Seawater carbonate minerals

The latter two assumptions are simplistic, considering the number of factors that affect pH and oxidation state in the oceans (e.g., Sillen, 1967 Holland, 1978 McDuff and Morel, 1980). Consumption and production of CO2 and O2 by plant and animal life, reactions among silicate minerals, dissolution and precipitation of carbonate minerals, solute fluxes from rivers, and reaction between convecting seawater and oceanic crust all affect these variables. Nonetheless, it will be interesting to compare the results of this simple calculation to observation. 

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. 

Zullig, J. J., and J. W. Morse, Interaction of organic acids with carbonate mineral surfaces in seawater and related solutions. I. Fatty acid adsorption , Geochim. Cosmochim. Acta, 52, 1667-1678 (1988). 

The resulting Soln. C is a predominantly NaCl solution similar to terrestrial seawater (Soln. D, Table 5.3). Had we chosen a concentration factor of 600-fold, the agreement would have been even better. In any case, the concentration factor is arbitrary. The point is that simple processes, starting with a dilute Fe-Mg-HC03-rich solution formed by reaction of water with ultra-mafic and mafic rocks, evaporation, and carbonate precipitation, converted the solution into an Earth-like seawater NaCl brine. The Na/Mg ratio of solution C is 9.9, while terrestrial seawater has a Na/Mg ratio of 8.8 (Soln. 5.3D). Note also the similar pH values (8.03 and 8.05, Table 5.3). This solution did not (cannot) evolve into an alkali soda-lake composition as some have hypothesized or assumed for Mars (e.g., Kempe and Kazmierczak 1997 Morse and Marion 1999) because the mass of hypothesized soluble iron and magnesium and the low solubility of their respective carbonate minerals are sufficient to precipitate most of the initial soluble bicarbonate/carbonate ions. 

A classic example of metastability is surface-seawater supersaturation with respect to calcite and other carbonate minerals (Morse and Mackenzie 1990 Millero and Sohl 1992). The degree of calcite supersaturation in surface seawater varies from 2.8- to 6.5-fold between 0 and 25 °C (Morse and Mackenzie 1990). In Fig. 3.18, experimental calcite solubility (metastable state) is approaching model calcite solubility (stable state) at subzero temperatures. In Table 5.1, the difference in seawater pH, assuring saturation or allowing supersaturation with respect to calcite, is 0.38 units. Moreover, in running these calculations, it was necessary to remove magnesite and dolomite from the minerals database (Table 3.1) because the latter minerals are more stable than calcite in seawater. But calcite is clearly the form that precipitates... 

One major concept applicable to problems dealing with the behavior of carbonic acid and carbonate minerals in seawater is the idea of a "constant ionic media". This concept is based on the general observation that the salt in seawater is close to constant in composition, i.e., the ratios of the major ions are the same from place to place in the ocean. Seawater in evaporative lagoons, pores of marine sediments, and near river mouths can be exceptions to this constancy. Consequently, the major ion composition of seawater can generally be determined from salinity. It has been possible, therefore, to develop equations in which the influences of seawater compositional changes on carbonate equilibria can be... 

Calculation of the saturation state of seawater with respect to carbonate minerals... 

One of the primary concerns in a study of the geochemistry of carbonates in marine waters is the calculation of the saturation state of the seawater with respect to carbonate minerals. The saturation state of a solution with respect to a given mineral is simply the ratio of the ion activity or concentration product to the thermodynamic or stoichiometric solubility product. In seawater the latter is generally used and Qmjneral is the symbol used to represent the ratio. For example ... 

CALCULATION OF THE SATURATION STATE OF SEAWATER WITH RESPECT TO CARBONATE MINERALS... 

The equations and methods given in this chapter can be used to calculate the distribution of carbonic acid system components and the saturation state of a solution with respect to a carbonate mineral under varying temperature, pressure, and composition. To illustrate the type of changes that occur, a calculation has been done for seawater, and the results summarized for nine different cases in Table 1.12. Case 1 is used as a reference typical of surface, subtropical, Atlantic seawater in equilibrium with the atmosphere. In all other cases the salinity and total... 

In this chapter, we introduced the reader to some basic principles of solution chemistry with emphasis on the C02-carbonate acid system. An array of equations necessary for making calculations in this system was developed, which emphasized the relationships between concentrations and activity and the bridging concept of activity coefficients. Because most carbonate sediments and rocks are initially deposited in the marine environment and are bathed by seawater or modified seawater solutions for some or much of their history, the carbonic acid system in seawater was discussed in more detail. An example calculation for seawater saturation state was provided to illustrate how such calculations are made, and to prepare the reader, in particular, for material in Chapter 4. We now investigate the relationships between solutions and sedimentary carbonate minerals in Chapters 2 and 3. 

The applicability of scanning Auger spectroscopy to the analysis of carbonate mineral surface reactions was demonstrated by Mucci and Morse (1985), who carried out an investigation of Mg2+ adsorption on calcite, aragonite, magnesite, and dolomite surfaces from synthetic seawater at two saturation states. Results are summarized in Table 2.5. 

Aragonite is the only one of the four carbonate minerals examined that does not have a calcite-type rhombohedral crystal structure. For all the minerals examined, with the exception of aragonite, the two solution saturation states studied represent supersaturated conditions, because at a saturation state of 1.2 with respect to calcite, the seawater solution is undersaturated (0.8) with respect to aragonite. 

Table 2.5. The Mg to Ca concentration ratio on the surface of four carbonate mineral crystals after extended exposure to synthetic seawater at two different saturation states. (After Mucci and Morse, 1985.)...

Sulfate The coprecipitation of relatively few anions with carbonate minerals has been studied and, with the exception of sulfate, these studies have generally not been as detailed as many of those with cations. However, coprecipitation reactions can be important for the removal of ions such as fluoride, borate, and phosphate from seawater (e.g., Morse and Cook, 1978 Okumura et al., 1983). It is also probable that anions will eventually gain a greater stature in the study of diagenesis... 

A basic concept is that a given carbonate mineral will not dissolve in a solution that is supersaturated with respect to that mineral or precipitate from a solution undersaturated with respect to that mineral. If a solution is undersaturated with respect to all carbonate minerals, they may all dissolve with their relative dissolution rates determined by grain size, microstructure, and solution composition, among other factors. The idea that under universally undersaturated conditions mineral solubility may not simply control dissolution rates, even for grains of the same size, was confirmed by Walter and Morse (1985). They observed that relative dissolution rates in seawater could not be normalized directly to total surface areas, but rather depended strongly on microarchitecture (Figure 7.6). 

The rainwater of Bermuda is in near equilibrium with atmospheric Pc02 = 10-3.5 atm., and contains small amounts of sea salt (0.07 wt. % seawater). The rainfall of 147 cm y1 is seasonally distributed. The rain enters the saturated zone by two main paths direct rainfall on marshes and ponds, and percolation downward from the vadose zone as vadose seepage and flow through rocks during times of soil water excess (Vacher, 1978). Total annual recharge of the saturated zone is about 40 cm y-1 (Vacher and Ayers, 1980). The residence time of the groundwater has been calculated as 6.5 years, and the average age of the sampled water as 4 years (Vacher et al., 1989). Such estimates are necessary for calculations of carbonate mineral stabilization rates, as shown in a later section. 

Walter L.M. and Burton E.A. (1986) The effect of orthophosphate on carbonate mineral dissolution rates in seawater. Chem. Geol. 56, 313-323. 

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