President Putin ‘probably’ approved Litvinenko murder
The murder of ex-Russian spy Alexander Litvinenko in 2006 in the UK was “probably” approved by President Vladimir Putin, an inquiry has found.
Mr Putin is likely to have signed off the poisoning of Mr Litvinenko with polonium-210 in part due to personal “antagonism” between the pair, it said.
Home Secretary Theresa May said the murder was a “blatant and unacceptable” breach of international law.
But the Russian Foreign Ministry said the public inquiry was “politicised”.
It said: “We regret that the purely criminal case was politicised and overshadowed the general atmosphere of bilateral relations.”
The long-awaited report into Mr Litvinenko’s death found that two Russian men – Andrei Lugovoi and Dmitry Kovtun – deliberately poisoned the 43-year-old in London in 2006 by putting the radioactive substance polonium-210 into his drink at a hotel.
Sir Robert Owen, the public inquiry chairman, said he was “sure” Mr Litvinenko’s murder had been carried out by the two men and that they were probably acting under the direction of Moscow’s FSB intelligence service, and approved by the organisation’s chief, Nikolai Patrushev, as well as the Russian president.
He said Mr Litvinenko’s work for British intelligence agencies, his criticism of the FSB and Mr Putin, and his association with other Russian dissidents were possible motives for his killing.
There was also “undoubtedly a personal dimension to the antagonism” between Mr Putin and Mr Litvinenko, he said.
Polonium is a chemical element with symbol Po and atomic number 84, discovered in 1898 by Marie Curie and Pierre Curie. A rare and highly radioactive element with no stable isotopes, polonium is chemically similar to bismuth and tellurium, and it occurs in uranium ores. Applications of polonium are few. They include heaters in space probes, antistatic devices, and sources of neutrons and alpha particles. Because of its position in the periodic table, polonium is sometimes classified as a metalloid. Other sources say that on the basis of its properties and behavior, it is “unambiguously a metal”.
Polonium has 33 known isotopes, all of which are radioactive. They have atomic masses that range from 188 to 220 u. 210Po (half-life 138.376 days) is the most widely available. The longer-lived 209Po (half-life 125.2 ± 3.3 years, longest-lived of all polonium isotopes) and 208Po (half-life 2.9 years) can be made through the alpha, proton, or deuteron bombardment of lead or bismuth in a cyclotron.
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. A few curies (1 curie equals 37 gigabecquerels, 1 Ci = 37 GBq) of 210Po emit a blue glow which is caused by excitation of surrounding air.
Solid state form
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, with an edge length of 335.2 picometers; the beta form is rhombohedral. The structure of polonium has been characterized by X-ray diffraction and electron diffraction.
210Po (in common with 238Pu) 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). 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.
The chemistry of polonium is similar to that of tellurium and bismuth. 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+. 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.
Polonium has no common compounds, and almost all of its compounds are synthetically created; more than 50 of those are known. 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, PrPo melts at 1250 °C and TmPo at 2200 °C. PbPo is one of the very few naturally occurring polonium compounds, as polonium alpha decays to form lead.
Halides of the structure PoX2, PoX4 and PoX6 are known. They are soluble in the corresponding hydrogen halides, i.e., PoClX in HCl, PoBrX in HBr and PoI4 in HI. 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.
|Symmetry||Pearson symbol||Space group||No||a (pm)||b(pm)||c(pm)||Z||ρ (g/cm3)||ref|
|PoO2||pale yellow||500 (dec.)||885||fcc||cF12||Fm3m||225||563.7||563.7||563.7||4||8.94|||
Also tentatively called “radium F“, polonium was discovered by Marie and Pierre Curie in 1898, and was named after Marie Curie’s native land of Poland (Latin: Polonia). 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.
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.
In the United States, polonium was produced as part of the Manhattan Project‘s Dayton Project during World War II. It was a critical part of the implosion-type nuclear weapon design used in the Fat Man bomb on Nagasaki in 1945. Polonium and beryllium were the key ingredients of the ‘urchin‘ detonator at the center of the bomb’s spherical plutonium pit. The urchin ignited the nuclear chain reaction at the moment of prompt-criticality to ensure the bomb did not fizzle.
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.
By means of radiometric methods such as gamma spectroscopy (or a method using a chemical separation followed by an activity measurement with a non-energy-dispersive counter), it is possible to measure the concentrations of radioisotopes and to distinguish one from another. In practice, background noise would be present and depending on the detector, the line width would be larger which would make it harder to identify and measure the isotope. In biological/medical work it is common to use the natural 40K present in all tissues/body fluids as a check of the equipment and as an internal standard.
The best way to test for (and measure) many alpha emitters is to use alpha-particle spectroscopy. It is common to place a drop of the test solution on a metal disk which is then dried out to give a uniform coating on the disk. This is then used as the test sample. If the thickness of the layer formed on the disk is too thick then the lines of the spectrum are broadened; this is because some of the energy of the alpha particles is lost during their movement through the layer of active material. An alternative method is to use internal liquid scintillation where the sample is mixed with a scintillation cocktail. When the light emitted is then counted, some machines will record the amount of light energy per radioactive decay event. Due to the imperfections of the liquid scintillation method (such as a failure of all the photons to be detected, cloudy or coloured samples can be difficult to count) and the fact that random quenching can reduce the number of photons generated per radioactive decay, it is possible to get a broadening of the alpha spectra obtained through liquid scintillation. It is likely that these liquid scintillation spectra will be subject to a Gaussian broadening rather than the distortion exhibited when the layer of active material on a disk is too thick.
A third energy dispersive method for counting alpha particles is to use a semiconductor detector.
From left to right the peaks are due to 209Po, 210Po, 239Pu and 241Am. The fact that isotopes such as 239Pu and 241Am have more than one alpha line indicates that the nucleus has the ability to be in different discrete energy levels (like a molecule can).
Occurrence and production
Polonium is a very rare element in nature because of the short half-life of all its isotopes. 210Po, 214Po, and 218Po appear in the decay chain of 238U; thus polonium can be found in uranium ores at about 0.1 mg per metric ton (1 part in 1010), 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.
Because it is present in such small concentrations, isolation of polonium from natural sources is a very 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. Polonium is now obtained by irradiating bismuth with high-energy neutrons or protons.
- Synthesis by (n,γ) reaction
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. The final purification is done pyrochemically followed by liquid-liquid extraction techniques. Polonium may now be made in milligram amounts in this procedure which uses high neutron fluxes found in nuclear reactors. Only about 100 grams are produced each year, practically all of it in Russia, making polonium exceedingly rare.
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.
- Synthesis by (p,n) and (p,2n) reactions
It has been found that the longer-lived isotopes of polonium can be formed by proton bombardment of bismuth using a cyclotron. Other more neutron-rich isotopes can be formed by the irradiation of platinum with carbon nuclei.
Polonium-based sources of alpha particles were produced in the former Soviet Union. Such sources were applied for measuring the thickness of industrial coatings via attenuation of alpha radiation.
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. For instance, 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).
The alpha particles emitted by polonium can be converted to neutrons using beryllium oxide, at a rate of 93 neutrons per million alpha particles. Thus Po-BeO mixtures or alloys are used as a neutron source, for example in a neutron trigger or initiator for nuclear weapons and for inspections of oil wells. About 1500 sources of this type, with an individual activity of 1,850 Ci (68 TBq), have been used annually in the Soviet Union.
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. Alpha particles emitted by polonium ionize air molecules that neutralize charges on the nearby surfaces. 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.
Tobacco smoke from cigarettes contains a small amount of polonium isotope 210, which can become deposited inside smokers’ airways and deliver radiation directly to surrounding cells.
The lungs of smokers can be exposed to four times more polonium than those of non-smokers and specific parts may get a hundred times more radiation. One study estimated that someone smoking one and half packs a day receives the equivalent amount of radiation as someone having 300 chest X-rays a year.
Biology and toxicity
Polonium is highly dangerous and has no biological role. 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). The main hazard is its intense radioactivity (as an alpha emitter), which makes it very 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. 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.
It has been reported that some microbes can methylate polonium by the action of methylcobalamin. 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.
The median lethal dose (LD50) for acute radiation exposure is generally about 4.5 Sv. The committed effective dose equivalent 210Po is 0.51 µSv/Bq if ingested, and 2.5 µSv/Bq if inhaled. So 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) 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, still an extremely small amount. For comparison, one grain of table salt is about 0.06 mg = 60 μg.
Long term (chronic) effects
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. 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 of the estimated 15,000–22,000 lung cancer deaths in the US every year that have been attributed to indoor radon. Tobacco smoking causes additional exposure to polonium.
Regulatory exposure limits and handling
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. The maximum permissible workplace concentration of airborne 210Po is about 10 Bq/m3 (6990300000000000000♠3×10−10 µCi/cm3). The target organs for polonium in humans are the spleen and liver. 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).
210Po is widely used in industry, and readily available with little regulation or restriction. 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).” 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.
Polonium and its compounds must be handled in a glove box, which is further enclosed in another box, maintained at a slightly higher pressure than the glove box to prevent the radioactive materials from leaking out. Gloves made of natural rubber do not provide sufficient protection against the radiation from polonium; surgical gloves are necessary. Neoprene gloves shield radiation from polonium better than natural rubber.
Well-known poisoning case
Polonium was administered to humans for experimental purposes from 1943 to 1947; it was injected into four hospitalised patients, and orally given to a fifth. Studies such as this were funded by the Manhattan Project and the AEC, and conducted at the University of Rochester. The objective was to obtain data on human excretion of polonium to correlate with more extensive data from rats. Patients selected as subjects were chosen because experimenters wanted persons who had not been exposed to polonium either through work or accident. All subjects had incurable diseases. Excretion of polonium was followed, and an autopsy was conducted at that time on the deceased patient to determine which organs absorbed the polonium. Patients’ ages ranged from ‘early thirties’ to ‘early forties.’ The experiments were described in a Studies of polonium metabolism in human subjects, Chapter 3 of Biological Studies with Polonium, Radium, and Plutonium, National Nuclear Energy Series, Volume VI-3, McGraw-Hill, New York, 1950. Not specified is the isotope under study, but at the time polonium-210 was the most readily available polonium isotope. The DoE factsheet submitted for this experiment reported no follow up on these subjects.
It has also been suggested that Irène Joliot-Curie was the first person to die from the radiation effects of polonium. She was accidentally exposed to polonium in 1946 when a sealed capsule of the element exploded on her laboratory bench. In 1956, she died from leukemia.
According to the 2008 book The Bomb in the Basement, several deaths in Israel during 1957–1969 were caused by 210Po. 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 died from cancer. One of his students died of leukemia, and two colleagues died after a few years, both from cancer. The issue was investigated secretly, and there was never any formal admission that a connection between the leak and the deaths had existed.
The cause of death in the 2006 murder of Russian dissident Alexander Litvinenko was determined to be 210Po poisoning. According to Prof. Nick Priest of Middlesex University, an environmental toxicologist and radiation expert, speaking on Sky News on December 2, Litvinenko was probably the first person to die of the acute α-radiation effects of 210Po.
Abnormally high concentrations of 210Po were detected in July 2012 in clothes and personal belongings of the Palestinian leader Yasser Arafat, a heavy smoker, who died on 11 November 2004 of uncertain causes. The spokesman for the Institut de Radiophysique in Lausanne, Switzerland, where those items were analyzed, stressed that the “clinical symptoms described in Arafat’s medical reports were not consistent with polonium-210 and that conclusions could not be drawn as to whether the Palestinian leader was poisoned or not”, and that “the only way to confirm the findings would be to exhume Arafat’s body to test it for polonium-210.” On 27 November 2012 Arafat’s body was exhumed and samples were taken for separate analysis by experts from France, Switzerland and Russia. On 12 October 2013, The Lancet published the group’s finding that high levels of the element were found in Arafat’s blood, urine, and in saliva stains on his clothes and toothbrush. The French tests later found some polonium but stated it was from “natural environmental origin.” Following later Russian tests, Vladimir Uiba, the head of the Russian Federal Medical and Biological Agency, stated in December 2013 that Arafat died of natural causes, and they had no plans to conduct further tests.
It has been suggested that chelation agents such as British Anti-Lewisite (dimercaprol) can be used to decontaminate humans. 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 after 5 months.
Detection in biological specimens
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.
Commercial products containing polonium
210Po is contained in anti-static brushes, which are used in some printing presses. Some anti-static brushes contain up to 500 microcuries (20 MBq) of 210Po as a source of charged particles for neutralizing static electricity. In USA, the devices with no more than 500 µCi (19 MBq) of (sealed) 210Po per unit can be bought in any amount under a “general license”, which means that a buyer need not be registered by any authorities.
Tiny amounts of such radioisotopes 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 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. According to United Nuclear, they typically sell between four and eight sources per year.
Occurrence in humans and the biosphere
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 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.
As early as the 1920s Antoine Lacassagne, using polonium provided by his colleague Marie Curie, showed that the element has a very specific pattern of uptake in rabbit tissues, with high concentrations particularly in liver, kidney and testes. More recent evidence suggests that this behavior results from polonium substituting for sulfur in sulfur-containing amino-acids or related molecules and that similar patterns of distribution occur in human tissues. 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.
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.
The presence of polonium in tobacco smoke has been known since the early 1960s. 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.
Polonium is also found in the food chain, especially in seafood.[