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Selenium

[si-lee-nee-uhm]

Selenium is a chemical element with the atomic number 34, represented by the chemical symbol Se, an atomic mass of 78.96. It is a nonmetal, chemically related to sulfur and tellurium, and rarely occurs in its elemental state in nature. It is toxic in large amounts, but trace amounts of it are necessary for cellular function in most, if not all, animals, forming the active center of the enzymes glutathione peroxidase and thioredoxin reductase (which indirectly reduce certain oxidized molecules in animals and some plants) and three known deiodinase enzymes (which convert one thyroid hormone to another). Selenium requirements in plants differ by species, with some plants apparently requiring none.

Isolated selenium occurs in several different forms, the most stable of which is a dense purplish-gray semi-metal (semiconductor) form that is structurally a trigonal polymer chain. It conducts electricity better in the light than in the dark, and is used in photocells (see allotropic section below). Selenium also exists in many non-conductive forms: a black glass-like allotrope, as well as several red crystalline forms built of eight-membered ring molecules, like its lighter chemical cousin sulfur.

Selenium is found in economic quantities in sulfide ores such as pyrite, partially replacing the sulfur in the ore matrix. Minerals that are selenide or selenate compounds are also known, but all are rare.

Occurrence

Selenium occurs naturally in a number of inorganic forms, including selenide, selenate and selenite. In soils, selenium most often occurs in soluble forms like selenate (analogous to sulfate), which are leached into rivers very easily by runoff.

Selenium has a biological role, and is found in organic compounds such as dimethyl selenide, selenomethionine, selenocysteine and methylselenocysteine. In these compounds selenium plays an analogous role to sulfur.

Selenium is most commonly produced from selenide in many sulfide ores, such as those of copper, silver, or lead. It is obtained as a byproduct of the processing of these ores, from the anode mud of copper refineries and the mud from the lead chambers of sulfuric acid plants. These muds can be processed by a number of means to obtain free selenium.

Natural sources of selenium include certain selenium-rich soils, and selenium that has been bioconcentrated by certain toxic plants such as locoweed. Anthropogenic sources of selenium include coal burning and the mining and smelting of sulfide ores.

Isotopes

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 halflife of 295,000 years, and ⁸²Se which has a very long half life (~10²⁰ yr, decaying via double beta decay to ⁸²Kr) and for practical purposes can be considered to be stable. 23 other unstable isotopes have been characterized.

See also Selenium-79 for more information on recent changes in the halflife of this fission product important for the dose calculations performed in the frame of the geological disposal of long-lived radioactive waste.

History and global demand

Selenium (Greek σελήνη selene meaning "Moon") was discovered in 1817 by Jöns Jakob Berzelius who found the element associated with tellurium (named for the Earth).

Growth in selenium consumption was historically driven by steady development of new uses, including applications in rubber compounding, steel alloying, and selenium rectifiers. Selenium is also an essential material in the drums of laser printers and copiers. By 1970, selenium in rectifiers had largely been replaced by silicon, but its use as a photoconductor in plain paper copiers had become its leading application. During the 1980s, the photoconductor application declined (although it was still a large end-use) as more and more copiers using organic photoconductors were produced. Presently, the largest use of selenium world-wide is in glass manufacturing, followed by uses in chemicals and pigments. Electronic use, despite a number of continued applications, continues to decline.

In 1996, continuing research showed a positive correlation between selenium supplementation and cancer prevention in humans, but widespread direct application of this important finding would not add significantly to demand owing to the small doses required. In the late 1990s, the use of selenium (usually with bismuth) as an additive to plumbing brasses to meet no-lead environmental standards, became important. At present, total world selenium production continues to increase modestly.

Health effects

Although it is toxic in large doses, selenium is an essential micronutrient for animals. 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). It is a component of the unusual amino acids selenocysteine and selenomethionine. In humans, selenium is a trace element nutrient which functions as cofactor for reduction of antioxidant enzymes such as glutathione peroxidases and certain forms of thioredoxin reductase found in animals and some plants (this enzyme occurs in all living organisms, but not all forms of it in plants require selenium).

Glutathione peroxidase (GSH-Px) catalyzes certain reactions which remove reactive oxygen species such as peroxide:

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

Selenium also plays a role in the functioning of the thyroid gland by participating as a cofactor for the three known thyroid hormone deiodinases.

Dietary selenium comes from nuts, cereals, meat, fish, and eggs. 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). High levels are found in kidney, tuna, crab and lobster, in that order.

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. 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.

Elemental selenium and most metallic selenides have relatively low toxicities because of their low bioavailability. By contrast, selenate and selenite are very toxic, the acute toxicity differs from the chronic toxicity which for selenite the chronic toxic dose for human beings is about 2400 to 3000 micrograms of selenium per day for a long time. , and have an oxidant mode of action similar to that of arsenic. 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. Nano-size selenium has equal efficacy, but much lower toxicity.

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

Deficiency

Selenium deficiency is relatively rare in healthy well-nourished individuals. It can occur in patients with severely compromised intestinal function, those undergoing total parenteral nutrition, and also on advanced aged people (over 90). Alternatively, people dependent on food grown from selenium-deficient soil are also at risk.

Controversial health effects

Cancer: Several studies have suggested a link between cancer and selenium deficiency. A study conducted on the effect of selenium supplementation on the recurrence of skin cancers did not demonstrate a reduced rate of recurrence of skin cancers, but did show a significantly reduced occurrence of total cancers. Dietary selenium prevents chemically induced carcinogenesis in many rodent studies. In these studies, organic seleno-compounds are more potent and less toxic than selenium salts (e.g., selenocyanates, selenomethionine, selenium-rich Brazil nuts, or selenium-enriched garlic or broccoli). Selenium may help prevent cancer by acting as an antioxidant or by enhancing immune activity. Not all studies agree on the cancer-fighting effects of selenium. 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 that low-dose supplementation (with 120 mg of ascorbic acid, 30 mg of vitamin E, 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. The SELECT study is currently investigating the effect of selenium and vitamin E supplementation on incidence of prostate cancer. However, selenium has been proven to 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. Studies of cancer cells in vitro showed that chemotherapeutic drugs, such as Taxol and Adriamycin, were more toxic to strains of cancer cells grown in culture when selenium was added. HIV/AIDS: Some research has indicated a geographical link between regions of selenium deficient soils and peak incidences of HIV/AIDS infection. 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. 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. Selenium normally acts as an antioxidant, so low levels of it may increase oxidative stress on the immune system leading to more rapid decline of the immune system. Others have argued that HIV encodes for the human selenoenzyme glutathione peroxidase, which depletes the victim's selenium levels. Depleted selenium levels in turn lead to a decline in CD4 helper T-cells, further weakening the immune system.

Regardless of the cause of depleted selenium levels in AIDS patients, studies have shown that selenium deficiency does strongly correlate with the progression of the disease and the risk of death. Tuberculosis: Some research has suggested that selenium supplementation, along with other nutrients, can help prevent the recurrence of tuberculosis.Diabetes: A well-controlled study showed that selenium intake is positively correlated with the risk of developing type II 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.Mercury: Experimental findings have demonstrated an interaction between selenium and methylmercury, but epidemiological studies have found little evidence that selenium helps to protect against the adverse effects of methylmercury.

Production and allotropic forms

Selenium is a common byproduct of copper refining, or the production of sulfuric acid. Isolation of selenium is often complicated by the presence of other compounds and elements. Commonly, production begins by oxidation with sodium carbonate to produce selenium dioxide. The selenium dioxide is then mixed with water producing selenous acid. The selenous acid is finally bubbled with sulfur dioxide producing elemental red amorphous selenium.

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 most thermodynamically stable and dense form of selenium is the electrically conductive gray (trigonal) form, which is composed of long helical chains of selenium atoms. The conductivity of this form is notably light sensitive. Selenium also exists in three different deep red crystalline monoclinic forms, which are composed of Se₈ molecules, similar to many allotropes of sulfur.

Non-biological applications

Chemistry: Selenium is a catalyst in many chemical reactions and is widely used in various industrial and laboratory syntheses, especially Organoselenium chemistry. It is also widely used in structure determination of proteins and nucleic acids by X-ray crystallography (incorporation of one or more Se atoms helps with MAD and SAD phasing.)Manufacturing and materials use: The largest use of selenium world-wide is in glass and ceramic manufacturing, where it is used to give a red color to glasses, enamels and glazes as well as to remove color from glass by counteracting the green tint imparted by ferrous impurities.

Selenium is used with bismuth in brasses to replace more toxic lead. It is also used to improve abrasion resistance in vulcanized rubbers.Electronics: Because of its photovoltaic and photoconductive properties, selenium is used in photocopying, photocells, light meters and solar cells. It was once widely used in rectifiers. 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 than metal oxide varistors.

Sheets of amorphous selenium convert x-ray images to patterns of charge in xeroradiography and in solid-state flat panel x-ray cameras.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.Nondestructive testing: Selenium is a highly effective Gamma source used in Industrial radiography.

Biological applications

Medical use: The substance loosely called selenium sulfide, SeS₂, actually selenium disulfide or selenium (IV) sulfide, is the active ingredient in some dandruff shampoos. The effect of the active ingredient is to kill 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.

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. 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. Venturi et al. suggested that algal cells required a protective antioxidant action, in which selenium and iodides, through peroxidase enzymes, have had this specific role. 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 antioxidant enzymes (GSH-Px). In fact, seaweeds accumulate high quantity of selenium and iodine. In 2008, Küpper et al., 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 today’s humans.

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. Selenoprotein families of GSH-Px and deiodinase of eukaryotic cells seem to have a bacterial phylogenetic origin. The selenocysteine-containing form occurred in green algae, diatoms, sea urchin, fish and chicken, too. One family of selenium-containing molecules as glutathione peroxidases repairs damaged cell membranes, while another (glutathione S-transferases) repairs damaged DNA and prevents mutations.

When 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.) was a challenge to the evolution of terrestrial life. Trace elements involved in GSH-Px and superoxide dismutases enzymes activities, i.e. selenium, vanadium, magnesium, copper and zinc, may have been lacking in some terrestrial mineral-deficient areas. Marine organisms apparently 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 of vertebrates, aquatic life supports selenium utilization, whereas terrestrial habitats lead to reduced use of this trace element. Marine fishes and vertebrate thyroid glands have the highest concentra¬tion 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, flavonoids, tocopherols etc. A few of these appeared more recently, in last 200-50 Mya, 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.

The deiodinase isoenzymes constituted the second family of eukaryotic selenoproteins with identified enzyme function. Deiodinases are able to extract electrons from iodides, and iodides from iodothyronines. So, are involved in thyroid hormone regulation, participating in the protection of thyrocytes from damage by H₂O₂ produced for thyroid hormone biosynthesis. About 200 Mya, new selenoproteins were developed as mammalian GSH-Px enzymes.