Thermal and haline effects on the calculation of air-sea CO₂ fluxes revisited

Abstract. The presence of vertical temperature and salinity gradients in the upper ocean and the occurrence of variations in temperature and salinity on time scales from hours to many years complicate the calculation of the flux of carbon dioxide (CO₂) across the sea surface. Temperature and salinity affect the interfacial concentration of aqueous CO₂ primarily through their effect on solubility with lesser effects related to saturated vapour pressure and the relationship between fugacity and partial pressure. The effects of temperature and salinity profiles and changes in the aqueous concentration act primarily through the partitioning of the carbonate system. Contrary to some recent analysis, it is shown that the effect on CO₂ fluxes of a cool skin on the sea surface is large and ubiquitous. An opposing effect on calculated fluxes is related to the occurrence of warm layers near the surface; this effect can be locally large but will usually coincide with periods of low exchange. A salty skin and salinity anomalies in the upper ocean also affect CO₂ flux calculations, though the haline effects are generally weaker than the thermal effects.