Baryte, barite or barytes ([7] or [8]) is a mineral consisting of barium sulfate (BaSO4).[3] Baryte is generally white or colorless, and is the main source of the element barium. The baryte group consists of baryte, celestine (strontium sulfate), anglesite (lead sulfate), and anhydrite (calcium sulfate). Baryte and celestine form a solid solution (Ba,Sr)SO4.[2]
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The unit cell of baryteThe radiating form, sometimes referred to as Bologna Stone,[9] attained some notoriety among alchemists for specimens found in the 17th century near Bologna by Vincenzo Casciarolo. These became phosphorescent upon being calcined.[10][11]
Carl Scheele determined that baryte contained a new element in , but could not isolate barium, only barium oxide. Johan Gottlieb Gahn also isolated barium oxide two years later in similar studies. Barium was first isolated by electrolysis of molten barium salts in by Sir Humphry Davy in England.[12]
The American Petroleum Institute specification API 13/ISO , which governs baryte for drilling purposes, does not refer to any specific mineral, but rather a material that meets that specification.[13] In practice, however, this is usually the mineral baryte.[14]
The term "primary barytes" refers to the first marketable product, which includes crude baryte (run of mine) and the products of simple beneficiation methods, such as washing, jigging, heavy media separation, tabling, and flotation. Most crude baryte requires some upgrading to minimum purity or density. Baryte that is used as an aggregate in a "heavy" cement is crushed and screened to a uniform size. Most baryte is ground to a small, uniform size before it is used as a filler or extender, an addition to industrial products, in the production of barium chemicals or as a weighting agent in petroleum well drilling mud.[15]
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The name baryte is derived from the Ancient Greek: βαρύς, romanized: barús, 'heavy'. The American spelling is barite.[3][16] The International Mineralogical Association initially adopted "barite" as the official spelling, but recommended adopting the older "baryte" spelling later. This move was controversial and was notably ignored by American mineralogists.[17]
Other names have been used for baryte, including barytine,[18] barytite,[18] barytes,[19] heavy spar,[3] tiff,[4] and blanc fixe.[20]
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Baryte with galena and hematite from Poland Baryte (top) and dolomite from Cumbria, England Abandoned baryte mine shaft near Aberfeldy, Perthshire, ScotlandBaryte occurs in many depositional environments, and is deposited through many processes including biogenic, hydrothermal, and evaporation, among others.[2] Baryte commonly occurs in lead-zinc veins in limestones, in hot spring deposits, and with hematite ore. It is often associated with the minerals anglesite and celestine. It has also been identified in meteorites.[21]
Baryte has been found at locations in Australia, Brazil, Nigeria, Canada, Chile, China, India, Pakistan, Germany, Greece, Guatemala, Iran, Ireland (where it was mined on Benbulben[22]), Liberia, Mexico, Morocco, Peru, Romania (Baia Sprie), Turkey, South Africa (Barberton Mountain Land),[23] Thailand, United Kingdom (Cornwall, Cumbria, Dartmoor/Devon, Derbyshire, Durham, Shropshire,[24] Perthshire, Argyllshire, and Surrey[3]) and in the US from Cheshire, Connecticut, De Kalb, New York, and Fort Wallace, New Mexico. It is mined in Arkansas, Connecticut, Virginia, North Carolina, Georgia, Tennessee, Kentucky, Nevada, and Missouri.[3]
The global production of baryte in was estimated to be around 9.5 million metric tons, down from 9.8 million metric tons in .[25] The major barytes producers (in thousand tonnes, data for ) are as follows: China (3,600), India (1,600), Morocco (1,000), Mexico (400), United States (330), Iran (280), Turkey (250), Russia (210), Kazakhstan (160), Thailand (130) and Laos (120).[26]
The main users of barytes in were (in million tonnes) US (2.35), China (1.60), Middle East (1.55), the European Union and Norway (0.60), Russia and CIS (0.5), South America (0.35), Africa (0.25), and Canada (0.20). 70% of barytes was destined for oil and gas well drilling muds. 15% for barium chemicals, 14% for filler applications in automotive, construction, and paint industries, and 1% other applications.[26]
Natural baryte formed under hydrothermal conditions may be associated with quartz or silica.[27] In hydrothermal vents, the baryte-silica mineralisation can also be accompanied by precious metals.[28]
Information about the mineral resource base of baryte ores is presented in some scientific articles.[29]
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Worldwide, 69&#;77% of baryte is used as a weighting agent for drilling fluids in oil and gas exploration to suppress high formation pressures and prevent blowouts. As a well is drilled, the bit passes through various formations, each with different characteristics. The deeper the hole, the more baryte is needed as a percentage of the total mud mix. An additional benefit of baryte is that it is non-magnetic and thus does not interfere with magnetic measurements taken in the borehole, either during logging-while-drilling or in separate drill hole logging. Baryte used for drilling petroleum wells can be black, blue, brown or gray depending on the ore body. The baryte is finely ground so that at least 97% of the material, by weight, can pass through a 200-mesh (75 μm) screen, and no more than 30%, by weight, can be less than 6 μm diameter. The ground baryte also must be dense enough so that its specific gravity is 4.2 or greater, soft enough to not damage the bearings of a tricone drill bit, chemically inert, and containing no more than 250 milligrams per kilogram of soluble alkaline salts.[16] In August , the American Petroleum Institute published specifications to modify the 4.2 drilling grade standards for baryte to include 4.1 SG materials.
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Baryte (salmon-colored) with cerussite from MoroccoIn the deep ocean, away from continental sources of sediment, pelagic baryte precipitates and forms a significant amount of the sediments. Since baryte has oxygen, systematics in the δ18O of these sediments have been used to help constrain paleotemperatures for oceanic crust.
The variations in sulfur isotopes (34S/32S) are being examined in evaporite minerals containing sulfur (e.g. baryte) and carbonate associated sulfates (CAS) to determine past seawater sulfur concentrations which can help identify specific depositional periods such as anoxic or oxic conditions. The use of sulfur isotope reconstruction is often paired with oxygen when a molecule contains both elements.[30]
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Dating the baryte in hydrothermal vents has been one of the major methods to determine their ages.[31][32][33][34][35] Common methods to date hydrothermal baryte include radiometric dating[31][32] and electron spin resonance dating.[33][34][35]
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Baryte is used in added-value applications which include filler in paint and plastics, sound reduction in engine compartments, coat of automobile finishes for smoothness and corrosion resistance, friction products for automobiles and trucks, radiation shielding concrete, glass ceramics, and medical applications (for example, a barium meal before a contrast CT scan). Baryte is supplied in a variety of forms and the price depends on the amount of processing; filler applications commanding higher prices following intense physical processing by grinding and micronising, and there are further premiums for whiteness and brightness and color.[16] It is also used to produce other barium chemicals, notably barium carbonate which is used for the manufacture of LED glass for television and computer screens (historically in cathode ray tubes); and for dielectrics.
Historically, baryte was used for the production of barium hydroxide for sugar refining, and as a white pigment for textiles, paper, and paint.[3]
Although baryte contains the toxic alkaline earth metal barium, it is not detrimental for human health, animals, plants and the environment because barium sulfate is extremely insoluble in water.
It is also sometimes used as a gemstone.[36]
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This article incorporates public domain material from Barite (PDF). United States Geological Survey.
Barium sulfate (or sulphate) is the inorganic compound with the chemical formula BaSO4. It is a white crystalline solid that is odorless and insoluble in water. It occurs in nature as the mineral barite, which is the main commercial source of barium and materials prepared from it. Its opaque white appearance and its high density are exploited in its main applications.[4]
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About 80% of the world's barium sulfate production, mostly purified mineral, is consumed as a component of oil well drilling fluid. It increases the density of the fluid,[5] increasing the hydrostatic pressure in the well and reducing the chance of a blowout.
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Barium sulfate in suspension is often used medically as a radiocontrast agent for X-ray imaging and other diagnostic procedures. It is most often used in imaging of the GI tract during what is colloquially known as a "barium meal". It is administered orally, or by enema, as a suspension of fine particles in a thick milk-like solution (often with sweetening and flavoring agents added). Although barium is a heavy metal, and its water-soluble compounds are often highly toxic, the low solubility of barium sulfate protects the patient from absorbing harmful amounts of the metal. Barium sulfate is also readily removed from the body, unlike Thorotrast, which it replaced. Due to the relatively high atomic number (Z = 56) of barium, its compounds absorb X-rays more strongly than compounds derived from lighter nuclei.
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The majority of synthetic barium sulfate is used as a component of white pigment for paints. In oil paint, barium sulfate is almost transparent[citation needed], and is used as a filler or to modify consistency. One major manufacturer of artists' oil paint sells "permanent white" that contains a mixture of titanium white pigment (TiO2) and barium sulfate. The combination of barium sulfate and zinc sulfide (ZnS) is the inorganic pigment called lithopone. In photography it is used as a coating for certain photographic papers.[5] It is also used as a coating to diffuse light evenly.
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Barium sulfate is highly reflective, of both visible and ultraviolet light.[6] Researchers used it as an ingredient in paint that reflects 98.1% of solar radiation, allowing surfaces to which it has been applied to stay cooler in sunlit conditions. Commercially available white paints only reflect 80 - 90% of solar radiation.[7] By using hexagonal nanoplatelet boron nitride, the thickness of a coat of this type of paint was reduced to 0.15 mm.[6]
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A thin layer of barium sulfate called baryta is first coated on the base surface of most photographic paper to increase the reflectiveness of the image, with the first such paper introduced in in Germany.[8] The light-sensitive silver halide emulsion is then coated over the baryta layer. The baryta coating limits the penetration of the emulsion into the fibers of the paper and makes the emulsion more even, resulting in more uniform blacks.[9] Further coatings may then be present for fixing and protection of the image. Baryta has also been used to brighten papers intended for ink-jet printing.[10]
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Barium sulfate is commonly used as a filler for plastics to increase the density of the polymer in vibrational mass damping applications. In polypropylene and polystyrene plastics, it is used as a filler in proportions up to 70%. It has an effect of increasing acid and alkali resistance and opacity. Such composites are also used as X-ray shielding materials due to their enhanced radio-opacity.[11] In cases where machinability and weight are a concern, composites with high mass fraction (70&#;80%) of barium sulfate may be preferred to the more commonly used steel shields.[12]
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Barium sulfate is used in soil testing. Tests for soil pH and other qualities of soil use colored indicators, and small particles (usually clay) from the soil can cloud the test mixture and make it hard to see the color of the indicator. Barium sulfate added to the mixture binds with these particles, making them heavier so they fall to the bottom, leaving a clearer solution.
In colorimetry, barium sulfate is used as a near-perfect diffuser when measuring light sources.
In metal casting, the moulds used are often coated with barium sulfate in order to prevent the molten metal from bonding with the mould.
It is also used in brake linings, anacoustic foams, powder coatings, and root canal filling.
Barium sulfate is an ingredient in the "rubber" pellets used by Chilean police.[13] This together with silica helps the pellet attain a 96.5 Shore A hardness.[13]
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Barium sulfate is used as a catalyst support when selectively hydrogenating functional groups that are sensitive to overreduction. With a low surface area, the contact time of the substrate with the catalyst is shorter and thus selectivity is achieved. Palladium on barium sulfate is also used as a catalyst in the Rosenmund reduction.
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As barium compounds emit a characteristic green light when heated at high temperature, barium salts are often used in green pyrotechnic formulas, although nitrate and chlorate salts are more common. Barium sulfate is commonly used as a component of "strobe" pyrotechnic compositions.
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As barium sulfate has a high melting point and is insoluble in water, it is used as a release material in casting of copper anode plates. The anode plates are cast in copper molds, so to avoid the direct contact of the liquid copper with the solid copper mold, a suspension of fine barium sulfate powder in water is used as a coating on the mold surface. Thus, when the molten copper solidifies in form of an anode plate it can be easily released from its mold.
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Barium sulfate is sometimes used, besides polytetrafluoroethylene (PTFE), to coat the interior of integrating spheres due to the high reflectance of the material and near Lambertian characteristics.
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Barium sulfate is listed among the materials acceptable to the Bureau of Alcohol, Tobacco, Firearms and Explosives (BATFE) for the manufacturing of firearms and/or components that are made of plastic, to achieve compliance with the U.S. federal requirement that an X-ray machine must be able to accurately depict the shape of the plastic firearm or component.[14]
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Almost all of the barium consumed commercially is obtained from barite, which is often highly impure. Barite is processed by thermo-chemical sulfate reduction (TSR), also known as carbothermal reduction (heating with coke) to give barium sulfide:
In contrast to barium sulfate, barium sulfide is soluble in water and readily converted to the oxide, carbonate, and halides. To produce highly pure barium sulfate, the sulfide or chloride is treated with sulfuric acid or sulfate salts:
Barium sulfate produced in this way is often called blanc fixe, which is French for "permanent white". Blanc fixe is the form of barium encountered in consumer products, such as paints.[5]
In the laboratory barium sulfate is generated by combining solutions of barium ions and sulfate salts. Because barium sulfate is the least toxic salt of barium due to its insolubility, wastes containing barium salts are sometimes treated with sodium sulfate to immobilize (detoxify) the barium. Barium sulfate is one of the most insoluble salts of sulfate. Its low solubility is exploited in qualitative inorganic analysis as a test for Ba2+ ions, as well as for sulfate.
Untreated raw materials such as natural baryte formed under hydrothermal conditions may contain many impurities, a.o., quartz, or even amorphous silica.[15]
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Barium sulfate is reduced to barium sulfide by carbon. The accidental discovery of this conversion many centuries ago led to the discovery of the first synthetic phosphor.[4] The sulfide, unlike the sulfate, is water-soluble.
During the early part of the 20th century, during the Japanese colonization period, hokutolite was found to exist naturally in the Beitou hot-springs area near Taipei City, Taiwan. Hokutolite is a radioactive mineral composed mostly of PbSO4 and BaSO4, but also containing traces of uranium, thorium and radium. The Japanese harvested these elements for industrial uses, and also developed dozens of &#;therapeutic hot-spring baths&#; in the area.[16]
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Although soluble salts of barium are moderately toxic to humans, barium sulfate is nontoxic due to its insolubility. The most common means of inadvertent barium poisoning arises from the consumption of soluble barium salts mislabeled as BaSO4. In the Celobar incident (Brazil, ), nine patients died from improperly prepared radiocontrast agent. In regards to occupational exposures, the Occupational Safety and Health Administration set a permissible exposure limit at 15 mg/m3, while the National Institute for Occupational Safety and Health has a recommended exposure limit at 10 mg/m3. For respiratory exposures, both agencies have set an occupational exposure limit at 5 mg/m3.[17]
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