Ocean Science
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2009
10.5194/os-5-285-2009
http://www.ocean-sci.net/5/285/2009/
http://www.ocean-sci.net/5/285/2009/os-5-285-2009.html
http://www.ocean-sci.net/5/285/2009/os-5-285-2009.pdf
285
291
2009-07-21
Precipitation of solid phase calcium carbonates and their effect on application of seawater <i>S<sub>A</sub></i>–<i>T</i>–<i>P</i> models
G. M. Marion
giles.marion@dri.edu
F. J. Millero
R. 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
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 (<i>S<sub>A</sub></i>), temperature (<i>T</i>) and pressure (<i>P</i>). Such
models rely on fixed compositional ratios of the major components (e.g.,
Na/Cl, Mg/Cl, Ca/Cl, SO<sub>4</sub>/Cl, etc.). As seawater evaporates or freezes,
solid phases [e.g., CaCO<sub>3</sub>(s) or CaSO<sub>4</sub>2H<sub>2</sub>O(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 CO<sub>2</sub>
increase. A geochemical model (FREZCHEM) was used to quantify the <i>S<sub>A</sub></i>−<i>T</i>
boundaries at <i>P</i>=0.1 MPa and the range of these boundaries for future
atmospheric CO<sub>2</sub> increases. An omega supersaturation model for
CaCO<sub>3</sub> minerals based on pseudo-homogeneous nucleation was extended from
25–40°C to 3°C. CaCO<sub>3</sub> minerals were the boundary defining
minerals (first to precipitate) between 3°C (at <i>S<sub>A</sub></i>=104 g kg<sup>−</sup>) and 40°C (at <i>S<sub>A</sub></i>=66 g kg<sup>−</sup>). At 2.82°C,
calcite(CaCO<sub>3</sub>) transitioned to ikaite(CaCO<sub>3</sub>6H<sub>2</sub>O) as the
dominant boundary defining mineral for colder temperatures, which culminated
in a low temperature boundary of −4.93°C. Increasing atmospheric
CO<sub>2</sub> from 385 μatm (390 MPa) (in Year 2008) to 550 μatm
(557 MPa) (in Year 2100) would increase the <i>S<sub>A</sub></i> and t boundaries as much as
11 g kg<sup>−1</sup> 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 CaCO<sub>3</sub> mineral that precipitates during
seawater freezing.
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