Dickite

Abstract: Phyllosilicates, and among them clay minerals, are of great interest not only for the scientific community but also for their potential applications in many novel and advanced areas. However, the correct application of these minerals requires a thorough knowledge of their crystal chemical properties. This chapter provides crystal chemical and structural details related to phyllosilicates and describes the fundamental features leading to their different behaviour in different natural or technical processes, as also detailed in other chapters of this book. Phyllosilicates, described in this chapter, are minerals of the (i) kaolin-serpentine group (e.g. kaolinite, dickite, nacrite, halloysite, hisingerite, lizardite, antigorite, chrysotile, amesite, carlosturanite, greenalite); (ii) talc and pyrophyllite group (e.g. pyrophyllite, ferripyrophyllite); (iii) mica group, with particular focus to illite; (iv) smectite group (e.g. montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite); (v) vermiculite group; (vi) chlorite group; (vii) some 2:1 layer silicates involving a discontinuous octahedral sheet and a modulated tetrahedral sheet such as kalifersite, palygorskite and sepiolite; (viii) allophane and imogolite and (ix) mixed layer structures with particular focus on illite-smectite.

Abstract: Thin-section/scanning electron microscope studies of thousands of sandstones representing many ages. compositions, and depositional environments indicate authigenic clays are far more common than previously recognized. Authigenic clays occur as pore linings, pore fillings, pseudomorphous replacements, and fracture fillings. Sandstones also contain allogenic clays. Allogenic clays originate as terrigenous material (dispersed matrix, sand-sized floccules, sand- to cobble-sized mud or shale clasts) or are introduced subsequent to deposition as a result of bioturbation or infiltration. An authigenic origin can be established on the basis of clay composition, structure, morphology and distribution, and sandstone textural properties. However, no individual criterion is an infallible indicat r of authigenic origin. The most reliable criteria are a) delicacy of clay morphology, which precludes sedimentary transport, b) occurrence of the clay as pore linings absent only at grain contacts, and c) composition radically different than associated allogenic clays. Distinctions between authigenic and allogenic clays become difficult if the latter are recrystallized or if either is extensively deformed by burial or tectonism. Studies of authigenic clays utilizing a combination of thin-section, scanning electron microscope with nondispersive elemental analyzer, and x-ray diffraction show that each of the major clay groups exhibit a limited number of distinctive morphologies. Smectite occurs as highly wrinkled or honeycomb-like pore linings, the individual flakes of which are not resol able. Illite forms pore-lining overlapping flakes whose edges tend to curl away from the grain surface and from which highly elongate lath-like projections may extend. Mixed-layer smectite/illite morphologies resemble those of both smectite and illite. Chlorite occurs primarily as pore-lining pseudohexagonal flakes with a cardhouse, honeycomb, or rosette arrangement. Kaolinite and dickite most commonly form pore-filling books of stacked pseudohexagonal flakes. Occasionally, they form thin pore-lining sheets of overlapping pseudohexagonal flakes. Authigenic clays are a major control on reservoir quality. Permeability and water saturation are particularly sensitive to the relative abundance of clays. Interpretations of depositional environment and provenanco based on sandstone composition nd texture may be inaccurate if the presence of authigenic clay is overlooked.

Abstract: Summary The results obtained by the author in the study of clay-minerals diagenesis are compared critically with the principal publications in this field, giving a general picture of the transformation of sheet silicates. Kaolinite minerals are related to the surficial zones of the earth's crust where they are formed. They are characterized by the hexacoordination of aluminium. They furnish paleogeographic indications in ancient sediments. During diagenesis they are very sensitive to the geochemical environment, stable in acid conditions, unstable in alkaline conditions. However, the increase in temperature by burial causes their destruction sooner or later. In the transitional zone to metamorphism (anchizone), kaolinite is not present. Only dickite and nacrite can be observed, provided that the environment is acid. Montmorillonites are hydrated minerals. The rise in temperature and above all in pressure during burial expels water from the interlayers. Concentrated interstitial solutions of diagenesis provide cations which replace molecules of water between the layers. It is an irreversible reaction which produces 14-A minerals (chlorites) or 10-A minerals (illites), passing generally through mixed-layer structures. The lack of montmorillonite is normal in formations which have undergone a marked burial. Mixed-layers are intermediate stages which occur during degradation by weathering and during aggradation by deep diagenesis. This aggradation is the result of an incorporation of certain cations taken up from interstitial solutions, and of a rearrangement within the lattice. There are two major pathways: a potassium and sodium pathway, which produces the illites, then the micas, passing possibly by regular mixed-layering of the allevardite-rectorite type; and a magnesium pathway, which produces the chlorites, passing possibly by a regular mixed-layering of the corrensite type. These mixed-layers can remain stable until the border of meta-morphism (anchizone). Micaceous clay minerals or illites form a very heterogenous group in the sediments which have been hardly diagenetized. Particles of diverse origin are found. They become more regular during burial. In deep diagenesis and the anchizone, crystallo-graphic parameters of the illite are sufficiently well defined to serve as a scale of recrystallization, a zoneographic index. The morphology of the particles changes. Polymorphic types 1Md and 1M are replaced by the 2M-type. The sharpness of the 10-A peak, conventionally called “crystallinity”, is an interesting quantitative criterium, together with the intensity ratio of the 5-A and 10-A peaks, which is related to the chemical composition of the octahedral layer. Micas in low-grade metamorphism, called sericites by petrographers, replace the illites discussed above. They are different from the true micas by a weaker layer charge, less than 0.9 by half-cell. They often contain sodium (paragonitic muscovites and paragonites). The octahedral charge (zero for the muscovite) is generally high, due to the replacement of Al by Fe2+ and Mg (phengites). These transformations should not obscure the fact that metamorphism is also accompanied by crystalline growth and massive neoformation. Chlorites are the least well-known clay minerals in diagenesis. Detrital particles can be aggraded to chlorite during early diagenesis by passing through the mixed-layer stage of corrensite. A massive growth of chlorite is observed in late diagenesis and the anchizone. Illite and chlorite slates give place to sericite and chlorite schists. At present, general data are not available on the crystal chemistry of chlorites in the anchizone and the greenschist facies. The stages in the diagenetic evolution of clay minerals are too little understood to be able to give them precise limits. However, the following provisional scheme can be proposed: (1) Early diagenesis (= “diagenesis” of Russian authors; = the “shallow-burial stage” of Muller, 1967a). In this stage all the clay minerals are stable; some undergo aggradation by adsorption of Mg, K and Na (various mixed-layers); some are neoformed (montmorillonites). (2) Middle diagenesis (= “early catagenesis or epigenesis” of Russian authors; the “deep-burial stage” of Muller, 1967a, includes this stage and all the following until metamorphism). In this stage the sediment becomes compact. It has lost at least 50% of its connate water. Porosity is high and circulation still plays an essential part. Some detrital minerals, such as biotite, are unstable. All the clay minerals are still stable, but many types of replacement take place, due to interstitial circulation. Dickitization of kaolinite and illitization of montmorillonite can already be observed. (3) Deep or late diagenesis (= “late catagenesis or epigenesis” of Russian authors). In this stage the temperature is greater than 100 °C, pressure increases and porosity becomes very weak. Montmorillonites and irregular mixed-layers disappear. Kaolinite recrystallizes as dickite in acid environment. These changes are irreversible. (4) Anchizone (= “metagenesis” of Russian authors; = “zone anchimetamorphique” of Kubler, 1964). This is the transitional zone to metamorphism. It agrees with temperatures around 200 °C. Illite and chlorite are almost the only sheet silicates. However, dickite can be observed as well as pyrophyllite generally associated with allevardite. The crystallographic parameters of illite define the limit of the following zone, the metamorphic epizone or greenschist facies. The crystallochemical processes that take place during the diagenetic evolution of clay minerals are schematically the following: (1) Gradual tetracoordination of aluminium. (2) Filling of octahedral sites either by interlayer cations, either by cations derived from outside the lattice, without the distinction dioctahedral-trioctahedral becoming very clear. (3) Interlayer exchange between crystal lattice and interstitial solution. Gradual closing of the layers by alkaline cations or octahedral brucite-like sheets. (4) Massive crystalline growth in the anchizone and the epizone. These processes are roughly symmetrical with those which occur during weathering. This review is a summary of the conclusions drawn in a Docteur-es-Sciences thesis (G. Dunoyer de Segonzac, 1969: Les Mineraux argileux dans la Diagenese. Passage au Metamorphisme, 339 p., 45 tables, 110 illus.) to be published as part of the series Memoires du Service de la Carte Geologique d'Alsace et de Lorraine. Most of the evidence on which these conclusions have been based is not cited directly in this article, but can be found in the thesis mentioned above, to which the reader is referred.