Selenium
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{{infobox selenium}}
'''Selenium''' ({{pronEng|səˈliːniəm}}) is a [[chemical element]] with the [[atomic number]] 34, represented by the chemical symbol '''Se'''. 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.<ref>http://cals.arizona.edu/arec/pubs/rmg/1%20rangelandmanagement/2%20poisonousplants93.pdf</ref>
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 [[photocell]]s (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 [[Chemical bond|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 [[sodium selenite|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 [[bioaccumulation|bioconcentrated]] by certain toxic plants such as [[locoweed]]. Anthropogenic sources of selenium include coal burning and the mining and smelting of sulfide ores.<ref>http://www.atsdr.cdc.gov/toxprofiles/tp92-c1.pdf</ref>
''See also [[:Category:Selenide minerals|Selenide minerals]].''
==Isotopes==
{{main|isotopes of selenium}}
Selenium has six naturally occurring [[isotope]]s, five of which are stable: <sup>74</sup>Se, <sup>76</sup>Se, <sup>77</sup>Se, <sup>78</sup>Se, and <sup>80</sup>Se. The last three also occur as [[fission products]], along with [[Se-79|<sup>79</sup>Se]] which has a [[halflife]] of 295,000 years, and <sup>82</sup>Se which has a very long half life (~10<sup>20</sup> yr, decaying via double beta decay to [[Krypton|<sup>82</sup>Kr]]) and for practical purposes can be considered to be stable. 23 other unstable isotopes have been characterized.{{Fact|date=May 2008}}
''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 language|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]]. 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.<ref>http://minerals.usgs.gov/minerals/pubs/commodity/selenium/830398.pdf</ref>
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]] [[brass]]es 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 [[dietary mineral|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).<ref>http://cals.arizona.edu/arec/pubs/rmg/1%20rangelandmanagement/2%20poisonousplants93.pdf</ref> It is a component of the unusual [[amino acid]]s [[selenocysteine]] and [[selenomethionine]]. In humans, selenium is a [[dietary mineral|trace element]] nutrient which functions as [[cofactor]] for [[redox|reduction]] of [[antioxidant]] enzymes such as [[glutathione peroxidase]]s 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+ H<sub>2</sub>O<sub>2</sub>---------GSH-Px → GSSG + 2 H<sub>2</sub>O
Selenium also plays a role in the functioning of the [[thyroid]] gland by participating as a [[Cofactor (biochemistry)|cofactor]] for the three known [[thyroid hormone]] [[deiodinase]]s.<ref>[http://lpi.oregonstate.edu/infocenter/minerals/selenium/ Linus Pauling Institute at Oregon State University<!-- Bot generated title -->]</ref>
Dietary selenium comes from nuts, cereals, meat, fish, and eggs. [[Brazil nut]]s 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.<ref>{{cite journal |last=Barclay |first=Margaret N. I. |authorlink= |coauthors=Allan MacPherson, James Dixon |year=1995 |month= |title=Selenium content of a range of UK food |journal=Journal of food composition and analysis |volume=8 |issue= |pages=307–318 |id=0889-1575|doi=10.1006/jfca.1995.1025 }}</ref><ref> A list of selenium rich foods can be found on [http://ods.od.nih.gov/factsheets/selenium.asp#h2 The Office of Dietary Supplements Selenium Fact Sheet].</ref>
===Toxicity===
Although selenium is an essential [[dietary mineral|trace element]], it is toxic if taken in excess. Exceeding the [[Dietary Reference Intake|Tolerable Upper Intake Level]] of 400 micrograms per day can lead to [[selenosis]].<ref>[http://ods.od.nih.gov/factsheets/selenium.asp#h7 Dietary Supplement Fact Sheet: Selenium<!-- Bot generated title -->]</ref> 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.<ref name="tp92-c3">[http://www.atsdr.cdc.gov/toxprofiles/tp92-c3.pdf DRAFT<!-- Bot generated title -->]</ref>
Elemental selenium and most metallic [[selenide]]s have relatively low toxicities because of their low [[bioavailability]]. By contrast, [[selenate]] and [[selenous acid|selenite]] are very toxic, and have modes of action similar to that of arsenic. [[Hydrogen selenide]] is an extremely toxic, corrosive gas.<ref>http://www.tc.gc.ca/canutec/erg_gmu/search/guide.asp?Guide=117&Lang=EN</ref> 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. [[Nanotechnology|Nano]]-size selenium has equal efficacy, but much lower toxicity.<ref>{{cite journal |author=Zhang J, Wang X, Xu T |title=Elemental selenium at nano size (Nano-Se) as a potential chemopreventive agent with reduced risk of selenium toxicity: comparison with se-methylselenocysteine in mice |journal=Toxicol. Sci. |volume=101 |issue=1 |pages=22–31 |year=2008 |pmid=17728283 |doi=10.1093/toxsci/kfm221}}</ref><ref>{{cite journal |author=Gao X, Zhang J, Zhang L |title=[Acute toxicity and bioavailability of nano red elemental selenium] |language=Chinese |journal=Wei Sheng Yan Jiu |volume=29 |issue=1 |pages=57–8 |year=2000 |pmid=12725047 |doi=}}</ref><ref>{{cite journal |author=Zhang JS, Gao XY, Zhang LD, Bao YP |title=Biological effects of a nano red elemental selenium |journal=Biofactors |volume=15 |issue=1 |pages=27–38 |year=2001 |pmid=11673642 |doi=}}</ref><ref>{{cite journal |author=Zhang J, Wang H, Yan X, Zhang L |title=Comparison of short-term toxicity between Nano-Se and selenite in mice |journal=Life Sci. |volume=76 |issue=10 |pages=1099–109 |year=2005 |pmid=15620574 |doi=10.1016/j.lfs.2004.08.015}}</ref><ref>{{cite journal |author=Jia X, Li N, Chen J |title=A subchronic toxicity study of elemental Nano-Se in Sprague-Dawley rats |journal=Life Sci. |volume=76 |issue=17 |pages=1989–2003 |year=2005 |pmid=15707881 |doi=10.1016/j.lfs.2004.09.026}}</ref><ref>{{cite journal |author=Wang H, Zhang J, Yu H |title=Elemental selenium at nano size possesses lower toxicity without compromising the fundamental effect on selenoenzymes: comparison with selenomethionine in mice |journal=Free Radic. Biol. Med. |volume=42 |issue=10 |pages=1524–33 |year=2007 |pmid=17448899 |doi=10.1016/j.freeradbiomed.2007.02.013}}</ref><ref>{{cite journal |author=Peng D, Zhang J, Liu Q, Taylor EW |title=Size effect of elemental selenium nanoparticles (Nano-Se) at supranutritional levels on selenium accumulation and glutathione S-transferase activity |journal=J. Inorg. Biochem. |volume=101 |issue=10 |pages=1457–63 |year=2007 |pmid=17664013 |doi=10.1016/j.jinorgbio.2007.06.021}}</ref>
[[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.<ref>http://www.webpages.uidaho.edu/~childers/3_31_05%20selenium.pdf</ref>
===Deficiency===
Selenium deficiency is relatively rare in healthy well-nourished individuals. It can occur in patients with severely compromised [[intestine|intestinal]] function, or those undergoing [[total parenteral nutrition]]. Alternatively, people dependent on food grown from selenium-deficient soil are also at risk. In the USA, the [[Dietary Reference Intake]] for adults is 55 µg/day. In the UK it is 75 µg/day for adult males and 60 µg/day for adult females. 55 µg/day recommendation is based on full expression of plasma [[glutathione peroxidase]]. [[Selenoprotein P]]<ref name="pmid17508906">{{cite journal |author=Papp LV, Lu J, Holmgren A, Khanna KK |title=From selenium to selenoproteins: synthesis, identity, and their role in human health |journal=Antioxid. Redox Signal. |volume=9 |issue=7 |pages=775–806 |year=2007 |pmid=17508906 |doi=10.1089/ars.2007.1528}}</ref> is a better indicator of selenium nutritional status, and full expression of it would require more than 66 µg/day.<ref name="pmid15817859">{{cite journal |author=Xia Y, Hill KE, Byrne DW, Xu J, Burk RF |title=Effectiveness of selenium supplements in a low-selenium area of China |journal=Am. J. Clin. Nutr. |volume=81 |issue=4 |pages=829–34 |year=2005 |pmid=15817859 |doi=}}</ref>
Selenium deficiency can lead to [[Keshan disease]], which is potentially fatal. Selenium deficiency also contributes (along with iodine deficiency) to Kashin-Beck disease.<ref>[http://www.atsdr.cdc.gov/toxprofiles/tp92-c3.pdf DRAFT<!-- Bot generated title -->]</ref> The primary symptom of Keshan disease is [[myocardium|myocardial]] [[necrosis]], leading to weakening of the heart. Kashin-Beck disease results in [[atrophy]], degeneration and [[necrosis]] of [[cartilage]] tissue.<ref>[http://content.nejm.org/cgi/content/short/339/16/1112 NEJM - Kashin-Beck Osteoarthropathy in Rural Tibet in Relation to Selenium and Iodine Status<!-- Bot generated title -->]</ref> Keshan disease also makes the body more susceptible to illness caused by other nutritional, biochemical, or infectious diseases. These diseases are most common in certain parts of China where the soil is extremely deficient in selenium. Studies in [[Jiangsu Province]] of China have indicated a reduction in the prevalence of these diseases by taking selenium supplements.
Selenium is also necessary for the conversion of the thyroid hormone [[thyroxine]] (T4) into its more active counterpart, [[triiodothyronine]], and as such a deficiency can cause symptoms of [[hypothyroidism]], including extreme fatigue, mental slowing, [[goitre]], [[cretinism]] and [[habitual abortion|recurrent miscarriage]].<ref name="tp92-c3"/>
===Controversial health effects===
;Cancer: Several studies have suggested a link between cancer and selenium deficiency.<ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=%209290116&dopt=Abstract Plasma selenium levels and the risk of colorectal ...[Nutr Cancer. 1997] - PubMed Result<!-- Bot generated title -->]</ref><ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=8993799&dopt=Abstract Naturally occurring selenium compounds in cancer c...[Cancer Epidemiol Biomarkers Prev. 1997] - PubMed Result<!-- Bot generated title -->]</ref><ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=%209829869&dopt=Abstract Is low selenium status a risk factor for lung canc...[Am J Epidemiol. 1998] - PubMed Result<!-- Bot generated title -->]</ref><ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=9279064&dopt=Abstract Dietary selenium repletion may reduce cancer incid...[Nutr Rev. 1997] - PubMed Result<!-- Bot generated title -->]</ref><ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=3923345&dopt=Abstract The genotoxicity of selenium. [Mutat Res. 1985] - PubMed Result<!-- Bot generated title -->]</ref><ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=10335455&dopt=Abstract Intervention studies on cancer. [Eur J Cancer Prev. 1999] - PubMed Result<!-- Bot generated title -->]</ref><ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=2136228&dopt=Abstract Blood serum selenium in the province of Mérida, Ve...[J Trace Elem Electrolytes Health Dis. 1990] - PubMed Result<!-- Bot generated title -->]</ref> 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.<ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=8971064&dopt=Abstract Effects of selenium supplementation for cancer pre...[JAMA. 1996] - PubMed Result<!-- Bot generated title -->]</ref> Dietary selenium prevents chemically induced carcinogenesis in many rodent studies.<ref>[http://www.inra.fr/reseau-nacre/sci-memb/corpet/indexan.html Chemoprevention Database]</ref> 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.<ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=7707436&dopt=Abstract Prospective study of toenail selenium levels and c...[J Natl Cancer Inst. 1995] - PubMed Result<!-- Bot generated title -->]</ref> The SU.VI.MAX study<ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=9503043&dopt=Abstract Background and rationale behind the SU.VI.MAX Stud...[Int J Vitam Nutr Res. 1998] - PubMed Result<!-- Bot generated title -->]</ref> 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 31% 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.<ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=15557412&dopt=Citation The SU.VI.MAX Study: a randomized, placebo-control...[Arch Intern Med. 2004] - PubMed Result<!-- Bot generated title -->]</ref> The SELECT study<ref>[http://www.crab.org/select/ Selenium and Vitamin E Cancer Prevention Trial (SELECT) Home Page<!-- Bot generated title -->]</ref> 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.<ref>[http://nutrition-health.info/index.php/Selenium_and_Chemotherapeutic_Drugs Selenium and Chemotherapy - Nutrition Health<!-- Bot generated title -->]</ref> One study<ref>[http://nutrition-health.info/index.php/Selenium_Cancer_1 Selenium Cancer 1 - Nutrition Health<!-- Bot generated title -->]</ref> 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<ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=10608913&dopt=Abstract Nutrients and HIV: part one - beta carotene and s...[Altern Med Rev. 1999] - PubMed Result<!-- Bot generated title -->]</ref> 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.<ref>[http://ods.od.nih.gov/factsheets/selenium.asp#h6 Dietary Supplement Fact Sheet: Selenium<!-- Bot generated title -->]</ref> 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-cell]]s, further weakening the immune system.<ref>http://www.hdfoster.com/index.html#Publications</ref>
: 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.<ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=9342257&dopt=Abstract High risk of HIV-related mortality is associated w...[J Acquir Immune Defic Syndr Hum Retrovirol. 1997] - PubMed Result<!-- Bot generated title -->]</ref><ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=10225235&dopt=Abstract Mortality risk in selenium-deficient HIV-positive ...[J Acquir Immune Defic Syndr Hum Retrovirol. 1999] - PubMed Result<!-- Bot generated title -->]</ref><ref>[http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=9481135&dopt=Abstract Micronutrient status in relationship to mortality ...[Nutr Rev. 1998] - PubMed Result<!-- Bot generated title -->]</ref>
;Tuberculosis: Some research has suggested that selenium supplementation, along with other nutrients, can help prevent the recurrence of tuberculosis.<ref name="pmid18471061">{{cite journal |author=Villamor E, Mugusi F, Urassa W, ''et al'' |title=A Trial of the Effect of Micronutrient Supplementation on Treatment Outcome, T Cell Counts, Morbidity, and Mortality in Adults with Pulmonary Tuberculosis |journal=J. Infect. Dis. |volume=197 |issue=11 |pages=1499–1505 |year=2008 |month=June |pmid=18471061 |doi=10.1086/587846 |url=http://www.nutraingredients-usa.com/news/ng.asp?id=84945-micronutrients-tuberculosis-selenium}}</ref>
;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.<ref>[http://care.diabetesjournals.org/cgi/content/abstract/30/4/829 Serum Selenium and Diabetes in U.S. Adults - Bleys et al. 30 (4): 829 - Diabetes Care<!-- Bot generated title -->]</ref>
;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.<ref>{{cite journal |journal= Tohoku J Exp Med |date=2002 |volume=196 |issue=2 |pages=71–7 |title= Modification of mercury toxicity by selenium: practical importance? |author= Watanabe C |doi=10.1620/tjem.196.71 |pmid=12498318 |url=http://www.jstage.jst.go.jp/article/tjem/196/2/71/_pdf |format=PDF}}</ref>
==Production and allotropic forms==
Selenium is a common byproduct of copper refining, or the production of sulfuric acid.<ref>http://www.atsdr.cdc.gov/toxprofiles/tp92-c5.pdf</ref><ref>[http://periodic.lanl.gov/elements/34.html Selenium<!-- Bot generated title -->]</ref><ref>[http://www.webelements.com/webelements/elements/text/Se/key.html Chemistry : Periodic Table : selenium : key information<!-- Bot generated title -->]</ref> Isolation of selenium is often complicated by the presence of other compounds and elements. Commonly, production begins by oxidation with sodium carbonate to produce sodium selenite. The sodium selenite is then acidified with sulfuric acid 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 Se<sub>8</sub> molecules, similar to many allotropes of sulfur.<ref>[http://www.chemistryexplained.com/A-Ar/Allotropes.html Allotropes - Group 13, Group 14, Group 15, Group 16<!-- Bot generated title -->]</ref>
==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 [[Multi-wavelength anomalous dispersion|MAD]] and [[Single-wavelength anomalous dispersion|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, [[vitreous enamel|enamels]] and [[ceramic glaze|glazes]] as well as to remove color from glass by counteracting the green tint imparted by ferrous impurities.
: Selenium is used with [[bismuth]] in [[brass]]es to replace more toxic [[lead]]. It is also used to improve abrasion resistance in [[vulcanization|vulcanized]] [[rubber]]s.
;Electronics: Because of its [[photovoltaics|photovoltaic]] and [[photoconductivity|photoconductive]] properties, selenium is used in [[photocopying]], [[photocell]]s, [[light meter]]s and [[solar cell]]s. It was once widely used in [[rectifier]]s. 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 varistor]]s.
: 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 [[photographic print toning|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 ray|Gamma]] source used in [[Industrial radiography]]{{Fact|date=February 2008}}.
==Biological applications==
;Medical use: The substance loosely called [[selenium sulfide]], '''SeS<sub>2</sub>''', actually selenium disulfide or selenium (IV) sulfide, is the active ingredient in some dandruff shampoos.<ref>[http://pharmacycode.com/Selenium(IV)_sulfide.html Accessed Dec. 25, 2007]</ref> 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.<ref>[http://dermnetnz.org/treatments/selenium.html Selenium sulfide. DermNet NZ<!-- Bot generated title -->]</ref>
;Nutrition: Selenium is used widely in [[vitamin]] preparations and other [[dietary supplement]]s, in small doses (typically 50 to 200 micrograms per day for adult humans). Some livestock [[fodder|feed]]s 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.<ref name=venturi>Venturi S, Donati FM, Venturi A, Venturi M. 2000 . Environmental iodine deficiency: A challenge to the evolution of terrestrial life? Thyroid. 10 (8):727-9.</ref> 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.<ref name=venturi /><ref name=venturi2>Venturi S, Venturi M. Evolution of Dietary Antioxidant Defences. 2007. European Epi-Marker. 11, 3 :1-12. http://web.tiscali.it/iodio/</ref> 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,<ref>Cocchi M, Venturi S. 2000. Selenium and Iodide: ancient antioxidants of cellular membranes? 7th Internat. Symp. on Selenium in Biology and Medicine. Venice (Italy). Abs. P-88 :134</ref> is a primitive mineral antioxidant, greatly present in the sea and prokaryotic cells, where it is an essential component of family of glutathione peroxidase antioxidant enzymes (GSH-Px). In fact, [[seaweed]]s accumulate high quantity of selenium and iodine.<ref name=venturi /> In 2008, Küpper et al.,<ref>Küpper FC, Carpenter LJ, McFiggans GB, et al. 2008. Iodide accumulation provides kelp with an inorganic antioxidant impacting atmospheric chemistry. Proc Natl Acad Sci USA.13;105(19):6954-8.</ref> 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,<ref name=glady>Gladyshev VN, Hatfield DL. 1999 . Selenocysteine-containing proteins in mammals. J Biomed Sci. 6:151-160.</ref> 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.<ref>Stadtman TC. 1996 . Selenocysteine. Annu Rev Biochem. 65:83-100.</ref>
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.<ref name=venturi /> 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.<ref name=glady /> 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 [[vertebrate]]s, aquatic life supports selenium utilization, whereas terrestrial habitats lead to reduced use of this trace element.<ref>Lobanov AV, Fomenko DE, Zhang Y, et al. 2007. Evolutionary dynamics of eukaryotic selenoproteomes: large selenoproteomes may associate with aquatic life and small with terrestrial life. Genome Biol. 8(9):R198.</ref> 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 H<sub>2</sub>O<sub>2</sub> produced for thyroid hormone biosynthesis.<ref name=venturi /><ref name=venturi2 /> About 200 Mya, new selenoproteins were developed as mammalian GSH-Px enzymes.<ref>Castellano S, Novoselov SV, Kryukov GV, et al. 2004. Reconsidering the evolution of eukaryotic selenoproteins: a novel non-mammalian family with scattered phylogenetic distribution. EMBO Rep. 5 (1):71-7.</ref><ref>Kryukov GV, Gladyshev VN. 2004. The prokaryotic selenoproteome. EMBO Rep. (5) :538-43. </ref><ref>Wilting R, Schorling S, Persson BC, Bock A. 1997. Selenoprotein synthesis in archaea: identification of an mRNA element of ''[[Methanococcus jannaschii]]'' probably directing selenocysteine insertion. J Mol Biol. 266 (4) :637-41.</ref><ref>Zhang Y, Fomenko DE, Gladyshev VN. 2005. The microbial selenoproteome of the Sargasso Sea. Genome Biol. 6 (4) :R37.</ref>
==Compounds==
*[[Copper indium gallium selenide]] Cu(Ga,In)Se<sub>2</sub>
*[[Mercury selenide]] (HgSe)
*[[Hydrogen selenide]] (H<sub>2</sub>Se)
*[[Lead(II) selenide|Lead selenide]] (PbSe)
*[[Selenium dioxide]] (SeO<sub>2</sub>)
*[[Selenic acid]] (H<sub>2</sub>SeO<sub>4</sub>)
*[[Selenous acid]] (H<sub>2</sub>SeO<sub>3</sub>)
*[[Selenium sulfide]]s: Se<sub>4</sub>S<sub>4</sub>, SeS<sub>2</sub>, Se<sub>2</sub>S<sub>6</sub>
*[[Sodium selenite]] (Na<sub>2</sub>SeO<sub>3</sub>)
*[[Zinc selenide]] (ZnSe)
Selenium also occurs in the III oxidation state, but only in the Se<sub>4</sub><sup>12+</sup> cation; Se(III) compounds are not otherwise known.<ref>{{cite web|url=http://www.webelements.com/webelements/compounds/text/Se/N4Se4-12033884.html|title=Selenium : Selenium nitride compound data|accessdate=2007-12-10|publisher=WebElements.com}}</ref>
''See also [[:Category:Selenium compounds|Selenium compounds]] and [[organoselenium chemistry]].''
==Reference in popular culture==
In the plot of the hit movie [[Evolution (film)|Evolution]] staring [[David Duchovny]] It is discovered that selenium, an ingredient in some dandruff shampoos, is as poisonous to invading alien life-forms as arsenic is to humans.
==References==
{{reflist}}
== External links ==
{{Commons|Selenium}}
{{wiktionary|selenium}}
*[http://periodic.lanl.gov/elements/34.html Los Alamos National Labs Chemistry Division - Selenium]
*[http://www.webelements.com/webelements/elements/text/Se/index.html WebElements.com - Selenium]
*[http://ods.od.nih.gov/factsheets/selenium.asp National Institutes of Health page on Selenium]
*[http://www.atsdr.cdc.gov/toxprofiles/tp92.html ATSDR - Toxicological Profile: Selenium]
*[http://elements.vanderkrogt.net/elem/se.html Peter van der Krogt elements site]
{{clear}}
{{compact periodic table}}
[[Category:Antioxidants]]
[[Category:Chalcogens]]
[[Category:Chemical elements]]
[[Category:Dietary minerals]]
[[Category:Element toxicology]]
[[Category:Nonmetals]]
[[Category:Selenium|*]]
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