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Determination of complex formation constants of neptunium(V) with propionate and lactate in 0.5–2.6 m NaCl solutions at 22–60°C using a solvent extraction technique

  • Aleksandr N. Vasiliev , Nidhu L. Banik , Rémi Marsac , Stepan N. Kalmykov and Christian M. Marquardt EMAIL logo
Published/Copyright: May 21, 2019
Radiochimica Acta
From the journal Radiochimica Acta Volume 107 Issue 7

Abstract

Natural clay rocks like Opalinus (OPA) and Callovo-Oxfordian (COx) clay rock are considered as potential host rocks for deep geological disposal of nuclear waste. However, small organic molecules such as propionate and lactate exist in clay rock pore water and might enhance Np mobility through a complexation process. Therefore, reliable complex formation data are required in the frame of the Safety Case for a nuclear waste repository. A solvent extraction technique was applied for the determination of NpO2+ complexation with propionate and lactate. Extraction was conducted from isoamyl alcohol solution containing 10−3 M TTA and 5 · 10−4 M 1,10-phenanthroline. Experiments were performed in 0.5–2.6 m NaCl solutions at temperatures ranging from 22 to 60 °C. Formation of 1:1 Np(V) complexes for propionate and lactate was found under the studied conditions. The SIT approach was applied to calculate equilibrium constants β°(T) at zero ionic strength from the experimental data. Log β°(T) is found linearly correlated to 1/T for propionate and lactate, evidencing that heat capacity change is near 0. Molal reaction enthalpy and entropy (ΔrHm∘ and ΔrSm∘) could therefore be derived from the integrated van’t Hoff equation. Data for log β° (298.15 K) are in agreement with literature values for propionate and lactate. Np(V) speciation was calculated for concentrations of acetate, propionate and lactate measured in clay pore waters of COx. In addition, the two site protolysis non-electrostatic surface complexation and cation exchange (2SPNE SC/CE) model was applied to quantitatively describe the influence of Np(V) complexation on its uptake on Na-illite, a relevant clay mineral of OPA and COx.

Keywords: Np(V); complexation; complex formation constant; lactate; propionate; solvent extraction

Dedicated to: The memory of Professor Günter Herrmann.

Acknowledgements

Günter Herrmann was my (C.M. Marquardt) doctoral thesis supervisor. In those days he gave me the opportunity to work in the framework of a R&D Programme of the European Commission on Management of Radioactive Waste and Storage. The here presented work shows that this scientific issue is still up-to-date and that I remained true to this branch of science to date. This work has been supported by the German Federal Ministry of Economic Affairs and Energy (BMWi) under Contract No. 02E10961 and German Academic Exchange Service (DAAD). Bundesministerium für Wirtschaft und Technologie.

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Received: 2019-01-17
Accepted: 2019-04-01
Published Online: 2019-05-21
Published in Print: 2019-07-26

©2019 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Preface
  3. Günter Herrmann (1925–2017): A tribute to his research and organizational achievements
  4. The research reactor TRIGA Mainz – a strong and versatile neutron source for science and education
  5. Copper-catalyzed click reactions: quantification of retained copper using 64Cu-spiked Cu(I), exemplified for CuAAC reactions on liposomes
  6. Reactions of fission products from a 252Cf source with NO and mixtures of NO and CO in an inert gas
  7. From SRAFAP to ARCA and AIDA – developments and implementation of automated aqueous-phase rapid chemistry apparatuses for heavy actinides and transactinides
  8. Production and study of chemical properties of superheavy elements
  9. Precise ground state properties of the heaviest elements for studies of their atomic and nuclear structure
  10. Modeling the sorption of Np(V) on Na-montmorillonite – effects of pH, ionic strength and CO2
  11. Determination of complex formation constants of neptunium(V) with propionate and lactate in 0.5–2.6 m NaCl solutions at 22–60°C using a solvent extraction technique
  12. Nuclear forensics on uranium fuel pellets
  13. Recent developments in resonance ionization mass spectrometry for ultra-trace analysis of actinide elements
  14. Measurement of the laser resonance ionization efficiency for lutetium
https://doi.org/10.1515/ract-2019-3107
Keywords for this article
Np(V); complexation; complex formation constant; lactate; propionate; solvent extraction

Articles in the same Issue

  1. Frontmatter
  2. Preface
  3. Günter Herrmann (1925–2017): A tribute to his research and organizational achievements
  4. The research reactor TRIGA Mainz – a strong and versatile neutron source for science and education
  5. Copper-catalyzed click reactions: quantification of retained copper using 64Cu-spiked Cu(I), exemplified for CuAAC reactions on liposomes
  6. Reactions of fission products from a 252Cf source with NO and mixtures of NO and CO in an inert gas
  7. From SRAFAP to ARCA and AIDA – developments and implementation of automated aqueous-phase rapid chemistry apparatuses for heavy actinides and transactinides
  8. Production and study of chemical properties of superheavy elements
  9. Precise ground state properties of the heaviest elements for studies of their atomic and nuclear structure
  10. Modeling the sorption of Np(V) on Na-montmorillonite – effects of pH, ionic strength and CO2
  11. Determination of complex formation constants of neptunium(V) with propionate and lactate in 0.5–2.6 m NaCl solutions at 22–60°C using a solvent extraction technique
  12. Nuclear forensics on uranium fuel pellets
  13. Recent developments in resonance ionization mass spectrometry for ultra-trace analysis of actinide elements
  14. Measurement of the laser resonance ionization efficiency for lutetium
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