Stability of alkalinity in ocean alkalinity enhancement (OAE) approaches -consequences for durability of CO2 storage

According to modelling studies, ocean alkalinity enhancement (OAE) is one of the proposed carbon dioxide removal (CDR) approaches with large potential, with the beneficial side effect of counteracting ocean acidification. The real-world application of OAE, however, remains unclear as most basic assumptions are untested. Before largescale deployment can be considered, safe and sustainable procedures for the addition of alkalinity to seawater must be identified and governance established. One of the concerns is the stability of alkalinity when added to seawater. The surface ocean is already supersaturated with respect to calcite and aragonite, and an increase in total alkalinity (TA) together with a corresponding shift in carbonate chemistry towards higher carbonate ion concentrations would result in a further increase in supersaturation, and potentially to solid carbonate precipitation. Precipitation of carbonate minerals consumes alkalinity and increases dissolved CO2 in seawater, thereby reducing the efficiency of OAE for CO2 removal. In order to address the application of alkaline solution as well as fine particulate alkaline solids, a set of six experiments was performed using natural seawater with alkalinity of around 2400 mu mol kgsw(-1). The application of CO2- equilibrated alkaline solution bears the lowest risk of losing alkalinity due to carbonate phase formation if added total alkalinity (ATA) is less than 2400 mu mol kgsw(-1). The addition of reactive alkaline solids can cause a net loss of alkalinity if added ATA > 600 mu mol kgsw(-1) (e.g. for Mg(OH)(2)). Commercially available (ultrafine) Ca(OH)(2) causes, in general, a net loss in TA for the tested amounts of TA addition, which has consequences for suggested use of slurries with alkaline solids supplied from ships. The rapid application of excessive amounts of Ca(OH)(2), exceeding a threshold for alkalinity loss, resulted in a massive increase in TA (> 20 000 mu mol kgsw(-1)) at the cost of lower efficiency and resultant high pH values > 9.5. Analysis of precipitates indicates formation of aragonite. However, unstable carbonate phases formed can partially redissolve, indicating that net loss of a fraction of alkalinity may not be permanent, which has important implications for real-world OAE application. Our results indicate that using an alkaline solution instead of reactive alkaline particles can avoid carbonate formation, unless alkalinity addition via solutions shifts the system beyond critical supersaturation levels. To avoid the loss of alkalinity and dissolved inorganic carbon (DIC) from seawater, the application of reactor techniques can be considered. These techniques produce an equilibrated solution from alkaline solids and CO2 prior to application. Differing behaviours of tested materials suggest that standardized engineered materials for OAE need to be developed to achieve safe and sustainable OAE with solids, if reactors technologies should be avoided.

Automated summary

Ocean alkalinity enhancement (OAE) is a carbon dioxide removal (CDR) approach with potential for countering ocean acidification. However, its real-world application requires safe and sustainable procedures for adding alkalinity to seawater. The stability of alkalinity when added to seawater is a concern, as it can lead to carbonate precipitation and reduce the efficiency of CO2 removal. Experiments show that using CO2-equilibrated alkaline solution poses the lowest risk of losing alkalinity, while the addition of reactive alkaline solids can cause net loss if added alkalinity exceeds certain levels. Precipitates formed can partially redissolve, suggesting that net loss of alkalinity may not be permanent.