This review of the research on the marine CO2 system spans the time between the mid-19th century and the first years after World War II. It covers the period from the first attempts to determine the amount of CO2 dissolved in seawater to the first complete physico-chemical characterization of the marine CO2 system. The development of the latter was significantly influenced by the theoretical and experimental work of the Finnish chemical oceanographer Kurt Buch (1881–1967) during the first half of the 20th century. To acknowledge his outstanding achievements in Chemical Oceanography, this review is dedicated to him.The first part of our discussion is organized along the characteristic variables of the marine CO2 system. The analytical procedures that led successively to the definition of total CO2, alkalinity (“neutral carbonate”), the CO2 partial pressure (“CO2 tension”) and pH are briefly described. We trace the attempts to connect these variables quantitatively through the mass action law. After several failed attempts, CO2 dissociation constants were finally determined with the support of the International Council for the Exploration of the Sea (1931). Their results constituted the basis of the marine CO2 studies conducted after World War II.The second focus of our review refers to the various field studies, including early measurements of total CO2 and alkalinity during Norwegian (1878) and Danish expeditions (1895/96) in the North Atlantic and Arctic Ocean and the first measurements of surface water pCO2 in the North Atlantic, in 1902. Furthermore, we acknowledge the achievements of the German Atlantic expedition (1925–1927) for the characterization of the vertical and horizontal distribution of pH, pCO2 and CaCO3 saturation in the Atlantic Ocean. Among Buch's field studies of the CO2 system, we consider the Finnish monitoring program, in which pH and alkalinity were measured at over 70 stations in the northern Baltic Sea.Whenever it is appropriate, we show the connection between past scientific ideas, concepts and knowledge with current efforts and developments concerning the understanding of the marine carbon cycle and its response to increasing atmospheric CO2.
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