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 **Sider ...
with the chemical formula Mg3Ca(CO3)4. Huntite crystallizes in the
trigonal In crystallography, the hexagonal crystal family is one of the six crystal family, crystal families, which includes two crystal systems (hexagonal and trigonal) and two lattice systems (hexagonal and rhombohedral). While commonly confused, the tr ...
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 . It generally occurs associated with the weathering products of magnesium containing minerals such as serpentine group, serpentine or brucite. It occurs as incrustations a ...
as a
flame retardant Flame retardants are 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 combustion, ignition source and pr ...
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,
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 r ...
, and
hydromagnesite Hydromagnesite is a hydrated magnesium carbonate mineral with the formula . It generally occurs associated with the weathering products of magnesium containing minerals such as serpentine group, serpentine or brucite. It occurs as incrustations a ...
. Large deposits of huntite occur in
Turkey Turkey, officially the Republic of Türkiye, is a country mainly located in Anatolia in West Asia, with a relatively small part called East Thrace in Southeast Europe. It borders the Black Sea to the north; Georgia (country), Georgia, Armen ...
and
Greece Greece, officially the Hellenic Republic, is a country in Southeast Europe. Located on the southern tip of the Balkan peninsula, it shares land borders with Albania to the northwest, North Macedonia and Bulgaria to the north, and Turkey to th ...
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 is a chemical compound with the chemical formula . It is made up of molecules that each have one carbon atom covalent bond, covalently double bonded to two oxygen atoms. It is found in a gas state at room temperature and at norma ...
and leaving a residue of
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 ...
and
calcium oxide Calcium oxide (formula: Ca O), 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 ...
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, sometimes called the Arabian Gulf, is a Mediterranean seas, mediterranean sea in West Asia. The body of water is an extension of the Arabian Sea and the larger Indian Ocean located between Iran and the Arabian Peninsula.Un ...
, in seasonal salt lakes of Turkey, in various playa lakes of
British Columbia British Columbia is the westernmost Provinces and territories of Canada, province of Canada. Situated in the Pacific Northwest between the Pacific Ocean and the Rocky Mountains, the province has a diverse geography, with rugged landscapes that ...
(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, New Mexico (US); in the Castleguard Cave (Alberta, Canada); in the Grotte de Clamouse,
France France, officially the French Republic, is a country located primarily in Western Europe. Overseas France, Its overseas regions and territories include French Guiana in South America, Saint Pierre and Miquelon in the Atlantic Ocean#North Atlan ...
; in various caves of the
Transvaal Province The Province of 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 "Transvaal" refers to the province's ...
of
South Africa South Africa, officially the Republic of South Africa (RSA), is the Southern Africa, southernmost country in Africa. Its Provinces of South Africa, nine provinces are bounded to the south by of coastline that stretches along the Atlantic O ...
; in Clearwater Cave, Mulu, Sarawak in the
Jenolan Caves The Jenolan Caves (Tharawal language, Tharawal: ''Binoomea'', ''Bindo'', ''Binda'') are limestone cave, limestone caves located within the Jenolan Karst Conservation Reserve in the Central Tablelands region, west of the Blue Mountains (New Sout ...
,
Australia Australia, officially the Commonwealth of Australia, is a country comprising mainland Australia, the mainland of the Australia (continent), Australian continent, the island of Tasmania and list of islands of Australia, numerous smaller isl ...
; and in the Castañar Cave near Cáceres,
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 ...
.


Syntheses

In 1962, huntite was first synthesized by Biedl and Preisinger in experiments conducted at 100 °C and 3.2 bar 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, sal soda, and soda crystals) is the inorganic compound with the formula and its various hydrates. All forms are white, odourless, water-soluble salts that yield alkaline solutions in water ...
solution to concentrated
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 ...
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 () io ...
. 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 ( ) are a group of autotrophic gram-negative bacteria that can obtain biological energy via oxygenic photosynthesis. The name "cyanobacteria" () refers to their bluish green (cyan) color, which forms the basis of cyanobacteri ...
) to seawater 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 r ...
, and
aragonite Aragonite is a carbonate mineral and one of the three most common naturally occurring crystal forms of calcium carbonate (), the others being calcite and vaterite. It is formed by biological and physical processes, including precipitation fr ...
. In 2012, Hopkinson et al. synthesized the mineral at 52 °C by reacting magnesium calcite with nesquehonite (MgCO3·3H2O).


Genesis

Huntite, dolomite and magnesite appear to be so very closely related that a genetic relationship seems to be implied. In some instances, all three carbonates are found in close association; for example, Faust (1953) described huntite occurring together with dolomite and magnesite (amongst other minerals); Carpenter (1961) found huntite associated with aragonite, magnesium calcite and dolomite; Larrabee (1969) reported on huntite together with (amongst many others) aragonite,
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 ...
, dolomite and magnesite in
serpentinite Serpentinite is a metamorphic rock composed predominantly of serpentine group minerals formed by serpentinization of mafic or ultramafic rocks. The ancient origin of the name is uncertain; it may be from the similarity of its texture or color ...
on a weathered dunite rock. A weathered
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 ...
in Australia was found to contain huntite in association with magnesite (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 occurs in a weathered serpentinite near Hrubšice,
Czech Republic The Czech Republic, also known as Czechia, and historically known as Bohemia, is a landlocked country in Central Europe. The country is bordered by Austria to the south, Germany to the west, Poland to the northeast, and Slovakia to the south ...
according to Němec (1981) According to the mineral and locations database of "mindat.org" huntite, together with aragonite, calcite, dolomite and magnesite, 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 . It generally occurs associated with the weathering products of magnesium containing minerals such as serpentine group, serpentine or brucite. It occurs as incrustations a ...
as a
flame retardant Flame retardants are 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 combustion, ignition source and pr ...
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 An endothermic process is a chemical or physical process that absorbs heat from its surroundings. In terms of thermodynamics, it is a thermodynamic process with an increase in the enthalpy (or internal energy ) of the system.Oxtoby, D. W; Gillis, ...
, meaning that it absorbs heat, which helps to cool the burning material, slowing the fire's spread. These mixtures are alternatives to the more commonly used
aluminium hydroxide Aluminium hydroxide, , is found 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 and acidic propert ...
.


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 where the mineral ''conite'' can be found. Originally, Retzius had found the new carbonate in a mineral collection and recognized it as a new species because it was harder than any known carbonate (even so hard that it would spark when struck with steel). Still, no indication was given regarding where this ''conite'' had been found. Some 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 North Hesse, northern Hesse, in Central Germany (geography), central Germany. It is the administrative seat of the Regierungsbezirk Kassel (region), Kassel and the d ...
, Germany. However, this ''conite'' had been found 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, with around 41,000 inhabitants. The city lies in the foreland of the Ore Mountains, in the Saxon urbanization axis, which runs along the northern edge of the Elster and ...
(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 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