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ANALYSIS [Link]/ees | Energy & Environmental Science

CO2 capture and storage: are we ready?

Franklin M. Orr, Jr.*
Received 9th December 2008, Accepted 20th February 2009
First published as an Advance Article on the web 13th March 2009
DOI: 10.1039/b822107n

Options for capture and storage of CO2 that would otherwise be released into the atmosphere by
combustion of fossil fuels are considered. This paper assesses whether CO2 can be captured, whether
sufficient potential capacity exists for storage in geologic formations, describes physical mechanisms
that can prevent escape of the CO2 from the subsurface, delineates methods for monitoring the
movement of CO2 in the subsurface and for detecting leaks, and describes field experience with CO2
injection. While much remains to be learned about the design of specific storage projects, the current
state of knowledge of carbon capture and storage is sufficient to permit testing at the scale of large
power plants.
Published on [Link] | doi:10.1039/B822107N

Introduction industrial processes. Improved energy efficiency has the potential

to reduce CO2 emissions relatively rapidly and quite significantly,
Around 86% of world primary energy use is currently based on and often at costs that are more than offset by reduced energy
fossil fuels, coal, petroleum, and natural gas, and energy use is costs. Use of renewable energy resources other than hydroelectric
the dominant contributor to greenhouse gas emissions associated
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generation (wind, solar, biomass, and geothermal, for example)

with human activities. Concentrations of two greenhouse gases is growing rapidly, but from a relatively small base. Given the
associated with energy use have increased significantly: CO2 size of the world’s energy systems, projected growth in energy
concentration in the atmosphere has increased by a third over demand, and the magnitude of investments in energy infra-
preindustrial levels, from about 280 ppm to 385 ppm, and the structure that will be required, it is likely that worldwide tran-
concentration of methane has more than doubled.1 The impact of sitions to large-scale use of those resources will take decades. The
these emissions can already be discerned in global average existing infrastructure for fossil fuels, particularly coal, is so large
temperatures, high latitude ice cover, changes in snow cover, and that it is likely that methods to reduce CO2 emissions from fossil
a decrease in upper ocean pH, among many others, but what fuel use, particularly for electric power generation, will be needed
matters more is the potential impact of future emissions, which in addition to the worldwide effort to substitute primary energy
are currently projected to increase substantially in this century in resources that are not based on fossil carbon.
the absence of significant changes in energy systems. Recent US CO2 emissions account for about a quarter of world
estimates by the Intergovernmental Panel on Climate Change1 emissions, and coal-fired power plants provide about half of
indicate that deep reductions from current CO2 emissions will be electric power generation. Hence, examination of the potential
required by midcentury if we are to stabilize atmospheric role of CCS in the US illustrates many of the issues that will have
concentrations of CO2, even at levels substantially higher than at to be faced. How is CO2 emitted in the US? Fig. 1 shows the CO2
present but low enough to limit predicted global average emissions associated with various sectors of the US economy.
temperature rises to about 2
C. Electric power generation is the largest source of CO2 emissions
The obvious first option for emissions reduction is to make for the US (2.4 billion metric tons, Gt CO2, in 2007, mainly from
more efficient use of energy, in homes, businesses, vehicles, and coal and natural gas2,3), but transportation, at 2 Gt CO2, is
a close second.3 The quantities of CO2 reported for industrial,
residential, and commercial sectors include the CO2 that comes
Global Climate and Energy Project, Stanford University, Yang and Yama
saki Building, Suite 324, 473 Via Ortega, Stanford, California,
from electric power generation.
94305-4230, USA. E-mail: fmorr@[Link].; Fax: +1 650 725 9190; Power plants are large, stationary sources of CO2, which are
Tel: +1 650 725 6270 obvious targets for CO2 capture. though other industrial

Broader context
One option for reducing emissions of CO2 to the atmosphere is the capture and storage of CO2 from carbon combustion reactions or
from industrial sources. Processes to capture CO2 have been demonstrated at commercial scale, though the energy required to
separate the CO2, and therefore the cost, is significant. To have an impact on overall CO2 emissions, large quantities of CO2 will have
to be stored in porous rocks in the deep subsurface: oil and gas reservoirs, deep formations that contain salt water, coal beds, and
possibly basalt formations. Geologic storage of CO2 in oil reservoirs and deep saline formations has also been demonstrated on
a commercial scale. The next important step is to demonstrate the integration of carbon capture and storage at the scale of large
power plants in a variety of geologic settings.

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CO2 emissions, it makes sense to focus on relatively large

stationary sources, where quantities large enough to make
a difference and economies of scale might be available.
One option for reducing emissions is to capture a portion of
the CO2 that would otherwise be emitted and store it in a location
that isolates it from the atmosphere on time scales of centuries to
millennia. Whether carbon capture and storage (CCS) can be
done at large scale in the decade ahead depends on the answers to
questions that include:
 Can we capture the CO2 efficiently and at an acceptable cost?
 Do we have a sufficient variety of geologic settings and
sufficient volume to store enough CO2 to have an impact on
emissions distributed around the globe?
 Are there sufficient physical mechanisms that will trap the
CO2 in the subsurface to allow design of safe storage projects that
will not leak?
 Can the movement of fluids in the subsurface be monitored
Fig. 1 US CO2 emissions by sector.3 Note that the total electric power and leaks be detected and if necessary, remediated?
Published on [Link] | doi:10.1039/B822107N

generation for each sector is also included in the values for that sector.
 Do we have enough experience with actual operations to
Data for 2007 are preliminary.
undertake storage at a scale large enough to have an impact on
processes (petroleum refining, ammonia, cement, and steel, emissions?
production, natural gas cleanup, for example) that emit about 1 This paper offers an assessment of where we stand on these
Gt CO2 in addition to the CO2 from electricity offer opportu- questions.
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nities as well. It is also possible that transportation will make

greater use of electricity (particularly if battery energy density
and durability improve) through plug-in hybrids and electric
CO2 capture
vehicles. Residential and commercial uses (largely for space Fig. 2 shows that a range of options is currently available for CO2
heating with natural gas) each account for about 0.6 Gt CO2 in separation from effluent gases from electric power production or
addition to electricity generation. As a first step towards reducing industrial processes. Any one of several separations can be used

Fig. 2 CO2 capture options (IPCC 2005: IPCC Special Report on Carbon Capture and Storage, prepared by Working Group III of the Intergov-
ernmental Panel on Climate Change, Figure TS.3, Cambridge University Press).4 In post-combustion capture, CO2 is separated from nitrogen and
oxygen in combustion product gases. In pre-combustion capture, oxygen is separated from air for gasification of a fuel, and then CO2 is separate from
hydrogen produced by shift reactions. An alternative is to use the oxygen directly for combustion, with separation of the CO2 by condensing water
present in the combustion products.

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to obtain relatively pure CO2 for storage: CO2 from N2 or from commercial experience in gasification has been gained in the
CH4, O2 from N2, or H2 from CO2. manufacture of hydrogen for use in ammonia synthesis, for
If CO2 is to be separated from some gas stream, the starting example.
point will often be combustion product gases, which typically Because the gasification and shift reactions are often performed
contain from 3–15% CO2 along with nitrogen and traces of other at elevated pressure, the separation can be done with physical
gases. Natural gas combustion turbines produce lower CO2 solvents (selexol or rectisol, for example), and the separated CO2
concentrations (because excess air is used to control tempera- is also captured at an elevated pressure, which reduces the total
tures in the hot section of the turbines). Coal combustion amount and the cost of compression to the pressure required for
generates concentrations at the high end of the range. Other gas transportation and storage compared to that for lower pressure
streams may also provide opportunities. Still higher CO2 separations. Relatively recent cost and efficiency estimates2 indi-
concentrations (15–30%) can occur in cement production, where cate that oxyfuel and IGCC plants could produce electricity with
a fossil fuel is typically burned to convert calcium carbonate to 90% capture of CO2 for about 7.0 and 6.5 cents kWh1, estimated
calcium oxide, which liberates CO2 from the calcium carbonate costs that are slightly lower than similar estimates for pulverized
in addition to the CO2 from combustion. Natural gas sometimes coal plants. It should be noted that construction costs for new
contains CO2 as a contaminant with widely varying concentra- plants rose sharply in 2007 and early 2008 but may have declined
tions. High concentration gas streams are likely to be the early since then due to the worldwide economic downturn. Operation
favorites for CO2 capture because they provide a larger of IGCC plants at full commercial scale with carbon capture and
concentration driving force for CO2 separation. storage has not yet been demonstrated.
Published on [Link] | doi:10.1039/B822107N

Post combustion capture and separation of CO2 from natural The CO2 and O2 separation processes described above are all
gas typically make use of chemisorption, often in solvents such as currently used at commercial scale, though not at the scale that
an ethanolamine. The gas stream is mixed with solvent in would be required for a large power plant (say 500 MW or more).
a contacting tower, the CO2 transfers to the liquid phase, and the Other approaches are being investigated, however. Improved
liquid solution is then separated physically from the remaining solvents, membrane separations, oxygen separation with ion
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gas. Next, the separated solution is heated to recover the CO2, transport membranes and ionic liquids, solid sorbents, and
and the regenerated solvent is then recycled to absorb more CO2 chemical looping are among the methods being developed. The
in the contacting tower. The energy required to move the fluids, solvent-based separations that are currently used are thermo-
recover the CO2, and compress it for transportation by pipeline dynamically relatively inefficient, requiring six or seven times as
to a storage site reduces the energy available for electric power much energy as the minimum based on the chemical potentials of
production. For a subcritical pulverized coal electric power the mixed and separated gases. Thus, there is room for
plant, according to estimates of a recent study, the addition of improvements that would reduce the cost and energy penalties of
90% carbon capture reduces the thermal efficiency of the power separations. Most estimates indicate that the cost of separation is
plant from about 34% to about 25%, a significant penalty2 that the largest component of the overall cost of CCS, so improve-
implies a corresponding increase in the estimated levelized cost of ments in the energy efficiency and cost of capture could have
electricity, from about 4.8 to about 8.2 cents kWh1 (2006 significant impact on the extent to which CCS can be imple-
dollars), an increase of almost 70%. For a more efficient, ultra- mented at acceptable cost.
supercritical plant, which operates with higher boiler tempera-
tures and pressures, the estimated reduction is from about 43% to
Geologic settings and potential storage volumes
34%, and the estimated cost of electricity increases from 4.7 to 7.3
cents kWh1. Thus, the addition of post-combustion capture Porous rocks that might be used for storage are widely distrib-
with amines would increase the low cost of electric power from uted around the world, as Fig. 3 shows, but they are not collo-
coal significantly, though the increased cost would still be cated everywhere with large CO2 sources. Fig. 4 indicates,
significantly lower than current estimates of the cost of electricity however, that the United States is well endowed with regions that
for photovoltaics and solar thermal electricity and roughly include the three types of geologic formations most commonly
comparable to current cost estimates for electric power from considered for storage: oil and gas reservoirs, deep formations
wind turbines. that contain salt water, and coal beds that are too deep to be
Precombustion and oxyfuel schemes for CO2 capture typically mined. Storage in basalts, deep ocean sediments, and olivine,
start with a cryogenic separation of O2 from air (see Fig. 2). That settings that are less well defined, has also been proposed.
separation also requires energy, of course. Oxyfuel combustion The existence of porous rocks alone does not guarantee that
produces CO2 and H2O (and small amounts of contaminants), they will be suitable for storage, of course, and specific sites will
and the separation of the H2O is accomplished by condensation have to be selected and evaluated carefully.4 Sites that are
of water as a liquid. Some recycling of CO2 to dilute the O2 is appropriate will have rock layers above the storage formation
typically required to control temperature of combustion. Gasi- that prevent vertical flow to the surface. Oil and gas fields always
fication methods (typically in a form known as integrated gasi- have such seal rocks (also called caprocks). If they did not, the
fication and combined cycle, or IGCC, power plants) use partial buoyant oil and gas would have long since escaped. Specific
oxidation of a feedstock such as coal, biomass, or petroleum coke saline aquifers or coal beds may or may not have suitable seal
to make a synthesis gas (CO and H2), which can than be rocks. Porous formations will need to be deep enough that the
combined with steam to produce H2 and CO2 with a shift reac- pressure is sufficient to make the CO2 relatively dense: depths
tion. The CO2 is separated, and the H2 can then be used as a fuel below about 800–1000 m are generally sufficient for oil, gas, and
for a gas turbine or for other chemical syntheses. Significant aquifer settings. Coal beds must be deep enough that there is no

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Fig. 3 Sedimentary basins that have formations potentially suitable for CO2 storage. White dots are significant sources of CO2 emissions. Green regions
include sedimentary rocks with storage potential, grey zones do not, and white areas have not been assessed. Areas with large CO2 sources (white dots)
within 300 km are outlined in red.31
Published on [Link] | doi:10.1039/B822107N
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Fig. 4 US locations of large CO2 sources and geologic formations (oil and gas fields, deep saline aquifers, and deep coal beds) potentially suitable for
storage.2 (a) Spatial distributions of permeability. (b) Spatial distributions and fraction of pore space occupied by injected CO2.

possibility they will be mined, but depths shallower than 1000 m Table 1 Estimated US subsurface CO2 storage resources
could be considered because the storage mechanism for coals
Estimated Estimated
involves adsorption rather than storage of CO2 as a free phase. Storage setting capacity5/Gt CO2 capacity6/Gt CO2
Formations will need to be large enough that a significant
quantity of CO2 can be stored without exceeding the pressure Oil and gas reservoirs 82 126
that would fracture the rocks or activate faults that might leak. Deep saline aquifers 919–3378 2991
Coal beds 156–184 52
Areas with potential leak paths (nonsealing faults or unsealed Shales 107
abandoned wells) will clearly be unsuitable. The permeability (a Basalts 100
measure of how rapidly a fluid flows in a rock under a given
pressure gradient) will also need to be large enough that the CO2
can be injected at a reasonable rate in a reasonable number of as well as shales and basalts. The total potential storage capacity
wells. (in billion metric tons of CO2, Gt CO2) is large compared to the
DOE-supported regional teams have completed a preliminary current annual CO2 emissions from electric power generation
assessment of the potential storage volume resource.5 Table I and industrial sources in the US (about 3 Gt CO2). It is impor-
reports the results of those assessments along with related esti- tant to remember that these are resource estimates, and specific
mates compiled by Vidas et al.6 that include offshore formations site evaluation will be required to determine which subset of

452 | Energy Environ. Sci., 2009, 2, 449–458 This journal is ª The Royal Society of Chemistry 2009
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formations will meet cost, impact of surface facilities, safety, and multiple low-permeability barriers to flow (shales, evaporites, or
other constraints. sealing faults) with high capillary entry pressures that prevent
Oil and gas reservoirs, if they are available within a reasonable significant vertical movement of injected CO2.
distance, will be preferred sites, because an effective seal exists, High pressure CO2, at depths typical of those considered for
because some of the required infrastructure (wells, for example) storage, has a relatively low viscosity (a few hundredths of
may be available, because there is an existing regulatory structure a centipoise). The low-viscosity CO2 will flow preferentially
for CO2 injection, and because it may be possible to offset some through layers with higher permeability than surrounding layers,
of the cost of storage by the value of additional oil or gas and the brine in those layers will be displaced relatively ineffi-
recovered. But oil and gas reservoirs are not as widely distributed ciently. And the difference in density between CO2 and brine will
as deep saline aquifers (see Fig. 4), and their capacity is limited. cause formation of a gravity ‘‘tongue’’, as the CO2 makes its way
Deep saline aquifers offer much larger volumes, however, and upwards to the seal rocks and flows horizontally away from the
the combination of the potential storage volumes available in all injection well.
three storage settings means that many CO2 sources will be Fig. 5a illustrates some of these effects in simulations of CO2
located within reasonable distance of a potential storage injection into vertical cross sections of saline formations with two
formation. Dooley, et al.7 estimated that 95% of the 500 largest spatial arrangements of permeability.12 The first is a set of
CO2 sources in the US are within 80 km of a potential storage random variations, and the second is a three layer system in
formation. A variation on the idea of storage in saline aquifers is which two high permeability layers are separated by a lower
injection of CO2 into deep sea sediments.8 This approach takes permeability layer. CO2 is injected over the bottom quarter of the
Published on [Link] | doi:10.1039/B822107N

advantage of the low temperature and high pressure at depths left side until about 7% of the pore volume of the formation has
below 2700 m in the ocean. At those conditions, CO2 is more been injected. In these displacements, gravity is quite important,
dense than sea water, and it forms hydrates rapidly.9 Below the and despite the fact that the CO2 is injected at the bottom of the
ocean-bottom sediment surface, temperature rises with depth due formation, it quickly flows upward and forms a gravity tongue
to the geothermal gradient. Hence CO2 injected at greater under the impermeable layer that bounds the top of the porous
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depths, where CO2 is less dense than brine, would rise due to formation in both cross sections (see Fig. 5b, part (i)). In the
buoyancy, but would then cool, become dense enough to stop layered example, a second tongue forms beneath the low-
further rise, and form solid hydrates. Storage in sediments at permeability layer. Thus, the combination of gravity segregation
shallower depths where CO2 would be buoyant but less dense and heterogeneity means that the CO2 does not displace the brine
and less mobile than in deep onshore saline aquifers has also been uniformly. Instead, it sweeps only a relatively small fraction of
proposed.10 the formation, and it has high saturation (the fraction of the pore
Some investigators have also proposed that basalt formations space occupied by CO2) at the top of the formation just beneath
could also be used to store CO2.11 That possibility has been the caprock.
investigated much less extensively, however, and it has not yet When injection ceases, a slow process of gravity-driven redis-
been tested in the field. Further study will be needed to refine tribution begins. The location of the injected CO2 at the end of
estimates of potential storage volumes in that setting. the injection period is shown in part (i) of Fig. 5b, and the cor-
The combination of potential storage volumes and locations responding locations of CO2 at the end of the gravity-relaxation
that are widely distributed suggests that there is sufficient period are shown in part (ii). As the CO2 migrates upward, its
potential capacity available to allow storage at a scale large saturation at the base of the gravity tongue declines as water
enough to have an impact on emissions if other constraints can invades from below and replaces the CO2 moving upwards. As
be met. that happens, an important mechanism known as capillary
trapping begins to immobilize CO2 in isolated bubbles that
occupy a few pores. This trapping is the result of an instability
Physical mechanisms of storage
that occurs as a bubble of CO2 is displaced through a pore. The
In a well-designed geologic storage project, there will be multiple curvature of the CO2–brine interface at a pore throat causes
physical mechanisms that limit the movement of CO2, and the brine to flow through thin films on rock surfaces to form a neck
security of storage will increase with time.4 Injected CO2 will be in the pore throat that snaps off to isolate the bubble. Once
a relatively dense supercritical phase at typical subsurface trapped, these bubbles are very difficult to move, so any trapped
conditions, but it will buoyant compared to oil or water, so it is CO2 is not available to leak. This mechanism is well studied
essential that seal rocks prevent vertical migration while other because it is a primary way that oil can be trapped and left behind
mechanisms act to limit the potential for subsequent escape of during the secondary recovery process of waterflooding to
the CO2. Thus the first line of defence against leakage of CO2 to displace oil from reservoir rocks.13 Part (iii) of Fig. 5b shows the
the near surface zone will be rock layers with low permeability, distribution of trapped CO2 at the end of the relaxation period
which occurs when they have very small pores. If the perme- (note the different saturation scale for these panels). The trapped
ability is low, the flow through the porous rock that is induced by saturation varies spatially because the amount that is trapped
a pressure gradient occurs slowly. In addition, a bubble of depends on the maximum CO2 saturation reached before the
supercritical CO2 can penetrate into such a layer only if its brine began to invade behind the CO2. Capillary trapping can
pressure is significantly higher than the pressure in surrounding immobilize a significant fraction of the injected CO2 on time
brine (this pressure difference is called the capillary pressure) in scales of a few injection periods in horizontal formations.12
order to overcome the effects of interfacial tension at the curved Those periods are likely to be decades in full scale projects. Water
interface of the bubble as it enters the pore. Good sites will have injection after CO2 injection can speed trapping further,12

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Published on [Link] | doi:10.1039/B822107N

Fig. 5 Permeability and CO2 saturations in two vertical cross sections of deep saline formations. (a) The two cross sections have differing permeability
distributions. One is heterogeneous with random variations in permeability, and the other consists of two high permeability layers with a low
permeability layer between them. (b) The saturation maps for the two permeability arrangements in (a). Part (i) shows the location of injected CO2 at the
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end of the injection period, typically multiple decades in a full-scale project. Parts (ii) and (iii) show CO2 saturations at the end of the gravity relaxation
period. Part (ii) shows the total saturation of CO2, and (iii) shows the saturation of CO2 that is unable to flow because it has been trapped by capillary
snap-off. (note the different scale for trapped saturation). In these simulations, the CO2 remains in a separate phase, and the effects of dissolution are
ignored.

a process that is similar to walter-alternating-gas or WAG less-dense brine, an unstable situation. Fingers of dense brine
injection in enhanced oil recovery by gas injection. In formations will then descend through uncontacted brine, speeding disso-
that are not horizontal, even a few degrees of inclination can also lution over the rate that would be observed if diffusion alone
aid trapping.12,14 were responsible for transport of CO2 away from zones of high
CO2 is relatively soluble in brine, and hence, the injected CO2 saturation.15,16 Fig. 6 illustrates what will happen, according to
will dissolve over time. At typical subsurface conditions, about high resolution, high order simulations, at least. Many fingers
20 volumes of brine will be required to dissolve a given volume develop initially, but nonlinear interactions reduce the number
of CO2. In most storage projects, the CO2 will displace a small and produce larger-scale plumes at later times. The length of
enough fraction of the brine that sufficient brine will remain to time it takes for plumes to initiate, develop, and descend
dissolve a large fraction of the CO2. How long that will take through the formation can be weeks to thousands of years,
depends on the setting. Consider, for example the distributions depending on permeability (with shorter times in high perme-
of mobile and trapped CO2 in Fig. 5. Brine that is in contact ability formations), and the size (width) can be less than 1 m to
with CO2 will be saturated quickly. Surprisingly, brine satu- greater than 100 m.16 Thus, dissolution removes the driving
rated with CO2 is slightly more dense than brine alone. As force for CO2 to migrate upwards toward the surface, though
a result, CO2 dissolving in the neighborhood of the gravity the time required is generally long enough that an effective seal
tongue will cause more-dense saturated brine to lie above is still required.

Fig. 6 Simulation of the mixing of low-density CO2 with brine in a porous sedimentary formation.12 The CO2 saturates the brine at the top boundary
(high concentrations of dissolved CO2 are indicated by the red color), forming a mixture that is slightly more dense than brine alone. The resulting
gravitational instability leads to downward convection as fingers or plumes.

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The effect of CO2 injection on pressure in the subsurface

formation and displacement of brine must also be considered.
Some deep formations that contain brine are connected over very
long distances. In those settings, the overall compressibility of
the rock/brine system, even though it is small, is sufficient to
accommodate injection of large quantities of CO2 with small
overall pressure increases, and the amount of lateral displace-
ment of brine is small compared to the scale of the formation. In
smaller, confined formations, however, total CO2 injection will
be limited to insure that pressure in the formation does not rise to
the point of fracturing the formation and caprock or activating
pathways for flow along faults.17,18 Assessment of the impact of
injection on formation pressure and geomechanics is part of the
evaluation of a potential storage site.
Geochemical reactions can also act to immobilize dissolved
CO2 in the form of solid minerals. When CO2 dissolves it lowers
pH and forms both carbonate (CO32) and bicarbonate (HCO3)
ions, which can react to dissolve CaCO3 or silicate minerals. Fig. 7 Adsorption of gases on a powdered coal sample (Jessen et al.21).
Published on [Link] | doi:10.1039/B822107N

Dissolution of silicate minerals can raise pH enough to precipi- Significantly more CO2 adsorbs than does CH4 or N2 at a given pressure.
tate Ca, Fe, or Mg carbonates, among other minerals, depending Hysteresis is also observed. As the pressure increases, the gases adsorb,
on the details of brine composition and the chemical composition but upon reduction in pressure more gas remains adsorbed than would
of the sedimentary rocks and cements.11 These reactions can adsorb at the same pressure during pressure increases.
occur as dissolved CO2 encounters and reacts with components
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in the brine and rock in the subsurface19 or they can occur as difficulty that could limit wide application of storage in coal.
a result of mixtures created at the surface by mining silicate Low rates of injection could be increased by drilling more wells,
minerals that are then contacted by water containing dissolved by using horizontal wells, or by fracturing the coal, though that
CO2.20 These reactions are relatively slow, and hence any injected approach would have to be undertaken carefully to avoid
CO2 must be contained in the subsurface during the time creating pathways for leakage. Whether similar issues will arise
required for the reaction to occur. A version of mineralization for storage in shales has not yet been investigated in detail, but
has been considered for basalts,11 which are widely distributed on shales often have quite low permeability, which will likely limit
the Earth and contain more of the reactive Ca, Mg, and Fe injection rates.
bearing minerals than typical sedimentary rocks do. Basalt The storage mechanisms described above act on a range of
reaction rates observed in laboratory experiments11 were signif- time scales. Seals work immediately to limit vertical migration of
icantly faster than those envisioned for saline aquifers19 CO2. Pressure in the subsurface will rise as injection proceeds.
(hundreds to thousands of years). How much and how rapidly depends on the overall size and
CO2 can also be immobilized by adsorption on surfaces of compressibility of the fluids and rock formation. The maximum
organic materials such as coal or shales that are rich in organic pressure rise will have to be limited to pressures below which the
material. Fig. 7 compares amounts of CO2, CH4, and N2 that caprocks do not fracture or faults activate. Dissolution happens
adsorb on a crushed Powder River Basin coal, for example.21 N2 quickly where CO2 encounters brine, but the time required to
adsorbs weakly, CH4 does so more strongly, and about three dissolve all of the CO2 is much longer, typically hundreds to
times as much CO2 adsorbs as does CH4. Adsorbed CH4 in coals thousands of years. Pressure will decline after injection ceases, as
is the source of coal bed methane that now accounts for about gravity redistributes CO2 in the formation and as CO2 dissolves
10% of US natural gas production. Because CO2 adsorbs more or adsorbs (it occupies less volume in those states). Capillary
strongly than CH4, it can replace the CH4, and hence it is possible trapping takes place wherever water invades a zone saturated
to recover some CH4 and store CO2 simultaneously. In fact, Seto with CO2. That typically begins at the end of the injection period,
et al.22 showed that a coal bed can also be used to separate CO2 and several times the injection time period of 20–30 years will
from N2 (as in a flue gas). The CO2 adsorbs and is retarded, and likely be required for most capillary trapping to occur, though it
the N2 flows ahead, recovering CH4 as adsorbed CH4 equili- may be possible to reduce this time by injecting water during or
brates with the flowing N2 with low partial pressure of CH4. The after CO2 injection.12 Mineralization reactions also act on
price of that separation, however, is the requirement that large a range of time scales, but in sedimentary rock systems they are
amounts of flue gas be compressed for injection, and because N2 likely to require much longer times than the other mechanisms.
propagates quickly through the coal, CH4 recovered after Over time, these storage mechanisms reduce the driving forces
injected gas reaches production wells would have to be separated (buoyancy and pressure) for leakage and the mobility of CO2,
from the N2. When large quantities of CO2 adsorb, however, the and hence storage security should increase with time.4
permeability of the coal decreases. That permeability is mainly Thus, several physical mechanisms, acting on a range of time
associated with natural fractures present in the coal, and as the scales, are available to retain CO2 in the subsurface. With careful
coal takes up CO2, which still occupies some volume when it is attention to the combination of physical mechanisms of storage
adsorbed, fracture permeability declines. Permeability reduc- and specific site considerations, it should be possible to store CO2
tions limit the rate at which CO2 can be injected, a potential essentially permanently (on human time scales, at least).

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Monitoring of subsurface CO2 injection and sampling of tracers, fluid composition measurements, electro-
magnetic methods that detect changes in conductivity of fluids, and
Monitoring will be an essential feature of any CO2 storage soil gas and eddy covariance methods that detect CO2 at the surface.
project, just as it is a normal part of operations of a gas injection For a detailed review and many references see the comprehensive
project for oil recovery. Wells are the most likely leak path for IPCC Special Report on CO2 Capture and Storage.4
any project,23 though well problems are frequently dealt with by More monitoring efforts will be needed early on in the life of
what are known as workovers in the oil industry. Hence a project than will be required later, but appropriate methods will
measurement of injection rates and injection well pressures will need to be established for the various stages of a project. During
be a routine part of operations. The location of CO2 in the region the injection period, safe operations will require monitoring for
near a well bore can be detected by logging methods used in the leaks from pipelines, surface facilities, and wells.23 At low
oil industry.4 Those methods can be used to determine whether concentrations, CO2 is not dangerous. It is a normal constituent
the injected CO2 is entering and remaining in the target forma- of air, and large power plants currently emit millions of tonnes per
tion near the injection well. year directly into the atmosphere. At high concentrations,
A variety of other subsurface monitoring techniques have however, it is an asphyxiant and is toxic. A concentration of 4%
potential to determine the location of injected CO2 away from the CO2 is immediately dangerous to health; the NIOSH and OSHA
injection well. Seismic methods, which include time-lapse reflec- exposure limits are 5000 ppm (0.5%).27 Because CO2 is more dense
tion24 or tomographic imaging25 can be used to detect subsurface than air, making sure that leaking CO2 does not collect in low-
migration and leaks. Fig. 8 shows an example of time-lapse lying areas or depressions is essential. After CO2 injection ceases,
Published on [Link] | doi:10.1039/B822107N

reflection imaging of the subsurface flow in a CO2 injection the potential for leakage declines over time, and hence, the need
project at the Sleipner Field in the North Sea, where CO2 sepa- for monitoring movement of CO2 in the subsurface will also
rated from natural gas is injected into a sandstone formation that decline over time. The range of monitoring techniques available
lies above the formation from which the natural gas is produced. indicates that a monitoring protocol can be developed to permit
The difference in density and compressibility of the supercritical safe operation of a project and to detect problems if they occur.
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CO2 phase from that of the resident brine causes reflections of

seismic waves that allow detection of the location of the CO2
Field experience
plume. The sequence of seismic images of the vertical cross section
in the upper series and the areal views in the lower series confirm Experience with large scale CO2 injection is accumulating around
that the injected CO2 has stayed in the intended formation.24,26 the world. Part of the experience comes from gas injection projects
Gravity measurements and deformation methods such as for enhanced oil recovery. For example, CO2 has been injected for
synthetic aperture radar or tiltmeter measurements also have about 35 years for the purpose of enhanced oil recovery in west
potential,4 though they will provide lower resolution indications of Texas, though most of the CO2 injected is from natural sources of
fluid movement. Many other methods are also available: injection CO2 rather than anthropogenic CO2. Those projects make use of an

Fig. 8 Time-lapse seismic images of the injected CO2 plume at the Sleipner field.22 The upper series shows a cross-sectional image, and the lower series
shows an areal view. The 1994 image was taken before the start of CO2 injection. Injection of about 1 Mt CO2 yr1 began in 1996. Subsequent images
show the evolution of the CO2 plume as the CO2 flows through the sandstone formation under the caprock and intermediate shale layers within the
sandstone.

456 | Energy Environ. Sci., 2009, 2, 449–458 This journal is ª The Royal Society of Chemistry 2009
 View Online

infrastructure of 5600 km of pipelines23 that deliver CO2 from demonstrate combined CO2 capture at the scale of a large coal-fired
natural occurrences in New Mexico and Colorado and natural gas power plant with storage in a variety of geological settings. That will
separation facilities to 70 oil fields. About 30 Mt CO2 is injected per be an important next step if CCS is to be implemented at a scale
year in these projects, several of which inject CO2 in quantities that large enough to have an impact on CO2 emissions. It is worth
are comparable to or larger than the emissions of a large coal-fired remembering that large scale is very large indeed. For densities of
power plant (500 MW).4 The experience gained in transporting and 500–700 kg/m3, which are typical of pressures and temperatures in
injecting large quantities of CO2 gives reasonable assurance that the subsurface, 1 GtCO2/yr is equivalent in volume to 25–35 million
with careful site selection,4 project design, and operation,21 CO2 can barrels per day of injection, roughly 50% bigger than current
be transported over significant distances and injected into forma- petroleum use in the US. Hence, it will take 330–1000 projects of the
tions that can be expected to retain the CO2 indefinitely. 1–3 Mt CO2/yr scale to eliminate about half of the current US
Projects that inject CO2 that would have been emitted to the emissions of CO2 from electric power generation. It is equally clear
atmosphere and that are monitored are shown in Fig. 9. The that other ways to reduce emissions will also be needed.
projects shown are at various stages of planning and execution,
and some are commercial-scale tests while others are small pilot
projects. More than 10 Mt CO2 have been injected (at about 1 Mt
Conclusions
CO2 yr1) through a single well into the very large and quite This paper has examined whether enough is known about carbon
permeable Utsira Formation at Sleipner in the North Sea.4,24,26 capture and storage (CCS) that implementation can be tested at
At In Salah in Algeria, CO2 separated from natural gas is injected large scale:
Published on [Link] | doi:10.1039/B822107N

at a rate of about 1 Mt CO2 yr1 through three long horizontal Can CO2 be captured efficiently and at an acceptable cost?
wells into a much lower permeability zone at the base of the gas Technologies to capture CO2 are used widely at commercial
reservoir.29 A combined CO2 storage and enhanced oil recovery scale. They are still relatively expensive in terms of energy costs
project is being conducted at the Weyburn Field in Saskatch- and therefore in dollar costs for application to power plants.
ewan, Canada.30 For that project, CO2 containing a small Integration of capture and storage at the scale of a large power
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amount of H2S (0.8–2%) is separated at a coal gasification facility plant (500 MW or more) has not yet been demonstrated.
in North Dakota and transported by pipeline 320 km to the oil Is there sufficient variety of geologic settings and sufficient
field. The presence of H2S, a very hazardous substance, imposes volume to store enough CO2 to have an impact on emissions?
special safety considerations.23 That project is injecting about 1.8 Estimates of total volumes of potentially suitable pore space
Mt CO2 yr1, a little over half the rate of CO2 emissions from a 500 indicate that there is sufficient volume available to permit
MW coal-fired power plant (about 3 Mt CO2 yr1). significant impact on emissions. The combination of potential
Thus, the large enhanced oil recovery and CO2 storage projects storage in oil and gas reservoirs, deep saline formations, coal
have provided significant operating experience that can be applied beds, basalts, and shales provides potential storage locations
to guide large-scale CO2 storage. What has not yet been done is to within reasonable distance of many large sources of CO2.

Fig. 9 Active CO2 storage projects worldwide.26 The largest projects currently injecting CO2 are SACROC in west Texas, Sleipner in the North Sea, In
Salah in Algeria, and Weyburn in Canada. Image courtesy of CO2CRC, Australia.

This journal is ª The Royal Society of Chemistry 2009 Energy Environ. Sci., 2009, 2, 449–458 | 457
 View Online

Are there sufficient physical mechanisms that will trap the CO2 10 K. Z. House and D. P. Schrag, The immobility of CO2 in deep sea
in the subsurface to allow design of safe storage projects that will sediments, presented at the Ninth Greenhouse Gas Technology
Conference, Washington, D.C, Nov. 16–20, 2008.
not leak? Retention by seal rocks, dissolution, adsorption, 11 B. P. McGrail and et al., Potential for carbon dioxide sequestration in
capillary trapping, and mineralization reactions are among the flood basalts, J. Geophys. Res.-Solid Earth, 2006, 111, p. ARTN B12201.
mechanisms that can be used to retain CO2 in the subsurface 12 T. Ide, K. Jessen and F. M. Orr, Jr., Storage of CO2 in saline aquifers:
indefinitely. The fact that natural systems store large quantities Effects of gravity, viscous,and capillary forces on amount and timing
of trapping, Intl. J. Greenhouse Gas Control, 2007, 1, 481–491.
of buoyant fluids (oil, natural gas, and even CO2) provides 13 J. G. Roof, Snap-Off of Oil Droplets in Water-Wet Pores, Soc. Pet.
confidence that long-term storage is possible. Eng. J., 1970, 85–90.
Can the movement of fluids in the subsurface be monitored and 14 M. A. Hesse, F. M. Orr, Jr and Tchelepi, Gravity Currents with
Residual Trapping, J. Fluid Mech., 2008, 611, 35–60.
leaks be detected and if necessary, remediated? A wide range of 15 J. Ennis-King and L. Paterson, 2003, Role of convective mixing in the
monitoring techniques is available, with differing sensitivities and long-term storage of carbon dioxide in deep saline formations, SPE
resolutions. Surface monitoring can detect hazards associated 84344 pp. 1–12.
with surface leakage of CO2 and subsurface methods (well logs, 16 A. Riaz, M. Hesse, H. Tchelepi and F. M. Orr, Jr., Onset of
Convection in a Gravitationally Unstable, Diffusive Boundary
pressure measurements, and seismic surveys, etc.) can determine Layer in Porous Media, J. Fluid Mech., 2006, 548, 87–111.
where CO2 migration is taking place. Technology available today 17 L. G. H. van der Meer and F. Yavuz, CO2 storage calculations for the
is sufficient to allow safe operation of well-sited, well-engineered, Dutch subsurface, presented at the Ninth Greenhouse Gas Technology
Conference, Washington, D.C, Nov. 16–20, 2008.
and carefully operated subsurface storage projects.
18 L. Chiaramonte, M. D. Zoback, J. Friedmann and V. Stamp, Seal
Do we have enough experience with actual operations to undertake integrity and feasibility of CO2 sequestration in the Teapot Dome
Published on [Link] | doi:10.1039/B822107N

storage at a scale large enough to have an impact on emissions? There EOR pilot: Geomechanical site characterization, Environ. Geol.,
is sufficient experience with commercial-scale separation and CO2 2008, 54, 1667–1675.
19 J. W. Johnson, J. K. Nitao and K. G. Knauss, 2004, Reactive
injection in enhanced oil recovery projects and in specifically transport modelling of CO2 storage in saline aquifers to elucidate
designed storage projects to warrant moving to the stage of fundamental processes, trapping mechanisms, and sequestration
demonstrating CCS at the scale of large coal-fired power plants. partitioning, in Geological Storage of Carbon Dioxide, ed. S. J.
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Progress to date suggests, therefore, that while there is more to Baines and R. H. Worden, Geol. Soc. Spec. Publ., 233, 107–128.
20 K. S. Lackner, D. P. Butt and C. H. Wendt, Progress on binding CO2
be learned about operating at scale and reducing costs, enough is in mineral substrates, Energy Conver. Manage., 1997, 38, S259–S264.
known now about CCS to suggest that it can contribute signifi- 21 K. Jessen, G.-Q. Tang and A. R. Kovscek, Laboratory and
cantly to reductions in CO2 emissions, even as many other Simulation Investigation of Enhanced Coalbed Methane Recovery
by Gas Injection, Transport in Porous Media, 2008, 73, 141–159,
approaches are applied over the same time period. DOI: 10.1007/s11242-007-9165-9.
22 C. J. Seto, K. Jessen, and F. M. Orr, Jr., A Multicomponent, Two-Phase
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SPE 102376, SPE Annual Technical Conference, San Antonio,
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ford University is acknowledged with gratitude. 23 I. J. Duncan, J.-P. Nicot, and J.-W. Choi, Risk Assessment for future
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458 | Energy Environ. Sci., 2009, 2, 449–458 This journal is ª The Royal Society of Chemistry 2009