Applications of Transuranics as Tracers and Chronometers in the Environment

  • Michael E. KettererEmail author
  • Jian Zheng
  • Masatoshi Yamada
Part of the Advances in Isotope Geochemistry book series (ADISOTOPE)


The transuranic elements (TRU) Np, Pu, Am, and Cm have prominently emerged as powerful tracers of earth and environmental processes, applicable to the recent, post nuclear-era timescale. Various long-lived isotopes of these elements are found in the earth’s surface environment, almost exclusively as a result of nuclear weapons production, testing, or nuclear fuel cycle activities. A globally recognizable signal, of consistent composition, from stratospheric fallout derived from 1950–1960 above-ground weapons tests is itself useful in tracing applications; in specific local/regional settings, stratospheric fallout is mixed with or dominated by other TRU sources with contrasting isotopic signatures. Both decay-counting and MS approaches have been utilized to measure the concentrations and isotopic ratios of TRU and are useful as discriminators for source characterization, provenance, and apportionment. Examples include the activity ratios 238Pu/239+240Pu, 241Am/239+240Pu, and 241Pu/239+240Pu; atom ratios such as 240Pu/239Pu, 237Np/239Pu, 241Pu/239Pu, and 242Pu/239Pu are also used in this context. Of the TRU elements, Pu is by far the most widely studied; accordingly, this chapter mainly emphasizes the use of Pu activities and/or atom ratios as tracers and/or chronometers. Nevertheless, Pu is sometimes measured in combination with one or more isotopes of other elements. The TRU elements offer several prominent applications in environmental/geochemical tracing: (1) chronostratigraphy of sediments and related recent Holocene deposits; (2) using fallout TRU as quantitative probes of soil erosion, transport and deposition; (3) investigating water mass circulation, the transport and scavenging of particulate matter, and tracking the marine geochemical behavior of the TRU elements themselves in the marine environment; and (4) studies of the local/regional transport, deposition and inventories of non-fallout TRU in the surficial environment.


Thermal Ionization Mass Spectrometry Alpha Spectrometry Global Fallout Tsushima Basin Fallout Deposition 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



The authors thank J.W. Mietelski for providing the alpha spectrum shown in Fig. 20.3. The authors are indebted to J.W. Mietelski, T.C. Kenna, one anonymous reviewer, and the editorship of M. Baskaran for constructive criticisms of the manuscript. MEK acknowledges ICPMS instrumentation support from Intel Corp., NSF MRI Award No. CHE0118604, and the State of Arizona Technology Research and Innovation Fund. MEK also owes thanks for nearly two decades of rich and productive interactions with many students and collaborators, and is gratefully indebted to JAK for perspective and inspiration towards facing apparent difficulties in life.


  1. Agarande M, Benzoubir S, Bouisset P et al (2001) Determination of 241Am in sediments by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS). Appl Radiat Isot 55:161–165Google Scholar
  2. Baskaran M, Santschi PH (2002) Particulate and dissolved 210Pb activities in the shelf and slope regions of the Gulf of Mexico waters. Continent Shelf Res 22:1493–1510Google Scholar
  3. Baskaran M, Asbill S, Santschi P et al (1995) Distribution of 239,240Pu and 238Pu concentrations in sediments from the Ob and Yenisey Rivers and the Kara Sea. Appl Radiat lsot 46:1109–1119Google Scholar
  4. Baskaran M, Asbill S, Santschi P et al (1996) Pu, 137Cs and excess 210Pb in Russian Arctic sediments. Earth Planet Sci Lett 140:243–257Google Scholar
  5. Baskaran M, Hong G-H, Santschi PH (2009) Radionuclide analysis in seawater. In: Wurl O (ed) Practical guidelines for the analysis of seawater. CRC, Boca Raton, FLGoogle Scholar
  6. Beck HL, Bennett BG (2002) Historical overview of atmospheric nuclear weapons testing and estimates of fallout in the continental United States. Health Phys 82:591–608Google Scholar
  7. Becker JS, Zoriy M, Halicz L et al (2004) Environmental monitoring of plutonium at ultratrace level in natural water (Sea of Galilee – Israel) by ICP-SFMS and MC-ICP-MS. J Anal At Spectrom 19:1–6Google Scholar
  8. Bennett BG (2002) Worldwide dispersion and deposition of radionuclides produced in atmospheric tests. Health Phys 82:644–655Google Scholar
  9. Bertine KK, Chow TJ, Koide M et al (1986) Plutonium isotopes in the environment: some existing problems and some new ocean results. J Environ Radioact 3:189–201Google Scholar
  10. Boulyga SF, Zoriy M, Ketterer ME et al (2003) Depth profiling of Pu, 241Am and 137Cs in soils from southern Belarus measured by ICP-MS and a and γ spectrometry. J Environ Monit 5:661–666Google Scholar
  11. Bowen VT, Noshkin VE, Livingston HD et al (1980) Fallout radionuclides in the Pacific Ocean: vertical and horizontal distributions, largely from GEOSEC stations. Earth Planet Sci Lett 49:411–434Google Scholar
  12. Buesseler KO (1996) The isotopic signature of fallout plutonium in the north Pacific. J Environ Radioact 36:69–83Google Scholar
  13. Carter MW, Moghissi AA (1977) Three decades of nuclear testing. Health Phys 33:55–71Google Scholar
  14. Chen Q, Dahlgaard H, Nielsen SP et al (2002) 242Pu as tracer for simultaneous determination of 237Np and 239,240Pu in environmental samples. J Radioanal Nucl Chem 253:451–458Google Scholar
  15. Chiappini R, Pointurier F, Millies-Lacroix JC et al (1999) 240Pu/239Pu isotopic ratios and 239+240Pu total measurements in surface and deep waters around Mururoa and Fangataufa atolls compared with Rangiroa atoll (French Polynesia). Sci Total Environ 237(238):269–276Google Scholar
  16. Choppin GR (2007) Actinide speciation in the environment. J Radioanal Nucl Chem 273:695–703Google Scholar
  17. Cizdziel JV, Ketterer ME, Farmer D et al (2008) 239,240,241Pu fingerprinting of plutonium in western US soils using ICPMS: solution and laser ablation measurements. Anal Bioanal Chem 390:521–530Google Scholar
  18. Curtis D, Fabryka-Martin J, Dixon P et al (1999) Nature’s uncommon elements: plutonium and technetium. Geochim Cosmochim Acta 63:275–285Google Scholar
  19. Dong W, Zheng J, Guo QJ et al (2010) Characterization of plutonium in deep-sea sediments of the Sulu and South China Seas. J Environ Radioact 101:622–629Google Scholar
  20. Everett SE, Tims SG, Hancock GJ et al (2008) Comparison of Pu and 137Cs as tracers of soil and sediment transport in a terrestrial environment. J Environ Radioact 99:383–393Google Scholar
  21. Fifield LK (2008) Accelerator mass spectrometry of the actinides. Quat Geochron 3:276–290Google Scholar
  22. Godoy MLDP, Godoy JM, Roldão LA (2007) Application of ICP-QMS for the determination of plutonium in environmental samples for safeguards purposes. J Environ Radioact 97:124–136Google Scholar
  23. Hardy EP, Volchok HL, Livingston HD et al (1980) Time pattern of off-site plutonium deposition from Rocky Flats plant by lake sediment analyses. Environ Int 4:21–30Google Scholar
  24. Harley JH (1980) Plutonium in the environment – a review. J Radiat Res 21:83–104Google Scholar
  25. Holm E, Roos P, Aarkrog A et al (2002) Curium isotopes in Chernobyl fallout. J Radioanal Nucl Chem 252:211–214Google Scholar
  26. Hong G-H (2011) Applications of anthropogenic radionuclides as tracers to investigate marine environmental processes. In: Baskaran M (ed) Handbook of environmental isotope geochemistry. Springer, HeidelbergGoogle Scholar
  27. Hotchkis MAC, Child D, Fink D et al (2000) Measurement of 236U in environmental media. Nucl Instrum Meth Phys Res B 172:659–665Google Scholar
  28. Huh CA, Su CC (2004) Distribution of fallout radionuclides (7Be, 137Cs, 210Pb and 239,240Pu) in soils of Taiwan. J Environ Radioact 77:87–100Google Scholar
  29. Jaakkola T, Tolonen K, Huttunen P et al (1983) The use of fallout 137Cs and 239,240Pu for dating of lake sediments. Hydrobiology 103:15–19Google Scholar
  30. Kaste JM, Heimsath AM, Hohmann M (2006) Quantifying sediment transport across an undisturbed prairie landscape using cesium-137 and high resolution topography. Geomorpholgy 76:430–440Google Scholar
  31. Kelley JM, Bond LA, Beasley TM (1999) Global distribution of Pu isotopes and 237Np. Sci Total Environ 237(238):483–500Google Scholar
  32. Kenna TC (2002) Determination of plutonium isotopes and neptunium-237 in environmental samples by inductively coupled plasma mass spectrometry with total sample dissolution. J Anal At Spectrom 17:1471–1479Google Scholar
  33. Kenna TC, Sayles FL (2002) The distribution and history of nuclear weapons related contamination in sediments from the Ob River, Siberia as determined by isotopic ratios of plutonium and neptunium. J Environ Radioact 60:105–137Google Scholar
  34. Kershaw PJ, McCubbin D, Leonard KS (1999) Continuing contamination of north Atlantic and Arctic waters by Sellafield radionuclides. Sci Total Environ 237(238):119–132Google Scholar
  35. Ketterer ME, Szechenyi SC (2008) Determination of plutonium and other transuranic elements by inductively coupled plasma mass spectrometry: a historical perspective and new frontiers in the environmental sciences. Spectrochim Acta B 63:719–737Google Scholar
  36. Ketterer ME, Watson BR, Matisoff G et al (2002) Rapid dating of recent aquatic sediments using Pu activities and 240Pu/239Pu as determined by quadrupole inductively coupled plasma mass spectrometry. Environ Sci Technol 36:1307–1311Google Scholar
  37. Ketterer ME, Hafer KM, Jones VJ et al (2004a) Rapid dating of recent sediments in Loch Ness: inductively coupled plasma mass spectrometric measurements of global fallout plutonium. Sci Total Environ 322:221–229Google Scholar
  38. Ketterer ME, Hafer KM, Mietelski JW (2004b) Resolving Chernobyl vs. global fallout contributions in soils from Poland using Plutonium atom ratios measured by inductively coupled plasma mass spectrometry. J Environ Radioact 73:183–201Google Scholar
  39. Kim CK, Kim CS, Chang BU et al (2004) Plutonium isotopes in seas around the Korean Peninsula. Sci Total Environ 318:197–209Google Scholar
  40. Kim CS, Kim CK, Martin P et al (2007) Determination of plutonium concentrations and isotope ratio by inductively coupled plasma mass spectrometry: a review of analytical methodology. J Anal At Spectrom 22:827–841Google Scholar
  41. Koide M, Bertine KK, Chow TJ et al (1985) The 240Pu/239Pu ratio, a potential geochronometer. Earth Planet Sci Lett 72:1–8Google Scholar
  42. Krey PW, Leifer R, Benson WK et al (1979) Atmospheric burn-up of the Cosmos-954 reactor. Science 205:583–585Google Scholar
  43. Lariviere D, Taylor VF, Evans RD et al (2006) Radionuclide determination in environmental samples by inductively coupled plasma mass spectrometry. Spectrochim Acta B 61:877–904Google Scholar
  44. Lee T, Teh-Lung K, Hsiao-Ling L et al (1993) First detection of fallout Cs-135 and potential applications of 137Cs/135Cs ratios. Geochim Cosmochim Acta 57:3493–3497Google Scholar
  45. Lee S, Huh C, Su C et al (2004) Sedimentation in the Southern Okinawa Trough: enhanced particle scavenging and teleconnection between the Equatorial Pacific and western Pacific margins. Deep Sea Res I 51:1769–1780Google Scholar
  46. Liao H, Zheng J, Wu F et al (2008) Determination of plutonium isotopes in freshwater lake sediments by sector-field ICP-MS after separation using ion-exchange chromatography. Appl Radiat Isot 66:1138–1145Google Scholar
  47. Lindahl P, Lee S, Worsfold P et al (2010) Plutonium isotopes as tracers for ocean processes: a review. Mar Environ Res 69:73–84Google Scholar
  48. Livingston HD, Povinec PP (2002) A millennium perspective on the contribution of global fallout radionuclides to ocean science. Health Phys 82:656–668Google Scholar
  49. Mackereth FJH (1969) A short core sampler for sub-aqueous deposits. Limnol Oceanogr 14:145–151Google Scholar
  50. Masqué P, Cochran JK, Hebbeln D et al (2003) The role of sea ice in the fate of contaminants in the Arctic Ocean: plutonium atom ratios in the Fram Strait. Environ Sci Technol 37:4848–4854Google Scholar
  51. Matisoff G, Whiting PJ (2011) Measuring soil erosion rates using natural (7Be, 210Pb) and anthropogenic (137Cs, 239,240Pu) radionuclides. In: Baskaran M (ed) Handbook of environmental isotope geochemistry. Springer, HeidelbergGoogle Scholar
  52. Maxwell SL III (2008) Rapid method for determination of plutonium, americium and curium in large soil samples. J Radioanal Nucl Chem 275:395–402Google Scholar
  53. Mietelski JW, Was B (1995) Plutonium from Chernobyl in Poland. Appl Radiat Isot 46:1203–1211Google Scholar
  54. Mietelski JW, Was B (1997) Americium, curium and rare earths radionuclides in forest litter samples from Poland. Appl Radiat lsot 48:705–713Google Scholar
  55. Mietelski JW, Dorda J, Was B (1999) Pu-241 in samples of forest soil from Poland. Appl Radiat lsot 51:435–447Google Scholar
  56. Miller AJ, Kuehl SA (2009) Shelf sedimentation on a tectonically active margin: a modern sediment budget for poverty continental shelf, New Zealand. Mar Geol 270:175–187Google Scholar
  57. Montero PR, Sanchez AM (2001) Plutonium contamination from accidental release or simply fallout: study of soils at Palomares (Spain). J Environ Radioact 55:157–165Google Scholar
  58. Morris K, Butterworth JC, Livens FR (2000) Evidence for the remobilization of Sellafield waste radionuclides in an intertidal salt Marsh, West Cumbria, U.K. Estuar Coast Shelf Sci 51:613–625Google Scholar
  59. Muramatsu Y, Hamilton T, Uchida S et al (2001) Measurement of 240Pu/239Pu isotopic ratios in soils from the Marshall Islands using ICP-MS. Sci Total Environ 278:151–159Google Scholar
  60. Myers WA, Lindner M (1971) Precise determination of the natural abundance of 237Np and 239Pu in Katanga pitchblende. J Inorg Nucl Chem 33:3233–3238Google Scholar
  61. Nelson DM, Lovett MB (1978) Oxidation state of plutonium in the Irish Sea. Nature 276:599–601Google Scholar
  62. Nesje A (1992) A piston corer for lacustrine and marine sediments. Arctic Alpine Res 24:257–259Google Scholar
  63. Nunnemann M, Erdmann N, Hasse H-U et al (1998) Trace analysis of plutonium in environmental samples by resonance ionization mass spectroscopy (RIMS). J Alloy Comp 271–273:45–48Google Scholar
  64. Nygren U, Rodushkin I, Nilsson C et al (2003) Separation of plutonium from soil and sediment prior to determination by inductively coupled plasma mass spectrometry. J Anal At Spectrom 18:1426–1434Google Scholar
  65. Ofan A, Ahmad I, Greene JP et al (2006) Development of a detection method for 244Pu by resonance ionization mass spectrometry. New Astron Rev 50:640–643Google Scholar
  66. Olivier S, Bajo S, Fifield LK et al (2004) Plutonium from global fallout recorded in an ice core from the Belukha Glacier, Siberian Altai. Environ Sci Technol 38:6507–6512Google Scholar
  67. Pöllänen R, Ketterer ME, Lehto S et al (2006) Multi-technique characterization of a nuclear bomb particle from the Palomares accident. J Environ Radioact 90:15–28Google Scholar
  68. Povinec PP, Badie C, Baeza A et al (2002) Certified reference material for radionuclides in seawater IAEA-381 (Irish Sea Water). J Radioanal Nucl Chem 251:369–374Google Scholar
  69. Ravichandran M, Baskaran M, Santschi PH et al (1995) Geochronology of sediments in the Sabine-Neches estuary, Texas, USA. Chem Geol 125:291–306Google Scholar
  70. Reynolds RL, Mordecai JS, Rosenbaum JG et al (2010) Compositional changes in sediments of subalpine lakes, Uinta Mountains (Utah): evidence for the effects of human activity on atmospheric dust inputs. J Paleolimnol 44:161–175Google Scholar
  71. Ritchie JC, McHenry JR (1990) Application of radioactive fallout cesium-137 for measuring soil erosion and sediment accumulation rates and patterns: a review. J Environ Qual 19:215–233Google Scholar
  72. Roy JC, Turcotte J, Cote JE et al (1981) The detection of the 21st Chinese nuclear explosion in eastern Canada. Health Phys 41:449–454Google Scholar
  73. Sam AK, Ahamed MMO, Khangi FE et al (2000) Plutonium isotopes in sediments from the Sudanese coast of the Red Sea. J Radioanal Nucl Chem 245:411–414Google Scholar
  74. Sanders CJ, Smoak JM, Sanders LM et al (2010) Intertidal mangrove mudflat 240+239Pu signatures, confirming a 210Pb geochronology on the southeastern coast of Brazil. J Radioanal Nucl Chem 283:593–596Google Scholar
  75. Schiff CJ, Kaufman DS, Wallace KL et al (2010) An improved proximal tephrochronology for Redoubt Volcano, Alaska. J Volcanol Geoth Res 193:203–214Google Scholar
  76. Schneider DL, Livingston HD (1984) Measurement of curium in marine samples. Nucl Instrum Meth Phys Res 223:510–516Google Scholar
  77. Sholkovitz ER (1983) The geochemistry of Pu in fresh and marine water environments. Earth Sci Rev 19:95–161Google Scholar
  78. Sill CW (1975) Some problems in measuring plutonium in the environment. Health Phys 29:619–626Google Scholar
  79. Skipperud L (2004) Plutonium in the arctic marine environment – a short review. Sci World J 4:460–481Google Scholar
  80. Taylor DM (1995) Environmental plutonium in humans. Appl Radiat Isot 46:1245–1252Google Scholar
  81. Taylor DM (2001) Environmental plutonium – creation of the universe to twenty-first century mankind. In: Kudo A (ed) Plutonium in the environment. Elsevier Science, AmsterdamGoogle Scholar
  82. Taylor RN, Warneke T, Milton JA et al (2001) Plutonium isotope ratio analysis at femtogram to nanogram levels by multicollector ICP-MS. J Anal At Spectrom 16:279–284Google Scholar
  83. Thakkar AH (2002) A rapid sequential separation of actinides using Eichrom’s extraction chromatographic material. J Radioanal Nucl Chem 252:215–218Google Scholar
  84. Tims SG, Pan SM, Zhang R (2010) Plutonium AMS measurements in Yangtze River estuary sediment. Nucl Instrum Meth Phys Res B 268:1155–1158Google Scholar
  85. Ulsh B, Rademacher S, Whicker FW (2000) Variations of 137Cs depositions and soil concentrations between alpine and montane soils in northern Colorado. J Environ Radioact 47:57–70Google Scholar
  86. Vajda N, Kim C (2010) Determination of Pu isotopes by alpha spectrometry: a review of analytical methodology. J Radioanal Nucl Chem 283:203–223Google Scholar
  87. Van Pelt RS, Ketterer ME, Zobeck T et al. Anthropogenic radioisotopes to estimate rates of soil redistribution by wind (manuscript in preparation)Google Scholar
  88. Wallner C, Faestermann T, Gerstmann U et al (2004) Supernova produced and anthropogenic 244Pu in deep sea manganese encrustations. New Astron Rev 48:145–150Google Scholar
  89. Warwick PE, Croudace IW, Carpenter R (1996) Review of analytical techniques for the determination of americium-241 in soils and sediments. Appl Radiat lsot 47:627–642Google Scholar
  90. Yamada M, Aono T (2002) Large particle flux of 239+240Pu on the continental margin of the East China Sea. Sci Total Environ 287:97–105Google Scholar
  91. Yamada M, Zheng J (2010) Temporal variability of 240Pu/239Pu atom ratio and 239+240Pu inventory in water columns of the Japan Sea. Sci Total Environ 408:5951–5957Google Scholar
  92. Yamada M, Zheng J, Wang Z (2006) 137Cs, 239 + 240Pu and 240Pu / 239Pu atom ratios in the surface waters of the western North Pacific Ocean, eastern Indian Ocean and their adjacent seas. Sci Total Environ 366:242–252Google Scholar
  93. Zheng J, Yamada M (2004) Sediment core record of global fallout and bikini close-in fallout Pu in Sagami Bay, Western Northwest Pacific Margin. Environ Sci Technol 38:3498–3504Google Scholar
  94. Zheng J, Yamada M (2005) Vertical distributions of 239+240Pu activities and 240Pu/239Pu atom ratios in sediment cores: implications for the sources of Pu in the Japan Sea. Sci Total Environ 340:199–211Google Scholar
  95. Zheng J, Yamada M (2006a) Inductively coupled plasma-sector field mass spectrometry with a high-efficiency sample introduction system for the determination of Pu isotopes in settling particles at femtogram levels. Talanta 69:1246–1253Google Scholar
  96. Zheng J, Yamada M (2006b) Determination of Pu isotopes in sediment cores in the Sea of Okhotsk and the NW Pacific by sector field ICP-MS. J Radioanal Nucl Chem 267:73–83Google Scholar
  97. Zheng J, Yamada M (2006c) Plutonium isotopes in settling particles: transport and scavenging of Pu in the western northwest Pacific. Environ Sci Technol 40:4103–4108Google Scholar
  98. Zheng J, Yamada M (2007) Precise determination of Pu isotopes in a seawater reference material using ID-SF-ICP-MS combined with two-stage anion-exchange chromatography. Anal Sci 23:611–615Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2012

Authors and Affiliations

  • Michael E. Ketterer
    • 1
    Email author
  • Jian Zheng
    • 2
  • Masatoshi Yamada
    • 2
  1. 1.Department of Chemistry and BiochemistryNorthern Arizona UniversityFlagstaffUSA
  2. 2.Environmental Radiation Effects Research GroupNational Institute of Radiological SciencesChibaJapan

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