Actinides in the environment
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The actinide series is a group of chemical elements with atomic numbers ranging from 89 to 102,[note 1] including notable elements such as uranium and plutonium. The nuclides (or isotopes) thorium-232, uranium-235, and uranium-238 occur primordially, while trace quantities of actinium, protactinium, neptunium, and plutonium exist as a result of radioactive decay and (in the case of neptunium and plutonium) neutron capture of uranium.[note 2] These elements are far more radioactive than the naturally occurring thorium and uranium, and thus have much shorter half-lives. Elements with atomic numbers greater than 94 do not exist naturally on Earth, and must be produced in a nuclear reactor.[2] However, certain isotopes of elements up to californium (atomic number 98) still have practical applications which take advantage of their radioactive properties.[3][4]
While all actinides are radioactive, actinides and actinide compounds comprise a significant portion of the Earth's crust.[5] There is enough thorium and uranium to be commercially mined, with thorium having a concentration in the Earth's crust about four times that of uranium.[6] The global production of uranium in 2021 was over six million tons, with Australia having been the leading supplier.[7] Thorium is extracted as a byproduct of titanium, zirconium, tin, and rare earths from monazite, from which thorium is often a waste product. Despite its greater abundance in the Earth's crust, the low demand for thorium in comparison to other metals extracted alongside thorium has led to a global surplus.[8]
The primary hazard associated with actinides is their radioactivity, though they may also cause heavy metal poisoning if absorbed into the bloodstream.[9] Generally, ingested insoluble actinide compounds, such as uranium dioxide and mixed oxide (MOX) fuel, will pass through the digestive tract with little effect since they have long half-lives, and cannot dissolve and be absorbed into the bloodstream.[10] Inhaled actinide compounds, however, will be more damaging as they remain in the lungs and irradiate lung tissue.
Actinium
[edit]Actinium can be found naturally in traces in uranium ore as 227Ac, an α and β emitter with half-life 21.773 years. Uranium ore contains about 0.2 mg of actinium per ton of uranium. It is more commonly made in milligram amounts by neutron irradiation of 226Ra in a nuclear reactor. Natural actinium almost exclusively consists of one isotope, 227Ac, with only minute traces of other shorter-lived isotopes (225Ac and 228Ac) occurring in other decay chains.[11]
Thorium
[edit]
In India, a large amount of thorium ore can be found in the form of monazite in placer deposits of the Western and Eastern coastal dune sands, particularly in the Tamil Nadu coastal areas. The residents of this area are exposed to a naturally occurring radiation dose ten times higher than the worldwide average.[12]
Occurrence
[edit]Thorium is found at low levels in most rocks and soils, where it is about three times more abundant than uranium and about as abundant as lead. On average, soil commonly contains around 6 parts per million (ppm) thorium.[13] Thorium occurs in several minerals; the most common is the rare earth-thorium-phosphate mineral monazite, which contains up to 12% thorium oxide. Several countries have substantial deposits. 232Th decays very slowly (its half-life is about three times the age of the Earth). Other isotopes of thorium occur in the thorium and uranium decay chains. These are shorter-lived and hence much more radioactive than 232Th, though on a mass basis they are negligible.
Effects in humans
[edit]Thorium has been linked to liver cancer. In the past, thoria (thorium dioxide) was used as a contrast agent for medical X-ray radiography but its use has been discontinued. It was sold under the name Thorotrast.
Protactinium
[edit]Protactinium-231 occurs naturally in uranium ores such as pitchblende, to the extent of 3 ppm in some ores. Protactinium is naturally present in soil, rock, surface water, groundwater, plants and animals in very low concentrations (on the order of 1 ppt[Unclear whether this means parts per thousand or parts per trillion] or 0.1 picocuries per gram (pCi/g).
Uranium
[edit]Uranium is a natural metal which is widely found. It is present in almost all soils and it is more plentiful than antimony, beryllium, cadmium, gold, mercury, silver, or tungsten, and is about as abundant as arsenic or molybdenum. Significant concentrations of uranium occur in some substances such as phosphate rock deposits, and minerals such as lignite, and monazite sands in uranium-rich ores (it is recovered commercially from these sources).
Seawater contains about 3.3 parts per billion of uranium by weight[14] as uranium (VI) forms soluble carbonate complexes. Extraction of uranium from seawater has been considered as a means of obtaining the element. Because of the very low specific activity of uranium the chemical effects of it upon living things can often outweigh the effects of its radioactivity. Additional uranium has been added to the environment in some locations, from the nuclear fuel cycle and the use of depleted uranium in munitions.
Neptunium
[edit]Like plutonium, neptunium has a high affinity for soil.[15] However, it is relatively mobile over the long term, and diffusion of neptunium-237 in groundwater is a major issue in designing a deep geological repository for permanent storage of spent nuclear fuel. 237Np has a half-life of 2.144 million years and is therefore a long-term problem; but its half-life is still much shorter than those of uranium-238, uranium-235, or uranium-236, and 237Np therefore has higher specific activity than those nuclides. It is used only to make plutonium-238 when bombarded with neutrons in a lab.
Plutonium
[edit]Sources
[edit]Plutonium in the environment has several sources. These include:
- Atomic batteries
- In space
- In pacemakers
- Bomb detonations
- Bomb safety trials
- Nuclear crime
- Nuclear fuel cycle
- Nuclear power plants
Environmental chemistry
[edit]Plutonium, like other actinides, readily forms a plutonium dioxide (plutonyl) core (PuO2). In the environment, this plutonyl core readily complexes with carbonate as well as other oxygen moieties (OH−, NO2−, NO3−, and SO42−) to form charged complexes which can be readily mobile with low affinities to soil.
- PuO2CO32−
- PuO2(CO3)24−
- PuO2(CO3)36−
PuO2 formed from neutralizing highly acidic nitric acid solutions tends to form polymeric PuO2 which is resistant to complexation. Plutonium also readily shifts valences between the +3, +4, +5 and +6 states. It is common for some fraction of plutonium in solution to exist in all of these states in equilibrium.
Plutonium is known to bind to soil particles very strongly; see above[where?] for an X-ray spectroscopic study of plutonium in soil and concrete. While caesium has very different chemistry from the actinides, it is well known that both caesium and many actinides bind strongly to the minerals in soil. It has been possible to use 134Cs-labeled soil to study the migration of Pu and Cs is soils. It has been shown that colloidal transport processes control the migration of Cs (and will control the migration of Pu) in the soil at the Waste Isolation Pilot Plant.[16]
Americium
[edit]Americium often enters landfills from discarded smoke detectors. The rules for the disposal of smoke detectors are very relaxed in most municipalities. For instance, in the UK it is permissible to dispose of a smoke detector containing americium by placing it in the dustbin with normal household rubbish, but each dustbin worth of rubbish is limited[clarification needed][by law?] to only containing one smoke detector. The manufacture of products containing americium (such as smoke detectors) as well as nuclear reactors and explosions may also release the americium into the environment.[17]
In 1999, a truck transporting 900 smoke detectors in France was reported to have caught fire; it is claimed that this led to a release of americium into the environment.[18] In the U.S., the "Radioactive Boy Scout" David Hahn was able to buy thousands of smoke detectors at remainder prices and concentrate the americium from them.
There have been cases of humans being exposed to americium. The worst case was that of Harold McCluskey, who was exposed to an extremely high dose of americium-241 after an accident involving a glove box. He was subsequently treated with chelation therapy. It is likely that the medical care which he was given saved his life; despite similar biodistribution and toxicity to plutonium, the two radioactive elements have different solution-state chemistries.[19] Americium is stable in the +3 oxidation state, while the +4 oxidation state of plutonium can form in the human body.[20]
The most common isotope americium-241 decays (half-life 432 years) to neptunium-237 which has a much longer half-life, so in the long term, the issues discussed above for neptunium apply.[21]
Americium released into the environment tends to remain in soil and water at relatively shallow depths and may be taken up by animals and plants during growth; shellfish such as shrimp take up americium-241 in their shells, and parts of grain plants can become contaminated by exposure.[22] In a 2021 paper, J.D. Chaplin et al. reported advances in the diffusive gradients in thin films technique, which have provided a method to measure labile bioavailable americium in soils, as well as in freshwater and seawater.[23]
Curium
[edit]Atmospheric curium compounds are poorly soluble in common solvents and mostly adhere to soil particles. Soil analysis revealed about 4,000 times higher concentration of curium in the sandy soil particles than in water present in the soil pores. An even higher ratio of about 18,000 was measured in loam soils.[24]
Californium
[edit]Californium is fairly insoluble in water, but it adheres well to ordinary soil, and concentrations of it in the soil can be 500 times higher than in the water surrounding the soil particles.[25]
Notes
[edit]- ^ Lawrencium, element 103, is sometimes included in the actinide series despite being a part of the 6d transition series.
- ^ It is suspected, though unconfirmed, that the long-lived isotope 244Pu may exist primordially.[1]
See also
[edit]References
[edit]- ^ Wu, Yang; Dai, Xiongxin; Xing, Shan; Luo, Maoyi; Christl, Marcus; Synal, Hans-Arno; Hou, Shaochun (2022). "Direct search for primordial 244Pu in Bayan Obo bastnaesite". Chinese Chemical Letters. 33 (7): 3522–3526. doi:10.1016/j.cclet.2022.03.036. Retrieved 29 January 2024.
- ^ Seaborg, Glenn T.; Segrè, Emilio (June 1947). "The Trans-Uranium Elements". Nature. 159 (4052): 863–865. Bibcode:1947Natur.159..863S. doi:10.1038/159863a0. PMID 20252546.
- ^ "Americium in Ionization Smoke Detectors". www.epa.gov. Environmental Protection Agency. 27 November 2018.
- ^ Ellis, Jason K. "ORNL's californium-252 will play pivotal role in new reactor startups | ORNL". www.ornl.gov. Oak Ridge National Laboratory.
- ^ Herring, J. Stephen (2012). Encyclopedia of sustainability science and technology. New York: Springer. p. 11202. ISBN 978-0-387-89469-0.
- ^ Herring, p. 11203
- ^ "Uranium Mining Overview - World Nuclear Association". world-nuclear.org. World Nuclear Association.
- ^ Herring, pp. 11204-11205
- ^ Briner, Wayne (25 January 2010). "The Toxicity of Depleted Uranium". International Journal of Environmental Research and Public Health. 7 (1): 303–313. doi:10.3390/ijerph7010303. PMID 20195447.
- ^ Keith, S; Faroon, O; Roney, N; Scinicariello, F; Wilbur, S; Ingerman, L; Llados, F; Plewak, D; Wohlers, D; Diamond, G (February 2013). "Public Health Statement for Uranium". Toxicological Profile for Uranium. PMID 24049861.
{{cite book}}:|journal=ignored (help) - ^ Peppard, D. F.; Mason, G. W.; Gray, P. R.; Mech, J. F. (1952). "Occurrence of the (4n + 1) series in nature" (PDF). Journal of the American Chemical Society. 74 (23): 6081–6084. doi:10.1021/ja01143a074.
- ^ "Compendium Of Policy And Statutory Provisions Relating To Exploitation Of Beach Sand Minerals". Government Of India. Archived from the original on 2008-12-04. Retrieved 2008-12-19.
- ^ THORIUM Agency for Toxic Substances and Disease Registry. July 1999.
- ^ "Uranium: the essentials". WebElements. Retrieved 2008-12-19.
- ^ "Neptunium" (PDF). Argonne National Laboratory, EVS. August 2005. Archived from the original (PDF) on 2008-12-19. Retrieved 2008-12-19.
- ^ Whicker, R.D.; S.A. Ibrahim (2006). "Vertical migration of 134Cs bearing soil particles in arid soils: implications for plutonium redistribution". Journal of Environmental Radioactivity. 88 (2): 171–188. doi:10.1016/j.jenvrad.2006.01.010. PMID 16564117.
- ^ Bunzl, K.; Kracke, W. (1994). "Fate of fall-out plutonium and americium in the environment: selected examples". Journal of Alloys and Compounds. 213–214. Elsevier B.V.: 212–218. doi:10.1016/0925-8388(94)90906-7.
- ^ "Radiological Agent: Americium-241". CBWInfo.com. Archived from the original on 2009-01-08. Retrieved 2008-12-19.
- ^ Taylor, David M. (July 1989). "The biodistribution and toxicity of plutonium, americium and neptunium". Science of the Total Environment. 83 (3): 217–225. Bibcode:1989ScTEn..83..217T. doi:10.1016/0048-9697(89)90094-6. PMID 2781271.
- ^ PubChem. "Americium". pubchem.ncbi.nlm.nih.gov. Retrieved 2019-12-13.
- ^ Stoll 2017-10-10T22:55:00Z, Carol (10 October 2017). "Facts About Neptunium". livescience.com. Retrieved 2019-12-13.
{{cite web}}: CS1 maint: numeric names: authors list (link) - ^ "Public Health Statement for Americium". CDC - ATSDR. Retrieved 11 September 2016.
- ^ Chaplin J, Warwick P, Cundy A, Bochud F, Froidevaux P (25 August 2021). "Novel DGT Configurations for the Assessment of Bioavailable Plutonium, Americium, and Uranium in Marine and Freshwater Environments". Analytical Chemistry. 93 (35): 11937–11945. doi:10.1021/acs.analchem.1c01342. PMID 34432435. S2CID 237307309.
- ^ Human Health Fact Sheet on Curium Archived 2006-02-18 at the Wayback Machine, Los Alamos National Laboratory
- ^ "Human Health Fact Sheet: Californium" (PDF). Argonne National Laboratory. August 2005. Archived from the original (PDF) on July 21, 2011.
- Burakov, B. E.; Ojovan, M. I.; Lee, W. E. (2010). Crystalline Materials for Actinide Immobilisation. London: Imperial College Press. ISBN 978-1-84816-418-5. Archived from the original on 2012-03-09.
Further reading
[edit]- Hala, Jiri, and James D. Navratil. Radioactivity, Ionizing Radiation and Nuclear Energy. Konvoj: Brno, Czech Republic, 2003. ISBN 80-7302-053-X.
External links
[edit]- "Why do mechanisms matter in radioactive waste management?" – Royal Society for Chemistry
- "Spectroscopies for Environmental Studies of Actinide Species" – Federation of American Scientists
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