Technetium-99, 99Tc
General
Symbol99Tc
Namestechnetium-99, 99Tc, Tc-99
Protons (Z)43
Neutrons (N)56
Nuclide data
Natural abundancetrace
Half-life (t1/2)211100±1200 years
Spin9/2+
Excess energy−87327.9±0.9 keV
Binding energy8613.610±0.009 keV
Decay products99Ru
Decay modes
Decay modeDecay energy (MeV)
Beta decay0.2975
Isotopes of technetium
Complete table of nuclides

Technetium-99 (99Tc) is an isotope of technetium which decays with a half-life of 211,000 years to stable ruthenium-99, emitting beta particles, but no gamma rays. It is the most significant long-lived fission product of uranium fission, producing the largest fraction of the total long-lived radiation emissions of nuclear waste. Technetium-99 has a fission product yield of 6.0507% for thermal neutron fission of uranium-235.

The metastable technetium-99m (99mTc) is a short-lived (half-life about 6 hours) nuclear isomer used in nuclear medicine, produced from molybdenum-99. It decays by isomeric transition to technetium-99, a desirable characteristic, since the very long half-life and type of decay of technetium-99 imposes little further radiation burden on the body.

Radiation

The weak beta emission is stopped by the walls of laboratory glassware. Soft X-rays are emitted when the beta particles are stopped, but as long as the body is kept more than 30 cm away these should pose no problem. The primary hazard when working with technetium is inhalation of dust; such radioactive contamination in the lungs can pose a significant cancer risk.

Role in nuclear waste

Yield, % per fission[1]
Thermal Fast 14 MeV
232Th not fissile 2.919 ± .076 1.953 ± .098
233U 5.03 ± .14 4.85 ± .17 3.87 ± .22
235U 6.132 ± .092 5.80 ± .13 5.02 ± .13
238U not fissile 6.181 ± .099 5.737 ± .040
239Pu 6.185 ± .056 5.82 ± .13  ?
241Pu 5.61 ± .25 4.1 ± 2.3  ?

Due to its high fission yield, relatively long half-life, and mobility in the environment, technetium-99 is one of the more significant components of nuclear waste. Measured in becquerels per amount of spent fuel, it is the dominant producer of radiation in the period from about 104 to 106 years after the creation of the nuclear waste.[2] The next shortest-lived fission product is samarium-151 with a half-life of 90 years, though a number of actinides produced by neutron capture have half-lives in the intermediate range.

Releases

Long-lived fission products
Nuclide t1⁄2 Yield Q[a 1] βγ
(Ma) (%)[a 2] (keV)
99Tc 0.2116.1385294 β
126Sn 0.2300.10844050[a 3] βγ
79Se 0.3270.0447151 β
135Cs 1.33 6.9110[a 4]269 β
93Zr 1.53 5.457591 βγ
107Pd 6.5  1.249933 β
129I 15.7  0.8410194 βγ
  1. ↑ Decay energy is split among β, neutrino, and γ if any.
  2. ↑ Per 65 thermal neutron fissions of 235U and 35 of 239Pu.
  3. ↑ Has decay energy 380 keV, but its decay product 126Sb has decay energy 3.67 MeV.
  4. ↑ Lower in thermal reactors because 135Xe, its predecessor, readily absorbs neutrons.

An estimated 160 TBq (about 250 kg) of technetium-99 was released into the environment up to 1994 by atmospheric nuclear tests.[2] The amount of technetium-99 from civilian nuclear power released into the environment up to 1986 is estimated to be on the order of 1000 TBq (about 1600 kg), primarily by outdated methods of nuclear fuel reprocessing; most of this was discharged into the sea. In recent years, reprocessing methods have improved to reduce emissions, but as of 2005 the primary release of technetium-99 into the environment is by the Sellafield plant, which released an estimated 550 TBq (about 900 kg) from 1995–1999 into the Irish Sea. From 2000 onwards the amount has been limited by regulation to 90 TBq (about 140 kg) per year.[3]

In the environment

The long half-life of technetium-99 and its ability to form an anionic species make it (along with 129I) a major concern when considering long-term disposal of high-level radioactive waste. Many of the processes designed to remove fission products from medium-active process streams in reprocessing plants are designed to remove cationic species like caesium (e.g., 137Cs, 134Cs) and strontium (e.g., 90Sr). Hence the pertechnetate escapes through these treatment processes. Current disposal options favor burial in geologically stable rock. The primary danger with such a course is that the waste is likely to come into contact with water, which could leach radioactive contamination into the environment. The natural cation-exchange capacity of soils tends to immobilize plutonium, uranium, and caesium cations. However, the anion-exchange capacity is usually much smaller, so minerals are less likely to adsorb the pertechnetate and iodide anions, leaving them mobile in the soil. For this reason, the environmental chemistry of technetium is an active area of research.

In 2012 the crystalline compound Notre Dame Thorium Borate-1 (NDTB-1) was presented by researchers at the University of Notre Dame. It can be tailored to safely absorb radioactive ions from nuclear waste streams. Once captured, the radioactive ions can then be exchanged for higher-charged species of a similar size, recycling the material for re-use. Lab results using the NDTB-1 crystals removed approximately 96 percent of technetium-99.[4][5]

Separation of technetium-99

Several methods have been proposed for technetium-99 separation including: crystallization,[6][7] liquid-liquid extraction,[8][9][10] molecular recognition methods,[11] volatilization , and others.

Transmutation of technetium to stable ruthenium-100

An alternative disposal method, transmutation, has been demonstrated at CERN for technetium-99. This transmutation process bombards the technetium (99
Tc as a metal target) with neutrons, forming the short-lived 100
Tc (half-life 16 seconds) which decays by beta decay to stable ruthenium (100
Ru). Given the relatively high market value of Ruthenium[12] and the particularly undesirable properties of Technetium, this type of nuclear transmutation appears particularly promising.

See also

References

  1. ↑ "Cumulative Fission Yields". IAEA. Retrieved 18 December 2020.
  2. 1 2 K. Yoshihara, "Technetium in the Environment" in "Topics in Current Chemistry: Technetium and Rhenium", vol. 176, K. Yoshihara and T. Omori (eds.), Springer-Verlag, Berlin Heidelberg, 1996.
  3. ↑ Tagami, Keiko (2003). "Technetium-99 Behavior in the Terrestrial Environment". Journal of Nuclear and Radiochemical Sciences. 4 (1): A1–A8. doi:10.14494/jnrs2000.4.A1. ISSN 1345-4749.
  4. ↑ William G. Gilroy (Mar 20, 2012). "New Method for Cleaning Up Nuclear Waste". Science Daily.
  5. ↑ Wang, Shuao; Yu, Ping; Purse, Bryant A.; Orta, Matthew J.; Diwu, Juan; Casey, William H.; Phillips, Brian L.; Alekseev, Evgeny V.; Depmeier, Wulf; Hobbs, David T.; Albrecht-Schmitt, Thomas E. (2012). "Selectivity, Kinetics, and Efficiency of Reversible Anion Exchange with TcO4− in a Supertetrahedral Cationic Framework". Advanced Functional Materials. 22 (11): 2241–2250. doi:10.1002/adfm.201103081. S2CID 96158262.
  6. ↑ Xie, Rongzhen; Shen, Nannan; Chen, Xijian; Li, Jie; Wang, Yaxing; Zhang, Chao; Xiao, Chengliang; Chai, Zhifang; Wang, Shuao (2021-05-03). "99 TcO 4 – Separation through Selective Crystallization Assisted by Polydentate Benzene-Aminoguanidinium Ligands". Inorganic Chemistry. 60 (9): 6463–6471. doi:10.1021/acs.inorgchem.1c00187. ISSN 0020-1669.
  7. ↑ Volkov, Mikhail A.; Novikov, Anton P.; Grigoriev, Mikhail S.; Kuznetsov, Vitaly V.; Sitanskaia, Anastasiia V.; Belova, Elena V.; Afanasiev, Andrey V.; Nevolin, Iurii M.; German, Konstantin E. (January 2023). "New Preparative Approach to Purer Technetium-99 Samples—Tetramethylammonium Pertechnetate: Deep Understanding and Application of Crystal Structure, Solubility, and Its Conversion to Technetium Zero Valent Matrix". International Journal of Molecular Sciences. 24 (3): 2015. doi:10.3390/ijms24032015. ISSN 1422-0067. PMC 9916763.
  8. ↑ Bulbulian, S. (1984-11-01). "Methyl ethyl ketone extraction of Tc species". Journal of Radioanalytical and Nuclear Chemistry. 87 (6): 389–395. doi:10.1007/BF02166797. ISSN 1588-2780.
  9. ↑ Moir, D. L.; Joseph, D. L. (June 1997). "Determination of99Tc in fuel leachates using extraction chromatography". Journal of Radioanalytical and Nuclear Chemistry. 220 (2): 195–199. doi:10.1007/bf02034855. ISSN 0236-5731.
  10. ↑ Kołacińska, Kamila; Samczyński, Zbigniew; Dudek, Jakub; Bojanowska-Czajka, Anna; Trojanowicz, Marek (July 2018). "A comparison study on the use of Dowex 1 and TEVA-resin in determination of 99Tc in environmental and nuclear coolant samples in a SIA system with ICP-MS detection". Talanta. 184: 527–536. doi:10.1016/j.talanta.2018.03.034.
  11. ↑ Paučová, Veronika; Remenec, Boris; Dulanská, Silvia; Mátel, Ľubomír; Prekstová, Martina (2012-08-01). "Determination of 99Tc in soil samples using molecular recognition technology product AnaLig® Tc-02 gel". Journal of Radioanalytical and Nuclear Chemistry. 293 (2): 675–677. doi:10.1007/s10967-012-1710-5. ISSN 1588-2780.
  12. ↑ "Daily Metal Price: Ruthenium Price Chart (USD / Kilogram) for the Last 2 years".
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