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By Miguel Álvarez Uriarte

El presente texto describe la producción, consumo, comercialización, importaciones, exportaciones y el ácido fluohídrico de la fluorita. El espato flúor o fluorita es un mineral no metálico libre de impurezas que contiene 48. 7% de flúor y 51.3% de calcio y se presenta de forma cristalizada y en diferentes coloraciones. De acuerdo al contenido de fluoruro de calcio, varían sus calidades y usos tales como: fundente de metales para aumentar la fluidez del acero fundido; industria de vidrio por sus propiedades opalecentes y colorantes; la industria de esmaltado en el acabado de estufas, refrigeradores, mosaicos; la industria de la cerámica para darle un aspecto vidrioso a las vajillas; y el grado óptico para la fabricación de lentes por el bajo índice de refracción y débil poder disperso de los colores.

Sep 1, 1975

By Miguel Álvarez Uriarte

Como consecuencia de las bajas cotizaciones internacionales que hubo para la fluorita en la primera mitad del decenio de 1960, su producción creció lentamente respecto a los requerimientos del consumo mundial. Dicha escasez se reflejó en una recuperación de los precios y fue suficiente incentivo, junto con otros factores, para que la producción mundial del metaloide aumentará notablemente en 1971. En ese sentido, el presente texto describe el panorama de la fluorita en México a través del Instituto Mexicano de la Fluorita y así obtener información actualizada sobre el mercado y producciones mundiales, la situación de proyectos mineros de fluorita en otros países y sobre el desarrollo y usos de sustitutos de la fluorita.

Nov 1, 1975

By Thomas L. Watson

MY thanks are due to Mr. Frank Firmstone, Easton, Pa., who has called my attention to the statement in my papers that " Barite, fluorite and quartz, though not observed in the Tennessee area," . . . as possibly misleading to the reader, if construed to mean that such a discovery had never been made. Mr. Firmstone is correct in assuming that this statement referred only to the study of the worked areas of the metallic ores, especially zinc, made in the course of the survey upon which my paper was based. The occurrence of barite and fluorite with lead-ores in Tennessee was reported by Prof. Safford,2 in 1869, and by Safford and Killebrew,3 in 1887, with the further statement that about 1,000,000 lb. of barite were annually mined in Greene, Washington and Jefferson counties, Tenn., and that considerable deposits occur also in McMinn, Smith and other counties. It is also noted that the barite ".usually occurs in veins, associated with galena." The present worked areas of barite are, however, distinct barite propositions, without workable quantities of either lead or zinc, so far as mining operations have gone, and the areas are more or less removed from the present areas of zinc-ores. Mr. Firmstone informs me also that, in 1892, he observed, in the magnesian limestone at Watauga Point, in Carter county, on the left bank of the Watauga river, a little below the mouth of Buffalo creek, small quantities of galena and some fluorite.

Jan 1, 1907

By Z. D. Hora

The major fluorite producer in British Columbia was the Rock Candy Mine, inactive since 1942. Other deposits of economic interest include the Rexspar deposit, in which fluorite is associated with uranium and rare earth mineralization, and the Eaglet and Liard River occurrences. THE former Rock Candy fluorite mine, located 26 km north of Grand Forks, is the only major past producer of fluorite in British Columbia. The deposit was in production from 1918 to 1929 and again in 1942; total output was about 36,000 tonnes with average grade between 22 and 32 per cent CaF2. The fluorite body occupies a steeply-dipping vein structure, approximately 175 m long and up to 12 m wide, in porphyritic syenite. The chief vein-filling minerals are quartz and fluorite with local small len ses of barite. Fluorite content decreases with depth and the deposit becomes silicified. The Rexspar (or Birch Island) fluorite deposit is located 130 km north of Kamloops. The deposit is complex with rare earth elements and high uranium values, but !1uorite mineralization forms an independent zone adjacent to the uranium orebodies. Fluorite is present as fine-grained impregnations and as breccia cement in strongly schistose or brecciated alkali feld spar porphyry. Reported reserves are 1,088,000 tonnes of 22 per cent CaF2 or 450,000 tonnes of 29 per cent CaF2. 268 Another potential deposit of fluorite is Eaglet, situated on the north side of Quesnel Lake. Fluorite occurs as a stock work with scattered veins and irregular lenses up to 20 centimetres wide and as impregnations in altered Proterozoic Kaza Group feld spathic gneiss over an area of 1,500 metres by 500 metres. To date (1983) approximately $2 million have been spent on the exploration of this property and reserves of 18.8 mimon tonnes grading 11.59 per cent CaF2 have been outlined . A group of significant occurrences is known from north of Liard River Hot Springs Park , where fluorite occurs in small zones up to 17 m thick along the interface between Middle Devonian Dunedin Formation limestone and Middle Devonian to Mississippian Besa River Formation argillite. Fluorite, associated with witherite, barytocalcite and barite, is present as replacement bodies, breccia fillings and minor veins.

Jan 1, 1984

By P. R. A. Andrews, R. K. Collings

"There are more than 300 occurrences of fluorite in Canada. Deposits of economic significance, however, are confined to Newfoundland and Nova Scotia in eastern Canada, Ontario in central Canada, and British Columbia in western Canada. Fluorite has been mined and processed intermittently in Ontario and Newfoundland until November 1990, when Canada's only producer Minworth Ltd., a U.K. based company, with a mine and concentrator near St. Lawrence on the Burin Peninsula, Newfoundland, closed its operation.CANMET has processed ore samples from each of the major mineralized areas, and thirty-one studies were conducted between 1920and 1970. A summary of the important aspects of the various testwork studies is presented. The production of acid-grade fluorite was possible by flotation, and ceramic-grade, by flotation and gravity concentration methods. Gravity concentration methods included heavy media separation, jigging and tabling. Flotation was by direct and reverse techniques; associated minerals, quartz, calcite, barite, etc. were depressed by a variety of depressants. The function of the major depressants is discussed briefly. The various uses offluorite which include hydrofluoric acid, chlorofluorocarbons, aluminum production, petroleum alkylation, fluxing and ceramic applications etc. are discussed briefly."

Jan 1, 1993

By R. B. Strathmore Cooke, Eugene L. Talbot

The perfluoro acids and derivatives show unusual surface-active properties that qualify them as possible flotation reagents. They lower the surface tension of water from 15 to 20 dynes below that obtainable with the corresponding hydrocarbon compounds. Fluorochemicals adsorb very strongly on solid surfaces to give films that exhibit larger contact angles than films of the corresponding hydro-carbons. The large contact angles probably result from the terminal –CF3 group. The perfluoro acids are made by electrolysis of the corresponding carboxylic acid in anhydrous hydrogen fluoride. From the perfluoro acids many derivatives may be obtained, such as amides, amines, alcohols, xanthates, ethers and esters and others.

Nov 1, 1955

By S. L. Weber, V. Castranova, D. E. Banks, J. K. H. Ma, Y. Rojanasakul, J. Y. C. Ma, M. Bhat

"The mechanism of bleomycin-induced pulmonary fibrosis is not ye: clear. Recent studies have shown that alveolar macrophages (AM) can be stimulated by bleomycin in vitro releasing inflammatory cytokines, suggesting that the interaction of bleomycin with AM is an important step in the drug-induced fibrotic process. Bleomycin is known to bind DNA and generate oxygen radicals through complexation with Fe2+ and oxygen. To provide,more insight into the cellular oxidative property of bleomycin, v.s have developed a fluoromicroscopic method using 2',7'-dichlorofluorescin diacetate (DCFHDA) as an oxidative fluorescence probe to study the deomycin-induced intracellular oxidation in rat AM and the inhibition of the oxida¬tion by taurine, a compound known to inhibit the bleomycin-induced fibrosis. Bleomycin at 5 to 20 ug/ml has a moderate stimulatory effect (1.87- to 2.66-fold) on the secretion of superoxide anion. A high concentration of bleomycin (20 ug/ml), however, inhibits cell response to zymosan-induced secretion of superoxide anion. At 4 ug/ml, bleomycin has no effect on cell membrane integrity or morphology but results in a significant increase in intracellular oxidation. This oxidative process is Fe2-,-dependent and is accompanied by an increase in intracellular calcium (35 nM). Both the intracellular oxidation and calcium rise induced by internalized bleomycin are inhibited by pretreatment of cells with varying concentrations of taurine (25, 125, and 187.5 uM). The inhibitory effect on intracellular oxidation .vas found to be 36, 57, and 60%, respectively. These results demonstrate a stimulation-inhibition relationship between bleomycin and taurine on re cellular oxidation at a subcytotoxic dose of bleomycin, suggesting that the oxidative effect of the intracellular bleomycin-Fe2 complex is important in the initiation of the fibrotic process. — Environ Health Perspect 102 (Suppl10):91-96 (1994) IntroductionThe pulmonary system is most susceptible to oxygen radical-induced diseases due to its constant exposure to the highest oxygen tension, and the potential encounters with oxidant gases such as ozone, nitrogen oxides, and toxic doses of dust particles. The lung is also a well-perfused organ and thereby vulnerable to the effect of circulating xenobiotics such as paraquat, and, bleomycin, which is known to cause pulmonary injuries (1). Alveolar macrophages (AM), which act as a means of defense by phagocytizing inhaled dust particles and microorganisms while increasing production of reactive oxidative species, have been shown to play an important role in mechanisms leading to oxidative lung injury and fibrosis (2-4)."

Dec 1, 1995

By Henry Siegmann

HISTORY OF PRODUCTION AND USE In 1899 the consumption of fluorspar in the United States was reported as 16,000 tons. The invention of the open-hearth method of steel manufacture, plus the beginnings of a fluorine chemical industry, pushed consumption of fluorspar to 250,000 tons by 1918. In contrast to these consumption statistics of the past, the most recent statistics available (1972) indicate a total fluorspar usage in the United States of 1.352 million st (Table 15.4D.1). Fluorspar remains the world's cheapest source of fluorine, and its unique properties make the mineral the most desirable fluxing agent for steel refining. The linking of fluorine with carbon in the late 1930s resulted in the production of fluorocarbon, and constant growth in production over the years has formed the backbone of a strong fluorine chemical industry. For example, in 1972 it is estimated that total fluorocarbon production amounted to 2.113 million tons, and that, in this process, over 1.351 million tons of acid-grade fluorspar was consumed. The producers of primary aluminum long have been concerned about the fast dwindling reserves of natural cryolite. They found the solution to their problem by utilizing fluorspar for the manufacture of synthetic cryolite and aluminum fluoride. Nuclear weapons, as well as the growing number of peaceful uses for atomic reactors, constitute a market for uranium hexafluoride. This chemical and chlorine pentafluoride, used as an oxidizer with rocket fuels, are products that are as much a novelty as fluorocarbons were 25 years ago. Judging from past success in the field of fluorine chemistry research, it is safe to assume that the market for these chemicals will grow in the future. Three major industries account for the bulk of the fluorspar consumption: steel refining, fluorine chemical, and primary aluminum production. These industries have had a pattern of fabulous growth in the past, and their future plans point to a continuation of this pattern. It seems logical that the fluorspar usage also should continue its upward trend. Considering the growth of the fluorspar industry since 1899, and the obvious dependence on imports of fluorspar as a raw material, one of the most puzzling aspects of the past has been the apparent lack of coordination between fluorspar production and fluorspar consumption. A few authoritative voices have spoken out concerning the need to expand fluorspar production in order to meet consumption of the future. During World War II, the U.S. Government took positive steps in this direction by authorizing purchases at attractive prices for its "stockpile program." As a consequence, new fluorspar producing facilities were built, not only in

Jan 1, 1976

By Robert B. Fulton, Gill Montgomery

Fluorspar is the commercial name for fluorite, a mineral that is calcium fluoride, CaF2. The name, derived from the Latin word fluere (to flow), refers to its low melting point and its early use in metallurgy as a flux. It is the principal industrial source of the element fluorine. Two other minerals, cryolite and fluorapatite, have significant fluorine content. Cryolite, sodium aluminum fluoride, Na3AlF,, is a rare mineral that has been found in commercial quantities only in Greenland. The natural material has been supplanted by synthetic cryolite for its principal industrial use in the manufacture of aluminum. Fluorapatite, Ca5F(PO3)2, is a source of phosphate for fertilizer manufacture, containing a small percentage of fluorine. Commercially mined deposits of apatite have varying amounts of fluorine, chlorine, hydroxyl, and carbonate. HISTORY Fluorspar was used by the early Greeks and Romans for ornamental purposes as vases, drinking cups, and table tops. Various peoples, including the Chinese and the American Indians, carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola in 16th century Europe. Fluorspar mining began in England about 1775 and at various places in the United States between 1820 and 1840. Production grew substantially following the development of basic open hearth steelmaking, wherein it is used as a flux. Use was stimulated by growth of the steel, aluminum, chemical, and ceramic industries, particularly during World Wars I and 11. Fluorocarbons entered the picture in 1931. The use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel began in 1942. Differential flotation for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s and the application of heavy media concentrating methods to the treatment of low grade ores in the 1940s were outstanding technological advances that facilitated increased production. Pelletizing and briquetting of flotation concentrates for use in steel furnaces and the development of flotation schemes for beneficiating ores containing abundant dolomite and barite have been major improvements in the industry. USES OF FLUORITE Fluorspar is used to make hydrogen fluoride (HF), also called hydrofluoric acid, an intermediate for fluorocarbons, aluminum fluoride, and synthetic cryolite. It is used as a flux in the steel and ceramic industries, in iron foundry and ferroalloy practice, and has many minor specialized uses. Hydrogen fluoride is produced by reacting acid grade (97% CaF,) fluorspar with sulfuric acid in a heated kiln or retort to produce HF gas and calcium sulfate. After purification by scrubbing, condensing, and distillation; the HF is marketed as anhydrous HF, a colorless fuming liquid, or it may be absorbed in water to form the aqueous acid, usually 70% HF. Synthetic cryolite, organic and inorganic fluoride chemicals, and elemental fluorine are made from hydrofluoric acid. The acid itself is important in catalysis in the manufacture of alkylate, an ingredient in high-octane fuel for aircraft and automobiles; in steel pickling, enamel stripping, and glass etching and polishing; and in various electroplating operations. The manufacture of one ton of virgin aluminum requires about 12 to 29 kg of fluorine content in synthetic cryolite and aluminum fluoride. This quantity, through improved technology and recovery practices, is being lowered significantly in countries with the most advanced technology (i.e., Australia and Sweden), while others (i.e., Surinam and South Africa), remain at the high end. Elemental fluorine is prepared from anhydrous hydrofluoric acid by electrolysis. Gaseous at room temperature and pressure, fluorine is compressed to a liquid for shipment in cylinders or in tank trucks. Elemental fluorine is used to make uranium hexafluoride, sulfur hexafluoride, and halogen fluorides. Gaseous uranium hexafluoride is used in separating U235 from U233 by the diffusion process. Sulfur hexafluoride is a stable high dielectric gas used in coaxial cables, transformers, and radar wave guides. Halogen fluorides have important applications, mostly as substitutes for elemental fluorine, which is more difficult to handle. Emulsified perfluorochemicals, organic compounds in which all hydrogen atoms have been replaced by fluorine, are undergoing investigation as promising blood substitutes. They transport oxygen and, in conjunction with a simulated blood serum, perform many functions of whole blood. With further development, these organic compounds may ultimately, in emergencies, be useful in saving lives of animals and humans during periods of acute shortages of natural blood. Inorganic fluorides are used as insecticides, preservatives, antiseptics, ceramic additives, and fluxes and in electroplating solutions, antioxidants, and many other products. Boron trifluoride is an important catalyst. Organic fluorides are volume leaders in the fluorine chemical industry. Fluorinated chlorocarbons and fluorocarbons are prepared by the interaction of anhydrous HF with chloroform, perchlorethylene and carbon tetrachloride, and are characterized by low toxicity and notable chemical stability. They perform outstandingly as refrigerants, aerosol propellants, solvents, and cleaning agents and as intermediates for polymers such as fluorocarbon resins and elastomers. Fluorocarbon resins are inert compounds that have unusually low coefficients of friction and have found a number of applications as lubricants for parts that cannot be oiled, e.g., bearings for window raising equipment located inside of automobile doors, in small electronic equipment, for the manufacture of chem-

Jan 1, 1994

By C. B. Rash, W. W. Fowler, Gill Montgomery

INTRODUCTION Fluorspar is the common term used for the mineral fluorite, which is naturally occurring calcium fluoride (CaF2). It is the principal source of fluorine, the most reactive of the chemical elements, from which a great variety of unique and strategically important chemicals are produced. Commercial deposits of fluorspar are widespread throughout the world, and its availability is essential to the industrial progress of all nations. GEOLOGY AND MINERALOGY In its pure form fluorspar, CaF2, contains 51.1% calcium and 48.9% fluorine, and has a sp gr of 3.18 and a hardness of 4. It is commonly a glassy mineral. colorless, white, or grayish. but may also be various shades of purple, pink, blue, green, yellow, or tan. It belongs to the cubic system mineralogically, and commonly crystallizes into cubic shapes in vugs and cavities, although most of it is massive, with interlocking crystals. Minable fluorspar deposits, in descending order of importance, occur as bedded limestone replacement deposits along fault zones; fissure-filling vein deposits; breccia filling in limestones, dolomites,

Jan 1, 1985

By William I. Weisman

The annual consumption of fluorspar in the United States, in the last 10 years has doubled. In 1971, when 1,344,742 tons were consumed, almost 45 percent of this amount was used in the production of steel and nearly 50 percent was consumed in the manufacture of hydrofluoric acid. Of the hydrofluoric acid produced, about one-third was used in the manufacture of aluminum electrolytes for production of primary aluminum metal and the balance was consumed in the manufacture of a variety of fluorocarbons and other chemicals. A small amount of fluorspar, constituting less than five percent of total consumption, was used in the foundry industry, and in the manufacture of glass, enamel, cement and other products. It is apparent that a continuing supply of fluorspar will be required to meet the demands for these vital metals and chemicals in our expanding industrial society. Domestic fluorspar production meets only approximately 20 percent of our needs. Hence, it is essential that the United States maintain a healthy domestic fluorspar industry in order to have adequate domestic reserves available at times of emergency and to protect this country from becoming solely dependent on foreign sources for this strategic commodity.

Jan 1, 1973

By C. M. Bartley

Fluorspar, in addition to its familiar uses as a metallurgical flux and as a source of the electrolyte for aluminum production, has become important as an essential raw material in the rapidly growing fluorine chemical industry. The unique ability of fluorine to react and form compounds with al-most all other chemicals has made it one of the important elements in modern chemistry. Research and development over the past thirty years have resulted in a current annual production of fluorine chemicals that is both technically and economically important to industry. Because many of these chemicals and products are relatively new, and most have properties that are not duplicated by other materials, the present uses are expanding rapidly and new applications are being reported continually. Fluorspar, the only immediate and practical source of fluorine, is therefore an important mineral. This fact has been recognized in major industrial areas such as the United States and Western Europe, but has received little attention in Canada.

Jan 1, 1962

By Gill Montgomery

The strong upward curve of fluorspar consumption continued through 1968, with domestic producers unable to furnish more than 30% of U.S. requirements. Stocks of all grades were quite short at all points during most of 1968. This resulted in price increases as both domestic and foreign producers sought to cover spiralling labor costs. Further increases are probable for 1969. All Illinois mines were closed by strikes in January and February. The strong trend in metallurgical imports reflects the increased use of fluorspar in steelmaking, as new oxygen process steel plants come into production. The growth of use of all fluorocarbon chemicals continues to require additional acid grade fluorspar, with military uses a major factor. Several new aluminum smelting facilities coming into production are adding to the aluminum fluoride needs, bringing further pressure upon the world supply of acid grade fluorspar. The world-wide consumption pressure on all grades of fluorspar is pushing prices up, and no end to the tight supply is in sight, even assuming that all the new projects cited here are finished on schedule.

Jan 3, 1969

By Robert M. Grogan, Gill Montgomery

Fluorspar, the commercial name for fluorite, is a mineral composed of calcium fluoride, CaF,. Its valuable properties are due to its content of fluorine, and it is the principal commercial source of that element. The name is derived from the Latin word "fluere," to flow, because the mineral has a low melting point and is used in metallurgy as a flux. Cryolite is a sodium aluminum fluoride, Na,AlF,. It is a rare mineral which has been found in commercial quantities in only one place in the world, Greenland. Small amounts of it are shipped from stock in that country, and its place in industry has been taken over almost completely by synthetic cryolite. Because of the relative unimportance of cryolite, discussion of it has been relegated to a short section at the end of this chapter, which is principally concerned with fluorspar. History Fluorspar was used for ornamental purposes by the Greeks and Romans, who fashioned such things as vases, drinking cups, and table tops from it. Various peoples including the Chinese and the American Indians carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola (1564), who wrote about it in 1546. Mining began in England about 1775 and at various places in the United States during the period 1820 to 1840. Production became substantial following the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage were stimulated by growth in the steel, aluminum, chemical, and ceramic industries and were accelerated by World Wars I and II. Fluorocarbons entered the picture in 193 1 and the use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920s, a differential flotation scheme for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low grade ores in the 1940s were outstanding technological contributions that enabled increased production of fluorspar concentrates. In recent years the development of pelletizing and briquetting processes for making flotation concentrates into gravel-size particles for use in steel furnaces and the development of more efficient and selective flotation schemes for treating crude ores containing abundant dolomite and barite have been major improvements in the industry.

Jan 1, 1975

By Robert B. Fulton, Gill Montgomery

Fluorspar is the commercial name for fluorite, a mineral that is calcium fluoride, CaF2. The name, derived from the Latin word fluere (to flow), refers to its low melting point and its early use in metallurgy as a flux. It is the principal industrial source of the element fluorine. Cryolite, sodium aluminum fluoride, Na3AlF6, is a rare mineral which has been found in commercial quantities only in Greenland. The natural material has been supplanted by synthetic cryolite for its principal industrial use in the manufacture of aluminum. History Fluorspar was used by the early Greeks and Romans for ornamental purposes as vases, drinking cups, and table tops. Various peoples, including the Chinese and the American Indians, carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola in sixteenth century Europe. Fluorspar mining began in England about 1775 and at various places in the United States between 1820 and 1840. Production grew substantially following the development of basic open-hearth steelmaking, wherein it is used as a flux. Use was stimulated by growth of the steel, aluminum, chemical, and ceramic industries, particularly during World Wars I and II. Fluorocarbons entered the picture in 1931. The use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel began in 1942. Differential flotation for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940s were outstanding technological advances that facilitated increased production. Recently, pelletizing and briquetting of flotation concentrates for use in steel furnaces and the development of flotation schemes for beneficiating ores containing abundant dolomite and barite have been major improvements in the industry. Uses of Fluorspar Fluorspar is used to make hydrogen fluoride, also called hydrofluoric acid, an intermediate for fluorocarbons, aluminum fluoride, and synthetic cryolite. It is used as a flux in the steel and ceramic industries, in iron foundry and ferroalloy practice, and has many minor specialized uses. Hydrogen fluoride (HF) is produced by reacting acid grade (97% CaF2) fluorspar with sulfuric acid in a heated kiln or retort to produce HF gas and calcium sulfate. After purification by scrubbing, condensing, and distillation, the HF is marketed as anhydrous HF, a colorless fuming liquid, or it may be absorbed in water to form the aqueous acid, usually 70% HF. Synthetic cryolite, organic and inorganic fluoride chemicals, and elemental fluorine are made from hydrofluoric acid. The acid itself is important in catalysis in the manufacture of alkylate, which is an ingredient in high-octane fuel for aircraft and automobiles, in steel pickling, enamel stripping, glass etching and polishing, and in various electroplating operations. The manufacture of one ton of virgin aluminum requires about 50 to 60 lb of fluorine content in synthetic cryolite and alumnium fluoride. This quantity, through improved technology and recovery practices, is being lowered significantly.

Jan 1, 1983

By Henry T. Mudd

FLUORSPAR is a nonmetallic mineral aggregate or mass containing a sufficient quantity of fluorite (CaF2) to be of commercial interest. It has only moderate value per unit of weight and its cost as a percentage of the cost of finished consumer products is nearly negligible. Nevertheless, it has wide and great industrial importance. In periods of national emergency it is a mineral without which many very necessary manufacturing processes would be greatly handicapped; a few could not exist. Fluorite contains 51.1 pct calcium and 48.9 pct fluorine. Industrial grades of fluorspar prepared for the consumer normally contain from 85 to 98 pct fluorite, depending on the use. The ores may contain as little as 30 pct fluorite, depending on many factors such as accessibility to transportation and markets, character of ore, and prices. Fluorite is a lustrous, glasslike mineral, generally translucent to transparent; it may be clear and colorless or range in color from slightly bluish through various shades of violet, amethyst, purple, green, and yellow. It crystallizes in the isometric system and possesses perfect octahedral cleavage. Commonly it occurs in masses of very pure crystal- line material with aggregates of cubical crystals in open spaces, but - it is also found in fine to coarse granular form. Banded veins and masses with fibrous, radiating structure occur locally. It is usually found associated more or less intimately with other minerals and rocks, from which it must be separated for commercial use. The specific gravity of fluorite is 3.18 and the hardness is 4 in the Mohs scale, compared with 7 for quartz and 3 for calcite. It is distinguished from calcite by its failure to effervesce with dilute hydrochloric acid. Heated with sulphuric acid, it gives off fumes of hydro- fluoric acid, which etch glass.22,25,33.34,35.41

Jan 1, 1949

By Robert M. Grogan

Fluorspar is the commercial name for fluorite, which is the mineral having the composition CaF2, calcium fluoride. Its valuable properties are due to its content of fluorine, and it is the only important commercial source of that element. The name is derived from the Latin fluere, to flow, because the mineral melts easily and is a good flux. History The mineral has been known since Greek and Roman times, when it was used for drinking cups and ornamental slabs. Various peoples including the Chinese and the American Indians have carved ornaments from large crystals. Its usefulness as a flux was known to Agricola, who wrote about it in 1546.1 Mining began in England about 1775 15 and at various places in the United States during the period 1820 to 1840.28 Substantial production was achieved first in the period 1888 to 1900 in consequence of the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage was stimulated by growth in the steel, aluminum, chemical, and ceramic industries and accelerated by World Wars I and II. The organic fluorides called "Freons" entered the picture in 1931, and the use of anhydrous HF as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920's, a differential flotation scheme for separating fluorspar from galena, sphalerite, and other minerals in the 1930's, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940's were outstanding technological contributions that enabled increased production of fluorspar concentrates. Composition and Properties Fluorite in its purest form contains 51.1 pct calcium and 48.9 pct fluorine. Substitution of small percentages of cerium and yttrium for calcium have been noted.4 Mechanical inclusions of gases and fluids such as petroleum and water, and of other solid minerals such as pyrite, marcasite, and chalcopyrite are common. The fluorspar of commerce contains attached and admixed mineral impurities, chiefly calcite, quartz, barite, celestite, and various sulfides. It is interesting that the purest commercial form in which the mineral is sold, acid grade concentrate, contains a minimum of 97 pct CaF2, and as such is of comparable purity to many reagents used in chemical laboratories. Fluorite has a marked tendency to occur in large, well-formed crystals sometimes six to ten inches on a side. It crystallizes in the isometric system, frequently forming cubic and octahedral crystals or combinations thereof. The mineral also occurs in massive and in earthy forms, and in crusts or globular aggregates with radial fibrous texture. Crystalline fluorspar exhibits a great array of colors, from colorless and water clear to yellow, blue, purple, green, rose, red, bluish and purplish black, and brown. The colors are often arranged in alternating bands parallel to cube faces. They may be altered by exposure to X-rays, heat, ultraviolet light, and pressure, and are caused by a variety of factors including the presence of trace impurities and displaced ions in the lattice. Sometimes the changes induced by X-rays can be reversed by ultraviolet radiation. The mineral has a hardness of 4, and is the model of that hardness on the Mobs scale.

Jan 1, 1960

By E. L. BROKENSHIRE

FLUORSPAR, a little known non-metallic mineral, referred to technically as fluorite, chemically as calcium fluoride, is a compound of calcium and fluorine in the ratio of one molecule of calcium to two of fluorine. By weight it is composed of 51.3 per cent of calcium and 48.7 per cent of fluorine. Its specific gravity is 3.2. It is brittle, has a hardness of four and can be easily scratched with a knife. It weighs about 200 Ib. per cubic foot and has a melting point of 1650" F. The color of fluorspar ranges from pure white and opaque white, according to its purity, to various hues of yellow, green, pink, lavender, blue and brown, to bluish black. Although the lumps have color, when ground the fluorspar becomes pure white. The reason for this is because the mineral usually carries no fixed pigment, the color being produced by the re- fraction of light rays within the crystal structure and small quantities of organic matter which readily oxidizes. It crystallizes in the isometric system with perfect octahedral cleavages.

Jan 1, 1929

The fluorspar deposits at Okorusu, Namibia are closely related to an alkaline igneous ring complex of late Cretaceous age (125¦7 Ma). The fluorite ores consist of relatively fine-grained purple replacement fluorite and subsequent coarser-grained purple and green vug-filling fluorite crystals. Homogenisation temperature measurements for 38 primary fluid inclusions shows that main stage purple to green fluorite crystals were deposited over a temperature range from 166¦C to 144¦C, and minor late yellow fluorite was deposited at lower temperatures from 132¦C to 128¦C. Homogenisation and freezing temperatures measured for 18 primary fluid inclusions shows that the fluorite-depositing fluids were less saline than Mississippi Valley-Type (MVT) ore fluids and overlap the lower temperature range of fluids that deposited epithermal ore deposits. Mining in three open pits (A, B and C) at Okorusu has gradually provided exposures which reveal that the fluorite orebodies have been emplaced primarily by the preferential replacement of carbonatites. Evidence for the replacement of carbonatite includes: replacement remnants of carbonatite within the fluorite ores; goethite pseudomorphs after the carbonatite minerals, pyroxene, pyrrhotite and magnetite, which are disseminated in the fluorite ores; andpartial replacement by fluorite of a large sill-like carbonatite body in the A pit. Electron microprobe analyses of minerals in unreplaced portions of the carbonatites show that their mineralogy consists of titaniferous magnetite, diopside pyroxene, apatite, biotite and calcite. Magnetite contains 6.97 per cent to 10.46 per cent TiO2, averages 8.44 per cent TiO2, and has an average V2O3 content of 0.35 per cent. At high magnifications under the scanning electron microscope (SEM), the magnetite shows abundant fine ulv÷spinel exsolution lamellae arranged in a cloth texture. Apatite contains moderately high fluorine contents that range from 3.21 to 5.0 per cent and average 4.2 per cent, and apatite crystals range in total rare earth oxides from 1.7 per cent to 2.61 per cent. Pyroxenes in the carbonatites are iron-rich diopside, and they contrast to pyroxenes in the fenites that are aegirine-augite. All of the microprobe analyses for mica crystals in the carbonatites give biotite compositions. Microscopic examination of fluorite concentrates from Okorusu provides mineralogical information important to the resolution of beneficiation problems. Fluorite ores that are related to carbonatites are typically accompanied by phosphorus benefication problems. The cause for the presence of phosphate in some of the Okorusu fluorite concentrates is a function of the presence of binary locked fluorite-apatite particles. The fluorite ores have also replaced marble locally in the A pit, especially along the A band in the B pit, and dominantly in the orebody proposed for the new C pit. Those ores are characterised by fine grain sizes, faint remnant bedding, lack of carbonatite mineral pseudomorphs and local presence of remnants of unreplaced marble. Concentrates derived from those fluorite ores are devoid of phosphorus, but commonly have elevated silica contents due the presence of free quartz. Carbonatite and marble were preferentially replaced by fluorite because the calcite was readily soluble in the presence of the fluorite-depositing fluids and the dissolution of calcite provided calcium for the formation of fluorite. 

Jan 1, 2008

By J. L. Gillson

IN a brief summary of the many occurrences of fluorspar in our western states, it is not possible to go into detail in regard to the geology, mining and milling methods, and reserves about individual deposits. Rather a broad review is made of the occurrences and an analysis of how the western deposits may fit into our future domestic economy is presented. GENERAL STATEMENT ON FLUORSPAR SITUATION Fluorspar has been used for years as a flux in the manufacture of basic open-hearth steel, in foundry cupolas for melting pig iron, in the manufacture of opalescent glass and in the preparation of hydrofluoric acid. In 1880 the annual production of fluorspar in the United States was around 4000 tons per year. By 1900 it was up to 21,656 tons and between 1902 and 1908 it averaged about 40,000 tons annually. Prices were then so low, by present standards, that it seems impossible to believe now that mining could have been performed profitably at the price levels then prevailing. In 1890 fluorspar sold at the mines for $6.70 per ton, in I901 for $5.81, in 1916 for $5.92. When the United States entered World War I, fluorspar production and price skyrocketed; the production reached 263,817 tons in 1918, with prices above $20.00 per ton, and prices were even higher in 1919 and 1920. After 1920, the domestic production fell from the 1918 level to about 125,000 tons annually and the average price dropped back to about $I8.00 per ton. By 1935 the average price had fallen to $15.00, but in 194o with a rising demand the average price of all grades had gone back up to $20.31. Today it is 75 per cent higher than in 1940 and presumably the price of acid grade at least would be even higher if it were not for price ceilings. The first subsequent year that the domestic production exceeded that of 1918 was 1941, and the 1944 production is expected to exceed 400,000 tons, 'or over one and a half times that of 1918. In five-year periods, average production and imports were as are shown in Table I. [ ] Many people concerned with the consumption of fluorspar believe that the postwar period ahead will show a repetition of price trends of the last such period. They believe that imports will be- again an important factor in the available supply and the price will fall back gradually toward the prewar level. The following basic factors are pertinent in analyzing this conclusion:

Jan 1, 1945