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Selenium, 34Se
|
General properties |
Pronunciation | (sə-LEE-nee-əm) |
Appearance | black, red, and gray (not pictured) allotropes |
Standard atomic weight (Ar, standard) | 78.971(8)[1] |
Selenium in the periodic table |
|
Atomic number (Z) | 34 |
Group | group 16 (chalcogens) |
Period | period 4 |
Element category | reactive nonmetal, sometimes considered a metalloid |
Block | p-block |
Electron configuration | [Ar] 3d10 4s2 4p4 |
Electrons per shell
| 2, 8, 18, 6 |
Physical properties |
Phase at STP | solid |
Melting point | 494 K (221 °C, 430 °F) |
Boiling point | 958 K (685 °C, 1265 °F) |
Density (near r.t.) | gray: 4.81 g/cm3
alpha: 4.39 g/cm3
vitreous: 4.28 g/cm3 |
when liquid (at m.p.) | 3.99 g/cm3 |
Critical point | 1766 K, 27.2 MPa |
Heat of fusion | gray: 6.69 kJ/mol |
Heat of vaporization | 95.48 kJ/mol |
Molar heat capacity | 25.363 J/(mol·K) |
Vapor pressure
P (Pa)
|
1
|
10
|
100
|
1 k
|
10 k
|
100 k
|
at T (K)
|
500
|
552
|
617
|
704
|
813
|
958
|
|
Atomic properties |
Oxidation states | 6, 5, 4, 3, 2, 1,[2] −1, −2 (a strongly acidic oxide) |
Electronegativity | Pauling scale: 2.55 |
Ionization energies |
- 1st: 941.0 kJ/mol
- 2nd: 2045 kJ/mol
- 3rd: 2973.7 kJ/mol
-
|
Atomic radius | empirical: 120 pm |
Covalent radius | 120±4 pm |
Van der Waals radius | 190 pm |
|
Miscellanea |
Crystal structure | hexagonal
|
Speed of sound thin rod | 3350 m/s (at 20 °C) |
Thermal expansion | amorphous: 37 µm/(m·K) (at 25 °C) |
Thermal conductivity | amorphous: 0.519 W/(m·K) |
Magnetic ordering | diamagnetic[3] |
Magnetic susceptibility | −25.0·10−6 cm3/mol (298 K)[4] |
Young's modulus | 10 GPa |
Shear modulus | 3.7 GPa |
Bulk modulus | 8.3 GPa |
Poisson ratio | 0.33 |
Mohs hardness | 2.0 |
Brinell hardness | 736 MPa |
CAS Number | 7782-49-2 |
History |
Naming | after Selene, Greek goddess of the moon |
Discovery and first isolation | Jöns Jakob Berzelius and Johann Gottlieb Gahn (1817) |
Main isotopes of selenium |
|
Selenium is a
chemical element with symbol
Se and
atomic number 34. It is a
nonmetal with properties that are intermediate between the elements above and below in the
periodic table,
sulfur and
tellurium, and also has similarities to
arsenic. It rarely occurs in its elemental state or as pure ore compounds in the Earth's crust. Selenium (from
Ancient Greek σελήνη (selḗnē) "Moon") was discovered in 1817 by
Jöns Jacob Berzelius, who noted the similarity of the new element to the previously discovered
tellurium (named for the Earth).
Selenium is found in
metal sulfide ores,
where it partially replaces the sulfur. Commercially, selenium is
produced as a byproduct in the refining of these ores, most often during
production. Minerals that are pure selenide or selenate compounds are
known but rare. The chief commercial uses for selenium today are
glassmaking and
pigments. Selenium is a
semiconductor and is used in
photocells. Applications in
electronics, once important, have been mostly replaced with
silicon semiconductor devices. Selenium is still used in a few types of DC power
surge protectors and one type of
fluorescent quantum dot.
Selenium salts are toxic in large amounts, but trace amounts are
necessary for cellular function in many organisms, including all
animals. Selenium is an ingredient in many multivitamins and other
dietary supplements, including
infant formula. It is a component of the antioxidant enzymes
glutathione peroxidase and
thioredoxin reductase (which indirectly reduce certain
oxidized molecules in animals and some plants). 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 requiring relatively large amounts and others apparently
requiring none.
[5]
Characteristics
Physical properties
Structure of hexagonal (gray) selenium
Selenium forms several
allotropes
that interconvert with temperature changes, depending somewhat on the
rate of temperature change. When prepared in chemical reactions,
selenium is usually an
amorphous, brick-red powder. When rapidly melted, it forms the black, vitreous form, usually sold commercially as beads.
[6]
The structure of black selenium is irregular and complex and consists
of polymeric rings with up to 1000 atoms per ring. Black Se is a
brittle, lustrous solid that is slightly soluble in
CS2.
Upon heating, it softens at 50 °C and converts to gray selenium at
180 °C; the transformation temperature is reduced by presence of
halogens and
amines.
[7]
The red α, β, and γ forms are produced from solutions of black
selenium by varying the evaporation rate of the solvent (usually CS
2). They all have relatively low,
monoclinic crystal symmetries and contain nearly identical puckered Se
8 rings with different arrangements, as in
sulfur. The packing is most dense in the α form. In the Se
8 rings, the Se-Se distance is 233.5 pm and Se-Se-Se angle is 105.7°. Other selenium allotropes may contain Se
6 or Se
7 rings.
[7]
The most stable and dense form of selenium is gray and has a
hexagonal crystal lattice consisting of helical polymeric chains, where
the Se-Se distance is 237.3 pm and Se-Se-Se angle is 130.1°. The minimum
distance between chains is 343.6 pm. Gray Se is formed by mild heating
of other allotropes, by slow cooling of molten Se, or by condensing Se
vapor just below the melting point. Whereas other Se forms are
insulators, gray Se is a semiconductor showing appreciable
photoconductivity. Unlike the other allotropes, it is insoluble in CS
2.
[7] It resists oxidation by air and is not attacked by nonoxidizing
acids.
With strong reducing agents, it forms polyselenides. Selenium does not
exhibit the changes in viscosity that sulfur undergoes when gradually
heated.
[6][8]
Optical properties
Owing to its use as a photoconductor in flat-panel x-ray detectors (see
below), the optical properties of amorphous selenium (α-Se) thin films have been the subject of intense research.
[9][10][11]
Isotopes
Selenium has seven natural
isotopes, including
79Se, which occurs in minute quantities in
uranium ores, as well as 23 other synthetic isotopes.
Selenium isotopes of greatest stability
Isotope
|
Nature
|
Origin
|
Half-life
|
74Se
|
Natural
|
|
Stable
|
76Se
|
Natural
|
|
Stable
|
77Se
|
Natural
|
Fission product
|
Stable
|
78Se
|
Natural
|
Fission product
|
Stable
|
79Se
|
Trace
|
Fission product
|
327000 yr[12][13]
|
80Se
|
Natural
|
Fission product
|
Stable
|
82Se
|
Natural
|
Fission product[14]
|
~1020 yr[15]
|
Chemical compounds
Selenium compounds commonly exist in the
oxidation states −2, +2, +4, and +6.
Chalcogen compounds
Selenium forms two
oxides:
selenium dioxide (SeO
2) and
selenium trioxide (SeO
3). Selenium dioxide is formed by the reaction of elemental selenium with oxygen:
[6]
- Se8 + 8 O2 → 8 SeO2
Structure of the polymer SeO2: The (pyramidal) Se atoms are yellow.
It is a
polymeric solid that forms monomeric SeO
2 molecules in the gas phase. It dissolves in water to form
selenous acid, H
2SeO
3. Selenous acid can also be made directly by oxidizing elemental selenium with
nitric acid:
[16]
- 3 Se + 4 HNO3 + H2O → 3 H2SeO3 + 4 NO
Unlike sulfur, which forms a stable
trioxide, selenium trioxide is thermodynamically unstable and decomposes to the dioxide above 185 °C:
[6][16]
- 2 SeO3 → 2 SeO2 + O2 (ΔH = −54 kJ/mol)
Selenium trioxide is produced in the laboratory by the reaction of
anhydrous potassium selenate (K
2SeO
4) and sulfur trioxide (SO
3).
[17]
Salts of selenous acid are called selenites. These include
silver selenite (Ag
2SeO
3) and
sodium selenite (Na
2SeO
3).
Hydrogen sulfide reacts with aqueous selenous acid to produce
selenium disulfide:
- H2SeO3 + 2 H2S → SeS2 + 3 H2O
Selenium disulfide consists of 8-membered rings. It has an approximate composition of SeS
2, with individual rings varying in composition, such as Se
4S
4 and Se
2S
6. Selenium disulfide has been used in shampoo as an anti
dandruff agent, an inhibitor in polymer chemistry, a glass dye, and a reducing agent in
fireworks.
[16]
Selenium trioxide may be synthesized by dehydrating
selenic acid, H
2SeO
4, which is itself produced by the oxidation of selenium dioxide with
hydrogen peroxide:
[18]
- SeO2 + H2O2 → H2SeO4
Hot, concentrated selenic acid can react with gold to form gold(III) selenate.
[19]
Halogen compounds
Iodides of selenium are not well known. The only stable
chloride is
selenium monochloride (Se
2Cl
2), which might be better known as selenium(I) chloride; 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 Se
7). It is prepared by treating selenium with
sulfuryl chloride (SO
2Cl
2).
[20] Selenium reacts with
fluorine to form
selenium hexafluoride:
- Se8 + 24 F2 → 8 SeF6
In comparison with its sulfur counterpart (
sulfur hexafluoride),
selenium hexafluoride (SeF
6) is more reactive and is a toxic
pulmonary irritant.
[21]
Some of the selenium oxyhalides, such as
selenium oxyfluoride (SeOF
2) and
selenium oxychloride (SeOCl
2) have been used as specialty solvents.
[6]
Selenides
Analogous to the behavior of other chalcogens, selenium forms
hydrogen selenide, H
2Se. It is a strongly
odiferous, toxic, and colorless gas. It is more acidic than H
2S. In solution it ionizes to HSe
−. The selenide dianion Se
2−
forms a variety of compounds, including the minerals from which
selenium is obtained commercially. Illustrative selenides include
mercury selenide (HgSe),
lead selenide (PbSe),
zinc selenide (ZnSe), and
copper indium gallium diselenide (Cu(Ga,In)Se
2). These materials are
semiconductors. With highly electropositive metals, such as
aluminium, these selenides are prone to hydrolysis:
[6]
- Al2Se3 + 3 H2O → Al2O3 + 3 H2Se
Alkali metal selenides react with selenium to form polyselenides,
Se2−
n, which exist as chains.
Other compounds
Tetraselenium tetranitride, Se
4N
4, is an explosive orange compound analogous to
tetrasulfur tetranitride (S
4N
4).
[6][22][23] It can be synthesized by the reaction of
selenium tetrachloride (SeCl
4) with
[((CH
3)
3Si)
2N]
2Se.
[24]
Selenium reacts with
cyanides to yield selenocyanates:
[6]
- 8 KCN + Se8 → 8 KSeCN
Organoselenium compounds
Selenium, especially in the II oxidation state, forms stable bonds to
carbon, which are structurally analogous to the corresponding
organosulfur compounds. Especially common are selenides (R
2Se, analogues of
thioethers), diselenides (R
2Se
2, analogues of
disulfides), and
selenols (RSeH, analogues of
thiols). Representatives of selenides, diselenides, and selenols include respectively
selenomethionine,
diphenyldiselenide, and
benzeneselenol. The
sulfoxide
in sulfur chemistry is represented in selenium chemistry by the
selenoxides (formula RSe(O)R), which are intermediates in organic
synthesis, as illustrated by the
selenoxide elimination reaction. Consistent with trends indicated by the
double bond rule, selenoketones, R(C=Se)R, and selenaldehydes, R(C=Se)H, are rarely observed.
[25]
History
Selenium (
Greek σελήνη
selene meaning "Moon") was discovered in 1817 by
Jöns Jakob Berzelius and
Johan Gottlieb Gahn.
[26] Both chemists owned a chemistry plant near
Gripsholm, Sweden, producing
sulfuric acid by the
lead chamber process. The pyrite from the
Falun mine
created a red precipitate in the lead chambers which was presumed to be
an arsenic compound, so the pyrite's use to make acid was discontinued.
Berzelius and Gahn wanted to use the pyrite and they also observed that
the red precipitate gave off a smell like
horseradish when burned. This smell was not typical of arsenic, but a similar odor was known from
tellurium compounds. Hence, Berzelius's first letter to
Alexander Marcet stated that this was a tellurium compound. However, the lack of tellurium compounds in the
Falun mine
minerals eventually led Berzelius to reanalyze the red precipitate, and
in 1818 he wrote a second letter to Marcet describing a newly found
element similar to
sulfur and tellurium. Because of its similarity to tellurium, named for the Earth, Berzelius named the new element after the
Moon.
[27][28]
In 1873,
Willoughby Smith found that the electrical resistance of grey selenium was dependent on the ambient light.
[29] This led to its use as a cell for sensing light. The first commercial products using selenium were developed by
Werner Siemens in the mid-1870s. The selenium cell was used in the
photophone developed by
Alexander Graham Bell
in 1879. Selenium transmits an electric current proportional to the
amount of light falling on its surface. This phenomenon was used in the
design of
light meters and similar devices. Selenium's semiconductor properties found numerous other applications in electronics.
[30][31][32] The development of
selenium rectifiers began during the early 1930s, and these replaced
copper oxide rectifiers because they were more efficient.
[33][34][35]
These lasted in commercial applications until the 1970s, following
which they were replaced with less expensive and even more efficient
silicon rectifiers.
Selenium came to medical notice later because of its toxicity to
human beings
working in industries. Selenium was also recognized as an important
veterinary toxin, which is seen in animals that have eaten high-selenium
plants. In 1954, the first hints of specific biological functions of
selenium were discovered in
microorganisms by biochemist,
Jane Pinsent.
[36][37] It was discovered to be essential for mammalian life in 1957.
[38][39] 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, selenocysteine was shown to be encoded by the
codon UGA. The recoding mechanism was worked out first in
bacteria and then in
mammals (see
SECIS element).
[40]
Occurrence
Native (i.e., elemental) selenium is a rare mineral, which does not
usually form good crystals, but, when it does, they are steep
rhombohedra or tiny acicular (hair-like) crystals.
[41] Isolation of selenium is often complicated by the presence of other compounds and elements.
Selenium occurs naturally in a number of inorganic forms, including
selenide,
selenate, and
selenite, but these minerals are rare. The common mineral
selenite is not a selenium mineral, and contains no
selenite ion, but is rather a type of
gypsum
(calcium sulfate hydrate) named like selenium for the moon well before
the discovery of selenium. Selenium is most commonly found as an
impurity, replacing a small part of the sulfur in sulfide ores of many
metals.
[42][43]
In living systems, selenium is found in the amino acids
selenomethionine,
selenocysteine, and
methylselenocysteine. In these compounds, selenium plays a role analogous to that of sulfur. Another naturally occurring
organoselenium compound is dimethyl selenide.
[44][45]
Certain solids are selenium-rich, and selenium can be
bioconcentrated
by some 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.
[42][43] Ocean water contains significant amounts of selenium.
[46][47]
Anthropogenic sources of selenium include coal burning, and the mining and smelting of sulfide ores.
[48]
Production
Selenium is most commonly produced from
selenide in many
sulfide ores, such as those of
copper,
nickel, or
lead. Electrolytic metal refining is particularly productive of selenium as a byproduct, obtained from the
anode mud of copper refineries. Another source was the mud from the
lead chambers of
sulfuric acid
plants, a process that is no longer used. Selenium can be refined from
these muds by a number of methods. However, most elemental selenium
comes as a byproduct of
refining copper or producing
sulfuric acid.
[49][50] Since its invention,
solvent extraction and electrowinning (SX/EW) production of copper produces an increasing share of the worldwide copper supply.
[51]
This changes the availability of selenium because only a comparably
small part of the selenium in the ore is leached with the copper.
[52]
Industrial production of selenium usually involves the extraction of
selenium dioxide from residues obtained during the purification of copper. Common production from the residue then begins by oxidation with
sodium carbonate to produce selenium dioxide, which is mixed with water and
acidified to form
selenous acid (
oxidation step). Selenous acid is bubbled with
sulfur dioxide (
reduction step) to give elemental selenium.
[53][54]
About 2,000 tonnes of selenium were produced in 2011 worldwide,
mostly in Germany (650 t), Japan (630 t), Belgium (200 t), and Russia
(140 t), and the total reserves were estimated at 93,000 tonnes. These
data exclude two major producers, the United States and China. A
previous sharp increase was observed in 2004 from 4–5 to $27/lb. The
price was relatively stable during 2004–2010 at about US$30 per pound
(in 100-pound lots) but increased to $65 /lb in 2011. The consumption in
2010 was divided as follows: metallurgy – 30%, glass manufacturing –
30%, agriculture – 10%, chemicals and pigments – 10%, and electronics –
10%. China is the dominant consumer of selenium at 1,500–2,000
tonnes/year.
[55]
Applications
Manganese electrolysis
During the
electro winning of manganese, the addition of selenium dioxide decreases the power necessary to operate the
electrolysis cells.
China is the largest consumer of selenium dioxide for this purpose. For
every tonne of manganese, an average 2 kg selenium oxide is used.
[55][56]
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 color to
glass. This color cancels out the green or yellow tints that arise from
iron impurities typical for most glass. For this purpose, various
selenite and selenate salts are added. For other applications, a red
color may be desired, produced by mixtures of CdSe and CdS.
[57]
Alloys
Selenium is used with
bismuth in
brasses to replace more toxic
lead. The regulation of lead in drinking water applications with the
Safe Drinking Water Act of 1974 made a reduction of lead in brass necessary. The new brass is marketed under the name EnviroBrass.
[58] Like lead and sulfur, selenium improves the machinability of steel at concentrations around 0.15%.
[59][60] Selenium produces the same machinability improvement in copper alloys.
[61]
Lithium–selenium batteries
Lithium–selenium (Li–Se) battery is one of the most promising system for energy storage in the family of lithium batteries.
[62] Li–Se battery is an alternative to
Lithium–sulfur battery with an advantage of high electrical conductivity.
Solar cells
Copper indium gallium selenide is a material used in solar cells.
[63]
Photoconductors
Amorphous selenium (α-Se) thin films have found application as photoconductors in
flat panel x-ray detectors.
[64] These detectors utilize the amorphous selenium to capture and convert incident x-ray photons directly into electric charge.
[65]
Other uses
Small amounts of organoselenium compounds have been used to modify the catalysts used for the
vulcanization for the production of rubber.
[52]
The demand for selenium by the electronics industry is declining.
[55] Its
photovoltaic and
photoconductive properties are still useful in
photocopying,
[66][67][68][69] photocells,
light meters and
solar cells.
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 organic photoconductors. Though once widely used,
selenium rectifiers have mostly been replaced (or are being replaced) by silicon-based devices. 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.
Zinc selenide was the first material for blue
LEDs, but gallium nitride dominates that market.
[70] Cadmium selenide was an important component in
quantum dots. Sheets of amorphous selenium convert
X-ray images to patterns of charge in
xeroradiography and in solid-state, flat-panel X-ray cameras.
[71] Ionized selenium (Se+24) is one of the active mediums used in X-ray lasers.
[72]
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 selenium atoms in place of sulfur helps with multiple-wavelength anomalous dispersion and
single wavelength anomalous dispersion phasing.
[73]
Selenium is used in the
toning of photographic prints,
and it is sold as a toner by numerous photographic manufacturers.
Selenium intensifies and extends the tonal range of black-and-white
photographic images and improves the permanence of prints.
[74][75][76]
75Se is used as a gamma source in industrial radiography.
[77]
Biological role
NFPA 704
fire diamond
|
|
Fire diamond for elemental selenium
|
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).
[5] See more on plant nutrition below.
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[78] 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).
The
glutathione peroxidase family of enzymes (GSH-Px) catalyze certain reactions that remove reactive oxygen species such as
hydrogen peroxide and organic
hydroperoxides:
- 2 GSH + H2O2----GSH-Px → GSSG + 2 H2O
The thyroid gland and every cell that uses thyroid hormone use
selenium, which is a cofactor for the three of the four known types of
thyroid hormone deiodinases, which activate and then deactivate various thyroid hormones and their metabolites; the
iodothyronine deiodinases
are the subfamily of deiodinase enzymes that use selenium as the
otherwise rare amino acid selenocysteine. (Only the deiodinase,
iodotyrosine deiodinase, which works on the last breakdown products of thyroid hormone, does not use selenium.)
[79]
Selenium may inhibit
Hashimoto's disease,
in which the body's own thyroid cells are attacked as alien. A
reduction of 21% on TPO antibodies is reported with the dietary intake
of 0.2 mg of selenium.
[80]
Increased dietary selenium reduces the effects of mercury toxicity,
[81][82][83] although it is effective only at low to modest doses of mercury.
[84]
Evidence suggests that the molecular mechanisms of mercury toxicity
includes the irreversible inhibition of selenoenzymes that are required
to prevent and reverse oxidative damage in brain and endocrine tissues.
[85][86]
An antioxidant, selenoneine, which is derived from selenium and has
been found to be present in the blood of bluefin tuna, is the subject of
scientific research regarding its possible roles in inflammatory and
chronic diseases, methylmercury detoxification, and oxidative damages.
[87][88]
Evolution in biology
From about three billion years ago, prokaryotic selenoprotein
families drive the evolution of selenocysteine, an amino acid. Selenium
is incorporated into several prokaryotic selenoprotein families in
bacteria, archaea, and eukaryotes as selenocysteine,
[89]
where selenoprotein peroxiredoxins protect bacterial and eukaryotic
cells against oxidative damage. 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 the small reducing molecules
glutathione and
thioredoxin. One family of selenium-bearing molecules (the
glutathione peroxidases)
destroys peroxide and repairs damaged peroxidized cell membranes, using
glutathione. Another selenium-bearing enzyme in some plants and in
animals (
thioredoxin reductase)
generates reduced thioredoxin, a dithiol that serves as an electron
source for peroxidases and also the important reducing enzyme
ribonucleotide reductase that makes DNA precursors from RNA precursors.
[90]
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.
[89]
Marine organisms retained and sometimes expanded their selenoproteomes,
whereas the selenoproteomes of some terrestrial organisms were reduced
or completely lost. These findings suggest that, with the exception of
vertebrates, aquatic life supports selenium use, whereas terrestrial habitats lead to reduced use of this trace element.
[91]
Marine fishes and vertebrate thyroid glands have the highest
concentration of selenium and iodine. From about 500 million years ago,
freshwater and terrestrial plants slowly optimized the production of
"new" endogenous antioxidants such as
ascorbic acid (vitamin C),
polyphenols (including flavonoids),
tocopherols,
etc. 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.
[citation needed]
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 H
2O
2 produced for thyroid-hormone biosynthesis.
[92] About 200 million years ago, new selenoproteins were developed as mammalian GSH-Px enzymes.
Nutritional sources of selenium
Dietary selenium comes from nuts, cereals and mushrooms.
Brazil nuts
are the richest dietary source (though this is soil-dependent, since
the Brazil nut does not require high levels of the element for its own
needs).
[97][98]
The U.S.
Recommended Dietary Allowance
(RDA) for teenagers and adults is 55 µg/day.
Selenium as a dietary supplement is available in many forms, including
multi-vitamins/mineral supplements, which typically contain 55 or
70 µg/serving. Selenium-specific supplements typically contain either
100 or 200 µg/serving.
In June 2015 the U.S.
Food and Drug Administration (FDA) published its final rule establishing the requirement of minimum and maximum levels of selenium in
infant formula.
[99]
The selenium content in the human body is believed to be in the 13–20 milligram range.
[100]
Indicator plant species
Certain
species of plants are considered indicators of high selenium content of
the soil because 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 (
Oonopsis sp.)
[101]
Detection in biological fluids
Selenium
may be measured in blood, plasma, serum, or urine to monitor excessive
environmental or occupational exposure, to confirm a diagnosis of
poisoning in hospitalized victims, or investigate a suspected case of
fatal overdose. 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 elimination in the urine. Cancer
patients receiving daily oral doses of selenothionine may achieve very
high plasma and urine selenium concentrations.
[102]
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.
[103] This 400
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.
[104]
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 avoid creating an
imbalance of nutrients in the diet and to accord with data from other
countries.
[105] 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.
[106]
Signs and 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 exhibit
cirrhosis of the liver,
pulmonary edema, or death.
[107] Elemental selenium and most metallic
selenides have relatively low toxicities because of low
bioavailability. By contrast,
selenates and
selenites
have an oxidant mode of action similar to that of arsenic trioxide and
are very toxic. The chronic toxic dose of selenite for humans is about
2400 to 3000 micrograms of selenium per day.
[108]
Hydrogen selenide is an extremely toxic, corrosive gas.
[109] 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.
On 19 April 2009, 21
polo
ponies died 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 that had been incorrectly prepared
by a
compounding pharmacy. Analysis of blood levels of
inorganic compounds in the supplement indicated the selenium concentrations were ten to fifteen times higher than normal in the
blood samples, and 15 to 20 times higher than normal in the liver samples. Selenium was later confirmed to be the toxic factor.
[110]
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. Selenium pollution of waterways also occurs when selenium is leached
from coal flue ash, mining and metal smelting, crude oil processing, and
landfill.
[111]
The resultant high selenium levels in waterways were found to cause
congenital disorders in oviparous species, including wetland birds
[112] and fish.
[113] Elevated dietary methylmercury levels can amplify the harm of selenium toxicity in oviparous species.
[114][115]
Relationship between survival of juvenile salmon and concentration of selenium in their tissues after 90 days (Chinook salmon
[116]) or 45 days (Atlantic salmon
[117])
exposure to dietary selenium. The 10% lethality level (LC10=1.84 µg/g)
was derived by applying the biphasic model of Brain and Cousens
[118]
to only the Chinook salmon data. The Chinook salmon data comprise two
series of dietary treatments, combined here because the effects on
survival are indistinguishable.
In fish and other wildlife, selenium is necessary for life, but toxic
in high doses. For salmon, the optimal concentration of selenium is
about 1 microgram selenium per gram of whole body weight. Much below
that level, young salmon die from deficiency;
[117] much above, they die from toxic excess.
[116]
The
Occupational Safety and Health Administration (OSHA) has set the legal limit (
Permissible exposure limit) for selenium in the workplace at 0.2 mg/m
3 over an 8-hour workday. The
National Institute for Occupational Safety and Health (NIOSH) has set a
Recommended exposure limit (REL) of 0.2 mg/m
3 over an 8-hour workday. At levels of 1 mg/m
3, selenium is
immediately dangerous to life and health.
[119]
Deficiency
Selenium deficiency can occur in patients with severely compromised
intestinal function, those undergoing
total parenteral nutrition, and
[120] in those of advanced age (over 90). Also, people dependent on food grown from selenium-deficient soil are at risk. Although
New Zealand soil has low levels of selenium, adverse health effects have not been detected in the residents.
[121]
Selenium deficiency, defined by low (<60 a="" activity="" additional="" an="" and="" as="" brain="" class="reference" endocrine="" exposures="" high="" id="cite_ref-122" in="" is="" level="" levels="" linked="" low="" mercury="" normal="" occurs="" of="" only="" selenium="" selenoenzyme="" stress="" such="" sup="" tissues="" to="" when="" with="">
[122] 60>or increased oxidant stress from vitamin E deficiency.
[123]
Selenium interacts with other nutrients, such as
iodine and
vitamin E. The effect of selenium deficiency on health remains uncertain, particularly in relation to
Kashin-Beck disease.
[124] Also, selenium interacts with other minerals, such as
zinc and
copper.
High doses of Se supplements in pregnant animals might disturb the
Zn:Cu ratio and lead to Zn reduction; in such treatment cases, Zn levels
should be monitored. Further studies are needed to confirm these
interactions.
[125]
In the regions (e.g. various regions within North America) where
low selenium soil levels lead to low concentrations in the plants, some
animal species may be deficient unless selenium is supplemented with
diet or injection.
[126] Ruminants
are particularly susceptible. In general, absorption of dietary
selenium is lower in ruminants than other animals, and is lower from
forages than from grain.
[127] Ruminants grazing certain forages, e.g., some
white clover varieties containing
cyanogenic glycosides, may have higher selenium requirements,
[127] presumably because cyanide is released from the
aglycone by
glucosidase activity in the rumen
[128] and glutathione peroxidases is deactivated by the cyanide acting on the glutathione
moiety.
[129] Neonate ruminants at risk of
white muscle disease may be administered both selenium and vitamin E by injection; some of the WMD
myopathies respond only to selenium, some only to vitamin E, and some to either.
[130]
Controversial health effects
A number of correlative epidemiological studies have implicated
selenium deficiency (measured by blood levels) in a number of serious or
chronic diseases, such as cancer,
[131][132] diabetes,
[131] HIV/AIDS,
[133] and
tuberculosis.
In addition, selenium supplementation has been found to be a
chemopreventive for some types of cancer in some types of rodents.
One study of 118 exocrine pancreatic cancer (EPC) patients and 399
hospital controls in eastern Spain found high selenium concentrations to
be inversely associated with the risk of EPC.
[134] In
randomized, blinded, controlled prospective trials in humans, selenium supplementation has not succeeded in reducing the incidence of any disease, nor has a
meta-analysis of such selenium supplementation studies detected a decrease in overall mortality.
[135] However, selenium supplementation may be beneficial in cancer patients receiving
radiotherapy.