Polonium production

The polonium production in an LBE-cooled reactor is so high that in the 80 MW, LBE-cooled ADS developed in the 5th Framework Program of Euratom, the polonium inventory within the primary coolant circuit was evaluated to be 2 kg at equilibrium. This amount of polonium generates a decay heat in the primary system that, 5 days after a reactor shutdown, would equal the decay heat power of the fuel itself (Cinotti et al., 2011). 

Pure lead is not completely exempt firom polonium formation because Pb (the most abundant natural isotope of lead) transmutes into Bi, and Po is eventually produced from neutron capture by ° Bi. The rate of polonium production in pure lead is, however, much lower than in the case of LBE, and it is negligible in terms of decay heat power. In fact, the polonium inventory at equilibrium in the primary system of a 1500 MWth, pure lead-cooled reactor (ie, ELSY) has been calculated to be less than 1 g after 40 years of irradiation (Cinotti et al., 2011). 

Gr. aktis, aktinos, beam or ray). Discovered by Andre Debierne in 1899 and independently by F. Giesel in 1902. Occurs naturally in association with uranium minerals. Actinium-227, a decay product of uranium-235, is a beta emitter with a 21.6-year half-life. Its principal decay products are thorium-227 (18.5-day half-life), radium-223 (11.4-day half-life), and a number of short-lived products including radon, bismuth, polonium, and lead isotopes. In equilibrium with its decay products, it is a powerful source of alpha rays. Actinium metal has been prepared by the reduction of actinium fluoride with lithium vapor at about 1100 to 1300-degrees G. The chemical behavior of actinium is similar to that of the rare earths, particularly lanthanum. Purified actinium comes into equilibrium with its decay products at the end of 185 days, and then decays according to its 21.6-year half-life. It is about 150 times as active as radium, making it of value in the production of neutrons. 

Radon-222 [14859-67-7] Rn, is a naturally occuriing, iaert, radioactive gas formed from the decay of radium-226 [13982-63-3] Ra. Because Ra is a ubiquitous, water-soluble component of the earth s cmst, its daughter product, Rn, is found everywhere. A major health concern is radon s radioactive decay products. Radon has a half-life of 4 days, decayiag to polonium-218 [15422-74-9] Po, with the emission of an a particle. It is Po, an a-emitter having a half-life of 3 min, and polonium-214 [15735-67-8] Po, an a-emitter having a half-life of 1.6 x lO " s, that are of most concern. Polonium-218 decays to lead-214 [15067-28A] a p-emitter haviag = 27 min, which decays to bismuth-214 [14733-03-0], a p-emitter haviag... 

An alplia p uticle is an energetic helium nucleus. The alplia particle is released from a radioactive element witli a neutron to proton ratio tliat is too low. The helium nucleus consists of two protons and two neutrons. The alplia particle differs from a helimn atom in that it is emitted witliout any electrons. The resulting daughter product from tliis tj pe of transformation lias an atomic number Uiat is two less tluin its parent and an atomic mass number tliat is four less. Below is an e. aiiiple of alpha decay using polonium (Po) polonium has an atomic mass number of 210 (protons and neutrons) and atomic number of 84. 

It will be recalled that is 100% abundant and is the heaviest stable nuclide of any element (p. 550), but it is essential to use very high purity Bi to prevent unwanted nuclear side-reactions which would contaminate the product Po in particular Sc, Ag, As, Sb and Te must be <0.1 ppm and Fe <10ppm. Polonium can be obtained directly in milligram amounts by fractional vacuum distillation from the metallic bismuth. Alternatively, it can be deposited spontaneously by electrochemical replacement onto the surface of a less electropositive metal... 

PoS forms as a black precipitate when H2S is added to acidic solutions of polonium compounds. Its solubility product is 5 X 10-2 The... 

The final member of the group, actinium, was identified in uranium minerals by A. Debieme in 1899, the year after P. and M. Curie had discovered polonium and radium in the same minerals. However, the naturally occurring isotope, Ac, is a emitter with a half-life of 21.77 y and the intense y activity of its decay products makes it difficult to study. 

Eighteen isotopes of sulfur, 17 of selenium, 21 of tellurium, and 27 of polonium have been registered of these, 4 sulfur, 6 selenium, and 8 tellurium isotopes are stable, while there is no stable isotope of polonium. None of the naturally occurring isotopes of Se is radioactive its radioisotopes are by-products of the nuclear reactor and neutron activation technology. The naturally occurring, stable isotopes of S, Se, and Te are included in Table 1.2. 

There are a series of papers that focus on the behavior of the radon decay products and their interactions with the indoor atmosphere. Previous studies (Goldstein and Hopke, 1983) have elucidated the mechanisms of neutralization of the Po-218 ionic species in air. Wilkening (1987) reviews the physics of small ions in the air. It now appears that the initially formed polonium ion is rapidly neutralized, but can become associated with other ions present. Reports by Jonassen (1984) and Jonassen and McLaughlin (1985) suggest that only 5 to 10% of the decay products are associated with highly mobile ions and that much of the activity is on large particles that have a bipolar charge distribution. 

Radium F is thought to be identical with Polonium ( 87). Another product is also obtained by these decompositions, with which we shall deal later (94). 

Most of the known chemistry of polonium is based on the naturally occurring radioactive isotope polonium-210, which is a natural radioactive decay by-product of the uranium decay series. Its melting point is 254°C, its boiling point is 962°C, and its density is 9.32g/cm. ... 

Polonium is found only in trace amounts in the Earths crust. In nature it is found in pitchblende (uranium ore) as a decay product of uranium. Because it is so scarce, it is usually artificially produced by bombarding bismuth-209 with neutrons in a nuclear (atomic) reactor, resulting in bismuth-210, which has a half-hfe of five days. Bi-210 subsequently decays into Po-210 through beta decay The reaction for this process is Bi( ) Bi — °Po + (3-. Only small commercial milligram amounts are produced by this procedure. 

Radon is the heaviest of the noble gases and is the only one that is radioactive. It is the decay product of radium, thorium, and uranium ores and rocks found underground. As it decays, it emits alpha particles (hehum nuclei) and is then transmuted to polonium and finally lead. The Earth s atmosphere is just 0.0000000000000000001% radon, but because radon is 7.5 times heavier than air, it can collect in basements and low places in buildings and homes. 

Radon s source is a step in the transmutation of several elements uranium —> thorium — radium —> radon —> polonium —> lead. (There are a number of intermediate decay products and steps involved in this process.) Radon-222 forms and collects just a few inches below the surface of the ground and is often found in trapped pockets of air. It escapes through porous soils and crevices. 

In the environment, thorium and its compounds do not degrade or mineralize like many organic compounds, but instead speciate into different chemical compounds and form radioactive decay products. Analytical methods for the quantification of radioactive decay products, such as radium, radon, polonium and lead are available. However, the decay products of thorium are rarely analyzed in environmental samples. Since radon-220 (thoron, a decay product of thorium-232) is a gas, determination of thoron decay products in some environmental samples may be simpler, and their concentrations may be used as an indirect measure of the parent compound in the environment if a secular equilibrium is reached between thorium-232 and all its decay products. There are few analytical methods that will allow quantification of the speciation products formed as a result of environmental interactions of thorium (e.g., formation of complex). A knowledge of the environmental transformation processes of thorium and the compounds formed as a result is important in the understanding of their transport in environmental media. For example, in aquatic media, formation of soluble complexes will increase thorium mobility, whereas formation of insoluble species will enhance its incorporation into the sediment and limit its mobility. 

Because of its radioactivity and alpha emission, polonium forms many types of radiolytic oxidation-reduction products. 

The deposition of polonium on to copper does not give a good separation of the element from bismuth (83, 111), but bismuth powder itself provides a quite successful process (25). In practice, the irradiated bismuth is dissolved in a mixture of hydrochloric and nitric acids, and after elimination of the latter, the solution is stirred with a few grams of powdered bismuth the polonium is deposited completely on to the bismuth. The product is dissolved in acid and the whole process repeated with decreasing amounts of metallic bismuth, until the proportion of polonium to bismuth is high enough for the former to be precipitated as the metal with stannous chloride. 

The radiation decomposition in 10-3 M polonium solution ( 1 curic/ml) causes a visible evolution of gas (5, 34). The radiolysis products are strongly oxidizing, which adds difficulty to the study of the element in its lower, bipositive, state. Peroxide formation appears to be the factor which prevents a study of solutions of the element in the sexapositive state (13), at any rate on the milligram scale. 

The physical properties of the metal (Table II) resemble those of thallium, lead and bismuth, its neighbors in the Periodic Table, rather than those of tellurium, its lower homologue. The low melting and boiling points are particularly noteworthy an attempted study of the Hall effect in polonium metal has also been reported (90). In chemical properties the metal is very similar to tellurium, the most striking resemblance being in its reactions with concentrated sulfuric acid (or sulfur trioxide) and with concentrated selenic acid. The products are the bright red solids, PoSOs and... 

A white solid, possibly polonium tetrafluoride, is obtained by treating polonium hydroxide or tetrachloride with dilute aqueous hydrofluoric acid treatment of this solid, in suspension in dilute hydrofluoric acid, with sulfur dioxide yields a bluish grey product (possibly PoF2) which rapidly reverts to the original white solid on standing, presumably owing to radio-lytic oxidation 12). The solubility of polonium(IV) in aqueous hydrofluoric acid increases rapidly with acid concentration, indicating complex ion formation (/ft), p. 48). 

There have been some unsuccessful attempts to prepare a volatile hexafluoride from fluorine and polonium-210 26, 104), but recently such a fluoride has been prepared in this way from polonium-208 plated on platinum 132). The product appears to be stable while in the vapor phase, but on cooling a nonvolatile compound is formed, probably polonium tetrafluoride resulting from radiation decomposition of the hexafluoride. Analytical data are not recorded for any polonium fluoride, largely owing to the difficulty of determining fluoride ion accurately at the microgram level. 

Complexes with organic compounds have been reported. Solubility studies with tributyl phosphate (TBP) indicate the formation of a complex PoC14-2TBP (IS). Weighable amounts of polonium tetrachloride in dilute hydrochloric acid can be titrated to a colorless end point with ethylene-diamine tetra-acetic acid (EDTA) the results suggest a complex with two molecules of EDTA, but solubility studies favor a 1 1 complex. The EDTA complex is soluble in alkali and is more stable in alkaline than in acid media, but the ligand is rapidly destroyed by the radiation and solvent radiolysis products 12). However, EDTA can apparently be used to complex trace polonium in the separation of radium D-E-F mixtures (129). 

Bipositive polonium in hydrochloric acid solution (pink) is oxidized to polonium(lV) by hydrogen peroxide, by hypochlorous acid or by the radiolysis products of the alpha bombardment of the solvent. Solutions of polonium(II) in acid are obtained by the reduction of polonium(lV) with sulfur dioxide or hydrazine in the cold, or with arsenious oxide on warming. Polonium (IV) is not reduced in hydrochloric acid by either hydroxylamine or oxalic acid, even on boiling 6). 

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