Carbonate minerals solubility

Marion GM (2001) Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-S04-0H-HC03-C03-C02-H20 system. Geochim Cos-mochim Acta 65 1883-1896... 

Temperature and pressure variations in natural systems exert major influences on carbonate mineral solubility and the distribution of carbonic acid chemical species. For example, the solubility of calcite decreases with increasing temperature, as does the solubility of CO2 gas in water. These two effects on solubilities can lead to precipitation of calcite as a cement in a marine sediment-pore water system that undergoes moderate burial. 

A central concept important in studies of the geochemistry of carbonate systems is that of carbonate mineral solubility in natural waters. It is the touchstone against which many of the most important processes are described. In the previous chapter, methods for the calculation of the saturation state of a solution relative to a given carbonate mineral were presented. In addition, equations were given for... 

In spite of these major limitations, considerable progress has been made in understanding many of the important factors that influence subsurface water chemistry. Na+, Ca2+ and Cl- account for the major portion of dissolved components in most brines (Figure 8.6). Ca2+, which can comprise up to 40% of the cations, usually increases relative to Na+ with depth (Figure 8.7). Br and organic acids are commonly found at concentrations of 1 to 2 g L1 (Land, 1987). The bicarbonate concentration is largely limited by carbonate mineral solubility, and sulfate is generally found in low concentrations as a result of bacterial and thermal reduction processes. 

It is useful to construct a graph relating carbonate mineral solubilities to CO2 pressure. This can be done for calcite starting with equilibrium constant expression (6.2) above. If done rigorously, the derivation accounts for the effects of ion activity coefficients and the presence of CaHCOI and CaCOf ion pairs and of CaOH. Considering all complexation, the exact charge-balance equation for a pure water in which calcite is dissolving is... 

Although we have discussed separately the natural processes affecting carbonate mineral solubilities, in fact such processes often act together. For example, the calcite supersaturation observed in lakes and streams and shallow ocean embayments may result from the simultaneous operation of three processes. These include evaporation, CO2 removal by photosynthesis, and increases in temperature that reduce the solubilities of both CO2 and the carbonate minerals. 

Major carbonate mineral solubilities and their associated ion pairs are reliable except for dolomite, siderite and rhodocrosite, for which ranges of Ksp values are estimated. 

Figure 2.42 Carbonate minerals solubility vs. water pH. Their solubility is minimal at pH > pK of carbonic acid and proportionate with H+ concentrations at pH < pK. Curve slant is defined by salt stoichiometry.

The potassium carbonate is soluble and washes away, but the aluminosilicate remains as the clay. Cements are obtained when aluminosilicates are roasted with limestone and other minerals and then allowed to solidify (see Section 14.10). 

Almost all the Earth s carbon is found in the lithosphere as carbonate sediments that have precipitated from the oceans. Shells of aquatic animals also contribute CaC03 to the lithosphere. Carbon returns to the hydrosphere as carbonate minerals dissolve in water percolating through the Earth s crust. This process is limited by the solubility products for carbonate salts, so lithospheric carbonates represent a relatively inaccessible storehouse of carbon. 

Coprecipitation is a partitioning process whereby toxic heavy metals precipitate from the aqueous phase even if the equilibrium solubility has not been exceeded. This process occurs when heavy metals are incorporated into the structure of silicon, aluminum, and iron oxides when these latter compounds precipitate out of solution. Iron hydroxide collects more toxic heavy metals (chromium, nickel, arsenic, selenium, cadmium, and thorium) during precipitation than aluminum hydroxide.38 Coprecipitation is considered to effectively remove trace amounts of lead and chromium from solution in injected wastes at New Johnsonville, Tennessee.39 Coprecipitation with carbonate minerals may be an important mechanism for dealing with cobalt, lead, zinc, and cadmium. 

Mineral acids include hydrochloric acid and blends of hydrochloric and hydrofluoric acid (usually 12% HCl/3% HF). Hydrochloric acid is used to acidize carbonate formations. Its advantages are relatively low cost, high carbonate mineral dissolving power, and the formation of soluble reaction products (which minimizes formation damage). The primary disadvantage of hydrochloric acid is its corrosive nature. 

Phosphate is remineralized during the oxidation of organic matter and dissolution of hard parts, such as bones and teeth, that are composed of the minerals hydroxyapatite and fluoroapatite. Unlike the other products of remineralization, pore-water phosphate concentrations are regulated only by mineral solubility, such as through vivianite (iron phosphate) and francolite (carbonate fluoroapatite). Redox reactions are not significant because phosphorus exists nearly entirely in the h-5 oxidation state. 

In acids soils, particularly those with kaolinite clay minerals, soluble Fe + concentrations tend to rise to high levels because of low CEC and because conditions do not favour precipitation of Fe(II) oxides or carbonates or synthesis of silicates. 

Cadmium is found naturally deep in the subsurface in zinc, lead, and copper ores, in coal, shales, and other fossil fuels it also is released during volcanic activity. These deposits can serve as sources to ground and surface waters, especially when in contact with soft, acidic waters. Chloride, nitrate, and sulfate salts of cadmium are soluble, and sorption to soils is pH-dependent (increasing with alkalinity). Cadmium found in association with carbonate minerals, precipitated as stable solid compounds, or coprecipitated with hydrous iron oxides is less likely to be mobilized by resuspension of sediments or biological activity. Cadmium absorbed to mineral surfaces (e.g., clay) or organic materials is more easily bioaccumulated or released in a dissolved state when sediments are disturbed, such as during flooding. 

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). 

The interplay of factors leading to the formation of carbonate rocks is extremely complicated, but several avenues of investigation have yielded fruitful results. These approaches include studies of surface energies, isotopic composition and radiochemistry (including the use of carbon-14 to study the rates of carbonate deposition), solubilities under ambient conditions, and the effect of magnesium-calcium ratios in the solutions from which carbonate minerals are precipitated. 

Only a few of the reactions summarized in Table 3.3 are actually based on data at subzero temperatures. In most cases, the lower temperature for data is 0°C. This could potentially be a serious limitation for the FREZCHEM model. For example, quantifying carbonate chemistry requires specification of Ah,co2 -ftcb - 2 and Kw all of these reactions are only quantified for temperatures > 0 °C (Table 3.3). Figure 3.9 demonstrates how six of the most important relationships of Table 3.3 extrapolate to subzero temperatures. We were able, based on these extrapolations, to quantify the solubility product of nahcolite (NaHCOa) and natron (Na2CO3 10H2O) to temperatures as low as — 22°C (251 K) (Marion 2001). Even for highly soluble bicarbonate and carbonate minerals such as nahcolite and natron, their solubilities decrease rapidly with temperature (Marion 2001). For example, for a hypothetical saline, alkaline brine that initially was 4.5 m alkalinity at 25 °C, the final alkalinity at the eutectic at —23.6°C was 0.3m (Marion 2001). At least for carbonate systems it is not necessary to extrapolate much beyond about —25 °C to quantify this chemistry, which we believe can reasonably be done using existing equation extrapolations (Fig. 3.9). 

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 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 ... 

A basic premise of solubility considerations is that a solution in contact with a solid can be in an equilibrium state with that solid so that no change occurs in the composition of solid or solution with time. It is possible from thermodynamics to predict what an equilibrium ion activity product should be for a given mineral for a set of specified conditions. As will be shown later in this chapter, however, it is not always possible to obtain a solution of the proper composition to produce the equilibrium conditions if other minerals of greater stability can form from the solution. It shall also be shown that while it is possible to calculate what mineral should form from a solution based on equilibrium thermodynamics, carbonate minerals usually behave in a manner inconsistent with such predictions. 

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