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Sphalerite
Black crystals of sphalerite with minor chalcopyrite and calcite
General
CategorySulfide mineral
Formula
(repeating unit)		(Zn,Fe)S
Strunz classification2.CB.05a
Dana classification02.08.02.01
Crystal systemCubic
Crystal classHextetrahedral (43m)
H-M symbol: (4 3m)
Space groupF43m (No. 216)
Unit cella = 5.406 Å; Z = 4
Structure
Jmol (3D)Interactive image
Identification
ColorLight to dark brown, red-brown, yellow, red, green, light blue, black and colourless.
Crystal habitEuhedral crystals – occurs as well-formed crystals showing good external form. Granular – generally occurs as anhedral to subhedral crystals in matrix.
TwinningSimple contact twins or complex lamellar forms, twin axis [111]
Cleavageperfect
FractureUneven to conchoidal
Mohs scale hardness3.5-4
LusterAdamantine, resinous, greasy
Streakbrownish white, pale yellow
DiaphaneityTransparent to translucent, opaque when iron-rich
Specific gravity3.9–4.2
Optical propertiesIsotropic
Refractive indexnα = 2.369
Other characteristicsnon-radioactive, non-magnetic, fluorescent and triboluminescent.
References[1][2][3]

Sphalerite ((Zn, Fe)S) is a mineral and ore of zinc.[4][5] It was discovered in 1847 by Ernst Friedrich Glocker, who named it based on the Greek work "sphaleros" meaning deceiving due to sphalerite being hard to identify.[6] When the iron content is high, sphalerite is an opaque black variety called marmatite.[7] Sphalerite is found in association with galena, chalcopyrite, pyrite (and other sulfides), calcite, dolomite, quartz, rhodochrosite and fluorite.[8] Miners have been known to refer to sphalerite as zinc blende, black-jack and ruby blende.[9] Sphalerite is found in a variety of deposit types, but it is primarily in sedimentary exhalative, Mississippi-Valley type and volcanogenic massive sulfide deposits.[10] It is primarily used for metal, brass, bronze, gemstone, galvanization, pharmaceuticals and cosmetics.[11]

Crystal habit and structure

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Sphalerite belongs to the hextetrahedral crystal class (), as part of the cubic (isometric) crystal system.[12] In the crystal structure, sulfur atoms form stacked layers, and zinc and iron fill in-between the layers and are tetrahedrally coordinated to the sulfur atoms.[8] Minerals similar to sphalerite include those in the sphalerite group, consisting of sphalerite, colaradoite, hawleyite, metacinnabar, stilleite and tiemannite.[13] The structure is closely related to the structure of diamond.[12] The hexagonal polymorph of sphalerite is wurtzite, and the trigonal polymorph is matraite.[13] Wurtzite is the higher temperature polymorph, sphalerite will become wurtzite at 1020°C.[14] The lattice constant for zinc sulfide in the zinc blende crystal structure is 0.541 nm.[15] Sphalerite has been found as a pseudomorph, taking the crystal structure of galena, tetrahedrite, barite and calcite.[16][14] Sphalerite can have Spinel Law twins, where the twin axis is [111].[13]

  • The crystal structure of sphalerite
    The crystal structure of sphalerite

The chemical formula of sphalerite is (Zn,Fe)S; the iron content generally increases with increasing formation temperature and can reach up to 40%.[8] All natural sphalerite contains concentrations of various impurities, which generally substitute for zinc in the cation position in the lattice; the most common cation impurities are cadmium, mercury and manganese, but gallium, germanium and indium may also be present in relatively high concentrations (hundreds to thousands of ppm).[4][17] Cadmium can replace up to 1% of zinc and manganese is generally found in sphalerite with high iron abundances.[13] Sulfur in the anion position can be substituted for by selenium and tellurium.[13] The abundances of these impurities are controlled by the conditions under which the sphalerite formed; formation temperature, pressure, element availability and fluid composition are important controls.[17]

Properties

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Physical properties

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Sphalerite displays a wide variety of colors, it is commonly yellow, brown, or gray to gray-black.[12] However, varieties have also been found to be emerald, lime green, amber, red, pink and black.[5] The color is mainly a function of iron content, the mineral becomes darker with increasing iron; the pale yellow and red varieties have very little iron.[8] Other impurities also affect the color, for example green sphalerite is a result of cobalt in the crystal structure.[14][18] Sphalerite is transparent to translucent, and its luster is adamantine, resinous or submetallic for high iron varieties.[12] Sphalerite has a yellow or light brown streak, a Mohs hardness of 3.5–4, and a specific gravity of 3.9–4.1.[8] Additional properties include sphalerite being triboluminescent, pyroelectric and fluorescent under longwave ultraviolet light; the triboluminescence is orange and the fluorescence is orange, blue, yellow, green, lavender or pink.[19]

  • Sphalerite fluorescing under ultra violet light. Sternberg Museum of Natural History, Kansas, USA
    Sphalerite fluorescing under ultra violet light. Sternberg Museum of Natural History, Kansas, USA

Optical properties

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In thin section, sphalerite exhibits very high positive relief and appears colorless to pale yellow or brown, with no pleochroism.[8] It possesses perfect dodecahedral cleavage, having six cleavage planes.[12] The refractive index of sphalerite (as measured via sodium light, average wavelength 589.3 nm) ranges from 2.37 when it is pure ZnS to 2.50 when there is 40% iron content.[8] Sphalerite is isotropic under cross-polarized light, however sphalerite can experience birefringence if intergrown with its polymorph wurtzite; the birefringence can increase from 0 (0% wurtzite) up to 0.022 (100% wurtzite).[14][8]

Varieties

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Gemmy, colorless to pale green sphalerite specimens from Franklin, New Jersey (see Franklin Furnace), are highly fluorescent orange and/or blue under longwave ultraviolet light and are known as cleiophane, an almost pure ZnS variety.[20] Cleiophane contains less than 0.1% of iron in the sphalerite crystal structure.[13] Marmatite or christophite is an opaque black variety of sphalerite and its coloring is due to high quantities of iron, which can reach up to 25%; marmatite is named after Marmato mining district in Colombia and christophite is named for the St.Christoph mine in Breitenbrunn, Saxony.[20] Both marmatite and cleiophane are not recognized by the International Mineralogical Association (IMA).[21] Red, orange or brownish-red sphalerite is termed ruby blende or ruby zinc, whereas dark colored sphalerite is termed black-jack.[20]

Deposit types

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Sphalerite is amongst the most common sulfide minerals, and it found worldwide and in a variety of deposit types.[9] The reason for the wide distribution of sphalerite is that is appears in many types of deposits; it is found in skarns[22], hydrothermal deposits[23], sedimentary beds[24], volcanogenic massive sulfide deposits (VMS)[25], Mississippi-valley type deposits (MVT)[26][27], granite[13] and coal[28].

Sedimentary exhalative

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Approximately 50% of zinc (from sphalerite) and lead comes from Sedimentary exhalative (Sedex) deposits, which are stratiform Pb-Zn sulfides that form at seafloor vents.[11] The metals precipitate from hydrothermal fluids and are hosted by shales, carbonates and organic-rich siltstones in back-arc basins and failed continental rifts.[10] The main ore minerals in Sedex deposits are sphalerite, galena, pyrite, pyrrhotite and marcasite, with minor sulfosalts such as tetrahedrite-freibergite and boulangerite; the Zn + Pb grade typically ranges between 10-20%.[10] Important Sedex mines are Red Dog in Alaska, Sullivan in British Columbia, Mount Isa and Broken Hill in Australia and Mehdiabad in Iran.[29]

Mississippi-Valley type

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Similar to Sedax, Mississippi-Valley type (MVT) deposits are also a Pb-Zn deposit which contains sphalerite.[30] However, they only account for 15-20% of zinc and lead, are 25% smaller in tonnage than Sedex deposits and have lower grades of 5-10% Pb + Zn.[10] MVT deposits form from the replacement of carbonate host rocks such as dolostone and limestone by ore minerals; they are located in platforms and foreland thrust belts.[10] Furthermore, they are stratabound, typically Phanerozoic in age and epigenetic (form after the lithification of the carbonate host rocks).[31] The ore minerals are the same as Sedex deposits: sphalerite, galena, pyrite, pyrrhotite and marcasite, with minor sulfosalts.[31] Mines that contain MVT deposits include Polaris in the Canadian arctic, Mississippi River in United States, Pine Point in Northwest Territories, and Admiral Bay in Australia.[32]

Volcanogenic massive sulfide

[edit]

Volcanogenic massive sulfide (VMS) deposits can be Cu-Zn- or Zn-Pb-Cu-rich, and account for 25% of Zn in reserves.[10] There are various types of VMS deposits with a range of regional contexts and host rock compositions; a common characteristic is that they are all hosted by submarine volcanic rocks.[11] They form from metals such as copper and zinc being transferred by hydrothermal fluids (modified seawater) which leach them from volcanic rocks in the oceanic crust; the metal-saturated fluid rises through fractures and faults to the surface, where it cools and deposits the metals as a VMS deposit.[33] The most abundant ore minerals are pyrite, chalcopyrite, sphalerite and pyrrhotite.[10] Mines that contain VMS deposits include Kidd Creek in Ontario, Urals in Russia, Troodos in Cyprus and Besshi in Japan.[34]

Localities

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The top producers of sphalerite include the United States, Russia, Mexico, Germany, Australia, Canada, China, Ireland, Peru, Kazakhstan and England.[35][36]

Sources of high quality crystals include:

Place Country
Freiberg, Saxony,

Neudorf, Harz Mountains

Germany
Lengenbach Quarry, Binntal, Valais Switzerland
Horni Slavkov and Příbram Czech Republic
Rodna Romania
Madan, Smolyan Province, Rhodope Mountains Bulgaria
Aliva mine, Picos de Europa Mountains, Cantabria [Santander] Province Spain
Alston Moor, Cumbria England
Dalnegorsk, Primorskiy Kray Russia
Watson Lake, Yukon Territory Canada
Flin Flon, Manitoba Canada
Tri-State district including deposits near

Baxter Springs, Cherokee County, Kansas; Joplin, Jasper County, Missouri

and Picher, Ottawa County, Oklahoma

USA
Elmwood mine, near Carthage, Smith County, Tennessee USA
Eagle mine, Gilman district, Eagle County, Colorado USA
Santa Eulalia, Chihuahua Mexico
Naica, Chihuahua Mexico
Cananea, Sonora Mexico
Huaron Peru
Casapalca Peru
Huancavelica Peru
Zinkgruvan Sweden

Uses

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Metal

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Sphalerite is an important ore of zinc; around 95% of all primary zinc is extracted from sphalerite ore.[37] However, due to its variable trace element content, sphalerite is also an important source of several other metals such as cadmium,[38] gallium[39] germanium,[40] and indium[41] which replace zinc.

Brass and bronze

[edit]

The zinc in sphalerite is used to produce brass, an alloy of copper with 3-45% zinc.[12] Major element alloy compositions of brass objects provide evidence that sphalerite was being used to produce brass by the Islamic as far back as the medieval ages between the 7th and 16th century CE.[42] Sphalerite may have also been used during the cementation process of brass in Northern China during the 12th-13th century CE (Jin Dynasty). [43] Similarly to brass, the zinc in sphalerite can also be used to produce certain types of bronze; bronze is dominantly copper which is alloyed with other metals such tin, zinc, lead, nickel, iron and arsenic.[44]

Other

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  • Yule Marble - sphalerite is found as intrusions in yule marble, which is used as a building material for the Lincoln Memorial and Tomb of the Unknown.[45]
  • Galvanized iron - zinc from sphalerite is used as a protective coating to prevent corrosion and rusting; it is used on power transmission towers, nails and automobiles. [36]
  • Pharmaceuticals and cosmetics - zinc is important to human health (as well as animals and plants) and is used in the body to grow, taste, smell, heal and by the immune system; a zinc deficiency can cause many side effects.[46] Mined zinc from sphalerite can be used to produce zinc supplements, for food fortification and agronomic biofortification.[47] Furthermore, zinc is used is products such as makeup, soap and especially sunscreen because it is useful in blocking ultraviolet radiation form the sun.[11]
  • Batteries[48]
  • Gemstone[49][50]
[edit]
  • Sphalerite and barite from Cumberland Mine, Tennessee, USA
    Sphalerite and barite from Cumberland Mine, Tennessee, USA
  • Sphalerite on dolostone, from Millersville Quarry, Ohio, USA
    Sphalerite on dolostone, from Millersville Quarry, Ohio, USA
  • Tan crystal of calcite attached to a cluster of black sphalerite crystals
    Tan crystal of calcite attached to a cluster of black sphalerite crystals
  • Sharp, tetrahedral sphalerite crystals with minor associated chalcopyrite from the Idarado Mine, Telluride, Ouray District, Colorado, USA
    Sharp, tetrahedral sphalerite crystals with minor associated chalcopyrite from the Idarado Mine, Telluride, Ouray District, Colorado, USA
  • Gem quality twinned cherry-red sphalerite crystal (1.8 cm) from Hunan Province, China
    Gem quality twinned cherry-red sphalerite crystal (1.8 cm) from Hunan Province, China
  • Sphalerite crystals from Áliva, Camaleño, Cantabria (Spain)
    Sphalerite crystals from Áliva, Camaleño, Cantabria (Spain)
  • Purple fluorite and sphalerite, from the Elmwood mine, Smith county, Tennessee, US
    Purple fluorite and sphalerite, from the Elmwood mine, Smith county, Tennessee, US
  • Shalerite crystal in geodized brachiopod
    Shalerite crystal in geodized brachiopod

References

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  1. ^ Sphalerite. Webmineral. Retrieved on 2011-06-20.
  2. ^ Sphalerite. Mindat.org. Retrieved on 2011-06-20.
  3. ^ "Handbook of Mineralogy" (PDF).
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  6. ^ Friedrich., Glocker, Ernst. Generum et specierum mineralium, secundum ordines naturales digestorum synopsis, omnium, quotquot adhuc reperta sunt mineralium nomina complectens. : Adjectis synonymis et veteribus et recentioribus ac novissimarum analysium chemicarum summis. Systematis mineralium naturalis prodromus. OCLC 995480390.{{cite book}}: CS1 maint: multiple names: authors list (link)
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  22. ^ Ye, Lin; Cook, Nigel J.; Ciobanu, Cristiana L.; Yuping, Liu; Qian, Zhang; Tiegeng, Liu; Wei, Gao; Yulong, Yang; Danyushevskiy, Leonid (2011). "Trace and minor elements in sphalerite from base metal deposits in South China: A LA-ICPMS study". Ore Geology Reviews. 39 (4): 188–217. doi:10.1016/j.oregeorev.2011.03.001.
  23. ^ Knorsch, Manuel; Nadoll, Patrick; Klemd, Reiner (2020). "Trace elements and textures of hydrothermal sphalerite and pyrite in Upper Permian (Zechstein) carbonates of the North German Basin". Journal of Geochemical Exploration. 209: 106416. doi:10.1016/j.gexplo.2019.106416.
  24. ^ Zhu, Chuanwei; Liao, Shili; Wang, Wei; Zhang, Yuxu; Yang, Tao; Fan, Haifeng; Wen, Hanjie (2018). "Variations in Zn and S isotope chemistry of sedimentary sphalerite, Wusihe Zn-Pb deposit, Sichuan Province, China". Ore Geology Reviews. 95: 639–648. doi:10.1016/j.oregeorev.2018.03.018.
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  27. ^ Viets, John G.; Hopkins, Roy T.; Miller, Bruce M. (1992). "Variations in minor and trace metals in sphalerite from mississippi valley-type deposits of the Ozark region; genetic implications". Economic Geology. 87 (7): 1897–1905. doi:10.2113/gsecongeo.87.7.1897. ISSN 1554-0774.
  28. ^ Cheng, Siwei; Liu, Guijian; Liu, Yuan; Wu, Dun (2018-03-29). "Cadmium in Chinese coals: Abundance, distribution, occurrence, and environmental effects". Human and Ecological Risk Assessment: An International Journal. 25 (3): 527–547. doi:10.1080/10807039.2018.1450136. ISSN 1080-7039.
  29. ^ Emsbo, Poul; Seal, Robert R.; Breit, George N.; Diehl, Sharon F.; Shah, Anjana K. (2016). "Sedimentary exhalative (sedex) zinc-lead-silver deposit model". Scientific Investigations Report. doi:10.3133/sir20105070n. ISSN 2328-0328.
  30. ^ Misra, Kula C. (2000), "Mississippi Valley-Type (MVT) Zinc-Lead Deposits", Understanding Mineral Deposits, Dordrecht: Springer Netherlands, pp. 573–612, ISBN 978-94-010-5752-3, retrieved 2021-03-26
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  33. ^ Roland., Shanks, Wayne C. Thurston, (2012). Volcanogenic massive sulfide occurrence model. U.S. Dept. of the Interior, U.S. Geological Survey. OCLC 809680409.{{cite book}}: CS1 maint: extra punctuation (link) CS1 maint: multiple names: authors list (link)
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  35. ^ Muntyan, Barbara L. (1999). "Colorado Sphalerite". Rocks & Minerals. 74 (4): 220–235. doi:10.1080/00357529909602545. ISSN 0035-7529.
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  40. ^ Frenzel, Max; Ketris, Marina P.; Gutzmer, Jens (2014-04-01). "On the geological availability of germanium". Mineralium Deposita. 49 (4): 471–486. Bibcode:2014MinDe..49..471F. doi:10.1007/s00126-013-0506-z. ISSN 0026-4598. S2CID 129902592.
  41. ^ Frenzel, Max; Mikolajczak, Claire; Reuter, Markus A.; Gutzmer, Jens (June 2017). "Quantifying the relative availability of high-tech by-product metals – The cases of gallium, germanium and indium". Resources Policy. 52: 327–335. doi:10.1016/j.resourpol.2017.04.008.
  42. ^ Craddock, P.T. (1990). Brass in the medieval Islamic world; 2000 years of zinc and brass. British Museum Publications Ltd. pp. 73–101. ISBN 0 86159 050 3.
  43. ^ Xiao, Hongyan; Huang, Xin; Cui, Jianfeng (2020). "Local cementation brass production during 12th–13th century CE, North China: Evidences from a royal summer palace of Jin Dynasty". Journal of Archaeological Science: Reports. 34: 102657. doi:10.1016/j.jasrep.2020.102657.
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  45. ^ S., McGee, E. (1999). Colorado Yule marble : building stone of the Lincoln Memorial : an investigation of differences in durability of the Colorado Yule marble, a widely used building stone. U.S. Dept. of the Interior, U.S. Geological Survey. ISBN 0-607-91994-9. OCLC 1004947563.{{cite book}}: CS1 maint: multiple names: authors list (link)
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  48. ^ Hai, Yun; Wang, Shuonan; Liu, Hao; Lv, Guocheng; Mei, Lefu; Liao, Libing (2020). "Nanosized Zinc Sulfide/Reduced Graphene Oxide Composite Synthesized from Natural Bulk Sphalerite as Good Performance Anode for Lithium-Ion Batteries". JOM. 72 (12): 4505–4513. doi:10.1007/s11837-020-04372-5. ISSN 1047-4838.
  49. ^ Voudouris, Panagiotis; Mavrogonatos, Constantinos; Graham, Ian; Giuliani, Gaston; Tarantola, Alexandre; Melfos, Vasilios; Karampelas, Stefanos; Katerinopoulos, Athanasios; Magganas, Andreas (2019-07-29). "Gemstones of Greece: Geology and Crystallizing Environments". Minerals. 9 (8): 461. doi:10.3390/min9080461. ISSN 2075-163X.{{cite journal}}: CS1 maint: unflagged free DOI (link)
  50. ^ Murphy, Jack; Modreski, Peter (2002-08-01). "A Tour of Colorado Gemstone Localities". Rocks & Minerals. 77 (4): 218–238. doi:10.1080/00357529.2002.9925639. ISSN 0035-7529.
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