Calcite temperature effect

Carbonate rocks and foraminifera tests (a sample of mixed species) are consistently lower in 5 Mg than Mg from seawater by several per mil. In addition. Mg in calcite is consistently lower in 5 Mg than Mg in dolomite by approximately 2%o (Fig. 1). These data together with the samples of coeval speleothem calcite and waters show that the heavy isotopes of Mg partition to water relative to carbonate minerals. In this respect the Mg isotopes behave much like the isotopes of Ca (Gussone et al. 2003 Schmitt et al. 2003). There is not yet sufficient data to assess with confidence the temperature dependence of the fractionation of Mg isotopes between carbonates and waters, although Galy et al. (2002) concluded that the evidence so far is that temperature effects are below detection in the range 4-18°C. 

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). 

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

Regarding the surfactant type and rock type, nonionic surfactants have much higher adsorption on a sandstone surface than anionic surfactants (Liu, 2007). However, Liu s initial experiments indicated that the adsorption of nonionic surfactant on calcite was much lower than that of anionic surfactant without the presence of NaaCOs and was of the same order of magnitude as that of anionic surfactant with the presence of Na2C03. Thus, nonionic surfactants might be candidates for use in carbonate formations from the adsorption point of view. The role of salinity is much less important, but the temperature effect is much more important for nonionics than for anionics (Salager et al 1979a). More factors that affect adsorption were discussed by Somasundaran and Hanna (1977). 

The TG curves of large and small single crystals of calcite. 1.57045 g and 1.62 mg, respectively, are very different. These curves, as shown in Figure222. were obtained by Wiedemann and Bayer (113). The smaller crystal exhibited a lower decomposition temperature than that found for the larger crystal of calcite. The effect is even more pronounced when it is noted that two different thermobalance recording sensitivities were used, 0.1 and LOO mg/in.. respectively. 

Stability. AH calcitic and dolomitic limestones are extremely stable compounds, decomposing only in fairly concentrated strong acids or at calcining temperatures of 898°C for high calcium and about 725°C for dolomitic stones at 101.3 kPa (1 atm). A very mild destabilizing effect is caused by C02-saturated water, as described in the preceding section on solubihty. Aragonite, however, is not as stable as calcite. In sustained contact with moisture,... 

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. 

This equation shows that activity of Ca + is related to pH, concentration of H2CO3 and temperature. Because pH is related to the concentration of Cl for the equilibrium curves 1 and 2 in Fig. 2.14, the relationship between the concentrations of Ca " " and Cl" can be derived for calcite-albite-sericite-K-feldspar-quartz equilibrium (curves 4 and 7 in Fig. 2.14) and calcite-albite-sericite-Na-montmorillonite-quartz equilibrium (curves 5 and 8 in Fig. 2.14) with constant w2h2C03- The range of zh2C03 in the solution in equilibrium with calcite is assumed to be 10 to 10 . The other equilibrium curves for the assemblage including Ca minerals are also drawn (Fig. 2.14). These assemblages are wairakite-albite-sericite-K-feldspar-quartz (curve 3), Ca-montmotillonite-albite-sericite-Na-montmorillonite-quartz (curve 6), Ca-montmorillonite-albite-sericite-K-feldspar-quartz (curve 9) and anhydrite (curve 10). The effect of solid solution on the equilibrium curves is not considered because of the lack of thermochemical data of solid solution. 

The saturation state of aragonite (Fig. 24.5), on the other hand, is affected little by temperature. Aragonite remains supersaturated by a factor of about ten (one log unit) over the gamut of analyses. The supersaturation probably arises from the effect of orthophosphate, present at concentrations of about 100 mg kg-1 in Mono Lake water orthophosphate is observed in the laboratory (Bischoff et al., 1993) to inhibit the precipitation of calcite and aragonite. 

Free energy variations with temperature can also be used to estimate reaction enthalpies. However, few studies devoted to the temperature dependence of adsorption phenomena have been published. In one such study of potassium octyl hydroxamate adsorption on barite, calcite and bastnaesite, it was observed that adsorption increased markedly with temperature, which suggested the enthalpies were endothermic (26). The resulting large positive entropies were attributed to loosening of ordered water structure, both at the mineral surface and in the solvent surrounding octyl hydroxamate ions during the adsorption process, as well as hydrophobic chain association effects. 

In precipitation studies (4 7, 4 ) it has been shown that, below a certain Mg/Ca concentration ratio in the aqueous solution, the rate of nucleation of calcite was faster than that of aragonite. Above that Mg/Ca ratio the order was reversed. This was explained by the effect of Mg2+ ions on the interfacial tension between the solution and precipitate, which apparently is larger for calcite than for aragonite (49). At still higher Mg/Ca ratios dolomite can be formed (50). Such low temperature precipitates of dolomite contain ordering defects. The number of defects increases when precipitation proceeds in a shorter time interval or at lower temperatures C51 ). 

Romanek CS, Grossman EL, Morse JW (1992) Carbon isotopic fractionation in synthetic aragonite and calcite Effects of temperature and precipitation rate. Geochim Cosmochim Acta 56 419-430 Rowe MW, Clayton RN, Mayeda TK (1994) Oxygen isotopes in separated components of Cl and CM meteorites. Geochim Cosmochim Acta 58 5341-5347... 

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. 

Romanek C. S., Grossman E. L. and Morse J. W. (1989). Carbon isotope fractionation in aragonite and calcite Experimental study of temperature and kinetic effects. Geol Soc. Amer. Abstr. Prog., 2LA76. 

On a relative basis, i.e. residues per 1000, there is virtually no one species like the other. In contrast, different shell samples from the same species and obtained from the same natural habitat yield identical amino acid patterns. It is of interest that (1) the structure of carbonates (aragonite-calcite-vaterite), (2) the content in trace elements, and (3) the stable isotope distribution are markedly effected by fluctuations in salinity, water temperature, Eh/pH conditions, and some anthropogenic factors. The same environmental parameters determine to a certain degree the chemical composition of the shell organic matrix. This feature suggests a cause-effect relationship between mineralogy and organic chemistry of a shell. In the final analysis, however, it is simply a reflection of the environmentally-controlled dynamics of the cell. 

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