Greigite

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Greigite
Greigite structure 110 SFe4 tetrahedra.png
Greigite structure, SFe4 tetrahedra
General
Category Sulfide mineral
Thiospinel group
Spinel structural group
Formula
(repeating unit)
Fe2+Fe3+2S4
IMA symbol Grg [1]
Strunz classification 2.DA.05
Crystal system Cubic
Crystal class Hexoctahedral (m3m)
H-M symbol: (4/m 3 2/m)
Space group Fd3m
Unit cell a = 9.876 Å; Z = 8
Identification
ColorPale pink, tarnishes to metallic blue-black
Crystal habit Spheres of intergrown octahedra and as disseminated microscopic grains
Mohs scale hardness4 to 4.5
Luster Metallic to earthy
Diaphaneity Opaque
Specific gravity 4.049
Other characteristicsStrongly magnetic
References [2] [3] [4]

Greigite is an iron sulfide mineral with the chemical formula Fe2+Fe3+2S4. It is the sulfur equivalent of the iron oxide magnetite (Fe3O4). It was first described in 1964 for an occurrence in San Bernardino County, California, and named after the mineralogist and physical chemist Joseph W. Greig (1895–1977). [4] [5]

Contents

Natural occurrence and composition

It occurs in lacustrine sediments with clays, silts and arkosic sand often in varved sulfide rich clays. It is also found in hydrothermal veins. Greigite is formed by magnetotactic bacteria and sulfate-reducing bacteria. [2] Greigite has also been identified in the sclerites of scaly-foot gastropods. [6]

The mineral typically appears as microscopic (< 0.03 mm) isometric hexoctahedral crystals and as minute sooty masses. Association minerals include montmorillonite, chlorite, calcite, colemanite, veatchite, sphalerite, pyrite, marcasite, galena and dolomite. [2] [3]

Common impurities include Cu, Ni, Zn, Mn, Cr, Sb and As. [3] Ni impurities are of particular interest because the structural similarity between Ni-doped greigite and the (Fe,Ni)S clusters present in biological enzymes has led to suggestions that greigite or similar minerals could have acted as catalysts for the origin of life. [7] In particular, the cubic Fe4S4 unit of greigite is found in the Fe4S4 thiocubane units of proteins of relevance to the acetyl-CoA pathway.

Crystal structure

Greigite has the spinel structure. The crystallographic unit cell is cubic, with space group Fd3m. The S anions form a cubic close-packed lattice, and the Fe cations occupy both tetrahedral and octahedral sites. [2] [8]

Magnetic and electronic properties

Like the related oxide magnetite (Fe3O4), greigite is ferrimagnetic, with the spin magnetic moments of the Fe cations in the tetrahedral sites oriented in the opposite direction as those in the octahedral sites, and a net magnetization. It is a mixed-valence compound, featuring both Fe(II) and Fe(III) centers in a 1:2 ratio. Both metal sites have high spin quantum numbers. The electronic structure of greigite is that of a half metal. [9] [10]

Related Research Articles

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<span class="mw-page-title-main">Bornite</span> Sulfide mineral

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<span class="mw-page-title-main">Iron(II) oxide</span> Inorganic compound with the formula FeO

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Ferrihydrite (Fh) is a widespread hydrous ferric oxyhydroxide mineral at the Earth's surface, and a likely constituent in extraterrestrial materials. It forms in several types of environments, from freshwater to marine systems, aquifers to hydrothermal hot springs and scales, soils, and areas affected by mining. It can be precipitated directly from oxygenated iron-rich aqueous solutions, or by bacteria either as a result of a metabolic activity or passive sorption of dissolved iron followed by nucleation reactions. Ferrihydrite also occurs in the core of the ferritin protein from many living organisms, for the purpose of intra-cellular iron storage.

<span class="mw-page-title-main">Mackinawite</span> Iron nickel sulfide mineral

Mackinawite is an iron nickel sulfide mineral with the chemical formula (Fe,Ni)
1+x
S
. The mineral crystallizes in the tetragonal crystal system and has been described as a distorted, close packed, cubic array of S atoms with some of the gaps filled with Fe. Mackinawite occurs as opaque bronze to grey-white tabular crystals and anhedral masses. It has a Mohs hardness of 2.5 and a specific gravity of 4.17. It was first described in 1962 for an occurrence in the Mackinaw mine, Snohomish County, Washington for which it was named.

<span class="mw-page-title-main">Carrollite</span>

Carrollite, CuCo2S4, is a sulfide of copper and cobalt, often with substantial substitution of nickel for the metal ions, and a member of the linnaeite group. It is named after the type locality in Carroll County, Maryland, US, at the Patapsco mine, Sykesville.

<span class="mw-page-title-main">Iron oxide nanoparticle</span>

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Magnetic mineralogy is the study of the magnetic properties of minerals. The contribution of a mineral to the total magnetism of a rock depends strongly on the type of magnetic order or disorder. Magnetically disordered minerals contribute a weak magnetism and have no remanence. The more important minerals for rock magnetism are the minerals that can be magnetically ordered, at least at some temperatures. These are the ferromagnets, ferrimagnets and certain kinds of antiferromagnets. These minerals have a much stronger response to the field and can have a remanence.

Cuprospinel is a mineral. Cuprospinel is an inverse spinel with the chemical formula CuFe2O4, where copper substitutes some of the iron cations in the structure. Its structure is similar to that of magnetite, Fe3O4, yet with slightly different chemical and physical properties due to the presence of copper.

Iron(II,III) sulfide is a blue-black (sometimes pinkish) chemical compound of iron and sulfur with formula Fe3S4 or FeS·Fe2S3, which is much similar to iron(II,III) oxide. It occurs naturally as the sulfide mineral greigite and is magnetic. It is a bio-mineral produced by and found in magnetotactic bacteria. It is a mixed valence compound, featuring both Fe2+ and Fe3+ centers, in 1:2 ratio.

The spinels are any of a class of minerals of general formulation AB
2
X
4
which crystallise in the cubic (isometric) crystal system, with the X anions arranged in a cubic close-packed lattice and the cations A and B occupying some or all of the octahedral and tetrahedral sites in the lattice. Although the charges of A and B in the prototypical spinel structure are +2 and +3, respectively, other combinations incorporating divalent, trivalent, or tetravalent cations, including magnesium, zinc, iron, manganese, aluminium, chromium, titanium, and silicon, are also possible. The anion is normally oxygen; when other chalcogenides constitute the anion sublattice the structure is referred to as a thiospinel.

Filipstadite is a very rare mineral of the spinel group, with the formula (Mn,Mg)(Sb5+0.5Fe3+0.5)O4. It is isometric, although it was previously though to be orthorhombic. When compared to a typical spinel, both the octahedral and tetrahedral sites are split due to cation ordering. Filipstadite is chemically close to melanostibite. The mineral comes from Långban, Sweden, a manganese skarn deposit famous for many rare minerals.

References

  1. Warr, L.N. (2021). "IMA–CNMNC approved mineral symbols". Mineralogical Magazine. 85 (3): 291–320. Bibcode:2021MinM...85..291W. doi: 10.1180/mgm.2021.43 . S2CID   235729616.
  2. 1 2 3 4 Anthony, John W.; Bideaux, Richard A.; Bladh, Kenneth W.; Nichols, Monte C., eds. (1990). "Greigite" (PDF). Handbook of Mineralogy. Vol. I (Elements, Sulfides, Sulfosalts). Chantilly, VA, US: Mineralogical Society of America. ISBN   0962209708 . Retrieved December 5, 2011.
  3. 1 2 3 Greigite. Mindat.org
  4. 1 2 Greigite. Webmineral
  5. Skinner, Brian J.; Erd, Richard C.; Grimaldi, Frank S. (1964). "Greigite, the thio-spinel of iron; a new mineral" (PDF). American Mineralogist. 49: 543–55.
  6. "Armor-Plated Snail Discovered in Deep Sea". news.nationalgeographic.com. Archived from the original on November 10, 2003. Retrieved 2016-08-29.
  7. Russell, Michael J.; Martin, William (2004). "The rocky roots of the acetyl-CoA pathway". Trends in Biochemical Sciences. 29 (7): 358–363. doi:10.1016/j.tibs.2004.05.007. ISSN   0968-0004. PMID   15236743.
  8. Vaughan, D. J.; Craig, J. R. “Mineral Chemistry of Metal Sulfides" Cambridge University Press, Cambridge: 1978. ISBN   0-521-21489-0.
  9. Devey, A.J.; Grau-Crespo, R.; Leeuw, N.H. (2009). "Electronic and magnetic structure of Fe3S4: GGA+U investigation". Physical Review B. 79 (19): 195126. Bibcode:2009PhRvB..79s5126D. doi:10.1103/PhysRevB.79.195126.
  10. Wang, Jun; Cao, Shi-He; Wu, Wei; Zhao, Guo-Meng (2011). "The Curie temperature and magnetic exchange energy in half-metallic greigite Fe3S4". Physica Scripta. 83 (4): 045702. Bibcode:2011PhyS...83d5702W. doi:10.1088/0031-8949/83/04/045702. S2CID   121375069.