Energy Procedia 4 (2011) 32243230

Energy
Procedia
www.elsevier.com/locate/procedia

Energy Procedia 00 (2010) 000000

www.elsevier.com/locate/XXX

GHGT-10

Environmental Consequences of Potential Leaks of CO2 in Soil

Yang Weia,1*, Mercedes Maroto-Valera, Michael D Stevenb
a
Centre for Innovation in Carbon Capture and Storage (CICCS)
Fuels & Power Technology Research Division Faculty of Engineering
University of Nottingham
University Park, Nottingham, NG7 2RD, United Kingdom
b
School of Geography, University of Nottingham, Nottingham NG7 2RD

Elsevier use only: Received date here; revised date here; accepted date here

Abstract
Carbon Capture and Storage (CCS) is expected to make a key contribution to the mitigation of climate change as a safe and
effective short-term way to reduce the atmospheric emissions of CO2 produced by human activity. However, during the CCS
process, there is a small possibility of leakage via pipeline transportation, through abandoned wells near the storage place or
through natural pathways such as fractures and faults in the host formation. The stored gas may contain impurities that are more
toxic and dangerous than pure CO2, potentially causing more serious environmental issues. Therefore, it is critical to assess the
potential risks caused by CO2 leakage to ensure public acceptance of CCS as safe and reliable strategy for global warming
mitigation.
With 100% CO2 incubation in a pressure reactor, a direct correlation was found between the soil moisture and the uptake of CO 2
during the process. Small changes in CaCl 2-exchangeable metal concentration were observed after CO2 incubation, for example
increases in Mg, K, Al, Cr, Mn, Fe, Pb, while there were decreases in Zn and Cd. However, the mobilised metal concentrations
remained below plant tolerance levels.
Further research will investigate the potential environmental consequences (on soil and plants) of leaks of impure CO 2, focusing
on the effects of controlled exposure to different concentrations of CO2/SO2 mixtures in a new continuous flow reactor.
c 2010

2011 Published
by Elsevier
Ltd.
Open access under CC BY-NC-ND license.

Elsevier Ltd.
All rights
reserved
Keyword: CCS; CO2 Leakage; Environmental Impacts; Soil;

1. Introduction
Cleaner use of fossil fuels, supplemented by Carbon Capture and Storage (CCS) techniques is considered to be
one of the main short-term contenders for addressing the global climate change problem and is expected to make a
key contribution to mitigation of global anthropogenic CO2 emissions [1, 2]. In order to progress to large scale
application, it is essential to assess all the potential risks and provide evidence to inform governments and the public
that potential impacts are well controlled.

* Yang Wei. Tel.: +44 (0)115 95 15383; fax: +44 (0)115 951 5249.
E-mail address: lgxyw2@nottingham.ac.uk

doi:10.1016/j.egypro.2011.02.239

Y. Wei et al. / Energy Procedia 4 (2011) 32243230

Wei, Y., M. Maroto-Valer, and M.D. Steven/ Energy Procedia 00 (2010) 000000

3225

A major risk related to carbon dioxide transportation is pipeline failure, which could be caused by third party
interference, acidic gas corrosion, construction or material faults such as welds or other operator errors [3, 4].
During geological storage, there is potential for leakage of gas through failure of well or cap-rock integrity.
Unexpected seismic events such as faulting could also cause leakage. Among all these pathways, injection wells and
abandoned wells are considered as one of the most probable migration pathways for CO 2 storage projects [5]. Any
leakage could cause CO2 release back to the atmosphere and have relevant environmental impacts.
Since the first reports relating to potential environmental impacts in 2003 [5], further research has examined the
effects of CO2 leakage on natural ecosystems as well as natural analogues such as the CO2 gas venting test site at
Latera, Italy, near a volcanic area and soil acidification caused by long-term climate change or acid deposition [6-8].
It is reported that soil pH decreases with elevation of CO2 concentration in the soil. Noticeable but non-significant
changes in mineralogy such as K-feldspar, quartz, and mica were found, together with changes in trace elements
like As and Cr [7-9]. Moreover, there are changes in Cation Exchange Capacity (CEC), and the presence of oxides
like CaO, MgO, Fe2O3, and Mn3O4 in some experiments [10-12]. Leakage of CO2 may also cause changes of
groundwater taste, colour or smell, reduce groundwater pH and cause significant deterioration in the quality of
potable groundwater by altering groundwater chemistry [6, 13]. CO2 leakage rising to sub-soil levels may also cause
changes in subsurface microbial populations either by favouring species or restricting them, depending on species
and site characteristics [14, 15].
The effects found in these studies are slightly different from each other, which may be due to different soil
characteristics. The overall tendency in surface and subsurface soil chemistry changes with CO2 leakage is not very
clear and the effects of chronic (long-term, low level) exposure for both surface and subsurface terrestrial
ecosystems is poorly characterised [6, 9]. Also, most research to date has focused on the impacts of pure CO2 on the
ecosystem. However, even after purification during carbon capture, the captured flue gas may still contain up to 7%
vol. H2O and 0.9% vol. N2 and 0-1.5% vol. SO2, which could have serious environmental impacts in a leak scenario
[16, 17]. Therefore, it is also important to assess impacts on soil geochemistry due to various concentrations of
impurities in the CO2 stream.
The research reported here focuses on the effects on soil of pure CO2, to study the potential influence on soil and
plants caused by leakage.
2. Methodology
2.1

Experimental study- Stage I

2.1.1
Sampling site description
All the soils used are from an untreated area of the ASGARD field facility, located at the Sutton Bonington
Campus, University of Nottingham. The main purpose of this facility is to observe and monitor the effects of the
elevated soil CO2 concentrations caused by a CCS leak on various crops and plants, soil microbes/invertebrates and
soil geochemistry [7]. The site was previously used as a sheep pasture and has remain grassland for over 10 years.
The soil is mainly sandy loam incorporating some red clay of the Mercia Mudstone Group.
2.1.2
Soil sample preparation
When sampling, all the plants and grass above the soil surface were removed and the soil extracted from various
depths. For this study, only the topsoil (8 to 12 cm depth) was used. After collection from the site, the soils were
oven-dried at 40C then gently crushed by hand and sieved through a 2000m sieve to remove large roots and rock
fragments, vegetable matter, and other particles larger than 2 mm in size. Later, the soils were mixed by a raffle
splitter. The prepared samples were stored in clean plastic zip-lock bags for the following experiments and analysis.
2.1.3
Investigation process
2.1.3.1 High Pressure/ High Temperature Reactor for carbon sequestration
The prepared soil samples were put into a high pressure/ high temperature Parr reactor model 4843 (Figure 1),
and then incubated with CO2. The gas was injected into the reactor up to the required pressure.

3226

Y. Wei et al. / Energy Procedia 4 (2011) 32243230

Wei, Y., M. Maroto-Valer, and M.D. Steven/ Energy Procedia 00 (2010) 000000

Figure 1 High pressure-high temperature experimental set-up in the laboratory

2.1.3.2 Incubation condition
Although a gas leak in the natural environment would be close to ambient pressure and temperature, higher
temperature and pressure were applied in these experiments to speed up the reaction process. The parameters were
selected to keep CO2 as gas phase. The experiments were therefore run at 25qC with a pressure of 25 bars for 3 days.
In the following analysis, the reacted samples are numbered as follows.
No.
S1
S2
S3
S4
S5
S6
S7
S8
S9
S10

Top-soil
Top-soil
Top-soil
Top-soil
Top-soil
Top-soil
Top-soil
Top-soil
Top-soil
Top-soil

DESCRIPTION
no incubation
oven-dried and incubated
oven-dried and incubated
oven-dried and incubated
16.7% moisture content and incubated
16.7% moisture content and incubated
16.7% moisture content and incubated
28.6% moisture content and incubated
28.6% moisture content and incubated
28.6% moisture content and incubated

2.1.4
Analysis methods
2.1.4.1 Soil characterisation
Before the incubation, X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) were used to define
the characterization of crystalline materials in soil and the morphology of soils.
2.1.4.2 Soil pH
Before and after the incubation in the reactor, two levels of 2 ml scoops of soil was collected and placed in the
sample container, mixed with up to 10ml deionised water, and the soil pH was determined by a pH electrode.
2.1.4.3 Exchangeable metals
In order to determine small changes in metal concentration caused by carbonic acid (H2CO3), the exchangeable
fraction of metals in pore water was extracted with 0.01M CaCl 2 extraction solution [18-20], and determined by
ICP/MS. First, a 5.0g soil was weighted and placed into a centrifuge tube. Then, 25ml 0.01M CaCl2 was added into
the centrifuge tube and the tube was shaken overnight by machine. Later, the solution was centrifuged at 3700
rev./min for 10 minutes and filtered into a test tube. 100l 50% Nitric Acid was added into each solution to keep the
metal concentrations stable. Then the solution was ready for ICP/MS.

Y. Wei et al. / Energy Procedia 4 (2011) 32243230

Wei, Y., M. Maroto-Valer, and M.D. Steven/ Energy Procedia 00 (2010) 000000

3227

3. Results and discussion

3.1

Soil characterisation

The soil (8cm-12cm depth) from ASGARD field contains 8.91% clay, 22.89% silt and 68.2% sand. The main
component of the soil is quartz, which is over 90% of the dry weight. The soil contains minor amounts of
anorthoclase, albite, dolomite and kaolinite, illite|mica and montmorillonite.
3.2

Pressure record

There was a slow leakage of gas from the reactor during the incubation process. To compensate for this, a blank
sample was run and used to correct the pressure change. The original data are shown in Figure 2 and the corrected
pressure drop during incubation is shown in Figure 3, normalised to absolute pressure, Pdiff/P. The data show that
CO2 is taken up by soil over the time of incubation, with a greater pressure drop occurring with more moisture in the
soil. The absorption of CO2 may occur either by reacting with pore water in the soils or through filling in voids
between soil particles. Each of the trendlines in the graph is associated with different moisture contents measured in
three replicate incubations with 100% CO2. The rate of pressure drop decreases with time, which implies that the
uptake of CO2 is slowing down as incubation goes on. However, this change is reasonably well compensated by the
pressure normalisation. The greater pressure drop with wet soil can be explained as more CO2 is absorbed by the
pore water within soils to form H2CO3 in soil solution.

Figure 2 Pressure change during CO2 incubation

3.3

Figure 3 Change in pressure difference (relative to

blank) normalised to actual pressure

Metal concentration

ICP/MS was done for the non-incubated soil, S1, and incubated soil samples, S5, S6, S7, S8, S9, and S10. The
results shows an increase with incubation of several CaCl2-exchangable metal concentrations in soil solution: Mg,
K, Al, Ti, V, Cr, Mn, Fe, Co, Cu, Rb, Sr, Mo, Cs, Ba, Pb, Th, and U all increase, while the metal Zn and Cd
concentrations decrease. Other trace elements do not show a regular trend. Figure 4 shows the differences in soil
solution concentrations for four metals: Al, Mn, Fe, and Cd.
For non-incubated soil S1, the Al concentration within soil solution of S1 is 1.82mg/kg. After 100% CO2 gassing,
the Al concentrations in S5-S7 all increased by an average of 59%, compared to S1. Al concentrations in S8-S10
were approximately 254% higher than S1 and 123% higher than S5-S7. The change suggests that Al is mobilised
and released from soil when CO2 is present, with greater CO2 uptake by pore water and the more Al mobilisation in
moister soils. When CO2 is taken up by pore water, H2CO3 is formed, the pH of soil solution is decreased, and H+ is
present in the soil solution. Soil has a buffering capacity and clay minerals start to weather to neutralize the pH by
releasing minerals to exchange with H+, leading to an increase in the CaCl2-exchangeable concentration of Al.
However, the concentration of Al found in this study is still much lower than plant tolerance limits, which are up to
40M-60M depending on species [21, 22].

3228

Y. Wei et al. / Energy Procedia 4 (2011) 32243230

Wei, Y., M. Maroto-Valer, and M.D. Steven/ Energy Procedia 00 (2010) 000000

Similar trends can also be observed in Mn concentration changes, but more pronounced, as Mn is more sensitive
to soil acidity [23]. The Mn concentration in S5-S8 increased by 112% compared to S1, with a pressure drop of
around 1 bar; the Mn concentration in S8-S10 increased by 490% compared to S1, with a pressure drop of about 2
bars. These results indicate that the more moisture is contained in the soil, the more CO 2 uptake during the
incubation, and the more metal mobilised by the soil. There are also small increases in the concentration of Fe, Pb
and Cu. The concentration of these metals all have the highest concentration in S8-S10, and the lowest concentration
in S1, which suggest that these metals are slightly mobilised by CO2 gassing.
The Cd concentration in soil solution shows a different trend from the above metals. On average, the CaCl 2exchangeable Cd concentration decreases after exposure to CO2. The concentration in S8-S10 is 20% below S1 and
in S5-S7 it is 10% below S1. However these differences are insignificant. For all the soils, the pH is within the range
5.5-6.8. According to previous work [23, 24], a significant increase in Cd concentration appears when pH is below
5.0. When pH decreases from neutral to 5.5, it appears that the mobilised Cd will be absorbed onto ion exchange
surfaces and/or complexed with soil organic matter, which leads to the decrease in CaCl2-exchangeable Cd.
Apart from the elements mentioned above, no significant trends were observed for CaCl 2-exchangeable metals.

Figure 4 Concentrations of CaCl2-exchangeable metals of different incubated soils

4. Conclusions and future work
When soil was exposed to 100% CO2, the gas is absorbed either by the soil pore water leading to the weathering
of clay minerals in the soil, or by filling in voids between soil particles. For soils with different moisture levels,
greater moisture in the soil results in higher CO2 uptake during the incubation. For sandy soils, small changes in
CaCl2-exchangeable metal concentration are observed after CO2 incubation. CaCl2-exchangable metal
concentrations in soil solution increase for Mg, K, Al, Ti, V, Cr, Mn, Fe, Co, Cu, Rb, Sr, Mo, Cs, Ba, Pb, Th and U,
while the metal concentrations decrease for Zn and Cd. Other trace elements do not show a regular trend. Although
changes were seen after exposing to CO2, the concentration of these elements is still below plant tolerance limits. In
the future it is proposed to test the effects of impure CO2 with up to 1% SO2 in the mixture to assess the potential
impacts caused by impurities.

Y. Wei et al. / Energy Procedia 4 (2011) 32243230

Wei, Y., M. Maroto-Valer, and M.D. Steven/ Energy Procedia 00 (2010) 000000

3229

For these experiments, a temperature of 25qC and 25bars pressure were utilised to speed up reactions and give
guidance for future work. In order to simulate a more realistic environment, a continuous flow reactor is currently
being designed. The main structure of the system is represented by a vertical Plexiglas column, which will be filled
with pre-mixed soils of different compositions. During the process, soil pore water will be collected and analysed to
assess the metal concentration mobilised by acid soil condition. Also, moisture content, soil pH and flow rate and
concentrations of the gas mixture at inlet and outlet, as well as gas concentrations at different depths in the soil core
will be measured via sampling points during gassing.

Acknowledgment
We thank the EPSRC for sponsorship via CICCS (EPSRC, EP/F012098/1). Thanks also to Dr. Giorgio Caramanna
for useful comments on this paper. YW thanks her family and friends for giving her their support.

References
[1] Pacala, S. and R. Socolow, Stabilization Wedges: Solving the Climate Problem for the Next 50 Years with
Current Technologies. Science, 2004. 305(5686): p. 968-72.
[2] Van der Zwaan, B. and K. Smekens, CO2 Capture and Storage with Leakage in an Energy-Climate Model.
Environmental Modeling & Assessment, 2009. 14(2): p. 135-48.
[3] Koornneef, J., et al., Uncertainties in Risk Assessment of CO2 Pipelines. Energy Procedia, 2009. 1(1): p. 158794.
[4] Gale, J. and J. Davison, Transmission of CO2-Safety and Economic Considerations. Energy, 2004. 29(9-10): p.
1319-28.
[5] Damen, K., A. Faaij, and W. Turkenburg, Health, Safety and Environmental Risks of Underground CO 2 Storage
- Overview of Mechanisms and Current Knowledge. Climatic Change, 2006. 74(1-3): p. 289-318.
[6] Stenhouse, M., R. Arthur, and W. Zhou, Assessing Environmental Impacts from Geological CO2 Storage.
Energy Procedia, 2009. 1(1): p. 1895-1902.
[7] West, J.M., et al., The Impact of Controlled Injection of CO2 on the Soil Ecosystem and Chemistry of an English
Lowland Pasture. Energy Procedia, 2009. 1(1): p. 1863-70.
[8] Beaubien, S.E., et al., The Impact of a Naturally Occurring CO2 Gas Vent on the Shallow Ecosystem and Soil
Chemistry of a Mediterranean Pasture (Latera, Italy). International Journal of Greenhouse Gas Control, 2008. 2(3):
p. 373-87.
[9] Kruger, M., et al., Ecosystem Effects of Elevated CO2 Concentrations on Microbial Populations at a Terrestrial
CO2 Vent at Laacher See, Germany. Energy Procedia, 2009. 1(1): p. 1933-39.
[10] Billett, M.F., et al., FOREST SOIL CHEMICAL-CHANGES BETWEEN 1949/50 AND 1987. Journal of Soil
Science, 1990. 41(1): p. 133-45.
[11] Blake, L., et al., Temporal changes in chemical properties of air-dried stored soils and their interpretation for
long-term experiments. European Journal of Soil Science, 2000. 51(2): p. 345-53.
[12] Goulding, K.W.T., et al., Nitrogen deposition and its contribution to nitrogen cycling and associated soil
processes. New Phytologist, 1998. 139(1): p. 49-58.
[13] Jaffe, P.R., et al., Potential Effect of CO2 Releases from Deep Reservoirs on the Quality of Fresh-Water
Aquifers, in Greenhouse Gas Control Technologies - 6th International Conference. 2003, Pergamon: Oxford. p.
1657-60.
[14] Tian, S., et al., Evaluation of the use of high CO2 concentrations and cold storage to control of Monilinia
fructicola on sweet cherries. Postharvest Biology and Technology, 2001. 22(1): p. 53-60.
[15] Jossi, M., et al., How Elevated pCO2 Modifies Total and Metabolically Active Bacterial Communities in the
Rhizosphere of Two Perennial Grasses Grown under Field Conditions. FEMS Microbiology Ecology, 2006. 55: p.
339-50.

3230

Y. Wei et al. / Energy Procedia 4 (2011) 32243230

Wei, Y., M. Maroto-Valer, and M.D. Steven/ Energy Procedia 00 (2010) 000000

[16] Radosz, M., et al., Flue-Gas Carbon Capture on Carbonaceous Sorbents: Toward a Low-Cost Multifunctional
Carbon Filter for "Green" Energy Producers. Industrial & Engineering Chemistry Research, 2008. 47(10): p. 378394.
[17] Lee, J.-S., et al., Effects of SO2 and NO on growth of Chlorella sp. KR-1. Bioresource Technology, 2002.
82(1): p. 1-4.
[18] Feng, M.-H., et al., A comparison of the rhizosphere-based method with DTPA, EDTA, CaCl2, and NaNO3
extraction methods for prediction of bioavailability of metals in soil to barley. Environmental Pollution, 2005.
137(2): p. 231-40.
[19] Novozamsky, I., T.M. Lexmond, and V.J.G. Houba, A Single Extraction Procedure of Soil for Evaluation of
Uptake of Some Heavy Metals by Plants. International Journal of Environmental Analytical Chemistry, 1993. 51(1):
p. 47-58.
[20] Van Gestel, C.A.M., Physico-chemical and biological parameters determine metal bioavailability in soils.
Science of the Total Environment, 2008. 406(3): p. 385-95.
[21] Poschenrieder, C., et al., A glance into aluminum toxicity and resistance in plants. Science of the Total
Environment, 2008. 400(1-3): p. 356-68.
[22] Taylor, G.J., F.P.C. Blamey, and D.G. Edwards, Antagonistic and synergistic interactions between aluminum
and manganese on growth of Vigna unguiculata at low ionic strength. Physiologia Plantarum, 1998. 104(2): p. 18394.
[23] Blake, L. and K.W.T. Goulding, Effects of atmospheric deposition, soil pH and acidification on heavy metal
contents in soils and vegetation of semi-natural ecosystems at Rothamsted Experimental Station, UK. Plant and Soil,
2002. 240(2): p. 235-51.
[24] Wren, C.D. and G.L. Stephenson, The effect of acidification on the accumulation and toxicity of metals to
freshwater invertebrates. Environmental Pollution, 1991. 71(2-4): p. 205-41.