References

Ocean Science

Ocean Sci.

1812-0792

Copernicus Publications

Göttingen, Germany

10.5194/os-5-285-2009

Precipitation of solid phase calcium carbonates and their effect on application of seawater SA–T–P models

Marion

G. M.

¹ Millero

F. J.

² Feistel

Desert Research Institute, 2215 Raggio Parkway, Reno, NV 89512, USA

University of Miami, 4600 Rickenbacker Causeway, Miami, FL 33149, USA

Leibniz Institute for Baltic Sea Research IOW, Seestr. 15, 18119, Warnemünde, Germany

21 07 2009

5 3 285 291

2009

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At the present time, little is known about how broad salinity and temperature ranges are for seawater thermodynamic models that are functions of absolute salinity (SA), temperature (T) and pressure (P). Such models rely on fixed compositional ratios of the major components (e.g., Na/Cl, Mg/Cl, Ca/Cl, SO4/Cl, etc.). As seawater evaporates or freezes, solid phases [e.g., CaCO3(s) or CaSO42H2O(s)] will eventually precipitate. This will change the compositional ratios, and these salinity models will no longer be applicable. A future complicating factor is the lowering of seawater pH as the atmospheric partial pressures of CO2 increase. A geochemical model (FREZCHEM) was used to quantify the SA−T boundaries at P=0.1 MPa and the range of these boundaries for future atmospheric CO2 increases. An omega supersaturation model for CaCO3 minerals based on pseudo-homogeneous nucleation was extended from 25–40°C to 3°C. CaCO3 minerals were the boundary defining minerals (first to precipitate) between 3°C (at SA=104 g kg−) and 40°C (at SA=66 g kg−). At 2.82°C, calcite(CaCO3) transitioned to ikaite(CaCO36H2O) as the dominant boundary defining mineral for colder temperatures, which culminated in a low temperature boundary of −4.93°C. Increasing atmospheric CO2 from 385 μatm (390 MPa) (in Year 2008) to 550 μatm (557 MPa) (in Year 2100) would increase the SA and t boundaries as much as 11 g kg−1 and 0.66°C, respectively. The model-calculated calcite-ikaite transition temperature of 2.82°C is in excellent agreement with ikaite formation in natural environments that occurs at temperatures of 3°C or lower. Furthermore, these results provide a quantitative theoretical explanation (FREZCHEM model calculation) for why ikaite is the solid phase CaCO3 mineral that precipitates during seawater freezing.

References 1

Assur, A.: Composition of sea ice and its tensile strength, in: Arctic Sea Ice, Publication 598, National Acad. Sci.-Nat. Res. Council, Washington, DC, 106–138, 1958.

Bischoff, J. L., Fitzpatrick, J. A., and Rosenbauer, R. J.: The solubility and stabilization of ikaite (CaCO36H2O) from 0° to 25°C: Environmental and paleoclimatic implications for thinolite tufa, J. Geol., 101, 21–33, 1993.

Dieckmann, G. S., Nehrke, G., Papadimitriou, S., Göttlicher, J., Steininger, R., Kennedy, H., Wolf-Gladrow, D., and Thomas, D. N.: Calcium carbonate as ikaite crystals in Antarctic sea ice, Geophys. Res. Lett., 35, L08501, https://doi.org/10.1029/2008GL033540, 2008.

Feistel, R.: A new extended Gibbs thermodynamic potential of seawater, Progr. Ocean., 58, 43–114, 2003.

Feistel, R.: A Gibbs function for seawater thermodynamics for −6°C to 80°C and salinity up to 120 g/kg, Deep-Sea Res. I, 55, 1639–1671, 2008.

Feistel, R. and Marion, G. M.: A Gibbs-Pitzer function for high-salinity seawater thermodynamics, Progr. Ocean., 74, 515–539, 2007.

Feistel, R. and Weinreben, S.: Is Practical Salinity conservative in the Baltic Sea? Oceanologia, 50, 73–82, 2008.

Feistel, R., Nausch, G., and Wasmund, N.: State and Evolution of the Baltic Sea, 1952–2005. A Detailed 50-Year Survey of Meteorology and Climate, Physics, Chemistry, Biology, and Marine Environment, John Wiley & Sons, Inc., Hoboken, NJ, 2008.

Gitterman, K. E.: Thermal analysis of sea water, CRREL TL 287, USACRREL, Hanover, New Hampshire, 1937.

Hardie, L. A.: Secular variations in Precambrian seawater chemistry and the timing of Precambrian aragonite seas and calcite seas, Geology, 31, 785–788, 2003.

Larsen, D.: Origin and paleoenvironmental significance of calcite pseudomorphs after ikaite in the Oligocene Creede Formation, Colorado, J. Sed. Res., A64, 593–603, 1994.

Maldonado, C. F. E., Giroir, G., Dandurand, J. L., and Schott, J.: The dissolution of calcite in seawater from 40° to 90°C at atmospheric pressure and 35\permil salinity, Chem. Geol., 97, 113–123, 1992.

Marion, G. M.: Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O system, Geochim. Cosmochim. Acta, 65, 1883–1896, 2001.

Marion, G. M.: A molal-based model for strong acid chemistry at low temperatures (<200 to 298 K), Geochim. Cosmochim. Acta, 66, 2499–2516, 2002.

Marion, G. M., Catling, D. C., and Kargel, J. S.: Modeling aqueous ferrous iron chemistry at low temperatures with application to Mars, Geochim. Cosmochim. Acta, 67, 4251–4266, 2003.

Marion, G. M., Catling, D. C., and Kargel, J. S.: Modeling gas hydrate equilibria in electrolyte solutions, CALPHAD, 30, 248–259, 2006.

Marion, G. M., Catling, D. C., and Kargel, J. S.: Br/Cl partitioning in chloride minerals in the Burns formation on Mars, Icarus, 200, 436–445, 2009a.

Marion, G. M., Crowley, J. K., Thomson, B. J., Kargel, J. S., Bridges, N. T., Hook, S. J., Baldridge, A., Brown, A. J., Ribeiro da Luz, B., and de Souza Filho, C. R.: Modeling aluminum-silicon chemistries and application to Australian acidic playa lakes as analogues for Mars, Geochim. Cosmochim. Acta, 73, 3493–3511, 2009b.

Marion, G. M. and Farren, R. E.: Mineral solubilities in the Na-K-Mg-Ca-Cl-SO4-H2O system: A re-evaluation of the sulfate chemistry in the Spencer-Møller-Weare model, Geochim. Cosmochim. Acta, 63, 1305–1318, 1999.

Marion, G. M. and Kargel, J. S.: Cold Aqueous Planetary Geochemistry with FREZCHEM: From Modeling to the Search for Life at the Limits, Springer, Heidelberg, Germany, 2008.

Marion, G. M., Kargel, J. S., and Catling, D. C.: Modeling ferrous-ferric iron chemistry with application to Martian surface geochemistry, Geochim. Cosmochim. Acta, 72, 242–266, 2008.

Marion, G. M., Kargel, J. S., Catling, D. C., and Jakubowski, S. D.: Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa, Geochim. Cosmochim. Acta, 69, 259–274, 2005.

McCaffrey, M. A., Lazar, B., and Holland, H. D.: The evaporation path of seawater and the coprecipitation of Br$^-$ and K$^+$ with halite, J. Sed. Petrology, 57, 928–937, 1987.

Millero, F. J.: Physical Chemistry of Natural Waters, Wiley-Interscience, New York, 2001.

Millero, F. J.: The marine inorganic carbon cycle, Chem. Rev., 107, 308–341, 2007.

Millero, F. J., Feistel, R., Wright, D. G., and McDougall, T. J.: The composition of Standard Seawater and the definition of the Reference-Composition Salinity Scale, Deep-Sea Res., 55, 50–72, 2008.

Millero, F. J. and Kremling, K.: The densities of Baltic waters, Deep-Sea Res., 23, 1129–1138, 1976.

Millero, F. J. and Sohn, M. L.: Chemical Oceanography, CRC Press, Boca Raton, 1992.

Morse, J. W., Arvidson, R. S., and Lüttge, A.: Calcium carbonate formation and dissolution, Chem. Rev., 107, 342–381, 2007.

Morse, J. W. and He, S.: Influences of $T$, $S$ and $P_\rm CO_2$ on the pseudo-homogeneous precipitation of CaCO3 from seawater: implications for whiting formation, Mar. Chem., 41, 291–297, 1993.

Morse, J. W. and Mackenzie, F. T.: Geochemistry of Sedimentary Carbonates, Elsevier, Amsterdam, 1990.

Morse, J. W., Wang, Q., and Tsio, M. Y.: Influences of temperature and Mg:Ca ratio on CaCO3 precipitates from seawater, Geol., 25, 85–87, 1997.

Omelon, C. R., Pollard, W. H., and Marion, G. M.: Seasonal formation of ikaite (CaCO36H2O) in saline spring discharge at Expedition Fiord, Canadian High Arctic: Assessing conditional constraints for natural crystal growth, Geochim. Cosmochim. Acta, 65, 1429–1437, 2001.

Pauly, H.: "Ikaite", a new mineral from Greenland, Arctic, 16, 263–264, 1963.

Pitzer, K. S.: Ion interaction approach: Theory and data correlation, in: Activity Coefficients in Electrolyte Solutions, 2nd Ed., CRC Press, Boca Raton, 75–153, 1991.

Pitzer, K. S.: Thermodynamics, 3rd Ed., McGraw-Hill, New York, 1995.

Pytkowicz, R. M.: Calcium carbonate retention in supersaturated seawater, Am. J. Sci., 273, 515–522, 1973.

Richardson, C.: Phase relationships in sea ice as a function of temperature, J. Glaciol., 17, 507–519, 1976.

Ringer, W. E.: Über die veränderungen in der Zusammensetzung des Meereswasseralzes beim Ausfrieren, Verh. Rijksinst. Onderz. Zee, 3, 1–55, 1906.

Rohde, K.-H.: Untersuchungen über die Calcium- und Magnesiumanomalie in der Ostsee, Beitr. Meeresk., 19, 18–31, 1966.

Steel, R. G. D., Torrie, J. H., and Dickey, D. A.: Principles and Procedures of Statististics: A Biometrical Approach, 3rd Ed., McGraw-Hill, Boston, 1997.

Weeks, W. F. and Ackley, S. F.: The growth, structure, and properties of sea ice, CRREL Monograph 82-1, USACRREL, Hanover, New Hampshire, 1982.

Zuddas, P. and Mucci, A.: Kinetics of calcite precipitation from seawater: II. The influence of the ionic strength, Geochim. Cosmochim. Acta, 62, 757–766, 1998.