Hostname: page-component-77c89778f8-cnmwb Total loading time: 0 Render date: 2024-07-16T17:56:58.896Z Has data issue: false hasContentIssue false
  • English
  • Français

37.—The Thermodynamic Description of the CO2 System in Sea Water: Development and Current Status.

Published online by Cambridge University Press:  05 December 2011

John M. Edmond
John M. Edmond
Affiliation:
Department of Earth and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, Mass., USA.
Get access

Extract

Two thermodynamic schemes have been developed to describe the CO2 system in sea water. The ‘pure’ treatment is based on the theory of dilute solutions and is general. The ‘pseudo’ treatment uses ‘stoichiometric’ constants related to the acidity constants of Bronsted (1928). It is empirical and specific to the medium in which the measurements are made. The pure thermodynamic treatment developed from the early attempts to characterise the various equilibria involving CO2, carbonic acid and its anions and was much influenced by the work of biochemists and physiologists on the blood plasma system. These attempts were initiated before the concepts of complete dissociation or of activities were developed. The subsequent application of these concepts was immediate and fruitful. By 1927, especially as a result of the work of Warburg and of Hastings and Sendroy, a consistent scheme had been developed for the NaCl—NaHCO3—Na2CO3 system. This work had also been extended to phosphate, citrate and blood plasma solutions and the discrepancies between the apparent activity coefficients discussed and tentatively ascribed to complex formation.

Johnston and co-workers developed the thermodynamic treatment of the carbonate system in natural waters and by 1920 understood the relation between ΣCO2, alkalinity and carbonate solubility and had identified and solved the major analytical difficulties.

The discovery of the interference due to complexing prompted various workers to determine empirical 'apparent' or stoichiometric constants. These are derived from the experimental data by assuming that a function analogous to the pure constant, but defined in terms of total species concentrations rather than activities, will behave like the pure constant over the temperature, salinity and pressure range of interest and will not vary with the concentration of any of the species it describes. Starting with the work of Moberg and Buch in the early 1930s, a complete scheme has been developed based on this treatment. The apparent constants for carbonic and boric acids in sea water are now known with sufficient accuracy to allow detailed study of the effect of water chemistry on the formation and dissolution of carbonates under any oceanic conditions.

Type
Physics and Chemistry
Information
Proceedings of the Royal Society of Edinburgh, Section B: Biological Sciences , Volume 72 , Issue 1 , 1972 , pp. 371 - 380
Copyright
Copyright © Royal Society of Edinburgh 1972

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

References to Literature

Baxter, M. S. and Walton, A., 1970. A theoretical approach to the Suess effect. Proc. Roy. Soc. A, 318, 213–230.Google Scholar
Baxter, M. S. and Walton, A., 1971. Fluctuations of atmospheric carbon-14 concentrations during the past century. Proc. Roy. Soc. A, 321, 105–127.Google Scholar
Belyaeva, N. L., 1969. The distribution of planktonic foraminifers in water and sediment of the Antarctic Ocean, Okeanologiia, 9, 1063–1070 (In Russian.)Google Scholar
Berger, W. H., 1968. Planktonic foraminifera: selective solution and paleoclimatic interpretation. Deep Sea Res., 15, 31–44.Google Scholar
Berner, R. A., 1965. Activity coefficients of bicarbonate, carbonate and calcium ions in sea water. Geochim. Cosmochim. Acta, 29, 947–965.CrossRefGoogle Scholar
Berner, R. A. and Wilde, P., 1972. Dissolution kinetics of calcium carbonate in sea-water. 1. Saturation state parameters for kinetic calculations. Am. J. Sci. (In press.)CrossRefGoogle Scholar
Bramlette, M. N., 1961. Pelagic Sediments in Oceanography (Ed. Sears, M.), 301–322. Washington: A.A.A.S.Google Scholar
Brander, E., 1932. Uber den Einfiuss des Druckes auf die Leitfahigkeit der Elektrolyte. Commentat. Physico-Math., 6, 1–108.Google Scholar
Bronsted, J. N., 1928. Acid and Base Catalysis. Chem. Rev., 5, 237–338.CrossRefGoogle Scholar
Buch, K., 1930. Die Kohlensaurefaktoren des Meerwassers, Rapp. P.-V. Réun. Cons. Perm. Int. Explor. Mer, 67, 14–31.Google Scholar
Buch, K. and Gripenbero, S., 1932. Uber den Einfluss des Wasserdruches auf pH und das Kohlensauregleichgewicht in grosseren Meersteifen. J. Cons. Perm. Int. Explor. Mer., 7, 233–245.CrossRefGoogle Scholar
Buch, K., Harvey, H. W., Wattenberg, H. and Gripenberg, S., 1932. Uber der Kohlensauresystem in Meerswasser. Rapp. P.-V. Réun. Cons. Perm. Int. Explor. Mer., 79, 1–70.Google Scholar
Chave, K. E. and Suess, E., 1967. Suspended minerals in sea-water. Trans. N.Y. Acad. Sci. (II), 29, 991–1000.CrossRefGoogle Scholar
Culberson, C. and Pytkowicz, R. M., 1968. Effect of pressure on carbonic acid, boric acid and the pH of sea water. Limnol. Oceanogr., 13, 403–417.CrossRefGoogle Scholar
Culberson, C, Pytkowicz, R. M. and Hawley, J. E., 1970. Alkalinity determination by the pH method. J. Mar. Res., 28, 15–21.Google Scholar
Debye, P., 1928. Polar Molecules. Chemical Catalog Co. (Reprinted Dover, 1958.)Google Scholar
Distèche, A., 1959. pH measurement with a glass electrode withstanding 1500 kg/cm2 hydrostatic pressure. Rev. Sci. Instrum., 30, 474–478.CrossRefGoogle Scholar
Distèche, A. and Disteche, S., 1967. The effect of pressure on the dissociation of carbonic acid from measurements with buffered glass electrode cells; the effects of NaCl KC1, Mg2+, Ca2+ and and of boric acid with special reference to sea water. J. Electrochem. Soc., 114, 330–340.CrossRefGoogle Scholar
Duedall, I. W., 1972. The partial molal volume of calcium carbonate in sea water. Geochim. Cosmochim. Acta. (In press.)CrossRefGoogle Scholar
Edmond, J. M., 1970 a. The carbonic acid system in sea water, 174 pp. Ph. D. thesis, Univ. Calif., San Diego.Google Scholar
Duedall, I. W., 1970 b. Carbonate and silicate dissolution in the deep ocean. Proc. Int. Symp. Hydrogeochem. Biogeochem., IAGC Tokyo, Japan. (In press.)Google Scholar
Duedall, I. W., 1970 c, High precision determination of titration alkalinity and total carbon dioxide content of sea water by potentiometric titration. Deep Sea Res., 17, 737–750.Google Scholar
Duedall, I. W., 1972. Alkalinity determinations at the Geosecs intercalibration stations. Am. Geophys. Un. Abstr. (In press.)Google Scholar
Edmond, J. M. and Gieskes, J. M. T. M., 1970. On the calculation of the degree of saturation of sea water with respect to calcium carbonate under in situ conditions. Geochim. Cosmochim. Acta, 34, 1261–1291.CrossRefGoogle Scholar
Garrels, R. M., 1967. Genesis of some ground waters from igneous rocks. In Researches in Geochemistry, 2, 405–420. (Ed. Abelson, P. H..)Google Scholar
Garrels, R. M. and Mackenzie, F. T., 1971. Evolution of Sedimentary Rocks, 397 pp. New York: Norton.Google Scholar
Hastings, A. B., Murray, C. D. and Sendroy, J. Jr.,, 1927. The solubility of calcium carbonate in salt solutions and biological fluids. J. Biol. Chem., 71, 723–781.CrossRefGoogle Scholar
Hastings, A. B. and Sendroy, J. Jr.,, 1925. The effect of variation in ionic strength on the apparent first and second dissociation constants of carbonic acid. J. Biol. Chem., 65, 445–455.CrossRefGoogle Scholar
Ingri, N., 1963. Equilibrium studies of polyanions. XI. Polyborates in 3·0 M NaBr, 3·0 M Li Br and 2·0 M KBr: a comparison with data obtained in 3·0 M NaCl4. Acta Chem. Scand., 17, 581–589.CrossRefGoogle Scholar
Johnston, J., 1916. The determination of carbonic acid, combined and free, in solution, particularly in natural waters. J. Am. Chem. Soc, 38, 947–975.CrossRefGoogle Scholar
Johnston, J. and Williamson, E. D., 1916. The complete solubility curve of calcium carbonate. J. Am. Chem. Soc, 38, 975–983.CrossRefGoogle Scholar
Keeling, C. D., 1968. Carbon Dioxide in surface ocean waters, 4, Global distribution. J. Geophys. Res., 73, 4543–553.CrossRefGoogle Scholar
Kelly, J. J. Jr., 1970. Carbon dioxide in the surface waters of the North Atlantic Ocean and the Barents and Kara Seas. Limnol. Oceanogr., 15, 80–87.CrossRefGoogle Scholar
Lewis, A. N., 1907. Outlines of a new system of thermodynamic chemistry. Proc. Am. Acad. Sci., 43, 259–293.CrossRefGoogle Scholar
Li, Y. H., Takahashi, T. and Broecker, W. S., 1969. The degree of saturation of CaCo3 in the oceans. J. Geophys. Res., 74, 5507–5525.CrossRefGoogle Scholar
Lyman, J. 1957. Buffer mechanism of sea water, 196 pp. Ph. D. thesis, Univ. Calif., Los Angeles.Google Scholar
Millero, F. J. and Berner, R. A., 1972. Effect of pressure on carbonate equilibria in sea water. Geochim. Cosmochim. Ada, 36, 92–98.CrossRefGoogle Scholar
Moberg, E. G., Greenberg, D. M., Revelle, R. and Allen, E. C, 1934. The buffer mechanism of sea water. Bull. Scripps Instn Oceanogr., Tech. Ser., 3, 231–278.Google Scholar
Murray, J. and Renard, A. F., 1891. Deep sea deposits based on the specimens collected during the voyage of H.M.S. Challenger in the years 1872 to 1876. Rep. Scient. Res. Voy. HMS Challenger, 525 pp. (Johnson Reprint, London: 1965).Google Scholar
Peterson, M. N. A., 1966. Calcite: rates of dissolution in a vertical profile in the central Pacific. Science, N.Y., 154, 1542–1544.CrossRefGoogle Scholar
Pytkowicz, R. M., 1965. Rates of inorganic calcium carbonate nucleation. J. Geol., 73, 196–199.CrossRefGoogle Scholar
Pytkowicz, R. M. and Connors, V. N., 1964. High pressure solubility of CaCO3 in sea water. Science, N.Y., 144, 840–841.CrossRefGoogle Scholar
Pytkowicz, R. M., Distéche, A. and Distéche, S., 1967. Calcium carbonate solubility in sea water at in situ pressures. Earth Planet. Sci. Lett., 2, 430–432.CrossRefGoogle Scholar
Pytkowicz, R. M. and Fowler, G. A., 1967. Solubility of foraminifera in sea water at high pressure. Geochem. J., 1, 169–182.CrossRefGoogle Scholar
Siever, R., 1968. Sedimentological consequences of a steady-state ocean-atmosphere. Sedimentology, 11, 5–29.CrossRefGoogle Scholar
Strickland, J. D. H. and Parsons, T. R., 1960. A Manual of Sea Water Analysis. Bull. Fish. Res. Bd Can., 125.Google Scholar
Suess, H. E., 1969. Bristlecone pine calibration of the radio-carbon time scale 5200 bc to the present. In Radiocarbon variations and absolute chronology (12th Nobel Symposium). (Ed. Olsson, I. U..) New York: Wiley.Google Scholar
Takahashi, T., Weiss, R. F., Culberson, C. H., Edmond, J. M., Hammond, D. E., Wong, C. S., Li, Y. H. and Brainbridge, A. E., 1970. A carbonate chemistry profile at the 1969 Geosecs intercalibration station in the Eastern Pacific Ocean. J. Geophys. Res., 75, 7648–7666.CrossRefGoogle Scholar
Warburg, E. J., 1922. Studies on carbonic acid compounds and hydrogen ion activities in blood and salt solutions. Biochem. J., 16, 153–340.CrossRefGoogle ScholarPubMed
Wattenberg, H., 1933. Uber die Titrationsalkalinitat und den Kalziumkarbonatgehalt des Meers-wassers. Wiss. Ergebn. Dt. Atlant. Exped. Meteor, 8 (2), 122–231.Google Scholar
Weiss, R. F., Gieskes, J. M. T. M., Edmond, J. M. and Li, Y. H., 1972. CO2 in the oceans; recent Geosecs intercalibrations and results. Am. Geophys. Un. Abstr., 53, 400.Google Scholar
Weyl, P. K., 1967. The solution behaviour of carbonate minerals in sea water. Stud. Trop. Oceanogr. Miami, 5, 178–228.Google Scholar