Clay minerals

Clay minerals

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Clay minerals are hydrous aluminium
Aluminium
Aluminium or aluminum is a silvery white member of the boron group of chemical elements. It has the symbol Al, and its atomic number is 13. It is not soluble in water under normal circumstances....

 phyllosilicates, sometimes with variable amounts of iron
Iron
Iron is a chemical element with the symbol Fe and atomic number 26. It is a metal in the first transition series. It is the most common element forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust...

, magnesium
Magnesium
Magnesium is a chemical element with the symbol Mg, atomic number 12, and common oxidation number +2. It is an alkaline earth metal and the eighth most abundant element in the Earth's crust and ninth in the known universe as a whole...

, alkali metal
Alkali metal
The alkali metals are a series of chemical elements in the periodic table. In the modern IUPAC nomenclature, the alkali metals comprise the group 1 elements, along with hydrogen. The alkali metals are lithium , sodium , potassium , rubidium , caesium , and francium...

s, alkaline earths, and other cations. Clays have structures similar to the mica
Mica
The mica group of sheet silicate minerals includes several closely related materials having highly perfect basal cleavage. All are monoclinic, with a tendency towards pseudohexagonal crystals, and are similar in chemical composition...

s and therefore form flat hexagonal sheets. Clay mineral
Mineral
A mineral is a naturally occurring solid chemical substance formed through biogeochemical processes, having characteristic chemical composition, highly ordered atomic structure, and specific physical properties. By comparison, a rock is an aggregate of minerals and/or mineraloids and does not...

s are common weathering
Weathering
Weathering is the breaking down of rocks, soils and minerals as well as artificial materials through contact with the Earth's atmosphere, biota and waters...

 products (including weathering of feldspar
Feldspar
Feldspars are a group of rock-forming tectosilicate minerals which make up as much as 60% of the Earth's crust....

) and low temperature hydrothermal alteration products. Clay minerals are very common in fine grained sedimentary rock
Sedimentary rock
Sedimentary rock are types of rock that are formed by the deposition of material at the Earth's surface and within bodies of water. Sedimentation is the collective name for processes that cause mineral and/or organic particles to settle and accumulate or minerals to precipitate from a solution....

s such as shale
Shale
Shale is a fine-grained, clastic sedimentary rock composed of mud that is a mix of flakes of clay minerals and tiny fragments of other minerals, especially quartz and calcite. The ratio of clay to other minerals is variable. Shale is characterized by breaks along thin laminae or parallel layering...

, mudstone
Mudstone
Mudstone is a fine grained sedimentary rock whose original constituents were clays or muds. Grain size is up to 0.0625 mm with individual grains too small to be distinguished without a microscope. With increased pressure over time the platey clay minerals may become aligned, with the...

, and siltstone
Siltstone
Siltstone is a sedimentary rock which has a grain size in the silt range, finer than sandstone and coarser than claystones.- Description :As its name implies, it is primarily composed of silt sized particles, defined as grains 1/16 - 1/256 mm or 4 to 8 on the Krumbein phi scale...

 and in fine grained metamorphic slate
Slate
Slate is a fine-grained, foliated, homogeneous metamorphic rock derived from an original shale-type sedimentary rock composed of clay or volcanic ash through low-grade regional metamorphism. The result is a foliated rock in which the foliation may not correspond to the original sedimentary layering...

 and phyllite
Phyllite
Phyllite is a type of foliated metamorphic rock primarily composed of quartz, sericite mica, and chlorite; the rock represents a gradation in the degree of metamorphism between slate and mica schist. Minute crystals of graphite, sericite, or chlorite impart a silky, sometimes golden sheen to the...

.

Clays are ultrafine-grained (normally considered to be less than 2 micrometres in size on standard particle size classifications) and so require special analytical techniques. Standards include x-ray diffraction, electron diffraction
Electron diffraction
Electron diffraction refers to the wave nature of electrons. However, from a technical or practical point of view, it may be regarded as a technique used to study matter by firing electrons at a sample and observing the resulting interference pattern...

 methods, various spectroscopic methods such as Mössbauer spectroscopy, infrared spectroscopy
Infrared spectroscopy
Infrared spectroscopy is the spectroscopy that deals with the infrared region of the electromagnetic spectrum, that is light with a longer wavelength and lower frequency than visible light. It covers a range of techniques, mostly based on absorption spectroscopy. As with all spectroscopic...

, and SEM-EDS or automated mineralogy
Automated mineralogy
Automated mineralogy is a generic term describing a range of analytical solutions, areas of commercial enterprise, and a growing field of scientific research and engineering applications involving largely automated and quantitative analysis of minerals, rocks and man-made...

 solutions. These methods can be augment polarized light microscopy
Petrographic microscope
A petrographic microscope is a type of optical microscope used in petrology and optical mineralogy to identify rocks and minerals in thin sections. The microscope is used in optical mineralogy and petrography, a branch of petrology which focuses on detailed descriptions of rocks...

, a traditional technique establishing fundamental occurrences or petrologic relationships.

Clays are commonly referred to as 1:1 or 2:1. Clays are fundamentally built of tetrahedral sheets and octahedral sheets, as described in the structure section below. A 1:1 clay would consist of one tetrahedral sheet and one octahedral sheet, and examples would be kaolinite and serpentine. A 2:1 clay consists of an octahedral sheet sandwiched between two tetrahedral sheets, and examples are illite, smectite, attapulgite, and chlorite (although chlorite has an external octahedral sheet often referred to as "brucite").

Clay minerals include the following groups:
  • Kaolin group which includes the minerals kaolinite
    Kaolinite
    Kaolinite is a clay mineral, part of the group of industrial minerals, with the chemical composition Al2Si2O54. It is a layered silicate mineral, with one tetrahedral sheet linked through oxygen atoms to one octahedral sheet of alumina octahedra...

    , dickite
    Dickite
    Dickite has molecular weight of 258.16 grams. It is a phyllosilicate clay mineral chemically composed of aluminium, silicon, hydrogen and oxygen contributing 20.90%, 21.76%, 1.56%, and 55.78% each respectively. It has the same composition as kaolinite, nacrite, and halloysite, but with a...

    , halloysite
    Halloysite
    Halloysite is a 1:1 aluminosilicate clay mineral with the empirical formula Al2Si2O54. Its main constituents are aluminium , silicon , and hydrogen . Halloysite typically forms by hydrothermal alteration of alumino-silicate minerals. It can occur intermixed with dickite, kaolinite, montmorillonite...

    , and nacrite
    Nacrite
    Nacrite Al2Si2O54 is a clay mineral that is a polymorph of kaolinite. It crystallizes in the monoclinic system. X-ray diffraction analysis is required for positive identification....

     (polymorphs of Al2Si2O5(OH)4).
    • Some sources include the kaolinite-serpentine group due to structural similarities (Bailey 1980).
  • Smectite group which includes dioctahedral smectites such as montmorillonite
    Montmorillonite
    Montmorillonite is a very soft phyllosilicate group of minerals that typically form in microscopic crystals, forming a clay. It is named after Montmorillon in France. Montmorillonite, a member of the smectite family, is a 2:1 clay, meaning that it has 2 tetrahedral sheets sandwiching a central...

     and nontronite
    Nontronite
    Nontronite is the iron rich member of the smectite group of clay minerals. Nontronites typically have a chemical composition consisting of more than ~30% Fe2O3 and less than ~12% Al2O3 . Nontronite generally does not exist in economic deposits like montmorillonite, although it is not an uncommon...

     and trioctahedral smectites for example saponite
    Saponite
    Saponite is a trioctahedral mineral of the smectite group. Its chemical formula is Ca0.2532·n. It is soluble in sulfuric acid. It was first described in 1840 by von Svanberg. Varieties of saponite are griffithite, bowlingite and sobotkite.It is soft, massive, and plastic, and exists in veins and...

    .
  • Illite
    Illite
    Illite is a non-expanding, clay-sized, micaceous mineral. Illite is a phyllosilicate or layered alumino-silicate. Its structure is constituted by the repetition of tetrahedron – octahedron – tetrahedron layers. The interlayer space is mainly occupied by poorly hydrated potassium cations...

     group which includes the clay-micas. Illite is the only common mineral.
  • Chlorite group
    Chlorite group
    The chlorites are a group of phyllosilicate minerals. Chlorites can be described by the following four endmembers based on their chemistry via substitution of the following four elements in the silicate lattice; Mg, Fe, Ni, and Mn....

     includes a wide variety of similar minerals with considerable chemical variation.
  • Other 2:1 clay types exist such as sepiolite
    Sepiolite
    Sepiolite is a clay mineral, a complex magnesium silicate, a typical formula for which is Mg4Si6O152·6H2O. It can be present in fibrous, fine-particulate, and solid forms....

     or attapulgite, clays with long water channels internal to their structure.


Mixed layer clay variations exist for most of the above groups. Ordering is described as random or regular ordering, and is further described by the term reichweite, which is German for range or reach. Literature articles will refer to a R1 ordered illite-smectite, for example. This type would be ordered in an ISISIS fashion. R0 on the other hand describes random ordering, and other advanced ordering types are also found (R3, etc). Mixed layer clay minerals which are perfect R1 types often get their own names. R1 ordered chlorite-smectite is known as corrensite, R1 illite-smectite is rectorite.

History


Knowledge of the nature of clay became better understood in the 1930s with advancements in x-ray diffraction technology necessary to analyze the molecular nature of clay particles. Standardization in terminology arose during this period as well with special attention given to similar words that resulted in confusion such as sheet and plane.

Structure


Like all phyllosilicates, clay minerals are characterised by two-dimensional sheets of corner sharing SiO4 and AlO4 tetrahedra. These tetrahedral sheets have the chemical composition (Al,Si)3O4, and each tetrahedron shares 3 of its vertex oxygen atoms with other tetrahedra forming a hexagonal array in two-dimensions. The fourth vertex is not shared with another tetrahedron and all of the tetrahedra "point" in the same direction; i.e. all of the unshared vertices are on the same side of the sheet.

In clays the tetrahedral sheets are always bonded to octahedral sheets formed from small cations, such as aluminium or magnesium, coordinated by six oxygen atoms. The unshared vertex from the tetrahedral sheet also form part of one side of the octahedral sheet but an additional oxygen atom is located above the gap in the tetrahedral sheet at the center of the six tetrahedra. This oxygen atom is bonded to a hydrogen atom forming an OH group in the clay structure. Clays can be categorised depending on the way that tetrahedral and octahedral sheets are packaged into layers. If there is only one tetrahedral and one octahedral group in each layer the clay is known as a 1:1 clay. The alternative, known as a 2:1 clay, has two tetrahedral sheets with the unshared vertex of each sheet pointing towards each other and forming each side of the octahedral sheet.

Bonding between the tetrahedral and octahedral sheets requires that the tetrahedral sheet becomes corrugated or twisted, causing ditrigonal distortion to the hexagonal array, and the octahedral sheet is flattened. This minimizes the overall bond-valence distortions of the crystallite.

Depending on the composition of the tetrahedral and octahedral sheets, the layer will have no charge, or will have a net negative charge. If the layers are charged this charge is balanced by interlayer cations such as Na+ or K+. In each case the interlayer can also contain water. The crystal structure is formed from a stack of layers interspaced with the interlayers.