Radiochemistry

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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. This is very different from radiation chemistry where the radiation levels are kept too low to influence the chemistry.

Contents

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

Main decay modes

All radioisotopes are unstable isotopes of elements— that undergo nuclear decay and emit some form of radiation. The radiation emitted can be of several types including alpha, beta, gamma radiation, proton, and neutron emission along with neutrino and antiparticle emission decay pathways.

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 the 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. γ (gamma) radiation—the emission of electromagnetic energy (such as gamma 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 of 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. A high-energy most interesting object which has been studied in this way is the hair of Napoleon's head, which has been examined for its arsenic content. [1]

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 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 that 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 (half-life 15 h) but with increasing time the 239Np (half-life 2.4 d after formation from parent 239U with half-life 24 min) and finally the 60Co activity (5.3 yr) would predominate.

Biology applications

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

Another example is the work that 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, [2] 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 that did not contain the cobalt compound did not form the volatile polonium compound. [3] 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.

In medicine PET (Positron Emission Tomography) scans are commonly used for diagnostic purposes in. A radiative tracer is injected intravenously into the patient and then taken to the PET machine. The radioactive tracer releases radiation outward from the patient and the cameras in the machine interpret the radiation rays from the tracer. PET scan machines use solid state scintillation detection because of their high detection efficiency, NaI(Tl) crystals absorb the tracer's radiation and produce photons that get converted into an electrical signal for the machine to analyze. [4]

Environmental

Radiochemistry also includes the study of the behaviour of radioisotopes in the environment; for instance, a forest or grass fire can make radioisotopes mobile again. [5] 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 can 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 [6] [7] [8] and dissolve in water and thus enter drinking water [9] In addition, human activities such as bomb tests, accidents, [10] 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 [11] 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. This includes work on both solutions of relatively simple complexes [12] [13] and work on colloids [14] 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. [15]

Movement of colloids

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 that bear the radioactive metal can migrate as colloidal particles through the soil. This has been shown to occur using soil particles labeled with 134Cs, these are able to move through cracks in the soil. [16]

Normal background

Radioactivity is present everywhere on Earth since its formation. 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). [17]

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). [18] Other researchers have also worked on the fixing of uranium using bacteria , Francis R. Livens et al. (Working at Manchester) have suggested that the reason why Geobacter sulfurreducens can reduce UO2+
2 cations to uranium dioxide is that the bacteria reduce the uranyl cations to UO+
2 which then undergoes disproportionation to form UO2+
2 and UO2. This reasoning was based (at least in part) on the observation that NpO+
2 is not converted to an insoluble neptunium oxide by the bacteria. [19]

Education

Despite the growing use of nuclear medicine, the potential expansion of nuclear power plants, and worries about protection against nuclear threats and the management of the nuclear waste generated in past decades, the number of students opting to specialize in nuclear and radiochemistry has decreased significantly over the past few decades. Now, with many experts in these fields approaching retirement age, action is needed to avoid a workforce gap in these critical fields, for example by building student interest in these careers, expanding the educational capacity of universities and colleges, and providing more specific on-the-job training. [20]

Nuclear and Radiochemistry (NRC) is mostly being taught at the university level, usually first at the Master- and PhD-degree level. In Europe, substantial effort is being done to harmonize and prepare the NRC education for the industry's and society's future needs. This effort is being coordinated in projects funded by the Coordinated Action supported by the European Atomic Energy Community's 7th Framework Program: The CINCH-II project - Cooperation in education and training In Nuclear Chemistry.

Related Research Articles

The actinide or actinoid series encompasses the 14 metallic chemical elements with atomic numbers from 89 to 103, actinium through Lawrencium. The actinide series derives its name from the first element in the series, actinium. The informal chemical symbol An is used in general discussions of actinide chemistry to refer to any actinide.

<span class="mw-page-title-main">Curium</span> Chemical element, symbol Cm and atomic number 96

Curium is a synthetic chemical element; it has symbol Cm and atomic number 96. This transuranic actinide element was named after eminent scientists Marie and Pierre Curie, both known for their research on radioactivity. Curium was first intentionally made by the team of Glenn T. Seaborg, Ralph A. James, and Albert Ghiorso in 1944, using the cyclotron at Berkeley. They bombarded the newly discovered element plutonium with alpha particles. This was then sent to the Metallurgical Laboratory at University of Chicago where a tiny sample of curium was eventually separated and identified. The discovery was kept secret until after the end of World War II. The news was released to the public in November 1947. Most curium is produced by bombarding uranium or plutonium with neutrons in nuclear reactors – one tonne of spent nuclear fuel contains ~20 grams of curium.

<span class="mw-page-title-main">Polonium</span> Chemical element, symbol Po and atomic number 84

Polonium is a chemical element; it has symbol Po and atomic number 84. A rare and highly radioactive metal 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 in uranium ores, as it is the penultimate daughter of natural uranium-238. Though longer-lived isotopes exist, such as the 125.2 years half-life of polonium-209, 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.

<span class="mw-page-title-main">Uranium</span> Chemical element, symbol U and atomic number 92

Uranium is a chemical element; it has symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium radioactively decays by emitting an alpha particle. The half-life of this decay varies between 159,200 and 4.5 billion years for different isotopes, making them useful for dating the age of the Earth. The most common isotopes in natural uranium are uranium-238 and uranium-235. Uranium has the highest atomic weight of the primordially occurring elements. Its density is about 70% higher than that of lead and slightly lower than that of gold or tungsten. It occurs naturally in low concentrations of a few parts per million in soil, rock and water, and is commercially extracted from uranium-bearing minerals such as uraninite.

A radionuclide (radioactive nuclide, radioisotope or radioactive isotope) is a nuclide that has excess numbers of either neutrons or protons, giving it excess nuclear energy, and making it unstable. This excess energy can be used in one of three ways: emitted from the nucleus as gamma radiation; transferred to one of its electrons to release it as a conversion electron; or used to create and emit a new particle (alpha particle or beta particle) from the nucleus. During those processes, the radionuclide is said to undergo radioactive decay. These emissions are considered ionizing radiation because they are energetic enough to liberate an electron from another atom. The radioactive decay can produce a stable nuclide or will sometimes produce a new unstable radionuclide which may undergo further decay. Radioactive decay is a random process at the level of single atoms: it is impossible to predict when one particular atom will decay. However, for a collection of atoms of a single nuclide the decay rate, and thus the half-life (t1/2) for that collection, can be calculated from their measured decay constants. The range of the half-lives of radioactive atoms has no known limits and spans a time range of over 55 orders of magnitude.

<span class="mw-page-title-main">Radioactive waste</span> Unusable radioactive materials

Radioactive waste is a type of hazardous waste that contains radioactive material. Radioactive waste is a result of many activities, including nuclear medicine, nuclear research, nuclear power generation, nuclear decommissioning, rare-earth mining, and nuclear weapons reprocessing. The storage and disposal of radioactive waste is regulated by government agencies in order to protect human health and the environment.

<span class="mw-page-title-main">Nuclear fuel cycle</span> Process of manufacturing and consuming nuclear fuel

The nuclear fuel cycle, also called nuclear fuel chain, is the progression of nuclear fuel through a series of differing stages. It consists of steps in the front end, which are the preparation of the fuel, steps in the service period in which the fuel is used during reactor operation, and steps in the back end, which are necessary to safely manage, contain, and either reprocess or dispose of spent nuclear fuel. If spent fuel is not reprocessed, the fuel cycle is referred to as an open fuel cycle ; if the spent fuel is reprocessed, it is referred to as a closed fuel cycle.

<span class="mw-page-title-main">Radioactive decay</span> Emissions from unstable atomic nuclei

Radioactive decay is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is considered radioactive. Three of the most common types of decay are alpha, beta, and gamma decay. The weak force is the mechanism that is responsible for beta decay, while the other two are governed by the electromagnetism and nuclear force.

<span class="mw-page-title-main">Decay chain</span> Series of radioactive decays

In nuclear science, the decay chain refers to a series of radioactive decays of different radioactive decay products as a sequential series of transformations. It is also known as a "radioactive cascade". The typical radioisotope does not decay directly to a stable state, but rather it decays to another radioisotope. Thus there is usually a series of decays until the atom has become a stable isotope, meaning that the nucleus of the atom has reached a stable state.

<span class="mw-page-title-main">Nuclear chemistry</span> Branch of chemistry dealing with radioactivity, transmutation and other nuclear processes

Nuclear chemistry is the sub-field of chemistry dealing with radioactivity, nuclear processes, and transformations in the nuclei of atoms, such as nuclear transmutation and nuclear properties.

Polonium-210 (210Po, Po-210, historically radium F) is an isotope of polonium. It undergoes alpha decay to stable 206Pb with a half-life of 138.376 days (about 4+1⁄2 months), the longest half-life of all naturally occurring polonium isotopes (210–218Po). First identified in 1898, and also marking the discovery of the element polonium, 210Po is generated in the decay chain of uranium-238 and radium-226. 210Po is a prominent contaminant in the environment, mostly affecting seafood and tobacco. Its extreme toxicity is attributed to intense radioactivity, mostly due to alpha particles, which easily cause radiation damage, including cancer in surrounding tissue. The specific activity of 210
Po is 166 TBq/g, i.e., 1.66 × 1014 Bq/g. At the same time, 210Po is not readily detected by common radiation detectors, because its gamma rays have a very low energy. Therefore, 210
Po can be considered as a quasi-pure alpha emitter.

<span class="mw-page-title-main">Neutron activation</span> Induction of radioactivity by neutron radiation

Neutron activation is the process in which neutron radiation induces radioactivity in materials, and occurs when atomic nuclei capture free neutrons, becoming heavier and entering excited states. The excited nucleus decays immediately by emitting gamma rays, or particles such as beta particles, alpha particles, fission products, and neutrons. Thus, the process of neutron capture, even after any intermediate decay, often results in the formation of an unstable activation product. Such radioactive nuclei can exhibit half-lives ranging from small fractions of a second to many years.

<span class="mw-page-title-main">Nuclear fuel</span> Material fuelling nuclear reactors

Nuclear fuel is material used in nuclear power stations to produce heat to power turbines. Heat is created when nuclear fuel undergoes nuclear fission.

Neptunium (93Np) is usually considered an artificial element, although trace quantities are found in nature, so a standard atomic weight cannot be given. Like all trace or artificial elements, it has no stable isotopes. The first isotope to be synthesized and identified was 239Np in 1940, produced by bombarding 238
U
 with neutrons to produce 239
U
, which then underwent beta decay to 239
Np
.

Plutonium (94Pu) is an artificial element, except for trace quantities resulting from neutron capture by uranium, and thus a standard atomic weight cannot be given. Like all artificial elements, it has no stable isotopes. It was synthesized long before being found in nature, the first isotope synthesized being 238Pu in 1940. Twenty plutonium radioisotopes have been characterized. The most stable are plutonium-244 with a half-life of 80.8 million years, plutonium-242 with a half-life of 373,300 years, and plutonium-239 with a half-life of 24,110 years. All of the remaining radioactive isotopes have half-lives that are less than 7,000 years. This element also has eight meta states; all have half-lives of less than one second.

Americium (95Am) is an artificial element, and thus a standard atomic weight cannot be given. Like all artificial elements, it has no known stable isotopes. The first isotope to be synthesized was 241Am in 1944. The artificial element decays by ejecting alpha particles. Americium has an atomic number of 95. Despite 243
Am being an order of magnitude longer lived than 241
Am, the former is harder to obtain than the latter as more of it is present in spent nuclear fuel.

<span class="mw-page-title-main">Environmental radioactivity</span> Radioactivity naturally present within the Earth

Environmental radioactivity is produced by radioactive materials in the human environment. While some radioisotopes, such as strontium-90 (90Sr) and technetium-99 (99Tc), are only found on Earth as a result of human activity, and some, like potassium-40 (40K), are only present due to natural processes, a few isotopes, e.g. tritium (3H), result from both natural processes and human activities. The concentration and location of some natural isotopes, particularly uranium-238 (238U), can be affected by human activity.

<span class="mw-page-title-main">Plutonium in the environment</span> Plutonium present within the environment

Since the mid-20th century, plutonium in the environment has been primarily produced by human activity. The first plants to produce plutonium for use in cold war atomic bombs were at the Hanford nuclear site, in Washington, and Mayak nuclear plant, in Chelyabinsk Oblast, Russia. Over a period of four decades, "both released more than 200 million curies of radioactive isotopes into the surrounding environment – twice the amount expelled in the Chernobyl disaster in each instance".

<span class="mw-page-title-main">Isotope</span> Different atoms of the same element

Isotopes are distinct nuclear species of the same chemical element. They have the same atomic number and position in the periodic table, but differ in nucleon numbers due to different numbers of neutrons in their nuclei. While all isotopes of a given element have almost the same chemical properties, they have different atomic masses and physical properties.

<span class="mw-page-title-main">Discovery of the neutron</span> Scientific background leading to the discovery of subatomic particles

The discovery of the neutron and its properties was central to the extraordinary developments in atomic physics in the first half of the 20th century. Early in the century, Ernest Rutherford developed a crude model of the atom, based on the gold foil experiment of Hans Geiger and Ernest Marsden. In this model, atoms had their mass and positive electric charge concentrated in a very small nucleus. By 1920, isotopes of chemical elements had been discovered, the atomic masses had been determined to be (approximately) integer multiples of the mass of the hydrogen atom, and the atomic number had been identified as the charge on the nucleus. Throughout the 1920s, the nucleus was viewed as composed of combinations of protons and electrons, the two elementary particles known at the time, but that model presented several experimental and theoretical contradictions.

References

  1. ↑ H. Smith, S. Forshufvud and A. Wassén, Nature, 1962, 194(26 May), 725–726
  2. ↑ 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
  3. ↑ 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
  4. ↑ Saha, Gopal B. (2010). "PET Scanning Systems". Basics of PET Imaging. Springer, New York, NY. pp. 19–39. doi:10.1007/978-1-4419-0805-6_2. ISBN   9781441908049.
  5. ↑ 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 Radioact86:143–63 PMID   16213067
  6. ↑ Janja Vaupotič and Ivan Kobal, "Effective doses in schools based on nanosize radon progeny aerosols", Atmospheric Environment, 2006, 40, 7494–7507
  7. ↑ Michael Durand, Building and Environment, "Indoor air pollution caused by geothermal gases", 2006, 41, 1607–1610
  8. ↑ Paolo Boffetta, "Human cancer from environmental pollutants: The epidemiological evidence", Mutation Research/Genetic Toxicology and Environmental Mutagenesis, 2006, 608, 157–162
  9. ↑ M. Forte, R. Rusconi, M. T. Cazzaniga and G. Sgorbati, "The measurement of radioactivity in Italian drinking waters". Microchemical Journal, 2007, 85, 98–102
  10. ↑ 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
  11. ↑ Rabideau, S.W., Journal of the American Chemical Society, 1957, 79, 6350–6353
  12. ↑ 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
  13. ↑ 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
  14. ↑ 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
  15. ↑ 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
  16. ↑ 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.
  17. ↑ "Generic Procedures for Assessment and Response during a Radiological Emergency", International Atomic Energy Agency TECDOC Series number 1162, published in 2000
  18. ↑ 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.
  19. ↑ 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.
  20. ↑ Assuring a Future U.S.-Based Nuclear and Radiochemistry Expertise. Board on Chemical Sciences and Technology. 2012. ISBN   978-0-309-22534-2.
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