
A smectite (; ; )
is a mineral mixture of various swelling sheet silicates (
phyllosilicate
Silicate minerals are rock-forming minerals made up of silicate groups. They are the largest and most important class of minerals and make up approximately 90 percent of Earth's crust.
In mineralogy, the crystalline forms of silica (silicon dio ...
s), which have a three-layer 2:1 (TOT) structure and belong to the clay minerals. Smectites mainly consist of
montmorillonite
Montmorillonite is a very soft phyllosilicate group of minerals that form when they precipitate from water solution as microscopic crystals, known as clay. It is named after Montmorillon in France. Montmorillonite, a member of the smectite grou ...
, but can often contain secondary minerals such as
quartz
Quartz is a hard, crystalline mineral composed of silica (silicon dioxide). The Atom, atoms are linked in a continuous framework of SiO4 silicon–oxygen Tetrahedral molecular geometry, tetrahedra, with each oxygen being shared between two tet ...
and
calcite
Calcite is a Carbonate minerals, carbonate mineral and the most stable Polymorphism (materials science), polymorph of calcium carbonate (CaCO3). It is a very common mineral, particularly as a component of limestone. Calcite defines hardness 3 on ...
.
[
]
Terminology
In clay mineralogy, smectite is synonym of montmorillonite (also the name of a pure clay mineral phase) to indicate a class of swelling clays. The term smectite is commonly used in Europe and in the UK while the term montmorillonite is preferred in North America, but both terms are equivalent and can be used interchangeably. For industrial and commercial applications, the term bentonite is mostly used in place of smectite or montmorillonite.
Mineralogical structure

The 2:1 layer (TOT) structure consists of two
silica
Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , commonly found in nature as quartz. In many parts of the world, silica is the major constituent of sand. Silica is one of the most complex and abundant f ...
(SiO
2)
tetrahedral
In geometry, a tetrahedron (: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular Face (geometry), faces, six straight Edge (geometry), edges, and four vertex (geometry), vertices. The tet ...
(T) layers which are electrostatically cross-linked via an Al
2O
3 (
gibbsite), or Fe
2O
3,
octahedral
In geometry, an octahedron (: octahedra or octahedrons) is any polyhedron with eight faces. One special case is the regular octahedron, a Platonic solid composed of eight equilateral triangles, four of which meet at each vertex. Many types of i ...
(O) central layer. The TOT elementary layers are not rigidly connected to each other but are separated by a free space: the interlayer hosting hydrated
cation
An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
s and
water molecules. Smectite can swell because of the reversible incorporation of water and cations in the interlayer space.
The TOT layers are negatively charged because of the isomorphic substitution of Si(IV) atoms by Al(III) atoms in the two external silica tetrahedral layers and because of the replacement of Al(III) or Fe(III) atoms by Mg
2+ or Fe
2+ cations in the inner gibbsite octahedral layer. As the +4 charges born by Si(IV), and normally compensated by −4 charges from the surrounding oxygen atoms, become +3 due to the substitution of Si(IV) by Al(III), an electrical imbalance occurs: +3 −4 = −1. The excess of negative charges in the TOT layer has to be compensated by the presence of positive cations in the interlayer. The same reasoning also applies to the gibbsite central layer of the TOT elementary unit when an Al
3+ ion is replaced by a Mg
2+ ion in a gibbsite octahedra. The electrical imbalance is: +2 −3 = −1.
Role of interlayer cations in the swelling process

The main
cation
An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
s in the smectite interlayers are Na
+ and Ca
2+. The
sodium
Sodium is a chemical element; it has Symbol (chemistry), symbol Na (from Neo-Latin ) and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the peri ...
cations are responsible for the highest swelling of smectite while
calcium
Calcium is a chemical element; it has symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to it ...
ions have lower swelling properties. Calcium smectite has significantly less swelling capacity than sodium smectite but is also less prone to shrinking when desiccated.
The degree of hydration of the cations and their corresponding hydrated radii explain the swelling or the shrinking behaviour of phyllosilicates. Other cations such as Mg
2+ and K
+ ions exhibit even a more contrasted effect: highly hydrated
magnesium
Magnesium is a chemical element; it has Symbol (chemistry), 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 ...
ions are "swellers" as in
vermiculite
Vermiculite is a hydrous phyllosilicate mineral which undergoes significant expansion when heated. Exfoliation occurs when the mineral is heated sufficiently; commercial furnaces can routinely produce this effect. Vermiculite forms by the weathe ...
(totally expanded interlayer) while poorly hydrated
potassium
Potassium is a chemical element; it has Symbol (chemistry), symbol K (from Neo-Latin ) and atomic number19. It is a silvery white metal that is soft enough to easily cut with a knife. Potassium metal reacts rapidly with atmospheric oxygen to ...
ions are "collapsers" like in
illite
Illite, also called hydromica or hydromuscovite, is a group of closely related non-expanding clay minerals. Illite is a secondary mineral precipitate, and an example of a phyllosilicate, or layered alumino-silicate. Its structure is a 2:1 sandw ...
(totally collapsed interlayer).
As the interlayer space of smectites is more open and so more easily accessible to water and cations, smectites exhibit the highest
cation-exchange capacity
Cation-exchange capacity (CEC) is a measure of how many cations can be retained on soil particle surfaces. Negative charges on the surfaces of soil particles bind positively-charged atoms or molecules (cations), but allow these to exchange with ot ...
(CEC) of clay minerals commonly found in the soils. Only more expandable
vermiculite
Vermiculite is a hydrous phyllosilicate mineral which undergoes significant expansion when heated. Exfoliation occurs when the mineral is heated sufficiently; commercial furnaces can routinely produce this effect. Vermiculite forms by the weathe ...
and some rarer alumino-silicate minerals (
zeolite
Zeolites are a group of several microporous, crystalline aluminosilicate minerals commonly used as commercial adsorbents and catalysts. They mainly consist of silicon, aluminium, oxygen, and have the general formula ・y where is either a meta ...
s) with inner channel structure can exhibit a higher CEC than smectite.
Formation process

Smectites are formed from the
weathering
Weathering is the deterioration of rocks, soils and minerals (as well as wood and artificial materials) through contact with water, atmospheric gases, sunlight, and biological organisms. It occurs '' in situ'' (on-site, with little or no move ...
of
basalt
Basalt (; ) is an aphanite, aphanitic (fine-grained) extrusive igneous rock formed from the rapid cooling of low-viscosity lava rich in magnesium and iron (mafic lava) exposed at or very near the planetary surface, surface of a terrestrial ...
,
gabbro
Gabbro ( ) is a phaneritic (coarse-grained and magnesium- and iron-rich), mafic intrusive igneous rock formed from the slow cooling magma into a holocrystalline mass deep beneath the Earth's surface. Slow-cooling, coarse-grained gabbro is ch ...
, and silica-rich
volcanic glass (e.g.,
pumice
Pumice (), called pumicite in its powdered or dust form, is a volcanic rock that consists of extremely vesicular rough-textured volcanic glass, which may or may not contain crystals. It is typically light-colored. Scoria is another vesicula ...
,
obsidian
Obsidian ( ) is a naturally occurring volcanic glass formed when lava extrusive rock, extruded from a volcano cools rapidly with minimal crystal growth. It is an igneous rock. Produced from felsic lava, obsidian is rich in the lighter element ...
,
rhyolite
Rhyolite ( ) is the most silica-rich of volcanic rocks. It is generally glassy or fine-grained (aphanitic) in texture (geology), texture, but may be porphyritic, containing larger mineral crystals (phenocrysts) in an otherwise fine-grained matri ...
,
dacite
Dacite () is a volcanic rock formed by rapid solidification of lava that is high in silica and low in alkali metal oxides. It has a fine-grained (aphanitic) to porphyritic texture and is intermediate in composition between andesite and rhyolite. ...
). Many smectites are formed in
volcanic
A volcano is commonly defined as a vent or fissure in the crust of a planetary-mass object, such as Earth, that allows hot lava, volcanic ash, and gases to escape from a magma chamber below the surface.
On Earth, volcanoes are most often fo ...
hydrothermal
Hydrothermal circulation in its most general sense is the circulation of hot water (Ancient Greek ὕδωρ, ''water'',Liddell, H.G. & Scott, R. (1940). ''A Greek-English Lexicon. revised and augmented throughout by Sir Henry Stuart Jones. with th ...
system (such as
geyser
A geyser (, ) is a spring with an intermittent water discharge ejected turbulently and accompanied by steam. The formation of geysers is fairly rare and is caused by particular hydrogeological conditions that exist only in a few places on Ea ...
system) where hot water percolating through the
porous matrix or the
cracks of the
volcanic ash
Volcanic ash consists of fragments of rock, mineral crystals, and volcanic glass, produced during volcanic eruptions and measuring less than 2 mm (0.079 inches) in diameter. The term volcanic ash is also often loosely used to r ...
deposit (
pumice
Pumice (), called pumicite in its powdered or dust form, is a volcanic rock that consists of extremely vesicular rough-textured volcanic glass, which may or may not contain crystals. It is typically light-colored. Scoria is another vesicula ...
,
pozzolan) dissolves most of
amorphous
In condensed matter physics and materials science, an amorphous solid (or non-crystalline solid) is a solid that lacks the long-range order that is a characteristic of a crystal. The terms "glass" and "glassy solid" are sometimes used synonymousl ...
silica
Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , commonly found in nature as quartz. In many parts of the world, silica is the major constituent of sand. Silica is one of the most complex and abundant f ...
(up to 50 wt.% of SiO
2 can be dissolved), leaving smectite in place. This mechanism is responsible for the formation of the bentonite deposit (Serrata de
Nijar) of
Cabo de Gata in the south-east region of
Almeria in
Andalusia
Andalusia ( , ; , ) is the southernmost autonomous communities of Spain, autonomous community in Peninsular Spain, located in the south of the Iberian Peninsula, in southwestern Europe. It is the most populous and the second-largest autonomou ...
(
Spain
Spain, or the Kingdom of Spain, is a country in Southern Europe, Southern and Western Europe with territories in North Africa. Featuring the Punta de Tarifa, southernmost point of continental Europe, it is the largest country in Southern Eur ...
). Wyoming MX-80
bentonite
Bentonite ( ) is an Absorption (chemistry), absorbent swelling clay consisting mostly of montmorillonite (a type of smectite) which can either be Na-montmorillonite or Ca-montmorillonite. Na-montmorillonite has a considerably greater swelli ...
was formed in a similar way during the
Cretaceous Period
The Cretaceous ( ) is a geological period that lasted from about 143.1 to 66 million years ago (Mya). It is the third and final period of the Mesozoic Era, as well as the longest. At around 77.1 million years, it is the ninth and longest geologi ...
when volcanic ashes were falling in an inner sea on the American continent. The highly
porous
Porosity or void fraction is a measure of the void (i.e. "empty") spaces in a material, and is a fraction of the volume of voids over the total volume, between 0 and 1, or as a percentage between 0% and 100%. Strictly speaking, some tests measure ...
(with a large and easily accessible
specific surface) and very reactive volcanic ashes rapidly reacted with
seawater
Seawater, or sea water, is water from a sea or ocean. On average, seawater in the world's oceans has a salinity of about 3.5% (35 g/L, 35 ppt, 600 mM). This means that every kilogram (roughly one liter by volume) of seawater has approximat ...
. Because of silica
hydrolysis
Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...
, most of
silica
Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , commonly found in nature as quartz. In many parts of the world, silica is the major constituent of sand. Silica is one of the most complex and abundant f ...
was dissolved in seawater and removed from the ashes giving rise to the formation of smectites. Smectites found in many marine clay deposits are often formed in this way as it is the case for the Ypresian Clays found in Belgium and very rich in smectites.
Industrial applications
Smectites are commonly used in very diverse industrial applications. In civil engineering works, it is routinely used as a thick
bentonite
Bentonite ( ) is an Absorption (chemistry), absorbent swelling clay consisting mostly of montmorillonite (a type of smectite) which can either be Na-montmorillonite or Ca-montmorillonite. Na-montmorillonite has a considerably greater swelli ...
slurry when excavating deep and narrow trenches in the ground to support the lateral walls and to avoid their collapse. It is also used as
mud
Mud (, or Middle Dutch) is loam, silt or clay mixed with water. Mud is usually formed after rainfall or near water sources. Ancient mud deposits hardened over geological time to form sedimentary rock such as shale or mudstone (generally cal ...
for
drilling fluid
In geotechnical engineering, drilling fluid, also known as drilling mud, is used to aid the drilling of boreholes into the earth. Used while drilling oil and natural gas wells and on exploration drilling rigs, drilling fluids are also use ...
s. Smectites, more commonly called bentonite, are candidate as buffer and backfill materials to fill the space around high-level
radioactive waste
Radioactive waste is a type of hazardous waste that contains radioactive material. It is a result of many activities, including nuclear medicine, nuclear research, nuclear power generation, nuclear decommissioning, rare-earth mining, and nuclear ...
in deep geological repositories. Smectites also serve as additive in
paint
Paint is a material or mixture that, when applied to a solid material and allowed to dry, adds a film-like layer. As art, this is used to create an image or images known as a painting. Paint can be made in many colors and types. Most paints are ...
s or as
thickening agent for various preparations.
See also
*
Argillaceous minerals
Clay minerals are hydrous aluminium phyllosilicates (e.g. kaolin, Al2 Si2 O5( OH)4), sometimes with variable amounts of iron, magnesium, alkali metals, alkaline earths, and other cations found on or near some planetary surfaces.
Clay minera ...
*
Bentonite
Bentonite ( ) is an Absorption (chemistry), absorbent swelling clay consisting mostly of montmorillonite (a type of smectite) which can either be Na-montmorillonite or Ca-montmorillonite. Na-montmorillonite has a considerably greater swelli ...
*
Clay
Clay is a type of fine-grained natural soil material containing clay minerals (hydrous aluminium phyllosilicates, e.g. kaolinite, ). Most pure clay minerals are white or light-coloured, but natural clays show a variety of colours from impuriti ...
*
Clay chemistry
*
Clay mineral
Clay minerals are hydrous aluminium phyllosilicates (e.g. kaolin, Al2 Si2 O5( OH)4), sometimes with variable amounts of iron, magnesium, alkali metals, alkaline earths, and other cations found on or near some planetary surfaces.
Clay minera ...
*
Clay–water interaction
*
Expansive clay
Expansive clay, also called expansive soil, is a clay soil prone to large volume changes (swelling and shrinking) directly related to changes in water content. Soils with a high content of expansive minerals can form deep cracks in drier seasons ...
*
Hectorite
*
Montmorillonite
Montmorillonite is a very soft phyllosilicate group of minerals that form when they precipitate from water solution as microscopic crystals, known as clay. It is named after Montmorillon in France. Montmorillonite, a member of the smectite grou ...
*
Nontronite
*
Saponite
Saponite is a trioctahedral mineral of the smectite group. Its chemical formula is . It is soluble in sulfuric acid. It was first described in 1840 by Lars Fredrik Svanberg, Svanberg. Varieties of saponite are griffithite, bowlingite and sobotk ...
References
Further reading
*
* Mitchell, J. K. (2001). Physicochemistry of soils for geoenvironmental engineering. In Geotechnical and geoenvironmental engineering handbook (pp. 691–710). Springer, Boston, MA.
* Mitchell, J. K., & Soga, K. (2005). Fundamentals of soil behavior (Vol. 3). New York: John Wiley & Sons.
* Mackenzie, R. C., & Mitchell, B. D. (1966). Clay mineralogy. Earth-Science Reviews, 2, 47–91.
* Jeans, C. V., Merriman, R. J., Mitchell, J. G., & Bland, D. J. (1982). Volcanic clays in the Cretaceous of southern England and Northern Ireland. Clay Minerals, 17(1), 105–156. https://doi.org/10.1180/claymin.1982.017.1.10
* Wagner, J. F. (2013). Chapter 9: Mechanical properties of clays and clay minerals. In: Developments in Clay Science, 5, 347–381. Elsevier. https://doi.org/10.1016/B978-0-08-098258-8.00011-0
External links
{{Phyllosilicates
Clay minerals group
Bentonite
Aluminium minerals
Calcium minerals
Sodium minerals
Medicinal clay
Phyllosilicates