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Chapter 6: Ocean storage 291 calcite saturation state, which they contend would not induce precipitation. This approach does not rely on deep-sea release, avoiding the need for energy to separate, transport and inject CO2 into the deep ocean. The wastewater generated by this carbonate-neutralization approach has been conjectured to be relatively benign (Rau and Caldeira, 1999). For example, the addition of calcium bicarbonate, the primary constituent of the effluent, has been observed to promote coral growth (Marubini and Thake, 1999). This approach will not remove all the CO2 from a gas stream, because excess CO2 is required to produce a solution that is corrosive to carbonate minerals. If greater CO2 removal were required, this approach could be combined with other techniques of CO2 capture and storage. CO2 slurry is required for flow assurance (Tsouris et al., 2004). Water-CaCO3-CO2 emulsion. Mineral carbonate could be used to physically emulsify and entrain CO2 injected in sea water (Swett et al. 2005); a 1:1 CO2:CaCO3 emulsion of CO2 in water could be stabilized by pulverized limestone (CaCO3). The emulsion plume would have a bulk density of 40% greater than that of seawater. Because the emulsion plume is heavier than seawater, the CaCO3coated CO2 slurries may sink all the way to the ocean floor. It has been suggested that the emulsion plume would have a pH that is at least 2 units higher than would a plume of liquid CO2. Carbonate minerals could be mined on land, and then crushed, or fine-grained lime mud could be extracted from the sea floor. These fine-grain carbonate particles could be suspended in sea water upstream from the CO2-rich plume emanating from the direct CO2 injection site. The suspended carbonate minerals could then be transported with the ambient sea water into the plume, where the minerals could dissolve, increasing ocean CO2 storage effectiveness and Process wastewater could be engineered to contain different ratios of added carbon and calcium, and different ratios of flue gas CO2 to dissolved limestone (Caldeira and Wickett, 2005). Processes involving greater amounts of limestone dissolution per mole CO2 added lead to a greater CO2 fraction being retained. The effluent from a carbonate-dissolution reactor could have the same pH, pCO2, or [CO32–] as ambient seawater, although processing costs may be reduced by allowing effluent composition to vary from these values (Caldeira and Rau, 2000). Elevation in Ca2+ and bicarbonate content from this approach is anticipated to be small relative to the already existing concentrations in sea water (Caldeira and Rau, 2000), but effects of the new physicochemical equilibria on physiological performance are unknown. Neutralization of carbon acidity by dissolution of carbonate minerals could reduce impacts on marine ecosystems associated with pH and CO32– decline (Section 6.7). diminishing the pH impacts of direct injection. Emplacement in carbonate sediments. Murray et al. (1997) Carbonate neutralization approaches require large amounts of carbonate minerals. Sedimentary carbonates are abundant with estimates of 5 x 1017 tonnes (Berner et al., 1983), roughly 10,000 times greater than the mass of fossil-fuel carbon. Nevertheless, up to about 1.5 mole of carbonate mineral must be dissolved for each mole of anthropogenic CO2 permanently stored in the ocean (Caldeira and Rau, 2000); therefore, the mass of CaCO3 used would be up to 3.5 times the mass of CO2 stored. Worldwide, 3 Gt CaCO3 is mined annually (Kheshgi, 1995). Thus, large-scale deployment of carbonate neutralization approaches would require greatly expanded mining and transport of limestone and attendant environmental impacts. In addition, impurities in dissolved carbonate minerals may cause deleterious effects and have yet to be studied. Direct flue-gas injection. Another proposal is to take a power plant flue gas, and pump it directly into the deep ocean without any separation of CO2 from the flue gas, however costs of compression are likely to render this approach infeasible. 6.2.3 Other ocean storage approaches Solid hydrate. Water reacts with concentrated CO2 to form a solid hydrate (CO2·6H2O) under typical ocean conditions at quite modest depths (Løken and Austvik, 1993; Holdren and Baldwin, 2001). Rehder et al. (2004) showed that the hydrate dissolves rapidly into the relatively dilute ocean waters. The density of pure CO2 hydrate is greater than seawater, and this has led to efforts to create a sinking plume of released CO2 in the ocean water column. Pure CO2 hydrate is a hard crystalline solid and thus will not flow through a pipe, and so some form of Storage capacity for CO2 in the ocean can be defined relative to an atmospheric CO2 stabilization concentration. For example, roughly 2,300 to 10,700 GtCO2 (above the natural pre-industrial background) would be added to the ocean in equilibrium with atmospheric CO2 stabilization concentrations, ranging from 350 ppmv to 1000 ppmv, regardless of whether the CO2 is initially released to the ocean or the atmosphere (Table 6.1, Figure 6.3; Kheshgi et al., 2005; Sorai and Ohsumi, 2005). The capacity of the ocean for CO2 storage could be increased with the addition of alkalinity to the ocean (e.g., dissolved limestone). have suggested emplacement of CO2 into carbonate sediments on the sea floor. Insofar as this CO2 remained isolated from the ocean, this could be categorized as a form of geological storage (Chapter 5). Dry ice torpedoes. CO2 could be released from a ship as dry ice at the ocean surface (Steinberg,1985). One costly method is to produce solid CO2 blocks (Murray et al., 1996). With a density of 1.5 t m–3, these blocks would sink rapidly to the sea floor and could potentially penetrate into the sea floor sediment. 6.3 Capacity and fractions retained 6.3.1 Capacity The physical capacity for storage of CO2 in the ocean is large relative to fossil-fuel resources. The degree to which this capacity will be utilized may be based on factors such as cost, equilibrium pCO2, and environmental consequences. 6.3.2 Measures of fraction retained Effectiveness of ocean CO2 storage has been reported in aPDF Image | CARBON DIOXIDE CAPTURE AND STORAGE
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