Cinnabar

Cinnabar (/ˈsɪnəbɑːr/) or 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
(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

General

Category Sulfide mineral

Formula Mercury(II) sulfide,

(repeating unit) HgS

Strunz classification 2.CD.15a

Crystal system Trigonal

Crystal class Trapezohedral (32)

(same H–M symbol)

Space group P3121, P3221

Unit cell a = 4.145(2) Å, c =

9.496(2) Å, Z = 3

Identification

C l C hi l d t d
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
 pieces

Specific gravity 8.176

Optical properties Uniaxial (+)

Refractive index nω = 2.905 nε = 3.256

Birefringence δ = 0.351

Solubility 1.04 × 10−25 g/100 ml

water
(Ksp at 25 °C =
2 × 10−32)[1]

References [2][3][4][5]

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
approximately 3.2, a hardness between
2.0 and 2.5, and a specific gravity of
approximately 8.1. The color and
properties derive from a structure that is
a hexagonal crystalline lattice belonging
to the trigonal 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 Yangshao
culture, where it was used in coloring
stoneware.

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: ‫ ﺷﻨﮕﺮف‬shangarf (Arabicized as
‫ زﻧﺠﻔﺮة‬zinjifra), a word of uncertain origin.
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 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
nonmetallic 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, United States

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 Almadén (Spain). This
mine was exploited from Roman times
until 1991, being for centuries the most
important cinnabar deposit in the world.
Good cinnabar crystals have also been
found there.[13][14]. Cinnabar deposits
also appear in Giza (Egypt);

Cinnabar crystals of an individual size of one

centimeter, on quartz. Almadén (Ciudad Real) Spain.
Coll. Museum of the School of Mining Engineers of
Madrid.
Puerto Princesa (Philippines); New
Almaden (California); Hastings Mine and
St. John's Mine, Vallejo, California (United
States);[15] Idrija (Slovenia); New Idria,
California (United States);
Moschellandsberg near Obermoschel in
the Palatinate; La Ripa, at the foot of the
Apuan Alps and in the Mount Amiata
(Tuscany, Italy); the mountain Avala
(Serbia); Huancavelica (Peru);
Murfreesboro, Arkansas (United States);
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 near its sulfur springs
at the southern end of the island along
the west coast.

Cinnabar is still being deposited at the

present day, such as 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,[16] cinnabar has been mined for
thousands of years, even as far back as
the Neolithic Age.[17] During the Roman
Empire it was mined both as a
pigment,[18][19] and for its mercury
content.[19]: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.[20] Because of its mercury content,
cinnabar can be toxic to human beings.
Overexposure to mercury, mercurialism,
was seen as an occupational disease to
the ancient Romans. 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 suggests
that mercury was retorted from cinnabar
and the workers were exposed to the
toxic mercury fumes."[21] "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."[22]

Decorative use
Cinnabar has been used for its color
since antiquity in the Near East, including
as a rouge-type cosmetic,[20] in the New
World since the Olmec culture, and in
China for writing on Oracle bones as
early as the Zhou dynasty. Later in the
Song dynasty it was used in coloring
lacquerware.

Cinnabar's use as a color in the New

World, since the Olmec culture,[23] is
exemplified by its use in royal burial
chambers during the peak of Maya
civilization, most dramatically in the 7th-
century Tomb of the Red Queen in
Palenque, 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.[24]
The most popularly known use of
cinnabar is in Chinese carved
lacquerware, a technique that apparently
originated in the Song dynasty.[25] The
danger of mercury poisoning may be
reduced in ancient lacquerware by
entraining the powdered pigment in
lacquer,[26] 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.
Chinese carved cinnabar lacquerware, late Qing
dynasty. Adilnor Collection, Sweden.

Two female mummies dated A.D. 1399 to

1475 found in Cerro Esmeralda in Chile in
1976 had clothes colored with the deadly
toxin.[27]

Other forms
Hepatic cinnabar or paragite is an
impure brownish variety[28] from the
mines of Idrija in the Carniola region of
Slovenia, in which the cinnabar is
mixed with bituminous and earthy
matter.[29]
Hypercinnabar, crystallizes at high
temperature in the hexagonal crystal
system.[30]
Metacinnabar is a black-colored form
of mercury(II) sulfide, which
crystallizes in the cubic crystal
system.[31]
Synthetic cinnabar is produced by
treatment of mercury(II) salts with
hydrogen sulfide to precipitate black,
synthetic metacinnabar, which is then
heated in water. This conversion is
promoted by the presence of sodium
sulfide.[32]
See also
China red
Classification of minerals
List of minerals
Mercury cycle

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". Journal of
Chemical Education. 63: 689.
2. "Cinnabar" . Mineralienatlas.
3. "Cinnabar (HgS)" (PDF).
rruff.geo.arizona.edu. Retrieved
 2015-07-24.
4. "Cinnabar: Cinnabar mineral
information and data" . Mindat.
Retrieved 2015-07-24.
5. "Cinnabar Mineral Data" .
Webmineral. Retrieved 2015-07-24.
6. Chisholm, Hugh, ed. (1911).
"Cinnabar"  . Encyclopædia
Britannica. 6 (11th ed.). Cambridge
University Press. p. 376.
7. "Cinnabar" . Online Etymology
Dictionary. Retrieved 2012-05-22.
8. Thompson, Daniel V. (1956). The
Materials and Techniques of
Medieval Painting. Chicago, IL: 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; Hurlbut, Cornelius S.,
Jr (1985). Manual of Mineralogy
(20th ed.). Wiley. p. 281. ISBN 0-471-
80580-7.
11. Schumann, W. (1997). Gemstones of
the World . New York, NY: Sterling.
ISBN 0-8069-9461-4.
12. Wells, A. F. (1984). Structural
Inorganic Chemistry. Oxford, Oxon:
 Clarendon Press. ISBN 0-19-855370-
6.
13. Calvo, Miguel (2003). Minerales y
Minas de España. Vol. II. Sulfuros y
sulfosales. Vitoria, Spain: Sulfuros y
sulfosales. Museo de Ciencias
Naturales de Alava. pp. 355–359.
ISBN 84-7821-543-3.
14. "Cinnabar. Spain" . Mindat.
15. Hogan, C. Michael; Papineau, Marc;
et al. (Sep 1989). Environmental
Assessment of the Columbus
Parkway Widening between Ascot
Parkway and the Northgate
Development, Vallejo (Report). Earth
 Metrics Inc. Report 7853. California
State Clearinghouse.
16. "Natural Sources: Mercury" .
Environment Canada. Retrieved
2015-07-24.
17. 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 .
18. Vitruvius. De architectura. VII. 4–5.
19. Pliny. Natural History. XXXIII. 36–42.
20. Stewart, Susan (2014). " 'Gleaming
and deadly white': Toxic cosmetics in
 the Roman world". In Wexler, Philip
(ed.). History of Toxicology and
Environmental Health: Toxicology in
Antiquity . II. New York, NY:
Academic Press. p. 84. ISBN 978-0-
12-801634-3. Retrieved 2015-07-24.
21. Petersen, G. (2010). Mining and
Metallurgy in Ancient Peru. Boulder,
CO: The Geological Society of
America.
22. Hayes, A. W. (2014). Principles and
Methods of Toxicology (6th ed.).
New York, NY: Informa Healthcare.
p. 10. ISBN 978-1-842-14537-1.
23. "New World's Oldest" . Time
Magazine. 1957-07-29.
24. Healy, Paul F.; Blainey, Marc G.
(2011). "Ancient Maya mosaic
mirrors: Function, symbolism, and
meaning". Ancient Mesoamerica. 22
(2): 230.
doi:10.1017/S0956536111000241 .
25. Rawson, Jessica, ed. (2007). The
British Museum Book of Chinese Art
(2nd ed.). British Museum Press.
p. 178. ISBN 9780714124469.
26. Dietrich, R. V. (2005). "Cinnabar" .
Gemrocks: Ornamental & Curio
Stones. Ann Arbor, MI: University of
Michigan.
27. "Dressed to Kill: Chilean Mummies'
Clothes Were Colored with Deadly
 Toxin" . livescience.com.
28. "Hepatic Cinnabar: Hepatic Cinnabar
mineral information and data" .
mindat.org.
29. Shepard, Charles Upham (1832).
Treatise on Mineralogy. Hezekiah
Howe. p. 132.
30. "Hypercinnabar: Hypercinnabar
mineral information and data" .
Mindat.
31. "Metacinnabar: Metacinnabar
mineral information and data" .
Mindat.
32. Holleman, A. F.; Wiberg, E. (2001).
Inorganic Chemistry. San Diego, CA:
 Academic Press. ISBN 0-12-352651-
5.

Further reading
Stewart, Susan (2014). " 'Gleaming and
deadly white': Toxic cosmetics in the
Roman world". In Wexler, Philip (ed.).
History of Toxicology and Environmental
Health: Toxicology in Antiquity. II. New York,
NY: Academic Press. p. 84. ISBN 978-0-12-
801634-3.
Barone, G.; Di Bella, M.; Mastelloni, M. A.;
Mazzoleni, P.; Quartieri, S.; Raneri, S.;
Sabatino, G.; Vailati, C. (2016). Pottery
Production of the Pittore di Lipari: Chemical
and Mineralogical Analysis of the Pigments.
Minerals, Fluids and Rocks: Alphabet and
 Words of Planet Earth. Rimini: 2nd
European Mineralogical Conference
(EMC2016) 11–15 Sep 2016. p. 716.

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