The internal consistency of the North Sea carbonate system

Abstract

In 2002 (February) and 2005 (August), the full suite of carbonate system parameters (total alkalinity (AT), dissolved inorganic carbon (DIC), pH, and partial pressure of CO2 (pCO2) were measured on two re-occupations of the entire North Sea basin, with three parameters (AT, DIC, pCO2) measured on four additional re-occupations, covering all four seasons, allowing an assessment of the internal consistency of the carbonate system. For most of the year, there is a similar level of internal consistency, with AT being calculated to within ±6μmolkg−1 using DIC and pH, DIC to ±6μmolkg−1 using AT and pH, pH to ±0.008 using AT and pCO2, and pCO2 to ±8μatm using DIC and pH, with the dissociation constants of Millero et al. (2006). In spring, however, we observe a significant decline in the ability to accurately calculate the carbonate system. Lower consistency is observed with an increasing fraction of Baltic Sea water, caused by the high contribution of organic alkalinity in this water mass, not accounted for in the carbonate system calculations. Attempts to improve the internal consistency by accounting for the unconventional salinity–borate relationships in freshwater and the Baltic Sea, and through application of the new North Atlantic salinity–boron relationship (Lee et al., 2010), resulted in no significant difference in the internal consistency.