Dissolution, congruent

Dissolution of CaCOs is a congruent reaction the entire mineral is weathered and results completely in soluble products. The above reaction is driven to the right by an increase of CO2 partial pressure and by the removal of the Ca and/or bicarbonate. Any impurities present in the calcareous rock, such as silicates, oxides, organic compounds, and others, are left as residue. As the calcium and bicarbonate leach... 

Calcareous minerals and evaporite minerals (halides, gypsum) are very soluble and dissolve rapidly and, in general, congruently (i.e., yielding upon dissolution the same stoichiometric proportions in the solution as the proportions in the dissolving mineral and without forming new solid phases). Their contribution to the total dissolved load in rivers can be estimated by considering the mean composition of river... 

The weathering of silicates has been investigated extensively in recent decades. It is more difficult to characterize the surface chemistry of crystalline mixed oxides. Furthermore, in many instances the dissolution of a silicate mineral is incipiently incongruent. This initial incongruent dissolution step is often followed by a congruent dissolution controlled surface reaction. The rate dependence of albite and olivine illustrates the typical enhancement of the dissolution rate by surface protonation and surface deprotonation. A zero order dependence on [H+] has often been reported near the pHpzc this is generally interpreted in terms of a hydration reaction of the surface (last term in Eq. 5.16). 

Schematic illustration of initial incongruent dissolution. In the initial stages, a mineral grain may develop a cation depleted layer e, but eventually congruent dissolution is observed and the rate of dissolution of A (dA/dt) must equal B (dB/dt) for a 1 1 stoichiometry.

The thickness, y, of the cation depleted layer at steady state with decrease with increasing [H+] in the solution. Therefore congruent dissolution will result immediately from low pH solution. 

Congruent surface-controlled dissolution follows after the initial incongruent period. 

The term incongruent is generally used, if a mineral upon dissolution reacts to form a new solid or if the reversal of a dissolution process leads to a different composition. In natural environments incongruent solubility is probably more prevalent, e.g., in weathering of many clays, than congruent dissolution. 

The term congruent dissolution often refers to a process by which a mineral is dissolved in stoichiometric proportions into solution without formation of a new solid phase, and this usage is convenient for isotopic studies because it constrains the phases or components that may... 

Figure 2. Isotopic effects of congruent partial dissolution of hematite. Within the 2a error of the analyses, there is no significant Fe isotope fractionation over wide ranges of percent dissolution. Gray bars denote bulk composition (2a) of the two hematite grains. Data from Skulan et al. (2002) and Beard et al. (2003a).

Figure 5. Possible pathways by which Fe isotopes may be fractionated during dissimilatory Fe(III) reduction (DIR). Dissolution, if it occurs congruently, is unlikely to produce isotopic fractionation (Afi. If Fe(II) is well complexed in solution and conditions are anaerobic, precipitation of new ferric oxides (A3) is unlikely to occur. Significant isotopic fractionation is expected during the reduction step (A2), possibly reflecting isotopic fractionation between soluble pools of Fe(III) and Fe(II). The soluble Fe(III) component is expected to interact with the cell through an electron shuttle compound and/or an outer membrane protein, and is not part of the ambient pool of aqueous Fe. Sorption of aqueous or soluble Fe(II) to the ferric oxide/hydroxide substrate (A4) is another step in which isotopic fractionation may occur. Modified from Beard et al. (2003a).

The sulfete and chloride minerals in evaporites (gypsum, anhydrite, halite) undergo congruent dissolution to produce Ca (aq), S04 (aq), Na (aq), and Cl (aq). The dissolution of evaporite and biogenic carbonates (limestone, dolomite, and calcite) generates... 

Galvez et al. (1999) demonstrated that phosphorus up to a P/Fe mol ratio of 0.03 mol mol , can be incorporated into the hematite structure by heating P-con-taining 2-line ferrihydrite. Support for structural incorporation comes from a higher unit cell c (1.3776 => 1.3824 nm), IR-stretching bands of P-OH, a lowered intensity ratio of the XRD 104/113 lines and congruent release of Fe and P upon dissolution. 

Aicagan ite. can incorporate up to 0.06 mol mol Cu and much smaller amounts of Cr, Mn, Co, Ni and Zn in the structure (Inouye et al., 1974 Holm, 1985 Buch-wald Clarke, 1989). Incorporation of Al, Cr and Ga has also been reported (Lorenz Kempe, 1987). Cornell (1992) produced akaganeite from acid Si-containing Fe " solutions and found by congruent dissolution that up to 0.04 mol mol Si could be incorporated. The Si species were probably located in the tunnels (0.5 nm ) of the akaganeite structure. 

The effect of these substituents has not been fully explained. It is not, in most cases, due to formation of a protective layer of the substituent at the surface because (M = trivalent substituent) and Fe usually dissolve congruently. Crystal defects (e. g. vacancies) created by substitution should accelerate dissolution, but this is not... 

Equations such as equation (1) above imply that the oxidative dissolution of pyrite is congruent, directly liberating Fe2+, SO4, and H+ to solution. However, in the common circumstance that water is insufficiently abundant to immediately transport the oxidation products away from the mineral surfaces, pyrite oxidation more commonly results initially in the accumulation of various hydroxysulphate evaporite minerals. These minerals form efflorescent crusts, typically white and yellow in colour, on the surfaces of pyrite-rich coals and mudstones (Fig. 1), and they effectively store the oxidation products in a readily soluble form until some hydro-logical event delivers sufficient water to dissolve and transport them away. Because pyrite often occurs in mudstones, where Al-bearing clay minerals are in contact with acidic pyrite oxidation waters, A1 is frequently released from the clays and is also stored in these hydroxysulphate phases. When these minerals finally dissolve, they result in abrupt and extreme increases in dissolved acidity. For this reason, they have been termed acid generating salts (AGS) (Bayless... 

After one day, a direct correlation between leachant pH and release of Si in the solution can be seen (Fig. 9a). Later on (3- and 10-day corrosion), the increase in pH becomes much slower, suggesting that the leaching of alkaline elements is not a congruent process, and pH stabilizes rapidly during matrix dissolution. In fact, the proportion of CaO in the matrix of HT materials (11-38 wt%) directly controls the amount of Ca that will be readily leached out (see Fig. 9b). It can thus be expected that Ca-poor/Si-rich HT materials possess a higher durability than Ca-rich/Si-poor ones. The relationship between CaO in the matrix of HT materials, Ca2+ extracted into solution by the leachant, and pH is given by ... 

Sulfates Gypsum Anhydrite CaS04-2H20 CaS04 Congruent dissolution in H20... 

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