Radiochemistry

Radiochemistry is the chemistry of radioactive materials, where radioactive isotopes of elements are used to study the properties and chemical reactions of non-radioactive isotopes (often within radiochemistry the absence of radioactivity leads to a substance being described as being "inactive" as the isotopes are "stable"). Much of radiochemistry deals with the use of radioactivity to study ordinary chemical reactions.

Radiochemistry includes the study of both natural and man-made radioisotopes.

Main decay modes

All radioisotopes are unstable isotopes of elements—undergo nuclear decay and emit some form of radiation. The radiation emitted can be one of three types, called alpha, beta, or gamma radiation.

1. α (alpha) radiation - the emission of an alpha particle (which contains 2 protons and 2 neutrons) from an atomic nucleus. When this occurs, the atom’s atomic mass will decrease by 4 units and atomic number will decrease by 2.

2. β (beta) radiation - the transmutation of a neutron into an electron and a proton. After this happens, the electron is emitted from the nucleus into the electron cloud.

3. gamma radiation - the emission of electromagnetic energy (such as X-rays) from the nucleus of an atom. This usually occurs during alpha or beta radioactive decay.

These three types of radiation can be distinguished by their difference in penetrating power.

Alpha can be stopped quite easily by a few centimetres in air or a piece of paper and is equivalent to a helium nucleus. Beta can be cut off by an aluminium sheet just a few millimetres thick and are electrons. Gamma is the most penetrating of the three and is a massless chargeless high energy photon. Gamma radiation requires an appreciable amount of heavy metal radiation shielding (usually lead or barium-based) to reduce its intensity.

Activation analysis

By neutron irradiation of objects it is possible to induce radioactivity, this activation of stable isotopes to create radioisotopes is the basis of neutron activation analysis. One of the most interesting objects which has been studied in this way is the hair of Napoleon's head, which have been examined for their arsenic content. [H. SMITH, S. FORSHUFVUD & A. WASSÉN, "Nature", 1962, 194(26 May), 725-726]

A series of different experimental methods exist, these have been designed to enable the measurement of a range of different elements in different matrices. To reduce the effect of the matrix it is common to use the chemical extraction of the wanted element "and/or" to allow the radioactivity due to the matrix elements to decay before the measurement of the radioactivity. Since the matrix effect can be corrected for by observing the decay spectrum, little or no sample preparation is required for some samples, making neutron activation analysis less susceptible to contamination.

The effects of a series of different cooling times can be seen if a hypothetical sample which contains sodium, uranium and cobalt in a 100:10:1 ratio was subjected to a very short pulse of thermal neutrons. The initial radioactivity would be dominated by the ²⁴Na activity but with increasing time the ²³⁹Np and finally the ⁶⁰Co activity would predominate.

Biochemical uses

One biological application is the study of DNA using radioactive phosphorus-32. In these experiments stable phosphorus is replaced by the chemical identical radioactive P-32, and the resulting radioactivity is used in analysis of the molecules and their behaviour.

Another example is the work which was done on the methylation of elements such as sulfur, selenium, tellurium and polonium by living organisms. It has been shown that bacteria can convert these elements into volatile compounds, [N. Momoshima, Li-X. Song, S. Osaki and Y. Maeda, "Biologically induced Po emission from fresh water", "Journal of Environmental Radioactivity", 2002, 63, 187-197] it is thought that methylcobalamin (vitamin B12 alkylates these elements to create the dimethyls. It has been shown that a combination of Cobaloxime and inorganic polonium in sterile water forms a volatile polonium compound, while a control experiment which did not contain the cobalt compound did not form the volatile polonium compound. [N. Momoshima, Li-X. Song, S. Osaki and Y. Maeda, "Formation and emission of volatile polonium compound by microbial activity and polonium methylation with methylcobalamin", "Environmental Science and Technology", 2001, 35, 2956-2960] For the sulfur work the isotope ³⁵S was used, while for polonium ²⁰⁷Po was used. In some related work by the addition of ⁵⁷Co to the bacterial culture, followed by isolation of the cobalamin from the bacteria (and the measurement of the radioactivity of the isolated cobalamin) it was shown that the bacteria convert available cobalt into methylcobalamin.

Environmental

Radiochemistry also includes the study of the behaviour of radioisotopes in the environment; for instance, a forest or grass fire can make radioisotopes become mobile again. [Yoschenko VI "et al" (2006) Resuspension and redistribution of radionuclides during grassland and forest fires in the Chernobyl exclusion zone: part I. Fire experiments "J Envir Radioact" 86:143-63 PMID 16213067] In these experiments, fires were started in the exclusion zone around Chernobyl and the radioactivity in the air downwind was measured.

It is important to note that a vast number of processes are able to release radioactivity into the environment, for example the action of cosmic rays on the air is responsible for the formation of radioisotopes (such as ¹⁴C and ³²P), the decay of ²²⁶Ra forms ²²²Rn which is a gas which can diffuse through rocks before entering buildings [Janja Vaupotič and Ivan Kobal, "Effective doses in schools based on nanosize radon progeny aerosols", "Atmospheric Environment", 2006, 40, 7494-7507] [Michael Durand, Building and Environment, "Indoor air pollution caused by geothermal gases", 2006, 41, 1607-1610] [Paolo Boffetta, "Human cancer from environmental pollutants: The epidemiological evidence", "Mutation Research/Genetic Toxicology and Environmental Mutagenesis", 2006, 608, 157-162] and dissolve in water and thus enter drinking water [M. Forte, R. Rusconi, M.T. Cazzaniga and G. Sgorbati, "The measurement of radioactivity in Italian drinking waters", "Microchemical Journal", 2007, 85, 98-102] in addition human activities such as bomb tests, accidents, [R. Pöllänen, M.E. Ketterer, S. Lehto, M. Hokkanen, T.K. Ikäheimonen, T. Siiskonen, M. Moring, M.P. Rubio Montero and A. Martín Sánchez, "Multi-technique characterization of a nuclearbomb particle from the Palomares accident", "Journal of Environmental Radioactivity", 2006, 90, 15-28] and normal releases from industry have resulted in the release of radioactivity.

Chemical form of the actinides

The environmental chemistry of some radioactive elements such as plutonium is complicated by the fact that solutions of this element can undergo disproportionation [Rabideau, S.W., "Journal of the American Chemical Society", 1957, 79, 6350-6353] and as a result many different oxidation states can coexist at once. Some work has been done on the identification of the oxidation state and coordination number of plutonium and the other actinides under different conditions has been done. [http://www.fas.org/sgp/othergov/doe/lanl/pubs/00818043.pdf] This includes work on both solutions of relatively simple complexes [P. G. Allen, J. J. Bucher, D. K. Shuh, N. M. Edelstein, and T. Reich, "Investigation of Aquo and Chloro Complexes of UO22+, NpO2+, Np4+, and Pu3+ by X-ray Absorption Fine Structure Spectroscopy ", "Inorganic Chemistry", 1997, 36, 4676-4683] [David L. Clark, Steven D. Conradson, D. Webster Keogh Phillip D. Palmer Brian L. Scott and C. Drew Tait, "Identification of the Limiting Species in the Plutonium(IV) Carbonate System. Solid State and Solution Molecular Structure of the [Pu(CO3)5] 6- Ion", "Inorganic Chemistry", 1998, 37, 2893-2899] and work on colloids [Jörg Rothe, Clemens Walther, Melissa A. Denecke, and Th. Fanghänel, "XAFS and LIBD Investigation of the Formation and Structure of Colloidal Pu(IV) Hydrolysis Products ", "Inorganic Chemistry", 2004, 43, 4708-4718] Two of the key matrixes are soil/rocks and concrete, in these systems the chemical properties of plutonium have been studied using methods such as EXAFS and XANES. [M. C. Duff, D. B. Hunter, I. R. Triay, P. M. Bertsch, D. T. Reed, S. R. Sutton, G. Shea-McCarthy, J. Kitten, P. Eng, S. J. Chipera, and D. T. Vaniman, "Mineral Associations and Average Oxidation States of Sorbed Pu on Tuff", "Environ. Sci. Technol", 1999, 33, 2163-2169] [http://www.wmsym.org/Abstracts/2002/Proceedings/6b/188.pdf] [http://www.lanl.gov/orgs/nmt/nmtdo/AQarchive/02spring/synchrotron.html]

Movement of colloids

It is important to note that while binding of a metal to the surfaces of the soil particles can prevent its movement through a layer of soil, it is possible for the particles of soil which bear the radioactive metal can migrate as colloidal particles through soil. This has been shown to occur using soil particles labeled with ¹³⁴Cs, these have been shown to be able to move through cracks in the soil. [R.D. Whicker and S.A. Ibrahim, "Vertical migration of 134Cs bearing soil particles in arid soils: implications for plutonium redistribution", "Journal of Environmental Radioactivity", 2006, 88, 171-188.]

Normal background

It is important to note that radioactivity is present everywhere (and has been since the formation of the earth). According to the International Atomic Energy Agency, one kilogram of soil typically contains the following amounts of the following three natural radioisotopes 370 Bq ⁴⁰K (typical range 100-700 Bq), 25 Bq ²²⁶Ra (typical range 10-50 Bq), 25 Bq ²³⁸U (typical range 10-50 Bq) and 25 Bq ²³²Th (typical range 7-50 Bq). [Generic Procedures for Assessment and Response during a Radiological Emergency, International Atomic Energy Agency TECDOC Series number 1162, published in 2000 [http://www-pub.iaea.org/MTCD/publications/PubDetails.asp?pubId=5926] ]

Action of microorganisms

The action of micro-organisms can fix uranium; Thermoanaerobacter can use chromium(VI), iron(III), cobalt(III), manganese(IV) and uranium(VI) as electron acceptors while acetate, glucose, hydrogen, lactate, pyruvate, succinate, and xylose can act as electron donors for the metabolism of the bacteria. In this way the metals can be reduced to form magnetite (Fe₃O₄), siderite (FeCO₃), rhodochrosite (MnCO₃), and uraninite (UO₂). [Yul Roh, Shi V. Liu, Guangshan Li, Heshu Huang, Tommy J. Phelps, and Jizhong Zhou, "Isolation and Characterization of Metal-Reducing Thermoanaerobacter Strains from Deep Subsurface Environments of the Piceance Basin, Colorado", "Applied and Environmental Microbiology", 2002, 68, 6013-6020.] Other researchers have also worked on the fixing of uranium using bacteria [http://www.physorg.com/news67270244.html] [http://biology.plosjournals.org/perlserv/?request=get-document&doi=10.1371%2Fjournal.pbio.0040282] [http://www.pnl.gov/news/release.asp?id=175] , Francis R. Livens "et al." (Working at Manchester) have suggested that the reason why "Geobacter sulfurreducens" can reduce UO₂²⁺ carions to uranium dioxide is that the bacteria reduce the uranyl cations to UO₂⁺ which then undergoes disproportionation to form UO₂²⁺ and UO₂. This reasoning was based (at least in part) on the observation that NpO₂⁺ is not converted to an insoluble neptunium oxide by the bacteria. [Joanna C. Renshaw, Laura J. C. Butchins, Francis R. Livens, Iain May, John M. Charnock, and Jonathan R. Lloyd, "Environ. Sci. Technol.", 2005, 39(15), 5657-5660.]

References