Clay minerals are
hydrous
In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was underst ...
aluminium
Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. It ha ...
phyllosilicates (e.g. kaolin,
Al2 Si2 O5(
OH)
4), sometimes with variable amounts of
iron
Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in ...
,
magnesium
Magnesium is a chemical element with the symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 of the periodic ...
,
alkali metal
The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
s,
alkaline earth
The alkaline earth metals are six chemical elements in group 2 of the periodic table. They are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).. The elements have very similar properties: they are all ...
s, and other
cations found on or near some
planetary surfaces.
Clay minerals form in the presence of water and have been important to life, and many theories of
abiogenesis involve them. They are important constituents of
soils, and have been useful to humans since ancient times in
agriculture
Agriculture or farming is the practice of cultivating plants and livestock. Agriculture was the key development in the rise of sedentary human civilization, whereby farming of domesticated species created food surpluses that enabled people ...
and
manufacturing
Manufacturing is the creation or production of goods with the help of equipment, labor, machines, tools, and chemical or biological processing or formulation. It is the essence of secondary sector of the economy. The term may refer to ...
.
Properties
Clay
Clay is a type of fine-grained natural soil material containing clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4).
Clays develop plasticity when wet, due to a molecular film of water surrounding the clay pa ...
is a very fine-grained geologic material that develops
plasticity when wet, but becomes hard, brittle and non–plastic upon drying or
firing. It is a very common material, and is the oldest known
ceramic
A ceramic is any of the various hard, brittle, heat-resistant and corrosion-resistant materials made by shaping and then firing an inorganic, nonmetallic material, such as clay, at a high temperature. Common examples are earthenware, porcelain, ...
. Prehistoric humans discovered the useful properties of clay and used it for making
pottery
Pottery is the process and the products of forming vessels and other objects with clay and other ceramic materials, which are fired at high temperatures to give them a hard and durable form. Major types include earthenware, stoneware and ...
. The chemistry of clay, including its capacity to retain nutrient cations such as
potassium
Potassium is the chemical element with the symbol K (from Neo-Latin '' kalium'') and atomic number19. Potassium is a silvery-white metal that is soft enough to be cut with a knife with little force. Potassium metal reacts rapidly with atmos ...
and
ammonium, is important to soil fertility.
Because the individual particles in clay are less than in size, they cannot be characterized by ordinary optical or physical methods. The crystallographic structure of clay minerals became better understood in the 1930s with advancements in the
x-ray diffraction (XRD) technique indispensable to deciphering their crystal lattice.
Clay particles were found to be predominantly
sheet silicate (phyllosilicate) minerals, now grouped together as clay minerals. Their structure is based on flat hexagonal sheets similar to those of the
mica group of minerals.
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.
Because clay minerals are usually (but not necessarily) ultrafine-grained, special analytical techniques are required for their identification and study. In addition to X-ray crystallography, these include
electron diffraction methods,
various spectroscopic methods such as
Mössbauer spectroscopy,
infrared spectroscopy
Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or functi ...
,
[ Raman spectroscopy, and SEM- EDS or ]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 mi ...
[ processes. These methods can be augmented by polarized light microscopy, a traditional technique establishing fundamental occurrences or petrologic relationships.
]
Occurrence
Clay mineral
In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid chemical compound with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. (2 ...
s are common weathering
Weathering is the deterioration of rocks, soils and minerals as well as wood and artificial materials through contact with water, atmospheric gases, and biological organisms. Weathering occurs '' in situ'' (on site, with little or no movement ...
products (including weathering of feldspar
Feldspars are a group of rock-forming aluminium tectosilicate minerals, also containing other cations such as sodium, calcium, potassium, or barium. The most common members of the feldspar group are the ''plagioclase'' (sodium-calcium) felds ...
) and low-temperature hydrothermal alteration products. Clay minerals are very common in soils, in fine-grained sedimentary rock
Sedimentary rocks are types of rock that are formed by the accumulation or deposition of mineral or organic particles at Earth's surface, followed by cementation. Sedimentation is the collective name for processes that cause these particles ...
s such as shale, mudstone, and siltstone and in fine-grained metamorphic slate and phyllite.[
Given the requirement of water, clay minerals are relatively rare in the ]Solar System
The Solar System Capitalization of the name varies. The International Astronomical Union, the authoritative body regarding astronomical nomenclature, specifies capitalizing the names of all individual astronomical objects but uses mixed "Solar ...
, though they occur extensively on Earth where water has interacted with other minerals and organic matter. Clay minerals have been detected at several locations on Mars
Mars is the fourth planet from the Sun and the second-smallest planet in the Solar System, only being larger than Mercury. In the English language, Mars is named for the Roman god of war. Mars is a terrestrial planet with a thin at ...
, including Echus Chasma, Mawrth Vallis, the Memnonia quadrangle
The Memnonia quadrangle is one of a series of 30 quadrangle maps of Mars used by the United States Geological Survey (USGS) Astrogeology Research Program. The Memnonia quadrangle is also referred to as MC-16 (Mars Chart-16).
The quadrangle is ...
and the Elysium quadrangle. Spectrography has confirmed their presence on asteroids including the dwarf planet Ceres and Tempel 1, as well as Jupiter's moon Europa
Europa may refer to:
Places
* Europe
* Europa (Roman province), a province within the Diocese of Thrace
* Europa (Seville Metro), Seville, Spain; a station on the Seville Metro
* Europa City, Paris, France; a planned development
* Europa Clif ...
.
Structure
Like all phyllosilicates, clay minerals are characterised by two-dimensional ''sheets'' of corner-sharing tetrahedra or octahedra. The sheet units have the chemical composition . Each silica tetrahedron shares three of its vertex oxygen ions with other tetrahedra, forming a hexagonal array in two dimensions. The fourth oxygen ion is not shared with another tetrahedron and all of the tetrahedra "point" in the same direction; i.e. all of the unshared oxygen ions are on the same side of the sheet. These unshared oxygen ions are called apical oxygen ions.
In clays, the tetrahedral sheets are always bonded to octahedral sheets formed from small cations, such as aluminum or magnesium, and coordinated by six oxygen atoms. The unshared vertex from the tetrahedral sheet also forms 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 categorized 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+ or by a lone octahedral sheet. The interlayer may also contain water. The crystal structure is formed from a stack of layers interspaced with the interlayers.
Classification
Clay minerals can be classified as 1:1 or 2:1. A 1:1 clay would consist of one tetrahedral sheet and one octahedral sheet, and examples would be kaolinite
Kaolinite ( ) is a clay mineral, with the chemical composition Al2 Si2 O5( OH)4. It is an important industrial mineral. It is a layered silicate mineral, with one tetrahedral sheet of silica () linked through oxygen atoms to one octahed ...
and serpentinite
Serpentinite is a rock composed predominantly of one or more serpentine group minerals, the name originating from the similarity of the texture of the rock to that of the skin of a snake. Serpentinite has been called ''serpentine'' or ''s ...
. A 2:1 clay consists of an octahedral sheet sandwiched between two tetrahedral sheets, and examples are talc, vermiculite, and montmorillonite. The layers in 1:1 clays are uncharged and are bonded by hydrogen bonds between layers, but 2:1 layers have a net negative charge and may be bonded together either by individual cations (such as potassium in illite or sodium or calcium in smectites) or by positively charged octahedral sheets (as in chlorites).[
Clay minerals include the following groups:
* ]Kaolin
Kaolinite ( ) is a clay mineral, with the chemical composition Al2 Si2 O5( OH)4. It is an important industrial mineral. It is a layered silicate mineral, with one tetrahedral sheet of silica () linked through oxygen atoms to one octahedra ...
group which includes the minerals kaolinite
Kaolinite ( ) is a clay mineral, with the chemical composition Al2 Si2 O5( OH)4. It is an important industrial mineral. It is a layered silicate mineral, with one tetrahedral sheet of silica () linked through oxygen atoms to one octahed ...
, dickite, halloysite, and nacrite
Nacrite Al2 Si2 O5( OH)4 is a clay mineral that is polymorphous (or polytypic) with kaolinite. It crystallizes in the monoclinic system. X-ray diffraction analysis is required for positive identification.
Nacrite was first described in 1807 f ...
( polymorphs of ).
** Some sources include the kaolinite-serpentine group due to structural similarities.
* Smectite group which includes dioctahedral smectites, such as montmorillonite, nontronite and beidellite, and trioctahedral smectites, such as saponite. In 2013, analytical tests by the Curiosity rover
''Curiosity'' is a car-sized Mars rover designed to explore the Gale crater on Mars as part of NASA's Mars Science Laboratory (MSL) mission. ''Curiosity'' was launched from Cape Canaveral (CCAFS) on November 26, 2011, at 15:02:00 UTC and la ...
found results consistent with the presence of ''smectite clay minerals'' on the planet Mars
Mars is the fourth planet from the Sun and the second-smallest planet in the Solar System, only being larger than Mercury. In the English language, Mars is named for the Roman god of war. Mars is a terrestrial planet with a thin at ...
.
* Illite group which includes the clay-micas. Illite is the only common mineral in this group.
* Chlorite group
The chlorites are the group of phyllosilicate minerals common in low-grade metamorphic rocks and in altered igneous rocks. Greenschist, formed by metamorphism of basalt or other low-silica volcanic rock, typically contains significant amou ...
includes a wide variety of similar minerals with considerable chemical variation.
* Other 2:1 clay types exist such as palygorskite (also known as attapulgite) and sepiolite, clays with long water channels internal to their structure.
Mixed layer clay variations exist for most of the above groups.[ Ordering is described as a random or regular order and is further described by the term reichweite, which is German for range or reach. Literature articles will refer to an R1 ordered illite-smectite, for example. This type would be ordered in an illite-smectite-illite-smectite (ISIS) 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.
''X-ray rf(001)'' is the spacing between layers in nanometers, as determined by X-ray crystallography. ''Glycol (mg/g)'' is the adsorption capacity for glycol, which occupies the interlayer sites when the clay is exposed to a vapor of ]ethylene glycol
Ethylene glycol ( IUPAC name: ethane-1,2-diol) is an organic compound (a vicinal diol) with the formula . It is mainly used for two purposes, as a raw material in the manufacture of polyester fibers and for antifreeze formulations. It is an o ...
at for eight hours. ''CEC'' is the cation exchange capacity of the clay. '' (%)'' is the percent content of potassium oxide in the clay. ''DTA'' describes the differential thermal analysis curve of the clay.
Clay and the origins of life
Biomedical applications of clays
The structural and compositional versatility of clay minerals gives them interesting biological properties. Due to disc-shaped and charged surfaces, clay interacts with a range of drugs, protein, polymers, DNA, or other macromolecules. Some of the applications of clays include drug delivery, tissue engineering, and bioprinting.
Mortar applications
Clay minerals can be incorporated in lime-metakaolin mortars to improve mechanical properties. Electrochemical separation helps to obtain modified saponite-containing products with high smectite-group minerals concentrations, lower mineral particles size, more compact structure, and greater surface area. These characteristics open possibilities for the manufacture of high-quality ceramics and heavy-metal sorbents from saponite-containing products.
Furthermore, tail grinding occurs during the preparation of the raw material for ceramics; this waste reprocessing is of high importance for the use of clay pulp as a neutralizing agent, as fine particles are required for the reaction. Experiments on the histosol deacidification with the alkaline clay slurry demonstrated that neutralization with the average pH level of 7.1 is reached at 30% of the pulp added and an experimental site with perennial grasses proved the efficacy of the technique. Moreover, the reclamation of disturbed lands is an integral part of the social and environmental responsibility of the mining company and this scenario addresses the community necessities at both local and regional levels.
The tests which verify that clay minerals are present
The results of glycol adsorption, cation exchange capacity, X-ray diffraction, differential thermal analysis, and chemical tests all give data that may be used for quantitative estimations. After the quantities of organic matter, carbonates, free oxides, and nonclay minerals have been determined, the percentages of clay minerals are estimated using the appropriate glycol adsorption, cation exchange capacity, K20, and DTA data. The amount of illite is estimated from the K20 content since this is the only clay mineral containing potassium.
Argillaceous rocks
Argillaceous rocks are those in which clay minerals are a significant component. For example, ''argillaceous limestones'' are limestones consisting predominantly of calcium carbonate, but including 10-40% of clay minerals: such limestones, when soft, are often called marls. Similarly, ''argillaceous sandstones'' such as greywacke, are sandstones
Sandstone is a clastic sedimentary rock composed mainly of sand-sized (0.0625 to 2 mm) silicate grains. Sandstones comprise about 20–25% of all sedimentary rocks.
Most sandstone is composed of quartz or feldspar (both silicates) ...
consisting primarily of quartz
Quartz is a hard, crystalline mineral composed of silica ( silicon dioxide). The atoms are linked in a continuous framework of SiO4 silicon-oxygen tetrahedra, with each oxygen being shared between two tetrahedra, giving an overall chemical f ...
grains, with the interstitial spaces filled with clay minerals.
See also
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* Mudstone/clays on planet Mars
Mars is the fourth planet from the Sun and the second-smallest planet in the Solar System, only being larger than Mercury. In the English language, Mars is named for the Roman god of war. Mars is a terrestrial planet with a thin at ...
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References
Works cited
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Soil chemistry
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