Halides

Fluorite CaF2
Fluorite

Cubic

n 1.4331.435
Dispersion Weak
D (g/cm3) 3.18
H 4
Cleavage {111} perfect
Twinning {111}, commonly as interpenetrant cubes
Colour Extremely variable: colourless, white, yellow, green, blue and purple varieties are the most
common; colourless, pale green or pale violet in thin section
Unit cell a 5.463 Å
Z = 4; space group Fm3m
Special features Soluble in H2SO4 with evolution of HF; slightly soluble in HCl

Fluorite occurs typically as late-stage accessory mineral in granites and greisens, and is also found
as a product of hydrothermal mineralization in limestones.

Structure sometimes known as antozonite. Some dark purple

The calcium ions in fluorite are arranged on a cubic
face-centred lattice, while each fluorine ion is at the
centre of one of the smaller cubes obtained by dividing
the unit cube into eight parts (Fig. 314). Each Ca is thus
coordinated by eight F ions and each F is surrounded by
four Ca ions arranged at the corners of a regular
tetrahedron. This is the simplest of the structures
commonly assumed by AX2 compounds and represents
the highest possible coordination (8:4), the radius ratio
condition being that RA:RX > 0.732.
Chemistry
fluorite may contain hydrocarbons, and in particular
the Blue John fluorite from Treak Cliff, Castleton,
Derbyshire, has yielded as much as 0.27% carbon. Dark
purple fluorites have also been reported to be relatively
rich in strontium, containing up to 1% Sr.
Fluorite can be prepared artificially by the evapora-
tion of a solution of CaF2 in HCl. Large synthetic
crystals for optical purposes have been obtained by
fusing precipitated CaF2 in a graphite crucible in a
vacuum furnace; PbF2 may be added to act as a
scavenger for impurities. The name is derived from the
Latin fluo, I flow, in allusion to its readily fusible nature
and its commercial use as a flux in smelting.

Most fluorite is at least 99% CaF2, and the small
amounts of Si, Al and Mg reported are probably due to
impurities or inclusions. The chief substitutions which
can occur are the replacement of part of the Ca by Sr or
by Y and Ce: in the variety yttrofluorite, (Ca,Y)F23,
the YF3 component may amount to 1020% with minor
amounts of CeF3. Some fluorites are reported to contain
free fluorine, and on grinding these specimens may give
a strong odour of ozone and HF: this variety is
Optical and physical properties
The low refractive index, small dispersion and
isotropic nature make colourless fluorite a suitable
material for optical use. For fluorite with substantial
substitution of Y for Ca, the refractive index is
considerably increased.
The problem of colour in fluorite has been
extensively discussed. The theories put forward include

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Fig. 314. The crystal structure of fluorite (CrystalMaker image).
Blue: calcium; green: fluorine.
physical defects in the crystal structure, radioactive
inclusions or emanations from nearby radioactive
material, traces of rare earths, and the presence of
inclusions of carbonaceous material or MnO2. Purple
fluorite found in association with radioactive minerals
becomes colourless on heating above about 175ºC: the
colour is associated with an increase in refractive index
and a decrease in density.
Recent studies have shown that complex ‘centres’
involving rare-earth ions and/or oxygen give rise to
many of the various colours observed. These include
yttrium-associated F centres (blue), coexisting yttrium-
and cerium-associated F centres (yellowish green), the
YO2 centre (rose) and the ionized O2 molecule (O 3)
(yellow), cf. halite colours p. 483. Divalent rare-earth
ions also contribute to the coloration as in green fluorite
(Sm2+). Strong irradiation of the crystals with ionizing
radiation leads to coagulation of colour centres and to
precipitation of metallic Ca colloids which may be
Fig. 315. Chondrite-normalized plots of REE in (1) fluorescent
green fluorite from Weardale and (2) Blue John fluorite,
Castleton, Derbyshire (after Howie, R.A., Pegram, E. & Walsh,
J.N., 1982, J. Russell Soc., 1, 225).
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Fluorite
responsible for the deep blue colour of Blue John-type
fluorite. The fluorescence (a phenomenon which derives
its name from fluorite) is commonly strong and has been
correlated with relatively high contents of the rare earths
Eu, La and Ce (Fig. 315); Y and Sm may also be
important in the green varieties.
Distinguishing features
In hand specimen fluorite may be distinguished by its
perfect octahedral cleavage, its vitreous lustre and its
cubic habit. The colour is so variable as to be of little
help, but varying shades of purple and violet are
common colours, as are green and yellow, and the
colourless material is not rare. Fluorite is relatively soft,
does not effervesce with acid as calcite does, but is
attacked by H2SO4. Under the microscope its isotropic
character and very low refractive index are character-
istic: purple varieties often have sufficient depth of
colour to remain purple or violet in thin section.
Cryolite (Na3AlF6) has an even lower relief, is very
weakly birefringent, and has a pseudocubic {001}
cleavage. Halite has a perfect {001} cleavage and a
higher refractive index.
Paragenesis
In igneous rocks fluorite may occur as a late-
crystallizing, mainly hydrothermal product, especially
in granites, syenites and greisen: it is a rather common
accessory mineral in some granitic pegmatites.
Examination of liquid inclusions in pegmatite fluorites
by the decrepitation method has given a range of
crystallization temperatures of 450550ºC. It is found in
the Alnö Island alkaline complex where it occurs in
calcitefluorite dykes, and has been reported from
nepheline syenite, and from apatite-rich deposits in
alkaline rocks in the Transvaal where it occurs in
economically important quantities. Some Newfoundland
deposits, in granite, consist of veins 1.56 m thick,
 Non-silicates
containing 7595% CaF2. Fluorite has also been
recorded in the drusy cavities of blocks ejected from
volcanoes, and as a volcanic sublimate. In these igneous
occurrences associated minerals include cassiterite,
topaz, apatite and lepidolite for the pneumatolytic
deposits, and calcite, pyrite and apatite for the
hydrothermal product.
Fluorite is commonly found associated with typical
hydrothermal minerals not known to be directly related to
any igneous body. Such hydrothermal vein deposits may
also carry baryte, sphalerite, galena, calcite and
chalcedony or quartz. In the English Pennines purple
and green fluorite occur towards the centre of the fluorite
zone whereas in the outer portion yellow fluorite is
found, and it is commonly associated with baryte.
Homogenization studies on primary fluid inclusions in
hydrothermal fluorite from the North Pennine
(Pb,Zn,Ba)fluorite deposits indicate depositional
temperatures of 92220ºC; the fluids are highly saline
with 1525 equivalent wt.% NaCl. The ore-forming fluid
was probably a concentrated (Na,Ca,K)-chloride brine
similar to modern oilfield waters found at depth in
sedimentary basins; at a flow rate of 0.51.0 cm/s, the
formation of a typical vein might take 1000 years. The
Illinois-Kentucky fluorite deposits are epigenetic and
include vein deposits and bedding replacement deposits:
physical guides were structural and stratigraphical.
Dilution of mineralizing fluids by groundwater, and the
change in temperature gradient on contact with excess
groundwater, are considered to be the major chemical
factors governing the formation of these fluorite deposits.
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Fluorite is sometimes found as a cementing material
in sandstone: violet grains of fluorite are fairly common
as a detrital mineral in sands, being derived from acid
igneous rocks and hydrothermal deposits. The mineral is
known from geodes, with calcite, baryte and sphalerite
in limestone, where it is probably hydrothermal in
origin. The variety of fluorite known as Blue John
occurs in spheroidal nodular masses with a radiating
crystalline structure, and contains blue bands of varying
intensity arranged concentrically, parallel to the nodular
surface, and between these, colourless, yellow or paler
blue bands: this variety is virtually restricted to an area
near Castleton, Derbyshire.
Further reading
Allen, R.D. (1952) Variations in chemical and physical properties of
fluorite. American Mineralogist, 37, 910930.
Bill, H. and Calas, G. (1978) Color centers, associated rare-earth ions
and the origin of coloration in natural fluorites. Physics and
Chemistry of Minerals, 3, 117131.
Braithwaite, R.S.W., Flowers, W.T. Hazeldine, R.N. and Russell, M.
(1973) The cause of the colour of Blue John and other purple
fluorites. Mineralogical Magazine, 39, 401411.
Naldrett, D.L., Lachaine, A. and Naldrett, S.N. (1987) Rare earth
elements, thermal history, and the colour of natural fluorites.
Canadian Journal of Earth Sciences, 24, 20822088.
Nordstrom, D.K. and Jenne, E.A. (1977) Fluorite solubility equilibria
in selected geothermal waters. Geochimica et Cosmochimica Acta,
41, 175188.
Rogers, P.J. (1978) Fluid inclusion studies on fluorite from the
Askrigg Block. Transactions of the Institution of Mining &
Metallurgy (Section B: Applied Earth Science), 87, 125131.