Fluorapatite

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Fluorapatite
Fluorapatite-Muscovite-tuc8-098a.jpg
Fluorapatite (pink) on top of muscovite (green)
General
Category Phosphate mineral
Apatite group
Formula
(repeating unit)
Ca5(PO4)3F
IMA symbol Fap [1]
Strunz classification 8.BN.05
Crystal system Hexagonal
Crystal class Dipyramidal (6/m)
H-M symbol: (6/m)
Space group P63/m
Identification
ColorSea-green, violet, purple, blue, pink, yellow, brown, white, colorless, may be zoned
Crystal habit Massive to prismatic crystalline
Twinning Contact twins rare
Cleavage Indistinct
Fracture Brittle to conchoidal
Mohs scale hardness5
Luster Vitreous, resinous to dull
Streak White
Diaphaneity Transparent to opaque
Specific gravity 3.1 to 3.2
Optical propertiesUniaxial (−)
Refractive index nω = 1.631 – 1.650 nε = 1.633 – 1.646
Birefringence δ = 0.002
Ultraviolet fluorescence Fluorescent and phosphorescent
References [2] [3] [4]

Fluorapatite, often with the alternate spelling of fluoroapatite, is a phosphate mineral with the formula Ca5(PO4)3F (calcium fluorophosphate). Fluorapatite is a hard crystalline solid. Although samples can have various color (green, brown, blue, yellow, violet, or colorless), the pure mineral is colorless, as expected for a material lacking transition metals. Along with hydroxylapatite, it can be a component of tooth enamel, but for industrial use both minerals are mined in the form of phosphate rock, whose usual mineral composition is primarily fluorapatite but often with significant amounts of the other. [5]

Contents

Fluorapatite crystallizes in a hexagonal crystal system. It is often combined as a solid solution with hydroxylapatite (Ca5(PO4)3OH or Ca10(PO4)6(OH)2) in biological matrices. Chlorapatite (Ca5(PO4)3Cl) is another related structure. [5] Industrially, the mineral is an important source of both phosphoric and hydrofluoric acids.

Fluorapatite as a mineral is the most common phosphate mineral. It occurs widely as an accessory mineral in igneous rocks and in calcium rich metamorphic rocks. It commonly occurs as a detrital or diagenic mineral in sedimentary rocks and is an essential component of phosphorite ore deposits. It occurs as a residual mineral in lateritic soils. [2]

Fluorapatite is found in the teeth of sharks and other fishes in varying concentrations. It is also present in human teeth that have been exposed to fluoride ions, for example, through water fluoridation or by using fluoride-containing toothpaste. The presence of fluorapatite helps prevent tooth decay or dental caries. [6] Fluoroapatite has a mild bacteriostatic property as well, which helps decrease the proliferation of Streptococcus mutans , the predominant bacterium related to dental caries. [7]

Synthesis

Fluorapatite grains in carbonate groundmass. Photomicrographs of thin section from Siilinjarvi apatite ore. Thin section microscopy Siilinjarvi R301 6170 apatite.jpg
Fluorapatite grains in carbonate groundmass. Photomicrographs of thin section from Siilinjärvi apatite ore.
Fluorapatite. Sao Geraldo do Baixio, Doce valley, Minas Gerais, Brazil. Fluorapatite-382311.jpg
Fluorapatite. São Geraldo do Baixio, Doce valley, Minas Gerais, Brazil.

Fluorapatite can be synthesized in a three step process. First, calcium phosphate is generated by combining calcium and phosphate salts at neutral pH. This material then reacts further with fluoride sources (often sodium monofluorophosphate or calcium fluoride (CaF2)) to give the mineral. This reaction is integral in the global phosphorus cycle. [8]

3 Ca2+
+ 2 PO3−
4
Ca
3
(PO
4
)
2
3 Ca
3
(PO
4
)
2
+ CaF
2
→ 2 Ca
5
(PO
4
)
3
F

Applications

Fluorapatite as a naturally occurring impurity in apatite generates hydrogen fluoride as a byproduct during the production of phosphoric acid, as apatite is digested by sulfuric acid. The hydrogen fluoride byproduct is now one of the industrial sources of hydrofluoric acid, which in turn is used as a starting reagent for synthesis of a range of important industrial and pharmaceutical fluorine compounds.

Synthetic fluorapatite doped with manganese-II and antimony-V formed the basis for the second generation of fluorescent tube phosphors referred to as halophosphors. When irradiated with 253.7 nm mercury resonance radiation they fluoresced with broad emission which appeared within the range of acceptable whites. The antimony-V acted as the primary activator and produced a broad blue emission. Addition of manganese-II produced a second broad peak to appear at the red end of the emission spectrum at the expense of the antimony peak, excitation energy being transferred from the antimony to the manganese by a non radiative process and making the emitted light appear less blue and more pink. Replacement of some of the fluoride ions with chloride ions in the lattice caused a general shift of the emission bands to the longer wavelength red end of the spectrum. These alterations allowed phosphors for Warm White, White and Daylight tubes, (with corrected color temperatures of 2900, 4100 and 6500 K respectively), to be made. The amounts of the manganese and antimony activators vary between 0.05 and 0.5 mole percent. The reaction used to create halophosphor is shown below. The antimony and manganese must be incorporated in the correct trace amounts if the product is to be fluorescent.

6 CaHPO
4
+ (3+x) CaCO
3
+ (1−x) CaF
2
+ (2x) NH
4
Cl
→ 2 Ca
5
(PO
4
)
3
(F
1−x
Cl
x
)
+ (3+x) CO
2
+ (3+x) H
2
O
+ (2x) NH
3

Sometimes some of the calcium was substituted with strontium giving narrower emission peaks. For special purpose or colored tubes the halophosphor was mixed with small quantities of other phosphors, particularly in De-Luxe tubes with higher color rendering index for use in food market or art studio lighting.

Prior to the development of halophosphor in 1942, the first generation willemite latticed, manganese-II activated zinc orthosilicate and zinc beryllium orthosilicate phosphors were used in fluorescent tubes. Due to the respiratory toxicity of beryllium compounds the obsolescence of these early phosphor types were advantageous to health.

Since about 1990 the third generation tri-phosphors, three separate red, blue and green phosphors activated with rare earth ions and mixed in proportions to produce acceptable whites, have largely replaced halophosphors. [9]

Fluorapatite can be used as a precursor for the production of phosphorus. It can be reduced by carbon in the presence of quartz:

4 Ca
5
(PO
4
)
3
F
+ 21 SiO
2
+ 30 C → 20 CaSiO
3
+ 30 CO + SiF
4
+ 6 P
2

Upon cooling, white phosphorus (P4) is generated:

2 P
2
P
4

Fluorapatite is also used as a gemstone. [10]

Related Research Articles

<span class="mw-page-title-main">Phosphorus</span> Chemical element, symbol P and atomic number 15

Phosphorus is a chemical element; it has symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Earth. It has a concentration in the Earth's crust of about one gram per kilogram. In minerals, phosphorus generally occurs as phosphate.

<span class="mw-page-title-main">Phosphate</span> Chemical compound

In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid, a.k.a. phosphoric acid H3PO4.

<span class="mw-page-title-main">Apatite</span> Mineral group, calcium phosphate

Apatite is a group of phosphate minerals, usually hydroxyapatite, fluorapatite and chlorapatite, with high concentrations of OH, F and Cl ion, respectively, in the crystal. The formula of the admixture of the three most common endmembers is written as Ca10(PO4)6(OH,F,Cl)2, and the crystal unit cell formulae of the individual minerals are written as Ca10(PO4)6(OH)2, Ca10(PO4)6F2 and Ca10(PO4)6Cl2.

<span class="mw-page-title-main">Phosphoric acid</span> Chemical compound (PO(OH)3)

Phosphoric acid is a colorless, odorless phosphorus-containing solid, and inorganic compound with the chemical formula H3PO4. It is commonly encountered as an 85% aqueous solution, which is a colourless, odourless, and non-volatile syrupy liquid. It is a major industrial chemical, being a component of many fertilizers.

Alforsite is a barium phosphate chloride mineral with formula: Ba5(PO4)3Cl. It was discovered in 1981, and named to honor geologist John T. Alfors (1930–2005) of the California Geological Survey for his work in the area where it was discovered.

<span class="mw-page-title-main">Calcium phosphate</span> Chemical compound

The term calcium phosphate refers to a family of materials and minerals containing calcium ions (Ca2+) together with inorganic phosphate anions. Some so-called calcium phosphates contain oxide and hydroxide as well. Calcium phosphates are white solids of nutritional value and are found in many living organisms, e.g., bone mineral and tooth enamel. In milk, it exists in a colloidal form in micelles bound to casein protein with magnesium, zinc, and citrate–collectively referred to as colloidal calcium phosphate (CCP). Various calcium phosphate minerals are used in the production of phosphoric acid and fertilizers. Overuse of certain forms of calcium phosphate can lead to nutrient-containing surface runoff and subsequent adverse effects upon receiving waters such as algal blooms and eutrophication (over-enrichment with nutrients and minerals).

<span class="mw-page-title-main">Brazilianite</span>

Brazilianite, whose name derives from its country of origin, Brazil, is a typically yellow-green phosphate mineral, most commonly found in phosphate-rich pegmatites.

<span class="mw-page-title-main">Sodium fluoride</span> Ionic compound (NaF)

Sodium fluoride (NaF) is an inorganic compound with the formula NaF. It is a colorless or white solid that is readily soluble in water. It is used in trace amounts in the fluoridation of drinking water to prevent tooth decay, and in toothpastes and topical pharmaceuticals for the same purpose. In 2021, it was the 291st most commonly prescribed medication in the United States, with more than 600,000 prescriptions. It is also used in metallurgy and in medical imaging.

<span class="mw-page-title-main">Phosphorite</span> Sedimentary rock containing large amounts of phosphate minerals

Phosphorite, phosphate rock or rock phosphate is a non-detrital sedimentary rock that contains high amounts of phosphate minerals. The phosphate content of phosphorite (or grade of phosphate rock) varies greatly, from 4% to 20% phosphorus pentoxide (P2O5). Marketed phosphate rock is enriched ("beneficiated") to at least 28%, often more than 30% P2O5. This occurs through washing, screening, de-liming, magnetic separation or flotation. By comparison, the average phosphorus content of sedimentary rocks is less than 0.2%. The phosphate is present as fluorapatite Ca5(PO4)3F typically in cryptocrystalline masses (grain sizes < 1 μm) referred to as collophane-sedimentary apatite deposits of uncertain origin. It is also present as hydroxyapatite Ca5(PO4)3OH or Ca10(PO4)6(OH)2, which is often dissolved from vertebrate bones and teeth, whereas fluorapatite can originate from hydrothermal veins. Other sources also include chemically dissolved phosphate minerals from igneous and metamorphic rocks. Phosphorite deposits often occur in extensive layers, which cumulatively cover tens of thousands of square kilometres of the Earth's crust.

<span class="mw-page-title-main">Hydroxyapatite</span> Naturally occurring mineral form of calcium apatite

Hydroxyapatite is a naturally occurring mineral form of calcium apatite with the formula Ca5(PO4)3(OH), often written Ca10(PO4)6(OH)2 to denote that the crystal unit cell comprises two entities. It is the hydroxyl endmember of the complex apatite group. The OH ion can be replaced by fluoride or chloride, producing fluorapatite or chlorapatite. It crystallizes in the hexagonal crystal system. Pure hydroxyapatite powder is white. Naturally occurring apatites can, however, also have brown, yellow, or green colorations, comparable to the discolorations of dental fluorosis.

<span class="mw-page-title-main">Fluoride therapy</span> Medical use of fluoride

Fluoride therapy is the use of fluoride for medical purposes. Fluoride supplements are recommended to prevent tooth decay in children older than six months in areas where the drinking water is low in fluoride. It is typically used as a liquid, pill, or paste by mouth. Fluoride has also been used to treat a number of bone diseases.

<span class="mw-page-title-main">Herderite</span> Phosphate mineral

Herderite is a phosphate mineral belonging to the apatite, phosphate group, with formula CaBe(PO4)(F,OH). It forms monoclinic crystals, often twinned and variable in colour from colourless through yellow to green. It forms a series with the more common hydroxylherderite, which has more hydroxyl ion than fluoride.

<span class="mw-page-title-main">Phosphate mineral</span> Nickel–Strunz 9 ed mineral class number 8 (isolated tetrahedral units, mainly)

Phosphate minerals contain the tetrahedrally coordinated phosphate (PO43−) anion, sometimes with arsenate (AsO43−) and vanadate (VO43−) substitutions, along with chloride (Cl), fluoride (F), and hydroxide (OH) anions, that also fit into the crystal structure.

<span class="mw-page-title-main">Tricalcium phosphate</span> Chemical compound

Tricalcium phosphate (sometimes abbreviated TCP), more commonly known as Calcium phosphate, is a calcium salt of phosphoric acid with the chemical formula Ca3(PO4)2. It is also known as tribasic calcium phosphate and bone phosphate of lime (BPL). It is a white solid of low solubility. Most commercial samples of "tricalcium phosphate" are in fact hydroxyapatite.

<span class="mw-page-title-main">Monocalcium phosphate</span> Chemical compound

Monocalcium phosphate is an inorganic compound with the chemical formula Ca(H2PO4)2 ("AMCP" or "CMP-A" for anhydrous monocalcium phosphate). It is commonly found as the monohydrate ("MCP" or "MCP-M"), Ca(H2PO4)2·H2O. Both salts are colourless solids. They are used mainly as superphosphate fertilizers and are also popular leavening agents.

<span class="mw-page-title-main">Sodium monofluorophosphate</span> Chemical compound

Sodium monofluorophosphate, commonly abbreviated SMFP, is an inorganic compound with the chemical formula Na2PO3F. Typical for a salt, MFP is odourless, colourless, and water-soluble. This salt is an ingredient in some toothpastes.

<span class="mw-page-title-main">Phosphorus cycle</span> Biogeochemical movement

The phosphorus cycle is the biogeochemical cycle that describes the movement of phosphorus through the lithosphere, hydrosphere, and biosphere. Unlike many other biogeochemical cycles, the atmosphere does not play a significant role in the movement of phosphorus, because phosphorus and phosphorus-based compounds are usually solids at the typical ranges of temperature and pressure found on Earth. The production of phosphine gas occurs in only specialized, local conditions. Therefore, the phosphorus cycle should be viewed from whole Earth system and then specifically focused on the cycle in terrestrial and aquatic systems.

<span class="mw-page-title-main">Cesanite</span>

Cesanite is the end member of the apatite-wilkeite-ellestadite series that substitutes all of apatite's phosphate ions with sulfate ions and balances the difference in charge by replacing several calcium ions with sodium ions. Currently very few sites bearing cesanite have been found and are limited to a geothermal field in Cesano, Italy from which its name is derived, Măgurici Cave in Romania, and in the San Salvador Island caves in the Bahamas.

<span class="mw-page-title-main">Fluorellestadite</span> Nesosilicate mineral

Fluorellestadite is a rare nesosilicate of calcium, with sulfate and fluorine, with the chemical formula Ca10(SiO4)3(SO4)3F2. It is a member of the apatite group, and forms a series with hydroxylellestadite.

Tetracalcium phosphate is the compound Ca4(PO4)2O, (4CaO·P2O5). It is the most basic of the calcium phosphates, and has a Ca/P ratio of 2, making it the most phosphorus poor phosphate. It is found as the mineral hilgenstockite, which is formed in industrial phosphate rich slag (called "Thomas slag"). This slag was used as a fertiliser due to the higher solubility of tetracalcium phosphate relative to apatite minerals. Tetracalcium phosphate is a component in some calcium phosphate cements that have medical applications.

References

  1. Warr, L.N. (2021). "IMA–CNMNC approved mineral symbols". Mineralogical Magazine. 85 (3): 291–320. Bibcode:2021MinM...85..291W. doi: 10.1180/mgm.2021.43 . S2CID   235729616.
  2. 1 2 "Fluorapatite" Archived 2012-02-08 at the Wayback Machine . Handbook of Mineralogy.
  3. Apatite-(CaF) Mineral Data Archived 2016-10-30 at the Wayback Machine . webmineral.com.
  4. "Fluorapatite". mindat.org. Archived from the original on 2018-03-08. Retrieved 2013-11-17.
  5. 1 2 Klein, Cornelis; Hurlbut, Cornelius Searle; Dana, James Dwight (1999), Manual of Mineralogy (21 ed.), Wiley, ISBN   0-471-31266-5
  6. "How does fluoride protect my teeth and make them strong?". UCSB Science Line. Regents of the University of California. Archived from the original on 27 October 2017. Retrieved 3 June 2016.
  7. Trushkowsky, Richard. "The science of caries diagnosis" Archived 2016-07-01 at the Wayback Machine . Dentistry IQ.
  8. Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN   0-12-352651-5.
  9. Henderson and Marsden, Lamps and Lighting, Edward Arnold Press, 1972, ISBN   0-7131-3267-1
  10. Gemstones of the World By Walter Schumann, p. 18, 23, 29, 34, 56, 83