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Abstract. Seawater absorption of anthropogenic atmospheric carbondioxide ( CO2 ) has led to a range of changes in carbonate chemistry,collectively referred to as ocean acidification. Stoichiometric dissociationconstants used to convert measured carbonate system variables (pH, pCO2 , dissolved inorganic carbon, total alkalinity) into globallycomparable parameters are crucial for accurately quantifying these changes.The temperature and salinity coefficients of these constants have generallybeen experimentally derived under controlled laboratory conditions. Here, weuse field measurements of carbonate system variables taken from the GlobalOcean Data Analysis Project version 2 and the Surface Ocean CO2 Atlas data products to evaluate the temperature dependence of the carbonic acid stoichiometric dissociation constants. By applying a novel iterativeprocedure to a large dataset of 948 surface-water, quality-controlledsamples where four carbonate system variables were independently measured,we show that the set of equations published by Lueker et al. (2000),currently preferred by the ocean acidification community, overestimates thestoichiometric dissociation constants at temperatures below about 8  ∘ C. We apply these newly derived temperature coefficients tohigh-latitude Argo float and cruise data to quantify the effects onsurface-water pCO2 and calcite saturation states. These findings highlight the critical implications of uncertainty in stoichiometric dissociation constants for future projections of ocean acidification in polar regions and the need to improve knowledge of what causes the CO2 system inconsistencies in cold waters.

ocean science

Current estimates of K&amp;lt;sub&amp;gt;1&amp;lt;/sub&amp;gt;* and K&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;* appear inconsistent with measured CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; system parameters in cold oceanic regions