Clay Minerals Aluminosilicates

The name clay is often used in various contexts (1) to indicate particle size ( 2 in. [ 0.005 mm]), (2) to indicate a rock composed predominantly of clay minerals, and (3) to indicate a name for a group of minerals, the clay minerals. 

These minerals are hydrated aluminosilicates which are characterized by a sheetlike structure and can be conveniently divided into three groups (1) the kaolinite group, (2) the mont-morillonite group, and (3) the potash clay (or hydrous mica) group (Table 7.7). In the kaolinite group, all have the same chemical composition and differ only in individual crystal structures. The montmorillonite group can be represented by means of ion substitutions in the general chemical formula. For example, in montmorillonite itself, approximately 16% of the aluminum 

Potassium Magnesium Sodium Silicon Titanium Organic sulfur Pyritic sulfur Sulfate sulfur Total sulfur 

Source Ruch. R.R. et al.. Environmental Geology Note No. 72, Illinois State Geological Survey, Urbana, IL, 1974, p. 18. 

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. 

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In general the characteristic temperatures obtained under oxidizing conditions are higher than the reducing counterparts. This can be traced to iron that fluxes clay minerals (aluminosilicates) in the ferrous state (Fe/FeO) much more effective than as ferric oxide (Fe203). Typical iron species show the following behavior under reducing conditions ... 

After the blends have been prepared (either in the dry or wet process), these materials are fed at a uniform rate into a long rotary kiln. The materials are gradually heated to a liquid state. At temperatures up to about I,600°F the free water evaporates, the clay minerals dehydroxylate and crystallize, and CaCO, decomposes. At temperatures above 1,600°F the CaCO, and CaO react with aluminosilicates and the materials become liquids. Heating is continued to as high as 2,800°F. 

Taking this one step further, perhaps even an inorganic gene may have been provided by clay mineral sources. Earliest clay samples are of a mineral called montmorillonite that consists of sheets of aluminosilicates in which Fe2+, Fe3+ and Mg2+ are substituted for some of the Al3+, and Al3+ is substituted for Si4+. The oxygen content of the layers does not change and the alternative valencies allow the production of positive and negatively charged layers. Dramatically, Paecht-Horowitz and co-workers showed that the amino acid adenylate could be polymerised with up to 50 units on the montmorillonite surface in aqueous solution. Similar condensation reactions for carbohydrates on hydrotalcite surfaces have... 

It has often been argued that clay minerals cannot be used as models for soils in surface chemistry because soil clays are too heterogeneous and impure. The work reported here shows that, for both equilibrium and kinetic studies, standard aluminosilicates are useful models for soils. 

Clay mineral A layered aluminosilicate, such as kaolinite, dUte, chlorite, and montmordlonite. Most are formed by chemical weathering of rocks on land. 

As a function of their structural properties, clays interact differently with organic and inorganic contaminants. Two major groups of clay minerals are selected for discussion here (a) kaolinite, with a 1 1 layered structured aluminosilicate and a surface area ranging from 6 to 39 m g" (Schofield and Samson 1954) and (b) smectites with a 2 1 silicate layer and a total surface area of about 800m g" (Borchardt 1989). 

Clays are silicate minerals that may be platy or fibrous and are usually of exceedingly fine grain size, ranging from colloidal, a few nanometers in diameter, to a maximum of about a tenth of a micrometer. Similarly to other aluminosilicates, clays show considerable range in chemical composition with concomitant structural modifications (Fig. 2.13). A few of the clay minerals described as fibrous are briefly mentioned here. 

The concept zeolites conventionally served as the synonym for aluminosilicates with microporous host lattice structures. Upon removal of the guest water, zeolites demonstrate adsorptive property at the molecular level as a result they are also referred to as molecular sieves. Crystalline zeosils, AlPO s, SAPO s, MAPO s (M=metal), expanded clay minerals and Werner compounds are also able to adsorb molecules vitally on reproval of any of the guest species they occlude and play an Important role in fields such as separation and catalysis (ref. 1). Inclusion compounds are another kind of crystalline materials with open framework structures. The guest molecules in an inclusion compound are believed to be indispensable to sustaining the framework structure their removal from the host lattice usually results in collapse of the host into a more compact crystal structure or even into an amorphous structure. 

Coal contains detrital minerals that were deposited along with the plant material, and authigenic minerals that were formed during coalification. The abundance of mineral matter in coal varies considerably with its source, and is reported to range between 9.05 and 32.26 wt% (Valkovic 1983). Minerals found in coal include (Table 2) aluminosilicates, mainly clay minerals carbonates, such as, calcite, ankerite, siderite, and dolomite sulphides, mainly pyrite (FeS2) chlorides and silicates, principally quartz. Trace elements in coal are commonly associated with one or more of these minerals (see Table 2). 

Many clay minerals have aluminosilicate layer structures. For example, in kaolinite, Al2(0H)4[Si205] (Fig. 7.5), the Al3+ are all in octahedral locations. Clay minerals of the smectite or swelling type, such as montmo-rillonite, can absorb large amounts of water between the aluminosilicate... 

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... 

Alkali leach methods axe exemplified by the Bayer process for the preparation of pure a-A C for electrolysis (Section 17.5) from the mineral bauxite. Bauxite consists mainly of a-AlO(OH) (diaspore) and/or 7-A10(0H) (boehmite), the difference between these being essentially that the oxygen atoms form hep and ccp arrays, respectively. The chief contaminants are silica, some clay minerals, and iron(III) oxides/hydroxides, which impart a red-brown color to the mineral. Aluminum (III) is much more soluble than iron(III) or aluminosilicates in alkali, so that it can be leached out with aqueous NaOH (initially 10-15 mol L 1) at 165 °C under approximately 0.6 MPa pressure, leaving a red mud of iron (and other transition metal) oxides/hydroxides and aluminosilicates ... 

The retardation of subsurface transport of TNT arises from this compound s absorption into NOM and adsorption onto mineral siloxane surfaces covered with weakly hydrated cations like potassium (but not sodium and calcium). While components of feldspars exhibit some siloxane surfaces, here we anticipate that most of the silox-anes occur in the aluminosilicate clay minerals (e.g., illite) because these particles have such high specific surface areas (Table 11.3). Hence, the total for TNT may be found at this site ... 

The mineralogical composition of Sahara dust particles shows the predominance of aluminosilicates (clays). Illite is also present in many cases while quartz particles are rare. Scanning Electron Microscopy (SEM) results on dust composition transported over different regions in the Mediterranean Basin have shown that Al-rich clay minerals such as illite and kaolinite are very common in PM10 for Cypms and dominant for Crete. Dust particles are also very rich in calcium which is distributed between calcite, dolomite and sulphates and Ca-Si particles (e.g. smectites) whereas iron oxides are often detected [43]. 

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