Clay minerals, layered silicates

Phyllosilicates (clay minerals) - layered silicates such as Al4Si4O10(OH)8 (kaolinite) and (Ca,Na)o.7(Al,Mg,Fe)4(Si,Al)802o(OH)4.nH20 (montmorillonite, also called smectite). 

Layer-silicates Recent studies have also demonstrated the potential microbial influence on clay mineral (layer silicates) formation at hydrothermal vents. Bacterial cells covered (or completely replaced) with a Fe-rich silicate mineral (putative nontronite), in some cases oriented in extracellular polymers (as revealed by TEM analysis), were found in deep-sea sediments of Iheya Basin, Okinawa Trough (Ueshima Tazaki, 2001), and in soft sediments, and on mineral surfaces in low-temperature (2-50°C) waters near vents at Southern Explorer Ridge in the northeast Pacific (Fortin etal., 1998 Fig. 8.6). The Fe-silicate is believed to form as a result of the binding and concentration of soluble Si and Fe species to reactive sites (e.g. carboxyl, phosphoryl) on EPS (Ueshima Tazaki, 2001). Formation of Fe-silicate may also involve complex binding mechanisms, whereas metal ions such as Fe possibly bridge reactive sites within cell walls to silicate anions to initiate silicate nucleation (Fortin etal., 1998). Alt (1988) also reported the presence of nontronite associated with Mn- and Fe-oxide-rich deposits from seamounts on the EPR. The presence of bacteria-like filaments within one nontronite sample was taken to indicate that bacterial activity may have been associated with nontronite formation. Although the formation of clay minerals at deep-sea hydrothermal vents has not received much attention, it seems probable that based on these studies, biomineralisation of clay minerals is ubiquitous in these environments. 

Clays are layer silicates (phyllosilicates) of particle size less than about 4 pm, produced by the weathering of aluminosilicate rocks. Clay minerals fall roughly into two structural classes the kaolinite type, based on paired sheets of tetrahedral (SiC>44-) and octahedral [A10n(0H) g " or... 

The clay minerals are silicates and aluminosilicates with sheet-like structures. They result from the weathering of granite and other rocks. The layers have enormous inner surfaces that can absorb large amounts of H2O. Clay mixtures often occur as minute platelets with a very large total surface area. When wet, the clays are easily shaped. When heated to high temperatures, they lose H2O when fired in a furnace, they become very rigid. 

Clay minerals have silicate layer structures of either type 1 1 or 2 1. Kaolinite is of type 1 1 and... 

Layer silicates, sheet-like phyllosilicates such as the familiar micas, are in primary rocks and in soils. The soil minerals are often called clay minerals. Since other components can also be in the clay fraction, layer silicates is a mom accurate term. A typical layer silicate is a combination of a layer of Al-, Mg-, or Fe(II)-0 octahedra plus one or two layers of Si-0 tetrahedra. The tetrahedral and octahedral sheets bond together by sharing oxygens at the corners of the tetrahedra and octahedra. Layer silicate minerals are differentiated by (1) the number and sequence of tetrahedral and octahedral sheets, (2) the layer charge per unit cell, (3) the type of interlayer bond... 

The natural montmorillonite clays consist of several hundred individual platelike particles of dimensions 1 jum x 1 jum x 1 nm, held together by electrostatic forces with a gap of approximately 0.3 nm between two adjacent particles. The structure at the atomic level is shown in Figure 13.28 (77). The sodium montmorillonite layer is a crystalline 2 1 layered clay mineral in which a central alumina octahedral sheet is sandwiched between two silica tetrahedral sheets. These structures are sometimes called smectite clays, because of their layered structure see Figure 7.1. Note that this clay mineral comprises silicate layers in which the fundamental unit is planar. In the gap between the silicate layers are sodium ions. The gap is widely known as a gallery or an interlayer. The density of montmorillonite clays vary slightly with composition, but is generally near 2.5 g/crn (78). 

The template synthetic method is based on the in situ hydrothermal crystallization of clay mineral layers (from a gel) using selected water-soluble polymers as templates [61]. Template synthesis is essentially limited to water-soluble polymers, and the synthetic clay mineral formed under the conditions described by the authors is a poorly ordered fluorohectorite. On the other hand, the method is potentially capable of promoting the dispersion of silicate layers in a one-step process. 

Silicates with layer. structures include some of the most familiar and important minerals known to man, partieularly the clay minerals [such as kaolinite (china clay), montmorillonite (bentonite, fuller s earth), and vermiculite], the micas (e.g. muscovite, phlogopite, and biotite), and others such as chrysotile (white asbestos). 

Two classes of clays are known [3] (i) cationic clays (or clay minerals) that have negatively charged alumino-silicate layers balanced by small cations in the interlayer space (e.g. K-10 montmorillonite) and (ii) anionic clays which have positively charged brucite-type metal hydroxide layers balanced by anions and water molecules located interstitially (e.g. hydrotalcite, Mg6Al2(0H)igC034H20. 

A specific example of this would be the weathering of K-feldspar and the formation of kao-linite (see Table 8-1 for mineral definitions), a layer-silicate clay ... 

Secondary minerals. As weathering of primary minerals proceeds, ions are released into solution, and new minerals are formed. These new minerals, called secondary minerals, include layer silicate clay minerals, carbonates, phosphates, sulfates and sulfides, different hydroxides and oxyhydroxides of Al, Fe, Mn, Ti, and Si, and non-crystalline minerals such as allophane and imogolite. Secondary minerals, such as the clay minerals, may have a specific surface area in the range of 20-800 m /g and up to 1000 m /g in the case of imogolite (Wada, 1985). Surface area is very important because most chemical reactions in soil are surface reactions occurring at the interface of solids and the soil solution. Layer-silicate clays, oxides, and carbonates are the most widespread secondary minerals. 

Layer-silicate structure, as in other silicate minerals, is dominated by the strong Si-O bond, which accounts for the relative insolubility of these minerals. Other elements involved in the building of layer silicates are Al, Mg, or Fe coordinated with O and OH. The spatial arrangement of Si and these metals with O and OH results in the formation of tetrahedral and octahedral sheets (see Fig. 8-2). The combination of the tetrahedral and octahedral sheets in different groupings, and in conjunction with different metal oxide sheets, generates a number of different layer silicate clays (see Table 8-1). 

Once a layer-silicate clay forms, it does not necessarily remain in the soil forever. As conditions change it too may weather and a new mineral may form that is more in equilibrium with the new conditions. For example, it is common in young soils for the concentrations of cations such as K, Ca, or Mg in the soil solution to be high, but as primary minerals are weathered and disappear, cation concentrations will decrease. With a decrease in solution cations, a layer-silicate such as vermiculite will no longer be stable and can weather. In its place. 

Fig. 8-2 Structure of a 1 1 (kaolinite) and a (montmorillonite) layer-silicate clay mineral.

Main gangue minerals of the Se-type deposits comprise quartz, adularia, illite/ smectite interstratified mixed layer clay mineral, chlorite/smectite interstratified mixed layer clay mineral, smectite, calcite, Mn-carbonates, manganoan caleite, rhodoehrosite, Mn-silicates (inesite, johannsenite) and Ca-silicates (xonotlite, truscottite). 

Principal gangue minerals in base-metal vein-type deposits are quartz, chlorite, Mn-carbonates, calcite, siderite and sericite (Shikazono, 1985b). Barite is sometimes found. K-feldspar, Mn-silicates, interstratified mixed layer clay minerals (chlorite/smectite, sericite/smectite) are absent. Vuggy, comb, cockade, banding and brecciated textures are commonly observed in these veins. 

In the Se-type gangue minerals comprise quartz, adularia, illite/smectite inter-stratified mixed layer clay mineral, smectite, calcite, Mn carbonates (manganoan calcite, rhodochrosite), Mn silicates (inesite, johansenite) and Ca silicates (xonotlite, truscottite). In comparison, the Te-type contains fine-grained, chalcedonic quartz, sericite, barite, adularia and chlorite/smectite interstratified mixed layer clay mineral. Carbonates and Mn minerals are very poor in the Te-type and they do not coexist with Te minerals. Carbonates are abundant and barite is absent in the Se-type. Grain size of quartz in the Te-type is very fine, while large quartz crystals are common in the Se-type. 

Layer silicate minerals have a high selectivity of trace transition and heavy metals and greater irreversibility of their adsorption. Some chemisorbing sites such as -SiOH or AlOH groups may be at clay edges and form hydroxyl polymers at the mineral surface. Another possible reason for the high selectivity may be hydrolysis of the metal and strong adsorption of the hydrolysis ion species. 

Boyd SA, Jaynes WF (1994) Role of layer charge in organic contaminant sorption by organo-clays. In Mermut AR (ed) Layer charge characteristics of 2 1 silicate clay minerals. CMS Workshop Lecture Series, vol 6, The Clay Minerals Society, Boulder, CO, pp 48-77... 

Weiss A (1963) Mica-type layer silicates with alkylammonium ions. Clays Clay Miner 10 191-224... 

---