Ocean alkalinity enhancement - avoiding runaway CaCO3 precipitation during quick and hydrated lime dissolution

Abstract

Ocean alkalinity enhancement (OAE) is a method that can remove carbon dioxide (CO2) from the atmosphere and counteract ocean acidification through the dissolution of alkaline minerals. Currently, critical knowledge gaps exist regarding the dissolution of different minerals suitable for OAE in natural seawater. Of particular importance is to understand how much alkaline mineral can be dissolved before secondary precipitation of calcium carbonate (CaCO3) occurs, since secondary CaCO3 precipitation reduces the atmospheric CO2 uptake potential of OAE. Using two types of mineral proposed for OAE, quick lime (CaO) and hydrated lime (Ca(OH)2), we show that both (<63 μm of diameter) dissolved in seawater within a few hours. No CaCO3 precipitation occurred at a saturation state (ωA) of ∼5, but CaCO3 precipitation in the form of aragonite occurred above an ωA value of 7. This limit is lower than expected for typical pseudo-homogeneous precipitation, i.e. in the presence of colloids and organic matter. Secondary precipitation at low ωA (∼ 7) was the result of heterogeneous precipitation onto mineral surfaces, most likely onto the added CaO and Ca(OH)2 particles. Most importantly, runaway CaCO3 precipitation was observed, a condition where significantly more total alkalinity (TA) was removed than initially added. Such runaway precipitation could reduce the OAE CO2 uptake efficiency from ∼ 0.8 mol of CO2 per mole of added TA down to 0.1 mol of CO2 per mole of TA. Runaway precipitation appears to be avoidable by dilution below the critical ωA threshold of 5, ideally within hours of the mineral additions to minimise initial CaCO3 precipitation. Finally, OAE simulations suggest that for the same ωA threshold, the amount of TA that can be added to seawater would be more than 3 times higher at 5 °C than at 30 °C. The maximum TA addition could also be increased by equilibrating the seawater to atmospheric CO2 levels (i.e. to a pCO2 of ∼ 416 μatm) during addition. This would allow for more TA to be added in seawater without inducing CaCO3 precipitation, using OAE at its CO2 removal potential.