Cinnabar

This article is about the mineral. For the plant resin, see Dragon's blood. For the moth, see Cinnabar moth. For the theatre in Petaluma, California, see Cinnabar Theater.
Cinnabar

Cinnabar
General
Category Sulfide mineral
Formula
(repeating unit)		 Mercury(II) sulfide, HgS
Strunz classification 2.CD.15a
Crystal system Trigonal
Crystal class Trapezohedral (32)
H-M symbol: (32)
Space group P3121, P3221
Unit cell a = 4.145(2) Å, c = 9.496(2) Å, Z = 3
Identification
Color Cochineal-red, towards brownish red and lead-gray
Crystal habit Rhombohedral to tabular; granular to massive and as incrustations
Twinning Simple contact twins, twin plane {0001}
Cleavage Prismatic {1010}, perfect
Fracture Uneven to subconchoidal
Tenacity Slightly sectile
Mohs scale hardness 2.0-2.5
Luster Adamantine to dull
Streak Scarlet
Diaphaneity Transparent in thin pieces
Specific gravity 8.176
Optical properties Uniaxial (+)
Refractive index nω = 2.905 nε = 3.256
Birefringence δ = 0.351
Solubility 1.04 x 10−25 g per 100 ml water (Ksp at 25°C = 2 x 10−32)[1]
References [2][3][4][5]

Cinnabar (/ˈsɪnəbɑːr/) and cinnabarite (/sɪnəˈbɑːraɪt/), likely deriving from the Ancient Greek: κιννάβαρι[6] (kinnabari), refer to the common bright scarlet to brick-red form of mercury(II) sulfide, formula HgS, that is the most common source ore for refining elemental mercury, and is the historic source for the brilliant red or scarlet pigment termed vermilion and associated red mercury pigments.

Cinnabar generally occurs as a vein-filling mineral associated with recent volcanic activity and alkaline hot springs. The mineral resembles quartz in symmetry and in its exhibiting birefringence; cinnabar has a mean refractive index of ~3.2, a hardness between 2 and 2.5, and a specific gravity of ~8.1. The color and properties derive from a structure that is a rhombohedral crystalline lattice belonging to the hexagonal crystal system, crystals that sometimes exhibit twinning.

Cinnabar has been used for its color since antiquity in the Near East, including as a rouge-type cosmetic, in the New World since the Olmec culture, and in China since as early as the Song dynasty, where it was used in coloring lacquerware.

Associated modern precautions for use and handling of cinnabar arise from the toxicity of the mercury component, which was recognized as early as ancient Rome.

Etymology

The name comes from Ancient Greek: κιννάβαρι[6] (kinnabari),[7] a Greek word most likely applied by Theophrastus to several distinct substances.[6] Other sources say the word comes from the Persian: شنگرف‎‎ shangarf (Arabicized as زنجفرة zinjifrah), a word of uncertain origin (also compare, Sanskrit सुगर sugara). In Latin it was sometimes known as minium, meaning also "red cinnamon", though both of these terms now refer specifically to lead tetroxide.[8]

Properties and structure

Properties

Cinnabar

Cinnabar is generally found in a massive, granular or earthy form and is bright scarlet to brick-red in color, though it occasionally occurs in crystals with a non-metallic adamantine luster.[9][10] It resembles quartz in its symmetry. It exhibits birefringence, and it has the highest refractive index of any mineral. Its mean refractive index is 3.08 (sodium light wavelengths),[11] versus the indices for diamond and the non-mineral gallium(III) arsenide (GaAs), which are 2.42 and 3.93, respectively. The hardness of cinnabar is 2.0–2.5 on the Mohs scale, and its specific gravity 8.1.[5]

Structure

Crystal structure of cinnabar: yellow = sulfur, grey = mercury, green = cell

Structurally, cinnabar belongs to the trigonal crystal system.[5] It occurs as thick tabular or slender prismatic crystals or as granular to massive incrustations.[3] Crystal twinning occurs as simple contact twins.[4]

Note, mercury(II) sulfide, HgS, adopts the cinnabar structure described, and one additional structure, i.e. it is dimorphous.[12] Cinnabar is the more stable form, and is a structure akin to that of HgO: each Hg center has two short Hg-S bonds (each 2.36 Å), and four longer Hg•••S contacts (with 3.10, 3.10, 3.30, and 3.30 Å separations). In addition, HgS is found in a black, non-cinnabar polymorph (metacinnabar) that has the zincblende structure.[4]

Occurrence

Cinnabar mercury ore from Nevada, USA

Cinnabar generally occurs as a vein-filling mineral associated with recent volcanic activity and alkaline hot springs. Cinnabar is deposited by epithermal ascending aqueous solutions (those near surface and not too hot) far removed from their igneous source. It is associated with native mercury, stibnite, realgar, pyrite, marcasite, opal, quartz, chalcedony, dolomite, calcite and barite.[3]

Cinnabar is essentially found in all mineral extraction localities that yield mercury, notably Puerto Princesa (Philippines); Almadén (Spain); New Almaden (California); Hastings Mine and St. John's Mine, Vallejo, California;[13] Idrija (Slovenia); New Idria (California); Giza, Egypt; Moschellandsberg near Obermoschel in the Palatinate; Ripa, at the foot of the Apuan Alps and in the Mount Amiata (Tuscany); the mountain Avala (Serbia); Huancavelica (Peru); Murfreesboro, Arkansas; Terlingua, Texas (United States); and the province of Guizhou in China, where fine crystals have been obtained. It was also mined near Red Devil, Alaska on the middle Kuskokwim River. Red Devil was named after the Red Devil cinnabar mine, a primary source of mercury. It has been found in Dominica, Lesser Antilles near its sulfur springs at the southern end of the island along the west coast.

Cinnabar is still being deposited, e.g., at the present day from the hot waters of Sulphur Bank Mine in California and Steamboat Springs, Nevada.

Mining and extraction of mercury

Apparatus for the distillation of cinnabar, Alchimia, 1570

As the most common source of mercury in nature,[14] cinnabar has been mined for thousands of years, even as far back as the Neolithic Age.[15] During the Roman Empire it was mined both as a pigment,[16][17] and for its mercury content.[17]:XLI

To produce liquid mercury (quicksilver), crushed cinnabar ore is roasted in rotary furnaces. Pure mercury separates from sulfur in this process and easily evaporates. A condensing column is used to collect the liquid metal, which is most often shipped in iron flasks.

Toxicity

Associated modern precautions for use and handling of cinnabar arise from the toxicity of the mercury component, which was recognized as early as in ancient Rome.[18] Because of its mercury content, cinnabar can be toxic to human beings. Though people in ancient South America often used cinnabar for art, or processed it into refined mercury (as a means to gild silver and gold to objects) "the toxic properties of mercury were well known. It was dangerous to those who mined and processed cinnabar, it caused shaking, loss of sense, and death. Data suggest that mercury was retorted from cinnabar and the workers were exposed to the toxic mercury fumes."[19] Overexposure to mercury, mercurialism, was seen as an occupational disease to the ancient Romans, "Mining in the Spanish cinnabar mines of Almadén, 225 km (140 mi) southwest of Madrid, was regarded as being akin to a death sentence due to the shortened life expectancy of the miners, who were slaves or convicts."[20]

Decorative use

Cinnabar has been used for its color since antiquity in the Near East, including as a rouge-type cosmetic,[18] in the New World since the Olmec culture, and in China since as early as the Song dynasty, where it was used in coloring lacquerware.

Cinnabar's use as a color in the New World, since the Olmec culture,[21] is exemplified by its use in royal burial chambers during the peak of Maya civilization, most dramatically in the Tomb of the Red Queen in Palenque (600–700 AD), where the remains of a noble woman and objects belonging to her in her sarcophagus were completely covered with bright red powder made from cinnabar.[22]

The most popularly known use of cinnabar is in Chinese carved lacquerware, a technique that apparently originated in the Song dynasty. The danger of mercury poisoning may be reduced in ancient lacquerware by entraining the powdered pigment in lacquer,[23] but could still pose an environmental hazard if the pieces were accidentally destroyed. In the modern jewelry industry, the toxic pigment is replaced by a resin-based polymer that approximates the appearance of pigmented lacquer.

Other forms

See also

References

  1. ↑ Myers, R.J. (1986). "The new low value for the second dissociation constant of H2S. Its history, its best value, and its impact on teaching sulfide equilibria". J. Chem. Ed. 63: 689, 687–690.
  2. ↑ Mineralienatlas
  3. 1 2 3 "Cinnabar (Hgs)" (PDF). Rruff.geo.arizona.edu. Retrieved 2015-07-24.
  4. 1 2 3 "Cinnabar: Cinnabar mineral information and data". Mindat.org. Retrieved 2015-07-24.
  5. 1 2 3 "Cinnabar Mineral Data". Webmineral.com. Retrieved 2015-07-24.
  6. 1 2 3  Chisholm, Hugh, ed. (1911). "Cinnabar". Encyclopædia Britannica. 6 (11th ed.). Cambridge University Press. p. 376.
  7. ↑ "Cinnabar". Online Etymology Dictionary. Retrieved 22 May 2012.
  8. ↑ Daniel V. Thompson, 1956, The Materials and Techniques of Medieval Painting, Chicago, IL, USA: Dover (R.R. Donnelley-Courier), pp. 100–102.
  9. ↑ King, R. J. (2002). "Minerals Explained 37: Cinnabar". Geology Today. 18 (5): 195–199. doi:10.1046/j.0266-6979.2003.00366.x.
  10. ↑ Klein, Cornelis and Cornelius S. Hurlbut, Jr.; Manual of Mineralogy, Wiley, 20th ed., 1985, p. 281 ISBN 0-471-80580-7
  11. ↑ Schumann, W. (1997). Gemstones of the World. New York, NY, USA: Sterling. ISBN 0-8069-9461-4.
  12. ↑ Wells, A. F. (1984). Structural Inorganic Chemistry. Oxford, OXF, GBR: Clarendon Press. ISBN 0-19-855370-6.
  13. ↑ C.Michael Hogan, Marc Papineau et al., Environmental Assessment of the Columbus Parkway Widening between Ascot Parkway and the Northgate Development, Vallejo, Earth Metrics Inc. Report 7853, California State Clearinghouse, September 1989, pp. TBD.
  14. ↑ "Environment Canada : Natural Sources". Ec.gc.ca. Retrieved 2015-07-24.
  15. ↑ Martín-Gil, J.; Martín-Gil, F. J.; Delibes-de-Castro, G.; Zapatero-Magdaleno, P.; Sarabia-Herrero, F. J. (1995). "The first known use of vermillion". Experientia. 51 (8): 759–761. doi:10.1007/BF01922425. ISSN 0014-4754. PMID 7649232.
  16. ↑ Vitruvius, De architectura VII; IV–V.
  17. 1 2 Pliny, Natural History; XXXIII.:XXXVI–XLII
  18. 1 2 Susan Stewart, 2014, "'Gleaming and deadly white': Toxic cosmetics in the Roman world," pp. 84f, 79-88, in History of Toxicology and Environmental Health: Toxicology in Antiquity II (Philip Wexler, Ed.), New York, NY, USA:Academic Press, ISBN 0-12-801634-5, see , accessed 24 July 2015.
  19. ↑ Petersen, G. (2010). Mining and Metallurgy in Ancient Perú. Boulder, CO, USA: The Geological Society of America. p. TBD..
  20. ↑ Hayes, A. W. (2014). Principles and Methods of Toxicology (6th ed.). New York, NY, USA: Informa Healthcare. p. 10. ISBN 978-1-842-14537-1.
  21. ↑ "New World's Oldest". Time Magazine. Jul 29, 1957.
  22. ↑ Healy, Paul F.; Marc G. Blainey (2011). "Ancient Maya mosaic mirrors: Function, symbolism, and meaning". Ancient Mesoamerica. 22 (2): 230, 229–244. doi:10.1017/S0956536111000241. Retrieved July 23, 2015.
  23. ↑ R. V. Dietrich (2005). "Cinnabar". Gemrocks: Ornamental & Curio Stones. Ann Arbor, MI, USA: University of Michigan. p. TBD..
  24. ↑ "Hepatic Cinnabar: Hepatic Cinnabar mineral information and data.". mindat.org.
  25. ↑ Shepard, Charles Upham; Treatise on Mineralogy, Hezekiah Howe, 1832, p. 132
  26. ↑ "Hypercinnabar: Hypercinnabar mineral information and data.". mindat.org.
  27. ↑ "Metacinnabar: Metacinnabar mineral information and data.". mindat.org.
  28. ↑ Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego, CA, USA: Academic Press. p. TBD.. ISBN 0-12-352651-5.

Further reading

Barone G., Di Bella M., Mastelloni M.A., Mazzoleni P., Quartieri S., Raneri S., Sabatino G., Vailati C.,Pottery production of the pittore di lipari: chemical and mineralogical analysis of the pigments, in 2 end European Mineralogical Conference, emc2016 “Minerals, fluids and rocks: alphabet and words of planet earth”, Rimini, 11-15 sett. 2016, p. 716

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