BG Biogeosciences BG Biogeosciences 1726-4189 Copernicus Publications Göttingen, Germany 10.5194/bg-10-7411-2013 A short history of ocean acidification science in the 20th century: a chemist's view Brewer P. G. 1 Monterey Bay Aquarium Research Institute (MBARI), 7700 Sandholdt Road, Moss Landing, CA 95039, USA 19 11 2013 10 11 7411 7422 Copyright: © 2013 P. G. Brewer 2013 This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit https://creativecommons.org/licenses/by/3.0/ This article is available from https://bg.copernicus.org/articles/10/7411/2013/bg-10-7411-2013.html The full text article is available as a PDF file from https://bg.copernicus.org/articles/10/7411/2013/bg-10-7411-2013.pdf

This review covers the development of ocean acidification science, with an emphasis on the creation of ocean chemical knowledge, through the course of the 20th century. This begins with the creation of the pH scale by Sørensen in 1909 and ends with the widespread knowledge of the impact of the "High CO<sub>2</sub> Ocean" by then well underway as the trajectory along the IPCC scenario pathways continues. By mid-century the massive role of the ocean in absorbing fossil fuel CO<sub>2</sub> was known to specialists, but not appreciated by the greater scientific community. By the end of the century the trade-offs between the beneficial role of the ocean in absorbing some 90% of all heat created, and the accumulation of some 50% of all fossil fuel CO<sub>2</sub> emitted, and the impacts on marine life were becoming more clear. This paper documents the evolution of knowledge throughout this period.

 References Andersen, N. R. and Malahoff, A.: The Fate of Fossil Fuel CO<sub>2</sub> in the Oceans, Plenum Press, 749 pp. 1977 Bolin, B.: On the exchange of carbon dioxide between the atmosphere and the sea, Tellus, 12, 274–281, 1960. Bradshaw, A. L., Brewer, P.G., Shafer, D. K., and Williams, R. T.: Measurements of total carbon dioxide and alkalinity by potentiometric titration in the GEOSECS program. Earth Planet, Sci. Lett., 55, 99–115, 1981. Brewer, P. G.: Direct observation of the oceanic CO<sub>2</sub> increase, Geophys. Res. Lett., 5, 997–1000, 1978. Brewer, P. G.: Carbon Dioxide and the Oceans, in: Changing Climate, Report of the Carbon Dioxide Assessment Committee, National Academy Press, Washington, DC, 186–215, 1983. Brewer, P. G.: What controls the variability of carbon dioxide in the surface ocean?, A plea for complete information, in: Dynamic Processes in the Chemistry of the Upper Ocean, NATO ARI, Jouy-en-Jossas, 1983, edited by: Burton, J. D., Brewer, P. G., and Chesselet, R., Plenum Press, New York, 215-281, 1986. Brewer, P. G.: Ocean chemistry of the fossil fuel signal: The haline signature of "Business as Usual", Geophys. Res. Lett., 24, 1367–1369, 1997. Brewer, P. G.: Foreword. In: "Ocean Biogeochemistry: The role of the ocean carbon cycle in global change", I –VIII, edited by: Fasham, M. J., Springer, 2003. Brewer, P. G. and Goldman, J. C.: Alkalinity changes generated by phytoplankton growth, Limnol. Oceanogr., 21, 108–117, 1976. Brewer, P. G., Wong, G. T. F., Bacon, M. P., and Spencer, D. W.: An oceanic calcium problem? Earth Planet, Sci. Lett., 26, 81–87, 1975. Brewer, P. G., Sarmiento, J. L., and Smethie, W. M.: The Transient Tracers in the Ocean (TTO) Program: The North Atlantic Study, 1981; The Tropical Atlantic Study, 1983, J. Geophys. Res., 90, 6903–6905, 1985. Brewer, P. G., Friederich, G., Peltzer, E. T., and Orr, F. M. Jr.: Direct Experiments on the Ocean Disposal of Fossil Fuel CO<sub>2</sub>, Science, 284, 943–945, 1999. Broecker, W. S. and Peng, T. H.: Tracers in the Sea, Eldigio Press, 690 pp., 1982. Broecker, W. S., Takahashi, T. and Peng, T.-H.: Reconstruction of the past atmospheric CO<sub>2</sub> contents of the contemporary ocean: An evaluation (US Department of Energy, Washington, DC) Rep. DOE/OR 857, 1985. Bromley, D. A.: The President's Scientists: Reminiscences of a White House Science Advisor, Yale University Press, 273 pp., 1994. Bruland, K. W. and Coale, K. H.: Surface water <sup>234</sup>Th/<sup>238</sup>U disequilibria: spatial and temporal variations of scavenging rates within the Pacific Ocean, in: Dynamic Processes in the Chemistry of the Upper Ocean, NATO ARI, Jouy-en-Jossas, 1983, edited by: Burton, J. D., Brewer, P. G., and Chesselet, R., Plenum Press, New York, 159–171, 1986. Buck, R. P., Rondini, S., Covington, A. K., Baucke, F. G. K., Brett, C. M. A., Camões, M. F., Milton, M. J. T., Mussini, T., Naumann, R., Pratt, K. W., Spitzer, P., and Wilson, G. S.: Measurement of pH. Definition, standards, and procedures. Pure Appl. Chem., 74, 2169–2200, 2002. Burton, J.D., Brewer, P. G., and Chesselet, R., (Eds.): Dynamic Processes in the Chemistry of the Upper Ocean, NATO ARI, Jouy-en-Jossas, 1983, Plenum Press, New York, 246 pp., 1986. Byrne, R.H. and Breland, J. A.: High precision multiwavelength pH determinations in seawater using cresol red, Deep-Sea Res., 36, 803–810, 1989. Caldeira, K. and Wickett, M. E.: Anthropogenic carbon and ocean pH, Nature, 425, 365 pp., 2003. Caldeira, K., Akai, M., Brewer, P., Chen, B., Haugan, P., Iwama, T., Johnston, P., Kheshgi, H., Li, Q., Ohsumi, T., Poertner, H., Sabine, C., Shirayama, Y., and Thomson, J.: Ocean Storage, in: Carbon Dioxide Capture and Storage: A Special Report of IPCC Working Group III, Cambridge University Press, Cambridge UK, 2005. Callendar, G. S.: The artificial production of carbon dioxide and its influence on temperature. Quarterly Journal Roy, Met. Soc., 64, 223–240, 1938. Chen, C. T. and Millero, F. J.: Gradual increase of oceanic CO<sub>2</sub>, Nature, 277, 205–206, 1979. Cicerone, R., Orr, J., Brewer, P. G., Haugan, P., Merlivat, L., Ohsumi, T., Pantoja, S., and Portner, H. O.: The ocean in a high CO<sub>2</sub> world, Eos, 85, 351–353, 2004. Clark, W. M.: The Determination of Hydrogen Ions, 3rd Edn., Williams and Wilkins: Baltimore, MD, 1928. Dickson, A. G.: The measurement of sea water pH, Mar. Chem., 4, 131–142, 1993. Dickson, A. G., Afghan, J. D., and Anderson, G. C.: Reference materials for oceanic CO<sub>2</sub> analysis: a method for the certification of total alkalinity, Mar. Chem., 80, 185–197, 2003. Dore, J.E., Lukas, R., Sadler, D. W., Church, M. J., and Karl, D. M.: Physical and biogeochemical modulation of ocean acidification in the central North Pacific, Proc. Natl. Acad. Sci. USA, 106, 12235–12240, 2009. Dyrssen, D.: A Gran titration of seawater on board <i>Sagitta</i>, Acta Chem. Scand., 19, p. 1265, 1965. Dyrssen, D. and Sillen, L. G.: Alkalinity and total carbonate in sea water: a plea for P-T independent data, Tellus , XIX, 113–121, 1967. Edmond, J. M.: High precision determination of titration alkalinity and total carbon dioxide content of sea water by potentiometric titration, Deep-Sea Res., 17, 737–750, 1970. Fairhall, A. W.: Accumulation of fossil CO2 in the atmosphere and the sea, Nature, 245, 20–23 (Erratum Nature v. 246, 106), 1973. Fasham, M. J. R.: "Ocean Biogeochemistry: The role of the ocean carbon cycle in global change", Springer, 297 pp., 2003. Forch,, C., Knudsen, M., and Sørensen, S. P. L.: Berichte über die Konstantenbestimmungenzur Aufstellung der hydrografischen Tabellen, K. Danske Vidensk, Selsk. Sk., 6. Raekke, Naturvidenske og Mathem. Afd., 12, 1–151, 1902. Francois, R. E. and Garrison, G. R.: Sound absorption based on ocean measurements. Part II: Boric acid contribution and equation for total absorption, J. Acoust. Soc. Am., 72, 1879–1890, 1982. Gattuso, J.-P., Frankignoulle, M., Smith, J. V., and Wollast, R., Coral reefs and carbon dioxide, Science, 271, 1298–1300, 1996. Gattuso, J.-P., Frankignoulle, M., and Smith, S. V.: Measurement of community metabolism and significance in the coral reef CO<sub>2</sub> source-sink debate, Proc. Natl. Acad. Sci. USA, 96, 13017–13022, 1999. Goldman, J. C. and Brewer, P. G: Effect of nitrogen source and growth rate on phytoplankton-mediated changes in alkalinity, Limnol. Oceanogr., 25, 352–357, 1980. Gorshkov, S. G. (Ed.): World Ocean Atlas, Volume 2, Atlantic and Indian Oceans, Pergamon, New York, 1978. Handa, N. and Ohsumi, T.: Direct Ocean Disposal of Carbon Dioxide Terra Pub, Tokyo, 274 pp., 1995. Haugan, P. M.: On the production and use of scientific knowledge about ocean sequestration, in: Greenhouse Gas Control Technologies, edited by: J. Gale and Y. Kaya, Pergamon, Elsevier UK, 1, 719–724, 2003. Horibe, Y., Endo, K., and Tsubota, H.: Calcium in the South Pacific, and its correlation with carbonate alkalinity, Earth Planet. Sci. Lett., 23, 136–140, 1974. Houghton, J. T., Jenkins, G. J., and Ephraums, J. J.: Climate Change: The IPCC Scientific Assessment, Cambridge University Press, 364 pp., 1990. Houghton, J. T., Meira Filho, L. G., Callander, B. A., Harris, N., Kattenberg, A., and Maskell, K. (Eds.): Climate Change 1995: The Science of Climate Change, Cambridge University Press, 572 pp., 1996. Jensen, W. B.: The symbol for pH, J. Chem. Educ, , 81, 21–22, 2004. Johnson, K .M., King, A. E., and Sieburth, J. M. N.: Coulometric TCO<sub>2</sub> analyses for marine studies: an introduction, Mar. Chem., 16, 61–82, 1985. Keeling, C. D.: The influence of Mauna Loa observatory on the development of of atmospheric CO<sub>2</sub> research, in: "Mauna Loa Observatory: a 20th Anniversary Report", NOAA Special Report, 1978. Kleypas, J. A., Buddemeier, R. W., Archer, D., Gattuso, J.-P., Langdon, C., and Opdyke, B. N.: Geochemical consequences of increased atmospheric carbon dioxide on coral reefs, Science, 284, 118–120, https://doi.org/0.1126/science.284.5411.118, 1999. Kleypas, J. A., Buddemeier, R. W., and Gattuso, J.-P.: The future of coral reefs in an age of global change, Int. J. Earth. Sci., 90, 426–437, 2001. Langdon, C., Takahashi, T., Sweeney, C., Chipman, D., Goddard, J., Marubini, F., Aceves, H., Barnett, H., and Atkinson, M. J.: Effect of calcium carbonate saturation state on the calcification rate of an experimental coral reef, Global. Biogeochem. Cy., 14, 639–654, 2000. Lemon, E.: The Land's response to more carbon dioxide. In: "The Fate of Fossil Fuel CO<sub>2</sub> in the Oceans", edited by: N. R. Andersen and A. Malahoff, Plenum Press, 749 pp., 1977. Long, S. P., Ainsworth, E. A., Leakey, A. B., Nosberger, J., and Ort, D. R.: Food for thought: Lower-than-expected crop yield stimulation with rising CO<sub>2</sub> concentrations, Science, 312, 1918–1921, 2006. Marchetti, C.: On Geoengineering and the CO<sub>2</sub> problem, Climatic Change, 1, 59–68, 1977. Melillo, J. M., Callaghan, T. V., Woodward, F. I., Salati, E., and Sinha, S. K.: Effects on Ecosystems, CH. 10, 287–310, in: Climate Change: The IPCC Scientific Assessment, IPCC, Cambridge University Press, edited by: J. T. Houghton, Jenkins, G. J., and Ephraums, J. J., 364 pp., 1990. PCAST (President's Council of Advisors on Science and Technology), 1997: Federal Energy Research and Development Agenda for the Challenges of the Twenty-First Century, US Dept. of Energy, Washington, DC, November. Powers, E. B.: The physiology of the respiration of fishes in relation to the hydrogen ion concentration of the medium, J. Gen. Physiol., 305–317, 1922. Redfield, A. C.: On the proportions of organic derivatives in sea water and their relation to the composition of plankton, James Johnstone Memorial Volume, Liverpool, 177–192, 1934. Redfield, A. C. and Goodkind, R.: The significance of the Bohr effect in the respiration and asphyxiation of the squid, Loligo Pealei, J. Exp. Biol., 6, 340–349, 1929. Revelle, R. and Suess, H. E.: Carbon dioxide exchange between atmosphere and ocean and the question of an increase of atmospheric CO<sub>2</sub> during past decades, Tellus, 9, 18–27, 1957. Riebesell, U., Zondervan, I., Rost, B., Tortell, P. D., Zeebe, R. E., and Morel, F. M. M.: Reduced calcification in marine plankton in response to increased atmospheric CO<sub>2</sub>, Nature, 407, 634–637, 2000. Rubey, W. W.: Geologic history of seawater: An attempt to state the problem, Bull. Geol. Soc. Am., 62, 1111–1148, 1951. Sabine, C. L. et al.: The oceanic sink for anthropogenic CO<sub>2</sub>, Science, 305, 367–371, 2004. Sears, M. (Ed.): Oceanography, Am. Assoc. Advanc. Sci., Washington, DC, 654 pp., 1961. Shirayama, Y. and Kogure, K.(Eds.): Special Section: Advances in biological research for CO<sub>2</sub> ocean sequestration, J. Oceanogr., 60, 691–816, 2004. Sillén, L. G.: The Physical Chemistry of Sea Water, in: Oceanography, M. Sears, ed., Am. Assoc. Advanc. Sci., Washington, DC, 1961 Sørensen, S. P. L.: Enzymstudien II: Uber die Messung und die Bedeutung der Wasserstoffionenkonzentration bei enzymatischen Prozessen, See especially, Biochem. Zeit, 21, 131–200, p. 134., 1909. Sørensen, S. P. L. and Palitzsch, S.: Über die Messung die Wasserstoffionenkonzentration des Meerwassers, Biochemische Zeitschrift, 24, 387–415, 1909. Sverdrup, H. U.,Johnson, M. W., and Fleming, R. H.: The Oceans: Their Physics, Chemistry, and General Biology, Prentice-Hall, 1087 pp., 1942. Takahashi, T., Weiss, R. F., Culberson, C. H., Edmond, J. M., Hammond, D. E, Wong, C. S., Li, Y.-H., and Bainbridge, A. E.: A carbonate chemistry profile at the 1969 Geosecs intercalibration station in the eastern Pacific Ocean, J. Geophys. Res., 75, 7648–7666, 1970. Turekian, K. K.: Results of the 1969 Geosecs test station. J. Geophys. Res., 75, p. 7639, 1970. Wattenberg, H.: Über die Titrationsalkalinität und den Kalziumkarbonatgehalt des Meerwassers, Deutsche Atlantische Exped, Meteor 1925–1927, Wiss. Erg., Bd 8, 2 Teil, 122–231, 1933. Whitfield, M.: Accumulation of fossil fuel CO<sub>2</sub> in the atmosphere and the sea, Nature, 247, 523–525, 1974. Wolf-Gladrow, D., Riebesell, U., Burkhardt, S., and Bijima, J.: Direct effects of CO<sub>2</sub> concentration on growth and isotopic composition of marine plankton, Tellus, 51B, 461–476, 1999. Zeebe, R. E. and Ridgwell, A.: Past changes in ocean carbonate chemistry. In: Ocean Acidification, edited by: J.-P. Gattuso and L. Hansson, Oxford, 326 pp., 2011.