Christopher A. Rochelle

Natural occurrences as analogues for the geological disposal of carbon dioxide

It is now generally accepted that anthropogenic CO2 emissions are contributing to the global rise in atmospheric CO2 concentrations. One possibility for reducing carbon dioxide emissions is to remove it from the flue gases of coal-fired power stations and dispose of it in underground geological reservoirs, possibly offshore in the North Sea. The feasibility of this option has been studied in detail by a consortium of European partners. As part of this study, natural occurrences of carbon dioxide were identified and preliminary information from these was obtained. The best characterised are found in the United States where the carbon dioxide reserves are exploited for use in tertiary enhanced oil recovery (EOR) programs in the Texas oilfields. The carbon dioxide reserves occur in geological structures and lithologies which are similar to those present in the North Sea. As such, these fields offer an ideal natural analogue for the disposal of carbon dioxide, since the interactions with groundwaters and reservoir lithologies have occurred on both spatial and temporal scales relevant to geological processes. Those carbon dioxide fields currently being exploited have already been studied to a limited extent by the oil companies involved. However, further study is required to provide information on the potential effects that disposing of large quantities of carbon dioxide might have on groundwaters and reservoir quality. In addition, more detailed information will be obtained on the interactions which occur during EOR using carbon dioxide. This paper presents data on some of the natural carbon dioxide fields, and compares the effects of these natural fluid-rock interactions with those observed in laboratory experiments performed to establish what reactions occur during the geological disposal of carbon dioxide.

The impact of chemical reactions on CO2 storage in geological formations: a brief review

Abstract The sequestration of CO2 in the deep geosphere is one potential method for reducing anthropogenic emissions to the atmosphere without a drastic change in our energy-producing technologies. Immediately after injection, the CO2 will be stored as a free phase within the host rock. Over time it will dissolve into the local formation water and initiate a variety of geochemical reactions. Some of these reactions could be beneficial, helping to chemically contain or ‘trap’ the CO2 as dissolved species and by the formation of new carbonate minerals; others may be deleterious, and actually aid the migration of CO2. It will be important to understand the overall impact of these competing processes. However, these processes will also be dependent upon the structure, mineralogy and hydrogeology of the specific lithologies concerned and the chemical stability of the engineered features (principally, the cement and steel components in the well completions). Therefore, individual storage operations will have to take account of local geological, fluid chemical and hydrogeological conditions. The aim of this paper is to review some of the possible chemical reactions that might occur once CO2 is injected underground, and to highlight their possible impacts on long-term CO2 storage.

Rate and mechanism of the reaction of silicates with cement pore fluids

Abstract The reaction mechanisms and rates of reaction of a number of the common rock-forming silicates with synthetic cement pore fluids have been evaluated in a series of laboratory experiments at 70°C. Mass transfer is dominated by the dissolution of the primary silicate and the precipitation of a range of Na-K-Al substituted calcium silicate hydrates, and a possible zeolite. Calcium was lost from, and silicon gained by, the fluid phase as a result of the reactions. Secondary solids formed thick layers on primary silicates, but dissolution of the silicates was not diffusion-limited. The rate of dissolution of the silicates was determined to be 2–3 orders of magnitude greater at pH 12–13 than at neutral pH, and confirm measurements by other authors. The rate of growth of calcium silicate hydrates was limited by the rate of supply of silicon from the primary silicates. Although the results of the laboratory experiments were dominated by the loss of calcium from the fluid and the precipitation of calcium silicate hydrates, thermodynamic modelling suggests that these may be replaced by zeolites and/or feldspars when groundwater residence times are considered.

Chemical containment of waste in the geosphere

Abstract The aim of this introductory paper is to highlight those underlying chemical principles that are common to all forms of waste management by geological means, and that rely to some extent upon chemical containment. Until recently, chemical processes were usually considered mainly because they can affect the physical performance of engineered containment systems. However, in recent years, many researchers have recognized that chemical processes themselves can offer containment to wastes. Thus, it is no longer possible to view physical and chemical containment processes separately. The containment system can be optimized only if both the engineered and natural barriers are considered together, and if the engineered barrier system is designed taking the features of the geosphere into account. However, there has been relatively little reliance upon the geosphere itself as a chemical barrier. It is concluded that the potential for chemical containment should be considered in all forms of geological waste management. Even if the chemical barrier function of the geosphere is not relied upon to meet safety targets, the confidence of regulators and public alike will be enhanced if it can be demonstrated that the geosphere at the site functions as a chemical barrier.

Can CO2 hydrate assist in the underground storage of carbon dioxide

Abstract The sequestration of CO2 in the deep geosphere is one potential method for reducing anthropogenic emissions to the atmosphere without necessarily incurring a significant change in our energy-producing technologies. Containment of CO2 as a liquid and an associated hydrate phase, under cool conditions, offers an alternative underground storage approach compared with conventional supercritical CO2 storage at higher temperatures. We briefly describe conventional approaches to underground storage, review possible approaches for using CO2 hydrate in CO2 storage generally, and comment on the important role CO2 hydrate could play in underground storage. Cool underground storage appears to offer certain advantages in terms of physical, chemical and mineralogical processes, which may usefully enhance trapping of the stored CO2. This approach also appears to be potentially applicable to large areas of sub-seabed sediments offshore Western Europe.

Analcime reactions at 25–90°C in hyperalkaline fluids

Abstract Extensive use of cement and concrete is envisaged in the construction of geological disposal facilities for radioactive wastes. The hyperalkaline porefluids typical of groundwaters that have reacted with these materials have the potential to react chemically with other engineered barrier components such as bentonite, potentially degrading their performance. Analcime, NaAlSi2O6‧H2O, has been identified from previous modelling and experimental studies as a potential alteration product of bentonite. Laboratory experiments to investigate the stability of analcime under hyperalkaline porefluid conditions have been performed. Experiments used both batch and fluidized bed equipment at 25, 50, 70 and 90°C in K-based pH buffer solutions, both under- and over-saturated with respect to analcime. Results from dissolution experiments demonstrate that release of Na was greatly enhanced (by up to a factor of thirty) over that for Si and Al, particularly at pH 10 and 11. However, enhanced release of both Na and Al occurred in the batch experiments at pH 12-13. Near stoichiometric dissolution was observed in fluidized bed experiments under steady-state conditions at 70°C. Sodium was removed from the analcime structure by ion exchange for K, without involving dissolution and re-precipitation of the analcime framework. Scanning electron microscopy of reacted analcime grains showed that some grains had pronounced cracks parallel to original cleavage traces. These cracks were a result of volume decrease due to the substitution of K for Na ions and water molecules in the analcime structure to form leucite, KAlSi2O6. Synthesis of the dissolution data shows that the rate of dissolution increased with increasing temperature in the range 25-70°C and with pH at each temperature. Absolute rates of dissolution ranged from 10-10 mol m-2 s-1 at pH 9.5 at 25°C to 10-7 mol m-2 s-1 at pH 12 at 70 and 90°C. The rate of dissolution at any temperature was pH-dependent, such that the rate could be described by k (aH⁺)n, where k is the rate constant and n is -0.3 at 25°C, -0.4 at 50°C, -0.6 at 70°C and -0.7 at 90°C. Attempts to measure the growth rate of analcime in supersaturated solutions at 70 and 90°C were unsuccessful, although a limiting rate at 70°C, pH 10 was calculated to be 4 × 10-11 mol m-2 s-1, roughly 100× less than the rate of dissolution under the same conditions. These results imply that any trace amounts of analcime in bentonite will be converted to leucite by reaction with cement fluids with a high K/Na ratio. In some instances, leucite may thus incorporate K+ in preference to other phases (e.g. illite, K-feldspar) during alteration of bentonite by cement porefluids.

Subsurface characterization and geological monitoring of the CO2 injection operation at Weyburn, Saskatchewan, Canada

Abstract The IEA Weyburn Carbon Dioxide (CO2) Monitoring and Storage Project analysed the effects of a miscible CO2 flood into a Lower Carboniferous carbonate reservoir rock at an onshore Canadian oilfield. Anthropogenic CO2 is being injected as part of a commercial enhanced oil recovery operation. Much of the research performed in Europe as part of an international monitoring project was aimed at analysing the long-term migration pathways of CO2 and the effects of CO2 on the hydrochemical and mineralogical properties of the reservoir rock. The pre-CO2 injection hydrochemical, hydrogeological and petrographical conditions in the reservoir were investigated in order to recognize changes caused by the CO2 flood and to assess the long-term fate of the injected CO2. The Lower Carboniferous (Mississippian) aquifer has a salinity gradient in the Weyburn area, where flows are oriented SW–NE. Hydrogeological modelling indicates that dissolved CO2 would migrate from Weyburn in an ENE direction at a rate of about 0.2 m/annum under the influence of regional groundwater flow. Baseline gas fluxes and CO2 concentrations in groundwater were also investigated. The gas dissolved in the reservoir waters allowed potential transport pathways to be identified. Analysis of reservoir fluids proved that dissolved CO2 and methane (CH4) increased significantly in the injection area between 2002 and 2003. Most of the injected CO2 exists in a supercritical state, lesser amounts are trapped in solution and there is little apparent mineral trapping. The CO2 has already reacted with the reservoir rock sufficiently to mask some of the strontium isotope signature caused by 40 years of water flooding. Experimental studies of CO2–porewater–rock interactions in the Midale Marly Unit indicated slight dissolution of carbonate and silicate minerals, followed by relatively rapid saturation with respect to carbonate minerals. Carbon dioxide flooding experiments on similar rock samples demonstrated that porosity and gas permeability increased significantly through dissolution of calcite and dolomite. Several microseismic events were recorded over a six-month period and these are provisionally interpreted as being related to small fractures formed by injection-driven fluid migration within the reservoir, as well as other oilfield operations. Experimental studies on the overlying and underlying units show similar reaction processes; however secondary gypsum precipitation was also observed. Reaction experiments were conducted with CO2 and borehole cements. The size and tensile strength of the cement blocks were unaffected, however their densities increased. Pre- and post-injection soil gas survey data are consistent with a shallow biological origin for the measured CO2 in soil gases. Isotopic (δ13C) data values are higher than in the injected CO2, and confirm this interpretation. No evidence for leakage of the injected CO2 to ground level has been detected. The long-term safety and performance of CO2 storage was assessed by the construction of a features, events and processes (FEP) database that provides a comprehensive knowledge base for the geological storage of CO2.

Fluid-rock interactions during continental red bed diagenesis: implications for theoretical models of mineralization in sedimentary basins

Abstract Continental red beds are first-cycle, immature sediments which are deposited in oxidizing conditions and owe their red colouration to the early diagenetic development of hematite. Previously published work on the fluid/rock interactions which occur during the diagenesis of such sediments highlights that pH and redox are critical fluid parameters which control diagenesis and ore formation. However, except in modern surface water and shallow groundwater systems, these parameters cannot be measured directly, and must be estimated from theoretical considerations. These suggest that mixing between fluids of different redox states is likely to be a critical control on heavy metal mobility. Many diagenetic features can be explained largely by the chemical heterogeneity of red beds, and by the diagenetic ranges of redox conditions and pH which are among the greatest for any type of sediment. Such features include: the formation of red bed-hosted ore deposits; the extensive development of hematite; and the development of early diagenetic non-ferroan carbonate and late diagenetic ferroan carbonate cements. In order to develop theoretical models of fluid/rock interactions during such diagenesis, it is important to consider the interrelationships between fluid flow, mineral dissolution and precipitation, and sorption. At the present time such models are at an early stage of development.

Sediment-hosted gas hydrates : new insights on natural and synthetic systems

Abstract In the publics imagination, hydrates are seen as either a potential new source of energy to be exploited as the world uses up its reserves of oil and gas or as a major environmental hazard. Scientists, however, have expressed great uncertainty as to the global volume of hydrates and have reached little agreement on how they might be exploited. Both of these uncertainties can be reduced by a better understanding of how hydrates are held within sediments. There are conflicting ideas as to whether hydrates are disseminated within selected lithologies or trapped within fractures comparable to mineral lodes. To resolve this, hydrates have to be examined at all scales ranging from using seismics to microscopic studies. Their position within sediments also influences the stability of methane hydrate in responding to pressure and temperature and how the released gas might transfer to the ocean, atmosphere, or to a transport mechanism for recovery. These results also run parallel with the studies of carbon dioxide hydrate, which is being considered as a potential sequestion medium.

The underground sequestration of carbon dioxide: containment by chemical reactions in the deep geosphere

Abstract Anthropogenic emissions of carbon dioxide (CO2) have been linked to increasing levels in the atmosphere and to potential global climate change. The capture of CO2 from large point sources, followed by its sequestration as a supercritical fluid into the deep geosphere, is one potential method for reducing such emissions without a drastic change in our energy-producing technologies. Once emplaced underground, geochemical and hydrogeological processes will act to ‘trap’ the CO2 as dissolved species and in carbonate minerals. Although dry supercritical CO2 appears to cause little reaction with the host rocks, once dissolved in water mineral dissolution and precipitation reactions can result. From a geochemical standpoint, sandstones appear to be preferable to carbonates for sequestration operations because fluid-mineral reactions within them have a better capacity for pH buffering. However, individual host lithologies will vary in structure, mineralogy and hydrogeology, and individual sequestration operations will have to take account of local geological, fluid chemical and hydrogeological conditions. This paper summarizes some of the recent laboratory experimental, natural analogue and computer modelling approaches directed at understanding reactions involved in the chemical containment of CO2.