Huntite
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Huntite is a
carbonate mineral Carbonate minerals are those minerals containing the carbonate ion, . Carbonate divisions Anhydrous carbonates *Calcite group: trigonal ** Calcite CaCO3 ** Gaspéite (Ni,Mg,Fe2+)CO3 ** Magnesite MgCO3 **Otavite CdCO3 ** Rhodochrosite MnCO3 ...
with the chemical formula Mg3Ca(CO3)4. Huntite crystallizes in the
trigonal In crystallography, the hexagonal crystal family is one of the six crystal families, which includes two crystal systems (hexagonal and trigonal) and two lattice systems (hexagonal and rhombohedral). While commonly confused, the trigonal crystal ...
system and typically occurs as platy crystals and powdery masses. For most of recorded history its main use was as a white pigment. Today the most common industrial use of huntite is as a natural mixture with
hydromagnesite Hydromagnesite is a hydrated magnesium carbonate mineral with the formula Mg5(CO3)4(OH)2·4H2O. It generally occurs associated with the weathering products of magnesium containing minerals such as serpentine or brucite. It occurs as incrustations ...
as a
flame retardant The term flame retardants subsumes a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an ignition source and ...
or
fire retardant A fire retardant is a substance that is used to slow down or stop the spread of fire or reduce its intensity. This is commonly accomplished by chemical reactions that reduce the flammability of fuels or delay their combustion. Fire retardants ...
additive for polymers.


Discovery

In 1953 a paper by George Faust announced the discovery of a new carbonate mineral found in Currant Creek, Nevada (US). Faust acknowledged that the mineral probably had been discovered previously, but it had been misidentified as impure magnesite by W. E. Ford in 1917. Faust named the new mineral "huntite" in honour of his former teacher, Walter Frederick Hunt (1882–1975), Professor of Petrology at the University of Michigan. Faust carried out analyses of the mineral, and found amongst others that in differential thermal analysis huntite showed two endothermic peaks, which could be attributed to the dissociation of MgCO3 and CaCO3 respectively. Chemical analyses showed huntite to consist of Mg3Ca(CO3)4.


Properties

Huntite often occurs in combination with other Mg/Ca carbonates such as
dolomite Dolomite may refer to: *Dolomite (mineral), a carbonate mineral *Dolomite (rock), also known as dolostone, a sedimentary carbonate rock *Dolomite, Alabama, United States, an unincorporated community *Dolomite, California, United States, an unincor ...
,
magnesite Magnesite is a mineral with the chemical formula ( magnesium carbonate). Iron, manganese, cobalt, and nickel may occur as admixtures, but only in small amounts. Occurrence Magnesite occurs as veins in and an alteration product of ultramafic ...
, and
hydromagnesite Hydromagnesite is a hydrated magnesium carbonate mineral with the formula Mg5(CO3)4(OH)2·4H2O. It generally occurs associated with the weathering products of magnesium containing minerals such as serpentine or brucite. It occurs as incrustations ...
. Large deposits of huntite occur in Turkey and Greece and these are commercially exploited because of its fire retardant properties. Huntite thermally decomposes over a temperature range of about 450–800 °C, releasing
carbon dioxide Carbon dioxide ( chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is t ...
and leaving a residue of
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 ...
and
calcium oxide Calcium oxide (CaO), commonly known as quicklime or burnt lime, is a widely used chemical compound. It is a white, caustic, alkaline, crystalline solid at room temperature. The broadly used term "'' lime''" connotes calcium-containing inorganic ...
s.


Occurrences

Huntite has been found in a variety of environments. For example, it occurs in the modern carbonate sediments of the tidal flats bordering the
Persian Gulf The Persian Gulf ( fa, خلیج فارس, translit=xalij-e fârs, lit=Gulf of Fars, ), sometimes called the ( ar, اَلْخَلِيْجُ ٱلْعَرَبِيُّ, Al-Khalīj al-ˁArabī), is a mediterranean sea in Western Asia. The bo ...
, in seasonal salt lakes of Turkey, in various playa lakes of
British Columbia British Columbia (commonly abbreviated as BC) is the westernmost province of Canada, situated between the Pacific Ocean and the Rocky Mountains. It has a diverse geography, with rugged landscapes that include rocky coastlines, sandy beaches, for ...
(Canada), in lacustrine deposits of Greece and in modern sabkha sediments in Tunisia. Caves seem to be well suited for the low-temperature formation of huntite. For example, it has been reported from the caves of the
Carlsbad Caverns National Park Carlsbad Caverns National Park is an American national park in the Guadalupe Mountains of southeastern New Mexico. The primary attraction of the park is the show cave Carlsbad Cavern. Visitors to the cave can hike in on their own via the natural ...
, New Mexico (USA); in the
Castleguard Cave Castleguard Cave is a limestone cave located at the north end of Banff National Park in the Rocky Mountains of Alberta, Canada. With of surveyed passages (as of 2007), it is Canada's longest cave, and its fifth deepest at . Castleguard Cave a ...
(Alberta, Canada); in the Grotte de Clamouse, France; in various caves of the
Transvaal Province The Province of the Transvaal ( af, Provinsie van Transvaal), commonly referred to as the Transvaal (; ), was a province of South Africa from 1910 until 1994, when a new constitution subdivided it following the end of apartheid. The name "Trans ...
of South Africa; in the
Jenolan Caves The Jenolan Caves ( Tharawal: ''Binoomea'', ''Bindo'', ''Binda'') are limestone caves located within the Jenolan Karst Conservation Reserve in the Central Tablelands region, west of the Blue Mountains, in Jenolan, Oberon Council, New South Wa ...
, Australia; and in the Castañar Cave near Cáceres, Spain.


Syntheses

In 1962, huntite was first synthesized by Biedl and Preisinger in experiments conducted at 100 °C and 3.2 bar CO2 pressure. In 1983 Oomori et al. claimed laboratory synthesis of huntite at 33 °C when adding a
sodium carbonate Sodium carbonate, , (also known as washing soda, soda ash and soda crystals) is the inorganic compound with the formula Na2CO3 and its various hydrates. All forms are white, odourless, water-soluble salts that yield moderately alkaline solutions ...
solution to concentrated sea water saturated with
calcium bicarbonate Calcium bicarbonate, also called calcium hydrogencarbonate, has the chemical formula Ca(HCO3)2. The term does not refer to a known solid compound; it exists only in aqueous solution containing calcium (Ca2+), bicarbonate (), and carbonate () ions ...
. In 2006, Zaitseva et al noted the precipitation of huntite at room temperature and atmospheric pressure. In laboratory experiments originally intended to synthesize magnesium calcite, they had added cultures of ''Microcoleus chtonoplastes'' (
cyanobacteria Cyanobacteria (), also known as Cyanophyta, are a phylum of gram-negative bacteria that obtain energy via photosynthesis. The name ''cyanobacteria'' refers to their color (), which similarly forms the basis of cyanobacteria's common name, bl ...
) to sea water brine. After 10 months of continuously shaking the samples they found huntite,
magnesite Magnesite is a mineral with the chemical formula ( magnesium carbonate). Iron, manganese, cobalt, and nickel may occur as admixtures, but only in small amounts. Occurrence Magnesite occurs as veins in and an alteration product of ultramafic ...
, and
aragonite Aragonite is a carbonate mineral, one of the three most common naturally occurring crystal forms of calcium carbonate, (the other forms being the minerals calcite and vaterite). It is formed by biological and physical processes, including pre ...
. In 2012, Hopkinson et al. synthesized the mineral at 52 °C by reacting magnesium calcite with nesquehonite (MgCO3·3H2O).


Genesis

Huntite,
dolomite Dolomite may refer to: *Dolomite (mineral), a carbonate mineral *Dolomite (rock), also known as dolostone, a sedimentary carbonate rock *Dolomite, Alabama, United States, an unincorporated community *Dolomite, California, United States, an unincor ...
and
magnesite Magnesite is a mineral with the chemical formula ( magnesium carbonate). Iron, manganese, cobalt, and nickel may occur as admixtures, but only in small amounts. Occurrence Magnesite occurs as veins in and an alteration product of ultramafic ...
appear to be so very closely related, that a genetic relationship seems to be implied. In a number of instances all three carbonates are found in close association; for example Faust (1953) described huntite occurring together with dolomite and
magnesite Magnesite is a mineral with the chemical formula ( magnesium carbonate). Iron, manganese, cobalt, and nickel may occur as admixtures, but only in small amounts. Occurrence Magnesite occurs as veins in and an alteration product of ultramafic ...
(amongst other minerals); Carpenter (1961) found huntite associated with
aragonite Aragonite is a carbonate mineral, one of the three most common naturally occurring crystal forms of calcium carbonate, (the other forms being the minerals calcite and vaterite). It is formed by biological and physical processes, including pre ...
, magnesium calcite and dolomite; Larrabee (1969) reported on huntite together with (amongst many others)
aragonite Aragonite is a carbonate mineral, one of the three most common naturally occurring crystal forms of calcium carbonate, (the other forms being the minerals calcite and vaterite). It is formed by biological and physical processes, including pre ...
,
calcite Calcite is a carbonate mineral and the most stable polymorph of calcium carbonate (CaCO3). It is a very common mineral, particularly as a component of limestone. Calcite defines hardness 3 on the Mohs scale of mineral hardness, based on scratc ...
, dolomite and
magnesite Magnesite is a mineral with the chemical formula ( magnesium carbonate). Iron, manganese, cobalt, and nickel may occur as admixtures, but only in small amounts. Occurrence Magnesite occurs as veins in and an alteration product of ultramafic ...
in
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 ...
on a weathered
dunite Dunite (), also known as olivinite (not to be confused with the mineral olivenite), is an intrusive igneous rock of ultramafic composition and with phaneritic (coarse-grained) texture. The mineral assemblage is greater than 90% olivine, w ...
rock. A weathered
basalt Basalt (; ) is an 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 surface of a rocky planet or moon. More than 90 ...
in Australia was found to contain huntite in association with
magnesite Magnesite is a mineral with the chemical formula ( magnesium carbonate). Iron, manganese, cobalt, and nickel may occur as admixtures, but only in small amounts. Occurrence Magnesite occurs as veins in and an alteration product of ultramafic ...
(Cole & Lancucki, 1975). Huntite together with magnesite was found by Calvo et al. (1995) in lake sediments of Northern Greece. Huntite in combination with
magnesite Magnesite is a mineral with the chemical formula ( magnesium carbonate). Iron, manganese, cobalt, and nickel may occur as admixtures, but only in small amounts. Occurrence Magnesite occurs as veins in and an alteration product of ultramafic ...
occurs in a weathered
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 ...
near Hrubšice, Czech Republic according to Němec (1981) According to the mineral and locations database of "mindat.org" huntite, together with
aragonite Aragonite is a carbonate mineral, one of the three most common naturally occurring crystal forms of calcium carbonate, (the other forms being the minerals calcite and vaterite). It is formed by biological and physical processes, including pre ...
,
calcite Calcite is a carbonate mineral and the most stable polymorph of calcium carbonate (CaCO3). It is a very common mineral, particularly as a component of limestone. Calcite defines hardness 3 on the Mohs scale of mineral hardness, based on scratc ...
, dolomite and
magnesite Magnesite is a mineral with the chemical formula ( magnesium carbonate). Iron, manganese, cobalt, and nickel may occur as admixtures, but only in small amounts. Occurrence Magnesite occurs as veins in and an alteration product of ultramafic ...
can be found in the "U Pustého Mlýna" quarry near Hrubšice, Czech Republic.


Industrial use

The most common industrial use of huntite is as a natural mixture with
hydromagnesite Hydromagnesite is a hydrated magnesium carbonate mineral with the formula Mg5(CO3)4(OH)2·4H2O. It generally occurs associated with the weathering products of magnesium containing minerals such as serpentine or brucite. It occurs as incrustations ...
as a
flame retardant The term flame retardants subsumes a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an ignition source and ...
or
fire retardant A fire retardant is a substance that is used to slow down or stop the spread of fire or reduce its intensity. This is commonly accomplished by chemical reactions that reduce the flammability of fuels or delay their combustion. Fire retardants ...
additive for polymers. The heat of a fire will cause huntite to decompose releasing carbon dioxide into the flames. This helps to slow the spread of the fire. The release of carbon dioxide is
endothermic In thermochemistry, an endothermic process () is any thermodynamic process with an increase in the enthalpy (or internal energy ) of the system.Oxtoby, D. W; Gillis, H.P., Butler, L. J. (2015).''Principle of Modern Chemistry'', Brooks Cole. ...
, meaning that it takes in heat, this action helps to cool the burning material, again slowing the spread of the fire. These types of mixtures are used as alternatives to the more commonly used
aluminium hydroxide Aluminium hydroxide, Al(OH)3, is found in nature as the mineral gibbsite (also known as hydrargillite) and its three much rarer polymorphs: bayerite, doyleite, and nordstrandite. Aluminium hydroxide is amphoteric, i.e., it has both basic ...
.


Conite

A mineral with exactly the same composition as that of huntite has been known for more than 200 years; in 1812 for example, John and Stromeyer described it as having a chemical composition of CaCO3 : MgCO3 = 1 : 3 . In those days the mineral was known as ''conite'' (in German: Konit); a name given to it by Retzius (1798).Retzius, A. J. (1798): Versuch einer Aufstellung des Mineralreiches. S. L. Crusius, Leipzig, 376 p. However, a serious problem concerns the exact location where the mineral ''conite'' can be found. Originally Retzius had found the new carbonate in a mineral collection, and had recognized it as a new species because it was harder than any of the known carbonates (even so hard, that it would spark when struck with steel) but no indication was given as to the site where this ''conite'' had been found. A number of papers describing ''conite'' are known, without the exact location where it can be found. In 1804, Ludwig stated that the sample of ''conite'' studied by him, came "from Iceland". In 1805 Leonhard wrote that the ''conite'' he had analyzed, came "from Scandinavia". Somewhat more exact was Stromeyer in 1812, who claimed that his sample of ''conite'' had been found near the village of Frankenhayn, on the eastern slope of the Hoher Meissner near
Kassel Kassel (; in Germany, spelled Cassel until 1926) is a city on the Fulda River in northern Hesse, Germany. It is the administrative seat of the Regierungsbezirk Kassel and the district of the same name and had 201,048 inhabitants in December 2020 ...
, Germany. However, this ''conite'' had been found there as a loose boulder, and no outcrop of the new mineral was mentioned. In 1833 Blum summed up how ''conite'' could be found in mines near
Freiberg Freiberg is a university and former mining town in Saxony, Germany. It is a so-called ''Große Kreisstadt'' (large county town) and the administrative centre of Mittelsachsen district. Its historic town centre has been placed under heritage c ...
(Germany), as boulders on the slopes of Mount Meissner (Germany) and on Iceland. In 1849, Hirzel repeated that ''conite'' could be found on the eastern slope of Mount Meissner, and in 1882 Schrauf reported the mineral from the magnesite deposits on the borders of the Schöninger Bach at
Křemže Křemže (german: Krems) is a market town in Český Krumlov District in the South Bohemian Region of the Czech Republic. It has about 3,000 inhabitants. Administrative parts Villages of Bohouškovice, Chlum, Chlumeček, Chmelná, Lhotka, Loučej ...
near Budweis, Czech Republic.Schrauf, A. (1882): Beiträge zur Kenntnis des Associationskreises des Magnesiasilicate. '' Zeitschrift für Krystallographie und Mineralogie'', vol.6, pp.321-388. Because of the absence of a type locality for the mineral ''conite'', a historical priority of its description over that of huntite cannot be claimed.


References

{{Reflist, 2 Calcium minerals Carbonate minerals Magnesium minerals Trigonal minerals Minerals in space group 155 Flame retardants Minerals described in 1953