Illite solid solution

The general character of low charge and high Si-content of illites can be attributed to solid solution with a chemical component such as pyrophyllite in the aluminous system or chlorite in an Fe-Mg system. 

Figure 11 indicates the necessary change in composition which a muscovite would need to become stable under conditions in a sedimentary rock where chlorite is present (x to y). The solid solution for mica-illites is delimited by the shaded area which represents a much larger variation than is possible under metamorphic or igneous conditions. The detrital muscovite (composition x) is in itself stable if the bulk composition of the sediment as projected into the coordinates is found at x. 

The most important observation which can be made after the analysis of the chemical and phase equilibria information is that illite and glauconite mineral series, do not overlap. Solid solution is not continuous, neither in the mica-like phase alone nor in mixed layering between mica and expanding layers. Glauconite is not a subspecies of illite. 

If we now consider the bulk compositions of the mixed-layered minerals which contain both expandable and non-expandable layers, two series are apparent, one between theoretical beidellite and illite and one between theoretical montmorillonite and illite (Figure 25). The intersection of the lines joining muscovite-montmorillonite and beidellite-celadonite (i.e., expandable mineral to mica), is a point which delimits, roughly, the apparent compositional fields of the two montmorillonite-illite compositional trends for the natural mixed layered minerals (Figure 26). That is, the natural minerals appear to show a compositional distribution due to solid solutions between each one of the two montmorillonite types and the two mica types—muscovite and celadonite. There is no apparent solid solution between the two highly expandable (80% montmorillonite) beidellitic and montmorillonitic end members. The point of intersection of the theoretical substitutional series beidellite = celadonite and muscovite-montmorillonite is located at about 30-40% expandable layers— 70-60% illite. This interlayering is similar to the "mineral" allevardite as defined previously. It appears that as the expandability of the mixed... 

As we have seen in the previous section, the bulk chemical compositions of montmorillonites taken from the literature are dispersed over the field of fully expandable, mixed layered and even extreme illite compositions. Just what the limits of true montmorillonite composition are cannot be established at present. We can, nevertheless, as a basis for discussion, assume that the ideal composition of beidellite with 0.25 charge per 10 oxygens and of montmorillonite with the same structural charge do exist in nature and that they form the end-members of montmorillonite solid solutions. Using this assumption one can suppose either solid solution between these two points or intimate mixtures of these two theoretical end-member fully expandable minerals. In either case the observable phase relations will be similar, since it is very difficult if not impossible to distinguish between the two species by physical or chemical methods should they be mixed together. As the bulk chemistry of the expandable phases suggests a mixture of two phases, we will use this hypothesis and it will be assumed here that the two montmorillonite... 

Once the illite-chlorite zone is entered, i.e., the facies where dioctahedral mica-montmorillonite mineral solid-solutions are no longer stable, how does the assemblage change into muscovite-chlorite The major... 

Fig. 2. Logarithmic activity diagram depicting equilibrium phase relations among aluminosilicates and sea water in an idealized nine-component model of tire ocean system at the noted temperatures, one atmosphere total pressure, and unit activity of H20. The shaded area represents (lie composition range of sea water at the specified temperature, and the dot-dash lines indicate the composition of sea water saturated with quartz, amotphous silica, and sepiolite, respectively. The scale to the left of the diagram refers to calcite saturation foi different fugacities of CO2. The dashed contours designate the composition (in % illite) of a mixed-layer illitcmontmorillonitc solid solution phase in equilibrium with sea water (from Helgesun, H, C. and Mackenzie, F T.. 1970. Silicate-sea water equilibria in the ocean system Deep Sea Res.).

From HemleyJs work on the potassium system (11) one may infer that kaolinite, quartz, and K-mica ( illite) may be stable together, and the equilibrium constant [K+]/[H+] may be extrapolated, (from 200°C.) to 106 at 25°C.—e.g., Hollands (15) value of 10,50 O5. Hem-ley s work on the sodium system (12) in the same way indicates that quartz, Na-montmorillonite, and kaolinite can form a stable assemblage, and a somewhat risky extrapolation of the equilibrium ratio [Na+]/[H+] from 300° to 25°C. gives 107° (15). These ratios are not far from the corresponding ratios in sea water. One could not expect them to be exactly the same since the hydromica and montmorillonite phases in sea water are solid solutions, containing more components than the phases in Hemley s experiments. His experiments surely do not contradict the idea that the previously mentioned phases could exist together at equilibrium. 

Ransom, B., and H. C. Helgeson. 1993. Compositional end members and thermodynamic components of illite and dioctahedral aluminous smectite solid solutions. Clays Clay Minerals 41(5) S37-50. 

Fig. 11. Comparison of experimental dispersion data with those computed from model [12] - Illite-NaCl solution aggregate. Water content 159 % (weight water/dry weight of clay). Pore fluid aqueous NaCl solution, conductivity 10 crrr. Dielectric constant. Conductivity. Solid lines are calculated from optimized (bestfitting) model parameters.

Cs NMR results for Cs on the surfaces of illite, kaolinite, boehmite and silica gel (Figure 3) show that for this large, low charge cation the surface behavior is quite similar to the interlayer behavior. They also illustrate the capabilities of NMR methods to probe surface species and the effects of RH on the structural environments and dynamical behavior of the Cs. The samples were prepared by immersing 0.5 gm of powdered solid in 50 ml of O.IM CsCl solution at 2 5°C for 5 days. Final pHs were between 4.60 and 7.77, greater than the zero point of charge, except for boehmite, which has a ZPC... 

The formation and survival of unstable or metastable micas and clays in sediments and soils at low temperatures reflects kinetic as well as thermodynamic factors. First, the rates of reactions involving solid-aqueous and especially solid-solid transformations in dilute solutions are very slow at low temperatures (most natural waters are dilute )- The slow kinetics of clay transformations reflects small differences in free energy between stable and metastable clays. Also, the occurrence of specific clays is related to the chemistry and crystal structure of source minerals. Thus, illite often results from the weathering of muscovite, and vermiculite results from the weathering of biotite (cf. Drever 1988), consistent with the similar chemistries and structures of these pairs of T 0 T minerals. 

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