Vivianite

Vivianite (Fe2+
Fe2+
2(PO
4)
2·8H
2O) is a hydrated iron phosphate mineral found in a number of geological environments. Small amounts of manganese Mn2+, magnesium Mg and calcium Ca may substitute for iron Fe2+ in the structure.[4] Pure vivianite is colorless, but the mineral oxidizes very easily, changing the color, and it is usually found as deep blue to deep bluish green prismatic to flattened crystals.
Vivianite crystals are often found inside fossil shells, such as those of bivalves and gastropods, or attached to fossil bone.

Vivianite
Vivianite tabular crystal, transparent, with a deep green color. Crystal size: 82 mm x 38 mm x 11 mm. From Huanuni mine, Dalence Province, Oruro Department, Bolivia
General
CategoryPhosphate mineral
Vivianite group
Formula
(repeating unit)		Fe2+
Fe2+
2(PO
4)
2·8H
2O
Strunz classification8.CE.40 (10 ed)
7/C.13-40 (8 ed)
Dana classification40.3.6.1
Crystal systemMonoclinic
Crystal classPrismatic (2/m)
(same H-M symbol)
Space groupB2/m
Unit cella = 10.086 Å, b = 13.441 Å
c = 4.703 Å; β = 104.27°; Z = 2
Identification
Formula mass501.61 g/mol
ColorColorless, very pale green, becoming dark blue, dark greenish blue, indigo-blue, then black with oxidation
Crystal habitFlattened, elongated prismatic crystals, may be rounded or corroded; as stellate groups, incrustations, concretionary, earthy or powdery
TwinningTranslation gliding
CleavagePerfect on {010}
FractureFibrous
TenacityFlexible, sectile
Mohs scale hardness1.5-2
LusterVitreous, pearly on the cleavage, dull when earthy
StreakWhite, altering to dark blue, brown
DiaphaneityTransparent to translucent
Specific gravity2.68
Optical propertiesBiaxial (+)
Refractive indexnα = 1.579–1.616, nβ = 1.602–1.656, nγ = 1.629–1.675[1]
Birefringenceδ = 0.050–0.059
PleochroismVisible; X = blue, deep blue, Indigo-blue; Y = pale yellowish green, pale bluish green, yellow-green; Z = pale yellowish green, olive-yellow
2V angleMeasured: 63° to 83.5°, Calculated: 78° to 88°
Dispersionr < v, weak
Ultraviolet fluorescenceNot fluorescent
Melting point1,114 °C (2,037 °F)
SolubilityEasily soluble in acids
Alters toMetavivianite
References[1][2][3]
Vivianite from South Dakota, USA
Vivianite and Childrenite from the Siglio XX Mine
Vivianite from Bavaria
Vivianite and Albite from Brazil

It was named by Abraham Gottlob Werner in 1817, the year of his death, after either John Henry Vivian (1785–1855), a Welsh-Cornish politician, mine owner and mineralogist living in Truro, Cornwall, England, or after Jeffrey G. Vivian, an English mineralogist.[5] Vivianite was discovered at Wheal Kind, in St Agnes, Cornwall.[2]

Vivianite group

Vivianite group minerals have the general formula A3(XO4)2·8H2O, where A is a divalent transition metal cation and X is either phosphorus or arsenic, and they are monoclinic.[6][7]
Group members are:

MineralChemical formulaCrystal system
AnnabergiteNi3(AsO4)2·8H2OMonoclinic
ArupiteNi3(PO4)2·8H2OMonoclinic
Baricite(Mg2+,Fe2+)3(PO4)2·8H2OMonoclinic
ErythriteCo3(AsO4)2·8H2OMonoclinic
HörnesiteMg3(AsO4)2·8H2OMonoclinic
KöttigiteZn3(AsO4)2·8H2OMonoclinic
Manganohörnesite(Mn2+,Mg)3(AsO4)2·8H2OMonoclinic
PakhomovskyiteCo3(PO4)2·8H2OMonoclinic
ParasymplesiteFe2+3(AsO4)2·8H2OMonoclinic
VivianiteFe2+3(PO4)2·8H2OMonoclinic
Related:
  • Bobierrite Mg3(PO4)2·8H2O
  • Symplesite Fe2+3(AsO4)2·8H2O
  • Metaköttigite Zn3(AsO4)2·8H2O
  • Metavivianite (Fe2+3−x,Fe3+x)(PO4)2(OH)x·(8-x)H2O.[4]
  • Note: Metavivianite, that vivianite readily alters to, is not a member of the vivianite group because it contains trivalent Fe3+ cations.

Structure

In pure end member vivianite all the iron is divalent, Fe2+, but there are two distinct sites in the structure that these ions can occupy. In the first site the Fe2+ is surrounded by four water molecules and two oxygens, making an octahedral group. In the second site the Fe2+ is surrounded by two water molecules and four oxygens, again making an octahedral group. The oxygens are part of the phosphate groups (PO4)−3, that are tetrahedral. The vivianite structure has chains of these octahedra and tetrahedra that form sheets perpendicular to the a crystal axis. The sheets are held together by weak bonds, and that accounts for the perfect cleavage between them.[4]
The crystals are monoclinic, class 2/m, space group C 2/m, with two formula units per unit cell (Z = 2). The approximate values of the unit cell parameters are

a = 10.1 Å, b = 13.4 Å, c = 4.7 Å and β = 104.3°,

with slightly different values given by different sources:

a = 10.086 Å, b = 13.441 Å, c = 4.703 Å, β = 104.27°[2][4]
a = 10.06 Å, b = 13.41 Å, c = 4.696 Å, β = 104.3°[3]
a = 10.034–10.086 Å, b= 13.434–13.441 Å, c= 4.687–4.714 Å, β = 102.65–104.27°[1]
a = 10.024(6) Å, b = 13.436(3) Å, c = 4.693(4) Å, β = 102.30(5)°[8]

Appearance

The mineral may occur as crystals, or as masses or concretions.[4] The crystals are usually prismatic parallel to the c crystal axis, and flattened perpendicular to the b axis. Equant crystals are rarer.[1][2][4] They may also occur as stellate (star-shaped) groups, or encrustations with a bladed or fibrous structure.[4] Unaltered specimens are colorless to very pale green, but they oxidize on exposure to light (and possibly also in situ) to blue, then darker green, brown, purple and purplish black. The streak is white, altering to dark blue or brown. Crystals are transparent to translucent with a vitreous luster, pearly on the cleavage surface, or dull and earthy.[1][2][3][4]

Optical properties

Vivianite is biaxial (+) with refractive indices approximately

nα = 1.58, nβ = 1.6, nγ = 1.6, but different sources give somewhat different values
nα = 1.579, nβ = 1.602, nγ = 1.637[4]
nα = 1.579–1.616 nβ = 1.602–1.656 nγ = 1.629–1.675[1][2]
nα=1.58–1.626, nβ=1.598–1.662, nγ=1.627–1.699[3]

Birefringence: δ = 0.050–0.059[2] or 0.0470–0.0730[3]

The refractive indices increase with increasing oxidation, the birefringence decreases, and the pleochroism on {010} becomes stronger.[2][4]
The angle between the optic axes, 2V, has been measured as between 63° and 83.5°; it can also be calculated from the refractive indices, giving a value between 78° and 88°.[2][3] The dispersion of the optic axes is weak, with r<v[1][2][4] or non-existent.[3]
Vivianite is pleochroic with X= blue, deep blue or indigo-blue; Y= pale yellowish green, pale bluish green or yellow-green; Z= pale yellowish green or olive-yellow. X is parallel to the b crystal axis and Z is inclined to the c crystal axis at an angle of 28.5°.[1][2][4] It is not fluorescent.[2][3]

Physical properties

Vivianite is a soft mineral, with Mohs hardness only ​1 1⁄2 to 2, and specific gravity 2.7. It splits easily, with perfect cleavage perpendicular to the b crystal axis, due to the sheet-like structure of the mineral. It is sectile, with a fibrous fracture, and thin laminae parallel to the cleavage plane are flexible. It is easily soluble in acids.[2][4]
It has a melting point of 1,114 °C (2,037 °F),[2] it darkens in color in H2O2[2] and is not radioactive.[3]

Geological setting

Vivianite is a secondary mineral found in a number of geologic environments: The oxidation zone of metal ore deposits, in granite pegmatites containing phosphate minerals, in clays and glauconitic sediments, and in recent alluvial deposits replacing organic material such as peat, lignite, bog iron ores and forest soils (All). Bones and teeth buried in peat bogs are sometimes replaced by vivianite.[9] Some authors say that it is particularly associated with gossan, but this is disputed by Petrov.[9]

Associated minerals include metavivianite, ludlamite, pyrite, siderite and pyrrhotite.[1][9] Hydrothermal veins produce the best crystal specimens with the classic gemmy green color.[9]

The type locality is Wheal Kind (Wheal Kine), West Wheal Kitty group, St Agnes, St Agnes District, Cornwall, England.[2]

Oxidation

Oxidation of vivianite is an internal process; no oxygen or water enters or leaves the mineral from the outside. A visible light photon knocks a proton out of a water molecule leaving a hydroxide ion (OH−). In turn a divalent iron Fe2+ loses an electron to become Fe3+, i.e., it is oxidized and balances the charge. This process starts when visible light falls on the vivianite, and it can occur within a few minutes, drastically changing the color of the mineral. Eventually the vivianite changes to a new species, metavivianite Fe2+2Fe3+(PO4)2(OH)·(H2O)7, which usually occurs as paramorphs after vivianite.[10]

Pigment

Vivianite was known as a pigment since Roman times but its use in oil painting was rather limited.[11] It has been found in Vermeer's The Procuress in the blue-grey parts of the carpet in the foreground.[12]

Johannes Vermeer, The Procuress, 1656

Localities

See also

References
  1. John W. Anthony; Richard A. Bideaux; Kenneth W. Bladh & Monte C. Nichols (2005). "Handbook of Mineralogy" (PDF). Mineral Data Publishing. Cite journal requires |journal= (help)
  2. Vivianite (Mindat.org)
  3. Webmineral data
  4. Gaines et al (1997) Dana’s New Mineralogy Eighth Edition. Wiley
  5. Although mindat.org claims "J. G. Vivian" is a typo for "J. H. Vivian", there is at least one reference that gives a full first name. The original description of Vivianit in Abraham Gottlob Werner, Letztes Mineral-System, Freiberg/Wien, 1817, p. 42 reads „Der Name ist vom Hrn. B. R. Werner zu Ehren des Hrn. J. Vivian aus Truro in Cornwall, dem Er die Kentnis des Fossils verdankt, gebildet.“ [“The name is formed by Mr. B. R. Werner in honour of Mr. J. Vivian from Truro in Cornwall, to whom he owes the memory of the fossil.”] It is ambiguous (and puzzling in its reference to B. R. Werner). As for Jeffrey G. Vivian, no other trace of him can be found in Google Books.
  6. Journal of the Russell Society (2006) 9:3
  7. Back, Malcolm E. (2014). Fleischer's Glossary of Mineral Species (11 ed.). Tucson AZ: Mineralogical Record Inc. p. 434.
  8. Banno Yasuyuki; Bunno Michiaki; Haruna Makoto & Kono Masahide (1999). "Vivianite from Nagasawa, Iwama-machi, Ibaraki Prefecture, Japan. New finding from meta-pelitic rocks". Bulletin of the Geological Survey of Japan (in Japanese). 50 (2): 117–121. ISSN 0016-7665. Archived from the original on 2012-02-29. Retrieved 2008-03-20.
  9. Petrov, Alfredo (1 January 2008). "Alfredo Petrov - A Scientific Study of the Absorption of Evil by Vivianite". Mindat.org. Retrieved 23 September 2018.
  10. Alfredo Petrov, 2006 on Mindat
  11. Vivianite at ColourLex
  12. H. Stege, C. Tilenschi und A. Unger. Bekanntes und Unbekanntes – neue Untersuchungen zur Palette Vermeers auf dem Gemälde „Bei der Kupplerin“. In: Uta Neidhardt und Marlies Giebe (Ed.), Johannes Vermeer – Bei der Kupplerin, Ausstellungskatalog Dresden 2004, pp. 76–82.
  13. The Mineralogical Record (2004) 35-2:156
  14. The Mineralogical Record (2004) 35-3:252
  15. The Mineralogical Record (2006) 37-2:156
  16. The Mineralogical Record (2007) 38-4:290
  17. Calvo, Miguel (2015). Minerales y Minas de España. Fosfatos, Arseniatos y Vanadatos. Escuela Técnica Superior de Ingenieros de Minas de Madrid. Fundación Gómez Pardo. Madrid, Spain. p. 297. ISBN 978-84-95063-96-0.
  18. The Mineralogical Record (2010) 41-4:366
  19. Cochran, U., Goff, J., Hannah, M., and Hull, A. (1999) Relative stability on a tectonically active coast: paleoenvironment during the last 7000 years at Lake Kohangapiripiri, Wellington, New Zealand, Quaternary International, 56, 53–63
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