Fundamental Thermodynamics of Aqueous Carbon Dioxide Systems

"Many investigations are being performed with the goal of removing carbon dioxide from the atmosphere and permanently storing it in geologically stable settings. At the same time, carbon dioxide in the form of dissolved carbonate is steadily accumulating in the world's oceans. Both carbon dioxide sequestration and oceanic accumulation are constrained by the aqueous thermodynamics of the carbonate system. These constraints are illustrated using the STABCAL computer model to generate potential-pH and aqueous distribution diagrams of seawater in contact with various pressures of carbon dioxide gas. STABCAL diagrams and titration simulations are also used to model some potentially useful cation-carbonate sequestrationsystems.IntroductionAtmospheric carbon dioxide concentrations have risen dramatically in the past couple of centuries and are rising still, primarily as a result of human activities, especially the burning of fossil fuels. Increased atmospheric carbon dioxide concentrations have been implicated as a main cause of global warming but have other effects as well.Rising levels of atmospheric carbon dioxide result in increased concentrations of dissolved carbonate complexes in water, including the oceans. These dissolved carbonates interact with other dissolved substances, altering overall seawater chemistry, most noticeably causing lowered pH levels.Some of these chemical changes are observed directly, for instance the general drop in oceanic pH, [1], while others can be inferred and predicted using thermodynamic modeling. The chemistry of dissolved carbonate in seawater is not especially intricate, as such chemical systems go, but neither is it simple enough to be worked out on the back of an envelope. Interactions between the several simple carbonate species and all the major dissolved cations in seawater should be considered, as well as the effects of competing anions, especially chloride and sulphate, since they are much more abundant than carbonate in seawater."