actinides in the environment

{{Pollution sidebar|Radiation}}

The actinide series is a group of chemical elements with atomic numbers ranging from 89 to 102,{{refn | group = note | Lawrencium, element 103, is sometimes included in the actinide series despite being a part of the 6d transition series.}} 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.{{refn | group = note | It is suspected, though unconfirmed, that the long-lived isotope 244Pu may exist primordially.{{cite journal |last1=Wu |first1=Yang |last2=Dai |first2=Xiongxin |first3=Shan |last3=Xing |first4=Maoyi |last4=Luo |first5=Marcus |last5=Christl |first6=Hans-Arno |last6=Synal |first7=Shaochun |last7=Hou |date=2022 |title=Direct search for primordial 244Pu in Bayan Obo bastnaesite |url=http://www.ccspublishing.org.cn/article/doi/10.1016/j.cclet.2022.03.036?pageType=en |journal=Chinese Chemical Letters |volume=33 |issue=7 |pages=3522–3526 |doi=10.1016/j.cclet.2022.03.036 |access-date=29 January 2024|url-access=subscription }}}} 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.{{cite journal |last1=Seaborg |first1=Glenn T. |last2=Segrè |first2=Emilio |title=The Trans-Uranium Elements |journal=Nature |date=June 1947 |volume=159 |issue=4052 |pages=863–865 |doi=10.1038/159863a0|pmid=20252546 |bibcode=1947Natur.159..863S }} However, certain isotopes of elements up to californium (atomic number 98) still have practical applications which take advantage of their radioactive properties.{{cite web |title=Americium in Ionization Smoke Detectors |url=https://www.epa.gov/radtown/americium-ionization-smoke-detectors#:~:text=Ionization%20smoke%20detectors%20have%20a,when%20they%20are%20properly%20handled. |website=www.epa.gov |publisher=Environmental Protection Agency |language=en |date=27 November 2018}}{{cite web |last1=Ellis |first1=Jason K. |title=ORNL's californium-252 will play pivotal role in new reactor startups {{!}} ORNL |url=https://www.ornl.gov/news/ornls-californium-252-will-play-pivotal-role-new-reactor-startups |website=www.ornl.gov |date=2 December 2020 |publisher=Oak Ridge National Laboratory}}

While all actinides are radioactive, actinides and actinide compounds comprise a significant portion of the Earth's crust.{{cite book |last1=Herring |first1=J. Stephen |title=Encyclopedia of sustainability science and technology |date=2012 |publisher=Springer |location=New York |isbn=978-0-387-89469-0 | page = 11202}} 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.Herring, p. 11203 The global production of uranium in 2021 was over six million tons, with Australia having been the leading supplier.{{cite web |title=Uranium Mining Overview - World Nuclear Association |url=https://world-nuclear.org/information-library/nuclear-fuel-cycle/mining-of-uranium/uranium-mining-overview |website=world-nuclear.org |publisher=World Nuclear Association}} 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.Herring, pp. 11204-11205

The primary hazard associated with actinides is their radioactivity, though they may also cause heavy metal poisoning if absorbed into the bloodstream.{{cite journal |last1=Briner |first1=Wayne |title=The Toxicity of Depleted Uranium |journal=International Journal of Environmental Research and Public Health |date=25 January 2010 |volume=7 |issue=1 |pages=303–313 |doi=10.3390/ijerph7010303|doi-access=free |pmid=20195447 |pmc=2819790 }} 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.{{cite book |last1=Keith |first1=S |last2=Faroon |first2=O |last3=Roney |first3=N |last4=Scinicariello |first4=F |last5=Wilbur |first5=S |last6=Ingerman |first6=L |last7=Llados |first7=F |last8=Plewak |first8=D |last9=Wohlers |first9=D |last10=Diamond |first10=G |title=Toxicological Profile for Uranium. |chapter=Public Health Statement for Uranium |date=February 2013 |publisher=Agency for Toxic Substances and Disease Registry (US) |pmid=24049861 |chapter-url=https://www.ncbi.nlm.nih.gov/books/NBK158804/}} Inhaled actinide compounds, however, will be more damaging as they remain in the lungs and irradiate lung tissue.

Actinium

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.{{cite journal |last1=Peppard |first1=D. F. |last2=Mason |first2=G. W. |last3=Gray |first3=P. R. |last4=Mech |first4=J. F. |title=Occurrence of the (4n + 1) series in nature |journal=Journal of the American Chemical Society |date=1952 |volume=74 |issue=23 |pages=6081–6084 |doi=10.1021/ja01143a074 |bibcode=1952JAChS..74.6081P |url=https://digital.library.unt.edu/ark:/67531/metadc172698/m2/1/high_res_d/metadc172698.pdf }}

Thorium

File:MonaziteUSGOV.jpg

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.{{cite web| url= http://www.dae.gov.in/iandm/minesback.htm| title= Compendium Of Policy And Statutory Provisions Relating To Exploitation Of Beach Sand Minerals| publisher= Government Of India| access-date= 2008-12-19| archive-url= https://web.archive.org/web/20081204114125/http://www.dae.gov.in/iandm/minesback.htm| url-status= dead| archive-date= 2008-12-04}}

= Occurrence =

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.[http://www.atsdr.cdc.gov/tfacts147.pdf THORIUM] Agency for Toxic Substances and Disease Registry. July 1999. 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 =

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

{{Unreferenced-section|date=October 2024}}

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{{Fix|text=Unclear whether this means parts per thousand or parts per trillion}} or 0.1 picocuries per gram (pCi/g).

Uranium

{{Main|Uranium in the environment}}

{{Further|Uranium#Human exposure}}

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{{cite web|url=http://www.webelements.com/webelements/elements/text/U/geol.html|title=Uranium: the essentials|publisher=WebElements|access-date=2008-12-19}} 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

Like plutonium, neptunium has a high affinity for soil.{{cite web|url=http://www.ead.anl.gov/pub/doc/neptunium.pdf |title=Neptunium |date=August 2005 |publisher=Argonne National Laboratory, EVS |access-date=2008-12-19 |archive-url=https://web.archive.org/web/20081219162631/http://www.ead.anl.gov/pub/doc/neptunium.pdf |url-status=dead |archive-date=2008-12-19 }} 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

{{main|Plutonium in the environment}}

= Sources =

Plutonium in the environment has several sources. These include:

= Environmental chemistry =

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|date=August 2024}} 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.{{cite journal|last=Whicker |first=R.D.|author2=S.A. Ibrahim|date=2006|journal=Journal of Environmental Radioactivity|volume=88|pages=171–188|pmid=16564117|title=Vertical migration of 134Cs bearing soil particles in arid soils: implications for plutonium redistribution.|issue=2|doi=10.1016/j.jenvrad.2006.01.010}}

Americium

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{{clarify|date=August 2024}}{{Fix|text=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.{{cite journal|last1=Bunzl|first1=K.|last2=Kracke|first2=W.|title=Fate of fall-out plutonium and americium in the environment: selected examples|journal=Journal of Alloys and Compounds|volume=213-214|pages=212–218|doi=10.1016/0925-8388(94)90906-7|publisher=Elsevier B.V.|year=1994}}

File:David Hahn.jpg

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.{{cite web|url=http://www.cbwinfo.com/Radiological/radmat/am241.shtml |title=Radiological Agent: Americium-241 |publisher=CBWInfo.com |access-date=2008-12-19 |archive-url=https://web.archive.org/web/20090108002036/http://www.cbwinfo.com/Radiological/radmat/am241.shtml |url-status=dead |archive-date=2009-01-08 }} 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.{{Cite journal|last=Taylor|first=David M.|date=July 1989|title=The biodistribution and toxicity of plutonium, americium and neptunium|journal=Science of the Total Environment|volume=83|issue=3|pages=217–225|doi=10.1016/0048-9697(89)90094-6|pmid=2781271 |bibcode=1989ScTEn..83..217T }} Americium is stable in the +3 oxidation state, while the +4 oxidation state of plutonium can form in the human body.{{Cite web|url=https://pubchem.ncbi.nlm.nih.gov/compound/23966|title=Americium|last=PubChem|website=pubchem.ncbi.nlm.nih.gov|language=en|access-date=2019-12-13}}

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.{{Cite web|url=https://www.livescience.com/39808-facts-about-neptunium.html|title=Facts About Neptunium|last=Stoll 2017-10-10T22:55:00Z|first=Carol|website=livescience.com|date=10 October 2017 |language=en|access-date=2019-12-13}}

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.{{cite web|title=Public Health Statement for Americium|url=https://www.atsdr.cdc.gov/phs/phs.asp?id=809&tid=158|website=CDC - ATSDR|access-date=11 September 2016}} 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.{{cite journal |vauthors = Chaplin J, Warwick P, Cundy A, Bochud F, Froidevaux P |title=Novel DGT Configurations for the Assessment of Bioavailable Plutonium, Americium, and Uranium in Marine and Freshwater Environments |journal=Analytical Chemistry |date=25 August 2021 |volume=93 |issue=35 |pages=11937–11945 |doi=10.1021/acs.analchem.1c01342 |pmid=34432435 |s2cid=237307309 |doi-access=free }}

Curium

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.[http://www.ead.anl.gov/pub/doc/curium.pdf Human Health Fact Sheet on Curium] {{Webarchive|url=https://web.archive.org/web/20060218162709/http://www.ead.anl.gov/pub/doc/curium.pdf |date=2006-02-18 }}, Los Alamos National Laboratory

Californium

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.{{cite web|url=http://www.evs.anl.gov/pub/doc/Californium.pdf |title=Human Health Fact Sheet: Californium |date=August 2005 |publisher=Argonne National Laboratory |url-status=dead |archive-url=https://web.archive.org/web/20110721032736/http://www.evs.anl.gov/pub/doc/Californium.pdf |archive-date=July 21, 2011 }}

Notes

{{reflist | group = note}}

See also

References

{{Reflist}}

=General references=

  • {{cite book |first1=B. E. |last1=Burakov |first2=M. I. |last2=Ojovan |first3=W. E. |last3=Lee |title=Crystalline Materials for Actinide Immobilisation |publisher=Imperial College Press |location=London |date=2010 |url=http://www.icpress.co.uk/engineering/p652.html |archive-url=https://web.archive.org/web/20120309093650/http://www.icpress.co.uk/engineering/p652.html |url-status=dead |archive-date=2012-03-09 |isbn=978-1-84816-418-5}}

Further reading

  • Hala, Jiri, and James D. Navratil. Radioactivity, Ionizing Radiation and Nuclear Energy. Konvoj: Brno, Czech Republic, 2003. {{ISBN|80-7302-053-X}}.