coal, the dry sample had 1.18 mol/kg of coal react with CO2 and induce inorganic/biomineralization of CO2. CO2
retained at the end of desorption while the wet sample had 0.65 mol/kg reduces the water-wettability of coal and, as pressure increases, in­
coal retained in the coal. These findings support the discussion of less creases CO2 solubility in water. This induces a low pH and the dissolu­
amount of CO2 enter the nano/micropores that has been occupied by the tion of inorganic salts, which destabilises the double layer surrounding
water. the coal surface and renders it hydrophobic, thereby increasing CO2
At lower and intermediate pressures (< 6.1 MPa), there was good adsorption. The phenomenon of wettability in CO2-coal-water is inde­
agreement between experimental adsorption isotherms of intact samples pendent of coal rank (Ibrahim and Nasr-El-Din, 2016; Tokunaga and
and Langmuir model results (Figs. 6b and c). The experimental results Wan, 2013; Sun et al., 2022).
deviated from the model to show the high-density adsorption build-up at The inorganic mineralisation phenomenon can be understood by the
high pressures (from 6.1 MPa to 6.4 MPa). This was evident in the intact pH buffering capacity of the coal samples. The Fig. 8b shows the pH of
samples of 18 ft. AB (0.78% water content) where high density CO2 the water samples were increased after equilibrating with coal because
adsorption occurs within microfractures of intact coal (Figs. 6b) and fit of the mineral dissolution. The concentrations of cations released from
very well with the BET model. However, at a similar pressure range, the the coal during the equilibration indicate the possible dissolution of
experimental results of the powdered samples of 18 ft. AB with 0.78% alkali minerals (example, dissolution of calcium increases alkalinity)
and 1.2% water contents were in good agreement with the Langmuir from the coal surface. For example, carbonic acid (H2 CO3 ) causes the
model, indicating that water molecules adsorb on the exposed hydro­ pH 5.8 of the deionised water. After equilibrating with coal, the pH rises
philic sites and prevent the high-density CO2 adsorption (Fig. 6c), to 6.56 (Table 3). The measured cations concentration for the corre­
showing the influence of sample fabric and water. The BET model did sponding coal-water mix confirms the alkali mineral dissolution
not fit well with the powder samples of dry and wet 18 ft. AB (Fig. 6c). It (Table 3) is the reason for the pH neutralisation. The dissolution of alkali
is likely that the adsorbed water on the large surface area available for minerals from coal was previously studied by Massarotto et al. (2010).
water molecules cannot be easily displaced by gas molecules, preventing Their results were similar to that obtained in this study. This clearly
the CO2 access to the pores to form high dense layers. For a dry sample of suggests that the released alkali minerals from the coal, particularly
18 ft. AB (Fig. 6c), the lower density adsorbed phase on large, exposed calcium, would interact with H2CO3 to precipitate as CaCO3 and influ­
surface area reflected on the isotherm and fitted better with the Lang­ ence the CO2 retention behaviour on coal.
muir model than that of BET, signifying the influence of sample fabric
(Almolliyeh et al., 2023). 3.1.2. Biofilm on coal surface
It has been hypothesized that surface biofilms on coal samples could
3.1.1. Water-coal interaction trigger the biomineralization of carbon dioxide. The scanning electron
The resulted adsorption capacities may not be occurred only by the microscope images of coal samples are shown in Fig. 9. Fig. 9a shows
physical gas adsorption on coal surface. Other factors such as physi­ evidence of some biofilm on the surface cracks of the coal sample and
ochemical nature of water and biological conditions might have greater naturally occurring bacteria can be seen. These images clearly show the
influence. The water wettability and capillary phenomena must be presence of intact rod-shaped bacteria growing on small chunks of coal
widely investigated for the water-coal-CO2 system. The Fig. 8a shows Fig. 9b. These bacteria likely belong to the genus Bacillus, which is often
the water holding capacity of the two coal samples (9 ft. AB intact and found in coal seams (Mitchell et al., 2008, 2009). To identify the bacteria
powder) at varying suction condition. According to Allardice et al. found on the natural coal sample, the images were compared with SEM
(2003), it has been observed that anthracite coals exhibit a lower degree images of coal samples with laboratory grown Bacillus mojavensis. Bac­
of hydrophilicity compared to bituminous coal. The hydrophobic char­ teria was grown on the 9 ft. AB coal using laboratory procedure
acteristics of anthracite coals are evident in their diminished water described in supplementary section. The scanning electron microscope
retention capacity. The investigation of the water retention character­ images of the laboratory grown Bacillus mojavensis on 9 ft. AB coal
istics of coal contributes to the advancement of knowledge regarding the sample is shown in Fig. 9c. The morphology of the bacteria in each set of

Fig. 8. (a) Water retention characteristics and (b) pH buffering capacity of 9 ft. AB coal.

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M. Almolliyeh et al. International Journal of Coal Geology 277 (2023) 104340

Table 3
pH buffering capacity of 9 ft. Aberpergwm coal.
Initial pH pH Ca Na K Mg Mn B Ba
after 24 h (mg/g of coal) (mg/g of coal) (mg/g of coal) (mg/g of coal) (mg/g of coal) (mg/g of coal) (mg/g of coal)

2.73 6.96 0.031 0.005 0.013 0.005 0.0004 0.0002 0.00009

3.69 7.6 0.018 0.004 0.01 0.002 0.0002 0.0002 0.00002
4.26 7.4 0.019 0.005 0.011 0.003 0.0002 0.0002 0.00036
5.8 6.56* 0.02 0.004 0.004 0.007 0.0003 0.0002 0.00001
11.85 11.26 0.001 ** 0.012 0 0 0.0001 0.0002

* Natural pH with DI water, **NaOH is used for adjusting the pH.

Fig. 9. Scanning electron photomicrographs of intact 9 ft Aberpergwm coal showing a) sign of biofilm on the surface cracks, b) rod-shaped species, similar to that of
the genus Bacillus, and c) scanning electron photomicrographs of the laboratory grown bacteria on 9 ft Aberpergwm coal.

images were near-identical (Fig. 8). The typical length of Bacillus reaction and forming secondary carbonate minerals (Montegrossi et al.,
mojavensis cells is 2 μm to 4 μm and a width of 0.5 μm to 1 μm (Roberts 2022). This may be the possible reason that the rock sample R1 had a
et al., 1994). Bacillus mojavensis are commonly present in these types of higher adsorption capacity compared to the rock sample R2.
samples and have been identified in previous works as particularly Previous experiments in the subcritical range of CO2 showed 3.18 g/
resilient to high pressure CO2 (Mitchell et al., 2008, 2009). kg (0.07 mol CO2/kg) sandstone at 1 MPa equilibrium pressure and
21.18 g/kg (0.48 mol CO2/kg) sandstone at 2 MPa equilibrium pressure
(Tajnik et al., 2013), with the adsorption isotherm fitting very well to the
3.2. CO2 adsorption isotherms of caprock constituents
Langmuir-type (monolayer) model (Jedli et al., 2016). Fakher and
Imqam (2020) found that shale rocks could adsorb 16.72 g/kg (0.38 mol
3.2.1. East Irish Sea rock samples
of CO2/kg) of rock using a volumetric adsorption setup very similar to
The manometric adsorption experiments were performed only on
the one used in this study. More relevant to the coal seam context, the
two rock samples due to the longer period to attain equilibrium for intact
manometric adsorption experiments conducted with a carboniferous
undisturbed samples. However, it has been previously documented in
black shale from a depth of 745 m containing coal-associated sediments
literatures that manometric set up can be used to measure the CO2
showed an adsorption capacity of 7.7 g of CO2/kg of coal (Khosrokhavar
adsorption capacity more accurately (Khosrokhavar et al., 2014). The
et al., 2014). The leakage scenario must be site-specific, and the minerals
East Irish Sea rock sample R1 (CaO = 20.25% and FeO = 4.9%) and R2
from the overburden must be studied for their adsorption capacity. The
(CaO = 9.54% and FeO = 1.18%) were chosen for adsorption experi­
adsorption capacity of sandstone rock samples, predominantly found
ments due to their differences in calcium and iron content. The CO2
above the coal seams focused on in the current study, to adsorb CO2
adsorption isotherm pattern of the East Irish Sea rock samples is
varied with depth, clay content, mineral composition, water content,
depicted in Fig. 10a. The rock sample R1 had a low adsorption capacity
and biofilm content (Botan et al., 2010; McGrail et al., 2009; Kwak et al.,
of 4.4 g/kg of rock (0.1 mol of CO2/kg) up to an equilibrium pressure of
2011; Loring et al., 2011; Shao et al., 2011; Tokunaga and Wan, 2013;
2 MPa and which increased to 39.61 g/kg (0.9 mol of CO2/kg) of rock at
Kamihira et al., 1987; Enomoto et al., 1997; Zhang et al., 2006). Sepa­
an equilibrium pressure of 3.5 MPa (Fig. 10a). The rock sample R2 had a
rate adsorption experiments were conducted on sand (dry, wet, and
lower adsorption capacity of 1.23 g/kg (0.028 mol of CO2/kg) of rock
biofilm loaded), MX80 bentonite and Speswhite kaolinite samples to
compared to R1 (Fig. 10a). When the pressure was increased, a clear
understand the adsorption behaviour of each mineral constituent in the
Langmuir type isotherm pattern was observed. The CO2 interaction with
sandstone, and the results are discussed in the subsequent section.
shale containing carbonate and pyrite minerals undergo dissolution

9
M. Almolliyeh et al. International Journal of Coal Geology 277 (2023) 104340

Fig. 10. (a) CO2 adsorption isotherms of rock samples, (b) adsorption isotherms of clays, (c) dry sand, wet sand and sand with bacteria, and (d) adsorption-
desorption isotherms of wet sand and sand with bacteria.

3.2.2. CO2 adsorption on clay minerals, dry sand, wet sand, and sand maximum adsorption capacity was approximately 0.15 mol CO2/kg of
loaded with Bacillus mojavensis kaolinite, while Chen and Lu (2015) reported that Georgia kaolinite's
Fig. 10b shows the CO2 adsorption isotherm pattern of MX80 maximum adsorption capacity was 0.3 mol CO2/kg of kaolinite. The
bentonite and Speswhite kaolin. At an equilibrium pressure of 3.59 MPa, reported values were comparable to the current study's adsorption ca­
MX80 bentonite had a maximum CO2 adsorption capacity of 24.65 g/kg pacity value.
(0.56 mol/kg (Fig. 10b). Jeon et al. (2014) reported a comparable Bacillus mojavensis bacteria are native to sandstone rock strata and
adsorption capacity of about 26.41 (0.6 mol of CO2/kg) of bentonite at could affect the interaction of CO2 with caprock (Mitchell et al., 2008;
an equilibrium pressure of 3.5 MPa. Previous studies reported an Mitchell et al., 2009; Peet et al., 2015). The Bacillus mojavensis type
adsorption capacity ranging from 0.16 to 0.25 mol of CO2/kg of Na- strain grows well in the CO2-water-rock environment. The biofilms
bentonite at equilibrium pressures (3.5 MPa) (Volzone, 2006). Previ­ formed by Bacillus mojavensis are resilient to high-pressure CO2 and can
ous studies have shown CO2 molecules can penetrate the interlayer enhance the solubility trapping, mineralisation of CO2 through ure­
spacing of swelling clays (bentonite) and expand the basal spacing olysis, and CaCO3 precipitation. CO2 gas adsorption tests were per­
(Okolo et al., 2019; Loring et al., 2012; Ilton et al., 2012; Schaef et al., formed on Bacillus mojavensis loaded sand samples and compared to the
2012). However, non-polar fluids such as CO2 cannot simply replace the dry and wet sand samples.
cations and expel the interlayer water but diffuse into the water to reach Fig. 10c shows the CO2 adsorption and desorption isotherm patterns
the interlayer space of the expanding clay minerals such as bentonite. of dry sand, sand with water, sand with Nutrient Broth E and sand with
The CO2 adsorption mechanism on kaolinite was ascribed to CO2 mol­ bacteria, respectively. Dry sand showed a slightly reduced adsorption
ecules adsorbing on the intragranular porosity and was characterised as capacity (0.16 mol/kg) at a maximum equilibrium pressure of 3.5 MPa
physical sorption (Chen and Lu, 2015; Hu et al., 2019). Speswhite kaolin (Fig. 10c) than wet samples. Wet sand had a maximum adsorption ca­
exhibited a maximum adsorption capacity of 8.36 g/kg (0.19 mol of pacity of about 0.2 mol of CO2/kg (Fig. 10c). A control adsorption test
CO2/kg) of kaolinite at an equilibrium pressure range of 3.51 MPa was performed using Nutrient Broth E-loaded sand that had been used to
(Fig. 10b). Volzone (2006) reported that the kaolinite mineral's grow Bacillus mojavensis bacteria and results are presented in the

10
M. Almolliyeh et al. International Journal of Coal Geology 277 (2023) 104340

supplementary section. deviated from the model and increased linearly, indicating that more
The maximum adsorption capacity of biofilm-loaded sand samples than one adsorption mechanism influences CO2 adsorption on biofilm-
was 9.24 g/kg (0.21 mol /kg) (Fig. 10c). In comparison, the adsorption loaded sand.
capacities of wet and biofilm-loaded sand samples were comparable The Langmuir maximum adsorption capacities of the sand samples
(Fig. 10c). The dry sand showed lower capacity of 9.04 g/kg (0.16 mol/ were approximately 7.37 g of CO2/ kg of dry sand, 10.08 g of CO2/ kg of
kg). The dry sand reached equilibrium around 2 MPa in the isotherm wet sand, and 10.08 g of CO2/ kg of Bacillus mojavensis loaded sand. The
patterns shown in Fig. 10c, whereas the wet sand and biofilm-loaded Langmuir pressures (b) were about 5.39 × 10− 6 Pa− 1 for dry sand, 1.14
sand showed a linear increase with pressure increase up to 3.5 MPa × 10− 6 Pa− 1 for dry sand, 9.69 × 10− 7 Pa− 1 for dry sand (Table 4). While
and 4 MPa equilibrium pressures, respectively. the current study only examined a restricted number of samples, the
Interestingly, the desorption pattern for Bacillus mojavensis-loaded adsorption capacities of various rock types, including sandstone (3.2 g of
sand demonstrated no discernible CO2 gas desorption upon decreasing CO2/kg of coal), claystone-sandstone (11 g of CO2/kg of coal), siltstone
equilibrium pressure (Fig. 10d). on other hand, it displayed an (12.4 g of CO2/kg), siltstone, and limestone (1.6 g of CO2/kg), extracted
increasing amount of CO2 adsorbed. This behaviour demonstrates from the overburden of a coal mine in Slovenia (Tajnik et al., 2013),
definitively that a significant portion of the 0.21 mol/kg biofilm-loaded were found to be similar to the findings reported in the current study
sand may have been mineralized/chemisorbed, and that mineralisation (refer to Table 4). In a study conducted by Zhang et al. (2018), it was
or chemisorption occurs regardless of pressure. The adsorption- observed that the adsorption of CO2 on quartz crystals followed a
desorption experiment lasted 12 days in total and yielded an adsorp­ Langmuir-type adsorption behaviour. Furthermore, molecular simula­
tion capacity of 17.6 g/kg (0.4 mol of CO2) per kg of biofilm-coated sand tions performed by Carchini et al. (2020) demonstrated that the
specimen (Fig. 10d). A similar pattern was observed for sand with water adsorption of CO2 on the quartz surface is of a physical nature. In a
(Fig. 10d) showed adsorption rather than desorption during the pressure simulation study (Yang et al., 2022), the energy of physical adsorption
step down desorption stages, indicating that water/biofilms may on the sand was given as 22 kJ/mol, which is comparable to the
enhance solubility trapping of CO2 (Mitchell et al., 2010). While dry adsorption energy calculated in the current study (29.8 kJ/mol for the
sand contains a limited number of activated sites within the quartz dry sand: Table 4).
nanopores, wet sand retains the CO2 at the water activated hydrophilic
sites in the quartz and fills the nanopores with increased density (Sun 3.3. Limitations and uncertainties
et al., 2016b).
The current study's sample size is not exhaustive, and sample sizes
3.2.3. Evaluation of CO2 adsorption on rocks and clays using the Langmuir may cause uncertainty in the study's results. Biological effects, for
model example, are very small, and such small effects cannot be statistically
The Langmuir model was used to fit equilibrium CO2 adsorption data represented by small samples. As a result, geomaterials with varying
obtained with dry sand, wet sand, sand with biofilm, MX80 bentonite biogeochemical conditions are proposed to provide a comprehensive
and Speswhite kaolin (Langmuir, 1916, 1917, 1918). Figs. 10b represent data set. However, the current study's samples were chosen to mimic the
the Langmuir adsorption isotherm model compared with experimental similar coal bearing strata of the coal samples chosen from and relevant.
isotherms for MX80 bentonite and Speswhite kaolin. The experimental The adsorption pressure data deviating from the pressure measurement
data of MX80 bentonite and Speswhite kaolin fit the Langmuir model transducers were plotted against a secondary transducer fitted in the
very well (Fig. 10b). The Langmuir maximum adsorption capacity of measurement cell with a ± 15 Pa deviation uncertainty for any experi­
MX80 bentonite was about 28.62 g/kg, and the Langmuir pressure b ment conducted up to 6.5 MPa for the validity and data acceptance of
(half-loading pressure) was approximately 1.5 × 10− 6 Pa− 1 (Table 4). the smaller sample size. The adsorption capacity data yielded in this
For a half-loading pressure of 4.53 × 10− 6 Pa− 1, the Langmuir maximum study were comparable to previously documented research.
adsorption capacity of the Speswhite kaolinite was approximately 8.64
g/kg of kaolinite (Table 4). The adsorption energy of MX80 bentonite 3.4. Implications for current knowledge of geological CO2 sequestration
was − 23.31 kJ/mol and that of Speswhite kaolinite was − 29.02 kJ/mol
(Table 4). One of the goals of CO2 sequestration in geological formations is to
Figs. 10c depict the experimental data fitted to the Langmuir model retrofit existing and decommissioned coal mines/coal seams as CO2
for dry sand, wet sand and sand with biofilm, respectively. The experi­ storage units with the possibility of extracting coal bed methane (CBM).
mental data for dry sand agrees very well with the model, indicating that Recent developments in CO2 sequestration in coal seams have focused
the sand has a limited number of available sites for CO2 gas molecules on the operational and technical feasibility of new potential engineering
and that the sites are saturated at around 2 MPa equilibrium pressure. practises such as horizontal well injection to improve CO2-coal contact
Wet sand and Bacillus mojavensis-loaded sand, on the other hand, area and injectivity (ROCCS Project, 2023). Laboratory-measured
adsorption capacity can be used to determine the potential of these
engineering practises. The current study's findings have an impact on
Table 4 current research focused on European coal seams by feeding adsorption
Langmuir parameters and energy of adsorption obtained for dry, wet, Bacillus capacity data of geomaterials to large-scale ex-situ experiments and in-
mojavensis loaded sand, MX80 bentonite and Speswhite kaolin. situ pilot-scale studies testing the CO2-CBM.
Sample Langmuir Langmuir maximum ΔHad ΔG0ad
description pressure b adsorption capacity, kJ/mol (kJ/ 4. Conclusions
(Pa− 1) m∞, g of CO2/kg of coal mol)

Dry sand 5.39 × 10− 6 7.37 − 29.84 − 30.07 This work comprehensively presented the CO2 adsorption on geo­
Sand with 1.14 × 10− 6 10.08 − 25.21 − 33.93 materials in the perspective of CO2 storage in coal seams. Wet coal
water samples of intact samples showed lower adsorption capacity than the
Sand with 9.67 × 10− 7 10.08 − 24.81 − 34.32
lower moisture content sample at lower pressure range of the subcritical
Bacillus
mojavensis region (<1 MPa). At elevated pressures (up to 6.4 MPa) the comparable
MX80 1.5 × 10− 6 28.62 − 23.31 − 33.24 adsorption capacity of the wet and dry samples was attributed to the
bentonite volume expulsion, water mineralisation and biomineralization of CO2.
Speswhite 4.53 × 10− 6 8.64 − 29.02 − 34.02 However, the wet powdered samples showed lower adsorption capacity
kaolin
as the water molecules at the exposed hydrophilic sites were not easily

11
M. Almolliyeh et al. International Journal of Coal Geology 277 (2023) 104340

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