The recommended dissociation constants for carbonic acid in seawater

A coherent representation of carbonate dissociation constants and measured inorganic carbon species is essential for a wide range of environmentally important issues such as oceanic uptake of anthropogenic CO2 and carbon cycle depictions in ocean circulation models. Previous studies have shown varying degrees of discordance between calculated and measured CO2-system parameters. It is unclear if this is due to errors in thermodynamic models or in measurements. In this work, we address this issue using a large field dataset (15,300 water samples) covering all ocean basins. Our field data, obtained using laboratory-calibrated measurement protocols, are most consistent with calculated parameters using the dissociation constants of Mehrbach et at. [1973] as refit by Dickson and Millero [1987]. Thus, these constants are recommended for use in the synthesis of the inorganic carbon data collected during the global CO2 survey during the 1990s and for characterization of the carbonate system in seawater.