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Selenium is a chemical element with atomic number 34, chemical symbol Se, and an atomic mass of 78.96. It is a nonmetal, whose properties are intermediate between those of adjacent chalcogen elements sulfur andtellurium. It rarely occurs in its elemental state in nature, but instead is obtained as a side-product in the refining of other elements.Sony VAIO VPCF11S1E Battery

Selenium is found in sulfide ores such as pyrite, where it partially replaces the sulfur. Minerals that are selenide or selenate compounds are also known, but are rare. The chief commercial uses for selenium today are in glassmaking and inpigments. Uses in electronics, once important, have been supplanted by silicon semiconductor devices.Sony VAIO VPCF11S1E/B Battery

It is a semiconductorwith the unusual property of conducting electricity better in the light than in the dark, and is used in photocells. Selenium is a trace mineral that is essential to good health but required only in small amounts. Selenium is incorporated into proteins to make selenoproteins, which are important antioxidant enzymes.Sony VAIO VPCF11Z1E Battery

The antioxidant properties of selenoproteins help prevent cellular damage from free radicals. Free radicals are natural by-products of oxygen metabolism that may contribute to the development of chronic diseases such as cancer and heart disease. Other selenoproteins help regulate thyroid function and play a role in the immune system.Sony VAIO VPCF11Z1E/BI Battery

Selenium salts are toxic in large amounts, but trace amounts are necessary for cellular function in many organisms. It is a component of the enzymes glutathione peroxidase and thioredoxin reductase (which indirectly reduce certain oxidized molecules in animals and some plants).Sony VAIO VPCF11ZHJ Battery

It is also found in three deiodinase enzymes, which convert one thyroid hormone to another. Selenium requirements in plants differ by species, with some plants, it seems, requiring none.

Physical

The most stable allotrope of selenium is a dense purplish-gray solid. In terms of structure, it adopts a helical polymeric chain.Sony VAIO VPCF127HGBI Battery

The Se-Se distance is 2.37 Å and the Se-Se-Se angle is 103°. It is a semiconductor with the unusual property of conducting electricity better in the light than in the dark, and is used in photocells. Gray selenium resists oxidation by air and is not attacked by non-oxidizing acids. With strong reducing agents, it forms polyselenides.Sony VAIO VPCF137HG/BI Battery

Red Se and related molecular allotropes

The second major allotrope of Se is red selenium. The solid consists of individual molecules of eight-membered ringmolecules, like its lighter cousin sulfur. The Se-Se distance is 2.34 Å and the Se-Se-Se angle is 106°. Unlike sulfur, however, the red form converts to the gray polymeric allotrope with heat. Other rings with the formula Sen are also known.Sony VAIO VPC-P111KX/B Battery

Elemental selenium produced in chemical reactions invariably appears as the amorphous red form: an insoluble, brick-red powder. When this form is rapidly melted, it forms the black, vitreous form, which is usually sold industrially as beads. The red allotrope crystallises in three habits.Sony VAIO VPC-P111KX/D Battery

Selenium does not exhibit the unusual changes in viscosity that sulfur undergoes when gradually heated.

Selenium has six naturally occurring isotopes, five of which are stable: 74Se, 76Se, 77Se, 78Se, and 80Se. The last three also occur as fission products, along with 79Se, which has a half-life of 327,000 years.Sony VAIO VPC-P111KX/G Battery

The final naturally occurring isotope, 82Se, has a very long half-life (~1020 yr, decaying via double beta decay to 82Kr), which, for practical purposes, can be considered to be stable. Twenty-three other unstable isotopes have been characterized.Sony VAIO VPC-P111KX/P Battery

See also Selenium-79 for more information on recent changes in the measured half-life of this long-lived fission product, important for the dose calculations performed in the frame of the geological disposal of long-lived radioactive waste.Sony VAIO VPC-P111KX/W Battery

Occurrence

Native selenium is a rare mineral, which does not usually form good crystals, but, when it does, they are steep rhombohedrons or tiny acicular (hair-like) crystals. Isolation of selenium is often complicated by the presence of other compounds and elements.Sony VAIO VPC-P112KX/B Battery

Selenium occurs naturally in a number of inorganic forms, including selenide-,selenate-, and selenite-containing minerals.

In living systems, selenium is found in the amino acids selenomethionine, selenocysteine, and methylselenocysteine.Sony VAIO VPC-P112KX/D Battery

In these compounds, selenium plays a role analogous to that of sulfur. Another naturally occurring organoselenium compounds is dimethyl selenide.

Certain solids are selenium-rich, and selenium can be bioconcentrated by certain plants. In soils, selenium most often occurs in soluble forms such as selenate (analogous to sulfate), which are leached into rivers very easily by runoff.Sony VAIO VPC-P112KX/G Battery

Anthropogenic sources of selenium include coal burning and the mining and smelting of sulfide ores.

Production

Selenium is most commonly produced from selenide in many sulfide ores, such as those ofcopper, silver, or lead.Sony VAIO VPC-P112KX/P Battery

It is obtained as a byproduct of the processing of these ores, e.g., from the anode mud of copper refineries and the mud from the lead chambers ofsulfuric acid plants. These muds can be processed by a number of means to obtain selenium. Specifically, most elemental selenium comes as a byproduct of refining copperor producing sulfuric acid.Sony VAIO VPC-P112KX/W Battery

Industrial production of selenium often involves the extraction of selenium dioxide from residues obtained during the purification of copper. Common production begins by oxidation with sodium carbonate to produce selenium dioxide. The selenium dioxide is then mixed with water and the solution is acidified to form selenous acid (oxidation step).Sony VAIO VPCP113KX/B Battery

Selenous acid is bubbled with sulfur dioxide (reduction step) to give elemental selenium.

Chalcogen compounds

Selenium forms two stable oxides: selenium dioxide (SeO2) and selenium trioxide (SeO3). Selenium dioxide is formed by the reaction of elemental selenium with oxygen:Sony VAIO VPC-P113KX/B Battery

It is a polymeric solid that forms monomeric SeO2 molecules in the gas phase. It dissolves in water to form selenous acid, H2SeO3. Selenous acid can also be made directly by oxidising elemental selenium with nitric acid:

3 Se + 4 HNO3 ? 3 H2SeO3 + 4 NO

Unlike sulfur, which forms a stable trioxide, selenium trioxide is unstable and decomposes to the dioxide above 185 °C:Sony VAIO VPCP113KX/D Battery

2 SeO3 ? 2 SeO2 + O2 (?H = ?54 kJ/mol)

Salts of selenous acid are called selenites. These include silver selenite (Ag2SeO3) and sodium selenite (Na2SeO3).

Hydrogen sulfide reacts with aqueous selenous acid to produce selenium disulfide:

H2SeO3 + 2 H2S ? SeS2 + 3 H2O

Selenium disulfide consists of 8-membered rings of a nearly statistical distribution of sulfur and selenium atoms.Sony VAIO VPC-P113KX/D Battery

It has an approximate composition of SeS2, with individual rings varying in composition, such as Se4S4 and Se2S6. Selenium disulfide has been use in shampoo as an anti-dandruff agent, an inhibitor in polymer chemistry, a glass dye, and a reducing agent in fireworks.Sony VAIO VPCP113KX/G Battery

Selenium trioxide may be synthesized by dehydrating selenic acid, H2SeO4, which is itself produced by the oxidation of selenium dioxide with hydrogen peroxide:

SeO2 + H2O2 ? H2SeO4

Hot, concentrated selenic acid is capable of dissolving gold, forming gold(III) selenate.Sony VAIO VPC-P113KX/G Battery

Halogen compounds

Iodides of selenium are not well known. The only stable chloride is Se2Cl2; the corresponding bromide is also known. These species are structurally analogous to the corresponding disulfur dichloride. Selenium dichloride is an important reagent in the preparation of selenium compounds (e.g. the preparation of Se7).Sony VAIO VPCP113KX/P Battery

It is prepared by treating selenium with SO2Cl2. Selenium reacts with fluorine to form selenium hexafluoride:

Se8 + 24 F2 ? 8 SeF6

In comparison with its sulfur counterpart (sulfur hexafluoride), SeF6 is more reactive and is toxic pulmonary irritant. Some of the selenium oxyhalides, such asSeOF2 and selenium oxychloride have been used as specialty solvents.Sony VAIO VPC-P113KX/P Battery

Selenides

Analogous to the behavior of other chalcogens, selenium forms a dihydride H2Se. It is a strongly odiferous, toxic, and colourless gas. It is more acidic than H2S. In solution it ionizes to HSe-. The selenide dianion Se2- forms a variety of compounds, including the minerals from which selenium is obtained commercially.Sony VAIO VPCP113KX/W Battery

Illustrative selenides include mercury selenide (HgSe), lead selenide (PbSe), zinc selenide (ZnSe), and copper indium gallium diselenide (Cu(Ga,In)Se2). These materials are semiconductors. With highly electropositive metals, such as aluminium, these selenides are prone to hydrolysis:Sony VAIO VPC-P113KX/W Battery

Al2Se3 + 6 H2O ? 8 Al2O3 + H2Se

Alkali metal selenides react with selenium to form polyselenides, Sex2-, which exist as chains.

Other compounds

Tetraselenium tetranitride, Se4N4, is an explosive orange compound analogous to S4N4. It can be synthesized by the reaction of SeCl4 with[((CH3)3Si)2N]2Se.Sony VAIO VPC-P114KX/B Battery

Selenium reacts with cyanides to yield selenocyanates:

8 KCN + Se8 ? 8 KSeCN

Organoselenium compounds

Selenium, especially in the II oxidation state, forms stable bonds to carbon.Sony VAIO VPC-P114KX/D Battery

Typical compounds include selenols with the formula RSeH (e.g., benzeneselenol), selenides with the formula RSeR (e.g., diphenylselenide), and diselenides, with the formula RSeSeR (e.g., diphenyldiselenide). Selenoxides, with the formula RSe(O)R, and selenyl chlorides, with the formula RSeCl, are useful intermediates in organic chemistry.Sony VAIO VPC-P114KX/G Battery

History and global demand

Selenium (Greek ?????? selene meaning "Moon") was discovered in 1817 by Jöns Jakob Berzelius, who found the element associated with tellurium (named for the Earth). It was discovered as a byproduct of sulfuric acid production.Sony VAIO VPC-P114KX/P Battery

It came to medical notice later because of its toxicity to humans working in industry. It was also recognized as an important veterinary toxin, seen in animals eating high-selenium plants. In 1954, the first hints of specific biological functions of selenium were discovered in microorganisms.Sony VAIO VPC-P114KX/W Battery

Its essentiality for mammalian life was discovered in 1957. In the 1970s, it was shown to be present in two independent sets of enzymes. This was followed by the discovery of selenocysteine in proteins. During the 1980s, it was shown that selenocysteine is encoded by the codon TGA.Sony VAIO VPCP115JC Battery

The recoding mechanism was worked out first in bacteria and then in mammals(see SECIS element).

Health effects and nutrition

Although it is toxic in large doses, selenium is an essential micronutrient for animals.Sony VAIO VPCP115JC/B Battery

In plants, it occurs as a bystander mineral, sometimes in toxic proportions in forage (some plants may accumulate selenium as a defense against being eaten by animals, but other plants such as locoweed require selenium, and their growth indicates the presence of selenium in soil). See more on plant nutrition below.Sony VAIO VPCP115JC/D Battery

Selenium is a component of the unusual amino acids selenocysteine and selenomethionine. In humans, selenium is a trace element nutrient that functions as cofactor for reduction of antioxidant enzymes, such as glutathione peroxidases and certain forms of thioredoxin reductase found in animals and some plantsSony VAIO VPCP115JC/G Battery

(this enzyme occurs in all living organisms, but not all forms of it in plants require selenium).

The glutathione peroxidase family of enzymes (GSH-Px) catalyze certain reactions that remove reactive oxygen species such as hydrogen peroxide and organic hydroperoxides:Sony VAIO VPCP115JC/P Battery

2 GSH + H2O2----GSH-Px ? GSSG + 2 H2O

Selenium also plays a role in the functioning of the thyroid gland and in every cell that uses thyroid hormone, by participating as a cofactor for the three known thyroid hormone deiodinases, which activate and then deactivate various thyroid hormones and their metabolites.Sony VAIO VPCP115JC/W Battery

It may inhibitHashimotos's disease, in which the body's own thyroid cells are attacked as alien. A reduction of 21% on TPO antibodies was reported with the dietary intake of 0.2 mg of selenium.

Dietary sources of Se

Dietary selenium comes from nuts, cereals, meat, mushrooms, fish, and eggs.Sony VAIO VPCP115KG Battery

Brazil nuts are the richest ordinary dietary source (though this is soil-dependent, since the Brazil nut does not require high levels of the element for its own needs). In descending order of concentration, high levels are also found in kidney, tuna,crab, and lobster.Sony VAIO VPCP116KG Battery

The human body's content of selenium is believed to be in the 13–20 milligram range.

Indicator plants

Certain species of plants are considered indicators of high selenium content of the soil, since they require high levels of selenium to thrive. The main selenium indicator plants are Astragalus species (including some locoweeds), prince's plume (Stanleya sp.), woody asters (Xylorhiza sp.), and false goldenweed (Oonopsissp.)Sony VAIO VPC-P116KX/B Battery

Toxicity

Although selenium is an essential trace element, it is toxic if taken in excess. Exceeding the Tolerable Upper Intake Level of 400 micrograms per day can lead to selenosis. This 400 microgram (µg) Tolerable Upper Intake Level is based primarily on a 1986 study of five Chinese patients who exhibited overt signs of selenosis and a follow up study on the same five people in 1992.Sony VAIO VPC-P116KX/D Battery

The 1992 study actually found the maximum safe dietary Se intake to be approximately 800 micrograms per day (15 micrograms per kilogram body weight), but suggested 400 micrograms per day to not only avoid toxicity, but also to avoid creating an imbalance of nutrients in the diet and to account for data from other countries.Sony VAIO VPC-P116KX/G Battery

In China, people who ingested corn grown in extremely selenium-rich stony coal (carbonaceous shale) have suffered from selenium toxicity. This coal was shown to have selenium content as high as 9.1%, the highest concentration in coal ever recorded in literature.Sony VAIO VPC-P116KX/P Battery

Symptoms of selenosis include a garlic odor on the breath, gastrointestinal disorders, hair loss, sloughing of nails, fatigue, irritability, and neurological damage. Extreme cases of selenosis can result in cirrhosis of the liver, pulmonary edema, and death.Sony VAIO VPC-P116KX/W Battery

Elemental selenium and most metallic selenides have relatively low toxicities because of their low bioavailability. By contrast, selenates and selenites are very toxic, having an oxidant mode of action similar to that of arsenic trioxide. The chronic toxic dose of selenite for humans is about 2400 to 3000 micrograms of selenium per day for a long time.Sony VAIO VPCP118JC Battery

Hydrogen selenide is an extremely toxic, corrosive gas. Selenium also occurs in organic compounds, such as dimethyl selenide, selenomethionine, selenocysteine and methylselenocysteine, all of which have high bioavailability and are toxic in large doses.Sony VAIO VPCP118JC/B Battery

On 19 April 2009, twenty-one polo ponies began to die shortly before a match in the United States Polo Open. Three days later, a pharmacy released a statement explaining that the horses had received an incorrect dose of one of the ingredients used in a vitamin/mineral supplement compound, with which the horses had been injected.Sony VAIO VPCP118JC/P Battery

Such nutrient injections are common to promote recovery after a match, but this mixture had been compounded by a compounding pharmacy not familiar with it. Analysis of blood levels of inorganic compounds in the supplement indicated the selenium concentrations were ten to fifteen times higher than normal in the horses'blood samples, and 15 to 20 times higher than normal in their liver samples.Sony VAIO VPCP118JC/W Battery

It was later confirmed that selenium was the ingredient in question. Selenium is active in only tiny amounts, and has a history of causing accidental poisonings in supplements when the dose that is supposed to be in micrograms is given by mistake in milligrams (1000 times as much).Sony VAIO VPC-P118KX/B Battery

Selenium poisoning of water systems may result whenever new agricultural runoff courses through normally dry, undeveloped lands. This process leaches natural soluble selenium compounds (such as selenates) into the water, which may then be concentrated in new "wetlands" as the water evaporates.Sony VAIO VPC-P118KX/D Battery

High selenium levels produced in this fashion have been found to have caused certain congenital disorders in wetland birds.

Deficiency

Selenium deficiency is rare in healthy, well-nourished individuals. It can occur in patients with severely compromised intestinal function, those undergoing total parenteral nutrition, and in those of advanced age (over 90).Sony VAIO VPC-P118KX/G Battery

Also, people dependent on food grown from selenium-deficient soil are at risk. Although New Zealandhas low levels of selenium in its soil, adverse health effects have not been detected.

Selenium deficiency may only occur when a low selenium status is linked with an additional stress, such as chemical exposure or increased oxidant stress due to vitamin E deficiency.Sony VAIO VPC-P118KX/P Battery

There are interactions between selenium and other nutrients, such as iodine and vitamin E. The interaction is observed in the etiology of many deficiency diseases in animals and pure selenium deficiency is rare. The effect of selenium deficiency on health remains uncertain, particularly in relation to Kashin-Beck disease.Sony VAIO VPC-P118KX/W Battery

Controversial health effects

Several studies have suggested a possible link between cancer and selenium deficiency. One study, known as the NPC, was conducted to test the effect of selenium supplementation on the recurrence of skin cancers on selenium-deficient men.Sony VAIO VPCP119JC Battery

It did not demonstrate a reduced rate of recurrence of skin cancers, but did show a reduced occurrence of total cancers, particularly for lung, colorectal and prostate cancers (Relative Risk 0.63). There was also a significant reduction in total cancer mortality (?50 %), although without a statistically significant change in overall mortality.Sony VAIO VPCP119JC/BI Battery

The preventative effect observed in the NPC was greatest in those with the lowest baseline selenium levels.[49] In 2009, the 5.5 year SELECT study reported selenium and vitamin E supplementation, both alone and together, did not significantly reduce the incidence of prostate cancer in 35,000 men who "generally were replete in selenium at baseline".Sony VAIO VPCP11S1E/B Battery

The SELECT trial reported vitamin E did not reduce prostate cancer as it had in the alpha-tocopherol, beta carotene (ATBC) study, but the ATBC had a large percentage of smokers, while the SELECT trial did not. There was a slight trend toward more prostate cancer in the SELECT trial, but in the vitamin E only arm of the trial, where no selenium was given.Sony VAIO VPC-P11S1E/B Battery

Dietary selenium prevents chemically induced carcinogenesis in many rodent studies. It has been proposed that selenium may help prevent cancer by acting as anantioxidant or by enhancing immune activity. Not all studies agree on the cancer-fighting effects of selenium.Sony VAIO VPCP11S1E/D Battery

One study of naturally occurring levels of selenium in over 60,000 participants did not show a significant correlation between those levels and cancer. The SU.VI.MAX study concluded low-dose supplementation (with 120 mg of ascorbic acid, 30 mg of vitamin E,Sony VAIO VPC-P11S1E/D Battery

6 mg of beta carotene, 100 µg of selenium, and 20 mg of zinc) resulted in a 30% reduction in the incidence of cancer and a 37% reduction in all-cause mortality in males, but did not get a significant result for females.A Cochrane review of studies concluded that there is no convincing evidence that individuals,Sony VAIO VPCP11S1E/G Battery

particularly those who are adequately nourished, will benefit from selenium supplementation with regard to their cancer risk.However, there is evidence selenium can help chemotherapy treatment by enhancing the efficacy of the treatment, reducing the toxicity of chemotherapeutic drugs, and preventing the body's resistance to the drugs.Sony VAIO VPC-P11S1E/G Battery

Studies of cancer cells in vitro showed that chemotherapeutic drugs, such as taxol andAdriamycin, were more toxic to strains of cancer cells when selenium was added.

In March 2009, vitamin E (400 IU) and selenium (200 micrograms) supplements were reported to affect gene expression and can act as a tumor suppressor.Sony VAIO VPCP11S1E/P Battery

Eric Klein, MD from the Glickman Urological and Kidney Institute in Ohio said the new study “lend[s] credence to the previous evidence that selenium and vitamin E might be active as cancer preventatives”. In an attempt to rationalize the differences between epidemiological and in vitro studies and randomized trials like SELECT,Sony VAIO VPCP11S1E/W Battery

Klein said randomized controlled trials “do not always validate what we believe biology indicates and that our model systems are imperfect measures of clinical outcomes in the real world”.

HIV/AIDS

Some research has indicated a geographical link between regions of selenium-deficient soils and peak incidences of HIV/AIDS infection.Sony VAIO VPC-P11S1E/W Battery

For example, much of sub-Saharan Africa is low in selenium. However, Senegal is not, and also has a significantly lower level of AIDS infection than the rest of the continent. AIDS appears to involve a slow and progressive decline in levels of selenium in the body.Sony VAIO VPCP11Z9E/B Battery

Whether this decline in selenium levels is a direct result of the replication of HIV or related more generally to the overall malabsorption of nutrients by AIDS patients remains debated.

Low selenium levels in AIDS patients have been directly correlated with decreased immune cell count and increased disease progression and risk of death.Sony VAIO VPCS111FM/S Battery

Selenium normally acts as an antioxidant, so low levels of it may increase oxidative stress on the immune system, leading to its more rapid decline. Others have argued T-cell-associated genes encode selenoproteins similar to human glutathione peroxidase. Depleted selenium levels in turn lead to a decline in CD4 helper T-cells, further weakening the immune system.Sony VAIO VPCS115EC Battery

Regardless of the cause of depleted selenium levels in AIDS patients, studies have shown selenium deficiency does strongly correlate with the progression of the disease and the risk of death.

Tuberculosis

Some research has suggested selenium supplementation, along with other nutrients, can help prevent the recurrence of tuberculosis.Sony VAIO VPCS115FG Battery

Diabetes

A well-controlled study showed selenium levels are positively correlated with the risk of having type 2 diabetes. Because high serum selenium levels are positively associated with the prevalence of diabetes, and because selenium deficiency is rare, supplementation is not recommended in well-nourished populations, such as the U.S.Sony VAIO VPCS117GG Battery

More recent studies, however, have indicated selenium may help inhibit the development of type 2 diabetes in men, though the mechanism for the possible preventative effect is not known.

Applications

The demand for Se was around 2300 tonnes/y in the years 1989–1991.Sony VAIO VPCS117GGB Battery

Glass production

The largest commercial use of Se, accounting for about 50% of consumption, is for the production of glass. Se compounds confer a red colour to glass. This colour cancels out the green or yellow tints that arise from iron impurities that are typical for most glass.Sony VAIO VPCS118EC Battery

For this purpose various salts of selenite and selenate are added. For other application, the red colour is desirable, in which case mixtures of CdSe and CdS are added.

Rubber industry

Small amounts of organoselenium compounds are used to modify the vulcanization catalysts used in the production of rubber.Sony VAIO VPCS119FJ/B Battery

Uses in the laboratory

Selenium is a catalyst in some chemical reactions but it is not widely used because of issues with toxicity. In X-ray crystallography, incorporation of one or more Se atoms helps with MAD and SAD phasing.

Alloys

Selenium is used with bismuth in brasses to replace more toxic lead.Sony VAIO VPCS119GC Battery

Electronics

The demand for Se by the electronics industry is declining, despite a number of continuing applications. Because of its photovoltaic and photoconductiveproperties, selenium is used in photocopying, photocells, light meters and solar cells.Sony VAIO VPCS11AFJ Battery

Its use as a photoconductor in plain-paper copiers once was a leading application but in the 1980s, the photoconductor application declined (although it was still a large end-use) as more and more copiers switched to the use of organic photoconductors. It was once widely used in selenium rectifiers.Sony VAIO VPCS11AGJ Battery

These uses have mostly been replaced by silicon-based devices or are in the process of being replaced. The most notable exception is in power DC surge protection, where the superior energy capabilities of selenium suppressors make them more desirable thanmetal oxide varistors.Sony VAIO VPCS11AHJ Battery

Sheets of amorphous selenium convert x-ray images to patterns of charge in xeroradiography and in solid-state, flat-panel x-ray cameras.

Zinc selenide is used in blue and white LEDs.Sony VAIO VPCS11AVJ Battery

Photography

Selenium is used in the toning of photographic prints, and it is sold as a toner by numerous photographic manufacturers including Kodak and Fotospeed. Its use intensifies and extends the tonal range of black-and-white photographic images as well as improving the permanence of prints.Sony VAIO VPCS11J7E/B Battery

Early photographic light meters used selenium, but this application is now obsolete.

Biological role

The substance loosely called selenium sulfide (approximate formula SeS2) is the active ingredient in some anti-dandruff shampoos.Sony VAIO VPCS11M1E/W Battery

The selenium compound kills the scalp fungus Malassezia, which causes shedding of dry skin fragments. The ingredient is also used in body lotions to treat Tinea versicolor due to infection by a different species of Malassezia fungus.

Nutrition

Selenium is used widely in vitamin preparations and other dietary supplements, in small doses (typically 50 to 200 micrograms per day for adult humans). Some livestock feeds are fortified with selenium as well.Sony VAIO VPCS11V9E Battery

Detection in biological fluids

Selenium may be measured in blood, plasma, serum or urine to monitor excessive environmental or occupational exposure, confirm a diagnosis of poisoning in hospitalized victims or to assist in a forensic investigation in a case of fatal overdosage. Sony VAIO VPCS11V9E/B Battery

Some analytical techniques are capable of distinguishing organic from inorganic forms of the element. Both organic and inorganic forms of selenium are largely converted to monosaccharide conjugates (selenosugars) in the body prior to being eliminated in the urine.Sony VAIO VPCS11X9E/B Battery

Cancer patients receiving daily oral doses of selenothionine may achieve very high plasma and urine selenium concentrations.

Evolution in biology

Over three billion years ago, blue-green algae were the most primitive oxygenic photosynthetic organisms and are ancestors of multicellular eukaryotic algae.Sony VAIO VPCS123FGB Battery

Algae that contain the highest amount of antioxidant selenium, iodide, and peroxidase enzymes were the first living cells to produce poisonous oxygen in the atmosphere. It has been suggested that algal cells required a protective antioxidant action, in which selenium and iodides, through peroxidase enzymes, have had this specific role.Sony VAIO VPCS125EC Battery

Selenium, which acts synergistically with iodine, is a primitive mineral antioxidant, greatly present in the sea and prokaryotic cells, where it is an essential component of the family of glutathione peroxidase (GSH-Px) antioxidant enzymes; seaweeds accumulate high quantity of selenium and iodine.Sony VAIO VPCS128EC Battery

In 2008, a study showed that iodide also scavenges reactive oxygen species (ROS) in algae, and that its biological role is that of an inorganic antioxidant, the first to be described in a living system, active also in an in vitro assay with the blood cells of today’s humans."Sony VAIO VPCS129GC Battery

From about three billion years ago, prokaryotic selenoprotein families drive selenocysteine evolution. Selenium is incorporated into several prokaryotic selenoprotein families in bacteria, archaea and eukaryotes as selenocysteine, where selenoprotein peroxiredoxins protect bacterial and eukaryotic cells against oxidative damage.Sony VAIO VPCS12C7E/B Battery

Selenoprotein families of GSH-Px and the deiodinases of eukaryotic cells seem to have a bacterial phylogenetic origin. The selenocysteine-containing form occurs in species as diverse as green algae, diatoms, sea urchin, fish and chicken. Selenium enzymes are involved in utilization of the small reducing molecules glutathione and thioredoxin.Sony VAIO VPCS12L9E/B Battery

One family of selenium-containing molecules (the glutathione peroxidases) destroy peroxide and repair damaged peroxidized cell membranes, using glutathione. Another selenium-containing enzyme in some plants and in animals (thioredoxin reductase) generates reduced thioredoxin,Sony VAIO VPCS12V9E/B Battery

a dithiol that serves as an electron source for peroxidases and also the important reducing enzyme ribonucleotide reductase that makes DNA presursors from RNA precursors.

At about 500 Mya, plants and animals began to transfer from the sea to rivers and land, the environmental deficiency of marine mineral antioxidants (as selenium, iodine, etc.)Sony VAIO VPCW111XX/P Battery

was a challenge to the evolution of terrestrial life.[75] Trace elements involved in GSH-Px and superoxide dismutase enzymes activities, i.e. selenium,vanadium, magnesium, copper, and zinc, may have been lacking in some terrestrial mineral-deficient areas.Sony VAIO VPCW111XX/PC Battery

Marine organisms retained and sometimes expanded their seleno-proteomes, whereas the seleno-proteomes of some terrestrial organisms were reduced or completely lost. These findings suggest that, with the exception ofvertebrates, aquatic life supports selenium utilization, whereas terrestrial habitats lead to reduced use of this trace element.Sony VAIO VPCW111XX/T Battery

Marine fishes and vertebrate thyroid glands have the highest concentration of selenium and iodine. From about 500 Mya, freshwater and terrestrial plants slowly optimized the production of “new” endogenous antioxidants such as ascorbic acid (Vitamin C), polyphenols (including flavonoids), tocopherols, etc.Sony VAIO VPCW111XX/W Battery

A few of these appeared more recently, in the last 50–200 million years, in fruits and flowers of angiosperm plants. In fact, the angiosperms (the dominant type of plant today) and most of their antioxidant pigments evolved during the late Jurassic period.Sony VAIO VPCW111XXP Battery

The deiodinase isoenzymes constitute another family of eukaryotic selenoproteins with identified enzyme function. Deiodinases are able to extract electrons from iodides, and iodides from iodothyronines. They are, thus, involved in thyroid-hormone regulation, participating in the protection of thyrocytes from damage by H2O2produced for thyroid-hormone biosynthesis.Sony VAIO VPCW111XXT Battery

About 200 Mya, new selenoproteins were developed as mammalian GSH-Px enzymes.

Bromine is achemical element with the symbol Br, an atomic number of 35, and an atomic mass of 79.904. It is in the halogen element group.Sony VAIO VPCW111XXW Battery

The element was isolated independently by two chemists, Carl Jacob Löwig and Antoine Jerome Balard, in 1825–1826. Elemental bromine is a fuming red-brown liquid at room temperature, corrosive and toxic, with properties between those ofchlorine and iodine.Sony VAIO VPCW115XG Battery

Free bromine does not occur in nature, but occurs as colorless soluble crystalline mineral halide salts, analogous to table salt.

Bromine is rarer than about three-quarters of elements in the Earth's crust, however the high solubility of bromide ion has caused its accumulation in the oceans,Sony VAIO VPCW115XGP Battery

and commercially the element is easily extracted from brine pools, mostly in the United States, Israel and China. About 556,000 tonnes were produced in 2007, an amount similar to the far more abundant element magnesium.

At high temperatures, organobromine compounds are easily converted to free bromine atoms, a process which acts to terminatefree radical chemical chain reactions.Sony VAIO VPCW115XW/P Battery

This makes such compounds useful fire retardants and this is bromine's primary industrial use, consuming more than half of world production of the element. The same property allows volatile organobromine compounds, under the action of sunlight, to form free bromine atoms in the atmosphere which are highly effective in ozone depletion.Sony VAIO VPCW115XW/T Battery

This unwanted side-effect has caused many common volatile brominated organics like methyl bromide, a pesticide that was formerly a large industrial bromine consumer, to be abandoned. Remaining uses of bromine compounds are in well-drilling fluids, as an intermediate in manufacture of organic chemicals, and in film photography.Sony VAIO VPCW115XW/W Battery

Bromine has no essential function in mammals, though it is preferentially used over chloride by one antiparasitic enzyme in the human immune system. Organobromides are needed and produced enzymatically from bromide by some lower life forms in the sea, particularly algae, and the ash of seaweed was one source of bromine's discovery.Sony VAIO VPCW117XC/P Battery

As a pharmaceutical, simple bromide ion, Br–, has inhibitory effects on the central nervous system, and bromide salts were once a major medical sedative, before being replaced by shorter-acting drugs. They retain niche uses as antiepileptics.

Physical

Elemental bromine exists as a diatomic molecule, Br2.Sony VAIO VPCW117XC/T Battery

It is a dense, mobile, slightly transparent reddish-brown liquid, that evaporates easily at standard temperature and pressures to give an orange vapor (its color resembles nitrogen dioxide) that has a strongly disagreeable odor resembling that of chlorine. It is one of only two elements on the periodic table that are liquids at room temperature (mercury is the other, althoughcaesium, gallium, and rubidium melt just above room temperature).Sony VAIO VPCW117XC/W Battery

At a pressure of 55 GPa bromine converts to a metal. At 75 GPa it converts to a face centered orthorhombic structure. At 100 GPa it converts to a body centered orthorhombic monoatomic form.Sony VAIO VPCW119XJ Battery

Chemical

Being less reactive than chlorine but more reactive than iodine, bromine reacts vigorously with metals, especially in the presence of water, to give bromide salts. It is also reactive toward most organic compounds, especially upon illumination, conditions that favor the dissociation of the diatomic molecule into bromine radicals:Sony VAIO VPCW119XJ/P Battery

Br2 2 Br·

It bonds easily with many elements and has a strong bleaching action.

Bromine is slightly soluble in water, but it is highly soluble in organic solvents such as carbon disulfide, carbon tetrachloride, aliphatic alcohols, and acetic acid.Sony VAIO VPCW119XJ/W Battery

Bromine has two stable isotopes, 79Br (50.69 %) and 81Br (49.31%). At least 23 other radioisotopes are known. Many of the bromine isotopes are fission products. Several of the heavier bromine isotopes from fission are delayed neutron emitters. All of the radioactive bromine isotopes are relatively short lived.Sony VAIO VPCW11AXJ Battery

The longest half-life is the neutron deficient 77Br at 2.376 days. The longest half-life on the neutron rich side is 82Br at 1.471 days. A number of the bromine isotopes exhibit metastable isomers. Stable 79Br exhibits a radioactive isomer, with a half-life of 4.86 seconds. It decays by isomeric transition to the stable ground state.Sony VAIO VPCW11S1E/P Battery

Bromine was discovered independently by two chemists, Carl Jacob Löwig and Antoine Balard, in 1825 and 1826, respectively.

Balard found bromide chemicals in the ash of seaweed from the salt marshes of Montpellier. The seaweed was used to produce iodine, but also contained bromine.Sony VAIO VPCW11S1E/T Battery

Balard distilled the bromine from a solution of seaweed ash saturated with chlorine. The properties of the resulting substance resembled that of an intermediate of chlorine and iodine; with those results he tried to prove that the substance was iodine monochloride (ICl),Sony VAIO VPCW11S1E/W Battery

but after failing to do so he was sure that he had found a new element and named it muride, derived from the Latin word muria for brine.

Löwig isolated bromine from a mineral water spring from his hometown Bad Kreuznach in 1825.Sony VAIO VPCW121AX Battery

Löwig used a solution of the mineral salt saturated with chlorine and extracted the bromine with diethyl ether. After evaporation of the ether a brown liquid remained. With this liquid as a sample for his work he applied for a position in the laboratory of Leopold Gmelin inHeidelberg. The publication of the results was delayed and Balard published his results first.Sony VAIO VPCW126AG Battery

After the French chemists Louis Nicolas Vauquelin, Louis Jacques Thénard, and Joseph-Louis Gay-Lussac approved the experiments of the young pharmacist Balard, the results were presented at a lecture of the Académie des Sciences and published in Annales de Chimie et Physique.Sony VAIO VPCW127JC/P Battery

In his publication Balard states that he changed the name from muride to brômeon the proposal of M. Anglada. (Brôme (bromine) derives from the Greek ?????? (stench). ) Other sources claim that the French chemist and physicist Joseph-Louis Gay-Lussac suggested the name brôme for the characteristic smell of the vapors.Sony VAIO VPCW127JC/T Battery

Bromine was not produced in large quantities until 1860.

The first commercial use, besides some minor medical applications, was the use of bromine for the daguerreotype. In 1840 it was discovered that bromine had some advantages over the previously used iodine vapor to create the light sensitive silver halide layer used for daguerreotypy.Sony VAIO VPCW127JC/W Battery

Potassium bromide and sodium bromide were used as anticonvulsants and sedatives in the late 19th and early 20th centuries, until they were gradually superseded bychloral hydrate and then the barbiturates.

The diatomic element Br2 does not occur naturally. Instead, bromine exists exclusively asbromide salts in diffuse amounts in crustal rock.Sony VAIO VPCW127JC/WZ Battery

Owing to leaching, bromide salts have accumulated in sea water at 65 part per million (ppm), which is less than chloride. Bromine may be economically recovered from bromide-rich brine wells and from the Dead Seawaters (up to 50,000 ppm). It exists in the Earth's crust at an average concentration of 0.4 ppm, making it the 62nd most abundant element.Sony VAIO VPCW12AAJ Battery

The bromine concentration in soils varies normally between 5 and 40 ppm, but some volcanic soils can contain up to 500 ppm. The concentration of bromine in the atmosphere is extremely low, at only a few ppt. 

A large number of organobromine compounds are found in small amounts in nature.Sony VAIO VPCW12AKJ Battery

China's bromine reserves are located in the Shandong Province and Israel's bromine reserves are contained in the waters of the Dead Sea. The largest bromine reserve in the United States is located in Columbia County and Union County, Arkansas, U.S.Sony VAIO VPCW12AVJ Battery

Production

Bromine production is rather dynamic and has increased sixfold since the 1960s. Approximately 556,000 tonnes (worth around US $2.5 billion) was produced in 2007 worldwide, with the predominant contribution from the United States (226,000 t) and Israel(210,000 t).Sony VAIO VPCW12S1E/P Battery

US production was excluded from the United States Geological Survey after 2007, and from the 380,000 tonnes mined by other countries in 2010, 140,000 t were produced by China, 130,000 t by Israel and 80,000 t by Jordan.

Bromide-rich brines are treated with chlorine gas, flushing through with air. In this treatment, bromide anions are oxidized to bromine by the chlorine gas.Sony VAIO VPCW12S1E/T Battery

2 Br? + Cl2 ? 2 Cl? + Br2


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