Calcite solubility, effect

Bertram M. (1989) Temperature effects on magnesian calcite solubility and reactivity Application to natural systems. M.S. thesis, Univ. Hawaii. 

Example 7.9. Effect of Pressure and Temperature on Calcite Solubility in Seawater An enclosed sample of the surface seawater, as discussed in Example 7.8 (25°C pH = 8.2 [Ca ] = 1.06 x 10" M [Carb-Alk] = 2.4 x 10" eq liter" ), is cooled to 5°C and then subjected to increases in total pressure of up to 1000 atm (equivalent to exposing the sample to increased water depths of approximately 10,000 m). How does the composition, pH, [CO3"], [Ca "], and extent of oversaturation change as a result of the temperature change at 1 atm and as a result of the pressure change at 5°C The water is incipiently oversaturated with respect to calcite. Assume that CaC03... 

Table V. Effect of Acetic Acid Addition on Calcite Solubility. Modeled with...

For instance, calcite solubility increases in the presence of CO due to the formation of H COj and HCOj, and of silicon - due to increase in pH because of dissociation of orthosilicic add H SiO (see below). Figure 2.29 shows correlation of gypsum effective solubility vs. various electrolytes. 

The solubility of calcite and aragonite increases with increasing pressure and decreasing temperature in such a way that deep waters are undersaturated with respect to calcium carbonate, while surface waters are supersaturated. The level at which the effects of dissolution are first seen on carbonate shells in the sediments is termed the lysocline and coincides fairly well with the depth of the carbonate saturation horizon. The lysocline commonly lies between 3 and 4 km depth in today s oceans. Below the lysocline is the level where no carbonate remains in the sediment this level is termed the carbonate compensation depth. 

Fig. 14.6. Effect of C02 fugacity on the solubility of calcite (top) and on pH (bottom), calculated at 25 °C using a sliding fugacity path.

Calcium carbonate solubility is also temperature and pressure dependent. Pressure is a 6r more important fector than temperature in influencing solubility. As illustrated in Table 15.1, a 20°C drop in temperature boosts solubility 4%, whereas the pressure increase associated with a 4-km increase in water depth increases solubility 200-fold. The large pressure effect arises from the susceptibility of the fully hydrated divalent Ca and CO ions to electrostriction. Calcite and aragonite are examples of minerals whose solubility increases with decreasing temperature. This unusual behavior is referred to as retrograde solubility. Because of the pressure and temperature effects, calcium carbonate is fer more soluble in the deep sea than in the surfece waters (See the online appendix on the companion website). 

All surface seawater is presently supersaturated with respect to biogenic calcite and aragonite with Cl ranging from 2.5 at high latitudes and 6.0 at low latitudes. The elevated supersaturations at low latitude reflect higher [COj ] due to (1) the effect of temperature on CO2 solubility and the for HCO3, and (2) density stratification. At low latitudes, enhanced stratification prevents the upwelling of C02-rich deep waters. 

As with the calcareous tests, BSi dissolution rates depend on (1) the susceptibility of a particular shell type to dissolution and (2) the degree to which a water mass is undersaturated with respect to opaline silica. Susceptibility to dissolution is related to chemical and physical factors. For example, various trace metals lower the solubility of BSi. (See Table 11.6 for the trace metal composition of siliceous shells.) From the physical perspective, denser shells sink fester. They also tend to have thicker walls and lower surface-area-to-volume ratios, all of which contribute to slower dissolution rates. As with calcivun carbonate, the degree of saturation of seawater with respect to BSi decreases with depth. The greater the thermodynamic driving force for dissolution, the fester the dissolution rate. As shown in Table 16.1, vertical and horizontal segregation of DSi does not significantly coimter the effect of pressure in increasing the saturation concentration DSi. Thus, unlike calcite, there is no deep water that is more thermodynamically favorable for BSi preservation they are all corrosive to BSi. 

The other reason why the average salinity of seawater is 35%o lies in the fundamental chemistry of major ions. For example, the sevenfold increase in the Na /K ratio between river water and seawater (Table 21.8) reflects the lower affinity of marine rocks for sodium as compared to potassium. In other words, the sodium sink is not as effective as the one for potassium. Thus, more sodium remains in seawater, with its upper limit, in theory, being controlled by the solubility of halite. Likewise, the Ca /Mg ° ratio in seawater is 12-fold lower than that of river water due to the highly effective removal of calcium through the formation of biogenic calcite. 

Advantages of the carbonate-exchange technique are (1) experiments up to 1,400°C, (2) no problems associated with mineral solubility and (3) ease of mineral separation (reaction of carbonate with acid). Mineral fractionations derived from hydrothermal and carbonate exchange techniques are generally in good agreement except for fractionations involving quartz and calcite. A possible explanation is a salt effect in the quartz-water system, but no salt effect has been observed in the calcite-water system (Hu and Clayton 2003). 

---