Fluorite

Gregory Fischer

Stockton University

Abstract

Fluorite is a halide mineral with four perfect cleavage planes and an isometric structure.

Although usually represented by the chemical formula CaF2, it can have impurities

substituting for calcium such as Ce and Y. Point defects in its crystal lattice allow for

electron color centers; these and the presence of cation activators cause many fluorite

crystals to be fluorescent. Fluorite is typically found in metal-rich hydrothermal deposits;

famous localities include the Blue John mine in England and the French and Swiss Alps.

Fluorspar (the industrial term for fluorite) is used in metallurgy, ceramics, optics, jewelry,

and most importantly, the production of hydrofluoric acid. Due to increasing regulation of

fluorocarbon chemicals, the worldwide production of and demand for fluorspar has

decreased in recent years.

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 Introduction

Fluorite is a fairly common mineral which humanity has used for over a

millennium. Originally called fluorspar, it gets its name from the Latin verb fluere,

meaning ‘to flow’, due to its usefulness as a flux, as well as the German ‘spat’, which is

used to describe non-metallic minerals (Origin Stones, 2017). This paper will explore

fluorite’s chemistry, structure, physical and optical properties, provenance and localities,

and various societal uses.

Fluorite Chemistry

Fluorite is a simple halide mineral, meaning that it is a salt containing alkali earth

metal (Britannica, 2013). In its pure form, it has a formula of CaF2. Commonly, however,

it is marked by impurities such as Y, Yb, Ce, Si, Al, Fe, Mg, Eu, and Sm, which can

replace up to 20% of the calcium present in the crystal (Nesse, 2017). Yttrium, cerium,

europium, and samarium are perhaps the most important impurities found in fluorite, as

rare earth elements like these are becoming extremely valuable as technology progresses.

Structure and Morphology

Fluorite is isometric, and typically forms cubes. It can, however, form

octahedrons, as well as hexoctahedrons, tetrahexahedrons, and combinations of these

forms, such as cubes with modified corners and edges (Figure 1). It belongs to the space

group Fm3m, and has an equilibrium lattice constant of 5.15 Å with a unit cell volume of

163.00 ų (Khenata et al., 2005). Fluorite’s calcium ions form a ccp arrangement,

occupying the corners and center of each face on the unit cell cube. The fluoride ions

2
occupy tetrahedral sites; four calcium ions surround them. This arrangement is due to the

fluoride ion’s coordination number of four. The calcium ions occupy half of the

tetrahedral sites, causing each to be surrounded by eight fluoride ions. Other minerals

with the same structure (and general formula MX2) include fluorocronite (PbF2) and

strontiofluorite (SrF2).

One of fluorite’s most common structural defects is twinning. Twining usually

occurs as interpenetrating cubes, but sometimes as contact spinel twins (Figure 2)

(Instituto di Cristallografia, 2017). Penetration twinning has the appearance of crystals

passing through one another; spinel twins occur when two octahedral crystals twin at

their base. Frenkel-type point defects, involving interstitial fluoride ions, are also present

in fluorite. This is because the fluoride anions have a lower electrical charge than the

calcium cations, and they therefore find it relatively easy to move closer to one another.

These Frenkel point defects create a vacancy in the crystal lattice (Lufaso, 2015).

Linear defects can also occur. Bontinck and Amelinckx (1956) proposed that a

combination of edge dislocations and screw defects led to the occurrence of helicoidal

dislocation lines in both natural and synthetic fluorite crystals. They theorized that edge

dislocations climb from one lattice plane to the next; when two edge dislocations do this with

a screw dislocation between them, they eventually bend, and pull the screw dislocation with

them. This process creates a helix with a step equal to the Burgers vector of the screw

dislocation (Bontinck and Amelinckx, 1956).

Physical Properties

Like all minerals, fluorite’s physical properties are based on its chemistry.

Fluorite displays ionic bonding, which involves the transfer of valence electrons from one
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ion to another so that both achieve filled valence shells. The energy of an ionic bond is

inversely proportional to its length; the larger the ion, the weaker the bond. Fluorite’s

ionic bonds give it a hardness of 4 on the Mohs scale, and their characteristic weak shear

strength leads to fluorite’s well-defined 4 planes of cleavage. Fluorite’s ionic bonding

also makes it a poor conductor of heat and electricity.

Fluorite’s other physical properties, such as streak, luster, specific gravity, and

fracture are arguably less important than others like cleavage and hardness, as they are

not diagnostic properties of the mineral. However, they are still worth mentioning. It has

a white streak, vitreous luster, and a specific gravity (mineral density compared to

water’s density) of 3.0 to 3.2. Unlike other minerals such as quartz which fracture

conchoidally, fluorite has an uneven fracture.

Optical Properties

Fluorite is known for its wide variety of colorations; in fact, it displays the widest

range of colors of any single mineral. It can occur as purple, green, yellow, black, brown,

pink, red, or white; when it is completely pure, however, it is colorless. Most commonly,

it is found colorless, purple, blue, or green (Farndon, 2012). Fluorite’s color is mainly

caused by color centers, which occur when electrons are mislocated in the crystal lattice.

Electron color centers, which occur frequently in fluorite, are formed by an electron

trapped in a vacant site in the lattice (Figure 3). Flaws, such as Frenkel and Schottky

point defects, are always present in natural crystals. In the case of these point defects in

fluorite, a missing fluoride anion’s position can be filled by an electron, whose negative

charge maintains the neutrality of the crystal. An electron will only fill the vacancy when

4
the crystal absorbs high-energy radiation, which raises the electron’s energy state. The

electron will then attempt to return to its original energy level; the positive charge of

nearby cations, however, will prevent this. The absorption of incident light with energy

Ebd excites the electron, which then returns to the color center while emitting light.

Because fluorite is an isometric mineral, it is also isotropic. In thin section, when

viewed on a petrographic microscope in cross-polarized light, fluorite will appear extinct.

This is because its refractive index stays consistently between 1.433 - 1.448 (higher when

impurities, particularly Yttrium, are present) throughout the crystal; its optical indicatrix

is therefore a sphere, with all circular cross sections. Unlike anisotropic minerals, light

that enters fluorite is not split into a fast and slow ray. Instead, light remains travelling in

its original direction and speed as it passes through the crystal. Therefore, it can be said

that fluorite has a birefringence of 0. While this normally results in a lack of interference

color (extinction), fluorite can occasionally display weak anomalous color in lamellae

(Mindat, 2017).

Other optical properties of fluorite include moderate relief and a lack of

pleochroism. In plane polarized light, crystals will be either colorless or paler versions of

the hand sample’s color. The color does not change as the stage rotates because fluorite is

an isotropic mineral; it does not experience the double refraction that causes pleochroism

(Nesse, 2017).

Fluorescence

Perhaps fluorite’s most well-known characteristic is its fluorescence. In fact,

fluorescence was named after fluorite when it was first observed by physicist George

Stokes in 1852 (King, 2017). The effects of fluorescence are seen when a mineral appears

5
to be a different color under ultraviolet light. In the case of fluorite, it appears blue

(Figure 4). It is ultimately caused by light energy absorbed by a crystal; when an electron

is displaced in the creation of a color center as previously explained, the vacancy it leaves

at the lower energy level is filled by a higher energy electron. That higher energy

electron’s vacancy is also filled, etc., until all electrons are at their lowest possible energy

state. When a higher energy electron’s energy state is decreased, it releases energy in the

form of electromagnetic radiation; if the radiation is in the visible spectrum, and stops

when the light source is turned off, the mineral is considered fluorescent. Ultraviolet light

is typically used to produce fluorescence because the fluorescent light is less energetic

than the original source; it therefore has a longer wavelength, which means using

ultraviolet light creates fluorescent light visible to us in the lower energy visible spectrum

(Nesse, 2017). Studies have shown that traces of europium and ytterbium, along with

other rare earth element impurities, act as activators for fluorescence in fluorite (Przibram,

1935).

Fluorite can also exhibit phosphorescence, thermoluminescence, and/or

triboluminescence (Mindat, 2017). Phosphorescence is similar to fluorescence, with the

difference being that a phosphorescent mineral will continue to emit light energy after the

incident radiation ceases. This is due to the length of time it takes electrons to return to

their ground state. In a fluorescent mineral, lower energy electron vacancies are filled in

10-8 second; phosphorescent minerals’ electrons take longer. Thermoluminescent

minerals emit visible light energy when heated; this usually requires the mineral to be

previously exposed to light or radiation, exciting its electrons to higher energy positions

where they are then trapped (i.e. by a color center). Exposure to heat can then provide the

6
activation energy necessary to allow the electrons down to their ground state; they emit

light as this occurs (Nesse, 2017). Triboluminescent minerals produce a faint amount of

light when crushed, scratched, struck, or rubbed; this light is emitted when the mineral’s

chemical bonds are broken. Both thermoluminescence and triboluminescence require

near total darkness to be seen (King, 2017).

Provenance and Associated Minerals

Fluorite is commonly found in many different environments. The most typical

fluorite-forming environment is metal-rich lode hydrothermal replacement deposits.

Commonly, in these deposits, it will be associated with galena, barite, and pyrite (see

Figure 5); it can also be found with silver (Chesterman, 1979). In this case, minerals are

precipitated from a hydrothermal solution and both replace the host rock as well as fill

openings in it (Britannica, 2013). The high temperatures in this system can cause

fluorite’s habit to vary from octahedral to dodecahedral (Farndon, 2012).

Fluorite can also be found in epithermal veins, which are hydrothermal deposits

formed at shallow depths beneath a boiling hot spring. Here, it is associated with calcite,

rhodochrosite, and chalcedony. In carbonate rocks, fluorite is typically found with albite

and pyrite. In hornfels, which are formed by contact metamorphism, it is associated with

calcite and spinel. Fluorite can also occur as an accessory mineral in A-type granitic

rocks, including some granite pegmatites (Chesterman, 1979).

7
 Localities

Impressive fluorite samples with varying chemistry/properties have been

discovered in many locations on every continent. One of the most famous is the Blue

John, first discovered at the Blue John Mine in Castleton, England. This variety is

characterized by its white and purple banding which formed as impurity levels

increased/decreased during crystallization. Stink-Fluss, most commonly found (and

discovered) in Wölsendorf, Germany, is a dark purple/black color, and emits an odor of

hydrogen fluoride and ozone (ozone’s smell is what we commonly associate with rain)

when grinded. This variety has an unusually high amount of free fluorine and calcium,

whose interaction with water upon grinding cause the odor for which it is named.

Ratokvite, found in the Moscow area, is a fine-disperse (nearly microcrystalline) variety

with a deep violet coloration; it is thought to be of sedimentary origins (Mindat, 2017).

Tiffany stone, a fine-grained, purple, non-fluorescent variety with intergrown

chalcedony, bertrandite, opal, and/or quartz is found in Spor Mountain (Thomas Range)

in Utah (Figure 6). The Western Kentucky Fluorspar District is a more well-known US

locality, which consists mostly of Mississippi Valley-type (MVT) hydrothermal deposits

(Kentucky Geological Survey, 2017).

The most highly valued fluorite (for collecting) is found in the Swiss and French

Alps; these samples contain pink-red octahedral crystals up to 10 cm long. However, the

most classic (type) localities are the lead, iron and tin mines of England, as well as

hydrothermal deposits throughout Germany (Farndon, 2012).

8
 Societal Uses

Processing

Before fluorite can be used, it must be processed. Beneficiation, the process by

which the valuable constituents of the ore are separated and concentrated, can be divided

into two parts: manual election and floatation. Massive fluorite ore is separated into

several sizing grades by several screens, after which the largest pieces are manually

elected (hand-picked) out. The rest of the ore is crushed, grinded, and floated. After

floatation, the powdered fluorite concentrate is elected out (Zoneding, 2017). A recent

study found that there are, in fact, differences in the floatation characteristics between

colorless, green, and purple fluorite. When sodium oleate was used as a collector,

colorless fluorite had the best flotation response, followed by green fluorite and then

purple fluorite. This indicates some level of discrepancy in the interfacial properties

between the varieties of fluorite, despite the samples being from the same deposit and

having a similar CaF2 content (Zheng et al., 2017).

Hydrofluoric Acid

The majority of industrially-extracted fluorite (still referred to as fluorspar when

sold in bulk/processed form) is used to produce hydrofluoric acid (HF); HF is the

intermediary from which humanity gets all of its fluorine. Acid grade fluorspar, which is

the most pure, is the type of fluorspar used by the chemical industry; it contains over 97%

CaF2. Hydrofluoric acid is then used to produce a wide variety of products, including

refrigerants, foam blowing agents, fire extinguishers, solvents, and other fluorocarbon

chemicals (King, 2017). Many of these fluorocarbon chemicals unfortunately act as

9
greenhouse gases, and have led to the decrease of ozone in the stratosphere; as such, their

manufacture and use is being phased out under the Montreal Protocol, an international

environmental treaty. Hydrofluoric acid is also the source of fluorine used in dental and

water treatments used to prevent cavities (Nesse, 2017).

Ceramics

The second-most pure grade of fluorspar, which contains between 85-96% CaF2,

is used in the manufacturing of ceramics, specialty glass, and enamelware. Specifically, it

is used to make glazes and other treatments which change the surface properties of

commercially-sold glass objects to make them more attractive or durable. Hard, glossy

surfaces as well as opalescent surfaces are both made with fluorspar; Teflon, a non-stick

cooking surface, is perhaps the most widespread example of fluorite’s contributions to

the ceramics industry (King, 2017).

Metallurgy

Metallurgic grade fluorspar, the lowest grade, contains between 60-85% CaF2.

Typically, it is used as a flux in the production of iron, steel, and other metals. Fluxes can

be used for many purposes, such as preventing oxides from forming on the surface of

molten metal, purging chemical impurities, lowering melting temperature, and reducing

slag viscosity at low temperatures. Fluorspar is used to remove impurities like

phosphorus and sulfur, as well as decrease the viscosity of slag. Usually, only 20-60

pounds of fluorspar is used for every ton of iron/steel produced (King, 2017).

10
Optical Uses

Some fluorite has such great optical clarity that it is used to create lenses.

Fluorite’s low refractive index and low dispersion (separation of visible light into

different colors) allow fluorite lenses to produce extremely sharp pictures/images.

Chromatic aberration, usually seen as green or purple ‘fuzziness’, is an issue caused by

dispersion in normal glass lenses; it is significantly reduced in fluorite lenses (Figure 7).

Fluorite lenses are therefore very valuable tools in microscopy and telescopy. Canon, Inc.

has developed synthetic fluorite crystals to use in their high-end telephoto lenses

(Geology IN, 2015). Other imaging companies like Nikon also produce synthetic fluorite

lenses, as well as a fluorine coating for glass lenses, which is a less expensive alternative

(Nikon, 2017). Even NASA’s Hubble Space Telescope has a coating of magnesium

fluoride on its primary mirror (NASA, 2017).

Lapidary Uses

Some fluorite samples with excellent clarity and color can be cut by lapidaries

and used as gemstones (Figure 8). Because of its low hardness, this is not very common.

Until recently, this industry reserved fluorite for carving bowls, vases, and figurines.

Some jewelers, however, who are willing to take the risk selling a fragile gem, now sell

green fluorite as a cheaper alternative to emerald. To reduce the chance of damaging the

fluorite, it is typically sold in pendants (Federman, 2006). Carved objects such as vases

and figurines usually have to be treated with a protective coating to prevent scratches

(King, 2017).

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Fluid Inclusion Studies

Like many minerals, fluorite can contain fluid inclusions, which are formed when

crystals grow in the presence of a fluid phase (Bodnar, 2003). In addition to providing

insight on the conditions of the mineral’s formation, these fluid inclusions have also been

used in paleoclimate studies. Fluorite’s lack of hydrogen and oxygen makes it especially

useful for this application, as post-entrapment isotope exchange is impossible. A 1993

study examining fluid inclusions (of meteoric origin) in Idaho’s Bayshore mining district

found that isotopic ratios of the Eocene fluids were comparable to today’s; this indicates

that Eocene climate in that area was similar to today’s (Seal and Rye, 1993).

Indicator for REE and Lead/Silver Ores

Fluorite is commonly found as a gangue mineral in many rare earth element

(REE) deposits in carbonatites, peralkaline intrusions, zinc and lead-bearing

hydrothermal deposits, as well as epithermal precious metal deposits. Fluorite is believed

to have potential as an indicator mineral for the exploration of specialty metals including

Nb and REE, particularly in carbonatites; however, more research is required on this

subject. Currently, carbonatite-related fluorite can be easily distinguished from MVT

fluorite by comparing REE concentrations, but compositional overlaps in sedimentary,

igneous, and metamorphic rock-hosted fluorites suggest fluorite REE concentration is

independent of that in the host rock (Makin, et al., 2014). The Northern Pennines in

England are home to a vast deposit of silver-bearing galena and fluorite that has been

mined for over 1000 years; there is also hope that fluorite can serve as an indicator for

similar silver-bearing ores elsewhere (Dunham et al., 2001).

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Metaphysical/Medicinal Uses

Although dismissed by most modern science and religion, some people believe

that fluorite has metaphysical and medicinal properties. Metaphysical properties include

the ability to calm the spirit and mind in preparation for meditation, increase objectivity

and concentration, and clarify decision-making processes; it has been used in traditional

Chinese medicine for insomnia, anxiety, coughing and wheezing, and excessive

menstrual bleeding (Celestial Earth Minerals, 2017).

USGS Usage Data

According to the USGS, little fluorspar was produced in the United States in

2016; most of the US demand was met by imports and small amounts of synthetic

fluorspar. The vast majority of imported fluorspar (72%) was sourced from Mexico; other

sources include China (9%), South Africa (9%), and Mongolia (4%). The passing of the

Frank R. Lautenberg Chemical Safety for the 21st Century Act, in addition to the already

adverse market conditions (demand dropped when many fluorocarbons were banned), has

affected many fluorspar mining projects. Although mines in five European and African

countries have closed, a new mine is under construction in Canada. This, along with the

construction of a new hydrofluoroolefin HFO-1234yf plant in Texas, may indicate a

somewhat brighter future for the fluorspar industry (McRae, 2017).

13
 Conclusions

Fluorite’s chemistry and properties make it a useful material for many industrial

and consumer applications. Although fluorspar demand has decreased in recent years,

new chemical products, along with its use as a REE indicator, may trigger a comeback

for the mineral. With a successful outcome of these new proposed uses, fluorite will

continue to play an important societal role as humanity progresses.

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 Figures

Figure 1: Crystal Morphology

(Friedman, 2017)

Figure 2: Contact Spinel Twins

(Mine Rat Minerals, 2017)

Figure 3: Electron Color Center

(Flynn, 2017)

15
Figure 4: Fluorescence

(King, 2017)

Figure 5: Fluorite with Galena

(Celestial Earth Minerals, 2017)

Figure 6: Tiffany Stone at Materion Beryllium Mine, Utah

(Gregory Fischer)

16
Figure 7: Reduced Chromatic Aberration

(Geology IN, 2015)

Figure 8: Fluorite as Gemstones

(King, 2017)

17
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