Advertisement

Ocean Carbonate Chemistry: The Aquatic Chemistry Fundamentals

Conference paper
Part of the NATO Science Series book series (NAIV, volume 40)

Abstract

Some of the main questions we consider when studying the global carbon cycle are the exchange of CO2 between the ocean and atmosphere and internal redistribution of carbon species within the ocean due to uptake and remineralization of organic matter and calcium carbonate. A schematic representation of these processes is shown in Figure 1. When CO2 evades from or invades to the ocean it changes the equilibrium that exists between the species of dissolved inorganic carbon (H2CO3, HCO3 - and CO3 2) already there. Some of the CO2 is taken75 up by phytoplankton to make algal protoplasm.lasm. Some CO3 2 reacts with Ca2+ and is taken up in the form of calcium carbonate shells. Both organic matter and CaCO3 are contained in the particles that sink from the surface ocean into the deep sea. The biologically driven fluxes are called the “Biological Pump”. These particles are remineralized through respiration of the organic carbon and solubilization of the CaCO3. The reactions control the distribution of carbonate species and pH in the deep sea. The pH of seawater is a master variable that reflects the net effect of all acid and base producing aquatic geochemical processes. Some of these particles reach the sediments where their input drives an extensive set of reactions termed sedimentary diagenesis. All of these processes involve various species of the ocean dissolved inorganic carbon (DIC) system, thus the fundamental aquatic chemistry aspects of these equilibrium reactions of the carbonate system need to be understood.

Keywords

Dissolve Inorganic Carbon Carbonic Acid Total Alkalinity Carbonate Species Total Inorganic Carbon 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Bradshaw, A.L. and Brewer, P.G. (1988) High precision measurements of alkalinity and total carbon dioxide in seawater by potentiometric titration 1. Presence of unknown protolytes. Marine Chemistry 23, 69–86CrossRefGoogle Scholar
  2. Bradshaw, A.L. and Brewer, P.G. (1988) High precision measurements of alkalinity and total carbon dioxide in seawater by potentiometric titration 2. Measurements on standard solutions. Marine Chemistry 24, 155–162.CrossRefGoogle Scholar
  3. Brewer, P.G., Wong, G.T.F., Bacon, M.P. and Spencer D.W. (1975) An oceanic calcium problem? Earth and Planetary Science Letters, 26, 81–87.CrossRefGoogle Scholar
  4. Brewer, P.G. and Goldman, J. C. (1976) Alkalinity changes generated by phytoplankton growth. Limnology and Oceanography, 21, 108–117.CrossRefGoogle Scholar
  5. Brewer, P.G., Bradshaw, A. and Williams, R. (1986) Measurements of total carbon dioxide and alkalinity in the North Atlantic Ocean in 1981. In The Changing Carbon Cycle, A Global Analysis, edited by J. Trabalka and D. Reichle, pp 358–381, Springer-Verlag, New YorkGoogle Scholar
  6. Butler, J.N. (1964a) Ionic Equilibrium, a Mathematical Approach, Addison-Wesley, Reading, Mass.Google Scholar
  7. Butler, J.N. (1964b) Solubility and pH Calculations. Addison-Wesley, Reading, Mass.Google Scholar
  8. Butler, J.N. (1991) Carbon Dioxide Equilibria and their Applications, Lewis Publishers, Chelsea, Michigan, 259pp.Google Scholar
  9. Byrne R.H. (1987) Standardization of standard buffers by visible spectrometry. Analytical Chemistry 59, 1479–1481.CrossRefGoogle Scholar
  10. Byrne, R.H., Robert-Baldo, G., Thompson S.W., and Chen, C.T.A. (1988) Seawater pH measurements: an at-sea comparison of spectrophotometric and potentiometric methods. Deep-Sea Research 35, 1405–1410.CrossRefGoogle Scholar
  11. Byrne, R.H. and Breland, J.A. (1989) High precision multiwavelength pH determinations in seawater using cresol red. Deep-Sea Research 36, 803–810.CrossRefGoogle Scholar
  12. Chipman, D.W., Marra, J. and Takahashi, T. (1993) Primary production at 47oN and 20°W in the North Atlantic Ocean: A comparison between the 14C incubation method and the mixed layer carbon budget. Deep-Sea Research, 40, 151–169.CrossRefGoogle Scholar
  13. Clayton, T.D. and Byrne, R.H. J. (1993) Spectrophotometric seawater pH measurements: total hydrogen ion concentration scale calibration of m-cresol purple and at-sea results. Deep-Sea Research 40, 2315–2329.CrossRefGoogle Scholar
  14. Dickson, A.G. (1981) An exact definition of total alkalinity and a procedure for the estimation of alkalinity and total inorganic carbon from titration data. Deep-Sea Research 28, 609–623.CrossRefGoogle Scholar
  15. Dickson, A.G. (1984) pH scales and proton-transfer reactions in saline media such as seawater. Geochimica et Cosmochimica Acta, 48, 2299–2308.CrossRefGoogle Scholar
  16. Dickson, A.G. (1993) The measurement of seawater pH. Marine Chemistry 44, 131–142.CrossRefGoogle Scholar
  17. Dickson, A.G. (1993) pH buffers for seawater media based on the total hydrogen ion concentration scale. Deep-Sea Research 40, 107–118.CrossRefGoogle Scholar
  18. Garrels, R.M. and Thompson, M.E. (1962) A chemical model for seawater at 25°C and one atmosphere total pressure. American Journal of Science, 260, 57–66.CrossRefGoogle Scholar
  19. Goldman, J.C. and Brewer, P.G. (1980) Effect of nitrogen source and growth rate on phytoplankton-mediated changes in alkalinity. Limnology and Oceanography, 25, 352–357CrossRefGoogle Scholar
  20. Goyet C. and Poisson, A. (1989) New determination of carbonic acid dissociation constants in seawater as a function of temperature and salinity. Deep-Sea Research 36, 1635–1654.CrossRefGoogle Scholar
  21. Gran, G. (1952) Determination of the equivalence point in potentiometric titrations. Part II. Analyst, 77, 661–671CrossRefGoogle Scholar
  22. Johnson, K.M., King, A.E. and Sieburth, J.M. (1985) Coulometric TCO2 analyses for marine studies: An Introduction. Marine Chemistry, 16, 61–82.CrossRefGoogle Scholar
  23. Johnson, K.M., Dickson, A.G., Eischeid, G., Goyet, C., Guenther, P., Key, R.M., Millero, F.J., Purkerson, D., Sabine, C.L., Schottle, R.G., Wallace, D.R.W., Wilke R.J., and Winn, C.D. (1998) Coulometric total carbon dioxide analyses for marine studies: Assessment of the quality of total inorganic carbon measurements made during the US Indian Ocean CO2 Survey 1994–1996. Marine Chemistry 63, 21–37.CrossRefGoogle Scholar
  24. Lewis, E. and Wallace, D. (1997) CO2SYS.EXE A Program Developed for CO2 system calculations. Web site available at: http://cdiac.esd.ornl.gov/oceans/co2rprt.html.Google Scholar
  25. MacInnes, D.A. (1961) The Principles of Electrochemistry. Dover Pubs., New York 478ppGoogle Scholar
  26. McNeil, B.I., Matear, R.J., Key, R.M., Bullister, J.L. and Sarmiento, J.L. (2003) Anthropogenic CO2 uptake by the ocean based on the global chlorofluorocarbon data set. Science, 299, 235–239.CrossRefGoogle Scholar
  27. Millero, F.J. (1995) Thermodynamics of the carbon dioxide system in the oceans. Geochemica et Cosmochimica Acta 59, 661–677.CrossRefGoogle Scholar
  28. Mucci, A. (1983) The solubility of calcite and aragonite in seawater at various salinities, temperatures and one atmosphere total pressure. American Journal of Science 283, 780–799.CrossRefGoogle Scholar
  29. Perez, F.F. and Fraza, F. (1987) A precise and rapid analytical procedure for alkalinity determination. Marine Chemistry 21, 169–182.CrossRefGoogle Scholar
  30. Revelle, R. and Suess, H.E. (1957) Carbon dioxide exchange between atmosphere and ocean and the question of an increase of atmospheric CO2 during the past decade. Tellus, 9, 1827CrossRefGoogle Scholar
  31. Roy, R.N., Roy, L.N., Vogel, K.M., Moore, C.P., Pearson, T., Good, C.E., Millero F.J., and Campbell, C.D. (1993) Determination of the ionization constants of carbonic acid in seawater. Marine Chemistry 44, 249–268.CrossRefGoogle Scholar
  32. Sillen, L.G. (1959) Graphic Presentation of Equilibrium Data. In Treatise on Analytical Chemistry Part 1, Vol., 2, I.M. Kolthoff and P.J. Elving, Eds., Interscience, New York.Google Scholar
  33. Stumm, W. and Morgan, J.J. (1996) Aquatic Chemistry, Third Edition. Wiley, New York, 780pp.Google Scholar
  34. Sundquist, E. T., Plummer, L.N. and Wigley, T.M.L. (1979) Carbon Dioxide in the Ocean Surface: The Homogeneous Buffer Factor. Science, 204, 1203–1205CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2004

Authors and Affiliations

  1. 1.School of OceanographyUniversity of WashingtonSeattleUSA

Personalised recommendations