Electrolytic Seawater Mineralization and the Mass Balances That Demonstrate Carbon Dioxide Removal.

We present the mass balances associated with carbon dioxide (CO) removal (CDR) using seawater as both the source of reactants and as the reaction medium via electrolysis following the "" (") process. This process, extensively detailed in La Plante E.C.; ACS Sustain. Chem. Eng.2021, 9, ( (3), ), 1073-1089, involves the application of an electric overpotential that splits water to form H and OH ions, producing acidity and alkalinity, i.e., in addition to gaseous coproducts, at the anode and cathode, respectively. The alkalinity that results, i.e., via the "continuous electrolytic pH pump" results in the instantaneous precipitation of calcium carbonate (CaCO), hydrated magnesium carbonates (e.g., nesquehonite: MgCO·3HO, hydromagnesite: Mg(CO)(OH)·4HO, etc.), and/or magnesium hydroxide (Mg(OH)) depending on the CO ion-activity in solution. This results in the trapping and, hence, durable and permanent (at least ∼10 000-100 000 years) immobilization of CO that was originally dissolved in water, and that is additionally drawn down from the atmosphere within: (a) mineral carbonates, and/or (b) as solvated bicarbonate (HCO) and carbonate (CO) ions (i.e., due to the absorption of atmospheric CO into seawater having enhanced alkalinity). Taken together, these actions result in the net removal of ∼4.6 kg of CO per m of seawater catholyte processed. Geochemical simulations quantify the extents of net CO removal including the dependencies on the process configuration. It is furthermore indicated that the efficiency of realkalinization of the acidic anolyte using alkaline solids depends on their acid neutralization capacity and dissolution reactivity. We also assess changes in seawater chemistry resulting from Mg(OH) dissolution with emphasis on the change in seawater alkalinity and saturation state. Overall, this analysis provides direct quantifications of the ability of the process to serve as a means for technological CDR to mitigate the worst effects of accelerating climate change.