CO2 Air–Sea Exchange due to Calcium Carbonate and Organic Matter Storage, and its Implications for the Global Carbon Cycle

Release of CO2 from surface ocean water owing to precipitation of CaCO3 and the imbalance between biological production of organic matter and its respiration, and their net removal from surface water to sedimentary storage was studied by means of a quotient θ = (CO2 flux to the atmosphere)/(CaCO3 precipitated). θ depends not only on water temperature and atmospheric CO2 concentration but also on the CaCO3 and organic carbon masses formed. In CO2 generation by CaCO3 precipitation, θ varies from a fraction of 0.44 to 0.79, increasing with decreasing temperature (25 to 5°C), increasing atmospheric CO2 concentration (195–375 ppmv), and increasing CaCO3 precipitated mass (up to 45% of the initial DIC concentration in surface water). Primary production and net storage of organic carbon counteracts the CO2 production by carbonate precipitation and it results in lower CO2 emissions from the surface layer. When atmospheric CO2 increases due to the ocean-to-atmosphere flux rather than remaining constant, the amount of CO2 transferred is a non-linear function of the surface layer thickness because of the back-pressure of the rising atmospheric CO2. For a surface ocean layer approximated by a 50-m-thick euphotic zone that receives input of inorganic and organic carbon from land, the calculated CO2 flux to the atmosphere is a function of the CaCO3 and Corg net storage rates. In general, the carbonate storage rate has been greater than that of organic carbon. The CO2 flux near the Last Glacial Maximum is 17 to 7×1012 mol/yr (0.2–0.08 Gt C/yr), reflecting the range of organic carbon storage rates in sediments, and for pre-industrial time it is 38–42×1012 mol/yr (0.46–0.50 Gt C/yr). Within the imbalanced global carbon cycle, our estimates indicate that prior to anthropogenic emissions of CO2 to the atmosphere the land organic reservoir was gaining carbon and the surface ocean was losing carbon, calcium, and total alkalinity owing to the CaCO3 storage and consequent emission of CO2. These results are in agreement with the conclusions of a number of other investigators. As the CO2 uptake in mineral weathering is a major flux in the global carbon cycle, the CO2 weathering pathway that originates in the CO2 produced by remineralization of soil humus rather than by direct uptake from the atmosphere may reduce the relatively large imbalances of the atmosphere and land organic reservoir at 102–104-year time scales.