Illite-chlorite-montmorillonite

Mixed-layer illite-montmorillonite is by far the most abundant (in the vicinity 90%) mixed-layer clay. The two layers occur in all possible proportions from 9 1 to 1 9. Many of those with a 9 1 or even 8 2 ratio are called illites or glauconites (according to Hower, 1961, all glauconites have some interlayered montmorillonite) and those which have ratios of 1 9 and 2 8 are usually called montmorillonite. This practice is not desirable and js definitely misleading. Other random mixed-layer clays are chlorite-montmorillonite, biotite-vermiculite, chlorite-vermiculite, illite-chlorite-montmorillonite, talc-saponite, and serpentine-chlorite. Most commonly one of the layers is the expanded type and the other is non-expanded. 

K is obtained from associated K-feldspars and micas. The layer charge is increased by the reduction of iron in the octahedral sheet and incorporation of Al, entering through the ditrigonal holes in the basal oxygen plane, into the tetrahedral sheets (Weaver and Beck, 1971a Pollard, 1971). Weaver and Beck have presented evidence that indicates mixed-layer clays formed in this manner contain 20—30% chloritic layers and are actually mixed-layer illite-chlorite-montmorillonite clays. 

Interstratifications between three and more types of minerals should also be possible, e.g., illite-chlorite-montmorillonite (Weaver [1956] Powers [1957] Engelhardt et al. 

The diagenetic effects are related to the alteration of rock mineral, shales in particular. Under certain conditions, montmorillonite clays change to illites, chlorites and kaolinites. The water of hydration that desorbs in the form of free water occupies a larger volume. This volume increase will cause abnormal pressures if the water cannot escape. 

Some of the clays that enter the ocean are transported by river input, but the vast majority of the riverine particles are too large to travel fer and, hence, settle to the seafloor close to their point of entry on the continental margins. The most abundant clay minerals are illite, kaolinite, montmorillonite, and chlorite. Their formation, geographic source distribution and fete in the oceans is the subject of Chapter 14. In general, these minerals tend to undergo little alteration until they are deeply buried in the sediments and subject to metagenesis. 

The global distribution patterns of kaolinite, chlorite, montmorillonite, and illite in pelagic sediments are listed in Table 14.3 and illustrated in Figures 14.8 through 14.11. 

Oceanic Area Chlorite Montmorillonite Kaolinite Illite... 

Three MER diagrams (Figs. 2, 3, 4) collectively illustrate the mineralogical controls observed in each of the Meguma Supergroup formations. Because these metamorphosed rocks derive from proximal and distal flysch sediments, they likely once contained quartz, K-feldspar, albite, muscovite, illite, smectite (montmorillonite-beidellite), chlorite... 

Figure 31b indicates the compositional spread of chlorites from six rocks in the illite-montmorillonite mixed layered mineral facies and from the illite-chlorite zone in the French Alps (Velde, unpublished). The grains analyzed with the microprobe are chlorites replacing isolated grains of detrital mica or were newly formed grains. They are usually 15 microns in the smallest dimension. 

Figure 49. Possible phase relations in systems with variable Fe content. Chi = chlorite ML = mixed layered illite-montmorillonite I = illite. a) montmorillonites and mixed layered phase stable b) mixed layered phase unstable.

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... 

Figure 2. Projection on planes Na—K—Mg and Ca—K—Mg of the composition of possible equilibrium phases and of marine sediment minus carbonate. CH = chlorite, IL — illite (hydromica), = montmorillonite, PH = phillipsite, SED = sediments [according to Goldschmidt (7)], CA = average calcareous, SI = average siliceous, AR = average argillaceous sediments (from Ref. 22), OW = ocean water, GL = glauconite,...

Clay minerals occur in all types of sediments and sedimentary rocks and are a common constituent of hydrothermal deposits. They are the most abundant minerals in sedimentary rocks perhaps comprising as much as 40% of the minerals in these rocks. Half or more of the clay minerals in the earth s crust are illites, followed, in order of relative abundance, by montmorillonite and mixed-layer illite-montmorillonite, chlorite and mixed-layer chlorite-montmorillonite, kaolinite and septachlorite, attapulgite and sepiolite. The clay minerals are fine-grained. They are built up of tetrahedrally (Si, Al, Fe3+) and octahedrally (Al, Fe3+, Fe2, Mg) coordinated cations organized to form either sheets or chains. All are hydrous. 

At a temperature near 150°C kaolinite starts to decompose and the Al as hy-droxy-Al moves into the interlayer position increasing the proportion of dioctahedral chlorite layers. At this stage some of the chlorite layers form packets with a sufficient number of layers to diffract as the discrete mineral chlorite. Some additional Al may move into the tetrahedral sheet at this stage and some packets of 10A layers form (the K derived from K-feldspar). Thus, the amount of discrete 10A illite and dioctahedral chlorite has increased slightly but the majority of the clay consists of a mixed-layer illite-chlorite with a lesser amount of montmorillonite. 

A number of Al chlorites in which both octahedral sheets are dioctahedral have recently been described. Dioctahedral Al chlorites have been reported in bauxite deposits (Bardossy, 1959 Caillere, 1962). These chlorites appear to have been formed by the precipitation-fixation of Al hydroxide in the interlayer position of stripped illite or montmorillonite. A similar type of chlorite, along with dioctahedral chlorite-vermiculite, occurs in the arkosic sands and shales of the Pennsylvanian Minturn Formation of Colorado (Raup, 1966). Bailey and Tyler (1960) have described the occurrence of dioctahedral chlorite and mixed-layer chlorite-montmorillonite in the Lake Superior iron ores. Hydrothermal occurrences have been described by Sudo and Sato (1966). 

Of special significance with respect to their properties as sorbents are the clay minerals (e.g. kaolinite, montmorillonite, vermiculite, illite, chlorite), mainly due to their high exchange capacity. 

The most widespread fill material is reddish brown (2.5 YR 4/4, 5 YR 4/4) loam with a minor admixture of relatively large oolitic bauxite pebbles (derived from the Late Triassic - Camian - beds) and coarse clasts of black chert. Pilot X-ray diffraction analysis revealed mostly muscovite/illite, plus mixed-layer clay minerals of illite/montmorillonite type, chlorite plus mixed-layer clay minerals of chlorite/montmorillonite type, calcium montmorillonite, and diaspore plus gibbsite, or just traces of bauxite minerals (Misic, 2000). The mineral composition is not as uniform as might be expected, and further research, intended for application of factorial analysis, is in progress. A potential sediment source area in the present Cerkniscica River basin (Fig. 1) appears obvious at first glance, but similar outcrops of bauxite and chert do also appear at other sites that are not much more remote. 

The components making up the fine-grained fractions of the terrigenous-halitic complex are essentially Mg-rich trioctahedral well-crystallized chlorites without swelling layers as well as Fe-illites, the structure of which does not contain swelling layers (see model in Fig. 2.10). At the same time there are no mixed-layer species of the chlorite-montmorillonite type which were so characteristic of the carbonate-terrigenous complex (dolomite-sulfate facies). Mixed-layer clays of the illite-montmoriUonite type also diminish throughout the complex. 

Clay minerals are the most commonly occurring inorganic constituents of coals (Gluskoter, 1975) (as well as the strata associated with coals) and, therefore, can act as the source of a wide variety of metals in substantial or trace amounts. The most common clay minerals found in coals are kaolinite and illite while montmorillonite, chlorite, and sericite have also been regularly reported to occur in various coals. 

The development of vermiculite minerals in soils at the expense of micas is now well established as a common phenomenon, more particularly by the work of Jackson and his collaborators e.g., Jackson et al. [1952], Schmehl and Jackson [1956], Jackson [1959,1963], Brown and Jackson [1958]) as well as by others e.g., Fieldes and Swindale [1954], Rich [1958], Cook and Rich [1962], Millot and Camez [1963], Nelson [1963]). In spite of the frequent occurrence of dioctahedral clay vermiculites in soils, dioctahedral clay micas, in general, appear to resist decomposition better than their trioctahedral counterparts and, where direct comparison is possible, the dioctahedral type may remain unaffected, whereas the trioctahedral mica in the same profile is almost completely altered (Mitchell [1955]). Vermiculitelike minerals, however, may also develop in soils by other routes, for example, from montmorillonite (Bundy and Murray [1959], Jackson [1963]) or from chlorite (Droste and Tharin [1958], Brown and Jackson [1958], Droste et al. [1962], Millot and Camez [1963]). Such alterations are reversible, and they depend on a chemical equilibrium between the mineral and the soil solution. Hence clay chlorites, illites, and montmorillonites may develop from clay vermiculites in an appropriate environment, and intermediate types are common. The alteration of clay vermiculites to kaolinite in podzols has also been proposed (Walker [1950], Brown [1953], Jackson et al. [1954], McAleese and Mitchell [1958a]). 

This equation has been programmed for a HIPAC 103 Computer by Sato [1965], for combinations of illite-montmorillonite, chlorite-montmorillonite, and others. 

A mineral found in the mudstone of the tertiary beds at Yokokawa, Gumma Prefecture, Japan, by Kizaki [1961] has been interpreted as a mixed-layer mineral with two and one molecular layers of water. The transformation of degraded illite (Brown [1953]) to chlorite has been noted in the Chesapeake Bay Area by Powers [1953]. Schroeder [1954, 1955] has found transition minerals between illite and montmorillonite in L5tz profiles. 

In their model they used a kaolinite-like clay for the degraded silicate and allowed Na, Mg, and K to react to form sodic montmorillonite, chlorite, and illite respectively. The balance is essentially complete with only small residuals for H4Si04 and HCOT The newly formed clays would constitute about 7% of the total mass of sediments. 

The data are "normalized" with regard to the ion exchange capacity C of the sorbents. The sorption curves of the illite and of the < 40-pm chlorite are strongly non-linear, whereas that of the montmorillonite approaches linearity. 

The adsorption of transition metal complexes by minerals is often followed by reactions which change the coordination environment around the metal ion. Thus in the adsorption of hexaamminechromium(III) and tris(ethylenediamine) chromium(III) by chlorite, illite and kaolinite, XPS showed that hydrolysis reactions occurred, leading to the formation of aqua complexes (67). In a similar manner, dehydration of hexaaraminecobalt(III) and chloropentaamminecobalt(III) adsorbed on montmorillonite led to the formation of cobalt(II) hydroxide and ammonium ions (68), the reaction being conveniently followed by the IR absorbance of the ammonium ions. Demetallation of complexes can also occur, as in the case of dehydration of tin tetra(4-pyridyl) porphyrin adsorbed on Na hectorite (69). The reaction, which was observed using UV-visible and luminescence spectroscopy, was reversible indicating that the Sn(IV) cation and porphyrin anion remained close to one another after destruction of the complex. 

The CEC of clay minerals is partly the result of adsorption in the interlayer space between repeating layer units. This effect is greatest in the three-layer clays. In the case of montmorillonite, the interlayer space can expand to accommodate a variety of cations and water. This causes montmorillonite to have a very high CEC and to swell when wetted. This process is reversible the removal of the water molecules causes these clays to contract. In illite, some exchangeable potassium is present in the interlayer space. Because the interlayer potassium ions are rather tightly held, the CEC of this illite is similar to that of kaolinite, which has no interlayer space. Chlorite s CEC is similar to that of kaolinite and illite because the brucite layer restricts adsorption between the three-layer sandwiches. 

Rivers transport clay minerals primarily as part of their suspended load (silts and clays). The silt-size fraction is composed of quartz, feldspars, carbonates, and polycrystalline rocks. The clay-sized fraction is dominated by the clay minerals illite, kaolinite, chlorite, and montmorillonite. In addition to suspended particles, rivers carry as a bed load larger size fractions. The bed load constitutes only 10% of the total river load of particles and is predominantly quartz and feldspar sands. 

This information is reported as the percentage that each of the clay mineral type contributes to total identifiable clay mineral content of the noncarbonate clay-sized fraction of the surface sediments. These percentages were determined by x-ray diffraction, which is luiable to identify noncrystalline solids. Using this technique, clay minerals were found to comprise about 60% of the mass of carbonate-free fine-grained fraction. Most of the noncrystalline soUds are probably mixed-layer clay minerals. Carbonate was removed to facilitate the x-ray diffraction characterization of the clay minerals. In some cases, roimd off errors cause the sum of the percentages of kaolinite, illite, montmorillonite, and chlorite to deviate slightly from 100%. 

Kaolin - Kaolinite 4, 5, 6, Dickite 16. 27 Mica - Biotite, Phologopite, Muscovite Illite - Illite 36, Illite-Bearing Shale Mixed-Layer Clays - Metabentonite 37, 42 Montmorillonite - 21. 22A, 22B, 24, 25, 26. 31 Feldspars - Albite, Anorthite, Orthoclase Chlorite - Chlorite... 

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