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Köttigite | |
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General | |
Category | Arsenate mineral |
Formula (repeating unit) | Zn3(AsO4)2·8H2O |
IMA symbol | Köt [1] |
Strunz classification | 8.CE.40 (10 ed.) VII/C.13-90 (8 ed.) |
Dana classification | 40.3.6.5 |
Crystal system | Monoclinic |
Crystal class | Prismatic (2/m) (same H-M symbol) |
Space group | C2/m |
Identification | |
Formula mass | 618.13 g/mol |
Colour | Colourless, pink, red, red-orange or brown; light rose-pink in transmitted light |
Crystal habit | Crystals prismatic [001] and flattened {010}. Also in crusts with a crystalline surface and fibrous structure |
Cleavage | Perfect on {010} |
Fracture | Fibrous fracture yields a silky lustre |
Tenacity | Flexible |
Mohs scale hardness | 2+1⁄2 to 3 |
Lustre | Resinous or waxy, silky on fracture |
Streak | Reddish-white to white |
Diaphaneity | Translucent |
Specific gravity | 3.33 |
Optical properties | Biaxial (+) |
Refractive index | nα = 1.622 nβ = 1.638 nγ = 1.671 |
Birefringence | δ = 0.049 |
Pleochroism | Visible. X, Y = colourless, Z = pale red. |
Solubility | Soluble in acids |
Other characteristics | Not fluorescent |
References | [2] [3] [4] [5] [6] [7] |
Köttigite is a rare hydrated zinc arsenate which was discovered in 1849 and named by James Dwight Dana in 1850 in honour of Otto Friedrich Köttig (1824–1892), a German chemist from Schneeberg, Saxony, who made the first chemical analysis of the mineral. [6] It has the formula Zn3(AsO4)2·8H2O and it is a dimorph of metaköttigite, which means that the two minerals have the same formula, but a different structure: köttigite is monoclinic and metaköttigite is triclinic. [8] There are several minerals with similar formulae but with other cations in place of the zinc. Iron forms parasymplesite Fe2+3(AsO4)2·8H2O; cobalt forms the distinctively coloured pinkish purple mineral erythrite Co3(AsO4)2·8H2O and nickel forms annabergite Ni3(AsO4)2·8H2O. Köttigite forms series with all three of these minerals [4] [6] [8] and they are all members of the vivianite group.
The Vivianite Group is a group of monoclinic phosphates and arsenates with divalent cations. The group members are annabergite, arupite, babanekite, baricite, erythrite, hornesite, kottingite, manganhornesite, pakhomovskyite, parasymplesite and vivianite. [6]
Köttigite belongs to the monoclinic crystal system, so it has two crystal axes, a and c, inclined to each other at angle β, and a third axis, the b axis, at right angles to both a and c. It belongs to point group 2/m, which means that it has a two-fold axis of rotational symmetry parallel to b, and a mirror plane perpendicular to it. The space group is C2/m, which means that the unit cell is centred on the C face. [2] [3]
Although zinc is the only transition metal that appears in the formula, köttigite usually contains significant quantities of cobalt and nickel, [3] and these three elements are randomly distributed over the cation sites to form complex slabs perpendicular to the b axis. These sheets are held together by hydrogen bonding alone, which is quite weak, hence the perfect cleavage in this direction. [3]
There are two formula units per unit cell (Z = 2) and the cell parameters are a = 10.24 Å, b = 13.405 Å, c = 4.757 Å and β = 105.21°. [3]
Pure end-member köttigite is colourless, but frequently samples are coloured pink, red, red-orange or brown by elements substituting for the zinc. It is light rose-pink in transmitted light, translucent with a reddish-white to white streak and a resinous or waxy lustre, silky on fractures. [6] Crystals are small, prismatic parallel to the c axis and flattened perpendicular to the b axis. It also occurs as massive crusts with a crystalline surface and fibrous structure. [4] [6]
The mineral is biaxial (+) with refractive indices nα = 1.622, nβ = 1.638 and nγ = 1.671. [2] The maximum birefringence δ is the difference between the largest and the smallest refractive index, and is equal to 0.049.
Biaxial crystals have two optic axes, and the angle between them is known as the optic angle, 2V. [9] For köttigite 2V has a measured value of 74°, and a calculated value of 72°. [6]
Biaxial crystals have three mutually perpendicular principal optical direction, named X, Y and Z. Light travels at different speeds in different directions through the crystal. X is the direction of travel at the highest speed, Z at the lowest, and Y intermediate. The orientation is given by expressing the relationship of X, Y and Z to the crystallographic axes a, b and c. In monoclinic crystals one of the principal optical directions X, Y and Z coincides with the b axis. Since X, Y and Z are mutually perpendicular, it suffices to define just two of them, then the third is determined. [9] For köttigite X=b and Z^c=37°. [2]
Pleochroism is visible, with the crystal appearing colourless when viewed along X or Y, and pale red when viewed along Z. Pleochroism should not be present if the mineral is colourless. [6] It is not fluorescent. [6]
Köttigite is soft, with Mohs hardness only 2+1⁄2 to 3, even softer than calcite, which has a hardness of 3. It is also fairly light, with specific gravity 3.33. [2] Because of its sheetlike structure it has perfect cleavage perpendicular to the b axis; [2] it is flexible, and has a fibrous fracture giving it a silky lustre on cleavage surfaces. [6] It is soluble in acids. [4] [6]
It is formed by the alteration of smaltite (Co,Fe,Ni)As2 and sphalerite ZnS. [4] [7] in oxidized zones of arsenical ores containing zinc. The type locality is the Daniel Mine (St. Daniel Mine), Neustädtel, Schneeberg District, Erzgebirge, Saxony, Germany, where it occurs in oxidized veins in a hydrothermal sulfide ore deposit, associated with roselite Ca2(Co2+,Mg)(AsO4)2·8H2O. [6]
At the Ojuela Mine, Mapimí Municipality, Mexico, it occurs in sprays of bladed crystals to 6 mm, which is large for the species, [4] associated with symplesite Fe2+3(AsO4)2·8H2O, parasymplesite Fe2+3(AsO4)2·8H2O, adamite Zn2(AsO4)(OH), legrandite Zn2(AsO4)(OH)·H2O, metaköttigite Zn3(AsO4)2·8H2O and gypsum Ca(SO4)·2H2O. [5]
At the Hilton Mine, Cumbria, England, köttigite has been found in a specimen of galena PbS and gersdorffite NiAsS (but no sphalerite), on a surface coated with annabergite Ni3(AsO4)2·8H2O and an earthy crust. The individual crystals are colourless, transparent, and very small, the largest being about 1 mm. [8]
At Bou Azzer, Taznakht, Morocco, köttigite has been identified in a sample of vein quartz SiO2 rich in chalcopyrite CuFeS2 and sphalerite ZnS. The sample has turquoise-blue secondary minerals including devilline CaCu4(SO4)2(OH)6·3H2O, and also lath-shaped, blue-grey to pinkish grey crystals of köttigite with a habit resembling erythrite Co3(AsO4)2·8H2O, measuring less than 2 mm. The crystals are relatively rich in iron and cobalt, with traces of copper and nickel. [10]
Vivianite (Fe(II)
3(PO
4)
2·8H
2O) is a hydrated iron(II) phosphate mineral found in a number of geological environments. Small amounts of manganese Mn2+, magnesium Mg2+, and calcium Ca2+ may substitute for iron Fe2+ in its structure. 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 can also appear on the iron coffins or on the corpses of humans as a result of a chemical reaction of the decomposing body with the iron enclosure.
Erythrite, also known as red cobalt, is a secondary hydrated cobalt arsenate mineral with the formula Co
3(AsO
4)
2•8H
2O. Erythrite and annabergite, chemical formula Ni
3(AsO
4)
2•8H
2O, or nickel arsenate form a complete series with the general formula (Co,Ni)
3(AsO
4)
2•8H
2O.
Alstonite, also known as bromlite, is a low temperature hydrothermal mineral that is a rare double carbonate of calcium and barium with the formula BaCa(CO
3)
2, sometimes with some strontium. Barytocalcite and paralstonite have the same formula but different structures, so these three minerals are said to be trimorphous. Alstonite is triclinic but barytocalcite is monoclinic and paralstonite is trigonal. The species was named Bromlite by Thomas Thomson in 1837 after the Bromley-Hill mine, and alstonite by August Breithaupt of the Freiberg Mining Academy in 1841, after Alston, Cumbria, the base of operations of the mineral dealer from whom the first samples were obtained by Thomson in 1834. Both of these names have been in common use.
Barytocalcite is an anhydrous barium calcium carbonate mineral with the chemical formula BaCa(CO3)2. It is trimorphous with alstonite and paralstonite, that is to say the three minerals have the same formula but different structures. Baryte and quartz pseudomorphs after barytocalcite have been observed.
Annabergite is an arsenate mineral consisting of a hydrous nickel arsenate. It is considered a member of the vivianite group and known for its ability to form crystals in a characteristic apple-green color.
Leadhillite is a lead sulfate carbonate hydroxide mineral, often associated with anglesite. It has the formula Pb4SO4(CO3)2(OH)2. Leadhillite crystallises in the monoclinic system, but develops pseudo-hexagonal forms due to crystal twinning. It forms transparent to translucent variably coloured crystals with an adamantine lustre. It is quite soft with a Mohs hardness of 2.5 and a relatively high specific gravity of 6.26 to 6.55.
Todorokite is a complex hydrous manganese oxide mineral with generic chemical formula (Na,Ca,K,Ba,Sr)
1-x(Mn,Mg,Al)
6O
12·3-4H
2O. It was named in 1934 for the type locality, the Todoroki mine, Hokkaido, Japan. It belongs to the prismatic class 2/m of the monoclinic crystal system, but the angle β between the a and c axes is close to 90°, making it seem orthorhombic. It is a brown to black mineral which occurs in massive or tuberose forms. It is quite soft with a Mohs hardness of 1.5, and a specific gravity of 3.49 – 3.82. It is a component of deep ocean basin manganese nodules.
Vauxite is a phosphate mineral with the chemical formula Fe2+Al2(PO4)2(OH)2·6(H2O). It belongs to the laueite – paravauxite group, paravauxite subgroup, although Mindat puts it as a member of the vantasselite Al4(PO4)3(OH)3·9H2O group. There is no similarity in structure between vauxite and paravauxite Fe2+Al2(PO4)2(OH)2·8H2O or metavauxite Fe3+Al2(PO4)2(OH)2·8H2O, even though they are closely similar chemically and all minerals occur together as secondary minerals. Vauxite was named in 1922 for George Vaux Junior (1863–1927), an American attorney and mineral collector.
Lavendulan is an uncommon arsenate mineral in the lavendulan group. It is known for its characteristic intense electric blue colour. Lavendulan is very similar to Lemanskiite, the analogue trihydrate mineral, to the point of them being considered dimorphs. Lemanskiite is tetragonal, but lavendulan is monoclinic. Lavendulan has the same structure as sampleite, and the two minerals form a series. It is the calcium analogue of zdenĕkite and the arsenate analogue of sampleite.
Tsumebite is a rare phosphate mineral named in 1912 after the locality where it was first found, the Tsumeb mine in Namibia, well known to mineral collectors for the wide range of minerals found there. Tsumebite is a compound phosphate and sulfate of lead and copper, with hydroxyl, formula Pb2Cu(PO4)(SO4)(OH). There is a similar mineral called arsentsumebite, where the phosphate group PO4 is replaced by the arsenate group AsO4, giving the formula Pb2Cu(AsO4)(SO4)(OH). Both minerals are members of the brackebuschite group.
Vladimirite is a rare calcium arsenate mineral with a formula of Ca5(HAsO4)2(AsO4)2·5H2O. It is named after the Vladimirovskoye deposit in Russia, where it was discovered in the 1950s.
Warikahnite is a rare zinc arsenate mineral of the triclinic crystal system with Hermann-Mauguin notation 1, belonging to the space group P1. It occurs in the Tsumeb mine in Namibia on corroded tennantite in the second oxidation zone under hydrothermal conditions in a dolomite-hosted polymetallic ore deposit. It is associated with adamite, stranskiite, koritnigite, claudetite, tsumcorite, and ludlockite. The origin of discovery was in a dolomite ore formation within an oxidized hydrothermal zone, in the E9 pillar, 31st level of the Tsumeb Mine in Namibia, Southwest Africa. It has also been found at Lavrion, Greece and Plaka, Greece as microscopic white needles.
Tsumcorite is a rare hydrated lead arsenate mineral that was discovered in 1971, and reported by Geier, Kautz and Muller. It was named after the TSUMeb CORporation mine at Tsumeb, in Namibia, in recognition of the Corporation's support for mineralogical investigations of the orebody at its Mineral Research Laboratory.
Penikisite was discovered by Alan Kulan and Gunar Penikis near Rapid Creek, Yukon Territory. The mineral is a member of the bjarebyite group along with kulanite, ideally BaFe2+2Al2(PO4)3(OH)3, and bjarebyite, ideally BaMn2+2Al2(PO4)3(OH)3. It is among several new minerals that have been discovered in the Rapid Creek and Big Fish areas of Yukon Territory. Kulanite is similar in many ways to penikisite in appearance and properties. The chemical formula for penikisite is Ba(Mg,Fe,Ca)Al2(PO4)2(OH)3. It has a hardness of about 4 and a density of 3.79 g/cm3. Penikisite is unique among the bjarebyite group in being monoclinic and has a biaxial optical class. It comes in shades of blue and green and, when rubbed on a streak plate, is pale green to white in color. Although penikisite and kulanite both range from blue to green, penikisite zones are easily distinguishable from kulanite zones in kulanite-penikisite crystals because they are lighter than the darker kulanite in color. Penikisite is a phosphate and is different from kulanite in that it is a magnesium-rich phosphate whereas kulanite is an iron-rich phosphate.
Ianbruceite is a rare hydrated zinc arsenate with the formula [Zn2(OH)(H2O)(AsO4)](H2O)2; material from the Driggith mine has traces of cobalt. It was first discovered at Tsumeb, approved by the International Mineralogical Association as a new mineral species in 2011, reference IMA2011-49, and named for Ian Bruce, who founded "Crystal Classics" in the early 1990s, and was heavily involved in attempts to reopen the famous Tsumeb mine for specimen mining.
In 2013 new occurrences of ianbruceite were reported from the neighbouring Driggith and Potts Gill mines on High Pike in the Caldbeck Fells, Cumbria, England. Here the mineral is probably a post-mining product. Caldbeck Fells and Tsumeb are the only reported localities for ianbruceite to date (May 2013).
Brianyoungite is a secondary zinc carbonate mineral. The Commission on New Minerals, Nomenclature and Classification (CNMNC) of the International Mineralogical Association (IMA) classifies it as a carbonate with the formula Zn3(CO3)(OH)4, but sulfate groups SO4 also occupy the carbonate CO3 positions, in the ratio of about one sulfate to three carbonates, so other sources give the formula as Zn3(CO3,SO4)(OH)4, and Gaines et al. classify the mineral as a compound carbonate. It is similar in appearance to hydrozincite, another zinc carbonate. It was discovered in 1991 and designated IMA1991-053. In 1993 it was named "brianyoungite" after Brian Young (born 1947), a field geologist with the British Geological Survey, who provided the first specimens.
Carminite (PbFe3+2(AsO4)2(OH)2) is an anhydrous arsenate mineral containing hydroxyl. It is a rare secondary mineral that is structurally related to palermoite (Li2SrAl4(PO4)4(OH)4). Sewardite (CaFe3+2(AsO4)2(OH)2) is an analogue of carminite, with calcium in sewardite in place of the lead in carminite. Mawbyite is a dimorph (same formula, different structure) of carminite; mawbyite is monoclinic and carminite is orthorhombic. It has a molar mass of 639.87 g. It was discovered in 1850 and named for the characteristic carmine colour.
Serpierite (Ca(Cu,Zn)4(SO4)2(OH)6·3H2O) is a rare, sky-blue coloured hydrated sulfate mineral, often found as a post-mining product. It is a member of the devilline group, which has members aldridgeite (Cd,Ca)(Cu,Zn)4(SO4)2(OH)6·3H2O, campigliaite Cu4Mn2+(SO4)2(OH)6·4H2O, devilline CaCu4(SO4)2(OH)6·3H2O, kobyashevite Cu5(SO4)2(OH)6·4H2O, lautenthalite PbCu4(SO4)2(OH)6·3H2O and an unnamed dimorph of devilline. It is the calcium analogue of aldridgeite and it is dimorphous with orthoserpierite CaCu4(SO4)2(OH)6·3H2O.
Mottramite is an orthorhombic anhydrous vanadate hydroxide mineral, PbCu(VO4)(OH), at the copper end of the descloizite subgroup. It was formerly called cuprodescloizite or psittacinite (this mineral characterized in 1868 by Frederick Augustus Genth). Duhamelite is a calcium- and bismuth-bearing variety of mottramite, typically with acicular habit.
Talmessite is a hydrated calcium magnesium arsenate, often with significant amounts of cobalt or nickel. It was named in 1960 for the type locality, the Talmessi mine, Anarak district, Iran. It forms a series with β-Roselite, where cobalt replaces some of the magnesium, and with gaitite, where zinc replaces the magnesium. All these minerals are members of the fairfieldite group. Talmessite is dimorphic with wendwilsonite.