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Polonium
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| Polonium | |||||||||||||||||||||||||||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Pronunciation | /pəˈloʊniəm/ ⓘ | ||||||||||||||||||||||||||||||||||||
| Allotropes | α, β | ||||||||||||||||||||||||||||||||||||
| Appearance | silvery | ||||||||||||||||||||||||||||||||||||
| Mass number | [209] | ||||||||||||||||||||||||||||||||||||
| Polonium in the periodic table | |||||||||||||||||||||||||||||||||||||
| Atomic number (Z) | 84 | ||||||||||||||||||||||||||||||||||||
| Group | group 16 (chalcogens) | ||||||||||||||||||||||||||||||||||||
| Period | period 6 | ||||||||||||||||||||||||||||||||||||
| Block | p-block | ||||||||||||||||||||||||||||||||||||
| Electron configuration | [Xe] 4f14 5d10 6s2 6p4 | ||||||||||||||||||||||||||||||||||||
| Electrons per shell | 2, 8, 18, 32, 18, 6 | ||||||||||||||||||||||||||||||||||||
| Physical properties | |||||||||||||||||||||||||||||||||||||
| Phase at STP | solid | ||||||||||||||||||||||||||||||||||||
| Melting point | 527 K (254 °C, 489 °F) | ||||||||||||||||||||||||||||||||||||
| Boiling point | 1235 K (962 °C, 1764 °F) | ||||||||||||||||||||||||||||||||||||
| Density (near r.t.) | α-Po: 9.196 g/cm3 β-Po: 9.398 g/cm3 | ||||||||||||||||||||||||||||||||||||
| Heat of fusion | ca. 13 kJ/mol | ||||||||||||||||||||||||||||||||||||
| Heat of vaporization | 102.91 kJ/mol | ||||||||||||||||||||||||||||||||||||
| Molar heat capacity | 26.4 J/(mol·K) | ||||||||||||||||||||||||||||||||||||
Vapor pressure
| |||||||||||||||||||||||||||||||||||||
| Atomic properties | |||||||||||||||||||||||||||||||||||||
| Oxidation states | common: −2, +2, +4 +5[1] +6,[2] | ||||||||||||||||||||||||||||||||||||
| Electronegativity | Pauling scale: 2.0 | ||||||||||||||||||||||||||||||||||||
| Ionization energies |
| ||||||||||||||||||||||||||||||||||||
| Atomic radius | empirical: 168 pm | ||||||||||||||||||||||||||||||||||||
| Covalent radius | 140±4 pm | ||||||||||||||||||||||||||||||||||||
| Van der Waals radius | 197 pm | ||||||||||||||||||||||||||||||||||||
| Other properties | |||||||||||||||||||||||||||||||||||||
| Natural occurrence | from decay | ||||||||||||||||||||||||||||||||||||
| Crystal structure | cubic α-Po | ||||||||||||||||||||||||||||||||||||
| Crystal structure | rhombohedral β-Po | ||||||||||||||||||||||||||||||||||||
| Thermal expansion | 23.5 µm/(m⋅K) (at 25 °C) | ||||||||||||||||||||||||||||||||||||
| Thermal conductivity | 20 W/(m⋅K) (?) | ||||||||||||||||||||||||||||||||||||
| Electrical resistivity | α-Po: 0.40 µΩ⋅m (at 0 °C) | ||||||||||||||||||||||||||||||||||||
| Magnetic ordering | nonmagnetic | ||||||||||||||||||||||||||||||||||||
| CAS Number | 7440-08-6 | ||||||||||||||||||||||||||||||||||||
| History | |||||||||||||||||||||||||||||||||||||
| Naming | after Polonia, Latin for Poland, homeland of Marie Curie | ||||||||||||||||||||||||||||||||||||
| Discovery | Pierre and Marie Curie (1898) | ||||||||||||||||||||||||||||||||||||
| First isolation | William H. Beamer and Charles R. Maxwell (1946) | ||||||||||||||||||||||||||||||||||||
| Isotopes of polonium | |||||||||||||||||||||||||||||||||||||
| |||||||||||||||||||||||||||||||||||||
Polonium is a chemical element; it has symbol Po and atomic number 84. A rare and highly radioactive metal (although sometimes classified as a metalloid) with no stable isotopes, polonium is a chalcogen and chemically similar to selenium and tellurium, though its metallic character resembles that of its horizontal neighbors in the periodic table: thallium, lead, and bismuth. Due to the short half-life of all its isotopes, its natural occurrence is limited to tiny traces of the fleeting polonium-210 (with a half-life of 138 days) in uranium ores, as it is the penultimate daughter of natural uranium-238. Though two longer-lived isotopes exist (polonium-209 with a half-life of 124 years and polonium-208 with a half-life of 2.898 years), they are much more difficult to produce. Today, polonium is usually produced in milligram quantities by the neutron irradiation of bismuth. Due to its intense radioactivity, which results in the radiolysis of chemical bonds and radioactive self-heating, its chemistry has mostly been investigated on the trace scale only.
Polonium was discovered on 18 July 1898 by Marie Skłodowska-Curie and Pierre Curie, when it was extracted from the uranium ore pitchblende[4] and identified solely by its strong radioactivity: it was the first element to be discovered in this way.[5] Polonium was named after Marie Skłodowska-Curie's homeland of Poland, which at the time was partitioned between three countries. Polonium has few applications, and those are related to its radioactivity: heaters in space probes, antistatic devices, sources of neutrons and alpha particles, and poison (e.g., poisoning of Alexander Litvinenko). It is extremely dangerous to humans.
Characteristics
[edit]210Po is an alpha emitter that has a half-life of 138.4 days; it decays directly to its stable daughter isotope, 206Pb. A milligram (5 curies) of 210Po emits about as many alpha particles per second as 5 grams of 226Ra,[6] which means it is 5,000 times more radioactive than radium. A few curies (1 curie equals 37 gigabecquerels, 1 Ci = 37 GBq) of 210Po emit a blue glow which is caused by ionisation of the surrounding air.
About one in 100,000 alpha emissions causes an excitation in the nucleus which then results in the emission of a gamma ray with a maximum energy of 803 keV.[7][8]
Solid state form
[edit]
Polonium is a radioactive element that exists in two metallic allotropes. The alpha form is the only known example of a simple cubic crystal structure in a single atom basis at STP (space group Pm3m, no. 221). The unit cell has an edge length of 335.2 picometers; the beta form is rhombohedral.[9][10][11] The structure of polonium has been characterized by X-ray diffraction[12][13] and electron diffraction.[14]
210Po has the ability to become airborne with ease: if a sample is heated in air to 55 °C (131 °F), 50% of it is vaporized in 45 hours to form diatomic Po2 molecules, even though the melting point of polonium is 254 °C (489 °F) and its boiling point is 962 °C (1,764 °F).[15][16][1] More than one hypothesis exists for how polonium does this; one suggestion is that small clusters of polonium atoms are spalled off by the alpha decay.[17]
Chemistry
[edit]The chemistry of polonium is similar to that of tellurium, although it also shows some similarities to its neighbor bismuth due to its metallic character. Polonium dissolves readily in dilute acids but is only slightly soluble in alkalis. Polonium solutions are first colored in pink by the Po2+ ions, but then rapidly become yellow because alpha radiation from polonium ionizes the solvent and converts Po2+ into Po4+. As polonium also emits alpha-particles after disintegration, this process is accompanied by bubbling and emission of heat and light by glassware due to the absorbed alpha particles; as a result, polonium solutions are volatile and will evaporate within days unless sealed.[18][19] At pH about 1, polonium ions are readily hydrolyzed and complexed by acids such as oxalic acid, citric acid, and tartaric acid.[20]
Compounds
[edit]Polonium has no common compounds, and almost all of its compounds are synthetically created; more than 50 of those are known.[21] The most stable class of polonium compounds are polonides, which are prepared by direct reaction of two elements. Na2Po has the antifluorite structure, the polonides of Ca, Ba, Hg, Pb and lanthanides form a NaCl lattice, BePo and CdPo have the wurtzite and MgPo the nickel arsenide structure. Most polonides decompose upon heating to about 600 °C, except for HgPo that decomposes at ~300 °C and the lanthanide polonides, which do not decompose but melt at temperatures above 1000 °C. For example, the polonide of praseodymium (PrPo) melts at 1250 °C, and that of thulium (TmPo) melts at 2200 °C.[22] PbPo is one of the very few naturally occurring polonium compounds, as polonium alpha decays to form lead.[23]
Polonium hydride (PoH
2) is a volatile liquid at room temperature prone to dissociation; it is thermally unstable.[22] Water is the only other known hydrogen chalcogenide which is a liquid at room temperature; however, this is due to hydrogen bonding. The three oxides, PoO, PoO2 and PoO3, are the products of oxidation of polonium.[24]
Halides of the structure PoX2, PoX4 and PoF6 are known. They are soluble in the corresponding hydrogen halides, i.e., PoClX in HCl, PoBrX in HBr and PoI4 in HI.[25] Polonium dihalides are formed by direct reaction of the elements or by reduction of PoCl4 with SO2 and with PoBr4 with H2S at room temperature. Tetrahalides can be obtained by reacting polonium dioxide with HCl, HBr or HI.[26]
Other polonium compounds include the polonite, potassium polonite; various polonate solutions; and the acetate, bromate, carbonate, citrate, chromate, cyanide, formate, (II) or (IV) hydroxide, nitrate, selenate, selenite, monosulfide, sulfate, disulfate or sulfite salts.[25][27]
A limited organopolonium chemistry is known, mostly restricted to dialkyl and diaryl polonides (R2Po), triarylpolonium halides (Ar3PoX), and diarylpolonium dihalides (Ar2PoX2).[28][29] Polonium also forms soluble compounds with some ligands, such as 2,3-butanediol and thiourea.[28]
| Formula | Color | m.p. (°C) | Sublimation temp. (°C) |
Symmetry | Pearson symbol | Space group | No | a (pm) | b(pm) | c(pm) | Z | ρ (g/cm3) | ref |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| PoO | black | ||||||||||||
| PoO2 | pale yellow | 500 (dec.) | 885 | fcc | cF12 | Fm3m | 225 | 563.7 | 563.7 | 563.7 | 4 | 8.94 | [31] |
| PoH2 | -35.5 | ||||||||||||
| PoCl2 | dark ruby red | 355 | 130 | orthorhombic | oP3 | Pmmm | 47 | 367 | 435 | 450 | 1 | 6.47 | [32] |
| PoBr2 | purple-brown | 270 (dec.) | [33] | ||||||||||
| PoCl4 | yellow | 300 | 200 | monoclinic | [32] | ||||||||
| PoBr4 | red | 330 (dec.) | fcc | cF100 | Fm3m | 225 | 560 | 560 | 560 | 4 | [33] | ||
| PoI4 | black | [34] |
Isotopes
[edit]- All nuclear data not otherwise stated is from the standard source:[35]
There are 42 known isotopes of polonium (84Po), all radioactive, stretching from 186Po to 227Po. The isotopes 210 through 218 occur naturally in the four principal decay chains; of these, 210Po with a half-life of 138.376 days has the longest half-life and is, therefore, the most abundant by mass. It is also the most easily synthesized isotope, by neutron capture on natural bismuth,[36] and so by far the most abundant artificial isotope as well.
Two other isotopes have longer lives: 209Po with a half-life of 124 years and 208Po with a half-life of 2.898 years. Both are made by using a cyclotron to bombard bismuth with protons.[37]
History
[edit]Tentatively called "radium F", polonium was discovered by Marie and Pierre Curie in July 1898,[38][39] and was named after Marie Curie's native land of Poland (Latin: Polonia).[40][41] Poland at the time was under Russian, German, and Austro-Hungarian partition, and did not exist as an independent country. It was Curie's hope that naming the element after her native land would publicize its lack of independence. Polonium may be the first element named to highlight a political controversy.[42]
This element was the first one discovered by the Curies while they were investigating the cause of pitchblende radioactivity. Pitchblende, after removal of the radioactive elements uranium and thorium, was more radioactive than the uranium and thorium combined. This spurred the Curies to search for additional radioactive elements. They first separated out polonium from pitchblende in July 1898, and five months later, also isolated radium.[18][38][43] German scientist Willy Marckwald successfully isolated 3 milligrams of polonium in 1902, though at the time he believed it was a new element, which he dubbed "radio-tellurium", and it was not until 1905 that it was demonstrated to be the same as polonium.[44][45]
In the United States, polonium was produced as part of the Manhattan Project's Dayton Project during World War II. Polonium and beryllium were the key ingredients of the 'Urchin' initiator at the center of the bomb's spherical pit.[46] 'Urchin' initiated the nuclear chain reaction at the moment of prompt-criticality to ensure that the weapon did not fizzle. 'Urchin' was used in early U.S. weapons; subsequent U.S. weapons utilized a pulse neutron generator for the same purpose.[46]
Much of the basic physics of polonium was classified until after the war. The fact that a polonium-beryllium (Po-Be) initiator was used in the gun-type nuclear weapons was classified until the 1960s.[47]
The Atomic Energy Commission and the Manhattan Project funded human experiments using polonium on five people at the University of Rochester between 1943 and 1947. The people were administered between 9 and 22 microcuries (330 and 810 kBq) of polonium to study its excretion.[48][49][50]
Occurrence and production
[edit]Polonium is a very rare element in nature because of the short half-lives of all its isotopes. Nine isotopes, from 210 to 218 inclusive, occur in traces as decay products: 210Po, 214Po, and 218Po occur in the decay chain of 238U; 211Po and 215Po occur in the decay chain of 235U; 212Po and 216Po occur in the decay chain of 232Th; and 213Po and 217Po occur in the decay chain of 237Np. (No primordial 237Np survives, but traces of it are continuously regenerated through (n,2n) knockout reactions in natural 238U.)[51] Of these, 210Po is the only isotope with a half-life longer than 3 minutes.[52]
Polonium can be found in uranium ores at about 0.1 mg per metric ton (1 part in 1010),[53][54] which is approximately 0.2% of the abundance of radium. The amounts in the Earth's crust are not harmful. Polonium has been found in tobacco smoke from tobacco leaves grown with phosphate fertilizers.[55][56][57]
Because it is present in small concentrations, isolation of polonium from natural sources is a tedious process. The largest batch of the element ever extracted, performed in the first half of the 20th century, contained only 40 Ci (1.5 TBq) (9 mg) of polonium-210 and was obtained by processing 37 tonnes of residues from radium production.[58] Polonium is now usually obtained by irradiating bismuth with high-energy neutrons or protons.[18][36]
In 1934, an experiment showed that when natural 209Bi is bombarded with neutrons, 210Bi is created, which then decays to 210Po via beta-minus decay. By irradiating certain bismuth salts containing light element nuclei such as beryllium, a cascading (α,n) reaction can also be induced to produce 210Po in large quantities.[59] The final purification is done pyrochemically followed by liquid-liquid extraction techniques.[60] Polonium may now be made in milligram amounts in this procedure which uses high neutron fluxes found in nuclear reactors.[36] Only about 100 grams are produced each year, practically all of it in Russia, making polonium exceedingly rare.[61][62]
This process can cause problems in lead-bismuth based liquid metal cooled nuclear reactors such as those used in the Soviet Navy's K-27. Measures must be taken in these reactors to deal with the unwanted possibility of 210Po being released from the coolant.[63][64]
The longer-lived isotopes of polonium, 208Po and 209Po, can be formed by proton or deuteron bombardment of bismuth using a cyclotron. Other more neutron-deficient and more unstable isotopes can be formed by the irradiation of platinum with carbon nuclei.[65]
Applications
[edit]Polonium-based sources of alpha particles were produced in the former Soviet Union.[66] Such sources were applied for measuring the thickness of industrial coatings via attenuation of alpha radiation.[67]
Because of intense alpha radiation, a one-gram sample of 210Po will spontaneously heat up to above 500 °C (932 °F) generating about 140 watts of power. Therefore, 210Po is used as an atomic heat source to power radioisotope thermoelectric generators via thermoelectric materials.[6][18][68][69] For example, 210Po heat sources were used in the Lunokhod 1 (1970) and Lunokhod 2 (1973) Moon rovers to keep their internal components warm during the lunar nights, as well as the Kosmos 84 and 90 satellites (1965).[66][70]
The alpha particles emitted by polonium can be converted to neutrons using beryllium oxide, at a rate of 93 neutrons per million alpha particles.[68] Po-BeO mixtures are used as passive neutron sources with a gamma-ray-to-neutron production ratio of 1.13 ± 0.05, lower than for nuclear fission-based neutron sources.[71] Examples of Po-BeO mixtures or alloys used as neutron sources are a neutron trigger or initiator for nuclear weapons[18][72] and for inspections of oil wells. About 1500 sources of this type, with an individual activity of 1,850 Ci (68 TBq), had been used annually in the Soviet Union.[73]
Polonium was also part of brushes or more complex tools that eliminate static charges in photographic plates, textile mills, paper rolls, sheet plastics, and on substrates (such as automotive) prior to the application of coatings.[74] Alpha particles emitted by polonium ionize air molecules that neutralize charges on the nearby surfaces.[75][76] Some anti-static brushes contain up to 500 microcuries (20 MBq) of 210Po as a source of charged particles for neutralizing static electricity.[77] In the US, devices with no more than 500 μCi (19 MBq) of (sealed) 210Po per unit can be bought in any amount under a "general license",[78] which means that a buyer need not be registered by any authorities. Polonium needs to be replaced in these devices nearly every year because of its short half-life; it is also highly radioactive and therefore has been mostly replaced by less dangerous beta particle sources.[6]
Tiny amounts of 210Po are sometimes used in the laboratory and for teaching purposes—typically of the order of 4–40 kBq (0.11–1.08 μCi), in the form of sealed sources, with the polonium deposited on a substrate or in a resin or polymer matrix—are often exempt from licensing by the NRC and similar authorities as they are not considered hazardous. Small amounts of 210Po are manufactured for sale to the public in the United States as "needle sources" for laboratory experimentation, and they are retailed by scientific supply companies. The polonium is a layer of plating which in turn is plated with a material such as gold, which allows the alpha radiation (used in experiments such as cloud chambers) to pass while preventing the polonium from being released and presenting a toxic hazard.[citation needed]
Polonium spark plugs were marketed by Firestone from 1940 to 1953. While the amount of radiation from the plugs was minuscule and not a threat to the consumer, the benefits of such plugs quickly diminished after approximately a month because of polonium's short half-life and because buildup on the conductors would block the radiation that improved engine performance. (The premise behind the polonium spark plug, as well as Alfred Matthew Hubbard's prototype radium plug that preceded it, was that the radiation would improve ionization of the fuel in the cylinder and thus allow the motor to fire more quickly and efficiently.)[79][80]
Biology and toxicity
[edit]Overview
[edit]Polonium can be hazardous and has no biological role.[18] By mass, polonium-210 is around 250,000 times more toxic than hydrogen cyanide (the LD50 for 210Po is less than 1 microgram for an average adult (see below) compared with about 250 milligrams for hydrogen cyanide[81]). The main hazard is its intense radioactivity (as an alpha emitter), which makes it difficult to handle safely. Even in microgram amounts, handling 210Po is extremely dangerous, requiring specialized equipment (a negative pressure alpha glove box equipped with high-performance filters), adequate monitoring, and strict handling procedures to avoid any contamination. Alpha particles emitted by polonium will damage organic tissue easily if polonium is ingested, inhaled, or absorbed, although they do not penetrate the epidermis and hence are not hazardous as long as the alpha particles remain outside the body and do not come near the eyes, which are living tissue. Wearing chemically resistant and intact gloves is a mandatory precaution to avoid transcutaneous diffusion of polonium directly through the skin. Polonium delivered in concentrated nitric acid can easily diffuse through inadequate gloves (e.g., latex gloves) or the acid may damage the gloves.[82]
Polonium does not have toxic chemical properties.[83]
It has been reported that some microbes can methylate polonium by the action of methylcobalamin.[84][85] This is similar to the way in which mercury, selenium, and tellurium are methylated in living things to create organometallic compounds. Studies investigating the metabolism of polonium-210 in rats have shown that only 0.002 to 0.009% of polonium-210 ingested is excreted as volatile polonium-210.[86]
Acute effects
[edit]The median lethal dose (LD50) for acute radiation exposure is about 4.5 Sv.[87] The committed effective dose equivalent 210Po is 0.51 μSv/Bq if ingested, and 2.5 μSv/Bq if inhaled.[88] A fatal 4.5 Sv dose can be caused by ingesting 8.8 MBq (240 μCi), about 50 nanograms (ng), or inhaling 1.8 MBq (49 μCi), about 10 ng. One gram of 210Po could thus in theory poison 20 million people, of whom 10 million would die. The actual toxicity of 210Po is lower than these estimates because radiation exposure that is spread out over several weeks (the biological half-life of polonium in humans is 30 to 50 days[89]) is somewhat less damaging than an instantaneous dose. It has been estimated that a median lethal dose of 210Po is 15 megabecquerels (0.41 mCi), or 0.089 micrograms (μg), still an extremely small amount.[90][91] For comparison, one grain of table salt is about 0.06 mg = 60 μg.[92]
Long term (chronic) effects
[edit]In addition to the acute effects, radiation exposure (both internal and external) carries a long-term risk of death from cancer of 5–10% per Sv.[87] The general population is exposed to small amounts of polonium as a radon daughter in indoor air; the isotopes 214Po and 218Po are thought to cause the majority[93] of the estimated 15,000–22,000 lung cancer deaths in the US every year that have been attributed to indoor radon.[94] Tobacco smoking causes additional exposure to polonium.[95]
Regulatory exposure limits and handling
[edit]The maximum allowable body burden for ingested 210Po is only 1.1 kBq (30 nCi), which is equivalent to a particle massing only 6.8 picograms.[96] The maximum permissible workplace concentration of airborne 210Po is about 10 Bq/m3 (3×10−10 μCi/cm3).[97] The target organs for polonium in humans are the spleen and liver.[98] As the spleen (150 g) and the liver (1.3 to 3 kg) are much smaller than the rest of the body, if the polonium is concentrated in these vital organs, it is a greater threat to life than the dose which would be suffered (on average) by the whole body if it were spread evenly throughout the body, in the same way as caesium or tritium (as T2O).[99][100]
210Po is widely used in industry, and readily available with little regulation or restriction.[101][102] In the US, a tracking system run by the Nuclear Regulatory Commission was implemented in 2007 to register purchases of more than 16 curies (590 GBq) of polonium-210 (enough to make up 5,000 lethal doses). The IAEA "is said to be considering tighter regulations ... There is talk that it might tighten the polonium reporting requirement by a factor of 10, to 1.6 curies (59 GBq)."[101] As of 2013, this is still the only alpha emitting byproduct material available, as a NRC Exempt Quantity, which may be held without a radioactive material license.[citation needed]
Polonium and its compounds must be handled with caution inside special alpha glove boxes, equipped with HEPA filters and continuously maintained under depression to prevent the radioactive materials from leaking out. Gloves made of natural rubber (latex) do not properly withstand chemical attacks, a.o. by concentrated nitric acid (e.g., 6 M HNO3) commonly used to keep polonium in solution while minimizing its sorption onto glass. They do not provide sufficient protection against the contamination from polonium (diffusion of 210Po solution through the intact latex membrane, or worse, direct contact through tiny holes and cracks produced when the latex begins to suffer degradation by acids or UV from ambient light); additional surgical gloves are necessary (inside the glovebox to protect the main gloves when handling strong acids and bases, and also from outside to protect the operator hands against 210Po contamination from diffusion, or direct contact through glove defects). Chemically more resistant, and also denser, neoprene and butyl gloves shield alpha particles emitted by polonium better than natural rubber.[103] The use of natural rubber gloves is not recommended for handling 210Po solutions.
Cases of poisoning
[edit]Despite the element's highly hazardous properties, circumstances in which polonium poisoning can occur are rare. Its extreme scarcity in nature,[104] the short half-lives of all its isotopes, the specialised facilities and equipment needed to obtain any significant quantity, and safety precautions against laboratory accidents all make harmful exposure events unlikely. As such, only a handful of cases of radiation poisoning specifically attributable to polonium exposure have been confirmed.[105]
20th century
[edit]In response to concerns about the risks of occupational polonium exposure, quantities of 210Po were administered to five human volunteers at the University of Rochester from 1944 to 1947, in order to study its biological behaviour. These studies were funded by the Manhattan Project and the AEC. Four men and a woman participated, all suffering from terminal cancers, and ranged in age from their early thirties to early forties; all were chosen because experimenters wanted subjects who had not been exposed to polonium either through work or accident.[106] 210Po was injected into four hospitalised patients, and orally given to a fifth. None of the administered doses (all ranging from 0.17 to 0.30 μCi kg−1) approached fatal quantities.[107][106]
The first documented death directly resulting from polonium poisoning occurred in the Soviet Union, on 10 July 1954.[108][109] An unidentified 41-year-old man presented for medical treatment on 29 June, with severe vomiting and fever; the previous day, he had been working for five hours in an area in which, unknown to him, a capsule containing 210Po had depressurised and begun to disperse in aerosol form. Over this period, his total intake of airborne 210Po was estimated at 0.11 GBq (almost 25 times the estimated LD50 by inhalation of 4.5 MBq). Despite treatment, his condition continued to worsen and he died 13 days after the exposure event.[108]
From 1955 to 1957 the Windscale Piles had been releasing polonium-210. The Windscale fire brought the need for testing of the land downwind for radioactive material contamination, and this is how it was found. An estimate of 8.8 terabecquerels (240 Ci) of polonium-210 has been made.
It has also been suggested that Irène Joliot-Curie's 1956 death from leukaemia was owed to the radiation effects of polonium. She was accidentally exposed in 1946 when a sealed capsule of the element exploded on her laboratory bench.[110]
As well, several deaths in Israel during 1957–1969 have been alleged to have resulted from 210Po exposure.[111] A leak was discovered at a Weizmann Institute laboratory in 1957. Traces of 210Po were found on the hands of Professor Dror Sadeh, a physicist who researched radioactive materials. Medical tests indicated no harm, but the tests did not include bone marrow. Sadeh, one of his students, and two colleagues died from various cancers over the subsequent few years. The issue was investigated secretly, but there was never any formal admission of a connection between the leak and the deaths.[112]
The Church Rock uranium mill spill 16 July 1979 is reported to have released polonium-210. The report states animals had higher concentrations of lead-210, polonium-210 and radium-226 than the tissues from control animals.[113]
21st century
[edit]The cause of the 2006 death of Alexander Litvinenko, a former Russian FSB agent who had defected to the United Kingdom in 2001, was identified to be poisoning with a lethal dose of 210Po;[114][115] it was subsequently determined that the 210Po had probably been deliberately administered to him by two Russian ex-security agents, Andrey Lugovoy and Dmitry Kovtun.[116][117] As such, Litvinenko's death was the first (and, to date, only) confirmed instance in which polonium's extreme toxicity has been used with malicious intent.[118][119][120]
In 2011, an allegation surfaced that the death of Palestinian leader Yasser Arafat, who died on 11 November 2004 of uncertain causes, also resulted from deliberate polonium poisoning,[121][122] and in July 2012, concentrations of 210Po many times more than normal were detected in Arafat's clothes and personal belongings by the Institut de Radiophysique in Lausanne, Switzerland.[123][124] Even though Arafat's symptoms were acute gastroenteritis with diarrhoea and vomiting,[125] the institute's spokesman said that despite the tests the symptoms described in Arafat's medical reports were not consistent with 210Po poisoning, and conclusions could not be drawn.[124] In 2013 the team found levels of polonium in Arafat's ribs and pelvis 18 to 36 times the average,[126][127] even though by this point in time the amount had diminished by a factor of 2 million.[128] Forensic scientist Dave Barclay stated, "In my opinion, it is absolutely certain that the cause of his illness was polonium poisoning. ... What we have got is the smoking gun - the thing that caused his illness and was given to him with malice."[125][126] Subsequently, French and Russian teams claimed that the elevated 210Po levels were not the result of deliberate poisoning, and did not cause Arafat's death.[129][130]
It has also been suspected that Russian businessman Roman Tsepov was killed with polonium. He had symptoms similar to Aleksander Litvinenko.[131]
Treatment
[edit]It has been suggested that chelation agents, such as British anti-Lewisite (dimercaprol), can be used to decontaminate humans.[132] In one experiment, rats were given a fatal dose of 1.45 MBq/kg (8.7 ng/kg) of 210Po; all untreated rats were dead after 44 days, but 90% of the rats treated with the chelation agent HOEtTTC remained alive for five months.[133]
Detection in biological specimens
[edit]Polonium-210 may be quantified in biological specimens by alpha particle spectrometry to confirm a diagnosis of poisoning in hospitalized patients or to provide evidence in a medicolegal death investigation. The baseline urinary excretion of polonium-210 in healthy persons due to routine exposure to environmental sources is normally in a range of 5–15 mBq/day. Levels in excess of 30 mBq/day are suggestive of excessive exposure to the radionuclide.[134]
Occurrence in humans and the biosphere
[edit]Polonium-210 is widespread in the biosphere, including in human tissues, because of its position in the uranium-238 decay chain. Natural uranium-238 in the Earth's crust decays through a series of solid radioactive intermediates including radium-226 to the radioactive noble gas radon-222, some of which, during its 3.8-day half-life, diffuses into the atmosphere. There it decays through several more steps to polonium-210, much of which, during its 138-day half-life, is washed back down to the Earth's surface, thus entering the biosphere, before finally decaying to stable lead-206.[135][136][137]
As early as the 1920s, French biologist Antoine Lacassagne, using polonium provided by his colleague Marie Curie, showed that the element has a specific pattern of uptake in rabbit tissues, with high concentrations, particularly in liver, kidney, and testes.[138] More recent evidence suggests that this behavior results from polonium substituting for its congener sulfur, also in group 16 of the periodic table, in sulfur-containing amino-acids or related molecules[139] and that similar patterns of distribution occur in human tissues.[140] Polonium is indeed an element naturally present in all humans, contributing appreciably to natural background dose, with wide geographical and cultural variations, and particularly high levels in arctic residents, for example.[141]
Tobacco
[edit]Polonium-210 in tobacco contributes to many of the cases of lung cancer worldwide. Most of this polonium is derived from lead-210 deposited on tobacco leaves from the atmosphere; the lead-210 is a product of radon-222 gas, much of which appears to originate from the decay of radium-226 from fertilizers applied to the tobacco soils.[57][142][143][144][145]
The presence of polonium in tobacco smoke has been known since the early 1960s.[146][147] Some of the world's biggest tobacco firms researched ways to remove the substance—to no avail—over a 40-year period. The results were never published.[57]
Food
[edit]Polonium is found in the food chain, especially in seafood.[148][149]
In popular culture
[edit]Polonium poisoning has been used as a plot point on the American daytime television show General Hospital for many years.[150]
See also
[edit]References
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Bibliography
[edit]- Bagnall, K. W. (1962) [1962]. "The Chemistry of Polonium". Advances in Inorganic Chemistry and Radiochemistry. Vol. 4. New York: Academic Press. pp. 197–226. doi:10.1016/S0065-2792(08)60268-X. ISBN 978-0-12-023604-6. Retrieved 14 June 2012.
{{cite book}}: ISBN / Date incompatibility (help) - Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth–Heinemann. ISBN 978-0080379418.
External links
[edit]- Polonium at The Periodic Table of Videos (University of Nottingham)
Polonium
View on GrokipediaPolonium is a chemical element with the atomic number 84 and chemical symbol Po.[1] It belongs to the chalcogen group (group 16) in the periodic table and occurs as a rare, silvery-gray post-transition metal that is solid at room temperature.[2] Discovered in 1898 by Marie Skłodowska-Curie and Pierre Curie through the chemical analysis of pitchblende ore, polonium was the first element found to be more radioactive than uranium and was named in honor of Poland, Marie Curie's homeland.[2] All isotopes of polonium are radioactive, with no stable forms; the primordial isotope polonium-210, arising from the decay of uranium and thorium in the Earth's crust, has the longest half-life among naturally occurring variants at approximately 138.4 days, decaying via alpha emission to stable lead-206.[1][3] Polonium exhibits two allotropic forms: a simple cubic structure stable below approximately 75 °C and a rhombohedral form at higher temperatures, reflecting its metallic yet brittle nature with low thermal conductivity compared to other metals.[4] Its extreme rarity—estimated at less than 100 grams total in Earth's crust—stems from rapid radioactive decay rather than scarcity in formation, making isolation challenging and typically achieved via chemical separation from uranium ores or neutron irradiation of bismuth.[2] Due to its high specific activity and alpha-particle emission, polonium-210 serves niche industrial applications, including as a source of heat in thermoelectric generators for space probes, in antistatic devices to neutralize static electricity on film or machinery, and mixed with beryllium for portable neutron sources in research. However, polonium's defining hazard is its radiotoxicity: ingestion or inhalation of microgram quantities can deliver lethal radiation doses internally, as alpha particles cause severe tissue damage while being harmless externally; it is estimated to be millions of times more toxic than hydrogen cyanide by mass.[5] This property has precluded widespread use and highlighted its potential in targeted radiological harm, underscoring the empirical trade-off between its energetic decay utility and inherent danger.
Properties
Physical Characteristics
Polonium is a silvery-gray, radioactive metal with a metallic luster observable in thin films or deposits.[2] [6] It exists as a solid at standard temperature and pressure, with a density of 9.196 g/cm³ for its alpha allotrope measured at room temperature.[7] [8] The element has a melting point of 254 °C (527 K) and a boiling point of 962 °C (1235 K).[2] [7] Polonium displays two allotropes: the low-temperature alpha form adopts a simple cubic crystal structure with a lattice constant of 3.352 Å, unique among elemental metals, and a calculated density of approximately 9.14 g/cm³; the high-temperature beta form is rhombohedral.[9] [8] The alpha phase is stable below approximately 36–50 °C, transitioning to the beta phase upon heating, though precise measurements are limited due to the element's scarcity and intense radioactivity.[9] Thermal conductivity of polonium is estimated at 20 W·m⁻¹·K⁻¹, reflecting its metallic character despite belonging to group 16.[10] Due to rapid self-heating from alpha decay, especially in the common isotope polonium-210, bulk samples exhibit elevated temperatures, complicating direct physical measurements.Chemical Properties and Compounds
Polonium, as the heaviest stable member of group 16 in the periodic table, displays chemical behavior transitional between nonmetals and metals, with greater metallic character than tellurium due to relativistic effects stabilizing the 6s electrons and inert-pair tendency favoring lower oxidation states.[12] Its electronegativity is 2.0 on the Pauling scale, reflecting moderate electron affinity.[6] The element dissolves readily in dilute mineral acids such as HCl and HNO₃, forming cationic species, and reacts slowly with dry oxygen at ambient temperatures to yield PoO₂, with reaction rates accelerating markedly above 200°C.[12] Alpha self-irradiation promotes autooxidation, generating higher valent species even in inert atmospheres.[12] The predominant oxidation states are +2 and +4, with +4 being the most stable in solid compounds and +6 accessible under strong oxidizing conditions; the -2 state occurs in polonide salts analogous to chalcogenides.[12] In aqueous media, Po(IV) hydrolyzes to form colloidal species at low acidity (pH > 1), while Po(II) is less stable and prone to disproportionation or oxidation; Po(VI) exists transiently as perpolonate ions (PoO₆⁶⁻) but decomposes rapidly.[13] Polonium forms stable anionic complexes in halide media, such as PoCl₆²⁻ in concentrated HCl, facilitating solvent extraction separations.[12] Key compounds include oxides such as polonium(IV) oxide (PoO₂), a pale yellow solid prepared by air oxidation or hydrolysis of Po(IV) salts, which is amphoteric and dissolves in strong bases to form polonates.[12] Polonium(VI) oxide (PoO₃) has been inferred from spectroscopic and extraction data but remains poorly characterized due to instability.[12] Halides exhibit volatility and covalent character: PoCl₄ is a yellow, hygroscopic solid subliming at ~300°C, PoBr₄ red and similarly volatile, PoI₄ black with decomposition above 200°C; lower valent PoCl₂ (ruby-red) and PoBr₂ (purple) disproportionate in water.[12] Polonium monosulfide (PoS) precipitates from acidic solutions with extremely low solubility (K_{sp} ≈ 5 × 10^{-29}), while the hydroxide Po(OH)₄ (or Po(OH)₂ for +2) has K_{sp} ≈ 10^{-37}, underscoring its tendency to hydrolyze.[12] Organo-polonium compounds, such as dialkyl derivatives, are rare and unstable owing to the element's radioactivity and weak Po-C bonds.[14]Isotopes and Radioactivity
Polonium has no stable isotopes; all known isotopes, numbering 42 and spanning mass numbers from ^{186}Po to ^{227}Po, are radioactive with half-lives ranging from microseconds to over a century.[15] The longest-lived isotope overall is ^{209}Po, with a half-life of approximately 102 years, decaying primarily by alpha emission.[16] Most polonium isotopes decay via alpha particle emission, characteristic of heavy elements near the end of the actinide decay chains, though shorter-lived ones may also undergo beta decay or electron capture.[17] The predominant naturally occurring isotope is ^{210}Po, which accounts for virtually all polonium in environmental samples at low concentrations (typically 0.1–1 parts per trillion in uranium-bearing ores) as a decay product in the uranium-238 series: ^{238}U → ... → ^{222}Rn → ^{210}Pb → ^{210}Po → ^{206}Pb.[18] [19] ^{210}Po has a half-life of 138.376 days and decays exclusively by alpha emission (5.304 MeV particles, 100% branching ratio) to stable ^{206}Pb, yielding a specific activity of about 4.42 × 10^{14} Bq/g (12 Ci/mg), making it one of the most intensely radioactive substances per unit mass among alpha emitters.[19] [20] Trace amounts of other isotopes such as ^{211}Po, ^{214}Po, ^{215}Po, ^{216}Po, and ^{218}Po occur naturally in uranium and thorium decay chains, but their half-lives are brief—ranging from 0.52 seconds (^{211}Po) to 3.10 minutes (^{218}Po)—limiting their environmental persistence.[21] [22] Longer-lived artificial isotopes like ^{208}Po (half-life 2.90 years, alpha and beta decay) and ^{209}Po are produced in nuclear reactors or accelerators via neutron capture on bismuth or lead, but they contribute negligibly to natural radioactivity.[16] Polonium's radioactivity stems from its position in alpha decay sequences, where high atomic number facilitates energetically favorable alpha emission over beta decay, resulting in rapid depletion of any polonium sample through sequential decay to lead isotopes.[3]| Isotope | Half-life | Primary Decay Mode | Notes |
|---|---|---|---|
| ^{208}Po | 2.90 years | Alpha (53%), beta-minus (47%) | Reactor-produced; minor natural traces |
| ^{209}Po | 102–125 years | Alpha | Longest-lived overall; artificial |
| ^{210}Po | 138.376 days | Alpha (100%, 5.304 MeV) | Dominant natural isotope; high specific activity |
| ^{214}Po | 164.3 μs | Alpha (99.99%) | Transient in uranium chain; branches to ^{210}Pb |
| ^{218}Po | 3.10 minutes | Alpha (99.98%) | Short-lived radon daughter |
History
Discovery and Naming
Polonium was discovered in 1898 by Pierre Curie and Marie Skłodowska-Curie during their investigation of uranium ore residues from pitchblende, motivated by observations of unexplained radioactivity beyond that of uranium itself.[23] On April 12, 1898, the Curies announced to the Paris Academy of Sciences their hypothesis of an unknown radioactive element present in a bismuth fraction exhibiting four times the activity of uranium.[24] By July 18, 1898, they had isolated this substance through fractional precipitation and confirmed its distinct properties, publishing their findings in a communication to the Academy titled "Sur une substance nouvelle radio-active, contenue dans la pitchblende" (On a new radioactive substance contained in pitchblende).[25] The element's identification relied on its intense radioactivity, measured via ionization effects on electroscopes, though pure isolation proved impossible due to its chemical instability and short-lived isotopes; the Curies worked primarily with polonium-210, which has a half-life of 138 days.[26][2] The name "polonium" derives from Polonia, the Latin term for Poland, Marie Curie's native country, which had been partitioned and lacked sovereignty since 1795.[2] Marie proposed the name to honor her homeland, reflecting her Polish patriotism amid her French scientific career; this choice carried symbolic weight, as Poland's independence was not restored until 1918.[24] The Curies' announcement marked polonium as the first element discovered through radioactivity studies, preceding their December 1898 identification of radium from a barium fraction of the same residues.[23] Subsequent verification by spectroscopists like Eugène Demarçay confirmed the element's spectral lines, solidifying its place as atomic number 84 in the periodic table.[27]Early Research and Challenges
Following the discovery of polonium in July 1898 by Marie and Pierre Curie, early research focused on isolating the element from the bismuth fractions of pitchblende residues, after uranium had been chemically extracted. The Curies processed several tons of the ore, handling batches of up to 20 kilograms each in a makeshift laboratory shed, using tedious fractional crystallizations and precipitation techniques to concentrate the highly radioactive substance, which exhibited approximately 300 times the activity of uranium.[27] [26] Initial characterization relied on measurements with the piezo-electric quartz electrometer invented by Pierre Curie, revealing polonium's intense alpha radiation but yielding only impure compounds due to its chemical similarity to bismuth and tellurium.[27] [5] A primary challenge was polonium's inherent instability, as its predominant isotope, polonium-210, has a half-life of 138 days, causing rapid decay during prolonged isolation attempts; Marie Curie never obtained a pure sample, a limitation not fully explained until the later development of radioactive decay theory.[26] The element's scarcity in natural sources—present in trace amounts—necessitated processing vast ore quantities for minuscule yields, compounded by self-heating and radiolysis effects from its radioactivity, which disrupted chemical bonds and complicated purification.[24] Determining fundamental properties like atomic mass proved arduous, requiring until 1910 for spectroscopic studies to record its emission spectrum and confirm its identity independently.[24] Working conditions exacerbated these technical hurdles: the unheated, drafty shed with a glass roof and bituminous floor exposed researchers to toxic dust, radon gas, and unshielded radiation, leading to physical exhaustion from stirring boiling cauldrons with heavy iron rods and resulting in scarred hands and chronic fatigue for Marie Curie.[27] Early handling lacked awareness of long-term health risks, with no standardized protocols for alpha-emitting materials, limiting experimental scale and reproducibility; subsequent efforts by other chemists in the early 1900s similarly struggled with contamination and decay losses during electrodeposition or precipitation methods.[26] [5] These obstacles delayed comprehensive chemical studies until trace-scale techniques and nuclear production methods emerged decades later.Occurrence and Production
Natural Sources
Polonium occurs naturally in trace quantities primarily as the isotope ^{210}Po, formed through the decay chain of uranium-238 in the Earth's crust.[3] Its primordial abundance is negligible, with most environmental polonium resulting from ongoing radioactive decay rather than stable primordial isotopes.[28] The principal natural reservoir is uranium ores, where polonium concentrations reach about 100 micrograms per metric ton, representing roughly 0.2% of radium's abundance in such deposits.[28][29] Extraction from these ores is uneconomical due to the low yields, as one ton of uranium ore yields only approximately 0.0001 grams of polonium.[30] Traces also appear in thorium-bearing minerals via the thorium-232 decay series, though at even lower levels.[3] In the broader environment, ^{210}Po disperses at low concentrations through soil (typically 20–240 Bq/kg), surface water, and air (0.03–0.3 Bq/m³ at ground level).[31][32] These levels stem from radium-226 decay in crustal materials, atmospheric deposition, and minor contributions from volcanic emissions, wildfires, and soil dust resuspension.[13] Polonium bioaccumulates in certain plants, notably tobacco, where electrically charged ^{210}Po ions from soil radium concentrate in leaves, reaching elevated activities relative to other vegetation.[30]Industrial Production Methods
Polonium-210, the primary isotope produced industrially, is manufactured in nuclear reactors through neutron irradiation of bismuth-209 targets.[33] The process begins with the capture of a thermal neutron by bismuth-209, yielding bismuth-210 via the reaction , which undergoes beta decay with a half-life of approximately 5 days to form polonium-210.[3] This method allows production in milligram quantities, though yields are limited by the low neutron capture cross-section of bismuth-209, typically requiring extended irradiation periods in high-flux reactors.[34] Following irradiation, polonium-210 is chemically separated from the bismuth matrix and impurities, often via distillation under vacuum or selective precipitation and solvent extraction techniques, exploiting its volatility and chalcogen-like chemistry.[35] Worldwide annual production is estimated at less than 100 grams, primarily for applications such as static eliminators and neutron sources, with Russia accounting for the majority at facilities like the Avangard plant, producing around 85 grams per year as of the mid-2000s.[33] Natural extraction from uranium ore decay chains is not viable for industrial scales due to polonium's scarcity, occurring at parts-per-trillion levels even in high-grade ores.[33] Alternative production routes, such as alpha-particle bombardment of bismuth-209 to generate astatine-210 (which decays to polonium-210), are employed in research settings but lack the throughput for commercial needs due to accelerator requirements and lower efficiency.[36] United States production ceased in 1971, shifting reliance to imported material under strict regulatory oversight.[37]Applications
Civilian and Industrial Uses
Polonium-210 is primarily utilized in industrial static elimination devices, where its alpha emissions ionize surrounding air to neutralize electrostatic charges in manufacturing processes. These devices prevent hazards such as material adhesion or sparking in operations involving paper rolling, sheet plastic production, textile mills, and wire drawing.[33][35][3] Antistatic brushes and brushes incorporating polonium-210 have been applied to remove dust from photographic films and plates, as well as in semiconductor fabrication to dissipate static on silicon chips and other sensitive components.[2] In laboratory settings, small polonium-210 sources, typically containing 0.1 microcurie or less, calibrate radiation detection instruments and maintain static-free environments for precise weighing on analytical balances.[33][30] When alloyed with beryllium, polonium-210 forms compact neutron sources for industrial gauging, such as measuring material density in oil well logging and other non-destructive testing applications.[38] Global production of polonium-210, around 8 grams annually as of recent estimates, supports these limited but specialized uses, with devices regulated to contain emissions and replaced periodically due to the isotope's 138-day half-life.[35][3]Scientific and Potential Military Roles
Polonium-210, the most stable and commonly used isotope, functions as a high-intensity alpha particle source in nuclear physics research, where its emissions facilitate calibration of alpha spectrometers and detectors for precise measurement of radioactive decay processes.[39] These sources are prepared via microprecipitation techniques, such as with copper sulfide or tellurium coprecipitation, to create thin-layer deposits suitable for alpha spectrometry in analyzing environmental radionuclides.[39] [40] In experimental settings, polonium's alpha particles interact with beryllium to generate neutrons through (α,n) reactions, producing approximately 93 neutrons per million alpha particles and enabling neutron-based studies in nuclear reactions and material testing.[41] This neutron source capability has supported research in artificial nuclear transmutations since the early 20th century, following Ernest Rutherford's use of polonium alphas for pioneering scattering experiments that revealed atomic structure.[24] Historically, polonium played a direct military role as a component in neutron initiators for fission weapons during the Manhattan Project, where polonium-210 and beryllium mixtures provided the initial neutron burst to trigger supercritical chain reactions.[42] In the implosion-type design, known as the "Urchin" initiator, polonium was electroplated onto beryllium hemispheres separated by a thin nickel-gold barrier; compression from the explosive shockwave mixed the materials, releasing neutrons at the precise moment of core assembly.[42] This system was implemented in the Trinity test device, detonated on July 16, 1945, and in the Fat Man plutonium bomb dropped on Nagasaki on August 9, 1945.[42] Production of polonium for these initiators involved irradiating bismuth targets in nuclear reactors, such as the Clinton pile, with scaling efforts led by Monsanto's Dayton Project starting in July 1943 to meet wartime demands exceeding initial projections.[42] Although effective for immediate deployment, polonium-210's half-life of 138 days required ongoing replenishment, limiting its practicality for stockpiled weapons and leading to its replacement by longer-lived alternatives like deuterium-tritium generators in subsequent designs.[38] Potential modern military applications remain constrained by this decay rate and proliferation risks, with no verified ongoing use in advanced arsenals.[38]Toxicity and Biological Effects
Mechanisms of Action
Polonium-210 exerts its toxic effects primarily through radiotoxicity as an alpha-particle emitter, with a half-life of 138.4 days and alpha particles of 5.3 MeV energy that deposit high linear energy transfer (LET) over a short tissue range of approximately 40-70 micrometers.[5] These particles cause dense ionization along their tracks, generating free radicals and direct hits on cellular components, far exceeding the damage from beta or gamma radiation due to the high relative biological effectiveness (RBE) of alphas, often 10-20 times greater for DNA damage and cell killing.[41] Unlike external alpha exposure, which is shielded by skin, internal contamination allows particles to originate within or near sensitive cells, amplifying lethality; a dose as low as 0.074 MBq/kg can be fatal via hematopoietic syndrome.[43] Upon ingestion or inhalation, polonium-210 is absorbed through the gastrointestinal tract with an efficiency of about 0.05-0.1, depending on solubility and chemical form, entering the bloodstream and distributing nonuniformly to organs rich in reticuloendothelial cells, such as the spleen, liver, kidneys, and bone marrow.[43] It accumulates preferentially in these sites, forming "hot spots" of high local concentration that intensify radiation exposure, while soluble forms enable broader dissemination, leading to systemic effects including oxidative stress and inflammation.[5] Chemical interactions, such as binding to thiols or mimicking sulfur in biomolecules, may contribute secondarily but are overshadowed by the dominant ionizing radiation effects.[41] At the cellular level, alpha particles induce clustered DNA double-strand breaks (DSBs) and other irreparable lesions that overwhelm repair mechanisms like non-homologous end joining, triggering apoptosis, necrosis, or mitotic catastrophe, particularly in rapidly proliferating cells.[5] This genotoxicity promotes mutagenesis and carcinogenesis, with stochastic risks elevated due to the particles' inefficiency in traversing cells—often killing them outright rather than allowing survival with mutations—though survivors face heightened oncogenic potential from chromosomal aberrations.[41] Free radical production exacerbates damage via indirect oxidative pathways, compounding direct ionization in mitochondria and nuclei.[5] Organ-specific mechanisms reflect distribution patterns: in bone marrow, massive stem cell depletion causes pancytopenia and acute radiation syndrome; hepatic and renal cells suffer necrosis from localized hot spots; and gastrointestinal mucosa experiences rapid sloughing due to epithelial turnover disruption.[43] Overall, polonium-210's action exemplifies internal alpha emitters' profile, where short-range, high-LET radiation yields deterministic effects at high doses (e.g., organ failure) and stochastic outcomes at lower exposures (e.g., leukemia, solid tumors), with no threshold for the latter based on linear no-threshold models supported by animal data.[41][18]Acute and Chronic Health Impacts
Polonium-210, the predominant isotope, exerts acute toxic effects primarily through alpha particle irradiation following ingestion or inhalation, concentrating rapidly in the bone marrow, spleen, liver, and kidneys, where it delivers high localized doses leading to cellular necrosis and systemic radiation syndrome.[41] Doses above 0.1–1 microgram are typically fatal within days to weeks, initiating with prodromal gastrointestinal distress—nausea, vomiting, and diarrhea—progressing to bone marrow aplasia, pancytopenia, immunosuppression, hemorrhage, and multi-organ failure, as evidenced in animal studies and human cases where polonium ingestion mimics but exceeds chemical toxin profiles in rapidity and lethality.[43][44] In the 2006 Alexander Litvinenko incident, an estimated ingestion of several micrograms produced initial flu-like symptoms indistinguishable from viral infection, escalating to refractory bone marrow failure and death 23 days post-exposure despite intensive supportive care.00144-6/abstract)[45] Chronic low-level exposure to polonium-210, often via inhalation of insoluble particles, elevates cancer risk through cumulative alpha-induced DNA damage and mutations, with the International Agency for Research on Cancer classifying it as a confirmed human carcinogen based on epidemiological correlations and rodent bioassays demonstrating lung, liver, and hematopoietic malignancies.[46] Inhalation risks are amplified in scenarios like tobacco smoke, where polonium-210 adheres to tar and delivers chronic bronchial doses equivalent to 0.1–1 rad per year in heavy smokers, contributing to elevated lung cancer incidence independent of other tobacco carcinogens.[47] Prolonged internal deposition also impairs hematopoiesis, renal function, and reproductive tissues, with human autopsies revealing polonium accumulation correlating to fibrosis and neoplastic changes in exposed organs, though thresholds for non-cancer effects remain poorly quantified due to rarity of documented cases.[41][48] No safe chronic exposure level exists, as even trace amounts—below 1 nanogram—pose stochastic oncogenic hazards via irreparable double-strand breaks in genomic DNA.[46]Exposure Limits and Safety Protocols
Occupational exposure to polonium-210, primarily an internal alpha radiation hazard via inhalation or ingestion, is regulated under general ionizing radiation standards rather than substance-specific permissible exposure limits (PELs) from OSHA or NIOSH, as no dedicated PEL exists for the element.[49] The U.S. Nuclear Regulatory Commission (NRC) establishes derived air concentrations (DACs) and annual limits on intake (ALIs) in 10 CFR Part 20, Appendix B, with Po-210 inhalation DAC at 3 × 10^{-10} µCi/mL for lung class D (slow clearance) and ALI at 3 µCi for occupational workers, corresponding to a committed effective dose limit of approximately 5 rem (50 mSv) per year. These values aim to restrict chronic exposures to below the 5 rem annual effective dose limit for radiation workers, emphasizing monitoring of air and surface contamination due to Po-210's high specific activity (around 166 Ci/g) and potential for aerosolization.[50] Safety protocols for handling polonium prioritize containment to prevent internal uptake, as external exposure from its alpha emissions is negligible through intact skin or clothing.[18] Laboratory procedures require operations in certified fume hoods or gloveboxes for any manipulation risking volatilization, with minimum personal protective equipment (PPE) including disposable nitrile gloves, lab coats, and safety glasses; double gloving and respiratory protection (e.g., full-face respirators with HEPA filters) are mandated for higher activities or potential spills.[51] Contamination surveys using alpha-sensitive detectors (e.g., zinc sulfide scintillators) must follow each session, with immediate decontamination via chelating agents like DTPA if uptake is suspected, and strict prohibitions on eating, drinking, or applying cosmetics in work areas to avoid inadvertent ingestion.[52] Storage and waste protocols involve sealed, labeled containers in locked, posted areas with restricted access, compliant with NRC exempt quantity limits (e.g., up to 100 µCi without specific licensing for certain devices) and dosimetry for personnel exceeding basic thresholds.[33] Emergency response includes prompt medical evaluation for potential exposure, including bioassay (urine analysis for Po-210 via alpha spectrometry), as the element's 138-day half-life allows detection windows but demands rapid intervention to mitigate bone marrow suppression from doses exceeding 0.2–0.6 µCi intake.[53] International guidelines from the IAEA align with these, stressing engineering controls over administrative measures for high-risk alpha emitters.[54]| Parameter | Value (Occupational) | Notes |
|---|---|---|
| Inhalation ALI | 0.2–3 µCi/year | Varies by clearance class; corresponds to ~5 rem effective dose.[53] |
| Ingestion ALI | 0.6 µCi/year | Primary route concern in labs.[53] |
| DAC (air) | 3 × 10^{-10} µCi/mL | For 1700-hour work year; monitor to stay below. |
| Effective Dose Coefficient (ingestion) | 1.2 × 10^{-6} Sv/Bq | ICRP basis for public/worker calculations.[55] |
Detection and Treatment Approaches
Detection of polonium exposure, primarily from the isotope polonium-210, relies on bioassay techniques analyzing biological samples such as urine, feces, blood, or tissue, as external detection via whole-body counters is ineffective due to its alpha-emitting nature, which produces no penetrating gamma radiation.[56] Alpha spectrometry following radiochemical separation is the standard method, involving sample digestion, purification to isolate polonium (e.g., via co-precipitation with bismuth or tellurium carriers), and deposition onto a substrate for counting.[57] Chemical recovery yields typically range from 60-90% in validated protocols, enabling detection limits as low as 0.1 mBq/L in urine for emergency assessments.[58] Rapid techniques, such as spontaneous auto-deposition of polonium onto silver discs from acidified urine, allow results within hours, critical for acute exposure scenarios.[59] In blood samples, polonium-210 can be quantified from as little as 10 mL via solvent extraction or ion-exchange chromatography prior to alpha counting, with historical studies confirming detectability at trace levels corresponding to occupational exposures.[60] Fecal analysis is particularly sensitive for ingested polonium, as up to 50% of intake may be excreted unabsorbed in the first days, though absorption efficiency can exceed 70% in soluble forms, necessitating combined urine-feces monitoring for accurate dosimetry.[61] Environmental or forensic confirmation often cross-validates bioassay data with surface swipe tests using alpha track detectors or liquid scintillation counting, but human exposure confirmation prioritizes internal dosimetry models incorporating ICRP biokinetic data.[62] Treatment approaches for polonium-210 poisoning emphasize rapid decorporation to mitigate alpha-particle-induced cellular damage, primarily through chelating agents that exploit polonium's affinity for sulfur-containing ligands, alongside supportive care for bone marrow suppression, gastrointestinal hemorrhage, and multi-organ failure. Dimercaprol (2,3-dimercaptopropanol, BAL), administered intramuscularly at doses of 2.5-3 mg/kg every 4-6 hours, is the primary chelator recommended, as it forms stable complexes promoting urinary excretion and reducing tissue retention by up to 50% in rodent models when given within hours of exposure.[63] Penicillamine serves as an oral alternative for milder cases, while dimercaptosuccinic acid (DMSA) and its derivatives have demonstrated superior mobilization of polonium from liver and spleen in animal studies, decreasing lethality by enhancing fecal and urinary output.[64] No antidote fully reverses severe intoxication, as polonium's rapid tissue distribution—concentrating in bone marrow, kidneys, and spleen—leads to irreversible ionization damage; efficacy diminishes sharply after 24-48 hours post-ingestion, as evidenced by the 2006 Litvinenko case where an estimated 10 μg dose overwhelmed chelation efforts despite BAL administration, resulting in death from acute radiation syndrome after 23 days.00144-6/fulltext) Supportive measures include granulocyte colony-stimulating factor for neutropenia, broad-spectrum antibiotics for infection risk, and hemodialysis in renal failure, though Prussian blue (for cesium/thallium) shows limited utility due to polonium's distinct chemistry.[63] Experimental protocols stress immediate gastric lavage or activated charcoal for ingestion, but these are ineffective against absorbed fractions exceeding 90% in some compounds.[65] Overall, survival odds plummet with doses above 1 μg, underscoring prevention via exposure limits (e.g., 40 Bq/day annual intake per ICRP guidelines) over post-exposure interventions.[66]Poisoning Incidents and Investigations
Pre-2000 Cases
Prior to 2000, documented instances of acute polonium poisoning were exceedingly rare, with no confirmed cases of intentional use as a toxin. The sole verified fatal exposure involved accidental inhalation of polonium-210 by an individual in Russia during the 1990s, resulting in death from acute radiation effects; this incident was later identified during forensic reviews as the only prior known lethality attributable to polonium ingestion or inhalation.[67] Limited details emerged publicly, but the case underscored polonium's extreme alpha-particle toxicity when internalized, delivering localized cellular destruction without significant external radiation signature. No other laboratory mishandlings, industrial accidents, or criminal applications involving polonium were reliably attributed to causing poisoning fatalities before 2000, reflecting its scarcity outside specialized nuclear facilities and the challenges in detection due to its short half-life of 138 days and low gamma emission.[68] Chronic low-level exposures, such as from polonium-210 in tobacco smoke, contributed to elevated lung cancer risks but did not manifest as discrete poisoning events.[69]The 2006 Litvinenko Case
Alexander Litvinenko, a former officer in Russia's Federal Security Service (FSB) who had defected to the United Kingdom in 2000 and become a vocal critic of the Russian government, met with Andrei Lugovoy and Dmitri Kovtun, both former KGB officers, at the Pine Bar of London's Millennium Hotel on November 1, 2006.[70] During the meeting, Litvinenko consumed green tea later found to contain polonium-210, an alpha-emitting radioactive isotope with high toxicity due to its rapid cellular damage from alpha particle emission.[70] [71] He fell acutely ill hours later, experiencing severe vomiting and diarrhea, symptoms initially misattributed to possible thallium or other heavy metal poisoning.[72] Litvinenko was hospitalized at University College Hospital in London on November 3, 2006, where his condition deteriorated progressively, marked by bone marrow suppression, pancytopenia, and multiple organ failure consistent with acute radiation syndrome from internal polonium-210 exposure.[68] Radiation tests confirmed polonium-210 ingestion around November 1, with autopsy on December 1 revealing lethal concentrations retained in organs such as the liver, kidneys, and spleen, estimating an intake of approximately 10 micrograms—thousands of times the lethal dose for alpha emitters.[71] [73] He died on November 23, 2006, after 22 days of hospitalization, with post-mortem analysis describing the procedure as one of the most hazardous due to contamination risks.[74] British authorities traced polonium-210 contamination to multiple sites, including the Millennium Hotel bar, Litvinenko's home, and commercial flights from Moscow to London used by Lugovoy and Kovtun in October 2006, indicating the isotope's transport from Russia, where production is state-controlled via nuclear reactors.[75] Scotland Yard charged Lugovoy and Kovtun with murder in 2007, asserting the poisoning occurred during the November 1 meeting, but Russia refused extradition, citing constitutional prohibitions.[76] The 2016 UK public inquiry, chaired by Sir Robert Owen, concluded that Litvinenko's murder was a "state-sponsored" operation by the FSB, with Lugovoy and Kovtun acting as agents and the killing "probably approved" by Russian President Vladimir Putin and FSB Director Nikolai Patrushev, based on forensic evidence, witness testimony, and the operation's sophistication requiring access to weapons-grade polonium-210.[70] [77] Russian officials denied involvement, attributing the death to possible British or other adversaries and questioning the inquiry's impartiality.[76] The case highlighted polonium-210's viability as a covert poison due to its scarcity, detectability challenges, and rapid lethality from targeted alpha irradiation of tissues.[75]Post-2006 Suspicions and Analyses
The public inquiry into Alexander Litvinenko's death, initiated in 2015 and concluding on January 21, 2016, determined that he was murdered through the deliberate ingestion of polonium-210, with the operation likely approved by Russian President Vladimir Putin and conducted by agents Andrei Lugovoi and Dmitry Kovtun under FSB direction.[76][78] The inquiry highlighted forensic evidence of polonium traces along a trail from Moscow to London, including contaminated sites visited by the suspects, supporting the conclusion of state-sponsored assassination.[79] Autoradiography of Litvinenko's hair revealed elevated polonium-210 activity from an earlier exposure in October 2006, indicating at least two poisoning attempts prior to the fatal November incident.[80] Analyses emphasized Russia's dominance in polonium-210 production, with the isotope generated via neutron irradiation of bismuth-209 primarily at the state-controlled Avangard facility near Sarov, making non-Russian sourcing improbable for the quantities involved.[81] The inquiry noted the polonium's high purity and the logistical challenges of its transport, reinforcing attributions to Russian intelligence capabilities rather than independent actors.[70] Post-2006 suspicions extended to the 2004 death of Palestinian leader Yasser Arafat, revived after Litvinenko's case drew attention to polonium-210 as a covert poison.[82] Exhumation of Arafat's remains on November 26, 2012, yielded Swiss forensic tests showing polonium-210 levels in rib bones approximately 18 times background norms, prompting moderate support for an acute poisoning hypothesis from the Institute of Radiation Physics.[83] However, contemporaneous French and Russian analyses found no anomalous polonium or supporting symptoms like myelosuppression and alopecia, attributing residues potentially to environmental contamination or post-mortem factors; France closed its investigation in September 2015 without establishing criminal poisoning.[84][85][86] No other verified polonium-210 poisoning incidents have been documented since 2006, though the element's rarity and detectability have fueled unconfirmed speculation in select political contexts.[68]Environmental Distribution
Presence in Tobacco and Food Chains
Polonium-210 enters tobacco plants primarily through root uptake from soil contaminated by phosphate fertilizers, which are derived from phosphate rock containing uranium-238 decay series radionuclides such as radium-226, radon-222, and lead-210, ultimately yielding polonium-210.[87] Tobacco exhibits hyperaccumulation of polonium compared to many crops, with activity concentrations in cigarette tobacco typically ranging from 16 to 52 Bq/kg across various global brands and regions, including 16.1 ± 1.0 Bq/kg in Turkish samples and 22.8–51.6 Bq/kg (average 36.5 Bq/kg) in Sudanese varieties.[88][89] Upon combustion, approximately 13.6% ± 4.1% of the polonium-210 activity transfers to mainstream smoke in conventional cigarettes, with lead-210 transfer at about 7%, resulting in smokers inhaling 0.1–0.3 Bq per cigarette and accumulating tissue concentrations roughly double those of nonsmokers, particularly in lungs and bones.[90][91] This polonium contributes significantly to the alpha radiation dose in smokers, estimated at 0.16–1.0 μSv per cigarette, or up to 20% of total annual radiation exposure for heavy smokers beyond other tobacco carcinogens.[92][93] In terrestrial food chains beyond tobacco, polonium-210 uptake by plants occurs via similar soil and fertilizer pathways, though at lower levels in most crops (e.g., trace amounts in vegetables like cereals and leafy greens from phosphate-amended soils), with potential elevation in root vegetables or wild plants from uranium-rich soils.[87] Animals grazing on such plants or ingesting soil transfer polonium biomagnifies modestly, appearing in meat and dairy at sub-Bq/kg levels, while wild game or mushrooms can concentrate it higher due to direct soil contact.[94] Marine food chains demonstrate pronounced bioaccumulation of polonium-210, driven by its affinity for soft tissues and biomagnification from plankton to higher trophic levels, with concentrations reaching 37.3–44.9 Bq/kg in yellowfin tuna muscle and up to 548 Bq/kg in viscera.[95] Shellfish such as crustaceans and bivalves exhibit even higher assimilation, often exceeding 100 Bq/kg in edible parts due to filter-feeding and pollutant retention, facilitating trophic transfer to predators including humans.[96] Seafood thus dominates dietary polonium-210 intake, accounting for over 50% of human internal exposure in coastal populations, with ingestion as the primary pathway yielding committed effective doses of 0.1–1.0 μSv per kg consumed, far surpassing terrestrial sources.[57][94] Overall, while atmospheric deposition and natural decay chains seed environmental polonium, anthropogenic enhancements via fertilizers amplify its persistence in both tobacco and aquatic food webs.[87]Biospheric and Human Endogenous Levels
Polonium-210 (²¹⁰Po), the most abundant naturally occurring isotope of polonium, enters the biosphere primarily through the decay of uranium-238 and radon-222 in the uranium decay series, resulting in trace concentrations across environmental compartments.[3] In soils, ²¹⁰Po activity concentrations typically range from 2 to 22,000 Bq/kg dry weight, though common values fall between 10 and 100 Bq/kg, varying with soil type, organic content, and proximity to uranium deposits; for instance, agricultural soils in some regions average around 4–57 Bq/kg.[97] [98] In seawater, dissolved ²¹⁰Po concentrations are low, often 0.4–2.2 mBq/L, but total levels including particulates can reach higher due to adsorption onto suspended matter, with bioconcentration factors exceeding 10⁴ in marine organisms.[99] Atmospheric concentrations average 0.02–0.3 mBq/m³ near ground level, derived mainly from radon emanation and soil dust resuspension.[100] These environmental levels contribute to baseline human exposure via inhalation (about 10–20% of intake) and ingestion through the food chain, establishing endogenous ²¹⁰Po burdens in the body at equilibrium.[56] The average adult human body burden is approximately 40–60 Bq, with annual intake around 58 Bq from natural sources, predominantly seafood, grains, and vegetables; smokers exhibit 2–4 times higher burdens due to tobacco accumulation.[56] [101] Tissue distributions show concentrations of 0.1–2 Bq/kg wet weight in soft tissues like muscle and lung, rising to 1–7 Bq/kg in high-uptake organs such as spleen, liver, and kidneys, where ²¹⁰Po localizes due to its alpha-emitting properties and chemical affinity for sulfur-containing proteins.[43] Bone contains around 1.3–2.4 Bq/kg, reflecting incorporation via lead-210 decay.[102] These endogenous levels pose negligible acute risk but contribute to chronic low-dose alpha radiation, with biokinetic models indicating a biological half-life of 30–50 days in most tissues.[103] Variations occur geographically, with higher burdens in populations reliant on marine diets or residing near radon-prone areas.[46]References
- https://pubchem.ncbi.nlm.nih.gov/compound/Polonium

