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Adaptation of an Analytical Procedure for Concurrent Determination of Np and Pu in clay samples

Published online by Cambridge University Press:  01 January 2024

Tobias Renz ,
Markus Plaschke ,
Francesca Quinto ,
Andreas Bauer ,
Markus Lagos ,
Heinrich Taubald  and
Horst Geckeis
Tobias Renz*
Affiliation:
Institute for Nuclear Waste Disposal, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany Department of Geoscience, University of Tuebingen, Wilhelmstraße 56, 72074, Tübingen, Germany
Markus Plaschke
Affiliation:
Institute for Nuclear Waste Disposal, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany
Francesca Quinto
Affiliation:
Institute for Nuclear Waste Disposal, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany
Andreas Bauer
Affiliation:
Institute for Nuclear Waste Disposal, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany
Markus Lagos
Affiliation:
Steinmann Institute, University of Bonn, Poppelsdorfer Schloss, 53115, Bonn, Germany
Heinrich Taubald
Affiliation:
Department of Geoscience, University of Tuebingen, Wilhelmstraße 56, 72074, Tübingen, Germany
Horst Geckeis
Affiliation:
Institute for Nuclear Waste Disposal, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany
*
*E-mail address of corresponding author: tobias.renz@web.de
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Abstract

Np and Pu are two important actinides of concern for the safe long-term disposal of nuclear waste. Both actinides are, in addition, constituents of global nuclear fallout. Investigation of their environmental behavior requires ultra-sensitive analytical methods, but current methods for a concurrent determination in clay minerals are lacking. In the present study, a Pu isotope was investigated for use as a non-isotopic yield tracer for Np in extraction, purification, and mass spectrometric determination of Np and Pu isotopes in clay materials. Inductively coupled plasma mass spectrometry was used in this developmental study, but the method is intended for future ultra-trace analysis of global-fallout Np and Pu in clay-rich soil materials by the more sensitive accelerator mass spectrometry. Another field of application may be the investigation of diffusion patterns of actinides in compacted clay liners and potential host rocks for radioactive waste disposal. The analytical procedure includes the following steps: (1) extraction of Np and Pu from clay samples; (2) adjustment of Np and Pu to Np(IV) and Pu(III); (3) pre-concentration of Np and Pu by co-precipitation with iron hydroxide; (4) adjustment of Pu to Pu(IV); (5) extraction chromatographic separation of Pu and Np from iron and matrix elements; and (6) determination of Np and Pu by mass spectrometry. The analytical procedure was applied successfully to spiked montmorillonite and illite test portions of up to 1 g. High chemical yields near 90% were obtained for both Np and Pu. The suitability of Pu as a non-isotopic tracer for Np was indicated by Np/Pu chemical yield ratios close to unity. Accurate pH adjustment during the reductive co-precipitation and short processing times are vital to obtain high chemical yields and Np/Pu yield ratios close to unity.

Keywords

ClayExtraction ChromatographyICP-MSNeptuniumNon-isotopic TracerPlutonium
Type
Original Paper
Information
Clays and Clay Minerals , Volume 67 , Issue 3 , June 2019 , pp. 183 - 189
Copyright
Copyright © Clay Minerals Society 2019

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References

Chen, Q., Dahlgaard, H., Nielsen, S. P., & Aarkrog, A. (2002). 242Pu as tracer for simultaneous determination of 237Np and 239,240Pu in environmental samples. Journal of Radioanalytical and Nuclear Chemistry, 253, 451–458.CrossRefGoogle Scholar
Chen, Q., Dahlgaard, H., Nielsen, S. P., Aarkrog, A., Christensen, I., & Jensen, A. (2001). Determination of 237Np in marine sediment and seawater. Journal of Radioanalytical and Nuclear Chemistry, 249, 527–533.Google Scholar
Dai, X., Christl, M., Kramer-Tremblay, S., & Synal, H.-A. (2015). Ultra-trace determination of neptunium-237 and plutonium isotopes in urine samples by compact accelerator mass spectrometry. CNL Nuclear Review, 4, 125–130.Google Scholar
Denecke, M. A., Bryan, N., Kalmykov, S., Morris, K., & Quinto, F. (2018). Sources and behaviour of actinide elements in the environment. In Gibson, J. K. & de Jong, W. A., (Eds.), Experimental and theoretical approaches to actinide chemistry (pp. 378–444) New Jersey, USA: Wiley, HobokenCrossRefGoogle Scholar
Jerome, S. M., Carney, K., Essex, R., Fassbender, M. E., Goldberg, S., Kinlaw, M., LaMont, S. P., Mackney, D., Morrison, J. J., & Nortier, F. M. (2017). Reference materials for neptunium determination. Applied Radiation and Isotopes, 126, 44–48.CrossRefGoogle ScholarPubMed
Kim, C. S., Kim, C. K., & Lee, K. J. (2004). Simultaneous analysis of 237Np and Pu isotopes in environmental samples by ICP-SF-MS coupled with automated sequential injection system. Journal of Analytical Atomic Spectrometry, 19, 743–750.CrossRefGoogle Scholar
Kim, J.-I. (2006). Significance of actinide chemistry for the long-term safety of waste disposal. Nuclear Engineering and Technology, 38, 459–482.Google Scholar
Matteson, B. S., Hanson, S. K., Miller, J. L., & Oldham, W. J. Jr. (2015). Concurrent determination of 237Np and Pu isotopes using ICP-MS: Analysis of NISTenvironmental matrix standard reference materials 4357, 1646a, and 2702. Journal of Environmental Radioactivity, 142, 62–67.CrossRefGoogle ScholarPubMed
Qiao, J., Hou, X., Roos, P., & Miró, M. (2010). Rapid and simultaneous determination of neptunium and plutonium isotopes in environmental samples by extraction chromatography using sequential injection analysis and ICP-MS. Journal of Analytical Atomic Spectrometry, 25, 1769–1779.CrossRefGoogle Scholar
Qiao, J., Hou, X., Roos, P., & Miró, M. (2011a). High-throughput sequential injection method for simultaneous determination of plutonium and neptunium in environmental solids using macroporous anion-exchange chromatography, followed by inductively coupled plasma mass spectrometric detection. Analytical Chemistry, 83, 374–381.CrossRefGoogle ScholarPubMed
Qiao, J., Hou, X., Roos, P., & Miró, M. (2011b). Reliable determination of 237Np in environmental solid samples using 242Pu as a potential tracer. Talanta, 84, 494–500.CrossRefGoogle ScholarPubMed
Qiao, J., Hou, X., & Roos, P. (2013a). Method for determination of neptunium in large-sized urine samples using manganese dioxide coprecipitation and 242Pu as yield tracer. Analytical Chemistry, 85, 1889–1895.CrossRefGoogle ScholarPubMed
Qiao, J., Hou, X., Roos, P., Lachner, J., Christl, M., & Xu, Y. (2013b). Sequential injection approach for simultaneous determination of ultratrace plutonium and neptunium in urine with accelerator mass spectrometry. Analytical Chemistry, 85, 8826–8833.CrossRefGoogle ScholarPubMed
Qiao, J., Hou, X., Steier, P., & Golser, R. (2013c). Sequential injection method for rapid and simultaneous determination of 236U, 237Np, and Pu isotopes in seawater. Analytical Chemistry, 85, 11026–11033.CrossRefGoogle ScholarPubMed
Quinto, F., Hrnecek, E., Krachler, M., Shotyk, W., Steier, P., & Winkler, S. R. (2013a). Determination of 239Pu, 240Pu, 241Pu and 242Pu at femtogram and attogram levels – evidence for the migration of fallout plutonium in an ombrotrophic peat bog profile. Environmental Science: Processes & Impacts, 15, 839–847.Google Scholar
Quinto, F., Hrnecek, E., Krachler, M., Shotyk, W., Steier, P., & Winkler, S. R. (2013b). Measurements of 236U in ancient and modern peat samples and implications for postdepositional migration of fallout radionuclides. Environmental Science & Technology, 47, 5243–5250.CrossRefGoogle ScholarPubMed
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